JOURNAL OF CHEMICAL RESEARCH 2008 729
1360, 990 (C=S and C-N). MS: m/z (%) = 395 [M+] (28), 364 (19),
336 (38), 201 (46), 150 (39), 135 (64), 133 (72), 93 (100), 77 (76).
C2oH17N304S(395.43): Calcd C, 60.75; H, 4.33; N, 10.63; S, 8.11.
Found C, 60.94; H, 4.22; N, 10.82; S, 8.26%.
(34),269 [M+-PhNCS] (57),224 (41), 180 (21), 154 (19), 150 (56),
135 (94),103 (79),91 (100),77 (74), 65 (63). C21HI~403S (404.44):
Ca1cd C, 62.36; H, 3.99; N, 13.85; S, 7.93. Found C, 62.18; H, 4.12;
N, 14.06; S, 8.11%.
Methyl [3-(4-chlorophenyl)-4-oxo-I-(phenylthiocarbamoyl)-4, 5-
Ethyl [3-(4-methoxyphenyl)-4-oxo-I-(phenylthiocarbamoyl)-4, 5-
dihydro-IH-pyrazol-5-ylidene}ethanoate
(10e): Pale yellow crystals
dihydro-IH-pyrazol-5-ylidene}cyanoacetate
(15b): Brown crystals
(0.58 g, 73%), m.p. 302-304°C (acetonitrile). IH NMR: 15= 9.90
(hr, lH, Ph-NH), 7.16-7.77 (m, 9H, aryl H), 6.69 (s, lH, methylene
H), 3.78 (s, 3H, COOCH3). IR (KEr): v (em-I) = 3275 (NH), 1710
(CO), 1685 (COO), 1620 (C=N), 1560 (NH def. and C-N str.), 1360,
1005 (C=S and C-N). MS: m/z (%) = 401/399 [M+] (56), 363 (36),
332 (44), 304 (44),169 (54),150 (61),138 (64),135 (69), 91 (62),77
(100),65 (81). CI~14ClN303S (399.85): Ca1cdC, 57.07; H, 3.53; C1,
8.87; N, 10.51; S, 8.02. Found C, 56.88; H, 3.44; CI, 9.06; N, 10.73;
S,7.84%.
(0.265 g, 61%), m.p. 316-318°C (methanol). IH NMR: 15= 9.9 (hr,
lH, Ph-NH), 7.09-7.74 (m, 9H, aryl H), 4.22 (q, 2H, OCH2,J= 7.08
Hz), 3.84 (s, 3H, OCH3), 1.21 (t, 3H, CH3, J = 7.08 Hz). 13CNMR: 15
= 190.76 (C-4), 178.84 (C=S), 170.84 (C-5), 166.51 (COO), 160.63
(pheny14-MeO-C), 155.89 (C-3), 138.76, 137.96 (aryl qC); 129.54,
128.66, 127.66, 127.24, 126.63 (aryl CH); 118.06 (CN), 103.14
(methylene qC), 60.94 (OCH2), 55.10 (OCH3), 14.29 (OCH2CH3).
