Selective transformation of furfural to cyclopentanone

Article abstract of DOI:10.1016/j.catcom.2012.03.020

An entirely new route for highly selective preparation of cyclopentanone from furfural is described. It has been found that furfural dissolved in water is converted to cyclopentanone with very high selectivity at temperatures above 140 °C and hydrogen pressures > 30 bar. The selectivity of this reaction is strongly influenced by the heterogeneous catalyst and depends on the reaction conditions. Prolongation of the reaction time leads to the hydrogenation of cyclopentanone to cyclopentanol. If instead of water other solvents are used, the main products of reaction are well known hydrogenated derivatives of furfural, i.e. furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran and 2-methyltetrahydrofuran. In the presence of 5% Pt/C catalyst, 76.50 mol% yield of cyclopentanone (81.32 mol% comprehensive yield of cyclopentanone and cyclopentanol) is obtained after 30 min of reaction at 160 °C and a hydrogen pressure of 80 bar.

Full text of DOI:10.1016/j.catcom.2012.03.020

Catalysis Communications 24 (2012) 100–104
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Selective transformation of furfural to cyclopentanone
Milan Hronec ⁎, Katarina Fulajtarová
Department of Organic Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia
a r t i c l e i n f o
a b s t r a c t
Article history:
An entirely new route for highly selective preparation of cyclopentanone from furfural is described. It has
been found that furfural dissolved in water is converted to cyclopentanone with very high selectivity at tem-
peratures above 140 °C and hydrogen pressures >30 bar. The selectivity of this reaction is strongly influ-
enced by the heterogeneous catalyst and depends on the reaction conditions. Prolongation of the reaction
time leads to the hydrogenation of cyclopentanone to cyclopentanol. If instead of water other solvents are
used, the main products of reaction are well known hydrogenated derivatives of furfural, i.e. furfuryl alcohol,
tetrahydrofurfuryl alcohol, 2-methylfuran and 2-methyltetrahydrofuran. In the presence of 5% Pt/C catalyst,
76.50 mol% yield of cyclopentanone (81.32 mol% comprehensive yield of cyclopentanone and cyclopentanol)
is obtained after 30 min of reaction at 160 °C and a hydrogen pressure of 80 bar.
Received 30 January 2012
Received in revised form 9 March 2012
Accepted 13 March 2012
Available online 21 March 2012
Keywords:
Furfural
Cyclopentanone
Liquid phase
Rearrangement
Hydrogenation
© 2012 Elsevier B.V. All rights reserved.
1
. Introduction
The growing interest for application of renewable materials has
Cyclopentanone is a versatile compound used for the synthesis of
fungicides, pharmaceuticals, rubber chemicals, and flavor and fra-
grance chemicals. Potentionally, it can be used for preparation of
polyamides [12]. Cyclopentanone can be prepared by the catalytic
vapor-phase cyclization of 1,6-hexanediol [13] or adipic esters
[14,15] or by the liquid phase oxidation of cyclopentene with nitrous
oxide [16,17]. In all these processes petroleum-based products are
used as feedstocks.
To our knowledge there is no published study describing the se-
lective transformation of furfural, especially to cyclopentanone in
the presence of metal catalysts. In the present work we describe a
new route for efficient and cheap synthesis of cyclopentanone from
lignocellulose-derived furfural.
accelerated the development of new catalytic processes for prepara-
tion of chemicals, presently produced from petroleum feedstock. Bio-
mass derived furfural and 5-hydroxymethyl furfural are appropriate
starting materials which can be converted to various important
chemical products [1,2]. Gas and liquid phase hydrogenation of furfu-
ral has been widely studied for preparation of tetrahydrofurfuryl al-
cohol, 2-methylfuran and tetrahydrofuran [3–7]. Preferred catalysts
in these hydrogenation reactions are Cu–Cr and nickel based cata-
lysts. The catalysts based on Pd, Pt, Ru and Cu or modified with Fe,
Ce, Co, Sn or heteropolyacids were often studied in the hydrogenation
of furfural in the liquid phase in the absence and presence of a sol-
vent. In general, depending on the catalyst type, the nature of the
solvent can influence the kinetics of hydrogenation reaction and the
distribution of reaction products. Thus, in the presence of bimetallic
PtSn catalyst, furfural dissolved in 2-propanol is hydrogenated to
furfuryl alcohol with high selectivity (96–98%), whereby the use of
ethanol and especially toluene and n-heptane makes the reaction to
become slower, reaching a conversion of about 12% after 8 h of reac-
tion [1]. Both high activity and selectivity toward furfuryl alcohol
2. Experimental
2.1. Chemicals
Furfural (99%) was purified by distillation and stored at −15 °C.
