Note: Descriptions are shown in the official language in which they were submitted.
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A NOVEL CATALYTIC FORMULATION AND ITS PREPARATION
TECHNICAL FIELD
The present invention relates to a new class of heterogeneous catalysts, the
methodology for which is useful in preparing solid catalysts for a variety of
chemical
reactions. Particularly, this invention relates to a catalyst system
comprising of chemical
formulation constituting an insoluble material having desired catalytic
properties and
support, assembled together by a specific technique. The said catalyst is
useful for
promoting reactions in gas or liquid phase. The unique feature of this
catalyst system is
that entire catalytic formulation remains as a composite solid material
without
disassembling during the course of reaction. The invention primarily describes
a technique
whereby soluble catalyst is converted to insoluble material by appropriate
molecular
modification. The invention further relates to preferred methods for
preparation of such
catalytic foimulations.
BACKGROiJND ART
Sol?.zble molecular catalysts, particularly complexes of transition metals are
well
known in the art. Such catalysts are also known to catalyze a variety of
useful organic
transformations. These transformations for instance include hydrogenation,
hydroformylation, carbonylation, amination, isomerization, telomerization,
Heck
olefination, Suzuki coupling, metathesis, epoxidation etc. Such
transformations find a
variety of useful applications for the synthesis of pharmaceuticals,
pesticides, solvents and
other valuable products of industrial and consumer significance.
Amongst the established practices known in the prior art, catalytically active
transition metal complexes have principally been applied in homogeneous form,
as
solution in a reactant phase. For example, in case of hydroformylation of
olefins using
rhodium and phosphine ligand complex catalyst wherein phosphine ligand is free
of ionic
charge such as tributyl phosphine, triphenyl phosphine" etc. and soluble in
the reaction
medium. Although such catalysts are highly effective, in terms of productivity
and
selectivity, its applicability on practical grounds is often limited to
volatile products. In
case of reactions catalyzed by homogeneous catalysts involving high molecular
weight and
especially nonvolatile products catalyst separation is a critical problem.
High cost of
catalyst, susceptibility to high temperatures and stringent product
specification demand
quantitative catalyst separation. Common unit operations such as distillation
and
crystallization are least significant since, organometallic complexes being
delicate in
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2
nature and cannot withstand separation stresses especially thermal stresses as
encountered
in distillation. Other separation techniques being inefficient in separating
such a small
quantity of catalyst cannot be used in effective manner. Moreover high purity
of the
product is of importance in products such as pharmaceuticals, demanding
rigorous
separation of catalyst from product stream. Thus use of homogeneous catalyst
as such has
suffered from inherent difficulties in the recovery of the catalysts from
reaction products.
Efficient catalyst recovery and recycle is the pivotal issue for the economic
viability of the
process since, complexes and ligands are often expensive.
It is also known in the art to use aqueous solutions of sulfonated aryl
phosphines
and many other water-soluble compounds and transition metal complex catalyst
derived
from it to effect reactions. As disclosed in patent (U.S. patent No.
4,248,802) all such
reactions are operated in biphasic conditions wherein catalyst phase is
aqueous and
products and reactants dissolved in organic phase. Similarly reverse biphasic
techniques
are also applicable wherein catalyst is dissolved in organic phase and product
and reactants
in aqueous phase. A judicious choice is necessary while utilizing biphasic
catalytic systems
depending upon solubility of reactants and products. In either case at the end
of reaction
catalyst and product phases are separated wherefore catalyst phase is recycled
and product
phase is directed for further downstream processing.
It is however recognized that catalytic activity is low in biphasic medium due
to
limited solubility of organic reactants in the catalyst phase. Moreover such
biphasic
reactions require high reactor pressure in case of gas-liquid reactions. To
achieve practical
rates of reactions catalyst loading has to be increased or alternatively using
larger process
equipment, which is usually cost prohibitive. Further, these reactions require
numerous
accessory equipment's to separate liquid-liquid fractions under reaction
conditions.
Over the past quarter of century many attempts have been made to heterogenize
this versatile class of soluble catalysts. Several methods were developed with
central theme
being retention of high activity and selectivity as that of native catalytic
species and
facilitate separation by simple filtration, centrifugation or gravity
settling.
One of the techniques to form a solid catalyst involves interaction of metal
salt or
precursor complex with solid support that is appropriately functionalized with
organic
functional groups that are capable of forming coordination bonds with metal.
The support
used in this context is either organic-polymeric or inorganic matrix. These
supports are
chemically functionalized to bear amino, phosphino and carboxylato functional
groups on
the surface of the support. Work related to this technique is described in,
Catalysis
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3
Reviews, 16, 17-37 (1974); Chemical Reviews, 81, 109, (1981); Tetrahedron
Asynzmetry, 6,
1109-1116 (1995); Tetrahedron Letters, 37, 3375-3378 (1996). "Catalysis by
supported
complexes", Studies in surface science and catalysis, volume 8, Elsevier
Publishing Co.
Amsterdam, 1981 describes the complexes grafted to inorganic supports.
From practical stand point these catalysts are not widely used since their
activities
are frequently lower than corresponding homogeneous catalysts in addition
there are
various complications that are inherent due to polymeric nature of the support
for example
swelling and shrinking of the matrix, which alters diffusion resistance. It is
also found that
in long run and upon exposure to oxygen metal attached to support is lost in
the solution
thereby degeneration of the activity of the catalyst.
Supported liquid phase catalyst such as those described in US patent 3,855,307
(1974) and US patent 4,994,427 (1991) are critically sensitive to the
character of the
reaction medium and are often leached in to reaction medium depending upon the
nature of
the solvent. The applicability of such catalyst is limited to only vapor phase
reactions. The
technique as described in US patent 4,994,427(1991) wherein solution of water-
soluble
catalyst is distributed on high surface area solid. The aqueous film of
catalyst containing
solution remains insoluble in nonpolar organic phase thus, after reaction
solid catalyst can
be recovered by simple filtration. Applicability of such catalyst is limited
to reactions
involving water insoluble reaction media. Moreover such catalysts are
sensitive to content
of water.
Entrapment of the catalyst in porous material such as zeolite has been
described by
Balkus, et al in J. Inclusion Plzenona. Mol. Recognit. Clzem., 21(1-4), 159-84
(English)
1995 The catalyst is encapsulated in three-dimensional network of zeolites
wherein,
catalyst because of size exclusion can not diffuse out of zeolite but smaller
sized reactants
diffuse inside the zeolite and products formed subsequently diffuse out. Yet
another article
J. Catal, 163(2), 457-464 1996 have described the method to entrap catalyst
within the
polymer matrix but because of diffusion resistance, catalyst efficiency is
doubtful.
Despite several known techniques for heterogenization of soluble molecular
catalysts there is no known method, which can be conveniently used for
diversity of
catalytic entities using a common protocol. Furthermore catalyst formed by
such protocol
is required to provide a solid catalyst that can be used for polar as well as
nonpolar reaction
media. Certainly a particular need exists for such technique of catalyst
formulation and
present invention is aimed to fulfill these needs.
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4 DISCLOSURE OF THE INVENTION
Importantly in the general as well as specific background of the art there is
no
teaching or suggestion of heterogeneous catalyst analogous to supported metal
catalyst
wherein, catalytically active material is physically distributed on the solid
surface and the
formulation as a whole can be employed as heterogeneous catalyst which is
useful for
catalyzing reactions in polar as well as nonpolar solvents. Thus it is an
object of this
invention to provide a novel catalyst useful for promoting a variety of
chemical reactions.
More particularly, this invention relates to a catalyst system comprising of
calcium,
strontium, barium salt of ligand containing at least two or more acidic
functional groups
and an organometallic catalyst generated from it. These salts are supported on
the solid
surface of inert vehicle or carrier. This catalyst is useful for promoting
reactions in
aqueous, polar and non-polar organic mediums.
Many anionically charged phosphines, and other coordinating compounds as well
as variety of their salts are known in the art. It is also known that these
ligands and
complexes thereof are water-soluble but importantly there is no disclosure or
suggestion in
open literature, patent or any known reference, indicating an appreciation of
any
significance, of the formation of insoluble material as alkaline earth metal
salts of
anionically charged ligands and complexes thereof. Moreover there is no
teaching,
disclosure or suggestion in any reference known to applicants, evidencing any
significance
of particular type, class or characteristic of such insoluble organometallic
complexes or
catalytic application thereof as it relates directly to recovery and recycle
of the catalyst.
It has now been discovered that reactions that are catalyzed otherwise by
soluble
catalyst can be catalyzed by solid catalyst of this invention. The solid
catalyst as said
herein is not a chemically defined single component catalyst system but a
formulation
wherein solid support and catalytically active material are assembled together
to form a
solid catalyst. The support is components, which by itself is a catalytically
inactive but
provides a physical vehicle, filler and provide a high surface area whereupon
catalytically
active material is placed. This conglomerate of support and catalytically
active material is
not a simple random physical mixture but assembled in a specific manner such
that support
surface is covered or deposited with catalytically active material. Such
concepts are known
earlier as described in the background of the invention but providing a
catalyst suitable
only for gas phase or for specific liquid phases. For example supported
aqueous phase
catalysts (hereafter termed as SAPC) or supported liquid phase catalysts
(hereafter termed
as SLPC). SAPC for instance can only be employed in cases where reaction
medium is
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water immiscible organic media. Similarly SLPC are suitable only in gas phase
but not in
general liquid phases.
The surprising element of this invention is that a generic technique is
discovered
whereby native catalyst, which is otherwise soluble, can be converted to a
solid material,
5 which is practically insoluble in organic and aqueous medium. Catalytically
active material
as said herein is constructed from secondary construction blocks that are
derived from
catalytically active moieties, when placed over a high surface area solid,
catalyze a
reaction which is otherwise catalyzed by native building species in
homogeneous phase but
at the same time remaining as solid placed on the support. Due to such reason
catalyst as a
whole can be separated from reaction mixture by simple solid-liquid
separation.
Such catalytic formulation provides a tremendous advantage than catalyzing a
reaction by homogeneous or heterogeneous catalyst. This catalyst was conceived
in
manner analogous to supported heterogeneous catalyst but supported active
phase is
constructed fronl molecular entities, which in reality catalyze actual
reaction. This
particular formulation synergistically combines the desired facile separation
and high
specificity of the molecular catalysts. The advantages that were obvious to
the inventors
are;
(a) Solid catalyst providing inherent separation
(b) Activity and selectivity similar to soluble molecular catalysts since
active sites are
structurally isotropic
(c) Formulation as a whole is mechanically robust material
(d) Modularity of the assembly is such that desired selecting entities,
support and
additives depending on the need one can assemble the catalyst.
As described herein central theme of this discovery is the invention whereby a
soluble catalytic material is converted to a solid that is practically
insoluble in diversity of
liquid media by a systematic molecular modification. It was realized that when
soluble
catalytic species is modified in such a way that it bears two or more anionic
groups
existing along with proton, alkali metal ammonium and quaternary ammonium
salts. The
soluble catalyst modification mentioned here implies that anionic functional
groups are
introduced while synthesizing components of catalyst or otherwise modifying
catalyst as
such. Said anionically functionalized salts when interacted with group IIA
metal salts
provide a solid material that is insoluble in variety of liquid media. This
solid material is
composed of building blocks of catalytic entities bridged with group IIA metal
cation.
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Surprisingly in previous patents (US 4,248,802 and US 4,994,427) alkali earth
metal salts of such anionically functionalized compounds were claimed in
general as
aqueous soluble. In this invention disclosure we disclose that alkaline earth
metal salts of
said anionically functionalized compounds are insoluble in organic media or
sparingly
soluble or insoluble in aqueous media. Therefore in order to suppress aqueous
solubility
admixture of catalytically inactive insoluble salts is employed. This
admixture is primarily
intended to suppress solubility of ionic solids by phenomenon commonly known
as
common ion effect.
In a manner described earlier wide diversity of catalytic complexes can be
lo converted in to solid material by a common protocol. Such solid materials
are found to be
stable under commonly encountered reaction environments. In another respect
soluble
catalysts for diverse classes of reactions, such as for instance
hydrogenation,
hydroformylation, carbonylation, olefination, telomerization, isomarization
oxidation etc.
can be solidified. Yet another aspect of the present invention is the
formulation of this
material and a solid support to form a catalyst. The support involved here can
be chosen
independent of catalytic entity being formulated and catalytically inactive
additive that is
admixed. The most interesting aspect of the present invention is that said
catalytic
formulation alternatively termed as catalytic ensemble or catalytic assembly,
remain as a
solid without its components being disintegrated by dissolution. Said ensemble
can be
employed for catalyzing chemical reactions in slurry or fixed bed reactor
configurations.
Thus the precise object of the present invention is to provide a solid
catalyst
wherein catalytic entities responsible are molecularly defined and isotropic
species. More
over technique of synthesis should be common set of techniques whereby desired
catalytic
species can be heterogenized by simple means. The essential object of the
present
invention is that catalytically active solid formulation should not
disintegrate or
disassemble under the conditions of reaction as well as under liquid flow.
Another desired
but not essential object is to provide a solid catalyst that chemically
imitates the its soluble
analogue but at the same time providing facile separation due to inherent
advaritages of
solid catalysts. The term 'native' used to mean in this context as a catalytic
entity before
modification and interaction with group IIA metal salts to yield a solid.
Other objects and
advantages of this invention will become readily apparent from the following
written
description and appended claims.
Accordingly, generic aspect of the invention can be described as the discovery
of a
common technique whereby a solid catalyst can be prepared. The family of
catalysts that
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are similar in composition, feature and advantages are referred here by the
term generic.
The feature of this family of catalyst is that these are heterogeneous but
active sites are
chemically defined organometallic entities physically existing as solid. These
organometallic entities are analogues derived from equivalent homogeneous
catalytic
entities. Homogeneous catalytic entities referred herein encompass entire
class of soluble
catalysts. These native structures are chemically modified to introduce
negatively charged
functional groups such as -S03", -P032- or -COO". When such material are
synthesized,
they exists as soluble salts depending on the counter ion accompanying anionic
functional
group. The most intriguing phenomenon realized in this invention itself
qualifies to term
invention as generic, which is organometallic entities modified as described
earlier can be
converted to a solid material by interacting them with group IIA metal salts.
The solid
formed is ultimately a salt of group IIA metals this observation is validated
by converting
large diversity of chemical structures to insoluble solids as described
earlier moreover
methods have been developed to assemble such solids on the surface of the
supports.
Brief description of the drawings
Figure 1 is the schematic representation of the conceptual representation of
the
catalyst formulation
Figure 2 is the semi realistic enlarged view of the catalyst formulation
surface. A
support upon which catalytically active material is deposited, multiple or
single reactants arrive to this catalytic material, which contains active site
whereupon reactants are transformed in to products and released back in to
bulk liquid
Figure 3 is the schematic of the continuos liquid extractor for solids
wherein, a is the
unidirectional gas bubbler connected to condenser, b is the condenser, c is
the extraction vessel holding magnetic needle and solid to be
leached/extracted, d is the magnetic stirrer unit, e is the vessel holding
extraction liquid, f is the high temperature bath
Figure 4 is the schematic of the fluidized bed in which catalyst formulation
is
processed wherein, a is the jacket through which constant temperature fluid
is circulated, b is the atomizer through which liquids are sprayed in the
fluidized bed, c is the gas solid separation mesh, d is the inlet for solution
A, e is the inlet for solution B, Vl and V2 are valves
Figure 5 is the schematic of the catalyst preparation unit with simultaneous
removal
of liquid wherein, a is the inert gas inlet, b is the inlet for solutions A
and B,
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c is the vessel holding magnetic needle, support and liquid, d inert gas
outlet, e is the condenser, f is the liquid collector, g is the collection arm
for
liquid.
Figure 6 is the schematic of the catalyst preparation unit wherein, a is the
inlet for
solution A and B, b is the vacuum line, c motor for coating pan, d is the
coating pan, e is the nozzle for liquids A and B, f is the high temperature
bath, g is the collection vessel for condensed liquid
DESCRIPTION OF THE PREFERRED EMBODIMENTS
For the purposes of promoting an understanding of the principles of the
invention,
reference will now be made to several embodiments illustrated in the examples
and
specific description will be made to describe the same. It will nevertheless
be understood
that no limitation of the scope of the invention is thereby intended, such
alterations and
further modifications in these embodiments, and such further applications of
the principles
of the invention as described herein being contemplated as would normally
occur to one
skilled in the art to which this invention relates.
In one embodiment of the inventiuon, provides a novel heterogeneous catalytic
composition comprising a solid support having deposited thereon a
catalytically active
material which is practically insoluble in variety of liquid media, the said
solid material
consisting of catalytically active anionic entities with group IIA metal ions
and the
catalytic active material is molecularly well defined.
In another embodiment of the invention, the catalytically active entity is
deposited
on the external and the pore surfaces of the solid support, pores of which are
predominantly of diameter greater than about 20 A and the pores of solid
support having a
pore diameters ranging from about 3 -3000 A .
In still another embodiment, the solid support is chemically inactive solid
material,
exists as powder, granules, flakes or pallets of regular or irregular shapes,
sheets, monolith,
ropes and woven fabric of fibrous solids and the porous solid support is
mechanically
robust and thermally stable solid, insoluble in reaction media.
In still another embodiment, the catalytically active entity is insoluble in
reaction
media, which are selected from organic, aqueous, flours, non-aqueous ionic
liquids and
supercritical fluid phases and is thermally stable solid material having
melting point
greater than 100 C.
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In yet another embodiment, the catalytically active material is a non-
subliming
solid.
In yet another embodiment of the invention providesd a catalyst comprising of
solid support having deposited thereon catalytically active entity which
remains as a stable
composite solid in gas, liquid and gas-liquid phases and the liquid phase is
selected from
organic, aqueous, flours, non-aqueous ionic liquids and supercritical fluid
phases or
mixture thereof containing reactants, products and promoters.
In yet another embodiment, the catalyst remains as a physically stable
composite
solid in gas or liquid phases over a temperature range of -78 to 300 C and
over pressure
ranging from 5 to 5000 psi.
In yet another embodiment, group IIA metal used is a cation having +2 charge
and
is selected from calcium, strontium, barium and mixtures thereof.
In yet another embodiment, group IIA metal used is selected independently or
in
combination with other group IIA metals.
In yet another embodiment, thecatalytically active entity is an anion having
two or
more negative charges and is independently selected from metal complexes,
quaternary
compounds, metaloxoanions, polyoxometallates and combinations thereof.
In yet another embodiment provides a catalyst wherein, the metal complexes
having a general formula
(M)X(I-)y(I-*)Z
wherein M is catalytic metal atom or ion of a coordination complex is a
transition
metal from group IITB, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements
and is selected independently, x is ranging from 1 to 60, L is selected from
aliphatic,
aromatic and heterocyclic compound containing at least one radical from 0, N,
S, Se, Te,
P, As, Sb, Bi, Si, olefin, carbene having attached thereto oxy, alkyl, aryl,
arylalkyl,
alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at least one or more negatively
charged
functional groups independently selected from -S03",-SO2 -P032", -COO-, -0-,
AsO32- and
-S" , y is at least 1, L* is a radical selected from organic anion, inorganic
anion and
coordinating compound containing at least one radical from 0, N, S, Se, Te, P,
As, Sb, Bi,
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Si, olefin, carbene, =C: having attached thereto oxy, alkyl, aryl, arylalkyl,
alkylaryl,
alcoxy, arlyoxy, cycloalkyl and Z is ranging from 0 to 7.
In yet another embodiment, the quaternary compound is having a general formula
[(Y+)(R*)i ] [Z]
5 wherein, I = 4 for Y+ = N+, P+, As+ ; I = 3 for Y+ = S+ and R* is selected
independently from alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy,
cycloalkyl bearing at
least one or more negatively charged functional groups independently selected
from -S03",-
S02- -PO32", -COO-, -O", AsO32- and -S" and Z is an anion selected from
organic anion,
inorganic anion and coordination complex anion.
10 In yet another embodiment, the insoluble catalytically active material
optionally
comprising catalytically inert additive, inert additive is an anion having two
or more
negative charges and which is independently selected from organic, inorganic
anions or in
combination thereof.
In yet another embodiment, the catalytically inert additive is selected from
ligand
compounds wherein, ligand compounds contain at least one radical from 0, N, S,
Se, Te,
P, As, Sb, Bi, Si, olefin, carbene having attached thereto oxy, alkyl, aryl,
arylalkyl,
alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at least one or more negatively
charged
functional groups independently selected from -S03 ,-SOZ -P03Z", -COO-, -O",
As032- and
-S-.
In yet another embodiment, the amount of catalytically active entity employed
is 40
% weight or less and the amount of catalytically inert additive employed is in
the
proportion of 0 to 200-weight % of catalytically active entity.
In yet another embodiment, the catalyst can be employed to catalyze reactions
in
gas phase or in slurry phase.
In yet another embodiment, the catalyst further comprising a film of high
boiling
liquid deposited on the solid catalyst.
As stated herein above, primary aspect of applicants' invention is directed to
a solid
formulation as a catalyst comprising of a solid support having deposited
thereon a
catalytically active solid material. Thus, the catalytic formulation referred
herein is
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primarily a solid in physical sense and an organized ensemble of chemical
components put
together to perform the task of catalyzing the reaction. The definition of
assembly is
narrowly put down in embodiments that will follow, to conceive a real life
catalyst. This
multi-component catalyst is the balanced compromise between supposed fluid
flow around
catalytic particle, activity and a physical integrity. The relative importance
of these factors
directly affects the reaction, reactor design, process conditions and
economics. Although
many catalytic materials are composed of single components such as zeolites,
pillared
clays, metals alloys and metal oxides they certainly cannot catalyze the wide
diversity of
reactions. Whereas multi-component catalysts as considered in this embodiment
offer a
choice of physicochemical properties that can be selected from different
materials as salts,
oxides, metal aggregates or organometallic materials. In order to achieve
earlier stated
features, this embodiment describes the general architectural draft of
catalytic formulation
of this invention as illustrated in the figure 1 and 2
Referring to the figure detailed in figure 1 components of the said
formulation is
distinguished into two categories. These two categories are catalytically
passive and
catalytically active. Passive components are supports and other additives that
necessarily
impart solid character to catalyst formulation and may be selected independent
of active
entity depending upon application. Of course it is understood that choice of
supports
cannot be made randomly and selection is totally dependent on the process. For
example
silica supports cannot be utilized in strong alkali solutions, as it will
dissolve causing the
loss of integrity. Thus supports in the context of this embodiment are
considered as agents
to impart physical shape and form to catalyst particle and act as a vehicle to
enhance the
maneuverability.
From previous discussion it is explicit enough to judge that catalytically
active
material is often expensive and sometimes precious, later is often true for
reaction that are
catalyzed by organometallic complex catalysts. The activity of such materials
when
supported on solid depends on factors such as surface area, porosity, geometry
and
resistance to surface fouling. In an effort to optimize these factors, it is
common practice to
disperse active ingredients on the surface of the inactive solids
conventionally known as
supports or carriers. Although these materials are considered as diluents,
they sometimes
play an important multifunctional role in directing catalytic activity. This
may include
chemical reaction with catalytically active material and they are designated
as inactive only
to distinguish themselves from bi-functional catalysts, in which support plays
a major role
in catalytic function. The present embodiment implicitly assumes the
possibility of
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12
formation of such synergistic multifunctional combination in certain cases.
Accordingly, purpose of employing a support is strongly reasoned due to
numerous
factors such as economic, process needs and desired physico-chemical
properties. The
economic reasons as conceived by inventors are mainly cost reduction by
extending
accessibility of expensive catalytically active material. Further more process
needs as
recognized by inventors were sufficient mechanical strength imparted to the
catalyst,
adjustment of bulk density of formed catalyst, to provide heat sink or heat
buffer and to
dilute the overactive phase. In addition to these, inventors have recognized
geometric
needs of catalyst that are primarily satisfied by the support can be described
as increased
the surface area of the catalyst, optimization of porosity of the overall
design. Other
chemical features inventor feel necessary to state explicitly in this
embodiment are
supports provide a means to reduce sintering or deactivation and may also
provide acidic
or basic centers which function in synergy with catalytically active material.
Although in principle any stable solid material of high surface area,
porosity,
strength and required texture is suitable, depending on the particular
application under
consideration. Most stable range of solids employable herein is alumina,
silica, magnesia,
Titania, zirconia aluminophosphates, charcoal, organic polymers, and compacted
clays.
These materials are preferred due to their high surface areas, porosity and
strength. Apart
from these properties they also have low coefficient of thermal expansion.
Nearly all the insulating solids are useful as supports, although on economic
grounds alumina and silica are preferred supports. It is recognized from
previous reports
that oxides such as alumina, silica, zirconia and thoria tend to be acidic.
These properties
are either of no importance or can be eliminated by selective poisoning. Many
naturally
occurring materials belong to this group such as pumice asbestos, calcined
clays such as
bentonite, sepiolite and diatomacious earth such as keisulghur. As a result of
wide
variation in structure, solids offer range of surface areas and porosity.
Although synthetic
versions of some materials may be preferred in that they offer more closely
defined range
of properties. In cases where concerted reactions are required wherein one of
the reaction
may be catalyzed by support it self. The support can catalyze reaction due to
acidic and
basic sites available on it or metallic sites purposely formed on it. In such
cases support by
itself is another solid catalyst formed from metal supported on solid support.
Illustrative
supports belonging to these category of supports are 5% Pd on carbon, 1% Ni on
alumina
copper-chromite calcined and reduced before use, ruthenium on silica, platinum
sulfide on
carbon, etc. In considering the individual factors, which dictate the choice
of the support, it
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13
is realized that the final choice depends on the weighing of these factors in
the context of
the use to which catalyst are to be employed.
As evident, the rate of a catalytic reaction is dictated by the rate of the
chemical
reaction on the surface when observed activity is the function of the surface
area of the
solid support. In practice however overall rate of reaction is usually
affected by mass or
heat transfer, in which case porosity and geometry of the catalyst particle
become
increasingly important. As a result choice of support depends on the surface
area of the
catalyst that can be made available to the reactants and on the porosity of
the catalyst.
In context of present invention optimization of surface area is an important
factor,
which is related to other properties such as texture and the strength. Thus
surface area and
porosity are closely related, and it can be easily extrapolated further that
porosity and
mechanical strength is also interrelated. It is obvious to the designer to
ensure long life for
which catalyst needs a stable structure that is strongly bound together.
Certainly this is not
the case if porosity is too high. In case of supports of natural origin it is
difficult to tailor
degree of porosity in systematic fashion. Zeolites or carbon molecular sieves
have most of
their surface area within the channels, which due to their narrow width
restrict passage of
reactant molecules. Some gamma aluminas have pore size distribution in the
range of 100-
200 A , while foamed aluminas have few micropores. Pore diameter can also be
increased
by careful precipitation of material in pore mouth.
Accordingly in addition to acting as a physical vehicle for the catalytic site
support
can have appreciable effect on the catalytic reaction it self, wherein for
example local pH
can be different or bulk of the support can stearically influence course of
the reaction and
even prevent its occurrence.
As discussed earlier it is understood that apart from chemical behavior of the
active
phases support plays important role in defining catalyst properties. Such
properties could
be utilized depending on the process requirements. A considerable advantage
would be
gained if support effects on the active catalytic phases could be minimized
which is often
difficult in heterogeneous catalysts. By separating effects of active phases
and support on
can tailor the morphology of the catalyst by selecting support and active
phases
independent of each other.
Accordingly said support in the catalytic formulation is porous solid pores of
which
are predominantly of diameter greater than about 20 A and have a pore
diameter in the
range of about 3-3000 A . It is also preferred that support material be inert
towards
substrate, intermediates, products and solvent of the reaction unless
concerted tandem
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14
sequence of reaction is desired of which one or more reactions is catalyzed by
support
itself. The suitable catalyst support is any solid that is insoluble in
reaction medium and
which is thermally stable and high melting solid. The support materials are
exemplified but
not limited by pumice, alumina-gel, silica gel, silica-alumina-gel, aged or
deactivated
silica-alumina cracking catalyst, magnesia, diatomaceous earth, bauxite,
titania, zirconia,
clays, both natural and acid treated, attapulgite, bentonite, diatomaceous
earth, keisulghur,
lime, calcium carbonate, calcium silicate, magnesium silicate, carborundum,
activated and
inactivated charcoal, adsorptive carbon, zeolites, zeolite molecular sieves,
hydrotalcite,
solid foams such as ceramic honeycombs, porous organic polymers such as
macroreticular
ion exchange resins, poromeric polymers, porous crosslinked polystyrene-
sulfonated,
calcium alginate, barium sulfate, powdered cellulose, woven cotton mesh,
foamed paper,
functionalized polymers. It is also possible that the support may be a
supported metal
catalyst. Above said support materials may be used as regular and irregular
particles,
capillary tubes, meshes, fabric meshes and inter-spacing elements such as
shapes,
extrudates, ceramic rods, balls, broken pieces, raschig rings, tiles. Support
materials can
also have modifiers or deactivators present from impregnation or spraying
processes, or
other forming operations.
As described in the earlier embodiment present invention is concerned with
solid
phase multi-component formulation in which the catalytically active material
is placed on
the surface of the solid support. It is invented that soluble catalytic
material such as
organometallic complexes if rendered insoluble can form said catalytically
active solid
phases wherein active sites are defined isotropic molecular entities otherwise
existing only
in solution state. Such insoluble material when dispersed and supported on the
surface of
the solid support can form simple solid catalyst of the choice. The
illustration as depicted
in figure 2 outline the strategy as envisaged by the inventors.
Active components are composed of solid phase that is catalytically active
i.e.,
which is primarily responsible for desired chemical transformation. Unlike
support
generality of choice for such material is seldom available and composition
must be
rationally developed within the framework of laws of relevant chemistry. As it
is well
understood that diversity of materials can catalyze same reaction but one
material may not
necessarily catalyze diverse range of reactions. It is therefore another
specific embodiment
of the present invention whereby soluble nzolecular catalyst are appropriately
modified
such that they can be incorporated in the said solid material
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The desired properties of such catalytically active solid material are:
1. Material should not be dissolved or withered in wide variety of reaction
medium
and conditions;
2. Said material should have sufficient mechanical and fracture strength;
5 3. Such material should be generated from organic organometallic building
blocks;
4. Material should have strong cohesive tendency towards support and total
formulation should remain as composite material throughout reaction conditions
such as temperatures from -78 to 300 C, in liquids comprising aqueous,
organic
and combination thereof as well as in acidic and alkaline conditions;
10 5. Said material should be high melting and non subliming;
6. Catalytically active solid material should be thermally stable should not
pyrolyze at
reaction temperatures; and
7. One of the building block of the material is molecular component
responsible for
particular reaction to be catalyzed.
15 The reaction media as said earlier is quite broad class of liquids and may
be
selected depending on solubility of substrates and other components as well as
it should
provide clean recovery of products. The liquids usable as reaction media are
exemplified
but not limited by petroleum fractions of different boiling ranges, cyclo
alkanes such as
cyclohexane, cycloheptane, cyclodecane, aromatics such as benzene, toluene,
xylenes,
ethyl benzene, butylbenzene, alcohols including methanol, ethanol, propanol,
butanol,
amyl alcohols (linear and branched) higher alcohols, cyclohexanol, phenol,
xylinol, cresol,
acids such as acetic, propionic, butyric, amides such as formamide, dimethyl
formamide,
pyrolidone, n methyl pyrolidone, nitriles such as acetonitrile, propinitrile,
benzonitrile,
esters such as ethylacetate, methylacetate, methyl propionate, methyl benzoate
methyl
propionate, ethers such as diethylether, dibutyl ether, diphenylether,
tetrahydrofuran,
dioxane, furan, ketones such as acetone, methylethylketon,e, pentane 2 one,
cyclohexanone,
nitroaliphatics such as nitromethane, nitroethane, nitropropane,
nitroaromatics such as
nitrobenzene, 2-nitrotoluene, halogenated solvents such as dichloromethane,
chloroform,
carbon tetra chloride, 1,2 dichloroethane, chlorobenzene, dichlobenzene other
high boiling
solvents used for specific purpose include, hexadecane, octadecane,
hexatracontane,
squalene, chlorinated hydrocarbon oil, liquid paraffin, mineral oil,
naphthalene,
phenanthrene, methyl naphthalene, high boiling substituted and non substituted
organic
alcohols, glycol, polyglycols, ethers, polyethers, such as glycerol, carbitol,
dulcitol,
erythritol, polyethyleneglycol, propyleneglycol, diglycerol, diethyleneglycol,
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16
polypropylene glycol, tetraethyleneglycol, 2 ethyl 1 3 hexane diol, 1,5
pentanediol,
methoxypolyethylene glycol, diethylene glycolmonomethyl ether,
polybutyleneglycol,
1,2,4-butanetriol, polyphenylether, methylbenzylether,
bis(phenoxyphenyl)ether,
tetraethylene glyco dimethylether, high boiling esters such as
diisooctylphthalate, dibutyl
phthalate, dioctylphthalate, bis(2-ethylhexyl) phthalate, dinonyl phthalate,
butyl benzyl
phthalate, bis(2-tetrahydrofurfuryl) phthalate, dipropyl tetrachloro
phthalate, dioctyl
sebacate,bis(2-ethylhexyl)sebacate, inorganic solvents employable are water,
room
temperature ionic liquids, flours solvents and super critical dense phases. It
is also possible
that combination of one or more solvent media be used for reactions depending
on
lo solubility of reactants and products. The criteria for selection of solvent
are chemical
physical requirements of the reaction than the catalyst formulation
components. The
catalyst formulation as a whole is stable in diverse reaction media so
practically any liquid
can be used as solvent of the reaction as in case of conventional
heterogeneous catalysts.
Of course it is understood that for optimum performance of the catalyst very
few liquids
are suitable and must be selected accordingly.
Properties described earlier for catalytically active solid material are
generally
found in materials such as ceramics. It is well known in the art that ceramics
contain
metallic and non-metallic elements that are bonded ionically, covalently or
both. These
materials can be classified according to their structural composition of which
A,Y,Xn is most
common example. A is polyvalent metal cation having +m charge and X is
polyvalent
anion having -n charge. These materials being ionic lack free electrons making
them poor
conductor of heat and electricity. Moreover ionic bonds being highly stable
and directional
also impart high melting range to ceramics. Usually ceramics are also more
hard and
resistant to physical and chemical changes. Other factors influencing the
structure and
property relationship of ceramic materials can be described as radius ratio
and
electronegativity difference between positive and negative ions although net
negative
charge on the material is nil. It was thus clearly envisaged that catalytic
material should
have properties similar to ceramics
It is thus another embodiment of this work to develop a solid material wherein
unit
blocks are composed of defined catalytic entities. Another purpose of the
present work is
that development of a strategy without limiting said catalytic formulation to
one particular
class of complexes or reaction following certain mechanism according to some
particular
theory. It was conceived that materials of AmXn type if formed where in Am is
a alkaline
earth metal cation and X being anion having structure responsible for
catalyzing particular
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17
reaction then resultant material would have properties similar to ceramics. It
was further
speculated that such materials being ionic would not be soluble in organic
solvent which
are customarily used as solvents at the same time such materials due to their
negligibly low
solubility in aqueous solvents can be employed wherein media is aqueous.
In order to validate and universally substantiate this hypothesis several
comparative
experiments as referred in examples were undertaken. Anions having two or more
negative
charges were interacted with group IIA metal cations in solutions. Variety of
group IIA
compounds including salts, complexes, alkyls and hydrides were interacted with
variety of
anions having negative charge ranging from -1 to -3 and polyanionic compounds.
Various
group IIA compounds used for this were selected from magnesium chloride,
magnesium
acetate, magnesium nitrate, magnesium acac, magnesium complex of ethylene
diamine
tetraacetic acid disodium salt bytyl magnesium chloride, calcium hydroxide,
calciurn
chloride, calcium nitrate, calcium hydride, calcium acac, calcium complex of
ethylene
diamine tetra acetic acid disodium salt, strontium acetate, strontium
chloride, strontium
acac, strontium complex of ethylene diamine tetra acetic acid disodium salt,
barium
nitrate, barium hydroxide, barium acetate, barium chloride. Such compounds
were used as
source for group IIA cations in solution. These cations were interacted with
anions bearing
-1, -2, -3 negative charge and polyanionic compounds. Such anions in solution
were
obtained from sodium nitrate, sodium propionate, p-toluene sulfonate sodium, m
benzene
disulfonate disodium, disodium oxalate, disodium sulfate, disodium phenyl
phosphonate;
disodium hydrogen phosphate, sodium hydrogen phthalate, ammonium molybdate,
sodium
carboxy methyl cellulose, sodium polyvinyl sulfonate. It was conclusively
verified that
iigroup IIA metal ions except magnesium ions form insoluble salts when
interacted with
anion having at least two or more negative charge. Such salts are insoluble in
organic,
mixture of aqueous organic and have extremely low solubility in water.
Accordingly the hypothesis is confirmed that alkali metal salts containing
cation
(An+ wherein n>1) when interacted with polyanions (X), provide a material that
is
insoluble in majority of solvents including organic as well as aqueous. Such
proposition
was validated by interacting variety of anionic compounds as described in
experiment 1
based on diversity of anion structure it was realized that salts of alkaline
earth metal and
anion having 2 or more negative charges would provide a solid. Contemplative
conclusions
were drawn by systematically varying molecular volumes of the polyanions,
electron
density of the anionic functional groups and alkali metal cations. It was
realized that sole
requirement for material to form insoluble matter is that anion (X) as
described earlier
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18
should have at least two anionically charged functional groups. From the
experiments
detailed subsequently it was realized that anions as small as oxalate to poly
anions as large
as polyvinyl sulfonate form sparingly to almost insoluble material in water
and totally
insoluble in organic solvents. If polyanionic nature is introduced on the
peripheral
positions of the catalyst molecules such that introduction of such groups does
not interfere
or affect catalytic reaction, would provide anions (X) as said earlier.
Said anionic compounds are those which in conventional sense are acids with
proton as counter cation. It is also preferred that strongly acidic functional
groups be
introduced on the native catalytically active species. Strongly acidic groups
are preferred
for the reason that these cannot be further protonated in contact with
stronger acid that may
exist in the reaction medium. It is therefore preferred that strongly acidic
functional groups
be selected such as for example -SO31-, -P032-, etc though other groups are
also suitable for
example -COO- provided reaction medium is not acidic.
The catalytically active species described in earlier embodiment is a
molecular
entity having structural features necessary for intended catalysis. Such
molecular entities
for example are metal complex catalyst, metal oxoanions or ion pair.
Peripheral positions
of such catalytically active entities are substituted with anionic functional
g'roups such as -
S031-, -P03'", -COO- and degree of substitution being essentially > 1.
The substitution/modification as said herein is specifically meant molecular
modification of the entity such that it bears said anionic functional groups
such as for
example -COO", -S03", -P032" etc. The term modification doesn't necessarily
mean that
modified entity is chemically derived from parent entity but it is the
analogue of parent
structure synthesized independently. It is further specified that such anionic
functional
groups be attached to one of the carbon atoms of the parent entity.
Thus the explicit statement of preferred embodiment is, said catalytic
formulation is a
combination of solid support as described in earlier embodiment having
deposited thereon
catalytically active solid material and ensemble as a whole exists as a stable
composite
solid in gas or liquid phases. The said liquid phases are comprised of
aqueous, organic
liquids or mixture thereof containing reactants, products and promoters. The
catalytic
formulation of this embodiment as a physically stable composite solid in gas
or liquid
phases over a temperature range of -78 to 300 C and remain as a physically
stable
composite solid in gas or liquid phases over pressure ranging from 5 to 5000
psi. The
catalytically active materials of the embodiment are insoluble salts
comprising of group
IIA metal, catalytically active inert additive and catalytically active
entities. To state
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19
further the group IIA metal exists as a cation having +2 charge. The group IIA
metal cation
of the said catalytically active material is selected from calcium, strontium
and barium.
And specifically excludes magnesium. The group IIA metal forming catalytically
active
material may be selected independently or in combination with other group IIA
metals.
The said catalytic material is formed by precipitation of polyanionic
catalytically active
entity and catalytically inactive polyanionic entity along with earlier stated
group IIA metal
ions.
The addition of inert additive is strongly reasoned for reducing solubility of
catalytically 'active solid in aqueous solvent. As said material is ionic
tends to, dissociate in
water and thereby dissolves in liquid phase if it is incidentally liquid. In
order to suppress
this, other ionic material is required to be additionally present for
sacrificial solubility and
reduction of solubility by common ion effect, phenomenon that is well known in
the
literature. Additionally it is also envisaged that addition of such additive
provides a
microporosity to this material. Addition of catalytically inert material,
which by itself is
one of the components of the metal ligand complex, provides a surplus
coordination
capacity to the solid material which acts as significant buffer permitting
retention of
coordinated transition metal in the complex. Conversely it implies that
presence of
additional ligand as catalytically active additive prevents the loss of
transition metal as
well. It is further understood that catalytically inert additive may be
present optionally
depending on adsorptivity of the support, fluid stresses on the solid
particles and
coordination tendency of the reactants and solvents. The catalytically active
entity or
entities can be independently selected from metal complexes, quatemary
compounds,
metal oxo anions and polyoxometalletes or combination thereof.
The metal complexes as described earlier has a general formula
(M)x(I-)y(I-)z
wherein M is catalytic metal atom or ion of coordination complex is a
transition metal
from group IIIB, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements and may
be selected independently suitable transition metal ions and atoms include Sc,
Y, Ti, Zr,
Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn.
Preferably
the metal complex will contain metal atom or ion from group VIII of periodic
table of
elements, the suffix x stands for number metal atoms or ions being present
from 1 to 60, L
is aliphatic, aromatic and heterocyclic compounds containing at least one
radical from 0,
N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene having attached thereto oxy,
alkyl, aryl,
arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at least one or more
negatively
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charged functional groups independently selected from -S03 ,-SOZ ,-P032", -COO-
, -0-,
As032- and -S- . the suffix y is required to be at least one. L* is a radical
selected from
organic anion, inorganic anion and coordinating compound containing at least
one radical
from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, =C: having
optionally attached
5 thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, aryloxy, cycloalkyl,
hydrido, carbonyl,
acyl and alkyl and Z is from 0 to 7.
As described in earlier embodiment catalytically inert additive is optionally
selected from ligand compounds wherein, ligand compounds contain at least one
radical
from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene having attached
thereto oxy, alkyl,
10 aryl, arylalkyl, alkylaryl, alcoxy, aryloxy, cycloalkyl bearing at least
one or more
negatively charged functional groups independently selected from -S03 ,-S02 -
PO32", -
COO", -O", As032- and -S".
The quaternary compound of as described in one of the previous embodiments has
general formula
15 [(Y+)(R*)I ] [Z]
wherein, I= 4 for Y+ = N, P+ , As+ and I = 3 for Y+ = S+ and R* is selected
independently
from alkyl, aryl, arylalkyl, alkylaryl, alcoxy, aryloxy, cycloalkyl bearing at
least one or
more negatively charged functional groups independently selected from -S03 ,-
SOZ -P032-,
-COO-, -O", As032" and -S- and Z is anion selected from organic anion,
inorganic anion or
20 coordination complex anion.
Such type of anionically charged ligands sulfonated tertiary phosphine metal
salts
ligands employable in this invention and/ or their methods for their
manufacture are well
known or obvious as seen e.g. by procedures described in " J. Chem. Soc.", pp.
276-288
(1958), US patent nos. 4,483,802 and 4,731,486 for instance such ligands can
be prepared
by sulfonating corresponding aromatic tertiary phosphine with fuming sulfuric
acid under
controlled temperature conditions to form predominantly protonated di or poly
sulfonated
phosphines, e.g.
R1
R2H
rJ03-
R1,R2 are aryl aryl alky or alkyl
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21
For example the solid phosphine is added to fuming sulfuric acid in portions
while
controlling temperature below 5 C and then heated, e.g. to 20 -80 C until
desired degree
of sulfonation is achieved. The reaction mixture is then cooled immediately to
stop any
further sulfonation or oxidation of phosphine and without waiting water is
added to this
avoiding temperature raising above 30 C and said protonated phosphine salt is
neutralized
with alkali solution. The mixture containing alkali sulfonate and alkali
sulfate is
concentrated by evaporating water. During the evaporation of water alkali
sulfate
precipitate, which is removed by filtration and methanol, was mixed to this
mother liquor.
Most of the alkali sulfate precipitate and sulfonated phosphine is extracted
in the methanol.
Evaporation of methanol affords sulfonated phosphine as solid. Dissolving in
suitable
solvent such as water or ethanol and recrystallizing it therefrom may further
purify the
crude tertiary phosphine metal sulfonate.
The sulfonation can also be carried out in concentrated sulfuric acid media
using
boric acid and sulfur trioxide complex as described by Albanese et al US
5684181 and
US5780674. The advantage of such procedure is that it reduces phosphine oxide
formation. Similarly work up of the sulfonation reaction may also be modified
by
extracting quenched sulfonation mixture by tributyl phosphite or tri iso octyl
amine
organic phase which is subsequently extracted with alkali solution advantage
of such
procedures being phosphines can be selectively separated from corresponding
oxides.
Oxides of phosphines are frequent contaminants in such sulfonated phosphine
ligands.
Presence of phosphine oxide as such doesn't affect catalytic behavior of the
ligand in
combination with transition metal. It is understood that such phosphine oxides
don't
coordinate with metal so contamination due to phosphine oxide may be tolerated
for the
purpose of catalyzing reactions. The presence of phosphine oxides may be
intolerant in
cases such as bidentate ligands and bidentate chiral ligands. Those experts in
the field since
can easily realize the situation since phosphine mono oxide of the bidentate
ligand will
display different coordination behavior. The situation is further complicated
while
preparing catalysts for enantio selective reactions. In such case phosphine
oxide removal is
desired and may be achieved by extractive separation from tributyl phosphite
or tri iso
octylamine solutions or by fractionating from gels of modified dextran such as
SEPHADEX G15 (TM) as described by Hermann et al Angew. Chem. Int. Eng. Ed. 29
(1990) No (4) 391-393.
Such ligands that are sulfonated can be prepared by various methods employing
lithium phosphides, Grignard reagent and phosphorus trichloride etc. Knowledge
and
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22
understanding of such ligands is taught in literature known to artisan skilled
in the art. For
example Kosolapoft G. M., Maier L. Organic Phosphorus Compounds, Volume 1,
288,
Wiley Interscience, New York, 1972./Engl R. synthesis of carbon phosphorus
bonds,
CRC Press 1988./ Tripett S. A. A specialist Periodical Report of
Organophosphorus
Chemistry, Chemical Society London 1970/ specific example of such synthesis
is
explained in (Mann, F. G. et al, J. Chem. Soc. 1937, 527-535; US 4,483,802 and
US
4,731,486) Similarly nitrogen containing ligands can be prepared by specific
chemical
synthesis known in the art (Eit Drent, US 5,166,411). Synthesis, manufacture
and
purification of such ligands is clearly out of purview of this application. It
is clearly
understood knowledge concerning sulfonation of such ligands is also well
known.
Similarly ligands bearing other anionically charged functional groups for
example -COO",
-P03 2- can also be prepared by sequence of specific organic synthesis
(synthesis of
phosphonic and carboxylic containing ligands) This invention claims further
utilization of
such well known ligands for preparation of generic catalyst formulation which
is a solid
and employed as a catalyst. This utilization of such known ligands by further
processing is
within the scope and purview of this application and is one of the preferred
embodiments
of this invention. Illustrative preferred anionic ligands and their transition
metal complexes
and quaternary compounds include, as follows. It is implicit that these are
only illustrative
and not comprehensive.
Anionic ligand
So3
oss P
~ \ I \
S03
/
P
- 3S ~cr
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23
So3' o3
P
P
sQ3 so3
~ So3
03S
N
S Q3
SO3
I / ..
