Synthesis of 4,6-dimethyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile by condensation of cyanothioacetamide with acetaldehyde and 1-(Prop-1-en-2-yl)piperidine

Article abstract of DOI:10.1134/S1070428016010061

Three-component condensation of cyanothioacetamide with acetaldehyde and 1-(prop-1-en-2-yl)-piperidine afforded 4,6-dimethyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile which was alkylated with alkyl halides to obtain substituted 2-alkylsulfanyl-4,6-dimethylpyridine-3-carbonitriles, (3-amino-4,6-dimethylthieno-[2,3-b]pyridin-2-yl)(4-cyclohexylphenyl)methanone, and 2,2′-[ethane-1,2-diylbis(sulfanediyl)]bis(4,6-dimethylpyridine-3-carbonitrile).

Full text of DOI:10.1134/S1070428016010061

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 1, pp. 32–36. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © I.V. Dyachenko, V.D. Dyachenko, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 1, pp. 40–43.
Synthesis of 4,6-Dimethyl-2-thioxo-1,2-dihydropyridine-
3-carbonitrile by Condensation of Cyanothioacetamide
with Acetaldehyde and 1-(Prop-1-en-2-yl)piperidine
I. V. Dyachenko and V. D. Dyachenko
Taras Shevchenko Lugansk University, ul. Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: dyachvd@mail.ru
Received March 21, 2015
Abstract—Three-component condensation of cyanothioacetamide with acetaldehyde and 1-(prop-1-en-2-yl)-
piperidine afforded 4,6-dimethyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile which was alkylated with alkyl
halides to obtain substituted 2-alkylsulfanyl-4,6-dimethylpyridine-3-carbonitriles, (3-amino-4,6-dimethylthieno-
[2,3-b]pyridin-2-yl)(4-cyclohexylphenyl)methanone, and 2,2′-[ethane-1,2-diylbis(sulfanediyl)]bis(4,6-di-
methylpyridine-3-carbonitrile).
DOI: 10.1134/S1070428016010061
Alkyl-substituted 2-oxo(thioxo)-1,2-dihydropyri-
dines are known as biologically active compounds
possessing antitumor [1, 2], anti-HIV [3–5], and anti-
diabetic properties [6]. They are also used for the treat-
ment of Parkinson’s [7] and Alzheimer’s diseases [8].
Therefore, development of new methods for the syn-
thesis of 2-oxo(thioxo)-1,2-dihydropyridine derivatives
and study of their chemical and biological properties
are topical problems.
the action of atmospheric oxygen) yields substituted
1,2-dihydropyridine 4 (Scheme 1). The structure of 4
was confirmed by its chemical transformations. The
alkylation of 4 with alkyl halides 5a–5n in DMF in
the presence of aqueous potassium hydroxide gave
sulfides 6a–6n, which is consistent with the general
behavior of 2-thioxo-3-cyanopyridines [17–19].
When α-bromo ketone 7 was used as alkylating
agent, we isolated 2-(4-cyclohexylbenzoyl)-4,6-di-
methylthieno[2,3-b]pyridin-3-amine (8) as a result of
facile intramolecular cyclization of intermediate 6,
which is typical of substituted pyridines with vicinal
alkylsulfanyl and cyano groups [20–22]. Thienopyri-
dine 8 may be promising for the design of antistress
[23] and antibacterial agents [24]. By reaction of
2 equiv of 4 with 1,2-dibromoethane (9) we obtained
2,2′-[ethane-1,2-diylbis(sulfanediyl)]bis(4,6-dimethyl-
pyridine-3-carbonitrile) (10).
In continuation of our studies on the synthesis of
alkyl-substituted pyridinechalcogenones starting from
aliphatic aldehydes [9–12], in the present work we
examined three-component condensation of cyanothio-
acetamide (1), acetaldehyde (2), and 1-(prop-1-en-2-
yl)piperidine (3) in anhydrous ethanol at 20°C. As
a result, we isolated 4,6-dimethyl-2-thioxo-1,2-dihy-
dropyridine-3-carbonitrile (4) which was synthesized
previously by condensation of acetylacetone with
cyanothioacetamide [13], as well as by Michael-type
reaction (exchange of methylene components) of
2-cyano-2-cyclohexylidenethioacetamide with acetyl-
acetone [14].
