Electrolytic reduction of 2-butyne-1,4-diol as a route to trans-2-butene-1,4-diol

Article abstract of DOI:10.1134/S1070427206120287

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.

Full text of DOI:10.1134/S1070427206120287

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.
BRIEF
COMMUNICATIONS
Electrolytic Reduction of 2-Butyne-1,4-diol as a Route
to trans-2-Butene-1,4-diol
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.
DOI: 10.1134/S1070427206120287
Among the starting compounds for preparing poly-
urethanes [1], detergents, alkyd resins [2], Endosulfan
insecticide, plasticizers, and drugs [3], 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.
presence of CrSO4 on stationary solid cathodes. In
this case, the reduction of Cr2(SO4)3 to CrSO4 with
hydrogen liberated at the cathode occurs in aqueous
solution at atmospheric pressure:
2Cr3+ + H02
2Cr2+ + 2H+,
H
CH2OH
H
2H+, 2e
HOH2C C C CH2OH
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.
HOH2C
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 20 60 C, pH 2 3, cathodic
EXPERIMENTAL
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
[8]. 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.
2
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), 60 70%, with 98 99% selectivity with respect
to the desired product and 97 98% 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,
To simplify the synthesis of the target product, we
attempted electrochemical reduction of BYD in the
2037

2038
Effect of cathode material on electrolytic reduction of BED
BYD conversion BED yield based on BYD Selectivity with respect to trans-BED
PYATNITSYNA et al.
Cathode material
%
Smooth Cr18Ni10Ti steel
Copper
Porous Cr18Ni10Ti steel
Nickel
Lead
Zinc
66.8
90.0
62.5
31.5
99.2
72.6
64.0
12.2
32.5
42.5
17.3
66.1
15.5
17.3
13.5
33.7
100.0
18.1
98.8
23.7
18.0
Iron
zinc, and iron cathodes, both the product yield and the
selectivity of the cathodic reduction were low (see
table).
CONCLUSIONS
(1) Electrolytic reduction of butyne-1,4-diol on a
lead cathode is a stable process at 20 60 C and cath-
odic current density of 10 90 A dm .
For the electrochemical synthesis we used a cell in
the form of a cylindrical glass vessel (serving as a
cathode chamber) with a temperature-control jacket.
The vessel lid had opening for the anode chamber,
thermometer, current lead to the cathode, and stirrer.
The cathode and anode compartments were separated
by a porous tubular diaphragm with a blind bottom.
The anode was platinum, the anolyte was 15% sul-
furic acid, and the catholyte was purified BYD in
0.2 M chromium(III) sulfate.
2
(2) The lowest amount of the passed electricity
ensuring complete reduction of butyne-1,4-diol is
2.5 A h per gram of the starting compound; the cur-
rent efficiency by 2-butene-1,4-diol is 53%.
(3) Freshly prepared Cr2(SO4)3 solution can be
used repeatedly without a decrease in the yield of
trans-2-butene-1,4-diol.
REFERENCES
To purify BYD, a commercial solution of BYD
was boiled with activated charcoal to remove tars.
The resulting solution was evaporated in a vacuum,
and BYD was crystallized from a mixture of ethyl
acetate with methylene chloride.
1. Sokol’skii, D.V., Pak, A.M., and Ten, E.I., in Doklady
IV Vsesoyuznoi konferentsii po khimii atsetilena (Proc.
IV All-Union Conf. on Acetylene Chemistry), Alma-
Ata: Inst. Khim. Nauk Akad. Nauk Kaz. SSR, 1972,
vol. 3, pp. 254 259.
The initial and final reaction products were ana-
lyzed with a Tsvet-104 chromatograph under the fol-
lowing conditions: column length 2.0 m, inside diam-
eter 3 mm; carrier gas nitrogen; column temperature
60 200 C; support Chromaton Super 0.16 0.20 mm;
stationary phase polyethylene glycol 15000. For
better separation of cis- and trans-BED, the samples
were acetylated by the procedure described in [9].
2. FRG Patent 2412341.
3. Mel’nikov, N.N., Khimiya i tekhnologiya pestitsidov
(Chemistry and Technology of Pesticides), Moscow:
Khimiya, 1974.
4. Stepanov, N.A., Ovchinnikova, T.F., Kryukov, S.I.,
et al., in Osnovnoi organicheskii sintez i neftekhimiya:
Mezhvuzovskii sbornik nauchnykh trudov (Basic Or-
ganic Synthesis and Petroleum Chemistry: Intercol-
legiate Coll. of Scientific Works), Yaroslavl: Yaroslav.
Politekh. Inst., 1975, issue 4, pp. 39 43.
The reaction product was isolated as follows. After
the disappearance of the initial BYD from the chroma-
togram, the contents of the cathode chamber were
neutralized with a concentrated ammonia solution to
pH 8 9, after which the precipitate of chromium(III)
hydroxide was filtered off on a Buchner funnel. Water
was distilled off from the filtrate in a water-jet-pump
vacuum under heating on a water bath. The residue
was distilled in a vacuum (10 mm Hg), and the frac-
tion boiling at 125 127 C was collected. The yield of
trans-BED was about 66%. The isomeric purity of
the product exceeded 98%.
5. JPN Patent 51 18927.
6. JPN Patent 12333.
7. JPN Patent 56 18584.
8. Castro, C.E., J. Am. Chem. Soc., 1961, vol. 83,
pp. 3262 3267.
9. Dorofeenko, T.N., Zhdanov, Yu.A., Dumenko, V.I.,
et al., Khlornaya kislota i ee soedineniya v organi-
cheskom sinteze (Perchloric Acid and Its Compounds
in Organic Synthesis), Rostov-on-Don: Rostov. Gos.
Univ., 1965.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 79 No. 12 2006