4-alkyl-6-amino-4-N 3,N 5-diaryl-2-thioxo-1,2,3,4- tetrahydropyridine-3,5-dicarboxamides: I. Tandem synthesis and alkylation. Molecular and crystal structure of 6-allylsulfanyl-2-amino-4-isobutyl-N 3,N 5-di-m-to

Article abstract of DOI:10.1134/S1070363213070153

4-Alkyl-6-amino-4-N ³,N ⁵-diaryl-2-thioxo-1,2,3,4- tetrahydropyridine-3,5-dicarboxamides were obtained via tandem synthesis involving the Knoevenagel reaction, Michael reaction and intramolecular condensation. Alkylation of the obtai

Full text of DOI:10.1134/S1070363213070153

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 7, pp. 1394–1401. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.D. Dyachenko, E.N. Karpov, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 7, pp. 1143–1150.
4-Alkyl-6-amino-4-N3,N5-diaryl-2-thioxo-1,2,3,4-
tetrahydropyridine-3,5-dicarboxamides: I. Tandem Synthesis
and Alkylation. Molecular and Crystal Structure
of 6-Allylsulfanyl-2-amino-4-isobutyl-N3,N5-di-m-tolyl-3,4-
dihydropyridine-3,5-dicarboxamide
V. D. Dyachenko and E. N. Karpov
Shevchenko Lugansk National University, ul. Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: chem@luguniv.edu.ua
Received July 3, 2012
Abstract—4-Alkyl-6-amino-4-N3,N5-diaryl-2-thioxo-1,2,3,4-tetrahydropyridine-3,5-dicarboxamides were obtained
via tandem synthesis involving the Knoevenagel reaction, Michael reaction and intramolecular condensation.
Alkylation of the obtained dicarboxamides proceeds regioselectively at the S atom to form the corresponding
thioethers. Structure of 6-allylsulfanyl-2-amino-4-isobutyl-N3,N5-di-m-tolyl-3,4-dihydropyridine-3,5-dicarbox-
amide was uniquely determined by XRD analysis.
DOI: 10.1134/S1070363213070153
Currently tandem reactions are widely used in
organic synthesis [1–3]. This approach to construct
complex structures from simple molecules has been
previously used by us to obtain the nitrogen-containing
heterocyclic compounds: pyrrolines [4], pyridines [5],
dihydropyridines [6], and fused pyrimidines [7].
In the present work we examined a condensation of
aliphatic aldehydes Ia–If with a double excess of 3-
amino-3-thioxopropaneanilides IIa–IIc in anhydrous
ethanol at 20°C in the presence of sodium ethoxide.
This condensation consists in a tandem of several
reactions and results in new 4-alkyl-6-amino-N3,N5-
O
Ar
Alk
O
O
Alk O
O
NH
II
EtONa
_H2O
Ar
Ar
Ar
Alk
+
2
N
H
N
H
N
H
NH2
S
NH2
S
NH2
S
NH2
S
Iа_If
IIа_IIc
А
B
O
Alk
O
O
Alk
N
O
S
O
Alk
O
R
Hlg
Ar
Ar
Ar
Ar
Ar
Ar
KOH
_H2O
IVa_IVf
N
H
N
H
N
H
N
H
N
H
N
_H2S
H
H2N
N
S K+
H2N
N
H
S
H2N
IIIа_IIIg
Vа_Vo
R
C
I, Alk = i-Bu (a), Et (b), i-Pr (c), Me (d), n-C6H13 (e), CH((Ph)CH3 (f); II, Ar = Ph (a), 2-MeC6H4 (b), 3-MeC6H4 (c); III,
Alk = i-Bu, Ar = 2-MeC6H4 (a); i-Bu, 3-MeC6H4 (b); i-Pr, 2-MeC6H4 (c); Et, 2-MeC6H4 (d); n-C6H13, 2-MeC6H4 (e);
CH(Ph)CH3, Ph (f); Me, Ph (g); IV, R = COOEt (a), Ph (b), 4-BrC6H4NHC(O) (c), 4-MeOC6H4NHC(O) (d), CH=CH2 (e),
n-С8Н17 (f); V, Alk = i-Bu, Ar = 2-MeC6H4, R = CH=CH2 (a); i-Bu, 2-MeC6H4, COOEt (b); i-Bu, 2-MeC6H4,
4-MeOC6H4NHC(O) (c); i-Bu, 3-MeC6H4, CH=CH2 (d); i-Bu, 3-MeC6H4, Ph (e); i-Pr, 2-MeC6H4, CH=CH2 (f); Et,
2-MeC6H4, CH=CH2 (g); Et, 2-MeC6H4, COOEt (h); n-C6H13, 2-MeC6H4, CH=CH2 (i); n-C6H13, 2-MeC6H4, Ph (j); CH(Ph)
CH3, Ph, CH=CH2 (k); CH(Ph)CH3, Ph, 4-BrC6H4NHC(O) (l); Me, Ph, 4-MeOC6H4NHC(O) (m); Me, Ph, CH=CH2 (n);
Me, Ph, n-С8Н17 (o).
1394

4-ALKYL-6-AMINO-4-N3,N5-DIARYL-2-THIOXO-1,2,3,4-…: I.
1395
diaryl-2-thioxo-1,2,3,4-tetrahydropyridine-3,5-dicar-
boxamides IIIa–IIIg. Apparently, alkene A was
initially formed as a result of the Knoevenagel
reaction. Then the Michael reaction occurs to form the
corresponding adduct B. The latter was chemoselec-
tively transformed into the final product III via an
intramolecular cyclocondensation.
the presence of two doublet signals with the coupling
2
constants J of 12–16 Hz characteristic of this type of
compounds [8, 9]. The doubling with equal intensity of
the signals from С3Н, С4Н, and СНМе protons in the
1H NMR spectrum of compound IIIf indicates the
presence of a chiral center in a phenylethyl moiety.
The structure of 6-allylsulfanyl-2-amino-4-isobutyl-
N3,N5-di-m-tolyl-3,4-dihydropyridine-3,5-dicarbox-
amide Vd was studied by XRD in order to establish
unambiguously the chemoselectivity of cyclization of
the Michael adduct B and the regioselectivity of alkyla-
tion of compounds IIIa–IIIg and also to determine the
position of double bonds in the dihydropyridine ring
(commonly 2,5 location in the fully substituted 2-
alkylsulfanyldihydropyridines [10–12]).
The structures of compounds IIIa–IIIg were con-
firmed by the spectral methods and also by chemical
transformations. Thus, their alkylation with alkyl
halides IVa–IVf results in the corresponding thioethers
Va–Vo. This reaction proceeds smoothly in ethanol at
20°C in the presence of an equimolar amount of an
aqueous KOH solution and apparently includes the
formation of an intermediate salt C.
