ꢀ
10402
E. Bokor et al. / Tetrahedron 69 (2013) 10391e10404
refluxed for 3 h, then the solvent was removed under diminished
pressure. The residue was purified by column chromatography (1:4
EtOAc/toluene) to yield 0.12 g (60%) white amorphous solid. Rf: 0.33
165.6, 165.3 (C]O), 158.4, 154.7 (triazole C-3, C-5), 148.6,
133.9e133.3, 129.8e129.6, 129.0, 128.8, 128.5e128.2, 125.9, 118.6
(aromatics), 77.1, 73.4, 73.3, 71.1, 69.2 (C-10eC-50), 63.2 (C-60). Anal.
Calcd for C42H31N5O13 (813.72): C, 61.99; H, 3.84; N, 8.61. Found: C,
61.89; H, 3.93; N, 8.71.
(1:3 EtOAc/toluene); [
a]
ꢁ8 (c 0.11, CHCl3); 1H NMR (CDCl3)
D
d
(ppm): 7.93 (2H, d, J¼8.0 Hz, aromatics), 7.90e7.87 (4H, m, aro-
matics), 7.81 (2H, d, J¼7.4 Hz, aromatics), 7.74 (2H, d, J¼8.0 Hz,
aromatics), 7.42 (1H, t, J¼7.3 Hz, aromatics), 7.35e7.06 (11H, m,
aromatics), 6.98 (2H, J¼8.6 Hz, aromatics), 6.37, 6.21, 6.05 (3ꢂ1H, 3
pseudo t, J¼9.9, 9.2 Hz in each, H-20, H-30, H-40), 5.40 (1H, d,
J¼9.9 Hz, H-10), 4.62 (2H, m, H-60a, H-60b), 4.48 (1H, ddd, J¼9.9, 5.5,
4.4.14. 5-(Acetoxymethyl)-3-(20,30,40,60-tetra-O-benzoyl-
pyranosyl)-1,2,4-triazole (11j). From tosyl-amidrazone 4 (1.00 g,
1.26 mmol) and acetoxyacetyl chloride (204 L, 1.89 mmol)
b-D-gluco-
m
according the general procedure V. After extraction and evapora-
tion the crude mixture was dissolved in THF (30 mL), 1 M solution
of Bu4NF in THF (2.53 mL) was added and the mixture was refluxed
for 1.5 h, then the solvent was removed under diminished pres-
sure. The residue was purified by column chromatography (1:1
EtOAc/hexane) to yield 0.55 g (61%) white amorphous solid. Rf:
4.3 Hz, H-50), 2.21 (3H, s, CH3); 13C NMR (CDCl3)
d (ppm): 169.1,
166.2, 165.9, 165.1, 165.0 (C]O), 157.7, 156.9 (triazole C-3, C-5),
151.7, 133.2e132.8, 129.7e129.4, 129.0, 128.8, 128.8, 128.6, 128.5,
128.2e127.6, 125.3, 125.1, 121.7 (aromatics), 76.5, 74.4, 74.0, 71.3,
69.5 (C-10eC-50), 63.2 (C-60), 20.8 (CH3). Anal. Calcd for C44H35N3O11
(781.76): C, 67.60; H, 4.51; N, 5.38. Found: C, 67.69; H, 4.62; N, 5.26.
0.45 (2:3 EtOAc/hexane); [
a
]
D þ16 (c 0.50, CHCl3); 1H NMR (CDCl3)
d
(ppm): 10.19 (1H, br s, triazole NH), 7.94e7.90 (6H, m, aromatics),
4.4.11. 3-(20,30,40,60-Tetra-O-benzoyl-
b
-
D
-glucopyranosyl)-5-(3,4,5-
7.71 (2H, d, J¼7.0 Hz, aromatics), 7.43e6.88 (12H, m, aromatics),
6.36, 6.22, 6.12 (3ꢂ1H, 3 pseudo t, J¼9.6, 8.8 Hz in each, H-20, H-30,
H-40), 5.36 (1H, d, J¼9.6 Hz, H-10), 5.10 (2H, s, CH2), 4.71e4.62 (2H,
m, H-60a, H-60b), 4.49 (1H, ddd, J¼9.6, 4.9, 2.6 Hz, H-50), 1.87 (3H, s,
trimethoxyphenyl)-1,2,4-triazole (11g). From tosyl-amidrazone 4
(0.20 g, 0.25 mmol) and 3,4,5-trimethoxybenzoyl chloride (87 mg,
0.38 mmol) according to general procedure V. Purified by column
chromatography (3:7 EtOAc/hexane) to yield 0.11 g (54%) white
CH3); 13C NMR (CDCl3)
d (ppm): 170.3, 166.0, 165.6, 164.9, 164.7
solid. Mp: 125e127 ꢀC; [
a]
þ10 (c 0.39, CHCl3); 1H NMR (CDCl3)
(C]O), 157.1, 154.3 (triazole C-3, C-5), 133.1e132.8, 129.6e129.2,
129.0, 128.5, 128.2, 128.1e127.7 (aromatics), 76.6, 74.1, 73.9, 71.3,
69.3 (C-10eC-50), 63.2 (C-60), 57.3 (CH2), 20.0 (CH3). Anal. Calcd for
D
d
(ppm): 8.65 (1H, br s, triazole NH), 7.93e7.91 (6H, m, aromatics),
7.75 (2H, d, J¼6.6 Hz, aromatics), 7.50e7.22 (10H, m, aromatics),
7.08e7.05 (4H, m, aromatics), 6.23, 6.14, 5.99 (3ꢂ1H, 3 pseudo t,
J¼10.6, 9.2 Hz in each, H-20, H-30, H-40), 5.31 (1H, d, J¼9.2 Hz, H-10),
4.67e4.62 (2H, m, H-60a, H-60b), 4.42 (1H, ddd, J¼9.2, 5.3, 4.0 Hz, H-
50), 3.80 (3H, s, OMe), 3.62 (6H, s, 2ꢂOMe); 13C NMR (CDCl3)
C39H33N3O11 (719.69): C, 65.09; H, 4.62; N, 5.84. Found: C, 65.18; H,
4.73; N, 5.73.
