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N. H. Metwally et al. / Carbohydrate Research 345 (2010) 1135–1141
1H, H-40), 5.36 (t, J = 9 Hz, 1H, H-30), 6.10 (t, J = 9 Hz, 1H, H-20), 6.34
(d, J = 9.6 Hz, 1H, H-10). Anal. Calcd for C23H29NO10S2 (543): C,
50.82; H, 5.38; N, 2.58; S, 11.80. Found: C, 50.76; H, 5.49; N,
2.45; S, 11.87.
(727.5): C, 54.43; H, 4.15; N, 5.77; S, 8.81. Found: C, 54.55; H,
4.05; N, 5.74; S, 8.76.
4.22. N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-5-[(3-(4-
bromophenyl)-1-phenyl-1H-pyrazol-4-yl)methylene]-2-thioxo-
4-thiazolidinone 11e
4.18. N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-5-[(1,3-
diphenyl-1H-pyrazol-4-yl)methylene]-2-thioxo-4-
thiazolidinone 11a
Yield 45%; yellow crystals, mp 247–249 °C; (ethanol–dioxane);
IR (KBr) v 1747 (CH3CO) cmꢀ1 1H NMR (300 MHz, CDCl3) d 1.87,
;
1.96, 2.01, 2.02 (4s, 12H, 4CH3CO), 3.82 (m, 1H, H-50), 4.17 (m,
2H, H-6a0, H-6b0), 5.20 (t, J = 9.9 Hz, 1H, H-40), 5.30 (t, J = 9.3 Hz,
1H, H-30), 6.02 (t, J = 9.3 Hz, 1H, H-20), 6.26 (d, J = 9 Hz, 1H, H-10),
7.34–7.72 (m, 10H, Ar-H + @CH), 8.06 (s, 1H, pyrazolyl-H). Anal.
Calcd for C33H30BrN3O10S2 (773): C, 51.30; H, 3.91; N, 5.44; S,
8.30. Found: C, 51.39: H, 4.00; N, 5.53; S, 8.39.
Yield 69%; yellow crystals, mp 194 °C; (ethanol); IR (KBr) v 1746
(CH3CO) cmꢀ1 1H NMR (300 MHz, CDCl3) d 1.95, 2.04, 2.06, 2.10
;
(4s, 12H, 4CH3CO), 3.89 (m, 1H, H-50), 4.25 (m, 2H, H-6a0, H-6b0),
5.26 (t, J = 9.9 Hz, 1H, H-40), 5.39 (t, J = 9.6 Hz, 1H, H-30), 6.12 (t,
J = 9 Hz, 1H, H-20), 6.35 (d, J = 9.6 Hz, 1H, H-10), 7.38, 7.55, 7.68,
7.82 (4m, 11H, Ar-H + @CH), 8.16 (s, 1H, pyrazolyl). 13C NMR
(300 MHz, CDCl3) d 20.3, 20.50, 20.53, 20.7 (4CH3CO), 61.6 (C-20),
67.5 (C-60), 67.9 (C-40), 73.2 (C-30), 74.8 (C-50), 81.9 (C-10), 116.4
(C@C for rhod.), 118.6, 119.5, 124.9, 127.5, 127.8, 128.9, 129.1,
129.6, 131.1, 139.0, 155.2 (Ar-C), 165.3 (C@O), 169.2, 169.5,
170.0, 170.5 (CH3CO), 192.6 (C@S); MS: m/z (%) = 693 (M+, 4),
692 (8), 364 (16), 276 (31), 169 (100), 109 (99), 77 (31). Anal. Calcd
for C33H31N3O10S2 (693): C, 57.13; H, 4.50; N, 6.06; S, 9.24. Found:
C, 57.26; H, 4.40; N, 5.89; S, 9.35.
