5-氨基-3-氯异噻唑-4-甲腈 | 3889-68-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 中文名称: 5-氨基-3-氯异噻唑-4-甲腈
• 英文名称: 5-amino-3-chloroisothiazole-4-carbonitrile
• 英文别名: 5-amino-3-chloro-isothiazole-4-carbonitrile；3-chloro-4-cyano-5-amino isothiazole；3-Chlor-5-amino-4-thiazolcarbonitril；5-Amino-3-chlor-4-cyanisothiazol；5-amino-3-chloro-1,2-thiazole-4-carbonitrile
• CAS: 3889-68-7
• 化学式: C₄H₂ClN₃S
• 分子量: 159.599
• InChiKey: BOTARCWBHNBEFS-UHFFFAOYSA-N

物化性质

• 熔点：
  210-212℃
• 沸点：
  229.4±40.0 °C(Predicted)
• 密度：
  1.63±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 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：
  90.9
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  5-氨基-3-氯异噻唑-4-甲腈 在 溴 、 亚硝酸异戊酯 作用下， 以 硝基甲烷 为溶剂， 反应 0.17h， 以69%的产率得到5-bromo-3-chloroisothiazole-4-carbonitrile
  参考文献：
  名称：

  Regioselective hydrodehalogenation of 3,5-dihaloisothiazole-4-carbonitriles: synthesis of 3-haloisothiazole-4-carbonitriles

  摘要：

  3,5-Dibromoisothiazole-4-carbonitrile 1 treated with Zn or In dust (5 equiv) and HCO2H undergoes regioselective hydrodebromination to give 3-bromoisothiazole-4-carbonitrile 3 in 70-74% yield. Similarly, 5-bromo and iodo 3-chloroisothiazole-4-carbonitriles 8 and 9 give 3-chloroisothiazole-4-carbonitrile 4 in 77 and 85% yields, respectively. Also hydrodeamination of 5-amino-3-chloroisothiazole-4-carbonitrile 7 using isoamyl nitrite gives the latter in 95% yield. The dibromoisothiazole 1 reacts with Zn dust in either DCO2D or HCO2D to give 3-bromo-5-deuterioisothiazole-4-carbonitrile 10 in 71 and 58% yields, respectively. The 3-bromoisothiazole 3 reacts with cyclic dialkylamines to give the corresponding 2-(dialkylaminomethylene)-malononitriles and not the expected 3-dialkylaminoisothiazole-4-carbonitriles. Finally, the 3-bromoisothiazole 3 is readily converted into both 3-bromoisothiazole-4-carboxamide 19 and the carboxylic acid 20. All products are fully characterized. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.03.065
• 作为产物：
  描述：

  3,5-二氯-4-异噻唑甲腈 在 氨 作用下， 以 四氢呋喃 为溶剂， 生成 5-氨基-3-氯异噻唑-4-甲腈
  参考文献：
  名称：

  The Synthesis of Isothiazoles. I. 3,5-Dichloro-4-isothiazolecarbonitrile and Its Derivatives

  摘要：

  DOI：

  10.1021/jo01026a033

文献信息

• New regiospecific isothiazole C–C coupling chemistry
  作者：Irene C. Christoforou、Panayiotis A. Koutentis

  DOI：10.1039/b607442a

  日期：——

  Regioselective palladium catalysed coupling reactions are achieved in good to high yields, starting from either 3,5-dichloro- or 3,5-dibromoisothiazole-4-carbonitriles 1 and 2, providing 3-halo-5-(hetero/aryl, alkenyl and alkynyl)isothiazoles 3, 4, 6–9 from Stille couplings, 3-halo-5-(hetero/arylethynyl)isothiazoles 14–19 from Sonogashira and 5,5′-bi(3-chloroisothiazole-4-carbonitrile) (13) from an Ullmann type coupling. 3,5-Dibromoisothiazole-4-carbonitrile 2 is more reactive than the dichloroisothiazole-4-carbonitrile 1 and effective enough for Stille, Negishi and Sonogashira couplings. 5,5-Bi(3-chloroisothiazole-4-carbonitrile) (13) is prepared by a palladium catalysed Ullmann coupling from 3-chloro-5-iodoisothiazole-4-carbonitrile (11). A variety of 3-substituted isothiazoles (3-substituents = Cl, Br, OMs, OTs and OTf) are less reactive and fail to give successful Suzuki couplings at the isothiazole C-3 position. The 3-iodo-5-phenyl-isothiazole-4-carbonitrile (28), prepared via Sandmeyer iodination, participates successfully in Suzuki, Ullmann type, Stille, Negishi and Sonogashira coupling reactions. All products are fully characterized.

