Reaction of 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles with hydrochloric acid

Full text of DOI:10.1134/S1070428009030269

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 3, pp. 475–476. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © O.V. Ershov, K.V. Lipin, V.N. Maksimova, A.V. Eremkin, Ya.S. Kayukov, O.E. Nasakin, 2009, published in Zhurnal Organicheskoi
Khimii, 2009, Vol. 45, No. 3, pp. 484–485.
SHORT
COMMUNICATIONS
Reaction of 4-Aryl-4-oxobutane-1,1,2,2-tetracarbonitriles
with Hydrochloric Acid
O. V. Ershov, K. V. Lipin, V. N. Maksimova, 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 June 10, 2008
DOI: 10.1134/S1070428009030269
We previously reported that tetracyanoalkanones
react with hydrohalic acids to give alkyl-substituted
2-halopyridine-3,4-dicarbonitriles [1] or 2-halo-6-hy-
droxy-1,4,5,6-tetrahydropyridine-3,4,4-tricarbonitriles
[2]. In the present communication we describe a novel
path of this reaction, which is possible only with aryl-
substituted tetracyanoalkanones. 4-Aryl-4-oxobutane-
1,1,2,2-tetracarbonitriles Ia–Ic were found to react
with hydrochloric acid to produce either 6-aryl-
2-chloropyridine-3,4-dicarbonitriles IIa–IIc or
3a-(2-aryl-2-oxoethyl)perhydropyrrolo[3,4-c]pyrrole-
1,3,4,6-tetraones IIIa–IIIc.
nitrile (Ia) in propan-2-ol. After some time, the pre-
cipitate was filtered off and washed with water and
propan-2-ol. Yield 0.41 g (76%), mp 133–134°C. IR
1
spectrum: ν 2228 cm–1 (C≡N). H NMR spectrum, δ,
ppm: 3.87 s (3H, OCH3), 7.14 d and 8.21 d (2H each,
C6H4, J = 9 Hz), 8.79 s (1H, 5-H). Mass spectrum: m/z
269 (Irel 100%). Found, %: C 62.75; H 2.79; N 14.89.
C14H8ClN3O. Calculated, %: C 62.35; H 2.99; N 15.58.
Compounds IIb and IIc were synthesized in
a similar way.
2-Chloro-6-(3,4-dimethoxyphenyl)pyridine-3,4-
dicarbonitrile (IIb). Yield 0.47 g (78%), mp 139–
1
140°C. IR spectrum: ν 2221 cm–1 (C≡N). H NMR
No data were reported previously on the effect of
water on reactions of tetracyanoalkanones with hydro-
gen halides. According to our results, this factor is very
important in the reactions with aryl-substituted tetracy-
anoalkanones: pyridines IIa–IIc are formed in anhy-
drous medium, whereas diimides IIIa–IIIc are ob-
tained in the presence of water. The structure of
compounds IIa–IIc and IIIa–IIIc was confirmed by
the IR, 1H NMR, and mass spectra.
spectrum, δ, ppm: 3.87 s and 3.88 s (3H each, OCH3),
7.17 d (1H, Harom, J = 9 Hz), 7.74 s (1H, Harom, J =
9 Hz), 7.89 d (1H, Harom, J = 9 Hz), 8.86 s (1H, 5-H).
Mass spectrum: m/z 299 (Irel 100%). Found, %:
C 59.75; H 3.45; N 13.42. C15H10ClN3O2. Calculated,
%: C 60.11; H 3.36; N 14.02.
2-Chloro-6-(4-methoxyphenyl)-5-methylpyri-
dine-3,4-dicarbonitrile (IIc). Yield 0.40 g (75%),
mp 141–142°C. IR spectrum: ν 2228 cm–1 (C≡N).
1H NMR spectrum, δ, ppm: 2.59 s (3H, CH3), 3.87 s
(3H, OCH3), 7.11 d and 7.65 d (2H each, C6H4, J =
9 Hz). Mass spectrum: m/z 283 (Irel 100%). Found, %:
2-Chloro-6-(4-methoxyphenyl)pyridine-3,4-di-
carbonitrile (IIa). Acetyl chloride, 1.5–2 ml, was
added to a suspension of 0.56 g (2 mmol) of
4-(4-methoxyphenyl)-4-oxobutane-1,1,2,2-tetracarbo-
H
CN
Ar
N
O
O
O
O
NC
CN
CN
O
R
CN
CN
HCl, H2O
HCl
CN
Ar
R
Ar
N
R
O
N
H
IIa–IIc
Ia–Ic
IIIa–IIIc
R = H, Ar = 4-MeOC6H4 (a), 3,4-(MeO)2C6H3 (b); R = Me, Ar = 4-MeOC6H4 (c).
475

