引用本文	doi: 10.1016/S1674-6384(14)60025-3

Li-feng Han, Kaunda Joseph Sakah, Li-li Liu, Agyemang Kojo, Tao Wang, Yi Zhang. Saponins from Roots of Panax notoginseng[J]. Chinese Herbal Medicines (CHM) , 2014, 6(2): 159-163. 复制到剪切板

Saponins from Roots of Panax notoginseng

Li-feng Han¹, Kaunda Joseph Sakah², Li-li Liu², Agyemang Kojo², Tao Wang^1,2, Yi Zhang^1,2

1. Institute of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 300193, China
2. Tianjin State Key Laboratory of ModernChinese Medicine, Tianjin 300193, China

Received: August 13, 2013; Revised: October 10, 2013; Accepted: January 7, 2014; Available online: March 24, 2014

Corresponding author: Zhang Y Address: Institute of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, 312 Anshanxi Road, Nankai District, Tianjin 300193, China Email: zhwwxzh@hotmail.com Tel/Fax: +86-22-5959-6163

Abstract: Objective To study the chemical constituents in the dried roots of Panax notoginseng. MethodsThe constituents were isolated and purified with chromatographic methods. Their structures were elucidated by spectroscopic methods (1D, 2D NMR, UV, IR, [α]D, and HRESI-TOF-MS) and chemical analyses. Results Twenty saponins including 20(S)-ginsenoside Rh1(1), 6-O-β-D-(6′-acetyl)-glucopyranosyl-24-ene-dammar-3β, 6α,12β,20S-tetraol (2), ginseno- side Rf (3), notoginsenoside R2(4), ginsenoside Rg2(5), ginsenoside Rg1(6), notoginsenoside Rt (7), koryoginsenoside R1(8), 6-O-(β-Dglucopyranosyl)-20-O-(β-D-xylopyranosyl)-3β,6α,12β,20(S)-tetrahydroxy-dammar- 24-ene (9), pseudoginsenoside Rt3(10), notoginsenoside R1(11), ginsenoside Re (12), notoginsenoside N (13), ginsenoside F1(14), ginsenoside U (15), ginsenoside Rk3 (16), 3β,12β-dihydroxydammar-(E)-20(22),24-diene-6-O-β-D-xylopyranosyl-(1→2)-β-D- glucopyranoside (17), ginsenoside Rh4(18), pseudoginsenoside Rt5(19), and vinaginsenoside R22(20) were obtained. Conclusion Compounds 2, 19, and 20are isolated from this species for the first time. The ¹H-NMR data of compound 19and ¹H-NMR and ¹³C-NMR data of compound 20are first reported. Meanwhile, the NMR data of β-D-xylopyranosyl group in compound 9is corrected.

Key words: Araliaceae Panax notoginseng pseudoginsenoside Rt₅ saponins vinaginsenoside R₂₂

1. Introdution

Panax notoginseng(Burk.)F. H. Chen(Araliaceae)is a Chinese medicinal herb，distributed throughout the southwest of China，Burma， and Nepal. It was first used by national minorities in southwest China and widely accepted during the Ming Dynasty. It has been reported to have antihypertensive，antithrombotic，anti-atherosclerotic， and neuroprotective activities(Ng，2006; Liu et al，2011). The dried roots of P. notoginseng are used for promoting blood circulation. There are various chemical constituents in the dried roots of P. notoginseng，including ginsenosides，notoginsenosides，flavonoids，volatile oils，amino acids， and polysaccharide(Gao and Zhe， 2010; Cao et al，2013). In our studies on the constituents from this plant by using chromatographies such as silica gel，ODS， and HPLC，20 known saponins were identified by the chemical and physical methods，especially spectral analyse. Among them，compounds 2，19， and 20 were isolated from this species for the first time， and the NMR data of compound 20 were first reported. In this paper，the NMR data of all the compounds were determined by 1D and 2D NMR spectra including ¹H-¹H COSY，HSQC，HMBC， and HSQC-TOCSY，which would make up the lack of accuracy of data assignment elucidated only by ¹H-NMR and ¹³C-NMR experiments. On the other h and ，the data of the chemical constituents in the roots of P. notoginseng were supplemented，which could provide the basic data for the development and utilization of P. notoginseng.

