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Monoterpenoid and phenylethanoid glycosides from Ligustrum pedunculare
Pefgamon
Phytorhmwry,
MONOTERPENOID
ZHENG-DAN
HE,
Vol 36. No. 3. pp. 709 -716, 1994
Copyri&t0 19!94EbcvinSoeaocLtd Printed ia C&al Brims.All rightsmstved 0031+422/w s7.m+ 0.00
SHNCHI
AND PHENYLETHANOID GLYCOSIDES LIGUSTRUM PEDUNCULARE
UEDA, MASAKO AKAJI, TETSURO FUJITA, KENICHIRO INOUE*
and
FROM
CHONG-REN
YANG~
Faculty of Pharmaceutical Sciences, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan; lGifu Pharmaceutical University, S-6-1 Mitahora-higashi, Gifu 502, Japan; TLaboratory of Phytochemistry, Kunming Institute of Botany, Chinese Academy of Sciences, 650204, Kunming Yunnan, China
(Received 25 October 1993) Key Word Index--Ligustrum pedunculare; Oleaceae; leaves; phenylethanoid A-I, A-II; monoterpene glycosides; lipedosides B-I-B-VI.
glycosides;
lipedosides
Abstract-Two new phenylethanoid glycosides, lipedosides A-I and A-II as well as six new monoterpene glycosides, lipedosides B-I-B-VI were isolated together with three known constituents, osmanthuside B, anatolioside and linalool from L&strum pedunculare. Their structures have been elucidated by chemical and spectroscopic methods.
INTRODUCTION Ku-Ding-Cha, a well known traditional drinking tea, has been used in south China for a long time. Many species belonging to different families and genera are used as its original materials (Table 1) [l]. Ligustrum pedunculare has long been used as a variety of Ku-Ding-Cha. In continuation of our investigations on the constituents of oleaceous plants and Ku-Ding-Cha [l-3], we have isolated linalool (12), three phenylethanoid glycosides and seven monoterpene glycosides from L. pedunculare. This paper describes the isolation and structural elucidation of two new phenylethanoid glycosides, lipedosides A-I (1) and A-II (2), as well as six new monoterpene glycosides, lipedosides B-I (6), B-II (7). B-III (8), B-IV (9), B-V (10) and B-VI (11).
RESULTS AND DlSCUSSlON
A methanolic extract of the dry leaves of L. pedunculare was fractionated as described in the Experimental section Table 1. Original species of Ku-Ding-Cha in different areas of China species
Family
Oleaceae L&strum pedunculare Rehd. Oleaceae L. purjmrascens Y.C. Yang L. joponicum var. pubescens Koidz. Oleaceae Oleaceae L. robustrum (Roxb.) Bl. Aquifoliaceae Ilex cornuta Lindl. ex Paxt. Aquifoliaceae I. kudincha C. J. Tseng Aquifoliaceae 1. latvolia Thunb. Cratoxylum prun@lium (Kutz) Dyer Guttiferae rhyrsijoro (S. et Z.) Nakai Ehretiaceae Rosaceae Photinia serruiata Lindl. Ehretio
Place Sichuan Yunnan Guizhou Guizhou Zhejiang Guangxi Zhejiang Hunan Guangxi Guangxi Zhejiang
to give two new phenylethanoid glycosides, lipedosides A-I (1) and A-II (2), as well as six new monoterpene glycosides, lipedosides B-I (6), B-II (7), B-III (8), B-IV (9), B-V (10) and B-VI (11) together with three known compounds, linalool (12). osmanthuside B (3) [4] and anatolioside (5) [7]. Lipedoside A-I (l), a powder, analysed for Cz9H,,01* from its HR-FAB mass spectrum (m/z 609.2214 [M + H] ‘). The UV (2::” nm: 200, 213, 225, 317) and IR (vki; cm - I.. 3400, 1700, 1630, 1610, 1515) suggested the presence of hydroxyl, ester and conjugated aromatic groups. The ‘H NMR spectrum at the aromatic region exhibited an A,B, system belonging to a p-coumaroyl moiety Ca6.79 (2H, d, J=8.6 Hz), 67.45 (2H, d, J =8.6 Hz)]. The two olefinic proton signals which ap peared as an AB-system (J= 15.9 Hz) indicated a transgeometry in the moiety. ‘H NMR signals of two anomeric protons at 65.20 (lH, d, J= 1.6 Hz) and 64.32 (lH, d, J =8.0 Hz), as well as one secondary methyl group of rhamnose at 6 1.08 (3H, d, J =6.3 Hz) are consistent with the configurations for r+rhamnose and @-glucose. Comparing the 13C NMR signals of 1 with those of 3 [4]. the chemical shifts assignable to C-3 of the aglycone moiety in 1 shifted downfield to 6 144.6, while chemical shifts of C-2, C-4 and C-6 shifted upfield to 6 116.3,6 146.1 and 6 121.3, respectively (Table 2). An ABX-system assignable to the aglycone moiety appeared at 66.48 (1 H, dd, J=8.2, 1.8 Hz), 66.56 (lH, d, J= 1.8 Hz) and 66.67 (lH, d, J=8.2 Hz) (Table 3) [S]. These results indicate that two hydroxyl groups are located at C-3 and C-4 of the aglycone of 1. Alkali hydrolysis of 1 gave a compound, whose spectral and physical data were in good accord-
ance with those of [2-(3,4-dihydroxyphenyl)-ethyl]-(3-0a-L-rhamnopyranosyl~p-r>-glucopyranoside (4) (Tables 2 and 3). Thus, lipedoside A-I (1) was identified as [2-(3,4-dihydroxyphenyl)-ethyl]-(3-O-a-L-rhamnopyranosyl)-(4-O-p-coumaroyl)-B_D-glucopyranoside. 709
ZHENG-DAN
710
d
Me HO
MC HO zil
HE et al.
0
OH
OH
1
R]=OH,
2
R’=OH, R*=H, R3=pcoumaroyt
3 4
R’=R3=H, R’=OH.
R*=p-mumaroyl.
