1-chloro-2-(trifluoromethyl)hexafluorocyclopent-1-ene | 247170-18-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 1-chloro-2-(trifluoromethyl)hexafluorocyclopent-1-ene
• 英文别名: 1-chloro-2-methyl perfluorocyclopentene；1-Chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopentene
• CAS: 247170-18-9
• 化学式: C₆ClF₉
• mdl: MFCD01075258
• 分子量: 278.505
• InChiKey: SPJMTEPSABEJSM-UHFFFAOYSA-N

物化性质

• 沸点：
  45.9±40.0 °C(Predicted)
• 密度：
  1.71±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1-chloro-2-(trifluoromethyl)hexafluorocyclopent-1-ene 在 potassium fluoride 、 18-冠醚-6 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 生成 1,3,3,4,4,5,5-七氟-2-(三氟甲基)环戊烯
  参考文献：
  名称：

  摘要：

  Reactions were studied between 1-chloro-2-(trifluoromethyl)-hexafluorocyclopent-1-ene with anions [CpFe(CO)(2)](-), [Re(CO)(5)](-), [Mn(CO)(5)](-), [CpMo(CO)(3)](-), and [CpW(CO3](-). The effect of proton donors on the composition of reaction products was established. The reactions with [Re(CO)(5)](-) and [Mn(CO)(5)](-) were shown to proceed quantitatively along nucleophilic route (S(N)2Vin) resulting in a-vinyl complexes of rhenium and manganese. The [CpMo(CO)(3)](-) and [CpW(CO)(3)](-) anions turned Out to be 10(4) times less nucleophilic than [Mn(CO)(5)](-). In this case the main course of the reaction is the metal-halogen exchange with concurrent nucleophilic substitution. In reaction of [CpMo(CO)(3)](-) and [CpW(CO)(3)](-) with 1-chloro-2- (trifluoromethyl)-hexafluorocyclopent-1-ene the sigma -vinyl complexes arise along an unusual autocatalytic mechanism: the reaction of carbonyl occurs not with the initial substrate but with pentafluoromethylcyclopent-1-ene that forms from the substrate under the action of a fluoride ion. In an extremely fast reaction of the same Substrate with [CpFe(CO)(2)]K the main process is carbonylate oxidation along unestablished mechanism. The reaction between carbonylates and 1-chloro-2-(perfluoro-tert-butyl)hexafluorocyclopent-1-ene proceeds exclusively as metal-halogen exchange that with [Re(CO)(5)](-) furnishes anionic acyl complex cis[C9F15C(O)Re(CO)(4)Cl](-). The reaction of Z and E isomers of beta -chloro-alpha,beta -difluorostyrenes with [CpFe(CO)(2)](-) in the presence of proton donors confirmed the previously assumed (S(N)2Vin) mechanism of nucleophilic substitution and also the intermediate formation of alkenyl carbanions in the parallel redox process.

  DOI：

  10.1023/a:1012469516433

文献信息

• Dualism of Ion-Pairing Effects in Nucleophilic Vinylic Substitution with Transition-Metal Carbonyl Anions
  作者：Petr K. Sazonov、Irina P. Beletskaya

  DOI：10.1002/cplu.201300171

  日期：2013.9

  Ion pairing with cations has a marked but nonuniform effect on the chemistry of carbonylmetalate anions and can either inhibit or facilitate their reactions. A study of the effect of cation-solvating agents ([18]crown-6, hexamethylphosphoramide) on the reactions of carbonylmetalates [Na(K)][M(CO)n L] with vinyl halides activated with strong electron-withdrawing groups, which at the same time could

  阳离子与离子配对对羰基金属酸盐阴离子的化学作用具有显着但不均匀的影响，并且可以抑制或促进其反应。阳离子溶剂（[18] cro-6，六甲基磷酰胺）对羰基金属盐[Na（K）] [M（CO）n L]与强吸电子基团活化的乙烯基卤化物的反应的研究，它同时可以作为钠或钾阳离子的硬供体中心。在THF溶液中加入阳离子溶剂后，Na [Re（CO）5]或K [Mn（CO）5]与所研究的氯乙烯的反应速率急剧下降。效应（kobs（THF）/ kobs（THF + [18] crown-6））沿以下顺序增加：PhCClC（CN）2（4）<（Z）-PhC（CN）CHCl（17）CN≫CF使我们能够解释阳离子协调对这些群体中供体中心的协助，从而稳定了过渡状态。离子对的作用还取决于卤化乙烯中的离去基团，对于（Z）-PhC（CN）CHBr几乎消失，而对于（E）-PhCOCHCHI仅观察到少量的阳离子助剂。这促使我们