
%0 Journal Article
%A Bizilj, S 
%A Kelly, DP 
%A Serelis, AK 
%A Solomon, DH 
%A White, KE 
%T The Self-Reactions of 1-Methoxycarbonyl-1-methylethyl and Higher Ester Radicals: Combination vs Disproportionation and Oligomeric Products from Secondary Reactions
%J Australian Journal of Chemistry
%D 1985/11/01
%V 38
%N 11
%P 1657-1673
%K 
%R https://doi.org/10.1071/CH9851657
%U https://www.publish.csiro.au/paper/CH9851657 
%X The geminate self-reactions of the title methyl, ethyl and butyl ester radicals-(2a-c), formed by decomposition of the corresponding azo precursors (1a-c) in the presence of stable nitroxide radical scavengers, were found on the basis of product analysis to comprise combination and disproportionation in the ratios 56 : 44 (methyl), 58 : 42 (ethyl) and 47 : 53 (butyl). In the absence of radical scavengers, extensive oligomerization is observed. Hydrogenation and degradation were used in conjunction with g.l.c.-m.s . to deduce the identities of the dimeric, trimeric and tetrameric products, which were in most cases subsequently confirmed by isolation and n.m.r . analysis. Of particular interest is the highly regioselective disproportionation of radical (3) to give dimethyl 4-methylpent-1-ene-2,4-dicarboxylate (8), and the further reaction of (8) with (2a) to form branched oligomers (10) and (15). 