R3=H
12b
R*=p-cuumaroyl
R*= R3=H
34
0
HO HO
0
Me OH
HO
6a
R=H
6b
R=H
73
R=c&xoumaroyl
7b
R=cic-p-coumaroyl
8a
Rdranvp-coumaroyl
8b
R=wnr-pccumaroyl
HO
OH HO 5
Compound
1 formerly obtained from L. purpurascens of Z and E isomers [I]. Thus, optically active lipcdoside A-I (I) is a new phcnylethanoid glycoside. Lipedoside A-II (2). a powder, analysed for C,,HJ,O,, from its HR-FAB mass spectrum (m/z609.2191 [M + HI’). The UV and IR spectra were similar to those of 1. The ‘H NMR spectrum of 2 was also very similar to that of 1, indicating an A,B,- and an ABX-system which belong to the rrans-p-coumaroyl and the same aglycone moiety, respectively (Table 3). When comparing the ‘H NMR signals of 2 with those of 1, the chemical shift assignable to H-4 of 2 in the glucosyl moiety shifted upfield from 64.90 (IH, f, 5=8 Hz) to 63.47 (lH, t, J = 8 Hz), but the chemical shift of HZ-6 shifted downfield from 63.67 (IH. dd, J= 12, 5.5 Hz) and 63.90 (IH, dd, J =12,2Hz)to64.34(lH,dd,.l=l2.6Hz)and64.52(lH, was a mixture
OH
OH 9
R=H
10
Rric-psoumaroyl
11
R=lranr-p-coumaroyl
dd, J = 12, 2 Hz), respectively (Table 3). The signal of C-6 of 2 compared with that of 1 shifted downfield from 662.4 to 664.7 (Table 2). Thus, the p-coumaroyl moiety should be located at the C-6 of the glucosyl moiety in 2 [6]. Furthermore, alkali hydrolysis of 2 gave a known compound 4. The structure of lipedoside A-II (2) has thus been elucidated as [2-(3,4-dihydroxyphenyl)-ethyl]-(3-0z-L-rhamnopyranosyl)-(6-O-p-coumaroyI)-~-n-glucopyranoside. Lipedoside B-l (6). a powder, analysed for C,,H,,O,, from its HR-FAB mass spectrum (m/z 485.2352 [M + Na] ‘). The IR spectrum showed characteristic absorptions at 3400 (OH groups) and 1640 (C=C) cm. ‘. The ‘H NMR spectrum showed the following signals belonging to a monoterpene moiety: (i) an ABX system of three olefinic protons on a monosubstituted double bond at 65.18 (lH, dd, .I= 10.8, 1.3 Hz, H-la), (is.22 (IH. dd, J
712
ZHENG-DAN HF. et al.
Table H
3. ‘H NMR spectral data of glycosides
I
Aglycone 2 3 5 6 7 8
6.67 6.48 2.80 3.73 4.02
3
2
6.56(1H.
d, 1.8)
(1 H, d, 8.2) (I H. dd, 8.2. I .8) (2H. r. 6.7) (m) (m)
6.65 (lH, d, 2.1) 6.69 6.55 2.79 3.72 4.05
l-4 (in CD,OD)
(I H, dd. 8.0) (I H. dd, 8.0, 2.1) (2H. r, 7.0) (m)
(m)
4
d. 8.6) d, 8.6) d. 8.6) d, 8.6) I, 6.8)
6.71 (I H. d. 2.0)
4.38 (1H, 3.47(1H. 3.62(1H, 4.91 (IH, 3.57(1H. 3.65(1H, 3.85 (I H,
d, 8.1) r, 8.1) r. 8.1) r, 8.1) dd, 12, 6) dd, 12. 2)
4.30 (I H. 3.45 (1 H. 3.60 (I H, 3.45 (1 H, 3.58 (IH, 3.62(lH, 3.85(lH,
d. 1.6) m) r, 9.2) m) d, 6.1)
5.18 (IH, d, 1.5) 3.69 (ZH,‘m) 3.42 (1H, r, 9.2) 3.95 (IH. m) l.lO(lH. d, 6.3)
d, d, d. d,
7.07 6.72 6.72 7.07 2.84 3.74 4.1 I
(1 H, (1H, (IH, (I H. (2H. (m) (m)
6.73 (IH. d, 8.1) 6.52(1H. dd. X.1, 2.0) 2.78 (2H. r. 7.2) 3.66 (m) 3 91 (m)
GlUCOSyl
I 2 3 4 5 6 Rhamnosyl I 2.3 4 5 6 p-Coumaroyl 2.6 3,5 7 8 Coupling
4.32 (I H, 3.49 (1H, 3.61 (IH, 4.90 (1 H. 3.59 (IH. 3.67 (I H, 3.90(IH.
d, 8.0) r, 8.0) r. 8.0) I, 8.0) m) dd, 12. 5.5) dd. 12. 2)
4.34 (1 H. d, 7.9) 3.43 (I H, r, 7.9) 3.58 (1 H, r, 8.0) 3.47 (1 H, r, 8.0) 36O(lH, m) 434(1H,dd, 12.6) 4.52(lH. dd, 12, 2)
5.2O(lH. 3 72 (ZH, 3.40 (1 H, 4.OO(lH, 1.08 (3H,
d, 1.6) m) r. 9.5) m) d, 6.3)
5.20(IH, 3.70 (2H, 3.43(lH, 3.91 (IH. 1.06 (3H.
d, 1.6) r, 9.1) m) d, 6.2)
5.22 (IH. 3.73 (2H, 3.41 (1H. 3.9O(IH. l.lO(3H.
7.45 (ZH, 6.79 (2H. 765(lH, 6.33(lH.
d, d. d, d.
7.46 6.80 7.62 6.34
d. d, d, d,
7.46 (ZH, 6.81 (2H. 767(lH. 6.34(1H.
constants
8.6) 8.6) 15.9) 15.9)
m)
(ZH, (ZH, (IH, (1 H.
