Synthesis of 4-methylmorpholinium 6-amino-3,5-dicyano-4-(furan-2-yl)pyridine-2-thio(seleno)lates and 3-[aryl(hetaryl)]-2-cyanoprop-2-enethioamides by michael reaction

Article abstract of DOI:10.1134/S1070428014120185

Michael reaction of dimethyl (furan-2-ylmethylidene)malonate with 2-cyanoethanethio(seleno)amides and 4-methylmorpholine afforded 4-methylmorpholinium 6-amino-3,5-dicyano-4-(furan-2-yl)pyridine-2-thio(seleno)lates via exchange of the CH acid components. Aryl(hetaryl)methylidenemalononitriles reacted with cyanoethanethioamide under analogous conditions to give 3-aryl(hetaryl)-2-cyanoprop-2-enethioamides which were converted into 3-aryl(hetaryl)-2-(1,3-thiazol-2-yl)prop-2-enenitriles according to Hantzsch.

Full text of DOI:10.1134/S1070428014120185

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 12, pp. 1821–1825. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © I.V. Dyachenko, E.Yu. Ramazanova, V.D. Dyachenko, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 12,
pp. 1839–1843.
Synthesis of 4-Methylmorpholinium 6-Amino-3,5-dicyano-
4-(furan-2-yl)pyridine-2-thio(seleno)lates and 3-[Aryl(hetaryl)]-
2-cyanoprop-2-enethioamides by Michael Reaction
I. V. Dyachenkoa, E. Yu. Ramazanovab, and V. D. Dyachenkoa
a Taras Shevchenko Lugansk National University, ul.Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: dyachvd@mail.ru
b Donbas State Technical University, pr. Lenina 16, Alchevsk, Lugansk oblast, 94200 Ukraine
Received July 16, 2014
Abstract—Michael reaction of dimethyl (furan-2-ylmethylidene)malonate with 2-cyanoethanethio(seleno)-
amides and 4-methylmorpholine afforded 4-methylmorpholinium 6-amino-3,5-dicyano-4-(furan-2-yl)pyridine-
2-thio(seleno)lates via exchange of the CH acid components. Aryl(hetaryl)methylidenemalononitriles reacted
with cyanoethanethioamide under analogous conditions to give 3-aryl(hetaryl)-2-cyanoprop-2-enethioamides
which were converted into 3-aryl(hetaryl)-2-(1,3-thiazol-2-yl)prop-2-enenitriles according to Hantzsch.
DOI: 10.1134/S1070428014120185
Michael reaction is widely used in the synthesis of
carbo- and heterocycles [1]. One of its versions in-
volving exchange of CH acid components has been
reported in a few publications [2]. This path is typical
of reactions of cyanoacetohydrazides with cinnamo-
nitriles [3], cyanoacetanilides with 2-cyano-3-(furan-2-
yl)-prop-2-enethioamide [4], 2-(benzothiazol-2-yl)-
ethanenitrile with (pyrrol-2-ylmethylidene)malono-
nitrile [5], malononitrile with 2-cyano-3-cycloalkyl-
prop-2-enamides [6], 2-cyanoethanamide with 2-ben-
zoyl-3-(4-nitrophenyl)prop-2-enenitrile [7], 2-[1-aryl-
(hetaryl)ethylidene]malononitriles with 3-aryl-
(hetaryl)-2-cyanoprop-2-enethioamides [8], and 2-cy-
anoethanethioamide with diethyl benzylidenemalonate
or 3-benzylidenepyrazol-2-one [9].
chemoselective intramolecular cyclization yields sub-
stituted pyridine III. Compounds IIIa and IIIb were
isolated as stable 4-methylmorpholinium salts which
were identified by comparing their spectral parameters
with published data [10, 11]. In addition, the alkylation
of IIIa and IIIb with halomethyl compounds IVa and
IVb and N-(4-bromophenyl)-2-chloroethanamide (V)
led to the formation of selenides VIa and VIb and
thieno[2,3-b]pyridine derivative VII. Compound VII
was formed as a result of intramolecular cyclization of
intermediate D through carbanion E. The proposed
scheme for the formation of morpholinium salts IIIa
and IIIb is confirmed by the fact that their yield in-
creased when 2 equiv of CH acid IIa or IIb was used.
