I.V. DYACHENKO, V.D. DYACHENKO
634
cyanoethanethioamide 2a, and 1.1 mL (10 mmol) of N-
methylmorpholine in 30 mL of ethanol at 20°C was
stirred for 1 h, 10 mmol of α-chloroacetonitrile 3d was
added, the mixture was stirred for 1 h and left standing
for 24 h. Then at stirring 15 mL of DMF and 5.6 mL
(10 mmol) of 10% aqueous KOH solution was added
to the reaction mixture, it was stirred for 4 h and
diluted with an equal volume of water. The formed
precipitate was filtered off, washed with water,
ethanol, and hexane. Yield 2.4 g (77%), yellow
powder, mp 192–194°C (BuOH). IR spectrum, ν, cm–1:
3385, 3311, 3205 (NH2), 2209 (C≡N), 1642 [δ(NH2)].
1H NMR spectrum, δ, ppm: 6.54 br.s (2H, NH2), 6.85
d (1H, H3furan, J 3.0 Hz), 7.32 d.d (1H, H4thiophene, J
6.0 Hz), 7.42–7.64 m (4H, Harom), 8.13 s (1H, H5pyridine),
8.15–8.30 m (2H, Harom). Mass spectrum, m/z (Irel, %):
318 (100) [M + 1]+. Found, %: C 67.96; H 3.32; N
13.14. C18H11N3OS. Calculated, %: C 68.12; H 3.49; N
13.24. M 317.342.
7.61 d (2H, Ar, J 7.7 Hz), 7.95 d (1H, H3thiophene, J
4.5 Hz), 8.18 d (1H, H5thiophene, J 3.6 Hz), 13.9 br.s (1H,
NH). Mass spectrum, m/z (Irel, %): 310 (11) [M + 2]+,
309 (16) [M + 1]+, 308 (100) [M]+, 307 (25) [M – 1]+,
293 (26) [M – Me]+, 275 (9), 264 (7), 233 (5), 134 (8),
140 (7), 113 (91), 100 (7), 91 (5) [C6H4Me]+, 89 (7),
60 (8). Found, %: C 66.04; H 3.81; N 8.95.
C17H12N2S2. Calculated, %: C 66.20; H 3.92; N 9.08.
M 308.427.
REFERENCES
1. Tasaka, S., Kine, A., Omori, H., Tanabe, Y., and Gomi, N.,
EP Patent Appl. no. 1055672, 2000; Chem. Abstr.,
2001, no. 19O117P.
2. Burke, P.J. and Kuox, R.J., GB Patent Appl.
no. 2365338, 2002; Ref. Zh. Khim., 2002, no. 19O62P.
3. Tirzite, D., Krauze, A., Zubareva, A., Tirzitis, G., and
Duburs, G., Chem. Heterocycl. Compd., 2002, vol. 38,
p. 795.
4. Sirisha, K., Bikshapathi, D., Achaiah, G., and
Reddy, V.M., Eur. J. Med. Chem., 2011, vol. 46,
p. 1564.
5. Gein, V.L., Kazantseva, M.I., Kurbatova, A.A., and
Voronina, E.V., Pharm. Chem. J., 2011, vol. 45,
p. 474.
6. Nakajo, A., Tokumasu, M., Kito, M., Takahara, A.,
Ono, Y., Takeda, T., Kajiagava, Y., and Kaganei, H.,
US Patent no. 6610717, 2003; Ref. Zh. Khim., 2004,
no. 19O83P.
N-(4-Bromophenyl)-3-amino-4,6-di(thiophen-2-
yl)-thieno[2,3-b]pyridine-2-carboxcamide (7b) was
obtained similarly from 2.2 g (10 mmol) of chalcone
1a and 2.5 g (10 mmol) of N-(4-bromophenyl)-α-
chloroacetamide 3c. Yield 3.6 g (71%), yellow
powder, mp 243–245°C (BuOH). IR spectrum, ν, cm–1:
3398, 3300, 3214 (NH, NH2), 1668 (CONH), 1644
1
[δ(NH2)]. H NMR spectrum, δ, ppm: 6.28 br.s (2H,
NH2), 7.11 t (1H, H4thiophene, J 5.1 Hz), 7.23 t (1H,
H4'thiophene, J 5.0 Hz), 7.03 d (1H, H3thiophene, J 4.5 Hz),
7.35 d (2H, Ar, J 7.5 Hz), 7.48 d (1H, H3'thiophene, J
4.5 Hz), 7.58 s (1H, H5pyridine), 7.61 d (1H, H5thiophene, J
3.5 Hz), 7.69 d (2H, Ar, J 7.5 Hz), 7.76 d (1H,
H5'thiophene, J 3.5 Hz), 9.15 br.s (1H, NH). Mass spec-
trum, m/z (Irel, %): 514 (92) [M + 2]+, 512 (100) [M]+.
Found, %: C 51.42; H 2.60; N 8.04. C22H14BrN3OS3.
Calculated, %: C 51.56; H 2.75; N 8.20. M 512.472.
7. Jacobson, K.A. and Li, A.-H., US Patent no. 6376521,
2002; Ref. Zh. Khim., 2003, no. 19O87P.
8. Krauze, A., Baumane, L., Sile, L., Chernova, L.,
Vilums, M., Vitolina, R., Duburs, G., and
Stradins, J., Chem. Heterocycl. Compd., 2004, vol. 40,
p. 876.
9. Barfacker, L., Kolkhof, P., Schlemmer, K.-H., Gros-
ser, R., and Nitsche, A., German Patent Appl.
no. 102006044696, 2008; Ref. Zh. Khim., 2009,
no. 19O121P.
10. Osolodkin, D.I., Kozlovskaya, L.I., Dueva, E.V.,
Dotsenko, V.V., Rogova, Y.V., Frolov, K.A.,
Krivokolysko, S.G., Romanova, E.G., Morozov, A.S.,
Karganova, G.G., Palyulin, V.A., Pentovski, V.M., and
Zefirov, N.S., Med. Chem. Lett., 2013, vol. 4, p. 869.
11. Nakujo, A., Tokumasu, M., Kito, M., Takahara, A.,
Ono, Y., Takeda, T., Kajigaya, Y., and Koganei, H., EP
Patent Appl., no. 1191022, 2002; Ref. Zh. Khim., 2002,
no. 19O69P.
4-(2-Methylphenyl)-2-thioxo-6-(thiophen-2-yl)-
1,2-dihydropyridine-3-carbonitrile (8). A mixture of
2.3 g (10 mmol) of chalcone 1d, 1.0 g (10 mmol) of 2-
cyanoethanethioamide 2a, and 1.1 mg (10 mmol) of N-
methylmorpholine in 20 mL of ethanol at 20°C was
stirred for 1 h and left standing for 24 h. Then the
reaction mixture was diluted with 10% hydrochloric
acid till pH 5, and the mixture was left standing for
48 h. The separated precipitate was filtered off, washed
with water, ethanol, and hexane. Yield 2.4 g (77%),
yellow powder, mp 236–238°C (AcOH). IR spectrum,
1
ν, cm–1: 3345 (NH), 2220 (C≡N). H NMR spectrum,
12. Niwa, S., Ohno, S., Takahara, A., and Kito, M., EP
Patent Appl., no. 1123923, 2001; Ref. Zh. Khim., 2002,
no. 19O112P.
δ, ppm: 2.41 s (3H, Me), 6.99 s (1H, H5pyridine), 7.24 t
(1H, H4thiophene, J 5.2 Hz), 7.35 d (2H, Ar, J 7.7 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 5 2015