Tetrahydrofurfuryl alcohol (99%), 2-methyltetrahydrofuran (99.5%),
cyclopentanol (99%), cyclopentanone (99%), furfuryl alcohol (98%),
and 2-methylfuran (99%) were used without purification. All
chemicals were purchased from Sigma Aldrich. 2-propanol (99%), n-
butanol (98%), n-decanol (97%) and dichloromethane, are all pur-
chased from Microchem Slovakia.
2 3
exhibit amorphous MoNiB/γ-Al O alloy catalyst in methanol [8]
and Raney nickel catalysts modified with salts of heteropolyacids in
the absence of solvent [9]. In the case of hydrogenation of furfural
to tetrahydrofurfuryl alcohol in the absence of solvent [10] or in
aqueous solution [11] highly active are the supported nickel catalysts.
2.2. Catalysts
5
% Pt/C, 5% Pd/C, and 5% Ru/C, all on activated carbon powder,
standard reduced, and nominally 50% water wet were purchased
from Johnson Matthey Co. The nickel catalyst Actimet C was
⁎
Corresponding author. Tel.: +421 2 59325328.
E-mail address: milan.hronec@stuba.sk (M. Hronec).
1566-7367/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2012.03.020

M. Hronec, K. Fulajtarová / Catalysis Communications 24 (2012) 100–104
101
purchased from BASF. The CoMnCr catalyst was prepared according
to the US Patent no. 5 210 335. The resulting solid was calcined at
effect on the distribution of products of furfural hydrogenation.
When water was used as the solvent, the main products were not
products from hydrogenation of the carbonyl group or the furan
ring. Unexpectedly, cyclopentanone was obtained from the furan
ring rearrangement.
5
00 °C in air. Before reaction, the catalyst was activated in hydrogen
atmosphere at 480 °C for 5 h.
2
.3. Catalytic tests
The transformation of furfural to cyclopentanone is the result of
the effect of water, which plays a key role in the ring rearrangement,
whereas it is strongly influenced also by other factors. To avoid the ef-
fect of solubility of reaction products in the aqueous phase, i.e. their
homogeneity, only 2.4–4.8 wt.% solutions of furfural were used for
the reaction. Table 2 shows the effect of heterogeneous metal cata-
lysts on the selectivity of furfural transformation to cyclopentanone
or cyclopentanol, as the product of consecutive hydrogenation of
cyclopentanone. The evaluation of metal catalysts on the basis of
the yields of cyclopentanone was done at two reaction conditions.
As it is evident from experimental results, the influence of reaction
temperature and hydrogen pressure on the yield of cyclopentanone
is significantly different for each catalyst studied. Influenced is also
the ratio of reaction products which are produced by furan ring rear-
rangement and by hydrogenation of the furan ring and the aldehyde
group. For example, at lower reaction temperature and hydrogen
pressure, palladium catalyst affords higher yields of cyclopentanone
than platinum or ruthenium catalysts. However, at higher reaction
temperature and hydrogen pressure the preferred reactions in the
presence of Pd/C catalyst are hydrogenation of the furan ring and
the aldehyde group, while in the presence of Pt and Ru catalysts it is
the furan ring rearrangement. At these reaction conditions and even
Catalytic transformation of furfural was performed in a 100 ml
stainless steel reactor equipped with a stirrer, an electric temperature
controller and a sample port for liquid samples. For a typical reaction,
2
0 ml of water, 1.0 g of furfural and a given amount of metal catalyst
were added to the reactor vessel. After sealing, the reactor was sever-
al times flushed with low pressure hydrogen and then pressurized
with hydrogen, usually to 30–80 bar (at ambient temperature). The
reactor was then heated to the desired temperature and the stirring
speed fixed to 1500 rpm to eliminate the diffusion effects. After an
appropriate reaction time, the reactor was quickly cooled down, the
reactor content was then poured out to a vial and the catalyst was
separated from the aqueous phase by centrifugation. The aqueous
phase was analyzed using gas chromatography (Hewlett Packard
5
890 Series II, with FID detector) with a 1.4 m×3 mm glass column
packed with 5% C20M+5% SE. The quantitative determination of
the reaction products was done by the external standard method
using aqueous solutions of each product with known concentration
and response factor. A gas chromatograph–mass spectrometer combi-
nation (GC/MS QP 5000 Shimadzu with HP-1, 50 m×0.2 mm capil-
lary column) was used to identify the organic compounds. Prior to
GC/MS analysis, the aqueous phase saturated with NaCl was several
in the presence of half
a concentration of platinum catalyst
times extracted with dichloromethane. In selected reaction samples
76.5 mol% yield of cyclopentanone was obtained after 30 min of
reaction.
