Chemical Components of Seriphidium santolium Poljak

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1 Journal of the Chinese Chemical Society, 2004, 51, Chemical Components of Seriphidium santolium Poljak Yan-Ru Deng ( ), Ai-Xin Song ( ) and Han-Qing Wang* ( ) State Key Laboratory of SS, Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences, Lanzhou , P. R. China A new biflavonoid glucoside, apigenin-7-- -D-glucopyranoside-(3 --7 )-quercetin-3 -methyl ether (1) together with twenty known compounds, apigenin (2), luteolin (3), chrysoeriol (4), tricin (5), hispidulin (6), pectolinarigenin (7), eupatilin (8), 5,7-dihydroxy-6,3,4,5 -tetramethoxyflavone (9), 5,7,4 -trihydroxy- 6,3,5 -trimethoxyflavone (10), 3,6--dimethylquercetagetin-7-- -D-glucoside (11), 6-hydroxy-5,7-dimethoxy-coumarin (12), taraxerol (13), taraxeryl acetate (14), a mixture of -sitosterol (15) and stigmasterol (16), a mixture of the n-alkyl trans-p-coumarates (17), a mixture of the n-alkyl trans-ferulates (18), 2-hydroxy-4,6-dimethoxyacetophenone (19), 4-hydroxy-2,6-dimethoxyphenol-1-- -D-glucopyranoside (20), and 2-hydroxycinnamoyl- -D-glucopyranoside (21), were isolated from the whole plant of Seriphidium santolium Poljak. The structures of these compounds were determined by means of spectral and chemical studies. Keywords: Seriphidium santolium Poljak; Compositae; Flavonoids. INTRDUCTIN The genus Seriphidium belonging to the family Compositae is grown in China in about 31 species. 1 Several members of this genus are used in folk medicine as antihelminthics. 2 Seriphidium santolium Poljak, a species of Seriphidium, is widespread in Xinjiang Uigour Autonomous Region, P. R. China. 1 The phytochemical studies of Seriphidium santolium Poljak have not been reported. We have now investigated the chemical constituents of this plant and have isolated a novel biflavonoid glucoside and twenty known compounds. From our research the whole plant contains many flavonoids, which have potential antioxidant activity and antiproliferation of the lung carcinoma A549 cell and liver carcinoma Bel7402 cell. In this paper, we report the isolation and identification of these 21 compounds, that is apigenin D-glucopyranoside-(3 --7 )-quercetin-3 -methyl ether (1), apigenin (2), 3 luteolin (3), 4 chrysoeriol (4), 5 tricin (5), 6 hispidulin (6), 7 pectolinarigenin (7), 8 eupatilin (8), 9 5,7-dihydroxy-6,3,4 5 -tetramethoxyflavone (9), 10 5,7,4 trihydroxy-6,3 -trimethoxyflavone (10), 11 3,6--dimethylquercetagetin-7-- -D-glucoside (11), 12 6-hydroxy-5,7- dimethoxy-coumarin (12), 13 taraxerol (13), 14 taraxeryl acetate (14), 15 a mixture of -sitosterol (15) and stigmasterol (16), 16 a mixture of the n-alkyl trans-p-coumarates (17), 17 a mixture of the n-alkyl trans-ferulates (18), 18 2-hydroxy-4,6- dimethoxyacetophenone (19), 19 4-hydroxy-2,6-dimethoxyphenol-1-- -D-glucopyranoside (20), 20 2-hydroxycinnamoyl- -D-glucopyranoside (21). 