New synthesis of 3-aroylcyclopropane-1,1,2,2-tetracarbonitriles

Full text of DOI:10.1134/S1070428007080295

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 8, pp. 1252−1253. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © I.N. Bardasov, O.V. Kayukova, Ya.S. Kayukov, O.V. Ershov, O.E. Nasakin, 2007, published in Zhurnal Organicheskoi
Khimii, 2007, Vol. 43, No. 8, pp. 1254−1255.
SHORT
COMMUNICATIONS
New Synthesis of 3-Aroylcyclopropane-1,1,2,2-tetracarbonitriles
I. N. Bardasov, O. V. Kayukova, Ya. S. Kayukov, O. V. Ershov, and O. E. Nasakin
Chuvash State University, Cheboksary, 428015 Russia
e-mail: barkas12@mail.ru
Received August 21, 2006
DOI: 10.1134/S1070428007080295
Many 1,1,2,2-tetracyanocyclopropanes were
successfully prepared by Wideqvist reaction. The process
consists in treating carbonyl compounds with
monobromomalonodinitrile in ethanol or water at room
temperature for 0.5–12 h in the presence of potassium
iodide as reductant [1, 2].
and six electron-withdrawing substituents were known
to actively react with iodides [3–6].
Our synthesis of 3-aroylcyclopropane-1,1,2,2-
tetracarbonitriles involves a treatment of substituted
phenylglyoxal monohydrates in 2-propanol solution with
an excess of monobromomalonodinitrile which
simultaneously acts as a reductant converting into
dibromomalonodinitrile.
We developed a new synthesis method for
3-aroylcyclopropane-1,1,2,2-tetracarbonitriles IIa–IIc
based on Wideqvist reaction but without potassium
iodide. The latter was excluded from the reaction to avoid
side processes since the cyclopropanes containing five
We assume the following reaction scheme: The
formed dicyanomethylene derivatives of phenylglyoxal
A react with the second monobromomalonodinitrile
molecule leading to compounds IIa–IIc.
H
CN
CN
O
O
NC
Compounds analogous to cyclopropanes IIa–IIc were
formerly obtained by the reaction of ω-chlorinated
acetophenones with tetracyanoethylene in dioxane
medium [7]. Hence the method we developed is a new
procedure for preparation of 3-aroylcyclopropane-
1,1,2,2-tetracarbonitriles.
Br
Br
OH
OH
Ar
Ar
CN
_H2O
OH
CN
CN
_
Ia Ic
O
H
CN
Br
Br
CN
CN
The structure of synthesized cyclopropanes IIa–IIc
was confirmed by IR, 1H NMR, and mass spectra.
_
Ar
_H2O
,
Br
CN
3-Benzoylcyclopropane-1,1,2,2-tetracarbonitrile
(IIa). To a solution of 1.52 g (0.01 mol) of phenylglyoxal
monohydrate (Ia) in 20 ml of 2-propanol was added at
stirring in one portion 4.35 g (0.03 mol) of monobromo-
malonodinitrile. The mixture was stirred for 15 min, the
separated precipitate was filtered off and washed in
succession with small portions of 2-propanol and water.
Yield 1.96 g (80%), mp 211–212°C (decomp.). IR
spectrum ν, cm–1: 1692.31 (C=O), 2264.03 (C≡N),
A
H
CN
CN
O
NC
CN
Br
Ar
H
Br
CN
NC
O
CN
CN
Ar
_HBr
1
3033.24 (CH). H NMR spectrum (DMSO-d6), δ, ppm:
8.25 d, 7.8 t, 7.6 t (5H, C6H5), 5.65 s (1H, CH of
cyclopropane). Mass spectrum, m/z (Irel, %): 246 (15)
[M]+, 105 (100) [M – 141]+, 77 (60), 51 (40), 38 (10).
CN
IIa IIc
NC
_
Compounds IIb and IIc were prepared similarly.
Ar = C6H5 (a), p-BrC6H4 (b), p-CH3OC6H4 (c).
1252

NEW SYNTHESIS OF 3-AROYLCYCLOPROPANE-1,1,2,2-TETRACARBONITRILES
1253
3-(4-Bromobenzoyl)cyclopropane-1,1,2,2-tetra-
carbonitrile (IIb). Yield 2.76 g (85%), mp 214–215°C
(decomp.). IR spectrum, ν, cm–1: 1691.97 (C=O),
500.13 MHz, solvent DMSO-d6, internal reference TMS.
Mass spectra were measured on Finnigan MAT-INCOS
50 instrument (electron impact 70 eV).
1
2261.30 (C≡N), 3052.48 (C–H). H NMR spectrum
(DMSO-d6), δ, ppm: 8.15 d, 7.85 d (4H, 4-BrC6H4),
5.6 s (1H, CH of cyclopropane). Mass spectrum, m/z
(Irel, %): 324 (10) [M]+, 183 (100) [M – 141]+, 155 (50),
105 (30), 76 (75), 50 (80), 38 (25).
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p. 1220.
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3-(4-Methoxybenzoyl)cyclopropane-1,1,2,2-
tetracarbonitrile (IIc). Yield 2.20 g (80%), mp 204–
205°C (decomp.). IR spectrum, ν, cm–1: 1670.90 (C=O),
3. Yashkanova, O.V., Nasakin, O.E., Urman, Ya.G., Khrusta-
lev, V.N., Nesterov, V.N., Antipin, M.Yu., and Lukin, P.M.,
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1
2260.63 (C≡N), 3023.30 (CH). H NMR spectrum
(DMSO-d6), δ, ppm: 8.2 d, 7.15 d (4H, 4-CH3OC6H4),
3.9 s (3H, CH3O), 5.65 s (1H, CH of cyclopropane).
Mass spectrum, m/z (Irel, %): 276 (25) [M]+, 171 (50)
[M – 105]+, 135 (100) [M – 141]+, 107 (10), 92 (25), 77
(30), 64 (20), 38 (10).
The purity of compounds synthesized was checked
by TLC on Silufol UV-254 plates, development under
UV irradiation, with iodine vapor, or by thermal
decomposition. IR spectra were recorded on a Fourier
spectrometer FSM-1202 from thin film of mulls in
1
mineral oil. H NMR spectra were registered on
a spectrometer Bruker DRX-500, operating frequency
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007