3-(p-(trifluoromethyl)phenyl)diazirine | 95911-64-1

• 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-(p-(trifluoromethyl)phenyl)diazirine
• 英文别名: 3H-Diazirine, 3-bromo-3-[4-(trifluoromethyl)phenyl]-；3-bromo-3-[4-(trifluoromethyl)phenyl]diazirine
• CAS: 95911-64-1
• 化学式: C₈H₄BrF₃N₂
• 分子量: 265.032
• InChiKey: OWUXQKYUGTZWKE-UHFFFAOYSA-N

物化性质

• 沸点：
  220.6±50.0 °C(Predicted)
• 密度：
  1.81±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 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：
  5

反应信息

• 作为反应物：
  描述：

  3-(p-(trifluoromethyl)phenyl)diazirine 在 叠氮化四丁基铵 作用下， 以 乙腈 为溶剂， 以83%的产率得到对三氟甲基苯腈
  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：

  对三氟甲基苯腈 在 sodium hypobromide 、 sodium methylate 、 氯化铵 、 lithium bromide 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 反应 73.0h， 生成 3-(p-(trifluoromethyl)phenyl)diazirine
  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

文献信息

• Reactivity of 1-Chloro-3-phenyldiazirines
  作者：Tomas Martinu、William P. Dailey

  DOI：10.1021/jo060341g

  日期：2006.6.1

  p-Substituted 1-chloro-3-phenyldiazirines (5), the putative intermediates of the reaction of N,N,N'-trichlorobenzamidines (10) with excess of bromide ions, react further to afford mixtures of 3-bromo- (4) and 3-chloro-3-phenyldiazirines (6). The 6:4 ratios inversely correlate with the Hammett σp and σp+ constants of the p-substituents. The formation of 4, proposed to proceed by anti-SN2‘ mechanism

  对位取代的1-氯-3-苯基重氮（5）是N，N，N'-三氯苯甲m（10）与过量溴离子反应的推定中间体，进一步反应生成3-溴-（4）和3-氯-3-苯基重氮（6）。该6：4的比率用哈米特σ负相关p和σ p +的常数p -取代基。4的形成，建议通过反S N进行2'机理主要是吸电子的p-取代基。化合物6是具有给电子性p取代基的主要产物，它可以由5通过极性过渡结构12进行氯的[1,3]-σ位移而从5中产生。气相DFT（B3LYP / 6-31 + G *）对这两种机理的研究结果与实验一致。
• Reactions and Reactivity of Acyloxycarbenes
  作者：Robert A. Moss、Song Xue、Weiguo Liu、Karsten Krogh-Jespersen

  DOI：10.1021/ja9626244

  日期：1996.1.1

  phenyl(benzoyloxy)carbene, photolytically generated from diazirine precursors in pentane at 25 °C, efficiently rearranged by 1,2-acyl migrations to give high yields of the appropriate 1,2-diketones. The kinetics of these rearrangements were determined by laser flash photolysis. Substituent effects on the acyl migrations and ab initio electronic structure calculations on ground state carbenes and transition

  苯基乙酰氧基卡宾、苯基（新戊酰氧基）卡宾和苯基（苯甲酰氧基）卡宾，在 25 °C 下从戊烷中的二氮嗪前体光解生成，通过 1,2-酰基迁移有效地重排，以高产率获得合适的 1,2-二酮。这些重排的动力学由激光闪光光解确定。取代基对酰基迁移的影响和基态卡宾和过渡态的从头电子结构计算被用来分析重排机制。苯乙酰氧基卡宾向烯烃的加成以良好的产率进行，代替了 1,2-酰基转移；获得了两亲性卡宾的这些反应的绝对速率常数。（苯氧基甲基）乙酰氧基卡宾仅产生 1,2-H 位移；潜在的竞争性 1,2-乙酰基迁移受到抑制。
• Activation parameters for the additions of arylhalocarbenes to alkenes
  作者：Robert A. Moss、Witold. Lawrynowicz、Nicholas J. Turro、Ian R. Gould、Yuan. Cha

  DOI：10.1021/ja00282a030

  日期：1986.10

  an opportunity to directly examine Skell's suggestions,' as well as certain of Houk's prediction^.^ At present, sensitivity considerations have restricted laser flash photolytic studies to carbenes that contain an aromatic chromo- phore.6 Within that restriction, and on the basis of our previous re~earch,~ it was clear that the widest reactivity range of readily available singlet carbenes would be afforded

  通过使用纳秒激光闪光光解方法，获得了对（三氟甲基1）苯基溴卡宾（CF3C6H4CBr）、苯基溴卡宾（PhCBr）、苯基氯卡宾（PhCCI）、苯基氟卡宾（PhCF）和对甲氧基苯基氟卡宾（CH30C6H4CF）添加的绝对速率常数到四甲基乙烯 (TME) 和 1-己烯。速率常数范围从 1.7 X IO9 (CF3C6H4CBr/TME) 到 5.0 X lo4 L/(Ms) (CH30C6H4CF/l-己烯)；遵守经典结构/反应性关系。在 3 15 和 200 K 之间的温度下测定速率常数给出了 10 个反应的 E、log A、AH*、AS' 和 AG*。所有的反应都以AS'为主。最快和最慢反应的 AG* 范围为 5.0 至 11 kcal/mol。对于在较高温度下的一些较快反应，观察到 E 的负值。这些结果是根据单步加成反应分析的，其中 AG* 由 AS' 主导，或者，根据通过卡宾 - 烯烃配合物进行的两步机制进行分析。近
• 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）。
• 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.