黄小燕1,2, 马国需2,陈路3,邹节明4,钟小清4,周艳林4, 吕高荣4,苏作林5,杨峻山2,许旭东2 , 袁经权1,3*
摘要:目的 研究金樱根药材来源之一的小果蔷薇Rosa cymosa Tratt. 根的化学成分。方法:用多种色谱方法对小果蔷薇根70%乙醇提取物进行分离纯化,结合波谱技术与化学方法进行结构鉴定。结果:从小果蔷薇根的乙醇提取物中分离鉴定了16个化合物,包括:2-乙酰基-洋委陵菜酸 (1),2-氧代-坡模酸 (2),2α,3α,19α-三羟基齐墩果烷-12-烯-28-O-β-D-吡喃葡萄糖苷 (3),构莓苷 F1 (4),野蔷薇亭 (5),23-羟基-委陵菜酸 (6),阿江榄仁亭 (7),2α,3α,19α,23-四羟基乌苏烷-12-烯-28-O-β-D-吡喃葡萄糖苷 (8),1β,3α,19α,23-四羟基乌苏烷-12-烯-28-O-β-D-吡喃葡萄糖苷 (9),儿茶素 (10),3,4-二羟基苯乙醇8-O-β-D-葡萄糖苷 (11),3,4,5-三甲氧基苯酚-O-β-D-芹糖-(1→6)-O-β-D-葡萄糖苷 (12),4-羟基-3-甲氧基-1-苯基-O-(6′-O-没食子酰基)-β-D-吡喃葡萄糖苷 (13),没食子酸乙酯 (14),3,4,5-三甲氧基苯酚-β-D-葡萄糖苷 (15),3,4,5-三甲氧基苄基β-D-葡萄糖苷 (16)。结论:化合物9、11~13、15、16为首次从蔷薇属分离得到,化合物3、9、11~16为首次从该种植物中分离得到。
关键词:小果蔷薇;蔷薇科;化学成分;三萜类;金樱根
金樱根为大宗原料药材之一,是我国三金片、金鸡胶囊、妇科千金片、王老吉凉茶等著名中成药的重要原料。小果蔷薇为金樱根药材的三种同属基源植物之一,是蔷薇科(Rosaceae)蔷薇属Rosa植物Rosa cymosa Tratt.的根[1,2],主要分布在我国南方地区,具有祛风除湿、收涩固脱、解毒消肿等功效,主要用于风湿关节痛,跌打损伤,腹泻,治疗痈疖疮疡,烧烫伤等症[3]。现代药理研究表明小果蔷薇具有一定的活性作用,如抗菌、抗炎、抗氧化等作用。为进一步开发利用该植物资源,系统阐明金樱根物质基础,本研究对小果蔷薇根的化学成分进行研究,从中分离得到16个化合物,分别鉴定为2-乙酰基-洋委陵菜酸 (1),2-氧代-坡模酸 (2),2α,3α,19α-三羟基齐墩果烷-12-烯-28-O-β-D-吡喃葡萄糖苷 (3),构莓苷 F1 (4),野蔷薇亭(5),23-羟基-委陵菜酸 (6),阿江榄仁亭 (7),2α,3α,19α,23-四羟基乌苏烷-12-烯-28-O-β-D-吡喃葡萄糖苷 (8),1β,3α,19α,23-四羟基乌苏烷-12-烯-28-O-β-D-吡喃葡萄糖苷 (9),儿茶素 (10),3,4-二羟基苯乙醇8-O-β-D-葡萄糖苷 (11),3,4,5-三甲氧基苯酚-O-β-D-芹糖-(1→6)-O-β-D-葡萄糖苷 (12),4-羟基-3-甲氧基-1-苯基-O-(6′-O-没食子酰基)-β-D-吡喃葡萄糖苷 (13),没食子酸乙酯 (14),3,4,5-三甲氧基苯酚-β-D-葡萄糖苷 (15),3,4,5-三甲氧基苄基β-D-葡萄糖苷 (16)。其中化合物9、11~13、15、16为首次从蔷薇属分离得到,化合物3、9、11~16为首次从该种植物中分离得到。
1仪器与材料
Bruker Avance Ⅲ 600型核磁共振波谱仪(德国Bruker公司);赛默飞世(Thermofisher)LTQ-Obitrap XL液质联用仪(美国Thermo公司);Lumtech 高效液相色谱仪(K501四元低压半制备),创新通恒科技有限公司;RE-2000A型旋转蒸发仪(上海振捷实验设备有限公司);色谱柱为Agilent SB-Phenyl(5µm,9.4 mm×250 mm)(美国安捷伦公司),Kromasil 100-5 C18 半制备色谱柱(5µm,10 mm×250 mm)(瑞士 Kromasil公司);Sephadex LH-20凝胶(Pharmacia公司);MCI gel (75-150 µm, Mitsubishi Chemical Corporation, Japan);ODS gel (40-60 µm, Daiso Co., Ltd., Japan);D101大孔吸附树脂(天津波鸿树脂科技有限公司);10-40 µm薄层色谱用硅胶GF254(青岛海洋化工有限公司);100~200目、200~300目、300~400目柱色谱用硅胶(青岛海洋化工有限公司);常规试剂均为分析纯(中国医药集团上海化学试剂公司)。
药材由桂林三金药业股份有限公司提供,产地为桂林雁山镇,经广西壮族自治区民族医药研究院戴斌研究员鉴定为蔷薇科蔷薇属植物小果蔷薇Rosa cymosa Tratt.根。
