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 to react with (la) is discussed. (alpha),p-Dinitrocumene (Ib) reacts with piperidine in DMSO, at ca. 30(DEGREES), in the light to give the alkylated amine in 77% yield. Evidence is presented in support of the view that these reactions proceed via a radical anion chain sequence (equations 1-4). It is especially significant that oxygen completely suppresses alkylation: thus, p-nitrocumyl chloride is converted to p-nitrocumyl alcohol and p-nitrocumyl hydroperoxide on exposure to quinuclidine or piperidine under an oxygen atmosphere. Equally significant is the ability of 1 mole percent of oxygen to completely inhibit the reaction of (la) with quinuclidine for more than 2 hours. The radical anion chain mechanism also accounts for the following facts: light greatly speeds up these reactions; a catalytic amount of lithium 2-propanenitronate greatly increases the rate of alkylation in the 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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