APP下载

金橘化学成分的研究(Ⅰ)

2022-12-29刘宏栋刘红宁

中成药 2022年2期
关键词:金橘二氯甲烷石油醚

王 倩, 刘宏栋, 刘 勇, 刘红宁, 陈 杰, 李 斌*

(1.江西中医药大学院士工作站,江西 南昌 330004;2.江西中医药大学药学院,江西 南昌 330004;3.江西中医药大学中医基础理论分化发展研究中心,江西 南昌 330004)

金橘Fortunellamargarita(Lour.)Swingle为芸香科金橘属植物果实,又名金弹和金柑,主要分布在福建、江西和浙江等省,因其口味酸甜,营养丰富有益于健康而被世界各地引进种植[1]。《本草纲目》记载其性温,味辛、甘,有理气解郁、消食化痰、醒酒止咳之功效[2],主治脘腹痞胀、主胸闷郁结、食滞纳呆等症[3]。文献显示,金橘在抗氧化、抗菌、抗炎、抗肿瘤、抗癌和降血脂等方面有广泛的药理活性[4-9]。为研究金橘果实中的药理活性成分,本实验对金橘95%乙醇提取物的石油醚部位、二氯甲烷部位和乙酸乙酯部位的化学成分进行研究,得到17个化合物,其中化合物1~2、4~5、7~10、13、16~17为首次从该植物中分离得到,化合物16为金橘属植物中首次分离得到。

1 材料

AVANCE Ⅲ600 MHz核磁共振仪(德国Bruker公司);Waters 515制备液相色谱仪、Waters 2487制备液相色谱(美国Waters公司);SHIMADZU LC-20AT 高效液相色谱仪(日本岛津公司);AB 5600+高分辨飞行时间质谱联用仪(美国AB SCIEX公司);ODS柱层析填料和MCI柱层析填料(日本YMC公司);柱层析硅胶、GF254硅胶板(青岛海洋化工厂)。其余试剂均为国产分析纯和色谱纯。

金橘果实于2018年12月购于江西遂川,经江西中医药大学刘勇教授鉴定为金橘属金橘Fortunellamargarita(Lour.)Swingle的果实。

2 提取与分离

将50 kg金橘果实捣碎,95%乙醇回流提取2次,每次1 h,合并提取液并减压浓缩得总浸膏15.2 kg,取其中1.5 kg浸膏经硅胶柱,依次用石油醚、二氯甲烷、乙酸乙酯、丙酮和甲醇洗脱,浓缩后得石油醚部位3 g、二氯甲烷部位12 g、乙酸乙酯部位24 g、丙酮部位40 g、甲醇部位1 318 g。

石油醚部位浸膏(3 g)经硅胶柱,石油醚-乙酸乙酯(100∶1~1∶1)梯度洗脱,得到5个馏分Fr.S1~Fr.S5。Fr.S3部位(0.8 g)经硅胶柱,石油醚-丙酮(50∶1~1∶1)梯度洗脱,分离得到10个馏分Fr.S3-1~Fr.S3-10。Fr.S3-5部位析出白色结晶,得化合物1(3.1 mg)。Fr.S3-6部位(180 mg)经反复硅胶柱,石油醚-乙酸乙酯(40∶1~2∶1)梯度洗脱,得化合物2(2.8 mg)、4(2.1 mg)、5(1.6 mg)。Fr.S3-7部位(170 mg)经硅胶柱,石油醚-乙酸乙酯(30∶1~1∶1)梯度洗脱,得化合物3(20.1 mg)、8(2.3 mg)。

二氯甲烷部位浸膏(12 g)经ODS柱,甲醇-水(1∶5~1∶0)梯度洗脱,得到8个馏分Fr.E1~Fr.E8。Fr.E4部位(1.9 g)经硅胶柱,石油醚-丙酮(12∶1~1∶1)梯度洗脱,得化合物6(11.2 mg)。Fr.E5部位(3.2 g)经硅胶柱,二氯甲烷-甲醇(35∶1~5∶1)梯度洗脱,再经半制备HPLC,甲醇-水(3∶2、13∶7)洗脱,得化合物13(3.8 mg)、10(5.6 mg)、15(7.2 mg)。Fr.E7部位(2.3 g)经硅胶柱,石油醚-丙酮(25∶1~3∶1)、石油醚-乙酸乙酯(15∶1~3∶1)洗脱,得化合物7(4.1 mg)、9(2.1 mg)。

