2-(Dichloromethylene)-1,3-dithiolane | 144558-78-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫杂环戊烷
• 英文名称: 2-(Dichloromethylene)-1,3-dithiolane
• 英文别名: 2-(Dichloromethylidene)-1,3-dithiolane
• CAS: 144558-78-1
• 化学式: C₄H₄Cl₂S₂
• 分子量: 187.114
• InChiKey: QBSYYYLGLGYBAX-UHFFFAOYSA-N

物化性质

• 沸点：
  222.6±40.0 °C(Predicted)
• 密度：
  1.568±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(Dichloromethylene)-1,3-dithiolane 、 1,2-苯二硫醇 在 正丁基锂 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 二苯并四硫富瓦烯 、 2-(1,3-Benzodithiole-2-ylidene)-1,3-dithiolane
  参考文献：
  名称：

  A variable mechanism for the nucleophilic vinylic substitutions in a series of gem-dihalogenated alkenes by a bidentate sulfur nucleophile: an experimental and AM1 theoretical study

  摘要：

  The nucleophilic substitutions of a series of gem-dihalogenated alkenes 3,5,7,8, and 9 (RS)2C=CX2 (X = Cl, F) with 1,2-benzenedithiolate b have been studied. Depending on the structures of the R groups (alkyl, saturated and unsaturated cycloalkyls, aromatic ring), the course of the reactions and the structures of the yielded products are modified. In the frame of the addition-elimination-type mechanism for these nucleophilic substitutions, the energy contents of the anionic intermediates, resulting from the additions of the nucleophile b to the unsaturated centers, is calculated at the AM1 method level. For the compounds 5, 7, 8, and 9, the calculated energies nicely corroborate the experimental results. For 3, anionic intermediates are no longer found by calculation, and a synchronous single-step substitution is strongly suggested.

  DOI：

  10.1021/jo00069a035
• 作为产物：
  描述：

  2-(三氯甲基)-1,3-二噻戊环 在 N,N-二异丙基乙胺 作用下， 以 二甲基亚砜 为溶剂， 以90%的产率得到2-(Dichloromethylene)-1,3-dithiolane
  参考文献：
  名称：

  A variable mechanism for the nucleophilic vinylic substitutions in a series of gem-dihalogenated alkenes by a bidentate sulfur nucleophile: an experimental and AM1 theoretical study

  摘要：

  The nucleophilic substitutions of a series of gem-dihalogenated alkenes 3,5,7,8, and 9 (RS)2C=CX2 (X = Cl, F) with 1,2-benzenedithiolate b have been studied. Depending on the structures of the R groups (alkyl, saturated and unsaturated cycloalkyls, aromatic ring), the course of the reactions and the structures of the yielded products are modified. In the frame of the addition-elimination-type mechanism for these nucleophilic substitutions, the energy contents of the anionic intermediates, resulting from the additions of the nucleophile b to the unsaturated centers, is calculated at the AM1 method level. For the compounds 5, 7, 8, and 9, the calculated energies nicely corroborate the experimental results. For 3, anionic intermediates are no longer found by calculation, and a synchronous single-step substitution is strongly suggested.

  DOI：

  10.1021/jo00069a035
• 作为试剂：
  描述：

  1,2-苯二硫醇 在 正丁基锂 、 2-(Dichloromethylene)-1,3-dithiolane 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 二苯并四硫富瓦烯 、 2-(1,3-Benzodithiole-2-ylidene)-1,3-dithiolane
  参考文献：
  名称：

  A variable mechanism for the nucleophilic vinylic substitutions in a series of gem-dihalogenated alkenes by a bidentate sulfur nucleophile: an experimental and AM1 theoretical study

  摘要：

  The nucleophilic substitutions of a series of gem-dihalogenated alkenes 3,5,7,8, and 9 (RS)2C=CX2 (X = Cl, F) with 1,2-benzenedithiolate b have been studied. Depending on the structures of the R groups (alkyl, saturated and unsaturated cycloalkyls, aromatic ring), the course of the reactions and the structures of the yielded products are modified. In the frame of the addition-elimination-type mechanism for these nucleophilic substitutions, the energy contents of the anionic intermediates, resulting from the additions of the nucleophile b to the unsaturated centers, is calculated at the AM1 method level. For the compounds 5, 7, 8, and 9, the calculated energies nicely corroborate the experimental results. For 3, anionic intermediates are no longer found by calculation, and a synchronous single-step substitution is strongly suggested.

  DOI：

  10.1021/jo00069a035

文献信息

• Synthesis of Tetrathiafulvalene Derivatives by the Use of Organoaluminium Reagents
  作者：Takehiko Mori、Hiroo Inokuchi

  DOI：10.1246/cl.1992.1873

  日期：1992.9

  Bis(dimethylaluminium) salts of ethanedithiol, 1,2-benzenedithiol, and ethylenedithiol react with 1,3-dithiolane-2-carboxylate esters to give dihydro- and tetrahydro-tetrathiafulvalenes as well as tetrathiafulvalene derivatives.

  乙二硫醇、1,2-苯二硫醇和乙二硫醇的双（二甲基铝）盐与 1,3-二硫戊环-2-羧酸酯反应生成二氢和四氢四硫富瓦烯以及四硫富瓦烯衍生物。
• A variable mechanism for the nucleophilic vinylic substitutions in a series of gem-dihalogenated alkenes by a bidentate sulfur nucleophile: an experimental and AM1 theoretical study
  作者：Yves Gimbert、Alec Moradpour、Georges Dive、Dominique Dehareng、Khaled Lahlil

  DOI：10.1021/jo00069a035

  日期：1993.8

  The nucleophilic substitutions of a series of gem-dihalogenated alkenes 3,5,7,8, and 9 (RS)2C=CX2 (X = Cl, F) with 1,2-benzenedithiolate b have been studied. Depending on the structures of the R groups (alkyl, saturated and unsaturated cycloalkyls, aromatic ring), the course of the reactions and the structures of the yielded products are modified. In the frame of the addition-elimination-type mechanism for these nucleophilic substitutions, the energy contents of the anionic intermediates, resulting from the additions of the nucleophile b to the unsaturated centers, is calculated at the AM1 method level. For the compounds 5, 7, 8, and 9, the calculated energies nicely corroborate the experimental results. For 3, anionic intermediates are no longer found by calculation, and a synchronous single-step substitution is strongly suggested.