Kinetic and Thermodynamic Study of the Base-Catalyzed Oxidative Cleavage of 1,1-Bis(p-chlorophenyl)-2,2,2-trichloroethanol

Article abstract of DOI:10.1021/jo00332a007

The kinetics and mechanism of the base-catalyzed oxidative cleavage of 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol (1a) and 1,1-diphenyl-2,2,2-trichloroethanol (1b) have been studied as a function of base concentration, solvent, and temperature.The pseudo-first-order rate constant for the disappearance of both 1a and 1b increases linearly at low base concetration, reaching a plateau at high hydroxide ion concetration.From data obtained in the plateau region values of 18.7 kcal/mol, 21.3 kcal/mol, and 8.8 eu were determined for the free energy, enthalpy, and entropyof activation of 1a, respectively.The values of the activation parameters for compound 1b are similar to those described for 1a.The data obtained are consistent with an ElcB-type mechanism.