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11
1H NMR (DMSO-d6) d: 7.85 (d, J = 8.7 Hz, 2H), 7.46–7.23 (m, 9H),
6.55 (s, 1H), 4.24 (q, J = 7,3 Hz, 2H), 3.8 (s, 2H), 1.32 (t, J = 7,3 Hz,
3H). IR (cmꢀ1: neat): 1736, 1343, 1164. LC–MS (APCI+) m/z: 386
(M+H)+.
4.1.36. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-p-
cyanophenyl-1H-pyrazole (3e)
The title compound was prepared from ester 2e according using
the same procedure as for 3a to give 3e as white crystal (yield:
10%), mp 201–203 °C. 1H NMR (DMSO-d6) d: 7.90 (d, J = 8.5 Hz,
2H), 7.80 (d, J = 8.5 Hz, 2H), 7.45 (s, 2H), 7.40 (m, 4H), 6.80 (s,
1H), 5.30 (t, J = 5.8 Hz, 1H), 4.50 (d, J = 5.8 Hz, 2H). IR (cmꢀ1: neat):
2235, 1344, 1165. LC–MS (APCI+) m/z: 355 (M+H)+. Anal. Calcd for
4.1.31. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-phenyl-
1H-pyrazole (3a)
The ethyl ester (4.8 mmol, 1.4 g) was dissolved in tetrahydrofu-
ran (20 mL) and then a suspension of LiAlH4 (9.6 mmol, 0.37 g) in
tetrahydrofuran (5 mL) was slowly added. After 3 h of reaction at
20 °C, an aqueous solution of HCl 1 N was added dropwise until a
neutral pH. The reaction mixture was concentrated under reduced
pressure the residue was taken into ethyl acetate and washed with
water and brine. The organic layer was dried over MgSO4 and con-
centrated under reduced pressure. The residue was recrystallized
in acetonitrile. The alcohol (3a) give a white crystal (yield: 84%),
mp 186–188 °C 1H NMR (DMSO-d6) d: 7.79 (d, J = 8.4 Hz, 2H),
7.45 (m, 7H), 7.25 (m, 2H), 6.64 (s, 1H), 5.27 (t, J = 5.8 Hz, 1H),
4.76 (s, 2H). IR (cmꢀ1: neat): 3297, 1593. LC–MS (APCI+) m/z: 330
(M+H)+. Anal. Calcd for C16H15N3O3S: C, 58.35; H, 4.59; N, 12.76.
Found: C, 58.42; H, 4.68; N, 12.86.
C17H14N4O3S: C, 57.62; H, 3.98; N, 15.81. Found: C, 57.69; H, 4.31;
N, 15.98.
4.1.37. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-
(4-methoxyphenyl)-1H-pyrazole (3f)
The title compound was prepared from ester 2f using the same
procedure as for 3a to give 3f as white crystal (yield: 32%), mp
114–116 °C. 1H NMR (DMSO-d6) d: 7.80 (d, J = 8.7 Hz, 2H), 7.44
(s, 2H), 7.41 (d, J = 8.7 Hz, 2H), 7.17 (d, J = 8.7 Hz, 2H), 6.96 (d,
J = 8.7 Hz, 2H), 6.55 (s, 1H), 5.22 (t, J = 5.8 Hz, 1H), 4.50 (d,
J = 5.8 Hz, 2H), 3.76 (s, 3H). IR (cmꢀꢀ1: neat): 1336, 1161. LC–MS
(APCI+) m/z: 360 (M+H)+. Anal. Calcd for C17H17N3O4S: C, 56.81;
H, 4.77; N, 11.69. Found: C, 56.98; H, 4.63; N, 11.78.
4.1.32. 1-(4-Aminosulfonylphenyl)-5-hydroxymethyl-3-phenyl-
1H-pyrazole (3a0)
4.1.38. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-
(3-methoxyphenyl)-1H-pyrazole (3g)
The title compound was prepared from ester 2a0 using the same
procedure as for 3a to give 3a0 as yellow crystal (yield: 64%), mp
200–202 °C. 1H NMR (DMSO-d6) d: 7.8 (d, J = 8.7 Hz, 2H), 7.44 (m,
7H), 7.24 (m, 2H), 6.64 (s, 1H), 5.27 (t, J = 5.8 Hz, 1H), 4.53 (d,
J = 5.8 Hz, 2H). IR (cmꢀ1: neat): 3336, 1336, 1167. LC–MS (APCI+)
m/z: 330 (M+H)+Å Anal. Calcd for C16H15N3O3S: C, 58.35; H, 4.59;
N, 12.76. Found: C, 58.32; H, 4.74; N, 12.90.
The title compound was prepared from ester 2g using the same
procedure as for 3a to give 3g as white crystal (yield: 59%), mp
177–179 °C 1H NMR (DMSO-d6) d: 7.81 (d, J = 8.7 Hz, 2H), 7.46 (s,
2H), 7.42 (d, J = 8.7 Hz, 2H), 7.30 (t, J = 7.9 Hz, 1H), 6.97 (d,
J = 8.1 Hz, 1H), 6.83 (s, 1H), 6.77 (d, J = 7.7 Hz, 1H), 6.66 (s, 1H),
5.27 (t, J = 5.7 Hz, 1H), 4.52 (d, J = 5.7 Hz, 2H), 3.69 (s, 3H). IR
(cmꢀ1: neat): 1164. LC–MS (APCI+) m/z: 360 (M+H)+. Anal. Calcd
for C17H17N3O4S: C, 56.81; H, 4.77; N, 11.69. Found: C, 56.68; H,
4.87; N, 11.83.
