NEW AND FACILE SUBSTITUTION REACTIONS AT TERTIARY CARBON
Abstract
p-Nitrocumyl chloride (Ia) reacts with quinuclidine, DABCO,piperidine, pyrrolidine, ammonia, methylamine, dimethylamine,trimethylamine, n-butylamine and di-n-butylamine in DMSO, at ca.35(DEGREES), in the light to form the alkylated amines (III) in 27-91% yields.The failure of tri-n-butylamine, pyridine and N,N-dimethylaniline toreact with (la) is discussed. (alpha),p-Dinitrocumene (Ib) reacts withpiperidine in DMSO, at ca. 30(DEGREES), in the light to give the alkylatedamine in 77% yield. Evidence is presented in support of the viewthat these reactions proceed via a radical anion chain sequence(equations 1-4). It is especially significant that oxygen completelysuppresses alkylation: thus, p-nitrocumyl chloride is converted top-nitrocumyl alcohol and p-nitrocumyl hydroperoxide on exposureto quinuclidine or piperidine under an oxygen atmosphere. Equallysignificant is the ability of 1 mole percent of oxygen to completelyinhibit the reaction of (la) with quinuclidine for more than 2 hours.The radical anion chain mechanism also accounts for the followingfacts: light greatly speeds up these reactions; a catalytic amount oflithium 2-propanenitronate greatly increases the rate of alkylation inthe dark; and, p,p'-dinitrobicumyl is isolated in up to 34% yields when tri-n-butylamine is allowed to react with (Ia). . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of school.) UMI
Degree
Ph.D.
Subject Area
Organic chemistry
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