2. Materials and methods 2.1 General

Optical rotations were measured on a Rudolph Autopol^® IV Automatic Polarimeter(l = 50 mm)，IR data were recorded on a Varian 640-IR FT-IR Spectrophotometer. ¹H-NMR and ¹³C-NMR spectra were determined on a Bruker 500 MHz NMR Spectrometer(Avance III 500MR)at 500 MHz for ¹H-NMR and 125 MHz for ¹³C-NMR with tetramethylsilane(TMS)as internal st and ard. Positive-ion HRESI-TOF-MS was recorded on an Agilent Technologies 6520 Accurate- Mass Q-Tof LC/MS Spectrometer.

A highly-porous synthetic resin(D101)was purchased from Haiguang Chemical Co.，Ltd.(Tianjin，China). Silica gel column chromatography(CC)was obtained from Qingdao Haiyang Chemical Co.，Ltd.，(48−75 mm，Qingdao，China). HPLC was performed on ODS(Cosmosil 5C18−MS−II，Tokyo，Japan; F = 20 mm，L = 250 mm，flow rate: 9.0 mL/min)， and the eluate was monitored with a UV Detector(Shimadzu RID−10A UV-Vis，Japan). Pre-coated TLC plates with silica gel GF₂₅₄(Tianjin Silida Technology Co.，Ltd.，China)were used to detect the purity of the isolate achieved by spraying with 10% aqueous H₂SO₄-EtOH，followed by heating.

2.2 Plant materials

The dried rootsof Panax notoginseng(Burk)，F. H. Chen were collected from Wenshan，Yunnanprovince，China and identified by Dr. Tian-xiang Li. The voucher specimen(No. 20120505)was deposited at Tianjin University of Traditional Chinese Medicine.

2.3 Extraction and isolation

The dried roots of P.notoginseng(5.0 kg)were refluxed with 70% ethanol-water twice. Evaporation of the solvent under reduced pressure provided a 70% ethanol-water extract(480.2 g). The residue was dissolved in H₂O and subjected to D101 CC [EtOH-H₂O(0:100®50:50®100:0)to afford EtOH eluent. The EtOH eluent(120.0 g)was subjected to silica gel CC [CHCl₃→CHCl₃-MeOH(100:3→100:7)→CHCl₃-MeOH- H₂O(10:3:1→7:3:1→6:4:1，lower layer)] to give 12 fractions(Frs. 1—12). Fr. 7(8.0 g)was subjected to silica gel CC and PHPLC to yield 20(S)-ginsenoside Rh₁(1，54.9 mg)，6-O-b- D-(6′-acetyl)-glucopyranosyl-24-en-dammar-3b，6a，12b，20S- tetraol(2，36.9 mg)，ginsenosides F₁(14，75.5 mg)，Rk₃(16，50.2 mg)，Rh₄(18，438.6 mg)， and pseudoginsenoside Rt₅(19，4.4 mg). Fr. 8(4.0 g)was separated by ODS CC and PHPLC CC，repeatedly. And notoginsenoside R₂(4，225.3 mg)，notoginsenoside Rt(7，40.3 mg)，koryoginsenoside R₁(8，4.4 mg)，6-O-(b-D-glucopyranosyl)-20-O-(b-D-xylopyranosyl)-3b，6α，12b，20(S)-tetrahydroxydammar-24-ene(9，20.0 mg)，pseudoginsenoside Rt₃(10，7.6 mg)， and 3b，12b-dihydroxy- dammar-(E)-20(22)，24-diene-6-O-b-D-xylopyranosyl-(1→2)-b-D-glucopyranoside(17， 38.9 mg)were produced. Fr. 9(16.0 g)was subjected to ODS CC and further purified by PHPLC to give notoginsenoside R₂(4，452.6 mg)，ginsenoside Rg₂(5，426.1 mg). ginsenoside Rg₁(6，12.56 g)， and 6-O-(b-D-glucopyranosyl)-20-O-(b-D-xylopyranosyl)-3b，6α，12b，20(S)-tetrahydroxydammar-24-ene(9，19.0 mg). Fr. 10(3.6 g)was subjected to ODS CC，silica gel CC， and PHPLC to give ginsenosides Rf(3， 10.7 mg)，Rg₁(6，22.0 mg)，Re(12，108.1 mg)，U(15，30.7 mg)，notoginsenosides R₁(11，992.2 mg) and N(13，23.8 mg)，3b，6a-20(S)-6，20- bis(b-D-glucopyranosyloxy)-3-hydroxy dammar-24-en-12-one(10，9.3 mg)， and vinaginsenoside R₂₂(20，23.9 mg).