21 Among them, compound 1 is a new biflavonoid glucoside; compounds 2-21 were isolated from this plant for the first time. The structures of these compounds were elucidated by means of spectroscopy. RESULTS AND DISCUSSIN Compound 1 was obtained as a pale yellow powder, mp C.The IR spectrum showed the absorption bands of hydroxyl (3351 cm -1 ), carbonyl (1656 cm -1 ), and aromatic (1603, 1499 cm -1 ) groups. UV max (Me) 268, 333 nm, and positive results of Molish and Mg/HCl reactions suggested that 1 was a flavonoid compound. Acid hydrolysis of 1 in refluxing 15% HCl benzene afforded D-glucose, identified by PC using EtAC-pyridine-H 2 (12:5:4). The FABMS showed the ion [M-162+H] + at m/z 585, corresponding to the molecular formula C 37 H This was corroborated by the 13 C NMR and DEPT spectra, which showed 37 carbon resonances. The molecular formula and the presence of two carbonyl resonances at and suggested that 1 could be a biflavonoid glucoside. The 1 H NMR spectrum of 1 exhibited a two ABX coupling system, one set of signals at H 7.58 (1H, d, J = 2.0 Hz), 7.48 (1H, dd, J = 8.8, 2.0 Hz) and 6.93 (1H, d, J = 8.8 Hz) for H-2 and 5 of E-ring, respectively, the other set of signals at H 7.42 (1H, dd, J = 8.4, 2.0 Hz), 7.40 (1H, d, J = 2.0

2 630 J. Chin. Chem. Soc., Vol. 51, No. 3, 2004 Deng et al.. 1'''' A C ' 6' 5' B 4' 2' 3' 7'' 6'' 8'' D 5'' F 4'' 2''' 2'' 1''' E 3'' 6''' CH 3 3''' 4''' 5''' 1 R 1 R 1 H R 2 H R 2 H 3 C R 3 2 R 1 =H, R 2 = 6 R 1 =R 3 =H, R 2 = 3 R 1 =R 2 = 7 R 1 =R 3 =H, R 2 =CH 3 4 R 1 =CH 3,R 2 = 8 R 1 =R 2 =CH 3,R 3 =H 9 R 1 =R 2 =R 3 =CH 3 10 R 1 =R 3 =CH 3,R 2 = CH 3 H H CH 3 CH 3 H 3 C 5 12 CH 2 H 3 C CH 3 11 Hz) and 6.91 (1H, d, J = 8.4 Hz) for H-6,2 and 5 of B-ring, respectively, indicating the presence of the C-3, C-4 disubstituted B-ring moiety and C-3, C-4 disubstituted E-ring moiety. Five downfield signals at H 12.98, 12.70, 10.02, 9.84 and 9.41 were assigned as the hydroxyl groups located at C-5, C-5, C-4, C-4 and C-3, respectively. Two pairs of meta-protons at H 6.78, 6.75, 6.43 and 6.40 were located at the C-8, C-8, C-6 and C-6, respectively. The sharp signal at H 6.74 (1H, s) was assigned to be the H-3 of A-ring. ne methoxyl group at H 3.78 (3H, s) is placed at carbon C-3 ( C 137.9) of the F-ring due to the HMBC (Table 2) correlation between each other. An anomeric proton at H 5.08 (1H, d, J =

