Synthesis of 2,2,3,3-tetracyanocyclopropyl ketones and their reactions with oxygen-centered nucleophiles

Article abstract of DOI:10.1134/S1070428009090048

A procedure for the synthesis of 2,2,3,3-tetracyanocyclopropyl ketones has been developed on the basis of three-component Wideqvist reaction of dihydroxymethyl ketones, 2-bromomalononitrile, and malononitrile. The presence of five electron-withdrawing groups in the resulting cyclopropyl ketones determines high acidity of proton in the cyclopropane ring. Facile deprotonation by the action of bases promotes opening of the three-membered ring with formation of either 1,1,3,3-tetracyanopropenides or (in the presence of alcohols or oximes), [2-alkoxy(aminooxy)-5-amino-4-cyanofuran-3(2H)-ylidene] malononitriles. The reaction with acetone oxime was not accompanied by cleavage of the three-membered ring, and nucleophilic attack was directed at the cyano groups in the trans position with respect to the carbonyl group to give the corresponding (1R*,5S*,6R*)-4-amino-2,2-bis(prop-2- ylideneaminooxy)-3-azabicyclo[3.1.0]hex-3-ene-1,5-dicarbonit riles.

Full text of DOI:10.1134/S1070428009090048

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 9, pp. 1325–1335. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © I.N. Bardasov, O.V. Kayukova, Ya.S. Kayukov, O.V. Ershov, O.E. Nasakin, V.A. Tafeenko, 2009, published in Zhurnal
Organicheskoi Khimii, 2009, Vol. 45, No. 9, pp. 1340–1351.
Synthesis of 2,2,3,3-Tetracyanocyclopropyl Ketones
and Their Reactions with Oxygen-Centered Nucleophiles
I. N. Bardasova, O. V. Kayukovaa, Ya. S. Kayukova, O. V. Ershova,
O. E. Nasakina, and V. A. Tafeenkob
a I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: barkas12@mail.ru
b Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
Received August 13, 2008
Abstract—A procedure for the synthesis of 2,2,3,3-tetracyanocyclopropyl ketones has been developed on the
basis of three-component Wideqvist reaction of dihydroxymethyl ketones, 2-bromomalononitrile, and malono-
nitrile. The presence of five electron-withdrawing groups in the resulting cyclopropyl ketones determines high
acidity of proton in the cyclopropane ring. Facile deprotonation by the action of bases promotes opening of the
three-membered ring with formation of either 1,1,3,3-tetracyanopropenides or (in the presence of alcohols or
oximes), [2-alkoxy(aminooxy)-5-amino-4-cyanofuran-3(2H)-ylidene]malononitriles. The reaction with acetone
oxime was not accompanied by cleavage of the three-membered ring, and nucleophilic attack was directed at
the cyano groups in the trans position with respect to the carbonyl group to give the corresponding
(1R*,5S*,6R*)-4-amino-2,2-bis(prop-2-ylideneaminooxy)-3-azabicyclo[3.1.0]hex-3-ene-1,5-dicarbonitriles.
DOI: 10.1134/S1070428009090048
One of the main procedures for the synthesis
of 1,1,2,2-tetracyanocyclopropanes is based on the
Wideqvist reaction which implies treatment of carbon-
yl compounds with 2-bromomalononitrile in aqueous
alcohol at room temperature over a period of 0.5–12 h
in the presence of potassium iodide as reducing agent
[1–4]. However, the scope of this procedure is essen-
tially limited: it cannot be used for the synthesis of
tetracyanocyclopropanes having five or six electron-
withdrawing substituents. Potassium iodide is capable
of reacting with cyclopropanes, leading to cleavage of
the three-membered ring with formation of cyano-sub-
stituted propenides [5–8].
As we showed previously, activated carbonyl com-
pounds that could give rise to stable hydrates may be
converted into tetracyanocyclopropanes via reaction
with 2-bromomalononitrile in the absence of potassium
iodide [9, 10]. It was presumed that in this case bromo-
malononitrile acts as reducing agent thus being
oxidized to dibromomalononitrile. Using this proce-
dure we successfully synthesized a series of 3-aroyl-
cyclopropane-1,1,2,2-tetracarbonitriles [10]. We pro-
Scheme 1.
O
O
CN
O
CN
CHBr(CN)2
–H2O
CH2(CN)2
OH
Br
CN
R
R
R
CN
–CHBr(CN)2, –H2O
OH
Ia–Ih
OH
CN
H
O
NC
CN
CHBr(CN)2
Br
CN
CN
CN
R
R
–HBr
CN
IIa–IIh
NC
O
R = Ph (a), 4-BrC6H4 (b), 4-MeOC6H4 (c), 3,4-(MeO)2C6H3 (d), 3-O2NC6H4 (e), Me (f), t-Bu (g), 2-thienyl (h).
1325

BARDASOV et al.
1326
posed to use malononitrile as reducing agent; during
the reaction it is converted into bromomalononitrile
which may return to the process. Our new approach to
the synthesis of cyclopropanes is based on three-com-
ponent reaction of dihydroxymethyl ketone Ia–Ih with
malononitrile and 2-bromomalononitrile at a ratio of
1:1:1. The yields of 2,2,3,3-tetracyanocyclopropyl
ketones IIa–IIh obtained in such a way were 68–82%.
Phenylglyoxal failed to react with malononitrile (in
contrast to bromomalononitrile) in the absence of
a catalyst; therefore, we presumed that the reaction
begins just with attack on bromomalononitrile and that
malononitrile acts as reducing and debrominating
agent (Scheme 1).
analogous transformations reported until recently.
An example is the reaction of tetracyanocyclopropane-
1,1-dicarboxylate with ammonia, which resulted in the
formation of ammonium 1,1,3,3-tetracyano-2-ethoxy-
carbonylpropenide [19]. Likewise, pentacyanoprope-
nide and products of its further transformations were
formed in reactions of pentacyanocyclopropanecarbox-
ylate with some nucleophiles [17]. In the case of tetra-
cyanocyclopropanes obtained from acetylacetone [16],
dimedone [20], and indandione [14], such reactions are
preceded by acyl cleavage. Cyclopropyl anion can be
generated as intermediate by the action of bases on cy-
clopropanes having five electron-withdrawing groups.
We recently showed that 3-benzoylcyclopropane-
1,1,2,2-tetracarbonitrile reacts with alkoxides to give
dihydrofuran derivatives, presumably through interme-
diate formation of cyclopropanide and propenide [21].
The structure of cyclopropanes IIa–IIh was con-
firmed by the IR, 1H NMR, and mass spectra. All com-
pounds IIa–IIh possess a hydrogen atom in the three-
membered ring; it gives rise to a singlet at δ 5.32–
Our study on reactions of tetracyanocyclopropyl
ketones IIa–IIh with alkoxides and oximates showed
that the formation of dihydrofuran derivatives is gen-
eral. Cyclopropyl ketones IIa–IIh reacted with sodium
methoxide and sodium 2-hydroxyethoxide in the corre-
sponding alcohols to give (after neutralization with an
acid) [2-alkoxy-5-amino-4-cyanofuran-3(2H)-ylidene]-
malononitriles IIIa–IIIn, while in the reactions with
acetone and acetaldehyde oxime sodium salts
[5-amino-4-cyano-2-(alkylideneaminooxy)furan-
3(2H)-ylidene}malononitriles IVa–IVn were obtained
in 19–87% yields (Scheme 2).
