Unexpected result of the reaction of 6(7)-acetyl-and 6(7)-benzoyl-1H- naphtho[1,8-de][1,2,3]triazines with vinyl butyl ether

Full text of DOI:10.1007/s10593-008-0147-9

Chemistry of Heterocyclic Compounds, Vol. 44, No. 8, 2008
UNEXPECTED RESULT OF THE
REACTION OF 6(7)-ACETYL-
AND 6(7)-BENZOYL-1H-NAPHTHO-
[1,8-de][1,2,3]TRIAZINES WITH
VINYL BUTYL ETHER
A. V. Aksenov, I. V. Aksenova, D. A. Lobach, and A. M. Zhirov
Keywords: 3H-1-azaphenalenes, vinyl butyl ether, 1H-naphtho[1,8-de][1,2,3]triazines.
Flowerday and Perkins [1] have shown that peri annelation of a carbocyclic ring may be accomplished
by means of the stepwise condensation of two carbonyl compounds with subsequent cyclization. We proposed
that the reaction of 6(7)-acetyl- and 6(7)-benzoyl-1H-naphtho[1,8-de][1,2,3]triazines with vinyl butyl ether
should lead to ring closure and formation of the corresponding 1,2,3-triazapyrenes. Unexpectedly, we found that
heating 1 mmol 1 compound with 3 mmol vinyl butyl ether 2 in benzene at reflux gave a mixture of the
corresponding acyl derivatives of 3H-1-azaphenalene 3 and 4 in quantitative yield. We were unable to separate
the mixture of isomers into pure compounds due to their similar chromatographic mobility.
N
N
N
N
N
NH
N
N
PhH
+
OBu
+
2
O
R
O
R
O
R
HO
R
1a,b
3a,b
4a,b
1–3 a R = Me, b R = Ph
This reaction probably proceeds through a set of steps involving cycloaddition and cycloelimination.
The reaction mixture of products occurs since starting triazine 1 may exist as either of two isomers due to
prototropic tautomerism in solution.
Only photochemical variants of such conversions have been reported previously [2].
The 1H NMR spectra were obtained on a Bruker WP-200 spectrometer at 200 MHz in CDCl3 with TMS
as the internal standard.
__________________________________________________________________________________________
Stavropol State University, Stavropol 355009, Russia; e-mail: k-biochem-org@stavsu.ru. Translated
from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1266-1267, August, 2008. Original article submitted
April 23, 2008.
1022
0009-3122/08/4408-1022©2008 Springer Science+Business Media, Inc.

6-Acetyl-3H-1-azaphenalene (3a, C14H11NO). 1H NMR spectrum, δ, ppm (J, Hz): 1.71 (2H, d, J = 6.1,
H-3); 2.61 (3H, s, CH3); 5.81 (1H, d, J = 6.1, H-2); 6.81 (1H, d, J = 8.2, H-4); 7.39 (1H, d, J = 7.6, H-9); 7.61
(1H, dd, J8,9 = 7.6, J7,8 = 8.2, H-8); 7.92 (1H, d, J = 8.2, H-5); 8.94 (1H, d, J = 8.2, H-7).
7-Acetyl-3H-1-azaphenalene (4a, C14H11NO). 1H NMR spectrum, δ, ppm (J, Hz): 1.71 (2H, d, J = 6.1,
H-3); 2,64 (3H, s, CH3); 5.76 (1H, d, J = 6.1, H-2); 7.02 (1H, d , J = 7.6, H-4); 7.13 (1H, d, J = 8.1, H-9); 7.42
(1H, dd, J4,5 = 7.6, J5,6 = 8.2, H-5); 7.97 (1H, d, J = 8.1, H-8); 8.51 (1H, d, J = 8.2, H-6). Found, %: C 80.53;
H 5.24; N 6.58. C14H11NO. Calculated, %: C 80.36; H 5.30; N 6.69.
1
6-Benzoyl-3H-1-azaphenalene (3b, C19H13NO). H NMR spectrum, δ, ppm (J, Hz): 1.77 (2H, d,
J = 6.4, H-3); 5.78 (1H, d, J = 6.1, H-2); 6.76 (1H, d, J = 8.2, H-4); 7.41 (1H, d, J = 7.6, H-9); 7.51-7.57 (5H, m,
H-5, H-8, 3,4,5-C6H5); 8.32 (1H, d, J = 8.2, H-7).
1
7-Benzoyl-3H-1-azaphenalene (4b, C19H13NO). H NMR spectrum, δ, ppm (J, Hz): 1.77 (2H, d,
J = 6.4, H-3); 5.79 (1H, d, J = 6.4, H-2); 6.96 (1H, d, J = 7.6, H-4); 7.13 (1H, d, J = 8.1, H-9); 7.31 (1H, dd,
J4,5 = 7.63, J5,6 = 8.2, H-5); 7.51-7.57 (4H, m, H-8, 3,4,5-C6H5); 7.8 (2H, d, J = 7.1, 2,6-C6H5); 7.97 (1H, d,
J = 8.2, H-6). Found, %: C 84.29; H 4.74; N 5.07. C19H13NO. Calculated, %: C 84.11; H 4.83; N 5.16.
REFERENCES
1.
2.
P. Flowerday and M. J. Perkins, J. Am. Chem. Soc., 91, 1035 (1969).
I. K. Lewis and R. D. Topsom, Austr. J. Chem., 923 (1965).
1023