IR (KEr): v (cm-I) = 3280 (NH), 2220 (CN), 1715 (CO), 1675 (COO),
1630 (C=N), 1570 (NH-def. and C-N str.), and 1360,990 (C=S and
C-N). MS: m/z (%): 434 [W] (26),299 (41), 268 (26),223 (46), 179
(52), 152 (36), 150 (64), 135 (71), 133 (58), 91 (88), 77 (100), 65
(69). C22HISN404S(434.47): Ca1cd C, 60.82; H, 4.18; N, 12.90; S,
7.38. Found C, 61.04; H, 4.09; N, 13.14; S, 7.59%.
Methyl
[3-(2-hydroxyphenyl)-4-oxo-I-(phenylthiocarbamoyl)-
(10d): Yellow crystals
4,5-dihydro-IH-pyrazol-5-ylidene}ethanoate
(0.57 g, 75%), m.p. 278-279°C (acetonitrile). IH NMR: 15= 9.94
(hr, lH, Ph-NH), 9.58 (hr, lH, OH), 7.08-7.73 (m, 9H, aryl H), 6.72
(hr, lH, methylene H), 3.75 (s, 3H, COOCH3). IR (KEr): v (em-I) =
3465 (OH), 3285 (NH), 1720 (CO), 1680 (COO), 1620 (C=N), 1570
(NH def. and C-N str.), 1355, 995 (C=S and C-N). MS: m/z (%) =
381 [M+] (56),350 (34), 332 (25), 197 (39), 150 (53), 135 (66), 129
(45), 93 (100), 77 (86), 65 (79). CI9HISN304S (381.41): Ca1cd C,
59.83; H, 3.96; N, 11.02; S, 8.41. Found C, 60.09; H, 4.05; N, 10.84;
S,8.63%.
Methyl [3-(2-thienyl)-4-oxo-I-(phenylthiocarbamoyl)-4, 5-dihydro-
IH-pyrazol-5-ylidene}ethanoate (10e): Pale yellow crystals (0.56 g,
76%), m.p. 263-264°C (acetonitrile). IH NMR: 15= 9.88 (hr, lH,
Ph-NH), 7.17-7.73 (m, 8H, phenyl and thieny1 H), 6.70 (s, lH,
methylene H), 3.76 (s, 3H, COOCH3). 13CNMR: 15= 191.75 (C-4),
178.65 (C=S), 167.12 (COO), 163.65 (C-5), 155.26 (C-3); 138.59,
133.26 (aryl qC), 129.18, 128.41, 127.43, 127.28, 126.64, 126.26
(phenyl and thieny1 CH), 116.83 (methylene CH), 52.04 (COOCH3).
IR (KEr): v (em-I) = 3285 (NH), 1715 (CO), 1685 (COO), 1625
(C=N), 1565 (NH def. and C-N str.), 1360, 1000 (C=S and C-N).
MS: m/z (%) = 371 [W] (53),340 (27), 312 (44),177 (56), 150 (52),
135 (71), 109 (65), 77 (100), 65 (53). C17H13N303S2(371.43): Calcd
C, 54.97; H, 3.53; N, 11.31, S, 17.27. Found C, 55.16; H, 3.43; N,
11.16; S, 17.45%.
Methyl [3-(2-furyl)-4-oxo-I-(phenylthiocarbamoyl)-4,5-dihydro-
IH-pyrazol-5-ylidene}ethanoate (lOt): Pale yellow crystals (0.52 g,
73%), m.p. 237-238 °c (acetonitrile). IH NMR: 15= 9.83 (hr, lH, Ph-
NH), 6.98-7.64 (m, 8H, phenyl and fury1H), 6.70 (s, lH, methylene
H), 3.78 (s, 3H, COOCH3). 13CNMR: 15= 191.65 (C-4), 178.83
(C=S), 167.10 (COO), 163.58 (C-5), 155.18 (C-3), 143.86 (fury1 C-
2), 141.65 (fury1 C-5), 138.62 (phenyl qC); 129.36, 128.51, 126.64,
125.94, 125.76 (phenyl and fury1 CH); 116.82 (methylene CH),
51.79 (COOCH3). IR (KEr): v (em-I) = 3275 (NH), 1720 (CO), 1680
(COO), 1620 (C=N), 1570 (NH def. and C-N str.), 1360,995 (C=S
and C-N). MS: m/z (%) = 355 [M+] (31),324 (19), 296 (43), 161
(55), 150 (48), 135 (59), 93 (86), 77 (100), 65 (53). C17H13N304S
(355.37): Calcd C, 57.46; H, 3.69; N, 11.82, S, 9.02. Found C, 57.67;
H, 3.58; N, 12.06; S, 8.89%.
Reactions of 1a-f with diethyl (E)-2,3-dicyanobutenedioate (7):
A solution of 222 mg (1.0 mmo1) of 7 in 20 m1 ethyl acetate was
treated with 1.0 mmo1 of 1a-f (in 20 m1of ethyl acetate). The mixture
was refluxed for 14-18 hours with stirring (the reaction was monitored
by TLC). The reaction time of 1a-f with 7 was as follows for 1a
(15 h), 1b, e (14 h), 1d (16 h), Ie (17 h) and If (18 h). After
concentration of the reaction mixture to dryness, the residues were
dissolved in 5 m1 of acetone and subjected to PLC using to1uene/
ethyl acetate (4:1) as eluent. Chromatographic separation of the
residue gave numerous zones, two of which (with high intensity)
were removed and extracted. The fastest moving zone contained
compounds 24a-f, while the slowest moving zone contained the
pyrazo10ne derivatives 15a-f. Extraction of the zones with acetone
and crystallisation gave the pure compounds.