(J values in Hz) arc shown
8.6) 8.6) 16.1) 16.1)
in parentheses
of 6 from 65.09 to 3.37 in 9 (Table 4). The “C NMR signal of the aglycone C-6 and C-7 of 9 also shifted upfield from 6 125.6 and 132.1 in 6 to 6 80.1 and 674.1, respectively (Table 5). These results indicate that the aglycone of 9 was 3,7-dimethyloct-l-ene-3,6,7-trio1 [lo]. In addition, the ‘H NMR spectrum of 9 displayed two anomeric protons at 64.45 (J 17.8 Hz) and 65.15 (J = 1.6 Hz) which were consistent with the configurations for ~-D-glucose and z-r.-rhamnose. One methyl group of rhamnose was observed at 6 1.24 (J=6.3 Hz). The ‘% NMR spectrum of 9 also showed signals for glucosyl and rhamnosyl groups. The chemical shifts of the sugar moieties of 9 were similar to those of 6. From a ‘H “C long range COSY experiment on 9: two anomeric carbons of the glucosyl and rhamnosyl groups were shown to be joined to C-l of the aglycone and C-3 of the glucosyl moiety, respectively. Thus, the structure of lipedoside B-IV was concluded to be 3-(6,7-dihydroxy-3,7dimethyloct-lenyl)-3-O-z-L-rhamnopyranosyl)-~-D-glucopyranoside (9). Lipedoside B-V (lo), a powder analysed for C3,H46014 by its HR-FAB mass spectrum (m/z 643.2932 [M +H]‘). Its UV and IR spectra showed similar absorption bands to those of 7. Comparison of the iH and “CNMR data of 10 and 9 suggested that their aglycone moieties were identical (Tables 4 and 5). In addition to the glucosyl and rhamnosyl moieties, a set of cis-p-coumaroyl signals was observed in 10. Alkaline signal
8.7) X.7) 16.0) 16.0)
m)
d, 8.3) d, 8.3) d, 8.3) d, 8.3) m) dd, 12.1. 6) dd, 12.1. 2)
hydrolysis of 10 gave 9. A ‘H-‘%Z long range COSY experiment on 10, in a similar way to that described for 7, led to the structure of lipedoside B-V being deduced as 3(6,7-dihydroxy-3,7-dimethyloct-l-enyl)-(3-cr-t.-rhamnopyranosyl)-(4-O-cis-p-coumaroyl)-B_D-glycopyranoside (IO). Lipedoside B-VI (ll), a powder, analysed for C,,H,60,, by its HR-FAB mass spectrum (m/z 643.2942 [M+H]+). The ‘H and i3CNMR spectra of 11 were similar to those of 10,except for the appearance ofa transp-coumaroyl unit in 11 instead of the cis-p-coumaroyl unit in 10 (Tables 4 and 5). The ‘H-‘H, 1H-‘3CCOSY and ‘H---‘3C long range COSY experiments on 11 were also carried out to reveal the 3.J interaction between the anomeric proton of the rhamnosyl and the C-3 of glucosyl moieties. Alkaline hydrolysis of 11 gave 9. Thus, the structure of lipedoside B-VI was established to be 3-(6,7-dihydroxy-3,7-dimethyloct-l-enyl)-(3-~-L-rhamnopyranosyl)~4-0-tra,ts-p-coumaroyl)-P-D-glucopyranoside (11). EXPERIMENTAL
*H (200 and 300 MHz) and 13C (50 and 75 MHz) NMR: TMS as int. standard. HR-FAB-MS, FAB-MS: glycerol as matrix. CC and TLC: silica gel. Si 60 (Lobar, 40-63 pm, length: 250 mm, diameter: 25 mm, Merck), Rp-18 (Lobar, 40-63 pm, length: 250 mm, diameter: 25 mm, Merck) and Diaion HP-20 (Mitsubishi Kasei).
Coupling
2.6 3.5 7 8
Rhamnosyl 1 2 3 4 5 6 pCoumaroy1
6 8 9 10 Glucosyl 1 2 3 4 5 6
lb 2 4 5
la
H
m) s) s) s)
5.00 1.66 1.59 1.38
10.8, 18.0, 18.0, 10.5.
1.3) 1.3) 10.8) 5.1)
constants
d, 1.7) dd, 1.7, 3.4) dd, 3.4, 9.5) t, 9.5) m) d, 6.2)
5.14(1H, d, 1.7) 3.92(lH, dd, 1.7, 3.5) 3.70 (1 H,dd, 3.5, 9.5) 3.43 (1 H, 1, 9.5) 4.06(1H, m) 1.25 (3H. d, 6.1) 7.71 6.76 6.93 5.78
(2H, (2H, ( 1H, (lH,
d, d, d, d, 8.7) 8.7) 12.9) 12.9)
7.46 6.81 7.66 6.33
(2H, (2H, (lH, (lH,
5.19(1H, 3.92 (lH, 3.59 (1 H, 3.29 (1 H, 3.56 (IH, 1.08 (3H,
(1 H, (lH, (1H, (1 H, (lH, (m)
1.2) 1.2) 10.9) 5.0)
d, d, d, d,
8.7) 8.7) 16.0) 16.0)
d, 1.7) dd, 1.7, 3.5) dd, 3.5, 9.6) 1, 9.6) m) d, 6.2)
-
7.72 (ZH, 6.79 (2H, 6.94(1H, 5.80(lH,
d, d, d, d,
8.6) 8.6) 12.8) 12.8)
(IH, d, 1.6) (1 H,dd, 1.6, 3.5) (1 H. dd, 3.5, 9.7) (1 H, dd, 9.7) (1 H, m) (3H, d, 6.2)
7.45 6.83 7.67 6.31
(ZH, (ZH, (lH, (IH,
5.20(1H, 3.91 (IH, 3.60 (1 H, 3.29 (lH, 3.55(1H, 1.09 (3H,
3.38 (lH, m) 3.54 (m)
3.43-3.37 (m) 3.48 (lH, dd. 12.1, 5.6) 3.58(lH, dd. 12.1, 2.1) 5.21 3.93 3.61 3.40 3.66 1.15
3.51 (lH, dd, 7.9, 9.0) 4.92 (1 H. 1,9.0)
3.74 (lH, I, 9.3) 4.86 (1 H, 1, 9.3)
d, d, d, d,
8.6) 8.6) 15.9) 15.9)
d, 1.6) dd, 1.6, 3.5) dd, 3.4, 9.5) t, 9.5) m) d, 6.2)
s) s) s) 4.56 (1 H, d, 7.9) 3.5 1 (1 H, dd, 7.9, 9.0)
s) s) s) 4.48 (1 H, d, 7.9) 3.43-3.37 (m)
s) s) s) d, 7.8) dd, 7.8, 9.2) t, 9.2) t, 9.2) m) dd, 12, 6) dd, 12. 2)
dd, 17.8, 11.0) dd, 11.0, 1.6) dd, 17.8, 1.6) br I, 12.9) br dr, 12.9, 4.2) br dl, 12.9, 4.2)
594(1H, 5.21 (IH, 5.26(1H, 1.77 (2H, 1.67(lH, 1.93(lH, 3.47 (m) l.l7(3H, l.l2(3H, 1.40 (3H,
52O(lH, 5.27(1H, 5.93(lH, 1.77 (ZH, 1.68(1H, 1.95(lH, 3.45 (m) 1.18 (3H, l.l2(3H, 1.39 (3H_
dd, 10.9, 1.3) dd, 17.8, 1.3) dd, 17.8, 10.9) br I, 12.5) br dt, 12.j. 4.3) br dt, 12.5. 4.3)
dd, 11.0, 1.6) dd, 17.5, 1.6) dd, 17.5, 11.0) br t, 12.9) brdr. 13.0.4.1) br dt, 13.0,4.1)
11
10
5.15 (lH, d, 1.6) 3.95 (IH, dd, 1.6, 3.5) 3.72 (1 H, dd. 3.5, 9.6) 3.48 (1 H, t. 9.6) 4.1 (lH, m) 1.24 (3H, d, 6.3)
4.45 ( 1H, 3.42 (1 H, 3.44 (1 H, 3.33 (lH, 3.20 (lH, 3.66(1H, 3.87 (1 H,
5.17(1H, 5.24(1H, 5.92(1H, 1.71 (2H, 1.54 il H, 1.88 (lH, 3.37 (m) 1.16 (3H. l.l2(3H, 1.37 (3H,
9
S-11 in (CD,OD)
d, 7.9) dd, 7.9, 9.2) dd, 7.9, 9.2) 1, 9.2) m)
4.43 3.52 3.78 4.90 3.36 3.52
d, 7.9) (m) t, 9.2) 1, 9.2) (m) dd, 12, 5.7) dd, 12, 2)
5.17(1H, d, 1.7) 3.93 (1 H,dd, 1.7, 3.4) 3.60 (1H. dd, 3.4, 9.6) 3.39 (IH, 1, 9.6) 3.64(1H, m) 1.16 (3H, d, 6.2)
4.40 (1 H, 3.40-3.35 3.72 (1 H. 4.85 (1 H, 3.40-3.35 3.48 (lH, 3.58 (1 H,
d, 7.8) t, 7.8) I, 7.8) 1, 7.8) m) dd, 12, 6.2) dd, 12, 2)
(1 H, (1 H, (IH, (1 H, (lH, (1 H, (1 H,
4.35 3.28 3.48 3.32 3.18 3.68 3.82
m) d, 0.6) d, 0.6) s)
S.lO(lH, 1.66 (3H, 1.59 (3H, 1.39 (3H,
10.9. 17.8, 17.8, 10.5,
m) d, 0.7) d, 0.7) s)
1.3) 1.3) 10.9) 5.1 Hz)
dd, dd, dd, dd, m)
10.9, 17.8, 17.8, 10.5,
8
data of glycosides
5.22(1H, 5.25(1H, 5.93(1H, 1.60(2H, 2.04 i2H,
dd, dd, dd. dd, m)
5.21 (lH, 5.24(1H, 5.92(lH, 1.60(2H, 2.04 i2H, 5.10(1H, 1.66 (3H, 1.59 (3H, 1.38 (3H.
