A. Hemamalini et al. / Carbohydrate Research 346 (2011) 1814–1819
1817
4.2.4. Physicochemical and spectral data for (E)-1-(4,6-O-
J = 4.2 Hz, 3H, Sac-H), 3.22–3.19 (m, 2H, Ha, Sac-H), 2.98 (dd,
J = 6.0 Hz, J = 15.6 Hz, 1H, Sac-H), 1.65–1.58 (m, 2H, –CH2), 1.45–
1.37 (m, 2H, –CH2), 0.93–0.88 (t, 3H, J = 7.5 Hz, –CH3); 13C NMR
(75 MHz, CDCl3): d 131.9, 131.0, 127.2, 122.0, 103.2, 102.5, 80.3,
78.7, 75.1, 73.2, 70.6, 68.3, 36.2, 28.6, 17.5, 13.9; Anal. Calcd for
butylidene-b-
D
-glucopyranosyl)-4-(3-indole)but-3-en-2-one
(5f)
To a solution of 1-C-(4,6-O-butylidene-b-
D
-glucopyranosyl)pro-
pane-2-one (3b) (0.27 g, 1 mmol) in CH2Cl2, 0.1 mL (30 mol %) of
pyrrolidine was added with stirring. To the stirred solution in-
dole-3-carbaldehyde (0.18 g, 1.2 mmol) was added, and the reac-
tion mixture was monitored by TLC. The pale-brown residue thus
obtained was purified by column chromatography (1:1 hexane–
EtOAc). Yield: 0.30 g (75%); mp 195–198 °C; 1H NMR (300 MHz,
CDCl3 + DMSO-d6): d 11.23 (s, 1H, –NH), 7.86 (d, J = 16.2 Hz, 1H,
Alk-H), 7.61–7.47 (m, 3H, Ar-H), 7.25–7.22 (m, 1H, Ar-H), 6.81 (d,
J = 15.9 Hz, 1H, Alk-H), 4.96–4.90 (m, 1H, Sac-H), 4.70–4.64 (m,
1H, Sac-H), 4.55 (t, J = 5.1 Hz, 1H, Ace-H), 4.12–4.08 (dd,
J = 9.0 Hz, J = 3.3 Hz, 1H, Sac-H), 3.93 (t, J = 7.5 Hz, 1H, Sac-H),
3.65 (t, J = 7.5 Hz, 1H, Sac-H), 3.43 (t, J = 9.6 Hz, 1H, Sac-H), 3.33–
3.26 (m, 3H, Hb, Sac-H), 3.18–3.12 (m, 2H, Ha, Sac-H), 2.88–2.80
(m, 1H, Sac-H), 1.68–1.59 (m, 2H, –CH2), 1.47–1.39 (m, 2H,
–CH2), 0.91 (t, J = 7.2 Hz, 3H, –CH3); 13C NMR (75 MHz,
CDCl3 + DMSO-d6): d 202.8, 142.5, 142.4, 135.9, 130.1, 127.6,
126.1, 125.9, 124.9, 117.5, 117.2, 107.0, 85.4, 79.8, 79.6, 75.4,
73.1, 48.0, 41.0, 22.1, 18.7; Anal. Calcd for C22H27NO6: C, 65.82;
H, 6.78; N, 3.49. Found: C, 65.51; H, 6.42; N, 3.81.
C
20H25BrN2O5: C, 52.99; H, 5.56; N, 6.18. Found: C, 53.45; H,
5.29; N, 6.39.
4.3.2. Physicochemical and spectral data for 5-(5-bromo-3-
pyridyl)-3-(4,6-O-butylidene-b-D-glucopyranosylmethyl)-1H-
pyrazole (6b)
Yellow solid; Yield: 0.36 g (81%); mp 102–104 °C; FTIR (KBr,
m
cmꢀ1): 1656, 1556; 1H NMR (300 MHz, CDCl3): d 8.87 (s, 1H, Ar-
H), 8.56 (s, 1H, Ar-H), 8.16 (s, 1H, Ar-H), 6.43 (s, 1H, Pyr-H), 4.51
(t, J = 6.0 Hz, 1H, Ace-H), 4.16 (dd, J = 4.5 Hz, J = 10.5 Hz, 1H, Sac-
H), 3.72 (t, J = 8.4 Hz, 1H, Sac-H), 3.55–3.63 (m, 2H, Sac-H), 3.47
(t, J = 9.9 Hz, 1H, Sac-H), 3.31 (t, J = 8.4 Hz, 1H, Sac-H), 3.28 (m,
2H, Hb, Sac-H), 3.23–3.17 (m, 3H, Ha, Sac-H), 2.97 (dd, J = 4.8 Hz,
J = 15.0 Hz, 1H, Sac-H), 1.67–1.58 (m, 2H, –CH2), 1.43–1.31 (m,
2H, –CH2), 0.88–0.83 (m, 3H, –CH3); 13C NMR (75 MHz, CDCl3): d
153.7, 149.8, 139.7, 107.5, 107.0, 85.2, 83.6, 79.6, 78.4, 75.4, 73.1,
41.0, 36.2, 32.8, 22.1, 18.7; Anal. Calcd for C19H24BrN3O5: C,
50.23; H, 5.32; N, 9.25. Found: C, 50.66; H, 4.99; N, 9.38.
