2-碘-3-（对甲苯磺酰氧基）苯基醚的选择性合成

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。

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

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 ¹H-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 ¹H-NMR, ¹³C-NMR and HRMS, et al.