N-(3-溴苯基)-N-羟基-2,2-二甲基丙酰胺 | 114838-67-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: N-(3-溴苯基)-N-羟基-2,2-二甲基丙酰胺
• 英文名称: N-(3-bromophenyl)-N-hydroxy-2,2-dimethylpropanamide
• CAS: 114838-67-4
• 化学式: C₁₁H₁₄BrNO₂
• 分子量: 272.142
• InChiKey: JGAXBABUEPFYSE-UHFFFAOYSA-N

物化性质

• 沸点：
  361.2±44.0 °C(Predicted)
• 密度：
  1.449±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(3-溴苯基)-N-羟基-2,2-二甲基丙酰胺 、 丙烯酸甲酯（MA） 在 sodium hydride 作用下， 生成 methyl N-(m-bromophenyl)aziridine-2-carboxylate
  参考文献：
  名称：

  N-hydroxy-N-pivaloylanilines: a new aziridinating agent

  摘要：

  描述了由异羟肟酸和缺电子烯烃有效合成2-官能化N-芳基氮丙啶的方法。

  DOI：

  10.1039/c39930000038
• 作为产物：
  描述：

  m-bromophenylhydroxylamine 、 三甲基乙酰氯 在 碳酸氢钠 作用下， 以 乙醚 为溶剂， 生成 N-(3-溴苯基)-N-羟基-2,2-二甲基丙酰胺
  参考文献：
  名称：

  Asymmetric synthesis of N-aryl aziridines

  摘要：

  The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (-)-8-phenylmenthol, (-)-quinine and (-)-Oppolzer's sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer's auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantio selection and a mechanism is proposed for the aziridination reaction. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00548-1

文献信息

• Synthesis of Asymmetric<i>N</i>-Arylaziridine Derivatives Using a New Chiral Phase-Transfer Catalyst
  作者：Eagambaram Murugan、Ayyanar Siva

  DOI：10.1055/s-2005-869976

  日期：——

  Substituted N-arylaziridine derivatives were synthesized in an enantioselective manner from N-acyl-N-arylhydroxylamine and electron deficient olefins using chiral phase-transfer catalysts (CPTCs) derived from cinchona alkaloids. The structures of the CPTCs were ascertained through various spectral techniques such as FT-IR, 1H NMR, 13C NMR, and mass spectroscopy, as well as elemental analyses. The efficiency and chiral behavior of a range of CPTCs were studied with respect to both yield and ee. The chemical yields were in the range of 24-92% and ee was 29-95%. It was observed that the S-enantiomers were more predominant than the R-enantiomers with cinchonidine as catalyst; whereas the R-enantio­mers were more predominant in the case of cinchonine based CPTC. We propose here a suitable mechanism for the formation of chiral aziridines as well as optimized procedures for a range of N-arylaziridine derivatives.

  利用从金鸡纳生物碱中提取的手性相转移催化剂（CPTCs），以对映体选择性方式从 N-酰基-N-芳基羟胺和缺电子烯烃合成了取代的 N-芳基氮丙啶衍生物。通过各种光谱技术（如傅立叶变换红外光谱、1H NMR、13C NMR 和质谱）以及元素分析，确定了 CPTC 的结构。研究了一系列 CPTC 在产率和ee方面的效率和手性。化学收率在 24-92% 之间，ee 为 29-95%。据观察，在以辛可尼丁为催化剂的情况下，S-对映体比 R-对映体更占优势；而在以辛可尼丁为催化剂的 CPTC 情况下，R-对映体更占优势。我们在此提出了形成手性氮丙啶的合适机制以及一系列 N-芳基氮丙啶衍生物的优化程序。
• A new enantioselective synthesis of N-arylaziridines by phase-transfer catalysis
  作者：João Aires-de-Sousa、Ana M Lobo、Sundaresan Prabhakar

  DOI：10.1016/0040-4039(96)00490-x

  日期：1996.4

  Chiral N-arylaziridines are obtained from N-acyl-N-arylhydroxylamines using quaternary salts of Cinchona alkaloids as phase-transfer catalysts.

  使用金鸡纳生物碱的季盐作为相转移催化剂，从N-酰基-N-芳基羟胺获得手性N-芳基氮丙啶。
• Boche, Gernot; Bosold, Ferdinand; Schroeder, Stefan, Angewandte Chemie, 1988, vol. 100, # 7, p. 965 - 966
  作者：Boche, Gernot、Bosold, Ferdinand、Schroeder, Stefan

  DOI：——

  日期：——
• BOCHE, GERNOT;BOSOLD, FERDINAND;SCHRODER, STEFAN
  作者：BOCHE, GERNOT、BOSOLD, FERDINAND、SCHRODER, STEFAN

  DOI：——

  日期：——
• Asymmetric synthesis of N-aryl aziridines
  作者：João Aires-de-Sousa、Sundaresan Prabhakar、Ana M. Lobo、Ana M. Rosa、Mário J.S. Gomes、Marta C. Corvo、David J. Williams、Andrew J.P. White

  DOI：10.1016/s0957-4166(01)00548-1

  日期：2002.1

  The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (-)-8-phenylmenthol, (-)-quinine and (-)-Oppolzer's sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer's auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantio selection and a mechanism is proposed for the aziridination reaction. (C) 2002 Elsevier Science Ltd. All rights reserved.