Bi(OTf)3催化乙烯基硫醚对邻亚甲基苯醌的硫杂迈克尔加成反应合成邻羟基苄硫醚衍生物

doi:10.3976/j.issn.1002-4026.2020.06.008

山东科学 ›› 2020, Vol. 33 ›› Issue (6): 55-63.doi: 10.3976/j.issn.1002-4026.2020.06.008

Bi(OTf)₃催化乙烯基硫醚对邻亚甲基苯醌的硫杂迈克尔加成反应合成邻羟基苄硫醚衍生物

石新华¹，彭丹¹，王峰¹，牟秋红¹，李金辉¹，于一涛¹，赵宁¹，李冰¹，张硕^1*，刘琳^2*

1.齐鲁工业大学（山东省科学院）山东省科学院新材料研究所山东省特种含硅新材料重点实验室，山东济南 250014；2.山东省海河淮河小清河流域水利管理服务中心，山东济南 250001

收稿日期:2020-07-02 出版日期:2020-12-09 发布日期:2020-12-10
通信作者: 张硕(1986—)，男，助理研究员，研究方向为有机合成，有机硅材料研发。E-mail:e50687e@163.com 刘琳(1982—)，女，工程师，研究方向为分析化学、色谱分析。E-mail:liu3259938@163.com E-mail:ami-research@sdas.org
作者简介:石新华(1989—)，女，研究实习员，研究方向为有机化学、有机合成方法学。E-mail:ami-research@sdas.org
基金资助:
山东省重大科技创新工程 (2019JZZY010350，2019JZZY010316)；山东省重点研发计划(2019GGX102024，2019GGX102076)

Bi(OTf)₃ catalyzed thia-Michael addition of vinyl thioethers to ortho-Qinone Methides: an efficient access to ortho-hydroxybenzyl thioethers

SHI Xin-hua¹，PENG Dan¹，WANG Feng¹，MU Qiu-hong¹，LI Jin-hui¹，YU Yi-tao¹，ZHAO Ning¹，LI Bing¹，ZHANG Shuo^1*，LIU Lin^2*

1.Shandong Provincial Key Laboratory of Special Silicon-Containing Materials, Advanced Materials Institute, Qilu University of Technology (Shandong Academy of Sciences),Jinan 250014，China；2. Haihe River, Huaihe River and Xiaoqinghe River basin water conservancy management and service center of Shandong Province, Jinan 250001, China

Received:2020-07-02 Online:2020-12-09 Published:2020-12-10

摘要/Abstract

摘要： 以2-[羟基(苯基)甲基]苯酚类化合物和乙烯基硫醚为原料，1,2-二氯乙烷为溶剂，在Bi(OTf)₃催化下原位生成邻亚甲基苯醌，而后与乙烯基硫醚发生选择性硫杂迈克尔加成反应构建邻羟基苄硫醚。该反应在30 ℃下搅拌3 h即可完成，目标产物收率78％~88％。该反应化学选择性好，底物适用范围广，底物中2-[羟基(苯基)甲基]苯酚类化合物苯环上具有不同吸电子和给电子取代基，对于苯基乙烯基硫醚和乙基乙烯基硫醚，该反应均可以顺利得到相应产物，并且可放大至克级规模反应。

关键词: 邻亚甲基苯醌, 硫杂迈克尔加成反应, Bi(OTf)₃, 乙烯基硫醚, 邻羟基苄硫醇

Abstract: In the present study, the Bi(OTf)₃ catalyzed thia-Michael addition to ortho-quinone methides for the synthesis of ortho-hydroxybenzyl thioethers with 2-［hydroxy(phenyl)methyl］ phenols and vinyl thioethers in 1,2-dichloroethane was developed. The reaction could be achieved at 30 ℃ for 3 h and the products were obtained in moderate to good yields (78%~88%). The prominent features of the present strategy are good chemical selectivity and with wide substrate scope. For 2-［hydroxy(phenyl)methyl］ phenols, electron-withdrawing groups and electron-donating groups on aromatic rings could react soothly to obtain corresponding products. Also, the reaction could be achieved with phenyl vinyl thioether and ethyl vinyl thioether. Furthermore, the reaction could be scaled up to multigram scale.

Key words: ortho-Quinone, thia-Michael addition, Bismuth(III) trifluoromethanesulfonate, vinyl thioethers , ortho-hydroxybenzyl thioethers

中图分类号:

O622.7

石新华, 彭丹, 王峰, 牟秋红, 李金辉, 于一涛, 赵宁, 李冰, 张硕, 刘琳. Bi(OTf)₃催化乙烯基硫醚对邻亚甲基苯醌的硫杂迈克尔加成反应合成邻羟基苄硫醚衍生物[J]. 山东科学, 2020, 33(6): 55-63.

SHI Xin-hua, PENG Dan, WANG Feng, MU Qiu-hong, LI Jin-hui, YU Yi-tao, ZHAO Ning, LI Bing, ZHANG Shuo, LIU Lin. Bi(OTf)₃ catalyzed thia-Michael addition of vinyl thioethers to ortho-Qinone Methides: an efficient access to ortho-hydroxybenzyl thioethers[J]. Shandong Science, 2020, 33(6): 55-63.

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Bi(OTf)₃催化乙烯基硫醚对邻亚甲基苯醌的硫杂迈克尔加成反应合成邻羟基苄硫醚衍生物

Bi(OTf)₃ catalyzed thia-Michael addition of vinyl thioethers to ortho-Qinone Methides: an efficient access to ortho-hydroxybenzyl thioethers

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