ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
On the Knowledge of the Catalytic Dimerization of Acrylic Acid Derivatives by Palladium Complexes. III Reactions of β-Palladio Acrylates and Their Relation to the Catalytic ReactionComplexes of the type L2PdCl(CH = CHCOOCH3) (L2 = 2 PPh3 or Ph2PCH2CH2PPh2) were decomposed to dimethyl muconate by pyrolysis or by substraction of the phosphine ligands with (CH3CN)2PdCl2 in acetonitrile. The last mentioned reaction gave Δ3-dimethyl dihydromuconate in the presence of hydrochloric acid. Δ3-Dimethyl dihydromuconate was also formed by decomposition of (Ph2PCH2CH2PPh2) PdCl (CH = CHCOOCH3) with HBF4 in acetonitrile, but the analogous reaction in methyl acrylate as solvent gave Δ2-dimethyl dihydromuconate. Thus, we have simulated the formation of the two main products of the catalytic dimerization of methyl acrylate with palladium(II)chloride in a stoichiometric manner. Mechanisms with hydride and carbene intermediates are discussed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19803220514
