Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) vanadium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.

CROSS-REFERENCE TO RELATED APPLICATION 
Our copending application, Ser. No. 280,218, filed concurrently herewith, 
assigned to the assignee hereof, and hereby expressly incorporated by 
reference in its entirety and relied upon. 
BACKGROUND OF THE INVENTION 
1. Field of the Invention: 
The present invention relates to the hydrocarbonylation and/or 
carbonylation of alkyl carboxylates, in particular methyl carboxylates and 
alkyl acetates, in the presence of water. The subject process is, 
moreover, conveniently represented by the following equation: 
EQU R--CO--O--R'+CO+H.sub.2 .fwdarw.R'--CO--O--CH.sub.2 --R', 
R--CO--O--CH.sub.2 --R', R'--CH.sub.2 --OH, R'--CHO, R--CO--OH, 
R'--CO--OH. (1) 
in which R represents a linear or branched chain alkyl radical having from 
1 to 16 carbon atoms, a cycloalkyl radical having from 3 to 6 carbon 
atoms, a phenyl radical (C.sub.6 H.sub.5 --), a radical C.sub.6 H.sub.5 
--C.sub.x H.sub.2x -- or a radical C.sub.x H.sub.2x+1 --C.sub.6 H.sub.4 
--, with x being an integer ranging from 1 to 6 (1.ltoreq.x.ltoreq.6), and 
R' represents a linear or branched chain alkyl radical having from 1 to 5 
carbon atoms or a radical C.sub.6 H.sub.5 --C.sub.x H.sub.2x --, with x 
being as above defined, it also being possible for R and R' to be 
identical. 
The process according to this invention is admirably suited to the 
preparation of one or more of the compounds acetaldehyde, acetic acid, 
ethanol and ethyl acetate, from methyl carboxylates, and especially from 
methyl acetate. 
2. Description of the Prior Art: 
Certain authors (compare Journal of the American Chemical Society, 100: 19, 
1978, pages 6,238--6,239) have reported that it is possible to prepare, in 
particular, ethyl acetate by the hydrocarbonylation of methyl acetate in 
the simultaneous presence of ruthenium, an iodine-containing promoter and 
a proton donor (which is either the HI initially employed in the reaction, 
or formed in situ from CH.sub.3 I, or a carboxylic acid). 
However, the industrial-scale development of a technique of this type, the 
value of which is not contested in principle, is markedly compromised by 
the low activity of the catalyst system used. 
It has recently been proposed (compare French Patent Application No. 
78/20,843) to carry out such reaction in the presence of a cobalt salt and 
iodine. However, the high pressures required for the catalyst system to 
develop an acceptable activity hardly make it possible to envisage 
industrial development of such a process. 
Parallel to this, examination of the specialized literature reveals that 
numerous attempts to hydrocarbonylate methanol in order to selectively 
obtain either acetaldehyde or ethanol have not resulted in satisfactory 
solutions. A survey of the various techniques proposed for this purpose 
can be found, for example, in the introductory portion of U.S. Pat. No. 
4,133,966. 
It is clearly apparent from this analysis that it would be desirable to 
have available an efficient process which makes it possible, if 
appropriate, to prepare aldehydes, carboxylic acids, "homologous" 
alcohols and, more particularly, alkyl carboxylates from their lower 
homologs. The term "homologous alcohol" is to be understood as connoting 
the alcohol R'--CH.sub.2 --OH shown in equation (1) above, which thus 
contains one carbon atom more than the alcohol (R'--OH) from which the 
starting ester is derived. A first category of alkyl carboxylates which 
can be obtained according to the present invention is represented by the 
formula R--CO--O--CH.sub.2 --R' in equation (1) above. This type of ester 
contains one carbon atom more than the starting ester and can thus be 
considered as a "higher homolog" of the starting ester. To simplify the 
account below, the alkyl carboxylates of the formula R'--CO--O--CH.sub.2 
--R' shown in equation (1) above will also be referred to as "homologous 
esters". 
SUMMARY OF THE INVENTION 
Accordingly, and which is a major object of the present invention, a novel 
process is hereby provided which quite unexpectedly, enables 
hydrocarbonylation and/or carbonylation of alkyl carboxylates in an 
aqueous medium in order to obtain one or more of the compounds comprising 
the carboxylic acids, aldehydes, alcohols and homologous alkyl 
carboxylates, according to equation (1) above, in an extremely efficent 
manner, provided that the reaction is carried out in the presence of 
hydrogen, ruthenium, cobalt, at least one iodine-containing promoter and 
vanadium (or a vanadium compound). 
