N-<1-(3-tert-butyladamantyl)>acetamide | 60931-66-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 甲亚胺酸及其衍生物
• 英文名称: N-<1-(3-tert-butyladamantyl)>acetamide
• 英文别名: N-(3-t-butyl-1-adamantyl)acetamide；1-Acetamido-3-t-butyladamantan；N-(3-tert-butyl-1-adamantyl)acetamide
• CAS: 60931-66-0
• 化学式: C₁₆H₂₇NO
• 分子量: 249.396
• InChiKey: NLGVKTJZWRQBBL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  29.1
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  1-tert-Butyladamantan 在 ammonium cerium(IV) nitrate 作用下， 以 乙腈 为溶剂， 反应 4.0h， 生成 N-<1-(3-tert-butyladamantyl)>acetamide 、 3-t-butyl-1-adamantyl nitrate
  参考文献：
  名称：

  Oxidative Functionalization of Adamantane and Some of Its Derivatives in Solution

  摘要：

  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.

  DOI：

  10.1021/jo951645y

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。
• 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.