New catalytic reactions in the presence of Mo-V-phosphoric heteropoly acid solutions

Article abstract of DOI:10.1007/s11167-005-0386-9

The possibility of performing new catalytic reactions in the presence of solutions of H _x+3PMo_12-x . V_xO₄₀ Mo-V-phosphoric heteropoly acids was examined.

Full text of DOI:10.1007/s11167-005-0386-9

Russian Journal of Applied Chemistry, Vol. 78, No. 5, 2005, pp. 758 764. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5,
005, pp. 772 778.
Original Russian Text Copyright
2
2005 by Zhizhina, Simonova, Russkikh, Matveev.
CATALYSIS
New Catalytic Reactions in the Presence of Mo V-Phosphoric
Heteropoly Acid Solutions
E. G. Zhizhina, M. V. Simonova, V. V. Russkikh, and K. I. Matveev
Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk, Russia
Vorozhtsov Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, Russia
Received September 30, 2004; in final form, February 2005
Abstract The possibility of performing new catalytic reactions in the presence of solutions of Hx + 3PMo12 x
V O Mo V-phosphoric heteropoly acids was examined.
x
40
Solutions of Mo V-phosphoric heteropoly acids
HPAs) of the Keggin structure and the composition
EXPERIMENTAL
(
Hx+3PMo12 xV O (HPA-x, x = 2 6) find expand-
In all the processes, HPA solutions were regen-
erated at 150 160 C and oxygen pressure of 6 9 atm
4, 5]. Almost complete regeneration of the activity of
x
40
ing application as effective catalysts of oxidation of
organic compounds with oxygen [1 3]. In the pres-
ence of HPAs, these reactions often proceed in two
steps performed in different reactors. In step (1), sub-
[
HPA solutions allowed their multiple reuse.
Oxidation of aniline and o-toluidine. Aniline
strate H Su is oxidized with HPA to form the reaction
and other aromatic amines are often oxidized with
2
product SuO and reduced HPA H HPA. In step (2),
strong oxidants such as NaClO , K Cr O , etc.
m
3 2 2 7
Depending on the oxidant and conditions, the reac-
tion can yield 1,4-benzoquinone (BQ) or polyani-
line (PAn), a product of oxidative polymerization
HPA is regenerated with oxygen. Catalytic reac-
tion (3) is a sum of these reactions; it proceeds in
the mode of non-steady-state catalysis. In these reac-
tions, HPA acts as reversible oxidant.
{scheme (4) [6 8]}. Polyaniline can be quantitatively
oxidized to BQ [8]:
m/4H Su + m/4H O + HPA
m/4SuO + H HPA, (1)
m
2
2
NH2
[O]
H HPA + m/4O
HPA + m/2H O,
(2)
(3)
m
2
2
HPA
(
HN
HN
)z (N
N
)y
H Su + O
SuO + H O.
2
2
2
[
O]
In HPA solutions, only vanadium ions undergo
reversible redox transformations: V(V) V(IV).
Separate performance of reactions (1) and (2) provides
high selectivity of reaction (1).
O
O. (4)
Being a conducting polymer, PAn is widely used in
In this work we studied the oxidation of new sub-
strates [aniline (An), o-toluidine (TD), hydroquinone
chemical current sources [9, 10] and as stable black
dye [11]. Development of environmentally safe proce-
dures for catalytic oxidation of aniline to form PAn is
an urgent problem.
(
HQ), and partially hydrogenated quinones of naph-
thalene and anthracene series] in the presence of 0.2
.25 M aqueous solutions of HPAs-x (x = 3 6, where
0
We attempted to solve this problem using solutions
of HPAs-x (x = 3, 4). Here we report the data on oxi-
dation of AN and TD in HPA solutions; depending on
the reaction conditions, either PAn or BQ can be
obtained.
x is the number of vanadium atoms in the molecule).
Also, synthesis of 9,10-anthraquinone (AQ) was per-
formed by combining the diene synthesis and oxida-
tion of the adducts.
