5782
N. Go¨khan-Kelekc¸i et al. / Bioorg. Med. Chem. 15 (2007) 5775–5786
thiophen aldehyde according to the methods given
before.48,49
H5), 7.24 (d; 2H; phenyl H3,H5), 7.45 (s; 1H; NH), 7.63
(d; 2H; phenyl H2,H6), 10.4 (br; 1H; NH); MS (70 eV,
EI): 324 (M+ꢀ, 94.31%), (M+2+ꢀ, 8.27%), 291 (M+–SH,
15.37%), 268 (M+–NHC3H5, 88.88%), 224 (M+–
CSNHC6H5, 27.05%), 151 (M+–C12H14N 100%), 93
4.3. Preparation of 1-thiocarbamoyl-3,5-diphenyl-2-pyr-
azolines (3a–3l) (general procedure)
(M+–C13H14N2S, 25.51%), 41
(M+–C15H14N4S,
To a solution of chalcone derivatives (0.01 mol) and
substituted thiosemicarbazide (0.012 mol) in 25 ml of
ethanol, a solution of sodium hydroxide (0.025 mol) in
5 ml of water was added and refluxed for 8 h. The prod-
ucts were poured into crushed ice and the solid mass
which separated out was filtered, dried and crystallized
from appropriate solvents affording the corresponding
3a–3l. Yields, melting points, spectral and analytical
data of synthesized compounds are given below.
13.83%); Analysis calculated for C18H19N4S.
4.3.4. 1-N-Phenylthiocarbamoyl-3-(4-methylphenyl)-5-(2-
pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 38%; mp 170–
20
D
172 ꢁC (chloroform–methanol); ½aꢂ +28 (c 0.2, CHCl3);
IR (KBr): 3355 (N–H), 1524 (C@N), 1451 (C@C), 1346
1
(C@S); H NMR d (ppm): 2.38 (s; 3H; Ph–CH3), 3.40
(dd; 1H; HA, JAB: 17.52 Hz, JAX: 2.96 Hz), 3.80 (m;
3H; HB, JAB: 17.52 Hz, JBX: 10.96 Hz), 6.50 (dd; 1H;
HX, JAX: 2.96 Hz, JBX: 10.96 Hz), 6.91 (dd; 1H; pyrrole
H4), 7.06 (d; 1H; pyrrole H3), 7.69–7.16 (m; 10H; pyrrole
H5 ve phenyl H), 9.19 (s; 1H; NH), 10.6 (br; 1H; NH);
MS (70 eV, EI): m/z (%): 360 (M+ꢀ, 70.19%), (M+2+ꢀ,
4.87%), 327 (M+–SH, 35.07%), 268 (M+–NHC6H5,
33.32%), 151 (M+–C15H14N, 100%), 77 (M+–
4.3.1. 1-N-Methylthiocarbamoyl-3-(4-methylphenyl)-5-
(2-pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 59%; mp
20
D
CHCl3); IR (KBr): 3366 (N–H), 2908 (C–H), 1537
228–230 ꢁC (chloroform–methanol); ½aꢂ +20 (c 0.2,
(C@N), 1415 (C@C), 1353 (C@S) cmꢀ1 1H NMR d
;
(ppm): 2.41 (s; 3H; Ph–CH3), 3.20 (d; 3H; J: 4.83 Hz,
C15H14N4S, 38.63%);
C21H19N4S.
Analysis
calculated
for
NH–CH3), 3.34 (dd; 1H; HA, JAB: 17.44 Hz, JAX
3.08 Hz), 3.73 (dd; 1H; HB, JAB: 17.44 Hz, JBX
11.12 Hz), 6.40 (dd; 1H; HX, JAX: 3.08 Hz, JBX
:
:
:
4.3.5. 1-N-Methylthiocarbamoyl-3-(4-chlorophenyl)-5-(2-
pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 55%; mp 219–
11.12 Hz), 6.92 (t; 1H; pyrrole H4), 7.05 (d; 1H; pyrrole
H3), 7.17 (d; 1H; pyrrole H5), 7.26 (d; 2H; phenyl
H3,H5), 7.45 (d; 1H; J: 4.83 Hz, NH), 7.66 (d; 2H; phen-
yl H2,H6), 10.45 (br; 1H; NH); MS (70 eV, EI): m/z (%):
298 (M+ꢀ, 100%), 300 (M+2+ꢀ, 10.34%), 265 (M+–SH,
39.02%), 224 (M+–CSNHCH3, 35.83%), 166 (M+–
C10H11, 92.05%), 93 (M+–C11H12N2S, 16.89%). Analysis
calculated for (C16H17N4S).
20
D
220 ꢁC (chloroform–methanol); ½aꢂ +25 (c 0.2, CHCl3);
IR (KBr): 3370 (N–H), 2922 (C–H), 1528 (C@N), 1352
(C@S); 1H NMR d (ppm): 3.17 (d; 3H; J: 4.78 Hz, NH–
CH3), 3.30 (dd; 1H; HA, JAB: 17.48 Hz, JAX: 3.12 Hz),
3.72 (dd; 1H; HB, JAB: 17.48 Hz, JBX: 11.14 Hz), 6.41
(dd; 1H; HX, JAX: 3.12 Hz, JBX: 11.14 Hz), 6.90 (dd;
1 H; pyrrol H4), 7.02 (d; 1H; pyrrole H3), 7.16 (d;1H;
pyrrole H5), 7.40 (d; 2H; phenyl H3,H5), 7.66 (d; 2H;
phenyl H2,H6), 10.4 (br; 1H; NH); MS (70 eV, EI):
318 (M+ꢀ, 79.34%), (M+2+ꢀ, 33.65%), 285 (M+–SH,
26.81%), 244 (M+–CSNHCH3, 26.91%), 166 (M+–
C9H8Cl, 100%), 93 (M+–C10H9ClN2S, 22.66%); Analy-
sis calculated for C15H14ClN4S.
