中草药  2015, Vol. 46 Issue (23): 3460-3465
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引用本文doi: 10.7501/j.issn.0253-2670.2015.23.003
肖云川, 赵曼茜, 闫翠起, 王炜, 黄全书, 梁凯, 孟保华, 柯潇, 叶亮. 马尾松鲜松叶的化学成分研究[J]. 中草药, 2015, 46(23): 3460-3465.
XIAO Yun-chuan, ZHAO Man-xi, YAN Cui-qi, WANG Wei, HUANG Quan-shu, LIANG Kai, MENG Bao-hua, KE Xiao, YE Liang. Studies on chemical constituents from fresh pineneedles of Pinus massoniana[J]. Chinese Traditional and Herbal Drugs, 2015, 46(23): 3460-3465.
马尾松鲜松叶的化学成分研究
肖云川, 赵曼茜, 闫翠起, 王炜, 黄全书, 梁凯, 孟保华, 柯潇, 叶亮     
成都康弘药业集团股份有限公司, 四川 成都 610036
收稿日期: 2015-07-02;
作者简介: 肖云川(1986-),女,博士,从事天然药物化学成分研究工作。
通讯作者: 叶亮,男,博士,高级工程师,主要从事新药研发工作。Tel:(028)87510917 E-mail:yeliang@cnkh.com
摘要: 目的 对马尾松Pinus massoniana鲜松叶的化学成分进行研究。方法 运用硅胶、Sephadex LH-20、ODS、SBC MCI等柱色谱进行分离纯化,根据理化性质和波谱数据鉴定化合物的结构。结果 从马尾松鲜松叶中分离得到14个化合物,分别鉴定为 (+)-儿茶素(1)、(+)-没食子儿茶素(2)、3,5-二羟基苯基-1-O-β-D-吡喃葡萄糖苷(3)、tachioside(4)、3,4-二甲氧基苯基-1-O-β-D-吡喃葡萄糖苷(5)、3,4-二甲氧基苯基-1-O-(3-O-甲氧基-α-L-鼠李糖基)-1→2-β-D-吡喃葡萄糖苷(6)、citrusin D(7)、(6S,7E,9R)-长寿花糖苷(8)、4-(2-丁酮)-苯基-1-O-β-D-吡喃葡萄糖苷(9)、(-)-10-α-O-β-D-葡萄糖基-刺参-4-酮(10)、massonianoside D(11)、massonianoside B(12)、异落叶松脂醇-9'-O-α-L-阿拉伯糖苷(13)、(2R,3R)-花旗松素-3'-O-β-D-吡喃葡萄糖苷(14)。结论 化合物2～6、10为首次从该属植物中分离得到,7～9为首次从该植物中分离得到。
关键词: 马尾松     (+)-没食子儿茶素     3,4-二甲氧基苯基-1-O-β-D-吡喃葡萄糖苷     (6S,7E,9R)-长寿花糖苷     (-)-10-α-O-β-D-葡萄糖基-刺参-4-酮    
Studies on chemical constituents from fresh pineneedles of Pinus massoniana
XIAO Yun-chuan, ZHAO Man-xi, YAN Cui-qi, WANG Wei, HUANG Quan-shu, LIANG Kai, MENG Bao-hua, KE Xiao, YE Liang    
Chengdu Kanghong Pharmaceutical Co., Ltd., Chengdu 610036, China
Abstract: Objective To study the chemical constituents from the fresh pineneedles of Pinus massoniana. Methods Certain chromatography means were used in the isolation and purification, and the structures of all the compounds were identified by means of spectroscopic analysis and physicochemical properties. Results Fourteen compounds were elucidated respectively as (+)-catechin (1), (+)-gallcatechin (2), phlorin (3), tachioside (4), 3,4-dimethoxyphenyl-1-O-β-D-glucopyranoside (5), 3,4-dimethoxyphenyl-1-O-(3-O-methyl-α-L-rhamnopyranosyl)-1→2-β-D-glucopyranoside (6), citrusin D (7), (6S,7E,9R)-roseoside (8), raspberry ketone-O-β-D-glucopyranoside (9), (-)-oplopan-4-one-10-α-O-β-D-glucose (10), massonianoside D (11), massonianoside B (12), isolariciresinol-9'-O-α-L-arabinofuranoside (13), and (2R,3R)-taxifolin-3'-O-β-D-glucopyranoside (14). Conclusion Compounds 2—6, and 10 are isolated from the plants of Pinus L. for the first time, and compounds 7—9 are obtained from P. massoniana for the first time.
Key words: Pinus massoniana Lamb.     (+)-gallcatechin     phlorin     3,4-dimethoxyphenyl-1-O-β-D-glucopyranoside     (6S,7E,9R)-roseoside     (-)-oplopan-4-one-10-α-O-β-D-glucose    

