Selective oxidation of sulfides to sulfoxides with poly[4-hydroxy(tosyloxy) iodo]styrene

Article abstract of DOI:10.1080/00397910500283446

Sulfides can be selectively converted to corresponding sulfoxides in excellent yields under mild conditions by linear and 1% cross-linked poly[4-hydroxy(tosyloxy)iodo]styrene (PSHTIB). Copyright Taylor & Francis, Inc.

Full text of DOI:10.1080/00397910500283446

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Selective Oxidation of Sulfides to Sulfoxides
With Poly[4‐Hydroxy(tosyloxy)iodo]styrene
Ping Liu a , Shi‐juan Liu b , Ji‐Zhen Zhang c & Guan‐rong Tian a
a Department of Chemistry , Yanbian University , Yanji, Ji Lin, China
b College of Chemistry , Jilin Normal University , Siping, China
c Provincial Key Constructive Laboratory of Precious Metals Processing
Technology and Application , Jiangsu Teachers University of Technology ,
Changzhou, China
Published online: 20 Aug 2006.
To cite this article: Ping Liu , Shi‐juan Liu , Ji‐Zhen Zhang & Guan‐rong Tian (2005) Selective Oxidation of
Sulfides to Sulfoxides With Poly[4‐Hydroxy(tosyloxy)iodo]styrene, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 35:24, 3173-3177
To link to this article: http://dx.doi.org/10.1080/00397910500283446
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Synthetic Communicationsw, 35: 3173–3177, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500283446
Selective Oxidation of Sulfides to Sulfoxides
With Poly[4-Hydroxy(tosyloxy)iodo]styrene
Ping Liu
Department of Chemistry, Yanbian University, Yanji, Ji Lin, China
Shi-juan Liu
College of Chemistry, Jilin Normal University, Siping, China
Ji-Zhen Zhang
Provincial Key Constructive Laboratory of Precious Metals Processing
Technology and Application, Jiangsu Teachers University
of Technology, Changzhou, China
Guan-rong Tian
Department of Chemistry, Yanbian University, Yanji, Ji Lin, China
Abstract: Sulfides can be selectively converted to corresponding sulfoxides in
excellent yields under mild conditions by linear and 1% cross-linked poly[4-hydroxy(-
tosyloxy)iodo]styrene (PSHTIB).
Keywords: Poly[4-hydroxy(tosyloxy)iodo]styrene, sulfide, sulfoxide
Oxidation of sulfides is an important method for preparing sulfoxides
and sulfones. Trifluoroperacetic acid,[1] sodium bromite,[2] an MeNO2
solution in dilute HNO3/H2SO4,[3] mercury(II) oxide–iodine reagent,[4] and
iodic acid[5] are frequently used as oxidation reagents. At present, many
low-molecular-mass hypervalent iodine reagents that can selectively oxidize
Received in Japan May 19, 2005
Address correspondence to Guan-rong Tian, Department of Chemistry, Yanbian
University, Yanji, Ji Lin, 133002, China. Tel.: 0086-433-2732289; Fax: 0086-433-
2758088; E-mail: grtn@ybu.edu.cn
3173

3174
P. Liu et al.
sulfides to the corresponding sulfoxides are available, for example phenyliodo
diacetate,[6] iodosobenzene (PhI55O),[7] hydroxy(tosyloxy)iodobenzene
(HTIB, Koser’s reagent),[8] and dichloroiodobenzene.[9]
Characteristics of these reagents include ease of preparation, low toxicity,
mild reaction conditions, high selectivity, and reasonable cost. However, the
oxidation product is easily contaminated with iodobenzene after reaction.
Recently, Togo and coworkers reported a method for the oxidation of
sulfides to sulfoxides and sulfones that employs recycling of poly[(4-diacetoxy-
iodo)styrene] in chloroform–water (1%).[10] Their method is credited with
overcoming the product-contamination drawback inherent in the use of low-
molecular-mass hypervalent iodine reagents.
We studied the environmentally benign reagents poly[4-hydroxy(tosyloxy)-
iodo]styrene (PSHTIB) and poly[(4-diacetoxyiodo)styrene],[11] and describe
the utility of the former as an oxidizing reagent for sulfides in this
communication.
Linear PSHTIB and 1% cross-linked PSHTIB was prepared using a
method reported previously.[12] The loading capacities (measured by
iodometry) of linear PSHTIB and 1% cross-linked PSHTIB were
1.91 mmol/g and 1.72 mmol/g, respectively.
Linear PSHTIB (1.3 g) or 1% cross-linked PSHTIB (1.5 g) in dichloro-
methane reacted with sulfides (2 mmol) at room temperature to produce the
corresponding sulfoxides (Scheme 1) (Table 1).
Our results showed that both hypervalent iodine reagents had high
selectivity and produced single sulfoxides, the yields of which approached
those obtained using low-molecular-mass hypervalent reagents. The polyiodo-
benzene formed from PSHTIB was easily separated from the reaction products
by filtration, avoiding the inconvenience of separating and refining iodoben-
zene formed from HTIB. In addition, the recycled reagent contained almost
the same functional group as the original reagent. The polystyrene-
supported hypervalent iodine reagents conform to environmental and
economic criteria.[13]
EXPERIMENTAL
Linear polystyrene was purchased from J & K Chemical Ltd. (Peking). Cross-
linked polystyrene (1%, 200–400 mesh) was obtained from Nankai Share
Group (Tianjin). Melting points were determined by a capillary method and
are uncorrected. Elemental analyses were performed using a PE 2400
Scheme 1.