1
070-4272/05/7805-0758 2005 Pleiades Publishing, Inc.

NEW CATALYTIC REACTIONS
759
Aromatic amines were oxidized in a 100-ml flask
at stirring with a magnetic stirrer. Aniline (5.5 mmol)
was added to a 0.2 M aqueous solution of HPA-3
Table 1. Yield of PAn in oxidation with HPA-3 solution
at 22 C for 30 min; An content 0.5115 g (5.5 mmol)
Amount of HPA-3 : AN Amount of
PAn : An
(
3.66 mmol), and a black precipitate (0.4858 g) that
formed upon stirring of the reaction mixture for
0 min at 22 C was filtered off. The properties of this
An, mmol molar ratio
PAN, g
weight ratio
3
4
3
1
.58
.66
.83
0.83
0.67
0.33
0.3802
0.4858
0.0912
0.74
0.95
0.18
black compound correspond to those of PAn prepared
by noncatalytic oxidation of aniline [7, 12]. This
product is insoluble in organic solvents, organic acids
(
e.g., acetic, oxalic, and tartaric acids), and concen-
*
PAn was separated from HPA-3 solution by filtration, washed,
trated HCl, and is poorly soluble in concentrated KOH
and NaOH. It is soluble only in concentrated H SO
and dried over CaCl .
2
2
4
and, with oxidation, in concentrated HNO . Except
Our data show that, depending on the experimental
3
the 1000 800 cm 1 range, the IR spectrum of this
compound essentially coincided with the IR spectrum
of PAn [poly(p-phenylenaminimine)] [12].
conditions, An and TD are oxidized in HPA-x solu-
tions yielding either the corresponding PAn or the cor-
responding 1,4-quinone. Regeneration of HPA-x with
oxygen by reaction (2) [4, 5] closes the catalytic cycle
and thus allows development of a catalytic process for
synthesis of PAn in the presence of HPA solutions.
The composition of this product is as follows, %:
C 59.36, H 4.39, and N 11.98. Calculated composi-
tion of PAn {z = y in scheme (1) [7]}, %: C 79.56,
H 4.97, and N 15.47. The C/N ratio in our compound
and in those prepared in [7] is 4.95 and 5.14, respec-
tively. This difference is probably due the fact that
x and z in the formula of the PAn obtained in our
Preparation of 1,4-benzoquinone, 1,4-naphtho-
quinone, and 9,10-anthraquinone by oxidative de-
hydrogenation. p-Quinones are usually obtained by
oxidation of appropriate substrates with strong oxi-
dants. For example, BQ is prepared by oxidation of
hydroquinone with salts of copper(II) [13], iron(III)
work differ from those in the formula C H4.5N {z = y,
scheme (1) [7]}.
6
[
14], chromium(VI) [15], and sodium nitrosodisulfo-
o-Toluidine was oxidized under the similar condi-
tions (22 C, 30 min). For this purpose, the substrate
5.5 mmol) was added to a 0.2 M aqueous solution
of HPA-3 (3.66 mmol). As a result, we obtained
methylated PAn (0.5620 g) of the following composi-
tion, %: C 60.62, H 6.30, and N 6.59 [calculated, %:
C 82.76, H 3.45, and N 13.79]. Higher content of H
and C in the product is due to the additional methyl
group in the monomer.
nate (Fremy salt) [16]. 1,4-Naphthoquinone (NQ) is
prepared by oxidation of naphthalene with salts of
chromium(VI) and cerium(IV) [17]. Anthraquinone is
most often prepared from anthracene by oxidation
with air at 360 380 C in the presence of V O cata-
lyst [18] or with such strong oxidants as ZnCr O
3
ally inefficient because of high cost of the oxidant;
moreover, they are environmentally hazardous because
of significant amount of wastes requiring utilization.
Therefore, development of environmentally safe
catalytic processes to prepare p-quinones is urgent.
Owing to high oxidative power and reversible redox
cycle [1, 19], the use of HPA-x solutions as oxidation
catalysts seems promising.
