5,5'-bis(3-chloroisothiazole-4-carbonitrile) | 915395-43-6

• 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: 5,5'-bis(3-chloroisothiazole-4-carbonitrile)
• 英文别名: 3,3'-dichloro-5,5'-biisothiazole-4,4'-dicarbonitrile；3,3a(2)-Dichloro[5,5a(2)-biisothiazole]-4,4a(2)-dicarbonitrile；3-chloro-5-(3-chloro-4-cyano-1,2-thiazol-5-yl)-1,2-thiazole-4-carbonitrile
• CAS: 915395-43-6
• 化学式: C₈Cl₂N₄S₂
• 分子量: 287.153
• InChiKey: DZYZRXFBUNYEAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  130
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  3-chloro-5-iodoisothiazole-4-carbonitrile 在 palladium diacetate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 27.5h， 以86%的产率得到5,5'-bis(3-chloroisothiazole-4-carbonitrile)
  参考文献：
  名称：

  New regiospecific isothiazole C–C coupling chemistry

  摘要：

  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。

  DOI：

  10.1039/b607442a

文献信息

• Silver-Mediated Palladium-Catalyzed Direct C−H Arylation of 3-Bromoisothiazole-4-carbonitrile
  作者：Heraklidia A. Ioannidou、Panayiotis A. Koutentis

  DOI：10.1021/ol200196m

  日期：2011.3.18

  Silver(I) fluoride-mediated Pd-catalyzed C-H direct arylation/heteroarylation of 3-bromolsothiazole-4-carbonitrile (1a) gives twenty-four 5-aryl/heteroaryl-3-bromolsothiazole-4-carbonitriles. The reaction was partially optimized with respect to catalyst, ligand, and base. During this study 3,3'-dibromo-5,5'-blisothiazole-4,4'-dicarbonitrile (3a) was Isolated as a byproduct and subsequently prepared via the silver-mediated Pd-catalyzed oxidative dimerization of 3-bromolsothiazole-4-carbonitrile in 67% yield. The analogous phenylation and oxidative dimerization of 3-chloroisothiazole-4-carbonitrile (1b) gave 3-chloro-5-phenylIsothiazole-4-carbonitrile (4) and 3,3'-dichloro-5,5'-bilsothiazole-4,4'-dicarbonitrile (3b) In 96% and 69% yields, respectively.
• 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。