Oxidation of cyclooctene to suberic acid using perrhenate-containing composite ionic liquids as green catalysts

Article abstract of DOI:10.1134/S1070363215100254

A series of quaternary ammonium perrhenate/3-hexyl-1-methyl-imidazolium hydrogen sulfate ([Hmim]HSO₄) composite ionic liquids has been prepared. For the first time, the composite ionic liquids are used both as catalyst and solvent in oxidation of cyclooctene to suberic acid in the presence of hydrogen peroxide as a green oxidant. It was found that organic perrhenate salts play the important role in improving the selectivity of cyclooctene oxidation to suberic acid. The yield of suberic acid under the mild conditions is from good to high.

Full text of DOI:10.1134/S1070363215100254

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 10, pp. 2378–2385. © Pleiades Publishing, Ltd., 2015.
Oxidation of Cyclooctene to Suberic Acid
Using Perrhenate-Containing Composite
Ionic Liquids as Green Catalysts1
J. Y. Wanga,b, M. D. Zhoua, Y. G. Yuana, N. H. Fua, and S. L. Zanga,b
a School of Chemistry and Materials Science, Liaoning Shihua University, 113001 Fushun, China
e-mail: ShuliangZang@163.com
b College of Chemical Engineering, China University of Petroleum, 266580 Qingdao, China
Received July 17, 2015
Abstract—A series of quaternary ammonium perrhenate/3-hexyl-1-methyl-imidazolium hydrogen sulfate
([Hmim]HSO4) composite ionic liquids has been prepared. For the first time, the composite ionic liquids are
used both as catalyst and solvent in oxidation of cyclooctene to suberic acid in the presence of hydrogen
peroxide as a green oxidant. It was found that organic perrhenate salts play the important role in improving the
selectivity of cyclooctene oxidation to suberic acid. The yield of suberic acid under the mild conditions is from
good to high.
Keywords: oxidation, suberic acid, organic perrhenate, composite ionic liquid
DOI: 10.1134/S1070363215100254
INTRODUCTION
“green” catalytic methods using cyclohexene as
substrate and aqueous hydrogen peroxide as oxidant
have been reported. WO3 [14, 15], H2WO4 [16, 17],
Na2WO4·2H2O [18, 19], organic peroxytungstates
[20, 21], and other compounds [22] are widely used
efficient catalysts. Small amount of Na2WO4·2H2O, as
metal salt catalyst, [CH3(n-C8H17)3N]HSO4, as phase-
transfer catalyst, and 30% hydrogen peroxide, as
oxidant, are applied in oxidation of cyclohexene to
acidic acid in the Noyori’s et al. method [18, 19].
Further, Deng et al. have developed similar method for
direct oxidation of cyclohexene with 30% aqueous
hydrogen peroxide, in which organic peroxotungstate
with the anion structure of [W(O)(O2)2L2]2– served as
green catalyst, with the yield by adipic acid under mild
conditions also comparable [20, 21].
Dicarboxylic acids are the important key raw
materials, widely used in the preparation of nylon,
lubricants, electrolyte, cosmetics, polyamides, adhesives,
greases, polyesters, and many other fine chemicals
[1, 2]. Among them, adipic acid has found the most
wide industrial application as precursor for nylon-6,6
production [3, 4]. To important succinic, suberic,
azelaic, dodecanedioic and other acids belong to
dicaboxylic acids. The above dicarboxylic acids, for
example adipic and suberic acids, can be produced by
the oxidation of castor oil, cyclic diols, or ketones in
the presence of nitric acid as oxidant [5, 6]. Some other
long-chain dicarboxylic acids, such as dodecanedioic
acid, can be prepared by the alkali fission or
fermentation of long-chain alkanes [7, 8]. However,
nitric acid oxidation includes air pollution and
corrosive processes [9–11]. Due to the environ-mental
restrictions, replacement of conventional methods is
desirable. An alternative method would be the
replacement of nitric acid for aqueous hydrogen
peroxide, which gives only water as byproduct [12, 13]
and, therefore is a comparatively “green” method. For
preparing adipic acid under mild conditions, various
Li et al. [23] have shown that in oxidation of
cyclohexenes in the presence of quaternary ammonium
salts as co-catalysts, the highest catalytic activity
among three polyoxometalates (POMs), H3PW12O40,
H3PMo12O40, and H4SiW12O40, has H3PW12O40.
