N-(2-chloro-1-phenylpropylidene)isopropylamine | 1117849-85-0

• 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: N-(2-chloro-1-phenylpropylidene)isopropylamine
• 英文别名: N-isopropyl-1-phenyl-2-chloropropanimine；2-chloro-1-phenyl-N-propan-2-ylpropan-1-imine
• CAS: 1117849-85-0
• 化学式: C₁₂H₁₆ClN
• 分子量: 209.719
• InChiKey: IBCDYOGCBMJLEU-UHFFFAOYSA-N

物化性质

• 沸点：
  262.5±32.0 °C(predicted)
• 密度：
  1.00±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(2-chloro-1-phenylpropylidene)isopropylamine 在 吡啶 、 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 23.5h， 生成 2-chloro-1-(4-chlorophenyl)-3-isopropylimino-2-methyl-3-phenylpropyl methanesulfonate
  参考文献：
  名称：

  Diastereoselective Aldol Reaction of Zincated 3-Chloro-3-methyl-1-azaallylic Anions as Key Step in the Synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines

  摘要：

  Zincated 3-chloro-3-methyl-1-azaallylic anions undergo a stereoselective aldol addition across aromatic aldehydes and subsequent mesylation to produce syn alpha-chloro-beta-mesyloxyketimines, which were isolated in 80-84% yield and high diastereomeric excess (dr > 97/3) after purification via flash chromatography. The syn alpha-chloro-beta-mesyloxyketimines were further stereoselectively reduced to give stereochemically defined 3-aminopropyl mesylates, which were cyclized to 1,2,3,4-tetrasubstituted 3-chloroazetidines containing three contiguous stereogenic centers. DFT calculations on the key aldol addition revealed the presence of a highly ordered bimetallic six-membered twist-boat-like transition state structure with a tetra-coordinated metal cyclic structure. DFT calculations revealed that chelation of both zinc and lithium cations in the transition state structure leads to the experimentally observed high syn diastereoselectivity of aldol reactions.

  DOI：

  10.1021/jo300203t
• 作为产物：
  描述：

  2-chloro-3-isopropylimino-2-methyl-1,3-diphenylpropan-1-ol 在 potassium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 N-(2-chloro-1-phenylpropylidene)isopropylamine 、 1-[(2R,3S)-2-methyl-3-phenyloxiran-2-yl]-1-phenyl-N-propan-2-ylmethanimine 、 1-[(2R,3R)-2-methyl-3-phenyloxiran-2-yl]-1-phenyl-N-propan-2-ylmethanimine 、 苯甲醛
  参考文献：
  名称：

  Diastereoselective Aldol Reaction of Zincated 3-Chloro-3-methyl-1-azaallylic Anions as Key Step in the Synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines

  摘要：

  Zincated 3-chloro-3-methyl-1-azaallylic anions undergo a stereoselective aldol addition across aromatic aldehydes and subsequent mesylation to produce syn alpha-chloro-beta-mesyloxyketimines, which were isolated in 80-84% yield and high diastereomeric excess (dr > 97/3) after purification via flash chromatography. The syn alpha-chloro-beta-mesyloxyketimines were further stereoselectively reduced to give stereochemically defined 3-aminopropyl mesylates, which were cyclized to 1,2,3,4-tetrasubstituted 3-chloroazetidines containing three contiguous stereogenic centers. DFT calculations on the key aldol addition revealed the presence of a highly ordered bimetallic six-membered twist-boat-like transition state structure with a tetra-coordinated metal cyclic structure. DFT calculations revealed that chelation of both zinc and lithium cations in the transition state structure leads to the experimentally observed high syn diastereoselectivity of aldol reactions.

  DOI：

  10.1021/jo300203t

文献信息

• Insight into the Solvation and Isomerization of 3-Halo-1-azaallylic Anions from Ab Initio Metadynamics Calculations and NMR Experiments
  作者：Reinout Declerck、Bart De Sterck、Toon Verstraelen、Guido Verniest、Sven Mangelinckx、Jan Jacobs、Norbert De Kimpe、Michel Waroquier、Veronique Van Speybroeck

  DOI：10.1002/chem.200800948

  日期：2009.1.5

  Long live the Z isomer! The solvation and isomerization properties of lithiated 3‐chloro‐1‐azaallylic anions in tetrahydrofuran are revealed. Extensive and convincing evidence is obtained from state‐of‐the‐art first‐principle molecular dynamics and metadynamics simulations in an explicit periodic solvent model, together with detailed NMR experiments.

  Z 异构体万岁！揭示了四氢呋喃中锂化的3-氯-1-氮杂烯丙基丙烯酸盐的溶剂化和异构化性质。在明确的周期性溶剂模型中，通过最新的第一性原理分子动力学和元动力学模拟以及详细的NMR实验，获得了广泛而令人信服的证据。