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www.sciencedirect.comPreliminary communication/CommunicationZeolite nanoparticles (H-ZSM5) as a highly efficient, green,
and reusable heterogeneous catalyst for selective oxidation
of sulfides to sulfoxides under mild conditions
Amin Rostami*, Noosheen Saedmocheshi, Zeinab Shirvandi
Department of Chemistry, Faculty of Science, University of Kurdistan, 66177-15175 Sanandaj, Irana r t i c l e i n f o
Article history:
Received 15 March 2018
Accepted 15 May 2018
Available online 9 June 2018
Keywords:
Sulfide
Sulfoxide
Oxidation
Zeolite nanoparticles
Hydrogen peroxide* Corresponding author.
E-mail address: arostami372@gmail.com (A. Ros
https://doi.org/10.1016/j.crci.2018.05.004
1631-0748/© 2018 Académie des sciences. Publishea b s t r a c t
H-ZSM5 is applied as an efficient, highly reusable, and heterogeneous catalyst for the
oxidation of sulfides to sulfoxides using 30% H2O2 under solvent-free conditions at room
temperature. A variety of aromatic and aliphatic sulfides with different functional groups
were successfully oxidized with good to excellent yields in short reaction times. The
catalyst can be easily recovered by simple filtration and recycled for several consecutive
runs without any significant loss of its catalytic activity.
© 2018 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.1. Introduction
The selective oxidation of sulfides to sulfoxides is an
important reaction in organic chemistry, because sulfoxides
play an important role as versatile and synthetic in-
termediates for the production of various chemically and
biologically active molecules, and also activation of en-
zymes [1e4]. Therefore, various oxidizing agents (e.g.,
metal oxidants, organic oxidant, halogens, peroxides, and
air) have been proposed for this type of transformation [5
e7], but some of these methods have limitations such as
the use of stoichiometric toxic reagents, lowatomefficiency,
tedious work up of products, and the formation of large
amounts of toxic waste [8]. Among oxidizing agents,
hydrogenperoxide is themost attractive oxidant, because of
its environmental implications, lower costs, and is readily
available and produces water as the only byproduct [9e11],
but major drawback of hydrogen peroxide is its poor
oxidizing power; hence extensive studies have beentami).
d by Elsevier Masson SAS. Aundertaken to develop new catalysts (homogeneous and
heterogeneous catalysts) for this reaction [12e14].
Although these methods have partly addressed problem of
the stoichiometric reagents, some of these methods require
the transition metal catalyst for the selective oxidation of
sulfides, which have a number of disadvantages such as
preparation of complex catalyst, using toxic transitionmetal
compounds, and removing or recovery of the expensive
catalyst and remaining metals in products [15e19].
In recent years, one of the main objectives of moderni-
zations in catalytic processes is the development of new
and efficient technologies to improve environmental con-
ditions and industries related to fine chemicals. Porous
solids are particularly attractive, because they were re-
ported for potential applications such as catalysts, catalyst
supports, and as adsorbents [20e23].
Zeolites are porous crystalline materials that are defined
as aluminosilicates with discrete uniform particlewith high
internal surface area, small pore size, and flexible frame-
works [24,25], which are useful catalysts in petroleum
cracking, petrochemical industry, reforming processes, and
chemical reactions [26e28]. Also, zeolites can have bothll rights reserved.
Scheme 1. H-ZSM5 catalyzed the oxidation of sulfides to sulfoxides using
H2O2.
A. Rostami et al. / C. R. Chimie 21 (2018) 835e839836Brønsted and Lewis acid sites and can be used as a solid acid
to activate oxygenated molecules containing carbonyl and
hydroxyl groups, that is noncorrosive, and as a stabile, low-
cost, and commercially available reagent [29e31].
2. Experimental section
2.1. Materials and physical measurements
Sulfides, solvents (such as ethyl acetate and n-hexane),
and H2O2 (30%) were purchased from Merck chemical
company and used without further purification. H-ZSM5 is
commercially available from Zeolyst International. Melting
points were recorded using an Electrothermal 9100 appa-
ratus. 1H NMR spectra were recorded using a Bruker
400 MHz spectrometer in CDCl3 as solvent. Chemical shifts
are reported in ppm with Tetramethylsilane (TMS) as an
internal standard.
