. ~ ~ ~~.~~4Q9
WO 94/18149 - ~ PCTIEP94/00346
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PROCESS FOR MAKING 1,3-DIOLS AND 3-HYDROXYALDEHYDES
This invention relates to a process for making 1,3-diols and
3-hydroxyaldehydes by hydroformylating 1,2-epoxides using selected
ditertiary phosphine-modified cobalt carbonyl catalysts.
3-Hydroxyaldehydes are useful chemical intermediates. They can
be readily converted to 1,3-diols which <are useful as antifreese
agent (1,3-propanediol) and as a chemica:L intermediates in the
formation of polyethers, polyesters, pol=,~oxyalkalene glycols which
find use in fibers, additives, stabilize:cs and the like.
US Patents Nos. 3,463,819 and 3,456,017 teach a process for
the hydroformylation of epoxides to produce 3-hydroxyaldehydes and
1,3-diols using phosphine-modified cobalt carbonyl catalysts. These
references use a large amount of catalyst compared to the starting
epoxide amounts used. The use of large amounts of catalyst is
expensive and can make a commercial process uneconomical. The
hydroformylation of epoxides of higher carbon number than ethylene
oxide produces lower selectivities and yields of product when
compared to the hydroformylation of ethylene oxide.
US Patent No. 3,687,981 uses dicobalt octacarbonyl as a
catalyst and discloses hydroquinone as a catalyst stabilizer in the
hydroformylation of ethylene oxide. Inorganic halogen-containing
compounds, such as hydrochloric acid, are disclosed hydroformyla-
tion promoters, i.e., compounds that increase the conversion of
ethylene oxide to the desired product. Trace amounts are said to be
useful.
In US Patents Nos. 3,401,204 and 3,527,818 ditertiary phos-
phine ligands and cobalt catalysts prepared therefrom are described
as being suitable for hydroformylating olefins to alcohols.
It is an object of this invention to use an improved catalyst
system comprising cobalt-ditertiary phosphine ligand catalyst to
hydroformylate epoxides having 3 or more carbon numbers to the
corresponding 3-hydroxyaldehyde and 1,3-diol products in a high
CA 02155409 2004-05-10
WO 94/18149 YCT/EP94/00346
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yield. Accordingly, this invention provides a process for making
1,3-diols and 3-hydroxyaldehydes by hydroformylating 1,2-epoxi.des
which process comprises intimately contacting
(a) a 1,2-epoxide having at least 2 carbon atoms,
(b) ditertiary phosphine-modified cobalt carbonyl catalyst, said
phosphine comprising a hydrocarbylene-bis(monophosphabicyclo-
alkane) in which each phosphorus atom is joined to hydro-
carbylene and is a member of a bridge linkage without being a
bridgehead atom and which hydrocarbylene-bis(monophospha-
bicycloalkane) has 11 to 300, preferably 11 to 200, more
preferably 11 to 100 and most preferably 18 to 80 carbon
atoms, of which 5 to 12, preferably 6 to 12, more preferably 7
to 12 and most preferably 8 carbon atoms together with a
phosphorus atom are members of each of the two bicyclic
skeletal structures,
(c) carbon monoxide, and
(d) hydrogen, the molar ratio of carbon monoxide to hydrogen being
from 4:1 to 1:6, preferably from 1:1 to 1:4
in liquid-phase solution in an inert reaction solvent, at a temper-
ature of from 30 to 150°C and a pressure of from 345 to 68948 kPa
(50 to 10,000 psi).
1,2-Epoxides are hydroformylated by reaction with carbon
monoxide and hydrogen in the presence of a catalyst system compris-
ing a ditertiary phosphine-modified cobalt carbonyl catalyst. The
reaction products comprise primarily 3-hydroxyaldehydes (and
oligomers thereof) and 1,3-diols. The ratio of the two products can
be adjusted by adjusting the amounts of catalysts present in the
reaction mixture, the reaction temperature and/or the amount of
hydrogen present in the reaction mixture. When the term "3-hydroxy-
aldehyde" is used herein is understood to mean the monomer as well
as dimers, trirners and higher oligomers of the 3-hydroxyaldehyde.
The 3-hydroxyaldehyde and/or 1,3-diol product will have one more
carbon atom that the reactant epoxide. In a preferred embodiment,
lower amounts of catalyst are used to produce primarily the alde-
hyde and its oligomers which are then hydrogenated to the 1,3-diol
WO 94/18149 -
PCT/EP94/00346
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in a separate hydrogenation step using conventional hydrogenation
catalyst and hydrogen. The use of the particular ditertiary
phos-
phines as complexing ligands for the cobalt catalyst results
in
catalysts providing very high yields of 'hydroformylated
products,
higher than that provided by the use of conventional phosphine
ligands.
The epoxide reactant comprises an organic compound, two
carbons of which are connected by an oxy linkage as well
as by a
carbon-carbon single bond. The preferred compounds are
those having
the oxy linkage at the 1,2-position. In general terms the
compounds
comprise hydrocarbyl-epoxides, having carbon numbers of
at least 2,
preferably having carbon numbers ranging from 2 to 30,
more prefer-
ably from 2 to 20, and most preferably from 2 to 10. The
hydro-
carbyl moiety may be any nonacetylenic acyclic or cyclic
organic
radical. Wide variation is possible in that the (nonacetylenic)
acyclic or cyclic hydrocarbyl group may be aryl, alkyl,
alkenyl,
aralkyl, cycloalkyl, straight chain, branched chain, large
or
small. Preferred compounds are 1,2-epoxyalkanes and 1,2-epoxyal-
kenes. Suitable examples of 1,2-epoxyalkanes include ethylene
oxide, propylene oxide, isobutylene oxide, 1,2-epoxypentane,
1,2-epoxy-4-methylpentane, 1,2-epoxyoctane, 3-cyclohexyl-1,2-epoxy-
propane, 1,2-epoxy-2,2,4-trimethylhexane, 1,2-epoxydecane
and
1,2-epoxydodecane. Suitable examples of 1,2-epoxyalkenes
include
1,2-epoxypent-4-ene, 1,2-epoxyhex-5-ene, 1,2-epoxy-4-methylhex-5-
ene, 1,2-epoxyoct-5-ene, 1,2-epoxydec-9-ene and 1,2-epoxydodec-11-
ene. Ethylene oxide and propylene oxide are most preferred.
The process is conducted, in one modification, by charging
the
epoxide reactant, catalysts, optional catalyst promoters)
and
reaction solvent to an autoclave or similar pressure reactor
and
introducing the hydrogen and carbon monoxide while the
reaction
mixture is maintained at reaction temperature. Alternatively,
the
process is conducted in a continuous manner as by contacting
the
reactants, catalysts and optional catalyst promoters) during
passage through a reactor which is typically tubular in
form. For
best results the process is conducted under conditions
of elevated
WO 94/18149 PCT/EP94/00346
215 409
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temperature and pressure. Reaction temperatures range from 30 to
150°C, preferably from 50 to 125°C, and most preferably from 70
to
110°C. The reaction pressure is desirably in the range of from 345
,,
to 68948 kPa (50 to 10,000 psi), preferably from 3447 to 20684 kPa
(500 to 3000 psi). In one modification of~the process, inert
gaseous diluent is present, e.g., inert gaseous diluents such as
argon, helium, methane, nitrogen and the like, in which case the
reaction pressure is properly considered to be the sum of the
partial pressures of the materials other than the diluent. In the
preferred modification o,f the process, however, the reaction is
conducted in the substantial absence of added diluent.
