N-methyl-(1-phenylethylidene)amine | 10557-02-5

• 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-methyl-(1-phenylethylidene)amine
• 英文别名: (Z)-N-methyl-1-phenylethan-1-imine；anti-N-Methyl-methyl-benzalamin；Z-Acetophenon-methylimin
• CAS: 10557-02-5
• 化学式: C₉H₁₁N
• 分子量: 133.193
• InChiKey: KDUZUMYJQDSBRY-NTMALXAHSA-N

物化性质

• 沸点：
  111 °C(Press: 28 Torr)
• 密度：
  0.974 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.13
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  N-methyl-(1-phenylethylidene)amine 在 [2,3,4,5-Ph4(η⁵-C4COH)Ru2(CO)2H] 作用下， 以 二氯甲烷-D2 为溶剂， 生成 N-methyl-N-(1-phenylethyl)amine
  参考文献：
  名称：

  Mechanistic Study of Hydrogen Transfer to Imines from a Hydroxycyclopentadienyl Ruthenium Hydride. Experimental Support for a Mechanism Involving Coordination of Imine to Ruthenium Prior to Hydrogen Transfer

  摘要：

  Reaction of [2,3,4,5-Ph-4(eta(5)-C4COH) Ru(CO)(2)H] (2) with different imines afforded ruthenium amine complexes at low temperatures. At higher temperatures in the presence of 2, the complexes decomposed to give [Ru-2(CO)(4)(mu-H)(C4Ph4COHOCC4Ph4)] (1) and free amine. Electron-rich imines gave ruthenium amine complexes with 2 at a lower temperature than did electron-deficient imines. The negligible deuterium isotope effect (k(RuHOH)/k(RuDOD) = 1.05) observed in the reaction of 2 with N-phenyl[1-(4-methoxyphenyl) ethylidene]amine (12) shows that neither hydride (RuH) nor proton (OH) is transferred to the imine in the rate-determining step. In the dehydrogenation of N-phenyl-1-phenylethylamine (4) to the corresponding imine 8 by [2,3,4,5-Ph-4(eta(4)-C4CO) Ru(CO)(2)] (A), the kinetic isotope effects observed support a stepwise hydrogen transfer where the isotope effect for C-H cleavage (k(CHNH)/k(CDNH) = 3.24) is equal to the combined (C-H, N-H) isotope effect (k(CHNH)/k(CDND) = 3.26). Hydrogenation of N-methyl(1-phenylethylidene) amine (14) by 2 in the presence of the external amine trap N-methyl-1-(4-methoxyphenyl) ethylamine (16) afforded 90-100% of complex [2,3,4,5-Ph-4(eta(4)-C4CO)] Ru(CO)(2)NH(CH3)(CHPhCH3) (15), which is the complex between ruthenium and the amine newly generated from the imine. At -80 degrees C the reaction of hydride 2 with 4-BnNHsC(6)H(9)=NPh (18), with an internal amine trap, only afforded [2,3,4,5-Ph-4(eta(4)-C4CO)](CO)(2)RuNH(Ph)(C6H10-4-NHBn) (19), where the ruthenium binds to the amine originating from the imine, showing that neither complex A nor the diamine is formed. Above -8 degrees C complex 19 rearranged to the thermodynamically more stable [Ph-4(eta(4)-C4CO)](CO)(2)RuNH(Bn)(C6H10-4-NHPh) (20). These results are consistent with an inner sphere mechanism in which the substrate coordinates to ruthenium prior to hydrogen transfer and are difficult to explain with the outer sphere pathway previously proposed.

  DOI：

  10.1021/ja061494o
• 作为产物：
  描述：

  苯乙酮 、 甲胺 在 4 A molecular sieve 作用下， 以 乙醇 为溶剂， 反应 20.0h， 以90%的产率得到N-methyl-(1-phenylethylidene)amine
  参考文献：
  名称：

  Mechanistic Study of Hydrogen Transfer to Imines from a Hydroxycyclopentadienyl Ruthenium Hydride. Experimental Support for a Mechanism Involving Coordination of Imine to Ruthenium Prior to Hydrogen Transfer