The structure of compounds VIa, VIb, and VII was
confirmed by spectral data. In the IR spectra of VIa,
VIb, and VII, absorption bands due to stretching vi-
brations of the carbonyl and conjugated cyano groups
were located at 1711–1714 and 2218–2224 cm–1,
The present article describes new Michael reactions
following the above pattern. Dimethyl (furan-2-yl-
methylidene)malonate (I) reacted with 2-cyanoethane-
thioamide (IIa) and 2-cyanoethaneselenoamide (IIb)
in anhydrous ethanol in the presence of an equimolar
amount of N-methylmorpholine at 20°C under argon to
give 4-methylmorpholinium 6-amino-3,5-dicyano-4-
(furan-2-yl)pyridine-2-thio(seleno)lates IIIa and IIIb
(Scheme 1). Presumably, initially formed Michael
adduct A loses dimethyl malonate molecule with
formation of intermediate B. The latter then acts as
Michael acceptor toward initial CH acid II (Michael
donor) to produce new Michael adduct C whose
1
respectively. The H NMR spectra of VIa and VIb
contained signals from protons in the amino group,
furan ring, and SeCH2C(O)Z fragment (see Experi-
1
mental). Compound VII showed in the H NMR spec-
trum signals from protons in the two amino groups as
broadened singlets at δ 6.34 (3-NH2) and 7.55 ppm
(6-NH2), which is typical of such systems [12].
Under analogous conditions, the Michael reaction
of 2-cyanoethanethioamide (IIa) with [aryl(hetaryl)-
1821

DYACHENKO et al.
1822
Scheme 1.
O
COOMe
X
COOMe
NH2
NMM
COOMe
X
NC
O
+
NH2
–CH2(COOMe)2
O
COOMe
X
NC
CN
NH2
I
IIa, IIb
A
B
O
X
CN
CN
O
NC
NC
Hlg
Z
X–
Se
O
O
IIa, IIb
NH2
O
O
IVa, IVb
Z
H
N
X
–H2X, –2[H]
X = Se
N
N
NC
NC
Me
NH2
NH2
IIIa, IIIb
NH2
C
VIa, VIb
CN
O
H
N
S
O
C6H4Br-4
Cl
C6H4Br-4
IIIa +
N
O
NC
NH2
V
D
O
N
O
C6H4Br-4
KOH
NH2
S
O
NC
O
N
NH2
NC
S
HN C6H4Br-4
H2N
N
E
VII
NMM is N-methylmorpholine; II, III, X = S (a), Se (b); IV, Hlg = Cl, Z = OCH2Ph (a); Hlg = Br, Z = 2-oxo-2H-chromen-3-yl (b);
VI, Z = OCH2Ph (a), 2-oxo-2H-chromen-3-yl (b).
methylidene]malononitriles VIIIa–VIIIe also involved
exchange of the methylene components (path a in
Scheme 2) and produced 3-aryl(hetaryl)-2-cyanoprop-
2-enethioamides IXa–IXe. Presumably, elimination of
malononitrile from primary Michael adduct F yields
poorly soluble unsaturated thioamide IX, and the
equilibrium is displaced toward the latter.
The structure of IXa–IXe was consistent with their
spectral parameters (see Experimental) and was also
confirmed by chemical transformations and indepen-
dent synthesis from aromatic aldehydes Xa–Xe and
cyanothioacetamide (IIa) according to Knoevenagel
(path b). As a qualitative test for thioamide group,
compounds IXa–IXe were brought into the Hantzsch
condensation with α-halocarbonyl compounds XIa–
XId and XII, which afforded the corresponding substi-
tuted thiazoles XIIIa–XIIId and XIV through inter-
mediate sulfides G. Thiazoles XIIIa–XIIId and XIV
attract interest as potential pharmaceutical agents [13].