The course of the reaction is easily followed by observing the
pressure decrease within the reactor, by in situ infrared absorp-
tion techniques or by periodic withdrawal and analysis of samples
from the reaction system. At the conclusion of reaction, the
product mixture is separated by conventional methods such as
selective extraction, fractional distillation, decantation, selec-
five crystallization and the like. The unreacted starting material
as well as the catalyst and reaction solvent are suitably recycled
for further reaction.
The catalysts employed in the process of the invention are
ditertiary phosphine-modified cobalt carbonyl complexes. Particu-
larly preferred ditertiary phosphines are chosen from a,f2-hydro-
carbylene-P,P'-bis(monophosphabicyclononanes) in which ring systems
(a) each phosphorus atom is a member of a bridge linkage, (b) each
phosphorus atom is not in a bridgehead position, and (c) each
phosphorus atom is not a member of the bicyclic system of the
other, and (d) the smallest phosphorus-containing rings contain at
least four, preferably at least five atoms. In addition to the
hydrocarbylene substitution on the phosphorus atoms, the ring
carbons may also be substituted. The hydrocarbylene is preferably
selected from ethylene, propylene and butylene. Most preferably the
hydrocarbylene is ethylene and each of the monophosphabicyclononane
moieties of the ditertiary phosphine is independently selected from
9-phosphabicyclo[4.2.1]-nonane and 9-phosphabicyclo[3.3.1]nonane.
215~4~9
WO 94/18149 ,~ PCT/EP94/00346
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As used herein the term "9-phosphabicyclononyl" or "9-phospha-
bicyclononane" will refer to phosphabicyclo[4.2.1]nonane and
9-phosphabicyclo[3.3.1]nonane moieties and mixtures thereof.
In general terms the ditertiary phosphine ligands used to form
the cobalt-carbonyl-phosphine complexes comprise bicyclic hetero-
cyclic ditertiary phosphines. One class of such compounds has from
11 to 300, preferably 11 to 200, more preferably 11 to 100 and most
preferably 18 to 80 carbon atoms, and is represented by the formula
Rz R R Rz
C C C C\
( R2~ \ / \ ( CCR~> ) z ,~
_ II ( CRz ) y
C Y P - 1
( z ) R C ~ P t:R-,
z
~C C~ ~C / - C
Rz R R Rz
where Q represents hydrocarbylene of up to 30 carbon atoms; R
independently represents hydrogen and hydrocarbyl of 1 to 30 carbon
atoms; y and z represent zero or positive integers whose sum is
from 0 to 7; y' and z', independent of the values of y and z,
represent zero or positive integers whose sum is from 0 to 7;
preferably y and z represent positive integers whose sum is from 1
to 7, more preferably from 2 to 7 and most preferably 3 with each
of which having a minimum value of I; y' and z', independent of the
values of y and z, represent positive integers whose sum is from 1
to 7, more preferably from 2 to 7 and most preferably 3 with each
of which having a minimum value of 1. It is to be understood that
in the foregoing graphic formula and those appearing hereinafter
the line portion of the structure represents a conventional organic
chemical covalent bond with saturated carbon atom at each indicated
intersection, the saturation being by the required number of
hydrogen atoms or lower alkyl radicals.
Hence, a preferred group of bicyclic heterocyclic ditertiary
phosphines includes those represented by Formula I where Q repre-
Bents hydrocarbylene of 2 to 30 carbons and especially of 2 to 20;
y and z represent positive integers whose sum is 3 and each of
WO 94/18149 PCT/EP94/00346
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which has a minimum value of 1; y' and z', independent of the
values of y and z, represent positive integers whose sum is 3 and
each of which has a minimum value of I; and R represents hydrogen
and optionally hydrocarbyl of from 1 to 20 carbons.
The term "hydrocarbylene" is used in its accepted meaning as
representing a diradical formed by removal of two~~hydrogen atoms
from a carbon atom or preferably one hydrogen ~."~om from each of two
°~..
different carbon atoms of a hydrocarbon. The hy:3rocarbylene groups
represented by Q in the formula above may be any nonacetylenic
acyclic or cyclic organic radical composed solely of carbon and
hydrogen. Wide variation is possible in that the (nonacetylenic)
acyclic or cyclic hydrocarbylene group may be arene, alkylene,
alkenylene, aralkylene, cycloalkylene, straight chain, branched
chain, large or small. Representative hydrocarbylene groups include
methylene, ethylene, trimethylene, tetramethylene, butylene,
pentamethylene, pentylene, methylpentylene, hexamethylene, hexenyl-
ene, ethylhexylene, dimethylhexylene, octamethylene, octenylene,
cyclooctylene, methylcyclooctylene, dimethylcyclooctylene, iso-
octylene, dodecamethylene, hexadecenylene, octadecamethylene,
eicosamethylene, hexacosamethylene, triacontamethylene, phenylene-
diethylene, and the like. A particularly useful class of bicyclic
heterocyclic ditertiary phosphines is that containing only carbon,
hydrogen, and phosphorus atoms. Substituted hydrocarbylene groups
are also contemplated and may contain a functional group such as
the carbonyl, carboxyl, vitro, amino, hydroxy (e. g. hydroxyethyl),
cyano, sulfonyl, and sulfoxyl groups. A particularly useful group
of ditertiary phosphines consists of those in which Q is hydro-
carbylene of up to 30 carbon atoms, preferably of from 2 to 30
carbon atoms; more preferably from 2 to 20 carbons, even more
preferably from 2 to 10. In a preferred embodiment Q is ethylene,
propylene or butylene, more preferably ethylene.
The term "hydrocarbyl" is used in its accepted meaning as
representing a radical formed by removal of one hydrogen atom from
a carbon atom of a hydrocarbon. The hydrocarbyl groups represented
by R in the formula above may be any nonacetylenic acyclic or
WO 94/18149 ~ _ PCTIEP94/00346
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cyclic organic radical composed solely of carbon and hydrogen. Wide
variation is possible in that the (nonacetylenic) acyclic or cyclic
hydrocarbyl group may be aryl, alkyl, alkenyl, aralkyl, cycloalkyl,
straight chain, branched chain, large or small. Representative
hydrocarbyl,groups include methyl, ethyl, butyl, pentyl,
methyl-
pentyl, hexenyl, ethylhexyl, dimethylhexyl, octamethyl,
octenyl,
cyclooctyl, methylcyclooctyl, dimethylcyclooctyl, isooctyl,
dode-
cyl, hexadecenyl, octyl, eicosyl, hexacosyl, triacontyl,
phenyl-
ethyl, and the like. Substituted hydrocarbyl groups are
also
contemplated and may contain a functional group such as
the car-
bonyl, carboxyl, vitro, amino, hydroxy (e. g. hydroxyethyl),
cyano,
sulfonyl, and sulfoxyl groups. Preferably R is hydrogen
or hydro-
carbyl, preferably alkyl, having 1 to 30, preferably 1
to 20 and
most preferably from 8 to 20 carbon atoms.
