3-fluoro-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)penta-2,4-dien-1-al | 186953-29-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-fluoro-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)penta-2,4-dien-1-al
• 英文别名: (2E,4E)-3-fluoro-5-(2,6,6-trimethylcyclohexen-1-yl)penta-2,4-dienal
• CAS: 186953-29-7
• 化学式: C₁₄H₁₉FO
• 分子量: 222.303
• InChiKey: FWWCQNNWSGHBFF-ZYUHXDNHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-fluoro-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)penta-2,4-dien-1-al 在 N,N-二甲基丙烯基脲 、 正丁基锂 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 生成 (2E,4E,6E,8E)-7-Fluoro-3-methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraen-1-ol
  参考文献：
  名称：

  Synthesis of Retinals Fluorinated at Odd-Numbered Side-Chain Positions and of the Corresponding Fluorobacteriorhodopsins

  摘要：

  Conventional Horner-Wadsworth-Emmons and Wittig condensations were used to fluorinate the odd-numbered positions of the retinal side chain past C-7. The stereochemically labile cis-fluororetinals were easily converted into the most stable trans-flouretinals, which were incubated with bacterio-opsin. Contrary to expectations, the fluorinated retinals provided artificial pigments with near normal absorption properties, showing that any electrostatic interactions between the fluorine atoms and protein groups were insufficient to prevent normal binding. The new artificial pigments had smaller opsin shifts than did native bacteriorhodopsin, which is interpreted as due either to greater electrostatic interaction between the protonated imine and its counterion, or to local interactions between the fluorine substituents and nearby polar protein groups.

  DOI：

  10.1021/jo961355x
• 作为产物：
  描述：

  (2E,4E)-tert-butyldiphenylsilyl 3-fluoro-5-(2,6,6-trimethylcyclohex-1-en-1-yl)penta-2,4-dien-1-yl ether 在 manganese(IV) oxide 、 四丁基氟化铵 、 sodium carbonate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 3-fluoro-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)penta-2,4-dien-1-al
  参考文献：
  名称：

  Synthesis of Retinals Fluorinated at Odd-Numbered Side-Chain Positions and of the Corresponding Fluorobacteriorhodopsins

  摘要：

  Conventional Horner-Wadsworth-Emmons and Wittig condensations were used to fluorinate the odd-numbered positions of the retinal side chain past C-7. The stereochemically labile cis-fluororetinals were easily converted into the most stable trans-flouretinals, which were incubated with bacterio-opsin. Contrary to expectations, the fluorinated retinals provided artificial pigments with near normal absorption properties, showing that any electrostatic interactions between the fluorine atoms and protein groups were insufficient to prevent normal binding. The new artificial pigments had smaller opsin shifts than did native bacteriorhodopsin, which is interpreted as due either to greater electrostatic interaction between the protonated imine and its counterion, or to local interactions between the fluorine substituents and nearby polar protein groups.

  DOI：

  10.1021/jo961355x

文献信息

• 9-Demethyl-9-haloretinals by Wadsworth−Emmons Coupling− Easy Preparation of Pure (all-E), (9Z) and (11Z) Isomers
  作者：Yajie Wang、Wei Sein Woo、Ineke van der Hoef、Johan Lugtenburg

  DOI：10.1002/ejoc.200400005

  日期：2004.5

  quantitative yield as a mixture of (9Z) and (all-E) isomers. Even the corresponding fluoro derivative could be obtained in good yield as (9Z) and (all-E) isomers. In the case of a double bond having a halogen substituent, the IUPAC rules have the (E) nomenclature for a cis double bond and the (Z) for a trans double bond. Simple column chromatography gave the pure (9Z) and (all-E) form. Optimizing the Wadsworth−Emmons

  5-(2',6',6'-Trimethyl-1'-cyclohexen-1'-yl)-4-penten-2-yn-1-al 以β-紫罗兰酮为原料，一锅法制备几乎定量的产量。使用 1,4- 亲核加成反应，相应的 9-Cl、9-Br、9-I β-亚亚乙基乙醛体系可以作为（9Z）和（全 E）异构体的混合物一步以定量收率获得。甚至相应的氟衍生物也可以作为（9Z）和（全-E）异构体以良好的收率获得。在双键具有卤素取代基的情况下，IUPAC 规则对顺式双键使用 (E) 命名法，对反式双键使用 (Z) 命名法。简单的柱色谱得到纯的 (9Z) 和 (all-E) 形式。优化 Wadsworth-Emmons 偶联得到相应的 (all-E)- 和 (9Z)- 视黄腈定量产率。随后的 DIBAL-H 减少产生相应的视网膜。为了制备对视觉至关重要的 (11Z) 异构体，我们发现 Wadsworth-Emmons