ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 4, pp. 585−589. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © M.M. El’chaninov, E.V. Pyatnitsyna, I.M. El’chaninov, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 4, pp. 553−557.
ORGANIC SYNTHESIS AND INDUSTRIAL
Step Mechanism of 1-Butanol Formation in the Course
of Liquid-Phase Catalytic Hydrogenation
M. M. El’chaninov, E. V. Pyatnitsyna, and I. M. El’chaninov
Platov South-Russian State Polytechnic University (Novocherkassk Polytechnic Institute),
ul. Procveshcheniya 132, Novocherkassk, Rostov oblast, 346428 Russia
Received February 3, 2015
Abstract—Exhaustive hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol on suspended palladium and Raney
nickel catalysts under atmospheric pressure at 40°C was studied with the aim to determine the mechanism of
1-butanol formation. The previously unknown pathway of 1-butanol synthesis is realized under these conditions.
The content of 1-butanol precursors in hydrogenation catalyzates was estimated by gas–liquid chromatography.
The graphic dependence of the content of the intermediates and 1-butanol on time was found. The possibility of
increasing the hydrogenation selectivity on Raney Ni catalysts with respect to the target product was revealed.
The selectivity of hydrogenation of 2-butyne-1,4-
diol (BYD) to 1,4-butanediol (BAD) is determined by
high rage of hydrogenation of the labile intermediate,
2-butene-1,4-diol (BED), on the majority of nickel,
copper, platinum, palladium, and other catalysts [1–3].
However, in most cases the reaction selectivity decreased
because of the 1-butanol formation.
In this study we examined the mechanism of formation
of this by-product, decreasing the target product yield.
To this end, we critically analyzed the published and
newly obtained experimental data on the transformations
of BYD under the conditions of catalytic hydrogenation
on palladium (Pd/C-2) and Raney nickel catalysts.
According to the published data , hydrogenation of
acetylenic glycol 1 occurs in steps with the formation
of BED (2), which either takes up the second mole
of hydrogen to form BAD (3) or isomerizes into
γ-hydroxybutyraldehyde (HBA), which successively
1 2 3
2 4 5
5 6 7