(3β,12α) 3-acetyl-12-hydroxy-18β-olean-28-oic acid 28,13-lactone | 62498-83-3

• 物质功能分类: 天然产物 - 萜类
• 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: (3β,12α) 3-acetyl-12-hydroxy-18β-olean-28-oic acid 28,13-lactone
• 英文别名: 3β-acetoxy-12α-hydroxyoleanan-13β,28-olide；3β-acetoxy-12α-hydroxyoleanan-28,13β-olide；3β-acetoxy-12α-hydroxyolean-28,13β-olide；3β-acetoxy-12α-hydroxyolean-28,13-olide；3-O-acetyl-12α-hydroxyoleanolic lactone；3β-acetoxy-12α,13-dihydroxy-oleanan-28-oic acid-13-lactone；3-O-Acetyloleanderolide；[(1S,4S,5R,8R,10S,13R,14R,16S,17S,18R)-16-hydroxy-4,5,9,9,13,20,20-heptamethyl-23-oxo-24-oxahexacyclo[15.5.2.01,18.04,17.05,14.08,13]tetracosan-10-yl] acetate
• CAS: 62498-83-3
• 化学式: C₃₂H₅₀O₅
• 分子量: 514.746
• InChiKey: SFSFDBPTPLSWRM-KXNUYETHSA-N

物化性质

• 熔点：
  285-287 °C(Solv: ethyl acetate (141-78-6); ligroine (8032-32-4))
• 沸点：
  600.5±55.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)
• 溶解度：
  溶于氯仿、二氯甲烷、乙酸乙酯、DMSO、丙酮等。

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  37
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3β,12α) 3-acetyl-12-hydroxy-18β-olean-28-oic acid 28,13-lactone 在 氨 、 lithium 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 齐墩果酸
  参考文献：
  名称：

  The chemical and biological potential of C ring modified triterpenoids

  摘要：

  A convenient and elegant route has been developed to separate the natural regioisomers triterpenoids ursolic acid (UA) and oleanolic acid (OA) as well as derivatives thereof. Eleven unknown derivatives of OA were designed, synthesized, and their cytotoxicity was investigated. Further sixteen compounds were prepared to correlate all compounds in a SAR study. It could be shown that C-ring modifications of OA and UA have only a moderate influence onto the cytotoxic activity of the compounds but a significant impact onto the ability to trigger apoptosis in ovarian cancer cells (cell line A2780). (C) 2013 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2013.11.025
• 作为产物：
  描述：

  齐墩果酸 在 吡啶 、 臭氧 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 3.5h， 生成 (3β,12α) 3-acetyl-12-hydroxy-18β-olean-28-oic acid 28,13-lactone
  参考文献：
  名称：

  由齐墩果酸和山梨酸部分合成C环衍生物。通过化学和光化学异构化过程形成数个三烯系统

  摘要：

  从橄榄油压榨固体废物中所含的齐墩果酸半合成了一些在C环上改性的三萜类化合物。齐墩果酸和山lin酸的相应酯使产物具有二烯体系，其通过电环反应产生类似于维生素原D 2的油烯酮。这些化合物的化学和光化学异构化反应产生了两种不同的三烯，其结构与速甾醇和维生素D 2相似。

  DOI：

  10.1016/j.tet.2003.12.023

文献信息

• Oxidative transformations of triterpenoids of the ursane and oleanane skeleta with hydrogen peroxide. introduction of 11,12-double bond and 13(28)oxide moiety in the ursane system
  作者：P.L. Majumder、A. Bagchi

  DOI：10.1016/s0040-4020(01)91841-1

  日期：1983.1

  12-hydroxy-γ-lactone 3b. The total absence of the 12-ketodihydro acid 4b among the oxidation products of 1b has been rationalised. The results of this reaction with several isomeric pairs of triterpenoids of the ursane and oleanane skeleta bearing functional groups at C-17 other than a carboxyl group show that for any appreciable oxidation involving the intermediacy of a 12β,13β-epoxide 6a or 6b, the 17-carboxyl

  在沸腾的HOAc中用H 2 O 2处理齐墩果酸乙酸酯（1b），得到环氧-γ-内酯2b和12-羟基-γ-内酯3b。在1b的氧化产物中完全不存在12-酮二氢酸4b。该反应与在C-17上带有除羧基以外的带有功能基团的ursane和leanane skeleta的几个三萜类异构体的三对异构体的反应结果表明，对于涉及12β，13β-环氧化合物6a或6b的任何明显的氧化反应， 17-羧基是必要条件。12,13-双键的分子内环氧化已经设想了在图1a和1b中由17-过羧酸原位形成。描述了旨在在乌烷体系中引入11,12-双键和13（28）-氧化物部分的反应。通过用TsOH处理三醇1p获得所需的化合物2c。然而，用H 2 O 2 / TsOH，除2c外，还给出了1p，重排产物8a。已经解释了1p和1q在化学行为上的差异。H 2 O 2处理2e在沸腾的HOAc中得到环氧化物2f。根据该观察结果，讨论了2a和2b的形成机理。
• Oxyfunctionalization Products of Terpenoids with Dimethyldioxirane and Their Biological Activity
  作者：Shoujiro Ogawa、Keiji Hosoi、Noriaki Ikeda、Mitsuko Makino、Yasuo Fujimoto、Takashi Iida

  DOI：10.1248/cpb.55.247

  日期：——

  Oxyfunctionalization of the bioactive terpenoids, ursolic acid acetate (1), oleanolic acid acetate (5), lupeol acetate (12), and kaurenic acid (17), with dimethyldioxirane (DMDO) was investigated. Treatment of the terpenoids with DMDO under mild conditions afforded a variety of oxidation and oxydegradation products to yield naturally occurring and/or novel compounds in one step. After chromatographic separation, the structures of the individual isolated products were determined using spectroscopic methods including several homonuclear (1H–1H) and heteronuclear (1H–13C) shift-correlated 2D-NMR techniques. The inhibitory activity of the terpenoid derivatives against α-glucosidase was investigated and compounds 1, 3, 7, and 9 were found to exhibit potent activity.