乙酸乙酯部位浸膏(24 g)经MCI柱色谱,甲醇-水(0∶1~1∶0)梯度洗脱,得5个馏分Fr.EA1~Fr.EA5。Fr.EA3部位(6.2 g)经硅胶柱,二氯甲烷-甲醇(30∶1~5∶1)梯度洗脱,再经Sephadex LH-20柱色谱,甲醇纯化,得化合物11(9.6 mg)、12(8.3 mg)、14(10.4 mg)。Fr.EA4部位(3.4 g)经ODS柱色谱,甲醇-水(1∶1~1∶0)梯度洗脱,再经半制备HPLC以甲醇-水(52∶48、1∶1)洗脱,得化合物16(6.8 mg)、17(7.1 mg)。

3 结构鉴定

化合物1:白色结晶(石油醚),ESI-MSm/z:427.7[M+H]+。1H-NMR (600 MHz,CDCl3)δ:2.39 (1H,m,H-4),0.88 (3H,s,H-23),0.72 (3H,s,H-24),0.87 (3H,s,H-25),0.95 (3H,s,H-26),1.05 (3H,s,H-27),1.18 (3H,s,H-28),1.00 (3H,s,H-29),1.01 (3H,s,H-30);13C-NMR (150 MHz,CDCl3)δ:22.4 (C-1),41.7 (C-2),213.5 (C-3),58.4 (C-4),42.3 (C-5),41.4 (C-6),18.4 (C-7),53.2 (C-8),37.6 (C-9),59.6 (C-10),35.8 (C-11),30.7 (C-12),39.8 (C-13),38.4 (C-14),32.2 (C-15),36.2 (C-16),30.2 (C-17),42.9 (C-18),35.5 (C-19),28.3 (C-20),32.9 (C-21),39.4 (C-22),7.0 (C-23),14.8 (C-24),18.1 (C-25),20.4 (C-26),18.8 (C-27),32.6 (C-28),35.2 (C-29),31.9 (C-30)。以上数据与文献[10]基本一致,故鉴定为无羁萜。

化合物2:白色结晶(石油醚),EI-MSm/z:427.7[M+H]+。1H-NMR (600 MHz,CDCl3)δ:5.26 (1H,d,J=4.2 Hz,H-12),3.25 (1H,m,H-3),1.07 (3H,d,J=6.2 Hz,H-29),1.07,1.05,1.02,0.96,0.95,0.84 (各3H,s,H-23,24,25,26,27,28),0.82 (3H,d,J=6.2 Hz,H-30);13C-NMR (150 MHz,CDCl3)δ:38.9 (C-1), 27.4 (C-2),79.2 (C-3),38.9 (C-4),55.3 (C-5),18.5 (C-6),33.1 (C-7),40.1 (C-8),47.8 (C-9),37.2 (C-10),23.4 (C-11),124.5 (C-12),139.7 (C-13),42.2 (C-14),26.8 (C-15),28.2 (C-16),33.9 (C-17),59.2 (C-18),39.7 (C-19),39.8 (C-20),31.4 (C-21),41.7 (C-22),28.3 (C-23),15.8 (C-24),15.8 (C-25),17.0 (C-26),23.5 (C-27),28.9 (C-28),17.6 (C-29),21.6 (C-30)。以上数据与文献[11]基本一致,故鉴定为α-香树脂醇。

