Synthesis of 1-thia-5,7-diazacyclopenta-[c,d]phenalenes, a new heterocyclic system

Full text of DOI:10.1007/s10593-010-0623-x

Chemistry of Heterocyclic Compounds, Vol. 46, No. 8, 2010
SYNTHESIS OF 1-THIA-5,7-DIAZACYCLOPENTA-
[c,d]PHENALENES, A NEW HETEROCYCLIC SYSTEM
A. S. Lyakhovnenko1, A. V. Aksenov1**, A. V. Andrienko1, and I. V. Aksenova1
Keywords: benzoic acid, 1-perimidines, PPA, 1-thia-5,7-diazacyclopenta[c,d]phenalenes, peri annelation,
benzoylation.
In previous work, we developed a number of methods for the peri annelation of the pyrrole ring to give
perimidines [1, 2]. The considerable biological activity of thiophene derivatives has led us to develop a method
for the peri annelation of the thiophene ring to give perimidines. Heating thiols 1 (1 mmol) and benzoic acid
(0.244 g, 2 mmol) in PPA* (2-3 g) at 100-110°C for 4 h with monitoring by thin-layer chromatography gave
previously unreported 1-thia-5,7-diazacyclopenta[c,d]phenalenes 2a,b in 78 and 82% yield, respectively.
R
R
N
S
N
N
NH
SH
PhCOOH
PPA
Ph
1a,b
2a,b
1, 2 a R = Н, b R = Ме
The 1H NMR spectra were taken on a Bruker WP-200 spectrometer at 200 MHz in DMSO-d6 with TMS
as the internal standard. The reaction course and purity of the products were monitored by thin-layer
chromatography on Silufol UV-254 plates with ethyl acetate as the eluent.
The reaction mixture was treated with 50 ml water and brought to pH 8-9 by adding ammonium
hydroxide. The precipitate formed was filtered off. The mother liquor was extracted with three 50-ml portions of
hot benzene. The solvent was evaporated off and the residue was combined with the precipitate. The products
obtained were purified by recrystallization.
_______
* The PPA sample used was prepared according to Uhlig [3] and contained 86% P2O5.
** 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. 8, pp. 1268-1269, August, 2010.
Original article submitted June 3, 2010.
0009-3122/10/4608-1029©2010 Springer Science+Business Media, Inc.
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2-Phenyl-1-thia-5,7-diazacyclopenta[c,d]phenalene (2a) was obtained in 78% yield (0.223 g);
mp 283-285°C (dec., benzene). 1H NMR spectrum, , ppm (J, Hz): 7.50 (3H, m, H-3, H-4, H-5 Ph); 7.81 (1H, d,
J = 9.8, H-3); 7.95 (2H, d, J = 7.7, H-2, H-6 Ph); 8.15 (1H, d, J = 9.1, H-9); 8.53 (1H, d, J = 9.8, H-4); 8.91 (1H,
d, J = 9.1, H-8); 9.58 (1H, s, H-6). Found, %: C 75.68; H 3.46; N 9.83. C18H10N2S. Calculated, %: C 75.50;
H 3.52; N 9.78.
6-Methyl-2-phenyl-1-thia-5,7-diazacyclopenta[c,d]phenalene (2b) was obtained in 82% yield
(0.246 g); mp >300°C (benzene). 1H NMR spectrum, , ppm (J, Hz): 3.12 (3H, s, CH3); 7.50 (3H, m, H-3, H-4,
H-5 Ph); 7.87 (1H, d, J = 9.8, H-3); 7.95 (2H, d, J = 7.7, H-2, H-6 Ph); 8.13 (1H, d, J = 9.1, H-9); 8.56 (1H, d,
J = 9.8, H-4); 8.90 (1H, d, J = 9.1, H-8). Found, %: C 76.12; H 3.92; N 9.28. C19H12N2S. Calculated, %:
C 75.97; H 4.03; N 9.33.
This work was carried out with the financial support of the Russian Basic Research Fund
(Grant 10-03-00193a).
REFERENCES
1.
A. V. Aksenov, A. S. Lyakhovnenko, and I. Ts. Karaivanov, Khim. Geterotsikl. Soedin., 146 (2010).
[Chem. Heterocycl. Comp., 46, 127 (2010)].
2.
3.
A. V. Aksenov, A. S. Lyakhovnenko, A. V. Andrienko, and I. I. Levina, Tetrahedron, 51, 2406 (2010).
F. Uhlig, Angew. Chem., 66, 435 (1954).
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