Homologation of carbonyloxy containing compounds

This invention produces higher homologs, i.e., differing by at least a --CH.sub.2 -unit, of carbonyloxy-containing compounds by treating the carbonyloxy-containing compounds with carbon monoxide and hydrogen in the presence of a ruthenium-containing compound, a proton donor, an iodide promoter, and optionally, a manganese-containing compound.

GENERAL DESCRIPTION OF THE INVENTION 
This invention is directed to the formation of higher homologs, i.e., 
differing by at least a --CH.sub.2 unit, of carbonyloxy-containing 
compounds. This process treats carbonyloxy-containing compounds with 
carbon monoxide and hydrogen in the presence of a ruthenium-containing 
compound, a proton donor, a halogen promoter, and optionally, a 
manganese-containing compound whereby such carbonyloxy-containing compound 
is converted to a higher homolog differing by at least an additional 
--CH.sub.2 -unit in the position alpha to the carbonyl of the carbonyloxy 
group. 
DISCUSSION OF THE PRIOR ART 
D. J. Cram and G. S. Hammond in "Organic Chemistry", McGraw-Hill, 2nd Ed., 
1964, p. 18, describe a homologous series as a series of compounds in 
which each member differs from the next member by a constant amount, the 
members being homologs of one another. 
On page 496 of this text is described the Arndt-Eistert synthesis, in which 
a carboxylic acid is converted to its next-higher homolog (homologated) by 
a multi-step procedure involving diazomethane. 
Belgium Patent No. 857,270, published July 28, 1976, describes the 
homologation of esters wherein the alcohol portion of the ester is 
increased by the addition of CH.sub.2. According to the Belgium patent, an 
ether or an ester is reacted with carbon monoxide and hydrogen at a 
temperature of 150.degree.-350.degree. C. and a pressure of 50-1000 
atmospheres in the presence of a catalyst containing a ruthenium carbonyl 
and as a promoter, HI, or a solution of mineral or tetralkylammonium 
iodides or bromides, or their mixtures in a carboxylic acid. Illustrative 
of the kinds of products produced is shown in an example, which shows the 
carbonylation and homologation of dimethyl ether using tricarbonyl allyl 
ruthenium chloride and methyl iodide as the catalyst and promoter, 
respectively. The reaction is effected in an autoclave to which hydrogen 
and carbon monoxide are added at a temperature of 200.degree. C. and a 
pressure of 240 atmospheres. The molar ratio of hydrogen to carbon 
monoxide is 2:1. The products of the reaction are 12.8% methane, 13% 
alcohols, 4.5% ether, 42.5% methyl acetate (the carbonylation product), 
16% ethyl acetate (the carbonylation and homologation product), and 6% 
acids (indicating the presence of acetic and propionic acid). The origin 
of the propionic acid is not discussed and it is only a very minor 
component of the total products. 
Belgium Patent No. 857,270 discloses that carboxyl acids may be employed as 
solvents for the process of Belgium Patent No. 857,270 and that if acetic 
acid is employed as the solvent in the carbonylation reaction of 
dimethylether in ethyl acetate that methyl acetate is formed and may be 
considered as an intermediate product. The use of carboxyl acids as 
solvents is further exemplified in examples 5 and 10 to 18 of Belgium 
Patent No. 857,270. 
The advance of the technology of this invention is the ability to introduce 
one or more --CH.sub.2 -groups adjacent or alpha to the carbonyl of a 
carbonyloxy group. This process has heretofore never been achieved in one 
step. 
During the present process, the homologation of the carbonyloxy-containing 
compound is achieved in a single reactor essentially at one period of 
time. The utility of this process is that it allows the production, in a 
single step, of higher homologs of carbonyloxy-containing compounds 
differing from the starting compound by at least one methylene group. 
Also, the present process may be used to produce compounds which may not 
be produced conveniently by other synthesis methods. 
Therefore, the process of this invention is fundamentally unconcerned with 
the structure of the carbonyloxy-containing compound since whatever 
carbonyloxy-containing compound is used, homologation is achieved and the 
benefits of the invention will be realized. Moreover, should a carboxylic 
acid, ester, or anhydride become altered in any way in the present 
process, such will be in addition to the alteration achieved by 
homologation. 
THE INVENTION 
This invention relates to the formation of higher homologs, i.e., differing 
by at least a --CH.sub.2 -unit, of carbonyloxy-containing compounds. More 
particularly, this invention is concerned with the treatment of 
carbonyloxy-containing compounds with carbon monoxide and hydrogen in the 
presence of a ruthenium-containing compound, a proton donor, an iodide 
promoter, and optionally, a manganese-containing compound whereby such 
carbonyloxy-containing compounds are converted to a higher homolog 
differing by at least an additional --CH.sub.2 -unit, in some instances 
differing by (--CH.sub.2 -).sub.n units, wherein n has a value of 1 to 
about 6, or more, in the position alpha to the carbonyl of the carbonyloxy 
groups of the compounds. 
