N-chloro-3-azabicyclo[3.3.0]octane | 187329-14-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: N-chloro-3-azabicyclo[3.3.0]octane
• 英文别名: 2-chloro-3,3a,4,5,6,6a-hexahydro-1H-cyclopenta[c]pyrrole
• CAS: 187329-14-2
• 化学式: C₇H₁₂ClN
• 分子量: 145.632
• InChiKey: UUQAPWCBIKNPSQ-UHFFFAOYSA-N

物化性质

• 沸点：
  190.6±23.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-chloro-3-azabicyclo[3.3.0]octane 在 sodium hydroxide 作用下， 以 水 为溶剂， 生成 3-azabicyclo-[3,3,0]oct-2-ene
  参考文献：
  名称：

  Kinetics of dehydrohalogenation ofN-chloro-3-azabicyclo[3,3,0]octane in alkaline medium. NMR and ES/MS evidence of the dimerization of 3-azabicyclo[3,3,0]oct-2-ene

  摘要：

  The formation of 3-azabicyclo[3,3,0]oct-2-ene in the course of the synthesis of N-amino-3-azabicyclo[3,3,0]octane using the Raschig process results from the following two consecutive reactions: chlorine transfer between the monochloramine and the 3-azabicyclo[3,3,0]octane followed by a dehydrohalogenation of the substituted haloamine. The kinetics of the reaction were studied by HPLC and UV as a function of temperature (15 to 44 degrees C), and the concentrations of NaOH (0.1 to 1 M) and the chlorinated derivative (1 to 4 X 10(-3) M). The reaction is bimolecular (k = 103 x 10(-6) M-1 s(-1); Delta H-0# = 89 kJ mol(-1); and Delta S-0# = -33.6 J mol(-1) K-1) and has an E2 mechanism. The spectral data of 7-azabicyclo[3,3,0]oct-2-ene were determined. 1R, NMR, and ES/MS analysis show dimerization of the water-soluble monomer into a white insoluble dimer. (C) 1998 John Wiley & Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1998)30:2<129::aid-kin4>3.0.co;2-u
• 作为产物：
  描述：

  八氢环戊烷[C]吡咯 在 sodium hypochlorite 作用下， 以100%的产率得到N-chloro-3-azabicyclo[3.3.0]octane
  参考文献：
  名称：

  Study of a reduction step during the continuous synthesis of N-amino-3-azabicyclo[3.3.0]octane. Kinetics, modelling, and optimization

  摘要：

  The reduction of N-chloro-3-azabicyclo[3.3.0]octane with sodium borohydride at different pH values and variable concentrations of the haloamine and reducing agent was studied. The reaction was found to be second order and exhibited a specific acid catalysis. The enthalpy and entropy of activation were determined at pH 12.89. A mathematical treatment of the kinetic data allowed a complete characterization of the final state and the determination of percentage of haloamine reduced as a function of temperature, [NaBH(4)]/[haloamine] ratio, arid pH. A reaction mechanism is proposed.

  DOI：

  10.1134/s0023158410040105

文献信息

• Kinetics of reduction of chloramines by sodium borohydride
  作者：C�cile Duriche、Chaza Darwich、Mazen Elkhatib、Mohamad Tabcheh、Henri Delalu

  DOI：10.1002/poc.504

  日期：2002.7

  The reduction of chloramine, methylchloramine, dimethylchloramine and N-chloro-3-azabicyclo­[3.3.0]octane by sodium borohydride was studied according to pH, temperature and concentrations of haloamine and reducing agent. The interaction is bimolecular and exhibits a specific acid catalysis. The enthalpy and entropy of activation were determined at pH 12.89. A mathematical treatment of the reaction

  根据pH值，温度，卤胺和还原剂的浓度，研究了硼氢化钠对氯胺，甲基氯胺，二甲基氯胺和N-氯-3-氮杂双环[3.3.0]辛烷的还原作用。相互作用是双分子的，并表现出特定的酸催化作用。在pH 12.89下确定活化的焓和熵。通过对反应动力学进行数学处理，可以完整表征最终状态，并可以根据[NaBH 4 ] / [R 1 R 2 NCl]比，pH和温度确定还原卤代胺的百分比。提出了一种反应机理。版权所有©2002 John Wiley＆Sons，Ltd.
• PROCESS FOR THE PREPARATION OF A VIRAL PROTEASE INHIBITOR AND INTERMEDIATES THEREOF
  申请人：DIPHARMA FRANCIS S.r.I.

  公开号：US20140323689A1

  公开（公告）日：2014-10-30

  Process for the preparation of a viral protease inhibitor and intermediates useful in its preparation.

  制备病毒蛋白酶抑制剂及其制备中有用的中间体的过程。
• Process for the preparation of a viral protease inhibitor and its intermediates
  申请人：Dipharma Francis S.r.l.

  公开号：EP2801566A1

  公开（公告）日：2014-11-12

  Process for the preparation of a viral protease inhibitor and intermediates useful in its preparation.

  制备病毒蛋白酶抑制剂及其制备中有用的中间体的过程。
• Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3-azabicyclo[3,3,0]octane
  作者：M. Elkhatib、A. Marchand、L. Peyrot、J. J. Counioux、H. Delalu

  DOI：10.1002/(sici)1097-4601(1997)29:2<89::aid-kin2>3.0.co;2-g

  日期：——

  The chlorine transfer reaction between 3-azabicyclo[3,3.0]octane ''AZA'' and chloramine was studied over pH 8-13 in order to follow both the amination and halogenation properties of NH2Cl. The results show the existence of two competitive reactions which lead to the simultaneous formation of N-amino- and N-chloro- 3-azabicyclo[3,3,0]octane by bimolecular kinetics. The halogenation reaction is reversible and the chlorine derivative obtained, which is thermolabile and unstable in the pure state, was identified by electrospray mass spectrometry. These phenomena were quantified by a reaction between neutral species according to an apparent S(N)2-type mechanism for the amination process and a ionic mechanism involving a reaction between chloramine and protonated amine for the halogenation process. Amination occurs only in strongly basic solutions (pH greater than or equal to 13) while chlorination occurs at lower pH's (pH less than or equal to 8). At intermediate pH's, a mixture of these two compounds is obtained. The relative proportions of the products are a function of intrinsic rate constants, pH and pK(a) of the reactants. The rate constants and thermodynamic activation parameters are the following: k(1) = 45.5 X 10(-3) M(-1) s(-1); Delta H-1(0#) = 59.8 kJ mol(-1); Delta S-1(0#) = -86.5 J mol(-1) K-1 for amination; k(2) = 114 X 10(-3) M(-1) s(-1); Delta H-2(0#) = 63.9 kJ mol(-1); and Delta S-2(0#) = -48.3 J mol(-1) K-1 for chlorination. The ability of an interaction corresponding to a specific (NH3Cl+/RR'NH) or general (NH2Cl/RR'NH) acid catalysis has been also discussed. (C) 1997 John Wiley & Sons, Inc.