Synthesis of 4-alkyl(aryl, hetaryl)-2-thioxo-5,6,7,8-tetrahydroquinoline-3- carbonitriles and their derivatives by cross-recyclization of 4-alkyl(aryl, hetaryl)-2,6-diamino-4H-thiopyran-3,5-dicarbonitriles with 4-(cyclohex-1-en-1- yl)-morpholine, alkyl halides, and cyclohexanone

Article abstract of DOI:10.1134/s1070428008030172

Cross recyclization of 4-substituted 2,6-diamino-4H-thiopyran-3,5- dicarbonitriles with 4-(cyclohex-1-en-1-yl)morpholine, alkyl halides, and cyclohexanone gave the corresponding substituted 2-thioxo-1,2,5,6,7,8- hexahydroquinoline-3-carbonitriles, 2-alkylsulfanyl-5,6,7,8-tetrahydroquinoline- 3-carbonitriles, 3-amino-5,6,7,8-tetrahydrothieno[2,3-b]quinoline-2- carboxamides, and 4-oxo-2,2-pentamethylene-1,2,3,4,7,8,9,10- octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinolines. The structure of 3-(4-bromophenyl)-2,2-pentamethylene-11-(2-thienyl)-1,2,3,4,7,8,9,10- octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinoline was proved by X-ray analysis.

Full text of DOI:10.1134/s1070428008030172

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 3, pp. 412–420. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.D. Dyachenko, A.D. Dyachenko, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 3, pp. 415–422.
Synthesis of 4-Alkyl(aryl, hetaryl)-2-thioxo-5,6,7,8-tetrahydro-
quinoline-3-carbonitriles and Their Derivatives by Cross-
Recyclization of 4-Alkyl(aryl, hetaryl)-2,6-diamino-4H-
thiopyran-3,5-dicarbonitriles with 4-(Cyclohex-1-en-1-yl)-
morpholine, Alkyl Halides, and Cyclohexanone
V. D. Dyachenko and A. D. Dyachenko
Taras Shevchenko National Pedagogical University, ul. Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: dvd_lug@online.lg.ua
Received August 9, 2005
Abstract—Cross recyclization of 4-substituted 2,6-diamino-4H-thiopyran-3,5-dicarbonitriles with 4-(cyclo-
hex-1-en-1-yl)morpholine, alkyl halides, and cyclohexanone gave the corresponding substituted 2-thioxo-
1,2,5,6,7,8-hexahydroquinoline-3-carbonitriles, 2-alkylsulfanyl-5,6,7,8-tetrahydroquinoline-3-carbonitriles,
3-amino-5,6,7,8-tetrahydrothieno[2,3-b]quinoline-2-carboxamides, and 4-oxo-2,2-pentamethylene-
1,2,3,4,7,8,9,10-octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinolines. The structure of 3-(4-bromophenyl)-2,2-
pentamethylene-11-(2-thienyl)-1,2,3,4,7,8,9,10-octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinoline was proved
by X-ray analysis.
DOI: 10.1134/S1070428008030172
It was shown previously [1] that cross-recyclization
of 4-aryl-2,6-diamino-4H-thiopyran-3,5-dicarbonitriles
with hydrazines leads to the formation of 4-aryl-2,6-
dihydrazinopyridine-3,5-dicarbonitriles [1]. Cross-
recyclization of the same thiopyran derivatives with
pyridinium ylides gives substituted 3,4-trans-4-aryl-5-
cyano-3-pyridinio-1,2,3,4-tetrahydropyridine-6-
thiolates [2], while analogous reactions with ketones
and 1,3-diketones provide substituted 4-aryl-3-cyano-
pyridine-2(1H)-thiones and 2-amino-4-aryl-3-cyano-
5,6,7,8-tetrahydro-4H-benzo[b]pyran-5-ones [3].
Presumably, the examined cross-recyclization in-
volves opening of the thiopyran ring with formation of
malononitrile (IV) and R-methylidene(cyano)thioacet-
amide A. Stork alkylation of the latter with enamine II
[8] gives intermediate C which undergoes hetero-
cyclization to substituted octahydroquinoline C. De-
pending on the R substituent, quinoline derivatives C
can be transformed along two pathways. The first of
these is dehydrogenation to 4-methyl-2-sulfanyl-8a-
morpholino-1,5,6,7,8,8a-hexahydroquinoline-3-carbo-
nitrile (V), and the second involves simultaneous dehy-
drogenation and elimination of morpholine to form
4-substituted 2-thioxo-1,2,5,6,7,8-hexahydroquinoline-
3-carbonitriles IIIa–IIIg (Scheme 1). The structure of
compounds IIIa–IIIg and V was confirmed by their
physical constants and spectral data (see Experimen-
tal), as well as by chemical tranformations. Alkylation
of thiol V with chloroacetamide (VIa) and chloro-
acetonitrile (VIb) in DMF in the presence of potassium
hydroxide as a base gave sulfides VIIa and VIIb,
respectively. Elimination of morpholine molecule from
compound VIIa on heating in glacial acetic acid result-
ed in the formation of tetrahydroquinoline VIII.
In the present article we report on a new cross-
recyclization of 4-alkyl(aryl, hetaryl)-2,6-diamino-4H-
thiopyran-3,5-dicarbonitriles Ia–Ij with 4-(cyclohex-1-
en-1-yl)morpholine (II) in boiling anhydrous ethanol.
The products were the corresponding 4-substituted
2-thioxo-1,2,5,6,7,8-hexahydroquinoline-3-carboni-
triles IIIa–IIIg (Scheme 1). The same compounds
were synthesized previously from aryl(hetaryl)methyli-
dene(cyano)thioacetamides and cyclohexanone [4] or
4-(cyclohex-1-en-1-yl)morpholine [5], as well as by
condensation of 2-arylmethylidenecyclohexan-1-ones
with cyano(thioacetamide) [6] or recyclization of
4-amino-6-aryl-2,2-pentamethylene-1,3-dithiacyclo-
hex-4-ene-5-carbonitriles [7].
The alkylation of partially hydrogenated substituted
quinolinethiones IIIa–IIIg with alkyl halides VIc–VIg
412

SYNTHESIS OF 4-ALKYL(ARYL, HETARYL)-2-THIOXO-5,6,7,8-...
413
Scheme 1.
