8-Quinolineselanyl chloride in the synthesis of peri-fused selenium and nitrogen systems

Full text of DOI:10.1007/s10593-011-0815-z

Chemistry of Heterocyclic Compounds, Vol. 47, No. 5, August 2011 (Russian original Vol. 47, No. 5, May, 2011)
8-QUINOLINESELANYL CHLORIDE
IN THE SYNTHESIS OF PERI-FUSED
SELENIUM AND NITROGEN SYSTEMS
A. V. Borisov1*, Zh. V. Matsulevich1, V. K. Osmanov1, and G. N. Borisova1
Key words: alkenes, 8-quinolineselanyl chloride, heterocyclization.
In previous work [1–3], we synthesized a number of 2,3-dihydro[1,4]thiazino[2,3,4-ij]quinolinium-4
derivatives by the reaction of 8-quinolinesulfenyl chloride with alkenes. 8-Quinolineselanyl chloride (1) was
obtained in a study of the feasibility of using this method for the synthesis of analogous selenium-nitrogen-
containing heterocycles. The reactions of chloride 1 with indene 2 and styrene 3 were investigated.
The reaction of selanyl chloride 1 with unsaturated compounds 2 and 3 in methylene chloride at 20°C
leads to peri-fused systems 4 and 5 in 91 and 82% yield, respectively.
1H NMR spectroscopy showed that these reactions proceed regio- and stereospecifically.
–
Cl
–
Cl
Ph
Ph
N+
Se
H
N+
Se
3
2
N
SeCl
H
5
1
4
1
The IR spectra were taken on a Shimadzu IR-Prestige-21 spectrometer for KBr pellets. The H NMR
spectra were taken on a Bruker AM-300 spectrometer at 300 MHz in DMSO-d6 with TMS as internal standard.
8-Quinolineselanyl Chloride (1). A solution of sulfuryl chloride (0.068 g, 0.5 mmol) in methylene
chloride (15 ml) was added to a solution of di-(8-quinolinyl) diselenide (0.207 g, 0.5 mmol) prepared according
to Spyer [4] in methylene chloride (20 ml) at 20°C. After 1 h, the precipitate of chloride 1 (0.194 g, 80%) was
filtered off and the filtrate was evaporated in vacuum. Recrystallization of the residue from the methylene
_______________
*To whom correspondence should be addressed, e-mail: avb1955@rambler.ru.
1 R. E. Alekseev Nizhny Novgorod Technical University, 24 Minina Str., Nizhny Novgorod 603950, Russia.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 787–789, May, 2011. Original
article submitted April 1, 2011.
0009-3122/11/4705-0654©2011 Springer Science+Business Media, Inc.
654

chloride filtrate gave an addition 0.036 g (15%) chloride 1, mp 170–172°C. IR spectrum, , cm–1: 1618, 1589,
1533, 1373, 1273, 1194, 1039, 824, 762, 582. Found, %: C 44.47; H 2.42; N 5.75. C9H6ClNSe. Calculated, %:
C 44.58; H 2.49; N 5.78.
Reactions of 8-Quinolineselanyl Chloride 1 with Unsaturated Compounds 2 and 3. (General
Method). A solution of unsaturated compounds 2 or 3 (0.4 mmol) in methylene chloride (5 ml) was added to a
suspension of selanyl chloride 1 (0.097 g, 0.4 mmol) in methylene chloride (15 ml) at 20°C. In 48 h, after
complete dissolution of selanyl chloride 1, the solvent was evaporated in vacuum. Recrystallization of the
residue from methylene chloride gave compounds 4 or 5.
cis-8,12b-Dihydro-7aH-indeno[1',2':5,6][1,4]selenazino[2,3,4-i,j]quinolinium-13 Chloride (4) was
obtained in 91% yield; mp 230–232°C. IR spectrum, , cm–1: 1609, 1557, 1478, 1429, 1288, 1175, 788, 761.
2
2
3
1H NMR spectrum, , ppm (J, Hz): 3.27 (1H, d, J = 16.8, H-8); 3.63 (1H, dd, J = 16.8, J = 4.7, H-8); 4.88
3
3
3
3
(1H, t, J = 4.7, H-7a); 6.62 (1H, d, J = 7.6, H-12); 6.92 (1H, d, J = 4.7, H-12b); 7.16 (1H, t, J = 7.5, H-11);
7.36 (1H, t, J = 7.5, H-10); 7.50 (1H, d, J = 7.5, H-9); 7.85 (1H, t, J = 7.8, H-5); 8.25 (1H, dd, J = 7.5,
J = 1.3, H-6); 8.30 (1H, dd, J = 8.1, J = 1.3, H-4); 8.39 (1H, dd, J =8.3, J = 5.8, H-2); 9.49 (1H, dd, J = 8.4,
J = 1.4, H-3); 9.76 (1H, dd, J = 6.0, J = 1.3, H-1). Found, %: C 60.10; H 3.83; N 3.84. C18H14ClNSe.
3
3
3
3
3
3
3
3
3
Calculated, %: C 60.28; H 3.93; N 3.91.
3-Phenyl-2,3-dihydropyrido[1,4]selenazino[2,3,4,-i,j]quinolinium-4 Chloride (5) was obtained in
1
82% yield; mp 130–132°C. IR spectrum, , cm–1: 1608, 1552, 1481, 1431, 1292, 1170, 796, 765. H NMR
2
3
2
3
spectrum,, ppm (J, Hz): 3.87 (1H, dd, J = 13.2, J = 4.4, H-2); 4.12 (1H, dd, J = 13.2, J = 2.9, H-2); 6.77
3
3
3
3
(1H, t, J = 4.4, J = 2.9, H-3); 6.81, 7.07, and 7.35 (5H, all br. s, 1:1:3, C6H5); 7.89 (1H, t, J = 8.8, J = 7.3,
H-9); 8.23 (1H, dd, 3J = 8.8, 3J = 5.9, H-6); 8.33 (1H, d, 3J = 7.3, H-10); 8.45 (1H, d, 3J = 8.8, H-8); 9.45 (1H, d,
3J = 8.8, H-7); 9.63 (1H, d, J = 5.9, H-5). Found, %: C 58.81; H 3.98; N 3.95. C17H14ClNSe. Calculated, %:
3
C 58.90; H 4.07; N 4.04.
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2.
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4.
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