2,2-dibromovinyl trifluoromethyl ketone | 444797-09-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dibromovinyl trifluoromethyl ketone
• 英文别名: 4,4-dibromo-1,1,1-trifluorobut-3-en-2-one
• CAS: 444797-09-5
• 化学式: C₄HBr₂F₃O
• 分子量: 281.855
• InChiKey: JLUNMHHPNGQXOF-UHFFFAOYSA-N

物化性质

• 沸点：
  146 °C
• 密度：
  2.204±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  乙基肼 、 2,2-dibromovinyl trifluoromethyl ketone 在 三乙胺 作用下， 以 乙醚 为溶剂， 以88%的产率得到5-bromo-1-ethyl-3-(trifluoromethyl)pyrazole
  参考文献：
  名称：

  Chloro(bromo)vinyl ketones and 2,2-Dichloroacrolein in Reactions with Hydrazines

  摘要：

  Reactions of 2,2-dichlorovinyl and 2,2-dibromovinyl ketones with alkylhydrazines afford respectively 1-R-3-alkyl(aryl)-5-chloro- or 5-bromopyrazoles in preparative yields. The dichloroacrolein forms with alkylhydrazines and dimethylhydrazine only the corresponding hydrazones. Quantum-chemical calculations were performed characterizing the structure of the obtained ketones and dichloroacrolein C, alkylhydrazones, of dichloroacrolein dimethylhydrazone, of 1-alkyl-5-chloropyrazolinium halides, and 1-alkyl-5-chloropyrazoles.

  DOI：

  10.1023/b:rujo.0000010172.72180.4f
• 作为产物：
  描述：

  三氟乙酰氯 、 1,1-二氯乙烯 在 aluminum tri-bromide 、 三氯化铁 作用下， 反应 3.0h， 以70%的产率得到2,2-dibromovinyl trifluoromethyl ketone
  参考文献：
  名称：

  摘要：

  DOI：

  10.1023/a:1015327430360

文献信息

• Structure and Properties of 2,2-Dibromovinyl Trifluoromethyl Ketone
  作者：G. V. Bozhenkov、Yu. L. Frolov、D. S. -D. Toryashinova、G. G. Levkovskaya、A. N. Mirskova

  DOI：10.1023/b:rujo.0000003156.65761.7b

  日期：2003.6

  It was established by IR spectroscopy and quantum-chemical calculations along nonempirical DFT method in B3LYP version with the basis set 6-311 G(d,p) that 2,2-dibromovinyl trifluoromethyl ketone consisted of a mixture of s-cis planar conformer and s-trans-form deviating from a plane by 13degrees, whereas the s-cis-form is more energetically stable than the s-trans one (DeltaE -5.07 kcal mol(-1)). Also in 2,2-dibromovinyl methyl ketone the planar s-cis conformer is more stable. Chlorine-containing analogs, 2,2-dichlorovinyl trifluoromethyl ketone and 2,2-dichlorovinyl methyl ketone, are more stable in the planar s-trans-conformation. Charge distribution and polarization in the dibromovinyl ketones are analogous to those in dichlorovinyl ketones in agreement with the established reactivity of dibromovinyl trifluoromethyl ketone. By reaction of 2,2-dibromovinyl trifluoromethyl ketone with 2,4-dinitrophenyl-, alkylhydrazines, N,N-dimethylhydrazine, N,N-, N,O-, N,S-binucleophiles were respectively obtained hydrazone, derivatives of pyrazole, imidazole, oxazole, and 1,3-thiazine containing, a trifluoromethyl group.
• Distinguishing Features of reactions of 2-chloro-and 2,2-dichloro(bromo)vinyl ketones with alkyl-and arylhydrazines
  作者：G. V. Bozhenkov、V. A. Savosik、L. I. Larina、L. V. Klyba、E. R. Zhanchipova、A. N. Mirskova、G. G. Levkovskaya

  DOI：10.1134/s1070428008070129

  日期：2008.7

  2-Chlorovinyl alkyl ketones react with alkylhydrazines to give mixtures of 1-R-3-R'- and 1-R-5-R'-pyrazoles: The 1-R-3-R'-pyrazoles form through the heterocyclization of 2-chlorovinyl ketone alkylhydrazones whereas in the heterocyclization into 1-R-5-R'-pyrazoles N1-alkyl-N2-(2-acylvinyl) hydrazines are involved. The regiospecific heterocyclization of 2-chloro- and 2,2-dichlorovinyl ketones with arylhydrazines and also of 2,2-dichloro(bromo) vinyl trifluoromethyl ketones with C alkylhydrazines into pyrazoles and 5-chloro(bromo)pyrazoles proceeds through a stage of haloenones hydrazones formation. The study of the structure of the obtained 1-alkyl-3(5)-alkylpyrazoles by means of two-dimenaional H-1 and C-13 NMR spectroscopy and GC-MS method made it possible to assign the proton and carbon signals of isomeric pyrazoles and to establish the diagnostic ions for the pair of 1,3- and 1,5-isomers.
• ——
  作者：G. G. Levkovskaya、G. V. Bozhenkov、L. I. Larina、A. N. Mirskova

  DOI：10.1023/a:1022564707537

  日期：——

  A new regioselective heterocyclization was revealed in the reaction of 2-chloro- and 2,2-dichloro(bromo)vinyl ketones with N,N-dimethylhydrazine to afford 3-substituted 1-methyl(5-halo)pyrazoles. The reaction is accompanied by elimination of methyl halide and formation of up to 90% of N,N,N-trimethylhydrazinium halide as the second product.