Ditertiary phosphine ligands and cobalt catalysts prepared
therefrom are known in the art and their method of preparation
are
described in detail in US Patents Nos. 3,401,204 and 3,527,818.
Generically, the ditertiary phosphine-modified cobalt complex-
es are characterized as dicobalt hexacarbonyl complexes
of addi-
tionally present ditertiary phosphine ligand sufficient
to provide
one phosphorus complexing atom for each atom of cobalt
present
within the complexed molecule.
The phosphine ligands may also be partially oxidized to
phosphine oxides in order to enhance the activity of the
cobalt-
ligand complex. The oxidation is carried. out with an oxidant
under
mild oxidizing conditions such that an oxygen will bond
to a
phosphorus, but phosphorus-carbon, carbon-carbon and carbon-hydro-
gen bonds will not be disrupted. By suitable selection
of tempera-
tures, oxidants and oxidant concentrations such mild oxidation
can
occur. The oxidation of the phosphine ligands is carried
out prior
to the forming of the catalyst complex.
Suitable oxidizing agents include peroxy-compounds, persul-
fates, permanganates, perchromates and ~,aseous oxygen.
Preferred
compounds, for ease of control, are the peroxy-compounds.
Peroxy-
compounds are those which contain the peroxy (-0-0-) group.
WO 94/18149 ~ ~ ~ ~ ~ ~ PCT/EP94/00346
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Suitable peroxy-compounds may be inorganic or organic. Suitable
inorganic compounds include hydrogen peroxide as well as inorganic
compounds which in contact with water liberate hydrogen peroxide,
such compounds include the mono-valent, di-valent and trivalent
metal peroxides as well as hydrogen peroxide addition compounds.
.
Also suitable are the organic peroxy-:~iimpounds, including hydro-
peroxides; a-oxy- and a-peroxy- hydroperoxides and peroxides;
peroxides; peroxyacids; diacyl peroxides; and peroxyesters. Suit-
able peroxyorgano-compounds include t-butyl hydroperoxide, cumene
hydroperoxide, dibenzoyl peroxide and peroxyacetic acid. Peroxy-
compounds suitable for carrying out the oxidation process are known
in the art, and suitable examples can be found in The Encyclopedia
of Chemical Technology, Vol. 17, pp. 1-89, Third Edition (John
Wiley & Sons, 1982).
Typically oxidation is carried out by adding to the ligand a
measured amount of oxidizing agent, sufficient to carry out the
degree of oxidation required. The ligand may be dissolved in a
suitable solvent. The oxidizing agent is typically added slowly
over a period of time to control the oxidizing conditions. The
temperature is maintained to provide mild oxidizing conditions.
When hydrogen peroxide is used as the oxidizing agent, the tempera-
ture is typically maintained at room temperature.
The oxidation of the ligand is carried out to provide no more
than 0.5 oxygen atoms per phosphorus atoms, on the average, in the
oxidized ligand product. Preferably the ratio of oxygen atoms to
phosphorus atoms in the oxidized ligand will range, on the average,
from 0.01:1 to 0.5:1, and more preferably from 0.05:1 to 0.3:1.
The cobalt catalysts can be prepared by a diversity of meth-
ods. A convenient method is to combine a cobalt salt, organic or
inorganic, with the desired phosphine ligand, for example, in
liquid phase followed by reduction and carbonylation. Suitable
cobalt salts comprise, for example, cobalt carboxylates such as
acetates, octanoates, etc., which are preferred, as well as cobalt
salts of mineral acids such as chlorides, fluorides, sulfates,
sulfonates, etc. Operable also are mixtures of these cobalt salts.
WO 94/18149 ~ 21 ~ ~ 4 0 9 ~ PCT/EP94/00346
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It is preferred, however, that when mixtures are used, at least one
component of the mixture be cobalt alkanoate of 6 to 12 carbon
atoms. The valence state of the cobalt many be reduced and the
cobalt-containing complex formed by heating the solution in an
atmosphere of hydrogen and carbon monoxide. The reduction may be
performed prior to the use of the catalysts or it may be accom-
plished simultaneously with the hydroformylation process in the
hydroformylation zone. Alternatively, thE; catalysts can be prepared
from a carbon monoxide complex of cobalt. For example, it is
possible to start with dicobalt octacarbonyl and, by heating this
substance with a suitable phosphine ligand, the ligand replaces one
or more, preferably at least two, of the carbon monoxide molecules,
producing the desired catalyst. When this latter method is executed
in a hydrocarbon solvent, the complex ma:,~ be precipitated in
crystalline form by cooling the hot hydrocarbon solution. This
method is very convenient for regulating the number of carbon
monoxide molecules and phosphine ligand molecules in the catalyst.
Thus, by increasing the proportion of phosphine ligand added to the
dicobalt octacarbonyl, more of the carbon monoxide molecules are
replaced.
The optimum ratio of 1,2-epoxide feed to phosphine-modified
cobalt carbonyl complex will in part depend upon the particular
cobalt complex employed. However, molar ratios of 1,2-epoxide to
cobalt complex from 2:1 to 10,000:1 are generally satisfactory,
with molar ratios of from 50:1 to 500:1 being preferred. When batch
processes are used, it is understood that. the above ratios refer to
the initial starting conditions. In one modification, the diter-
tiary phosphine-modified cobalt carbonyl complex is employed as a
preformed material, being prepared as by reaction of a cobalt salt
with carbon monoxide and hydrogen in the presence of the ditertiary
phosphine ligand, then isolated and subsequently utilized in the
present process. In an alternate modification, the ditertiary
phosphine-modified cobalt complex is prepared in situ as by addi-
tion to the reaction mixture of a cobalt salt or dicobalt
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octacarbonyl together with the ditertiary phosphine ligand whose
introduction into the catalyst complex is desired.
In practice, it is preferable to employ the ditertiary phos
phine-modified cobalt complex in coiZjunction~.~~aith a minor propor
~>
tion of excess ditertiary phosphine ligand°acatiich is the same as or
t d
is different from the ditertiary phosphi~e'~ligand(s) of the cobalt
complex. Although the role of the excess''phosphine is not known
with certainty, the presence thereof in the reaction system appears
to promote or otherwise modify catalyst activity. Phosphorus: cobalt
atom ratios utilized in conjunction with the catalyst complex will
range from 0.1:1 to 3:1, preferably from 0.5:1 to 2:1, more prefer-
ably from 1:1 to 1.5:1. A ratio of about 1.25:1 is particularly
preferred.
In another modification of the process of the invention, an
additional ruthenium catalyst is present in the catalyst system
employed in the process of the invention. The ruthenium should be
present in concentrations dependent upon that of the primary cobalt
component. It should be present in Co:Ru atom ratio ranging from
1000:1 to 1:100, preferably from 100:1 to 1:10 and more preferably
from 50:1 to 1:5.
The form of the ruthenium is not critical. Thus, it may be
present in the form of a soluble homogeneous component or as a
finely divided metal or supported on a carrier which is suspended
in the reaction mixture or utilized in a fixed bed.
