1652
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
Mamedov et al.
6ꢀNitroꢀ3ꢀ(2ꢀoxoꢀ2ꢀphenylethylidene)ꢀ3,4ꢀdihydroquinoxꢀ
alinꢀ2(1H)ꢀone (4d) was obtained from 4ꢀbenzoylꢀ3ꢀhydroxyꢀ
2(5H)ꢀfuranone and 4ꢀnitroꢀ1,2ꢀphenylenediamine. The yield
was 59%, m.p. 304—306 °C. Found (%): C, 62.28; H, 3.51;
N, 13.61. C16H11N3O4. Calculated (%): C, 62.14; H, 3.58;
N, 13.59. IR, ν/cm–1: 3433, 3379, 3082, 2939, 1696, 1623,
1603, 1536, 1494, 1464, 1441, 1338, 1247, 1225, 1160, 1090,
1060, 1024, 875, 831, 807, 784, 746, 709, 573. 1H NMR, δ: 6.89
(s, 1 H, H(1´)); 7.24 (d, 1 H, H(8), J = 8.8 Hz); 7.56—7.58 (m, 2 H,
Hm); 7.62 (t, 1 H, Hр, J = 6.9 Hz); 7.97—8.02 (m, 3 H, Ho, H(7));
8.61 (s, 1 H, H(5)); 12.41 (s, 1 H, NH); 13.29 (s, 1 H, NH).
3ꢀ[2ꢀOxoꢀ2ꢀ(pꢀtolyl)ethylidene]ꢀ3,4ꢀdihydroquinoxalinꢀ2(1H)ꢀ
one (4e) was obtained from 3ꢀhydroxyꢀ4ꢀ(4´ꢀmethylbenzoyl)ꢀ
2(5H)ꢀfuranone and 1,2ꢀphenylenediamine. The yield was 74%,
m.p. 252—253 °C. Found (%): C, 73.46; H, 4.99; N, 10.10.
C17H14N2O2. Calculated (%): C, 73.37; H, 5.07; N, 10.07.
IR, ν/cm–1: 3440, 3044, 3007, 2966, 2922, 2884, 1678, 1607,
1582, 1547, 1370, 1336, 1270, 1248, 1183, 1060, 801, 746, 570.
1H NMR, δ: 2.40 (s, 3 H, Me); 6.82 (s, 1 H, H(1´)); 7.14—7.16
(m, 3 H, H(5), H(7), H(8)); 7.36 (d, 2 H, Hm, J = 8.2 Hz);
7.50—7.52 (m, 1 H, H(6)); 7.91 (d, 2 H, Ho, J = 8.2 Hz); 12.01
(s, 1 H, NH).
6´ꢀChloroꢀ3ꢀphenylꢀ1´(H)ꢀspiro[2ꢀpyrazolineꢀ5,2´ꢀquinoxꢀ
alin]ꢀ3´(4´H)ꢀone (5c) was obtained similarly to 5a from
3,4ꢀdihydroquinoxalinꢀ2(1H)ꢀone 4c (0.12 g, 0.4 mmol) and
NH2NH2•H2O (0.22 g, 4 mmol) (90%). The yield was 0.08 g
(64%), m.p. 243—246 °C. Found (%): C, 61.52; H, 4.10;
Cl, 11.30; N, 17.79. C16H13ClN4O. Calculated (%): C, 61.45;
H, 4.19; Cl, 11.34; N, 17.91. IR, ν/cm–1: 3443, 3304, 3274,
3112, 2924, 1680, 1663, 1615, 1601, 1498, 1446, 1387, 1369,
1353, 1307, 1221, 1083, 1059, 1001, 871, 852, 812, 757, 688.
1H NMR, δ: 3.05 (d, 1 H, CHAHB, J = 17.1 Hz); 3.91 (d, 1 H,
CHAHB, J = 17.5 Hz); 6.73—6.75 (m, 1 H, H(8')); 6.86—6.88
(m, 2 H, H(7), NH); 7.35 (t, 1 H, Hp, J = 7.7 Hz, J = 7.2 Hz);
7.42 (dd, 2 H, Hm, J = 8.1 Hz, J = 7.2 Hz); 7.50 (s, 1 H, H(5'));
7.67 (d, 2 H, Ho, J = 7.2 Hz); 8.07 (br.s, 1 H, NH); 10.77 (br.s,
1 H, NH).
7´ꢀNitroꢀ3ꢀphenylꢀ1´(H)ꢀspiro[2ꢀpyrazolineꢀ5,2´ꢀquinoxalin]ꢀ
3´(4´H)ꢀone (5d) was obtained similarly to 5a from 3,4ꢀdihydroꢀ
quinoxalinꢀ2(1H)ꢀone 4d (0.15 g, 0.5 mmol) and NH2NH2•H2O
(0.28 g, 5 mmol) (90%). The yield was 0.116 g (73%),
m.p. 235—238 °C. Found (%): C, 59.57; H, 3.94; N, 21.52.
