3-fluoroadamantan-1-ol | 58652-35-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-fluoroadamantan-1-ol
• CAS: 58652-35-0
• 化学式: C₁₀H₁₅FO
• 分子量: 170.227
• InChiKey: IKFPOBOOYIGIDD-UHFFFAOYSA-N

物化性质

• 熔点：
  174 °C(bomb tube)
• 沸点：
  237.8±23.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-fluoroadamantan-1-ol 在 氢碘酸 作用下， 以 正己烷 、 苯 为溶剂， 反应 84.0h， 生成 3-iodoadamantan-1-ol
  参考文献：
  名称：

  Transmission of polar substituent effects in saturated systems: synthesis and fluorine-19 NMR study of 3-substituted adamant-1-yl fluorides

  摘要：

  DOI：

  10.1021/jo00379a008
• 作为产物：
  描述：

  1-金刚烷醇 在 乙酸乙酯 、 N-氟代双苯磺酰胺 作用下， 反应 2.0h， 以37.9%的产率得到3-fluoroadamantan-1-ol
  参考文献：
  名称：

  未活化 C(sp3)-H 键的机械化学直接氟化

  摘要：

  使用N-氟苯磺酰亚胺作为氢原子转移试剂的前体和稳定的氟源，实现了未活化的 C( sp 3 )-H 键的机械化学氟化。对照实验表明，机械能对于实现这一反应至关重要。

  DOI：

  10.1002/adsc.202200206

文献信息

• Chemical process
  申请人：Research Institute for Medicine and Chemistry Inc.

  公开号：US04036864A1

  公开（公告）日：1977-07-19

  Saturated organic compounds containing a hydrogen atom bound to a tertiary carbon atom may be electrophilically fluorinated by reaction with an electrophilic fluorinating agent such as molecular fluorine or trifluoromethyl hypofluorite under conditions whereby the formation of free fluorine radicals is suppressed, e.g. by the presence of a free radical inhibitor such as oxygen or nitrobenzene, the reactants being substantially homogeneously dispersed in a liquid medium, e.g. a solvent medium such as fluorotrichloromethane or chloroform/fluorotrichloromethane, so that the said hydrogen atom is electrophilically replaced by a fluorine atom. The fluoroination is highly selective and, in the case of complex substrates such as saturated steroids which contain a number of tertiary C--H bonds, may be substantially completely confined to replacement of the hydrogen atom at the tertiary carbon atom which has the highest electron density about the C--H bond. The electron density and thus the direction of the fluorination may be controlled by appropriate selection of substituent groupings in the substrate molecule. Novel 14.alpha.-fluorosteroids are also disclosed, including compounds having valuable androgenic or progestational activity and useful synthetic intermediates.

  含有氢原子与三级碳原子相结合的饱和有机化合物可以通过与亲电性氟化试剂反应来进行亲电性氟化，例如与分子氟或三氟甲基次氟酸盐反应，在抑制自由氟自由基形成的条件下，例如通过存在自由基抑制剂如氧气或硝基苯，使得反应物在液体介质中基本均匀分散，例如在溶剂介质中如氟三氯甲烷或氯仿/氟三氯甲烷中，从而使得该氢原子被氟原子亲电性取代。氟化反应具有高度选择性，在饱和类固醇等复杂底物的情况下，可以基本完全限制在替换具有最高电子密度的三级碳原子上的氢原子。通过适当选择底物分子中的取代基团，可以控制电子密度和因此氟化的方向。该文还公开了新型14α-氟类固醇，包括具有有价值的雄激素或孕激素活性以及有用的合成中间体的化合物。
• Visible-Light-Induced Decarboxylative Fluorination of Aliphatic Carboxylic Acids Catalyzed by Iron
  作者：Yu Zhang、Jiahui Qian、Miao Wang、Yahao Huang、Peng Hu

