trans-10,11-dibromo-10,11-dihydro-5H-dibenzazepine-5-carbonyl chloride | 40421-03-2

• 物质功能分类: 分析化学 - 标准品 - 药典标准品和杂质标准品
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: trans-10,11-dibromo-10,11-dihydro-5H-dibenzazepine-5-carbonyl chloride
• 英文别名: 10,11-Dibrom-10,11-dihydro-5-chlorcarbonyl-5H-dibenzazepin；10,11-Dibrom-10,11-dihydro-5-chlorcarbonyl-5H-dibenz[b,f]azepin；(5S,6S)-5,6-dibromo-5,6-dihydrobenzo[b][1]benzazepine-11-carbonyl chloride
• CAS: 40421-03-2；56875-24-2
• 化学式: C₁₅H₁₀Br₂ClNO
• 分子量: 415.512
• InChiKey: VZIGUCCPGWDDML-KBPBESRZSA-N

物化性质

• 沸点：
  430.3±45.0 °C(Predicted)
• 密度：
  1.808±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（轻微、加热、超声处理）、DMSO（轻微、超声处理）

计算性质

• 辛醇/水分配系数(LogP)：
  6.07
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

制备方法与用途

应用

卡马西平杂质4可作为分析标准品和对照品，主要用于实验室研发过程和化工生产过程中。

反应信息

• 作为反应物：
  描述：

  trans-10,11-dibromo-10,11-dihydro-5H-dibenzazepine-5-carbonyl chloride 以 various solvent(s) 为溶剂， 反应 24.0h， 以65%的产率得到亚氨基芪甲酰氯
  参考文献：
  名称：

  Reversibility of bromonium ion formation and its effect on olefin reactivity in electrophilic bromination. New evidence from the 5H-dibenz[b,f]azepine system

  摘要：

  DOI：

  10.1021/ja00210a039
• 作为产物：
  描述：

  亚氨基芪甲酰氯 在 溴 作用下， 以 1,2-二氯乙烷 为溶剂， 生成 trans-10,11-dibromo-10,11-dihydro-5H-dibenzazepine-5-carbonyl chloride
  参考文献：
  名称：

  Reversibility of bromonium ion formation and its effect on olefin reactivity in electrophilic bromination. New evidence from the 5H-dibenz[b,f]azepine system

  摘要：

  DOI：

  10.1021/ja00210a039

文献信息

• Kinetic evidence for rate determination during the nucleophilic step of olefin bromination. The case of 5H-dibenz[b,f]azepine-5-carbonyl chloride
  作者：Giuseppe Bellucci、Cinzia Chiappe

  DOI：10.1021/jo00077a039

  日期：1993.12

  The bromination of 5H-dibenz[b,f]azepine-5-carbonyl chloride has been investigated in 1,2-dichloroethane at 5, 25, and 50-degrees-C. Working at reagent concentrations where the bromination was very slow, the formation of a 1:1 charge-transfer complex (CTC) was shown spectrophotometrically by the presence of a large difference absorption with respect to the olefin and to Br2 alone. Although the formation constant of this CTC was too low (K(f) less-than-or-equal-to 0.1 M-1) to be determined, the products (K(fepsilonCT) at the three temperatures were obtained from the slopes of the linear plots of the difference absorbances against the olefin concentrations, and a value of the formation enthalpy, DELTAH = -0.9 (0.05) kcal mol-1, was obtained from a plot of In (K(fepsilonCT) against 1/T. The kinetics of bromination were measured at variable temperature and reagent concentrations. At 50-degrees-C and [Br2] ranging between 2 x 10(-2) and 5 x 10(-1) M the usual third-order kinetics were observed. The same rate law was obeyed at 25-degrees-C and [Br2] less-than-or-equal-to 5 x 10(-2) M, whereas neither a third-order nor a fourth-order rate law was followed at 5 x 10(-1) M Br2 and olefin. At 5-degrees-C and [Br2] less-than-or-equal-to 5 x 10(-2) M the third-order rate law was again observed, but at 5 x 10(-1) M Br2 and olefin an overall fourth-order (third-order in Br2) rate law was cleanly obeyed. A very small apparent activation energy, E(a(obsd)) = 3.45(0.1) kcal mol-1, was found for the third-order process. A significant conductivity, which was highest at the lowest temperature, was found during the course of the reactions. trans-10,11-Dibromo-10,11-dihydro-5H-dibenz[b,flazepine-5-carbonyl chloride was the only reaction product. It was shown by D NMR measurements to exist in 1,2-dichloroethane solution in two forms, both having anti-oriented bromine atoms and being nonequivalent because of different bond angles and bond lengths at C(10) and C(11). They are interconverted through a seven-membered ring inversion by torsion about the C(4a)-N(5)-C(5a) bonds, with a free activation energy DETAG(double dagger) = 16.6(0.2) kcal mol-1. Introducing the values of E(a(obsd)) for the third-order bromination and of DELTAH for the CTC formation in the equation E(a(obsd)) = E(a) + DELTAH[1/ (1 + K(f)[Ol])] gives a true activation energy, E(a), too small for a reaction as slow as the investigated one. This shows that the rate-determining step of this reaction cannot be the CTC ionization, but is rather the collapse of bromonium-tribromide intermediates having a large and negative formation enthalpy. Low temperatures and high Br2 concentrations favor the transformation of the tribromide counteranion into pentabromide, and the third-order dependence of the rate on Br2 results from the fact that the rate-determining step involves a species containing three Br2 and one olefin molecules. This shift from an overall third-order to a fourth-order rate law with decreasing temperature and increasing [Br2] could provide a mechanistic criterium for rate determination during the nucleophilic step of olefin bromination.