N
_O3S
So3
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24
N
0 0
N
so;
S03_
iN
~
N
~
SO-
3
S03
S03
P
S ~3
'
P 1 ~
s o3
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S~3
so3
N ~
~
~
s _
3
. /i N
. ~ ~
s0_
3
so3
so3
p
so_
3
p
sQ3
( \ _
3
~
1 ~
so3
sQ3
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26
_o3S P
S03
CH3
1
CH2)n
a3s P
S 3
ooc _o0c P
6
S _
3
R R
03 $ P
so3
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27
So3
P
) /
Q3s SQ3
1 \ \
P So3
So3
P (CH2)n
S031.3
S 03
F
_ xcx:03
F
sQ3
P
S03
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28
coo-
I /
~
p
C00 COO -
I \
/
P
P032~
s0_
3
EC P
P
- / ~ SQ3
s03
Me
e Me
P
PO 2_
3
_ O3S S03
OH HO
N N
u
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29
So3
N
I \ \
/N N~ ~
/
-03S N I S03
Jr03
Some of the illustrative quaternary compounds are
Anionic quaternary compounds
So3
-ID3S +.CH3 OH-
N
S03
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WO 02/078842 PCT/IN01/00083
s03
Me.,
N S03
6so-
3
s03
Jf'Q3 \ ~ +
/ ~ N=CH
3
s03
'N'
s03
CH3
OOC
+-CH3
OOC N~CH3
iH3
Poly anionic ligands and quaternary compounds as described above exist as
salts of
alkali metal, quaternary ammonium or proton. It is well known in the art that
such compounds
are water soluble combination of such ligands with transition metals provide
access to fheir
5 complexes. Some of illustrative catalytically active entities are:
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31
Catalytically active anionic entity
SO - S03
_ 1 \ SO-
_ S&
3
S03
H
P-Rh P
I 'P
-~ CO
S03_ S03
\
SO3
S03
_ s03
sO
\~
P s O 3
~\
H
GO
P S0_
3
I I
S03
S 3
s03
N
''d(Ac)2
N
s0_
3
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32
so3 so3
x Ci
so; Pd,P
P ci
// I S03
\
so3 ~3
S03 0
9
,Ru(CI)2
\ \ ~
_ \ I
S03 SQ3
P
Rh+PF6- NBD
P
- / ~
S03 0 0 / \ So3
Co
N N-
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33
Q3 SQ3
P
_ PePtCI-SnCl3 S03
S03
SQ3
S03
SO3
I \
N
N-M--N ~ I \
S0 I
3 - N I gp3
- S03
0,0
sMo
=
-O 0
I \
~
Rh(CO)
212
H3C---N+
1
CA 02442288 2003-09-26
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34
qso;
3 OH-
~
1
i s
S03
Complexes as said earlier can be prepared by various methods kr,own in
literature
descriptions. Broadly such metal complexes can be classified as follows:
1. Synthesis of inetal complexes from metal salts and anionic ligands
2. Displacement of a labile ligand by anionic ligand
For example complexes such as PdC12 bis (triphenyl phosphine trisulfonate
trisodium) is prepared by reacting PdCI~Z' with triphenyl triphenyl phosphine
trisulfonate
trisodium in aqueous ethanol, ruthenium chloride with triphenyl triphenyl
phosphine
trisulfonate trisodium, where as complexes such as HRhCO(TPPTS)3, RuCI2 BINAP,
are
prepared by displacement of labile ligands such as cyclooctadiene or
acetylacetonate.
Complexes such as sulfonated pthalocynine are prepared by simultaneous
formation of
ligand and complex. As said earlier synthesis of such complexes is a well-
known
knowledge to those experts in the art. The synthesis of such complexes is
beyond the scope
and purview of this invention. Yet utilization of such complexes to form
insoluble solid
formulation for catalytic application is the explicit embodiment of this
invention.
Several different metal complexes containing different metals and diversity of
ligands were synthesized. Such metal complexes whenever interacted with group
IIA metal
compounds except magnesium compounds provided solids, which were insoluble in
water,
organic solvents. The precipitates were solids up to 200 C and were non-
subliming.
Several experiments as described in examples were carried out to verify
proposed
hypothesis to deduce a logical conclusion that when poly-anions when
interacted with a
group CIA metal, form a precipitate that is insoluble 'in variety of liquids.
It is yet another
preferred embodiment of this application that the admixture of catalytically
active poty
aiiion and catalytically inactive anion is prefcrred to form a precipitate
that is insoluble in
majority of riquids. Additional presence of catalytically inactive additive is
reasoned to
CA 02442288 2003-09-26
WO 02/078842 PCT/1N01/00083
reduce solubility of precipitated complex in water by well-known phenomena of
common
ion effect. It is also preferred to add additional ligand that is used to form
complex. The
presence of additional ligand is preferred especially in cases where catalytic
formulation is
intended to be used in liquid phases that are coordinating or ligand involved
is
5 monodentate.
The catalytically active material of the said catalyst formulation is formed
from
interaction of solution of catalytically inactive additive; catalytically
active entity and a
solution of group IIA metal cation by precipitation. The solution of
catalytically inactive
additive, catalytically active entity when contacted with a solution of group
IIA metal
10 cation, two solution start diffusing and subsequently whenever cation of
group IIA metal
encounters collision with poly anion solidification is initiated and cluster
of solid is slowly
formed. Such precipitation wherein, catalytically inactive additive is
independently
selected from anions having at least two or more negative charges, ligand
compounds
containing at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si,
olefin, having
15 attached thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, aryloxy,
cycloalkyl bearing at
least one or more negatively charged functional groups independently selected
from -S03-,-
SOZ -P032-, -COO", -O", AsO32- and -S", and combination thereof and
catalytically active
entity is independently selected from metal complexes, quatemary compounds,
metal oxo
anions and polyoxometallates or combinations thereof
20 The catalytically active may be selected such that metal complexes has a
general
formula
(M)X(I-)y(L*)Z
wherein M is catalytic metal atom or ion of coordination complex is a
transition metal
from group IIIB, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements and may
25 be selected independently suitable transition metal ions and atoms include
Sc, Y, Ti, Zr,
Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn.
Preferably
the metal complex will contain metal atom or ion from group VIII of periodic
table of
elements, x is from 1 to 60, L is aliphatic, aromatic and heterocyclic
compounds containing
at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene
having attached
30 thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl
bearing at least one
or more negatively charged functional groups independently selected from -
S03",-SO2-
-PO32-, -COO", -0-, As032" and -S-, y is at least 1, L* is a radical selected
from organic
anion, inorganic anion and coordinating compound containing at least one
radical from 0,
N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, =C: having attached thereto
oxy, alkyl, aryl,
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36
arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl, z is from 0 to 7 and
quaternary
ammonium compound has a general formula
[(Y})(R*), ] [Z ]
wherein, I = 4 for Y+ = N+, P+, As+
I= 3 for Y+ = S+ and R* is selected independently from alkyl, aryl, arylalkyl,
alkylaryl,
alcoxy, arlyoxy, cycloalkyl bearing at least one or more negatively charged
functional
groups independently selected from -S03 ,-S02 -P032-, -COO-, -0-, As032- and -
S" and Z
is anion selected from organic anion, inorganic anion or coordination complex
anion.
Accordingly as described in earlier embodiment inventors have developed a
common technique for solidification of pluralistic catalytic entities,
functioning according
to different theories and mechanisms. Such solidification is achieved by
incorporating
earlier said catalytic entities in ionic solid, which by itself is formed by
interaction of poly
anionic catalytic entity, polyanionic additive and group IIA metal ion.
The catalytic formulation of this invention wherein earlier said catalytic
material is
supported on the surface of the solid support. It is recalled that formed
catalytic material
being insoluble cannot be dissolved in liquid and then supported on the solid
support
accordingly technique was required to form such material directly on the
surface of the
solid support by precipitation.
The final formation of composite catalyst can thus be carried out by
precipitation of
catalytically active material on the support surface. The formation of
catalyst by
precipitation or co precipitation is thus centrally important in this respect.
However
precipitation is a complex phenomenon and demand several ancillary techniques
to be
developed in order to deposit catalyst on the support surface. Nevertheless,
for several
catalytically relevant materials especially for support materials
precipitation is most
frequently applied method. In this respect such precipitation is troublesome
as it may
generate clusters and particles in the bulk of liquid. Dealing specifically
formation of solid
catalytically active material is better described by term co precipitation as
two components
categorized as group IIA metal ion and poly anionic. entity when interacted
yields a
precipitate. Co precipitation is extremely suitable technique for generation
of uniform
distribution of such material on the support material, as stoichometry of
interacting species
is definite. Form earlier experiences it is known fact that co precipitation
can provide good
dispersion of the support surface which is otherwise difficult to achieve
catalyst assembly
that is under consideration. Thus the bulk co precipitation process needs to
be modified to
achieve assembly of composite catalyst system.
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37
Preferably, the co precipitation is carried out in such a manner that
precursor
solutions containing anionic entities (catalytically active entity and
catalytically, inert
additive) and group IIA salt solutions diffuse near the surface of the support
or the
formation of insoluble clusters initiate near the surface of the support.
Hereinafter solution
containing anionic component is designated as solution A and solution
containing group
IIA metal is designated as solution B. It is another embodiment of the present
invention
that outlines various methods for assembling catalytic formulation of earlier
said
embodiments. These assembly techniques are broadly classified according to
various
techniques of precipitation and are described in ensuing description of
embodiments.
One of the process for the preparation of a heterogeneous catalytic
formulation as a
solid composite comprising of porous solid support having deposited thereon a
catalytically active solid is characterized by suspending insoluble solid
support in a liquid
phase to which a solution of catalytically inert additive and catalytically
active entity and a
solution of group IIA metal cation are added simultaneously or sequentially
with vigorous
agitation and allowed to age for 1 to 48 hours wherein, support is a
mechanically robust
and thermally stable solid in reaction media, having a mean pore diameter in
the range of
about 3-3000 A and existing as powder, granules, flakes or pallets of regular
or irregular
shapes, sheets, monolith, ropes and woven fabric of fibroius solids and
catalytically
inactive additive is independently selected from anions having at least two or
more
negative charges which may be organic, inorganic, or a compound containing at
least one
radical form 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene having
attached thereto oxy,
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at
least one or more
negatively charged functional groups independently selected from -S03 ,-SOa -
P032", -
COO", -O", As032- and -S".
The catalytically active entity is independently selected from metal
complexes,
quaternary compounds, metal oxo anions and polyoxometallates or combinations
thereof
such that metal complexes having a general formula
(M)X(I-)y(I-*)Z
wherein M is catalytic metal atom or ion of coordination complex is a
transition metal
from group IIIB, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements and may
be selected independently suitable transition metal ions and atoms include Sc,
Y, Ti, Zr,
Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn.
Preferably
the metal complex will contain metal atom or ion from group VIII of periodic
table of
elements, x is from 1 to 60, L is aliphatic, aromatic and heterocyclic
compounds containing
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38
at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene
having attached
thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl
bearing at least one
or more negatively charged functional groups independently selected from -
S03",-SO2 -
P032", -COO", -O", As032" and -S- and y is at least 1 and L* is a radical
selected from
organic anion, inorganic anion and coordinating conipound containing at least
one radical
from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, =C: having attached
thereto oxy,
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl, z is from 0 to
7 and the
quaternary ammonium compound has a general formula
[(Y+)(R*)i ] [Z]
wherein, I = 4 for Y+ = N+, P+, As+, I = 3 for Y+ = S+ and R* is selected
independently from
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at
least one or more
negatively charged functional groups independently selected from -SO3,-S02 ' -
P032",
-COO", -O", AsO32- and -S" and Z is anion selected from organic anion,
inorganic anion or
coordination complex anion. The group IIA metal cation is selected from
compounds of
Ca2+, Siz+ and Ba2+.
The above said process is carried out in the temperature ranging from -78 to
200 C
preferably between -5 to 100 C. The solvent for the process is selected from
aqueous,
water miscible organic or mixture thereof.
The process as described above wherein solution of catalytically inert
additive and
catalytically active entity and a solution of group IIA metal cation are added
simultaneously over a period of 10 to 1500 min. After completion of this
treatment the
catalyst is recovered by centrifugation, decantation, gravity settling or
other techniques of
solid liquid separation and dried subsequently in vacuum. The method as
described herein
is employable when components of precipitate slowly produce solid material
under the
influence of viscosity, solvent media and solubility modifiers. As seeds of
solid material
develop slowly and there is enough time for seeds of the precipitate to settle
on the support
surface. Other methods described herein after are suitable for co-
precipitation that occurs
instantaneously. Such methods are usually critical due to specialized unit
operation
required for them and also require specific equipment for the manufacture.
Another process for the preparation of a heterogeneous catalytic formulation
as a
solid composite comprising of porous solid support having deposited thereon a
catalytically active solid is characterized by impregnating the solid support
with
catalytically active entity and catalytically inert additive followed by
drying, dried support
having deposited thereon catalytically active entity and catalytically inert
additive is added
CA 02442288 2003-09-26
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39
to a solution of group IIA metal compound, with simultaneous agitation. The
suspension is
aged for 1 to 48 hours with agitation, the process is accordingly carried out
in the
temperatures ranging from -78 to 200 C preferably between -5 to 100 C
The support in this case is a mechanically robust and thermally stable solid
in
reaction media, having a mean pore diameter in the range of about 3-3000 A
and existing
as powder, granules, flakes or pallets of regular or irregular shapes, sheets,
monolith, ropes
and woven fabric of fibrous solids and catalytically inactive additive is
independently
selected from anions having at least two or more negative charges which may be
organic,
inorganic, or a compound containing at least one radical form 0, N, S, Se, Te,
P, As, Sb,
Bi, Si, olefin, carbene having attached thereto oxy, alkyl, aryl, arylalkyl,
alkylaryl, alcoxy,
arlyoxy, cycloalkyl bearing at least one or more negatively charged functional
groups
independently selected from -S03 ,-SOZ -P032-, -COO-, -O", As032- and -S"
The catalytically active entity is independently selected from metal
complexes,
quatemary compounds, metal oxo anions and polyoxometallates or combinations
thereof
such that metal complexes having a general formula
(M)X(L)y(I-*)Z
wherein M is catalytic metal atom or ion of coordination complex is a
transition metal
from group IIIB, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements and may
be selected independently suitable transition metal ions and atoms include Sc,
Y, Ti, Zr,
Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn.
Preferably
the metal complex will contain metal atom or ion from group VIII of periodic
table of
elements, x is from 1 to 60, L is aliphatic, aromatic and heterocyclic
compounds
containing at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si,
olefin, carbene
having attached thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy,
arlyoxy, cycloalkyl
bearing at least one or more negatively charged functional groups
independently selected
from -S03-,-SO2 -P032-, -COO-, -O", As032' and -S- and y is at least 1 and L*
is a radical
selected from organic anion, inorganic anion and coordinating compound
containing at
least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene,
=C: having
attached thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy,
cycloalkyl, z is from
0 to 7 and quaternary ammonium compound has a general formula
[(Y+)(R*)r ] [Z ]
wherein, I = 4 for Y+ = N+, P+, As+; I = 3 for Y+ = S+ and R* is selected
independently
from alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at
least one or
more negatively charged functional groups independently selected from -S03-, -
SO2-,
CA 02442288 2003-09-26
WO 02/078842 PCT/IN01/00083
-P032-, -COO-, -0-, AsO32" and -S" and Z is anion selected from organic anion,
inorganic
anion or coordination complex anion. The group IIA metal cation is selected
from
compounds C2+, Sr2+ and Ba2+. According to process under consideration
solvents used to
dissolve anionic components and group IIA metal cations are aqueous, water
miscible
5 organic or mixture thereof
The process modification may be adopted wherein support having deposited
thereon catalytically active entity and catalytically inert additive is added
to a solution of
group IIA metal compound, with simultaneous agitation over a period of 10 to
1500 min,
depending upon specific process requirements. The process accordingly
concludes by
10 recovering catalyst by centrifugation, decantation, gravity settling or
other techniques of
solid liquid separation and drying subsequently in vacuum
Yet according to another preferred process for the preparation of a
heterogeneous
catalytic formulation as a solid composite comprising of porous solid support
having
deposited thereon a catalytically active solid is characterized by
impregnation of support
15 with a solution of catalytically inactive additive and catalytically active
entity followed by
drying. Solid support having deposited thereon catalytically inactive additive
and
catalytically active entity is suspended in water immiscible solvent to which
a solution of
group IIA metal compound is added with vigorous agitation and concurrent
removal of low
boiling or azeotropic fraction of a solvent. Suspension is allowed to age for
1 to 48 hours,
20 wherein the process is accordingly carried out in the temperature ranging
from 70 to 200 C
The support in this case is a mechanically robust and thermally stable solid
in
reaction media, having a mean pore diameter in the range of about 3-3000 A
and existing
as powder, granules, flakes or pallets of regular or irregular shapes, sheets,
monolith, ropes
and woven fabric of fibrous solids and catalytically inactive additive is
independently
25 selected from anions having at least two or more negative charges which may
be organic,
inorganic, or a compound containing at least one radical form 0, N, S, Se, Te,
P, As, Sb,
Bi, Si, olefin, carbene having attached thereto oxy, alkyl, aryl, arylalkyl,
alkylaryl, alcoxy,
arlyoxy, cycloalkyl bearing at least one or more negatively charged functional
groups
independently selected from -S03-,-SO2 -P032-, -COO-, -0-, As032- and -Sy
30 The catalytically active entity is independently selected from metal
complexes,
quaternary compounds, metal oxo anions and polyoxometallates or combinations
thereof
such that metal complexes having a general formula
(M)X(L)y(L*)Z
wherein M is catalytic metal atom or ion of coordination complex selected from
a
CA 02442288 2003-09-26
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41
transition metal groups IIIB, IVB, VB, VIB, VIIB, IB or IIB of the periodic
table of
elements and may be selected independently suitable transition metal ions and
atoms
include Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni,
Pd, Pt, Cu,
Ag, Au, Zn. Preferably the metal complex contains metal atom or ion from group
VIII of
periodic table of elements, x is ranging from 1 to 60, L is selected from
aliphatic, aromatic
and heterocyclic compounds containing at least one radical from 0, N, S, Se,
Te, P, As,
Sb, Bi, Si, olefin, carbene having attached thereto oxy, alkyl, aryl,
arylalkyl, alkylaryl,
alcoxy, arlyoxy, cycloalkyl bearing at least one or more negatively charged
functional
groups independently selected from -S03-,-SO2 -PO32-, -COO-, -0-, AsO32" and -
S- and y is
at least 1 and L* is a radical selected from organic anion, inorganic anion
and coordinating
compound containing at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi,
Si, olefin,
carbene, =C: having attached thereto oxy, alkyl, aryl, arylalkyl, alkylaryl,
alcoxy, arlyoxy,
cycloalkyl, z is from 0 to 7 and the quaternary ammonium compound has a
general
formula
[(Y+)(R*)i ] [Z]
wherein, I = 4 for Y+ = N+, P+, As+, I = 3 for Y+ = S+ and R* is selected
independently from alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy,
cycloalkyl bearing at
least one or more negatively charged functional groups independently selected
from -S03-,-
S02 ,-P032-, -COO", -O", AsO32" and -S" and Z is anion selected from organic
anion,
inorganic anion or coordination complex anion. The group IIA metal cation is
selected
from compounds of Ca2+, Sr2+ and Ba2+.
The solvents employed to forrn a solution of group IIA metal ion are aqueous,
water miscible organic or mixture thereof and solvent employed to suspend
support is
water immiscible organic solvent having boiling point in the range 40 to 200
C, the
present process is concludes by recovering catalyst by centrifugation,
decantation, gravity
settling or other techniques of solid liquid separation and dried subsequently
in vacuum
Process for the preparation of a heterogeneous catalytic formulation as a
solid
composite comprising of porous solid support having deposited thereon a group
IIA metal
compound followed by drying. Solid support having deposited thereon group IIA
metal is
suspended in water immiscible solvent to which a solution of catalytically
active entity and
catalytically inactive additive is added with vigorous agitation and
concurrent removal of
low boiling or azeotropic fraction of solvent. The process of azeotropic
distillation is
accordingly carried out in the temperature ranging from 70 to 200 C. The
liquid medium
employed for the process of azeotropic removal of solvent is water immiscible
organic
CA 02442288 2003-09-26
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42
solvent having boiling point in the range 40 to 200 C. There after suspension
is allowed to
age for 1 to 48 hours.
The support in this case is a mechanically robust and thermally stable solid
in
reaction media, having a pore diameter in the range of about 3-3000 A and
existing as
powder, granules, flakes or pallets of regular or irregular shapes, sheets,
monolith, ropes
and woven fabric of fibrous solids and catalytically inactive additive is
independently
selected from anions having at least two or more negative charges which may be
organic,
inorganic, or a compound containing at least one radical form 0, N, S, Se, Te,
P, As, Sb,
Bi, Si, olefin, carbene having attached thereto oxy, alkyl, aryl, arylalkyl,
alkylaryl, alcoxy,
arlyoxy, cycloalkyl bearing at least one or more negatively charged functional
groups
independently selected from -S03-, -S02y -P032-, -COO-, -O", As032- and -S-
The catalytically active entity is independently selected from metal
complexes,
quatemary compounds, metal oxo anions and polyoxometallates or combinations
thereof
such that metal complexes has a general formula
(M)X(L)y(L*)Z
wherein M is catalytic metal atom or ion of coordination complex selected from
transition
metal group IIIB, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements and is
selected independently suitable transition metal ions and atoms include Sc, Y,
Ti, Zr, Hf,
V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn.
Preferably the
metal complex will contain metal atom or ion from group VIII of periodic table
of
elements, x is from 1 to 60, L is aliphatic, aromatic and heterocyclic
compounds containing
at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene
having attached
thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl
bearing at least one
or more negatively charged functional groups independently selected from -S03-
,-SOZ -
PO32-, -COO", -O", AsO32- and -S- and y is at least 1 and L* is a radical
selected from
organic anion, inorganic anion and coordinating compound containing at least
one radical
from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, =C: having attached
thereto oxy,
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl, z is from 0 to
7 and the
quaternary ammonium compound has a general formula
[(Y+)(R*)r ] [Z ]
wherein, I = 4 for Y+ = N+, P+, As+, I = 3 for Y+ = S+ and R* is selected
independently from
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at
least one or more
negatively charged functional groups independently selected from -S03 ,-S02 -
P032-,
-COO-, -O", As032" and -S" and Z is anion selected from organic anion,
inorganic anion or
CA 02442288 2003-09-26
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43
coordination complex anion. The group IIA metal cation is selected from
compounds of
Ca2+, Sr2+ and Ba2+. And solvent employed to form a solution of group IIA
metal ion is
aqueous, water miscible organic or mixture thereof. After removal of organic
immiscible
and low boiling liquids, centrifugation, decantation, gravity settling or
other techniques of
solid liquid separation and dried subsequently in vacuum to recover the
catalyst
Process for the preparation of a heterogeneous catalytic formulation as a
solid
composite comprising of fluidizing solid support in the current of gasses.
Solution of
catalytically active entity and catalytically inert additive is sprayed in
such a way that
catalytically active entity and catalytically inert additive is deposited on
the solid support
the fluidization of solid is continued for. 1 to 48 hours. Solution of group
IIA metal
compound is subsequently sprayed and fluidization of solid is further
continued for 1 to 48
hours and solids are recovered. The process of fluidization is carried out in
the temperature
ranging from 20 to 200 C, wherein the support in this case is a mechanically
robust and
thermally stable solid in reaction media, having a mean pore diameter in the
range of about
3-3000 A and existing as powder, granules, flakes or pallets of regular or
irregular shapes,
sheets, monolith, ropes and woven fabric of fibrous solids and catalytically
inactive
additive is independently selected from anions having at least two or more
negative
charges which may be organic, inorganic, or a compound containing at least one
radical
form 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene having attached
thereto oxy, alkyl,
aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at least one
or more
negatively charged functional groups independently selected from -S03, -S02 -
P032 ,
-COO-, -0-, As032- and -S" the catalytically active entity is independently
selected from
metal complexes, quatemary compounds, metal oxo anions and polyoxometallates
or
combinations thereof such that metal complexes has a general formula
(M)X(L)y(I,*)Z
wherein M is catalytic metal atom or ion of coordination complex is a
transition metal
from group II1B, IVB, VB, VIB, VIIB, IB or IIB of the periodic table of
elements and may
be selected independently suitable transition metal ions and atoms include Sc,
Y, Ti, Zr,
Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn.
Preferably
the metal complex will contain metal atom or ion from group VIII of periodic
table of
elements, x is from 1 to 60, L is aliphatic, aromatic and heterocyclic
compounds containing
at least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene
having attached
thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl
bearing at least one
or more negatively charged functional groups independently selected from -S03-
,-SO2-
CA 02442288 2003-09-26
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44
-P032-, -COO-, -O", AsO32" and -S" and y is at least 1 and L* is radical
selected from
organic anion, inorganic anion and coordinating compound containing at least
one radical
from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene, =C: having attached
thereto oxy,
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl, z is froni 0
to 7 and quaternary
ammonium compound has a general formula
[(Z'+)(R*)i I [Z ]
wherein, I = 4 for Y+ = N+, P+, As+, I = 3 for Y+ = S+ and R* is selected
independently
from alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at
least one or
more negatively charged functional groups independently selected from -S03", -
SOZ
-P032-, -COO-, -0-, AsO32- and -S- and Z is anion selected from organic anion,
inorganic
anion or coordination complex anion. The group IIA metal cation are selected
from
compounds of Ca2}, Sr2} and Ba2+.The solvent employed to form a solution of
group IIA
metal ion is aqueous, water miscible organic or mixture thereof.
This invention further extends another preferred method for making catalysts
according to present invention. According to this method an anionically
charged entity and
anionically charged additive are deposited on the solid support and are
subsequently cured
by spraying group IIA metal salt solution with simultaneous removal of
solvent.
Accordingly, process for the preparation of a heterogeneous catalytic
formulation
as a solid composite comprises of tumbling solid support in the rotating pan
under current
of inert gasses. Solution of catalytically active entity and catalytically
inert additive is
sprayed in such a way that catalytically active entity and catalytically inert
additive is
uniformly deposited on the solid support the tumbling of solid is continued
for 1 to 48
hours. Solution of group IIA metal compound is subsequently sprayed and
tumbling of wet
solid is further continued for 1 to 48 hours and solids are recovered. The
process described
accordingly is carried out in the temperature ranging from 20 to 200 C.
Either heating the
inert gas stream or rotating pan, which contains support, may achieve the
process
temperature. The laboratory apparatus employed to form present formulation is
represented
in figure 6 and such apparatus may be suitably scaled depending upon volume
requirements.
The support material employable herein is a mechanically robust and thermally
stable solid in reaction media, having a mean pore diameter in the range of
about 3-3000
A and existing as powder, granules, flakes or pallets of regular or irregular
shapes, sheets,
monolith, ropes and woven fabric of fibrous solids.
The catalytically inactive additive is independently selected from anions
having at
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least two or more negative charges which may be organic, inorganic, or a
compound
containing at least one radical form 0, N, S, Se, Te, P, As, Sb, Bi, Si,
olefin, carbene
having attached thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy,
arlyoxy, cycloalkyl
bearing at least one or more negatively charged functional groups
independently selected
5 from -S03",-SOZ -P032", -COO", -O", As032" and -Sy. Additionally this
catalytically
inactive additive may be polymer bearing multiple anionic charges.
Catalytically active entity is independently selected from metal complexes,
quaternary compounds, metal oxo anions and polyoxometallates or combinations
thereof
The metal complex entity that is catalytically active can be selected such
that metal
10 complexes have a general formula
(M)X(I-)y(I-*)Z
wherein M is catalytic metal atom or ion of coordination complex is a
transition metal
from group IIIB, IVB, VB, VIB, VIIB,IB or IIB of the periodic table of
elements and may
be selected independently suitable transition metal ions and atoms include Sc,
Y, Ti, Zr,
15 Hf, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au,
Zn. Preferably
the metal complex will contain metal atom or ion from group VIII of periodic
table of
element. The suffix x indicates number of such catalytic transition metal
present in the
complex. The number of such metal entities ranges from 1 to 60. The component
L of the
metal complex is aliphatic, aromatic and heterocyclic compounds containing at
least one
20 radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene having
attached thereto oxy,
alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at
least one or more
negatively charged functional groups independently selected from -S03, -S02 -
P032-,
-COO-, -O", As032" and -S". The suffix y indicate the number of coordinating
ligands that
hold metal in the lower oxidation state and it is necessary that y is at least
1. L* is a radical
25 selected from organic anion, inorganic anion and coordinating compound
containing at
least one radical from 0, N, S, Se, Te, P, As, Sb, Bi, Si, olefin, carbene,
=C: having
attached thereto oxy, alkyl, aryl, arylalkyl, alkylaryl, alcoxy, arlyoxy,
cycloalkyl. Suffix z
indicates number of such non-participating ligands. These ligands may be
identical if
present in multiple or different but total number ranges from 0 to 7.
Alternatively another
30 class of catalytically active entity, which is employable alone or in
combination with above
said transition metal complex, is quaternary compound which, has a general
formula
[(Y+)(R*)I 1 [Z ]
wherein, compounds that are elected can belong to quaternized compounds of
nitrogen
phosphorus, arsenic and sulfur. Instances when quatemary compound belongs to
nitrogen,
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46
phosphorus, arsenic containing compounds suffix I = 4 for Y+ = N+, P+, and for
sulfur
compounds I = 3 for Y+ = S+ R* is selected independently from alkyl, aryl,
arylalkyl,
alkylaryl, alcoxy, arlyoxy, cycloalkyl bearing at least one or more negatively
charged
functional groups independently selected from -S03 ,-SO2 -P032", -COO", -0-,
As032-
and -S", Z is anion selected from organic anion, inorganic anion or
coordination complex
anion. In majority cases it is implicit that actual catalytic entity is anion
Z- Quaternary
compound provides an anchor for solidification as well as for providing
required
electrostatic field such that anion z- does not get away
The group IIA metal cation is selected from compounds of Ca2+, Sr2+ and Ba2+.
The
lo process for formation of catalyst in coating pan as described earlier
wherein the solvent
employed to form solutions is preferably aqueous, water miscible organic or
mixture
thereof. Such solutions according to process are sprayed simultaniously or
sequentially
Irrespective of the processes employed to form catalytic formulation said
solid
catalytic ensemble could be employed to catalyze diversity of reactions in gas
phase or in
liquid slurry. The catalyst being robust solid provides an opportunity to
select suitable
reactor configuration for manufacture of organic compounds in variety of
reactor
configurations such as fixed bed, trickel bed, fluidized bed and slurry
reactors depending
on the physical state and properties of reactants and products.
The solid catalyst of the present invention can be optionally modified wherein
a
film of high boiling liquid or low melting solid is optionally deposited on
the solid catalyst.
This modification can be adopted to enhance local solubility of reactants or
modify
environment of the catalytic sites to obtain high selectivity for required
products.
The catalyst to be formulated according to earlier described embodiments for
particular reaction is selected from analogous catalysts that catalyze such
reaction in liquid
phase; analogues entity is derived from such parent catalyst of homogeneous
system by
appropriate functionalization so as to introduce negative charges on it.
Catalytically active
entity is independently derived from metal complexes, quatemary compounds,
metal oxo
anions and polyoxometallates or combinations thereof depending upon
requirement.
Except anionic functional groups rest structure of catalytic entity in
immaterial for
solidification of such entity. Some of illustrative derivations of anionically
charged entities
from respective soluble catalysts are displayed in following table. Reaction
classes
represented are exemplary only and catalytic entities are within the purview
of appended
claims. It is thus explicit clarification of the embodiment that solid
catalyst formulation is
described wherein the catalytic entities are solidified by generic technique
irrespective of
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47
reaction they catalyze. Such catalytic entities are clearly claimed in claims.
Some of the illustrative examples of anionically functionalized soluble
catalytic
entities and their applications are listed in following table.
Reaction type Soluble catalyst Analogus anionic entity
H droform lation HRhCO(TPP)3 HRhCO(TPPTS)3
HRhCO(BISBI)3 HRhCO(BISBIS)3
C02CO4[P(,aBu)3]2 Co2CO4[TPPTS]2
SnC13PtC1(TPP)2 SnC13PtC1(TPPTS)2
Hydrogenation
RhCI(TPP)3 RhCI(TPPTs)3
RuC12(C6H5)BINAP(S) RuC12(C6H5)BINAP(S)
RhC1O4Chiraphos (S,S) RhC1O4Chiraphossulfonate
d (S,S)
Carbonylation
PdAcPTSA(TPP)2 PdAcPTSA(TPP)2
Rh(CO)2I2-[MeN+(Ph)3] Rh(CO)2I2 [MeN+(PhmSO3
)3]
Heck olefination
PdC12(PPh3)2 PdC12(TPPTS)2
Suzuki coupling
PdC12(PPh3)2 PdC12(TPPTS)2
Isomarization
PtC12(PPh3)2 PtC12(TPPTS)2
RhCI(TPP)3 RhCl(TPPTs)3
Wacker oxidation
Pd(Ac)2BIPY Pd(Ac)2BIPYDS
Oxidation
CoPthalocynine CoPthalocyninetetrasulfonat
ed
Michel and
Knoven el reactions
NaOH OH-[MeN(PhrnSO3 )3]
NaOMe MeO-[MeN+(PhmSO3 )3]
The supported catalysts according to the invention are extremely active as is
born
out by the tests in the description, which is given in the examples, which
follow. In fact
these examples relate to the application of such supported catalysts to the
diversity of
reactions catalyzed by different mechanisms and according to known theories of
molecular
catalysts. A comparison of the reactions of these supported catalysts in
homogeneous
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48
phase establishes that while retaining catalyst activity to considerable
extent facile
separation can be easily achieved. This makes catalyst suitable for continuous
process
thereby enhancing catalyst process economics. The said catalyst formulation
being
inherently solid can be easily recovered after the desired catalytic
conversion in the
heterogeneous phase. They can then be reused to catalyze new charge of
reactants, this
operation being either continuos or repeatable wherein the catalyst can be
recycled for
several times. The advantageous fact is catalytic formulation being repeatable
several times
without their activity being appreciably degenerating.
Before subjecting catalysts for purpose of catalyzing reactions it is
essential that
stability and incompatibilities be assessed. For this reason various chemical
stresses were
applied to simulate stresses encountered by the catalytic formulation when
they are applied
to actual reaction. The stresses encountered during reaction or during post
processing are
solvation stresses due to solvents and media. Ranges of solvents that are
applicable are
liquids employed for reaction and post processing such as washing. Washing is
preferred
process to regenerate catalyst to remove adsorbed material and for activation
by other
chemical treatment.
For this reason various catalysts containing different metals such as rhodium,
ruthenium, iridium, palladium, platinum, cobalt, nickel, molybdenum and iron
were
prepared according to methods described earlier and extracted at boiling
temperatures of
the solvents like, water, acetic acid, methanol, isopropanol, ether,
tetrahydrofuran, ethyl
acetate, acetone, acetonitrile, toluene, cyclohexane in the apparatus detailed
in figure 3.
The extraction was continued for several hours and subsequently solvent was
changed. No
appreciable loss of metal content was and physical morphology by visual
comparison was
detected. It is obviously true that sites containing hydroxy, methoxy and
other basic
radicals would be destroyed. These experiments indicate that catalyst would be
stable in
diverse range of solvents and need not be restricted to particular class of
solvents.
Similarly catalysts were leached in aqueous acids and alkaline solutions and
loss of metals
including transition metal or group IIA metal was detected
The activity of the catalyst studied has been measured in the examples in
conventional manner by ~ the turnover number which defines number of molecules
converted by the catalytic reaction for a catalytically active entity per unit
time under
idealized conditions or as yield over a defined period of time.
Various exploratory experiments were. carried out to ascertain applicability
of the
catalyst of the invention. The exploratory experiments were aimed at
=understanding
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49
molecular catalysis. Due to this reason reaction was selected where two
products are
formed with dissymetric regioselectivity. Hydroformylation is one such
reaction wherein;
reaction rates and regioselectivities are significantly altered because of
variation of
molecular environment. Due to these reasons hydrofomiylation of hexene with
HRhCO(TPPTS)3 was considered as suitable probe to understand catalysis in
reaction
conditions.
Hydroformylation reaction was carried out for hexene as substrate and
HRhCO(TPPTS)3 as active catalytic entity (g of rhodium/g of support), moisture
content
(ppm), silica as support and no excess of ligand. Total conversion was
obtained and the
catalyst was recovered by centrifugation, washed with toluene, and dried in
vacuum. Dry
catalyst powder was reused for hydroformylation of allyl alcohol in water
catalyst was
active for hydroformylation providing aldehydes. Catalyst after reaction was
recovered by
centrifugation, dried in vacuum, reused for hexene hydroformylation, and found
to produce
aldehydes. This experiment indicated feasibility of catalyzing reaction in
various solvents
successively irrespective of substrate.
Accordingly need of support was identified by precipitating HRhCO(TPPTS)3 with
barium nitrate precipitate was used to catalyze hexene hydroformylation. After
24 hours,
conversion was below 1%.
In order to identify that reactions take place in solid state and not by
leaching of
complex under reaction conditions, which eventually return to solid. This is
verified by
using criteria of mobility of catalyst species and additional ligand. In case
of soluble
catalyst wherein additional ligand is in mobile condition due to which it can
interact with
active species and there by giving lower rates and high n/I ratio. When
catalysts were
prepared with additional ligand present no change in activity and selectivity
was observed.
This observation was attributed to immobile state of ligands and catalyst. Due
to
immobility of ligands their interaction with active species is totally
retarded thereby not
affecting rates and n/i ratio.
Immobility of catalyst was further verified by addition of water to the solid
catalyst. At lower water content (ppm/g) high conversions were obtained. When
moisture
content was increased activity was considerably reduced. Same catalyst when
dried
resumed its original activity. This experiment conclusively verifies that
reaction occurs in
solid state.
Accordingly the crucial evaluation indicating life of the catalyst, its
stability and
the durability was performed in a tubular fixed bed reactor by subjecting
catalyst to
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hydroformylation in tubular trical bed reactor (o 'h") at 80 C and 300 psi
H2/CO (1:1)
using 5 g. of catalyst. 5 % decene in toluene was pumped continuously at the
feed rate of
10 ml/hr conversion levels were 20 % for aldehydes (n/i 2.1) after attaining
steady state.
The reaction was continued for 72 hr without loss of activity. Reaction was
arrested by
5 discontinuing the liquid feed and water was pumped for 1 hr. thereafter
reactant feed was
resumed. Initially there was no conversion, which was steadily resumed over
the period of
10 hr. This observation was attributed to formation of water film on the
catalyst surface,
which physically retards contact of decene with catalyst surface. Moreover
water does not
wash out complex catalyst, which provides conclusive proof that reaction
occurs in the
10 solid state.
The technique of solid catalyst formulation is established in present
invention
according to which solid catalyst can be formulated and applied for catalyzing
reactions in
diversity of solvents. The catalytic formulation referred herein was applied
to variety of
reactions according to yet another embodiment. An exemplary reaction class for
which
15 catalytic formulation was employable is described in subsequent sections.
Reaction classes
that are described here are only exemplary and limited by scope of
catalytically active
entity as said earlier. Variety of reaction classes described herein are
intended to outline
the scope of catalytic formulation that is under consideration wherein
emphasis given on
catalyst separation, stability and convenience of operation when applied to
manufacture of
20 plurality of organic compounds. Classes of reaction described herein are
hydroformylation,
hydrogenation, carbonylation, carbon-carbon bond formation by Heck and Suziki
type
reactions, isomarization, epoxidation, Wacker oxidation, Michel addition and
Knovengel
condensation.
Metal catalyzed addition of carbon monoxide and hydrogen to olefin provides
25 access to aldehydes and in certain cases followed by hydrogenation. Wide
diversity of
olefins can be hydroformylated to corresponding aldehydes various olefins were
hydroformylated with analogue of classical Wilkinson's catalyst. Various
olefins such as
hexene, styrene, cyclohexene and vinylacetate were hydroformylated. Similarly
hexene
was hydroformylated with rhodium modified with different ligands to control
selectivity.
30 Accordingly other metals active for hydroformylation were also tested such
as cobalt and
platinum.
Palladium phosphine complexes catalyze Carbonylation of halides, alcohols and
olefins in homogeneous reaction systems. Analogues of such palladium complexes
were
formulated and tested for styrene, styryl alcohol, phenyl acetylene and
bromobenzene.
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51
Reasonable activities were obtained in each case and catalyst can be reused.
Various phosphine amines, phosphite complexes of Zr, Hf, V, Cr, Mo, W, Mn, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, are useful for hydrogenation of variety of
functional
groups. Hydrogenation of olefins, carbonyl, and nitroaromatics were tested
with the
catalyst formulated with this invention.
The extension of substituted alkenes by direct carbon - carbon bond formation
at
vinylic carbon center is useful reaction for manufacture of variety of organic
synthesis.
Such synthetic procedure is difficult to achieve by conventional organic
synthesis. The
palladium complexes (PdO) have proved to be effective in this sense. Various
palladium
complexes including phosphine, metalated phosphine and phosphites are useful
catalysts
other metal such, as nickel and platinum are also useful in this respect.
Olefination of aryl
bromides was demonstrated with catalytic formulation of the invention.
Palladium catalyzed cross-coupling reactions of aryl or vinyl boronic acids
with
aryl halides are well known in the art. Such coupling reactions are carried
out in polar as
well as non-polar media. Palladium phosphine complexes are useful in this
respect.
Varieties of biaryl compounds are accessible through this reaction. The
catalytic
formulation of this invention is also suitable for this class of reactions.
Double bond isomarization is useful reaction in converting olefins to
isomarized
olefins. Various transition metal complexes catalyze this type of reaction.
Metal complexes
useful in this respect are platinum, palladium, rhodium and cobalt. The
catalytic
formulation of present invention is also useful in catalyzing this reaction
Present catalytic formulation is also suitable for oxidation of olefins to
epoxides
and acids. For example molybdate ion when hetereogenized as quaternary
ammonium ion
pair can catalyze epoxidation of olefins. Various pthalocyanines are also
useful in this
respect.
Nucleophilic addition of mesomeric anion to activated olefins such as a(3
unsaturated olefins is known as Michel reaction. Compounds containing electron-
withdrawing groups having relatively acidic protons . are suitable compounds
to form
mesomeric anions such compounds are for example R-CH2-Z wherein Z is electron-
withdrawing group such as CN, COOR, NO2, CHO etc. and R may be alky aryl or Z
as
defined earlier. In presence of strong base these compounds for anion R-CH (-)-
Z which
adds to a-(3- unsaturated olefins at 0 position. The activated olefins may be
represented as
C=C-Z where in carbon attached to Z is a and adjacent carbon is P.
Generally catalyst employed to form said mesomeric ions are strong bases such
as
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52
If, OH", MeO-, etc. Anion fragments as such are difficult to solidify
therefore counter
cation selected for such is quaternary ammonium compounds, which are
functionalized
with anionic functional groups, and ion pair as a whole is precipitated on
solid support. In
cases where quaternary ammonium compounds exist as alcoxy ion pair, solidified
quaternary compound formulation is successively washed with solution of alcoxy
anion
prior to use. Condensation of diethyl malonate with ethyl acrylate, diethyl
maleate,
acrylonitrile, are demonstrated in examples appended hereinafter.
Condensation of aldehydes or ketones, usually not containing an a hydrogen
with
compounds of the form R-CH2-Z to form olefins is called as Knovengel reaction
(Jones,
Org. react. 1967, 15, 204-599) wherein Z may be CHO, COR, COOH, COOR, CN, NO2.
The catalysts generally employable for this reaction are basic amines,
hydroxyl anion or,
alcoxy anion. Anion fragments as such are difficult to solidify therefore
counter cation
selected for such is quaternary ammonium compound, which is functionalized
with anionic
functional groups, and ion pair as a whole is precipitated on solid support.
In cases where
quatemary ammonium compounds exist as alkoxy ion pair, solidified quaternary
compound formulation is successively washed with solution of alcoxy anion
prior to use.
Condensation of butyraldehyde to 2-ethylhexenal, benzaldehyde and acetone to
dibenzyledene acetone, benzaldehyde and acetonitrile to cinnamonitrile are
demonstrated
in examples appended hereinafter
It would be evident from these descriptions that wide diversity of soluble
catalysts
can be formulated by appropriately forming catalytic entities that are
anionically charged.
These entities are structurally analogues to the soluble catalytic entities.
The catalysts that
are employable in this context are metal complexes, quatemary ammonium
compounds
wherein complimentary anion is catalyst (complimentary anion can be metal
complex,
organometallic anion or inorganic anion).
The present invention was conceived without limiting the said solid catalytic
formulation to one particular class of complexes or reaction catalyzed by them
following
certain mechanism, according to some particular theory. It is perceived that
solid support
having high surface area provides a mechanical strength and a surface upon
which
insoluble catalytic material is physically implanted. The insoluble material
is generated
from interaction of otherwise soluble complex catalyst containing two or more
anionic
functional groups and calcium, strontium and barium salt solutions. This
material, is
formed on the surface of the solid support as a vehicle. The composite solid
assembly
resulting therefrom can be suitably used as solid catalyst.
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53
Moreover, recycling and regeneration of applicants' preferred catalytic
formulations is readily accomplished using known methods and procedures, for
example
when acceptable conversion level has occurred in a given batch run whether it
is
determined by elapsed time or monitored by consumption of substrate or some
other
parameter. The vessel need only be brought to ambient temperatures and vented
off
residual pressure if any. The reaction mixture thereafter may simply be
separated from
catalyst by simple decanting. The catalytic formulation is filtered and
possibly washed
with suitable liquid for later reuse or simply recharged with feedstock as
needed and a
subsequent reaction begun.
As catalyst lifetimes are better understood through working with a particular
catalyst formulation in repeated recycling in either laboratory or in
commercial settings it
may be further desirable to regenerate catalyst time to time either by washing
with suitable
liquid or by specific chemical treatment. Continuos reaction processes are
also practicable
for applicants preferred catalysts in view of their insolubility and
resistance to leaching or
other disintegration. Such processes can be designed and implemented using
common and
known procedures in the art.
For the purpose of further promoting a better understanding of the catalysts
and
processes of the present invention, reference will now be made in the examples
below to
specific instances of their preparation and use. These examples are exemplary
only and no
limitation of the scope or breadth of applicants' invention is intended
thereby. Various
modifications and variations of this invention will be obvious to a worker
skilled in the art
and it is to be understood that such modifications and variations are to be
included within
the purview of this application and the spirit and the scope of the appended
claims
Examples
Experiment 1
(Verification of the hypothesis)
This comparative example illustrates the validation of the hypothesis that
anions
having two or more negative charges when interacted with group IIIA metal
cations except
Mg+2 invariably result in to a precipitate which is practically insoluble in
organic solvents
(including nonpolar, polar (protic and aprotic) and sparingly soluble in
aqueous solvent in
certain cases). This hypothesis was verified as follows. Solutions of
different anions were
interacted with group IIA metal ions. 0.1 molar solutions of anionic component
(solution
A) and 0.1 molar solutions of group 11A cation (solution B) component were
prepared. 10
ml of solution B was mixed with 50 ml of solution A in boiling tubes solutions
were
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54
thoroughly mixed on shaker for 10 hr. resulting suspensions were centrifuged
and
precipitate was removed by decanting supernatant liquid. Residual precipitate
was diluted
with distilled water followed by centrifugation and decantation was repeated
thrice. To this
precipitate 10 ml methanol was added and centrifugation and decantation
procedure was
repeated resulting wet precipitates were vaccume dried at 50 C. Mixtures
where
precipitate was not observed were discarded. Dried precipitate barium and
strontium were
found insoluble in water, methanol, ethanol, propanol, butanol, acetic acid,
benzene
xylene, petroleum ether, ethyl acetate, acetone methyl ethyl ketone,
acetonitrile,
dimethylformamide, chloroform, tetrahydrofuran. Where as some salts of calcium
were
found sparingly soluble.
Results are summarized in following table.
