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Phenolic compounds from Viburnum dilatatum
0031-9422i92 %5.00+0.00 Q 1992 PergamonPress Ltd
Phytochemistry, Vol. 31, No. 10, pp. 3654-3656, 1992 Printedin Great Britain.
PHENOLIC COMPOUNDS
FROM VIBURNUM
KOICHI MACHIDA
MASAO
and
DILATATUM*
KIKUCHI
Tohoku College of Pharmacy, 4-1, Komatsushima 4-chome, Aobaku, Sendai, Miyagi 981, Japan
(Received 2 January Key Word Index-viburnum
dilatatum; Caprifoliaceae;
1992)
dilignols;
quinic acid esters.
Abstract-Three new phenolic compounds have been isolated from the leaves of Viburnum dilatatum and their structures elucidated as 1~4’-hydroxy-3’-methoxyphenyl)-2-[~’-hydroxy-~-(3”‘-hydroxypropyl)]-1,3-propanediol l0-I-D-glucopyranoside (erythro isomer), neochlorogenic acid methyl ester and cryptochlorogenic acid methyl ester by spectroscopic studies.
INTRODUCTION
We have recently obtained a number of compounds from flowers, fruits [l, 23 and leaves [3, 43 of Viburnum dilatatum THUNB. In the course of further studies on the constituents of the above plant, a new dilignol glycoside and two new quinic acid esters with several known compounds have been isolated from the leaves.
a2-$?2 1”’
-YOR’
R2 RESULTS AND DISCUSSION
OR’
Compound 1 [ l-(4’-hydroxy-3’-methoxyphenyl)]-2[2”-hydroxy-4”-(3”‘-hydroxypropyl)phenoxyl]-1,3-propanediol l-O-/?-D-glucopyranoside (threo isomer) [S], a mixture of 3 (lyoniside) [6] and 4 (nudiposide) [6-83, 5 (neochlorogenic acid) [9], 6 (crypochlorogenic acid) [9], 7 (3-0-p-coumaroylquinic acid) [9] and 8 (4-O-p-coumaroylquinic acid) [9] were identified by comparison of various diagnostic data with reported values and authentic samples. Compounds 1 and 2 were converted to their respective octaacetates (la and 2a), for the purposes of characterization. Compound 1 has been isolated from Pinus
sylvestris
la 2 2a
*Part 5 in the series ‘Studies on the Constituents of Viburnum Species. Iv’. For Part 4 see Machida K. and Kikuchi M. (1990) Tohoku Yakka Daigaku Kenkyu Nenpo 31, 57.
H AC H AC
Glc@ythro) Glc(OAc), GlcW) Glc(OAc),
,,,/&a
R’Q,
1
01 2
Rzo”“‘
34
z
&3
OR4
9 9a IO IOa
R’
R2
R3
H AC H H
Caffwyl Caffeoyl(Ac) H H
H H AC AC Caffwyl H Caffeoyl (AC) H
R4
H&.+~,
[S].
Compound 2a was obtained as an amorphous powder. The UV spectrum showed absorption maxima at 220 (4.51) and 273 (3.51) nm (log E).The FAB mass spectrum afforded [M + Na]+ at m/z 885, [M + K]+ at m/z 901 and [M + H + TEA]’ at m/z 1012, which were very similar to those of la. The ‘H and ‘%NMR spectra resembled those of la except for the signals due to H-l and C-l. In the ‘HNMR spectrum, the H-l signal was observed at 65.11 (d, J = 2.6 Hz), showing a downfield shift (0.29 ppm) and a small coupling constant compared with those of la (J = 5.9 Hz) [lo]. In the 13CNMR spectrum, the C-l signal (678.9) of 2a was shifted upfield by 2.6 ppm compared with that of la [ll]. From these data, 1 was determined to be 1-(4’-hydroxy-3’-methoxyphenyl)-2[2”-hydroxy-4”-(3”-hydroxypropyl)phenoxy]-l,3-propanediol 1-O-P-D-glucopyranoside, which is the erythro isomer of 1.
