Effect of added Dimethyl sulphoxide on the Solvolysis of Cinnamoyl Chloride in Aqueous Acetone and Acetonitrile

Kinetic studies on solvolysis of cinnamoyl chloride in aqueous acetone and acetonitrile with lesser water content shows an order 2.6 with respect to water and it is comparable to that of benzoyl chloride. The relatively greater enthalpy and lesser negative entropy of activation compared to benzoyl chloride favours an SN2 mechanism for cinnamoyl chloride rather than addition elimination mechanism. A sharp increase in rate observed in presence of small amounts of DMSO is due to its, strong basic and hydrogen bonding character leading to the liberation of strong nucleophile OH-, relatively greater stabilization of transition state than intial state which lowers the enthalpy and free energy of activation, distruction and interpenetration into the solvation shell of water and its direct interaction with the substrate.