3
56 J ournal of Natural Products, 2002, Vol. 65, No. 3
Itoh et al.
topyranoside (3.3 mg), and isorhamnetin 3-O-(6-O-R-L-rham-
nopyranosyl)-â-D-glucopyranoside (2.0 mg); fraction 11, stric-
tosamide (6.2 mg).
H-2 of galactosefC-1 of rhamnose-II, H
2
-6 of galactosefC-1
of rhamnose-III, H-1 of rhamnose-IIIfC-6 of galactose, H-âfCO
(δ 167.7), H -2′′, 6′′fC-â, H-âfC -2′′, 6′′, H-RfC-1′′; HR-SIMS
m/z 1061.3098 (calcd for C49 26, 1061.3140).
Isor h a m n etin
2
2
57
H O
Qu er cetin 3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-r h a m -
n op yr a n osyl(1f2)]-(4-O-tr a n s-p-cou m a r oyl)-â-D-ga la cto-
p yr a n osid e-7-O-r-L-r h a m n op yr a n osid e (1): yellow powder;
3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-
r h a m n op yr a n osyl(1f2)]-(4-O-tr a n s-fer u loyl)-â-D-ga la c-
2
4
MeOH
max
[
2
(
R]
D
-193° (c 1.0, MeOH); UV λ
nm (log ꢀ) 227sh (4.35),
top yr a n osid e-7-O-r-L-r h a m n op yr a n osid e (6): yellow pow-
der; [R]26
-185° (c 0.34, MeOH); UV λmax nm (log ꢀ) 250
MeOH
56.5 (4.31), 270sh (4.27), 299sh (4.33), 315.5 (4.40), 364sh
D
KBr
max
-1
1
KBr
max
-1
4.14); IR ν
cm 3394, 1699, 1655, 1605, 1516, 1495; H
(4.43), 270sh (4.27), 290sh (4.23), 332 (4.43); IR ν
cm
1
3
-
1
13
NMR, Table 1; C NMR, Table 2; SIMS m/z 1047 [M - H] ,
01, 755; ROESY H-6/H-1 of rhamnose-I, H-8/H-1 of rhamnose-
I, H-1 of rhamnose-II/H-2 of galactose, H-1 of rhamnose-III/
-6 of galactose; HMBC H-2′fC-2, H-6′fC-2, H-1 of rhamnose-
3421, 1697, 1653, 1599, 1516; H NMR, Table 1; C NMR,
-
9
Table 2; SIMS m/z 1091 [M - H] , 945, 915; ROESY H-2′/
OMe (δ 4.04), H-2′′/OMe (δ 3.96), H-6/H-1 of rhamnose-I, H-8/
H-1 of rhamnose-I, H-â/H-2′′, H-â/H-6′′; HMBC H-2′fC-2,
H-6′fC-2, H-1 of rhamnose-IfC-7, H-1 of rhamnose-IIfC-2
of galactose, H-1 of rhamnose-IIIfC-6 of galactose, H-4 of
galactosefCO (δ 168.7), H-RfCO (δ 168.7), H-âfCO (δ 168.7),
H-RfC-1′′, H-âfC-2′′, H-âfC-6′′, H-2′′fC-â, H-6′′fC-â; HR-
H
2
IfC-7, H-1 of galactosefC-3, H-1 of rhamnose-IIfC-2 of
galactose, H-1 of rhamnose-IIIfC-6 of galactose, H-4 of
galactosefCO (δ 165.9), H-RfCO (δ 165.9), H-âfCO (δ 165.9),
H-RfC-1′′; HR-SIMS m/z 1047.2951 (calcd for C48
047.2983).
55 26
H O ,
1
59
SIMS m/z 1091.3256 (calcd for C50H O27, 1091.3245).
Qu er cetin 3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-r h a m -
Alk a lin e Met h a n olysis of 1. A solution of compound 1
(20.0 mg) in 0.05 M NaOMe (0.2 mL) was stirred at room
temperature for 7 h. After neutralization with Amberlite IR-
n op yr a n osyl(1f2)]-(3-O-tr a n s-p-cou m a r oyl)-â-D-ga la cto-
p yr a n osid e-7-O-r-L-r h a m n op yr a n osid e (2): yellow powder;
[
2
(
2
1
MeOH
max
+
R]
D
-160° (c 1.0, MeOH); UV λ
nm (log ꢀ) 228sh (4.42),
120 (H form), the reaction mixture was concentrated and the
55.5 (4.40), 270sh (4.34), 300sh (4.42), 317.5 (4.49), 361sh
residue was subjected to preparative HPLC (MeOH-H
2
O,
KBr
max
-1
1
9
:11) to afford quercetin 3-O-R-L-rhamnopyranosyl(1f6)-[R-
4.24); IR ν
cm 3410, 1695, 1655, 1605, 1516, 1493; H
1
3
-
L-rhamnopyranosyl(1f2)]-â-D-galactopyranoside-7-O-R-L-rham-
nopyranoside (7) (4.5 mg) and methyl trans-p-coumarate (2.1
mg).