(
2
5
2
7
H O or AcO H [17]. These processes are economic-
2 2
1
The GLC and H NMR data show that, at 90
1
00 C, PAn prepared by low-temperature oxidation of
An dissolves in excess HPA-3 or HPA-4 to form BQ
at the molar ratio HPA-x : aniline = 3, recalculated to
the initial An concentration. This result agrees with
published data [8] and additionally confirms forma-
tion of PAn. If An is oxidized directly in excess
HPA-x (x = 3, 4) at temperature higher than 70 C,
BQ is formed in a quantitative yield.
It was found [20 22] that alkyl-substituted phenols
of the benzene and naphthalene series can be oxidized
in the presence of HPA solutions to form the corre-
sponding p-quinones with high selectivity (85 99%).
These reactions are usually carried out in two-phase
systems (e.g., HPA aqueous solution + solution of
substrate and reaction products in organic solvent). In
this study, we also used HPA solutions for catalytic
oxidation with air (oxidative dehydrogenation) of par-
tially hydrogenated phenols of benzene, naphthalene,
and anthracene series to prepare the corresponding
p-quinones [23].
As seen from Table 1, the yield of PAn depends on
the HPA-3 : An molar ratio. The yield of PAn is low
at HPA-3 deficiency due to incomplete An conver-
sion, whereas at HPA-3 excess it decreases owing to
partial oxidation of An to BQ. In HPA-4 solutions the
highest yield of PAn is observed at the molar ratio
HPA-4 : An = 0.5, which is due to larger number of
vanadium(V) atoms than in HPA-3, i.e., to greater
oxidative power.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 5 2005

760
ZHIZHINA et al.
Table 2. Oxidative dehydrogenation of partially hydrogenated quinones in a 0.25 M solution of HPA-4 (H PMo V O ,
7
8 4 40
5
.62 mmol)
Yield, %
Substrate,
mmol
HPA : substrate
molar ratio
Substrate
conversion, %
Solvent, ml
T,
C
, h
quinone dihydroquinone
DDN:
1-Octanol:
NQ:
1
2
4
5.62
2.81
1.40
10
4
4
65
68
68
2.5
2.5
1
67
62
68
100
100
100
DHN:
DHA:
4
4
1.40
1.40
1.40
1.40
Chloroform, 5
Hexane, 5
50
70
60
70
1
1
1
1
30
82
71
96
59
6
11
97
100
92
4
THN, 4
THA:
4
100
AQ:
1.40
1.40
1.56
80
90
60
1
3
3
5
49
33
67
37
67
72
100
100
4
Octanol, 4
4
*
HQ:
Chloroform:
BQ:
4
8
1.40
0.70
7
5
45
24
0.5
0.5
82
97
100
100
*
Experiment was performed with 0.25 M solution of HPA-6 (H PMo V O , 25 ml, 5.62 mmol).
9 6 6 40
Oxidative dehydrogenation was carried out with
tion heated to a required temperature before switch-
ing on stirring. As the initial substrate we can use
4a,5,5,8a-tetrahydronaphthtalenedione (THN), and not
the product of its isomerization (DDN). In this case,
the yield of NQ reached 96%. No DHN was found in
the reaction mixture (Table 2):
stirring in a 100-ml temperature-controlled conical
flask equipped with a reflux condenser. In the case of
two-phase systems, the reaction products are separated
from the catalyst by phase separation. If the reaction
was performed in the absence of organic solvent, the
solid products were filtered off from the HPA solu-
tion. For more complete isolation of the reaction prod-
ucts, they were extracted with an organic solvent
HPA-4
THN
NQ.
96%
(6)
70 C, 1 h
(
chloroform, benzene); the extracts were dried over
These data suggest that the known procedure [24,
5] for preparing NQ [scheme (7)], which requires
preliminary isomerization of THN in DDN and sub-
sequent two-stage oxidation first into DHN and then
into NQ using two different oxidants, can be sig-
nificantly simplified and performed in one stage in
the presence of HPA solutions:
CaCl and evaporated to dryness. The components of
the residue were separated chromatographically (SiO ,
hexane, benzene, and chloroform eluents). The yields
of the products were determined from the H NMR
spectra. The data on the oxidative dehydrogenation of
several compounds studied are listed in Table 2.
