One-Pot Synthesis of 2-Ylidene-1,3-dithiolanes

Article abstract of DOI:10.1134/S1070428019020246

A one-pot synthesis of 2-ylidene-1,3-dithiolanes, involving the reaction of carbon disulfide with methylene-active compounds in the presence of sodium ethylate followed by adding 1,2-dichloralkanes to the reaction mixture, is developed.

Full text of DOI:10.1134/S1070428019020246

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 2, pp. 276–278. © Pleiades Publishing, Ltd., 2019.
Russian Text © K.V. Lipin, O.V. Ershov, M.Yu. Belikov, S.V. Fedossev, 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 2, pp. 314–316.
SHORT
COMMUNICATIONS
One-Pot Synthesis of 2-Ylidene-1,3-dithiolanes
a,
a
a
a
K. V. Lipin *, O. V. Ershov , M. Yu. Belikov , and S. V. Fedossev
a
Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, Chuvashia, 428015 Russia
e-mail: lipinkost@mail.ru
*
Received May 16, 2018; revised May 22, 2018; accepted August 15, 2018
Abstract—A one-pot synthesis of 2-ylidene-1,3-dithiolanes, involving the reaction of carbon disulfide with
methylene-active compounds in the presence of sodium ethylate followed by adding 1,2-dichloralkanes to the
reaction mixture, is developed.
Keywords: sulfur-containing heterocycles, dithiolanes, one-pot synthesis, methylene-active compound,
multicomponent synthesis
DOI: 10.1134/S1070428019020246
1
,3-Dithiolanes bearing electron-acceptor
dimedone (5,5-dimethylcyclohexane-1,3-dione)
(Scheme 1) and ethyl cyanoacetate (Scheme 2).
substituents are applied in the synthesis of compounds
with valuable optical and electronic properties [1–7].
For this reason, searching for rational synthetic
approaches to such 1,3-dithiolanes is an urgent
problem. We previously reported a method of synthesis
of 2-ylidene-1,3-dithiolanes, which involves the
reaction of sodium 2,2-disubstituted 1,1-
ethenebisthiolates with 1,2-dichloroalkanes [8] and
described a one-pot synthesis of dithiolanes from
malononitrile and cyanoacetamide. Proceeding with
this research, we found that other methylene-active
compounds, too, can be involved in the three-
component reaction. As a result, a one-pot synthesis of
The reaction with ethyl cyanoacetate gives,
according to the NMR data, a 1 : 1 mixture of the E
and Z isomers of ethyl 2-cyano-2-(4-methyl-1,3-
dithiolan-2-ylidene)acetate 2b.
The structure of the synthesized compounds was
1
confirmed by IR and Н NMR spectroscopy and mass
spectrometry.
The IR spectra of dithiolanes 1 and 2 display strong
stretching absorption bands of the C=O and С=С
–1
bonds at 1706–1715 and 1458–1468 cm , respectively.
The IR spectra of compounds 2 also contain
characteristic signals of the conjugated cyano group.
2
-ylidene-1,3-dithiolanes 1a, 1b and 2a, 2b, which
includes the reaction of carbon disulfide with a
methylene-active compounds in the presence of
sodium ethylate followed by adding 1,2-
dichloroalkanes to the reaction mixture (Schemes 1
and 2). The yields of the reaction products were 85–
1
The Н NMR spectra of compounds 1a and 1b show
1
alkyl proton signals at 0.95–4.04 ppm. The Н NMR
spectra of compounds 2a and 2b also contain signals
of the ester alkyl groups. The mass spectra display
molecular ion peaks (20–100%).
9
6%. As methylene-active compounds we used
Scheme 1.
O
O
R
Cl
Cl
R
S
S
H C
EtONa
3
+
CS +
2
H C
3
H C
3
O
H C
3
O
1
a, 1b
R = H (a); CH
76
3
(b).
2

