Hydrogen abstraction from diarylamines (4-X-C(6)H(4))(2)NH [X = H, CH(3), C(8)H(17), CH(3)O, and Br] by the 2-methyl-2-phenylpropyl radical in n-dodecane solution was investigated by thermolysis of 3-methyl-3-phenylbutanoyl peroxide in the presence of various concentrations of the amines. The reaction is a non-chain process in which the 2-methyl-2-phenylpropyl radical and its rearrangement product, the 2-benzylpropan-2-yl radical, abstract hydrogen from both the solvent and the amine. Cross-disproportionation reactions of the rearranged radical led to the formation of significant amounts of beta,beta-dimethylstyrene. Rate constants for hydrogen abstraction by the unrearranged, primary alkyl radical from n-dodecane (k(373K) = 3.5 x 10(3) M(-)(1) s(-)(1)), diphenylamine (k(373K) = 1.3 x 10(6) M(-)(1) s(-)(1)), and the substituted diarylamines were determined from the product yields and the known rate constant for the radical rearrangement. From kinetic experiments with N-deuteriodiphenylamine the deuterium kinetic isotope effect,k(NH)/k(ND), was found to be 2.3 at 373 K.

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The nitration and hydrogen exchange in the 4-position of the title compounds and corresponding N-methyl cations are studied kinetically. Criteria previously developed to distinguish between reaction on the free-base or conjugate-acid forms of six-membered heterocyclic aromatic compounds are applied. Both hydrogen-exchange and nitration occur on the free-base form of 3.5-dimethylisoxazole. For 1,3,5-trimethylpyrazole and 3.5-dimethylisothiazole, nitration occurs on the conjugate acids, while hydrogen-exchange undergoes a changeover from free-base to conjugate-acid reaction as the acidity is increased.The kinetic rates are compared with those for related compounds and the influence of N, 0, S. and NMe atomic groupings discussed.

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