1
5.66 ppm in the H NMR spectra, and the IR spectra
contain an absorption band at 3023–3061 cm–1 due to
stretching vibrations of the C–H bond. In addition,
absorption bands belonging to unconjugated cyano
groups and carbonyl group were present in the regions
2260–2271 and 1652–1729 cm–1, respectively, and sig-
nals from protons in alkyl, aryl, or thiophene substit-
uents were observed in the 1H NMR spectra. All cyclo-
propanes II (except for IIg) displayed in the mass
spectra molecular ion peaks with low to medium
intensity (10–45%).
It is known that electron-deficient cyclopropanes
having four and more electron-withdrawing groups
exhibit high reactivity toward nucleophiles [5–8, 11–
17]. The direction and depth of their transformations in
reactions with nucleophiles are largely determined by
the nature of nucleophile and electron-withdrawing
groups in the substrate. Two main reaction directions
are usually considered. The first of these involves
initial attack by nucleophile on carbon atoms in the
three-membered ring, leading to opening of the latter
[5–8], while the second begins with attack on electron-
withdrawing group (carbonyl or cyano), and such
reactions often occur with conservation of the cyclo-
propane ring [11–15].
The structure of compounds IIIa–IIIn and IVa–
IVn was confirmed by the IR, H NMR, and mass
1
spectra. In the IR spectra of these compounds, stretch-
ing vibrations of conjugated cyano groups gave rise to
absorption bands in the region 2203–2225 cm–1;
absorption bands at 3074–3280 cm–1 were assigned to
stretching vibrations of the amino group; and the C=C
bond in the dicyanomethylene fragment was charac-
terized by absorption at 1669–1695 cm–1. The 1H NMR
spectra contained downfield signals from protons in
the amino group (δ 10.12–10.49 ppm) and signals from
alkyl, aryl, or thienyl substituent.
Due to effect of five electron-withdrawing substit-
uents, the hydrogen atom in the cyclopropane ring of
2,2,3,3-tetracyanocyclopropyl ketones IIa–IIh be-
comes so labile that it can readily be removed as
proton by the action of bases. Its acidity also follows
One more reaction direction is possible; it involves
carbanion ring cleavage which is likely to follow four-
electron electrocyclic mechanism [5, 16–18]. Such re-
actions are favored by the presence of electron-with-
drawing groups which stabilize the resulting allyl-type
anion, i.e., propenide. Most frequently, carbanion
cleavage preceded formation of cyclopropyl anion in
1
from downfield position of its signal in the H NMR
spectrum (δ 5.32–5.66 ppm). Presumably, in the first
step alkoxide (oximate) as a base abstracts proton from
cyclopropane IIa–IIh to afford cyclopropanide A
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

SYNTHESIS OF 2,2,3,3-TETRACYANOCYCLOPROPYL KETONES
1327
Scheme 2.
O
CN
CN
CN
CN
NC
CN
CN
OH
HO
RO–
ROH
IIa–IIh
R'
CN
R'
CN
R'
–ROH
CN
NC
NC
O
A
B
C
CN
CN
CN
CN
NC
NC
H2SO4
R'
RO
R'
RO
NH
NH2
O
O
D
IIIa–IIIn, IVa–IVn
III, R = Me, R′ = Ph (a), 4-BrC6H4 (b), 4-MeOC6H4 (c), 3,4-(MeO)2C6H3 (d), 3-O2NC6H4 (e), Me (f), t-Bu (g), 2-thienyl (h);
R = HOCH2CH2, R′ = Ph (i), 4-BrC6H4 (j), 4-MeOC6H4 (k), 3,4-(MeO)2C6H3 (l), Me (m), t-Bu (n); IV, R = MeCH=N, R′ = Ph (a),
4-BrC6H4 (b), 4-MeOC6H4 (c), 3,4-(MeO)2C6H3 (d), Me (e), t-Bu (f), 2-thienyl (g); R = Me2C=N, R′ = Ph (h), 4-BrC6H4 (i),
4-MeOC6H4 (j), 3,4-(MeO)2C6H3 (k), 3-O2NC6H4 (l), Me (m), 2-thienyl (n).
which undergoes opening of the three-membered ring
(probably following electrocyclic mechanism) with
formation of resonance-stabilized propenide ion B.
Next follows nucleophilic addition of oxygen-centered
nucleophile (alcohol or oxime) at the carbonyl group,
leading to hemiacetal C, and subsequent heterocycliza-
tion involving the hydroxy group and spatially close
cyano group gives dihydrofuran derivative D. Upon
acidification of the reaction mixture anion D is con-
verted into final product IIIa–IIIn or IVa–IVn.
tion of propenide Vg (yield 87%), whereas dihydro-
furan derivative could not be obtained (Scheme 3).
We tried to isolate the corresponding propenides by
reacting cyclopropanes IIa–IIh with compounds that
are fairly strong bases but weak nucleophiles. We
found that propenides V are formed in reactions of cy-
clopropanes IIa–IIh sodium or ammonium formates,
acetates, and carbonates. The best results were ob-
tained with the use of acetates; 2-acyl-1,1,3,3-tetracy-
anopropenides Va–Vh were formed in almost quanti-
tative yield (86–93%; Scheme 4).
The rate of the reaction of cyclopropanes IIa–IIh
with alkoxides and oximates and the yields of the
resulting dihydrofurans depend on both O-nucleophile
nature and substituent in the substrate. Nucleophile ad-
dition at the carbonyl group is likely to be the slowest
process. Therefore, the reaction with the least sterically
hindered methyl tetracyanocyclopropyl ketone (IIf) is
the most facile, and the yield of the corresponding
product is the highest. The aromatic ring in cyclo-
propanes IIa–IIe does not hamper attack by nucleo-
phile, but donor substituents in the aromatic ring de-
activate the carbonyl group, and the reaction rate
decreases. The tert-butyl radical in cyclopropane IIg
shields the carbonyl group, so that addition of a bulky
nucleophile is hindered, and the reaction (e.g., with
acetone oxime sodium salt) stops at the stage of forma-
Scheme 4.
NC
CN
CN
MeCOO– M+
–MeCOOH
IIa–IIh
R'
M+
CN
O
O
CN
R
CN
M+
NC
CN
Va–Vh
M = Na (a–e, g, h), NH4 (f); R = Ph (a, f), 4-BrC6H4 (b),
4-MeOC6H4 (c), 3,4-(MeO)2C6H3 (d), 3-O2NC6H4 (e),
t-Bu (g), 2-thienyl (h).
Scheme 3.
O
CN
CN
NC
CN
CN
The structure of compound Vf was proved by X-ray
analysis, and the IR spectra of propenides Va–Ve, Vg,
and Vh were similar to the spectrum of Vf. Figure 1
shows the structure of molecule Vf with atom num-
bering. The C2=O1 carbonyl group is turned through
Me2C=NOH
t-Bu
CN
t-Bu
–Me2C=NOH
CN
NC
O
IIg
Vg
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

BARDASOV et al.
tion of the carbonyl group with the benzene ring is
1328
N4
C4
C11
C10
reflected in shortened C2–O3 bond [1.473(2) Å] rela-
tive to the C2–C1 bond [1.522(3) Å]. The dicyano-
methyl fragments C9(CN)2 and C10(CN)2 are turned by
an angle of 10.8° with respect to each other due to
steric interactions between the C14≡N3 and C12≡N5
groups. In crystal, the carbonyl oxygen atom and N2
and N5 cyano nitrogen atoms are involved in hydrogen
bonding with the ammonium ion (Fig. 2). The O1i, N2ii,
and N5iii atoms are characterized by the following sym-
metry elements: i: 1 – x, 2 – y, –z; ii: 1 + x, 1 + y, z; iii:
1 – x, 3 – y, –z.
