Reactions of nitrogen dioxide with hexenes. The mechanistic and structural factors controlling the product composition

Abstract

The reaction of nitrogen dioxide with a number of hexenes has been investigated using several solvents and the major products have been identified. The heterolytic reaction path has been effectively eliminated by the use of hexane as solvent. The mechanism of the heterolytic reaction path is discussed with the aid of ab initio molecular orbital calculations on possible nitrosating agents with particular reference to the syn and anti forms of nitrosyl nitrate. A new mechanism is proposed for the formation of certain trisubstituted derivatives.