Reaction of 2-Nitropropan-2-ide Ion with m-Nitrobenzylidene Dibromide and Dichloride

Abstract

The reactions of m-nitrobenzylidene dichloride and dibromide with lithium 2-nitropropan-2-ide in dimethyl sulfoxide give a complex mixture of products (unlike the p-nitro isomers), which include: 1-chloro(bromo)-2-methyl-2-nitro-1-m-nitrophenylpropane and β,β-dimethyl-m-nitrostyrene, formed by S_RN1 and E_RC1 processes; 1-(1-methyl-1-nitroethyl)-2(and 4)-(2-methylprop-1-enyl)-4(and 2)- nitrobenzene, formed by nucleophilic ring attack; and acetone O-m-nitrobenzoyloxime and m-nitrobenzoic acid formed by radical and/or ionic processes. Several routes to 2-methyl-2-nitro-1-m-nitrophenylpropan-1-one, proposed as an intermediate leading to the above oxime ester, are proposed. Inhibitory and catalytic effects on these reactions are discussed.