The structure of 6a–6n, 8, and 10 was confirmed by
1
spectral methods. Their H NMR spectra contained
singlets from methyl protons (see Experimental) and
a signal from 5-H in the pyridine ring at δ 6.81–
7.12 ppm. The SCH2 protons of 6a–6n resonated in the
1H NMR spectra as a singlet at δ 4.01–4.76 ppm,
which was not observed in the spectrum of 8. Instead,
the latter displayed a broadened singlet at δ 7.99 ppm
due to protons of the amino group, which is typical of
structurally related systems [25–27]. In the IR spectra
It is reasonable to presume intermediate formation
of Knoevenagel condensation product A which reacts
with enamine 3 according to Stork [15] to give adduct
B. Intramolecular transamination [16] of the latter
leads to closure of tetrahydropyridine ring (interme-
diate C), and dehydrogenation of C (presumably, by
32

SYNTHESIS OF 4,6-DIMETHYL-2-THIOXO-1,2-DIHYDROPYRIDINE-3-CARBONITRILE
33
Scheme 1.
CH2
Me
Me
N
Me
CN
CN
S
H2N
3
CN
+
MeCHO
H2N
··
H2N
–H2O
N
Me
S
S
1
2
A
B
Me
Me
Me
N
CN
S
CN
S
CN
[O]
RHlg (5a–5n), KOH
NH
–
Me
N
H
Me
N
H
Me
SR
C
4
6a–6n
Me
NH2
O
Me
KOH
4
+
N
Br
S
O
7
8
Me
Me
CN
N
KOH
S
Br
4
+
Br
S
N
NC
Me
Me
9
10
5, 6, Hlg = Br, R = BuOC(O)CH2 (a), 2-(2-oxo-2H-chromen-3-yl)-2-oxoethyl (b), 3,4-(HO)2C6H3C(O)CH2 (c), 4-FC6H4C(O)CH2 (d),
2-oxo-2-(thiophen-2-yl)ethyl (e), PhC(O)CH2 (f), PhC(O)CHCHMe2 (g), 2-MeC6H4CH2 (h), HC≡CCH2 (i), 2-ClC6H4CH2 (j);
Hlg = Cl, (Me)2CHOC(O)CH2 (k), PrOC(O)CH2 (l), PhCH2 (m), PhCHC(O)NH2 (n).
tored by TLC on Silufol-254 plates using acetone–
hexane (3:5) as eluent; spots were visualized by
treatment with iodine vapor and under UV light.
of 6a–6n and 10 we observed a characteristic absorp-
tion band at 2214‒2225 cm–1 due to stretching vibra-
tions of the conjugated cyano group and carbonyl
stretching band at 1695‒1714 cm–1.
4,6-Dimethyl-2-thioxo-1,2-dihydropyridine-3-
carbonitrile (4). A mixture of 0.6 mL (10 mmol) of
freshly distilled acetaldehyde (2), 1.0 g (10 mmol) of
cyanothioacetamide (1), and a drop of N-methylmor-
pholine in 20 mL of anhydrous ethanol was stirred for
20 min at 20°C, 1.3 g (10 mmol) of enamine 3 was
added, and the mixture was stirred for 1 h and left to
stand for 24 h. The mixture was then treated with 10%
aqueous HCl until pH 5 and kept for 5 h, and the pre-
cipitate was filtered off and washed with ethanol and
hexane. Yield 1.1 g (70%), yellow crystals, mp 263‒
265°C (from EtOH); published data [13]: mp 264°C.
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 spectrometer at 400.397 MHz from solutions in
DMSO-d6 containing tetramethylsilane as internal
standard. The mass spectra (electron impact, 70 eV)
were obtained on an Agilent GC/MS instrument;
samples were introduced in a CF3COOH matrix. The
elemental compositions were determined on a Perkin
Elmer CHN analyzer. The melting points were mea-
sured on a Kofler hot stage. The progress of reactions
and the purity of the isolated compounds were moni-
Alkylation of compound 4 (general procedure). To
a mixture of 1.64 g (10 mmol) of compound 4 and
15 mL of DMF we added under stirring in succession
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

I. DYACHENKO, V. DYACHENKO
34
5.6 mL (10 mmol) of 10% aqueous KOH and 10 mmol
of alkylating agent 5a–5n or 7. The mixture was stirred
for 4 h and diluted with an equal volume of water, and
the precipitate of 6a–6n or 8 was filtered off, and
washed with water, ethanol, and hexane.
