Zeolite nanoparticles (H-ZSM5) as a highly efficient, green, and reusable heterogeneous catalyst for selective oxidation of sulfides to sulfoxides under mild conditions

Article abstract of DOI:10.1016/j.crci.2018.05.004

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.

Full text of DOI:10.1016/j.crci.2018.05.004

C. R. Chimie xxx (2018) 1e5
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Preliminary communication/Communication
Zeolite 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, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
H-ZSM5 is applied as an efficient, highly reusable, and heterogeneous catalyst for the
oxidation of sulfides to sulfoxides using 30% H O under solvent-free conditions at room
2 2
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.
Received 15 March 2018
Accepted 15 May 2018
Available online xxxx
Keywords:
Sulfide
©
2018 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Sulfoxide
Oxidation
Zeolite nanoparticles
Hydrogen peroxide
1. Introduction
undertaken to develop new catalysts (homogeneous and
heterogeneous catalysts) for this reaction [12e14].
The selective oxidation of sulfides to sulfoxides is an
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 transition metal
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 particle with 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 both
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, lowatom efficiency,
tedious work up of products, and the formation of large
amounts of toxic waste [8]. Among oxidizing agents,
hydrogenperoxide is the most 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 been
*
Corresponding author.
E-mail address: arostami372@gmail.com (A. Rostami).
https://doi.org/10.1016/j.crci.2018.05.004
631-0748/© 2018 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.
1
Please cite this article in press as: A. Rostami, et al., Zeolite nanoparticles (H-ZSM5) as a highly efficient, green, and reusable
heterogeneous catalyst for selective oxidation of sulfides to sulfoxides under mild conditions, Comptes Rendus Chimie (2018),
https://doi.org/10.1016/j.crci.2018.05.004

2
A. Rostami et al. / C. R. Chimie xxx (2018) 1e5
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
2 4
with brine (5 mL) and dried over anhydrous Na SO . 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
Scheme 1. H-ZSM5 catalyzed the oxidation of sulfides to sulfoxides using
2.3.1. Methyl phenyl sulfoxide
H
2
O
2
.
1
H NMR (400 MHz, CDCl
3
)
d
¼ 7.70e7.62 (m, 2H),
7
1
59e7.48 (m, 3H), 2.72 (s, 3H) ppm; IR (KBr); 3030,
488, 1451, 1296, 1128, 1029, 696 cm .
ꢀ1
Brønsted 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
.3.2. Didodecyl sulfoxide
1
H NMR (400 MHz, CDCl
3
)
d
¼ 2.75e261 (m, 4H),
1.85e1.75 (br, 4H), 1.45e1.29 (m, 36H), 0.91 (t, J ¼ 4 Hz,
6
H) ppm; IR (KBr); 2920, 2849, 1466, 1011.
2
. Experimental section
3. Results and discussion
2
.1. Materials and physical measurements
In continuation of our studies on environmentally
Sulfides, solvents (such as ethyl acetate and n-hexane),
and H O (30%) were purchased from Merck chemical
2 2
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
00 MHz spectrometer in CDCl as solvent. Chemical shifts
3
are reported in ppm with Tetramethylsilane (TMS) as an
internal standard.
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-
2 2
oxides using 30% H O (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
4
2
.2. General procedure for the oxidation of sulfides to
sulfoxides using 30% H
catalyst
O
2 2
in the presence of H-ZSM5 as a
2 2
completed using H O (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
H-ZSM5 (12 mg) was added to a mixture of sulfide
1 mmol) and 30% H (2.4 equiv), then the mixture was
stirred at room temperature under solvent-free conditions
and the progress of the reaction was monitored by
2 2
30% H O were used both sulfoxide and sulfone were ob-
(
2
O
2
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 catalyst
Table 1
2 2
Optimization of the reaction conditions with respect to the effect of the amount of H-ZSM5 and 30% H O
on the oxidation reaction of methyl phenyl sulfide.a
Entry
H-ZSM5 (mg)
H
2
O
2
(equiv)
Time
Conversion (%)b
Yield of sulfoxide (%)
Yield of sulfone (%)
1
2
3
4
5
e
4.8
4.8
4.8
2.4
2.4
24 h
24 h
60 min
60 min
60 min
80
70
65
98
98
98
0
35
0
0
0
50
25
25
12
100
100
100
100
c
a
Reaction conditions unless stated otherwise: sulfide (1 mmol), solvent-free, rt.
Conversion was determined by GC.
The bold values represent the most effective reaction conditions.
b
c
Please cite this article in press as: A. Rostami, et al., Zeolite nanoparticles (H-ZSM5) as a highly efficient, green, and reusable
heterogeneous catalyst for selective oxidation of sulfides to sulfoxides under mild conditions, Comptes Rendus Chimie (2018),
https://doi.org/10.1016/j.crci.2018.05.004

