6610 Thanh et al.
Asian J. Chem.
12.5, 4.75 Hz, H-6'a), 3.99 (dd, 1H, J = 12.25, 1.75 Hz, H-
6'b), 4.11 (ddd, 1H, J = 9.88, 4.63, 2.22 Hz, H-5'), 7.81 (d,
1H, J = 9.5 Hz, H-5"), 7.29-7.27 (m, 2H, H-8" & H-6"), 7.20
(s, 1H, H-3"), 2.00-1.94 (s, 12H, CH3CO), 2.43 (s, 3H, 7"-
CH3), 13C NMR (DMSO-d6) δ (ppm): 137.1 (CH=N), 179.0
(C=S), 170.0-169.3 (CH3CO ester), 160.1 (C=O lacton), 81.7
(C-1'), 70.8 (C-2'), 72.7 (C-3'), 67.8 (C-4'), 72.4 (C-5'), 61.7
(C-6'), 114.5 (C-3"), 143.1 (C-4"), 117.0 (C-4"a), 125.8 (C-
5"), 124.4 (C-6"), 144.3 (C-7"), 111.5 (C-8"), 153.6 (C-8"a),
20.5-20.3 (CH3CO ester), 21.0 (CH3, 7"-methyl); ESI-MS:
C26H29N3O11S, calcd. for [M-H]+ = 590 Da, found: m/z 590.
4-Formyl-7-ethoxycoumarin 4-(2,3,4,6-tetra-O-acetyl-
β-D-glucopyranosyl)thiosemicarbazone (4b):Yellow solid,
m.p. 137-140 ºC, yield 67 %; IR (KBr, νmax, cm-1) : 3563, 3299,
1748, 1721, 1614, 1524, 1500, 1233, 1039, 1090; 1H NMR
(DMSO-d6) δ (ppm): 8.53 (s, 1H, CH=N), 12.29 (s, 1H, NH-
2), 9.10 (d, 1H, J = 9.5 Hz, NH-4), 5.99 (t, 1H, J = 9.25 Hz, H-
1'), 5.35 (t, 1H, J = 9.25 Hz, H-2'), 5.42 (t, 1H, J = 9.25 Hz, H-
3'), 4.97 (t, 1H, J = 9.75 Hz, H-4'), 4.23 (dd, 1H, J = 12.5, 5.0
Hz, H-6'a), 3.99 (dd, 1H, J = 10.5 Hz, H-6'b), 4.12-4.08 (m,
1H, H-5'), 7.84 (d, 1H, J = 8.5 Hz, H-5"), 7.05-7.02 (m, 2H,
H-8"), 7.05-7.02 (m, 2H, H-6"), 7.06 (s, 1H, H-3"), 2.00-1.91
(s, 12H, CH3CO ester), 0.93 (t, 3H, J = 7.5 Hz, CH3, 7"-butoxy),
1.44 (sextet, H, J = 7.5 Hz, CH2, 7"- butoxy), 4.09 (q, 2H, J =
6.5 Hz, CH2O, 7"-butoxy); 13C NMR (DMSO-d6) δ (ppm):
137.4 (CH=N), 179.0 (C=S), 170.0-169.3 (CH3CO ester),
160.3 (C=O lacton), 81.6 (C-1'), 70.8 (C-2'), 72.7 (C-3'), 67.8
(C-4'), 72.4 (C-5'), 61.7 (C-6'), 109.0 (C-3"), 147.4 (C-4"),
110,3 (C-4"a), 101.5 (C-5"), 161.9 (C-6"), 112.9 (C-7"), 125.8
(C-8"), 155.5 (C-8"a), 20.5-20.3 (CH3CO ester), 68.0 (OCH2,
7"-butoxy), 30.5 (CH2, 7"-butoxy), 18.6 (CH2, 7"-butoxy), 13.6
(CH3, 7"-butoxy); ESI-MS: C29H35N3O12S, calcd. for [M-H]+
= 648 Da, found: m/z 648.
