A selective and convenient oxidation of acetylenic sulfides to acetylenic sulfoxides using trichloroisocyanuric acid

Article abstract of DOI:10.1081/SCC-120001999

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

Full text of DOI:10.1081/SCC-120001999

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A SELECTIVE AND CONVENIENT OXIDATION OF
ACETYLENIC SULFIDES TO ACETYLENIC SULFOXIDES
USING TRICHLOROISOCYANURIC ACID
Ping Zhong a , Meng-Ping Guo a & Nan-Ping Huang a
a Department of Chemistry , Yichun Normal Institute , Yichun, 336000, P. R. China
Published online: 16 Aug 2006.
To cite this article: Ping Zhong , Meng-Ping Guo & Nan-Ping Huang (2002) A SELECTIVE AND CONVENIENT OXIDATION OF
ACETYLENIC SULFIDES TO ACETYLENIC SULFOXIDES USING TRICHLOROISOCYANURIC ACID, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:2, 175-179, DOI: 10.1081/
SCC-120001999
To link to this article: http://dx.doi.org/10.1081/SCC-120001999
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SYNTHETIC COMMUNICATIONS, 32(2), 175–179 (2002)
A SELECTIVE AND CONVENIENT
OXIDATION OF ACETYLENIC SULFIDES
TO ACETYLENIC SULFOXIDES USING
TRICHLOROISOCYANURIC ACID
Ping Zhong,* Meng-Ping Guo, andNan-Ping Huang
Department of Chemistry, Yichun Normal Institute,
Yichun, 336000, P. R. China
ABSTRACT
Acetylenic sulfides are readily oxidized to acetylenic sulfoxides
by a solution of pyridine, water, benzoic acid and trichloroiso-
cyanuric acidin acetonitrile andmethylene chloride.
Acetylenic sulfoxides are useful building blocks in organic synthesis.1
The selective oxidation of sulfides to sulfoxides is an attractive and extre-
mely important method. Acetylenic sulfides can be converted into acetylenic
sulfoxides using various oxidizing agents.1–5 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 it has been used to oxidized secondary alcohol
7
to ketones in goodyields.
We have now foundthat trichloroisocyan-
uric acid[1,3,5-trichloro-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione] ( 2) is very
efficient, highly selective reagent for oxidation of acetylenic sulfides into
acetylenic sulfoxides.
*Corresponding author.
175
Copyright & 2002 by Marcel Dekker, Inc.
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176
ZHONG, GUO, AND HUANG
A solution of acetylenic sulfide 1, pyridine, water, benzoic acid and 2
in acetonitrile and methylene chloride underwent oxidation to produce
the corresponding acetylenic sulfoxide 3 along with cyanuric acid 4 and
hydrogen chloride. Yields are good to excellent (Scheme 1 and Table 1).
Scheme 1.
Although acetonitrile generally workedwell, in some instances other
solvents such as methelene chloride were more suitable due to that some
acetylenic sulfides have relative poor solubility in acetonitrile. To enhance
the rate of oxidation a trace of water was added to the acetylenic sulfide
reaction mixture. In absolute anhydrous condition the reaction hardly
proceed under similar conditions. But excessive water will reduce the rate
Table 1. Synthesis of Compounds 3a–i
a
Product
R1
R2
Yield(%)
3a
3b
3bb
3c
3d
3e
3f
3g
3h
3i
Ph
Ph
Ph
Ph
Ph
86
89
58
90
91
88
94
93
90
82
n-C4H9
n-C4H9
n-C5H11
Ph
n-C3H7
n-C4H9
n-C5H11
n-C6H13
CH3OCH2
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
aIsolatedyield.
bWithout benzoic acid.

