842
Vol. 61, No. 8
1H-NMR (CDCl3) δ: 2.06 (3H, s, CH3), 2.16–2.22 (1H, m, CH), thionyl chloride were removed. The residue was then refluxed
2.68–2.72 (1H, m, CH), 2.88–2.92 (1H, m, CH), 7.68–8.06 in sodium methoxide (10mL) for 3h. The reaction mixture
(6H, m, Ar-H+ex, NH2). IR (KBr) cm−1: 3421, 3201 (NH2), poured onto ice water, then extracted with chloroform. The
3066, 3047 (CH aromatic), 2924, 2845 (CH aliphatic), 2260 extract was washed with water, dried over anhydrous Na2SO4,
(CN), 1705 (C=O), 1338, 1161 (SO2). MS m/z: 294 (M++2). and concentrated under vaccum, dried and crystallized from
Anal. Calcd for C12H12N4O3S (292.31): C, 49.31; H, 4.14; N, ethanol.
19.17. Found: C, 49.29; H, 4.31; N, 19.43.
Methyl 2-(1-(4-Chlorophenyl)-3-methyl-5-oxo-4,5-dihydro-
4-(4-(Cyanomethyl)-5-oxo-3-phenyl-4,5-dihydro-1H- 1H-pyrazol-4-yl)acetate (7a): Yield 40%. mp 115–116°C
1
pyrazol-yl)benzenesulfonamide (5d): Yield 61% as oil. (decompose). H-NMR (CDCl3) δ: 1.84 (3H, s, CH3), 2.38–
1H-NMR (CDCl3) δ: 2.23–2.29 (1H, m, CH), 2.52–2.57 (1H, 2.52 (1H, m, CH), 2.67–2.72 (1H, m, CH), 3.10–3.16 (1H,
m, CH), 2.90–2.93 (1H, m, CH), 7.35–8.00 (11H, m, Ar-H+ m, CH), 3.88 (3H, s, OCH3), 7.42–7.79 (4H, m, Ar-H). IR
ex, NH2). IR (KBr) cm−1: 3050 (CH aromatic), 2900, 2850 (CH (KBr) cm−1: 2924, 2850 (CH aliphatic), 1770, 1631 (2C=O).
aliphatic), 2260 (CN), 1707 (C=O), 1371, 1159 (SO2). MS m/z: MS m/z: 282 (M++2), 280 (M+). Anal. Calcd for C13H13ClN2O3
356 (M++2). Anal. Calcd for C17H14N4O3S (354.38): C, 57.62; (280.70): C, 55.62; H, 4.67; N, 9.98. Found: C, 55.67; H, 4.72;
H, 3.98; N, 15.81. Found: C, 57.71; H, 4.07; N, 16.12.
General Procedure for the Synthesis of Compounds 6a–d
N, 10.13.
Methyl 2-(1-(4-Chlorophenyl)-5-oxo-3-phenyl-4,5-dihydro-
A solution of 5a–d (10mmol) in 65% sulfuric acid (40mL) 1H-pyrazol-4-yl)acetate (7b): Yield 45%. mp above 350°C.
was refluxed 3h and poured into ice water. The solid was fil- 1H-NMR (CDCl3) δ: 2.05–2.08 (1H, m, CH), 2.86–2.88 (1H,
tered, washed with water, dried and crystallized from ethanol. m, CH), 2.94–2.96 (1H, m, CH), 3.71 (3H, s, OCH3), 7.44–
2-(1-(4-Chlorophenyl)-3-methyl-5-oxo-4,5-dihydro-1H- 8.04 (9H, m, Ar-H). IR (KBr) cm−1: 3059 (CH aromatic), 2924,
pyrazol-4-yl)acetic Acid (6a): Yield 47%. mp 168–170°C. 2854 (CH aliphatic), 1774, 1716 (2C=O). MS m/z: 343
1H-NMR (DMSO-d6) δ: 2.18–2.34 (4H, m, CH3+CH), (M++1), 341 (M−1). Anal. Calcd for C18H15ClN2O3 (342.77): C,
2.72–2.77 (1H, m, CH), 2.90–2.95 (1H, m, CH), 7.48–7.65 (4H, 63.07; H, 4.41; N, 8.17. Found: C, 63.16; H, 4.47; N, 8.31.
m, Ar-H), 7.27 (1H, s, ex, OH). IR (KBr) cm−1: 3406–2503
Methyl 2-(3-Methyl-5-oxo-1-(4-sulfamoylphenyl)-4,5-dihy-
(OH carboxylic), 2924, 2850 (CH aliphatic), 1716 (C=O). MS dro-1H-pyrazol-4-yl)acetate (7c): Yield 70%. mp 222–
1
m/z: 268 (M++2), 266 (M+). Anal. Calcd for C12H11ClN2O3 223°C. H-NMR (DMSO-d6) δ: 2.14 (3H, s, CH3), 2.05–2.11
(266.68): C, 54.05; H, 4.16; N, 10.50. Found: C, 54.12; H, 4.19; (1H, m, CH), 2.40–2.43 (1H, m, CH), 2.65–2.70 (1H, m, CH),
N, 10.77.
