3-(4-pyridyl)-3-chlorodiazirine | 74671-01-5

• 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: 3-(4-pyridyl)-3-chlorodiazirine
• 英文别名: 3-Chlor-3-(4-pyridyl)-3H-1,2-diazirin；4-pyridylchlorodiazirine；4-(3-chloro-3H-diazirin-3-yl)pyridine；3-chloro-3-(4-pyridyl)diazirine；4-(3-Chlorodiazirin-3-yl)pyridine
• CAS: 74671-01-5
• 化学式: C₆H₄ClN₃
• 分子量: 153.571
• InChiKey: OUJXCGRKTFGYJS-UHFFFAOYSA-N

物化性质

• 熔点：
  -25 °C
• 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)：
  1.4
• 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-(4-pyridyl)-3-chlorodiazirine 在 四丁基氟化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 以14%的产率得到3-fluoro-3-(4-pyridyl)diazirine
  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：

  4-amidinopyridine hydrochloride 在 sodium hypochlorite 、 lithium chloride 、 sodium chloride 作用下， 以 二甲基亚砜 、 正戊烷 为溶剂， 以24%的产率得到3-(4-pyridyl)-3-chlorodiazirine
  参考文献：
  名称：

  氯二氮嗪促进碳原子插入吡咯和吲哚

  摘要：

  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。

  DOI：

  10.1021/jacs.1c06287

文献信息

• Formation of indolizines by the addition of α-chloroacrylonitrile to pyridinium ylides: regioselectivity and Hammett correlation
  作者：Roland Bonneau、Michael T. H. Liu、René Lapouyade

  DOI：10.1039/p19890001547

  日期：——

  Cycloaddition of pyridinium ylides to α-chloroacrylonitrile give indolizines: the regioselectivity of the reaction can be rationalized in terms of nucleophilic attack by the ylides on the olefin.

  吡啶鎓碘化物与α-氯丙烯腈的环加成反应会产生吲哚类化合物：反应的区域选择性可以根据烯烃上的酰化物对亲核的攻击来合理化。
• Intramolecular Addition of Nucleophilic Carbenes to Acceptor-Substituted Alkenyl Groups: Synthesis and transformation of homobenzofurans and synthesis of a homoindole
  作者：Chunbao Li、Andrea Vasella

  DOI：10.1002/hlca.19930760114

  日期：1993.2.10

  The intramolecular addition of unsaturated alkoxycarbenes leads in high yields and diastereoselectively to fused cyclopropanes (Scheme 1). Reaction of the halodiazirines 2, 10, 11, and 20 with the unsaturated phenolates 1, 8, and 9 yielded intermediate alkoxydiazirines, and hence the homobenzofurans 5, 12–16, 22, and 26 (Scheme 2). The intermediate alkoxydiazirine 25 was isolated at low temperature

  分子内添加不饱和烷氧基卡宾导致高产率并且非对映选择性地产生稠合的环丙烷（方案1）。所述halodiazirines的反应2，10，11，和20与不饱和酚1，8，和9个得到中间alkoxydiazirines，因此homobenzofurans 5，12 - 16，22，和26（方案2）。在低温下分离出中间体烷氧基二嗪25（方案3）。环丙烷衍生物12和27以及14和28之间的平衡建立在120°。在200°，通过环丙烷环的旋旋打开，然后将其电环化，将12重排至色烯29。的氢化29，得到（清一色顺式） -苯并二氢吡喃32（方案4）。推测通过34和10的S RN 1反应以高收率获得均吲哚35（方案5）。
• Berneth, Horst; Huenig, Siegfried, Chemische Berichte, 1980, vol. 113, # 5, p. 2040 - 2042
  作者：Berneth, Horst、Huenig, Siegfried

  DOI：——

  日期：——
• C-Azidodiazirines in the SRN1 reaction of azide ion with arylchlorodiazirines. Further insights into reaction mechanism
  作者：Xavier Creary

  DOI：10.1021/jo00079a014

  日期：1993.12

  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).
• BONNEAU, ROLAND;LIU, MICHAEL T. H.;LAPOUYADE, RENE, J. CHEM. SOC. PERKIN TRANS. PT 1,(1989) N, C. 1547-1548
  作者：BONNEAU, ROLAND、LIU, MICHAEL T. H.、LAPOUYADE, RENE

  DOI：——

  日期：——