  DOI：10.1021/acs.orglett.2c02242

  日期：2022.8.19

  An efficient and inexpensive protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed with iron salts under visible light is presented. This new method allows the facile fluorination of a diverse array of carboxylic acids even on gram scale using a Schlenk flask without loss of efficiency. Mechanistic studies suggest that the photoinduced ligand-to-metal charge transfer

  提出了一种在可见光下用铁盐催化脂肪族羧酸直接脱羧氟化的有效且廉价的方案。这种新方法允许使用 Schlenk 烧瓶对多种羧酸进行轻松氟化，即使在克规模上也不会降低效率。机理研究表明，光诱导配体-金属电荷转移过程能够产生生成羧基自由基中间体的关键步骤。
• Using Mechanochemistry to Activate Commodity Plastics as Initiators for Radical Chain Reactions of Small Organic Molecules
  作者：Koji Kubota、Julong Jiang、Yuri Kamakura、Reon Hisazumi、Tsubura Endo、Daiyo Miura、Shotaro Kubo、Satoshi Maeda、Hajime Ito

  DOI：10.1021/jacs.3c12049

  日期：2024.1.10

  conditions. We postulated that a more convenient and safer alternative for radical chain initiation could be developed by mechanical activation of thermodynamically stable covalent bonds. Here, we show that commodity plastics such as polyethylene and poly(vinyl acetate) are capable of acting as efficient initiators for radical chain reactions under solvent-free mechanochemical conditions. In this approach, polymeric

  偶氮化合物和有机过氧化物等自由基引发剂已被广泛用于促进自由基的多种转化，从而能够有效合成结构复杂的分子、天然产物、聚合物和功能材料。然而，这些高能试剂具有潜在的爆炸性，因此通常需要特殊的预防措施或微妙的操作条件。我们假设可以通过热力学稳定共价键的机械活化来开发一种更方便、更安全的自由基链引发替代方案。在这里，我们表明，聚乙烯和聚乙酸乙烯酯等商品塑料能够在无溶剂机械化学条件下充当自由基链反应的有效引发剂。在这种方法中，通过球磨提供的机械能使聚合物链均裂而产生的聚合物机械自由基与三(三甲基甲硅烷基)硅烷反应，引发有机卤化物的自由基链脱卤。初步计算支持我们提出的力诱导自由基链机制。
• Metal-Free Fluorination of C(sp³)–H Bonds Using a Catalytic <i>N</i>-Oxyl Radical
  作者：Yuuki Amaoka、Masanori Nagatomo、Masayuki Inoue

  DOI：10.1021/ol4006757

  日期：2013.5.3

  A direct conversion of C(sp(3))-H bonds to C(sp(3))-F bonds has been developed. In this process, a catalytic N-oxyl radical generated from N,N-dihydroxypyromellitimide abstracts hydrogen from the C(sp(3))-H bond and Selectfluor acts to trap the resulting carbon radical to form the C(sp(3))-F bond. This simple metal-free protocol enables the chemoselective introduction of a fluorine atom into various aromatic and aliphatic compounds and serves as a powerful tool for the efficient synthesis of fluorinated molecules.
• Triethylborane-Initiated Radical Chain Fluorination: A Synthetic Method Derived from Mechanistic Insight
  作者：Cody Ross Pitts、Bill Ling、Ryan Woltornist、Ran Liu、Thomas Lectka

  DOI：10.1021/jo501520e

  日期：2014.9.19

  We offer a mild, metal-free sp(3) C-H fluorination alternative using Selectfluor and a substoichiometric amount of triethylborane--an established radical initiator in the presence of O2. This radical-chain-based synthetic method is particularly noteworthy as an offspring of the insight gained from a mechanistic study of copper-promoted aliphatic fluorination, constructively turning O2 from an enemy to an ally. Furthermore, BEt3/O2 is a preferred initiator in industrial processes, as it is economical, is low in toxicity, and lends way to easier workup.