DYACHENKO, SOLODUKHA
1344
2-thiolate (IІb). Yield 1.23 g (57%), bright yellow
powder, mp 191–193°C (from MeCN). IR spectrum, ν,
carbonitrile (IІІb). Yield 0.27 g (90%), bright yellow
powder, mp 176–178°C. IR spectrum, ν, cm–1: 3437
(NH), 2240 (C≡N), 1633 (C=O). 1H NMR spectrum, δ,
ppm: 0.94 s and 1.04 s (3H each, Me), 2.15 d and
1
cm–1: 3432 (NH), 2173 (C≡N), 1605 (C=O). H NMR
spectrum, δ, ppm: 0.83 s and 0.96 s (3H, Me), 1.88 d
2
2
2.27 d (1H each, 6-H, J = 16.0 Hz), 2.57 d (1H, 8-H,
and 1.83 d (1H each, 6-H, J = 16.0 Hz), 2.29 s (2H,
2J = 16.0 Hz; the other 8-H signal was overlapped by
8-H), 3.08 t (4H, CH2NCH2, J = 4.6 Hz), 3.74 t (4H,
CH2OCH2, J = 4.6 Hz), 4.22 s (1H, 4-H), 7.08 d (2H,
the residual solvent signal), 4.26 s (1H, 4-H), 5.20–
4
5.29 m (2H, =CH2), 5.69 t (1H, CH=, J = 4.0 Hz),
H
arom, J = 7.2 Hz), 7.24 d (2H, Harom, J = 7.2 Hz),
7.16 d (2H, Harom, J = 8.0Hz), 7.40 d (2H, Harom, J =
8.0 Hz), 12.48 br.s (1H, NH). 13C NMR spectrum, δC,
ppm: 27.05, 27.91, 32.38, 38.57, 42.56, 49.66, 58.20,
81.43, 89.89, 113.49, 116.99, 128.49, 129.94, 132.61,
136.18, 148.33, 148.42, 194.52, 206.52. Mass spec-
trum, m/z (Irel, %): 384 (41) [M + 2]+, 383 (44) [M + 1]+,
382 (100) [M]+, 381 (64) [M – 1]+, 326 (34), 271 (36),
162 (11), 127 (9), 83 (19). Found, %: C 65.75; H 4.82;
N 7.23. C21H19ClN2OS. Calculated, %: C 65.87;
H 5.00; N 7.32. M 382.9.
8.56 br.s (1H, NH). Found, %: C 61.02; H 5.92;
N 9.66. C22H26ClN3O2S. Calculated, %: C 61.17;
H 6.07; N 9.73.
Morpholinium 3-cyano-7,7-dimethyl-5-oxo-4-
phenyl-1,4,5,6,7,8-hexahydroquinoline-2-thiolate
(IІc). Yield 1.29 g (65%), yellow powder, mp 185–
187°C (from EtOH). IR spectrum, ν, cm–1: 3433 (NH),
2188 (C≡N), 1603 (C=O). 1H NMR spectrum, δ, ppm:
0.85 s and 0.94 s (3H each, Me), 1.96–2.11 m (4H,
6-H, 8-H), 2.83 t (4H, CH2NCH2, J = 4.5 Hz), 3.59 t
(4H, CH2OCH2, J = 4.5 Hz), 5.03 s (1H, 4-H), 7.02–
7.21 m (2H, Harom), 7.37–7.44 m (3H, Harom), 8.60 br.s
(1H, NH). Found, %: C 66.31; H 6.70; N 10.42.
C22H27N3O2S. Calculated, %: C 66.47; H 6.85; N 10.57.
3-Allenyl-7,7-dimethyl-5-oxo-4-phenyl-2-thioxo-
1,2,3,4,5,6,7,8-octahydroquinoline-3-carbonitrile
(IІІc). Yield 0.08 g (80%), orange–yellow powder,
mp 175–176°C. IR spectrum, ν, cm–1: 3436 (NH),
1
2240 (C≡N), 1632 (C=O). H NMR spectrum, δ, ppm:
Morpholinium 4-(4-bromophenyl)-3-cyano-7,7-
dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-2-
thiolate (IІd). Yield 1.48 g (62%), bright yellow
powder, mp 230–233°C (from PrOH); published data
[6]: mp 228–231°C.