The solub_e ruthenium components may be added in any of a
number of forms including inorganic salts such as ruthenium ni-
trate, ruthenium sulfate, ruthenium fluoride, ruthenium chloride,
ruthenium bromide, ruthenium iodide, ruthenium oxide and ruthenium
phosphate or organic ruthenium salts such as ruthenium formate,
ruthenium acetate, ruthenium propionate, ruthenium butyrate,
ruthenium acetonylacetonate, etc., or aromatic ruthenium salts such
as ruthenium benzoate, ruthenium phthalate, ruthenium naphthenate,
etc., or as carbonyls such as bis-[ruthenium tricarbonyl dichlo-
ride] or bis-[ruthenium tricarbonyl dibromide], etc.
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Ruthenium complexes are often more soluble than the salts
and
are, therefore, more desirable if high concentrations of
homoge-
neous ruthenium solutions are desired. These complexes
include
ruthenium(III)tris-(2,4-pentanedionate), triruthenium dodeca-
carbonyl, ruthenium(II)dichlorotris-(triphenylphosphine),
rutheni-
um(II)dichlorotetrakis-(triphenylphosphine), ruthenium(II)hydrido-
chlorotris-(triphenylphosphine), or other soluble ruthenium
com-
plexes within the spirit of this group. Particularly suitable
are
ruthenium complexes of the phosphines described above which
are
used to form the cobalt carbonyl complexes.
The insoluble or heterogeneous ruthenium forms may be intro-
duced as any of the forms given above which under a sufficiently
hydrogen-rich atmosphere or reducing environment will give
finely
divided ruthenium. Alternatively, the insoluble ruthenium
may be
produced by reducing a soluble rutheniu~r form in the presence
of a
suitable support to give finely divided ruthenium deposited
on
supports including activated charcoal, alumina, silica
gel, or
zeolites. Other forms may be included if they can be divided
finely
enough by mechanical means such as ruthenium powder, ingot,
shot,
sponge, or wire.
The process of the invention is conducted in liquid-phase
solution in an inert solvent. A variety of solvents which
are inert
to the reactants and catalyst and which are liquid at reaction
temperature and pressure are in part operable. Illustrative
of
suitable solvent are hydrocarbons, particularly aromatic
hydrocar-
bons of up to 16 carbon atoms such as benzene, toluene,
xylene,
ethylbenzene, and butylbenzene; alkanes such as hexanes,
octaves,
dodecanes, etc.; alkenes such as hexenes, octenes, dodecenes,
etc.;
alcohols such as t-butyl alcohol, hexanol, dodecanol, including
alkoxylated alcohols; nitriles such acetonitrile, propionitrile,
etc.; ketones, particularly wholly aliphatic ketones, i.e.,
alka-
nones, of up to 16 carbon atoms such as acetone, methyl
ethyl
ketone, diethyl ketone, methyl isobutyl ketone, ethyl hexyl
ketone
and dibutyl ketone; esters of up to 16 carbon atoms, particularly
lower alkyl esters of carboxylic acids which are aliphatic
or
WO 94/18149 ~ , PCT/EP94/00346
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aromatic carboxylic acids having one or more carboxyl groups,
preferably from 1 to 2, such as ethyl acetate, methyl propionate,
propyl butyrate, methyl benzoate, diethyl glutarate, diethyl
phthalate and dimethyl terephthalate; and, ethers of up to 16 carbon
atoms and up to 4 ether oxygen atoms, which ethers are cyclic or
acyclic ethers and which are wholly al~~~hatic ethers, e.g., diethyl
ether, diisopropyl ether, dibutyl ether, ethyl hexyl ether, methyl
octyl ether, dimethoxyethane, diethylene glycol dimethyl ether,
diethylene glycol diethyl ether, diethylene glycol dibutyl ether,
tetraglyme, glycerol trimethyl ether, 1,2,6-trimethoxyhexane,
tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane and
2,4-dimethyl-1,3-dioxane, or which are at least partially aromatic,
e.g., diphenyl ether, phenylmethyl ether, 1-methylnaphthalene,
phenylisopropyl ether, halogenated hydrocarbons, such as chloro-
benzene, dichlorobenzene, fluorobenzene, methyl chloride, methylene
dichloride. Mixtures of solvents can also be utilized.
The amount of solvent to be employed is not critical. Typical
molar ratios of reaction solvent to ethylene oxide reactant vary
from 5:1 to 150:1.
Suitable selection of solvents can enhance product recovery.
By selecting solvents with suitable polarity, a two phase system
will form upon cooling of the reaction mixture with selective
distribution of the catalyst and ligand in one phase and product
3-hydroxypropanal and 1,3-propanediol in a second phase. This will
allow for easier separation of catalyst and ligand and recycle
thereof back to the reactor. When a two phase separation process is
used, solvents that would not be desirable in the reaction mixture,
such as water and acids, can be used to enhance distribution of
product to one phase and catalyst/ligand to the other phase.
Illustrative solvents for use in a one phase system are
diethylene glycol, tetraglyme, tetrahydrofuran, t-butyl alcohol,
and dodecanol. Illustrative solvents for use to provide a two phase
system upon cooling are toluene, 1-methylnaphthalene, xylenes,
diphenyl ether and chlorobenzene. '
2~.~5~~9
WO 94/18149 " PCT/EP94/00346
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The process of the invention comprises contacting the 1,2-
epoxide reactant and catalyst with carbon monoxide and molecular
hydrogen. The molar ratio of carbon monoxide to hydrogen
most
suitably employed is from 4:1 to 1:6, with best results
being
obtained when ratios of from 1:1 to 1:4 are utilized. No
1 special
precautions need~to be taken with regard to the carbon monoxide
and
hydrogen and commercial grades of these reactants are satisfactory.
The carbon monoxide and hydrogen are suitable employed as
separate
materials although it is frequently advantageous to employ
commer-
cial mixtures of these materials, e.g., synthesis gas.
The addition of small amounts of acids and promoting metal
salts to the hydroformylation reaction mixture can further
enhance
or promote the conversion of ethylene oxide by increasing
the
activity of the catalyst. Acids are defined herein to mean
those
compounds which can donate a proton under reaction conditions.
Suitable acids can include inorganic acids such HCl, HBr,
HI,
boric acid and organic acids in amounts ranging from trace
amounts
up to two times the molar amount of catalyst utilized. Suitable
organic acids include the organo-acids having carbon numbers
of 1
to 16, such as carboxylic acids, sulfonic acids, phosphonic
acids,
phosphinic acids as well as other organic compounds that
will
donate protons under reaction conditions such as imidazole,
benzo-
imidazole, pyridinium salts, pyrazinium salts, pyrimidinium
salts,
particularly salts of the aforementioned acids. Non-limiting
examples of organic acids include acetic acid, propionic
acid,
hexanoic acid, 2-ethylhexanoic acid, oct.anoic acid,
3-(phenylsulfonyl)-propionic acid, para-toluenesulfonic
acid,
2-carboxyethylphosphonic acid, ethylphos~phonic acid, n-butylphos-
phonic acid, t-butylphosphonic acid, phenylphosphonic acid,
phenyl-
phosphenic acid, phenyl boric acid, pyridinium para-toluenesulfo-
nate and pyridinium octoate.