the presence of cyclopentanone was also verified by the 1H and
13
C
NMR analysis (Varian VNMRS-600) [Supplementary data]. The com-
position of the gas phase was determined using gas chromatography
At the applied reaction temperatures and hydrogen pressures the
keto group of cyclopentanone can be hydrogenated to hydroxyl
group. In the literature there are no published data concerning the
equilibrium concentrations of cyclopentanone–cyclopentanol in the
liquid phase at the conditions of the presented experiments. Some in-
formation about the equilibrium concentrations of the cyclopenta-
none–cyclopentanol mixture in water provides the experiments
with cyclopentanone and cyclopentanol conducted at the tempera-
ture of 175 °C and hydrogen pressure of 30 bar in the presence of Pt
and Ru catalysts (Table 3). From these results it is evident that
under the given temperature and hydrogen pressure the hydrogena-
tion–dehydrogenation equilibrium is shifted toward cyclopentanol.
Although the hydrogenation–dehydrogenation equilibrium is a func-
tion of temperature and hydrogen pressure it is clear that within the
range of our experimental conditions and at reaction time, cyclopen-
tanol and not cyclopentanone should be the dominant product of the
furan ring rearrangement. As it is evident from Fig. 1a, the prolonga-
tion of the reaction time decreases the yield of cyclopentanone and
almost proportionally increases the yield of cyclopentanol. To deter-
mine the accurate reaction time and to avoid the reaction of furfural
during heating of the reaction mixture to the desired temperature
(usually it lasts 15–20 min), in these experiments the catalyst was
(
Shimadzu GC-17A equipped with TC and FID detectors). We found
only trace amounts of carbon oxides, methanol and light hydrocar-
bons in the gas phase. The yields of all reaction products were calcu-
lated on the amount of furfural charged into the reactor. The mass
balance of carbon was estimated as the sum of the yields of products
determined by using standard compounds and unconverted furfural.
The mass loss is ascribed to other not identified compounds analyzed
by GC and mostly to the water soluble oligomers formed during the
reaction.
3
. Results and discussion
Both the gas-phase [3,18] and the liquid phase hydrogenation of
furfural in the absence of solvent [9,10] or in alcohol as solvent [5,6]
lead to the reduction of the C_O group and/or the furan ring. Our
study of the liquid phase hydrogenation of furfural in an aqueous so-
lution has led to the finding that under specific reaction conditions
and the presence of certain heterogeneous metal catalyst furfural
can be converted to cyclopentanone with a very high selectivity.
The results given in Table 1 show that the solvent has significant
Table 1
Effect of solvent on the transformation of furfural.
