1-nitroxy-3-(nitroxymethyl)adamantane | 157774-23-7

• 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: 1-nitroxy-3-(nitroxymethyl)adamantane
• 英文别名: (3-nitrooxy-1-adamantyl)methyl nitrate
• CAS: 157774-23-7
• 化学式: C₁₁H₁₆N₂O₆
• 分子量: 272.258
• InChiKey: DYVWPKPLLGAYNZ-UHFFFAOYSA-N

物化性质

• 熔点：
  62-64 °C
• 沸点：
  361.9±11.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-nitroxy-3-(nitroxymethyl)adamantane 在 硝酸 、 溶剂黄146 作用下， 反应 5.0h， 以84%的产率得到3-nitroxymethyl-1-adamantanol
  参考文献：
  名称：

  Klimochkin, Yu. N.; Zhilkina, E. O.; Abramov, O. V., Russian Journal of Organic Chemistry, 1993, vol. 29, # 7.1, p. 1126 - 1131

  摘要：

  DOI：
• 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 1-nitroxy-3-(nitroxymethyl)adamantane
  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

• Synthesis of (3-Hydroxyadamantan-1-yl)methanols
  作者：E. A. Ivleva、A. V. Pogulyaiko、Yu. N. Klimochkin

  DOI：10.1134/s107042801809004x

  日期：2018.9

  of adamantan-1-ylmethanols with fuming nitring acid and subsequent reduction of intermediate nitric acid esters with hydrazine hydrate. The title diols have also been obtained by the reduction of 1-nitroxy-3-(nitroxymethyl)adamantanes. The nitroxylation process is accompanied by oxidation with the formation of substituted adamantane-1-carboxylic acids.

  已经开发了一种便利的方法，用于以烟酰胺硝化酸将金刚烷-1-基甲醇硝化并随后用水合肼还原中间体硝酸酯来合成（3-羟基金刚烷-1-基）-甲醇。通过还原1-硝基-3-（硝基甲基）金刚烷也获得了标题二醇。硝基氧化过程伴随着氧化，形成取代的金刚烷-1-羧酸。
• 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。