SYNTHESIS OF NEW FUNCTIONALLY SUBSTITUTED 2-OXO(THIOXO)NICOTINIC
1339
(C≡N); 1663, 1638 (C=O). 1H NMR spectrum, δ, ppm:
(XIVc). Yield 2.22 g (60%), mp 220–223°C (from
BuOH). IR spectrum, ν, cm–1: 3485, 3347, 3251 (NH,
NH2); 2216 (C≡N); 1645, 1627 (C=O, δNH2). 1H NMR
spectrum, δ, ppm: 2.29 s (3H, Me), 2.56 s (3H, MeS),
2.45 s (3H, MeS), 3.79 s (3H, MeO), 6.91 m (1H,
Harom), 7.00 m (2H, Harom), 8.28 d (1H, Harom, J =
8.0 Hz), 8.91 br.s (1H, NHCO), 11.21 br.s (1H, N1H);
no SH signal was observed, presumably because of
fast exchange. Mass spectrum, m/z (Irel, %): 346 (2)
[M – 1]+, 238 (11), 224 (50) [M – 2-MeOC6H4NH]+,
212 (38), 149 (56), 135 (81), 123 (48) [2-MeOC6H4-
NH2]+, 108 (45), 79 (42), 52 (51), 47 (100). Found, %:
C 51.77; H 3.69; N 12.02. C15H13N3O3S2. Calculated,
%: C 51.86; H 3.77; N 12.10.
2-Allylsulfanyl-6-amino-N3-aryl-5-cyano-4-
methylsulfanylpyridine-3-carboxamide XIVa–XIVd
(general procedures). a. Compounds XIVa–XIVd
were synthesized from malononitrile II, CH acid IVa–
IVe, and allyl bromide according to the procedure de-
scribed above for compound VIII.
2-Allylsulfanyl-6-amino-5-cyano-N3-(3-methyl-
phenyl)-4-methylsulfanylpyridine-3-carboxamide
(XIVa). Yield 2.47 g (67%), mp 180–183°C (from
MeOH). IR spectrum, ν, cm–1: 3486, 3348, 3259 (NH,
NH2); 2216 (C≡N), 1644 (C=O), 1628 (δ NH2).
1H NMR spectrum, δ, ppm: 2.28 s (3H, Me), 2.49 s
(3H, MeS), 3.79 d (2H, SCH2, J = 7.2 Hz), 5.07 d (1H,
3.83 d (2H, SCH2, J = 7.2 Hz), 5.09 d (1H, =CH2, Jcis
=
10.0 Hz), 5.36 d (1H, =CH2, Jtrans = 17.2 Hz), 5.83–
5.92 m (1H, CH), 7.12 t (1H, Harom, J = 7.6 Hz), 7.18–
7.24 m (2H, Harom), 7.24 br.s (2H, NH2), 7.46 d (1H,
Harom, J = 7.6 Hz), 9.88 br.s (1H, NHCO). Mass spec-
trum, m/z (Irel, %): 370 (2) [M]+, 358 (4), 329 (100)
[M – C3H5]+, 264 (96) [M – 2-MeC6H4NH]+, 157 (22),
106 (39) [2-MeC6H4NH]+, 41 (51) [C3H5]+. Found, %:
C 58.28; H 4.77; N 15.00. C18H18N4OS2. Calculated,
%: C 58.35; H 4.90; N 15.12.
2-Allylsulfanyl-6-amino-5-cyano-N3-(2-methoxy-
phenyl)-4-methylsulfanylpyridine-3-carboxamide
(XIVd). Yield 2.78 g (72%), mp 235–237°C (from
AcOH). IR spectrum, ν, cm–1: 3462, 3334, 3304, 3221
(NH, NH2); 2221 (C≡N); 1659, 1634 (C=O, δNH2).