Solvent
Conversion,
%
Yield, mol%
∑
C
PON
C
POL
FAL
THFAL
2-MeF
2-MeTHF
Water
n-Butanol
n-Butanol/water
100
99.3
99.7
40.23
0.08
10.13
36.23
0.19
2.44
0
0.29
5.87
7.27
5.02
40.43
30.84
9.44
1.85
0
91.15
96.98
51.67
47.86
0.69
(1:1 vol)
n-Decanol
Tetrahydrofuran
94.5
99.4
0.18
0.24
0.13
0.10
26.34
19.28
4.78
4.62
23.17
0
1.09
0
61.10
24.84
Reaction conditions: 1.0 g FA, 0.1 g 5% Pt/C, 20 ml solvent, reaction temperature 175 °C, hydrogen pressure 80 bar, reaction time 30 min; FA — furfural, CPON — cyclopentanone, CPOL
cyclopentanol, FAL — furfuryl alcohol, THFAL — tetrahydrofurfuryl alcohol, 2-MeF — 2-methylfuran, 2-MeTHF — 2-methyltetrahydrofuran, ∑ — the sum of the yields and
unconverted FA.
—

102
M. Hronec, K. Fulajtarová / Catalysis Communications 24 (2012) 100–104
Table 2
Effect of catalyst.
Exp.
no.
Catalyst
React.
temp. °C
Hydrogen
pressure bar
Conversion
%
Yield, mol%
Σ
C
PON
C
POL
FAL
1.52
0
0
0
0
0
0
0
THFAL
2-MeF
2-MeTHF
1
2
3
4
5
6
7
8
9
5% Pt/C
160
30
80
80
80
80
30
80
30
80
80
80
30
96.5
100
100
51.13
76.50
55.74
40.23
48.40
67.08
38.89
12.73
57.33
4.48
3.76
4.82
7.91
36.23
6.45
0.74
3.54
0.57
9.50
0
0
0
4.92
3.44
3.20
5.02
1.79
2.37
2.97
0.14
3.38
2.88
0.37
6.55
0.23
0.43
0.76
9.44
5.40
6.17
10.31
0.05
3.16
7.55
0.46
4.74
65.06
85.19
67.61
91.15
66.13
80.59
91.30
54.89
79.42
68.64
53.49
92.33
a
160
160
a,b
175
100
0.23
2.17
2.03
35.59
1.50
6.05
4.90
16.49
23.40
c
175
98.08
97.8
100
60.1
100
100
100
100
5% Pd/C
5% Ru/C
160
175
d
160
175
0
0
e
10
11
12
175
48.83
16.42
40.01
CoMnCrf
Raney Ni
Actimet C
175
7.63
17.46
12.12
0.17
g
160
Reaction conditions: 1.0 g FA, 20 ml water, catalyst 0.10 g, reaction time 60 min.
a
0
.05 g catalyst, 30 min.
b
c
d
e
f
Reaction time 150 min.
The stirring speed ca. 350 rpm.
3
0 min.
From the reaction mixture of exp. no. 9 Ru/C catalyst was separated and after the addition of 0.1 g of fresh 5% Pt/C catalyst the reaction proceeded for 60 min.
.5 g FA, 0.15 g catalyst, 30 min.
.20 g catalyst.
0
0
g
separated from the aqueous solution of furfural. The catalyst was
placed into a Teflon-made vessel (volume ca. 0.5 ml) which was
inserted inside the reactor. At the start of the reaction the vessel
was turned out by a stirrer bar and then, the catalyst was mixed
with the liquid phase. After the given reaction time the reactor was
quickly cooled down with water. These measurements have shown
that at 175 °C and 80 bar of hydrogen pressure the transformation
of furfural to cyclopentanone in the presence of 5% Pt/C catalyst is
very rapid and also highly selective. At lower reaction temperature
A small effect on the shift of the cyclopentanol/cyclopentanone
ratio to equilibrium has also the reaction temperature (Table 4). In
the temperature range 145–190 °C and at constant hydrogen pres-
sure, the yield of cyclopentanol surprisingly remains almost the
same, but the yield of cyclopentanone increases. On the other hand,
when the reaction is performed at the same reaction temperature
(175 °C) but at different hydrogen pressures, the yields and also the
ratios of both desired products are dramatically changed. At a hydro-
gen pressure of 11 bar, despite high furfural conversion, the yields of
the desired products are only about 3 mol% (Table 4). When the same
reaction is conducted at 30 bar of hydrogen, the yield of cyclopenta-
none sharply increases to 44.60 mol%, but the yield of cyclopentanol
increases only slightly. A high yield of cyclopentanol (35.11 mol%) is
reached at 80 bar of hydrogen (Fig. 1a); however, also at this hydrogen
pressure cyclopentanone is still the dominant product (40.23 mol%
yield).