1.3) 1.3) 10.8) 5.1)
m) s) s) s)
10.8, 17.6, 17.6, 10.5,
7
4. ‘H NMR spectral
5.09(lH, 1.65 (3H, 1.58 (3H, 1.37 (3H,
5.18(lH, dd, 5.22(1H,dd, 5.92(1H, dd, 1.60(2H. dd, 2.04 i2H. m)
6
(J values in Hz) are shown in pa:enthe.ses.
5.3O(lH, 3.95 (1 H, 3.71 (lH, 3.46 (IH, 4.11 (IH, 1.22 (3H,
4.42 (1 H, d, 7.4) 3.41 (1 H, dd, 7.4, 9.5) 3.45 (lH, t, 9.5) 3.30 (1 H,1, 9.5) 3.19 (lH, m) 3.68 (lH, dd, 12, 6) 3.85(lH, dd, 12, 2)
(1 H, (3H, (3H, (3H,
dd, dd. dd, dd, m)
5.18(IH, 5.24(1H, 5.94(1H, 1.60(2H, 2.01 i2H;
s
Tabk
n
3 P F? z L 9
{
z 3
z
3 k
116
ZHENG-DAN HF. et al.
extracted with Et,O. The solvent was distilled off to give (S)-linalool (12b) containing 13% of (R)-linalool (12a), which was confirmed by [a&,, GC-MS [9]. The H,O phase was neutralized with 0.1 M NaOH, th,:n coned to give a residue, which was fractionated by silica gel CC with CHCI,--MeOH-H,O (14:6: 1) to yield r-rhamnose (6.1 mg) and D-glucose (5.7 mg). L-Rhamnose: TLC, R,0.46 (CHCl,.-MeOH-H,O, 14:6: 1,2 developments); [g]A” +7.8” (H,O; ~0.16). D-Glucose: TLC, R,0.12 (CHCI,-MeOH-H,O, 14:6: 1, 2 developments); [z]:’ +41.3” (H,O; ~0.08). Alkaline hydrolysis o/compound 7. A soln of the glycoside (30.1 mg) in MeOH (3 ml) and 1 M NaOH (3ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI. then extracted with Et,0 and EtOAc. The Et,0 extract gave a cis-trans mixt. (molar ratio 1:2.5) of Me pcoumarate. The EtOAc extract was chromatographed on a silica gel column eluting with CHCI, MeOH (9: 1) to afford 6 (14.2 mg). Alkuline hydrolysis of compound 8. A soln of the glycoside (30.5 mg) in MeOH (3 ml) and 1 M NaOH (3 ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI, then extracted with Et,0 and EtOAc. The Et10 extract gave a cis--tran.s mixt. (molar ratio 1: 2.5) of Me pcoumarate. The EtOAc extract was chromatographed on a silica gel column eluting with CHCI,-MeOH (9: 1) to alford 6 (I 2.3 mg). Alkaline hydrolysis oj’ compound 10. A soln of the glycoside (45.2 mg) in MeOH (3 ml) and I M NaOH (3 ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI, then extracted with Et,0 and EtOAc. The Et,0 extract gave a cis- trans mixture of Me p-coumarate. The EtOAc extract was chromatographed on a silica gel column eluting with CHCI,-MeOH (9:2) to alford 9 (18.3mg). Alknline hydrolysis of compound 11. A soln of the glycoside (43.9 mg) in MeOH (3 ml) and 1 M NaOH (3 ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI, then extracted with Et20 and EtOAc. The Et,0 extract gave a (is--[runs mixt. of Me p-coumarate. The EtOAc extract was chromatographed on a silica gel
column eluting (16.3 mg)
with CHCI,-MeOH
(9:2) to afford
9
Acknowledgements--We
are grateful to Dr N. Akimoto, Faculty of Pharmaceutical Sciences, Kyoto University, for the determination of HR-FAB mass spectra, the members of the Microanalytical Center, Kyoto University for elemental analyses, MS T. Terada, Institute for Chemical Research, Kyoto University, for determination of FAB mass spectra, Profs M. Shimada and T. Umezawa, Wood Research Institute. Kyoto University for providing the opportunity to use a I-DEX 120 fusedsilica capillary column and Dr M. Yoshikura and Mr K. Ohsaki, San-Ei Gen F. F. I., Inc. for standard samples of (R) and (Qlinalool and for capillary column GC and GCMS respectively. REFERENCES
He, Z. D., Liu, Y. Q. and Yang, C. R. (1992) Actu But. Yunnun 14, 328. He, Z. D., Shi, Z. M. and Yang, C. R. (1990) Actu Bat. Sinicu 32, 544. Kuwajima, H., Morita, M., Takaishi, K., Inoue, K., Fujita, T.. He, Z. D. and Yang. C. R. (1992) Phytochemistry
31, 1277.
Kobayashi, H., Kardsawa, H., Miyase, T. and Fukushima, S. (1984) Chem. Pharm. Bull. 32, 3880. He, Z. D. and Yang, C. R. (1991) Phytochemistry 30, 701.
