1-fluorobenzene-4-d | 589-94-6

• 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: 1-fluorobenzene-4-d
• 英文别名: p-Deuterofluorobenzene；1-deuterio-4-fluorobenzene
• CAS: 589-94-6
• 化学式: C₆H₅F
• 分子量: 97.0962
• InChiKey: PYLWMHQQBFSUBP-MICDWDOJSA-N

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：

  1-fluorobenzene-4-d 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：

  1-氯-4-氟苯 在 氘代乙腈 、 3C₈H₂₀N⁽¹⁺⁾*CeCl₆^(3-) 、 四乙基氯化铵 作用下， 反应 16.0h， 生成 1-fluorobenzene-4-d
  参考文献：
  名称：

  Hexachlorocerate(III) 阴离子：一种强效、台式稳定且易于使用的紫外线 A 芳基氯化物光敏剂

  摘要：

  发现六氯铈 (III) 阴离子 [CeIIICl6]3- 在乙腈溶液中是一种有效的光还原剂，与 Cp2Fe0/+ 相比，估计激发态还原电位为 -3.45 V。尽管 22.1(1) ns 的寿命很短，但阴离子表现出 0.61(4) 的光致发光量子产率和对有机卤素的快速淬灭动力学，允许其应用于芳基氯底物的光催化还原。

  DOI：

  10.1021/jacs.6b05712

文献信息

• Photoinduced catalyst-free deborylation–deuteration of arylboronic acids with D₂O
  作者：Yatao Lang、Xiangjun Peng、Chao-Jun Li、Huiying Zeng

  DOI：10.1039/d0gc01649g

  日期：——

  deborylation–deuteration of arylboronic acids with D2O is reported. The protocol was compatible with a variety of functionalities, including halogen, alkoxy, cyano, sulfonyl, trimethylsilyl, trifluoromethoxy, alkyl, hydroxyl, free acid, amide, and heteroaromatic rings. A wide range of deuterated products were obtained in good yields with a high level of deuteration. This method provides a green and practical

  在本文中，报道了用D 2 O进行的新型光诱导的无催化剂脱芳基化-芳基硼酸氘化反应。该方案与多种功能兼容，包括卤素，烷氧基，氰基，磺酰基，三甲基甲硅烷基，三氟甲氧基，烷基，羟基，游离酸，酰胺和杂芳族环。以高收率和高收率获得了多种氘代产品。该方法为在温和条件下合成氘标记的化合物提供了绿色实用的途径。
• 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。
• 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。
• Phenylchromium(III) Chemistry Revisited 100 Years after <i>Franz Hein</i> (Part III): From (Ar)_3–<i>n</i>CrCl<i>_n</i>(L)<i>_x</i> (Ar = Ph, <i>p</i>-F-C₆H₄, C₆D₅; <i>n</i> = 0, 1, 2; L = thf, dme, tmeda, 12C4) to Bis(π-arene)chromium Complexes
  作者：Reinald Fischer、Helmar Görls、Regina Suxdorf、Matthias Westerhausen

  DOI：10.1021/acs.organomet.2c00072

  日期：2022.4.25

  products. Final phase: Deficit of Mg(Ar)2 hinders formation of bis(π-arene)chromium complexes. “Ph2CrCl(thf)x” forms an equilibrium in THF solution with 3-thf3 and PhCrCl2(thf)x (1-Cl). During heating of a solution of 3-thf3, CrCl3(thf)3, and H2O (3:1:1) in THF o-metalation of a phenyl group leads to formation of mixed-valent tetranuclear [Ph4Cr4(μ4-OH)(μ-Cl)2(μ3-Cl)(μ3-C6H4)(thf)4] (4-Cr4) besides biphenyl

  一个世纪前，Franz Hein于 1919 年 1 月首次发表论文，开始了备受推崇的芳基铬化学。根据Hein的方案，双（π-芳烃）铬化合物的形成是在 (Ar) 3型纯底物上进行的– n CrCl n (L) x ( n = 0, 1, 2; Ar = Ph, C 6 D 5 , p -FC 6 H 4 , L = 中性Lewis具有不同碱基强度和齿数的碱基）作为无卤化镁条件下的模型化合物。苯基的 σ-π 转移的三个主要合成阶段已被识别和模拟： 初始阶段（MgPh 2过量）：Ph 3 Cr(thf) 3 ·0.25 dx·( 3-thf 3 , dx = 1, 4-二恶烷）在 C 6 D 6中可逆地消除四氢呋喃 (THF) ，产生蓝绿色 [Ph 3 Cr(thf) 2 ] ( 3-thf 2 )，在 5 °C 以上不可逆反应生成黑褐色联苯溶液、苯和“(η 6 -Ph 2 )CrI(μ-η