Synthesis of a new heterocyclic system, 1,2,3,7-tetraazapyrene [6]

Full text of DOI:10.1007/s10593-007-0209-4

Chemistry of Heterocyclic Compounds, Vol. 43, No. 10, 2007
SYNTHESIS OF A NEW HETEROCYCLIC
SYSTEM, 1,2,3,7-TETRAAZAPYRENE
A. V. Aksenov, I. V. Borovlev, I. V. Aksenova, and D. A. Kovalev
Keywords: 1H-naphtho[1,8-de][1,2,3]triazine, PPA, 1,2,3,7-tetraazapyrenes, 1,3,5-triazines, 1,2,3-triaza-
phenalene, ring fusion.
In previous work [1], we developed a method for the acylation (formylation) of perimidines based on
their reaction with 1,3,5-triazines 2 in PPA. We unexpectedly found that the use of
1
1
H-naphtho[1,8-de][1,2,3]triazine (1,2,3-triazaphenalene) (1) as the substrate in the reaction with substituted
,3,5-triazines leads to a change in the direction of this reaction. Thus, we discovered that heating 1
(
(
1 mmol) with 1,3,5-triazines (1.5 mmol) in 3-4 g PPA* for 1.5 h at 70°C and then for 3 h at 100°C (2a), 140°C
2b), or 150°C (2c) (isolation common for such reactions) leads to previously unreported
1
,2,3,7-tetraazapyrenes 3 in 55-64% yield. The reaction probably proceeds through the following sequence of
steps:
N
H
N
N
N
H
R
N
R
N
N
H+
N
N
PPA
+
R
R
N
H
R
1
2a-c
N
N
R
N
H
N
H
N
N
N
N
N
N
N
R
+
HN
NH2
R
R
R
+
R
N
N
NH2
R
N
R
R
N
N
NH2
R
3
a-c
2,3 a R = H, b R = Me, c R = Ph
_______
*
The sample of PPA used was prepared according to Uhlig [2] and contained 86% P O5
2
_
_________________________________________________________________________________________
Stavropol State University, Stavropol 355009, Russia; e-mail: k-biochem-org@stavsu.ru. Translated
from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1590-1591, October, 2007. Original article submitted
June 20, 2007.
0
009-3122/07/4310-1353©2007 Springer Science+Business Media, Inc.
1353

1
The H NMR spectra were taken on a Bruker WP-200 spectrometer at 200 MHz using TMS as the
internal standard.
,2,3,7-Tetraazapyrene (3a). Yield 0.132 g (64%); mp 212-214°C (ethyl acetate). H NMR spectrum in
DMSO-d , δ, ppm (J, Hz): 8.35 (2H, d, J = 9.5, H-5,9); 8.92 (2H, d, J = 9.5, H-4,10); 9.83 (2H, s, H-6,8). Found,
1
1
6
%
: C 70.06; H 2.86; N 27.08. C H N . Calculated, %: C 69.90; H 2.93; N 27.17.
12 6 4
6
,8-Dimethyl-1,2,3,7-tetraazapyrene (3b). Yield 0.129 g (55%); mp 192-194°C (ethyl acetate).
1
H NMR spectrum in CDCl , δ, ppm (J, Hz): 3.49 (6H, s, CH ); 8.40 (2H, d, J = 9.5, H-5,9); 8.81 (2H, d, J = 9.5,
3
3
H-4,10). Found, %: C 71.92; H 4.22; N 23.86. C H N . Calculated, %: C 71.78; H 4.30; N 23.92.
1
4
19
4
6
,8-Diphenyl-1,2,3,7-tetraazapyrene (3c). Yield 0.208 g (58%), mp 205-207°C (ethyl acetate).
H NMR spectrum in CDCl , δ, ppm (J, Hz): 7.61 (6H, m, 3,4,5-C ); 7.96 (4H, d, J = 7.4, 2,6-C ); 8.33
2H, d, J = 9.5, H-5,9); 8.79 (2H, d, J = 9.5, H-4,10). Found, %: C 80.63; H 3.88; N 15.49. C H N . Calculated,
1
3
6
H
5
6 5
H
(
2
4
14
4
%: C 80.43; H 3.94; N 15.63.
REFERENCES
1
2
.
.
A. V. Aksenov, I. V. Borovlev, A. S. Lyakhovnenko, and I. V. Aksenova, Khim. Geterotsikl. Soedin.,
29 (2007). [Chem. Heterocycl. Comp., 43, 527 (2007)].
F. Uhlig, Angew. Chem., 66, 435 (1954).
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