R
CN
R
N
O
S
NC
CN
NC
NH2
S
II
·
NH2
·
N
CH2(CN)2 (IV)
R
NH
O
H2N
S
NH2
O
Ia–Ij
A
B
R
Me
Me
CN
CN
SH
CN
HlgCH2Z (VIa, VIb)
KOH
–2[H]
SH
N
H
N
H
N
H
S
Z
N
N
N
R = Me
O
O
O
C
V
VIIa, VIIb
Me
CN
Δ
NH2
N
S
O
–
O
VIII
R
R
R
CN
CN
S
CN
S
VIc–VIg, KOH
C
–2[H]
a
N
SH
N
N
Z
O
–
H
D
IIIa–IIIg
IXa–IXl
NH
VIa, VIk, KOH
O
b
b
VIh, VIk, KOH
b
VIc–VIj, KOH
R
N
R
N
HN
NH2
R'
N
KOH
IXa–IXl
Z
a
a
O
S
S
XIa, XIb
Xa, Xb
I, R = Me2CHCH2 (a), 2-MeC6H4 (b), 4-O2NC6H4 (c), 4-BrC6H4 (d), Ph (e), 4-FC6H4 (f), 2-thienyl (g), Me (h), 5-methylfuran-2-
yl (i), 4-Me2CHC6H4 (j); III, R = 2-MeC6H4 (a), 4-FC6H4 (b), Ph (c), 4-BrC6H4 (d), Me2CHCH2 (e), 2-thienyl (f), 4-O2NC6H4 (g);
VI, Hlg = Cl (a, b, h, i, k), Br (c–g, j); Z = CONH2 (a), CN (b), 2-oxo-2H-chromen-3-ylcarbonyl (c), 4-ClC6H4CO (d), naphthalen-
2-ylcarbonyl (e), CH2=CH (f), 4-BrC6H4CO (g), PhNHCO (h), 3,4-(HO)2C6H3CO (i), EtOCO (j), 4-BrC6H4NHCO (k); VII, Z =
CONH2 (a), CN (b); IX, R = 4-FC6H4, Z = 4-ClC6H4CO (a), R = 4-FC6H4, Z = 2-oxo-2H-chromen-3-ylcarbonyl (b), R =
Me2CHCH2, Z = naphthalen-2-ylcarbonyl (c), R = 4-O2NC6H4, Z = 2-oxo-2H-chromen-3-ylcarbonyl (d); R = 4-BrC6H4, Z =
4-BrC6H4CO (e); R = 4-BrC6H4, Z = CH2=CH (f); R = Ph, Z = 4-ClC6H4CO (g); R = 4-Me2CHC6H4, Z = 2-oxo-2H-chromen-3-yl-
carbonyl (h); R = 4-Me2CHC6H4, Z = PhNHCO (i); R = 5-methylfuran-2-yl, Z = EtOCO (j); R = 5-methylfuran-2-yl, Z =
4-ClC6H4CO (k); R = 5-methylfuran-2-yl, Z = 3,4-(HO)2C6H3CO (l); X, R = 4-Me2CHC6H4, Z = PhNHCO (a); R = 2-thienyl, Z =
4-BrC6H4NHCO (b); XI, R = 2-thienyl, R′ = 4-BrC6H4 (a), R = Me2CHCH2, R′ = H (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

V. DYACHENKO, A. DYACHENKO
414
under analogous conditions regioselectively afforded
sulfides IXa–IXl (method a). Compounds IX can also
be synthesized in a one-pot mode from the correspond-
ing thiopyrans I, enamine II, and alkyl halides VI
without intermediate isolation of tetrahydroquinolines
III (method b).
2225 cm–1 due to stretching vibrations of the conjugat-
ed cyano group. No such band was present in the IR
spectra of 3-aminothienoquinolines X; instead, stretch-
ing and bending vibrations of the amino group in X
gave rise to absorption bands at 3190–3480 and 1645–
1
1666 cm–1, respectively. The H NMR spectra of IX
contained signals from protons in the tetrahydroquino-
line fragment and substituents therein (see Experimen-
tal) and singlets from the SCH2 protons at δ 4.01–
4.89 ppm. The latter signal was lacking in the spectra
of compounds X, but broadened singlets from protons
in the amino group appeared in the region δ 5.64–
6.13 ppm; these data are consistent with the cyclization
of IX into substituted partially hydrogenated thieno-
quinolines X. Apart from spectral methods (see Experi-
mental), the structure of compounds X was proved by
chemical transformations. The known condensation of
cyclohexanone with heterocyclic compounds contain-
ing amino and carboxamide groups at neighboring car-
bon atoms [10, 12] gave the corresponding spiro-fused
heterocyclic systems XIa and XIb (method a) which
are potential antimicrobial agents [12]. The same com-
pounds were synthesized by one-pot reaction of thio-
pyrans I with enamine II, alkyl halides VIa and VIk,
and cyclohexanone (method b).
Sulfides IX are convenient as starting compounds
for the synthesis of fused systems containing a tetrahy-
droquinoline fragment, e.g., 5,6,7,8-tetrahydrothieno-
[2,3-b]quinoline [9] and 1,2,3,4,7,8,9,10-octahydropyr-
imido[4′,5′:4,5]thieno[2,3-b]quinoline [10]. Treatment
of substituted 2-(phenylcarbamoylmethylsulfanyl)-
5,6,7,8-tetrahydroquinoline IXi with alkali gave
3-amino-2-phenylcarbamoyl-5,6,7,8-tetrahydrothieno-
[2,3-b]quinoline Xa (method a) which attracts interest
as intermediate product for the synthesis of compounds
possessing antimicrobial activity [11]. Compounds Xa
and Xb are also readily obtained by cross-recyclization
of thiopyrans Ia and Ig with morpholinocyclohexene
II and alkyl halides VIc and VIj, followed by treat-
ment of the reaction mixture with alkali (method b).
Presumably, in this case intermediate thiol D under-
goes alkylation to sulfide IX, and the subsequent intra-
molecular cyclization of IX yields substituted thieno-
quinolines X.
