3-Bromo-3-(p-methylphenyl)diazirine | 95911-62-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-Bromo-3-(p-methylphenyl)diazirine
• 英文别名: 3-bromo-3-(4-methylphenyl)diazirine；bromo(4-methylphenyl)diazirine；3H-Diazirine, 3-bromo-3-(4-methylphenyl)-
• CAS: 95911-62-9
• 化学式: C₈H₇BrN₂
• 分子量: 211.061
• InChiKey: LDVTZOYGPONILP-UHFFFAOYSA-N

物化性质

• 沸点：
  228.9±50.0 °C(Predicted)
• 密度：
  1.61±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Bromo-3-(p-methylphenyl)diazirine 在 叠氮化四丁基铵 作用下， 以 乙腈 为溶剂， 以90%的产率得到对甲苯腈
  参考文献：
  名称：

  卤代二氮嗪的叠氮和氟化物交换反应

  摘要：

  制备 d'une 系列 fluoro-3 aryl-3 diazirines etude des反应 d'arylhalogenodiazirines avec l'ion azoture

  DOI：

  10.1021/ja00295a029
• 作为产物：
  描述：

  4-甲基苯甲脒盐酸盐 在 sodium hypobromide 、 sodium bromide 作用下， 以 正己烷 、 水 、 二甲基亚砜 为溶剂， 生成 3-Bromo-3-(p-methylphenyl)diazirine
  参考文献：
  名称：

  Dimerization and trapping of diazirinyl radicals

  摘要：

  利用计算和实验方法研究了重氮异二唑自由基的简易二聚化过程。通过密度泛函理论研究了两种可能的二聚体。两者均显示出导致形成HCN和N2的低能垒反应坐标。采用交叉实验确定了C-N和N-N二聚体对产物形成的相对贡献。在当前条件下，发现N-N二聚化占主导地位，并使用耦合簇方法进一步探讨了相应的反应坐标能量学。详细展示了二聚体分解的机制。在高稀释条件下，探究了重氮异二唑自由基单分子反应和双分子反应之间的竞争。作为氮原子转移剂的重氮异二唑自由基的高度活性表明，在烃类燃烧中，重氮异二唑自由基作为中间体参与的“即时”NO形成过程可能涉及双分子反应的贡献。

  DOI：

  10.1039/b310148g

文献信息

• Dimerization and trapping of diazirinyl radicals
  作者：Robert A. Thompson、Joseph S. Francisco、John B. Grutzner

  DOI：10.1039/b310148g

  日期：——

  Computational and experimental methods have been utilized to examine the facile dimerization of diazirinyl radicals. Two potential dimers were investigated using density functional theory. Both were shown to have low-barrier reaction coordinates leading to formation of HCN and N2. A cross-over experiment was employed to establish the relative contributions of C–N and N–N dimers towards product formation. The N–N dimerization was found to be dominant under the current conditions, and the corresponding reaction coordinate energetics were further explored using coupled-cluster methods. A detailed mechanism for dimer decomposition is presented. The competition between unimolecular and bimolecular reactions of diazirinyl radicals is explored under high dilution conditions. The high reactivity of the diazirinyl radical as a nitrogen atom transfer agent suggests a possible bimolecular contribution for “prompt” NO formation in hydrocarbon combustion with diazirinyl radicals as intermediates.

  利用计算和实验方法研究了重氮异二唑自由基的简易二聚化过程。通过密度泛函理论研究了两种可能的二聚体。两者均显示出导致形成HCN和N2的低能垒反应坐标。采用交叉实验确定了C-N和N-N二聚体对产物形成的相对贡献。在当前条件下，发现N-N二聚化占主导地位，并使用耦合簇方法进一步探讨了相应的反应坐标能量学。详细展示了二聚体分解的机制。在高稀释条件下，探究了重氮异二唑自由基单分子反应和双分子反应之间的竞争。作为氮原子转移剂的重氮异二唑自由基的高度活性表明，在烃类燃烧中，重氮异二唑自由基作为中间体参与的“即时”NO形成过程可能涉及双分子反应的贡献。
• Synthesis of µ-carbene and µ-carbyne complexes of rhodium and cobalt from substituted diazirines. Crystal structures of [Rh₂(η⁵-C₅Me₅)₂(CO)₂{µ-C(C₆H₄F-4)(OMe)}] and [Rh₂(η⁵-C₅Me₅)₂(µ-CO)(µ-C₆H₄Me-4)][BPh₄]
  作者：Anthony G. Avent、Stephen A. Benyunes、Penny A. Chaloner、Nigel G. Gotts、Peter B. Hitchcock