3. Results and discussion

Compound 2: white powder. Positive-ion HRESI-TOF- MS m/z 703.4409 [M + Na]⁺(calcd for C₃₈H₆₄O₁₀Na 703.4392). ¹H-NMR(C₅D₅N，500 MHz)d: 0.95(3H，s，H₃-30)，1.06(3H，s，H₃-19)，1.25(3H，s，H₃-18)，1.42(3H，s，H₃-21)，1.55(3H，s，H₃-29)，1.64(3H，s，H₃-27)，1.66(3H，s，H₃-26)，2.07(3H，s，H₃-28)，3.51(1H，dd，J = 4.5，11.5 Hz，H-3)，3.93(1H，m，H-12)，4.40(1H，ddd，J = 3.0，10.5，10.5 Hz，H-6)，5.03(1H，d，J = 8.0 Hz，H-1′)，5.32(1H，t，J = 7.0 Hz，H-24). Compound 2 was identified as 6-O-b-D-(6′-acetyl)- glucopyranosyl-24-ene-dammar-3b，6a，12b，20S-tetraol bycomparison of the physical，¹H-NMR and ¹³C-NMR data(Table 1)with the reported data(Jia and Wang， 2009).

Table 1 ¹³C-NMR(125 MHz)data of compounds 1—11

Position	1	2	3	4	5	6	7	8	9	10	11
1	39.4	39.4	39.4	39.4	39.4	39.3	39.5	39.5	39.5	39.5	39.4
2	27.9	27.9	28.7	27.7	27.7	27.7	27.9	27.9	28.0	27.9	27.7
3	78.6	78.6	78.7	78.7	78.4	78.6	78.7	78.7	78.7	78.7	78.9
4	40.4	40.3	40.2	40.2	40.0	40.4	40.3	40.3	40.4	40.3	40.2
5	61.5	61.4	61.4	61.3	60.8	61.3	61.4	61.5	61.4	61.4	61.3
6	80.1	79.7	79.9	79.4	74.4	80.0	79.8	80.1	80.1	79.7	79.5
7	45.2	45.5	45.1	45.0	46.0	45.0	45.5	45.6	45.1	45.2	44.9
8	41.1	41.2	41.2	41.1	41.1	41.0	41.3	41.3	41.1	41.2	41.1
9	50.2	50.2	50.1	50.1	49.8	49.9	50.0	50.0	50.0	50.0	49.9
10	39.7	39.7	39.7	39.6	39.6	39.5	39.7	39.8	39.7	39.7	39.6
11	32.1	32.1	32.1	32.0	32.0	30.7	30.9	31.0	31.0	31.0	30.9
12	71.0	71.0	71.0	71.0	71.0	70.3	70.3	70.2	70.2	70.2	70.3
13	48.3	48.4	48.3	48.2	48.2	48.9	49.2	49.2	49.2	49.3	49.1
14	51.7	51.7	51.7	51.6	51.7	51.3	51.4	51.4	51.4	51.4	51.4
15	31.4	31.6	31.2	31.2	31.3	30.6	30.9	31.0	30.7	30.8	30.7
16	26.8	26.8	26.8	26.8	26.8	26.5	26.6	26.7	26.6	26.6	26.6
17	54.8	54.8	54.8	54.7	54.7	51.7	51.6	51.7	51.7	51.5	51.6
18	17.4	17.4	17.4	17.3	17.2	17.4	17.6	17.7	17.6	17.6	17.5
19	17.7	17.7	17.6	17.6	17.6	17.6	17.6	17.6	17.6	17.6	17.5
20	73.0	73.0	73.0	73.0	73.0	83.3	83.3	83.3	83.0	83.3	83.3
21	27.1	26.8	27.0	27.0	27.0	22.4	22.4	22.4	22.2	22.3	22.4
22	35.8	35.9	35.8	35.8	35.8	35.9	36.1	36.1	36.0	36.2	36.0
