2-Hydroxy-2-(cyclopentanon-2-yl)-trifluorpropionic acid methyl ester | 404576-82-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Hydroxy-2-(cyclopentanon-2-yl)-trifluorpropionic acid methyl ester
• 英文别名: methyl 2-hydroxy-2-(2-oxocyclopentan-1-yl)-3,3,3-trifluoropropanoate；methyl 2-hydroxy-2-(2-oxocyclopentyl)-3,3,3-trifluoropropanoate；Methyl 3,3,3-trifluoro-2-hydroxy-2-(2-oxocyclopentyl)propanoate
• CAS: 404576-82-5
• 化学式: C₉H₁₁F₃O₄
• 分子量: 240.179
• InChiKey: OFXIGDQZISCCMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-Hydroxy-2-(cyclopentanon-2-yl)-trifluorpropionic acid methyl ester 在 sodium tetrahydroborate 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 为溶剂， 反应 720.0h， 生成 cis-4-hydroxy-4-trifluoromethyl-2-oxabicyclo[3.3.0]octan-3-one
  参考文献：
  名称：

  Fluorinated butanolides and butenolides

  摘要：

  2-Hydroxy-2-trifluoromethylbutan-4-olides (8-10) were prepared by a four step synthesis starting from a ketone and methyl 3,3,3-trifluoropyruvate (1) as a building block. Uncatalyzed chemospecific aldolization of ketones with 1 afforded 2 hydroxy-4-oxoesters 2-4 that were selectively reduced at the oxo group by sodium borohydride to the corresponding 2,4-dihydroxyesters 5-7. Acid-catalyzed cyclization of dihydroxysters 5-7 to lactones 8-10 was strongly dependent on their structure. The lactone-ring closure with the hydroxy group at the hydroxylated cyclopentane ring afforded bicyclic lactone (10) with cyclopentane cis-annulation. 2-Hydroxy-2 trifluoromethylbutanolides appeared to be highly resistent to dehydration or eliminations of the corresponding mesylates or triflates. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(01)00450-x
• 作为产物：
  描述：

  三氟丙酮酸甲酯 、 环戊酮 在 2-氨基苯甲酰胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 144.0h， 以41.3%的产率得到2-Hydroxy-2-(cyclopentanon-2-yl)-trifluorpropionic acid methyl ester
  参考文献：
  名称：

  在三组分多米诺环化的机制新亲核重排，得到氟烷基（吡咯并）喹唑啉

  摘要：

  以下机构的步骤进行验证为具有三种成分的多米诺环化，得到（吡咯），从2-（氨基甲基）苯胺，很活泼的氧代化合物和“通常”氧代喹唑啉化合物。第一步是使反应性很强的羰基化合物（三氟丙酮酸或六氟丙酮）与苄基氨基快速反应，形成半胱氨酸，但不能形成亚胺。第二步是使羰基化合物与芳族氨基反应生成亚胺（席夫碱），其烯胺形式处于平衡状态。第三步骤是通过烯胺碳后跟一个新亲核重排以形成四氢周期的半缩醛胺的碳的分子内攻击; 第四步骤是内酰胺环的闭合，如果酯基团是可作为三氟丙酮。

  DOI：

  10.1016/j.jfluchem.2013.10.017

文献信息

• Novel and Convenient Aldolization of Methyl 3,3,3-Trifluoropyruvate Using Enamines Instead of Ketones
  作者：Oldřich Paleta、Jiří Paleček

  DOI：10.1055/s-2004-815954

  日期：——

  Piperidine enamines derived from acetone, acetophenone, cyclopentanone and cyclohexanone react easily in minutes with methyl 3,3,3-trifluoropyruvate (1) to afford products of the aldol condensation in high yields at room temperature, which is in contrast to the direct aldolization of 1 with the ketones.

  从丙酮、苯乙酮、环戊酮和环己酮中提取的哌啶烯胺与 3,3,3-三氟丙酮酸甲酯（1）很容易在几分钟内发生反应，并在室温下以高产率得到醛醇缩合产物，这与 1 与酮的直接醛化形成鲜明对比。
• The condensation of methyl trifluoropyruvate with carbonyl compounds
  作者：A. S. Golubev、M. V. Galakhov、A. F. Kolomiets、A. V. Fokin

  DOI：10.1007/bf00957801

  日期：1989.9
• GOLUBEV, A. S.;GALAXOV, M. V.;KOLOMIETS, A. F.;FOKIN, A. V., IZV. AN CCCP. CEP. XIM.,(1989) N, S. 2127-2130
  作者：GOLUBEV, A. S.、GALAXOV, M. V.、KOLOMIETS, A. F.、FOKIN, A. V.

  DOI：——

  日期：——
• New nucleophilic rearrangement in the mechanism of the three-component domino cyclisation affording fluoroalkylated (pyrrolo)quinazolines
  作者：Oldřich Paleta、Bohumil Dolenský、Jiří Paleček、Jaroslav Kvíčala

  DOI：10.1016/j.jfluchem.2013.10.017

  日期：2014.1

  steps were verified for the three-component domino cyclisation affording (pyrrolo)quinazolines from 2-(aminomethyl)aniline, a very reactive oxo compound and “usual” oxo compound. The first step was a rapid reaction of very reactive oxo compound (trifluoropyruvate or hexafluoroacetone) with benzylic amino group to form hemiaminal, but not imine; the second step was the reaction of oxo compound with aromatic

  以下机构的步骤进行验证为具有三种成分的多米诺环化，得到（吡咯），从2-（氨基甲基）苯胺，很活泼的氧代化合物和“通常”氧代喹唑啉化合物。第一步是使反应性很强的羰基化合物（三氟丙酮酸或六氟丙酮）与苄基氨基快速反应，形成半胱氨酸，但不能形成亚胺。第二步是使羰基化合物与芳族氨基反应生成亚胺（席夫碱），其烯胺形式处于平衡状态。第三步骤是通过烯胺碳后跟一个新亲核重排以形成四氢周期的半缩醛胺的碳的分子内攻击; 第四步骤是内酰胺环的闭合，如果酯基团是可作为三氟丙酮。
• Fluorinated butanolides and butenolides
  作者：Oldřich Paleta、Jiřı́ Paleček、Bohumil Dolenský

  DOI：10.1016/s0022-1139(01)00450-x

  日期：2001.10

  2-Hydroxy-2-trifluoromethylbutan-4-olides (8-10) were prepared by a four step synthesis starting from a ketone and methyl 3,3,3-trifluoropyruvate (1) as a building block. Uncatalyzed chemospecific aldolization of ketones with 1 afforded 2 hydroxy-4-oxoesters 2-4 that were selectively reduced at the oxo group by sodium borohydride to the corresponding 2,4-dihydroxyesters 5-7. Acid-catalyzed cyclization of dihydroxysters 5-7 to lactones 8-10 was strongly dependent on their structure. The lactone-ring closure with the hydroxy group at the hydroxylated cyclopentane ring afforded bicyclic lactone (10) with cyclopentane cis-annulation. 2-Hydroxy-2 trifluoromethylbutanolides appeared to be highly resistent to dehydration or eliminations of the corresponding mesylates or triflates. (C) 2001 Elsevier Science B.V. All rights reserved.