卤盐离子液体/氧气催化芳硫酚与异色满反应
Halogen salt ionic liquid/O2 catalyzed reaction of aromatic thiophenol and isochroman
吴丰田 1吴玲2
作者信息
- 1. 东华理工大学 江西省合成化学重点实验室,江西 南昌 330013;东华理工大学 江西省聚合物微纳制造与器件重点实验室,江西 南昌 330013
- 2. 东华理工大学 江西省聚合物微纳制造与器件重点实验室,江西 南昌 330013
- 折叠
摘要
以1-羧乙基-3-甲基咪唑氯盐([COOH-EtMIm][Cl])/O2体系催化异色满与取代苯硫酚发生脱氢偶联反应,合成了1-(取代苯硫基)异色满.通过单因素实验对反应影响因素进行了筛选,得到适宜反应条件为:4-甲基苯硫酚(62 mg,0.5 mmol)、异色满(134 mg,1.0 mmol)、[COOH-EtMIm][Cl](95 mg,0.5 mmol)、O2(0.10 MPa)、反应温度120℃、反应时间12 h.在该条件下,催化剂可使用4次,实现了1-(4-甲基苯硫基)异色满克级合成,底物拓展后得到 12 种 1-(取代苯硫基)异色满,产率为 52%～96%.提出了[COOH-EtMIm][Cl]阴阳离子通过氢键分别活化苯硫酚与异色满,经O2氧化,脱氢得到1-(取代苯硫基)异色满的反应机理.
Abstract
1-Substituted thiophenol isochromans were obtained via 1-carboxyethyl-3-methylimidazolium chloride([COOH-EtMIm][Cl])-catalyzed dehydrogenation coupling reaction of subsituted thiophenols and isochroman in the presence of O2.The influencing factors were screened by single factor experiments,and the optimal reaction conditions were obtained as follows:p-toluenethiol(62 mg,0.5 mmol),isochroman(134 mg,1.0 mmol),[COOH-EtMIm][Cl](95 mg,0.5 mmol),O2 pressure 0.10 MPa,reaction temperature 120℃,and reaction time 12 h.Under the optimum reaction conditions,the catalyst could be recycled for 4 times,while the gram-scale synthesis of 1-thiophenol isochroman was accomplished and 12 kinds of 1-substituted thiophenol isochromans with yields ranging from 52%to 96%were obtained.In addition,activation of thiophenol and isochroman by anion and cation ions of[COOH-EtMIm][Cl],respectively,followed by O2 oxidation and final dehydrogenation to form 1-thiophenol isochroman,was proposed as the reaction mechanism.
关键词
离子液体/氧气/氧化/芳硫酚/异色满/精细化工中间体Key words
ionic liquids/oxygen/oxidation/aromatic thiophenols/isochroman/fine chemicals intermediates引用本文复制引用
基金项目
江西省教育厅科技项目(GJJ210718)
江西省合成化学重点实验室开放基金(JXSC202202)
江西省聚合物微纳制造与器件重点实验室开放基金(PMND202107)
出版年
2024
NETL
NSTL
维普
万方数据