2
2
2
1
The oxidative dehydrogenation of 1,4-dihydroxy-
O
H H
O
5
,8-dihydronaphthalene (DDN) in 0.25 M solution of
HPA-4 at 50 70 C gives NQ in a yield from 30 to
2% and 5,8-dihydronaphthalene-1,4-dione (DHN) in
H
8
a yield of up to 59% [scheme (5)]. With increasing
temperature, the yield of NQ increases:
H
O
H H
O
THN
O
BQ
H H OH
H H
HPA-4
DDN
DHN + NQ.
59% 30 82%
(5)
50 70 C,
Isomerization
(7)
NQ.
1
2.5 h
_
_
2
H
2H
This reaction can be performed without organic
solvent. A solid substrate is added into an HPA solu-
H H OH
DDN
H H
O
DHN
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 5 2005

NEW CATALYTIC REACTIONS
761
The oxidative dehydrogenation of 1,4,4a,9a-tetra-
hydro-9,10-anthraquinone (THA) to 1,4-dihydro-
then dehydrated in the presence of various hetero-
geneous catalysts to form AQ [30].
9
,10-anthraquinone (DHA) (Table 2) in the presence
Diene synthesis is one of the commercial proce-
dures for preparing THA, DHA, and AQ. It is based
on the catalytic gas-phase oxidation of naphthalene
into NQ and its subsequent reaction with 1,3-buta-
diene [26]. The primary addition products (adducts)
are obtained in organic solvents either at elevated
pressure of 1,3-butadiene of 0.3 2.0 MPA or in the
presence of organic acids to decrease the pressure.
In the presence of oxygen or alkalis, THA (adduct
of diene synthesis) isomerizes to form 1,4-dihydro-
9,10-dihydroxyanthracene, and this product is then
oxidized in DHA and AQ with strong oxidants in
acidic solutions or with atmospheric oxygen in an
alkaline medium.
of HPA-4 solutions proceeds under more severe con-
ditions than hydrogenation of THN and DDN:
HPA-4
THA
DHA + AQ.
(8)
6
0 90 C, 1 3 h 37 67% 5 49%
On the contrary, hydroquinone is readily oxidized
into BQ even at room temperature with a high yield
(
up to 98%), and with increasing temperature the yield
of BQ decreases:
HPA-4
4 25 C, 0.5 h 82 98%
HQ
BQ.
(9)
2
The above data show that p-quinones of the ben-
zene, naphthalene, and anthracene series can be pre-
pared by oxidation of their partially hydrogenated
derivatives in HPA solutions. Since DDN and THA
are rather expensive, commercial synthesis of NQ and
AQ should be based on more available substrates.
However, the successful oxidative dehydrogenation of
various substrates (Table 2) shows that the HPA solu-
tions can be used as bifunctional catalysts for prepar-
ing 1,4-naphthoquinone and 9,10-anthraquinone.
All modern procedures for preparing AQ and its
derivatives are multistage and environmentally hazard-
ous; each step produces significant amount of wastes
including strong acids, spent acid catalysts, and oxi-
dants, e.g., toxic compounds of chromium(VI) and
(III), which require recycling.
Growing demand for AQ and its derivatives cannot
be complied using outmoded and environmentally
hazardous processes. Russia has no large-scale com-
mercial production of AQ, and only foreign com-
panies supply the required reagent. Hence, develop-
ment of the domestic environmentally safe production
of AQ and its derivatives is a very urgent problem.