Solution of group IIA metal Solution of anion (0.1 molar) observation
cation (0.lmolar)
Magnesium chloride Sodium nitrate No precipitate
Calcium chloride Sodium nitrate No precipitate
Strontium chloride Sodium nitrate No precipitate
Barium chloride Sodium nitrate No precipitate
Magnesium chloride Sodium propionate No precipitate
Calcium chloride Sodium propionate No precipitate
Strontium chloride Sodium propionate No precipitate
Barium chloride Sodium propionate No precipitate
Magnesium chloride p-toluene sulfonate sodium No precipitate
Calcium chloride p-toluene sulfonate sodium No precipitate
Strontium chloride p-toluene sulfonate sodium No precipitate
Barium chloride p-tolune sulfonate sodium No precipitate
Magnesium chloride m- benzene disulfonate No precipitate
disodium
Calcium chloride m- benzene disulfonate White precipitate
disodium
Strontium chloride m- benzene disulfonate White precipitate
disodium
Barium chloride m- benzene disulfonate White precipitate
disodium
Magnesium chloride di-sodium oxalate No precipitate
Calcium chloride di-sodium oxalate White precipitate
Strontium chloride di-sodium oxalate White precipitate
Barium chloride di-sodium oxalate White precipitate
Magnesium chloride Sodium sulfate No precipitate
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Calcium chloride Sodium sulfate White precipitate
Strontium chloride Sodium sulfate White precipitate
Barium chloride Sodium sulfate White precipitate
Magnesium chloride di-sodium phenyl phosphonate No precipitate
Calcium chloride di-sodium phenyl phosphonate White precipitate
Strontium chloride di-sodium phenyl phosphonate White precipitate
Barium chloride di-sodium phenyl phosphonate White precipitate
Magnesium chloride Na2HPOd No precipitate
Calcium chloride Na2HPO4 White precipitate
Strontium chloride Na2HPO4 White precipitate
Barium chloride NazHPO4 White precipitate
Magnesium chloride di-sodium phthalate No precipitate
Calcium chloride di-sodium phthalate White precipitate
Strontium chloride di-sodium phthalate White precipitate
Barium chloride di-sodium phthalate White precipitate
Magnesium chloride Ammonium molybdate No precipitate
Calcium chloride Ammonium molybdate White precipitate
Strontium chloride Ammonium molybdate White precipitate
Barium chloride Ammonium molybdate White precipitate
Magnesium chloride Sodium carboxy methyl No precipitate
cellulose
Calcium chloride Sodium carboxy methyl White precipitate
cellulose
Strontium chloride Sodium carboxy methyl White precipitate
cellulose
Barium chloride Sodium carboxy methyl White precipitate
cellulose
Magnesium chloride Sodium polyvinyl sulfonate No precipitate
Calcium chloride Sodium polyvinyl sulfonate White precipitate
Strontium chloride Sodium polyvinyl sulfonate White precipitate
Barium chloride Sodium polyvinyl sulfonate White precipitate
In addition to these, EDTA acetyl acetonate, hydride compounds of calcium were
interacted with sodium sulfate, sodium phosphate to yield insoluble
precipitate.
5 Experiment 2
Synthesis of high purity oleum
2 lit. Three-necked flask was attached with distillation condenser, addition
funnel
and to another end collection vessel with bottom drain valve. Distillation
condenser was
also provided with pressure relief non-return valve. In flask magnetic bar was
placed and
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56
500 g. P205 was charged. 45 ml conc. H2S04 was placed in collection vessel.
400 ml conc.
H2S04 was placed in addition funnel. Addition was started with simultaneous
magnetic
agitation over the period of 2 hours. Temperature of flask was raised slowly
until slow
distillation of sulfur trioxide was started. Sulfur trioxide was collected in
conc. H2S04 in
collection vessel after total volume of liquid in collection vessel reached to
148 ml, heating
was stopped and assembly was dismantled.
Experiment 3
Synthesis of Triphenyl phosphine trisulfonate
Triphenyl phosphine trisulfonate was synthesized by following procedure.
Triphenylphosphine 50 g. was placed in sulfonation reaction followed by
vaccume argon
degassing and blanketed with argon. Sulfonation reactor was cooled to 5 C and
200 g
sulfuric acid was charged in the sulfonation reactor without allowing
temperature of
reactor to cross 10 C. Addition of sulfuric acid was carried out with
constant stirring with
mechanical stirrer over a period of 2 hours. Reaction mixture assumed pale
yellow color.
To this reactor 280 g of 65 % oleum prepared as per previous expe,riment was
charged over
a period of 60 min. temperature of the sulfonation reactor was raised to 22 C
and reaction
was continued for 76 hours. There after temperature of the reaction was
lowered to 0 C and
50 ml distilled and degassed water was introduced in the sulfonation reactor
without
allowing temperature to rise beyond 5 C over a period of three to four hours.
This solution
was further diluted with 500 ml water. The diluted solution was transferred to
3-lit jacketed
vessel and chilled to 5 C and consequently neutralized with 50 % w/w NaOH in
water,
which was previously degassed. At neutralization point solution assumed
distinct yellow
color at this instance NaOH addition was discontinued and pH was lowered to 6
by
addition of con sulfuric acid. During neutralization formed sodium sulfate
partially
precipitates which was removed by filtration and resulting solution was
concentrated under
vacuum to 300 ml. formed sodium sulfate was removed by filtration. Mother
liquor
containing TPPTS was further diluted with 2000 ml degassed methanol and
refluxed for
two hours during which most of the sodium sulfate precipitated, supematant
extract of
TPPTS in methanol was removed by filtration TPPTS extract in methanol was
evaporated
to dry ness and white colored solid was obtained (purity above 95% by P31NMR).
This
solid was dissolved in minimum amount of water and reprecipitated with
degassed ethanol
to obtain TPPTS with purity > 99 %.
Experiment 4
Synthesis of disodium P-phenyl-3, 3'-phosphine dialy bis (benzene sulfonate)
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Orthoboric acid (48 g) was dissolved in concentrated sulfuric acid 98% (200
ml) to
this was added 65% oleum 200 ml. the temperature of the solution was raised to
60 C and
excess sulfur trioxide was removed in high vaccume by providing a gas trap
attachment
containing calcium oxide (trap was chilled to -10 C) solution of orthoboric
acid and sulfur
trioxide was cooled to 5 C and 30 g triphenyl phosphine was added under argon
blanket.
Resulting mixture was agitated by mechanical stirrer and temperature of the
reactor was
raised to 58 C and reaction was continued for 90 hours. The temperature was
reduced to
0 C and hydrolyzed with 500 ml degassed water. This solution was neutralized
with 50%
w/w sodium hydroxide in water until neutralization and formed precipitate was
removed
by filtration and mother liquor was concentrated to 300ml and diluted with
1000 ml
methanol and refluxed for 2 hours. Resulting precipitate was removed by
filtration. The
extract in methanol was evaporated to obtain a solid which was suspended in
1000 ml
methanol and to this 50 g microcrystalline cellulose avicel was added followed
by 20 ml
conc. H2S04 and refluxed for 6 hours under argon blanket. Solution was cooled
and
filtered to remove avicel. To this 50 g. AvicelT"' was again added and
refluxed for another
6 hours suspension was filtered and methanolic extract was neutralized with 50
% NaOH
w/w and filtered. Solution was evaporated to obtain white compound correct
elemental
analysis.
Experiment 5
Synthesis of trisodium 3,3', 3"-phosphine trial tris (4 methyl benzene
sulfonate)
Orthoboric acid (g., 6.6 mmol) was dissolved in concentrated sulfuric acid
(96%,
3.75 ml) to this (2-methylphenyl) phosphine (0.50 g., 1.4 mmol) was dissolved
in reaction
mixture. Oleum (6.75 ml, 65 % w/w) was added drop wise while temperature of
reaction
mixture was 0 C. After stirring for 72 hours at 25 C, the temperature was
lowered to 0 C
and the mixture was hydrolyzed by addition of 5 ml degassed water. This
solution was
neutralized with 50 % w/w sodium hydroxide in water until neutralization and
formed
precipitate was removed by filtration and mother liquor was concentrated to 3
ml and
diluted with 10 ml methanol and refluxed for 2 hours. Resulting precipitate
was removed
by filtration. The extract in methanol was evaporated to obtain a solid which
was
suspended in 10 ml methanol and to this 0.5 g microcrystalline cellulose
avicel was added
followed by 0.5 ml conc. H2S04 and refluxed for 6 hours under argon blanket.
Solution
was cooled and filtered to remove avicel. To this 0.5 g. aviel was again added
and refluxed
for another 6 hours suspension was filtered and methanolic extract was
neutralized with 50
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% NaOH w/w and filtered. Solution was evaporated to obtain white compound
correct
elemental analysis.
Experiment 6
Synthesis of sodium salt of sulfonated tribenzyl phosphine
Sulfonation of tribenzyl phosphine was carried out anoaloguous to triphenyl
phosphine except exact degree of sulfonation was not established reaction
mixture
containing di and tri sulfonated phosphine was used for further experiments.
Experiment 7
Sulfonation of 1-3 bis -diphenyl phosphino propane
4.95 g. (12 mmol) of diphenylphosphino propane was dissolved in a solution of
4 g. (64.7
mmol) orthoboric acid in 37.5 ml (98%) reaction mixture was cooled to 0 C, to
this 65%
oleum 67.5 ml was added drop wise over a period of 2 hours. After addition
reaction
mixture was brought to 25 C and stirred for 48 hours. After this reaction
mixture was
brought to 0 C and hydrolyzed with 50 ml degassed water. This solution was
neutralized
with 50 % w/w sodium hydroxide in water until pH 7 and formed precipitate was
removed
by filtration and mother liquor was concentrated to 30 ml and diluted with 100
ml
methanol and refluxed for 2 hours. Resulting precipitate was removed by
filtration. The
extract in methanol was evaporated to obtain a solid which was suspended in
100 ml
methanol and to this 5 g microcrystalline cellulose avicel was added followed
by 1 ml conc
H2SO4 and refluxed for 6 hours under argon blancket. Solution was cooled and
filtured to
remove avicel. To this 5 g. avicel was again added and refluxed for another 6
hours
suspension was filtered and methanolic extract was neutralized with 50 % NaOH
w/w and
filtered. Solution was evaporated to obtain a white compound
Experiment 8
Sulfonation of 1-2 bis-diphenyl phosphino ethane
Preparation was carried out in analogous manner as explained in previous
experiment
Experiment 9
2,2'-bis(diphenylphosphinomethyl)-1,1'biphenyl (Bisbi) synthesis and
sulfonation
Equip a three litre three-necked flask with a sealed mechanical stirrer, a
reflux
condenser and a thermometer. Dissolve 89 g. (0.5 mol) of phenanthrene in one
litre glacial
acetic acid in the flask and warm to 85 C on a water bath. Introduce 345 ml of
30%
hydrogen peroxide solution (4 mol) during 40 min. temperature falls to about
80 C
continue for 6 hr. remove acetic acid and water under reduced pressure to
obtain brown
color solid digest this residue in 2N sodium hydroxide solution and add 4 g of
powdered
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59
charcoal and warm the mixture to 75 C and filter. Filtrate was acidified to pH
2 with the
conc. HC1 white precipitate was filtered and dried at 50 C MP 109 C, 83 g 69 %
material
obtained is of sufficient purity for further synthesis.
Equip a three litre three-necked flask with a sealed mechanical stirrer, a
reflux
condenser and a thermometer. Flask was cooled to 0 C in ice salt bath.
Reaction vessel
was charged with 24.2g (0.1 mol) diphenic acid and 15.12 g (0.4 mol) sodium
borohydride
to this solid powder 200 ml dry tetrahydro furan was added in such a way that
there is,
minimum effervescence. After 1 hour suspension becomes uniform and to this
(0.2 mol
H2S04 in 100 ml tetrahydrofuran was added over a period of 2 hours while
maintaining
temperature at 0 C. after addition was over mixture was allowed to stirr for
24 hours at
room temperature. To this white suspension 100 ml 30 % NaOH was added and
refluxed
for 4 hours and liquid was braught to room temperature and extracted with
chloroform to
yield white solide. Which was used further without purification.
Diol intermediate (0.08 mol) from above said preparation was dissolved in
chloroform and transferred to two necked flask attached with condenser and
guard tube,
pressure equalizing addition vessel. One drop of pyridine was added to flask
and (0.2 mol)
thionyl chloride was dissolved in 25 ml chloroform and charged in addition
vessel. Thionyl
chloride was added to round bottom flask at room temperature. During addition
considerable amount of sulfur dioxide and hydrogen chloride escaped from guard
tube.
The temperature of the flask was raised until chloroform started refluxing.
After 5 hours
reaction was quenched by addition of water. Chloroform was exteracted with
bicarbonate
solution followed by water and dried by passing through bed of sodium sulfate.
Chloroform was evaporated under vaccume at 50 C to yild yellow colored oil
(irritant and
inflammatory to skin), which was distilled, in high vaccume to yield pale
yellow colored
oil.
(Following procedure was adopted from US patent 4,879,416).
To a 500m1 flask equipped with a mechanical stirrer, thermowell, addition
funnel
and condencer was added triphenyl phosphine 16.77 g , 0.064 mols ,
tetrahydrofuran 64 ml
and lithium wire 0.88 g, 0.128 atoms. The flask was cooled to 15 C reaction
mixture was
stirred overnight to yield red colored solution with complete dissolution of
lithium. The
flask was cooled further to 5 C and tertiary butyl chloride 5.92 g 0.064 mols
was added
and temperature was raised to 50 C and maintained for 2 hours. Reaction
mixture was
cooled and to this 7.5 g of above said dichloride was slowly added.
Temperature of the
reaction mixture was raised such that it gently boils. Reaction was quenched
by addition of
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5 ml methanol. The reaction mixture was evaporated to yield sticky mass, which
was
dissolved in sufficient diethyl ether and washed with water. Evaporation of
diethyl ether
yields pale yellow colored sticky mass, which was recrystallized from
THF/Methanol to
yild fine crystals of white material.
5 This material was sulfonated according to method described for diphenyl
phosphino propane. To produce white coloured compound, which was soluble in
water.
Experiment 10
Sulfonation of (R) BINAP (2, 2' -bisdiphenylphosphino -1,1' binapthyl)
Procedure of sulfonation was adopted from US patent 5756838. 0.5 g. of (R)
10 BINAP was dissolved in 1.75 ml of concentrated sulfuric acid at 10 C under
argon.
Afterwards, 7.5 ml of oleum 40 % w/w was added dropwise over 2-3 hours the
resulting
mixture was stirred at 10 C for 76 hours. After stirring this mixture was
slowly poured
over 100 g ice followed by dropwise addition of 50 % w/w NaOH untill solution
was
neutralized to pH 7. The resulting solution was concentrated under vaccume to
30 ml. to
15 this 100 ml methanol was added in order to precipitate sodium sulfate.
Methanolic
extracted was evaporated under vaccume to obtain solid, which was dissolved in
methanol
and filtered. Methanol was evaporated to obtain white solid.
Similarly s BINAP was sulfonated.
Experiment 11
20 Sulfonation of (S, S chiraphos) (S) (S) 2,3 bisdiphenylphosphino butane.
Procedure of sulfonation was adapted from Alario et al, J. Chem. Soc., Chem.
Commun., 1986,202
Experiment 12
Sulfonation of R prophos 1, 2(S) bisdiphenylphosphino propane
25 Procedure of sulfonation was adapted from Amrani et al Organometallics
1989, 8, 542
Experiment 13
Sulfonation of R, R 2-5,bis diphenylphosphino penatne
Procedure of sulfonation was adapted from Amrani et al Organometallics 1989,
8,
542 Sulfonation of 2-pyridyl phosphine
30 Experiment 14
Synthesis of sodium salt of sulphonate of triphenylamine.
2 g of Triphenyl amine was charged into a reactor, and 20 cc of concentrated
sulfuric acid was added to it. This mixture was stirred until the amine
dissolved. 20 cc of
oleum 65% was added to this mixture under rapid stirring, and the reactor was
cooled to
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61
about 20 C. After the addition of oleum, the reactants and contents were
heated to 50 C
and maintained at this temperature for 48 hours. The reactor and its contents
were cooled,
and distilled water (10cc) was added to the reaction mixture to quench the
oleum. 50%
NaOH solution was added to this solution, under cooling (10 C) until the
sulfuric acid
solution was neutralized. The solution was concentrated and then methanol was
added to
extract the water-soluble ligand from the sodium sulfate powder. The methanol
was
evaporated to yield the water-soluble sodium salt of triphenyl amino sulfonic
acid [1.6g].
The product consists of mixtures of the bis and grater than 95 % tris
sulfonation products.
These can be used as such in synthesis of metal complexes for catalysis.
Experiment 15
Trisodium salt of tribenzyiamine trisulfonate
2 g of Tribenzyl amine was charged into a reactor, and 20 cc of concentrated
sulfuric acid
was added to it. This mixture was stirred until the amine dissolved. 20 cc of
oleum 65%
was added to this mixture under rapid stirring, and the reactor was cooled to
about 20 C.
After the addition of oleum, the reactants and contents were heated to 50 C
and maintained
at this temperature for 48 hours. The reactor and its contents were cooled,
and distilled
water (10cc) was added to the reaction mixture to quench the oleum. 50% NaOH
solution
was added to this solution, under cooling (10 C) until the sulfuric acid
solution was
neutralized. The solution was concentrated and then methanol was added to
extract the
water-soluble ligand from the sodium sulfate powder. The methanol was
evaporated to
yield the water-soluble sodium salts of Tribenzyl amino sulfonic acid [1.7 g]
degree of
sulfonation was established by H1 NMR and elemental analysis.
Experiment 16
Synthesis of sodium salt of sulphonate of 2,2'bipyridine.
2 g of 2,2'Bipyridine was charged into a reactor, and 20 cc of concentrated
sulfuric
acid was added to it. This mixture was stirred until the amine dissolved. 20
cc of oleum
65% was added to this mixture under rapid stirring, and the reactor was cooled
to about
20 C. After the addition of oleum, the reactants and contents were heated to
50 C and
maintained at this temperature for 48 hours. The reactor and its contents were
cooled, and
distilled water (10cc) was added to the reaction mixture to quench the oleum.
50% NaOH
solution was added to this solution, under cooling (10 C) until the sulfuric
acid solution
was neutralized. The solution was concentrated and then methanol was added to
extract the
water-soluble ligand from the sodium sulfate powder. The methanol was
evaporated to
yield the water-soluble sodium salt of 2,2'bipyridine di sulfonic acid. [1.2
g] The product
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consists of mixtures of the bis sulfonation products as indicated by elemental
analysis and
lh NMR. These can be used as such in synthesis of metal complexes for
catalysis.
Experiment 17
Sulfonation of 2 phenyl pyridine
2 g of 2,phenylpyridine was charged into a reactor, and 20 cc of concentrated
sulfuric acid was added to it. This mixture was stirred until the amine
dissolved. 20 cc of
oleum 65% was added to this mixture under rapid stirring, and the reactor was
cooled to
about 20 C. After the addition of oleum, the reactants and contents were
heated to 50 C
and maintained at this temperature for 48 hours. The reactor and its contents
were cooled,
and distilled water (10cc) was added to the reaction mixture to quench the
oleum. 50%
NaOH solution was added to this solution, under cooling (10 C) until the
sulfuric acid
solution was neutralized. The solution was concentrated and then methanol was
added to
extract the water-soluble ligand from the sodium sulfate powder. The methanol
was
evaporated to yield the water-soluble sodium salt of 2-phenylpyridine sulfonic
acid. [1.2 g]
The product consists of mixtures of the bis sulfonation products as indicated
by elemental
analysis. These can be used as such in synthesis of metal complexes for
catalysis.
Experiment 18
Synthesis of 2-3 bisdiphenylphosphino, succinic acid sodium salt
To a reaction system comparising a solution of dimethyl maleate (50 g.) in
chloroform
(100 ml) was added a solution of bromine (15 ml) in chloroform 100 ml over a
period of 2
hours. The reaction mixture was stirred for 2 hours at the end of reaction
mixture was
washed twice with 100 ml saturated sodium thiosulphate and then twice with 100
ml water.
Organic part was passed through 5 g. sodium sulphate and sub sequently treated
with
activated charcoal. Chloroform was stripped off to yield 60 g oil.
Subsequent reaction was set up with 250 ml. three necked glass vessel equipped
with
addition funnel magnetic stirrer and rubber septum. Assembly was flushed with
argon. To
this vessel finely cut lithium ribbon (500 mg.) was added and assembly was
evaccuated
and refiilled with argon. To this assebly 50 ml tetra hydrofuran was added
with gas tight
syringe maintaining argon blanket 8.3 ml chlorodiphenyl phosphine was placed
in addition
funnel set up was evacuated and refilled with argon contents of addition
funnel were
dropped in the lithium suspension, during lithium dissolution solution started
assuming red
color and reacction mixture was stirred for 4 hours after complete dissolution
of lithium.
To another 250 ml vessel equipped with reflux condenser and rubber septum 30
ml
dry tetrahydrofuran was placed by syringe and assembly was evaccuated and
refilled with
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63
argon. To this 4.52 g of brominated diethyl maleate was transferred by syringe
followed by
30 ml of lithium phosphied soultion (red colored). Contents of the reaction
mixture were
maintained at 80 C for 12 hours. To this reaction mixture 1 ml methanol was
added and
tetrahydrofuran was removed under vacuum. Syrupy orange coloured liquid was
washed
twice with 25 ml ether. 1 g of this syrupy orange product was transferred to
three necked
round bottomed flask attached with reflux condencer the set up was thoroughly
flushed
with argon and 20 ml 2 % sodium hydroxide were refluxed the reaction mixture
was
cooled to 5 C and precipitated white material of diphosphine was recovered by
filtration
yield 1 g.
Experiment 19
Quaternization of tribenzyl amine tri sulfonate with benzyl chloride
To a mixture of (0.1 mol) tribenzylamine trisulfonate and benzyl chloride (0.2
mol)
was added 50 ml water and 50 ml dimethyl formamide. Solution was stirred at 70
C for 76
hours and reaction was monitored by disappearance of benzyl chloride. Reaction
mixture
was evaporated under vacuum to yield a solid mass, which was dissolved in
minimal
amount of water, and aqueous solution was washed with diethyl ether. Aqueous
extract
was dried under vacuum and solid was stored in dry condition.
Experiment 20
Synthesis of quaternary ammonium hydroxide
17 g. (0.1 mol) of silver nitrate was dissolved in 170 ml of distilled water
and
warmed to 85 C and 3.9g (0.097 mol) sodium hydroxide was added to it. Mixture
was
agitated vigorously until coagulation of precipitation is complete.
Precipitate was
recovered by centrifugation and suspended in 100 ml water to which was added
(0.09 mol)
of above quaternaryammonium compound. Reaction mixture was stirred for 3 hours
under
nitrogen and filtured. Liquid was evaporated under vacuum at room temperature
to obtain a
solid.
Experiment 21
Quaternization of triphenyl amine with benzyl chloride
To a mixture of (0.1 mol) triphenylamine trisulfonate and benzyl chloride (0.2
mol)
was added 50 ml water and 50 ml dimethyl formamide. Solution was stirred at 70
C for 76
hours and reaction was monitored by disappearance of benzyl chloride. Reaction
mixture
was evaporated under vacuum to yield a solid mass, which was dissolved in
minimal
amount of water, and aqueous solution was washed with diethyl ether. Aqueous
extract
was dried under vacuum and solid was stored in dry condition.
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Experiment 22
Formation of quaternary ammonium hydroxide of quaternary ammonium salt of n
benzyl
triphenyl amine.
Experiment 23
Synthesis of hydridocarbonyl tris (trisodiumtriphenylphosphine trisulfonate)
rhodium (I)
The procedure was adopted from US patent 4, 994,427 dated Feb. 19, 1991 to
Davis et al.
500 mg. Acetyl acetonate dicarbonyl rhodium (I) was added to vigorously
stirred 10 ml
deaerated solution of 4 g. of sodium triphenylphosphine trisulfonate in water.
After
dissolution was complete stirring was continued for six hours under atmosphere
of 1;1
H2/CO. solution was then centrifugend to remove precipitated rhodium. To this
solution 80
ml absolute ethanol saturated with 1:1 H2/CO were added to precipitate desired
complex.
Precipitate was recovered and vaccume dried.
Experiment 24
Dichloro bis (tris triphenylphosphine sulfonato trisodium) palladium (II)
This procedure was adapted from Jiang et al J. Mol. Catal. A: Chemical 130
(1998) 79-84,
100 mg PdC12 and 2 ml 2 M HCl were added to a schlenk flask and the mixture
was stirred
at 50 C until PdC12 was dissolved completely. After the flask was cooled to
room
temperature and flushed with argon, 0.80 g. TPPTS was added in to the flask
under
stirring. The color of the solution changed from dark red to yellow
immediately. After 10
min stirring, 15-m1 ethanol was added, alight yellow powder precipitated and
mixture was
stirred for 30 min. The filtered precipitate was washed three times with 30-
m1. warm 95 %
ethanol and dried in vacuum.
Experiment 25
Synthesis of trans-PtC12 (TPPTS) 2
The platinum complex PtC12 (NCPh) 2 235 mg (0.5 mmol) was dissolved in 10 ml
toluene
to this solution was added to aqueous solution of TPPTS (568 mg 1 mmol) in 10
ml water
to this mixture isopropanol 3 ml was added and reaction mixture was stirred at
50 C for 10
h complex was recovered from aqueous phase by evaporation 620 mg of PtC12
(TPPTS) 2.
6 H20.
Experiment 26
Synthesis of NiC12/ TPPTS
Nickel chloridehexahydrate (0.05 mols) was reacted with tppts (0.12 mols) in
water
sufficient to dissolve and formed complex was precipitated by ethanol
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Experiment 27
Syntheis of IrCI (COD) / TPPTS
IrCl (COD) (0.01 mol) was dissolved in minimum amount of tolune and exchanged
with). 04 mols of tppts dissolved in minimum amound of water. Tolune layer was
removed
5 and aqueous layer was dried.
Experiment 28
Synthesis of [Ru (Cl) ( -Cl) (TPPTS) 21
The method was adopted from M. Hernandez et al, J. Mol. Catal. A: Chemical 116
(1997)
117-130. RuC12 (PPh3)3 5.8 g. 6 mmol was dissolved in 150 ml of
tetrahydrofuran and
10 heated to 60 C. A 30 ml water solution of TPPTS (6.3g 10.1 mol was added
drop wise
under vigorous stirring. The biphasic medium was stirred further for 30 min at
60 C. After
cooling to room temperature, 140 ml of orange organic layer was removed. The
resulting
solution was filtered out. Then the deep red aqueous phase was evaporated to
dryness and
further dried in vacuum.
15 Experiment 29
Synthesis of [Ru(H)(Cl)(TPPTS)3]
The method was adopted from M. Hernandez et al, J. Mol. Catal. A: Chemical 116
(1997)
117-130. This complex was prepared from [Ru(H)(Cl)(PPh3)3]. PhCH3 3 g. 3.3
mmol
dissolved in 120 ml tetra hydrofuran; TPPTS 5 g. (8 mmol); H20 30 ml. a bright
purple
20 coloured solid was recovered from aqueous layer.
Experiment 30
Synthesis of [Ru(H)2(TPPTS)4]
0.1 g. (0.38 mmol) of RuC13. 3H20 and 1.07 g TPPTS 1.72 mmol were dissolved in
10 ml of distilled water. The deep brown coloured solution was stirred at room
temperature
25 while passing stream of hydrogen. After 10 min 0.17 g. (-4.5 mmol) of
NaBH4were added.
Solution turned instantaniously brown yellow with vigorous effervescence. The
mixture
was heated to 50 C for 10 min after cooling and evaporation to dryness solid
was obtained
Experiment 31
Synthesis of Ru/Binapts complex
30 Ruthenium binap 4 SO3Na catalyst was prepared by reacting (0.01 g) of
[Ru(benzene)C12]2
with two equivalents of (0.05 g) R- binap 4 SO3Na in a 1:8 benzene ethanole
mixture 4.5
ml to yield [Ru(benzene)Cl] R- binap 4 SO3Na. Resulting solution was vaccume
dried
Experiment 32
Synthesis of Rh/ chiraphos tetra sulfonate complex
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66
Rh+/ chiraphos tetra sulfonate catalyst was prepared by reacting [Rh (COD)
Cl]2 ,
with two mole equivalents of sulfonated ligand in water at room temperature in
presence of
excess sodium perchlorate to form cationic complex
Exaperiment 33
Synthesis of palladium acetate sulfonated bypyridyl complex
Synthesis procedure was adopted from brink et al Chem. Commun, 1998, 2359-
2360. Pd(OAc)2 0.1 mmol and sulfonated bypyridyl 0.1 mmol were stirred
overnight with
42.5 g of water to afford a clear orange colored solution which was evaporated
to dryness.
Experiment 34
Tetrasodium salt of Cobalt (II) 4,4', 4", 4"', - Tetrasulfophthalocynine
(procedure is
adopted from Inorg. Chem. Vo14, No. 4 April 1965, 469-471)
The monosodium salt of 4-sulfopthalic acid (4.32 g., 0.0162 mol.), ammonium
chloride (0.47 g., 0.009 mol.), urea (5.8 g., 0.097 mol.) ammonium molybdate
(0.068g.,
0.00006 mol), and cobalt (II) sulfate 2 H20 (1.36 g., 0.0048 mol) and 100 ml
celite were
ground together in nitrobenzene to form a homogeneous paste and diluted to 50
ml with
nitrobenzene in round bottomed flask attached with reflux condenser. The
reaction mixture
was heated to 180 C. The reaction mixture was heated slowly with overhead
stirring while
maintaining temperature 180 - 190 C. The heterogeneous mixture was heated for
6 hours
at 180 C. The crude= product was recovered by cooling reaction mixture and
removing
nitrobenzene. Solid cake was washed with hexane followed by methanol until
nitrobenzene
was removed. The solid residue was transferred to 110 ml 1 N hydrochloric acid
saturated
with sodium chloride. The mixture was heated briefly to boiling, cooled to
room
temperature and filtered. The resulting solution was dissolved in 70 ml of 0.1
N NaOH.
The solution was heated to 80 C and insoluble impurities were immediately
separated by
filtration. Sodium chloride (27 g. was added to solution and slurry was heated
to 80 C
until ammonia evolution ceased. Reaction mixture was cooled to room
temperature and
filtered. This re-precipitation process was repeated twice and solid was
filtered and washed
with 80 % ethanol until filtrate was chloride free as tested by silver nitrate
solution. This
solid was refluxed in 20-m1 ethanol for 4 hours to get pure product, which was
dried over
P205 yield 65 %correct elemental
Experiment 35
Tetrasodium salt of copper(II) 4, 4', 4", 4"', - Tetrasulfophthalocynine
The compound was prepared using similar mole ratios of the reactant except
0.0048 mol
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67
of copper sulfate 5.H20. and purified as described for Tetrasodium salt of
Cobalt(II)4,4',
4", 4"', - Tetrasulfophthalocynine
Experiment 36
Tetrasodium salt of Manganese(II) 4, 4', 4", 4"', - Tetrasulfophthalocynine
The compound was prepared using similar mole ratios of the reactant except
0.0048 mol
of manganese acetate and purified as described for Tetrasodium salt of
Cobalt(II)4,4', 4",
4"', - Tetrasulfophthalocynine
Experiment 37
Tetrasodium salt of iron(III) 4, 4', 4", 4"', - Tetrasulfophthalocynine oxygen
adduct
The compound was prepared using similar mole ratios of the reactant except
0.0048 mol of
Fe (III) chloride and purified as described for Tetrasodium salt of Cobalt
(II) 4,4', 4", 4"
- Tetrasulfophthalocynine.
Experiment 38
Water soluble cobalt II complex N, N' - ethylenebis (salycyldiamine 5- sodium
sulfonate)
Synthesis of this comples was performed according to Kevin et al. J. Chem.
Soc., Dalton
Trans. 1982, 109.
N- phenyl salicyldimine (35 g.) was added to concentrated sulfuric acid 95 cm
3 and
mixture was heated for two hours, with occasional stirring while keeping
temperature in
the range of 100 +-5 C and after cooling solution was slowly poured over ice
water to
obtain yellow precipitate which was subsequently recrystallized from water to
obtain
crystalline yellow compound (20 g).
25.5 g of above product was dissolved in 500 ml water and to this solution 8.4
g. unhydrus
sodium carbonate was slowly added and stirred until effervescence ceased
aniline was
steam distilled aqueous solution was vaccume dried to obatin a solid which was
purified by
precipitation from water and ethanol.
Na2[Co (S03sal)]. 3 H20
The compound CoC12. 6H20 (6 g. 25 mmol) was dissolved in 30 cc ater and added
to a
solution of disodium salicsyldehyde 5 sulfonic acid (13.2 g 50 mmol) in 20 cc
water and
mixture was heated for 10 min. After filtration solution was concentrated and
cooled to
obtain 12 g of crystalline complex.
N, N' - ethylenebis (salycyldiamine 5- sodium sulfonate)
Ethanol 100cc water 15 cc and ethylene diamine (0.6 g. 10 mmol) were added to
Na2 [Co
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(SO3sal)]z. 3 H2O (5.5 g. 10 mmol and mixture was refluxed under nitrogen
atmosphere for
1 hr. dark brown feathery precipitate was recovered
Experiment 39
Preparation of supports for catalyst preparation
All support materials were sourced from commercial suppliers and were used
without
further size reduction. Specifications of supports are provided with
appropriate
specifications. Support materials were extracted with hexane, ether methanol
and water
using assembly described in figure 3.
Surface saturation with group IIA ions
Each support was divided in to a lot of 25 g and suspended in 500 ml solution
of 5 %
barium nitrate solution. The suspension was refluxed for 24 hours. Suspension
was brought
to room temperature and solid were filtered and transferred to extractor
described in figure
3 and extracted with 500 ml of water, acetone and petroleum ether (bp 60- 80
C) solids
were vacuum dried and stored for further use.
Degassing supports as described above were degassed immediately before use by
following procedure. Required amount was transferred to round bottomed flask
equipped
with two-way valve and evacuated at 0.1 mm Hg and temperature was raised to
150 C and
kept at this temperature for 1 hour at this temperature while maintaining
vacuum. Vacuum
inlet was closed and argon was introduced and flask was cooled to room
temperature. The
procedure was repeated at least thrice and solid was stored under argon for
further use.
Following supports were prepared accordingly, silica, gamma alumina, zirconia,
titania,
keisulghur, bentonite, hyflosupercel, asbestos powder, magnesium hydrotalcite,
barium
sulfate, charcoal, bone ash.
Example 1 to 84
Preparation of catalytic formulation by co-precipitation
The following examples illustrate one of the procedures for the preparation of
the
catalytic formulation of the invention in accordance with the method of
formulation known
as co precipitation in bulk liquid.
The general procedure for the preparation of heterogeneous catalytic
formulation is
3o described herein as making of a solution of anionically charged catalytic
entity,
catalytically inert anionic additive (termed as solution A) and solution of
group II A metal
ions (termed as solution B). A support pretreated as described in earlier is
suspended in
aqueous or water miscible solvent and resulting suspension is vigorously
agitated to this
suspension solution A and solution B were added over a prolonged period of
time and
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resulting suspension is further agitated for specified time. Suspension was
centrifuged and
solids were repeatedly washed with water, methanol and diethyl ether followed
by drying
in vacuum. Dry powder was stored under argon in gas tight vessel and can be
used for
appropriate reaction depending upon catalytically active entity incorporated
in it.
Notel: solution A is prepared by dissolving anionic components including
anionic
complex and additives to make homogeneous solution in degassed solvents. The
resulting
solution is also degassed by purging argon.
Note 2: solution B is prepared by dissolving dissolving group IIA metal salts.
Solution was degassed prior to use.
Note 3 addition of A and B is carried out at ambient temperature unless
stated.
Example Solution A Solution B Procedure
1 HRhCO(TPPTS)3, 50 mg, Saturated barium A suspension of 2 gm DavisilTM in 10
ml water was
TPPTS 200 mg. nitrate in water 2 nil formed and resulting suspension was
vigorously
Dissolved in water.2 ml agitated to this suspension solution A and solution B
were added simultaniously over a 3 hours in 50 i
portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
2 HRhCO(TPPTS) 3, 50 mg, Saturated strondum Solution A and solution B were
added to a suspension
TPPTS 200 mg. chloride in water 2ml of 2 gm Davisil in 10 ml water and
resulting suspension
Dissolved in water 2 ml is vigorously agitated to this suspension solution A
and
solution B were added simultaniously over a 3 hours in
50 l portions resulting suspension is further agitated
for 10 hours to yield pale yellow colored solid powder.
3 HI2hCO(TPPTS)3, 50 mg, 500 mg of calcium Solution A and solution B were
added to a suspension
TPPTS 200 mg. chloride in 2 nil of 5 gm Davisil in 10 ml water and resulting
suspension
Dissolved in water 2 ml water is vigorously agitated to this suspension
solution A and
solution B were added simultaniously over a 3 hours in
50 l porfions resulting suspension is farther agitated
for 10 hours to yield pale yellow colored solid powder.
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4 HRhCO(TPPTS)3 50 mg, Barium nitrate Solution A and solution B were added to
a suspension
TPPTS 200 mg. saturated solution in of 2 gm y-alumina in 10 ml water and
resulting
Dissolved in water 2 ml water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaniously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yild pale yellow colored
solid powder
5 HRhCO(TPPTS)3, 50 mg, Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 200 mg. saturated solution in of 2 gm y-alumina in 10 ml water and
resulting
Dissolved in water 2 nil water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaniously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yild pale yellow color
solid powder
6 HRhCO(TPPTS)3 50 mg, Calcium chloride 500 Solution A and solution B were
added to a suspension
TPPTS 200 mg. mg solution in 2 nil of 2 gm y-alumina in 10 ml water and
resulting
Dissolved in water 2 ml water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaniously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yild pale yellow color
solid powder
7 HRhCO (TPPTS)3, 50 mg, Barium nitrate Solution A and solution B were added
to a suspension
TPPTS 200 mg. saturated solution in of 2 gm bentonite in 10 ml water and
resulting
suspension is vigorously agitated to this suspension
Dissolved in water 2 ml water solution A and solution B were added
simultaniously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yild pale yellow colored
solid powder
8 HRhCO (TPPTS)3, 50 mg, Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 200 mg. saturated solution in of 2 gm bentonite in 10 inl water and
resulting
I suspension is vigorously agitated to this suspension
Dissolved in water 2 ml water
solution A and solution B were added simultaniously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yild pale yellow color
solid powder
9 HRhCO (TPPTS)3, 50 mg, Calcium chloride 500 Solution A and solution B were
added to a suspension
TPPTS 200 mg. mg solution in 2 ml of 2 gm bentonite in 10 ml water and
resulting
Dissolved in water 2 ml water = suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaniously
over a 3 hours in 50 Ntl portions resulting suspension is
further agitated for 10 hours to yild pale yellow color
solid powder
10 HRhCO (TPPTS)3, 50 mg, Barium nitrate Solution A and solution B were added
to a suspension
TPPTS 200 mg. saturated solution in of 2 gm charcoal in 10 ml water and
resulting
Dissolved in water 2 ml water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaneously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 2 hours to yield black colored solid
powder
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11 HRhCO (TPPTS)3, 50 mg, Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 200 mg. saturated solution in of 2 gm charcoal in 10 ml water and
resulting
Dissolved in water 2 ml water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaneously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 2 hours to yield black colored solid
powder.
12 HRhCO (TPPTS)3, 50 mg, Calcium chloride 500 Solution A and solution B were
added to a suspension
TPPTS 200 mg. mg solution in 2 ml of 2 gm charcoal in 10 ml water and
resulting
Dissolved in 2 ml water water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaneously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 2 hours to yield black colored solid
powder
13 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate Solution A and solution B were added
to a suspension
TPPTS 200 mg saturated solution in of 2 gm Davisil in 10 ml water and
resulting suspension
Dissolved in 2 ml water 2 n-d water is vigorously agitated to this suspension
solution A and
solution B were added simultaniously over a 3 hours in
50 l portions resulting suspension is further agitated
for 10 hours to yild light brown colored solid powder.
14 Ru(H)(CI)(TPPTS)3 50 mg Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 200 mg saturated solution in of 2 gm Davisil in 10 ml water and
resulting
Dissolved in 2 ml water. 2 ml water suspension is vigorously agitated to this
suspension
solution A and solution B were added simultaniously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield light brown
colored solid powder.
15 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate Solution A and solution B were added
to a suspension
TPPTS 200 mg Dissolved in saturated solution in of 2 gm y-alumina in 10 ml
water and resulting
2 ml water 2 ml water suspension is vigorously agitated to this suspension
solution A and solution B were added simultaneously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield light brown
colored solid powder.
16 Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 200 mg Dissolved in saturated solution in of 2 gm y-alumina in 10 ml
water and resulting
2 ml water 2 nil water suspension is vigorously agitated to this suspension
solution A and solution B were added simultaneously
over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield light brown
colored solid powder.
17 Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 200 mg saturated solution in of 2 gm y-alumina in 10 ml water and
resulting
Sodium polyvinylsulfonate 2 ml water suspension is vigorously agitated to this
suspension
500 mg Dissolved in 2 mi solution A and solution B were added simultaneously
water over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield light brown
colored solid powder.
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18 Ru (H)(C1)(TPPTS) 3 50 mg Barium = nitrate Solution A and solution B were
added to a suspension
TPPTS 200 mg saturated solution in of 2 gm y-alumina in 10 ml water and
resulting
Sodium polyvinylsulfonate 2 ml water suspension is vigorously agitated to this
suspension
500 mg Dissolved in 2 mi solution A and solution B were added simultaneously
water over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield light brown
colored solid powder.
19 Ru (H)(Cl)(TPPTS) 3 50 mg Barium nitrate Solution A=and solution B were
added to a suspension
TPPTS 200 mg saturated solution in of 2 gm titania in 10 ml water and
resulting suspension
Sodium polyvinylsulfonate 2 ml water is vigorously agitated to this suspension
solution A and
500 mg Dissolved in 2 ml solution B were added simultaneously over a 3 hours
in
water 50 l portions resulting suspension is further agitated
for 10 hours to yield liglrt brown colored solid powder.
20 Ru (H)(C1)(TPPTS) s 50 mg Barium nitrate Solution A and solution B were
added to a suspension
TPPTS 200 mg saturated solution in of 2 gm zirconia in 10 ml water and
resulting
Sodium polyvinylsulfonate 2 ml water suspension is vigorously agitated to this
suspension
500 mg Dissolved in 2 ml solution A and solution B were added simultaneously
water over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield light brown
colored solid powder.
21 Ru (H)(C1)(TPPTS)3 50 mg Barium nitrate Solution A and solution B were
added to a suspension
TPPTS 200 mg saturated solution in of 2 gm activated charcoal in 10 ml water
and resulting
Sodium polyvinylsulfonate 2 ml water suspension is vigorously agitated to this
suspension
500 mg Dissolved in 2 nil solution A and solution B were added simultaneously
water over a 3 hours in 50 l portions resulting suspension is
further agitated for 10 hours to yield black colored
solid powder.
22 PdCi2 (TPPTS), 10 mg Barium nitrate Solution A and solution B were added to
a suspension
TPPTS 100 mg saturated solution 5 of 2 gm shreded asbestos roap in 20 ml water
and
Poly acrylic acid sodium salt ml resulting suspension is vigorously agitated
to this
in 5 mi suspension solution A and solution B was added s over
a period of 3 hours in 50 l portions resulting
suspension is further agitated for 10 hours to yield
yellow gray colored solid powder.
23 PdCl2 (TPPTS) 2 10 mg Strontium chloride Solution A and solution B were
added to a suspension
TPPTS 100 mg saturated solution 5 of 2 gin shreded asbestos roap in 20 ml
water and
Poly acrylic acid sodium salt ml resulting suspension is vigorously agitated
to this
in 5 ml suspension solution A and solution B was added over a
3 hours in 50 p.l portions resulting suspension is further
agitated for 10 hours to yield yellow gray colored solid
powder.
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24 PdCIZ (TPPTS) 2 10 mg 500 mg calcium Solution A and solution B were added
to a suspension
TPPTS 100 mg chloride in 5 ml of 2 gm shreded asbestos roap in 20 ml water and
Poly acrylic acid sodium salt water. resulting suspension is vigorously
agitated to this
in 5 nil suspension solution A and solution B was added over a
3 hours in 50 l portions resulting suspension is further
agitated for 10 hours to yield yellow gray colored solid
powder.
25 PdAc2BYPYDS 25 mg Barium nitrate Solution A and solution B were added to a
suspension
BYPYDS 100 mg saturated solution of 2 gm davisil in 20 ml water and resulting
suspension
Dissolved in 2 ml water 5m1 is vigorously agitated to this suspension solution
A and
solution B was added over a 3 hours in 50 l portions
resulting suspension is furtlier agitated for 10 hours to
yield pale orange colored solid powder.
26 PdAcZBYPYDS 25 mg Strontiurn chloride Solution A and solution B were added
to a suspension
BYPYDS 100 mg saturated solution of 2 gm davisil in 20 ml water and resulting
suspension
Dissolved in 2 ml water 5nil is vigorously agitated to this suspension
solution A and
solution B was added over a 3 hours in 50 l portions
resulting suspension is further agitated for 10 hours to
yield pale orange colored colored solid powder.
27 PdAc2BYPYDS 25 mg 500 mg calcium Solution A and solution B were added to a
suspension
BYPYDS 100 mg chloride in 5 ml of 2 gm davisil in 20 ml water and resulting
suspension
Dissolved in 2 ml water water is vigorously agitated to this suspension
solution A and
solution B was added over a 3 hours in 50 l portions
resulting suspension is further agitated for 10 hours to
yield pale orange colored solid powder.
28 PdAc2BYPYDS 25 mg Barium nitrate Solution A and solution B were added to a
suspension
BYPYDS 100 mg saturated solution of 2 gm bentonite in 20 ml water and
resulting
Dissolved in 2 ml water 5m1 suspension is vigorously agitated to this
suspension
solution A and solution B was added over a 3 hours in
50 }tl portions resulting suspension is further agitated
for 10 hours to yield light orange colored solid powder.
29 PdAc2 tri (o) tolyl phosphine Barium nitrate Solution A and solution B were
added to a suspension
trisulfonated 25 mg saturated solution of 2 gm bentonite in 20 ml water and
resulting
Tri (o) tolyl phosphine 5m1 suspension is vigorously agitated to this
suspension
trisulfonated 100 mg solution A and solution B was added over a 3 hours in
Dissolved in 2 nil water 50 l portions resulting suspension is further
agitated
for 10 hours to yield pale yellow ocher colored solid
powder.
30 PdAc2 tri (o) tolyl phosphine Strontium chloride Solution A and solution B
were added to a suspension
trisulfonated 25 mg saturated solution of 2 gm bentonite in 20 ml water and
resulting
Tri (o)tolyl phosphine 5ml suspension is vigorously agitated to this
suspension
trisulfonated 100 mg solution A and solution B was added over a 3 hours in
Dissolved in 2 ml water 50 1 portions resulting suspension is further
agitated
for 10 hours to yield pale yellow ocher colored solid
powder.
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31 PdAc2 trio tolyl phosphine Barium nitrate Solution A and solution B were
added to a suspension
trisulfonated 25 mg saturated solution of 2 gm alumina in 20 ml water and
resulting
Tri ortho tolyl phosphine 5m1 suspension is vigorously agitated to this
suspension
trisulfonated 100 mg solution A and solution B was added over a 3 hours in
Dissolved in 2 ml water 50 l portions resulting suspension is further
agitated
for 10 hours to yield pale yellow ocher colored solid
powder.
32 PdAc2 tri ortho tolyl Barium nitrate Solution A and solution B were added
to a suspension
phosphine trisulfonated 25 saturated solution of 2 gm charcoal in 20 ml water
and resulting
mg 5m1 suspension is vigorously agitated to this suspension
Tri ortho tolyl phosphine solution A and solution B was added over a 3 hours
in
trisulfonated 100 mg 50 l portions resulting suspension is further agitated
Dissolved in 2 ml water for 10 hours to yield black colored solid powder.
33 NiC12.(TPPTS)2 25 mg Saturated barium A suspension of 1 gm davisil in 5 ml
water was formed
TPPTS 100 mg nitrate in 2 ml water and resulting suspension was vigorously
agitated to this
Sodium carboxy metliyl suspension solution A and solution B were added
cellulose 100 mg simultaneously over a 3 hours in 50 l portions
Dissolved in 2 ml resulting suspension is furflier agitated for 10 hours to
yield solid powder almost white with blue tinge.
