N-Allylcyclopentylideneamine | 30533-03-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-Allylcyclopentylideneamine
• 英文别名: N-Cyclopentylidenallylamin；Allylcylopentylidenamin；N-prop-2-enylcyclopentanimine
• CAS: 30533-03-0
• 化学式: C₈H₁₃N
• 分子量: 123.198
• InChiKey: MQLXFGQCHCMVLL-UHFFFAOYSA-N

物化性质

• 沸点：
  151.6±19.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-Allylcyclopentylideneamine 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以87%的产率得到N-烯丙基环戊基胺
  参考文献：
  名称：

  Lewis acid-promoted 3-aza-Cope rearrangement of N-alkyl-N-allyl enamines

  摘要：

  The 3-aza-Cope rearrangement of the N-alkyl-N-allylenamines derived from isobutyraldehyde, which proceeds thermally at 250-degrees-C, has been accelerated by a variety of electrophilic reagents to give gamma,delta-unsaturated imines. Protic acids, such as HCl (0.5 equiv), and the Lewis acidic reagents TiCl4 (0.1-0.2 equiv), Et2O.BF3 (0.5 equiv), and AlMe3 (1.0 equiv) produced complete [3,3] rearrangement of substrates at 111-degrees-C. By increasing the Lewis acidity of the aluminum reagents, this transformation was achieved at 50-degrees-C with ClAlMe2, Cl2AlMe, and methylaluminum bis(2,6-diphenylphenoxide). Reaction conditions were studied initially by GLC analysis of the N-isobutyl derivative. These optimum conditions were then used to obtain isolated yields of 59-99% for rearrangement and in situ LiAlH4 reduction of the analogous N-methylcyclohexyl substrate to the corresponding delta,epsilon-unsaturated amine. Substrates derived from 2-phenylpropanal, n-butanal, cyclohexanone, and cyclopentanone were used to examine the general effectiveness of HCl, TiCl4, and AlMe3 as reagents for acceleration of the [3,3] rearrangement. The most versatile and efficient reagent for promoting this reaction, AlMe3, produced overall yields of 83-96% for the two-step rearrangement and reduction of these substrates.

  DOI：

  10.1021/jo00028a016
• 作为产物：
  描述：

  环戊酮 、 丙烯胺 以 苯 为溶剂， 生成 N-Allylcyclopentylideneamine
  参考文献：
  名称：

  一种亚胺加成/闭环复分解方法，用于盐酸和品尼酸的螺环核心。

  摘要：

  [反应：见正文]已围绕亚胺烯丙基化/闭环复分解序列设计了盐酸盐和松果酸螺环核心的方法。此序列已用于生成多个azabicylo [n.5]模型系统。新报道的复分解催化剂显示出对于这些系统的环化非常有效。

  DOI：

  10.1021/ol005903b

文献信息

• Regioselective aza-Cope rearrangement of .alpha.-halogenated and nonhalogenated imines
  作者：John T. Welch、Bart De Corte、Norbert De Kimpe

  DOI：10.1021/jo00304a002

  日期：1990.8
• Heteroaromatization of aliphatic imines in the presence of an aluminum-potassium catalyst
  作者：G. Ya. Kondrat'eva、Yu. S. Dol'skaya、E. A. Aleksandrova、B. A. Kazanskii

  DOI：10.1007/bf00475225

  日期：1972.7
• Preparation of 3-aza-Cope rearrangement of N-alkyl-N-allyl enamines
  作者：Gregory R. Cook、John R. Stille

  DOI：10.1021/jo00019a021

  日期：1991.9

  The [3,3] charge-accelerated rearrangement of N-allyl-N-isobutyl enamine substrates to gamma,delta-unsaturated imine products and subsequent reduction to the corresponding N-alkyl delta,epsilon-unsaturated amines is reported. Several routes to the N-allyl-N-isobutyl enamines were established for the enamine prepared from isobutyraldehyde. With use of the most efficient route developed, enamines derived from butanal, 2-phenylpropanal, cyclohexanone, and cyclopentanone were prepared in 58 to 92% overall yield in three steps from allylamine. In the case of butanal, the E isomer was formed exclusively, while the enamine from 2-phenylpropanal was prepared with an E to Z selectivity of 86:14. Heating these N-allyl-N-isobutyl enamines in refluxing dioxane with 0.5 equiv of HCl produced [3,3] rearrangement for substrates derived from isobutyraldehyde, 2-phenylpropanal, and cyclohexanone; the enamines of n-butanal and cyclopentanone were found to react through alternate pathways.
• WELCH, JOHN T.;DE, CORTE BART;DE, KIMPE NORBERT, J. ORG. CHEM., 55,(1990) N7, C. 4911-4913
  作者：WELCH, JOHN T.、DE, CORTE BART、DE, KIMPE NORBERT

  DOI：——

  日期：——
• An Imine Addition/Ring-Closing Metathesis Approach to the Spirocyclic Core of Halichlorine and Pinnaic Acid
  作者：Dennis L. Wright、James P. Schulte、Melissa A. Page

  DOI：10.1021/ol005903b

  日期：2000.6.1

  [reaction: see text] An approach to the spirocyclic core of halichlorine and pinnaic acid has been designed around an imine allylation/ring-closing metathesis sequence. This sequence has been used to generate several azabicylo[n.5] model systems. A newly reported metathesis catalyst was show to be highly effective for cyclization of these systems.

  [反应：见正文]已围绕亚胺烯丙基化/闭环复分解序列设计了盐酸盐和松果酸螺环核心的方法。此序列已用于生成多个azabicylo [n.5]模型系统。新报道的复分解催化剂显示出对于这些系统的环化非常有效。