芳香硫醇及相關衍生物，比如硫醚，二硫化物在氧化性氯化試劑存在下，均能夠較容易的轉變成磺酰氯。因此，芳香硫醇及其衍生物也是合成芳香磺酰氯的一類重要前體。
文獻報道：對硝基硫酚在以下兩種條件下都可以很容易的轉變成對硝基苯磺酰氯【 de vries et al; Recl Trav. Chim. Pays-Bas; 70; 1951; 696; Park, young jun et al; Chem.Lett.; EN; 8; 1992】。
Andrews,Stephen P. 報道：將如下底物懸浮于醋酸水中，導入氯氣，就能以76％的收率得到磺酰氯【Andrews, Stephen P. et al; J. Org. Chem. EN; 68; 14; 2003;5525-5533)】。
二硫化物也是一類可以通過氯氣處理或氧化性氯化試劑轉化成磺酰氯的重要前體。如Berryman, K. A. 報道?！綛erryman, K. A. ; Bioorg. Med. Chem.; EN; 6; 9; 1998;1447】
反應實例
4-Nitro-3-trifluoromethyl-benzenethiol 47g was dissolved in AcOH (100 mL),chlorine gas was bubbled into the mixture at 0－10 oC, TLC indicate thereaction completed. The precipitate wascollected by filtration, washed with water. Taken into CH2Cl2 (200 mL). Dried upon anhydrous MgSO4,filtered, concentrated to afford the desired sulfonyl chloride (22.3 g) as an yellow oil, this samplecould be used in next step without further purification.
Chlorinegas was bubbled through a suspension of methyl4-benzylsulfanyl-3-nitrobenzoate (25.4 g, 83.7 mmol) in acetic acid/water (2:3, 500 mL) for 1.5 h. Themixture was stirred under the chlorine atmosphere for 19 h when the system waspurged with nitrogen and the solvent wasconcentrated in vacuo. The resulting yellow precipitate was collected byfiltration, washed with hexane (2 × 50 mL), and recrystallized fromchloroform/hexane to afford the sulfonyl chloride as a white crystal (17.8 g, 76%).
【Andrews, Stephen P. et al; J. Org. Chem. EN; 68; 14; 2003;5525-5533)】
To above compound 1 (6.55 g, 14.4 mmol) and potassium nitrate (4.37 g, 43.0 mmol) in acetonitrile (45mL) was added sulfuryl chloride (3.45 mL, 43.0 mmol) dropwise over 7 min andthe reaction mixture was stirred at room temperature. After 5 h sodiumbicarbonate (500 mL, aq satd) was added and the solution extracted with ethyl acetate(600 mL). The organic phase was washed with brine (400 mL), dried withmagnesium sulfate, and evaporated in vacuo to give the title compound (6.6 g, 78%) as an oil. Used withoutfurther purification.
【Berryman, K. A. ; Bioorg. Med. Chem.; EN; 6; 9; 1998;1447】
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