The process is effected by reacting a carbonyloxy-containing compound with 
a mixture of carbon monoxide and hydrogen in the presence of a 
ruthenium-containing compound, preferably a ruthenium carbonyl complex, 
either formed in situ or formed prior to the reaction, in the presence of 
a proton donor such as an acid, an iodide promoter, and optionally, a 
manganese-containing compound. 
The carbonyloxy-containing compound which can be homologated according to 
the process of this invention is essentially any carbonyloxy-containing 
compound, ranging from formic acid to fatty acids, and to essentially any 
carboxylic acid, and esters and anyhdrides thereof. As long as a compound 
contains the carbonyloxy radical: 
##STR1## 
in which the free valence of the oxy(--O--) group is bonded to carbon or 
hydrogen, it can be used in the process of this invention to form higher 
homologous compounds. 
Preferred carbonyloxy-containing compounds are of the formulae: 
##STR2## 
wherein R and R.degree. are monovalent radicals such as hydrogen, 
hydroxyl, carboxyl and any organic radical bonded to the --C.dbd.O, and R' 
is a monovalent organic radical bonded to the oxide of the carbonyloxy 
group; R together with R' or R together with R.degree. can form a cyclic 
compound. These carbonyloxy-containing compounds produce a higher homolog 
of the formulae: 
##STR3## 
wherein n and m have values of at least 1 and typically not in excess of 
about 6 and R and R.degree. are as previously defined. 
Illustrative of such carbonyloxy containing compounds are the following 
polycarboxylic acids, esters, or anhydrides of the formula: 
##STR4## 
wherein R" is any polyvalent organic radical or a bond joining two 
--COOR"' groups; R"' is H or a monovalent organic radical; a is 0 or 1; b 
is equal to the free valence of R" or 2 when a is 0. The size and 
composition of R" or R"' are not important to the process of this 
invention, since they do not affect the operativeness of the process. 
Further illustrative carbonyloxy-containing compounds include the 
following: carbonic acid, the esters of carbonic acid, whether monomers or 
polymers (viz., polycarbonates), formic acid and its esters regardless of 
the size and composition of the ester moiety, fatty acids of C.sub.1 to 
greater than C.sub.20 in size, regardless of whether they are normal, 
secondary or tertiary carboxylic acids, aromatic monocarboxylic acid 
esters and their anyhdrides, ethylenically unsaturated carboxylic acids 
such as tiglic acid, ricinoleic acid and their esters regardless of the 
size and composition of the ester moiety, cycloaliphatic monocarboxylic 
acids such as cyclohexanecarboxylic acid, 2-norbornyl carboxylic acid, 
2-norborn-5-enyl carboxylic acid and their esters regardless of the size 
and composition of the ester moiety, aromatic monocarboxylic acid, such as 
benzoic, benzylic, toluic, naphthaoic acids and their esters regardless of 
the size and composition of the ester moiety, substituted alkanoic acids, 
such as the protein acids, glycolic acids, hydroxyl carboxylic acids, 
phenyl-substituted fatty acids (larger than benzylic, illustrated above), 
carboxymethyl-cellulose, ascorbic acids, tannic acid, steroid acids such 
as cholanic acid, ferrocenyl carboxylic acid, and the like, and their 
esters regardless of the size and composition of the ester moiety, 
aliphatic dicarboxylic acids starting from oxalic acid, malonic acid 
through maleic acid, fumaric acid, adipic acid to 1,12-dicarboxydodecane 
and their esters regardless of the size and composition of the ester 
moiety, aromatic dicarboxylic acids such as phthalic acid, isophthalic 
acid, terephthalic acid, naphthyl dioic acids, anthracyl dioic acids, 
polyphenylene dioic acids, and their esters regardless of the size and 
composition of the ester moiety, cycloaliphatic dicarboxylic acids such as 
1, 4-cyclohexane dicarboxylic acid, 1, 3-cyclohexane dicarboxylic acid, 
and their esters regardless of the size and composition of the ester 
moiety, tricarboxylic acids such as trimellitic and pyromellitic acid and 
their esters regardless of the size and composition of the ester moiety, 
tetracarboxylic acids, such as ethylene diamine-N,N',N",N"'-tetraacetic 
acid, telomers of acrylic acid, and their esters, regardless of the size 
and composition of the ester moiety, polymeric carboxylic acids, such as 
the homopolymers of acrylic acid, and methacrylic acid. 
