2-adamantyl nitrate | 64662-51-7

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机含氧阴离子化合物
• 英文名称: 2-adamantyl nitrate
• 英文别名: 10-Adamantyl nitrate
• CAS: 64662-51-7
• 化学式: C₁₀H₁₅NO₃
• 分子量: 197.234
• InChiKey: UIIPDKFTAUKBLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-adamantyl nitrate 在 甲基(三氟甲基)-1,3-二环氧丙烷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 C₁₀H₁₅NO₄
  参考文献：
  名称：

  关于 C(sp3)–H σ-键的反应性：用甲基（三氟甲基）二环氧乙烷氧化

  摘要：

  一系列 2-取代金刚烷 2 的 C-H σ-键对甲基（三氟甲基）二环氧乙烷 (1) 的反应性显示出对取代基的吸电子能力的一致依赖性，无论是通过感应还是通过共振。结果被解释为底物分子在反应路径开始时使反应中心的电子扰动离域的能力。该模型表明，来自反应性 C-H σ 键的电子需求通过一系列超共轭相互作用沿基板传输，其相对强度取决于所涉及的 σ 键。底物分子同时向反应中心提供正负稳定超共轭相互作用，它们的平衡定义了反应路径开始时系统的几何形状。该模型构成了一种新的实验方法，用于测量由对相邻 C-H σ 键具有显着共振贡献的取代基引起的扰动。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  DOI：

  10.1002/ejoc.200700773
• 作为产物：
  描述：

  2-溴代金刚烷 在 silver nitrate 作用下， 以 乙醚 为溶剂， 生成 2-adamantyl nitrate
  参考文献：
  名称：

  Hyperconjugative Control by Remote Substituents of Diastereoselectivity in the Oxygenation of Hydrocarbons

  摘要：

  The oxidation of 2-substituted adamantanes (2) with TFDO (1) is reported. The data show a stereodifferentiation of the chemical environments induced by remote electron-withdrawing substituents which produces remarkable Z/E diastereoselectivity in the oxidation of the tertiary C-5-H and C-7-H bonds. The results show a bell-shaped correlation between the Z/E stereoselectivity and the substituent constant sigma(1), which is interpreted in terms of hyperconjugative stabilization of the diastereomeric transition states.

  DOI：

  10.1021/ol000017m

文献信息

• Photochemical oxidation and autoxidation of some cycloalkanes promoted by ceric ammonium nitrate in acetonitrile
  作者：Enrico Baciocchia、Tiziana Del Giacco、Giovanni Vittorio Sebastiani

  DOI：10.1016/s0040-4039(00)96015-5

  日期：1987.1

  The oxidation and autoxidation of adamantane, norbornane and cyclohexane can be photochemically promoted by ceric ammonium nitrate in acetonitrile at room temperature, both processes being extremely efficient and selective with adamantane.

  在室温下，硝酸铈铈铵在乙腈中可光化学促进金刚烷，降冰片烷和环己烷的氧化和自氧化，这两个过程均非常有效且对金刚烷具有选择性。
• Highly selective N- and O-functionalization of adamantane utilizing nitrogen oxides. Kyodai-nitration of aliphatic hydrocarbons
  作者：Hitomi Suzuki、Nobuaki Nonoyama

  DOI：10.1039/cc9960001783

  日期：——

  In the presence of ozone at –78 ° C, nitrogen dioxide selectively reacts rapidly with adamantane at the bridgehead position to give the corresponding nitration product, while in the presence of methanesulfonic acid at 0 °C, dinitrogen pentoxide readily reacts with this hydrocarbon at the same position exclusively to afford the corresponding nitrooxylation product, the yields of both products being quite satisfactory.

  在-78 °C的臭氧存在下，二氧化氮选择性地与桥头位置的金刚烷快速反应，生成相应的硝化产物，而在 0 °C 的甲磺酸存在下，五氧化二氮很容易与同一位置的碳氢化合物发生反应，生成相应的硝基氧化产物，两种产物的产量都相当令人满意。
• 1-Adamantyl chalcones for the treatment of proliferative disorders
  申请人：Anderson L. Gloria

  公开号：US20050065152A1

  公开（公告）日：2005-03-24

  The present invention relates to the compounds of the general formula (I), a composition for and a method of treating breast cancer or other proliferative disorders in a subject using a compound of general formula [I], wherein the substituents are as defined in the specification.

  本发明涉及通式(I)化合物、使用通式[I]化合物治疗乳腺癌或其他增殖性疾病的组合物和方法、 其中取代基如说明书中所定义。
• Oxidative Functionalization of Adamantane and Some of Its Derivatives in Solution
  作者：M. Mella、M. Freccero、T. Soldi、E. Fasani、A. Albini

  DOI：10.1021/jo951645y

  日期：1996.1.1

  1,2,4,5-Benzenetetracarbonitrile (TCB) is irradiated in the presence of adamantane (1) and some of its derivatives. The singlet excited state of TCB is a strong oxidant, and there is various evidence, including time-resolved spectroscopy, to prove that SET from the alkane to TCB1* takes place and yields the corresponding radical ions. The adamantane radical cation deprotonates from the bridgehead position, and the resulting radical couples with TCB-.. Deprotonation via the radical cation occurs with a number of substituted adamantanes and remains the exclusive or predominating reaction also with derivatives containing a potential electrofugal group, such as one of the following carbocations: t-Bu, CH(2)OMe, CH2OH (notable here is that C-H deprotonation is more efficient than O-H deprotonation). A carboxy group is lost more efficiently than a proton, however. In contrast, detaching of such cations is the main process when the radical cations of substituted adamantanes is produced anodically. This different behavior is explained on the basis of thermochemical calculation and of the different environments experienced by the radical cation in the two cases, viz reaction from the solvated radical cation in the first case and from the substrate adsorbed on the anode in the latter one. 1-Methoxyadamantane deprotonates from the methyl group, a reaction explained by the different structure of the radical cation. On the other hand, the radical NO3., conveniently produced by photolysis of cerium(IV) ammonium nitrate, reacts by hydrogen abstraction with selective attack at the bridgehead position and little interference by substituents and thus offers a useful way for the selective oxidative functionalization of adamantanes.
• Suzuki, Hitomi; Nonoyama, Nobuaki, Journal of the Chemical Society. Perkin transactions I, 1997, # 20, p. 2965 - 2971
  作者：Suzuki, Hitomi、Nonoyama, Nobuaki

  DOI：——

  日期：——