B. Cyanothioacetamide (2 g, 20 mmol), then over 5 min 2-thienoyltrifluoroacetone (4.44 g, 20 mmol),
and finally N-methylmorpholine (2.52 ml, 25 mmol) were added with stirring at 20°C to a mixture of
2-chlorobenzaldehyde (2.25 g, 20 mmol) and N-methylmorpholine (3 drops) in ethanol (30 ml). After 30 min
the reaction mixture was treated as in method A. The ethanol solvate of thione 1 was obtained (3.49 g, 71%, A;
1
6.38 g, 65%, B); mp 125-127°C. IR spectrum, , cm-1: 3330-3480 (NH, OH), 2250 (CN), 1680 (CO). H NMR
ν
spectrum, δ, ppm: 1.08 t and 3.45 q (5H,
EtOH); 4.80 (3H, m, 3-, 4-, 5-H); 7.11 m, 7.34 d, 7.84 m (7H, Ar and
Het); 8.15 (1H, br. s, OH); 11.12 (1H, br. s, NH). Found, %: C 48.71; H 3.84; N 5.53; S 13.19.
C18H12ClF3N2O2S2·C2H5OH. Calculated, %: C 48.93; H 3.70; N 5.71; S 13.06.
2-Allylthio-4-(2-chlorophenyl)-3-cyano-6-hydroxy-5-(2-thienoyl)-6-trifluoromethyl-1,4,5,6-tetra-
hydropyridine (2). Aqueous KOH (2.8 ml, 10%, 5 mmol) was added to a suspension of the solvate of thione 1
(2.46 g, 5 mmol) in ethanol (30 ml, 80%), followed by the addition of allyl bromide (0.42 ml, 5 mmol) over
5 min. The precipitate which formed over 1 h was filtered off, washed with ethanol and hexane to give
compound 2 (1.87 g, 77%); mp 155-157°C. IR spectrum, , cm-1: 3210-3300 (NH, OH), 2195 (CN), 1620, 1650
ν
3
3
(CO). 1
J (Hz): 3.72 (d, J = 7.5, SCH2); 4.3 (d, J = 12.1, 5-HA); 4.42 (br. s, 4-HB and
H NMR spectrum, δ, ppm,
3
5-HB); 4.84 (d, J = 12.1, 4-HA); 5.22 (m, CH2=); 5.92 (m, CH=); 7.15, 7.30, 7.70, 7.89 (four m, Ar and Het);
7.43 (br. s, OH); 8.28 (br. s, NH). Found, %: C 52.26; H 3.12; N 5.93; S 13.37. C21H16ClF3N2O2S2.
Calculated, %: C 52.10; H 3.33; N 5.78; S 13.22.
X-ray Crystallographic Study of a Monocrystal of Compound 1 was carried out at room temperature
with an automatic four-circle Enraf-Nonius CAD-4 diffractometer (λMo α radiation, graphite monochromator,
K
relative rate of scanning ω/θ = 1.2, θmax
= 24°, segment of the sphere 0
h
16, 0
k
12, -16
l
16).
≤
≤
≤
≤
≤
≤
eflexions with 12 < θ <13° were used to determine the unit cell parameters and the orientation matrices of a
22 R
crystal with the linear dimensions 0.12 × 0.24 × 0.47 mm. A total of 3754 reflexions were collected of which
3470 were symmetrically independent (R factor averaged 0.11). Crystals were monoclinic, a = 14.171(2),
3
β = 104.76(2)°;
3; μ = 0.410 mm-1
;
b = 11.004(3), c = 14.729(3) Å;
V = 2221.0(8) Å ; Z = 4; dcalc = 1.486 g/cm
F(000) = 1008, space group P21/n. The structure was solved by direct methods and refined by mean squares
method in the full matrix anisotropic approximation by use OF SHELXS and SHELXL-93 programs [8, 9].
1639 Reflexions were used in the refinement (280 parameters refined) for a ratio of reflexions to parameters of
(F ) + (AP) ] was used, where P = (F +2Fc2)/3 and the coefficient of
the weighting scheme A = 0.0572; a correction for anomalous absorption was included, but no correction for
absorption was used. Most of the hydrogen atoms (75%) were revealed objectively, the remainder were found
using geometric constraints. However all were refined with fixed thermal and geometric parameters. The final
residual factors were R1 (F) = 0.0677 and Rw = 0.1305, Go 1.038. The residual electron densities on a difference
Fairer map were 0.23 and -0.32 e/Å3. The atomic coordinates are cited in Table 2.
5.85, the weighting scheme ω = 1/[σ2 σ2
σ2
2
This work was carried out with financial assistance from the Russian fund for fundamental research
(project No. 99-03-32965).
REFERENCES
1.
2.
S. G. Krivokolysko, V. D. Dyachenko, V. N. Nesterov, and V. P. Litvinov, Khim. Geterotsikl. Soedin.,
929 (2001).
L. M. Yagupol'skii, Aromatic and Heterocyclic Compounds with Fluorine Containing Substituents
[in Russian]. Naukova Dumka, Kiev (1988), 320.
3.
4.
N. S. Zefirov and V. A. Palyulin, Dokl. Akad. Nauk SSSR, 252, 111 (1980).
R. W. Alder, N. C. Goode, T. J. King, J. M. Mellor, and B. W. Miller, J. Chem. Soc., Chem. Commun.,
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991
Krivokolysko
