Synthesis and properties of triethylammonium 4-aryl(hetaryl)-3, 5-dicyano-6-OXO-1, 4, 5, 6-tetrahydro-pyridine-2-selenolates

Article abstract of DOI:10.1007/s10593-012-1012-4

The reaction of (hetero)aromatic aldehydes, cyanoselenoacetamide, and 1-(cyanoacetyl)-3, 5-dimethyl-pyrazole in the presence of triethylamine gives a mixture of the cis and trans diastereomers of triethylammonium 4-aryl(hetaryl)-3, 5-dicyano-6-oxo-1, 4, 5, 6-tetrahydropyridine-2-selenolates. The selenolates obtained react with alkyl halides to form the corresponding selenides.

Full text of DOI:10.1007/s10593-012-1012-4

Chemistry of Heterocyclic Compounds, Vol. 48, No. 3, June, 2012 (Russian Original Vol. 48, No. 3, March, 2012)
SYNTHESIS AND PROPERTIES OF TRIETHYLAMMONIUM
4-ARYL(HETARYL)-3,5-DICYANO-6-OXO-1,4,5,6-TETRAHYDRO-
PYRIDINE-2-SELENOLATES
K. A. Frolov1**, V. V. Dotsenko1, S. G. Krivokolysko1, and V. P. Litvinov*2
The reaction of (hetero)aromatic aldehydes, cyanoselenoacetamide, and 1-(cyanoacetyl)-3,5-dimethyl-
pyrazole in the presence of triethylamine gives a mixture of the cis and trans diastereomers of
triethylammonium 4-aryl(hetaryl)-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridine-2-selenolates. The
selenolates obtained react with alkyl halides to form the corresponding selenides.
Keywords: 1-cyanoacetyl-3,5-dimethylpyrazole, cyanoselenoacetamide, (hetero)aromatic aldehydes,
tetrahydropyridine-2-selenolates, heterocyclization.
Despite the high toxicity of many selenium compounds, a series of effective medications,
superconducting materials, and dyes have been prepared on the basis of selenium-containing heterocycles [1, 2].
Due to the limited range of methods of preparing selenium-containing pyridines, they remain to this time a
poorly studied group of organic compounds [3, 4], and there are only single examples in the literature of the
synthesis of their tetrahydropyridine analogs [5].
R
NC
CN
Se
BH+
H2N
N
H
NC
CN
B, EtOH
20°C
5
Me
+
+
O
R
CO2Et
H2N
Se
CHO
2a
NC
O
CN
4
3
N
H
Se
BH+
1'
R = 2-MeOC6H4; В = N-methylmorpholine
We have previously developed convenient methods for preparing polyfunctional reagents, namely,
N-methylmorpholinium 4-aryl-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolates based on the reaction of
_______
*Deceased.
**To whom correspondence should be addressed, e-mail: ka.frolov@ukr.net.
1"ChemEx" Laboratory, Vladimir Dal' East-Ukrainian National University, 20a/7 Molodezhny Kv., Lugansk
91034, Ukraine.
2N. D. Zelinsky Institute of Organic Chemistry, 47 Leninsky Ave., Moscow 117913, Russia.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 471-477, March, 2012. Original
article submitted August 19, 2010.
442
0009-3122/12/4803-0442©2012 Springer Science+Business Media, Inc.

aromatic aldehydes with cyanothioacetamide and cyanoacetate ester or 2-(cyanoacetyl)-3,5-dimethylpyrazole
[6-8]. In this work, we have studied the potential use of the indicated routes in preparing the triethylammonium
4-aryl(hetaryl)-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridine-2-selenolates 1a-d.
It was found that reaction of 2-methoxybenzaldehyde (2a) with cyanoselenoacetamide (3) and
cyanoacetate (4) in the presence of N-methylmorpholine gave the known 6-amino-3,5-dicyano-4-(2-methoxy-
phenyl)-1,4-dihydropyridine-2-selenolate (5) [9] in 39% yield (as a result of a concurrent process of
condensation of 2 equivalents of the selenoamide 3 with the aldehyde 2a) instead of the expected selenolate 1'.
