Synthesis of Novel [1,2,4]triazino[5,6-f]-1,10-phenanthrolines Based on the Azolyl-1-carboxamidrazones

Full text of DOI:10.1007/s10593-013-1202-8

Chemistry of Heterocyclic Compounds, Vol. 48, No. 11, February, 2013 (Russian Original Vol. 48, No. 11, November, 2012)
SYNTHESIS OF NOVEL [1,2,4]TRIAZINO[5,6-f]-
1,10-PHENANTHROLINES BASED ON THE
AZOLYL-1-CARBOXAMIDRAZONES
A. S. Bunev1*, E. V. Sukhonosova2, V. E. Statsyuk1,
G. I. Ostapenko1, and P. P. Purygin2
Keywords: amidrazones, 1,2,4-triazine, [1,2,4]triazino[5,6-f]-1,10-phenanthroline, phenanthroline.
The possibility to obtain certain [1,2,4]triazino[5,6-f]-1,10-phenanthrolines and novel complex
compounds based on them as promising photoactivated cytotoxins has been demonstrated in the studies [1-3]. It
should be noted that the starting ligands were obtained by prolonged refluxing in alcohol of 1,10-phen-
anthroline-5,6-dione with amidrazones, in which the amidrazone fragment was linked with a carbon atom
belonging to a heteroaromatic system.
In continuation of our work on the reactivity of N-heterocyclic amidrazones, we propose a convenient
method for the preparation of azolyl-substituted [1,2,4]triazino[5,6-f]-1,10-phenanthrolines 3 and 6 from the
different amidrazones 2 and 5, in which the carboxamido hydrazone fragment is bonded to a nitrogen of the
heterocycle. The starting amidrazones 2 and 5 were synthesized by treating hydrazine hydrate with the readily
available N-cyanoheterocycles 1 and 4 (the preparation of which we have reported before [4]). The target
compounds 3 and 6 were prepared in 68 and 74% yield respectively by brief (20 min) refluxing of compounds 2
or 5 with 1,10-phenanthroline-5,6-dione in isopropanol, which points to an increased reactivity of the
carboxamido hydrazone fragment bonded to a heterocyclic nitrogen in heterocyclization reactions with
1,2-diketones.
Hence we propose a convenient method for preparing the previously unknown azolyl-substituted
[1,2,4]triazino[5,6-f]-1,10-phenanthrolines as promising ligands, based on readily available N-heterocyclic
amidrazones.
1
13
IR spectra were recorded on an FSM-1201 instrument for KBr pellets. The H and C NMR spectra
were recorded on a Bruker AM-400 instrument (400 and 100 MHz, respectively) using DMSO-d6 with TMS as
internal standard. Elemental analysis was carried out on a vario EI cube analyzer. Melting points were measured
on a Boetius hot stage apparatus and are not corrected.
The benzimidazol-1-ylcarboxamidohydrazone (5) was prepared by method [5].
_______
*To whom correspondence should be addressed, e-mail: a.s.bunev@gmail.com.
1Institute of Chemistry and Environmental Engineering, Togliatti State University, 14 Belorusskaya St.,
Togliatti 445667, Russia.
2 Samara State University, 1 Akademika Pavlova St., Samara 443011, Russia; e-mail: puryginpp2002@mail.ru.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1843-1845, November, 2012.
Original article submitted October 26, 2012.
1728
0009-3122/13/4811-1728©2013 Springer Science+Business Media New York

