1,2,3-三(二十碳五烯酰基)甘油 | 99660-94-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 甘油脂
• 中文名称: 1,2,3-三(二十碳五烯酰基)甘油
• 中文别名: 二十碳五烯酸甘油三酯(CIS-5,8,11,14,17)
• 英文名称: trieicosapentaenoylglycerol
• 英文别名: TG(20:5(5Z,8Z,11Z,14Z,17Z)/20:5(5Z,8Z,11Z,14Z,17Z)/20:5(5Z,8Z,11Z,14Z,17Z))；2,3-bis[[(5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoyl]oxy]propyl (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoate
• CAS: 99660-94-3
• 化学式: C₆₃H₉₂O₆
• 分子量: 945.42
• InChiKey: SHYCFZYQNVKAAU-UZBXBHHFSA-N

物化性质

• 溶解度：
  DMF：10mg/mL；乙醇：10mg/mL；乙醇:PBS(pH 7.2) (1:1): 0.5mg/ml
• 物理描述：
  Solid

计算性质

• 辛醇/水分配系数(LogP)：
  17.4
• 重原子数：
  69
• 可旋转键数：
  47
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 储存条件：
  -20°C，密闭保存，并确保环境干燥。

制备方法与用途

Trieicosapentaenoyl glycerol (EPA-TG) is a glycerol ester derived from eicosapentaenoic acid, an essential ω-3 fatty acid.

反应信息

• 作为反应物：
  描述：

  1,2,3-三(二十碳五烯酰基)甘油 生成 全顺式二十碳五烯酸
  参考文献：
  名称：

  YAMATO, MASATOSI

  摘要：

  DOI：
• 作为产物：
  描述：

  全顺式二十碳五烯酸 、 甘油 在 immobilized lipase from Candida Antarctica 作用下， 65.0 ℃ 、13.33 Pa 条件下， 反应 30.0h， 以84%的产率得到1,2,3-三(二十碳五烯酰基)甘油
  参考文献：
  名称：

  脂肪酶合成二十碳五烯酸和二十二碳六烯酸均相甘油三酸酯

  摘要：

  通过固定化的南极假丝酵母的非区域特异性酵母脂肪酶高效合成纯二十碳五烯酸1或二十二碳六烯酸2的均质甘油三酸酯描述。使用了两种方法：三丁酸甘油酯的酯交换和分别以化学计量的99％EPA或DHA的乙基酯和游离脂肪酸的甘油直接酯化。两种方法均在真空下于65°C且无任何溶剂的条件下进行。将挥发性副产物冷凝到冷却的阱中，从而使平衡朝着完成方向移动。在所有情况下，都可以在不到72小时的时间内完成完全掺入，但是发现直接酯化比酯交换要快得多，这两个过程都涉及EPA和DHA。高场11 H NMR光谱分析提供了在直接酯化反应过程中对中间甘油酯的详细研究。以优异的产率提供的所得粗产物的纯度非常高。

  DOI：

  10.1016/0040-4020(94)00983-2

文献信息

• Synthesis of triacylglycerol from polyunsaturated fatty acid by immobilized lipase
  作者：Yoshitsugu Kosugi、Naoki Azuma

  DOI：10.1007/bf02541362

  日期：1994.12

  More than 95% of polyunsaturated acid (PUFA) was converted to triacylglycerol by immobilized lipase fromCandida antarctica orRhizomucor miehei. The esterification was carried out at 50–60°C with shaking and dehydration for 24 h. The substrates consisted of glycerol and free fatty acid or ethyl esters of the fatty acid at a 1∶3 molar ratio. The docosahexaenoic acid (DHA) or eicosapentaenoic acid (EPA) in the substrate polymerized during the reaction, and they required 5–10% more than the stoichiometric amount to compensate for the PUFA loss. On the contrary, ethyl esters of DHA and EPA were not polymerized. Pure tridocosahexaenoyl, trieicosapentaenoly and triarachidonoyl glycerol were isolated after passing the product through a basic aluminum oxide column. Industrial feasibility of this process was discussed for the ethyl ester as substrate.

