全 文 ：水红木中两个新的酚苷成分*
朱向东, 汪 琼, 王易芬, 鞠 鹏, 罗士德**
(中国科学院昆明植物研究所植物化学与西部植物资源可持续利用国家重点实验室, 云南昆明 650204)
摘要: 从水红木 ( Viburnum cylindricum ) 植物中分离出 2 个新化合物, 1-phloroglucinyl- ( 6-methybutyryl )-B-D-gluco-
pyranoside命名为 cylindrin A ( 1) , 1- [ 4- ( 3-hydroxy-l propyl ) ]- pyrocatechol- ( 6-methybutyryl )-B-D-glucopyranoside, 命
名为 cylindrin B ( 2) , 以及 7 个已知化合物 tachioside ( 3) , syingic acid-4-B-D-glucopyran oside ( 4) , 1-B-D-glucopyr-
anosyloxy-3-methoxy-5-hydroxybenzene ( 5 ) , 4-hydroxy-3-methoxypheno-l 1-O-B-D-glucoside ( 6 ) , 4-hydroxy-2, 6-dime-
thoxypheno-l 1-O-B-D-glucoside ( 7) , phlorogluc ino-l 1-O-B-D-glucoside ( 8 ) , 1-B-D-glucosyloxy-2- ( 3-methoxy-4-hydroxy-
phenyl) propane-1, 3-diol ( 9) . 它们的结构经波谱方法得到鉴定。3~ 9 为首次从该种植物中分离得到。
关键词: 水红木; 酚苷; cylindrin A; cylindrin B
中图分类号: Q 946 文献标识码: A 文章编号: 0253- 2700( 2006) 01- 091- 04
Two New Phenolic Glycosides from Viburnum cylindricum ( Caprifoliaceae)
ZHU Xiang-Dong, WANGQiong, WANG Y-i Fen, JU Peng, LUO Sh-i De
* *
( StateK ey Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany,
Chinese Academy of Sciences, Kunming 650204, China)
Abstract: Viburnum cylindricum has been used in folk medicine in Yunnan. Two new phenolic glycosides, 1-phloroglucinyl-
( 6-methybutyryl )-B-D-glucopyranoside named cylindrin A ( 1) , and 1- [ 4-3-hydroxy-l propyl ) ]-pyrocatechol- ( 6-methybutyryl )-
B-D-glucopyranoside named cylindrin B ( 2) , along with seven known phenolic glycosides tachioside ( 3) , syingic acid-4-B-D-
glucopyran oside ( 4) , 1-B-D-glucopyranosyloxy-3-methoxy-5-hydroxybenzene ( 5 ) , 4-hydroxy-3-methoxypheno-l 1-O-B-D-glu-
coside ( 6) , 4-hydroxy-2, 6-dimethoxypheno-l 1-O-B-D-glucoside ( 7) , phlorogluc ino-l 1-O-B-D-glucoside ( 8) , 1-B-D-glucosy-
loxy-2- ( 3-methoxy-4-hydroxyphenyl) propane-1, 3-diol ( 9) have been isolated from the EtOAc extracts of its aerial parts. Their
structures were elucidated by means of spectroscopic method. Compounds 3- 9 were isolated from this plant for the first time.
Key words: Viburnum cylindricum ; Phenolic glycoside; cylindrin A; cylindrin B
Viburnum cylindricum Buch is widely distributed in
tropical area of Asia, which has been used in folk med-i
cine in Yunnan for the treatment of common cold, diar-
rhea, rheumatoid arthrit is and tumefaction ( Institutum
Botanicum Kunmingense Academiae Sinicae, 1991 ) .
However, few chemical data are available on this plant.
Several phytochemical investigations on other species of
the genus Viburnum have shown that these species present
diterpenoids ( Miwa et al , 2001) , irridoids ( Nedyalka
et al , 1988) , triterpenoids ( Yoshiyasu and Hiroyuki,
2002) and phenolic glycosides (Koichi et al , 1991) . In
our phytochemical investigation of the EtOAc-soluble frac-
t ion of an ethanol extracts of V1 cylindricum , 1-phloro-
glucinyl- ( 6-methybutyryl )-B-D-glucopyranoside ( 1 ) ,
1- [ 4- ( 3-hydroxy-l propyl ) ]-pyrcoatechol- ( 6-methybu-
tyryl )-B-D-glucopyranoside ( 2 ) , were isolated along
with seven known phenolic glycosides ( 3- 9) .
