1-Chloro-4-(3-chloro-2,3,3-trifluoroprop-1-enyl)benzene

• 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-Chloro-4-(3-chloro-2,3,3-trifluoroprop-1-enyl)benzene
• 化学式: C₉H₅Cl₂F₃
• 分子量: 241.04
• InChiKey: PEODANLNBXOIJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  苯甲醚 、 1-Chloro-4-(3-chloro-2,3,3-trifluoroprop-1-enyl)benzene 以 三氟甲磺酸 为溶剂， 反应 2.0h， 以65%的产率得到(Z)-3-(4-chlorophenyl)-2-fluoro-1-(4-methoxyphenyl)prop-2-en-1-one
  参考文献：
  名称：

  超酸性条件下芳烃与2-Halogeno-2-CF3-苯乙烯的Friedel-Crafts烷基化反应。获得三氟甲基化的乙烷和乙烯。

  摘要：

  相应苄基阳离子[ArHC + -CH（X）CF3]的形成使E- / Z-2-卤代-2-CF3苯乙烯[ArCH = C（X）CF3，X = F，Cl，Br ]在超强酸中。通过NMR和理论DFT计算研究了这些新的亲电试剂的结构。根据这些数据，在溴衍生物的情况下，形成的阳离子最有可能以环状溴离子的形式存在，但是在氯和氟衍生物的情况下，开放形式是更优选的。这些苄基阳离子与芳烃的随后反应以弗瑞德-克来福特烷基化反应进行，以高收率得到1,1-二芳基-2-卤代-3,3,3-三氟丙烷[Ar（Ar'）CH-CH（X）CF3] （最多96％）是两种非对映异构体的混合物。通过用碱（KOH或t-BuOK）进行脱卤化氢反应，可以轻松地将制得的卤代丙烷转化为E- / Z-三氟甲基化二芳烃的相应混合物[Ar（Ar'）C = CCF3]（产率高达96％）。消除机理（E2和Ecb）取决于离去基团的性质和反应条件。

  DOI：

  10.1021/acs.joc.6b00419
• 作为产物：
  描述：

  1,1,2-三氯三氟乙烷（CFC-113） 、 (4-chlorobenzylidene)hydrazine 在 乙二胺 、 copper(l) chloride 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以49%的产率得到1-Chloro-4-(3-chloro-2,3,3-trifluoroprop-1-enyl)benzene
  参考文献：
  名称：

  摘要：

  The mechanism of formation of alkene stereoisomers in the catalytic olefination reaction of carbonyl compounds was studied. 4-Chlorobenzaldehyde hydrazone 1 stereoselectively reacts with a number of F-, Cl-, Br-, and I-containing polyhaloalkanes in the presence of catalytic amounts of CuCl to give omega-substituted styrenes 2 with the more thermodynamically stable alkene isomer being the major product. A model for the formation of the stereoisomers of alkenes 2 in the olefination reaction is proposed. Stereoselectivity of the reaction is determined by elimination of copper(II) halides from the lowest-lying conformers of organocopper intermediates II. According to quantum-chemical calculations, the elimination should involve the staggered conformations with antiperiplanar arrangement of C-Hal and C-Cu bonds and proceed by the E2 anti-elimination mechanism. The results of quantum-chemical calculations are in good agreement with the experimental E/Z alkene isomer ratios.

  DOI：

  10.1023/a:1026077309403

文献信息

• Fragmentation of Trifluoromethylated Alkenes and Acetylenes by <i>N</i>,<i>N</i>-Binucleophiles. Synthesis of Imidazolines or Imidazolidines (Oxazolidines) Controlled by Substituent
  作者：Valentine G. Nenajdenko、Vasiliy M. Muzalevskiy、Aleksey V. Shastin、Elizabeth S. Balenkova、Evgeniy V. Kondrashov、Igor A. Ushakov、Alexander Yu. Rulev

  DOI：10.1021/jo101107t

  日期：2010.8.20

  The reaction of β-halogeno-β-polyfluoromethylstyrenes with N,N- or N,O-binucleophiles leads to unexpected fragmentation products (imidazolines) or to heterocyclization giving CF3-substituted imidazolidines (N,N-) and oxazolidines (N,O-) depending on aryl substituent. The scope and the reaction mechanism are discussed.