  区域选择性钯催化的偶联反应以良好至高产率实现，从3,5-二氯或3,5-二溴异噻唑-4-腈1和2出发，通过Stille偶联反应得到3-卤代-5-(杂/芳基、烯基和炔基)异噻唑3、4、6–9，通过Sonogashira反应得到3-卤代-5-(杂/芳基炔基)异噻唑14–19，以及通过Ullmann型偶联反应得到5,5'-二(3-氯异噻唑-4-腈)13。3,5-二溴异噻唑-4-腈2比3,5-二氯异噻唑-4-腈1更具反应活性，足以有效进行Stille、Negishi和Sonogashira偶联反应。5,5-二(3-氯异噻唑-4-腈)13通过钯催化的Ullmann偶联反应由3-氯-5-碘异噻唑-4-腈11制备。多种3-取代异噻唑（3-取代基=Cl、Br、OMs、OTs和OTf）反应活性较低，未能成功在异噻唑C-3位置进行Suzuki偶联反应。通过Sandmeyer碘化法制备的3-碘-5-苯基异噻唑-4-腈28成功参与了Suzuki、Ullmann型、Stille、Negishi和Sonogashira偶联反应。所有产物均经过充分表征。
• Pesticidal methods and compounds
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0623282A1

  公开（公告）日：1994-11-09

  The invention provides a method of combating caterpillar pests, using a compound of general formula where X represents a halogen atom, R represents a hydrogen atom or an optionally substituted alkyl group, and Q represents an optionally substituted aryl or heteroaryl group. Certain compounds of general formula I are novel.

  本发明提供了一种对抗毛虫害的方法，使用一种通式为X代表卤素原子，R代表氢原子或可选择性取代的烷基团，Q代表可选择性取代的芳基或杂环芳基团的化合物。其中，某些通式I的化合物是新颖的。
• The conversion of isothiazoles into pyrazoles using hydrazine
  作者：Heraklidia A. Ioannidou、Panayiotis A. Koutentis

  DOI：10.1016/j.tet.2009.06.041

  日期：2009.8

  The conversion of isothiazoles into pyrazoles on treatment with hydrazine is investigated. The influence of various C-3, C-4 and C-5 isothiazole substituents and some limitations of this ring transformation are examined. When the isothiazole C-3 substituent is a good nucleofuge, 3-aminopyrazoles are obtained. However, when the 3-substituent is not a leaving group it is retained in the pyrazole product. Treatment of 4-bromo-3-chloro-5-phenylisothiazoie 56 or 3-chloro-4,5-diphenylisothiazole 57 with anhydrous hydrazine at ca. 200 degrees C for a few minutes gives the corresponding 3-hydrazinoisothiazoles 61 and 64 respectively in high yields; the stability of these new hydrazines is investigated. 5,5'-Diphenyl-3,3'-biisothiazole-4,4'-dicarbonitrile 78 reacts with hydrazine to give 5,5'-diphenyl-3,3'-bi(1H-pyi-azole)-4,4'-dicarbonitrile 79. Methylhydrazine reacts with 3-chloro-5-phenytisothiazole-4-carbonitrile 1 to give 3-(1-methylhydrazino)-5-phenylisothiazole-4-carbontrile 83 and 3-amino-lmethyl-5-phenylpyrazole-4-carbonitrile 84. All products are fully characterised and rational mechanisms for the isothiazole into pyrazole transformation are proposed. (C) 2009 Elsevier Ltd. All rights reserved.
• The Synthesis of Isothiazoles. I. 3,5-Dichloro-4-isothiazolecarbonitrile and Its Derivatives
  作者：W. R. Hatchard

  DOI：10.1021/jo01026a033

  日期：1964.3
• Regioselective hydrodehalogenation of 3,5-dihaloisothiazole-4-carbonitriles: synthesis of 3-haloisothiazole-4-carbonitriles
  作者：Heraklidia A. Ioannidou、Panayiotis A. Koutentis

  DOI：10.1016/j.tet.2011.03.065

  日期：2011.5

  3,5-Dibromoisothiazole-4-carbonitrile 1 treated with Zn or In dust (5 equiv) and HCO2H undergoes regioselective hydrodebromination to give 3-bromoisothiazole-4-carbonitrile 3 in 70-74% yield. Similarly, 5-bromo and iodo 3-chloroisothiazole-4-carbonitriles 8 and 9 give 3-chloroisothiazole-4-carbonitrile 4 in 77 and 85% yields, respectively. Also hydrodeamination of 5-amino-3-chloroisothiazole-4-carbonitrile 7 using isoamyl nitrite gives the latter in 95% yield. The dibromoisothiazole 1 reacts with Zn dust in either DCO2D or HCO2D to give 3-bromo-5-deuterioisothiazole-4-carbonitrile 10 in 71 and 58% yields, respectively. The 3-bromoisothiazole 3 reacts with cyclic dialkylamines to give the corresponding 2-(dialkylaminomethylene)-malononitriles and not the expected 3-dialkylaminoisothiazole-4-carbonitriles. Finally, the 3-bromoisothiazole 3 is readily converted into both 3-bromoisothiazole-4-carboxamide 19 and the carboxylic acid 20. All products are fully characterized. (C) 2011 Elsevier Ltd. All rights reserved.