Induced decomposition of t-butyl peroxide in solution

Abstract

THE thermal decomposition of t-butyl peroxide has been studied extensively.1 Earlier work has shown that the peroxide has little tendency to undergo induced decomposition and that its rate of decomposition is solvent independent.2 In the few instances where induced decomposition has been detected this occurs largely by hydrogenabstraction.lq3 In contrast, we now show that t-butyl peroxide undergoes considerable induced decomposition in substituted benzyl methyl ethers, ArCH,OMe, which probably involves attack by the solvent radical ArCHOMe on the 0-0 bond in the peroxide. Decomposition of t-butyl peroxide in p-chlorobenzyl methyl ether a t 110 gave a-t-butoxy-pchlorobenzyl methyl ether (I) (36%), among other products (see Table) known to be derived from the solvent radical ArkHOMe.4 The structure of (I) was determined by elemental analysis, and by comparison (i.r. and v.P.c.) with an authentic sample prepared from a-chloro-+chlorobenzyl methyl ether and sodium t-butoxide in dimethyl sulphoxide and isolated through preparative V.P.C. Similarly, decomposition of the peroxide in mchlorobenzyl methyl ether yielded the acetal (11) (1776) . The structure of (11) was determined by