M. Abid, A. Azam / Bioorg. Med. Chem. 13 (2005) 2213–2220
2217
4.3.3. 3-(3-Chlorophenyl)-2-pyrazoline-1-(N-propyl)thio-
carboxamide (3). Yield: 22%; dark yellow solid; Rf
4.3.7. 3-Phenyl-2-pyrazoline-1-(N-butyl)thiocarboxamide
(7). Yield: 24%; creamish yellow solid; R 0.65; mp
f
0
5
1
3
1
.80; mp 119 ꢁC; Anal. Calcd (C H N SCl): C,
94 ꢁC; Anal. Calcd (C H N S): C, 64.37; H, 7.28; N,
1
3
16
3
14 19
3
5.42; H, 5.68; N, 14.92. Found: C, 55.55; H, 5.69; N,
16.09. Found: C, 64.41; H, 7.29; N, 16.11%; UV: k
max
ꢀ
1
ꢀ1
4.91%; UV: kmax (nm): 324, 237, 210; IR: mmax/cm
353 (NH), 3021 (arom. C–H), 2923 (aliph. C–H),
:
(nm): 363.3, 325.5, 214.5, 204.3; IR: mmax/cm : 3368
(NH), 3069 (arom. C–H), 2995 (aliph. C–H), 1540
1
1
525 (C@N), 1124 (C–N), 1078 (C@S); H NMR
(C@N), 1168 (C–N), 1034 (C@S); H NMR (CDCl ):
3
(CDCl ): (d, ppm) 8.07 (1H, s, –NH), 7.18–7.89 (4H,
m, aryl), 4.47 (2H, t, –CH , J = 8.97 Hz), 3.54 (2H, q,
(d, ppm) 8.01 (1H, s, –NH), 7.16–7.67 (5H, m, aryl),
4.41 (2H, t, –CH , J = 7.69 Hz), 3.72 (2H, q, –CH ,
J = 5.77 Hz), 3.29 (2H, t, –CH , J = 9.61 Hz), 1.61–
3
2
2
2
–
1
–
1
1
CH , J = 6.45 Hz), 3.29 (2H, t, –CH , J = 10.03 Hz),
2
2
2
.37–1.67 (2H, m, –CH , J = 5.89 Hz), 1.13 (3H, t,
2
CH , J = 6.01 Hz);
3
1.71 (2H, m, –CH , J = 7.95 Hz), 1.37–1.49 (2H, m,
2
1
3
C NMR (CDCl ): (d, ppm)
–CH , J = 6.81 Hz), 1.00 (3H, t, CH , J = 7.95 Hz);
3
3
2
1
3
77.2 (C@S), 155.4 (C@N), 136.2, 133.2, 131.4, 129.2,
C NMR (CDCl ): (d, ppm) 177.4 (C@S), 154.8
3
25.4, 122.8 (aryl–C), 75.3 (CH ), 55.5 (CH ), 46.9
(C@N), 132.2, 130.3, 129.6, 126.6, 124.7, 121.8 (aryl–
2
2
(
CH ), 31.9 (CH ), 15.1 (CH ).
3
C), 77.0 (CH ), 56.2 (CH ), 46.6 (CH ), 32.9 (CH ),
25.5 (CH ), 14.3 (CH ).
