2-碘-3-(对甲苯磺酰氧基)苯基醚的选择性合成  

Selective synthesis of 2-iodophenyl-3-(p-tosyloxy)4-methylbenzenesulfonate

作　　者：潘峰 王磊 郭怡 沈金滢 潘晓峰 郑卫新[1] PAN Feng;WANG Lei;GUO Yi;SHEN Jinying;PAN Xiaofeng;ZHENG Weixin(College of Material,Chemistry&Chemical Engineering,Hangzhou Normal University,Hangzhou 311121,China)

机构地区：[1]杭州师范大学材料与化学化工学院,浙江杭州311121

出　　处：《浙江大学学报（理学版）》2021年第5期579-583,628,共6页Journal of Zhejiang University（Science Edition）

基　　金：国家自然科学基金资助项目(20972037).

摘　　要：磺酰氧基卤代芳基醚是一种多功能化合物,在众多研究领域具有广泛应用价值。以2-碘间苯二酚为原料,经化学计量的双磺酰化、选择性单侧水解及与溴化物的亲核取代反应,合成系列2-碘-3-(对甲苯磺酰氧基)苯基醚。结果表明,双磺酰化产物的选择性单侧水解比2-碘间苯二酚通过单烃基化进行原料中2个对称羟基的选择性官能化更有优势。以低成本碱为水解试剂,探索反应时间、温度等因素对2,6-双(对甲苯基磺酰氧基)碘苯单侧选择性水解的影响,水解产物核磁纯度>99%,为对甲苯磺酰氧基碘代芳基醚的合成提供一种操作简便、反应条件温和、成本低和选择性高的方法。所有化合物结构均经1H-NMR、13C-NMR与高分辨质谱等方法确定。Halogenated sulfonyloxyaromatic ether has been regarded as the polyfunctionalized organic compound with wide applications in lots of fields.Using 2-iodoresorcinol as the starting material,series of iodonated alkyloxy 4-methylbenzenesulfonate were synthesized in high yields via stoichiometrical bissulfonylation,selective monohydrolysis of 2-iodo-1,3-phenylene bis(4-methylbenzenesulfonate)followed by nucleophilic substitution to various organobromides.Procedure for preparation of 3-hydroxy-2-iodophenyl-(4-methylbenzenesulfonate)was explored.It was found that the monodesulfonylation of bissulfonate was much more favorite than monohydrocarbylation for selective functionalization of the two symmetrical hydoxyls in 2-iodoresorcinol.Using low-cost alkali system,the reaction time,temperature of the monohydrolysis of the 2,6-bis(tosyloxy)iodobenzene had been investigated.The monohydrolysis product,3-hydroxy-2-iodophenyl-(4-methylbenzenesulfonate),were obtained in the purity of above 99%in ^(1)H-NMR without further purification.This study provides a synthetic method of 3-alkyloxy-2-iodophenyl 4-methylbenzenesulfonate,which had the advantages of simple operation,mild reaction conditions,low cost and high selectivity.The structures of all the products were verified by ^(1)H-NMR,^(13)C-NMR and HRMS,et al.

关 键 词：磺酰氧基碘代苯基醚 合成 选择性水解 

分 类 号：O627[理学—有机化学]