The synthesis of selenolates 1a-d was successfully achieved by exchanging the cyanoacetate 4 for the
more active cyanoacetylating agent 1-(cyanoacetyl)-3,5-dimethylpyrazole (6). Hence, the aldehydes 2a-d,
cyanoselenoacetamide (3), and compound 6 in the presence of excess triethylamine in acetone take part in a
multicomponent cascade heterocyclization to give the triethylammonium tetrahydropyridine-2-selenolates 1a-d
in 26-53% yield.
Et3N+H
Se
RCHO
2a–d
R
NC
Et3N
Me2CO
CN
NC
Me
N
Me
+
N
10°C
NH2
NC
O
Se
NH2
N
N
O
Me
6
3
7a–d
Me
Me
N
–
NH
Me
R
R
HalCH2C(O)R1
CN
Se
NC
O
CN
Se
NC
8a–f
R1
EtOH, H2O
Et3N+H
N
O
N
H
H
O
1a–d
9a–n
1a, 2a, 9а R = 2-MeOC6H4; 1b, 2b, 9b–f R = 2-furyl; 1c, 2c, 9g,h R = 2-thienyl; 1d, 2d, 9i–n R = Ph;
8a, 9b,i R1 = OMe; 8b, 9j R1 = OEt; 8c, 9a,c,g,k R1 = Ph; 8d, 9d,h,l R1 = 4-MeC6H4;
8e, 9e,m R1 = PhNH; 8f, 9f,n R1 = 4-MeC6H4NH; 8a,b,e,f Hal = Cl; 8c,d Hal = Br;
Probably the intermediates in this reaction are the Michael adducts 7a-d. Short heating of compounds
1a-d with an equimolar amount of the alkyl halides 8a-f gives the corresponding selenides 9a-n in 24-96%
yield. It was found that the selenolates 1a-d and their derivatives 9a-n exist as a mixture of diastereomers with
different ratios of the mutually cis- and trans-orientated (het)aryl substituent at C-4 and the cyano group at C-5
in the pyridine ring.
1
The H NMR spectra of compounds 1a-d and 9a-n show the H-4 and H-5 protons of the cis
diastereomers as two doublets with spin-spin coupling of 6.1-8.2 Hz or as a broadened singlet whereas the
corresponding protons of the trans diastereomers show a coupling of 11.5-13.0 Hz.
The IR spectra of the selenolates 1a-d show the presence of a weak absorption band for the non-
conjugated 5-CN group at 2260-2265 cm-1 and a strong band for the conjugated 3-CN group at 2175-2215 cm-1.
The spectroscopic data for compounds 1a-d is in a good agreement with that for the corresponding sulfur
analogs reported in the studies [8, 10]. It should be noted that the method developed by us remains the only
method for the preparation of 4-aryl(hetaryl)-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridine-2-selenolates since
earlier attempts [11] led only to the formation of their dehydrogenation products - 4-aryl(hetaryl)-3,5-dicyano-
6-oxo-1,6-dihydropyridine-2-selenolates.
443

EXPERIMENTAL
1
IR spectra were recorded on an IKS-29 spectrophotometer using vaseline oil. H NMR spectra were
recorded on a Bruker Avance II 400 instrument (400 MHz) using DMSO-d6 with TMS as internal standard. The
elemental analysis for compound 5 was performed on a Carlo-Erba 1106 elemental analyzer and the remaining
compounds on a Perkin-Elmer CHN analyzer. Monitoring of the purity of the compounds prepared was carried
out by TLC using Silufol UV-254 plates with acetone–hexane (1:1) as eluent and visualized using iodine vapor
and a UV detector. Melting points were determined on a Koffler block and are not corrected. All of the
syntheses were carried out in an argon atmosphere.
