3-Chloro-1-dichloromethylene-1H-indene-2-carbonitrile | 175793-48-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 3-Chloro-1-dichloromethylene-1H-indene-2-carbonitrile
• 英文别名: 1H-Indene-2-carbonitrile, 3-chloro-1-(dichloromethylene)-；1-chloro-3-(dichloromethylidene)indene-2-carbonitrile
• CAS: 175793-48-3
• 化学式: C₁₁H₄Cl₃N
• 分子量: 256.518
• InChiKey: XGGGTALNFKKMSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  哌啶 、 3-Chloro-1-dichloromethylene-1H-indene-2-carbonitrile 以 二氯甲烷 为溶剂， 反应 3.0h， 以45%的产率得到3-Chloro-1-(di-piperidin-1-yl-methylene)-1H-indene-2-carbonitrile
  参考文献：
  名称：

  Cyclopenta-1,2-dithioles, Cyclopenta-1,2-thiazines, and Methylenoindenes from New Molecular Rearrangements

  摘要：

  The cyclobutanone oxime 6 reacts with disulfur dichloride, N-chlorosuccinimide, and Hunig's base to give three unexpected 10 pi pseudo azulenes in low yield: the dark blue cyclopenta-1,2-dithiole 7, its red isomer 10, and the orange cyclopenta-1,2-thiazine 8. The benzo derivative 14 of oxime 6 gives an analogous benzo product 15 together with the methylenoindene 16 in high yield. The formation of all of these products can be explained by a unified mechanism based on initial abnormal Beckmann rearrangement of the oximes to cyanides followed by cyclization and/or exhaustive chlorination and dehydrochlorination. The 1,2-dithiole 7 is synthesized independently from 1-(cyanomethyl)cyclopentene 11 and the above reagents, and 1-cyanomethylindene 17 is similarly converted into methylenoindenes 18 and 19, which are isomers of product 16. Structures 7 and 15 are confirmed by X-ray crystallography, and compounds 7, 8, 15, 16, 18, and 19 show birefringence on heating in a hot stage polarizing microscope indicating, most unexpectedly, liquid crystalline behavior.

  DOI：

  10.1021/jo9612234
• 作为产物：
  描述：

  2,3-benzo-cis-bicyclo<3.2.0>heptan-6-one oxime 在 二氯化二硫 、 N-氯代丁二酰亚胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 76.5h， 生成 3-Chloro-1-dichloromethylene-1H-indene-2-carbonitrile
  参考文献：
  名称：

  Cyclopenta-1,2-dithioles, Cyclopenta-1,2-thiazines, and Methylenoindenes from New Molecular Rearrangements

  摘要：

  The cyclobutanone oxime 6 reacts with disulfur dichloride, N-chlorosuccinimide, and Hunig's base to give three unexpected 10 pi pseudo azulenes in low yield: the dark blue cyclopenta-1,2-dithiole 7, its red isomer 10, and the orange cyclopenta-1,2-thiazine 8. The benzo derivative 14 of oxime 6 gives an analogous benzo product 15 together with the methylenoindene 16 in high yield. The formation of all of these products can be explained by a unified mechanism based on initial abnormal Beckmann rearrangement of the oximes to cyanides followed by cyclization and/or exhaustive chlorination and dehydrochlorination. The 1,2-dithiole 7 is synthesized independently from 1-(cyanomethyl)cyclopentene 11 and the above reagents, and 1-cyanomethylindene 17 is similarly converted into methylenoindenes 18 and 19, which are isomers of product 16. Structures 7 and 15 are confirmed by X-ray crystallography, and compounds 7, 8, 15, 16, 18, and 19 show birefringence on heating in a hot stage polarizing microscope indicating, most unexpectedly, liquid crystalline behavior.

  DOI：

  10.1021/jo9612234

文献信息

• Cyclopenta-1,2-dithioles and cyclopenta-1,2-thiazines from new molecular rearrangements
  作者：Oleg A. Rakitin、Charles W. Rees、Tom�s Torroba

  DOI：10.1039/cc9960000427

  日期：——

  The cyclobutanone oxime 6 reacts with disulfur dichloride to give two unexpected 10π pseudoazulenes in low yield: the dark blue cyclopenta-1,2-dithiole 7 and the orange cyclopenta-1,2-thiazine 8; the benzo derivative 14 of this oxime gives the analogous benzo product 15 together with the methylene indene 16 in high yield; mechanisms based on abnormal Beckman rearrangements are proposed for the formation of all of these products.

  环丁酮肟 6 与二氯化二硫反应，以较低的产率得到两种意想不到的 10π 伪唑烯：深蓝色的环戊二烯-1,2-二硫杂环 7 和橙色的环戊二烯-1,2-噻嗪 8；该肟的苯并衍生物 14 以较高的产率得到类似的苯并产物 15 和亚甲基茚 16；对于所有这些产物的形成，提出了基于异常贝克曼重排的机理。