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Studies on Diarylheptanoids from Qinglongyi
YANG Bingyou, ,MENG Ying, ZHOU Yuan-yuan
(HeilongjiangUniversity of Traditional ChineseMedicine,Teachering and Researching Room of Chinese Herbal Medicine Chemistry, Harbin,China)
[Abstract] Objective:To study the natural anticancer products from Qinglongyi. Methods:
The compounds were isolated by chro-matography with silica gel columns and AB-8 resin etc.,and were identified by NMR analysis. Results: They are galleon(I), JuglaninA(II), pterocarine(III) ,3',4''-epoxy-1-(4'-hydroxyphenyl)-7-(3'-methoxylphenyl)-heptane-2-hydroxy-3-one(IV),4"-epoxy-1-(4'-hydroxyphenyl)-7-(3"-methoxylphenyl)-heptane-3-hydroxy(V). Conclusion :Compound I,III,IV,V were isolated from this plant for the first time.
[Key words] Qinglongyi; chemical constituents; diarylheptanoids
Introduction
Juglans Mandshurica maxim is one of the most important medical plants,of which the pericarps,leaf and bark all can be medically used.We called the immature pericarps Qinglongyi.It was recorded in the book named «Kaibao herbs} which indicated the properities and functions of this material. Qinglongyi was used as a folk medicine in many aspert,such as in clearing away heat,detoxicating ang treating dysentery erc.Modern medical research found its most prominent is the pharmacological effects of the anti-tumor efficacy which is the hotspot in development. This article make a systerm separation for Qinglongyi anti-tumor activity site,total separation five diarylheptanoids,they were galeon(I),walnut glycosidesA(n),Maplesalicin(III),3',4"-epoxy-1-(4'-hydroxy-phenyl)-7-(3''-methoxyl-phenyl)-heptane-2-hydroxy-3-one(IV),4''-epoxy-1-(4'-hydroxyphenyl)-7-(3''-metho-xylphenyl)-heptane-3-hydroxy(V),among compound I, III, IV,Vfirst isolated from the plant.
Materials and methods
1.Materials
Bruker-400 superconducting NMR spectrometer;MS-2010 spectrometer and Finnigan LCQ LC-MS Hyphenated instrument;Shimadzu corporation FTIR-8400S infrared spectomrter; column chromatography silica gel (200~300) produced from Qingdao marine chemical; AB-8 resin produced by Nankai university chenmical factory; other reagents were AR. In 2007 Qinglongyi medicines purchased in Heilongjiang province medicine company and identify by Wang zhenyue teacher who come from Heilongjianguniversity of Chinese medicine identification deparment.
2.Methods
2.1Extraction Samsh five kilogram dried Qinglongyi herbs, 95% ethanol reflux extraction three times,depressurize inspissation get ethanol extract (376g).After extract for right amount water
suspended,ethyl acetate and chloroform made two-phase reflowr,after ecover organic reagents,get ethyl acetate extract is 33g,through AB-8 punch adsorption resin column chromatography,H2O,50% ethanol and 95% ethanol followed by elution,among 95% ethanol elution constituent were 12g,repeat silica gel column chromatography get compound I(20 mg),compound II(18mg),compound III( 16 mg).CHCl3elution fraction were 40g ,repeat silica gel column chromatography get compound IV(31 mg), compound V(23 mg).Chemical formula figure 1.