Likewise, the reaction of (1H-indol-3-ylmethyli-
dene)malononitrile (VIIIe) with 2,2-dimethyl-1,3-di-
oxan-4,6-dione (XV, Meldrum’s acid) in ethanol at
20°C in the presence of an equimolar amount of
4-methylmorpholine gave previously unknown
Meldrum’s acid derivative XVI. Compounds XIIIa–
XIIId, XIV, XVI characteristically showed in the
1H NMR spectra a singlet from the vinylic proton at
δ 7.66–8.55 ppm.
EXPERIMENTAL
The IR spectra were recorded on an IKS-40 spec-
trometer from samples dispersed in mineral oil. The
1H NMR spectra were measured on a Varian Mercury-
400 instrument at 400.397 MHz using DMSO-d6 as
solvent and tetramethylsilane as internal reference. The
mass spectra (electron impact, 70 eV) were obtained
on a Hewlett Packard 5890/5972 GC/MS system
(HP-5 MS column); samples were injected as solutions
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014

SYNTHESIS OF 4-METHYLMORPHOLINIUM 6-AMINO-3,5-DICYANO-...
1823
Scheme 2.
R
CN
CN
IIa, NMM
NC
CN
S
IIa
R
S
R
RCHO
b
a
–CH2(CN)2
CN
CN
H2N
NH2
IXa–IXe
VIIIa–VIIIe
F
Xa–Xe
CN
S
NC
S
N
R'
R
Br
IXa, IXc, IXe
+
–HBr
–H2O
O
R
H2N
R'
O
R'
XIa–XId
G
XIIIa–XIIId
CN
O
S
NMe2
IXb
+
–HBr, –H2O
N
Br
XII
XIV
O
O
O
O
VIIIe
+
O
O
–CH2(CN)2
Me
Me
Me
Me
NH
O
O
XV
XVI
NMM is N-methylmorpholine; VIII–X, R = 3,4-(MeO)2C6H3 (a), 4-Me2HC6H4 (b), 5-phenylfuran-2-yl (c), 5-bromofuran-2-yl (d),
1H-indol-3-yl (e); XI, R′ = Ph (a), thiophen-2-yl (b), 4-MeC6H4 (c), Me2CHCH2 (d); XIII, R = 3,4-(MeO)2C6H3, R′ = Me2CHCH2 (a);
R = 5-phenylfuran-2-yl, R′ = 4-MeC6H4 (b), thiophen-2-yl (c); R = 1H-indol-3-yl, R′ = Ph (d).
in methylene chloride. The melting points were deter-
mined on a Kofler hot stage. The progress of reactions
and the purity of products were monitored by TLC on
Silufol UV254 plates using acetone–hexane (3:5) as
eluent; spots were detected by treatment with iodine
vapor or under UV light.
4-Methylmorpholinium 6-amino-3,5-dicyano-4-
(furan-2-yl)pyridine-2-thiolate (IIIa). Dimethyl (fu-
ran-2-ylmethylidene)malonate (I), 2.1 g (10 mmol),
was dissolved in 25 mL of anhydrous ethanol, 2.0 g
(20 mmol) of CH acid IIa and 1.1 mL (10 mmol) of
4-methylmorpholine were added under stirring at
20°C, and the mixture was stirred for 15 min until it
became homogeneous and left to stand for 48 h. The
precipitate was filtered off and washed with ethanol
and hexane. Yield 2.2 g (63%), mp 233–234°C; pub-
lished data [11]: mp 230–232°C.
3.9 g (10 mmol) of morpholinium salt IIIb and
1.52 mL (10 mmol) of ester IVa in 15 mL of DMF was
stirred for 5 h at 20°C. The mixture was diluted with
an equal volume of water, and the precipitate was fil-
tered off and washed with water, ethanol, and hexane.
Yield 3.1 g (72%), violet needles, mp 192–194°C
(from EtOH). IR spectrum, ν, cm–1: 3384, 3311, 2910
(NH2); 2222 (C≡N), 1714 (C=O), 1645 (δ NH2).
1H NMR spectrum, δ, ppm: 4.24 s (2H, OCH2), 5.16 s
(2H, SeCH2), 7.65 s (1H, 3′-H), 7.30–7.39 m (5H, Ph),
7.44 s (1H, 4′-H), 8.00 br.s (2H, NH2), 8.11 s (1H,
5′-H). Mass spectrum: m/z 438 (Irel 100%) [M + 1]+.
