N-benzyl-2-methyloctan-1-amine | 358720-69-1

• 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-benzyl-2-methyloctan-1-amine
• CAS: 358720-69-1
• 化学式: C₁₆H₂₇N
• 分子量: 233.397
• InChiKey: MPXXOTMENHHKJE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-2-methyloctan-1-amine 、 对甲苯磺酰氯 在 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 16.0h， 以153 mg的产率得到N-benzyl-4-methyl-N-(2-methyloctyl)benzenesulfonamide
  参考文献：
  名称：

  Hydroaminoalkylation of Unactivated Olefins with Dialkylamines

  摘要：

  The intermolecular addition of the a-C-H bonds of unactivated dialkylamines to unactivated olefins in the presence of the chloro amido complex [TaCl3(NEt2)(2)](2) (2) is described. This process forms the branched insertion products in high yields (up to 96%) and selectivities, and a rare example of an intermolecular amine-olefin coupling reaction that does not require preactivation of either substrate. The reaction is shown to encompass the addition of the primary C-H bonds in linear- and branched-methylamines, as well as secondary C-H bonds in higher dialkylamines. The related chloroanilido complex [TaCl3(NMePh)(2)](2) (4) is also shown to catalyze the addition of N-alkyl-arylamines to olefins at temperatures as low as 90 degrees C. H-1 NMR spectroscopy, identification of the catalyst structure, and deuterium-labeling experiments all suggest that reactions catalyzed by 2 and 4 occur by turnover-limiting generation of an eta(2)-imine complex. These labeling studies also imply that more favorable partitioning of the eta(2)-imine complex toward reaction with alkene versus regeneration of the starting bis-amido complex accounts for the higher reactivity of the mixed halide amido catalyst versus a homoleptic amido complex.

  DOI：

  10.1021/ja806367e
• 作为产物：
  描述：

  辛烯 、 N-甲基苄胺 在 [Ta(NEt2)2Cl3]2 、 苯甲醚 作用下， 以 氘代苯 为溶剂， 反应 24.0h， 以47%的产率得到N-benzyl-2-methyloctan-1-amine
  参考文献：
  名称：

  Hydroaminoalkylation of Unactivated Olefins with Dialkylamines

  摘要：

  The intermolecular addition of the a-C-H bonds of unactivated dialkylamines to unactivated olefins in the presence of the chloro amido complex [TaCl3(NEt2)(2)](2) (2) is described. This process forms the branched insertion products in high yields (up to 96%) and selectivities, and a rare example of an intermolecular amine-olefin coupling reaction that does not require preactivation of either substrate. The reaction is shown to encompass the addition of the primary C-H bonds in linear- and branched-methylamines, as well as secondary C-H bonds in higher dialkylamines. The related chloroanilido complex [TaCl3(NMePh)(2)](2) (4) is also shown to catalyze the addition of N-alkyl-arylamines to olefins at temperatures as low as 90 degrees C. H-1 NMR spectroscopy, identification of the catalyst structure, and deuterium-labeling experiments all suggest that reactions catalyzed by 2 and 4 occur by turnover-limiting generation of an eta(2)-imine complex. These labeling studies also imply that more favorable partitioning of the eta(2)-imine complex toward reaction with alkene versus regeneration of the starting bis-amido complex accounts for the higher reactivity of the mixed halide amido catalyst versus a homoleptic amido complex.

  DOI：

  10.1021/ja806367e

文献信息

• [EN] GROUP 5 METAL COMPLEXES FOR CATALYTIC AMINE FUNCTIONALIZATION<br/>[FR] COMPLEXES MÉTALLIQUES DU GROUPE 5 POUR LA FONCTIONNALISATION CATALYTIQUE D'AMINE
  申请人：UNIV BRITISH COLUMBIA

  公开号：WO2018213938A1

  公开（公告）日：2018-11-29

  This application pertains to group 5 metal complexes having the structure of Formula I; and their potential utility in catalyzing α-alkylation of secondary amine-containing moieties.