2 提取分离
小果蔷薇根10.0 kg,阴干,粉碎,以70%乙醇加热回流提取3次,过滤,提取液减压回收乙醇,并浓缩至无醇味。所得流浸膏分散于水中,依次石油醚、乙酸乙酯萃取,萃取液分别回收溶媒,浸膏分别另存。水相经D101大孔树脂吸附,依次用水、35%乙醇、75%乙醇和95%乙醇洗脱,洗脱液分别浓缩至干。95%乙醇洗脱部位干浸膏( 7 g ),经硅胶柱(100~200目)柱色谱分离,用石乙酸乙酯洗脱,浓缩Fr.1( 2 g ) 经硅胶(100~200目)柱色谱分离,氯仿-甲醇(80:1)洗脱得到化合物1 ( 3 mg )。75%乙醇洗脱部位干浸膏 ( 40 g ),经硅胶柱 (100~200目) 柱色谱分离,以二氯甲烷-甲醇(40:1 - 0:1)梯度洗脱,洗脱液浓缩得到5个部位Fr.A~ Fr.E。Fr.A ( 2 g ) 先后经硅胶(100~200目)柱色谱分离,氯仿-甲醇梯度洗脱,HPLC半制备色谱分离(Agilent SB-Phenyl 5µm,9.4×250 mm,75% 甲醇)得到化合物2 ( 2 mg )。Fr.B ( 4 g )先后经硅胶(100~200目)柱色谱分离,氯仿-甲醇梯度洗脱,HPLC半制备色谱分离(C18柱,9.4×250 mm,65% 甲醇)得到化合物3 ( 2 mg ),4 ( 80 mg ),5 ( 8 mg ),6 ( 2 mg )。Fr.C ( 4 g ) 经HPLC半制备色谱分离(C18柱,9.4×250 mm,58% 甲醇)得到化合物7 ( 6 mg )。Fr.D ( 5 g ) 经HPLC半制备色谱分离(C18柱,9.4×250 mm,58% 甲醇)得到化合物8 ( 20 mg ),9 ( 7 mg )。35%乙醇洗脱部位干浸膏 ( 60 g ),经硅胶柱(100~200目)柱色谱分离,以二氯甲烷-甲醇(20:1 - 0:1)梯度洗脱,洗脱液浓缩得到5个部位Fr.F~ Fr.J。Fr.G ( 7 g ) 先后经硅胶(100~200目)柱色谱分离,氯仿-甲醇梯度洗脱,得到6个部位Fr.G1~Fr.G6。Fr.G2部分经Sephadex LH-20凝胶柱色谱层析,以甲醇洗脱,得到化合物10 ( 50 mg )。Fr.G4经反相MCI中压柱色谱分离,以甲醇-水(30:70-100:0)梯度洗脱,以薄层示踪合并相同流分,得到30个流分,Fr.G4-26-30 经HPLC半制备色谱分离(Agilent SB-Phenyl 5µm,9.4×250 mm,20% 甲醇)得到化合物11 ( 5 mg ),12 ( 4 mg )。Fr.G5经HPLC半制备色谱分离(Agilent SB-Phenyl 5µm,9.4×250 mm,20% 甲醇)得到化合物13 ( 2 mg )。Fr.F ( 3 g ) 经硅胶(200-300目)柱色谱分离,氯仿-甲醇梯度洗脱,以薄层示踪合并相同流分,得到20个流分。Fr.F2经HPLC半制备色谱分离(C18柱,9.4×250 mm,30% 甲醇)得到化合物14 ( 30 mg )。Fr.F11经HPLC半制备色谱分离(C18柱,9.4×250 mm,38% 甲醇)得到化合物15 ( 3 mg ),16 ( 4 mg )。
3结构鉴定
化合物1:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 553.3484 [M+Na]+,分子式 C32H50O5。1H-NMR (pyridine-d5, 600 MHz) δ: 0.76 (3H, s, 23-CH3), 1.05 (3H, s, 24-CH3), 1.07 (3H, s, 26-CH3), 1.12 (3H, d, J =6.6 Hz, 30-CH3), 1.23 (3H, s, 25-CH3), 1.44 (3H, s, 29-CH3), 1.62 (3H, s, 27-CH3), 2.02 (3H, s, 32-CH3), 3.05 (1H, s, H-18), 3.49 (1H, d, J =9.6 Hz, H-3), 5.57 (1H, br s, H-12)。13C-APT (pyridine-d5, 150 MHz) δC: 44.9 (C-1), 74.0 (C-2), 80.1 (C-3), 38.8 (C-4), 56.0 (C-5), 19.3 (C-6), 33.8 (C-7), 40.8 (C-8), 48.0 (C-9), 38.9 (C-10), 24.5 (C-11), 127.6 (C-12), 140.4 (C-13), 42.6 (C-14), 29.7 (C-15), 26.8 (C-16), 48.7 (C-17), 55.0 (C-18), 73.1 (C-19), 42.8 (C-20), 27.3 (C-21), 40.7 (C-22), 27.3 (C-23), 17.9 (C-24), 17.2 (C-25), 17.5 (C-26), 25.1 (C-27), 181.0 (C-28), 27.4 (C-29), 16.9 (C-30), 171.2 (C-31), 21.8 (C-32)。以上数据与文献报道数据基本一致[4],故推断该化合物为2-乙酰基-洋委陵菜酸(2-acetyl tormentic acid)。
