N-ethyl-3-methylnonan-2-amine | 1071539-63-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-ethyl-3-methylnonan-2-amine
• CAS: 1071539-63-3
• 化学式: C₁₂H₂₇N
• 分子量: 185.353
• InChiKey: KPXSBYILBBOZOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  13
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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-ethyl-3-methylnonan-2-amine 、 对甲苯磺酰氯 在 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 11.0h， 以310 mg的产率得到N-ethyl-4-methyl-N-(3-methylnonan-2-yl)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 、 二乙胺 在 [Ta(NEt2)2Cl3]2 、 苯甲醚 作用下， 以 氘代苯 为溶剂， 反应 25.0h， 以91%的产率得到N-ethyl-3-methylnonan-2-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

• Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts
  作者：Layal F. Yaacoub、Maha A. Aljuhani、Abdesslem Jedidi、Manal S. Al-Harbi、Walid Al Maksoud、Wiebke Wackerow、Edy Abou-Hamad、Jérémie D. A. Pelletier、Mohamad El Eter、Luigi Cavallo、Jean-Marie Basset

  DOI：10.1021/acs.organomet.0c00246

  日期：2020.7.13

  metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.

  单点氧化硅负载的IV族金属酰胺络合物[Ti（NMe 2）4 ]给出了三（酰胺基）负载的片段[（≡Si–O-）Ti（-NMe 2）3]，其通过两个酰胺基配体之间的α-H转移转化为三元金属环（称为金属氮丙啶）。当三元金属环与1-辛烯反应时，通过将双键插入金属氮丙啶的MC键中，得到五元金属环。根据表面有机金属化学（SOMC）的概念和步骤，分离并充分表征了这两个金属环，它们是末端烯烃的氢氨基烷基化催化循环中的关键中间体。本文表明，表面有机金属化学可用于鉴定和全面表征烯烃的氢氨基烷基化中的钛的三元和五元金属环。
• Hydroaminoalkylation of Unactivated Olefins with Dialkylamines
  作者：Seth B. Herzon、John F. Hartwig

  DOI：10.1021/ja806367e

  日期：2008.11.12

  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.