all-trans-13-demethyl-14-methylretinal | 53121-26-9

• 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: all-trans-13-demethyl-14-methylretinal
• 英文别名: (2E,4E,6E,8E)-2,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
• CAS: 53121-26-9
• 化学式: C₂₀H₂₈O
• 分子量: 284.442
• InChiKey: CRXMTROZEGVYPY-ORROCPSMSA-N

物化性质

• 沸点：
  422.4±14.0 °C(Predicted)
• 密度：
  0.948±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  all-trans-13-demethyl-14-methylretinal 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.17h， 生成 all-trans-13-demethyl-14-methylretinol
  参考文献：
  名称：

  类维生素A和相关化合物。第14部分。共轭4-亚烷基丁烯内酯的新颖合成及其光谱表征

  摘要：

  描述了类胡萝卜素亚烷基丁烯内酯的新合成方法（砜法）以及后者的光谱表征。

  DOI：

  10.1039/p19930000987
• 作为产物：
  描述：

  4-(1,4-二甲基-1-乙基)戊基酚 在 硫酸 、 sodium ethanolate 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 19.0h， 生成 all-trans-13-demethyl-14-methylretinal
  参考文献：
  名称：

  类维生素A和相关化合物。第14部分。共轭4-亚烷基丁烯内酯的新颖合成及其光谱表征

  摘要：

  描述了类胡萝卜素亚烷基丁烯内酯的新合成方法（砜法）以及后者的光谱表征。

  DOI：

  10.1039/p19930000987

文献信息

• Synthesis of C11-to-C14 methyl-shifted all-<i>trans</i>-retinal analogues and their activities on human aldo-keto reductases
  作者：Aurea Rivas、Raquel Pequerul、Vito Barracco、Marta Domínguez、Susana López、Rafael Jiménez、Xavier Parés、Rosana Alvarez、Jaume Farrés、Angel R. de Lera

  DOI：10.1039/d0ob01084g

  日期：——

  The synthesis of these retinoids was based on the formation of a C10–C11 single bond of the pentaene skeleton starting from a trienyl iodide and the corresponding dienylstannanes and dienylsilanes, using the Stille–Kosugi–Migita and Hiyama–Denmark cross-coupling reactions, respectively. Since these reagents differ by the location and presence of methyl groups at the dienylorganometallic fragment, the

  人醛基酮还原酶（AKR）是参与将所有反式-视网膜还原为全反式-视黄醇（维生素A）的酶，因此有助于控制生物体中类维生素A的水平。一系列C11-C14甲基转移（相对于天然C13-甲基）全反式的构效关系研究已经报道了-视网膜类似物作为AKR的假定底物。这些类维生素A的合成基于戊烯骨架的C10–C11单键的形成，分别从Stille–Kosugi–Migita和Hiyama–Denmark交叉偶联反应开始，从三苯基碘化物以及相应的二苯基锡烷和二苯基硅烷开始。 。由于这些试剂的不同之处在于二烯基有机金属片段上甲基的位置和存在，因此该研究还提供了对不同位置异构体进行交叉偶联的能力以及这些过程对位阻的敏感性的见解。所得的C11至C14甲基转移的全反式尽管已注意到底物特异性的相关差异，但在用AKR1B1和AKR1B10酶进行测试时，发现视网膜类似物是活性底物。对于AKR1B1，所有类似物均比母体全反式视网膜表现出更高的催化效率（k
• Bestmann, Hans Juergen; Ermann, Peter; Rueppel, Hartmann, Liebigs Annalen der Chemie, 1986, # 3, p. 479 - 498
  作者：Bestmann, Hans Juergen、Ermann, Peter、Rueppel, Hartmann、Sperling, Walter

  DOI：——

  日期：——
• Experimental and Theoretical Analysis of the Steric Tolerance of the Binding Site of Bacterioopsin with the Use of Side-Chain Methyl-Shifted Retinal Analogs
  作者：Angel R. de Lera、Beatriz Iglesias、Jesus Rodriguez、Rosana Alvarez、Susana Lopez、Xavier Villanueva、Esteve Padros

  DOI：10.1021/ja00136a021

  日期：1995.8

  Four positional isomers of trans-retinal (1) differing in the location of the side-chain methyl groups have been prepared by a combination of Wittig and highly stereocontrolled Suzuki coupling reactions. The incubation of 9-demethyl-10-methylretinal (5) with bacterioopsin yielded an artificial pigment with an opsin shift of 4630 cm(-1) The other three analogs, namely 13-demethyl-14-methylretinal (3), 13-demethyl-12-methylretinal (4), and 9-demethyl-8-methylretinal (6) did not bind to the apoprotein. In order to rationally address the intrinsic structural differences among analogs which could be relevant to the discrimination exhibited by the protein binding site, ab initio calculations with complete optimization at the 3-21G level were performed on model N-methylretinal iminium salts derived from aldehydes 1 and 3-6. The validity of the approach was inferred from the remarkable coincidence between the minimized structure of N-methylretinal Schiff base (PSB-1) and the structural parameters displayed by N-methyl-N-phenylretinal iminium perchlorate (38b). Computations clearly show that the location of the methyl groups on the polyene side chain is of the utmost importance in determining the overall shape of the retinal ligands. Those structural effects, added to the dominant steric and electronic restrictions of the binding pocket, would explain the observed discrimination among the analogs 3-6, with minor structural changes, and perhaps among other retinals reported in the literature. Additionally, the theoretical and experimental results obtained with 9-demethyl-8-methylretinal (6) provide further indirect evidence of the importance of the 6-s-trans conformation for the native chromophore in bacteriorhodopsin.
• Effects of the terminal-methyl position and of the length of the conjugated chain on the cis isomers produced by photo-isomerization: analysis by HPLC and configurational determination by 1H-NMR spectroscopy of isomeric analogues of retinal and β-apo-12′-carotenal
  作者：Ying Hu、Akio Okumura、Yasushi Koyama、Yumiko Yamano、Masayoshi Ito

  DOI：10.1016/s1386-1425(96)01863-x

  日期：1997.6

  An analogue of retinal (beta-apo-12'-carotenal), its terminal-methyl group being shifted from the 13 to 14 (from 13' to 14') position, was subjected to direct (iodine-sensitized) photo-isomerization. The configurations of five (seven) isomers of the retinal (beta-apo-12'-carotenal) analogue were determined by H-1-NMR spectroscopy to be all-trans, 7-, 9- and 11-mono-cis and 9,11-di-cis (all-trans, 9-, 13- and 13'-mono-cis and 9,13-, 9,13'- and 13,13'-di-cis). Comparative direct photo-isomerization in acetonitrile of the above parent and analogue aldehydes showed that the kinds and the amounts of cis isomer produced in the stationary-state mixtures are drastically affected by the terminal-methyl position and by the length of the conjugated chain. The results are discussed in terms of enhanced polarization upon excitation in the terminal C=O and the neighbouring C=C bonds in the conjugated chain. (C) 1997 Published by Elsevier Science B.V.
• USE OR RETINOIDS TO LOWER PLASMA LEVELS OF LIPOPROTEIN (a)
  申请人：WARNER-LAMBERT COMPANY

  公开号：EP0808159A1

  公开（公告）日：1997-11-26