Synthesis of 5-chloro-10,11-dihydro-5H-dibenzo[a,d] cycloheptene-5,10-sulfide and -5,11-dichloro-10,11-dihydro-5H-dibenzo[a,d] cycloheptene-5,10-sulfide and their oxidation

摘要

The chlorination of 5-thioxo-10,11-dihydro-5H-dibenzo[a,d] cycloheptene 2a gave 5-chloro-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5,10-sulfide 4. Chlorination of 5-thioxo-5H-dibenzo[a,d] cycloheptene 2b gave the two isomers cis- and trans-5,11-dichloro-10,11-dihydro-5H-dibenzo[a,d] cycloheptene-5,10-sulfide 7a,b. The two sulfides 4 and 7a,b were oxidized by using mCPBA or H_2O_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-5H-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.