Note: Descriptions are shown in the official language in which they were submitted.
~ 6 ~ 10,556
This invention is concerned with the manufacture
of polyhydric alcohols, their ether and ester derivatives,
and oligomers of such alcohols. This invention also
produces monohydric alcohols such as methanol, and their
ether and ester derivatives.
It is known that monofunctîonal compounds
such as methanol can be obtained by reaction between
carbon monoxide and hydrogen at elevated pressures,
e.g., up to about 1000 atmospheres, and témperatures
ranging from 250C to 500C, using mixtures of copper9
chromium and zinc oxides as the catalyst therefor. It
is disclosed in U.S. Patent No. 2,451,333 that polyhydroxyl
compounds are produced by reaction of formaldehyde,
carbon monoxide, a~d hydrogen in the presence of
hydrogenation catalysts. It h~s-also been reported
that formaldehyde can be produced by reaction between
carbon monoxide and hydrogen at elevated pressures
but repeated attempts to carry out this synthesis of
formaldehyde have invariably ~ailed to yield any
substantial quantity of the desired product. It is
generally recognized that the previously disclosed
processes for the synthesis of formaldehyde from carbon
monoxide and hydrogen at high pressures are either com-
pletely inoperative or else give rise to insignificantly
small quantities o~ formaldehyde.
~ 9 z ~ ~ ~ ' 10,556
In British 655,237, publi,shed July 11, 1951,
there is disclosed the reaction between carbon monoxide
and hydrogen at elevated pre~ures and temperatures, e.g.,
above 1500 atmospher~ at temperatures up t~ 400C., using
certain hydrogenation catalysts as exemplified by cobalt-
containing compounds. U. S. Patents No. 2,534,018,
2,570,792, and 2,636,046 are substantially similar in
disclosure to the above said British patent. The only
catalysts employed in the numbered examples of said
~.S. 2,636,046 are those which contain cobalt.
l It is also well-known that nickel is predomin-
antly a catalyst for synthesis and for reforming,methane
~ccording to the reaction
C0 + 3H2 4 2
whose equilibrium favors the right hand side of the
equation at temperatures below about 500~C. and the left
hand side of the equation at higher temperatures; see
Kirk-Othmer, Encyclopedia of Chemical Technology, Second
' Edition~ ~olume 4, pages 452-453, John Wiley and Sons,
New York (1964).
Polyhydric alcohols are presently being produced
synthetically by the oxidation of petroleum derived
materials. Owing to the limited availability of petroleum
sources 9 the cost of these petroleum derived materials has
been steadily increasing. Many have raised the dire
prediction of a significant oil shortage in the future.
,
'' ' 3.
~ 9 Z 1 ~ 10,556
The consequence of this has been the recognition of the
need for a new lo~ cost source of chemicals which can
be converted into such polyhydric alcohols.
This invention is oriented to the process of
making alkane diols and triols J containing 2, 3 or 4
carbon atoms, and derivatives such as their esters. Key
products of the process of this invention are ethylene
glycol and its ester derivatives. Byproducts of this
invention are the lesser valuable, but valuable never-
theless, monohydric alkanols such as methanol, ethanoland propa~ols, and their ether and ester derivatives.
The products o~ the process of this invention contain
carbon, hydrogen and oxygen.
There is described in U.S. Patent 3,833,634,
issu~d September 3, 1974, a process for reacting hydro-
gen and oxides of carbon in the presence of rhodium
carbonyl complex catalysts. The conditions, broadly
speaking, employed in that process involve reacting
a mixtur~ of an oxide of carbon and hydrogen wi~h a
catalytic amount o~ rhodium in complex combination
with carbon monoxide, at a temperature of between
about 100C. to about 375C. and a pressure of between
about 500 p.s.i.a. to about 50,000 p.s.i.a. The patent
discusses the use of catalyst complexes which have
"ligands" as a component thereof. Illustrative of such
"ligands" are oxygen and/or nitrogen organic compounds.
similar description can be found in U.S. Patent
3,g57,857, issued May 18, 1976, which is commonly
assigned. Both patents speak about the use of such
4.
L
10,556
~ ~ 2~
"ligands" as well as a number of amines which can ~e
used in the catalytic process.
It has been found that such "ligands" and
amines enhance the glycol producing capacity of the
rhodium carbonyl complex catalyst. In that sense, the
"ligands" and amines can be considered to promote the
actîvity of the catalyst. Since the filing of the
applications which issued to U.S. Patent 3,833,634, the
mechanism of action of such "ligands" and amines with
the rhodium carbonyl complex has not been clearly
defined. They may be functioning as ligands and/or
forming counter-ions under the reaction conditions
of the present process or they may be functioning just
merely as Lewis bases and neutralizing or tying up a
molecular species which if allowed to remain "free"
or in its non-bound state would adversely affect
the productivity of the present invention. Because of
this, it is more favorable to look at their presence
in this process in terms of the results they achieve;
hence, for the purpose of this invention they are
defined as catalyst promoters or rhodium carbonyl
complex catalyst promoters.
Even though such promoters were recognized
to be beneficial in such a process for making alkane
polyols as the important product of manufacture, there
was a lack of appreciation that if employed in certain
concentrations the productivity of such polyols would
be materially and unexpectedly enhanced. It has now
. 5.
~ 9 Z ~6 ~ 10,556
been found that there is a specific concentration for
each such promoter which will provide the optimum yield
of alkane polyol that is ob~ainable under each selected
condition of reaction and catalyst concentration.
It follows from ~his that there now exists a recogni-
tion of a specific concentration of such promoter which
creates the most favorable balance between the promoting
and inhibiting effects of such promoters.
The process of this invention, as stated
previously, involves the production of alkane polyols
of two to four carbon atoms. The primary product of
the process is ethylene glycol mainly in terms of
cpmmercial value and secondly in terms of product
efficiency. The process involves providing oxides of
carbon, particula~ly carbon monoxide, and hydrogen in a
homogeneous liquid phase reaction mixture containing a
rhodium carbonyl complex in combination with a nitrogen
Lewis base promotèr. The catalyst concentration, the
. temperature and the pressure during the reaction are
correlated so as to result in the production of alkane
polyol, The promoter provided;to the mixture is present
in an amount determined from the promoter's basicity to
achieve the optimum rate of formation of said alkane
polyol at said correlated catalyst concentration,
temperature 8nd pressure of such reaction mixture.
Suitable nitrogen Lewis bases used as promot-
ers generally contain hydrogen and nitrogen atoms. They
may also contaln carbon and/or oxygen a~oms. They may
be organic or-~norganic compounds. With respect to the
6, ;~
~L~9Zl~ lo, 5s6 i ~'
organic compounds, the carbon atoms can be part of an
acyclic and/or cyclic radical such as aliphatic, cyclo-
aliphatic, aromatic (including fused and bridged)
carbon radicals and the like. Preferably, the organic
Lewis bases contain from 2 to 60, most preferably 2 to
40 carbon atoms. The nitrogen atoms can be in the
form of imino (-N=), amino (-N-), nitrilo (N-), etc.