DETAILED DESCRIPTION OF THE INVENTION 
More particularly according to this invention, one of the essential 
constituents of the catalyst system consistent herewith is ruthenium. The 
precise form in which the ruthenium is employed in the reaction is not 
critical. Ruthenium carbonyls, such as Ru.sub.3 (CO).sub.12, [Ru(CO.sub.3 
Br.sub.2 ].sub.2 and Ru(CO).sub.4 I.sub.2, and more generally any 
ruthenium compound which is capable of giving rise to, under the reaction 
conditions, the appearance of ruthenium carbonyls in situ, are 
particularly suitable for carrying out the subject process. Ruthenium 
metal in finely divided form, ruthenium tribromide, ruthenium triiodide, 
ruthenium carboxylates (in particular ruthenium acetate) and ruthenium 
acetylacetonate are exemplary in this respect. 
The amount of ruthenium to be used is also not critical. As the proportion 
of ruthenium in the reaction medium has a beneficial influence on the 
reaction rate, it will be determined as a function of the rate which it 
will be judged suitable to attain. 
In general, an amount ranging from 0.5 to 100 milligram atoms or ruthenium 
per liter of reaction medium (mg atoms/liter) affords satisfactory 
results. The reaction is preferably carried out with a proportion of 
ruthenium ranging from 1 to 50 mg atoms/liter of ruthenium. 
The second essential, or critical constituent of the catalyst system is 
cobalt. Any source of cobalt which is capable of reacting with carbon 
monoxide in the reaction medium to provide cobalt carbonyl complexes can 
be used within the scope of the present process. 
Examples of typical sources of cobalt are finely divided cobalt metal, 
inorganic salts, such as cobalt nitrate or carbonate, and organic salts, 
in particular carboxylates. Cobalt carbonyls or hydrocarbonyls can also be 
employed. 
Cobalt formate, acetate and halides, and more particularly cobalt iodide, 
and dicobalt octacarbonyl are also exemplary of the cobalt derivatives 
suitable for carrying out the process according to the invention. 
The precise amount of cobalt employed in the reaction too is not of 
fundamental importance. In general, the reaction is carried out with an 
amount of cobalt such that the atomic ratio Co/Ru ranges from 0.01 to 100 
(0.01.ltoreq.Co/Ru.ltoreq.100). This ratio preferably ranges from 0.1 to 
10. 
The presence of an iodine-containing promoter is also required for carrying 
out the process according to the present invention. Free or combined 
iodine can be used for this purpose. 
A first category of iodine-containing promoters suitable for carrying out 
the subject process consists of alkyl or acyl iodides of the respective 
formulae R"--I and R"--CO--I, in which R", which can be identical to or 
different from R', has the meaning given for R'. In this catetory, it is 
preferred to use alkyl iodides having a maximum of 4 carbon atoms and more 
particularly methyl or ethyl iodide. 
A second category of iodine-containing promoters which can be used within 
the scope of the present process consists of ionic iodides, the cations of 
which are selected from among alkali metal cations, alkaline earth metal 
cations and the quaternary ammonium or phosphonium cations represented by 
the formulae I to III below: 
##STR1## 
in which A represents a nitrogen or phosphorus atom, and R.sub.1, R.sub.2, 
R.sub.3 and R.sub.4, which can be identical or different, represent 
hydrogen or preferably organic radicals, the free valency of which is 
carried by a carbon atom, it optionally being possible for any two of 
these various radicals to together form a single divalent radical. 
More specifically, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are advantageously 
linear or branched chain alkyl radicals, cycloalkyl radicals, aralkyl 
radicals (for example, benzyl) or monocyclic aryl radicals, which have at 
most 16 carbon atoms and which, if appropriate, can be substituted by 1 to 
3 alkyl radicals having from 1 to 4 carbon atoms, it optionally being 
possible for two of the radicals R.sub.1 to R.sub.4 to together form a 
single divalent alkylene or alkenylene radical containing 3 to 6 carbon 
atoms and, if appropriate, 1 or 2 ethylenic double bonds, and it being 
possible for the said radical to bear 1 to 3 alkyl substituents having 
from 1 to 4 carbon atoms. 
##STR2## 
in which R.sub.5, R.sub.6, R.sub.7 and R.sub.8, which are identical or 
different, represent alkyl radicals having from 1 to 4 carbon atoms, it 
also being possible for one of the radicals R.sub.7 or R.sub.8 to 
represent hydrogen and it optionally being possible for R.sub.7 and 
R.sub.8 to together form a single divalent alkylene radical containing 
from 3 to 6 carbon atoms, for example, tetramethylene or hexamethylene; 
R.sub.6 and R.sub.7 or R.sub.8 can together form a single divalent 
alkylene or alkenylene radical containing 4 carbon atoms and, if 
appropriate, 1 or 2 ethylenic double bonds, the nitrogen atom then being 
included in a heterocyclic ring to form, for example, a pyridinium cation. 
