Sulfonated condensed polynuclear aromatic (S-COPNA)) resin catalyzed selective oxidation of sulfides to sulfoxides or sulfones using hydrogen peroxide

Article abstract of DOI:10.1080/10426507.2011.621909

Sulfonated condensed polynuclear aromatic (S-COPNA) resin was found to be a highly efficient, environmentally friendly, recyclable heterogeneous catalyst for the oxidation of alkyl and aryl sulfides to the corresponding sulfoxides or sulfones, in good yields under mild reaction conditions using 30% hydrogen peroxide as an oxidant. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Synthesis of the S-COPNA resin catalyst. Spectroscopic data for compounds.

Full text of DOI:10.1080/10426507.2011.621909

This article was downloaded by: [b-on: Biblioteca do conhecimento online UL]
On: 06 May 2014, At: 01:37
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
Sulfonated Condensed Polynuclear
Aromatic (S-Copna) Resin Catalyzed
Selective Oxidation of Sulfides to
Sulfoxides or Sulfones Using Hydrogen
Peroxide
Arash Shokrolahi a & Abbas Zali a
a Department of Chemistry , Malek-Ashtar University of Technology ,
Shahin-Shahr , I. R. Iran
Published online: 31 Jan 2012.
To cite this article: Arash Shokrolahi & Abbas Zali (2012) Sulfonated Condensed Polynuclear
Aromatic (S-Copna) Resin Catalyzed Selective Oxidation of Sulfides to Sulfoxides or Sulfones Using
Hydrogen Peroxide, Phosphorus, Sulfur, and Silicon and the Related Elements, 187:4, 454-460, DOI:
10.1080/10426507.2011.621909
To link to this article: http://dx.doi.org/10.1080/10426507.2011.621909
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 187:454–460, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.621909
SULFONATED CONDENSED POLYNUCLEAR AROMATIC
(S-COPNA) RESIN CATALYZED SELECTIVE OXIDATION
OF SULFIDES TO SULFOXIDES OR SULFONES USING
HYDROGEN PEROXIDE
Arash Shokrolahi and Abbas Zali
Department of Chemistry, Malek-Ashtar University of Technology,
Shahin-Shahr, I. R. Iran
GRAPHICAL ABSTRACT
Abstract Sulfonated condensed polynuclear aromatic (S-COPNA) resin was found to be a
highly efficient, environmentally friendly, recyclable heterogeneous catalyst for the oxidation
Received 14 August 2011; accepted 2 September 2011.
Address correspondence to Arash Shokrolahi, Department of Chemistry, Malek-Ashtar University of Tech-
nology, Shahin-Shahr, P.O. Box 83145-115, I. R. Iran. E-mail: ar shokrolahi@mut-es.ac.ir
454

(S-COPNA) RESIN CATALYZED SELECTIVE OXIDATION
455
of alkyl and aryl sulfides to the corresponding sulfoxides or sulfones, in good yields under mild
reaction conditions using 30% hydrogen peroxide as an oxidant.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental
resource: Synthesis of the S-COPNA resin catalyst. Spectroscopic data for compounds.
Keywords Sulfonated condensed polynuclear aromatic (S-COPNA) resin; hydrogen peroxide;
sulfide; sulfoxide, sulfone
INTRODUCTION
Sulfones and sulfoxides are valuable intermediates for the synthesis of chemically
and biologically important and significant molecules.1–3 For this reason in recent years, the
oxidation of sulfides to sulfoxides or sulfones has been the subject of many studies.4–11
Several types of oxygen donors such as H2O2, m-CPBA, ozone, and t-BuOOH have
been used for the sulfoxidation process in solution and the solid phase.12–14 Among these,
hydrogen peroxide is a low cost and environmentally friendly oxidant.15–17 However, it is a
relatively weak oxidizing agent, and therefore, various kinds of acids and transition-metal-
based systems have been used to activate hydrogen peroxide.10,18
Solid acids have many advantages in both industry and the synthetic laboratory such
as simplicity in handling, fewer reactor, and plant corrosion problems and environmentally
safe disposal.19
Recently, Tanemura and coworkers reported the synthesis of a sulfonated condensed
polynuclear aromatic (S-COPNA) resin with high acid activities. This solid acid has some
advantages. First, it exhibited higher performance than conventional solid acids and insol-
uble to boiling water and many hot organic solvents. Second, the products could be easily
separated from the reaction mixture and the catalyst is recoverable without decreasing its
activity. Third, it can be successfully used instead of sulfuric acid as a catalyst.20
Herein, we report the selective oxidation of sulfides to sulfoxides or sulfones with
H2O2 in the presence of a catalytic amount of S-COPNA as a heterogeneous catalyst
(Scheme 1).
O
O
O
S
S
S
1.2 eq. H2O2
4 eq. H2O2
R
R'
R
R'
R
R'
S-COPNA (0.07 g)
S-COPNA (0.15 g)
Scheme 1
RESULTS AND DISCUSSION
The procedure is simple: Hydrogen peroxide was added into the stirred mixture of
sulfide substrate and S-COPNA at refluxing temperature. Diphenyl sulfide was selected as a
model substrate for the optimization, and the oxidation of this substrate in various condition
was studied. Results of these optimization experiments are presented in Tables 1 and 2. The
effect of various solvents such as dichloroethane, acetonitrile, xylene, dichloromethane,
and ethanol on oxidation of diphenyl sulfide to diphenyl sulfoxide using S-COPNA