化合物3:白色针晶(石油醚),EI-MSm/z:414.7[M]+。1H-NMR (600 MHz,CDCl3)δ:3.52 (1H,ddd,J=15.9,11.1,4.6 Hz,H-3),5.35 (1H,d,J=5.2 Hz,H-6),1.01 (3H,s,H-29),0.92 (3H,d,J=6.5 Hz,H-27),0.85 (3H,d,J=7.4 Hz,H-26),0.83 (3H,d,J=6.8 Hz,H-21),0.81 (3H,d,J=6.8 Hz,H-19),0.68 (3H,s,H-18);13C-NMR (150 MHz,CDCl3)δ:37.4 (C-1),19.2 (C-2),72.0 (C-3),42.4 (C-4),140.9 (C-5),121.9 (C-6),32.0 (C-7),32.1 (C-8),50.3 (C-9),36.7 (C-10), 21.2 (C-11),39.9 (C-12),42.5 (C-13),56.9 (C-14),24.5 (C-15),28.4 (C-16),56.2 (C-17),12.0 (C-18),18.9 (C-19),36.3 (C-20),31.8 (C-21),34.1 (C-22),26.2 (C-23),46.0 (C-24),29.3 (C-25),20.0 (C-26),19.6 (C-27),23.2 (C-28),12.1 (C-29)。以上数据与文献[12]基本一致,故鉴定为β-谷甾醇。

化合物4:白色结晶(石油醚),ESI-MSm/z:449.7[M+Na]+。1H-NMR (600 MHz,CDCl3)δ:4.56 (1H,dd,J=2.4,1.3 Hz,H-29a),4.68 (1H,d,J=2.4 Hz,H-29b),3.18 (1H,dd,J=7.5,4.0 Hz,H-3),2.33 (1H,m,H-19),0.76,0.88,0.89,0.92,0.94,0.98,1.68 (各3H,s,H-23,24,25,26,27,28,30);13C-NMR (150 MHz,CDCl3)δ:39.0 (C-1),27.5 (C-2),79.2 (C-3),39.9 (C-4),55.4 (C-5),18.5 (C-6),34.4 (C-7),41.8 (C-8),50.6 (C-9),37.3 (C-10),21.1 (C-11),25.9 (C-12),38.2 (C-13),43.0 (C-14),27.6 (C-15),35.7 (C-16),43.1 (C-17),48.4 (C-18),48.1 (C-19),151.1 (C-20),29.6 (C-21),41.0 (C-22),28.1 (C-23),15.6 (C-24),16.3 (C-25),16.1 (C-26),14.7 (C-27),18.1 (C-28),109.5 (C-29),19.5 (C-30)。以上数据与文献[13]基本一致,故鉴定为羽扇豆醇。

化合物5:白色结晶(石油醚),ESI-MSm/z:427.3[M+H]+。1H-NMR (600 MHz,CDCl3)δ:3.22 (1H,ddd,J=11.3,4.7,2.2 Hz,H-3),5.15 (1H,dt,J=34.2,3.7 Hz,H-13),1.13,1.07,0.96,0.95,0.94,0.91,0.83,0.80 (各3H,s,8×CH3);13C-NMR (150 MHz,CDCl3)δ:38.7 (C-1),26.8 (C-2),79.2 (C-3),38.9 (C-4),55.3 (C-5),18.5 (C-6),32.6 (C-7),41.7 (C-8),47.4 (C-9),37.1 (C-10),23.5 (C-11),121.9 (C-12),145.4 (C-13),41.9 (C-14),28.6 (C-15),26.3 (C-16),34.9 (C-17),47.8 (C-18),47.0 (C-19),31.4 (C-20),33.9 (C-21),37.0 (C-22),28.3 (C-23),15.7 (C-24),15.7 (C-25),17.0 (C-26),26.2 (C-27),27.1 (C-28),33.5 (C-29),23.7 (C-30)。以上数据与文献[14]基本一致,故鉴定为β-香树脂醇。

