ISSN:
0894-3230
Keywords:
aryliminodimagnesium
;
condensation with NO2 and CO groups
;
addition to CN group
;
single electron transfer efficiency
;
σ-complexation ability
;
inter- and intramolecular competition
;
bifunctional substrates
;
positional effect of functional groups
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
---The reactions of aryliminodimagnesium [ArN(MgBr)2, IDMg] with p′-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 σ-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. © 1997 John Wiley & Sons, Ltd.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
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