Unexpected reaction of 1,8-naphthylenediamine and perimidines with 1,3,5-triazine in the presence of benzonitrile in polyphosphoric acid

Full text of DOI:10.1007/s10593-008-0127-0

Chemistry of Heterocyclic Compounds, Vol. 44, No. 7, 2008
UNEXPECTED REACTION
OF 1,8-NAPHTHYLENEDIAMINE
AND PERIMIDINES WITH 1,3,5-TRIAZINE
IN THE PRESENCE OF BENZONITRILE
IN POLYPHOSPHORIC ACID
I. V. Aksenova, A. V. Aksenov, A. S. Lyakhovnenko, and I. V. Borovlev
Keywords: benzonitrile, 1,8-naphthylenediamine, perimidines, PPA, 1,3,7-triazapyrenes, 1,3,5-triazine,
annelation.
We have developed a method for the acylation (formylation) of perimidines based on their reaction with
1,3,5-triazines 2 [1], and 1,3,7-triazapyrenes, based on the reaction of 1,8-naphthalenediamine (1) with nitriles in
PPA [2]. In the reaction of diamine 1 (1 mmol) with 1,3,5-triazine 2 (3 mmol) and benzonitrile (5 mmol) in
3-4 g PPA* at 70-80°C for 8 h (separation is normal for similar reactions) 6-phenyl-1,3,7-triazapyrene (4a)
(72%) was isolated from an unexpected mixture of products. It is probable that the reaction went via the
intermediate formation of the perimidine 3a, because when the compounds 3a-c were used in this reaction (with
2 mmol of compound 2), the triazapyrenes 4a-c were isolated in 71-75% yield.
R
R
N
N
NH
NH2
N
NH2
N
PPA
2, PhCN
+
N
N
PPA
Ph
1
3a–c
3, 4 a R = H, b R = Me, c R = Ph
2
N
4a–c
1H NMR spectra were recorded with a Bruker WP-200 (200 MHz) spectrometer with TMS as internal
standard. Mass spectra were recorded with a MAT-311A instrument. The reactions and the purity of the
synthesized products were controlled on Silufol UV-254 plates with ethyl acetate as solvent. Column
chromatography was carried out on L 40/100 silica gel, with ethyl acetate as eluent.
_______
* The PPA used, made by a standard method [3], contained 86% P2O5.
__________________________________________________________________________________________
Stavropol State University, Stavropol 355009, Russia; e-mail: k-biochem-org@stavsu.ru. Translated
from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1106-1107, July, 2008. Original article submitted
October 14, 2007.
0009-3122/08/4407-0891©2008 Springer Science+Business Media, Inc.
891

6-Phenyl-1,3,7-triazapyrene (4a). Yield from perimidine was 0.211 g (75%), from 1,8-naphthalene-
1
diamine 0.2 g (71%); mp 174-176°C (nonane). H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 7.68 (3H, m,
3,4,5-C6H5); 7.91 (2H, br. d, J = 8.0, 2,6-C6H5); 8.29 (1H, d, J9,10 = 9.5, H-10); 8.33 (1H, d, J4,5 = 9.1, H-4); 8.75
(1H, d, J9,10 = 9.5, H-9); 8.91 (1H, d, J4,5 = 9.1, H-5); 9.86 (1H, s, H-8); 9.89 (1H, s, H-2). Mass spectrum (70
eV), m/z (Irel, %): 281 [M]+ (100). Found, %: C 81.27; H 3.87; N 14.86. C19H11N3. Calculated, %: C 81.12;
H 3.94; N 14.94.
1
2-Methyl-6-phenyl-1,3,7-triazapyrene (4b). Yield 0.21 g (71%); mp 246-248°C (nonane). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 3.19 (3H, s, CH3); 7.63 (3H, m, 3,4,5-C6H5); 7.88 (2H, dd, J = 8.1, J = 1.3,
2,6-C6H5); 8.18 (1H, d, J9,10 = 9.5, H-10); 8.24 (1H, d, J4,5 = 9.2, H-4); 8.60 (1H, d, J4,5 = 9.2, H-5); 8.76 (1H, d,
J9,10 = 9.5, H-9); 9.69 (1H, s, H-8). Found, %: C 81.44; H 4.38; N 14.18. C20H13N3. Calculated, %: C 81.34;
H 4.44; N 14.23.
1
2,6-Diphenyl-1,3,7-triazapyrene (4c). Yield 0.264 g (74%); mp 197-199°C (nonane). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.63 (6H, m, 3,4,5-(2)C6H5, 3,4,5-(6)C6H5); 7.90 (2H, dd, J = 8.1, J = 1.6,
2,6-(6)C6H5); 8.30 (1H, d, J9,10 = 9.5, H-10); 8.35 (1H, d, J4,5 = 9.2, H-4); 8.63 (1H, d, J4,5 = 9.2, H-5); 8.76 (1H,
d, J9,10 = 9.5, H-9); 8.84 (2H, dd, J = 8.1, J = 1.6, 2,6-(2)C6H5); 9.68 (1H, s, H-8). Found, %: C 84.14; H 4.19;
N 11.67. C25H15N3. Calculated, %: C 84.01; H 4.23; N 11.76.
REFERENCES
1.
2.
3.
A. V. Aksenov, I. V. Borovlev, A. S. Lyakhovnenko, and I. V. Aksenova, Khim. Geterotsikl. Soedin.
629 (2007). [Chem. Heterocycl. Comp., 43, 527 (2007)].
I. V. Aksenova, I. V. Borovlev, A. S. Lyakhovnenko, S. I. Pisarenko, and A. V. Aksenov, Khim.
Geterotsikl. Soedin. 788 (2007). [Chem. Heterocycl. Comp., 43, 665 (2007)].
F. Uhlig, Angew. Chem., 66, 435 (1954).
892