1
5’
6
For structural elucidation, the mixture of 9 and 10 was separated by acetylation. Compound 9a was assigned the molecular formula C27H30014 (HRMS, [M]’ 578.1608). The ‘HNMR spectrum exhibited signals belonging to a caffeic moiety, a quinic acid moiety and a methoxy group. The signals of H-3 (es), H-4 (ax) and H-5 (ax) of the quinic acid moiety were assigned according to their multiplicity, and their spin-spin coupling constants [12]. The position of caffeoyl substitution and the location of the methoxy group on the quinic acid moiety were confirmed as follows. The HMBC spectrum showed a correlation between the signal of H-3 (65.63) and a carboxyl carbon signal (6 165.4). The carboxyl carbon signal was also found to be correlated with two trans olefinic proton signals, while a methoxy proton signal (63.74) showed correlation with
3654
Short Reports C-7 (6 170.7).From these spectral data, the location of the caffeoyl substitution must be at the C-3 position of the quinic acid methyl ester moiety. The structure of 9 is, therefore, that of neochlorogenic acid methyl ester. Compound 1011 was obtained as an amorphous powder. The spectral data were very similar to those of 9a. The location of the caffeoyl substitution on the quinic acid methyl ester moiety was determined by the HMBC spectrum. The signal at 65.12 due to H-4 of the quinic acid methyl ester moiety showed a correlation with the carboxyl carbon signal at 6165.4. These results established the location of the caffeoyl substitution as being at the C-4 position of the quinic acid methyl ester moiety. The structure of 10is, therefore, that of cryptochlorogenic acid methyl ester. Compounds 5 and 6 were each dissolved in methanol-water containing a small amount of acetic acid and heated at reflux temperature for 6 hr. The solvents were evaporated off in uucuo to give residues. The ‘H NMR spectrum of each residue showed no methoxy group signal and thus established that compounds 9 and 10are not artifacts of the extraction and isolation procedures. Compounds 2, 9 and 10 are new natural compounds; 1,3,4, !#-g have now been found for the first time in the genus Viburnum. EXPERIMENTAL ‘H and %NMR: relative to TMS as int. standard, Prep. HPLC: Tosoh HPLC system using ODS-120A (7.8 mm i.d. x 30 cm) or ODS-8OTM (6.0 mm i.d. x 15 cm) column, flow rate l.Omlmin-‘, MeOH-Hz0 (3:1, 2:1, l:l, 1:3 and 1:4), detection at 285 nm. Extraction and isolation. Fresh leaves of Viburnum dilatatum (3 kg) collected in September 1988, in Sendai, Japan, were extracted with MeOH at room temp. The MeOH extract was coned and the resultant aqueous suspension was extracted with CHCI,, EtzO, EtOAc and n-BuOH, successively. The n-BuOH extract (62.3 g) was chromatographed on a silica