化合物2:白色粉末,10%浓硫酸-乙醇溶液显紫红色,HR-ESI-MS, m/z 509.3431 [M+Na]+,分子式 C30H46O5。1H-NMR (pyridine-d5, 600 MHz) δ: 0.93 (3H, s, 24-CH3), 0.98 (3H, s, 26-CH3), 1.08 (3H, s, 25-CH3), 1.11 (3H, d, J = 6.6 Hz, 30-CH3), 1.24 (3H, s, 23-CH3), 1.42 (3H, s, 29-CH3), 1.68 (3H, s, 27-CH3), 3.04 (1H, s, H-18), 3.10 (1H, dt, J = 13.2, 9.0 Hz, H-16), 3.90 (1H, s, H-3), 5.57 (1H, br s, H-12)。13C-APT (pyridine-d5, 150 MHz) δC: 51.9 (C-1), 213.7 (C-2), 83.6 (C-3), 45.6 (C-4), 55.2 (C-5), 20.4 (C-6), 33.6 (C-7), 42.8 (C-8), 48.1 (C-9), 41.2 (C-10), 24.9 (C-11), 127.7 (C-12), 140.5 (C-13), 43.3 (C-14), 29.7 (C-15), 26.8 (C-16), 48.8 (C-17), 55.0 (C-18), 73.1 (C-19), 43.0 (C-20), 27.3 (C-21), 38.8 (C-22), 28.2 (C-23), 17.2 (C-24), 25.1 (C-25), 17.2 (C-26), 24.9 (C-27), 180.8 (C-28), 27.5 (C-29), 17.1 (C-30)。以上数据与文献报道数据基本一致[5],故推断该化合物为2-氧代-坡模酸(2-oxo-pomolic acid)。
化合物3:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 673.4009 [M+Na]+,分子式 C36H58O10 。1H-NMR (pyridine-d5, 600 MHz) δ: 0.90 (3H, s, 24-CH3), 0.96 (3H, s, 30-CH3), 1.02 (3H, s, 25-CH3), 1.12 (3H, s, 29-CH3), 1.17 (3H, s, 26-CH3), 1.24 (3H, s, 23-CH3), 1.51 (3H, s, 27-CH3), 3.51 (1H, br s, H-19), 3.53 (1H, d, J = 2.4 Hz, H-3), 5.49 (1H, br s, H-12), 6.37 (1H, d, J = 8.4 Hz, H-1′)。13C-APT (pyridine-d5, 150 MHz) δC: 42.6 (C-1), 66.5 (C-2), 79.7 (C-3), 39.2 (C-4), 49.3 (C-5), 19.1 (C-6), 33.4 (C-7), 40.9 (C-8), 48.6 (C-9), 39.3 (C-10), 24.6 (C-11), 123.7 (C-12), 144.7 (C-13), 43.1 (C-14), 28.4 (C-15), 28.4 (C-16), 46.9 (C-17), 45.0 (C-18), 81.5 (C-19), 36.0 (C-20), 29.4 (C-21), 33.6 (C-22), 29.8 (C-23), 22.6 (C-24), 17.0 (C-25), 18.1 (C-26), 25.2 (C-27), 177.7 (C-28), 29.1 (C-29), 25.1 (C-30), 96.3 (C-1′), 74.5 (C-2′), 79.3 (C-3′), 71.5 (C-4′), 79.8 (C-5′), 62.6 (C-6′)。以上数据与文献报道数据基本一致[6],故推断该化合物为2α,3α,19α-三羟基齐墩果烷-12-烯-28-O-β-D-吡喃葡萄糖苷(2α,3α,19α-trihydroxy-olean-12-en-28-O-β-D-glucopyranoside)。