The 1H NMR spectra of compounds IIIa–IIIg
contain characteristic proton signals of the substituents
of tetrahydropyridine ring in the respective areas and
the signals of N1H, C3H and С4Н proton in the range of
12.45–13.25, 3.74–4.10 and 3.69–3.98 ppm, respec-
The molecule of compound Vd contains two chiral
centers, the C2 and C3 atoms, with the same absolute
configuration. The dihydropyridine ring has an inter-
mediate conformation between a semi-chair and twist-
boat (see figure). The fragment C1N1C5C4 is nonplanar
[torsion angle 20.6(5)°], the C2 and C3 atoms are out of
the median plane of this fragment by 0.404(7) and
–0.343(7) Å, respectively. The substituents at the C2
and C3 atoms have axial orientation [∠C1C2C3C14
–70.3(4)°, ∠N2C1C2C6 –99.5(4)°]. The carbonyl group
of the О1С6N3 amide fragment has sc-orientation with
respect to the bond С2–С3 [∠С3С2С6О1 7.1(5)°], which
is probably due to formation of an intramolecular
hydrogen bond N4–H4···O1 (H···O 2.24°, N–H···O
147°). Tolyl substituent at the N3 atom is slightly
turned with respect to the plane of the amide group
[torsion angle is C6N3C7C12 35.2(6)°]. Due to steric
1
tively. In the H NMR spectra of compounds Va–Vo
there are characteristic proton signals of C3H and С4Н
groups at δ 3.43–4.34 ppm, and the signals of amino
group and a SCH2 fragment. It should be noted that the
nature of the proton signals of the last groups indicates
the absence of free rotation. Thus, the signal of amino
group is split in two broadened singlets instead of the
expected one broad singlet, which may indicate the
formation of a hydrogen bond confirmed by X-ray
diffraction analysis for compound Vd. The absence of
free rotation of alkylsulfanyl groups and non-
equivalence of the SCH2-protons is also confirmed by
General view of the molecule of Vd according to XRD data.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1396
DYACHENKO, KARPOV
N2–H2a···N1i [i: 1/2 – x, 1/2 – y, z] (H···N 2.31 Å,
N–H···N 146°). These dimers form the chains along
the axis а due to the weak hydrogen bonding
N3–H3···O2ii [ii: 1 + x, y, z] (H···O 2.47 Å, N–H···O
128°) and N2–H2b···S1ii (H···S 2.97 Å, N–H···S 132°).
Table 1. The bond lengths (Å) in the structure of Vd
Bond
d
Bond
d
S1
S1
C5
C26
C6
C18
C1
C5
C1
C6
C7
C18
C19
C2
C3
C6
C4
C14
C5
C18
C8
1.775(3)
1.822(5)
1.223(4)
1.241(4)
1.298(4)
1.401(4)
1.332(4)
1.351(4)
1.418(4)
1.347(4)
1.418(4)
1.508(5)
1.524(4)
1.527(5)
1.529(4)
1.543(5)
1.334(4)
1.482(4)
1.377(5)
C7
C8
C9
C9
C12
C9
1.383(5)
1.371(5)
1.379(5)
1.503(5)
1.385(5)
1.379(5)
1.519(5)
1.535(6)
1.520(7)
1.374(4)
1.377(4)
1.392(4)
1.377(5)
1.505(5)
1.371(5)
1.371(5)
1.487(6)
1.279(7)
EXPERIMENTAL
O1
O2
N1
N1
N2
N3
N3
N4
N4
C1
C2
C2
C3
C3
C4
C4
C7
C10
C13
C11
C12
C15
C16
C17
C20
C24
C21
C22
C25
C23
C24
C27
C28
Crystals of compound Vd are rhombic,
C28H34N4O2S; at 298 K: a 8.1384(5), b 36.179(3), c
18.5955(16) Å; V 5475.3(7) Å3, M 490.65, Z 8, space
group Pccn, dcalc 1.19 g cm–3, μ(MoKα) 0.149 mm–1,
F(000) 2096. The unit cell parameters and intensities
of 40295 reflections (4857 independent, Rint 0.125)
were measured on a Xcalibur 3 four-circle automatic
diffractometer (MoKα, graphite monochromator, CCD-
detector, ω-scanning, 2θmax 50.0°). The structure was
solved by the direct method using SHELX-97 program
[14]. Positions of the hydrogen atoms were calculated
C10
C11
C14
C15
C15
C19
C19
C20
C21
C21
C22
C23
C26
C27
geometrically and refined in a rider model with Uiso
=
nUeq of the carrier atom (n = 1.5 for methyl groups, n =
1.2 for the other hydrogen atoms). The structure was
refined with respect to F2 using a full-matrix
anisotropic approximation for nonhydrogen atoms to
wR2 0.173 for 4857 reflections [R1 0.067 for 2443 ref-
lections with F > 4σ(F), S 0.99]. In the crystal a
disordered solvent molecule, apparently ethanol, is
present whose contribution to the electron density was
removed from F02 at the final refining step by means of
SQUEEZE procedure in PLATON program [15]. The
bond lengths and bond angles are listed in Tables 1 and
2, respectively.
1
hindrances (a short intramolecular contact H3a···H4
2.07 Å against the sum of the van der Waals radii of
2.32 Å [13]) and also due to the intramolecular
hydrogen bond N4–H4···O1 there is a rotation of the
amide group O2–C18–N4 relative to the plane of the
double bond С4=С5 [∠C5C4C18O2 –49.7(5)°]. Tolyl
substituent at the N4 atom is in the plane of the amide
group [∠С18N4C19C20 –6.9(6)°]. This orientation is
additionally stabilized by the formation of an
intramolecular hydrogen bond C20–H20···O2 (H···O 2.35
Å, C–H···O 122°). The bond S1–C26 is non-co-planar
with the heterocycle plane [∠C26S1C5N1 39.8(3)°], which
should lead to some disruption of conjugation between
the lone electron pairs of the sulfur atom and the π-
system of the heterocycle. Probably, this is
compensated by the formation of the shortened
intramolecular contacts N1···H26b 2.48 Å (sum of the
van der Waals radii 2.66 Å [13]). In the crystal, the
molecules form dimers by hydrogen bonds
The H NMR spectra were recorded on a Bruker
AVANCE DRX-500 (500 MHz) (Vd, Vh, Vl) and
Bruker AVANCE II-400 (400 MHz) spectrometers
(IIIa–IIIg, Va–Vc, Ve–Vg, Vi–Vk, Vm–Vo) in a
DMSO-d6 solution, internal reference TMS). The 13C
NMR spectrum of compound Vd was taken on a
Bruker AVANCE DRX-500 spectrometer (125.75 MHz).