4.23. 1,4-Bis[N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2-
thioxo-4-thiazolidinon-5-ylidenemethyl]benzene 13
Compound 13 was prepared by the method described above for
the synthesis of compounds 5a–f, 8a,b, 11a–e, and 17. However,
DMF in the presence of Et3N was used as the basic medium instead
of potassium hydroxide. Yield 30%; red crystals, mp 242–244 °C;
(ethanol–dioxane); IR (KBr) v 1746 (CH3CO) cmꢀ1
;
1H NMR
(300 MHz, DMSO-d6) d 1.85, 1.93, 1.98, 2.00 (4s, 24H, 8CH3CO),
3.88 (m, 2H, H-50, H-500), 4.29 (m, 4H, H-6a0, H-6b0, H-6a00, H-6b00),
5.01 (t, J = 9.6 Hz, 2H, H-40, H-400), 5.52 (t, J = 9.3 Hz, 2H, H-30, H-
300), 5.85 (t, J = 9.3 Hz, 2H, H-20, H-200), 6.46 (d, J = 9.3 Hz, 2H, H-10,
H-100), 7.51 (s, 2H, 2 @CH), 7.70 (m, 4H, Ar-H). Anal. Calcd for
C42H44N2O20S4 (1024): C, 49.21; H, 4.33; N, 2.73; S, 15.51. Found:
C, 49.11; H, 4.25; N, 2.63; S, 15.62.
4.19. N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-5-[(3-(4-
methylphenyl)-1-phenyl-1H-pyrazol-4-yl)methylene]-2-thioxo-
4-thiazolidinone 11b
Yield 81%; yellow crystals, mp 200–202 °C; (ethanol–dioxane);
IR (KBr) v 1740 (CH3CO) cmꢀ1 1H NMR (300 MHz, CDCl3) d 1.95,
;
2.04, 2.06, 2.10 (4s, 12H, 4CH3CO), 2.45 (s, 3H, CH3), 3.90 (m, 1H,
H-50), 4.22 (m, 2H, H-6a0, H-6b0), 5.26 (t, J = 9.9 Hz, 1H, H-40), 5.41
(t, J = 9.6 Hz, 1H, H-30), 6.17 (t, J = 9 Hz, 1H, H-20), 6.33 (d,
J = 9.6 Hz, 1H, H-10), 7.32–7.78, 7.81 (2m, 10H, Ar-H + @CH), 8.14
(s, 1H, pyrazolyl H). Anal. Calcd for C34H33N3O10S2 (707): C,
57.70; H, 4.70; N, 5.94; S, 9.06. Found: C, 57.53; H, 4.76; N, 5.88;
S, 9.01.
4.24. 4-[5-(4-((N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-4-
oxo-2-thioxothiazolidin-5-
ylidene)methyl)phenoxy)pentyloxy]benzaldehyde 17
Yield 25%; yellow crystals, mp 106–108 °C; (ethanol); IR (KBr) v
1752 (CH3CO) cmꢀ1; 1H NMR (300 MHz, DMSO-d6) d 1.79–1.83 (m,
10H, pentyl-H), 1.88, 1.96, 2.00, 2.02 (4s, 12H, 4CH3CO), 4.08 (m, 1H,
H-50), 4.27 (m, 2H, H-6a0, H-6b0), 5.01 (t, J = 9.6 Hz, 1H, H-40), 5.59 (t,
J = 9.3 Hz, 1H, H-30), 5.92 (t, J = 9.3 Hz, 1H, H-20), 6.53 (d, J = 9.3 Hz,
1H, H-10), 7.10, 7.22, 7.61, 7.85 (4d, 8H, Ar-H), 7.77 (s, 1H, @CH),
9.85 (s, 1H, CHO). Anal. Calcd for C36H39NO13S2 (757): C, 57.06; H,
5.19; N, 1.85; S, 8.46. Found: C, 57.16; H, 5.08; N, 1.73; S, 8.42.