##STR3## 
in which R.sub.5 and A.sup.+ have the meaning given above, R.sub.9, which 
can be identical to R.sub.5, represents an alkyl radical having from 1 to 
4 carbon atoms or a phenyl radical and y is an integer ranging from 1 to 
10 (1.ltoreq.y.ltoreq.10) and preferably from 1 to 6 
(.ltoreq.1.ltoreq.y.ltoreq.6). The following are exemplary of quaternary 
ammonium iodides suitable for carrying out the present process: 
tetramethylammonium, triethylmethylammonium, tributylmethylammonium, 
trimethyl-(n-propyl)-ammonium, tetraethylammonium, tetrabutylammonium, 
dodecyltrimethylammonium, benzyltrimethylammonium, 
benzyldimethylpropylammonium, benzyldimethyloctylammonium, 
dimethyldiphenylammonium, methyltriphenylammonium, 
N,N-dimethyl-trimethyleneammonium, N,N-diethyl-trimethyleneammonium, 
N,N-dimethyltetramethyleneammonium, N,N-diethyl-tetramethyleneammonium, 
N-methylpyridinium, N-ethylpyridinium and N-methylpicolinium iodides. 
The following are exemplary quaternary phosphonium iodides also suitable 
for carrying out the present process: tetramethylphosphonium, 
ethyltrimethylphosphonium, trimethylpentylphosphonium, 
octyltrimethylphosphonium, dodecyltrimethylphosphonium, 
trimethylphenylphosphonium, diethyldimethylphosphonium, 
dicyclohexyldimethylphosphonium, dimethyldiphenylphosphonium, 
cyclohexyltrimethylphosphonium, triethylmethylphosphonium, 
methyl-tri-(isopropyl)-phosphonium, methyl-tri-(n-propyl)-phosphonium, 
methyl-tri-(n-butyl)-phosphonium, 
methyl-tris-(2-methylpropyl)-phosphonium, methyltricyclohexylphosphonium, 
methyltriphenylphosphonium, methyltribenzylphosphonium, 
methyl-tris-(4-methyl-phenyl)-phosphonium, methyltrixylylphosphonium, 
diethylmethylphenylphosphonium, dibenzylmethylphenylphosphonium, 
ethyltriphenylphosphonium, tetraethylphosphonium, 
ethyl-tri-(n-propyl)-phosphonium, triethylpentylphosphonium, 
ethyltriphenylphosphonium, n-butyl-tri-(n-propyl)-phosphonium, 
butyltriphenylphosphonium, benzyltriphenylphosphonium, 
(.beta.-phenylethyl)-dimethylphenylphosphonium, tetraphenylphosphonium and 
triphenyl-(4-methylphenyl)-phosphonium iodides. 
The precise nature of the quaternary ammonium or phosphonium cation is not 
of fundamental importance within the scope of the present process. The 
choice from among these compounds is governed more by considerations of a 
practical nature, such as solubility in the reaction medium, the 
availability and the convenience of use. 
In this respect, the quaternary ammonium or phosphonium iodides represented 
either by the formula (I) in which any one of the radicals R.sub.1 to 
R.sub.4 is selected from among linear alkyl radicals having from 1 to 4 
carbon atoms, or by the formulae (II) or (III) in which R.sub.5 or R.sub.6 
is also an alkyl radical having from 1 to 4 carbon atoms, are particularly 
suitable. 
Moreover, the preferred ammonium iodides are those in which the cations 
correspond to the formula (I) in which all the radicals R.sub.1 to R.sub.4 
are selected from among linear alkyl radicals having from 1 to 4 carbon 
atoms, and in which at least three of same are identical. 
Likewise, the preferred quaternary phosphonium iodides are those in which 
the cations correspond to the formula (I) in which any one of the radicals 
R.sub.1 to R.sub.4 represents a linear alkyl radical having from 1 to 4 
carbon atoms, the other three radicals being identical and selected from 
among phenyl, tolyl or xylyl radicals. 
The alkali metal iodides, in particular lithium, potassium and sodium 
iodides, constitute a preferred class of ionic iodides within the scope of 
the present invention. The quaternary phosphonium iodides, and more 
particularly those in which the cations correspond to the formula (I) 
above, in which one of the radicals R.sub.1 to R.sub.4 is an alkyl radical 
having from 1 to 4 carbon atoms, the other three radicals being identical 
and selected from among phenyl, tolyl or xylyl radicals, constitute 
another preferred class of ionic iodides which are particularly effective 
for carrying out the present invention. 
