11,13-dicis-retinal | 564-88-5

• 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: 11,13-dicis-retinal
• 英文别名: 11, 13-cis-Retinal (>65%)；(2Z,4Z,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
• CAS: 564-88-5
• 化学式: C₂₀H₂₈O
• 分子量: 284.442
• InChiKey: NCYCYZXNIZJOKI-PXXZYBOJSA-N

物化性质

• 沸点：
  421.4±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)：
  6.2
• 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：

  11,13-dicis-retinal 以 甲基环己烷 为溶剂， 生成 13-顺式视黄醇
  参考文献：
  名称：

  Stereospecific thermal rearrangement of the four labile isomers of retinal. Activation parameters and FT-IR data

  摘要：

  We have determined enthalpy and entropy of activation and FT-IR spectra of the four thermally labile isomers of retinal (11,13-dicis, 7,11,13-tricis, 9,11,13-tricis, and all-cis). The data are in agreement with the postulated Kluge-Lillya mechanism of isomerization, involving consecutive 6e-electrocyclization reactions for the stereospecific reactions.

  DOI：

  10.1021/jo00030a015
• 作为产物：
  描述：

  视黄醛 以 正己烷 为溶剂， 生成 11,13-dicis-retinal
  参考文献：
  名称：

  Selective isomerization of retinal upon two-photon excitation

  摘要：

  The products of photo-isomerization when excited directly up to the two-photon-allowed (1)A(g)(-) excited state of alltrans and five cis isomers of retinal were determined. The composition of the isomers at the photo-stationary state was drastically changed as compared to one-photon excitation. The production of the 13-cis isomer was selectively increased, and the production of the dicis isomers was observed in the case of a direct excitation upon the 3(1)A(g)(-) state, although they were hard to be produced by one-photon excitation in n-hexane solution. These results clearly evidenced that there exist isomerization pathways via two-photon-allowed excited states. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0009-2614(02)02034-1

文献信息

• Complex Thermal Behavior of 11-<i>cis</i>-Retinal, the Ligand of the Visual Pigments
  作者：Carlos Silva López、Rosana Álvarez、Marta Domínguez、Olalla Nieto Faza、Ángel R. de Lera

  DOI：10.1021/jo801899k

  日期：2009.2.6

  competition between two mechanisms of very different nature. A classical internal rotation around the C11−C12 cis double bond, via a diradical transition state, accounts for the formation of the all-trans isomer. An intricate sequence of pericyclic reactions, namely a reversible [1,7]-H sigmatropic shift and a reversible 6-π-oxa-electrocyclic reaction, is responsible for the formation of 13-cis-retinal. Experiments

  在加热至80℃时，11-顺-视网膜产生全反式-视网膜和13-顺-视网膜的混合物。已经通过密度泛函理论方法研究了这种异构化，并且计算结果表明性质非常不同的两种机理之间存在密切竞争。周围的C11-C12甲古典内旋顺式双键，通过二价基团的过渡状态下，占形成所有-反式异构体。周环反应的复杂序列，即可逆的[1,7] -Hσ位移和可逆的6-π-氧杂-电环反应，负责13-顺-视网膜的形成。使用11-顺式进行实验-在C19处标记有氘的视网膜证实了该机制，并且还揭示了同位素同位素产物的空前结果。
• Transient phenomena in the pulse radiolysis of retinyl polyenes. 2. Protonation kinetics
  作者：K. Bobrowski、P. K. Das

  DOI：10.1021/ja00370a043

  日期：1982.3

  In the cases of retinol and retinyl acetate, the initial H/sup +/ adduct undergoes loss of water and acetic acid, respectively, producing the retinyl carbonium ion (lambda/sub max/585 nm), which, in turn, decays with first-order kinetics (t/sub 1///sub 2/ = 10 +/- 3 ..mu..s). The rate constants for protonation are in the range 1 x 10/sup 7/ - 4 x 10/sup 9/ M/sup -1/ s/sup -1/. In the cases of polyene

  研究结果涉及各种视黄基衍生物与在含有 0.5 M 丙酮和 0.2 M 四氯化碳的充气 2-丙醇中以辐射方式释放脉冲的氢离子的反应动力学。对于视黄醛和多烯席夫碱，它们的质子化形式比未质子化的底物吸收更长的波长，并通过动力学分光光度法进行监测。在视黄醇和视黄醇乙酸酯的情况下，最初的 H/sup +/ 加合物分别失去水和乙酸，产生视黄基碳正离子（λ/sub max/585 nm），反过来，首先衰变-阶动力学（t/sub 1//sub 2/ = 10 +/- 3 ..mu..s）。质子化的速率常数在 1 x 10/sup 7/ - 4 x 10/sup 9/ M/sup -1/ s/sup -1/ 的范围内。在多烯席夫碱的情况下，随着多烯链长度的增加，质子化速率常数略有增加，11-顺式-视黄醛席夫碱的质子化速率常数高于其全反式对应物。在脉冲辐解质子化的早期阶段观察到的质子化多烯席夫碱的吸收光谱最大值红移了大约
• HINDERED CIS ISOMERS OF VITAMIN A AND RETINENE: THE STRUCTURE OF THE NEO-B ISOMER
  作者：George Wald、Paul K. Brown、Ruth Hubbard、William Oroshnik

  DOI：10.1073/pnas.41.7.438

  日期：1955.7.15
• Thermal sigmatropic rearrangements of vinylallenes leading to 11-cis-retinoids and the novel properties of 9-cis,11-cis,13-cis-retinal and 11-cis,13-cis-retinal
  作者：Christopher G. Knudsen、Roshantha A. S. Chandraratna、Leslie P. Walkeapaa、Yeshpal S. Chauhan、Stephen C. Carey、Thomas M. Cooper、Robert R. Birge、William H. Okamura

  DOI：10.1021/ja00344a034

  日期：1983.3
• Ruzziconi, Renzo; Schlosser, Manfred, Angewandte Chemie, 1982, vol. 94, # 11, p. 865 - 866
  作者：Ruzziconi, Renzo、Schlosser, Manfred

  DOI：——

  日期：——