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1 This article was downloaded by: [ ] On: 09 June 2015, At: 08:26 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: Registered office: Mortimer House, Mortimer Street, London W1T 3JH, UK Bioscience, Biotechnology, and Biochemistry Publication details, including instructions for authors and subscription information: New Phenolic Compounds from Kokuto, Noncentrifuged Cane Sugar Kensaku TAKARA a, Daigo MATSUI a, Koji WADA a, Toshio ICHIBA b, Isao CHINEN a & Yoko NAKASONE a a Laboratory of Applied Biochemistry, Department of Bioscience and Biotechnology, Faculty of Agriculture, University of the RyukyusSenbaru 1, Nishihara-cho, Okinawa , Japan b Okinawa Industrial Technology Center Published online: 22 May To cite this article: Kensaku TAKARA, Daigo MATSUI, Koji WADA, Toshio ICHIBA, Isao CHINEN & Yoko NAKASONE (2003) New Phenolic Compounds from Kokuto, Non-centrifuged Cane Sugar, Bioscience, Biotechnology, and Biochemistry, 67:2, , DOI: /bbb To link to this article: PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content ) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at

2 Biosci. Biotechnol. Biochem., 67 (2), , 2003 Note New Phenolic Compounds from Kokuto, Non-centrifuged Cane Sugar Kensaku TAKARA, 1, Daigo MATSUI, 1 Koji WADA, 1 Toshio ICHIBA, 2 Isao CHINEN, 1 andyokonakasone 1 1 Laboratory of Applied Biochemistry, Department of Bioscience and Biotechnology, Faculty of Agriculture, University of the Ryukyus, Senbaru 1, Nishihara-cho, Okinawa , Japan 2 Okinawa Industrial Technology Center, Suzaki 12-2, Gushikawa-shi, Okinawa , Japan Received June 21, 2002; Accepted October 2, 2002 Five new phenolic compounds, 4-(b-D-glucopyranosyloxy)-3,5-dimethoxyphenyl-propanone (8), 3-[5- [(threo) 2,3-dihydro-2-(4-hydroxy-3-methoxyphenyl)-3- hydroxymethyl-7-methoxybenzofurany]]-propanoic acid (12), 2-[4-(3-hydroxy-1-propenyl)-2,6-dimethoxyphenoxy]-3-hydroxy-3-(4-hydroxy-3,5-dimethoxyphenyl)propyl-b-D-glucopyranoside (13), 4-[(erythro) 2,3-dihydro-3(hydroxymethyl)-5-(3-hydropropyl)-7- methoxy-2-benzofuranyl]-2,6-dimethoxyphenyl-b-dglucopyranoside (14), 9-O-b-D-xylopyranoside of icariol A 2 (15), and known phenolic compounds were isolated from Kokuto, non-centrifuged cane sugar (Saccharum o cinarum L.). Their structures were determined by a spectral investigation. Key words: cane sugar; Saccharum o cinarum L.; Kokuto; phenolic compounds In the course of our screening program for hydroxyl radical scavengers, we have isolated seventeen phenolic compounds from the CH 2 Cl 2 extracts and nine phenolic compounds from the 40z methanol and 60z methanol eluates by Amberlite XAD-2 column chromatography of Kokuto, non-centrifuged cane sugar. 1 3) Further examination of the constituents has now resulted in the isolation of ˆve new phenolic compounds (8, 12 15), as well as the nine known compounds (1 7, 9 11) previously reported. 