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OXIDATION OF ACETYLENIC SULFIDES
177
of oxidation and give poor yields. Since hydrogen chloride is produced in
the reaction andit can then react with 2 to form chlorine,8 pyridine is used
to react with hydrogen chloride to form pyridine hydrochloride. Without
benzoic acidin the reaction mixture the products 3 were produced in only
50–60% yields along with a few byproducts.
Although the ease of the reactions is dependent on the electrosteric
properties of the acetylenic sulfides, it should be emphasized that the reac-
tions couldbeen performedcleanly andcontrolledto stop at the sulfoxides
stage. There was no evidence for the formation of any sulfones, which
enabledeasy isolation of the sulfoxides.
Acetylenic sulfoxides 3 have recently emergedas valuable reagents for
organic synthesis. For example, acetylenic sulfoxide 3a was transformed
into (Z )-((2-phenylethenyl)sulfinyl)benzene 5 in 93% yieldby treatment
with [RhCl(PPh3)3] under hydrogen. (Scheme 2)
Scheme 2.
EXPERIMENTAL
1H NMR spectra were recorded on AZ-300 spectrometer with TMS as
internal standard. IR spectra were determined on PE-683 instrument as neat
films. Silica gel 60 GF254 was usedfor analytical andpreparative TLC. All
products were characterized by comparison with authentic samples using
1
IR, H NMR andGC retention time. The acetylenic sulfides were prepared
from aryl sulfenyl chlorides and acetylenic lithium.3
General Procedure for the Synthesis of 3a–i: In a 25 ml two-neck flask
were placed2 mmol of acetylenic sulfide 1, 2 mmol of benzoic acid, 2 ml of
acetonitrile, 2 ml of methylene chloride, 0.1 ml of water. The mixture in flask
was allowedto stir for 5 min before the addition of the solution of
2 was
started. The solution of 2 (1.5 mmol) in 1 ml of acetonitrile was added
dropwise through a syringe. After a few minutes, the reaction temperature
began to rise. The addition took a total of 15 min and that was followed
by an additional 30 min of stirring at 40ꢀC. Excess 2 was destroyed by the
slow addition of saturated NaHSO3 solution. During this process, wet
iodide-starch test paper was used to periodically test for the presence
of oxidizing power. The precipitate of cyanuric acid 4 was removedby

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178
ZHONG, GUO, AND HUANG
filtration andwashedwith diethyl ether. Most of the solvent was removed
from the filtrate with a rotary evaporator and the residue was diluted with
20 ml of diethyl ether. The ether solution was washed with 1 N NaOH
(2 ꢁ 3 ml), 1 N HCl (2 ꢁ 3 ml), andsaturatedNaCl solution (2 ꢁ 3 ml) and
dried over MgSO4. After filtration andconcentration, the crude product was
purifiedby preparative TLC on silica gel andelutedwith hexane andethyl
acetate (5/1).
1
3a: oil. H NMR: d ¼ 7.70–7.20 (m, 10H); IR (film) n ¼ 3082, 2175,
1525, 1480, 1455, 1045, 1020 cmꢂ1. Calc. for C11H10OS: C, 74.31; H, 4.45.
Found: C, 74.45; H, 4.43%.
3b: oil. 1H NMR: d ¼ 7.57–7.92 (m, 5H, C6H5), 2.33 (m, 2H), 0.63–1.53
(m, 7H); IR (film) n ¼ 3070, 3030, 2950, 2180, 1550, 1450, 1088, 1055,
1030 cmꢂ1. Calc. for C12H14OS: C, 69.86; H, 6.84. Found: C, 69.45; H, 6.78%.
3c: oil. 1H NMR: d ¼ 7.60–710 (m, 5H, C6H5), 2.28 (m, 2H), 0.65–1.50
(m, 9H); IR (film) n ¼ 2980, 2185, 1600, 1500, 1085, 1045, 1015 cmꢂ1. Calc.
for C13H16OS: C, 70.87; H, 7.32. Found: C, 70.49; H, 7.43%.
3d9: a yellow solid, mp: 78–79ꢀC (lit.9: 78–79ꢀC). 1H NMR: d ¼
7.70–7.00 (m, 9H), 2.30 (s, 3H); IR (film) n ¼ 3080, 2940, 2900, 2150,
1495, 1450, 1055, 1020 cmꢂ1. Calc. for C15H12OS: C, 74.97; H, 5.03.
Found: C, 75.12; H, 5.01%.
1
3c10: oil. H NMR: d ¼ 7.60 (d, J ¼ 8 Hz, 2H, C6H4), 7.25 7.22 (d,
J ¼ 8 Hz, 2H, C6H4), 2.43 (s, 3H, CH3C6H4) 2.38 (t, J ¼ 7 Hz, 2H), 1.60–
1.00 (m, 5H); IR (film) n ¼ 2900, 2190, 1600, 1495, 1090, 1055, 1020 cmꢂ1
.
Calc. for C12H14OS: C, 69.86; H, 6.84. Found: C, 69.45; H, 6.78%
1
3f10: oil. H NMR: d ¼ 7.58 (d, J ¼ 8 Hz, 2H, C6H4), 7.22 (d, J ¼ 8 Hz,
2H, C6H4), 2.42 (s, 3H, CH3C6H4) 2.36 (t, J ¼ 6 Hz, 2H), 1.85–0.85 (m, 7H);
IR (film) n ¼ 2900, 2190, 1600, 1495, 1090, 1055, 1020 cmꢂ1. Calc. for
C13H16OS: C, 70.87; H, 7.32. Found: C, 70.59; H, 7.43%.
3g10: oil. 1H NMR: d ¼ 7.60 (d, J ¼ 8 Hz, 2H, C6H4), 7.24 (d, J ¼ 8 Hz,
2H, C6H4), 2.42 (s, 3H, CH3C6H4) 2.36 (t, J ¼ 6 Hz, 2H), 1.85–0.90 (m, 9H);
IR (film) n ¼ 2980, 2190, 1600, 1495, 1090, 1055, 1020 cmꢂ1. Calc. for
C14H18OS: C, 71.75; H, 7.74. Found: C, 71.66; H, 7.63%.
3h10: oil. 1H NMR: d ¼ 7.68 (d, J ¼ 8 Hz, 2H, C6H4), 7.32 (d, J ¼ 8 Hz,
2H, C6H4), 2.44 (s, 3H, CH3C6H4) 2.36 (t, J ¼ 6 Hz, 2H), 1.80–0.90 (m,
11H): IR (film) n ¼ 2980, 2190, 1600, 1495, 1090, 1055, 1020 cmꢂ1. Calc.
for C15H20OS: C, 72.53; H, 8.11. Found: C, 72.72; H, 8.03%.
1
3i1: oil. H NMR: d ¼ 7.65 (d, J ¼ 8 Hz, 2H, C6H4), 7.25 (d, J ¼ 8 Hz,
2H, C6H4), 4.25 (s, 3H, CH2O), 3.35 (s, 2H, CH3O), 2.43 (s, 3H, CH3C6H4);
IR (film) n ¼ 2940, 2825, 2180, 1595, 1105, 1060, 1015 cmꢂ1. Calc. for
C11H12O2S: C, 63.43; H, 5.81. Found: C, 63.59; H, 5.87%.
The Synthesis of (Z )-((2-Phenylethenyl)sulfinyl)benzene 5: A solution of
3a (1 mmol) in anhydrous benzene (15 ml), degassed twice by lyophilization