gel column using CHCl,-MeOH-Hz0 (30: 10: 1) and on a Sephadex LH-20 column using MeOH-Hz0 (1: 1) to yield a mixture of compounds that were grouped according to their R, values. The components that were positive in the FeCl, test were fractionated by prep. HPLC to give 5 (5 mg), 6 (4 mg), 7 (4 mg) and 8 (3 mg). The crude powders containing mixtures of 1 and 2,3 and 49 and 10 were acetylated with Ac,O in pyridine, respectively. After usual work-up, the crude products were purified by prep. HPLC to give la (4 mg), 2a (3 mg), a mixt. of 3a and 4a (3 mg), 9s (5 mg) and 10s(6 mg). Compound la. An amorphous powder. [alo -9.9” (MeGH, c 0.3) FABMS m/z: 885 [M+Na]+ and 1012 [M+H+TEA]+; UV1:::” nm (log E): 220 (3.97) and 273 (3.23); IRvzz’ cm-i: 1757,1608,1509,1040,!907; ‘H NMR (400 MHz, CDCI,): 61.93 (3H, MeCOz), 1.98 (6H, 2 x MeCO,), 2.0 (3H, MeCO,), 2.05 (6H, 2 x MeCO,), 2.26 (3H, MeCO,), 2.29 (3H, MeCO,), 2.62 (2H, t, J =7.7 Hz, H-l”‘), 3.83 (3H, s, OMe), 4.0 (2H, m, H-3), 4.55 (lH, m, H-2),4.78(1H,d,J=8.1 Hz,GlcH-1),4.82(1H,d,J=5.9Hz,Hl), 6.86-7.03 (6H, m, arom. proton& i3CNMR (100 MHz, CDCl,): 820.2, 20.5, 20.6, 20.9 (each MeCO,), 30.1 (C-2”‘), 31.2 (C-l”‘), 55.9 (OMe), 61.8 (Glc C-6), 62.6 (C-3), 63.6 (C-3”‘), 68.3 (Glc C-4), 71.4 (Glc C-2), 71.8 (Glc C-5), 729 (Glc C-3), 80.2 (C-2), 81.5 (C-l), 101.4 (Glc C-l), 111.7 (C-2’), 116.0 (G6”), 119.4 (C-6’), 122.4 (C-S), 123.0 (C-3”), 126.6 (GS), 135.4 (C-4”), 136.1 (Cl’), 139.8 (C-2”), 140.8 (C-4’), 147.9 (C-l”), 151.0 (G3’), 168.7, 168.8, 169.3, 169.4, 170.2, 170.4, 170.5, 171.1 (each MeCO,). Compound 2~. An amorphous powder. [alo -35.0” (MeOH, c Mps:
uncorr;
3655
0.2). FABMS m/z: 885 [M+Na]+ 901 [M+K]+ and 1012 [M +H+TEA]+; UVAE$‘” nm (log E): 220 (4.51), 273 (3.51); IRv~:“cm-‘: 1757,1607,1509,1040,907; ‘H NMR (400 MHz, CDCl,): al.93 (3H, MeCOz), 2.00 (3H, MeCO,), 2.02 (3H, MeCO,), 2.06 (6H, 2 x MeCO,), 2.15 (3H, MeCO,), 2.30 (3H, MeCO,), 2.36 (3H, MeCO,), 2.64 (2H, t, J=7.7 Hz, H-l”‘), 3.84 (3H, s, OMe), 4.07 (lH, m, H-3& 4.47 (lH, m, H-3& 4.68 (lH, m, H-2),4.94(1H,d,J=8.1 Hz,GlcH-1),5.11(1H,d,J=26Hz,Hl), 6.W7.08 (6H, m, arom. protons); i3C NMR (100 MHz, CDCl,): 620.5, 20.6, 20.7, 20.9 (each MeCO,), 29.9 (C-2”‘), 31.2 (C-l”‘), 55.9 (OMe), 61.6 (Glc C-6), 61.7 (C-3), 63.6 (C-3”‘), 68.3 (Glc C-4), 71.5 (Glc C-5), 71.6 (Glc C-2), 72.7 (Glc C-3), 78.9 (C-l), 80.9 (C-2), 100.7 (Glc C-l), 110.9 (C-2’), 114.9 (C-6”), 118.2 (C-6’), 122.4 (C-S), 123.4 (C-3”), 126.7 (C-5”), 135.4 (C-4”), 136.2 (C-l’), 139.3 (C-T), 140.5 (C-4’), 147.4 (C-l”), 151.0 (C-3’), 168.9, 169.3, 169.4, 169.7, 170.2, 170.5, 170.7, 171.1 (each MeCO,). Compound 9a. An amorphous powder. [a]n -28.6” (CHCl,; c 0.3). EIMS m/r 578 [Ml’; HRMS m/z 578.1608 (calcd Cz,Hs,O,,: 578.1636); UVI~~“nm (log