The mechanism of lead tetraacetate decarboxylation. II. 2,3,3-Trimethylbutanoic and Adamantane-2-carboxylic acids

Abstract

Oxidative decarboxylation of 2,3,3-trimethylbutanoic acid with lead tetraacetate in benzene or acetic acid affords mainly 3,3-dimethylbut-2-yl acetate; the major product from the cupric salt catalysed reaction is 3,3-dimethylbut-1-ene. The low yields detected of rearrangement products provide evidence for the intermediacy of organolead and organocopper compounds which decompose by S_Ni displacement or cyclic cis-elimination. Other reactions discussed are oxidative decarboxylation of adamantane-2-carboxylic acid, deamination of 3,3-dimethylbut-2-ylamine, and thermolysis of bis(2,3,3-trimethylbutanoyl) peroxide and of t-butyl adamantane-2-percarboxylate. A reinterpretation of previous results on the oxidative decarboxylation of exo- and endo-nor- bornane-2-carboxylic acid with lead tetraacetate is presented.