Miyase, T., Ishino, M., .Akahori, C., Ueno, A., Ohkawa, Y. and Tanizawa, H. (1991) Phytochemistrp 36, 2015.
Calis, I., Yuruker, A., Wright, A. D. and Sticher, 0. (1991) Plunta Med. 57, Suppl. 2, A80. Calis, I., Yuruker, A., Ruegger, H., Wright, A. D. and Sticher, 0. (1993) He/r:. Chim. Acta 76, 416. Tanaka N., Sakai, H., Murakami, T., Saiki, Y., Chen, C. M. and litaka, Y. (1986) Chem. Pharm. Bull. 34, 1015. 10. Williams, P. J., Strauss, C. R. and Wilson, B. (1980) Phytochemistry 19, I 137.
Phytorhmwry,
MONOTERPENOID
ZHENG-DAN
HE,
Vol 36. No. 3. pp. 709 -716, 1994
Copyri&t0 19!94EbcvinSoeaocLtd Printed ia C&al Brims.All rightsmstved 0031+422/w s7.m+ 0.00
SHNCHI
AND PHENYLETHANOID GLYCOSIDES LIGUSTRUM PEDUNCULARE
UEDA, MASAKO AKAJI, TETSURO FUJITA, KENICHIRO INOUE*
and
FROM
CHONG-REN
YANG~
Faculty of Pharmaceutical Sciences, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan; lGifu Pharmaceutical University, S-6-1 Mitahora-higashi, Gifu 502, Japan; TLaboratory of Phytochemistry, Kunming Institute of Botany, Chinese Academy of Sciences, 650204, Kunming Yunnan, China
(Received 25 October 1993) Key Word Index--Ligustrum pedunculare; Oleaceae; leaves; phenylethanoid A-I, A-II; monoterpene glycosides; lipedosides B-I-B-VI.
glycosides;
lipedosides
Abstract-Two new phenylethanoid glycosides, lipedosides A-I and A-II as well as six new monoterpene glycosides, lipedosides B-I-B-VI were isolated together with three known constituents, osmanthuside B, anatolioside and linalool from L&strum pedunculare. Their structures have been elucidated by chemical and spectroscopic methods.
INTRODUCTION Ku-Ding-Cha, a well known traditional drinking tea, has been used in south China for a long time. Many species belonging to different families and genera are used as its original materials (Table 1) [l]. Ligustrum pedunculare has long been used as a variety of Ku-Ding-Cha. In continuation of our investigations on the constituents of oleaceous plants and Ku-Ding-Cha [l-3], we have isolated linalool (12), three phenylethanoid glycosides and seven monoterpene glycosides from L. pedunculare. This paper describes the isolation and structural elucidation of two new phenylethanoid glycosides, lipedosides A-I (1) and A-II (2), as well as six new monoterpene glycosides, lipedosides B-I (6), B-II (7). B-III (8), B-IV (9), B-V (10) and B-VI (11).
RESULTS AND DlSCUSSlON
A methanolic extract of the dry leaves of L. pedunculare was fractionated as described in the Experimental section Table 1. Original species of Ku-Ding-Cha in different areas of China species
Family
Oleaceae L&strum pedunculare Rehd. Oleaceae L. purjmrascens Y.C. Yang L. joponicum var. pubescens Koidz. Oleaceae Oleaceae L. robustrum (Roxb.) Bl. Aquifoliaceae Ilex cornuta Lindl. ex Paxt. Aquifoliaceae I. kudincha C. J. Tseng Aquifoliaceae 1. latvolia Thunb. Cratoxylum prun@lium (Kutz) Dyer Guttiferae rhyrsijoro (S. et Z.) Nakai Ehretiaceae Rosaceae Photinia serruiata Lindl. Ehretio
Place Sichuan Yunnan Guizhou Guizhou Zhejiang Guangxi Zhejiang Hunan Guangxi Guangxi Zhejiang
to give two new phenylethanoid glycosides, lipedosides A-I (1) and A-II (2), as well as six new monoterpene glycosides, lipedosides B-I (6), B-II (7), B-III (8), B-IV (9), B-V (10) and B-VI (11) together with three known compounds, linalool (12). osmanthuside B (3) [4] and anatolioside (5) [7]. Lipedoside A-I (l), a powder, analysed for Cz9H,,01* from its HR-FAB mass spectrum (m/z 609.2214 [M + H] ‘). The UV (2::” nm: 200, 213, 225, 317) and IR (vki; cm - I.. 3400, 1700, 1630, 1610, 1515) suggested the presence of hydroxyl, ester and conjugated aromatic groups. The ‘H NMR spectrum at the aromatic region exhibited an A,B, system belonging to a p-coumaroyl moiety Ca6.79 (2H, d, J=8.6 Hz), 67.45 (2H, d, J =8.6 Hz)]. The two olefinic proton signals which ap peared as an AB-system (J= 15.9 Hz) indicated a transgeometry in the moiety. ‘H NMR signals of two anomeric protons at 65.20 (lH, d, J= 1.6 Hz) and 64.32 (lH, d, J =8.0 Hz), as well as one secondary methyl group of rhamnose at 6 1.08 (3H, d, J =6.3 Hz) are consistent with the configurations for r+rhamnose and @-glucose. Comparing the 13C NMR signals of 1 with those of 3 [4]. the chemical shifts assignable to C-3 of the aglycone moiety in 1 shifted downfield to 6 144.6, while chemical shifts of C-2, C-4 and C-6 shifted upfield to 6 116.3,6 146.1 and 6 121.3, respectively (Table 2). An ABX-system assignable to the aglycone moiety appeared at 66.48 (1 H, dd, J=8.2, 1.8 Hz), 66.56 (lH, d, J= 1.8 Hz) and 66.67 (lH, d, J=8.2 Hz) (Table 3) [S]. These results indicate that two hydroxyl groups are located at C-3 and C-4 of the aglycone of 1. Alkali hydrolysis of 1 gave a compound, whose spectral and physical data were in good accord-
ance with those of [2-(3,4-dihydroxyphenyl)-ethyl]-(3-0a-L-rhamnopyranosyl~p-r>-glucopyranoside (4) (Tables 2 and 3). Thus, lipedoside A-I (1) was identified as [2-(3,4-dihydroxyphenyl)-ethyl]-(3-O-a-L-rhamnopyranosyl)-(4-O-p-coumaroyl)-B_D-glucopyranoside. 709
ZHENG-DAN
710
d
Me HO
MC HO zil
HE et al.
0
OH
OH
1
R]=OH,
2
R’=OH, R*=H, R3=pcoumaroyt
3 4
R’=R3=H, R’=OH.
R*=p-mumaroyl.