e): 217 (4.13), 285 (4.09), 328 (3.89); IRvz” cm-‘: 1745, 1638, 1604, 1505; ‘HNMR (400 MHz, CD&): 61.95 (lH, m, H-6d, 2.02 (3H, MeCOz), 2.05 (3H, MeCO,), 2.08 (3H, MeCOz), 2.31 (3H, MeCO,), 2.32 (3H, MeCO,), 2.39 (lH, m, H-2d, 2.63 (lH, m, H6B), 2.76(1H, m, H-2,), 3.74(3H,s,CO,Me),5.07(1H,dd, J=3.5, 10.0 Hz, H-4), 5.52 (lH, ddd, J=4.5, 10.0, H-5), 5.63 (lH, ddd, J =3.5Hz,H-3),6.36(1H,d,J=16.1,H-8’h7.25(1H,d,J=8.5Hz, H-5’), 7.38 (lH, d, J= 1.8 Hz, H-2’), 7.42 (lH, dd, J= 1.8, 8.5 Hz, H-6’), 7.66 (lH, d, J=16.1 Hz, H-7’); %NMR (100 MHz, CDCl,): 620.6,20.7,20.9,21.2 (each MeCO,), 32.2 (C-2), 36.7 (C6), 52.9 (G8), 66.5 (C-3), 68.3 (C-5), 71.7 (C-4), 78.7 (C-l), 118.5 (C8’), 122.9 (C-2’), 124.1 (C-S), 126.4 (C-6’), 132.9 (C-l’), 142.6 (C-4’), 143.8 (C-3’), 143.9 (C-7’), 165.4 (C-9’), 167.9, 168.0, 169.7, 169.9 (each MeCO,). Compound 101.An amorphous powder. [a]o - 27.7” (CHCl,; ~0.4). EIMS m/z 578 [Ml’, HRMS m/z 578.1657 (calcd C,,H,,O,,: 578.1636); UVli$“‘nm (log s): 217 (4.12), 283 (4.07), 327 (3.67); IRv::” cm-‘: 1746, 1640, 1604, 1504, ‘HNMR (4OOMHz, CDCl,): 6201 (lH, m, H-6,), 2.02 (3H, MeCO,), 2.07 (3H, MeCO,), 2.14 (3H, MeCOz), 2.30 (3H, MeCO,), 2.31(3H, MeCO,), 2.40 (lH, m, H-2,), 259 (lH, m, H6& 2.68 (lH, m, H&), 3.75 (3H, s, COzMe), 5.12 (lH, dd, J=3.5, 10.0 Hz, H-4), 5.54(1H, ddd, J=4.5, 10.0 HZ, H-5), 5.61 (lH, ddd, J=3.5 Hz, H-3), 6.31 (lH, d, J=15.8 HZ, H-8’), 7.23 (lH, d, J =8.5 Hz, H-S), 7.37 (lH, d, J= 1.8 Hz, H-2’), 7.40 (lH, dd, J = 1.8, 8.5 Hz, H-6’), 7.61 (lH, d, J= 15.8 Hz, H-7’); 13CNMR (lOOMHz, CDCI,): 620.6, 20.7, 20.8, 20.9, 21.0, 21.1 (each MeCO,), 32.1 (C-2), 36.7 (C-6), 52.9 (G8), 66.5 (C-3), 67.8 (C-5), 71.8 (C-4), 78.7 (C-l), 118.1 (C-8’), 122.8 (G2’), 124.0 (C-5’), 126.7 (C-6’), 132.9 (C-l’), 142.5 (C-4’), 143.7 (C-3’), 144.0 (C-7’), 165.4 (C9’), 167.9, 168.1, 169.6, 169.7, 169.9 (each MeCO,). Compounds M were identified by comparison of various data with reported values and authentic samples. Acknowledgements-We are grateful to Prof. Y. Sashida (Tokyo College of Pharmacy) for samples of lyoniside and nudiposide. Our thanks are also due to Dr S. Suzuki and Dr K. Hisamichi of this college for measurements of the mass and NMR spectra, respectively. REFERENCES
1. Kurihara, K. and Kikuchi, M. (1975) Yakuaaku Zasshi 95, 1098. 2. Kurihara, K. and Kikuchi, M. (1977) Tohoku Yakko Daigaku Kenkyu Nempc 24, 123. 3. Machida, K., Nakano, Y. and Kikuchi, M. (1991) Phytochemistry 30, 2013.
3656
Short Reports
4. Machida, K. and Kikuchi, M. (1990) Tohoku Yakka Daigaku Kenkyu Nempo 31, 51. 5. Popoff, T. and Theander, 0. (1977) Acta Chem. Stand. B31,
329. 6. Karikome, H., Mimaki, Y. and Sashida, Y. (1984) Phytochemistry 30, 315. I. Ogawa, M. and Ogiwara, Y. (1976) Chem. Pharm. Bull. 24, 2102.
