1-fluorooctadecane | 1649-73-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: 1-fluorooctadecane
• 英文别名: 1-fluoro-octadecane；1-Fluor-octadecan
• CAS: 1649-73-6
• 化学式: C₁₈H₃₇F
• 分子量: 272.49
• InChiKey: PVQXITGZQAYAAL-UHFFFAOYSA-N

物化性质

• 熔点：
  29°C
• 沸点：
  357.41°C (rough estimate)
• 密度：
  0.8620 (estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  19
• 可旋转键数：
  16
• 环数：
  0.0
• 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：
  1

反应信息

• 作为反应物：
  描述：

  1-fluorooctadecane 在 potassium dihydrogenphosphate 、 一水合硫酸镁 、 盐酸硫胺 、 monosodium glutamate 作用下， 以 aq. phosphate buffer 、 十二烷 为溶剂， 以37 %的产率得到oleyl fluoride
  参考文献：
  名称：

  直链烷烃的选择性末端官能化**

  摘要：

  据报道，一种两步序贯策略，涉及生物催化脱氢/远程加氢官能化作为一种​​统一且通用的方法，选择性地将直链烷烃转化为大量有价值的官能化脂肪族衍生物。该反应在直链烷烃的非反应性伯 CH 键处进行位点选择性官能化，并避免使用直链 α-烯烃。

  DOI：

  10.1002/anie.202306343
• 作为产物：
  描述：

  4-氯苯磺酸十八烷基酯 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 1-fluorooctadecane
  参考文献：
  名称：

  无水四丁基氟化铵

  摘要：

  四丁基氟化铵 (TBAF) 是通过六氟苯与氰化四丁基铵的亲核芳香取代在低温下制备的。在此合成过程中，外来水被生成的六氰基苯清除，在碱性条件下很容易加水。与预期相反，TBAF 在无水条件下在极性非质子溶剂中对霍夫曼消除是稳定的。添加的羟基溶剂显示出催化 TBAF 的分解并催化与 DMSO 的质子交换。简要描述了这种盐的合成用途。

  DOI：

  10.1021/ja0440497

文献信息

• Tetrabutylammonium biflouride: A versatile and efficient flourinating agent
  作者：Pilar Bosch、Francisco Camps、Esther Chamorro、Vicens Gasol、Angel Guerrero

  DOI：10.1016/s0040-4039(00)96612-7

  日期：1987.1

  The use of tetrabutylammonium, biflouride as stable and easily available source of flouride ion in nucleophilic substitution process with different substrates is reported.

  据报道，在不同底物的亲核取代过程中，四氟二丁基铵，氟化二氟醚作为稳定和易于获得的氟化物离子来源已得到报道。
• Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydrofunctionalization and Formal Retro-hydrofunctionalization
  作者：Steven Hanna、Trevor W. Butcher、John F. Hartwig

  DOI：10.1021/acs.orglett.9b02695

  日期：2019.9.6

  We report a contra-thermodynamic isomerization of internal olefins to terminal olefins driven by redox reactions and formation of Si-F bonds. This process involves chain-walking hydrosilylation of internal olefins and subsequent formal retro-hydrosilylation. The process rests upon the high activities of platinum hydrosilylation catalysts for isomerization of metal alkyl intermediates and a new, metal-free

  我们报告了由还原反应和形成Si-F键驱动的内部烯烃对末端烯烃的反热力学异构化。该过程涉及内部烯烃的链走氢化硅烷化和随后的正式逆向氢化硅烷化。该方法取决于铂氢化硅烷化催化剂对金属烷基中间体的异构化的高活性，以及​​基于烷基硅烷向烯烃转化的无金属新方法。通过这种方法，将1,2-二取代和三取代的烯烃转化为末端烯烃。
• Fluorination of Secondary and Primary Alcohols by Thermal Decomposition of Electrochemically Generated Alkoxy Triphenylphosphonium Tetrafluoroborates.
  作者：Hatsuo MAEDA、Takashi KOIDE、Sayaka MATSUMOTO、Hidenobu OHMORI

  DOI：10.1248/cpb.44.1480

  日期：——

  Replacement of hydroxyl groups in secondary and primary alcohols (1) with a fluorine atom arising from tetrafluorobote anion has been performed by the electrochemical formation of alkoxy triphenylphosphonium tetrafluoroborarates (2) from 1, followed by their thermal decomposition. The procedure is quite simple, involving : (1) constant-current electrolysis of a mixture of 1, Ph3P, and Ph3PH·BF4 in CH2Cl2 in an undivided cell; (2) refluxing a tetrahydrofuran or dioxane solution of the residue afforded by evaporation of the solvent in vacuo after the electrolysis. Cyclic secondary alcohols such as 3β-hydroxy steroids and 2-adamantanol are transformed into the corresponding fluorides in satisfactory yields when the geometry of the leaving group in 2 is suitable for the substitution or an elimination process for 2 to give an alkene is stereochemically forbidden. The fluorination of steroidal alcohols and 4-phenyl-1-cyclohexanol proceeded with complete inversion, demonstrating that a fluorine atom from the tetrafluoroborate anion attacks from the side opposite to the phosphonium moiety in 2 via an SN2 mechanism rather than as SN1 mechanism. The fluorination of acyclic secondary and primary alcohols was performed by the present method in reasonable yields, although the reaction for the latter required more forcing conditions, such as refluxing in dioxane.