4.2.5. Physicochemical and spectral data for (E)-1-(2,3-di-O-
4.3.3. Physicochemical and spectral data for 5-(4-
acetyl-4,6-O-butylidene-b-
D
-glucopyranosyl)-4-(4-
allyloxyphenyl)-3-(4,6-O-butylidene-b-D-
bromophenyl)but-3-en-2-one (5h)
glucopyranosylmethyl)-1H-pyrazole (6c)
To a solution of compound 5b (0.44 g, 1.0 mmol) in Ac2O
(0.94 mL, 10 mmol), NaOAc (0.08 g, 1.0 mmol) was added, the mix-
ture was heated under reflux for 1 h. The reaction mixture was
then poured over crushed ice. The white solid that precipitated
was then filtered off and dried. Yield: 0.45 g (85%); mp 146–
148 °C; 1H NMR (300 MHz, CDCl3): d 7.55–7.39 (m, 5H, Ar-H, Alk-
H), 6.70 (d, J = 15.9 Hz, 1H, Alk-H), 5.23 (t, J = 9.0 Hz, 1H, Ace-H),
4.93 (t, J = 9.3 Hz, 1H, Sac-H), 4.48 (t, J = 5.1 Hz, 1H, Sac-H), 4.19–
4.13 (m, 3H, Hb, Sac-H), 3.40 (d, J = 7.5 Hz, 2H, Ha, Sac-H), 2.97–
2.88 (dd, J = 8.7 Hz, J = 15.2 Hz, 1H, Sac-H), 2.68–2.61 (dd,
J = 3.3 Hz, J = 16.2 Hz, 1H, Sac-H), 2.03 (s, 6H, –COCH3), 1.50–1.54
(m, 2H, –CH2), 1.43–1.31 (m, 2H, –CH2), 0.92–0.87 (t, J = 7.5 Hz,
3H, –CH3); 13C NMR: (75 MHz, CDCl3): d 195.9, 170.2, 142.2,
133.2, 132.3, 131.9, 129.7, 128.4, 126.6, 125.1, 102.6, 78.4, 74.5,
73.1, 72.5, 70.8, 68.1, 43.0, 36.0, 20.8, 17.4, 13.8; Anal. Calcd for
Yellow solid; Yield: 0.34 g (83%); mp 135–137 °C; ½a D28
ꢁ
ꢀ354.1
(c 30 mmol, CHCl3); 1H NMR (300 MHz, CDCl3):
d 7.18 (d,
J = 6.9 Hz, 2H, Ar-H), 6.86 (d, J = 6.3 Hz, 2H, Ar-H), 6.09–5.98 (m,
1H, Alk-H), 6.32 (s, 1H, Pyr-H), 5.43–5.27 (dd, J = 17.1 Hz,
J = 10.5 Hz, 2H, Alk-H), 4.51 (t, J = 9.0 Hz, 2H, Ace-H, Sac-H), 4.08
(dd, J = 3.6 Hz, J = 9.0 Hz, 1H, Sac-H), 3.89 (t, J = 6.5 Hz, 1H, Sac-H),
3.70–3.58 (m, 2H, Sac-H), 3.37–3.41 (m, 3H, Hb, Sac-H), 3.24 (d,
J = 8.1 Hz, 2H, Sac-H), 3.20–3.04 (m, 3H, Ha, Sac-H), 2.74–2.60 (m,
1H, Sac-H), 1.45–1.37 (m, 2H, –CH2), 1.05–1.00 (m, 2H, –CH2),
0.89 (t, J = 6.0 Hz, 3H, –CH3); 13C NMR (75 MHz, CDCl3): d 127.3,
126.9, 115.0, 114.8, 102.4, 102.0, 80.5, 78.3, 74.8, 73.7, 70.6, 69.6,
68.9, 68.4, 45.2, 36.2, 32.4, 22.6, 17.5, 13.9. Anal. Calcd for
C23H30N2O6: C, 64.17; H, 7.02; N, 6.51. Found: C, 63.65; H, 7.36;
N, 5.76.
