SYNTHESIS OF NEW 1-(3,4-DIMETHYLPHENYL)-1,5-DIHYDROPYRAZOLO[3,4-d]...
597
(OCH2), 112.34 (Fu), 112.94 (Fu), 115.84, 119.22,
120.92, 124.06, 124.93, 129.90, 130.16, 135.84,
136.74, 137.03 (C5), 137.40 (C3), 139.25, 143.49 (Fu),
146.39 (Fu), 146.54 (C4), 157.17 (4″-C=O), 160.29
(FuC=O), 165.41 (4-C=O). Mass spectrum: m/z 473
[M + H]+. Found, %: C 66.12; H 5.10; N 11.83.
C26H24N4O5. Calculated, %: C 66.09; H 5.12; N 11.86.
M 472.50.
367 (7), 357 (7), 356 (26), 341 (4), 289 (3), 198 (9),
183 (2), 169 (2), 155 (1), 128 (1), 118 (1), 105 (1), 103
(10), 95 (7), 91 (2), 79 (12), 77 (12), 53 (1), 39 (1).
Mass spectrum (HESI): m/z 411 [M + H]+. Found, %:
C 70.11; H 5.69; N 13.04. C25H22N4O2. Calculated, %:
C 70.08; H 5.65; N 13.08. M 410.63.
Compounds 10b and 10c were synthesized
in a similar way.
Methyl 4-({1-(3,4-dimethylphenyl)-5-[(furan-2-
ylcarbonyl)amino]-1H-pyrazole-4-carbonyl}amino)-
benzoate (9e). Yield 91%, white powder, mp 208–
1-(3,4-Dimethylphenyl)-6-(furan-2-yl)-5-(4-
methylphenyl)-1,5-dihydro-4H-pyrazolo[3,4-d]-
pyrimidin-4-one (10b). Yield 79%, gray powder,
1
1
210°C. H NMR spectrum, δ, ppm: 2.24 s (6H, CH3),
mp 230–235°C. H NMR spectrum, δ, ppm: 2.31 s
3.83 s (3H, OCH3), 6.70 d.d (1H, 4-HFu, J = 1.2,
3.3 Hz), 7.24–7.28 m (4H, Harom), 7.36 s (1H, Harom),
7.86 d (2H, Harom, J = 9.0 Hz), 7.94 d (3H, J = 9.0 Hz),
8.40 s (1H), 10.26 (1H, NH), 10.40 (1H, NH).
13C NMR spectrum, δ, ppm: 19.01 (4′-CH3), 19.42
(3′-CH3), 51.94 (OCH3), 112.34 (Fu), 112.94 (Fu),
115.84, 119.22, 120.92, 124.06, 124.93, 129.90,
130.23, 135.84, 136.74, 137.03 (C5), 137.41 (C3),
139.25, 143.49 (Fu), 146.39 (Fu), 146.54 (C4), 157.17
(4″-C=O), 160.29 (FuC=O), 165.41 (4-C=O) Mass
spectrum: m/z 459 [M + H]+. Found, %: C 65.52;
H 4.86; N 12.19. C25H22N4O5. Calculated, %: C 65.49;
H 4.84; N 12.22. M 458.48.
(3H, CH3), 2.34 s (3H, CH3), 2.43 s (3H, CH3), 5.58 d
(1H, HFu, J = 3.5 Hz), 6.48 d.d (1H, 4-HFu, J = 1.2,
3.3 Hz), 7.32 d (3H, Harom, J = 8.0 Hz), 7.37 t (3H,
H
H
arom, J = 9.0 Hz), 7.88 m (2H, Harom), 7.91 s (1H,
arom), 8.37 s (1H, 3-H). C NMR spectrum, δC, ppm:
13
19.03 (3′-CH3), 19.74 (4′-CH3), 20.93 (4″-CH3),
105.07 (C3a), 112.23 (Fu), 112.52 (Fu), 117.74, 119.09,
122.73, 128.97, 130.09, 130.14, 134.79, 135.48,
136.22, 137.38, 139.18 (C3), 144.75, 146.61 (Fu),
148.06 (Fu), 150.50 (C6), 160.37 (C4). Mass spectrum:
m/z 397 [M + H]+. Found, %: C 69.59; H 5.37;
N 13.49. C24H20N4O3. Calculated, %: C 69.55; H 5.35;
N 13.52. M 396.45.
1,5-Bis(3,4-dimethylphenyl)-6-(furan-2-yl)-1,5-
dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one (10a).
A mixture of 1.0 g (2.3 mmol) of compound 9a and
5 mg (0.037 mmol) of calcined zinc(II) chloride was
heated at 220–240°C until water no longer evolved
(~30 min). The mixture was cooled, 10 mL of ethanol
was added, and the mixture was refluxed for 5 min.
The dark brown solution was cooled to 0°C, and
the precipitate was filtered off, washed with ethanol
(3×10 mL), and dried for 1 h at 50°C under reduced
pressure (15 mm). Yield 0.73 g (78%), gray powder,
1-(3,4-Dimethylphenyl)-5-(4-ethoxyphenyl)-
6-(furan-2-yl)-1,5-dihydro-4H-pyrazolo[3,4-d]py-
rimidin-4-one (10c). Yield 71%, dark gray powder,
mp 245–249°C. H NMR spectrum, δ, ppm: 1.38 t
(3H, CH3CH2, J = 7 Hz), 2.31 s (3H, CH3), 2.35 s (3H,
1
CH3), 4.11 q (2H, CH2, J = 7.0 Hz), 5.60 d (1H, Harom
,
J = 6.5 Hz), 6.50 d.d (1H, 4-HFu, J = 1.2, 3.3 Hz),
7.10 d (2H, Harom, J = 9.0 Hz), 7.35 t (3H, Harom, J =
9.0 Hz), 7.88 s (1H, Harom), 7.90 s (1H, Harom), 7.92 s
(1H, Harom), 8.37 s (1H, 3-H). Mass spectrum: m/z 427
[M + H]+. Found, %: C 67.58; H 5.46; N 12.57.
C25H22N4O3. Calculated, %: C 67.55; H 5.44; N 12.60.
M 426.48.
1
mp 190–193°C, Rf 0.49. H NMR spectrum, δ, ppm:
2.28 s (3H, CH3), 2.31 s (3H, CH3), 2.34 s (3H, CH3),
2.35 s (3H, CH3), 5.55 d (1H, Harom, J = 4.5 Hz),
6.48 d.d (1H, 4-HFu, J = 1.2, 3.3 Hz), 7.15 d.d (1H,
Harom, J = 8.0, 1.5 Hz), 7.22 s (1H, Harom), 7.35 d.d
(2H, Harom, J = 13.0, 8.0 Hz), 7.88 s (1H, Harom), 7.89 s
(1H, Harom), 7.92 s (1H, Harom), 8.36 s (1H, 3-H).
13C NMR spectrum, δC, ppm: 19.03 (CH3), 19.27
(CH3), 19.37 (CH3), 19.74 (CH3), 105.02 (C4), 112.36
(Fu), 112.82 (Fu), 117.83, 119.07, 122.72, 126.35,
129.73, 130.12, 130.47, 134.47, 134.86, 135.46,
136.20, 137.37, 137.81 (C3), 137.97 (C7a), 146.63 (Fu),
148.02 (Fu), 150.49 (C6), 157.47 (C4). Mass spectrum
(EI), m/z (Irel, %): 412 (4), 411 (28), 410 (100) [M]+,
409 (12), 394 (12), 393 (40), 382 (8), 381 (5), 379 (1),
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 4 2017