3 Chemical Components of Seriphidium santolium Poljak J. Chin. Chem. Soc., Vol. 51, No. 3, H Ac H 15 H 16 -(CH 2 )nch 3 -(CH 2 )nch 3 H H 3 C n = 19, 21, 23 n = 19, 21, C-CH 3 Glc H 3 C CH 3 H 3 C -Glc CH Hz) indicated the presence of -D-glucosyl moiety. The above spectral data suggested that 1 could be a biflavonoid consisting of a flavone glucoside unit linked to a flavonol unit through a C--C bond. The supporting evidence (Table 1) came from the 13 C NMR spectral data of 1 which showed a close resemblance to those of apigenin D-glucoside and quercetin-3-methyl ether. Further comparison of 13 C NMR spectral data of 1 with those of apigenin D-glucoside and quercetin-3-methyl ether showed that C-3 of ring B should be involved in the interflavonoid ether linkage with C-7 of ring D as the resonance of C-3 has shifted downfield by 29.8 ppm from the corresponding

4 632 J. Chin. Chem. Soc., Vol. 51, No. 3, 2004 Deng et al. Table C NMR Spectral Data of Compound 1, Apigenin-7-- -D-glucoside, and Quercetin-3-methyl ether (100 MHz, DMS-d 6 ) No. 1 Apigenin D-glucoside No. 1 Quercetin-3-methyl ether Glc Me Table 2. 1 Hand 13 C Long-rang Correlations of 1 in HMBC Carbon Correlative H Carbon Correlative H C-2 H-3, H-2, H-6 C-2 H-2, H-6 C-3 C-3 CH 3 --C-3 C-4 H-3 C-4 C-5 H-6 C-5 H-6 C-6 H-8 C-6 H-8 C-7 H-6, H-8, H-1 C-7 H-6, H-8 C-8 H-6 C-8 H-6 C-9 H-8 C-9 H-8 C-10 H-6 C-10 H-6 C-1 H-2, H-5,H-6 C-1 H-2, H-5, H-6 C-2 H-6 C-2 H-6 C-3 H-2, H-5 C-3 H-2, H-5 C-4 H-2, H-5 C-4 H-2, H-5 C-5 H-6 C-5 H-6 C-6 H-2, H-5 C-6 H-2, H-5 carbon resonance of apigenin-7-- -D-glucoside The HMBC spectrum of 1 further confirmed the involvement of C-3 and C-7 in the interflavonoid ether linkage as these carbon s correlations with H-2 and H-5, and H-6 and H-8,respectively. Hence, from the foregoing spectral and chemical studies, the structure of compound 1 was deduced to be apigenin-7-- -D-glucopyranoside-(3 --7 )-quercetin-3 methyl ether. The known compounds were isolated and their structures were identified on the basis of their spectroscopic data (IR, UV, MS, 1 H NMR and 13 C NMR) and comparison with literature data EXPERIMENTAL SECTIN General Methods Melting points were determined on a X-4 micromelting point apparatus and were uncorrected. IR spectra were recorded on an IFR-120HR spectrometer. UV spectra were recorded on a HP-8453 spectrometer. NMR spectra were performed on an INVA-400 using TMS as an internal standard. NMR experiments include 1 H- 1 H CSY, HMQC and HMBC. FABMS, and EIMS were measured on a VG- ZAB-HS mass spectrometer. Plant Material The whole plants of Seriphidium santolium Poljak were collected from Fukang County, Xinjiang Uigour Autonomous Region of China in August 2001, and were identified by Prof. Li-Yun Zhang, Xinjiang Institute of Ecology and Geog-

