3-(CH_2)_nCO_2C_2H_5-1,5-苯并硫氮杂的合成、晶体结构及抑真菌活性  

Synthesis,Crystal Structure and Antifungal Activities of 3-(CH_2)_nCO_2C_2H_5-1,5-Benzothiazepines

作　　者：邱召来[1] 李文红[2] 朱海菲[1] 刘倩[1] 李媛[1] 

机构地区：[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

出　　处：《高等学校化学学报》2013年第3期579-589,共11页Chemical Journal of Chinese Universities

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

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.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.

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 

分 类 号：O626[理学—有机化学]