化合物4:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 673.3898 [M+Na]+,分子式 C36H58O10。1H-NMR (pyridine-d5, 600 MHz) δ: 0.89 (3H, s, 24-CH3), 1.02 (3H, s, 25-CH3), 1.04 (3H, d, J = 6.6 Hz, 30-CH3), 1.20 (3H, s, 26-CH3), 1.23 (3H, s, 23-CH3), 1.35 (3H, s, 29-CH3), 1.58 (3H, s, 27-CH3), 2.90 (1H, s, H-18), 3.74 (1H, d, J = 2.4 Hz, H-3), 5.52 (1H, br s, H-12), 6.28 (1H, d, J = 8.4 Hz, H-1′)。13C-APT (pyridine-d5, 150 MHz) δC: 42.6 (C-1), 66.5 (C-2), 79.4 (C-3), 39.2 (C-4), 49.2 (C-5), 19.1 (C-6), 33.9 (C-7), 41.2 (C-8), 48.1 (C-9), 39.1 (C-10), 24.5 (C-11), 128.8 (C-12), 139.7 (C-13), 43.4 (C-14), 29.6 (C-15), 26.5 (C-16), 49.0 (C-17), 54.8 (C-18), 73.1 (C-19), 42.5 (C-20), 27.1 (C-21), 38.1 (C-22), 29.8 (C-23), 22.7 (C-24), 17.1 (C-25), 17.9 (C-26), 24.9 (C-27), 177.3 (C-28), 27.4 (C-29), 17.1 (C-30), 96.2 (C-1′), 74.5 (C-2′), 79.6 (C-3′), 71.7 (C-4′), 79.7 (C-5′), 62.8 (C-6′)。以上数据与文献报道数据基本一致[7, 8],故推断该化合物为构莓苷F1 (kaji-ichigoside F1)。
化合物5:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 673.4024 [M+Na]+,分子式 C36H58O10。1H-NMR (pyridine-d5, 600 MHz) δ: 1.05 (3H, s, 25-CH3), 1.05 (3H, d, J = 6.6 Hz, 30-CH3), 1.08 (3H, s, 24-CH3), 1.20 (3H, s, 26-CH3), 1.24 (3H, s, 23-CH3), 1.38 (3H, s, 29-CH3), 1.66 (3H, s, 27-CH3), 2.92 (1H, s, H-18), 3.37 (1H, d, J = 9.6 Hz, H-3), 5.53 (1H, br s, H-12), 6.29 (1H, d, J = 7.8 Hz, H-1′)。13C-APT (pyridine-d5, 150 MHz) δC: 48.4 (C-1), 69.1 (C-2), 84.3 (C-3), 38.9 (C-4), 56.4 (C-5), 19.5 (C-6), 33.9 (C-7), 41.1 (C-8), 48.3 (C-9), 40.2 (C-10), 24.6 (C-11), 128.8 (C-12), 139.7 (C-13), 42.6 (C-14), 29.6 (C-15), 26.5 (C-16), 49.1 (C-17), 54.8 (C-18), 73.1 (C-19), 42.5 (C-20), 27.1 (C-21), 38.1 (C-22), 29.8 (C-23), 17.9 (C-24), 17.1 (C-25), 18.0 (C-26), 25.0 (C-27), 177.4 (C-28), 27.4 (C-29), 17.4 (C-30), 96.3 (C-1′), 74.5 (C-2′), 79.4 (C-3′), 71.7 (C-4′), 79.6 (C-5′), 62.8 (C-6′)。以上数据与文献报道数据基本一致[9],故推断该化合物为野蔷薇亭(rosamultin)。