34 NiC12.(TPPTS)Z 25 mg Saturated barium A suspension of 1 gm alumina in 5 ml
water was
TPPTS 100 mg nitrate in 2 ml water formed and resulting suspension was
vigorously
Sodium carboxy methyl agitated to this suspension solution A and solution B
cellulose 100 mg were added simultaneously over a 3 hours in 50 l
Dissolved in 2 ml portions resulting suspension is further agitated for 10
hours to yield solid powder almost white with blue
tinge.
35 NiC12.(TPPTS)2 25 mg Saturated barium A suspension of 1 gm zirconia in 5 ml
water was
TPPTS 100 mg nitrate in 2 ml water formed and resulting suspension was
vigorously
Sodium carboxy methyl agitated to this suspension solution A and solution B
cellulose 100 mg were added simultaneously over a 3 hours in 50 l
Dissolved in 2 ml portions resulting suspension is further agitated for 10
hours to yield solid powder almost white with blue
tinge.
36 NiC12.(TPPTS)2 25 mg Saturated strontium A suspension of 1 gm zirconia in 5
ml water was
TPPTS 100 mg chloride in 2 ml formed and resulting suspension was vigorously
Sodium carboxy methyl water agitated to this suspension solution A and
solution B
cellulose 100 mg were added simultaneously over a 3 hours in 50 l
Dissolved in 2 ml portions resulting suspension is further agitated for 10
hours to yield solid powder almost white with blue
tinge.
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37 NiC1,.(TPPTS)2 25 mg Saturated strontium A suspension of 1 gm titania in 5
ml water was formed
TPPTS 100 mg chloride in 2 ml and resulting suspension was vigorously agitated
to this
Sodium carboxy methyl water suspension solution A and solution B were added
cellulose 100 mg simultaneously over a 3 hours in 50 l portions
Dissolved in 2 ml resulting suspension is further agitated for 10 hours to
yield solid powder almost white with blue tinge.
38 NiC12.(TPPTS)2 25 mg Saturated strontium A suspension of 1 gm asbestos in 5
ml water was
TPPTS 100 mg chloride in 2 nil formed and resulting suspension was vigorously
Sodium carboxy methyl water agitated to this suspension solution A and
solution B
cellulose 100 mg were added simultaneously over a 3 hours in 50 l
Dissolved in 2 ml portions resulting suspension is further agitated for 10
hours to yield gray colored solid powder.
39 (IrC1COD) 5 mg exchanged Saturated strontium A suspension of 1 gm davisil
in 5 ml water was formed
with TPPTS 100 mg. chloride in 2 ml and resulting suspension was vigorously
agitated to this
Poly acrylic acid sodium salt water suspension solution A and solution B were
added
100 mg simultaneously over a 3 hours in 50 l portions
In 2 ml water resulting suspension is further agitated for 10 hours to
yield pale yellow colored solid powder.
40 (IrCICOD) 5 mg exchanged Saturated strontium A suspension of I gm
keisulghur in 5 ml water was
with TPPTS 100 mg. chloride in 2 ml formed and resulting suspension was
vigorously
Poly acrylic acid sodium salt water agitated to this suspension solution A and
solution B
100 mg were added simultaneously over a 3 hours in 50 l
In 2 ml water portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
41 (IrC1COD) 5 mg exchanged Saturated strontium A suspension of I gm bentonite
in 5 ml water was
with TPPTS 100 mg. chloride in 2 ml formed and resulting suspension was
vigorously
Poly acrylic acid sodium salt water agitated to this suspension solution A and
solution B
100 mg were added simultaneously over a 3 hours in 50 1
In 2 ml water portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
42 (RuC1zCOD) 5 mg exchanged Saturated strontium A suspension of 1 gm davisil
in 5 ml water was formed
with diphenyl phosphino chloride in 2 ml and resulting suspension was
vigorously agitated to this
ethane tetrasulfonate 100 mg. water suspension solution A and solution B were
added
Poly acrylic acid sodium salt simultaneously over a 3 hours in 50 l portions
100 mg resulting suspension is further agitated for 10 hours to
In 2 ml water yield pale yellow colored solid powder.
43 (RuCI2COD) 5 mg exchanged Saturated strontium A suspension of I gm davisil
in 5 ml water was formed
with diphenyl phosphino chloride in 2 ml and resulting suspension was
vigorously agitated to this
ethane tetrasulfonate 100 mg. water suspension solution A and solution B were
added
Poly acrylic acid sodium salt simultaneously over a 3 hours in 50 l portions
100 mg resulting suspension is further agitated for 10 hours to
In 2 ml water yield pale yellow colored solid powder.
44 (RuC12COD) 5 mg exchanged 500 mg calcium A suspension of I gm davisil in 5
ml water was formed
with diphenyl phosphino chloride in 2 ml and resulting suspension was
vigorously agitated to this
ethane tetrasulfonate 100 mg. water suspension solution A and solution B were
added
Poly acrylic acid sodium salt simultaneously over a 3 hours in 50 l portions
100 mg resulting suspension is further agitated for 10 hours to
In 2 ml water yield pale yellow colored solid powder.
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45 Rh(COD)PFe/ S,S chiraphos Saturated strontium A suspension of 1 gm davisil
in 5 ml water was formed
tetrasulfonate 25 mg chloride solution 2 and resulting suspension was
vigorously agitated to this
S,S chiraphos tetrasulfonate ml suspension solution A and solution B were
added
25 mg simultaneously over a 3 hours in 50 l portions
Sodium alginate 100 mg resulting suspension is further agitated for 10 hours
to
dissolved in 2 ml water yield pale yellow colored solid powder.
46 Rh(COD)PF6/ S,S chiraphos Saturated barium A suspension of I gm davisil in
5 ml water was formed
tetrasulfonate 25 mg nitrate solution 2 ml and resulting suspension was
vigorously agitated to this
S,S chiraphos tetrasulfonate suspension solution A and solution B were added
25 mg simultaneously over a 3 hours in 50 l portions
Sodium alginate 100 mg resulting suspension is further agitated for 10 hours
to
dissolved in 2 ml water yield pale yellow colored solid powder.
47 Rh (COD) PF6/ S,S chiraphos Saturated barium A suspension of 1 gm alumina
in 5 ml water was
tetrasulfonate 25 mg nitrate solution 2 ml formed and resulting suspension was
vigorously
S,S chiraphos tetrasulfonate agitated to this suspension solution A and
solution B
25 mg were added simultaneously over a 3 hours in 50 l
Sodium alginate ' 100 mg portions resulting suspension is further agitated for
10
dissolved in 2 ml water hours to yield pale yellow colored solid powder.
48 Rh(COD)PFc! S,S chiraphos Saturated barium A suspension of 1 gm titania in
5 ml water was formed
tetrasulfonate 25 mg nitrate solution 2 ml and resulting suspension was
vigorously agitated to this
S,S chiraphos tetrasulfonate suspension solution A and solution B were added
25 mg simultaneously over a 3 hours in 50 l portions
Sodium alginate 100 mg resulting suspension is further agitated for 10 hours
to
dissolved in 2 ml water yield pale yellow colored solid powder.
49 HRhCO (TPATS) 3 500 mg Calcium A suspension of 1 gm titania in 5 ml water
was formed
mg chloride solution in and resulting suspension was vigorously agitated to
this
100 mg TPATS water 5 ml suspension solution A and solution B were added
Carboxy methyl cellulose simultaneously over a 3 hours in 50 l portions
sodium 100 mg in 1 ml water resulting suspension is further agitated for 10
hours to
yield pale yellow colored solid powder.
50 HRhCO (TPATS) 3 Strontium chloride A suspension of 1 gm alumina in 5 ml
water was
10 mg saturated solution in formed and resulting suspension was vigorously
100 mg TPATS water 5 ml agitated to this suspension solution A and solution B
carboxy methyl cellulose were added simultaneously over a 3 hours in 50 l
sodium 100 mg in 1 ml water portions resulting suspension is further agitated
for 10
hours to yield pale yellow colored solid powder.
51 HRhCO (TPATS) 3 Barium nitrate A suspension of 1 gm bentonite in 5 ml water
was
10 mg saturated solution in formed and resulting suspension was vigorously
100 mg TPATS water 5 ml agitated to this suspension solution A and solution B
carboxy methyl cellulose were added simultaneously over a 3 hours in 50 l
sodium 100 mg in 1 ml water portions resulting suspension is further agitated
for 10
hours to yield pale yellow colored solid powder.
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52 HRhCO (TPATS) 3 Strontium chloride A suspension of 1 gm titania in 5 ml
water was formed
mg saturated solution in and resulting suspension was vigorously agitated to
this
100 mg TPATS water 5 mi suspension solution A and solution B were added
Carboxy methyl cellulose simultaneously over a 3 hours in 50 l portions
sodium 100 mg in 1 ml water resulting suspension is further agitated for 10
hours to
yield pale yellow colored solid powder.
53 HRhCO (TPATS) 3 Strontium chloride A suspension of 1 gm Davisil in 5 ml
water was formed
10 mg saturated solution in and resulting suspension was vigorously agitated
to this
100 mg TPATS water 5 mi suspension solution A and solution B were added
Carboxy methyl cellulose simultaneously over a 3 hours in 50 l portions
sodium 100 mg in I ml water resulting suspension is further agitated for 10
hours to
yield pale yellow colored solid powder.
54 HRhCO (BISBIS) 50 mg Saturated barium A suspension of 2 gm Davisil in 5 ml
water was
BISBIS 200 mg nitrate solution is 5 formed and resulting suspension was
vigorously
200 mg sodium sulfate nil water agitated to this suspension solution A and
solution B
Dissolved in 2 ml water were added simultaneously over a 3 hours in 50 l
portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
55 HRhCO (BISBIS) 50 mg 1 g calcium chloride A suspension of 2 gm Davisil in
10 ml water was
BISBIS 200 mg solution In 5 ml formed and resulting suspension was vigorously
200 mg polyvinyl sulfonic water agitated to this suspension solution A and
solution B
acid dissolved in 2 ml water were added simultaneously over a 3 hours in 50 l
portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
56 HRhCO(BISBIS) 50 mg Saturated barium A suspension of 2 gm titania in 10 ml
water was
BISBIS 200 mg nitrate solution is 5 formed and resulting suspension was
vigorously
200 mg polyacrylic acid ml water agitated to this suspension solution A and
solution B
sodium salt dissolved in 2 ml were added simultaneously over a 3 hours in 50
l
water portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.7
57 HRhCO(BISBIS) 50 mg Saturated strontium A suspension of 2 gm alumina in 10
ml water was
BISBIS 200 mg chloride solution is 5 formed and resulting suspension was
vigorously
200 mg polyvinyl sulfonic ml water agitated to this suspension solution A and
solution B
acid dissolved in 2 ml water were added simultaneously over a 3 hours in 50 l
portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
58 HRhCO(BISBIS) 50 mg Saturated barium A suspension of 2 gm bentonite in 10
ml water was
BISBIS 200 mg nitrate solution is 5 formed and resulting suspension was
vigorously
200 mg polyvinyl sulfonic ml water agitated to this suspension solution A and
solution B
acid dissolved in 2 ml water were added simultaneously over a 3 hours in 50 l
portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
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59 HRhCO(BISBIS) 50 mg Saturated barium A suspension of 2 gm Davisil in 10 ml
water was
BISBIS 200 mg nitrate solution is 5 formed and resulting suspension was
vigorously
200 mg polyvinyl sulfonic ml water agitated to this suspension solution A and
solution B
acid dissolved in 2 ml water were added simultaneously over a 3 hours in 50 l
portions resulting suspension is further agitated for 10
hours to yield pale yellow colored solid powder.
60 PtC12(TPPTS)2 50 mg Saturated solution of A suspension of 2 gm of davisil
in 10 ml butane diol
TPPTS 100 mg barium nitrate 5 ml was formed and resulting suspension was
vigorously
100 mg sodium alginate agitated to this suspension solution A was added over a
dissolved in 2 ml water period of 2 hours and further agitated for 5 hours
solution B was then added in portions of 50 1 over a
period of 3 hours resulting suspension is further
agitated for 24 hours to yield gray colored solid
powder.
61 PtC1z(TPPTS)Z 50 mg Saturated solution of A suspension of 2 gm of y-alumina
in 10 nil butane
TPPTS 100 mg barium nitrate 5 ml diol was formed and resulting suspension was
100 mg oxalic acid sodium vigorously agitated to this suspension solution Awas
salt. added over aperiod of 2 hours and further agitated for 5
Dissolved in 2 ml water hours solution B was then added in portions of 50 1
over a period of 3 hours resulting suspension is further
agitated for 24 hours to yield pale yellow colored solid
powder.
62 PtC1Z(TPPTS)2 50 mg Saturated solution of A suspension of 2 gm of davisil
in 10 ml ethylene
TPPTS 100 mg strontium chloride 5 glycol was formed and resulting suspension
was
100 mg citric acid ml vigorously agitated to this suspension solution A was
Dissolved in 2 ml water added over aperiod of 2 hours and further agitated for
5
hours solution B was then added in portions of 50 1
over a period of 3 hours resulting suspension is further
agitated for 24 hours to yield pale yellow colored solid
powder.
63 PtC12(TPPTS)2 50 mg Saturated solution of A suspension of 2 gm of davisil
in 10 ml butane diol
TPPTS 100 mg barium nitrate 5 ml was formed and resulting suspension was
vigorously
100 mg polyacrylic acid agitated to this suspension solution A was added over
sodium salt. aperiod of 2 hours and further agitated for 5 hours
Dissolved in 2 ml water solution B was then added in portions of 50 1 over a
period of 3 hours resulting suspension is further
agitated for 24 hours to yield pale yellow colored solid
powder.
64 PtCI2(TPPTS)2 50 mg Saturated solution of A suspension of 2 gm of shreded
asbestos roap in 10
TPPTS 300 mg barium nitrate 5 nil ml butane diol was formed and resulting
suspension
Dissolved in 2 ml water was vigorously agitated to this suspension solution
Awas added over aperiod of 2 hours and further
agitated for 5 hours solution B was then added in
portions of 50 1 over a period of 3 hours resulting
suspension is further agitated for 24 hours to yield gray
colored solid powder.
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65 Cobalt N, N'ethylene bis Saturated barium A suspension of 2 gm davisil in
10 ml tetrahydrofuran
(salicyldiamine) 5-sulfonato nitrate solution in 50 % in water was formed and
resulting suspension
sodium 100 mg. water 5m1 was vigorously agitated to this suspension solution A
Sodium phosphate. 500 mg. and solution B were added at simultaniously in
In 5 ml water portions of 50 1 over a period of 3 hours resulting
suspension is further agitated for 24 hours to yield pale
brown colored solid powder.
66 Cobalt N, N'ethylene Saturated barium A suspension of 2 gm alumina in 10 ml
tetrahydrofuran
bis (salicyldiamine) 5- nitrate solution in 50 % in water was formed and
resulting suspension
sulfonato sodium 100 water 5m1 was vigorously agitated to this suspension
solution A
and solution B were added at simultaniously in
mg= portions of 50 1 over a period of 3 hours resulting
Sodium silicate 500 mg. suspension is further agitated for 24 hours to yield
pale
In 5 ml water brown colored solid powder.
67 Cobalt N, N'ethylene bis Saturated barium A suspension of 2 gm titania in
10 ml tetrahydrofuran
(salicyldiamine) 5-sulfonato nitrate solution in 50 % in water was formed and
resulting suspension
sodium 100 mg. water 5m1 was vigorously agitated to this suspension solution A
Polyvinyl sulfonate sodium. and solution B were added at simultaniously in
500 mg. portions of 50 1 over a period of 3 hours resulting
In 5 ml water suspension is further agitated for 24 hours to yield pale
brown colored solid powder.
68 Cobalt N, N'ethylene bis Saturated barium A suspension of 2 gm zirconia
asbesto rope in 10 ml
(salicyldianiine) 5-sulfonato nitrate solution in tetrahydrofuran 50 % in
water was formed and
sodium 100 mg. water 5m1 resulting suspension was vigorously agitated to this
Polyvinyl sulfonate sodium. suspension solution A and solution B were added at
500 mg. simultaniously in portions of 50 1 over a period of 3
In 5 ml water hours resulting suspension is further agitated for 24
hours to yield pale brown colored solid powder.
69 Cobalt N, N'ethylene 2- calcium chloride A suspension of 2 gm shreded
asbesto rope in 10 ml
solution in water Smt tetrahydrofuran 50 % in water was formed and
bis (salicyldiamine) 5- resulting suspension was vigorously agitated to this
sulfonato sodium 100 suspension solution A and solution B were added at
mg. simultaniously in portions of 50g1 over a period of 3
Polyvinyl sulfonate hours resulting suspension is further agitated for 24
sodium. 500 mg. hours to yield pale brown colored solid powder.
In 5 ml water
70 Cobalt (II), 4, 4', 4",4"'- Saturated strontium A suspension of 2 gm
shreded asbesto rope in 10 ml
tetrasulfopthalocynine oxygen chloride in 5 ml methanol was formed and
resulting suspension was
adduct. 500 mg water vigorously agitated to this suspension solution A was
And 500 mg sodium sodium added and stirred for 15 min and solution B was added
poly vinyl sulfonate in 5 ml at once resulting suspension is further agitated
for 3
water hours to yield steel gray colored solid powder.
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71 Cobalt (II), 4, 4', 4",4"'- Saturated barium A suspension of 2 gm
keisulghur in 10 ml methanol
tetrasulfopthalocynine. 500 nitrate in 5 ml water was formed and resulting
suspension was vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium stirred for 15 min and solution B was added at once
phosphate in 5 ml water resulting suspension is further agitated for 3 hours
to
yield light blue colored solid powder.
72 Cobalt (II), 4, 4', 4",4"'- Saturated strontium A suspension of 2 gm
keisulghur in 10 ml methanol
tetrasulfopthalocynine . 500 chloride in 5 ml was formed and resulting
suspension was vigorously
mg water agitated to this suspension solution A was added and
And 500 mg sodium stirred for 15 min and solution B was added at once
phosphate in 5 ml water resulting suspension is further agitated for 3 hours
to
yield light blue colored solid powder.
73 Cobalt (II), 4, 4', 4",4"'- 500mg. CaCIZ in 5 nil A suspension of 2 gm
keisulghur in 10 ml methanol
tetrasulfopthalocynine. 500 water was formed and resulting suspension was
vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium stirred for 15 min and solution B was added at once
phosphate in 5 ml water resulting suspension is further agitated for 3 hours
to
yield light blue colored solid powder.
74 Copper (II), 4, 4', 4",4"'- 500mg. CaCIZ in 5 ml A suspension of 2 gm
keisulghur in 10 ml methanol
tetrasulfopthalocynine. 500 water was formed and resulting suspension was
vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium sulfate in stirred for 15 min and solution B was added at
once
5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
75 Copper (II), 4, 4', 4",4"'- Saturated strontium A suspension of 2 gm
keisulghur in 10 ml methanol
tetrasulfopthalocynine. 500 chloride in 5 ml was formed and resulting
suspension was vigorously
mg water agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 niin and solution B was added at
once
in 5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
76 Copper (Il), 4, 4', 4",4"'- Saturated barium A suspension of 2 gm
keisulghur in 10 ml methanol
tetrasulfopthalocynine. 500 nitrate in 5 ml water was formed and resulting
suspension was vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 niin and solution B was added at
once
in 5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
77 Copper (II), 4, 4', 4",4"'- Saturated barium A suspension of 2 gm bentonite
in 10 ml methanol was
tetrasulfopthalocynine . 500 nitrate in 5 ml water formed and resulting
suspension was vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 min and solution B was added at once
in 5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
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78 Copper (II), 4, 4', 4",4"'- Saturated strontiun A suspension of 2 gm
bentonite in 10 ml methanol was
tetrasulfopthalocynine. 500 chloride in 5 ml formed and resulting suspension
was vigorously
mg water agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 min and solution B was added at once
in 5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
79 Manganese(II), 4, 4', 4",4"'- Saturated strontiun A suspension of 2 gm
Davisil in 10 ml methanol was
tetrasulfopthalocynine. 500 chloride in 5 ml formed and resulting suspension
was vigorously
mg water agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 min and solution B was added at once
in 5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
80 Manganese(II), 4, 4', 4",4"'- Saturated barium A suspension of 2 gm Davisil
in 10 nil methanol was
tetrasulfopthalocynine. 500 nitrate in 5 ml water formed and resulting
suspension was vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 niin and solution B was added at
once
in 5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
81 Manganese(II), 4, 4', 4",4"'- Saturated barium A suspension of 2 gm y-
alumina in 10 ml methanol
tetrasulfopthalocynine. 500 nitrate in 5 ml water was formed and resulting
suspension was vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium silicate stirred for 15 min and solution B was added at once
in 5 nil water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
82 Manganese(II), 4, 4', 4",4"1- Saturated barium A suspension of 2 gm y-
alumina in 10 ml methanol
tetrasulfopthalocynine 500 nitrate in 5 ml water was formed and resulting
suspension was vigorously
mg agitated to this suspension solution A was added and
And 500 mg sodium stirred for 15 min and solution B was added at once
polyvinyl sulfonate in 5 ml resulting suspension is further agitated for 3
hours to
water yield light blue colored solid powder.
83 Iron (111), 4, 4', 4",4"'- Saturated strontium A suspension of 2 gm Davisil
in 10 ml methanol was
tetrasulfopthalocynine oxygen chloride in 5 mi formed and resulting suspension
was vigorously
adduct. 500 mg water agitated to this suspension solution A was added and
And 500 mg sodium sulfate in stirred for 15 min and solution B was added at
once
ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
84 Iron (III), 4, 4', 4",4"'- Saturated barium A suspension of 2 gm Davisil in
10 nil methanol was
tetrasulfopthalocynine oxygen nitrate in water 5 ml formed and resulting
suspension was vigorously
adduct. 500 mg agitated to this suspension solution A was added and
And 500 mg sodium sulfate in stirred for 15 min and solution B was added at
once
5 ml water resulting suspension is further agitated for 3 hours to
yield light blue colored solid powder.
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Examples 85 to 168
Preparation of catalytic formulation by deposition precipitation
The following examples illustrate one of the procedures for the preparation of
the
catalytic formulation of the invention in accordance with the method of
formulation known
as co precipitation near the surface of the solid support.
The general procedure for the preparation of heterogeneous catalytic
formulation is
described herein as making of a solution of anionically charged catalytic
entity,
catalytically inert anionic additive (termed as solution A) and solution of
group II A metal
ions (termed as solution B). The specified amount of support pretreated as
described in
earlier is impregnated with solution A by wetting solids with solution
followed by
evaporation to obtain dry solid support bearing anionic components of solution
A. this
solid powder is gradually added to the solution B over a specified period of
time. Resulting
suspension is further agitated for specified time. Suspension was centrifuged
and solids
were repeatedly washed with water and dried in vacuum. Dry powder was stored
under
argon in gas tight vessel. These solid catalytic formulations can be used for
appropriate
reactions depending upon catalytically active entity incorporated in it.
Notel: solution A is prepared by dissolving anionic components including
anionic
complex and additives to make homogeneous solution in degassed solvents. And
resulting
solution is also degassed by purging argon.
Note 2: solution B is prepared by dissolving dissolving group IIA metal salts.
Solution was degassed prior to use
Note 3: the impregnation of solution on solid support is carried out by
wetting
solids with solution A and evaporating in vacuum at 50 C unless stated
Note 4: addition of impregnated solids with components of A to solution B is
carried out at ambient temperature unless stated.
Example Solution A Solution B Procedure
85 HRhCO (TPPTS)3 50 mg, Saturated barium 2 gm Davisil was wetted with 100 1
portion of
TPPTS 200 mg. nitrate in water 2 mi solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml with simultanious tumbling remining solution A was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
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86 HRhCO (TPPTS) 3 50 mg, Saturated strontium 2 gm Davisil was wetted with 100
1 portion of
TPPTS 200 mg. chloride in water 2m1 solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml with simultanious tumbling remining solution A was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
87 HRhCO (TPPTS)3, 50 mg, 500 mg of calcium 2 gm Davisil was wetted with 100
l portion of
TPPTS 200 mg. chloride in 2 mi solution A and evaporated under vaccume 10 mm
Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
88 HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm y-alumina was wetted with 100 l
portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling reniining solution A
was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
89 HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm y-alumina was wetted with 100
l portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water 2m1 with simultanious tumbling remining solution
A was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
90 HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm y-alumina was wetted with
100 1 portion of
TPPTS 200 mg. mg solution in 2 mi solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling reniining solution A
was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours,
filtered to yild pale yellow colored solid powder.
91 HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm bentonite was wetted with 100 1
portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water 2 ml with simultanious tumbling remining
solution A was
added in 100 l fractions and solid was isolated
(moisture content -20 % )this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
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92 HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm bentonite was wetted with 100
l portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
93 HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm bentonite was wetted with
100 1 portion of
TPPTS 200 mg. mg solution in 2 nil solution A and evaporated under vaccume 10
nnn Hg
Dissolved in water 2 nil water with simultanious tumbling remining solution A
was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
94 HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm charcoal was wetted with 100 91
portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
black colored solid powder.
95 HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm charcoal was wetted with 100
1 portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
black colored solid powder.
96 HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm charcoal was wetted with
100 1 portion of
TPPTS 200 mg. mg solution in 2 ml solution A and evaporated under vaccume 10
mm Hg
Dissolved in 2 ml water water with simultanious tumbling remining solution A
was
added in 100 1 fractions and solid was isolated
(moisture content -20 % )this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours to yild
black colored solid powder.
97 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm Davisil was wetted with 100 l
portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in 2 ml water 2 ml water with simultanious tumbling remining
solution A was
added in 100 1 fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtured to yield light brown colored solid powder..
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98 Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm Davisil was wetted with 100
l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in 2 ml water. 2 rnl water with simultanious tumbling remining
solution A was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtured to yield light brown colored solid powder.
99 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-alumina was wetted with 100
p.l portion of
TPPTS 200 mg Dissolved in saturated solution in solution A and evaporated
under vaccume 10 mm Hg
2 ml water 2 ml water with simultanious tumbling remining solution A was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield light brown colored solid powder.
100 Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm y-alumina was wetted with
100 l portion of
TPPTS 200 mg Dissolved in saturated solution in solution A and evaporated
under vaccume 10 mm Hg
2 ml water 2 ml water with simultanious tumbling remining solution A was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield light brown colored solid powder.
101 Ru(H)(C1)(TPPTS)3 50 mg Strontium chloride 2 gm y-alumina was wetted with
100 l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Sodium polyvinylsulfonate 2 ml water with simultanious tumbling remining
solution A was
500 mg Dissolved in 2 ml added in 100 l fractions and solid was isolated
water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield light brown colored solid powder.
102 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-alunrina was wetted with 100
l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Sodium polyvinylsulfonate 2 ml water with simultanious tumbling remining
solution A was
500 mg Dissolved in 2 ml added in 100 l fractions and solid was isolated
water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield light brown colored solid powder..
103 Ru(H)(C1)(TPPTS)3 50 mg Barium nitrate 2 gm titania was wetted with 100 l
portion of solution
TPPTS 200 mg saturated solution in A and evaporated under vaccume 10 mm Hg
with
Sodium polyvinylsulfonate 2 ml water simultanious tumbling renrining solution
A was added
500 mg Dissolved in 2 ml in 100 l fractions and solid was isolated (moisture
water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield light
brown colored solid powder.
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104 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm zirconia was wetted with 100
l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Sodium polyvinylsulfonate 2 ml water with simultanious tumbling remining
solution A was
500 mg Dissolved in 2 ml added in 100 l fractions and solid was isolated
water (moisture content -20 % )this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield light brown colored solid powder..
105 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm activated charcoal was wetted
with 100 l portion
TPPTS 200 mg saturated solution in of solution A and evaporated under vaccume
10 mm
Sodium polyvinylsulfonate 2 ml water Hg with simultanious tumbling remining
solution A
500 mg Dissolved in 2 ml was added in 100 l fractions and solid was isolated
water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield black colored solid powder.
106 PdC12(TPPTS)2 10 mg Barium nitrate 2 gm shreaded asbestos roap was wetted
with 100 l
TPPTS 100 mg saturated solution 5 portion of solution A and evaporated under
vaccume 10
Poly acrylic acid sodium salt nil mm Hg with simultanious tumbling remining
solution
in 5 ml A was added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield yellow gray colored solid powder.
107 PdCIz(TPPTS)210 mg Strontium chloride 2 gm shreaded asbestos roap was
wetted with 100 l
TPPTS 100 mg saturated solution 5 portion of solution A and evaporated under
vaccume 10
Poly acrylic acid sodium salt ml mm Hg with simultanious tumbling remining
solution
in 5 nil A was added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield yellow gray colored solid powder.
108 PdCIZ(TPPTS)210 mg 500 mg calcium 2 gm shreaded asbestos roap was wetted
with 100 l
TPPTS 100 mg chloride in . 5 ml portion of solution A and evaporated under
vaccume 10
Poly acrylic acid sodium salt water. mm Hg with simultanious tumbling remining
solution
in 5 ml A was added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield yellow gray colored solid powder.
109 PdAc2BYPYDS 25 mg Barium nitrate 2 gm davisil was wetted with 100 l
portion of solution
BYPYDS 100 mg saturated solution A and evaporated under vaccume 10 mm Hg with
Dissolved in 2 ml water 5nil simultanious tumbling remining solution A was
added
in 100 l fractions and solid was isolated (moisture
content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield loght
orange colored solid powder.
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110 PdAc2BYPYDS 25 mg Strontium chloride 2 gm davisil was wetted with 100 l
portion of solution
BYPYDS 100 mg saturated solution A and evaporated under vaccume 10 mm Hg with
Dissolved in 2 n-d water 5m1 simultanious tumbling remining solution A was
added
in 100 l fractions and solid was isolated (moisture
content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield loght
orange colored solid powder.
111 PdAc2BYPYDS 25 mg 500 mg calcium 2 gm davisil was wetted with 100 l
portion of solution
BYPYDS 100 mg chloride in 5 ml A and evaporated under vaccume 10 mm Hg with
Dissolved in 2 ml water water simultanious tumbling remining solution A was
added
in 100 l fractions and solid was isolated (moisture
content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield loght
orange colored solid powder.
112 PdAc2BYPYDS 25 mg Barium nitrate 2 gm bentonite was wetted with 100 l
portion of
BYPYDS 100 mg saturated solution solution A and evaporated under vaccume 10 mm
Hg
Dissolved in 2 ml water 5m1 with simultanious tumbling remining solution A was
added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield loght orange colored solid powder.
113 PdAc2 trio tolyl phosphine Barium nitrate 2 gm bentonite was wetted with
100 l portion of
trisulfonated 25 mg saturated solution solution A and evaporated under vaccume
10 mm Hg
trio tolyl phosphine 5m1 with simultanious tumbling remining solution A was
trisulfonated 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale brown colored solid powder.
114 PdAc2 - trio tolyl phosphine Strontium chloride 2 gm bentonite was wetted
with 100 1 portion of
trisulfonated 25 mg saturated solution solution A and evaporated under vaccume
10 mm Hg
trio tolyl phosphine 5m1 with simultanious tumbling remining solution A was
trisulfonated 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale brown colored solid powder.
115 PdAc2 trio tolyl phosphine Barium nitrate 2 gm alumina was wetted with 100
l portion of
trisulfonated 25 mg saturated solution solution A and evaporated under vaccume
10 mrn Hg
trio tolyl phosphine 5m1 with simultanious tumbling remining solution A was
trisulfonated 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 nil water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale brown colored solid powder.
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116 PdAc2 trio tolyl phosphine Barium nitrate 2 gm charcoal was wetted with
100 l portion of
trisulfonated 25 mg saturated solution solution A and evaporated under vaccume
10 mm Hg
trio tolyl phosphine 5m1 with simultanious tumbling remining solution A was
trisulfonated 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 24 hours
filtered to yield black colored solid powder.
117 NiCi2.(TPPTS)2 25 mg Saturated barium 1 gm davisil was wetted with 100 l
portion of solution
TPPTS 100 mg nitrate in 2 ml water A and evaporated under vaccume 10 mm Hg
with
Sodium carboxy methyl simultanious tumbling remining solution A was added
cellulose 100 mg in 100 l fractions and solid was isolated (moisture
Dissolved in 2 ml content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
blue colored solid powder.
118 NiCL2.(TPPTS)2 25 mg Saturated barium 1 gm alumina was wetted with 100 l
portion of
TPPTS 100 mg nitrate in 2 ml water solution A and evaporated under vaccume 10
mm Hg
Sodium carboxy methyl with simultanious tumbling remining solution A was
cellulose 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 ml (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
119 NiCh.(TPPTS)Z 25 mg Saturated barium I gm zirconia was wetted with 100 l
portion of
TPPTS 100 mg nitrate in 2 ml water solution A and evaporated under vaccume 10
mm Hg
Sodium carboxy methyl with simultanious tumbfing remining solution A was
cellulose 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 ml (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
120 NiCl2.(TPPTS)2 25 mg Saturated strontium 1 gm zirconia was wetted with 100
l portion of
TPPTS 100 mg chloride in 2 ml solution A and evaporated under vaccume 10 mm Hg
Sodium carboxy methyl water with simultanious tumbling remining solution A was
cellulose 100 mg added in 100 l &acflons and solid was isolated
Dissolved in 2 ml (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
121 NiC12.(TPPTS)2 25 mg Saturated strontium I gm titania was wetted with 100
1 portion of solution
TPPTS 100 mg chloride in 2 ml A and evaporated under vaccume 10 mm Hg with
Sodium carboxy methyl water simultanious tumbling remining solution A was
added
cellulose 100 mg in 100 i fractions and solid was isolated (moisture
Dissolved in 2 nil content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
blue colored solid powder.
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122. NiC12.(TPPTS)2 25 mg Saturated strontium 1 gm asbestos was wetted with
100 l portion of
TPPTS 100 mg chloride in 2 ml solution A and evaporated under vaccume 10 mm Hg
Sodium carboxy methyl water with simultanious tumbling remining solution A was
cellulose 100 mg added in 100 l fractions and solid was isolated
Dissolved in 2 ml (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
123. (IrC1COD) 5 mg exchanged Saturated strontium 1 gm davisil was wetted with
100 l portion of solution
with TPPTS 100 mg. chloride in 2 ml A and evaporated under vaccume 10 mm Hg
with
Poly acrylic acid sodium salt water simultanious tumbling remining solution A
was added
100 mg in 100 }ll fractions and solid was isolated (moisture
In 2 ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
124. (IrC1COD) 5 mg exchanged Saturated strontium I gm keisulghur was wetted
with 100 l portion of
with TPPTS 100 mg. chloride in 2 ml solution A and evaporated under vaccume 10
mm Hg
Poly acrylic acid sodium salt water with simultanious tumbling remining
solution A was
100 mg added in 100 l fractions and solid was isolated
In 2 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow colored solid powder.
125. (IrC1COD) 5 mg exchanged Saturated strontium 1 gm bentonite was wetted
with 100 t portion of
with TPPTS 100 mg. chloride in 2 mi solution A and evaporated under vaccume 10
mm Hg
Poly acrylic acid sodium salt water with simultanious tumbling remining
solution A was
100 mg added in 100 l fractions and solid was isolated
In 2 m1 water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow colored solid powder.
126. (RuC12COD) 5 mg exchanged Saturated strontium I gm davisil was wetted
with 100 l portion of solution
with diphenyl phosphino chloride in 2 ml A and evaporated under vaccume 10 mm
Hg with
ethane tetrasulfonate 100 mg. water simultanious tumbling remining solution A
was added
Poly acrylic acid sodium salt in 100 l fractions and solid was isolated
(moisture
100 mg content -20 %) this powder was added to solution B in
In 2 ml water equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
127. (RuC1ZCOD) 5 mg exchanged Saturated strontium 1 gm davisil was wetted
with 100 l portion of solution
with diphenyl phosphino chloride in 2 ml A and evaporated under vaccume 10 mm
Hg with
ethane tetrasulfonate 100 mg. water simultanious tumbling remining solution A
was added
Poly acrylic acid sodium salt in 100 1 fractions and solid was isolated
(moisture
100 mg content -20 %) this powder was added to solution B in
In 2 ml water equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
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128. (RuC12COD) 5 mg exchanged 500 mg calcium 1 gm davisil was wetted with 100
}tl portion of solution
with diphenyl phosphino chloride in 2 ml A and evaporated under vaccume 10 mm
Hg with
ethane tetrasulfonate 100 mg. water simultanious tumbling remining solution A
was added
Poly acrylic acid sodium salt in 100 l fractions and solid was isolated
(moisture
100 mg content -20 %) this powder was added to solution B in
In 2 ml water equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield light
brown- yellow colored solid powder.
129. Rh(COD)PF6/ S,S chiraphos Saturated strontium I gm davisil was wetted
with 100 l portion of solution
tetrasulfonate 25 mg chloride solution 2 A and evaporated under vaccume 10 mm
Hg with
S,S chiraphos tetrasulfonate ml simultanious tumbling remining solution A was
added
25 mg in 100 l fractions and solid was isolated (moisture
Sodium alginate 100 mg content -20 %) this powder was added to solution B in
dissolved in 2 ml water equal fractions over a period of 2 hours and
suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
130. Rh(COD)PFe/ S,S chiraphos Saturated barium I gm davisil was wetted with
100 l portion of solution
tetrasulfonate 25 mg nitrate solution 2 ml A and evaporated under vaccume 10
mm Hg with
S,S chiraphos tetrasulfonate simultanious tumbling reniining solution A was
added
25 mg in 100 l fractions and solid was isolated (moisture
Sodium alginate 100 mg content -20 %) this powder was added to solution B in
dissolved in 2 ml water equal fractions over a period of 2 hours and
suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
131. Rh(COD)PF6! S,S chiraphos Saturated barium I gm alumina was wetted with
100 l portion of
tetrasulfonate 25 mg nitrate solution 2 ml solution A and evaporated under
vaccume 10 mm Hg
S,S chiraphos tetrasulfonate with simultanious tumbling remining solution A
was
25 mg added in 100 l fractions and solid was isolated
Sodium alginate 100 mg (moisture content -20 %) this powder was added to
dissolved in 2 ml water solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow colored solid powder.
132. Rh(COD)PF6/ S,S chiraphos Saturated barium 1 gm titania was wetted with
100 i.tl portion of solution
tetrasulfonate 25 mg nitrate solution 2 ml A and evaporated under vaccume 10
mm Hg with
S,S chiraphos tetrasulfonate simultanious tumbling remining solution A was
added
25 mg in 100 l fractions and solid was isolated (moisture
Sodium alginate 100 mg content -20 %) this powder was added to solution B in
dissolved in 2 ml water equal fractions over a period of 2 hours and
suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
133. HRhCO(TPATS)3 500 mg Calcium 1 gm titania was wetted with 100 l portion
of solution
10 mg chloride solution in A and evaporated under vaccume 10 nun Hg with
100 mg TPATS water 5 mi simultanious tumbling reniining solution A was added
carboxy methyl cellulose in 100 l fractions and solid was isolated (moisture
sodium 100 mg in 1 nil water content -20 %) this powder was added to solution
B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
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134. HRhCO(TPATS)3 Strontium chloride 1 gm aluniina was wetted with 100 gl
portion of
mg saturated solution in solution A and evaporated under vaccume 10 mm Hg
100 mg TPATS water 5 ml with simultanious tumbling remining solution A was
carboxy methyl cellulose added in 100 1 fractions and solid was isolated
sodium 100 mg in 1 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow-green colored solid
powder.
135. HRhCO(TPATS)3 Barium nitrate 1 gm bentonite was wetted with 100 1
portion of
10 mg saturated solution in solution A and evaporated under vaccume 10 mm Hg
100 mg TPATS water 5 nil with simultanious tumbling remining solution A was
carboxy methyl cellulose added in 100 1 fractions and solid was isolated
sodium 100 mg in 1 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow-green colored solid
powder.
136. HRhCO(TPATS)3 Strontium chloride 1 gm titania was wetted with 100 l
portion of solution
10 mg saturated solution in A and evaporated under vaccume 10 mm Hg with
100 mg TPATS water 5 mi simultanious tumbling remining solution A was added
carboxy methyl cellulose in 100 l fractions and solid was isolated (moisture
sodium 100 mg in 1 ml water content -20 %) this powder was added to solution B
in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
137. HRhCO(TPATS)3 Strontium chloride I gm davisil was wetted with 100 l
portion of solution
10 mg saturated solution in A and evaporated under vaccume 10 mm Hg with
100 mg TPATS water 5 mi simultanious tumbling renaining solution A was added
carboxy methyl cellulose in 100 1 fractions and solid was isolated (moisture
sodium 100 mg in 1 ml water content -20 %) this powder was added to solution B
in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
138. HRhCO(BISBIS) 50 mg Saturated barium 2 gm davisil was wetted with 100 1
portion of solution
BISBIS 200 mg nitrate solution is 5 A and evaporated under vaccume 10 mm Hg
with
200 mg sodium sulfate ml water simultanious tumbling remining solution A was
added
dissolved in 2 nil water in 100 1 fractions and solid was isolated (moisture
content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
139. HRhCO(BISBIS) 50 mg 1 g calcium chloride 2 gm davisil was wetted with 100
1 portion of solution
BISBIS 200 mg solution In 5 ml A and evaporated under vaccume 10 mm Hg with
200 mg polyvinyl sulfonic water simultanious tumbling remining solution A was
added
acid in 100 l fractions and solid was isolated (moisture
dissolved in 2 nil water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
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140. HRhCO(BISBIS) 50 mg Saturated barium 2 gm titania was wetted with 100 1
portion of solution
BISBIS 200 mg nitrate solution is 5 A and evaporated under vaccume 10 nun Hg
with
200 mg polyacrylic acid ml water simultanious tumbling remining solution A was
added
sodium salt in 100 l fractions and solid was isolated (moisture
dissolved in 2 ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow colored solid powder.
141. HRhCO(BISBIS) 50 mg Saturated strontium 2 gm alumina was wetted with 100
l portion of
BISBIS 200 mg chloride solution is 5 solution A and evaporated under vaccume
10 nnn Hg
200 mg polyvinyl sulfonic ml water with simultanious tumbling remining
solution A was
acid added in 100 l fractions and solid was isolated
dissolved in 2 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow colored solid powder.
142. HRhCO(BISBIS) 50 mg Saturated barium 2 gm bentonite was wetted with 100
1 portion of
BISBIS 200 mg nitrate solution is 5 solution A and evaporated under vaccume 10
mm Hg
200 mg polyvinyl sulfonic ml water with simultanious tumbling remining
solution A was
acid added in 100 l fractions and solid was isolated
dissolved in 2 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow colored solid powder.
143. HRhCO(BISBIS) 50 mg Saturated barium 2 gm davisil was wetted with 100 l
portion of solution
BISBIS 200 mg nitrate solution is 5 A and evaporated under vaccume 10 mm Hg
with
200 mg polyvinyl sulfonic ml water simultanious tumbling remining solution A
was added
acid in 100 l fractions and solid was isolated (moisture
dissolved in 2 ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
144. PtC1Z(TPPTS)2 50 mg Saturated solution of 2 gm davisil was wetted with
100 l portion of solution
TPPTS 100 mg barium nitrate 5 ml A and evaporated under vaccume 10 mm Hg with
100 mg sodium alginate simultanious tumbling remining solution A was added
Dissolved in 2 ml water and in 100 l fractions and solid was isolated
(moisture
0.5 ml butane diol content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
145. PtC12(TPPTS)2 50 mg Satumted solution of 2 gm aluniina 'was wetted with
100 l portion of
TPPTS 100 mg barium nitrate 5 ml solution A and evaporated under vaccume 10 mm
Hg
100 mg oxalic acid sodium with simultanious tumbling remining solution A was
salt. added in 100 l fractions and solid was isolated
Dissolved in 2 ml water and (moisture content -20 %) this powder was added to
0.5 ml butane diol solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow-green colored solid
powder.
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146. PtClz(TPPTS)2 50 mg Saturated solution of 2 gm davisil was wetted with
100 l portion of solution
TPPTS 100 mg strontium chloride 5 A and evaporated under vaccume 10 mm Hg with
100 mg citric acid ml simultanious tumbling remining solution A was added
Dissolved in 2 ml water and in 100 l fractions and solid was isolated
(moisture
0.5 ml ethylene glycol content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
147. PtClz(TPPTS)z 50 mg Saturated solution of 2 gm davisil was wetted with
100 l portion of solution
TPPTS 100 mg barium nitrate 5 ml A and evaporated under vaccume 10 mm Hg with
100 mg polyacrylic acid simultanious tumbling reniining solution A was added
sodium salt. in 100 l fractions and solid was isolated (moisture
Dissolved in 2 ml water and content -20 %) this powder was added to solution B
in
0.5 ml butane diol equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
yellow-green colored solid powder.
148. PtCI2(TPPTS)2 50 mg Saturated solution of 2 gm shreded asbestos roap was
wetted with 100 l
TPPTS 300 mg barium nitrate 5 ml portion of solution A and evaporated under
vaccume 10
Dissolved in 2 ml water mm Hg with simultanious tumbling remining solution
A was added in 100 l fractions and solid was isolated
(moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale yellow-green colored solid
powder.
149. Cobalt N, N'ethylene bis Saturated barium 2 gm davisil was wetted with
100 l portion of solution
(salicyldianiine) 5-sulfonato nitrate solution in A and evaporated under
vaccume 10 mm Hg with
sodium 100 mg. water 5ni1 simultanious tumbling remining solution A was added
Sodium phosphate. 500 mg. in 100 l fractions and solid was isolated (moisture
In 5 ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
brown colored solid powder.
150. Cobalt N, N'ethylene bis Saturated barium 2 gm alumina was wetted with
100 l portion of
(salicyldiamine) 5-sulfonato nitrate solution in solution A and evaporated
under vaccume 10 nun Hg
sodium 100 mg. water 5m1 with simultanious tumbling remining solution A was
Sodium silicate 500 mg. added in 100 l fractions and solid was isolated
In 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale brown colored solid powder.
151. Cobalt N, N'effiylene bis Saturated barium 2 gm titania was wetted with
100 l portion of solution
(salicyldiamine) 5-sulfonato nitrate solution in A and evaporated under
vaccume 10 mm Hg with
sodium 100 mg. water 5nil simultanious tumbling reniining solution A was added
Polyvinyl sulfonate sodium. in 100 l fractions and solid was isolated
(moisture
500 mg. content -20 %) this powder was added to solution B in
In 5 ml water equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
brown colored solid powder.
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152. Cobalt N, N'ethylene bis Saturated barium 2 gm zirconia was wetted with
100 l portion of
(saflcyldiamine) 5-sulfonato nitrate solution in solution A and evaporated
under vaccume 10 mm Hg
sodium 100 mg. water 5m1 with simultanious tumbling reniining solution A was
Polyvinyl sulfonate sodium. added in 100 l fractions and solid was isolated
500 mg. (moisture content -20 %) this powder was added to
In 5 ml water solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale brown colored solid powder.
153. Cobalt N, N'ethylene bis 2g calcium chloride 2 gm shreded asbestos roap
was wetted with 100 l
(salicyldiamine) 5-sulfonato solution in water 5m1 portion of solution A and
evaporated under vaccume 10
sodium 100 mg. mm Hg with simultanious tumbling remining solution
Polyvinyl sulfonate sodium. A was added in 100 l fractions and solid was
isolated
500 mg. (moisture content -20 %) this powder was added to
In 5 ml water solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield gray colored solid powder.
154. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm shreded asbestos
roap was wetted with 100 l
tetrasulfopthalocynine. 500 chloride in 5 ml portion of solution A and
evaporated under vaccume 10
mg water mm Hg with simultanious tumbling remining solution
And 500 mg sodium sodium A was added in 100 l fractions and solid was
isolated
poly vinyl sulfonate in 5 ml (moisture content -20 %) this powder was added to
water solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield blue-gray colored solid powder.