Of course, hydriodic acid can also be used as the iodine-containing 
promoter; it is also possible to employ iodine-containing compounds such 
as CoI.sub.2, RuI.sub.3 and Ru(CO).sub.4 I.sub.2, by themselves or, 
preferably, mixed with one or more iodine-containing promoters belonging 
to one or another of the aforenoted categories. 
In general, the amount of iodine-containing promoter is such that the 
atomic ratio I/Ru is equal to at least 0.01; it serves no purpose to 
exceed a value of 2,000 for this ratio. This ratio advantageously ranges 
from 0.05 to 500. 
According to a preferred embodiment of the subject process, an alkyl or 
acyl iodide (a member of the first category of iodine-containing promoters 
described above) is used simultaneously with an ionic iodide belonging to 
the second category of iodine-containing promoters mentioned above. 
It too has been found that good results are obtained if an alkyl iodide 
(R"--I) is used simultaneously with an alkali metal iodide. 
The simultaneous use of methyl iodide and an alkali metal iodide is 
particularly advantageous within the scope of the present process. 
Another essential characteristic of the present invention is the use of 
vanadium or a vanadium compound. Although finely divided vanadium metal 
can be used, it is preferred to use vanadium compounds in which the 
vanadium is in oxidation state 4 or 5, namely, at least one compound 
selected from the group comprising the oxides, the halides and the 
oxyhalides of vanadium (IV) or vanadium (V) and vanadyl 
bis-acetylacetonate. The following are exemplary of vanadium compounds 
suitable for carrying out the present process: VCl.sub.4, VOCl.sub.2, 
VOBr.sub.2, VO(C.sub.5 H.sub.7 O.sub.2).sub.2, V.sub.2 O.sub.5, VOCl.sub.3 
and VOBr.sub.3. 
Among the vanadium (IV) compounds, vanadyl bis-acetylacetonate, VO(C.sub.5 
H.sub.7 O.sub.2).sub.2, is especially effective. 
The amount of vanadium (or vanadium compound) employed in the reaction is 
generally such that the atomic ratio V/Ru ranges from 0.5 to 500 
(0.5&lt;V/Ru&lt;500). This ratio preferably ranges from 1 to 200. 
According to the present invention, a mixture containing carbon monoxide 
and hydrogen is thus reacted with an alkyl carboxylate in the presence of 
water and the catalyst system defined above. In general, the water 
represents at least 1% by volume of the initial reaction medium and can be 
as high as 25% of the said volume. The reaction is advantageously carried 
out in the liquid phase under a pressure in excess of atmospheric. In 
general, it is carried out under a total pressure of at least 50 bars; a 
pressure of as much as 1,000 bars serves no purpose. To carry out the 
invention satisfactorily, a total pressure of 80 to 350 bars is 
recommended. The molar ratio of the carbon monoxide to the hydrogen can 
vary over wide limits. 
If it is desired to assist the carbonylation of the starting material (the 
production of the carboxylic acid R'--CO--OH), the reaction is carried out 
with a mixture comprising a preponderant proportion of carbon monoxide and 
a small proportion of hydrogen; in general, a molar ratio CO/H.sub.2 of 
more than 5 leads to satisfactory results in this case. 
If it is desired to assist the hydrocarbonylation of the starting material 
(the production of R'--CHO, R'--CH.sub.2 OH, R--CO--O--CH.sub.2 --R' and 
R'--CO--O--CH.sub.2 --R'), the reaction is carried out with a mixture 
containing carbon monoxide and hydrogen in a molar ratio CO/H.sub.2 
ranging from 1/10 to 10/1 and preferably ranging from 1/5 to 5/1. 
In all cases, substantially pure carbon monoxide and hydrogen, as available 
commercially, are employed. However, the presence of impurities, such as, 
for example, carbon dioxide, oxygen, methane and nitrogen, is not 
detrimental. 
The reaction temperature is generally above 120.degree. C. However, it 
serves no purpose to exceed a temperature of 300.degree. C. Good results 
are obtained within the temperature range from 160.degree. to 250.degree. 
C. 
