Reaction of α,β-Unsaturated Carboxylic Acids with Manganese(III) Acetate in the Presence of Chloride Ion

• Published in: Bulletin of the Chemical Society of Japan Vol. 59; no. 10; pp. 3153 - 3159
• Main Authors: Yonemura, Hiroshi, Nishino, Hiroshi, Kurosawa, Kazu
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 01.10.1986; Chemical Society of Japan
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Inorganic free radical; Chemical reaction; Carboxylic acid; Chlorides; Decarboxylation; Chlorocarbon; Radical mechanism; Vinylic compound; Addition reaction; Benzenic compound; Chloro complex; Aromatic compound; Manganese III Complexes; Oxidation
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.59.3153

The reaction of 3-phenylpropenoic acids with manganese(III) acetate–Cl− complex yielded 1,2,2-trichloro-1-phenylethanes, 1-acetoxy-2,2-dichloro-1-phenylethanes, and 2,2-dichloro-1-phenylethanols. (E)-2,3-Diphenylpropenoic acids gave 2,2-dichloro-1,2-diphenylethanones and 2-acetoxy-1,2-diphenylethanones. 3,3-Diphenylpropenoic acids yielded 2,2-dichloro-1,1-diphenylethenes, 1-acetoxy-2,2-dichloro-1,1-diphenylethanes, 2,2-dichloro-1,1-diphenyl-1-ethanols, and 2-hydroxy-2,2-diphenylethanal. Fluorenylideneacetic acid gave 9-chloro-9-(dichloromethyl)fluorene, 9-acetoxy-9-(dichloromethyl)fluorene, and 9-fluorenone. 1-Cyclohexenecarboxylic acid yielded 1,2-dichlorocyclohexanecarboxylic acid and 1-acetoxy-2-chlorocyclohexanecarboxylic acid. The reaction can be explained in terms of a free-radical mechanism involving manganese(III) acetate–Cl− complexation, addition of Cl− radical, decarboxylation, and the oxidation of chloroethenes which are the reaction intermediates.