化合物6:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 527.3412 [M+Na]+,分子式 C30H48O6。1H-NMR (pyridine-d5, 600 MHz) δ: 1.06 (3H, s, 24-CH3), 1.08 (3H, s, 26-CH3), 1.10 (3H, d, J = 6.6 Hz, 30-CH3), 1.12 (3H, s, 25-CH3), 1.40 (3H, s, 27-CH3), 1.64 (3H, s, 29-CH3), 3.04 (1H, br s, H-18), 3.72 (1H, d, J = 10.8 Hz, H-23a), 4.18 (1H, d, J = 9.0 Hz, H-23b), 4.19 (1H, s, H-3), 4.37 (1H, t, J = 13.2, 6.6 Hz, H-2), 5.57 (1H, br s, H-12)。13C-APT (pyridine-d5, 150 MHz) δC: 48.7 (C-1), 69.3 (C-2), 78.8 (C-3), 44.0 (C-4), 48.5 (C-5), 19.1 (C-6), 33.6 (C-7), 40.9 (C-8), 48.2 (C-9), 38.9 (C-10), 24.6 (C-11), 128.4 (C-12), 140.4 (C-13), 42.6 (C-14), 29.7 (C-15), 26.8 (C-16), 48.7 (C-17), 55.0 (C-18), 73.1 (C-19), 42.8 (C-20), 27.3 (C-21), 38.8 (C-22), 67.1 (C-23), 14.7 (C-24), 17.2 (C-25), 17.8 (C-26), 25.1 (C-27), 180.1 (C-28), 27.5 (C-29), 17.7 (C-30)。以上数据与文献报道数据基本一致[10],故推断该化合物为23-羟基-委陵菜酸(23-hydroxy-tormentic acid)。
化合物7:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 673.3912 [M+Na]+,分子式 C36H58O10。1H-NMR (pyridine-d5, 600 MHz) δ: 0.97 (3H, s, 26-CH3), 1.04 (3H, s, 25-CH3), 1.08 (3H, s, 24-CH3), 1.13 (3H, s, 30-CH3), 1.16 (3H, s, 29-CH3), 1.25 (3H, s, 23-CH3), 1.60 (3H, s, 27-CH3), 3.37 (1H, d, J = 9.6 Hz, H-3), 4.41 (1H, d, J = 3.6 Hz, H-19), 5.49 (1H, br s, H-12), 6.37 (1H, d, J = 7.8 Hz, H-1′)。13C-APT (pyridine-d5, 150 MHz) δC: 48.0 (C-1), 69.0 (C-2), 84.3 (C-3), 39.1 (C-4), 56.5 (C-5), 19.5 (C-6), 33.4 (C-7), 40.7 (C-8), 48.8 (C-9), 40.2 (C-10), 24.7 (C-11), 124.0 (C-12), 144.8 (C-13), 42.6 (C-14), 29.4 (C-15), 28.4 (C-16), 46.9 (C-17), 45.0 (C-18), 81.5 (C-19), 35.9 (C-20), 29.4 (C-21), 33.6 (C-22), 29.7 (C-23), 18.1 (C-24), 17.3 (C-25), 18.0 (C-26), 25.1 (C-27), 177.7 (C-28), 29.1 (C-29), 25.3 (C-30), 96.3 (C-1′), 74.6 (C-2′), 79.4 (C-3′), 71.6 (C-4′), 79.7 (C-5′), 62.6 (C-6′)。以上数据与文献报道数据基本一致[6],故推断该化合物为阿江榄仁亭(arjunetin)。
