Oxidation of γ-oxo sulfides with chlorine dioxide

Article abstract of DOI:10.1134/S1070428008120087

γ-Oxo sulfides were oxidized to the corresponding sulfoxides with an aqueous solution of chlorine dioxide.

Full text of DOI:10.1134/S1070428008120087

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 12, pp. 1773–1775. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.V. Loginova, E.V. Ashikhmina, S.A. Rubtsova, Yu.V. Krymskaya, A.V. Kuchin, 2008, published in Zhurnal Organicheskoi Khimii,
2008, Vol. 44, No. 12, pp. 1799–1801.
Oxidation of γ-Oxo Sulfides with Chlorine Dioxide
I. V. Loginova, E. V. Ashikhmina, S. A. Rubtsova, Yu. V. Krymskaya, and A. V. Kuchin
Institute of Chemistry, Komi Research Center, Ural Division, Russian Academy of Sciences,
ul. Pervomaiskaya 48, Syktyvkar, 167982 Russia
e-mail: loginova-iv@chemi.komisc.ru
Received April 8, 2008
Abstract—γ-Oxo sulfides were oxidized to the corresponding sulfoxides with an aqueous solution of chlorine
dioxide.
DOI: 10.1134/S1070428008120087
Oxidation of oxo sulfides to the corresponding
sulfoxides and sulfones attracts increasing attention
due to prospects in using oxo sulfoxides as reagents in
asymmetric synthesis [1], palladium and platinum ex-
tractants, plant growth regulators, flotation agents [2],
and metal complexones [3].
In the present article we report on the oxidation of
some oxo sulfides to the corresponding oxo sulfoxides
with the use of chlorine dioxide. We previously de-
monstrated high chemoselectivity in the oxidation of
dialkyl, diaryl, alkyl aryl, and dibenzyl sulfides to sulf-
oxides with that reagent [10–14]. Initial γ-oxo sulfides
I–III were synthesized according to the procedure
described in [3] for methylsulfanylation of ketones [3].
Oxo sulfoxides can be synthesized by condensation
of sulfinyl anion with esters [4], oxidation of 6-substi-
tuted 2,3-dihydro-1,4-oxathiines with subsequent ring
opening [5], and oxidation of oxo sulfides with various
oxidants [6–9].
The oxidation of sulfides I–III with an aqueous so-
lution of chlorine dioxide was performed at 20°C, the
substrate-to-oxidant molar ratio being 1:0.5 for com-
Scheme 1.
O
O
8
7
14
11
2
1
Me
ClO2
13
12
S
S
Me
9
3
4
6
5
O
10
Me
Me
Me
Me
O
I
IV
O
8
7
14
1
4
ClO2
13
12
S
S
6
2
3
9
5
O
10
11
II
V
O
O
S
S
O
9
1
4
16
10
8
7
2
3
15
14
S
6
11
12
17
5
O
ClO2
S
13
24
21
18
23
22
19
20
III
VI
1773

