Kumar R, Weintraub S T, McManus L M, Pinckard R N, Hanahan D J
J Lipid Res. 1984 Feb;25(2):198-208.
A facile route to the semi-synthesis of acetyl glycerylether phosphoethanolamine and, subsequently, its choline analogue (platelet-activating factor) has been developed. In essence, this technique takes advantage of the fact that the phosphatidylethanolamine fraction of bovine erythrocytes contains 75-80% of a 1-O-alkyl-2 fatty acyl derivative. Isolation of the latter by silicic acid chromatography followed by base-catalyzed methanolysis allowed good recovery (60-70%) of the 1-O-alkyl-(lyso)-sn-glyceryl-3-phosphoethanolamine, which contained a mixture of long chain alkyl ethers. This compound was treated with acetic anhydride in the presence of trace amounts of perchloric acid for 45 sec to give, in excellent yield, 1-O-alkyl-2-acetyl-sn-glyceryl-3-phosphoethanolamine (AGEPE). This procedure gave a 70% yield of purified AGEPE, based on the starting component, 1-O-alkyl-(lyso)-sn-glyceryl-3-phosphoethanolamine. Separation of AGEPE into fractions individually enriched in the 16:0, 18:0, and 18:1 alkylether substituents was accomplished by silica gel G combined with silver nitrate-impregnated silica gel H thin-layer chromatography. The AGEPE or its individual molecular species can be converted in high yields to the corresponding 1-O-alkyl-2-acetyl-sn-glyceryl-3-phosphocholine (AGEPC) analogues by reaction with methyl iodide in the presence of a crown ether. Characterization of the derivatives was achieved through thin-layer chromatography, infrared spectroscopy, gas-liquid chromatography, and combined gas-liquid chromatography-mass spectrometry. The ability of these analogues to induce irreversible aggregation and secretion of serotonin from washed rabbit platelets was evaluated.
已开发出一种简便的半合成乙酰甘油醚磷酸乙醇胺及其胆碱类似物(血小板活化因子)的方法。从本质上讲,该技术利用了牛红细胞的磷脂酰乙醇胺部分含有75 - 80%的1 - O - 烷基 - 2 - 脂肪酰基衍生物这一事实。通过硅酸色谱法分离后者,随后进行碱催化的甲醇解,可良好地回收(60 - 70%)1 - O - 烷基 - (溶血) - sn - 甘油 - 3 - 磷酸乙醇胺,其含有长链烷基醚的混合物。该化合物在痕量高氯酸存在下用乙酸酐处理45秒,以优异的产率得到1 - O - 烷基 - 2 - 乙酰 - sn - 甘油 - 3 - 磷酸乙醇胺(AGEPE)。基于起始成分1 - O - 烷基 - (溶血) - sn - 甘油 - 3 - 磷酸乙醇胺,该方法得到了70%产率的纯化AGEPE。通过硅胶G与硝酸银浸渍的硅胶H薄层色谱法将AGEPE分离成分别富含16:0、18:0和18:1烷基醚取代基的馏分。AGEPE或其单个分子种类可通过在冠醚存在下与甲基碘反应,高产率地转化为相应的1 - O - 烷基 - 2 - 乙酰 - sn - 甘油 - 3 - 磷酸胆碱(AGEPC)类似物。通过薄层色谱法、红外光谱法、气 - 液色谱法以及气 - 液色谱 - 质谱联用对衍生物进行了表征。评估了这些类似物诱导洗涤过的兔血小板不可逆聚集和5 - 羟色胺分泌的能力。