456
A. SHOKROLAHI AND A. ZALI
Table 1 The effect of various solvents on oxidation of diphenyl sulfide to diphenyl sulfoxide
Reaction time
(min) (Reflux)
Entry
Solvent
Yield (%)a
1
2
3
4
5
1,2-Dichloroethane
Acetonitrile
Xylene
Dichloromethane
Ethanol
15
25
60
25
25
95
92
55
75
60
aIsolated yield.
(0.07 g)/H2O2 (1.2 eq.) system is shown in Table 1 and clearly indicates that dichloroethane
to be most suitable solvent for this reaction.
Several oxidation reactions of diphenyl sulfide were performed with different amounts
of hydrogen peroxide and catalyst in order to find the most adequate condition and opti-
mizing of the oxidation reaction. The yield and selectivity of oxidation diphenyl sulfide to
the corresponding sulfoxide or sulfone as a function of time is indicated in Table 2.
In the absence of the acid catalyst, the conversion of diphenyl sulfide to diphenyl
sulfoxide was 75% in duration 24 h after beginning of reaction (Table 2, Entry 1). When the
catalyst was added, the times were reduced considerably and the yield increased to 95%.
The optimum ratio of sulfide to H2O2 (1:1.2 eq.) in the presence of S-COPNA (0.07 g) was
found to be ideal for complete conversion of sulfides to sulfoxide (Table 2, Entries 2–5).The
use of excess reagent (H2O2 (4.0 eq.) and S-COPNA (0.15 g)) led to the corresponding
sulfone in a clean reaction (Table 2, Entries 6–11).
The generality of the protocol was investigated by oxidation a variety of alkyl,
aryl, and aromatic sulfides as shown in Table 3. All the substrates studied were smoothly
converted to the corresponding sulfoxide or sulfones in good yields. Hindered sulfides such
as dibenzothiophene could also be oxidized using this protocol but required longer reaction
times and gave the moderate yields (Table 3, Entry 12).
Table 2 Optimization of the amounts of H2O2 and S-COPNA for the selective oxidation of diphenyl sulfide to
diphenyl sulfoxide or diphenyl sulfone
Yield (%)a
Entry
H2O2 (eq.)
S-COPNA (mg)
Time
Sulfoxide
Sulfone
1
2
3
4
5
6
7
8
9
1.5
0.6
1.2
1.6
1.2
2.5
3.5
4.0
2.5
3.5
4.0
3.5
0
24 h
75
51
95
95
95
7
5
5
3
Trace
—
—
Trace
—
71
77
82
79
93
0.07
0.07
0.07
0.1
0.1
0.1
60 min
10 min
10 min
10 min
30 min
15 min
15 min
25 min
15 min
15 min
24 h
0.1
0.15
0.15
0.15
0.0
10
11
12
—
—
30
95
48
aIsolated yield.

(S-COPNA) RESIN CATALYZED SELECTIVE OXIDATION
Table 3 Oxidation of sulfides to sulfoxides or sulfone with hydrogen peroxide in the presence of S-COPNA
Sulfoxide Sulfone
Time (min)
457
Entry
1b
Substrate
Time (min)
Yield (%)a
Yield (%)a
95
10
10
10
95, 95, 93, 95
13
15
18
S
2
3
95
93
96
94
S
CH3
S
S
4
5
10
10
88
91
15
23
89
92
S
6
7
7
7
76
79
10
12
93
94
S
S
S
8
7
94
10
93
9
20
86
25
88
S
S
S
CH3
CH3
CH3
Cl
Br
10
11
12
20
30
50
85
90
70
25
45
90
86
85
78
O2N
S
aIsolated yield.
bThe same reagent was used for each of the four runs.