化合物6:淡黄色粉末,ESI-MSm/z:493.5[M+Na]+。1H-NMR (600 MHz,CDCl3)δ:4.03 (1H,d,J=2.2 Hz,H-1),2.97 (1H,dd,J=16.7,2.9 Hz,H-2b),2.68 (1H,d,J=16.7 Hz,H-2a),2.85 (1H,t,J=15.2 Hz,H-6b),2.46 (1H,dd,J=14.5,3.0 Hz,H-6a),2.23 (1H,dd,J=15.7,3.2 Hz,H-5),2.55 (1H,d,J=12.4 Hz,H-9),1.94~1.74 (2H,m,H-11),1.55~1.44 (2H,m,H-12),4.03 (1H,s,H-15),5.46 (1H,s,H-17),1.17 (3H,s,H-18),4.46 (2H,J=13.1 Hz,H-19),7.40 (1H,d,J=8.6 Hz,H-21),6.34 (1H,s,H-22),7.40 (1H,d,J=8.6 Hz,H-23),1.07,1.29,1.17 (各3H,s,H-24,25,26);13C-NMR (150 MHz,CDCl3)δ:79.5 (C-1),36.0 (C-2),169.5 (C-3),80.7 (C-4),60.9 (C-5),36.7 (C-6),206.5 (C-7),51.7 (C-8),48.5 (C-9),46.3 (C-10),19.3 (C-11),31.2 (C-12),38.3 (C-13),65.7 (C-14),54.2 (C-15),167.0 (C-16),78.2 (C-17),21.1 (C-18),66.0 (C-19),120.3 (C-20),143.6 (C-21),110.0 (C-22),141.5 (C-23),18.0 (C-24),30.5 (C-25),21.7 (C-26)。以上数据与文献[15]基本一致,故鉴定为柠檬苦素。

化合物7:白色粉末,ESI-MSm/z:427.6[M-H]-。1H-NMR (600 MHz,CDCl3)δ:3.72 (1H,m,H-3),0.93 (3H,s,H-23),0.96 (3H,s,H-24),0.86 (3H,d,J=0.9 Hz,H-25),1.00 (3H,s,H-26),0.98 (3H,s,H-27),0.99 (3H,s,H-28),0.94 (3H,s,H-29),1.17 (3H,s,H-30);13C-NMR (150 MHz,CDCl3)δ:15.9 (C-1),35.3 (C-2),72.9 (C-3),49.3 (C-4),37.2 (C-5),41.9 (C-6),17.7 (C-7),53.3 (C-8),38.5 (C-9),61.6 (C-10),35.7 (C-11),30.8 (C-12),38.0 (C-13),39.8 (C-14),32.6 (C-15),36.2 (C-16),30.2 (C-17),43.0 (C-18),35.5 (C-19),28.3 (C-20),32.9 (C-21),39.4 (C-22),11.8 (C-23),16.5 (C-24),18.4 (C-25),18.8 (C-26),20.4 (C-27),31.9 (C-28),35.3 (C-29),32.3 (C-30)。以上数据与文献[16]报道一致,故鉴定为表无羁萜醇。

化合物8:白色粉末,ESI-MSm/z:207.2[M+H]+。1H-NMR (600 MHz,CDCl3)δ:6.29 (1H,d,J=9.5 Hz,H-3),7.62 (1H,d,J=9.4 Hz,H-4),6.85 (1H,s,H-5),6.85 (1H,s,H-8),3.95,3.92 (各3H,s,6-OCH3,7-OCH3);13C-NMR (150 MHz,CDCl3)δ:161.6 (C-2),113.7 (C-3),143.4 (C-4),100.2 (C-5),153.0 (C-6),150.2 (C-7),108.1 (C-8),146.5 (C-9),111.6 (C-10),56.5 (6-OCH3),56.5 (7-OCH3)。以上数据与文献[17]基本一致,故鉴定为滨蒿内酯。

化合物9:无色油状物(二氯甲烷),ESI-MSm/z:193.2[M+H]+。1H-NMR (600 MHz,CDCl3)δ:6.27 (1H,d,J=9.5 Hz,H-3),7.60 (1H,d,J=9.4 Hz,H-4),6.85 (1H,s,H-5),3.96 (3H,s,6-OCH3),6.13 (1H,s,7-OH),6.92 (H,s,H-8);13C-NMR (150 MHz,CDCl3)δ:161.8 (C-2),113.8 (C-3),143.6 (C-4),111.9 (C-4a),103.6 (C-5),150.0 (C-6),144.3 (C-7),150.6 (C-8a),107.8 (C-8),56.8 (6-OCH3)。以上数据与文献[18]基本一致,故鉴定为东莨菪内酯。