  这种应用涉及具有公式I结构的5族金属配合物；以及它们在催化含有次要胺基团的α-烷基化中的潜在用途。
• [EN] GROUP 5 METAL COMPLEXES FOR PRODUCING AMINE-FUNTIONALIZED POLYOLEFINS<br/>[FR] COMPLEXES MÉTALLIQUES DU GROUPE 5 POUR LA PRODUCTION DE POLYOLÉFINES À FONCTION AMINE
  申请人：UNIV BRITISH COLUMBIA

  公开号：WO2019222834A1

  公开（公告）日：2019-11-28

  This application pertains to group 5 metal complexes having the structure of Formula I: and their potential utility in catalyzing amination of polyolefins having alkene groups.amine-

  这种应用涉及具有Formula I结构的5族金属配合物，以及它们在催化具有烯烃基团的聚烯烃氨化反应中的潜在用途。
• Efficient hydroaminomethylation of olefins catalyzed by Rh-complex ligated by P,O-hybrid ligand with chelating effect
  作者：Xiao-Chao Chen、Tian Lan、Kai-Chun Zhao、Lin Guo、Yong Lu、Ye Liu

  DOI：10.1016/j.jcat.2022.05.010

  日期：2022.7

  Tandem hydroaminomethylation (HAM) represents one of the most important catalytic protocols for the one-pot synthesis of amines using low-cost and widely available olefins, syngas and amines as starting materials. In this work, the applied P,O-hybrid ligand containing phosphino-fragment and carboxylic group [L1, 2-(diphenylphosphino)benzoic acid] could stoichiometrically react with Rh(acac)(CO)2 to

  串联加氢氨基甲基化 (HAM) 代表了使用低成本和广泛可用的烯烃、合成气和胺作为起始材料的一锅法合成胺的最重要的催化方案之一。在这项工作中，所应用的含有膦基片段和羧基的 P,O-杂化配体 [ L1 , 2-(二苯基膦基)苯甲酸] 可以与 Rh(acac)(CO) 2进行化学计量反应，得到稳定的 Rh-络合物Z [dicarbonyl-2-(diphenylphosphino)benzoato rhodium (I)]，其中来自L1的更实质性的 P,O-螯合作为去质子化时的双齿钳以及热力学上有利的六元环结构保证了其稳定性。发现Z可以作为高活性催化剂来加速HAM中每个单独步骤的反应速率，有利于完全抑制烯烃加氢的副反应。原位高压 FT-IR 光谱分析首次证明L1的参与极大地促进了两种活性 Rh-H 中间体的形成（A'和A , v 2012 和 2043 cm -1 ) 保持良好的使用寿命。并且D
• VERFAHREN ZUR HERSTELLUNG VON AMINEN DURCH HYDROAMINOMETHYLIERUNG VON OLEFINEN IN GEGENWART VON IONISCHEN FLÜSSIGKEITEN
  申请人：Bayer Aktiengesellschaft

  公开号：EP1265844A1

  公开（公告）日：2002-12-18
• [DE] VERFAHREN ZUR HERSTELLUNG VON AMINEN DURCH HYDROAMINOMETHYLIERUNG VON OLEFINEN IN GEGENWART VON IONISCHEN FLÜSSIGKEITEN<br/>[EN] METHOD FOR PRODUCING AMINES BY THE HYDROAMINOMETHYLATION OF OLEFINS IN THE PRESENCE OF IONIC LIQUIDS<br/>[FR] PROCEDE DE PREPARATION D'AMINES PAR HYDROAMINOMETHYLATION D'OLEFINES EN PRESENCE DE LIQUIDES IONIQUES
  申请人：BAYER AG

  公开号：WO2001064621A1

  公开（公告）日：2001-09-07

  Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Aminen durch Katalytische Hydroaminomethylierung von Olefinen in Gegenwart einer ionischen Flüssigkeit.