The problem of furan ring rearrangement and non-equilibrium
composition of reaction mixtures in the process of furfural transfor-
mation cannot be ascribed to the mass-transfer effects, though they
influence the rate and selectivity of the reaction. The experiments
performed with different stirring speeds have shown that the furan
ring rearrangement is not caused by the mass-transfer effects. More-
over, they supported the suggestion that hydrogen concentration in
the liquid phase has a significant effect on the course of reaction
and the equilibrium composition of cyclopentanol/cyclopentanone
in the reaction mixture (Table 2, exp. 4 and 5). Although these exper-
iments were performed at high hydrogen pressure, the lower stirring
speed probably causes the majority of hydrogen dissolved in the liq-
uid phase to be consumed for the furan ring rearrangement and not
for the consecutive hydrogenation of primary formed cyclopenta-
none. This observation can explain why a relatively higher amount
of cyclopentanone is formed in the experiment with lower stirring
speed. However, similarly as in the experiment performed at low hy-
drogen pressure (Table 4), insufficient concentration of hydrogen dis-
solved in the liquid phase causes that a larger part of furfural is
converted to undesirable products.
(
160 °C) and hydrogen pressure (30 bar) the rate of cyclopentanone
formation was significantly lower (Fig. 1b). The prolongation of the
reaction time led to the consecutive hydrogenation of cyclopenta-
none to cyclopentanol. In both experiments, after 60 min of reaction,
the comprehensive yields of cyclopentanone and cyclopentanol were
almost the same, about 72 mol%.
Based on the data given in Table 3, in experiments depicted in
Fig. 1 the ratio of cyclopentanol/cyclopentanone in the reaction mix-
tures measured after 60 min of reaction should be about 9:1. This
ratio was never observed in the above described experiments per-
formed in the presence of different catalysts and at various reaction
temperatures and hydrogen pressures (Table 2). Unexpectedly, in
all these experiments the preferred product was cyclopentanone.
The attempt to reach the quasi-equilibrium ratio of cyclopentanol/
cyclopentanone in the reaction mixture by prolongation of the reac-
tion time to 150 min was not effective. As can be seen from the results
(
Table 2, exp. 2 and 3) despite slight increase of cyclopentanol yield,
the ratio of cyclopentanol/cyclopentanone in the reaction mixture re-
mains very far from equilibrium. The lower comprehensive yield of
cyclopentanone and cyclopentanol is probably caused by the subse-
quent hydrogenolysis of cyclopentanol.
Table 3
Hydrogenation–dehydrogenation of cyclopentanone and cyclopentanol.
Catalyst, 0.1 g
% Pt/C
Composition of reaction mixture, %
5
5% Ru/C
C
PON
C
POL
Both the low rate of consecutive hydrogenation of cyclopentanone
and the difficulty to reach the quasi-equilibrium ratio of cyclopenta-
nol/cyclopentanone are probably caused by intermediates or by-
products formed during the catalytic reaction. Such compounds are
strongly attached to the metal surface where they compete with the
ketone for active sites. The occupation of catalyst sites by adsorbing
Cyclopentanone
Cyclopentanol
10.2
11.25
8.70
7.27
89.66
88.10
91.28
92.36
Cyclopentanone
Cyclopentanol
Reaction conditions: 1.0 g cyclopentanone or cyclopentanol; 20 ml water, reaction
temperature 175 °C, hydrogen pressure 30 bar, and reaction time 60 min.

M. Hronec, K. Fulajtarová / Catalysis Communications 24 (2012) 100–104
103
determined at 175 °C and 30 bar of hydrogen (Table 3). The lower
comprehensive yield of cyclopentanone and cyclopentanol obtained
in the second step is probably the reason of subsequent hydrogenoly-
sis of cyclopentanol.