8. Takai, M., Ohya, K. and Takahashi, K. (1979) Chem. Pharm. Bull. 27, 1422. 9. Morishita, H. (1984) J. Chromatogr. 315, 253. 10. Miyase, T., Ueno, A., Takizawa, N., Kobayashi, H. and Oguchi, H. (1987) Chem. Pharm. Bull. 35, 3713. 11. Matsushita, H., Miyasc, T. and Ueno, A (1991) Phytochemistry 30, 2025. 12. Karplus, M. (1959) J. Chem. Phys. 30, 11.
Phytochemistry, Vol. 31, No. 10, pp. 3654-3656, 1992 Printedin Great Britain.
PHENOLIC COMPOUNDS
FROM VIBURNUM
KOICHI MACHIDA
MASAO
and
DILATATUM*
KIKUCHI
Tohoku College of Pharmacy, 4-1, Komatsushima 4-chome, Aobaku, Sendai, Miyagi 981, Japan
(Received 2 January Key Word Index-viburnum
dilatatum; Caprifoliaceae;
1992)
dilignols;
quinic acid esters.
Abstract-Three new phenolic compounds have been isolated from the leaves of Viburnum dilatatum and their structures elucidated as 1~4’-hydroxy-3’-methoxyphenyl)-2-[~’-hydroxy-~-(3”‘-hydroxypropyl)]-1,3-propanediol l0-I-D-glucopyranoside (erythro isomer), neochlorogenic acid methyl ester and cryptochlorogenic acid methyl ester by spectroscopic studies.
INTRODUCTION
We have recently obtained a number of compounds from flowers, fruits [l, 23 and leaves [3, 43 of Viburnum dilatatum THUNB. In the course of further studies on the constituents of the above plant, a new dilignol glycoside and two new quinic acid esters with several known compounds have been isolated from the leaves.
a2-$?2 1”’
-YOR’
R2 RESULTS AND DISCUSSION
OR’
Compound 1 [ l-(4’-hydroxy-3’-methoxyphenyl)]-2[2”-hydroxy-4”-(3”‘-hydroxypropyl)phenoxyl]-1,3-propanediol l-O-/?-D-glucopyranoside (threo isomer) [S], a mixture of 3 (lyoniside) [6] and 4 (nudiposide) [6-83, 5 (neochlorogenic acid) [9], 6 (crypochlorogenic acid) [9], 7 (3-0-p-coumaroylquinic acid) [9] and 8 (4-O-p-coumaroylquinic acid) [9] were identified by comparison of various diagnostic data with reported values and authentic samples. Compounds 1 and 2 were converted to their respective octaacetates (la and 2a), for the purposes of characterization. Compound 1 has been isolated from Pinus
sylvestris
la 2 2a
*Part 5 in the series ‘Studies on the Constituents of Viburnum Species. Iv’. For Part 4 see Machida K. and Kikuchi M. (1990) Tohoku Yakka Daigaku Kenkyu Nenpo 31, 57.
H AC H AC
Glc@ythro) Glc(OAc), GlcW) Glc(OAc),
,,,/&a
R’Q,
1
01 2
Rzo”“‘
34
z
&3
OR4
9 9a IO IOa
R’
R2
R3
H AC H H
Caffwyl Caffeoyl(Ac) H H
H H AC AC Caffwyl H Caffeoyl (AC) H
R4
H&.+~,
[S].
