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Catalysis Communications 9 (2008) 859–863

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Carbon-based solid acid catalyzed highly efficient oxidations

of organic compounds with hydrogen peroxide
Arash Shokrolahi *, Abbas Zali, Hamid Reza Pouretedal, Mohammad Mahdavi
Chemistry Department, Malek-ashtar University of Technology, Shahin-Shahr, P.O. Box 83145-115, Islamic Republic of Iran

Received 28 April 2007; received in revised form 5 September 2007; accepted 10 September 2007
Available online 18 September 2007

Abstract

Carbon-based solid acid was found to be highly efficient, environmentally friendly and recyclable heterogeneous catalyst for oxidation
of sulfides to sulfones, tertiary amines to N-oxides, secondary alcohols to esters/lactones and aldehydes to methyl esters in excellent yields
under mild reaction conditions using hydrogen peroxide 30% as oxidant.
Ó 2007 Elsevier B.V. All rights reserved.

Keywords: Carbon-based solid acid; Oxidation; Hydrogen peroxide; Heterogeneous catalyst

1. Introduction Michikazu Hara and co-workers reported the synthesis

Sulfuric acid is an essential catalyst for the production
of industrially chemicals. However such liquid-acid catalyst
requires special processing in the form of neutralization
which involves costly and inefficient catalyst separation
from product and result in an unrecyclable sulfate waste.
According to the principal of the ‘‘green chemistry’’
production method should be refined so as to minimize
adverse effect on the environment or human health [1].
The migration to strong acids, which are recyclable and
nontoxic, from liquid-acids such as sulfuric acid is there-
fore a desirable goal [2,3]. Solid acids are conventional
materials that have wide applications in chemical produc-
tion, separation/purification, and polymer–electrolyte
fuel-cell (PEFC) technologies, and the chemical industry
is currently searching for a highly active and stable solid
acid to improve the environmental safety of the produc-
tion of chemicals and energy. An ideal solid material
for the applications considered here should have high sta-
bility and numerous strong protonic acid sites [4,5].
*
Corresponding author. Tel.: +98 312 522 0520; fax: +98 312 522 0420.
E-mail address: arshokrolahi@gmail.com (A. Shokrolahi).
of a carbon-based solid acid with a high density of sul-
fonic acid (SO3H). Such carbon-based solid acids can
be readily prepared by heating aromatic compounds such
as naphthalene in sulfuric acid at 473–573 K. In this syn-
thesis, the sulfonation of the aromatic compounds is the
first stage of the reaction. The resulting sulfonated aro-
matic compounds are incompletely carbonized, which
results in the formation of a solid with a nominal sample
composition of CH0.35O0.35S0.14. The resulting black pow-
der is insoluble in the solvents such as water, methanol,
ethanol, benzene, and hexane even at boiling tempera-
tures [6–8].
Various reagent including high valent metal and non-
metal oxides or their mineral salts such as potassium per-
manganate, potassium bromate, organic peroxides and
hydrogen peroxide can be used to oxidize organic function-
alities [9,10]. The usages of mineral oxidants are limited,
because they demand rigorous control of the experimental
conditions. Moreover the lack of selectivity in multistage
organic synthesis and tedious work-up are the other impor-
tant disadvantages of the mineral oxidants [11]. In this
work the carbon-based solid acid as heterogeneous catalyst
was used for oxidation of some organic compounds using
H2O2 as oxidant.

1566-7367/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.09.011
860 A. Shokrolahi et al. / Catalysis Communications 9 (2008) 859–863

Table 1 Table 2
Oxidation of sulfides to sulfones with hydrogen peroxide/carbon-base Oxidation of tertiary amines to N-oxide with hydrogen peroxide/carbon-
solid acid base solid acid
Entry R–S–R 0 Reaction time (min) Yielda (%) Entry Amine Reaction time (min) Yielda (%)
1 R@R 0 @C6H5 10 95 1 2-Picoline 65 90
2 R@C6H5; R 0 @CH3 10 95 2 3-Picoline 65 85
3 R@C6H5; R 0 @CH2C6H5 10 98 3 4-Picoline 55 90
4 R@C6H5; R 0 @n-C4H9 10 93 4 Pyridine 75 85
5 R@R 0 CH2C6H5 8–10 95 5 4-Cyanopyridine 110 72
6 R@R 0 @n-C4H9 5–7 95 6 N,N-Dimethylaniline 50 90
7 R@R 0 @n-C3H7 5–7 97 7 4-Methylmorpholine 60 95
8 R@CH2C6H5; R 0 @n-C4H9 10 98 a
Isolated yields.
9 Dibenzothiophene 40 75
a
Isolated yields.

Table 3
Oxidation of secondary alcohols to methylesters with hydrogen peroxide/carbon-base solid acid
Entry sec-Alcohol Product Reaction time (min) Yielda (%)
1 110 78
OH O

2 60 90
OH O

3 90 80
OH O

CH3 H3C

4 110 85
OH O

t-Bu t-Bu

5 180 70
O
CH
O
OH

6 170 75
CH3 O
CH OH
O CH3

a
Isolated yields.
 A. Shokrolahi et al. / Catalysis Communications 9 (2008) 859–863 861

2. Experimental Table 4
Oxidation of aldehydes to esters with hydrogen peroxide/nafion, H2SO4
and carbon-base solid acid in the same condition
Chemicals were purchased from Fluka, Merck and
Aldrich chemicals companies. The products were charac- Entry Aldehyde Time (min)/Yielda (%)
terized by comparison of their spectral (IR, 1H NMR), Nafion H2SO4 Carbon-based
TLC and physical data with the authentic samples. [12] solid acid
1 CHO 300/80 55/84 80/80
2.1. General experimental procedure