Desirably, the Lewis base nitrogen atoms are in the
form of imino nitrogen and/or amino nitrogen. The
oxy~en atoms can be in the form of groups such as
hydro~yl (aliphatic or phenolic), carboxyl (-COH),
O
carbonyloxy (-bo-) oxy (-o-) carbonyl (-C-~, e~c.,
all of said groups containing Lewis base oxygen atoms.
In,this respect, it is the "hydroxyl" oxygen in the
O O
-COH group and the "oxy" oxygen in the -CO- ~roup that
are acting as the Lewis base ~toms. The organic Lewis
bases may also contain other atoms and/or groups, as
~- substituents of the aforementioned radicals, such as
alkyl, cycloalkyl, aryl, chloro, trialkylsilyl sub-
stitue`nts.
Illustrative of organic aza-oxa Lewis bases
are, for example, the alkanolamines, such as ethanol-
amine, diethanolamine, isopropanolamine, di-n-propanol-
amine, and the like; N,N-dimethylglycine, N,N-diethyl-
~lycine; iminodiacetic acid, N-methyliminodiacetic
acid; N-methyldiethanolamine; 2-hydroxypyridine,
_
~92~ o, ss6
2,4-dihydroxypyridine, 2-methoxypyridine, 2,6-dimethoxy-
pyridine, 2-ethoxypyridine; lower allcyl substituted
hydroxypyridines, such as 4-methyl-2-hydroxypyridine,
4-methyl-2-6-dihydroxypyridine, and the like; morpho-
line, substituted morpholines, such as 4-methylmorpho-
line, 4-phenylmorpholine; picolinic acid, methyl-
substituted picolinLc acid; nitrilotriacetic acid,
215-dicarboxypiperazine, N-(2-hydroxyethyl)-imino-
diacetLc acid, ethylenediaminetetraacetic acid;
10 2,6-d~carboxypyridine; 8-hydroxyquinoline, 2-carboxy-
quinoline, cyclohexane-1,2-diamine-N,N,N',N'-tetra-
acetic acid, the tetramethyl ester of ethylenediamine-
tetraacetic acid, and the likeO
Illustrative of suitable inorganic amine pro-
moters are, e.g., ammonia, hydroxylamine, and hydrazine.
Any primary, secondary, or tertiary organic amine is
suitable as a promoter in the practice of the present
- invention. This includes the m~no- and polyamines
(such as di-, tri-, tetraamines, etc.) and those com-
20 pounds in which the Lewis base nitrogen fonms part of
a ring structure as in pyridine, quinoline, pyrimidine,
- morpholine, hexamethylenetetraamine, and the like. In
additlon any compound capable of yielding an amino
nitrogen under the reaction conditions of the present
invention is suitable, as in the case of an amide,
~uch as formamide, cyanamide, and urea,
. _ . . . _
~0~ 6~ lo, 556
or an oxime. Further illustrative of these Lcwis base
nitrogen compounds are alipha~ic amines such as methyl-
amine, ethylamine, n-propylamine, isopropylamine, octyl-
amine, dimethylamine, diethylamine, diisoamylamine,
methylethylamine, diisobutylamine, trimethylamine,
methyldiethylamine, triisobutylamine, tridecylamine,
and the like; aliphatic and aromatic di- and polyamines
such as 1,2-ethanediamine, 1,3-propanediamine, N,N,N',N'-
tetramethylenediamine, N,N,N',N'-tetraethylethylene-
diamine, N,N,N',N'-te~ra-n-propylethylenediamine,
N,N,N',N'-tetrabutylethylenediamine, o-phenylene-
diamine, m-phenylenediamine, ~-phenylenediamine,
~-tolylenediamine, o-tolidene, N,N,N',N'-tetra-
methyl-l-phenylenediamine~ N,N,N',N'-tetraethyl-
4,4'-biphenyldiamine, and the like; aromatic amines
such as aniline, l-naphthylamine, 2-naphthylamine,
~-toluidine, o-3-xylidine~ p-2-xylidine, benzylamine,
diphenylamine, dimethylaniline, diethylaniline,
N-Phenyl-l-naphthylamine, bis-(1,8)-dimethylamino-
~0 naphthalene, and the like; alicyclic amines such as
. cyclohexylamine, dicyclohexylamine, and the like;
heterocyclic amines such as piperidine; substituted
piperidines such as 2-methylpiperidine, 3-methyl-
piperidine, 4-ethylpiperidine, and 3-phenylpiperidine;
pyridine; 6ubstituted pyridines such as 2-methyl-
pyridine, 2-phenylpyridine, 2-methyl-4-ethylpyridine,
2,4,~- trimethylpyridine, 2-dodecylpyridine,
2-chloropyridinç, and 2-(dimethylamino)pyridine;
quinoline; substituted quinolines, such as` 2-(dimethyl-
_.. . ... . .
10 ~ 556
amino)-6-methoxyquinoline; 4,5-phenanthroline; 1,8-
phenanthroline; 1,5-phenanthL-oline, piperazine; sub-
stituted piperazines such as N-methylpiperazine,
N-ethylpiperazine, 2-methyl-N-methylpiFe~zine; 2,2'-
dipyridyl, methyl-substituted 2,2'-dipyridyl; ethyl-
substituted 2,2'-dipyridyl; 4-triethylsilyl-2,2'-
dipyridyl; l,~-diazabicyclo[2O2.2]octane, methyl
substituted 1,4-diazabicyclo[2.2.2]octane, purine
and the like.
As stated previously, the promoter is pro-
vided in the homogeneous reaction mixture in an amount
determined from its basicity to achieve the maximum
yield of the alkane polyols, such as ethylene glycol.
For the purposes of discussion o the above provision
of the promoter in the reaction, the promoter shall
be characterized initially in terms of basicity as
either a strong or weak base. However, it is import-
ant to bear in mind that this determination of promoter
concentration predicated on basicity is not intended
to mean that of necessity the promoter is or becomes acation in the homogeneous mixture as noted in the pre-
vious discussion relative to the so-called "ligands"
and amines, and their function in the catalyticreaction.
It has been ~ound that the optimum concen-
tration of a strongly basic nitrogen Lewis base
promoter in the process of this invention is a minimum
concentration that provides the optimum results.
This means th~t a relat~v~ly small amount of
- such promo~er achieves the Qptimum yield obtainable
10.
~ 10,556
with that promoter. On the other hand, it has bcen
found that as the base becomes progressively wealcer,
a ~reater and greater amount of the base is needed to
achieve the maximum yield of the allcane polyol.
The following (defined in terms of an amine
as representative of a nitrogen Lewis base) postulate
possible mechanisms which would result in the observed
behavior discussed above:
a.) the inhibitor function of thè amine
is of higher kinetic order in amine than is the
promoter function;
b.) the promoter function of the amine has
a stoichiometric limit after which only the inhibitor
function of the amine remains.