Compound 2a was obtained as an amorphous powder. The UV spectrum showed absorption maxima at 220 (4.51) and 273 (3.51) nm (log E).The FAB mass spectrum afforded [M + Na]+ at m/z 885, [M + K]+ at m/z 901 and [M + H + TEA]’ at m/z 1012, which were very similar to those of la. The ‘H and ‘%NMR spectra resembled those of la except for the signals due to H-l and C-l. In the ‘HNMR spectrum, the H-l signal was observed at 65.11 (d, J = 2.6 Hz), showing a downfield shift (0.29 ppm) and a small coupling constant compared with those of la (J = 5.9 Hz) [lo]. In the 13CNMR spectrum, the C-l signal (678.9) of 2a was shifted upfield by 2.6 ppm compared with that of la [ll]. From these data, 1 was determined to be 1-(4’-hydroxy-3’-methoxyphenyl)-2[2”-hydroxy-4”-(3”-hydroxypropyl)phenoxy]-l,3-propanediol 1-O-P-D-glucopyranoside, which is the erythro isomer of 1.
1
5’
6
For structural elucidation, the mixture of 9 and 10 was separated by acetylation. Compound 9a was assigned the molecular formula C27H30014 (HRMS, [M]’ 578.1608). The ‘HNMR spectrum exhibited signals belonging to a caffeic moiety, a quinic acid moiety and a methoxy group. The signals of H-3 (es), H-4 (ax) and H-5 (ax) of the quinic acid moiety were assigned according to their multiplicity, and their spin-spin coupling constants [12]. The position of caffeoyl substitution and the location of the methoxy group on the quinic acid moiety were confirmed as follows. The HMBC spectrum showed a correlation between the signal of H-3 (65.63) and a carboxyl carbon signal (6 165.4). The carboxyl carbon signal was also found to be correlated with two trans olefinic proton signals, while a methoxy proton signal (63.74) showed correlation with
3654
Short Reports C-7 (6 170.7).From these spectral data, the location of the caffeoyl substitution must be at the C-3 position of the quinic acid methyl ester moiety. The structure of 9 is, therefore, that of neochlorogenic acid methyl ester. Compound 1011 was obtained as an amorphous powder. The spectral data were very similar to those of 9a. The location of the caffeoyl substitution on the quinic acid methyl ester moiety was determined by the HMBC spectrum. The signal at 65.12 due to H-4 of the quinic acid methyl ester moiety showed a correlation with the carboxyl carbon signal at 6165.4. These results established the location of the caffeoyl substitution as being at the C-4 position of the quinic acid methyl ester moiety. The structure of 10is, therefore, that of cryptochlorogenic acid methyl ester. Compounds 5 and 6 were each dissolved in methanol-water containing a small amount of acetic acid and heated at reflux temperature for 6 hr. The solvents were evaporated off in uucuo to give residues. The ‘H NMR spectrum of each residue showed no methoxy group signal and thus established that compounds 9 and 10are not artifacts of the extraction and isolation procedures. Compounds 2, 9 and 10 are new natural compounds; 1,3,4, !