  摘要：

  Reaction of [2,3,4,5-Ph-4(eta(5)-C4COH) Ru(CO)(2)H] (2) with different imines afforded ruthenium amine complexes at low temperatures. At higher temperatures in the presence of 2, the complexes decomposed to give [Ru-2(CO)(4)(mu-H)(C4Ph4COHOCC4Ph4)] (1) and free amine. Electron-rich imines gave ruthenium amine complexes with 2 at a lower temperature than did electron-deficient imines. The negligible deuterium isotope effect (k(RuHOH)/k(RuDOD) = 1.05) observed in the reaction of 2 with N-phenyl[1-(4-methoxyphenyl) ethylidene]amine (12) shows that neither hydride (RuH) nor proton (OH) is transferred to the imine in the rate-determining step. In the dehydrogenation of N-phenyl-1-phenylethylamine (4) to the corresponding imine 8 by [2,3,4,5-Ph-4(eta(4)-C4CO) Ru(CO)(2)] (A), the kinetic isotope effects observed support a stepwise hydrogen transfer where the isotope effect for C-H cleavage (k(CHNH)/k(CDNH) = 3.24) is equal to the combined (C-H, N-H) isotope effect (k(CHNH)/k(CDND) = 3.26). Hydrogenation of N-methyl(1-phenylethylidene) amine (14) by 2 in the presence of the external amine trap N-methyl-1-(4-methoxyphenyl) ethylamine (16) afforded 90-100% of complex [2,3,4,5-Ph-4(eta(4)-C4CO)] Ru(CO)(2)NH(CH3)(CHPhCH3) (15), which is the complex between ruthenium and the amine newly generated from the imine. At -80 degrees C the reaction of hydride 2 with 4-BnNHsC(6)H(9)=NPh (18), with an internal amine trap, only afforded [2,3,4,5-Ph-4(eta(4)-C4CO)](CO)(2)RuNH(Ph)(C6H10-4-NHBn) (19), where the ruthenium binds to the amine originating from the imine, showing that neither complex A nor the diamine is formed. Above -8 degrees C complex 19 rearranged to the thermodynamically more stable [Ph-4(eta(4)-C4CO)](CO)(2)RuNH(Bn)(C6H10-4-NHPh) (20). These results are consistent with an inner sphere mechanism in which the substrate coordinates to ruthenium prior to hydrogen transfer and are difficult to explain with the outer sphere pathway previously proposed.

  DOI：

  10.1021/ja061494o

文献信息

• Disulfonimide‐Catalyzed Asymmetric Reduction of <i>N</i> ‐Alkyl Imines
  作者：Vijay N. Wakchaure、Philip S. J. Kaib、Markus Leutzsch、Benjamin List

  DOI：10.1002/anie.201504052

  日期：2015.9.28

  A chiral disulfonimide (DSI)‐catalyzed asymmetric reduction of N‐alkyl imines with Hantzsch esters as a hydrogen source in the presence of Boc2O has been developed. The reaction delivers Boc‐protected N‐alkyl amines with excellent yields and enantioselectivity. The method tolerates a large variety of alkyl amines, thus illustrating potential for a general reductive cross‐coupling of ketones with diverse

  在Boc 2 O存在的情况下，已开发出一种以Hantzsch酯为氢源的手性二磺酰亚胺（DSI）催化N烷基亚胺的不对称还原。该反应可提供具有出色收率和对映选择性的Boc保护的N-烷基胺。该方法可耐受多种烷基胺，从而说明了酮与各种胺的一般还原性交叉偶联的潜力，并已用于药物（S）-利伐斯的明，NPS R-568盐酸盐的合成，以及（R）-芬迪林。
• Direct Asymmetric Hydrogenation of <i>N</i>-Methyl and <i>N</i>-Alkyl Imines with an Ir(III)H Catalyst
  作者：Ernest Salomó、Albert Gallen、Giuseppe Sciortino、Gregori Ujaque、Arnald Grabulosa、Agustí Lledós、Antoni Riera、Xavier Verdaguer

  DOI：10.1021/jacs.8b11547

  日期：2018.12.12

  A novel cationic [IrH(THF)(P,N)(imine)] [BArF] catalyst containing a P-stereogenic MaxPHOX ligand is described for the direct asymmetric hydrogenation of N-methyl and N-alkyl imines. This is the first catalytic system to attain high enantioselectivity (up to 94% ee) in this type of transformation. The labile tetrahydrofuran ligand allows for effective activation and reactivity, even at low temperatures

  描述了一种新型阳离子 [IrH(THF)(P,N)(亚胺)] [BArF] 催化剂，该催化剂含有 P-立体异构 MaxPHOX 配体，用于 N-甲基和 N-烷基亚胺的直接不对称氢化。这是第一个在此类转化中实现高对映选择性（高达 94% ee）的催化系统。即使在低温下，不稳定的四氢呋喃配体也能实现有效的活化和反应。密度泛函理论计算使得反应的立体化学过程合理化。
• Disulfonimides versus Phosphoric Acids in Brønsted Acid Catalysis: The Effect of Weak Hydrogen Bonds and Multiple Acceptors on Complex Structures and Reactivity
  作者：Kerstin Rothermel、Matej Žabka、Johnny Hioe、Ruth M. Gschwind