2
2
2
2
2
2
2
3
4.3.4. 3-Phenyl-2-pyrazoline-1-(N-isopropyl)thiocarbox-
amide (4). Yield: 27%; cream solid; Rf 0.73; mp
4.3.8. 3-(3-Bromophenyl)-2-pyrazoline-1-(N-butyl)thio-
carboxamide (8). Yield: 18%; brown solid; R 0.56; mp
1
32 ꢁC; Anal. Calcd (C H N S): C, 63.16; H, 6.88;
1
3
17
3
f
N, 17.00. Found: C, 63.12; H, 6.85; N, 17.02%; UV: k
96 ꢁC; Anal. Calcd (C H N SBr): C, 49.41; H, 5.29;
max
14 18
3
ꢀ1
(
nm): 373, 323.3, 242, 212; IR: mmax/cm : 3325 (NH),
N, 12.35. Found: C, 49.39; H, 5.19; N, 12.37%; UV: k
max
1
ꢀ
3
1
7
029 (arom. C–H), 2933 (aliph. C–H), 1559 (C@N),
(nm): 329, 295.4, 242.4, 208.5; IR: mmax/cm : 3365
1
166 (C–N), 1061 (C@S); H NMR (CDCl ): (d, ppm)
(NH), 3025 (arom. C–H), 2975 (aliph. C–H), 1541
3
1
.96 (1H, s, –NH), 7.13–7.64 (5H, m, aryl), 4.51–4.66
(C@N), 1211 (C–N), 1078 (C@S); H NMR (CDCl ):
3
(
J = 8.04 Hz), 3.28 (2H, t, –CH , J = 10.71 Hz), 1.32
1H, m, –CH, J = 7.21 Hz), 4.40 (2H, t, –CH2,
(d, ppm) 8.06 (1H, s, –NH), 7.19–7.88 (4H, m, aryl),
4.43 (2H, t, –CH , J = 8.33 Hz), 3.73 (2H, q, –CH ,
J = 6.66 Hz), 3.26 (2H, t, –CH , J = 9.00 Hz), 1.62–
2
2
2
1
3
(
6H, d, –CH , J = 5.36 Hz); C NMR (CDCl ): (d,
3
3
2
ppm) 176.7 (C@S), 155.2 (C@N), 133.4, 130.5, 127.9,
1.72 (2H, m, –CH , J = 8.74 Hz), 1.33–1.51 (2H, m, –
2
1
26.3, 124.4, 121.5 (aryl–C), 77.2 (CH ), 57.3
CH , J = 7.28 Hz), 1.01 (3H, t, –CH , J = 5.82 Hz);
2
2
3
1
3
(
(
CH), 46.3 (CH ), 18.5 (2CH ); MS (ESI) m/z: 246
2
Mꢀ1).
C NMR (CDCl ): (d, ppm) 183.7 (C@S), 161.1
(C@N), 136.4, 135.2, 131.8, 127.3, 125.1, 122.3 (aryl–
3
3
C), 78.7 (CH ), 58.2 (CH ), 49.7 (CH ), 31.6 (CH ),
23.2 (CH ), 15.1 (CH ).
2
2
2
2
4.3.5. 3-(3-Bromophenyl)-2-pyrazoline-1-(N-isopropyl)-
thiocarboxamide (5). Yield: 21%; light yellow solid; Rf
2
3
0
4
1
.75; mp 155 ꢁC; Anal. Calcd (C H N SBr): C,
4.3.9. 3-(3-Chlorophenyl)-2-pyrazoline-1-(N-butyl)thio-
carboxamide (9). Yield: 14%; dark yellow solid; Rf
0.51; mp 108 ꢁC; Anal. Calcd (C H N SCl): C,
1
3
16
3
7.85; H, 4.91; N, 12.88. Found: C, 47.87; H, 4.89; N,
2.91%; UV: k (nm): 376, 318, 237.2, 215.3; IR:
max
14 18
3
ꢀ
1
mmax/cm : 3326 (NH), 3019 (arom. C–H), 2914 (aliph.
C–H), 1541 (C@N), 1164 (C–N), 1061 (C@S);
NMR (CDCl ): (d, ppm) 8.06 (1H, s, –NH), 7.11–7.88
56.85; H, 6.09; N, 14.21; found: C, 56.81; H, 6.07; N,
1
H
14.24%; UV: k
mmax/cm : 3345 (NH), 3033 (arom. C–H), 2927 (aliph.
