N-<1-<3-(hydroxymethyl)>adamantyl>acetamide

• 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-(hydroxymethyl)>adamantyl>acetamide
• 英文别名: N-[3-(hydroxymethyl)adamantan-1-yl]acetamide；1-acetylamino-3-hydroxymethyladamantane；N-[3-(hydroxymethyl)-1-adamantyl]acetamide
• 化学式: C₁₃H₂₁NO₂
• 分子量: 223.315
• InChiKey: SJCXRNZCJBKIGB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-adamantylmethyl methyl ether 在 ammonium cerium(IV) nitrate 、 silica gel 作用下， 反应 4.0h， 生成 N-<1-<3-(hydroxymethyl)>adamantyl>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

• Nucleophilic Substitution Reactions of 1-Nitroxy-3-(nitroxymethyl)adamantanes
  作者：E. A. Ivleva、M. R. Khamzina、M. S. Zaborskaya、Yu. N. Klimochkin

  DOI：10.1134/s1070428022070065

  日期：2022.7

  Abstract A series of new polyfunctional cage compounds were synthesized by reactions of 1-nitroxy-3-(nitroxymethyl)adamantanes with nucleophiles in 100% sulfuric acid. The replacement of nitroxy group at the bridgehead position was accompanied by hydrolysis of the nitroxymethyl fragment.

  摘要 1-nitro-3-(nitrooxymethyl)金刚烷与亲核试剂在100%硫酸中反应合成了一系列新型多官能笼化合物。桥头位置的硝氧基基团的取代伴随着硝氧基甲基片段的水解。
• Adamantane derivative
  申请人：DAICEL CHEMICAL INDUSTRIES, LTD.

  公开号：EP1574494A1

  公开（公告）日：2005-09-14

  In the presence of an imide compound (e.g., N-hydroxyphthalimide) shown by the following formula (1):    wherein R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group and a cycloalkyl group, and R1 and R2 may bond together to form a double bond, or an aromatic or non-aromatic ring, and Y is an O or OH, and n denotes 1 to 3; a substrate is allowed to contact with at least one reactant selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen to be introduced with at least one functional group selected from a nitro group and a carboxyl group. The nitrogen oxide includes, for example, a compound represented by the formula NxOy (e.g., N2O3, NO2). The substrate includes, for example, a compound having a methine carbon atom (e.g., adamantane), a compound having a methyl group or a methylene group at an adjacent moiety of an aromatic ring. According to such reaction, the substrate can be efficiently nitrated or carboxylated even in a mild or moderate condition.

  在存在下式（1）所示的酰亚胺化合物（如 N-羟基邻苯二甲酰亚胺）的情况下： 其中 R1 和 R2 代表氢原子、卤素原子、烷基、芳基和环烷基，R1 和 R2 可键合在一起形成双键或芳香环或非芳香环，Y 是 O 或 OH，n 表示 1 至 3； 让基质与至少一种反应物接触，该反应物选自 (i) 氮氧化物和 (ii) 一氧化碳和氧的混合物，并引入至少一种选自硝基和羧基的官能团。例如，氮氧化物包括由式 NxOy 表示的化合物（如 N2O3、NO2）。底物包括例如具有甲基碳原子的化合物（如金刚烷）、在芳香环的相邻分子上具有甲基或亚甲基的化合物。根据这种反应，底物即使在温和或中等条件下也能被有效地硝化或羧化。
• Adamantane derivatives
  申请人：DAICEL CHEMICAL INDUSTRIES, LTD.

  公开号：EP1574495A1

  公开（公告）日：2005-09-14

  An adamantane derivative shown by the following formula (2):

  下式（2）所示的金刚烷衍生物：
• NITRATION OR CARBOXYLATION CATALYSTS
  申请人：DAICEL CHEMICAL INDUSTRIES, LTD.

  公开号：EP0897747B1

  公开（公告）日：2006-04-05
• US6468487B1
  申请人：——

  公开号：US6468487B1

  公开（公告）日：2002-10-22