REACTION OF ARYLIMODIMAGNESIUM WITH AROMATIC BIFUNCTIONAL NITRILES: COMPETITION AND/OR COOPERATION OF FUNCTIONAL GROUPS AFFECTED BY ELECTRON-ACCEPTING ABILITY AND LOCATION
✍ Scribed by Masao Okubo; Masayo Sakata; Yuko Iwatsu; Nobuyuki Tsurusaki; Sawako Nakashima; Yoshihito Iwamoto; Harumi Nonaka; Akira Yamauchi; Koji Matsuo
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 193 KB
- Volume
- 10
- Category
- Article
- ISSN
- 0894-3230
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✦ Synopsis
The reactions of aryliminodimagnesium [ArN(MgBr) 2 , IDMg] with pЈ-substituted p-cyanobenzophenones, 1-cyano-9-fluorenone, o-, m-and p-dicyanobenzenes and o-, m-and p-nitrobenzonitriles were examined, and the relative yields of products were referred to the previous results of electron spin resonance studies. The products of condensation with carbonyl and nitro groups and of addition to cyano groups were formed. From the variations of the yields caused by the molar ratio of the magnesium reagent versus substrates and by the substituents of both reactants, the preferred groups were determined. The groups of p-and m-substrates are consistent with the position of highest density of free electrons in the anion radicals, whereas those of the o-substrates are inconsistent. The consistency indicates competition of functional groups reflecting the relative ability of single electron acceptance from the reagent, whereas the inconsistency is ascribed to cooperation of neighbouring groups for -complexation with the Mg atom of the reagent. The categories of competition and cooperation are discussed in relation to fundamental features and general governing factors proposed for the IDMg reactions of monofunctional substrates.