Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1985-12-17
1987-02-10
Trousof, Natalie
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
502102, 502160, 502165, 502166, 502167, 502223, 502225, 502230, 502326, 502331, 560193, C07C 6738
Patent
active
046423745
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for the oxidative carbonylation of alkenes using platinum group metal/copper catalysts. In particular, the present invention relates to a process for the production of esters of dicarboxylic acids by the oxidative carbonylation of alkenes in an alcohol using a platinum group metal/copper catalyst.
Esters of dicarboxylic acids, for example esters of succinic acid, find wide application as plasticisers in a variety of synthetic resins. They are also used as additives to lubricating oils and as intermediates in the manufacture of succinic acid.
The carbonylation of alkenes or alkynes in the presence of hydrogen by a number of soluble homogeneous transition metal catalysts, in particular rhodium, are well known chemical reactions. In such "hydroformylation" reactions an alkene, for example, is reductively carbonylated to produce an aldehyde derivative. ##STR1##
It is also known, for example from U.S. Pat. No. 3,397,225 that alkenes can be oxidatively carbonylated to esters of carboxylic acids by reaction of the alkene with carbon monoxide and an alcohol in the presence of a platinum group metal/copper catalyst. The process described in this reference however produces unsaturated monocarboxylic acid esters e.g. acrylate esters.
A serious drawback with all the oxidative carbonylation processes described in the prior art is that during the carbonylation reaction the catalyst is reduced to a lower oxidation state having no catalytic activity. To run such a process on an industrial scale it is therefore necessary to reactivate the catalyst continuously by reoxidising with oxygen or air. The need to reoxidise the catalyst continuously leads to operationl difficulties since either the catalyst must be removed from the reactor in which the carbonylation reaction takes place and oxidised separately or it must be oxidised in situ. The first option leads to the need for expensive extra catalyst separation/transfer steps, while, if the second option is chosen, serious risk of explosion from carbon monoxide/oxygen mixtures arises.
A process has now been devised which allows the catalyst to be reoxidised in situ within the carbonylation reactor while decreasing considerably the risk of an explosive reaction occuring. This is achieved by using a dihydrocarbyl peroxide as an oxidising agent instead of air or gaseous oxygen. By using dihydrocarbyl peroxides the formation of water is also avoided. This is of importance since not only does the presence of water in the carbonylation reactor complicate product separation, but it also causes deactivation of the catalyst and enhances the formation of carbon dioxide as an unwanted byproduct.
Accordingly, the present invention provides a process for the production of an ester of a dicarboxylic acid by the carbonylation of an alkene which process comprises reacting the alkene with carbon monoxide, an alcohol and a dihydrocarbyl peroxide in the presence of an effective amount of a catalyst comprising a platinum group metal and a copper compound.
The esters produced in the present process are suitably diesters and are the ones formed by adding a --CO.sub.2 E group where E is a hydrocarbyl group to the alkene. Thus when the alkene is ethylene, the diester produced is a diester of succinic acid.
It will be appreciated by those skilled in the art, however, that if a dialkene, e.g. butadiene, is used the ester formed can be one having two or four ester groups. It is intended that the term diester should be construed, in the context of the present invention, as relating to compounds having two or a multiple of two ester groups, the multiple being dependent upon the number of carbon-carbon double bonds in the alkene.
The ester groups attached to the dicarboxylic acid are suitably derived from the alcohol reactant. Thus the product of the reaction between ethylene, ethanol, carbon monoxide and di-tertiary-butyl peroxide is mainly diethyl succinate. However, since during the reaction the dihydrocarbyl peroxide is converted into the equivalent hydrocarby
REFERENCES:
patent: 4138580 (1979-02-01), Umemura et al.
patent: 4160107 (1979-07-01), Agnes et al.
Lucy Andrew R.
Morris George E.
Clarke Vera C.
The British Petroleum Company p.l.c.
Trousof Natalie
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