Mass spectra were registered on a Chrommas GC/MS-
Hewlett-Packard 5890/5972 instrument (column HP-
5MS, chemical ionozation, 70 eV) in СН2Сl2 solutions.
The IR spectra were recorded on a Perkin-Elmer
Spectrum One FTIR instrument from KBr pellets.
Melting points were measured on a Koeffler heating
block. The reaction progress and purity of the
compounds obtained were monitored by TLC (Silufol
UV-254 plates) eluting with an acetone–hexane
mixture (3:5) and detecting with iodine vapors.
Synthesis of 4-alkyl-6-amino-N3,N5-diaryl-2-thioxo-
1,2,3,4-tetrahydropyridine-3,5-dicarboxamides (IIIa–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

4-ALKYL-6-AMINO-4-N3,N5-DIARYL-2-THIOXO-1,2,3,4-…: I.
Table 2. Bond angles (deg) in the structure of Vd
1397
Angle
S1
deg
Angle
C9
C9
deg
C5
C1
C6
C18
N1
N1
N2
C1
C1
C3
C2
C2
C4
C5
C5
C18
N1
C4
C4
O1
O1
N3
C8
C8
C12
C9
C26
C5
C7
C19
N2
C2
C2
C3
C6
C6
C4
C14
C14
C3
C18
C3
S1
100.78(19)
117.1(3)
128.5(3)
130.9(3)
119.2(3)
122.6(3)
118.1(3)
107.3(3)
111.7(3)
112.0(3)
108.0(3)
111.0(3)
111.8(3)
117.5(3)
122.3(3)
120.0(3)
114.2(3)
122.2(2)
123.5(3)
122.6(3)
123.2(3)
114.1(3)
118.0(3)
119.5(3)
122.4(3)
122.3(4)
C8
C8
C10
C9
C12
C11
C15
C14
C14
C17
O2
C10
C13
C13
C11
C10
C7
118.5(4)
121.2(4)
120.3(4)
119.6(4)
121.7(4)
118.3(4)
114.8(3)
109.0(4)
112.2(4)
108.0(5)
123.8(3)
122.5(3)
113.7(3)
123.4(3)
119.2(3)
117.3(3)
120.9(3)
120.9(3)
119.0(3)
120.2(3)
119.8(3)
121.0(4)
120.0(4)
112.7(3)
126.3(6)
N1
N3
N4
C1
C1
C1
C2
C2
C2
C3
C3
C3
C4
C4
C4
C5
C5
C5
C6
C6
C6
C7
C7
C7
C8
C9
C10
C11
C12
C14
C15
C15
C15
C18
C18
C18
C19
C19
C19
C20
C21
C21
C21
C22
C23
C24
C26
C27
C3
C16
C17
C16
N4
C4
C4
N4
C24
N4
C21
C25
C20
C25
C21
C24
C19
S1
O2
N4
C20
C20
C24
C19
C20
C22
C22
C23
C22
C23
C27
C28
S1
N1
N3
C2
C2
N3
C12
N3
C7
C26
1
IIIg) (general procedure). To a solution of 5 mmol
(0.115 g) of metallic sodium in 20 ml of anhydrous
ethanol was added under stirring 5 mmol of appro-
priate 3-amino-N-aryl-3-thioxopropanamide IIa–IIc
and 5 mmol of aldehyde Ia–If. After 10 min to the
mixture was added another 5 mmol of appropriate 3-
amino-N-aryl-3-thioxopropanamide IIa–Iic. The mix-
ture was kept for 48 h at room temperature. The
formed precipitate was filtered off, washed with water,
cold ethanol, and hexane.
6-Amino-4-isobutyl-2-thioxo-N3,N5-di-o-tolyl-
1,2,3,4-tetrahydropyridine-3,5-dicarboxamide (IIIa).
Yield 1.18 g (52%), yellow powder, mp 162–164°C
(EtOH). IR spectrum, ν, cm–1: 3235–3412 (NH, NH2),
1672 (СОNH), 1646 [δ(NH2)], 1211 (С=S). Н NMR
spectrum, δ, ppm: 0.93 d (3Н, СН3, J 6.2 Hz), 0.97 d
(3Н, СН3, J 6.2 Hz), 1.11–1.32 m (2Н, СН2), 1.51–
1.77 m (1Н, СНMe2), 2.12 s (3Н, СН3), 2.34 s (3Н,
СН3), 3.83 s (1Н, С3Н), 3.97 t (1Н, С4Н, J 7.0 Hz),
6.87 t (1Н, Нarom, J 7.3 Hz), 6.96–7.28 m (8Н, 6Нarom
,
NH2), 8.20 d (1Н, Нarom, J 7.9 Hz), 9.72 br.s (1Н,
NHCO), 10.18 br.s (1Н, NHCO), 12.45 br.s (1Н, N1H).
Mass spectrum, m/z (Irel, %): 451.2 (100) [М + 1]+.
Found, %: С 66.52; Н 6.65; N 12.29. С25H30N4O2S.
Calculated, %: С 66.64; Н 6.71; N 12.43. M 450.608.
6-Amino-4-isobutyl-2-thioxo-N3,N5-di-m-tolyl-
1,2,3,4-tetrahydropyridine-3,5-dicarboxamide (IIIb).
Yield 1.23 g (55%), yellow powder, mp 180–182°C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1398
DYACHENKO, KARPOV
(EtOH). IR spectrum, ν, cm–1: 3228–3411 (NH, NH2),
1.48 m (10Н, 5СН2), 2.11 s (3Н, СН3), 2.33 s (3Н,
СН3), 3.81–3.94 br.s (2Н, С3Н and С4Н), 6.84–6.91 m
(1Н, Нarom), 7.00–7.25 m (8Н, 6Нarom, NH2), 8.19 d
(1Н, Нarom, J 8.0 Hz), 9.75 br.s (1Н, NHСО), 10.30
br.s (1Н, NHСО), 12.46 br.s (1Н, N1H). Mass
spectrum, m/z (Irel, %): 479.2 (100) [М + 1]+. Found,
%: С 67.69; Н 7.22; N 11.58. С27H34N4O2S.
Calculated, %: С 67.75; Н 7.16; N 11.71. M 478.663.
