N-<1-(3-cyanoadamantyl)>acetamide | 51314-15-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-<1-(3-cyanoadamantyl)>acetamide
• 英文别名: 1-Cyano-3-acetamidoadamantan；N-(3-cyano-1-adamantyl)acetamide
• CAS: 51314-15-9
• 化学式: C₁₃H₁₈N₂O
• 分子量: 218.299
• InChiKey: USKDHRAUCCMCMU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  52.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-氰基金刚烷 在 ammonium cerium(IV) nitrate 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以28%的产率得到N-<1-(3-cyanoadamantyl)>acetamide
  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

• A Facile and Efficient One-Pot Synthesis of Nitriles from Carboxylic Acids
  作者：Kata Mlinarić-Majerski、Renato Margeta、Jelena Veljković

  DOI：10.1055/s-2005-871967

  日期：——

  Direct transformation of aliphatic carboxylic acids to the corresponding nitriles can be easily performed with acetonitrile in the presence of sulfuric acid.

  在硫酸存在下，用乙腈可以很容易地将脂肪族羧酸直接转化为相应的腈。
• Selective Phthalimido-N-oxyl (PINO)-Catalyzed C–H Cyanation of Adamantane Derivatives
  作者：Jan-Philipp Berndt、Frederik Erb、Lukas Ochmann、Jaqueline Beppler、Peter Schreiner

  DOI：10.1055/s-0037-1610403

  日期：2019.3

  present a new method for the selective C(sp3)–H cyanation of adamantane derivatives with PINO as the hydrogen abstracting reagent. A cyano radical is thereby transferred from p -toluenesulfonyl cyanide, allowing the cyanation of adamantane derivatives in up to 71% yield. The protocol presents a novel way to orthogonally functionalized adamantanes that are otherwise difficult to prepare. Mechanistic studies

  我们提出了一种以 PINO 作为夺氢试剂对金刚烷衍生物进行选择性 C(sp3)-H 氰化的新方法。氰基由此从对甲苯磺酰氰转移，使金刚烷衍生物氰化的产率高达 71%。该协议提出了一种新的方法来正交功能化金刚烷，否则很难制备。机理研究支持激进途径的假设。
• Anodic chemistry of adamantyl compounds. Scissible carbon, halogen, hydrogen, and oxygen substituents
  作者：Victor R. Koch、Larry L. Miller

  DOI：10.1021/ja00807a022

  日期：1973.12