  摘要 利用固定化脂肪酶将95%以上的多不饱和脂肪酸（PUFA）转化为三酰甘油。底物包括甘油和游离脂肪酸或脂肪酸乙酯，摩尔比为 1∶3。底物中的二十二碳六烯酸（DHA）或二十碳五烯酸（EPA）在反应过程中聚合，它们需要比化学计量量多 5-10% 的量来补偿 PUFA 的损失。相反，DHA 和 EPA 的乙酯没有聚合。产品通过碱性氧化铝柱后，分离出了纯净的三二十六烯酰、三二十五烯酰和三丙烯酰甘油。讨论了以乙酯为底物进行该工艺的工业可行性。
• Enzymatic synthesis of symmetrical 1,3-diacylglycerols by direct esterification of glycerol in solvent-free system
  作者：Roxana Rosu、Mamoru Yasui、Yugo Iwasaki、Tsuneo Yamane

  DOI：10.1007/s11746-999-0074-7

  日期：1999.7

  Abstract1,3‐Diacylglycerols were synthesized by direct esterification of glycerol with free fatty acids in a solvent‐free system. Free fatty acids with relatively low melting points (<45°C) such as unsaturated and medium‐chain saturated fatty acids were used. With stoichiometric ratios of the reactants and water removal by evaporation at 3 mm Hg vacuum applied at 1 h and thereafter, the maximal 1,3‐diacylglycerol content in the reaction mixture was: 84.6% for 1,3‐dicaprylin, 84.4% for 1,3‐dicaprin, 74.3% for 1,3‐dilinolein, 71.7% for 1,3‐dieicosapentaenoin, 67.4% for 1,3‐dilaurin, and 61.1% for 1,3‐diolein. Some of the system's parameters (temperature, water removal, and molar ratio of the reactants) were optimized for the production of 1,3‐dicaprylin, and the maximal yield reached 98%. The product was used for the chemical synthesis of 1,3‐dicapryloyl‐2‐eicosapentaenoylglycerol. The yield after purification was 42%, and the purity of the triacylglycerol was 98% (both 1,3‐dicapryloyl‐2‐eicosapentaenoylglycerol and 1,2‐dicapryloyl‐3‐eicosapentaenoylglycerol included) by gas chromatographic analysis, of which 90% was the desired structured triacylglycerol (1,3‐dicapryloyl‐2‐eicosapentaenoylglycerol) as determined by silver ion high‐performance liquid chromatographic analysis.
• Enzymatic synthesis of 1,3-dicapryloyl-2-eicosapentaenoylglycerol
  作者：Roxana Irimescu、Mamoru Yasui、Yugo Iwasaki、Nobuyoshi Shimidzu、Tsuneo Yamane

  DOI：10.1007/s11746-000-0080-y

  日期：2000.5

  Abstract1,3‐Dicapryloyl‐2‐eicosapentaenoylglycerol (CEC) was synthesized by interesterification of trieicosapentaenoylglycerol (EEE) with ethyl caprylate (EtC) catalyzed by LipozymeTM. After some of the reaction conditions were optimized, the maximal molar content of CEC in the glycerides of the reaction mixture was 91%. Among the parameters studied in the optimization, the critical ones were: (i) the water content, which influenced the conversion of EEE to CEC and 1‐capryloyl‐2‐eicosapentaenoylglycerol (CEOH), and (ii) the timing of water removal under reduced pressure for the reesterification of CEOH to form CEC. The complete synthesis of CEC from ethyl eicosapentaenoate (EtE) was performed in three steps: (i) hydrolysis of EtE to free eicosapentaenoic acid (EPA), (ii) esterification of glycerol with EPA to form EEE, and (iii) interesterification of EEE with EtC under the optimized conditions. The first two steps were catalyzed by NovozymTM and the third by LipozymeTM. The total yield over all the steps was 88%, and no purification of the intermediates was necessary. The regioisomeric purity of the product was 100% by silver‐ion high‐pressure liquid chromatography.
• Utilization of reaction medium-dependent regiospecificity of Candida antarctica lipase (Novozym 435) for the synthesis of 1,3-dicapryloyl-2-docosahexaenoyl (or eicosapentaenoyl) glycerol
  作者：Roxana Irimescu、Kiyomi Furihata、Kazuhiko Hata、Yugo Iwasaki、Tsuneo Yamane