1
1670 (СОNH), 1640 [δ(NH2)], 1191 (С=S). Н NMR
spectrum, δ, ppm: 0.88 d (3Н, СН3, J 5.6 Hz), 0.96 d
(3H, СН3, J 5.6 Hz), 1.08–1.29 m (2Н, СН2), 1.56–
1.72 m (1Н, СНМе2), 2.26 s (6Н, 2СН3), 3.71–3.81 m
(1Н, С4Н), 3.84 s (1Н, С3Н), 6.73 d (1Н, Нarom, J
6.9 Hz), 6.87 d (1Н, Нarom, J 7.0 Hz), 7.10 t (1Н, Нarom
,
J 7.2 Hz), 7.17 t (1Н, Нarom, J 7.2 Hz), 7.25–7.36 m
(2Н, Нarom), 7.36–7.48 m (2Н, Нarom), 8.56 br.s (1Н,
NH2), 9.48 br.s (1Н, NH2), 10.27 br.s (2Н, 2NHCO),
13.18 br.s (1Н, N1H). Mass spectrum, m/z (Irel, %):
451.2 (82) [М + 1]+. Found, %: С 66.50; Н 6.64; N
12.37. С25H30N4O2S. Calculated, %: С 66.64; Н 6.71;
N 12.43. M 450.608.
6-Amino-2-thioxo-N3,N5-diphenyl-4-(1-phenyl-
ethyl)-1,2,3,4-tetrahydropyridine-3,5-dicarbox-
amide (IIIf). Yield 0.65 g (28%), yellow powder, mp
188–190°C (EtOH). IR spectrum, ν, cm–1: 2930–3444
(NH, NH2), 1683 (СОNH), 1601 [δ(NH2)], 1167
1
(С=S). Н NMR spectrum, δ, ppm: 1.08 d (3Н, СН3,
6-Amino-4-isopropyl-2-thioxo-N3,N5-di-o-tolyl-
1,2,3,4-tetrahydropyridine-3,5-dicarboxamide (IIIc).
Yield 0.46 g (21%), white powder, mp 188–190°C
(EtOH). IR spectrum, ν, cm–1: 3195–3340 (NH, NH2),
J 6.5 Hz), 2.83 br.s and 2.97 br.s (1Н, СНМе), 3.98
br.s and 4.10 br.s (1Н, С3Н), 4.27 br.s and 4.36 br.s
(1Н, С4Н), 6.70–7.65 m (17Н, 15Нarom, NH2), 9.68 br.s
(1Н, NHСО), 10.41 br.s (1Н, NHСО), 13.24 br.s (1Н,
N1H). Mass spectrum, m/z (Irel, %): 471.2 (100) [М + 1]+.
Found, %: С 68.86; Н 5.42; N 11.84. С27H26N4O2S.
Calculated, %: С 68.91; Н 5.57; N 11.91. M 470.598.
1
1681 (СОNH), 1653 [δ(NH2)], 1200 (С=S). Н NMR
spectrum, δ, ppm: 0.94 d (6Н, 2СН3, J 6.3 Hz), 1.55–
1.62 m (1Н, СНМе2), 2.10 s (3H, СН3), 2.34 s (3Н,
СН3), 3.70 d (1Н, С4Н, J 7.4 Hz), 4.03 s (1Н, С3Н),
6.88 t (1Н, Нarom, J 7.2 Hz), 6.95–7.31 m (6Н, Нarom),
8.19 d (1Н, Нarom, J 8.0 Hz), 8.51 br.s (Н, NH2), 9.36
br.s (Н, NH2), 9.81 br.s (1Н, NHCO), 10.25 br.s (1Н,
NHCO), 12.55 br.s (1Н, N1H). Mass spectrum, m/z
(Irel, %): 437.2 (100) [М + 1]+. Found, %: С 66.18; Н
6.35; N 12.74. C24H28N4O2S. Calculated, %: С 66.03;
Н 6.47; N 12.83. M 436.581.
6-Amino-4-methyl-2-thioxo-N3,N5-diphenyl-
1,2,3,4-tetrahydropyridine-3,5-dicarboxamide (IIIg).
Yield 0.65 g (34%), yellow powder, mp 211–213°C
(EtOH). IR spectrum, ν, cm-1: 3188–3398 (NH, NH2),
1
1674 (СОNH), 1615 [δ(NH2)], 1173 (С=S). Н NMR
spectrum, δ, ppm: 1.02 d (3Н, СН3, J 6.4 Hz), 3.75 d
(1Н, С4Н, J 6.4 Hz), 3.80 s (1Н, С3Н), 6.92 t (1Н,
Н
arom, J 7.2 Hz), 7.05 t (1Н, Нarom, J 6.8 Hz), 7.22 t
6-Amino-2-thioxo-N3,N5-di-o-tolyl-4-ethyl-1,2,3,4-
tetrahydropyridine-3,5-dicarboxamide (IIId). Yield
0.50 g (47%), white powder, mp 178–180°C (EtOH).
IR spectrum, ν, cm–1: 3314–3158 (NH, NH2), 1668
(СОNH), 1638 [δ(NH2)], 1195 (С=S). 1Н NMR
spectrum, δ, ppm: 0.92 t (3Н, СН3, J 6.9 Hz), 1.23–
1.38 m (1Н, СН2), 1.40–1.51 m (1Н, СН2), 2.12 s (3H,
СН3), 2.34 s (3Н, СН3), 3.84 s (1Н, С3Н), 3.86–3.91 m
(1Н, С4Н), 6.88 t (1Н, Нarom, J 7.3 Hz), 7.00–7.25 m
(6Н, Нarom), 8.19 s (1Н, Нarom), 8.21 br.s (1Н, NH2),
9.50 br.s (1Н, NH2), 9.73 br.s (1Н, NHСО), 10.29 br.s
(1Н, NHСО), 12.45 br.s (1Н, N1H). Mass spectrum,
m/z (Irel, %): 423.2 (100) [М + 1]+. Found, %: С 65.49;
Н 6.07; N 13.10. C23H26N4O2S. Calculated, %: С
65.38; Н 6.20; N 13.26. M 422.53.
(2Н, Нarom, J 7.2 Hz), 7.30 t (2Н, Нarom, J 7.2 Hz),
7.45–7.72 m (4Н, Нarom), 9.20 br.s (2Н, NH2), 10.44
br.s (2Н, 2NHCO), 13.25 br.s (1Н, N1H). Mass
spectrum, m/z (Irel, %): 381.1 (100) [М + 1]+. Found,
%: С 63.22; Н 5.37; N 14.84. С20H20N4O2S.
Calculated, %: С 63.14; Н 5.30; N 14.73. M 380.463.
Synthesis of compounds (Va–Vo) (general proce-
dure). To a suspension of 0.5 mmol of compound
IIIa–IIIg in 15 ml of ethanol under stirring was added
0.26 ml (0.5 mmol) of 10% aqueous KOH solution.
After 10 min to the reaction mixture was added
0.5 mmol of appropriate alkyl halide IVa–IVf. The
mixture was kept for 24 h. The formed precipitate was
filtered off, washed with water, cold methanol and
ethanol, then dried in a vacuum.
6-Amino-4-n-hexyl-N3,N5-di-o-tolyl-2-thioxo-
1,2,3,4-tetrahydropyridine-3,5-dicarboxamide (IIIe).