化合物10:白色粉末,ESI-MSm/z:302.1[M+H]+。1H-NMR (600 MHz,CD3OD)δ:7.72 (1H,d,J=9.4 Hz,H-8),7.17 (1H,dd,J=7.7,1.6 Hz,H-6),7.13 (1H,t,J=7.8 Hz,H-7),6.42 (1H,s,H-2),3.95 (3H,s,3-OCH3),3.81 (3H,s,4-OCH3),3.76 (3H,s,10-NCH3);13C-NMR (150 MHz,CD3OD)δ:161.3 (C-1),94.7 (C-2),161.4 (C-3),131.4 (C-4),143.6 (C-4a),149.8 (C-5),121.0 (C-6),124.0 (C-7),116.8 (C-8),125.6 (C-8a),183.9 (C-9),107.2 (C-9a),143.6 (C-10a),56.8 (3-OCH3),60.7 (4-OCH3),47.0 (10-NCH3)。以上数据与文献[19]基本一致,故鉴定为citrusinine-Ι。

化合物11:黄色粉末,ESI-MSm/z:287.2[M+H]+。1H-NMR (600 MHz,CD3OD)δ:8.08 (2H,d,J=8.9 Hz,H-2′,6′),6.90 (2H,d,J=8.9 Hz,H-3′,5′),6.39 (1H,d,J=2.1 Hz,H-8),6.17 (1H,d,J=2.1 Hz,H-6);13C-NMR (150 MHz,CD3OD)δ:148.0 (C-2),137.1 (C-3),177.4 (C-4),162.5 (C-5),99.3 (C-6),165.6 (C-7),94.5 (C-8),158.3 (C-9),104.5 (C-10),123.7 (C-1′),130.7 (C-2′,6′),160.6 (C-4′),116.3 (C-3′,5′)。以上数据与文献[20]基本一致,故鉴定为山柰酚。

化合物12:黄色粉末,ESI-MSm/z:611.2[M+H]+。1H-NMR (600 MHz,CD3OD)δ:6.21 (1H,d,J=2.1 Hz,H-6),6.40 (1H,d,J=2.1 Hz,H-8),5.11 (1H,d,J=7.7 Hz,H-1″),6.87 (1H,d,J=8.4 Hz,H-5′),7.63 (1H,dd,J=8.4,2.2 Hz,H-6′),7.66 (1H,d,J=2.2 Hz,H-2′);13C-NMR (150 MHz,CD3OD)δ:158.5 (C-2),135.6 (C-3),179.4 (C-4),163.0 (C-5),99.9 (C-6),166.1 (C-7),94.8 (C-8),159.3 (C-9),105.6 (C-10),123.1 (C-1′),116.0 (C-2′),145.8 (C-3′),149.8 (C-4′),117.7 (C-5′),123.5 (C-6′),104.7 (C-1″),75.7 (C-2″),78.2 (C-3″),71.4 (C-4″),77.2 (C-5″),68.5 (C-6″),102.4 (C-1‴),72.2 (C-2‴),72.1 (C-3‴),73.9 (C-4‴),69.7 (C-5‴),17.9 (C-6‴)。以上数据与文献[21]基本一致,故鉴定为芦丁。

化合物13:黄色油状物(甲醇),ESI-MSm/z:275.3[M+Na]+。1H-NMR (600 MHz,CD3OD)δ:7.10 (2H,d,J=8.6 Hz,H-2,6),7.01 (1H,d,J=8.5 Hz,H-2′,6′),6.71 (2H,d,J=8.5 Hz,H-3,5),6.69 (2H,d,J=2.0 Hz,H-3′,5′),6.45 (1H,d,J=11.4 Hz,H-7),5.98 (1H,m,H-8′),5.61 (1H,dd,J=11.5,10.0 Hz,Ha-8),5.09 (1H,d,J=9.7 Hz,Ha-9′),5.07 (1H,d,J=1.4 Hz,Hb-9′),4.44 (1H,dd,J=9.7,6.2 Hz,H-7′);13C-NMR (150 MHz,CD3OD)δ:129.6 (C-1),130.9 (C-2,6),116.0 (C-3,5),157.7 (C-4),129.9 (C-7),132.4 (C-8),135.7 (C-1′),129.6 (C-2′,6′),116.3 (C-3′,5′),156.9 (C-4′),48.4 (C-7′),142.7 (C-8′),114.7 (C-9′)。以上数据与文献[22]基本一致,故鉴定为(+)-nyasol。

