The effect of pressure on cyclic reactions

Abstract

Rates of the cyclization of 4-chlorobutanol and of some analogous non- cyclic solvolysis reactions have been measured in water, methanol, and aqueous acetone at pressures up to 3000 atm. The volume of activation of the cyclic reaction is less negative than those of the linear reactions, in each solvent, but it is suggested that the transition states of both types of reaction may be solvated to about the same extent. The volume of activation for the formation of an eight-membered ring in the cyclization of 4-bromobutylcatechol monoether was also determined.