化合物8:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 689.3980 [M+Na]+,分子式 C36H58O11。1H-NMR (pyridine-d5, 600 MHz) δ: 0.84 (3H, s, 24-CH3), 1.03 (3H, d, J = 6.6 Hz, 30-CH3), 1.04 (3H, s, 25-CH3), 1.19 (3H, s, 26-CH3), 1.34 (3H, s, 29-CH3), 1.60 (3H, s, 27-CH3), 3.00 (1H, s, H-18), 3.70 (1H, d, J = 10.8 Hz, H-23b), 3.87 (1H, d, J = 10.8 Hz, H-23a), 4.02 (1H, br s, H-2), 4.10 (1H, br s, H-3), 5.51 (1H, br s, H-12), 6.26 (1H, d, J = 8.4 Hz, H-1′)。13C-APT (pyridine-d5, 150 MHz) δC: 43.1 (C-1), 66.6 (C-2), 79.2 (C-3), 42.5 (C-4), 48.1 (C-5), 18.8 (C-6), 33.5 (C-7), 41.0 (C-8), 43.9 (C-9), 38.8 (C-10), 24.5 (C-11), 128.7 (C-12), 139.6 (C-13), 42.2 (C-14), 29.5 (C-15), 26.4 (C-16), 48.9 (C-17), 54.7 (C-18), 73.0 (C-19), 42.4 (C-20), 27.0 (C-21), 38.0 (C-22), 71.5 (C-23), 17.0 (C-24), 17.4 (C-25), 18.1 (C-26), 24.9 (C-27), 177.4 (C-28), 27.3 (C-29), 17.9 (C-30), 96.1 (C-1′), 74.3 (C-2′), 79.2 (C-3′), 71.6 (C-4′), 79.5 (C-5′), 62.7 (C-6′)。以上数据与文献报道数据基本一致[11],故推断该化合物为2α,3α,19α,23-四羟基乌苏烷-12-烯-28-O-β-D-吡喃葡萄糖苷(2α,3α,19α,23-tetrahydroxy-urs-12-en-28-O-β-D-glucopyranoside)。
化合物9:白色粉末,10%浓硫酸-乙醇溶液显紫红色。HR-ESI-MS, m/z 689.3970 [M+Na]+,分子式 C36H58O11。1H-NMR (pyridine-d5, 600 MHz) δ: 0.94 (3H, s, 24-CH3), 1.04 (3H, d, J = 6.6 Hz, 30-CH3), 1.22 (3H, s, 23-CH3), 1.30 (6H, s, 25,26-CH3), 1.35 (3H, s, 29-CH3), 1.63 (3H, s, 27-CH3), 2.91 (1H, s, H-18), 3.84 (1H, d, J = 2.4 Hz, H-3), 4.10 (1H, d, J = 9.6 Hz, H-1), 4.16 (1H, d, J = 3.0 Hz, H-2), 5.57 (1H, br s, H-12), 6.29 (1H, d, J = 7.8 Hz, H-1′)。13C-APT (pyridine-d5, 150 MHz) δC: 81.4 (C-1), 71.7 (C-2), 79.3 (C-3), 38.8 (C-4), 49.1 (C-5), 19.3 (C-6), 34.2 (C-7), 41.8 (C-8), 48.8 (C-9), 44.2 (C-10), 27.1 (C-11), 130.3 (C-12), 138.5 (C-13), 42.5 (C-14), 29.6 (C-15), 26.6 (C-16), 49.0 (C-17), 54.7 (C-18), 73.0 (C-19), 42.5 (C-20), 28.4 (C-21), 38.1 (C-22), 29.7 (C-23), 22.8 (C-24), 13.5 (C-25), 18.2 (C-26), 24.9 (C-27), 177.4 (C-28), 27.3 (C-29), 17.0 (C-30), 96.2 (C-1′), 74.5 (C-2′), 79.6 (C-3′), 71.7 (C-4′), 80.1 (C-5′), 62.8 (C-6′)。以上数据与文献报道数据基本一致[12],故推断该化合物为1β,3α,19α,23-四羟基乌苏烷-12-烯-28-O-β-D-吡喃葡萄糖苷(1β,2α,3α,19α-tetrahydroxyurs-12-en-28-O-β-D-glucopyranoside)。
