Prinz Sonja, Müllner Ursula, Heilmann Jörg, Winkelmann Karin, Sticher Otto, Haslinger Ernst, Hüfner Antje
Department of Applied BioSciences, Institute of Pharmaceutical Sciences, Swiss Federal Institute of Technology (ETH) Zurich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
J Nat Prod. 2002 Nov;65(11):1530-4. doi: 10.1021/np010656l.
Abietic acid (1) and its methyl ester (2) were investigated under various storage conditions to provide an indication of their preferred oxidation mechanisms and to investigate the most susceptible positions for modification in the abietane skeleton. Six known compounds, methyl 7alpha,13beta-dihydroxyabiet-8(14)-enoate (4a), methyl 7alpha,13alpha-dihydroxyabiet-8(14)-enoate (4b), methyl 12-oxoabietate (6), methyl 7-oxodehydroabietate (7), methyl 7alpha-hydroxydehydroabietate (8), and 13,14-seco-13,14-dioxoabiet-7(8)-enoic acid (11), were identified. Compounds 7 and 8 are regarded as potent allergens. In addition, six new oxidation products were isolated, methyl 13beta-ethoxy-7alpha-hydroxyabiet-8(14)-enoate (3a), methyl 13alpha-ethoxy-7alpha-hydroxyabiet-8(14)-enoate (3b), methyl 7alpha-hydroperoxy-13alpha-hydroxyabiet-8(14)-enoate or methyl 13alpha-hydroperoxy-7alpha-hydroxyabiet-8(14)-enoate (5), 7alpha,13beta-dihydroxyabiet-8(14)-enoic acid (9a), 7alpha,13alpha-dihydroxyabiet-8(14)-enoic acid (9b), and 7alpha,15-dihydroxydeydroabietic acid (10). Their structures were characterized on the basis of spectroscopic data interpretation. The cytotoxicity of several compounds against KB cells was evaluated, and weak activity was observed for 6, 7, and 8 with IC(50) values of 12.5, 4.5, and 5.8 microg/mL, respectively.
对枞酸（1）及其甲酯（2）在各种储存条件下进行了研究，以表明其优先氧化机制，并研究枞烷骨架中最易发生修饰的位置。鉴定出六种已知化合物，7α,13β - 二羟基枞 - 8(14) - 烯酸甲酯（4a）、7α,13α - 二羟基枞 - 8(14) - 烯酸甲酯（4b）、12 - 氧代枞酸甲酯（6）、7 - 氧代脱氢枞酸甲酯（7）、7α - 羟基脱氢枞酸甲酯（8）和13,14 - 裂 - 13,14 - 二氧代枞 - 7(8) - 烯酸（11）。化合物7和8被认为是强效过敏原。此外，分离出六种新的氧化产物，13β - 乙氧基 - 7α - 羟基枞 - 8(14) - 烯酸甲酯（3a）、13α - 乙氧基 - 7α - 羟基枞 - 8(14) - 烯酸甲酯（3b）、7α - 氢过氧基 - 13α - 羟基枞 - 8(14) - 烯酸甲酯或13α - 氢过氧基 - 7α - 羟基枞 - 8(14) - 烯酸甲酯（5）、7α,13β - 二羟基枞 - 8(14) - 烯酸（9a）、7α,13α - 二羟基枞 - 8(14) - 烯酸（9b）和7α,15 - 二羟基脱氢枞酸（10）。根据光谱数据解释对它们的结构进行了表征。评估了几种化合物对KB细胞的细胞毒性，观察到化合物6、7和8具有较弱活性，IC(50)值分别为12.5、4.5和5.8μg/mL。