(84%), mp 115‒116°C (from AcOH). IR spectrum, ν,
cm–1: 2214 (C≡N), 1700 (C=O). 1H NMR spectrum, δ,
ppm: 2.15 s (3H, Me), 2.38 s (3H, Me), 4.74 s (2H,
CH2), 7.03 s (1H, 5-H), 7.29 d.d (1H, 4′-H, J =
5.2 Hz), 8.04 d (1H, 3′-H, J = 4.6 Hz), 8.18 d (1H,
5′-H, J = 3.7 Hz). Mass spectrum: m/z 289 (Irel 100%)
[M + 1]+. Found, %: C 58.22; H 4.06; N 9.67.
C14H12N2OS2. Calculated, %: C 58.31; H 4.19; N 9.71.
M 288.392.
Butyl 2-(3-cyano-4,6-dimethylpyridin-2-ylsul-
fanyl)acetate (6a). Yield 2.2 g (79%), mp 56°C (from
MeOH). IR spectrum, ν, cm–1: 2225 (C≡N), 1695
(C=O). 1H NMR spectrum, δ, ppm: 0.84 t (3H, Me, J =
6.2 Hz), 1.09‒1.68 m (4H, CH2), 2.42 s (6H, Me),
4.01 s (2H, SCH2), 4.07 t (2H, OCH2, J = 6.6 Hz),
7.12 s (1H, 5-H). Mass spectrum: m/z 279 (Irel 100%)
[M + 1]+. Found, %: C 60.28; H 6.41; N 9.95.
C14H18N2O2S. Calculated, %: C 60.41; H 6.52;
N 10.06. M 278.375.
4,6-Dimethyl-2-[(2-oxo-2-phenylethyl)sulfanyl]-
pyridine-3-carbonitrile (6f). Yield 2.2 g (78%),
mp 118–120°C (from AcOH). IR spectrum, ν, cm–1:
1
2218 (C≡N), 1705 (C=O). H NMR spectrum, δ, ppm:
1.19 s (3H, Me), 1.33 s (3H, Me), 4.62 s (2H, CH2),
6.81 s (1H, 5-H), 7.41 t (2H, Ph, J = 7.0 Hz), 7.52 t
(1H, Ph, J = 7.0 Hz), 7.91 d (2H, Ph, J = 7.03 Hz).
Mass spectrum: m/z 283 (Irel 100) [M + 1]+. Found, %:
C 67.94; H 4.88; N 9.80. C16H14N2OS. Calculated, %:
C 68.06; H 5.00; N 9.92. M 282.364.
4,6-Dimethyl-2-{[2-oxo-2-(2-oxo-3,4-dihydro-2H-
1-benzopyran-3-yl)ethyl]sulfanyl}pyridine-3-carbo-
nitrile (6b). Yield 2.5 g (72%), mp 212‒214°C (from
AcOH). IR spectrum, ν, cm–1: 2219, 1703, 1699
1
(C=O). H NMR spectrum, δ, ppm: 2.27 s (3H, Me),
4,6-Dimethyl-2-[(3-methyl-1-oxo-1-phenylbutan-
2-yl)sulfanyl]pyridine-3-carbonitrile (6g). Yield
2.5 g (77%), mp 113‒115°C (from AcOH). IR spec-
2.38 s (3H, Me), 4.76 s (2H, CH2), 7.05 s (1H, 5-H),
7.31‒7.58 m (2H, Harom), 7.78 d (1H, Harom, J =
7.5 Hz), 7.98 d (1H, Harom, J = 8.0 Hz), 8.72 s (1H,
4′-H). Mass spectrum: m/z 351 (Irel 100) [M + 1]+.
Found, %: C 65.02; H 3.89; N 7.88. C19H14N2O3S.
Calculated, %: C 65.13; H 4.03; N 8.00. M 350.399.
