The 9-Decalyl and Related cations VII. Solvolysis of 3-(Cyclohex-1′-enyloxy)propyl p-Nitrobenzenesulfonate

Abstract

The solvolysis of 3-(cyclohex-1′-enyloxy) propyl p- nitrobenzenesulfonate (5) in ethanol buffered separately with sodium ethoxide and triethylamine and 2,2,2-trifluoroethanol buffered with triethylamine has been investigated. Kinetic determinations and product studies have been carried out.

In ethanol buffered with sodium ethoxide , π-bond participation in the above ester occurs to the extent of 30%; this is raised to 84% when triethylamine is used as the buffering agent.

With buffered trifluoroethanol as solvent, π-bond participation in the ester is complete; k_unsat/k_sat = 920 and a quantitative yield of cyclized products is obtained.

Kinetic evidence indicates a lack of significant involvement of a lone pair on oxygen (enol ether system) in the solvolysis of the sulfonate ester; in trifluoroethanol , the compound solvolyses only 1.15 times more rapidly than does 4-(cyclohex-1′-enyl)butyl p-nitrobenzenesulfonate (2), its carbon analogue.