SYNTHESIS AND BIOLOGICAL ACTIVITY OF PYRAZOLO[1,5-c][1,3]BENZOXAZINES
593
7.89 m (1H, Harom, CH=), 12.67 br.s (1H, NH).
Found, %: C 69.19; H 4.50; N 8.81. C27H21N3O3S.
Calculated, %: C 69.36; H 4.53; N 8.99.
(1H, CH2, J = 16.4, 9.5 Hz), 5.44 d (1H, 10b-H, J =
9.1 Hz), 6.34 s (1H, 5-H), 6.87 d (1H, Harom, J =
8.1 Hz), 7.03 t (1H, Harom, J = 7.4 Hz), 7.17 t (1H,
Harom, J = 7.8 Hz), 7.28 d (1H, Harom, J = 7.5 Hz),
7.30–7.36 m (3H, Harom), 7.50–7.54 m (2H, Harom),
7.76 d (2H, Harom, J = 8.2 Hz), 7.87–7.91 m (3H,
Harom, CH=). Found, %: C 67.14; H 4.30; N 8.81.
C27H21N3O2S2. Calculated, %: C 67.06; H 4.38;
N 8.69.
5-{4-[2-(3-Methoxyphenyl)-1,10b-dihydropyra-
zolo[1,5-c][1,3]benzoxazin-5-yl]benzylidene}-1,3-
thiazolidine-2,4-dione (6c). Yield 0.42 g (87%),
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mp 222–223°C. H NMR spectrum, δ, ppm: 3.31–
3.35 m (1H, CH2), 3.52–3.55 m (1H, CH2), 3.71 s
(1.38H, OCH3), 3.78 s (1.62H, OCH3), 4.80 d (0.54H,
10b-H, J = 9.5 Hz), 5.43 d (0.46H, 10b-H, J = 9.0 Hz),
6.32 s (0.46H, 5-H), 6.82–7.36 m (8.54H, Harom, 5-H),
7.61 d (1H, Harom, J = 8.4 Hz), 7.68 d (1H, Harom, J =
8.4 Hz), 7.71 d (1H, Harom, J = 8.4 Hz), 7.76 s (0.54H,
CH=), 7.85–7.87 m (1.46H, Harom, CH=), 12.67 br.s
(1H, NH). Found, %: C 67.15; H 4.47; N 8.48.
C27H21N3O4S. Calculated, %: C 67.07; H 4.38; N 8.69.
3-Methyl-5-{4-[2-(4-methylphenyl)-1,10b-dihy-
dropyrazolo[1,5-c][1,3]benzoxazin-5-yl]benzyli-
dene}-2-sulfanylidene-1,3-thiazolidin-4-one (7b).
1
Yield 0.48 g (96%), mp 232–234°C. H NMR spec-
trum, δ, ppm: 2.25 s (3H, CH3), 3.31 d (1H, CH2, J =
16.7 Hz), 3.42 s (3H, NCH3), 3.50 d.d (1H, CH2, J =
16.7, 9.2 Hz), 5.41 d (1H, 10b-H, J = 9.2 Hz), 6.33 s
(1H, 5-H), 6.87 d (1H, Harom, J = 8.2 Hz), 7.02 t (1H,
Harom, J = 7.8 Hz), 7.10–7.20 m (3H, Harom), 7.27 d
(1H, Harom, J = 7.6 Hz), 7.40 d (2H, Harom, J = 8.1 Hz),
7.76 d (2H, Harom, J = 8.4 Hz), 7.84–7.92 m (3H,
Harom, CH=). Found, %: C 67.38; H 4.61; N 8.32.
C28H23N3O2S2. Calculated, %: C 67.58; H 4.66;
N 8.44.
5-{4-[2-(4-Methoxyphenyl)-1,10b-dihydropyra-
zolo[1,5-c][1,3]benzoxazin-5-yl]benzylidene}-1,3-
thiazolidine-2,4-dione (6d). Yield 0.40 g (83%),
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mp 216–217°C. H NMR spectrum, δ, ppm: 3.31–
3.34 m (1H, CH2), 3.43–3.57 m (1H, CH2), 3.72 s
(1.2H, OCH3), 3.77 s (1.8H, OCH3), 4.76 d (0.6H,
10b-H, J = 9.2 Hz), 5.39 d (0.4H, 10b-H, J = 9.1 Hz),
6.30 s (0.4H, 5-H), 6.83–6.98 m (4H, Harom, 5-H),
6.99–7.06 m (1H, Harom), 7.11–7.19 m (1H, Harom),
7.26 d (0.6H, Harom, J = 7.4 Hz), 7.45 d (1H, Harom, J =
8.9 Hz), 7.58–7.73 m (4H, Harom), 7.76 s (0.6H, CH=),
7.83–7.88 m (1.4H, Harom, CH=), 12.67 br.s (1H, NH).
