Synthesis of a novel heterocyclic system 6h-pyrrolo[2',3',4':4,5]naphtho[1, 8-de][1,2,3]triazines

Full text of DOI:10.1007/s10593-010-0519-9

Chemistry of Heterocyclic Compounds, Vol. 46, No. 3, 2010
SYNTHESIS OF A NOVEL HETEROCYCLIC SYSTEM
6H-PYRROLO[2',3',4':4,5]NAPHTHO[1,8-de][1,2,3]TRIAZINES
A. S. Lyakhovnenko1, A. V. Aksenov1*, and A. V. Andrienko1
Keywords: 6H-pyrrolo[2',3',4':4,5]naphtho[1,8-de][1,2,3]triazines, PPA, sodium azide, 1H-1,5,6,7-
tetraazacyclopenta[c,d]phenalenes, peri annelation, Schmidt reaction.
We have previously developed a series of methods of peri annelation of six-membered rings to a
1H-naptho[1,8-de][1,2,3]triazine [1, 2]. With the high biological activity of a significant number of indole
derivatives we have now developed a method for the peri annelation of a pyrrole ring to this compound. It was
found that the reaction of 1 mmole of ketone 1 and NaN3 (0.07 g, 1.08 mmol) in PPA* (2-3 g; the PPA used had
an 86% P2O5 content and was prepared by method [3]) at 60-70ºC for 1 h followed by addition of acetic or
benzoic acid (2 mmol) with heating at 100-110ºC for 4 h (monitoring by TLC) gave the previously unknown
1H-1,5,6,7-tetraazacyclopenta[c,d]phenalenes 3a,b in 41 and 34% yield respectively
N
N
N
N
N
NH
N
NH
N
RCO2H
PPA
NaN3
PPA
N
H
HN
O
O
R
Me
3a,b
Me
1
2
3 a R = Me, b R = Ph
The reaction included an intermediate formation of the amide 2 which could be separated.
1H NMR spectra were recorded on a Bruker WP-200 (200 MHz) instrument using DMSO-d6 with TMS
as internal standard. Monitoring of the reaction course and the purity of the synthesized compounds was carried
out on Silufol UV-254 plates with ethyl acetate as solvent. The reaction mixture was treated with water (50 ml)
and basified with ammonia solution to pH 8-9. The precipitate formed was filtered off. The mother liquor was
extracted with hot benzene (3×50 ml). The solvent was evaporated and the residue was combined with the
precipitate. The compounds obtained were purified by recrystallization.
_______
* To whom correspondence should be addressed, e-mail: k-biochem-org@stavsu.ru.
1Stavropol State University, Stavropol 355009, Russia.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 462-464. March, 2010. Original
article submitted February 2, 2010.
370
0009-3122/10/4603-0370©2010 Springer Science+Business Media, Inc.

N-(1H-Naphtho[1,8-de][1,2,3]triazin-6(7)-yl)acetamide (2). Yield 0.147 g (65%); mp 225-226ºC
(decomp., ethyl acetate). 1H NMR spectrum, , ppm (J, Hz): 2.13 (3H, s, COCH3); 6.93 (1H, d, J = 7.7, H-9(4));
7.31 (1H, dd, J = 8.4 and J = 7.7, H-8(5)); 7.38 (1H, d, J = 8.1, H-4(9)); 7.46 (1H, d, J = 8.4, H-7(6)); 8.31 (1H,
d, J = 8.1, H-5(8)); 9.60 (1H, br. s, NHCO); 11.0 (1H, br. s, NH). Found, %: C 63.87; H 4.42; N 24.68.
C12H10N4O. Calculated, %: C 63.71; H 4.46; N 24.76.
7-Methyl-6H-pyrrolo[2',3',4':4,5]naphtho[1,8-de][1,2,3]triazine (3a). Yield 0.085 g (41%); mp
1
271-273ºC (decomp., benzene). H NMR spectrum, , ppm (J, Hz): 2.96 (3H, s, CH3); 7.63 (1H, d, J = 9.0,
H-9); 7.82 (1H, d, J = 9.0, H-3); 8.34 (1H, d, J = 9.0, H-4); 8.54 (1H, d, J = 9.0, H-8); 13.1 (1H, br. s, NH).
Found, %: C 69.38; H 3.79; N 26.83. C12H8N4. Calculated, %: C 69.22; H 3.87; N 26.91.
7-Phenyl-6H-pyrrolo[2',3',4':4,5]naphtho[1,8-de][1,2,3]triazine (3b). Yield 0.092
g
(34%);
1
mp 284-286ºC (decomp., benzene). H NMR spectrum, , ppm (J, Hz): 7.55 (3H, m, H-3,4,5 Ph); 7.69 (1H, d,
J = 9.0, H-3); 7.82 (1H, d, J = 8.8, H-9); 8.21 (2H, d, J = 7.7, H-2,6 Ph); 8.38 (1H, d, J = 8.8, H-8); 8.74 (1H, d,
J = 9.0, H-4); 12.8 (1H, br. s, NH). Found, %: C 75.71; H 3.65; N 20.64. C17H10N4. Calculated, %: C 75.54;
H 3.73; N 20.73.
This work was carried out with the financial support of the Russian Fund for Basic Research (grant
No. 10-03-00193a).
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