1766
H.-M. Liu et al. / Carbohydrate Research 337 (2002) 1763–1767
1
1751 (CꢀO), 1644 (CꢀC), 891 cm−1 (ꢀC-H); H NMR
(acetone-d6): l 7.52 (s, 1 H, H-14), 6.90 (dd, 1 H, J
10.0, 16.0 Hz, H-11), 6.18 (d, 1 H, J 16.0 Hz, H-12),
4.86 (s, 2 H, H2-15), 4.75, 4.49 (s, each 1 H, H2-17),
4.29 (d, 1 H, J 6.4 Hz, H-1%), 3.96, 3.21 (d, each 1 H, J
10.8 Hz, H2-19), 3.87 (m, 1 H, H-3%), 3.75 (d, 1 H, J 4.0
Hz, H-4%), 3.71 (m, 2 H, H-6%), 3.56 (dd, 1 H, J 3.6, 11.6
Hz, H-3), 3.51 (d, 1 H, J 4.0 Hz, H-5%), 3.48 (m, 1 H,
H-2%), 1.22, 0.83 (s, each 3 H, CH3×2); ESIMS (m/z):
517 ([M+Na]+); Anal. Calcd for C26H38O9 (494.57):
C, 63.14; H, 7.44. Found: C, 26.95; H, 7.26.
2), 1.22, 1.19 (s, each 3 H, CH3×2); ESIMS (m/z): 673
([M+Na]+), 668 ([M+H2O]+); Anal. Calcd for
C33H46O13 (650.71): C, 60.91; H, 7.13. Found: C, 60.81;
H, 7.34.
6-(2%-O-acetyl-b-D-glucopyranosyl)-7:14-O-isopro-
pylideneoridonin (15): mp 154–156 °C; IR (KBr): 1738,
1
1712 (CꢀO), 1647 (CꢀC), 908 cm−1 (ꢀC-H); H NMR
(acetone-d6): l 5.81, 5.32 (s, each 1 H, H2-17), 5.15 (d,
1 H, J 8.0 Hz, H-1%), 4.87 (d, 1 H, J 1.2 Hz, H-14), 4.78
(m, 1 H, H-2%), 4.30 (m, 2 H, H-6, H-20), 3.95 (m, 2 H,
H-20, H-6%), 3.71 (m, 1 H, H-6%), 3.44 (m, 3 H, H-3%,
H-3, H-5%), 3.30 (m, 1 H, H-4%), 2.94 (br s, 1 H, H-13),
1.92 (s, 3 H, CH3CO), 1.60, 1.32, 1.21, 1.15 (s, each 3
H, CH3×4); ESIMS (m/z): 631 ([M+Na]+), 571
([M−CH3COOH+Na]+); Anal. Calcd for C31H44O12
(608.67): C, 61.17; H, 7.29. Found: C, 60.89; H, 7.11.
19-O-b-D-Glucopyranosyl-14-deoxy-11,12-didehy-
droandrographiside (12): mp 138–140 °C; IR (KBr):
1
1751 (CꢀO), 1644 (CꢀC), 893 cm−1 (ꢀC-H); H NMR
(acetone-d6): l 7.53 (s, 1 H, H-14), 6.95 (dd, 1 H, J
10.0, 15.6 Hz, H-11), 6.18 (d, 1 H, J 15.8 Hz, H-12),
4.87 (d, 2 H, J 1.6 Hz, H2-15), 4.76, 4.51 (d, 1 H, J 1.6
Hz, H2-17), 4.38 (d, 1 H, J 7.6 Hz, H-1%), 4.26 (m, 1 H,
H-4%), 3.96, 3.23 (d, 1 H, J 11.2 Hz, H-19), 3.81 (dd, 1
H, J 2.4, 11.6 Hz, H-6%), 3.66 (dd, 1 H, J 5.6, 11.6 Hz,
H-6%), 3.59 (dd, 1 H, J 4.0, 12.0 Hz, H-3), 3.37 (t, 1 H,
J 2.0 Hz, H-3%), 3.31 (m, 1 H, H-5%), 3.14 (t, 1 H, J 2.0
Hz, H-2%), 1.22, 0.83 (s, each 3 H, CH3×2); ESIMS
(m/z): 517 ([M+Na]+), 495 ([M+H]+); Anal. Calcd
for C26H38O9 (494.57): C, 63.14; H, 7.44. Found: C,
63.01; H, 7.40.
