脂肪磺酰氯大部分是由相应的硫醇及其衍生物用氯磺化试剂（比如氯气）作用得来。前期已经介绍了硫醇的制备和硫醇制备磺酰氯的方法。下面简单介绍硫类得衍生物（包括硫脲，异硫氰酸酯，硫代乙酸酯，磺原酸酯等等）合成磺酰氯的方法。

一、通过烷基硫脲合成脂肪磺酰氯

1、烷基硫脲的合成

硫脲极易发生烃化反应生成S-烃基异硫脲盐，收率一般在（40％－90％）。烷基硫脲是所有脂肪类硫醇衍生物中最重要的一类，它可以从前体卤代烷烃经硫脲处理得来。反应条件比较温和。如下例所示： 

本法的一种改良是在浓盐酸或浓氢溴酸存在下，醇与硫脲直接反应，即可生成S－烃基异硫脲盐，不必由醇制备卤代烃再进行反应。

2、通过烷基硫脲合成芳香磺酰氯

目前有两种常用的方法将脂肪硫脲转变为脂肪磺酰氯，一是用NaClO4在酸性溶液中处理得来。另一种是在酸性介质中通入氯气制得。

文献报道：

【Lee Jae Koo. Et al; J. Agric. Food Chem.; EN; 50; 7; 2002; 1791-1803】

反应实例

3-[4-(4-chlorophenoxy)phenyl]-7-iodo-hept-2-enoate (59.8 g) and thiourea (9.39 g) in ethanol (123 ml) was refluxedfor 24 hours. The resulting mixture was cooled and evaporated to give ethyl7-amidinothio-3-[4-(4-chlorophenoxy)phenyl]hept-2-enoate hydroiodide (70.2 g) (E:Z = 1:1 mixture) as slightlyyellow oil.This sample was then dissolved inAcOH (1000 mL), chlorine gas was bubbled into the mixture at 0－10 oC, TLCindicate the reaction completed.  Theprecipitate was collected by filtration, washed with water.  Re-dissolved in CH2Cl2(1000 mL).  Dried upon anhydrous MgSO4,filtered, concentrated to afford the target sulfonyl chloride (52 g, 65 %).

二、通过烷基异硫氰酸酯合成芳香磺酰氯

1、烷基异硫氰酸酯的合成

烷基异硫氰酸酯是脂肪硫醇的另一类重要的衍生物。它也可以由烷基卤代烃作为前体与异硫氰酸钾反应生成。如：

2、通过烷基异硫氰酸酯合成芳香磺酰氯

异硫氰酸酯类化合物用氯气处理后也能得到磺酰氯：

反应实例

A mixture of 1-iodo-3-methylbutane (12 g) and potassium thiocyanate (5.9 g) in acetone (110 ml) was refluxed for 4 hours.After precipitate was filtered off, the filtrate was evaporated in vacuo. Waterwas added to the residue followed by extraction with chloroform. The extractwas dried over magnesium sulfate and evaporated under reduced pressure to givethe thiocyanate (8.3 g).A solution of above thiocyanate was bubbled with chlorine gas for 1 hour underice-cooling (below 0.deg. C.) with stirring followed by extraction withdiisopropyl ether. After extract was dried over sodium sulfate, the solvent wasevaporated in vacuo to give sulfonyl chloride (9.0 g). To a 28percent ammonium hydroxide (50 ml) wasadded dropwise crude sulfonyl chloride in dichloromethane (15 ml) over 20minutes at approximately 0.deg. C. The reaction mixture was stirred vigorouslyovernight at ambient temperature. The phases were separated. The aqueous phasewas extracted with chloroform/methanol (5/1). The combined organic extractswere washed with half-brine, dried over magnesium sulfate and evaporated underreduced pressure. The residue was purified by column (chloroform/methanol=95/5)to give 3-methyl-1-butanesulfonamide (4.3 g).

三、通过羧酸硫醇酯合成芳香磺酰氯

1、羧酸硫醇酯的合成

 羧酸硫醇酯的制备一般都是通过卤代烷烃同乙酸硫醇钾反应生成。如：

2、通过羧酸硫醇酯合成脂肪磺酰氯

羧酸硫醇酯也是通过氯气的处理得到脂肪磺酰氯。如：

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