马尾松Pinus massoniana Lamb. 为松科（Pinaceae）松属Pinus L. 植物，广泛分布于我国亚热带东部湿润地区，并延至北热带，秦国峰[1]通过研究提出四川盆地的马尾松种源是我国古老马尾松的原始类型。其针叶具有祛风行气、活血止痛、舒筋、止血的功能，主治心血管疾病、咳嗽、胃及十二指肠疾病、习惯性便秘、湿疹、黄水疮、外伤出血等。药理实验表明马尾松松针具有抗氧化、抗衰老[2]、抑菌[3]、心血管保护作用[4]、调血脂[5]、抗肿瘤[6]等活性。国内外对该植物的化学成分研究主要集中于挥发油[7]、木脂素及其苷类[8]、黄酮及其苷类[9]、莽草酸[10]、原花青素[11]等类化合物。马尾松鲜松叶作为国内中成药松龄血脉康胶囊的君药，其化学成分研究相对较少，为进一步研究马尾松鲜叶的物质基础，本实验对其醋酸乙酯和正丁醇部位进行化学成分研究，从中分离得到14个化合物，分别鉴定为 (+)-儿茶素[(+)-catechin，1]、(+)-没食子儿茶素 [(+)-gallcatechin，2]、3,5-二羟基苯基-1-O-β-D-吡喃葡萄糖苷（phlorin，3）、tachioside（4）、3,4-二甲氧基苯基-1-O-β-D-吡喃葡萄糖苷（3,4-dimethoxy- phenyl-1-O-β-D-glucopyranoside，5）、3,4-二甲氧基苯基-1-O-(3-O-甲氧基-α-L-鼠李糖基)-1→2-β-D-吡喃葡萄糖苷 [3,4-dimethoxyphenyl-1-O-(3-O-methyl- α-L-rhamnopyranosyl)-1→2-β-D-gluco- pyranoside，6]、citrusin D（7）、(6S,7E,9R)-长寿花糖苷 [(6S,7E,9R)- roseoside，8]、4-(2-丁酮)-苯基-1-O-β-D-吡喃葡萄糖苷 [raspberry ketone-O-β-D-glucopyranoside，9]、(−)-10-α-O-β-D-葡萄糖基-刺参-4-酮 [(−)-oplopan-4- one-10-α-O-β-D-glucose，10]、massonianoside D（11）、massonianoside B（12）、异落叶松脂醇-9′-O- α-L-阿拉伯糖苷（isolariciresinol-9′-O-α-L-arabino- furanoside，13）、(2R,3R)-花旗松素-3′-O-β-D-吡喃葡萄糖苷 [(2R,3R)-taxifolin-3′-O-β-D-glucopyra- noside，14]。化合物2～6，10为首次从该属植物中分离得到，7～9为首次从该植物中分离得到。

1 仪器与材料

Bruker AV-400核磁共振仪；柱色谱硅胶（青岛海洋化工厂）、葡聚糖凝胶Sephadex G25（GE Healthcare Life Sciences）、葡聚糖凝胶Sephadex LH-20（GE Healthcare Life Sciences）、小孔树脂凝胶SBC MCI Gel（成都科普生物有限公司）、C18烷基键合硅胶GP-C18（Sepax Technologies Inc.）。其他有机试剂均为分析纯。

马尾松鲜松叶于2014年3月采自四川富顺，由成都中医药大学药学院严铸云教授鉴定为马尾松Pinus massoniana Lamb. 的鲜松叶。

2 提取与分离

取马尾松鲜松叶24kg，用50%乙醇加热回流提取合并提取液，减压浓缩得到总浸膏1 L。依次用石油醚、醋酸乙酯、水饱和正丁醇萃取，分别得到石油醚萃取浸膏83 g、醋酸乙酯萃取浸膏114 g、水饱和正丁醇萃取浸膏200 g。

