11,12-二去氢视黄醇 | 29443-88-7

• 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
• 中文名称: 11,12-二去氢视黄醇
• 中文别名: 11,12-二氢视黄醇
• 英文名称: 11,12-dehydroretinol
• 英文别名: (2E,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,6,8-trien-4-yn-1-ol；11,12-Didehydro-[7t,9t,13t]retinol；3.7-Dimethyl-1t-(2.2.6-trimethyl-cyclohexen-(6)-yl)-nonatrien-(1.3t.7t)-in-(5)-ol-(9)；11,12-Didehydro Retinol；(2E,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,6,8-trien-4-yn-1-ol
• CAS: 29443-88-7
• 化学式: C₂₀H₂₈O
• 分子量: 284.442
• InChiKey: GCOWPJRSSDVABG-YSVSHSNWSA-N

物化性质

• 溶解度：
  可溶于氯仿（少许）、乙酸乙酯（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  11,12-二去氢视黄醇 在 copper diacetate 水 、 silver nitrate 、 锌 作用下， 以 甲醇 为溶剂， 以95%的产率得到9-cis,11-cis,13-cis-retinol
  参考文献：
  名称：

  Accurate Measurements of ¹³C−¹³C J-Couplings in the Rhodopsin Chromophore by Double-Quantum Solid-State NMR Spectroscopy

  摘要：

  A new double-quantum solid-state NMR pulse sequence is presented and used to measure one-bond 13C-13C J-couplings in a set of 13C2-labeled rhodopsin isotopomers. The measured J-couplings reveal a perturbation of the electronic structure at the terminus of the conjugated chain but show no evidence for protein-induced electronic perturbation near the C11-C12 isomerization site. This work establishes NMR methodology for measuring accurate 1JCC values in noncrystalline macromolecules and shows that the measured J-couplings may reveal local electronic perturbations of mechanistic significance.

  DOI：

  10.1021/ja0581604
• 作为产物：
  描述：

  (E)-2-methyl-4-(2,6,6-trimethyl-1-cyclohexenyl)-2-butenal 生成 11,12-二去氢视黄醇
  参考文献：
  名称：

  Khristoforov,V.L. et al., Journal of Organic Chemistry USSR (English Translation), 1973, vol. 9, p. 1868 - 1872

  摘要：

  DOI：

文献信息

• Synthesis of 11-<i>cis</i>-Retinoids by Hydrosilylation-Protodesilylation of an 11,12-Didehydro Precursor: Easy Access to 11- and 12-Mono- and 11,12-Dideuteroretinoids
  作者：Julián Bergueiro、Javier Montenegro、Carlos Saá、Susana López

  DOI：10.1002/chem.201202260

  日期：2012.10.29

  An expeditious, highly efficient approach to 11‐cis‐retinoids was achieved by semihydrogenation of a readily available 11‐yne precursor through a hydrosilylation–protodesilylation protocol. The complete chemo‐, regio‐, and syn‐stereoselectivity of the method also allowed direct access to 11‐ and 12‐monodeutero‐, and 11,12‐dideutero‐11‐cis‐retinoids. The analogous trans series was not accessible by

  一种快速，高效的11-顺-维甲酸类化合物的方法是通过氢化硅烷化-脯氨酰化方法对现成的11-炔前体进行半氢化而实现的。完整的化疗，区域选择性和SYN方法-stereoselectivity也让其11-和12- monodeutero-，和11,12二氘11-直达顺-retinoids。通过该途径无法获得类似的反式序列，并且是通过Hiyama耦合合成的。
• Unique properties of the 11-cis and 11,11′-di-cis isomers of β-carotene as revealed by electronic absorption, resonance Raman and 1H and 13C NMR spectroscopy and by HPLC analysis of their thermal isomerization
  作者：Ying Hu、Hideki Hashimoto、Gérard Moine、Urs Hengartner、Yasushi Koyama

  DOI：10.1039/a703763e

  日期：——

  of other isomers. (2) The frequencies of the CC stretching Raman lines of these isomers are the same as that of the all-trans isomer, and do not follow the general trend of high-frequency shifts found in other mono-cis and di-cis isomers. The Raman lines due to the out-of-plane C–H wagging and methyl rocking modes appear in the 11,11′-di-cis isomer. (3) The 1H chemical shifts of these isomers indicate

  与β-胡萝卜素的全反式和其他顺式异构体相比，11-顺式和11,11'-二顺式异构体表现出以下独特的性质。（1）B的波长ü + â†甲克-（0-0）这两种异构体的吸收是类似于清一色的反式异构体，并且不按它的蓝移的一般规则在发现其他单顺和二顺式异构体。它们的消光系数明显低于其他异构体。（2）这些异构体的C C拉伸拉曼线的频率与全反式的频率相同异构体，而没有按照高频率偏移的其他单中发现大势顺和二顺式异构体。由于11：11'-顺式异构体出现面外CH摆动和甲基摇摆模式而产生的拉曼线。（3）这些异构体的1 H化学位移表明甲基和烯属1 H原子在11-顺式弯曲的凹面之间存在严重的空间相互作用，而它们的13 C化学位移表明顺式C11 C12发生扭曲和极化键。（4）这些异构体的热异构化速率远高于15-顺式异构体，即先前已知的最不稳定的异构体。
• Syntheses of 13C2-labelled 11Z-retinals
  作者：Neville J. McLean、Axel Gansmuller、Maria Concistre、Lynda J. Brown、Malcom H. Levitt、Richard C.D. Brown

  DOI：10.1016/j.tet.2011.07.092

  日期：2011.10

  To enable solid-state NMR investigations of the rhodopsin chromophore and its photointermediates, a series of 11Z-retinal isotopomers have been synthesised containing pairs of adjacent C-13 labels at C9/C10, C10/C11 or C11/C12, respectively. The C9 labelled carbon atom was introduced through the Heck reaction of a C-13-labelled Weinreb acrylamide derivative, and the label at the C12 position derived from a C-13-containing ethoxy Bestmann-Ohira reagent. The C-13 labels at C10 and C11 were introduced through the reaction of beta-ionone with labelled triethyl phosphonoacetate. (C) 2011 Elsevier Ltd. All rights reserved.
• THE SYNTHESIS AND CONFIGURATION OF NEO-b VITAMIN A AND NEORETINENE b
  作者：William Oroshnik

  DOI：10.1021/ja01592a095

  日期：1956.6
• Efficient Synthesis of 11-cis-Retinoids
  作者：Babak Borhan、María L. Souto、Joann M. Um、Bishan Zhou、Koji Nakanishi

  DOI：10.1002/(sici)1521-3765(19990401)5:4<1172::aid-chem1172>3.0.co;2-q

  日期：1999.4.1

  The light sensitivity and unstable nature of 11-cis-retinoids makes them ideal visual chromophores in nature. The synthesis of 11-cis-retinal analogues is of paramount importance in bioorganic studies of rhodopsin, the photoreceptor of the visual transduction pathway, but the instability of 11-cis-retinoids complicates their synthesis and there is no general synthetic route. Common strategies to the cis geometry have failed in the case of 11-cis-retinoids, and most often low yields and complex isomeric mixtures are obtained. Herein we report an efficient, general, and mild preparation of 11-cis-retinoids by semi-hydrogenation of 11-yne-retinoid precursors with Cu/Ag-activated zinc dust.