4 12) Compound 8 isolated as a colorless amorphous powder had the molecular formula C 17 H 24 O 9 (positive HR-ESIMS, m W z [M+Na] + ). The NMR spectra of 8 indicated the presence of 1-(4- hydroxy-3,5-dimethoxyphenyl)-propanone and a D- glucopyranose moiety. In the 1 H-NMR spectrum, the coupling constant of an anomeric proton at d5.09 was J=7.6 Hz, showing a b-linkage. In the HMBC spectrum, the carbon signals at d140.4 (C-4) showed correlation with the anomeric proton at d5.09, suggesting the glucose moiety to be connected to C-4. Further assignment of the proton and carbon signals was achieved by a combination of 1 H 1 HCOSYand HMQC spectral data. The structure of 8 was thus determined to be 1-[4-(b-D-glucopyranosyloxy)-3,5- dimethoxyphenyl]-1-propanone. Compound 12 isolated as a colorless oil had the molecular formula C 20H 22O 7 (negative HR- APCIMS, mwz [M-H] ). The NMR spectra of 12 were similar to those of dehydrodiconiferyl alcohol reported in the preceding paper of this series, 2) except for the presence of two methylene carbons and a carboxyl group. The assignment of the proton and carbon signals was achieved by a combination of the HMQC, HMBC, DEPT, and 1 H 1 H COSY spectral data. The coupling of 6.3 Hz between the H-7 and H-8 protons suggested a threo type of relative con- ˆguration. 11) Compound 12 was therefore determined to be 3[5-[(threo) 2,3-dihydro-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-7-methoxybenzofuranyl]]-propanoic acid. The absolute conˆgurations at C-7 and C-8 could not be determined, because the amount of the sample was too small. Compound 13 was isolated as a colorless oil, and it had the molecular formula C 28 H 38 O 14 (negative HR- APCIMS, m W z [M-H] ). The NMR spectra of 13 indicated the presence of one sinapyl alcohol, one syringoylglycerol, and one glucopyranose moiety. In addition, acid hydrolysis of 13 with 0.2 N H 2 SO 4 ašorded glucose. Further spectral evidence enabled 13 to be deduced as analogous to 3-hydroxy- 1-(4-hydroxy-3,5-dimethoxyphenyl)-2-[4-(3-hydroxy- 1-(E )-propenyl)-2,6-dimethoxyphenoxy]propyl-b-dglucopyranoside (13-a) with had previously been isolated in our study. 3) In the HMBC spectrum, the carbon signals at d69.6 (C-9) showed correlation with the anomeric proton at d4.31 ( J=7.8 Hz), suggesting To whom correspondence should be addressed. k-takara@agr.u-ryukyu.ac.jp Abbreviations: HMQC, 1 H-detected heteronuclear multiple quantum coherence; HMBC, 1 H-detected heteronuclear multiple bond correlation; 1 H 1 HCOSY, 1 H 1 H correlation spectroscopy; DEPT, distortionless enhancement by polarization transfer; FAB-MS, fast atom bombardment mass spectrometry; APCI-MS, atmospheric pressure chemical ionization mass spectrometry; ESI-MS, electrospray ionization mass spectrometry; HRMS, high-resolution mass spectrometry