Diene synthesis of 9,10-anthraquinone. Anthra-
quinone and its derivatives are intermediate products
in synthesis of dyes, analytical reagents, and drugs
[
26]. 9,10-Anthraquinone is used as a catalyst of redox
reactions, in particular, in production of hydrogen
peroxide [27]. Moreover, AQ and its derivatives cata-
lyze wood delignification and increase the yield of
cellulose, degree of its bleaching, and its strength
properties [28]. For this purpose, soluble AQ, i.e.,
sodium salt of THA (intermediate product in the diene
synthesis of 9,10-anthraquinone), is widely used [29].
Catalysts based on HPA show promise for this
purpose. For example, condensation of NQ with 2,3-
dimethyl-1,3-butadiene (Diels Alder reaction) in
the presence of tungsten HPA (H PW O
and
3
12 40
Ce0.87H0.4PW O ) yields substituted THA (70
12
40
80%) [31]. No oxidation of this product was observed
because these HPAs exhibit no oxidative power [1,
Known procedures for preparing AQ can be sub-
divided in two groups. The first group includes oxida-
tion of anthracene into AQ with atmospheric oxygen
and other oxidants at 350 400 C [17, 26], and the
second group is based on the cyclization reactions
involving inter- and intramolecular acylation and
Diels Alder diene synthesis [26]. In the case of acyla-
tion, benzene and phthalic anhydride are the initial
3
1].
In the diene synthesis, we used solutions of HPA-x
(x = 4 6) [23], which are both strong acids catalyzing
Diels Alder reaction and strong reversible oxidants.
In contrast to Meuzelaar et al. [31], we succeeded in
combining the diene synthesis with oxidation of
the adducts in the presence of HPA solutions [23].
reagents and synthesis is carried out in several steps. 9,10-Anthraquinone and its derivatives were prepared
The first stage yields 2-benzoylbenzoic acid, which is
by one-pot synthesis:
OH
O
O
O
O
O
O
O
HPA
HPA
HPA
HPA
_
,
_
_
+
_
(10)
_
+
_
_
+
_
_
+
2
e, 2H
2e, 2H
2e, 2H
O
OH
BQ
THN
DHN
NQ
HQ
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 5 2005

762
ZHIZHINA et al.
Table 3. Preparation of a mixture of THA, DHA, and AQ from HQ in 0.25 M solution of HPA-6 (H PMo V O )
9
6 6 40
by the Diels Alder reaction. 1,3-Butadiene medium, initial content of HQ 5 mmol, reaction time 10 h, conversion of HQ
100%; content of the reaction products in the reaction mixture was determined chromatographically
Reaction products, %
DHA THA
HPA-6, mmol
HPA-6 : HQ molar ratio
Solvent, ml
T,
C
AQ
NQ
6
6
6
6
.25
.25
.25
.25
1.25
1.25
1.25
1.25*
2.5
Chloroform, 5
Trichloroethylene, 5
23
1
2
3
4
9
4
23
46
67
65
45
49
71
47
15
17
21
22
23
23
23
23
40
9
10
19
19
12.5
2.5
1
2.5
*
0.25 M solution of HPA-6 acidic salt NaH PMo V O was used in the experiment.
8
6
6 40
O
O
O
O
O
O
HPA
HPA
HPA
.
(11)
+
_
_
_
_
+
_
_
+
2
e, 2H
2e, 2H
O
O
DHA
AQ
NQ
THA
Hydroquinone was used as the initial substrate
schemes (10), (11)]. It was oxidized to BQ and then
condensed with 1,3-butadiene. The adducts of the
diene synthesis were oxidized to NQ in the same
HPA-x solution. In the second step of the process
soluble products (AQ, DHA, THA) were filtered off
[
from the aqueous solution of H HPA. The solution of
m
HPA-x was regenerated at 150 160 C under oxygen
pressure, as in the case of oxidation of aniline, which
allows multiple reuse of the HPA solutions.
