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MOUSTAFA et al.
exchange with D2O), 7. 29 s (2H, NH2, exchange with
D2O), 7.67 d (2H, J = 8.40 Hz, Ar-H), 7.81 d (2H, J =
8.40 Hz, Ar-H), 10.61 s (1H, NH, exchange with D2O),
12.68 br (1H, NH, exchange with D2O). 13C NMR spec-
trum, δ, ppm: 114.9, 126.5, 127.2, 138.9, 144.7, 149.8,
158.2. Found, %: C 38.18; H 3.62; N 29.85. C9H10N6O3S.
Calculated, %: C 38.29; H 3.57; N 29.77.
Ar-H), 6.91 s (2H, NH2, exchange with D2O), 7.47 d (2H,
J = 8.40 Hz, Ar-H). 13C NMR spectrum, δ, ppm: 9.00,
112.4, 122.6, 123.7, 127.2, 127.4, 130.0, 151.9. Found,
%: C 47.22; H 4.72; N 25.01. C11H13N5O2S. Calculated,
%: C 47.30; H 4.69; N 25.07.
4-[(5-Cyano-2,4-dimethyl-6-oxo-1,6-dihydropyr-
idin-3-yl)diazenyl]benzenesulfonamide (7). A mix-
ture of compound 3b (10 mmol) with cyanacetamide
(10 mmol) in 0.56 g KOH (10 mmol) and 20 mL of abso-
lute ethanol was refluxed for 6 h, then cooled down and
poured into 50 mL of cold water, and acidified with dil.
HCl. The yellow precipitate was filtered off, dried, and
recrystallized from ethanol/acetic acid. Yellow powder,
yield 92%, mp 240–242°C. IR spectrum, ν, cm–1: 3278
(NH2 and NH), 2232 (C≡N), 1656 (C=O, amide), 1583
4-[2-(3-Amino-5-oxo-1-phenyl-1H-pyrazol-4(5H)-
ylidene)hydrazinyl]benzenesulfonamide (4b). Yield
84%, mp 208–210°C. IR spectrum, ν, cm–1: 3357, 3254
(2NH2 and NH), 1687 (C=O, amide), 1593 (C=N), 1252
1
(asym. SO2). H NMR spectrum, δ, ppm: 2.77 s (2H,
NH2, exchange with D2O), 2.79 s (2H, NH2, exchange
with D2O), 7.34 m (2H, Ar-H), 7.60 d (2H, J = 8.40 Hz,
Ar-H), 7.68 m (3H,Ar-H), 7.85 d (2H, J = 8.40 Hz,Ar-H),
12.40 s (1H, NH, exchange with D2O), 12.98 br (1H, NH,
exchange with D2O). 13C NMR spectrum, δ, ppm: 105.7,
106.4, 111.2, 115.5, 116.0, 116.3, 139.7, 140.4, 143.7,
144.7, 160.1, 160.6. Found, %: C 50.36; H 3.90; N 23.39.
C15H14N6O3S. Calculated, %: C 50.27; H 3.94; N 23.45.
1
(N=N), 1262 (asym. SO2). H NMR spectrum, δ, ppm:
2.14, 2.36 2s (6H, 2CH3, pyridine), 5.98 s (2H, NH2, ex-
change with D2O), 7.64 d (2H, J = 8.80 Hz, Ar-H), 7.86
d (2H, J = 8.40 Hz, Ar-H), 8.12 s (1H, NH, exchange
with D2O), 12.32 br (1H, NH, exchange with D2O). 13C
NMR spectrum, δ, ppm: 12.20, 13.42, 110.8, 113.5, 115.8,
127.3, 129.5, 141.5, 134.7, 151.8, 160.8, 169.2. Found,
%: C 50.76; H 3.96; N 21.16. C14H13N5O3S. Calculated,
%: C 50.75; H 3.95; N 21.14.