The structure of compounds IX and X is confirmed
by spectral data. Sulfides IX characteristically dis-
played in the IR spectra absorption band at 2218–
The structure of 3-(4-bromophenyl)-2,2-pentameth-
ylene-11-(2-thienyl)-1,2,3,4,7,8,9,10-octahydropyri-
mido[4′,5′:4,5]thieno[2,3-b]quinoline (XIa) was un-
C16
C28
C15
S2
C17
C27
C14
C25
C7
C18
C26
N2
C5
C4
C13
C6
C1
C10
C8
N3
C19
C24
C23
C3
C9
C12
C11
Br
C20
C2
C22
C21
N1
S1
O1
Structure of the molecule of 3-(4-bromophenyl)-2,2-pentamethylene-11-(2-thienyl)-1,2,3,4,7,8,9,10-octahydropyrimido[4′,5′:4,5]-
thieno[2,3-b]quinolin-4-one (XIa) according to the X-ray diffraction data. Principal bond lengths (Å) and bond angles (deg):
S1–C9 1.77(1), S1–C11 1.76(1), N1–C1 1.34(1), N1–C9 1.32(1), N2–C10 1.37(1), N2–C13 1.48(1), N3–C12 1.33(1), N3–C13 1.51(1),
C9S1C11 90.2(5), C1N1C9 115.4(9), C10N2C13 117.6(7), C12N3C113 120.2(7).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

SYNTHESIS OF 4-ALKYL(ARYL, HETARYL)-2-THIOXO-5,6,7,8-...
415
ambiguously proved by X-ray analysis (see figure). We
thus confirmed the direction of cross-recyclization of
thiopyrans I with enamine II. The central bicyclic
fragment S1N1C1C6–C11 in molecule XIa is planar
within 0.025Å; the dihedral angle between the
N1C1C6–C9 and S1C1C9–C11 rings is as small as 1.3°.
The bond length distribution in the bicyclic system
suggests essential electron density delocalization. The
S2C25–C28 thiophene ring is almost orthogonal to the
above plane for steric reasons: the corresponding di-
hedral angle is equal to 86.0°. The six-membered ring
N2N3C11–C13 is appreciably nonplanar: deviations of
atoms therein from the mean-square plane reach
0.294 Å; it adopts a half-chair conformation with the
following Cramer–Pople parameters [13]: S = 0.63,
Ψ = 7.6, and θ = 53.1°. The benzene ring C19–C24
forms with the N2N3C11–C13 ring a dihedral angle of
74.9°. The cyclohexane ring C13–C18 has an almost un-
distorted chair conformation which is typical of cyclo-
hexane derivatives: the endocyclic angles vary within
a narrow range, from 53.5 to 55.7°. On the other hand,
the C1–C6 cyclohexane ring fused to the bicyclic
system S1N1C1C6–C11 exists in a half-boat conforma-
tion (S = 0.69, Ψ = 28.7, θ = 37.6º). The N3 atom has
a planar–trigonal bond configuration [the sum of the
bond angles is 358(2)°]. Effective conjugation between
the lone electron pair on N3 and π system of the
C1=O1 double bond induces shortening of the N3–C12
bond to 1.37(1) Å against the standard purely single
N(sp2)–C(sp2) bond (1.43–1.45 Å [14, 15]).
synthesis of electron density, and the positions of the
other hydrogen atoms were calculated from geometry
considerations. All hydrogen atoms were included in
the refinement procedure with fixed thermal and posi-
tional parameters. Chebyshev’s weight scheme [17]
with the following four parameters was used: 1.22,
–0.91, 0.73, –0.39. The final divergence factors were
R = 0.061 and RW = 0.061, goodness of fit 1.171. The
residual electron density from the Fourier difference
series was 0.55 and –0.59 e/Å3. Absorption by the
crystal was taken into account by the azimuthal scan-
ning technique [18].
The IR spectra were recorded in mineral oil on
1
an IKS-40 spectrometer. The H NMR spectra were
measured on Bruker WP-100SY (100 MHz; V, VIIa,
VIIb, VIII, IXa, IXb, IXf, IXg, IXk), Gemini-200
(199.975 MHz; IIIa–IIIe, XIa), Bruker AC-200
(200.13 MHz; IXi), Bruker WM-250 (250.13 MHz;
IXc), Bruker AM-300 (300.13 MHz; IXj, IXl), Varian
Mercury-400 (400.397 MHz; Ii, Ij, IXh, XIb), and
Bruker DRX 500 instruments (500.13 MHz; IXd, IXe,
Xa, Xb) using DMSO-d6 as solvent and tetramethyl-
silane as internal reference. The mass spectra (electron
impact, 70 eV) were obtained on a Kratos MS-890
mass spectrometer with direct sample admission into
the ion source (IXe, IXj, Xa, Xb) and a Hewlett–
Packard Chrommas 5890/5972 GC–MS system (IIIf,
XIb; HP-5 MS column; samples were injected as solu-
tions in methylene chloride). The melting points were
determined on a Kofler hot stage. The progress of
reactions and the purity of products were monitored by
TLC on Silufol UV-254 plates using acetone–hexane
(3:5) as eluent; spots were visualized by treatment
with iodine vapor and UV irradiation.
EXPERIMENTAL
The X-ray diffraction data for a 0.37-mm spherical
single crystal of XIa were acquired at room tempera-
ture on an Enraf–Nonius CAD-4 automatic four-circle
diffractometer (MoKα irradiation, λ = 0.71169 Å, scan
rate ratio 2θ/ω = 1.2, θmax = 27º, spherical segment
0 ≤ h ≤ 13, 0 ≤ k ≤ 30, –12 ≤ l ≤ 12). Total of 4916
reflections were measured, 4488 of which were sym-
metry-independent (Rint = 0.062). Monoclinic crystals
with the following unit cell parameters: a = 10.418(2),
b = 23.859(3), c = 10.060(4) Å; β = 92.56(2)º; V =
2948(2) Å3; Z = 4; dcalc = 1.50 g/cm3; μ = 18.1 cm–1;
F(000) = 1155.6, space group P21/c (no. 14). The
structure was solved by the direct method and was
refined by the least-squares procedure in full-matrix
anisotropic approximation using CRYSTALS software
package [16]. The refinement procedure involved
1593 reflections with I > 2σ(I) (316 refined param-
eters, 5.1 reflections per parameter). The positions of
90% of hydrogen atoms were determined by difference
4-Substituted 2,6-diamino-4H-thiopyran-3,5-dicar-
bonitriles Ia–Ij were synthesized according to the pro-
cedure described in [19]. The properties of compounds
Ia [20], Ib [21], Ic [22], Id–If [19], Ig [23], and Ih
[24] were reported previously.
