马桑化学成分研究及熊果酸糖苷的合成

【作者】 王克让；

【导师】 张雁冰；

【作者基本信息】 郑州大学 ， 有机化学， 2006， 硕士

【摘要】 本论文包括两部分，第一部分是马桑化学成分的研究，第二部分是熊果酸糖苷的合成。 第一部分：马桑化学成分研究 马桑(Coriaria sinica Maxim)为马桑科马桑属植物。通过硅胶柱、大孔吸附树脂、ODS反相柱等分离手段，对马桑叶中黄酮类化合物进行了系统研究，共分离了8个黄酮类化合物，鉴定了它们的结构，分别是山奈酚(Kaempferol)(1)，山奈酚-3-O-α-L-鼠李糖(Kaempferol-3-O-α-L-rhamnoside) (2)，山奈酚-3-O-β-D-半乳糖(Kaempferol-3-O-β-D-galactoside) (3)，山奈酚-3-O-α-L-阿拉伯糖(Kaempferol-3-O-α-L-arabinoside) (4)，槲皮素(Quercetin) (5)，槲皮素3-O-α-L-阿拉伯糖(Quercetin-3-O-α-L-arabinoside)(6)，槲皮素-3-O-β-D-半乳糖(Quercetin-3-O-β-D-galactoside) (7)，槲皮素-3-O-β-D-葡萄糖(Quercetin-3-O-β-D-glucoside) (8)。8个都为已知的化合物，其中(2)、(3)、(4)、(6)为首次从马桑叶中分到。 此外还对马桑叶、马桑果实、马桑籽进行研究，共分离得到5个萜类化合物，他们的结构为三萜类：熊果酸(Ursolic acid) (9)、齐墩果酸(Oleanolic acid)(10) ；二萜类：7α，11α，14β-三羟基-20α-乙酰氧基-15-酮-16-贝壳杉烯(Actylkamebakaurinin) (11)；倍半萜类：羟基马桑毒素(Tutin) (12)、马桑亭(Coriatin) (13)。其中化合物(10)、(11)为首次从马桑中分到，化合物(11)为首次从马桑科中分到二萜类化合物。 采用紫外分光光度法在548 nm波长处，以熊果酸为标准品，以5％香草醛—冰乙酸和高氯酸为显色剂，测定了马桑叶中的总三萜酸含量。 第二部分 熊果酸糖苷的合成 熊果酸(ursolic acid)又名乌苏酸，属三萜类化合物。通过Koenigs-Knorr反应、酯化反应与4-氯4-脱氧-α-D-半乳糖反应，分别合成了熊果酸3位、28位以及3位、28位同时连糖的衍生物。在试验过程中发现0.1 mol／L稀盐酸可以选择性脱除糖上的乙酰基，得到糖的2位保留乙酰基的产物。为了研究这个现象，又合更多还原

【Abstract】 1. Studies of the components of Coriaria sinica MaximCoriaria sinica Maxim is a bush of Coriaria L. Eight flavonal compounds were isolated from the leaves of Coriaria sinica Maxim by using various chromatogram and were elucidated by NMR, MS, IR, et al. The structural of the compounds were: Kaempferol (1), Kaempferol-3-O-α-L-rhamnoside (2), Kaempferol-3-O-β-D-galacto-side (3), Kaempferol-3-O-α-L-arabinoside (4), Quercetin (5), Quercetin-3-O-α-L-arabinoside (6), Quercetin-3-O-β-D-galactoside (7), Quercetin-3-O-β-D-glucoside (8). Four compounds were isolated from this plant for the first time, which were (2), (3), (4),(6).Five terpenoids were isolated from the leaves, fruits, seeds of Coriaria sinica Maxim, which were ursolic acid (9), Oleanolic acid (10), Actylkamebakaurinin (11), Coriatin (12), Tutin (13). Compound (10) and (11) were firstly isolated from the plant.Ursolic acid as the standard, 5% vanillin-acetic acid and perchloric acid as the developer, used the ultraviolet spectrophotometnc method to determine the content of the tritepenoidic acid in the leaves of Coriaria sinica Maxim.2. Synthesis of the saponins of ursolic acidUrsolic acid is a pentacyclic triterpene. The ursolic acid saponins bearing 4-chloro-4-deoxy-β-D-galactopyranose at C-3 and C-28 position of ursolic acid were designed and synthesized. In the study, an interesting fact was found: the dilute hydrochloric acid could selectively hydrolyze the acetyl group at the different position of the sugar moieties. The saponins of ursolic acid were obtained, which remained acetyl group in the C-2 of the sugar. In order to explain this fact, 3-hydroxyl ursolic acid-28-O-(2", 3", 4", 6"-tert-O-acetyl-β-D-galactopyranosyl) ester and o-nitro phenol-(2’, 3’, 6’-tri-acetyl-O-4-chloro-4-deoxy-β-D-galactopyranosyl) were also synthesized. Then hydroly- zed by the 0.1 mol/L diluted hydrochloric acid, 3-hydroxyl ursolic acid-28-O-(2", 3", 4", 6"-tert-O-acetyl-β-D-galactopyranosyl) ester formed a mixture of deacetylated compounds, but no all deacetylated compounds were obtained.更多还原