Three-component synthesis of 2-(4-amino-2,5-dihydro-1H-imidazol-5-ylidene) malononitriles

Article abstract of DOI:10.1134/S1070428008040179

2-(4-Amino-2,5-dihydro-1H-imidazol-4-ylidene)malononitriles were synthesized by three-component reaction of tetracyanoethylene, carbonyl compound, and ammonium acetate. The synthesis can be performed in two steps with intermediate isolation of 2-aminoethe

Full text of DOI:10.1134/S1070428008040179

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 4, pp. 570–576. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © O.V. Ershov, A.V. Eremkin, Ya.S. Kayukov, A.N. Lyshchikov, O.E. Nasakin, V.A. Tafeenko, 2008, published in Zhurnal
Organicheskoi Khimii, 2008, Vol. 44, No. 4, pp. 575–581.
Three-Component Synthesis of 2-(4-Amino-2,5-dihydro-
1H-imidazol-5-ylidene)malononitriles
O. V. Ershova, A. V. Eremkina, Ya. S. Kayukova, A. N. Lyshchikova,
O. E. Nasakina, and V. A. Tafeenkob
a I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: oleg.ershov@mail.ru
b Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
Received November 18, 2006
Abstract—2-(4-Amino-2,5-dihydro-1H-imidazol-4-ylidene)malononitriles were synthesized by three-com-
ponent reaction of tetracyanoethylene, carbonyl compound, and ammonium acetate. The synthesis can be
performed in two steps with intermediate isolation of 2-aminoethene-1,1,2-tricarbonitrile, as well as using
preliminarily prepared 2-aminoethene-1,1,2-tricarbonitrile and 1,3,5-trisubstituted 2,4-diazapentadienes.
DOI: 10.1134/S1070428008040179
Reactions of tetracyanoethylene with ketones
underlie many syntheses of aliphatic, alicyclic, and
heterocyclic compounds that are difficult to obtain by
other methods [1–5]. Despite considerable progress in
studying the chemistry of 4-oxoalkane-1,1,2,2-tetracar-
bonitriles (tetracyanoethylene adducts with ketones),
analogous reactions with aldehydes were not reported.
Presumably, the reason is that tetracyanoalkanals are
difficult to isolate under the classical reaction condi-
tions due to their high reactivity. Therefore, we pre-
sumed that three-component transformations are fea-
sible. Such reactions ensure self-assembly of hetero-
cyclic or alicyclic systems from simple precursors via
one-pot processes [6]. Following this approach, we
succeeded in effecting three-component reactions of
tetracyanoethylene with aldehydes and obtaining sub-
stituted 6-imino-2,7-dioxabicyclo[3.2.1]octane-4,4,5-
tricarbonitriles [7], 5,5-dialkyl-2-halo-6-hydroxy-5,6-
dihydro-1H-pyridine-3,4,4-tricarbonitriles [8], and
2,4-dialkyl-7-imino-6-oxabicyclo[3.2.1]oct-3-ene-
1,8,8-tricarbonitriles [9].
While continuing systematic studies on reactions of
tetracyanoethylene with aldehydes, we have found that
these compounds in the presence of ammonium acetate
(as source of ammonia) give rise to substituted
2-(4-amino-2-alkyl-2,5-dihydro-1H-imidazol-5-
ylidene)malononitriles IIa–IIc in 36–42% yield
(Scheme 1). The reaction sequence is likely to include
initial formation of aminotricyanoethylene I and alde-
hyde imine A. It is known that tetracyanoethylene
having an electron-deficient double bond readily reacts
with electron-rich compounds [10]. An example is its
Scheme 1.
NH
NC
NC
CN
CN
NC
NC
CN
+
RCHO + 2NH4OAc
+
–HCN, –H2O, –2AcOH
R
H
NH2
I
A
H2N
CN
CN
H
N
R
N
NC
NC
R
N
NH2 CN
H
B
IIa–IIc
R = i-Pr (a), Et2CH (b), BuEtCH (c).
570