155. Cobalt (II), 4, 4', 4",4"'- Saturated barium 2 gm kesilghur was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 nitrate in 5 ml water solution A and evaporated
under vaccume 10 mm Hg
mg with simultanious tumbling remining solution A was
And 500 mg sodium added in 100 l fractions and solid was isolated
phosphate in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
156. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm kesilghur was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 chloride in 5 ml solution A and evaporated under
vaccume 10 mm Hg
mg water with simultanious tumbling remining solution A was
And 500 mg sodium added in 100 l fractions and solid was isolated
phosphate in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
157.
Cobalt (II), 4, 4', 4",4"'- 500mg. CaClz in 5 ml 2 gm kesilghur was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 water solution A and evaporated under vaccume 10
mm Hg
mg with simultanious tumbHng remining solution A was
And 500 mg sodium added in 100 l fractions and solid was isolated
phosphate in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
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158. Copper (II), 4, 4', 4",4"'- 500mg. CaCIZ in 5 ml 2 gm kesilghur was
wetted with 100 l portion of
tetrasulfopthalocynine. 500 water solution A and evaporated under vaccume 10
mm Hg
mg with simultanious tumbling reniining solution A was
And 500 mg sodium sulfate in added in 100 l fractions and solid was isolated
5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
159. Copper (II), 4, 4', 4",4"'- Saturated strontium 2 gm kesilghur was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 chloride in 5 ml solution A and evaporated under
vaccume 10 nnn Hg
mg water with simultanious tumbling reniining solution A was
And 500 mg sodium silicate added in 100 1 fractions and solid was isolated
in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
160. Copper (II), 4, 4', 4",4"'- Saturated barium 2 gm kesilghur was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 nitrate in 5 ml water solution A and evaporated
under vaccume 10 nun Hg
mg with simultanious tumbling remining solution A was
And 500 mg sodium silicate added in 100 l fractions and solid was isolated
in 5 nil water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
161. Copper (II), 4, 4', 4", 4"'- Saturated barium 2 gm bentonite was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 nitrate in 5 ml water solution A and evaporated
under vaccume 10 nnn Hg
mg with simultanious tumbhng reniining solution A was
And 500 mg sodium silicate added in 100 l fractions and solid was isolated
in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
162. Copper (II), 4, 4', 4",4"'- Saturated strontiun 2 gm bentonite was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 chloride in 5 mi solution A and evaporated under
vaccume 10 mm Hg
mg water with simultanious tumbling remining solution A was
And 500 mg sodium silicate added in 100 l fractions and solid was isolated
in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
163.
Manganese(II), 4, 4', 4",4"'- Saturated strontiun 2 gm davisil was wetted with
100 l portion of solution
tetrasulfopthalocynine. 500 chloride in 5 ml A and evaporated under vaccume 10
mm Hg with
mg water simultanious tumbling remining solution A was added
And 500 mg sodium silicate in 100 l fractions and solid was isolated
(moisture
in 5 ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
blue colored solid powder.
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164. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm davisil was wetted
with 100 1 portion of solution
tetrasulfopthalocynine. 500 nitrate in 5 ml water A and evaporated under
vaccume 10 nun Hg with
mg simultanious tumbling remining solution A was added
And 500 mg sodium silicate in 100 l fractions and solid was isolated
(moisture
in 5 ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
blue colored solid powder.
165. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm alumina was wetted
with 100 l portion of
tetrasulfopthalocynine. 500 nitrate in 5 ml water solution A and evaporated
under vaccume 10 mm Hg
mg with simultanious tumbling remining solution A was
And 500 mg sodium silicate added in 100 l fractions and solid was isolated
in 5 ml water (moisture content -20 %) this powder was added to
solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
166. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm alumina was wetted
with 100 1 portion of
tetrasulfopthalocynine. 500 nitrate in 5 ml water solution A and evaporated
under vaccume 10 mm Hg
mg with simultaneous tumbling remaining solution A was
And 500 mg sodium added in 100 l fractions and solid was isolated
polyvinyl sulfonate in 5 ml (moisture content -20 %) this powder was added to
water solution B in equal fractions over a period of 2 hours
and suspension was further agitated for 10 hours
filtered to yield pale blue colored solid powder.
167. Iron (III), 4, 4', 4",4"'- Saturated strontium 2 gm davisil was wetted
with 100 l portion of solution
tetrasulfopthalocynine oxygen chloride in 5 ml A and evaporated under vaccume
10 mm Hg with
adduct. 500 mg water simultanious tumbling remining solution A was added
And 500 mg sodium sulfate in in 100 l fractions and solid was isolated
(moisture
ml water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
blue colored solid powder.
168. Iron (III), 4, 4', 4",4"'- Saturated barium 2 gm davisil was wetted with
100 l portion of solution
tetrasulfopthalocynine oxygen nitrate in water 5 ml A and evaporated under
vaccume 10 mm Hg with
adduct. 500 mg simultanious tumbling remining solution A was added
And 500 mg sodium sulfate in in 100 l fractions and solid was isolated
(moisture
5 nil water content -20 %) this powder was added to solution B in
equal fractions over a period of 2 hours and suspension
was further agitated for 10 hours filtered to yield pale
blue colored solid powder.
Examples 169 to 252
Preparation of catalytic formulation by deposition precipitation with
simultaneous
5 removal of water.
The following examples illustrate one of the procedures for the preparation of
the
catalytic formulation of the invention in accordance with the method of
formulation known
as co precipitation near the surface of the solid support.
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The general procedure for the preparation of heterogeneous catalytic
formulation is
described herein as making of a solution of anionically charged catalytic
entity,
catalytically inert anionic additive (termed as solution A) and solution of
group II A metal
ions (termed as solution B). The specified amount of support pretreated as
described in
earlier is impregnated with solution A by wetting solids with solution
followed by
evaporation to obtain dry solid support bearing anionic components of solution
A. This
solid powder was suspended in water immiscible solvent or a solvent that forms
azeotrope
with solvent component of solution B. the suspension was agitated and
temperature was
raised such that solvent starts distilling. Under this condition solution B
was slowly
pumped in. simultaneously solvent in which solids are suspended is also pumped
in with
rate similar to that of distillation. Once all solution B was added suspension
was stirred for
specified period of time. Resulting suspension is further agitated for
specified time.
Suspension was centrifuged and solids were repeatedly washed with water and
dried in
vacuum. Dry powder was stored under argon in gas tight vessel. These solid
catalytic
formulations can be used for appropriate reactions depending upon
catalytically active
entity incorporated in it.
Notel: solution A is prepared by dissolving anionic components including
anionic
complex and additives to make homogeneous solution in degassed solvents. And
purging
argon also degasses resulting solution.
Note 2: solution B is prepared by dissolving dissolving group IIA metal salts.
Solution was degassed prior to use
Note 3: the impregnation of solution on solid support is carried out by
wetting
solids with solution A and evaporating in vacuum at 50 C unless stated
Note 4: addition of impregnated solids with components of A to solution B is
carried out at ambient temperature unless stated.
Note 5: the impregnation of solution A may be bypassed instead following
procedure may be employed. Support is suspended in solvent to which solution
is pumped
in with simultaneous removal of solvent component of solution A. solvent is
also pumped
in such a rate that liquid volume of the container remain same. After this
solution B
addition aging and solid isolation is carried out as described earlier.
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Example Solution A Solution B Procedure
169 HRhCO(TPPTS)3, 50 mg, Saturated barium 2 gm Davisil was wetted with 100 l
portion of
TPPTS 200 mg. nitrate in water 2 ml solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml with simultanious tumbling remining solution A was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder. -
170 HRhCO(TPPTS)3, 50 mg, Saturated strontium 2 gm Davisil was wetted with 100
l portion of
TPPTS 200 mg. chloride in water 2m1 solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml with simultanious tumbling reniining solution A was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
171 HRhCO (TPPTS)3, 50 mg, 500 mg of calcium 2 gm Davisil was wetted with 100
l portion of
TPPTS 200 mg. chloride in 2 mi solution A and evaporated under vaccume 10 mm
Hg
Dissolved in water 2 nil water with simultanious tumbling renrining solution A
was
added in 100 1 fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
172 HRhCO (TPPTS)3, 50 mg, Barium nitrate 2 gm y-alumina was wetted with 100
l portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
173 HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm y-alumina was wetted with
100 l portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water 2m1 with simultanious tumbling remining solution
A was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 nil in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
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174. HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm r-alumina was wetted with
100 l portion of
TPPTS 200 mg. mg solution in 2 mi solution A and evaporated under vaccume 10
nun Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
175. HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm bentonite was wetted with 100
l portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water 2 ml with simultanious tumbling renlining
solution A was
added in 100 I fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
176. HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm bentonite was wetted with
100 l portion of
TPPTS 200 mg. saturated solution in solution .A and evaporated under vaccume
10 mm Hg
Dissolved in water 2 nil water with simultanious tumbling remining solution A
was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 inl in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
177. HRhCO (TPPTS)3, 50 mg, Calcium chloride 500 2 gm bentonite was wetted
with 100 l portion of
TPPTS 200 mg. mg solution in 2 mi solution A and evaporated under vaccume 10
nun Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
pale yellow colored solid powder.
178. HRhCO (TPPTS)3, 50 mg, Barium nitrate 2 gm charcoal was wetted with 100
i portion of
'IPPTS 200 mg. saturated solution in solution A and evaporated under vaccume
10 nun Hg
Dissolved in water 2 ml water with simultanious tumbling renlining solution A
was
added in 100 1 fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
black colored solid powder.
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179. HRhCO (TPPTS)3, 50 mg, Strontium chloride 2 gm charcoal was wetted with
100 l portion of
TPPTS 200 mg. saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in water 2 ml water with simultanious tumbling remining solution A
was
added in 100 1 fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
black colored solid powder.
180. HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm charcoal was wetted with
100 l portion of
TPPTS 200 mg. mg solution in 2 mi solution A and evaporated under vaccume 10
mm Hg
Dissolved in 2 ml water water with simultanious tumbling remining solution A
was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours to yild
black colored solid powder.
181. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm davisil was wetted with 100
l portion of solution
TPPTS 200 mg saturated solution in A and evaporated under vaccume 10 mm Hg
with
Dissolved in 2 ml water 2 ml water simultanious tumbling remining solution A
was added
in 100 1 fractions and solid was isolated this powder
was added to benzene 25 ml in apparatus described in
fig.relux was started and solution B was added in equal
fractions over a period of 2 hours while simultanious
removal of azeotropic waer and suspension was further
agitated for 10 hours filtured to yield light brown
colored solid powder.
182. Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm davisil was wetted with
100 l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Dissolved in 2 ml water. 2 ml water with simultanious tumbling remining
solution A was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 nil in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtured to
yield light brown colored solid powder..
183. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-alumina was wetted with 100
l portion of
TPPTS 200 mg Dissolved in saturated solution in solution A and evaporated
under vaccume 10 mm Hg
2 ml water 2 ml water with simultanious tumbling remining solution A was
added in 100 l fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtered to
yield light brown colored solid powder.
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184. Ru(H)(Cl)(TPP'I'S)3 50 mg Strontium chloride 2 gm y-aluniina was wetted
with 100 l portion of
TPPTS 200 mg Dissolved in saturated solution in solution A and evaporated
under vaccume 10 mm Hg
2 ml water 2 ml water with simultanious tumbling remining solution A was
added in 100 I fractions and solid was isolated this
powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtered to
yield light brown colored solid powder.
185. Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm y-alumina was wetted with
100 l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Sodium polyvinylsulfonate 2 ml water with simultanious tumbling remining
solution A was
500 mg Dissolved in 2 ml added in 100 l fractions and solid was isolated this
water powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtered to
yield light brown colored solid powder.
186. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-alumina was wetted with 100
l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Sodium polyvinylsulfonate 2 ml water with siniultanious tumbling remining
solution A was
500 mg Dissolved in 2 ml added in 100 l fractions and solid was isolated this
water powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtered to
yield light brown colored solid powder.
187. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm titania was wetted with 100
l portion of
TPPTS 200 mg saturated solution in solution A and evaporated under vaccume 10
mm Hg
Sodium polyvinylsulfonate 2 ml water with simultanious tumbling remining
solution A was
500 mg Dissolved in 2 ml added in 100 l fractions and solid was isolated this
water powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtered to
yield light brown colored solid powder.
188. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm zirconia 2 gm r-aluniina was
wetted with 100 l
TPPTS 200 mg saturated solution in portion of solution A and evaporated under
vaccume 10
Sodium polyvinylsulfonate 2 ml water mm Hg with simultanious tumbling remining
solution
500 mg Dissolved in 2 ml A was added in 100 l fractions and solid was
isolated
water this powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic waer and
suspension was further agitated for 10 hours filtered to
yield light brown colored solid powder.
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189. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm activated charcoal was wetted
with 100 l portion
TPPTS 200 mg saturated solution in of solution A and evaporated under vaccume
10 mm
Sodium polyvinylsulfonate 2 n-fl water Hg with simultanious tumbling remining
solution A
500 mg Dissolved in 2 ml was added in 100 l fractions and solid was isolated
water this powder was added to benzene 25 ml in apparatus
described in fig.relux was started and solution B was
added in equal fractions over a period of 2 hours while
simultanious removal of azeotropic water and
suspension was further agitated for 10 hours filtered to
yield black colored solid powder.
190. PdC1Z(TPPTS)210 mg Barium nitrate 2 gm shreaded asbestos roap was
suspended in benzene
TPPTS 100 mg saturated solution 5 25 ml in apparatus described in fig
agitated. The
Poly acrylic acid sodium salt ml temperature of the suspension was slowly
raised such
in 5 ml that it gently refluxes to which was added 100 l
portion of solution A and solvent component was
azeotropically removed, remining solution A was
added in 100 1 fractions untill uniform suspension
volume of suspension was maintained while
maintaining volume by pumping benzene. and solution
B was added in equal fractions over a period of 2 hours
and simultanious removal of azeotropic water and
suspension was further continued . Formed suspension
was agitated.10 hours filtered to yield yellow gray
colored solid powder.
191. PdC12(TPPTS)210 mg Strontium chloride 2 gm shreaded asbestos roap was
suspended in benzene
TPPTS 100 mg saturated solution 5 25 ml in apparatus described in fig
agitated. The
Poly acrylic acid sodium salt ml temperature of the suspension was slowly
raised such
in 5 ml that it gently refluxes to which was added 100 l
portion of solution A and solvent component was
azeotropically removed, renrining solution A was
added in 100 l fractions untill uniform suspension
volume of suspension was maintained while
maintaining volume by pumping benzene and solution
B was added in equal fractions over a period of 2 hours
and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension
was agitated for 10 hours filtered to yield yellow gray
colored solid powder.
192. PdC1Z(TPPTS)Z 10 mg 500 mg calcium chloride 2 gm shreaded asbestos roap
was suspended in benzene 25 m]
TPPTS 100 mg in 5 ml water. in apparatus described in fig agitated. The
temperature of the
Poly acrylic acid sodium salt in 5 suspension was slowly raised such that it
gently refluxes to
nil which was added 100 l portion of solution A and solvent
component was azeotropically removed, remining solution A
was added in 100 l fractions until] uniform suspension volume
of suspension was maintained while maintaining volume by
pumping benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued. Formed
suspension was agitated for.10 hours filtered to yield yellow
gray colored solid powder.
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193. PdAc2BYPYDS 25 mg Barium nitrate 2 gm davisil was suspended in benzene 25
ml in
BYPYDS 100 mg saturated solution apparatus described in fig agitated. The
temperature of
Dissolved in 2 ml water 5ni1 r the suspension was slowly raised such that it
gently
refluxes to which was added 100 l portion of solution
A and solvent component was azeotropically removed,
reniining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B'was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours filtered to
yield loght orange colored solid powder.
194. PdAc2BYPYDS 25 mg Strontium chloride 2 gm davisil was suspended in
benzene 25 ml in
BYPYDS 100 mg saturated solution apparatus described in fig agitated. The
temperature of
Dissolved in 2 ml water 5m1 the suspension was slowly raised such that it
gently
refluxes to which was added 100 l portion of solution
A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield loght orange colored solid powder.
195. PdAc2BYPYDS 25 mg 500 mg calcium 2 gm davisil was suspended in benzene 25
nil in
BYPYDS 100 mg chloride in 5 ml apparatus described in fig agitated. The
temperature of
Dissolved in 2 ml water water the suspension was slowly raised such that it
gently
refluxes to which was added 100 l portion of solution
A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was farther continued.
Formed suspension was agitated for. 10 hours filtered to
yield loght orange colored solid powder.
196. PdAcZBYPYDS 25 mg Barium nitrate saturated 2 gm bentonite was suspended
in benzene 25 nil in apparatus
BYPYDS 100 mg solution 5m1 described in fig agitated. The temperature of the
suspension
Dissolved in 2 ml water was slowly raised such that it gently refluxes to
which was
added 100 l portion of solution A and solvent component was
azeotropically removed, remining solution A was added in 100
1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield Ioght orange colored solid
powder.
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197.
PdAc2 tri ortho tolyl Barium nitrate 2 gm bentonite was suspended in benzene
25 ml in
phosphine trisulfonated 25 saturated solution apparatus described in fig
agitated. The temperature of
mg 5ml the suspension was slowly raised such that it gently
Tri ortho tolyl phosphine refluxes to which was added 100 l portion of
solution
trisulfonated 100 mg A and solvent component was azeotropically removed,
Dissolved in 2 ml water remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow brown colored solid powder.
198. PdAc2 tri ortho tolyl phosphine Strontium chloride 2 gm bentonite was
suspended in benzene 25 ml in apparatus
trisulfonated 25 mg saturated solution 5nil described in fig agitated. The
temperature of the suspension
Tri ortho tolyl phosphine was slowly raised such that it gently refluxes to
which was
trisulfonated 100 mg added 100 l portion of solution A and solvent component
was
Dissolved in 2 nil water azeotropically removed, remining solution A was added
in 100
g1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for .10 hours filtered to yield pale yellow brown
colored solid powder.
199. PdAc2 trio tolyl phosphine Barium nitrate saturated 2 gm alumina was
suspended in benzene 25 nil in apparatus
trisulfonated 25 mg solution 5m1 described in fig agitated. The temperature of
the suspension
Tri ortho tolyl phosphine was slowly raised such that it gently refluxes to
which was
trisulfonated 100 mg added 100 l portion of solution A and solvent component
was
Dissolved in 2 nil water azeotropically removed, remining solution A was added
in 100
g1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow brown
colored solid powder.
200.
PdAc2 tri ortho tolyl phosphine Barium nitrate saturated 2 gm charcoal was
suspended in benzene 25 ml in apparatus
trisulfonated 25 mg solution 5m1 described in fig agitated. The temperature of
the suspension
Tri ortho tolyl phosphine was slowly raised such that it gently refluxes to
which was
trisulfonated 100 mg added 100 l portion of solution A and solvent component
was
Dissolved in 2 ml water azeotropically removed, remining solution A was added
in 100
g1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for24 hours filtered to yield black colored solid
powder.
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201.
NiC12.(TPPTS)2 25 mg Saturated barium 1 gm davisil was suspended in benzene 25
ml in
TPPTS 100 mg nitrate in 2 ml water apparatus described in fig agitated. The
temperature of
Sodium carboxy methyl the suspension was slowly raised such that it gently
cellulose 100 mg refluxes to which was added 100 l portion of solution
Dissolved in 2 ml A and solvent component was azeotropically removed,
remining solution A was added in 100 gl fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale solid powder of white color with blue tinge.
202.
NiC12.('1'PPTS)2 25 mg Saturated barium I gm alumina was suspended in benzene
25 ml in
TPPTS 100 mg nitrate in 2 ml water apparatus described in fig agitated. The
temperature of
Sodium carboxy methyl the suspension was slowly raised such that it gently
cellulose 100 mg refluxes to which was added 100 l portion of solution
Dissolved in 2 ml A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultaniousremoval of
azeotropic water and suspension was further continued.
Formed suspension was agitated for for 10 hours
filtered to yield solid powder of white color with blue
tinge.
203
NiC12.(TPPTS)2 25 mg Saturated barium 1 gm zirconia was suspended in benzene
25 ml in
TPPTS 100 mg nitrate in 2 ml water apparatus described in fig agitated. The
temperature of
Sodium carboxy methyl the suspension was slowly raised such that it gently
cellulose 100 mg refluxes to which was added 100 l portion of solution
Dissolved in 2 ml A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale blue colored solid powder.
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204. NiC12.(TPPTS)2 25 mg Saturated strontium 1 gm zirconia was suspended in
benzene 25 ml in
TPPTS 100 mg chloride in 2 ml apparatus described in fig agitated. The
temperature of
Sodium carboxy methyl water the suspension was slowly raised such that it
gently
cellulose 100 mg refluxes to which was added 100 l portion of solution
Dissolved in 2 ml A and solvent component was azeotropically removed,
reniining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield solid powder of white color with slight blue
tinge.
205. NiCI2.(TPPTS)2 25 mg Saturated strontium 1 gm titania was suspended in
benzene 25 nil in apparatus
TPPTS 100 mg chloride in 2 ml water described in fig agitated. The temperature
of the suspension
Sodium carboxy methyl cellulose was slowly raised such that it gently refluxes
to which was
100 mg added 100 1 portion of solution A and solvent component was
Dissolved in 2 ml azeotropically removed, remining solution A was added in 100
l fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield solid powder of white
color with blue tinge.
206. NiC1Z.(TPPTS)Z 25 mg Saturated strontium 1 gm asbestos was suspended in
benzene 25 ml in apparatus
TPPTS 100 mg ' chloride in 2 ml water described in fig agitated. The
temperature of the suspension
Sodium carboxy methyl cellulose was slowly raised such that it gently refluxes
to which was
100 mg added 100 1 portion of solution A and solvent component was
Dissolved in 2 ni1 azeotropically removed, remining solution A was added in
100
1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield gray colored solid
powder.
207. (IrCICOD) 5 mg exchanged with Saturated strontium 1 gm davisil was
suspended in benzene 25 ml in apparatus
TPPTS 100 mg. chloride in 2 ml water described in fig agitated. The
temperature of the suspension
Poly acrylic acid sodium salt 100 was slowly raised such that it gently
refluxes to which was
mg added 100 1 portion of solution A and solvent component was
In 2 ml water azeotropically removed, remining solution A was added in 100
1 fractions unti11 uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow colored solid
powder.
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208. (IrCICOD) 5 mg exchanged Saturated strontium I gm keisulghur was
suspended in benzene 25 ml in
with TPPTS 100 mg. chloride in 2 ml apparatus described in fig agitated. The
temperature of
Poly acrylic acid sodium salt water the suspension was slowly raised such that
it gently
100 mg refluxes to which was added 100 l portion of solution
In 2 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
209. (IrCICOD) 5 mg exchanged Saturated strontium 1 gm bentonite was suspended
in benzene 25 ml in
with TPPTS 100 mg. chloride in 2 ml apparatus described in fig agitated. The
temperature of
Poly acrylic acid sodium salt water the suspension was slowly raised such that
it gently
100 mg refluxes to which was added 100 1 portion of solution
In 2 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated 10 hours filtered to
yield pale yellow colored solid powder.
210. (RuCIZCOD) 5 mg exchanged Saturated strontium 1 gm davisil was suspended
in benzene 25 ml in apparatus
with diphenyl phosphino ethane chloride in 2 ml water described in fig
agitated. The temperature of the suspension
tetrasulfonate 100 mg. was slowly raised such that it gently refluxes to which
was
Poly acrylic acid sodium salt 100 added 100 1 portion of solution A and
solvent component was
mg azeotropically removed, remining solution A was added in 100
In 2 ml water 1 fractions untill uniform suspension voluma of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and sirnultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow-brown
colored solid powder.
211. (RuC12COD) 5 mg exchanged Saturated strontium 1 gm davisil was suspended
in benzene 25 ml in
with diphenyl phosphino chloride in 2 ml apparatus described in fig agitated.
The temperature of
ethane tetrasulfonate 100 mg. water the suspension was slowly raised such that
it gently
Poly acrylic acid sodium salt refluxes to which was added 100 1 portion of
solution
100 mg A and solvent component was azeotropically removed,
In 2 ml water remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow-brown colored solid powder.
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212. (RuC12COD) 5 mg exchanged 500 mg calcium 1 gm davisil was suspended in
benzene 25 ml in
with diphenyl phosphino chloride in 2 rrtl apparatus described in fig
agitated. The temperature of
ethane tetrasulfonate 100 mg. water the suspension was slowly raised such that
it gently
Poly acrylic acid sodium salt refluxes to which was added 100 l portion of
solution
100 mg A and solvent component was azeotropically removed,
In 2 ml water remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow-brown colored solid powder.
213. Rh(COD)PF6/ S,S chiraphos Saturated strontium 1 gm davisil was suspended
in benzene 25 nil in
tetrasulfonate 25 mg chloride solution 2 apparatus described in fig agitated.
The temperature of
S,S chiraphos tetrasulfonate ml the suspension was slowly raised such that it
gently
25 mg refluxes to which was added 100 l portion of solution
Sodium alginate 100 mg A and solvent component was azeotropically removed,
dissolved in 2 ml water remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
214. Rh(COD)PF6/ S,S chiraphos Saturated barium nitrate I gm davisil was
suspended in benzene 25 ml in apparatus
tetrasulfonate 25 mg solution 2 ml described in fig agitated. The temperature
of the suspension
S,S chiraphos tetrasulfonate 25 was slowly raised such that it gently refluxes
to which was
mg added 100 l portion of solution A and solvent component was
Sodium alginate 100 mg dissolved azeotropically renioved, remining solution A
was added in 100
in 2 nil water l fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was fiuther continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow colored solid
powder.
215. Rh(COD)PF6/ S,S chiraphos Saturated barium 1 gm alumina was suspended in
benzene 25 ml in
tetrasulfonate 25 mg nitrate solution 2 ml apparatus described in fig
agitated. The temperature of
S,S chiraphos tetrasulfonate the suspension was slowly raised such that it
gently
25 mg refluxes to which was added 100 l portion of solution
Sodium alginate 100 mg A and solvent component was azeotropically removed,
dissolved in 2 nil water remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
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216. R1t(COD)PF6! S,S chiraphos Saturated barium 1 gm titania was suspended in
benzene 25 ml in
tetrasulfonate 25 mg nitrate solution 2 ml apparatus described in fig
agitated. The temperature of
S,S chiraphos tetrasulfonate the suspension was slowly raised such that it
gently
25 mg refluxes to which was added 100 l portion of solution
Sodium alginate 100 mg A and solvent component was azeotropically removed,
dissolved in 2 ml water remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
217. HRhCO(TPATS)3 500 mg Calcium 1 gm titania was suspended in benzene 25 ml
in
mg chloride solution in apparatus described in fig agitated. The temperature
of
100 mg TPATS water 5 ml the suspension was slowly raised such that it gently
carboxy methyl cellulose refluxes to which was added 100 l portion of
solution
sodium 100 mg in I ml water A and solvent component was azeotropically
removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow-green colored solid powder.
218. HRhCO(TPATS)3 Strontium chloride I gm alumina was suspended in benzene 25
ml in apparatus
10 mg saturated solution in described in fig agitated. The temperature of the
suspension
100 mg TPATS water 5 ml was slowly raised such that it gently refluxes to
which was
carboxy methyl cellulose sodium added 100 g1 portion of solution A and solvent
component was
100 mg in I nil water azeotropically removed, remining solution A was added in
100
l fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow-green colored
solid powder.
219. HRhCO(TPATS)3 Barium nitrate 1 gm bentonite was suspended in benzene 25
ml in
10 mg saturated solution in apparatus described in fig agitated. The
temperature of
100 mg TPATS water 5 ml the suspension was slowly raised such that it gently
carboxy methyl cellulose refluxes to which was added 100 l portion of
solution
sodium 100 mg in 1 ml water A and solvent component was azeotropically
removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow-green colored solid powder.
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220. HRhCO(TPATS)3 Strontium chloride I gm titania was suspended in benzene 25
nil in
mg saturated solution in apparatus described in fig agitated. The temperature
of
100 mg TPATS water 5 ml the suspension was slowly raised such that it gently
carboxy methyl cellulose refluxes to which was added 100 I portion of
solution
sodium 100 mg in I ml water A and solvent component was azeotropically
removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow-green colored solid powder.
221. HRhCO(TPATS)3 Strontium chloride I gm davisil was suspended in benzene 25
ml in
10 mg saturated solution in apparatus described in fig agitated. The
temperature of
100 mg TPATS water 5 ml the suspension was slowly raised such that it gently
carboxy methyl cellulose refluxes to which was added 100 l portion of
solution
sodium 100 mg in 1 ml water A and solvent component was azeotropically
removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow-green colored solid powder.
222. HRhCO(BISBIS) 50 mg Saturated barium nitrate 2 gm davisil was suspended
in benzene 25 ml in apparatus
BISBIS 200 mg solution is 5 ml water described in fig agitated. The
temperature of the suspension
200 mg sodium sulfate was slowly raised such that it gently refluxes to which
was
dissolved in 2 nil water added 100 1 portion of solution A and solvent
component was
azeotropically removed, remining soludon A was added in 100
1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow colored solid
powder.
223. HRhCO(BISBIS) 50 mg 1 g calcium chloride 2 gm davisil was suspended in
benzene 25 ml in
BISBIS 200 mg solution In 5 ml apparatus described in fig agitated. The
temperature of
200 mg polyvinyl sulfonic water the suspension was slowly raised such that it
gently
acid dissolved in 2 ml water refluxes to which was added 100 l portion of
solution
A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
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224. HRhCO(BISBIS) 50 mg Saturated barium 2 gm titania was suspended in
benzene 25 ml in
BISBIS 200 mg nitrate solution is 5 apparatus described in fig agitated. The
temperature of
200 mg polyacrylic acid ml water the suspension was slowly raised such that it
gently
sodium salt dissolved in 2 ml refluxes to which was added 100 l portion of
solution
water A and solvent component was azeotropically removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
225. HRhCO (BISBIS) 50 mg Saturated strontium 2 gm alumina was suspended in
benzene 25 ml in
BISBIS 200 mg chloride solution is 5 apparatus described in fig agitated. The
temperature of
200 mg polyvinyl sulfonic ml water the suspension was slowly raised such that
it gently
acid dissolved in 2 ml water refluxes to which was added 100 l portion of
solution
A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
226. HRhCO(BISBIS) 50 mg Saturated barium nitrate 2 gm davisil was suspended
in benzene 25 m] in apparatus
BISBIS 200 mg solution is 5 rnl water described in fig agitated. The
temperature of the suspension
200 mg polyvinyl sulfonic acid was slowly raised such that it gently refluxes
to which was
dissolved in 2 ml water added 100 l portion of solution A and solvent
component was
azeotropically removed, remining solution A was added in 100
l fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow colored solid
powder.
227. HRhCO(BISBIS) 50 mg Saturated barium 2 gm davisil was suspended in
benzene 25 ml in
BISBIS 200 mg nitrate solution is 5 apparatus described in fig agitated. The
temperature of
200 mg polyvinyl sulfonic n-fl water the suspension was slowly raised such
that it gently
acid dissolved in 2 ml water refluxes to which was added 100 gl portion of
solution
A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B. was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
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228. PtClh(TPPTS)z 50 mg Saturated solution of 2 gm davisil was suspended in
benzene 25 ml in
TPPTS 100 mg barium nitrate 5 ml apparatus described in fig agitated. The
temperature of
100 mg sodium alginate the suspension was slowly raised such that it gently
Dissolved in 2 ml water and refluxes to which was added 100 l portion of
solution
0.5 ml butane diol A and solvent component was azeotropically removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
229. PtC12(TPPTS)2 50 mg Saturated solution of 2 gm alumina 2 gm was suspended
in benzene 25 ml
TPPTS 100 mg barium nitrate 5 ml in apparatus described in fig agitated. The
temperature
100 mg oxalic acid sodium of the suspension was slowly raised such that it
gently
salt. refluxes to which was added 100 1 portion of solution
Dissolved in 2 ml water and A and solvent component was azeotropically
removed,
0.5 ml butane diol remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
230. PtCIZ(TPPTS)Z 50 mg Saturated solution of 2 gm davisil was suspended in
benzene 25 ml in apparatus
TPPTS 100 mg strontium chloride 5 ml described in fig agitated. The
temperature of the suspension
100 mg citric acid was slowly raised such that it gently refluxes to which was
Dissolved in 2 ml water and 0.5 added 100 1 portion of solution A and solvent
component was
ml ethylene glycol azeotropically removed, remining solution A was added in
100
1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping benzene
and solution B was added in equal fractions over a period of 2
hours and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension was
agitated for 10 hours filtered to yield pale yellow colored solid
powder.
231. PtC12(TPPTS)2 50 mg Saturated solution of 2 gm davisil was suspended in
benzene 25 ml in
TPPTS 100 mg barium nitrate 5 ml apparatus described in fig agitated. The
temperature of
100 mg polyacrylic acid the suspension was slowly raised such that it gently
sodium salt. refluxes to which was added 100 l portion of solution
Dissolved in 2 ml water and A and solvent component was azeotropically
removed,
0.5 ml butane diol remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for 10 hours filtered to
yield pale yellow colored solid powder.
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232. PtClz(TPPTS)z 50 mg Saturated solution of 2 gm slrreded asbestos roap 2
gm zirconia was
TPPTS 300 mg barium nitrate 5 nil suspended in benzene 25 ml in apparatus
described in
Dissolved in 2 ml water fig agitated. The temperature of the suspension was
slowly raised such that it gently refluxes to which was
added 100 l portion of solution A and solvent
component was azeotropically removed, remining
solution A was added in 100 l fractions untill uniform
suspension volume of suspension was maintained while
maintaining volume by pumping benzene.and solution
B was added in equal fractions over a period of 2 hours
and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension
was agitated forlO hours filtered to yield pale yellow-
gray colored solid powder.
233. Cobalt N, N'ethylene bis Saturated barium nitrate 2 gm davisil was
suspended in benzene 25 ml in apparatus
(salicyldiamine) 5-sulfonato solution in water 5m1 described in fig agitated.
The temperature of the suspension
sodium 100 mg. was slowly raised such that it gently refluxes to which was
Sodium phosphate. 500 mg. added 100 l portion of solution A and solvent
component was
In 5 ml water azeotropically removed, remining solution A was added in 100
l fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions over a
period of 2 hours and simultanious removal of azeotropic water
and suspension was further continued. Formed suspension was
agitated forlO hours filtered to yield pale brown colored solid
powder.
234. Cobalt N, N'ethylene bis Saturated barium 2 gm alumina was suspended in
benzene 25 nil in
(salicyldiamine) 5-sulfonato nitrate solution in apparatus described in fig
agitated. The temperature of
sodium 100 mg. water 5m1 the suspension was slowly raised such that it gently
Sodium silicate 500 mg. refluxes to which was added 100 l portion of solution
In 5 nil water A and solvent component was azeotropically removed,
remining solution A was added in 100 gl fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for10 hours filtered to
yield pale brown colored solid powder.
235. Cobalt N, N'ethylene bis Saturated barium 2 gm titania was suspended in
benzene 25 ml in
(salicyldiamine) 5-sulfonato nitrate solution in apparatus described in fig
agitated. The temperature of
sodium 100 mg. water 5m1 the suspension was slowly raised such that it gently
Polyvinyl sulfonate sodium. refluxes to which was added 100 l portion of
solution
500 mg. A and solvent component was azeotropically removed,
In 5 ml water remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated forlO hours filtered to
yield pale brown colored solid powder.
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236. Cobalt N, N'ethylene bis Saturated barium nitrate 2 gm z'vconia was
suspended in benzene 25 nil in apparatus
(salicyldiamine) 5-sulfonato solution in water 5m1 described in fig agitated.
The temperature of the suspension
sodium 100 mg. was slowly raised such that it gently refluxes to which was
Polyvinyl sulfonate sodium. 500 added 100 l portion of solution A and solvent
component was
m& azeotropically removed, remining solution A was added in 100
In S nil water i fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions over a
period of 2 hours and simultanious removal of azeotropic water
and suspension was further continued. Fonned suspension was
agitated forlO hours filtered to yield pale brown colored solid
powder.
237. Cobalt N, N'ethylene bis 2g calcium chloride 2 gm shreded asbestos roap
was suspended in benzene 25 m] in
(salicyldiamine) 5-sulfonato solution in water 5m1 apparatus described in fig
agitated. The temperature of the
sodium 100 mg. suspension was slowly raised such that it gently refluxes to
Polyvinyl sulfonate sodium. 500 which was added 100 111 portion of solution A
and solvent
mg= component was azeotropically removed, remining solution A
In 5 nil water was added in 100 i fractions untill uniform suspension volume
of suspension was maintained while maintaining volume by
pumping benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued. Formed
suspension was agitated for. 10 hours filtered to yield gray
colored solid powder.
238. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm shreded asbestos
roap was suspended in benzene
tetrasulfopthalocynine . 500 chloride in 5 ml 25 ml in apparatus described in
fig agitated. The
mg water temperature of the suspension was slowly raised such
And 500 mg sodiurXt sodium that it gently refluxes to which was added 100 1
poly vinyl sulfonate in 5 ml portion of solution A and solvent component was
water azeotropically removed, remining solution A was
added in 100 1 fractions untill uniform suspension
volume of suspension was maintained while
maintaining volume by pumping benzene.and solution
B was added in equal fractions over a period of 2 hours
and simultanious removal of azeotropic water and
suspension was further continued. Formed suspension
was agitated for. 10 hours filtered to yield blue-gray
colored solid powder.
239. Cobalt (II), 4, 4', 4",4"'- Saturated barium 2 gm keisulghur was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 nitrate in 5 ml water apparatus described in fig
agitated. The temperature of
mg the suspension was slowly raised such that it gently
And 500 mg sodium refluxes to which was added 100 1 portion of solution
phosphate in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder
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240. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm keisulghur was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 chloride in 5 ml apparatus described in fig
agitated. The temperature of
mg water the suspension was slowly raised such that it gently
And 500 mg sodium refluxes to which was added 100 l portion of solution
phosphate in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder
241. Cobalt (II), 4, 4', 4",4"'- 500mg. CaCIZ in 5 ml 2 gm keisulghur was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 water apparatus described in fig agitated. The
temperature of
mg the suspension was slowly raised such that it gently
And 500 mg sodium refluxes to which was added 100 1 portion of solution
phosphate in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder
242. Copper (li), 4, 4', 4",4"'- 500mg. CaCIZ in 5 ml 2 gm keisulghur was
suspended in benzene 25 ml in apparatus
tetrasulfopthalocynine. 500 mg water described in fig agitated. The
temperature of the suspension
And 500 mg sodium sulfate in 5 was slowly raised such that it gently refluxes
to which was
nil water added 100 1 portion of solution A and solvent component was
azeotropically removed, remining solution A was added in 100
p1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions over a
period of 2 hours and simultanious removal of azeotropic water
and suspension was further continued. Formed suspension was
agitated for.10 hours and filtered to yield pale blue colored
solid powder
243. Copper (I1), 4, 4', 4",4"'- Saturated strontium 2 gm keisulghur was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 chloride in 5 ml apparatus described in fig
agitated. The temperature of
mg water the suspension was slowly raised such that it gently
And 500 mg sodium silicate refluxes to which was added 100 g1 portion of
solution
in 5 ml water A and solvent component was azebtropically removed,
remining solution A was added in 100 gl fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder
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244. Copper (II), 4, 4', 4",4"'- Saturated barium 2 gm keisulghur was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 nitrate in 5 ml water apparatus described in fig
agitated. The temperature of
mg the suspension was slowly raised such that it gently
And 500 mg sodium silicate refluxes to which was added 100 l portion of
solution
in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder.
245. Copper (II), 4, 4', 4",4"'- Saturated barium 2 gm bentonite was suspended
in benzene 25 ml in
tetrasulfopthalocynine. 500 nitrate in 5 nil water apparatus described in fig
agitated. The temperature of
mg the suspension was slowly raised such that it gently
And 500 mg sodium silicate refluxes to which was added 100 1 portion of
solution
in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder.
246. Copper (II), 4, 4', 4",4"'- Saturated strontiun 2 gm bentonite was
suspended in benzene 25 ml in apparatus
tetrasulfopthalocynine. 500 mg chloride in 5 ml water described in fig
agitated. The temperature of the suspension
And 500 mg sodium silicate in 5 was slowly raised such that it gently refluxes
to which was
ml water added 100 ] portion of solution A and solvent component was
azeotropically removed, remining solution A was added in 100
1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping
benzene.and solu8on B was added in equal fractions over a
period of 2 hours and simultanious removal of azeotropic water
and suspension was further continued. Formed suspension was
agitated for.10 hours and filtered to yield pale blue colored
solid powder.
247. Manganese(II), 4, 4', 4",4"'- Saturated strontiun 2 gm davisil was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 chloride in 5 ml apparatus described in fig
agitated. The temperature of
mg water the suspension was slowly raised such that it gently
And 500 mg sodium silicate refluxes to which was added 100 l portion of
solution
in 5 nil water A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder.
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248. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm davisil was suspended
in benzene 25 ml in
tetrasulfopthalocynine. 500 nitrate in 5 ml water apparatus described in fig
agitated. The temperature of
mg the suspension was slowly raised such that it gently
And 500 mg sodium silicate refluxes to which was added 100 l portion of
solution
in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 .1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder.
249. Manganese(II), 4, 4', 411,4"'- Saturated barium 2 gm alumina was
suspended in benzene 25 ml in
tetrasulfopthalocynine. 500 nitrate in 5 ml water apparatus described in fig
agitated. The temperature of
mg the suspension was slowly raised such that it gently
And 500 mg sodium silicate refluxes to which was added 100 l portion of
solution
in 5 ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 l fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder.
250. Manganese(II), 4, 4', 4",4"'- Saturated barium nitrate 2 gm alumina was
suspended in benzene 25 ml in apparatus
tetrasulfopthalocynine. 500 mg in 5 ml water described in fig agitated. The
temperature of the suspension
And 500 mg sodium polyvinyl was slowly raised such that it gently refluxes to
which was
sulfonate in 5 ml water added 100 l portion of solution A and solvent
component was
azeotropically removed, remining solution A was added in 100
1 fractions untill uniform suspension volume of suspension
was maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions over a
period of 2 hours and simultanious removal of azeotropic water
and suspension was further continued. Formed suspension was
agitated for.10 hours and filtered to yield pale blue colored
solid powder.
251. Iron (III), 4, 4', 4",4"'- Saturated strontium 2 gm davisil was suspended
in benzene 25 ml in
tetrasulfopthalocynine oxygen chloride in 5 nil apparatus described in fig
agitated. The temperature of
adduct. 500 mg water the suspension was slowly raised such that it gently
And 500 mg sodium sulfate in refluxes to which was added 100 1 portion of
solution
ml water A and solvent component was azeotropically removed,
remining solution A was added in 100 1 fractions
untill uniform suspension volume of suspension was
maintained while maintaining volume by pumping
benzene.and solution B was added in equal fractions
over a period of 2 hours and simultanious removal of
azeotropic water and suspension was further continued.
Formed suspension was agitated for.10 hours and
filtered to yield pale blue colored solid powder.
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252. Iron (III), 4, 4', 4",4"'- Saturated barium 2 gm davisil was suspended in
benzene 25
tetrasulfopthalocynine nitrate in water 5 ml in apparatus described in fig
agitated.
oxygen adduct. 500 mg ml The temperature of the suspension was
And 500 mg sodium slowly raised such that it gently refluxes to
sulfate in 5 ml water which was added 100 l portion of solution
A and solvent component was
azeotropically removed, remining solution
A was added in 100 l fractions untill
uniform suspension volume of suspension
was maintained while maintaining volume
by pumping benzene.and solution B was
added in equal fractions over a period of 2
hours and simultanious removal of
azeotropic water and suspension was further
continued. Formed suspension was agitated
for.10 hours and filtered to yield pale blue
colored solid powder.
Examples 253 -336
Preparation of catalytic formulation by deposition precipitation in fluidized
bed
The following examples illustrate one of the procedures for the preparation of
the
catalytic formulation of the invention in accordance with the method of
formulation known
as co precipitation near the surface of the solid support in fluidized bed.
The general procedure for the preparation of heterogeneous catalytic
formulation is
described herein as making of a solution of anionically charged catalytic
entity,
catalytically inert anionic additive (termed as solution A) and solution of
group II A metal
ions (termed as solution B). The specified amount of support pretreated as
described in
earlier is charged in fluidization vessel and solids were fluidized with flow
of argon.
Temperature of the fluidization chamber was raised to specified temperature.
Solution A
was sprayed over the bed over the specified period of time in such a way that
solids donot
form lumps. Fluidization was continued further for specified period of time
and solution B
was similarly sprayed and fluidization was continued for specified period of
time. Solids
were discharged from vessel and aged for specified time. Catalytic formulation
thus
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formed were washed with water, methanol, diethyl ether and dried in vacuum.
Dry powder
was stored under argon in gas tight vessel. These solid catalytic formulations
can be used
for appropriate reactions depending upon catalytically active entity
incorporated in it.
Notel: solution A is prepared by dissolving anionic components including
anionic
complex and additives to make homogeneous solution in degassed solvents. And
resulting
solution is also degassed by purging argon.
Note 2: solution B is prepared by dissolving group IIA metal salts. Solution
was
degassed prior to use
Note 3: fluidized bed deposition was carried out in equipment described in
figure
(4).
Example Solution A Solution B Procedure
253 HRhCO(TPPTS)3, 50 mg, Saturated barium 2 gm Davisil was fluidized in the
current of argon and
TPPTS 200 mg. 500 1 nitrate in water 2 ml temperature of the fluidization
vessel was raised to 50
ethylene glycol dissolved in C and solution A was sprayed over a period of 2
hours
water 2 ml once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow colored solid powder.
254 HRhCO(TPPTS)3, 50 mg, Saturated strontium 2 gm Davisil was fluidized in
the current of argon and
TPPTS 200 mg. 500 1 chloride in water 2m1 temperature of the fluidization
vessel was raised to 50
ethylene glycol dissolved in C and solution A was sprayed over a period of 2
hours
water 2 nil once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow colored solid powder.
255 HRhCO(TPPTS)3, 50 mg, 500 mg of calcium 2 gm Davisil was fluidized in the
current of argon and
TPPTS 200 mg. 500 1 chloride in 2 ml temperature of the fluidization vessel
was raised to
ethylene glycol dissolved in water 50 C and solution A was sprayed over a
period of 2
water 2 ml hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
256 HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm y-aluniina was fluidized in the
current of argon
TPPTS 200 mg. 500 1 saturated solution in and temperature of the fluidization
vessel was raised to
ethylene glycol dissolved in water 50 C and solution A was sprayed over a
period of 2
water 2 ml hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
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257. HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm 7-alumina was fluidized in
the current of argon
TPPTS 200 mg. 500g1 saturated solution in and temperature of the fluidization
vessel was raised to
ethylene glycol dissolved in water 2m1 50 C and solution A was sprayed over a
period of 2
water 2 ml hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
258. HRhCO (TPPTS) 50 mg, Calcium chloride 500 2 gm y-alumina was was
fluidized in the current of
TPPTS 200 mg. 500 1 mg solution in 2 ml argon and temperature of the
fluidization vessel was
ethylene glycol dissolved in water raised to 50 C and solution A was sprayed
over a
water 2 ml = period of 2 hours once solids were free flowing
solution B was sprayed over 2 hours and fluidization
was continued fourther 2 hours. Solids were discharged
and aged for 24 hours to yield pale yellow colored solid
powder.
259. HRhCO(TPPTS) 50 mg, Barium nitrate 2 gm was fluidized in the current of
argon and
TPPTS 200 mg. 500g1 saturated solution in temperature of the fluidization
vessel was raised to 50
ethylene glycol dissolved in water 2 ml C and solution A was sprayed over a
period of 2 hours
water 2 ml once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow colored solid powder.