2,6-Diamino-4-(5-methylfuran-2-yl)-4H-thiopyr-
an-3,5-dicarbonitrile (Ii). Yield 1.83 g (71%), color-
less wool-like material, mp 182–184°C (from AcOH).
IR spectrum, ν, cm–1: 3212, 3333, 3479 (NH2); 2210 sh
1
(C≡N); 1647 (δNH2). H NMR spectrum, δ, ppm:
2.26 s (3H, Me), 4.18 s (1H, 4-H), 6.89 d (1H, 3′-H,
J = 2.95 Hz), 6.98 d (1H, 4′-H), 6.67 br.s (4H, NH2).
Found, %: C 55.71; H 3.77; N 21.50. C12H10N4OS.
Calculated, %: C 55.80; H 3.90; N 21.69.
2,6-Diamino-4-(4-isopropylphenyl)-4H-thiopyr-
an-3,5-dicarbonitrile (Ij). Yield 2.40 g (81%), yellow
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

V. DYACHENKO, A. DYACHENKO
416
crystals, mp 236–239°C (from EtOH). IR spectrum, ν,
cm–1: 3190, 3327, 3465 (NH2); 2200 sh (C≡N); 1650
(δNH2). H NMR spectrum, δ, ppm: 1.24 d (6H, Me,
J = 7.12 Hz), 2.86 m (1H, CHMe2), 4.15 s (1H, 4-H),
6.54 br.s (4H, NH2), 7.16 d and 7.22 d (2H each, C6H4,
J = 7.13 Hz). Found, %: C 64.69; H 5.28; N 18.75.
C16H16N4S. Calculated, %: C 64.84; H 5.44; N 18.90.
M 296.39.
4-(4-Nitrophenyl)-2-thioxo-1,2,5,6,7,8-hexa-
hydroquinoline-3-carbonitrile (IIIg). Yield 2.46 g
(79%), yellow powder, mp 252–254°C (from AcOH);
published data [4]: mp 250°C (decomp.).
1
4-Methyl-8a-morpholino-2-sulfanyl-1,5,6,7,8,8a-
hexahydroquinoline-3-carbonitrile (V). 4-(Cyclo-
hex-1-en-1-yl)morpholine (II), 1.64 ml (10 mmol),
was added to a suspension of 1.92 g (10 mmol) of
thiopyran Ih in 25 ml of anhydrous ethanol, and the
mixture was heated for 2 h under reflux. The mixture
was cooled, and the precipitate was filtered off and
washed with anhydrous ethanol and hexane. Yield
2.2 g (75%), yellow powder, mp 237–239°C (sublimes
at 210°C). IR spectrum, ν, cm–1: 3366 (NH), 2223
(C≡N). 1H NMR spectrum, δ, ppm: 1.70 m (4H, CH2),
2.30 s (3H, Me), 2.44 t (2H, CH2, J = 7.12 Hz), 2.68 t
(2H, CH2, J = 7.41 Hz), 3.03 t (4H, CH2NCH2, J =
4.28 Hz), 3.70 t (4H, CH2OCH2), 8.43 br.s (2H, NH,
SH). Found, %: C 61.72; H 7.19; N 14.25. C15H21N3OS.
Calculated, %: C 61.82; H 7.26; N 14.42. M 291.42.
4-Substituted 2-thioxo-1,2,5,6,7,8-hexahydro-
quinoline-3-carbonitriles IIIa–IIIg (general proce-
dure). 4-(Cyclohex-1-en-1-yl)morpholine (II), 1.64 ml
(10 mmol), was added to a suspension of 10 mmol of
the corresponding thiopyran I in 25 ml of anhydrous
ethanol, and the mixture was heated for 2 h under
reflux. The mixture was cooled, diluted with 10% hy-
drochloric acid to pH 5, and left to stand for 24 h. The
precipitate was filtered off and washed with water,
ethanol, and hexane.
4-(2-Methylphenyl)-2-thioxo-1,2,5,6,7,8-hexa-
hydroquinoline-3-carbonitrile (IIIa). Yield 1.79 g
(64%), yellow powder, mp 226–228°C (from AcOH).
IR spectrum, ν, cm–1: 3335 (NH), 2225 (C≡N). 1H NMR
spectrum, δ, ppm: 1.65 m (4H, CH2), 1.80 m (2H,
CH2), 2.12 s (3H, Me), 2.79 t (2H, CH2, J = 6.18 Hz),
7.04 d (1H, Harom, J = 6.14 Hz), 7.30 m (3H, Harom),
13.86 br.s (1H, NH). Found, %: C 72.71; H 5.60;
N 10.11. C17H16N2S. Calculated, %: C 72.82; H 5.75;
N 9.99.
(3-Cyano-4-methyl-8a-morpholino-1,5,6,7,8,8a-
hexahydroquinolin-2-ylsulfanyl)acetamide (VIIa).
Hexahydroquinoline V, 2.91 g (10 mmol), was dis-
solved in 10 ml of dimethylformamide, 5.6 ml
(10 mmol) of 10% aqueous potassium hydroxide and
0.94 g (10 mmol) of chloroacetamide (VIa) were add-
ed in succession, and the mixture was stirred for 2 h
and diluted with an equal volume of water. The precip-
itate was filtered off and washed with water, ethanol,
and hexane. Yield 2.92 g (84%), white powder,
mp 175–177°C. IR spectrum, ν, cm–1: 3159, 3311,
3402, 3478 (NH, NH2); 2228 (C≡N); 1690 (CONH).
1H NMR spectrum, δ, ppm: 1.74 m (4H, CH2), 2.32 s
(3H, Me), 2.44 m (2H, CH2), 2.79 m (2H, CH2),
3.04 m (4H, CH2OCH2), 3.86 m (6H, SCH2,
CH2NCH2), 7.12 br.s and 7.49 br.s (1H each, NH2),
7.87 br.s (1H, NH). Found, %: C 58.49; H 7.09;
N 15.88. C17H24N4O2S. Calculated, %: C 58.60; H 6.94;
N 16.08. M 348.47.
4-(4-Fluorophenyl)-2-thioxo-1,2,5,6,7,8-hexa-
hydroquinoline-3-carbonitrile (IIIb). Yield 1.96 g
(69%), yellow crystals, mp 256–258°C (from AcOH);
published data [25]: mp 258–259°C.
