
TY  - JOUR
A1  - Bizilj, S 
A1  - Kelly, DP 
A1  - Serelis, AK 
A1  - Solomon, DH 
A1  - White, KE 
T1  - The Self-Reactions of 1-Methoxycarbonyl-1-methylethyl and Higher Ester Radicals: Combination vs Disproportionation and Oligomeric Products from Secondary Reactions
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1985
VL  - 38
IS  - 11
SP  - 1657
EP  - 1673
KW  - 
UR  - https://doi.org/10.1071/CH9851657 
N2  - 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). 
ER  -