260. HRhCO(TPPTS) 50 mg, Strontium chloride 2 gm bentonite was fluidized in
the current of argon
TPPTS 200 mg. 500 1 saturated solution in and temperature of the fluidization
vessel was raised to
ethylene glycol dissolved in water 50 C and solution A was sprayed over a
period of 2
water 2 ml hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
261. HRhCO(TPPTS) 50 mg, Calcium chloride 500 2 gm bentonite was fluidized in
the current of argon
TPPTS 200 mg. 500 1 mg solution in 2 ml and temperature of the fluidization
vessel was raised to
effiylene glycol dissolved in water 50 C and solution A was sprayed over a
period of 2
water 2 ml hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
262. HRhCO(TPPTS) 50 mg, Barium nitrate 2 gm charcoal was fluidized in the
current of argon and
TPPTS 200 mg. 500g1 saturated solution in temperature of the fluidization
vessel was raised to 50
ethylene glycol dissolved in water C and solution A was sprayed over a period
of 2 hours
water 2 ml once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield black colored solid powder.
263. HRhCO(TPPTS) 50 mg, Strontium chloride 2 gm charcoal was fluidized in the
current of argon and
TPPTS 200 mg. 500 1 saturated solution in temperature of the fluidization
vessel was raised to 50
ethylene glycol dissolved in water C and solution A was sprayed over a period
of 2 hours
water 2 ml once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield black colored solid powder.
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264. HRhCO(TPPTS) 50 mg, Calcium chloride 500 2 gm charcoal was fluidized in
the current of argon and
TPPTS 200 mg. S00 1 Ing solution in 2 ml temperature of the fluidization
vessel was raised to 50
ethylene glycol dissolved in 2 water C and solution A was sprayed over a
period of 2 hours
ml water once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield black colored solid powder.
265. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm Davisil was fluidized in the
current of argon and
500 1 ethylene glycol saturated solution in temperature of the fluidization
vessel was raised to 50
TPPTS 200 mg dissolved in 2 ml water C and solution A was sprayed over a
period of 2 hours
2 ml water once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield light brown colored solid powder.
266. Ru(Ii)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm Davisil was wetted with
100 l portion of solution A
500 1 ethylene glycol saturated solution in 2 and evaporated under vaccume 10
mm Hg with simultanious
TPPTS 200 mg dissolved in 2 ml rn1 water tumbling remining solution A was
added in 100 l fractions
water. and solid was isolated (moisture content -20 %) this powder
was added to solution B in equal fractions over a period of 2
hours and suspension was further agitated for 10 hours filtured
to yield light brown colored solid powder.
267. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-aluniina was fluidized in
the current of argon
500 1 ethylene glycol saturated solution in and temperature of the
fluidization vessel was raised to
TPPTS 200 mg Dissolved in 2 ml water 50 C and solution A was sprayed over a
period of 2
2 ml water hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield light brown colored solid powder.
268. Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 grn y-aluniina was fluidized
in the current of argon
500 1 ethylene glycol saturated solution in and temperature of the
fluidization vessel was raised to
TPPTS 200 mg dissolved in 2 2 rrtl water 50 C and solution A was sprayed over
a period of 2
ml water hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield light brown colored solid powder.
269. Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm y-aluniina was fluidized
in the current of argon
TPPTS 200 mg saturated solution in and temperature of the fluidization vessel
was raised to
500 1 ethylene glycol 2 ml water 50 C and solution A was sprayed over a
period of 2
Sodium polyvinylsulfonate hours once solids were free flowing solution B was
500 mg dissolved in 2 nil sprayed over 2 hours and fluidization was continued
water fourther 2 hours. Solids were discharged and aged for
24 hours to yield yield light brown colored solid
powder.
270. Ru(H)(C1)(TPPTS)3 50 mg Barium nitrate 2 gm y-aluniina was fluidized in
the current of argon
TPPTS 200 mg saturated solution in and temperature of the fluidization vessel
was raised to
500 I ethylene glycol 2 ml water 50 C and solution A was sprayed over a
period of 2
Sodium polyvinylsulfonate hours once solids were free flowing solution B was
500 mg Dissolved in 2 nil sprayed over 2 hours and fluidization was continued
water further 2 hours. Solids were discharged and aged for 24
hours to yield light brown colored solid powder.
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271 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm titania was fluidized in the
current of argon and
TPPTS 200 mg saturated solution in temperature of the fluidization vessel was
raised to 50
500 1 ethylene glycol 2 ml water C and solution A was sprayed over a period
of 2 hours
Sodium polyvinylsulfonate once solids were free flowing solution B was sprayed
500 mg Dissolved in 2 ml over 2 hours and fluidization was continued fourther
2
water hours. solids were discharged and aged for 24 hours to
yield light brown colored solid powder..
272 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm zirconia was fluidized in the
current of argon and
500 1 ethylene glycol saturated solution in temperature of the fluidization
vessel was raised to 50
TPPTS 200 mg 2 ml water C and solution A was sprayed over a period of 2 hours
Sodium polyvinylsulfonate once solids were free flowing solution B was sprayed
500 mg dissolved in 2 ml over 2 hours and fluidization was continued fourther
2
water hours. Solids were discharged and aged for 24 hours to
yield light brown colored solid powder..
273 Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm activated charcoal was
fluidized in the current of
TPPTS 200 mg saturated solution in argon and temperature of the fluidization
vessel was
500 1 ethylene glycol 2 ml water raised to 50 C and solution A was sprayed
over a
Sodium polyvinylsulfonate period of 2 hours once solids were free flowing
500 mg Dissolved in 2 ml solution B was sprayed over 2 hours and fluidization
water was continued fourther 2 hours. Solids were discharged
and aged for 24 hours to yield black colored solid
powder.
274 PdCIZ(TPPTS)210 mg Barium nitrate 2 gm shreaded asbestos roap was
fluidized in the
TPPTS 100 mg saturated solution 5 current of argon and temperature of the
fluidization
500 1 ethylene glycol ml vessel was raised to 50 C and solution A was sprayed
Poly acrylic acid sodium salt over a period of 2 hours once solids were free
flowing
in 5 ml solution B was sprayed over 2 hours and fluidization
was continued fourther 2 hours. Solids were discharged
and aged for 24 hours to yield yellow gray colored
solid powder.
275 PdC12(TPPTS)z 10 mg Strontium chloride 2 gm shreaded asbestos roap was
fluidized in the
TPPTS 100 mg saturated solution 5 current of argon and temperature of the
fluidization
500 1 ethylene glycol ml vessel was raised to 50 C and solution A was sprayed
Poly acrylic acid sodium salt over a period of 2 hours once solids were free
flowing
in 5 ml solution B was sprayed over 2 hours and fluidization
was continued fourther 2 hours. Solids were discharged
and aged for 24 hours to yield yellow gray colored
solid powder.
276 PdC12(TPPTS)2 10 mg 500 mg calcium 2 gm shreaded asbestos roap was
fluidized in the
TPPTS 100 mg chloride in 5 ml current of argon and temperature of the
fluidization
500 1 ethylene glycol water. vessel was raised to 50 C and solution A was
sprayed
Poly acrylic acid sodium salt over a period of 2 hours once solids were free
flowing
in 5 ml water solution B was sprayed over 2 hours and fluidization
was continued fourther 2 hours. Solids were discharged
and aged for 24 hours to yield yellow gray colored
solid powder.
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277. PdAc2BYPYDS 25 mg Barium nitrate 2 gm davisil was fluidized in the
current of argon and
BYPYDS 100 mg saturated solution temperature of the fluidization vessel was
raised to
500 1 ethylene glycol 5ml 50 C and solution A was sprayed over a period of 2
dissolved in 2 ml water hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield loght orange colored solid powder.
278. PdAczBYPYDS 25 mg Strontium chloride 2 gm davisil was fluidized in the
current of argon and
BYPYDS 100 mg saturated solution temperature of the fluidization vessel was
raised to 50
500 1 ethylene glycol 5m] C and solution A was sprayed over a period of 2
hours
dissolved in 2 nil water once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield light orange colored solid powder.
279. PdAc2BYPYDS 25 mg 500 mg calcium 2 gm davisil was fluidized in the
current of argon and
BYPYDS 100 mg chloride in 5 ml temperature of the fluidization vessel was
raised to 50
500 1 ethylene glycol water C and solution A was sprayed over a period of 2
hours
dissolved in 2 nil water once solids were free flowing solution B was sprayed
over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield light orange colored solid powder.
280. PdAczBYPYDS 25 mg Barium nitrate 2 gm bentonite was fluidized in the
current of argon
BYPYDS 100 mg saturated solution and temperature of the fluidization vessel
was raised to
500 lethylene glycol 5ml 50 C and solution A was sprayed over a period of 2
dissolved in 2 ml water hours once solids were free flowing solution B was
sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield loght orange colored solid powder.
281. PdAc2 tri ortho tolyl Barium nitrate 2 gm bentonite was fluidized in the
current of argon
phosphine trisulfonated 25 saturated solution and temperature of the
fluidization vessel was raised to
mg 5ml 50 C and solution A was sprayed over a period of 2
500 1 ethylene glycol hours once solids were free flowing solution B was
tri ortho tolyl phosphine sprayed over 2 hours and fluidization was continued
trisulfonated 100 mg fourther 2 hours. Solids were discharged and aged for
dissolved in 2 ml water 24 hours to yield pale brown colored solid powder.
282. PdAc2 tri ortho tolyl Strontium chloride 2 gm bentonite was fluidized in
the current of argon
phosphine trisulfonated 25 saturated solution and temperature of the
fluidization vessel was raised to
mg 5ml 50 C and solution A was sprayed over a period of 2
500 1 ethylene glycol hours once solids were free flowing solution B was
Tri ortho tolyl phosphine sprayed over 2 hours and -fluidization was continued
trisulfonated 100 mg fourther 2 hours. Solids were discharged and aged for
dissolved in 2 ml water 24 hours to yield pale brown colored solid powder.
283. PdAcz trio tolyl phosphine Barium nitrate 2 gm aluniina was fluidized in
the current of argon and
trisulfonated 25 mg saturated solution temperature of the fluidization vessel
was raised to 50
500 1 ethylene glycol 5m1 C and solution A was sprayed over a period of 2
hours
Tri ortho tolyl phosphine once solids were free flowing solution B was sprayed
trisulfonated 100 mg over 2 hours and fluidization was continued fourther 2
dissolved in 2 ml water hours. Solids were discharged and aged for 24 hours to
yield pale brown colored solid powder.
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284. PdAcZ trio tolyl phosphine Barium nitrate 2 gm charcoal was fluidized in
the current of argon and
trisulfonated 25 mg saturated solution temperature of the fluidization vessel
was raised to 50
500 1 ethylene glycol 5m1 C and solution A was sprayed over a period of 2
hours
tri ortho tolyl phosphine once solids were free flowing solution B was sprayed
trisulfonated 100 mg over 2 hours and fluidization was continued fourther, 2
dissolved in 2 ml water hours. Solids were discharged and aged for 24 hours to
yield black colored solid powder.
285. NiC12.(TPPTS)z 25 mg Saturated barium 1 gm davisil was fluidized in the
current of argon and
TPPTS 100 mg nitrate in 2 ml water temperature of the fluidization vessel was
raised to 50
500 1 ethylene glycol C and solution A was sprayed over a period of 2 hours
Sodium carboxy methyl once solids were free flowing solution B was sprayed
cellulose 100 mg dissolved in over 2 hours and fluidization was continued
fourther 2
2 ml hours. Solids were discharged and aged for 24 hours to
yield solid powder of white color with blue tinge.
286. NiCIZ.(TPPTS)Z 25 mg Saturated barium 1 gm alumina was fluidized in the
current of argon and
TPPTS 100 mg nitrate in 2 ml water temperature of the fluidization vessel was
raised to 50
500 1 ethylene glycol C and solution A was sprayed over a period of 2 hours
Sodium carboxy methyl once solids were free flowing solution B was sprayed
cellulose 100 mg dissolved in over 2 hours and fluidization was continued
fourther 2
2 ml hours. Solids were discharged and aged for 24 hours to
yield solid powder of white color with blue tinge.
287. NiC12.(TPPTS)2 25 mg Saturated barium 1 gm zirconia was fluidized in the
current of argon and
500 1 ethylene glycol nitrate in 2 ml water temperature of the fluidization
vessel was raised to 50
TPPTS 100 mg C and solution A was sprayed over a period of 2 hours
Sodium carboxy methyl once solids were free flowing solution B was sprayed
cellulose 100 mg dissolved in over 2 hours and fluidization was continued
fourther 2
2 ml hours: Solids were discharged and aged for 24 hours to
yield solid powder of white color with blue tinge..
288.
NiCI2.(TPPTS)2 25 mg Saturated strontium 1 gm zirconia was fluidized in the
cun=ent of argon and
500 1 ethylene glycol chloride in 2 ml temperature of the fluidization vessel
was raised to 50
TPPTS 100 mg water C and solution A was sprayed over a period of 2 hours
Sodium carboxy methyl once solids were free flowing solution B was sprayed
cellulose 100 mg dissolved in over 2 hours and fluidization was continued
fourther 2
2 ml hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
289.
NiCIZ.(TPPTS)z 25 mg Saturated strontium 1 gm titania was fluidized in the
current of argon and
500 1 ethylene glycol chloride in 2 ml temperature of the fluidization vessel
was raised to 50
TPPTS 100 mg water C and solution A was sprayed over a period of 2 hours
Sodium carboxy methyl once solids were free flowing solution B was sprayed
cellulose 100 mg dissolved in over 2 hours and fluidization was continued
fourther 2
2 ml hours. Solids were discharged and aged for 24 hours to
yield solid powder of white color with blue tinge..
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290. NiCI2.(TPPTS)2 25 mg Saturated strontium 1 gm asbestos was fluidized in
the current of argon and
500 1 ethylene glycol chloride in 2 ml temperature of the fluidization vessel
was raised to 50
TPPTS 100 mg water C and solution A was sprayed over a period of 2 hours
Sodium carboxy methyl once solids were free flowing solution B was sprayed
cellulose 100 mg over 2 hours and fluidization was continued fourther 2
Dissolved in 2 ml hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
291. (IrCICOD) 5 mg exchanged Saturated strontium 1 gm davisil was fluidized
in the current of argon and
with TPPTS 100 mg. chloride in 2 ml temperature of the fluidization vessel was
raised to
Poly acrylic acid sodium salt water 50 C and solution A was sprayed over a
period of 2
500 1 ethylene glycol hours once solids were free flowing solution B was
100 mg dissolved in 2 ml sprayed over 2 hours and fluidization was continued
water fourther 2 hours . Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
292. (IrCICOD) 5 mg exchanged Saturated strontium I gm keisulghur was
fluidized in the current of argon
with TPPTS 100 mg. chloride in 2 ml and temperature of the fluidization vessel
was raised to
Poly acrylic acid sodium salt water 50 C and solution A was sprayed over a
period of 2
50091 ethylene glycol hours once solids were free flowing solution B was
100 mg dissolved in 2 mi sprayed over 2 hours and fluidization was continued
water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
293. (IrC1COD) 5 mg exchanged Saturated strontium 1 gm bentonite was fluidized
in the current of argon
with TPPTS 100 mg. chloride in 2 ml and temperature of the fluidization vessel
was raised to
Poly acrylic acid sodium salt water 50 C and solution A was sprayed over a
period of 2
500111 ethylene glycol hours once solids were free flowing solution B was
100 mg dissolved in 2 ml sprayed over 2 hours and fluidization was continued
water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
294. (RuC12COD) 5 mg exchanged Saturated strontium 1 gm davisil was fluidized
in the current of argon and
with diphenyl phosphino chloride in 2 ml temperature of the fluidization
vessel was raised to 50
ethane tetrasulfonate 100 mg. water C and solution A was sprayed over a
period of 2 hours
Poly acrylic acid sodium salt once solids were free flowing solution B was
sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
100 mg dissolvd in 2 ml hours. Solids were discharged and aged for 24 hours to
water yield pale yellow colored solid powder.
295. (RuCI2COD) 5 mg exchanged Saturated strontium 1 gm davisil was fluidized
in the current of argon and
with diphenyl phosphino chloride in 2 ml temperature of the fluidization
vessel was raised to
ethane tetrasulfonate 100 mg. water 50 C and solution A was sprayed over a
period of 2
Poly acrylic acid sodium salt hours once solids were free flowing solution B
was
100 mg sprayed over 2 hours and fluidization was continued
500 1 ethylene glycol fourther 2 hours. Solids were discharged and aged for
dissolved in 2 ml water 24 hours to yield pale yellow colored solid powder.
296.
(RuC12COD) 5 mg exchanged 500 mg calcium 1 gm davisil was fluidized in the
current of argon and
with diphenyl phosphino chloride in 2 ml temperature of the fluidization
vessel was raised to 50
ethane tetrasulfonate 100 mg. water C and solution A was sprayed over a
period of 2 hours
Poly acrylic acid sodium salt once solids were free flowing solution B was
sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
100 mg dissolved in 2 ml hours. Solids were discharged and aged for 24 hours
to
water yield light brown- yellow colored solid powder.
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297. Rh(COD)PF6/ S,S chiraphos Saturated strontium 1 gm davisil was fluidized
in the current of argon and
tetrasulfonate 25 mg chloride solution 2 temperature of the fluidization
vessel was raised to 50
S,S chiraphos tetrasulfonate ml C and solution A was sprayed over a period of
2 hours
25 mg once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
Sodium alginate 100 mg hours. Solids were discharged and aged for 24 hours to
dissolved in 2 ml water yield pale yellow colored solid powder.
298. Rh(COD)PF6/ S,S chiraphos Saturated barium 1 gm davisil was fluidized in
the current of argon and
tetrasulfonate 25 mg nitrate solution 2 ml temperature of the fluidization
vessel was raised to 50
S,S chiraphos tetrasulfonate C and solution A was sprayed over a period of 2
hours
25 mg once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
Sodium alginate 100 mg hours. Solids were discharged and aged for 24 hours to
dissolved in 2 ml water yield pale yellow colored solid powder.
299. Rh(COD)PF6/ S,S chiraphos Saturated barium 1 gm alumina was fluidized in
the current of argon and
tetrasulfonate 25 mg nitrate solution 2 ml temperature of the fluidization
vessel was raised to 50
S,S chiraphos tetrasulfonate C and solution A was sprayed over a period of 2
hours
25 mg once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
Sodium alginate 100 mg hours. Solids were discharged and aged for 24 hours to
dissolved in 2 ml water yield pale yellow colored solid powder.
300. Rh(COD)PF6/ S,S chiraphos Saturated barium 1 gm titania was fluidized in
the current of argon and
tetrasulfonate 25 mg nitrate solution 2 ml temperature of the fluidization
vessel was raised to 50
S,S chiraphos tetrasulfonate C and solution A was sprayed over a period of 2
hours
25 mg once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
Sodium alginate 100 mg hours. Solids were discharged and aged for 24 hours to
dissolved in 2 ml water yield pale yellow colored solid powder.
301. HRhCO(TPATS)3 500 mg Calcium 1 gm titania was fluidized in the current of
argon and
mg chloride solution in temperature of the fluidization vessel was raised to
50
100 mg TPATS water 5 ml C and solution A was sprayed over a period of 2 hours
500 1 ethylene glycol once solids were free flowing solution B was sprayed
Carboxy methyl cellulose over 2 hours and fluidization was continued fourther
2
sodium 100 mg dissolved in hours. Solids were discharged and aged for 24 hours
to
I ml water yield pale yellow-green colored solid powder.
302. HRhCO(TPATS)3 Strontium chloride 1 gm alumina was fluidized in the
current of argon and
10 mg saturated solution in temperature of the fluidization vessel was raised
to 50
500 1 ethylene glycol water 5 ml C and solution A was sprayed over a period
of 2 hours
100 mg TPATS once solids were free flowing solution B was sprayed
Carboxy methyl cellulose over 2 hours and fluidization was continued fourther
2
sodium 100 mg dissolved in 1 hours. Solids were discharged and aged for 24
hours to
ml water yield pale yellow-green colored solid powder.
303. HRhCO(TPATS)3 Barium nitrate 1 gm bentonite was fluidized in the current
of argon
10 mg saturated solution in and temperature of the fluidization vessel was
raised to
100 mg TPATS water 5 ml 50 C and solution A was sprayed over a period of 2
Carboxy methyl cellulose hours once solids were free flowing solution B was
500 1 ethylene glycol sprayed over 2 hours and fluidization was continued
sodium 100 mg dissolved in 1 fourther 2 hours. Solids were discharged and aged
for
ml water 24 hours to yield pale yellow-green colored solid
powder.
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304. HRhCO(TPATS)3 Strontium chloride 1 gm titania was fluidized in the
current of argon and
mg saturated solution in temperature of the fluidization vessel was raised to
50
100 mg TPATS water 5 ml C and solution A was sprayed over a period of 2 hours
Carboxy methyl cellulose once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
sodium 100 mg dissolved in 1 hours. Solids were discharged and aged for 24
hours to
ml water yield pale yellow-green colored solid powder.
305. HRhCO(TPATS)3 Strontium chloride 1 gm davisil was fluidized in the
current of argon and
10 mg saturated solution in temperature of the fluidization vessel was raised
to 50
100 mg TPATS water 5 ml C and solution A was sprayed over a period of 2 hours
Carboxy methyl cellulose once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
sodium 100 mg dissolved in 1 hours. Solids were discharged and aged for 24
hours to
ml water yield pale yellow-green colored solid powder.
306. HRhCO(BISBIS) 50 mg Saturated barium 2 gm davisil was fluidized in the
current of argon and
BISBIS 200 mg nitrate solution is 5 temperature of the fluidization vessel was
raised to 50
200 mg sodium sulfate ml water C and solution A was sprayed over a period of
2 hours
500 1 ethylene glycol once solids were free flowing solution B was sprayed
dissolved in 2 ml water over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow colored solid powder.
307.
HRhCO(BISBIS) 50 mg 1 g calcium chloride 2 gm davisil was fluidized in the
current of argon and
BISBIS 200 mg solution In 5 ml temperature of the fluidization vessel was
raised to
200 mg polyvinyl sulfonic water 50 C and solution A was sprayed over a period
of 2
acid hours once solids were free flowing solution B was
500 1 ethylene glycol sprayed over 2 hours and fluidization was continued
dissolved in 2 ml water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
308.
HRhCO(BISBIS) 50 mg Saturated barium 2 gm titania was fluidized in the current
of argon and
BISBIS 200 mg nitrate solution is 5 temperature of the fluidization vessel was
raised to 50
200 mg polyacrylic acid ml water C and solution A was sprayed over a period
of 2 hours
sodium salt once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
dissolved in 2 ml water hours. Solids were discharged and aged for 24 hours to
yield pale yellow colored solid powder.
309.
HRhCO(BISBIS) 50 mg Saturated strontium 2 gm alumina was fluidized in the
current of argon and
BISBIS 200 mg chloride solution is 5 temperature of the fluidization vessel
was raised to 50
200 mg polyvinyl sulfonic n-il water C and solution A was sprayed over a
period of 2 hours
acid once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
dissolved in 2 ml water hours. Solids were discharged and aged for 24 hours to
yield pale yellow colored solid powder.
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310. HRhCO(BISBIS) 50 mg Saturated barium 2 gm bentonite was fluidized in the
current of argon
BISBIS 200 mg nitrate solution is 5 and temperature of the fluidization vessel
was raised to
200 mg polyvinyl sulfonic ml water 50 C and solution A was sprayed over a
period of 2
acid hours once solids were free flowing solution B was
500 1 ethylene glycol sprayed over 2 hours and fluidization was continued
dissolved in 2 ml water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale yellow colored solid powder.
311. HRhCO(BISBIS) 50 mg Saturated barium 2 gm davisil was fluidized in the
current of argon and
BISBIS 200 mg nitrate solution is 5 temperature of the fluidization vessel was
raised to 50
200 mg polyvinyl sulfonic ml water C and solution A was sprayed over a period
of 2 hours
acid once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
dissolved in 2 ml water hours. Solids were discharged and aged for 24 hours to
yield pale yellow-green colored solid powder.
312. PtC12(TPPTS)2 50 mg Saturated solution of 2 gm davisil was fluidized in
the current of argon and
TPPTS 100 mg barium nitrate 5 ml temperature of the fluidization vessel was
raised to 50
100 mg sodium alginate C and solution A was sprayed over a period of 2 hours
dissolved in 2 ml water and once solids were free flowing solution B was
sprayed
0.5 ml butane diol over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow-green colored solid powder.
313. PtClz(TPPTS)z 50 mg Saturated solution of 2 gm alumina was fluidized in
the current of argon and
TPPTS 100 mg barium nitrate 5 ml temperature of the fluidization vessel was
raised to 50
100 mg oxalic acid sodium C and solution A was sprayed over a period of 2
hours
salt dissolved in 2 ml water once solids were free flowing solution B was
sprayed
and 0.5 ml butane diol over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow-green colored solid powder.
314. PtCIz(TPPTS)Z 50 mg Saturated solution of 2 gm davisil was fluidized in
the current of argon and
TPPTS 100 mg strontium chloride 5 temperature of the fluidization vessel was
raised to 50
100 mg citric acid ml C and solution A was sprayed over a period of 2 hours
Dissolved in 2 nil water and once solids were free flowing solution B was
sprayed
0.5 ml ethylene glycol over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale yellow-green colored solid powder.
315. PtCI2(TPPTS)z 50 mg Saturated solution of 2 gm davisil was fluidized in
the current of argon and
TPPTS 100 mg barium nitrate 5 ml temperature of the fluidization vessel was
raised to 50
100 mg polyacrylic acid C and solution A was sprayed over a period of 2 hours
sodium salt. once solids were free flowing solution B was sprayed
Dissolved in 2 nil water and over 2 hours and fluidization was continued
fourther 2
0.5 n-d butane diol hours. Solids were discharged and aged for 24 hours to
yield pale yellow-green colored solid powder.
316. PtClz(TPPTS)z 50 mg Saturated solution of 2 gm shreded asbestos roap was
fluidized in the current
TPPTS 300 mg barium nitrate 5 ml of argon and temperature of the fluidization
vessel was
500 1 ethylene glycol raised to 50 C and solution A was sprayed over a
Dissolved in 2 ml water period of 2 hours once solids were free flowing
solution B was sprayed over 2 hours and fluidization
was continued fourther 2 hours. Solids were discharged
and aged for 24 hours to yield pale yellow-green
colored solid powder.
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317. Cobalt N, N'ethylene bis Saturated barium 2 gm davisil was fluidized in
the current of argon and
(salicyldiamine) 5-sulfonato nitrate solution in temperature of the
fluidization vessel was raised to 50
sodium 100 mg. water 5m1 C and solution A was sprayed over a period of 2
hours
Sodium phosphate. 500 mg. once solids were free flowing solution B was sprayed
500 1 ethylene glycol over 2 hours and fluidization was continued fourther 2
dissolved in 5 ml water hours. Solids were discharged and aged for 24 hours to
yield pale brown colored solid powder.
318. Cobalt N, N'ethylene bis Saturated barium 2 gm alumina was fluidized in
the current of argon and
(salicyldiamine) 5-sulfonato nitrate solution in temperature of the
fluidization vessel was raised to 50
sodium 100 mg. water 5m1 C and solution A was sprayed over a period of 2
hours
500 1 ethylene glycol once solids were free flowing solution B was sprayed
Sodium silicate 500 mg over 2 hours and fluidization was continued fourther 2
dissolved in 5 ml water hours . Solids were discharged and aged for 24 hours
to
yield pale brown colored solid powder.
319. Cobalt N, N'ethylene bis Saturated barium 2 gm titania was fluidized in
the current of argon and
(salicyldiamine) 5-sulfonato nitrate solution in temperature of the
fluidization vessel was raised to 50
sodium 100 mg. water 5m1 C and solution A was sprayed over a period of 2
hours
500 1 ethylene glycol once solids were free flowing solution B was sprayed
Polyvinyl sulfonate sodium, over 2 hours and fluidization was continued
fourther 2
500 mg dissolved in 5 ml hours. Solids were discharged and aged for 24 hours
to
water yield pale brown colored solid powder.
320. Cobalt N, N'ethylene bis Saturated barium 2 gm zirconia was fluidized in
the current of argon and
(salicyldiamine) 5-sulfonato nitrate solution in temperature of the
fluidization vessel was raised to 50
sodium 100 mg. water 5m1 C and solution A was sprayed over a period of 2
hours
500 .1 ethylene glycol once solids were free flowing solution B was sprayed
Polyvinyl sulfonate sodium. over 2 hours and fluidization was continued
fourther 2
500 mg dissolved in 5 nil hours. Solids were discharged and aged for 24 hours
to
water yield pale brown colored solid powder.
321. Cobalt N, N'ethylene bis 2g calcium chloride 2 gm shreded asbestos roap
was fluidized in the current
(salicyldiamine) 5-sulfonato solution in water 5m1 of argon and temperature of
the fluidization vessel was
sodium 100 mg. raised to 50 C and solution A was sprayed over a
500 .1 ethylene glycol period of 2 hours once solids were free flowing
Polyvinyl sulfonate sodium. solution B was sprayed over 2 hours and
fluidization
500 mg dissolved in 5 ml was continued fourther 2 hours. Solids were
discharged
water and aged for 24 hours to yield gray colored solid
powder.
322. Cobalt (lI), 4, 4', 4",4111- Saturated strontium 2 gm shreded asbestos
roap was fluidized in the current of
tetrasulfopthalocynine. 500 chloride in 5 ml water argon and temperature of
the fluidization vessel was raised to
mg500 1 ethylene glycol and 500 50 C and solution A was sprayed over a period
of 2 hours
mg sodium sodium poly vinyl once solids were free flowing solution B was
sprayed over 2
sulfonate in 5 ml water hours and fluidization was continued fourther 2 hours
. solids
were discharged and aged for 24 hours to yield blue-gray
colored solid powder.
323. Cobalt (II), 4, 4', 4",4"'- Saturated barium 2 gm kesilghur was fluidized
in the current of argon
tetrasulfopthalocynine. 500 nitrate in 5 nil water and temperature of the
fluidization vessel was raised to
mg50091 ethylene glycol and 50 C and solution A was sprayed over a period of
2
500 mg sodium phosphate hours once solids were free flowing solution B was
dissolved in 5 ml water sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
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324. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm kesilghur was
fluidized in the current of argon
tetrasulfopthalocynine 500 chloride in 5 ml and temperature of the
fluidization vessel was raised to
mg500 1 ethylene glycol and water 50 C and solution A was sprayed over a
period of 2
500 mg sodium phosphate hours once solids were free flowing solution B was
dissolved in 5 ml water sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
325. Cobalt (II), 4, 4', 4",4"'- 500mg. CaC12 in 5 ml 2 gm kesilghur was
fluidized in the current of argon
tetrasulfopthalocynine 500 water and temperature of the fluidization vessel
was raised to
mg 50 C and solution A was sprayed over a period of 2
500 1 ethylene glycol and hours once solids were free flowing solution B was
500 mg sodium phosphate sprayed over 2 hours and fluidization was continued
dissolved in 5 ml water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
326. Copper (II), 4, 4', 4",4"'- 500mg. CaCI2 in 5 ml 2 gm kesilghur was
fluidized in the current of argon
tetrasulfopthalocynine. 500 water and temperature of the fluidization vessel
was raised to
mg 50 C and solution A was sprayed over a period of 2
500 1 ethylene glycol and hours once solids were free flowing solution B was
500 mg sodium sulfate sprayed over 2 hours and fluidization was continued
dissolved in 5 nil water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
327. Copper (II), 4, 4', 4",4"'- Saturated strontium 2 gm kesilghur was
fluidized in the current of argon
tetrasulfopthalocynine. 500 chloride in 5 ml and temperature of the
fluidization vessel was raised to
mg water 50 C and solution A was sprayed over a period of 2
500 1 ethylene glycol and hours once solids were free flowing solution B was
500 mg sodium silicate sprayed over 2 hours and fluidization was continued
dissolved in 5 ml water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
328. Copper (II), 4, 4', 4",4"'- Saturated barium 2 gm kesilghur was fluidized
in the current of argon
tetrasulfopthalocynine. 500 nitrate in 5 ml water and temperature of the
fluidization vessel was raised to
mg 50 C and solution A was sprayed over a period of 2
500 1 ethylene glycol hours once solids were free flowing solution B was
And 500 mg sodium silicate sprayed over 2 hours and fluidization was continued
in 5 ml water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
329. Copper (II), 4, 4', 4",4"1- Saturated barium 2 gm bentonite was fluidized
in the current of argon
tetrasulfopthalocynine 500 1 nitrate in 5 ml water and temperature of the
fluidization vessel was raised to
ethylene glycol 50 C and solution A was sprayed over a period of 2
adduct. 500 mg and 500 mg hours once solids were free flowing solution B was
sodium silicate dissolved in 5 sprayed over 2 hours and fluidization was
continued
ml water fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
330.
Copper (II), 4, 4', 4",4"'- Saturated strontiun 2 gm bentonite was fluidized
in the current of argon
tetrasulfopthalocynine. 500 chloride in 5 ml and temperatnre of the
fluidization vessel was raised to
mg 500 1 ethylene glycol water 50 C and solution A was sprayed over a period
of 2
and 500 mg sodium silicate hours once solids were free flowing solution B was
dissolved in 5 ml water sprayed over 2 hours and fluidization was continued
fourther 2 hours. Solids were discharged and aged for
24 hours to yield pale blue colored solid powder.
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331. Manganese(II), 4, 4', 4",4"'- Saturated strontiun 2 gm davisil was
fluidized in the current of argon and
tetrasulfopthalocynine. 500 chloride in 5 ml temperature of the fluidization
vessel was raised to 50
mg 500 1 ethylene glycol water C and solution A was sprayed over a period of
2 hours
and 500 mg sodium silicate once solids were free flowing solution B was
sprayed
dissolved in 5 ml water over 2 hours and fluidization was contlnued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
332. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm davisil was fluidized
in the current of argon and
tetrasulfopthalocynine. 500 nitrate in 5 ml water temperature of the
fluidization vessel was raised to 50
mg 500 1 ethylene glycol and C and solution A was sprayed over a period of 2
hours
500 mg sodium silicate once solids were free flowing solution B was sprayed
dissolved in 5 nil water over 2 hours and fluidization was continued fourther
2
hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
333. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm alumina was fluidized
in the cun=ent of argon and
tetrasulfopthalocynine. 500 nitrate in 5 m] water temperature of the
fluidization vessel was raised to 50
mg 500 1 ethylene glycol and C and solution A was sprayed over a period of 2
hours
500 mg sodium silicate once solids were free flowing solution B was sprayed
dissolved in 5 ml water over 2 hours and fluidization was continued fourther 2
hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
334. Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm aluniina was
fluidized in the current of argon and
tetrasulfopthalocynine. 500 nitrate in 5 ml water temperature of the
fluidization vessel was raised to 50
mg C and solution A was sprayed over a period of 2 hours
500 1 ethylene glycol once solids were free flowing solution B was sprayed
And 500 mg sodium over 2 hours and fluidization was continued fourther 2
polyvinyl sulfonate in 5 ml hours. Solids were discharged and aged for 24
hours to
water yield pale blue colored solid powder.
335. Iron (111), 4, 4', 4",4"'- Saturated strontium 2 gm davisil was fluidized
in the current of argon and
tetrasulfopthalocynine oxygen chloride in 5 ml temperature of the fluidization
vessel was raised to 50
adduct. 500 mg, 500 1 water C and solution A was sprayed over a period of 2
hours
ethylene glycol and 500 mg once solids were free flowing solution B was
sprayed
sodium sulfate dissolved in 5 over 2 hours and fluidization was continued
fourther 2
nil water hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
336. Iron (III), 4, 4', 4",4"'- Saturated barium 2 gm davisil was fluidized in
the current of argon and
tetrasulfopthalocynine oxygen nitrate in water 5 ml temperature of the
fluidization vessel was raised to 50
adduct 500 mg, 500 1 C and solution A was sprayed over a period of 2 hours
ethylene glycol and 500 mg once solids were free flowing solution B was
sprayed
sodium sulfate dissolved in 5 over 2 hours and fluidization was continued
fourther 2
nil water hours. Solids were discharged and aged for 24 hours to
yield pale blue colored solid powder.
Examples 337-420
Preparation of catalytic formulation by deposition precipitation in coating
pan
The following examples illustrate one of the procedures for the preparation of
the
catalytic formulation of the invention in accordance with the method of
formulation known
as co precipitation near the surface of the solid support.
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The general procedure for the preparation of heterogeneous catalytic
formulation is
described herein as making of a solution of anionically charged catalytic
entity,
catalytically inert anionic additive (termed as solution A) and solution of
group II A metal
ions (termed as solution B). The specified amount of support pretreated as
described in
earlier was charged in a pan, which was subsequently set in to rotation.
During this
procedure solids were tumbled. Temperature of the rotating pan was raised to
desired
temperature under the flow of argon solution a was sprayed on the bed of
solids over a
specified period followed by spraying solution B resulting solids were tumbled
for
specified period of time and dried in vacuum. Solids were washed with water,
methanol
and diethylether and dried. Dry powder was stored under argon in gas tight
vessel. These
solid catalytic formulations can be used for appropriate reactions depending
upon
catalytically active entity incorporated in it.
Notel: solution A is prepared by dissolving anionic components including
anionic
complex and additives to make homogeneous solution in degassed solvents. And
resulting
solution is also degassed by purging argon.
Note 2: solution B is prepared by dissolving dissolving group I1A metal salts.
Solution was degassed prior to use.
Example Solution A Solution B Procedure
337 HRhCO(TPPTS)3, 50 mg, Saturated barium 2 gm Davisil was charged in a pan,
which was
TPPTS 200 mg. 500 1 nitrate in water 2 ml subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in solids were tumbled. Temperature of the rotating
pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
338 HRhCO(TPPTS)3, 50 mg, Saturated strontium 2 gm Davisil was charged in a
pan, which was
TPPTS 200 mg. 500 1 chloride in water 2ml subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in solids were tumbled. Temperature of the rotating
pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
339 HRhCO(TPPTS) 50 mg, 500 mg of calcium 2 gm Davisil was charged in a pan,
which was
TPPTS 200 mg. 500 1 chloride in 2 ml subsequently set in to rotation. During
this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
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340. HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm y-alumina was charged in a pan,
which was
TPPTS 200 mg. 500 1 saturated solution in subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
341. HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm y-aluniina was charged in a
pan, which was
TPPTS 200 mg. 500 1 saturated solution in subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water 2m1 solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
342. HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm ~(-alumina was charged in
a pan, which was
TPPTS 200 mg. 500 1 mg solution in 2 mi subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
343. HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm bentonite was charged in a pan,
which was
TPPTS 200 mg. 500 1 saturated solution in subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water 2 mi solids were tumbled. Temperature of
the rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
344.
HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm bentonite was charged in a pan,
which was
TPPTS 200 mg. 500 1 saturated solution in subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
345.
HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm bentonite was charged in a pan
which was
TPPTS 200 mg. 500 1 mg solution in 2 ml subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
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346. HRhCO(TPPTS)3, 50 mg, Barium nitrate 2 gm charcoal was charged in a pan,
which was
TPPTS 200 mg. 500 1 saturated solution in subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield black colored solid powder.
347. HRhCO(TPPTS)3, 50 mg, Strontium chloride 2 gm charcoal was charged in a
pan, which was
TPPTS 200 mg. 5001i1 saturated solution in subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in water solids were tumbled. Temperature of the
rotating pan
water 2 ml was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield black colored solid powder.
348. HRhCO(TPPTS)3, 50 mg, Calcium chloride 500 2 gm charcoal was charged in a
pan, which was
TPPTS 200 mg. 500 1 mg solution in 2 ml subsequently set in to rotation.
During this procedure
ethylene glycol dissolved in 2 water solids were tumbled. Temperature of the
rotating pan
nil water was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
liours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield black colored solid powder.
349. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm Davisil was charged in a pan,
which was
500 1 ethylene glycol saturated solution in subsequently set in to rotation.
During this procedure
TPPTS 200 mg dissolved in 2 2 ml water solids were tumbled. Temperature of the
rotating pan
ml water was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder.
350.
Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm Davisil was charged in a pan,
which was
500 1 ethylene glycol saturated solution in subsequently set in to rotation.
During this procedure
TPPTS 200 mg dissolved in 2 2 ml water solids were tumbled. Temperature of the
rotating pan
n-A water. was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder.
351.
Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-alumina was charged in a pan,
which was
50091 ethylene glycol saturated solution in subsequently set in to rotation.
During this procedure
TPPTS 200 mg Dissolved in 2 ml water solids were tumbled. Temperature of the
rotating pan
2 ml water was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder..
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352. Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm y-alumina was charged in
a pan, which was
500 1 ethylene glycol saturated solution in subsequently set in to rotation.
During this procedure
TPPTS 200 mg dissolved in 2 2 ml water solids were tumbled. Temperature of the
rotating pan
ml water was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder.
353. Ru(H)(Cl)(TPPTS)3 50 mg Strontium chloride 2 gm y-alumina was charged in
a pan, which was
TPPTS 200 mg saturated solution in subsequently set in to rotation. During
this procedure
500 1 ethylene glycol 2 ml water solids were tumbled. Temperature of the
rotating pan
Sodium polyvinylsulfonate was raised to 70 C, under the flow of argon
solution A
500 mg dissolved in 2 ml was sprayed on the bed of solids over a period of 4
water hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield yield light brown colored solid powder.
354. Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm y-alumina was charged in a
pan, which was
TPPTS 200 mg saturated solution in subsequently set in to rotation. During
this procedure
500 1 ethylene glycol 2 ml water solids were tumbled. Temperature of the
rotating pan
Sodium polyvinylsulfonate was raised to 70 C, under the flow of argon
solution A
500 mg dissolved in 2 ml was sprayed on the bed of solids over a period of 4
water hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder.
355. Ru(H)(CI)(TPPTS)3 50 mg Barium nitrate 2 gm titania was charged in a pan,
which was
TPPTS 200 mg saturated solution in subsequently set in to rotation. During
this procedure
500 1 ethylene glycol 2 ml water solids were tumbled. Temperature of the
rotating pan
Sodium polyvinylsulfonate was raised to 70 C, under the flow of argon
solution A
500 mg dissolved in 2 ml was sprayed on the bed of solids over a period of 4
water hours followed by spraying solution B. resulting solids
were forther tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder.
356.
Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm zirconia was charged in a pan,
which was
500 1ethylene glycol saturated solution in subsequently set in to rotation.
During this procedure
TPPTS 200 mg Sodium 2 ml water solids were tumbled. Temperature of the
rotating pan
polyvinylsulfonate 500 mg was raised to 70 C, under the flow of argon
solution A
dissolved in 2 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown colored solid powder.
357.
Ru(H)(Cl)(TPPTS)3 50 mg Barium nitrate 2 gm activated charcoal was charged in
a pan, which
TPPTS 200 mg saturated solution in was subsequently set in to rotation. During
this
500 1 ethylene glycol 2 ml water procedure solids were tumbled. Temperature of
the
Sodium polyvinylsulfonate rotating pan was raised to 70 C, under the flow of
500 mg dissolved in 2 nil argon solution A was sprayed on the bed of solids
over
water a period of 4 hours followed by spraying.solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield black colored solid powder.
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358. PdC1Z(TPPTS)210 mg Barium nitrate 2 gm shreaded asbestos roap was charged
in a pan,
TPPTS 100 mg saturated solution 5 which was subsequently set in to rotation.
During this
500 1 ethylene glycol ml procedure solids were tumbled. Temperature of the
Poly acrylic acid sodium salt rotating pan was raised to 70 C, under the flow
of
dissolved in 5 ml water argon solution A was sprayed on the bed of solids over
a period of 4 hours followed by spraying solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield yellow gray colored solid
powder.
359. PdCl2(TPPTS)Z 10 mg Strontium chloride 2 gm shreaded asbestos roap was
charged in a pan,
TPPTS 100 mg saturated solution 5 which was subsequently set in to rotation.
During this
500 1 ethylene glycol ml procedure solids were tumbled. Temperature of the
Poly acrylic acid sodium salt rotating pan was raised to 70 C, under the flow
of
dissolved in 5 ml water argon solution A was sprayed on the bed of solids over
a period of 4 hours followed by spraying solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield yellow gray colored solid
powder.
360. PdC12(TPPTS)z 10 mg 500 mg calcium 2 gm shreaded asbestos roap was
charged in a pan,
TPPTS 100 mg chloride in 5 mI which was subsequently set in to rotation.
During this
500 1 ethylene glycol water. procedure solids were tumbled. Temperature of the
Poly acrylic acid sodium salt rotating pan was raised to 70 C, under the flow
of
dissolved in 5 ml water argon solution A was sprayed on the bed of solids over
a period of 4 hours followed by spraying solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield yellow gray colored solid
powder.
361. PdAc2BYPYDS 25 mg Barium nitrate 2 gm davisil was charged in a pan, which
was
BYPYDS 100 mg saturated solution subsequently set in to rotation. During this
procedure
500 1 ethylene glycol 5mI soHds were tumbled. Temperature of the rotating pan
dissolved in 2 ml water was raised to 70 C, under the flow of argon solution
A
was sprayed on the bed of sofids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield loght orange colored solid powder.
362. PdAc2BYPYDS 25 mg Strontium chloride 2 gm davisil was charged in a pan,
which was
BYPYDS 100 mg saturated solution subsequently set in to rotation. During this
procedure
500 1 ethylene glycol 5m1 solids were tumbled. Temperature of the rotating pan
dissolved in 2 ml water was raised to 70 C, under the flow of argon solution
A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light orange colored solid powder.
363. PdAc2BYPYDS 25 mg 500 mg calcium 2 gm davisil was charged in a pan, which
was
BYPYDS 100 mg chloride in 5 mi subsequently set in to rotation. During this
procedure
500 1 ethylene glycol water solids were tumbled. Temperature of the rotating
pan
dissolved in 2 ml water was raised to 70 C, under the flow of argon solution
A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light orange colored solid powder.
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364. PdAc2BYPYDS 25 mg Barium nitrate 2 gm bentonite was charged in a pan,
which was
BYPYDS 100 mg saturated solution subsequently set in to rotation. During this
procedure
5001i1 ethylene glycol 5nil solids were tumbled. Temperature of the rotating
pan
dissolved in 2 ml water was raised to 70 C, under the flow of argon solution
A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield loght orange colored solid powder.
365. PdAcZ tri ortho tolyl Barium nitrate 2 gm bentonite was charged in a pan,
which was
phosphine trisulfonated 25 saturated solution subsequently set in to rotation.
During this procedure
mg 5m] solids were tumbled. Temperature of the rotating pan
500 1 ethylene glycol was raised to 70 C, under the flow of argon solution A
tri ortho tolyl phosphine was sprayed on the bed of solids over a period of 4
trisulfonated 100 mg hours followed by spraying solution B. resulting solids
dissolved in 2 ml water were further tumbled for 2 hours and dried in vacuum
to yield pale brown colored solid powder.
366. PdAc2 tri ortho tolyl Strontium chloride 2 gm bentonite was charged in a
pan, which was
phosphine trisulfonated 25 saturated solution subsequently set in to rotation.
During this procedure
mg 5m1 solids were tumbled. Temperature of the rotating pan
500 1 ethylene glycol was raised to 70 C, under the flow of argon solution A
tri ortho tolyl phosphine was sprayed on the bed of solids over a period of 4
trisulfonated 100 mg hours followed by spraying solution B. resulting solids
dissolved in 2 ml water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow brown colored solid powder.
367. PdAc2 tri ortho tolyl Barium nitrate 2 gm alumina was charged in a pan,
which was
phosphine trisulfonated 25 saturated solution subsequently set in to rotation.
During this procedure
mg 5nil solids were tumbled. Temperature of the rotating pan
500 1 ethylene glycol was raised to 70 C, under the flow of argon solution A
tri ortho tolyl phosphine was sprayed on the bed of solids over a period of 4
tri'sulfonated 100 mg hours followed by spraying solution B. resulting solids
Dissolved in 2 ml water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow brown colored solid powder.
368.
PdAc2 tri ortho tolyl Barium nitrate 2 gm charcoal was charged in a pan, which
was
phosphine trisulfonated 25 saturated solution subsequently set in to rotation.
During this procedure
mg 5m1 solids were tumbled. Temperature of the rotating pan
500 1 ethylene glycol was raised to 70 C, under the flow of argon solution A
tri ortho tolyl phosphine was sprayed on the bed of solids over a period of 4
trisulfonated 100 mg hours followed by spraying solution B. resulting solids
dissolved in 2 ml water were further tumbled for 2 hours and dried in vacuum
to yield black colored solid powder.
