Methyl 16,16,16-trifluororetinoate | 123522-20-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Methyl 16,16,16-trifluororetinoate
• 英文别名: methyl (2E,4E,6E,8E)-9-[2,6-dimethyl-6-(trifluoromethyl)cyclohexen-1-yl]-3,7-dimethylnona-2,4,6,8-tetraenoate
• CAS: 123522-20-3；131758-94-6
• 化学式: C₂₁H₂₇F₃O₂
• 分子量: 368.439
• InChiKey: JRMFECXSAFMSKX-YCNIQYBTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 16,16,16-trifluororetinoate 在 manganese(IV) oxide 、 二异丁基氢化铝 作用下， 生成 16,16,16-Trifluororetinal
  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：

  4-二乙基膦酰基-3-甲基-2-丁烯酸甲酯 在 manganese(IV) oxide 、 正丁基锂 、 二异丁基氢化铝 作用下， 反应 2.25h， 生成 Methyl 16,16,16-trifluororetinoate
  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

文献信息

• Trifluoromethyl group on quarternary carbon; synthesis of 16,16,16-trifluororetinal
  作者：Yuji Hanzawa、Makoto Suzuki、Yoshiro Kobayashi

  DOI：10.1016/s0040-4039(00)95257-2

  日期：1989.1
• 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：——
• HANZAWA, YUJI;SUZUKI, MAKOTO;KOBAYASHI, YOSHIRO, TETRAHEDRON LETT., 30,(1989) N 5, C. 571-574
  作者：HANZAWA, YUJI、SUZUKI, MAKOTO、KOBAYASHI, YOSHIRO

  DOI：——

  日期：——
• Construction of trifluoromethylated quaternary carbons via Diels-Alder reactions of 2-(trifluoromethyl)propenoic acid derivatives: application to the synthesis of 16,16,16-trifluororetinal
  作者：Yuji Hanzawa、Makoto Suzuki、Yoshiro Kobayashi、Takeo Taguchi、Yoichi Iitaka

  DOI：10.1021/jo00005a014

  日期：1991.3

  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.