Found, %: C 66.92; H 4.24; N 8.67. C27H21N3O4S.
Calculated, %: C 67.07; H 4.38; N 8.69.
5-{4-[2-(3-Methoxyphenyl)-1,10b-dihydropyra-
zolo[1,5-c][1,3]benzoxazin-5-yl]benzylidene}-3-
methyl-2-sulfanylidene-1,3-thiazolidin-4-one (7c).
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Yield 0.46 g (89%), mp 201–203°C. H NMR spec-
trum, δ, ppm: 3.32–3.35 m (1H, CH2), 3.39 s (1H,
NCH3), 3.42 s (2H, NCH3), 3.47–3.60 m (1H, CH2),
3.71 s (2H, OCH3), 3.78 s (1H, OCH3), 4.79 d (0.33H,
10b-H, J = 9.2 Hz), 5.43 d (0.67H, 10b-H, J = 9.2 Hz),
6.34 s (0.67H, 5-H), 6.84–7.37 m (7.33H, Harom, 5-H),
7.65–7.72 m (1H, Harom), 7.75–7.81 m (2H, Harom),
7.85–7.91 m (3H, Harom, CH=). Found, %: C 65.27;
H 4.41; N 8.09. C28H23N3O3S2. Calculated, %:
C 65.48; H 4.51; N 8.18.
5-{4-[2-(4-Chlorophenyl)-1,10b-dihydropyra-
zolo[1,5-c][1,3]benzoxazin-5-yl]benzylidene}-1,3-
thiazolidine-2,4-dione (6e). Yield 0.44 g (90%),
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mp 223–224°C. H NMR spectrum, δ, ppm: 3.31–
3.36 m (1H, CH2), 3.50–3.61 m (1H, CH2), 4.82 d
(0.6H, 10b-H, J = 9.4 Hz), 5.46 d (0.4H, 10b-H, J =
5-{4-[2-(4-Methoxyphenyl)-1,10b-dihydropyra-
zolo[1,5-c][1,3]benzoxazin-5-yl]benzylidene}-3-
methyl-2-sulfanylidene-1,3-thiazolidin-4-one (7d).
9.2 Hz), 6.34 s (0.4H, 5-H), 6.85–6.97 m (2.4H, Harom
,
5-H), 7.01–7.05 m (1H, Harom), 7.12–7.20 m (1H,
Harom), 7.27 d (0.4H, Harom, J = 7.6 Hz), 7.39 d (0.8H,
Harom, J = 8.5 Hz), 7.47 d (1.2H, Harom, J = 8.5 Hz),
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Yield 0.48 g (94%), mp 225–227°C. H NMR spec-
trum, δ, ppm: 3.31–3.36 m (1H, CH2), 3.40 s (1H,
NCH3), 3.42 s (2H, NCH3), 3.46–3.58 m (1H, CH2),
3.73 s (2H, OCH3), 3.78 s (1H, OCH3), 4.77 d (0.33H,
10b-H, J = 9.3 Hz), 5.40 d (0.67H, 10b-H, J = 9.1 Hz),
6.30 s (0.67H, 5-H), 6.84–6.98 m (3.67H, Harom, 5-H),
7.01–7.07 m (1H, Harom), 7.12–7.19 m (1H, Harom),
7.27 d (0.67H, Harom, J = 7.8 Hz), 7.43–7.48 m (1.33H,
7.52 d (0.8H, Harom, J = 8.6 Hz), 7.61 d (1.2H, Harom
,
J = 8.3 Hz), 7.65–7.74 m (3H, Harom), 7.76 s (0.6H,
CH=), 7.83–7.88 m (1.2H, Harom, CH=), 12.66 br.s
(1H, NH). Found, %: C 64.13; H 3.59; N 8.46.
C26H18ClN3O3S. Calculated, %: C 64.00; H 3.72;
N 8.61.
3-Methyl-5-[4-(2-phenyl-1,10b-dihydropyra-
zolo[1,5-c][1,3]benzoxazin-5-yl)benzylidene]-2-
sulfanylidene-1,3-thiazolidin-4-one (7a). Yield 0.46 g
(95%), mp 222–224°C. H NMR spectrum, δ, ppm:
3.34–3.36 m (1H, CH2), 3.43 s (3H, CH3), 3.54 d.d
Harom), 7.60–7.73 m (2H, Harom), 7.75 d (1.33H, Harom
,
J = 8.4 Hz), 7.79 s (0.33H, CH=), 7.89 m (2H, Harom
,
CH=). Found, %: C 65.57; H 4.40; N 8.12.
C28H23N3O3S2. Calculated, %: C 65.48; H 4.51;
N 8.18.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 4 2020