取醋酸乙酯浸膏，经硅胶柱色谱，二氯甲烷-乙醇（4∶1）洗脱，分离得到4个部分，取含2个主斑点的第3部分，经硅胶柱色谱，石油醚-醋酸乙酯（2∶3）洗脱，去掉前后杂质，收集中间两主斑点部分；中间部分继续用二氯甲烷-乙醇（4.5∶1）洗脱，去掉前后杂质收集中间2主斑点部分；将中间部分经Sephadex LH-20凝胶柱色谱，20%、50%乙醇洗脱分别得化合物1（2.1 g）和2（58 mg）。取正丁醇浸膏，经大孔树脂D101吸附水洗脱，再经SBC MCI（水-100%乙醇）梯度洗脱分离得到5个部分Pr. 1～5。Pr. 1经Sephadex G25水洗脱，再经Sephadex LH-20水洗脱纯化得到化合物3（27 mg）。Pr. 2经Sephadex LH-20水洗脱，SBC MCI 20%乙醇洗脱，再经ODS 20%乙醇洗脱纯化得到化合物5（32 mg）和6（21 mg）。Pr. 3经Sephadex G25水洗脱，得到3个部分Pr. 3-1～3-3。Pr. 3-1经SBC MCI柱，20%乙醇洗脱，再经硅胶柱色谱，醋酸乙酯-乙醇（5∶1）洗脱，然后过Sephadex LH-20凝胶柱（20%乙醇洗脱）和ODS柱（20%乙醇洗脱），得化合物4（44 mg）、8（80 mg）和9（36 mg）。Pr. 3-3经Sephadex LH-20水洗脱，再经硅胶柱色谱醋酸乙酯- 乙醇（5∶1）洗脱纯化得到化合物7（53 mg）。Pr. 4经Sephadex G25柱（水洗脱），得到3个部分Pr. 4-1～4-3。Pr. 4-1经SBC MCI柱（20%～50%乙醇梯度洗脱），再经ODS柱（30%～50%乙醇梯度洗脱），最后经硅胶柱色谱，二氯甲烷-乙醇（5∶1）、石油醚-丙酮（1∶3）洗脱纯化得到化合物10（188 mg）。Pr. 4-2经SBC MCI柱，20%～50%乙醇梯度洗脱，再经硅胶柱色谱，二氯甲烷-乙醇（5∶1）、石油醚-丙酮（1∶3）洗脱纯化得到化合物11（208 mg）和12（37 mg）。Pr. 4-3经SBC MCI柱（20%、30%乙醇）梯度洗脱，再经ODS柱（20%乙醇洗脱）和Sephadex LH-20凝胶柱色谱（20%乙醇洗脱），最后经硅胶柱色谱，二氯甲烷-乙醇（5∶1）、石油醚-丙酮（1∶3）洗脱纯化得到化合物13（25 mg）和14（200 mg）。

3 结构鉴定

化合物1：白色粉末，5%香草醛显红色。1H-NMR (400 MHz, DMSO-d6) δ: 6.72 (1H, d, J = 2.0 Hz, H-2′), 6.68 (1H, d, J = 8.0 Hz, H-5′), 6.59 (1H, dd, J = 8.0, 2.0 Hz, H-6′), 5.89 (1H, s, H-8), 5.68 (1H, s, H-6), 4.47 (1H, d, J = 6.4 Hz, H-2), 3.80 (1H, m, H-3), 2.64 (1H, dd, J = 16.0, 5.6 Hz, H-4a), 2.34 (1H, dd, J = 16.0, 8.0 Hz, H-4b)；13C-NMR (100 MHz, DMSO-d6) δ: 156.9 (C-7), 156.7 (C-9), 155.8 (C-5), 145.3 (C-3′, 4′), 131.1 (C-1′), 119.0 (C-6′), 115.7 (C-2′), 114.9 (C-5′), 99.6 (C-10), 95.7 (C-6), 94.4 (C-8), 81.4 (C-2), 66.8 (C-3), 28.1 (C-4)。以上数据与文献报道一致[12]，故鉴定化合物1为儿茶素。

化合物2：白色粉末，5%香草醛显红色。1H-NMR (400 MHz, DMSO-d6)δ: 9.14 (1H, s, ph-5-OH), 8.91 (1H, s, ph-7-OH), 8.75 (2H, s, ph-3′, 5′-OH), 7.99 (1H, s, ph-4′-OH), 6.25 (2H, s, H-2′, 6′), 5.88 (1H, d, J = 2.4 Hz, H-8), 5.69 (1H, d, J = 2.4 Hz, H-6), 4.83 (1H, d, J = 5.2 Hz, 3-OH), 4.43 (1H, d, J = 7.2 Hz, H-2), 3.78 (1H, m, H-3), 2.61 (1H, dd, J = 16.0, 5.2 Hz, H-4a), 2.34 (1H, dd, J = 16.0, 7.6 Hz, H-4b)；13C-NMR (100 MHz, DMSO-d6) δ: 156.4 (C-7), 156.2 (C-9), 155.3 (C-5), 145.6 (C-3′, 5′), 132.4 (C-4′), 129.8 (C-1′), 105.9 (C-2′, 6′), 98.9 (C-10), 95.0 (C-8), 93.8 (C-6), 80.9 (C-2), 66.3 (C-3), 27.3 (C-4)。以上数据与文献报道一致[13]，故鉴定化合物2为没食子儿茶素。

