Synthesis of a novel biheterocyclic system, 2,2'-bi-1,3,7-triazapyrenes

Full text of DOI:10.1007/s10593-012-1130-z

Chemistry of Heterocyclic Compounds, Vol. 48, No. 8, November, 2012 (Russian Original Vol. 48, No. 8, August, 2012)
LETTERS TO THE EDITOR
SYNTHESIS OF A NOVEL BIHETEROCYCLIC SYSTEM,
2,2'-BI-1,3,7-TRIAZAPYRENES
A. V. Aksenov1*, M. Kh. Magamadova1, D. A. Lobach1,
I. V. Aksenova1, and S. N. Ovcharov1
Keywords: 2,2'-biperimidine, 2,2'-bi-1,3,7-triazapyrenes, 1H-perimidines, polyphosphoric acid, 1,3,7-tri-
azapyrenes, 1,3,5-triazines, peri-annelation.
The chemistry of polyazapyrenes, which are a rather young class of compounds, continues to grow
thanks to the useful applied properties found amongst the known members of this series, i.e., anticancer activity
[1] and their ability to intercalate [2, 3]. In connection with the rapid expansion of supramolecular chemistry
over the last decades, close attention has been fixed on polyazapyrenes relating to the possible construction of
so called molecular devices [4] based on them and their use in coordination chemistry [5, 6].
We have previously reported a method for the peri-annelation of a pyridine nucleus to 1H-perimidines,
which is based on their reaction with 1,3,5-triazines in polyphosphoric acid (PPA) [7, 8].
In continuing these studies, we have carried out synthesis of 2,2'-bi-1,3,7-triazapyrenes by using 1,3,5-tri-
azines/PPA as the reagent system.
The reaction of the biperimidine 1 with a 2.5-fold excess of 1,3,5-triazines 2a-c in PPA at 100ºC (for
compound 2a) or at 130ºC (for compounds 2b,c) gave the previously unknown aromatic biheterocycles 3a-c.
R
H
N
N
N
N
PPA
+
100–130°C
5 h
N
H
N
R
N
2a–c
R
1
R
R
N
R
N
N
N
R
N
N
3a–c
2, 3 a R = H, b R = Me, c R = Ph
______
*To whom correspondence should be addressed, e-mail: alexaks05@rambler.ru.
1North Caucasus Federal University, 1a Pushkin St., Stavropol 355009, Russia.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1360-1361, August, 2012.
Original article submitted March 20, 2012.
0009-3122/12/4808-1267©2012 Springer Science+Business Media New York
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This reaction apparently occurs in full agreement with the mechanism reported in the studies [7, 8].
1H NMR spectra were recorded on a Bruker WP-200 instrument (200 MHz) using DMSO-d6 with TMS
as internal standard. Elemental analysis was carried out on a KOVO CHN-1 CHN analyzer. Melting points were
determined on a PTP-M apparatus (Khimlaborpribor). Monitoring of the reaction course and the purity of the
synthesized compounds was carried out on Silufol UV-254 plates with EtOAc–EtOH (1:1) as eluent.
2,2'-Bi-1,3,7-triazapyrenes 3a-c (General Method). A mixture of compound 1 (0.334 g, 1 mmol), the
triazine 2a-c (2.5 mmol), and 86% PPA (3-4 g) was heated with vigorous stirring for 5 h at 100ºC (for
compound 2a) or at 130ºC (for compounds 2b,c). At the end of the reaction the mixture was poured into water
(30 ml) and neutralized with ammonia solution to pH ~ 7-8. The precipitate formed was filtered off, thoroughly
washed with EtOAc and dried. The residue was purified by recrystallization from decane.
1
2,2'-Bi-1,3,7-triazapyrene (3a). Yield 0.28 g (68%). Mp > 300ºC. H NMR spectrum, , ppm (J, Hz):
8.52 (4H, d, J = 9.1, H-5,5',9,9'); 8.96 (4H, d, J = 9.1, H-4,4',10,10'); 9.86 (4H, s, H-6,6',8,8'). Found, %:
C 76.55; H 2.91; N 20.54. C26H12N6. Calculated, %: C 76.46; H 2.96; N 20.58.
1
6,8,6',8'-Tetramethyl-2,2'-bi-1,3,7-triazapyrene (3b). Yield 0.33 g (72%); mp > 300ºC. H NMR
spectrum, , ppm (J, Hz): 3.14 (12H, s, 4CH3); 8.16 (4H, d, J = 9.2, H-5,5',9,9'); 8.89 (4H, d, J = 9.2,
H-4,4',10,10'). Found, %: C 77.62; H 4.32; N 18.06. C30H20N6. Calculated, %: C 77.57; H 4.34; N 18.09.
1
6,8,6',8'-Tetraphenyl-2,2'-bi-1,3,7-triazapyrene (3c). Yield 0.55 g (77%); mp > 300ºC. H NMR
spectrum, , ppm (J, Hz): 7.62-7.76 (12H, m, H-3,4,5 Ph); 7.95 (8H, d, J = 7.3, H-2,6-Ph); 8.57 (4H, d, J = 9.2,
H-5,5',9,9'); 8.95 (4H, d, J = 9.2, H-4,4',10,10'). Found, %: C 84.31; H 3.92; N 11.77. C50H28N6. Calculated, %:
C 84.25; H 3.96; N 11.79.
This work was carried out with the financial support of the Russian Foundation for Basic Research
(grant 10-03-00193a).
REFERENCES
1.
I. Steiner-Biocic, L. Glavas-Obrovac, I. Karner, I. Piantanida, M. Zinic, K. Pavelic, and J. Pavelic,
Anticancer Res., 16, 3705 (1996).
2.
3.
4.
A. M. Brun and A. Harriman, J. Am. Chem. Soc., 113, 8153 (1991).
I. Piantanida, V. Tomisic, and M. Zinic, J. Chem. Soc., Perkin Trans. 2, 375 (2000).
V. Balzani, A. Credi, S. J. Langford, F. M. Raymo, J. F. Stoddart, and M. Venturi, J. Am. Chem. Soc.,
122, 3542 (2000).
5.
6.
7.
P. J. Stang, B. Olenyuk, J. Fan, and A. M. Arif, Organometallics, 15, 904 (1996).
P. J. Stang, D. H. Cao, S. Saito, and A. M. Arif, J. Am. Chem. Soc., 117, 6273 (1995).
A. V. Aksenov, I. V. Borovlev, I. V. Aksenova, S. V. Pisarenko, and D. A. Kovalev, Tetrahedron Lett.,
49, 707 (2008).
8.
A. V. Aksenov and I. V. Aksenova, Khim. Geterotsikl. Soedin., 167 (2009). [Chem. Heterocycl.
Compd., 45, 130 (2009)].
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