N-benzylperhydroazocine | 65486-43-3

• 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-benzylperhydroazocine
• 英文别名: 1-benzylazocane；N-benzylheptamethyleneimine；benzylazocane
• CAS: 65486-43-3
• 化学式: C₁₄H₂₁N
• 分子量: 203.327
• InChiKey: RWUPUQOEWJZKFS-UHFFFAOYSA-N

物化性质

• 沸点：
  286.7±9.0 °C(Predicted)
• 密度：
  0.962±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzylperhydroazocine 、 四氧化钌 生成 苯甲酸
  参考文献：
  名称：

  TANGARI, N.;GIOVINE, M.;MORLACCHI, F.;VETUSCHI, C., GAZZ. CHIM. ITAL., 1985, 115, N 6, 325-328

  摘要：

  DOI：
• 作为产物：
  描述：

  5-hexenyl methanesulfonate 在 dirhodium tetraacetate 、 氢气 、 6,6′-[(3,3′-二叔丁基-5,5′-二甲氧基-1,1′-二苯基-2,2′-二基)双(氧)]双(二苯并[d,f][1,3,2]二噁磷杂庚英) 作用下， 以 苯 为溶剂， 60.0~80.0 ℃ 、2.76 MPa 条件下， 反应 38.0h， 生成 N-benzylperhydroazocine
  参考文献：
  名称：

  Synthesis of Medium and Large Cyclic Amines in Rhodium-Catalysed Reactions of Aminoalkenes with H2/CO

  摘要：

  在铑催化下，N-苄基或 N-苄基或 N-烷基氨基烯烃 (6) 与 H2/CO 催化反应，可以得到环胺 (7)（7-13 个环）。 大小），而且产量极高。 对于较小的环，氨基烯的氢化会成为一个竞争反应。 但可以通过使用 H2/CO 气体比率为 为 1 : 5。2- 烯氧基苄胺 (13) 的反应生成了 9-、12- 和 17 元环 (14)，收率为 30-40%，但二聚体的形成 (16) 和/或氢化是竞争反应。类似的反应还有 烯酰胺和邻位烯基苯胺的类似反应只能生成 非环化氨基醛作为产物，分离产率较低。

  DOI：

  10.1071/ch00112

文献信息

• Oxidations of <i>N</i>-(3-Indoleethyl) Cyclic Aliphatic Amines by Horseradish Peroxidase:  The Indole Ring Binds to the Enzyme and Mediates Electron-Transfer Amine Oxidation
  作者：Ke-Qing Ling、Wen-Shan Li、Lawrence M. Sayre

  DOI：10.1021/ja075905s

  日期：2008.1.1

  Although oxidations of aromatic amines by horseradish peroxidase (HRP) are well-known, typical aliphatic amines are not substrates of HRP. In this study, the reactions of N-benzyl and N-methyl cyclic amines with HRP were found to be slow, but reactions of N-(3-indoleethyl) cyclic amines were 2-3 orders of magnitude faster. Analyses of pH-rate profiles revealed a dominant contribution to reaction by the amine-free base forms, the only species found to bind to the enzyme. A metabolic study on a family of congeneric N-(3-indoleethyl) cyclic amines indicated competition between amine and indole oxidation pathways. Amine oxidation dominated for the seven- and eight-membered azacycles, where ring size supports the change in hybridization from sp(3) to sp(2) that occurs upon one-electron amine nitrogen oxidation, whereas only indole oxidation was observed for the six-membered ring congener. Optical difference spectroscopic binding data and computational docking simulations suggest that all the arylalkylamine substrates bind to the enzyme through their aromatic termini with similar binding modes and binding affinities. Kinetic saturation was observed for a particularly soluble substrate, consistent with an obligatory role of an enzyme-substrate complexation preceding electron transfer. The significant rate enhancements seen for the indoleethylamine substrates suggest the ability of the bound indole ring to mediate what amounts to medium long-range electron-transfer oxidation of the tertiary amine center by the HRP oxidants. This is the first systematic investigation to document aliphatic amine oxidation by HRP at rates consistent with normal metabolic turnover, and the demonstration that this is facilitated by an auxiliary electron-rich aromatic ring.
• TMSCF ₂ Br‐Enabled Fluorination–Aminocarbonylation of Aldehydes: Modular Access to α‐Fluoroamides
  作者：An Liu、Chuanfa Ni、Qiqiang Xie、Jinbo Hu

  DOI：10.1002/anie.202115467

  日期：2022.2.14

  AbstractA protocol for the modular assembly of the α‐fluoroamide motif has been developed, which provides a practical method for the efficient synthesis of structurally diverse α‐fluoroamides from easily available aldehydes and tertiary amines through a three‐component fluorination–aminocarbonylation process. The key to the success of this process is taking advantage of the multiple roles of the unique difluorocarbene reagent TMSCF2Br (TMS=trimethylsilyl). The mechanism of the process involves the 1,2‐fluorine and oxygen migrations of the in situ formed TMS‐protected α‐aminodifluoromethyl carbinol intermediates, which represents a new type of deoxyfluorination reaction.
• Tangari, Nicola; Giovine, Maria; Morlacchi, Flaviano, Gazzetta Chimica Italiana, 1985, vol. 115, # 6, p. 325 - 328
  作者：Tangari, Nicola、Giovine, Maria、Morlacchi, Flaviano、Vetuschi, Claudio

  DOI：——

  日期：——
• A direct route to medium and large cyclic amines from aminoalkenes
  作者：David J. Bergmann、Eva M. Campi、W.Roy Jackson、Antonio F. Patti、Dilek Saylik

  DOI：10.1016/s0040-4039(99)01020-5

  日期：1999.7

  Rhodium-catalysed reactions of aminoalkenes with H-2/CO give cyclic amines with a range of medium and large ring sizes in yields lip to 85%. High regioselectivity for non-branched products can be obtained when BIPHEPHOS is used as a ligand in the hydroformylation reaction. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of Medium and Large Cyclic Amines in Rhodium-Catalysed Reactions of Aminoalkenes with H2/CO
  作者：David J. Bergmann、Eva M. Campi、W. Roy Jackson、Antonio F. Patti、Dilek Saylik

  DOI：10.1071/ch00112

  日期：——

  Rhodium-catalysed reactions of N-benzyl- or N-alkyl-aminoalkenes (6) with H2/CO can give cyclic amines (7) (7–13 ring size) in good to excellent yields when BIPHEPHOS is used as a ligand. Hydrogenation of the aminoalkene becomes a competing reaction for the smaller rings but can be overcome by using a H2/CO gas ratio of 1 : 5. Reactions of 2-alkenyloxybenzylamines (13) gave 9-, 12- and 17-membered rings (14) in 30–40% yield, but dimer formation (16) and/or hydrogenation were competing reactions. Similar reactions of alkenylamides and ortho-alkenylanilines gave only non-cyclized amino aldehydes as products in low isolated yields.

  在铑催化下，N-苄基或 N-苄基或 N-烷基氨基烯烃 (6) 与 H2/CO 催化反应，可以得到环胺 (7)（7-13 个环）。 大小），而且产量极高。 对于较小的环，氨基烯的氢化会成为一个竞争反应。 但可以通过使用 H2/CO 气体比率为 为 1 : 5。2- 烯氧基苄胺 (13) 的反应生成了 9-、12- 和 17 元环 (14)，收率为 30-40%，但二聚体的形成 (16) 和/或氢化是竞争反应。类似的反应还有 烯酰胺和邻位烯基苯胺的类似反应只能生成 非环化氨基醛作为产物，分离产率较低。