C16H13N5O3. Calculated (%): C, 59.44; H, 4.05; N, 21.66.
IR, ν/cm–1: 3444, 3306, 3274, 1684, 1669, 1602, 1533, 1496,
1
3ꢀ[2ꢀ(pꢀChlorophenyl)ꢀ2ꢀoxoethylidene]ꢀ3,4ꢀdihydroquinoxꢀ
alinꢀ2(1H)ꢀone (4f) was obtained from 4ꢀ(4´ꢀchlorobenzoyl)ꢀ
3ꢀhydroxyꢀ2(5H)ꢀfuranone and 1,2ꢀphenylenediamine. The
yield was 66%, m.p. 285—286 °C (cf. Ref. 15: m.p. 285—286 °C
(ethanol)).
1475, 1448, 1409, 1330, 1089, 880, 763, 744, 690. H NMR, δ:
3.11 (d, 1 H, CHAHB, J = 17.6 Hz); 3.96 (d, 1 H, CHAHB,
J = 17.5 Hz); 7.03 (d, 1 H, H(6'), J = 8.5 Hz); 7.38 (t, 1 H, Hp,
J = 7.2 Hz); 7.44 (dd, 2 H, Hm, J = 7.7 Hz, J = 7.2 Hz); 7.60
(s, 1 H, H(8')); 7.68—7.70 (m, 3 H, Ho, H(5')); 7.97 (s, 1 H,
NH); 8.21 (s, 1 H, NH); 11.30 (s, 1 H, NH).
3ꢀPhenylꢀ1´(H)ꢀspiro[2ꢀpyrazolineꢀ5,2´ꢀquinoxalin]ꢀ3´(4´H)ꢀ
one (5a). A solution of 3,4ꢀdihydroquinoxalinꢀ2(1H)ꢀone 4a
(0.13 g, 0.5 mmol) and NH2NH2•H2O (0.28 g, 5 mmol) (90%)
in BunOH (10 mL) after reflux for 16 h was kept for ~14 h.
Crystals formed were filtered off, washed with EtOH (2×10 mL),
and dried in air. The yield was 0.07 g (51%), m.p. 310—312 °C.
The filtrate was half concentrated and kept for ~14 h at ~20 °C.
Crystals of 5a formed were filtered off, washed with EtOH
(2×5 mL), dried in air. After recrystallization from MeCN, spiroꢀ
quinoxaline 5a was obtained (0.04 g, 30%). Found (%):
C, 69.13; H, 4.92; N, 20.19. C16H14N4O. Calculated (%):
C, 69.05; H, 5.07; N, 20.13. IR, ν/cm–1: 3445, 3318, 3261,
3080, 2960, 1664, 1617, 1604, 1504, 1446, 1413, 1377, 1356,
3ꢀ(pꢀTolyl)ꢀ1´(H)ꢀspiro[2ꢀpyrazolineꢀ5,2´ꢀquinoxalin]ꢀ
3´(4´H)ꢀone (5e) was obtained similarly to 5a from 3,4ꢀdihydroꢀ
quinoxalinꢀ2(1H)ꢀone 4e (0.4 g, 1.4 mmol) and NH2NH2•H2O
(0.77 g, 14 mmol) (90%). The yield was 0.315 g (77%),
m.p. 230—231 °C. Found (%): C, 69.98; H, 5.43; N, 19.05.
C17H16N4O. Calculated (%): C, 69.85; H, 5.52; N, 19.16.
IR, ν/cm–1: 3447, 3314, 3261, 3212, 3171, 3122, 3085, 3044,
2962, 2917, 1669, 1605, 1505, 1415, 1373, 1311, 1247, 1215,
1
1116, 1073, 1035, 1000, 916, 871, 812, 736. H NMR, δ: 2.34
(s, 3 H, Me); 3.01 (d, 1 H, CHAHB, J = 17.1 Hz); 3.90 (d, 1 H,
CHAHB, J = 17.1 Hz); 6.70 (dd, 1 H, H(6'), J = 7.7 Hz,
J = 7.7 Hz); 6.74 (d, 1 H, H(8), J = 7.7 Hz); 6.83 (dd, 1 H,
H(7), J = 7.7 Hz, J = 8.1 Hz); 6.85 (d, 1 H, H(5), J = 7.7 Hz);
7.23 (d, 2 H, Hm, J = 7.7 Hz); 7.29 (s, 1 H, NH); 7.56 (d, 2 H,
Ho, J = 8.1 Hz); 7.83 (s, 1 H, NH); 10.60 (s, 1 H, NH).