Yield 1.27 g (53%), yellow powder, mp 188–190°C
(EtOH). IR spectrum, ν, cm–1: 3188–3415 (NH, NH2),
6-Allylsulfanyl-2-amino-4-isobutyl-N3,N5-di-o-
tolyl-3,4-dihydropyridine-3,5-dicarboxamide (Va).
Yield 0.12 g (50%), white powder, mp 224–226°C
(EtOH). IR spectrum, ν, cm–1: 3211–3412 (NH, NH2),
1
1670 (СОNH), 1635 [δ(NH2)], 1198 (С=S). Н NMR
1
1666 (СОNH), 1641 [δ(NH2)]. Н NMR spectrum, δ,
spectrum, δ, ppm: 0.82 t (3Н, СН3, J 6.4 Hz), 1.10–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

4-ALKYL-6-AMINO-4-N3,N5-DIARYL-2-THIOXO-1,2,3,4-…: I.
1399
ppm: 0.93 d (6Н, 2СН3, J 5.3 Hz), 1.06–1.20 m (1Н,
СН2), 1.28–1.40 m (1Н, СН2), 1.66–1.81 m (1Н,
СНМе2), 2.16 s (3H, СН3), 2.23 s (3Н, СН3), 3.39 br.s
Yield 0.19 g (79%) of yellow crystals, mp 158–160°C
(EtOH). IR spectrum, ν, cm–1: 3154, 3304, 3429 (NH,
NH2), 1675 (СОNH), 1627 [δ(NH2)]. 1Н NMR
spectrum, δ, ppm: 0.88 d (6Н, 2СН3, J 5.7 Hz), 1.03–
1.11 m (1Н, СН2), 1.26–1.36 m (1Н, СН2), 1.63–1.73
m (1Н, СНМе2), 2.27 s (3H, СН3), 2.28 s (3Н, СН3),
3.24 s (1Н, С3Н), 3.28–3.45 m (2Н, С4Н, SСН2), 3.73
d.d (1Н, SСН, J 13.5, J 6.3 Hz), 4.86 d (1Н, =СН2,
Jcis 9.8 Hz), 5.07 d (1Н, =СН2, Jtrans 16.7 Hz), 5.77–
5.87 m (1Н, СН=), 6.83 d (1Н, Нarom, J 7.1 Hz), 6.89 d
(1Н, Нarom, J 7.2 Hz), 7.15 t (1Н, Нarom, J 7.7 Hz), 7.20
t (1Н, Нarom, J 7.8 Hz), 7.29–7.51 m (6Н, 4Нarom, NH2),
9.21 br.s (1Н, NHСО), 9.60 br.s (1Н, NHСО). 13С
NMR spectrum, δС, ppm: 21.62, 21.67, 22.92, 23.94,
25.03, 33.17, 34.62, 42.91, 48.76, 111.45, 116.48,
117.10, 117.29, 120.39, 120.63, 123.91, 124.63, 128.81,
129.00, 136.47, 138.08, 138.30, 139.31, 139.90, 149.26,
159.04, 167.03, 167.08. Mass spectrum, m/z (Irel, %):
491.2 (100) [М + 1]+. Found, %: С 68.38; Н 6.87; N
11.30. C28H34N4O2S. Calculated, %: С 68.54; Н 6.99;
N 11.42. M 490.674.
2
3
(2Н, С3Н and С4Н), 3.47 d.d (1Н, SСН2, J 13.2, J
6.3 Hz), 3.74 d.d (1Н, SСН2, 2J 13.3, 3J 6.4 Hz), 4.87 d
(1Н, =СН2, Jcis 9.4 Hz), 5.11 d (1Н, =СН2, Jtrans 16.6 Hz),
5.76–5.90 m (1Н, СН=), 7.02 t (1Н, Нarom, J 8.0 Hz),
7.15–7.24 m (5Н, Нarom), 7.34 d (1Н, Нarom, J 7.6 Hz),
7.47 br.s (2Н, NH2), 7.65 d (1Н, Нarom, J 7.7 Hz), 8.74
br.s (1Н, NHСО), 8.88 br.s (1Н, NHСО). Mass
spectrum, m/z (Irel, %): 491.2 (100) [М + 1]+. Found,
%: С 68.37; Н 6.84; N 11.37. C28H34N4O2S.
Calculated, %: С 68.54; Н 6.98; N 11.42. M 490.674.
2
3
Ethyl-2-[6-amino-4-isobutyl-3,5-di(o-tolylcarba-
moyl)-4,5-dihydropyridine-2-ylsulfanyl]acetate (Vb).
Yield 0.086 g (32%), white powder, mp 161–163°C
(EtOH). IR spectrum, ν, cm–1: 3214–3433 (NH, NH2),
1
1712 (С=О), 1666 (СОNH), 1635 [δ(NH2)]. Н NMR
spectrum, δ, ppm: 0.80–1.05 m (6Н, 2СН3), 1.11 t (3Н,
СН3, J 7.0, Hz), 1.20–1.37 m (2Н, СН2), 1.66–1.77 m
(1Н, СНМе2), 2.15 s (3H, СН3), 2.22 s (3Н, СН3),
2
3.35 br.s (2Н, С3Н and С4Н), 3.68 d (1Н, SСН2, J
2-Amino-6-benzylsulfanyl-4-isobutyl-N3,N5-di-
m-tolyl-3,4-dihydropyridine-3,5-dicarboxamide (Ve).
Yield 0.16 g (58%), white powder, mp 192–194°C
(EtOH). IR spectrum, ν, cm–1: 3198–3413 (NH, NH2),
2
15.9 Hz), 3.85 d (1Н, SСН2, J 15.9 Hz), 3.97 m (2Н,
ОСН2), 7.00–7.35 m (7Н, Нarom), 7.51 d (1Н, Нarom, J
8.0 Hz), 7.54 br.s (1Н, NH2), 7.61 br.s (1Н, NH2), 8.64
br.s (1Н, NHСО), 8.72 br.s (1Н, NHСО). Mass
spectrum, m/z (Irel, %): 537.4 (100) [М + 1]+. Found,
%: С 64.73; Н 6.64; N 10.38. C29H36N4O4S. Cal-
culated, %: С 64.90; Н 6.76; N 10.44. M 536.70.