As indicated in equation (1), the starting material is an alkyl carboxylate 
of the formula R--CO--O--R', in which R represents a linear or branched 
chain alkyl radical having from 1 to 16 carbon atoms, a cycloalkyl radical 
having from 3 to 6 carbon atoms, a phenyl radical (C.sub.6 H.sub.5 --), a 
radical C.sub.6 H.sub.5 --C.sub.x H.sub.2x -- or a radical C.sub.x 
H.sub.2x+1 --C.sub.6 H.sub.4 --, with x being an integer ranging from 1 to 
6 (1.ltoreq.x.ltoreq.6), and R' represents a linear or branched chain 
alkyl radical having from 1 to 5 carbon atoms, it furthermore being 
possible for R and R' to be identical. R' is preferably a methyl radical. 
R is advantageously an alkyl radical having at most 4 carbon atoms or a 
radical C.sub.6 H.sub.5 --CH.sub.2 --. Alkyl acetates and benzoates, and 
more particularly methyl acetate and benzoate, are particularly suitable 
starting materials within the scope of the present invention. 
Of course, the alkyl carboxylate (starting material) can be formed in situ 
from the corresponding carboxylic acid and alcohol of the formulae RCOOH 
and R'OH respectively. 
It has also been determined that good results are obtained if the reaction 
medium also initially contains a carboxylic acid of the formula R"'COOH, 
in which R"' has the meaning given for R, it being possible for R"' and R 
to be identical or different. The initial reaction medium can contain up 
to 90% by volume of carboxylic acid (R"'COOH). 
According to another preferred embodiment of the present process, the 
initial reaction mixture contains from 1 to 20% by volume of water and 
from 5 to 50% by volume of carboxylic acid. 
If the initial reaction medium contains a carboxylic acid (R"'COOH) which 
is different from the acid RCOOH from which the starting alkyl carboxylate 
is derived, the presence, among the reaction products, of the ester of the 
formula: R"'COOCH.sub.2 R', in which R' has the above meaning, is noted in 
certain instances. 
If it is desired to carry out the reaction initially in the presence of a 
carboxylic acid (R"'COOH), acetic, propionic, butyric, benzoic or toluic 
acid is preferably used. 
As indicated above, the present process has a particularly advantageous 
application in the preparation of one or more compounds selected from 
among acetaldehyde, acetic acid, ethanol and ethyl acetate, from methyl 
carboxylates and especially from methyl acetate. 
As far as it is possible to determine, and without implying any limitation, 
the subject process which leads to the formation of the main products 
referred to above, can be directed towards the preferential production of 
one or other of the classes of products in question. 
Thus, a reduction in the reaction temperature and/or in the proportion of 
hydrogen in the CO/H.sub.2 mixture is capable of assisting the production 
of acetic acid. (Of course, in the case where the starting material is 
methyl acetate, some of the acetic acid formed orginates from the 
hydrolysis reaction of the starting material.) On the other hand, an 
increase in the reaction temperature and/or in the proportion of hydrogen 
in the CO/H.sub.2 mixture and, if appropriate, the presence of an 
increased proportion of ruthenium in the reaction medium seem to direct 
the reaction towards the preferential formation of ethyl acetate or 
ethanol. 
An increase in the temperature and/or in the proportion of hydrogen in the 
CO/H.sub.2 mixture, coupled with a reduction in the reaction time, would 
tend to assist the production of acetaldehyde. 
Thus, it is possible to obtain free acetaldehyde, namely, acetaldehyde 
which is not substantially converted to dimethylacetal, in contrast to 
that which occurs to a more or less marked extent when attempting to 
obtain this product starting from free methanol. Those skilled in the art 
will appreciate the fact that the recovery of the acetaldehyde from the 
reaction medium is facilitated, especially if the reaction is carried out 
in the presence of a heavy carboxylic acid, such as benzoic acid, and/or 
if a heavy methyl carboxylate (for example, methyl benzoate) is selected 
as the starting material. 
Upon completion of the reaction, the products obtained can easily be 
separated, for example, by fractional distillation of the resulting 
mixture. 
In order to further illustrate the present invention and the advantages 
thereof, the following specific examples are given, it being understood 
that same are intended only as illustrative and in nowise limitative. 
In said examples which follow, the following technique was employed: 
The alkyl carboxylate (starting material), the catalyst system, distilled 
water and, if appropriate, a carboxylic acid were introduced into a Z-8 
CNDT 17-12 stainless steel autoclave (AFNOR Standard Specification) having 
a capacity of 250 ml. After closing the autoclave, a pressure of 140 bars 
(unless otherwise indicated) was established with the aid of a mixture of 
carbon monoxide and hydrogen in a fixed molar ratio, as indicated in each 
of the following examples. 
Shaking by means of a reciprocating system was commenced and the autoclave 
was then heated to the selected temperature over the course of about 25 
minutes. 
