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金铁锁地上部分化学成分研究

2014-02-10沈云亨

天然产物研究与开发 2014年5期
关键词:第二军医大学铁锁药学院

文 波,李 博,沈云亨*

1福建中医药大学 药学院,福州 350108;2中国人民解放军第二军医大学 药学院 天然药物化学教研室,上海 200433

Introduction

Psammosilene tunicoides W.C.Wu et C.Y.Wu is the only species in the genus Psammosilene growing in Sichuan,Yunnan,Tibet and Guizhou provinces of China.As a Yunnan folk medicine,it has been long used for stopping bleeding,relieving pain and promoting blood circulation[1].The crude saponins obtained from this plant exhibited relieving pain,anti-inflammation and regulating the immune function[2].In searching for bioactive constituents from this plant,several kinds of compounds have been reported from the roots of this plant,including triterpenoid saponins,cyclic peptides,and carboline alkaloids[3].To our best knowledge,however,the chemical investigation of the aerial parts of P.tunicoides had not yet been investigated.In this study,the isolation and structural elucidation of 11 known compounds from the ethanol extract of the aerial parts of P.tunicoides are presented.All compounds were isolated from P.tunicoides for the first time.

Experimental

General experimental procedures

NMR spectral data were recorded on Bruker Avance 500 and 600 MHz NMR spectrometers.Chemical shifts were recorded as δ values.The ESI-MS data were acquired on an Agilent-1100-LC/MSD-Trap-XCT mass spectrometer (Agilent,USA).TLC was done on precoated silica gel 254 plates (Huanghai,0.15-0.20 mm thick for TLC analysis,0.40-0.50 mm thick for preparative TLC).Column chromatography was performed using silica gel (200-300 mesh and 100-200 mesh)(Huiyou Silica Gel Development Co.Ltd,Yantai,P.R.China),RP-C18(GHODS AQ 12S50,Japan)and Sephadex LH-20 (GE Healthcare Bio-Science AB,Sweden).

Plant materials

The aerial parts of P.tunicoides were collected in Lijiang,Yunnan province,China,in July 2006 and identified by Prof.Li-Shan Xie,Kunming Institute of Botany,the Chinese Academy of Sciences,China.The voucher specimen (No.2006071015)was deposited with the Herbarium of the School of Pharmacy,Second Military Medical University.

Extraction and isolation

The aerial parts of P.tunicoides (13 kg)was macerated and repeatedly extracted with 80% ethanol.The combined extracts were subjected to silica gel column chromatography eluted with petroleum ether,CH2Cl2,EtOAc,and MeOH,and resulting in four fractions,respectively.The MeOH extract (813.5 g)was separated by silica gel column chromatography eluted with EtOAc-MeOH (20∶1-1∶1)and re-crystallizated to afford compound 1 (115.3 mg).The EtOAc extract (88 g)was separated into seven fractions (A-E)by CC(ODS,MeOH∶H2O 1 ∶9-1 ∶0).Fr.B (22.5 g)was separated over silica gel column chromatography (petroleum ether:EtOAc:MeOH 3∶3∶0-3∶3∶2;then Sephadex LH-20 column chromatography (MeOH)to yield compounds 2 (8.1 mg),3 (3.4 mg),4 (4.7 mg),5(7.2 mg),6 (10.5 mg),7 (7.3 mg),8 (13.9 mg),9 (15.2 mg),10 (17.3 mg),11 (740.8 mg).Fr.C(9.5 g)was purified onto a silica gel column chromatography eluted with CHCl3∶MeOH (100∶1-5∶1)and followed Sephadex LH-20 column chromatography(MeOH)to yield 12 (22.8 mg),13 (6.9 mg).

Structural identification

Compound 1 C6H6O3;White solid;ESI-MS m/z 149[M+Na]+;1H NMR (CD3OD,500 MHz)δH:7.95(1H,d,J=5.5 Hz,H-5),6.41 (1H,d,J=5.5 Hz,H-6),2.36 (3H,s);13C NMR (CD3OD,125 MHz)δC:152.2 (C-2),144.6 (C-3),175.3 (C-4),114.4 (C-5),156.3 (C-6),14.4 (C-7).The NMR data was consistent with the data reported in literature[4].Hence,compound 1 was identified as maltol.

