4-acetoxy-9-(2,2,2-trifluoroethoxy)-diamantane | 1058167-69-3

• 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: 4-acetoxy-9-(2,2,2-trifluoroethoxy)-diamantane
• CAS: 1058167-69-3
• 化学式: C₁₈H₂₃F₃O₃
• 分子量: 344.374
• InChiKey: CODLNWYBSAFUKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-acetoxy-9-(2,2,2-trifluoroethoxy)-diamantane 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 0.83h， 以63%的产率得到4-acetoxy-9-bromodiamantane
  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：

  9-(2,2,2-trifluoroethoxy)-diamantan-4-ol 、 乙酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以94%的产率得到4-acetoxy-9-(2,2,2-trifluoroethoxy)-diamantane
  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

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。
• MONOETHERIFIED DIOLS OF DIAMONDOIDS
  申请人：Schreiner Peter R.

  公开号：US20110124912A1

  公开（公告）日：2011-05-26

  The invention at hand describes functionalized diols of diamondoids, in which one of the two hydroxy groups is masked by a protective group, as well as methods for producing these functionalized diols. The protective group is a group —CHR 1 R 2 , wherein R 1 and R 2 stand for alkyl groups and the protective group comprises at least one halogen atom. The monoethers of the diamondoid diols according to the present invention are produced by reacting the diamondoid diol with a halogenated alcohol CHOHR 1 R 2 in the presence of a catalyst acid. The monoetherified diols allow for the targeted production of derivatives of diamondoids, for example, of the corresponding aminoalcohols and aminocarboxylic acids. For that purpose, the diamondoid monoether is reacted in a first step with a halogen nitrile in a Ritter reaction to the corresponding monoether amide. From this monoether amide, the corresponding aminoalcohol can be produced by reacting the protective group —CHR 1 R 2 first with trifluoroacetic acid to the alkanoyloxy group and by subsequently obtaining the aminoalcohol by reaction with thiourea, ethanol and glacial acetic acid. The aminoalcohol can be reacted with a sulfuric acid/formic acid or oleum/formic acid to the corresponding aminocarboxylic acid. The amino, hydroxy and carboxylic groups of the diamondoids can be converted into many other functional groups.

  这项发明描述了钻石烷的官能化二元醇，其中两个羟基中的一个被保护基掩盖，以及制备这些官能化二元醇的方法。保护基是一个基团—CHR1R2，其中R1和R2代表烷基，保护基包含至少一个卤素原子。根据本发明，钻石烷二元醇的单醚是通过在催化酸的存在下将钻石烷二元醇与卤代醇CHOHR1R2反应而制备的。单醚化的二元醇允许有针对性地生产钻石烷的衍生物，例如相应的氨基醇和氨基羧酸。为此，首先将钻石烷单醚与卤代腈在里特反应中反应得到相应的单醚酰胺。从这个单醚酰胺中，通过将保护基—CHR1R2先与三氟乙酸反应成烷酰氧基，然后通过与硫脲、乙醇和冰醋酸反应获得氨基醇。氨基醇可以与硫酸/甲酸或油酸/甲酸反应成相应的氨基羧酸。钻石烷的氨基、羟基和羧基可以转化为许多其他官能团。