1-fluoroazulene | 67949-59-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-fluoroazulene
• 英文别名: 2-fluoroazulene
• CAS: 67949-59-1
• 化学式: C₁₀H₇F
• 分子量: 146.164
• InChiKey: LRBRLOWDPFYOMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-fluoroazulene 在 二异丁基氢化铝 、 三氯氧磷 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 14.0h， 生成 1-氟-3-甲基薁
  参考文献：
  名称：

  氟芴的合成与性质。二、用 N-氟试剂亲电氟化 Azulenes

  摘要：

  1-氟-和1,3-二氟-和1,3-二氟-和1-二氟-和1,3-二氟- azulenes 是第一次通过用N-氟试剂对azulenes 进行亲电氟化来合成。1-氟丁烯的选择性制备是通过甲基 azulene-1-carboxylates 的氟化，然后在 100% H3PO4 中脱甲氧基羰基化来进行的。2-取代的芘以更高的产率被氟化。在 1-氟芴的 1H NMR 中，与 1-氟萘相比，在 H-2 和 H-8 处未观察到长程 JFH 值。由于所谓的 +Iπ 效应，1-氟原子会导致薁的可见光吸收发生显着的红移。

  DOI：

  10.1246/bcsj.69.1645
• 作为产物：
  描述：

  奥苷菊环 在 二氟代氙 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以22%的产率得到1-fluoroazulene
  参考文献：
  名称：

  Synthesis and N.M.R. Study of 1-, 4-, 5- and 6-Fluoroazulenes

  摘要：

  介绍了五种可能的氟偶氮烯中四种的制备方法。其 19F 化学位移与相关的 芳香系统的化学位移进行了比较。1H 和 13C n.m.r. 光谱是根据 19F/13C 耦合和 1H/13C 相关性。问题 概述了尝试合成 2-氟唑烯过程中出现的问题。

  DOI：

  10.1071/c97142

文献信息

• The First Synthesis of 1-Fluoro- and 1,3-Difluoroazulenes
  作者：Tetsuya Ueno、Haruhiko Toda、Masafumi Yasunami、Masaaki Yoshifuji

  DOI：10.1246/cl.1995.169

  日期：1995.3

  1-Fluoro- and 1,3-difluoroazulenes were synthesized by the reaction of azulene with N-fluoropyridinium salts in acetonitrile. Methyl azulene-1-carboxylates were also fluorinated to give the corresponding 3-fluoro derivatives. On the basis of the UV-visible absorption spectra, the fluorine atom acts as an electron-donating group to the azulene π-system due to the +Iπ effect.

  通过将蒽烯与N-氟吡啶盐在乙腈中反应，合成了1-氟和1,3-二氟蒽烯。同时，甲基蒽烯-1-羧酸酯也经历了氟化反应，生成相应的3-氟衍生物。根据紫外-可见吸收光谱分析，氟原子由于+Iπ效应，作为电子给体作用于蒽烯的π体系。
• Formation of Azulenequinone Derivatives from Variously Functionalized Azulenes by Bromine-oxidation
  作者：Paw-Wang Yang、Jhy-An Chen、Hidetsugu Wakabayashi、Kimio Shindo、Teruo Kurihara、Chi-Phi Wu、Masafumi Yasunami、The Late Tetsuo Nozoe

  DOI：10.1002/jccs.199700002

  日期：1997.2

  AbstractVariously functionalized 1,5‐ and 1,7‐azulenequinones were easily derived in one‐pot in 30‐50% yield from the bromine‐oxidation of 2‐methoxyazulene and 2‐methyl derivatives of 1‐cyano‐, 1‐methoxycarbonyl‐ and its 7‐isopropyl derivatives, while 1‐methoxycarbonylazulene afforded several unstable products from which we could not isolate any azulenequinones. 1‐Acetylazulene afforded 3‐bromo‐1,5‐ and ‐1,7‐azulenequinones via side‐chain brominated intermediates in high yield. 1,3‐Dichloroazulene afforded a mixture of 3‐chloro‐1,5‐ and −1,7‐azulenequinones, while 1‐fluoro‐ and 1,3‐diiodoazulene gave a mixture of 3‐bromoazulenequinones. Analogous oxidation of 1,3‐difluoroazulene produced 3‐fluoroazulenequinones, but we could not isolate them due to its instability. Hydroxy group of 2‐(3‐hydroxypropyl)azulene was intact during this quinone formation reaction.
• Facile one-pot fluorination of polycyclic aromatic hydrocarbons (PAHs) with N-fluoro-2,4-dinitroimidazole; scope and limitation
  作者：Kenneth K. Laali、Mutsuo Tanaka、Farhad Forohar、Michael Cheng、John C. Fetzer