N5
C6
C8
C5
C12
N1
C7
C2
C3
C1
C9
b
c
a
C14
N3
O1
C13
N2
Fig. 1. Structure of the molecule of ammonium 2-benzoyl-
1,1,3,3-tetracyanopropenide (Vf) according to the X-ray dif-
fraction data.
The transformation sequence shown in Scheme 2 is
confirmed by the reaction of propenide Va with
methanol in the presence of sodium hydroxide. It was
also found that propenide Va does not react with
methanol in neutral medium but reacts in the presence
of sulfuric acid to give 78% of dihydrofuran derivative
a dihedral angle of 16.3° relative to the benzene ring
plane, and the dihedral angle between that group and
the tetracyanopropenide fragment is 63.6°. Conjuga-
Scheme 5.
O
CN
CN
OH
CN
CN
CN
MeO
OH
H+
–Na+
MeOH
–H+
CN
Na+
CN
CN
NC
NC
CN
NC
Va
E
CN
CN
H+
CN
CN
NC
NC
Ph
MeO
Ph
MeO
NH
NH2
O
O
IIIa
Scheme 6.
Me
N
N
O
O
H
NC
NC
Me
O
Me
Me
OH
Me
NH
R
NC
H
Me
II
+
N
O
N
CN
R
NH
CN
Me
Me
Me
OH
N
N
O
O
O
N
N
NC
Me
Me
R
Me
H
NC
NH2
VIa–VIe
R = Ph (a), 4-MeOC6H4 (b), 3,4-(MeO)2C6H3 (c), t-Bu (d), 2-thienyl (e).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

SYNTHESIS OF 2,2,3,3-TETRACYANOCYCLOPROPYL KETONES
IIIa (Scheme 5). Presumably, acid catalysis implies
1329
protonation of propenide Va at the carbonyl oxygen
atom (rather than at carbon atoms of the allylic frag-
ment) with formation of zwitterionic intermediate E.
According to published data, compounds possess-
ing a tetracyanoethyl fragment react with oximes to
form pyrrole derivatives [22]. Nucleophilic attack on
the carbonyl group in cyclopropyl ketones II could
give rise to furan derivatives [22]. We found that tetra-
cyanocyclopropanes IIa, IIc, IId, IIg, and IIh react
with acetone oxime in MeCN to give (1R*,5S*,6R*)-
4-amino-2,2-bis(prop-2-ylideneaminooxy)-6-R-car-
bonyl-3-azabicyclo[3.1.0]hex-3-ene-1,5-dicarbonitriles
VIa–VIe in 35–73% yield (Scheme 6).
O1
N1
N5
N1
c
a
b
N5
N2
The structure of compounds VIa–VIe was con-
firmed by the IR and 1H NMR spectra; in addition, the
13C NMR spectrum of VIb was recorded. The IR
spectra of these compounds contained an absorption
band at 3045–3077 cm–1 due to stretching vibrations of
the cyclopropane C–H bond, and bands belonging to
vibrations of unconjugated cyano groups (2246–
2249 cm–1), carbonyl group (1668–1674 cm–1), and
amino group (3262–3378 cm–1) were present. The
Fig. 2. Hydrogen bonds between the anions and cations in
the crystalline structure of ammonium 2-benzoyl-1,1,3,3-
tetracyanopropenide (Vf).
1
cyclopropane proton signal appeared in the H NMR
spectra at δ 3.38–4.01 ppm, and protons in the amino
group resonated in the region δ 7.48–7.56 ppm.
C18
C19
C17
Closure of pyrrole ring is possible both at the side
of the acyl group and at the side of the hydrogen atom.
According to the NMR data, only one among possible
stereoisomers is formed. The structure of compound
VId was proved by X-ray analysis (Fig. 3). The inter-
atomic distances and bond angles in molecule VId are
typical of such compounds, so that no detailed con-
sideration is necessary. Molecules VId in crystal are
linked to centrosymmetric dimers via hydrogen bonds
N6–H62 · · · N1i (1 – x, 1 – y, –z; N1i · · · H62 2.16Ǻ,
∠N1H62N1i 165°). Thus the addition occurs at the side
opposite to the acyl group, which is likely to be deter-
mined by steric factor.
a
N3
c
b
C16
C15
O2
C2
C14
H62′
N2
N4
N1
O1
N1i
C13
C3
C6
C5
C4
C12
N6
H62
C10
O3
C7
C9
C8
C11
EXPERIMENTAL
The progress of reactions and the purity of products
were monitored by thin-layer chromatography on
Silufol UV-254 plates; spots were visualized under UV
light, by treatment with iodine vapor, or by heating.
The IR spectra were recorded from samples dispersed
in mineral oil on an FSM-1202 spectrometer with
Fig. 3. A fragment of centrosymmetric dimer formed by
molecules of 4-amino-2,2-bis(isopropylideneaminooxy)-6-
(2,2-dimethyl-1-oxopropyl)-3-azabicyclo[3.1.0]hex-3-ene-
1,5-dicarbonitrile (VId) in crystal. Molecular structure of
one molecule is shown; the H62′ and N1i atoms belong to the
other molecule.
1
Fourier transform. The H NMR spectra were meas-
ured on a Bruker DRX-500 spectrometer (500.13 MHz)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

BARDASOV et al.
1330
using DMSO-d6 as solvent and tetramethylsilane as
internal reference. The mass spectra (electron impact,
70 eV) were obtained on a Finnigan MAT INCOS-50
instrument.
3-(3-Nitrobenzoyl)cyclopropane-1,1,2,2-tetra-
carbonitrile (IIe). Yield 78%, mp 219–220°C
(decomp.). IR spectrum, ν, cm–1: 3061 (C–H), 2271
(C≡N), 1698 (C=O). 1H NMR spectrum, δ, ppm: 5.88 s
(1H, CH); 7.96 t, 8.42 d, 8.57 s, and 8.61 d (4H, C6H4).
Mass spectrum: m/z 291 (Irel = 15%). Found, %:
C 57.80; H 1.68; N 24.01. C14H5N5O3. Calculated, %:
C 57.74; H 1.73; N 24.05.
The X-ray diffraction data were acquired from
single crystals of compounds Vf and VId on an Enraf–
Nonius CAD-4 four-circle automatic diffractometer
(CuKα irradiation for Vf and MoKα irradiation for VId,
graphite monochromator, ω-scanning). The structures
were solved by the direct methods using SHELXS-97
software package. The positions and thermal param-
eters of non-hydrogen atoms were refined in full-
matrix anisotropic approximation. Hydrogen atoms in
structure Vf were localized from the Fourier difference
syntheses, and their positions were refined in isotropic
approximation. The positions of hydrogen atoms in
structure VId were calculated and refined using the
riding model. The crystallographic data for compounds
Vf and VId were deposited to the Cambridge Crystal-
lographic Data Centre, entry nos. CCDC 694326 (Vf)
and 694327 (VId), and are available upon request
(CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK;
http://www.ccdc.cam.ac.uk; fax: +(44123)3336033;
e-mail: deposit@ccdc.cam.ac.uk;).
3-Acetylcyclopropane-1,1,2,2-tetracarbonitrile
(IIf). Yield 68%, mp 182–183°C (decomp.); published
data [23]: mp 196–197°C (decomp.).
3-(2,2-Dimethyl-1-oxopropyl)cyclopropane-
1,1,2,2-tetracarbonitrile (IIg). Yield 73%, mp 204–
205°C (decomp.); published data [23]: mp 166–167°C
(decomp.).