3 New Phenolic Compounds from Kokuto 377 Fig. 1. the b-glucose moiety to be connected to the C-9 carbon. The position of the sinapyl alcohol moiety linkage indicated that C-4? of sinapyl alcohol was connected at C-8 by an ether linkage, compared with that of 13-a. The structure of 13 was therefore determined to be 2-[4-(3-hydroxy-1-propenyl)-2,6-dimethoxyphenoxy]-3-hydroxy-3-(4-hydroxy-3,5-dimethoxyphenyl)propyl-b-D-glucopyranoside. Compound 14 isolated as a colorless oil showed the molecular formula C 27H 36O 12 (positive HR-ESIMS, m W z [M+Na] + ). The NMR spectra of 14 were similar to those of 2-(4-hydroxy-3,5-dimethoxy- phenyl)-3-hydroxymethyl-5-(3-hydroxy-1-propenyl)- 7-methoxycoumarane reported in the previous paper, 2) except for the presence of one additional methoxyl group, one D-glucopyranose moiety, and a hydroxyl propane group instead of a hydroxyl propenyl group. In the HMBC spectrum, the carbon signals at d137.2 showed correlation with the anomeric proton at d4.90 ( J=7.8 Hz), suggesting the b- glucose moiety to be connected to the phenolic carbon (C-4). The coupling of 5.8 Hz between the H-7 and H-8 protons suggested an erythro type of relative conˆguration. 12) Compound 14 was therefore determined to be 4-[(erythro) 2,3-dihydro-3-hydroxymethyl-5-(3-hydroxypropyl)-7-methoxy-2-benzofuranyl]-2,6-dimethoxyphenyl-b-D-glucopyranoside. The absolute conˆgurations at C-1 and C-8 could not be determined, because the amount of the sample was too small. Compound 15 wasisolatedasacolorlessoiland Chemical Structures of the New Phenolic Compounds Isolated from Kokuto. had the molecular formula C 27H 36O 13 (positive HR- FABMS, mwz [M+Na] + ). The 13 C-NMR spectrum indicated the presence of two symmetrical parts and one sugar moiety. The 1 H-NMR spectrum indicated the presence of a 2,5-diaryl tetrahydrofuran type of lignan. The 13 C signal pattern of the sugar moiety and coupling constant ( J=7.5 Hz) of the anomeric proton suggested that 15 contained b-dxylopyranose. In the HMBC spectrum, the carbon signal at d69.1 (C-9) showed correlation with the anomeric proton, suggesting the xylose moiety to be connected to C-9. Further assignment of the proton and carbon signals was achieved by a combination of 2D-NMR and comparison with icariol A 2, 13) the planar structure of 15 indicating the 9-O-b-Dxylopyranoside of icariol A 2. Compounds 8, 12, 13, 14 and 15 are new phenolic compounds. Experimental The instruments used and the experimental conditions for obtaining spectral data and for chromatography were the same as those reported in the preceding paper. 3) Extraction and Isolation. The sample material and extraction methods were the same as those described in the previous paper. 3) The 80z methanol and 100z methanol eluates by Amberlite XAD-2 column chromatography of Kokuto (2.4 kg) were combined and then partitioned between water and n-butanol. The