5 Chemical Components of Seriphidium santolium Poljak J. Chin. Chem. Soc., Vol. 51, No. 3, raphy, Chinese Academy of Sciences, Urumqi, P. R. China. A voucher specimen is deposited in the Herbarium of the Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, P. R. China. Extraction and Isolation The air-dried whole plants of Seriphidium santolium Poljak (4 Kg) were powdered and extracted with Et ( 6) at room temperature. The extract was evaporated in vacuo to give a dark brown syrup (350 g). The syrup was suspended in water and extracted with petroleum ether, CHCl 3, EtAc and n-bu, successively. The petroleum ether layer was concentrated to give a black syrup (70 g) which was subjected to chromatography on silica gel (1.0 Kg, mesh), and eluted with a gradient of petroleum ether and EtAc (60:1, 40:1, 20:1, 10:1, 5:1, 2:1, 1:1) to afford 13 (30 mg), 14 (50 mg), a mixture of 15 and 16 (60 mg), 17 (20 mg), 18 (25 mg), and 19 (15 mg). The CHCl 3 layer was concentrated to give a brown syrup (60 g) which was subjected to chromatography on silica gel (900 g mesh), and eluted with a gradient of petroleum ether and EtAc (40:1, 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, EtAc) to give six fractions. Fraction II was recrystallized from petroleum ether EtAc to give 2 (10 mg) and 3 (8 mg). Fraction III was recrystallized from petroleum ether EtAc to give 4 (15 mg). Fraction V (3.0 g) was subjected to chromatography on silica gel (60 g, mesh), and eluted with CHCl 3 to give 6 (30 mg), 7 (25 mg), and 8 (33 mg). The EtAc layer was concentrated to give a brown syrup (60 g) which was subjected to chromatography on silica gel (900 g, mesh), and eluted with a gradient of CHCl 3 and Me (60:1, 40:1, 20:1, 10:1, 5:1, 2:1, 1:1, Me) to give seven fractions. Fraction II was recrystallized from CHCl 3 -Me to give 9 (15 mg) and 10 (25 mg). Fraction III was recrystallized from CHCl 3 -Me to give 5 (18 mg). Fraction VI (10 g) was subject to chromatography on silica gel (200 g, mesh) and eluted with a combination system of CHCl 3 and Me to give 1 (25 mg), 11 (30 mg), and 21 (14 mg). The n-bu layer was concentrated to give a brown syrup (40 g) which was subjected to chromatography on silica gel (600 g, mesh), and eluted with a gradient of CHCl 3 and Me to afford 12 (10 mg) and 20 (12 mg). Apigenin-7-- -D-glucopyranoside-(3 --7 )-quercetin-3 methyl ether (1) Pale yellow powder; mp C; UV max (Me) nm (log ): 268, 333; IR (KBr) max : 3351 (), 1656 (C=), 1603 and 1499 (Ar), 1445, 1212, 1176, 1098, 816 cm -1 ; FAB- MS m/z: 585[M-162+H] + ; 1 H NMR (400 MHz, DMS-d 6 ): 7.58 (1H, d, J = 2.0 Hz, H-2 ), 7.48 (1H, dd, J = 8.8, 2.0 Hz, H-6 ), 6.93 (1H, d, J = 8.8 Hz, H-5 ), 7.42 (1H, dd, J = 8.4, 2.0 Hz, H-6 ), 7.40 (1H, d, J = 2.0 Hz, H-2 ), 6.91 (1H, d, J = 8.4 Hz, H-5 ), 6.78 (1H, d, J = 2.0 Hz, H-8), 6.75 (1H, d, J = 2.0 Hz, H-8 ), 6.74 (1H, s, H-3), 6.43 (1H, d, J = 2.0 Hz, H-6), 6.40 (1H, d, J = 2.0 Hz, H-6 ), 5.08 (1H, d, J = 6.8 Hz, Glc, H-1 ), 3.78 (3H, s, 3 -Me), (1H, s, 5-), (1H, s, 5 -), (1H, s, 4 -), 9.84 (1H, s, 4 -), 9.41 (1H, s, 3 -); 13 C NMR (DMS-d 6 ) see Table 1. Apigenin (2) Yellow powder; mp > 310 C; UV max (Me) nm (log ): 270, 320, 325; IR (KBr) max 3287, 3094 (), 2924, 1653 (C=), 1608 and 1502 (Ar), 1444, 1181, 829 cm -1 ; EIMS m/z (%): 270 (M +, 100), 269 (18), 242 (11), 153 (5), 121 (2), 118 (1); 1 H NMR (400 MHz, DMS-d 6 ): 7.92 (2H, d, J = 8.8 Hz, H-2,6 ), 6.92 (2H, d, J = 8.8 Hz, H-3,5 ), 6.77 (1H, s, H-3), 6.48 (1H, d, J = 1.6 Hz, H-8), 6.18 (1H, d, J = 1.6 Hz, H-6), (1H, s, 5-), and (each 1H, s, 7- and 4 -). Luteolin (3) Yellow powder; mp > 310 C; UV max (Me) nm (log ): 254, 291, 351; EIMS m/z (%): 286 (M +, 100), 258 (15), 153 (26), 134 (10); 1 H NMR (400 MHz, DMS-d 6 ): 7.41 (2H, m, H-2, 6 ), 6.88 (1H, d, J = 8.4 Hz, H-5 ), 6.66 (1H, s, H-3), 6.43 (1H, s, H-8), 6.17 (1H, s, H-6), (1H, s, 5-), (1H, s, 7-), 9.93, 9.41 (each 1H, s, 3 -, 4 -). Chrysoeriol (4) Yellow powder; mp > 310 C; UV max (Me) nm (log ): 242, 277, 341; IR (KBr) max : 3351 (), 3086, 2960, 1651 (C=), 1598 and 1508 (Ar), 1299, 1033, 836 cm -1 ; 1 H NMR (400 MHz, DMS-d 6 ): 7.54 (2H, m, H-2, 6 ), 6.93 (1H, d, J = 8.4 Hz, H-5 ), 6.90 (1H, s, H-3), 6.50 (1H, d, J = 2.0 Hz, H-8), 6.18 (1H, d, J = 2.0 Hz, H-6), (1H, s, 5-), (1H, s, 7-), 9.97 (1H, s, 4 -), 3.87 (3H, s, 3 -CH 3 ). Tricin (5) Yellow powder; mp C; UV max (Me) nm (log ): 270, 348; IR (KBr) max : 3450 (), 1660, 1610 and 1500 (Ar), 1095, 1075, 1028 cm -1 ; 1 H NMR (400 MHz, DMS-d 6 ): 7.25 (1H, s, H-2, 6 ), 6.82 (1H, s, H-3), 6.45

6 634 J. Chin. Chem. Soc., Vol. 51, No. 3, 2004 Deng et al. (1H, d, J = 1.6 Hz, H-8), 6.18 (1H, d, J = 1.6 Hz, H-6), 3.86 (6H, s, 3 -CH 3 and 5 -CH 3 ), (1H, s, 5-). Hispidulin (6) Pale yellow needles; mp C, UV max (Me) nm (log ): 274, 334; IR (KBr) max : 3360 (), 1654 (C=) 1605 and 1505 (Ar), 1263, 1149, 1024, 836 cm -1 ; EIMS m/z (%): 300 (M +, 100), 299 (14), 285 (68), 282 (61), 271 (10), 257 (71), 167 (19), 139 (24), 121 (5); 1 H NMR (400 MHz, DMS-d 6 ): 7.92 (2H, d, J = 8.4 Hz, H-2,6 ), 6.91 (2H, d, J = 8.4 Hz, H-3, 5 ), 6.77 (1H, s, H-3), 6.57 (1H, s, H-8), 3.73 (3H, s, 6-CH 3 ), (1H, s, 5-), (1H, s, 7-), (1H, s, 4 -). Pectolinarigenin (7) Yellow needles; mp C; UV max (Me) nm (log ): 274, 330; IR (KBr) max : 3290 (), 1650 (C=), 1603 and 1506 (Ar) cm -1 ; EIMS m/z (%): 314 (100), 313 (11), 285 (22), 167 (19), 135 (21), 111 (10); 1 H NMR (400 MHz, DMS-d 6 ): 8.05 (2H, d, J = 8.8 Hz, H-2, H-6 ), 7.12 (2H, d, J = 8.8 Hz, H-3, H-5 ), 6.88 (1H, s, 3-H), 6.62 (1H, s, H-8), 3.75, 3.86 (each 3H, s, 4 -CH 3 and 6-CH 3 ). Eupatilin (8) Yellow crystals; mp: C; UV max (Me) nm (log ): 238, 272, 340; IR (KBr) max : 3320 (), 1654 (C=), 1620, 1577 and 1495 (Ar), 1262, 992, 816 cm -1 ; EIMS m/z (%): 344 (M + 100), 343 (8), 329 (70), 301 (10), 167 (14), 165 (6), 139 (22), 111 (5); 1 H NMR (400 MHz, DMS-d 6 ): 7.68 (1H, dd, J = 8.8, 2.0 Hz, H-6 ), 7.55 (1H, d, J = 2.0 Hz, H-2 ), 7.12 (1H, d, J = 8.8 Hz, H-5 ), 6.96 (1H, s, H-3), 6.63 (1H, s, H-8), 3.76 (3H, s, 6-CH 3 ), 3.85, 3.88 (each 3H, s, 3 -, 4 -CH 3 ), (1H, s, 5-), (1H, s, 7-). 