Competing SNAr displacements of nitrite and SN2 displacements on the alkyl groups of alkyl p-nitrobenzoates and o-nitrobenzoates

Article abstract of DOI:10.1021/jo00321a022

Several p-nitrobenzoate and o-nitrobenzoate esters have been found to undergo competing S_NAr and S_N2 reactions with azide, alkoxide, and thiophenoxide ions. S_NAr displacement of the nitro group even competes with S_N2 displacement on the methyl group of methyl esters 1c and 11. Esters 1a and 1b undergo predominately S_NAr displacements with azide, whereas 1c undergoes predominately an S_N2 displacement with azide. Both 1b and 1c undergo predominately S_NAr reactions with alkoxides and thiophenoxide. The S_NAr products from the azide reactions consist of mixtures of p-azidobenzoates, p-aminobenzoates, and 4,4′-azodibenzoates whose compositions depend upon the reaction conditions.