(Z)-N-(α-Methylbenzylidene)-(S)-1-phenylethylamine | 100483-18-9

• 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: (Z)-N-(α-Methylbenzylidene)-(S)-1-phenylethylamine
• 英文别名: (Z)-N-<1-phenylethylidene>-1-phenylethylamine；(Z)-(S)-1-phenyl-N-(1-phenylethylidene)ethanamine；(Z)-N-(1-(S)-phenylethyl)ethan-1-(phenyl)-1-imine；(S)-N-(phenylethylidene)-1-phenylethylamine
• CAS: 100483-18-9
• 化学式: C₁₆H₁₇N
• 分子量: 223.318
• InChiKey: HXVFIDKQGMXDOK-FSLWVPIDSA-N

物化性质

• 沸点：
  310.9±25.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (S)-(-)- α-甲基苄胺 、 (Z)-N-(α-Methylbenzylidene)-(S)-1-phenylethylamine 生成 (S)-(-)-N-(methyldibenzylidene)-α-methylbenzylamine
  参考文献：
  名称：

  BOYD, D. R.;JENNINGS, W. B.;WARING, L. C., J. ORG. CHEM., 1986, 51, N 7, 992-995

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-(-)-N-(methyldibenzylidene)-α-methylbenzylamine 以 氘代二甲亚砜 为溶剂， 生成 (Z)-N-(α-Methylbenzylidene)-(S)-1-phenylethylamine
  参考文献：
  名称：

  Dynamic stereochemistry of imines and derivatives. 19. Mutarotation and E-Z isomerization of chiral imines in [2H4]methanol solution

  摘要：

  DOI：

  10.1021/jo00357a007

文献信息

• An investigation of the observed, but counter-intuitive, stereoselectivity noted during chiral amine synthesis via <i>N</i>-chiral-ketimines
  作者：Thomas C Nugent、Richard Vaughan Williams、Andrei Dragan、Alejandro Alvarado Méndez、Andrei V Iosub

  DOI：10.3762/bjoc.9.247

  日期：——

  The default explanation for good to high diastereomeric excess when reducing N-chiral imines possessing only mediocre cis/trans-imine ratios (>15% cis-imine) has invariably been in situ cis-to-trans isomerization before reduction; but until now no study unequivocally supported this conclusion. The present study co-examines an alternative hypothesis, namely that some classes of cis-imines may hold conformations that erode the inherent facial bias of the chiral auxiliary, providing more of the trans-imine reduction product than would otherwise be expected. The ensuing experimental and computational (DFT) results favor the former, pre-existing, explanation.

  将默认解释为在还原仅具有中等cis/trans-亚胺比率（>15% cis-亚胺）的N-手性亚胺时获得良好至高对映体过量的解释一直是在还原之前发生原位cis到trans异构化；但直到现在，没有研究明确支持这一结论。本研究同时考虑了另一种假设，即一些类别的cis-亚胺可能具有侵蚀手性辅助体固有面部偏好的构象，提供比预期更多的trans-亚胺还原产物。随后的实验和计算（DFT）结果支持了前者，即已存在的解释。
• Diastereoselective nucleophilic additions to imines attached to tricarbonyl(arene)chromium moieties
  作者：Dorothy M. David、Leon A. P. Kane-Maguire、Stephen G. Pyne

  DOI：10.1039/dt9940000289

  日期：——

  A range of imine complexes has been prepared which possess planar chirality associated with the attached tricarbonyl(1,2-disubstituted arene)chromium moiety. Nucleophilic addition to the imine group of these complexes occurs with high diastereoselectivity, providing an efficient route to the asymmetric synthesis of chiral amines. The stereochemical outcome of the additions may be rationalized in terms

  已制备了具有与连接的三羰基（1,2-二取代的芳烃）铬部分相关的平面手性的一系列亚胺配合物。这些络合物向亚胺基的亲核加成反应具有很高的非对映选择性，为手性胺的不对称合成提供了一条有效途径。该加法的立体化学结果可以在用于复合青睐的构象异构体的加以推理，对亚胺的面部存在的亲核攻击抗到空间要求的Cr（CO）3团体。还已经对亚胺配合物进行了相关研究，其中手性助剂是与亚胺N原子相连的碳中心。在这些后面的系统中，也观察到了高非对映选择性，但并不优于相关的游离胺所获得的非对映选择性。
• Iron catalyzed diastereoselective hydrogenation of chiral imines
  作者：D. Brenna、S. Rossi、F. Cozzi、M. Benaglia

  DOI：10.1039/c7ob01123g

  日期：——

  Cyclopentadienone-based iron complexes were used for the first time to succesfully catalyze the diastereoselective hydrogenation of enantiopure imines. Chiral amines, including valuable biologically active products, were obtained often as enantiomerically pure compounds. Computational studies helped to elucidate the chemical and stereochemical aspects of the iron-catalyzed reaction.