Compared to well-known catalytic methods of
cyclohexene oxidation, the oxidation of cyclooctene,
which is also an important industrial raw material, is
studied little. Although the Novori’s method is
efficient for cyclohexene, in the case of cyclooctene it
provides only 9% yield by suberic acid.
1 The text was submitted by the authors in English.
2378

OXIDATION OF CYCLOOCTENE TO SUBERIC ACID
It is known that many high-oxidation state transi-
2379
tion metal complexes show good catalytic activity in
oxidation reactions. In particular, a versatile organo-
rhenium compound, methyltrioxorhenium (MTO),
which was first synthesized by Beattie and Jones in
1979 [24] and was first used as oxidation catalyst in
1991 [25], has received considerable attention during
the past decades [26–30]. However, such homo-
geneous catalysts are expensive and must be recycled.
Unfortunately, immobilization of MTO onto hetero-
geneous carriers is difficult and a significant amount of
the catalyst is commonly lost upon leaching [31].
Fig. 1. ORTEP view of [(n-C4H9)4N]ReO4 (4) showing
vibrational ellipsoids at the 50% probability level. H atoms
are omitted for clarity.
An alternative method is the immobilization of
MTO and related compounds in ionic liquids (ILs)
[32]. Due to negligible volatility, excellent thermal
stability, marked solubility, and a variety of the
available structures, ILs have received great attention
as environmentally benign solvents to replace volatile
organic solvents in a wide variety of chemical
reactions, and in separation and manufacturing
processes [33–36]. ILs are already used in industrial
catalytic processes [37], in BASF-BASIL process in
particular [38]. However, the decomposition of MTO
to perrhenates may occur in the ionic liquid-mediated
catalytic reactions. For decades, perrhenates have been
considered as notorious “dead end” compounds for
most catalytic processes. However, it was surprising to
find that many perrhenate-based ionic liquids can
activate olefin epoxidation reactions, ensuring from
good to excellent yield by epoxide for a variety of
olefin substrates. More important, the perrhenate-based
ionic liquids can be repeatedly recycled and reused
without significant loss of activity, which provides an
easy-handle and solvent-free oxidation method [39].
The above results have stimulated us to perform a
further study on the catalytic behavior of the
perrhenate-based ionic liquids. Recently, a series of
quaternary ammonium perrhenate ionic liquids was
synthesized in our group and then combined with
Hmim[HSO4], which was used both as efficient
catalyst and a solvent in cyclooctene oxidation.
lengths were prepared in our studies, according to the
published procedures [40–42]. The structures are
shown in Scheme 1.
The synthesized perrhenate salts were characterized
1
by the FT-IR, H NMR, and elemental analyses (see
Experimental). The melting point was determined with
a micromelting point apparatus and the decomposition
temperature, by the thermogravimetric analysis (TGA).
These organic salts are not conventional ionic liquids,
since they are solids below 100°C. However, these
salts can be completely dissolved in [Hmim]HSO4 to
form colorless or yellow composite ionic liquids,
which were used both as catalyst and a solvent in
cyclooctene oxidation. The TGA data indicate that
compounds 1–5 have good thermal stability and start
to decompose between 220–300°C. The compounds’
spectra have strong bands due to the Re–O bond
vibrations between 890–920 cm–1, which are typical of
ReO4 [43].
The solid-state single crystal structure of the
compound 4 is shown in Fig. 1. The structure is
somewhat disordered with respect to the carbon atoms
on the butyl groups, which sets the limit for the
determination of bond lengths and bond angles.
Herein, we report our original study on a green
oxidation of cyclooctene to suberic acid in the
presence of perrhenate-containing composite ionic
liquids as catalysts and a 30% aqueous hydrogen
peroxide as oxidant.