5,7-Dihydroxy-6,3,4,5 -tetramethoxyflavone (9) Yellow powder; mp C; UV max (Me) nm (log ): 277, 333; EIMS m/z (%): 374 (M +, 100), 373 (7), 359 (60), 344 (15), 331 (40), 193 (7); 1 H NMR (400 MHz, DMS-d 6 ): 7.32 (2H, s, H-2, H-6 ), 7.06 (1H, s, H-3), 6.67 (1H, s, H-8), 3.73 (3H, s, 4 -CH 3 ), 3.74 (6H, s, 3 -, 5 - CH 3 ), 3.88 (3H, s, 6-CH 3 ), (1H, s, 5-), (1H, s, 7-). 5,7,4 -Trihydroxy-6,3,5 -trimethoxyflavone (10) Pale yellow powder; mp C; UV max (Me) nm (log ): 276, 351; IR (KBr) max : 3450 (), 1651 (C=), 1604, 1520 and 1470 (Ar), 1360, 1170, 1012, 830 cm -1 ; EIMS m/z (%): 360 (M +, 100), 359 (10), 345 (79), 317 (37), 179 (13), 167 (9), 153 (5), 139 (10); 1 H NMR (400 MHz, DMS-d 6 ): 7.17 (2H, d, J = 2.0 Hz, H-2, H-6 ), 6.93 (1H, s, H-3), 6.60 (1H, s, H-8), 3.75, 3.76 (each 3H, s, CH 3,3 -, 5 - CH 3 ), 3.89 (3H, s, 6-CH 3 ), (1H, s, 5-), (1H, s, 7-), 9.67 (1H, s, 4 -). 3,6--dimethylquercetagetin-7-- -D-glucoside (11) Yellow powder; mp C; UV max (Me) nm (log ): 260, 272, 355; IR (KBr) max : 3450, 1660, 1605, 1468, 1035, 1028, 848, 802 cm -1 ; FAB-MS m/z: 509[M+H] + ; 1 H NMR (400 MHz, DMS-d 6 ): 7.58 (1H, d, J = 2.4 Hz, H-2 ), 7.45 (1H, dd, J = 8.4 Hz, 2.4 Hz, H-6 ), 6.98 (1H, d, J = 8.4 Hz, H-5 ), 6.79 (1H, s, H-8), 5.46 (1H, d, J = 7.0 Hz, Glc H-1 ), 3.67, 3.80 (each 3H, s, 3-CH 3 and 6-CH 3 ), (1H, s, 5-), 9.86, 9.42 (each 1H, s, 3 -, 4 -). 6-Hydroxy-5,7-dimethoxy-coumarin (12) White needles; mp C; IR (KBr) max : 3240 (), 2986, 2948, 1694, 1570, 1498, 1413, 1325, 1028, 845; EIMS m/z (%): 222 (M +, 100), 207 (33), 179 (10), 123 (23), 95 (12), 79 (13), 51 (16); 1 H NMR (400 MHz, DMS-d 6 ): 7.95 (1H, d, J = 9.6 Hz, H-4), 6.64 (1H, s, H-8), 6.39 (1H, d, J = 9.6 Hz, H-3), 3.77 (3H, s, 7-CH 3 ), 3.82 (3H, s, 5-CH 3 ); 13 C NMR (100 MHz, DMS-d 6 ): (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), (C-8), (C-9), (C-10), 60.5 (7-CH 3 ), 55.9 (5-CH 3 ). Taraxerol (13) White crystals; mp C; IR (KBr) max : 3485 (), 3052, 2997, 2932, 2855, 1640, 1471, 1381, 1376 cm -1 ; EIMS m/z (%): 426 (M +, 20), 411 (12), 302 (44), 204 (100), 189 (34); 1 H NMR (400 MHz, CDCl 3 ): 5.51 (1H, dd, J = 10.8, 2.8 Hz, H-15), 3.17 (1H, dd, J = 9.2, 4.4 Hz, H-3), 1.08, 0.96, 0.94, 0.92, 0.89, 0.87, 0.80, 0.77 (each 3H, s, 8 CH 3 ). Taraxeryl acetate (14) White powder; mp C; IR (KBr) max : 3435 (), 3052, 2932, 2908, 2832, 1724, 1473, 1376, 1250 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ): 5.52 (1H, dd, J = 8.4, 3.6 Hz, H-15), 4.45 (1H, dd, J = 10.0, 6.4 Hz, H-3), 2.02 (3H, s, CH 3 ), 1.06, 0.96, 0.94, 0.90, 0.88, 0.85, 0.83, 0.79 (each 3H, s, 8 CH 3 ). -Sitosterol (15) and stigmasterol (16) White slices; mp C; EIMS m/z: 414 (M + ) and 412 (M + ) (3:2); physical data were consistent with literature value.