R3=H
12b
R*=p-cuumaroyl
R*= R3=H
34
0
HO HO
0
Me OH
HO
6a
R=H
6b
R=H
73
R=c&xoumaroyl
7b
R=cic-p-coumaroyl
8a
Rdranvp-coumaroyl
8b
R=wnr-pccumaroyl
HO
OH HO 5
Compound
1 formerly obtained from L. purpurascens of Z and E isomers [I]. Thus, optically active lipcdoside A-I (I) is a new phcnylethanoid glycoside. Lipedoside A-II (2). a powder, analysed for C,,HJ,O,, from its HR-FAB mass spectrum (m/z609.2191 [M + HI’). The UV and IR spectra were similar to those of 1. The ‘H NMR spectrum of 2 was also very similar to that of 1, indicating an A,B,- and an ABX-system which belong to the rrans-p-coumaroyl and the same aglycone moiety, respectively (Table 3). When comparing the ‘H NMR signals of 2 with those of 1, the chemical shift assignable to H-4 of 2 in the glucosyl moiety shifted upfield from 64.90 (IH, f, 5=8 Hz) to 63.47 (lH, t, J = 8 Hz), but the chemical shift of HZ-6 shifted downfield from 63.67 (IH. dd, J= 12, 5.5 Hz) and 63.90 (IH, dd, J =12,2Hz)to64.34(lH,dd,.l=l2.6Hz)and64.52(lH, was a mixture
OH
OH 9
R=H
10
Rric-psoumaroyl
11
R=lranr-p-coumaroyl
dd, J = 12, 2 Hz), respectively (Table 3). The signal of C-6 of 2 compared with that of 1 shifted downfield from 662.4 to 664.7 (Table 2). Thus, the p-coumaroyl moiety should be located at the C-6 of the glucosyl moiety in 2 [6]. Furthermore, alkali hydrolysis of 2 gave a known compound 4. The structure of lipedoside A-II (2) has thus been elucidated as [2-(3,4-dihydroxyphenyl)-ethyl]-(3-0z-L-rhamnopyranosyl)-(6-O-p-coumaroyI)-~-n-glucopyranoside. Lipedoside B-l (6). a powder, analysed for C,,H,,O,, from its HR-FAB mass spectrum (m/z 485.2352 [M + Na] ‘). The IR spectrum showed characteristic absorptions at 3400 (OH groups) and 1640 (C=C) cm. ‘. The ‘H NMR spectrum showed the following signals belonging to a monoterpene moiety: (i) an ABX system of three olefinic protons on a monosubstituted double bond at 65.18 (lH, dd, .I= 10.8, 1.3 Hz, H-la), (is.22 (IH. dd, J
712
ZHENG-DAN HF. et al.
Table H
3. ‘H NMR spectral data of glycosides
I
Aglycone 2 3 5 6 7 8
6.67 6.48 2.80 3.73 4.02
3
2
6.56(1H.
d, 1.8)
(1 H, d, 8.2) (I H. dd, 8.2. I .8) (2H. r. 6.7) (m) (m)
6.65 (lH, d, 2.1) 6.69 6.55 2.79 3.72 4.05
l-4 (in CD,OD)
(I H, dd. 8.0) (I H. dd, 8.0, 2.1) (2H. r, 7.0) (m)
(m)
4
d. 8.6) d, 8.6) d. 8.6) d, 8.6) I, 6.8)
6.71 (I H. d. 2.0)
4.38 (1H, 3.47(1H. 3.62(1H, 4.91 (IH, 3.57(1H. 3.65(1H, 3.85 (I H,
d, 8.1) r, 8.1) r. 8.1) r, 8.1) dd, 12, 6) dd, 12. 2)
4.30 (I H. 3.45 (1 H. 3.60 (I H, 3.45 (1 H, 3.58 (IH, 3.62(lH, 3.85(lH,
d. 1.6) m) r, 9.2) m) d, 6.1)
5.18 (IH, d, 1.5) 3.69 (ZH,‘m) 3.42 (1H, r, 9.2) 3.95 (IH. m) l.lO(lH. d, 6.3)
d, d, d. d,
7.07 6.72 6.72 7.07 2.84 3.74 4.1 I
(1 H, (1H, (IH, (I H. (2H. (m) (m)
6.73 (IH. d, 8.1) 6.52(1H. dd. X.1, 2.0) 2.78 (2H. r. 7.2) 3.66 (m) 3 91 (m)
GlUCOSyl
I 2 3 4 5 6 Rhamnosyl I 2.3 4 5 6 p-Coumaroyl 2.6 3,5 7 8 Coupling
4.32 (I H, 3.49 (1H, 3.61 (IH, 4.90 (1 H. 3.59 (IH. 3.67 (I H, 3.90(IH.
d, 8.0) r, 8.0) r. 8.0) I, 8.0) m) dd, 12. 5.5) dd. 12. 2)
4.34 (1 H. d, 7.9) 3.43 (I H, r, 7.9) 3.58 (1 H, r, 8.0) 3.47 (1 H, r, 8.0) 36O(lH, m) 434(1H,dd, 12.6) 4.52(lH. dd, 12, 2)
5.2O(lH. 3 72 (ZH, 3.40 (1 H, 4.OO(lH, 1.08 (3H,
d, 1.6) m) r. 9.5) m) d, 6.3)
5.20(IH, 3.70 (2H, 3.43(lH, 3.91 (IH. 1.06 (3H.
d, 1.6) r, 9.1) m) d, 6.2)
5.22 (IH. 3.73 (2H, 3.41 (1H. 3.9O(IH. l.lO(3H.
7.45 (ZH, 6.79 (2H. 765(lH, 6.33(lH.
d, d. d, d.
7.46 6.80 7.62 6.34
d. d, d, d,
7.46 (ZH, 6.81 (2H. 767(lH. 6.34(1H.
constants
8.6) 8.6) 15.9) 15.9)
m)
(ZH, (ZH, (IH, (1 H.