Triethylammonium 4-Aryl(hetaryl)-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridine-2-selenolates (1a-d)
(General Method). A mixture of the corresponding aldehyde 2a-d (1.0 mmol), freshly prepared
cyanoselenoacetamide (3) (1.47 g, 1.0 mmol), acetone (2 ml), and triethylamine (1 drop) was stirred at 10ºC for
10 min. 1-(Cyanoacetyl)-3,5-dimethylpyrazole (6) (1.67 g, 1.0 mmol) was added followed by dropwise addition
of triethylamine (2 ml, 1.5 mmol). The mixture obtained was stirred for 30 min with cooling on an ice bath and
then left for 12 h in a fridge (3-4ºC). The precipitate formed was filtered off and washed with acetone and
hexane.
Triethylammonium 3,5-Dicyano-4-(2-methoxyphenyl)-6-oxo-1,4,5,6-tetrahydropyridine-2-selenolate
(1a). Yield 2.34 g (53%). Yellow, finely crystalline substance, mp 146-148ºC. IR spectrum, , cm-1: 1700
1
(C=O), 2190 and 2260 (2C≡N), 3180 (NH). H NMR spectrum, , ppm (J, Hz): (ratio of cis and trans isomers
~ 1:2): 1.22 (9H, t, 3J = 7.1, N(CH2CH3)3); 3.00 (6H, q, 3J = 7.1, N(CH2CH3)3); 3.78-3.86 (3H, m, OCH3); 4.28
3
3
(0.33H, br. s, cis-4-CH); 4.43 (0.67H, d, J = 12.2, trans-4-CH); 4.65 (0.67H, d, J = 12.2, trans-5-CH); 4.77
(0.33H, br. s, cis-5-CH); 6.92-7.37 (4H, m, H Ar); 10.63 (1H, br. s, NH). Found, %: C 54.96; H 6.11; N 12.76.
C14H10N3O2Se·C6H16N. Calculated, %: C 55.42; H 6.05; N 12.93.
Triethylammonium 3,5-Dicyano-4-(2-furyl)-6-oxo-1,4,5,6-tetrahydropyridine-2-selenolate (1b).
Yield 1.53 g (41%). Light-yellow, finely crystalline substance, mp 149-151ºC. IR spectrum, , cm-1: 1695
1
(C=O), 2175 and 2265 (2C≡N), 3150 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers
3
3
~ 1:3): 1.07 (9H, t, J = 6.9, N(CH2CH3)3); 2.67 (6H, q, J = 6.9, N(CH2CH3)3); 4.28 (0.25H, br. s, cis-4-CH);
4.43 (0.75H, br. s, trans-4-H); 4.66 (0.75H, br. s, trans-5-CH); 4.75 (0.25H, br. s, cis-5-CH); 6.37-6.51 (2H, m,
cis- and trans-3,4-CH furyl); 7.52 (0.75H, br. s, trans-5-CH furyl); 7.58 (0.25H, br. d, 3J = 6.3, cis-5-CH furyl);
10.77 (1H, br. s, NH). Found, %: C 51.39; H 5.67; N 14.16. C11H6N3O2Se·C6H16N. Calculated, %: C 51.91;
H 5.64; N 14.24.
Triethylammonium 3,5-Dicyano-6-oxo-4-(2-thienyl)-1,4,5,6-tetrahydropyridine-2-selenolate (1c).
Yield 1.75 g (43%). Light-yellow, finely crystalline substance, mp 153-155ºC. IR spectrum, , cm-1: 1695
1
(C=O), 2190 and 2263 (2C≡N), 3148 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers
~ 3:2): 1.15 (9H, t, 3J = 7.1, N(CH2CH3)3); 2.89 (6H, q, 3J = 7.1, N(CH2CH3)3); 4.29 (0.4H, d, 3J = 11.1, trans-
3
4-CH); 4.37 (0.6H, br. s, cis-4-CH); 4.48 (0.4H, d, J = 11.1, trans-5-CH); 4.73 (0.6H, br. s, cis-5-CH);
6.97-7.38 (3H, m, H thienyl); 10.33 (1H, br. s, NH). Found, %: C 49.61; H 5.45; N 13.51.
C11H6N3OSSe·C6H16N. Calculated, %: C 49.87; H 5.42; N 13.68.
Triethylammonium 3,5-Dicyano-6-oxo-4-phenyl-1,4,5,6-tetrahydropyridine-2-selenolate (1d).
