夏郭平,馮 煦,陳 雨,王 鳴,董云發(fā)

江蘇省藥用植物研究開發(fā)中心江蘇省中國科學院植物研究所,南京 210014

Introduction

SalicorniaL.(Chenopodiaceae)is a genus of annual apparently leafless halophytic herbs that have articulated,succulent stems.S.herbaceais used as traditional medicine treating hypertension,cephalalgia and scurvy.[1]In Korea,it is also used in the trea tment of constipation,obesity,diabetes and cancer.[2-5]Indian people useS.brachiatato treatmange and pruritus.[6]S. bigeloviiwas evaluated as an oilseed crop and seasoned vegetable for direct seawater irrigation.[7]Although the economic value of this plant has already been discovered and developed,the medicinal value has been ignored for a long time.The present studywas carried out to examine the chemical constituents ofSalicornia bigeloviito support the further pharmaceutical research.

Materials andM ethods

General

Silica gel(200-300 mesh)for column chromatography and GF254for TLC were produced by Qingdao Haiyang Chemical Co.Ltd,China.Sephadex LH-20,ODS and D101 macroporous resin were purchased from Amersham Biosciences Inc,USA,Y MC Co.Ltd,Japan and Tianjin Haiguang Chemical Co.Ltd,China separately. Allother chemicals used in this studywere of analytical grade.Melting pointswere determined on a Boetiusmic romelting point apparatus(uncorrected).NMR spectra were obtained on a BrukerAvance DRX2500 spectrometer(1H∶300,500 MHz;13C∶125 MHz)using CD3OD,CDCl3orDMSO-d6as solvent.

Plantmater ial

The whole plant ofSalicornia bigeloviiTorr.was collected from Yancheng,China,in August2007 and identified by Prof.Yuan Chang-qi.A voucher specimen was deposited in the Herbarium of Institute ofBotany,Jiangsu Province&Chinese Academy of Sciences.

Extraction and isolation

The fresh plant material(48 Kg)was extracted with EtOH under room temperature.After the removal the solvent by evaporationin vacuo,the residue was suspended in water and extracted with petroleum ether, EtOAc and water.The EtOAc fraction(42 g)was chromatographed on a silica gel by a gradient with CHCl3and MeOH to afford compounds 1(20∶1,3 mg),6(20∶1,12 mg),3(15∶1,7 mg),4(10∶1,11 mg),and 5(10∶1,9 mg).The water fraction(3 Kg) was through the D101 macroporous resin to obtain compounds 2(90%EtOH,2 mg)and 6(90%EtOH,2 mg).All those compoundswere further purified by gel filtration and reversed phase chromatographing.

Result and Conclusion

Scopoletin(1) Colorless needle crystal(acetone), mp.203-205℃;Strong blue fluorescence under sunlight.1H NMR(CD3OD,300 MHz)δ:7.86(1H,d,J =9.4 Hz,H-4),7.12(1H,s,H-8),6.77(1H,s,H-5),6.20(1H,d,J=9.4 Hz,H-3),3.91(3H,s, OCH3);13C NMR(CD3OD,125 MHz)δ:163.2(C-2),152.0(C-7),150.6(C-9),146.1(C-6),145.1 (C-4),112.0(C-3),111.7(C-10),109.1(C-5), 103.0(C-8),55.8(OCH3).Compared with the published data,Compound 1 was identified as scopoletin[8].

Jun iper camphor(2) Colorless needle crystal(acetone),mp.164-166℃;1H NMR(CDCl3,500 MHz) δ:0.96(3H,s,15-CH3),1.06(1H,m,H-1),1.11 (1H,d,J=3 Hz,H-8),1.13(3H,s,H-14),1.15 (1H,bs,H-10),1.31(1H,m,H-6),1.39(1H,m,H-8),1.42(1H,m,H-1);1.53(2H,m,H-7),1.62 (1H,bs,H-4),1.67(3H,s,13-CH3),1.69(3H,s, 12-CH3),1.79(1H,m,H-6),1.90(1H,m,H-2), 2.48(1H,m,H-2),2.80(1H,m,H-4);13C NMR (CDCl3,125 MHz)δ:131.4(C-3),121.0(C-11), 72.3(C-5),55.8(C-10),45.3(C-1),43.7(C-6), 41.1(C-8),34.9(C-9),25.5(C-2),24.7(C-4), 22.1(C-14),20.3(C-7),20.1(C-12),20.0(C-13), 18.1(C-15).Compound 2 was identified as Juniper camphor by the comparison with the published data[9].

