KOZ’MINYKH et al.
866
b. Compound IIe was also synthesized by reaction
of Ib with N′-isopropylidene-4-nitrobenzohydrazide,
following an analogous procedure.
Methyl [3-hydroxy-2-(4-nitrobenzoyl)-4-oxo-6-
phenyl-1,2,3,4-tetrahydropyridazin-3-yl]acetate
(IIe). Yield 1.77 g (86%) (a), 1.38 g (67%) (b),
mp 153–154°C (decomp., from ethanol). IR spectrum,
ν, cm–1: 3385 (N–H); 3280 (O–H); 1734 (C=O, ester);
1716 (C4=O); 1678, 1656, 1635 (C=O, amide; C=C,
Methyl [2-acetyl-3-hydroxy-6-(4-methylphenyl)-
4-oxo-1,2,3,4-tetrahydropyridazin-3-yl]acetate
(IIa). Yield 0.70 g (44%), mp 149–150°C (decomp.,
from ethanol). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.12 s (3H, 4-CH3C6H4), 2.45 s (3H, COCH3), 3.42 d.d
(2H, 3-CH2, J = 15.8 Hz), 3.72 s (3H, COOCH3),
4.05 s (2H, 5-H, tautomer B), 7.30–7.95 m (4H, C6H4).
Found, %: C 60.54; H 5.89; N 8.61. C16H18N2O5. Cal-
culated, %: C 60.37; H 5.70; N 8.80.
1
C=Carom). H NMR spectrum (CDCl3), δ, ppm: 3.77 s
(3H, COOCH3), 3.82 d.d (2H, 3-CH2, J = 9.8 Hz),
5.62 s (1H, 5-H, tautomer A), 6.11 s (1H, 3-OH), 7.25–
8.08 m (9H, C6H5, C6H4), 8.17 s (1H, 1-H). Found, %:
C 58.70; H 4.32; N 9.88. C20H17N3O7. Calculated, %:
C 58.39; H 4.17; N 10.21.
2-Benzoyl-3-[2-(4-chlorophenyl)-2-oxoethyl]-3-
hydroxy-6-phenyl-2,3-dihydropyridazin-4(1H)-one
(IIf). Yield 1.59 g (71%), mp 162–163°C (decomp.,
Methyl [2-benzoyl-3-hydroxy-6-(4-methylphen-
yl)-4-oxo-1,2,3,4-tetrahydropyridazin-3-yl]acetate
(IIb). Yield 1.50 g (79%), mp 139–140°C (decomp.,
from acetonitrile). 1H NMR spectrum (CDCl3), δ, ppm:
2.31 s (3H, 4-CH3C6H4), 3.65 d.d (2H, 3-CH2, J =
9.2 Hz), 3.71 s (3H, COOCH3), 5.82 s (1H, 5-H,
tautomer A), 7.05–7.89 m (9H, C6H4, C6H5), 7.95 s
(1H, 1-H). Found, %: C 66.20; H 5.48; N 7.22.
C21H20N2O5. Calculated, %: C 66.31; H 5.30; N 7.36.
1
from acetonitrile). H NMR spectrum (DMSO-d6), δ,
ppm: 3.55 d.d (2H, 3-CH2, J = 16.4 Hz), 4.95 s (2H,
5-H, tautomer B, 72%), 7.05 s (1H, 5-H, tautomer A,
28%), 7.55–8.10 m (15H, C6H5, C6H4, 1-H). Found, %:
C 67.06; H 4.45; Cl 7.81; N 6.10. C25H19ClN2O4. Cal-
culated, %: C 67.19; H 4.29; Cl 7.93; N 6.27.
3-[2-(4-Chlorophenyl)-2-oxoethyl]-3-hydroxy-2-
(4-methoxybenzoyl)-6-phenyl-2,3-dihydropyrida-
zin-4(1H)-one (IIg). Yield 2.00 g (85%), mp 180–
Methyl (2-benzoyl-3-hydroxy-4-oxo-6-phenyl-
1,2,3,4-tetrahydropyridazin-3-yl)acetate (IIc). Yield
1.43 g (78%), mp 118–119°C (decomp., from ethanol).
1H NMR spectrum (CDCl3), δ, ppm: 3.63 d.d (2H,
3-CH2, J = 8.5 Hz), 3.73 s (3H, COOCH3), 5.37 s (1H,
5-H, tautomer A), 7.33–8.05 m (10H, C6H5), 8.10 s
(1H, 1-H). Found, %: C 65.32; H 5.18; N 7.49.