23	23.0	23.0	23.0	23.0	23.0	23.2	23.3	23.2	23.2	23.2	23.3
24	126.4	126.3	126.3	126.3	126.3	125.8	126.0	126.0	125.9	126.0	125.9
25	130.8	130.8	130.8	130.8	130.8	131.0	131.0	131.0	131.1	131.0	131.0
26	25.8	25.8	25.8	25.8	25.8	25.8	25.8	25.8	25.8	25.8	25.8
27	17.7	17.7	17.7	17.7	17.7	17.8	17.8	17.8	17.8	17.8	17.8
28	31.7	31.4	32.1	31.7	32.2	31.6	31.6	31.6	31.8	31.6	31.7
29	16.4	16.5	16.8	16.8	17.6	16.3	16.5	16.5	16.4	16.5	16.7
30	16.8	17.0	16.8	16.7	16.9	17.0	17.4	17.3	17.2	17.4	17.1
1′	106.1	105.9	103.9	103.5	101.8	105.8	105.9	106.1	106.0	106.7	103.5
2′	75.5	75.4	79.6	79.8	78.6	75.3	75.4	75.4	75.5	75.3	79.8
3′	79.6	79.2	79.9	80.1	79.4	79.4	79.2	79.2	79.7	79.4	80.0
4′	71.9	71.4	72.3	71.7	72.6	71.7	71.5	71.5	71.9	71.2	71.7
5′	78.1	75.1	77.9	78.0	78.4	77.9	75.1	75.2	78.1	67.1	78.0
6′	63.1	65.2	63.4	62.8	63.1	62.9	65.2	65.1	63.1		62.8
1′′		170.9	103.8	104.7	101.9	98.1	98.3	98.3	98.9	98.3	104.7
2′′		21.0	76.0	75.8	72.4	75.0	75.2	75.2	75.0	75.2	75.8
3′′			78.4	78.8	72.3	78.9	79.3	79.3	79.2	79.2	78.7
4′′			71.7	71.2	74.3	71.4	71.6	71.7	71.0	71.7	71.2
5′′			78.1	67.2	69.5	78.1	78.3	78.3	67.1	78.3	67.2
6′′			62.9		18.7	62.6	62.9	62.9		63.0
1′′′											98.2
2′′′											75.1
3′′′											79.2
4′′′											71.5
5′′′											78.2
6′′′											62.9
CH₃CO							170.9
CH₃CO							21.0

Table 1 ¹³C-NMR(125 MHz)data of compounds 1—11

Compound 9: white powder. Positive-ion HRESI-TOF- MS m/z 793.4734 [M + Na]⁺(calcd for C₄₁H₇₀O₁₃Na 793.4709). ¹H-NMR(C₅D₅N，500 MHz)d: 0.81(3H，s，H₃-30)，1.03(3H，s，H₃-19)，1.17(3H，s，H₃-18)，1.52(3H，s，H₃-26)，1.60(3H，s，H₃-21)，1.63(3H，s，H₃-29)，1.64(3H，s，H₃-27)，2.06(3H，s，H₃-28)，3.51(1H，dd，J = 5.0，11.5 Hz，H-3)，4.12(1H，m，H-12)，4.42(1H，ddd，J = 2.5，10.5，10.5，H-6)，5.01(1H，d，J = 8.0 Hz，H-1′)，5.03(1H，d，J = 8.0 Hz，H-1″)，5.29(1H，t，J = 7.0 Hz，H-24). Compound 9 was identified as 6-O-(b-D-glucopyranosyl)-20-O-(b-D-xylopyranosyl)-3b，6α，12b，20(S)-tetrahydroxydammar-24-ene(Liu et al，2011)，but the ¹³C-NMR data(Table 1)of b-D-xylopyranosyl in the compound should be corrected.