3-(2-Thienylcarbonyl)cyclopropane-1,1,2,2-
tetracarbonitrile (IIh). Yield 76%, mp 201–202°C
(decomp.). IR spectrum, ν, cm–1: 3061 (C–H), 2260
(C≡N), 1652 (C=O). 1H NMR spectrum, δ, ppm: 5.54 s
(1H, CH); 7.40 t, 8.27 d, 8.55 d (3H, C4H3S). Mass
spectrum: m/z 252 (Irel = 45%). Found, %: C 57.10;
H 1.66; N 22.23. C12H4N4OS. Calculated, %: C 57.14;
H 1.60; N 22.21.
2-[5-Amino-4-cyano-2-methoxy-2-phenylfuran-
3(2H)-ylidene]malononitrile (IIIa). a. A suspension
of 2.46 g (0.01 mol) of cyclopropane Ia in 10 ml of
methanol was added under stirring to a solution of
0.05 g (0.02 mol) of sodium in 10 ml of methanol. The
mixture was kept for 24 h, neutralized with 5% sulfuric
acid, and extracted with ethyl acetate. The organic
phase was dried over calcined sodium sulfate, the
solvent was distilled off, and the residue was ground
with 10 ml of water. The precipitate was filtered off
and washed with water. Yield 2.36 g (83%), mp 138–
139°C (decomp.). IR spectrum, ν, cm–1: 3280, 3140
3-Benzoylcyclopropane-1,1,2,2-tetracarbonitrile
(IIa). 2,2-Dihydroxy-1-phenylethanone, 1.52 g
(0.01 mol), and malononitrile, 0.66 g (0.01 mol), were
dissolved in 15 ml of isopropyl alcohol, 1.45 g
(0.01 mol) of 2-bromomalononitrile was added to the
solution under stirring, and the mixture was stirred for
15 min. The precipitate was filtered off and washed
with isopropyl alcohol. Yield 1.92 g (78%), mp 211–
212°C (decomp.) [10].
Compounds IIb–IIh were synthesized in a similar
way.
1
3-(4-Bromobenzoyl)cyclopropane-1,1,2,2-tetra-
carbonitrile (IIb). Yield 82%, mp 214–215°C
(decomp.) [10].
(NH2); 2225 (C≡N); 1683 (C=C). H NMR spectrum,
δ, ppm: 3.48 s (3H, OCH3), 7.52 m (5H, C6H5), 10.33 s
(2H, NH2). Mass spectrum, m/z 278 (Irel = 30%).
Found, %: C 64.55; H 3.66; N 20.10. C15H10N4O2. Cal-
culated, %: C 64.74; H 3.62; N 20.13.
3-(4-Methoxybenzoyl)cyclopropane-1,1,2,2-
tetracarbonitrile (IIc). Yield 76%, mp 204–205°C
(decomp.) [10].
b. A 5% solution of sulfuric acid, 1 ml, was added
under stirring to a solution of 2.68 g (0.01 mol) of
propenide Va in 10 ml of methanol. The mixture was
kept for 24 h, diluted with 10 ml of water, and ex-
tracted with ethyl acetate. The organic phase was dried
over calcined sodium sulfate, the solvent was distilled
off, and the residue was ground with 10 ml of water.
The precipitate was filtered off and washed with water.
Yield 2.87 g (78%), mp 137–138°C (decomp.).
3-(3,4-Dimethoxybenzoyl)cyclopropane-1,1,2,2-
tetracarbonitrile (IId). Yield 75%, mp 186–187°C
(decomp.). IR spectrum, ν, cm–1: 3027 (C–H), 2261
(C≡N), 1673 (C=O). 1H NMR spectrum, δ, ppm: 3.86 s
and 3.9 s (3H each, OCH3); 5.66 s (1H, CH); 7.19 d,
7.65 s, and 7.98 d (3H, C6H3). Mass spectrum: m/z 306
(Irel = 10%). Found, %: C 62.75; H 3.32; N 18.33.
C16H10N4O3. Calculated, %: C 62.74; H 3.29; N 18.29.
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SYNTHESIS OF 2,2,3,3-TETRACYANOCYCLOPROPYL KETONES
1331
Compounds IIIb–IIIh were synthesized in a simi-
lar way according to method a.
mp 147–148°C (decomp.). IR spectrum, ν, cm–1: 3261,
3180 (NH2); 2218 (C≡N), 1677 (C=C). 1H NMR spec-
trum, δ, ppm: 3.45 s (3H, OCH3); 7.10 t, 7.29 d, and
7.75 d (3H, C4H3S); 10.37 s (2H, NH2). Found, %:
C 54.87; H 2.94; N 19.80. C13H8N4O2S. Calculated, %:
C 54.92; H 2.84; N 19.71.
2-[5-Amino-2-(4-bromophenyl)-4-cyano-2-me-
thoxyfuran-3(2H)-ylidene]malononitrile (IIIb).
Yield 79%, mp 205–206°C (decomp.). IR spectrum, ν,
cm–1: 3255, 3177 (NH2); 2219 (C≡N); 1695 (C=C).
1H NMR spectrum, δ, ppm: 3.48 s (3H, OCH3), 7.47 d
and 7.68 d (2H each, C6H4), 10.43 s (2H, NH2). Found,
%: C 50.47; H 2.50; N 15.75. C15H9BrN4O2. Calculat-
ed, %: C 50.44; H 2.54; N 15.69.
2-[5-Amino-4-cyano-2-(2-hydroxyethoxy)-2-
phenylfuran-3(2H)-ylidene]malononitrile (IIIi).
A suspension of 2.46 g (0.01 mol) of cyclopropane Ia
in 10 ml of ethylene glycol was added under stirring to
a solution of 0.05 g (0.02 mol) of sodium in 10 ml of
ethylene glycol. The mixture was kept for 24 h,
neutralized with 5% sulfuric acid, and extracted with
ethyl acetate. The organic phase was dried over cal-
cined sodium sulfate, the solvent was distilled off, and
the residue was ground with 10 ml of water. The pre-
cipitate was filtered off and washed with water. Yield
85%, mp 132–133°C (decomp.). IR spectrum, ν, cm–1:
3270, 3150 (NH2); 2223 (C≡N); 1685 (C=C). 1H NMR
spectrum, δ, ppm: 3.6–3.72 m (4H, CH2CH2), 4.93 t
(1H, OH), 7.45–7.57 m (5H, C6H5), 10.34 s (2H, NH2).
Mass spectrum: m/z 308 (Irel = 10%). Found, %:
C 62.37; H 3.94; N 18.20. C16H12N4O3. Calculated, %:
C 62.33; H 3.92; N 18.17.
2-[5-Amino-4-cyano-2-methoxy-2-(4-methoxy-
phenyl)furan-3(2H)-ylidene]malononitrile (IIIc).
Yield 73%, mp 137–138°C (decomp.). IR spectrum, ν,
cm–1: 3261, 3155 (NH2); 2213 (C≡N); 1677 (C=C).
1H NMR spectrum, δ, ppm: 3.44 s and 3.79 s (3H each,
OCH3), 7.00 d and 7.44 d (2H each, C6H4), 10.29 s
(2H, NH2). Found, %: C 62.37; H 3.94; N 18.20.
C16H12N4O3. Calculated, %: C 62.33; H 3.92; N 18.17.
2-[5-Amino-4-cyano-2-(3,4-dimethoxyphenyl)-2-
methoxyfuran-3(2H)-ylidene]malononitrile (IIId).
Yield 58%, mp 123–124°C (decomp.). IR spectrum, ν,
cm–1: 3280, 3198 (NH2); 2213 (C≡N); 1688 (C=C).