r5
CO CO
CO
CO
OH
2.2 Structure identification
2.2.1 compound II was white amorphous powder (MeOH), EI-MS give 356[M]+,showed that molecular weight should be 326.1H-NMR(400MHz,CDCl3)D:2.97,2.83(2H,ddd,J=0.8, 10.8,16.0Hz,H-1);2.36,2.24(2H,ddd,J=2.0,8.0,16.8Hz,H-2);1.95,1.51(2H,m,H-4);1.52(2H,m,H-5); 1.77(dd,J=5.2,12.8Hz,H-6a),1.56(m,H-6b);2.83,2.63(2H,dt,J=4.8,13.2Hz,H-7);5.56(1H, d,J=2.0Hz,H-2');6.83(1H,d,J=8.0Hz,H-5');6.62(1H,dd,J=2.0,8.0Hz,H-6');6.86(1H,d,J=2.0Hz,H-2'');7.02(1H,d,J=8.4Hz,H-5'');6.88(1H,d,J=2.0,8.4Hz,H-6'');3.73(3H,s,3''-0CH3);5.59(1H,brs,4'-0H).1H-NMR(400MHz,CDCl3)D:27.5(C-1),41.4(C-2),210.2(C-3),46.4(C-4),19.1(C-5), 27.4(C-
6),36.0(C-7),133.4(C-1'),112.3(C-2'),147.3(C-3'),143.2(C-4'),115.0(C-5'),122.0(C-6'), 140.2(C-1''),115.0(C-2'')',152.2(C-3''),142.9(C-4''),124.1(C-5''),122.1(C-6''),56.1(3''-0CH3).NMR data consistent with the literature[2] of galeon,so compound I was galleon.
2.2.2 compound II was white amorphous powder (MeOH),EI-MS give 356[M]+, showed that molecular weight should be 356.1H-NMR (400MHz,CDCl3) D:2.99,2.74(2H,ddd,J=2.0, 9.2,16.4Hz,H-1);2.29(2H,m,H-2)2.08,1.75(2H,ddd,J=5.6,10.8, 16.0Hz,H-4);1.59(2H,m,H-5); 1.80,1.65(2H,m,H-6);3.16,2.37(2H,ddd,J=5.6,13.2,16.8Hz,H-7); 5.56(1H,d,J=2. 0 Hz, H-2');
6. 82(1H, d,J=8.4Hz,H-5'); 6.62(1H,dd,J=2.0,8.0Hz,H-6');6.58(1H, d,J=8.4Hz,H-5'');6.90(1H, d,J=8.4Hz,H-6'');3.94(3H,s,4'-0CH3);3.98(3H,s,3''-0CH3);5.95(1H,brs,2''-0H.13C-NMR(400MHz,CDCl3)D:27.1(C-1),41.1(C-2),210.1(C-3),46.2(C-4),19.0(C-5),24.7(C-6),29.9(C-
7),134.3(C-1'),113.1(C-2''),149.0(C-3'),146.4(C-4'),111.9(C-5'),122.0(C-6'),124.8(C-1''),147.9(C-2''),139.8(C-3''),145.6(C-4''),115.9(C-5''),126.1(C-6''),56.1(4''-0CH3),61.6(3''-0CH3).NMR data consistent with the literature[3] of Juglanin A,so compound II was galleon Juglanin A.
2.2.3 compound III was white amorphous powder (Me0H), EI-MS give 312[M]+, showed that molecular weight should be 312.1H-NMR (400 MHz,CDCl3)D:2.89, 2.82(2H, ddd,J=1.0, 10. 8,16.4 Hz,H-1); 2.36, 2.28(2H, ddd,J=2.4, 8.2, 16. 8 Hz,H-2); 1.91,1.83(2H,m,H-4);1. 54(2H,m,H-5); 1.68, 1.64( 2H,m,H-6);2.73,2.68(2H, dt,J=4. 8, 13. 2 Hz,H-7); 5.55(1H, d,J=2. 2Hz,H-2');6. 83(1H, d,J=8. 0 Hz,H-5'); 6.63(1H, dd,J=2. 2, 8. 0 Hz,H-6'); 6. 94(1H, d,J=2. 0 Hz,H-2''); 6. 88(1H, d,J=8. 4 Hz,H-5''); 6. 84(1H, d,J=2.0, 8.4Hz,H-6''); 5.79(1H, brs, 4''-0H); 5. 72(1H, brs,3''-0H).13C-NMR(400 MHz, CDCl3)D:27.3(C-1), 41.2(C-2), 210. 4(C-3), 46. 4(C-4),19.1(C-5),27.3(C-6),35.8(C-7),133.7(C-1'),112.5(C-2'),147.0(C-3'),143.1(C-4'),115.5(C-5'), 122. 7 (C-6')
V OH
Figure1 five diarylheptanoids compounds structure
,140. 4 (C-1''), 118. 2 (C-2''), 149.1(C-3''). 141.2(C-4"),123.5(C-5"), 122.7 (C-6'').NMRdata consistent with maple salicin that study of Liu hongbing,so the compound III was maple salicin.