(J values in Hz) arc shown
8.6) 8.6) 16.1) 16.1)
in parentheses
of 6 from 65.09 to 3.37 in 9 (Table 4). The “C NMR signal of the aglycone C-6 and C-7 of 9 also shifted upfield from 6 125.6 and 132.1 in 6 to 6 80.1 and 674.1, respectively (Table 5). These results indicate that the aglycone of 9 was 3,7-dimethyloct-l-ene-3,6,7-trio1 [lo]. In addition, the ‘H NMR spectrum of 9 displayed two anomeric protons at 64.45 (J 17.8 Hz) and 65.15 (J = 1.6 Hz) which were consistent with the configurations for ~-D-glucose and z-r.-rhamnose. One methyl group of rhamnose was observed at 6 1.24 (J=6.3 Hz). The ‘% NMR spectrum of 9 also showed signals for glucosyl and rhamnosyl groups. The chemical shifts of the sugar moieties of 9 were similar to those of 6. From a ‘H “C long range COSY experiment on 9: two anomeric carbons of the glucosyl and rhamnosyl groups were shown to be joined to C-l of the aglycone and C-3 of the glucosyl moiety, respectively. Thus, the structure of lipedoside B-IV was concluded to be 3-(6,7-dihydroxy-3,7dimethyloct-lenyl)-3-O-z-L-rhamnopyranosyl)-~-D-glucopyranoside (9). Lipedoside B-V (lo), a powder analysed for C3,H46014 by its HR-FAB mass spectrum (m/z 643.2932 [M +H]‘). Its UV and IR spectra showed similar absorption bands to those of 7. Comparison of the iH and “CNMR data of 10 and 9 suggested that their aglycone moieties were identical (Tables 4 and 5). In addition to the glucosyl and rhamnosyl moieties, a set of cis-p-coumaroyl signals was observed in 10. Alkaline signal
8.7) X.7) 16.0) 16.0)
m)
d, 8.3) d, 8.3) d, 8.3) d, 8.3) m) dd, 12.1. 6) dd, 12.1. 2)
hydrolysis of 10 gave 9. A ‘H-‘%Z long range COSY experiment on 10, in a similar way to that described for 7, led to the structure of lipedoside B-V being deduced as 3(6,7-dihydroxy-3,7-dimethyloct-l-enyl)-(3-cr-t.-rhamnopyranosyl)-(4-O-cis-p-coumaroyl)-B_D-glycopyranoside (IO). Lipedoside B-VI (ll), a powder, analysed for C,,H,60,, by its HR-FAB mass spectrum (m/z 643.2942 [M+H]+). The ‘H and i3CNMR spectra of 11 were similar to those of 10,except for the appearance ofa transp-coumaroyl unit in 11 instead of the cis-p-coumaroyl unit in 10 (Tables 4 and 5). The ‘H-‘H, 1H-‘3CCOSY and ‘H---‘3C long range COSY experiments on 11 were also carried out to reveal the 3.J interaction between the anomeric proton of the rhamnosyl and the C-3 of glucosyl moieties. Alkaline hydrolysis of 11 gave 9. Thus, the structure of lipedoside B-VI was established to be 3-(6,7-dihydroxy-3,7-dimethyloct-l-enyl)-(3-~-L-rhamnopyranosyl)~4-0-tra,ts-p-coumaroyl)-P-D-glucopyranoside (11). EXPERIMENTAL
*H (200 and 300 MHz) and 13C (50 and 75 MHz) NMR: TMS as int. standard. HR-FAB-MS, FAB-MS: glycerol as matrix. CC and TLC: silica gel. Si 60 (Lobar, 40-63 pm, length: 250 mm, diameter: 25 mm, Merck), Rp-18 (Lobar, 40-63 pm, length: 250 mm, diameter: 25 mm, Merck) and Diaion HP-20 (Mitsubishi Kasei).
Coupling
2.6 3.5 7 8
Rhamnosyl 1 2 3 4 5 6 pCoumaroy1
6 8 9 10 Glucosyl 1 2 3 4 5 6
lb 2 4 5
la
H
m) s) s) s)
5.00 1.66 1.59 1.38
10.8, 18.0, 18.0, 10.5.
1.3) 1.3) 10.8) 5.1)
constants
d, 1.7) dd, 1.7, 3.4) dd, 3.4, 9.5) t, 9.5) m) d, 6.2)
5.14(1H, d, 1.7) 3.92(lH, dd, 1.7, 3.5) 3.70 (1 H,dd, 3.5, 9.5) 3.43 (1 H, 1, 9.5) 4.06(1H, m) 1.25 (3H. d, 6.1) 7.71 6.76 6.93 5.78
(2H, (2H, ( 1H, (lH,
d, d, d, d, 8.7) 8.7) 12.9) 12.9)
7.46 6.81 7.66 6.33
(2H, (2H, (lH, (lH,
5.19(1H, 3.92 (lH, 3.59 (1 H, 3.29 (1 H, 3.56 (IH, 1.08 (3H,
(1 H, (lH, (1H, (1 H, (lH, (m)
1.2) 1.2) 10.9) 5.0)
d, d, d, d,
8.7) 8.7) 16.0) 16.0)
d, 1.7) dd, 1.7, 3.5) dd, 3.5, 9.6) 1, 9.6) m) d, 6.2)
-
7.72 (ZH, 6.79 (2H, 6.94(1H, 5.80(lH,
d, d, d, d,
8.6) 8.6) 12.8) 12.8)
(IH, d, 1.6) (1 H,dd, 1.6, 3.5) (1 H. dd, 3.5, 9.7) (1 H, dd, 9.7) (1 H, m) (3H, d, 6.2)
7.45 6.83 7.67 6.31
(ZH, (ZH, (lH, (IH,
5.20(1H, 3.91 (IH, 3.60 (1 H, 3.29 (lH, 3.55(1H, 1.09 (3H,
3.38 (lH, m) 3.54 (m)
3.43-3.37 (m) 3.48 (lH, dd. 12.1, 5.6) 3.58(lH, dd. 12.1, 2.1) 5.21 3.93 3.61 3.40 3.66 1.15
3.51 (lH, dd, 7.9, 9.0) 4.92 (1 H. 1,9.0)
3.74 (lH, I, 9.3) 4.86 (1 H, 1, 9.3)
d, d, d, d,
8.6) 8.6) 15.9) 15.9)
d, 1.6) dd, 1.6, 3.5) dd, 3.4, 9.5) t, 9.5) m) d, 6.2)
s) s) s) 4.56 (1 H, d, 7.9) 3.5 1 (1 H, dd, 7.9, 9.0)
s) s) s) 4.48 (1 H, d, 7.9) 3.43-3.37 (m)
s) s) s) d, 7.8) dd, 7.8, 9.2) t, 9.2) t, 9.2) m) dd, 12, 6) dd, 12. 2)
dd, 17.8, 11.0) dd, 11.0, 1.6) dd, 17.8, 1.6) br I, 12.9) br dr, 12.9, 4.2) br dl, 12.9, 4.2)
594(1H, 5.21 (IH, 5.26(1H, 1.77 (2H, 1.67(lH, 1.93(lH, 3.47 (m) l.l7(3H, l.l2(3H, 1.40 (3H,
52O(lH, 5.27(1H, 5.93(lH, 1.77 (ZH, 1.68(1H, 1.95(lH, 3.45 (m) 1.18 (3H, l.l2(3H, 1.39 (3H_