If the carbonyloxy-containing compound possesses groups which for one 
reason or another will inhibit or inactivate the catalyst, a simple 
technique for overcoming the inhibition of the reaction is to provide an 
additional amount of catalyst to exceed the capacity of the inhibiting 
component from preventing homologation. 
The ruthenium-containing compounds which effect the homologation reaction 
herein may be one or more of the following compounds: 
RuO.sub.2 
Ru(CO).sub.5 
Ru.sub.3 (CO).sub.12 
H.sub.2 Ru.sub.4 (CO).sub.13 
H.sub.4 Ru.sub.4 (CO).sub.12 
Ru(CO).sub.3 L.sub.2 
Ru(CO).sub.4 L 
Ru.sub.3 (CO).sub.11 L 
Ru.sub.3 (CO).sub.10 L.sub.2 
Ru.sub.3 (CO).sub.9 L.sub.3 
RuX.sub.2 L.sub.4, X=Cl, Br, I 
RuX.sub.2 L.sub.3, X=Cl, Br, I 
RuX.sub.2 (CO).sub.2 L.sub.2, X=Cl, Br, I 
RuX.sub.3 L.sub.2 (CH.sub.3 OH), X=Cl, Br, I 
[C.sub.6 H.sub.5 NH] [RuX.sub.4 (CO)(C.sub.6 H.sub.5 N)], X=Cl, Br, I 
[Ru(CO).sub.3 X.sub.2 ].sub.2, X=Cl, Br, I 
Ru(CO).sub.2 X.sub.2 [(C.sub.6 H.sub.5).sub.2 P CH.sub.2 CH.sub.2 P(C.sub.6 
H.sub.5).sub.2 ], X=Cl, Br, I 
RuXHL.sub.3, X=Cl, Br, I 
RuH.sub.2 L.sub.4 
RuH.sub.4 L.sub.3 
RuH.sub.2 (N.sub.2) L.sub.3 
RuH.sub.2 (CO) (L).sub.3 
RuX.sub.3 (NO)L.sub.2, X=Cl, Br, I 
Ru(NO).sub.2 L.sub.2 
RuH.sub.2 (CH.sub.3 CN)L.sub.3 
Ru(OAc)H(L).sub.3 
[RuX.sub.3 (NO)].sub.n, X=Cl, Br, I 
[As(C.sub.6 H.sub.5).sub.4 ][RuX.sub.4 (CO)], X=Cl, Br, I 
[LH][RuX.sub.4 L.sub.2 ]X=Cl, Br, I 
Ru.sub.2 X.sub.3 (SnX.sub.3) (CO).sub.2 L.sub.4, X=Cl, Br, I 
(n.sup.6 -C.sub.6 H.sub.6) Ru (CH.sub.3) XL, X=Cl, Br, I 
[(n.sup.6 -C.sub.6 H.sub.6)(n.sup.5 -C.sub.5 H.sub.5)Ru]X, X=Cl, Br, I 
[(n.sup.6 -C.sub.6 H.sub.6)RuX.sub.2 ].sub.2, X=Cl, Br, I 
Suitable classes of triorgano-containing ligands (L in the formulas, supra) 
which are contemplated in the practice of the invention include the 
trialkylphosphites, the tricycloalkylphosphites, the triarylphosphites, 
the triarylphosphines, the triarylstibines, and the triarylarsines. 
Desirably, each organo moiety in the ligand does not exceed 18 carbon 
atoms. The triarylphosphites and the triarylphosphines represent the 
preferred classes of ligands. Specific examples of ligands which re 
suitable for use herein include: 
P(CH.sub.3).sub.3 
P(C.sub.2 H.sub.5).sub.3 
P(n-C.sub.3 H.sub.7).sub.3 
P(n-C.sub.4 H.sub.9).sub.3 
P(iso-C.sub.4 H.sub.9).sub.3 
P(n-C.sub.5 H.sub.9).sub.3 
P(2-n-C.sub.4 H.sub.9 OC.sub.2 H.sub.4).sub.3 
P(2-C.sub.6 H.sub.5 C.sub.2 H.sub.4).sub.3 
P(C.sub.6 H.sub.11).sub.3 
P(CH.sub.3) (C.sub.2 H.sub.5).sub.2 
P(CH.sub.3).sub.2 (C.sub.2 H.sub.5) 
P(CH.sub.3).sub.2 (C.sub.6 H.sub.5) 
P(C.sub.2 H.sub.5).sub.2 (C.sub.6 H.sub.5) 
P(C.sub.6 H.sub.11).sub.2 (2-CNC.sub.2 H.sub.4) 
P(CH.sub.3).sub.2 (2-CNC.sub.2 H.sub.4) 
P(n-C.sub.4 H.sub.9).sub.2 (2-CNC.sub.2 H.sub.4) 
P(n-C.sub.3 H.sub.17).sub.2 (2-CNC.sub.2 H.sub.4) 
P(p-CH.sub.3 OC.sub.6 H.sub.4).sub.3 
P(C.sub.6 H.sub.5).sub.3 
P(C.sub.6 H.sub.5).sub.2 (C.sub.2 H.sub.5) 
P(C.sub.6 H.sub.5).sub.2 (n-C.sub.4 H.sub.9) 
P(O-n-C.sub.4 H.sub.9).sub.3 
P(OCH.sub.3).sub.3 
P(OC.sub.6 H.sub.5).sub.3 
The aforementioned ruthenium compounds should not be considered to be the 
defined catalyst effecting the homologation reaction. These ruthenium 
compounds are precursors and during the operation of the process it is 
believed that the catalytic species which helps promote the homologation 
reaction is formed. Thus, a considerable number of different ruthenium 
compounds may be employed herein. Particularly useful are the ruthenium 
compounds which contain iodine as aforedescribed, since the iodine can be 
utilized as part of the promoter enhancing the homologation reaction. 
