Allylic carbonium ions. Part II. Solvolysis and cyclisation of some monoterpene 2,4-dinitrophenyl ethers

Abstract

The acetolyses of the 2,4-dinitrophenolates of nerol, geraniol, linalool, and α-terpineol are examined. Rates of reaction under various conditions are reported, and products are identified and analysed. Suggestions are made for harmonising proposals made earlier for solvolyses in other solvents and involving other leaving groups. The detailed mechanism of the acetolysis process is considered in terms of the Ingold S_N1–S_N2 and the Sneen ionpair hypotheses, and difficulties encountered by either of these schemes are discussed.