1,3-二氟金刚烷 | 54043-61-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 中文名称: 1,3-二氟金刚烷
• 英文名称: 1,3-difluoroadamantane
• 英文别名: 1,3-Difluoradamantan
• CAS: 54043-61-7
• 化学式: C₁₀H₁₄F₂
• 分子量: 172.218
• InChiKey: BWHJRYOYZZDMLO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-二氟金刚烷 在 (trimethylstannyl)lithium 、 碘代三甲硅烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 金刚烷
  参考文献：
  名称：

  Mechanistic definition of trimethylstannylation of 1,3-dihaloadamantanes: delocalized radical anions as possible intermediates

  摘要：

  A series of 1,3-dihaloadamantanes (3, X = Y = halogens) have been synthesized, characterized, and treated with (trimethylstannyl) alkali reagents (Me3SnM, M = Li or Na) in the absence and presence of tert-butylamine (TBA) and dicyclohexylphosphine (DCPH). The product distributions of these reactions have been established by C-13 and Sn-119 NMR spectroscopy and vapor-phase chromatographic analyses. Tin substitution via an S(RN)1-type pathway is shown to be a significant reaction for several of the derivatives of 3 (X = F, Y Br or I; X = Cl, Y = Br or I; X = Y = Br) but not for the bromo iodide or diiodide (3, X = Br, Y = I and X = Y = I). For the latter two compounds, the formation of 1,3-dehydroadamantane or propellane 8 is the predominant reaction product while tin substitution is insignificant. Propellane 8 formation is also a significant reaction product for some of the other dihalo derivatives of 3 (X = Cl, Y = I and X = Y = Br) but not for others (3, X = F, Y = Br or I and X = Cl, Y = Br). The mechanism of formation of 8 is perplexing in light of the trapping experiments in the presence of TBA and DCPH. A possible pathway is proposed in which the key intermediate is a delocalized radical anion.

  DOI：

  10.1021/jo00078a009
• 作为产物：
  描述：

  金刚烷 在 iodine pentafluoride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以75%的产率得到1,3-二氟金刚烷
  参考文献：
  名称：

  五氟化碘直接氟化金刚烷

  摘要：

  金刚烷的直接氟化是通过五氟化碘实现的，并在金刚烷的叔碳上选择性地引入一个或两个氟原子。

  DOI：

  10.1055/s-2008-1067205

文献信息

• Fluorination with caesium fluoroxysulphate. Part XI.
  作者：Stojan Stavber、Marko Zupan

  DOI：10.1016/s0040-4020(01)80103-4

  日期：1989.1

  Several hydrocarbons reacted with caesium fluoroxysulphate in acetonitrile at 35°C yielding mono and disubstituted products. Fluorocyclohexane, fluorocycloheptane, and 2-exo-fluoronorbornane formed in the reactions with the corresponding hydrocarbons were accompanied by up to 15% of other unidentified fluoro products, but their amount was strongly diminished when fluorination was performed in the presence

  几种碳氢化合物与氟代硫酸铯在乙腈中于35°C反应，生成单取代和二取代的产物。与相应的烃类反应生成的氟代环己烷，氟代环庚烷和2-exo-fluoronorbornane伴随着多达15％的其他未鉴定的氟代产物，但是当在硝基苯存在下进行氟化时，它们的数量大大减少了。金刚烷的氟化产生1-氟，2-氟和1,3-二氟取代的产物，其中叔碳原子上的取代强烈占优势。当反应在乙腈中进行时，硝基苯的存在不影响反应速率和产物分布，
• Preparation and carbon-13 NMR spectroscopic study of fluoroadamantanes and -diamantanes: study of carbon-13-fluorine-19 NMR coupling constants
  作者：George A. Olah、Joseph G. Shih、V. V. Krishnamurthy、Brij P. Singh

  DOI：10.1021/ja00328a032

  日期：1984.8

  Etude des deplacements chimiques et des valeurs de n J CF lors de l'addition de fluor a un squelette d'adamantane. Analyse en terme de nombre et type d'interaction gauche present dans le systeme

  Etude des deplacements chimiques et des valeurs de n J CF lors de l'addition de fluor a un scelette d'adamantane。分析 en terme de nombre et type d'interaction gauche present dans le systeme
• Thermically-Initiated Fluorinations at Saturated Carbon Atoms with Xenon Difluoride
  作者：Barbara Zajc、Marko Zupan

  DOI：10.1246/bcsj.59.1659

  日期：1986.5

  The heating of several hydrocarbons with xenon difluoride at 95–120 °C in stainless steel reactors equipped with teflon jackets resulted in mono-, di-, and trisubstituted products.

  在配备聚四氟乙烯夹套的不锈钢反应器中，用二氟化氙在 95-120 °C 下加热几种碳氢化合物，产生单、二和三取代的产物。
• Selective Fluorination of Adamantanes by an Electrochemical Method
  作者：Motoshi Aoyama、Tsuyoshi Fukuhara、Shoji Hara

  DOI：10.1021/jo8004759

  日期：2008.6.1

  Selective fluorination of adamantanes was achieved by the electrochemical fluorination method, using Et3N−5HF as electrolyte and a fluorine source. Mono-, di-, tri-, and tetrafluoroadamantanes were selectively prepared from adamantanes by controlling the oxidation potential, and the fluorine atoms were introduced selectively at the tertiary carbons. Adamantanes that have functional groups such as ester

  使用Et 3 N-5HF作为电解质和氟源，通过电化学氟化方法实现了金刚烷类的选择性氟化。通过控制氧化电位，从金刚烷选择性地制备单，二，三和四氟金刚烷，并将氟原子选择性地引入叔碳。具有官能团如酯，氰基和乙酰氧基甲基的金刚烷也被选择性氟化。
• Curable polycyclic compounds and process for the production thereof
  申请人：Takenaka Junji

  公开号：US20060252911A1

  公开（公告）日：2006-11-09

  The present invention discloses a curable polycyclic compound represented by the following formula (1): wherein A is a di- to hexa-valent group derived from a polycyclic hydrocarbon compound; R 1 is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; n is an integer of 0 to 2; m is an integer of 2 to 4; and Y is a group represented by the following formula (2) or (3): (wherein R 2 , R 3 , R 5 and R 6 are each independently a hydrogen atom, a fluorine atom or an alkyl group of 1 to 4 carbon atoms; R 4 is a methyl group or an ethyl group; and p and q are each independently an integer of 0 to 4)}.

  本发明披露了一种可固化的多环化合物，其表示如下式（1）：其中A是从多环碳氢化合物衍生的二至六价基团；R1是1至4个碳原子的烷基、1至4个碳原子的全氟烷基或氟原子；n是0至2的整数；m是2至4的整数；Y是以下式（2）或（3）所表示的基团：（其中R2，R3，R5和R6各自独立地是氢原子、氟原子或1至4个碳原子的烷基；R4是甲基或乙基基团；p和q各自独立地是0至4的整数）。