1H NMR spectrum, δ, ppm: 3.47 s, 3.75 s, and 3.79 s
(3H each, OCH3); 6.94 d, 7.01 d, and 7.07 s (3H,
C6H3); 10.32 s (2H, NH2). Found, %: C 60.37; H 4.14;
N 16.60. C17H14N4O4. Calculated, %: C 60.35; H 4.17;
N 16.56.
Compounds IIIj–IIIn were synthesized in a similar
way.
2-[5-Amino-2-(4-bromophenyl)-4-cyano-2-(2-
hydroxyethoxy)furan-3(2H)-ylidene]malononitrile
(IIIj). Yield 81%, mp 170–171°C (decomp.). IR spec-
trum, ν, cm–1: 3255, 3147 (NH2); 2211 (C≡N); 1690
2-[5-Amino-4-cyano-2-methoxy-2-(3-nitrophen-
yl)furan-3(2H)-ylidene]malononitrile (IIIe). Yield
67%, mp 227–228°C (decomp.). IR spectrum, ν, cm–1:
3276, 3178 (NH2); 2216 (C≡N); 1684 (C=C). 1H NMR
spectrum, δ, ppm: 3.53 s (3H, OCH3); 7.79 t, 7.95 d,
8.33 s, and 8.38 d (4H, C6H4); 10.49 s (2H, NH2).
Mass spectrum: m/z 323 (Irel = 50%). Found, %:
C 55.67; H 2.80; N 21.70. C15H9N5O4. Calculated, %:
C 55.73; H 2.81; N 21.66.
1
(C=C). H NMR spectrum, δ, ppm: 3.59–3.68 m (4H,
CH2CH2), 4.93 t (1H, OH), 7.42 d and 7.70 d (4H,
C6H4), 10.40 s (2H, NH2). Found, %: C 49.59; H 2.94;
N 14.41. C16H11BrN4O3. Calculated, %: C 49.63;
H 2.86; N 14.47.
2-[5-Amino-4-cyano-2-(2-hydroxyethoxy)-2-(4-
methoxyphenyl)furan-3(2H)-ylidene]malononitrile
(IIIk). Yield 59%, mp 112–113°C (decomp.). IR spec-
trum, ν, cm–1: 3257, 3160 (NH2); 2218 (C≡N); 1691
2-[5-Amino-4-cyano-2-methoxy-2-methylfuran-
3(2H)-ylidene]malononitrile (IIIe). Yield (87%),
mp 239–240°C (decomp.); published data [16]:
mp 242–243°C (decomp.).
1
(C=C). H NMR spectrum, δ, ppm: 3.57–3.73 m (4H,
CH2CH2), 3.80 s (3H, OCH3), 6.98 d and 7.47 d (2H
each, C6H4), 10.30 s (2H, NH2). Found, %: C 60.37;
H 4.24; N 16.50. C17H14N4O4. Calculated, %: C 60.35;
H 4.17; N 16.56.
2-[5-Amino-2-tert-butyl-4-cyano-2-methoxyfu-
ran-3(2H)-ylidene]malononitrile (IIIg). Yield 74%,
mp 200–201°C (decomp.). IR spectrum, ν, cm–1: 3266,
3107 (NH2); 2217 (C≡N); 1691 (C=C). 1H NMR spec-
trum, δ, ppm: 1.00 s (9H, t-Bu), 3.37 s (3H, OCH3),
10.16 s (2H, NH2). Found, %: C 60.37; H 5.55;
N 21.60. C13H14N4O2. Calculated, %: C 60.45; H 5.46;
N 21.69.
2-[5-Amino-4-cyano-2-(3,4-dimethoxyphenyl)-2-
(2-hydroxyethoxy)furan-3(2H)-ylidene]malononi-
trile (IIIl). Yield 42%, mp 115–116°C (decomp.). IR
spectrum, ν, cm–1: 3248, 3157 (NH2); 2212 (C≡N);
1
1701 (C=C). H NMR spectrum, δ, ppm: 3.59–3.76 m
2-[5-Amino-4-cyano-2-methoxy-2-(2-thienyl)fu-
ran-3(2H)-ylidene]malononitrile (IIIh). Yield 76%,
(4H, CH2CH2); 3.78 s and 3.80 s (3H each, OCH3);
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BARDASOV et al.
1332
6.96 d, 7.02 d, and 7.13 s (3H, C6H3); 10.30 s (2H,
NH2). Found, %: C 58.65; H 4.41; N 15.17.
C18H16N4O5. Calculated, %: C 58.69; H 4.38; N 15.21.
CH3), 3.82 s (3H, OCH3), 7.05 d and 7.48 d (2H each,
C6H4), 7.99 q (1H, CHCH3), 10.29 s and 10.31 s (2H,
NH2). Mass spectrum: m/z 335 (Irel = 10%). Found, %:
C 60.80; H 3.96; N 20.90. C17H13N5O3. Calculated, %:
C 60.89; H 3.91; N 20.89.
2-[5-Amino-4-cyano-2-(2-hydroxyethoxy)-2-
methylfuran-3(2H)-ylidene]malononitrile (IIIm).
Yield 82%, mp 221–222°C (decomp.); published data
[16]: mp 212–215°C.
2-[5-Amino-4-cyano-2-(ethylideneaminooxy)-2-
(3,4-dimethoxyphenyl)furan-3(2H)-ylidene]malono-
nitrile (IVd). Yield 61%, mp 162–163°C (decomp.).
IR spectrum, ν, cm–1: 3281, 3198 (NH2); 2210 (C≡N);
2-[5-Amino-2-tert-butyl-4-cyano-2-(2-hydroxy-
ethoxy)furan-3(2H)-ylidene]malononitrile (IIIn).
Yield 72%, mp 208–209°C (decomp.). IR spectrum, ν,
cm–1: 3270, 3100 (NH2); 2212 (C≡N); 1682 (C=C).
1H NMR spectrum, δ, ppm: 1.00 s (9H, t-Bu), 3.48 t
(2H, OCH2CH2OH), 3.59 m (2H, OCH2CH2OH),
4.76 t (1H, OH), 10.12 s (2H, NH2). Found, %:
C 58.37; H 5.54; N 19.50. C14H16N4O3. Calculated, %:
C 58.32; H 5.59; N 19.43.
1
1682 (C=C). H NMR spectrum, δ, ppm: 1.93 d (3H,
CH3); 3.78 s and 3.80 s (3H each, OCH3); 7.02 d,
7.04 s, and 7.08 d (3H, C6H3); 8.00 q (1H, CHCH3);
10.28 s and 10.30 s (2H, NH2). Found, %: C 59.25;
H 4.16; N 19.20. C18H15N5O4. Calculated, %: C 59.18;
H 4.14; N 19.17.
2-[5-Amino-4-cyano-2-(ethylideneaminooxy)-
2-methylfuran-3(2H)-ylidene]malononitrile (IVe).
Yield 78%, mp 207–208°C (decomp.). IR spectrum,
ν, cm–1: 3251, 3199 (NH2); 2220 (C≡N); 1669 (C=C).
1H NMR spectrum, δ, ppm: 1.85 d (3H, CHCH3),
1.88 s (3H, CH3), 7.75 q (1H, CHCH3), 10.29 s (2H,
NH2). Mass spectrum: m/z 243 (Irel 20%). Found, %:
C 54.25; H 3.76; N 28.80. C11H9N5O2. Calculated, %:
C 54.32; H 3.73; N 28.79.
2-[5-Amino-4-cyano-2-(ethylideneaminooxy)-2-
phenylfuran-3(2H)-ylidene]malononitrile (IVa).
