吖辛因,1-苯甲酰八氢- | 17721-46-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 吖辛因,1-苯甲酰八氢-
• 英文名称: azocan-1-yl(phenyl)methanone
• 英文别名: 1-benzoyl-octahydro-azocine；1-Benzoyl-octahydro-azocin；1-Benzoylazocane
• CAS: 17721-46-9
• 化学式: C₁₄H₁₉NO
• mdl: MFCD02973621
• 分子量: 217.311
• InChiKey: VCEKELYMIZRCFL-UHFFFAOYSA-N

物化性质

• 沸点：
  162-162.5 °C(Press: 3 Torr)
• 密度：
  1.034±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  吖辛因,1-苯甲酰八氢- 在 lithium aluminium tetrahydride 作用下， 生成 N-benzylperhydroazocine
  参考文献：
  名称：

  Oxidations of N-(3-Indoleethyl) Cyclic Aliphatic Amines by Horseradish Peroxidase:  The Indole Ring Binds to the Enzyme and Mediates Electron-Transfer Amine Oxidation

  摘要：

  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.

  DOI：

  10.1021/ja075905s
• 作为产物：
  描述：

  N-tosylazacyclooctane 在 盐酸 作用下， 生成 吖辛因,1-苯甲酰八氢-
  参考文献：
  名称：

  Mueller; Bleier, Monatshefte fur Chemie, 1930, vol. 56, p. 391,405

  摘要：

  DOI：

文献信息

• Electrophilic C–H Borylation and Related Reactions of B–H Boron Cations
  作者：Aleksandrs Prokofjevs、Janis Jermaks、Alina Borovika、Jeff W. Kampf、Edwin Vedejs

  DOI：10.1021/om400651p

  日期：2013.11.25

  Catalytic procedures are described for the amine-directed borylation of aliphatic and aromatic tertiary amine–boranes. Sequential double borylation is observed in cases where two or more C–H bonds are available that allow 5-center or 6-center intramolecular borylation. The HNTf2-catalyzed borylation of benzylamine–boranes provides a practical means for the synthesis of ortho-substituted arylboronic

  描述了脂肪族和芳香族叔胺-硼烷的胺导向硼化的催化程序。在两个或多个 C-H 键可用的情况下观察到顺序双硼化，允许 5 中心或 6 中心分子内硼化。HNTf 2催化的苄胺-硼烷硼化反应为合成邻位取代的芳基硼酸衍生物提供了实用的方法，适用于 Suzuki-Miyaura 交叉偶联应用。
• Tertiary amine synthesis via reductive coupling of amides with Grignard reagents
  作者：Lan-Gui Xie、Darren J. Dixon

  DOI：10.1039/c7sc03613b

  日期：——

  reductive coupling reaction of Grignard reagents and tertiary amides affording functionalised tertiary amine products via an efficient and technically-simple one-pot, two-stage experimental protocol, is reported. The reaction – which can be carried out on gram-scale using as little as 1 mol% Vaska's complex [IrCl(CO)(PPh3)2] and TMDS as the terminal reductant for the initial reductive activation step –

  报道了一种新的铱催化的格氏试剂和叔酰胺的还原偶联反应，该反应通过有效且技术上简单的一锅两阶段实验方案提供功能化的叔胺产物。反应–可以使用低至1 mol％的Vaska络合物[IrCl（CO）（PPh 3）2进行克级反应。]和TMDS作为初始还原活化步骤的末端还原剂–耐受从（杂）芳族到脂肪族（支链，直链和甲酰基）的各种叔酰胺，以及各种烷基（直链，支链），乙烯基，炔基和（杂）芳基格氏试剂。该新方法已直接应用于生物活性分子合成，并且在药物分子的后期功能化中已利用了酰胺的还原偶联的高化学选择性。叔酰胺的这种还原功能化为叔胺合成提供了一种新的实用解决方案。
• Reaction of aminocarbene complexes of chromium with alkynes 10. From large to small cyclic amines: single versus double alkyne insertions
  作者：Sophie Lafollée-Bezzenine、Andrée Parlier、Henri Rudler、Jacqueline Vaissermann、Jean-Claude Daran

  DOI：10.1016/s0022-328x(98)00671-8

  日期：1998.9

  of comparing the reaction of various aminocarbene complexes of chromium with alkynes and to ascertain several points of the mechanism of their interaction, a series of complexes derived from large cyclic amines, HN(CH2)n (n≥6) and from a small cyclic amine (n=2) was synthesized. In the case of the larger amines, all the complexes examined herein, led to the expected bridgehead lactams 12 as the major

  为了比较铬的各种aminocarbene复合物与炔烃和，以确定它们之间的相互作用，从大环胺衍生的一系列复合物的机构的几个点的反应的目的，HN（CH 2）Ñ（Ñ ≥6）和从合成了小的环状胺（n = 2）。在较大的胺的情况下，本文检查的所有配合物均导致预期的桥头内酰胺12作为主要产物，为中间氮-羟基配合物如4的一致重排提供了有力的证据。内酰胺复合物12d（n为了确定开环和十二个碳原子的烷基链从氮到γ碳的迁移，已建立= 12）。有趣的是，最后一种可能性是，在络合物10b（n = 7）的情况下，发生了从氮到氧的4迁移，到目前为止尚未观察到，但根据计算也应该是可能的，但仍可能发生。以低收率，烷氧基吡咯14。还观察到了由无CO插入的环化反应产生的次要产物。对于衍生自甲基氮丙啶的氨基卡宾络合物（n= 2），已经获得了重要的结果，证实了以前的观察结果，尤其是在涉及插入反应机理方面：开环反应的区域选择性可以
• Catalytic N‐Acylation of Cyclic Amines by Arylglyoxylic Acids via Radical‐Radical Cross‐Coupling
  作者：Ajijur Rahaman、Anupam Kumar Singh、Aniket Gupta、Sukalyan Bhadra

  DOI：10.1002/ejoc.202100381

  日期：2021.4.22

  A unique copper‐based catalyst system allows for the N‐acylation of cyclic amines by arylglyoxylic acids via radical‐radical cross‐coupling strategy. As evidenced by EPR, UV‐Vis, and mass spectrometric analysis, the amide linkage formation proceeds through a Cu(I)/Cu(II) catalytic cycle involving a twofold SET process.

  独特的铜基催化剂体系可通过自由基-自由基交叉偶联策略使芳基乙醛酸对环胺进行N酰化。正如EPR，UV-Vis和质谱分析所证明的那样，酰胺键的形成过程通过涉及双重SET过程的Cu（I）/ Cu（II）催化循环进行。
• [EN] A METHOD FOR FLUORINATED RING-OPENING OF A SUBSTRATE<br/>[FR] PROCÉDÉ D'OUVERTURE DE CYCLE FLUORÉ SUR UN SUBSTRAT
  申请人：UNIV CALIFORNIA

  公开号：WO2019232245A1

  公开（公告）日：2019-12-05

  Disclosed herein, inter alia, are methods useful for making a fluoroalkyl amine and methods useful for making an α-oxygenated cyclic amine.

  在此披露的内容中，包括制备氟烷基胺的有用方法和制备α-含氧环状胺的有用方法。