(3beta,20beta)-20-羧基-11-氧代-30-去甲齐墩果-12-烯-3-基 2-O-beta-D-吡喃葡糖基-beta-D-吡喃葡糖苷酸 | 103000-77-7

• 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
• 中文名称: (3beta,20beta)-20-羧基-11-氧代-30-去甲齐墩果-12-烯-3-基 2-O-beta-D-吡喃葡糖基-beta-D-吡喃葡糖苷酸
• 中文别名: (3beta,20beta)-20-羧基-11-氧代-30-去甲齐墩果-12-烯-3-基2-O-beta-D-吡喃葡糖基-beta-D-吡喃葡糖苷酸
• 英文名称: glycyrrizhin
• 英文别名: glycyrrhizin；glycyrrhizic acid；β-glycyrrhizic acid；20β-carboxyl-11-oxo-30-norolean-12-en-3β-yl-2-O-β-D-glucopyranuronosyl-β-D-glucopyranosiduronic acid；uralsaponin A；(2S,3S,4S,5R,6R)-6-[(2R,3R,4S,5S,6S)-2-[[(3S,4aR,6aR,6bS,8aS,11S,12aR,14aR,14bS)-11-carboxy-4,4,6a,6b,8a,11,14b-heptamethyl-14-oxo-2,3,4a,5,6,7,8,9,10,12,12a,14a-dodecahydro-1H-picen-3-yl]oxy]-6-carboxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid
• CAS: 103000-77-7
• 化学式: C₄₂H₆₂O₁₆
• 分子量: 822.945
• InChiKey: LPLVUJXQOOQHMX-MOGLOQIBSA-N

物化性质

• 沸点：
  971.4±65.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)
• 颜色/状态：
  Crystals from glacial acetic acid
• 味道：
  Intensely sweet taste
• 熔点：
  220 °C decomposes
• 溶解度：
  Freely sol in hot water, alcohol; practically insol in ether
• 旋光度：
  Specific optical rotation: +46.2 deg @ 17 °C/D (alcohol, 1.5%)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  58
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  267
• 氢给体数：
  8
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  (3beta,20beta)-20-羧基-11-氧代-30-去甲齐墩果-12-烯-3-基 2-O-beta-D-吡喃葡糖基-beta-D-吡喃葡糖苷酸 在 盐酸 作用下， 以 乙醇 、 水 为溶剂， 反应 48.0h， 以0.53%的产率得到甘草次酸
  参考文献：
  名称：

  Self-assembly of a renewable nano-sized triterpenoid 18β-glycyrrhetinic acid

  摘要：

  来自甘草（Glycyrrhiza glabra）的纳米级三萜类物质18β-甘草酸在不同液体中自组装，形成主要为纳米到微米大小的球形和花状物体，这些物体由纤维网络构成，形成了可热可逆的凝胶。这些自组装结构已被用于CdS纳米颗粒的模板生长。

  DOI：

  10.1039/c2ra21051g
• 作为产物：
  描述：

  在 sodium hypochlorite 、 2,2,6,6-四甲基哌啶氧化物 、 10 wt% Pd(OH)2 on carbon 、 氢气 、 碳酸氢钠 、 potassium bromide 作用下， 以 乙醇 、 水 、 乙酸乙酯 为溶剂， 反应 16.25h， 生成 (3beta,20beta)-20-羧基-11-氧代-30-去甲齐墩果-12-烯-3-基 2-O-beta-D-吡喃葡糖基-beta-D-吡喃葡糖苷酸
  参考文献：
  名称：

  グリチルリチン酸及びガラクツログリチルリチン酸の製造方法並びに当該製造方法に用いられる中間体

  摘要：

  这是一种能够以简便且高收率生产高纯度甘草酸或甘草酸甘油醚的合成方法。该方法的解决方案是对甘草酸的3位羟基进行糖基化，然后选择性地在2'位进行半乳糖基化或糖基化，经过脱保护后，进行一级羟基的选择性氧化。

  公开号：

  JP2018104352A

文献信息

• Apioglycyrrhizin and araboglycyrrhizin, two new sweet oleanene-type triterpene oligoglycosides from the root of Glycyrrhiza inflata.
  作者：Isao KITAGAWA、Masahiro SAKAGAMI、Fumi HASHIUCHI、Jun Liang ZHOU、Masayuki YOSHIKAWA、Jiali REN

  DOI：10.1248/cpb.37.551

  日期：——

  Two new sweet oleanene-type triterpene oligoglycosides, named apioglycyrrhizin and araboglycyrrhizin, were isolated from the air-drie root of Glycyrrhiza inflata [Chinese Glycyrrhizae Radix, Shinkyo-kanzo in Japanese], and their structures have been determined on the basis of chemical and physicochemical evidence.

