3-deuteriofluorobenzene | 591-26-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-deuteriofluorobenzene
• 英文别名: fluorobenzene-3-d；m-deuteriofluorobenzene；1-Deuterio-3-fluor-benzol；Fluorbenzol-3d；1-deuterio-3-fluoro-benzene；3-D-Fluorbenzol；1-Deuterio-3-fluorobenzene
• CAS: 591-26-4
• 化学式: C₆H₅F
• 分子量: 97.0962
• InChiKey: PYLWMHQQBFSUBP-VMNATFBRSA-N

物化性质

• 沸点：
  82.5-83.5 °C(Press: 744 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• 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：

  3-deuteriofluorobenzene 在 氨 、 potassium amide 作用下， 生成 氟苯
  参考文献：
  名称：

  摘要：

  The kinetic isotope effects in deuterium and tritium exchange in benzene, fluorobenzene, pyridine, pyridine N-oxide, and quinoline with a solution of an alkali metal amide in liquid ammonia k(D)(NH3)/k(T)(NH3) were determined, where k(D)(NH3) and k(T)(NH3) are the experimental rate constants of protodedeuteration and protodetritiation, respectively. The variation of the tritium exchange rates in benzene in going from NH3 to ND3 (k(T)(NH3) and k(T)(ND3)) was evaluated. The deviation of the observed ratios k(D)(NH3)/k(T)(NH3) and k(H)(ND3)/k(T)(ND3) from the maximum possible values corresponding to the Swan-Shaad equation suggests the reaction mechanism in which both elementary stages, ionization of the CH acid and diffusion separation of the complex of the carbanion with the ammonia molecule, are partially limiting. A small decrease in the secondary isotope effect of the solvent, defined as k(T)(ND3)/k(T)(NH3) as compared to the theoretical maximum of 2.4, is assumed to be due to similar structures of the transition state and the equilibrium carbanion. A theoretical explanation was given for the observed dependences of the primary isotope effect of the substrate on pK(a) for deutero (tritio) derivatives of fluorobenzene [4D(t) < 3D(t) < 2D(t)], for reactions in the series pyridine-2D(t) < pyridine-3D(t) < quinoline3D(t), and for hydrogen exchange in pyridine-2D(t) N-oxide (k(D)(NH3)/k(T)(NH3) similar to 1).

  DOI：

  10.1023/a:1013134511332
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 乙醚 、 氘代盐酸 作用下， 生成 3-deuteriofluorobenzene
  参考文献：
  名称：

  Microwave Determination of the Structure of Fluorobenzene

  摘要：

  3D-, 4D-, and 2,4,6 D3-fluorobenzene have been prepared. Their microwave spectra have been recorded and analyzed. Values of their rotational constants together with known values of the rotational constants of ordinary fluorobenzene do not suffice for an unambiguous calculation of the 11 geometrical parameters of the molecule but by assistance from valence theory a small number of fairly probable models may be pointed out.

  DOI：

  10.1063/1.1743237

文献信息

• The thermal conversions of 6,6-difluorobicyclo[3.1.0]hex-2-enes to fluorobenzenes. An interesting dichotomy of mechanisms
  作者：W.R. Dolbier、J.J. Keaffaber、C.R. Burkholder、H. Koroniak、J. Pradhan

  DOI：10.1016/s0040-4020(01)81182-0

  日期：——

  1.0]hex-2-ene systems led to the conclusion that drastically different mechanisms operate for the two reactions. Activation parameters, solvent effects, kinetic isotope effects, isotope labelling experiments and observation of reactive intermediates all contributed to the conclusion that the reaction of 6,6-difluorobicyclo[3.1.0]hex-2-ene, 1, proceeds via a homolytic hydrogen-shift rearrangement, while

  对两个表面上相似的6,6-二氟双环[3.1.0] hex-2-ene系统进行热，脱氟化氢芳构化反应的动力学研究得出结论，两个反应的机理完全不同。活化参数，溶剂效应，动力学同位素效应，同位素标记实验和反应中间体的观察均有助于得出以下结论：6,6-二氟双环[3.1.0] hex-2-ene，1通过均溶氢进行反应-移位重排，而2,3-苯并-6,6-二氟双环[3.1.0]己-2-烯，6的反应，是通过溶剂分解机理进行的，该机理涉及速率确定碳阳离子的形成。
• Exchange Reactions of Deuterated Benzene Derivatives with Potassium Amide in Liquid Ammonia^1a
  作者：George E. Hall、Richard Piccolini、John D. Roberts

  DOI：10.1021/ja01622a033

  日期：1955.9

  The rates of deuterium-protium exchange have been determined for o-, m- and p-deuterated fluorobenzene, benzotri-fluoride and anisole in liquid ammonia solution in the presence of potassium amide. The exchange rates were found to be greatest for the ortho compounds and smallest for the para compounds. Deuterobenzene and o-deuterotoluene reacted too slowly for convenient measurement. The results are

