A selective and convenient oxidation of sulfides to sulfoxides with trichloroisocyanuric acid

Article abstract of DOI:10.1081/SCC-100000205

Sulfides are readily oxidized to sulfoxides by a solution of pyridine, water, and trichloroisocyanuric acid in acetonitrile and methylene chloride.

Full text of DOI:10.1081/SCC-100000205

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A SELECTIVE AND CONVENIENT OXIDATION
OF SULFIDES TO SULFOXIDES WITH
TRICHLOROISOCYANURIC ACID
Zi-Xing Xiong a , Nan-Ping Huang a & Ping Zhong b
a Department of Chemistry , Yichun Teachers College , 587 Huanchengbei Road, Yichun,
336000, P.R. China
b Department of Chemistry , Yichun Teachers College , 587 Huanchengbei Road, Yichun,
336000, P.R. China
Published online: 16 Aug 2006.
To cite this article: Zi-Xing Xiong , Nan-Ping Huang & Ping Zhong (2001) A SELECTIVE AND CONVENIENT OXIDATION OF
SULFIDES TO SULFOXIDES WITH TRICHLOROISOCYANURIC ACID, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 31:2, 245-248, DOI: 10.1081/SCC-100000205
To link to this article: http://dx.doi.org/10.1081/SCC-100000205
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SYNTHETIC COMMUNICATIONS, 31(2), 245–248 (2001)
A SELECTIVE AND CONVENIENT
OXIDATION OF SULFIDES
TO SULFOXIDES WITH
TRICHLOROISOCYANURIC ACID
Zhi-Xing Xiong, Nan-Ping Huang, and Ping Zhong∗
Department of Chemistry, Yichun Teachers College,
587 Huanchengbei Road, Yichun, 336000, P.R. China
ABSTRACT
Sulfides are readily oxidized to sulfoxides by a solution of
pyridine, water, and trichloroisocyanuric acid in acetonitrile and
methylene chloride.
The selective oxidation of sulfides to sulfoxides is an attractive and ex-
tremely important method, since sulfoxides are useful building blocks in organic
synthesis (1). Sulfides can be converted into sulfoxides using various oxidiz-
ing agents (2–5). Trichloroisocyanuric acid [1,3,5-trichloro-1,3,5-triazine-2,4,6-
(1H,3H,5H)-trione] has been a useful reagent in organic synthesis (6), and it
has been used to oxidize secondary alcohol to ketones in good yield (7). We
havenowfoundthattrichloroisocyanuricacid[1,3,5-trichloro-1,3,5-triazine-2,4,6-
(1H,3H,5H)-trione] (2) is a very efficient, highly selective reagent for the oxidation
of sulfides into sulfoxides.
A solution of a sulfide 1, pyridine, water, and 2 in acetonitrile and methylene
chloride will produce the corresponding sulfoxide 3, along with cyanuric acid 4 and
∗ To whom correspondence should be addressed.
245
Copyright ꢀ 2001 by Marcel Dekker, Inc.
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C

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XIONG, HUANG, AND ZHONG
Scheme 1.
hydrogen chloride (Scheme 1). The yield and the melting point of the sulfoxides
are shown in Table 1.
Although acetonitrile generally worked well, in some instances methylene
chloridewasmoresuitabletodissolvethesulfides. Toenhancetherateof oxidation,
a trace of water was added to the sulfide reaction mixture. In anhydrous conditions,
the reaction proceeded slowly. Excessive water reduced the rate of oxidation and
gave poor yield. Since hydrogen chloride is produced in the reaction and can react
with 2 to form chlorine (8), pyridine is added to the reaction mixture.
Although the ease of the reactions is dependent on the electrosteric properties
of the sulfides, it should be emphasized that the reactions performed cleanly and
Table 1. Synthesis of Compounds 3a–k
R1
R2
MP(◦C)
Found
MP(◦C)
Reported
Rfa
Yield (%)b
3a
3b
3c
3d
3e
3f
Ph
Ph
Ph
Ph
Ph
Ph
Ph
CH2C6H5
CH3
69–70
69–702
0.73
85
88
85
91
88
83
89
92
84
92
90
124–125 122–1242 0.72
33–34
32–332
0.80
4-NO2C6H4 106–107 105–1074 0.70
4-MeC6H4
4-ClC6H4
CH3
4-MeC6H4
CH3
70–71
44–45
42–43
94–95
47–48
69–705
44–455
42–432
92–954
46–472
0.74
0.72
0.79
0.68
0.78
3g 4-MeC6H4
3h 4-MeC6H4
3i
3j
3k
4-ClC6H4
4-ClC6H4
CH2C6H5
4-ClC6H4
CH2C6H5
140–141 140–1424 0.67
134–135 134–1352 0.70
aEluted with cyclohexane and ethyl acetate (1:1).
bIsolated yield.

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SULFIDES TO SULFOXIDES
247
were controlled to stop at the sulfoxides stage; there was no evidence for the
formation of any sulfones.
EXPERIMENTAL
1H NMR spectra were recorded on a PMX-60 spectrometer in CDCl3 as the
solvent with TMS as an internal standard. J values are given in Hz. IR spectra
were measured on a PE-683 spectrophotometer as KBr disks. Silica gel 60 GF254
was used for analytical and preparative TLC. All products were characterized by
comparison with authentic samples using IR, 1H NMR and GC retention time.
General Procedure for the Synthesis of 3a–k
In a 25-mL two-necked flask were placed 1 mmol of sulfide 1, 1 mL of
acetonitrile, 1 mL of methylene chloride, and 0.05 mL of water. The mixture was
allowed to stir for 5 min before a solution of 2 (0.8 mmol) in 1 mL of acetonitrile
was added dropwise through a syringe. After a few minutes, the temperature began
to rise, and the flask was placed in a water bath to keep the temperature below 40◦C.
The addition took a total of 15 min and was followed by an additional 30 min of
stirring at 40◦C. Excess 2 was destroyed by the slow addition of saturated NaHSO3
while cooling the flask in an ice bath. During this process, wet iodide-starch test
paper was used to periodically test for the presence of oxidizing agents. The pre-
cipitate of cyanuric acid 4 was removed by filtration and washed with diethyl ether.
Mostof thesolventwasremovedfromthe filtrateunder vacuumandtheresiduewas
diluted with 10 mL of diethyl ether. The ether solution was washed with 1 N NaOH
(2 × 3 mL), 1 N HCl (2 × 3 mL), and saturated NaCl solution (3 mL) and dried
over MgSO4. After filtration and concentration, the crude product was purified by
preparative TLC on silica gel, eluted with cyclohexane and ethyl acetate (1:1).
ACKNOWLEDGMENT
This work was supported by The Major Laboratory of Organic Chemistry,
Zhejiang University (Campus Xixi).
REFERENCES
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Proced. Int. 1996, 28, 705.

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XIONG, HUANG, AND ZHONG
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4. Folsom, H.E.; Castrillon, J. Synth. Commun. 1992, 22, 1799.
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156.
Received in the U.S.A. April 6, 2000

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