4.3.2. 1-N-Ethylthiocarbamoyl-3-(4-methylphenyl)-5-(2-
pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 60%; mp
20
D
CHCl3); IR (KBr): 3363 (N–H), 2960 (C–H), 1524
163–164 ꢁC (chloroform–methanol); ½aꢂ +23 (c 0.2,
1
(C@N), 1459 (C@C), 1336 (C@S); H NMR d (ppm):
1.26 (t; 3H; CH2–CH3), 2.39 (s; 3H; Ph–CH3), 3.30
(dd; 1H; HA, JAB: 17.44 Hz, JAX: 3 Hz), 3.70 (m; 3H;
4.3.6. 1-N-Ethylthiocarbamoyl-3-(4-chlorophenyl)-5-(2-
pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 51%; mp
219–220 ꢁC (chloroform–methanol); ½aꢂ +26 (c 0.2,
HB ve CH2–CH3), 6.40 (dd; 1H; HX, JAX: 3 Hz, JBX
:
20
D
CHCl3); IR (KBr): 3358 (N–H), 2930 (C–H), 1529
11.04 Hz), 6.92 (dd; 1H; pyrrole H4), 7.02 (d; 1H; pyr-
role H3), 7.16 (dd; 1H; pyrrole H5), 7.24 (d; 2H; phenyl
H3, H5), 7.35 (s; 1H; NH), 7.64 (d; 2H; phenyl H2,H6).
10.3 (br; 1H; NH); MS (70 eV, EI): m/z (%): 312 (M+ꢀ,
100%), 314 (M+2+ꢀ, 8.72%), 279 (M+–SH, 26.33%),
224 (M+–CSNHC2H5, 27.39%), 180 (M+–C9H10,
57.17%), 152 (M+–C11H15N, 24.42%), 93 (M+–
C12H14N2S, 17.57%), 44 (M+–C15H13N3S, 21.98%);
Analysis calculated for C17H19N4S.
1
(C@N), 1412 (C@C), 1341 (C@S); H NMR d (ppm):
1.28 (t; 3H; CH2–CH3), 3.29 (dd; 1H; HA, JAB
:
17.48 Hz, JAX: 3.08 Hz), 3.74 (m; 3H; HB ve CH2-
CH3), 6.40 (dd; 1H; HX, JAX: 3.08 Hz, JBX: 11.12 Hz),
6.92 (dd; 1H; pyrrole H4), 7.02 (d; 1H; pyrrole H3),
7.15 (d; 1H; pyrrole H5), 7.39–7.34 (s; 1H; NH), 7.40
(d; 2H; phenyl H3,H5), 7.67 (d; 2H; phenyl H2,H6),
10.5 (br; 1H; NH); MS (70 eV, EI): 332 (M+ꢀ, 100%),
334 (M+2+ꢀ, 39.74%), 299 (M+–SH, 24.24%), 244
(M+–CSNHC2H5, 27.03%), 180 (M+–C9H8Cl, 73.21%),
93 (M+–C11H11ClN2S, 28.02%), 44 (M+–C14H10ClN3S,
27.34); Analysis calculated for C16H16ClN4S.
4.3.3. 1-N-Allylthiocarbamoyl-3-(4-methylphenyl)-5-(2-
pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 37%; mp
20
D
164 ꢁC (chloroform–methanol); ½aꢂ +30 (c 0.2, CHCl3);
IR (KBr): 3329 (N–H), 1509 (C@N), 1460 (C@C), 1337
1
(C@S); H NMR d (ppm): 2.39 (s; 3H; Ph–CH3), 3.32
(dd; 1H; HA, JAB: 17.44 Hz, JAX: 2.96 Hz), 3.73 (dd;
1H; HB, JAB: 17.44 Hz, JBX: 11.04 Hz), 4.34 (m; 2H;
NH–CH2), 5.25 (dd; 2H; JAX: 17.08 Hz, JBX: 10.24 Hz,
CH@CH2), 5.98 (m; 1H; CH@CH2), 6.38 (dd; 1H; HX,
JAX: 2.96 Hz, JBX: 11.04 Hz), 6.90 (dd; 1H; pyrrole
H4), 7.02 (d; 1H; pyrrole H3), 7.16–7.15 (dd; 1H; pyrrole
4.3.7. 1-N-Allylthiocarbamoyl-3-(4-chlorophenyl)-5-(2-
pyrrolyl)-4,5-dihydro-(1H)-pyrazole. Yield 40%; mp
142–143 ꢁC (chloroform–methanol); ½aꢂ +24 (c 0.2,
20
D
CHCl3); IR (KBr): 3358 (N–H), 2919 (C–H), 1523
1
(C@N), 1411 (C@C), 1342 (C@S); H NMR d (ppm):
3.32 (d; 1H; HA, JAB: 17 Hz, JAX: 3 Hz), 3.75 (dd; 1H;