Another suitable method for providing promoter acids is
to use
as a catalyst precursor a cobalt salt of an organic acid,
which
will convert to cobalt carbonyl and the organic acid under
reaction
conditions. Such precursor salts include cobalt acetate,
cobalt
WO 94/18149 ~.'~~~ PCT/EP94/00346
- 14 -
2-ethylhexanoate, cobalt benzoate, cobalt formate and cobalt
oleate. The ratio of gram equivalents of acid promoter to gram
atoms of cobalt in the catalyst present in the reaction mixture
will generally range from 0.001:1 ta'4:1, preferably from 0.01:1 to
. ~ .~~.'.,.
2:1.
Promoting amounts of metal salts can also be added to the
reaction mixture along with the promoting amounts of acid to
provide an even further enhanced promoting effect. Promoting
amounts of one or more metal salts selected from a salt of a metal
of Group IA, IIA, Group IIB, Group IIIB and the Rare Earth Series
of the Periodic Table of the Elements (CAS version) are also added
to the reaction mixture along with the promoting amounts of acid.
Group IA comprises the alkali metals, lithium through cesium. Group
IIA comprises the alkaline earth metals, calcium through barium.
Group IIB comprises zinc, cadmium and mercury. Group IIIB comprises
scandium, yttrium and lanthanum. The Rare Earth Group comprises
cerium through lutetium. Any metal salt from the aforementioned
Groups that is at least partially soluble in the reaction mixture
is suitable. Both inorganic salts and organic salts are suitable.
Included in the inorganic salts are halides, chromates, sulfates,
borates, carbonates, bicarbonates, chlorates, phosphates, etc.
Particularly desirable organic salts are salts of carboxylic acids
having carbon numbers ranging from 1 to 20. Examples of metal salts
that have been found suitable as copromoters include halides, such
as bromides, iodides, and chlorides, carboxylates, such as ace-
tates, propionates and octoates, borates, nitrates, sulfates and
the like. In general a metal salt that does not react with the
1,2-epoxide, the reaction solvent or the hydroformylation products
is suitable as copromoters with acids. The ratio of gram equiva-
lents of metal of the salt promoter to gram atoms of cobalt in the
catalyst present in the reaction mixture will generally range from
0.001:1 to 2:1, preferably from 0.01:1 to 1:1, and more preferably
from 0.1:1 to 0.5:1.
In a preferred embodiment the product of the hydroformylation
reaction is further hydrogenated to produce a product comprising
CA 02155409 2004-05-10
WO 94/18149 PCT/EP94/00346
- 15 -
substantially 1,3-diol. The hydroformylated product is preferably
separated from the catalyst before being hydrogenated. Inert
solvent may be added to the product prior to hydrogenation, or, if
an inert (to hydrogenation) solvent was used in the hydroformyla-
tion reaction, it may be separated with the product and passed to
the hydrogenation reactor. The hydrogenation catalyst can be any of
the well known hydrogenation catalysts used in the art such as
Raney nickel, palladium, platinum, ruthenium, rhodium, cobalt and
the like. It is desirable to employ as the hydrogenation catalyst a
metal or a compound of a metal which may be easily and economically
prepared, which has a high degree of activity, and retains this
activity for extended periods of time. The hydrogenation catalyst
may be employed homogeneously, in a finely divided form and dis-
persed throughout the reaction mixture, or preferably it may be
employed on a support or carrier material such as alumina, carbon
or the like. Preferred catalysts are Raney nickel and supported
platinum, particularly platinum on carbon. Hydrogenation conditions
include pressures ranging from 345 to 68948 kPa (50 to 10,000 psi)
and temperatures ranging from 30 to 175°C. The hydrogenating gas
used is molecular hydrogen or a mixture of hydrogen and carbon
monoxide such as that used for the hydroformylation reaction.
The ranges and limitations provided in the instant specifica-
tion and claims are those which are believed to particularly point
out and distinctly claim the instant invention. It is, however,
understood that other ranges and limitations that perform substan-
tially the same function in substantially the same way to obtain
the same or substantially the same result are intended to be within
the scope of the instant invention as defined by the instant
specification and claims.
Illustrative Embodiment I
In the examples and tables the following abbreviations are
used:
EO/PDO/3-HPA ethylene oxide/1,3-propanediol/3-hydroxypropan a l,
PO/BDO/3-HBA propylene oxide/1,3-butanediol/3-hydroxybutanal,
9-PHOSPHA 1,2-bis(9-phosphabicylcononyl)ethane,
WO 94/18149 ~ ~ ~ PCT/EP94/00346
- 16 -
DIPHOS 1,2-bis(diphenylphosphino)ethane,
BDCHP 1,2-bis(dicyclohexylphosphino)ethane,
TBP tri-n-butylphosphine, and
TPP triphenylphosphine..
"EO Conv. Rate" refers to the rate in grams of EO converted per
y .w
hour."PDO Precursors" are hhose compounds which upon hydrogenation
produce PDO and include primarily 3-HPA with smaller amounts of
dimers, trimers and other oligomers of 3-HPA being present. Also
included are small amounts of acrolein and propionaldehyde. Most of
the acrolein is an artifact of the gas chromatographic (GC) measur-
ing process as a result of decomposition of 3-HPA during analysis.
In situ infrared spectroscopic analyses after completion of the
hydroformylation reactions showed no acrolein present in the
products. Lowering the temperature and chemically passifying the
injection port of the GC instrument dramatically lowered these
artifact peak heights, indicating that it is at most only a minor
product (1-2~).
In this illustrative embodiment catalysts complexed with the
preferred ligands are prepared and tested for hydroformylation of
ethylene oxide and compared with catalysts prepared from non-pre
ferred ligands.
In Situ Catalyst Preparation and Hydroformylation:
Examples 1-2
In an inert atmosphere, a 100 ml air-stirred Parr autoclave
was charged with 228 mg (0.66 mmole) of cobalt octoate, 155 mg
(0.50 mmole) of 9-PHOSPHA (as a mixture of [4.2.1] and [3.3.1J
isomers) and 23 ml of dry, nitrogen-purged toluene-clorobenzene
solution (5:1 volume ratio). The autoclave was sealed and pressured
to 9065 kPa (1300 psig) with a hydrogen-carbon monoxide gas mixture
(1:1 molar ratio). The reaction was stirred and heated at 130°C for
30 minutes at 10443 kPa (1500 psig). The reactor was then cooled to
an internal temperature of 5°C and the gases were vented to leave
the autoclave at ambient pressure.
EO (4.5 g, 102 mmole) was added to the reactor and the reactor
was then heated and stirred for 3 hours at 105°C at a pressure of
WO 94/18149 _ ~ PCTIEP94/00346
- 17 -
9754 to 10443 kPa (1400 to 1500 psig) o:E hydrogen-carbon monoxide
gas (1:1 molar ratio).
After cooling to 5°C, the reactor Haas purged with nitrogen and
the two-phase product mixture was collected to give about 29 grams
of solvent phase and about.2 grams of an oil phase. The two phases
were independently analyzed by gas chromatography. Results are
shown in Table 1 as Example 1.