  β-卤代-β-多氟甲基苯乙烯与N，N-或N，O-双亲核试剂的反应会导致意外的裂解产物（咪唑啉）或杂环化反应，生成CF 3取代的咪唑烷（N，N-）和恶唑烷（N，O -）取决于芳基取代基。讨论了反应的范围和机理。
• Catalytic olefination. Estimation of the reactivity of polyhaloalkanes
  作者：V. G. Nenaidenko、V. N. Korotchenko、A. V. Shastin、D. A. Tyurin、E. S. Balenkova

  DOI：10.1007/s11178-005-0093-2

  日期：2004.12

  Global electrophilicity indices and carbon-halogen bond energies of a wide series of halogen derivatives were calculated in terms of the density functional theory (DFT). The calculated values were used to estimate the reactivity of halogen derivatives under conditions of catalytic olefination. Reactions of N-unsubstituted hydrazones with polyhaloalkanes in the presence of CuCl afforded substituted alkenes. The relation between the structure of polyhaloalkanes and their reactivity was studied using the reaction with 4-chlorobenzaldehyde hydrazone as an example. It was found that increase in the global electrophilicity index and decrease in the C-Hlg bond energy are accompanied by increase in the “olefinating” power of halogen derivatives.

  根据密度泛函理论（DFT）计算了一系列卤素衍生物的整体亲电指数和碳-卤键能。计算值用于估计催化烯化条件下卤素衍生物的反应性。 N-未取代的腙与多卤代烷在 CuCl 存在下反应得到取代的烯烃。以与4-氯苯甲醛腙的反应为例，研究了多卤代烷烃的结构与反应活性的关系。研究发现，总体亲电指数的增加和C-Hlg键能的降低伴随着卤素衍生物“烯化”能力的增加。
• ——
  作者：V. N. Korotchenko、A. V. Shastin、V. G. Nenaidenko、E. S. Balenkova

  DOI：10.1023/a:1026007801456

  日期：——

  Hydrazones of carbonyl compounds at treatment with polyhaloalkanes in the presence of CuCl as catalyst are converted into substituted alkenes with formation of a new C=C bond.
• Friedel–Crafts Alkylation of Arenes with 2-Halogeno-2-CF₃-styrenes under Superacidic Conditions. Access to Trifluoromethylated Ethanes and Ethenes
  作者：Maria A. Sandzhieva、Anna N. Kazakova、Irina A. Boyarskaya、Alexandr Yu. Ivanov、Valentine G. Nenajdenko、Aleksander V. Vasilyev

  DOI：10.1021/acs.joc.6b00419

  日期：2016.6.17

  corresponding benzyl cations [ArHC+-CH(X)CF3] takes palace under protonation of E-/Z-2-halogeno-2-CF3 styrenes [ArCH=C(X)CF3, X = F, Cl, Br] in superacids. The structure of these new electrophiles were studied by means of NMR and theoretical DFT calculations. Accordingly to these data, in the case of bromo derivatives the formed cations, most probably, exist as cyclic bromonium ions, however in the cases of chloro

  相应苄基阳离子[ArHC + -CH（X）CF3]的形成使E- / Z-2-卤代-2-CF3苯乙烯[ArCH = C（X）CF3，X = F，Cl，Br ]在超强酸中。通过NMR和理论DFT计算研究了这些新的亲电试剂的结构。根据这些数据，在溴衍生物的情况下，形成的阳离子最有可能以环状溴离子的形式存在，但是在氯和氟衍生物的情况下，开放形式是更优选的。这些苄基阳离子与芳烃的随后反应以弗瑞德-克来福特烷基化反应进行，以高收率得到1,1-二芳基-2-卤代-3,3,3-三氟丙烷[Ar（Ar'）CH-CH（X）CF3] （最多96％）是两种非对映异构体的混合物。通过用碱（KOH或t-BuOK）进行脱卤化氢反应，可以轻松地将制得的卤代丙烷转化为E- / Z-三氟甲基化二芳烃的相应混合物[Ar（Ar'）C = CCF3]（产率高达96％）。消除机理（E2和Ecb）取决于离去基团的性质和反应条件。
• ——
  作者：V. G. Nenaidenko、V. N. Korotchenko、A. V. Shastin、D. A. Tyurin、E. S. Balenkova

  DOI：10.1023/a:1026077309403

  日期：——

  The mechanism of formation of alkene stereoisomers in the catalytic olefination reaction of carbonyl compounds was studied. 4-Chlorobenzaldehyde hydrazone 1 stereoselectively reacts with a number of F-, Cl-, Br-, and I-containing polyhaloalkanes in the presence of catalytic amounts of CuCl to give omega-substituted styrenes 2 with the more thermodynamically stable alkene isomer being the major product. A model for the formation of the stereoisomers of alkenes 2 in the olefination reaction is proposed. Stereoselectivity of the reaction is determined by elimination of copper(II) halides from the lowest-lying conformers of organocopper intermediates II. According to quantum-chemical calculations, the elimination should involve the staggered conformations with antiperiplanar arrangement of C-Hal and C-Cu bonds and proceed by the E2 anti-elimination mechanism. The results of quantum-chemical calculations are in good agreement with the experimental E/Z alkene isomer ratios.