N-<(E)-2-phenylethenyl>hexahydroazepin-2-one | 17179-94-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: N-<(E)-2-phenylethenyl>hexahydroazepin-2-one
• 英文别名: N-(E-2-phenylethenyl)-hexahydroazepin-2-one；(E)-N-(2-phenylethenyl)-2-azepanone；(E)-1-styrylazepan-2-one；trans-1-styryl-hexahydro-azepin-2-one；trans-1-Styryl-hexahydro-azepin-2-on；trans-N-Styryl-ε-caprolactam；N-(2-Phenyl-ethenyl)-3,4,5,6(2H)-tetrahydroazepin-7-one；1-[(E)-2-phenylethenyl]azepan-2-one
• CAS: 17179-94-1
• 化学式: C₁₄H₁₇NO
• 分子量: 215.295
• InChiKey: LNFWUFSAKKAWIZ-ZRDIBKRKSA-N

物化性质

• 熔点：
  117-118 °C(Solv: ethyl ether (60-29-7); benzene (71-43-2))
• 沸点：
  189 °C(Press: 2 Torr)
• 密度：
  1.133±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  N-<(E)-2-phenylethenyl>hexahydroazepin-2-one 在 正丁基锂 、 (R,R)-ethylene-1,2-bis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (R)-1,1'-binaphth-2,2'-diolate 、 苯硅烷 、 氢气 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 45.0 ℃ 、3.45 MPa 条件下， 反应 39.0h， 生成 (+)-2-phenyl-hexahydroazepine
  参考文献：
  名称：

  Catalytic Asymmetric Hydrogenation of Imines with a Chiral Titanocene Catalyst: Scope and Limitations

  摘要：

  The asymmetric hydrogenation of imines with a chiral titanocene catalyst derived from Brintzinger's ansatitanocene complex 1 proceeds to afford amines with good to excellent enantioselectivity. The catalyst is particularly effective for the reduction of cyclic imines. For these substrates enantiomeric excesses from 95 to 99% were achieved. For acyclic imines lower enantiomeric excesses were observed. The reason for this is likely due to the fact that the acyclic imines are mixtures of anti and syn isomers which interconvert during the reaction. The catalyst was found to be tolerant of many functional groups found in organic synthesis. Thus the reaction represents an effective method for the synthesis of chiral cyclic amines.

  DOI：

  10.1021/ja00099a012
• 作为产物：
  描述：

  己内酰胺 在 sodium 、 苯 作用下， 生成 N-<(E)-2-phenylethenyl>hexahydroazepin-2-one
  参考文献：
  名称：

  Ziegenbein; Franke, Chemische Berichte, 1957, vol. 90, p. 2291,2297

  摘要：

  DOI：

文献信息

• Iodine(III)‐Mediated Diazidation and Azido‐oxyamination of Enamides
  作者：Sophie Nocquet‐Thibault、Anita Rayar、Pascal Retailleau、Kevin Cariou、Robert H. Dodd

  DOI：10.1002/chem.201501782

  日期：2015.9.28

  In this study we demonstrate that the combination of bis(tert‐butylcarbonyloxy)iodobenzene and lithium azide in acetonitrile allows the diazidation of various enamide substrates. The azido‐oxyamination of the same substrates can be carried out in the presence of 2,2,6,6‐tetramethylpiperidine N‐oxide (TEMPO). Control experiments strongly suggest that this latter process occurs through a shift in nature

  在这项研究中，我们证明了双（叔丁基羰基氧基）碘代苯和叠氮化锂在乙腈中的组合可以使各种酰胺基被重氮化。相同底物的叠氮基氧化可在2,2,6,6-四甲基哌啶N-氧化物（TEMPO）存在下进行。对照实验强烈表明，后一种过程是通过原位生成的亲电子物种从自由基转变为阳离子而发生的。最后，还通过对其进行各种选择性反应来评估合成的新化合物的多功能性。
• Cesium Carbonate-Promoted Hydroamidation of Alkynes: Enamides, Indoles and the Effect of Iron(III) Chloride
  作者：María Teresa Herrero、Jokin Díaz de Sarralde、Raul SanMartin、Laura Bravo、Esther Domínguez

  DOI：10.1002/adsc.201200430

  日期：2012.11.12

  A series of enamide derivatives was prepared by a simple procedure for the hydroamidation of alkynes with amides and sulfonamides. The use of such a mild base as cesium carbonate promotes the latter transformation, and the addition of catalytic amounts of iron(III) chloride has a beneficial effect in the outcome of some of the presented hydroamidation reactions. A range of indoles was also synthesized

  通过简单的方法制备了一系列的酰胺衍生物，用于炔烃与酰胺和磺酰胺的加氢酰胺化。使用诸如碳酸铯之类的弱碱可以促进后者的转化，并且催化量的氯化铁（III）的添加在某些所述加氢酰胺化反应的结果中具有有益的作用。还通过两种互补方法从邻-炔基苯胺合成了一系列吲哚，这对于从邻-（2-氨基苯基炔基）苯胺构建吲哚并[1,2- c ]喹唑啉四环体系是有用的。
• Stereospecific One-pot Synthesis of Enamides and Enimides by the Copper Iodide Promoted Vinylic Substitution
  作者：Takuji Ogawa、Toshiyuki Kiji、Kazuo Hayami、Hitomi Suzuki

  DOI：10.1246/cl.1991.1443

  日期：1991.8

  Enamides and enimides were prepared stereospecifically from vinyl bromides by direct vinylic substitution in the presence of copper salt in aprotic polar solvents.

  在铜盐存在下，通过在非沸腾极性溶剂中直接进行乙烯基取代，以乙烯基溴化物为原料制备了立体定向的酰胺和酰亚胺。
• Zezza, Charles A.; Smith, Michael B., Synthetic Communications, 1987, vol. 17, # 6, p. 729 - 740
  作者：Zezza, Charles A.、Smith, Michael B.

  DOI：——

  日期：——
• Zezza, Charles A.; Kwon, Tae Woo; Sheu, JennLine, Heterocycles, 1992, vol. 34, # 7, p. 1325 - 1342
  作者：Zezza, Charles A.、Kwon, Tae Woo、Sheu, JennLine、Smith, Michael B.

  DOI：——

  日期：——