1,2,4-Triazolo[4,3-b][1,2,4]Triazines
1897
added charcoal (0.5 g), celite (0.4 g), and silica gel 60 GF254 (70–230 mesh; 0.1 g).
The later mixture was shaken for 1 hour, left at room temperature for another 1 hour,
filtered and the solvent was evaporated on a rotavap. The obtained residue was
recrystallised from dichloromethane/petroleum ether (bp 40–60°C) to give colorless
crystals of compounds 5a–d.
8-Amino-6-benzyl-2-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2,8-dihydro-3-
thioxo-1,2,4-triazolo[4,-3-b][1,2,4]-triazin-7(3H)-one pyridinium salt (5a). Using
the general procedure, 3a gave 5a (61%); mp 196°C; IR (KBr) 3425, 3256 (NH2), 1751
(C = O acetate), 1674 (C = O amide) cmÀ 1 1H NMR (DMSO-d6) d 8.78 (d, 2H,
;
J = 4.9 Hz, C5H5N), 8.31 (dt, 1H, J = 1.5, 7.8 Hz, C5H5N), 7.85 (t, 2H, J = 6.83 Hz,
C5H5N), 7.59–7.21 (m, 5H, ArH), 7.22 (d, 1H, J = 9.4 Hz, H-1’), 6.53 (s, 2H, NH2-
exchangeable), 5.48 (t, 1H, J = 9.5 Hz, H-2’), 5.41 (t, 1H, J = 9.5 Hz, H-3’), 5.01 (t,
1H, J = 9.5 Hz, H-4’), 4.23–4.07 (m, 5H, H-5’, H-6’, C6H5CH2), 2.07–1.93 (4s, 12H,
CH3CO). Anal. Calcd. for C25H28N6O10S.C5H5N: C, 52.70; H, 4.87; N, 14.34; S, 4.69.
Found: C, 52.78; H, 4.73; N, 14.26; S, 4.85.
8-Amino-6-(4-methylbenzyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2,8-
dihydro-3-thioxo-1,2,4-triazolo[4,3-b][1,2,4]-triazin-7(3H)-one pyridinium salt (5b).
Using the general procedure, 3b gave 5b (69%); mp 176°C; IR (KBr) 3448, 3248 (NH2),
1
1751 (C = O acetate), 1674 (C = O amide) cmÀ1; H NMR (DMSO-d6) d 8.84 (d, 2H,
J = 4.9 Hz, C5H5N), 8.37 (dt, 1H, J = 1.5, 7.1 Hz, C5H5N), 7.89 (t, 2H, J = 6.43 Hz,
C5H5N), 7.39, 7.32 (2d, 2H each, J = 7.3 Hz, ArH), 7.08 (d, 1H, J = 9.0 Hz, H-1’), 6.47 (s,
2H, NH2-exchangeable), 5.49 (t, 1H, J = 9.2 Hz, H-2’), 5.41 (t, 1H, J = 9.2 Hz, H-3’), 5.01
(t, 1H, J = 9.2 Hz, H-4’), 4.22–3.98 (m, 5H, H-5’, H-6’, 4-CH3C6H4CH2), 2.26 (s, 3H,
4-CH3C6H4CH2), 2.07–1.94 (4s, 12H, CH3CO). Anal. Calcd. for C26H30N6O10S.C5H5N:
C, 53.37; H, 5.06; N, 14.05. Found: C, 53.12; H, 4.97; N, 13.95.
8-Amino-6-(4-methoxybenzyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-
2,8-dihydro-3-thioxo-1,2,4-triazolo[4,3-b][1,2,4]-triazin-7(3H)-one pyridinium salt
(5c). Using the general procedure, 3c gave 5c (79%); mp 182°C; IR (KBr) 3448, 3248
(NH2), 1751 (C = O acetate), 1674 (C = O amide) cmÀ1; 1H NMR (DMSO-d6) d 8.91 (dt,
2H, J = 0.8, 5.9 Hz, C5H5N), 8.54 (t, 1H, J = 7.4 Hz, C5H5N), 8.03 (t, 2H, J = 7.04 Hz,
C5H5N), 7.36, 7.22 (2d, 2H each, J = 7.4 Hz, ArH), 6.91 (d, 1H, J = 9.0 Hz, H-1’), 6.45 (s,
2H, NH2-exchangeable), 5.51 (t, 1H, J = 9.3 Hz, H-2’), 5.41 (t, 1H, J = 9.3 Hz, H-3’), 5.01
(t, 1H, J = 9.3 Hz, H-4’), 4.22–3.95 (m, 5H, H-5’, H-6’, 4-CH3OC6H4CH2), 3.77 (s, 3H, 4-
CH3OC6H4CH2), 2.08–1.99 (4s, 12H, CH3CO). Anal. Calcd. for C26H30N6O11S.C5H5N:
C, 52.17; H, 4.94; N, 13.74. Found: C, 52.13; H, 4.72; N, 13.66.
8-Amino-6-(4-chlorobenzyl)-2-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2,8-
dihydro-3-thioxo-1,2,4-triazolo[4,3-b][1,2,4]-triazin-7(3H)-one pyridinium salt (5d).
Using the general procedure, 3d gave 5d (72%); mp 198–200°C; IR (KBr) 3447, 3242
1
(NH2), 1751 (C = O acetate), 1674 (C = O amide) cmÀ1; H NMR (DMSO-d6) d 8.92
(dt, 2H, J = 0.9, 5.8 Hz, C5H5N), 8.56 (t, 1H, J = 7.3 Hz, C5H5N), 8.01 (t, 2H, J = 7.1
Hz, C5H5N), 7.35, 7.21 (2d, 2H each, J = 7.3 Hz, ArH), 6.95 (d, 1H, J = 9.0 Hz, H-1’),
6.44 (s, 2H, NH2-exchangeable), 5.50 (t, 1H, J = 9.1 Hz, H-2’), 5.40 (t, 1H, J = 9.1 Hz,
H-3’), 5.01 (t, 1H, J = 9.1 Hz, H-4’), 4.21–3.96 (m, 5H, H-5’, H-6’, 4-ClC6H4CH2),