Yield 1.05 g (26%). Yellow, finely crystalline substance, mp 155-157ºC. IR spectrum, , cm-1: 1705 (C=O), 2200
and 2215 (sh), 2260 (2C≡N), 3140 (NH). 1H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 1:1:
3
3
1.15 (9H, t, J = 7.1, N(CH2CH3)3); 2.95 (6H, q, J = 6.9, N(CH2CH3)3); 3.91 (0.5H, br. s, cis-4-CH); 4.02
3
3
(0.5H, d, J = 10.5, trans-4-CH); 4.29 (0.5H, d, J = 10.5, trans-5-CH); 4.69 (0.5H, br. s, cis-5-CH); 7.21-7.46
(5H, m, H Ph); 9.65 (1H, br. s, NH). Found, %: C 56.13; H 6.08; N 13.70. C13H8N3OSe·C6H16N. Calculated, %:
C 56.57; H 6.00; N 13.89.
N-Methylmorpholinium 6-Amino-3,5-dicyano-4-(2-methoxyphenyl)-1,4-dihydropyridine-2-selenolate
(5). A mixture of 2-methoxybenzaldehyde (2a) (1.63 ml, 1.36 mmol), cyanoselenoacetamide (3) (2.0 g,
1.36 mmol), and N-methylmorpholine (1-2 drops) was stirred in ethanol (20 ml) for 10 min at 20ºC. The
444

cyanoacetate 4 (1.45 ml, 1.36 mmol) and N-methylmorpholine (1.9 ml, 2 mmol) were added dropwise. The
mixture obtained was stirred for 30 min and left for 12 h at 20ºC. The precipitate formed was filtered off and
washed with acetone and hexane. Yield 2.27 g (39%). Bordeaux colored, finely crystalline substance, mp
170-172ºC. IR spectrum, , cm-1: 2180, 2190 (2C≡N), 3255, 3315, 3420 (NH, NH2). 1H NMR spectrum, , ppm:
2.40 (3H, s, NMe); 2.64 (4H, m, O(CH2)2); 3.70 (4H, m, N(CH2)2); 3.86 (3H, s, OMe); 4.85 (1H, s, 4-CH); 5.74
(2H, s, NH2); 6.85-7.27 (4H, m, H Ar); 9.27 (1H, s, NH). Found, %: C 52.84; H 5.39; N 16.04.
C15H11N4OSe·C4H12NO. Calculated, %: C 52.78; H 5.36; N 16.20.
4-Aryl-2-oxo-6-[(2-oxo-2-phenylethyl)seleno]-1,2,3,4-tetrahydropyridine-3,5-dicarbonitriles 9a-n
(General Method). A mixture of the corresponding selenolate 1a-d (1 mmol) and the corresponding alkyl
halide 8a-f (1 mmol) in 70% aqueous ethanol (30 ml) was refluxed for 1-2 min and rapidly filtered through a
plaited filter paper. The reaction mixture was allowed to stand for 24 h at 20ºC. The precipitate formed was
filtered off and washed with ethanol and hexane to give the corresponding selenide 9 in an analytically pure
state. If needed, the sample is crystallized from a suitable solvent.
4-(2-Methoxyphenyl)-2-oxo-6-[(2-oxo-2-phenylethyl)seleno]-1,2,3,4-tetrahydropyridine-3,5-dicarbo-
nitrile (9a). Yield 0.2 g (48%). Yellow-green, finely crystalline substance, mp 61-63ºC (AcOH). IR spectrum,
1
, cm-1: 1710 (C=O), 2220, 2270 (2C≡N), 3135 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans
3
isomers ~ 4:3): 3.80 (0.57H, s, cis-OMe); 3.88 (0.43H, s, trans-OMe); 4.42 (0.57H, d, J = 8.2, cis-4-CH); 4.42
3
3
(0.43H, d, J = 13.0, trans-4-CH); 4.56 (0.43H, d, J = 13.0, trans-3-CH); 4.67-4.81 (2.57H, m, cis-3-CH,
SeCH2); 6.95-8.03 (9H, m, H Ar); 10.90 (0.57H, s, cis-NH); 11.04 (0.43H, s, trans-NH). Found, %: C 58.25;
H 3.84; N 9.27. C22H17N3O3Se. Calculated, %: C 58.67; H 3.80; N 9.33.
