3-hydroxy-β-ionol

• 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: 3-hydroxy-β-ionol
• 英文别名: 4-(3-Hydroxybut-1-enyl)-3,5,5-trimethylcyclohex-3-enol；4-[(E)-3-hydroxybut-1-enyl]-3,5,5-trimethylcyclohex-3-en-1-ol
• 化学式: C₁₃H₂₂O₂
• 分子量: 210.316
• InChiKey: JUFKQNCQDFHWFD-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  3-hydroxy-β-ionol 生成 3-hydroxy-β-ionone
  参考文献：
  名称：

  YASUDA, XITOSI;FUKATANI, TSUTOMU;OKANO, NORIMITSU;JOKOYAMA, KADZUMASA

  摘要：

  DOI：
• 作为产物：
  描述：

  (+/-)-3-hydroxy-7,8-dehydro-β-ionol 生成 3-hydroxy-β-ionol
  参考文献：
  名称：

  YASUDA, XITOSI;FUKATANI, TSUTOMU;OKANO, NORIMITSU;JOKOYAMA, KADZUMASA

  摘要：

  DOI：

文献信息

• New Synthesis of Megastigma-4,6,8-trien-3-ones, 3-Hydroxy-β-ionol, 3-Hydroxy-β-ionone, 5,6-Epoxy-3-hydroxy-β-ionol, and 3-Oxo-<i>a</i>-ionol
  作者：Osamu Takazawa、Hiroshi Tamura、Kunio Kogami、Kazuo Hayashi

  DOI：10.1246/bcsj.55.1907

  日期：1982.6

  The Lewis acid-catalysed reaction of 1-trimethylsiloxy-1,3-cyclohexadienes with aldehydes and trialkyl orthoformates afforded the corresponding 4-substituted 2-cyclohexenones. A new reaction of 2,4,6-trienones with m-chloroperbenzoic acid followed by the reduction with zinc in acetic acid gave 7-hydroxy-3,5-dienones. Utilizing these efficient reactions, megastigma-4,6,8-trien-3-ones, 3-hydroxy-β-ionol, 3-hydroxy-β-ionone, 5,6-epoxy-3-hydroxy-β-ionol, and 3-oxo-α-ionol were successfully synthesized.

  路易斯酸催化的1-三甲基硅氧基-1,3-环己二烯与醛和三烷基正戊酸酯的反应得到了相应的4-取代2-环己烯酮。2,4,6-三烯酮与对氯酸苯甲酸的反应，再经过醋酸中锌还原，得到7-羟基-3,5-二烯酮。利用这些高效反应，成功合成了megastigma-4,6,8-三烯-3-酮、3-羟基-β-离子醇、3-羟基-β-离子酮、5,6-环氧-3-羟基-β-离子醇以及3-氧基-α-离子醇。
• 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。
• Racemic and optically active 3-hydroxy-alpha-cyclocitral, its acetals
  申请人：BASF Aktiengesellschaft

  公开号：US04594456A1

  公开（公告）日：1986-06-10

  3-Hydroxy-.alpha.-cyclocitral derivatives of the general formula I ##STR1## where R.sup.1 is ##STR2## wherein R.sup.2 and R.sup.3 can be identical or different and are each straight-chain or branched alkyl of 1 to 6 carbon atoms, or R.sup.2 and R.sup.3 together form an ethylene or propylene group which can be substituted by methyl or ethyl, processes for their preparation and their use for the preparation of safranal and 3-hydroxy-.beta.-cyclocitral, as well as optically active - cyclocitral derivatives of the general formulae A and B ##STR3## where R.sup.1 is ##STR4## if X is hydrogen and Y is OH, but is otherwise ##STR5## where R.sup.2 and R.sup.3 have the above meanings, and X and Y together are oxygen, or X is hydrogen if Y is OH, and a process for the preparation of optically active 3-oxo-.alpha.-cyclocitral acetals, wherein a mixture of the corresponding racemic 3-oxo-.alpha.-cyclocitral acetals is separated into the optically active compounds by chromatography over a suitable chiral adsorbent. The novel compounds open up a novel advantageous route to optically active 3-hydroxy-.beta.-cyclocitrals, which are desirable because they are important intermediates for carotinoids identical to the natural products.

  本发明涉及一般式I的3-羟基-.alpha.-环柠檬醛衍生物，其中R.sup.1是##STR2##其中R.sup.2和R.sup.3可以相同也可以不同，它们各自是1到6个碳原子的直链或支链烷基，或者R.sup.2和R.sup.3一起形成一个乙烯或丙烯基，该基团可以被甲基或乙基取代，以及它们的制备方法和用于制备番红花醛和3-羟基-.beta.-环柠檬醛的用途，以及一般式A和B的光学活性-环柠檬醛衍生物##STR3##其中R.sup.1是##STR4##如果X是氢，Y是OH，否则是##STR5##其中R.sup.2和R.sup.3具有上述含义，且X和Y一起是氧，或者如果Y是OH，则X是氢，并且制备光学活性3-氧代-.alpha.-环柠檬醛缩醛的方法，其中相应的外消旋3-氧代-.alpha.-环柠檬醛缩醛的混合物通过在适当的手性吸附剂上进行色谱分离而分离成光学活性化合物。这些新化合物开辟了一种新的优势路线，用于制备与天然产物相同的类胡萝卜素的重要中间体3-羟基-.beta.-环柠檬醛。
• Cycloalkane derivatives and anti-peptic ulcer compositions containing same
  申请人：THE GREEN CROSS CORPORATION

  公开号：EP0270124A2

  公开（公告）日：1988-06-08

  A cycloalkane derivative represented by formula (I) : wherein A, R2, R3, R4, R5, R6, R7, Z, and n are as defined in the specification. The compounds of formula (I) exhibit activities against peptic ulcers and are useful as therapeutic and prophylactic agents for peptic ulcers.

  由式 (I) 表示的环烷衍生物：其中 A、R2、R3、R4、R5、R6、R7、Z 和 n 如说明书中所定义。 式 (I) 的化合物具有抗消化性溃疡的活性，可用作消化性溃疡的治疗剂和预防剂。
• 2-(2-Butenylidene)-3,3-dimethyl-5-(2-oxopropyl)tetrahydrofuran: A New Degradation Product of 3-Hydroxy-5,6-epoxy-.beta.-ionol
  作者：Wolfgang Neugebauer、Peter Winterhalter、Peter Schreier

  DOI：10.1021/jf00048a044

  日期：1994.12

  Identification of 2-(2-butenylidene)-3,3-dimethyl-5-(2-oxopropyl)tetrahydrofuran diastereomers (4, 5) in various leaves [stinging nettle; sloe tree; strawberry; vine (Riesling); sweet silique (Bunias orientalis)] was achieved by comparison of HRGC retention and spectral (MS; vapor phase FTIR) data with those of synthetic references. Model experiments revealed their acid-catalyzed formation from 3-hydroxy-5,6-epoxy-beta-ionol that was present in glycosidically bound form in the above-mentioned leaves. Assignment of the isomers 4a/4b and 5a/5b was established by NOE experiments. Enantiodifferentiation carried out by on-line coupled multidimensional gas chromatography-mass spectrometry revealed the occurrence of enantiomerically pure 5S enantiomers 4b/5b in the natural sources. A pathway for the selective formation of 4b/5b in nature is proposed.