化合物10:棕黄色粉末,三氯化铁显色阳性。HR-ESI-MS, m/z 313.0671 [M+Na]+,分子式 C15H14O6。1H-NMR (CD3OD, 600 MHz) δ: 6.84 (1H, d, J = 1.8 Hz, H-2′), 6.77 (1H, d, J = 8.4 Hz, H-5′), 6.72 (1H, dd, J = 8.4, 2.4 Hz, H-6′), 5.93 (1H, d, J = 2.4 Hz, H-8), 5.86 (1H, d, J = 2.4 Hz, H-6), 4.57 (1H, d, J = 7.8 Hz, H-2), 3.98 (1H, dd,J = 13.2, 7.8 Hz, H-3), 2.85 (1H, dd, J = 16.2, 5.4 Hz, H-4a), 2.51 (1H, dd, J = 15.6, 7.8 Hz, H-4b)。13C-NMR (CD3OD, 150 MHz) δ: 83.1 (C-2), 69.1 (C-3), 28.8 (C-4), 157.8 (C-5), 96.6 (C-6), 158.1 (C-7), 95.8 (C-8), 157.2 (C-9), 101.2 (C-10), 132.5 (C-1′), 116.4 (C-2′),146.5 (C-3′), 146.5 (C-4′), 115.6 (C-5′), 120.3 (C-6′)。 以上数据与文献报道数据基本一致[13],故推断该化合物为儿茶素(catechin)。
化合物11:黄色无定型粉末,HR-ESI-MS, m/z 339.1065 [M+Na]+,分子式 C14H20O8。1H-NMR (CD3OD, 600 MHz) δ: 2.72 (1H, dd, J = 14.4, 7.2 Hz, H-7b), 3.48 (2H, t, J = 7.8 Hz, H-8), 3.71 (1H, dd, J = 7.2, 13.8 Hz, H-7a), 4.75 (1H, d, J = 7.8 Hz, H-1′), 6.76 (1H, d, J = 8.4 Hz, H-5), 6.77 (1H, d, J = 7.2, 1.8 Hz, H-6), 7.08 (1H, d, J = 1.8 Hz, H-2)。13C-NMR (CD3OD, 150 MHz) δ: 132.3(C-1), 117.0(C-2), 146.9(C-3), 146.8(C-4), 117.2(C-5), 119.8(C-6), 39.7(C-7), 64.5(C-8), 104.6(C-1′), 75.1(C-2′), 77.9(C-3′), 71.6(C-4′), 78.5(C-5′), 62.7(C-6′)。以上数据与文献报道数据基本一致[14],故推断该化合物为3,4-二羟基苯乙醇8-O-β-D-葡萄糖苷(3,4-dihydroxyphenylethyl alcohol 8-O-β-D-glucopyranoside)。
化合物12:黄色无定型粉末,HR-ESI-MS, m/z 501.1602 [M+Na]+,分子式 C20H30O13。1H-NMR (CD3OD, 600 MHz) δ: 6.46 (2H, s, H-2, 6), 3.82 (6H, s, OCH3-3, 5), 3.71 (3H, s, OCH3-4), 4.80 (1H, d, J = 7.8 Hz, H-1′), 4.97 (1H, d, J = 3.0 Hz, H-1′′), 3.88 (1H, d, J = 2.4 Hz, H-2′′), 3.95 (1H, d, J = 9.6 Hz, H-4′′), 4.05 (1H, d, J = 9.0 Hz, H-4′′), 3.55 (2H, s, H-5′′)。13C-NMR (CD3OD, 150 MHz) δ: 135.3(C-1), 96.6(C-2), 155.0(C-3,5), 156.2(C-4), 96.4(C-6), 57.0(OCH3-3), 61.1(OCH3-4), 56.8(OCH3-5), 103.3(C-1′), 75.2(C-2′), 78.3(C-3′), 71.7(C-4′), 77.9(C-5′), 65.5(C-6′), 110.9(C-1′′), 77.9(C-2′′), 80.7(C-3′′), 75.0(C-4′′), 65.5(C-5′′)。以上数据与文献报道数据基本一致[15],故推断该化合物为3,4,5-三甲氧基苯酚-O-β-D-芹糖-(1→6)-O-β-D-葡萄糖苷(3,4,5-trimethoxyphenyl-1-O-β-apiofuranosyl (1′′→6′)-β-glucopyranoside)。