0.93 s and 1.02 s (3H each, Me), 2.12 d and 2.39 d (1H
2
each, 6-H, J = 16.0 Hz), the 8-H signal was over-
lapped by the residual solvent signal, 4.20 s (1H, 4-H,
4
5.21–5.23 m (2H, =CH2), 5.67 t (1H, CH=, J =
4.0Hz), 7.12 d (2H, Harom, J = 8.0 Hz ), 7.27 s (2H,
Harom), 12.43 br.s (1H, NH). Mass spectrum, m/z
(Irel, %): 350 (5) [M + 2]+, 349 (23) [M + 1]+, 348 (100)
[M]+, 347 (64) [M – 1]+, 346 (7) [M – 2]+, 292 (37),
220 (16), 128 (14), 32 (84). Found, %: C 72.22;
H 5.66; N 7.91. C21H20N2OS. Calculated, %: C 72.38;
H 5.79; N 8.04. M 348.5.
3-Allenyl-7,7-dimethyl-4-(2-nitrophenyl)-5-oxo-
2-thioxo-1,2,3,4,5,6,7,8-octahydroquinoline-3-
carbonitrile (IІІa). A suspension of 0.3 g (0.76 mmol)
of compound Ia in 10 ml of ethanol was heated for 5 h
under reflux. The precipitate was filtered off and
washed with ethanol and hexane. Yield 0.26 g (85%),
bright yellow powder, mp 165–167°C (from EtOH).
IR spectrum, ν, cm–1: 3460 (NH), 2247 (C≡N), 1649
3-Allenyl-4-(4-bromophenyl)-7,7-dimethyl-5-
oxo-2-thioxo-1,2,3,4,5,6,7,8-octahydroquinoline-3-
carbonitrile (IІІd). Yield 0.071 g (71%), yellow–
1
(C=O). H NMR spectrum, δ, ppm: 0.89 s and 1.02 s
1
(3H each, Me), 2.09 d and 2.23 d (1H each, 6-H, J =
green powder, mp 215–216°C. H NMR spectrum, δ,
16.0 Hz), 2.55 s (2H, 8-H), 5.12 s (1H, 4-H), 5.25–
ppm: 0.94 s and 1.03 s (3H each, Me), 2.15 d and
4
2
5.36 m (2H, =CH2), 5.70 t (1H, CH=, J = 4.0 Hz),
2.27 d (1H each, 6-H, J = 16.0 Hz), 2.30 s (1H, 8-H;
7.11 d (1H, Harom, J = 8.0 Hz), 7.56 t (1H, Harom, J =
8.0 Hz), 7.70 t (1H, Harom, J = 8.0 Hz), 8.02 d (1H,
the other 8-H signal was overlapped by the residual
solvent signal), 4.24 s (1H, 4-H), 5.23–5.26 m (2H,
=CH2), 5.70 t (1H, CH=, J = 4.0 Hz), 7.09 d (2H,
Harom, J = 8.0 Hz), 7.53 d (2H, Harom, J = 8.0 Hz),
12.49 br.s (1H, NH). Found, %: C 58.90; H 4.31;
N 6.44. C21H19BrN2OS. Calculated, %: C 59.02;
H 4.48; N 6.56.
4
Harom, J = 8.0 Hz), 12.61 br.s (1H, NH). Mass spec-
trum, m/z (Irel, %): 393 (1) [M]+, 376 (12), 320 (100),
290 (10), 164 (2), 120 (2), 83 (36). Found, %: C 64.00;
H 4.65; N 10.52. C21H19N3O3S. Calculated, %:
C 64.10; H 4.87; N 10.68. M 393.5.
Compounds IIIb–IIId were synthesized in a simi-
lar way.
REFERENCES
3-Allenyl-4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-
2-thioxo-1,2,3,4,5,6,7,8-octahydroquinoline-3-
1. Shestopalov, A.M., Goncharenko, M.P., Litvinov, V.P.,
and Sharanin, Yu.A., Dokl. Akad. Nauk SSSR, 1990,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011