NMR, Table 1; C NMR, Table 2; SIMS m/z 1047 [M - H] ,
01; ROESY H-6/H-1 of rhamnose-I, H-8/H-1 of rhamnose-I,
H-R/H -2′′, 6′′, H-â/H -2′′, 6′′; HMBC H-2′fC-2, H-6′fC-2, H-1
of rhamnose-IfC-7, H-2 of galactosefC-1 of rhamnose-II, H-1
of rhamnose-IIfC-2 of galactose, H -6 of galactosefC-1 of
9
2
2
Qu er cetin 3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-r h a m -
n op yr a n osyl(1f2)]-â-D-ga la ctop yr a n osid e-7-O-r-L-r h a m -
2
2
8
rhamnose-III, H-1 of rhamnose-IIIfC-6 of galactose, H-3 of
galactosefCO (δ 168.3), H-RfCO (δ 168.3), H-âfCO (δ 168.3),
n op yr a n osid e (7): yellow powder; [R]
D
-132° (c 0.34,
MeOH
MeOH); UV λmax nm (log ꢀ) 256 (4.28), 270sh (4.14), 297sh
KBr
max
-1
1
H-RfC-1′′, H
047.3003 (calcd for C48
Isor h a m n etin
2
-2′′, 6′′fC-â, H-âfC
26, 1047.2983).
3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-
2
-2′′, 6′′; HR-SIMS m/z
(
3.81), 356 (4.14); IR ν
cm 3405, 1655, 1601, 1493; H
1
H
55
O
13
-
NMR, Table 1; C NMR, Table 2; SIMS m/z 901 [M - H] ;
ROESY H-6/H-1 of rhamnose-I, H-8/H-1 of rhamnose-I; HMBC
H-2′fC-2, H-1 of rhamnose-IfC-7, H-1 of rhamnose-IIfC-2
of galactose, H-2 of galactosefC-1 of rhamnose-II, H-1 of
r h a m n op yr a n osyl(1f2)]-(4-O-tr a n s-p-cou m a r oyl)-â-D-ga -
la ctop yr a n osid e-7-O-r-L-r h a m n op yr a n osid e (3): yellow
2
2
MeOH
max
powder; [R]
D
-222° (c 1.0, MeOH); UV λ
nm (log ꢀ)
rhamnose-IIIfC-6 of galactose, H
rhamnose-III; HR-SIMS m/z 901.2583 (calcd for C39
01.2615).
3
Meth yl tr a n s-p-cou m a r a te: H NMR (CD OD, 200 MHz)
2
-6 of galactosefC-1 of
2
3
30sh (4.36), 254 (4.39), 268 (4.32), 300sh (4.39), 317.5 (4.46),
49 24
H O ,
KBr
max
-1
1
9
62sh (4.22); IR ν
cm 3421, 1653, 1603, 1516; H NMR
1
3
-
1
Table 1; C NMR Table 2; SIMS m/z 1061 [M - H] , 915, 769;
ROESY H-2′/OMe, H-6/H-1 of rhamnose-I, H-8/H-1 of rham-
δ 3.80 (3H, s, OMe), 6.30 (1H, d, J ) 16.0 Hz, H-R), 6.84 (2H,
nose-I, H-R/H
rhamnose-IfC-7, H-1 of galactosefC-3, H-2 of galactose fC-1
of rhamnose-II, H-1 of rhamnose-IIfC-2 of galactose, H -6 of
2
-2′′, 6′′, H-â/H
2
-2′′, 6′′; HMBC H-2′fC-2, H-1 of
d, J ) 8.5 Hz, H-3, H-5), 7.44 (2H, d, J ) 8.5 Hz, H-2, H-6),
+
7.64 (1H, d, J ) 16.0 Hz, H-â); EIMS m/z 178 [M] (100%),
147.
2
galactosefC-1 of rhamnose-III, H-1 of rhamnose-IIIfC-6 of
galactose, H-4 of galactosefCO (δ 168.7), H-RfCO (δ 168.7),
Acid Hyd r olysis of Com p ou n d 7. Compound 7 (1 mg) was
heated at 95 °C with dioxane (0.5 mL) and 5% H SO (0.5 mL)
2
4
-
H-âfCO (δ 168.7), H-RfC-1′′, H
HR-SIMS m/z 1061.3155 (calcd for C49
Isor h a m n etin
r h a m n op yr a n osyl(1f2)]-(3-O-tr a n s-p-cou m a r oyl)-â-D-ga -
la ctop yr a n osid e-7-O-r-L-r h a m n op yr a n osid e (4): yellow
2
-2′′, 6′′fC-â, H-âfC
26, 1061.3140).
