SYNTHESIS OF 4,7-PHENANTHROLINE METHYLDERIVATIVES
1667
3
3
7.32 m (10H arom, J 7.0 Hz), 7.23 d (H2, J 7.9 Hz),
H 4.93; Cl 16.03; N 6.28. C25H22Cl2N2O. Calculated, %:
C 68.67; H 5.04; Cl 16.23; N 6.41.
7.40 d, 7.72 d (H5,6, 3J 8.9 Hz), 8.20 d (H1, 3J 4.9 Hz),
9.62 s (NH). Found, %: C 80.36; H 5.74; N 6.04.
C30H26N2O2. Calculated, %: C 80.72; H 5.83; N 6.28.
12-(2,4-Dichlorophenyl)-3,9,9-trimethyl-
8,9,10,12-tetrahydro-7H-benzo[b][4,7]phen-
anthrolin-11-one (Vb). Yield 88%, mp 230231°C.
1H NMR spectrum, d, ppm: 0.91 s (Me), 1.08 s (Me),
2.12 d.d (2H8, 2J 16.2 Hz), 2.45 m (2H10), 2.55 s (Me),
5.91 s (H12), 7.027.12 m, 7.18 s (3H arom), 7.29 d (H2,
3J 7.8 Hz), 7.44 d, 7.73 d (H5,6, 3J 8.7 Hz), 8.35 d (H1,
3J 4.6 Hz), 9.63 s (NH). Found, %: C 68.50; H 4.99;
Cl 15.87; N 6.19. C25H22Cl2N2O. Calculated, %:
C 68.67; H 5.04; Cl 16.23; N 6.41.
3-Methyl-12-(2-pyridyl)-8,9,10,12-tetrahydro-
7H-benzo[b][4,7]phenanthrolin-11-one (IVw). Yield
77%, mp 297298°C. H NMR spectrum, d, ppm:
1
1.96 m (2H9), 2.26 m (2H8), 2.58 s (Me), 2.65 m (2H10),
5.93 s (H12), 6.97 m, 7.46 m, 7.53 m, 8.26 d (4H arom, 3J
4.9 Hz), 7.22 d (H2, 3J 8.0 Hz), 7.42 d, 7.69 d (H5,6, 3J
9.0 Hz), 8.50 d (H1, 3J 4.4 Hz), 9.60 s (NH). Found, %:
C 77.19; H 5.60; N 12.01. C22H19N3O. Calculated, %:
C 77.42; H 5.57; N 12.32.
3,9,9-Trimethyl-12-(3,4,5-trimethoxyphenyl)-
8 , 9 , 1 0 , 1 2 - t e t r a h y d r o - 7 H- b e n z o [ b ][4 , 7 ]-
phenanthrolin -11-one (Vc).Yield 82%, mp 242243°C.
1H NMR spectrum, d, ppm: 0.93 s (Me), 1.09 s (Me),
2.10 d.d (2H8, 2J 16.1 Hz), 2.46 m (2H10), 2.54 s (Me),
3.55 s (OMe), 3.61 s (2OMe), 5.79 s (H12), 6.44 s
(2H arom), 7.30 d (H2, 3J 7.6 Hz), 7.42 d, 7.70 d (H5,6, 3J
8.8 Hz), 8.20 d (H1, 3J 4.8 Hz), 9.62 s (NH). Found, %:
C 73.12; H 6.48; N 5.74. C28H30N2O2. Calculated, %:
C 73.36; H 6.55; N 6.11.
3-Methyl-12-(3-pyridyl)-8,9,10,12-tetrahydro-
7H-benzo[b][4,7]phenanthrolin-11-one (IVx). Yield
76%, mp 302303°C. H NMR spectrum, d, ppm:
1
1.91 m (2H9), 2.23 m (2H8), 2.55 s (Me), 2.62 m (2H10),
5.84 C (H12), 6.96 m, 8.32 s (4H arom), 7.26 d (H2,
3J 8.1 Hz), 7.41 d, 7.70 d (H5,6, 3J 9.0 Hz), 8.24 d (H1,
3J 4.8 Hz), 9.61 s (NH). Found, %: C 77.25; H 5.53;
N 12.14. C22H19N3O. Calculated, %: C 77.42; H 5.57;
N 12.32.