2.2. General procedure for the oxidation of sulfides to
sulfoxides using 30% H2O2 in the presence of H-ZSM5 as a
catalyst
H-ZSM5 (12 mg) was added to a mixture of sulfide
(1 mmol) and 30% H2O2 (2.4 equiv), then the mixture was
stirred at room temperature under solvent-free conditions
and the progress of the reaction was monitored byTable 1
Optimization of the reaction conditions with respect to the effect of the amount of
Entry H-ZSM5 (mg) H2O2 (equiv) Time Co
1 e 4.8 24 h 80
2 50 4.8 24 h 10
3 25 4.8 60 min 10
4 25 2.4 60 min 10
5 12 2.4 60 min 10
a Reaction conditions unless stated otherwise: sulfide (1 mmol), solvent-free,
b Conversion was determined by GC.
c The bold values represent the most effective reaction conditions.Thin-layer chromatography (TLC) (EtOAc/n-hexane, 1/2).
After completion of the reaction, EtOAc (5 mL) was added,
the catalyst was separated by filtration, and washed with
additional EtOAc (5 mL). The organic layer was washed
with brine (5mL) and dried over anhydrous Na2SO4. Finally,
the organic solvent was evaporated, and products were
obtained in good to high yield. All the products are known
and were characterized by comparing their spectral and
physical data with those of authentic samples.
2.3. Selected spectra data
2.3.1. Methyl phenyl sulfoxide
1H NMR (400 MHz, CDCl3) d¼ 7.70e7.62 (m, 2H),
759e7.48 (m, 3H), 2.72 (s, 3H) ppm; IR (KBr); 3030,
1488, 1451, 1296, 1128, 1029, 696 cm1.
2.3.2. Didodecyl sulfoxide
1H NMR (400 MHz, CDCl3) d¼ 2.75e261 (m, 4H),
1.85e1.75 (br, 4H), 1.45e1.29 (m, 36H), 0.91 (t, J¼ 4 Hz,
6H) ppm; IR (KBr); 2920, 2849, 1466, 1011.
3. Results and discussion
In continuation of our studies on environmentally
benign chemical processes [32e34], we report our results
about H-ZSM5 zeolite as a recyclable and effective hetero-
geneous catalyst for selective oxidation of sulfides to sulf-
oxides using 30% H2O2 (Scheme 1).
To optimize the reaction conditions, the oxidation re-
action of methyl phenyl sulfide to methyl phenyl sulfoxide
was selected as a model reaction. The effect of different
amounts of hydrogen peroxide and catalyst was investi-
gated on the model reaction under solvent-free conditions
at room temperature (Table 1). The oxidation of methyl
phenyl sulfide to methyl phenyl sulfoxide was not
completed using H2O2 (4.8 equiv) as an oxidant in the
absence of H-ZSM5 as a catalyst even after 24 h (Table 1,
entry 1). When 50 mg of H-ZSM5 catalyst and 4.8 equiv of
30% H2O2 were used both sulfoxide and sulfone were ob-
tained with 65% and 35%, respectively, within 24 h (Table 1,
entry 2). To control selectivity, the amounts of both catalyst
and oxidant were reduced. When the amount of catalystH-ZSM5 and 30% H2O2 on the oxidation reaction of methyl phenyl sulfide.a
nversion (%)b Yield of sulfoxide (%) Yield of sulfone (%)
70 0
0 65 35
0 98 0
0 98 0
0 98 0c
rt.
A. Rostami et al. / C. R. Chimie 21 (2018) 835e839 837was reduced to 25 mg, sulfoxide was found as only product
in 60min (Table 1, entry 3). The same resultwas obtained by
decreasing the amount of H2O2 to 2.4 equiv (Table 1, entry
4). After further investigation,12mgof H-ZSM5 catalyst and
2.4 equiv of 30%H2O2 under solvent-free conditions at room
temperature was found to be ideal for the complete con-
version of sulfide to sulfoxide (Table 1, entry 5).
To extend the general application of H-ZSM5 as a cata-
lyst, oxidation reactions of various sulfides were studied.
The sulfoxides were obtained in satisfactory yields in
relatively short reaction times and the results are shown in
Table 2. Interestingly, diphenyl sulfide as a model for theTable 2
Oxidation of sulfides to sulfoxides with 30% H2O2 in the presence of H-ZSM5 cat
Entry Sulfide Product
1 S
S
O
2 S
S
O
3
O
S
O
S
O
4 S Ph
PhS
O
5 C11H23 S C11H23
C11H23 C11H23S
O
6
Me
S
Me
Me Me
S
O
7 S
OH
OH
S
O
8 S
S
O
9 S OMe
O OMe
O
S
O
10 S
S
O
a Reaction conditions: sulfide (1 mmol), H2O2 (2.4 equiv), H-ZSM5 (12 mg), so
b Isolated yield.unreactive sulfides was also converted to the correspond-
ing sulfoxide at room temperature (Table 2, entry 10). Also,
to investigate the chemoselectivity of the described system,
oxidation of 2-(methylthio)ethanol as a model reactionwas
examined and which alcoholic groups remained intact
during the oxidation reactions (Table 2, entry 7).
