Reaction of tellurium with 2,3-dichloro-1-propene in the system hydrazine hydrate-alkali. A novel approach to synthesis of allene

Full text of DOI:10.1134/S1070363208100289

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 10, pp. 1980–1981. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © E.P. Levanova, V.Yu. Vshivtsev, V.A. Grabel’nykh, E.N. Sukhomazova, N.V. Russavskaya, A.I. Albanov, O.A. Tarasova,
N.A. Korchevin, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 10, pp. 1744–1745.
LETTERS
TO THE EDITOR
Reaction of Tellurium with 2,3-Dichloro-1-propene
in the System Hydrazine Hydrate–Alkali.
A Novel Approach to Synthesis of Allene
E. P. Levanova, V. Yu. Vshivtsev, V. A. Grabel’nykh, E. N. Sukhomazova,
N. V. Russavskaya, A. I. Albanov, O. A. Tarasova, and N. A. Korchevin
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received May 15, 2008
DOI: 10.1134/S1070363208100289
Allene is widely used in organic synthesis [1, 2]. In
laboratory or on small-scale chemical plants it is usualy
prepared by the action of zinc on 2,3-dibromo-1-propene
in alcohol solution [1, 3]. Large specific consumption of
zinc irretrievably lost in the process produces a vast
amount of highly toxic waste waters. Besides, the
formation of substantial amounts of 2-bromopropene and
propylene is observed in this method.
carbon atom. Tellurium formed in reaction (2) can be
reactivated by the system hydrazine hydrate–alkali
[reaction (1)]. Thus, in the sequence of reactions (1), and
(2), tellurium acts as a catalyst of dechlorination of 2,3-
dichloro-1-propene. No formation of allene was observed
when the reaction was carried out in the absence of
tellurium.
Allene. Reaction flask equipped with dropping
funnel, thermometer and condenser was charged with
2.8 g of KOH and 40 ml of hydrazine hydrate. The
solution formed was heated to 85°С and upon stirring
on a magnetic stirrer 6.38 g of tellurium was
introduced portionwise. The mixture was stirred during
3 h at 85–90°С, cooled to 30°С, the reaction system
was connected with two consecutively joined traps (the
first one was cooled to –35°С, the second was
graduated and cooled to –70°С) and 2.78 g of
dichloropropene (I) was added dropwise. The formed
allene was condensed in the second trap. The yield of
allene was determined by the volume of liquid (1.1 cm3)
in the trap (d4–70 0.7064 [3]). 1H NMR (CDCl3), δ, ppm:
4.65 s (=СН2). 13С NMR (CDCl3), δ, ppm: 73.70 (=СН2),
212.75 (=С=).
We found that 2,3-dichloro-1-propene (I) which is
easier available than 2,3-dibromo-1-propene readily reacts
with tellurium in the system hydrazine hydrate–KOH at
30–35°С to afford allene in 78% yield.
The process proceeds as follows. The system
hydrazine hydrate–KOH activates elemental tellurium to
form (for the molar ratio of the reagents Te : KOH = 1:1)
homogeneous solution of potassium telluride [4].
4Te + 4 KOH + N2H4·H2O → 2K2Te2 + N2 + 5H2O.
(1)
Reaction of K2Te2 with dichloropropene I gives rise
to formation of allene and complete recovery of the
starting tellurium:
K2Te2
CH2
CH2
C
CH2Cl
C
CH .
(2)
2
_2 KCl; _2 Te
NMR spectra were registered on a Bruker DPX-400
spectrometer (1Н 400.13 MHz, 13С 100.62 MHz) in
СDCl3, internal standard HMDS.
Cl
I
Reductive dehalogenation of vicinal dihalogenides
upon the action of telluride anions was mentioned earlier
[5, 6] although the described examples related to
saturated dihalogeno derivatives. In reaction (2), chlorine
is expelled both from the sp3- and the sp2-hydridized
ACKNOWLEDGMENTS
This work was financially supported by the Fund of
the President of Russian Federation for supportingo
leading scientific schools (Grant NSh-263.2008.3).
1980

REACTION OF TELLURIUM WITH 2,3-DICHLORO-1-PROPENE
1981
Afonin, A.V., Klyba, L.V., Baikalova, L.V., and
Mikhaleva, A.I., Russ. J. Org. Chem., 2003, vol. 39, no. 3,
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