C20H18N2O5. Calculated, %: C 65.57; H 4.95; N 7.65.
1
181°C (decomp., from ethanol). H NMR spectrum
(DMSO-d6), δ, ppm: 3.66 d.d (2H, 3-CH2, J =
16.0 Hz), 3.84 s (3H, MeO, tautomer B), 3.85 s (3H,
MeO, tautomer A), 4.72 s (2H, 5-H, tautomer B, 64%),
7.06 s (1H, 5-H, tautomer A, 36%), 7.50–8.10 m (14H,
C6H5, C6H4, 1-H). 13C NMR spectrum (CDCl3), δC,
ppm: 45.9 (C5, tautomer B), 49.1 (3-CH2), 55.2 (CH3O),
Methyl [3-hydroxy-2-(2-hydroxybenzoyl)-4-oxo-
6-phenyl-1,2,3,4-tetrahydropyridazin-3-yl]acetate
(IId). Yield 1.41 g (74%), mp 120–121°C (decomp.,
from chloroform–hexane, 1:1). IR spectrum, ν, cm–1:
3422 (N–H); 1730 (C=O, ester); 1711 (C4=O); 1665,
91.8 (C3), 93.3 (5-H, tautomer A), 113.6–176.7 (Carom
,
C6, 1-C=O), 194.3 and 197.2 (C4, tautomers A and B),
203.2 (4-ClC6H4CO). Found, %: C 65.79; H 4.15;
Cl 7.52; N 6.03. C26H21ClN2O5. Calculated, %:
C 65.48; H 4.44; Cl 7.43; N 5.87.
1
1647, 1620 (C=O, amide; C=C, C=Carom). H NMR
spectrum, δ, ppm: in DMSO-d6: 3.65 m (5H, 3-CH2-
COOCH3), 5.84 s (1H, 5-H, tautomer A), 7.06–8.10 m
(10H, C6H5, C6H4, 1-H), 10.35 br.s (1H, C6H4OH); in
DMSO-d6–CF3COOH (10:1): 3.70 d.d and 4.06 d.d
(1H each, 3-CH2, J = 9.6 Hz), 3.78 s (3H, COOCH3),
5.90 s (1H, 5-H, tautomer A), 7.12–8.17 m (9H, C6H5,
C6H4), 10.65 br.s (1H, HOC6H4). Mass spectrum, m/z
(Irel, %): 382 (3) [M]+, 351 (0.5) [M – CH3O]+, 281
(56) [M – CH3O – CH2CO]+, 263 (3) [M – CH3O –
CH2CO – H2O – H]+, 161 (88) [C6H5C(=NH)
CH2CONH]+, 160 (5) [C6H5C3H3N2O]+, 121 (100)
[HOC6H4C≡O]+, 103 (6) [C6H5C≡N]+, 93 (18)
[HOC6H4]+, 77 (14) [C6H5]+. Found, %: C 62.74;
H 4.85; N 7.46. C20H18N2O6. Calculated, %: C 62.82;
H 4.74; N 7.33. M 382.
3-[2-(4-Chlorophenyl)-2-oxoethyl]-3-hydroxy-2-
(2-hydroxybenzoyl)-6-phenyl-2,3-dihydropyridazin-
4(1H)-one (IIh). Yield 1.46 g (63%), mp 172–173°C
1
(decomp., from ethanol). H NMR spectrum
(DMSO-d6), δ, ppm: 3.54 d.d (2H, 3-CH2, J =
17.2 Hz), 4.91 s (2H, 5-H, tautomer B, 78%), 6.95 s
(1H, 5-H, tautomer A, 22%), 7.25–8.08 m (14H, C6H5,
C6H4, 1-H), 10.30 s (1H, 2-HOC6H4). Found, %:
C 64.70; H 4.28; Cl 7.48; N 5.91. C25H19ClN2O5. Cal-
culated, %: C 64.87; H 4.14; Cl 7.66; N 6.05.
1,2-Dibenzoylhydrazine (IIIa). Yield 0.18 g
(15%), mp 241–242°C (decomp., from toluene). Mass
spectrum, m/z (Irel, %): 240 (23) [M]+, 136 (1)
[C6H5CONHNH2]+, 121 (2) [C6H5CONH2]+, 105 (100)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 6 2007