铜催化C-H活化/C-S偶联反应合成环烷基芳基硫醚

The Syntheses of Cycloalkylaryl Sulfides via Copper-catalyzed C-H bond Activation/C-S Coupling Reaction

为设计一种利用廉价催化剂以达成C-H活化构建C-S的方法,本文研究了铜催化C-H活化/C-S偶联反应合成系列环烷基芳基硫醚化合物。以芳基磺酰肼与环烷烃为原料,溴化亚铜为催化剂,二叔丁基过氧化物(DTBP)为氧化剂,120℃反应24 h,经氧化脱氮C-H活化/C-S偶联串联反应过程,合成了系列环烷基芳基硫醚化合物。该反应适合环戊烷、环己烷、环庚烷、环辛烷和环十二烷等环烷烃和不同取代基团(甲氧基、硝基、氯和甲基)的芳基酰肼,合成得到了18个芳基硫醚类化合物,产率为41%~72%。其结构经^(1)H NMR、^(13)C NMR和HR-MS进行了表征。

In order to design a method of using cheap catalyst to achieve C-H bond activation and construct C-S bond.In this paper,copper-catalyzed C-H bond activation/C-S coupling reaction to synthesize a series of cycloalkylaryl sulfide compounds was studied.A series of cycloalkyl aryl sulfide compounds were synthesized via oxidative denitrogenation C-H bond/C-S coupling procedure using arylsulfonyl hydrazide and cycloalkane as raw materials,CuBr as catalyst,di-tert-butyl peroxide(DTBP)as oxidant,reacted at 120℃for 24 hours.The reaction is suitable for cycloalkanes such as cyclopentane,cyclohexane,cycloheptane,cyclooctane,cyclododecane and aryl hydrazides with different substituent groups(methoxy,nitro,chlorine,methyl).Eighteen aryl sulfide compounds were synthesized with the yields ranging from 41%to 72%.Their structures were characterized by ^(1)H NMR,^(13)C NMR and HR-MS.