ISSN 0012ꢀ5008, Doklady Chemistry, 2013, Vol. 451, Part 2, pp. 201–202. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.N. Proshin, I.V. Serkov, A.V. Chernyak, S.O. Bachurin, 2013, published in Doklady Akademii Nauk, 2013, Vol. 451, No. 4, pp. 408–409.
CHEMISTRY
New Spiro Derivatives of Isoselenourea
in 1,3ꢀSelenazine Series
A. N. Proshina, I. V. Serkova, A. V. Chernyakb,
and Corresponding Member of the RAS S. O. Bachurina
Received December 3, 2012
DOI: 10.1134/S0012500813080028
In recent time, the chemistry of selenium derivaꢀ
tives is a burgeoning field of modern chemistry [1].
Selenium derivatives attract interest not only as comꢀ
pounds with unique properties but also as biologically
active substances. Thus, recent studies showed that
selenium is an important component for functioning
of many biological systems [2].
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker
CXPꢀ200 spectrometer (Germany) using deuterioꢀ
chloroform as a solvent, chemical shifts are repreꢀ
sented on the scale relative to Me4Si. Melting points
δ
were determined on a Boetius hot stage apparatus and
were uncorrected. Solutions were evaporated on a
rotary evaporator in a vacuum of a waterꢀjet pump.
We have developed a method of synthesis of previꢀ
ously unknown 2ꢀaminospiroselenazines 5a–5d,
cyclic derivatives of isoselenourea without substituents
at the bicyclic fragment of molecule. The method is
based on the intramolecular cyclization of selenoureas
Procedure for the synthesis of Nꢀsubstituted 1ꢀselꢀ
enaꢀ3ꢀazaspiro[5.5]undecꢀ2ꢀenꢀ2ꢀylamines 5a–5d
A solution of 0.01 mol of substituted arylisoselenocyꢀ
anate in 20 mL of ether was added dropwise with stirꢀ
.
3a–3d containing
γ,σꢀunsaturated fragment (Scheme 1).
ring to a solution of 2'ꢀ(cyclohexenꢀ1ꢀyl)amine
2
Isoselenocyanates 1a–1d were used as starting comꢀ
(1.25 g, 0.01 mol) in 20 mL of ether. The reaction mixꢀ
ture was stirred at ambient temperature for 2–5 h until
precipitate formed. The resulting precipitate of seleꢀ
pounds. They were obtained by refluxing a mixture of
the corresponding arylformamides, phosgene, and
selenium powder in toluene in the presence of triethyꢀ
nourea 3 was separated by filtration, dried, suspended
lamine [3, 4]. Resulting isoselenocyanates 1a
converted to substituted selenoureas 3a 3d by the
reaction with ꢀunsaturated amine, 2ꢀ(cyclohexenꢀ
1ꢀyl)amine (
–1d were
in 10 mL of 48% hydrobromic acid, and refluxed for 5 h.
After completion of the reaction, the mixture was
cooled, diluted with 20 mL of water, and 50 mL of
methylene chloride was added. The organic layer was
separated and dried with sodium sulfate. The drying
agent was separated by filtration, and the filtrate was
concentrated. The residue was recrystallized from isoꢀ
propanol to give Nꢀsubstituted 1ꢀselenaꢀ3ꢀazaꢀ
–
γ,σ
2).
The selenoureas were refluxed in 48% aqueous
hydrobromic acid. An addition of hydrogen bromide
at the double bond of the cyclohexene fragment takes
place. Resulting 1''ꢀ[2'ꢀ(1ꢀbromocyclohexyl)ethyl]ꢀ
spiro[5.5]undecꢀ2ꢀenꢀ2ꢀylamine 5 as hydrobromide.
3''ꢀarylselenoureas 4а–4d immediately undergo
intramolecular cyclization to give the corresponding
Nꢀsubstituted 1ꢀselenaꢀ3ꢀazaspiro[5.5]undecꢀ2ꢀenꢀ
2ꢀylamines 5а–5d in total yield of 60–80%.
Phenyl(1ꢀselenaꢀ3ꢀazaspiro[5.5]undecꢀ2ꢀenꢀ2ꢀ
yl)amine hydrobromide 5a. Light brown crystals, mp
147–149
°
С, yield 79%.
1H NMR (
δ
, ppm): 1.37 (m, 3H, С(8)Н2
,
a Institute of Physiologically Active Substances,
Russian Academy of Sciences, Severnyi pr. 1, Chernogolovka,
Moscow oblast, 142432 Russia
b Institute of Problems in Chemical Physics, Russian Academy
of Sciences, pr. Akademika Semenova 1, Chernogolovka,
Moscow oblast, 142432 Russia
С(7)НН), 1.69 (m, 5H, С(6)НН, С(7)НН, С(9)Н2,
С(10)НН), 2.14 (m, 4H, С(6)НН, С(10)НН,
С(5)Н2), 3.71 (m, 2H, С(4)Н2), 7.28 (m, 2H, Harom),
7.40 (m, 3H, Harom), 10.92 (s, 1H, NH), 11.26 (s,
1H, NH).
201
Proshin
