2,3-dimethyl-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)-2,4-pentadienenitrile | 187392-26-3

• 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: 2,3-dimethyl-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)-2,4-pentadienenitrile
• 英文别名: (2E,4E)-2,3-dimethyl-5-(2,6,6-trimethylcyclohexen-1-yl)penta-2,4-dienenitrile
• CAS: 187392-26-3
• 化学式: C₁₆H₂₃N
• 分子量: 229.365
• InChiKey: GGORCLBEJXFUKK-CHBKHGQFSA-N

物化性质

• 沸点：
  353.6±11.0 °C(predicted)
• 密度：
  0.945±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,3-dimethyl-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)-2,4-pentadienenitrile 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 为溶剂， 生成 10-methyl-13-dm-retine-nitrile
  参考文献：
  名称：

  发色团取代基之间的空间位阻作为视紫质光异构化的驱动力：含视紫质的 10-甲基-13-去甲基视黄醛

  摘要：

  摘要：合成了一种视觉发色团类似物 10-甲基-13-去甲基 (dm) 视黄醛，并用漂白的牛视紫红质重构，形成了一种在 505 nm 处具有最大吸光度的视觉色素衍生物。最近使用 13-dm 视黄醛作为发色团的结果激发了对这种新化合物的研究，该结果显示量子效率显着降低（含 13-dm 视黄醛的视紫红质的 φ：0.30，Ternieden 和 Gartner，J. Photochem. Photobiol. B Biol. 33, 83–86, 1996)。通过使用重组视紫红质作为参考进行定量漂白，新颜料的量子效率确定为 0.59。视紫红质和新色素的非常相似的量子效率为最近提出的假设提供了实验支持，即 11-顺式-视黄醛中 10 和 13 位取代基之间的空间位阻在光异构化过程中升高，从而促进了光异构化的快速光异构化。视觉发色团（Peteanu 等人，Proc. Natl. Acad. Sci. USA

  DOI：

  10.1111/j.1751-1097.1997.tb01896.x
• 作为产物：
  描述：

  beta-紫罗酮 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 2,3-dimethyl-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)-2,4-pentadienenitrile
  参考文献：
  名称：

  Simple and Efficient Preparation of [10,20-¹³C₂]- and [10-CH₃,13-¹³C₂]-10-Methylretinal:  Introduction of Substituents at the 2-Position of 2,3-Unsaturated Nitriles

  摘要：

  In this paper, we present the synthesis of [10,20-C-13(2)] -10-methylretinal and [10-CH3,13-C-13(2)] -10-methylretinal, two doubly C-13-labeled chemically modified retinals that have been recently used to study the structural and functional details behind the photocascade of bovine rhodopsin (Verdegem et al. Biochemistry 1999, 38, 11316; de Lange et al. Biochemistry 1998, 37, 1411). To obtain both doubly C-13-labeled compounds, we developed a novel synthetic method to directly and regiospecifically introduce a methyl substituent on the 2-position of 3-methyl-5-(2',6',6'-trimethyl-1'cyclohexen-1'-yl)-2,4-pentadienenitrile. Encouraged by these results, we investigated the scope of this novel reaction by developing a general method for the introduction of a variety of substituents to the 2-position of 3-methyl-2,3-unsaturated nitriles, paving the way for simple and efficient synthesis of a wide variety of 10-, 14-, and 10,14-substituted chemically modified retinals, and other biologically important compounds.

  DOI：

  10.1021/jo0009595

文献信息

• Simple and Efficient Preparation of [10,20-¹³C₂]- and [10-CH₃,13-¹³C₂]-10-Methylretinal:  Introduction of Substituents at the 2-Position of 2,3-Unsaturated Nitriles
  作者：Peter J. E. Verdegem、Menno C. F. Monnee、Johan Lugtenburg

  DOI：10.1021/jo0009595

  日期：2001.2.1

  In this paper, we present the synthesis of [10,20-C-13(2)] -10-methylretinal and [10-CH3,13-C-13(2)] -10-methylretinal, two doubly C-13-labeled chemically modified retinals that have been recently used to study the structural and functional details behind the photocascade of bovine rhodopsin (Verdegem et al. Biochemistry 1999, 38, 11316; de Lange et al. Biochemistry 1998, 37, 1411). To obtain both doubly C-13-labeled compounds, we developed a novel synthetic method to directly and regiospecifically introduce a methyl substituent on the 2-position of 3-methyl-5-(2',6',6'-trimethyl-1'cyclohexen-1'-yl)-2,4-pentadienenitrile. Encouraged by these results, we investigated the scope of this novel reaction by developing a general method for the introduction of a variety of substituents to the 2-position of 3-methyl-2,3-unsaturated nitriles, paving the way for simple and efficient synthesis of a wide variety of 10-, 14-, and 10,14-substituted chemically modified retinals, and other biologically important compounds.
• Steric Hindrance between Chromophore Substituents as the Driving Force of Rhodopsin Photoisomerization: 10-Methyl-13-Demethyl Retinal Containing Rhodopsin
  作者：Daniel Koch、Wolfgang Gärtner

  DOI：10.1111/j.1751-1097.1997.tb01896.x

  日期：1997.1

  10‐methyl‐13‐demethyl (dm) retinal, was synthesized and reconstituted with bleached bovine rhodopsin to form a visual pigment derivative with absorbance maximum at 505 nm. The investigations with this new compound were stimulated from recent results using 13‐dm retinal as a chromophore that revealed a remarkable loss in quantum efficiency (φ of 13‐dm retinal‐containing rhodopsin: 0.30, Ternieden and Gartner

  摘要：合成了一种视觉发色团类似物 10-甲基-13-去甲基 (dm) 视黄醛，并用漂白的牛视紫红质重构，形成了一种在 505 nm 处具有最大吸光度的视觉色素衍生物。最近使用 13-dm 视黄醛作为发色团的结果激发了对这种新化合物的研究，该结果显示量子效率显着降低（含 13-dm 视黄醛的视紫红质的 φ：0.30，Ternieden 和 Gartner，J. Photochem. Photobiol. B Biol. 33, 83–86, 1996)。通过使用重组视紫红质作为参考进行定量漂白，新颜料的量子效率确定为 0.59。视紫红质和新色素的非常相似的量子效率为最近提出的假设提供了实验支持，即 11-顺式-视黄醛中 10 和 13 位取代基之间的空间位阻在光异构化过程中升高，从而促进了光异构化的快速光异构化。视觉发色团（Peteanu 等人，Proc. Natl. Acad. Sci. USA