2-(3-chloro-3H-diazirin-3-yl)pyridine | 127458-81-5

• 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: 2-(3-chloro-3H-diazirin-3-yl)pyridine
• 英文别名: 2-(3-Chlorodiazirin-3-yl)pyridine
• CAS: 127458-81-5
• 化学式: C₆H₄ClN₃
• 分子量: 153.571
• InChiKey: PJKIQSQWULDNAG-UHFFFAOYSA-N

物化性质

• 沸点：
  227.6±50.0 °C(Predicted)
• 密度：
  1.52±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 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：

  2-(3-chloro-3H-diazirin-3-yl)pyridine 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62%的产率得到2-(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
• 作为产物：
  描述：

  2-脒基吡啶盐酸盐 在 sodium hypochlorite 、 lithium chloride 作用下， 以 二甲基亚砜 、 正戊烷 为溶剂， 以40 %的产率得到2-(3-chloro-3H-diazirin-3-yl)pyridine
  参考文献：
  名称：

  氯二嗪的吲哚和吡咯的光化学介导的扩环：合成方法和热危害评估

  摘要：

  我们证明，吡啶盐和喹啉盐可以通过将芳基氯二嗪中的单个 C 原子插入母体 N-烷基吡咯或吲哚来获得。扩环的氮化产物被激活，进行氧化和氢化，加速了进一步的结构多样化。利用差示扫描量热法的洞察力，已经开发了使用二嗪嗪作为卡宾前体的更安全的方法。

  DOI：

  10.1002/anie.202305081

文献信息

• Carbon Atom Insertion into Pyrroles and Indoles Promoted by Chlorodiazirines
  作者：Balu D. Dherange、Patrick Q. Kelly、Jordan P. Liles、Matthew S. Sigman、Mark D. Levin

  DOI：10.1021/jacs.1c06287

  日期：2021.8.4

  calculations supporting a selectivity-determining cyclopropanation step. Computations surprisingly indicate that the stereochemistry of cyclopropanation is of little consequence to the subsequent electrocyclic ring opening that forges the pyridine core, due to a compensatory homoaromatic stabilization that counterbalances orbital-controlled torquoselectivity effects. The utility of this skeletal transform is

  在这里，我们报告了一种反应，该反应通过将芳基羰基阳离子等价物分别插入吡咯和吲哚核心选择性地产生 3-芳基吡啶和喹啉基序。通过使用 α-chlorodiazirines 作为相应氯卡宾的热前体，可以修改作为母体 Ciamician-Denstedt 重排核心的传统基于卤仿的协议，以直接提供 3-（杂）芳基吡啶和喹啉。通过氧化可商购的脒鎓盐可方便地在一个步骤中制备氯二氮嗪。检测了作为吡咯取代模式函数的选择性，并提出了基于空间效应的预测模型，DFT 计算支持确定选择性的环丙烷化步骤。计算出人意料地表明，环丙烷化的立体化学对随后形成吡啶核心的电环开环几乎没有影响，这是由于补偿性同芳族稳定化抵消了轨道控制的扭矩选择性效应。通过喹啉的制备和药学相关吡咯的骨架编辑进一步证明了这种骨架转化的效用。
• 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。
• Cyclopropanation of Alkenes with Halodiazirines as Halocarbene Precursors in Continuous Flow
  作者：Hoang‐Minh To、Thierry Ollevier

  DOI：10.1002/chem.202303969

  日期：——

  The preparation of substituted 3-chloro-3-aryl-cyclopropanes through the reaction of alkenes with photolytically-generated chlorocarbenes from chlorodiazirines is reported as an effective method. This approach facilitates the production of diverse 3-chloro-3-aryl-cyclopropanes (32 examples) in an continuous flow with a residence time of 5 minutes under the influence of light-emitting diode (LED) irradiation

  据报道，通过烯烃与氯二氮丙啶光解产生的氯卡宾反应制备取代的3-氯-3-芳基-环丙烷是一种有效的方法。这种方法有助于在发光二极管 (LED) 照射的影响下以 5 分钟的停留时间连续流动生产各种 3-氯-3-芳基-环丙烷（32 个实例）。 380 nm 照射条件的使用有效地扩展到取代的 3-溴-3-芳基-环丙烷的合成（3 个示例）。
• 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：——