804
H. Gao et al. / Phytochemistry 70 (2009) 795–806
NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5, 100 MHz)
spectroscopic data, see Table 1; +ESI-IT-MS m/z: 1373 [M+Na]+;
+ESI-IT-MS2 (1373) m/z: 903 [M+Naꢀ470]+, 859 [M+Naꢀ470
ꢀ44]+; +ESI-IT-MS3 (1373ꢀ903) m/z: 859 [(M+Naꢀ470)ꢀ44]+, 741
[(M+Naꢀ470)ꢀ162]+, 697 [(M+Naꢀ470)ꢀ162ꢀ44]+; -ESI-IT-MS m/
z: 1349 [MꢀH]ꢀ; -ESI-IT-MS2 (1349) m/z: 879 [MꢀHꢀ470]ꢀ, 717
[MꢀHꢀ470ꢀ162]ꢀ; -ESI-IT-MS3 (1349ꢀ879) m/z: 835 [(MꢀH
ꢀ470)ꢀ44]ꢀ, 717 [(MꢀHꢀ470)ꢀ162]ꢀ, 699 [(MꢀHꢀ470) ꢀ162
ꢀ18]ꢀ, 571 [(MꢀHꢀ470)ꢀ162ꢀ146]ꢀ, 553 [(MꢀHꢀ470) ꢀ162
ꢀ146ꢀ18]ꢀ, 439 [(MꢀHꢀ470)ꢀ162ꢀ146ꢀ132]ꢀ; +HR-ESI-Q-TOF-
MS m/z: 1373.6335 [M+Na]+ (calcd. for C64H102NaO30, 1373.6354).
for 1H NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5,
100 MHz) spectroscopic data, see Table 1; +ESI-IT-MS m/z: 1213
[M+Na]+; +ESI-IT-MS2 (1213) m/z: 889 [M+Naꢀ324]+, 743
[M+Naꢀ324ꢀ146]+; +ESI-IT-MS3 (1213-889) m/z: 845 [(M+Na
ꢀ324)ꢀ44]+, 757 [(M+Naꢀ324)ꢀ132]+, 743 [(M+Naꢀ324)ꢀ146]+,
713 [(M+Naꢀ324)ꢀ132ꢀ44]+, 699 [(M+Naꢀ324)ꢀ146ꢀ44]+, 611
[(M+Naꢀ324)ꢀ146ꢀ132]+; -ESI-IT-MS m/z: 1189 [MꢀH]ꢀ; -ESI-
IT-MS2 (1189) m/z: 865 [MꢀHꢀ324]ꢀ, 733 [MꢀHꢀ324ꢀ132]ꢀ,
719 [MꢀHꢀ324ꢀ146]ꢀ; -ESI-IT-MS3 (1189ꢀ865) m/z: 733
[(MꢀHꢀ324)ꢀ132]ꢀ, 719 [(MꢀHꢀ324)ꢀ146]ꢀ, 587 [(MꢀHꢀ324)
ꢀ132ꢀ146]ꢀ, 569 [(MꢀHꢀ324)ꢀ132ꢀ146ꢀ18]ꢀ, 455 [(MꢀHꢀ
324)ꢀ132ꢀ146ꢀ132]ꢀ; +HR-ESI-Q-TOF-MS m/z: 1213.5597
[M+Na]+ (calcd. for C57H90NaO26, 1213.5618).
