AbstLact -The monomethoxyl derivatives of various nelectron-deficient N-heteroaromatics reacted with phenylacetonitrile in tetrahydrofuran in the Presence of sodium hydride to give a-phenyl-N-heteraareneacetonitriles in the yields ranging from 45 to 7 8 % . On the contrary, the reaction of these methoxyl derivatives with ethyl cyanoacetate or malononitrile under Similar conditions was restricted within narrov limits. The synthesis of benzoyl-N-heteroaromatics by the air-oxidation of a-Phenyl-N-heteroareneacetonitriles was described additionally. In nucleophilic substitution at the a-and r-positions (active positions) of nelectron-deficient N-heteroaromatic compounds, aikoxyl groups are recognized to be very weak leaving groups, so that the reaction of the aikoxyl derivatives with nuCleOPhilic reagents, particularly with carbanions generated from active methylene compounds. is not uell investigated.' The reaction of 4-methoxyquinazol ine With nitrile-stabilized carbanions is an exceptional example, and the corresponding 4-subst i tuted products obtained.' As 11-lustrated in Scheme I. t t was suggested that at the highly active position of n-electron-deficient N-heteroaromatics, even aikoxyl groups might be replaced with nucleophilic reagents. Scheme 1 On the other hands, in 1954. Mizuno & LL have reported that phenylacetonitrile widely reacted with various chloro-N-heteroaromatics under basic conditions. and the a-phenyl-N-heteroareneacetonitriles were obtained in the yields ranging from 43 to Further, Panizzon has presented that phenylacetonitrile smoothly reacted with 2-chloropyridine which is known to be an inactive heteroaryl chlaride. although i t has a chlorine substituent at the u -~o s i t i o n .~ These findings demonstrate that phenylacetonitrile is an extremely powerful reagent comparing with Other active methylene compounds such as ethyl cyanoacetate, malononitrile, diethyl malonate, and acetylacetone From these points of view, we investigated the reaction o f various n-electrondeficient N-heteroaromaties containing a methaxyl group at their active Position with phenylacetonitrile under basic conditions in order to compare the reactivity of n-electron-deficient N-heteroaromatics for addition-elimination type nucleophilic substitutions. C, \ N OMe 6 m d q N N -OMe
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