Preparation of diselenides by the oxidation of selenols using trichloroisocyanuric acid

Article abstract of DOI:10.1081/SCC-100104062

Selenols are readily oxidized to diselenides by a solution of pyridine, water, benzoic acid, and trichloroisocyanuric acid in acetonitrile and methylene chloride.

Full text of DOI:10.1081/SCC-100104062

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PREPARATION OF DISELENIDES
BY THE OXIDATION
OF SELENOLS USING
TRICHLOROISOCYANURIC ACID
Ping Zhong a & Meng-Ping Guo a
a Department of Chemistry, Yichun Teachers
College, 587 Huanchengxi Road, Yichun, 336000,
P.R. China
Version of record first published: 02 Aug 2010.
To cite this article: Ping Zhong & Meng-Ping Guo (2001): PREPARATION OF
DISELENIDES BY THE OXIDATION OF SELENOLS USING TRICHLOROISOCYANURIC ACID,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 31:10, 1507-1510
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SYNTHETIC COMMUNICATIONS, 31(10), 1507–1510 (2001)
PREPARATION OF DISELENIDES BY THE
OXIDATION OF SELENOLS USING
TRICHLOROISOCYANURIC ACID
Ping Zhong* and Meng-Ping Guo
Department of Chemistry, Yichun Teachers College,
587 Huanchengxi Road, Yichun, 336000, P.R. China
ABSTRACT
Selenols are readily oxidized to diselenides by a solution of
pyridine, water, benzoic acid, and trichloroisocyanuric acid in
acetonitrile and methylene chloride.
Diselenides are important reagents in organic synthesis1–3 and
many methods for the synthesis of diselenides have been published.4–8
The oxidation of a selenol to a diselenide is one of the most important,5–8
and many reagents can be used to oxidize selenols to dislenides, such
as tris[trinitratocerium(IV)]-paraperiodate [(NO3)3Ce]3H2IO6,5 H2O2,6
and O2.7 Trichloroisocyanuric acid [1,3,5-trichloro-1,3,5-traizine-2,4,6-
(1H,3H,5H)-trione] 2 has been a useful reagent in organic synthesis.9 It
has been used to oxidized secondary alcohol to ketones in good yields.10
We have now found that trichloroisocyanuric acid [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 selenols into diselenides.
A solution of a selenol 1, pyridine, water, benezoic acid, and 2 in
acetonitrile and methylene chloride underwent oxidation to produce
* Corresponding author.
1507
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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ZHONG AND GUO
the corresponding diselenide 3, along with cyanuric acid 4 and hydrogen
chloride. Yields are good to excellent (Scheme 1 and Table 1).
Scheme 1.
Although acetonitrile generally worked well, in some instances, other
solvents such as methelene chloride were more suitable, due to the fact that
some selenols have relatively poor solubility in acetonitrile. To enhance the
rate of oxidation, a trace of water was added to the selenol reaction mixture.
However, excessive water will reduce the rate of oxidation and give
poor yields. Without benzoic acid in the reaction, the products 3 were
produced in only 50–60%, along with a few by-products. Since hydrogen
chloride is produced in the reaction and it can then react with 2 to form
chlorine,11 pyridine is used to react with hydrogen chloride to form
pyridine hydrochloride.
Table 1. Synthesis of Diselenides 3a–h
Product
R
M.p. (ꢀC)a
M.p. (lit.) (ꢀC)
60–614
Yield (%)b
3a
3ac
3b
3c
3d
3e
3f
Ph
Ph
61–62
61–62
82
54
85
60–614
4
4-MeC6H4
4-ClC6H4
4-MeOC6H4
4-BrC6H4
PhCH2
n-C6H13
n-C12H25
n-C12H25
45–4644–45
85–8686 89
–47 45–4646
108–109
91–92
4
80
84
75
72
81
76
109–1104
92–935
oil12
30–3112
50–5112
3g
3h
3i
oil
30–31
51–52
1
aAll products are characterized by MS, H NMR, IR and m.p.
bcrystallized from ethanol.
cwithout benzoic acid.

SELENOL OXIDATION
1509
1
Table 2. IR and H NMR Spectra Data for Diselenides 3
IR (KBr), ꢀ (cmꢁ1 1H NMR (CDCl3/TMS), d(ppm)
7.0–7.6(m, 10H)
3
)
3a
3b
3c
3d
3e
3f
3g
3h
3i
3040, 1585, 1475, 790
2930, 1620, 1385, 795
3050, 1460, 1000, 810
2930, 1640, 1380, 820
3045, 1465, 1020, 820
3035, 1600, 1495, 820
2900, 1460, 1240, 725
2905, 1460, 1235, 715
2900, 1460, 1225, 722
2.20(s, 6H), 6.85–7.40(q, J ¼ 8.8 Hz, 8H)
7.10–7.45 (q, J ¼ 8 Hz, 8H)
3.75(s, 6H), 6.70–7.50 (q, J ¼ 8.8 Hz, 8H)
7.00–7.40 (q, J ¼ 8.4 Hz, 8H)
3.37 (s, 4H), 7.18 (s, 10H)
0.88(t, 6H), 1.33(m, 12H), 1.73(m, 4H), 2.90(t, 4H)
0.89(t, 6H), l.33(m, 36H), l.75(m, 4H), 2.93(t, 4H)
0.92(t, 6H), 1.32(M, 52H), 1.73(m, 4H), 1.90(t, 4H)
Although the ease of the reactions is dependent on the electrosteric
properties of the selenols, it should be emphasized that the reactions could
be performed cleanly and controlled to stop at the diselenides stage. No
over-oxidation was observed in any instance, even when the reactions were
carried out with an excess of the reagent and different solvent media.
In view of the easily available starting materials, good yield, mild and
neutral conditions, we feel that the present work described herein may
provide a useful method for the preparation of diselenides. It should
noted, however, that trichloroisocyanuric acid is intolerant of some func-
tional groups and it is a possible limitation.
EXPERIMENTAL
1H NMR spectra were recorded on a PMX-60 spectrometer in CDCl3
as the solvent with TMS as an internal standard. IR spectra were determined
on PE-683 instrument as neat films. Silica gel 60 GF254 was used for ana-
lytical and preparative TLC. All products were characterized by comparison
1
with authentic samples using IR, H NMR, and m.p.
General Procedure for the Synthesis of 3a–i
In a 25-mL two-neck flask were placed 2 mmol of selenol 1, 2 mmol of
benzoic acid, 2 mL of acetonitrile, 2 mL of methylene chloride, and 0.1 mL
of water. The mixture was stirred for 5 min before the addition of the
solution of 2 was started. The solution of 2 (1.5 mmol) in 1 mL of acetoni-
trile was added dropwise through a syringe. After a few minutes the reaction

1510
ZHONG AND GUO
temperature began to rise. The addition took a total of 30 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 removed by filtra-
tion and washed with diethyl ether. Most of the solvent was removed from
the filtrate with a rotary evaporator and the residue was diluted with 10 mL
of diethyl ether and 10 mL of methylene chloride. The organic solution
was washed with 1 N NaOH (2 ꢂ 3 mL), 1 N HCl (2 ꢂ 3 mL), and saturated
NaCl solution (2 ꢂ 3 mL) and dried over MgSO4. After filtration and con-
centration, the crude product was purified by preparative TLC on silica gel
and eluted with hexane and ethyl acetate (20/1).
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Received in the UK May 2, 2000