cis-1-Hydroxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one | 162599-82-8

• 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: cis-1-Hydroxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one
• CAS: 162599-82-8
• 化学式: C₁₉H₂₆O₂
• 分子量: 286.414
• InChiKey: FPEFTCKSLXJNGP-IEDMXABZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.21
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 cis-1-Hydroxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one 反应 3.0h， 生成 cis-1-Acetoxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one
  参考文献：
  名称：

  Synthesis of 13-Acetoxy-13-demethylretinal, Its Pigment Formation with Bacteriopsin, and Apparent Dark-Inactivating Effect on the Pigment

  摘要：

  The title compound was designed to test for the involvement of nucleophilic catalysis, presumably by aspartate-212, in the dark cis-trans isomerizations of retinal in bacteriorhodopsin. beta-Ionylidenacetaldehyde was condensed with acetylacetaldehyde dimethyl acetal in the presence of NaH in THF forming 1,1-dimethoxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-4E,6E,8E-nonatrien-3-one (4) in good yield. 4 treated with LDA in THF followed by Ac2O/DMAP yields 13-acetoxy-13-desmethylretinal dimethyl acetal (5). Careful, controlled hydrolysis of 5 in acetone, catalyzed by Bio-Rad AG 50W-X1, leads to 13-cis- and all-trans-13-acetoxy-13-desmethylretinal (1), and cis-1-acetoxy- 7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one (6). Both 13-cis-1 and all-trans-1 are highly unstable in the presence of weakly acidic material such as silica gel. Both are converted to 6 in the presence of acid. AM1 calculations indicate that 6 is 4.8 kcal/mol more stable than all-trans-1. 13-cis-1 can be purified by HPLC on a cyano column and shown to form a pigment with bacterioopsin. The bacteriorhodopsin analogue, kept in the dark, slowly loses its absorption at 573 nm and in place develops absorption at 406 nm, signaling an alteration in the chromophore's binding to the protein as a protonated Schiff base (PSB). After a substantial drop in the 573 nm absorption, the retinal analogue can not be removed by the standard ethanol-delipidation method which would otherwise remove retinal, bound as a PSB, from native purple membrane or retinal oxime from photobleached purple membrane.

  DOI：

  10.1021/jo00110a022
• 作为产物：
  描述：

  1,1-Dimethyloxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-4E,6E,8E-nonatrien-3-one 在 Bio-Rad AG 50W-X₁ 水 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 cis-1-Hydroxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one
  参考文献：
  名称：

  Synthesis of 13-Acetoxy-13-demethylretinal, Its Pigment Formation with Bacteriopsin, and Apparent Dark-Inactivating Effect on the Pigment

  摘要：

  The title compound was designed to test for the involvement of nucleophilic catalysis, presumably by aspartate-212, in the dark cis-trans isomerizations of retinal in bacteriorhodopsin. beta-Ionylidenacetaldehyde was condensed with acetylacetaldehyde dimethyl acetal in the presence of NaH in THF forming 1,1-dimethoxy-7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-4E,6E,8E-nonatrien-3-one (4) in good yield. 4 treated with LDA in THF followed by Ac2O/DMAP yields 13-acetoxy-13-desmethylretinal dimethyl acetal (5). Careful, controlled hydrolysis of 5 in acetone, catalyzed by Bio-Rad AG 50W-X1, leads to 13-cis- and all-trans-13-acetoxy-13-desmethylretinal (1), and cis-1-acetoxy- 7-methyl-9-(2',6',6'-trimethyl-1-cyclohexen-1-yl)-1,4E,6E,8E-nonatetraen-3-one (6). Both 13-cis-1 and all-trans-1 are highly unstable in the presence of weakly acidic material such as silica gel. Both are converted to 6 in the presence of acid. AM1 calculations indicate that 6 is 4.8 kcal/mol more stable than all-trans-1. 13-cis-1 can be purified by HPLC on a cyano column and shown to form a pigment with bacterioopsin. The bacteriorhodopsin analogue, kept in the dark, slowly loses its absorption at 573 nm and in place develops absorption at 406 nm, signaling an alteration in the chromophore's binding to the protein as a protonated Schiff base (PSB). After a substantial drop in the 573 nm absorption, the retinal analogue can not be removed by the standard ethanol-delipidation method which would otherwise remove retinal, bound as a PSB, from native purple membrane or retinal oxime from photobleached purple membrane.

  DOI：

  10.1021/jo00110a022