Imidazol-1-ylcarboxamidohydrazone (2). Hydrazine hydrate (0.70 ml, 21.6 mmol) was added to a
stirred solution of compound 1 (2.00 g, 21.5 mmol) in MeCN (4 ml), and the temperature of the mixture was
maintained in the range from -5 to 0°C. Stirring was continued for 10 min and the precipitate formed was
filtered off, washed with cold EtOH, and recrystallized from MeCN. Yield 1.91 g (71%). White powder, turning
pink in air. Mp 102-104°C (decomp.). IR spectrum, , cm-1: 3321, 3101, 1693, 1643, 1493, 1327, 914, 768. 1H
NMR spectrum, , ppm (J, Hz): 8.12 (1H, s, H-2); 7.58-7.53 (1H, m, H-4); 7.05-6.98 (1H, m, H-5); 6.57 (2H,
br. s, =C–NH2); 4.98 (2H, br. s, =N–NH2). Found, %: C 38.25; H 5.67; N 56.09. C4H7N5. Calculated, %: C 38.39;
H 5.64; N 55.97.
3-(1H-Imidazol-1-yl)[1,2,4]triazino[5,6-f]-1,10-phenanthroline (3). 1,10-Phenanthroline-5,6-dione
(1.68 g, 8 mmol) was added to a warmed solution of compound 2 (1.00 g, 8 mmol) in 2-PrOH (30 ml) with
vigorous stirring. The solution was refluxed for 20 min, cooled, and the precipitate was filtered off,
recrystallized from EtOH, and dried in a drying oven for 24 h at 60°C. Yield 1.63 g (68%). Yellowish-green
crystalline powder. Mp > 300°C. IR spectrum, , cm-1: 3123, 3074, 1579, 1518, 1384, 1253, 1072, 758.
1H NMR spectrum, , ppm (J, Hz): 9.69 (1Н, dd, J = 4.3, J = 1.8, Н-10); 9.51 (1Н, dd, J = 4.3, J = 1.8, Н-7); 9.29
(1Н, ddd, J = 8.0, J = 1.8, J = 0.7, Н-5); 8.92 (1Н, ddd, J = 7.9, J = 1.8, J = 0.7, Н-12); 8.34 (1Н, s, Н-2');
8.02-7.98 (1H, m, Н-5'); 7.95 (1Н, dd, J = 7.9, J = 4.3, Н-11); 7.84 (1Н, dd, J = 8.0, J = 4.3, Н-6); 7.72-7.65
(1Н, m, Н-4'). 13C NMR spectrum, , ppm: 122.9 (С-6); 123.8 (С-11); 127.1 (С-4b); 127.8 (С-5'); 128.8
(С-12a); 131.0 (C-5); 131.5 (C-12); 131.9 (С-4'); 140.3 (C-12b); 144.0 (C-8a); 145.8 (C-8b); 146.0 (C-4a);
148.1 (СН-2'); 151.2 (C-7); 151.9 (C-10); 158.6 (C-3). Found, %: C 64.09; H 3.10; N 32.83. C16H9N7.
Calculated, %: C 64.21; H 3.03; N 32.76.
3-(1H-Benzimidazol-1-yl)[1,2,4]triazino[5,6-f]-1,10-phenanthroline (6) was prepared similarly from
the compound 5 (1.4 g, 8 mmol). The product was recrystallized from DMF and dried in a drying oven for 24 h
at 60°C. Yield 2.07 g (74%). Yellowish-green crystalline powder. Mp > 300°C. IR spectrum, , cm-1: 3135,
3066, 1571, 1507, 1487, 1451, 1383, 1074, 745. 1H NMR spectrum, , ppm (J, Hz): 9.71 (1Н, dd, J = 4.4, J = 1.9,
Н-10); 9.58 (1Н, dd, J = 4.4, J = 1.9, Н-7); 9.3 (1Н, ddd, J = 8.0, J = 1.9, J = 0.7, Н-5); 8.84 (1Н, ddd, J = 8.0,
1729

J = 1.9, J = 0.7, Н-12); 8.56 (1Н, s, Н-2'); 7.97 (1Н, dd, J = 8.0, J = 4.4, Н-11); 7.88 (1Н, dd, J = 8.0, J = 4.4,
Н-6); 7.79-7.77 (1Н, m, Н-4'); 7.73-7.68 (1Н, m, Н-7'); 7.40-7.37 (1Н, m, Н-6'); 7.32-7.30 (1Н, m, Н-5').
13C NMR spectrum, , ppm: 111.6 (С-7'); 120.5 (С-4'); 123.0 (С-6); 123.5 (С-5'); 123.7 (С-11); 125.1 (С-6');
126.7 (С-4b); 127.9 (С-12a); 131.1 (C-5); 131.5 (C-12); 139.2 (C-7a'); 140.0 (C-12b); 142.1 (C-3а'); 144.9
(C-8a); 145.2 (C-8b); 146.3 (C-4a); 150.7 (C-7); 150.9 (C-10); 152.6 (CH-2'); 159.2 (С-3). Found, %: C 68.59;
H 3.21; N 28.20. C20H11N7. Calculated %: C 68.76; H 3.17; N 28.06.
REFERENCES
1.
2.
3.
4.
5.
B. Sun, J. Chu, Y. Chen, F. Gao, L.-N. Ji, and H. Chao, J. Mol. Struct., 890, 203 (2008).
G. R. Pabst, O. C. Pfuller, and J. Sauer, Tetrahedron Lett., 39, 8825 (1998).
G. R. Pabst, O. C. Pfuller, and J. Sauer, Tetrahedron, 55, 8045 (1999).
P. P. Purygin and S. V. Pan'kov, Zh. Org. Khim., 31, 934 (1995).
А. V. Sokolov, A. V. Volgzhanina, and P. P. Purygin, Acta Crystallogr., Sect. E: Struct. Rep. Online,
E62, 03208 (2006).
1730