(S)-2,5,7,8-tetramethyl-6-hydroxy-2-(2-hydroxyethyl)-chroman | 94425-67-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (S)-2,5,7,8-tetramethyl-6-hydroxy-2-(2-hydroxyethyl)-chroman
• 英文别名: (S)-2-(3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-1-benzopyran-2-yl)ethanol；(2S)-(-)-3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-1-benzopyran-2-ethanol；(S)-(-)-2-[(+/-)-6-hydroxy-2,5,7,8-tetramethylchroman-2-yl]ethanol；(S)-2-(2-hydroxyethyl)-2,5,7,8-tetramethylchroman-6-ol；(S)-6-hydroxy-2,5,7,8-tetramethylchroman-2-ethanol；(S)-(-)-6-hydroxy-2,5,7,8-tetramethylchroman-2-ethanol；(2S)-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-3,4-dihydrochromen-6-ol
• CAS: 94425-67-9
• 化学式: C₁₅H₂₂O₃
• 分子量: 250.338
• InChiKey: RUYZTDOMKYWHFC-HNNXBMFYSA-N

物化性质

• 熔点：
  150-152 °C
• 沸点：
  412.5±45.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2,5,7,8-tetramethyl-6-hydroxy-2-(2-hydroxyethyl)-chroman 生成 (S)-(+)-2-(2-acetoxyethyl)-6-hydroxy-2,5,7,8-tetramethylchroman
  参考文献：
  名称：

  Novel optically active chroman derivatives, their preparation and novel

  摘要：

  利用一种方法制备一种具有一般式Ia和Ib的新型光学活性的色滤衍生物##STR1##其中R.sup.1、R.sup.2、R.sup.3和R.sup.4分别为氢或烷基，X为--OH、--O--CO-烷基、--O-烷基、--O-对甲苯磺酰基、--O-甲烷磺酰基、--O-苯甲磺酰基、Cl、Br或I，所述方法包括(a)将一般式I'的消旋体##STR2##在侧链中与羧酸酯化，然后与一般式III的光学活性羧酸卤化物##STR3##或相应的羧酸酐酰化，得到色滤衍生物IV##STR4##或(b)将消旋体I'在侧链中与III来源的羧酸酯化，如有必要，将得到的酯与羧酸卤化物酰化以得到IV'##STR5##所得的混合物IV或IV'，由两个对映异构体组成，通过分馏结晶进行分离，将对映异构体水解为醇Ia和Ib，如有需要，这些醇可以以常规方式转化为其他化合物Ia和Ib。还声明了有用的光学活性色滤衍生物Ia和Ib以及对映异构的色滤酰基酯IV和IV'。

  公开号：

  US04645845A1
• 作为产物：
  描述：

  D-甲瓦龙酸?酯 在 palladium on activated charcoal 4-二甲氨基吡啶 、 ammonium cerium(IV) nitrate 、 氨 、 氢气 、 lithium 、 二异丁基氢化铝 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 、 苯 为溶剂， -33.0~25.0 ℃ 、101.33 kPa 条件下， 反应 7.34h， 生成 (S)-2,5,7,8-tetramethyl-6-hydroxy-2-(2-hydroxyethyl)-chroman
  参考文献：
  名称：

  A Facile Conversion of Natural (R)-Mevalonolactone into a Vitamin E Key Intermediate

  摘要：

  DOI：

  10.3987/com-90-5387

文献信息

• Mechanistic Insight into Asymmetric Hetero-Michael Addition of α,β-Unsaturated Carboxylic Acids Catalyzed by Multifunctional Thioureas
  作者：Noboru Hayama、Ryuta Kuramoto、Tamás Földes、Kazuya Nishibayashi、Yusuke Kobayashi、Imre Pápai、Yoshiji Takemoto

  DOI：10.1021/jacs.8b07511

  日期：2018.9.26

  Carboxylic acids and their corresponding carboxylate anions are generally utilized as Brønsted acids/bases and oxygen nucleophiles in organic synthesis. However, a few asymmetric reactions have used carboxylic acids as electrophiles. Although chiral thioureas bearing both arylboronic acid and tertiary amine were found to promote the aza-Michael addition of BnONH2 to α,β-unsaturated carboxylic acids

  羧酸及其相应的羧酸根阴离子通常用作有机合成中的布朗斯台德酸/碱和氧亲核试剂。然而，一些不对称反应使用羧酸作为亲电子试剂。尽管发现同时带有芳基硼酸和叔胺的手性硫脲以中等至良好的对映选择性促进 BnONH2 与 α,β-不饱和羧酸的氮杂-迈克尔加成反应，但反应机理仍有待阐明。使用光谱分析和动力学研究对反应进行了详细研究，确定了包含两个羧酸根阴离子的四面体硼酸盐配合物作为反应中间体。通过添加 1 当量的苯甲酸，我们实现了产品对映选择性的显着提高。在这个 aza-Michael 反应中，硼酸不仅将羧酸盐配体作为路易斯酸与硫脲 NH 质子一起激活，而且还通过苯甲酰氧基阴离子作为布朗斯台德碱激活亲核试剂。此外，发现分子筛在生成三元硼酸盐配合物方面发挥着重要作用，这对于获得高对映选择性至关重要，如 DFT 计算所示。我们还设计了一种用于分子内 oxa-Michael 加成的新型硫脲催化剂，以利用催化剂和
• Novel Esters and Amides of Nonsteroidal Antiinflammatory Carboxylic Acids as Antioxidants and Antiproliferative Agents
  作者：Mark R. Hellberg、Abdelmoula Namil、Pete Delgado、Karen C. David、Timothy L. Kessler、Gustav Graff、Karen S. Haggard、Jon C. Nixon