4.4.15. 5-Methyl-3-(20,30,40,60-tetra-O-benzoyl-
b-D-glucopyranosyl)-
d
(ppm): 166.4, 165.9, 165.2, 165.0 (C]O), 158.3, 157.0 (triazole C-3,
1,2,4-triazole (11k). The tosyl-amidrazone 4 (0.60 g, 0.76 mmol)
treated with acetyl chloride (81 L, 1.14 mmol) according to general
procedure V gave 5-methyl-3-(20,30,40,60-tetra-O-benzoyl-
-glu-
C-5), 153.2, 139.2, 133.4e133.0, 129.8e129.5, 129.1, 129.0, 128.7,
128.6, 128.3e128.0, 123.6, 103.4 (aromatics), 76.9, 74.2, 74.1, 71.4,
69.5 (C-10eC-50), 63.3 (C-60), 60.7 (OMe), 55.8 (2ꢂOMe). Anal. Calcd
for C45H39N3O12 (813.80): C, 66.41; H, 4.83; N, 5.16. Found: C, 66.34;
H, 4.96; N, 5.28.
m
b-D
copyranosyl)-1-tosyl-1,2,4-triazole (17k). The crude product was
purified by column chromatography (3:7 EtOAc/hexane) to yield
0.43 g (69%) of white amorphous solid. Rf: 0.67 (1:1 EtOAc/hexane);
[
a
]
þ89 (c 0.23, CHCl3); 1H NMR (CDCl3)
d (ppm): 7.99, 7.90, 7.81
D
4.4.12. 5-(4-Nitrophenyl)-3-(20,30,40,60-tetra-O-benzoyl-
b
-
D
-gluco-
(3ꢂ2H, 3d, J¼7.9 Hz in each, aromatics), 7.74e7.72 (4H, m, aro-
matics), 7.54e7.25 (12H, m, aromatics), 7.05 (2H, d, J¼7.9 Hz, aro-
matics), 6.02, 5.95, 5.80 (3ꢂ1H, 3 pseudo t, J¼10.6, 9.2 Hz in each, H-
20, H-30, H-40), 4.97 (1H, d, J¼9.2 Hz, H-10), 4.60 (1H, dd, J¼11.9,
2.6 Hz, H-60a), 4.51 (1H, dd, J¼11.9, 5.3 Hz, H-60b), 4.28 (1H, ddd,
J¼9.2, 5.3, 2.6 Hz, H-50), 2.71 (3H, s, CH3), 2.28 (3H, s, CH3); 13C NMR
pyranosyl)-1,2,4-triazole (11h). From tosyl-amidrazone 4 (1.70 g,
2.15 mmol) and 4-nitrobenzoyl chloride (0.60 g, 3.20 mmol)
according to general procedure V. Purified by column chromatog-
raphy (3:7 EtOAc/hexane) to yield 0.94 g (57%) yellow solid. Mp:
183e185 ꢀC; [
a
]
D
þ35 (c 0.22, CHCl3); IR (KBr) nmax (cmꢁ1): 3430
(br, NH); 1H NMR (CDCl3)
d
(ppm): 8.08 (2H, d, J¼8.7 Hz, aromatics),
(CDCl3) d (ppm): 166.1, 165.8, 165.1, 164.4 (C]O), 159.1, 157.0 (tri-
8.00e7.89 (8H, m, aromatics), 7.75 (2H, d, J¼7.8 Hz, aromatics),
7.53e7.45 (3H, m, aromatics), 7.37e7.25 (7H, m, aromatics),
7.07e7.03 (2H, m, aromatics), 6.16, 6.02, 5.93 (3ꢂ1H, 3 pseudo t,
J¼9.7, 9.5 Hz in each, H-20, H-30, H-40), 5.24 (1H, d, J¼9.7 Hz, H-10),
4.73e4.63 (2H, m, H-60a, H-60b), 4.42 (1H, ddd, J¼9.7, 5.4, 2.7 Hz, H-
azole C-3, C-5), 146.4 (TsCqCH3), 133.4e133.0, 130.0e129.6, 129.4,
129.0, 128.8, 128.7, 128.3e128.0 (aromatics), 76.7, 74.4, 74.0, 70.7,
69.4 (C-10eC-50), 63.4 (C-60), 21.7 (CH3), 14.5 (CH3). Anal. Calcd for
C44H37N3O11S (815.84): C, 64.78; H, 4.57; N, 5.15. Found: C, 64.89; H,
4.44; N, 5.23.
