Preparation of pyridyl-substituted Monoazatriphenylenes

Full text of DOI:10.1007/s10593-013-1275-4

Chemistry of Heterocyclic Compounds, Vol. 49, No. 3, June, 2013 (Russian Original Vol. 49, No. 3, March, 2013)
PREPARATION OF PYRIDYL-SUBSTITUTED
MONOAZATRIPHENYLENES
D. S. Kopchuk1,2, G. V. Zyryanov1,2*, I. S. Kovalev1, A. F. Khasanov1,
A. S. Medvedevskikh1, V. L. Rusinov1,2, and O. N. Chupakhin1,2
Keywords: azatriphenylenes, enamine, 1,2,4-triazine, cycloaddition, Diels–Alder reaction.
Azatriphenylene derivatives are of considerable interest due to their promising photophysical and
coordinating properties [1] and to their presence in the composition of natural compounds [2, 3].
Azatriphenylenes are important in inorganic biochemistry thanks to their use as intercalating ligands [4, 5]. In
addition, azatriphenylenes have shown promise as luminescent chemosensors of organic anions and
nitroaromatic compounds [6].
The most frequently used method for preparing azatriphenylenes is the Skraup synthesis [7, 8] which
demands the use of forcing conditions. Contemporary synthetic methods broadly use a cycloaddition reaction of
hard to obtain alkenes or arylacetylenes with aromatic substrates catalyzed by transition metal salts [9, 10].
Finally, the cyclocondensation of phenanthrenequinone with hydrazones of (hetero)aromatic carboxylic acid
amides leads to the corresponding aryl- [11, 12] and hetaryl-substituted [13] triazatriphenylenes.
In this report, we propose an efficient method for the synthesis of cycloalkene-annelated derivatives of
monoazatriphenylenes based on an aza-Diels–Alder reaction of the previously uncharacterized 3-(pyridin-
2-yl)phenathro[9,10-e][1,2,4]triazine (1) [14] with 1-morpholinocycloalkenes. A method for preparing different
pyridine derivatives through reaction of the corresponding mononuclear 1,2,4-triazines has been known for
some time [15-17]. In our work, we have used this method for the first time in a single-stage synthesis of the
poorly available pyridyl-substituted monoazatriphenylenes 2a,b.
_______
*To whom correspondence should be addressed, e-mail: gvzyryanov@gmail.com.
1Ural Federal University named after the First President of Russia B. N. Yeltsin, 19 Mira St., Yekaterinburg
620002, Russia.
2I. Ya. Postovskii Institute of Organic Synthesis, 22 Akademicheskaya/20 S. Kovalevskoi St., Yekaterinburg
620219, Russia; e-mail: chupakhin@ios.uran.ru.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 535-537, March, 2013. Original
article submitted October 23, 2012.
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0009-3122/13/4903-0500©2013 Springer Science+Business Media New York

