聚芳硫醚新型中间体4-(苯硫基)苯甲亚砜(PSO)的合成  

Synthesis of a New Intermediate of Poly(Aryl Sulfide)4-(Phenylthio)Benzyl Sulfoxide(PSO)

作　　者：吴炳辉 马晓明[2,3] 陈康 刘建武 严生虎[2,3] 张跃 WU Bing-hui;MA Xiao-ming;CHEN Kang;LIU Jian-wu;YAN Sheng-hu;ZHANG Yue(School of Petrochemical Engineering,Changzhou University,Changzhou 213164,China;School of Pharmacy,Changzhou University,Changzhou 213164,China;Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry,Changzhou 213164,China;Jiangsu Suhua Group Co.,Ltd.,Suzhou 215006,China)

机构地区：[1]常州大学石油化工学院,江苏常州213164 [2]常州大学药学院,江苏常州213164 [3]石油和化工行业连续流技术工程实验室,江苏常州213164 [4]江苏苏化集团有限公司,江苏苏州215006

出　　处：《化学试剂》2023年第1期157-162,共6页Chemical Reagents

基　　金：国家工信部化学原料药环保安全技术服务平台项目(2020-0107-3-1);江苏省研究生科研与实践创新计划项目(KYCX22_3014)。

摘　　要：以廉价的二苯硫醚为起始原料,经氯磺化(Reed)反应并还原芳基磺酰氯合成了4-(苯硫基)苯硫醇,进一步以四丁基碘化铵(TBAI)催化端基硫醇,再与硫酸二甲酯发生甲基化反应,最终将甲基苯基硫醚高选择性地氧化成亚砜,得到聚芳硫醚合成的关键中间体4-(苯硫基)苯甲亚砜(PSO);考察了磺化试剂、磺酰氯还原体系(二氯二甲基硅烷-锌)、甲基化试剂、催化剂、溶剂和反应时间等对产率的影响,并对工艺进行了优化。该方法与其他路线相比,解决了使用液溴、硝酸等物质导致设备腐蚀问题的同时,大大提高了产率与纯度。Using inexpensive diphenyl sulfide as a starting material,the 4-(thiophenyl)benzenethiol was synthesized by chlorosulfonation(Reed reaction)and reduction of benzenesulfonyl chloride.Further,the terminal thiols were catalyzed by tetrabutylammonium iodide(TBAI),followed by methylation with dimethyl sulfate.Ultimately,4-(thiophenyl)benzyl sulfoxide(PSO),a key intermediate in the synthesis of poly(arylene sulfide),was obtained by highly selective oxidation of the Methyl phenyl sulfide to sulfoxide.The article investigated the effects of sulfonation reagent,sulfonyl chloride reduction system(dichlorodimethylsilane-Zn),methylation reagent,catalyst,solvent and reaction time on the yield,and determined the optimal reaction conditions,as well as optimized the reaction process.Compared with other routes,this method solved the problem of equipment corrosion caused by using liquid bromine and nitric acid,while greatly improving the yield and purity.

关 键 词：聚芳硫醚 硫鎓离子 PSO 硫醇氧化 端基硫醚 

分 类 号：TQ612.9[化学工程—精细化工]