Compound 2 C6H6N2O;white solid;ESI-MS m/z 145[M+Na]+;1H NMR (CD3OD,600 MHz)δH:9.03 (1H,br,H-2),8.70 (1H,br,H-6),8.27 (1H,m,H-4),7.54 (1H,dd,J=8.0,4.9 Hz,H-5);13C NMR (CD3OD,150 MHz)δC:152.8 (C-2),131.5(C-3),137.3 (C-4),125.1 (C-5),149.5 (C-6),169.8 (3-CONH2).The NMR data was identical with the data reported in literature[5].Therefore,compound 2 was identified as nicotinamide.

Compound 3 C9H12N2O6;yellow oil;ESI-MS m/z 267 [M+Na]+,511 [2M+Na]+,487 [2MH]-;1H NMR (CD3OD,600 MHz)δH:7.88 (1H,d,J=8.1 Hz,H-6),5.87 (1H,d,J=4.6 Hz,H-1'),5.85 (1H,d,J=8.1 Hz,H-5),4.27 (1H,t,J=5.0 Hz,H-2'),4.18 (1H,t,J=5.3 Hz,H-3'),4.08(1H,m,H-4'),3.87 (1H,dd,J=12.7,2.9 Hz,H-5(a),3.77 (1H,dd,J=12.7,4.1 Hz,H-5(b);13C NMR (CD3OD,150 MHz)δC:152.5 (C-2),166.9(C-4),103.1 (C-5),142.7 (C-6),90.4 (C-1),70.5 (C-2'),74.8 (C-3'),85.4 (C-4'),61.8 (C-5').The NMR data was in agreement with the data reported in literature[6]and determined compound 3 as uridine.

Compound 4 C9H12N2O5;colorless solid;ESI-MS m/z 251[M+Na]+;1H NMR (CD3OD,500 MHz)δH:7.97 (1H,d,J=8.1 Hz,H-6),6.26 (1H,t,J=6.6 Hz,H-1'),5.68 (1H,d,J=8.1 Hz,H-5).4.37 (1H,m,H-4'),3.93 (1H,m,H-3'),3.77(1H,d,J=12.0 Hz,H-5(a),3.71 (1H,d,J=12.0Hz,H-5(b),2.28 (1H,m,H-2(a),2.18 (1H,m,H-2(b);13C NMR (CD3OD,125 MHz)δC:152.2(C-2),166.3 (C-4),102.6 (C-5),142.5 (C-6),88.9 (C-1'),41.4 (C-2'),72.3 (C-3'),86.6 (C-4'),62.8 (C-5').Compound 4 was identified as deoxyuridine by comparison with the spectra data reported in literature[7].

Compound 5 C10H14N2O6;colorless solid;ESI-MS m/z 281 [M+Na]+,257 [M-H]-,515 [2MH]-;1H NMR (CD3OD,500 MHz)δH:7.85 (1H,s,H-6),5.90 (1H,d,J=4.5 Hz,H-1'),4.16 (1H,m,H-2'),3.99 (2H,m,H-3(,H-4'),3.84 (1H,dd,J=12.3,2.7 Hz,H-5(a),3.77 (1H,dd,J=12.3,3.0 Hz,H-5(b),1.98 (3H,s).13C NMR(CD3OD,125 MHz)δC:152.5 (C-2),166.5 (C-4),111.5 (C-5),138.4 (C-6),90.4 (C-1'),71.3 (C-2'),75.5 (C-3'),86.3 (C-4'),62.3 (C-5'),12.4(5-CH3).The above data was identical with the data reported in literature[8].Consequently,compound 5 was identified as thymidine.

Compound 6 C10H14N2O5;white crystal (MeOH);ESI-MS m/z 265 [M+Na]+,507 [2M+Na]+,241[M-H]-,483 [2M-H]-;1H NMR (CD3OD,500 MHz)δH:7.67 (1H,s,H-6),6.28 (1H,t,J=6.8 Hz,H-1'),4.46 (1H,m,H-4'),4.00 (1H,m,H-3'),3.83 (1H,dd,J=12.4,3.5 Hz,H-5(a),3.76(1H,dd,J=12.5,4.8 Hz,H-5(b),2.36 (2H,m,H-2'),1.89 (3H,s,CH3);13C NMR (CD3OD,125 MHz)δC:152.6 (C-2),167.4 (C-4),112.3 (C-5),138.4 (C-6),87.6 (C-1'),39.7 (C-2'),71.5 (C-3'),86.0 (C-4'),62.2 (C-5'),12.5 (5-CH3).The NMR data was in accordance with the data reported in literature[9],and identified as deoxythymidine.

