New method for the synthesis of benzene- and phenylmethanesulfonylmethyl- substituted 1,3-dithiolanes and 1,3-dithianes

Article abstract of DOI:10.1007/s10593-010-0628-5

The reactions of (E)-chlorovinyl sulfones with 1,2-ethanedithiol or 1,3-propanedithiol in the presence of triethylamine in toluene at 80°C lead to the selective formation of 1,3-dithiolane and 1,3-dithiane derivatives with yields of up to 49%.

Full text of DOI:10.1007/s10593-010-0628-5

Chemistry of Heterocyclic Compounds, Vol. 46, No. 9, 2010
NEW METHOD FOR THE SYNTHESIS OF BENZENE- AND
PHENYLMETHANESULFONYLMETHYL-SUBSTITUTED
1,3-DITHIOLANES AND 1,3-DITHIANES
J. Višņevska1, E. Abele1**, and E. Lukevics1*
The reactions of (E)-chlorovinyl sulfones with 1,2-ethanedithiol or 1,3-propanedithiol in the presence of
triethylamine in toluene at 80°C lead to the selective formation of 1,3-dithiolane and 1,3-dithiane
derivatives with yields of up to 49%.
Keywords: (E)-2-chlorovinyl sulfones, 1,3-dithianes, 1,3-dithiolanes,.
1,3-Dithiolanes [1; 2, p. 329] and 1,3-dithianes [1; 2, p. 724; 3] have attracted attention as an important
class of heterocyclic compounds widely used in organic synthesis. The 1,3-dithiolane and 1,3-dithiane rings are
also used as protecting groups in carbonyl compounds [2, 4]. In addition, there are published data on the
insecticidal activity of derivatives of 1,3-dithiolane [5] and 1,3-dithiane [6]. 1,3-Dithiane derivatives have also
been tested as agents acting on the central nervous system [7].
In the literature there are only two papers on the synthesis of arylsulfonylmethyl[1,3]dithiolanes and
arylsulfonylmethyl[1,3]dithianes and their derivatives. The principal method for the synthesis of 2-benzene-
sulfonylmethyl[1,3]dithiolane is based on the reaction of (Z)-1,2-bis(phenylsulfonyl)ethylene with 1,2-ethane-
dithiol in the presence of NaH in tetrahydrofuran [8]. Compounds of this type were also obtained by the reaction
of the respective arylsulfonylacetylenes with 1,2-etanedithiol or 1,2-benzenedithiol in the NaH–THF system [8,
9]. In many cases, however, the synthesis of arylsulfonylacetylenes is extremely complicated, while the
synthesis of arylsulfonyl methyl[1,3]dithiolanes requires the use of fire-hazardous sodium hydride. The aim of
our work was therefore to develop a simple method for the synthesis of benzene- and phenylmethane-
sulfonylmethyl-substituted 1,3-dithiolanes and 1,3-dithianes.
SH
( )
( )
S
O
R
O
O
O
n
O
O
R
/ Et3N / PhMe, 20°C
HS
n
Et3N
S
SH
S
S
( )
S
S
Cl
n
–HCl
R
3–6
1, 2
1,3,4 R = Ph; 2,5,6 R= PhCH2; 3,5 n = 1, 4,6 n = 2
_______
* Deceased.
** To whom correspondence should be addressed, e-mail: abele@osi.lv.
1Latvian Institute of Organic Synthesis, Riga LV-1006, Latvia.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1326-1328, September, 2010.
Original article submitted December 8, 2009. Revision submitted April 19, 2010.
1068
0009-3122/10/4609-1068©2010 Springer Science+Business Media, Inc.

