一种苯炔前体的合成研究  

Synthesis of a Kind of Aryne Precursor

作　　者：刘斌[1] 祝婷婷 张彦民 左振宇[2] Liu Bin;Zhu Tingting;Zhang Yanmin;Zuo Zhenyu(School of Pharmacy,Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province,Shaanxi Institute of International Trade&Commerce,Xi'an,Shaanxi 712046,China;College of Pharmacy,Shaanxi University of Chinese Medicine,Xi'an,Shaanxi 712046,China)

机构地区：[1]陕西国际商贸学院医药学院陕西省中药绿色制造技术协同创新中心,陕西西安712046 [2]陕西中医药大学药学院,陕西西安712046

出　　处：《化学世界》2020年第4期250-254,共5页Chemical World

基　　金：陕西省自然科学基础研究计划(面上)(No.2018JM7046);陕西省教育厅2018年度专项科学研究计划(No.18JK0954);2018年陕西省大学生创新创业(No.201849004);陕西国际商贸学院校级(No.SMXY201805),陕西国际商贸学院“中药药效物质研究”创新团队建设(No.SSY18TD01)资助项目。

摘　　要：报道一种苯炔前体的简便制备方法。以廉价易得的香豆灵酸甲酯和双(三甲基硅基)乙炔为原料,通过Diels-Alder反应得到3,4-二(三甲基硅基)苯甲酸甲酯,然后与碘苯二乙酸反应,再与三氟甲烷磺酸成盐得到目标化合物[5-(甲氧羰基)-2-(三甲基硅)苯基](苯基)碘鎓三氟甲烷磺酸盐。通过对两步反应条件进行研究,确定目标化合物的最佳反应工艺条件。目标化合物与呋喃在正丁基氟化铵作用下发生Diels-Alder反应得到1,4-二氢-1,4-环氧萘-6-甲酸甲酯,收率为78.5%。化合物及经~1H NMR和ESI-MS表征。[5-(Methoxycarbonyl)-2-(trimethylsilyl)phenyl](phenyl)iodonium trifluoromethanesulfonate,a new kind of aryne precursor,was synthesized by an efficient and practical method from methyl 2-oxo-2H-pyran-5-carboxylate and 1,2-bis(trimethylsilyl)ethyne through a two-step reaction.Methyl 3,4-bis(trimethylsilyl)benzoate was obtained by Diels-Alder reaction of methyl 2-oxo-2H-pyran-5-carboxylate and 1,2-bis(trimethylsilyl)ethyne,then reacted with iodobenzene diacetate and formed trifluoromethanesulfonate salt to afford the target compound[5-(methoxycarbonyl)-2-(trimethylsilyl)-phenyl](phenyl)iodonium trifluoromethanesulfonate.The optimal reaction conditions and application of the target compound was also investigated.Methyl 1,4-dihydro-1,4-epoxynaphthalene-6-carboxylate was obtained in a yield of 78.5%by the reaction of target compound and furan in the present of tetrabutylammonium fluoride.The structures of the product and intermediate were confirmed by^1H NMR and ESI-MS.

关 键 词：苯炔前体 DIELS-ALDER反应 1 4-二氢-1 4-环氧萘-6-甲酸甲酯 合成 

分 类 号：O621.3[理学—有机化学]