(2-Allyl-cyclopentyl)-isobutyl-amine | 135535-93-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2-Allyl-cyclopentyl)-isobutyl-amine
• 英文别名: N-(2-methylpropyl)-2-prop-2-enylcyclopentan-1-amine
• CAS: 135535-93-2
• 化学式: C₁₂H₂₃N
• 分子量: 181.321
• InChiKey: RSZFWHQHWMRPKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  [2-Allyl-cyclopent-(E)-ylidene]-isobutyl-amine 在 lithium aluminium tetrahydride 作用下， 生成 (2-Allyl-cyclopentyl)-isobutyl-amine
  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

文献信息

• 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.
• Lewis acid-promoted 3-aza-Cope rearrangement of N-alkyl-N-allyl enamines
  作者：Gregory R. Cook、Nancy S. Barta、John R. Stille

  DOI：10.1021/jo00028a016

  日期：1992.1

  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.