The term "inhibitor function" means that
function of the amine which results in a decrease in
- alkane polyol yield as amine concèntration increases.
Postulate a. can be illustrated by the
followin~ reaction scheme:
_ 20
(n-m)amine
(I) Rh ~ m(amine) ~ Rh(amine)m ' ~ Rh(amine)n
? *
alkane polyol
Promoter Function ' Inhibitor Fun~tion
* The looped arrow employed herein denotes several
undefined process steps.
;
.
2~
~?'
... ....
10,556
[Note: In the above reaction scheme the charge of
the rhodium carbonyl complex is n~t shown;
n and _ represent integers; Rh denotes a
species with a fixed number of rh~diums with
the option of a chan~in~ number of ~,O's anA
H's; the rate and equllibrium constants
implicitly contain any appropriate C0 and H2
concentrations.]
- In the above scheme, the amine aids produc-
tion of glycol by forming a more active catalyst and
hinders it by inactivating the active catalyst through
a mass law effect. Both of these functions of the
amine involve it as a ligand on rhodium. A conse-
quence of this reaction scheme is that, if the rate
of glycol formation passes through a maximum as a
function of the concentration of the amine, the amine
concentration which corresponds to the maximum increases
as K increases. [Note: K is the equilibrium constant
for dissociation of an amine ligand from rhodium to
yield ~he active catalyst.l Since K would be expected
to be larger for weaker bases, this scheme is consist-
ent with the aforementioned observed results.
A complementary or supplementary reaction
scheme may be characteri~ed as follows:
.
Z~ 0,556
a~ ~
~. o
~O
a~
J~
.,~ ..
.~ ~ U
~ a.~ ~1
._ ' ' '
~ U~' '
~d
Q~
h
,~
..
`
.- . ~J .
~J~.aL~3 ~L 10 ~ 556
In this scheme the aminc functions both as a rhodium-
and as a proton base. It aids production of alkane
polyol by forming a more active catalyst and hinders
it by deprotonating the active catalyst.
- The resulting kinetic equation for reaction
scheme (II) is -
(III)rate is proportional to (Rh) (amine)
m m
Kb(amine) T~
l + (amineH+) ~¦ Kai
- i=l
where the Kai's are successive acid dissociation con-
stants of the active catalyst, Kb is the proton affinity
of the amine.
Equation (III) supports the previously observed
result by showing that if the reaction is treated as
being specific base catalyzed [see: A. A. Frost & ~. G.
Pearson, "Rinetics ~ Mechanism", 2d Ed., John Wiley & Sons
; . (1961)], addition of increasing amounts of amine could
eventually become counter-productive. The equation (III)
predicts that if the nature of the amine affects Kb more
than it does the Kai's, and this is submitted to be a
plausible assumption, the amine concentration corres-
ponding to any maximum in yield of alkane polyol would
be greater the less basic the amine.
A third reaction scheme, illustrative of
postulate b., is characterized as follows:
.
14 .
. .
. 10,556
(IV) ~1 + amine ~ [~l~amine~l~ ~ Rh- ~ aminé~l~]
alkane pol~ol
~Note: Rh is defined as above in the note to equation
; (I).]
- In equation (IV) the amine acts as a promoter
because it helps to produce,the active catalyst and as
an inhibitor because its conjugate acid has an adverse
mass law effect on the equilibrium concentration of a
direct p,recursor of,the acti~e catalyst.
In terms of reaction scheme (I~), with the use
of a less basic amine, more amine would be necessary to.
insure that the first step of the equation'is guantitative.
After enough of such an amine is provided, any further
amine additions can have on'ly negative effects in regards
alkane polyol production because there is a consequent
production of more amineH~,, which serves to decrease Rh-
concentration. A consequence of the reaction scheme (IV)
is that the rate passes through a maximum as a function
.' of amine concentration and that as basicity of the amine
increases the optimum concentration of amine decreases to
a l~miting value co~responding to stoichiometric destructio
of Rh,
_ .
il~0~2~ P~L 10, 556
Consistent ~ith reaction scheme (IV) is the fact
that the optimum concentration of an amine as sole promoter
for Rh is less when the solvent employed has a high
dielectric constant. For example, the optimum
concentration of an amine as the sole promoter in
sulfolane* [~ =43] is less than that in tetraglyme*
=7.5]-
The concentration of the nitrogen Lewis basepromoter in the homogeneous liquid phase mixture of the
process of this invention has not been found to be critic-
ally dependent upon the temperature and pressure^of-the
reaction, the rhodium concentration or the solvent employed.#
Of these factors, the rhodium concentration will have the
more significant impact upon the optimum promoter concen-
tration while ~emperature, pressure and solvent choice
have minimum effect. However, the effect of rhodium
concentration on promoter concentration is considered to
be small and is hereafter discounted except for the purposes
o~ giving numerical values to the selection of an amoun~
of promoter for practicing this invention.
*For a description of the use of sulfolane, see
British Patent Specification No. 1,537,850, published
January 10, 1979, and for a description of tetraglyme,
see U.S. Patent No. 3,957,857, issued May 18, 1976.
#This statement refers to normal operation, which in
tetraglyme involves the use of a salt (see below3 in
addition to an amine as promoter, while the previous
paragraph refers to use of amine as sole promoter in
both solvents.
16.
, , .
~3 ~ 10,556
The ~erms strong or weak base are relative, and
in view of the precedin~ discussion, sucll relative values
are considered appropriate in defining this invention.
However, for convenience and to provide a numerical base
rom which it may be considered desirable to discuss this
invention, one may characterize a strong base as having
a pK greater than about S and a weak base as having a pK
less than 5, with the assu~ption that each is definitive
in the region of a pK of 5. Of course one may give values
more limiting in regards to such pK characteri~ations by
stating that a strong base has a pK o 5 to about 15 and
a weak base has a pK of 0 to aboùt 5. pK refers to
the acid dissociation constant of the conjugate acid of
the nitrogen ~ewis base in water at 25C.
The optimum concentration of an untried promoter
is determinable on a relative scale by comparing the pK
of that promoter to those set forth in Table I below
and selecting a concèntration according to the pK relation-
- ships and trends indicated. Overall,the concentration of
promoter one can employ will be within about 0.001 to about
10 molar. Obviously this range is definitive of the
potential scatter of concentrations predicated on the
varieties of promoter basicity available.
. 170
_ . . . .
