A New Glycoside from Sparganium stoloniferum
517
25.6 (C-28), 22.2 (C-26), 22.1 (C-27), 21.3 (C-6), 20.2 (6'-OAc; C=O), 171.4 (4'-OAc; C=O), 170.9 (1-OAc;
(C-9), 19.6 (C-30), 18.5 (C-21), 18.2 (C-18), 14.2 (C-29). C=O), 167.1 (C-9''), 149.2 (C-4''), 148.3 (C-3''), 146.9 (C-
7''), 126.4 (C-1''), 123.3 (C-6''), 115.3 (C-5''), 113.3 (C-
p
-Hydroxybenzaldehyde (2)
8''), 110.8 (C-2''), 102.2 (C-2), 89.6 (C-1'), 83.0 (C-5),
o
White amorphous powder, mp 113-114 C; FAB-MS 78.1 (C-3), 73.2 (C-2'), 73.0 (C-4), 72.4 (C-4'), 70.9 (C-
+
1
m/z: 123 [M+H] ; H-NMR (CD OD, 500 MHz):
δ
7.77 5'), 70.4 (C-3'), 64.8 (C-1), 62.3 (C-6, 6'), 55.4 (3''-
= 8.7 Hz, H- OCH ), 19.8 (2'-OAc; CH ), 19.6 (6'-OAc; CH ), 19.4 (4'-
, 5); C-NMR (CD OD, 125 MHz): δ 191.6 (C=O), OAc; CH ), 19.3 (1-OAc; CH ).
3
3
(
3
1
2H, d,
J
= 8.7 Hz, H-2, 6), 6.93 (2H, d,
J
3
3
3
1
3
3
3
64.1 (C-4), 132.3 (C-2, 6), 129.1 (C-1), 115.7 (C-3, 5).
β
-
D
-(6-
copyranoisde (7)
White amorphous powder, mp 231-232 C; FAB-MS Colorless amorphous solid, [
O
-
trans-Feruloyl)fructofuranosyl-
α
-
D
-
O
-glu-
Ferulic acid (3)
o
25
+58.8o
α]
(c
0.1 in
D
+
1
1
m/z: 195 [M+H] ; H-NMR (CD
1H, d, = 15.9 Hz, H-7), 7.19 (1H, d,
), 7.06 (1H, dd, = 8.1, 1.3 Hz, H-6), 6.80 (1H, d,
.1 Hz, H-5), 6.38 (1H, d, = 15.9 Hz, H-8), 3.89 (3H, HR-FAB-MS m/z: 541.1532 [M+Na] (calculated for
3
OD, 500 MHz):
δ
7.65 MeOH); IR (KBr):
νmax cm- : 3391, 2945, 1684, 1636,
1
(
J
J
= 1.3 Hz, H- 1601, 1519, 1457, 1278, and 1027 cm- ; UV
λmax (MeOH)
2
8
J
J
=
nm (log ε): 237 (4.33), 291 (4.23), and 324 (4.33) nm;
+
J
13
1
s, -OCH
49.1 (C-3), 147.9 (C-4), 144.5 (C-7), 123.0 (C-1), 121.3
C-6), 116.5 (C-8), 115.3 (C-5), 110.6 (C-2), 55.2 (-OCH
3
); C-NMR (CD
3
OD, 125 MHz):
δ
168.0 (C-9),
C
22
H
30
O
14Na, 541.1533); H-NMR (CD
7.63 (1H, d, = 15.8 Hz, H-7''), 7.18 (1H, d,
= 8.2, 1.7 Hz, H-6''), 6.81
= 8.2 Hz, H-5''), 6.37 (1H, d, = 15.8 Hz, H-
8''), 5.40 (1H, d, = 3.5 Hz, H-1'), 4.44 (2H, m, H-6),
White amorphous powder, mp 210-212 C; FAB-MS 4.44, 3.90 (2H, m, H-6'), 4.08 (1H, d, = 8.2 Hz, H-3),
7.62 4.03 (1H, m, H-5), 3.99 (1H, m, H-5'), 3.99 (1H, dd,
= 8.4 Hz, H-2, 8.2, 7.6 Hz, H-4), 3.90 (3H, s, H-3''-OCH ), 3.71 (1H,
3
OD, 500 MHz):
1
(
δ
J
J
= 1.7
3
). Hz, H-2''), 7.07 (1H, dd,
J
(1H, d,
J
J
p-Coumaric acid (4)
J
o
J
+
1
m/z: 165 [M+H] ; H-NMR (CD
1H, d, = 16.2 Hz, H-7), 7.44 (1H, d,
), 6.89 (2H, d,1 = 8.4 Hz, H-3, 5), 6.35 (1H, d,
3
OD, 500 MHz):
δ
J =
(
6
1
J
J
3
J
J
=
dd,
J = 9.9, 9.3 Hz, H-3'), 3.64 (2H, br s, H-1), 3.41
3
13
6.2 Hz, H-8); C-NMR (CD
3
OD, 125 MHz):
δ
167.1 (1H, dd,
J
= 9.9, 3.5 Hz, H-2'); C-NMR (CD
169.1 (C-9''), 150.7 (C-4''), 149.4 (C-3''), 147.0
(C-7''), 128.0 (C-1''), 124.2 (C-6''), 116.5 (C-5''), 115.2
C-8''), 111.7 (C-2''), 103.4 (C-2), 93.4 (C-1'), 80.8 (C-5),
78.9 (C-3), 76.8 (C-4), 73.6(C-3'), 73.1 (C-2'), 72.1 (C-4'),
White amorphous powder, mp 208-211 C; FAB-MS 71.6 (C-5'), 66.7 (C-6), 65.6 (C-6'), 64.1(C-1), 56.4(3''-
3
OD, 125
(
C-9), 160.2 (C-4), 145.7 (C-7) 135.5 (C-1), 130.1 (C-2, MHz):
δ
6), 116.5 (C-3, 5), 115.7 (C-8).
