1-Chloro-4-(2-chloro-2-fluoroethenyl)benzene | 19099-59-3

• 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-Chloro-4-(2-chloro-2-fluoroethenyl)benzene
• CAS: 19099-59-3
• 化学式: C₈H₅Cl₂F
• 分子量: 191.032
• InChiKey: OUTUMBGYGHSDLK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  一氟三氯甲烷 、 (4-chlorobenzylidene)hydrazine 在 乙二胺 、 copper(l) chloride 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以58%的产率得到1-Chloro-4-(2-chloro-2-fluoroethenyl)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

• A Novel Approach to 2-Chloro-2-fluorostyrenes
  作者：Valentine G. Nenajdenko、Alexey V. Shastin、Vasily N. Korotchenko、Georgy N. Varseev、Elisabeth S. Balenkova

  DOI：10.1002/ejoc.200390033

  日期：2003.1

  A new general catalytic olefination reaction (COR) of aromatic and heteroaromatic aldehydes and ketones was applied to synthesise 2-chloro-2-fluorostyrenes. The two-stage procedure includes the transformation of carbonyl compounds into hydrazones followed by treatment with CFCl3 mediated by copper catalysis. Trichlorofluoromethane was used as a chlorofluoromethylene transfer reagent. The reaction proceeds

  一种新的芳香族和杂芳香族醛和酮的通用催化烯化反应 (COR) 被应用于合成 2-氯-2-氟苯乙烯。两阶段程序包括将羰基化合物转化为腙，然后在铜催化下用 CFCl3 处理。三氯氟甲烷用作氯氟亚甲基转移试剂。该反应立体选择性地进行，以高产率获得目标烯烃。讨论了建议的反应机理。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• ——
  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.
• ——
  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.