1
1730, 1614, 1526, 1500, 1490, 1248, 1063, 1100; H NMR
(DMSO-d6) δ (ppm): 8.45 (s, 1H, CH=N), 12.22 (s, 1H, NH-
2), 9.12 (d, 1H, J = 9.5 Hz, NH-4), 5.99 (t, 1H, J = 9.25 Hz, H-
1'), 5.35 (t, 1H, J = 9.25 Hz, H-2'), 5.43 (t, 1H, J = 9.5 Hz, H-
3'), 4.97 (t, 1H, J = 9.75 Hz, H-4'), 4.23 (dd, 1H, J = 12.5, 4.5,
H-6'a), 3.99 (dd, 1H, J = 12.25, 1.75 Hz, H-6'b), 4.11 (ddd,
1H, J = 10.0, 4.5, 2.5 Hz, H-5'), 7.83 (d, 1H, J = 9.5 Hz, H-
5"), 7.02 (d, 1H, J = 2.5 Hz, H-8"), 7.03 (dd, 1H, J = 9.5, 2.5
Hz, H-6"), 7.07 (s, 1H, H-3"), 2.00-1.94 (s, 12H, CH3CO es-
ter), 1.36 (t, 3H, J = 7.0 Hz, CH3, 7"-ethoxy), 4.11 (q, 2H, J =
7.0 Hz, CH2O, 7"-ethoxy); 13C NMR (DMSO-d6) δ (ppm):
137.3 (CH=N), 179.0 (C=S), 169.9-169.3 (CH3CO ester),
160.2 (C=O lacton), 81.6 (C-1'), 70.8 (C-2'), 72.7 (C-3'), 67.8
(C-4'), 72.3 (C-5'), 61.7 (C-6'), 109.2 (C-3"), 144.3 (C-4"),
110.2 (C-4"a), 125.8 (C-5"), 112.9 (C-6"), 161.7 (C-7"), 101.6
(C-8"), 155.5 (C-8"a), 20.5-20.3 (CH3CO ester), 64.0 (OCH2,
7"-ethoxy), 14.3 (CH3, 7"-ethoxy); ESI-MS: C27H31N3O12S,
calcd. for [M-H]+ = 620 Da, found: m/z 620.
4-Formyl-6-ethoxycoumarin 4-(2,3,4,6-tetra-O-acetyl-
ß-D-glucopyranosyl)thiosemicarbazone (4e): Yellow solid,
m.p. 189-193 ºC, yield 79 %; IR (KBr, νmax, cm-1): 3593, 3249,
1
1760, 1716, 1600, 1523, 1500, 1242, 1034, 1090; H NMR
(DMSO-d6) δ (ppm): 8.57(s, 1H, CH=N), 9.19 (d, 1H, J = 9.5
Hz, NH-2), 12.12 (s, 1H, NH-4), 6.03 (t, 1H, J = 9.25 Hz, H-
1'), 5.30 (t, 1H, J = 9.25 Hz, H-2'), 5.43 (t, 1H, J = 9.5 Hz, H-
3'), 4.97 (t, 1H, J = 9.75 Hz, H-4'), 4.23 (dd, 1H, J = 12.5, 4.5
Hz, H-6'a), 3.99 (dd, 1H, J = 12.25, 1.5 Hz, H-6'b), 4.14-4.08
(m, 1H, H-5'), 7.28-7.25 (m, 1H, H-5"), 7.40 (d, 1H, J = 9.0
Hz, H-8"), 7.32(s, 1H, H-3"), 2.00-1.93 (s, 12H, CH3CO es-
ter), 1.37 (t, 3H, J = 7.0 Hz, CH3, 6"-ethoxy), 4.10 (q, 2H, J =
7.0 Hz, CH2O, 6"-ethoxy); 13C NMR (DMSO-d6) δ (ppm):
136.7 (CH=N), 178.9 (C=S), 170.0-169.3 (CH3CO ester),
160.1 (C=O lacton), 81.7 (C-1'), 71.0 (C-2'), 72.7 (C-3'), 67.8
(C-4'), 72.4 (C-5'), 61.8 (C-6'), 107.5 (C-3"), 147.7 (C-4"),
136.7 (C-4"a), 111.8 (C-5"), 154.8 (C-6"), 117.5 (C-7"), 118.0
(C-8"), 154.8 (C-8"a), 20.5-20.3 (CH3CO ester), 63.7 (OCH2,
6"-ethoxy), 14.5 (CH3, 6"-ethoxy); ESI-MS: C27H31N3O12S,
calcd. for [M-H]+ = 620 Da, found: m/z 620.
