1,1'-Dichlor-1,1'-diphenyl-1,1'-azoethan | 19727-23-2

• 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: 1,1'-Dichlor-1,1'-diphenyl-1,1'-azoethan
• 英文别名: Bis(1-chloro-1-phenylethyl)diazene
• CAS: 19727-23-2
• 化学式: C₁₆H₁₆Cl₂N₂
• 分子量: 307.222
• InChiKey: PUIMNSIPJXHACY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  20
• 可旋转键数：
  4
• 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：

  1,1'-Dichlor-1,1'-diphenyl-1,1'-azoethan 在 四丁基高氯酸铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 乙酰苯吖嗪
  参考文献：
  名称：

  The electrochemical reduction of 1,4-dichloroazoethanes: Reductive elimination of chloride to form aryl azines

  摘要：

  A series of 1,4-dichloroazoethanes (1-X/Y, X and Y = 4-NO2, 4-CN. 4-CH3 or 4-H) were studied in N,N-dimethylformamide using cyclic voltammetry. constant potential sweep voltammetry (CPSW) and constant potential electrolysis. The voltammograms of 1-X/Y exhibit an irreversible two-electron wave corresponding to dissociative electron transfer (DET) reduction of the carbon-chlorine bond resulting in formation of the azines 2-X/Y in quantitative yield. Additional redox waves correspond to the reversible reduction of the azines to the 2-X/Y center dot- radical anion and 2-X/Y2- dianion consecutively, with the exception of 1-NO2/NO2 where both NO2 groups are reduced simultaneously in a two-electron reversible wave. Thermodynamic and kinetic parameters were determined from CPSW: the standard reduction potentials (E degrees) vary between -0.7 and -1.3 V versus SCE as a function of electron-withdrawing substituent; the heterogeneous rate constants (k(het)) are consistent with a slow heterogeneous electron transfer with values ranging from 10(-3) to 10(-5) cm s(-1) : the transfer coefficients (alpha) for 1-NO2/NO2 and 1-NO2/H are greater than 0.5, indicative of a stepwise DET mechanism for the C-Cl bond cleavage while the remaining 1-X/Y compounds have alpha values between 0.35 and 0.5, and the intrinsic barriers are all significantly lower than predicted for a concerted DET. thereby also suggesting a stepwise DET mechanism. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.electacta.2010.04.080
• 作为产物：
  描述：

  乙酰苯吖嗪 在 氯 作用下， 以 二氯甲烷 为溶剂， 以50 %的产率得到1,1'-Dichlor-1,1'-diphenyl-1,1'-azoethan
  参考文献：
  名称：

  电子多样化 π 系统的安全实用异位氯化

  摘要：

  有机分子的直接氯化是有机合成的有力工具。然而，使用 Cl 2气体具有一些显着的安全和后勤缺陷。最近，开发了原位氯化程序来规避这些限制；然而，这些方法需要使用苛刻或昂贵的试剂，并且底物范围有限。在这里，我们描述了使用两室 COware 系统进行非原位氯生成的安全实用设置。使用这种策略，可以高效地实现缺电子、中性和富电子系统的氯化。总体而言，这种方法可作为当前报告协议的广泛适用替代方案，适用于学术环境中的实验室。

  DOI：

  10.1016/j.tetlet.2023.154591

文献信息

• Synthese und Zerfall von Azoinitiatoren, I
  作者：Dietrich Braun、Rolf Jakobi

  DOI：10.1007/bf00808940

  日期：1982.12
• Duismann,W. et al., Justus Liebigs Annalen der Chemie, 1974, p. 1348 - 1356
  作者：Duismann,W. et al.

  DOI：——

  日期：——
• Goldschmidt; Acksteiner, Chemische Berichte, 1958, vol. 91, p. 502,505
  作者：Goldschmidt、Acksteiner

  DOI：——

  日期：——
• The electrochemical reduction of 1,4-dichloroazoethanes: Reductive elimination of chloride to form aryl azines
  作者：Vittorio A. Sauro、David C. Magri、Jason L. Pitters、Mark S. Workentin

  DOI：10.1016/j.electacta.2010.04.080

  日期：2010.8

  A series of 1,4-dichloroazoethanes (1-X/Y, X and Y = 4-NO2, 4-CN. 4-CH3 or 4-H) were studied in N,N-dimethylformamide using cyclic voltammetry. constant potential sweep voltammetry (CPSW) and constant potential electrolysis. The voltammograms of 1-X/Y exhibit an irreversible two-electron wave corresponding to dissociative electron transfer (DET) reduction of the carbon-chlorine bond resulting in formation of the azines 2-X/Y in quantitative yield. Additional redox waves correspond to the reversible reduction of the azines to the 2-X/Y center dot- radical anion and 2-X/Y2- dianion consecutively, with the exception of 1-NO2/NO2 where both NO2 groups are reduced simultaneously in a two-electron reversible wave. Thermodynamic and kinetic parameters were determined from CPSW: the standard reduction potentials (E degrees) vary between -0.7 and -1.3 V versus SCE as a function of electron-withdrawing substituent; the heterogeneous rate constants (k(het)) are consistent with a slow heterogeneous electron transfer with values ranging from 10(-3) to 10(-5) cm s(-1) : the transfer coefficients (alpha) for 1-NO2/NO2 and 1-NO2/H are greater than 0.5, indicative of a stepwise DET mechanism for the C-Cl bond cleavage while the remaining 1-X/Y compounds have alpha values between 0.35 and 0.5, and the intrinsic barriers are all significantly lower than predicted for a concerted DET. thereby also suggesting a stepwise DET mechanism. (C) 2010 Elsevier Ltd. All rights reserved.