We developed a method for the synthesis of the 1,3-dithiolanes and 1,3-dithianes 3-6 in the 1,2-ethane-
dithiol (or 1,3-propanedithiol)–Et3N–toluene system at 80°C. The products were isolated by column chromato-
graphy with yields of 17-49% (see Experimental).
The reaction mechanism includes the reaction of compounds 1 or 2 with dithiols with the formation of
intermediates that add to the activated C=C bond with the formation of compounds 3-6.
EXPERIMENTAL
1
The H NMR spectra were recorded in CDCl3 on a Varian Mercury-200 instrument (200 MHz) with
HMDS as internal standard (δ 0.05 ppm). The mass spectra were obtained on a GC-MS HP 6890 instrument (70
eV). The reactions were monitored on Silufol UV-254 plates. The 1,2-ethanedithiol and 1,3-propanedithiol
(Acros) were used without additional purification.
The (E)-2-chlorovinyl sulfones 1 and 2 were obtained by the method in [10].
Synthesis of 1,3-Dithiolanes 3 and 5 and 1,3-Dithianes 4 and 6 by Nucleophilic Addition of
1,2-Ethanedithiol or 1,3-Propanedithiol to 2-Chlorovinyl Sulfones 1 and 2 (General Method). To a solution
of (E)-2-chlorovinyl sulfone 1 or 2 (1 mmol) and triethylamine (0.25 g, 2 mmol) in dry toluene (2 ml) we added
1,2-ethanedithiol or 1,3-propanedithiol (1 mmol). The mixture was stirred at 80°C for 72 h and filtered through a
thin layer of silica gel. The toluene was evaporated on a rotary evaporator. The products 3-6 were isolated by
1
column chromatography (eluent 2:1 toluene–ethyl acetate) in the form of yellow liquids and identified by H
NMR and mass spectroscopy. According to the data from gas chromatography the purity of the compounds was
higher than 95%.
1
2-Benzenesulfonylmethyl[3,1]dithiolane (3). The yield 31%. H NMR spectrum, δ, ppm (J, Hz):
2.72-2.79 (4Н, m, СН2СН2); 3.59 (2Н, d, J = 8.0, СН2); 4.78 (1H, t, J = 8.0, SCH); 7.54-7.72 (3Н, m, Н-3,4,5);
7.91-7.95 (2Н, m, Н-2,6). Mass spectrum, m/z (Irel, %): 141 [М−СН2(dithiolane)]+ (5), 118 [M−SO2Ph]+ (100),
105 (12), 91 (45), 77 (78), 59 (32), 51 (48), 45 (44). Found, %: С 45.61; Н 4.63. C10H12O2S3. Calculated, %:
С 46.12; Н 4.64.
2-Benzenesulfonylmethyl[1,3]dithiane (4). The yield 49%. Rf 0.37. 1H NMR spectrum, δ, ppm (J, Hz):
1.80-2.12 (2H, m, CH2СH2CH2); 2.52-2.95 (4H, m, SCH2); 3.51 (2H, d, J = 6.0, CH2); 4.48 (1H, t, J = 8.0,
SCH); 7.18-7.28 (1H, m, H-4); 7.52-7.67 (2H, m, H-3,5); 7.93-7.97 (2H, m, H-2,6). Mass spectrum, m/z (Irel,
%): 274 [M]+ (3), 132 (100), 105 (13), 91 (31), 77 (80), 59 (29), 45 (44). Found, %: C 48.40; H 4.88.
C11H14O2S3. Calculated, %: C 48.14; H 5.14.
1
2-Phenylmethanesulfonylmethyl[1,3]dithiolane (5). The yield 25%. Rf 0.53. H NMR spectrum, δ,
ppm (J, Hz): 2.96-3.07 (4H, m, CH2CH2); 3.42 (2H, d, J = 8.0, CH2); 4.17 (2H, s, PhCH2); 4.56 (1H, t, J = 8.0,
CH); 7.25-7.40 (5H, m, C6H5). Mass spectrum, m/z (Irel, %): 274 [M]+ (<1), 118 [M−SO2CH2Ph]+ (100), 91 (97),
65 (13). Found, %: C 48.16; H 5.11. C11H14O2S3. Calculated, %: C 48.14; H 5.14.
1
2-Phenylmethanesulfonylmethyl[1,3]dithiane (6). The yield 17%. Rf 0.5. H NMR spectrum, δ, ppm
(J, Hz): 1.80–2.04 (2H, m, CH2CH2CH2); 2.75–3.04 (4H, m, SCH2); 3.25 (2H, d, J = 6.0, O2SCH2CH); 4.43
(2H, s, PhCH2); 4.54 (1H, t, J = 6.0, CH); 7.35–7.45 (5H, m, C6H5). Mass spectrum, m/z (Irel, %): 288 [M]+ (<1),
132 (100), 91 (90), 73 (13), 65 (22), 45 (22). Found, %: C 48.31; H 5.00. C12H16O2S3. Calculated, %: C 49.97; H
5.59.
REFERENCES
1.
D. L. Rakhmankulov, V. V. Zorin, F. N. Latypova, S. S. Zlotskii, and R. A. Karakhanov, Usp. Khim.,
52, 619 (1983).
1069

2.
Т. W. Green and P. G. М. Wuts, Protective Groups in Organic Synthesis, Wiley-Intersci., New York
(1999).
3.
4.
M. Yus, С. Najera, and F. Foubelo, Tetrahedron, 59, 6147 (2003).
K. Tanemura, H. Dohya, M. Imamara, T. Suzuki, and T. Horiguchi, J. Chem. Soc, Perkin Trans. 1, 453
(1996).
5.
H. Uneme, H. Mitsudera, J. Yamada, T. Komikado, Y. Kono, Y. Manabe, and M. Numata, Biosci.
Biotechn. Biochem., 56, 1293 (1992).
6.
7.
8.
H. Mitsudera and K. Konishi, J. Pest. Sci., 16, 387 (1991).
I. Kapfer, J. E. Hawkinson, J. E. Casida, and M. P. Goeldner, J. Med. Chem., 37, 133 (1994).
S. Cossu, O. De Lucchi, F. Fabris, R. Ballini, and G. Bosica, Synthesis, 1481 (1996).
R. Medel and J. Plumet, Synthesis, 1339 (2006).
9.
10.
E. Ābele, J. Višņevska, Latv. J. Chem. 263 (2008).
1970