Compound 7 C4H4N2O2;colorless solid;ESI-MS m/z 135[M+Na]+;1H NMR (CD3OD,500 MHz)δH:7.40 (1H,d,J=7.7 Hz,H-6),5.42 (1H,d,J=7.7 Hz,H-5);13C NMR (CD3OD,125 MHz)δC:152.0 (C-2),142.7 (C-4),100.7 (C-5),164.8(C-6).By comparison the NMR data with the data reported in literature[8],compound 7 was identified as uracil.

Compound 8 C13H18O6;colorless oil;ESI-MS m/z 293 [M+Na]+,563 [2M+Na]+,539 [2MH]-;1H NMR(CD3OD,500 MHz)δH:7.27 (2H,d,J=8.4 Hz,H-2,H-6),7.02 (2H,d,J=8.4 Hz,H-3,H-5),5.40 (1H,d,J=2.0 Hz,H-1'),4.52(2H,s,H-7),3.96 (1H,m,H-2'),3.82 (1H,m,H-3'),3.62 (1H,dq,J=12.4,6.2 Hz,H-5'),3.44(1H,t,J=9.5 Hz,H-4'),1.20 (3H,d,J=6.2 Hz,H-6').13C NMR (CD3OD,125 MHz)δC:157.1(C-1),129.5 (C-2,C-6),117.4 (C-3,C-5),136.4(C-4),64.8 (C-7),99.8 (C-1'),72.1 (C-2'),72.2(C-3'),73.8 (C-4'),70.6 (C-5'),18.0 (C-6').Comparing NMR data with the data reported in literature[9],compound 8 was identified as 1-O-(4-hydroxymethylphenyl)α-L-rhamnopyranoside.

Compound 9 C13H18O6;colorless oil;ESI-MS m/z 293[M+Na]+,563[2M+Na]+,269[M-H]-,539[2M-H]-;1H NMR (CD3OD,500 MHz)δH:7.40(2H,m,H-3,H-5),7.30 (3H,m,H-2,H-4,H-6),4.92 (1H,d,J=11.8 Hz,H-7a),4.65 (1H,d,J=11.8 Hz,H-7b),4.34 (1H,d,J=7.7 Hz,H-1'),3.88 (1H,dd,J=11.9,2.0 Hz,H-6(a),3.67(1H,dd,J=11.7,5.3 Hz,H-6(b).3.20-3.31(4H,m,H-2 (,H-3 (,H-4 (,H-5');13C NMR(CD3OD,125 MHz)δC:138.9 (C-1),129.0 (C-2,C-6),129.1 (C-3,C-5),128.5 (C-4),103.1 (C-1'),74.9 (C-2'),77.9 (C-3'),71.5 (C-4'),77.9(C-5'),62.6 (C-6').The above data was consistent with the data reported in literature[10].Hence,compound 9 was identified as benzyl-β-D-glucopyranoside.

Compound 10 C19H30O7;colorless oil;ESI-MS m/z 393[M+Na]+,763[2M+Na]+,369[M-H]-,739[2M-H]-;1H NMR (CD3OD,500 MHz)δH:5.87(1H,s,H-4),5.76 (1H,dd,J=14.9,3.5 Hz,H-8),5.58 (1H,m,H-7),4.39 (2H,m,H-9,H-1'),3.81 (1H,d,J=11.8 Hz,H-6(a),3.64(1H,m,H-6(b),3.29 (2H,m,H-4(,H-5'),3.18 (2H,m,H-2(,H-3'),2.66 (1H,d,J=8.6 Hz,H-6),2.42(1H,d,J=16.7 Hz,H-2a),2.03 (1H,d,J=16.9 Hz,H-2b),1.93 (3H,s,H-13),1.28 (3H,d,J=6.3 Hz,H-10),1.00 (6H,m,H-11,H-12).13C NMR(CD3OD,125 MHz)δC:37.1 (C-1),48.2 (C-2),201.9 (C-3),126.1 (C-4),165.8 (C-5),56.7 (C-6),128.8 (C-7),138.2 (C-8),76.9 (C-9),21.0(C-10),27.6 (C-11),28.0 (C-12),23.8 (C-13),102.4 (C-1'),75.2 (C-2'),78.0 (C-3'),71.4 (C-4'),77.9 (C-5'),62.6 (C-6').The above data was in accordance with the data reported in literature[11].Consequently,compound 10 was identified as (6R,9R)-3-oxo-α-ionol-9-O-β-D-glucopyranoside.