The pressure in the autoclave then increased and was maintained 
substantially at the value indicated in each of the following examples by 
successively introducing additional amounts of the initial CO/H.sub.2 
mixture. When the reaction time fixed for each example, at the indicated 
temperature, was reached, the heating and shaking were terminated. The 
autoclave was then cooled and degassed. After dilution, the resulting 
reaction mixture was analyzed by gas chromatography. 
The results obtained are indicated in mols of products (in principle: 
acetaldehyde, ethanol, ethyl acetate and acetic acid) obtained per hour 
and per liter of reaction medium. The notation M/hour.times.liter is used 
for each product. 
The results relating to the acetic acid include neither the amount of 
acetic acid which may have been introduced initially, nor the amount which 
was formed by hydrolysis of the methyl acetate (starting material). 
Also, for a given product, Y indicates the selectivity of this product, 
relative to all of the products listed immediately above. 
The degree of conversion, referred to as DC in the following text, is 
defined as being the ratio of the total number of mols of products in the 
list given above to the number of mols of methyl acetate introduced, 
reduced by the number of mols (of this starting material) hydrolyzed. 
(That fraction of the starting material hydrolyzed during an experiment 
can be measured by determining the methanol present in the liquid product 
obtained upon completion of the experiment).

EXAMPLES 1 TO 11 
Using the autoclave and the procedure described above, a series of 
experiments was carried out on a charge containing 80 ml of methyl acetate 
(1,000 mmols), 20 ml of acetic acid (350 mmols), 3 ml of water (170 
mmols), cobalt, triruthenium dodecacarbonyl, vanadyl acetylacetonate, 
methyl iodide and/or sodium iodide. The particular conditions are reported 
in Table I(a) below, in which P.sub.T denotes the total pressure, T the 
reaction temperature and Co(OAc).sub.2 cobalt acetate tetrahydrate; the 
results obtained are reported in Table I(b) below, in which AcOH denotes 
acetic acid and MeOH methanol. Control experiment (a) was carried out in 
the absence of vanadium. 
TABLE I(a) 
__________________________________________________________________________ 
OPERATING CONDITIONS 
Ru Cobalt V 
Example 
mg mg mg CH.sub.3 I 
NaI P.sub.T Time 
No. atoms 
nature 
atoms 
atoms 
mmols 
mmols 
bars 
CO/H.sub.2 
T .degree.C. 
minutes 
__________________________________________________________________________ 
1 1.30 
Co(OAc).sub.2 
0.22 
17 35 0 250 
1/2 215 20 
2 1.30 
Co(OAc).sub.2 
0.22 
8.5 0 30 243 
1/2 212 20 
3 1.30 
Co.sub.2 (CO).sub.8 
0.22 
16.7 
3.52 
12 260 
1/2 216 40 
a 1.30 
Co.sub.2 (CO).sub.8 
0.22 
0 3.52 
12 260 
1/2 216 75 
4 1.30 
CoI.sub.2 
0.22 
16.7 
3.60 
0 260 
1/1 212 40 
5 1.30 
CoI.sub.2 
0.22 
16.7 
3.61 
15 260 
1/1 214 40 
6 1.30 
CoI.sub.2 
0.22 
16.7 
3.62 
30 260 
1/1 212 40 
7 1.30 
CoI.sub.2 
0.22 
4.1 3.79 
15 260 
1/1 215 40 
8 1.30 
CoI.sub.2 
0.22 
29.7 
3.67 
15 250 
1/1 215 40 
9 0.65 
CoI.sub.2 
0.22 
29.7 
3.54 
15 250 
1/1 214 40 
10 1.30 
CoI.sub.2 
2.89 
29.7 
0 15 260 
1/1 214 40 
11 1.30 
CoI.sub.2 
0.22 
29.7 
16.1 
15 260 
1/1 212 40 
__________________________________________________________________________ 
TABLE I(B) 
__________________________________________________________________________ 
RESULTS 
Acetaldehyde Ethanol Ethyl acetate 
Acetic acid 
Example 
M/hour 
Y M/hour 
Y M/hour 
Y M/hour 
Y DC 
No. .times. liter 
(%) 
.times. liter 
(%) 
.times. liter 
(%) 
.times. liter 
(%) (%) 
__________________________________________________________________________ 
1 0.41 6 1.51 22 3.56 51 1.51 22 23.3 
2 0.82 16 1.40 28 2.87 56 -- -- 17.4 
3 0.32 6 0.91 18 3.26 65 0.52 10 33.6 
a 0.18 9 0.32 16 1.45 72 0.06 3 25.1 
4 -- -- 0.08 11 0.41 58 0.22 31 3.2 
5 1.47 30 0.59 12 1.91 38 1.01 20 34.6 
6 1.31 30 0.29 7 1.70 39 1.09 25 31 
7 0.99 24 0.59 14 1.69 40 0.94 22 28.3 
8 1.14 26 0.29 7 1.97 45 0.99 23 30.7 
9 1.40 35 0.26 6 1.25 31 1.12 28 28.2 
10 1.84 30 0.39 6 1.83 30 2.14 34 44.6 
11 1.28 30 0.28 7 1.75 41 0.93 22 29.7 
__________________________________________________________________________ 
EXAMPLE 12 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 90 ml of methyl acetate 
(1,130 mmols); 
(ii) 5 ml of acetic acid 
(87.5 mmols); 
(iii) 10 ml of water (566 mmols); 
______________________________________ 
(iv) 0.24 mg atom of cobalt, in the form of cobalt acetate; 
(v) 1.31 mg atoms of ruthenium, in the form of ruthenium iodide; 
(vi) 29.7 mg atoms of vanadium, in the form of vanadyl acetylacetonate; and 
(vii) 10 mmols of potassium iodide. 
