Reductive activation of arenes: XVI. Anionic products from reduction of p-tolunitrile with sodium in liquid ammonia and their reaction with butyl bromide

Study of oxidation, protonation, and alkylation of the products obtained by one- and two-electron reduction of p-tolunitrile with sodium in liquid ammonia showed that these products are, respectively, p-tolunitrile radical anion and 1-cyano-4-methyl-2,5-cyclohexadienyl anion. The latter is formed by...

Full description

Saved in:
Bibliographic Details
Published inRussian journal of organic chemistry Vol. 39; no. 5; pp. 680 - 685
Main Authors Vaganova, TA, Starokon', EV, Shteingarts, VD
Format Journal Article
LanguageEnglish
Published NEW YORK Springer Nature 01.05.2003
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
RADICAL-ANIONS
BENZONITRILE
PHASE
ELECTRON-TRANSFER
ACIDITIES
ALKYL-HALIDES
Online AccessGet full text

Cover

More Information
Summary:Study of oxidation, protonation, and alkylation of the products obtained by one- and two-electron reduction of p-tolunitrile with sodium in liquid ammonia showed that these products are, respectively, p-tolunitrile radical anion and 1-cyano-4-methyl-2,5-cyclohexadienyl anion. The latter is formed by protonation of p-tolunitrile dianion with ammonia. The two-electron reduction involves protonation of p-tolunitrile dianion with initial p-tolunitrile, which gives rise to 4-cyanobenzyl anion. The yield of the latter depends on the order of mixing of the reactants. The anionic reduction products react with butyl bromide to afford products corresponding to ipso alkylation with respect to the cyano group, 4-butyltoluene and 3-butyl-3-cyano-6-methyl-1,4-cyclohexadiene, as well as the alkylation product at the benzylic position, 4-pentylbenzonitrile. The formation of 4-butyltoluene indicates the possibility for selective synthesis of p-alkyltoluenes by reductive alkylation of p-tolunitrile.
ISSN:1070-4280
1608-3393
DOI:10.1023/A:1026009329198