  DOI：10.1016/s0022-1139(98)00224-3

  日期：1998.9

  The synthetic utility of N-fluoro-2,4-dinitro-imidazole 'NF-2,4-DNI', a recently introduced NF fluorinating agent, has been tested for direct one-pot fluorination of several classes of polycyclic aromatic hydrocarbons, PAHs, namely pyrene, crowded alkyl(cycloalkyl)-pyrenes; hexahydro- and tetrahydro-pyrene; benzo[a] anthracene; benzo[a]- and benzo[e]pyrene; perylene; 2,7-di-tert-butylphenanthrene; chrysene; 9-methylanthracene and anthracene, as well as trans-15, 16-dimethyl-dihydropyrene; azuleno[1,2-a] acenaphthylene and azulene. Although the isolated yields are modest, the ease of handling of the reagent, simple operation (reflux in dichloroethane for 3 days) and the use of 1.1 equivalent of the reagent makes the procedure quite attractive for polynuclear aromatics, avoiding multi-step operations (NO2-PAH-->NH2-PAH-->N-2(+)-PAH-->F-PAH) or the use of toxic or costly reagents (CF3OF, XeF2, etc.); it provides direct one-pot access to a variety of F-PAHs that are not readily made using other fluorinating agents. (C) 1998 Elsevier Science S.A. All rights reserved.
• Synthesis and Reactivities of 1,5- and 1,7-Azulenequinone Derivatives. A Highly Convenient, One-Pot Synthesis of 3-Bromo-1,5- and −1,7-Azulenequinones by Bromination of Azulene,
  作者：Hidetsugu Wakabayashi、Teruo Kurihara、Kimio Shindo、Masaaki Tsukada、Paw-Wang Yang、Masafumi Yasunami、Tetsuo Nozoe

  DOI：10.1002/jccs.199800062

  日期：1998.6

  AbstractA very convenient, one‐pot synthesis (over 80% yield) of 3‐bromo‐1,5‐ and −1,7‐azulenequinones has been developed by bromination of azulene in aqueous tetrahydrofuran. Reduction of 3‐bromo‐1,5‐ and −1,7‐azulenequinones with tin or zinc powder in acetic acid gave the parent 1,5‐ and 1,7‐azulenequinones, and further reduction products.
• Synthesis and Properties of Fluoroazulenes. II. Electrophilic Fluorination of Azulenes with<i>N</i>-Fluoro Reagents
  作者：Tetsuya Ueno、Haruhiko Toda、Masafumi Yasunami、Masaaki Yoshifuji

  DOI：10.1246/bcsj.69.1645

  日期：1996.6

  3-difluoroazulenes were synthesized for the first time by the electrophilic fluorination of azulenes with N-fluoro reagents. Selective preparation of 1-fluoroazulenes were performed by the fluorination of methyl azulene-1-carboxylates, followed by demethoxycarbonylation in 100% H3PO4. 2-Substituted azulenes were fluorinated in higher yields. In the 1H NMR of 1-fluoroazulene, long-range JFH values were

  1-氟-和1,3-二氟-和1,3-二氟-和1-二氟-和1,3-二氟- azulenes 是第一次通过用N-氟试剂对azulenes 进行亲电氟化来合成。1-氟丁烯的选择性制备是通过甲基 azulene-1-carboxylates 的氟化，然后在 100% H3PO4 中脱甲氧基羰基化来进行的。2-取代的芘以更高的产率被氟化。在 1-氟芴的 1H NMR 中，与 1-氟萘相比，在 H-2 和 H-8 处未观察到长程 JFH 值。由于所谓的 +Iπ 效应，1-氟原子会导致薁的可见光吸收发生显着的红移。

表征谱图