2,2-二氟-1-苯基己烷-1,5-二酮 | 172289-46-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,2-二氟-1-苯基己烷-1,5-二酮
• 英文名称: 2,2-difluoro-1-phenylhexane-1,5-dione
• CAS: 172289-46-2
• 化学式: C₁₂H₁₂F₂O₂
• 分子量: 226.223
• InChiKey: FVYHWWMYYAUALC-UHFFFAOYSA-N

物化性质

• 沸点：
  327.4±42.0 °C(Predicted)
• 密度：
  1.159±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2-二氟-1-苯基己烷-1,5-二酮 在 氢氧化钾 作用下， 以45%的产率得到6-fluoro-[1,1'-biphenyl]-3-ol
  参考文献：
  名称：

  Convergent synthesis of fluoro and gem-difluoro compounds using trifluoromethyltrimethylsilane

  摘要：

  Trifluorotrimethylsilane reacts with acylsilanes to give the corresponding difluoroenoxysilanes via the Brook rearrangement of the alcoholate adducts. The difluoroenoxysilane reacts in situ with various types of electrophilic substrates, leading to gem-difluoro functionalized derivatives in a one-pot methodology. This paper describes reactions with Michael accepters, prenyl, benzyl and glycosyl donors leading to 2,2-difluoro-1,5-diketones, 4,4- or 6,6-difluorocyclohexenones, o- or p-fluorophenols, difluoro analogues of terpenes, and difluoro-C-glycosides. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-1139(99)00158-x
• 作为产物：
  描述：

  三甲基硅基苯甲酮 在 DFTPS ytterbium(III) triflate 作用下， 以 二氯甲烷 为溶剂， 生成 2,2-二氟-1-苯基己烷-1,5-二酮
  参考文献：
  名称：

  Convergent synthesis of fluoro and gem-difluoro compounds using trifluoromethyltrimethylsilane

  摘要：

  Trifluorotrimethylsilane reacts with acylsilanes to give the corresponding difluoroenoxysilanes via the Brook rearrangement of the alcoholate adducts. The difluoroenoxysilane reacts in situ with various types of electrophilic substrates, leading to gem-difluoro functionalized derivatives in a one-pot methodology. This paper describes reactions with Michael accepters, prenyl, benzyl and glycosyl donors leading to 2,2-difluoro-1,5-diketones, 4,4- or 6,6-difluorocyclohexenones, o- or p-fluorophenols, difluoro analogues of terpenes, and difluoro-C-glycosides. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-1139(99)00158-x

文献信息

• Mixed organofluorine-organosilicon chemistry. 8. One-pot synthesis of 2,2-difluoro-1,5 diketones from acylsilanes, trifluoromethyltrimethylsilane and enones, and their annulation reaction
  作者：Olivier Lefebvre、Thierry Brigaud、Charles Portella

  DOI：10.1016/s0040-4020(98)00224-5

  日期：1998.5

  We describe the synthesis of 2,2-difluoro-1,5-diketones in a one-pot procedure from an acylsilane and trifluoromethyltrimethylsilane, via reaction of difluoroenoxysilanes and enones under electrophilic activation. These diketones are interesting building blocks for the synthesis of gem-difluoro enones or substituted fluorophenols, depending on the annulation conditions. The annulation proceeds with complete regioselectivity controlled by the fluorine substitution. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis of .gamma.-(Electron-withdrawing group)-Substituted .alpha.,.alpha.-Difluoro Ketones by UV-Initiated Addition of Iododifluoromethyl Ketones with Electron-Deficient Alkenes
  作者：Zai-Ming Qiu、Donald J. Burton

  DOI：10.1021/jo00126a032

  日期：1995.10

  Under UV irradiation (254 nm), iododifluoromethyl phenyl, alkyl, and chlorodifluoromethyl ketones [RC(O)CF2I (1), R: Ph (a); n-C4H9 (b), n-C6H13 (c), ClCF2 (d)] were reacted with a series of alkyl acrylates (CH2=CHCO(2)R', R': Et, n-Bu, t-Bu, and Me), N,N-dimethylacrylamide, acrylonitrile, and vinyl methyl ketone in the absence of solvent at ambient temperature. High yields of the corresponding 1:1 addition products [RC(O)CF(2)CH(2)CHICO(2)Et (2)] were obtained when 1 reacted with ethyl acrylates (50-79%). The reaction of la with n-butyl acrylate gave a similar 1:1 adduct (51%). However, an addition-reduction product, PhC(O)CF2CH2CH2CO2H, was isolated in 44% yield when tert-butyl acrylate was reacted with la. More interestingly, both 1:1 and 1:2 [PhC(O)CF2CH2CH(CO(2)Me)CH(2)CHICO(2)Me] adducts were formed in a 1.3:1 ratio when la was reacted with methyl acrylate under similar conditions, which indicated that the ester group exhibited an important effect on reaction selectivity. In the reaction with la, ethyl and methyl acrylates also displayed significantly higher reactivity than that of n- or tert-butyl acrylates. 1 also reacted with N,N-dimethylacrylamide to afford high yields of the 1:1 adducts. However, telomeric products were obtained in the reaction of la with acrylonitrile, and the 1:1 and pure 1:2 addition products were isolated in low yield. The reaction of acrylonitrile with alkyl-substituted iododifluoromethyl ketone, Ib, gave only the reduced product, n-C4H9C(O)CF2H, under similar conditions. With vinyl methyl ketone, the reaction of la produced an addition-reduction product, PhC(O)CF2CH2CH2C(O)Me, in 50% yield. The reactivity of RC(O)CF2I (1) varied with the substituted R groups in the reaction with ethyl acrylate and N,N-dimethylacrylamide: R, CICF2 > Ph > n-C4H9 > n-C6H13. Correspondingly, the reaction of la with ethyl acrylate generated a polymer in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium. Treatment of the adducts with zinc in the presence of a catalytic amount of NiCl2 . 6H(2)O in moist THF afforded the corresponding gamma-(electron-withdrawing group)-substituted alpha,alpha-difluoro ketones in high yields.
• Convergent synthesis of fluoro and gem-difluoro compounds using trifluoromethyltrimethylsilane
  作者：Charles Portella、Thierry Brigaud、Olivier Lefebvre、Richard Plantier-Royon

  DOI：10.1016/s0022-1139(99)00158-x

  日期：2000.2

  Trifluorotrimethylsilane reacts with acylsilanes to give the corresponding difluoroenoxysilanes via the Brook rearrangement of the alcoholate adducts. The difluoroenoxysilane reacts in situ with various types of electrophilic substrates, leading to gem-difluoro functionalized derivatives in a one-pot methodology. This paper describes reactions with Michael accepters, prenyl, benzyl and glycosyl donors leading to 2,2-difluoro-1,5-diketones, 4,4- or 6,6-difluorocyclohexenones, o- or p-fluorophenols, difluoro analogues of terpenes, and difluoro-C-glycosides. (C) 2000 Elsevier Science S.A. All rights reserved.