  DOI：10.1021/jm980430o

  日期：1999.1.1

  affect antioxidant activity, but methylation of the 6-hydroxy substituent resulted in compound 6f which was devoid of antioxidant activity. Although indistinguishable in antioxidant activity, the amide derivatives tended to be more potent as antiproliferative agents than the corresponding esters. The IC50's for the amide derivatives (3, 5a-e, 8) ranged from 2 to 7 microM, while the IC50's for the structurally

  非甾体抗炎药萘普生的一系列酚类抗氧化剂酯和酰胺衍生物被设计为具有抗炎和细胞保护活性。在膜脂质过氧化测定中通过硫代巴比妥酸反应性物质（TBARS）的形成间接评估了化合物的抗氧化活性，并通过抑制了人类血管内皮细胞中DNA的合成来确定其抗增殖活性。该系列化合物表现出有效的抗氧化活性，IC50值（1.6-11.63 microM）比Trolox（6-羟基-2,5,7,8-四甲基苯并二甲酸）和400的IC50值低2-6倍。比维生素E低-1300倍。酯或酰胺亚结构的结构修饰（5a和6a）不影响抗氧化活性，但是6-羟基取代基的甲基化产生了没有抗氧化活性的化合物6f。尽管抗氧化剂活性没有区别，但是酰胺衍生物作为抗增殖剂往往比相应的酯更有效。酰胺衍生物（3、5a-e，8）的IC50范围为2至7 microM，而与结构相关的酯（1、2a-c，6a-e）的IC50范围为9至22 microM。此外，对化合物6a
• Process and intermediates for the manufacture of optically active chroman derivatives
  申请人：ASAHI DENKA KOGYO KABUSHIKI KAISHA

  公开号：EP0441116A2

  公开（公告）日：1991-08-14

  An optically active (S)- or (R)-chroman-2-ethanol compound of the general formula (I) wherein R₁, R₂ and R₃ independently represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and the chiral central carbon atom marked with a symbol * in the formula (I) alternatively has one of an R-configuration and an S-configuration, is disclosed. Further, intermediate products of the compound of the formula (I) are also disclosed. Still further, a process for manufacturing the above compounds is disclosed. The compound of the formula (I) is easily synthesized from an easily available optically active starting material.

  通式(I)的具有光学活性的(S)-或(R)-色满-2-乙醇化合物 其中 R₁、R₂ 和 R₃ 独立地代表氢原子或具有 1 至 4 个碳原子的低级烷基，且式 (I) 中标记为符号 * 的手性中心碳原子具有 R 构型和 S 构型中的一种。此外，还公开了式 (I) 化合物的中间产物。此外，还公开了制造上述化合物的工艺。式（I）化合物很容易从易于获得的光学活性起始材料中合成。
• Cardioselective Ammonium, Phosphonium, and Sulfonium Analogs of .alpha.-Tocopherol and Ascorbic Acid That Inhibit in Vitro and ex Vivo Lipid Peroxidation and Scavenge Superoxide Radicals
  作者：J. Martin Grisar、Gilbert Marciniak、Frank N. Bolkenius、Joelle Verne-Mismer、Eugene R. Wagner

  DOI：10.1021/jm00015a010

  日期：1995.7

  Analogues of alpha-tocopherol and ascorbic acid with permanently cationic substituents, i.e., phosphonium (8, 9), sulfonium (11), acylhydrazinium (13, 14), and ammonium (1, 16, 21), were synthesized, and the 2R and 2S enantiomers of the alpha-tocopherol analogues 1, 8, 11, and 13 were separated. The compounds were found to scavenge lipoperoxyl and superoxide radicals in vitro and accumulate in heart tissue (cardioselectivity) as demonstrated by measurement of ex vivo inhibition of lipid peroxidation in mouse heart homogenates and confirmed by HPLC determination of drug concentrations for 1 and 11. The 2R and 2S enantiomers of 1 inhibited ex vivo lipid peroxidation to an equal extent. Thus the in vivo uptake into myocytes (cardioselectivity) is independent of the geometry at the chiral center and common to permanently cationic compounds.
• ——
  作者：V. N. Odinokov、A. Yu. Spivak、G. A. Emel"yanova、G. D. Gamalevich、E. P. Serebryakov

  DOI：10.1023/a:1015001401902

  日期：——

  In the presence of lipase from the yeast Candida cylindracea, partial acetylation of (+/-)-2-[6-benzyloxy-2,5,7,8-tetramethylchroman-2-yl]ethanol with vinyl acetate gives S-(+)-acetate whose alkaline hydrolysis affords (S)-(-)-alcohol. Repeated enzymatic acetylation of the "residual" alcohol up to similar to39% conversion afforded the R-enantiomer. The enantiomeric alcohols were oxidized to (S)- or (R)-aldehydes having the same sign of \alpha\(D) as the original alcohols. These alcohols were converted into S-(+)- and R-(-)-enantiomers of the antioxidant MDL-73404, a hydrophilic analog of alpha-tocopherol.