3.3.3. 3-O-
(1 ? 2)]-
a
-
L
-arabinopyranosyl-(1 ? 3)-[
a-L-rhamnopyranosyl-
a
-L
-arabinopyranosyl-30-norhederagenin-28-O-a-L-
rhamnopyranosyl-(1 ? 4)-b-
D
-glucopyranosyl-(1 ? 6)-b-
D-
3.3.6. 3-O-b-D-xylopyranosyl-(1 ? 3)-[a-L-rhamnopyranosyl-
glucopyranosyl ester (3)
(1 ? 2)]- -arabinopyranosyl-30-norhederagenin-28-O-b-D-
glucopyranosyl-(1 ? 6)-b-D-glucopyranosyl ester (6)
a
-
L
White amorphous powder; ½a D27
ꢂ
9.9 (c 0.13, MeOH–H2O 1:1); IR
(KBr)
m
max (cmꢀ1) 3389, 2937, 1743, 1650, 1449, 1389, 1065; for 1H
White amorphous powder; ½a D27
ꢂ
10.2 (c 0.10, MeOH–H2O 1:1);
NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5, 100 MHz)
spectroscopic data, see Table 1; +ESI-IT-MS m/z: 1359 [M+Na]+;
+ESI-IT-MS2 (1359) m/z: 889 [M+Naꢀ470]+, 743 [M+Naꢀ
470ꢀ146]+, 493 [470+Na]+; +ESI-IT-MS3 (1359-889) m/z: 845
[(M+Naꢀ470)ꢀ44]+, 757 [(M+Naꢀ470)ꢀ132]+, 743 [(M+Naꢀ470)
ꢀ146]+, 713 [(M+Naꢀ470)ꢀ132ꢀ44]+, 699 [(M+Naꢀ470)ꢀ146
ꢀ44]+; +ESI-IT-MS3 (1359-493) m/z: 475, 447, 421, 405, 349, 347,
331, 289, 203; -ESI-IT-MS m/z: 1335 [MꢀH]ꢀ; -ESI-IT-MS2 (1335)
m/z: 865 [MꢀHꢀ470]ꢀ, 733 [MꢀHꢀ470ꢀ132]ꢀ, 719 [MꢀHꢀ470
ꢀ146]ꢀ; -ESI-IT-MS3 (1335-865) m/z: 733 [(MꢀHꢀ470)ꢀ132]ꢀ,
719 [(MꢀHꢀ470)ꢀ146]ꢀ, 587 [(MꢀHꢀ470)ꢀ132ꢀ146]ꢀ, 569
[(MꢀHꢀ470)ꢀ132ꢀ146ꢀ18]ꢀ, 455 [(MꢀHꢀ470)ꢀ132ꢀ146ꢀ
132]ꢀ; -ESI-IT-MS3 (1335-733) m/z: 587 [(MꢀHꢀ470ꢀ132)
ꢀ146]ꢀ, 569 [(MꢀHꢀ470ꢀ132)ꢀ146ꢀ18]ꢀ, 455 [(MꢀHꢀ470ꢀ
132)ꢀ146ꢀ132]ꢀ; -ESI-IT-MS3 (1335-719) m/z: 587 [(MꢀHꢀ470
ꢀ146)ꢀ132]ꢀ, 569 [(MꢀHꢀ470ꢀ146)ꢀ132ꢀ18]ꢀ, 455 [(MꢀHꢀ
470ꢀ146)ꢀ132ꢀ132]ꢀ; +HR-ESI-Q-TOF-MS m/z: 1359.6134
[M+Na]+ (calcd. for C63H100NaO30, 1359.6197).
IR (KBr) mmax (cmꢀ1) 3451, 2932, 1743, 1656, 1455, 1381, 1071;
for 1H NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5,
100 MHz) spectroscopic data, see Table 2; +ESI-IT-MS m/z: 1213
[M+Na]+; +ESI-IT-MS2 (1213) m/z: 889 [M+Naꢀ324]+, 743
[M+Naꢀ324ꢀ146]+; +ESI-IT-MS3 (1213ꢀ889) m/z: 845 [(M+Na
ꢀ324)ꢀ44]+, 757 [(M+Naꢀ324)ꢀ132]+, 743 [(M+Naꢀ324)ꢀ146]+,
713 [(M+Naꢀ324)ꢀ132ꢀ44]+, 699 [(M+Naꢀ324)ꢀ146ꢀ44]+, 611
[(M+Naꢀ324)ꢀ146ꢀ132]+; -ESI-IT-MS m/z: 1189 [MꢀH]ꢀ; -ESI-
IT-MS2 (1189) m/z: 865 [MꢀHꢀ324]ꢀ, 733 [MꢀHꢀ324ꢀ132]ꢀ;
-ESI-IT-MS3 (1189-865) m/z: 733 [(MꢀHꢀ324)ꢀ132]ꢀ, 719
[(MꢀHꢀ324)ꢀ146]ꢀ, 587 [(MꢀHꢀ324)ꢀ132ꢀ146]ꢀ, 569 [(MꢀH
ꢀ324)ꢀ132ꢀ146ꢀ18]ꢀ,
455
[(MꢀHꢀ324)ꢀ132ꢀ146ꢀ132]ꢀ;
+HR-ESI-Q-TOF-MS m/z: 1213.5584 [M+Na]+ (calcd. for C57H90
-
NaO26, 1213.5618).