云 南 植 物 研 究 2006, 28 ( 1) : 91~ 94
Acta Botanica Yunnanica

*
** 通讯联系人 Corresponding author
收稿日期: 2005- 06- 29, 2005- 08- 10接受发表
作者简介: 朱向东 ( 1965- ) 男, 在读博士, 主要从事药用植物化学研究。
基金项目: 国家高技术研究和发展计划 ( 863计划) ( 2004AA2Z3321) 资助
Result and Discussion
Compound 1 was obtained as an amorphous powder,
[A]
25
D - 53 ( c 014, MeOH) . The molecular formula was
assigned as C17H24O9 from the HREIMS ( mPz 37111348,
calcd. for mPz 37111342, C17H24O9 [ M-H]
-
) and the
negative FABMS ( mPz 371 [ M-H ] - ) . The 13 C NMR
spectrum showed signals of 17 carbons including two
methyl groups and a carboxyl carbon. It exhibited signals
belonging to a hexose moiety, a phloroglucinol and meth-
ylbutyryl moiety ( Samlipto et al , 1988) . They were ap-
proved by direct comparison with 1- [ ( 2-methylbutyryl )
phloroglucinyl ]-B-D-glucopyranoside ( A) ( Samlipto et
al , 1988) . Both the
1
H and the
13
C NMR spectra data
of 1were similar to those of 8 (Yeap et al , 1989) except
for methylbutyryl. Downf ield carbons resonances ( D
16017 and 2 @ 16011) , attributed to three oxygenated
carbons and three upfield methine carbon resonances (D
9811 and 2 @ 9619) , were observed together with the
hexose carbon resonances in the aliphatic region. Mythy-l
butyryl moiety was identified on the basis of HSQC and
HMBC data (Table 2) . The HSQC spectrum showed the
connectivity between C- 2d ( D 4212) and H- 2d (D
2144) , C- 3d (D 2713) and H- 3dA (D1164) , H- 3d
B (D 1145) , C- 4d (D 1118) and H- 4d (D 0186) , C
- 5d (D 1618) and H- 5d (D 1113) . The hexose moiety
of compound 1 was ident ified as D-glucopyranosyl by
means of its
1
H and
13
C NMR data ( Tables 1 and 2)
( Walker et al , 1976) . The attachment of the phloroglu-
cinol moiety at C- 1c and the attachment of the methylbu-
tyryl group at C- 6c on the glucose was proved by HMBC
experiments, according to a correlat ion betweenH- 1c (D
4182) and C- 1c (D 16017) , H- 6c (D 4139, 4113, )
and C- 1d (D 17815) . Comparied with 1- [ ( 2-methylbu-
tyryl) phloroglucinyl ]-B-D-glucopyranoside ( Samlipto et
al , 1988) , 1 differs structurally in subst ituent position
of methylbutyryl. Therefore, the structure of 1 is, 1-
phlorogluciny-l ( 6-methylbutyryl )-B-D-glucopyranoside,
named cylindrin A.
Table 1 1H-NMR assignment for compounds 1 ( 500MHz) and 2 (400MHz) ( CD3OD)
H
1
D H-H COSY
2
D H-H COSY
2 6105 1H, d ( J= 210) 4 6195 1H, d ( J = 117)
3 6195 1H, d ( J = 117) 5
4 5196 1H, t ( J = 210)
5 6174 1H, dd ( J = 117, 812) 3, 6
6 6105 1H, d ( J= 210) 4 6172 1H, d ( J = 812) 5
1c 4182 1H, d ( J= 618) 2c 4171 1H, d ( J = 618)
2c 3161 1H, m 3160 1H, m
3c 3143 1H, m 3151 1H, m
4c 3133 1H, m 3135 1H, m
5c 3135 1H, m 3144 1H, m
6cA 4141 1H, dd ( J = 1114, 210) 4147 1H, dd ( J = 1119, 212)
6cB 4122 1H, dd ( J = 1114, 618) 4117 1H, dd ( J = 1119, 614)
2d 2144 1H, m 5d, 3dA, 3dB 2143 1H, m 5d, 3dA, 3dB
3dA 1164 1H, m 2d, 3dB, 4d 1163 1H, m 2d, 3dB, 4d
3dB 1145 1H, m 2d, 3dA, 4d 1146 1H, m 2d, 3dB, 4d
4d 0186 3H, t ( J = 714) 3dA, 3dB 0185 3H, t ( J= 716) 3dA, 3dB