4-Phenyl-2-thioxo-1,2,5,6,7,8-hexahydroquino-
line-3-carbonitrile (IIIc). Yield 1.86 g (70%), yellow
powder, mp 240–242°C (from AcOH); published data
[6]: mp 238°C (decomp.).
4-(4-Bromophenyl)-2-thioxo-1,2,5,6,7,8-hexa-
hydroquinoline-3-carbonitrile (IIId). Yield 2.35 g
(68%), yellow crystals, mp 260–262°C (from AcOH);
published data [26]: mp 261–263°C.
2-(Cyanomethylsulfanyl)-4-methyl-8a-morpho-
lino-1,5,6,7,8,8a-hexahydroquinoline-3-carbonitrile
(VIIb) was synthesized in a similar way from 0.63 ml
(10 mmol) of chloroacetonitrile (VIb). Yield 2.61 g
(79%), white powder, mp 161–162°C. IR spectrum, ν,
4-Isobutyl-2-thioxo-1,2,5,6,7,8-hexahydroquino-
line-3-carbonitrile (IIIe). Yield 1.48 g (60%), yellow
powder, mp 199–201°C (from AcOH); published data
[27]: mp 198–200°C.
1
cm–1: 3321 (NH); 2258, 2222 (C≡N). H NMR spec-
4-(2-Thienyl)-2-thioxo-1,2,5,6,7,8-hexahydro-
quinoline-3-carbonitrile (IIIf). Yield 1.96 g (72%),
yellow crystals, mp 215–217°C (from AcOH); pub-
lished data [4]: mp 220–222°C. Mass spectrum:
m/z 273 (Irel = 100%) [M + 1]+.
trum, δ, ppm: 1.78 m (4H, CH2), 2.36 s (3H, Me),
2.44 m (2H, CH2), 2.88 m (6H, CH2, CH2NCH2),
3.02 m (4H, CH2OCH2), 4.29 s (2H, SCH2), 8.08 br.s
(1H, NH). Found, %: C 61.65; H 6.62; N 17.09.
C17H22N4OS. Calculated, %: C 61.79; H 6.71; N 16.96.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

SYNTHESIS OF 4-ALKYL(ARYL, HETARYL)-2-THIOXO-5,6,7,8-...
417
(3-Cyano-4-methyl-5,6,7,8-tetrahydroquinolin-2-
ylsulfanyl)acetamide (VIII) was obtained by recrys-
tallization of 3.48 g (10 mmol) of compound VIIa
from 15 ml of glacial acetic acid. Yield 2.01 g (77%),
colorless crystals, mp 181–184°C. IR spectrum, ν,
cm–1: 3302, 3407, 3479 (NH2); 2228 (C≡N); 1684
3-carbonitrile (IXd). Yield 3.88 g (78%), mp 259–
261°C (from BuOH). IR spectrum, ν, cm–1: 2219
(C≡N); 1730, 1712 (C=O). 1H NMR spectrum, δ, ppm:
1.59–1.84 m (4H, CH2), 2.33 m (2H, CH2), 2.79 m
(2H, CH2), 4.76 s (2H, SCH2), 7.41 m (2H, Harom),
7.61 d and 8.39 d (2H each, C6H4, J = 7.19 Hz), 7.75 m
(1H, Harom), 7.99 m (1H, Harom), 8.73 s (1H, 4′-H,
chromene). Found, %: C 65.00; H 3.72; N 8.33.
C27H19N3O5S. Calculated, %: C 65.19; H 3.85; N 8.45.
1
(CONH). H NMR spectrum, δ, ppm: 1.78 m (4H,
CH2), 2.32 s (3H, Me), 2.59 m (2H, CH2), 2.81 m (2H,
CH2), 3.88 s (2H, SCH2), 7.12 br.s and 7.53 br.s
(1H each, NH2). Found, %: C 59.60; H 5.66; N 15.88.
C13H15N3OS. Calculated, %: C 59.75; H 5.79; N 16.08.
2-(4-Bromobenzoylmethylsulfanyl)-4-(4-bromo-
phenyl)-5,6,7,8-tetrahydroquinoline-3-carbonitrile
(IXe). Yield 4.39 g (81%), mp 231–233°C (from
AcOH). IR spectrum, ν, cm–1: 2226 (C≡N), 1724
Compounds IXa–IXl were synthesized (method a)
as described above for sulfide VIIa from the corre-
sponding thioxoquinolines IIIa–IIIg and halogen
derivatives VIc–VIj.
1
(C=O). H NMR spectrum, δ, ppm: 1.33–1.82 m (4H,
CH2), 2.25 m (2H, CH2), 2.54 m (2H, CH2), 4.86 s (2H,
SCH2), 7.31 d and 7.72 d (2H each, C6H4, J = 7.79 Hz),
7.87 d and 8.18 d (2H each, C6H4CO, J = 8.02 Hz).
Found, %: C 52.98; H 3.21; N 4.95. C24H18Br2N2OS.
Calculated, %: C 53.16; H 3.35; N 5.17.
2-(4-Chlorobenzoylmethylsulfanyl)-4-(4-fluoro-
phenyl)-5,6,7,8-tetrahydroquinoline-3-carbonitrile
(IXa). Yield 3.22 g (74%), mp 222–224°C (from
AcOH). IR spectrum, ν, cm–1: 2220 (C≡N), 1710
1
(C=O). H NMR spectrum, δ, ppm: 1.45–1.84 m (4H,
2-Allylsulfanyl-4-(4-bromophenyl)-5,6,7,8-tetra-
hydroquinoline-3-carbonitrile (IXf). Yield 2.54 g
(66%), mp 172–174°C (from MeOH). IR spectrum, ν,
CH2), 2.30 t (2H, CH2, J = 17.12 Hz), 2.51 m (2H,
CH2), 4.81 s (2H, SCH2), 7.36 m (4H, 4-FC6H4),
7.65 d and 8.11 d (2H each, 4-ClC6H4, J = 7.92 Hz).
Found, %: C 65.81; H 4.01; N 6.29. C24H18ClFN2OS.
Calculated, %: C 65.98; H 4.15; N 6.41. M 436.94.
