ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 5, p. 786. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.D. Dyachenko, M.S. Nazarenko, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 5, p. 778.
SHORT
COMMUNICATIONS
Decomposition
of 5-Amino-1,8,8-trimethyl-3-dicyanomethylene-
2
-azabicyclo[2.2.2]oct-5-ene-4,6-dicarbonitrile
at Treatment with Hydrogen Sulfide
V. D. Dyachenko and M. S. Nazarenko
Taras Shevchenko Lugansk National University
Lugansk, 91011 Ukraine; e-mail: dvd_lug@online.lg.ua
Received November 29, 2010
DOI: 10.1134/S1070428011050228
5
-Amino-1,8,8-trimethyl-3-dicyanomethylene-2-
the mixture was maintained in a refrigerator for 24 h.
The formed precipitate was filtered off, washed with
ethanol and hexane. Yield 0.3 g (46%), yellow powder,
azabicyclo[2.2.2]oct-5-ene-4,6-dicarbonitrile (І) we
formerly synthesized by the reaction of malononitrile with
mesityl oxide [1]. Compound I formed also in the con-
densation of malononitrile with acetone in the presence
of bases [2] or of mixture KF–Al O [3]. Its boiling in
xylene results in decomposition into a mixture of 4-ami-
no-6-methyl-3,5-dicyano-2-dicyanomethylenepyridine
and isobutylene [3]. The other reactions of compound I
are unknown.
1
mp 188–190°S (212°C [4]). H NMR spectrum, δ, ppm:
3.79 s (2H, CN ), 9.32 br.s (2H, NH ), 9.62 br.s (2H,
2
2
1
3
NH2). C NMR spectrum was analogous to prebiously
described [5].
2
3
1N NMR spectrum was registered on a spectrometer
Varian Mercury-400 (400.397 MHz) from solution in
DMSO-d with TMS as internal reference. The melting
6
It was demonstrated for the first time that the reac-
tion of 5-amino-1,8,8-trimethyl-3-dicyanomethylene-
-azabicyclo[2.2.2]oct-5-ene-4,6-dicarbonitrile (І) with
hydrogen sulfide in pyridine at 20°S in the presence of
triethylamine afforded the malonic acid dithioamide (ІІ).
The mechanism of decomposition of bicyclic compound
I and its reactions with the other nucleophilic reagents
are under investigation.
point was measured on a Köffler heating block. The reac-
tion progress was monitored by TLC on Silufol UV-254
plates, eluent acetone–hexane, 3:5, development in iodine
vaor and under UV irradiation.
2
REFERENCES
1
. Nesterov, V.N., Dyachenko, V.D., Sharanin, Yu.A., and
Struchkov, Yu.T., Izv. Akad. Nauk, Ser. Khim., 1996, p. 169.
. Tafeenko, V.A., Abramenko, Yu.T., Ivashchenko, A.V., and
Medvedev, S.V., Abstracts of Papers, Vsesoyuzn. soveshch.
2
CN CN
CN
S
S
_
H N
H S Et N
2 3
2
“
Difraktsionnye metody v khimii” (Diffraction Methods in
H N
NH2
2
Chemistry), Suzdal’, 1988, vol. 1, p. 78; Ref. Zh. Khim.,
1989, 8Zh10.
N
H
NC
I
II
3. Nakano, Y., Shi, W.-Y., Nishii, Y., and Igorashi, M., J. Het-
erocycl. Chem., 1999, vol. 36, p. 33.
Malonic acid dithioamide (ІІ). To a dispersion of
.8 g (10 mmol) of compound I in 20 ml of pyridine was
added 1.4 ml (10 mmol) of triethylamine, and a moderate
4. Jehr, H., Guex, W., and Erlenmeyer, H. Helv. Chim. Acta,
1944, vol. 27, p. 970.
5. Afrashteh,A. and Hartke, K., Arch. Pharm., 1988, vol. 321,
p. 909.
2
flow of hydrogen sulfide was bubbled for 2 h.Afterwards
7
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Dyachenko
