Synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-dione…
-
1
2
70–272 °C; IR (KBr, mmax, cm ): 3450 and 3340 (asym. and sym. stretching of –
2
NH ), 2205 (C:N stretching), 1710 (ester C=O stretching), 1670 (C=O stretching),
1
655 (C=O stretching), 1210 (C–O–C ether stretching). H NMR (400 MHz,
1
DMSO-d ): 0.99 (t, 3H, CH ), 1.95, 2.25 (s, 6H, 2 9 CH ), 3.99 (q, 2H, OCH ),
6
3
3
2
1
.57 (s, 1H, C1H), 7.80–8.35 (m, 12H, Ar–H), 8.75 (s, 2H, NH2). C NMR
3
6
(
(
100 MHz, DMSO-d ) d: 14.50 (CH ), 13.07, 20.25 (Ar–CH ), 59.88 (C1), 63.22
6
3
3
OCH ), 82.45 (C2), 117.23, 124.16, 124.84, 127.11, 127.55, 128.15, 128.53,
2
1
30.18, 132.40, 132.81, 133.17, 133.99, 135.28, 146.80, 151.30, 153.37 155.12 (Ar–
C), 157.23 (C=O), 158.67 (C=O), 164.22 (COOEt); Anal. Calcd for C H N O
2 26 6 5
3
(
(
574.59 g/mol): C, 66.89; H, 4.56; N, 14.63 (%); Found: C, 67.16; H, 4.82; N, 14.77
?
%). MS: 574 [M ? H] .
3-Amino-1-(5-(4-fluorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)-7-nitro-5,10-dioxo-
5
2
–
1
,10-dihydro-1H-pyrazolo[1,2-b]phthalazine-2-carbonitrile (4i) Yield: 80 %; mp
-
1
35–237 °C; IR (KBr, mmax, cm ): 3400 and 3250 (asym. and sym. stretching of
NH ), 2205 (C:N stretching), 1685 (C=O stretching), 1670 (C=O stretching),
2
1
195 (C–O–C ether stretching). H NMR (400 MHz, DMSO-d ): d 2.44 (s, 3H,
6
1
3
CH ), d 6.50 (s, 1H, C1H), 7.61–8.58 (m, 12H, Ar–H), 8.90 (s, 2H, NH ). C NMR
3
2
(
100 MHz, DMSO-d ) d: 13.06, (Ar–CH ), 58.90 (C1), 61.02 (C2), 116.30, 125.75,
6
3
1
1
1
1
26.80, 127.45, 127.98, 128.19, 129.40, 129.60, 130.42, 131.14, 132.16, 134.17,
34.80, 146.40, 147.70, 151.93, 152.24, 154.70, 158.23 (Ar–C), 157.65 (C=O),
58.40 (C=O); Anal. Calcd for C H FN O (551.48 g/mol): C, 60.98; H, 3.29; N,
2
8
18
7 5
?
7.78 (%); Found: C, 61.19; H, 2.96; N, 17.93 (%). MS: 551 [M ? H] .
3-Amino-1-(5-(4-cyanophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)-7-nitro-5,10-dioxo-
5
2
–
1
,10-dihydro-1H-pyrazolo[1,2-b]phthalazine-2-carbonitrile (4j) Yield: 81 %; mp
-
1
46–248 °C; IR (KBr, mmax, cm ): 3385 and 3185 (asym. and sym. stretching of
NH ), 2200 (C:N stretching), 1680 (C=O stretching), 1660 (C=O stretching),
2
1
185 (C–O–C ether stretching). H NMR (400 MHz, DMSO-d ): d 2.31 (s, 3H,
6
1
3
CH ), 6.53 (s, 1H, C1H), 7.55–8.60 (m, 12H, Ar–H), 8.80 (s, 2H, NH ). C NMR
3
2
(
100 MHz, DMSO-d ) d: 13.01, (Ar–CH ), 59.67 (C1), 61.49 (C2), 116.18, 117.17,
6
3
1
24.95, 125.64, 126.30, 127.81, 128.55, 128.80, 129.30, 131.74, 132.18, 133.16,
34.11, 134.70, 135.85, 144.14, 148.23, 151.40, 152.56, 156.81 (Ar–C), 157.46
1
(
C=O), 158.38 (C=O); Anal. Calcd for C H N O (558.50 g/mol): C, 62.36; H,
29 18 8 5
?
.25; N, 20.06(%); Found: C, 62.47; H, 3.46; N, 19.87 (%). MS: 558 [M ? H] .
3
3-Amino-1-(5-(4-fluorophenoxy)-3-methyl-1-p-tolyl-1H-pyrazol-4-yl)-7-nitro-5,10-dioxo-
5
2
–
1
6
,10-dihydro-1H-pyrazolo[1,2-b]phthalazine-2-carbonitrile (4k) Yield: 76 %; mp
-
1
54–256 °C; IR (KBr, mmax, cm ): 3385 and 3200 (asym. and sym. stretching of
NH ), 2210 (C:N stretching), 1685 (C=O stretching), 1670 (C=O stretching),
2
1
205 (C–O–C ether stretching). H NMR (400 MHz, DMSO-d ): d 2.17, 2.39 (s,
6
H, 2 9 CH ), 6.60 (s, 1H, C1H), 7.25–8.60 (m, 11H, Ar–H), 8.70 (s, 2H, NH ).
3
2
1
3
C NMR (100 MHz, DMSO-d ) d: 13.15, 20.50 (Ar–CH ), 60.00 (C1), 61.90 (C2),
6
3
1
1
1
16.33, 124.17, 127.21, 127.84, 128.14, 128.70, 129.20, 130.05, 131.30, 133.08,
34.15, 135.50, 137.18, 143.40, 149.80, 150.16, 151.96, 154.30, 157.90 (Ar–C),
58.80 (C=O), 158.95 (C=O); Anal. Calcd for C H FN O (565.51 g/mol): C,
2
9
20
7 5
123