Example 1 was repeated except that the hydrogen/carbon monox
ide ratio was changed to 4:1. The results are presented in Table 1
as Example 2.
TABLE 1
EO EO --- mole ~ selectivity --
H2/CO Conv. Conv. PDO PDO CH3CH0
Example Ratio Rate Mole $ Precursor
1 1:1 0.37 21.2 93.4 0.8 5.8
2 4:1 0.48 31.2 92.3 2.1 5.6
Examp les 3-6
The hydroformylation f ethyleneo:Kide repeatedusing the
o was
procedure, catalyst and ditions Example1 except
con described
in
that varying amountsof 9-PHOSPHAligand cobaltolar ratios
the to m
were used. The ts shown
resul are in Table
2.
TABLE
2
EO EO --- mole ~ selectivity
---
P/Co Conv. Conv. PDO PDO CH3CH0
Example Ratio Rate mole ~ P:recursor
3 2.0 0.21 13.9 75.4 9.9 6.9
4 1.5 0.45 25.1 93.1 1.3 6.0
5 1.25 0.46 32.1 88.9 1.5 8.9
6 1.0 0.74 45.0 76.8 2.1 18.6
WO 94/18149 ~ PCT/EP94/00346
_ lg -
Examples 7-11
The hydroformylation of EO was repeated using the procedure
described in Example 1 with the following differences: reaction
temperature and ligands were change'd,in different examples and
,.
indicated in Table 3. Results a~'~e shown in Table 3. Phosphine
ligands, not of this inventions,' were also tested and the results
are shown in Table 3 (C-1 to~'C-8).
TABLE 3
Rxn EO -- mole ~ selectivity --
Temp. Conv. EO Conv. PDO PDO CH3CH0
Examples Liganda) °C Rate Mole ~ Precursor
C-1 TBP 115 3.2 - 21.0 69.0
C-2 TBP 105 1.8 - 30.0 70.0
C-3 DIPHOS 105 0.74 54.0 3.8 80.8 13.7
7 9-PHOSPHA 105 0.45 25.1 1.3 91.9 6.0
C-4 # 105 0.89 47.6 3.2 78.3 18.1
C-5 DIPHOS 100 0.64 44.6 2.3 88.1 8.4
8 9-PHOSPHA 100 0.37 21.3 0.9 95.8 4.5
C-6 DIPHOS 95 0.43 31.2 1.6 91.3 5.8
9 9-PHOSPHA 95 0.27 15.4 0.8 96.5 3.7
C-7 DIPHOS 90 0.32 22.0 3.1 89.0 6.4
9-PHOSPHA 90 0.20 11.5 0.6 98.5 -
C-8 .- 90 0.27 19.0 0.3 94.9 -
11 @ 90 0.29 14.1 9.0 81.6 9.3
a) # = 1-(9-phosphabicyclononyl)-2-(diphenylphosphino)ethane.
@ = 1,3-bis(9-phosphabicyclononyl)propane.
Examples 12-15
The hydroformylation of ethylene oxide was repeated using the
10 procedure of Example 1 except that dicobalt octacarbonyl (0.33
mmoles) was used as the cobalt source and various molar ratios of
9-PHOSPHA to cobalt was used. Results are shown in Table 4. '
~~.~~~~9
WO 94/18149 " ~ PCTlEP94100346
- 19
-
TABLE
4
EO EO --- mole ~ selectivity ---
P/Co Conv. Conv. PDO PDO CH3CH0
Example Ratio Rate Mole Precursor
~
12 2.0 0.01 0.7 100 - -
13 1.5 0.03 1.8 100 - -
14 1.0 0.17 8.9 70.3 1.3 0.2
15 1.0 0.27 15.8 74.3 1.8 -
Example 16-18
The hydroformylation of EO was repeated using the procedure
(and ligand) of Example 1 except that cobalt octacarbonyl was used
as the cobalt source. Various acids were used as promoters, except
for the control experiment in which no acid was used. The results
are shown in Table 5.
TABLE 5
EO EO --- mole $ selectivity --
Acid, Conv. Conv. PDO PDO CH3CH0
Example mmoles Rate Mole ~ Precursor
16 A,0.165 0.20 11.3 93.7 - -
17 B,0.165 0.19 11.4 91.9 1.2 4.5
18 B,0.33 0.25 13.6 92.0 - 4.8
Control - 0.04 2.1 100.0 - -
A = pyridinium para-toluene sulfonate
B = n-octanoic acid
The following acids when used as a promoter in the above
reaction were also found to increase the amount of EO converted
(mole ~): 2-carboxyethylphosphonic acid (13~), n-butylphosphonic
acid (16~), phenyl- phosphoric acid (14.50 , t-butylphosphonic acid
(18.5$), 3-(phenylsulfonyl)-propionic acid (22~), phenylboric acid
(18~), phenylphosphenic acid (36$), and imidazole (26$).
WO 94/18149 ~~~~ ~ PCT/EP94/00346
- 20 -
Examples 19 and 20
The hydroformylation of E0 was repeated using the procedure
(and ligand) of Example 1 except a reaction temperature of 90°C was
used. In Example 19 cobalt 2-ethylhexanoate was used as a cobalt
source and 0.21 mmoles of sodium acetate~was added in the catalyst
'~
preparation step as a catalyst cop~amoter. In Example 20 dicobalt
octacarbonyl was used as a cobalt source and 1.32 mmoles of 2-
ethylhexanoic acid and 0.21 mmoles of sodium acetate were added as
catalyst promoters. The results are shown in Table 6.
TABLE 6
EO EO - mole ~ selectivity -
Conv. Conv. PDO CH3CH0
Example Rate Moles ~ Precursor
19 0.65 39.2 96.5 3.1
20 0.64 40.1 98.6 3.1
Illustrative Embodiment II: Hydrogenation of Hydroformylation
Product:
Example 21
Ten grams of the reaction product from an EO hydroformylation
reaction such as example 1 above was charged to a 300 ml autoclave
along with 40 grams of deionized water and 2 grams of Raney nickel
catalyst. The autoclave was flushed with hydrogen, pressured with
hydrogen to 6996 kPa (1000 psig) and heated to 110°C for 5 hours.
The autoclave was cooled to room temperature, vented of excess gas,
and samples were removed for analysis by gas chromatography and
mass spectroscopy. This analysis showed PDO as the major product in
the water solution. The selectivity to PDO was estimated to be
about 90~ with greater than 80~ of 3-HPA converted to the diol.
Example 22
Example 21 was repeated except 18 grams of hydroformylation
product, 42 grams of water and 1.5 grams of molybdenum-promoted
Raney nickel catalyst were charged to the autoclave with a reaction
pressure of 4137 kPa (600 psi) and a reaction temperature of 60°C
WO 94/18149 PCT/EP94l00346
w~~~~4~9
- 21 -
being used. Analysis of the hydrogenated product showed that 3-HPA
was converted to PDO as the major product.
Illustrative Embodiment III
In this illustrative embodiment catalysts complexed with the
preferred ligands promoted by the acid/s;alt promoter of the instant
invention are prepared and tested for hydroformylation of EO and
compared with catalysts which are not promoted by the promoter
system of the instant invention.
