ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 1, p. 149.
Pleiades Publishing, Ltd., 2007.
Original Russian Text
No. 1, p. 159.
A.P. Zaraiskii, L.I. Velichko, N.A. Zaraiskaya, N.M. Anikeeva, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77,
LETTERS
TO THE EDITOR
Exhaustive Direct Methylthiomethylation
of Mesitylene and Durene
A. P. Zaraiskii, L. I. Velichko, N. A. Zaraiskaya, 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
Received August 30, 2006
DOI: 10.1134/S1070363207010239
We previously showed [1] that the use of methyl-
sulfanylmethyl acetate as reagent under acidic condi-
tions ensures direct introduction of a MeSCH2 group
into aromatic ring. Oda and Yamamoto [2] reported
on the methylthiomethylation of anisole, but the yield
of the product was poor. As a rule, the procedures for
the synthesis of MeSCH2-substituted derivatives im-
plied treatment of highly nucleophilic substrates
(phenols, naphthols, anilines) with appropriately ac-
tivated sulfur-containing reagents (DMSO, sulfides,
thiols), and the reaction conditions were difficult to
maintain (liquid ammonia, low temperature, etc [1]).
A general method for the preparation of such com-
pounds is based on the reaction of the corresponding
chloromethyl derivative with alkali metal thiolates.
Serious disadvantages of most known procedures
include a large number of steps, often poor yields, and
formation of by-products. Using mesitylene and
durene as examples we now demonstrate a modified
procedure [1] for the direct and exhaustive methyl-
thiomethylation at the aromatic ring.
from 0.66 g of durene, 2.7 ml of methylsulfanylme-
thyl acetate, 2.5 ml of n-nonane, and 2.5 ml of 45%
sulfuric acid we obtained 1.0 g (80%) of the product.
1
mp 166 C (from n-nonane). H NMR spectrum (ace-
tone-d6, TMC), , ppm: 2.12 s (6H, SCH3), 2.28 s
(12H, CH3), 3.78 s (4H, CH2). Found, %: C 66.30;
H 8.79; S 25.00. C14H22S2. Calculated, %: C 66.08;
H 8.72; S 25.20.
Under the above conditions, no more than two
methylsulfanylmethyl groups can be introduced into
the naphthalene ring. A mixture of 0.25 g naphthalene,
1.1 g of methylsulfanylmethyl acetate, 2.5 ml of
n-octane, and 2.5 ml of 45% sulfuric acid was heated
for 4 h at 115 C under stirring. The product was 1,4-
bis(methylsulfanylmethyl)naphthalene. Yield 0.34 g
1
(68%), mp 104 C (from n-octane). H NMR spectrum
(acetone-d6, TMC), , ppm: 2.06 s (6H, SCH3), 4.21 s
(4H, CH2), 7.40 s (2H, 2-H, 3-H), 7.52 d (2H, 5-H,
8-H), 8.26 d (2H, 6-H, 7-H). Found, %: C 67.75; H
6.53; S 25.72. C14H16S2. Calculated, %: C 67.69; H
6.49; S 25.81.
1,3,5-Trimethyl-2,4,6-tris(methylsulfanylme-
thyl)benzene. A heterogeneous mixture of 0.7 ml of
mesitylene, 3.3 ml of methylsulfanylmethyl acetate,
2.5 ml of n-nonane, and 2.5 ml of 45% sulfuric acid
was stirred at 115 C. After 3 h, the mixture was
cooled, 10 ml of chloroform and 5 ml of water were
added, the organic phase was separated and washed
with 5 ml of water, 5 ml of sodium hydrogen carbo-
nate, and 5 ml of water again and dried over an-
hydrous calcium chloride, and the solvent was distil-
led off. Yield 1.29 g (85%), mp 178 180 C (from
The fact that two peri positions in the naphthalene
molecule remained unoccupied indicates strong para-
orienting effect of methylsulfanylmethyl group and
considerable steric requirements of the reagent.
However, the relative ease of formation of exhaustively
substituted derivatives from mesitylene and durene is
not completely clear from the above viewpoint.
1
The H NMR spectra were recorded on a Varian
Gemini-200 instrument (200 MHz).
1
CCl4). H NMR spectrum (CD2Cl2, TMS), , ppm:
REFERENCES
2.09 s (9H, SCH3), 2.41 s (9H, CH3), 3.74 s (6H,
CH2). Found, %: C 60.72; H 8.59; S 30.61. C15H24S3.
Calculated, %: C 59.94; H 8.05; S 32.01.
1. Zaraiskii, A.P. and Kachurin, O.I., Russ. J. Org. Chem.,
2003, vol. 39, no. 11, p. 1572.
2. Oda, R. and Yamamoto, K., Chem. Abstr., 1963,
vol. 59, no. 4, p. 3806.
1,2,4,5-Tetramethyl-3,6-bis(methylsulfanylme-
thyl)benzene. Following an analogous procedure,
149
Zaraiskii
