Process for the carbonylation of diolefins

Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters

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560 81, 560183, 560198, 560204, 560206, 562483, 562590, 562592, 562595, C07C 6738

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042595193

ABSTRACT:
Conjugated diolefins (e.g., 1,3-butadiene) are carbonylated by the palladium-catalyzed addition of carbon monoxide and an alcohol of the formula ROH (e.g., benzyl alcohol) whereby polycarboxylic esters are formed in which the pair of double bonds of the conjugated diolefin has been transformed into a moiety having the formula: ##STR1## In the process, the olefin, carbon monoxide, and alcohol are reacted in the presence of a palladium(II) salt, a copper(II) salt, and a base, at certain concentrations and at a pressure and temperature sufficient to effect the carbonylation. The resulting unsaturated diester can be hydrolyzed and hydrogenated or vice versa to obtain the corresponding linear diacid (e.g., adipic acid).

REFERENCES:
patent: 3397226 (1968-08-01), Fenton
patent: 4171450 (1979-10-01), Kesling et al.
Carraro et al., Ger Offen. 1904429 as cited in Chem. Abstracts, 72, 12118u, (1970).
Pylander, Organic Syntheses with Noble Meta Catalysts, pp. 233-236 (1973).
James et al., JACS, 98:7, pp. 1810-1823 (1976).
Stille et al., J. Org. Chem. 44, 3474-3482 (1979).
James, as cited in Chem. Abstracts, 83, 205679p (12/22/75).

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