1
cm–1: 2228 (C≡N). H NMR spectrum, δ, ppm: 1.42–
1.95 m (4H, CH2), 2.34 t (2H, CH2, J = 6.82 Hz),
2.94 t (2H, CH2, J = 7.02 Hz), 3.94 d (2H, SCH2, J =
6.58 Hz), 5.12 d (1H, =CH2, Jcis = 9.55 Hz), 5.32 d
(1H, =CH2, Jtrans = 17.40 Hz), 5.79–6.14 m (1H, CH=),
7.34 d and 7.74 d (2H each, Harom, J = 7.25 Hz).
Found, %: C 59.06; H 4.22; N 7.09. C19H17Br2N2S.
Calculated, %: C 59.23; H 4.45; N 7.27.
4-(4-Fluorophenyl)-2-(2-oxo-2H-chromen-3-yl-
carbonylmethylsulfanyl)-5,6,7,8-tetrahydroquino-
line-3-carbonitrile (IXb). Yield 3.76 g (80%),
mp 245–247°C (from AcOH). IR spectrum, ν, cm–1:
2224 (C≡N); 1727, 1714 (C=O). 1H NMR spectrum, δ,
ppm: 1.64 m (4H, CH2), 2.30 t (2H, CH2, J = 7.12 Hz),
2.67 t (2H, CH2, J = 7.25 Hz), 4.79 s (2H, SCH2),
7.43–7.51 m (6H, Harom), 7.78 m (1H, Harom), 7.98 d
(1H, Harom, J = 8.01 Hz), 8.76 s (1H, 4′-H, chromene).
Found, %: C 68.84; H 3.95; N 5.81. C27H19FN2O3S.
Calculated, %: C 68.92; H 4.07; N 5.95.
2-(4-Chlorobenzoylmethylsulfanyl)-4-phenyl-
5,6,7,8-tetrahydroquinoline-3-carbonitrile (IXg).
Yield 3.01 g (72%), mp 198–200°C (from AcOH). IR
spectrum, ν, cm–1: 2226 (C≡N), 1727 (C=O). 1H NMR
spectrum, δ, ppm: 1.48–1.82 m (4H, CH2), 2.30 m
(2H, CH2), 2.85 m (2H, CH2), 4.81 s (2H, SCH2),
7.30–7.58 m (5H, Ph), 7.65 d and 8.11 d (2H each,
C6H4, J = 7.99 Hz). Found, %: C 68.69; H 4.42;
N 6.48. C24H19ClN2OS. Calculated, %: C 68.81;
H 4.57; N 6.69.
4-Isobutyl-2-(naphthalen-2-ylcarbonylmethyl-
sulfanyl)-5,6,7,8-tetrahydroquinoline-3-carbonitrile
(IXc). Yield 3.27 g (79%), mp 154–156°C (from
AcOH). IR spectrum, ν, cm–1: 2225 (C≡N), 1709
1
(C=O). H NMR spectrum, δ, ppm: 0.95 d (6H, Me,
b. Enamine II, 1.64 ml (10 mmol), was added to
a suspension of 10 mmol of the corresponding thio-
pyran Ia–Ij in 25 ml of anhydrous ethanol, and the
mixture was heated for 2 h under reflux. The mixture
was cooled, 5.6 ml (10 mmol) of 10% aqueous potas-
sium hydroxide and 10 mmol of the corresponding
halogen derivative VIc–VIg were added in succession
under stirring, and the mixture was stirred for 4 h and
diluted with an equal volume of water. The precipitate
was filtered off, washed with water, ethanol, and hex-
J = 5.13 Hz), 1.60–1.77 m (6H, CH2), 1.95 m (1H,
CHMe2), 2.54 m (2H, CH2), 2.66 d (2H, CH2, J =
5.16 Hz), 4.87 s (2H, SCH2), 7.51–7.73 m (2H, Harom),
7.90–8.05 m (3H, Harom), 8.11 d (1H, Harom, J =
6.02 Hz), 8.76 s (1H, 1′-H). Found, %: C 75.20;
H 6.19; N 6.58. C26H26N2OS. Calculated, %: C 75.33;
H 6.32; N 6.76.
4-(4-Nitrophenyl)-2-(2-oxo-2H-chromen-3-ylcar-
bonylmethylsulfanyl)-5,6,7,8-tetrahydroquinoline-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

V. DYACHENKO, A. DYACHENKO
418
ane, and recrystallized from glacial acetic acid. We
thus obtained compounds IXa–IXl; among these, sul-
fides IXa–IXg were identical in the IR spectra, TLC
data (Rf values), and melting points (no depression of
the melting point was observed on mixing) to those
synthesized according to method a. Yield, %: IXa, 74;
IXb, 68; IXc, 80; IXd, 78; IXe, 72; IXf, 64; IXg, 58.
2-(4-Chlorobenzoylmethylsulfanyl)-4-(5-methyl-
furan-2-yl)-5,6,7,8-tetrahydroquinoline-3-carboni-
trile (IXk). Yield 3.59 g (85%), mp 150–151°C (from
AcOH). IR spectrum, ν, cm–1: 2216 (C≡N), 1710
1
(C=O). H NMR spectrum, δ, ppm: 1.61–1.84 m (4H,
CH2), 2.42 s (3H, Me), 2.59 m (2H, CH2), 2.24 m
(2H, CH2), 4.69 s (2H, SCH2), 6.30 d (1H, 3′-H, J =
2.15 Hz), 6.87 d (1H, 4′-H, J = 2.15 Hz), 7.52 d and
8.07 d (2H each, C6H4, J = 8.57 Hz). Found, %:
C 65.13; H 4.39; N 6.52. C23H19ClN2O2S. Calculated,
%: C 65.32; H 4.53; N 6.62.