化合物14:黄色粉末,ESI-MSm/z:591.5[M-H]-。1H-NMR (600 MHz,DMSO-d6)δ:6.95 (1H,s,H-3),12.92 (1H,s,5-OH),6.38 (1H,d,J=2.0 Hz,H-6),6.80 (1H,d,J=2.0 Hz,H-8),8.04 (2H,d,J=9.0 Hz,H-2′,6′),7.13 (2H,d,J=9.0 Hz,H-3′,5′),3.86 (3H,s,-OCH3),Glu:5.24 (1H,d,J=7.5 Hz,H-1″),Rha:5.12 (1H,s,H-1‴),1.19 (3H,d,J=6.2 Hz,H-6‴);13C-NMR (150 MHz,DMSO-d6)δ:162.5 (C-2),103.9 (C-3),182.0 (C-4),157.0 (C-5),99.4 (C-6),163.8 (C-7),94.6 (C-8),161.1 (C-9),105.5 (C-10),122.7 (C-1′),128.4 (C-2′,6′),114.7 (C-3′,5′),162.6 (C-4′),55.6 (-OCH3),Glc:97.8 (C-1″),76.3 (C-2″),77.0 (C-3″),70.4 (C-4″),77.2 (C-5″),60.5 (C-6″),Rha:100.5 (C-1‴),70.5 (C-2‴),69.6 (C-3‴),71.9 (C-4‴),68.4 (C-5‴),18.1 (C-6‴)。以上数据与文献[23]基本一致,故鉴定为金柑苷。

化合物15:黄色粉末,ESI-MSm/z:593.1[M+H]+;1H-NMR (600 MHz,DMSO-d6)δ:6.88 (1H,s,H-3),6.27 (1H,s,H-6),13.10,10.90 (各1H,s,5-OH,7-OH),7.08 (2H,d,J=9.1 Hz,H-3′,5′),8.16 (2H,d,J=9.0 Hz,H-2′,6′),3.87 (3H,s,4′-OCH3),4.77 (1H,d,J=10.0 Hz,H-1″),4.04 (1H,m,H-2″),3.42(2H,m,H-3″,4″),5.23 (1H,d,J=5.0 Hz,3″-OH),5.06 (1H,d,J=5.4 Hz,4″-OH),3.24 (1H,m,H-5″),3.76 (1H,ddd,J=11.8,5.9,1.7 Hz,H-6″),4.66 (1H,t,J=5.7 Hz,6″-OH),4.97 (1H,d,J=1.2 Hz,H-1‴),3.57 (1H,m,H-2‴),3.08 (1H,ddd,J=9.1,5.8,3.1 Hz,H-3‴),2.91 (1H,td,J=9.4,4.1 Hz,H-4‴),2.11 (1H,m,H-5‴),4.30 (1H,d,J=5.8 Hz,3‴-OH),4.42 (2H,dd,J=5.2,4.2 Hz,2‴,4‴-OH),0.47 (3H,d,J=6.1 Hz,6‴-CH3);13C-NMR (150 MHz,DMSO-d6)δ:163.6 (C-2),103.2 (C-3),182.1 (C-4),160.7 (C-5),98.3 (C-6),162.4 (C-7),104.5 (C-8),155.8 (C-9),104.3 (C-10),123.2 (C-1′),128.9 (C-2′,6′),114.5 (C-3′,5′),162.4 (C-4′),55.6 (4′-OCH3),71.7 (C-1″),75.0 (C-2″),79.9 (C-3″),70.6 (C-4″),81.8 (C-5″),61.1 (C-6″),100.3 (C-1‴),70.4 (C-2‴),70.2 (C-3‴),71.5 (C-4‴),68.2 (C-5‴),17.7 (C-6‴)。以上数据与文献[24]基本一致,故鉴定为acacetin-8-C-neohesperidoside。