Ethyl
[3-(4-chlorophenyl)-4-oxo-I-(phenylthiocarbamoyl)-4, 5-
dihydro-IH-pyrazol-5-ylidene}cyanoacetate
(15e): Pale brown
crystals (0.228 g, 56%), m.p. 326-328°C (acetonitrile). IH NMR: 15=
9.90 (hr, lH, Ph-NH), 7.24-7.77 (m, 9H, aryl H), 4.22 (q, 2H, OCH2,
J = 7.05 Hz), 1.19 (t, 3H, CH3, J = 7.05 Hz). 13CNMR: 15= 190.86
(C-4), 178.56 (C=S), 171.05 (C-5), 165.96 (COO), 155.87 (C-3);
138.56, 136.64, 131.28 (aryl qC); 130.26, 129.22, 128.96, 128.28,
127.44 (aryl CH); 117.98 (CN), 103.11 (methylene qC), 60.96
(OCH2), 14.23 (OCH2CH3). IR (KEr): v (cm-I) = 3270 (NH), 2220
(CN), 1710 (CO), 1675 (COO), 1625 (C=N), 1570 (NH-def. and C-
N str.), and 1360, 995 (C=S and C-N). MS. m/z (%) = 440/438 [M+]
(54),402 (29), 267 (44), 222 (56), 178 (18), 152 (37), 150 (64), 139
(74), 135 (56),91 (100),77 (74), 65 (66). C21HISClN403S(438.89):
Ca1cd C, 57.47; H, 3.44; C1, 8.08; N, 12.77; S, 7.31. Found C, 57.29;
H, 3.58; C1, 7.92; N, 12.56; S, 7.54%.
Ethyl [3-(2-hydroxyphenyl)-4-oxo-I-(phenylthiocarbamoyl)-4,5-
dihydro-IH-pyrazol-5-ylidene}cyanoacetate
(15d): Brown crystals
(0.235 g, 56%), m.p. 308-309°C (methanol). IH NMR: 15= 9.92 (hr,
lH, Ph-NH), 9.54 (hr, lH, OH), 7.98-7.68 (m, 9H, aryl H), 4.19 (q,
2H, OCH2, J = 7.03 Hz), 1.24 (t, 3H, CH3, J = 7.03 Hz). 13CNMR:
15= 190.94 (C-4), 178.65 (C=S), 170.72 (C-5), 165.96 (COO),
161.16 (aryl C-OH), 156.09 (C-3); 138.76, 134.83 (aryl qC); 130.11,
129.76, 129.12, 128.46, 127.55, 127.12, 126.56 (aryl CH); 118.12
(CN), 102.96 (methylene qC), 61.11 (OCH2), 14.26 (OCH2CH3).
IR (KEr): v (cm-I) = 3465 (OH), 3260 (NH), 2215 (CN), 1715 (CO),
1680 (COO), 1620 (C=N), 1566 (NH-def. and C-N str.), and 1355,
980 (C=S and C-N). MS: m/z (%) = 420 [M+] (42), 285 (39), 240
(28), 196(34), 170 (18), 150 (49), 135 (66), 119 (74), 93 (100), 77
(86), 65 (44). C21HI~404S (420.44): Calcd C, 59.99; H, 3.84; N,
13.33; S, 7.63. Found C, 60.16; H, 3.71; N, 13.12; S, 7.81%.