3-Methyl-12-[2-(3-methyl)thienyl]-8,9,10,12-
12-(4-Benzyloxyphenyl)-3,9,9-trimethyl-
8,9,10,12-tetrahydro-7H-benzo[b][4,7]-phen-
anthrolin -11-one (Vd). Yield 70%, mp 296297°C.
1H NMR spectrum, d, ppm: 0.94 s (Me), 1.10 s (Me),
2.11 d.d (2H8, 2J 16.2 Hz), 2.44 m (2H10), 2.55 C (Me),
4.90 s (OCH2Ph), 5.78 s (H12), 6.71 d, 7.12 d, 7.31 m
(10H arom), 7.27 d (H2, 3J 7.3 Hz), 7.40 d, 7.71 d (H5,6,
3J 8.7 Hz), 8.19 d (H1, 3J 4.5 Hz), 9.60 s (NH). Found,
%: C 80.73; H 6.28; N 5.76. C32H30N2O2. Calculated,
%: C 81.01; H 6.33; N 5.91.
tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-one
1
(IVy). Yield 76%, mp 292293°C. H NMR spectrum,
d, ppm: 1.93 m (2H9), 2.22 m (2H8), 2.45 s (Me), 2.56 s
(Me), 2.63 m (2H10), 5.86 s (H12), 6.58 d, 6.96 d (2H
arom, 3J 7.0 Hz), 7.23 d (H2, 3J 8.2 Hz), 7.40 d, 7.72 d
3
3
(H5,6, J 8.8 Hz), 8.24 d (H1, J 4.9 Hz), 9.68 s (NH).
Found, %: C 73.26; H 5.60; N 7.54; S 8.65. C22H20N2OS.
Calculated, %: C 73.33; H 5.56; N 7.78; S 8.89.
3-Methyl-12-(cyclohexenyl)-8,9,10,12-
tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-one
1
(IVz). Yield 43%, mp 290291°C. H NMR spectrum,
REFERENCES
d, ppm: 1.201.76 (7H alicyclic), 1.92 m (2H9), 2.21 m
(2H8), 2.55 s (Me), 2.62 m (2H10), 4.86 s (CH=CH),
5.46 s (H12), 7.24 d (H2, 3J 8.2 Hz), 7.43 d, 7.70 d (H5,6,
3J 8.8 Hz), 8.21 d (H1, 3J 4.7 Hz), 9.60 s (NH). Found,
%: C 79.97; H 7.01; N 7.84. C23H24N2O. Calculated, %:
C 80.23; H 6.98; N 8.14.
1. CIBA, Ltd. Swiss Patent 290515, 1953; Chem. Abstr.,1955,
vol. 49, 7606g.
2. CIBA, Ltd. Swiss Patent 296573, 1954; Chem. Abstr., 1956,
vol. 50, 5040a.
3. Rittersdorf, W., Rey, H., Guethlein, W., and Rieckmann, P.,
German Patent 2235152, 1974;Chem. Abstr., 1974, vol. 80,
142769d.
4. Berger, D., Fey, G., Kuhr, M., and Werner, W., EPV Patent
14929 1980; Chem. Abstr., 1981, vol. 94, 43719z.
5. Jastzebska-Glapa, M., Mlochowski, J., and Sliwa, W., J. Pr.
Chem., 1977, vol. 319, p. 883.
12-(2,3-Dichlorophenyl)-3,9,9-trimethyl-
8 , 9 , 1 0 , 1 2 - t e t r a h y d r o - 7 H- b e n z o [ b ][4 , 7 ]-
phenanthrolin-11-one (Va). Yield 80%, mp 320321°C.
1H NMR spectrum, d, ppm: 0.94 s (Me), 1.10 s (Me),
2.10 d.d (2H8, 2J 16.0 Hz), 2.41 m (2H10), 2.53 s (Me),
6.06 s (H12), 7.08 t, 7.21 d, 7.32 d (3H arom, 3J 7.5 Hz),
7.28 d (H2, 3J 7.9 Hz), 7.41 d, 7.71 d (H5,6, 3J 8.9 Hz),
8.36 d (H1, 3J 4.5 Hz), 9.70 s (NH). Found, %: C 68.29;
6. Koneyukhov, V.N., Pyankova, L.N., and Pushkareva, Z.V.,
Zh. Obshch. Khim.,1962, vol. 32, p. 2745.
7. Eltsov,A.V., Nekrasov, S.V., and Smirnov, E.V., Zh. Org.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004