(rac)-(E)-4-(4-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-yl)-2,2-ethylenedioxy-3-butene | 1200125-02-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (rac)-(E)-4-(4-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-yl)-2,2-ethylenedioxy-3-butene
• 英文别名: (rac)-3-hydroxy-α-ionone ketal；3,5,5-trimethyl-4-[(E)-2-(2-methyl-1,3-dioxolan-2-yl)ethenyl]cyclohex-2-en-1-ol
• CAS: 1200125-02-5
• 化学式: C₁₅H₂₄O₃
• 分子量: 252.354
• InChiKey: GEICCRSWONBOLI-AATRIKPKSA-N

物化性质

• 沸点：
  328.8±42.0 °C(Predicted)
• 密度：
  1.116±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (rac)-(E)-4-(4-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-yl)-2,2-ethylenedioxy-3-butene 在 1,2-环氧丁烷 、 盐酸 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 水 、 丙酮 、 甲苯 为溶剂， 反应 4.0h， 生成 (2E,4E,6E,8E,10E,12E)-13-(4-hydroxy-2,6,6-trimethylcyclohex-1-en-1-yl)-2,7,11-trimethyltrideca-2,4,6,8,10,12-hexaenal
  参考文献：
  名称：

  Synthesis and Characterization of Quantum Dot Nanoparticles Bound to the Plant Volatile Precursor of Hydroxy-apo-10′-carotenal

  摘要：

  This study is focused on the synthesis and characterization of hydroxy-apo-10'-carotenal/quantum dot (QD) conjugates aiming at the in vivo visualization of β-ionone, a carotenoid-derived volatile compound known for its important contribution to the flavor and aroma of many fruits, vegetables, and plants. The synthesis of nanoparticles bound to plant volatile precursors was achieved via coupling reaction of the QD to C27-aldehyde which was prepared from α-ionone via 12 steps in 2.4% overall yield. The formation of the QD-conjugate was confirmed by measuring its fluorescence spectrum to observe the occurrence of fluorescence resonance energy transfer.

  DOI：

  10.1021/jo500605c
• 作为产物：
  描述：

  (E)-4-(4-oxo-2,6,6-trimethyl-2-cyclohexen-1-yl)-2,2-ethylenedioxy-3-butene 在 二异丁基氢化铝 作用下， 以 二氯甲烷 、 环己烷 为溶剂， 生成 (rac)-(E)-4-(4-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-yl)-2,2-ethylenedioxy-3-butene
  参考文献：
  名称：

  钯催化乙烯基醇的 S-烯丙基化——通过 Julia-Kocienski 烯化全合成类胡萝卜素

  摘要：

  钯催化紫罗兰酮（或共轭羰基）与 2-巯基-1,3-苯并噻唑 (BT-SH) 发生乙烯基甲醇的 S-烯丙基化反应，得到多用途的 C 15二烯基苯并噻唑基 (BT) 硫化物。这种Pd(dppe)Cl 2催化的S-烯丙基化在烯丙乙酸酯存在下对游离烯丙醇具有高度选择性，产生适合叶黄素合成的3-或4-乙酰氧基C 15二烯基BT-硫化物。相应的C 15二烯基BT-砜与C 10 2,7-二甲基-2,4,6-辛三烯二醛在温和条件下进行Julia-Kocienski烯化反应，生成类胡萝卜素天然产物。实现了一系列类胡萝卜素的高效合成，包括叶黄素（如异玉米黄质、玉米黄质和叶黄素）以及胡萝卜素（如 β-胡萝卜素、ε-胡萝卜素和 9'- Z-苯基胡萝卜素）。

  DOI：

  10.1002/adsc.202301055

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。
• Synthesis of (3S)- and (3R)-3-Hydroxy-β-ionone and Their Transformation into (3S)- and (3R)-β-Cryptoxanthin
  作者：Frederick Khachik、An-Ni Chang

  DOI：10.1055/s-0030-1258382

  日期：2011.2

  (3R)-3-Hydroxy-β-ionone and (3S)-3-hydroxy-β-ionone were synthesized in high enantiomeric purity from commercially available (±)-α-ionone. These ionones were then transformed into (3R)-β-cryptoxanthin and (3S)-β-cryptoxanthin by a C15+C10+C15 Wittig coupling strategy according to known methods. This methodology can considerably simplify the total synthesis of optically active carotenoids with 3-hydroxy-β-end

  （3R）-3-羟基-β-紫罗兰酮和（3S）-3-羟基-β-紫罗兰酮由对映体纯度高的市售（±）-α-紫罗兰酮合成。然后根据已知方法通过C 15 + C 10 + C 15 Wittig偶联策略将这些紫罗兰酮转化为（3 R）-β-隐黄质和（3 S）-β-隐黄质。这种方法可以极大地简化具有3-羟基-β-端基的旋光性类胡萝卜素的总合成，所述基团具有明显的生物活性。 羟基类胡萝卜素-类胡萝卜素前体-手性拆分-立体选择性合成-Wittig反应
• Identification of Apocarotenoids as Chemical Markers of In Vitro Anti-Inflammatory Activity for Spirulina Supplements
  作者：Karen C. Tan、Tho X. Pham、Yoojin Lee、Ji-Young Lee、Marcy J. Balunas

  DOI：10.1021/acs.jafc.1c03015

  日期：2021.11.3
• US8222458B2
  申请人：——

  公开号：US8222458B2

  公开（公告）日：2012-07-17