  从胀果甘草（中药名为甘草，日文名为新娇甘）的干燥根中分离出两种新的甘遂型三萜寡糖苷，分别命名为芹菜苷甘草酸和阿拉伯苷甘草酸，并通过化学和物理化学证据确定了它们的结构。
• Synthesis and anti-HIV-1 activity of new conjugates of 18β- and 18α-glycyrrhizic acids with aspartic acid esters
  作者：L. A. Baltina、E. S. Chistoedova、L. A. Baltina、R. M. Kondratenko、O. A. Plyasunova

  DOI：10.1007/s10600-012-0217-1

  日期：2012.5

  New conjugates of 18β- and 18α-glycyrrhizic acids (GAs) each containing two di- or α-methyl esters of L-aspartic acid in the carbohydrate part of the glycosides were synthesized by the activated ester method using the N-hydroxysuccinimide (HOSu) and N,N'-dicyclohexylcarbodiimide. It was found that the conjugate of 18β-GA with Asp(OMe)(OMe) (4) at a concentration of 250 μg/mL inhibited effectively RT of HIV-1 and the accumulation of virus antigen p24 in MT-4 cell culture (95–97 %) and protected cells from the cytopathogenic action of the virus.

  新型的18β-和18α-甘草酸（GAs）结合物被合成，每种结合物在糖苷的碳水化合物部分含有两个L-天冬氨酸的二醇或α-甲基酯，采用激活酯法合成，使用了N-羟基琥珀酰亚胺（HOSu）和N,N'-二环己基氨基甲烷。在浓度为250 μg/mL时，18β-GA与Asp(OMe)(OMe)（4）的结合物能够有效抑制HIV-1的逆转录（RT）和病毒抗原p24在MT-4细胞培养中的积累（95–97%），并保护细胞免受病毒的细胞病理作用。
• Targeting of liposomes surface-modified with glycyrrhizin to the liver. I. Preparation and biological disoposition.
  作者：Hideki TSUJI、Sayoko OSAKA、Hiroshi KIWADA

  DOI：10.1248/cpb.39.1004

  日期：——

  We consider glycyrrhizin to be a new ligand for liposomes to the liver because it is known that about 80% of glycyrrhizin is excreted into the bile after intravenous administration in rats. In order to modify the liposomal surface with glycyrrhizin, 30-stearyl glycyrrhizin (GLOSt), one of the lipophilic glycyrrhizin derivatives, was synthesized. The structure of this new compound was identified by nuclear magnetic resonance (NMR), infrared (IR) and mass spectra (MS). Sonicated liposomes were prepared from hydrogenated egg phosphatidylcholine-cholesterol-GLOSt or dicetyl phosphate (DCP)(4 : 4 : 1) and were labelled with [3H]inulin as an aqueous marker. It was confirmed by measuring the encapsulation efficiencies and the mean diameters that GLOSt-containing sonicated liposomes (GLOSt-SUV) were SUV-type as well as DCP-containing control liposomes (control-SUV). Four hours after intravenous injection into rats at a dose of 90 μmol as total lipid per kg of rat body weight, GLOSt-SUV showed 4-fold more accumulation (42.4%) in the liver than control-SUV. Therefore, glycyrrhizin is considered to be a useful new ligand on liposomes for targeting to the liver.

  我们认为甘草酸是一种新的脂质体肝靶向配体，因为已知在大鼠静脉注射后，约80%的甘草酸会排泄到胆汁中。为了用甘草酸修饰脂质体表面，合成了30-硬脂酰甘草酸（GLOSt），这是一种脂溶性甘草酸衍生物。通过核磁共振（NMR）、红外（IR）和质谱（MS）鉴定了这种新化合物的结构。从氢化卵磷脂-胆固醇-GLOSt或二鲸蜡磷酸（DCP）（4:4:1）制备了超声处理的脂质体，并以[3H]菊粉作为水相标记物进行标记。通过测量封装效率和平均直径确认，含有GLOSt的超声处理脂质体（GLOSt-SUV）与含有DCP的对照脂质体（对照-SUV）一样，都是小单层脂质体（SUV）类型。在大鼠静脉注射总脂质量为90 μmol/kg体重4小时后，GLOSt-SUV在肝脏中的积累比对照-SUV多4倍（42.4%）。因此，甘草酸被认为是一种有用的脂质体肝靶向新配体。
• Saponin and Sapogenol. XLIX. On the Constituents of the Roots of Glycyrrhiza inflata BATALIN from Xinjiang, China. Characterization of Two Sweet Oleanane-Type Triterpene Oligoglycosides, Apioglycyrrhizin and Araboglycyrrhizin.
  作者：Isao KITAGAWA、Kazuyuki HORI、Masahiro SAKAGAMI、Fumi HASHIUCHI、Masayuki YOSHIKAWA、Jiali REN

