ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 12, pp. 2037!2038. + Pleiades Publishing, Inc., 2006.
Original Russian Text + E.V. Pyatnitsyna, M.M. El’chaninov, A.P. Savost’yanov, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79,
No. 12, pp. 2061!2062.
Electrolytic Reduction of 2-Butyne-1,4-diol as a Route
E. V. Pyatnitsyna, M. M. El’chaninov, and A. P. Savost’yanov
South-Russian State Technical University (Novocherkassk Polytechnic Institute), Novocherkassk,
Rostov oblast, Russia
Received December 21, 2005; in final form, September 2006
Abstract-The effect of the cathode material on the electrochemical transformations of 2-butyne-1,4-diol
at atmospheric pressure was studied by chromatographic analysis. The optimal parameters of the selective
synthesis of trans-2-butene-1,4-diol were determined.
Among the starting compounds for preparing poly-
urethanes , detergents, alkyd resins , Endosulfan
insecticide, plasticizers, and drugs , compounds
containing the required functional groups are of par-
ticular importance. Among such compounds is 2-bu-
tene-1,4-diol (BED) whose synthesis by catalytic
hydrogenation of 2-butyne-1,4-diol (BYD) yields a
~90 : 10 mixture of cis and trans isomers.
With the aim to examine the effect of the trans
isomer on the properties of SKU-90 urethane rubber,
we developed in this study a procedure for regioselec-
tive synthesis of trans-BED.
Previously trans-BED has been prepared from di-
vinyl via dihalo derivatives [4, 5] and diacetoxy-2-
butene [6, 7]. The drawbacks of these methods are
multistep procedure, presence of isomers, and lacri-
mogenic properties of the intermediate dihalobutenes.
Another pathway involves chemical reduction of BYD
in a nitrogen atmosphere with chromium(II) sulfate
. However, such steps of this procedure as inter-
mediate reduction of chromium(III) sulfate with zinc
dust in a nitrogen atmosphere, followed by filtration
(also in an inert atmosphere), prevent commercial im-
plementation of the process.
To simplify the synthesis of the target product, we
attempted electrochemical reduction of BYD in the
presence of CrSO
on stationary solid cathodes. In
this case, the reduction of Cr
hydrogen liberated at the cathode occurs in aqueous
solution at atmospheric pressure:
To evaluate the qualitative and quantitative charac-
teristics of the BYD transformation, we examined the
effect of the cathode material on the electrolytic re-
duction. The electrolysis conditions were as follows:
catholyte temperature 203 60oC, pH 233, cathodic
current density 0.02 A cm
, BYD concentration
1.16 M, and cromium(III) sulfate concentration 0.2 M.
The amount of electricity passed was 300% of that
reqiured theoretically for complete conversion of
BYD into trans-BED.
The electrolytic reduction of BYD occurs on all
the electrodes examined, but only on lead cathodes
the BED yield based on BYD is reasonably high (see
table), 60370%, with 98399% selectivity with respect
to the desired product and 97398% isomeric purity.
Electrolysis on porous stainless steel provides high
selectivity with respect to the desired product, but its
yield based on BYD is lower. With copper, nickel,