1
1312, 1218, 1062, 1002, 915, 871, 755, 735, 687. H NMR, δ:
3.03 (d, 1 H, CHAHB, J = 17.4 Hz); 3.93 (d, 1 H, CHAHB,
J = 17.4 Hz); 6.70 (dd, 1 H, H(6'), J = 7.5 Hz, J = 7.5 Hz);
6.74 (d, 1 H, H(8'), J = 7.2 Hz); 6.84 (dd, 1 H, H(7'), J = 7.5 Hz,
J = 7.5 Hz); 6.85 (d, 1 H, H(5'), J = 7.5 Hz); 7.32 (br.s, 1 H,
NH); 7.35 (t, 1 H, Hp, J = 7.5 Hz); 7.42 (dd, 2 H, Hm, J = 7.9 Hz,
J = 7.2 Hz); 7.67 (d, 2 H, Ho, J = 7.2 Hz); 7.98 (br.s, 1 H, NH);
10.64 (br.s, 1 H, NH).
3ꢀ(pꢀChlorophenyl)ꢀ1´(H)ꢀspiro[2ꢀpyrazolineꢀ5,2´ꢀquinoxalin]ꢀ
3´(4´H)ꢀone (5f) was obtained similarly to 5a from 3,4ꢀdihydroꢀ
quinoxalinꢀ2(1H)ꢀone 4f (0.6 g, 2 mmol) and NH2NH2•H2O
(1.1 g, 20 mmol) (90%). The yield was 0.454 g (73%), m.p.
235—237 °C. Found (%): C, 61.49; H, 4.09; Cl, 11.31; N, 17.84.
C16H13ClN4O. Calculated (%): C, 61.45; H, 4.19; Cl, 11.34;
N, 17.91. IR, ν/cm–1: 3445, 3314, 3249, 3171, 3126, 3081,
1668, 1666, 1619, 1605, 1505, 1374, 1311, 1090, 999, 824, 741,
6´,7´ꢀDimethylꢀ3ꢀphenylꢀ1´(H)ꢀspiro[2ꢀpyrazolineꢀ5,2´ꢀ
quinoxalin]ꢀ3´(4´H)ꢀone (5b) was obtained similarly to 5a
from 3,4ꢀdihydroquinoxalinꢀ2(1H)ꢀone 4b (0.3 g, 1 mmol) and
NH2NH2•H2O (0.55 g, 10 mmol) (90%). The yield was 0.232 g
(76%), m.p. 237—240 °C. Found (%): C, 70.70; H, 5.88;
N, 18.13. C18H18N4O. Calculated (%): C, 70.57; H, 5.92; N, 18.29.
IR, ν/cm–1: 3440, 3308, 3264, 3104, 3054, 2968, 2916, 1679,
1660, 1605, 1516, 1448, 1401, 1356, 1308, 1245, 1062, 1003,
1
647. H NMR, δ: 3.02 (d, 1 H, CHAHB, J = 17.3 Hz); 3.91 (d,
1 H, CHAHB, J = 17.3 Hz); 6.71 (dd, 1 H, H(6'), J = 7.2 Hz,
J = 7.7 Hz); 6.74 (d, 1 H, H(8'), J = 7.7 Hz); 6.84 (dd, 1 H,
H(7), J = 7.2 Hz, J = 7.2 Hz); 6.86 (d, 1 H, H(5), J = 7.7 Hz);
7.32 (s, 1 H, NH); 7.47 (d, 2 H, Hm, J = 8.6 Hz); 7.68 (d, 2 H,
Ho, J = 8.6 Hz); 8.12 (s, 1 H, NH); 10.64 (s, 1 H, NH).
1
857, 753, 686. H NMR, δ: 2.10 (s, 6 H, 2 Me); 3.01 (d, 1 H,
CHAHB, J = 17.4 Hz); 3.90 (d, 1 H, CHAHB, J = 17.1 Hz); 6.54
(s, 1 H, H(8')); 6.63 (s, 1 H, H(5')); 7.04 (br.s, 1 H, NH); 7.34
(t, 1 H, Hp, J = 7.5 Hz, J = 7.2 Hz); 7.42 (dd, 2 H, Hm, J = 7.5 Hz,
J = 7.2 Hz); 7.66 (d, 2 H, Ho, J = 7.2 Hz); 10.47 (br.s, 1 H, NH).
2ꢀ(5ꢀPhenylꢀ1Hꢀpyrazolꢀ3ꢀyl)ꢀ1Hꢀbenzimidazole (8a).
A solution of spiroquinoxaline 5a (0.2 g, 0.7 mmol) in acetic
acid (10 mL) after reflux for 8 h was kept for ~14 h. The solvent
was evaporated in vacuo, a crystalline precipitate formed was