SELECTIVITY OF ATTACK IN NUCLEOPHILIC ALKYLATION OF NITROARENES WITH GRIGNARD-REAGENTS - REACTIVITY OF SOME SUBSTITUTED NITROBENZENES AND NITRONAPHTHALENES

Reactivity of some substituted nitrobenzenes and nitronaphthalenes with RMgX has been investigated. In all reactions C-alkylation products have been obtained. The entering alkyl group exhibits a great tendency to attack at unsubstituted positions. Examples of nucleophilic displacement of a nucleofugic group by an alkyl group are also reported. Our findings are discussed and compared with analogous studies on relative reactivities of differently substituted aromatic carbons toward nucleophiles. Anomalous behavior has been observed for reactions of methoxy derivatives which yield nitrocyelohexadienic or cyclohexenic compounds and lesser amounts of the expected nitroso derivatives. This unusual reactivity can be accounted for by a rapid aci-nitro tautomerization whichprevails over decomposition to nitroso compounds. © 1979, American Chemical Society. All rights reserved.