  DOI：10.1007/s11746-001-0258-3

  日期：2001.3

  AbstractA highly efficient enzymatic method for the synthesis of regioisomerically pure 1,3‐dicapryloyl‐2‐docosahexaenoyl glycerol (CDC) in two steps was established. 2‐Monoglyceride (2‐MG) formation by ethanolysis of tridocosahexaenoylglycerol (DDD) with immobilized Candida antarctica lipase (Novozym 435) as catalyst was the key step of the synthesis. CDC was finally obtained by reesterification of 2‐MG with ethylcaprylate (EtC) catalyzed by Rhizomucor miehei lipase (Lipozyme IM). The regiospecificity of Novozym 435 depended on the type of reaction and the initial composition of the reaction medium. It displayed strict 1,3‐regiospecificity for ethanolysis at a high excess of ethanol in the reaction mixture although it displayed no regiospecificity in transesterification and esterification reactions. The highest yield of CDC (85.4%) was obtained by ethanolysis at a 4∶1 weight ratio of ethanol/DDD for 6 h followed by reesterification at a 20∶1 molar ratio of EtC/initial DDD for 1.5 h. The regioisomeric purity of CDC was 100%. Good results were obtained also for the synthesis of 1,3‐dicapryloyl‐eicosapentaenoylglycerol (CEC) by the same method: 84.2% yield and 99.8% regioisomeric purity at the same reactant ratios as above. The yield of the reesterification step and the regioisomeric purity of the product were influenced by the molar ratio of the reactants for both CDC and CEC syntheses: higher excess of EtC favored higher yields and regioisomeric purity of the products.
• Comparison of acyl donors for lipase-catalyzed production of 1,3-dicapryloyl-2-eicosapentaenoylglycerol
  作者：Roxana Irimescu、Kazuhiko Hata、Yugo Iwasaki、Tsuneo Yamane

  DOI：10.1007/s11746-001-0221-3

  日期：2001.1

  AbstractSynthesis of 1,3‐dicapryloyl‐2‐eicosapentaenoylglycerol (CEC) catalyzed by Lipozyme IM (immobilized Rhizomucor miehei lipase) was performed by interesterification of trieicosapentaenoylglycerol (EEE) with caprylic acid (CA) (acidolysis) and EEE with ethyl caprylate (EtC) (interesterification). Both methods involved two steps: (i) transesterification at an optimized water content and temperature for the high yield conversion of the substrate to CEC, 1‐capryloyl‐2‐eicosapentaenoylglycerol (CEOH) and 2‐eicosapentaenoylglycerol (OHEOH), and (ii) reesterification of CEOH and OHEOH to CEC by water removal under reduced pressure. Interesterification had clear advantages over acidolysis. The reaction rates for interesterification were higher and the reaction times shorter. The final yield of CEC by interesterification was higher, and the extent of acyl migration, indicated by the tricapryloylglycerol content, was lower. The disadvantage of the higher price of EtC used for interesterification (approximately 10 times higher than the price of CA) was overcome by synthesizing it directly in the same reaction vessel prior to the interesterification step. EtC was rapidly synthesized by esterification of CA with ethanol in high yield (92% obtained in 2.5 h). The amount of water added to the reaction mixture and the reaction temperature influenced the yields of CEC, CEOH, and OHEOH in the transesterification step for both interesterification and acidolysis methods. The regioisomeric purity of CEC was 100% for both methods at temperatures of 40°C or less. The highest yield of CEC (81%) was obtained for the interesterification of EEE with EtC, formed directly in the same reaction vessel, at a CA/EEE molar ratio of 20∶1 and 30°C.