Compound 19: white powder. Positive-ion HRESI-TOF- MS m/z 677.4238 [M + Na]⁺(calcd for C₃₆H₆₂O₁₀Na 677.4235). ¹H-NMR(C₅D₅N，500 MHz)d: 0.77(3H，s，H₃-30)，1.02(3H，s，H₃-19)，1.20(3H，s，H₃-18)，1.25(6H，s，H₃-26 and 27)，1.46(3H，s，H₃-21)，1.60(3H，s，H₃-29)，2.07(3H，s，H₃-28)，3.52(1H，dd，J = 4.0，11.5 Hz，H-3)，3.70(1H，ddd，J = 5.0，10.5，10.5 Hz，H-12)，4.45(1H，ddd，J = 3.0，10.5，10.5 Hz，H-6)，5.03(1H，d，J = 8.0 Hz，H-1′)，4.10(1H，t，J = 7.5 Hz，H-24); ¹H-NMR(CD₃OD，500 MHz)d: 0.98(3H，s，H₃-30)，0.96(3H，s，H₃-19)，0.99(3H，s，H₃-29)，1.10(3H，s，H₃-18)，1.27(3H s，H₃-21)，1.22(3H，s，H₃-26)，1.13(3H，s，H₃-27)，1.32(3H，s，H₃-28)，3.11(1H，dd，J = 5.0，12.0 Hz，H-3)，3.48(1H，ddd，J = 5.0，11.0，11.0 Hz，H-12)，3.89(1H，t，J = 7.5 Hz，H-24)，4.10(1H，ddd，J = 3.0，10.5，10.5 Hz，H-6)，4.34(1H，d，J = 8.0 Hz，H-1′). Compound 19 was identified as pseudoginsenoside Rt₅ by comparison of the physical， and ¹³C-NMR data(Table 2)with the reported data(Tanaka et al，1985)， and the ¹H-NMR data reported here were determined by 1D and 2D NMR spectra.