One or more halogen components may be complexed with the ruthenium as 
ligands thereon. However, it is preferred to have an excess of the 
halogen, iodine, present in the catalyst system as a promoting component. 
By excess of iodine is meant an amount greater than 2 atoms of iodine per 
atom of ruthenium. This promoting component of the catalyst system may be 
iodine and/or an iodine compound such as hydrogen iodide, alkyl or aryl 
iodide, metal iodide, ammonium iodide, phosphonium iodide, arsonium 
iodide, stibonium iodide and the like. Exemplary suitable iodine providing 
or promoting components may be selected from the following iodine and/or 
iodine-containing compounds: 
R.sub.1 I wherein R.sub.1 is any alkyl or aryl group e.g., CH.sub.3 I, 
C.sub.6 H.sub.5 I, CH.sub.3 CH.sub.2 I, etc.; 
##STR5## 
wherein R.sub.2 is any alkyl or aryl group, e.g., 
##STR6## 
etc.; 
EQU R.sub.4 MI, R.sub.4 MI.sub.3, or R.sub.3 MI.sub.2 
wherein R is hydrogen or any alkyl, M is N, P, As, or Sb, e.g., NH.sub.4 I, 
PH.sub.4 I.sub.3, PH.sub.3 I.sub.2, (C.sub.6 H.sub.3).sub.3 PI.sub.2, 
and/or combination of R and M. 
A wide variety of manganese-containing compounds may also be used in the 
practice of this invention. Illustrative of suitable manganese-containing 
compounds are the following: manganese carbonyl, manganese halides, 
manganese carboxylates, manganese enolates, manganese oxides, manganese 
salts of other inorganic acids, manganese alkyls, arene complexes with 
manganese, olefin complexes with manganese, and the like. Specific 
illustrations of suitable manganese-containing compounds which may be used 
as cocatalysts in the practice of this invention are the following: 
Cyclopentadienyl Manganese Tricarbonyl 
C.sub.5 H.sub.5 Mn(CO).sub.3 
Dipyridine Manganese Dichloride 
(C.sub.5 H.sub.5 N).sub.2 MnCl.sub.2 
Manganese Acetate 
Mn(C.sub.2 H.sub.3 O.sub.2).sub.2 
Manganese Acetylacetonate (ic) 
Mn(CH.sub.3 COCHCOCH.sub.3).sub.3 
Manganese Acetylacetonate (ous) 
Mn(CH.sub.3 COCHCOCH.sub.3).sub.2 
Manganese (III) Benzoylacetonate 
Mn(C.sub.6 H.sub.5 COCHCOCH.sub.3).sub.3 
Manganese Carbonyl 
Mn.sub.2 (CO).sub.10 
Manganese Formate 
Mn(O.sub.2 CH).sub.2 
Manganese (II) Hexafluoroacetylacetonate 
(CF.sub.3 COCHCOCF.sub.3).sub.2 Mn 
Manganese Naphthenate 
Mn(Naphthenate).sub.2 
Manganese Octoate 
Mn[COO(C.sub.2 H.sub.5)CHC.sub.4 H.sub.9 ].sub.2 
Manganese Oxalate 
MnC.sub.2 O.sub.4.2H.sub.2 O 
Manganese Pentacarbonyl Bromide 
Mn(CO).sub.5 Br 
Manganese Stearate 
Mn(C.sub.18 H.sub.36 O.sub.2).sub.2 
Manganese (II) Trifluoroacetylacetonate 
Mn(CF.sub.3 COCHCOCH.sub.3).sub.2 
Methylcyclopentadienyl Manganese Tricarbonyl 
CH.sub.3 C.sub.5 H.sub.4 Mn(CO).sub.3 
bis-(Tripnenylphosphine)Imminium 
Pentacarbonylmanganate (PPh.sub.3).sub.2 Mn(CO).sub.5 
Manganese (II) bromide 
MnBr.sub.2.4H.sub.2 O 
Manganese (II) carbonate 
MnCO.sub.3 
Manganese (II) chloride, 
MnCl.sub.2 
Manganese (II) chloride, 
MnCl.sub.2.4H.sub.2 O 
Manganese (II) fluoride 
MnF.sub.2 
Manganese (III) fluoride 
MnF.sub.3 
Manganese (II) iodide 
MnI.sub.2.4H.sub.2 O 
Manganese (II) nitrate 