4-(4-Isopropylphenyl)-2-(2-oxo-2H-chromen-3-
ylcarbonylmethylsulfanyl)-5,6,7,8-tetrahydroquino-
line-3-carbonitrile (IXh). Yield 3.80 g (77%),
mp 240–242°C (from AcOH). IR spectrum, ν, cm–1:
1
2222 (C≡N), 1717 (C=O). H NMR spectrum, δ, ppm:
2-(3,4-Dihydroxybenzoylmethylsulfanyl)-4-
(5-methylfuran-2-yl)-5,6,7,8-tetrahydroquinoline-3-
carbonitrile (IXl). Yield 3.36 g (80%), white powder,
mp 171–173°C (from AcOH). IR spectrum, ν, cm–1:
1.26 d (6H, Me, J = 6.18 Hz), 1.61 m (2H, CH2),
1.70 m (2H, CH2), 2.35 t (2H, CH2, J = 6.28 Hz),
2.71 t (2H, CH2, J = 6.47 Hz), 2.99 m (1H, CHMe2),
4.74 s (2H, SCH2), 7.21 d and 7.38 d (2H each, C6H4,
J = 7.02 Hz), 7.42 t (1H, Harom, J = 7.62 Hz), 7.49 d
(1H, Harom, J = 7.58 Hz), 7.77 t (1H, Harom, J =
7.62 Hz), 7.96 d (1H, Harom, J = 7.85 Hz), 8.74 s (1H,
4′-H, chromene). Found, %: C 72.70; H 5.11; N 5.42.
C30H26N2O3S. Calculated, %: C 72.85; H 5.30; N 5.66.
1
3540 (OH), 2218 (C≡N), 1704 (C=O). H NMR spec-
trum, δ, ppm: 1.61–1.89 m (4H, CH2), 2.40 s (3H, Me),
2.62–2.81 m (4H, CH2), 4.68 s (2H, SCH2), 6.32 d
(1H, 3′-H, J = 2.84 Hz), 6.80–6.92 m (2H, Harom),
7.35–7.49 m (2H, Harom), 9.14 br.s and 9.62 br.s (1H
each, OH). Mass spectrum, m/z (Irel, %): [M]+ is miss-
ing, 283 (43) [M – 3,4-(HO)2C6H3CO]+, 270 (35), 269
(14), 241 (22), 227 (20), 209 (11), 200 (18), 152 (44),
137 (100) [3,4-(HO)2C6H3CO]+, 109 (33), 81 (22), 77
(17) [Ph]+, 65 (11), 63 (23). Found, %: C 65.52;
H 4.61; N 6.49. C23H20N2O4S. Calculated, %: C 65.70;
H 4.79; N 6.66. M 420.49.
2-[3-Cyano-4-(4-isopropylphenyl)-5,6,7,8-tetra-
hydroquinolin-2-ylsulfanyl]-N-phenylacetamide
(IXi). Yield 3.13 g (71%), mp 192–194°C (from
AcOH). IR spectrum, ν, cm–1: 2224 (C≡N), 1672
1
(CONH). H NMR spectrum, δ, ppm: 1.29 d (6H, Me,
J = 6.14 Hz), 1.52 m (2H, CH2), 1.79 m (2H, CH2),
2.38 t (2H, CH2, J = 6.27 Hz), 2.88 t (2H, CH2, J =
6.33 Hz), 2.99 m (1H, CHMe2), 4.13 s (2H, SCH2),
7.04 t (1H, C6H5, J = 6.95 Hz), 7.21 d and 7.39 d (2H
each, C6H4, J = 7.06 Hz), 7.28 t (2H, C6H5, J =
6.94 Hz), 7.58 d (2H, C6H5, J = 6.96 Hz), 10.14 br.s
(1H, NH). Mass spectrum, m/z (Irel, %): 442 (4)
[M + 1]+, 441 (9) [M]+, 440 (5) [M – 1]+, 349 (100)
[M – PhNH]+, 321 (72), 279 (84), 265 (10), 205 (11),
132 (8), 93 (32) [PhNH2]+, 77 (21) [Ph]+, 65 (14), 43
(12) [CHMe2]+. Found, %: C 73.28; H 5.95; N 9.38.
C27H27N3OS. Calculated, %: C 73.44; H 6.16; N 9.52.
M 441.60.
3-Amino-4-(4-isopropylphenyl)-N-phenyl-
5,6,7,8-tetrahydrothieno[2,3-b]quinoline-2-carbox-
amide (Xa). a. Compound IXi, 4.41 g (10 mmol), was
dissolved in 10 ml of DMF, 5.6 ml (10 mmol) of 10%
aqueous potassium hydroxide was added, and the mix-
ture was stirred for 5 h and diluted with an equal
volume of water. The precipitate was filtered off and
washed in succession with water, ethanol, and hexane.
Yield 3.66 g (83%), yellow crystals, mp 235–237°C
(from AcOH). IR spectrum, ν, cm–1: 3195, 3288, 3410
1
(NH2); 1674 (CONH), 1641 (δNH2). H NMR spec-
trum, δ, ppm: 1.31 d (6H, Me, J = 6.13 Hz), 1.72 m
(2H, CH2), 1.89 m (2H, CH2), 2.40 t (2H, CH2, J =
6.31 Hz), 3.02 m (3H, CH2, CHMe2), 5.64 br.s (2H,
NH2), 7.02 t (1H, Harom, J = 6.92 Hz), 7.28 m (4H,
Ethyl [3-cyano-4-(5-methylfuran-2-yl)-5,6,7,8-
tetrahydroquinolin-2-ylsulfanyl]acetate (IXj). Yield
2.88 g (81%), mp 92–93°C (from EtOH). IR spectrum,
ν, cm–1: 2214 (C≡N), 1740 (C=O). 1H NMR spectrum,
δ, ppm: 1.20 t (3H, CH2CH3, J = 6.19 Hz), 1.68 m
(2H, CH2), 1.77 m (2H, CH2), 2.36 s (3H, Me), 2.68 t
(2H, CH2, J = 6.22 Hz), 2.84 t (2H, CH2, J = 6.19 Hz),
4.01 s (2H, SCH2), 4.12 q (2H, OCH2, J = 6.19 Hz),
6.38 d (1H, 3′-H, J = 2.14 Hz), 6.93 d (1H, 4′-H,
J = 2.14 Hz). Found, %: C 63.89; H 5.42; N 7.76.
C19H20N2O3S. Calculated, %: C 64.02; H 5.66; N 7.86.
H
H
arom), 7.45 d (2H, Harom, J = 7.22 Hz), 7.63 d (2H,
arom, J = 7.34 Hz), 9.23 br.s (1H, NH). Mass spec-
trum, m/z (Irel, %): 443 (6) [M + 2]+, 442 (10) [M + 1]+,
441 (34) [M]+, 349 (100) [M – PhNH]+, 278 (42), 119
(18), 93 (29) [PhNH2]+, 77 (14) [Ph]+, 65 (15), 43 (22)
[CHMe2]+. Found, %: C 73.28; H 6.02; N 9.38.
