2,2,2-Trifluoroethyl 1-(trifluoromethyl)-3-methyl-4-oxo-2-cyclohexene-1-carboxylate | 131758-87-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,2,2-Trifluoroethyl 1-(trifluoromethyl)-3-methyl-4-oxo-2-cyclohexene-1-carboxylate
• 英文别名: 2,2,2-trifluoroethyl 3-methyl-4-oxo-1-(trifluoromethyl)cyclohex-2-ene-1-carboxylate
• CAS: 131758-87-7
• 化学式: C₁₁H₁₀F₆O₃
• 分子量: 304.189
• InChiKey: HZVXDNZDRRUZSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.95
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2,2,2-Trifluoroethyl 1-(trifluoromethyl)-3-methyl-4-oxo-2-cyclohexene-1-carboxylate 在 吡啶 、 chromium(VI) oxide 、 manganese(IV) oxide 、 potassium fluoride 、 正丁基锂 、 偶氮二异丁腈 、 甲基三苯氧基碘磷 、 三正丁基氢锡 、 二异丁基氢化铝 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 30.75h， 生成 (2E,4E)-3-Methyl-5-(2,6-dimethyl-6-(trifluoromethyl)-1-cyclohexen-1-yl)-2,4-pentadienal
  参考文献：
  名称：

  Construction of trifluoromethylated quaternary carbons via Diels-Alder reactions of 2-(trifluoromethyl)propenoic acid derivatives: application to the synthesis of 16,16,16-trifluororetinal

  摘要：

  Diels-Alder reactions of 2-(trifluoromethyl)propenoic acid (1) and its 2,2,2-trifluoroethyl ester 2 with various dienes gave adducts in good yields. In Lewis acid catalyzed Diels-Alder reactions of 2, the combination of the Lewis acid and solvent proved to be crucial. For example, polymerization occurred in the case of TiCl4-CH2Cl2 and adduct formation was observed with TiCl4-toluene and TiCl2(O-i-Pr)2-CH2Cl2. In the TiCl4-catalyzed Diels-Alder reaction of the 2-(trifluoromethyl)propenoate ester 3 of D-pantolactone with butadiene, the formation of the R configurational quaternary carbon bearing the trifluoromethyl group was confirmed by X-ray crystallographic analysis of the adduct 20. No polymerization of ester 3 could be detected in the presence of TiCl4 in CH2Cl2. The reactivity difference between 2 and 3 in TiCl4-catalyzed Diels-Alder reactions may possibly be attributable to the stabilization of the 3-TiCl4 complex or weakening of Lewis acidity by coordination of the bidentate ester group of 3. The synthesis of all-trans-16,16,16-trifluororetinal (4), which is considered to be an important analogue for the study of retinal-binding protein, was conducted on the basis of these results. Comparison of the absorption maximum (362 nm) of 4 with other trifluororetinal 34 (362 nm) and 35 (382 nm) reported previously suggests the possibility of a large torsion of the conjugated system between the ring and the polyenal side chain in 4.

  DOI：

  10.1021/jo00005a014
• 作为产物：
  描述：

  在 对甲苯磺酸 作用下， 生成 2,2,2-Trifluoroethyl 1-(trifluoromethyl)-3-methyl-4-oxo-2-cyclohexene-1-carboxylate
  参考文献：
  名称：

  Trifluoromethyl group on quarternary carbon; synthesis of 16,16,16-trifluororetinal

  摘要：

  DOI：

  10.1016/s0040-4039(00)95257-2

文献信息

• HANZAWA, YUJI;SUZUKI, MAKOTO;KOBAYASHI, YOSHIRO;TAGUCHI, TAKEO;IITAKA, YO+, J. ORG. CHEM., 56,(1991) N, C. 1718-1725
  作者：HANZAWA, YUJI、SUZUKI, MAKOTO、KOBAYASHI, YOSHIRO、TAGUCHI, TAKEO、IITAKA, YO+

  DOI：——

  日期：——