Kinetics and Selectivities for the Solvolysis of N,N-Diphenylcarbamoyl Chloride

Article abstract of DOI:10.1021/jo00111a022

Values for the specific rates of solvolysis of N,N-diphenylcarbamoyl chloride have been analyzed using the two-term Grunwald-Winstein equation, incorporating the N_T solvent nucleophilicity scale and the Y_Cl solvent ionizing power scale.The sensitivities of 0.23+/-0.04 to changes in N_T and of 0.58+/-0.03 to changes in Y_Cl are consistent with an S_N1 pathway with extensive internal nucleophilic assistance and a weak nucleophilic solvation of the developing carbocation.Product studies have been performed in mixtures of water with methanol, ethanol, and 2,2,2-trifluoroethanol (TFE) and in TFE-ethanol mixtures.Giving further support to the proposed S_N1 mechanism, both the sensitivity to changes in solvent nucleophilicity and the product selectivities in aqueous ethanol and methanol parallel closely those previously determined for solvolyses of p-methoxybenzoyl chloride.