  DOI：10.1039/dt9910001417

  日期：——

  The reaction of aryl(methoxy)diazirines with [M2(η5-C5Me5)2(µ-CO)2](M = Rh or Co) affords the µ-carbene complexes [M2(η5-C5Me5)(CO)2µ-CR(OMe)}](R = aryl) in excellent yield. The carbonyl groups are terminal in the rhodium complexes, as demonstrated conclusively in an X-ray diffraction study, but bridging for the cobalt complex. Thermolysis of the rhodium complexes results in loss of CO and the formation

  芳基（甲氧基）diazirines与反应[M 2（η 5 -C 5我5）2（μ-CO）2 ]（M =铑或Co）得到μ -卡宾配合物[M 2（η 5 -C 5 Me 5）（CO）2 µ-CR（OMe）}]（R =芳基），收率极高。X射线衍射研究已明确证明，羰基在铑配合物中是末端，但对于钴配合物则是桥接。在CO的损失和铑[Rh形成热解的铑的配合物的结果2（η 5 -C 5我5）2（µ-CO）µ-CR（OMe）}]。无论是单或二羰基铑络合物与HBF的质子化4导致了稳定的形成阳离子碳炔络合物，铑[Rh 2（η 5 -C 5我5）2（μ-CO）（μ-CR）] [BF 4 ]; 在衍射研究中确定了相关[BPh 4 ] –盐的结构。通过变温NMR光谱研究了配合物中的动态过程。
• 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）。
• Precise control of the formation of a covalent and an ionic bond in carbocation-carbanion combination reactions
  作者：Kenichi Takeuchi、Toshikazu Kitagawa、Atsushi Miyabo、Hideshi Hori、Koichi Komatsu

  DOI：10.1021/jo00073a047

  日期：1993.10

  The electronic effect on the selectivity of covalent or ionic bond formation was examined for the reaction of Kuhn's anion 1- (C67H39-; tris(7H-dibenzo[c,g]fluorenylidenemethyl)methide ion) and 1-aryl-2,3-dicyclopropylcyclopropenylium ions. The carbocation stability was progressively changed by varying the substituent on the phenyl ring, while the steric effect was kept essentially unchanged. The cations having the p-chlorophenyl (2a+), phenyl (2b+), m-methylphenyl (2c+), or m,m'-dimethylphenyl (2d+) group gave a covalent product, whereas a carbocation-carbanion salt was obtained from the cations having the p-methylphenyl (2e+) or p-methoxyphenyl (2f+) group. The reduction potentials E(red) of the cations, as determined by cyclic voltammetry, showed that the formation of the covalent or ionic product is switched by a small difference in stability (less-than-or-equal-to 0.4 kcal/mol) between 2d+ and 2e+. In chloroform, the salts 1-2e+ and 1-2f+ were transformed into covalent forms 1-2e and 1-2f, which can exist only in solution. When 1-(2a-d) and 1-2e,f+ were dissolved in DMSO, equilibrium between a covalent compound and ions was established. A plot of the free energy of heterolysis DELTAG(het)-degrees for 1-(2a-f) against the E(red) of the corresponding cations 2a-f+ showed that DELTAG(het)-degrees decreases as the cation is more stabilized. The heterolysis in DMSO was shown to be enhanced by ca. 13 kcal/mol both by the steric congestion in the covalent molecules and the stabilization of the cyclopropenylium ions by solvation.
• Reaction of arylhalodiazirines with thiophenoxide: a redox process
  作者：Xavier Creary、Anthony F. Sky、Gillian Phillips、David E. Alonso

  DOI：10.1021/ja00070a003

  日期：1993.8

  Phenylbromodiazirine reacts with thiophenoxide ion in methanol to give benzonitrile, benzamidine, ammonia, and diphenyl disulfide. The reaction is general for arylhalodiazirines, with electron-withdrawing groups on the aromatic ring exerting a small rate-enhancing effect. Three potential mechanisms are suggested for this redox process. These mechanisms include an N-sulfenylated diazirine, a diazirinyl radical, and a diazirinyl anion. Ring opening of these intermediates and subsequent transformations would lead to benzonitriles, benzamidine, and ammonia. A key intermediate in these transformations is PhSNH2, 32. This intermediate has been independently generated and found to rapidly convert to ammonia and diphenyl disulfide under the reaction conditions. Another proposed intermediate, N-(phenylthio)benzamidine, 38, has also been independently generated and subjected to the reaction conditions, where benzamidine and more diphenyl disulfide result. Theoretical calculations suggest the existence of isomeric diazirinyl anions. In addition to a diazirinyl ion with charge essentially on carbon, there is also an allylic-type ion with charge on the two nitrogen atoms. Single-electron reduction of a diazirinyl radical necessarily leads to a nitrogen-centered diazirinyl anion. Conversion of this anion to the carbon-centered diazirinyl anion is a forbidden process. These theoretical studies suggest that the diazirinyl anion may be a viable intermediate in solution.