ZEAXANTHIN玉米黄质 | 72002-36-9

• 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
• 中文名称: ZEAXANTHIN玉米黄质
• 中文别名: β,β-胡萝卜素-3,3'-二醇；玉米须提取物10:1；玉米黄素；玉米黄质
• 英文名称: (3S,3'S)-β,β-carotene-diol
• 英文别名: (3S,3'S)-zeaxanthin；zeaxanthin；(3S,3'S)-β,β-carotene-3,3'-diol；3R-3'R-zeaxanthin；Zeaxanthin, (3S,3'S)-；(1S)-4-[(1E,3E,5E,7E,9E,11E,13E,15E,17E)-18-[(4S)-4-hydroxy-2,6,6-trimethylcyclohexen-1-yl]-3,7,12,16-tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaenyl]-3,5,5-trimethylcyclohex-3-en-1-ol
• CAS: 72002-36-9
• 化学式: C₄₀H₅₆O₂
• 分子量: 568.883
• InChiKey: JKQXZKUSFCKOGQ-ANDPMPNWSA-N

物化性质

• 沸点：
  711.4±55.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)
• 物理描述：
  Solid
• 熔点：
  209-209.5°C

计算性质

• 辛醇/水分配系数(LogP)：
  10.9
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ZEAXANTHIN玉米黄质 、 1-(Vitamin-A-oyl)imidazol 在 吡啶 、 sodium hydride 作用下， 反应 2.5h， 以50%的产率得到(3S,3'S)-zeaxanthin monoretinoate
  参考文献：
  名称：

  Carotenoids with two chromophores: carotenoid retinoates

  摘要：

  In this study, carotenoid retinoates are described for the first time. The preparation was achieved by the azolide method. Various sec carotenols reacted with N-retinoylimidazol in the presence of catalytic amounts of sodium hydride. Mono- and diretinoates of (3R,3'R)-zeaxanthin and its (3S,3'S)-enantiomer, (9Z,9'Z; 3R,3'R)-alloxanthin, (3R,3'R)-7,8,7',8'-tetrahydro-3,3'-dihydroxy-,-carotene-8,8'-dione and (3R,6R,3'R,6'R)-epsilon,epsilon-carotene-3,3'-diol (lactucaxanthin), as well as monoretinoates of (3R,3'RS,6'R)-3'-methoxy-,epsilon-caroten-3-ol, (3R,3'RS,6'R)-3-methoxy-,epsilon-caroten-3'-ol, (2R,6'RS)-,epsilon-caroten-2-ol, (3R,3'S; meso)-astaxanthin and (2'R)-aleuriaxanthin are reported in this study. Spectroscopic properties (1H-NMR mass spectrometry, visible and circular dichroism spectra) are discussed. Studies on other carotenoid derivatives with two chromophores are referred to here.

  DOI：

  10.1080/14786419.2010.488629
• 作为产物：
  描述：

  玉米黄质 在 氢氧化钾 、 甲酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 生成 ZEAXANTHIN玉米黄质
  参考文献：
  名称：

  Sliwka, Hans-Richard; Liaaen-Jensen, Synnoee, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1987, vol. 41, # 7, p. 518 - 525

  摘要：

  DOI：

文献信息

• Process for Synthesis of (3S)- and (3R)-3-Hydroxy-Beta-Ionone, and Their Transformation to Zeaxanthin and Beta-Cryptoxanthin
  申请人：Khachik Frederick

