超声辅助水溶液中合成1,4-二氢吡啶衍生物

doi:10.3969/j.issn.1000-1565.2017.04.009

河北大学学报(自然科学版) ›› 2017, Vol. 37 ›› Issue (4): 386-392.DOI: 10.3969/j.issn.1000-1565.2017.04.009

超声辅助水溶液中合成1,4-二氢吡啶衍生物

尹晓刚,吴小云,王野,陈治明,陈卓

收稿日期:2016-02-20 出版日期:2017-07-25 发布日期:2017-07-25
通讯作者: 陈卓(1971—),女,河北唐山人,贵州师范大学教授,主要从事有机合成方法学研究.E-mail:chenzhuo19@163.com
作者简介:尹晓刚(1976—),男,浙江嘉兴人,贵州师范大学副教授,主要从事有机合成方法学研究. E-mail:m13885115516@163.com
基金资助:
国家自然科学基金资助项目(21362006);贵州省科技厅科技合作项目(黔科合LH字［2016］7218号);贵州省科技厅科技支撑项目(黔科合支撑［2016］2311)

Ultrasonic assisted synthesis of 1,4-dihydropyridine derivatives in water

YIN Xiaogang,WU Xiaoyun,WANG Ye,CHEN Zhiming,CHEN Zhuo

Key Laboratory of Functional Materials Chemistry of Guizhou Province, School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001, China

Received:2016-02-20 Online:2017-07-25 Published:2017-07-25

摘要/Abstract

摘要： 以芳香醛、乙酰乙酸乙酯(乙酰丙酮)及碳酸氢铵为原料,研究超声条件下蒙脱土固载路易斯酸催化合成1,4-二氢吡啶衍生物.单因素筛选法考察催化剂、溶剂、温度、超声时间、氮源对产率的影响.反应在水溶液中顺利进行,在反应温度80 ℃,超声时间15 min,芳香醛、乙酰乙酸乙酯及碳酸氢铵的物质的量比为1.2∶2.0∶1.0,催化剂为蒙脱土固载氯化铝,催化剂(醛的物质的量分数为10%)的最优条件下,合成的1,4-二氢吡啶衍生物产率最高可达93.7%.催化剂循环使用3次后产率仍可达85.9%.产物通过红外、核磁、熔点进行表征.该方法与现有合成方法相比,具有操作简便、收率高、用时短等优点,有潜在的应用前景.

关键词: 1, 4-二氢吡啶, 超声, 韩奇反应

Abstract: Using the aromatic aldehydes,ethyl acetoacetate(acetylacetonate)and ammonium bicarbonate as raw materials,under ultrasonic condition,montmorillonite/Lewis acid catalysis the synthesis of 1,4-dihydropyridine derivatives was performed.The effects of the reaction temperature,reaction time,solvent,catalyst and nitrogen source were investigated by single factor screening.Reaction was found to proceed smoothly in aqueous solution at a reaction temperature of 80 ℃,and ultrasonic time 15min.The molar ratio of aromatic aldehyde,ethyl acetoacetate and bicarbonate ammonium molar ratio of 1.2∶2.0∶1.0.Catalyst is immobilized aluminum chloride catalyst in an amount of 10%(molar ratio of aldehyde).Under optimal conditions,the synthesis of 1,4-dihydropyridine derivatives yield up to 93.7%.With the catalyst recycled three times,the production yield was still up to 85.9%.The product was characterized by IR,NMR,melting point.Compared with the conventional synthesis method,ultrasonic method is simple,high yield,rapid,showing potential applications.

Key words: 1,4-dihydropyridine, ultrasonic, hantzsch reaction

中图分类号:

O629.32

尹晓刚,吴小云,王野,陈治明,陈卓. 超声辅助水溶液中合成1,4-二氢吡啶衍生物[J]. 河北大学学报(自然科学版), 2017, 37(4): 386-392.

YIN Xiaogang,WU Xiaoyun,WANG Ye,CHEN Zhiming,CHEN Zhuo. Ultrasonic assisted synthesis of 1,4-dihydropyridine derivatives in water[J]. Journal of Hebei University (Natural Science Edition), 2017, 37(4): 386-392.

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超声辅助水溶液中合成1,4-二氢吡啶衍生物

Ultrasonic assisted synthesis of 1,4-dihydropyridine derivatives in water

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