Ethyl [3-(2-thienyl)-4-oxo-I-(phenylthiocarbamoyl)-4,5-dihydro-
IH-pyrazol-5-yli-dene}cyanoacetate (15e): Yellowish brown crystals
(0.234 g, 57%), m.p. 299-301°C (ethanol). IH NMR: 15= 9.89 (hr,
lH, Ph-NH), 7.14-7.72 (m, 8H, phenyl and thieny1 H), 4.23 (q,
2H, OCH2,J= 7.10 Hz), 1.21 (t, 3H, CH3,J= 7.10 Hz).13C NMR:
15= 190.82 (C-4), 178.61 (C=S), 170.64 (C-5), 165.83 (COO), 155.76
(C-3), 138.57 (phenyl qC), 136.14 (thieny1 C-2); 129.22, 128.41,
127.74, 127.36, 126.55, 126.38 (phenyl and thieny1 CH); 118.16
(CN), 103.18 (methylene qC), 61.08 (OCH2), 14.25 (OCH2CH3). IR
(KEr): v (cm-I) = 3280 (NH), 2220 (CN), 1705 (CO), 1675 (COO),
1620 (C=N), 1560 (NH-def. and C-N str.), and 1355, 990 (C=S and
C-N). MS. m/z (%) = 410 [W] (61),275 (48), 230 (52), 186 (39),
160 (17), 150 (33), 135 (67), 109 (81), 91 (86), 77 (100), 65 (74).
C19HI~403S2 (410.47): Ca1cd C, 55.60; H, 3.44; N, 13.65; S, 15.62.
Found C, 55.42; H, 3.58; N, 13.86; S, 15.40%.
Ethyl [3-(2-furyl)-4-oxo-I-(phenylthiocarbamoyl)-4,5-dihydro-IH-
pyrazol-5-ylidene}cyanoacetate (1St): Pale brown crystals (0.213 g,
54%), m.p. 278-279°C (ethanol). IH NMR: 15= 9.90 (hr, lH,
Ph-NH), 7.04-7.66 (m, 8H, aryl and fury1-H), 4.22 (q, 2H, OCH2,
J=7.05Hz), 1.18 (t, 3H,CH3,J=7.05 Hz). 13CNMR: 15=190.92 (C-4),
178.56 (C=S), 170.93 (C-5), 165.88 (COO), 155.54 (C-3), 143.22
(fury1 C-2), 141.72 (fury1 CH-5), 138.67 (aryl qC); 129.29, 128.67,
128.44, 126.14, 125.97 (phenyl and fury1 CH), 117.89 (CN), 102.92
(methylene qC), 60.93 (OCH2), 14.19 (CH3).IR (KEr): v (cm-I) = 3265
(NH), 2215 (CN), 1710 (CO), 1680 (COO), 1625 (C=N), 1565
(NH-def. and C-N str.), and 1360,995 (C=S and C-N). MS: m/z (%)
= 394 [W] (35),259 (27), 214 (56), 170 (61), 150 (48), 144 (19),
135 (76), 93 (66),77 (100), 65 (64). CI9HI4N404S (394.07): Ca1cd C,
57.86; H, 3.58; N, 14.21; S, 8.13. Found C, 58.11; H, 3.69; N, 13.98;
S,18.36%.
Ethyl [3-phenyl-4-oxo-I-(phenylthiocarbamoyl)-4,5-dihydro-IH-
pyrazol-5-ylidene}-cyanoacetate
(15a): Yellowish brown crystals
(0.234 g, 58%), m.p. 287-289°C (acetonitrile). IH NMR: 15= 9.94
(hr, lH, Ph-NH), 7.26-7.86 (m, lOH, phenyl H), 4.21 (q, 2H, OCH2,
J = 7.05 Hz), 1.18 (t, 3H, CH3, J = 7.05 Hz). 13CNMR: 15= 191.28
(C-4), 179.19 (C=S), 170.16 (C-5), 166.33 (COO), 156.17 (C-3);
138.64, 133.29 (phenyl qC); 130.76, 129.54, 129.14, 128.80, 128.44,
127.16 (phenyl CH); 117.96 (CN), 103.22 (methylene qC), 61.02
(OCH2), 14.36 (OCH2CH3). IR (KEr): v (cm-I) = 3275 (NH), 2220
(CN), 1720 (CO), 1680 (COO), 1625 (C=N), 1565 (NH-def. and
C-N str.), and 1365, 985 (C=S and C-N). MS: m/z (%): 404 [M+]