Mn(NO.sub.3).sub.2 
Manganese (II, III) oxide 
Mn.sub.3 O.sub.4 
Manganese (III) oxide 
Mn.sub.2 O.sub.3 
Manganese (IV) oxide 
MnO.sub.2 
Manganese (II) perchlorate 
Mn(ClO.sub.4).sub.2.6H.sub.2 O 
Manganese (II) sulfate 
MnSO.sub.4.H.sub.2 O 
Potassium hexacyanomanganate (II) 
K.sub.4 Mn(CN).sub.6.4H.sub.2 O 
Potassium permanganate 
KMnO.sub.4 
The amount of promoting component employed in the catalyst system of the 
present invention is such as to provide a ratio of halogen atoms to 
manganese atoms of from about 2:1 to 50,000:1 and higher. The preferred 
ratio is 3:1 to 5,000:1, while the more preferred ratio is 5:1 to 2500:1 
halogen atoms to manganese atoms. 
The quantity of the catalyst which is employed is not narrowly critical and 
can vary over a wide range. In general, the process of this invention is 
desirably conducted in the presence of a catalytically effective quantity 
of the active ruthenium species, or optionally, of the active ruthenium 
and manganese species which gives a suitable and reasonable reaction rate. 
The reaction proceeds when one employs as little as about 1.times.10.sup.6 
weight percent of ruthenium or even a lesser amount (calculated as the 
metal in the complex catalyst) based on the total quantity of reaction 
mixture. The upper concentration can be quite high, e.g., about ten weight 
percent or more of ruthenium based on the total quantity of reaction 
mixture. Higher concentrations may be used if desired. However, the upper 
concentration appears to be dictated by economics in terms of the cost of 
the catalyst to achieve the given reaction and ease of handling of the 
homogeneous phase reaction mixture during the course of reaction. 
Depending on various factors, such as the acyl compound of choice, the 
partial pressures of carbon monoxide and hydrogen, the total operative 
pressure of the system, the operative temperature, the choice of the 
solvent, if any, and other considerations a concentration of between about 
1.times.10.sup.-5 to about 10 weight percent of ruthenium or of each of 
ruthenium and manganese (contained in the complex catalyst) based on the 
total quantity of the homogenous liquid phase reaction mixture is 
generally suitable in the practice of this invention. 
The proton donor which may be used herein additionally includes hydrogen 
halides as well as other acids. The amount of proton donor which may be 
employed herein is such as to provide a molar ratio of proton donor to 
manganese plus ruthenium atoms of from about 2:1 to 50,000:1 and higher. 
The present process is typically effected in the presence of a liquid phase 
which may be homogeneous or heterogeneous depending upon the solubility of 
the carbonyloxy compound in the liquid phase. If the carbonyloxy compound 
is a highly cross-linked structure, then a solvent is selected which is 
sufficiently polar to allow sufficient wetting of the carbonyloxy moieties 
of the molecule, which allows the homologation to occur at the interface. 
Otherwise, there is no strict rule in the selection of a solvent. 