Although the exact role of H-ZSM5 catalyst is not clear,
on the basis of the already reported mechanism for the
oxidation of sulfides using hydrogen peroxide in the pres-
ence of an acid catalyst [11,39e41], in the first step, the H-
ZSM5 catalyst might act as protic acid, which activates the
OeO bond in hydrogen peroxide (Scheme 2).alyst under optimized reaction conditions.a
Time (min) Conversion (%) Yield (%)b MP (C) [Reference]
60 100 98 Oil [35]
73 100 99 Oil [35]
7 100 96 Oil [36]
304 100 89 114e115 [35]
170 100 87 86e88 [38]
10 100 94 Oil [37]
1 100 96 Oil [36]
65 100 82 Oil [37]
1 100 96 Oil [36]
50 100 98 59e61 [38]
lvent-free, rt.
Scheme 2. Proposed mechanism for the oxidation of sulfides to sulfoxides using H2O2 catalyzed by H-ZSM5.
A. Rostami et al. / C. R. Chimie 21 (2018) 835e839838To commercial applications of heterogeneous systems,
the reusability of the catalyst is an important factor.
Therefore, the recovery and recyclability of the H-ZSM5 as a
catalyst for the oxidation of methyl phenyl sulfide with
H2O2 was evaluated. After the completion of a reaction, the
catalyst was recovered by centrifuge technique, washed
with EtOAc and distilled water to remove residual product,
dried under vacuum at room temperature, and reused for
next runs. As shown in Fig. 1, the catalyst can be recovered
and reused for 20 runs without any significant loss of its
catalytic activity.Fig. 1. Recyclability of H-ZSM5 catalyst for the oxidation of methyl phenyl sulTo assess the efficiency of H-ZSM5 as a catalyst, we
compared the resultof theoxidationofmethyl phenyl sulfide
to methyl phenyl sulfoxide with previously reported results.
As shown in Table 3, the previously reported procedures
suffer fromone ormore limitations such asusing a transition
metal (Table 3, entries 2e5), the need for volatile and toxic
organic solvents (Table 3, entries 2e5), special efforts for the
preparation of catalyst (Table 3, entries 2e4), and longer
reaction times (Table 3, entries2e4). Theother advantagesof
H-ZSM5 are the commercial availability and the low cost,
nontoxicity, stability, easily separable, and highly reusable.fide with 30% H2O2 at room temperature under solvent-free conditions.
Table 3
Comparison of the activity of H-ZSM5 with the various catalysts in the oxidation of methyl phenyl sulfide with 30% H2O2.
Entry Catalyst/oxidant Reaction conditions Time (min) Yield (%) Reference
1 H-ZSM5 zeolite/H2O2 Solvent-free, rt 50 98 This study
2 Peroxotungstate supported on silica/H2O CH2Cl2/MeOH, 8 C 150 91.5 [42]
3 VO2F(dmpz)2/H2O2 CH3CN, 0e5 C 300 95 [17]
4 Ru-PVP/g-Al2O3/H2O2 CH3CN, rt 120 98 [43]
5 Cr(III)/H2O2 CH3CN, rt 72 93 [44]
A. Rostami et al. / C. R. Chimie 21 (2018) 835e839 8394. Conclusion
We have demonstrated that H-ZSM5 can be used as a
green, efficient, and reusable nanocatalyst for the oxidation
of sulfides to sulfoxides using 30% H2O2 at room tempera-
ture. The notable advantages of the present protocol and
this heterogeneous catalyst are the use of a commercially
available, eco-friendly, inexpensive, and chemically stabile
materials, the metal-free and mild reaction conditions, the
operational simplicity, practicability, good to high yields of
products, and good chemoselectivity. Furthermore, the
catalytic system can be easily recycled using simple filtra-
tion and reused for 20 times without any significant loss of
the activity, which makes it a promising material for
practical and large-scale applications.
Acknowledgments
The authors are grateful to the University of Kurdistan
Research Councils for partial support of this work.
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