In situ catalyst preparation and hydroformylation:
Example 23, 24
Example 1 was repeated, except that: 113 mg (0.33 mmole) of
dicobalt octacarbonyl and 117 mg (0.21 mmole) of sodium acetate
were used. The result is shown in Table 7.
Example 23 was repeated except that. 22$ mg (0.66 mmole) of
cobalt 2-ethylhexanoate was used as the cobalt source. The results
(example 24) are presented in Table 7. The use of cobalt acetate as
the cobalt provides similar results.
Examples 25 to 34, C-9 to C-13
Examples 25-34 in Table 7 are examF~les carried out in the same
fashion as example 23, but using 0.66 mmole of cobalt 2-ethylhexa-
noate as cobalt source and different salts as the salt promoter.
Examples C-9 through C-13 in Table 7 are comparative examples
in respect of embodiment III, carried out in the same fashion as
example 23, but without the acid promoter, the salt promoter or
both the acid and salt promoters.
Examples 35 to 41
Example 24 was repeated but using different amounts of salt
promoter. These results are shown in Table 8.
Examples 42 to 43
Example 24 was repeated at the temperatures indicated in Table
9 and at hydrogen to carbon monoxide ratio of 4:1 and a phosphorous
to cobalt ratio in the catalyst of 1.25:1. The results are shown in
Table 9.
WO 94/18149 ' PCT/EP94/00346
- 22 -
o .
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WO 94118149 ~ , . PCTIEP94100346
- 23 -
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WO 94/18149 PCT/EP94/00346 ,
~ x.55 4~'~
- 24
-
TABLE
8
EO EO --- mole selectivity
~ ---
a)
NaOAc Conv. Conv. PDO PDO CH3CH0
,
Example(mmoles) Rate Molc~: Precursor
$-
.
35 1.0 0.6I 36.4 62.5 0.2 4.8
36 0.66 0.70 39.6 60.4. 2.5 4.1
37 0.42 0.68 41.7 66.6 2.0 4.4
38 0.21 0.68 39.3 94.3 0.8 2.5
39 0.10 0.56 30.2 97.5 0.2 2.3
40 0.05 0.30 17.2 96.1 0.5 2.4
41 None 0.17 8.7 100 - -
a) NaOAc a Sodium acetate.
TABLE
9
Rxn EO EO --- mole selectivity ---
~
Temp. Conv. Conv. PDO PDO CH3CH0
ExampleC Rate Mole Precursor
~
42 80 0.77 43.4 97.3 2.7 -
43 90 0.48 27.3 97.8 2.2 -
Examples44 to
46
Example repeatedat 80C and at the essure indicated
24 pr
was
in Table10. The shown Table 10.
results in
are
TABLE
10
EO EO --- mole selectivity ---
$
Pressure Conv. Conv. PDO PDO CH3CH0
ExamplekPa Rate Mole Precursor
~
44 10342 0.77 43.4 97.4 2.7 -
45 6895 0.94 50.4 94.3 3.4 2.3
46 4137 0.59 34.1 75.5 3.8 4.7
WO 94/18149 - ~ 1 ~ ~ Q ~ PCT/EP94/00346
- 25 -
Illustrative Embodiment IV
In this illustrative embodiment the oxidation of the com-
plexing phosphine ligand is illustrated.
1.56 Grams of 9-PHOSPHA was loaded into a 100 ml three neck
round bottom flask, fitted with a rubber septum, thermometer and
gas stopcock. A stir bar was added, and 25 ml. of ethanol was
poured into the flask. The mixture was then degassed with argon.
An
argon filled balloon was attached to the gas inlet and the mixture
was stirred for 15 minutes at room temperature. 0.36 Grams of (30~
by vol.) aqueous hydrogen peroxide solution was weighed into a
ml two neck flask fitted with a rubber septum and gas stopcock.
Five ml. of ethanol was added via a syringe through the septum
and
the mixture was then degassed with argon. A length of teflon tubing
for a cannula was cut and each end was threaded through a 12 gauge
needle. The rubber septum on the smaller flask was pierced with
one
needle and the needle was then pulled out, leaving the tubing in
place above the liquid level. The argon flow was turned on to flush
through the tubing. The septum on the larger flask was pierced
with
the other needle, then the needle was withdrawn, leaving the tubing
in place approximately 0.5 inches above the liquid level. The
tubing in the small flask was carefully inserted into the liquid
as
far as possible and using the argon flow, the flow of liquid from
the peroxide mixture into the ligand mixture was regulated so that
it was transferred drop by drop. The solution was stirred at room
temperature for one hour.
The solution was then transferred to a 250 ml. round bottom
flask in a nitrogen atmosphere, using degassed ethanol to rinse out
the solids. The ethanol was removed from the solution using a
rotovapor, then the solid was dried under vacuum for several hours.
The resulting oxidized phosphine ligand was analyzed by phospho-
rus-31 NMR to determine the oxygen: phosphorus ratio.
WO 94/18149 PCT/EP94/00346
26 -
In situ catal~t preparationand hydroformylation:
Examples 47, 48-59
Example 1 wa s peated,except 113 mg 33 mmole) of
re that (0.
dicobalt octacarbonyl and mg {0.66 PHOSPHA which
204 mmole)
of 9-
had been oxidized as described.,-above provide oxygen to
to an
phosphorus of 0.2 0 re The resultis shown n Table 11.
we used. i
Example 47 w as epeatedexcept differingamounts of
r that
ligand to dicobal t tacarbonyl, ng reaction
oc differi temperatures
and differing amo untsof e phosphineligand were
oxidation
of
th
used. The results are presented 11 as
in Examples
Table 48-59.
TABLE 11
Rxn EO --- mole selectivity ---
$
0/P P/CoTemp. Conv. PDO PDO CH3CH0
Example Ratio Ratio Mole $ Precursor
C
47 0 2.0 105 1.0 100 - -
48 0 1.5 105 3.7 89.0 - 11.0
49 0 2.0 105 0.7 100 -
Trace
50 P = O 2.0 105 3.4 100 - -
51 0.07 1.9 105 8.7 94.7 - 5.3
52 0.07 2.0 105 10.1 98.5 1.5 -
53 0.13 2.0 110 17.7 86.3 1.9 4.9
54 0.20 2.5 105 21.2 90.1 3.6 4.0
55 0.20 2.0 105 33.9 86.9 3.2 7.2
56 0.20 1.5 105 42.9 65.9 1.5 18.2
57 0.20 2.0 100 20.9 90.3 4.0 4.0
58 0.30 1.4 105 47.0 81.3 3.3 15.5
59 0.30 1.4 90 30.3 90.0 4.2 3.8
~15~ 4~9
~ WD 94/18149 - ~ PCT/EP94/00346
- 27 _
Illustrative Embodiment V
In situ catalyst preparation and hydroformylation:
Example 60
Example 1 was repeated, however, using 228 mg (0.66 mmole) of
cobalt 2-ethylhexanoate, 221 mg (0.66 mmole) of 9-PHOSPHA and 74 mg
of [Ru(CO)3C12j2 (0.29 mmoles of ruthenium, basis metal). The
result is shown in Table 12 as Example 6t1.