369.
NiC12.(TPPTS)Z 25 mg Saturated barium 1 gm davisil was charged in a pan, which
was
TPPTS 100 mg nitrate in 2 ml water subsequently set in to rotation. During
this procedure
500 1 ethylene glycol solids were tumbled. Temperature of the rotating pan
Sodium carboxy methyl was raised to 70 C, under the flow of argon solution A
cellulose 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml of water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield solid powder of white color with blue tinge.
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370. NiC1z.(TPPTS)z 25 mg Saturated barium 1 gm alumina was charged in a pan,
which was
TPPTS 100 mg nitrate in 2 ml water subsequently set in to rotation. During
this procedure
500 I ethylene glycol solids were tumbled. Temperature of the rotating pan
Sodium carboxy methyl was raised to 70 C, under the flow of argon solution A
cellulose 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml of water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield solid powder of white color with blue tinge.
371. NiC1z.(TPPTS)2 25 mg Saturated barium 1 gm zirconia was charged in a pan,
which was
50091 ethylene glycol nitrate in 2 ml water subsequently set in to rotation.
During this procedure
TPPTS 100 mg solids were tumbled. Temperature of the rotating pan
Sodium carboxy methyl was raised to 70 C, under the flow of argon solution A
cellulose 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml of water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield solid powder of white color with blue tinge.
372. NiC12.(TPPTS)z 25 mg Saturated strontium 1 gm zirconia was charged in a
pan, which was
500 I ethylene glycol chloride in 2 ml subsequently set in to rotation. During
this procedure
TPPTS 100 mg water solids were tumbled. Temperature of the rotating pan
Sodium carboxy methyl was raised to 70 C, under the flow of argon solution A
cellulose 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml of water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield solid powder of white color with blue tinge.
373. NiC1z.(TPPTS)z 25 mg Saturated strontium 1 gm titania was charged in a
pan, which was
500g1 ethylene glycol chloride in 2 mi subsequently set in to rotation. During
this procedure
TPPTS 100 mg water solids were tumbled. Temperature of the rotating pan
Sodium carboxy methyl was raised to 70 C, under the flow of argon solution A
cellulose 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml of water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield solid powder of white color with blue tinge.
374.
NiClz.(TPPTS)z 25 mg Saturated strontium 1 gm asbestos was charged in a pan,
which was
500 1 ethylene glycol chloride in 2 mi subsequently set in to rotation. During
this procedure
TPPTS 100 mg water solids were tumbled. Temperature of the rotating pan
100 mg Sodium carboxy was raised to 70 C, under the flow of argon solution A
methyl cellulose was sprayed on the bed of solids over a period of 4
dissolved in 2 ml hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield gray blue colored solid powder.
375.
(IrC1COD) 5 mg exchanged Saturated strontium I gm davisil was charged in a
pan, which was
with TPPTS 100 mg. chloride in 2 mi subsequently set in to rotation. During
this procedure
100 mg Poly acrylic acid water solids were tumbled. Temperature of the
rotating pan
sodium salt 500 1 ethylene was raised to 70 C, under the flow of argon
solution A
glycol was sprayed on the bed of solids over a period of 4
dissolved in 2 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
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376. (IrC1COD) 5 mg exchanged Saturated strontium 1 gm keisulghur was charged
in a pan, which was
with TPPTS 100 mg. chloride in 2 ml subsequently set in to rotation. During
this procedure
100 mg Poly acrylic acid water solids were tumbled. Temperature of the
rotating pan
sodium salt 500 1 ethylene was raised to 70 C, under the flow of argon
solution A
glycol was sprayed on the bed of solids over a period of 4
dissolved in 2 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
377. (IrCICOD) 5 mg exchanged Saturated strontium 1 gm bentonite was charged
in a pan, which was
with TPPTS 100 mg. chloride in 2 mi subsequently set in to rotation. During
this procedure
Poly acrylic acid sodium salt water solids were tumbled. Temperature of the
rotating pan
5001i1 ethylene glycol was raised to 70 C, under the flow of argon solution A
100 mg dissolved in 2 ml was sprayed on the bed of solids over a period of 4
water hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
378. (RuCI2COD) 5 mg exchanged Saturated strontium 1 gm davisil was charged in
a pan, which was
with diphenyl phosphino chloride in 2 mi subsequently set in to rotation.
During this procedure
ethane tetrasulfonate 100 mg. water solids were tumbled. Temperature of the
rotating pan
100 mg Poly acrylic acid was raised to 70 C, under the flow of argon solution
A
sodium salt 500 1 ethylene was sprayed on the bed of solids over a period of 4
glycol dissolved in 2 ml water hours followed by spraying solution B.
resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
379. (RuC12COD) 5 mg exchanged Saturated strontium 1 gm davisil was charged in
a pan, which was
with diphenyl phosplrino chloride in 2 mi subsequently set in to rotation.
During this procedure
ethane tetrasulfonate 100 mg. water solids were tumbled. Temperature of the
rotating pan
100 mg Poly acrylic acid was raised to 70 C, under the flow of argon solution
A
sodium salt, 500 1 ethylene was sprayed on the bed of solids over a period of
4
glycol dissolved in 2 nil hours followed by spraying solution B. resulting
solids
water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
380.
(RuC12COD) 5 mg exchanged 500 mg calcium 1 gm davisil was charged in a pan,
which was
with diphenyl phosphino chloride in 2 ml subsequently set in to rotation.
During this procedure
ethane tetrasulfonate 100 mg. water solids were tumbled. Temperature of the
rotating pan
100 mg Poly acrylic acid was raised to 70 C, under the flow of argon solution
A
sodium salt, 500 1 ethylene was sprayed on the bed of solids over a period of
4
glycol dissolved in 2 ml water hours followed by spraying solution B.
resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield light brown- yellow colored solid powder.
381.
Rh(COD)PF6/ S,S chiraphos Saturated strontium 1 gm davisil was charged in a
pan, which was
tetrasulfonate 25 mg chloride solution 2 subsequently set in to rotation.
During this procedure
S,S chiraphos mi solids were tumbled. Temperature of the rotating pan
tetrasulfonate 25 mg, was raised to 70 C, under the flow of argon solution A
was sprayed on the bed of solids over a period of 4
SOO I ethylene glycol, hours followed by spraying solution B. resulting solids
Sodium alginate 100 mg were further tumbled for 2 hours and dried in vacuum
dissolved in 2 ml water to yield pale yellow colored solid powder.
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382. Rh(COD)PF6/ S,S chiraphos Saturated barium I gm davisil was charged in a
pan, which was
tetrasulfonate 25 mg nitrate solution 2 ml subsequently set in to rotation.
During this procedure
S,S chiraphos tetrasulfonate solids were tumbled. Temperature of the rotating
pan
25 mg was raised to 70 C, under the flow of argon solution A
500 1 ethylene glycol, was sprayed on the bed of solids over a period of 4
Sodium alginate 100 mg, hours followed by spraying solution B. resulting
solids
dissolved in 2 ml water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
383. Rh(COD)PF6/ S,S chiraphos Saturated barium I gm alumina was charged in a
pan, which was
tetrasulfonate 25 mg nitrate solution 2 ml subsequently set in to rotation.
During this procedure
S,S chiraphos tetrasulfonate solids were tumbled. Temperature of the rotating
pan
25 mg, 500 1 ethylene glycol, was raised to 70 C, under the flow of argon
solution A
Sodium alginate 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
384. Rh(COD)PFrJ S,S chiraphos Saturated barium 1 gm titania was charged in a
pan, which was
tetrasulfonate 25 mg nitrate solution 2 mi subsequently set in to rotation.
During this procedure
S,S chiraphos tetrasulfonate solids were tumbled. Temperature of the rotating
pan
25 mg, 50041 ethylene glycol, was raised to 70 C, under the flow of argon
solution A
Sodium alginate 100 mg was sprayed on the bed of solids over a period of 4
dissolved in 2 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
385. HRhCO(TPATS)3 500 mg Calcium I gm titania was charged in a pan, which was
mg chloride solution in subsequently set in to rotation. During this procedure
100 mg TPATS water 5 ml solids were tumbled. Temperature of the rotating pan
500 1 ethylene glycol was raised to 70 C, under the flow of argon solution A
Carboxy methyl cellulose was sprayed on the bed of solids over a period of 4
sodium 100 mg dissolved in 1 hours followed by spraying solution B. resulting
solids
ml water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
386. HRhCO(TPATS)3 Strontium chloride 1 gm alumina was cbarged in a pan, which
was
10 mg saturated solution in subsequently set in to rotation. During this
procedure
500 1 ethylene glycol water 5 ml solids were tumbled. Temperature of the
rotating pan
100 mg TPATS was raised to 70 C, under the flow of argon solution A
carboxy methyl cellulose was sprayed on the bed of solids over a period of 4
sodium 100 mg dissolved in hours followed by spraying solution B. resulting
solids
1 ml water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
387.
HRhCO(TPATS)3 Barium nitrate 1 gm bentonite was charged in a pan, which was
10 mg saturated solution in subsequently set in to rotation. During this
procedure
100 mg TPATS water 5 ml solids were tumbled. Temperature of the rotating pan
carboxy methyl cellulose was raised to 70 C, under the flow of argon solution
A
500 1 ethylene glycol was sprayed on the bed of solids over a period of 4
sodium 100 mg dissolved in 1 hours followed by spraying solution B. resulting
solids
ml water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
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388. HRhCO(TPATS)3 Strontium chloride 1 gm titania was charged in a pan, which
was
mg saturated solution in subsequently set in to rotation. During this
procedure
100 mg TPATS water 5 ml solids were tumbled. Temperature of the rotating pan
Carboxy methyl cellulose was raised to 70 C, under the flow of argon solution
A
500 lethylene glycol was sprayed on the bed of solids over a period of 4
sodium 100 mg dissolved in 1 hours followed by spraying solution B. resulting
solids.
nil water were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
389. HRhCO(TPATS)3 Strontium chloride 1 gm davisil was charged in a pan, which
was
10 mg saturated solution in subsequently set in to rotation. During this
procedure
100 mg TPATS, sodium water 5 mi solids were tumbled. Temperature of the
rotating pan
carboxy methyl cellulose 100 was raised to 70 C, under the flow of argon
solution A
mg, 500 .1 ethylene glycol, was sprayed on the bed of solids over a period of
4
dissolved in 1 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
390. HRhCO(BISBIS) 50 mg Saturated barium 2 gm davisila was charged in a pan,
which was
BISBIS 200 mg, nitrate solution is 5 subsequently set in to rotation. During
this procedure
200 mg sodium sulfate, ml water solids were tumbled. Temperature of the
rotating pan
500 1 ethylene glycol, was raised to 70 C, under the flow of argon solution A
dissolved in 2 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
391. HRhCO(BISBIS) 50 mg 1 g calcium chloride 2 gm davisil was charged in a
pan, which was
BISBIS 200 mg solution In 5 ml subsequently set in to rotation. During this
procedure
200 mg polyvinyl sulfonic water solids were tumbled. Temperature of the
rotating pan
acid, 500 1 ethylene glycol, was raised to 70 C, under the flow of argon
solution A
dissolved in 2 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
392.
HRhCO(BISBIS) 50 mg Saturated barium 2 gm titania was charged in a pan, which
was
BISBIS 200 mg nitrate solution is 5 subsequently set in to rotation. During
this procedure
200 mg polyacrylic acid ml water solids were tumbled. Temperature of the
rotating pan
sodium salt, 500 1 ethylene was raised to 70 C, under the flow of argon
solution A
glycol dissolved in 2 ml water was sprayed on the bed of solids over a period
of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
393.
HRhCO(BISBIS) 50 mg Saturated strontium 2 gm alumina was charged in a pan,
which was
BISBIS 200 mg chloride solution is 5 subsequently set in to rotation. During
this procedure
200 mg polyvinyl sulfonic ml water solids were tumbled. Temperature of the
rotating pan
acid, 500 1 ethylene glycol, was raised to 70 C, under the flow of argon
solution A
dissolved in 2 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow colored solid powder.
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394. HRhCO(BISBIS) 50 mg Saturated barium 2 gm bentonite was charged in a pan,
which was
BISBIS 200 mg, 200 mg nitrate solution is 5 subsequently set in to rotation.
During this procedure
polyvinyl sulfonic acid, 500111 ml water solids were tumbled. Temperature of
the rotating pan
ethylene glycol, dissolved in was raised to 70 C, under the flow of argon
solution A
2 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 liours and dried in vacuum
to yield pale yellow colored solid powder.
395. HRhCO(BISBIS) 50 mg Saturated barium 2 gm Davisil was charged in a pan,
which was
BISBIS 200 mg, 200 mg nitrate solution is 5 subsequently set in to rotation.
During this procedure
polyvinyl sulfonic acid, 500 I ml water solids were tumbled. Temperature of
the rotating pan
ethylene glycol, dissolved in was raised to 70 C, under the flow of argon
solution A
2 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
396. PtC12(TPPTS)2 50 mg Saturated solution of 2 gm davisil was charged in a
pan, which was
TPPTS 100 mg, 100 mg barium nitrate 5 ml subsequently set in to rotation.
During this procedure
sodium alginate dissolved in solids were tumbled. Temperature of the rotating
pan
2 ml water and 0.5 ml butane was raised to 70 C, under the flow of argon
solution A
diol was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
397. PtCI2(TPPTS)2 50 mg Saturated solution of 2 gm alumina was charged in a
pan, which was
TPPTS 100 mg, 100 mg barium nitrate 5 ml subsequently set in to rotation.
During this procedure
oxalic acid sodium salt, solids were tumbled. Temperature of the rotating pan
dissolved in 2 ml water and was raised to 70 C, under the flow of argon
solution A
0.5 ml butane diol was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
398.
PtC12(TPPTS)2 50 mg Saturated solution of 2 gm davisil was charged in a pan,
which was
TPPTS 100 mg, 100 mg citric strontium chloride 5 subsequently set in to
rotation. During this procedure
acid, dissolved in 2 ml water ml solids were tumbled. Temperature of the
rotating pan
and 0.5 ml ethylene glycol was raised to 70 C, under the flow of argon
solution A
was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
399.
PtCIZ(TPPTS)2 50 mg Saturated solution of 2 gm davisil was charged in a pan,
which was
TPPTS 100 mg, 100 mg barium nitrate 5 mi subsequently set in to rotation.
During this procedure
polyacrylic acid sodium salt, solids were tumbled. Temperature of the rotating
pan
dissolved in 2 ml water and was raised to 70 C, under the flow of argon
solution A
0.5 ml butane diol was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale yellow-green colored solid powder.
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400. PtCIZ(TPPTS)2 50 mg, TPPTS Saturated solution of 2 gm shreded asbestos
roap was charged in a pan,
300 mg, 500 1 ethylene barium nitrate 5 ml wliich was subsequently set in to
rotation. During this
glycol, Dissolved in 2 nil procedure solids were tumbled. Temperature of the
water rotating pan was raised to 70 C, under the flow of
argon solution A was sprayed on the bed of solids over
a period of 4 hours followed by spraying solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield pale yellow-green colored
solid powder.
401. Cobalt N, N'ethylene bis Saturated barium 2 gm davisil was charged in a
pan, which was
(salicyldianiine) 5-sulfonato nitrate solution in subsequently set in to
rotation. During this procedure
sodium 100 mg, Sodium water 5m1 solids were tumbled. Temperature of the
rotating pan
phosphate. 500 mg.,500 1 was raised to 70 C, under the flow of argon solution
A
ethylene glycol dissolved in 5 . was sprayed on the bed of solids over a
period of 4
ml water hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale brown colored solid powder.
402. Cobalt N, N'ethylene bis Saturated barium 2 gm alumina was charged in a
pan, which was
(salicyldianiine) 5-sulfonato nitrate solution in subsequently set in to
rotation. During this procedure
sodium 100 mg, 500 1 water 5mi solids were tumbled. Temperature of the
rotating pan
ethylene glycol, Sodium was raised to 70 C, under the flow of argon solution
A
silicate 500 mg dissolved in 5 was sprayed on the bed of solids over a period
of 4
nil water hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale brown colored solid powder.
403. Cobalt N, N'ethylene bis Saturated barium 2 gm titania was charged in a
pan, which was
(salicyldiamine) 5-sulfonato nitrate solution in subsequently set in to
rotation. During this procedure
sodium 100 mg,500 1 water 5m1 solids were tumbled. Temperature of the rotating
pan
ethylene glycol, Polyvinyl was raised to 70 C, under the flow of argon
solution A
sulfonate sodium. 500 mg was sprayed on the bed of solids over a period of 4
dissolved in 5 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale brown colored solid powder.
404. Cobalt N, N'ethylene bis Saturated barium 2 gm zirconia was charged in a
pan, which was
(salicyldiamine) 5-sulfonato nitrate solution in subsequently set in to
rotation. During this procedure
sodium 100 mg, 500 1 water 5m1 solids were tumbled. Temperature of the
rotating pan
ethylene glycol, polyvinyl was raised to 70 C, under the flow of argon
solution A
sulfonate sodium. 500 mg was sprayed on the bed of solids over a period of 4
dissolved in 5 ml water hours followed by spraying solution B. resulting
solids
were further tumbled for 2 hours and dried in vacuum
to yield pale brown colored solid powder.
405. Cobalt N, N'ethylene bis 2g calcium chloride 2 gm shreded asbestos roap
was charged in a pan,
(salicyldiamine) 5-sulfonato solution in water 5m1 which was subsequently set
in to rotation. During this
sodium 100 mg, 500 1 procedure solids were tumbled. Temperature of the
ethylene glycol, polyvinyl rotating pan was raised to 70 C, under the flow of
sulfonate sodium. 500 mg in argon solution A was sprayed on the bed of solids
over
ml water a period of 4 hours followed by spraying solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield gray colored solid powder.
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406. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm shreded asbestos
roap was charged in a pan,
tetrasulfopthalocynine 500 chloride in 5 nil which was subsequently set in to
rotation. During this
mg500 1 ethylene glycol and water procedure solids were tumbled. Temperature
of the
500 mg sodium sodium poly rotating pan was raised to 70 C, under the flow of
vinyl sulfonate in 5 ml water argon solution A was sprayed on the bed of
solids over
a period of 4 hours followed by spraying solution B.
resulting solids were further tumbled for 2 hours and
dried in vacuum to yield blue-gray colored solid
powder.
407. Cobalt (II), 4, 4', 4",4"'- Saturated barium 2 gm kesilghur was charged
in a pan, which was
tetrasulfopthalocynine 500 nitrate in 5 ml water subsequently set in to
rotation. During this procedure
mg500 1 ethylene glycol and solids were tumbled. Temperature of the rotating
pan
500 mg sodium phosphate in was raised to 70 C, under the flow of argon
solution A
ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
408. Cobalt (II), 4, 4', 4",4"'- Saturated strontium 2 gm kesilghur was
charged in a pan, which was
tetrasulfopthalocynine 500 chloride in 5 mi subsequently set in to rotation.
During this procedure
mg500 1 ethylene glycol and water solids were tumbled. Temperature of the
rotating pan
500 mg sodium phosphate in was raised to 70 C, under the flow of argon
solution A
5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
409. Cobalt (II), 4, 4', 4",4"'- 500mg. CaC12 in 5 ml 2 gm kesilghur was
charged in a pan, which was
tetrasulfopthalocynine 500 water subsequently set in to rotation. During this
procedure
mg, 500 1 ethylene glycol solids were tumbled. Temperature of the rotating pan
and 500 mg sodium was raised to 70 C, under the flow of argon solution A
phosphate in 5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
410.
Copper (rI), 4, 4', 4",4"'- 500mg. CaC12 in 5 ml 2 gm kesilghur was charged in
a pan, which was
tetrasulfopthalocynine. 500 water subsequently set in to rotation. During this
procedure
mg, 500 I ethylene glycol solids were tumbled. Temperature of the rotating pan
and 500 mg sodium sulfate in was raised to 70 C, under the flow of argon
solution A
5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
411. Copper (II), 4, 4', 4",4"'- Saturated strontium 2 gm kesilghur was
charged in a pan, which was
tetrasulfopthalocynine. 500 chloride in 5 mi subsequently set in to rotation.
During this procedure
mg, 500 1 ethylene glycol water solids were tumbled. Temperature of the
rotating pan
and 500 mg sodium silicate in was raised to 70 C, under the flow of argon
solution A
5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
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412. Copper (II), 4, 4', 4",4"1- Saturated barium 2 gm kesilghur was charged
in a pan, which was
tetrasulfopthalocynine. 500 nitrate in 5 ml water subsequently set in to
rotation. During this procedure
mg, 500 1 ethylene glycol solids were tumbled. Temperature of the rotating pan
and 500 mg sodium silicate in was raised to 70 C, under the flow of argon
solution A
ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
413. Copper (II), 4, 4', 4",4"'- Saturated barium 2 gm bentonite was charged
in a pan, which was
tetrasulfopthalocynine 500 1 nitrate in 5 ml water subsequently set in to
rotation. During this procedure
ethylene glycol, 500 mg and solids were tumbled. Temperature of the rotating
pan
500 mg sodium silicate in 5 was raised to 70 C, under the flow of argon
solution A
ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
414. Copper (II), 4, 4', 4",4"'- Saturated strontiun 2 gm bentonite was
charged in a pan, which was
tetrasulfopthalocynine 500 chloride in 5 nil subsequently set in to rotation.
During this procedure
mg, 500 1 ethylene glycol water solids were tumbled. Temperature of the
rotating pan
and 500 mg sodium silicate in was raised to 70 C, under the flow of argon
solution A
5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
415. Manganese(II), 4, 4', 4",4"'- Saturated strontiun 2 gm davisil was
charged in a pan, which was
tetrasulfopthalocynine. 500 chloride in 5 nil subsequently set in to rotation.
During this procedure
mg, 500 1 ethylene glycol water solids were tumbled. Temperature of the
rotating pan
and 500 mg sodium silicate in was raised to 70 C, under the flow of argon
solution A
5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
416.
Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm davisil was charged in a
pan, which was
tetrasulfopthalocynine. 500 nitrate in 5 nil water subsequently set in to
rotation. During this procedure
mg, 500 1 ethylene glycol solids were tumbled. Temperature of the rotating pan
and 500 mg sodium silicate in was raised to 70 C, under the flow of argon
solution A
5 ml water was sprayed on the bed of solids over a period of 4
hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield blue colored solid powder.
417.
Manganese(II), 4, 4', 4",4"'- Saturated barium 2 gm alumina was charged in a
pan, which was
tetrasulfopthalocynine. 500 nitrate in 5 ml water subsequently set in to
rotation. During this procedure
mg solids were tumbled. Temperature of the rotating pan
500 1 ethylene glycol was raised to 70 C, under the flow of argon solution A
And 500 mg sodium silicate was sprayed on the bed of solids over a period of 4
in 5 ml water hours followed by spraying solution B. resulting solids
were further tumbled for 2 hours and dried in vacuum
to yield pale blue colored solid powder.
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418. Manganese(II), 4, 4', Saturated barium 2 gm alumina was charged in a pan,
which
4",4"'- nitrate in 5 ml was subsequently set in to rotation. During
tetrasulfopthalocynine water this procedure solids were tumbled.
500 mg, 500 1 ethylene Temperature of the rotating pan was raised
glycol and 500 mg to 70 C, under the flow of argon solution A
sodium polyvinyl was sprayed on the bed of solids over a
sulfonate in 5 ml water period of 4 hours followed by spraying
solution B. resulting solids were further
tumbled for 2 hours and dried in vacuum to
yield pale blue colored solid powder.
419. Iron (III), 4, 4', 4",4"'- Saturated 2 gm davisil was charged in a pan,
which
tetrasulfopthalocynine strontium was subsequently set in to rotation. During
oxygen adduct. 500 mg, chloride in 5 ml this procedure solids were tumbled.
50o 1 ethylene glycol water Temperature of the rotating pan was raised
and 500 mg sodium to 70 C, under the flow of argon solution A
sulfate in 5 ml water was sprayed on the bed of solids over a
period of 4 hours followed by spraying
solution B. resulting solids were further
tumbled for 2 hours and dried in vacuum to
yield pale blue colored solid powder.
420. Iron (III), 4, 4', 4",4"'- Saturated barium 2 gm davisil was charged in a
pan, which
tetrasulfopthalocynine nitrate in water 5 was subsequently set in to rotation.
During
oxygen adduct. 500 mg ml this procedure solids were tumbled.
500 1 ethylene glycol Temperature of the rotating pan was raised
and 500 mg sodium to 70 C, under the flow of argon solution A
sulfate in 5 ml water was sprayed on the bed of solids over a
period of 4 hours followed by spraying
solution B. resulting solids were further
tumbled for 2 hours and dried in vacuum to
yield pale blue colored solid powder.
Examples 421 - 429
Catalyst stability in various organic solvents
These examples illustrate the stability of catalysts in liquid phases.
Stability of
catalyst was assessed in order to establish integrity and resilience of
catalyst in liquid
phase reactions. Apparatus according to figure 3 was assembled and 5g.
catalyst was added
in the extraction vessel. 0.5-liter solvent was charged in extraction vessel.
Solids in the
extractor were agitated and solvent in the round bottomed flask was set to
boiling. Solid
catalyst was continuously leached for 24 hours. Boiling liquid was brought to
room
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temperature and analyzed for group IIA metal and transition metal. No leaching
of
catalytically active material was apparent.
No Catalyst Extraction solvent Observation
421 Catalytic entity: Water No leaching detected
HRhCO(TPPTS)3 (10-6 mols) colour of solid remains
Additive: TPPTS 6* 10-6 mols/ unchanged
polyvinyl sulfonic acid 100 mg
Support: 5 g silica Davisil TM Methanol No leaching detected
Group IIA metal: barium colour of solid remains
Method of preparation: unchanged
deposition precipitation
Colour of catalyst : pale yellow Acetone No leaching detected
colour of solid remains
unchanged
Thf No leaching detected
colour of solid remains
unchanged
Acetonitrile No leaching detected
colour of solid becomes
light orange
DMF No leaching detected
colour of solid becomes
light orange
Chloroform No leaching detected
colour of solid remains
unchanged
Tolune No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
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422 Catalytic entity: Water No leaching detected
Ru(H)(Cl)(TPPTS)4 (10'6 mols) colour of solid remains
Additive: TPPTS 8* 10"6 mols/ unchanged
alginic acid 100 mg
Support: 5 g silica Davisil TM Methanol No leaching detected
Group IIA metal: strontium colour of solid remains
Method of preparation: unchanged
fluidized bed precipitation
Colour of catalyst: pale brown Acetone No leaching detected
colour of solid remains
unchanged
Thf No leaching detected
colour of solid remains
unchanged
Acetonitrile No leaching detected
colour of solid turns
slightly dark
DMF No leaching detected
colour of solid changes
slightly dark
Chloroform No leaching detected
colour of solid remains
unchanged
Toluene No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
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423 Catalytic entity: palladium Water No leaching detected
acetate bypyridine disulfonated colour of solid remains
-6 mols unchanged
Additive: bypyridine
disulfonated 10-5 mols/ Methanol No leaching detected
polyacrylic acid acid 100 mg colour of solid remains
Support: 5 g charcoal unchanged
Group IIA metal: strontium
Method of preparation: Acetone No leaching detected
fluidized bed precipitation colour of solid remains
Colour of catalyst: pale orange unchanged.
THF No leaching detected
colour of solid remains
unchanged
Acetonitrile No leaching detected
colour of solid remains
unchanged
DMF No leaching detected
colour of solid remains
unchanged
Chloroform No leaching detected
colour of solid remains
unchanged
Toluene No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
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424 Catalytic entity: Water No leaching detected
cobalt(II)4,4',4",4"colour of solid remains
tetrasulfopthalocynine 10 ~ mols unchanged
additive: sodium phosphate 100
mg Methanol No leaching detected
Support: 5 g gamma alumina colour of solid remains
Group IIA metal: barium unchanged
Method of preparation: coating
pan precipitation Acetone No leaching detected
Colour of catalyst: pale blue colour of solid remains
unchanged
THF No leaching detected
colour of solid remains
unchanged
Acetonitrile No leaching detected
colour of solid remains
unchanged
DMF No leaching detected
colour of solid remains
unchanged
Chloroform No leaching detected
colour of solid remains
unchanged
Toluene No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
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425 Catalytic entity: sulfonated Water No leaching detected
quaternary ammonium
hydroxide benzyl triphenyl Methanol No leaching detected
amine 10 -4 mols
additive: carboxymethyl
cellulose 100 mg Acetone No leaching detected
Support: 5 g activated charcoal
Group IIA metal: barium TBF No leaching detected
Method of preparation:
coprecipitation Chloroform No leaching detected
Toluene No leaching detected
Hexane No leaching detected
426 Catalytic entity: cobalt(II) N,N'- Water No leaching detected
ethylene bis(salicyldiamine 5- colour of solid remains
sodium sulfonate) 10 -4 mols unchanged
additive: sodium sulfate 200 mg
Support: 5 g asbestos
Group IIA metal: barium Methanol No leaching detected
Method of preparation: coating colour of solid remains
pan unchanged
Color of the catalyst: gray
brown Acetone No leaching detected
colour of solid remains
unchanged
THF No leaching detected
colour of solid remains
unchanged
Acetonitrile No leaching detected
colour of solid remains
unchanged
DMF No leaching detected
colour of solid remains
unchanged
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Chloroform No leaching detected
colour of solid remains
unchanged
Toluene No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
427 Catalytic entity: Water No leaching detected
NiC12(TPPTS)210 -4 mols Methanol No leaching detected
additive: tppts 20* 10-4 mols Acetone No leaching detected
Support: 5 g activated charcoal THF No leaching detected
Group IIA metal: strontium Acetonitrile No leaching detected
Method of preparation: DMF No leaching detected
fluidized bed precipitation Chloroform No leaching detected
Tolune No leaching detected
Hexane No leaching detected
Acetic acid No leaching detected
428 Catalytic entity: Rh +C1O4 (S,S) No leaching detected
chiraphos tetra sulfonated 10 --6 Water colour of solid remains
mols unchanged
additive: s,s chiraphos 20* 10-6 No leaching detected
mols Methanol colour of solid remains
Support: 5 g silica Davisil TM unchanged
Group IIA metal: barium
Method of preparation: coating Acetone No leaching detected
pan precipitation colour of solid remains
Color of the catalyst: pale unchanged
yellow No leaching detected
Thf colour of solid remains
unchanged
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Acetonitrile No leaching detected
colour of solid remains
unchanged
DMF No leaching detected
colour of solid remains
unchanged
Chloroform No leaching detected
colour of solid remains
unchanged
Tolune No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
429 Catalytic entity: Mo04- 10 Water No leaching detected
mols colour of solid remains
additive: sodium phosphate 500 unchanged
mg Methanol No leaching detected
Support: 5 g calcium silicate colour of solid remains
Group IIA metal: calcium unchanged
Method of preparation: Acetone No leaching detected
coprecipitation colour of solid remains
unchanged
Thf No leaching detected
colour of solid remains
unchanged
Acetonitrile No leaching detected
colour of solid remains
unchanged
DMF No leaching detected
colour of solid remains
unchanged
Chloroform No leaching detected
colour of solid remains
unchanged
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Tolune No leaching detected
colour of solid remains
unchanged
Hexane No leaching detected
colour of solid remains
unchanged
Acetic acid No leaching detected
colour of solid remains
unchanged
Example 430
Hydroformylation reaction as a probe
This example illustrates the applicability of the catalytic formulation to
liquid phase
reaction wherein two gases react with substrate in liquid phase. This example
also
illustrates how solid catalyst can be employed to catalyze reaction and a
preferred method
to recover and recycle it.
Catalyst specification
Catalytic entity HRhCO(TPPTS)3 (10.8 *. 10" mols)
Additive TPPTS 6* 10" mols/ polyvinyl sulfonic
acid 100 mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Colour of catalyst pale yellow
Metal content in solid 10.8 * 10 mols of rhodium.
Reaction procedure: Under a argon atmosphere the micro-reactor was charged
with
1 g. of catalyst and 25 ml of octene the reactor was flushed with HZ/ CO
mixture and
reactor was heated to 75 C and pressurized with H2/ CO mixture (1:lby mole) to
600 psi
and maintained at this temperature. Liquid suspension was stirred at 900 rpm.
Reaction
was continued for 240 min. analysis of the products confirmed conversion of
olefins to
aldehydes.
Conversion 14 * 10"3 mols of octene
Turn over frequencies at 60 min were 894 hour 1
Turnover number after 240 min was 1296.29 mols . mol-1 of catalyst
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n/i ratio after 240 min was 2.7 ( wherein n is linear aldehyde and I is iso
aldehyde)
Color of recovered catalyst: light brown
The catalyst was recovered by centrifugation and repeatedly washing reactor
with tolune
under nitrogen atmosphere. Solid catalyst was dried under vacuum. Which was
recycled to
perform reaction as described earlier to obtain equivalent activity and
selectivity. The color
of catalyst was light brown
Examples 431
Need of the support
These comparative examples illustrate the need of solid support in the
catalytic
formulation and effect of loading of catalytically active solid material on
solid support to
decide a protocol for optimum loading.
Hydroformylation of hexene
Catalyst specifications:
Catalytic entity HRhCO(TPPTS)3 (10 mols)
Additive TPPTS 6* 10 mols/ polyvinyl sulfonic
acid 100 mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Colour of catalyst pale yellow
Procedure:
Under a argon atmosphere the microreactor was charged with 2 g of catalyst and
0.5 g (5.2 * 10"4 mols) of hexene in 20 ml tolune the reactor was flushed with
H2/ CO
mixture and reactor was heated to 75 C and pressurized with H2/ CO mixture
(1: lby mole)
and,maintained at this temperature. Liquid suspension was stirred with
external magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 89 % Olefin was converted to aldehydes
with n/I
selectivity of 1.80.
Under identical conditions 4 * 10-7 mols of barium salt of rhodium catalyst
failed to
promote any reaction.
Example 432
Effect of the added ligand
These comparative examples illustrate the need of additional ligand in
catalytic
formulation. These examples also illustrate solid support in the catalytic
formulation and
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effect of loading of catalytically active solid material on solid support to
decide optimum
loading.
Catalyst preparation catalyst of varying specifications were prepared by
following
method:
Hydroformylation of hexene
Preparation of catalyst:
Catalyst specifications:
Catalyst A Catalyst B Catalyst C
Catalytic entity HRhCO(TPPTS)3 HRhCO(TPPTS)3 HRhCO(TPPTS)3
(10"6 mols) (10"6 mols) (10"6 mols)
Additive polyvinyl sulfonic TPPTS 6* 10 mols/ TPPTS 12* 10
acid 100 mg polyvinyl sulfonic mols/ polyvinyl
acid 100 mg sulfonic acid 100 mg
Support: 5 g silica Davisil TM 5 g silica Davisil TM 5 g silica Davisil TM
Group IIA metal barium barium barium
Method of deposition deposition deposition
preparation precipitation precipitation precipitation
Colour of catalyst pale yellow pale yellow pale yellow
Procedure:
Under a argon atmosphere the microreactor was charged with 2 g of catalyst and
0.5 g (5.2 * 10-4 mols) of hexene in 20 ml tolune the reactor was flushed with
H2/ CO
mixture and reactor was heated to 75 C and pressurized with H2/ CO mixture
(1: lby mole)
and maintained at this temperature. Liquid suspension was stirred with
external magnetic
agitation. Reaction was continued for 24 hours.
Analysis of the products confirmed conversion of olefins to aldehydes. About
89 %
Olefin was converted to aldehydes with n/I selectivity of 1.80.
Example 433
Effect of added water-Hydroformylation of hexene
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Catalyst specifications:
Catalytic entity HRhCO(TPPTS)3 (10 mols)
Additive TPPTS 6* 10" mols/ polyvinyl sulfonic
acid 100 mg
Support: 5 g silica Davisil TM
Group IIA metal Barium
Method of preparation deposition precipitation
Colour of catalyst pale yellow
Moisture content 2%
Procedure:
Under a argon atmosphere the microreactor was charged with 2 g of catalyst and
0.5 g (5.2 * 104 mols) of hexene in 20 ml tolune the reactor was flushed with
H2/ CO
mixture and reactor was heated to 75 C and pressurized with H2/ CO mixture
(1:lby mole)
and maintained at this temperature. Liquid suspension was stirred with
external magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 89% Olefin was converted to aldehydes with
n/I
selectivity of 1.80.
Under identical conditions in reaction charge lg water was added and after 24
hours only 5% conversion was obtained with similar n/I ratio.
Example 434
Continuous fixed bed experiment
Catalyst specifications:
Catalytic entity HRhCO(TPPTS)3 (10 mols)
Additive TPPTS 6* 10-6 mols/ polyvinyl sulfonic
acid 100 mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Colour of catalyst pale yellow
Procedure: Accordingly the crucial evaluation indicating life of the catalyst,
its stability
and the durability was performed in a tubular fixed bed reactor by subjecting
catalyst to
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hydroformylation in tubular trical bed reactor (o 1/2") at 80 C and 300 psi
H2/CO (1:1)
using 5 g. of catalyst. 5 % decene in toluene was pumped continuously at the
feed rate of
ml/hr conversion levels were 20 %(fluctuating by +-2.2 %) for aldehydes (n/i
2.1) after
attaining steady state (5 hours). The reaction was further continued for 76 hr
without loss
5 of activity. Reaction was arrested by discontinuing the liquid feed and
water was pumped
for 1 hr. thereafter reactant feed was resumed. Initially there was no
conversion, which was
steadily resumed to earlier levels over the period of 10 hr. This observation
was attributed
to formation of water film on the catalyst surface, which physically retards
contact of
decene with catalyst surface. Moreover water does not wash out complex
catalyst, which
10 provides conclusive proof that reaction occurs in the solid state.
Example 435
Hydroformylation of hexene
Catalyst specifications:
Catalytic entity IiRhCO(TPPTS)3 (10 mols)
Additive TPPTS 6* 10" mols/ polyvinyl sulfonic
acid 100 mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Procedure:
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05 g (5.2 * 10"4 mols) of hexene in 2 ml toluene the reactor was flushed
with H2/ CO
mixture and reactor was heated to 75 C and pressurized with H2/ CO mixture
(1:1by mole)
and maintained at this temperature. Liquid suspension was stirred with
external magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 89 % Olefin was converted to aldehydes
with n/I
selectivity of 1.91 the catalyst was recovered by washing reactor several
times with toluene
and catalyst was recovered by centrifugation, washing repeatedly with toluene
and diethyl
ether. Catalyst was dried under vacuum and recycled to obtain equivalent
activity.
Example 436
Hydroformylation of styrene
Preparation of catalysts
Catalyst specifications:
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Catalytic entity HRhCO(TPPTS)3 (10" mols)
Additive TPPTS 6* 10' mols/ polyvinyl sulfonic acid 100
mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05 g (4.8 * 10 "4) of styrene in 2 ml toluene the reactor was flushed
with H2/ CO
mixture and reactor was heated to 75 C and pressurized with H2/ CO mixture
(1:-lby mole)
and maintained at this temperature. Liquid suspension was stirred with
external magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 91 % Olefin was converted to aldehydes
with n/I ratio
of 0.449. The catalyst was recovered by washing reactor several times with
toluene and
catalyst was recovered by centrifugation, washing repeatedly with toluene and
diethyl
ether. Catalyst was dried under vacuum and recycled to obtain equivalent
activity.
Example 437
Hydroformylation of cyclohexene
Preparation of catalysts
Catalyst specifications:
Catalytic entity HRhCO(TPPTS)3 (10' mols)
Additive TPPTS 6* 10 mols/ polyvinyl sulfonic acid 100
mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05
g (6.1 * 10"4) of cyclohexene in 2 ml toluene the reactor was flushed with Hz/
CO mixture
and reactor was heated to 75 C and pressurized with H2/ CO mixture (1:1by
mole) and
maintained at this temperature. Liquid suspension was stirred with external
magnetic
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agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes.47 % Olefin was converted to aldehydes. The
catalyst
was recovered by washing reactor several times with toluene and catalyst was
recovered by
centrifugation, washing repeatedly with toluene and diethyl ether. Catalyst
was dried under
vacuum and recycled to obtain equivalent activity.
Example 438
Hydroformylation of allyl alcohol
Catalyst specifications:
Catalytic entity HRhCO(TPPTS)3 (10" mols)
Additive TPPTS 6* 10-6 mols/ polyvinyl sulfonic
acid 100 mg
Support: 5 g silica Davisil TM
Group IIA metal barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Procedure: Under a argon atmosphere the microreactor was charged with 200 mg
of
catalyst and 0.05 g (8.7 * 10-4 mols) of allyl alcohol in 2 ml water the
reactor was flushed
with H2/ CO mixture and reactor was heated to 75 C and pressurized with H2/
CO mixture
(1:1by mole) and maintained at this temperature. Liquid suspension was stirred
with
external magnetic agitation. Reaction was continued for 24 hours. Analysis of
the products
confirmed conversion of olefins to aldehydes. 20 % Olefin was converted to
aldehydes
with n/i ratio of 1. The catalyst was recovered by washing reactor several
times with
toluene and catalyst was recovered by centrifugation, washing repeatedly with
toluene and
diethyl ether. Catalyst was dried under vacuum and recycled to obtain
equivalent activity.
Example 439
Hydroformylation of hexene
Catalyst specifications:
Catalytic entity HRhCO(N(PhmSO3-)3)3 (10-6 mols)
Additive N(PhmSO3 )3 6* 10 mols/ polyvinyl
sulfonic acid 100 mg
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Support 5 g silica Davisil TM
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.5 g
(5.9 *10-4, mol) of hexene in 2 ml toluene the reactor was flushed with H2/ CO
mixture and
reactor was heated to 75 C and pressurized with H2/ CO mixture (1:1by mole)
and
maintained at this temperature. Liquid suspension was stirred with external
magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 68 % Olefin was converted to aldehydes
with n/I
selectivity of 1.78 the catalyst was recovered by washing reactor several
times with toluene
and catalyst was recovered by centrifugation, washing repeatedly with toluene
and diethyl
ether. Catalyst was dried under vacuum and recycled to obtain equivalent
activity.
Example 440
Hydroformylation of hexene
Catalyst specifications:
Catalytic entity HRhCO(BISBIS) (10-6 mols)
Additive BISBIS 6* 10 mols/ polyvinyl sulfonic
acid 100 mg
Support 5 g silica Davisil TM
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05
g (5.9 * 10"4, mol) of hexene in 2 ml toluene the reactor was flushed with Ha/
CO mixture
and reactor was heated to 75 C and pressurized with H2/ CO mixture (1:lby
mole) and
maintained at this temperature. Liquid suspension was stirred with external
magnetic
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agitation. Reaction was continued for 24 hours. Analysis of the products
confizmed
conversion of olefins to aldehydes. 78 % Olefin was converted to aldehydes
with n/I
selectivity of 17.88. The catalyst was recovered by washing reactor several
times with
toluene and catalyst was recovered by centrifugation, washing repeatedly with
toluene and
diethyl ether. Catalyst was dried under vacuum and recycled to obtain
equivalent activity.
Example 441
Hydroformylation of hexene
Catalyst specifications:
Catalytic entity HrhCO(succindiphos) (10-6 mols)
Additive succindiphos 6* 10" mols/ polyvinyl
sulfonic acid 100 mg
Support 5 g silica Davisil TM
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05 g (5.9 * 10"4, mol) of hexene in 2 ml toluene the reactor was flushed
with H2/ CO
mixture and reactor was heated to 75 C and pressurized with I-I2/ CO mixture
(1:lby mole)
and maintained at this temperature. Liquid suspension was stirred with
external magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 80 % Olefin was converted to aldehydes
with n/I
selectivity of 0.6. The catalyst was recovered by washing reactor several
times with
toluene and catalyst was recovered by centrifugation, washing repeatedly with
toluene and
diethyl ether. Catalyst was dried under vacuum and recycled to obtain
equivalent activity.
Example 442
Hydroformylation of hexene
Catalyst specifications:
Catalytic entity HRhCO(bypyds) (10" mols)
Additive bypyds 6* 10" mols/ polyvinyl sulfonic
acid 100 mg
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Support 5 g silica Davisil TM
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05
g (5.9 * 10"4, mol) of hexene in 2 ml toluene the reactor was flushed with H2/
CO mixture
and reactor was heated to 75 C and pressurized with H2/ CO mixture (l:lby
mole) and
maintained at this temperature. Liquid suspension was stirred with external
magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 80 % Olefin was converted to aldehydes
with n/I
selectivity of 0.92. The catalyst was recovered by washing reactor several
times with
toluene and catalyst was recovered by centrifugation, washing repeatedly with
toluene and
diethyl ether. Catalyst was dried under vacuum and recycled to obtain
equivalent activity.
Example 443
Cobalt catalyzed hydroformylation
Catalyst specifications:
Catalytic entity (Co(Ac)2/(P(PhmSO3 )3)3 (10 mols)
Additive P(Ph,,,SO3")3 6* 10" mols/ polyvinyl
sulfonic acid 100 mg
Support 5 g silica Davisil TM
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Under a argon atmosphere the microreactor was charged with 200 mg of catalyst
and 0.05
g (5.9 * 10"4, mol) of hexene in 2 ml toluene the reactor was flushed with H2/
CO mixture
and reactor was heated to 75 C and pressurized with HZ/ CO mixture (l:lby
mole) and
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maintained at this temperature. Liquid suspension was stirred with external
magnetic
agitation. Reaction was continued for 24 hours. Analysis of the products
confirmed
conversion of olefins to aldehydes. 30 % Olefin was converted to aldehydes
with n/i of
1.38. The catalyst was recovered by washing reactor several times with toluene
and
catalyst was recovered by centrifugation, washing repeatedly with toluene and
diethyl
ether. Catalyst was dried under vacuum and recycled to obtain equivalent
activity.
Example 444
Platinum catalyzed hydroformylation
Preparation of catalysts: heterogenized platinum chloride phosphine complex
was boiled
with dichloromethane and stannous chloride and subsequently extracted with
dichloromethane
Catalyst specifications:
Catalytic entity SnC12PtC12(P(Ph,,,SO3")3)2 (10" mols)
Additive N(PhmSO3-)3 6* 10 mols/ polyvinyl
sulfonic acid 100 mg
Support 5 g silica Davisil TM
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst pale yellow
Procedure: Under a argon atmosphere the microreactor was charged with 200 mg
of
catalyst and 0.05 g ( 5.9 *10"4, mol) of hexene in 2 ml toluene the reactor
was flushed with
H2/ CO mixture and reactor was heated to 75 C and pressurized with H2/ CO
mixture
(1:1by mole) and maintained at this temperature. Liquid suspension was stirred
with
external magnetic agitation. Reaction was continued for 24 hours. Analysis of
the products
confirmed conversion of olefins to aldehydes. 57 % Olefin was converted to
aldehydes
with n/I selectivity of 10.47. The catalyst was recovered by washing reactor
several times
with toluene and catalyst was recovered by centrifugation, washing repeatedly
with toluene
and diethyl ether. Catalyst was dried under vacuum and recycled to obtain
equivalent
activity.
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Example 445
Carbonylation of styrene
Catalyst specifications:
Catalytic entity Pd(Ac)2(P(PhmS03 )2(PyS03")) (10-11
mols)
Additive (P(PhmS03 )2(PyS03 ) 6* 10 mols/
polyvinyl sulfonic acid 100 mg
Support 5 g charcoal
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst Black
Metal content
Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
500 mg (4.90 10-3 mmol) styrene and 5 mg p toluene sulfonic, acid 25 mg N, N,
dimethyl
aniline and 10 ml methanol. Micro reactor was flushed with argon and
pressurized with
carbon monoxide 800 psi and mixture was stirred at 70 C for 24 hours.
Reaction mixture
was analyzed by gas chromatograph. 87 % phenyl acetylene was carbonylated with
99 %
selectivity for methyl 2phenyl propionate. Reaction mixture was centrifuged to
recover
solid catalyst, which was subsequently washed with methanol repeatedly.
Catalyst was
further washed with diethyl ether and dried under vacuum.
