Synthesis of 2-(vinylselanyl)pyridine

Full text of DOI:10.1134/S1070428015030288

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 3, pp. 443–444. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.A. Potapov, D.A. Malinovich, S.V. Amosova, K.K. Bhasin, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51,
No. 3, pp. 456–457.
SHORT
COMMUNICATIONS
Synthesis of 2-(Vinylselanyl)pyridine
V. A. Potapova, D. A. Malinovichb, S. V. Amosovaa, and K. K. Bhasinc
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: amosova@irioch.irk.ru
b Ezhevskii Irkutsk State Agricultural University, Molodezhnyi, Irkutsk oblast, 664038 Russia
c Department of Chemistry and Centre of Advanced Studies in Chemistry, Panjab University,
Chandigarh, 160014 India
Received November 21, 2014
DOI: 10.1134/S1070428015030288
Vinylselanyl derivatives are important intermediate
products and building blocks in modern organic syn-
thesis [1]. The main procedure for their preparation is
based on nucleophilic addition of organylselenolate or
selenide ions to acetylenes [1–3]. Organylselenolate
ions can be generated in situ by reduction of organic
diselenides [1, 2]. We have developed efficient meth-
ods for the preparation of divinyl selenide [4–6] and
alkyl vinyl selenides [7, 8] via nucleophilic addition of
selenolate and selenide ions.
Compound 1 is formed in four steps. The first step
is generation of potassium diselenide from elemental
selenium by the action of potassium hydroxide and
hydrazine hydrate. In the second step, potassium
diselenide reacts with 2-bromopyridine to give bis-
(pyridin-2-yl) diselenide (2). Diselenide 2 is then
reduced to potassium pyridine-2-selenolate with hydra-
zine in the presence of KOH, and the final step is
nucleophilic addition of pyridine-2-selenolate to acety-
lene (Scheme 2).
The second method is based on the reaction of
acetylene with bis(pyridin-2-yl) diselenide (2) in the
same basic reducing systems. This method ensures
formation of 1 in 82–90% yield.
Selenium is an important trace element, and many
organoselenium compounds exhibit high biological
activity [9]. Many drugs contain a pyridine ring which
may be regarded as a pharmacophoric group. Vinyl-
Prior to our studies, 2-(vinylselanyl)pyridine (1)
was not reported in the literature. We have developed
two procedure for the synthesis of this compound.
One-pot reaction of elemental selenium with acetylene
and 2-bromopyridine in a basic reducing system
(BRS), KOH–DMSO (DMF, HMPA)–N2H4–H2O,
afforded 40–52% of 1 (Scheme 1). The best yield of 1
(52%) was obtained in HMPA.
Scheme 1.
100–150°C
80–110°C
+
Se
+
HC CH
+ HC CH
N
Br
N
Se
N
+
Se Se
N
CH2
1
2
Scheme 2.
4Se
+
N2H4
+
4KOH
2K2Se2
+
4H2O
N2
Solv
140–150°C
BRS
80–110°C
HC CH
H2O
2
+ K2Se2
2
N
Br
N
Se Se
N
N
SeK
N
Se
CH2
2
1
BRS stands for basic reducing system: KOH–Solv–N2H4–H2O, Solv = DMSO, DMF, HMPA.
443

POTAPOV et al.
444
selanyl group can be subjected to functionalization, in
particular it can be involved in electrophilic additions
to a double bond [10]. Compound 1 is a promising
intermediate product for organic synthesis, and its
availability opens prospects in obtaining new biologi-
cally active alkylselanylpyridines.
The spectral data were obtained using the equip-
ment of the Baikal Joint Analytical Center (Siberian
Branch, Russian Academy of Sciences). This study
was performed under financial support by the Russian
Foundation for Basic Research (project no. 14-03-
92705_Ind).
2-(Vinylselanyl)pyridine (1). A mixture of 7.9 g
(0.1 mol) of selenium, 9.2 g (0.14 mol) of 85% KOH,
12 mL of hydrazine hydrate, 17.4 g (0.11 mol) of
2-bromopyridine, and 100 mL of anhydrous HMPA
was heated for 5 h at 140–150°C in a rotating high-
pressure reactor. The mixture was left overnight, a so-
lution of 20 g (3 mol) of 85% KOH in 20 mL of water
and 20 mL of hydrazine hydrate were added, and the
mixture was heated for 5 h at 100–110°C in a rotating
high-pressure reactor while supplying acetylene to
a pressure of 12 atm. The mixture was diluted with
water and extracted with ethyl acetate, the organic
phase was washed with water and dried over Na2SO4,
and the solvent was distilled off. The residue was
purified by column chromatography (silica gel; chloro-
form–hexane, 3:1). Yield 9.57 g (52%), light yellow
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