50); 13C NMR (CDCl3)
d
(ppm): 166.7, 165.8, 165.4, 165.2 (C]O),
This triazole 17k (0.35 g, 0.43 mmol) was dissolved in THF
(10 mL), a 1 M solution of Bu4NF in THF (0.86 mL, 0.86 mmol) was
added and the mixture was refluxed. After completion of the re-
action (2 h) monitored by TLC (1:1 EtOAc/hexane), the solvent was
removed under diminished pressure, and the residue was purified
by column chromatography (3:2 EtOAc/hexane) to yield 0.25 g
159.0, 155.4 (triazole C-3, C-5), 148.0, 135.6, 133.5e133.2,
130.0e129.5, 128.9,128.4e128.0,127.0, 123.7 (aromatics), 77.2, 73.7,
73.5, 71.4, 69.3 (C-10eC-50), 63.3 (C-60). Anal. Calcd for C42H32N4O11
(768.72): C, 65.62; H, 4.20; N, 7.29. Found: C, 65.73; H, 4.28; N, 7.17.
4.4.13. 5-(3,5-Dinitrophenyl)-3-(20,30,40,60-tetra-O-benzoyl-
b
-
D
-glu-
(88%) colourless syrup. Rf: 0.43 (3:1 EtOAc/hexane); [
0.22, CHCl3); IR (KBr) nmax (cmꢁ1): 3437 (br, NH); 1H NMR (CDCl3)
(ppm): 12.03 (1H, br s, triazole NH), 7.92e7.90 (4H, m, aromatics),
a
]
þ43 (c
D
copyranosyl)-1,2,4-triazole (11i). From tosyl-amidrazone 4 (1.70 g,
2.15 mmol) and 3,5-dinitrobenzoyl chloride (0.74 g, 3.22 mmol)
according to general procedure V. Purified by column chromatog-
raphy (3:7 EtOAc/hexane) to yield 0.90 g (55%) yellow solid. Mp:
d
7.80e7.78 (4H, m, aromatics), 7.50e7.18 (12H, m, aromatics), 6.28,
6.08, 5.95 (3ꢂ1H, 3 pseudo t, J¼9.8, 9.8 Hz in each, H-20, H-30, H-40),
5.18 (1H, d, J¼9.2 Hz, H-10), 4.62e4.53 (2H, m, H-60a, H-60b), 4.40
(1H, ddd, J¼9.2, 5.3, 2.6 Hz, H-50), 2.35 (3H, s, CH3); 13C NMR (CDCl3)
107e109 ꢀC; [
a
]
D
þ4.5 (c 0.47, MeOH); IR (KBr) nmax (cmꢁ1): 3429
(br, NH); 1H NMR (CDCl3)
d (ppm): 8.86 (2H, s, aromatics),
8.02e7.94 (6H, m, aromatics), 7.80 (2H, d, J¼8.2 Hz, aromatics),
7.56e7.30 (10H, m, aromatics), 7.16e7.12 (2H, m, aromatics), 6.18,
5.94e5.88 (3ꢂ1H, 3 pseudo t, J¼9.7, 9.6 Hz in each, H-20, H-30, H-40),
5.27 (1H, d, J¼9.8 Hz, H-10), 4.69 (2H, m, H-60a, H-60b), 4.45 (1H,
d (ppm): 166.3, 166.0, 165.2, 165.0 (C]O), 158.5, 154.7 (triazole C-3,
C-5), 133.3e133.0, 129.8e129.7, 129.4, 129.0, 128.8, 128.3e128.2
(aromatics), 76.6, 74.7, 74.3, 71.1, 69.5 (C-10eC-50), 63.4 (C-60), 12.1
(CH3). Anal. Calcd for C37H31N3O9 (661.66): C, 67.16; H, 4.72; N, 6.35.
Found: C, 67.29; H, 4.60; N, 6.24.
ddd, J¼9.5, 5.4, 2.6 Hz, H-50); 13C NMR (CDCl3)
d (ppm): 166.7, 165.8,