- 10~556
TABL~ I
Optimum* Concentration of Amine Promo~er
REACTION SYSTL~-See Examples (below)
Optimum*
Other moles
promoter amine/
~minepK~ Solvent Temp. present mole Rh
1,8 bis(dimethyl- 12.3 Sulfolane 240 - ~ 0.1
amino)-
naphthalene
Sparteine 12.0 " " - 0.2-0.3
" " " 260 - ~0.4-~.7
Dibutylamine 11.3 " 240 - 0,3-0.5
Piperidine 11.1 " 220 - -0.3-0.5
Triethylamine10.7 " 240 - 0,3
N-methyl-
pipPridine 1004 " " - 0.~-0.5
Piperazine 9,7 " 240 - 0.3-0,5
4-dimethylamino-
pyridine 9.6 " 220 - ^~ 0.2
Ammonia 9.3 " 240 -- 0.3
AmberliteTM
IRA-93 9,o ~ _ 0,3_0,5
1,4-diazabicyclo-
[2.2.2] octane 8,8 " 220 -- 0.1
" " " " 240 - 0.2-0.3
2,4,6-trimethyl-
pyridine 7,4 " 240 - 0.2-0.3
N-methylmorpholine 7.4 " " - 0,3-0,4
Trimethylenedi-
morpholine 7.3 " 260 - 0.5
.Pyridine 5.2 " 220 - 0.2-~.3
" " " 240 - ~ 0.1
" " " " (Ph~P)2NO Ac ~ 0.1
" " ~etraglyme 220 ~ 0.2-0.6
" " " " HC02CS 0,2-0.4
" '~ " 230 PhC02CS 0.3-0.6
l,10-phenanthro-
line 4.8 sulfolane240 - 1.6
Aniline 4.6 " " - 2-3
2-hydroxypyridine 0.8 tetraglyme 220 Cs2-pyri~
dinolate
pK of benzyldimPthylamine; 1RA-93 is an arylnlethyl dimethyl
amine ion exchange resin sold by Rohm ~ Haas Co., Phila., Pa.
* The smallest which maximizes the yield o glycol.
~ H20, 25.
.
18.
~0 9 Z~ ~ ~ 10,556
The prec~se role of the rhodium carbonyl
c~mplexes, such as the rhodium carbonyl clusters,
in the reaction of hydrogen with oxides of carbon to
produce polyhydric alcohols is not f~lly appreciated
at present. Under the reaction conditions of the
present process the carbonyl complexes are believed
to be anionic in their active forms. Rhodium carbonyl
anions are known to be involved in the following set
of reactions as indicated by SO Martinengo and P. Chini,
in Gazz. Chim~ Ital., 102, 344 (1972) and the references
cited therein.
(V)
[Rhl2(C0~4_3~ ~' LRh~2(CO ~] ~ ~h6(CO)~] + ~Rh6(CO)
~Rh(CO~
[Rh6(CO)~ ~h(CO~ + CO [Rh7(CO)1;33~Rh4(C0~2- + [Rh(CO)~-
*electron c
Infrared spectra under reaction conditions of
the present process have shown both RhtC0)4 and
~Rhl2(C0)3~_36~ anions, and other rhodium c~usters to
be prese~t at various concentra~ions at different times
of the reaction. Therefore the set of reactions and
equilibria shown in (V) above may represent the active
rhodium carbonyl species responsible for polyhydric
alcohol formation or may be merely symptomatic of some
further intermediate transitory rhodium carbonyl struc-
ture which serves to convert the carbon monoxide and
hydrogen to the polyhydric alcohol.
19 .
Z16~
lo, 556
The novel process is suita~ly effccted over a
wide superatmospheric pressure range of from about 800
psia to about 50,000 psia. Pressures as high as 50,000
psia, and higher can be employed but with no apparent
advantages attendant thereto which offset the unattractive
plant investment outlay required for such high pressure
equipment. Therefore, ~he upper pressure limitation is
desirably approximately 16,000 psia. Effecting the present
process below about 16,000 psia, especially below about
13,0~0 psia, and preferably at pressures below about 8000
psia, results in cost advantages which are associated with
low pressure equipment requirements. In attempting to
foresee a commercial operation of this process, pressures
between about 4,000 psia and 16,000 psia appear to represent
most realistic values.
In a preferred embodiment o~ the present invent-
ion the pressures referred to above represent the total
pressures of hydrogen and oxides of carbon in the reactor.
The process of this invention can also be carried
-20 out by providing salts in the homogeneous liquid phase
reaction mixture. Suitable salts include any organic or
inorganic salt which does not adversely affect the pro-
duction of polyhydric alcohols. Experimental work suggest
that any salt is beneficial as either a copromoter and/or
in aiding in maintaining rhodium in solution during the
react~on. Illustrative of the salts useful in the practice
of the present-invention are the ammonium salts and the
20.
~ ~ Z ~ ~ 10,556
salts of the metals of Group I and Group II of tlle Periodic
Table (Handbook of Cllemistry and Physics - 50th Edition)
for instance the halide, hydroxide, allcoxide, phenoxide
and carboxylate salts such as sodium fluoride, cesium
fluoride, cesium pyridinolate, cesium formate, cesium
acetate, cesium benzoate, cesium p-methylsulfonyl-
benzo`ate (CH3S02C6H4COO)Cs, rubidium acetate, magnesium
acetate, strontium acetate, ammonium formate, ammonium
benzoate and the like. Preferred are the cesium and
ammonium carboxylate salts, most preferably their
formate, benzoate and para-lower alkyl sulfonyl benzoate
salts.
. . Also useful in the practice of the present
invention are organic salts of the following formula:
21.
- . .
10,~56
~ ~ 2 1~ 1
II l R4 - N R2J Y
\ R3
quaternary ammonium salts
: ~ R R
III ~5 -P=~N-~P- R2 J Y
\ 3 /
bis(triorgano phosphine)iminium salts
wherein Rl through R6 in ormulas (II) and (III~
above are any organic radical6 which do not ad-
ve,sely affect the product:ion of polyhydric
: alcohols by reacting oxides of carbon with hydro-
gen in the presence of the ~foredefined rhodium
earbonyl complex, such as a str~ight or branched
chain alkyl group, having from 1 to 20 carbon
atoms in the alkyl chain, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, octyl, 2-
~thylhexyl, dodecyl, and the like; or a
eycloaliphatie group including the monocyclic
and blcyclic groups eyelopentyl, cyclohexyl,
and bicyclo~2.2.1] heptyl groups, and the like
22.
. . _ . . .