  已经确定了在氨化钾存在下在液氨溶液中邻、间和对氘化氟苯、三氟苯和苯甲醚的氘-氚交换率。发现邻位化合物的交换率最大，而对位化合物的交换率最小。氘代苯和邻氘代甲苯反应太慢，无法方便测量。根据取代基的综合感应和场效应的操作来解释结果，介观效应似乎不太重要。
• A Product Analytical Study of the Thermal and Photolytic Decomposition of Some Arenediazonium Salts in Solution
  作者：Peter S. J. Canning、Howard Maskill、Katharine McCrudden、Brian Sexton

  DOI：10.1246/bcsj.75.789

  日期：2002.4

  most solvents undergo unimolecular heterolysis to give singlet aryl cations which are captured by solvent. This mechanism is dominant for arenediazonium ions without electron-withdrawing substituents in all solvents, and the only reaction observed in water. Additionally, appreciable yields of fluoroarenes are obtained by fluoride abstraction by the aryl cation from fluorinated solvents and from tetrafluoroborate

  分析了 11 种重氮芳烃四氟硼酸盐在各种溶剂中的热和光化学反应产物。大多数溶剂中的所有化合物都经过单分子杂解，得到单线态芳基阳离子，这些阳离子被溶剂捕获。这种机制对于在所有溶剂中没有吸电子取代基的芳烃重氮离子占主导地位，并且是在水中观察到的唯一反应。此外，通过芳基阳离子从氟化溶剂中和从氟化溶剂中的四氟硼酸盐提取氟化物，可获得可观的氟芳烃产率。光化学过程的产量与热反应的产量非常相似，表明主要反应通过常见或非常相似的中间体进行。由离子对重氮离子形成的芳基阳离子可与反离子反应，但是解离的重氮离子的碎裂只会产生溶剂衍生的产物。某些溶剂中的某些芳烃重氮离子会发生另一种自由基反应导致...
• Metal-Free sp²-C–H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes
  作者：Konstantin Chernichenko、Markus Lindqvist、Bianka Kótai、Martin Nieger、Kristina Sorochkina、Imre Pápai、Timo Repo

  DOI：10.1021/jacs.6b00819

  日期：2016.4.13

  olefinic C-H bonds with 2-aminophenylboranes. Computational and experimental studies reveal that the metal-free C-H insertion proceeds via a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative action of the amine and boryl groups. The adapted geometry of the reactive B and N centers results in an unprecedentently low kinetic barrier for both insertion into the

  CH 硼酸化是一种强大且原子效率高的方法，可将廉价且丰富的化学品转化为用于生产精细化学品和功能材料的多功能有机试剂。在此，我们报告了芳香族和烯烃 CH 键与 2-氨基苯基硼烷的简便 CH 硼酸化。计算和实验研究表明，不含金属的 CH 插入是通过受挫的路易斯对机制进行的，该机制涉及通过胺和硼基团的协同作用使 CH 键异裂。反应性 B 和 N 中心的适应性几何结构导致了前所未有的低动力学障碍，用于插入 sp(2)-CH 键和 sp(2)-CB 键在 2-氨基苯基(芳基)中的分子内质子化-或-（烯基）硼酸盐。这种常见的反应模式可作为各种催化反应的平台，例如 CH 硼化和炔烃的氢化。特别是，我们证明了简单的 2-氨基吡啶鎓盐可以有效地催化环戊二烯与儿茶酚硼烷的 CH 硼化。该反应可能是由与 2-氨基苯基硼烷等电子的硼物种介导的。
• Mechanistic Insight into H/D Exchange by a Pentanuclear Ni–H Cluster and Synthesis and Characterization of Structural Analogues of Potential Intermediates
  作者：Manar M. Shoshani、Junyang Liu、Samuel A. Johnson

  DOI：10.1021/acs.organomet.7b00763

  日期：2018.1.8

  mechanistic insight into catalytic H/D exchange of unactivated arenes by [(iPr3P)Ni]5H6 (1) are described. The reaction order with respect to 1, arene substrate, and added iPr3P were determined, as well as the temperature dependence of reaction rate. Site-selectivity data were obtained by monitoring the reaction of 1 with fluorobenzene and 2-methoxynaphthalene. H/D exchange competition reactions between

  描述了通过机械手段了解未活化的芳烃通过[[ i Pr 3 P）Ni] 5 H 6（1）进行催化H / D交换的实验。相对于该反应，以1，芳烃底物，并加入我镨3 P含量确定的，以及反应速率的温度依赖性。通过监测1与氟苯和2-甲氧基萘的反应获得位点选择性数据。在与1起反应的芳烃之间进行H / D交换竞争反应。在1的溶液中添加过量的Hg提供了新的杂金属簇[[我镨3 P）的Ni] 5 ħ 6（μ 4 -Hg）（ 2）; 该物种也与C 6 D 6进行了H / D交换，尽管速度比1慢。簇的反应1与TLCP（CP = C 5 H ^ 5），得到（η 5 -CP）的Ni [（我镨3 P）的Ni] 4（μ 2 -H） 4（μ 4 -Tl）（ 3）与所述H 2的损失。当1出现类似的环戊二烯基向Ni的转移用MGCP反应2，得到（η 5 -CP）的Ni [（我镨3 P）的Ni] 4 ħ 6（μ 4 -MgCP）（4），但不为H