1H NMR spectrum, δ, ppm: 2.49 s (3H, MeS), 3.88 s
(3H, MeO), 3.90 d (2H, SCH2, J = 7.2 Hz), 5.07 d (1H,
=CH2, Jcis = 10.0 Hz), 5.33 d (1H, =CH2, Jtrans
16.8 Hz), 5.81–5.91 m (1H, =CH), 6.94 t (1H, Harom
J = 7.2 Hz), 7.04 d (1H, Harom, J = 8.0 Hz), 7.11 t (1H,
=
,
H
H
arom, J = 7.6 Hz), 7.22 br.s (2H, NH2), 8.04 d (1H,
arom, J = 7.2 Hz), 9.67 br.s (1H, NHCO). Mass
=CH2, Jcis = 10.0 Hz), 5.33 d (1H, =CH2, Jtrans
=
spectrum, m/z (Irel, %): 386 (6) [M]+, 374 (11),
345 (96) [M – C3H5]+, 327 (4), 264 (100) [M –
2 - M e O C 6 H 4 N H 2 ] + , 1 5 7 ( 2 1 ) , 1 2 3 ( 7 4 )
[2-MeOC6H4NH2]+, 41 (75) [C3H5]+. Found, %:
C 55.85; H 4.59; N 14.42. C18H18N4O2S2. Calculated,
%: C 55.94; H 4.69; N 14.50.
17.2 Hz), 5.81–5.91 m (1H, =CH), 6.91 d (1H, Harom
,
J = 7.6 Hz), 7.20 t (1H, Harom, J = 8.0 Hz), 7.29 br.s
(2H, NH2), 7.39 d (1H, Harom, J = 8.0 Hz), 7.50 s (1H,
Harom), 10.38 br.s (1H, NHCO). Mass spectrum:
m/z 371 (Irel 100%) [M + 1]+. Found, %: C 58.29;
H 4.82; N 15.02. C18H18N4OS2. Calculated, %:
C 58.35; H 4.90; N 15.12.
b. Pyridinethione XIIa, 3.16 g (10 mmol), was
dissolved in 15 ml of DMF, 5.6 ml (10 mmol) of 10%
aqueous potassium hydroxide and 0.85 ml (10 mmol)
of allyl bromide were added in succession under
stirring, and the mixture was stirred for 2 h and left to
stand for 24 h. The mixture was then diluted with
an equal volume of water, and the precipitate was
filtered off and washed with water, ethanol, and
hexane. Yield of XIVb 71%; the product was identical
in the melting point and chromatographic parameters
to a sample obtained as described above in a.
2-Allylsulfanyl-6-amino-5-cyano-4-methylsul-
fanyl-N3-phenylpyridine-3-carboxamide (XIVb).
Yield 1.99 g (56%), mp 195–198°C (from AcOH). IR
spectrum, ν, cm–1: 3456 br (NH, NH2), 2203 (C≡N),
1
1626 br (C=O, δNH2). H NMR spectrum, δ, ppm:
2.63 s (3H, MeS), 3.79 d (2H, SCH2, J = 7.2 Hz),
5.07 d (1H, =CH2, Jcis = 10.1 Hz), 5.33 d (1H, =CH2,
Jtrans = 17.1 Hz), 5.81–5.94 m (1H, CH=), 7.03 m (1H,
Harom), 7.24–7.29 m (4H, Harom, NH2), 7.83 d (2H,
Harom, J = 8.0 Hz), 10.41 br.s (1H, NHCO). Mass spec-
trum, m/z (Irel, %): 356 (3) [M]+, 344 (2), 315 (100)
[M – C3H5]+, 264 (11) [M – PhNH]+, 157 (18), 93 (66)
[PhNH2]+, 41 (50) [C3H5]+. Found, %: C 57.14;
H 4.41; N 15.68. C17H16N4OS2. Calculated, %:
C 57.28; H 4.52; N 15.72.
REFERENCES
1. Litvinov, V.P., Yakunin, Ya.Yu., and Dyachenko, V.D.,
Khim. Geterotsikl. Soedin., 2001, p. 41.
2. Elgemeie, G.H., Elghandour, A.H., Elzanate, A.M.,
and Abd Elaziz, G.W., Synth. Commun., 2003, vol. 33,
p. 253.
2-Allylsulfanyl-6-amino-5-cyano-N3-(2-methyl-
phenyl)-4-methylsulfanylpyridine-3-carboxamide
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011