Essentially any liquid in which the catalyst components are soluble may be 
utilized as a solvent in the practice of this invention. However, if 
selection of a solvent includes a material which would adversely affect 
the catalytic activity of the catalyst, then of course, under those 
circumstances an excess of catalyst is employed to overcome the poison 
effect of the solvent or a solvent is selected which is not a poison. The 
solvent may be inert to the reactions which are taking place in the 
process or may participate in the reaction in a homogeneous liquid phase 
reaction mixture to produce the desired product. In some respects, the 
solvent may be a material which will react with another material in the 
mixture to form a third material which acts as a solvent. The solvent may 
also include the products of the reaction. Particularly illustrative of 
solvents suitable for use in the practice of this invention are the 
following: saturated and aromatic hydrocarbons, e.g., hexane, octane, 
dodecane, naphtha, decalin, tetrahydronaphtnalene, kerosene, mineral oil, 
cyclohexane, cycloheptane, alkylcycloalkane, benzene, toluene, xylene, 
naphthalene, alkylnaphthalene, and the like; ethers such as 
tetrahydrofuran, tetrahydropyran, diethylether, 1,2-dimethoxybenzene 
1,2-diethoxybenzene, the mono- and dialkylethers of ethylene glycol, 
propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, 
oxyethylene glycol, and the like; alkanols such as methanol, ethanol, 
propanol, isobutanol, 2-ethylhexanol, and the like; esters such as methyl 
acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, 
ethyl butyrate, methyl laurate, and lactones such as butyrolactone, and 
the like; water; fluorinated hydrocarbons that are inert under the 
reaction conditions such as perfluoroethane, monofluorobenzene, and the 
like. Another class of solvents are sulfones such as dimethylsulfone, 
diethylsulfone, diphenylsulfone, sulfolane, and the like; and halogenated 
solvents such as 1,2-dichloroethylene, 1,2-dichloroethane, chloroform, 
1-chlorobutane, and 4-bromotoluene, and the like. Mixtures of the 
aforementioned solvents may be employed so long as they are compatible 
with each other under the conditions of the reaction and will adequately 
provide the homogeneous liquid phase for carrying out the process of this 
invention. Of the aforementioned classes of solvents, hydrocarbons, the 
sulfones, and the fluorinated hydrocarbons are typically inert in the 
present process, whereas esters, water and alcohols will in one manner or 
another enter into a reaction during the course of the process. The esters 
have the capability of entering into ester interchange and homologation 
reactions; the water into hydrolysis reactions; and the alcohol into 
alcohol interchange reactions with esters, into esterification with acyl 
compound or into carbonylation reactions. 
In the preferred embodiment of this invention, the solvent is the acid 
itself since many of the desirable commercial acids that one would seek to 
homologate are liquid under the conditions of the homologation reaction. 
The present reaction is effected at a temperature which can vary over a 
wide range, from moderate temperatures to elevated temperatures. In 
general, the process is conducted at a temperature of between about 
50.degree. C. and about 400.degree. C. 
Operating the process at temperatures lower than 50.degree. C. will not 
produce the desired products at an optimum rate so that the reaction will 
have to be operated over an extended period of time in order to obtain the 
desired product of reaction. When operating the process at temperatures 
higher than 400.degree. C. there is a tendency for the reaction products 
and organic materials contained therein to decompose. Also there is a 
tendency for the catalytic species to decompose which forms insoluble 
ruthenium compounds. The formation of insoluble ruthenium compounds can be 
controlled by increasing the reaction pressure which is generally 
sufficient to keep the ruthenium catalytic species in solution. In most 
cases, when operating at the lower end of the temperature range, it is 
desirable to utilize pressures in the higher end of the pressure range. 
The preferred temperature range is between about 150.degree. C. and 
350.degree. C., while the most preferred temperature range is between 
about 200.degree. C. and 330.degree. C. However, there are occasions when 
a preferred temperature range may include any of the more desirable ranges 
as well as the broadest temperature range such that the process may be 
operated at a temperature between 100.degree. C. and 325.degree. C. and as 
well as between about 50.degree. C. and 350.degree. C. 
The process of the present invention is effected under superatmospheric 
pressure conditions. Invariably, the pressure is produced by the hydrogen 
and carbon monoxide provided to the reaction. Pressures of between about 
500 psia (36.535 kg/cm.sup.2) and about 12,500 psia (878.8 kg/cm.sup.2) 
represent an operative limit for producing the desired products. However, 
when operating the process at the lower end of the pressure range, the 
rate of reaction becomes markedly slow and therefore the reaction period 
must be extended until the desired amount of reaction product is produced. 
On the other hand, when the process is operated at a pressure near the 
high end of the range, the rate of production of the desired products will 
be increased. However, operating the process at pressures in excess of the 
upper end of the pressure range is not economically justified. In the 
preferred practice of this invention, it is desirable to operate the 
process at a pressure of between about 1000 psia (70.31 kg/cm.sup.2) and 
about 10,000 psia (703.07 kg/cm.sup.2). In addition to the partial 
pressure exerted by carbon monoxide and by hydrogen, a partial pressure 
will also be exerted by inert gases such as argon, if these are employed 
in the reaction. 
The process of this invention is effected for a period of time sufficient 
to produce the desired products. In general the reaction time can vary 
from minutes to several hours, i.e., from a few minutes to approximately 
twenty-four hours, and longer. If the most sluggish reaction conditions 
are selected, then the reaction time will have to be extended until the 
desired product is produced. It is readily appreciated that the residence 
period will be influenced by the reaction temperature, concentration and 
choice of the ruthenium catalyst, the promoter, the total gas pressure, 
and the partial pressure exerted by its components, the concentration and 
choice of solvent, the particular acyl compound and other factors. The 
synthesis of the desired products by the reaction of hydrogen, carbon 
monoxide and the acyl compound is suitably conducted under operative 
conditions which give reasonable reaction rates and/or conversions. 
