4,9-dihydroxydiamantane | 39646-84-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,9-dihydroxydiamantane
• 英文别名: diamantane-4,9-diol；diamantan-4,9-diol；MDT-14；pentacyclo[7.3.1.14,12.02,7.06,11]tetradecane-4,9-diol
• CAS: 39646-84-9
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: GXAHVKOYBPXTKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,9-dihydroxydiamantane 在 二乙胺基三氟化硫 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以94%的产率得到4,9-difluorodiamantane
  参考文献：
  名称：

  氟化类金刚石的选择性制备[1]

  摘要：

  Abstractmagnified imageThe selective fluorination of diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane bromides and alcohols was achieved by using the fluorinating agents silver fluoride (AgF) and diethylaminosulfur trifluoride (DAST). Various mono‐, di‐, tri‐ and even tetrafluorinated diamondoid derivatives were prepared and characterized. We were also able to prepare the amino fluoro and the fluoro alcohol derivatives of diamantane from the corresponding monoprotected diamondoid diols. These reactions can be carried out in a highly selective manner and proceed without isomerizations. The fluorinated, unequally disubstituted derivatives are valuable compounds for the exploration of electronic, pharmacological, and material properties of functionalized diamondoids.

  DOI：

  10.1002/adsc.200800787
• 作为产物：
  描述：

  双金刚烷 在 硫酸 作用下， 生成 4,9-dihydroxydiamantane
  参考文献：
  名称：

  金刚烷的化学。第一部分合成和一些官能化反应

  摘要：

  气相中的七环十四烷Binor-S的四氢衍生物在氯化氢中在氯化铂-氧化铝催化剂上于150°或在含氯化铝的二氯甲烷的溶液中重排，可以高产率得到金刚烷。已经开发了用于将金刚烷官能化的方法。用氯化铝-乙酰氯在0°氯化时，生成的等量的1-和4-氯二金刚烷（所谓的带状和顶端衍生物），而在–5°处使用氯磺酸，则主要生成1-氯-异构体。氯化物的水解产生相应的醇，其可通过氧化铝色谱分离。氯化物和醇可以分别用氯化铝和浓硫酸平衡。用96％的硫酸在75°下氧化金刚烷，生成金刚烷酮，9-羟基-氧金刚烷-3-酮和金刚烷-4,9-二醇。用70％硫酸处理二金刚烷-3-醇产生一元醇，9-羟基二金刚烷-3-酮，金刚烷-3，9-二醇和金刚烷-4，9-二醇的混合物。

  DOI：

  10.1039/p19720002691

文献信息

• Monoprotection of Diols as a Key Step for the Selective Synthesis of Unequally Disubstituted Diamondoids (Nanodiamonds)
  作者：Hartmut Schwertfeger、Christian Würtele、Michael Serafin、Heike Hausmann、Robert M. K. Carlson、Jeremy E. P. Dahl、Peter R. Schreiner

  DOI：10.1021/jo801321s

  日期：2008.10.3

  (desymmetrization) of diamondoid, benzylic, and ethynyl diols has been achieved using fluorinated alcohols such as 2,2,2-trifluoroethanol (TFE) under acidic conditions. This practical acid-catalyzed S(N)1 reaction opens the door for the synthesis of novel bifunctional diamondoids. With diamantane as an example, we show that the resulting monoethers can be used to prepare selectively, for instance, amino

  使用氟化醇（例如2,2,2-三氟乙醇（TFE））在酸性条件下已实现了类金刚石，苄基和乙炔基二醇的单保护（脱对称）。这种实用的酸催化S（N）1反应为合成新型双功能类金刚石打开了大门。以金刚烷为例，我们表明所得的单醚可用于选择性制备，例如氨基或硝基醇和非天然氨基酸。在探索功能化纳米金刚石的电子，药理和材料特性方面，这些是重要的化合物。
• 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)
• Diamondoid Nanostructures as sp ³ ‐Carbon‐Based Gas Sensors
  作者：Oana Moncea、Juan Casanova‐Chafer、Didier Poinsot、Lukas Ochmann、Clève D. Mboyi、Houssein O. Nasrallah、Eduard Llobet、Imen Makni、Molka El Atrous、Stéphane Brandès、Yoann Rousselin、Bruno Domenichini、Nicolas Nuns、Andrey A. Fokin、Peter R. Schreiner、Jean‐Cyrille Hierso

  DOI：10.1002/anie.201903089

  日期：2019.7.15

  Diamondoids, sp3‐hybridized nanometer‐sized diamond‐like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp3‐C‐based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO2 and NH3 gases. This carbon‐based gas sensor technology allows reversible

  类金刚石，sp 3杂交的纳米级类金刚石碳氢化合物（纳米金刚石），被羟基和伯膦氧化物基团双官能化，能够通过气相沉积组装第一个基于sp 3 c的化学传感器。原始纳米金刚石和钯纳米层复合材料均可用于检测有毒的NO 2和NH 3气体。这项基于碳的气体传感器技术可实现低至50 ppb的可逆NO 2和NH 3的检测在25–100 ppm浓度下进行检测，并在100°C时具有快速响应和恢复过程。可逆的气体吸附和检测与50％的湿度条件兼容。半导体p型感测特性是通过基于伯膦-金刚烷醇的设备实现的，该设备的高比面积（ca. 140 m 2  g -1）和通道纳米孔隙率源自H键合。
• 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。
• Selective Apical Bromination of Diamantane and Conversion to the Dihydroxy and Dicarboxylic Acid Derivatives
  作者：Matthew C. Davis、Shenggao Liu

  DOI：10.1080/00397910600943428

  日期：2006.11.1

  Abstract New conditions have been found that provide for the selective bromination of diamantane at the 4,9‐positions. Subsequent hydrolysis and Koch–Haaf reaction gave the 4,9‐dihydroxy‐ and 4,9‐dicarboxylic acid derivatives, respectively.

  摘要 已发现新条件可在 4,9 位选择性溴化金刚烷。随后的水解和 Koch-Haaf 反应分别得到 4,9-二羟基和 4,9-二羧酸衍生物。