Transformation of dimethyl Sulfoxide into bis(methylsulfanyl)methane

Full text of DOI:10.1134/S1070428007110255

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 11, pp. 1728–1729. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.P. Zaraiskii, N.A. Zaraiskaya, L.I. Velichko, N.M. Anikeeva, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43,
No. 11, pp. 1727–1728.
SHORT
COMMUNICATIONS
Transformation of Dimethyl Sulfoxide
into Bis(methylsulfanyl)methane
A. P. Zaraiskii, N. A. Zaraiskaya, L. I. Velichko, and N. M. Anikeeva
Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine,
ul. R. Lyuksemburg 70, Donetsk, 83114 Ukraine
e-mail: azar@skif.net
Received August 27, 2006
DOI: 10.1134/S1070428007110255
We recently [1] revealed that methylsulfanylmethyl
acetate (I), which is readily available from DMSO ac-
cording to Pummerer [2], is rapidly and quantitatively
converted into bis(methylsulfanyl)methane (II) in the
presence of strong acids.
as well as with formaldehyde [reaction (5)] [5, 6]; as
a result, the corresponding dithioacetal is formed, and
the overall stoichiometry conforms to reaction (2).
+
[
H ]
[RS(H)CH Cl]+
2
RSCH Cl
2
+
Slow
[
H ]
+
MeSCH OAc
(MeS) CH2
(1)
RSH + [CH Cl]
2
2
2
I
II
H
+
2
O
RSH + HCHO
+
2 H+
+
Cl–
HCl
(3)
(4)
Reaction (1) attracts interest as an example of new
and probably general way of synthesis of thioacetals
from sulfoxides (cf. [3]), whose mechanism is not
clear. The goal of the present work was to elucidate the
mechanism of transformation (1) on the basis of pub-
lished data and demonstrate usefulness and perspec-
tives of the new method of synthesis of thioacetals
from sulfoxides.
RSH
RSCH Cl
(RS) CH2
+
2
2
+
[H ]
2
RSH
+
HCHO
(RS) CH2
+
H O
2
(5)
2
Böhme et al. [4] assumed that the process involves
autocatalysis due to liberation of hydrogen chloride.
However, the proposed mechanism was questioned by
Bordwell et al. [7] who studied the hydrolysis in 50%
As shown in [4], α-haloalkyl sulfides of the general
formula RSCH(Y)X (where R = Alk, Ph, Bzl; X = Cl,
Br, I, Y = H, Ph), which are structurally related to
methylsulfanylmethyl acetate, undergo hydrolysis in
aqueous dioxane according to Eq. (2); the reaction fol-
lows first-order kinetics.
aqueous dioxane. These authors advanced S 1 mech-
N
anism with intermediate formation of a carbenium–
sulfonium ion in the rate-determining stage and sub-
sequent fast attack by water molecule, leading to dis-
sociation of the hemithioacetal into thiol and aldehyde
[
8] [reaction (6)]. This mechanism is likely to involve
assistance by acid.
2
RSCH(Y)X
RS) CHY
+
H O
2
Slow
Cl–
RSCH OH
(
+
YCHO
+
2 HX
(2)
2
RSCH Cl
[RSCH2
RS=CH2]
2
–
Taking into account that reaction (1) was carried
out in aqueous media [1], we can presume that it
follows a mechanism analogous to the mechanism pro-
posed in [4], i.e., via hydrolysis to give the correspond-
ing thiol and aldehyde (as a result of cleavage of the
C−S bond) in the rate-determining stage. Thiol then
reacts with the initial compound [reaction (4)] [4, 5],
H O
2
RSH
+
HCHO
(6)
2
–H+
As noted in [9], α-acetoxymethyl sulfides
RSCH(Y)X (where R = Alk, Ar; Y = H; X = OAc) are
readily decomposed by the action of water to give the
1728