化合物3：白色粉末，5%香草醛显红色。1H-NMR (400 MHz, DMSO-d6) δ: 9.21 (2H, brs, ph-3, 5-OH), 5.90 (2H, s, H-2, 6), 5.87 (1H, s, H-4), 5.23 (1H, d, J = 5.2 Hz, 2′-OH), 5.05 (1H, d, J = 4.8 Hz, 3′-OH), 4.68 (1H, d, J = 7.6 Hz, H-1′), 4.54 (1H, t, J = 6.0 Hz, 6′-OH), 3.67 (1H, m, H-6′a), 3.44 (1H, m, H-6′b), 3.22 (2H, m, H-3′, 4′), 3.15 (2H, m, H-2′, 5′)；13C-NMR (100 MHz, D2O) δ: 158.2 (C-1), 157.1 (C-3, 5), 99.5 (C-1′), 97.2 (C-4), 95.8 (C-2, 6), 75.6 (C-5′), 75.1 (C-3′), 72.4 (C-2′), 69.0 (C-4′), 60.2 (C-6′)。以上数据与文献报道一致[14]，故鉴定化合物3为3,5-二羟基苯基-1-O-β-D-吡喃葡萄糖苷。

化合物4：白色粉末，5%香草醛显黄色。1H-NMR (400 MHz, DMSO-d6) δ: 8.52 (1H, s, ph-4-OH), 6.68 (1H, d, J = 2.8 Hz, H-2), 6.64 (1H, d, J = 8.4 Hz, H-5), 6.45 (1H, dd, J = 8.4, 2.8 Hz, H-6), 5.23 (1H, d, J = 4.8 Hz, 2′-OH), 5.05 (1H, d, J = 4.8 Hz, 3′-OH), 4.99 (1H, d, J = 5.2 Hz, 4′-OH), 4.66 (1H, d, J = 7.2 Hz, H-1′), 4.59 (1H, t, J = 6.0 Hz, 6′-OH), 3.73 (3H, s, 3-OMe), 3.69 (1H, m, H-6′a), 3.44 (1H, m, H-6′b), 3.26 (1H, m, H-3′), 3.20 (2H, m, H-4′, 5′), 3.10 (1H, m, H-2′)；13C-NMR (100 MHz, D2O) δ: 150.8 (C-1), 147.9 (C-3), 140.5 (C-4), 115.6 (C-5), 108.8 (C-6), 102.9 (C-2), 101.3 (C-1′), 76.1 (C-5′), 75.6 (C-3′), 73.0 (C-2′), 69.5 (C-4′), 60.6 (C-6′), 55.9 (3-OMe)。以上数据与文献报道一致[15, 16, 17]，故鉴定化合物4为tachioside。

化合物5：白色粉末，5%香草醛显黄色。1H-NMR (400 MHz, DMSO-d6) δ: 6.85 (1H, d, J = 8.8 Hz, H-2), 6.71 (1H, d, J = 2.8 Hz, H-5), 6.55 (1H, dd, J = 8.8, 2.8 Hz, H-6), 5.26 (1H, d, J = 4.8 Hz, 2′-OH), 5.07 (1H, d, J = 4.8 Hz, 3′-OH), 5.01 (1H, d, J = 5.2 Hz, 4′-OH), 4.72 (1H, d, J = 7.6 Hz, H-1′), 4.59 (1H, t, J = 6.0 Hz, 6′-OH), 3.72 (3H, s, 3-OMe), 3.71 (1H, m, H-6′a), 3.69 (3H, s, 4-OMe), 3.44 (1H, m, H-6′b), 3.31 (1H, m, H-3′), 3.22 (2H, m, H-4′, 5′), 3.12 (1H, m, H-2′)；13C-NMR (100 MHz, D2O) δ: 151.2 (C-1), 148.7 (C-3), 144.0 (C-4), 112.2 (C-5), 108.1 (C-6), 102.4 (C-2), 101.3 (C-1′), 76.1 (C-5′), 75.6 (C-3′), 73.0 (C-2′), 69.5 (C-4′), 60.6 (C-6′), 55.9 (3-OMe), 55.6 (4-OMe)。以上数据与文献中tachioside的数据基本一致[15, 16, 17]，仅少了1个酚羟基信号而多1个甲氧基信号，故鉴定化合物5为3,4-二甲氧基苯基-1- O-β-D-吡喃葡萄糖苷。

