New cross recyclizations of 4-aryl-2,6-diamino- 4H-thiopiran-3,5- dicarbonitriles

Full text of DOI:10.1134/S1070363211010312

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 1, pp. 160–161. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.D. Dyachenko, T.A. Ryl’skaya, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 1, pp. 162–163.
LETTERS
TO THE EDITOR
New Cross Recyclizations of 4-Aryl-2,6-diamino-
4
H-thiopiran-3,5-dicarbonitriles
V. D. Dyachenko and T. A. Ryl’skaya
Taras Shevchenko Lugansk National University, ul. Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: dvd_lug@online.lg.ua
Received March 11, 2010
DOI: 10.1134/S1070363211010312
Cross recyclization of 4-aryl-2,6-diamino-4H-thio-
pyran-3,5-dicarbonitriles with acetone leads to the
formation of 4-aryl-6-methyl-2-thioxo-1,2-dihydro-
pyridine-3-carbonitriles [1], the reaction with pyri-
dinium ylide gives 5-cyano-3-(1-pyridinio)-1,2,3,4-
tetrahydropyridin-6-thiolates [2], and 3-aryl-2-(thiazol-
methylamine we obtained 6-amino-1-methyl-4-phenyl-
2-thioxo-1,2-dihydropyridine-3,5-dicarbonitrile (IV).
Treatment of compound Ia with hydrogen sulfide in
pyridine solution in the presence of triethylamine
resulted in the formation of dithiomalonamide V.
Alkylation of pyridinethione IIIa with pentyl iodide
(VI) gave the corresponding sulfide VII. Mechanisms
of formation of compounds III–V and scopes of appli-
cation of the above reactions are now under study.
2
-yl)acrylonitriles were obtained in reactions with α-
bromo carbonyl compounds [3].
We now report for the first time on the cross recyc-
lization of thiopyrans Ia and Ib with acetoacetanilide
Initial thiopyrans Ia and Ib were synthesized ac-
cording to the procedure reported in [4].
(II) in boiling ethanol in the presence of N-methyl-
morpholine, which afforded 4-aryl-5-cyano-2-methyl-
N-phenyl-6-thioxo-1,6-dihydropyridine-3-carboxamides
IIIa and IIIb. By reaction of thiopyran Ia with
5-Cyano-2-methyl-N,4-diphenyl-6-thioxo-1,6-di-
hydropyridine-3-carboxamide (IIIa). Three drops of
R
Ph
O
NC
CN
S
O
O
CN
PhHN
R
PhHN
Me
H N
N
2
II
Me
N
S
MeNH2
H
Me
IV
IIIа, IIIb
NC
CN
C H11I
5
VI
H N
S
NH2
2
O
Ph
H2S
Iа, Ib
CN
S
S
PhHN
Me
Me
H N
NH2
2
N
S
V
VII
I, III, R = H (a), Cl (b).
60
1

