2,4-二甲基-2,2,2-三氟苯乙酮 | 16184-87-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,4-二甲基-2,2,2-三氟苯乙酮
• 英文名称: 2,2,2-trifluoro-1-(2,4-dimethylphenyl)ethanone
• 英文别名: trifluoromethyl 2,4-dimethylphenyl ketone；2,2,2-Trifluoro-1-(2,4-dimethylphenyl)-ethanone；2',4'-Dimethyl-2,2,2-trifluoroacetophenone；1-(2,4-dimethylphenyl)-2,2,2-trifluoroethanone
• CAS: 16184-87-5
• 化学式: C₁₀H₉F₃O
• 分子量: 202.176
• InChiKey: KYXIHKXHBSORRJ-UHFFFAOYSA-N

物化性质

• 沸点：
  63.5-64 °C(Press: 4 Torr)
• 密度：
  1.2098 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2914700090

反应信息

• 作为反应物：
  描述：

  2,4-二甲基-2,2,2-三氟苯乙酮 在 三丁基膦 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以50%的产率得到2,2,2-trifluoro-1-(2,4-dimethylphenyl)ethanol
  参考文献：
  名称：

  Reduction of 2,2,2-trifluoro-1-arylethanones with alkyl phosphines

  摘要：

  In the presence of alkyl phosphines, reduction of 2,2,2-trifluoro-1-arylethanones proceeded smoothly to give the corresponding reduction products in moderate to high yields at room temperature. The possible mechanism was discussed on the basis of deuterium labeling and control experiments, indicating that one hydrogen transfer took place from alkyl phosphine to the carbonyl group activated by a strongly electron-withdrawing trifluoromethyl group. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.09.084
• 作为产物：
  描述：

  O2NCF2C(2,4-(CH3)2C6H3)(OH)CF3 在 potassium carbonate 作用下， 生成 2,4-二甲基-2,2,2-三氟苯乙酮
  参考文献：
  名称：

  Reactions of polyfluoro ketones with aromatic compounds

  摘要：

  DOI：

  10.1007/bf00905999

文献信息

• Acid-Mediated Electrocyclic Domino Transformations of 5,5-Disubstituted 1-Amino-1-azapenta-1,4-dien-3-ones into Dihydrospiroindenepyrazole and Dihydroindenodiazepine Derivatives
  作者：Nugzar Ghavtadze、Roland Fröhlich、Ernst-Ulrich Würthwein

  DOI：10.1021/jo900270e

  日期：2009.6.19

  as a dicationic cyclization of a pentadien-1-one (“superelectrophilic solvation”), where one of the double bonds is part of an aromatic ring and a subsequent rearrangement to form an (monocationic) iminium ion, which either cyclizes to give five-membered spiro ring systems (compounds 5) or tricyclic dihydroindenodiazepine derivatives 6. Hückel- and Möbius-type transition states of the electrocyclization

  三氟甲基取代的1-氨基-1-azapenta-1,4-二烯-3-酮4在三步法中可从丙酮酸酯1中以高收率获得，并经过级联反应，其中包括用2处理后的两个电环化反应。大量过量的三氟甲磺酸生成新的二氢螺并茚并吡唑5a - o和二氢茚并二氮杂6a - j。我们根据量子化学计算将这一反应序列解释为戊二烯-1-酮的特殊环化反应（“超亲电溶剂化”），其中双键之一是芳环的一部分，随后进行重排形成一个（单阳离子）亚胺离子，它可以环化成五元螺环系统（化合物5）或三环二氢茚并二氮杂卓衍生物6。考虑到NICS计算的结果，讨论了电环化反应的Hückel型和Möbius型过渡态。一个1-氨基-1-戊-1,4-二烯-3-酮4和几种二氢螺并茚并吡唑5和二氢茚并二氮杂6 可以通过X射线衍射来表征。
• Superelectrophilic Intermediates in the Synthesis of Novel Indenole Derivatives via 1,5-Cyclization Reactions of 5-Aryl-1-azapenta-1,4-dien-3-ones
  作者：Ernst-Ulrich Würthwein、Nugzar Ghavtadze、Roland Fröhlich、Klaus Bergander

  DOI：10.1055/s-0028-1083188

  日期：——

  Oximes of 5,5-disubstituted 1-azapenta-1,4-dien-3-ones 3 underwent 1,5-cyclization reactions yielding indenole derivatives 4 in moderate to good yields upon treatment with an excess of tri­fluoromethanesulfonic acid. Similarly, the hydrazone 3g led to indenole 4f upon protonation. The reaction could also be successfully applied to the synthesis of benzo[b]cyclopenta[d]thiophene 5 starting from 3f. Products of a competing aza-Nazarov reaction were not observed. The reaction mechanism is explained by assuming the involvement of dicationic intermediates, generated by superelectrophilic solvation, similar to that of known Nazarov and aza-Nazarov-type transformations. Quantum chemical calculations of reaction energies and activation barriers are discussed with respect to the experimental results.

