Synthesis of derivatives of a new heterocyclic systems - 7-Thia-5,8,11-triazaindeno[1,2-c]fluorene [8]

Full text of DOI:10.1007/s10593-007-0081-2

Chemistry of Heterocyclic Compounds, Vol. 43, No. 4, 2007
SYNTHESIS OF DERIVATIVES OF A NEW HETEROCYCLIC
SYSTEMS – 7-THIA-5,8,11-TRIAZAINDENO[1,2-c]FLUORENE
V. V. Dotsenko1, S. G. Krivokolysko1, and V. P. Litvinov2*
Keywords: 7-thia-5,8,11c-triazaindeno[1,2-c]fluorine, thieno[2,3-b]pyridines, phthalic anhydride,
cyclocondensation.
Interest in the chemistry of derivatives of thieno[2,3-b]pyridine is linked, in the first place, to their
accessibility, and also to the broad potential of the practical use of compounds of this class [1]. In a continuation
of our investigations in the field of synthesis of condensed thienopyridines [2] we decided to study the
possibility of polycyclic products under conditions of cyclocondensation of phthalic anhydride with
thieno[2,3-b]pyridine 1, which is readily prepared from the thiolate 2 and α-chloroacetamide under Thorpe-
Ziegler conditions [3]. It was established that in boiling AcOH the reaction stopped at the stage of the
formation of the 3-phthalimido derivative 3 in 81% yield, whereas in boiling DMF a deeper condensation
occurred to give a derivative of a new heterocyclic system – 7-thia-5,8,11c-triazindeno[1,2-c]fluorene 4.
Ph
Ph
N
NH2
NH2
ClCH2CONH2
DMF, KOH
Me
S
O
O
N
H
O
N
H
S
NH+
O
1
2
O
O
O
DMF
O
AcOH
1
O
12
2
3
Ph
Ph
11c
11
9
N
11a
7a
N
O
11b
4a
10
4
O
5
N
6a
S
O
N
H
S
O
N
6
CONH2
7
H
8
3
4
_______
* Deceased
__________________________________________________________________________________________
1"ChemEx" Laboratory, Vladimir Dal' East-Ukrainian National University, Lugansk 91034, Ukraine;
2
e-mail: ksg@lep.lg.ua. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow
117913; e-mail: vpl@mail.ioc.ru Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 623-624,
April, 2007. Original article submitted September 28, 2006.
0009-3122/07/4304-0519©2007 Springer Science+Business Media, Inc.
519

Evidently the temperature and the low solubility of compound 3 in AcOH have an important influence on the
course of the condensation process.
1H NMR spectra of DMSO-d6 solutions with TMS as internal standard were recorded with a Varian
Gemini 200 (200 MHz) instrument. IR spectra of nujol mulls were recorded with an IKC-29 spectrophotometer.
Elemental analyses were carried out with a Perkin-Elmer CHN analyzer. The thiolate 2 was prepared by a known
method [4].
3-Amino-6-oxo-4-phenyl-4,5,6,7-tetrahydrothieno[2,3-b]pyridine-2-carboxamide (1) was obtained
by a modified procedure [3]: 10% KOH (15.7 ml, 30 mmol) was added to a solution of thiolate 2 (10 g,
30 mmol) in DMF (30 ml), and stirred with heating until solution was complete. The mixture was filtered to
α-chloroacetamide (3.0 g, 32 mmol) in DMF (5 ml), heated to boiling, stirred at ~50°C for 3 h, kept over night,
then more 10% KOH (15.7 ml) was added, boiled for 5 min, kept for 2 d, and then diluted with water (200 ml).
The precipitate which formed over 7 d was filtered off and washed with water. Yield 80%; mp 258-260°C (from
1
3:1 EtOH–AcOH). IR spectrum, ν, cm-1: 1677, 1644 (2C=O) 3165, 3305, 3455, 3483 (NH, 2 NH2). H NMR
spectrum, δ, ppm (J, Hz): 10.65 (1H, s, NH); 7.29-7.13 (5H, m C6H5); 6.44 (2H, br. s, CONH2); 6.32 (2H, br. s,
NH2); 4.27 (1H, br. pseudo d, H-4); 3.10 (1H, dd, 2J = 16.2, 3J = 7.6, H-5); 2.64 (1H, br. pseudo d, 2J = 16.2, H-
5). Found, %: C 58.98; H 4.58; N 14.58. C14H13N3O2S. Calculated, %: C 58.52; H 4.56; N 14.62.
6-Oxo-4-phenyl-3-phthalimido-4,5,6,7-tetrahydrothieno[2,3-b]pyridine-2-caroxamide
(3).
A
mixture of thienopyridine 1 (1.3 g, 3.5 mmol) and phthalic anhydride (1.3 g, 8.8 mmol) in AcOH (15 ml) was
boiled with stirring for 4 h, kept for 24 h at ~20°C, the precipitate was filtered off, and washed with hot EtOH to
give pure thienopyridine 3 as white crystals (1.18 g, 81), mp 350-355°C (dec). IR spectrum, ν, cm-1: broad
1
absorption band 1724-1643 (4C=O), 3150, 3373 (NH, NH2). H NMR spectrum, δ, ppm (J, Hz): 10.96 (1H, s,
NH); 7.79-7.65 (4H, m, Arphthalimid); 7.28 (2H, br. s, CONH2); 697-6.80 (5H, m, C6H5); 4.09 (1H, br. pseudo d,
H-4); 2.85-2.63 (2H, m, H-5). Found, %: C 63.66; H 3.63; N 10.03. C22H15N3O4S. Calculated, %: C 63.30;
H 3.62; N 10.07.
6,9,12-trioxo-11-phenyl-8,9,10,11-tetrahydro-6H,12H-7-thia5.8.11c-triazaindeno[1,2-c]fluorine 4.
A mixture of thienopyridine 1 (1 g, 3.5 mmol) and phthalic anhydride (1.3 g, 8.8 mmol) in DMF (13 ml) was
boiled for 10 h, kept for 24 h at ~20°C, the bright yellow product was filtered off and washed with hot EtOH.
Yield 0.74 g (53%); mp >350°C (from DMF). IR spectrum, ν, cm-1: 1773, 1696, 1677 ( 3C=O, C=N). 1H NMR
spectrum, δ, ppm (J, Hz): 11.25 (1H, s, NH); 7.97-7.77 (4H, m, Arphthalimid); 7.37-7.21 (5H, m, C6H5); 4.66 (1H,
br. pseudo d, H-4); 3.25-2.63 (2H, m, overlapping signals, H-5). Found, %: C 65.41; H 3.30; N 10.62.
C22H15N3O3S. Calculated, %: C 66.16; H 3.28; N 10.52.
This work was carried out as part of an agreement on scientific-technological cooperation between
Vladimir Dal' Eastern-Ukrainian National University (Lugansk, Ukraine) and the N. D. Zelinsky Institute of
Organic Chemistry, Russian Academy of Sciences and an Russian Fundamental Research Fund project
(No. 05-03032031).
REFERENCES
1
V. P. Litvinov, V. V. Dotsenko, and S. G. Krivokolysko, Chemistry of Thienopyridines and Related
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2
V. V. Dotsenko, S. G. Krivokolysko, A. N. Chernega, and V. P. Litvinov, Izvest. Akad. Nauk, Ser.
Khim., 918 (2003).
3
V. V. Dotsenko, S. G. Krivokolysko, and V. P. Litvinov, Khim. Geterotsikl. Soedin., 117 (2003).
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4
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