Synthesis of 1H-indazolo[1,2-b]phthalazinetrione derivatives
429
2,3,4,13-Tetrahydro-3,3-dimethyl-13-(3-phenoxyphenyl)-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4f, C29H24N2O4)
DSQ-II instrument with electron ionization (EI, 70 eV).
Elemental analysis was carried out on a Vario EL III
CHNOS elemental analyzer, and the results obtained
agreed favorably with calculated values.
Yellow powder, m.p.: 188–189 °C; IR (KBr): ꢀm = 1,635,
1,616, 1,452, 1,365, 1,311, 1,272, 1,240, 1,070, 985,
1
864 cm-1; H-NMR (500 MHz, CDCl3): = 1.16 (s, 3H),
Representative procedure for synthesis of 1H-
indazolo[1,2-b]phthalazinetrione derivatives
1.19 (s, 3H), 2.33 (s, 2H), 3.21 and 3.36 (AB system,
J = 19.0 Hz, 2H), 6.41 (s, 1H), 6.88 (dd, J = 8.0, 2.0 Hz,
1H), 6.98 (d, J = 8.0 Hz, 2H), 7.01 (t, J = 2.0 Hz, 1H),
7.08 (t, J = 7.5 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.27–
7.31 (m, 3H), 7.83–7.88 (m, 2H), 8.27–8.30 (m, 1H), 8.33–
8.36 (m, 1H) ppm; 13C-NMR (125 MHz, CDCl3):
d = 28.4, 28.7, 34.6, 38.0, 51.0, 64.6, 117.1, 118.3,
118.6, 119.1, 122.4, 123.4, 127.8, 128.0, 129.0, 129.1,
129.7, 129.9, 133.6, 134.6, 138.4, 151.0, 154.4, 156.0,
156.7, 157.6, 192.1 ppm; MS (ESI): m/z = 465 (M ? 1)?.
A mixture of 703 mg 1j (5 mmol), 700 mg 5,5-dimethyl-
1,3-cyclohexanedione (5.0 mmol), 820 mg 3 (5.0 mmol),
and 143 mg H4SiW12O40 (0.05 mmol) was heated at
100 °C. The reaction was monitored by TLC. After com-
pletion of the reaction, the mixture was cooled to room
temperature and washed with water. The solid product was
purified by recrystallization from aqueous EtOH to afford
1.93 g 4j (95%).
The spectroscopic and physical data for known com-
pounds 4a, 4c, 4e, 4g–4k, 4m, and 4n were found to be
identical to those described in the literature [31–34].
13-(3-Bromophenyl)-2,3,4,13-tetrahydro-3,3-dimethyl-1H-
indazolo[1,2-b]phthalazine-1,6,11-trione
(4l, C23H19BrN2O3)
ꢀ
Yellow powder, m.p.: 224–226 °C; IR (KBr): m = 1,635,
2,3,4,13-Tetrahydro-3,3-dimethyl-13-(3-methylphenyl)-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4b, C24H22N2O3)
1,618, 1,458, 1,419, 1,363, 1,309, 1,265, 1,120, 1,068, 952,
864 cm-1; 1H-NMR (500 MHz, CDCl3): d = 1.20 (s, 3H),
1.21 (s, 3H), 2.34 (s, 2H), 3.24 and 3.41 (AB system,
J = 19.0 Hz, 2H), 6.39 (s, 1H), 7.22 (t, J = 8.0 Hz, 1H),
7.41 (d, J = 8.0 Hz, 2H), 7.47 (t, J = 2.0 Hz, 1H), 7.85-
7.89 (m, 2H), 8.26–8.29 (m, 1H), 8.35–8.38 (m, 1H) ppm;
13C-NMR (125 MHz, CDCl3): d = 28.5, 28.6, 34.7, 38.0,
50.9, 64.3, 117.1, 122.8, 126.4, 127.8, 128.1, 129.0, 129.8,
130.2, 131.9, 133.7, 134.6, 138.7, 151.2, 154.4, 156.0,
192.0 ppm; MS (ESI): m/z = 452 (M ? 1)?.
