Use of a Sacrificial Aluminum Anode in the Acylation of Some Olefins

• Published in: Bulletin of the Chemical Society of Japan 1998-04, Vol.71 (4), p.899-904
• Main Authors: Vukicevic, Rastko D, Joksovic, Ljubinka, Konstantinovic, Stanimir, Markovic, Zoran, Mihailovic, Mihailo Lj
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.71.899

The acylation of some alicyclic and aliphatic alkenes by the electrochemical generation of a catalyst using a sacrificial aluminum anode was investigated. Substrates were electrolyzed in a dichloromethane solution of an appropriate electrolyte (tetraalkylammonium salts) in the presence of an acylating agent (acetyl chloride or anhydride). Thus, unsubstituted cycloalkenes, namely cyclohexene and cycloheptene, gave by that reaction conjugated ketones, i.e. the corresponding 1-acetylcycloalkenes, as the only unsaturated carbonyl compounds in moderate-to-good yields. Under the same reaction conditions their 1-methyl derivatives gave mixtures of the corresponding conjugated and β,γ-unsaturated isomeric ketones in which unconjugated compounds predominate. In both cases unsaturated ketones were accompanied by different amounts of side products. Terminal aliphatic alkenes (1-hexene, 1-heptene, and 1-dodecene) afforded only conjugated a ketone with a normal skeleton, but in lower yields. The acylation of cyclohexene was studied in more detail, altering the reaction conditions by changing the reaction temperature, the supporting electrolyte, the acylating agent and the electrochemical cell. Mechanistic considerations were made on the basis of the products distribution and some theoretical calculations being made by the MOPAC program package (version 7.0).