Hyperoside(3) Yellow amorphous powder (MeOH),mp.235-236℃.It responded positively to the Shinoda and the Molisch tests.1H NMR(DMSO-d6,300 MHz)δ:6.19(1H,d,J=1.6 Hz,6-H),6.39 (1H,d,J=1.6 Hz,8-H),6.81(1H,d,J=8.9 Hz, 5′-H),7.67(1H,dd,J=1.8 Hz,8.9 Hz,6′-H),7.52 (1H,d,J=1.8 Hz,2′-H),5.37(1H,d,J=7.1 Hz, Gal-1-H),5.12,4.85,4.43(3H,br,3×OH),12.63 (1H,s,5-OH);13C NMR(DMSO-d6,125 MHz)δ: 156.1(C-2),133.4(C-3),177.4(C-4),161.1(C-5),98.6(C-6),164.1(C-7),93.4(C-8),156.2(C-9),103.8(C-10),121.9(C-1′),115.1(C-2′),144.7 (C-3′),148.4(C-4′),115.9(C-5′),121.0(C-6′), 101.8(Gal-1),71.1(Gal-2),73.1(Gal-3),67.8 (Gal-4),75.7(Gal-5),60.0(Gal-6).Compared with the published data,Compound 3 was identified as hyperoside.[10]

Quercetin(4) Yellow amorphous powder(MeOH), mp.313-314℃.It responded positively to the Shinoda test.1H NMR(DMSO-d6,300 MHz)δ:7.67(1H,d,J =1.9 Hz,H-2′),7.53(1H,dd,J=8.5,1.9 Hz,H-6′),6.87(1H,d,J=8.5 Hz,H-5′),6.40(1H,d,J= 2.0 Hz,H-8),6.18(1H,d,J=1.9 Hz,H-6),12.48 (1H,s,5-OH),9.37(4H,brs,4×OH);13C NMR (DMSO-d6,125 MHz)δ:175.7(C-4),164.0(C-7), 160.2(C-9),156.2(C-5),147.6(C-4′),146.7(C-2),145.0(C-3′),135.6(C-3),121.9(C-1′),119.9 (C-6′),115.5(C-5′),115.0(C-2′),102.9(C-10), 98.1(C-8),93.3(C-6).Compared with the published data,Compound 4 was identified as quercetin.[11]

Isorhamnet in-3-O-β-D-glucopyranoside (5) Yellow amorphous powder,mp.243-245℃.Showed positive to the Shinoda and the Molisch tests.1H NMR (DMSO-d6,300 MHz)δ:6.20(1H,d,J=2.0 Hz,6-H),6.43(1H,d,J=2.0 Hz,8-H),6.90(1H,d,J= 8.0 Hz,5′-H),7.49(1H,dd,J=8.4,2.0 Hz,6′-H), 7.94(1H,d,J=2.0 Hz,2′-H),5.56(1H,d,J=7.4 Hz,Glc-1-H),5.16,5.07,4.96(3H,br,3×OH), 12.60(1H,s,5-OH),3.87(3H,s,-OCH3);13C NMR (DMSO-d6,125 MHz)δ:156.1(C-2),132.9(C-3), 177.3(C-4),161.1(C-5),98.7(C-6),164.3(C-7), 93.6(C-8),156.3(C-9),103.9(C-10),121.0(C-1′),113.5(C-2′),146.8(C-3′),149.3(C-4′), 115.9(C-5′),122.0(C-6′),55.6(OCH3),100.8(G-1),74.3(G-2),76.4(G-3),69.8(G-4),77.4(G-5),60.6(G-6).Compared with the published data, Compound 5 was identified as isorhamnetin-3-O-β-D-glucopyranoside.[12]

β-sitosterol(6) was elucidated by spectral analysis and comparison with the published data.[12]To the best of our knowledge,this is the first report on the isolation of scopoletin(1)and juniper camphor(2)from Genus Salicorniaand the isolation of quercetin(4)andβ-sitosterol(6)fromSalicornia bigelovii.

AcknowledgementWe thank the Open Fund of Jiangsu Center forResearch&DevelopmentofMedicinal Plants (No.200901)for financial support.

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