458
A. SHOKROLAHI AND A. ZALI
Table 4 Comparison of the activity of various catalysts in the oxidation of diphenyl sulfide using H2O2
Entry
Catalyst
S-COPNA
Silica sulfuric acid
MoO2Cl2
Conditions
Time
Yield
Ref.
1
2
3
4
5
6
7
8
9
C2H4Cl2, reflux
CH3CN, r.t.
Acetone, r.t.
CH3CN
MeOH, r.t.
MeOH, r.t.
CH3CN, reflux
C2H4Cl2, reflux
CH3CN
10 min
30 min
25 min
30 min
210 min
180 min
2 h
10 min
90 min
40 min
95
95
89
93.8
98
98
100
95
93
This work
10
18d
18e
21
21
22
23
24
25
TaCl5
Amberlite IR-400
Amberlyst 15
H5PMo11Al0.5V0.5O40
CBSA
L-proline
HNO3
10
EtOH, r.t.
92
The recyclability of the catalyst was also investigated using a model oxidation of
diphenyl sulfide to diphenyl sulfoxide under similar reaction conditions. After completion
of the reaction, the catalyst was separated by filtration and used as such for subsequent
experiments after adding fresh substrate and oxidant (aqueous 30% H2O2) under similar
reaction conditions. The activity of the catalyst did not show any significant decrease after
four runs (Table 3, Entry 1).
Table 4 compares the efficiency of the S-COPNA resin catalyst with the efficiency of
other catalysts in the oxidation of diphenyl sulfide to diphenyl sulfoxide obtained by some
other workers. The data in Table 4 show that some protocols took much longer time, no
recovery catalyst, or some used dangerous materials with reduced isolated yields.
In summary, we have demonstrated that S-COPNA is a superior acid catalyst for
oxidation of sulfides to sulfoxides or sulfones with the environmentally friendly 30% H2O2.
This procedure has the advantages of mild reaction conditions, high yields of products,
short reaction times, and simple experimental/product-isolation techniques, which make it
a useful and attractive process.
EXPERIMENTAL
Melting points were measured on an Electrothermal 9100 apparatus and are uncor-
rected. All chemicals were commercial products. Thin layer chromatography (TLC) was
used to monitor all reactions and all yields refer to isolated products. 1H NMR spectra were
recorded on a Bruker Avance AQS 300 MHz using tetramethylsilane (TMS) as an internal
standard. Fourier transform infrared (FT-IR) spectra were recorded on a Nicolet IMPACT
400D instrument. The S-COPNA resin catalyst was prepared according to the reported
procedure20a (see Supplemental Materials).
General Experimental Procedure for the Preparation of Sulfoxides
In a typical reaction, a mixture of S-COPNA (0.07 g equal to 0.36 mmol H+),
diphenyl sulfide (0.186 g, 1 mmol), hydrogen peroxide (aq. 30%, 1.2 mmol), and 1,2-
dichloroethane (5 mL) was refluxed for 10 min. The progress of reaction was monitored by
TLC method. At the end of the reaction, catalyst was removed by filtration and the resulting
solution was concentrated under reduced pressure. Then, residue was purified by column
chromatography on silica gel (n-hexane/EtOAc 6:1) to afford 0.193 g (95%) of diphenyl
sulfoxide as an white solid (Table 3).

