(α-hexahydroazepinylidene)-acetophenone | 64944-51-0

• 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: (α-hexahydroazepinylidene)-acetophenone
• 英文别名: 2-azepan-2-ylidene-1-phenylethanone；2-(Azepan-2-ylidene)-1-phenylethan-1-one；2-(azepan-2-ylidene)-1-phenylethanone
• CAS: 64944-51-0
• 化学式: C₁₄H₁₇NO
• 分子量: 215.295
• InChiKey: POCGQHMTIWSSTE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 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：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (α-hexahydroazepinylidene)-acetophenone 以 二氯甲烷 、 甲苯 为溶剂， 反应 4.5h， 生成 4-benzoyl-1,1-diphenyl-2-(4-methylphenyl)-2,5,6,7,8,9-hexahydro-1H-[1,2,4,3λ4]triazaborino[4,5-d]azepine
  参考文献：
  名称：

  A new bicyclic oxazaborines with a bridged nitrogen atom, their thermic rearrangement and fluorescence properties

  摘要：

  Cyclic beta-enaminones bearing secondary amino group react with 4-substituted benzenediazonium tetraphenylborates in dichloromethane to form substituted bicyclic [1,3,2 lambda(4)] oxazaborines The oxazaborines rearrange, on heating to 200 degrees C in the absence of solvent or in DMF or DMSO, to isomeric 2H-[1,2,4,3 lambda(4)] triazaborines. Previously prepared [1,3,2 lambda(4)] oxazaborines derived from acyclic beta-enaminones bearing secondary amino group either did not undergo the rearrangement or with a lot of difficulties and with negligible yield. The fluorescence behaviour of the prepared triazaborines was observed. These compounds fluoresce in 2-methyltetrahydrofurane and in solid state under low temperatures. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.11.004
• 作为产物：
  描述：

  1-氮杂-2-甲氧基-1-环庚烯 在 甲醇 、 bis(acetylacetonate)nickel(II) 、 sodium 作用下， 反应 25.0h， 生成 (α-hexahydroazepinylidene)-acetophenone
  参考文献：
  名称：

  A new bicyclic oxazaborines with a bridged nitrogen atom, their thermic rearrangement and fluorescence properties

  摘要：

  Cyclic beta-enaminones bearing secondary amino group react with 4-substituted benzenediazonium tetraphenylborates in dichloromethane to form substituted bicyclic [1,3,2 lambda(4)] oxazaborines The oxazaborines rearrange, on heating to 200 degrees C in the absence of solvent or in DMF or DMSO, to isomeric 2H-[1,2,4,3 lambda(4)] triazaborines. Previously prepared [1,3,2 lambda(4)] oxazaborines derived from acyclic beta-enaminones bearing secondary amino group either did not undergo the rearrangement or with a lot of difficulties and with negligible yield. The fluorescence behaviour of the prepared triazaborines was observed. These compounds fluoresce in 2-methyltetrahydrofurane and in solid state under low temperatures. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.11.004

文献信息

• Gold-Catalysed Synthesis of Exocyclic Vinylogous Amides and β-Amino Ketones: A Detailed Study on the 5-<i>exo</i>/6-<i>endo</i>-<i>dig</i>Selectivity, Methodology and Scope
  作者：Dina Scarpi、Stefano Begliomini、Cristina Prandi、Alberto Oppedisano、Annamaria Deagostino、Enrique Gómez-Bengoa、Béla Fiser、Ernesto G. Occhiato

  DOI：10.1002/ejoc.201500205

  日期：2015.5

  6-alkynyl-3,4-dihydro-2H-pyridines, which gives synthetically useful vinylogous amides (β-enaminones), has been studied in detail, in order to optimize the reaction conditions, enlarge the scope and gain insight into the mechanism and the structural features that selectively favour the 6-endo-dig oxyauration of the triple bond. Experimental studies and DFT calculations demonstrate that the 6-endo-dig approach

  已详细研究了 N-Boc 保护的 6-炔基-3,4-二氢-2H-吡啶的金（I）催化反应，该反应产生了合成有用的乙烯基酰胺（β-烯胺酮），以优化反应条件，扩大范围并深入了解选择性地有利于三键 6-endo-dig 氧化的机制和结构特征。实验研究和 DFT 计算表明，6-endo-dig 方法不适用于取代炔烃，而对于末端炔烃，5-exo-dig 环化占优势，尽管 C-6 处的角度大（120°）。用 N-Cbz 保护的 2-炔基哌啶观察到相同的选择性。使用这些化合物，由于 6-endo-dig 攻击取代的三键，获得了 β-氨基酮。
• Delbecq, Philippe; Bacos, Daniel; Celerier, Jean Pierre, Canadian Journal of Chemistry, 1991, vol. 69, # 8, p. 1201 - 1206
  作者：Delbecq, Philippe、Bacos, Daniel、Celerier, Jean Pierre、Lhommet, Gerard

  DOI：——

  日期：——
• A new bicyclic oxazaborines with a bridged nitrogen atom, their thermic rearrangement and fluorescence properties
  作者：František Josefík、Markéta Svobodová、Valerio Bertolasi、Petr Šimůnek、Vladimír Macháček、Numan Almonasy、Eva Černošková

  DOI：10.1016/j.jorganchem.2011.11.004

  日期：2012.2

  Cyclic beta-enaminones bearing secondary amino group react with 4-substituted benzenediazonium tetraphenylborates in dichloromethane to form substituted bicyclic [1,3,2 lambda(4)] oxazaborines The oxazaborines rearrange, on heating to 200 degrees C in the absence of solvent or in DMF or DMSO, to isomeric 2H-[1,2,4,3 lambda(4)] triazaborines. Previously prepared [1,3,2 lambda(4)] oxazaborines derived from acyclic beta-enaminones bearing secondary amino group either did not undergo the rearrangement or with a lot of difficulties and with negligible yield. The fluorescence behaviour of the prepared triazaborines was observed. These compounds fluoresce in 2-methyltetrahydrofurane and in solid state under low temperatures. (C) 2011 Elsevier B.V. All rights reserved.