ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 4, pp. 617–618. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © K.V. Lipin, V.N. Maksimova, O.V. Ershov, A.V. Eremkin, Ya.S. Kayukov, O.E. Nasakin, 2010, published in Zhurnal Organicheskoi
Khimii, 2010, Vol. 46, No. 4, pp. 623–624.
SHORT
COMMUNICATIONS
Three-Component Synthesis of 2-Chloropyridine-
3,4-dicarbonitriles
K. V. Lipin, V. N. Maksimova, O. V. Ershov, A. V. Eremkin,
Ya. S. Kayukov, and O. E. Nasakin
I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: oleg.ershov@mail.ru
Received November 19, 2008
DOI: 10.1134/S107042801004038X
According to published data, tetracyanoethylene
reacts with ketones in the presence of a catalytic
amount of hydrochloric acid to give 4-oxoalkane-
1,1,2,2-tetracarbonitriles [1, 2]. It is also known that
concentrated hydrochloric acid reacts with 4-oxoal-
kane-1,1,2,2-tetracarbonitriles to produce 2-chloropyri-
dine-3,4-dicarbonitriles [3]. These data suggest that
2-chloropyridine-3,4-dicarbonitriles could be prepared
via one-pot procedure, i.e., without isolation of 4-oxo-
alkane-1,1,2,2-tetracarbonitriles, which should make
their preparation simpler and less expensive.
ensured higher yield and shorter reaction time. Com-
pounds IIb and IId–IIf were not reported previously.
2-Chloro-5,6-dimethylpyridine-3,4-dicarbo-
nitrile (IIa). Tetracyanoethylene, 0.64 g (0.005 mol),
was added to a solution of 0.45 g (0.006 mol) of butan-
2-one in 10 ml of 1,4-dioxane, 5 ml of concentrated
hydrochloric acid was then added, and the mixture was
stirred for 1–2 h at 60–70°C. When the reaction was
complete (TLC), the mixture was diluted with water,
and the precipitate was filtered off, washed with water
and propan-2-ol, and recrystallized from propan-2-ol.
Yield 0.85 g (89%), mp 72–74°C [3]. IR spectrum, ν,
In fact, three-component reaction of tetracyano-
ethylene with the corresponding ketone Ia–If (ali-
phatic, aromatic, or heterocyclic) and hydrochloric
acid in 1,4-dioxane afforded substituted 2-chloropyri-
dine-3,4-dicarbonitriles IIa–IIf in 86–97% yield. The
structure of compounds IIa–IIf was confirmed by IR,
1H NMR, and mass spectra.
1
cm–1: 2233 (C≡N), 1561, 1535 (C=C). H NMR spec-
trum, δ, ppm: 2.56 s (3H, CH3), 2.68 s (3H, CH3).
Mass spectrum: m/z 191 (Irel 57%). Found, %: C 55.98;
H 3.15; N 21.58. C9H6ClN3. Calculated, %: C 56.41;
H 3.16; N 21.93. M 191.62.
Compounds IIb–IIf were synthesized in a simi-
lar way.
CN
O
2-Chloro-5-ethyl-6-methylpyridine-3,4-dicarbo-
nitrile (IIb). Yield 0.95 g (93%), mp 46–48°C. IR
spectrum, ν, cm–1: 2234 (C≡N), 1554 (C=C). 1H NMR
spectrum, δ, ppm: 1.19 t (3H, CH3, J = 8 Hz), 2.66 s
(3H, CH3), 2.86 q (2H, CH2, J = 8 Hz). Mass spec-
trum: m/z 205 (Irel 45%). Found, %: C 57.98; H 3.15;
N 20.02. C10H8ClN3. Calculated, %: C 58.41; H 3.92;
N 20.43. M 205.65.
NC
R2
+
+
HCl
CN
R1
CN
Ia–If
CN
R2
CN
Cl
R1
N
IIa–IIf
2-Chloro-5,6,7,8-tetrahydroquinoline-3,4-dicar-
bonitrile (IIc). Yield 1.05 g (97%), mp 95–96°C [3].
IR spectrum, ν, cm–1: 2222 (C≡N), 1539 (C=C).
1H NMR spectrum, δ, ppm: 1.90 m (4H, CH2), 2.89 t
(2H, CH2, J = 6 Hz), 3.09 t (2H, CH2, J = 6 Hz). Mass
spectrum: m/z 217 (Irel 100%). Found, %: C 59.96;
R1 = R2 = Me (a); R1 = Me, R2 = Et (b); R1R2 = (CH2)4 (c),
(CH2)6 (d); R1 = Ph, R2 = H (e); R1 = 2-thienyl, R2 = H (f).
Thus we proposed a one-pot procedure for the syn-
thesis of 2-chloropyridine-3,4-dicarbonitriles, which
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