7 Chemical Components of Seriphidium santolium Poljak J. Chin. Chem. Soc., Vol. 51, No. 3, A mixture of the n-alkyl trans-p-coumarates (17) White powder; mp C; IR (KBr) max cm -1 : 3384 (), 2952, 2921, 2847, 1674, 1602, 1585, 1514, 834, 721 cm -1 ; EIMS m/z (%): 500 (M c +, 0.6), 472 (M b +, 1.16), 444 (M a +, 1.31), 165 (31), 164 (100); 1 H NMR (400 MHz, CDCl 3 ): 7.62 (1H, d, J = 16.8 Hz, Ar-CH=), 7.41 (2H, d, J = 9.6 Hz, arom. H meta to ), 6.84 (2H, d, J = 9.6 Hz, arom. H ortho to ), 6.30 (1H, d, J = 16.8 Hz, =CH-C 2 R), 4.18 (2H, t, J = 6.8 Hz, -CCH 2 ), 1.70 (2H, quin, -CCH 2 CH 2 ), (about 38H, m, CH 2 ), 0.85 (3H, t, J = 6.8 Hz, CH 3 ). A mixture of the n-alkyl trans-ferulates (18) White powder; mp C; IR (KBr) max : 3510, 3464, 2954, 2919, 2849, 1723 (CR), 1684, 1601, 1517, 1177, 1027, 821, 722 cm -1 ; EIMS m/z (%): 530 (M c +, 0.89), 502 (M b +, 26), 474 (M a +, 49), 194 (100), 177 (78), 164 (100); 1 H NMR (400 MHz, CDCl 3 ): 7.63 (1H, d, J = 16.8 Hz, Ar-CH=), 7.09 (1H, dd, J = 8.0, 1.6 Hz, H-6), 7.04 (1H, d, J = 1.6 Hz, H-2), 6.93 (1H, d, J = 8.0 Hz, H-5), 6.30 (1H, d, J = 16.8 Hz, =CH-C 2 R), 5.87 (1H, s, 4-), 4.20 (2H, t, J = 6.8 Hz, -CCH 2 ), 3.93 (3H, s, 3-CH 3 ), 1.70 (2H, quin, -CCH 2 CH 2 ), (about 38H, m, CH 2 ), 0.86(3H, t, J = 6.8 Hz, CH 3 ). 2-Hydroxy-4,6-dimethoxyacetophenone (19) White needles; mp C; IR (KBr) max : 3100, 3007, 2944, 2849, 1619, 1570, 1503, 1458, 1367, 1157, 836 cm -1 ; EIMS m/z (%): 196 (M +, 3), 181 (100), 166 (9), 138 (6), 69 (9), 43 (16); 1 H NMR (400 MHz, CDCl 3 ): 6.02 (1H, d, J = 2.4 Hz, H-3), 5.89 (1H, d, J = 2.4 Hz, H-5), 3.82 (3H, s, CH 3 ), 3.77 (3H, s, CH 3 ), 2.57 (3H, s, CMe). 4-Hydroxy-2,6-dimethoxyphenol-1-- -D-glucopyranoside (20) Colorless powder; mp C; UV max (Me) nm (log ): 278; IR (KBr) max : 3385, 3003, 2940, 1608, 1518, 1225, 1123, 1029, 816 cm -1 ; FABMS m/z: 331[M-H] ; 1 H NMR (400 MHz, DMS-d 6 ): 8.53 (1H, s, 4-), 6.32 (2H, s, 3-, 5-H), 5.24 (1H, d, J = 8.4 Hz,, Glc, H-1 ), 3.88 (6H, s, 2 CH 3 ). 