Tsutomu Fujimoto, Ichiro Hirao
1974
Citations
0
Influential Citations
3
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The telomerization of methyl acetate and cyanoacetate with ethylene initiated by di-tert-butyl peroxide was investigated. Methyl esters of linear and α-branched alkanoic acids, and linear and α-branched alkyl acetates, as well as hydrocarbons, were identified in the system of methyl acetate. The methyl esters of linear and α-branched α-cyanoalkanoic acids were identified in the system of methyl cyanoacetate, but no alkyl cyanoacetates could be found. It was suggested that intramolecular 1,5-hydrogen transfer in telomer radicals with two ethylene units and a chain-transfer reaction to the telomers gave the branched telomers. The chain-transfer constants were estimated in the system of methyl cyanoacetate. The introduction of the cyano group to methyl acetate at the α-position gave a favorable system for chain-transfer reactions and facilitated intramolecular 1,5-hydrogen transfer in the telomer radicals. The relatively higher relative reactivity of the methoxy group to the acetyl group in methyl acetate in...