2.2.4 compound IV was white amorphous powder (MeOH), EI-MS give 342[M]+, showed that molecular weight should be 342.1H-NMR (400MHz,CDCl3)D:2. 94 (1H, dd,J=14.8, 2. 4 Hz,H-1a); 2.85 (1H, ddd,J=14.8,6.9 Hz,H-1b); 4.01 (1H, dd,J=6.6, 2.4Hz,H-2); 2.04,1.76 (2H, ddd,J=5.6, 10.8, 16.0 Hz,H-4); 1.56(2H,m,H-5); 1.83, 1. 62(2H,m,H-6); 2.72(2H,m,H-7);5. 58 (1H,d,J=2.2Hz,H-2'); 6.79 (1H, d,J=8. 2Hz,H-5'); 6. 65 (1H,dd,J=8.2, 2.2 Hz,H-6'); 6. 88 (1H, d,J=2. 0 Hz,H-2''); 7.00(1H, d,J=8. 0 Hz,H-5''); 6. 87(1H, dd,J=8.0, 2.0 Hz,H-6''); 3. 94(3H, s, 3''-OCH3); 5.59( 1H, brs, 4'-OH).13C-NMR(400MHz,CDCl3)D: 37.5 (C-1), 82.6 (C-2), 211. 2(C-3),45. 8(C-4), 19.2(C-5),27.9 (C-6),36.1(C-7),128.1(C-1'), 112.6 (C-2'), 147.4(C-3'), 143. 2(C-4'), 115. 2 (C-5'), 122. 1 (C-6'), 140. 3(C-1''),115. 8 (C-2''),152. 6(C-3"),142.7(C-4"), 124. 6(C-5''),122.1(C-6''),56.3(3''-OCH3).So compound IV was 3',4''-epoxy-1-(4'-hydroxyphenyl) -7-(3''-methoxylphenyl)-heptane-2-hydroxy-3-one.
2.2.5 compound V was pale yellow oily substance.EI-MS give 328[M]+, showed that molecular weight should be 328.1H-NMR(400MHz, CDC1 3)D: 2.86, 2.83(2H,ddd,J=2.2, 9.6, 16.4Hz,H-1);1.46(2H,m,H-2);3.22(1H,m,H-3);1.82,1.47(2H,m,H-4);1.49(2H,m,H-5);1.97(2H,m,H-6); 2.81, 2.53 (2H,m,H-7);5.64(1H, d,J=2.0Hz,H-2');6.68(1H, d,J=8.0 Hz,H-5');6. 57(1H, dd, J=2.
0.8. 0 Hz,H-6'); 6.96(1H, d,J=2.0 Hz,H-2'');7.04(1H,d,J=8. 0 Hz,H-5''); 6.89(1H, d,J=2.0,8.0Hz,H-6'');3.75(3H,s,3''-OCH3); 5.60 (1H,brs,4'-OH).1H-NMR(400 MHz ,CDC13) D: 28.4(C-1), 41.8 (C-2), 78.6 (C-3), 43.4 (C-4), 20. 2(C-5), 28.9 (C-6),36. 2(C-7), 133. 8 (C-1') ,112. 6 (C-2'), 147. 9 (C-3'), 143. 0(C-4') , 115. 5(C-5'),122. 3 (C-6'), 140.2 (C-1''), 115.1(C-2"),152.4(C-3"),142.7(C-4"), 124. 0(C-5''),122.1(C-6''),56.3(3''-OCH3),so compound was 4''-epoxy-1-(4'-hydroxyph-enyl)-7-(3''-methoxy-lphenyl)-heptane-3-hydroxy.
3.Conclusions
Currtetlly, Isolated from Qinglongyi diarylheptanoids mostly cyclic ether compounds Type. According to literature, this type components have significant anti-tumor effects, This type composition were one of pharmacodynamic material basic that Qinglongyi anti-tumor effects, subsequent separation of the work is still in progress o References
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