(nm): 376.4, 304.4, 233.3, 204.3; IR:
max
ꢀ
1
3
1
(
4H, m, aryl), 4.58–4.65 (1H, m, –CH, J = 6.25 Hz),
C–H), 1581 (C@N), 1178 (C–N), 1042 (C@S);
H
4
J = 12.5 Hz), 1.32 (6H, d, –CH , J = 4.69 Hz);
NMR (CDCl ): (d, ppm) 181.3 (C@S), 155.3 (C@N),
.42 (2H, t, –CH , J = 12.5 Hz), 3.25 (2H, t, –CH ,
2
NMR (CDCl ): (d, ppm) 8.12 (1H, s, –NH), 7.21–7.89
2
3
1
3
C
(4H, m, aryl), 4.39 (2H, t, –CH , J = 8.96 Hz), 3.73
(2H, q, –CH , J = 6.87 Hz), 3.23 (2H, t, –CH ,
3
2
3
2
2
1
32.6, 131.1, 129.7, 127.8, 125.3, 122.6 (aryl–C), 75.3
CH ), 55.6 (CH), 47.2 (CH ), 15.6 (2CH ); MS (ESI)
J = 9.61 Hz), 1.70–1.59 (2H, m, –CH , J = 7.71 Hz),
2
(
m/z: 326 (M ).
1.34–1.47 (2H, m, –CH , J = 6.39 Hz), 1.01 (3H, t,
2
2
2
3
+
13
–CH , J = 5.89 Hz);
3
C NMR (CDCl ): (d, ppm)
3
177.3 (C@S), 155.2 (C@N), 137.0, 134.2, 132.9, 127.3,
4.3.6. 3-(3-Chlorophenyl)-2-pyrazoline-1-(N-isopropyl)-
thiocarboxamide (6). Yield: 18%; brown solid; R 0.57;
124.8, 122.7 (aryl–C), 76.6 (CH ), 56.3 (CH ), 48.6
(CH ), 31.4 (CH ), 24.5 (CH ), 14.1 (CH ); MS (ESI)
2 2 2 3
2
2
f
+
m/z: 296 (M ).
mp 145 ꢁC; Anal. Calcd (C H N SCl): C, 55.42; H,
1
3
16
3
5
.68; N, 14.92. Found: C, 55.49; H, 5.65; N, 14.89%;
ꢀ
1
UV: kmax (nm): 361, 307.3, 235, 206.2; IR: mmax/cm
:
221 (NH), 3018 (arom. C–H), 2976 (aliph. C–H),
4.3.10. 3-Phenyl-2-pyrazoline-1-(N-isobutyl)thiocarboxa-
mide (10). Yield: 21%; cream solid; R 0.69; mp 115 ꢁC;
3
f
1
1
561 (C@N), 1168 (C–N), 1052 (C@S); H NMR
Anal. Calcd (C H N S): C, 64.36; H, 7.28; N, 16.09.
1
4
19
3
(CDCl ): (d, ppm) 7.98 (1H, s, –NH), 7.19–7.87 (4H,
m, aryl), 4.55–4.66 (1H, m, –CH, J = 6.38 Hz), 4.42
Found: C, 64.35; H, 7.26; N, 16.12%; UV: k
322, 222.1, 216.3; IR: mmax/cm : 3365 (NH), 3060
(nm):
max
3
ꢀ
1
(
J = 7.98 Hz), 1.34 (6H, d, –CH , J = 6.14 Hz);
2H, t, –CH , J = 9.57 Hz), 3.25 (2H, t, –CH ,
2
(arom. C–H), 2975 (aliph. C–H), 1532 (C@N), 1126
2
1
3
1
C
(C–N), 1056 (C@S); H NMR (CDCl ): (d, ppm) 8.00
3
3
NMR (CDCl ): (d, ppm) 177.2 (C@S), 156.4 (C@N),
(1H, s, –NH), 7.16–7.65 (5H, m, aryl), 4.42 (2H, t,
–CH , J = 10.13 Hz), 3.55 (2H, t, –CH , J = 6.08 Hz),
3
1
37.1, 134.9, 132.7, 130.6, 127.4, 126.3 (aryl–C), 77.4
CH ), 57.7 (CH ), 48.4 (CH ), 14.8 (2CH ); MS (ESI)
2
2
(
m/z: 282 (M ).
3.30 (2H, t, –CH , J = 10.13 Hz), 1.96–2.05 (1H, m,
2
–CH, J = 7.26 Hz), 1.01 (6H, d, –CH , J = 6.05 Hz);
3
2
2
2
3
+