Synthesis of 5-Chloro-10,11-Dihydro-5 H -Dibenzo[ a , d ]Cycloheptene-5,10-Sulfide and -5,11-Dichloro-10,11-Dihydro-5 H -Dibenzo[ A , D ]Cycloheptene-5,10-Sulfide and their Oxidation

Abstract

The chlorination of 5-thioxo-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene 2a gave 5-chloro-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene-5,10-sulfide 4 . Chlorination of 5-thioxo-5 H -dibenzo[ a,d ]cycloheptene 2b gave the two isomers cis - and trans -5,11-dichloro-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene-5,10-sulfide 7a,b . The two sulfides 4 and 7a,b were oxidized by using mCPBA or H 2 O 2 /AcOH to give the corresponding sulfoxides 5 and 8a,b , respectively. Treatment of the sulfide 7a,b with KI gave the primary ketone 1b together with trans -5-chloro-11-hydroxy-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene-5,10-sulfide 9 . The structures of the new compounds were established by different spectroscopic techniques as well as single crystal X-ray diffraction for compounds 4 and 9 .