  DOI：10.1248/cpb.41.1350

  日期：——

  Two sweet oleanane-type triterpene oligoglycosides named apioglycyrrhizin and araboglycyrrhizin were isolated from the air-dried roots of Glycyrrhiza inflata BATALIN, collected in Xinjiang province (Shinkyo-Kanzo in Japanese), together with glycyrrhizin (3), licorice-saponins A3 (8), G2 (10), and H2 (11) and known flavonoid glycosides. On the basis of chemical and physicochemical evidence, the structures of apioglycyrrhizin and araboglycyrrhizin have been determined to be expressed as 3-O-[β-D-apiofuranosyl(1→2)-β-D-glucuronopyranosyl]glycyrrhetic acid (1) and 3-O-[α-L-arabinopyranosyl(1→2)-β-D-glucuronopyranosyl]glycyrrhetic acid (2), respectively.During the course of these studies, it has been found that the hydroxyl groups in the oligosaccharide moiety of the glucuronide saponins may be partially methylated by prolonged treatment with diazomethane in methanol. The sweetness of the saponins hitherto isolated from various Glycyrrhizae Radix has been examined and a structure-sweetness relationship, as compared with glycyrrhizin, has been found.

  从新疆省（日文中的“新疆甘草”）采集的干燥甘草根中分离出两种甜味oleanane型三萜低聚糖苷，分别命名为apioglycyrrhizin和araboglycyrrhizin，同时分离出的还有甘草酸（3）、甘草皂苷A3（8）、G2（10）和H2（11）以及已知黄酮糖苷。根据化学和物理化学证据，确定apioglycyrrhizin和araboglycyrrhizin的结构分别为3-O-[β-D-apiofuranosyl(1→2)-β-D-glucuronopyranosyl]甘草亭酸（1）和3-O-[α-L-arabinopyranosyl(1→2)-β-D-glucuronopyranosyl]甘草亭酸（2）。在进行这些研究的过程中，发现通过在甲醇中长时间处理重氮甲烷，可以使葡萄糖苷皂苷的低聚糖部分中的羟基部分甲基化。对迄今为止从各种甘草根中分离出的皂苷的甜度进行了检测，并发现了与甘草酸相比的结构-甜度关系。
• Synthesis and Antiviral Activity of Glycyrrhizic-Acid Conjugates with Aromatic Amino Acids
  作者：L. A. Baltina、A. I. Fairushina、L. A. Baltina、M. Yu. Eropkin、N. I. Konovalova、P. A. Petrova、E. M. Eropkina

  DOI：10.1007/s10600-017-2209-7

  日期：2017.11

  Amino-acid conjugates of glycyrrhizic acid (GA) containing phenylalanine, tyrosine, and tryptophan in the carbohydrate and triterpene parts were synthesized using N-hydroxybenzotriazole (HOBt)-N,N′-dicyclohexylcarbodiimide (DCC) and sodium salts of the amino acids. GA conjugates containing two aminoacid residues in the glycoside carbohydrate part were synthesized using N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline

  使用 N-羟基苯并三唑 (HOBt)-N,N'-二环己基碳二亚胺 (DCC) 和氨基酸的钠盐合成了在碳水化合物和三萜部分中含有苯丙氨酸、酪氨酸和色氨酸的甘草酸 (GA) 的氨基酸缀合物。在糖苷碳水化合物部分含有两个氨基酸残基的 GA 缀合物使用 N-乙氧基羰基-2-乙氧基-1,2-二氢喹啉合成。具有酪氨酸的 GA 缀合物对流感病毒 A/St.-Petersburg/05/09 (H1N1)pdm09 表现出微弱但一致的抗病毒活性，与标准毒株 A/California/07/09 相似，并且对呼吸道合胞体具有明显的抗病毒活性病毒 (RSV) 和单纯疱疹病毒 (HSV-1)。