A solution of 2.46 g (0.01 mol) of cyclopropane IIa in
10 ml of acetonitrile was added under stirring to a so-
lution of 0.46 g (0.02 mol) of sodium in 10 ml of
acetaldehyde oxime. The mixture was kept for 24 h,
neutralized with 5% sulfuric acid, and extracted with
ethyl acetate. The organic phase was dried over cal-
cined sodium sulfate, the solvent was distilled off, and
the residue was ground with 10 ml of water. The pre-
cipitate was filtered off and washed with water. Yield
1.92 g (63%), mp 143–144°C (decomp.). IR spectrum,
ν, cm–1: 3255, 3189 (NH2); 2219 (C≡N); 1688 (C=C).
1H NMR spectrum, δ, ppm: 1.98 d (3H, CH3), 7.52 m
(5H, C6H5), 8.00 q (1H, CHCH3), 10.33 s and 10.37 s
(2H, NH2). Found, %: C 62.85; H 3.66; N 22.90.
C16H11N5O2. Calculated, %: C 62.95; H 3.63; N 22.94.
2-[5-Amino-2-tert-butyl-4-cyano-2-(ethylidene-
aminooxy)furan-3(2H)-ylidene]malononitrile (IVf).
Yield 76%, mp 228–229°C (decomp.). IR spectrum, ν,
cm–1: 3271, 3121 (NH2); 2213 (C≡N); 1689 (C=C).
1H NMR spectrum, δ, ppm: 1.02 m (9H, t-Bu), 1.91 d
(3H, CHCH3), 7.30 q (1H, CHCH3), 10.08 s and
10.15 s (2H, NH2). Mass spectrum: m/z 285 (Irel = 5%).
Found, %: C 58.85; H 5.36; N 24.60. C14H15N5O2. Cal-
culated, %: C 58.94; H 5.30; N 24.55.
2-[5-Amino-4-cyano-2-(ethylideneaminooxy)-2-
(2-thienyl)furan-3(2H)-ylidene]malononitrile (IVg).
Yield 69%, mp 122–123°C (decomp.). IR spectrum, ν,
cm–1: 3256, 3174 (NH2); 2203 (C≡N); 1682 (C=C).
1H NMR spectrum, δ, ppm: 1.92 d (3H, CH3); 7.14 t,
7.41 d, and 7.82 d (3H, C4H3S); 7.93 q (1H, CHCH3),
10.35 s and 10.38 s (2H, NH2). Found, %: C 54.05;
H 2.96; N 22.60. C14H9N5O2S. Calculated, %: C 54.01;
H 2.91; N 22.50.
Compounds IVb–IVg were synthesized in a similar
way.
2-[5-Amino-2-(4-bromophenyl)-4-cyano-2-(ethyl-
ideneaminooxy)furan-3(2H)-ylidene]malononitrile
(IVb). Yield 57%, mp 117–118°C (decomp.). IR spec-
trum, ν, cm–1: 3233, 3090 (NH2); 2216 (C≡N); 1693
1
(C=C). H NMR spectrum, δ, ppm: 1.93 d (3H, CH3),
7.50 d and 7.76 d (4H, C6H4), 8.01 q (1H, CHCH3),
10.36 s and 10.42 s (2H, NH2). Found, %: C 50.00;
H 2.66; N 18.30. C16H10BrN5O2. Calculated, %:
C 50.02; H 2.62; N 18.23.
2-[5-Amino-4-cyano-2-(isopropylideneamino-
oxy)-2-phenylfuran-3(2H)-ylidene]malononitrile
(IVh). Metallic sodium, 0.46 g (0.02 mol), was dis-
solved on slight heating in a mixture of 2.92 g
(0.04 mol) of acetone oxime and 10 ml of tert-butyl
alcohol, and a solution of 2.46 g (0.01 mol) of cyclo-
propane IIa in 10 ml of acetonitrile was added under
stirring. The mixture was kept for 24 h, neutralized
2-[5-Amino-4-cyano-2-(ethylideneaminooxy)-2-
(4-methoxyphenyl)furan-3(2H)-ylidene]malononi-
trile (IVc). Yield 72%, mp 181–182°C (decomp.). IR
spectrum, ν, cm–1: 3237, 3090 (NH2); 2220 (C≡N);
1
1691 (C=C). H NMR spectrum, δ, ppm: 1.93 d (3H,
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SYNTHESIS OF 2,2,3,3-TETRACYANOCYCLOPROPYL KETONES
1333
with 5% sulfuric acid, and extracted with ethyl acetate.
The organic phase was dried over calcined sodium
sulfate, the solvent was distilled off, and the residue
was ground with 10 ml of water. The precipitate was
filtered off and washed with water. Yield 2.87 g (90%),
mp 234–235°C (decomp.). IR spectrum, ν, cm–1: 3247,
3099 (NH2); 2216 (C≡N); 1688 (C=C). 1H NMR spec-
trum, δ, ppm: 1.97 s and 2.09 s (3H each, CH3), 7.50–
7.56 m (5H, C6H5), 10.30 s (2H, NH2). Found, %:
C 63.83; H 4.16; N 21.90. C17H13N5O2. Calculated, %:
C 63.94; H 4.10; N 21.93.
2-[5-Amino-4-cyano-2-(isopropylideneamino-
oxy)-2-methylfuran-3(2H)-ylidene]malononitrile
(IVm). Yield 73%, mp 228–229°C (decomp.); pub-
lished data [16]: mp 230–235°C (decomp.).
2-[5-Amino-4-cyano-2-(isopropylideneamino-
oxy)-2-(2-thienyl)furan-3(2H)-ylidene]malononitrile
(IVn). Yield 64%, mp 191–192°C (decomp.). IR spec-
trum, ν, cm–1: 3271, 3150 (NH2); 2218 (C≡N); 1685
1
(C=C). H NMR spectrum, δ, ppm: 1.95 s and 2.03 s
(3H each, CH3); 7.15 t, 7.39 d, and 7.82 d (3H,
C4H3S); 10.32 s (2H, NH2). Found, %: C 55.35;
H 3.46; N 21.60. C15H11N5O2S. Calculated, %:
C 55.38; H 3.41; N 21.53.
Compounds IVi–IVn were synthesized in a similar
way.
2-[5-Amino-2-(4-bromophenyl)-4-cyano-2-(iso-
propylideneaminooxy)furan-3(2H)-ylidene]malono-
nitrile (IVi). Yield 76%, mp 215–216°C (decomp.). IR
spectrum, ν, cm–1: 3272, 3128 (NH2); 2214 (C≡N);
Sodium 2-benzoyl-1,1,3,3-tetracyanopropenide
(Va). A solution of 0.82 g (0.01 mol) of sodium acetate
in 5 ml of water was added under stirring to a solution
of 2.46 g (0.01 mol) of cyclopropane IIa in 10 ml of
acetonitrile, and the mixture was stirred until the reac-
tion was complete (according to the TLC data). The
solution was evaporated to dryness, and the crystalline
residue was washed with dioxane and recrystallized
from aqueous isopropyl alcohol (1:1). Yield 2.39 g
(89%), mp 228–229°C (decomp.). IR spectrum, ν,
cm–1: 2205 (C≡N), 1655 (C=O).
1
1682 (C=C). H NMR spectrum, δ, ppm: 1.95 s and
2.08 s (6H, CH3), 7.52 d and 7.72 d (2H each, C6H4),
10.35 s (2H, NH2). Found, %: C 51.25; H 3.17;
N 17.50. C17H12BrN5O2. Calculated, %: C 51.27;
H 3.04; N 17.59.