  次级和初级醇(1)中的羟基被四氟硼酸根衍生的氟原子取代，通过电化学形成烷氧基三苯基膦四氟硼酸盐(2)，然后进行热分解来实现。该过程相当简单，包括：(1)在无隔膜电池中对1、Ph3P和Ph3PH·BF4的CH2Cl2混合物进行恒电流电解；(2)将电解后在真空下蒸发溶剂得到的残渣的四氢呋喃或二氧六环溶液回流。当2中的离去基团的构型适合取代或消除过程，且2生成烯烃的立体化学被禁止时，环状次级醇如3β-羟基甾体和2-金刚烷醇可转化为相应的氟化物，产率令人满意。甾醇和4-苯基-1-环己醇的氟化反应进行完全反转，表明四氟硼酸根阴离子中的氟原子通过SN2机制从2中膦部分的对面攻击，而不是SN1机制。通过本方法，无环次级和初级醇的氟化反应在合理产率下进行，尽管后者的反应需要更强烈条件，如在二氧六环中回流。
• Efficient protocol for the SO2F2-mediated deoxyfluorination of aliphatic alcohols
  作者：Cayo Lee、Joey Lai、Maxim Epifanov、Cindy Xinyun Wang、Glenn M. Sammis

  DOI：10.1016/j.jfluchem.2021.109888

  日期：2021.11

  the development of new synthetic methods to access these important fluorinated motifs. Herein we report the sulfuryl fluoride-mediated deoxyfluorination of alcohols using room temperature reaction conditions in only an hour. A wide range of primary aliphatic alcohols were efficiently converted to the corresponding fluoride in 46-70% isolated yields. Secondary alcohols were also effectively deoxyfluorinated

  烷基氟在制药和农业化学工业中都很普遍。因此，过去 40 年来，人们对开发新的合成方法以获取这些重要的氟化基序产生了浓厚的兴趣。在此，我们报告了使用室温反应条件仅在一小时内硫酰氟介导的醇的脱氧氟化。范围广泛的伯脂肪醇以 46-70% 的分离产率有效地转化为相应的氟化物。仲醇也被有效地脱氧氟化，产率为 50-92%。手性仲醇被干净地转化为相应的烷基氟，对映体富集只有轻微的恶化。类固醇衍生物也以 50% 的产率和 5.9:1 dr 进行脱氧氟化，
• AMINOALCOHOL LIPIDOIDS AND USES THEREOF
  申请人：Massachusetts Institute Of Technology

  公开号：EP3269395A1

  公开（公告）日：2018-01-17

  Aminoalcohol lipidoids are prepared by reacting an amine with an epoxide-terminated compound are described. Methods of preparing aminoalcohol lipidoids from commercially available starting materials are also provided. Aminoalcohol lipidoids may be prepared from racemic or stereochemically pure epoxides. Aminoalcohol lipidoids or salts forms thereof are preferably biodegradable and biocompatible and may be used in a variety of drug delivery systems. Given the amino moiety of these aminoalcohol lipidoid compounds, they are particularly suited for the delivery of polynucleotides. Complexes, micelles, liposomes or particles containing the inventive lipidoids and polynucleotide have been prepared. The inventive lipidoids may also be used in preparing microparticles for drug delivery. They are particularly useful in delivering labile agents given their ability to buffer the pH of their surroundings.

  本文介绍了通过胺与环氧化物封端化合物反应制备氨基醇脂质的方法。还提供了从市售起始原料制备氨基醇类脂质的方法。氨基醇脂质可由外消旋或立体化学纯环氧化物制备。氨基醇类脂质或其盐类最好具有生物降解性和生物相容性，可用于各种给药系统。考虑到这些氨基醇类脂化合物的氨基，它们特别适合用于多核苷酸的给药。现已制备出含有本发明类脂化合物和多核苷酸的复合物、胶束、脂质体或颗粒。本发明的类脂质还可用于制备给药微粒。由于本发明脂质具有缓冲周围环境 pH 值的能力，因此在递送易变药剂方面特别有用。