The chemistry of sulfenyl halides: Part III: Photochlorination of alkyl chlorides with trichloromethylsulfenyl chloride

✍ Scribed by H. Kloosterziel

• Publisher: Elsevier Science
• Year: 2010
• Tongue: English
• Weight: 370 KB
• Volume: 82
• Category: Article
• ISSN: 0165-0513
• DOI: 10.1002/recl.19630820511

✦ Synopsis

Abstract

The photochlorination of some alkyl chlorides with trichloromethylsulfenyl chloride has been investigated. Product distributions and reactivities relative to alkanes were determined. The results show the importance of polar effects and can be correlated with the polar substituent constants σ*. A chlorine atom reduces the reactivity of a neighbouring carbon‐hydrogen bond by a factor of 45. The reactivities at other positions correspond to a loss factor of 1.6. A methyl group exerts a slight activating polar effect.

A correlation with NMR chemical shifts suggests that the differences in reactivity of methylene groups in hydrocarbons, as reported in Part II ^2^, are also due to polar effects.