(S-COPNA) RESIN CATALYZED SELECTIVE OXIDATION
459
The resulting products were determined by their 1H NMR spectra and compared with
the authentic samples (sample 1H NMR data is presented in the Supplemental Materials).
General Experimental Procedure for the Preparation of Sulfones
A mixture of S-COPNA (0.15 g equal to 0.77 mmol H+), diphenyl sulfide (0.186 g,
1 mmol), hydrogen peroxide (aq. 30%, 4.0 mmol), and 1,2-dichloroethane (5 mL) was
refluxed for 13 min (see Table 3). After completion of the reaction, the product was worked
up similar to above to afford 0.208 g (95%) (Table 3).
REFERENCES
1. Patai, S.; Rappoport, Z.; Stirling, C. The Chemistry of Sulphone and Sulphoxide; John Wiley:
Chichester, UK, 1988.
2. Carreno, M. C. Chem. Rev. 1995, 95, 1717-1760.
3. Frenanez, I.; Khiar, N. Chem. Rev. 2003, 103, 3651-3706.
4. Iranpoor, N.; Firouzabadi, H.; Pourali, A.-R. Synlett 2004, 347-349.
5. Hajipour, A. R.; Kooshki, B.; Ruoho, A. E. Tetrahedron Lett. 2005, 46, 5503-5506.
6. Ozanne-Beaudenon, A.; Quideau, S. Tetrahedron Lett. 2006, 47, 5869-5873.
7. Stingl, K. A.; Tsogoeva, S. B. Tetrahedron: Asymmetry 2010, 21, 1055-1074.
8. Al-Ajlouni, A. M.; Daiafla, T. M.; El-Khateeb, M. J. Mol. Catal. A.: Chem. 2007, 275, 139-147.
9. Egami, H.; Katsuki, T. J. Am. Chem. Soc. 2007, 129, 8940-8941.
10. Shaabani, A.; Rezayan, A. H. Catal. Commun. 2007, 8, 1112-1116.
11. Khodaei, M. M.; Bahrami, K.; Khedri, M. Can. J. Chem. 2007, 85, 7-11.
12. Patek, M.; Drake, B.; Lebel, M. Tetrahedron Lett. 1995, 36, 2227-2230.
13. Sylvian, C.; Wanger, A.; Mioskowosky, C. Tetrahedron Lett. 1997, 38, 1043-1044.
14. Noyori, R.; Aoki, M.; Sato, K. Chem. Commun. 2003, 1977-1986.
15. Sheldon, R. A. Green Chem. 2000, 1, G1-G4.
16. Anastas, P. T.; Bartlett, L. B.; Kirchhoff, M. M.; Williamson, T. C. Catal. Today 2000, 55, 11-22.
17. Kaczorowska, K.; Kolarska, Z.; Mitka, K.; Kowalski, P. Tetrahedron 2005, 61, 8315-8327.
18. (a) Rama Raju, B.; Sarkar, S.; Chandramoulali Reddy, U.; Saikia, A. K. J. Mol. Catal. A:
Chem. 2009, 308, 169-173; (b) Matteucci, M.; Bhalay, G.; Bradley, M. Org. Lett. 2003, 5,
235-237; (c) Bahrami, K. Tetrahedron Lett. 2006, 47, 2009-2012; (d) Jeyakumar, K.; Chand,
D. K. Tetrahedron Lett. 2006, 47, 4573-4576; (e) Kirihara, M.; Yamamoto, J.; Noguchi, T.;
Hirai, Y. Tetrahedron Lett. 2009, 50, 1180-1183; (f) Wang, S. H.; Mandimutsira, B. S.; Todd, R.;
Ramdhanie, B.; Fox, J. P.; Goldberg, D. P. J. Am. Chem. Soc. 2004, 126, 18-19; (g) Du, G. D.;
Espenson, J. H. Inorg. Chem. 2005, 44, 2465-2471; (h) Barnes, I.; Hjorth, J.; Mihalopoulos, N.
Chem. Rev. 2006, 106, 940-975; (i) Carson, E. C.; Lippard, S. J. Inorg. Chem. 2006, 45, 837-848;
(j) Maurya, M. R.; Chandrakar, A. K.; Chand, S. J. Mol. Catal. A.: Chem. 2007, 263, 227-
237.
19. (a) Anastas, P. T.; Kirchhoff, M. M. Acc. Chem. Res. 2002, 35, 686-694; (b) DeSimone,
J. M. Science 2002, 297, 781-799; (c) Harton, B. Nature 1999, 400, 797-799; (d) Anastas,
P. T.; Zimmermann, J. B. Environ. Sci. Technol. 2003, 37, 94A-101A; (e) Clark, J. H. Acc. Chem.
Res. 2002, 35, 791-797; (f) Okuhara, T. Chem. Rev. 2002, 102, 3641-3666; (g) Hara, M.; Yoshida,
T.; Takagaki, A.; Takata, T.; Kondo, J. N.; Hayashi, S.; Domen, K. Angew. Chem. Int. Ed. 2004,
43, 2955-2958.
20. (a) Tanemura, K.; Suzuki, T.; Nishida, Y, Horaguchi, T. Tetrahedron 2011, 67, 1314-1319;
(b) Tanemura, K.; Suzuki, T.; Nishida, Y.; Horaguchi, T. Polym. Bull.; (c) Hara, M.; Yoshida, T.;
Takagaki, A.; Takata, T.; Kondo, J. N.; Hayashi, S.; Domen, K. Angew. Chem. Int. Ed. 2004, 43,
2955-2958.

460
A. SHOKROLAHI AND A. ZALI
21. Lakouraj, M. M.; Tajbakhsh, M.; Tashakkorian, H. Monatsh. Chem. 2007, 138, 83-88.
22. Romanelli, G. P.; Bennardi, D. O.; Palermo, V.; Vazquez, P. G.; Tundo, P. Lett. Org. Chem. 2007,
4, 544-549.
23. Zali, A.; Shokrolahi, A.; Keshavarz, M. H.; Zarei, M. A. Acta Chim. Slov. 2008, 55, 257-260.
24. Rajender Reddy, K.; Rajasekhar, C. V.; Ravindra, A. Synth. Commun. 2006, 36, 3761-3766.
25. Khodaei, M. M.; Bahrami, K.; Sheikh Arabi, M. J. Sulfur Chem. 2010, 31, 83-88.