1,2-dichloro-4-(difluoromethyl)benzene | 52126-13-3

• 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: 1,2-dichloro-4-(difluoromethyl)benzene
• CAS: 52126-13-3
• 化学式: C₇H₄Cl₂F₂
• 分子量: 197.012
• InChiKey: KREIQWZRXXJZIV-UHFFFAOYSA-N

物化性质

• 沸点：
  95-105 °C(Press: 90 Torr)
• 密度：
  1.394±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  1,2-dichloro-4-(difluoromethyl)benzene 生成 Methyl 5-[2-chloro-4-(difluoromethyl)phenoxy]-2-nitrobenzoate
  参考文献：
  名称：

  SWITHENBANK, COLIN

  摘要：

  DOI：
• 作为产物：
  描述：

  3,4-二氯碘苯 在 potassium fluoride 、 copper(l) iodide 、 水 、 potassium carbonate 作用下， 以 甲醇 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 29.0h， 生成 1,2-dichloro-4-(difluoromethyl)benzene
  参考文献：
  名称：

  A New Method for Aromatic Difluoromethylation: Copper-Catalyzed Cross-Coupling and Decarboxylation Sequence from Aryl Iodides

  摘要：

  A new methodology for aromatic difluoromethylation is described. Aryl iodides reacted with alpha-silyldifluoroacetates upon treatment with copper catalyst in DMSO or DME to give the corresponding aryldifluoroacetates in moderate to good yields. The subsequent hydrolysis of aryldifluoroacetates and KF-promoted decarboxylation afforded a variety of difluoromethyl aromatics.

  DOI：

  10.1021/ol202289z

文献信息

• Proton Magnetic Resonance Studies of Rotational Isomerism in Halotoluenes. X. Estimates of Conformational Preferences and Rotational Barriers in Benzal Fluoride and Some Dichloro Derivatives
  作者：J. Brian Rowbotham、Alexander Frank Janzen、James Peeling、Ted Schaefer

  DOI：10.1139/v74-077

  日期：1974.2.1

  4-, and 2,4-dichloro derivatives is followed by an analysis of their proton magnetic resonance spectra. The long-range spin–spin coupling constants are most consistent with a barrier to rotation about the sp2–sp3 carbon–carbon bond in benzal fluoride of less than 500 cal/mol, in semiquantitative agreement with an ab initio molecular orbital calculation. The 2,6-dichloro derivative has a conformation

  在合成苯并氟及其 2,6-、3,5-、3,4- 和 2,4-二氯衍生物之后，对其质子磁共振光谱进行了分析。长程自旋-自旋耦合常数与小于 500 cal/mol 的苯甲醛中 sp2-sp3 碳-碳键的旋转势垒最一致，与 ab initio 分子轨道计算半定量一致。2,6-二氯衍生物具有侧链的CH键位于芳环平面的构象。2,4-二氯衍生物有利于类似的构象，CH键与环氯原子顺式排列。与长程质子 - 质子偶联相反，长程质子 - 氟偶联本质上对环氯原子的取代基效应敏感。
• Nickel-Catalyzed Difluoromethylation of Arylboronic Acids with Bromodifluoromethane
  作者：Xia-Ping Fu、Yu-Lan Xiao、Xingang Zhang

  DOI：10.1002/cjoc.201700624

  日期：2018.2

  fluorine source, direct formation of difluoromethylated arenes with BrCF2H has not been reported. Herein, we describe an efficient method to access difluoromethylated arenes through a nickel‐catalyzed difluoromethylation of arylboronic acids with BrCF2H. The reaction exhibits high efficiency, good functional group tolerance and broad substrate scope, thus providing an efficient route for applications in

  尽管溴二氟甲烷（BrCF 2 H）是一种简单易用的氟源，但尚未见到与BrCF 2 H直接形成二氟甲基化芳烃的报道。本文中，我们描述了一种通过BrCF 2 H通过镍催化的芳基硼酸的二氟甲基化来访问二氟甲基化的芳烃的有效方法。该反应显示出高效率，良好的官能团耐受性和广泛的底物范围，从而为在药物发现中的应用提供了一条有效途径和发展。初步的机理研究表明该反应涉及二氟甲基。
• Synthesis, Reactivity, and Catalytic Applications of Isolable (NHC)Cu(CHF₂) Complexes
  作者：James R. Bour、Stavros K. Kariofillis、Melanie S. Sanford

  DOI：10.1021/acs.organomet.7b00025

  日期：2017.4.10

  Difluoromethyl copper complexes have been proposed as key intermediates in a variety of Cu-catalyzed difluoromethylation reactions. However, studies of these putative intermediates have been impeded by the low stability of these [Cu(CHF2)] species. This report describes the synthesis of isolable N-heterocyclic carbene ligated copper(I) difluoromethyl complexes. The stoichiometric reactions of these complexes with aryl electrophiles (i.e., diaryliodonium salts, aryl iodides, and aryl bromides) are described. In addition, N-heterocyclic carbene copper(I) species are demonstrated to serve as catalysts for the cross-coupling of aryl iodides with (difluoromethyl)trimethylsilane to afford difluoromethyl arene products.
• US4743703A
  申请人：——

  公开号：US4743703A

  公开（公告）日：1988-05-10
• A New Method for Aromatic Difluoromethylation: Copper-Catalyzed Cross-Coupling and Decarboxylation Sequence from Aryl Iodides
  作者：Kenichi Fujikawa、Yasutaka Fujioka、Akira Kobayashi、Hideki Amii

  DOI：10.1021/ol202289z

  日期：2011.10.21

  A new methodology for aromatic difluoromethylation is described. Aryl iodides reacted with alpha-silyldifluoroacetates upon treatment with copper catalyst in DMSO or DME to give the corresponding aryldifluoroacetates in moderate to good yields. The subsequent hydrolysis of aryldifluoroacetates and KF-promoted decarboxylation afforded a variety of difluoromethyl aromatics.