Full text of DOI:10.1134/S1070363217120271

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 12, pp. 2902–2903. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © P.A. Volkov, A.A. Telezhkin, K.O. Khrapova, N.I. Ivanova, A.I. Albanov, K.A. Apartsin, N.K. Gusarova, B.A. Trofimov, 2017,
published in Zhurnal Obshchei Khimii, 2017, Vol. 87, No. 12, pp. 2091–2093.
LETTERS
TO THE EDITOR
Unexpected Carbon–Selenium Bond Formation in the Reaction
of Secondary Phosphine Selenides with Benzoylphenylacetylene
P. A. Volkova, A. A. Telezhkina, K. O. Khrapovaa, N. I. Ivanovaa, A. I. Albanova,
K. A. Apartsinb, N. K. Gusarovaa, and B. A. Trofimova*
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: boris_trofimov@irioch.irk.ru
b Irkutsk Scientific Center of Surgery and Traumatology, ul. Bortsov Revolyutsii 1, Irkutsk, 664003 Russia
Received July 13, 2017
Abstract—Secondary phosphine selenides reacted as selenating agents with benzoylphenylacetylene in wet
acetonitrile (70–72°C) to give bis(2-benzoyl-1-phenylvinyl) selenide in up to 43% yield.
Keywords: secondary phosphine selenides, benzoylphenylacetylene, bis(2-benzoyl-1-phenylvinyl) selenide
DOI: 10.1134/S1070363217120271
It is known that benzoylphenylacetylene (1,3-di-
phenylprop-2-yn-1-one) reacts with secondary phos-
phine oxides and phosphine sulfides in THF in the
presence of potassium hydroxide to give mono- and
bis-adducts at the triple bond [1, 2] and that addition
products to the carbonyl group are formed under
noncatalytic conditions [3].
selenide 2 and oxygen donor for secondary phosphine
oxides 3.
Studies of the preparative scope and mechanism of
this reaction are now in progress.
Thus, we were the first to demonstrate that
secondary phosphine selenides can act as selenating
agents with respect to benzoylphenylacetylene. As a
result, we succeeded in obtaining a functional divinyl
selenide which is a reactive bulding block for the
synthesis of promising precursors to selenium-contain-
ing medicines [4–8], ligands for metal complex catalysts
[9–12], and materials for microelectronics [13].
We have found that the reaction of benzoyl-
phenylacetylene with secondary phosphine selenides
1a and 1b follows an unexpected path leading to the
formation of bis(2-benzoyl-1-phenylvinyl) selenide (2)
and the corresponding secondary phosphine oxides 3a
and 3b which were identified by 31P NMR. The
reaction was carried out by heating the reactants for
20 h at 70–72°C in commercial acetonitrile which was
not purified preliminarily. The yield of divinyl selenide
2 was 20% in the reaction with diphenylphosphine
selenide (1a) and 25% in the reaction with bis(2-
phenylethyl)phosphine selenide (1b) (Scheme 1).
3,3'-Selanediylbis(1,3-diphenylprop-2-en-1-one)
(2). A solution of benzoylphenylacetylene (0.412 g,
0.002 mol) and secondary phosphine selenide 1a or 1b
(0.001 mol) in 3 mL of unpurified acetonitrile (contain-
ing 0.05 mmol of water) was heated for 20 h at 70–72°C.
When the reaction was complete, the 31P NMR
spectrum of the mixture displayed signals of phosphine
Presumably, the reaction involves water present in
the solvent, which acts as hydrogen donor for divinyl
1
oxide 3a (δP 21.7 ppm, JPH = 487 Hz; published data
Scheme 1.
R
Ph
Ph
R
O
H
O
Se
H
H2O_MeCN
Ph
Ph
P
P
+
+
Ph
70_72οC, 20 h
Se
Ph
R
R
O
O
2
1а, 1b
3а, 3b
R = Ph (1а, 3а), Ph(CH2)2 (1b, 3b).
2902

UNEXPECTED CARBON–SELENIUM BOND FORMATION
2903
1
[15]: δP 21.8 ppm, JPH = 481 Hz) or 3b (δP 31.2 ppm,
ACKNOWLEDGMENTS
1JPH = 452 Hz; published data [16]: δP 30.6 ppm, 1JPH
=
This study was performed under financial support
by the Council for Grants at the President of the
Russian Federation (program for state support of leading
scientific schools, project no. NSh-7145.2016.3) using
the facilities of the Baikal Joint Analytical Center
(Siberian Branch, Russian Academy of Sciences).
453 Hz) and some unidentified organophosphorus
compounds (δP 31, 45, 56, 103 ppm). The solvent was
removed under reduced pressure, and the residue was
purified by column chromatography on silica gel
(eluent benzene–Et2O, 1:2) and neutral alumina
(hexane–Et2O, 1:2). Yield 0.098 g (20%) (from 1a),
0.123 g (25%) (from 1b); mixture of E,Z and Z,Z
isomers at a ratio of 1:0.75. Found, %: C 72.98; H
4.51; Se 15.83. C30H22O2Se. Calculated, %: C 73.02; H
4.49; Se 16.00.
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E,Z Isomer. H NMR spectrum (CDCl3), δ, ppm:
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