Oxidation of Sulfides to Sulfoxides
3175
Table 1. Results of the oxidation
Product
Yielda (lit.)
100
Yieldb
95
Mp (8C) (lit.)
IR n/cm21
PhS(O)Ph
70–71 (MeOH)
(70.4)[2]
120–121
1583, 1442, 1039,
695
PhS(O)Bn
Bn2SO
91 (100)[8]
100 (100)[8]
88 (95)[8]
90
95
1495, 1038, 747,
694
[2]
(MeOH) (123)
133–134
1494, 1456, 1032,
776, 701
(MeOH) (132–3)[4]
PhS(O)Et
PhS(O)Bu-n
BnS(O)Bu-n
2978, 1478, 1045,
751, 695
82 (97)[8]
2960, 1448, 1038,
750, 695
86 (94)[8]
1494, 1456, 1032,
776, 701
(Bu-n)2SO
(CH2)4SO
PhS(O)Ph
71
33 (MeOH)(34)[2]
70–71 (70.4)
2960, 1380, 1028
2934, 1444, 1031
1582, 1443, 1040,
693
78[4]
96c
91d
88d
PhS(O)Bn
88c
120–121 (123)
1494, 1039, 747,
695
aBy applying linear PSHTIB.
bBy applying 1% cross-linked PSHTIB.
cBy applying linear PSHTIB recycled.
dBy applying 1% cross-linked PSHTIB recycled.
(Perkin-Elmer) instrument. IR spectra were recorded using an FT-IR1730
(Perkin-Elmer) instrument.
General Procedure for Oxidation of Sulfides
Oxidation of Sulfides with Linear PSHTIB
Sulfide (2 mmol) was added to linear PSHTIB (1.3 g) in dichloromethane
(25 ml) at room temperature. After removing the solvent, anhydrous ethanol
(15 ml) was added to the residue and the poly(4-iodostyrene) was recovered
by filtration. The filtrate was evaporated, and dichloromethane (15 ml) was
added to the residue, which was then washed with 5% sodium hydroxide
solution (10 ml). The organic layer was dried over anhydrous magnesium
sulfate and concentrated, yielding the products.
Oxidation of Sulfides by 1% Cross-linked PSHTIB
Oxidation of sulfides by 1% cross-linked PSHTIB was carried out using the
procedure described for linear PSHTIB.

3176
P. Liu et al.
Regeneration of PSHTIB
Regeneration of 1% Cross-linked Poly[4-hydroxy(tosyloxy)iodo]styrene
Recovered 1% cross-linked poly(4-iodostyrene) (5.5 g) was washed with
dichloromethane (100 ml) using a scorbutic extractor, yielding neat 1%
cross-linked poly(4-iodostyrene) (5.3 g). This was treated using a method
described previously[12] to obtain 1% cross-linked poly[(4-diacetoxyiodo)-
styrene] (6.8 g) and poly[4-hydroxy(tosyloxy)iodo]styrene (7.5 g). IR (KBr)
3417, 1176, 1015, 814, 673 cm21. Anal. found: S, 5.38%. Its loading
capacity was 1.68 mmol/g.
Regeneration of Linear Poly[4-hydroxy(tosyloxy)iodo]styrene
Methanol (200 ml) was added slowly to the recovered linear poly(4-iodostyrene)
(4.5 g) in chloroform (70 ml) to yield neat linear poly(4-iodostyrene)
(3.5 g), which was treated by a previously reported method[12] to obtain
poly[(4-diacetoxyiodo)styrene] (4.8 g) and linear poly[4-hydroxy(tosyloxy)-
iodo]styrene (5.4 g). IR (KBr) 3407, 1180, 1016, 816, 675 cm21. Anal.
found: S, 6.12%. Its loading capacity was 1.93 mmol/g.
ACKNOWLEDGMENTS
This work was supported by the grants from the Science and Technology
Committee of Ji Lin Province, China.
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