C24H29BrO8: C, 54.87; H, 5.56. Found: C, 55.23; H, 5.13.
4.3.4. Physicochemical and spectral data for 3-(4,6-O-
butylidene-b-D-glucopyranosylmethyl)-5-(pyren-3-yl)-1H-
4.3. General procedure for the synthesis of sugar-pyrazole
derivatives, 6(a–f)
pyrazole (6d)
Brown syrup; Yield: 0.35 g (73%); ½a D28
ꢀ10.3 (c 30 mmol,
ꢁ
CHCl3); 1H NMR (300 MHz, CDCl3): d 8.50–8.47 (d, J = 9.2 Hz, 1H,
Ar-H), 8.24–7.91 (m, 8H, Ar-H), 6.55 (s, 1H, Pyr-H), 4.45 (t,
J = 6.0 Hz, 1H, Ace-H), 4.17 (dd, J = 4.5 Hz, J = 9.6 Hz, 1H, Sac-H),
3.78 (t, J = 8.7 Hz, 1H, Sac-H), 3.73–3.68 (m, 1H, Sac-H), 3.45 (t,
J = 9.0 Hz, 2H, Sac-H), 3.35 (dd, J = 4.5 Hz, 1H, Sac-H), 3.29 (d,
J = 6.6 Hz, 2H, Hb, Sac-H), 3.25–3.19 (m, 3H, Ha, Sac-H), 3.14–3.07
(dd, J = 5.4 Hz, J = 15.6 Hz, 1H, Sac-H), 1.59–1.55 (m, 2H, –CH2),
1.43–1.27 (m, 2H, –CH2), 0.90–0.83 (m, 3H, –CH3); 13C NMR
(75 MHz, CDCl3): d 131.3, 128.0, 127.8, 127.3, 127.0, 126.1, 125.4,
125.1, 124.9, 124.8, 124.7, 102.5, 80.4, 78.8, 75.2, 73.5, 70.6, 68.4,
36.2, 30.9, 29.7, 17.5, 13.9; Anal. Calcd for C30H30N2O5: C, 72.27;
H, 6.06; N, 5.62. Found: C, 71.79; H, 6.34; N, 5.91.
To a solution of (E)-1-(4,6-O-butylidene-b-D-glucopyranosyl)-4-
(phenyl)but-3-en-2-one, (1.0 mmol) in abs EtOH were added
hydrazine hydrate (11.0 mmol). After stirring under reflux for a gi-
ven period of time (see Table 2), the solvent was evaporated under
reduced pressure. The crude product was slurried using silica gel
and purified by flash column chromatography using 7:3 hexane–
EtOAc as eluent to get the corresponding sugar-pyrazole
derivatives.
4.3.1. Physicochemical and spectral data for 5-(4-
bromophenyl)-3-(4,6-O-butylidene-b-
1H-pyrazole (6a)
D-glucopyranosylmethyl)-
Yellow solid; Yield: 0.39 g (89%); mp 107–110 °C; ½a D28
ꢁ
ꢀ90.8 (c
4.3.5. Physicochemical and spectral data for 5-(anthracen-9-yl)-
3-(4,6-O-butylidene-b-D-glucopyranosylmethyl)-1H-pyrazole
90 mmol, CHCl3); FTIR (KBr,
m
cmꢀ1): 1661, 1561, 3251; 1H NMR
(300 MHz, CDCl3):
d
7.59 (d, J = 8.4 Hz, 2H, Ar-H), 7.51 (d,
(6e)
J = 8.4 Hz, 2H, Ar-H), 6.38 (s, 1H, Pyr-H), 4.52 (t, J = 6.0 Hz, 1H,
Ace-H), 4.18 (dd, J = 4.8 Hz, J = 10.2 Hz, 1H, Sac-H), 3.70 (t,
J = 8.7 Hz, 1H, Sac-H), 3.58–3.61 (m, 1H, Sac-H), 3.49 (t,
J = 10.2 Hz, 1H, Sac-H), 3.35–3.28 (m, 2H, Hb, Sac-H), 3.25 (d,
Yellow solid; Yield: 0.32 g (70%); mp 120–122 °C; FTIR (KBr, m
cmꢀ1) 1662, 1559; ½a 2D8
ꢁ
ꢀ10.4 (c 100 mmol, CHCl3); 1H NMR
(300 MHz, CDCl3): d 8.42–8.23 (m, 3H, Ar-H), 8.01–7.98 (m, 2H,
Ar-H), 7.46–7.41 (m, 4H, Ar-H), 6.70 (s, 1H, Pyr-H), 4.50