Effect of pressure on the rates of hydrolysis of allyl chlorides

Abstract

The pressure dependence of the rates of hydrolysis of allyl chloride and α-, β-, and γ-methyl allyl chlorides has been examined. The significance of the activation volumes, ΔV*, and their pressure dependence, dΔV*/dP, is discussed. These activation parameters indicate an SN2 mechanism for allyl and β-methyl allyl chloride and an SN1 or intermediate character mechanism for the other methyl substituted allyl chlorides investigated. The results are compared with the corresponding ΔH* and ΔCP* measurements of Robertson and co-workers. The temperature dependence of the activation volume, dΔV*/dT, for the solvolysis of the parent allyl chloride has been measured and found to be small and negative.