1,4-dinitroxydiamantane

• 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: 1,4-dinitroxydiamantane
• 英文别名: (1-Nitrooxy-4-pentacyclo[7.3.1.14,12.02,7.06,11]tetradecanyl) nitrate
• 化学式: C₁₄H₁₈N₂O₆
• 分子量: 310.307
• InChiKey: QTNKQOLOGFUZTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  7.0
• 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：

  1,4-dinitroxydiamantane 在 水 作用下， 以32%的产率得到diamantane-1,4-diol
  参考文献：
  名称：

  硝酸介质中二金刚烷衍生物的合成

  摘要：

  摘要 通过使金刚烷与硝酸或HNO 3 -AcOH混合物反应，然后添加含氮亲核试剂，可以合成1-单-和1,4-双官能金刚烷衍生物。由2-金刚烷-1-醇和硫氰酸甲酯在硫酸中合成了N-（二金刚烷-1-基）氨基甲磺酸甲酯。

  DOI：

  10.1134/s1070428021020081
• 作为产物：
  描述：

  双金刚烷 在 硝酸 作用下， 反应 24.0h， 生成 1,4-dinitroxydiamantane
  参考文献：
  名称：

  硝酸介质中二金刚烷衍生物的合成

  摘要：

  摘要 通过使金刚烷与硝酸或HNO 3 -AcOH混合物反应，然后添加含氮亲核试剂，可以合成1-单-和1,4-双官能金刚烷衍生物。由2-金刚烷-1-醇和硫氰酸甲酯在硫酸中合成了N-（二金刚烷-1-基）氨基甲磺酸甲酯。

  DOI：

  10.1134/s1070428021020081

文献信息

• Hydroxy Derivatives of Diamantane, Triamantane, and [121]Tetramantane: Selective Preparation of Bis-Apical Derivatives
  作者：Natalie A. Fokina、Boryslav A. Tkachenko、Anika Merz、Michael Serafin、Jeremy E. P. Dahl、Robert M. K. Carlson、Andrey A. Fokin、Peter R. Schreiner

  DOI：10.1002/ejoc.200700378

  日期：2007.10

  Functionalizations of diamantane, triamantane, and tetramantane with electrophilic reagents (Br2, nitric acid) lead to various apical and medial disubstituted products that were separated and characterized individually. The highly desirable and otherwise inaccessible thermodynamically more stable apical bis-derivatives were obtained with high preparative yields through acid catalyzed isomerizations

  使用亲电试剂（Br2、硝酸）对金刚烷、三金刚烷和四金刚烷进行官能化会产生各种顶端和中间双取代产物，这些产物被单独分离和表征。通过酸催化异构化以高制备产率获得了非常理想的和否则无法获得的热力学更稳定的顶端双衍生物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Method for Producing Substituted Diamantanes
  申请人：Schreiner Peter R.

  公开号：US20100036153A1

  公开（公告）日：2010-02-11

  The invention at hand provides at least dinitroxylated diamantanes. In addition, it provides methods for producing substituted diamantanes with high yields and selectivity. According to the invention, dinitroxylated diamantanes are suitable for being reacted with nucleophiles to form the corresponding disubstituted diamantanes. Surprisingly, it was discovered that at least dinitroxylated or hydroxylated diamantanes are rearranged in the presence of a strong acid, creating at least 4,9-nitroxylated or hydroxylated diamantanes. On the basis of this, 4,9-substituted diamantanes are able to be produced in a targeted manner by reaction with further nucleophiles. Thus, the invention at hand provides the following methods according to the present invention for producing at least disubstituted diamantanes: a) at least dinitroxylation, followed by the substitution of all nitroxy groups by a nucleophile or b) at least dinitroxylation, subsequent rearrangement in the presence of a strong acid, after realised rearrangement all nitroxy groups are replaced by a nucleophile or c) at least dinitroxylation, subsequent reaction with water (as nucleophile), rearrangement of the at least dihydroxylated compound in the presence of a strong acid, after realised rearrangement all hydroxy groups are replaced by another nucleophile.

  该发明提供至少二硝基化二莽烷。此外，它提供了一种高产率和选择性生产取代二莽烷的方法。根据该发明，二硝基化的二莽烷适合与亲核试剂反应，形成相应的二取代二莽烷。令人惊讶的是，在强酸存在的情况下发现，至少二硝基化或羟基化的二莽烷会重排，形成至少4,9-硝基化或羟基化的二莽烷。基于此，通过与进一步的亲核试剂反应，可以有针对性地生产4,9-取代的二莽烷。因此，该发明提供了以下根据本发明的方法，用于生产至少二取代的二莽烷：a) 至少二硝基化，然后用亲核试剂替换所有硝基团或b) 至少二硝基化，后在强酸存在下重排，重排后用亲核试剂替换所有硝基团或c) 至少二硝基化，后与水（作为亲核试剂）反应，在强酸存在下重排，重排后用另一亲核试剂替换所有羟基。
• US8716539B2
  申请人：——

  公开号：US8716539B2

  公开（公告）日：2014-05-06
• Synthesis of Diamantane Derivatives in Nitric Acid Media
  作者：Yu. N. Klimochkin、E. A. Ivleva、M. S. Zaborskaya

  DOI：10.1134/s1070428021020081

  日期：2021.2

  Abstract 1-Mono- and 1,4-difunctional diamantane derivatives were synthesized by the reaction of diamantane with nitric acid or a HNO3–AcOH mixture followed by the addition of nitrogen-containing nucleophiles. Methyl N-(diamantan-1-yl)carbamothioate was synthesized from diamantan-1-ol and methyl thiocyanate in sulfuric acid.

  摘要 通过使金刚烷与硝酸或HNO 3 -AcOH混合物反应，然后添加含氮亲核试剂，可以合成1-单-和1,4-双官能金刚烷衍生物。由2-金刚烷-1-醇和硫氰酸甲酯在硫酸中合成了N-（二金刚烷-1-基）氨基甲磺酸甲酯。