4 378 K. TAKARA et al. n-butanol layer (12 g) was chromatographed over silica gel [CH 2Cl 2 MeOH (30:1, 15:1, 5:1, 1:1), and MeOH] to give ˆve fractions (fractions 1 5). Vanillic acid (1, 47.9 mg) was isolated from fraction 1, and 4- hydroxybenzaldehyde (2, 42.3 mg) and 4-hydroxybenzoic acid (3, 5.8 mg) were isolated from fraction 2. Fraction 3 was subjected to Sephadex LH-20 column chromatography to give four fractions (frs ). Fraction 3-2 was crystallized from methanol to give 3,4-dimethoxyphenyl-O-b-D-glucopyranoside (4, 21.1 mg). The residue was subjected to LiChroprep RP-8 column chromatography to give 2,4,6-trimethoxyphenyl-b-D-glucopyranoside (7, 16.6 mg) and four fractions (frs ). 3,4,5- Trimethoxyphenylglycerol (5, 7.7 mg) and 3,4,5- trimethoxyphenyl-o-b-d-glucopyranoside (6,6.9mg) were isolated from fraction 3-2-3, and from fraction 3-2-4, 8 (6.7 mg) was isolated by HPLC (ODS). Fraction 3-3 (520 mg) was subjected to LiChroprep RP-8 column chromatography [MeOH H 2O (3:7 1:1)] to give seven fractions (frs ). Methylsalicylate-b-D-glucopyranoside (9, 23.2 mg) and 4-(b- D-glucopyranosyloxy)-3-methoxyphenyl-propanone (10, 4.7 mg) were isolated from fraction 3-3-5, and syringaresinol-4?-o-b-d-glucopyranoside (11, 29.2 mg) was isolated from fraction Fraction 3 4 yielded 12 (3.2 mg) after LiChroprep RP-8 column chromatography [MeOH H 2O (3:7 1:1)] and HPLC (ODS). Fraction 4 (2.59 g) was subjected to Sephadex LH-20 column chromatography [MeOH H 2O (1:5 3:2)] to give sixteen fractions (frs ). Fraction 4-4 (252 mg) was subjected to LiChroprep RP-8 column chromatography [MeOH H 2 O (1:4 1:1)] and HPLC (ODS) to give 13 (8.3 mg) and 14 (3.4 mg). Fraction 4 6 (112 mg) yielded 15 (21.1 mg) after LiChroprep RP-8 column chromatography [MeOH H 2O (30:70 35:65)] and HPLC (ODS). 4-(b-D-Glucopyranosyloxy)-3,5-dimethoxyphenylpropanone (8). APCI-MS (negative) m W z 371 [M-H]. HR-ESIMS (positive): calcd. for C 17H 24- O 9 Na, m W z ; found, [M+Na] +. UV l max (nm): 217, 275. IR n max cm 1 : 3400, 1678, 1589, H-NMR (CD 3OD) d: 7.33(2H,s,H-2, 6), 5.09 ( 1 H, J=7.6 Hz, H-1?), 3.90 (6H, s, 3, 5-OMe), 3.76 ( 1 H, J=11.9,5.3Hz,H-6?a), 3.64 ( 1 H, J=12.1,2.3Hz,H-6?b), 3.49 ( 1 H, m, H-2?), 3.41 (2H, m, H-3?, 4?), 3.21 (1H, m, H-3?), 3.04 (2H, q, J=7.33 Hz, H-8), 1.17 (3H, t, J=7.3 Hz, H-9). 13 C- NMR (CD 3OD) d: (C-7), (C-3, 5), (C-4), (C-1), (C-2, 6), (C-1?), 78.5 (C-3?), 77.9 (C-5?), 75.7 (C-2?), 71.3 (C-4?), 62.5 (C-6?), 57.1 (3, 5-OMe), 32.5 (C-8), 8.7 (C-9). 3-[5-[(Threo) 2,3-dihydro-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-7-methoxybenzofuranyl]]-propanoic acid (12). APCI-MS (negative) m W z 373 [M-H]. HR-APCIMS (negative): calcd. for C 20 H 21 O 7, ; found, [M-H].UV l max (nm): 203, 235 (sh), 280. IR n max cm 1 : 3440, 1716, 1610, 1502, 1276, H-NMR (CD 3OD) d: 6.84 (6.84, 1 H, d, J=2.0 Hz, H-2), 6.81 (1H, dd, J=8.6, 2.0 Hz, H-6), 6.75 (3H, m, H-5, 2?, 6?), 5.49 (1H, d, J=6.3Hz,H-7),3.84(3H,s,3?-OMe), 3.82 (1H, m, H-9a), 3.80 (3H, s, 3-OMe), 3.75 (1H, dd, J=11.1, 7.2 Hz, H-9b), 3.46 (1H, brbb, J=12.5, 6.3 Hz, H-8), 2.85 (2H, t, J=7.6 Hz, H-7?), 2.57 (2H, t, J=7.7 Hz, H-8?). 13 C-NMR (CD 3OD) d: (C-9?), (C-3), (C-4?), (C-4), (C-3?), (C-1?), (C-1), (C-5?), (C-6), (C-2?), (C-5), (C-6?), (C-2), 89.0 (C-7), 64.9 (C-9), 56.7 (3?