13-cis canthaxanthin

• 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: 13-cis canthaxanthin
• 英文别名: 2,4,4-trimethyl-3-[(1E,3E,5E,7E,9E,11Z,13E,15E,17E)-3,7,12,16-tetramethyl-18-(2,6,6-trimethyl-3-oxocyclohexen-1-yl)octadeca-1,3,5,7,9,11,13,15,17-nonaenyl]cyclohex-2-en-1-one
• 化学式: C₄₀H₅₂O₂
• 分子量: 564.852
• InChiKey: FDSDTBUPSURDBL-XHLTVIPNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.4
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  斑蝥黄 在 zinc(II) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 9-顺式角黄素 、 13-cis canthaxanthin
  参考文献：
  名称：

  Semiconductor Photocatalysis:  Photodegradation and Trans−Cis Photoisomerization of Carotenoids

  摘要：

  In the presence of semiconductor CdS or ZnO particles, irradiation (>350 nm) of all-trans-beta-carotene (II) in dichloromethane leads to rapid degradation of the carotenoid, which is relatively stable in the absence of the semiconductors. Canthaxanthin (I), however, undergoes significant photocatalyzed degradation only on ZnO, not on CdS. High-performance liquid chromatographic studies indicate that CdS catalyzes trans-cis photoisomerization of both I and II. As in the photoisomerization in the absence of semiconductor, the major cis isomers have the 9-cis and 13-cis configuration, but, under otherwise the same condition, the ratio of cis/trans isomers has doubled. In contrast to CdS, ZnO does not catalyze the photoisomerization of either I or II, although it enhances their rate of degradation. A photoisomerization mechanism involving carotenoid radicals formed by reaction with interstitial sulfur on the CdS surface is proposed.

  DOI：

  10.1021/jp980326i

文献信息

• Selected cis/trans isomers of carotenoids formed by bulk electrolysis and iron(III) chloride oxidation
  作者：Chih-Chang Wei、Guoqiang Gao、Lowell D. Kispert

  DOI：10.1039/a605027a

  日期：——

  Bulk electrolysis and chemical oxidation with FeCl3 of all-trans canthaxanthin (I) and 8′-apo-β-caroten-8′-al (II) gave primarily the 9- and 13-cis-isomers, which were separated by HPLC and identified by 1H NMR spectroscopy. Optical absorption measurements showed that the 15-cis, 9,13-di-cis isomers of I are also formed by these methods. In the case of the unsymmetrical compound II, additional isomers were formed. The cis isomers account for about 40–60% of products formed. Formation of the isomers is believed to occur by rotation about certain bonds in the cation radicals or dications, which are formed in the oxidation processes. The neutral cis species are then formed by an electron exchange reaction of the cis-cation radicals with neutral all-trans carotenoids in solution. The electrochemical and iron(III) chloride oxidation induced isomerization are shown to be efficient and improved methods for forming selected carotenoid isomers.

  大规模电解和氯化铁（FeCl3）化学氧化全反式的卡餐黄素（I）和8'-阿波-β-胡萝卜素-8'-醛（II）主要生成9-和13-顺式异构体，这些异构体通过高效液相色谱法（HPLC）分离，并通过1H NMR光谱鉴定。光学吸收测量表明，这些方法还形成了15-顺式和9,13-双顺式异构体I。在不对称化合物II的情况下，形成了额外的异构体。顺式异构体占生成的产品约40-60%。异构体的形成被认为是通过氧化过程生成的阳离子自由基或二阳离子在某些键周围的旋转而发生。随后，顺式中性物种通过顺式阳离子自由基与溶液中的中性全反式胡萝卜素之间的电子交换反应生成。电化学和铁（III）氯化物氧化诱导的异构化被证明是形成选定胡萝卜素异构体的有效且改进的方法。
• Application of Diphenyl Diselenide as a New Catalyst for Photochemical Stereoisomerization of Carotenoids.
  作者：Aase Strand、Synnøve Liaaen-Jensen、Kjell Undheim、Salo Gronowitz、Anna-Britta Hörnfeldt、Luis Juliá、Ola Persson

  DOI：10.3891/acta.chem.scand.52-1263

  日期：——

  In a comparative study, diphenyl diselenide was shown to be an alternative to iodine as a catalyst for photochemical E/Z isomerization of carotenoids. Suitable conditions for the stereomutation of zeaxanthin, violaxanthin, canthaxanthin and fucoxanthin are reported.Photochemical allenic isomerization with increased R to S conversion was achieved by employing diphenyl diselenide rather than iodine as the catalyst.Reproducible and expedient artificial light conditions, avoiding insolation (sunlight), are reported.Diphenyl diselenide tolerated the presence of Hunig's base upon stereoisomerization of acid-sensitive carotenoids.Diphenyl ditelluride effected E/Z stereomutation, but no allenic RIS isomerization of fucoxanthin.The presence of base decreased the isomerization rate in the absence of catalyst and may serve to decrease undesirable E/Z stereoisomerization of base-stable carotenoids.
• Semiconductor Photocatalysis:  Photodegradation and Trans−Cis Photoisomerization of Carotenoids
  作者：Guoqiang Gao、Yi Deng、Lowell D. Kispert

  DOI：10.1021/jp980326i

  日期：1998.5.1

  In the presence of semiconductor CdS or ZnO particles, irradiation (>350 nm) of all-trans-beta-carotene (II) in dichloromethane leads to rapid degradation of the carotenoid, which is relatively stable in the absence of the semiconductors. Canthaxanthin (I), however, undergoes significant photocatalyzed degradation only on ZnO, not on CdS. High-performance liquid chromatographic studies indicate that CdS catalyzes trans-cis photoisomerization of both I and II. As in the photoisomerization in the absence of semiconductor, the major cis isomers have the 9-cis and 13-cis configuration, but, under otherwise the same condition, the ratio of cis/trans isomers has doubled. In contrast to CdS, ZnO does not catalyze the photoisomerization of either I or II, although it enhances their rate of degradation. A photoisomerization mechanism involving carotenoid radicals formed by reaction with interstitial sulfur on the CdS surface is proposed.