碳酸催化二硫化物和醛反应合成苯并噻唑类衍生物
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- 英文论文题名：Synthesis of benzothiazole derivatives from aldehyde and disulfide catalyzed by carbonic acid
- 论文作者：柳磊 ; 刘波 ; 竺宁 ; 韩利民 ; 洪海龙
- 英文论文作者：Lei Liu ; Bo Liu ; Ning Zhu ; Limin Han ; Hailong Hong ; Chemical Engineering College ; Inner Mongolia University of Technology
- 年：2016
- 作者机构：内蒙古工业大学化工学院;
- 论文关键词：苯并噻唑 ; 硫氢化钠 ; 水 ; 碳酸
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十三分会：绿色化学
- 语种：中文
- 分类号：O626.25
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十三分会 ; 绿色化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：246k
- 原文格式：D
- 会议级别：全国
摘要
苯并噻唑及其衍生物是一类非常重要的杂环化合物,被广泛地用于医药、农业及工业等领域。因此苯并噻唑类衍生物的应用及合成方法受到了广泛的关注。二氧化碳在有机合成中具有特殊的化学作用。例如,二氧化碳不仅可以作为反应原料和反应介质,还可作调控试剂控制化学选择性和酸催化~([1])。二氧化碳加压冲入水中,可以暂时生成碳酸,进而提供一个临时的酸性环境,使体系的pH值降低~([2])。这种环境友好的二氧化碳-水体系可以作为酸催化剂来替代传统的酸,而且后期处理简单。故本课题组以水作溶剂,加入硫氢化钠,并通入2 MPa的二氧化碳形成碳酸,在80℃下催化二硫化物和醛反应合成了2-取代苯并噻唑类化合物。该合成方法具有操作简单,对环境友好和产率高等优点。二硫化物在硫氢化钠的作用下,发生动态交换断裂二硫键,并在碳酸条件下生成邻氨基苯硫酚,然后和苯甲醛反应生成苯并噻唑啉。苯并噻唑啉还可以作为还原剂,将二硫化物还原成邻氨基苯硫酚,而自身被氧化为苯并噻唑。过量的苯并噻唑啉继续被空气氧化成为苯并噻唑~([3])。
Benzothiazole derivatives are a very important class of heterocyclic compounds,this paper gave an approach to synthesize benzothiazole in high yield from the reaction of disulfide with aldehyde,catalyzed by H_2O-CO_2 system,in the presence of Na_2S·9H_2O.The S-S bonds was broken by Na_2S·9H_2O to form 2-aminobenzenethiol in carbonic acid environment,then the 2-aminobenzenethiol reacted with benzaldehyde to form 2-phenylbenzothiazoline.And2-phenylbenzothiazoline could reduce the disulfide into 2-aminobenzenethiol,which was simultaneously oxidized into the corresponding benzothiazole.And the remaining 2-phenylbenzothiazoline was also oxidized by air to form benzothiazole.CO_2 is nontoxic,so that this synthetic method is environmentally benign.
Benzothiazole derivatives are a very important class of heterocyclic compounds,this paper gave an approach to synthesize benzothiazole in high yield from the reaction of disulfide with aldehyde,catalyzed by H_2O-CO_2 system,in the presence of Na_2S·9H_2O.The S-S bonds was broken by Na_2S·9H_2O to form 2-aminobenzenethiol in carbonic acid environment,then the 2-aminobenzenethiol reacted with benzaldehyde to form 2-phenylbenzothiazoline.And2-phenylbenzothiazoline could reduce the disulfide into 2-aminobenzenethiol,which was simultaneously oxidized into the corresponding benzothiazole.And the remaining 2-phenylbenzothiazoline was also oxidized by air to form benzothiazole.CO_2 is nontoxic,so that this synthetic method is environmentally benign.
引文
[1]Hallett J.P.;Pollet P.;Liotta C.L.;et al.Acc.Chem.Res.,2008,41(3):458.
[2]Liu A.H.;Ma R.;Zhang M.;et al.Catal.Today,2012,194(1):38.
[3]Liu B.;Zhu N.;Hong H.;et al.Tetrahedron,2015,(71):9287.
[2]Liu A.H.;Ma R.;Zhang M.;et al.Catal.Today,2012,194(1):38.
[3]Liu B.;Zhu N.;Hong H.;et al.Tetrahedron,2015,(71):9287.