Free-radical reactions of halogenated bridged polycyclic compounds. Part VIII. The addition of thiols to 1,2,3,4,7,7-hexachloro-5,6-dimethylenenorborn-2-ene

Abstract

The addition of methanethiol and thiophenol to 1,2,3,4,7,7-hexachloro-5,6-dimethylenenorborn-2-ene affords 1,4,5,6,7,7-hexachloro-3-methylnorborna-2,5-dien-2-ylmethyl methyl and phenyl sulphide respectively. These products are derived from 1,4-addition to the diene system, and this preference for 1,4- rather than 1,2-addition is discussed. Attempts to add bromotrichloromethane resulted in polymer formation. A new method for the synthesis of 1,2,3,4,7,7-hexachloro-5,6-dimethylenenorborn-2-ene by the catalytic hydrogenolysis of 1,2,3,4,7,7-hexachloro-5,6-bischloromethylnorborna-2,5-diene is reported.