1
1677 (СОNH), 1640 [δ(NH2)]. Н NMR spectrum, δ,
ppm: 0.89 d (6Н, 2СН3, J 4.3 Hz), 1.05–1.19 m (1Н,
СН2), 1.23–1.37 m (1Н, СН2), 1.60–1.76 m (1Н,
СНМе2), 2.25 s (3H, СН3), 2.29 s (3Н, СН3), 3.36 t
(1Н, С4Н, J 6.4 Hz), 3.43 s (1Н, С3Н), 4.07 d (1Н,
SСН2, 2J 13.2 Hz), 4.33 d (1Н, SСН2, 2J 13.3 Hz), 6.80
d (1Н, Нarom, J 7.3 Hz), 6.89 d (1Н, Нarom, J 7.3 Hz),
7.01–7.65 m (13Н, 11Нarom, NH2), 8.96 br.s (1Н,
NHСО), 9.86 br.s (1Н, NHСО). Mass spectrum, m/z
(Irel, %): 541.2 (100) [М + 1]+. Found, %: С 71.12; Н
6.67; N 10.40. C32H36N4O2S. Calculated, %: С 71.08;
Н 6.71; N 10.36. М 540.73.
2-Amino-4-isobutyl-6-[2-(4-methoxyphenylamino)-
2-oxoethylsulfanyl]-N3,N5-di-o-tolyl-3,4-dihydro-
pyridine-3,5-dicarboxamide (Vc). Yield 0.163 g
(53%), yellowish green powder, mp 198–200°C
(EtOH). IR spectrum, ν, cm–1: 3212–3415 (NH, NH2),
1
1682 (СОNH), 1633 [δ(NH2)]. Н NMR spectrum, δ,
ppm: 0.93 d (6Н, 2СН3, J 5.8 Hz), 1.09–1.22 m (1Н,
СН2), 1.26–1.40 m (1Н, СН2), 1.68–1.82 m (1Н,
СНМе2), 2.14 s (3H, СН3), 2.20 s (3Н, СН3), 3.42 t
(1Н, С4Н, J 7.6 Hz), 3.48 s (1Н, С3Н), 3.64 d (1Н,
6-Allylsulfanyl-2-amino-4-isopropyl-N3,N5-di-o-
tolyl-3,4-dihydropyridine-3,5-dicarboxamide (Vf).
Yield 0.09 g (37%), yellowish green powder, mp 192–
194°C (EtOH). IR spectrum, ν, cm–1: 3208–3444 (NH,
NH2), 1666 (СОNH), 1634 [δ(NH2)]. 1Н NMR
spectrum, δ, ppm: 0.93 d (3Н, СН3, J 6.3 Hz), 0.97 d
(3Н, СН3, J 6.3 Hz), 1.56–1.74 m (1Н, СНМе2), 2.16 s
(3H, СН3), 2.22 s (3Н, СН3), 3.09 d (1Н, С4Н, J
7.2 Hz), 3.45 d.d (1Н, SСН2, 2J 13.4, 3J 6.6 Hz), 3.55 s
(1Н, С3Н), 3.73 d.d (1Н, СН2, 2J 13.4, 3J 6.6 Hz), 4.85
d (1Н, =СН2, Jcis 9.4 Hz), 5.10 d (1Н, =СН2, Jtrans 17.3
2
SСН2, J 14.2 Hz), 3.69 s (3Н, ОСН3), 3.89 d (1Н,
2
SСН2, J 14.2 Hz), 6.73 d (2Н, Нarom, J 8.5 Hz), 6.98–
7.27 m (7Н, Нarom), 7.32 d (2Н, Нarom, J 8.5 Hz), 7.46 d
(1Н, Нarom, J 7.6 Hz), 7.77 br.s (2Н, NH2), 8.86 br.s
(1Н, NHСО), 9.11 br.s (1Н, NHСО), 9.95 br.s (1Н,
NHСО). Mass spectrum, m/z (Irel, %): 614.4 (100)
[М + 1]+. Found, %: С 66.63; Н 6.32; N 11.47.
C34H39N5O4S. Calculated, %: С 66.53; Н 6.41; N
11.41. М 613.782.
6-Allylsulfanyl-2-amino-4-isobutyl-N3,N5-di-m-
tolyl-3,4-dihydropyridine-3,5-dicarboxamide (Vd).
Hz), 5.73–5.90 m (1Н, СН=), 7.02 t (1Н, Нarom
,
,
J 7.2 Hz), 7.05–7.27 m (5Н, Нarom), 7.34 d (1Н, Нarom
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1400
DYACHENKO, KARPOV
J 7.6 Hz), 7.49 br.s (2Н, NH2), 7.57 d (1Н, Нarom, J
7.6 Hz), 8.72 br.s (1Н, NHСО), 8.86 br.s (1Н, NHСО).
Mass spectrum, m/z (Irel, %): 477.2 (100) [М + 1]+.
Found, %: С 68.11; Н 6.82; N 11.59. C27H32N4O2S.
Calculated, %: С 68.04; Н 6.77; N 11.76. М 476.636.
(1Н, СН=), 6.90–7.65 m (10Н, 8Нarom, NH2), 8.71 br.s
(1Н, NHСО), 8.98 br.s (1Н, NHСО). Mass spectrum,
m/z (Irel, %): 519.3 (100) [М + 1]+. Found, %: С 69.52;
Н 7.25; N 10.71. C30H38N4O2S. Calculated, %: С
69.46; Н 7.38; N 10.80. М 518.729.
6-Allylsulfanyl-2-amino-4-ethyl-N3,N5-di-o-tolyl-
3,4-dihydropyridine-3,5-dicarboxamide (Vl). Yield
0.17 g (73%), white powder, mp 151–153°C (EtOH).
IR spectrum, ν, cm–1: 3295–3416 (NH, NH2), 1665
2-Amino-6-benzylsulfanyl-4-n-hexyl-N3,N5-di-o-
tolyl-3,4-dihydropyridine-3,5-dicarboxamide (Vj).
Yield 0.16g (58%), yellowish green crystals, mp 173–
175°C (EtOH). IR spectrum, ν, cm–1: 3198–3446 (NH,
NH2), 1672 (СОNH), 1630 [δ(NH2)]. 1Н NMR
spectrum, δ, ppm: 0.86 t (3Н, СН3, J 6.8 Hz), 1.10–
1.55 m (10Н, 5СН2), 2.11 s (6H, 2СН3), 3.45 m (1Н,
С4Н), 3.50 s (1Н, С3Н), 4.12 d (1Н, SСН2, 2J 13.2 Hz),
1
(СОNH), 1639 [δ(NH2)]. Н NMR spectrum, δ, ppm:
0.97 t (3Н, СН3, J 6.4 Hz), 1.25–1.40 m (1Н, СН2),
1.44–1.58 m (1Н, СН2), 2.15 s (3H, СН3), 2.22 s (3Н,
СН3), 3.39–3.54 m (3Н, С3Н, С4Н and SCH2), 3.75 d.d
2
3
2
(1Н, SСН2, J 13.2, J 6.3 Hz), 4.89 d (1Н, =СН2, Jcis
9.9 Hz), 5.12 d (1Н, =СН2, Jtrans 17.0 Hz), 5.78–5.93 m
(1Н, СН=), 7.02 t (1Н, Нarom, J 7.1 Hz), 7.06–7.25 m
(5Н, Нarom), 7.31 d (1Н, Нarom, J 7.6 Hz), 7.50 d (2Н,
NH2, J 19.6 Hz), 7.58 d (1Н, Нarom, J 7.9 Hz), 8.70 br.s
(1Н, NHСО), 8.95 br.s (1Н, NHСО). Mass spectrum,
m/z (Irel, %): 463.2 (100) [М + 1]+. Found, %: С 67.42;
Н 6.37; N 12.09. C26H30N4O2S. Calculated, %: С
67.51; Н 6.54; N 12.11. M 462.619.
