Step mechanism of 1-butanol formation in the course of liquid-phase catalytic hydrogenation of 2-butyne-1,4-diol

Article abstract of DOI:10.1134/S1070427215040059

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.

Full text of DOI:10.1134/S1070427215040059

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
ORGANIC CHEMISTRY
Step Mechanism of 1-Butanol Formation in the Course
of Liquid-Phase Catalytic Hydrogenation
of 2-Butyne-1,4-diol
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
e-mail: elchaninov-43@mail.ru
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.
DOI: 10.1134/S1070427215040059
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.
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 [4], 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
In this study we examined the mechanism of formation
of this by-product, decreasing the target product yield.
H2
(1)
Cat
H2
Cat
1
2
3
H2
H2O
(2)
Cat
Cat
2
4
5
H2
Cat
H2
(3)
Cat
5
6
7
585

586
EL’CHANINOV et al.
Table 1. Physicochemical characteristics of compounds 2 and 8–10
Compound
Parameter
2-Butene-1,4-diol (2) [5, 6]
Liquid with characteristic odor. Exists as trans and cis isomers.
Boiling point, °C/mmHg (MPa):
mixture of isomers: from 232 to 235/760 (0.1)
from 105 to 107/2 (0.0003)
cis isomer: 235/760 (0.1); 132/16 (0.002)
trans isomer: 131/13 (0.002); from 125 to 127/10 (0.001)
Refractive index:
mixture of isomers: from 1.476 to 1.478
cis isomer: 1.4782
trans isomer: 1.4755
Density at 20°C, g cm–3:
mixture of isomers: from 1.067 to 1.074
cis isomer: 1.0698
trans isomer: 1.0800
Crystallization point, °C:
cis isomer: 4
trans isomer: 25
2,3-Butadien-1-ol (8) [7]
Transparent lacrimatory liquid with sharp odor.
Boiling point, °C/mmHg (MPa):
from 140 to 140.5/780 (0.1)
from 126 to 127/756 (0.1)
from 68 to 70/57 (0.008)
from 68 to 69/45 (0.006)
Refractive index: 1.4759
Density at 20°C, g cm–3: 0.9164
2-Buten-1-ol (9) [8, 9]
Transparent lacrimatory liquid with sharp odor.
Boiling point, °C/mmHg (MPa):
cis isomer: from 122 to 123/760 (0.1)
trans isomer: 121.2/760 (0.1)
Refractive index:
cis isomer: 1.4342
trans isomer: 1.4285
Density at 20°C, g cm–3:
cis isomer: 0.8662
trans isomer: 0.8532
3-Buten-1-ol (10) [10]
Transparent colorless liquid with specific odor.
Boiling point, °C/mmHg (MPa): from 112.5 to 113.5/755 (0.1)
Refractive index: 1.4227
Density at 20°C, g cm–3: 0.8454
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 4 2015

STEP MECHANISM OF 1-BUTANOL FORMATION
587
transforms into 2-butenal (5), 1-butanal (6), and, finally,
1-butanol (7) (BTN).
and dehydration of 2-butene-1,4-diol (2) via С–ОН bond
into allenic alcohol, 2,3-butadien-1-ol (8), followed by its
hydrogenation into 3-buten-1-ol (9) or 2-buten-1-ol (crotyl
alcohol) (10) and then into 1-butanol (7):
As we found, 1-butanol (7) is also formed via one more,
previously unknown, pathway. It involves hydrogenolysis
H2O
Cat
(4)
2
8
9, 10
These intermediates were identified using reference
samples. The physicochemical characteristics of com-
pounds 2 and 8–10 are given in Table 1. Their content in
hydrogenation catalyzates was estimated by gas–liquid
chromatography.
end, we performed exhaustive hydrogenation of BYD at
40°С in a 100 cm3 long-necked reactor fixed in a shaking
machine. The required temperature in the reactor and buret
was maintained by feeding temperature-controlled water
into their jackets. The reactor was charged with 1.32 g of
crystalline BYD, 20 cm3 of water, and calculated amount
of finely dispersed catalyst (10 wt % relative to BYD). The
reaction completion was judged from the hydrogen uptake,
measured with a 300 cm3 gas buret. The Pd/C-2 catalyst
(2.0 wt % Pd on OUB coal) was prepared by application of
palladium(II) chloride from its hydrochloric acid solution
onto the support, followed by the palladium reduction to
metal with formaldehyde [12]. Selective nickel catalyst
W-6 was prepared by leaching of Raney nickel–aluminum
alloy with a 20 wt % NaOH solution [13].
EXPERIMENTAL
The hydrogenation catalyzates were analyzed on a
Tsvet-100М-152 chromatograph equipped with a flame
ionization detector. A metal column 2 m long and 3 mm
in diameter was packed with Chromaton N-Super or
N-AW-DMCS, fraction 0.16–0.20 mm, impregnated
with 15% polyethylene glycol (PEG) of molecular mass
15 000–20 000.
The kinetic curves of BYD consumption and accu-
mulation of the major hydrogenation products (BTN,
HBA, BED, BAD) on the above-indicated catalysts were
presented previously [11]. This study was focused exclu-
sively on intermediates of the 1-butanol synthesis. To this
The graphic dependences of the relative amounts
of the intermediates and 1-butanol on time were
constructed (Table 2; Figs. 1a, 1b). The composition of
the intermediates shows that 4-hydroxy-1-butanal (4)
c, wt %
(b)
(a)
c, wt %
τ, min
τ, min
Fig. 1. Kinetic curves of accumulation of intermediates preceding 1-butanol formation. (c) Concentration and (τ) time. Catalyst:
(a) Pd/C-2 and (b) Raney nickel. (a) (1) 2-buten-1-ol, (2) 3-buten-1-ol, (3) 2,3-butadien-1-ol, (4) 4-hydroxybutanal, and (5) 1-butanol;
(b) (1) 2-buten-1-ol, (2) 3-buten-1-ol, (3) 2,3-butadien-1-ol, (4) 2-butenal, and (5) 1-butanol.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 4 2015