Scheme 1. Structures of quaternary ammonium perrhenate
salts.
R
ReO4−
R
N+ R'
R
RESULTS AND DISCUSSION
1: R, R' = CH3, 2: R, R' = C2H5, 3: R = C2H5, R' = n-C4H9, 4:
R, R' = n-C4H9, 5: R = CH3, R' = n-C4H9.
Synthesis and properties. The quaternary ammo-
nium perrhenate salts bearing alkyl chains of different
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WANG et al.
Scheme 2. Pathway of the oxidation of cyclooctene to suberic acid.
O
OH
OH
O
[O]
[O]
H2O
OH
1
3
4
5
O
O
[O]
[O]
H2O
COOH
COOH
O
O
O
O
6
7
2
Oxidation of cyclooctene. According to our pre-
vious study [39], the H2O2 molecules can be activated
by organic perrhenate salts through hydrogen bonding
between ReO4– and H2O2, thus enabling epoxidation of
a variety of olefins with the forming active species
under mild conditions. According to the literature data
[18, 19], the oxidation of cyclooctene to suberic acid
includes several processes, such as formation of
epoxide, its hydrolysis to diol, oxidation of diol to
cyclic α-hydroxy ketone, the Baeyer–Villiger oxida-
tion of α-hydroxy ketone to α-hydroxy lactones, and
formation of suberic acid by hydrolysis (Scheme 2).
of cyclooctene to suberic acid will proceed under more
violent conditions.
Moreover, the existence of a phase-transfer catalyst
is also crucial for H2O2 oxidation reactions to provide
transfer of the forming active species or the reactants
between the inorganic and organic phases. In our
study, the acidic ionic liquid ([Hmim]HSO4) was
combined with compounds 1–5 into the composite
ionic liquids, which were used both as solvent and
catalyst for the oxidation of cis-cyclooctene to suberic
acid in the presence of a 30% aqueous hydrogen
peroxide as oxidant.
According to [39], the imidazolium-based perrhenates
assist cyclooctene epoxidation, providing an almost
100% selectivity towards the formation of epoxides.
Therefore, it can be concluded that catalytic oxidation
Details concerning the catalytic reaction are given
in the Experimental. No cyclooctene conversion was
observed in blank reactions proceeding in the presence
(a)
(b)
10
30
50
70
90
10
30
50
70
90
Time, min
Time, min
Fig. 2. (a) Conversion vs. time and (b) yield of suberic acid vs. time curves for cyclooctene oxidation at 60°C: (■, ♦) without 1 and
(*, ×) with 5 mol % of 1. Reactants: cis-cyclooctene (1 mmol, 0.11g), H2O2 (5 mmol, 0.5 mL), and [Hmim]HSO4 (1 mL).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 10 2015

OXIDATION OF CYCLOOCTENE TO SUBERIC ACID
Table 1. Optimization of the reaction conditionsa
2381
Amount of composite ionic liquid
Run no.
Temperature, °C
Conversionc, %
Yieldd,e, %
1, mol %b
[Hmim]HSO4, mL
1
2
0
1
3
5
5
5
5
5
8
5
5
5
5
5
5
1.0
1.0
1.0
1.0
0.1
0.3
0.5
0.8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
60
60
60
60
60
60
60
60
60
25
40
50
70
80
100
81
92
38 (31)
47 (36)
69 (10)
69 (10)
3 (25)
3
98
4
100
33
5
6
73
17 (50)
20 (45)
54 (25)
70 (10)
0 (60)
7
79
8
100
100
65
9
10
11
12
13
14
15
87
5 (58)
95
43 (41)
71 (10)
75 (15)
70 (15)
100
100
100
a
b
The reactions were carried out using cis-cyclooctene (1 mmol, 0.11 g) and H2O2 (5 mmol, 0.5 mL) for 6 h. Compound 1 was applied
according to the molar percentage of cyclooctene. c The conversion and yield were calculated based on GC analysis. Yield of
cyclooctene epoxide is given in the brackets. <5% of 1,2-cyclooctanediol and small amount of other unidentified byproducts can be
d
e
detected.
of excess amount of H2O2 and 1 mL of dichlorometane
as solvent and in the absence of the catalyst at 60°C.