#-g have now been found for the first time in the genus Viburnum. EXPERIMENTAL ‘H and %NMR: relative to TMS as int. standard, Prep. HPLC: Tosoh HPLC system using ODS-120A (7.8 mm i.d. x 30 cm) or ODS-8OTM (6.0 mm i.d. x 15 cm) column, flow rate l.Omlmin-‘, MeOH-Hz0 (3:1, 2:1, l:l, 1:3 and 1:4), detection at 285 nm. Extraction and isolation. Fresh leaves of Viburnum dilatatum (3 kg) collected in September 1988, in Sendai, Japan, were extracted with MeOH at room temp. The MeOH extract was coned and the resultant aqueous suspension was extracted with CHCI,, EtzO, EtOAc and n-BuOH, successively. The n-BuOH extract (62.3 g) was chromatographed on a silica gel column using CHCl,-MeOH-Hz0 (30: 10: 1) and on a Sephadex LH-20 column using MeOH-Hz0 (1: 1) to yield a mixture of compounds that were grouped according to their R, values. The components that were positive in the FeCl, test were fractionated by prep. HPLC to give 5 (5 mg), 6 (4 mg), 7 (4 mg) and 8 (3 mg). The crude powders containing mixtures of 1 and 2,3 and 49 and 10 were acetylated with Ac,O in pyridine, respectively. After usual work-up, the crude products were purified by prep. HPLC to give la (4 mg), 2a (3 mg), a mixt. of 3a and 4a (3 mg), 9s (5 mg) and 10s(6 mg). Compound la. An amorphous powder. [alo -9.9” (MeGH, c 0.3) FABMS m/z: 885 [M+Na]+ and 1012 [M+H+TEA]+; UV1:::” nm (log E): 220 (3.97) and 273 (3.23); IRvzz’ cm-i: 1757,1608,1509,1040,!907; ‘H NMR (400 MHz, CDCI,): 61.93 (3H, MeCOz), 1.98 (6H, 2 x MeCO,), 2.0 (3H, MeCO,), 2.05 (6H, 2 x MeCO,), 2.26 (3H, MeCO,), 2.29 (3H, MeCO,), 2.62 (2H, t, J =7.7 Hz, H-l”‘), 3.83 (3H, s, OMe), 4.0 (2H, m, H-3), 4.55 (lH, m, H-2),4.78(1H,d,J=8.1 Hz,GlcH-1),4.82(1H,d,J=5.9Hz,Hl), 6.86-7.03 (6H, m, arom. proton& i3CNMR (100 MHz, CDCl,): 820.2, 20.5, 20.6, 20.9 (each MeCO,), 30.1 (C-2”‘), 31.2 (C-l”‘), 55.9 (OMe), 61.8 (Glc C-6), 62.6 (C-3), 63.6 (C-3”‘), 68.3 (Glc C-4), 71.4 (Glc C-2), 71.8 (Glc C-5), 729 (Glc C-3), 80.2 (C-2), 81.5 (C-l), 101.4 (Glc C-l), 111.7 (C-2’), 116.0 (G6”), 119.4 (C-6’), 122.4 (C-S), 123.0 (C-3”), 126.6 (GS), 135.4 (C-4”), 136.1 (Cl’), 139.8 (C-2”), 140.8 (C-4’), 147.9 (C-l”), 151.0 (G3’), 168.7, 168.8, 169.3, 169.4, 170.2, 170.4, 170.5, 171.1 (each MeCO,). Compound 2~. An amorphous powder. [alo -35.0” (MeOH, c Mps:
uncorr;
3655
0.2). FABMS m/z: 885 [M+Na]+ 901 [M+K]+ and 1012 [M +H+TEA]+; UVAE$‘” nm (log E): 220 (4.51), 273 (3.51); IRv~:“cm-‘: 1757,1607,1509,1040,907; ‘H NMR (400 MHz, CDCl,): al.93 (3H, MeCOz), 2.00 (3H, MeCO,), 2.02 (3H, MeCO,), 2.06 (6H, 2 x MeCO,), 2.15 (3H, MeCO,), 2.30 (3H, MeCO,), 2.36 (3H, MeCO,), 2.64 (2H, t, J=7.7 Hz, H-l”‘), 3.84 (3H, s, OMe), 4.07 (lH, m, H-3& 4.47 (lH, m, H-3& 4.68 (lH, m, H-2),4.94(1H,d,J=8.1 Hz,GlcH-1),5.11(1H,d,J=26Hz,Hl), 6.W7.08 (6H, m, arom. protons); i3C NMR (100 MHz, CDCl,): 