4.1.33. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-
pyridinyl-1H-pyrazole (3b)
The title compound was prepared from ester 2b using the same
procedure as for 3a to give 3b as yellow crystal (yield: 57%), mp
154–156 °C 1H NMR (DMSO-d6) d: 8.55 (s, 1H), 8.46 (s, 1H), 7.82
(d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.1 Hz, 1H), 7.45 (m, 5H), 6.77 (s,
1H), 5.29 (t, J = 5.8 Hz, 1H), 4.54 (d, J = 5.8 Hz, 2H). IR (cmꢀ1: neat):
1333, 1158. LC–MS (APCI+) m/z: 331 (M+H)+. Anal. Calcd for
C15H14N4O3S: C, 54.54; H, 4.27; N, 16.96. Found: C, 54.45; H,
4.45; N, 16.90.
4.1.39. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-
(2-methoxyphenyl)-1H-pyrazole (3h)
The title compound was prepared from ester 2h using the same
procedure as for 3a to give 3h as white crystal (yield: 82%), mp
201–203 °C. 1H NMR (DMSO-d6) d: 7.72 (d, J = 8.7 Hz, 2H), 7.41 (t,
J = 7.9 Hz, 2H), 7.29 (m, 4H), 7.03 (t, J = 7.3 Hz, 1H), 6.97 (d,
J = 8.4 Hz, 1H), 6.49 (s, 1H), 5.22 (t, J = 5.8 Hz, 1H), 4.51 (d,
J = 5.8 Hz, 2H), 3.33 (s, 3H). IR (cmꢀ1: neat): 1327, 1162. LC–MS
(APCI+) m/z: 343 (M+H)+. Anal. Calcd for C17H17N3O4S: C, 56.81;
H, 4.77; N, 11.69. Found: C, 56.67; H, 4.78; N, 11.54.
4.1.34. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-p-tolyl-
1H-pyrazole (3c)
The title compound was prepared from ester 2c using the
same procedure as for 3a to give 3c as white crystal (yield:
73%), mp 166–168 °C. 1H NMR (DMSO-d6) d: 7.80 (d, J = 8.7 Hz,
2H), 7.44 (m, 3H), 7.39 (d, J = 8.7 Hz, 2H), 7.20 (d, J = 8.0 Hz,
1H), 7.13 (d, J = 8.0 Hz, 2H), 6.58 (s, 1H), 5.24 (t, J = 5.8 Hz, 1H),
4.51 (d, J = 5.8 Hz, 2H) 2.31 (s, 3H). IR (cmꢀ1: neat): 1327,
1162. LC–MS (APCI+) m/z: 344 (M+H)+. Anal. Calcd for
4.1.40. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-
(1-naphthyl)-1H-pyrazole (3i)
The title compound was prepared from ester 2i using the same
procedure as for 3a to give 3i as yellow crystal (yield: 96%), mp
190–192 °C. 1H NMR (DMSO-d6) d: 8.82 (m, 2H), 8.05 (d,
J = 1.4 Hz, 2H), 8.03 (m, 1H), 7.91 (m, 4H), 7.73 (m, 2H), 6.49 (m,
4H), 6.80 (s, 1H), 5.32 (t, J = 5.7 Hz, 1H). IR (cmꢀ1: neat): 3320,
1339, 1160. LC–MS (APCI+) m/z: 380 (M+H)+. Anal. Calcd for
C17H17N3O3S: C, 59.46; H, 4.99; N, 12.24. Found: C, 59.69; H,
5.08; N, 12.58.
C20H17N3O3S: C, 63.31; H, 4.52; N, 11.07. Found: C, 63.65; H,
4.59; N, 11.48.
4.1.35. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-p-
bromophenyl-1H-pyrazole (3d)
4.1.41. 1-(4-Aminosulfonylphenyl)-3-hydroxymethyl-5-
(2-naphthyl)-1H-pyrazole (3j)
The title compound was prepared from ester 2d using the same
procedure as for 3a to give 3d as white crystal (yield: 62%), mp
203–205 °C 1H NMR (DMSO-d6) d: 7.81 (d, J = 6.8 Hz, 2H), 7.62 (d,
J = 8.7 Hz, 2H), 7.44 (m, 4H), 7.22 (d, J = 8.7 Hz, 2H), 6.67 (s, 1H),
5.27 (t, J = 6.2 Hz, 1H), 4.53 (d, J = 6.2 Hz, 2H). IR (cmꢀ1: neat):
1396, 1159. LC–MS (APCI+) m/z: 408 [(M+H)+ 79Br] and 410
[(M+H)+ 81Br]. Anal. Calcd for C16H14BrN3O3S: C,47.07; H, 3.46; N,
10.29. Found: C, 47.40; H, 3.52; N, 10.34.
The title compound was prepared from ester 2j using the same
procedure as for 3a to give 3j as yellow crystal (yield: 23%), mp
226–228 °C. 1H NMR (DMSO-d6) d: 8.40 (s, 1H), 7.90 (m, 8H),
7.60 (m, 4H), 7.20 (s, 1H), 5.80 (t, J = 5.0 Hz, 1H), 4.80 (d,
J = 6.3 Hz, 2H). IR (cmꢀ1: neat): 3336, 1336, 1167. LC–MS (APCI+)
m/z: 380 (M+H)+. Anal. Calcd for C20H17N3O3S: C, 63.31; H, 4.52;
N, 11.07. Found: C, 63.45; H, 4.65; N, 11.28.