For the preparation of compounds 2a,b, we have synthesized the corresponding triazatriphenylene 1 by
direct heating of phenanthrenequinone with the pyridine-2-carboxylic acid amide hydrazone. The corresponding
monoazatriphenylenes 2a,b were prepared by heating compound 1 in the presence of a fivefold excess of the
corresponding enamine at 200ºC without solvent. The structures of the obtained compounds were confirmed by
1
1H and 13C NMR, and mass spectrometry and from elemental analytical data. Thus, the H NMR spectra of
compounds 2a,b show characteristic signals for the cycloalkene fragments as multiplet and triplets in the range
1.70-3.60 ppm and also signals for the aromatic fragments at 7.00-9.50 ppm. The mass spectra of compounds
2a,b show molecular ion peaks corresponding to the proposed structure.
Preliminary experiments to study the complex-forming properties of the obtained products have shown
a high potential of the monoazatriphenylenes 2a,b as ligands for transition metal cations.
Therefore, using an aza-Diels–Alder reaction we have, for the first time, carried out a single-stage
synthesis of the poorly available pyridyl-substituted monoazatriphenylenes as promising ligands for transition
metal cations.
1H and 13C NMR spectra were recorded on a Bruker DRX-400 instrument (400 and 100 MHz,
respectively) using CDCl3 with TMS as internal standard. Mass spectra (electrospray ionization) were recorded
on a Bruker Daltonics microTOF-Q II mass spectrometer. Elemental analysis was carried out on a Perkin-Elmer
PE 2400 series II CHN analyzer. Melting points were determined on a Boetius melting point apparatus. TLC
analysis was performed on Merck 60F254 silica gel plates and revealed using UV light. The pyridine-
2-carboxylic acid amide hydrazone was prepared by a reported method [18].
3-(Pyridin-2-yl)phenanthro[9,10-e][1,2,4]triazine (1). Phenanthrenequinone (1 g, 4.81 mmol) was
dissolved in ethanol (100 ml), and the pyridine-2-carboxylic acid amide hydrazone (0.65 g, 4.81 mmol) was
added. The mixture was refluxed for 10 h, and the precipitate formed was filtered off, washed with ethanol, and
1
dried. Yield 0.83 g (56%). Yellow crystals; mp 202-204ºC. H NMR spectrum, , ppm (J, Hz): 7.54 (1H, m,
3
4
H-5 Py); 7.73-7.93 (4Н, m, H Ar); 8.01 (1Н, td, J = 7.5, J = 1.8, Н-4 Py); 8.59 (2Н, m, H Ar); 8.89 (1Н, dd,
3J = 7.5, 4J = 1.2, Н-3 Py); 9.01 (1Н, dd, 3J = 4.9, 4J = 1.8, Н-6 Py); 9.47 (1Н, dd, 3J = 8.0, 4J = 1.2, Н-5); 9.53
3
4
13
(1Н, dd, J = 8.0, J = 1.2, Н-12). C NMR spectrum, , ppm: 122.9 (2C); 124.3; 125.1; 125.2; 127.0; 127.4;
127.7; 128.0; 128.5; 130.9; 131.2; 132.4; 133.7; 137.1; 143.1; 145.4; 150.5; 153.7; 160.5. Mass spectrum, m/z
(Irel, %): 309.11 [M+H]+ (100). Found, %: С 77.83; Н 3.79; N 18.02. C20H12N4. Calculated, %: С 77.91; Н 3.92;
N 18.17.
Synthesis of Monoazatriphenylenes 2a,b (General Method). A mixture of triazatriphenylene 1 (0.4 g,
1.3 mmol) and the corresponding 1-morpholinocycloalkene (6.49 mmol) was stirred under an argon atmosphere
at 200ºC for 2 h. An additional portion of the 1-morpholinocycloalkene (3.25 mmol) was added, and the mixture
was stirred at 200ºC for a further 1 h. The reaction mixture was cooled to room temperature, acetonitrile (30 ml)
was added, and stirring continued for 3 h. The precipitate formed was filtered off, washed with acetonitrile, and
dried.
10-(Pyridin-2-yl)-12,13-dihydro-11H-dibenzo[f,h]cyclopenta[c]quinoline (2a). Yield 0.35 g (78%).
1
Colorless crystals; mp 181-183ºC. H NMR spectrum, , ppm (J, Hz): 2.25 (2Н, m, 12-СН2); 3.63 (2Н, t,
3J = 7.2, 11-СН2); 3.73 (2Н, t, 3J = 7.2, 13-СН2); 7.33 (1Н, m, H-5 Py); 7.62-7.74 (4Н, m, H Ar); 7.92 (1Н, ddd,
3J = 7.5, 3J = 7.5, 4J = 1.8, Н-4 Py); 8.60 (1Н, m, Н-3 Py); 8.63-8.77 (4Н, m, Н-6 Py, H Ar); 9.51 (1Н, m, H-8).
13C NMR spectrum, , ppm: 26.1; 33.2; 37.4; 122.4; 122.9; 123.1; 123.3; 123.7; 126.1; 126.6; 127.2; 127.3;
127.7; 128.3; 130.1; 130.8; 131.1; 131.8; 136.4; 138.9; 144.9; 148.5; 150.3; 151.9; 158.9. Mass spectrum, m/z
(Irel, %): 347.15 [M+H]+ (100). Found, %: С 86.52; Н 5.11; N 7.88. C25H18N2. Calculated, %: С 86.68; Н 5.24;
N 8.09.
10-(Pyridin-2-yl)-11,12,13,14-tetrahydro-11H-dibenzo[f,h]cyclohexa[c]quinoline (2b). Yield 0.32 g
1
(68%). Colorless crystals; mp 174-176ºC. H NMR spectrum, , ppm (J, Hz): 1.71-1.74 (2Н, m, ArСН2CH2);
1.93-1.96 (2Н, m, ArСН2CH2); 3.23 (2Н, t, 3J = 7.1, 11-СН2); 3.53 (2Н, t, 3J = 7.1, 14-СН2); 7.36 (1Н, m, H-5
Py); 7.56-7.72 (4Н, m, H Ar); 7.92 (1Н, ddd, 3J = 7.5, 3J = 7.5, 4J = 1.8, Н-4 Py); 8.08 (1Н, m, H Ar); 8.50-8.58
(2Н, m, H-3 Py, H Ar); 8.68 (1Н, m, H Ar); 8.72 (1Н, dd, 3J = 4.9, 4J = 1.8, Н-6 Py); 9.30 (1Н, m, H-8). Mass
501

spectrum, m/z (Irel, %): 361.17 [M+H]+ (100). Found, %: С 86.48; Н 5.45; N 7.46. C26H20N2. Calculated, %:
С 86.64; Н 5.59; N 7.77.
This work was carried out with the support of the Ministry of Education and Science of the Russian
Federation (state contracts 14.740.11.1020 and 14.A18.21.0817), the Russian Foundation for Basic Research
(grant 12-03-31726) and the Grants Council of the President of the Russian Federation (grant MK-
1511.2013.3).
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