化合物6：白色粉末，5%香草醛显黄色。1H-NMR (400 MHz, DMSO-d6) δ: 6.85 (1H, d, J = 8.8 Hz, H-2), 6.66 (1H, d, J = 2.8 Hz, H-5), 6.53 (1H, d, J = 8.8, 2.8 Hz, H-6), 5.29 (1H, d, J = 5.6 Hz, 3′-OH), 5.15 (1H, d, J = 0.8 Hz, H-1″), 5.10 (1H, d, J = 5.6 Hz, 4′-OH), 4.90 (1H, d, J = 4.8 Hz, 2″-OH), 4.86 (1H, d, J = 7.2 Hz, H-1′), 4.72 (1H, d, J = 4.8 Hz, 4″-OH), 4.63 (1H, t, J = 5.6 Hz, 6′-OH), 3.96 (1H, dd, J = 9.6, 6.4 Hz, H-2″), 3.92 (1H, m, H-5″), 3.71 (3H, s, 3-OMe), 3.70 (1H, m, H-6′a), 3.69 (3H, s, 4-OMe), 3.44 (3H, m, H-6b, 2′, 3′), 3.34 (1H, m, H-4″), 3.30 (1H, m, H-5′), 3.26 (3H, s, 3″-OMe), 3.15 (1H, dt, J = 9.2, 5.6 Hz, H-4′), 3.07 (1H, dd, J = 9.2, 2.8 Hz, H-3″), 1.19 (3H, d, J = 6.4 Hz, H-6″)；13C-NMR (100 MHz, D2O) δ: 150.9 (C-1), 148.9 (C-3), 144.0 (C-4), 112.7 (C-5), 107.5 (C-6), 102.1 (C-2), 101.2 (C-1″), 99.2 (C-1′), 79.5 (C-3″), 79.0 (C-3′), 76.4 (C-2′), 76.1 (C-5′), 70.7 (C-4″), 69.4 (C-4′), 69.0 (C-5″), 65.8 (C-2″), 60.6 (C-6′), 56.1 (4-OMe), 56.0 (3-OMe), 55.7 (3″-OMe), 16.8 (C-6″)。以上数据与文献报道一致[18]，故鉴定化合物6为3,4-二甲氧基苯基-1-O-(3-O-甲氧基-α-L-鼠李糖基)-1→2-β-D-吡喃葡萄糖苷。

化合物7：白色粉末，5%香草醛显紫色。1H-NMR (400 MHz, DMSO-d6) δ: 7.02 (1H, d, J = 2.0 Hz, H-2), 6.82 (1H, dd, J = 8.0, 2.0 Hz, H-6), 6.72 (1H, d, J = 8.0 Hz, H-5), 6.52 (1H, d, J = 16.0 Hz, H-7), 6.17 (1H, dt, J = 16.0, 6.0 Hz, H-8), 5.02 (1H, d, J = 5.2 Hz, 2′-OH), 4.91 (1H, d, J = 4.4 Hz, 3′-OH), 4.87 (1H, d, J = 5.2 Hz, 4′-OH), 4.50 (1H, t, J = 6.0 Hz, 6′-OH), 4.40 (1H, dd, J = 13.6, 6.0 Hz, H-9), 4.20 (1H, d, J = 6.8 Hz, H-1′), 4.17 (1H, dd, J = 13.6, 6.0 Hz, H-9), 3.78 (3H, s, 3-OMe), 3.69 (1H, ddd, J = 12.0, 6.0, 2.0 Hz, H-6′), 3.45 (1H, m, H-6′), 3.15 (1H, m, H-3′), 3.08 (2H, m, H-4′, 5′), 2.98 (1H, m, H-2′)；13C-NMR (100 MHz, DMSO-d6) δ: 147.7 (C-3), 146.5 (C-4), 131.9 (C-7), 128.0 (C-1), 122.9 (C-8), 119.7 (C-6), 115.4 (C-5), 109.7 (C-2), 102.0 (C-1′), 76.8 (C-5′), 76.7 (C-3′), 73.5 (C-2′), 70.1 (C-4′), 68.8 (C-9), 61.1 (C-6′), 55.5 (3-OMe)。以上数据与文献报道一致[19]，故鉴定化合物7为citrusin D。