Methyl {[3,5-Dicyano-4-(2-furyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]seleno}acetate (9b). Yield
0.16 g (47%). Light-brown crystalline substance, mp 150-152ºC. IR spectrum, , cm-1: 1710 (C=O), 2210, 2270
1
(2C≡N), 3150 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 2:5): 3.67 (0.71H, s,
trans-OMe); 3.72 (0.29H, s, cis-OMe); 3.80-3.90 (2H, m, SeCH2); 4.42 (0.29H, m, cis-4-CH); 4.55 (0.71H, m,
trans-4-CH); 4.64 (0.71H, m, trans-5-CH); 4.81 (0.29H, m, cis-5-CH); 6.39-6.48 (2H, m, H-3,4 furyl); 7.55
(0.71H, br. d, 3J = 5.9, trans-H-5 furyl); 7.60 (0.29H, br. d, 3J = 5.9, cis-H-5 furyl); 11.12 (0.71H, s, trans-NH);
11.14 (0.29H, s, cis-NH). Found, %: C 45.91; H 3.07; N 11.43. C14H11N3O4Se. Calculated, %: C 46.17; H 3.04;
N 11.54.
4-(2-Furyl)-2-oxo-6-[(2-oxo-2-phenylethyl)seleno]-1,2,3,4-tetrahydropyridine-3,5-dicarbonitrile (9c).
Yield 0.18 g (45%). White, finely crystalline substance, mp 197-199ºC (AcOH). IR spectrum, , cm-1: 1725
1
(C=O), 2205, 2260 (2C≡N), 3135 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~
3
3
3
2:1): 4.38 (0.67H, d, J = 6.6, cis-4-CH); 4.53 (0.33H, d, J = 12.2, trans-4-CH); 4.61 (0.33H, d, J = 12.2,
3
trans-3-CH); 4.79 (0.67H, d, J = 6.6, cis-3-H); 4.70-4.83 (2H, m, SeCH2); 6.38-7.64 (6H, m, H-3,4,5 Ph and
H-3,4,5 furyl); 7.99 (2H, br. d, 3J = 7.8, H-2,6 Ph); 11.04 (1H, br. s, NH). Found, %: C 55.31; H 3.22; N 10.17.
C19H13N3O3Se. Calculated, %: C 55.62; H 3.19; N 10.24.
4-(2-Furyl)-6-{[2-(methylphenyl)-2-oxoethyl]seleno}-2-oxo-1,2,3,4-tetrahydropyridine-3,5-dicarbo-
nitrile (9d). Yield 0.24 g (59%). White, finely crystalline substance, mp 193-195ºC (AcOH). IR spectrum, , cm-1:
1
1712 (C=O), 2205, 2260 (2C≡N), 3120 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers
3
3
~2:1): 2.44 (3H, br. s, 4-CH3); 4.37 (0.67H, d, J = 6.6, cis-4-CH); 4.52 (0.33H, d, J = 12.1, trans-4-CH); 4.59
3
(0.33H, d, J = 12.1, trans-3-CH); 4.67-4.80 (2.67H, m, SeCH2, cis-3-CH); 6.39-6.48 (2H, m, H-3,4 furyl); 7.29
(2H, m, H-3,5 Ar); 7.53 (0.67H, m, cis-H-5 furyl); 7.58 (0.33H, m, trans-H-5 furyl); 7.90 (2H, m, H-2,6 Ar); 11.02
(1H, br. s, NH). Found, %: C 56.26; H 3.59; N 9.86. C20H15N3O3Se. Calculated, %: C 56.61; H 3.56; N 9.90.
2-{[3,5-Dicyano-4-(2-furyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]seleno}-N-phenylacetamide (9e).