Lfi IL
10 7 556
or an aryl, alkylaryl, or aralkyl group such as
phenyl, naphthyl, xylyl, tolyl, t-butylphenyl, benzyl,
beta-phenylethyl, 3-phenylpropyl and the like; or a
functionally substituted alkyl such as beta-hydroxy-
ethyl, ethoxymethyl, ethoxyethyl, phenoxy~thyl, and
the like; or a polyalkylene ether group of the formula
~CIlH2nO)X-OR wherein n has an average value from 1 to
4, x has an average value from 2 to about 150, and R
may be hydrogen or alkyl of 1 to about 12 carbon
atoms. Illustrative of such polyalkylene ether groups
are poly(oxyethylene~, poly(oxypropylene), poly(oxy-
ethyleneoxypropylene), poly(oxyethyleneoxybutylene~,
and the like. Y in formulas II and III above may be
any anion which does not adversely affect the produc-
tion of polyhydric alcohols in the practice of the
present invention such as hydroxide; a halide, for
instance fluoride, chloride, bromide and iodide; a
carboxylate group, such as formate, acetate, propionate,
and benzoate and the like; an alkoxide group such as
methoxide, ethoxide, phenoxide, and the like; a
functionally substituted alkoxide or phenoxide group
such as methox~ethoxide, ethoxyethoxide, phenoxy-
ethoxide and the like; a pyridinolate or quinolate
group; and others. Pre~erably Y in formulas II and III,
above, is a carboxylate, most preferably formate,
acetate and benzoate~
A suitable method for preparing the bis(tri-
organophosphine) iminium salts is disclosed in an
article by Appel, R. and Hanas, A. appearing in
Z. Anorg. u. Allg. Chem., 311, 290, (1961).
23.
~6
lO,556
Other organic salts u~eful in the practice
of the present invention include the quaternized hetero-
cyclic amine salts such as the pyridinium7 piperidinium,
morpholinium, quinolinium saltc and the like, e.g., N
ethylpyridinium fluoride, N-methylmorpholinium benzoate,
N-phenylpiperidinium hydroxide, N,N'-dimethyl-.2,2-
bipyridinium acetate, and the like.
In addition, the anion of the above salt may
be any of the rhodium carbonyl anions. Suitable rhodium
.10 carbonyl anions include 1Rh6(CO)15] ; [Rh6(CO)15Y]
wherein Y may be halogen, such as chlorine, bromine, or
iodine, [Rh6(C0)15(COOR"] wherein R" is lower alkyl or
aryl such as methyl, ethyl, or phenyl; [Rh6(CO)14]
[ 7( )16] ; [Rhl2(c0~o~2 ; Rhl3(oo~4~ ;and Rh~(C0~4H22
Under reaction conditions where a salt is employed
the salt is desirably added ~ith the intial charge of re-
actants in amount~ of from about 0;5 to about 2.0 moles,
preferably from about 0.8 to about 1.6 moles, and most
preferably from about 0.9 to 1.4 moles of salt for every
five atoms of rhodium present in the reaction mixture.
Illus~rative solvents which are generally suit-
able in making the homogPneous mixture include, for
example, ethers such as tetrahydrofuran, tetrahydropyran,.
diethyl ether, l,2 dimethoxybenzene, l,2-diethoxybenzene,
the mono- and dialkyi ethers of ethylene glycol, of
propylene glycol, of butylene glycol, of diethylene glycol,
of dipropylene glycol, of triethylene glycol, of tetra-
ethylene glycol, of dibutylene glycol, of oxyethylene-
propylene glycol, etc; alkanols such as methanol, ethanol,
.
- 24.
~ ~2 ~ 10,556
propanol, isobutanol, 2-ethylhexanol, etc.; ketones such
as acetone, methyl ethyl keton~, cyclohexanone, cyclo-
pentanone, etc.; esters such as methyl acetate, ethyl
acetate, propyl acetate, butyl acetate, methyl propionate,
ethyl butyrate, methyl laurate, etc.; wat~r; gamma-
butyrolactone, delta-valerolactone; substituted and
unsubstituted tetrahydrothiophene-l,l-dioxides (sulfolanes)
as disclosed in British Patent Specification No. 1,537,850,
published January 10, 1979; and others. The mono
and dialkyl ethers of tetraethylene glycol, gamma-butyro-
lactone, particularly sulfolane and 3,4-bis(2-methoxy-
ethoxy)sulfolane, are the preferred solvents.
The temperature which may be employed can vary
over a wide range of elevated temperatures. In general,
the process can be conducted at a temperature in the range
of from about 100C. and upwards to approximately 375C.,
and higher. Temperatures outside this stated range are
not excluded from the scope of the invention. At the
lower end of the temperature range, and lower, the rate
of reaction to desired product becomes markedly slow. At
the upper temperature range, and beyond, signs o~ some
catalyst instability are noted. Notwithstanding this
factor, reaction continues and alkane polyols and /or
thèir derivatives are produced. Additionally, one
should take notice of the equilibrium reaction for forming
ethylene glycol
2 CO + 3H ~ HOCH CH OH
At relatively high temperatures thè~-equilibrium increasing-
ly favors the left hand side of the equation. To drive the
~ 9 ~ 10,556
reaction to the formation of increased quantities o~
e~hylene glycol, higher partial pressures of carbon
monoxide and hydrogen are required, Processes based
on correspondingly higher pressures, however, do not
represent preferred embodiments of the invention in view
of the high investment rosts associated with erecting
chemical plants which utilize high pressure utilit~es
and the necessity of fabricating equipment capable of
withstanding such enormous pressures. Suitable tempera-
tures are between about 150C to about 320DC, and
desirably from about 210C to about 300C.
The novel process is effected for a period oftime sufficient to produce the alkane polyols and/or
der~vatives thereof. In general, the residence t~me can
vary from minu~es to severa:L hours, e.g., ~rom a few
minutes to approximately 24 hours, and longer. It is
readily appreciated that the residence period will be
-- ~nfluenced to a significant extent by the reaction tem-
perature, the concentration and choice of the catalyst,
the total gas pressure and the partial pressures exerted
by its componentsg the concentration and choice of
diluent, and other factors. The synthesis of the
desired product(s) ~y the reaction o hydrogen with an
oxide of carbon is suitably conducted under operative
.conditions which give reasonable reaction rates and/or
converslons. ~
The relative amounts of oxide of carbon
- and hydro~cn which are initially present in the
26.
. . .
~3~16.~ lo, 556
reaction mixture can be varied over a wide range.
In general, the mole ratio of CO:H2 is in the
range of from about 20:1 to about 1:20, suitably
from about 10:1 to about 1:10, and preferably
from about 5:1 to about 1:5.
It is to be understood, however, that
molar ratios outside the aforestated broad range
may be employed. Substances or reaction mixtures
which give rise to the formation of carbon monoxide
and hydrogen under the reaction conditions may be
employed instead of mixtures comprising carbon
monoxide and hydrogen which are used in preferred
embodiments in the practice of the invention.
For instance, polyhydric alcohols are obtained by
using mixtures containing carbon dioxide and
hydrogen. Mixtures of carbon dioxide, carbon
monoxide and hydrogen can also be employed. If
desired, the reaction mixture can comprise stea~
and carbon monoxide.
The novel process can be executed in
a batch, semi-continuous, or continuous fashion.
The reaction can be conducted in a single reaction
zone or a plurality of reaction zones, in series
or in parallel, or it may be conducted inter-
mittently or continuously in an elongated tubular
zone or series of such zones. The material of
construction should be such that it is inert
27.
