1-hydroxyhomoadamantan-2-one O-methyl oxime

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-hydroxyhomoadamantan-2-one O-methyl oxime
• 英文别名: 4-methoxyiminotricyclo[4.3.1.13,8]undecan-3-ol
• 化学式: C₁₂H₁₉NO₂
• 分子量: 209.288
• InChiKey: HBTVGNQBRULYFY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  41.82
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-hydroxyhomoadamantan-2-one O-methyl oxime 在 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 Methanesulfonic acid 4-[(Z)-methoxyimino]-tricyclo[4.3.1.1^3,8]undec-3-yl ester
  参考文献：
  名称：

  Foiled Conjugation in α-Oximino Carbocations

  摘要：

  The 4-CHNOCH3 group is a cation-stabilizing group when placed in the para-position of a cumyl cation. The effect of this group on cumyl cations when flanked by adjacent methyl groups has now been determined. Solvolysis rates of 3,5-(CH3)(2)-4-(CHNOCH3)cumyl trifluoroacetates are somewhat slower than that of 3,5-dimethylcumyl trifluoroacetate. This is attributed to steric inhibition of the cation-stabilizing resonance effect of the p-oximino group. In a l-adamantyl system, where an alpha-oximino group has been placed directly adjacent to a developing cationic center, solvolysis rates relative to l-adamantyl mesylate are slowed by a factor of 10(8). This is attributed a cation-destabilizing inductive effect where geometric constraints prevent stabilizing orbital overlap of the cationic center with the adjacent alpha-oximino group. This cation-destabilizing effect fades in the homoadamantyl and the bicyclo[3.3.1]nonyl systems, where rate-retarding effects are 1.6 x 10(4) and 1.5 x 10(2), respectively. The behavior of geometrically constrained alpha-oximino cations parallels that of analogously constrained allylic cations. Computational studies at the HF/6-31G* level indicate that twisting the alpha-oximino group out of planarity with a tertiary cationic center into a perpendicular arrangement decreases stabilization by 21 kcal/mol. These studies suggest that conjugative interactions, and not ground state destabilization, are the most important factors in controlling rates of formation of alpha-oximino cations from mesylates and trifluoroacetates.

  DOI：

  10.1021/jo960073u
• 作为产物：
  描述：

  甲氧基胺盐酸盐 、 3-hydroxy-4-homoadamantanone 以 吡啶 为溶剂， 反应 20.0h， 生成 1-hydroxyhomoadamantan-2-one O-methyl oxime
  参考文献：
  名称：

  Foiled Conjugation in α-Oximino Carbocations

  摘要：

  The 4-CHNOCH3 group is a cation-stabilizing group when placed in the para-position of a cumyl cation. The effect of this group on cumyl cations when flanked by adjacent methyl groups has now been determined. Solvolysis rates of 3,5-(CH3)(2)-4-(CHNOCH3)cumyl trifluoroacetates are somewhat slower than that of 3,5-dimethylcumyl trifluoroacetate. This is attributed to steric inhibition of the cation-stabilizing resonance effect of the p-oximino group. In a l-adamantyl system, where an alpha-oximino group has been placed directly adjacent to a developing cationic center, solvolysis rates relative to l-adamantyl mesylate are slowed by a factor of 10(8). This is attributed a cation-destabilizing inductive effect where geometric constraints prevent stabilizing orbital overlap of the cationic center with the adjacent alpha-oximino group. This cation-destabilizing effect fades in the homoadamantyl and the bicyclo[3.3.1]nonyl systems, where rate-retarding effects are 1.6 x 10(4) and 1.5 x 10(2), respectively. The behavior of geometrically constrained alpha-oximino cations parallels that of analogously constrained allylic cations. Computational studies at the HF/6-31G* level indicate that twisting the alpha-oximino group out of planarity with a tertiary cationic center into a perpendicular arrangement decreases stabilization by 21 kcal/mol. These studies suggest that conjugative interactions, and not ground state destabilization, are the most important factors in controlling rates of formation of alpha-oximino cations from mesylates and trifluoroacetates.

  DOI：

  10.1021/jo960073u

文献信息

• Foiled Conjugation in α-Oximino Carbocations
  作者：Xavier Creary、Ziqi Jiang

  DOI：10.1021/jo960073u

  日期：1996.1.1

  The 4-CHNOCH3 group is a cation-stabilizing group when placed in the para-position of a cumyl cation. The effect of this group on cumyl cations when flanked by adjacent methyl groups has now been determined. Solvolysis rates of 3,5-(CH3)(2)-4-(CHNOCH3)cumyl trifluoroacetates are somewhat slower than that of 3,5-dimethylcumyl trifluoroacetate. This is attributed to steric inhibition of the cation-stabilizing resonance effect of the p-oximino group. In a l-adamantyl system, where an alpha-oximino group has been placed directly adjacent to a developing cationic center, solvolysis rates relative to l-adamantyl mesylate are slowed by a factor of 10(8). This is attributed a cation-destabilizing inductive effect where geometric constraints prevent stabilizing orbital overlap of the cationic center with the adjacent alpha-oximino group. This cation-destabilizing effect fades in the homoadamantyl and the bicyclo[3.3.1]nonyl systems, where rate-retarding effects are 1.6 x 10(4) and 1.5 x 10(2), respectively. The behavior of geometrically constrained alpha-oximino cations parallels that of analogously constrained allylic cations. Computational studies at the HF/6-31G* level indicate that twisting the alpha-oximino group out of planarity with a tertiary cationic center into a perpendicular arrangement decreases stabilization by 21 kcal/mol. These studies suggest that conjugative interactions, and not ground state destabilization, are the most important factors in controlling rates of formation of alpha-oximino cations from mesylates and trifluoroacetates.