620.5, 20.6, 20.7, 20.9 (each MeCO,), 29.9 (C-2”‘), 31.2 (C-l”‘), 55.9 (OMe), 61.6 (Glc C-6), 61.7 (C-3), 63.6 (C-3”‘), 68.3 (Glc C-4), 71.5 (Glc C-5), 71.6 (Glc C-2), 72.7 (Glc C-3), 78.9 (C-l), 80.9 (C-2), 100.7 (Glc C-l), 110.9 (C-2’), 114.9 (C-6”), 118.2 (C-6’), 122.4 (C-S), 123.4 (C-3”), 126.7 (C-5”), 135.4 (C-4”), 136.2 (C-l’), 139.3 (C-T), 140.5 (C-4’), 147.4 (C-l”), 151.0 (C-3’), 168.9, 169.3, 169.4, 169.7, 170.2, 170.5, 170.7, 171.1 (each MeCO,). Compound 9a. An amorphous powder. [a]n -28.6” (CHCl,; c 0.3). EIMS m/r 578 [Ml’; HRMS m/z 578.1608 (calcd Cz,Hs,O,,: 578.1636); UVI~~“nm (log e): 217 (4.13), 285 (4.09), 328 (3.89); IRvz” cm-‘: 1745, 1638, 1604, 1505; ‘HNMR (400 MHz, CD&): 61.95 (lH, m, H-6d, 2.02 (3H, MeCOz), 2.05 (3H, MeCO,), 2.08 (3H, MeCOz), 2.31 (3H, MeCO,), 2.32 (3H, MeCO,), 2.39 (lH, m, H-2d, 2.63 (lH, m, H6B), 2.76(1H, m, H-2,), 3.74(3H,s,CO,Me),5.07(1H,dd, J=3.5, 10.0 Hz, H-4), 5.52 (lH, ddd, J=4.5, 10.0, H-5), 5.63 (lH, ddd, J =3.5Hz,H-3),6.36(1H,d,J=16.1,H-8’h7.25(1H,d,J=8.5Hz, H-5’), 7.38 (lH, d, J= 1.8 Hz, H-2’), 7.42 (lH, dd, J= 1.8, 8.5 Hz, H-6’), 7.66 (lH, d, J=16.1 Hz, H-7’); %NMR (100 MHz, CDCl,): 620.6,20.7,20.9,21.2 (each MeCO,), 32.2 (C-2), 36.7 (C6), 52.9 (G8), 66.5 (C-3), 68.3 (C-5), 71.7 (C-4), 78.7 (C-l), 118.5 (C8’), 122.9 (C-2’), 124.1 (C-S), 126.4 (C-6’), 132.9 (C-l’), 142.6 (C-4’), 143.8 (C-3’), 143.9 (C-7’), 165.4 (C-9’), 167.9, 168.0, 169.7, 169.9 (each MeCO,). Compound 101.An amorphous powder. [a]o - 27.7” (CHCl,; ~0.4). EIMS m/z 578 [Ml’, HRMS m/z 578.1657 (calcd C,,H,,O,,: 578.1636); UVli$“‘nm (log s): 217 (4.12), 283 (4.07), 327 (3.67); IRv::” cm-‘: 1746, 1640, 1604, 1504, ‘HNMR (4OOMHz, CDCl,): 6201 (lH, m, H-6,), 2.02 (3H, MeCO,), 2.07 (3H, MeCO,), 2.14 (3H, MeCOz), 2.30 (3H, MeCO,), 2.31(3H, MeCO,), 2.40 (lH, m, H-2,), 259 (lH, m, H6& 2.68 (lH, m, H&), 3.75 (3H, s, COzMe), 5.12 (lH, dd, J=3.5, 10.0 Hz, H-4), 5.54(1H, ddd, J=4.5, 10.0 HZ, H-5), 5.61 (lH, ddd, J=3.5 Hz, H-3), 6.31 (lH, d, J=15.8 HZ, H-8’), 7.23 (lH, d, J =8.5 Hz, H-S), 7.37 (lH, d, J= 1.8 Hz, H-2’), 7.40 (lH, dd, J = 1.8, 8.5 Hz, H-6’), 7.61 (lH, d, J= 15.8 Hz, H-7’); 13CNMR (lOOMHz, CDCI,): 620.6, 20.7, 20.8, 20.9, 21.0, 21.1 (each MeCO,), 32.1 (C-2), 36.7 (C-6), 52.9 (G8), 66.5 (C-3), 67.8 (C-5), 71.8 (C-4), 78.7 (C-l), 118.1 (C-8’), 122.8 (G2’), 124.0 (C-5’), 126.7 (C-6’), 132.9 (C-l’), 142.5 (C-4’), 143.7 (C-3’), 144.0 (C-7’), 165.4 (C9’), 167.9, 168.1, 169.6, 169.7, 169.9 (each MeCO,). Compounds M were identified by comparison of various data with reported values and authentic samples. Acknowledgements-We are grateful to Prof. Y. Sashida (Tokyo College of Pharmacy) for samples of lyoniside and nudiposide. Our thanks are also due to Dr S. Suzuki and Dr K. Hisamichi of this college for measurements of the mass and NMR spectra, respectively. REFERENCES
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