Table 2 ¹³C-NMR(125 MHz)data of compounds 12—20

Position	12	13	14^a	14	15	16	17	18	19^a	19	20
1	39.4	39.4	40.1	39.4	39.4	39.5	39.7	39.5	40.3	39.6	39.5
2	27.8	28.0	27.7	28.1	28.1	27.9	27.8	27.9	27.7	28.0	28.0
3	78.4	78.6	79.5	78.5	78.5	78.6	78.8	78.6	79.9	78.6	78.9
4	40.0	40.4	40.5	40.3	40.3	40.4	40.2	40.4	40.6	40.4	40.4
5	60.8	61.4	62.1	61.7	61.7	61.5	61.5	61.4	62.0	61.6	61.4
6	74.6	80.3	68.8	67.7	67.7	80.0	79.4	80.0	80.9	80.1	80.2
7	46.0	44.9	47.2	47.4	47.4	45.3	45.1	45.3	45.3	45.1	45.1
8	41.2	41.1	42.0	41.2	41.2	41.3	41.3	41.3	41.9	41.0	41.1
9	49.6	50.0	50.1	49.9	49.9	50.7	50.5	50.6	51.4	50.6	49.9
10	39.7	39.7	40.1	39.3	39.4	39.5	39.7	39.7	40.4	39.6	39.7
11	31.0	31.0	30.9	30.8	30.8	32.7	32.2	32.3	32.9	32.4	31.2
12	70.2	70.2	71.6	70.2	70.2	72.4	72.5	72.6	72.4	71.2	70.4
13	49.1	49.2	49.3	49.1	49.1	52.1	50.7	50.7	49.9	48.4	48.9
14	51.4	51.5	52.3	51.3	51.3	51.1	50.9	50.8	53.2	52.2	51.5
15	30.8	30.6	31.6	30.8	30.7	32.5	32.6	32.6	33.6	31.7	30.9
16	26.7	26.6	27.2	26.6	26.6	30.7	28.8	28.8	29.7	25.5	26.8
17	51.7	51.4	53.1	51.6	51.6	48.3	50.4	50.4	49.1	49.5	52.7
18	17.3	17.6	17.7	17.6	17.6	17.4	17.3	17.4	17.4	17.9	17.4
19	17.5	17.6	17.7	17.4	17.4	17.8	17.7	17.7	18.5	17.1	17.6
20	83.3	83.3	84.8	83.2	83.4	155.4	140.1	140.1	87.9	86.7	83.4
21	22.3	22.3	22.8	22.4	22.3	108.2	13.1	13.1	27.1	27.0	22.7
22	36.0	36.2	36.7	36.1	36.2	33.7	123.5	123.5	32.2	32.8	33.8
23	23.2	23.2	24.2	23.2	23.2	27.1	27.4	27.4	26.1	28.8	27.1
24	126.0	126.0	125.8	125.9	126.0	125.3	123.8	123.8	86.0	85.6	79.8
25	130.9	130.9	132.2	130.9	131.1	131.2	131.2	131.2	71.9	70.3	72.8
26	25.8	25.8	25.9	25.8	25.8	25.8	25.7	25.7	26.7	27.5	26.7
27	17.8	17.8	18.0	17.8	18.0	17.8	17.7	17.7	26.8	27.7	26.0
28	32.2	31.8	31.5	32.0	32.0	31.7	31.7	31.7	31.3	31.7	31.8
29	17.6	16.3	16.1	16.5	16.5	16.3	16.7	16.4	16.1	16.3	16.4
30	17.3	17.2	17.3	17.4	17.4	16.8	16.8	16.8	18.1	18.0	17.0
1′	101.9	105.7	98.2	98.2	98.0	106.0	103.5	106.0	105.6	106.0	106.0
2′	78.6	74.9	75.3	75.1	74.8	75.4	80.2	75.4	75.5	75.5	75.5
3′	79.4	78.9	78.2	79.2	79.2	79.6	79.8	79.6	79.1	79.7	79.7
4′	72.6	81.3	71.1	71.6	71.5	71.8	71.7	71.8	71.8	71.9	71.9
5′	78.3	76.5	77.9	78.2	77.0	78.1	78.0	78.0	77.7	78.2	78.1
6′	63.1	62.2	62.5	62.8	70.2	63.1	62.9	63.1	63.0	63.2	63.4
1′′	101.9	103.1			105.3		104.8				98.3
2′′	72.4	74.5			75.2		75.8				75.5
3′′	72.3	75.5			78.3		78.7				78.6
4′′	74.2	72.0			71.7		71.2				78.7
5′′	69.5	75.3			78.3		67.2				63.1
6′′	18.7	62.8			62.8
1′′′	98.3	98.2
2′′′	75.2	75.1
3′′′	79.2	79.4
4′′′	71.6	71.7
5′′′	78.2	78.3
6′′′	62.9	62.9