Comparative Example C-14
The above example was repeated, however, without using the
ruthenium co-catalyst. The results are shown in Table 12 as example
C-14. (comparative example in respect of embodiment V)
Examples 61-67
Example 65 was repeated varying the promoter salt used, the
phosphine ligand used and the ruthenium compound used. These
variations and the results are shown in 7.'able 12.
Examples 68-74
Example 60 was repeated using different promoter metal salts
and a reaction time of 1.5 hours. Triruthenium dodecacarbonyl was
used as the source of ruthenium. The results are shown in Table 13.
Example 75 -
Example 60 was repeated except a 130 mg (0.42 mmoles) of
9-PHOSPHA, 17 mg (0.21 mmoles) of sodium acetate and 1.0 g of
finely divided activated carbon having ds:posited on its surface 5
cwt of ruthenium metal were used. The EO converted was 63.2 mole
and the selectivity to 3-HPA was 5.0 ~mo.e and to PDO was 54.9
mole.
WO 94/ 8~4~C~ ~~~ ' PCT/EP94/00346
- -
28
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i WO 94/18149 . ~ _ 2 ~. ~ ~ 4 0 PCT/EP94/00346
- 29 -
EO Conv. - mole ~ selectivity -
Example Promoter Mole $ 3-HPA 1,2-PDO
' 68 Yb(OAc)3 59.5 17.5 76.3
69 Eu(OAc)3 50.8 17.1 75.0
70 Y(OAC)3 62.2 19.9 74.5
71 Er(OAc)3 53.2 19.3 73.3
72 La(OAc)3 39.5 17.6 74.9
73 Zn(Oac)2 33.0 4.0 89.2
74 Ca(OAc)2 30.7 17.8 74.2
Illustrative Embodiment VI
In this illustrative embodiment catalysts complexed with the
preferred ligands promoted by the acid/salt promoter of the instant
invention are prepared and tested for hydroformylation of EO and
compared with catalysts which are not promoted by the promoter
system of the instant invention.
In Situ Catalyst Preparation and Hydrofo:rmylation:
Example 1 was repeated, however, using 228 mg (0.66 mmole) of
cobalt 2-ethylhexanoate, 155 mg (0.50 mmole) of 9-PHOSPHA and 33 mg
(0.21 mmole) of calcium acetate. The result is shown in Table 14 as
example 80.
The above example was repeated usin;~ differing amounts of
promoter salt and different promoter sales with the difference that
a reaction time of 1.5 rather than 3 hours was used for examples 82
through 87. The results are shown in Tab:Le 14.
Example C-16 in Table 14 is a comparative example in respect
of embodiment VI, carried out in the same fashion as above, but
without the salt promoter.
WO 94/18149 ~~ PCT/EP94/00346
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WO 94/18149 ~ PCTlEP94/00346
- 31 -
Illustrative Embodiment VII
In this illustrative embodiment catalysts complexed with the
preferred ligands are prepared and tested for hydroformylation of
PO and compared with catalysts prepared j:rom non-preferred ligands.
In Situ Catalyst Preparation and Hydroformylation of P0:
Example 88
Example 1 was repeated, however, using 6.6 g (0.11 mole) of PO
instead of EO and heating the reaction mixture to 90°C for 3 hours.
The homogeneous reaction mixture was removed from the autoclave to
give 29.7 g of a clear liquid. The reaction mixture was analyzed by
gas chromatography and GC/mass spectrometry which showed 4.7~
conversion of PO to 81.0 3-HBA and a sm;311 amount of 2-butenal
by-product. The 2-butenal is thought to he an artifact of the GC
analysis, resulting from decomposition o:E' the 3-HBA on the GC
column. The small amounts of 2-butenal observed upon analysis has
been added to the 3-hydroxybutanal selectivities listed in the
Table 15.
Examples 89-97, C17-C18
Additional examples of PO hydroform:ylation were carried out
using different cobalt precursors, different salt and acid catalyst
promoters and different temperatures and these are shown in Table
15. Examples C17-18 are comparative in respect of Embodiment VII.
Examples 98 to 106
Example 1 was repeated, however, using 62 mg (0.097 mmol) of
t.rirutheniumdodecacarbonyl, 18 mg (0.21 mmol) of sodium acetate,
207 mg (0.66 mmole) of 9-PHOSPHA and 6.6 g (0.11 mole) of P0. The
reaction mixture was stirred and heated at 90°C for 3 hours. The
reaction mixture was removed from the autoclave to give 25.6 g of a
clear, low viscosity upper phase liquid and 3.1 g of a clear, more
viscous lower phase liquid. The two phases were analyzed by gas
chromatography and GC/mass spectrometry which showed 19~ conversion
of PO to products. The reaction product distribution was 2~ acetone
(rearrangement product of PO), 9~ 3-HBA, 87~ 1,3-butanediol and 2~
of miscellaneous products of which the majority was propene. These
results are summarized in Table 16 as example 99. A series of other
WO 94/18149 a~ PCT/EP94/00346
- 32 -
experiments, including comparative experiments, were run under
similar conditions and are shown in Table 16.
Illustrative Embodiment VIII '.,i-; a
In Situ Catalyst Preparation and'.Hydroformylation of 1 2-Epoxvhex-
v .. ~4.
5-ene and 1,2-Epoxyhexane - ~ '
..
Example 107
Example 1 was repeated, however, using 11.4 g (0.11 mole) of
1,2-epoxyhex-5-ene instead of E0 and heating the reactor to 90°C
for 3 hours. The reaction mixture was removed from the autoclave to
give 38.6 g of a homogeneous, clear, amber liquid. The reaction
mixture was analyzed by gas chromatography and GC/Mass Spectrometry
which showed 9.2~ conversion of 1,2-epoxyhex-5-ene to 81.0 3-
hydroxyhept-6-enal and several minor unidentified by-products.
Examples 108 and 109
Example 1 was repeated, however, using 62 mg (0.097 mmole) of
trirutheniumdodecacarbonyl, 18 mg (0.21 mmole) of sodium acetate,
207 mg (0.66 mmole) of 9-PHOSPHA and 11.4 g (0.11 mole) of 1,2-
epoxyhexane. The reaction was stirred and heated at 90°C for 3
hours. T.ie reaction mixture was removed from the autoclave to give
33.15 g of a homogeneous, clear liquid. The reaction mixture was
analyzed by gas chromatography and GC/Mass Spectrometry which
showed 8~ conversion of 1,2-epoxyhexane to products. The reaction
product distribution was 5$ 2-hexanone (rearrangement product of
1,2-epoxyhexane), 50~ 3-hydroxyheptanal, 18$ 1,3-heptanediol and
27~ of miscellaneous products consisting of 1-hexene, pentanal and
other unidentified products.
Another experiment was run under the same conditions with the
exception that the sodium acetate was deleted. Analysis showed 5~
conversion of 1,2-epoxyhexane to products. The reaction product
distribution was 3$ Z-hexanone (rearrangement product of 1,2-epoxy
hexane), 78~ 3-hydroxyheptanal, 0~ 1,3-heptanediol and 19$ of
miscellaneous products consisting of 1-hexene, pentanal and other -
unidentified products.
_ ~~~~~oo
WO 94/18149 ~ ~ PCT/EP94/00346
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