Heterocyclization in the reaction of pyridine-2-selanyl chloride with styrene [11]

Full text of DOI:10.1007/s10593-007-0084-z

Chemistry of Heterocyclic Compounds, Vol. 43, No. 4, 2007
HETEROCYCLIZATION IN THE REACTION OF PYRIDINE-
2-SELANYL CHLORIDE WITH STYRENE
A. V. Borisov, Zh. V. Matsulevich, V. K. Osmanov,
T. N. Borisova, and E. V. Savikhina
Keywords: pyridine-2-selanyl chloride, styrene, cyclization.
Selanylhalides are widely used inorganic synthesis, for example, in inducing selanating electrophilic
cyclization of cyclization of unsaturated compounds with ring closure involving a nucleophilic active group in
the molecule of the substrate [1-3]. However it is possible to bring about an alternative direction of cyclization in
which a unit in the initial selanating electrophile may participate as the nucleophilic partner. According to our
research this has not been investigated. We have tested this alternative approach for the synthesis of sulfur
containing heterocycles based on the reactions of unsaturated compounds with hetarenesulfenyl chlorides with
potentially nucleophilic atoms of nitrogen or oxygen in the hetaryl unit [4-6]. Taking into account these results it
can be predicted that corresponding selenium reagents are suitable for the preparation of heterocycles containing
selenium.
In the present work we have studied the reaction of pyridine-2-selanyl chloride (1) with styrene (2). As
shown previously in the reaction of the analogous electrophile, pyridine-2-selanyl bromide reacted with styrene
in methanol to give the solvoadduct – 1-methoxy-1-phenyl-2-(2-pyridylselanyl)ethane – in quantitative yield [7].
We have established that in the reaction of the selanyl chloride 1 with styrene in methylene chloride at 20°C the
condensed heterocycle 3, the product of cyclization with ring closure at the nitrogen atom of the selenium-
containing pyridine fragment, was formed in 98% yield.
–
Cl
CH2Cl2
+
N
+
N
SeCl
2
3
1
Se
1
By monitoring with H NMR spectroscopy, it was shown that the initial product of the reaction is
1-chloro-1-phenyl-2-(2-pyridylselanyl)ethane, which undergoes intramolecular cyclization.
1H NMR spectra were recorded on a Bruker AM-300 (300 MHz) machine.
3-Phenyl-2,3-dihydro[1,3]selenazolo[3,2-a]pyridinium-4 chloride (3). A solution of alkene 2 (0.52 g,
5 mmol) in methylene chloride (20 ml) was added with stirring at 20°C to a suspension of the selanyl chloride 1
(0.96 g, 5 mmol) in methylene chloride (20 ml). After 48 h when the selanyl chloride had dissolved completely,
__________________________________________________________________________________________
Nizhny Novgorod State Technical University, Nizhny Novgorod 603606, Russia; e-mail:
ifxf@nntu.nnov.ru. Translated from Khimiya Geterotsiklicheckikh Soedinenii, No.4, 628-629, April, 2007.
Original article submitted December 7, 2006
0009-3122/07/4304-0525©2007 Springer Science+Business Media, Inc.
525

the solvent was removed in vacuum. The residue was recrystallized from methylene chloride to give compound 3
1
(1.41 g, 95%); mp 205-207°C. IR spectrum, ν, cm-1: 3016, 1605, 1551, 1465, 1431, 1273, 1159, 763, 702. H
3
3
NMR spectrum (DMSO-d6): 8.54 (1H, d, J = 5.9, Het); 8.44 (1H, d, J = 8.3, Het); 8.33 (1H, ddd, J = 8.3, J =
7.3, J = 1.2, Het); 7.74 (1H, ddd, J = 7.3, J = 5.9, J = 1.3, Het); 7.49 m and 7.40 m (5H, C6H5); 6.64 (1H, t, 3J =
2
7.4, CHN+); 4.29 dd and 3.80 dd (2H, J = 11.0, CH2Se). Found, %: C 52.35; H 4.01; N 4.62. C13H12ClNSe.
Calculated, %: C 52.64; H 4.08; N 4.72.
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