1,1,1-trifluoro-2-penten-4-one | 75747-61-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1,1-trifluoro-2-penten-4-one
• 英文别名: 5,5,5-trifluoro-3-penten-2-one；5,5,5-Trifluoropent-3-en-2-one；5,5,5-trifluoropent-3-en-2-one
• CAS: 75747-61-4
• 化学式: C₅H₅F₃O
• 分子量: 138.089
• InChiKey: IQUVUQSZDQNGPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  1,1,1-trifluoro-2-penten-4-one 在 氢氧化钾 、 sodium carbonate 作用下， 以 甲醇 为溶剂， 反应 11.0h， 生成 3-(trifluoromethyl)-2,5-hexanedione
  参考文献：
  名称：

  Novel 2,5-Hexanedione Analogues. Substituent-Induced Control of the Protein Cross-Linking Potential and Oxidation Susceptibility of the Resulting Primary Amine-Derived Pyrroles

  摘要：

  The neurotoxic gamma -diketone, 2,5-hexanedione (2,5-HD), induces neurofilamentous swellings at prenodal sites in proximal axons as a consequence of pyrrolation of lysine E-amino groups on neurofilament proteins. However, there is disagreement as to whether pyrrole formation and the associated alteration of noncovalent interactions is sufficient to cause neurofilament accumulation, or whether pyrrole autoxidation and subsequent protein-protein cross-linking is an obligatory event. To investigate gamma -diketones that might form pyrroles inert to autoxidative-induced cross-linking, we synthesized 1,1,1-trifluoro-2,5-hexanedione, 3-(trifluoromethyl)-2,5-hexanedione (3-TFMHD), and two 3-(dialkylaminocarbonyl)-2,5-diketones and assessed their rates of pyrrole formation with amines, the oxidation susceptibility of the resulting pyrroles, and the protein cross-linking potential in vitro, relative to those of 3-methyl-2,5-hexanedione. 1,1,1-Trifluoro-2,5-hexanedione does not form pyrroles, but the three 2,5-HD analogues with an electron-withdrawing 3-substituent all rapidly formed pyrroles that were inert to autoxidation. Although 3-TMFHD nonetheless still induced cross-linking of ribonuclease A, by a nonoxidative mechanism independent of the pyrrole, the two 3-(dialkylaninocarbonyl)-2,5-diketones did not exhibit any protein cross-linking. As these two gamma -diketones possess aqueous-organic partitioning properties similar to those of 2,5-HD, they should serve as useful mechanistic probes in further studies.

  DOI：

  10.1021/tx000169q
• 作为产物：
  描述：

  2,2,2-三氟乙醛 、 1-三苯基膦-2-丙酮 以 乙醚 为溶剂， 反应 3.0h， 以75%的产率得到1,1,1-trifluoro-2-penten-4-one
  参考文献：
  名称：

  Electron Deficient Porphyrins III. Facile Syntheses of Perfluoroalkylporphyrins Including Water Soluble Porphyrin

  摘要：

  通过 β-全氟烷基 α、β-不饱和羰基化合物与对甲苯磺酰基甲基异氰酸酯的反应，制备了多种 3-全氟烷基吡咯，收率适中。在酸性介质中，通过 3-烷基-2-羟甲基-4-全氟烷基吡咯的氧化环化反应，很容易得到四(全氟烷基)卟啉，包括水溶性的 3,8,13,18-四(对羧基苄基)-2,7,12,17-四(三氟甲基)卟啉。其内氮的单质子化 pKa 值小于 1，而 Copro-I 的 pKa 值为 7.2。3,8,13,18-四(对甲氧基羧基苄基)-2,7,12,17-四(三氟甲基)卟啉的还原电位向较低的负值移动了 580 mV。

  DOI：

  10.1246/bcsj.70.937

文献信息

• Asymmetric Michael-Aldol Tandem Reaction of 2-Substituted Benzofuran-3-ones and Enones: A Facile Synthesis of Griseofulvin Analogues
  作者：Nan Dong、Xin Li、Feng Wang、Jin-Pei Cheng

  DOI：10.1021/ol402346c

  日期：2013.9.20

  A highly enantioselective Michael–aldol tandem reaction with respect to prochiral 2-substituted benzofuran-3-ones and enones by a facile primary amine catalyst was investigated. The approach provides rapid access to the desired pharmaceutically active griseofulvin analogues.