When 1 mL of [Hmim]HSO4 is introduced into the
system as the catalyst and solvent (Fig. 2a), the
conversion reaches ca. 81% after 4 h of reaction.
However, the reaction product is a complicated mix-
ture, with the suberic acid yield only 38% (Fig. 2b). To
our delight, the reaction can be accelerated in the
presence of the compound 1 containing [Hmim]HSO4
composite ionic liquid as catalyst and solvent, and the
selectivity of suberic acid can be also significantly
improved (Fig. 2b), i.e., organic perrhenates are
suitable to promote cyclooctene oxidation. In the
subsequent optimization of the reaction, we used the
compound 1 containing the composite ionic liquid as
the catalyst and solvent, and 30% aqueous hydrogen
peroxide as the oxidant.
Theoretically, 4 equiv. of H2O2 is necessary to
transfer the cyclooctene to suberic acid. In order to
completely convert the substrate, 5 equiv. of the
oxidant was applied in our experiments. All the reac-
tions give cyclooctene epoxide and suberic acids as
major products. Moreover, a small amount of 1,2-
cyclooctanediol, product of epoxide hydrolysis and
other non-identified products were also detected. In
general, the conversion of cyclooctene is significantly
affected by the amount of [Hmim]HSO4. The
conversion in the presence of 0.8 mL [Hmim]HSO4 at
60°C is 100% (Table 1). The yield by suberic acid
increases with the increase of the amount of
perrhenate. Moreover, the temperature is also the
crucial parameter to control the composition of the
products. At lower temperature of the reaction,
epoxide is major product (Table 1, nos. 10, 11). The
yield by suberic acid rapidly increases with increasing
temperature. The highest yield (75%) is obtained in the
presence of 5 mol % of perrhenate and 1 mL of
[Hmim]HSO4 at 80°C. However, with temperature
The data on the influence of reaction temperature,
composition of the ionic liquid, and amount of the
composite ionic liquid are given in Table 1.
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WANG et al.
Table 2. Cyclooctene oxidation in the presence of different composite ionic liquidsa
OH
H2O2
COOH
COOH
+
O +
NR4ReO4/HmimHSO4
OH
Yieldb,c, %
Run no.
Organic perrhenates
–
Conversionb, %
epoxide
diol
11
3
suberic acid
1
2
3
4
5
6
81
100
100
100
100
100
31
10
8
38
75
72
58
81
57
[(CH3)4N]ReO4 (1)
[(C2H5)4N]ReO4 (2)
3
[(C4H9)(C2H5)3N]ReO4 (3)
[(n-C4H9)4N]ReO4 (4)
[(C16H31)(CH3)3N]ReO4 (5)
15
4
3
3
20
4
a
The reactions were carried out using cis-cyclooctene (1 mmol, 0.11 g), H2O2 (5 mmol, 0.5 mL), Compounds 1–5: (0.05 mol), [Hmim]HSO4
(1 mL) at at 80°C. b Conversion and yield were calculated based on GC analysis. c <5% of 1,2-cyclooctanediol and small amount of other
un-identified byproducts can be determined.
increased further to 100°C, the yield is decreased,
which may be due to the decomposition of the oxidant
at the evaporation temperature.
yield by suberic acid is decreased from 75 to 53% after
recycling.
Oxidation of other olefins. The catalytic system
was also applied for other olefins, including cyclo-
hexene, styrene, 1-hexene, and 1-dodecene1-Dodecene
in order to further evaluate the catalytic performance
of the composite ionic liquids. The results indicate that
the catalytic system is also applicable for the oxidation
of cyclohexene, with a 88% yield by adipic acid
achieved in the presence of compound 1 containing a
composite ionic liquid. At the same time, in the case of
styrene, 1-hexene, and 1-dodecene, all reactions yield
diols as major products (Table 3).