Found, %: C 54.80; H 3.14; N 12.72. C20H14N4O3Se.
Calculated, %: C 54.93; H 3.23; N 12.81.
2-Amino-4-(furan-2-yl)-6-[2-oxo-2-(2-oxo-2H-
chromen-3-yl)ethylselanyl]pyridine-3,5-dicarboni-
trile (VIb) was synthesized as described above for
compound VIa from 2.7 g (10 mmol) of coumarin
derivative IVb. Yield 4.4 g (92%), colorless powder,
mp 245–247°C (from BuOH). IR spectrum, ν, cm–1:
3388, 3300, 3210 (NH2), 2218 (C≡N), 1711 (C=O),
4-Methylmorpholinium 6-amino-3,5-dicyano-4-
(furan-2-yl)pyridine-2-selenolate (IIIb) was synthe-
sized in a similar way from 2.9 g (20 mmol) of
2-cyanoethaneselenoamide (IIb). Yield 2.3 g (60%),
mp 317–320°C; published data [10]: mp 320–323°C.
1
1648 (δNH2). H NMR spectrum, δ, ppm: 4.64 s (2H,
Benzyl 2-[6-amino-3,5-dicyano-4-(furan-2-yl)-
pyridin-2-ylselanyl]ethanoate (VIa). A mixture of
SeCH2), 6.58 s (1H, 3′-H), 7.18–7.32 m (5H, Harom),
7.34 t (1H, Harom, J = 7.5 Hz), 7.95 br.s (2H, NH2),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014

DYACHENKO et al.
1824
8.63 s (1H, 4″-H). Mass spectrum: m/z 476 (Irel 100%)
[M + 1]+. Found, %: C 55.40; H 2.41; N 11.65.
C22H12N4O4Se. Calculated, %: C 55.59; H 2.55;
N 11.79.
and 9.66 br.s (1H each, NH2). Mass spectrum: m/z 232
(Irel 100%) [M + 1]+. Found, %: C 62.22; H 5.55;
N 18.08. C12H13N3S. Calculated, %: C 62.31; H 5.66;
N 18.17.
3,6-Diamino-N-(4-bromophenyl)-5-cyano-4-
(furan-2-yl)thieno[2,3-b]pyridine-2-carboxamide
(VII). To a solution of 3.43 g (10 mmol) of morpho-
linium salt IIIa and 2.5 g (10 mmol) of N-(4-bromo-
phenyl)-2-chloroethanamide (V) in 20 mL of DMF we
added under stirring at 20°C 5.6 mL (10 mmol) of 10%
aqueous potassium hydroxide. The mixture was stirred
for 4 h and diluted with an equal volume of water, and
the precipitate was filtered off and washed with water,
ethanol, and hexane. Yield 3.7 g (81%), yellow
powder, mp 263–265°C (from BuOH). IR spectrum, ν,
cm–1: 3395, 3311, 3198 (NH2); 2224 (C≡N), 1672
2-Cyano-3-(5-phenylfuran-2-yl)prop-2-enethio-
amide (IXc). Yield 1.8 g (70%) (a), 77% (b); red
crystals, mp 153–155°C (from EtOH). IR spectrum, ν,
1
cm–1: 2188–3395 (NH2), 2225 (C≡N). H NMR spec-
trum, δ, ppm: 7.14–7.49 m (4H, Harom), 7.61–8.02 m
(3H, Harom), 8.19 s (1H, CH=), 9.41 br.s and 10.02 br.s
(1H each, NH2). Mass spectrum: m/z 255 (Irel 100%)
[M + 1]+. Found, %: C 66.02; H 3.84; N 10.95.
C14H10N2OS. Calculated, %: C 66.12; H 3.96; N 11.02.
