基于四甲基久洛尼定为原料的香豆素衍生物的合成  

Synthesis of Coumarin Derivatives Based on Tetramethy Cjuloidine as Raw Material

作　　者：吴华彪[1] 韩亮[1] 祖晓燕 李郁锦[1] 叶青[1] 高建荣[1] 

机构地区：[1]浙江工业大学,浙江杭州310014

出　　处：《浙江化工》2014年第7期33-37,共5页Zhejiang Chemical Industry

基　　金：国家自然科学基金(No.21176223);浙江省重点创新团队项目(No.2010R50018-06);浙江省自然科学基金(No.LY13B020012)资助项目

摘　　要：以间氨基苯酚和溴代异戊烯为起始原料经过亲核取代制备了N,N-二(3-甲基-2-丁烯)-3-羟基苯胺氢溴酸盐,通过亲电取代关环合成了8-羟基-1,1,7,7-四甲基久洛尼定,再经Vilsmeir-Haack反应引入醛基获得了9-甲酰基-8-羟基-1,1,7,7-四甲基久洛尼定,总收率为25.7%。对N,N-二(3-甲基-2-丁烯)-3-羟基苯胺氢溴酸盐的合成进行了工艺探索,结果表明当间氨基苯酚和溴代异戊烯投料比为1:2,CaCO3为缚酸剂时得到的收率较佳。以9-甲酰基-8-羟基-1,1,7,7-四甲基久洛尼定为原料,分别与噻吩乙腈、对溴苯乙腈进行缩合反应制备得到3-芳基香豆素衍生物,对其结构进行了核磁鉴定,并对其紫外光谱进行了测试。N,N-Bis （3-methyl-2-butene）-3-hydroxyanilin hydrobromide was prepared from m-aminophenol and 1-bromo-3-methyl-2-butene via nucleophilic substitution reaction at first. Then 8-hydrox-y-1,1,7,7-tetramethyljulolidine was synthesized by electrophilic substitution. And aldehyde group was intro-duced to prepare 9-formyl-8-hydroxy-1,1,7,7-tetramethyljulolidine through Vilsmeir-Haack reaction. Reac-tion conditions for synthesis of N,N-bis （3-meyhyl-2-butene）-3-hydroxyanilin hydrobromide was explored, and the results showed that when the ratio of m-aminophenol and 1-bromo-3-methyl-2-butene was 1：2 and calcium carbonate was used as acid-binding agent, the yield was optimum. Then 9-formyl-8-hydroxy-1,1,7,7-tetramethyljulolidine reacted with 2-thiopheneacetonitrile or 4-bromophenylacetonitrile to prepare two 3-arylcoumarin derivatives. The structure of the derivative and products were identified by 1H NMR spectroscopy. And the UV spectra of target products were tested.

关 键 词：间氨基苯酚 溴代异戊烯 合成 四甲基久洛尼定 香豆素衍生物 

分 类 号：TQ25[化学工程—有机化工]