ERSHOV et al.
476
C 63.78; H 3.55; N 14.81. C15H10ClN3O. Calculated,
%: 63.50; H 3.75; N 15.01.
IR spectrum, ν, cm–1: 1667–1751 (C=O), 3225 (NH).
1H NMR spectrum, δ, ppm: 1.21 d (3H, CH3, J =
7 Hz), 3.86 s (3H, OCH3), 4.37 s (1H, 6a-H), 4.45 q
(1H, CHCH3, J = 7 Hz), 7.07 d and 7.97 d (2H each,
C6H4, J = 9 Hz), 11.73 s and 12.00 s (1H each, NH).
Mass spectrum: m/z 330 (Irel 2%). Found, %: C 61.29;
H 4.67; N 9.34. C16H14N2O6. Calculated, %: C 58.18;
H 4.27; N 8.48.
3a-[2-(4-Methoxyphenyl)-2-oxoethyl]perhydro-
pyrrolo[3,4-c]pyrrole-1,3,4,6-tetraone (IIIa). Con-
centrated hydrochloric acid, 10 ml, was added under
stirring to a suspension of 0.56 g (2 mmol) of com-
pound Ia in propan-2-ol. After 2–3 h, the precipitate
was filtered off and washed with water and propan-
2-ol. Yield 0.52 g (81%), mp 286–288°C (decomp.).
IR spectrum, ν, cm–1: 3309, 3184 (NH); 1670–1750
(C=O). 1H NMR spectrum, δ, ppm: 3.85 s (3H, OCH3),
3.91 s (2H, CH2), 3.93 s (1H, CH), 7.05 d and 7.94 d
(2H each, C6H4, J = 9 Hz), 11.82 s (2H, NH). Mass
spectrum: m/z 316 (Irel 2%). Found, %: C 56.06;
H 3.49; N 8.98. C15H12N2O6. Calculated, %: C 56.96;
H 3.82; N 8.86.
The IR spectra were recorded from samples
dispersed in mineral oil on an FSM-1202 spectrometer
1
with Fourier transform. The H NMR spectra were
measured on a Bruker DRX-500 instrument at
500.13 MHz using DMSO-d6 as solvent and tetra-
methylsilane as internal reference. The mass spectra
(electron impact, 70 eV) were obtained on a Finnigan
MAT Incos-50 spectrometer. The purity of the products
was checked by TLC on Silufol UV-254 plates; spots
were visualized under UV light, by treatment with
iodine vapor, or by thermal treatment.
Compounds IIIb and IIIc were synthesized in
a similar way.
3a-[2-(3,4-Dimethoxyphenyl)-2-oxoethyl]per-
hydropyrrolo[3,4-c]pyrrole-1,3,4,6-tetraone (IIIb).
Yield 0.53 g (76%), mp 231–232°C (decomp.). IR
spectrum, ν, cm–1: 3308, 3175 (NH); 1669–1747
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-97015r-Povolzh’e-a). The authors thank the
Nanotechnology Collective Use Center of the Chuvash
Republic for recording the IR and mass spectra.
1
(C=O). H NMR spectrum, δ, ppm: 3.81 s and 3.85 s
(3H each, OCH3), 3.93 s (2H, CH2), 3.94 s (1H, CH),
7.07 d (1H, Harom, J = 8 Hz), 7.42 s (1H, Harom), 7.65 d
(1H, Harom, J = 8 Hz), 11.81 s (2H, NH). Mass spec-
trum: m/z 346 (Irel 4%). Found, %: C 56.15; H 4.12;
N 8.34. C16H14N2O7. Calculated, %: C 55.49; H 4.07;
N 8.09.
REFERENCES
1. Nasakin, O.E., Nikolaev, E.G., Terent’ev, P.B., Bu-
lai, A.Kh., and Lavrent’eva, I.V., Khim. Geterotsikl.
Soedin., 1987, p. 653.
3a-[2-(4-Methoxyphenyl)-1-methyl-2-oxoethyl]-
perhydropyrrolo[3,4-c]pyrrole-1,3,4,6-tetraone
(IIIc). Yield 0.47 g (75%), mp 275–277°C (decomp.).
2. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E., Chernush-
kin, A.N., and Tafeenko, V.A., Russ. J. Org. Chem., 2002,
vol. 38, p. 1001.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009