化合物8：白色粉末，5%香草醛显土黄色。1H-NMR (400 MHz, DMSO-d6) δ: 5.77 (3H, m, H-4, 7, 8), 4.96 (1H, m, 2′-OH), 4.92 (1H, d, J = 4.8 Hz, 3′-OH), 4.87 (1H, d, J = 4.8 Hz, 4′-OH), 4.85 (1H, d, J = 4.4 Hz, 2-OH), 4.49 (1H, t, J = 5.6 Hz, 6′-OH), 4.32 (1H, m, H-9), 4.17 (1H, d, J = 7.6 Hz, H-1′), 3.64 (1H, m, H-6′a), 3.43 (1H, m, H-6′b), 3.12 (1H, m, H-3′), 3.03 (2H, m, H-4′, 5′), 2.93 (1H, m, H-2′), 2.42 (1H, d, J = 16.8 Hz, H-2b), 2.05 (1H, d, J = 16.8 Hz, H-2a), 1.81 (3H, s, 13-CH3), 1.18 (3H, d, J = 6.4 Hz, 10-CH3), 0.93 (3H, s, 11-CH3), 0.93 (3H, s, 12-CH3)；13C-NMR (100 MHz, DMSO-d6) δ: 197.3 (C-3), 164.0 (C-5), 133.3 (C-8), 130.3 (C-7), 125.6 (C-4), 100.8 (C-1′), 77.8 (C-6), 76.7 (C-5′), 76.7 (C-3′), 74.6 (C-2′), 73.6 (C-9), 70.0 (C-4′), 61.0 (C-6′), 49.3 (C-2), 40.8 (C-1), 24.0 (C-12), 23.0 (C-11), 20.8 (C-10), 18.8 (C-13)。以上数据与文献报道一致[20]，故鉴定化合物8为(6S,7E,9R)-长寿花糖苷。

化合物9：白色粉末，5%香草醛显紫红色。1H-NMR (400 MHz, DMSO-d6) δ: 7.10 (2H, d, J = 8.8 Hz, H-3, 5), 6.92 (2H, d, J = 8.8 Hz, H-2, 6), 5.25 (1H, d, J = 4.8 Hz, 2′-OH), 5.04 (1H, d, J = 4.4 Hz, 3′-OH), 4.98 (1H, d, J = 5.2 Hz, 4′-OH), 4.78 (1H, d, J = 7.6 Hz, H-1′), 4.53 (1H, t, J = 5.6 Hz, 6′-OH), 3.68 (1H, ddd, J = 12.0, 5.6, 2.0 Hz, H-6′a), 3.45 (1H, m, H-6′b), 3.24 (3H, m, H-3′, 4′, 5′), 3.14 (1H, dt, J = 9.2, 5.2 Hz, H-2′), 2.72 (4H, m, H-7, 8), 2.08 (3H, s, H-10)；13C-NMR (100 MHz, DMSO-d6) δ: 207.8 (C-9), 155.6 (C-1), 134.3 (C-4), 129.0 (C-3, 5), 116.1 (C-2, 6), 100.5 (C-1′), 77.0 (C-5′), 76.6 (C-3′), 73.2 (C-2′), 69.7 (C-4′), 60.7 (C-6′), 44.4 (C-8), 29.7 (C-7), 28.3 (C-10)。以上数据与文献报道一致[21]，故鉴定化合物9为4-(2-丁酮)-苯基-1-O-β-D-吡喃葡萄糖苷。

化合物10：白色粉末，5%香草醛显蓝色。1H-NMR (400 MHz, DMSO-d6) δ: 4.85 (1H, d, J = 4.8 Hz, 2′-OH), 4.83 (1H, d, J = 4.8 Hz, 3′-OH), 4.74 (1H, d, J = 4.8 Hz, 4′-OH), 4.35 (1H, t, J = 6.0 Hz, 6′-OH), 4.32 (1H, d, J = 7.6 Hz, H-1′), 3.62 (1H, dd, J = 10.4, 5.6 Hz, H-6′b), 3.44 (1H, m, H-6′a), 3.11 (1H, m, H-3′), 3.04 (2H, m, H-4′, 5′), 2.86 (1H, dt, J = 8.0, 4.8 Hz, H-2′), 2.63 (1H, m, H-5), 2.14 (3H, s, H-15), 1.84 (3H, m, H-7, 8b, 9a), 1.70 (1H, t, J = 9.6 Hz, H-6), 1.62 (1H, dt, J = 12.0, 4.8 Hz, H-1), 1.52 (1H, m, H-3a), 1.41 (3H, m, H-3b, 9b, 11), 1.24 (1H, m, H-2b), 1.14 (3H, s, H-14), 1.04 (2H, m, H-2a, 8a), 0.86 (3H, d, J = 6.8 Hz, H-12), 0.61 (3H, d, J = 6.8 Hz, H-13)；13C-NMR (100 MHz, DMSO-d6) δ: 210.9 (C-4), 96.3 (C-1′), 78.6 (C-10), 77.0 (C-5′), 76.5 (C-3′), 73.6 (C-2′), 70.2 (C-4′), 61.2 (C-6′), 54.7 (C-5), 53.6 (C-1), 48.5 (C-7), 45.8 (C-6), 37.8 (C-9), 29.1 (C-11), 28.8 (C-15), 28.0 (C-3), 25.3 (C-2), 22.2 (C-8), 21.8 (C-12), 17.8 (C-14), 15.5 (C-13)。以上数据与文献报道一致[22]，故鉴定化合物10为 (−)-10-α-O-β-D-葡萄糖基-刺参-4-酮。