A. Rostami et al. / C. R. Chimie xxx (2018) 1e5
3
was reduced to 25 mg, sulfoxide was found as only product
in 60 min (Table 1, entry 3). The same result was obtained by
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 reaction was
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).
decreasing the amount of H
2
O
2
to 2.4 equiv (Table 1, entry
). After further investigation,12 mg of H-ZSM5 catalyst and
.4 equiv of 30% H under solvent-free conditions at room
4
2
2 2
O
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 the
Table 2
2 2
Oxidation of sulfides to sulfoxides with 30% H O
in the presence of H-ZSM5 catalyst under optimized reaction conditions.a
ꢁ
Entry
1
Sulfide
Product
Time (min)
60
Conversion (%)
100
Yield (%)b
98
MP ( C) [Reference]
Oil [35]
S
S
O
S
2
73
100
99
Oil [35]
O
S
3
4
7
100
100
96
89
Oil [36]
O
S
S
O
O
304
114e115 [35]
S
Ph
O
S
Ph
5
6
170
10
100
100
87
94
86e88 [38]
C H
S
C H
11 23
O
S
11
23
C H
C H
11 23
1
1
23
Oil [37]
S
O
Me
S
Me
S
Me
O
Me
7
1
100
96
Oil [36]
OH
S
OH
8
9
65
1
100
100
82
96
Oil [37]
Oil [36]
S
O
S
S
OMe
O
S
OMe
O
O
10
50
100
98
59e61 [38]
S
O
S
a
2 2
Reaction conditions: sulfide (1 mmol), H O (2.4 equiv), H-ZSM5 (12 mg), solvent-free, rt.
Isolated yield.
b
Please cite this article in press as: A. Rostami, et al., Zeolite nanoparticles (H-ZSM5) as a highly efficient, green, and reusable
heterogeneous catalyst for selective oxidation of sulfides to sulfoxides under mild conditions, Comptes Rendus Chimie (2018),
https://doi.org/10.1016/j.crci.2018.05.004

4
A. Rostami et al. / C. R. Chimie xxx (2018) 1e5
2 2
Scheme 2. Proposed mechanism for the oxidation of sulfides to sulfoxides using H O catalyzed by H-ZSM5.
To commercial applications of heterogeneous systems,
To assess the efficiency of H-ZSM5 as a catalyst, we
compared the resultof theoxidationofmethyl phenylsulfide
to methyl phenyl sulfoxide with previously reported results.
As shown in Table 3, the previously reported procedures
suffer from one or more limitations such as using 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, entries 2e4). The otheradvantages of
H-ZSM5 are the commercial availability and the low cost,
nontoxicity, stability, easily separable, and highly reusable.
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
2 2
H O 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.
2 2
Fig. 1. Recyclability of H-ZSM5 catalyst for the oxidation of methyl phenyl sulfide with 30% H O at room temperature under solvent-free conditions.
Please cite this article in press as: A. Rostami, et al., Zeolite nanoparticles (H-ZSM5) as a highly efficient, green, and reusable
heterogeneous catalyst for selective oxidation of sulfides to sulfoxides under mild conditions, Comptes Rendus Chimie (2018),
https://doi.org/10.1016/j.crci.2018.05.004