After a reaction time of 40 minutes at 203.degree. C., with the pressure in 
the autoclave being maintained at about 200 bars by periodically 
introducing additional amounts of a 1/1 CO/H.sub.2 mixture, the formation 
of: 
(1) 0.07 M/hour.times.liter of acetaldehyde (Y=6%); 
(2) 0.34 M/hour.times.liter of ethanol (Y=28%); 
(3) 0.31 M/hour.times.liter of ethyl acetate (Y=25%); 
and 
(4) 0.51 M/hour.times.liter of acetic acid (Y=41%); was determined 
(DC=7.2%). 
EXAMPLE 13 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 75 ml of methyl acetate 
(940 mmols); 
(ii) 25 ml of acetic acid 
(437 mmols); 
(iii) 3 ml of water (170 mmols); 
______________________________________ 
(iv) 0.55 mg atom of cobalt, in the form of cobalt iodide; 
(v) 1.32 mg atoms of ruthenium, in the form of ruthenium acetylacetonate; 
(vi) 26 mg atoms of vanadium, in the form of vanadyl acetylacetonate; 
(vii) 10.5 mmols of methyl iodide; and 
(viii) 12 mmols of sodium iodide. 
After a reaction time of 40 minutes at 213.degree. C., with the pressure in 
the autoclave being maintained at about 150 bars by periodically 
introducing additional amounts of a 1/2 CO/H.sub.2 mixture, the formation 
of: 
(1) 0.22 M/hour.times.liter of acetaldehyde (Y=10%); 
(2) 0.21 M/hour.times.liter of ethanol (Y=9%); 
(3) 0.93 M/hour.times.liter of ethyl acetate (Y=41%); 
and 
(4) 0.93 M/hour.times.liter of acetic acid (Y=41%); was determined 
(DC=16.3%). 
EXAMPLE 14 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 80 ml of methyl acetate 
(1,000 mmols); 
(ii) 20 ml of acetic acid 
(350 mmols); 
(iii) 3 ml of water (170 mmols); 
______________________________________ 
(iv) 0.22 mg atom of cobalt, in the form of cobalt iodide; 
(v) 1.32 mg atoms of ruthenium, in the form of ruthenium acetylacetonate; 
(vi) 8.36 mg atoms of vanadium, in the form of vanadyl acetylacetonate; and 
(vii) 30 mmols of sodium iodide. 
After a reaction time of 20 minutes at 213.degree. C., with the pressure in 
the autoclave being maintained at about 260 bars by periodically 
introducing additional amounts of a 1/2 CO/H.sub.2 mixture, the formation 
of: 
(1) 1.04 M/hour.times.liter of acetaldehyde (Y=13%); 
(2) 1.55 M/hour.times.liter of ethanol (Y=20%); 
(3) 2.97 M/hour.times.liter of ethyl acetate (Y=38%); 
and 
(4) 2.35 M/hour.times.liter of acetic acid (Y=30%); was determined 
(DC=26.3%). 
EXAMPLE 15 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 60 ml of methyl acetate 
(750 mmols); 
(ii) 40 ml of acetic acid 
(700 mmols); 
(iii) 5 ml of water (280 mmols); 
______________________________________ 
(iv) 0.23 mg atom of cobalt, in the form of cobalt iodide; 
(v) 1.34 mg atoms of ruthenium, in the form of ruthenium chloride; 
(vi) 16.7 mg atoms of vanadium, in the form of vanadyl acetylacetonate; 
(vii) 5 mmols of iodine; and 
(viii) 20 mmols of lithium iodide. 