3-(5-Bromofuran-2-yl)-2-cyanoprop-2-enethio-
amide (IXd). Yield 2.0 g (77%) (a), 86% (b); yellow
powder, mp 148–150°C (from EtOH). IR spectrum, ν,
1
(C=O), 1649 (δNH2). H NMR spectrum, δ, ppm:
6.34 br.s (2H, 3-NH2), 6.89 d (1H, 3′-H, J = 2.9 Hz),
1
cm–1: 3195–3312 (NH2), 2202 (C≡N). H NMR spec-
trum, δ, ppm: 6.46 d (1H, 3′-H, J = 3.1 Hz), 7.43 d
(1H, 4′-H, J = 3.1 Hz), 7.94 s (1H, CH=), 9.38 br.s and
10.01 br.s (1H each, NH2). Mass spectrum: m/z 258
(Irel 100%) [M + 1]+. Found, %: C 37.28; H 1.85;
N 10.85. C8H5BrN2OS. Calculated, %: C 37.37;
H 1.96; N 10.90.
7.13 d.d (1H, 4′-H, J = 2.4, 1.1 Hz), 7.47 d (2H, Harom
J = 7.5 Hz), 7.55 br.s (2H, 6-NH2), 7.68 d (2H, Harom
,
,
J = 7.5 Hz), 8.09 d (1H, 5′-H, J = 1.1 Hz), 10.49 br.s
(1H, NHCO). Mass spectrum: m/z 455 (Irel 100%)
[M + 1]+. Found, %: C 50.11; H 2.58; N 15.32.
C19H12BrN5O2S. Calculated, %: C 50.23; H 2.66;
N 15.42.
2-Cyano-3-(1H-indol-3-yl)prop-2-enethioamide
(IXe). Yield 1.7 g (75%) (a), 85% (b); yellow powder,
mp 173–175°C (from EtOH); published data [16]:
mp 174–176°C.
Compounds IXa–IXe (general procedures).
a. A mixture of 10 mmol of [aryl(hetaryl)methylidene]-
malononitrile VIIIa–VIIIe, 1.0 g (10 mmol) of
2-cyanoethanethioamide (IIa), and 1.1 mL (10 mmol)
of 4-methylmorpholine in 20 mL of ethanol was stirred
for 5 h at 20°C and was left to stand for 24 h. The
precipitate was filtered off and washed with ethanol
and hexane.
Compounds XIIIa–XIIId (general procedure).
A mixture of 10 mmol of thioamide IXa–IXd and
10 mmol of α-bromo ketone XIa–XId in 15 mL of
DMF was stirred for 3 h at 20°C, diluted with an equal
volume of water, and left to stand for 24 h. The precip-
itate was filtered off and washed with water, ethanol,
and hexane.
b. A mixture of 10 mmol of aromatic aldehyde Xa–
Xe, 1.0 g (10 mmol) of 2-cyanoethanethioamide (IIa),
and three drops of 4-methylmorpholine in 20 mL of
ethanol was stirred for 5 h at 20°C and was then left to
stand for 24 h. The precipitate was filtered off and
washed with ethanol and hexane.
3-(3,4-Dimethoxyphenyl)-2-(4-isobutyl-1,3-thia-
zol-2-yl)prop-2-enenitrile (XIIIa). Yield 2.3 g (69%),
yellow powder, mp 68–70°C (from EtOH). IR spec-
1
trum: ν 2214 cm–1 (C≡N). H NMR spectrum, δ, ppm:
0.95 d (6H, Me, J = 6.5 Hz), 2.01–2.18 m (1H,
CHMe2), 2.60 d (2H, CH2, J = 7.0 Hz), 3.87 s and
3.88 s (3H each, MeO), 8.97 d (1H, Harom, J = 8.0 Hz),
7.05 s (1H, Harom), 7.45 d (1H, Harom, J = 8.0 Hz),
7.66 s (1H, CH=), 8.02 s (1H, 5″-H). Mass spectrum:
m/z 329 (Irel 100%) [M + 1]+. Found, %: C 65.70;
H 6.02; N 8.47. C18H20N2O2S. Calculated, %: C 65.83;
H 6.14; N 8.53.
2-Cyano-3-(3,4-dimethoxyphenyl)prop-2-ene-
thioamide (IXa). Yield 2.0 g (82%) (a), 75% (b);
yellow crystals, mp 198–200°C (from PhH); published
data [14]: mp 197–201°C.