5d 1113 3H, d ( J= 710) 2d 1112 3H, d ( J = 710) 2d
1Ê 2154 2H, t ( J= 714) 2d
2Ê 1176 2H, m 1Ê , 3Ê
3Ê 3152 2H, t ( J= 618) 2Ê
Compound 2 was obtained as amorphous powder, with
a molecular formula of C20H30O9 indicated by the quas-i
molecular ion peak at mPz 413 [ M-H] - in its negative
FABMS and mPz 41311804 [ M-H ] - in its HREIMS
( calcd. for C20H30O9 mPz 41311811) , which also was
supported by the
13
C NMR and DEPT spectral data. The
spectral data were similar to those of 1, except for three
more methylene signal. Its phenolic cycle is 1, 2, 4-
three subst itute because
1
H NMR spectrum gave H- 3 (D
6195, d, J= 117Hz) , H- 5 (D 6174, dd, J= 117,
812Hz) and H- 6 (D6172, d, J= 812Hz) . The at-
tachment of the 3-hydroxy-l propyl moiety at C - 4 was
92 云 南 植 物 研 究 28卷
proved by HMBC experiments. There was a correlated
cross-relaxation between the signal of H- 1Ê (D2154, t,
J= 714) with that of C- 4 (D135) and a correlation be-
tween H- 3 (D 6195) with C- 2 (D14614) and C- 4 (D
135) . There was also a correlation between H- 5 (D
6174) and H- 6 (D6172) with C- 1 (D14615) (Table 2
and Fig. 2) . The structure of 2 is , therefore, elucidat-
ed as 1- [ 4- ( 3-hydroxy-l propyl ) ]-pyrocatechol- ( 6-
methybutyryl )- B- D- glucopyranoside, named cylindrin
B.
Fig. 1 Structures of compounds 1, 2, 8
Fig. 2 Selected HMBC coorelat ions of 2
Compounds 3- 9 were characterized by comparing
their spectral data
1
H,
13
C NMR, MS, IR and UV with
those in the literature. Their structures ( Fig. 1) were
tachioside ( 3) ( Shogo et al , 1987) , syingic acid-4-B-
D-glucopyranoside ( 4) ( Kashiwada et al , 1986) , 1-B-
D-glucopyranosyloxy-3-methoxy-5-hydroxy benzene ( 5 )
(Koray et al , 1993) , 4-hydroxy-3-methoxypheno-l 1-O-
B-D-glucoside ( 6) ( Reiko et al , 1989) , 4-hydroxy-2,
6-dimethoxypheno-l 1-O-B-D-glucoside ( 7) ( Shogo et al ,
1987) , phloroglucino-l 1-O-B-D-glucoside ( 8) ( Yeap et
al , 1989) , 1-B-D-glucosyloxy-2- ( 3-methoxy-4-hydroxy-
phenyl) propane-1, 3-diol ( 9) ( Gilles et al , 1997) .
Table 2 13C-NMR assignment for compound 1 ( 125MHz)
and 2 ( 100 MHz) ( CD3OD)
C 1 Coupled to H 2 Coupled to H
D HMBC D HMBC
1 16017 2, 6, 1c 14615 5, 6, 1c
2 9619 4 14614 3
3 16011 2, 6 11912 1Ê
4 9811 2, 6 135 3, 5, 1Ê , 2Ê
5 16011 2, 6 12418 6, 1Ê
6 9619 4 117 5
1c 10119 2c 10414 2c, 3c
2c 7513 1c, 3c, 4c, 5c 7516 1c, 3c, 4c , 5c
3c 7719 2c, 4c, 5c 7714 2c, 4c, 5c
4c 7118 3c, 5c, 6cA, 6cB 7116 3c, 5c, 6cA, 6cB
5c 7418 4c, 6cA, 6cB 7418 4c, 6cA, 6cB
6c 6416 4c, 5c 6416 4c, 5c
1d 17815 6cA, 6cB, 2d, 17812 6cA, 6cB, 2d
3dA, 3dB, 5d 3dA, 3dB, 5d
2d 4212 3d, 4d, 5d 4213 3d, 4d, 5d
3d 2713 2d, 4d, 5d 2718 2d, 4d, 5d
4d 1118 2d, 3d 1119 2d, 3d
5d 1618 2d, 3d 17 2d, 3d
1Ê 3214 2Ê , 3Ê
2Ê 3516 1Ê , 3Ê
3Ê 6212 1Ê , 2Ê
Experimental
General Experimental Procedures Optical rotations were
measured on a JASCO-20 polarimeter. UV spectra were recorded on
a SHIMADZU 210A spectrophotometer. IR spectra were recorded
on a Bio-Rad FTS-135 infrared spectrophotometer with KBr pellets.