After a reaction time of 40 minutes at 211.degree. C., with the pressure in 
the autoclave being maintained at about 205 bars by periodically 
introducing additional amounts of a 1/2 CO/H.sub.2 mixture, the formation 
of: 
(1) 0.12 M/hour.times.liter of acetaldehyde (Y=5%); 
(2) 0.20 M/hour.times.liter of ethanol (Y=9%); 
(3) 1.01 M/hour.times.liter of ethyl acetate (Y=45%); 
and 
(4) 0.93 M/hour.times.liter of acetic acid (Y=41%); was determined 
(DC=20%). 
EXAMPLE 16 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 80 ml of methyl benzoate 
(635 mmols); 
(ii) 20 ml of acetic acid 
(350 mmols); 
(iii) 3 ml of water (170 mmols); 
______________________________________ 
(iv) 0.23 mg atom of cobalt, in the form of cobalt iodide; 
(v) 1.25 mg atoms of ruthenium, in the form of ruthenium acetylacetonate; 
(vi) 8.36 mg atoms of vanadium, in the form of vanadyl acetylacetonate; 
(vii) 5.25 mmols of methyl iodide; and 
(viii) 6 mmols of methyltriphenylphosphonium iodide. 
After a reaction time of 40 minutes at 213.degree. C., with the pressure in 
the autoclave being maintained at about 205 bars by periodically 
introducing additional amounts of a 1/2 CO/H.sub.2 mixture, the formation 
of: 
(1) 0.48 M/hour.times.liter of acetaldehyde; 
(2) 0.54 M/hour.times.liter of ethanol; 
(3) 0.96 M/hour.times.liter of ethyl acetate; and 
(4) 0.20 M/hour.times.liter of ethyl benzoate; was determined. 
EXAMPLE 17 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 80 ml of methyl acetate 
(1,000 mmols); 
(ii) 20 ml of acetic acid 
(350 mmols); 
(iii) 3 ml of water (170 mmols); 
______________________________________ 
(iv) 0.22 mg atom of cobalt, in the form of cobalt iodide; 
(v) 1.30 mg atoms of ruthenium, in the form of triruthenium dodecacarbonyl; 
(vi) 16.7 mg atoms of vanadium, in the form of vanadyl acetylacetonate; 
(vii) 3.53 mmols of methyl iodide; and 
(viii) 15 mmols of tetraethylammonium iodide. 
After a reaction time of 10 minutes at 214.degree. C., with the pressure in 
the autoclave being maintained at about 260 bars by periodically 
introducing additional amounts of a 1/1 CO/H.sub.2 mixture, the formation 
of: 
(1) 6.20 M/hour.times.liter of acetaldehyde (Y=69%); 
(2) 0.72 M/hour.times.liter of ethanol (Y=8%); 
and 
(3) 2.01 M/hour.times.liter of ethyl acetate (Y=23%); was determined 
(DC=14.9%). 
EXAMPLE 18 
Using the autoclave and the procedure described above, an experiment was 
carried out on a charge consisting of: 
______________________________________ 
(i) 80 ml of methyl acetate 
(1,000 mmols); 
(ii) 20 ml of acetic acid 
(350 mmols); 
(iii) 5 ml of water (280 mmols); 
______________________________________ 
(iv) 0.22 mg atom of cobalt, in the form of cobalt acetate tetrahydrate; 
(v) 1.30 mg atoms of ruthenium, in the form of triruthenium dodecacarbonyl; 
(vi) 8.36 mg atoms of vanadium, in the form of vanadyl acetylacetonate; and 
(vii) 30 mmols of sodium iodide. 
After a reaction time of 20 minutes at 214.degree. C., with the pressure in 
the autoclave being maintained at about 250 bars by periodically 
introducing additional amounts of a 13/1 CO/H.sub.2 mixture, the formation 
of: 
(1) 1.15 M/hour.times.liter of acetaldehyde (Y=25%); 
(2) 0.18 M/hour.times.liter of ethanol (Y=4%); 
(3) 0.42 M/hour.times.liter of ethyl acetate (Y=9%); 
and 
(4) 2.93 M/hour.times.liter of acetic acid (Y=63%); was determined 
(DC=15.5%). 
While the invention has been described in terms of various preferred 
embodiments, the skilled artisan will appreciate that various 
modifications, substitutions, omissions, and changes may be made without 
departing from the spirit thereof. Accordingly, it is intended that the 
scope of the present invention be limited solely by the scope of the 
following claims.