Based on the above studies, we performed the
cyclooctene oxidation with different perrhenate-
containing ionic liquids in order to compare the
catalytic performance of the perrhenate salts. The
results are summarized in Table 2. It was found that
compounds 1, 2, and 4 with the symmetric cationic
structure have higher selectivity towards suberic acid
and better solubility in the ionic liquid [Hmim]HSO4
than compounds 3 and 5. Dissolution of compounds 3
and 5 in [Hmim]HSO4 yields a composite ionic liquid
solution of a comparatively high viscosity, which
might be responsible for the low catalytic activity in
cyclooctene oxidation.
EXPERIMENTAL
General Remarks. All chemicals and solvents were
purchased from Sinopharm Chemical Reagent Co. or
Acros and used as received. Microanalyses of the
obtained products were performed with a Flash EA
1112 series elemental analyzer. 1H NMR spectra were
recorded on a 500-MHz Bruker Avance DPX-500
spectrometer. IR spectra were measured on a
PerkinElmer Frontier FT-IR spectrometer. ESI-MS
spectra were taken on a Finnigan LCQ Classic mass
spectrometer. Melting points were determined by an
X-6 micro melting point apparatus (Beijing Tech
Instrument). Thermogravimetric (TGA) and differential
scanning (DSC) analyses were conducted on a
Netzsch-STA 409 PC Instrument. Each sample (about
The recycling and reusability of composite ionic
liquids were also studied. After completing the
reactions, the products were extracted by ethyl acetate
and the residual composite ionic liquids were further
purified by extraction with n-hexane, dried under
vacuum below 80°C for 2 h, and used directly as the
catalyst and solvent for the next catalytic run.
However, the recycled ionic liquid became dark and
somewhat more viscous, as compared to the first run,
and its activity was also decreased, which may due to
the paritial decomposition of [Hmim]HSO4 during the
catalytic reactions. In the case of the compound 1
containing a composite ionic liquid as the catalyst, the
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OXIDATION OF CYCLOOCTENE TO SUBERIC ACID
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Table 3. Oxidation of other olefins using compound 1 containing a composite ionic liquida
Run no.
1
Olefin
Product
COOH
Conversionb, % Yieldb, %
100
88
COOH
OH
2
100
64
OH
3
4
56
84
58
76
OH
OH
OH
OH
a
The reactions were carried out using olefin (1 mmol), H2O2 (5 mmol, 0.5 mL), compound 1 (0.05 mmol), [Hmim]HSO4 (1 mL) at 80°C.
Conversion and yield were calculated based on GC analysis.
b
10 mg weight) was heated from 25 to 1000°C at a step
of 10 K/min. The catalytic runs were monitored by the
GC methods on an Agilent 6890 instrument equipped
with a FID detector (capillary column 30 m × 0.25 mm ×
0.25 μm).
Compound 3. IR spectrum, cm–1: 910 (Re=O),
1463, 2918, 3435. H NMR spectrum (D2O, 400 Hz,
1
r.t., ppm): 3.218–3.174 q (6H, 3CH2), 3.095–3.061 t
(2H, CH2), 1.610–1.546 m (2H, CH2), 1.343–1.314 m
(2H, CH2), 1.299–1.185 t (9H, 3CH3), 0.896–0.867 t
(3H, CH3). Calculated, %: C 29.40, H 5.92, N 3.43.
C10H24NO4Re. Found, %: C 29.42, H 5.90, N 3.45. M
408.51.
Compound 4. IR spectrum, cm–1: 906 (Re=O),
1389, 1474, 2965. 1H NMR spectrum (CDCl3, 400 Hz,
r.t., ppm): 3.232–3.176 t (8H, 4CH2), 1.680–1.577 m
(8H, 4CH2), 1.479–1.358, m (8H, 4CH2), 1.013–0.965
t (12H, 4CH3). Calculated, %: C 39.01, H 7.37, N 2.84.
C16H36NO4Re. Found, %: C 38.89, H 7.36, N 2.88. M
492.67.