A. Rostami et al. / C. R. Chimie xxx (2018) 1e5
5
Table 3
Comparison of the activity of H-ZSM5 with the various catalysts in the oxidation of methyl phenyl sulfide with 30% H
2 2
O .
Entry
Catalyst/oxidant
H-ZSM5 zeolite/H
Reaction conditions
Time (min)
Yield (%)
Reference
1
2
3
4
5
2
O
2
Solvent-free, rt
50
98
91.5
95
98
93
This study
[42]
[17]
[43]
[44]
ꢁ
Peroxotungstate supported on silica/H
VO F(dmpz) /H
2
O
CH
2
CH
3
CH
3
CH
3
Cl
2
/MeOH, 8
C
150
300
120
72
ꢁ
2
2
2
O
2
CN, 0e5
CN, rt
CN, rt
C
Ru-PVP/
Cr(III)/H
g
-Al
2
O
3
/H
2
O
2
2
O
2
4
. Conclusion
[16] H. Zhang, G. Wang, Tetrahedron Lett. 55 (2014) 56.
[
[
[
[
[
17] S. Hussain, D. Talukdar, S.K. Bharadwaj, M.K. Chaudhuri, Tetrahe-
dron Lett. 53 (2012) 6512.
18] B.M. Choudary, B. Bharathi, C.V. Reddy, M.L. Kantam, J. Chem. Soc.
Perkin. Trans. 1 (2002) 2069.
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% H at room tempera-
19] K. Bahrami, M.M. Khodaei, M. Sheikh-Arabi, J. Org. Chem. 75 (2010)
2 2
O
6208.
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.
20] P. Villabrille, G. Romanelli, P. V ꢀa zquez, C. C aꢀ ceres, Appl. Catal. A Gen.
334 (2008) 374.
21] M.A. Zolfigol, A. Khazaei, M. Safaiee, M. Mokhlesi, R. Rostamian,
M. Bagheri, M. Shiri, H. Gerhardus Kruger, J. Mol. Catal. A: Chem. 370
(
2013) 80.
[22] S.A. Al-Bogami, J. Moreira, H.I. de Lasa, Ind. Eng. Chem. Res. 52
2013) 17760.
(
[
[
23] A.P. Bolton, M.A. Lanewala, P.E. Picke, J. Org. Chem. 33 (1968) 3415.
24] A.D. Abell, M.D. Oldham, J. Org. Chem. 62 (1997) 1509.
[25] Y. Tao, H. Kanoh, L. Abrams, K. Kaneko, Chem. Rev. 106 (2006) 896.
[
[
26] I.P. Beletskaya, V.P. Ananikov, Chem. Rev. 111 (2011) 1596.
27] F. Hassan, J. Wang, P.I. Chigada, B. Al-Duri, S.P. Rigby, J. Wood, Ind.
Eng. Chem. Res. 50 (2011) 7161.
[28] L.B. Young, S.A. Butter, W.W. Kaeding, J. Catal. 76 (1982) 418.
Acknowledgments
[29] T.J. Kwok, K. Jayasuriya, J. Org. Chem. 59 (1994) 4939.
[
30] S.S. Vieira, Z.M. Magriotis, M. Filipa Ribeiro, I. Graça, A. Fernandes,
J.M.F.M. Lopes, S.M. Coelho, N.A.V. Santos, A.A. Saczk, Microporous
Mesoporous Mater. 201 (2015) 160.
The authors are grateful to the University of Kurdistan
Research Councils for partial support of this work.
[31] J. Wu, H. Zhu, Zh Wu, Zh Qin, L. Yan, B. Du, W. Fan, J. Wang, Green
Chem. 17 (2015) 2353.
[
32] A. Rostami, A. Rostami, N. Iranpoor, M.A. Zolfigol, Tetrahedron Lett.
7 (2016) 192.
References
5
[
33] K. Amiri, A. Rostami, S. Samadi, A. Rostami, Catal. Commun. 86
(2016) 108.
[