Yield 0.28 g (68%). Light-brown crystalline substance, mp 188-190ºC (AcOH). IR spectrum, , cm-1: 1725
1
(C=O), 2200, 2265 (2C≡N), 3135, 3400 (2NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans
isomers ~ 5:2): 3.85-4.01 (2H, m, SeCH2); 4.42 (0.71H, d, 3J = 6.7, cis-4-CH); 4.63 (0.29H, d, 3J = 12.5, trans-
4-CH); 4.67 (0.29H, d, 3J = 12.5, trans-5-CH); 4.87 (0.71H, d, 3J = 6.7, cis-5-CH); 6.39 (1.42H, br. s, cis-H-3,4
furyl); 6.43 (0.29H, m) and 6.49 (0.29H, m, trans-H-3,4 furyl); 7.04-7.59 (6H, m, H-5 furyl, H Ph); 10.33
445

(0.71H, s, cis-NHPh); 10.36 (0.29H, s, trans-NHPh); 11.38 (0.71H, s, cis-NH); 11.42 (0.29H, s, trans-NH).
Found, %: C 53.12; H 3.35; N 13.06. C19H14N4O3Se. Calculated, %: C 53.66; H 3.32; N 13.17.
2-{[3,5-Dicyano-4-(2-furyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]seleno}-N-(4-methylphenyl)acet-
amide (9f). Yield 0.25 g, (60%). Light-brown crystalline substance, mp 199-201ºC. IR spectrum, , cm-1: 1720
1
(C=O), 2205, 2260 (2C≡N), 3165, 3375 (2NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans
3
isomers ~ 2:1): 2.31 (3H, br. s, 4-CH3); 3.81-3.98 (2H, m, SeCH2); 4.39 (0.67H, d, J = 6.6, cis-4-CH); 4.60
(0.66H, br. s, trans-4-CH, trans-5-CH); 4.84 (0.67H, d, 3J = 6.6, cis-5-CH); 6.38 (1.34H, br. s, cis-H-3,4 furyl);
6.42 (0.33H, m) and 6.46 (0.33H, m, trans-H-3,4 furyl); 7.06-7.46 (4H, m, H Ar); 7.52 (0.67H, br. s, cis-H-5
furyl); 7.56 (0.33H, br. s, trans-H-5 furyl); 10.22 (0.67H, s, cis-NH Ar); 10.25 (0.33H, s, trans-NH Ar); 11.43
(0.67H, s, cis-NH); 11.50 (0.33H, s, trans-NH). Found, %: C 53.92; H 3.71; N 12.61. C20H16N4O3Se.
Calculated, %: C 54.68; H 3.67; N 12.75.
2-Oxo-6-[(2-oxo-2-phenylethyl)seleno]-4-(2-thienyl)-1,2,3,4-tetrahydropyridine-3,5-dicarbonitrile
(9g). Yield 0.40 g (96%). White crystalline substance, mp 195-197ºC (AcOH). IR spectrum, , cm-1: 1718
1
(C=O), 2200, 2260 (2C≡N), 3140 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers
~ 3:1): 4.54 (0.25H, d, 3J = 11.7, trans-4-CH); 4.62 (0.75H, d, 3J = 6.6, cis-4-CH); 4.75 (0.25H, d, 3J = 11.7, trans-
3
3-CH); 4.72-4.92 (2H, m, SeCH2); 4.87 (0.75H, d, J = 6.6, cis-3-CH); 7.02-7.17 (2H, m, H-3,4 thienyl); 7.42
(0.75H, m, cis-CH-5 thienyl); 7.46 (0.25H, m, trans-CH thienyl); 7.51-8.03 (5H, m, H Ph); 11.15 (0.25H, s, trans-
NH); 11.20 (0.75H, s, cis-NH). Found, %: C 53.17; H 3.11; N 9.79. C19H13N3O2SSe. Calculated, %: C 53.52;
H 3.07; N 9.86.
