3-chloro-3-(3-pyridyl)-3H-1,2-diazirine | 125330-17-8

• 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
• 英文名称: 3-chloro-3-(3-pyridyl)-3H-1,2-diazirine
• 英文别名: 3-pyridylchlorodiazirine；3-chloro-3-(3-pyridyl)diazirine；3-(3-Chlorodiazirin-3-yl)pyridine
• CAS: 125330-17-8
• 化学式: C₆H₄ClN₃
• 分子量: 153.571
• InChiKey: WODWTZPLHOCIRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 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：
  3

反应信息

• 作为反应物：
  描述：

  3-chloro-3-(3-pyridyl)-3H-1,2-diazirine 在 sodium azide 作用下， 以 氘代二甲亚砜 为溶剂， 生成 3-氰基吡啶
  参考文献：
  名称：

  C-Azidodiazirines in the SRN1 reaction of azide ion with arylchlorodiazirines. Further insights into reaction mechanism

  摘要：

  Mixtures of arylchlorodiazirines and sodium azide in DMSO form visible charge transfer complexes. Irradiation of these solutions with fluorescent room light leads to S(RN)1 displacement of chloride and the transient formation of C-azidodiazirines. Relative reactivity studies (using competition experiments) show that nitro-substituted arylchlorodiazirines are substantially more reactive than other arylchlorodiazirines. This is attributed to facile electron transfer in the propagation cycle, involving the nitro-substituted aromatic ring. C-Azidodiazirines can be isolated in solution and spectroscopically characterized when the S(RN)1 reaction is initiated by addition of catalytic amounts of the sodium salt of 2-nitropropane. These azidodiazirines readily decompose at room temperature by first order processes to give molecular nitrogen and benzonitriles. Solvent and substituent effects on decomposition rates are minimal. Computational studies on potential intermediate carbenes in the decomposition of azidodiazirines have been carried out at the HF/6-31G* level. Singlet alpha-azidocarbenes RCN3, where R = NH2, OH, F, vinyl, phenyl, and CH3, are energy minima at this computational level. Isodesmic calculations show that the azido group is comparable to OH in its carbene stabilizing ability. Subsequent loss of N2 from alpha-azidocarbenes, leading to nitriles, is a highly exothermic process (126 kcal when R = vinyl and 128 kcal when R = phenyl).

  DOI：

  10.1021/jo00079a014
• 作为产物：
  描述：

  3-甲脒基吡啶盐酸盐 以43%的产率得到3-chloro-3-(3-pyridyl)-3H-1,2-diazirine
  参考文献：
  名称：

  SRN1 reactions of arylhalodiazirines with azide ion

  摘要：

  DOI：

  10.1021/jo00294a010

文献信息

• Diazirine derivatives of aromatic heterocyclic compounds
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0432817A1

  公开（公告）日：1991-06-19

  Compounds of the formula in which Het represents an optionally substituted aromatic heterocycle having a sulphur or oxygen hetero atom and attached via a ring carbon atom, and X is halogen, alkyl, alkaryl, cyano, alkoxy, mono- or di-alkylamino, acyloxy or aryl,are useful intermediates to a range of cyclopropane derivatives. Processes for their preparation and their use in further synthetic processes are also described.

  式中的化合物 其中，Het 代表具有硫或氧杂环原子并通过环碳原子连接的任选取代的芳香杂环，X 代表卤素、烷基、烷芳基、氰基、烷氧基、单或双烷基氨基、酰氧基或芳基，它们是一系列环丙烷衍生物的有用中间体。此外，还介绍了它们的制备工艺以及在进一步合成工艺中的用途。
• 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.
• Baird, Mark S.; Bruce, Ian, Journal of Chemical Research, Miniprint, 1989, # 12, p. 2852 - 2871
  作者：Baird, Mark S.、Bruce, Ian

  DOI：——

  日期：——
• 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.
• Absolute Reactivity of (<i>N</i>-Methyl-3-pyridinium)chlorocarbene
  作者：Hui Cang、Robert A. Moss、Karsten Krogh-Jespersen

  DOI：10.1021/acs.jpca.5b01729

  日期：2015.4.16

  (N-Methyl-3-pyridinium)chlorocarbene tetrafluoroborate (MePyr(+)CCl BF4-, 4) is generated by laser flash photolysis (LFP) of the corresponding diazirine (5) and reacted with tetramethylethylene, cyclohexene, 1-hexene, 2-ethyl-1-butene, methyl acrylate, and acrylonitrile. Absolute rate constants are measured for these carbene-alkene addition reactions, and activation parameters are obtained for additions of MePyr(+)CCl BF4- to tetramethylethylene, cyclohexene, and 1-hexene. MePyr(+)CCl BF4- is computed to be a highly reactive, electrophilic, singlet carbene, and experiments are in accord with expectations. Its activation parameters are compared with those of CF3CCl, CCl2, CClF, and CF2. In all cases, enthalpy-entropy compensation is observed, with Delta H double dagger and Delta S double dagger decreasing in tandem as carbenic stability decreases. A qualitative explanation is offered for this phenomenon.