Compound 11 C29H44O7;white solid;ESI-MS m/z 527[M+Na]+,503 [M-H]-;1H NMR (C5D5N,500 MHz)δH:6.27 (1H,d,J=2.3 Hz,H-7),4.49(1H,dd,J=11.3,2.6 Hz,H-22),4.25 (1H,s,H-3),4.18 (1H,d,J=10.2 Hz,H-2),3.60(1H,m,H-9),3.01 (2H,m,H-5,H-17),2.66 (1H,td,J=12.9,4.7 Hz,H-15a),2.45 (1H,dd,J=20.8,10.2 Hz,H-16a),2.26-2.13 (3H,m,H-1a,H-15b,H-25),2.06 (3H,ddd,J=13.8,11.3,8.3 Hz,H-4a,H-16b,H-23a),1.94 (4H,m,H-1b,H-11a,H-12,H-23b),1.75 (2H,ddd,J=18.1,17.2,9.9 Hz,H-4b,H-11b),1.50 (3H,s,H-21),1.40(2H,m,H-24,H-241a),1.31 (3H,m,H-27),1.16(3H,s,H-18),1.09 (3H,s,H-19),1.05(1H,m,H-241b),0.71(3H,t,J=7.4 Hz,H-242);13C NMR (C5D5N,125 MHz)δC:38.4 (C-1),68.5 (C-2),68.4 (C-3),32.2 (C-4),51.3 (C-5),203.2 (C-6),121.6 (C-7),165.6 (C-8),34.1 (C-9),38.4 (C-10),20.8(C-11),31.7 (C-12),47.7 (C-13),83.9 (C-14),31.5 (C-15),21.2 (C-16),49.7 (C-17),17.8 (C-18),24.2 (C-19),75.5 (C-20),21.2 (C-21),85.7(C-22),29.4 (C-23),39.9 (C-24),41.2 (C-25),174.4 (C-26),15.5 (C-27),26.4 (C-241),10.0(C-242).The NMR data was consistent with the data reported in literature[12].Hence,compound 11 was identified as capitasterone.

1 Editor Board of Chinese Materia Medica of the state Administration of Traditional Chinese Medicine.Chinese Materia Medica.Shanghai:Shanghai Science and Technology Publisher,1999.2,782.

2 Zhao BS,Gui HS,ZHU YD,et al.Research progress in chemical compoents,pharmacological effectiveness and toxicity of Psammosilene tunicoides.Chin J Exp Tradit Med Form,2011,17:288-291.

3 Zhao J,Wang W,Gao R.Research progress of chemical composition and pharmacological of Psammosilene tunicoides.J Anhui Agric Sci,2009,37:11526-11529.

4 Zhou J,Chen C,Xie Y,et al.Studies on liposoluble constituents from fruit of Sophora japonica L..J Shanghai Jiaotong Univ,2006,11:015.

5 Li WC,Yan YM,Zhong HM.Chemical constituents from the roots of Calotropis procera.Nat Prod Res Dev,2012,24:1390-1392.

6 Song Y,Chen GT,Sun BH,et al.Chemical constituents of water-soluble part of Mentha spicata L..J Shenyang Pharm Univ,2008,25:705-707.

7 Xu XL,Song FH,Fan X,et al.Studies on the chemical constituents of Ascidian Amaroucium sp.Lishizhen Med Mater Med Res,2008,19:2632-2633.

8 Su GC,Zhang S,Qi SH.Chemical constituents of Amtipathes dichotoma.Chin Tradit Herb Drugs,2008,39:1606-1609.

9 Grond S,Papastavrou I,Zeeck A.Novel α-L-Rhamnopyranosides from a Single Strain of Streptomyces by supplement-induced biosynthetic Steps.Eur J Org Chem,2002,2002:3237-3242.

10 Kong CS,Um YR,Lee JI,et al.Constituents isolated from Glehnia littoralis suppress proliferations of human cancer cells and MMP expression in HT1080 cells.Food Chem,2010,120:385-394.

11 Kuang H,Yang B,Xia Y,et al.Chemical constituents from the flower of Datura metel L..Arch pharm res,2008,31:1094-1097.

12 Hiroshi H,et al.Structure of precyasterone,A Novel C29insect-moulting substance from Cyathula capitata.Chem PharmBull,1970,18:1078-1080.

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