As can be seen from the results in Tables 1, 2 and 4 the disagree-
ment in terms of mass balance indicates that undesirable products
and oligomeric by-products are formed during the reaction. A very
large amount of these by-products is produced in experiments con-
ducted in tetrahydrofuran and n-decanol as solvents. In aqueous solu-
tions these disagreements are typical for experiments where a less
active catalyst (CoMnCr) is used or the catalyst concentration is too
low (Pt/C). However, the crucial role seems to be played by hydrogen
pressure which prevents the formation of by-products. This is sug-
gested by experiments performed at near optimal conditions. In
these experiments the mass balance is more than 90%. Using mild re-
action conditions the conversion of furfural is decreased, however, it
significantly increases the formation of undesirable products, as
what is manifested by a very low mass balance. In order to avoid
the undesirable reactions, the concentration of hydrogen in the aque-
ous phase might be high enough, i.e. the reaction must proceed at suf-
ficient hydrogen pressure and rigorous mixing of the reaction
mixture. Under these conditions the rate of catalytic transformation
of furfural to the desired products is much higher than the rates of
condensation reactions of reactive intermediates.
The studied furan ring rearrangement proceeds only in the pres-
ence of the nucleophile, water, which clearly indicates that the reac-
tion intermediate is electrophilic in nature. One can speculate about
the intermediates and why this reaction is observed only in water.
It appears that the function of metal catalyst is the scission of the
C\O bond in the furfural or in its primary reaction products [20].
The intermediate is probably a cation which is strongly bound on
the metal surface through the oxygenated group and the furan ring.
Water contributes to the construction and reactivity of this interme-
diate species, which in the next step is converted to cyclopentanone.
At low concentration of hydrogen in the liquid phase the intermedi-
ate species attached to the metal surface undergo undesirable termi-
nation and condensation reactions. This explains the disagreement in
the mass balance. Understanding of the reaction mechanism and im-
portance of possible reaction pathways requires further studies.
4
. Conclusions
A novel, highly selective one-step transformation of furfural to
cyclopentanone is described. The selective rearrangement of furfural
is achieved in water as solvent at reaction temperatures of 140–
1
90 °C and hydrogen pressures of 30–80 bar. The reaction is catalyzed
by heterogeneous metal catalysts which significantly influence the
distribution of reaction products. By optimization of reaction temper-
ature, hydrogen pressure, reaction time and type and concentration
of metal catalyst it is possible to reach more than 76 mol% yield of
cyclopentanone, or more than 81 mol% comprehensive yield of
Fig. 1. Time dependence of furfural conversion (□, ■) and the yield of cyclopentanone
△, ▲) and cyclopentanol (○, ●) at (a) 175 °C/80 bar and (b) 160 °C/30 bar.
(
Table 4
ketone molecules was assumed to explain the decrease of the rate of
cyclopentanone hydrogenation in acetic acid as solvent with increas-
ing concentration of ketone [19]. The possible retardation of consecu-
tive hydrogenation of cyclopentanone by the formed intermediates or
by-products confirmed the experiment in which furfural transforma-
tion was conducted in two steps, while holding other conditions con-
stant (Table 2, exp. 9 and 10). In the first step, performed in the
presence of Ru/C catalyst, a reaction mixture containing cyclopenta-
none and cyclopentanol in the ratio of about 6:1 was obtained. After
separation of the catalyst, the mixture was in the second step hydro-
genated in the presence of fresh Pt/C catalyst. The formed reaction
mixture contained cyclopentanone and cyclopentanol in the ratio of
about 1:10, what is very close to the equilibrium composition
Effect of reaction temperature.
React.
temp. °C
Conversion Yield, mol%
%
Σ
C
PON
CPOL FAL THFAL 2-MeF 2-MeTHF
190
100
98.2
46.24 4.26
44.60 3.70
0
0
0
0
3.66
4.92
10.56
1.52
3.50
5.12
0.49
0.23
0
54.65
53.45
35.05
48.37
65.06
50.75
175
a
175
160
160
145
85.7
68.7
96.5
93.7
3.06 3.32 3.50 0.31
15.11 0.11 0.33
51.18 4.78 0.20
b
0
0
0
0.27
0.21
33.05 4.16 1.50 0.41
Reaction conditions: 1.0 g FA, 20 ml water, 0.1 g 5%Pt/C, hydrogen pressure 30 bar, re-
action time 30 min.
a
At 11 bar.
0.02 g catalyst.
b

104
M. Hronec, K. Fulajtarová / Catalysis Communications 24 (2012) 100–104
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