3.3.7. 3-O-
a
-L-arabinopyranosyl-(1 ? 3)-[a-L-rhamnopyranosyl-
(1 ? 2)]-
a-
L-arabinopyranosyl-hederagenin-28-O-a-L-
rhamnopyranosyl-(1 ? 4)-b-D-glucopyranosyl-(1 ? 6)-b-D-
glucopyranosyl ester (7)
3.3.4. 3-O-b-
D
-xylopyranosyl-(1 ? 3)-[
a
-
L
-rhamnopyranosyl-(1 ? 2)]
-rhamnopyranosyl-
-glucopyranosyl ester (4)
13.7 (c 0.12, MeOH–H2O 1:1);
White amorphous powder; ½a D27
ꢀ6.6 (c 0.13, MeOH–H2O 1:1);
ꢂ
-a-L-arabinopyranosyl-30-norhederagenin-28-O-
a-L
IR (KBr) m
max (cmꢀ1) 3322, 2936, 1740, 1648, 1456, 1383, 1066; for
(1 ? 4)-b-
D
-glucopyranosyl-(1 ? 6)-b-
D
1H NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5,
100 MHz) spectroscopic data, see Table 2; +ESI-IT-MS m/z: 1375
[M+Na]+; +ESI-IT-MS2 (1375) m/z: 905 [M+Naꢀ470]+, 493
[470+Na]+; +ESI-IT-MS3 (1375-905) m/z: 861 [(M+Naꢀ470)ꢀ44]+,
773 [(M+Naꢀ470)ꢀ132]+, 759 [(M+Naꢀ470)ꢀ146]+, 729 [(M+Na
ꢀ470)ꢀ132ꢀ44]+, 715 [(M+Naꢀ470)ꢀ146ꢀ44]+, 627 [(M+Naꢀ
470)ꢀ146ꢀ132]+; +ESI-IT-MS3 (1375-493) m/z: 475, 447, 421,
405, 349, 347, 331, 289, 203; -ESI-IT-MS m/z: 1351 [MꢀH]ꢀ;
-ESI-IT-MS2 (1351) m/z: 881 [MꢀHꢀ470]ꢀ, 749 [MꢀHꢀ
470ꢀ132]ꢀ, 735 [MꢀHꢀ470ꢀ146]ꢀ; -ESI-IT-MS3 (1351-881) m/z:
749 [(MꢀHꢀ470)ꢀ132]ꢀ, 735 [(MꢀHꢀ470)ꢀ146]ꢀ, 603 [(MꢀH
ꢀ470) ꢀ132ꢀ146]ꢀ, 585 [(MꢀHꢀ470)ꢀ132 ꢀ146ꢀ18]ꢀ, 471
White amorphous powder; ½a D28
ꢂ
IR (KBr) mmax (cmꢀ1) 3401, 2938, 1739, 1642, 1447, 1381, 1065;
for 1H NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5,
100 MHz) spectroscopic data, see Table 1; +ESI-IT-MS m/z: 1359
[M+Na]+; +ESI-IT-MS2 (1359) m/z: 889 [M+Naꢀ470]+, 845
[M+Naꢀ470ꢀ44]+, 743 [M+Naꢀ470ꢀ146]+, 493 [470+Na]+; +ESI-
IT-MS3 (1359-889) m/z: 845 [(M+Naꢀ470)ꢀ44]+, 757 [(M+Na
ꢀ470)ꢀ132]+, 743 [(M+Naꢀ470)ꢀ146]+, 713 [(M+Naꢀ470)ꢀ132
ꢀ44]+, 699 [(M+Naꢀ470)ꢀ146ꢀ44]+, 611 [(M+Naꢀ470)ꢀ146
