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35.1.1.1.1.4 Method 4: Reactions with Trichloromethanesulfenyl Chloride

DOI: 10.1055/sos-SD-035-00004

Hartung, J.Science of Synthesis, (20073525.

Visible-light photolysis of aliphatic or alicyclic hydrocarbons in the presence of trichloromethanesulfenyl chloride (perchloromethyl mercaptan) affords alkyl chlorides 9 in synthetically useful yields and selectivities (Scheme 7).[‌36‌,‌37‌] An increase in selectivity is possible by use of benzene as cosolvent. The reaction is inhibited by alkenes. Hydrogen chloride and bis(trichloromethyl) disulfide are formed as side products. The latter may be converted into trichloromethanesulfenyl chloride upon treatment with chlorine, if desired. Compared to trichloromethanesulfonyl chloride, trichloromethanesulfenyl chloride offers the advantage of being applicable over a wider temperature range. The high relative CH reactivity index has been attributed to the trichloromethylsulfanyl radical being the key intermediate, which constitutes a rare example of an efficient sulfur-based hydrogen-atom abstractor. The driving force for hydrogen-atom abstraction from the alkane in this case has been attributed to a comparatively strong SH bond in trichloromethanethiol. This compound is converted into bis(trichloromethyl) disulfide and hydrogen chloride by trichloromethanesulfenyl chloride.

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