-OMe), 56.4 (3-OMe), 55.4 (C-8), 37.5 (C-8?), 32.0 (C-7?). 2-[4-(3-Hydroxy-1-propenyl)-2,6-dimethoxyphenoxy]-3-hydroxy-3-(4-hydroxy-3,5-dimethoxyphenyl)propyl-b-D-glucopyranoside (13). APCI-MS (negative) m Wz 597 [M-H]. FAB-MS (positive, glycerol) m W z 621 [M+Na] +. HR-APCIMS (negative): calcd. for C 28H 37O 14, ; found, [M-H].UVl max (nm): 206, 225 (sh), 270. IR n max cm 1 : 3400, 1590, 1508, 1462, 1225, H- NMR (CD 3OD) d:6.73(2h,s,h-2?,6?), 6.65 (2H, s, H-2, 6), 6.54 (1H, d, J=15.9 Hz, H-7?), 6.31 (1H, dt, J=15.9, 5.6 Hz, H-8?), 4.88 (1H, d, J=4.6 Hz, H-7), 4.47 (1H, m, H-8a), 4.31 (1H, d, J=7.8 Hz, H-1!), 4.22 (2H, dd, J=5.7, 1.4 Hz, H-9?), 4.02 (1H, dd, J=11.3, 3.7 Hz, H-9), 3.94 (1H, dd, J=11.3, 5.7 Hz, H-8b), 3.84 (6H, s, 3, 5-OMe), 3.81 (1H, m, H-6!a),3.80(6H,s,3?,5?-OMe), 3.63 (1H, dd, J=11.9,5.5Hz,H-6!b),3.34(1H,m,H-5!), 3.27 (1H, m, H-4!), 3.22 (1H, m, H-3!), 3.17 (1H, dd, J=9.2, 7.9 Hz, H-2!). 13 C-NMR (CD 3OD) d: (C-3?, 5?), (C-3, 5), (C-4?), (C-4), (C-1?), (C-1), (C-7?), (C-8?), (C-2, 6), (C-1!), (C-2?, 6?), 86.1 (C-8), 78.0 (C-3!), 77.8 (C-5!), 75.2 (C-2!), 74.1 (C-7), 71.5 (C-4!), 69.6 (C-9), 63.6 (C-9?), 62.6 (C-6!),56.7(3,5,3?, 5?-OMe). Acid hydrolysis of compound 13. Compound 13 (1 mg) was dissolved in 0.2 N H 2SO 4 (2 ml) at 959C for 2 h. After cooling, the reaction mixture was extracted with EtOAc. The aqueous layer was neutralized with NaHCO 3, concentrated to dryness, and extracted with pyridine. The sugar in the pyridine extract was identiˆed as its acetyl derivative by GC. Conditions: column, J&W DB-1 30 m 0.25 mm; column temp, 1509C(1 min)ª59c Wminª1809Cª 29CWminª2109C(1 min); carrier gas, N 2; R t min (glucose acetate).

5 4-[(Erythro)2,3-dihydro-3(hydroxymethyl)-5-(3- hydropropyl)-7-methoxy-2-benzofuranyl]-2,6-dimethoxyphenyl-b-d-glucopyranoside (14). ESI-MS (positive) mwz 575 [M+Na] +. FAB-MS (positive, glycerol) m W z 575 [M+Na] +. FAB-MS (positive, glycerol) m Wz 591 [M+K] +. HR-ESIMS (positive): calcd. for C 27H 36O 12Na, ; found, [M+Na] +.UVl max (nm): 206, 236 (sh), 270. IR n max cm 1 : 3400, 1608, 1463, 1330, 1219, 1118, H- NMR (CD 3 OD) d: 6.73(3H,s,H-2,6,6?), 6.70 (1H, s, H-2?), 5.55 (1H, d, J=5.8 Hz, H-7), 4.90 (1H, d, J=7.8 Hz, H-1!), 3.87 (3H, s, 3?-OMe), 3.86 (1H, m, H-9a), 3.81 (6H, s, 3, 5-OMe), 3.78 (1H, m, H-6!a),3.76(1H,m,H-9b),3.65(1H,dd,J=11.9, 5.2 Hz, H-6!b), 3.55 (2H, t, J=6.4 Hz, H-9?), 3.47 (1H, m, H-2!), 3.44 (1H, m, H-8), 3.40 (2H, m, H-4!, 5!), 3.19 (1H, m, H-3!), 2.61 (2H, t, J=7.7 Hz, H-7?), 1.80 (2H, m, H-8?). 13 C-NMR (CD 3OD) d: (C-3, 5), (C-1), (C-3?), (C-4?), (C-1?), (C-4), (C-5?), (C-2?), (C-6?), (C-1!), (C-2, 6), 88.5 (C-7), 78.3 (C-3!), 77.8 (C-5!), 75.7 (C-2!), 71.3 (C-4!), 65.1 (C-9), 62.6 (C-6!), 62.2 (C-9?), 57.0 (3, 5-OMe), 56.8 (3?-OMe), 55.8 (C-8), 35.8 (C-8?), 32.9 (C-7?). 