1-(methoxycarbonyl)-4-methyl-2,4,6-triazatricyclo<5.2.1.0^2.6>dec-8-ene-3,5-dione | 146562-67-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-(methoxycarbonyl)-4-methyl-2,4,6-triazatricyclo<5.2.1.0^2.6>dec-8-ene-3,5-dione
• 英文别名: Methyl 4-methyl-3,5-dioxo-2,4,6-triazatricyclo[5.2.1.02,6]dec-8-ene-1-carboxylate
• CAS: 146562-67-6
• 化学式: C₁₀H₁₁N₃O₄
• 分子量: 237.215
• InChiKey: PGXZRRORNGSSCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  70.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(methoxycarbonyl)-4-methyl-2,4,6-triazatricyclo<5.2.1.0^2.6>dec-8-ene-3,5-dione 在 palladium on activated charcoal 甲醇 、 氢氧化钾 、 ammonium hydroxide 、 锂硼氢 、 氢气 、 potassium hydride 、 三乙胺 、 8-甲氧基-9-硼杂双环[3.3.1]壬烷 、 copper(l) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 、 氯苯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 85.0h， 生成 2,3-diaza-5-methylenebicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  Determination of the triplet lifetimes of 1,3-cyclopentanediyl biradicals derived from the photodenitrogenation of azoalkanes with time-resolved photoacoustic calorimetry

  摘要：

  The triplet lifetime of the parent 1,3-cyclopentanediyl (2a) and the 4-methylene and the 1-phenyl derivatives 2b and 2c were determined by time-resolved photoacoustic calorimetry (PAC). For the biradical 2b, PAC was the only suitable method to date for determining its hitherto inaccessible triplet lifetime. A comparison with results for biradicals 2a,c obtained in earlier studies shows that PAC is a reliable method for measuring triplet lifetimes of biradicals. The effect on the triplet lifetimes of allyl and benzyl conjugation at one radical center in 2b,c proved to be insignificant. In view of the large enhancement of the biradical lifetime as the result of benzylic conjugation at both radical sites, as in the diphenyl derivative 2d, the present results imply that the biradicals 2b,c are still flexible enough to enable effective intersystem crossing through pyramidalization. The much larger (ca. 200-fold) triplet lifetime of biradical 2b compared to its gem-dimethyl derivative 2e suggests that geminal substitution is a general phenomenon for the effective reduction of the lifetimes of triplet biradicals through changes in the singlet-triplet energy gap.

  DOI：

  10.1021/jo00058a031
• 作为产物：
  描述：

  环戊烯-1-羧酸甲酯 、 4-甲基-1,2,4-三吖啉-3,5-二酮 以 二氯甲烷 为溶剂， 生成 1-(methoxycarbonyl)-4-methyl-2,4,6-triazatricyclo<5.2.1.0^2.6>dec-8-ene-3,5-dione
  参考文献：
  名称：

  Determination of the triplet lifetimes of 1,3-cyclopentanediyl biradicals derived from the photodenitrogenation of azoalkanes with time-resolved photoacoustic calorimetry

  摘要：

  The triplet lifetime of the parent 1,3-cyclopentanediyl (2a) and the 4-methylene and the 1-phenyl derivatives 2b and 2c were determined by time-resolved photoacoustic calorimetry (PAC). For the biradical 2b, PAC was the only suitable method to date for determining its hitherto inaccessible triplet lifetime. A comparison with results for biradicals 2a,c obtained in earlier studies shows that PAC is a reliable method for measuring triplet lifetimes of biradicals. The effect on the triplet lifetimes of allyl and benzyl conjugation at one radical center in 2b,c proved to be insignificant. In view of the large enhancement of the biradical lifetime as the result of benzylic conjugation at both radical sites, as in the diphenyl derivative 2d, the present results imply that the biradicals 2b,c are still flexible enough to enable effective intersystem crossing through pyramidalization. The much larger (ca. 200-fold) triplet lifetime of biradical 2b compared to its gem-dimethyl derivative 2e suggests that geminal substitution is a general phenomenon for the effective reduction of the lifetimes of triplet biradicals through changes in the singlet-triplet energy gap.

  DOI：

  10.1021/jo00058a031

文献信息

• Determination of the triplet lifetimes of 1,3-cyclopentanediyl biradicals derived from the photodenitrogenation of azoalkanes with time-resolved photoacoustic calorimetry
  作者：Waldemar Adam、Herbert Platsch、Juergen Sendelbach、Jakob Wirz

  DOI：10.1021/jo00058a031

  日期：1993.3

  The triplet lifetime of the parent 1,3-cyclopentanediyl (2a) and the 4-methylene and the 1-phenyl derivatives 2b and 2c were determined by time-resolved photoacoustic calorimetry (PAC). For the biradical 2b, PAC was the only suitable method to date for determining its hitherto inaccessible triplet lifetime. A comparison with results for biradicals 2a,c obtained in earlier studies shows that PAC is a reliable method for measuring triplet lifetimes of biradicals. The effect on the triplet lifetimes of allyl and benzyl conjugation at one radical center in 2b,c proved to be insignificant. In view of the large enhancement of the biradical lifetime as the result of benzylic conjugation at both radical sites, as in the diphenyl derivative 2d, the present results imply that the biradicals 2b,c are still flexible enough to enable effective intersystem crossing through pyramidalization. The much larger (ca. 200-fold) triplet lifetime of biradical 2b compared to its gem-dimethyl derivative 2e suggests that geminal substitution is a general phenomenon for the effective reduction of the lifetimes of triplet biradicals through changes in the singlet-triplet energy gap.