NEW PROCEDURES FOR PREPARING 2,2,3,3-TETRACYANOCYCLOPROPYL KETONES
1433
formed cyclopropane. This fact may be responsible for
the relatively low yield.
of acetophenone were dissolved in a mixture of 10 ml of
isopropyl alcohol and 5 ml of water. The solution was
refluxed until the precipitation of metallic selenium was
complete. The precipitate was separated by decantation.
To the resulting solution, after cooling, we successively
added with stirring 0.66 g (0.01 mol) of malononitrile and
1.45 g (0.01 mol) of bromomalononitrile. The mixture
was stirred for 15 min. The precipitate that formed was
filtered off and washed with isopropyl alcohol. Yield
1.25 g (51%).
EXPERIMENTAL
The reaction progress and product purity were
monitored by TLC on Silufol UV-254 plates (development
by UV irradiation, treatment with iodine vapor, or heat
treatment). The IR spectra were recorded with an FSM-
1202 Fourier IR spectrometer from thin films of samples
1
(6) A solution of 1.52 g (0.01 mol) of phenylglyoxal,
1.32 g (0.02 mol) of malononitrile, and 2.06 g (0.02 mol)
of NaBr in a mixture of 30 ml of dioxane and 30 ml of
water was subjected to electrolysis in a diaphragmless cell
equipped with a C anode and a Fe cathode (area of each
electrode 2 cm2) at 20°C and a constant current density of
100 mAcm–2, with continuous stirring.After the reaction
completion (TLC monitoring), the solvent was separated
by decantation from a tarry liquid which was triturated
with isopropyl alcohol. The precipitate that formed was
filtered off and washed with several portions of isopropyl
alcohol and water. Yield 0.57 g (23%).
prepared as mulls in mineral oil. The H NMR spectra
were taken on a Bruker DRX-500 spectrometer, working
frequency 500.13 MHz, solvent DMSO-d6, internal
reference TMS. The mass spectra were measured with
a Shimadzu GCMS-QP2010S DI device (electron impact,
70 eV).
3-Benzoylcyclopropane-1,1,2,2-tetracarbonitrile
Ia. (1) 1.52 g (0.01 mol) of phenylglyoxal was dissolved
in 20 ml of ethanol, after which 2.9 g (0.02 mol) of
bromomalononitrile and 3.32 g (0.02 mol) of KI in
10 ml of water were added. The mixture was stirred for
15 min. The precipitate that formed was filtered off and
washed with ethanol. If necessary, the precipitate can be
CONCLUSIONS
recrystallized from dioxane. Yield 0.52 g (21%), Tdec
=
211–212°C. The IR and 1H NMR data coincide with those
reported previously [11].
(1) The use of bromomalononitrile or malononitrile
as debrominating agent instead of KI in the Wideqvist
reaction allows the yield of 2,2,3,3-tetracyanocyclopropyl
ketones to be increased and the range of glyoxals that can
be involved in the reaction to be expanded.
(2) 1.52 g (0.01 mol) of phenylglyoxal was dissolved in
20 ml of isopropyl alcohol, after which 4.35 g (0.03mol)
of bromomalononitrile was added, and the mixture was
stirred for 15 min. The precipitate that formed was
filtered off and washed with isopropyl alcohol. Yield
1.03 g (42%).
(2) The procedure allows multicomponent or one-pot
implementation.
ACKNOWLEDGMENTS
(3) To a solution of 1.52 g (0.01 mol) of phenylglyoxal
in 20 ml of isopropyl alcohol, we added 0.66 g
(0.01 mol) of malononitrile and then 1.45 g (0.01 mol) of
bromomalononitrile. The mixture was stirred for 15 min.
The precipitate that formed was filtered off and washed
with isopropyl alcohol. Yield 1.60 g (65%).
The authors are grateful to the Center for Shared Use
in the Field of Nanotechnologies of the Chuvash Republic
for measuring the IR and mass spectra.
REFERENCES
(4) 1.52 g (0.01 mol) of phenylglyoxal and 1.32 g
(0.02 mol) of malononitrile were dissolved in 10 ml of
isopropyl alcohol. To the resulting solution, a solution of
1.6 g (0.02 mol) of bromine in 10 ml of 1 : 1 isopropyl
alcohol–water mixture was added dropwise with vigorous
stirring with a magnetic stirrer. The precipitate that formed
was filtered off and washed with isopropyl alcohol. Yield
1.28 g (52%).
1. Lukin, P.M., Geksatsianotsiklopropan i ego analogi
(Hexacyanocyclopropane and Its Analogs), Cheboksary:
Poryadok, 2002.
2. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E., et al., Zh.
Org. Khim., 2000, vol. 70, no. 8, pp. 1334–1336.
3. Hart, H. and Freeman, F., J. Org. Chem., 1963, vol. 28,
no. 5, pp. 1220–1222.
(5) 1.11 g (0.01 mol) of SeO2 and 1.2 g (0.01 mol)
4. Freeman, F., Synthesis, 1981, no. 12, pp. 925–954.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 82 No. 8 2009