Synthesis of the first representatives of benzannelated dihydroselenochromenes [4]

Full text of DOI:10.1007/s10593-006-0253-5

Chemistry of Heterocyclic Compounds, Vol. 42, No. 10, 2006
SYNTHESIS OF THE FIRST REPRESENTATIVES
OF BENZANNELATED DIHYDROSELENOCHROMENES
Ya. B. Drevko and O. V. Fedotova
Keywords: 1,5-diketone, zinc selenide, 5,6-dihydrobenzo[h]selenochromene.
Benzannelated 5,6-dihydrothiochromenes became available relatively recently [1], but until now their
selenium-containing analogs have been unknown.
We have for the first time realized the synthesis of 2,4-diaryl-5,6-dihydrobenzo[h]selenochromenes 1
and 2 by the reaction of 2-(1,3-diaryl-3-oxopropyl)tetrahydronaphthalen-1-ones 3 and 4 with hydrogen selenide
in situ under the conditions of acid catalysis.
Ph
Ph
ZnSe/HCl/MeOH
P(OMe)3
-p
C6H4R
Se
C H R
-p
6 4
O
O
3, 4
1, 2
1, 3 R = H, 2, 4 R = Cl
The reaction was conducted in the presence of trimethoxyphosphine, produced by the reaction of
phosphorus(III) chloride with methanol. Here the necessary concentration of hydrogen chloride (7-8 M) was
created, and the secondary disproportionation processes of the dihydrobenzoselenochromenes were suppressed
[2]. The yields of the dihydrobenzoselenochromenes 1 and 2 amounted to 91 and 67% respectively.
Chromato-mass spectrometric investigations showed that thermal isomerization of the
dihydrobenzoselenochromene 1 occurs under the conditions of GLC (EI 70 eV, 280°C) with the formation of
four isomers (molecular ion m/z 400 for the Se80 isotope). In addition, the chromatogram contains signals for two
products with molecular ions m/z 398 and 402 (for Se80), which by analogy with 2,4-diphenyl-5,6-
dihydrobenzo[h]thiochromene [1] probably result from the disproportionation of compound 1 with the
participation of the heterocyclic and alicyclic fragments.
1
The H NMR spectra were recorded in CDCl3 on a Varian FT-80a instrument (80 MHz) with TMS as
internal standard.
2,4-Diphenyl-5,6-dihydrobenzo[h]selenochromene (1). To methanol (20 ml), placed in a flask with the
minimum amount of free space, we added with constant stirring and cooling PCl3 (9.42 g, 68 mmol), compound
3 (1.42 g, 4 mmol), and ZnSe (0.72 g, 5 mmol). The mixture was stirred at room temperature for 7 h. The
separated crystals were removed, washed with ethanol, and dried. We obtained 1.27 g of compound 1. The
__________________________________________________________________________________________
N. G. Chernyshevskii Saratov State University, Saratov, Russia; e-mail: drevko777@mail.ru,
fedotova_ov@rabmbler.ru, dekanat@chem.sgu.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii,
No. 10, pp. 1586-1587, 2006. Original article submitted June 6, 2006.
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0009-3122/06/4210-1372©2006 Springer Science+Business Media, Inc.

mixture was extracted with diethyl ether (50 ml), the extract was washed with water to a neutral reaction and
dried, and the solvent was evaporated. The oily product was passed through a column of Al2O3 (eluent 10:1
hexane–ether). A further 0.17 g of compound 1 was obtained (total yield 91%); mp 108-109°C (reprecipitated
1
from diethyl ether with ethanol). H NMR spectrum, δ, ppm (J, Hz): 6.87-7.49 (14H, m HAr); 6.30 (1H, d,
J = 5.8, β-H); 4.37 (1H, d, J = 5.8, γ-H); 2.88-2.67 (2H, m, CH2) 2.38-2.19 (2H, m, CH2). Found %: C 74.95;
H 5.27. C25H20Se. Calculated %: C 75.19; H 5.01.
2-(4-Chlorophenyl)-4-phenyl-5,6-dihydrobenzo[h]selenochromene (2). This compound was obtained
similarly to compound 1, and the reaction took 37 h. Yield 67%; mp 126-128°C (reprecipitated from diethyl
ether with ethanol). 1H NMR spectrum, δ, ppm (J, Hz): 7.05-7.49 (13H, m, HAr); 6.24 (1H, d, J = 5.4, β-H); 4.34
(1H, d, J = 5.9, γ-H), 2.86-2.49 (2H, m, CH2); 2.35-1.97 (2H, m, CH2). Found %: C 69.03; H 4.66. C25H19ClSe.
Calculated %: C 69.20; H 4.38.
The work was carried out with financial support from the Russian Fundamental Research Fund (grant
06-03-3266a).
REFERENCES
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2.
O. V. Fedotova, A. P. Kriven'ko, and V. G. Kharchenko, Zh. Org. Khim., 14, 1782 (1978).
B. I. Drevko, M. A. Suchkov, A. E. Filimonov, and V. G. Kharchenko, Zh. Obshch. Khim., 69, 84
(1999).
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