2-[5-Amino-4-cyano-2-(isopropylideneamino-
oxy)furan-3(2H)-ylidene]malononitrile (IVj). Yield
66%, mp 166–167°C (decomp.). IR spectrum, ν, cm–1:
3256, 3104 (NH2); 2214 (C≡N); 1687 (C=C). 1H NMR
spectrum, δ, ppm: 1.93 s and 2.08 s (3H each, CH3),
3.80 s (3H, OCH3), 7.03 d and 7.47 d (2H each, C6H4),
10.23 s (2H, NH2). Found, %: C 61.85; H 4.36;
N 20.12. C18H15N5O3. Calculated, %: C 61.89; H 4.33;
N 20.05.
Compounds Vb–Vh were synthesized in a similar
way.
Sodium 2-(4-bromobenzoyl)-1,1,3,3-tetracyano-
propenide (Vb). Yield 91%, mp 221–222°C
(decomp.). IR spectrum, ν, cm–1: 2205 (C≡N), 1681
(C=O).
Sodium 1,1,3,3-tetracyano-2-(4-methoxyben-
zoyl)propenide (Vc). Yield 92%, mp 223–224°C
(decomp.). IR spectrum, ν, cm–1: 2200 (C≡N), 1664
(C=O).
2-[5-Amino-4-cyano-2-(3,4-dimethoxyphenyl)-
2-(isopropylideneaminooxy]furan-3(2H)-ylidene]-
malononitrile (IVk). Yield 19%, mp 157–158°C
(decomp.). IR spectrum, ν, cm–1: 3279, 3164 (NH2);
1
2208 (C≡N); 1684 (C=C). H NMR spectrum, δ, ppm:
Sodium 1,1,3,3-tetracyano-2-(3,4-dimethoxyben-
zoyl)propenide (Vd). Yield 90%, mp 186–187°C
(decomp.). IR spectrum, ν, cm–1: 2226 (C≡N), 1661
(C=O).
1.96 s and 2.08 s (3H each, CH3); 3.78 s and 3.80 s
(3H each, OCH3); 7.04 d, 7.05 s, and 7.07 d (3H,
C6H3); 10.21 s (2H, NH2). Found, %: C 60.21; H 4.58;
N 18.35. C19H17N5O4. Calculated, %: C 60.15; H 4.52;
N 18.46.
Sodium 1,1,3,3-tetracyano-2-(3-nitrobenzoyl)-
propenide (Ve). Yield 90%, mp 213–214°C
(decomp.). IR spectrum, ν, cm–1: 2230 (C≡N), 1656
(C=O).
2-[5-Amino-4-cyano-2-(isopropylideneamino-
oxy)-2-(3-nitrophenyl)furan-3(2H)-ylidene]malono-
nitrile (IVl). Yield 63%, mp 220–221°C (decomp.). IR
spectrum, ν, cm–1: 3230, 3074 (NH2); 2218 (C≡N);
Ammonium 2-benzoyl-1,1,3,3-tetracyanopro-
penide (Vf). Yield 86%, mp 181–182°C (decomp.). IR
spectrum, ν, cm–1: 3257, 3155, 3067 (NH4+); 2192
(C≡N); 1659 (C=O).
1
1694 (C=C). H NMR spectrum, δ, ppm: 1.99 s and
2.50 s (3H each, CH3); 7.84 t, 8.04 d, 8.32 s, and
8.42 d (4H, C6H4); 10.46 s (2H, NH2). Found, %:
C 56.15; H 3.35; N 23.03. C17H12N6O4. Calculated, %:
C 56.05; H 3.32; N 23.07.
Crystallographic parameters: a = 8.1856(11), b =
9.5361(12), c = 10.1685(11) Å; α = 115.957(13), β =
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BARDASOV et al.
1334
102.087(12), γ = 103.220(12)°; V = 649.88(19) Å3; Z =
2; space group P1. Total number of reflections 2531;
number of reflections with I > 2σ(I) 2233; number of
refined parameters 218; divergence factor R = 0.038.
C 59.83; H 5.22; N 19.95. C21H22N6O4. Calculated, %:
C 59.71; H 5.25; N 19.89.
4-Amino-6-(3,4-dimethoxybenzoyl)-2,2-bis(iso-
propylideneaminooxy)-3-azabicyclo[3.1.0]hex-3-
ene-1,5-dicarbonitrile (VIc). Yield 58%, mp 186–
187°C (decomp.). IR spectrum, ν, cm–1: 3342, 3252
(NH2); 3075 (C–H); 2243 (C≡N); 1673 (C=O).
1H NMR spectrum, δ, ppm: 1.76 s, 1.86 s, 1.87 s, and
1.96 s (3H each, CH3); 3.83 s and 3.89 s (3H each,
OCH3); 4.05 s (1H, CH); 7.11 d, 7.49 s, and 7.67 d
(3H, C6H3); 7.53 s (2H, NH2). Found, %: C 58.36;
H 5.23; N 17.62. C22H24N6O5. Calculated, %: C 58.40;
H 5.35; N 18.57.
Sodium 1,1,3,3-tetracyano-2-(2,2-dimethyl-1-
oxopropyl)propenide (Vg). a. The procedure was
analogous to that described above for compound Va.
Yield 89%, mp 206–207°C (decomp.). IR spectrum, ν,
cm–1: 2206 (C≡N), 1678 (C=O).
b. Metallic sodium, 0.46 g (0.02 mol), was dis-
solved on slight heating in a mixture of 2.92 g
(0.04 mol) of acetone oxime and 10 ml of dioxane. The
resulting solution was added under stirring to a sus-
pension of 2.26 g (0.01 mol) of cyclopropane IIg in
10 ml dioxane. After some time, the precipitate was
filtered off and washed with water. Yield 87%,
mp 206–207°C (decomp.).
4-Amino-2,2-bis(isopropylideneaminooxy)-
6-(2,2-dimethyl-1-oxopropyl)-3-azabicyclo[3.1.0]-
hex-3-ene-1,5-dicarbonitrile (VId). Yield (73%),
mp 180–181°C (decomp.). IR spectrum, ν, cm–1: 3332,
3266 (NH2); 3077 (C–H); 2247 (C≡N); 1672 (C=O).
1H NMR spectrum, δ, ppm: 1.14 s (9H, t-Bu); 1.83 s,
1.85 s, 1.86 s, and 1.87 s (3H each, CH3); 3.39 s (1H,
CH); 7.48 s (2H, NH2). Found, %: C 58.25; H 6.56;
N 22.61. C18H24N6O3. Calculated, %: C 58.05; H 6.50;
N 22.57.
Sodium 1,1,3,3-tetracyano-2-(2-thienylcarbonyl)-
propenide (Vh). Yield 93%, mp 183–184°C
(decomp.). IR spectrum, ν, cm–1: 2205 (C≡N), 1633
(C=O).
4-Amino-6-benzoyl-2,2-bis(isopropylidene-
aminooxy)-3-azabicyclo[3.1.0]hex-3-ene-1,5-dicar-
bonitrile (VIa). Acetone oxime, 1.46 g (0.02 mol),
was added under stirring to a solution of 2.46 g
(0.01 mol) of cyclopropane IIa in 10 ml of acetonitrile.
After 24 h, the precipitate was filtered off and washed
with several portions of acetonitrile and water. Yield
2.43 g (62%), mp 195–196°C (decomp.). IR spectrum,
ν, cm–1: 3358, 3262 (NH2); 3063 (C–H); 2246 (C≡N);
1668 (C=O). 1H NMR spectrum, δ, ppm: 1.75 s, 1.85 s,
1.87 s, and 1.98 s (3H each, CH3); 4.09 s (1H, CH);
7.56 s (2H, NH2); 7.59 t, 7.75 t, and 7.99 d (5H, C6H5).