4.20. N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-5-[(3-(4-
nitrophenyl)-1-phenyl-1H-pyrazol-4-yl)methylene]-2-thioxo-4-
thiazolidinone 11c
Yield 25%; yellow crystals, mp 142–144 °C; (ethanol–dioxane);
IR (KBr) v 1743 (CH3CO) cmꢀ1 1H NMR (300 MHz, CDCl3) d 1.95,
;
2.01, 2.06, 2.09 (4s, 12H, 4CH3CO), 3.88 (m, 1H, H-50), 4.23 (m,
2H, H-6a0, H-6b0), 5.26 (t, J = 9.9 Hz, 1H, H-40), 5.4 (t, J = 9.3 Hz,
1H, H-30), 6.04 (t, J = 9.3 Hz, 1H, H-20), 6.31 (d, J = 9 Hz, 1H, H-10),
7.41–7.89, 8.21 (2m, 8H, Ar-H + @CH), 8.38 (m, 3H, Ar-H + pyrazol-
yl-H). Anal. Calcd for C33H30N4O12S2 (738): C, 53.65; H, 4.09; N,
7.58; S, 8.68. Found: C, 53.81; H, 4.20; N, 7.45; S, 8.61.
4.25. 5,50-[4,40-(Pentane-1,5-diylbis(oxy))bis(4,1-
phenylene)]bis(methan-1-yl-1-ylidene)bis[N-(2,3,4,6-tetra-O-
acetyl-b-D-glucopyranosyl)-2-thioxo-4-thiazolidinone] 18
Compound 18 was prepared by the same method described
above for the synthesis of compounds 5a–f, 8a,b, 11a–e, and 17.
However, DMF in the presence of Et3N was used as the basic medium
instead of potassium hydroxide. Yield 35%; yellow crystals, mp 231–
233 °C; (ethanol–dioxane); IR (KBr) v 1751 (CH3CO) cmꢀ1; 1H NMR
(300 MHz, DMSO-d6) d 1.79–1.83 (m, 10H, pentyl-H), 1.88, 1.95,
1.98, 2.02 (4s, 24H, 8CH3CO), 4.11 (m, 2H, H-50, H-500), 4.28 (m, 4H,
H-6a0, H-6b00, H-6a00, H-6b00), 5.01 (t, J = 9.6 Hz, 2H, H-40, H-400), 5.58
(t, J = 9.3 Hz, 2H, H-30, H-300), 5.91 (t, J = 9.3 Hz, 2H, H-20, H-200), 6.52
(d, J = 9.3 Hz, 2H, H-10, H-100), 7.12, 7.61 (2d, 8H, Ar-H), 7.77 (s, 2H,
2 @CH). Anal. Calcd for C53H58N2O22S4 (1203): C, 52.90; H, 4.86; N,
2.33; S, 10.66. Found: C, 52.86; H, 4.90; N, 2.29; S, 10.70.
4.21. N-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-5-[(3-(4-
chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)methylene]-2-thioxo-
4-thiazolidinone 11d
Yield 40%; yellow crystals, mp 234–236 °C; (ethanol–dioxane);
IR (KBr) v 1740 (CH3CO) cmꢀ1 1H NMR (300 MHz, CDCl3) d 1.95,
;
2.04, 2.06, 2.10 (4s, 12H, 4CH3CO), 3.91 (m, 1H, H-50), 4.23 (m,
2H, H-6a0, H-6b0), 5.26 (t, J = 9.9 Hz, 1H, H-40), 5.39 (t, J = 9.3 Hz,
1H, H-30), 6.09 (t, J = 9.3 Hz, 1H, H-20), 6.32 (d, J = 9 Hz, 1H, H-10),
7.41–7.72, 7.85 (2m, 10H, Ar-H + @CH), 8.15 (s, 1H, pyrazolyl-H).
13C NMR (300 MHz, CDCl3) d 20.3–20.7 (4CH3CO), 61.6 (C-20),
67.8 (C-60), 68.0 (C-40), 73.2 (C-30), 75.0 (C-50), 82.0 (C-10), 116.4
(C@C for rhod.), 118.8, 119.6, 124.2, 127.6, 128.0, 129.2, 129.7,
130.1, 135.4, 139.0 (Ar-C), 163.6 (C@O), 169.2, 169.5, 170.1,
170.5 (CH3CO), 192.5 (C@S). Anal. Calcd for C33H30ClN3O10S2
5. Antimicrobial assay
The antimicrobial activity of the tested samples was deter-
mined using a modified Kirby–Bauer disk diffusion method.33