LOGINOVA et al.
1774
1
pounds I and II and 1:1 for III. The conversion of
initial sulfides was 65–78%, and γ-oxo sulfoxides IV–
VI were formed in 62–74% yield; the products con-
tained no impurity of the corresponding sulfone.
The H and 13C NMR spectra were measured on
1
a Tesla BS467A spectrometer (80 MHz for H) using
CDCl3 as solvent. The elemental compositions were
determined on an EA1110 CHNS-O automatic
analyzer. Column chromatography was performed on
silica gel using gradient elution with benzene–ethanol.
Silufol plates were used for thin-layer chromatography
(benzene–ethanol, 4:1; the chromatograms were de-
veloped by treatment with a 5% solution of potassium
permanganate).
The structure of sulfoxides IV–VI was confirmed
by IR and NMR spectroscopy. The IR spectra of IV–
VI contained absorption bands typical of sulfoxide
1
group in the region 1020–1050 cm–1. In the H NMR
spectra of these compounds, signals from the methyl-
ene protons displaced downfield relative to the corre-
sponding signals of the initial sulfides. Compound IV
3-(Benzylsulfanylmethyl)-4-methylpentan-2-one
1
displayed in the H NMR spectrum signals belonging
(I). Yield 65%, bp 170°C (2 mm). IR spectrum, ν,
cm–1: 700 (C–S), 1750 (C=O). H NMR spectrum, δ,
1
to protons in the methyl and phenyl groups; protons on
C8 gave two singlets at δ 3.94 and 4.11 ppm. The
1H NMR spectrum of V contained signals from protons
in the cyclohexane and benzene rings. As in the spec-
trum of IV, two singlets from methylene protons were
present at δ 3.94 and 4.10 ppm.
ppm: 0.78 m (3H, C5H3), 0.91 m (3H, C6H3), 1.11 m
(1H, 4-H), 2.10 m (1H, 3-H), 2.17 s (3H, C1H3), 2.54 d
(2H, 7-H, J = 4 Hz), 3.65 s (2H, 8-H), 7.25 m (5H,
C6H5). C NMR spectrum, δC, ppm: 21.85 (C5), 22.22
13
(C6), 22.24 (C4), 29.23 (C1), 29.78 (C7), 52.25 (C8),
95.95 (C3), 126.56 (C12), 127.07 (C13), 127.26 (C11),
127.56 (C14), 128.42 (C10), 137.27 (C9), 208.13 (C2).
Found, %: C 71.22; H 8.52; S 13.61. C14H20OS. Cal-
culated, %: C 71.19; H 8.47; S 13.56.
The oxidation of oxo sulfide III involved both
sulfur atoms and led to the formation of bis-sulfoxide
1
VI. In the H NMR spectrum of VI, aromatic protons
resonated as multiplets at δ 7.29 and 7.92 ppm. The
signal from the C8H proton was retained, and protons
in positions 10 and 18 gave singlets at δ 3.87 and
4.04 ppm. The presence of a couple of singlets in the
1H NMR spectra of all oxidation products indicates
that compounds IV–VI are mixtures of diastereoiso-
mers. According to the signal intensities, the diastereo-
isomer ratio is 1:1. Presumably, the absence of dif-
ferentiating effect of the oxo group in the initial
sulfides is responsible for the lack of stereoselectivity.
Molecules IV and V possess chiral carbon atoms (C3
and C6, respectively), and a new chiral center appears
on the sulfur atom. Compound VI has two sulfoxide
groups, each being a chiral center. Splitting of the
signal from protons in the α-position with respect to
the sulfoxide group suggests diastereotopicity of these
protons.
2-(Benzylsulfanylmethyl)cyclohexan-1-one (II).
Yield 72%, bp 160°C (2 mm). IR spectrum, ν, cm–1:
1
695 (C–S), 1750 (C=O). H NMR spectrum, δ, ppm:
1.57 m (2H, 4-H), 1.81 m (2H, 3-H), 2.15 m (2H, 5-H),
2.33 m (2H, 2-H), 2.59 d (2H, 7-H, J = 16.0 Hz),
2.92 m (1H, 6-H), 3.59 d (2H, 8-H, J = 8.3 Hz), 7.28 m
(5H, C6H5). C NMR spectrum, δC, ppm: 24.67 (C4),
13
26.53 (C3, C5), 29.41 (C7), 33.89 (C8), 41.36 (C2),
48.64 (C6), 126.48 (C12), 128.01 (C11, C13), 128.49
(C10, C14), 128.98 (C9), 209.61 (C1). Found, %:
C 71.84; H 7.73; S 13.71. C14H18OS. Calculated, %:
C 71.79; H 7.69; S 13.67.
3-(Benzylsulfanyl)-2-(benzylsulfanylmethyl)-1-
phenylpropan-1-one (III). Yield 78%, bp 180°C
(2 mm). IR spectrum, ν, cm–1: 700 (C–S), 1700 (C=O).
1H NMR spectrum, δ, ppm: 1.22 d (4H, 9-H, 17-H,
J = 7.0 Hz), 2.61 s (4H, 10-H, 18-H), 3.77 m (1H,
8-H), 7.25 m (10H, C6H5), 7.88 m (5H, C6H5).
13C NMR spectrum, δC, ppm: 25.15 (C11), 25.90
(C9), 75.83 (C18), 78.37 (C10), 95.92 (C8), 127.19 (C4,
C17), 127.97 (C13, C15, C21, C23), 128.23 (C1, C5),
128.75 (C12, C16, C20, C24), 132.56 (C6), 129.02 (C3),
137.16 (C11, C19), 196.69 (C7). Found, %: C 73.43;
H 6.18; S 16.27. C24H24OS2. Calculated, %: C 73.47;
H 6.12; S 16.33.
The use of chloride dioxide as oxidant in the
synthesis of oxo sulfides seems to be fairly promising,
despite the lack of stereoselectivity. The latter factor
is a drawback intrinsic to most oxidants. Therefore,
further improvement of the proposed procedure may
be achieved via modification of the oxidant with chiral
reagents.
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
spectrometer from solutions in carbon tetrachloride.
3-(Benzylsulfinylmethyl)-4-methylpentan-2-one
(IV). An aqueous solution of chlorine dioxide, 15 ml
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 12 2008

OXIDATION OF γ-OXO SULFIDES WITH CHLORINE DIOXIDE
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1775
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1
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 12 2008