The relative amounts of carbon monoxide and hydrogen which are initially 
present in the reaction mixture can be varied over a wide range. In 
general, the mole ratio of carbon monoxide to hydrogen is in the range of 
between about 20:1 to 1:20, preferably between about 15:1 and about 1:15, 
and most preferably between about 10:1 and about 1:10. It is to be 
understood, however, that molar ratios outside the stated broad range may 
be employed. Substances or reaction mixtures which form carbon monoxide 
and hydrogen under the reaction conditions may be employed in lieu of the 
mixtures of carbon monoxide and hydrogen. For example, one may use 
mixtures containing carbon dioxide and hydrogen, mixtures of carbon 
dioxide, carbon monoxide and hydrogen as well as mixtures of steam and 
carbon monoxide. The intended purpose is to provide enough carbon monoxide 
in combination with hydrogen in the homogeneous liquid phase mixture to 
produce the desired product. The manner in which the carbon monoxide and 
hydrogen are provided in the homogeneous liquid phase reaction mixture is 
not important in the practice of this invention, as long as they are 
present in a sufficient quantity to effect the production of the desired 
products. 
The process of this invention can be carried out in a batch, 
semi-continuous or continuous manner. The reaction may be conducted in a 
single reaction zone or in a plurality of reaction zones, in series or in 
parallel. The reaction may be conducted intermittently or continuously in 
an elongated tubular zone or in a series of zones. The material of 
construction of the equipment should be such so as to be inert during the 
reaction. The equipment should also be able to withstand the reaction 
temperatures and pressures. The reaction zone can be fitted with internal 
and/or external heat exchangers to control undue-temperature fluctuations, 
or to prevent possible "run-away" reaction temperatures caused by the 
exothermic nature of the reaction. In a preferred embodiment of the 
present invention, agitation means to insure complete mixing of the 
reaction mixture should be employed. Mixing induced by vibration, shaker, 
stirrer, rotary, oscillation, ultrasonic etc., all are 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 batch wise. 
Alternatively, the catalyst may be introduced into the reaction zone, 
continuously or intermittently during the course of the synthesis 
reaction. Means to introduce the reactants into the reaction zone during 
the course of the reaction and/or means to adjust the reactants in the 
reaction zone during the reaction, either intermittently or continuously, 
can be conveniently utilized in the process to maintain the desired molar 
ratios of reactants and to maintain the partial pressures exerted by the 
reactants. 
The operative conditions of the present process may be adjusted to optimize 
the conversion of the desired product and/or the economics of the process. 
In a continuous process, for example, it is preferred to operate at 
relatively low conversions, and it is desirable to recirculate unreacted 
mixtures of carbon monoxide and hydrogen to the reactor with or without 
make-up carbon monoxide and hydrogen. Recovery of the desired product can 
be achieved by methods well-known in the art, such as by distillation, 
fractionation, extraction, and the like. 
Typically, in carrying out the process, the product contained in the 
homogeneous liquid phase reaction mixture would be withdrawn from the 
reaction zone and distilled to recover the desired product. Thereafter, if 
desired, a fraction comprising the catalyst components generally contained 
in the by-products and/or solvent or acyl compound, can be recycled to the 
reaction zone. All or a portion of such fraction can be removed for 
recovery or regeneration of the catalyst. Fresh catalyst components can be 
intermittently added to the reaction stream or can be added directly to 
the reaction zone, to replenish any catalyst which is lost in the process. 
In another aspect of this invention a novel ruthenium containing catalyst 
is described. This novel catalyst is capable of homologating 
carbonyloxy-containing compounds with carbon monoxide and hydrogen. The 
catalyst is defined as ruthenium complexes which will homologate a 
carbonyloxy-containing compound when existing in a homogeneous liquid 
phase mixture in the presence of carbon monoxide, hydrogen, proton donor 
and iodine promoter, when the mixture is maintained at a temperature of 
between about 50.degree. C. and about 400.degree. C. and a pressure of 
between about 500 psia (36.535 kg/cm.sup.2) and about 12,500 psia (878.8 
kg/cm.sup.2). The metal compounds supplied to the homogeneous liquid phase 
reaction mixture are not themselves catalysts unless hydrogen, carbon 
monoxide, proton donor and iodine promoter are present and the reaction 
conditions, as previously described, are maintained. Thus, the 
aforementioned description with respect to the promoter, the homogeneous 
liquid phase reaction mixture, the temperature and pressure and the 
characterization of the products of the reaction are all important in and 
bear a relationship to the nature of the novel catalyst of this invention.