  5,5-取代的1-氮杂戊-1,4-二烯-3-酮的亚胺在过量三氟甲磺酸处理下发生了1,5-环化反应，生成了中等至良好产率的茚烯衍生物。同样，肼缩合物在质子化后也生成了茚烯。该反应还成功应用于从3f合成苯并[b]环戊[d]噻吩。未观察到竞争性氮杂纳扎罗夫反应的产物。反应机理通过假设参与了二阳离子中间体来解释，这些中间体通过超电亲性溶剂化生成，类似于已知的纳扎罗夫和氮杂纳扎罗夫型转化。讨论了反应能量和活化能的量子化学计算结果，并与实验结果进行了比较。
• Highly enantioselective immobilized prolinamide-catalyzed aldol reactions in continuous-flow systems: effect of water on the catalyst lifetime and application in the synthesis of a chiral fenpentadiol analogue
  作者：Caizhen Yue、Yasuhiro Yamashita、Shū Kobayashi

  DOI：10.1039/d0gc04202a

  日期：——

  Catalytic enantioselective aldol reactions of trifluoroacetophenones with ketones under continuous-flow conditions have been developed for the first time by using polystyrene-supported prolinamides. The robustness of the flow system was demonstrated by the continuous synthesis of a variety of trifluoromethyl carbinols in high yields with high enantioselectivities. The unusually long lifetimes (>195

  通过使用聚苯乙烯负载的脯氨酰胺，在连续流动条件下，三氟苯乙酮与酮的催化对映选择性醛醇缩合反应是首次开发的。通过以高收率和高对映选择性连续合成各种三氟甲基甲醇来证明流动系统的坚固性。通过促进H 2可以达到这种流动过程异常长的寿命（> 195 h）O促进亚胺中间体在聚合物上的水解。机理研究表明，在常规间歇体系中，醛醇缩合反应具有消旋现象和固有的可逆性质，两者在连续流动条件下均被抑制。该流动过程的合成效用通过手性芬戊二醇类似物的正式连续流动合成得到了进一步证明。
• 2<i>H</i>-Pyrrole Derivatives from an Aza-Nazarov Reaction Cascade Involving Indole as the Neutral Leaving Group
  作者：Nugzar Ghavtadze、Roland Fröhlich、Ernst-Ulrich Würthwein

  DOI：10.1002/ejoc.200800384

  日期：2008.7

  chemical calculations the key step in the reaction cascade is the cleavage of the N–N bond of the hydrazone fragment of a protonated N-(indolin-1-yl)-1-aza-1,4-dien-3-one intermediate such as 10. This intermediate releases 3H-indole as an unusual, but very efficient neutral leaving group. Several 1-aza-1,4-dien-3-ones 4 and some 3-hydroxy-5H-pyrrole derivatives 8 were characterized by X-ray diffraction

  三氟甲基取代的 N-indolinyl-1-aza-1,4-dien-3-ones 4 可以从 indolinylimino 酯 6 以良好的产率在两步程序中获得，如果进行处理，会经历一种新型的氮杂-纳扎罗夫环化用强酸得到迄今为止未知的 3-羟基-5H-吡咯衍生物 8a-p。作为酸性反应介质的无溶剂多磷酸/酰基酐体系特别有效并且只需要很短的反应时间。根据量子化学计算，反应级联的关键步骤是质子化 N-(indolin-1-yl)-1-aza-1,4-dien-3- 腙片段的 N-N 键断裂一种中间体，例如 10。该中间体释放 3H-吲哚作为一种不寻常但非常有效的中性离去基团。几个 1-aza-1，
• Eine einfache Methode zur Darstellung von Aryl-trifluormethylketonen
  作者：Gerhard Simchen、Andreas Schmidt

  DOI：10.1055/s-1996-4444

  日期：1996.9

  A Simple Method for the Preparation of Aryl Trifluoromethyl Ketones. Caret4-Dimethylamino-1-trifluoroacetylpyrimidinium trifluoroacetate (2) is an effective, easy to handle and stable trifluoroacetylationagent. Aryl trifluormethyl ketones 4 are obtained in good yieldsby reaction of 2 with aromatic compounds 3 in thepresence of aluminum chloride.

  制备芳基三氟甲基酮的简单方法。Caret4-Dimethylamino-1-trifluoroacetylpyrimidinium trifluoroacetate (2) 是一种有效、易于处理且稳定的三氟乙酰化试剂。通过 2 与芳香族化合物 3 在氯化铝存在下的反应，可获得芳基三氟甲基酮 4，而且收率很高。