4-[(3,5-Dimethylisoxazol-4-yl)diazenyl]benzene-
sulfonamide (5). A mixture of compound 1b (10 mmol)
with hydroxylamine hydrochloride (10 mmol) dissolved
in 10 mL of dry pyridine was refluxed for 6 h, cooled
down and poured into 50 mL of cold water to give a
pale orange precipitate, which was filtered off, dried and
recrystallized from ethanol/acetic acid. Pale orange pow-
der, yield 65.5%, mp 198-200°C. IR spectrum, ν, cm–1:
Ethyl-2-cyano-2-[2-(1,5-dimethyl-3-oxo-2-phe-
nyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono]acetate
(10a). Yellow orange powder, yield 89%, mp 173–175°C.
IR spectrum, ν, cm–1: 3160 (NH), 22201 (C≡N), 1740
(C=O, ester), 1666 (C=O, amide). 1H NMR spectrum, δ,
ppm: 1.27 t (3H, J = 7.20 Hz, CH3CH2), 2.40 s (3H, CH3,
phenazone), 3.32 s (3H, NCH3, phenazone), 4.28 q (2H,
J = 6.80 Hz, CH2CH3), 7.36–7.53 m (5H, Ar-H), 11.31
br (1H, NH, exchange with D2O). 13C NMR spectrum,
δ, ppm: 10.74 (CH3CH2), 14.11, 35.46, 61.27, 103.5,
115.8, 124.3, 126.9, 129.1, 134.0, 145.1, 149.7, 158.3,
161.4. Found, %: C 58.83; H 5.21; N 21.34. C16H17N5O3.
Calculated, %: C 58.71; H 5.23; N 21.39.
1
3380 (NH2), 1589 (N=N), 1267 (asym. SO2). H NMR
spectrum, δ, ppm: 2.30 s (3H, CH3), 2.57 s (3H, CH3),
7.30 s (2H, NH2, exchange with D2O), 7.69 d (2H, J =
8.40 Hz, Ar-H), 7.85 d (2H, J = 8.40 Hz, Ar-H). Found,
%: C 47.04; H 4.30; N 20.05. C11H12N4O3S. Calculated,
%: C 47.13; H 4.32; N 19.99.
4-{2-[3,5-Dimethyl-4H-pyrazol-4(5H)-ylidene]-
hydrazinyl}benzenesulfonamide (6). To a solution of
compound 3b (10 mmol) in 15 mL of absolute etha-
nol and 5 mL of acetic acid, hydrazine hydrate (99%)
(10 mmol) was added. The reaction mixture was refluxed
for 6 h, then cooled to room temperature to give orange
precipitate, which was filtered off, dried and recrystal-
lized from ethanol–acetic acid (1 : 1). Orange powder,
yield 78.5%, mp 203–205°C. IR spectrum, ν, cm–1: 3348
(NH2), 3225 (NH), 1598 (C=N), 1258 (asym. SO2). 1H
NMR spectrum, δ, ppm: 2.00 s (6H, 2CH3, sym.), 5.80 s
(2H, NH2, exchange with D2O), 6.61 d (2H, J = 8.80 Hz,
3-[2-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-di-
hydro-1H-pyrazol-4-yl)hydrazono]pentane-2,4-dione
(10b). Yellow orange powder, yield 85%, mp 193–195°C.
IR spectrum, ν, cm–1: 3444 (NH), 1660 br. s (3C=O,
1
conjugated and amide). H NMR spectrum, δ, ppm:
2.36 s (3H, CH3, phenazone), 2.54 s (6H, 2CH3), 3.13 s
(3H, NCH3, phenazone), 7.36–7.55 m (5H, Ar-H), 11.20
br (1H, NH, exchange with D2O). 13C NMR spectrum,
δ, ppm: 11.33, 30.20, 35.59, 124.2, 127.1, 129.2, 133.5,
134.1, 143.9, 158.9, 172.6, 194.9. Found, %: C 61.05; H
5.79; N 17.87. C16H18N4O3. Calculated, %: C 61.13; H
5.77; N 17.82.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019