Table 2 ¹³C-NMR(125 MHz)data of compounds 12—20

Compound 20: white powder. Positive-ion HRESI-TOF- MS(m/z 857.4850 [M + Na]⁺，calcd for C₄₂H₇₄O₁₆Na 857.4869). The ¹H-NMR(C₅D₅N，500 MHz)spectrum of compound 20 showed the signals assignable to eight methyls [d 0.73，1.02，1.10，1.55，1.56，1.57，1.60，2.06(3H each，all s，H₃-30，19，18，27，26，21，29，28)，four methines bearing oxygen function [d 3.51(1H，dd，J =5.0，11.0 Hz，H-3)，3.74(1H，dd，J = 3.0，8.0 Hz，H-24)，3.92(1H，m，H-12)，4.40(1H，ddd，J = 3.0，10.5，10.5 Hz，H-6)]，together with two anomeric proton signals shown at d 5.00(1H，d，J = 8.0 Hz，H-1′)，5.22(1H，d，J = 7.5 Hz，H-1″). The ¹³C-NMR spectrum displayed 42 carbons including 30 carbons for the aglycon，12 carbons for two b-D-glucopyranosyl moieties. ¹H-NMR and ¹³C-NMR spectra suggested that compound 20 was a dammarane-type triterpene saponin derivative. The chemical shift of d 61.4(C-5)indicated that compound 20 was a protopanaxatriol type saponin [d 56 and 61(C-5)for protopanaxadiol and protopanaxatriol type saponin，respectively]. The ¹H-¹H COSY experiment on compound 20 indicated the presence of partial structure written in bold lines. And in HMBC experiment，long-range correlations were observed between the following protons and carbons: H₃-18 and C-7-9，14; H₃-19 and C-1，5，9，10; H₃-21 and C-17，20，22; H₃-26 and C-24，25，27; H₃-27 and C-24-26; H₃-28 and C-3-5，29; H₃-29 and C-3-5，28; H₃-30 and C-8，13-15; H-1′ and C-6; H-1″ and C-20. The stereochemistry of C-20 in compound 20 was clarified to be S by comparing the chemical shifts of 20–22-carbons of it with those of compounds 12–15. The absolute configuration of C-24(d 79.8)was identified as 24R on comparison with the chemical shift values of cyclounifolioside C(24R，C-24: d 80.3) and cyclocantogenin(24S，C-24: d 77.0)(Zhao et al，2008). On the basis of the above mentioned evidence，compound 20 was elucidated to be vinaginsenoside R₂₂(Duc et al，1999)，which was reported to presence in vietnamese ginseng by Duc et al，but there was no NMR data were given. In this paper，the NMR data were reported for the first time. The ¹H-NMR(C₅D₅N，500 MHz)d: 0.73(3H，s，H₃-30)，1.02(3H，s，H₃-19)，1.10(3H，s，H₃-18)，1.55(3H，s，H₃-27)，1.56(3H，s，H₃-26)，1.57(3H，s，H₃-21)，1.60(3H，s，H₃-29)，2.06(3H，s，H₃-28)，3.51(1H，dd，J = 5.0，11.0 Hz，H-3)，3.74(1H，dd，J = 3.0，8.0 Hz，H-24)，3.92(1H，m，H-12)，4.40(1H，ddd，J = 3.0，10.5，10.5 Hz，H-6)，5.00(1H，d，J = 8.0 Hz，H-1′)，5.22(1H，d，J = 7.5 Hz，H-1″).

The structures of 20(S)-ginsenoside Rh₁(1)(Li et al，2010)，ginsenoside Rf(3)(Sun et al，2009)，notoginsenoside R₂(4)(Dou et al，2003)，ginsenoside Rg₂(5)(Sun et al，2009)，ginsenoside Rg₁(6)(Teng et al，2002)，notoginsenoside Rt(7)(Li et al，2007)，koryoginsenoside R₁(8)(Kim et al，1995)，pseudoginsenoside Rt₃(10)(Liu et al，2011)，notoginsenoside R₁(11)(Zeng et al，2007)，ginsenoside Re(12)(Zeng et al，2007)，notoginsenoside N(13)(Yoshikawa et al，2001)，ginsenoside F₁(14)(Guo，Fi， and Dou，2006)，ginsenoside U(15)(Sun et al，2005)，ginsenoside Rk₃(16)(Park et al，2002)，3b，12b-dihydroxydammar-(E)-20(22)，24-diene-6-O-b-D-xylopyranosyl-(1→2)-b-D-glucopyranoside(17)(Chen et al，2007)， and ginsenoside Rh₄(18)(Zeng et al，2007)were identified by comparison of the physical，¹H-NMR， and ¹³C-NMR data(Tables 1 and 2)with the reported data，respectively.

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Chinese Herbal Medicines (CHM) 2014, Vol. 6 Issue (2): 159-163	0	PDF