REACTION OF ARYLIMODIMAGNESIUM WITH AROMATIC BIFUNCTIONAL NITRILES - COMPETITION AND OR COOPERATION OF FUNCTIONAL-GROUPS AFFECTED BY ELECTRON-ACCEPTING ABILITY AND LOCATION/

Citation
M. Okubo et al., REACTION OF ARYLIMODIMAGNESIUM WITH AROMATIC BIFUNCTIONAL NITRILES - COMPETITION AND OR COOPERATION OF FUNCTIONAL-GROUPS AFFECTED BY ELECTRON-ACCEPTING ABILITY AND LOCATION/, Journal of physical organic chemistry, 10(4), 1997, pp. 242-252
Citations number
25
Categorie Soggetti
Chemistry Physical","Chemistry Inorganic & Nuclear
ISSN journal
08943230
Volume
10
Issue
4
Year of publication
1997
Pages
242 - 252
Database
ISI
SICI code
0894-3230(1997)10:4<242:ROAWAB>2.0.ZU;2-4
Abstract
The reactions of aryliminodimagnesium [ArN(MgBr)(2)IDMg] with p'-subst ituted p-cyanobenzophenornes, 1-cyano-9-fluorenone, o-, m- and p-dicya nobenzenes and o-, m- and p-nitrobenzonitriles were examined, and the relative yields of products were referred to the previous results of e lectron spin resonance studies. The products of condensation with carb onyl and nitro groups and of addition to cyano groups were formed. Fro m the variations of the yields caused by the molar ratio of the magnes ium reagent versus substrates and by the substituents of both reactant s, the preferred groups were determined, The groups of p- and m-substr ates are consistent with the position of highest density of free elect rons in the anion radicals, whereas those of the o-substrates are inco nsistent. The consistency indicate competition of functional groups re flecting the relative ability of single electron acceptance from the r eagent, whereas the inconsistency is ascribed to cooperation of neighb ouring groups for sigma-complexation with the Mg atom of the reagent, The categories of competition and cooperation are discussed in relatio n to fundamental features and general governing factors proposed for t he IDMg reactions of monofunctional substrates. (C) 1997 by John Wiley & Sons, Ltd.