4-羟基-2,2,6-三甲基环己酮 | 20548-02-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-羟基-2,2,6-三甲基环己酮
• 英文名称: 4-hydroxy-2,2,6-trimethylcyclohexanone
• 英文别名: 4-Hydroxy-2,2,6-trimethylcyclohexanon；trans (4R,6R)-4-hydroxy-2,2,6-trimethylcyclohexanone；4-hydroxy-2,2,6-trimethylcyclohexan-1-one
• CAS: 20548-02-1
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: CSPVUHYZUZZRGF-UHFFFAOYSA-N

物化性质

• 沸点：
  239.1±33.0 °C(Predicted)
• 密度：
  0.986±0.06 g/cm3(Predicted)
• 稳定性/保质期：
  存在于烟叶中。

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-羟基-2,2,6-三甲基环己酮 在 bis-triphenylphosphine-palladium(II) chloride 、 四(三苯基膦)钯 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (E)-<3-(4-tert-Butyldimethylsilyloxy-2,6,6-trimethylcyclohex-1-enyl)allyl>sulfonylbenzene
  参考文献：
  名称：

  Masayoshi, Ito; Hirata, Yumiko; Shibata, Yuko, Journal of the Chemical Society. Perkin transactions I, 1990, # 1, p. 197 - 199

  摘要：

  DOI：
• 作为产物：
  描述：

  2,6,6-三甲基-2-环己烯-1,4-二酮 在 Ra-Ni 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、110.0 kPa 条件下， 反应 8.0h， 以98.1%的产率得到4-羟基-2,2,6-三甲基环己酮
  参考文献：
  名称：

  Ein neuer Zugang zu 2,6,6-Trimethylcyclohexa-2,4-dienon aus 4-Oxoisophoron

  摘要：

  从4-氧代异佛尔酮中获得2,6,6-三甲基环己-2,4-二烯酮的新途径

  DOI：

  10.1002/hlca.19890720223

文献信息

• [EN] OPSIN-BINDING LIGANDS, COMPOSITIONS AND METHODS OF USE<br/>[FR] LIGANDS DE LIAISON À L'OPSINE, COMPOSITIONS ET PROCÉDÉS D'UTILISATION
  申请人：BIKAM PHARMACEUTICALS INC

  公开号：WO2010147653A1

  公开（公告）日：2010-12-23

  Compounds and compositions of said compounds along with methods of use of compounds are disclosed for treating ophthalmic conditions related to mislocalization of opsin proteins, the misfolding of mutant opsin proteins and the production of toxic visual cycle products that accumulate in the eye. Compounds and compositions useful in the these methods, either alone or in combination with other therapeutic agents, are also described.

  本文披露了用于治疗与视蛋白蛋白质错位、突变视蛋白蛋白质的错误折叠以及在眼睛中积累的有毒视觉循环产物有关的眼科疾病的化合物及该化合物的组合物，以及使用该化合物的方法。还描述了在这些方法中有用的化合物和组合物，无论是单独使用还是与其他治疗剂联合使用。
• Fermentation of Fragrances: Biotransformation of ?-Ionone by Lasiodiplodia theobromae
  作者：Victor Krasnobajew、Daniel Helmlinger

  DOI：10.1002/hlca.19820650532

  日期：1982.7.28

  Pre-grown mycelia of Lasiodiplodia theobromae ATCC 28570 transform β-ionone (1) into a large variety of metabolites, by mainly degrading the side-chain of the β-ionone molecule by a C2-unity. The enzyme system responsible for this degradation is proposed to be an oxygenase, which gives rise to the formation of the main product β-cyclo-homogeraniol (8) in analogy to a Baeyer- Villiger oxidation. Further

  拉氏单胞菌ATCC 28570的预先生长的菌丝体主要通过C 2统一降解β-紫罗兰酮分子的侧链，从而将β-紫罗兰酮（1）转变为多种代谢产物。有人提出负责这种降解的酶系统是一种加氧酶，它类似于Baeyer- Villiger氧化反应，导致形成了主要产物β-环-香薄荷醇（8）。Lasiodiplodia的进一步酶促作用，例如氢化和羟基化，导致一些尚未描述的β-紫罗兰酮代谢物的积累。
• 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。
• Use of compounds to enhance synchrony of germination and emergence in
  申请人：National Research Council of Canada

  公开号：US05518995A1

  公开（公告）日：1996-05-21

  The present invention relates to a composition for enhancing synchrony of germination and emergence in plants and comprises an effective amount of a compound having the following general formula (I); ##STR1##

  本发明涉及一种用于增强植物萌发和出苗同步性的组合物，包括具有以下一般化学式(I)的化合物的有效量；##STR1##
• Abscisic acid-related plant growth regulators - germination promoters
  申请人：Her Majesty the Queen in right of Canada, as represented by the National

  公开号：US05201931A1

  公开（公告）日：1993-04-13

  Composition for enhancing germination and growth of plants which comprises an effective amount of at least one abscisic acid-related compound having the following formula (I): ##STR1##

  该组合物用于促进植物萌发和生长，其包含有效量的至少一种具有以下化学式（I）的脱落酸相关化合物： ##STR1##