2-Cyano-3-(4-dimethylaminophenyl)prop-2-ene-
thioamide (IXb). Yield 1.8 g (78%) (a), 84% (b);
yellow crystals, mp 230–232°C (from EtOH); pub-
lished data [15]: mp 231–232°C. IR spectrum, ν, cm–1:
1
3330, 3218, 3177 (NH2); 2200 (C≡N). H NMR spec-
2-[4-(4-Methylphenyl)-1,3-thiazol-2-yl]-3-(5-phe-
nylfuran-2-yl)prop-2-enenitrile (XIIIb). Yield 2.9 g
(79%), yellow crystals, mp 167–169°C (from BuOH).
trum, δ, ppm: 3.07 s (6H, Me), 6.83 d and 7.87 d (2H
each, Harom, J = 8.2 Hz), 8.07 s (1H, CH=), 9.12 br.s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014

SYNTHESIS OF 4-METHYLMORPHOLINIUM 6-AMINO-3,5-DICYANO-...
1825
1
IR spectrum: ν 2213 cm–1 (C≡N). H NMR spectrum,
δ, ppm: 2.38 s (3H, Me), 7.21–7.58 m (6H, Harom),
7.81–8.02 m (5H, Harom), 8.06 s (1H, CH=), 8.11 s (1H,
5″-H). Mass spectrum: m/z 369 (Irel 100%) [M + 1]+.
Found, %: C 74.89; H 4.25; N 7.52. C23H16N2OS. Cal-
culated, %: C 74.98; H 4.38; N 7.60.
8.75 s (1H, CH=), 9.34 s (1H, 2′-H), 12.90 br.s (1H,
NH). Mass spectrum: m/z 270 (Irel 100%) [M – 1]+.
Found, %: C 66.35; H 4.72; N 5.09. C15H13NO4. Cal-
culated, %: C 66.42; H 4.83; N 5.16.
REFERENCES
3-(5-Phenylfuran-2-yl)-2-[4-(thiophen-2-yl)-
1,3-thiazol-2-yl]prop-2-enenitrile (XIIIc). Yield 2.9 g
(80%), yellow powder, mp 143–145°C (from BuOH).
1. Sharanin, Yu.A., Goncharenko, M.P., and Litvinov, V.P.,
Russ. Chem. Rev., 1998, vol. 67, no. 5, p. 393.
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cheskoi khimii (Current Problems of Organic Chem-
istry), Ogloblin, K.A., Ed., Leningrad: Leningr. Gos.
Univ., 1975, p. 89.
3. Hadi, A., Martin, N., Mendez, C., Quinterio, M.,
Seoane, C., Soto, J.L., Albert, A., and Cano, F.H.,
J. Chem. Soc., Perkin Trans. 1, 1993, p. 1743.
1
IR spectrum: ν 2210 cm–1 (C≡N). H NMR spectrum,
δ, ppm: 7.02–7.18 m (2H, Harom), 7.32–7.68 m (7H,
H
arom), 7.85–7.93 m (2H, Harom), 8.05 s (1H, CH=).
Mass spectrum: m/z 361 (Irel 100%) [M + 1]+. Found,
%: C 66.50; H 3.22; N 7.69. C20H12N2OS2. Calculated,
%: C 66.64; H 3.36; N 7.77.
3-(1H-Indol-3-yl)-2-(4-phenyl-1,3-thiazol-2-yl)-
prop-2-enenitrile (XIIId). Yield 2.4 g (73%), yellow
crystals, mp 256–258°C (from BuOH). IR spectrum, ν,
4. Dyachenko, I.V., Dyachenko, V.D., and Rusanov, E.B.,
Russ. J. Org. Chem., 2007, vol. 43, p. 83.
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Czech. Chem. Commun., 1991, vol. 56, p. 418.
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Khim. Zh., 1990, vol. 56, p. 65.
