methyl 3-bromo-5-cyanoisothiazole-4-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: methyl 3-bromo-5-cyanoisothiazole-4-carboxylate
• 化学式: C₆H₃BrN₂O₂S
• 分子量: 247.072
• InChiKey: JSKAAZTXPSHSDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.56
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  62.98
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  吗啉 、 methyl 3-bromo-5-cyanoisothiazole-4-carboxylate 以 甲苯 为溶剂， 反应 1.0h， 以99%的产率得到methyl 5-cyano-3-(morpholin-4-yl)isothiazole-4-carboxylate
  参考文献：
  名称：

  Reactions of selected 3-bromoisothiazole-5-carbonitriles with the secondary dialkylamines pyrrolidine and morpholine

  摘要：

  Readily available 3-bromoisothiazole-5-carbonitriles bearing various C-4 substituents [H, CO2R C N and halogen (CI or Br)], react with either pyrrolidine or morpholine to give, in most cases, the 3-amino-substituted derivatives in high yields. The reaction of 3-bromoisothiazole-4,5-dicarbonitrile, however, varied with the nucleophilicity of the dialkylamine: pyrrolidine led to cleavage of the isothiazole ring to give 2-[di(pyrrolidin-1-yl)methylene]malononitrile while morpholine led to the expected 3-(morpholin-4-yl)isothiazole-4,5-dicarbonitrile. By comparison, 3-chloroisothiazole-4,5-dicarbonitrile reacted with pyrrolidine to give surprisingly, 3-chloro-5-(pyrrolidin-1-yl)isothiazole-4-carbonitrile as the major product, while with morpholine the major product was the expected 3-(morpholin-4-yl)isothiazole-4,5-dicarbonitrile. The mechanisms of the transformations are discussed, together with rationalization for the formation of side products. Furthermore, the hydrolytic decarboxylation of methyl and ethyl esters of 3-dialkylaminoisothiazoles using both conventional heating and microwave irradiation is reported. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.06.012
• 作为产物：
  描述：

  (Z)-methyl 2-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)-2-cyanoacetate 在 氢溴酸 作用下， 以 乙醚 为溶剂， 反应 5.0h， 以78%的产率得到methyl 3-bromo-5-cyanoisothiazole-4-carboxylate
  参考文献：
  名称：

  Ring transformation of (4-chloro-5H-1,2,3-dithiazol-5-ylidene)acetonitriles to 3-haloisothiazole-5-carbonitriles

  摘要：

  提供了改进的条件，用于将1,2,3-二噻唑转化为异噻唑-5-碳腈，并附带机理解释。

  DOI：

  10.1039/c3ra47261b