Synthesis of 3-Arylcyclopropane-1,1,2,2-tetracarbonitriles under Micellar Catalysis

Article abstract of DOI:10.1134/S1070428018120187

An environmentally benign procedure has been developed for the synthesis of 3-arylcyclopropane- 1,1,2,2-tetracarbonitriles in an aqueous surfactant solution.

Full text of DOI:10.1134/S1070428018120187

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 12, pp. 1839–1841. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © I.N. Bardasov, A.Yu. Alekseeva, D.A. Bezgin, O.V. Ershov, 2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54, No. 12,
pp. 1825–1826.
SHORT
COMMUNICATIONS
Synthesis of 3-Arylcyclopropane-1,1,2,2-tetracarbonitriles
under Micellar Catalysis
I. N. Bardasova,* A. Yu. Alekseevaa, D. A. Bezgina, b, and O. V. Ershova
a I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
*e-mail: bardasov.chem@mail.ru
b Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences,
Leninskii pr. 29, Moscow, 119991 Russia
Received May 16, 2018; revised November 16, 2018; accepted November 16, 2018
Abstract—An environmentally benign procedure has been developed for the synthesis of 3-arylcyclopropane-
1,1,2,2-tetracarbonitriles in an aqueous surfactant solution.
DOI: 10.1134/S1070428018120187
Cyclopropane ring is an important structural unit of
many synthetic and natural biologically active com-
pounds possessing anticancer [1, 2], anticonvulsant
[3], and antimicrobial activity [4, 5] and used in the
treatment of HIV [6] and varicella infections [7].
a surfactant [13]. We used a nonionic surfactant,
cocamidopropyl dimethylamine oxide (OKSIPAV AP),
which successfully catalyzed Knoevenagel condensa-
tion [14]. Well known Triton X-100 also provided
satisfactory results, but the yields were somewhat
lower, 75–86%. When the reaction was carried out in
the presence of an anionic surfactant, sodium lauryl
sulfate, the yield did not exceed 30%.
Most known methods of synthesis of 1,1,2,2-tetra-
cyanocyclopropanes are based on the Wideqvist reac-
tion [8], Michael addition of bromomalononitrile to
ylidene derivatives of malononitrile [9], and reactions
of diazo alkanes with tetracyanoethylene [10]. Later
on, some modifications of these methods have been
proposed, in particular one-pot syntheses [11, 12] and
reactions with electrochemically generated reagents
[13]. All these methods utilize organic solvents.
We believe that the process begins with the
Knoevenagel condensation of aldehyde 2a–2e with
malononitrile (3), which leads to the formation of
2-benzylidenemalononitriles 4. Simultaneously, the
bromination of 3 gives 2-bromomalononitrile (5). The
subsequent Michael addition of bromomalononitrile 5
to benzylidenemalononitrile 4, followed by cycliza-
tion, yields cyclopropanes 1a–1e.
Herein, we describe the synthesis of 1,1,2,2-tetra-
cyanocyclopropanes 1a–1e by multicomponent reac-
tion of aromatic aldehydes 2a–2e with malononitrile
(3) and bromine in aqueous medium in the presence of
Thus, we have developed a simple and environ-
mentally safe procedure for the synthesis of 3-aryl-
CN
Ar
ArCHO
+
H2C(CN)2
CN
–H2O
NC
H
CN
2a–2e
3
4
+
Ar
–HBr
CN
CN
NC
H2C(CN)2
+ Br2
–HBr
1a–1e
Br
CN
3
5
Ar = Ph (a), 2-ClC6H4 (b), 4-MeC6H4 (c), 4-MeOC6H4 (d), 3-O2NC6H4 (e).
1839