6-O-(2%-O-Acetyl-b-D-galactopyranosyl)-7:14-O-iso-
propylideneoridonin (16): mp 178–180 °C; IR (KBr):
1
1740, 1711 (CꢀO), 1647 (CꢀC), 907 cm−1 (ꢀC-H); H
NMR (acetone-d6): l 5.81, 5.32 (s, each 1 H, H2-17),
5.06 (m, 2 H, H-1%, H-2%), 4.85 (d, 1 H, J 1.6 Hz, H-14),
4.30 (d, 1 H, J 9.2 Hz, H-6), 4.26, 3.96 (d, each 1 H, J
10.0 Hz, H2-20), 3.93 (d, 1 H, J 2.8 Hz, H-4%), 3.84 (dd,
1 H, J 6.4, 10.8 Hz, H-6%), 3.77 (dd, 1 H, J 10.8, 5.6 Hz,
H-6%), 3.51 (m, 2 H, H-3%, H-5%), 3.43 (dd, 1 H, J 5.6,
11.2 Hz, H-1), 2.93 (d, 1 H, J 9.2 Hz, H-13), 2.47 (dt,
1 H, J 10.8, 13.6 Hz, H-12), 1.92 (s, 3 H, CH3CO), 1.59,
1.31, 1.18, 1.16 (s, each 3 H, CH3×4); ESIMS (m/z):
631 ([M+Na]+), 571 ([M−CH3COOH+Na]+);
Anal. Calcd for C31H44O12 (608.67): C, 61.17; H, 7.29.
Found: C, 61.40; H, 7.12.
1-O-Acetyl-6-(2-O-acetyl-b-D-glucopyranosyl)-7:14-
O-isopropylideneoridonin (13): mp 286–288 °C; IR
(KBr): 1743, 1728 (CꢀO), 1651 (CꢀC), 912 cm−1 (ꢀC-
1
H); H NMR (acetone-d6): l 5.82, 5.34 (s, each 1 H,
H2-17), 5.14 (d, 1 H, J 8.4 Hz, H-1%), 4.86 (s, 1 H,
H-14), 4.78 (m, 1 H, H-2%), 4.60 (dd, 1 H, J 5.6, 10.0
Hz, H-1), 4.35 (d, 1 H, J 9.2 Hz, H-6), 4.29, 4.09 (d,
each 1 H, J 10.0 Hz, H2-20), 3.93 (dd, 1 H, J 2.4, 11.2
Hz, H-6%), 3.72 (dd, 1 H, J 11.2, 5.6 Hz, H-6%), 3.45–
3.39 (m, 2 H, H-3%, H-5%), 3.30 (m, 1 H, H-4%), 2.94 (d,
1 H, J 10.0 Hz, H-13), 2.47 (dt, 1 H, J 8.4, 14.0 Hz,
H-12), 1.94, 1.92 (s, each 3 H, CH3CO×2), 1.88
(m, 1 H, H-11), 1.76 (dd, 1 H, J 5.2, 12.4 Hz, H-9), 1.67
(d, 1 H, J 9.2 Hz, H-5), 1.64–1.48 (m, 2 H, H-2, H-12),
1.46–1.12 (m, 4 H, H-2, H2-3, H-11), 1.61, 1.32, 1.24,
1.18 (s, each 3 H, CH3×4); ESIMS (m/z): 673 ([M+
Na]+), 613 ([M−CH3COOH+Na]+), 451 ([M−
{Glc-OAc}+Na]+). Anal. Calcd for C33H46O13
(650.71): C, 60.91; H, 7.13. Found: C, 60.70; H, 7.32.
Acknowledgements
We are grateful to NNSF of PRC and Natural
Science Found of Henan Province for financial support
of this work.
References
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1-O-Acetyl-6-(2%-O-acetyl-b-D-galactopyranosyl)-
7:14-O-isopropylideneoridonin (14): mp 277–279 °C;
IR (KBr): 1742 (CꢀO), 1651 (CꢀC), 909 cm−1 (ꢀC-H);
1H NMR (acetone-d6): l 5.82, 5.33 (s, each 1 H, H2-17),
5.10–5.03 (m, 2 H, H-1%, H-2%), 4.86 (d, 1 H, J 1.6 Hz,
H-14), 4.60 (dd, 1 H, J 5.6, 10.4 Hz, H-1), 4.34 (d, 1 H,
J 9.2 Hz, H-6), 4.28, 4.09 (d, each 1 H, J 9.2 Hz,
H2-20), 3.94 (m, 1 H, H-4%), 3.88–3.77 (m, 2 H, H-6%),
3.57–3.49 (m, 2 H, H-3%, H-5%), 2.94 (d, 1 H, J 8.0 Hz,
H-13), 2.46 (dt, 1 H, J 8.8, 14.0 Hz, H-12), 1.94, 1.92 (s,
each 3 H, CH3CO×2), 1.60, 1.31 (s, each 3 H, CH3×