Sulfonyl chlorides, desulfonations

Noncatalytic desulfonation takes place in the simple direct chlorination of sulfonyl chlorides at 100 °C. />-Toluenesulfonyl chloride is converted to / <2ra-chlorotoluene and, at a higher temperature, to />-chlorobenzotrichloride (equation 168)1088. 

Other reactions. Blum et a/.15 report that the organometallic complex causes decarbonylation of carbonyl compounds and desulfonation of aromatic sulfonyl chlorides. They noted also that 20-g. samples of ethylbenzene, fluorene, and ace-naphthene on being heated with 100 mg. of rhodium complex for 5 hrs. at 130° are oxidized to the extent of 10-60% to acetophenone, fluorenone, and acenaphthenone. 

GC analysis of LAS is only possible after derivatization into volatile derivatives. Desulfonation of LAS in the presence of strong acids like phosphoric acid leads to linear alkylbenzenes (LAB). The identification of every single LAB isomer by GC-FID is achieved with detection limits lower than 1 /rg/1. In an alternative derivatization method, LAS are converted into their alkylbenzene sulfonyl chlorides by PCI5, which can be directly analyzed by GC-FID. Derivatization reactions for aliphatic anionic surfactants have mainly been described for product analysis. Among the very few methods for environmental analysis, the derivatization of alkyl sulfates to their corresponding trimethylsilylesters followed by determination with GC-FID is mentioned here. ... 

Other Transformations. At high temperatures (>200°C) aromatic sulfonyl chlorides are desulfonated to the corresponding aryl halides in the presence of Wilkinson s catalyst (eq 55). Benzamides and malonamide also decompose under similar conditions, giving benzonitrile and acetamide, respectively. ... 

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