SNAr, SN2, and Aromatic Addition Processes in the Reactions of Picryl Ethers with Nitrogen and Carbon Bases

Article abstract of DOI:10.1021/jo00265a008

The reactions of methyl, cyclohexyl, and phenyl picryl ethers with diethyl- and triethylamine in chloroform, acetone, and 1,3-dicarbomethoxyacetone have been studied.A number of different processes were observed, depending on substrate structure.Both amine nitrogen and enolate carbon act as nucleophiles in these reactions.With unhindered picryl ethers like 2,4,6-trinitroanisole, dealkylation often occurs via S_N2 attack on the methyl group.With more hindered picryl ethers, addition to the ring is more common, resulting in covalent ? complexes, substituted picramides, or bicyclo <3.3.1> nitropropenenitronates.In this paper, structural features that influence reaction path are discussed.