MS spectra were taken on a VG Auto Spce-3000. The 1D and 2D
NMR experiments were performed on a BRUKER AM-400 or DRX-
500 instruments. Column chromatography ( CC) was performed with
931期 朱向东等: 水红木中两个新的酚苷成分
silica gel ( 200- 300 mesh, Qingdao Marine Chemical Inc. , Ch-i
na) , silica gel H ( 60 Lm, Qingdao Marine Chemical Inc. , Ch-i
na) , Lichroprep RP18 gel ( 40- 63Lm, Merck, Darmstadt, Ger-
many) , and Sephadex-LH-20 ( 25- 100Lm, Amersham Bioscienc-
es, Sweden) , TLC spots were detected by spraying with 5%
H2 SO4 in EtOH followed by heating.
Plant materials Dried stems and leaves of V1 cylindricum
were collected at Kunming, Yunnan, China in April 2004. The
plant was identified by Dr. Li Rong. A voucher specimen ( KUN
No. 0085118) has been deposited in the Herbarium of the Depart-
ment of Taxonomy, Kunming Institute of Botany Chinese academy of
Sciences.
Extraction and Isolation Dried stems and leaves of V1 cyl-
indricum ( 111 2 kg ) were extracted three times with 90% ethanol
under reflux apparatus, and the extract was filtered. After evapora-
tion of ethanol under reduced pressure, the concentrated extract was
suspended in water and extracted with petroleum benzine, EtOAc,
n-BuOH. The EtoAc extract ( 510 g) was subjected to column chro-
matography over silica gel ( 200- 300 mesh) , eluting with CHCl3-
MeOH ( 9B1- 8B2) and divided into ten fractions.
Fraction 7 ( 40 g ) as chromatographed on silica gel ( 200- 300
mesh) , developing with CHCl3-MeOH ( 9B1- 8B2) and divided into 14
subfractions ( 1- 14) . Subfractions 9- 13 was rechromatographed on si-l
ica gel H, sephadexLH-20 (methanol and CHCl3 1B1) , and purified
by RP18 gel column chromatography using MeOH-H2O ( 7B3) to yield
compounds 1 ( 14 mg) , 2 (16 mg) , 3 ( 13mg) , 6 ( 11 mg) .
Fraction 3 ( 3 g) were perform in same methods to yield com-
pounds 7 ( 17 mg) . Fraction 9 ( 60 g) was chromatographed on sil-i
ca gel ( 200- 300 mesh) , developing with CHCl3-MeOH ( 9B1- 8B
2) and divided into 16 subfractions ( 1- 16) . Subfractions 5- 8 was
rechromatographed on silica gel H, sephadexLH-20 ( methanol and
CHCl3 1B1) , and purified by RP18 gel column chromatography using
MeOH-H2O ( 6B4) to yield compounds 4 ( 316 mg ) , 5 ( 24 mg ) ,
8 ( 15 mg) , 9 ( 12 mg) .
Cylindrin A ( 1) , C17H24O9 , amorphous powder; [A]
25
D - 53
( c 014, MeOH ) . UV max ( MeOH ) : 204, 275 nm; IR bands
( KBr ) : 3421, 2925, 1714, 1610, 1462, 1159, 1074, 1010
cm- 1 ; Negative FAB-MS mPz : 371 [ M-H ] ; HREIMS mPz :
3711 1348 [ M-H] - ; 1H NMR ( CD3OD, 500 MHz) data see
Tab1e 1, 13C NMR ( CD3OD, 125MHz) data see Table 2.
Cylindrin B ( 2) , amorphous powder; [A] 25D - 2816 ( c 013
MeOH) ; UV max ( MeOH) : 203, 280 nm; IR bands ( KBr ) :
3429, 2934, 1719, 630, 1514, 1278, 1070 cm- 1 ; Negative
FAB-MS mPz : 413 [ M-H] ; HREIMS mPz : 41311804 [ M-H] - ;
1H NMR ( CD3OD, 400 MHz) data see Table1,
13 C NMR
( CD3OD, 100MHz) data see Table 2.
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