化合物16:白色粉末,ESI-MSm/z:579.2[M-H]-;1H-NMR (600 MHz,CD3OD)δ:6.67 (2H,s,H-2,6),6.73 (2H,s,H-2′,6′),4.78 (1H,d,J=4.1 Hz,H-7),4.73 (1H,d,J=4.5 Hz,H-7′),3.47 (m,1H,H-9β),4.24 (1H,m,H-9′β),3.93 (2H,dd,H-9α,9′α),3.14 (2H,m,H-8,8′),其中4.86 (1H,d,J=1.5 Hz,H-1″)为葡萄糖上其他质子信号,3.87 (6H,s)和3.85 (6H,s)为苯环上3,5,3′,5′上两两重叠的4个甲氧基质子;13C-NMR (150 MHz,CD3OD)δ:139.6 (C-1),104.8 (C-2,6),154.4 (C-3,5),135.6 (C-4),87.2 (C-7),55.5 (C-8),72.9 (C-9),133.1 (C-1′),105.3 (C-2′,6′),149.3 (C-3′,5′),136.2 (C-4′),87.6 (C-7′),55.7 (C-8′),72.9 (C-9′), 104.5 (C-1″),75.7 (C-2″),77.8 (C-3″),71.3 (C-4″),78.3 (C-5″),62.6 (C-6″),55.7 (3,5-OCH3),56.8 (3-′OCH3),57.1 (5′-OCH3)。以上数据与文献[25]基本一致,故鉴定为syringaresinol 4′-O-β-D-glucopyranoside。

化合物17:白色粉末,ESI-MSm/z:339.2[M+Na]+。1H-NMR (600 MHz,CD3OD)δ:7.69 (1H,d,J=2.3 Hz,H-3),7.04 (1H,d,J=9.2 Hz,H-5),7.70 (1H,s,H-6),4.60 (2H,s,H-7),3.93 (3H,s,H-8),5.18 (1H,d,J=7.7 Hz,H-1′),3.74~3.39 (6H,m,H-2′,3′,4′,5′,6′);13C-NMR (150 MHz,CD3OD)δ:135.7 (C-1),112.0 (C-2),151.4 (C-3),147.1 (C-4),117.2 (C-5),122.9 (C-6),65.1 (C-7),56.4 (C-8),104.7 (C-1′),75.7 (C-2′),78.2 (C-3′),71.2 (C-4′),78.4 (C-5′),62.6 (C-6′)。以上数据与文献[26]基本一致,故鉴定为vanilloloside。

4 结论

本研究从金橘成熟果实的石油醚、二氯甲烷和乙酸乙酯部位分离鉴定得到17个化合物,包括5个萜类(化合物1~2、4~5、7)、2个香豆素类(化合物8~9)、1个甾醇类(化合物3)、4个黄酮类(化合物11~12、14~15)、2个木脂素类(化合物13、16)、1个柠檬苦素类(化合物6)、1个生物碱类(化合物10)、1个糖苷类(化合物17)。查阅文献发现金橘黄酮类成分具有显著的降血脂作用。因此,金橘的化学成分及其药理作用值得深入研究,从而更好地促进金橘的开发利用。

猜你喜欢

金橘二氯甲烷石油醚
久咳不愈喝金橘茶
5种石油醚前处理对不同植物样品黄酮含量测定的影响
复序橐吾石油醚提取物的化学成分分析
金橘“打擂”
金橘连皮生吃好
气相色谱—质谱联用法测定塑料以及塑料制品中多环芳香烃的研究
二氯甲烷/石蜡油回收装置技术方案优化
菊芋叶片提取物对辣椒疫霉菌的抑菌效果及盆栽验证试验
融安:金橘推介会
狼毒大戟石油醚提取物和乙酸乙酯提取物的半数致死量测定