2,3-dicarbethoxy-7-(2,2-dicyclopropylmethylidene)-2,3-diazabicyclo<2.2.1>heptane | 174741-05-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: 2,3-dicarbethoxy-7-(2,2-dicyclopropylmethylidene)-2,3-diazabicyclo<2.2.1>heptane
• 英文别名: diethyl 7-(dicyclopropylmethylidene)-2,3-diazabicyclo[2.2.1]heptane-2,3-dicarboxylate
• CAS: 174741-05-0
• 化学式: C₁₈H₂₆N₂O₄
• 分子量: 334.415
• InChiKey: UALQSTXCZGLRHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  59.08
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2,3-dicarbethoxy-7-(2,2-dicyclopropylmethylidene)-2,3-diazabicyclo<2.2.1>heptane 在 氢氧化钾 、 氨 、 copper dichloride 作用下， 生成 7-(2,2-dicyclopropylmethylidene)-2,3-diazabicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  Influence of the Geminal Biscyclopropyl Group in the Reactions of Trimethylenemethane:  Reversible Intersystem Crossing

  摘要：

  The azo compound precursor to Berson's trimethylenemethane (TMM) biradical system, 8-methylene-1,3-cyclopentanediyl, was substituted with two cyclopropyl groups on the exomethylene. Generation of the TMM species by pyrolysis, direct photolysis, and benzophenone-sensitized photolysis resulted in formation of both cyclopropane ring-opened monomer and cyclopropane ring-unopened dimers whose ratio depended directly on temperature and extent of dilution. The ground state appears to be triplet on the basis of ESR spectrometry. The results contrast with previous work (Waldemar Adam) showing that monocyclopropyl substitution on Person's TMM species gives both ring-opened monomer and ring-unopened dimers upon pyrolysis and gives mostly ring-unopened dimer upon direct photolysis at 0-20 degrees C in what appear to be concentration-independent reactions. The observations with the biscyclopropyl-substituted species are consistent with steric effects retarding dimerization of the triplet allowing reversible intersystem crossing back to singlet and perhaps with reduction in the singlet-triplet gap as well.

  DOI：

  10.1021/jo9513727
• 作为产物：
  描述：

  双环丙基酮 在 palladium on activated charcoal 氢气 、 sodium 作用下， 以 乙醇 为溶剂， 生成 2,3-dicarbethoxy-7-(2,2-dicyclopropylmethylidene)-2,3-diazabicyclo<2.2.1>heptane
  参考文献：
  名称：

  Influence of the Geminal Biscyclopropyl Group in the Reactions of Trimethylenemethane:  Reversible Intersystem Crossing

  摘要：

  The azo compound precursor to Berson's trimethylenemethane (TMM) biradical system, 8-methylene-1,3-cyclopentanediyl, was substituted with two cyclopropyl groups on the exomethylene. Generation of the TMM species by pyrolysis, direct photolysis, and benzophenone-sensitized photolysis resulted in formation of both cyclopropane ring-opened monomer and cyclopropane ring-unopened dimers whose ratio depended directly on temperature and extent of dilution. The ground state appears to be triplet on the basis of ESR spectrometry. The results contrast with previous work (Waldemar Adam) showing that monocyclopropyl substitution on Person's TMM species gives both ring-opened monomer and ring-unopened dimers upon pyrolysis and gives mostly ring-unopened dimer upon direct photolysis at 0-20 degrees C in what appear to be concentration-independent reactions. The observations with the biscyclopropyl-substituted species are consistent with steric effects retarding dimerization of the triplet allowing reversible intersystem crossing back to singlet and perhaps with reduction in the singlet-triplet gap as well.

  DOI：

  10.1021/jo9513727

文献信息

• Influence of the Geminal Biscyclopropyl Group in the Reactions of Trimethylenemethane:  Reversible Intersystem Crossing
  作者：Gitendra C. Paul、Joseph J. Gajewski

  DOI：10.1021/jo9513727

  日期：1996.1.1

  The azo compound precursor to Berson's trimethylenemethane (TMM) biradical system, 8-methylene-1,3-cyclopentanediyl, was substituted with two cyclopropyl groups on the exomethylene. Generation of the TMM species by pyrolysis, direct photolysis, and benzophenone-sensitized photolysis resulted in formation of both cyclopropane ring-opened monomer and cyclopropane ring-unopened dimers whose ratio depended directly on temperature and extent of dilution. The ground state appears to be triplet on the basis of ESR spectrometry. The results contrast with previous work (Waldemar Adam) showing that monocyclopropyl substitution on Person's TMM species gives both ring-opened monomer and ring-unopened dimers upon pyrolysis and gives mostly ring-unopened dimer upon direct photolysis at 0-20 degrees C in what appear to be concentration-independent reactions. The observations with the biscyclopropyl-substituted species are consistent with steric effects retarding dimerization of the triplet allowing reversible intersystem crossing back to singlet and perhaps with reduction in the singlet-triplet gap as well.