6-{[2-(4-Methylphenyl)-2-oxoethyl]seleno}-2-oxo-4-(2-thienyl)-1,2,3,4-tetrahydropyridine-3,5-di-
carbonitrile (9h). Yield 0.33 g (76%). White crystalline substance, mp 200-202ºC (AcOH). IR spectrum, , cm-1:
1
1715 (C=O), 2204, 2265 (2C≡N), 3180 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers
~ 5:2): 2.43 (3H, m, CH3); 4.48 (0.29H, d, 3J = 11.7, trans-4-CH); 4.57 (0.71H, d, 3J = 6.1, cis-4-CH); 4.69-4.83
3
(2.29H, m, trans-3-CH, SeCH2); 4.85 (0.71H, d, J = 6.1, cis-4-CH); 7.01-7.15 (2H, m, H-3,4 thienyl); 7.29
3
3
(2H, br. d, J = 8.3, H-3,5 Ar); 7.37-7.43 (1H, m, H-5 thienyl); 7.89 (1.42H, d, J = 8.3, cis-H-2,6 Ar); 7.90
(0.58H, d, 3J = 8.3, trans-H-2,6 Ar); 11.10 (0.29H, s, trans-NH); 11.14 (0.71H, s, cis-NH). Found, %: C 54.16;
H 3.47; N 9.46. C20H15N3O2SSe. Calculated, %: C 54.55; H 3.43; N 9.54.
Methyl [(3,5-Dicyano-6-oxo-4-phenyl-1,4,5,6-tetrahydropyridin-2-yl)seleno]acetate (9i). Yield 0.2 g
(54%). White crystalline substance, mp 178-180ºC. IR spectrum, , cm-1: 1720 (C=O), 2205, 2270 (2C≡N),
3150 (NH). 1H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 1:1): 3.67 (1.5H, s, cis-OCH3);
3
3.73 (1.5H, s, trans-OCH3); 3.83-3.90 (2H, m, SeCH2); 4.24 (0.5H, d, J = 6.9, cis-4-CH); 4.35 (0.5H, d,
3J = 11.5, trans-4-CH); 4.55 (0.5H, d, 3J = 11.5, trans-5-CH); 4.86 (0.5H, d, 3J = 6.9, cis-5-CH); 7.23-7.44 (5H,
m, H Ph); 11.11 (0.5H, s, cis-NH); 11.14 (0.5H, s, trans-NH). Found, %: C 50.64; H 3.54; N 11.13.
C16H13N3O3Se. Calculated, %: C 51.35; H 3.50; N 11.23.
Ethyl [(3,5-Dicyano-6-oxo-4-phenyl-1,4,5,6-tetrahydropyridin-2-yl)seleno]acetate (9j). Yield 0.09 g
(24%). White, finely crystalline substance, mp 154-156ºC. IR spectrum, , cm-1: 1725 (C=O), 2200, 2265
1
(2C≡N), 3180 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 5:4): 1.25 (1.65H, t,
3
3J = 7.1, cis-OCH2CH3); 1.30 (1.35H, t, J = 7.1, trans-OCH2CH3); 3.82-3.90 (2H, m, SeCH2); 4.12 (1.1H, q,
3
3
3J = 7.1, cis-OCH2CH3); 4.22 (0.9H, q, J = 7.1, trans-OCH2CH3); 4.25 (0.55H, d, J = 6.9, cis-4-CH); 4.35
3
3
3
(0.45H, d, J = 12.5, trans-4-CH); 4.56 (0.45H, d, J = 12.5, trans-5-CH); 4.85 (0.55H, d, J = 6.9, cis-5-CH);
7.23-7.45 (5H, m, H Ph); 11.12 (0.45H, s, trans-NH); 11.14 (0.55H, s, cis-NH). Found, %: C 52.11; H 3.93;
N 10.78. C17H15N3O3Se. Calculated, %: C 52.59; H 3.89; N 10.82.
2-Oxo-6-[(2-oxo-2-phenylethyl)seleno]-4-phenyl-1,2,3,4-tetrahydropyridine-3,5-dicarbonitrile (9k).