Although this invention has been described with respect to a number of 
details, it is not intended that this invention should be limited thereby. 
The examples which follow are intended solely to illustrate the most 
favorable embodiments of this invention which to date have determined and 
are not intended in any way to limit the scope and the intent of this 
invention. 
EXAMPLE 1 
A 500 ml stainless steel bomb reactor containing a removable glass liner 
was charged with a mixture of 0.50 g Ru.sub.3 (CO).sub.12, 0.20 g Mn.sub.2 
(CO).sub.10, 2 ml of a solution of 57 percent HI and 50 ml of acetic acid. 
Equimolar amounts of carbon monoxide and hydrogen were then added to the 
reactor to attain a pressure therein of 3000 psi at 25.degree. C. The 
reactor was rocked and the contents heated to 230.degree. C. and 
maintained at this temperature for four hours with continued rocking of 
the reactor. The reactor was then cooled and vented. The contents of the 
reactor were removed and analyzed by gas chromatography. This analysis 
showed that the following products were produced: 0.08 g methyl acetate, 
4.5 g ethyl acetate, 6.5 g propionic acid and 0.9 g butyric acid. 
EXAMPLE 2 
The procedure of Example 1 was exactly repeated except that the reactor was 
charged with a mixture of 0.50 g Ru.sub.3 (CO).sub.12, 0.50 g MnI.sub.2, 
0.5 ml of a solution of 57 percent HI and 50 ml of acetic acid and the 
contents heated at 200.degree. C. for three hours. Analysis by gas 
chromatography showed that the following acid products were produced: 3.7 
g propionic acid and 0.7 g butyric acid. Esters were also present. 
EXAMPLE 3 
The procedure of Example 1 was exactly repeated except that the reactor was 
charged with a mixture of 0.50 g Ru.sub.3 (CO).sub.12, 0.20 g Mn.sub.2 
(CO).sub.10, 2 ml of a solution of 57 percent HI, 25 ml acetic acid and 25 
ml of acetic anhydride and the contents heated at 230.degree. C. for two 
hours. Analysis by gas chromatography showed that the following acid 
products were produced: 8.0 g propionic acid and 2.6 g butyric acid. 
Esters were also present. 
EXAMPLE 4 
The procedure of Example 2 was exactly repeated except that the reactor was 
charged with 50 ml of propionic acid rather than acetic acid and the 
contents heated at 250.degree. C. for two hours. Analysis by gas 
chromatography showed that the following acid products were produced: 3.2 
g butyric acid and 0.32 g valeric acid. Esters were also observed. 
EXAMPLE 5 
The reactor of Example 1 was charged with a mixture of 0.50 g Ru.sub.3 
(CO).sub.12, 1.0 g I.sub.2, and 50 ml. of acetic acid. Equimolar amounts 
of CO and H.sub.2 were then added to attain a pressure of 3000 psi at 
25.degree.. The contents were heated to 250.degree. and shaken for two 
hours. Analysis by gas chromatography showed that 9.55 g of propionic acid 
and 1.59 g of butyric acid had been produced. 
EXAMPLE 6 
The procedure of Example 5 was followed exactly except that 0.60 g of 
I.sub.2 was used instead of 1.0 g. Analysis by gas chromatography showed 
that 5.47 g of propionic acid and 1.00 g of butyric acid had been 
produced. 
EXAMPLE 7 
A 500 ml. stainless steel bomb reactor containing a removable glass liner 
was charged with a mixture of 1.0 gram of Ru.sub.3 (CO).sub.12, 2.0 ml. of 
a solution of 57 percent HI, and 50 ml. of acetic acid. Equimolar amounts 
of carbon monoxide and hydrogen were then added to the reactor to attain 
an initial pressure therein of 3000 psi at 25.degree. C. The reactor was 
rocked and the contents heated at 260.degree. C. and maintained at this 
temperature for two hours with continued rocking of the reactor. The 
reactor was then cooled and vented. The contents of the reactor were 
removed and analyzed by gas chromatography. This analysis showed the 
following products were produced: 8.51 grams of propionic acid, 1.26 grams 
of butyric acid, and much smaller amounts of esters. 
EXAMPLE 8 
The procedure of Example 7 was exactly repeated except that the reactor was 
charged with a mixture of 0.25 gram of Ru.sub.3 (CO).sub.12, 0.5 ml. of a 
solution of 57 percent HI, and 50 ml. of acetic acid. This analysis showed 
that the product mixture contained: 27.1 grams of acetic acid, 6.68 grams 
of propionic acid, 1.40 grams of butyric acid, and smaller amounts of 
esters.