4-Formyl-7-propoxycoumarin 4-(2,3,4,6-tetra-O-
acetyl-β-D-glucopyranosyl)thiosemicarbazone (4c):Yellow
solid, m.p. 173-175 ºC, yield 65 %; IR (KBr, νmax, cm-1): 3559,
1
3347, 3220, 1743, 1612, 1534, 1233, 1044, 1090; H NMR
(DMSO-d6) δ (ppm): 8.44 (s, 1H, CH=N), 12.22 (s, 1H, NH-
2), 9.10 (d, 1H, J = 9.0 Hz, NH-4), 5.99 (t, 1H, J = 9.25 Hz,
H-1'), 5.35 (t, 1H, J = 9.25 Hz, H-2'), 5.43 (t, 1H, J = 9.25 Hz,
H-3'), 4.97 (t, 1H, J = 9.75 Hz, H-4'), 4.23 (dd, 1H, J = 12.5,
4.5 Hz, H-6'a), 3.99 (dd, 1H, J = 12.0, 2.0 Hz, H-6'b), 4.11
(ddd, 1H, J = 12.0, 4.5, 2.0 Hz, H-5'), 7.84 (d, 1H, J = 8.0 Hz,
H-5"), 7.04 (d, 1H, J = 2.5 Hz, H-8"), 7.03 (dd, 1H, J = 8.0,
2.5 Hz, H-6"), 7.06 (s, 1H, H-3"), 2.00-1.94 (s, 12H, CH3CO
ester), 0.99 (t, 3H, J = 7.5 Hz, CH3-, 7"-propoxy), 1.76 (sex-
tet, 2H, J = 7.5 Hz, -CH2-, 7"-propoxy), 4.05 (t, 2H, J = 6.5
Hz, -CH2O-, 7"-propoxy); 13C NMR (DMSO-d6) δ (ppm):
137.4 (CH=N), 179.0 (C=S), 169.9-169.3 (CH3CO ester),
160.3 (C=O lacton), 81.6 (C-1'), 70.8 (C-2'), 72.7 (C-3'), 67.8
(C-4'), 72.3 (C-5'), 61.7 (C-6'), 109.2 (C-3"), 144.4 (C-4"),
110.3 (C-4"a), 125.8 (C-5"), 112.9 (C-6"), 161.9 (C-7"), 101.6
(C-8"), 155.5 (C-8"a), 20.5-20.3 (CH3CO ester), 69.8 (OCH2,
7"-propoxy), 21.8 (CH2, 7"- propoxy), 10.2 (CH3, 7"-
propoxy); ESI-MS: C28H33N3O12S, calcd. for [M-H]+ = 634 Da,
found: m/z 634.
4-Formyl-6-propoxycoumarin 4-(2,3,4,6-tetra-O-
acetyl-β-D-glucopyranosyl)thiosemicarbazone (4f):Yellow
solid, m.p. 121-135 ºC, yield 69 %; IR (KBr, νmax, cm-1): 3532,
3312, 1750, 1729, 1600, 1562, 1522, 1500, 1243, 1036, 1090;
1H NMR (DMSO-d6) δ (ppm): 8.55 (s, 1H, CH=N), 9.19 (d,
1H, J = 9.0 Hz, NH-2), 12.09 (s, 1H, NH-4), 6.03 (t, 1H, J =
9.0 Hz, H-1'), 5.30 (t, 1H, J = 9.25 Hz, H-2'), 5.43 (t, 1H, J =
9.5 Hz, H-3'), 4.97 (t, 1H, J = 9.75 Hz, H-4'), 4.23 (dd, 1H, J
= 12.5, 4.5 Hz, H-6'a), 4.02-3.98 (m, 1H, H-6'b), 4.13 (ddd,
1H, J = 10.0, 4.5, 2.0 Hz, H-5'), 7.28-7.26 (m, 1H, H-5"), 7.40
(d, 1H, J = 9.0 Hz, H-8"), 7.33 (s, 1H, H-3"), 2.00-1.93 (s,
12H, CH3CO ester), 1.01 (t, 3H, J = 7.0 Hz, CH3, 6"-propoxy),
1.77 (sextet, 2H, J = 7.0 Hz, CH2, 6"-propoxy), 4.00 (q, 2H, J
= 7.0 Hz, CH2O, 6"-propoxy); 13C NMR (DMSO-d6) δ (ppm):
136.7 (CH=N), 178.9 (C=S), 170.0-169.3 (CH3CO ester),
160.1 (C=O lacton), 81.7 (C-1'), 71.0 (C-2'), 72.7 (C-3'), 67.8
(C-4'), 72.4 (C-5'), 61.8 (C-6'), 107.5 (C-3"), 147.8 (C-4"),
136.7 (C-4"a), 111.9 (C-5"), 155.0 (C-6"), 117.5 (C-7"), 119.9
(C-8"), 154.8 (C-8"a), 20.5-20.3 (CH3CO ester), 69.6 (OCH2,
4-Formyl-7-butoxycoumarin 4-(2,3,4,6-tetra-O-acetyl-
β-D-glucopyranosyl)thiosemicarbazone (4d):Yellow solid,
m.p. 177-179 ºC, yield 70 %; IR (KBr, νmax, cm-1): 3502, 3267,