Yield 0.24 g (58%). White, finely crystalline substance, mp 195-197ºC. IR spectrum, , cm-1: 1715 (C=O),
2207, 2265 (2C≡N), 3148 (NH). 1H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 6:5): 4.23
3
3
3
(0.55H, d, J = 7.1, cis-4-CH); 4.33 (0.45H, d, J = 13.0, trans-4-CH); 4.55 (0.45H, d, J = 13.0, trans-3-CH);
4.72-4.88 (2.55H, m, cis-3-CH, SeCH2); 7.24-8.04 (10H, m, H Ph); 11.11 (1H, br. s, NH). Found, %: C 59.63;
H 3.63; N 9.89. C21H15N3O2Se. Calculated, %: C 60.01; H 3.60; N 10.00.
446

6-{[2-(4-Methylphenyl)-2-oxoethyl]seleno}-2-oxo-4-phenyl-1,2,3,4-tetrahydropyridine-3,5-dicarbo-
nitrile (9l). Yield 0.32 g (74%). White, finely crystalline substance, mp 205-207ºC. IR spectrum, , cm-1: 1717
1
(C=O), 2202, 2265 (2C≡N), 3150 (NH). H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers
3
3
~ 6:5): 2.44 (3H, br. s, CH3); 4.23 (0.55H, d, J = 7.1, cis-4-CH); 4.32 (0.45H, d, J = 13.0, trans-4-CH); 4.54
3
3
(0.45H, d, J = 13.0, trans-3-CH); 4.68-4.84 (2H, m, SeCH2); 4.86 (0.55H, d, J = 7.1, cis-3-CH); 7.24-7.93
(9H, m, H Ar); 11.07 (1H, br. s, NH). Found, %: C 60.41; H 3.98; N 9.57. C22H17N3O2Se. Calculated, %:
C 60.83; H 3.94; N 9.67.
2-[(3,5-Dicyano-6-oxo-4-phenyl-1,4,5,6-tetrahydropyridin-2-yl)seleno]-N-phenylacetamide (9m).
Yield 0.31 g (74%). White crystalline substance, mp 207-209ºC (AcOH). IR spectrum, , cm-1: 1745 (C=O), 2202,
1
2260 (2C≡N), 3150, 3430 (2NH) H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 7:6):
3
3
3.88-4.06 (2H, m, SeCH2); 4.26 (0.54H, d, J = 7.0, cis-4-CH); 4.38 (0.46H, d, J = 13.0, trans-4-CH); 4.64
(0.46H, d, 3J = 13.0, trans-5-CH); 4.95 (0.54H, d, 3J = 7.0, cis-5-CH); 7.04-7.62 (10H, m, H Ph); 10.35 (0.54H,
s, cis-NHPh); 10.37 (0.46H, s, trans-NHPh); 11.42 (0.46H, s, trans-NH); 11.44 (0.54H, s, cis-NH). Found, %:
C 57.36; H 3.74; N 12.79. C21H16N4O2Se. Calculated, %: C 57.94; H 3.70; N 12.87.
N-(4-Methylphenyl)-2-[(3,5-dicyano-6-oxo-4-phenyl-1,4,5,6-tetrahydropyridin-2-yl)seleno]acetamide
(9n). Yield 0.31 g (70%). Light-yellow crystalline substance, mp 206-208ºC. IR spectrum, , cm-1: 1725 (C=O),
2205, 2260 (2C≡N), 3148, 3400 (2NH). 1H NMR spectrum, , ppm (J, Hz) (ratio of cis and trans isomers ~ 10:9):
2.32 (1.59H, s, cis-CH3); 2.33 (1.41H, s, trans-CH3); 3.85-4.02 (2H, m, SeCH2); 4.21 (0.53H, d, 3J = 6.9, cis-4-CH);
4.32 (0.47H, d, 3J = 12.7, trans-4-CH); 4.56 (0.47H, d, 3J = 12.7, trans-5-CH); 4.89 (0.53H, d, 3J = 6.9, cis-5-CH);
7.07-7.50 (9H, m, H Ar); 10.24 (0.53H, s, cis-NHPh); 10.26 (0.47H, s, trans-NHPh); 11.48 (1H, br. s, NH).
Found, %: C 58.47; H 4.08; N 12.32. C22H18N4O2Se. Calculated, %: C 58.80; H 4.04; N 12.47.
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