~ 10,556
during the reaction and the fabrication of
the equipment should be able to withstand the
reaction tem~erature and pressure. The reaction
zone can be fitted with internal and/or external
heat exchanger(s) to thus control undue tempera-
ture fluctuations, or to prevent any possible
"run-away" reaction temperatures due to the
exothermic nature of the reaction. In preferred
embod-iments of the invention, agitation means to
vary the degree of mixing of the reaction mixture
can be suitably employed. Mixing induced by
vibration, shaker, stirrer, rotatory, oscillation,
ultrasonic, etc., are all illustrative of the
types of agitation means which are contemplated.
Such means are available and well-known to the art.
The catalyst may be initially introduced into the
reaction zone batchwise, or it may be continuously
or intermittently introduced into such zone during
the course of the synthesis reaction. Means to
~0 introduce and/or adjust the reactants, either
intermittently or continuously, into the reaction
; zone during the course of the reaction can be
conveniently utilized in the novel process e~pecially
to maintain the desired molar ratios of and the
partial pressures exerted by the reactants.
28.
~ 10,556 i~;
As intimatcd previously, thc operative conditions
can be adjusted to optimize the conversion of the desired
product and/or the economics o~ thc no~el process. In a
continuous process, ~or instance, when it is preferred to
operate at relatively low conversions, it is generally
desirable to recirculate unreactedsynthesis gas with/with-
out make-up carbon monoxide and hydrogen to the reaction.
Recovery of the desired product can be achieved by mcthods
well-known in the art such as by distillation, fraction-
ation, extraction, and the like. A fraction comprising
rhodium catalyst, generally contained in byproducts and/or
normally liquid organic diluent, can be recycled to the
re~action zone, if desired. All or a portion of such
fraction can be removed for recovery of the rhodium values
or regeneration to the ~ctive catalyst and intermittently
added to the recycLe stream or directly to the reaction
zone.
The active forms of the rhodium carbonyl clusters
_ may be prepared by various techniques. They can be
preformed and then introduced into the reaction zone or
they can be formed in situ.
The equipment arrangement and procedure which
provides the capability for determining the existence of
anionic rhodium carbonyl complexes or clusters having de-
fined infrared spectrum characteristics, during the course
of the manufacture of polyhydric alcohols from carbon
monoxide and hydrogen, pursuant to this invention is
29~
~3~ 10,556
dîsclosed and schematically depicted in U.S. Patent
3,957,857, issued May 18, 1976.
A particularly desirable infrared cell construct-
ion is described în U.S. Patent No. 3,886,364, issued
May 27, 1975.
The "oxide of carbon" as covered by the claims
and as used herein is intended to mean carbon monoxide
and mixtures of carbon dioxide and carbon monoxide,
either introduced as such or formed in the reaction.
Preferably, the oxide of carbon is carbon monoxide.
The following examples are merely illustrative
and are not presented as a definition of the limits
of the invention:
.
30.
10,556
Procedure employed in examples:
A 150 ml. capacity stainless steel reactvr
capable of withstanding pressures up to 7,000 at-
mospheres was charged with a premix oE 75 cubic
centimeters (cc) of solvent, 3.0 millimoles ~mmol),
0.77 grams, of rhodium dicarbonylacetylacetonate, and
promoter(s). The reactor was sealed and charged with
a gaseous mixture, containing equal molar amounts of
carbon monoxide and hydrogen, to a pressure of 8,000
pounds per square inch (psig). Heat was applied to
the reactor and its contents; when the temperature of
the mixture inside the reactor reached 190C, as
measured by a suitably placed thermocouple, an addi-
tional adjustment of carbon monoxide and hydrogen
(H2:C0=1:1 mole ratio) was made to bring the pressure
back to 8000 psig. The temperature (in G.) was main-
tained at the desired value for 4 hours. During this
period of time additional carbon monoxide and hydrogen
wa~ added whenever the pressure inside the reactor
dropped below about 7500 psig. With these added
repressurizations the pressure inside the reactor was
maintained at 8000 psig ~ 400 psig over the entire
4 hour period.
After the 4 hour period, the vessel and its
contents were cooled to room temperature, the excess
gas v~nted and the reaction product mixture was removed.
~z~
10 556
Analysis of the rcaction product mlxture was made by
gas chromatographic analysis using a Hewlett Packard
FM TM model 810 Research Chromatograph.
Rhodium recovery was detenmined by atomic
absorption analysis of the contents of the reactor
after the venting of the unreacted gases at the end
of the reaction. A further analysis was run on a
"wash" of the reactor. The wash of the reactor oon-
sisted of charging to the reactor 100 cc of the
solvent used for that experiment, and bringing the
reactor and its contents to a temperature of 160C
and a pressure of 14,000 to 15,~00 psig and main-
taining these conditions for a period of 30 minutes.
The reactor was then cooled and the unreacted gases
vented and an atomic absorption analysis for rhodium
was run on the reactor's contents. The rhodium
recovery values recited below are the percent
rhodium based on the total rhodium charged to the
reactor that is soluble or suspended in the reaction
mixture plus the wash after the specified reaction
time.
The same equipment and procedure were used
in all the examples in Tables A-V except for the
- reactants and conditions specified. The product
weights in the Tables are reported in grams.
.
;
32.
. . _ .
3~61 lo, ss6
lXAMPLlS
Table A. 1,8-Bis(dimcthylamino)-laphthalene as Promoter
~ miili~ Weight of
Conditions moles Product
and other of Amine
Reactant~ Promoter Methanol Glycol Rh Recover~, %
Sulfolane,
24~ 0.20 2.4 0.8 34 ~ 5
" " 0.31 2.9 6.0 78 ~ 3
" " 0.63 2.7 5.1 67 + 4
" " 0.94 2 8 5.0 66 + 3
" " 1.25 3.7 5.5 69 + 5
" " 2.5 2.7 4.6 72 ~ 4
" !' 5.0 3 7 4.3 85 ~ 2
" '' . 7.0 4.4 4.8 83 ~ 7
Table B. Sparteine as Promoter
milli~. .
Condi~ions moles Weight of
.and other of Amine Product
~ reactants Promoter Methanol Glycol Rh Recovery %
20 Sulfolane,
240 0.31 2.9 0.3 65 + 6
" " O.G3 3.3 5.7 79 + 8
" " 1.25 3,9 4.8 80 + 8
" " 5.0 ~.9 0.6 94 ~ 6
Sulfolane,
260~ 0.6 4 9 5.0 66 ~ 4
" " 1.25 5.1 6.3 84 ~ 5
" " 2.0 6.4 6.9 71 + 5
" " 3.0 5.4 . 4.8 83 + 5
.
33.
2 ~ 6
10,556
Table C, ~ib-ltylamine as Prom,oter.
. . ,~.
milli-
Conditions, n~oles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol _ Recovery, %
Sulfolane,
240 0.65 2.7 5.477 + 5
" " 1.25 3.5 6.277 + 6
" " 2.5 .4.3 4.986 + 5
" " '5.0 ' 4.7 4,077 + 6
'
0 ' Table D. Piperidine as Promoter ,
milli-
Conditions moles Weight of
and other of Amine _ Product
reactants Promoter Methanol Glycol Rh Recovery, %
Sulfolane,
' 22~ 0 0,4 0,011 ~ 21
" '" ' 0.63 1.2 1.574 + 7
" " 1.25 2.7 2.589 + 8
" " 2.5 3.4 2.294 + 6
.