TRANSFORMATION OF DIMETHYL SULFOXIDE
1729
corresponding thiol, formaldehyde, and acetic acid.
However, we found that hydrolysis of methylsulfanyl-
methyl acetate (I) with water (1:1) in the absence of
sulfuric acid occurs only under severe conditions: the
conversion is only 7% in 3 min on heating at the boil-
ing point under vigorous stirring.
hydrolysis with boiling water was determined by GLC
(internal standard technique with tridecane as refer-
ence). GLC analysis was performed on an LKhM-80
model 6 chromatograph [flame ionization detector;
stainless steel column, 3000×3 mm, packed with 5%
of QF-1 on Inerton Super (0.16–0.20 mm); carrier gas
helium; oven temperature 140°C.
Thus, uncertainty and inconsistency of published
data do not allow us to draw a definite conclusion on
the mechanism of reaction (1). Following the known
data, it is unlikely that acid-catalyzed reaction (1) in
the final stage can be represented as reaction (5) pre-
ceded by transformation sequence (6), for hemithio-
acetal is an intermediate product on the path to thio-
acetal which is usually obtained from thiol and
aldehyde. Thus the mechanism of transformation (1)
requires further study.
REFERENCES
1
. Zaraiskii, A.P., Velichko, L.I., Zaraiskaya, N.A., and
Anikeeva, N.M., Ukrainian Patent no. 67 370A, 2003;
Promisl. vlasn., 2004, no. 6.
2
3
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2
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skaya khimiya, Moscow: Khimiya, 1983, vol. 5, p. 189.
The proposed procedure is advantageous since it
requires no reduced temperature, highly reactive, vola-
tile, and toxic halogen-containing sulfides, formalde-
hyde, thiols, and gaseous hydrogen chloride. Initial
sulfoxides are readily accessible from sulfides that can
be easily prepared in a laboratory or are commercial
products [10]. The procedure for the synthesis of thio-
acetals from sulfoxides is simple and efficient, as
illustrated below by the synthesis of bis(methylsul-
fanyl)methane from DMSO as an example. As con-
cerns the selectivity aspect, it should be examined
separately for each particular sulfoxide involved in the
reaction.
4. Böhme, H., Fisher, H., and Frank, R., Justus Liebigs
Ann. Chem., 1949, vol. 563, p. 54.
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svoistva, primenenie galoidsul’fidov (Halo Sulfides:
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6
7
8
. Braun, M. and Seebach, D., Chem. Ber., 1975, vol. 109,
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(
Chemistry of Organic Sulfur Compounds), Moscow:
2
5 ml (25 g, 0.32 mol) of anhydrous dimethyl sulfox-
Khimiya, 1975, p. 110.
ide and 43.9 g (0.43 mol) of acetic anhydride was
heated to 130°C; the mixture vigorously boiled up and
was kept for 1 h at that temperature. It was then cooled
to room temperature, and 50 ml of 51% sulfuric acid
was added on stirring and cooling. The resulting solu-
tion was kept for 5 min and diluted with 50 ml of
water, 20 g of sodium sulfate was added, and the mix-
ture was stirred until the salt dissolved completely. The
mixture was allowed to settle down, and the organic
phase was separated, washed with 20 ml of water, and
9
. Oae, S., Organic Chemistry of Sulfur, New York:
Plenum, 1977, p. 407.
1
0. Darst, T., Comprehensive Organic Chemistry, Barton, D.
and Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 3.
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khimiya, Moscow: Khimiya, 1983, vol. 5, p. 258; Be-
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Khimiya organicheskikh soedinenii sery. Obshchie Vop-
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Aspects), Moscow: Khimiya, 1988, p. 181; Sintez sul’fi-
dov, tiofenov i tiolov tipa soedinenii, vstrechayushchikh-
sya v neftyakh (Synthesis of Sulfides, Thiophenes, and
Thiols Like Those Occurring in Oils), Karaulov, E.N.,
Ed., Moscow: Nauka, 1988, p. 23.
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949, vol. 82, p. 433.
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the Basis of Organomagnesium and Organozinc Com-
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Khim., 1981, no. 10Zh350.
dried over anhydrous MgSO . Yield 17.2 g (98%),
4
2
0
20
4
1
bp 147°C, n = 1.5340, d = 1.059 (cf. [11]). H NMR
D
spectrum, δ, ppm: 2.11 s (6H, CH ), 3.66 s (2H, CH )
3
2
(
cf. [12]). Found, %: C 32.96; H 7.49; S 55.54.
1
C H S . Calculated, %: C 33.29; H 7.46; S 59.23.
3
8 2
1
1
The H NMR spectrum was recorded on a Gemini-
00 spectrometer at 200 MHz using CD CN as solvent
1
2
3
and TMS as internal reference. Methylsulfanylmethyl
acetate (I) was synthesized according to the procedure
reported in [2]. The conversion of compound I in the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007