Found, %: C 61.25; H 5.26; N 21.30. C20H20N6O3. Cal-
culated, %: C 61.21; H 5.14; N 21.42.
Crystallographic parameters: a = 10.1568(14), b =
12.8889(16), c = 15.8516(15) Å; α = 90.00, β =
100.65(2), γ = 90.00°; V = 2039.4(4) Å3; Z = 4; space
group P21/c. Total number of reflections 3595; number
of reflections with I > 2σ(I) 1504; number of refined
parameters 264; divergence factor R = 0.075.
4-Amino-2,2-bis(isopropylideneaminooxy)-
6-(2-thienylcarbonyl)-3-azabicyclo[3.1.0]hex-3-ene-
1,5-dicarbonitrile (VIe). Yield 65%, mp 161–162°C
(decomp.). IR spectrum, ν, cm–1: 3378, 3266 (NH2);
3045 (C–H); 2249 (C≡N); 1668 (C=O). 1H NMR spec-
trum, δ, ppm: 1.73 s, 1.86 s, 1.87 s, and 1.94 s (3H,
CH3); 4.01 s (1H, CH); 7.34 t, 8.09 d, and 8.22 d (3H,
C4H3S); 7.54 s (2H, NH2). Found, %: C 54.25; H 4.67;
N 21.10. C18H18N6O3S. Calculated, %: C 54.26;
H 4.55; N 21.09.
Compounds VIb–VIe were synthesized in a similar
way.
4-Amino-2,2-bis(isopropylideneaminooxy)-6-
(4-methoxybenzoyl)-3-azabicyclo[3.1.0]hex-3-ene-
1,5-dicarbonitrile (VIb). Yield (65%), mp 182–183°C
(decomp.). IR spectrum, ν, cm–1: 3348, 3269 (NH2);
3069 (C–H); 2246 (C≡N); 1674 (C=O). 1H NMR spec-
trum, δ, ppm: 1.77 s, 1.85 s, 1.87 s, and 1.98 s (3H
each, CH3); 3.79 s (3H, OCH3); 4.01 s (1H, CH);
7.10 d and 7.97 d (2H each, C6H4); 7.54 s (2H, NH2).
13C NMR spectrum (DMSO-d6), δC, ppm: 15.95,
21.45, 21.75 (CH3); 34.42 (C5); 38.86 (C1); 41.14 (C6);
55.90 (OCH3); 111.93, 112.94 (CN); 114.29, 127.87,
131.39, 160.91 (C6H4); 123.17 (C2); 158.26, 157.21
(N=C); 164.46 (C4); 186.97 (C=O). Found, %:
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.
REFERENCES
1. Hart, H. and Freeman, F., J. Org. Chem., 1963, vol. 28,
p. 1220.
2. Freeman, F., Synthesis, 1981, p. 925.
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SYNTHESIS OF 2,2,3,3-TETRACYANOCYCLOPROPYL KETONES
1335
14. Yashkanova, O.V., Lukin, P.M., Nasakin, O.E., Ur-
man, Ya.G., Khrustalev, V.N., Nesterov, V.N., and Ant-
ipin, M.Yu., Russ. J. Org. Chem., 1997, vol. 33, p. 877.
3. Ramberg, L. and Wideqvist, S., Ark. Kemi, 1937, p. 1.
4. Ramberg, L. and Wideqvist, S., Ark. Kemi, 1941, p. 1.
5. Yashkanova, O.V., Nasakin, O.E., Urman, Ya.G., Khru-
stalev, V.N., Nesterov, V.N., Antipin, M.Yu., and Lu-
kin, P.M., Russ. J. Org. Chem., 1997, vol. 33, p. 475.
6. Nasakin, O.E., Lukin, P.M., Vershinin, E.V., Lyshchi-
kov, A.N., Urman, Ya.G., and Yashkanova, O.V., Russ. J.
Org. Chem., 1996, vol. 32, p. 361.
7. Siaka, S., Kayukova, O.V., Kayukov, Ya.S., Lukin, P.M.,
Khrustalev, V.N., Nesterov, V.N., Nasakin, O.E., and
Antipin, M.Yu., Russ. J. Org. Chem., 1998, vol. 34,
p. 1269.
8. Kayukova, O.V., Kayukov, Ya.S., Nikolaev, A.N., Tafe-
enko, V.A., Ershov, O.V., and Nasakin, O.E., Russ. J.
Org. Chem., 2005, vol. 41, p. 523.
9. Kayukova, O.V., Kayukov, Ya.S., Lapteva, E.S., Barda-
sov, I.N., Ershov, O.V., and Nasakin, O.E., Russ. J. Org.
Chem., 2006, vol. 42, p. 1414.
10. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S., Er-
shov, O.V., and Nasakin, O.E., Russ. J. Org. Chem.,
2007, vol. 43, p. 1252.
15. Siaka, S., Lukin, P.M., Nasakin, O.E., Antipin, M.Yu.,
and Khrustalev, V.N., Russ. J. Org. Chem., 1999,
vol. 35, p. 269.
16. Yashkanova, O.V., Nasakin, O.E., Urman, Ya.G., Khru-
stalev, V.N., Nesterov, V.N., Antipin, M.Yu., Lu-
kin, P.M., and Vershinin, E.V., Russ. J. Org. Chem.,
1997, vol. 33, p. 484.
17. Siaka, S., Lukin, P.M., Nasakin, O.E., Khrustalev, V.N.,
Nesterov, V.N., Antipin, M.Yu., and Pul’kherov-
skaya, O.V., Russ. J. Org. Chem., 1997, vol. 33, p. 838.
18. Reutov, O.A., Kurts, A.L., and Butin, K.P., Organi-
cheskaya khimiya (Organic Chemistry), Moscow:
Binom, 2004, vol. 4, p. 273.
19. Regan, T.H., J. Org. Chem., 1962, vol. 27, p. 2236.
20. Kayukova, O.V., Lukin, P.M., Kayukov, Ya.S., Nasa-
kin, O.E., Khrustalev, V.N., Nesterov, V.N., and An-
tipin, M.Yu., Khim. Geterotsikl. Soedin., 1998, no. 2,
p. 170.
21. Bardasov, I.N., Kayukova, O.V., Kayukov, Ya.S., Er-
shov, O.V., Nasakin, O.E., and Belikov, M.Yu., Russ. J.
Org. Chem., 2007, vol. 43, p. 1565.
11. Elison, M.N., Fedukovich, S.K., Zaimovskaya, T.A.,
Vereshchagin, A.N., and Nikishin, G.I., Izv. Ross. Akad.
Nauk, Ser. Khim., 2003, p. 2122.
12. Nasakin, O.E., Lukin, P.M., Lindeman, S.V., and
22. Lukin, P.M., Manzenkov, A.V., Urman, Ya.G., Khrusta-
lev, V.N., Nesterov, V.N., and Antipin, Yu.M., Russ. J.
Org. Chem., 2000, vol. 36, p. 226.
23. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E., Selyuni-
na, E.V., Tikhonova, I.G., Chernushkin, A.N., and Khru-
stalev, V.N., Russ. J. Gen. Chem., 2000, vol. 70, p. 1251.
Struchkov, Y.T., Mendeleev Commun., 1994, p. 185.
13. Nasakin, O.E., Lukin, P.M., Vershinin, E.V., Yashka-
nova, O.V., Lyshchikov, A.N., Urman, Ya.G., Linde-
man, S.V., Struchkov, Yu.T., and Bulai, A.Kh., Russ. J.
Org. Chem., 1995, vol. 31, p. 333.
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