1
trum, ν, cm–1: 2217 (C≡N), 1714 (C=O). H NMR
spectrum, δ, ppm: 1.01 d and 1.05 d (3H each, Me2CH,
J = 6.4 Hz), 2.07 s (3H, Me), 2.25–2.31 m (1H,
CHMe2), 2.35 s (3H, Me), 3.69 d (1H, SCH, J =
6.0 Hz), 7.00 s (1H, 5-H), 7.55 t (2H, Ph, J = 7.6 Hz),
7.66 t (1H, Ph, J = 7.6 Hz), 8.10 d (2H, Ph, J =
7.6 Hz). Mass spectrum: m/z 325 (Irel 100%) [M + 1]+.
Found, %: C 70.19; H 6.02; N 8.48. C19H20N2OS. Cal-
culated, %: C 70.34; H 6.21; N 8.63. M 324.447.
2-{[2-(3,4-Dihydroxyphenyl)-2-oxoethyl]sul-
fanyl}-4,6-dimethylpyridine-3-carbonitrile (6c).
Yield 2.5 g (80%), mp 109‒111°C (from EtOH). IR
spectrum, ν, cm–1: 3460, 3424 (OH); 2222 (C≡N);
1
1701 (C=O). H NMR spectrum, δ, ppm: 2.32 s (3H,
Me), 2.41 s (3H, Me), 4.66 s (2H, CH2), 6.81 d (1H,
Harom, J = 7.9 Hz), 6.99 s (1H, 5-H), 7.40 s (1H, Harom),
7.49 d (1H, Harom, J = 7.9 Hz), 9.09 br.s (1H, OH),
9.61 br.s (1H, OH). Mass spectrum: m/z 315
(Irel 100%) [M + 1]+. Found, %: C 60.98; H 3.33;
N 8.80. C16H14N2O3S. Calculated, %: C 61.13; H 4.49;
N 8.91. M 314.363.
4,6-Dimethyl-2-{[(2-methylphenyl)methyl]sul-
fanyl}pyridine-3-carbonitrile (6h). Yield 1.8 g
(68%), mp 82‒84°C (from EtOH). IR spectrum:
ν 2217 cm–1 (C≡N). 1H NMR spectrum, δ, ppm: 2.38 s
(3H, Me), 2.55 s (3H, Me), 4.53 s (2H, CH2), 7.06 s
(1H, 5-H), 7.12‒7.23 m (2H, Harom), 7.40 t (2H, Harom
,
J = 7.3 Hz). Mass spectrum: m/z 269 (Irel 100%)
[M + 1]+. Found, %: C 71.52; H 5.94; N 10.30.
C16H16N2S. Calculated, %: C 71.61; H 6.01; N 10.44.
M 268.381.
2-{[2-(4-Fluorophenyl)-2-oxoethyl]sulfanyl}-
4,6-dimethylpyridine-3-carbonitrile (6d). Yield 2.2 g
(72%), mp 113‒115°C (from AcOH). IR spectrum, ν,
cm–1: 2221 (C≡N), 1699 (C=O). 1H NMR spectrum, δ,
ppm: 2.23 s (3H, Me), 2.41 s (3H, Me), 4.72 s (2H,
CH2), 6.99 s (1H, 5-H), 7.22–7.43 m (2H, Harom), 8.09–
8.21 m (2H, Harom). Mass spectrum: m/z 301
(Irel 100%) [M + 1]+. Found, %: C 63.87; H 4.21;
N 9.16. C16H13FN2OS. Calculated, %: C 63.98; H 4.36;
N 9.33. M 300.354.
4,6-Dimethyl-2-(prop-2-yn-1-ylsulfanyl)pyri-
dine-3-carbonitrile (6i). Yield 2.4 g (70%), mp 87–
89°C (from AcOH). IR spectrum, ν, cm–1: 3310
(≡C−H), 2222 (C≡N), 2240 (C≡C). 1H NMR spectrum,
δ, ppm: 2.43 s (3H, Me), 2.51 s (3H, Me), 2.77 s (1H,
≡CH), 4.05 s (2H, CH2), 7.08 s (1H, 5-H). Mass spec-
trum: m/z 203 (Irel 100) [M + 1]+. Found, %: C 65.21;
H 4.80; N 13.69. C11H10N2S. Calculated, %: C 65.32;
H 4.98; N 13.85. M 202.28.
