磺酰氯合成法-.doc

磺酰氯合成法-060303磺酰氯合成法-060303
经典化学合成反应标准操作
磺酰氯合成法
经典合成反应标准操作—磺酰氯合成法
目录
1. 前言··········································································································2
2. 芳香磺酰氯的制备····················································································2
2. 1直接氯磺化法制备芳香磺酰氯··························································2
2. 2芳香磺酸或盐氯化制备芳香磺酰氯··················································3
2. 3芳香硫醇及相关衍生物氯代、氧化合成芳香磺酰氯
························8
2. 4. 芳香硫醇的制备·········································································· 11
2. 5 Sandermeyer 反应由芳胺合成芳香磺酰氯····································13
3. 脂肪磺酰氯的制备
3. 1 烷基硫醇的合成及通过烷基硫醇合成脂肪磺酰氯·························14
3. 2 通过烷基硫脲合成脂肪磺酰氯·······················································16
3. 3 通过烷基异硫氰酸酯合成芳香磺酰氯············································17
3. 4 通过羧酸硫醇酯合成芳香磺酰氯···················································17
3. 5 脂肪磺酰氯合成反应示例······························································
18
参考文献: ··································································································20
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经典合成反应标准操作—磺酰氯合成法
1. 前言
磺酰氯是有机化学中非常重要的一类化合物,它们可以作为重要的中间体进行修饰。比如,同胺类化合物作用生成的磺胺类药物是优良的化学治疗剂,开始应用于20世纪30年代。它们能抑制多种细菌,如链球菌、葡萄球菌、肺炎球菌、脑膜炎球菌、痢疾杆菌等的生长和繁殖,因此常用以治疗由上述细菌所引起的疾病。高碳烷基磺酸钠类化合物则是优良的合成洗涤剂。
磺酰氯主要分为脂肪族磺酰氯和芳香族磺酰氯。芳香磺酰氯的来源有以下几类:1)由硫酚,各种硫醚在酸性溶剂中导入氯气制得;2)芳香磺酸类化合物在氯化试剂作用下形成;3)磺化反应。脂肪族磺酰氯的来源主要是硫醇或相关衍生物氯代或氧化。
因此,作为磺酰氯的重要前体,磺酸和硫醇类化合物的引入,也是合成磺酰氯基团的重要手段。
2. 芳香磺酰氯的制备
芳香磺酰氯的制备一般分为以下几种方法, 直接用氯磺化法制备芳香磺酰氯。芳香磺酸或盐经氯化制备芳香磺酰氯。芳香硫醇及相关衍生物氯化,氧化合成芳香磺酰氯。 Sandermeyer反应由芳胺合成芳香磺酰氯。 2. 1直接氯磺化法制备芳香磺酰氯
氯磺酸是一类比较常用的直接氯磺化试剂,氯磺酸的活性比浓硫酸大,反应温度较低,同时可以直接得磺酰氯。氯磺化也是亲电反应,选择性也遵循芳环取代基定位效应及其规则。有规律可循。如果希望反应比较缓和,可以用氯仿或其它卤代烷烃作为稀释剂。反应温度一般都控制在0至20℃。
COOH
HOO
F
l
Cl
COOH
OO
F
如果芳环上存在至钝基团,像羧基等,直接氯磺化的温度要提的比较高,要达到100多度。1
COOH
ClSO3H140 oC
Br
ClO2S
BrCOOH
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经典合成反应标准操作—磺酰氯合成法当体系因为位阻,取代基定位效应劣势等等不能直接完成氯磺化时,就可以选择分
两步走,先引入磺酸基团。再转变为磺酰氯。