  首次使用基于环戊二烯酮的铁络合物成功催化对映纯亚胺的非对映选择性氢化。手性胺，包括有价值的生物活性产物，通常以对映体纯化合物的形式获得。计算研究有助于阐明铁催化反应的化学和立体化学方面。
• Process for producing 4,4,4,- trifluoro-3-hydroxybutyric acid
  申请人：CENTRAL GLASS COMPANY, LIMITED

  公开号：US20030088095A1

  公开（公告）日：2003-05-08

  A first process for producing an optically active perfluoroalkylcarbinol derivative includes (a) reacting an optically active imine with a compound that is a hemiacetal of a perfluoroalkylaldehyde or a hydrate of a perfluoroalkylaldehyde to obtain a condensate; and (b) hydrolyzing the condensate under an acid condition. A second process for increasing optical purity of an optically active 4,4,4-trifluoro 3-hydroxy-1-aryl-1-butanone derivative includes (a) precipitating a racemic crystal of the derivative, from the derivative; and (b) removing the racemic crystal from the derivative. A third process for increasing optical purity of the butanone derivative includes recrystallizing the derivative. Novel compounds are optically active and inactive 4,4,4-trifluoro-3-hydroxybutanoic aryl ester derivatives. A fourth process for producing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxybutyric acid aryl ester derivative includes oxidizing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative. A fifth process for increasing optical purity of the optically active aryl ester derivative includes recrystallizing the derivative. A sixth process for producing an optically active 4,4,4-trifluoro-1,3-butanediol includes reducing the optically active aryl ester derivative by a hydride. A seventh process for producing an optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl ester derivative includes reacting under an acid condition the optically active or optically inactive aryl ester derivative with a lower alcohol. It is possible to suitably combine at least two of the first to seventh processes.

  生产光学活性全氟烷基羟基甲基醇衍生物的第一种方法包括（a）将光学活性亚胺与半乙醇的全氟烷基醛或全氟烷基醛的水合物反应，以获得缩合物; （b）在酸性条件下水解缩合物。增加光学纯度的光学活性4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物的第二种方法包括（a）从该衍生物中沉淀出外消旋晶体; （b）将外消旋晶体从衍生物中去除。增加丁酮衍生物光学纯度的第三种方法包括重结晶该衍生物。新化合物是光学活性和非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物。生产光学活性或非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物的第四种方法包括将光学活性或非活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物氧化。增加光学活性芳基酯衍生物光学纯度的第五种方法包括重结晶该衍生物。生产光学活性4,4,4-三氟-1,3-丁二醇的第六种方法包括通过氢化还原光学活性芳基酯衍生物。生产光学活性或非活性的4,4,4-三氟-3-羟基丁酸烷基酯衍生物的第七种方法包括在酸性条件下将光学活性或非活性的芳基酯衍生物与低级醇反应。可以适当地组合第一至第七种方法中的至少两种方法。
• Process for producing 4,4,4-trifluoro-3-hydroxybutyric acid derivatives
  申请人：——

  公开号：US20020016511A1

  公开（公告）日：2002-02-07

  A first process for producing an optically active perfluoroalkylcarbinol derivative includes (a) reacting an optically active imine with a compound that is a hemiacetal of a perfluoroalkylaldehyde or a hydrate of a perfluoroalkylaldehyde to obtain a condensate; and (b) hydrolyzing the condensate under an acid condition. A second process for increasing optical purity of an optically active 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative includes (a) precipitating a racemic crystal of the derivative, from the derivative; and (b) removing the racemic crystal from the derivative. A third process for increasing optical purity of the butanone derivative includes recrystallizing the derivative. Novel compounds are optically active and inactive 4,4,4-trifluoro-3-hydroxybutanoic aryl ester derivatives. A fourth process for producing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxybutyric acid aryl ester derivative includes oxidizing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative. A fifth process for increasing optical purity of the optically active aryl ester derivative includes recrystallizing the derivative. A sixth process for producing an optically active 4,4,4-trifluoro-1,3-butanediol includes reducing the optically active aryl ester derivative by a hydride. A seventh process for producing an optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl ester derivative includes reacting under an acid condition the optically active or optically inactive aryl ester derivative with a lower alcohol. It is possible to suitably combine at least two of the first to seventh processes.

  生产光学活性全氟烷基醇衍生物的第一种方法包括：(a)将光学活性亚胺与半缩醛全氟烷基醛的半缩醛化合物或全氟烷基醛的水合物反应，获得缩合物；(b)在酸性条件下水解缩合物。第二种提高光学活性4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物光学纯度的方法包括：(a)从该衍生物中沉淀出一个外消旋晶体；(b)将外消旋晶体从该衍生物中移除。第三种提高丁酮衍生物光学纯度的方法包括重结晶该衍生物。新化合物包括光学活性和非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物。第四种生产光学活性或非活性4,4,4-三氟-3-羟基丁酸芳基酯衍生物的方法包括氧化光学活性或非活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物。第五种提高光学活性芳基酯衍生物光学纯度的方法包括重结晶该衍生物。第六种生产光学活性4,4,4-三氟-1,3-丁二醇的方法包括通过氢化还原光学活性芳基酯衍生物。第七种生产光学活性或非活性4,4,4-三氟-3-羟基丁酸烷基酯衍生物的方法包括在酸性条件下将光学活性或非活性芳基酯衍生物与低级醇反应。可以适当地结合第一到第七种方法中的至少两种方法。