高等学校化学学报

高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (3): 579.doi: 10.7503/cjcu20120781

• 有机化学 • 上一篇    下一篇

3-(CH2)n CO2 C2 H5-1,5-苯并硫氮杂卓的合成、晶体结构及抑真菌活性

邱召来1, 李文红2, 朱海菲1, 刘倩1, 李媛1   

  1. 1. 河北师范大学化学与材料科学学院, 石家庄 050024;
    2. 河北工业职业技术学院环境与化学工程系, 石家庄 050091
  • 收稿日期:2012-08-24 出版日期:2013-03-10 发布日期:2013-02-18
  • 通讯作者: 李媛,女,教授,主要从事有机合成研究.E-mail:liyuanhbsd@163.com E-mail:liyuanhbsd@163.com
  • 基金资助:

    国家自然科学基金(批准号:20972040)和河北省教育厅青年基金(批准号:Q2012001)资助.

Synthesis, Crystal Structure and Antifungal Activities of 3-(CH2)nCO2C2H5-1,5-Benzothiazepines

QIU Zhao-Lai1, LI Wen-Hong2, ZHU Hai-Fei1, LIU Qian1, LI Yuan1   

  1. 1. College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China;
    2. Environment and Chemical Engineering, Hebei College of Industry and Technology, Shijiazhuang 050091, China
  • Received:2012-08-24 Online:2013-03-10 Published:2013-02-18

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摘要：

为了寻找具有更高抗真菌活性的杂类化合物并对高活性的杂衍生物A进行构效关系研究, 设计合成了38个3-(CH2)nCO2C2H5-1,5-苯并硫氮杂衍生物6和7(n=1, 2), 其结构经核磁共振波谱、 质谱、 红外光谱及元素分析等确证; 并采用X射线单晶衍射技术测定了目标化合物的立体结构, 发现其分子中的七元杂环是扭曲的船式构象. 实验还考察了合成化合物的抑真菌活性, 结果表明, 当乙氧羰基烷基[(CH2)nCO2C2H5]在七元杂环的3位时杂的活性降低; 将Lewis CeCl3·7H2O-NaI用于催化含硫化合物与α,β-不饱和酮的迈克尔加成反应, 发现该催化剂能有效促进高位阻α,β-不饱和酮与邻氨基苯硫酚的迈克尔加成; 同时研究了中间体5的分子内缩合反应, 发现TiCl4是合成Schiff碱非常有效的促进剂.

关键词: 1,5-苯并硫氮杂, 抑真菌活性, CeCl3·7H2O-NaI, 迈克尔加成, Schiff碱

Abstract:

In order to find benzothiazepine derivatives with more effective activities against fungi and investigate the structure-activity relationship of ester-substituted 1,5-benzothiazepine derivatives(A), thirty-eight 3-(CH2)nCO2C2H5-1,5-benzothiazepines(n=1, 2) 6 and 7 were synthesized and characterized by 1H NMR, MS/HRMS, IR and elemental analysis. The crystal structures of compounds 6a and 7c were also studied by X-ray diffraction method and the results indicated that seven-membered ring in the molecules of compounds 6a and 7c adopts twist-boat conformation. The results of bioassay of compounds 6 and 7 showed that the antifungal activities decrease when the ethoxycarbonyl alkyl [(CH2)nCO2C2H5] was at C3 position on the heterocyclic ring in these 1,5-benzothiazepine derivatives. Meanwhile, the Michael addition of thiophenol to α,β-unsaturated compounds catalyzed by CeCl3·7H2O-NaI was explored. The results show that the combination of CeCl3·7H2O-NaI can promote the conjugate addition of 2-aminothiophenol to α,β-unsaturated ketones with high steric hindrance efficiently. The condensation reactions of compounds 5 catalyzed by TiCl4 were also studied. The results indicate that TiCl4 is an efficient promoter for the reaction.

Key words: 1,5-Benzothiazepine, Antifungal activity, CeCl3·7H2O-NaI, Michael addition, Schiff base

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