3-(3-氟-3H-二氮杂环丙烯-3-基)吡啶 | 141342-10-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 3-(3-氟-3H-二氮杂环丙烯-3-基)吡啶
• 英文名称: 3-pyridylfluoroaziridine
• 英文别名: 3-fluoro-3-(3-pyridyl)diazirine；3-(3-Fluorodiazirin-3-yl)pyridine
• CAS: 141342-10-1
• 化学式: C₆H₄FN₃
• 分子量: 137.116
• InChiKey: HMSVJQQKJPONAB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  37.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(3-氟-3H-二氮杂环丙烯-3-基)吡啶 以 异辛烷 为溶剂， 生成 fluoro(3-(3-fluoro-3H-diazirin-3-yl)pyridin-1-ium-1-yl)(pyridin-3-yl)methanide
  参考文献：
  名称：

  Absolute Reactivity of Halo(pyridyl)carbenes

  摘要：

  A comprehensive series of halo(pyridyl)carbenes was generated by laser flash photolysis of the appropriate diazirines. Only the chloro- and bromo(2-pyridyl)carbenes and the chloro- and bromo(3-pyridyl)carbenes could be directly observed, but the reactivity of all nine halo(pyridyl)carbenes could be directly studied using the standard and a modified pyridine-ylide approach. The carbenes were all ambiphilic, being highly reactive toward both electron-rich and election-deficient alkenes. Second-order rate constants for these reactions ranged from 2.9 x 10(6) to 3.5 x 10(9) M-1 s(-1) and depended on both the position of the nitrogen atom within the pyridine ring and the nature of the halogen group, as well as the electrophilicity or nucleophilicity of the alkene. A reactivity trend with respect to the location of the nitrogen within the pyridine ring was observed, with the 4-pyridyl carbenes being the most reactive followed by the 2-pyridylcarbenes and then the 3-pyridylcarbenes being the least reactive. This observed reactivity trend is consistent with the pyridyl ring acting as an overall electron-withdrawing group. The results also show that resonance delocalization of electron density into the nitrogen atom of the 4-pyridyl- and 2-pyridylcarbenes in the transition state significantly reduces the effect of the adjacent halogen (F, Cl, or Br) on the reactivity of the pyridyl carbenes with a series of alkenes.

  DOI：

  10.1021/jo802132z
• 作为产物：
  描述：

  3-chloro-3-(3-pyridyl)-3H-1,2-diazirine 在 四丁基氟化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以48%的产率得到3-(3-氟-3H-二氮杂环丙烯-3-基)吡啶
  参考文献：
  名称：

  Pyridylhalocarbenes and pyridiniumhalocarbenes

  摘要：

  Pyridylhalocarbenes and pyridiniumhalocarbenes can be generated from diazirines. Absolute rate constants have been determined for additions of 2- and 3-pyridylchlorocarbenes to alkenes.

  DOI：

  10.1016/s0040-4039(00)91638-1

文献信息

• Absolute Reactivity of Halo(pyridyl)carbenes
  作者：Reinaldo Moya-Barrios、Frances L. Cozens、Norman P. Schepp

  DOI：10.1021/jo802132z

  日期：2009.2.6

  A comprehensive series of halo(pyridyl)carbenes was generated by laser flash photolysis of the appropriate diazirines. Only the chloro- and bromo(2-pyridyl)carbenes and the chloro- and bromo(3-pyridyl)carbenes could be directly observed, but the reactivity of all nine halo(pyridyl)carbenes could be directly studied using the standard and a modified pyridine-ylide approach. The carbenes were all ambiphilic, being highly reactive toward both electron-rich and election-deficient alkenes. Second-order rate constants for these reactions ranged from 2.9 x 10(6) to 3.5 x 10(9) M-1 s(-1) and depended on both the position of the nitrogen atom within the pyridine ring and the nature of the halogen group, as well as the electrophilicity or nucleophilicity of the alkene. A reactivity trend with respect to the location of the nitrogen within the pyridine ring was observed, with the 4-pyridyl carbenes being the most reactive followed by the 2-pyridylcarbenes and then the 3-pyridylcarbenes being the least reactive. This observed reactivity trend is consistent with the pyridyl ring acting as an overall electron-withdrawing group. The results also show that resonance delocalization of electron density into the nitrogen atom of the 4-pyridyl- and 2-pyridylcarbenes in the transition state significantly reduces the effect of the adjacent halogen (F, Cl, or Br) on the reactivity of the pyridyl carbenes with a series of alkenes.
• Pyridylhalocarbenes and pyridiniumhalocarbenes
  作者：Robert A. Moss、Eun G. Jang、Hong-Rak Kim、Guo-Jie Ho、Mark S. Baird

  DOI：10.1016/s0040-4039(00)91638-1

  日期：1992.3

  Pyridylhalocarbenes and pyridiniumhalocarbenes can be generated from diazirines. Absolute rate constants have been determined for additions of 2- and 3-pyridylchlorocarbenes to alkenes.