Table E. Triethylamine as Promoter
milli- '
20 Condi tions moles Weight of
and ather of Amine _ Product
reactants Promoter Methanol Glycol ~ Recovery~_~
Sulfolane,
240 0.65 3.3 2.~71 ~ 7
" " 0.8 2.8 5.580 ~ 7
. " " 1.25 3,5 5.179 + 5
' " " 2,5 5,0 . 4.0' 81 + 8
." " 7.0 ~.~ 2,280 ~ 8
. 34.
L61 .
lo, 556
Table F. N-M~tllylpipcridine as Pr~moter
m;~
Conditions moles Weight of
and other of ~mine Product
reactants ~romoter Methanol Glycol ~t Recovery, %
Sulfolane,
240 0.63 3.0 3.0 66 + 3
" " 0.94 2.6 5.0 ~ ~ 65
" " 1.25 3.5 4.9 69 + 7
. " " 2,5 4.5 3,8 86 ~ 7
. Table G. Piperazine as Promo~er
milli- Weigkt of
and other of Amine Product
reactants Promoter Methanol G1YCO1 Rh Recovery, %
Sulfolane,
240 0.~5 2.5 4.6 60 + 14
" " 1.25 3,8 6.1 71 + 6
" " 2,5 4.6 5.1 83 ~ 4
Table H. 4-Dimethyiaminopyridine as Promoter
milli-
Conditions moles Weight of
and other of Amine Product
eactants Promoter Methanol Glycol Rh RecoverY, V/~
Sulfolane,
~ 220 ~ ~.4 0,O 11 + 21
" " 0.31 1.6 1.3 74 ~ 4
" " 0.63 2.6 2.3 90 + 9
" 1.25 3.3 1,6 92 + 8
.
. 35.
-
10,~56
Table 1. Ammonia as Promo~er
Conditions mmoles Wei~ht of Productand other of Amine
reactants Promoter _ethanol ~y~ Rh Recovery, %
Sulfolane,
`240 0.50 2.7 4.3 63 + 15
" " 0.65 2.2 4.7 79 ~ 5
" " 0.8~ 2.3, 2.4 4.9, 5.~ 81 + 6, 86 ~ 5
" " 1.0 3.2, 3.6, 2.8 6.6,5.3,5.2 84+6,77~,83+7
~' 1 1.~5 ~7, 3.3, 3.1 5.2,5P,S.1 69+4,8~+4,84+5
" " 1.5 3.6 4.8 81+5
" " 2.0 4.6 4.6 83+8
" " 2.5 4.6 4.8 78 + 5
" " 10. 2.3 1.6 84 + 5
~ .
Table J. AmberliteTM IRA- 93 as Promoter
_
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter* Methanol G1YCO1 Rh reCOVerY**~ %
.
Sulfolane,
240 0.62 1.8 3.9 51
" " 1.25 3~0 5.8 82
" " 2,5 3,0 5.0 63
" " 10. 2.7 3.2 64
mmoles of nitrogen.
** Wash not analyzed for rhodium,
36.
9~6~L
10, 5~6
Ta'ble K. 1,4DDiazab~cyclol2.2,2]octane ~s Promoter
Conditions ~noles ~eight of
and other of Amine Product
reactants Promoter Methanol Glycol Rh Recovery~ %
Sulfolane,
220 0 0.~ ~).0 11 ~ 21
" " 0.31 1.4 0.9 71 + 3
" " 0.63 -1.2 3.5 81 + 7
" " 1.25 2.9 2.6 87+6
" " 2.50 2.8 1.5 90 + 3
Sulfolane,
240 0.31 2.8 0.5 41 + 11
0 . 6 33 . 1 6 . 5 7 5 ~ 6
" " 1.25 4.4 6.1 76 + 4
" " 2.5 4.3 4.5 74 + 6
" " ~.0 4.4 3.7 75 + 7
Table L. 2.4,6-TrimethYlE~ridine as Promoter
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter Meth~nol Glycol Rh Recovery, %
Sulfolane,
240 0.31 2.6 1.0 60 + 3
" " 0 63 5 5.0 77 + 6
" " 1 25 3 6 4.3 71 + 4
" " 2.5 4.5 3.3 77 + 4
" " 5.0 4.9 2.5 76 + 3
37 .
Z~L6~
lo, 556
Table M. N-MeLIlylmorpholil-c as Promoter
~_ ... - . .
Conditions mmoles!~ Weigllt of
and other of ~mine Product
reactants Promoter Methanol Glycol Rh Recovery, %
_
Sulfolane,
2~0 0.63 3,2 4.2 66 + 5
" " 1.25 3,2 5.8 64 + 4
" " 2,5 4.5 5.4 74 + 4
" " 5.0 3.6 5.3 80 ~ 4
ll '' 7.0 4.1 5.4 82 + 2
Tetraglyme,
240,
0.65 mmoles
cesium
benzoate 0 2.2 2.9 27 + 52
" " 5,0 2.4 4.1 46 ~ 32
" '~ 10.0 1.7 3.0 12 + 64
Sulfolane,
250C 7.0 3.6 6.4 64 + 3
" " 11 0 4.6 6.0 67 + 7
" " 20 5.4 5.4 69 + 6
Table N. Trimethylenedimorpholine as Promoter
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol Rh Recovery, V/o
.
Sulfolane,
260 0.65 3.3 3,2 49 + 4
" " ~.25 4.~ 5.6 67 ~ 6
" " 7.0 4.9 6.1 78 ~ 6
" " 12.0 5.1 6.0 77 ~ 5
38,
.
10,556
~ ~ 2 1 6
Table O. Pyridine as Pr~moter
Conditions mmoles Weight of
and other of Amine Product Rh Recovery~ %
Reactants Promoter Methanol G~ycol
Sulfolane
220 0 0.4 0.0 11 + 21
" " 0.31 1.9 0.5 66 + 6
" " 0.63 2.2 3.8 91 + 8
" " 1.25 3~3 2.1 87 ~ 7
" " 2.50 3.4 1.2 97 + 7
Sulfolane,
240 0.31 2.4, 2.6 2.1,5.7 74 +4, 82+2
" " 0.63 2.7 5.7 76 + 4
" " 0.94 3.0 5.2 73 + 6
" " 1.25 3.4 4.7 76 + 3
" " 2.5 3.5 3.4 79 + 2
" " 5O0 2.6 2.0 87 + 3
Sulfolane,
240
0.75 mmoles
bis(triphenyl-
phosphine)
iminiun
acetate, i.e.