4.32 d (1Н, SСН2, J 13.2 Hz), 7.00 t (1Н, Нarom, J
7.2 Hz), 7.02–7.38 m (11Н, Нarom), 7.53 d (1Н, Нarom, J
7.6 Hz), 7.67 br.s (2Н, NH2), 8.63 br.s (1Н, NHСО),
8.94 br.s (1Н, NHСО). Mass spectrum, m/z (Irel, %):
569.2 (100) [М + 1]+. Found, %: С 71.64; Н 7.13; N
9.68. C34H40N4O2S. Calculated, %: С 71.80; Н 7.09; N
9.85. М 568.784.
2-Allylsulfanyl-6-amino-N3,N5-diphenyl-4-(1-phe-
nylethyl)-3,4-dihydropyridine-3,5-dicarboxamide
(Vk). Yield 0.10 g (39%), white powder, mp 215–217°C
(EtOH). IR spectrum, ν, cm–1: 3169–3403 (NH, NH2),
Ethyl-2-[6-amino-3,5-di(o-tolylcarbamoyl)-4-ethyl-
4,5-dihydropyridine-2-ylsulfanyl]acetate (Vh). Yield
0.09 g (36%), white powder, mp 158–160°C (EtOH).
IR spectrum, ν, cm–1: 3211–3408 (NH, NH2), 1715
(С=О), 1661 (СОNH), 1632 [δ(NH2)]. 1Н NMR
spectrum, δ, ppm: 0.96 t (3Н, СН3, J 7.1 Hz), 1.13 t
(3Н, СН3, J 7.1 Hz), 1.23–1.35 m (1Н, СН2), 1.46–
1.57 m (1Н, СН2), 2.16 s (3H, СН3), 2.20 s (3Н, СН3),
3.31 t (1Н, С4Н, J 6.5 Hz), 3.49 s (1Н, С3Н), 3.66 d
(1Н, SСН2, 2J 15.8 Hz), 3.84 d (1Н, SСН2, 2J 15.8 Hz),
3.91–4.04 m (2Н, OСН2), 6.99–7.24 m (6Н, Нarom),
7.28 d (1Н, Нarom, J 7.9 Hz), 7.41 d (1Н, Нarom, J 7.9 Hz),
7.50 br.s (1Н, NH2), 7.66 br.s (1Н, NH2), 8.66 br.s
(1Н, NHCO), 8.69 br.s (1Н, NHСО). Mass spectrum,
m/z (Irel, %): 509.1 (100) [М + 1]+. Found, %: С 63.60;
Н 6.27; N 11.18. C27H32N4O4S. Calculated, %: С
63.76; Н 6.34; N 11.02. М 508.646.
1
1670 (СОNH), 1631 [δ(NH2)]. Н NMR spectrum, δ,
ppm: 1.27 d (3Н, СН3, J 6.8 Hz), 2.64–2.77 m (1Н,
СНМе), 3.38–3.44 m (1Н, SСН2), 3.50 d (1Н, С4Н),
2
3
3.57 s (1Н, С3Н), 3.71 d.d (1Н, SСН2, J 13.4, J
6.5 Hz), 4.86 d (1Н, =СН2, Jcis 9.9 Hz), 5.07 d (1Н,
=СН2, Jtrans 17.0 Hz), 5.72–5.86 m (1Н, СН=), 6.95 t
(1Н, Нarom, J 7.2 Hz), 7.05 t (2Н, Нarom, J 7.2 Hz),
7.09–7.74 m (14Н, 12Нarom, NH2), 8.48 br.s (1Н,
NHСО), 9.52 br.s (1Н, NHСО). Mass spectrum, m/z
(Irel, %): 511.2 (100) [М + 1]+. Found, %: С 70.42; Н
5.80; N 10.84. С30H30N4O2S. Calculated, %: С 70.56;
Н 5.92; N 10.97. M 510.664.
2-Amino-6-[2-(4-bromophenylamino)-2-oxoethyl-
sulfanyl]-N3,N5-diphenyl-4-(1-phenylethyl)-3,4-di-
hydropyridine-3,5-dicarboxamide (Vl). Yield 0.17 g
(51%), yellowish green powder, mp 216–218°C
(EtOH). IR spectrum, ν, cm–1: 3176–3447 (NH, NH2),
6-Allylsulfanyl-2-amino-4-n-hexyl-N3,N5-di-o-
tolyl-3,4-dihydropyridine-3,5-dicarboxamide (Vi).
Yield 0.07g (27%), yellowish green powder, mp 147–
149°C (EtOH). IR spectrum, ν, cm–1: 3225–3407 (NH,
NH2), 1669 (СОNH), 1641 [δ(NH2)]. 1Н NMR
spectrum, δ, ppm: 0.86 t (3Н, СН3, J 6.6 Hz), 1.05–
1.60 m (10Н, 5СН2), 2.15 s (3H, СН3), 2.22 s (3Н,
СН3), 3.26–3.55 m (3Н, С3Н, С4Н and SCH2), 3.75 d.d
1
1666 (СОNH), 1633 [δ(NH2)]. Н NMR spectrum, δ,
ppm: 1.27 d (3Н, СН3, J 6.9 Hz), 2.73–2.81 m (1Н,
СНМе), 3.55–3.65 m (2Н, С3Н and С4Н), 3.80 d (1Н,
2
2
SСН2, J 15.0 Hz), 3.90 d (1Н, SСН2, J 15.0 Hz),
6.91–7.61 m (21Н, 19Нarom, NH2), 9.14 br.s (1Н,
NHСО), 9.50 br.s (1Н, NHCO), 10.29 br.s (1Н,
NHСО). Mass spectrum, m/z (Irel, %): 684.2 (100)
[М + 2]+. Found, %: С 61.63; Н 4.67; N 10.18.
2
3
(1Н, SСН2, J 13.2, J 6.5 Hz), 4.88 d (1Н, =СН2, Jcis
9.5 Hz), 5.11 d (1Н, =СН2, Jtrans 16.9 Hz), 5.74–5.90 m
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

4-ALKYL-6-AMINO-4-N3,N5-DIARYL-2-THIOXO-1,2,3,4-…: I.