Carbon-based solid acid (0.2 g), substrate (1 mmol) and

hydrogen peroxide (aq. 30%, 5 mmol) in 1,2-dichloroeth-
2 CHO 150/89 25/85 35/85
ane (5 ml) were prepared as a mixture and used at refluxing
temperature. In the case of aldehyde oxidation, methanol
was used as solvent and MgSO4 (1 g) as water absorbing MeO
agent. The progress of reaction was monitored by TLC
method. At the end of reaction the catalyst was removed CHO
3 180/86 30/85 45/85
by filtration and the solvent evaporated under reduced
pressure. The precipitated residue was purified by column
chromatography on silica gel. Evaporation of the solvent
can yield the oxidized product. The yields of the products OMe
and the reaction times for the oxidation of sulfides, tertiary
amines, secondary alcohols and aldehydes are presented in
Tables 1–4. All products are characterized and their spectra 4 CHO 210/85 35/82 50/85
and physical properties matched with those reported in the
literature. Me

3. Results and discussion

5 CHO 240/90 45/95 60/90
Carbon-based solid acid was prepared according to the
reported procedure by Hara et al. [6]. The density of Cl
SO3 H group was measured using NaOH (0.01 mol L1)
as titrant by acid–base potentiometric titration. The
6 CHO 210/92 35/95 50/95
SO3H amount of attached to polycyclic aromatic carbon
was obtained 4.75 mmol g1. The composition of prepared
catalyst was obtained CH0.4O0.3S0.12 from elementary anal- Cl
ysis using Vario EL III of Elementar Company.
The X-ray diffraction spectrum (Bruker, D8Advance) of
carbon-based solid acid exhibits two broad and weak peaks 7 CHO – 45/90 65/90
(2h = 10–30°, 34–45°) attributed to amorphous carbon
(Fig. 1). NO2
We have used the carbon-based solid acid as a heteroge-
neous catalyst in the presence of hydrogen peroxide as an
oxidizing agent for oxidation of sulfides, tertiary amines, 8 CHO 210/80 40/90 55/85
secondary alcohols and aldehydes. The oxidation results
for a variety of sulfides are depicted in Table 1. All of the O2N
studied substrates were smoothly converted to the corre-
sponding sulfones with excellent yields in short times. a
Isolated yields.
Among the various studied sulfides, dibenzothiophene as
a hindered sulfide could be oxidized in a longer reaction
time with yield of 75% (Table 1, entry 9). Whereas, ali- des in high yields. However aliphatic tertiary amines and
phatic and aryl sulfides were more reactive and reactions pyridines containing electron-donating groups were found
of these compounds were completed in short times and to be more reactive and required lesser reaction times.
excellent yields. The oxidation of secondary alcohols to corresponding
The oxidation of several tertiary amines was carried out esters/lactones also has been studied in the same condi-
under similar reaction conditions and those results are pre- tions, which are presented in Table 3. In general, among
sented in Table 2. As seen from Table 2 all of the employed the various alcohols studied, alicyclic alcohols (Table 3,
tertiary amines were oxidized to the corresponding N-oxi- entries 1–4) were found to be more reactive as compared
862 A. Shokrolahi et al. / Catalysis Communications 9 (2008) 859–863

Fig. 1. X-ray diffraction spectrum of carbon-based solid acid.

O
R S R'
R S R'
R
OH O
R' R
O
O R R'O
H2O2
C SO3H C S O OH N R'
R"
O R"
R' N O
R
RCHO + CH3OH
RCOOCH3

Scheme 1.

to the aromatic alcohols (Table 3, entries 5 and 6). The
reaction involves the formation of carbonyl compounds
followed by their Bayer–Villiger oxidation to correspond-
ing esters. The oxidation of a variety of aldehydes were also
studied using the protocol involving drop-wise addition of
the hydrogen peroxide to the stirring mixture of the alde-
hyde and carbon-based solid acid in methanol at refluxing
temperature in the presence of anhydrous MgSO4. All of
the aldehydes used were selectively converted to methyl
esters in excellent yields which are shown in Table 4. In
general, substituted aldehydes were found to be more reac-
tive as compared to the benzaldehyde. The presence of
water absorbing agent (MgSO4) was found to be essential
for this reaction, because the existence of water can covert
aldehyde to corresponding carboxylic acid. Moreover cata-
lytic activities of carbon-based solid acid, Nafion NR-50
and sulfuric acid were compared in Table 4.
To investigate reusability and recyclability of the cata-
lyst, the oxidation of dibutyl sulfide was performed four
times. After completion of the reaction, the catalyst was
separated by filtration which can be used again for subse-
quent experiments after adding fresh substrate and oxidant
(aq. 30% H2O2) under similar reaction conditions. It was
found that the activity of catalyst has remained unchanged
after four catalytic cycles.
The reaction probably involves the in situ formation of
persulfonic acid by the reaction of sulfonic acid group of
the carbon-based solid acid with hydrogen peroxide, fol-
lowed by the oxygen transfer to the organic substrate as
shown in Scheme 1.
4. Conclusions
In this work, we have reported a new and highly efficient
methodology for the oxidation of sulfides to sulfones, ter-
tiary amines to N-oxides, secondary alcohols to esters/lac-
tones and aldehydes to methyl esters with aqueous
hydrogen peroxide in the presence of catalytic amounts
of carbon-based solid acid under mild conditions. The
cheapness and the availability of the reagents, easy and
clean work-up, and good to high yields make this method
attractive for the large-scale operations. We believe that
the present methodology would be improvement existing
methodologies.
 A. Shokrolahi et al. / Catalysis Communications 9 (2008) 859–863
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