1
cm–1: 3300 (NH), 2215 (C≡N). H NMR spectrum, δ,
ppm: 7.24–7.33 m (2H, Harom), 7.40 t (1H, Harom, J =
7.9 Hz), 7.50 t (2H, Harom, J = 7.5 Hz), 7.58 d (1H,
H
arom, J = 7.5 Hz), 8.01 d (3H, Harom, J = 7.0 Hz),
8.16 s (1H, 5″-H), 8.51d (1H, Harom, J = 3.0 Hz), 8.55 s
(1H, CH=), 12.35 br.s (1H, NH). Mass spectrum:
m/z 328 (Irel 100%) [M + 1]+. Found, %: C 73.20;
H 3.84; N 12.72. C20H13N3S. Calculated, %: C 73.37;
H 4.00; N 12.83.
3-(4-Dimethylaminophenyl)-2-(4,5,6,7-tetra-
hydro-1,3-benzothiazol-2-yl)prop-2-enenitrile (XIV)
was synthesized in a similar way from 2.3 g (10 mmol)
of 2-cyano-3-(4-dimethylaminophenyl)prop-2-ene-
thioamide (IXb) and 1.8 g (10 mmol) of 2-bromo-
cyclohexan-1-one (XII). Yield 2.1 g (69%), yellow
crystals, mp 68–70°C (from PrOH). IR spectrum:
11. Sharanin, Yu.A., Krivokolysko, S.G., and Dyachen-
ko,V.D., Zh. Org. Khim., 1994, vol. 30, p. 581.
12. Dyachenko, V.D. and Litvinov, V.P., Russ. J. Org.
Chem., 1998, vol. 34, p. 554; Dyachenko, V.D., Krivo-
kolysko, S.G., Sharanin, Yu.A., and Litvinov, V.P., Russ.
J. Org. Chem., 1997, vol. 33, p. 1014.
1
ν 2216 cm–1 (C≡N). H NMR spectrum, δ, ppm: 1.81–
13. Bender, W., Betz, U., Kleymann, G., Baumeister, J.,
Eckenberg, P., Fischer, R., Handke-Ergueder, G.,
Hendrix, M., Henningen, K., Vensen, A., Keldemich, J.,
Reefschlöger, J., Schmidt, T., Schneider, U., and
Weber, O., FRG Patent Appl. no. 10210319, 2003; Ref.
Zh., Khim., 2004, no. 19O114P; Khellendal’, B.,
Lanski, A., Rendenbakh-Myuller, B., Bakh, A.,
Unger, L., Teshendorf, Kh.-Yu., and Vike, K., RF Patent
no. 2173687, 2001; Haap, W., Hölzl, W., Ochs, D.,
Puchler, K., and Schnyder, M., EU Patent Appl.
no. 1103180, 2001; Ref. Zh., Khim., 2001, no. 19O327P.
1.92 m (4H, CH2), 2.65–2.71 m (2H, CH2), 2.75–
2.81 m (2H, CH2), 3.08 s (6H, Me), 6.71 d and 7.79 d
(2H each, Harom, J = 8.1 Hz), 7.81 s (1H, CH=). Mass
spectrum: m/z 310 (Irel 100%) [M + 1]+. Found, %:
C 69.75; H 6.11; N 13.42. C18H19N3S. Calculated, %:
C 69.87; H 6.19; N 13.58.
5-[(1H-Indol-3-yl)methylidene]-2,2-dimethyl-
1,3-dioxane-4,6-dione (XVI) was synthesized as
described above for compounds IXa–IXe from 1.9 g
of (10 mmol) dinitrile VIIIe and 1.44 g (10 mmol) of
Meldrum’s acid (XV). Yield 1.9 g (70%), colorless
crystals, mp 234–235°C (from EtOH). IR spectrum, ν,
14. Bloxham, J. and Dell, C.P., J. Chem. Soc., Perkin
Trans. 1, 1994, p. 989.
15. Grinshtein, V.Ya. and Sherin’, L.A., Izv. Akad. Nauk
Latv. SSR, Ser. Khim., 1963, p. 469.
1
cm–1: 3325 (NH), 1714 (C=O). H NMR spectrum, δ,
ppm: 1.72 s (6H, Me), 7.32–7.37 m (2H, Harom), 7.62 d
(1H, Harom, J = 6.4 Hz), 7.91 d (1H, Harom, J = 5.9 Hz),
16. Dyachenko, V.D. and Dyachenko, A.D., Russ. J. Org.
Chem., 2006, vol. 42, p. 1091.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014