N-p-methoxybenzylnortrop-2-ene | 214326-28-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: N-p-methoxybenzylnortrop-2-ene
• 英文别名: 8-[(4-methoxyphenyl)methyl]-8-azabicyclo[3.2.1]oct-6-ene
• CAS: 214326-28-0
• 化学式: C₁₅H₁₉NO
• 分子量: 229.322
• InChiKey: IPVKOFQOBPZVOS-UHFFFAOYSA-N

物化性质

• 沸点：
  333.3±27.0 °C(Predicted)
• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  12.47
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N-p-methoxybenzylnortrop-2-ene 在 1-氯乙基氯甲酸酯 作用下， 生成 8-azabicyclo[3.2.1]oct-6-ene
  参考文献：
  名称：

  Manipulation of substituents at nitrogen in tropanes, homotropanes, and dehydro- derivatives

  摘要：

  Trop-6-ene (8-methyl-8-azabicyclo[3.2.1]oct-6-ene) and substituted N-benzylnortrop-6-enes are synthesised. N-Debenzylation of tropanes fails using a wide variety of non-hydrogenolytic conditions despite effective application in model piperidine derivatives; debenzylation of homotropanes is more successful, giving norhomotropane and norhomotrop-7-ene. Bridged N-benzyl compounds react more slowly than N-methyl analogues with chloroformates; the resulting quaternary intermediates are more prone than the N-methyl analogues to suffer competitive reversion to the starting amine, especially in the tropanes, consistent with slower S(N)2 attack at the benzylic carbon during decomposition; the use of an N-p-methoxybenzyl group does allow partial debenzylation to nortrop-6-ene, suggesting greater SNI character in the decomposition step in this case. 'Equatorial' attack is preferred in methylation of N-benzyl-nortrop-6-ene and -homotrop-7-ene with CH3I; subsequent reductive debenzylation of the quaternary salt achieves overall replacement of N-benzyl by N-methyl in both cases. VT NMR studies show the presence of a single 'equatorial' invertomer (Cl syn- to the 2C-bridge) in N-chloro-norhomotropanes and -7-enes and, by analogy, in the N-alkyl compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00643-7
• 作为产物：
  描述：

  1,3-环庚二烯 在 aluminum amalgam 、 lithium aluminium tetrahydride 、 二溴亚砜 、 tetramethylammonium metaperiodate 、 胸苷酸 作用下， 以 四氢呋喃 、 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 181.0h， 生成 N-p-methoxybenzylnortrop-2-ene
  参考文献：
  名称：

  Manipulation of substituents at nitrogen in tropanes, homotropanes, and dehydro- derivatives

  摘要：

  Trop-6-ene (8-methyl-8-azabicyclo[3.2.1]oct-6-ene) and substituted N-benzylnortrop-6-enes are synthesised. N-Debenzylation of tropanes fails using a wide variety of non-hydrogenolytic conditions despite effective application in model piperidine derivatives; debenzylation of homotropanes is more successful, giving norhomotropane and norhomotrop-7-ene. Bridged N-benzyl compounds react more slowly than N-methyl analogues with chloroformates; the resulting quaternary intermediates are more prone than the N-methyl analogues to suffer competitive reversion to the starting amine, especially in the tropanes, consistent with slower S(N)2 attack at the benzylic carbon during decomposition; the use of an N-p-methoxybenzyl group does allow partial debenzylation to nortrop-6-ene, suggesting greater SNI character in the decomposition step in this case. 'Equatorial' attack is preferred in methylation of N-benzyl-nortrop-6-ene and -homotrop-7-ene with CH3I; subsequent reductive debenzylation of the quaternary salt achieves overall replacement of N-benzyl by N-methyl in both cases. VT NMR studies show the presence of a single 'equatorial' invertomer (Cl syn- to the 2C-bridge) in N-chloro-norhomotropanes and -7-enes and, by analogy, in the N-alkyl compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00643-7

文献信息

• Manipulation of substituents at nitrogen in tropanes, homotropanes, and dehydro- derivatives
  作者：Nicola M. Howarth、John R. Malpass、Craig R. Smith

  DOI：10.1016/s0040-4020(98)00643-7

  日期：1998.9

  Trop-6-ene (8-methyl-8-azabicyclo[3.2.1]oct-6-ene) and substituted N-benzylnortrop-6-enes are synthesised. N-Debenzylation of tropanes fails using a wide variety of non-hydrogenolytic conditions despite effective application in model piperidine derivatives; debenzylation of homotropanes is more successful, giving norhomotropane and norhomotrop-7-ene. Bridged N-benzyl compounds react more slowly than N-methyl analogues with chloroformates; the resulting quaternary intermediates are more prone than the N-methyl analogues to suffer competitive reversion to the starting amine, especially in the tropanes, consistent with slower S(N)2 attack at the benzylic carbon during decomposition; the use of an N-p-methoxybenzyl group does allow partial debenzylation to nortrop-6-ene, suggesting greater SNI character in the decomposition step in this case. 'Equatorial' attack is preferred in methylation of N-benzyl-nortrop-6-ene and -homotrop-7-ene with CH3I; subsequent reductive debenzylation of the quaternary salt achieves overall replacement of N-benzyl by N-methyl in both cases. VT NMR studies show the presence of a single 'equatorial' invertomer (Cl syn- to the 2C-bridge) in N-chloro-norhomotropanes and -7-enes and, by analogy, in the N-alkyl compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.