588
EL’CHANINOV et al.
Table 2. Variation with time of the composition of intermediates preceding 1-butanol formation in the course of BYD
hydrogenation at 40°C
Weight fraction of reaction products in hydrogenation catalyzates, %
Pd/C catalyst (POUB-2)
Raney Ni catalyst
τ, min
2-buten- 3- buten- 2,3-butadien- 4-hydroxy-
2-buten- 3- buten- 2,3-butadien-
1-butanol
2-butenal 1-butanol
1-ol
1-ol
1-ol
butanal
1-ol
1-ol
1-ol
15
30
45
60
0
0
0
0
0
0
0
0.01
0.04
0.14
0.3
0.01
0.04
0.14
0.24
0.46
0.7
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.16
0.01
0.02
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.06
0.06
0.1
0
0
0
0.30
0.46
0.64
0.80
0.98
1.12
1.24
1.32
1.38
1.44
1.46
1.44
1.40
1.30
0.80
0
0
0
0.3
0.6
1.0
1.4
2.3
2.9
1.8
0.4
0.1
0
0
0
0
0
0
75 0.06
90 0.2
0.2
0.4
0.8
1.4
0.6
0.1
0.04
0
0.5
0
0
0.8
0
0
105 0.42
120 0.86
135 1.94
150 3.7
165 1.5
180 0.5
1.2
1.1
0.06
0.16
0.32
0.46
0.60
0.66
0.72
0.70
0.20
0
0
1.5
1.6
0
1.8
2.3
0
2.0
2.86
3.4
0
2.14
2.4
0
3.9
0
195
210
225
240
255
270
285
0
0
0
0
0
0
0
0
0
2.6
4.2
0
0
0
2.86
3.06
3.26
3.26
3.26
3.26
4.5
0.68
0.80
0.70
0.40
0.10
0
0.4
1.7
2.8
4.6
5.8
6.0
0
0
4.8
0.4
1.6
1.5
0.4
0
0
0
5.2
0
0
8.8
0
0
0
14.2
18.8
0
0
0
0
0
0
on palladium catalysts does not undergo dehydration to
2-butenal [scheme (2)] and therefore cannot transform
into 1-butanol (7), whereas on Raney Ni catalysts this
process is possible. However, 1-butanol (7) is formed
more probably via pathway (4). This assumption is
confirmed by the experimental data obtained in this study.
1,4-butanediol synthesis on suspended catalysts for
enhancing the process selectivity.
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Science Foundation (project no. 14-23-00078).
CONCLUSIONS
REFERENCES
(1) Experiments on exhaustive hydrogenation of
2-butyne-1,4-diol on suspended palladium and Raney Ni
catalysts at atmospheric pressure revealed the previously
unknown mechanism of 1-butanol formation.
1. Reppe, W., Ann., 1955, vol. 39, pp. 596–601.
2. GDR Patent 248113, 1987.
3. Polish Patent 138901, 1988.
(2) When the hydrogenation is performed on Raney
nickel catalysts, the 1-butanol yield is 3 times smaller.
This fact can be used in the modern technology for
4. Jonson,A.W., J. Chem. Soc., 1946, vol. 96, pp. 1009–1012.
5. Khimickeskii entsiklopedicheskii slovar’ (Chemical
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STEP MECHANISM OF 1-BUTANOL FORMATION
589
Encyclopedic Dictionary), Knunyants, I.L., Ed., Moscow:
Sov. Entsiklopediya, 1983.
10. Beilsteins Handbuch der organischen Chemie, 1918, 3rd
ed., vol. 1, p. 1896.
11. Pyatnitsyna, E.V. and El’chaninov, M.M., Russ. J. Appl.
Chem., 2013, vol. 86, no. 3, pp. 394–397.
6. Beilsteins Handbuch der organischen Chemie, 1918,
3th ed., vol. 1, pp. 2255–2256.
12. Mandel’shtam, T.V., Ioffe, B.V., Artsibasheva, Yu.P., and
Bolotov, B.A., Sovremennye metody organicheskogo
sinteza (Modern Methods of Organic Synthesis),
Leningrad: Leningr. Gos. Univ., 1974.
7. Carothers, W.H., J. Am. Chem. Soc., 1933, vol. 55,
pp. 2807–2812.
8. Yonng, W.G., J. Am. Chem. Soc., 1936, vol. 58, pp. 100–
107.
13. Adkins, H. and Billica, H.R., J. Am. Chem. Soc., 1955,
vol. 70, pp. 695–701.
9. Hatch, L.F., J. Am. Chem. Soc., 1950, vol. 72, pp. 727–733.
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