1-Nitroadamantan-4-one | 155396-14-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Nitroadamantan-4-one
• 英文别名: 5-Nitroadamantan-2-one
• CAS: 155396-14-8
• 化学式: C₁₀H₁₃NO₃
• 分子量: 195.218
• InChiKey: WKUXMNISQRVPIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-Nitroadamantan-4-one 在 sodium tetrahydroborate 、 水 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以85%的产率得到1-Nitroadamantan-4-ol
  参考文献：
  名称：

  Barabanova; Medzhinskii; Golod, Russian Journal of Organic Chemistry, 1997, vol. 33, # 8, p. 1079 - 1082

  摘要：

  DOI：
• 作为产物：
  描述：

  1,4-二硝基金刚烷 在 硫酸 、 水 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以88%的产率得到1-Nitroadamantan-4-one
  参考文献：
  名称：

  Barabanova; Medzhinskii; Golod, Russian Journal of Organic Chemistry, 1997, vol. 33, # 8, p. 1079 - 1082

  摘要：

  DOI：

文献信息

• Electrostatic vs Hyperconjugative Effects as Stereoinductive Factors in the Adamantane Ring System
  作者：William Adcock、Jason Cotton、Neil A. Trout

  DOI：10.1021/jo00086a044

  日期：1994.4

  A series of 5-substituted (X) adamant-2-yl derivatives 1 (Y = O and CH2) have been synthesized and their C-13 NMR spectra measured. The carbonyl and ethylenic C-13 substituent chemical shifts (SCS) are shown to be proportional to substituent field effects (sigma(F)). By use of the polar field susceptibility parameter (rho(F)) for the former shifts, polar field parameters (Delta sigma(F) values) have been calculated for a series of p-SC6H4 substituents. II-Facial diastereoselectivities for the reduction (NaBH4) and methylation (MeLi) of para-substituted (S) phenyl derivatives of 1 (Y = O; X = p-SC6H4) and, as well, for the hydrochlorination of similarly substituted alkenes 1 (Y = CH2; X = p-SC6H4) have been determined and correlated successfully against polar field parameters (Delta sigma(F) values). The slopes of these plots (log(10)[Z]/[E] vs Delta sigma(F)) provide polar-field susceptibility parameters (rho(FS)) which have been deployed to calculate appropriate diastereoselectivities of the aforementioned reactions for 5-substituted (X) derivatives of 1 (Y = O and CH2) in general. A comparison of these calculated values with observed diastereoselectivities for a wide range of substituents reveals that direct electrostatic field interactions play a dominant role in governing the phenomena for nucleophilic additions of the ketones 1 (Y = O) and that it is unnecessary to invoke Cieplak's transition-state hyperconjugative model. This appears to be also the case for electrophilic additions to 1 (Y = CH2) not involving final nucleophilic capture of an intermediate cation. However, hyperconjugation clearly impinges significantly on II-facial diastereoselectivity for those reactions mediated by 2-adamantyl cations. New results for methyl-substituted derivatives of 1 (Y = O and CH2, X = CH3) reinforces the sigma-electron-withdrawing character of this substituent with respect to gamma- and delta-interactions in the neutral ground-state and cationic species.