Chemistry of carbon compounds – Miscellaneous organic carbon compounds – C-metal
Patent
1984-04-23
1987-07-21
Shippen, Michael L.
Chemistry of carbon compounds
Miscellaneous organic carbon compounds
C-metal
560105, 560114, 560204, 560206, 560232, 560233, 560 97, 562406, 562497, 562522, C07C 6738
Patent
active
046817077
DESCRIPTION:
BRIEF SUMMARY
The present invention relates in general to a process for the production of carboxlyic acid esters and/or carboxylic acids and in particular to a process for the production of carboxylic acid esters and/or carboxylic acids by the catalysed reaction of an unsaturated hydrocarbon, carbon monoxide and either water or an alcohol, optionally in the presence of oxygen.
Processes for the production of esters by reacting an olefin with carbon monoxide and an alcohol in the presence of a catalyst and in the presence or absence of oxygen are known. Representative of the published art are U.S. Pat. No. 4,303,589, Belgian Pat. No. 877770, Japanese Patent Publication No. 53040709 and U.S. Pat. No. 3,780,074.
U.S. Pat. No. 4,303,589 (Monsanto) describes a process for the production of carboxylate esters by (a) reacting internal olefins with carbon monoxide and an alcohol at 170.degree. to 200.degree. C. and 1200-1800 psig in the presence of a cobalt catalyst and a pyridine promoter, (b) diluting the reaction mixture with a large amount of hydrocarbon to cause phase separation, (c) separating the ester from the other phase, which contains more than 90% of the cobalt catalyst and (d) recycling the catalyst to step (a).
Belgian Pat. No. 877770 describes the production of polycarboxylic esters by reacting an olefin containing at least two conjugated double bonds with carbon monoxide and an alcohol in the presence of a base and a palladium/copper catalyst.
Japanese Patent Publication No. 5 3040 709 describes the production of dicarboxylic acid diesters by reacting an olefin, carbon monoxide, oxygen and an alcohol in the presence of a catalyst containing (a) a palladium group metal or a compound thereof, (b) a copper salt and (c) a tertiary amine.
Finally, U.S. Pat. No. 3,780,074 describes the production of alkadienoic acid esters by reacting a 4-12 carbon acyclic conjugated aliphatic diolefin with a 1 to 20 carbon monohydroxy alcohol and carbon monoxide in the presence of zero valent palladium and a phosphine activator at 80.degree. to 160.degree. C. in the absence of oxygen.
Methods are also known for the hydroesterification of acetylene to produce isomeric esters. For example, G. P. Chiusli et al report in Chem. Ind., 977, (1968) the reaction of acetylene with carbon monoxide in the presence of 4% oxygen and thiourea and a palladium (II) chloride catalyst. A disadvantage of this process is that the selectivity to isomeric esters (cis and trans-diesters) is considerably reduced by the accompanying formation of polymeric materials and isomeric muconate esters.
We have now found that carboxylic acid esters and/or carboxylic acids can be produced by reacting an unsaturated hydrocarbon with carbon monoxide and either water or an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper, both in the presence and the absence of oxygen. In contrast with the majority of prior art processes which utilize a base as an essential reactant, the process of the present invention utilises an acid. The process of the invention in contrast with prior art processes can be operated under relatively mild conditions and exhibits a high regiospecificity to desirable products.
Accordingly, the present invention in one aspect provides a process for the production of a carboxylic acid ester which process comprises reacting an unsaturated hydrocarbon with carbon monoxide and an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper.
The unsaturated hydrocarbon may suitably be an olfein. The olefin may suitably be an acyclic olefin containing from 2 to 30 carbon atoms per molecule or a cyclic olefin containing from 5 to 30 carbon atoms per molecule. The olefin may have either 1, 2 or 3 olefinic carbon-carbon double bonds per molecule, which double bonds may be internal or terminal and may be conjugated or non-conjugated in olefins containing a plurality of
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Alper Howard
Despeyroux Bertrand
Smith David J. H.
Woell James B.
Shippen Michael L.
The British Petroleum Company p.l.c.
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