期刊信息

  • 刊名: 河北师范大学学报(自然科学版)Journal of Hebei Normal University (Natural Science)
  • 主办: 河北师范大学
  • ISSN: 1000-5854
  • CN: 13-1061/N
  • 中国科技核心期刊
  • 中国期刊方阵入选期刊
  • 中国高校优秀科技期刊
  • 华北优秀期刊
  • 河北省优秀科技期刊

串联反应一锅合成2-酯基多环稠合1,5-苯并硫氮杂䓬化合物

  • (河北师范大学 化学与材料科学学院,河北省有机功能分子重点实验室,河北 石家庄050024)
  • DOI: 10.13763/j.cnki.jhebnu.nse.202203013

Synthesis of 2-ester Polycyclic Fused 1, 5-benzothiazepines via One-pot Tandem Reactions

摘要/Abstract

摘要:

以取代的邻氨基苯硫酚、取代的1-茚酮、乙醛酸乙酯为原料,乙醇为溶剂,三氯化铈作催化剂,三组分串联一锅合成了10种2-酯基多环稠合1, 5-苯并硫氮杂䓬化合物.首先,取代的1-茚酮与乙醛酸乙酯经Knoevenagel 反应制得α, β-不饱和酯类化合物,不分离中间体,再与邻氨基苯硫酚上亲核性的巯基发生共轭加成,生成氨基酮中间体,其另一亲核性的氨基进攻羰基发生分子内亲核加成、脱水环合成亚胺或烯胺结构的多环稠合1, 5-苯并硫氮杂䓬化合物.该合成方法摒弃了传统的多步反应,具有原子经济、操作简便、反应条件温和、产率较高、选择性好且绿色环保的优点.

Abstract:

In this paper,ten novel 2-ester polycyclic fused 1, 5-benzothiazepine compounds were obtained via one-pot three-component tandem reactions with CeCl3 as catalyst in ethanol. These reactions were achieved by reacting substituted o-aminothiophenol,substituted 1indanone,ethyl glyoxylate.The reaction process was the Knoevenagel reaction between substituted 1-indanone and ethyl glyoxylate to require α, β-unsaturated ester compounds without separating intermediates.the aminoketone intermediate was formed by the conjugate addition of the nucleophilic sulfhydryl group on o-aminothiophenol.Then, the polycyclic fused 1, 5-benzothiazepine compounds of imine or enamine structure were formed by intramolecular nucleophilic addition and dehydration cyclization that another nucleophilic amino group attacks the carbonyl group. The synthesis method abandons the traditional multi-step reaction and has the advantages of atomic economy,simple operation,mild reaction conditions,high yield,good selectivity and environmental protection, respectively.

参考文献 7

  • [1] ZHAO Y Y,HUANG X Y,WU J P,et al.Molecular Basis for Ligand Modulation of a Mammalian Volta-gegated Ca2+ Channel [J]. Cell, 2019,177(6):1495-1506.doi:10.1016/j.cell.2019.04.043
  • [2] YOSHIZAWA K, NAKASHIMA K, TABUCHI M,et al.Benzothiazepines,Diltiazem and JTV-519,Exert an Anxiolyticlike Effect via Neurosteroid Biosynthesis in Mice [J].J Pharmacol Sci,2020,143(3) :234-237.doi:10.1016/j.jphs.2020.03.003
  • [3] WANG B, WANG L R, LIU L L,et al.A Novel Series of Benzothiazepine Derivatives as Tubulin Polymerization Inhibitors with Anti-tumor Potency [J]. Bioorg Chem,2021,108:104585. doi: 10.1016/j.bioorg.2020.104585
  • [4] SHAIK A B, BHANDARE R R, NISSANKARARAO S,et al.Synthesis,and Biological Screening of Chloropyrazine Conjugated Benzothiazepine Derivatives as Potential Antimicrobial,Antitubercular and Cytotoxic Agents [J]. Arabian J Chem,2021,14(2):102915.doi:10.1016/j.arabjc.2020.102915
  • [5] DAS S, DUTTA A.Recent Advances in Transition-metal-catalyzed Annulations for the Construction of a 1-indanone Core [J]. New J Chem, 2021,45(10):4545-4568.doi:10.1039/d0nj06318e
  • [6] KHATAB T K, EL-BAYOUKI K A M, BASYOUNI W M.A New and Facile Tetrachlorosilane-promoted One-pot Condensation for the Synthesis of a Novel Series of Tetracyclic 1, 5-thiazepines [J]. Tetrahedron Lett,2014,55(44):6039-6041.doi:10.1016/j.tetlet.2014.09.006
  • [7] PATI T K, AJARUL S, KUNDU M,et al.Synthesis of Functionalized Arylacetamido-2-pyridones Through Ortho-C(sp(2))-H-activated Installation of Olefins and Alkynes [J]. J Org Chem,2020,85(13) :8563-8579.doi:10.1021/acs.joc.0c00941