  DOI：10.1021/acs.joc.9b01811

  日期：2019.11.1

  N-alkylimine, which shows excellent reactivity and selectivity in reactions with DSI, reveals an enlarged structural space in complexes with the chiral phosphoric acid TRIP as potential explanation of its reduced reactivity and selectivity. Thus, considering factors such as flexibility and possible hydrogen bond sites is essential for catalyst development in Brønsted acid catalysis.

  在布朗斯台德酸催化中，氢键对于反应性和选择性起着至关重要的作用。然而，迄今为止，弱氢键或多受体的贡献尚不清楚，因为收集弱氢键的实验证据极其困难。在这里，我们利用氢键和布朗斯台德酸/亚胺复合物的结构来分析 BINOL 衍生的手性二磺酰亚胺 (DSI)/亚胺复合物。揭示了氢键非常弱的 DSI/亚胺络合物离子对的 1H 和 15N 化学位移以及 1JNH 耦合常数。DSI 的高酸性导致作为结构锚的氢键显着减弱。此外，DSI 的五个氢键受体允许亚胺在二元 DSI 配合物中具有巨大的迁移率。理论计算预测，与氧的氢键在能量上不太受青睐；然而，NOE 和交换数据通过实验证实了它们的相当大的数量。此外，N-烷基亚胺在与 DSI 的反应中表现出优异的反应性和选择性，揭示了与手性磷酸 TRIP 配合物中扩大的结构空间，这可能是其反应性和选择性降低的潜在解释。因此，考虑灵活性和可能的​​氢键位点等因素对于布朗斯台德酸催化中的催化剂开发至关重要。
• [EN] ASYMMETRIC IMINE HYDROGENATION PROCESSES<br/>[FR] PROCEDES D'HYDROGENATION ASYMETRIQUE DES IMINES
  申请人：ABDUR-RASHID KAMALUDDIN

  公开号：WO2005056513A1

  公开（公告）日：2005-06-23

  A process for the catalytic hydrogenation or asymmetric hydrogenation of imines of Formula (I) to the corresponding amines of Formula (II) is provided in which R1 is aryl ; R2 is aryl, cyclic, alkyl, alkenyl or alkynyl; and R3 is alky l. The catalytic system includes a ruthenium complex containing (1) a diamine and (2) a diphosphine or two monodentate phosphines ligands. Such process also relates to the asymmetric hydrogenation of prochiral imines to the chiral amines using chiral ruthenium complexes bearing chiral diphosphines or chiral monodentate phosphines and chiral diamines.

  提供了一种用于催化氢化或不对称氢化Formula(I)的亚胺至对应的Formula(II)胺的过程，其中R1是芳基；R2是芳基、环状、烷基、烯基或炔基；R3是烷基。催化系统包括一个含有(1)二胺和(2)二膦或两个单齿膦配体的钌配合物。这种过程还涉及使用手性钌配合物进行的对映选择氢化的过程，该钌配合物带有手性二膦或手性单齿膦和手性二胺。
• Asymmetric Imine Hydrogenation Processes
  申请人：Abdur-Rashid Kamaluddin

  公开号：US20070293681A1

  公开（公告）日：2007-12-20

  A process for the catalytic hydrogenation or asymmetric hydrogenation of imines of Formula (I) to the corresponding amines of Formula (II) is provided in which R 1 is aryl; R 2 is aryl, cyclic, alkyl, alkenyl or alkynyl; and R 3 is alkyl. The catalytic system includes a ruthenium complex containing (1) a diamine and (2) a diphosphine or two monodentate phosphines ligands. Such process also relates to the asymmetric hydrogenation of prochiral imines to the chiral amines using chiral ruthenium complexes bearing chiral diphosphines or chiral monodentate phosphines and chiral diamines.

  提供了一种用于催化氢化或不对称氢化式(I)亚胺至相应氨基式(II)的过程，其中R1为芳基；R2为芳香基，环状，烷基，烯基或炔基；R3为烷基。催化系统包括一种含有(1)二胺和(2)二膦或两个单齿膦配体的钌配合物。这种过程还涉及使用手性二膦或手性单齿膦和手性二胺的手性钌配合物对非手性亚胺进行不对称氢化，制备手性氨基化合物。