3-bromoisothiazole-4,5-dicarbonitrile | 470483-17-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 3-bromoisothiazole-4,5-dicarbonitrile
• 英文别名: 3-Bromo-1,2-thiazole-4,5-dicarbonitrile
• CAS: 470483-17-1
• 化学式: C₅BrN₃S
• 分子量: 214.045
• InChiKey: WBHNOEXEABWULZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  88.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-bromoisothiazole-4,5-dicarbonitrile 在 sodium hydroxide 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.08h， 以90%的产率得到3-bromo-4-cyanoisothiazole-5-carboxamide
  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
• 作为产物：
  描述：

  2-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)propanedinitrile 在 氢溴酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以96%的产率得到3-bromoisothiazole-4,5-dicarbonitrile
  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

文献信息

• Reactions of 1,2,3-dithiazoles with halogenated malononitriles
  作者：Irene C. Christoforou、Panayiotis A. Koutentis、Charles W. Rees

  DOI：10.1039/b202038f

  日期：2002.5.10

  Dibromomalononitrile 3a reacts with 4-chloro-1,2,3-dithiazole-5-thione 9 and monobromomalononitrile 3c reacts with 4,5-dichloro-1,2,3-dithiazolium chloride 4 (Appel salt) to give 4-chloro-5H-1,2,3-dithiazole-5-ylidenemalononitrile 1 in 76 and 73% yields, respectively, thus providing the best available synthesis of this key intermediate. The reactions were accompanied by the formation of 1-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)-1,2-dihaloethene-2-carbonitriles 5, the yields of which increased with reaction temperature. In refluxing toluene, dibromomalononitrile 3a and dithiazolethione 9 give directly 3-bromoisothiazole-4,5-dicarbonitrile 12 (59%); the probable intermediate (dicyanomethylene)dithiazole 1 is readily converted into bromoisothiazole 12 on treatment with anhydrous gaseous HBr at ca. 20 °C (83%). The addition of bromine to dithiazolethione 9 gives 5-bromosulfanyl-4-chloro-1,2,3-dithiazolium bromide 11 almost quantitatively. Mechanisms are proposed for all these reactions.

  二溴丙二腈 3a 与 4-氯-1,2,3-二噻唑-5-硫酮 9 反应，单溴丙二腈 3c 与 4,5-二氯-1,2,3-二噻唑氯化铵 4（阿贝尔盐）反应，分别得到 4-氯-5H-1,2,3-二噻唑-5-亚基丙二腈 1，收率分别为 76% 和 73%，从而提供了这一关键中间体的最佳合成方法。这些反应伴随着 1-(4-氯-5H-1,2,3-二噻唑-5-亚基氨基)-1,2-二卤乙烯-2-甲腈 5 的生成，其产率随反应温度的升高而增加。在回流甲苯中，二溴丙二腈 3a 和二噻唑硫酮 9 直接生成 3-溴异噻唑-4,5-二甲腈 12（59%）；可能的中间体（二氰基亚甲基）二噻唑 1 在约 20 °C 下用无水气态 HBr 处理后很容易转化成溴异噻唑 12（83%）。在二噻唑硫酮 9 中加入溴，几乎可以定量得到 5-溴硫基-4-氯-1,2,3-二噻唑溴化物 11。本文提出了所有这些反应的机理。
• Reactions of selected 3-bromoisothiazole-5-carbonitriles with the secondary dialkylamines pyrrolidine and morpholine
  作者：Andreas S. Kalogirou、Panayiotis A. Koutentis

  DOI：10.1016/j.tet.2014.06.012

  日期：2014.10

  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.