4,6-Dimethyl-2-{[2-oxo-2-(thiophen-2-yl)ethyl]-
sulfanyl}pyridine-3-carbonitrile (6e). Yield 2.4 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

SYNTHESIS OF 4,6-DIMETHYL-2-THIOXO-1,2-DIHYDROPYRIDINE-3-CARBONITRILE
35
cm–1: 3322, 3290, 3198 (NH2); 1711 (C=O); 1644
(δNH). H NMR spectrum, δ, ppm: 1.11–1.52 m (6H,
CH2), 1.64‒1.93 m (5H, CH2CHCH2), 2.51 s (3H, Me),
2-[(4-Chlorobenzyl)sulfanyl]-4,6-dimethylpyri-
dine-3-carbonitrile (6j). Yield 2.1 g (74%), mp 129–
131°C (from EtOH). IR spectrum: ν 2221 cm–1 (C≡N).
1H NMR spectrum, δ, ppm: 2.38 s (3H, Me), 2.53 s
(3H, Me), 4.50 s (2H, CH2), 7.11 s (1H, 5-H), 7.32 d
(2H, Harom, J = 7.9 Hz), 7.49 d (2H, Harom, J = 7.9 Hz).
Mass spectrum, m/z 289 (Irel 100%) [M + 1]+. Found,
%: C 62.19; H 4.39; N 9.62. C15H13ClN2S. Calculated,
%: C 62.38; H 4.54; N 9.70. M 288.801.
1
2.75 s (3H, Me), 7.08 s (1H, 5-H), 7.35 d (2H, Harom
,
J = 8.0 Hz), 7.70 d (2H, Harom, J = 8.0 Hz), 7.99 br.s
(2H, NH2). Mass spectrum: m/z 365 (Irel 100%)
[M + 1]+. Found, %: C 72.36; H 6.51; N 7.54.
C22H24N2OS. Calculated, %: C 72.49; H 6.64; N 7.69.
M 364.512.
2,2′-[Ethane-1,2-diylbis(sulfanediyl)]bis(4,6-di-
methylpyridine-3-carbonitrile) (10) was synthesized
as described above for compounds 6 using 0.45 mL
(5 mmol) of 1,2-dibromoethane (9) as alkylating agent.
Yield 1.2 g (66%), mp 193–195°C (from BuOH). IR
Isopropyl 2-(3-cyano-4,6-dimethylpyridin-2-yl-
sulfanyl)acetate (6k). Yield 2.4 g (90%), mp 80–82°C
(from i-PrOH). IR spectrum, ν, cm–1: 2223 (C≡N),
1
1714 (C=O). H NMR spectrum, δ, ppm: 1.19 d (6H,
Me, J = 5.1 Hz), 2.41 s (3H, Me), 2.43 s (3H, Me),
4.03 s (2H, CH2), 4.73–5.08 m (1H, CHMe2), 7.10 s
(1H, 5-H). Mass spectrum: m/z 265 (Irel 100%) [M + 1]+.
Found, %: C 58.97; H 5.95; N 10.49. C13H16N2O2S.
Calculated, %: C 59.07; H 6.10; N 10.60. M 264.349.
1
spectrum: ν 2225 cm–1 (C≡N). H NMR spectrum, δ,
ppm: 2.40 s (6H, Me), 2.44 s (6H, Me), 3.62 br.s (4H,
CH2), 7.06 s (2H, 5′-H). Mass spectrum: m/z 355
(Irel 100%) [M + 1]+. Found, %: C 60.84; H 5.02;
N 15.76. C18H18N4S2. Calculated, %: C 60.99; H 5.12;
N 15.81. M 354.499.
Propyl 2-(3-cyano-4,6-dimethylpyridin-2-ylsul-
fanyl)acetate (6l). Yield 1.8 g (70%), mp 53‒54°C
(from PrOH). IR spectrum, ν, cm–1: 2227 (C≡N), 1709
(C=O). 1H NMR spectrum, δ, ppm: 0.83 t (3H, Me, J =
6.2 Hz), 1.42–1.73 m (2H, CH2), 2.41 s (3H, Me),
2.42 s (3H, Me), 4.02 t (2H, OCH2, J = 4.7 Hz), 4.08 s
(2H, SCH2), 7.10 s (1H, 5-H). Mass spectrum: m/z 265
(Irel 100%) [M + 1]+. Found, %: C 58.97; H 5.95;
N 10.47. C13H16N2O2S. Calculated, %: C 59.07;
H 6.10; N 10.60. M 264.349.
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5.71 s (1H, SCH), 7.04 s (1H, 5-H), 7.11‒7.45 m (3H,
Ph, NH), 7.47–7.69 m (3H, Ph), 7.86 br.s (1H, NH).
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

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