化合物13:黄色无定型粉末,HR-ESI-MS, m/z 477.0991 [M+Na]+,分子式 C20H22O12。1H-NMR (CD3OD, 600 MHz) δ: 6.70 (1H, d, J = 2.4 Hz, H-2), 6.62 (1H, d, J = 8.4 Hz, H-5), 6.57(1H, dd, J = 8.4, 2.4 Hz, H-6), 3.70 (3H, s, OCH3-3), 4.73 (1H, d, J = 7.8 Hz, H-1′), 3.45 (m, H-2′), 3.47 (m, H-3′), 3.44 (m, H-4′), 3.82 (m, H-5′), 4.59 (1H, dd, J = 11.4, 1.8 Hz, H-6′a), 4.43 (1H, dd, J = 12.0, 7.2 Hz, H-6′b), 7.10 (2H, s, H-2′′, 6′′)。13C-NMR (CD3OD, 150 MHz) δ: 152.9(C-1), 104.2(C-2), 149.4(C-3), 143.4(C-4), 116.3(C-5), 110.5(C-6), 56.6(OCH3-3), 104.2(C-1′), 75.2(C-2′), 78.1(C-3′), 72.0(C-4′), 75.9(C-5′), 65.2(C-6′), 121.7(C-1′′), 110.5(C-2′′), 146.8(C-3′′), 140.1(C-4′′), 146.8(C-5′′), 110.5(C-6′′), 168.5(C-7′′)。以上数据与文献报道数据基本一致[16, 17],故推断该化合物为4-羟基-3-甲氧基-1-苯基-O-(6′-O-没食子酰基)-β-D-吡喃葡萄糖苷(4-hydroxy-3-methoxy-phenyl-1-O-(6′-O-galloyl)-β-D-glucopyranoside)。
化合物14:白色粉末,HR-ESI-MS, m/z 221.0433 [M+Na]+,分子式 C9H10O5。1H-NMR (CD3OD, 600 MHz) δ: 7.06 (2H, s, H-2,6), 4.26 (2H, q, J = 7.2 Hz, H-OCH2CH3 ), 1.33 (3H, t, J = 7.2 Hz, H-OCH2CH3 )。以上数据与文献报道数据基本一致[18],故推断该化合物为没食子酸乙酯(ethyl gallate)。
化合物15:黄色无定型粉末,HR-ESI-MS, m/z 369.1177 [M+Na]+,分子式 C15H22O9。1H-NMR (CD3OD, 600 MHz) δ: 3.33-3.47 (4H, m, H-2′,3′,4′,5′), 3.66 (1H, dd, J = 12.0, 6.6 Hz, H-6′a), 3.70 (3H, s, OCH3-4), 3.81 (6H, s, OCH3-3,5), 3.92 (1H, dd, J = 12.0, 1.8 Hz, H-6′b), 4.81 (1H, d, J = 7.2 Hz, H-1′), 6.49 (2H, s, H-2, 6)。以上数据与文献报道数据基本一致[19-21],故推断该化合物为3,4,5-三甲氧基苯酚-β-D-葡萄糖苷(3,4,5-trimethoxyphenyl-β-D-glucopyranoside)。
化合物16:棕黄色无定型粉末,HR-ESI-MS, m/z 383.1331 [M+Na]+,分子式为 C16H24O9。1H-NMR (CD3OD, 600 MHz) δ: 3.23-3.29 (4H, m, H-2′,3′,4′,5′), 3.69 (1H, dd, J = 12.0, 5.4 Hz, H-6′b), 3.75 (3H, s, OCH3-4), 3.84 (6H, s, OCH3-3,5), 3.90 (1H, dd, J = 12.0, 1.8 Hz, H-6′a), 4.32 (1H, d, J = 7.8 Hz, H-1′), 4.64 (1H, d, J = 12.0 Hz, H-7a), 4.84 (1H, d, J = 12.0 Hz, H-7b), 6.77 (2H, s, H-2, 6)。以上数据与文献报道数据基本一致[22, 23],故推断该化合物为3,4,5-三甲氧基苄基β-D-葡萄糖苷(3,4,5-trimethoxybenzyl β-D-glucopyranoside )。
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