  公开号：US20090311761A1

  公开（公告）日：2009-12-17

  (3R)-3-Hydroxy-β-ionone and (3S)-3-hydroxy-β-ionone are two important intermediates in the synthesis of carotenoids with β-end group such as lutein, zeaxanthin, β-cryptoxanthin, and their stereoisomers. Among the various stereoisomers of these carotenoids, only (3R,3′R,6′R)-lutein, (3R,3′R)-zeaxanthin, and (3R)-β-cryptoxanthin are present in commonly consumed fruits and vegetables. There are 3 possible stereoisomers for zeaxanthin, these are: dietary (3R,3′R)-zeaxanthin (1), non-dietary (3S,3′S)-zeaxanthin (2), and non-dietary (3R,3′S;meso)-zeaxanthin (3) which is a presumed metabolite of dietary lutein. Dietary lutein as well as 1 and 3 are accumulated in the human macula and have been implicated in the prevention of age-related macular degeneration. (3R)-β-Cryptoxanthin (4) is also present in selected ocular tissues at a very low concentration whereas its enantiomer (3S)-β-cryptoxanthin (5) is absent in foods and human plasma. The present invention relates to a process for the synthesis of (3R)-3-hydroxy-β-ionone and its (3S)-enantiomer in high optical purity from commercially available (rac)-α-ionone. The key intermediate for the synthesis of these hydroxyionones is 3-keto-α-ionone ketal that was prepared from (rac)-α-ionone after protection of this ketone as a 1,3-dioxolane. Reduction of 3-keto-α-ionone ketal followed by deprotection, lead to 3-hydroxy-α-ionone that was transformed into (rac)-3-hydroxy-β-ionone by base-catalyzed double bond isomerization in 46% overall yield from (rac)-α-ionone. The racemic mixture of these hydroxyionones was then resolved by enzyme-mediated acylation in 96% ee. (3R)-3-Hydroxy-β-ionone and its (3S)-enantiomer were respectively transformed to (3R)-3-hydroxy-(β-ionylideneethyl)triphenylphosphonium chloride [(3R)—C 15 -Wittig salt] and its (3S)-enantiomer [(3S)—C 15 -Wittig salt] according to known procedures. Double Wittig condensation of these Wittig salts with commercially available 2,5-dimethylocta-2,4,6-triene-1,8-dial provided all 3 stereoisomers of zeaxanthin (1-3). Similarly, (3R)—C 15 -Wittig and its (3S)-enantiomer were each coupled with β-apo-12′-carotenal to yield 4 and 5.

  (3R)-3-羟基-β-离子酮和(3S)-3-羟基-β-离子酮是合成带有β末端基团的类胡萝卜素如叶黄素、玉米黄质、β-隐黄素及其立体异构体的两个重要中间体。在这些类胡萝卜素的各种立体异构体中，只有(3R,3′R,6′R)-叶黄素、(3R,3′R)-玉米黄质和(3R)-β-隐黄素存在于常见的水果和蔬菜中。玉米黄质有3种可能的立体异构体，分别是：膳食(3R,3′R)-玉米黄质（1）、非膳食(3S,3′S)-玉米黄质（2）和非膳食(3R,3′S;meso)-玉米黄质（3），后者被认为是膳食叶黄素的代谢产物。膳食叶黄素以及1和3在人类黄斑中积累，并被认为有助于预防年龄相关性黄斑变性。 (3R)-β-隐黄素（4）也以极低浓度存在于选定的眼部组织中，而其对映异构体(3S)-β-隐黄素（5）在食物和人类血浆中不存在。本发明涉及一种从市售的（rac）-α-离子酮合成（3R）-3-羟基-β-离子酮及其（3S）对映体的高光学纯度的过程。合成这些羟基酮的关键中间体是从（rac）-α-离子酮制备的3-酮-α-离子酮缩酮，在保护该酮为1,3-二氧兰后得到。随后对3-酮-α-离子酮缩酮进行还原和去保护，得到3-羟基-α-离子酮，再经碱催化的双键异构化，从（rac）-α-离子酮中总产率为46%地转化为（rac）-3-羟基-β-离子酮。然后通过酶介导的酰化将这些羟基酮的外消旋混合物在96%纯度下分离。 (3R)-3-羟基-β-离子酮及其（3S）对映体分别按照已知程序转化为(3R)-3-羟基-(β-离子乙基)三苯基膦盐[(3R)—C15-Wittig盐]和其（3S）对映体[(3S)—C15-Wittig盐]。这些Wittig盐与市售的2,5-二甲基辛-2,4,6-三烯-1,8-二醛进行双Wittig缩合，提供了叶黄素的3种立体异构体（1-3）。类似地，(3R)—C15-Wittig及其（3S）对映体分别与β-脱氧-12'-类胡萝卜醛偶联，得到4和5。
• Process or synthesis of (3S)- and (3R)-3-hydroxy-beta-ionone, and their transformation to zeaxanthin and beta-cryptoxanthin
  申请人：University of Maryland, College Park