  研究人员用二甲基二氧环己烷（DMDO）对具有生物活性的萜类化合物熊果酸乙酸酯（1）、齐墩果酸乙酸酯（5）、羽扇豆醇乙酸酯（12）和高瑞香酸（17）进行了氧化官能化处理。在温和的条件下，用二甲基二氧环己烷处理萜类化合物，可产生多种氧化和氧降解产物，从而一步生成天然和/或新型化合物。色谱分离后，利用光谱方法（包括几种同核（1H-1H）和异核（1H-13C）位移相关的二维核磁共振技术）确定了各个分离产物的结构。研究了萜类衍生物对 α-葡萄糖苷酶的抑制活性，发现化合物 1、3、7 和 9 具有很强的活性。
• Bismuth(III) Triflate-Based Catalytic Direct Opening of Oleanolic Hydroxy-γ-lactones to Afford 12-Oxo-28-carboxylic Acids
  作者：Jorge A. R. Salvador、Vânia M. Moreira、Rui M. A. Pinto、Ana S. Leal、Christophe Le Roux

  DOI：10.1002/adsc.201100155

  日期：2011.10

  The bismuth(III) triflate-based catalytic direct opening of oleanolic hydroxy-γ-lactones affords the corresponding 12-oxo-28-carboxylic acid derivatives, in both acetonitrile and dichloromethane, at reflux, in high yields. Participation of an in situ generated Brønsted acid species from bismuth(III) triflate is most likely involved in the reaction mechanism. Full structural elucidation of the products

  齐墩果酸羟基-γ-内酯的基于三氟甲磺酸铋（III）的催化直接打开以高收率在乙腈和二氯甲烷中提供了相应的在乙腈和二氯甲烷中的12-氧代-28-羧酸衍生物。的参与原位生成从铋（III），三氟甲磺酸是最有可能参与反应机理布朗斯台德酸物质。已通过1D和2D NMR技术对所得产物进行了完整的结构阐明。
• Beckmann rearrangement within the ring C of oleanolic acid lactone: Synthesis, structural study and reaction mechanism analysis
  作者：Anna Froelich、Barbara Bednarczyk-Cwynar、Lucjusz Zaprutko、Andrzej Gzella

  DOI：10.1016/j.molstruc.2017.01.057

  日期：2017.5

  ic acid (Beckmann rearrangement reaction products) are described. Structural analysis revealed that the oxime group in the ring C in substrate molecule had an E-configuration. The nitrile product with retained lactone group was a result of major transformations within rings C and D of oleanane skeleton. In lactam product free carboxyl group and a double bond in ring D instead of lactone system were

  摘要 三种化合物的合成、光谱和 X 射线分析，即 3β-acetoxy-12-hydroxyimino-18β-oleanan-28,13β-olide（底物）和 3β-acetoxy-12-nitrile-12,13-seco-15 (14 → 13)-abeoolean-14(27)-en-28,13β-olide 和 3β-acetoxy-12-oxo-12a-aza-C-homoolean-13(18)-en-28-oic acid (Beckmann重排反应产物）进行了描述。结构分析表明底物分子中环C中的肟基团具有E-构型。保留内酯基团的腈产物是齐墩果骨架的 C 和 D 环内主要转化的结果。在内酰胺产物中，在贝克曼重排反应中形成了游离羧基和D环中的双键而不是内酯体系。
• Efficient oxidation of oleanolic acid derivatives using magnesium bis(monoperoxyphthalate) hexahydrate (MMPP): A convenient 2-step procedure towards 12-oxo-28-carboxylic acid derivatives
  作者：Jorge A R Salvador、Vânia M Moreira、Rui M A Pinto、Ana S Leal、José A Paixão

  DOI：10.3762/bjoc.8.17

  日期：——

  straightforward and high yielding procedure to convert oleanolic acid derivatives into the corresponding delta-hydroxy-gamma-lactones, by using the convenient oxidizing agent magnesium bis(monoperoxyphthalate) hexahydrate (MMPP) in refluxing acetonitrile, is reported. In addition, a two-step procedure for the preparation of oleanolic 12-oxo-28-carboxylic acid derivatives directly from Delta(12)-oleananes

  报道了通过在回流乙腈中使用方便的氧化剂双（单过氧邻苯二甲酸酯）六水合物 (MMPP) 镁，将齐墩果酸衍生物转化为相应的 δ-羟基-γ-内酯的一种新的、直接且高产的方法。此外，直接从 Delta(12)-齐墩果烷制备齐墩果酸 12-氧代-28-羧酸衍生物的两步程序，无需中间后处理，并在两个步骤中保持相同的反应溶剂, 被描述为应用于 3,12-dioxoolean-28-oic 酸的合成。