Trichloromethanesulfonyl chloride

In the chlorination by trichloromethanesulfonyl chloride, cyclohexane is about three times as reactive as toluene. 

Attempts to prepare sulfonyl cyanides from the corresponding sulfonyl chlorides according to the procedure described were unsuccessful when applied to mono-, di-, and trichloromethanesulfonyl chloride, to dimethylsulfamoyl chloride, and to ethylene- and 2,4-diiiitrophenylsulfonyl chloride. 

The oxidation of trichloromethanesulfenyl chloride by nitric acid or oxidative chlorination in the presence of water yields trichloromethanesulfonyl chloride [2547-61-7], CC13S02C1, which is a lacrimatory solid (mp 140—142.5°C), which is surprisingly stable to hydrolysis and can be steam-distilled. 

Trichloromethanesulfonyl chloride is a more selective reagent. The reaction is initiated by light or peroxides and involves hydrogen abstraction by the trichloromethanesulfonyl radical 128... 

Chlorination (-Butyl hypochlorite. N-Chiorosuccinimide. Cupric chloride. Dibenzoyl peroxide. Dimethylformamide. Phosphorus pentachloride. Phosphorus trichloride. Selenium oxychloride. Sodium chlorate. Sulfuryl chloride. Tetra- -butylammonium iodotetrachloride. N,2,4,6-Tetrachloroacetanilide. Thionyl chloride. Trichloromethanesulfonyl chloride. Triphenylphosphine dichloride. 

Radicals Azobisisobutyronitrile. a,T-Bis(diphenylene)-d-phenylallyL r-Butyl perbenzoate. 7-Butyrolactone. Dibenzoyl peroxide. Di-r-butyl nitroxidc. Di-r-butyl peroxide. Diphenyl-picrylhydrazyl. Galvinoxyl. Hydrogen peroxide-iron salts. Lead dioxide. N-Phenyl-N -benzoyldiimide. Potassium nitrosodisulfonate. Thiolacetic acid. Trichloromethanesulfonyl chloride. 

Ruthenium-catalyzed asymmetric addition of alkane- or arenesulfonyl chlorides to styrenes leads to optically active suifones22,23. When this conversion is conducted under mild conditions no C —C bond is formed, however, at higher temperatures (100 =C), enantioselective asymmetric carbohalogenation of styrene with trichloromethanesulfonyl chloride (accompanied by sulfur dioxide extrusion) can be achieved with tetrachlorotris[( + )- or (—)-Diop]diruthenium. Excellent yields (up to 100%), but only low asymmetric inductions (up to 13 %), arc observed12. Similar results are obtained with carbon tetrachloride. A mechanism with radical formation w ithin the metal coordination sphere ( radicaloid ) has been proposed. 

The chlorination has been compared with bromination by BrCClj carried out under radical chain conditions. In this reaction, cyclohexane is about one-fifth as reactive as toluene, but in the chlorination by trichloromethanesulfonyl chloride, cyclohexane is about three time more reactive that toluene. Does this information permit a choice between the chain sequences you have written in part (a) ... 

---