ꢀ132]+; +ESI-IT-MS3 (1359-493) m/z: 475, 447, 421, 405, 349,
347, 331, 289, 203; -ESI-IT-MS m/z: 1335 [MꢀH]ꢀ; -ESI-IT-MS2
(1335) m/z: 865 [MꢀHꢀ470]ꢀ, 733 [MꢀHꢀ470ꢀ132]ꢀ, 719
[MꢀHꢀ470ꢀ146]ꢀ; -ESI-IT-MS3 (1335-865) m/z: 733 [(MꢀHꢀ470)
ꢀ132]ꢀ, 719 [(MꢀHꢀ470)ꢀ146]ꢀ, 587 [(MꢀHꢀ470)ꢀ132ꢀ146]ꢀ,
569 [(MꢀHꢀ470)ꢀ132ꢀ146ꢀ18]ꢀ; -ESI-IT-MS3 (1335-733) m/z:
587 [(MꢀHꢀ470ꢀ132)ꢀ146]ꢀ, 569 [(MꢀHꢀ470ꢀ132)ꢀ146ꢀ18]ꢀ,
455 [(MꢀHꢀ470ꢀ132)ꢀ146ꢀ132]ꢀ; -ESI-IT-MS3 (1335-719) m/z:
587 [(MꢀHꢀ470ꢀ146)ꢀ132]ꢀ, 569 [(MꢀHꢀ470ꢀ146)ꢀ132ꢀ18]ꢀ,
455 [(MꢀHꢀ470ꢀ146)ꢀ132ꢀ132]ꢀ; +HR-ESI-Q-TOF-MS m/z:
1359.6147 [M+Na]+ (calcd. for C63H100NaO30, 1359.6197).
[(MꢀHꢀ
470)ꢀ132ꢀ146ꢀ132]ꢀ;
+HR-ESI-Q-TOF-MS
m/z:
1375.6485 [M+Na]+ (calcd. for C64H104NaO30, 1375.6510).
3.3.8. 3-O-b-
2)]- -arabinopyranosyl-hederagenin-28-O-
(1 ? 4)-b-
D
-xylopyranosyl-(1 ? 3)-[
a
-
L
-rhamnopyranosyl-(1 ?
a
-L
a-L
-rhamnopyranosyl-
D
-glucopyranosyl-(1 ? 6)-b- -glucopyranosyl ester (8)
White amorphous powder; ½a D27
ꢂ
ꢀD6.2 (c 0.10, MeOH–H2O 1:1);
IR (KBr) m
max (cmꢀ1) 3365, 2939, 1736, 1642, 1457, 1388, 1058; for
1H NMR (pyridine-d5, 400 MHz) and 13C NMR (pyridine-d5,
100 MHz) spectroscopic data, see Table 2; +ESI-IT-MS m/z: 1375
[M+Na]+; +ESI-IT-MS2 (1375) m/z: 905 [M+Naꢀ470]+, 759
[M+Naꢀ470ꢀ146]+, 493 [470+Na]+; +ESI-IT-MS3 (1375-905) m/z:
861 [(M+Naꢀ470)ꢀ44]+, 773 [(M+Naꢀ470)ꢀ132]+, 759 [(M+Na
ꢀ470)ꢀ146]+, 729 [(M+Naꢀ470)ꢀ132ꢀ44]+, 715 [(M+Naꢀ470)ꢀ
146ꢀ44]+, 627 [(M+Naꢀ470)ꢀ146ꢀ132]+; +ESI-IT-MS3 (1375-
3.3.5. 3-O-
(1 ? 2)]-
a
-
L
-arabinopyranosyl-(1 ? 3)-[
a-L-rhamnopyranosyl-
a
-L
-arabinopyranosyl-30-norhederagenin-28-O-b-D-
glucopyranosyl-(1 ? 6)-b- -glucopyranosyl ester (5)
D
White amorphous powder; ½a D27
ꢂ
17.4 (c 0.10, MeOH–H2O 1:1);
IR (KBr) mmax (cmꢀ1) 3451, 2930, 1739, 1653, 1454, 1388, 1072;