9-O-b-D-xylopyranoside of icariol A 2 (15). FAB- MS (negative, glycerol) m W z 567 [M-H].ESI-MS (positive) mwz 591 [M+Na] +. APCI-MS (negative) m W z 567 [M-H]. HR-FABMS (positive): calcd. for C 27H 36O 13Na, ; found, [M+Na] +. UV l max nm:206,236,270.irn max cm 1 : 3400, 1614, 1518, H-NMR (CD 3OD) d: 6.75(2H,s,H-2, 6),6.74(2H,s,H-2?, 6?), 5.03 (1H, d, J=8.2 Hz, H-7?), 4.99 (1H, d, J=8.4 Hz, H-7), 4.21 (1H, d, J=7.5 Hz, H-1!), 3.92 (1H, dd, J=10.1, 4.7 Hz, H-9a), 3.85 (6H, s, 2-, 6-, 2?-, 6?-OMe), 3.84 (1H, m, H-5!a), 3.78 (1H, dd, J=11.6, 3.7Hz, H-9?a), 3.73 (1H, dd, J=9.8, 3.7 Hz, H-9b), 3.63 (1H, dd, J=11.6, 3.9 Hz, H-9?b), 3.48 (1H, ddd, J=10.2, 8.9, 3.5 Hz, H-4!), 3.28 (1H, d, J=8.9 Hz, H-3!), 3.19 (2H, m, H-2!, 5!b),2.41(2H,m,H-8,8?). 13 C- NMR (CD 3OD) d: (C-3, 5, 3?, 5?), (C-1 or 1?), (C-1 or 1?), (C-4, 4?), (C-1!), (C-2, 6), (C-2?, 6?), 84.3 (C-7 or 7?), 84.0 (C-7 or 7?), 78.0 (C-3!), 75.0 (C-2!), 71.2 (C-4!), 69.1 (C-9), 67.1 (C-5!), 61.0 (C-9?), 56.8 (3-, 5-, 3?-, 5?-OMe), 54.3 (C-8 or C-8?), 52.1 (C-8 or C-8?). New Phenolic Compounds from Kokuto References 379 1) Nakasone, Y., Takara, K., Wada, K., Tanaka, J., and Yogi, S., Antioxidative compounds isolated from Kokuto, non-centrifuged cane sugar. Biosci. Biotechnol. Biochem., 60, (1996). 2) Takara, K., Kinjyo, A., Matsui, D., Wada, K., Nakasone, Y., and Yogi, S., Antioxidative phenolic compounds from the non-sugar fraction in Kokuto, non-centrifuged cane sugar. Nippon N šogeikagaku Kaishi (in Japanese), 74, (2000). 3) Takara, K., Matsui, D., Wada, K., Ichiba, T., and Nakasone, Y., New antioxidative phenolic glycosides isolated from Kokuto non-centrifuged cane sugar. Biosci. Biotechnol. Biochem., 66, (2002). 4) Matsuura, Y., Kimura, Y., and Okuda, H., EŠect of aromatic glucosides isolated from black sugar on intestinal absorption of glucose. Wakan-Yaku, 7, (1990). 5) Palla, G., Characterization of the main secondary components of the liquid sugars from cane molasses. J. Agric. Food Chem., 31, (1983). 6) Shimomura, H., Sashida, Y., Oohara, M., and Tenama, H., Phenolic glucosides from Parabenzoin praecox. Phytochem., 27, (1998). 7) Saijyo, R., Nonaka, G., and Nishioka, I., Phenol glucoside gallates from Mallotus japonicus. Phytochem., 28, (1989). 8) Chassagne, D., Crouzet, J., Bayonove, C. L., and Baumes, R. L., Glycosidically bound eugenol and methyl salicylate in the fruit of edible Passi ora species. J. Agric. Food Chem., 45, (1997). 9) Kitajima, J., Okamura, C., Ishikawa, T., and Tanaka, Y., New glycosides and furocoumarin from the Glehnia littoralis root and rhizoma. Chem. Pharm. Bull., 46, (1998). 10) Wang, C. Z., and Yu, D. Q., Ligana and acetylenic glycosides from Aster auriculatus. Phytochem., 48, (1998). 11) Changzeng, W., and Zhongjian, J., Lignan, phenylpropanoid and iridoid glycosides from Pedicularis torta. Phytochem., 45, (1997). 12) Wang, M., Li, J., Rangarajan, M., Shao, Y., LaVoie, E. J., Huang, T., and Ho, C., Antioxidative phenolic compounds from sage (Salvia o cinalis). J. Agric. Food Chem., 46, (1998). 13) Matsushita, H., Miyase, T., and Ueno, A., Lignan and terpene glycosides from Epimedium sagittatum. Phytochem., 30, (1991).