NEW CROSS RECYCLIZATIONS
161
N-methylmorpholine were added to a mixture of 0.51 g
2 mmol) of thiopyran Ia and 0.35 g (2 mmol) of
and washed with water, ethanol, and hexane. Yield
0.32 g (79%). In analogous reaction with thiopyran Ib,
the yield of V was 0.29 g (70%), mp 135–138°C [6].
(
acetoacetanilide (II) in 10 ml of ethanol, and the
mixture was heated for 6 h under reflux. The mixture
was cooled to room temperature, treated with 10%
hydrochloric acid to pH 2, and left to stand for 48 h.
The precipitate was filtered off and washed with
ethanol and hexane. Yield 0.32 g (76%), mp 262–264°C
5-Cyano-2-methyl-6-pentylsulfanyl-N,4-diphenyl-
pyridine-3-carboxamide (VII). Compound IIIa,
0
1
.69 g (2 mmol), was dissolved in 10 ml of DMF,
.12 ml (2 mmol) of 10% aqueous potassium
hydroxide and 0.26 ml (2 mmol) of pentyl iodide (VI)
were added in succession under stirring, and the
mixture was stirred for 2 h, diluted with 10 ml of
water, and left to stand for 24 h. The precipitate was
filtered off and washed with water, ethanol, and
(
from EtOH); published data [5]: mp 260–262°C.
+
Mass spectrum: m/z 346 ((I 100%) [M + 1] .
rel
4
-(4-Chlorophenyl)-5-cyano-2-methyl-N-phenyl-
6
-thioxo-1,6-dihydropyridine-3-carboxamide (IIIb)
1
was synthesized in a similar way from thiopyran Ib.
hexane. Yield 0.65 g (78%), mp 118–120°C. H NMR
1
Yield 0.5 g (65%), mp 260–262°C (EtOH). H NMR
spectrum, δ, ppm: 0.92 t (3H, Me, J = 6.2 Hz), 1.37–
spectrum, δ, ppm: 2.48 s (3H, Me), 7.07 t (1H, Harom
,
1.48 m (4H, CH ), 1.74 m (2H, CH ), 2.62 t (2H,
2
2
J = 7.5 Hz), 7.27 t (2H, Harom, J = 8.0 Hz), 7.33 d (2H,
Harom, J = 8.0 Hz), 7.47 d and 7.55 d (2H each, ClC H ,
SCH J = 7.2 Hz), 3.34 s (3H, 6-Me), 7.06–7.66 m
2,
(10H, Ph), 10.38 br.s (1H, NHCO). Mass spectrum:
6
4
+
J = 8.5 Hz), 10.32 s (1H, NHCO), 14.44 br.s (1H, NH).
m/z 416 (Irel 100%) [M + 1] . Found, %: C 72.14; H
+
Mass spectrum: m/z 380 (Irel 100%) [M + 1] . Found,
6.01; N 9.98. C H N OS. Calculated, %: C 72.26; H
25
25
3
%
: C 63.15; H 3.66; N 10.92. C H ClN OS.
6.06; N 10.11.
2
0
14
3
Calculated, %: C 63.24; H 3.72; N 11.06.
-Amino-1-methyl-4-phenyl-2-thioxo-1,2-dihyd-
ropyridine-3,5-dicarbonitrile (IV). A mixture of
.27 g (4 mmol) of methylamine hydrochloride, 0.17 g
1
The H NMR spectra were recorded on Bruker DR-
500 (500.13 MHz; compounds IIIa, IIIb, V, and VII)
and Bruker Avance II-400 (400.13 MHz; compound
IV) spectrometers. The mass spectra (electron impact,
70 eV) were obtained on Kratos MS-890 (IIIa, IIIb,
V, VII) and MKh-1321 (IV) instruments with direct
sample admission into the ion source.
6
0
(
(
2 mmol) of sodium hydrogen carbonate, and 0.51 g
2 mmol) of thiopyran Ia in 10 ml of water was heated
for 3 h at the boiling point. The mixture was cooled to
room temperature, treated with 10% hydrochloric acid
to pH 4, and left to stand for 48 h in the cold. The
precipitate was filtered off and washed with water,
REFERENCES
1
. Sharanin, Yu.A. and Shestopalov, A.M., Zh. Org. Khim.,
989, vol. 25, no. 6, p. 1331.
ethanol, and hexane. Yield 0.27 g (54%), mp 285–287°C
1
1
(
from AcOH). H NMR spectrum, δ, ppm: 3.96 s (3H,
Me), 7.45–7.55 m (5H, Ph), 8.61 br.s (2H, NH ). Mass
2. Shestopalov, A.M., Sharanin, Yu.A., and Litvinov, V.P.,
2
+
spectrum, m/z (I , %): 268 (5) [M + 2] , 267 (19) [M +
Zh. Org. Khim., 1991, vol. 27, no. 6, p. 1349.
rel
+
+
+
1
(
] , 266 (100) [M] , 251 (13) [M – Me] , 207 (15), 165
23), 77(21) [Ph] , 51(14). Found, %: C 63.02; H
3
4
. Dyachenko, V.D., Chernega, A.N., and Garasevich, S.G.,
Russ. J. Gen. Chem., 2005, vol. 75, no. 10, p. 1610.
+
3
3
.66; N 20.95. C H N S. Calculated, %: C 63.14; H
14 10 4
. Sharanin, Yu.A., Shestopalov, A.M., Nesterov, V.N.,
Melenchuk, S.N., Promanenkov, V.K., Shklover, V.E.,
Struchkov, Yu.T., and Litvinov, V.P., Zh. Org. Khim.,
.78; N 21.04.
Propanebis(thioamide) (V). Three drops of tri-
ethylamine were added to a mixture of 0.76 g
3 mmol) of thiopyran Ia and 20 ml of pyridine, and
1
989, vol. 25, no. 6, p. 1323.
(
5. Dyachenko, V.D., Krivokolysko, S.G., Nesterov, V.N.,
and Litvinov, V.P., Khim. Geterotsikl. Soedin., 1996,
no. 9, p. 1243.
hydrogen sulfide was bubbled through the mixture
over a period of 7 h. The mixture was diluted with a
fivefold volume of water and was left to stand in a
refrigerator. After 48 h, the precipitate was filtered off
6. Lehr, H., Guex, W., and Erlenmeyer, H., Helv. Chim.
Acta, 1944, vol. 27, no. 1, p. 970.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 1 2011