1] A. Bayat, M. Shakourian-Fard, M. Mahmoodi Hashemi, Catal. Com-
mun. 52 (2014) 16.
2] K. Rajender Reddy, C.V. Rajasekhar, A. Ravindra, Synthetic Commun.
[34] A. Rostami, B. Atashkar, J. Mol. Catal. A: Chem. 398 (2015) 170.
[35] T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghamarani, Appl.
Organomet. Chem. 32 (2017) 3974.
[
36 (2006) 3761.
[
[
[
[
3] F. Hosseinpoor, H. Golchoubian, Tetrahedron Lett. 47 (2006) 5195.
4] X.F. Wu, Tetrahedron Lett. 53 (2012) 4328.
5] G.P. Romanelli, P.G. V ꢀa zquez, P. Tundo, Synlett (2005) 75.
[36] T. Tamoradi, A. Ghorbani-Choghamarani, M. Ghadermazi, New J.
Chem. 41 (2017) 11714.
[37] M. Hajjami, F. Sharifirad, F. Gholamian, Appl. Organomet. Chem. 31
(2017) 3844.
6] K. Kaczorowska, Z. Kolarska, K. Mitka, P. Kowalski, Tetrahedron 61
(
2005) 8315.
[38] A. Ghorbani-Choghamarani, B. Ghasemi, Z. Safari, G. Azadi, Catal.
Commun. 60 (2015) 70.
[
[
7] K. Bahrami, Tetrahedron Lett. 47 (2006) 2009.
8] A. Ghorbani-Choghamarani, P. Zamani, J. Iran. Chem. Soc. 8 (2011)
[39] D.J. Robinson, L. Davies, N. McGuire, D.F. Lee, P. McMorn,
D.J. Willock, G.W. Watson, P.C.B. Page, D. Bethell, G.J. Hutchings,
Phys. Chem. Chem. Phys. 2 (2000) 1523.
142.
[9] B. Karimi, M. Ghoreishi-Nezhad, J.H. Clark, Org. Lett. 7 (2005) 625.
[
[
10] A. Shaabani, A. Hossein Rezayan, Catal. Commun. 8 (2007) 1112.
11] K. Sato, M. Hyodo, M. Aoki, X.Q. Zheng, R. Noyori, Tetrahedron 57
[40] H. Jafari, A. Rostami, F. Ahmad-Jangi, A. Ghorbani-Choghamarani,
Synthetic Commun. 42 (2012) 3150.
(
2001) 2469.
[41] A. Ghorbani-Choghamarani, H. Rabiei, B. Tahmasbi, B. Ghasemi,
F. Mardi, Res. Chem. Intermed. 42 (2016) 5723.
[
12] A. Ghorbani-Choghamarani, Z. Darvishnejad, B. Tahmasbi, Inorg.
Chim. Acta 435 (2015) 223.
13] A. Rostami, J. Akradi, Tetrahedron Lett. 51 (2010) 3501.
14] M. Kirihara, J. Yamamoto, T. Noguchi, Y. Hirai, Tetrahedron Lett. 50
[42] X.Y. Shi, J.F. Wei, J. Mol. Catal. A: Chem. 280 (2008) 142.
[43] P. Veerakumar, Z.Z. Lu, M. Velayudham, K.L. Lu, S. Rajagopal, J. Mol.
Catal. A: Chem. 332 (2010) 128.
[
[
(
2009) 1180.
[44] A.R. Supale, G.S. Gokav, Catal. Lett. 124 (2008) 284.
[15] M. De Rosa, M. Lamberti, C. Pellecchia, A. Scettri, R. Villano,
A. Soriente, Tetrahedron Lett. 47 (2006) 7233.
Please cite this article in press as: A. Rostami, et al., Zeolite nanoparticles (H-ZSM5) as a highly efficient, green, and reusable
heterogeneous catalyst for selective oxidation of sulfides to sulfoxides under mild conditions, Comptes Rendus Chimie (2018),
https://doi.org/10.1016/j.crci.2018.05.004