N-(p-toluenesulfonyl)-3,4-dimethylenepyrrole biradical | 151872-04-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(p-toluenesulfonyl)-3,4-dimethylenepyrrole biradical
• 英文别名: 3,4-dimethylidene-1-(4-methylphenyl)sulfonyl-2H-pyrrol-1-ium-2-ide
• CAS: 151872-04-7
• 化学式: C₁₃H₁₃NO₂S
• 分子量: 247.318
• InChiKey: HTLGJIPLRGMXQD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(p-toluenesulfonyl)-3,4-dimethylenepyrrole biradical 在 氧气 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  杂环单峰双自由基反应的绝对速率通过纳秒时间分辨吸收光谱来确定。烯烃和双氧的二聚和环加成

  摘要：

  Singlet biradicals of the 3,4-dimethyleneheterocycle series, where the heterocycle is furan, thiophene, or N-substituted pyrrole, with chromophores in the UV-vis region (560-640 nm), are generated by nanosecond laser flash photolysis of diazene precursors in fluid solution. The rate constants for disappearance of these transients are determined by time-resolved absorption spectroscopy using the long-wavelength band. The rate constants for dimerization are near the encounter-controlled rate. Rates of trapping by alkenes are well described by a frontier orbital model. Oxygen trapping rate constants range between 10(7) and 10(9) M-1 s-1. The ratios of rate constants for trapping of 3,4-dimethylene-N-(p-toluenesulfonyl)pyrrole by pairs of alkenes in preparative competition experiments are in good agreement with those determined by the flash photolytic method. This confirms assignments of the 3,4-dimethyleneheterocycle structure to the chromophore of the biradical transients.

  DOI：

  10.1021/j100152a047
• 作为产物：
  描述：

  N-(p-toluenesulfonyl)pyrrolo diazene 以 2-甲基四氢呋喃 为溶剂， 生成 N-(p-toluenesulfonyl)-3,4-dimethylenepyrrole biradical
  参考文献：
  名称：

  杂环单峰双自由基反应的绝对速率通过纳秒时间分辨吸收光谱来确定。烯烃和双氧的二聚和环加成

  摘要：

  Singlet biradicals of the 3,4-dimethyleneheterocycle series, where the heterocycle is furan, thiophene, or N-substituted pyrrole, with chromophores in the UV-vis region (560-640 nm), are generated by nanosecond laser flash photolysis of diazene precursors in fluid solution. The rate constants for disappearance of these transients are determined by time-resolved absorption spectroscopy using the long-wavelength band. The rate constants for dimerization are near the encounter-controlled rate. Rates of trapping by alkenes are well described by a frontier orbital model. Oxygen trapping rate constants range between 10(7) and 10(9) M-1 s-1. The ratios of rate constants for trapping of 3,4-dimethylene-N-(p-toluenesulfonyl)pyrrole by pairs of alkenes in preparative competition experiments are in good agreement with those determined by the flash photolytic method. This confirms assignments of the 3,4-dimethyleneheterocycle structure to the chromophore of the biradical transients.

  DOI：

  10.1021/j100152a047

文献信息

• Absolute rates of heterocyclic singlet biradical reactions determined by nanosecond time-resolved absorption spectroscopy. Dimerizations and cycloadditions to alkenes and to dioxygen
  作者：Richard B. Heath、Linda C. Busch、Xu Wu Feng、Jerome A. Berson、J. C. Scaiano、Alain B. Berinstain

  DOI：10.1021/j100152a047

  日期：1993.12

  Singlet biradicals of the 3,4-dimethyleneheterocycle series, where the heterocycle is furan, thiophene, or N-substituted pyrrole, with chromophores in the UV-vis region (560-640 nm), are generated by nanosecond laser flash photolysis of diazene precursors in fluid solution. The rate constants for disappearance of these transients are determined by time-resolved absorption spectroscopy using the long-wavelength band. The rate constants for dimerization are near the encounter-controlled rate. Rates of trapping by alkenes are well described by a frontier orbital model. Oxygen trapping rate constants range between 10(7) and 10(9) M-1 s-1. The ratios of rate constants for trapping of 3,4-dimethylene-N-(p-toluenesulfonyl)pyrrole by pairs of alkenes in preparative competition experiments are in good agreement with those determined by the flash photolytic method. This confirms assignments of the 3,4-dimethyleneheterocycle structure to the chromophore of the biradical transients.