3-氯-3-[4-(三氟甲基)苯基]-3H-双吖丙啶 | 115127-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3-氯-3-[4-(三氟甲基)苯基]-3H-双吖丙啶
• 英文名称: p-trifluoromethylphenylchloro diazirine
• 英文别名: 3H-Diazirine, 3-chloro-3-[4-(trifluoromethyl)phenyl]-；3-chloro-3-[4-(trifluoromethyl)phenyl]diazirine
• CAS: 115127-52-1
• 化学式: C₈H₄ClF₃N₂
• 分子量: 220.581
• InChiKey: RQIULBWQOACIEC-UHFFFAOYSA-N

物化性质

• 沸点：
  212.6±50.0℃ (760 Torr)
• 密度：
  1.54±0.1 g/cm3 (20 ºC 760 Torr)
• 闪点：
  82.4±30.1℃

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 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-氯-3-[4-(三氟甲基)苯基]-3H-双吖丙啶 在 sodium azide 作用下， 以 氘代二甲亚砜 为溶剂， 生成 对三氟甲基苯腈
  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：

  4-三氟甲基苯脒盐酸盐 在 sodium hypochlorite 、 lithium chloride 、 sodium chloride 作用下， 以 水 、 二甲基亚砜 、 正戊烷 为溶剂， 以31 %的产率得到3-氯-3-[4-(三氟甲基)苯基]-3H-双吖丙啶
  参考文献：
  名称：

  以卤二氮杂环为卤碳烯前体的连续流中烯烃的环丙烷化反应

  摘要：

  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）。

  DOI：

  10.1002/chem.202303969

文献信息

• Hammett Analysis of a Family of Carbene−Carbene Complex Equilibria
  作者：Lei Wang、Robert A. Moss、Jack Thompson、Karsten Krogh-Jespersen

  DOI：10.1021/ol200083a

  日期：2011.3.4

  p-X-substituted phenylchlorocarbenes (X = NO2, CF3, Cl, H, Me, and MeO) form π-type complexes with trimethoxybenzene in pentane. The carbenes and complexes are in equilibrium, and logarithms of the measured equilibrium constants are well correlated by Hammett σp constants with ρ = 2.48. The carbene complexes are characterized by UV−vis spectroscopy, and computational analysis is afforded by DFT calculations

  p -X取代的苯基氯卡宾（X = NO 2，CF 3，Cl，H，Me和MeO）与戊烷中的三甲氧基苯形成π型络合物。卡宾和配合物处于平衡状态，测得的平衡常数的对数与Hammettσp常数（ρ= 2.48）具有很好的相关性。卡宾配合物的特征在于紫外可见光谱，DFT计算提供了计算分析。
• Hammett analysis of absolute carbene addition rate constants
  作者：R.A. Moss、L.A. Perez、N.J. Turro、I.R. Gould、N.P. Hacker

  DOI：10.1016/s0040-4039(00)81498-7

  日期：1983.1

  Absolute rate constants were determined for the additions of 5 5-X-substituted ArCCl (X=CF3, Cl, H, CH3, CH3O) to tetramethylethylene, trimethylethylene, trans-pentene, and 1-hexene; good Hammett correlations were obtained with ϱ = +1.4 – 1.6.

  确定将5种5-X-取代的ArCCl（X = CF 3，Cl，H，CH 3，CH 3 O）加到四甲基乙烯，三甲基乙烯，反戊烯和1-己烯中的绝对速率常数。ϱ = +1.4 – 1.6获得了良好的哈米特相关性。
• Time-resolved flash spectroscopic investigations of the reactions of singlet arylhalocarbenes
  作者：I.R. Gould、N.J. Turbo、J. Butcher、C. Doubleday、N.P. Hacker、G.F. Lehr、R.A. Moss、D.P. Cox、W. Guo、R.C. Munjal、L.A. Perez、M. Fedorynski

  DOI：10.1016/s0040-4020(01)96399-9

  日期：1985.1

  reactions of phenylchlorocarbene and related carbenes with alkenes are summarized and systematized. The experiments described provide the basis for a detailed examination of carbenic reactivity-selectivity principles. The results of studies on the influence of temperature on the absolute rate constants for carbene reactions are consistent with the existence of transient carbene/alkene intermediates.

  审查了单线芳基卤代卡宾的时间分辨激光闪光光谱研究的结果。特别地，总结并系统化了苯基氯卡宾和相关的碳烯与烯烃的反应的绝对速率常数。所描述的实验为详细研究羧基反应性-选择性原理提供了基础。关于温度对卡宾反应的绝对速率常数的影响的研究结果与瞬态卡宾/烯烃中间体的存在是一致的。
• Addition of arylchlorocarbenes to .alpha.,.beta.-unsaturated esters. Absolute rates, substituent effects, and variable reactivities
  作者：N. Soundararajan、Matthew S. Platz、James E. Jackson、Michael P. Doyle、Su Min. Oon、Michael T. H. Liu、Surinder M. Anand

  DOI：10.1021/ja00229a031

  日期：1988.10

  La reaction des (aryl chloro) methylenes avec le maleate de diethyle produit des (aryl-3 chloro-3)cyclopropanedicarboxylates-1,2 de diethyle

  La 反应 des (aryl chloro) methylenes avec lemaleate de diethyle produit des (aryl-3 chloro-3)cyclopropanedicarboxylates-1,2 de diethyle
• Kinetics and spectroscopy of ylids from reaction of p-substituted phenylchlorocarbenes with acetone
  作者：N Soundararajan、James E Jackson、Matthew S Platz、Michael T.H Liu

  DOI：10.1016/0040-4039(88)85178-5

  日期：1988.1

  Laser flash photolysis of p-CF3 and p-Cl-phenylchloro diazirines produces the corresponding carbenes which react with acetone to produce easily detected ylids. The absolute rate constants of reaction of these carbenes with acetone, and the rate constants of reaction of the ylids with diethylfumarate have been determined. No reaction was found between these carbenes and simple esters or ethylene carbonate

  对-CF 3和对-Cl-苯氯二叠氮基的激光闪光光解产生相应的羧苯甲酸酯，它们与丙酮反应生成易于检测的羟基。已经确定了这些卡宾与丙酮的反应的绝对速率常数，以及缩醛与富马酸二乙酯的反应速率常数。在这些卡宾与简单的酯或碳酸亚乙酯之间未发现反应。