Example 446
Carbonylation of styryl alcohol
Preparation of catalysts
Catalyst specifications:
Catalytic entity Pd(Ac)2(P(PhmS03 )2(PyS03 )) (10 mols)
Additive (P(PhmS03 )2(PyS03 ) 6* 10 mols/ polyvinyl
sulfonic acid 100 mg
Support 5 g charcoal
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst Black
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Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
500 mg (8.9 * 10"3 mmol) styryl alcohol and 5 mg p toluene sulfonic, acid and
10 ml
methanol. Micro reactor was flushed with argon and pressurized with carbon
monoxide
800 psi and mixture was stirred at 100 C for 24 hours. Reaction mixture was
analyzed by
gas chromatograph. 52 % phenyl acetylene was carbonylated with 91 %
selectivity for
methyl 2 phenyl propionate over 2-phenyl propionate. Reaction mixture was
centrifuged to
recover solid catalyst, which was subsequently washed with methanol
repeatedly. Catalyst
was further washed with diethyl ether and dried under vacuum.
Example 447
lo Carbonylation of phenyl acetylene
Catalyst specifications:
Catalytic entity Pd(Ac)2(P(PhmSO3-)2(PySO3 )) (10" mols)
Additive (P(PhmSO3 )2(PySO3 ) 6* 10 mols/
polyvinyl sulfonic acid 100 mg
Support 5 g charcoal
Group IIA metal salt barium
Method of preparation deposition precipitation
Color of catalyst Black
Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
500 mg (4.90 10-3 mmol) phenyl acetylene and 5 mg p toluene sulfonic, acid 25
mg N, N,
dimethyl aniline and 10 ml methanol. Micro reactor was flushed with argon and
pressurized with carbon monoxide 100 psi and mixture was stirred at 90 C for
12 hours.
Reaction mixture was analyzed by gas chromatograph. 80 % phenyl acetylene was
carbonylated with 96 % selectivity for methyl dehydroatropate. Reaction
mixture was
centrifuged to recover solid catalyst, which was subsequently washed with
methanol
repeatedly. Catalyst was further washed with diethyl ether and dried under
vacuum.
Example 448
Hydrogenation of styrene
Catalyst specifications:
Catalytic entity RhC1COD(TPPTS)310 mols
Additive 10 mols of tppts/ 500 mg sodium carboxy
methyl cellulose
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Support kesilghur
Group IIA metal salt Strontium chloride saturated solution
Method of preparation Deposition precipitation
Color of catalyst Pale yellow
Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
500 mg (4.8 * 10"3 mmol) styrene in 10 ml ethanol. Micro reactor was flushed
with argon
and pressurized with hydrogen 500 psi and mixture was stirred at 90 C for 12
hours.
Reaction mixture was analyzed by gas chromatograph. 98 % styrene was
hydrogenated to
ethyl benzene. Reaction mixture was centrifuged to recover solid catalyst,
which was
subsequently washed with methanol repeatedly. Catalyst was further washed with
diethyl
ether and dried under vacuum. Catalyst was recycled to obtain equivalent
activity
Example 449
Hydrogenation of methyl cinnamate
Catalyst specifications:
Catalytic entity RhCICOD(TPPTS)310" mols
Additive 10" mols of tppts/ 500 mg sodium carboxy
methyl cellulose
Support kesilghur
Group IIA metal salt Strontium chloride saturated solution
Method of preparation Deposition precipitation
Color of catalyst Pale yellow
Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
500 mg (3.08 * 10"3 mmol) methyl cinnamate in 10 ml methanol. Micro reactor
was
flushed with argon and pressurized with hydrogen 1000 psi and mixture was
stirred at
50 C for 12 hours. Reaction mixture was analyzed by gas chromatograph. 80%
methyl
cinnamate was hydrogenated to methyl 3 phenyl propionate. Reaction mixture was
centrifuged to recover solid catalyst, which was subsequently washed with
methanol
repeatedly. Catalyst was further washed with diethyl ether and dried under
vacuum.
Catalyst was recycled to obtain equivalent activity.
Example 450
Hydrogenation of cinnamonitrile
Catalyst specifications:
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Catalytic entity RhC1COD(TPPTS)310" mols
Additive 10 mols of tppts/ 500 mg sodium carboxy
methyl cellulose
Support Kesilghur
Group IIA metal salt Strontium chloride saturated solution
Method of preparation Deposition precipitation
Color of catalyst Pale yellow
Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
500 mg (3.87 * 10-3 mmol) cinnamonitrile in 10 ml methanol. Micro reactor was
flushed
with argon and pressurized with hydrogen 500 psi and mixture was stirred at 50
C for 12
hours. Reaction mixture was analyzed by gas chromatograph. 79 % cinnamonitrile
was
hydrogenated with 60 % selectivity for 3-phenyl propionitrile. Reaction
mixture was
centrifuged to recover solid catalyst, which was subsequently washed with
methanol
repeatedly. Catalyst was further washed with diethyl ether and dried under
vacuum.
Catalyst was recycled to obtain equivalent activity.
Example 451
Hydrogenation of dehydronaproxen
Catalyst specifications:
Catalytic entity BINAPts RuCl2 10" mols
Additive BINAPts 10 mols/ 500 mg sodium
phosphate
Support Silica davisil lg
Group IIA metal salt Saturated solution of barium nitrate
Method of preparation Precipitation in coating pan
Color of catalyst Pale yellow
Procedure: 15 ml reactor with magnetic stirrer bar was charged with 200 mg
catalyst and
128 mg (1.26 * 10"3 mol) dehydro naproxen and 128 mg (1.26 * 10"3 mol)
triethyl amine
and 10 ml tolune: methanol (3:2 v/v). Micro reactor was flushed with argon and
pressurized with hydrogen 100 bar and mixture was stirred at 0 C for 48 hours.
Reaction
mixture was centrifuged to recover solid catalyst, which was subsequently
washed with
methanol repeatedly. All washings and reaction mixture were combined and dried
in
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vacuum. Solid thus obtained was thus dissolved in dichloromethane and washed
with
dilute HCl followed by water. Dichloromethane was evaporated to obtain
naproxen.
Analysis of products: products were analyzed by HPLC with WHELK-O column
(produced by Merck) yield of naproxen was 98 % and 92% e.e
Second recycle 98% and e.e. 94%
Example 452
Hydrogenation of heptaldehyde
Catalyst specifications:
Catalytic entity Ru(H)(Cl)(TPPTS)3 (10" mols)
Additive TPPTS (6 * 10 mols)/ 500 mg sodium alginate
Support Titania 5 g
Group IIA metal salt Strontium chloride saturated solution
Method of preparation coprecipitation
Color of catalyst Pale yellow
Procedure: 100 mg of the catalyst was charged in the microreactor to this 50
mg (4.38 *
10"4 mol) heptaldehyde was added as solution in 2 ml toluene. Microreactor was
flushed
with argon and heated to 90 C. Magnetic agitation was started. After
attaining temperature
reactor was pressurized with 500-psi hydrogen. The reactor was maintained
under these
conditions for 24 hours. Reaction was stopped by cooling reactor to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. 99 %
heptaldehyde was converted.
Catalyst was recovered by washing reactor with several portions of toluene
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with water,
methanol and diethyl ether and catalyst was dried under vacuum. This catalyst
was
recycled to obtain equivalent activity and selectivity. Catalyst was recycled
to obtain
equivalent conversion and selectivity.
Example 453
Hydrogenation of cinnamaldehyde
Catalyst specifications:
Catalytic entity Ru(H)2 (TPPTS)4 (10" mols)
Additive TPPTS (6 * 10 mols)/ 500 mg sodium alginate
Support Titania 5 g
Group IIA metal salt Strontium chloride saturated solution
Method of preparation coprecipitation
Color of catalyst Pale yellow
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Procedure: 100 mg of the catalyst was charged in the microreactor to this 500
mg (3.78
10"3 mol) cinnamaldehyde was added as solution in 2 ml tetrahydrofuran.
Microreactor was
flushed with argon and heated to 90 C. Magnetic agitation was started. After
attaining
temperature reactor was pressurized with 500-psi hydrogen. The reactor was
maintained
under these conditions for 24 hours. Reaction was stopped by cooling reactor
to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. 88 %
cinnamaldehyde was converted. Selectivity for cannamyl alcohol was 73 %.
Catalyst was recovered by washing reactor with several portions of
tetrahydrofuran
combined fractions were centrifuged to recover catalyst. Recovered catalyst
was washed
with water, methanol and diethyl ether and catalyst was dried under vacuum.
This catalyst
was recycled to obtain equivalent activity and selectivity. Catalyst was
recycled to obtain
equivalent conversion and selectivity.
Example 454
Hydrogenation of ethyl acetoacetate
Catalyst specifications:
Catalytic entity BINAPts RuC12 10 mols
Additive BINAPts 10 mols/ 500 mg sodium
phosphate
Support Silica davisil lg
Group IIA metal salt Saturated solution of barium nitrate
Method of preparation Precipitation in coating pan
Color of catalyst Pale yellow
Procedure: Procedure: lg of the catalyst was charged in the microreactor to
this 5g ethyl 3
oxobutanoate in 15 ml methanol. Resulting suspension was charged in
microreactor, which
was flushed with argon and hydrogen. Temperature of the reactor was raised to
90 C and
reactor was filled with hydrogen 150 psi. The reactor was maintained under
these
conditions for 24 hours. Reaction was stopped by cooling reactor to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. Ethyl
3 oxobutanoate was quantitatively converted to corresponding alcohol. Catalyst
was
recovered by washing reactor with several portions of methanol. Combined
fractions were
fractionated to recover catalyst. Recovered catalyst was washed with water,
methanol and
diethyl ether and catalyst was dried under vacuum. This catalyst was recycled
to obtain
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equivalent activity and selectivity. Catalyst was recycled to obtain
equivalent conversion
and selectivity.
Optical purity of product by fresh catalyst is 92 % and recycled catalyst is
94 %.
Example 455
Hydrogenation of benzyledene acetone
Catalyst specifications:
Catalytic entity Rh(C104 )(CODI)(TPPTS)3 (10-6 mols)
Additive TPPTS (6 * 10 mols)/ 500 mg sodium alginate
Support zirconia 5 g
Group IIA metal salt Strontium chloride saturated solution
Method of preparation coprecipitation
Color of catalyst Pale yellow
Procedure: Procedure: 100 mg of the catalyst was charged in the microreactor
to this 500
mg (3.42 * 10-3 mol) benzyledene acetone was added as solution in 2 ml
tetrahydrofuran.
Microreactor was flushed with argon and heated to 90 C. Magnetic agitation
was started.
After attaining temperature reactor was pressurized with 500-psi hydrogen. The
reactor
was maintained under these conditions for 24 hours. Reaction was stopped by
cooling
reactor to 0 C and depressurizing. Reactor was opened and liquid was analyzed
by gas
chromatograph. Total benzyledene acetone was converted. Catalyst was recovered
by
washing reactor with several portions of tetrahydrofuran combined fractions
were
centrifuged to recover catalyst. Recovered catalyst was washed with water,
methanol and
diethyl ether and catalyst was dried under vacuum. This catalyst was recycled
to obtain
equivalent activity and selectivity. Catalyst was recycled to obtain
equivalent conversion
and selectivity.
Example 456
Nitrotolune hydrogenation
Catalyst specifications:
Catalytic entity Ru(Cl)( Cl)(TPPTS)Z (10"6 mols)
Additive TPPTS (6 * 10 mols)/ 500 mg sodium alginate
Support Titania 5 g
Group IIA metal salt Strontium chloride saturated solution
Method of preparation coprecipitation
Color of catalyst Pale yellow
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Procedure: 100 mg of the catalyst was charged in the microreactor to this 500
mg (3.649 *
10-3 mol) o-nitro toluene was added as solution in 2 ml ethyl acetate.
Microreactor was
flushed with argon and heated to 90 C, magnetic agitation was started. After
attaining
temperature reactor was pressurized with 500-psi hydrogen. The reactor was
maintained
under these conditions for 24 hours. Reaction was stopped by cooling reactor
to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. Total
o-Nitrotolune was converted to o toludene.
Catalyst was recovered by washing reactor with several portions of ethyl
acetate combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with water,
methanol and diethyl ether and catalyst was dried under vacuum. This catalyst
was
recycled to obtain equivalent activity and selectivity. Catalyst was recycled
to obtain
equivalent conversion and selectivity.
Example 457
Hydrogenation o-chloro nitro benzene
Catalyst specifications:
Catalytic entity Ru(Cl)( Cl)(TPPTS)2 (10-6 mols)
Additive TPPTS (6 * 10 mols)/ 500 mg sodium
alginate
Support Titania 5 g
Group IIA metal salt Strontium chloride saturated solution
Method of preparation Coprecipitation
Color of catalyst Pale yellow
Procedure: 100 mg of the catalyst was charged in the microreactor to this 500
mg (3.952 *
10-3 mol) o-chloro nitrobenzene was added as solution in 2 ml ethyl acetate.
Microreactor
was flushed with argon and heated to 90 C. Magnetic agitation was started.
After attaining
temperature reactor was pressurized with 500-psi hydrogen. The reactor was
maintained
under these conditions for 24 hours. Reaction was stopped by cooling reactor
to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. Total
o-chloro nitrobenzene was converted to o chloro aniline.
Catalyst was recovered by washing reactor with several portions of ethyl
acetate combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with water,
methanol and diethyl ether and catalyst was dried under vacuum. This catalyst
was
recycled to obtain equivalent activity and selectivity. Catalyst was recycled
to obtain
equivalent conversion and selectivity.
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Example 458
Iodobenzene and methyl acrylate
Catalyst specifications:
Catalytic entity Pd (P(PhõiSO3 )3)3 (10" mols)
Additive P(PhrõSO3 )3 (4 * 10" mols)
Support Charcoal 1 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Deposition precipitation
Color of catalyst Black
Procedure: procedure: procedure: procedure: 100 mg of the catalyst was charged
in the
microreactor to this 1 mg tetrabutyl ammonium hydroxide, 0.41 mg (5 * 10"3 )
sodium
acetate 0.5 g (5 * 10"3) ethyl acrylate and 0.509 g (2.5 * 10"3) iodobenzene
was added as
solution in 5 ml toluene. Microreactor was flushed with argon and heated to 90
C,
magnetic agitation was started after attaining temperature. The reactor was
maintained
under these conditions for 48 hours. Reaction was stopped by cooling reactor
to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. 86 %
ethyl acrylate was converted to products. Catalyst was recovered by washing
reactor with
several portions of toluene combined fractions were centrifuged to recover
catalyst.
Recovered catalyst was washed with water, methanol and diethyl ether and
catalyst was
dried under vacuum. This catalyst was recycled to obtain equivalent activity
and
selectivity. Catalyst was recycled to obtain equivalent conversion and
selectivity.
Observation color of the recovered catalyst was dark yellow.
Example 459
lodobenzene and acrylonitrile
Catalyst specifications:
Catalytic entity Pd (P(Ph,,,SO3 )3)3 (10" mols)
Additive P(Ph,,,SO3-)3 (4 * 10" mols)
Support Charcoal 1 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Deposition precipitation
Color of catalyst Black
Procedure: procedure: procedure: procedure: 100 mg of the catalyst was charged
in the
microreactor to this 1 mg tetrabutyl ammonium hydroxide, 0.41 g sodium
acetate, 0.265 g
(5 * 10-3) acrylonitrile and 0.509 g(2.5 * 10'3) iodobenzene was added as a
solution in 5
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ml toluene. Microreactor was flushed with argon and heated to 90 C. Magnetic
agitation
was started after attaining temperature. The reactor was maintained under
these conditions
for 48 hours. Reaction was stopped by cooling reactor to 0 C and
depressurizing. Reactor
was opened and liquid was analyzed by gas chromatograph. 90 % acrylonitrile
was
converted to products.
Catalyst was recovered by washing reactor with several portions of toluene
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with water,
methanol and diethyl ether and catalyst was dried under vacuum. This catalyst
was
recycled to obtain equivalent activity and selectivity. Catalyst was recycled
to obtain
equivalent conversion and selectivity.
Observation color of the recovered catalyst was dark yellow.
Example 460
Iodobenzene and styrene
Catalyst specifications:
Catalytic entity Pd (P(Ph,T,SO3 )3)3 (10 mols)
Additive P(PhmSO3')3 (4 * 10 mols)
Support Charcoal 1 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Deposition precipitation
Color of catalyst Black
Procedure: Ig of the catalyst was charged in the microreactor to this 5 mg
tetrabutyl
ammonium hydroxide, 0.66 mg potassium carbonate 0.5g (4.8 * 10"3 mol) styrene
and
1.957 g (9.6 * 10-3 mol) iodobenzene was added as solution in 10 ml toluene.
Microreactor
was flushed with argon and heated to 90 C. Magnetic agitation was started
after attaining
temperature. The reactor was maintained under these conditions for 76 hours.
Reaction was
stopped by cooling reactor to 0 C. Reactor was opened and liquid was analyzed
by gas
chromatograph. 44 % styrene was converted to stilbene.
Catalyst was recovered by washing reactor with several portions of toluene
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with water,
methanol and diethyl ether and catalyst was dried under vacuum. This catalyst
was
recycled to obtain equivalent activity and selectivity. Catalyst was recycled
to obtain
equivalent conversion and selectivity.
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Example 461
Iodobenzene and ethylene
Catalyst specifications:
Catalytic entity Pd (Ac)a(P(o Me-PhmSO3")3)2 (10 mols)
Additive (P(o Me-Ph,,,SO3 )3)Z (4 * 10" mols)
Support Charcoal 1 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Deposition precipitation
Color of catalyst Black
Procedure: 100 mg of the catalyst was charged in the microreactor to this 1 mg
tetrabutyl
ammonium hydroxide, 0.41 g sodium acetate and 0.509 g (2.5 * 10"3) iodobenzene
was
added as solution in 10 ml acetonitrile. Microreactor was flushed with
nitrogen and heated
to 120 C. Reactor was pressurized with ethylene and magnetic agitation was
started. The
reactor was maintained under these conditions for 76 hours. Reaction was
stopped by
cooling reactor to 0 C. Reactor was depressurized by venting gas in the
reactor. Reactor
was opened and liquid was analyzed by gas chromatograph. 30 % iodobenzene was
converted to styrene.
Catalyst was recovered by washing reactor with several portions of toluene
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with water,
methanol and diethyl ether and catalyst was dried under vacuum. This catalyst
was
recycled to obtain equivalent activity and selectivity. Catalyst was recycled
to obtain
equivalent conversion and selectivity.
Example 462
Bromo benzene and o tolyl boronic acid
Catalyst specifications:
Catalytic entity Pd (P(PhmSO3")3)3 (10" mols)
Additive P(PhmSO3-)3 (4 * 10 mols)
Support Charcoal 1 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Deposition precipitation
Color of catalyst Black
Procedure: Thoroughly dried 500-m1 flask was equipped with thermometer,
magnetic
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stirrer bar, condenser, addition funnel and two-way valve. To the flask was
placed 12.2 g
(0.5 atom) of magnesium turnings. Assembly was thoroughly evacuated through
two-way
valve and nitrogen was filled and magnesium was stirred for 6 hours. To this
was added a
crystal of iodine, 100 ml of tetrahydrofuran distilled over sodium
benzophenone ketyl and
200 l of 1,2 dibromoethane. After surface of magnesium turns shiny white 78.5-
g (0.5
mol) bromobenzene was added with such a rate that temperature raises to
boiling. Reaction
was continued with intermittent cooling of the flask by removing heater-
stirrer. Once
r
reaction subsides mixture was refluxed until magnesium was dissolved. Reaction
mixture
was transferred to Shlenk tube plugged with glass wool.
m-tolyl boronic acid
To a thoroughly dried flanged flask attached with sealed mechanical stuffing
box
and a dropping funnel and reflux condenser attached with fused calcium
chloride guard
tubes was assembled. Temperature of the flask was brought to -75 C with
acetone and
liquid nitrogen. To the flask was added 40.5 g of tributyl borate in 150-ml
ether. With
fairly rapid stirring add solution of o tolyl magnesium bromide without
letting temperature
to rise above -70 C continue stirring for three hours at same temperature.
Temperature of
the flask was maintained to 5 C with ice bath for 12 hours. This reaction
mixture was
added to chilled 10 % sulfuric acid 150 ml. Extract with ether and evaporated
to this was
added 100 ml water and basified with NaOH to slightly alkaline. Acidify and
extract with
boiling water and collected as crystalline material (5 g).
1g of the catalyst was charged in the round-bottomed flask attached to reflux
condenser, magnetic bar was added to round bottomed flask. To this 1-mg
tetrabutyl
ammonium hydroxide, 75 mg. sodium carbonate, 0.136-g (10-3 mols) o- tolyl
boronic acid
and 0.224 g(1.1 * 10-3) iodobenzene was added as solution in 20m1 toluene.
Assembly was
flushed with nitrogen and heated to 90 C. The reactor was maintained under
these
conditions for 24 hours. Reaction was stopped by cooling reactor to 0 C.
Liquid was
analyzed by gas chromatograph. 95 % iodobenzene was converted to 2 methyl 1,
1'
biphenyl.
Catalyst was recovered by washing reactor with several portions of toluene
combined fractions were centrifuged to recover catalyst. Recovered catalyst
was washed
with sodium carbonate, water, methanol and diethyl ether and catalyst was
dried under
vacuum. This catalyst was recycled to obtain equivalent activity and
selectivity. Catalyst
was recycled to obtain equivalent conversion and selectivity.
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Example 463
Phenyl magnesium bromide and iodobenzene
Catalyst specifications:
Catalytic entity NiC12.dppe ts (5 * 10 atom of nickel)
Additive Dppe 0.806 mg
Support Silica davisil
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Fluid'ized bed
Color of catalyst Pale blue
Moisture content Not detectable by Karl Fischer
Procedure:
Preparation of Grignard reagent
Thoroughly dried 500-m1 flask was equipped with thermometer, magnetic stirrer
bar, condenser, addition funnel and two-way valve. To the flask was placed
0.61 g (0.025
atom) g of magnesium turnings. Assembly was thoroughly evacuated through two-
way
valve and nitrogen was filled and magnesium was stirred for 6 hours. To this
was added a
crystal of iodine, 50 ml of tetrahydrofuran distilled over sodium benzophenone
ketyl and
200 l of 1,2 dibromoethane. After surface of magnesium turns shiny white
3.922-g (0.025
mol) bromobenzene in 20-m1 thf was added with such a rate that temperature
raises to
boiling. Reaction was continued with intermittent cooling of the flask by
removing heater-
stirrer. Once reaction subsides mixture was refluxed until magnesium was
dissolved.
Reaction mixture was transferred to Shlenk tube plugged with glass wool.
Thoroughly dried 250 ml flask was equipped with thermometer, magnetic stirrer
bar, condenser, addition funnel and two way valve was charged with 5 g of
catalyst, 50 ml
tetrahydrofuran freshly distilled over sodium benzophenone ketyl of blue
color. Assembly
was filled with nitrogen as described earlier. To this was added 5.09g (0.025
mol of
iodobenzene) 60 ml Grignard reagent as prepared previously was charged in
addition
vessel. Grignard reagent was slowly added to contents of the flask which was
previously
cooled to 5 C. Temperature of the flask was maintained at 5 C for 24 h.
Reaction mixture
was cooled to room temperature to which was slowly added 20 ml water followed
by
saturated 20 ml ammonium chloride. Resulting suspension was fluttered to
remove solids
and subsequently washed thoroughly with tetrahydrofuran and water. Filtrates
were
extracted with dichloromethane to obtain biphenyl in 89 % yield residue left
after filtration
was washed with water, tetrahydrofuran and ether and dried under vacuum.
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Example 464
Isobutyl magnesium bromide and iodobenzene
Preparation of catalysts: catalyst was previously dried by extraction with
boiling THF over
sodium wire followed by vaccume and stored over phosphorus pentoxide catalyst
specifications:
Catalytic entity NiC12.dppe ts (5 * 10 atom of nickel)
Additive Dppe 0.806 mg
Support Silica davisil 5 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Fluidized bed
Color of catalyst Pale blue
Moisture content Not detectable by Karl Fischer
Procedure: preparation of Grignard reagent
Thoroughly dried 500-ml flask was equipped with thermometer, magnetic stirrer
bar,
condenser, addition funnel and two-way valve. To the flask was placed 2.44 g
(0.1 atom)
of magnesium turnings. Assembly was thoroughly evacuated through two-way valve
and
nitrogen was filled and magnesium was stirred for 6 hours. To this was added a
crystal of
iodine, 50 ml of tetrahydrofuran distilled over sodium benzophenone ketyl and
200 l of
1,2 dibromoethane. After surface of magnesium turns shiny white 9.2-g (0.1
mol) isobutyl
bromide was added with such a rate that temperature raises to boiling.
Reaction was
continued with intermittent cooling of the flask by removing heater-stirrer.
Once reaction
subsides mixture was refluxed until magnesium was dissolved. Reaction mixture
was
transferred to Shlenk tube using canula plugged with glass wool.,
Thoroughly dried 500 ml flask was equipped with thermometer, magnetic stirrer
bar, condenser, addition funnel and two way valve was charged with 5 g of
catalyst, 50-ml
tetrahydrofuran freshly distilled over sodium benzophenone ketyl of blue
color. Assembly
was filled with nitrogen as described earlier. To this was added 20.39 g (0.1
mol of
iodobenzene) 50 ml Grignard reagent as prepared previously was charged in
addition
vessel. Grignard reagent was slowly added to contents of the flask which were
cooled to
0 C. Temperature of the flask was raised to 50-OC temperatures. Reaction
mixture was
cooled to room temperature to, which was slowly added 25-m1 water followed by
25 ml
saturated ammonium chloride. Resulting suspension was filtered to remove
solids and
subsequently washed thoroughly with tetrahydrofuran and water. Filtrates were
extracted
with dichloromethane to obtain isobutyl benzene in 92 % yield residue left
after filtration
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was washed with water, thf and ether and dried under vacuum.
Example 465
Allylation of aryl boronates
Catalyst specifications:
Catalytic entity NiC12.(tppts)2 (96.5 rng(10-4 mols)
Additive tppts(83.6 mg(2 * 10- mols)
Support Silica davisil 2 g
Group IIA metal salt Barium nitrate saturated solution
Method of preparation Fluidized bed
Color of catalyst White with blue ting
Moisture content Not detectable by Karl Fischer
Procedure: to a 2 gm of catalyst was added 20 ml of tetrahydrofuran, to this
solution was
added 5 ml of cold solution containing 2.9 mmol of phenyl lithium. The mixture
was
cooled to 0 C under stirring and to this 0.42 ml (3.62 mmol) B(OCH3)3 was
slowly added
followed by 1.44 mmol allyl methyl carbonate. Temperature was then raised to
60 C and
reaction was continued for 12 hours. Liquid was separated from solid catalyst
and poured
in to mixture of 20 ml hexane and 20 ml of saturated ammonium chloride.
Organic layer
indicated formation of 3-phenyl propene.
Recovered catalyst was washed with saturated bicarbonate, tetrahydrofuran and
diethyl
ether and recycled after drying in vaccume
Example 466
Hexene isomarization
Catalyst specifications:
Catalytic entity Rh+(C1O4 )(tppts)3
Additive tppts
Support silica
Group IIA metal salt Saturated barium nitrate solution
Method of preparation Deposition precipitation
Color of catalyst Pale yellow
Procedure: Isomarization was carried out according following procedure. 5 gm
of catalyst
was charged in microreactor, which was subsequently flushed with nitrogen and
charged
with degassed mixture of 5 g 1-hexene (92 % purity), and 45-m1 cyclohexane.
Temperature
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of the reactor was raised to 100 C and maintained for 76 hours. Conversion of
I hexene
was 73 %. And two isomarized products were observed. Catalyst was centrifuged
and
liquid was separated. Catalyst was repeatedly washed by cyclohexane. Isolated
catalyst
was recycled under identical conditions to provide equivalent yields.
Example 467
N, N - Diethylneryl amine isomarization
Catalyst specifications:
Catalytic entity Rh(C1O4 )(binapts)3 (10-6 mol)
Additive Binapts (5 * 10-6 mol)
Support Silica 2g
Group IIA metal salt Saturated barium nitrate solution
Method of preparation Deposition precipitation
Color of catalyst Pale yellow
Procedure: catalyst drying
Isomarization was carried out as per procedure adopted from (Helvetica Chemica
Acta
vol.71, (1988) 897-920) modified to suit solid catalyst. 2 gm of catalyst was
charged in
Fischer-porter bottle and evacuated. Bottle was subsequently flushed with
nitrogen and
charged with degassed mixture of 11.37 g (50 mmol) (purity by area % on gc 92)
N, N -
Diethylneryl amine and 50 ml dry tetrahydrofuran. Temperature of the bottle
was raised to
80 C and maintained for 76 hours. Catalyst was centrifuged and liquid was
separated.
Repeated washings of catalyst by tetrahydrofuran were combined and evaporated
to obtain
pale yellow oil which was dissolved in 50 % acetic acid in water 50 ml at 0 C
stirred for 10
min and 50 ml hexane was added and liquid was stirred for 30 min at ambient
temperature.
Hexane layer was separated and aqueous layer was washed with hexane hexane
extract
was washed with sat bicarbonate solution. Fractionation of extract provided
7.35 g(S)
citronellol 90 % based on N, N - Diethylneryl amine. Optical purity of this
material found
by polarimetry c= 5, CHC13, lamp D at 20 C was 98 %, isolated catalyst was
recycled
under identical conditions to provide equivalent yields.
Example 468
1,4-diacetoxy butene isomarization
Catalyst specifications:
Catalytic entity C1O4 Rh+[P(PhmSO3 )313 (10 )
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Additive P(PhmSO3")3 (6 * 10 )
Support Bentonite 5 g
Group IIA metal salt Strontium chloride
Method of preparation Deposition precipitation in coating pan
Color of catalyst Pale yellow
Metal content
Procedure: isomarization was carried out according following procedure. 100 mg
of
catalyst was charged in microreactor which was subsequently flushed with
nitrogen and
charged with degassed mixture of 50 mg (3 * 10 "4mo1) 1,4-diacetoxy butene and
2 ml
toluene. Temperature of the reactor was raised to 100 C and maintained for 76
hours.
Catalyst was centrifuged and liquid was separated. Repeated washings of
catalyst by
toluene. Conversion of 1,4-diacetoxy butene was 57 %. Isolated catalyst was
recycled
under identical conditions to provide equivalent yields.
Example 469
Hexene wacker
Catalyst specifications:
Palladium acetate/bypyridyldisulfonate 22.4.mg :55 mg
bypyridyldisulfonate 218.4 mg(0.4 mmol)
Support Bentonite 2 gm
Group IIA metal salt Strontium chloride
Method of preparation Deposition precipitation by azeotropic
removal of water
Color of catalyst Light yellow orange
Metal content 0.46 miliatoms pre gm
Procedure: 100 mg of the catalyst was charged in the microreactor to this 1 ml
hexene was
added as 20 % v/v solution in hexane. Microreactor was pressurized with air
(450 psi) and
heated to 90 C. Magnetic agitation was started after attaining temperature.
The reactor was
maintained for 24 hours. Reaction was stopped by cooling reactor to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. 36%
cyclohexene was converted to products with 90 % selectivity for hexane 2 one.
Remainder
products were estimated to be isomarized olefins and some unidentified
products.
Catalyst was recovered by washing reactor with several portions of cyclohexane
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was
fortified with water
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to contain 50 % water by weight. This catalyst was recycled to obtain
equivalent activity
and selectivity.
Observation color of the recovered catalyst was dark yellow.
Example 470
Decene wacker
Catalyst specifications:
Palladium acetate/bypyridyldisulfonate 22.4.mg :55 mg
bypyridyldisulfonate 218.4 mg( 0.4 mmol)
Support Bentonite 2 gm
Group I.IA metal salt Strontium chloride
Method of preparation Deposition precipitation by azeotropic
removal of water
Color of catalyst Light yellow orange
Metal content 0.46 miliatoms pre gm
Procedure: procedure: 100 mg of the catalyst was charged in the microreactor
to this 1 ml
decene was added as 20 % solution in hexene. Microreactor was pressurized with
air (450
psi) and heated to 90 C. Magnetic agitation was started after attaining
temperature. The
reactor was maintained for 24 hours. Reaction was stopped by cooling reactor
to 0 C and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. 19 %
decene was converted to products with 87% selectivity for decane 2 one.
Remainder
products were estimated to be isomarized olefins and some unidentified
products.
Catalyst was recovered by washing reactor with several portions of cyclohexane
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was
fortified with water
to contain 50 % water by weight. This catalyst was recycled to obtain
equivalent activity
and selectivity.
Observation color of the recovered catalyst was dark yellow.
Example 471
Cyclohexene wacker
Catalyst specifications:
Palladium acetate/bypyridyldisulfonate 22.4.mg :55 mg
bypyridyldisulfonate 218.4 mg(0.4 mmol)-
Support Bentonite 2 gm
Group IIA metal salt Strontium chloride
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Method of preparation Deposition precipitation by azeotropic
removal of water
Color of catalyst Light yellow orange
Metal content 0.46 miliatoms per gm
Procedure: 100 mg of the catalyst was charged in the microreactor to this 1 ml
cyclohexene
was added as 20 % solution in hexene. Microreactor was pressurized with air
(450 psi) and
heated to 90 C. Magnetic agitation was started after attaining temperature.
The reactor
was maintained for 24 hours. Reaction was stopped by cooling reactor to 0 C
and
depressurizing. Reactor was opened and liquid was analyzed by gas
chromatograph. 7%
cyclohexene was converted to products with 30 % selectivity for cyclohexanone.
Remainder products were not estimated.
Catalyst was recovered by washing reactor with several portions of cyclohexane
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was
fortified with water
to contain 50 % water by weight. This catalyst was recycled to obtain
equivalent activity
and selectivity.
Observation color of the recovered catalyst was dark yellow.
Example 472
Styrene epoxidation
Preparation of catalysts: Ph(CH2)-N+(Ph11SO3 )3 .OH- was heterogenized as
described
according method described earlier as deposition precipitation in coating pan.
Solid was
suspended in water to which three mole equivalent of OH" present (estimated by
titration
with standard acid) suspension was stirred for 4 hours at 70 C. Solid was
recovered and
extracted with water for 12 hours followed by drying in vacuum.
Catalyst specifications:
Catalytic entity Ph(CH2)-N+(Ph11SO3 )3 . -2 (1 mili eq
of M04 2)
additive Sodium meta silicate 1 gm
Support keisulghur 5 gm
Group IIA metal salt Barium hydroxide saturated solution in
water.
Method of preparation Deposition precipitation in coating pan
Moisture content 20 % by weight.
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Procedure: 5 g of the catalyst was charged in the 500 ml glass reaction vessel
equipped
with mechanical stirrer, thermometer pocket and addition vessel, to this 30 g
(0.29 mol)
styrene in 75 ml acetic acid was added. Reaction vessel was cooled to 5 C with
circulating
fluid cryostat. Agitation was started after attaining temperature. 30m1 34 %
hydrogen
peroxide was added over the period of 30 min. temperature and agitation of the
reaction
vessel was maintained for 24 hours. Reactor was opened and liquid was analyzed
by gas
chromatograph. 72% styrene was converted to products with 89 % selectivity for
styrene
oxide. Remainder products were not estimated.
Catalyst was recovered by washing reactor with several portions of acetic acid
combined
fractions were centrifuged to recover catalyst. Recovered catalyst was washed
with
methanol, ether and dried. This catalyst was recycled to obtain equivalent
activity and
selectivity.
Example 473
Chlorophenol oxidation
Preparation of catalysts: catalyst was prepared according to method described
as
precipitation in fluidized bed.
Catalyst specifications:
Catalytic entity Iron(III) pthalocynine-4,4',4",4"'-
tetrasulfonic acid tetrasodium salt as
compound with oxygen 30.2 mg (3 * 10'3
mols)
Additive Sodium silicate 500 mg
Support Fullers earth 2g
Group lIA metal salt Barium nitrate saturated solution in water
Method of preparation Fluidized bed drier
Color of catalyst Pale blue
Moisture content 10 % by weight
Procedure: to a 50 ml round bottomed flask attached with a reflux condenser
was added 5
ml acetonitrile and 15 ml 0.1 M acetate buffer of pH 7 to which was added 181
mg (10-3
mols) of trichloro phenol. 2.5g catalyst was added and suspension was stirred
with
magnetic needle. Temperature of the suspension was raised to 60 C. To this
0.3 ml 34%
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H202 in water was added to above suspension. The reaction mixture was
continued for 5
hours. Total disappearance of trichlorophenol was observed and chloride ions
were
detected in solution with silver nitrate solution.
Example 474
Condensation of diethylfumarate and diethylmalonate to propane-1,1,2,3
tetracarboxylate
Catalyst specifications:
Catalytic entity Ph(CH2)-N+(PhmSO3 )3 . EtO- (1 milieq of
EtO-)
additive Sodium meta silicate 1 gm
Support Charcoal 5 gm
Group IIA metal salt Barium hydroxide
Method of preparation Deposition precipitation
Procedure: in a 100-ml flask fitted with an efficient reflux condenser,
magnetic stirrer bar
and dropping funnel was charged 5 gm of catalyst. With stirring 1.6 g (0.001
mol)
diethylmalonate and 25 ml dry ethanol was added. Reaction mixture was warnzed
and 1.4
gm (0.0081 mol) diethyl fumarate was added. Mixture was refluxed for 8 hours.
Reaction
mixture was cooled and suspension was centrifuged to recover catalyst.
Analysis of
reaction liquid indicated 90 % conversion for diethylmalonate. Product was
distilled under
vacuum 8 mm at 180-190 C to obtain propane-1,1,2,3 tetracarboxylate 85% yield.
Catalyst was recovered and washed with ethanol, diethyl ether and dried under
vacuum.
Catalyst was recycled to obtain equivalent activity.
Example 475
Diethymalonate and formaldehyde condensation to tetraethylpropane-1,1,3,3-
tetracarboxylate
Catalyst specifications:
Catalytic entity Ph(CH2)-N+(Ph,,,SO3')3 . HO" (1 milieq of
HO')
additive Sodium meta silicate 1 gm
Support Charcoal 5 gm
Group IIA metal salt Barium hydroxide
Method of preparation Deposition precipitation
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Procedure: mixture of 1.6 g(0.001 mol) of distilled diethyl malonate, 25 ml
ethanol and
0.4 g (5 * 10 "4 mol) of 40 % formaldehyde contained in 50 ml round bottomed
flask was
cooled to 0 C and 5 gm of catalyst was added and mixture was stirred at room
temperature
for 24 hours and then refluxed for 12 hours. Suspension was centrifuged to
recover
catalyst. Analysis of reaction liquid indicated 80 % conversion of diethyl
malonate. Liquid
was evaporated and extracted with diethyl ether. Extract was dried with sodium
sulfate.
Catalyst was washed with ethanol, diethyl ether and dried under vaccume.
Catalyst was
recycled to obtain equivalent activity.
Example 476
Condensation of acetone and chlorofonn to chlorbutol
Catalyst specifications:
Catalytic entity Ph(CH2)-N}(PhmSO3-)3 . OH" (1 milieq of
OIT) 0.659 mg
additive Sodium meta silicate 1 gm
Support Charcoal 5 gm
Group IIA metal salt Barium hydroxide
Method of preparation Deposition precipitation
Procedure: 100 ml round bottomed flask equipped with reflux condenser was
charged with
5 gm of catalyst to which solution of 1.19 g (0.01 mol) chloroform was charged
as solution
in 25 ml solution in acetone. Magnetic stirrer bar was added in the reaction
mixture
reaction mixture was stirred at ambient temperature for 24 hours. Suspension
was
centrifuged to recover catalyst. Analysis of reaction liquid indicated total
conversion of
chloroform. Catalyst was washed with ethanol, diethyl ether and dried under
vacuum.
Catalyst was recycled to obtain equivalent activity.
Example 477
Condensation of benzaldehyde and acetonitrile to cinnamonitrile.
Catalyst specifications:
Catalytic entity Ph(CH2)-N+(CH2PhmS03 )3 . Off (1 milieq
of Off) 0.701 mg
Additive Sodium meta silicate 1 gm
Support Charcoal 5 gm
Group IIA metal salt Barium hydroxide
Method of preparation Deposition precipitation
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Procedure: 250 ml round bottomed flask equipped with reflux condenser was
charged with
gm of catalyst to which solution of 10.6 g (0.1 mol) benzaldehyde was charged
as
solution in 100 ml solution in acetonitrile. Magnetic stirrer bar was added in
the reaction
mixture reaction mixture was stirred at reflux temperature for 24 hours.
Suspension was
5 centrifuged to recover catalyst. Analysis of reaction liquid indicated 88 %
conversion of
benzaldehyde and 98 % selectivity for cinnamonitrile. Cinnamonitrile was
recovered by
fractional distillation 80 % based on benzaldehyde
Catalyst was washed with ethanol, diethyl ether and dried under vacuum.
Catalyst was
recycled to obtain equivalent activity.
Example 478
Condensation of benzaldehyde and acetone to benzayledene acetone
Catalyst specifications:
Catalytic entity Ph(CH2)-N (CH2Ph11SO3-)3 OH- (1 milieq
of OH-) 0.701 mg
additive Sodium meta silicate 1 gm
Support Charcoal 5 gm
Group IIA metal salt Barium hydroxide
Method of preparation Deposition precipitation
Procedure: 250 ml round bottomed flask equipped with reflux condenser was
charged with
5 gm of catalyst to which solution of 10.6 g (0.1 mmol) benzaldehyde was
charged as
solution in 100 ml solution in acetone. Magnetic stirrer bar was added in the
reaction
mixture reaction mixture was stirred at ambient temperature for 24 hours.
Suspension was
centrifuged to recover catalyst. Analysis of reaction liquid indicated 77 %
conversion
benzaldehyde. Catalyst was washed with ethanol, diethyl ether and dried under
vaccume.
Catalyst was recycled to obtain equivalent activity.
Example 479
Condensation of butaraldehyde to 2ethyl hexenal
Catalyst specifications:
Catalytic entity Ph(CH2)-N+(Ph,,,SO3 )3 . OI-r (1 milieq of OH')
0.659 mg
Additive Sodium meta silicate 1 gm
Support Charcoal 5 gm
Group IIA metal salt Barium hydroxide
Method of preparation Deposition precipitation
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Procedure: 100 ml round bottomed flask equipped with reflux condenser was
charged with
gm of catalyst to which solution of 7.2 g (0.1 mmol) butaraldehyde was charged
as
solution in 50 ml solution in toluene. Magnetic stirrer bar was added in the
reaction
mixture reaction mixture was refluxed for 24 hours. Suspension was centrifuged
to recover
5 catalyst. Analysis of reaction liquid indicated 90 % conversion of
butaraldehyde. Catalyst
was washed with ethanol, diethyl ether and dried under vacuum. Catalyst was
recycled to
obtain equivalent activity.
Example 480
Iodobenzene phosphination catalyst specifications:
Catalytic entity NiC12.(bisdiphenylphosphinoethane
tetrasulfonate) [1 miliatom of nickel]
Additive bisdiphenylphosphinoethane tetrasulfonate
1 gm.
support y- alumina 5 gm
Cured with Barium nitrate
Method of preparation Deposition precipitation in coating pan
Color of catalyst Pale yellow
Metal content of prepared catalyst 0.93 miliatom of nickel
Procedure: round bottomed flask equipped with reflux condenser was charged
with
catalyst 5 gm. To this solution of diphenyl phosphine 1 ml (5.75 mmol) in 30
ml dry
degassed dimethylformamide was added at room temperature. Suspension was
degassed
with repetitive vaccume and argon flushing. After heating to 100 C for 30
min. 10 mmol
(2.04 gm.) iodobenzene and 20 mmol (2.25 gm) diazabicyclooctane in 30 ml
dimethylformamide was added and resulting solution was maintained at 100 C.
Three
additional portions of 1-ml diphenyl phosphine each were added at 12-hour
interval
thereafter. Reaction was continued for.76 hours. Reaction was stopped by
cooling flask to
room temperature. Catalyst was recovered by centrifugation and washed by
dimethylformamide. Filtrates were combined and evaporated to obtain sticky
residue,
which was diluted with 50-m1 tetrahydrofuran. Solution was analyzed with 31 P
NMR.
Following compounds were detected triphenylphosphine, triphenylphosphine
oxide,
diphenylphosphine and diphenylphosphineoxide.
Yield of triphenylphosphine based on iodobenzene was 92%; conversion of
iodobenzene
was complete as confirmed by gas chromatography.
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Observation color of recovered catalyst is darker than fresh catalyst.
Catalyst recovery and recycle: The recovered catalyst was recycled under
identical
conditions to obtain 88% triphenylphosphine based on iodobenzene. For third
recycle
catalyst was refluxed with 250 mg NiC12.6H20 dissolved in 50% ethanol in water
for 6
hours. Catalyst was extracted with water, ethanol and dried. This catalyst was
recycled to
obtain 90% triphenylphosphine
Fresh catalyst under identical conditions in cyclohexane as solvent does not
indicate
leaching of nickel but yield of triphenyl phosphine was about 10% after 76
hours.
Example 481
Bromoanisol phosphination
Catalyst preparation: catalyst was prepared according to method described as
deposition
precipitation in coating pan
Catalyst specifications:
Catalytic entity PdAcz.(bisdiphenylphosphinoethane
tetrasulfonate) [1 miliatom of palladium]
Additive bisdiphenylphosphinoethane tetrasulfonate
1 gm.
support Gamma alumina 5 gm
Cured with Barium nitrate
Method of preparation Deposition precipitation in coating pan
Color of catalyst Pale yellow
Metal content of prepared catalyst 0.93 miliatom of palladium
Procedure: round bottomed flask equipped with reflux condenser was charged
with catalyst
5 gm. To this solution of diphenyl phosphine 1 ml (5.75 mmol) in 30-m1 dry
degassed
dimethylformamide was added at room temperature. Suspension was degassed with
repetitive vaccume and argon flushing. After heating to 100 C for 30 min. 10
mmol (1.87
gm.) 2- bromoanisol and 20 mmol (2.25 gm) diazabicyclooctane in 30 ml
dimethylformamide was added and resulting solution was maintained at 100 C.
Three
additional portions of 1-ml diphenyl phosphine each were added at 12-hour
interval
thereafter. Reaction was continued for 76 hours. Reaction was stopped by
cooling flask to
room temperature. Catalyst was recovered by centrifugation and washed by
dimethylformamide. Filtrates were combined and evaporated to obtain sticky
residue,
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which was diluted with 50-m1 tetrahydrofuran. Solution was analyzed with 31P
NMR as
described in previous example. 83 % conversion of 2 bromoanisol was observed.
Quantitative estimation of phosphines was not determined.
Example 482
Duteriation of C6H6 to C6 D6
Catalyst specifications
Catalytic entity Diphenyl phosphinoethane tetrasulphonate
/ RuC12COD 15 mg
Additive Diphenyl phosphinoethane tetrasulphonate
25 mg / sodium phosphate50 mg
Support Bentonite 500 mg
Cured with Saturated strontium chloride solution in
water
Method of preparation Fluidized bed
Color of catalyst Pale yellow
Catalyst pretreatment: catalyst was refluxed twice with 3-ml deuterium oxide
recovered
with centrifugation and dried under vaccume. This was essential to remove
protons on the
solid support.
Procedure: 100 mg of the catalyst was charged in the microreactor equipped
with external
magnetic stirrer 0.01mol (0.78 g) benzene in 2 ml and deuterium oxide was
added.
Reaction vessel was heated to 110 C with external heating. Agitation was
started after
attaining temperature. Reactor was maintained at these conditions for 24
hours. Reactor
was cooled to -5 C liquids were recovered and organic liquid was analyzed by
NMR 88 %
labeling of deuterium using chloroform as internal standard.
Catalyst was recovered by centrifugation and recovered catalyst was dried
under vacuum.
This catalyst was recycled to obtain equivalent activity and selectivity.
While invention has been particularly shown and described with respect to
preferred embodiments thereof, it will be understood by those skilled in the
art that the
forgoing and the other changes in form and detail may be made without
departing from the
spirit and scope of the invention.