(
Vanillic acid (5)
o
+
1
m/z: 169 [M+H] ; H-NMR (CD
1H, dd, = 8.4, 1.5 Hz, H-6), 7.55 (1H, d,
H-2), 6.83 (1H, d, = 8.0 Hz, H-5), 3.90 (3H, s, -OCH3);
OD, 125 MHz): 168.8 (-COOH), 151.5 anosyl-
C-3), 147.5 (C-4), 124.2 (C-1), 122.0 (C-6), 114.7 (C-2), Colorless amorphous solid, [
3
OD, 500 MHz):
δ
7.56 OCH
3
).
(
J
J
= 1.5 Hz,
J
β-
D
-(1-
O
α
-Acetyl-3,6- trans-diferuloyl)fructofur-
O
-
1
3
C-NMR (CD
3
δ
-D-2',4',6'.-O-triacetylglucopyranoisde (8)
2
5
o
(
1
α
]
+36.3 (c 0.16 in
D
+
1
12.7 (C-5), 55.6 (-OCH3).
CHCl ); FAB-MS m/z: 863 [M+H] ; H-NMR (CD OD,
3
3
5
00 MHz):
δ
7.69 (1H, d,
J
= 15.8 Hz, H-7''), 7.67 (1H,
β
-
α-
D
D
-(1-
-2',4',6'.-
Colorless amorphous solid, [
O
-Acetyl-3-
O
-
trans-feruloyl)fructofuranosy-
d,
H-6'''), 7.10 (2H, br s, H-2'', H-2'''), 6.80 (2H, d,
+50.0 (c 0.1 in Hz, H-5'', H-5'''), 6.42 (2H, br d, = 15.8 Hz, H-8'', H-
= 3.5 Hz, H-1'), 5.38 (1H, d, = 7.6
= 15.8 Hz, H-7''), 7.28 (1H, Hz, H-3), 4.67 (1H, dd, = 9.9, 3.5 Hz, H-2'), 4.51 (1H,
= 8.2, 1.7 Hz, H- br s, = 4.7 Hz, H-6'), 4.45 (1H, t, = 7.6 Hz, H-4),
= 8.2 Hz, H-5''), 6.42 (1H, d, = 15.8 4.24 (1H, m, H-5), 4.24, 4.12 (2H, br s, H-1), 4.23 (1H,
Hz, H-8''), 5.63 (1H, d, = 3.5 Hz, H-1'), 5.35 (1H, d, m, H-5'), 4.15 (1H, m, H-4'), 4.13 (1H, m, H-6), 4.11
7.6 Hz, H-3), 4.75 (1H, dd, = 10.0, 3.5 Hz, H-2'), (1H, d, = 7.6 Hz, H-3'), 3.92 (3H, s, 3'''-OCH ), 3.90
= 7.6 Hz, H-4), 4.21, 4.10 (2H, br s, H-1), (3H, s, 3''-OCH ), 2.12 (3H, s, 6'-OAc), 2.10 (3H, s, 4'-
J
= 15.8 Hz, H-7'''), 7.10 (2H, br d,
J
= 9.9 Hz, H-6'',
O-triacetyglucopyranoisde (6)
J
= 8.2
2
5
o
α]
D
J
+
1
CHCl ); FAB-MS m/z: 687 [M+H] ; H-NMR (CD OD, 8'''), 5.69 (1H, d,
J
J
3
3
500 MHz):
δ
7.70 (1H, d,
J
J
d,
J
= 1.7 Hz, H-2''), 7.13 (1H, dd,
J
J
J
6''), 6.83 (1H, d,
J
J
J
J
=
J
J
3
4
4
9
3
.30 (1H, t,
J
3
13
.20 (1H, m, H-6'), 4.10 (1H, m, H-5'), 4.05 (1H, t,
J
=
OAc), 2.03 (3H, s, 2'-OAc), 1.88 (3H, s, 1-OAc); C-
OD, 125 MHz): 172.2 (6'-OAc; C=O), 172.1
.78 (1H, m, H-6), 2.11 (3H, s, 2'-OAc), 2.09 (3H, s, 6'- (4'-OAc; C=O), 171.0 (2'-OAc; C=O), 170.9 (1-OAc; C=O),
.9 Hz, H-3'), 3.95 (3H, s, 3''-OCH
3
), 3.94 (1H, m, H-6), NMR (CD
3
δ
13
OAc), 2.05 (3H, s, 4'-OAc), 1.98 (3H, s, 1-OAc); C- 167.8 (C-9''), 167.6 (C-9'''), 148.3 (C-4'''), 148.2 (C-4'', C-
NMR (CD OD, 125 MHz): 172.2 (2'-OAc; C=O), 171.6 7''), 147.5 (C-3'', C-3'''), 145.6 (C-7'''), 126.5 (C-1'', 1'''),
3
δ