Compound 5. IR spectrum, cm–1: 909 (Re=O),
1492, 2985, 3219. 1H NMR spectrum (CDCl3, 400 Hz,
r.t., ppm): 3.466–3.432 t (2H, CH2), 3.350 s (9H,
3CH3), 1.732–1.701 q (2H, CH2),1.348 m (4H, 2CH2),
1.246 m (22H, 11CH2), 0.881 t (3H CH3). Calculated,
%: C 42.67, H 7.92, N 2.62. C19H42NO4Re. Found, %:
C 42.70, H 7.93, N 2.60. M 534.75.
Preparation of quaternary ammonium perrhenates.
1.2 equiv. of KOH (0.269 g, 4.8 mmol) was added to a
solution of the quaternary ammonium bromine salts
(4 mmol) in 20 mL ethanol in argon, and the mixture
was stirred at room temperature for 6 h. The resulting
mixture was filtered through a Gooch funnel to remove
KBr and residual KOH, then 1.1 equiv. of NH4ReO4
(1.18 g, 4.4 mmol) was added, and after that, the
reaction temperature was increased to 80ºC and the
mixture was stirred for 2 h to remove NH3. After the
reaction was complete, the resulting solution was
concentrated to about 3 mL-volume and cooled down
to 0ºC, the obtained white precipitate was filtered,
triply washed with ethanol, and dried under vacuum at
70ºC to give the quaternary ammonium perrhenates.
Compound 1. IR spectrum, cm–1: 908 (Re=O),
1
1411, 1866, 3218. H NMR spectrum (D2O, 400 Hz,
r.t., ppm): 3.114 s (12H, 4CH3). Calculated, %: C
14.81, H 3.73, N 4.32. C4H12NO4Re. Found, %: C
14.79, H 3.75, N 4.36. M 324.35.
Catalytic reactions. In a typical reaction, cis-
cyclooctene (110 mg, 1 mmol) and the composite ionic
liquid containing 1–5 mol % of quaternary ammonium
perrhenates (1–5) and 1 mL of [Hmim]HSO4 ionic
liquid (catalyst and solvent) were mixed in the reaction
vessel at 80°C. The reaction was started with the
addition of hydrogen peroxide (5 mmol, 0.5 mL). The
course of the reactions was monitored by the
quantitative GC analysis. Samples were taken at
Compound 2. IR spectrum, cm–1: 908 (Re=O),
1
1488, 2919, 3413. H NMR spectrum (D2O, 400 Hz,
r.t., ppm): 3.201–3.158 q (8H, 4CH2), 1.197–1.170 t
(12H, 4CH3). Calculated, %: C 25.26, H 5.30, N 3.68.
C8H20NO4Re. Found, %: C 25.21, H 5.30, N 3.66. M
380.46.
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WANG et al.
regular time intervals, extracted with ethyl acetate, and
treated with a catalytic amount of MgSO4 and MnO2 to
remove water and destroy the unreacted H2O2. The
resulting slurry was filtered, and then filtrate was
injected into a GC column. The conversion of olefins
and the formation of epoxides were calculated from
calibration curves (r2 > 0.999) recorded prior to the
reaction. The residual solution was treated by washing
with ethyl acetate and then with dry n-hexane, and
finally, it was dried under vacuum at 70°C for 6 h to
obtain the recycled composite ionic liquid. The
composite ionic liquid was used directly for the next
catalytic run. The fresh substrate and H2O2 were then
added for a new reaction cycle.
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Five alkyl quaternary ammonium perrhenates are
prepared. The perrhenates are combined with [Hmim]
HSO4 to form the composite ionic liquids, which are
used as the catalyst and solvent for the oxidation of
cyclooctene to suberic acid. The results indicate that
the introduction of perrhenates can not only accelerate
the reaction but also increase the selectivity towards
suberic acid, with a highest product yield of 75%
obtained under the optimal conditions. To the best of
our knowledge, this is the first report on the oxidation
of cyclooctene to suberic acid, in which pherrhenate-
containing composite ionic liquids are used as effective
catalyst and hydrogen peroxide, as a green oxidant.
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