C27H27N3OS. Calculated, %: C 73.44; H 6.16; N 9.52.
M 484.44.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

SYNTHESIS OF 4-ALKYL(ARYL, HETARYL)-2-THIOXO-5,6,7,8-...
419
b. Compounds Xa and Xb. Enamine II, 1.64 ml
(10 mmol), was added to a suspension of 10 mmol of
thiopyran Ia or Ig in 25 ml of anhydrous ethanol, and
the mixture was heated for 2 h under reflux. The mix-
ture was allowed to cool down, 5.6 ml (10 mmol) of
10% aqueous potassium hydroxide and 10 mmol of
halogen derivative VIh or VIk was added, the mixture
was stirred for 4 h, an additional 5.6 ml (10 mmol) of
10% aqueous potassium hydroxide was added, and the
mixture was stirred for 4 h and diluted with an equal
volume of water. The precipitate was filtered off and
washed with water, ethanol, and hexane. Yield of Xa
3.22 g (73%).
the mixture was heated for 2 h under reflux. The mix-
ture was cooled, 5.6 ml (10 mmol) of 10% aqueous
potassium hydroxide and 10 mmol of halogen deriva-
tive VIa or VIk were added in succession under stir-
ring, the mixture was stirred for 4 h, an additional
5.6 ml (10 mmol) of 10% aqueous potassium hydrox-
ide was added, and the mixture was stirred for 4 h and
diluted with an equal volume of water. The precipitate
was filtered off and washed in succession with water,
ethanol, and hexane, 1.03 ml (10 mmol) of cyclohexa-
none and 25 ml of glacial acetic acid were added, and
the mixture was heated for 2 h under reflux. After
cooling, the precipitate was filtered off and washed
with glacial acetic acid and diethyl ether. Yield 4.79 g
(95%). The Rf value, IR spectrum, and melting point of
XIa coincided with the corresponding parameters of
a sample synthesized as described above according to
method a.
3-Amino-4-(2-thienyl)-5,6,7,8-tetrahydrothieno-
[2,3-b]quinoline-2-carboxamide (Xb). Yield 4.50 g
(93%), yellow–green powder, mp 277–278°C (from
AcOH; sublimes at 220°C); compound Xb shows
fluorescence upon UV urradiation. IR spectrum, ν,
cm–1: 3202, 3334, 3465 (NH2); 1668 (CONH); 1645
(δNH2). 1H NMR spectrum, δ, ppm: 1.70 m (2H, CH2),
1.84 m (2H, CH2), 2.52 m (2H, CH2), 3.00 t (2H, CH2,
J = 6.19 Hz), 6.13 br.s (2H, NH2), 7.20 d (1H, 3′-H,
J = 2.95 Hz), 7.25 d.d (1H, 4′-H, J = 2.40 Hz), 7.35 d
and 7.64 d (2H each, C6H4, J = 7.08 Hz), 7.79 d (1H,
5′-H, J = 3.71 Hz), 9.24 br.s (1H, NH). Mass spectrum,
m/z (Irel, %): 486 (4) [M + 2]+, 485 (10) [M + 1]+, 484
(11) [M]+, 313 (100) [M – BrC6H4NH]+, 171 (9)
[BrC6H4NH]+, 91 (14), 77 (8) [Ph]+, 40 (35). Found,
%: C 54.41; H 3.58; N 8.49. C22H18BrN3OS2. Calculat-
ed, %: C 54.55; H 3.75; N 8.67. M 484.43.
11-Isobutyl-2,2-pentamethylene-1,2,3,4,7,8,9,10-
octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinolin-
4-one (XIb). Yield 3.06 g (80%), white powder,
mp 219–221°C (fluoresces under UV irradiation). IR
spectrum, ν, cm–1: 3190–3266 (NH), 1684 (CONH).
1H NMR spectrum, δ, ppm: 0.92 d (6H, Me, J =
5.12 Hz), 1.27–1.73 m (8H, CH2), 1.84 m (2H, CH2),
2.03 d (2H, CH2CH, J = 5.48 Hz), 2.19 m (1H,
CH2CH), 2.76 m (2H, CH2), 2.93 m (6H, CH2),
5.19 br.s (1H, NH), 7.75 br.s (1H, NHCO). Mass spec-
trum: m/z 384 (Irel = 100%) [M + 1]+. Found, %:
C 68.69; H 7.48; N 11.12. C22H29N3OS. Calculated, %:
C 68.89; H 7.62; N 10.96. M 383.56.
3-(4-Bromophenyl)-2,2-pentamethylene-11-
(2-thienyl)-1,2,3,4,7,8,9,10-octahydropyrimido-
[4′,5′:4,5]thieno[2,3-b]quinolin-4-one (XIa).
a. A mixture of 4.84 g (10 mmol) of compound Xa and
1.03 ml (10 mmol) of cyclohexanone in 25 ml of
glacial acetic acid was heated for 2 h under reflux. The
mixture was cooled, and the yellow crystals were
filtered off and washed with glacial acetic acid and
diethyl ether. Yield 3.84 g (68%), mp 266–268°C. IR
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1
spectrum, ν, cm–1: 3410 (NH), 1712 (C=O). H NMR
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spectrum, δ, ppm: 0.82 m (4H, CH2), 1.01–1.44 m
(6H, CH2), 1.62–1.97 m (4H, CH2), 2.11 m (2H, CH2),
2.99 m (2H, CH2), 4.58 br.s (1H, NH), 7.14 d and
7.58 d (2H each, C6H4, J = 8.00 Hz), 7.32 m (2H, 3′-H,
4′-H), 7.89 d (1H, 5′-H). Found, %: C 59.41; H 4.38;
N 7.30. C28H26BrN3OS2. Calculated, %: C 59.57;
H 4.64; N 7.44. M 564.57.
5. Dyachenko, V.D. and Litvinov, V.P., Khim. Geterotsikl.
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Ser. Khim., 1985, p. 1768.
b. Compounds XIa and XIb. Enamine II, 1.64 ml
(10 mmol), was added to a suspension of 10 mmol of
thiopyran Ia or Ig in 25 ml of anhydrous ethanol, and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

V. DYACHENKO, A. DYACHENKO
420
17. Carruthers, J.R. and Watkin, D.J., Acta Crystallogr.,
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