2-Hydroxycinnamoyl- -D-glucopyranoside (21) White needles; mp C; UV max (Me) nm (log ): 272, 328; IR (KBr) max : 3381, 2928, 1699, 1628, 1492, 1235, 1075, 761 cm -1 ; 1 H NMR (400 MHz, DMD-d 6 ): 7.82 (1H, d, J = 16.0 Hz), 7.53 (1H, dd, J = 8.0, 2.0 Hz), 7.36 (1H, ddd, J = 8.0, 7.2, 2.0 Hz), 7.23 (1H, dd, J = 8.0, 2.0 Hz), 7.06 (1H, ddd, J = 8.0, 7.2, 2.0 Hz), 6.40 (1H, d, J = 16.0 Hz), 5.00 (1H, d, J = 7.6 Hz,, Glc, H-1 ). Hydrolysis of compound 1 Compound 1 (10 mg), 15% HCl (10 ml) and C 6 H 6 (10 ml) were mixed and refluxed for 10 hr. After neutralization of the aq. layer, the soln was filtered and concd. D-Glucose in compound 1 was identified by PC using EtAc-pyridine- H 2 (12:5:4) as developing solvent. 25 ACKNWLEDGEMENT We thank Professor Li-Yun Zhang (Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, Urumqi, P. R. China) for the plant identification. Received ctober 7, REFERENCES 1. Editorial Committee of Zhongguozhiwuzhi, Chinese Academy of Sciences, Zhongguozhiwuzhi; Science Press: Beijing, 1991, 76(2), p Boriky, D.; Berrada, M.; Talbl, M.; Keravis, G.; Rouessac, F. Phytochemistry 1996, 43, Cheng, J. Y.; Cheng, J. M.; Xiao, P. G. Tianranchanwuyanjiuyukaifa 1997, 9,5. 4. Markham, K. R.; Ternai, B.; Stanley, R.; Geiger, H.; Mabry, T. J. Tetrahedron 1978, 34, Wager, H.; Chari, V. M.; Sonnenbichler, J. Tetrahedron Letters 1976, 21, Li, F.; Liu, Y. L. Yaoxuexuebao 1988, 23, Kupchan, S. M.; Sigel, C. W.; Hemingway, R. J.; Knox, J. R.; Udayamurthy, M. S. Tetrahedron 1969, 25, Mues, R.; Timmermann, B. N.; hno, N.; Mabry, T. J. Phytochemistry 1979, 18, Liu, Y. L.; Mabry, T. J. Phytochemistry 1981, 20, Marco, J. A.; Barbera,.; Rodriguez, S.; Domingo, C.; Adell, J. Phytochemistry 1988, 27, Herz, W.; Govindan, S. V.; Riess-Maurer, I.; Kreil, B.; Wagner, H.; Farkas, L.; Strelisky, J. Phytochemistry 1980, 19, Bacon, J. D.; Urbatsch, L. E.; Bragg, L. H.; Mabry, T. J.; Neuman, P.; Jackson, D. W. Phytochemistry 1978, 17, Wagner, H.; Bladt, S. Phytochemistry 1975, 14, Sakurai, N.; Yaguchi, Y.; Inoue, T. Phytochemistry 1987, 26, Koul, Summon.; Razdan, T. K.; Andotra, C. S.; Kalla, A. K.; Koul, S.; Taneja, S. C.; Dhar, K. L. Phytochemistry 2000, 53,

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