Selenium- and tellurium-containing binucleophiles in selective synthesis of allene and methylacetylene from 2,3-dichloro-1-propene

Full text of DOI:10.1134/S1070363214010265

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 1, pp. 164–165. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © E.P. Levanova, V.S. Vakhrina, V.A. Grabel’nykh, N.V. Russavskaya, A.I. Albanov, I.B. Rozentsveig, N.A. Korchevin, 2014,
published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 1, pp. 157–158.
LETTERS
TO THE EDITOR
Selenium- and Tellurium-containing Binucleophiles
in Selective Synthesis of Allene and Methylacetylene
from 2,3-Dichloro-1-propene
E. P. Levanova, V. S. Vakhrina, V. A. Grabel’nykh, N. V. Russavskaya,
A. I. Albanov, I. B. Rozentsveig, and N. A. Korchevin
Favorskii Institute of Chemistry, Russian Academy of Sciences, Siberian Branch,
ul. Favorskogo 1, Irkutsk, 664033 Russia
е-mail: venk@irioch.irk.ru
Received August 5, 2013
DOI: 10.1134/S1070363214010265
Allene and methylacetylene are important reagents
in synthesis of unsaturated organic chemicals.
Development of synthetic methods involving them
often requires selective preparation of either allene or
methylacetylene [1]. However, these isomers are
readily interconverted or contaminated with the side
products (usually, with propylene).
Extending the studies of chalcogen-containing nucleo-
philes reactions with I, we here report on the behavior
of binucleophilic reagents, potassium 1,3-propane-
ditellurolate (IIа) and potassium 1,3-propanedi-
selenolate (IIb). Compounds IIа and IIb were pre-
pared by reductive decomposition of the respective poly-
(trimethylenedichalcogenides) [4, 5] in the hydrazine
hydrate–KOH medium. The so obtained salts IIа and
IIb were introduced in the reaction with I without isolation.
Recently, we have shown that pure allene is formed
in the reaction of K2Te2 with 2,3-dichloro-1-propene
(I) in the hydrazine hydrate – KOH medium [2]. In the
case of Se analog (K2Se2), the reaction with compound
I does not yield any gaseous products but rather gives
bis(2-chloro-1-propene-3-yl)selenide [3].
1,3-Propaneditellurolate IIа reacted with dichloro-
propene similarly to K2Te2, yielding allene (77% with
respect to I) and regenerating the initial poly(tri-
methyleneditelluride) (70% yield).
Cl
40_50oC
_2KCl
KTe
TeK
Cl
+
+
Te
Te
n
IIa
I
The so prepared allene contained only trace
amounts (< 1.0%) of methylacetylene.
To conclude, change of the chalcogen nature
allowed selective preparation of allene or methyl-
acetylene via the reaction of potassium 1,3-propane-
dichalcogenolates with 2,3-dichloro-1-propene.
Under the same conditions, 1,3-propanediselenolate
IIb yielded methylacetylene containing traces of allene
(< 0.5%). Se-containing products was a complex
mixture of organoselenium compounds, their structures
are under investigation and will be reported separately.
Allene. 4.82 g (0.016 mol) of poly(trimethylene-
ditelluride) was added to the solution of 4.55 g
(0.081 mol) of KOH in 20 mL of hydrazine hydrate
upon stirring at 85ºС. After polymer dissolution, the
reaction flask was connected to two traps (–30 and
–85ºС), and 3.6 g (0.0324 mol) of 2,3-dichloro-1-
propene was added dropwise at 40–50ºС. 1.0 g of
40_50oC
KSe
SeK
I +
_2KCl
IIb
164

SELENIUM- AND TELLURIUM-CONTAINING BINUCLEOPHILES
allene was collected in the second trap. The product
REFERENCES
165
spectral parameters were identical to those reported in
[2].
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Methylacetylene was prepared similarly from 4.0 g
(0.02 mol) of poly(trimethylenediselenide), solution of
5.61 g (0.10 mol) of KOH in 25 mL of hydrazine
hydrate, and 4.44 g (0.04 mol) of 2,3-dichloro-1-
propene. 1.0 g of methylacetylene was collected in the
1
second trap. H NMR spectrum (Bruker DPX 400,
400.13 MHz, solution in CDCl3, internal standard
TMS), δ, ppm: 1.805 s (CH≡), 1.811 s (CH3). 13С
NMR spectrum, δ, ppm: 3.16 (CH3), 67.42 (≡CH),
80.01 (–C≡).
ACKNOWLEDGMENTS
5. Russavskaya, N.V., Levanova, E.P., Sukhomazova, E.N.,
Grabel’nykh, V.A., Klyba, L.V., Zhanchipova, E.R.,
Albanov, A.I., and Korchevin, N.A., Russ. J. Gen.
Chem., 2006, vol. 76, no. 2, p. 229.
This work was partially carried out using the
facilities of the Collective Baikal Analytical Center
(Russian Academy of Sciences, Siberian Branch).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014