(Ph P) NOAc 0 3.2 5.2 79 + 4
" 3" 2 l~ 0.15 3-9 5.6 80 + 2
" " " 0.30 4.1 5.9 91 + 7
" " " 0.60 4.7 5.2 84 + 5
" " " 1.25 ~.4 4.3 73 + 7
Tetraglyme,
220
0.63 mmoles
(Ph P) NOAc0.63 1.4 5.3 91 + 7
" 3" 2 l ~.25 1.4 5.0 85 + 8
" " " 2.5 105 4.5 82 + 7
Tetraglyme,
0.5 mmoles
HCO Cs 0 1.2 2.8 69 + 3
"2" ~ 0.63 2.0 3.1 7~ + 13
" " " 1 25 2.2 3.1 78 + 12
~ " " " 2 5 2.8, 2.8 2.4, 2.5 74 + 9, 77+15
.. .. l 5.0 2.6 2.8 74 + 7
tt ~I ~1 10.0 3.2 2.2 78 + 6
"" " 20.0 3.1 1.6 72 + 7
39.
. 10,556
Table 0 (continued)_ PyrLdi.ne ~s Promoter
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol ~1 Recovery, %
Tetraglyme,
23no
....... .Ø65 mmole
cesium
. benzoate 0 2.2 3.5 63 + 24
" " 1.25 2,2 4.6 50 + 31
" " 2.5 3.3 5.2 65 + 22
ll " 5.0 3.5 4.6 66 + 5
Tetraglyme,
240,
0.65 mmole
cesium
benzoate 0 2.2 2.9 27 + 52
" " 1.25 2.6 3~6 42 + 38
" ~ " 5.0 1.4 2.1 10 + 72
Sulfolane,
250 0.63 3.8 6.4 68 + 9
" " 2.5 6.3 5.5 93 + 11
Table P. l,10-Phenanthroline as Promoter
ConditionS mmoles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol Rh Recovery %
Sulfolane,
240 0.50 3.4 1.7 61 + 6
" " 1.0 3.3 2.4 76 + 6
" " 2.0 3.6 4.0 76 + 6
" " 3.0 3,4 4.4 73 ~ 4
" " 5.0 3.4 5.3 77 + 5
" " 7.01.7, 2.~ 2.6 3.0,3.9,3.9 56+3,69+4,74+4
" " 10,03~0, 2.7 4.7,4.~ 77+3,77+~
" " 15, '3.2 4.9 74 ~ 5
" " 20. 2.5 4.3 77 ~ 5
_ 40
3Z~6.1~
o, 5s6
, .
Conditionsmmoles ~leight of
and otllerof Amine Product
reactants Promoter Methanol Glycol ~l Rccovery, %
Sulfolane,
2405.0 3.1 2,5 70 + 5
" " 10.0 2,9 3,3 64 + 10
" " 20, 2,2 3,1 61 + 9
Table R. 2-Hydroxypyridine as Pr~moter
Conditionsmmoles Weight of
~nd otherof Amine Product
reactants , Promoter Methanol Glycol Rh Recovery, %
Tetraglyme,
220,
0.5 mmole Cs
2-pyridino- .
late, 6mmoles
Rh(CO)2 acetyl-
acetonate 3.0 2,9 5,7 78 + 6
" " " 6.0 2,8 6.1 78 + 6
" " " l~.0 2,8 5.4 74 + 6
" " '' 20, 4.3 4.5 83 + 8
-_ Table S. Q_~nuclidine as Promoter
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol Rh Recover~ %
Sulfolane,
2~0 0 0.4 0,0 11 + 21
" " ~.63 2.5 3.5 7~ ~ 7
3~ " " 1.25 4.1 1.7 90 + 9
41,
.
9 2 ~ ~ ~
10,556
Table T. EthY~en~dim_rpholine as Promoter
Cond~tlons mmole~ We~ght of
and other Qf Amine Product
reactants Promoter Methanol Glycol h RecoverY, %
Sulfolane,
240 0.65 3.0 6.3 89 ~ 5
" " 1.25 3.5 6.3 78 + 5
" " 7.0 .- 4,6 4.9 78 ~ 5
Table U. TetramethYlened~morPholine as Promoter
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol Rh RecoverY. /~
Sulfolane,
260 0.65 3.~ 4.2 68 ~ 5
" " 1.25 4.5 5.3 73 + 5
~ I' 7.0 3.6 3.2 72 + 3
Table V. Hydroxypyrid~nes 8S PrGmoter
Conditions mmoles Weight of
and other of Amine Product
reactan~s Pr~moter Methanol G1YCO1 Recovery, %
DehydroxYPYridine (see Table O) (pK c 5.2)
2-Hvd~_r~ t (see also Table R) (pK = 0.8)
Tetraglyme,
220,
0,75 mmole
(Ph3P)2
NOAc 1.25 1.6 ~.7 82 + 6
Tetraglyme,
220 10.0 1.9 1.0 70 ~ 19
3~ Tetraglyme,
220,
0.5 mmole
Cs 2-pyrid- ~
inolate 10.. ~ 1.7 4.3 82 + 15
42.
10,5s6 ~ t .
Table V (contin~led~ ~ydroxy~yridin .~; Pro~ot~
Conditions mmoles Weight of
and other of Amine Product
reactants Promoter Methanol Glycol Rh Recovery, %
3-Hydroxypyridine (pK = 4.8)
Tetraglyme,
220 .10.0 . 3,2 0.4 99 ~ 15
Tetraglyme,
220
: 10 0,5 mmole
Cs 2-pyridin-
olate 10.0 2.5 2.3 85 + 13
Tetraglyme,
220,
0.75 mmole
(Ph3pl)2NoAc 1.25 ~ 5 2 ~ 8756 ++
4-Hydroxypyridine ~pK = 3.2)
Tetraglyme,
220 10.0 2.4 0.6 88 ~ 17
Tetraglyme,
220,
0.5 mmole
Cs 2-pyrid- -
inolate 10.0 . 2.6 1.5 78 + 10
Tetraglyme,
220
0.75 mmole
(Ph~P)2NOAc 3.0 1.3 4.6 87 ~ 9
" _ 1.5 2.9 76 + 11
- ` 43.
..
_
,
6 ~
10,556
Materials used in the examples possessed
the follo~ing characteristics: cesium benæoate
(recrystallized from H20, Analysis - Found: C, 32.62;
H, 1.90. Calcd. for C7H502Cs: C, 33.10; H, 1.98);
sparteine (bo 288-90); quinuclidine (sublimed, mp 161-2)
trimethylenedimorpholine [bo 5 ~100, nmr(CDC13) :
~= 6.2-6.5 (m, 8.0H), 7.4-7.8 (m, 12H) 8.1-8.6 (m, 2.0H)
tetramethylenedimorpholine [mp 51-4, nmr (CC14) :
~= 6.3-6.6 (m, 8.0H~, 7.5-7.9 (m, 12H), 8.4-8.7 (m, 4.0H).
44.