3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-
2
-2′′, 6′′;
for 1 h. After neutralization with Amberlite IRA-400 (OH
form), the reaction mixture was concentrated and the residue
was passed through a Sep-Pak C18 cartridge with H O. The
57
H O
2
eluate was concentrated, and the residue was treated with
L-cysteine methyl ester hydrochloride (1 mg) in pyridine (0.125
mL) at 60 °C for 1 h. The solution was then treated with N,O-
bis(trimethylsilyl)trifluoroacetamide (0.05 mL) at 60 °C for 1
h. The supernatant was applied to GLC; GLC conditions:
column, Supelco SPB-1, 30 m × 0.25 mm; column temperature,
2
5
MeOH
nm (log ꢀ)
max
powder; [R]
D
-92° (c 0.38, MeOH); UV λ
2
30sh (4.30), 253.5 (4.34), 267.5 (4.24), 299sh (4.32), 318.5
4.41), 360sh (4.17); IR ν
NMR, Table 1; C NMR, Table 2; SIMS m/z 1061 [M - H] ,
15, 769; ROESY H-2′/OMe, H-6/H-1 of rhamnose-I, H-8/H-1
of rhamnose-I, H-R/H -2′′, 6′′, H-â/H -2′′, 6′′; HMBC H-2′fC-
, H-6′fC-2, H-1 of rhamnose-IfC-7, H-1 of rhamnose-IIfC-2
KBr
max
-1
1
(
cm 3421, 1653, 1602, 1516; H
1
3
-
2
1
2 R
30 °C; N flow rate, 0.8 mL/min; t of derivatives, D-galactose
9
3.7 min, L-galactose 14.6 min, L-rhamnose 8.9 min. D-
Galactose and L-rhamnose were detected from 7.
2
2
2
of galactose, H-2 of galactosefC-1 of rhamnose-II, H-1 of
rhamnose-IIIfC-6 of galactose, H-3 of galactosefCO (δ 168.3),
Ack n ow led gm en t. We thank Dr. M. Sugiura (Kobe Phar-
maceutical University) for the NMR spectra and Dr. K. Saiki
Kobe Pharmaceutical University) for the MS measurements.
H-RfCO (δ 168.3), H-âfCO (δ 168.3), H-RfC-1′′, H
′′fC-â, H-âfC -2′′, 6′′; HR-SIMS m/z 1061.3158 (calcd for
26, 1061.3140).
Isor h a m n etin 3-O-r-L-r h a m n op yr a n osyl(1f6)-[r-L-
2
-2′′,
6
2
(
49 57
C H O
Refer en ces a n d Notes
r h a m n op yr a n osyl(1f2)]-(4-O-cis-p -cou m a r oyl)-â-D-ga -
la ctop yr a n osid e-7-O-r-L-r h a m n op yr a n osid e (5): yellow
(1) Atta-ur-Rahman; Qureshi, M. M.; Zaman, K.; Malik, S.; Ali, S. S.
2
0
MeOH
nm (log ꢀ)
max
Fitoterapia 1989, 60, 291-322.
2) Chatterjee, A.; Banerji, J .; Banerji, A. J . Indian Chem. Soc. 1974,
powder; [R]
D
-147° (c 0.45, MeOH); UV λ
(
2
3
1
30sh (4.37), 254 (4.44), 267 (4.36), 297sh (4.31), 320 (4.39),
3421, 1655, 1601, 1516, 1493,
456; H NMR, Table 1; C NMR, Table 2; SIMS m/z 1061
5
1, 156-170.
KBr
max
-1
55sh (4.31); IR ν
cm
(3) Ferrari, F.; Messana, I.; Botta, B. J . Nat. Prod. 1986, 49, 1150-1151.
(4) Erdelmeier, C. A. J .; Wright, A. D.; Orjala, J .; Baumgartner, B.; Rali,
T.; Sticher, O. Planta Med. 1991, 57, 149-152.
1
13
-
[
M - H] , 915, 769, 461, 315; ROESY H-2′/OMe, H-6/H-1 of
rhamnose-I, H-8/H-1 of rhamnose-I, H-â/H -2′′, 6′′; HMBC
H-2′fC-2, H-6′fC-2, H-1 of rhamnose-IIfC-2 of galactose,
(
(
5) El-Naggar, L. J .; Beal, J . L. J . Nat. Prod. 1980, 43, 649-707.
6) Ishimaru, K.; Sudo, H.; Satake, M.; Shimomura, K. Phytochemistry
1990, 29, 3823-3825.
2