BARDASOV et al.
1840
cyclopropane-1,1,2,2-tetracarbonitriles in 85–94%
yield. The reaction requires no base catalyst, and the
products crystallize directly from the reaction mixture.
(Irel 10%) [M]+. Found, %: C 67.80; H 3.35; N 22.41.
C14H8N4O. Calculated, %: C 67.74; H 3.25; N 22.57.
M 248.25.
3-Phenylcyclopropane-1,1,2,2-tetracarbonitrile
(1a). A solution of 0.160 g of bromine in 2 mL of 5%
aqueous potassium bromide was added dropwise to
a suspension of 0.106 g (1 mmol) of benzaldehyde 2a–
2e, 0.132 g (2 mmol) of malononitrile (3), and 0.046 g
(0.15 mmol) of cocamidopropyl dimethylamine oxide
in 5 mL of water. The mixture was stirred for 4 h at
room temperature (TLC) and diluted with 5 mL of
water, and the precipitate was filtered off and washed
with 10 mL of water and 5 mL of ethanol. Yield 92%,
mp 229–230°C; published data [9]: mp 227–230°C. IR
3-(3-Nitrophenyl)cyclopropane-1,1,2,2-tetra-
carbonitrile (1e). Yield 88%, mp 250–251°C;
published data [9]: mp 246–248°C. IR spectrum, ν,
1
cm–1: 3033 (C–H), 2242 (C≡N). H NMR spectrum
(DMSO-d6), δ, ppm: 5.46 s (1H, CH), 7.82 t (1H,
Harom, J = 8.0 Hz), 8.28–8.41 m (2H, Harom), 9.01 s
(1H, Harom). Mass spectrum: m/z 263 (Irel 5%) [M]+.
Found, %: C 59.43; H 1.98; N 26.47. C13H5N5O2.
Calculated, %: C 59.32; H 1.91; N 26.61. M 263.22.
The IR spectra were recorded on an FSM-1202
spectrometer with Fourier transform from samples
1
spectrum, ν, cm–1: 3035 (C–H), 2242 (C≡N). H NMR
1
dispersed in mineral oil. The H NMR spectra were
spectrum (DMSO-d6), δ, ppm: 5.27 s (1H, CH),
7.44–7.52 m (3H, Harom), 7.74–7.82 m (2H, Harom).
Mass spectrum, m/z (Irel, %): 218 (10) [M]+, 154 (100)
[M – 64]+. Found, %: C 71.63; H 2.81; N 25.52.
C13H6N4. Calculated, %: C 71.55; H 2.77; N 25.68.
M 218.22.
measured on a Bruker DRX-500 spectrometer from
solutions in DMSO-d6 using tetramethylsilane as
internal standard. The mass spectra (electron impact,
70 eV) were obtained on a Finnigan MAT INCOS-50
instrument. The elemental analyses were obtained on
a Vario Micro cube CHN analyzer. The melting points
were determined on an OptiMelt MPA100 automated
melting point apparatus. The progress of reactions was
monitored, and the purity of the isolated compounds
was checked, by TLC on Sorbfil PTSKh-AF-A-UF
plates using ethyl acetate as eluent; spots were visual-
ized under UV light, by treatment with iodine vapor, or
by thermal decomposition.
Compounds 1b–1f were synthesized in a similar
way.
3-(2-Chlorophenyl)cyclopropane-1,1,2,2-tetra-
carbonitrile (1b). Yield 94%, mp 246–247°C;
published data [9]: mp 246–248°C. IR spectrum, ν,
1
cm–1: 3030 (C–H), 2240 (C≡N). H NMR spectrum
(DMSO-d6), δ, ppm: 5.48 s (1H, CH), 7.48–7.62 m
(2H, Harom), 7.68–7.74 m (1H, Harom), 8.03–8.09 m
(1H, Harom). Mass spectrum, m/z (Irel, %): 254/252 (3/8)
[M]+, 190/188 (33/100) [M – 64]+. Found, %: C 61.89;
H 2.03; N 22.01. C13H5ClN4. Calculated, %: C 61.80;
H 1.99; N 22.18. M 252.66.
This study was performed under financial support
by the President of the Russian Federation (program
for state support of young Russian scientists, project
no. MK-2103.2017.3).
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SYNTHESIS OF 3-ARYLCYCLOPROPANE-1,1,2,2-TETRACARBONITRILES
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