[
scheme (11)], NQ was condensed with 1,3-butadiene
First we studied preparation of AQ and its hydro-
genated derivatives THA and DHA from HQ in HPA
solutions by reaction schemes (10) and (11). The ex-
perimental results are listed in Table 3. As seen, with
increasing temperature and HPA-6 : HQ molar ratio,
the content of AQ in the reaction mixture increases,
whereas addition of a solvent decreases the AQ yield.
to form THA, which was then oxidized to DHA and
AQ. All the above reactions were performed as one-
pot process owing to bifunctional properties of HPA
acting as both acid and oxidation catalyst. In the
course of this process, HPA was reduced to H HPA,
where m is the number of electrons accepted by the
m
HPA molecule. After the reaction completion, poorly
For better understanding of processes (10) and (11),
we studied separately step (11), i.e., preparation of
a mixture of AQ, THA, and DHA from NQ. These
data are also of independent importance. For example,
if NQ as initial substrate will be acceptable by a cheap
method (e.g., by oxidation of naphthalene), then the
one-pot process for preparing AQ from NQ will be
competitive, because at present HQ is a cheaper sub-
strate as compared to NQ.
,
, %
We found that the rate of reaction (11) strongly
depends on temperature. At 40 C, the rate of the diene
synthesis is low, but with increasing temperature to
T, C
Fig. 1. (1, 2) Conversion of NQ and (3) yield of AQ as
functions of temperature T. 1,3-Butadiene medium, 0.2 M
HPA-4 (25 ml), NQ 0.79 g. Conversion of NQ: (1) after 7 h
8
0 C the conversion of NQ and the yield of AQ rapid-
1
ly increase (Fig. 1). Simultaneously the solubility of
(
H NMR data) and (2) after 5 h (GLC data); (3) yield of
1
NQ in HPA-x solution also increases, which promotes
AQ in 7 h ( H NMR data).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 5 2005

NEW CATALYTIC REACTIONS
763
potential for a longer period, which provides higher
conversion in reaction (11).
,
mol %
CONCLUSIONS
(1) Aniline and o-toluidine in solutions of Mo V-
phosphoric heteropoly acids are oxidized to 1,4-ben-
zoquinone or undergo oxidative polymerization to
form polyanilines.
,
h
(2) The adducts of the Diels Alder reaction are
oxidized with heteropoly acid solutions to the corre-
sponding p-quinones.
Fig. 2. Changes in the composition of the reaction products
with reaction time . 1,3-Butadiene medium, 80 C, 0.2 M
HPA-4 (25 ml), NQ 0.79 g. (1) AQ, (2) DHA, (3) THA,
and (4) NQ.
(3) Solutions of heteropoly acids can be used as
bifunctional catalysts, i.e., acid catalysts in the Diels
Alder reaction and oxidation catalysts. In the presence
of HPA-x (x = 4 6) solutions, a mixture of the prod-
ucts is obtained with a high content of 9,10-anthra-
quinone and 1,4,4a,9a-tetrahydro-9,10-anthraquinone
at nearly quantitative conversion of the initial substrate
the reaction. The NQ conversion and AQ yield in-
crease with time. The dependence of the precipitate
composition on the reaction time (based on the
1
H NMR data) is shown in Fig. 2. As seen, the frac-
tion of DHA in the reaction mixture is greater than
that of THA. This suggests that the oxidation of DHA
in AQ is slower than the oxidation of THA to DHA.
(
hydroquinone, 1,4-benzoquinone, or 1,4-naphtho-
quinone). The one-pot process combines reactions of
diene synthesis and oxidation of its products.
We also studied the condensation of HPA-4 with
1
,3-butadiene as influenced by some organic solvents.
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We found that such solvents as toluene, benzene, and
chloroform do not noticeably affect the NQ conver-
sion and AQ yield. These results agree with the data
on the diene synthesis of NQ with 1,3-butadiene in
HPA-6 solution (Table 2).
1
2
. Kozhevnikov, I.V., Catalysis by Polyoxometalates,
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results are listed in Table 4.
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Table 4. AQ yield in the diene synthesis as influenced by
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HPA-4 (25 ml), time 5 h, temperature 80 C
8
. Willstatter, R. and Dorogi, S., Chem. Ber., 1909,
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Weighed portion
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