ONE-POT SYNTHESIS OF 2-YLIDENE-1,3-DITHIOLANES
277
Scheme 2.
O
Cl
Cl
R
R
O
EtO
S
S
EtONa
NC
+ CS +
2
OEt
NC
2
a, 2b
3
R = H (a); CH (b).
Dithiolanes 1b and 2b were synthesized for the first
time, and the method of synthesis of compounds 1a
and 2a is much more facile that those reported in [9–11].
56.38; H 6.45. C H O S . Calculated, %: C 56.22; H
12 16 2 2
6.29. М 256.38.
Ethyl 2-cyano-2-(1,3-dithiolan-2-ylidene)acetate
(
1
1
2a). Yield 0.4 g (92%), mp 104–105°С (104°С [10],
Thus, we developed an original one-pot synthesis of
-ylidene-1,3-dithiolanes, which allows heterocycles of
complex structures to be prepared in one stage. The
developed method contains less stages and takes less time.
–
1
05–106°С [11]). IR spectrum, ν, cm : 2200 (С≡N),
2
1
706 (С=О), 1461 (С=С). Н NMR spectrum (DMSO-
d ), δ, ppm: 1.22–1.25 t (3H, J 7.1 Hz, CH ), 3.68–
3
Mass spectrum, m/z (I , %): 215 (20) [M] . Found, %:
C 44.85; H 4.40. C H NO S . Calculated, %: C 44.63;
6
3
.75 m (4H, 2SCH ), 4.18–4.23 q (2H, J 7.1 Hz, CH ).
2
2
+
5
,5-Dimethyl-2-(1,3-dithiolan-2-ylidene)cyclohe-
rel
xan-1,3-dione (1а). A solution of 0.28 g (0.002 mol)
of dimedone in 1 mL of ethanol was added to sodium
ethylate obtained from 0.05 g (0.002 mol) of sodium and
mL of ethanol. Carbon disulfide, 0.15 mL (0.002 mol),
and a new portion of sodium ethylate from 0.05 g
0.002 mol) of sodium and 1 mL of ethanol were then
successively added to the mixture. The precipitate that
formed was dissolved in 4 mL of DMF, and 1 g (0.01 mol)
of dichloroethane was added to the solution. The
reaction mixture was stirred until reaction completion
8
9
2 2
H 4.21. М 215.29.
Ethyl 2-cyano-2-(4-methyl-1,3-dithiolan-2-
1
ylidene)acetate (2b). Yield 0.44 g (96%), mp 169–
1
(
ppm: 1.22–1.25 m (3H, СH CH ), 1.22–1.25 m (3H,
СH CH )*, 1.44 m (3H, СHCH ), 1.44 m (3H,
СHCH )*, 3.49–3.58 m (1Н, SCH ), 3.49–3.58 m (1Н,
SCH )*, 3.79–3.84 m (1Н, SCH ), 3.79–3.84 m (1Н,
SCH )*, 4.17–4.23 m (2Н, СH CH ), 4.17–4.23 m
(
m (1H, СHCH )*. Mass spectrum, m/z (I , %): 229
(100) [M] . Found, %: C 47.35; H 5.03. C H NO S .
–
1
70°С. IR spectrum, ν, cm : 2207 (С≡N), 1711
(
1
С=О), 1468 (С=С). Н NMR spectrum (DMSO-d ), δ,
6
2
3
2
3
3
3
2
2
2
(
1 h by TLC) and diluted with 4–5 volumes of water.
The precipitate that formed was filtered off, washed
with water, and recrystallized from propan-2-ol.
2
2
3
2Н, СH CH )*, 4.33–4.41 m (1H, СHCH ), 4.33–4.41
2 3 3
3
rel
+
Yield 0.41 g (85%), mp 202°С (201–202°С [9],
9 11 2 2
–
1
2
(
(
2
00°С [10]). IR spectrum, ν, cm : 1710 (С=О), 1458
Calculated, %: C 47.14; H 4.84. М 229.31.
1
С=С). Н NMR spectrum (DMSO-d ), δ, ppm: 0.96 s
6
The purity of the synthesized compounds was
controlled by TLC (eluent – ethyl acetate) of Sorbfil
PTSKh-AF-A-UF plates in with development in UV
light or iodine vapor, or by heating. The melting points
were measured on an OptiMelt MPA100 instrument. The
IR spectra were obtained on a FSM-1202 FTIR spectro-
meter in mineral oil. The NMR spectra were recorded
on a Bruker DRX-500 spectrometer at 500 ( H) МHz in
DMSO-d , internal reference ТМС. The mass spectra
were measured on a Shimadzu GCMS-QP 2010 SE
system (electron ionization, 70 eV). Elemental analysis
was performed on a Perkin Elmer-2400 CHN analyzer.
6H, 2CH ), 2.47 s (4H, 2COCH ), 3.39 s (4H,
3
2
+
SCH ). Mass spectrum, m/z (I , %): 242 (30) [M] .
2 rel
Found, %: C 54.75; H 5.99. C H O S . Calculated,
11
14
2 2
%
: C 54.52; H 5.82. М 242.35.
Compounds 1b, 2a, and 2b were prepared in a
similar way.
1
5
,5-Dimethyl-2-(4-methyl-1,3-dithiolan-2-ylide-
6
ne)cyclohehane-1,3-dione (1b). Yield 0.46 g (90%),
–
1
mp 175–176°С. IR spectrum, ν, cm : 1715 (С=О),
1
1
0
6
460 (С=С). Н NMR spectrum (DMSO-d ), δ, ppm:
6
.95 s (3H, CCH ), 0.97 s (3H, CCH ), 1.35 d (3H, J
3
3
.7 Hz, CHCH ), 2.46 m (4H, 2COCH ), 3.19–3.23 d.d
3
2
FUNDING
(
1H, J 12.1, 6.8 Hz, SCH ), 3.46–3.50 d.d (1H, J 12.1,
2
5
.8 Hz, SCH ), 3.97–4.04 m (1H, CHCH ). Mass
The work was supported by the grant of the
President of the Russian Federation, allocated for state
2
3
+
spectrum, m/z (I , %): 256 (50) [M] . Found, %: C
rel
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019

2
78
LIPIN et al.
support of young Russian scientists (grant no. MK-
4. Hanaki, N., Motoki, M., and Yawata, T., WO Patent
Appl. WO 2009022736, 2009.
5
518.2018.3)
5
6
7
8
. Suzuki, H. and Yamada, S., US Patent Appl. no.
2
009202921, 2009.
CONFLICT OF INTEREST
. Hanaki, N., Yawata, T., and Mikoshiba, H., US Patent
Appl. no 20100025642, 2010.
. Hanaki, N. and Yawata, T., US Patent Appl. no.
The authors declare no conflict of interest.
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