3.16 (3H, s, OCH3), 7.32–8.08 (6H, m, Ar-H+ex, NH2). IR
2-(1-(4-Chlorophenyl)-5-oxo-3-phenyl-4,5-dihydro-1H- (KBr) cm−1: 3344, 3251 (NH2), 3105, 3078 (CH aromatic),
pyrazol-4-yl)acetic Acid (6b): Yield 71%. mp 220–223°C. 2924, 2854 (CH aliphatic), 1724, 1620 (2C=O), 1327, 1157
1H-NMR (DMSO-d6) δ: 2.72–2.77 (1H, m, CH), 2.85–2.88 (SO2). MS m/z: 327 (M++2). Anal. Calcd for C13H15N3O5S
(1H, m, CH), 3.29–3.33 (1H, m, CH), 7.41–7.99 (10H, m, (325.34): C, 47.99; H, 4.65; N, 12.92. Found: C, 48.13; H, 4.42;
Ar-H+ex, OH). IR (KBr) cm−1: 3402–2495 (OH carboxylic), N, 13.16.
2927 (CH aliphatic), 1716 (C=O). MS m/z: 330 (M++2), 328
Methyl 2-(5-Oxo-3-phenyl-1-(4-sulfamoylphenyl)-4,5-dihy-
(M+). Anal. Calcd for C17H13ClN2O3 (328.74): C, 62.11; H, 3.99; dro-1H-pyrazol-4-yl)acetate (7d): Yield 67%. mp 229–230°C.
N, 8.52. Found: C, 62.19; H, 4.04; N, 8.68.
1H-NMR (DMSO-d6) δ: 2.22–2.44 (2H, m, CH2), 2.65–2.70
2-(3-Methyl-5-oxo-1-(4-sulfamoylphenyl)-4,5-dihydro-1H- (1H, m, CH), 3.16 (3H, s, OCH3), 7.29–8.20 (11H, m, Ar-H+
pyrazol-4-yl)acetic Acid (6c): Yield 65%. mp above 350°C. ex, NH2). IR (KBr) cm−1: 3363, 3259 (NH2), 3105, 3066
1H-NMR (DMSO-d6) δ: 2.04 – 2.30 (6H, m, CH3+CH2+CH), (CH aromatic), 2924, 2854 (CH aliphatic), 1728, 1620 (2C=
7.30–7.87 (6H, m, Ar-H+ex, NH2), 8.08 (1H, s, ex, OH). IR O), 1330, 1161 (SO2). MS m/z: 387 (M+). Anal. Calcd for
(KBr) cm−1: 3298–2669 (OH carboxylic), 3298, 3240 (NH2), C18H17N3O5S (387.40): C, 55.80; H, 4.42; N, 10.85. Found: C,
3101 (CH aromatic), 2920, 2850 (CH aliphatic), 1720 (C= 56.24; H, 4.63; N, 11.22.
O), 1330, 1157 (SO2). MS m/z: 312 (M++1); Anal. Calcd for
General Procedure for the Synthesis of Compounds 8a–d
C12H13N3O5S (311.31): C, 46.30; H, 4.21; N, 13.50. Found: C, To a suspension of 2a–d (6mmol) in isopropanol (12mL),
46.71; H, 4.42; N, 13.69. N,N-dimethylformamide diethylacetal (2.87mL, 19.50mmol)
2-(5-Oxo-3-phenyl-1-(4-sulfamoylphenyl)-4,5-dihydro-1H- was added and stirred for 2h at room temperature. An ad-
pyrazol-4-yl)acetic Acid (6d): Yield 69%. mp 235–236°C. ditional amount of N,N-dimethylformamide diethylacetal
1H-NMR (DMSO-d6) δ: 2.05–2.31 (3H, m, CH2+CH), 7.32 (0.95mL, 6.50mmol) was further added and the reaction mix-
(2H, s, ex, NH2), 7.42–8.06 (9H, m, Ar-H), 8.08 (1H, s, ex, ture was stirred at room temperature for another 20h. The
OH). IR (KBr) cm−1: 3352–2550 (OH carboxylic), 3352, 3251 formed precipitate was filtered off, washed with isopropanol,
(NH2), 3066 (CH aromatic), 2920, 2850 (CH aliphatic), 1720 dried and recrystallized from isopropanol.
(C=O), 1330, 1161 (SO2). MS m/z: 373 (M+). Anal. Calcd for
C17H15N3O5S (373.38): C, 54.68; H, 4.05; N, 11.25. Found: C, methyl-1H-pyrazol-5(4H)-one (8a): Yield 77%. mp 203–204°C.
54.97; H, 4.18; N, 11.38.
1H-NMR (CDCl3) δ: 2.14 (3H, s, CH3), 3.21 (3H, s, N(CH3)),
1-(4-Chlorophenyl)-4-((dimethylamino)methylene)-3-
General Procedure for the Synthesis of Compounds 7a–d 3.78 (3H, s, N(CH3)), 6.95 (1H, s, CHN(CH3)2), 7.28 (2H, d,
A suspension of 6a–d (5mmol) in thionyl chloride (5mL) was Ar-H, J=8.7Hz), 7.98 (2H, d, Ar-H, J=9.0Hz). 13C-NMR
heated gently under reflux until a homogenous solution was (CDCl3) δ: 13.7, 43.3, 48.0, 99.2, 120.1, 128.4, 128.6, 138.2,
obtained then for further 45min. The solution was then evapo- 152.2, 162.0. IR (KBr) cm−1: 3032 (CH aromatic), 2920 (CH
rated to dryness under vacuum in a water bath to remove aliphatic), 1674 (C=O). MS m/z: 265 (M++2), 263 (M+). Anal.
excess thionyl chloride. The residue was azeotroped three Calcd for C13H14ClN3O (263.72): C, 59.21; H, 5.35; N, 15.93.
times with dry benzene (5mL) each, where the last traces of Found: C, 59.36; H, 5.48; N, 16.26.