  研究了一种简便的伯胺催化剂对前手性2-取代的苯并呋喃-3-酮和烯酮的高度对映选择性的迈克尔-奥尔登串联反应。该方法提供了对所需药物活性灰黄霉素的类似物的快速访问。
• Asymmetric Synthesis of (Trifluoromethyl)piperidines: Preparation of Highly Enantioenriched α′-(Trifluoromethyl)pipecolic Acids
  作者：Jean-Louis Canet、Wahid Jatoi、Annabelle Bariau、Cécile Esparcieux、Gilles Figueredo、Yves Troin

  DOI：10.1055/s-2008-1072768

  日期：2008.5

  The first asymmetric synthesis of (trifluoromethyl)pipecolic acids is reported. The synthetic strategy involves as key step an intramolecular Mannich reaction of a homochiral α-Tfm-β-amino ketal, prepared with a high stereoselectively in four steps from a fluoral hemiacetal.

  报道了（三氟甲基）哌啶酸的第一个不对称合成。合成策略涉及作为关键步骤的同手性 α-Tfm-β-氨基缩酮的分子内曼尼希反应，该反应通过四步从氟代半缩醛以高立体选择性制备。
• Facile Syntheses of Perfluoroalkylporphyrins. Electron Deficient Porphyrins II
  作者：Katsuhiro Aoyagi、Hiroo TOI、Yasuhiro Aoyama、Hisanobu Ogoshi

  DOI：10.1246/cl.1988.1891

  日期：1988.11.5

  A variety of β-perfluoroalkylpyrroles were prepared from reaction of β-perfluoroalkyl-α,β-unsaturated ketones with p-toluenesulfonylmethylisocyanide in moderate yields. Tetrakis(perfluoroalkyl)porphyrins were readily obtained by oxidative cyclization of 2-hydroxymethyl-3-ethyl-4-perfluoroalkylpyrroles in acidic media.

  β-全氟烷基-α,β-不饱和酮与对甲苯磺酰基甲基异氰化物以中等产率反应制备了多种β-全氟烷基吡咯。四（全氟烷基）卟啉很容易通过 2-羟甲基-3-乙基-4-全氟烷基吡咯在酸性介质中的氧化环化获得。
• Oxidatively Resistant Ligands for Palladium-Catalyzed Aerobic Alcohol Oxidation
  作者：David M. Pearson、Nicholas R. Conley、Robert M. Waymouth

  DOI：10.1021/om101037k

  日期：2011.3.28

  The complex [(neocuproine)Pd(OAc)](2)[OTf](2) (1) catalyzes the aerobic oxidation of 2-heptanol at room temperature, but Competitive ligand oxidation leads to low catalyst lifetimes. In an effort to mitigate the oxidative degradation of the ligand, a variety of Pd complexes ligated by fluorinated phenanthrolines (bis-2,9-(trifluoromethyl)-1,10-phenanthroline (btfm-phen), 4-methyl-2-(trifluoromethyl)-1,10-phenanthroline (tfmm-phen), and 2-(o-difluoropheny1)-1,10-phenanthroline (odfp-phen)) were prepared and tested. Active catalyst precursors were generated by in situ conproportionation of (N- N)Pd(OAc)(2) and [(N-N)Pd(NCCH3)(2)[OTf](2). Pd complexes derived from tfmm-phen catalyzed the aerobic oxidation of 2-heptanol at room temperature with up to 22 turnovers, nearly double that of 1.
• 1,1,1-Trifluoro-2-penten-4-one as a building block of trifluoromethyl-substituted compounds
  作者：Hisanobu Ogoshi、Hiromoto Mizushima、Hiroo Toi、Yasuhiro Aoyama

  DOI：10.1021/jo00362a034

  日期：1986.6