化合物11：白色粉末，5%香草醛显紫色。1H-NMR (400 MHz, DMSO-d6) δ: 9.04 (1H, s, ph-4-OH), 6.90 (1H, s, H-2), 6.76 (2H, s, H-5, 6), 6.71 (1H, s, H-6′), 6.67 (1H, s, H-2′), 5.38 (1H, d, J = 6.8 Hz, H-7), 4.78 (1H, d, J = 4.4 Hz, 2″-OH), 4.76 (1H, d, J = 5.6 Hz, 4″-OH), 4.62 (1H, brs, H-1″), 4.57 (1H, d, J = 6.0 Hz, 3″-OH), 4.45 (1H, t, J = 5.2 Hz, 9′-OH), 3.78 (3H, s, 3′-OMe), 3.75 (3H, s, 3-OMe), 3.72 (1H, m, H-9a), 3.66 (1H, dd, J = 9.6, 5.2 Hz, H-9b), 3.61 (2H, m, H-2″, 8), 3.41 (4H, m, H-3″, 5″, 9′), 3.19 (1H, dt, J = 9.2, 5.6 Hz, H-4″), 2.54 (2H, m, H-7′), 1.70 (2H, m, H-8′), 1.13 (1H, d, J = 6.4 Hz, H-6″)；13C-NMR (100 MHz, D2O) δ: 147.3 (C-4), 145.3 (C-3), 145.0 (C-4′), 143.3 (C-3′), 135.8 (C-5′), 133.0 (C-1), 127.9 (C-1′), 118.7 (C-6), 116.1 (C-6′), 115.2 (C-5), 112.5 (C-2′), 109.9 (C-2), 99.6 (C-1″), 88.1 (C-7), 71.9 (C-4″), 70.4 (C-3″), 70.2 (C-2″), 68.7 (C-5″, 9), 61.2 (C-9′), 55.6 (3′-OMe), 55.5 (3-OMe), 50.3 (C-8), 33.6 (C-7′), 31.3 (C-8′), 16.8 (C-6″)。以上数据与文献报道一致[23, 24]，结合HMBC相关关系，故鉴定化合物11为massonianoside D。

化合物12：白色粉末，5%香草醛显紫色。1H-NMR (400 MHz, DMSO-d6) δ: 9.10 (1H, s, ph-3′-OH), 7.06 (1H, d, J = 8.4 Hz, H-5), 7.03 (1H, d, J = 1.2 Hz, H-2), 6.90 (1H, dd, J = 8.4, 1.2 Hz, H-5), 6.53 (1H, s, H-6′), 6.50 (1H, s, H-2′), 5.46 (1H, d, J = 6.0 Hz, H-7), 5.25 (1H, s, H-1″), 5.03 (1H, t, J = 5.2 Hz, 9-OH), 5.00 (1H, d, J = 4.4 Hz, 2″-OH), 4.86 (1H, d, J = 5.6 Hz, 4″-OH), 4.73 (1H, d, J = 6.0 Hz, 3″-OH), 4.43 (1H, t, J = 5.2 Hz, 9′-OH), 3.77 (3H, s, 3-OMe), 3.72 (1H, dd, J = 10.4, 5.2 Hz, H-9a), 3.64 (1H, m, H-9b), 3.59 (2H, m, H-2″, 8), 3.42 (4H, m, H-3″, 5″, 9′), 3.27 (1H, dt, J = 9.2, 5.6 Hz, H-4″), 2.45 (2H, m, H-7′), 1.65 (2H, m, H-8′), 1.10 (1H, d, J = 6.0 Hz, H-6″)；13C-NMR (100 MHz, DMSO-d6) δ: 150.0 (C-4), 144.7 (C-3), 144.6 (C-4′), 140.7 (C-3′), 136.7 (C-5′), 134.9 (C-1), 128.7 (C-1′), 118.0 (C-6), 117.8 (C-6′), 115.8 (C-2′), 114.9 (C-5), 110.5 (C-2), 99.6 (C-1″), 86.1 (C-7), 71.7 (C-4″), 70.4 (C-3″), 70.2 (C-2″), 69.6 (C-5″), 63.2 (C-9), 60.2 (C-9′), 56.0 (3-OMe), 53.7 (C-8), 34.7 (C-7′), 31.3 (C-8′), 17.8 (C-6″)。以上数据与文献报道一致[25]，故鉴定化合物12为massonianoside B。