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OXIDATION OF ACETYLENIC SULFIDES
179
and replacement with nitrogen, was added to RhCl(PPh3)3, (0.03 mmol)
under hydrogen. The mixture was hydrogenated overnight (24 h) at room
temperature under an atmospheric pressure. The mixture was diluted with
ether andpassedthrough a short column of silica gel. Removal of the
solvent under reduced pressure followed by chromatography of the residure
on silica gel (hexane/EtOAc, 5 :1), gave the (Z )-((2-phenylethenyl)sulfinyl)-
benzene 5 in 93% yield.
1
511: oil. H NMR: d ¼ 7.70–7.20 (m, 10H, Ph), 7.05 (d, J ¼ 10.5 Hz,
1H), 6.40 (d, J ¼ 10.5 Hz, 1H); IR (film) n ¼ 3085, 3010, 1605, 1500,
1040 cmꢂ1. Calc. for C14H12OS: C, 73.65; H, 5.30. Found: C, 73.59;
H, 5.41%.
ACKNOWLEDGMENT
This work was made possible thanks to The Major Laboratory of
Organic Chemistry, Zhejiang University (Campus Xixi).
REFERENCES
1. Villar, J.M.; Delgado, A.; Llebaria, A.; Moreto, J.M. Tetrahedron
1996, 52, 10525.
2. Russel, G.A.; Ochrymowyez, L.A. J. Org. Chem. 1970, 35, 2106.
3. Zhao, S.H.; Samuel, O.; Kagan, H.B. Tetrahedron 1987, 43, 5135.
4. Kabanyane, S.T.; MaGee, D.I. Can. J. Chem. 1992, 70, 2758.
5. Cardellicchio, C.; Fiandanese, V.; Naso, F. J. Org. Chem. 1992, 57,
1718.
6. Hiegel, G.A. In Encyclopedia of Reagents for Organic Synthesis,
Paquette, L.A., Ed.; Wiley: Chichester, Sussex, England, 1995, Vol. 7,
p. 5072.
7. Hiegel, G.A.; Nalbandy, M. Synth. Commun. 1992, 22, 1595.
8. Hiegel, G.A.; Abdala, M.H.; Burke, S.V.; Beard, D.P. J. Chem. Ed.
1987, 64, 156.
9. Louis, C.; Mill, S.; Mancuso, V.; Hootele, C. Can. J. Chem. 1994,
72(5), 1347.
10. Kosugi, H.; Kitaoka, M.; Tagami, K.; Takahashi, A.; Uda, H. J. Org.
Chem. 1987, 52, 1078.
11. Posner, G.H.; Tang, P.-W. J. Org. Chem. 1978, 43, 4131.
Receivedin the Netherlands February 15, 2000

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