ꢀ
Yellow needles, m.p.: 232–233 °C; IR (KBr): m = 1,639,
1,616, 1,419, 1,356, 1,315, 1,120, 1,066, 993, 952,
864 cm-1 1H-NMR (500 MHz, CDCl3): d = 1.20 (s,
;
3H), 1.21 (s, 3H), 2.32 (s, 3H), 2.33 (s, 2H), 3.23 and
3.41 (AB system, J = 19.0 Hz, 2H), 6.40 (s, 1H), 7.08 (d,
J = 7.5 Hz, 1H), 7.18–7.23 (m, 3H), 7.83–7.87 (m, 2H),
8.26–8.30 (m, 1H), 8.34–8.37 (m, 1H) ppm; 13C-NMR
(125 MHz, CDCl3): d = 21.5, 28.5, 28.6, 34.9, 38.1, 51.0,
65.0, 118.8, 124.1, 127.7, 127.9, 128.0, 128.6, 129.0,
129.2, 129.6, 133.4, 134.4, 136.3, 138.3, 150.7, 154.2,
156.1, 192.1 ppm; MS (EI): m/z = 386 (M?, 12), 295
(100).
2,3,4,13-Tetrahydro-3,3-dimethyl-13-[3-(trifluoro-
methyl)phenyl]-1H-indazolo[1,2-b]phthalazine-1,6,11-
trione (4o, C24H19F3N2O3)
ꢀ
Yellow needles, m.p.: 213–215 °C; IR (KBr): m = 1,635,
1,616, 1,359, 1,311, 1,263, 1,078, 983, 864 cm-1; H-NMR
1
13-(3,4-Dimethylphenyl)-2,3,4,13-tetrahydro-3,3-dimethyl-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4d, C25H24N2O3)
(500 MHz, CDCl3):d = 1.21 (s, 3H), 1.22(s, 3H), 2.34 (s, 2H),
3.24 and 3.43 (AB system, J = 19.0 Hz, 2H), 6.49 (s, 1H), 7.48
(t, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.60 (s, 1H),
7.68 (d, J = 8.0 Hz, 1H), 7.85–7.89 (m, 2H), 8.25–8.28 (m,
1H), 8.36–8.39 (m, 1H) ppm; 13C-NMR (125 MHz, CDCl3):
d = 28.3, 28.8, 34.7, 38.1, 50.9, 64.3, 117.1, 123.5, 123.6 (q,
J = 3.7 Hz), 125.6 (q, J = 3.6 Hz), 126.5 (q, J = 270.8 Hz),
127.8, 128.2, 128.9, 129.0, 129.2, 131.1, 131.2 (q, J =
37.5 Hz), 133.8, 134.7, 137.5, 151.4, 154.6, 156.1,
192.1 ppm; MS (EI): m/z = 440 (M?, 45), 295 (100).
ꢀ
Yellow needles, m.p.: 250–251 °C; IR (KBr): m = 1,635,
1,616, 1,419, 1,357, 1,315, 1,263, 1,120, 1,066, 993, 952,
1
864 cm-1; H-NMR (500 MHz, CDCl3): d = 1.20 (s, 3H),
1.21 (s, 3H), 2.19 (s, 3H), 2.22 (s, 3H), 2.33 (s, 2H),
3.23 and 3.42 (AB system, J = 19.0 Hz, 2H), 6.38
(s, 1H), 7.07–7.17 (m, 3H), 7.82–7.86 (m, 2H), 8.26–
8.28 (m, 1H), 8.33–8.36 (m, 1H) ppm; 13C-NMR
(125 MHz, CDCl3): d = 19.6, 19.9, 28.5, 28.7, 34.7,
38.1, 51.0, 64.9, 118.9, 124.5, 127.8, 127.9, 128.5, 129.0,
129.2, 130.0, 133.4, 133.7, 134.4, 136.9, 137.2, 150.7,
154.2, 156.1, 192.1 ppm; MS (EI): m/z = 400 (M?, 63),
295 (100).
13-Cyclohexyl-2,3,4,13-tetrahydro-3,3-dimethyl-1H-indaz-
olo[1,2-b]phthalazine-1,6,11-trione (4p, C23H26N2O3)
ꢀ
Yellow powder, m.p.: 221–222 °C; IR (KBr): m = 2,929,
2,853, 1,661, 1,469, 1,375, 1,361, 1,330, 1,269, 1,148,
123