Role of water traces in the liquid-phase catalytic hydrochlorination of olefins in organic solvents

Article abstract of DOI:10.1007/BF02498942

The liquid-phase hydrochlorination of 4,5,6,7,8,8,-hexachloro-3′,4,7,7′-tetrahydro-4,7-methanoindene (Chlordene) catalyzed by gallium or aluminum halides occurs in the presence of water traces in an aprotic organic solvent. Complexes H₂O · M₂X₆, where M is metal and X is halogen, catalyze this reaction. The reaction proceeds under homogeneous conditions. Under heterogeneous catalytic conditions, the solid phase in the AlCl₃-CCl₄ system attains the required concentration of AlCl₃ in the solution. It was shown using quantum-chemical PM3 calculations that the water molecule facilitates the transfer of proton in the form of the hydroxonium ion from an HCl molecule to olefin.