化合物13：白色粉末，5%香草醛显红色。1H-NMR (400 MHz, DMSO-d6) δ: 8.76, 8.44 (各1H, s, ph-OH), 6.70 (1H, d, J = 8.0 Hz, H-5′), 6.65 (1H, d, J = 1.6 Hz, H-2), 6.62 (1H, s, H-2′), 6.48 (1H, dd, J = 8.0, 1.6 Hz, H-6), 6.10 (1H, s, H-5′), 5.36 (1H, d, J = 5.2 Hz, 2″-OH), 5.08 (1H, d, J = 5.6 Hz, 3″-OH), 4.69 (1H, t, J = 5.6 Hz, 5″-OH), 4.56 (1H, d, J = 2.0 Hz, H-1″), 4.42 (1H, t, J = 5.2 Hz, 9-OH), 3.84 (2H, m, H-7, 2″), 3.71 (3H, s, 3′-OMe), 3.71 (3H, s, 3-OMe), 3.66 (3H, m, H-9a, 3″, 4″), 3.44 (4H, m, H-9′, 5″), 2.93 (1H, dd, J = 10.0, 2.0 Hz, H-9b), 2.72 (2H, m, H-7′), 1.89 (1H, m, H-8′), 1.75 (1H, m, H-8)；13C-NMR (100 MHz, DMSO-d6) δ: 147.8 (C-3), 146.0 (C-3′), 145.1 (C-4), 144.6 (C-4′), 137.2 (C-1), 132.9 (C-6′), 127.6 (C-1′), 121.8 (C-6), 116.6 (C-5′), 115.9 (C-5), 113.7 (C-2), 112.3 (C-2′), 109.1 (C-1″), 84.1 (C-4″), 82.5 (C-2″), 77.2 (C-3″), 66.2 (C-9), 63.3 (C-9′), 61.6 (C-5″), 56.1 (3-OMe), 56.0 (3′-OMe), 46.6 (C-7), 44.2 (C-8), 38.2 (C-8′), 32.8 (C-7′)。以上数据与文献报道一致[26, 27]，结合HMBC相关关系，鉴定化合物13为异落叶松脂醇-9′-O-阿拉伯糖苷。

化合物14：白色粉末，5%香草醛显红色。1H-NMR (400 MHz, DMSO-d6) δ: 11.92 (1H, s, ph-5-OH), 10.85 (1H, brs, ph-7-OH), 8.79 (1H, brs, ph-4′-OH), 7.26 (1H, d, J = 1.6 Hz, H-2′), 7.03 (1H, dd, J = 8.0, 1.6 Hz, H-6′), 6.85 (1H, d, J = 8.0 Hz, H-5′), 5.91 (1H, d, J = 2.0 Hz, H-6), 5.87 (1H, d, J = 2.0 Hz, H-8), 5.76 (1H, d, J = 6.0 Hz, 2″-OH), 5.53 (1H, brs, 3-OH), 5.12 (1H, m, 3″-OH), 5.03 (1H, d, J = 11.2 Hz, H-2), 5.03 (1H, t, J = 5.6 Hz, 6″-OH), 4.71 (1H, d, J = 7.2 Hz, H-1″), 4.59 (1H, dd, J = 11.2, 6.0 Hz, H-3), 4.37 (1H, m, 4″-OH), 3.70 (1H, m, H-6″a), 3.45 (1H, m, H-6″b), 3.30 (3H, m, H-2″, 3″, 5″), 3.19 (1H, m, H-4″)；13C-NMR (100 MHz, DMSO-d6) δ: 197.7 (C-4), 166.9 (C-7), 163.3 (C-5), 162.5 (C-9), 147.2 (C-4′), 144.9 (C-3′), 128.2 (C-1′), 122.9 (C-6′), 116.6 (C-2′), 115.5 (C-5′), 102.1 (C-1″), 100.4 (C-10), 96.1 (C-6), 95.1 (C-8), 82.9 (C-2), 77.2 (C-5″), 76.0 (C-3″), 73.3 (C-2″), 71.3 (C-3), 69.7 (C-4″), 60.6 (C-6″)。以上数据与文献报道一致[28]，故鉴定化合物14为 (2R,3R)-花旗松素-3′-O-β-D-吡喃葡萄糖苷。

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