dd, 10.9, 1.3) dd, 17.8, 1.3) dd, 17.8, 10.9) br I, 12.5) br dt, 12.j. 4.3) br dt, 12.5. 4.3)
dd, 11.0, 1.6) dd, 17.5, 1.6) dd, 17.5, 11.0) br t, 12.9) brdr. 13.0.4.1) br dt, 13.0,4.1)
11
10
5.15 (lH, d, 1.6) 3.95 (IH, dd, 1.6, 3.5) 3.72 (1 H, dd. 3.5, 9.6) 3.48 (1 H, t. 9.6) 4.1 (lH, m) 1.24 (3H, d, 6.3)
4.45 ( 1H, 3.42 (1 H, 3.44 (1 H, 3.33 (lH, 3.20 (lH, 3.66(1H, 3.87 (1 H,
5.17(1H, 5.24(1H, 5.92(1H, 1.71 (2H, 1.54 il H, 1.88 (lH, 3.37 (m) 1.16 (3H. l.l2(3H, 1.37 (3H,
9
S-11 in (CD,OD)
d, 7.9) dd, 7.9, 9.2) dd, 7.9, 9.2) 1, 9.2) m)
4.43 3.52 3.78 4.90 3.36 3.52
d, 7.9) (m) t, 9.2) 1, 9.2) (m) dd, 12, 5.7) dd, 12, 2)
5.17(1H, d, 1.7) 3.93 (1 H,dd, 1.7, 3.4) 3.60 (1H. dd, 3.4, 9.6) 3.39 (IH, 1, 9.6) 3.64(1H, m) 1.16 (3H, d, 6.2)
4.40 (1 H, 3.40-3.35 3.72 (1 H. 4.85 (1 H, 3.40-3.35 3.48 (lH, 3.58 (1 H,
d, 7.8) t, 7.8) I, 7.8) 1, 7.8) m) dd, 12, 6.2) dd, 12, 2)
(1 H, (1 H, (IH, (1 H, (lH, (1 H, (1 H,
4.35 3.28 3.48 3.32 3.18 3.68 3.82
m) d, 0.6) d, 0.6) s)
S.lO(lH, 1.66 (3H, 1.59 (3H, 1.39 (3H,
10.9. 17.8, 17.8, 10.5,
m) d, 0.7) d, 0.7) s)
1.3) 1.3) 10.9) 5.1 Hz)
dd, dd, dd, dd, m)
10.9, 17.8, 17.8, 10.5,
8
data of glycosides
5.22(1H, 5.25(1H, 5.93(1H, 1.60(2H, 2.04 i2H,
dd, dd, dd. dd, m)
5.21 (lH, 5.24(1H, 5.92(lH, 1.60(2H, 2.04 i2H, 5.10(1H, 1.66 (3H, 1.59 (3H, 1.38 (3H.
1.3) 1.3) 10.8) 5.1)
m) s) s) s)
10.8, 17.6, 17.6, 10.5,
7
4. ‘H NMR spectral
5.09(lH, 1.65 (3H, 1.58 (3H, 1.37 (3H,
5.18(lH, dd, 5.22(1H,dd, 5.92(1H, dd, 1.60(2H. dd, 2.04 i2H. m)
6
(J values in Hz) are shown in pa:enthe.ses.
5.3O(lH, 3.95 (1 H, 3.71 (lH, 3.46 (IH, 4.11 (IH, 1.22 (3H,
4.42 (1 H, d, 7.4) 3.41 (1 H, dd, 7.4, 9.5) 3.45 (lH, t, 9.5) 3.30 (1 H,1, 9.5) 3.19 (lH, m) 3.68 (lH, dd, 12, 6) 3.85(lH, dd, 12, 2)
(1 H, (3H, (3H, (3H,
dd, dd. dd, dd, m)
5.18(IH, 5.24(1H, 5.94(1H, 1.60(2H, 2.01 i2H;
s
Tabk
n
3 P F? z L 9
{
z 3
z
3 k
116
ZHENG-DAN HF. et al.
extracted with Et,O. The solvent was distilled off to give (S)-linalool (12b) containing 13% of (R)-linalool (12a), which was confirmed by [a&,, GC-MS [9]. The H,O phase was neutralized with 0.1 M NaOH, th,:n coned to give a residue, which was fractionated by silica gel CC with CHCI,--MeOH-H,O (14:6: 1) to yield r-rhamnose (6.1 mg) and D-glucose (5.7 mg). L-Rhamnose: TLC, R,0.46 (CHCl,.-MeOH-H,O, 14:6: 1,2 developments); [g]A” +7.8” (H,O; ~0.16). D-Glucose: TLC, R,0.12 (CHCI,-MeOH-H,O, 14:6: 1, 2 developments); [z]:’ +41.3” (H,O; ~0.08). Alkaline hydrolysis o/compound 7. A soln of the glycoside (30.1 mg) in MeOH (3 ml) and 1 M NaOH (3ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI. then extracted with Et,0 and EtOAc. The Et,0 extract gave a cis-trans mixt. (molar ratio 1:2.5) of Me pcoumarate. The EtOAc extract was chromatographed on a silica gel column eluting with CHCI, MeOH (9: 1) to afford 6 (14.2 mg). Alkuline hydrolysis of compound 8. A soln of the glycoside (30.5 mg) in MeOH (3 ml) and 1 M NaOH (3 ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI, then extracted with Et,0 and EtOAc. The Et10 extract gave a cis--tran.s mixt. (molar ratio 1: 2.5) of Me pcoumarate. The EtOAc extract was chromatographed on a silica gel column eluting with CHCI,-MeOH (9: 1) to alford 6 (I 2.3 mg). Alkaline hydrolysis oj’ compound 10. A soln of the glycoside (45.2 mg) in MeOH (3 ml) and I M NaOH (3 ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI, then extracted with Et,0 and EtOAc. The Et,0 extract gave a cis- trans mixture of Me p-coumarate. The EtOAc extract was chromatographed on a silica gel column eluting with CHCI,-MeOH (9:2) to alford 9 (18.3mg). Alknline hydrolysis of compound 11. A soln of the glycoside (43.9 mg) in MeOH (3 ml) and 1 M NaOH (3 ml) was stirred for 3 hr at room temp. and neutralized with 5% HCI, then extracted with Et20 and EtOAc. The Et,0 extract gave a (is--[runs mixt. of Me p-coumarate. The EtOAc extract was chromatographed on a silica gel
column eluting (16.3 mg)
with CHCI,-MeOH
(9:2) to afford
9
Acknowledgements--We
are grateful to Dr N. Akimoto, Faculty of Pharmaceutical Sciences, Kyoto University, for the determination of HR-FAB mass spectra, the members of the Microanalytical Center, Kyoto University for elemental analyses, MS T. Terada, Institute for Chemical Research, Kyoto University, for determination of FAB mass spectra, Profs M. Shimada and T. Umezawa, Wood Research Institute. Kyoto University for providing the opportunity to use a I-DEX 120 fusedsilica capillary column and Dr M. Yoshikura and Mr K. Ohsaki, San-Ei Gen F. F. I., Inc. for standard samples of (R) and (Qlinalool and for capillary column GC and GCMS respectively. REFERENCES
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