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Carboalkoxylation

Process for converting alkenes to esters

In industrial chemistry, carboalkoxylation is a process for converting alkenes to esters. This reaction is a form of carbonylation. A closely related reaction is hydrocarboxylation, which employs water in place of alcohols.

A commercial application is the carbomethoxylation of ethylene to give methyl propionate:

C2H4 + CO + MeOH → MeO2CC2H5

The process is catalyzed by Pd[C6H4(CH2PBu-t)2]2. Under similar conditions, other Pd-diphosphines catalyze formation of polyethyleneketone.

Methyl propionate ester is a precursor to methyl methacrylate, which is used in plastics and adhesives.

Carboalkoxylation has been incorporated into various telomerization schemes. For example carboalkoxylation has been coupled with the dimerization of 1,3-butadiene. This step produces a doubly unsaturated C9-ester:

2 CH2=CH−CH=CH2 + CO + CH3OH → CH2=CH(CH2)3CH=CHCH2CO2CH3

01Hydroesterification

Related to carboalkoxylation is hydroesterification, the insertion of alkenes and alkynes into the H-O bond of carboxylic acids. Vinyl acetate is produced industrially by the addition of acetic acid to acetylene in the presence of zinc acetate catalysts: Presently, zinc acetate is used as the catalyst:

CH3CO2H + C2H2 → CH3CO2CHCH2
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