1401
C35H32BrN5O3S. Calculated, %: С 61.58; Н 4.73; N
10.26. М 682.64.
Yield 0.05 g (20%), yellowish green powder, mp 156–
158°C (EtOH). IR spectrum, ν, cm–1: 3199–3418 (NH,
1
NH2), 1664 (СОNH), 1641 [δ(NH2)]. Н NMR spec-
2-Amino-4-methyl-6-[2-(4-methoxyphenylamino)-
2-oxoethylsulfanyl]-N3,N5-diphenyl-3,4-dihydropyri-
dine-3,5-dicarboxamide (Vm). Yield 0.15 g (54%),
yellowish green powder, mp 194–196°C (EtOH). IR
spectrum, ν, cm–1: 3198–3456 (NH, NH2), 1668
trum, δ, ppm: 0.85 d (3Н, СН3, J 6.4 Hz), 1.03 t (3Н,
СН3, J 6.8 Hz), 1.15–1.71 m (14Н, 7СН2), 2.71–2.84
m (2Н, SСН2), 3.00–3.15 m (2Н, С3Н and С4Н), 6.90–
7.11 m (2Н, Нarom), 7.18–7.44 m (4Н, Нarom), 7.48–
7.69 m (4Н, Нarom), 8.40 br.s (1Н, NH2), 9.32 br.s (1Н,
NH2), 9.85 br.s (1Н, NHСО), 10.02 br.s (1Н, NHСО).
Mass spectrum, m/z (Irel, %): 507.4 (100) [М + 1]+.
Found, %: С 68.61; Н 7.62; N 11.11. C29H38N4O2S.
Calculated, %: С 68.74; Н 7.56; N 11.06. М 506.70.
1
(СОNH), 1632 [δ(NH2)]. Н NMR spectrum, δ, ppm:
1.03 d (3Н, СН3, J 6.6 Hz), 3.43 s (1Н, С3Н), 3.45–
3.49 m (1Н, С4Н), 3.71 s (3H, ОСН3), 3.77 d (1Н,
SСН2, 2J 14.6 Hz), 3.86 d (1Н, SСН2, 2J 14.6 Hz), 6.84
d (2Н, Нarom, J 8.7 Hz), 6.99 t (1Н, Нarom, J 7.1 Hz),
7.04 t (1Н, Нarom, J 7.1 Hz), 7.15–7.33 m (4Н, Нarom),
7.47 d (2Н, Нarom, J 8.7 Hz), 7.58 d (2Н, Нarom, J
8.0 Hz), 7.65 d (2Н, Нarom, J 8.4 Hz), 7.79 br.s (2Н,
NH2), 9.45 br.s (1Н, NHСО), 9.93 br.s (1Н, NHСО),
10.06 br.s (1Н, NHСО). Mass spectrum, m/z (Irel, %):
544.2 (100) [М + 1]+. Found, %: С 64.01; Н 5.22; N
12.97. C29H29N5O4S. Calculated, %: С 64.07; Н 5.38;
N 12.88. М 543.65.
REFERENCES
1. Gorobets, E.V., Miftakhov, M.S., and Valeev, F.A.,
Usp. Khim., 2000, vol. 69, no. 12, p. 1091.
2. Tietze, Z.F., Chem. Rev., 1996, vol. 96, no. 1, p. 115.
3. Litvinov, V.P., Usp. Khim., 2003, vol. 72, no 1, p. 75.
4. Dyachenko, V.D., Khim. Geterotsikl. Soed., 2011, no. 6,
p. 939.
6-Allylsulfanyl-2-amino-4-methyl-N3,N5-diphenyl-
3,4-dihydropyridine-3,5-dicarboxamide (Vp). Yield
0.09 g (44%), yellowish green powder, mp 155–157°C
(EtOH). IR spectrum, ν, cm–1: 3202–3415 (NH, NH2),
5. Dyachenko, V.D., Zh. Org. Khim., 2011, vol. 47, no. 10,
p. 1508.
6. Dyachenko, V.D., Nesterov, V.N., and Dyachenko, I.V.,
Russ. J. Gen. Chem., 2011, vol. 81, no. 4, p. 751.
1
1672 (СОNH), 1638 [δ(NH2)]. Н NMR spectrum, δ,
7. Dyachenko, V.D., Pugach, Yu.Yu., and Shishkin, O.V.,
ppm: 1.02 d (3Н, СН3, J 6.5 Hz), 3.25–3.34 m (2Н,
Russ. J. Gen. Chem., 2011, vol. 81, no. 11, p. 2383.
С3Н and С4Н), 3.52 d.d (1Н, SСН2, 2J 13.0, 3J 7.7 Hz),
8. Dyachenko, V.D., Ukr. Khim. Zh., 2006, vol. 72, no. 3,
2
3
3.75 d.d (1Н, SСН2, J 13.0, J 7.7 Hz), 4.96 d (1Н,
=СН2, Jcis 9.8 Hz), 5.15 d (1Н, =СН2, Jtrans 17.0 Hz),
5.82–6.02 m (1Н, СН=), 6.99 t (1Н, Нarom, J 7.0 Hz),
7.03 t (1Н, Нarom, J 7.0 Hz), 7.26 t (2Н, Нarom, J
7.7 Hz), 7.31 t (2Н, Нarom, J 7.7 Hz), 7.40 br.s (1Н,
NH2), 7.48 br.s (1Н, NH2), 7.52–7.68 m (4Н, Нarom),
9.10 br.s (1Н, NHСО), 9.83 br.s (1Н, NHСО). Mass
spectrum, m/z (Irel, %): 421.2 (100) [М + 1]+. Found,
%: С 65.74; Н 5.52; N 13.28. C23H24N4O2S. Cal-
culated, %: С 65.69; Н 5.75; N 13.32. М 420.537.
p. 53.
9. Dyachenko, V.D., Zh. Org. Khim., 2007, vol. 43, no. 2,
p. 278.
10. Dyachenko, V.D. and Chernega, A.N., Khim.
Geterotsikl. Soed., 2006, no. 1, p. 51.
11. Dyachenko, V.D., Ukr. Khim. Zh., 2006, vol. 72, no. 4,
p. 96.
12. Litvinov, V.P., Usp. Khim., 2006, vol. 75l no. 7, p. 645.
13. Zefirov, Yu.V., and Zorkii, P.M., Usp. Khim., 1989,
vol. 58, no. 5, p. 713.
2-Amino-4-methyl-6-n-nonylsulfanyl-N3,N5-di-
phenyl-3,4-dihydropyridine-3,5-dicarboxamide (Vo).
14. Sheldrick, G., Acta Cryst. (A)., 2008, vol. 64, p. 112.
15. Spek, A.L., J. Appl. Cryst., 2003, vol. 36, p. 7.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013