  公开号：US08222458B2

  公开（公告）日：2012-07-17

  Disclosed is a process for the synthesis of (3R)-3-hydroxy-β-ionone and its (3S)-enantiomer in high optical purity from commercially available (rac)-α-ionone. The key intermediate for the synthesis of these hydroxyionones is 3-keto-α-ionone ketal that was prepared from (rac)-α-ionone after protection of this ketone as a 1,3-dioxolane. Reduction of 3-keto-α-ionone ketal followed by deprotection, lead to 3-hydroxy-α-ionone that was transformed into (rac)-3-hydrox-β-ionone by base-catalyzed double bond isomerization in 46% overall yield from (rac)-α-ionone. The racemic mixture of these hydroxyionones was then resolved by enzyme-mediated acylation in 96% ee. (3R)-3-Hydroxy-β-ionone and its (3S)-enantiomer were respectively transformed to (3R)-3-hydroxy-(β-ionylideneethyl)triphenylphosphonium chloride [(3R)-C15-Wittig salt] and its (3S)-enantiomer [(3S)-C15-Wittig salt] according to known procedures. Double Wittig condensation of these Wittig salts with commercial available 2,5- dimethtylocta-2,4,6-triene-1,8-dial provided all 3 stereoisomers of zeaxanthin. Similarly, (3R)-C15-Wittig and its (3S)-enantiomer were each coupled with β-apo-12′-carotenal.

  本文披露了一种从商业可获得的（rac）-α-离子酮合成（3R）-3-羟基-β-离子酮及其（3S）对映体的高光学纯度的过程。合成这些羟基离子酮的关键中间体是从（rac）-α-离子酮制备的3-酮-α-离子酮缩酮，经过将该酮保护为1,3-二氧杂环后得到。还原3-酮-α-离子酮缩酮，然后去保护，得到3-羟基-α-离子酮，通过碱催化的双键异构化，从（rac）-α-离子酮中总产率为46%转化为（rac）-3-羟基-β-离子酮。这些羟基离子酮的混合物随后通过酶介导的酰化在96%的ee下分离。（3R）-3-羟基-β-离子酮及其（3S）对映体分别按照已知程序转化为（3R）-3-羟基-(β-离子基乙基)三苯基膦盐[(3R)-C15-Wittig盐]和其（3S）对映体[(3S)-C15-Wittig盐]。将这些Wittig盐与商业可获得的2,5-二甲基辛二烯-1,8-二醛进行双Wittig缩合，得到所有3种类脂黄素的立体异构体。类似地，（3R）-C15-Wittig及其（3S）对映体分别与β-脱氧-12'-类胡萝卜素醛偶联。
• Synthese von optisch aktiven, natürlichen Carotinoiden und strukturell verwandten Naturprodukten. V. Synthese von (3R, 3′R)-, (3S, 3′S)- und (3R,3′S; meso)-Zeaxanthin durch asymmetrische Hydroborierung. Ein neuer Zugang zu Optisch aktiven Carotinoidbauste
  作者：August Rüttimann、Hans Mayer

  DOI：10.1002/hlca.19800630615

  日期：1980.9.17

  Synthesis of Optically Active Natural Carotenoids and Structurally Related Compounds. V. Synthesis of (3R, 3′R)-, (3S, 3′S)- and (3R,3′S; meso)-zeaxanthin by Asymmetric Hydroboration. A New Approach to Optically Active Carotenoid Building Units

  光学活性天然类胡萝卜素和结构相关化合物的合成。V.（3合成[R '，3 - [R - （，3）小号，3'小号-和（3）- [R，3' š ;内消旋通过不对称硼氢化-zeaxanthin）。光学活性类胡萝卜素构建单元的新方法
• Carotenoids Enhance Vitamin E Antioxidant Efficiency
  作者：Fritz Böhm、Ruth Edge、Edward J. Land、David J. McGarvey、T. George Truscott

  DOI：10.1021/ja962512c

  日期：1997.1.1
• CAROTENOID COMPOSITIONS AND USES THEREOF
  申请人：L.E.A.F. HOLDINGS GROUP LLC

  公开号：US20220409565A1

  公开（公告）日：2022-12-29

  Provided herein are pharmaceutical compositions comprising carotenoids, including liposomes that encapsulate carotenoids including ionizable carotenoids such as trans-crocetin. The provided compositions have uses in treating diseases, disorders and conditions associated with, but not limited to, infection, endotoxemia, inflammation, sepsis, ischemia, hypoxia, shock, stroke, lung injury, wound healing, traumatic injury, reperfusion injury, cardiovascular disease, kidney disease, liver disease, inflammatory disease, metabolic disease, pulmonary disorders, blood related disorders and hyperproliferative diseases such as cancer. Methods of making, delivering, and using the pharmaceutical compositions are also provided.