THREE-COMPONENT SYNTHESIS OF 2-(5-AMINO-3,4-DIHYDRO-...
N2
571
reaction with amines, which leads to R-aminotricyano-
ethylenes [10, 11]. The reaction of tetracyanoethylene
with ammonia gives no analogous derivative, but the
subsequent transformations result in the formation of
2-(1,2,2-tricyanovinylamino)ethene-1,1,2-tricarboni-
trile ammonium salt [10, 12].
C4
N1
C1
C5
The use of ammonium acetate allowed us to avoid
reactions originating from basic properties of the rea-
gent. Acetic acid and hydrogen cyanide accumulating
in the reaction mixture should stabilize enamino nitrile
I formed in the first stage even more strongly. To
verify this assumption, we examined the reaction of
tetracyanoethylene with excess ammonium acetate in
dioxane. As a result, we isolated 94% of 2-amino-
ethene-1,1,2-tricarbonitrile (I) whose structure was
proved by X-ray analysis (Fig. 1).
C3
N3
C2
N4
H1
H2
Fig. 1. Structure of the molecule of 2-aminoethene-1,1,2-tri-
carbonitrile (I) according to the X-ray diffraction data.
The formation of aminoethenetricarbonitrile I by
reaction of tetracyanoethylene with ammonium acetate
is likely to be accompanied by transformation of alde-
hydes into imines A. The latter are very unstable, for
they readily undergo hydrolysis or polymerization, and
they react in statu nascendi with vinylamine I to form
intermediate B. The amino group in the latter is in-
volved in intramolecular cyclization with participation
of the neighboring cyano group, yielding final imida-
zole derivatives II (Scheme 1).
than in the reactions shown in Schemes 1 and 2. We
thus succeeded in reacting aminoethenetricarbonitrile I
with hydrobenzamide (IIId) as synthetic equivalent of
benzaldehyde imine.
We proposed two schemes to rationalize the ob-
served transformations. According to the first of these,
the process begins with addition of the amino group in
aminoethenetricarbonitrile I at the C=N bond of com-
pounds III. This scheme is analogous to the reaction of
I with carbonyl compounds in the presence of ammo-
nium acetate (Scheme 1). The second path is shown in
Scheme 3. In this case, nucleophilic nitrogen atom in
Schiff base III attacks electrophilic carbon atom of
the cyano group in I, and next follows imidazole ring
closure. Presumably, the reactions following these
schemes are characterized by different rates, depend-
ing on steric factors related to the substituents.
To verify the proposed scheme of transformations,
we performed reaction of aminoethenetricarbonitrile I
with aldehydes in the presence of ammonium acetate.
In fact, the products were 2-(4-amino-2-alkyl-2,5-di-
hydro-1H-imidazol-5-ylidene)malononitriles IIa–IIc
(42–56%; Scheme 2). These data confirmed formation
of aminoethenetricarbonitrile I in the first stage.
Scheme 2.
The revealed reaction of tetracyanoethylene with
aldehydes, leading to imidazole derivatives IIa–IId,
I
+
RCHO
+
NH4OAc
IIa–IIc
–H2O, –2AcOH
N5
In order to refine the scheme of formation of com-
pounds IIa–IIc, we performed additional experiments
in which aminotricyanoethylene I was brought into
reactions with preliminarily prepared imines A. Taking
into account the above stated instability of aldehyde
imines (which cannot be isolated as individual sub-
stances), the reactions were carried out with their
structural analogs, 1,3,5-trisubstituted 2,4-diazapenta-
1,4-dienes IIIa–IIId. By reactions of compounds
IIIa–IIId with aminoethenetricarbonitrile I we also
obtained imidazolylidenemalononitriles IIa–IId
(Scheme 3). These reactions occurred at a higher rate,
and the yields of compounds II were greater (55–63%)
C6
C12
C13
C7
N4
C8
C5
C3
C11
C9
C10
N1
N3
C2
N2
Fig. 2. Structure of the molecule of 2-(3-amino-1,4-diaza-
spiro[4.5]dec-3-en-2-ylidene)malononitrile (IIe) according
to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

ERSHOV et al.
572
Scheme 3.
R
R
R
R
N
N
N
N
N
R
N
N
NC
NC
N
R
I
+
NC
NC
H2N
R
R
R
N
NH2
H
H
IIIa–IIId
HN
NH
N
2H2O
NC
NC
NC
NC
–2RCHO, –NH3
R
R
N
N
H
H
IIa–IId
R = i-Pr (a), Et2CH (b), BuEtCH (c), Ph (d).
Scheme 4.
H2N
N
NC
NC
CN
NH4OAc
–HCN, –AcOH
RR'C=O, NH4OAc
–HCN, –AcOH
NC
NC
I
R
R'
N
H
CN
IIe–IIi
RR′ = (CH2)5 (e), (CH2)2CH(Me)(CH2)2 (f), (CH2)2CH(Ph)(CH2)2 (g), CH(Me)(CH2)4 (h), (CH2)11 (i).
was extended to a number of ketones. The three-com-
ponent condensation of tetracyanoethylene with cyclo-
hexanone, substituted cyclohexanones, and cyclodo-
decanone in the presence of ammonium acetate gave
malononitriles IIe–IIi in 49–65% yield. As in the case
of aldehydes, compound IIe–IIi were also obtained
from the corresponding ketones and aminoethenetri-
carbonitrile I (yield 52–82%; Scheme 4). These data
confirmed that the process may involve intermediate
formation of imines A, for cyclic ketones cannot be
transformed into Schiff bases like III.
Thus we succeeded in effecting self-assembly of
2,5-dihydro-1H-imidazole ring along three approaches:
(1) direct synthesis from tetracyanoethylene, aldehyde,
and ammoniun acetate (Schemes 1, 4); (2) two-step
process with preliminary isolation of intermediate
aminoethenetricarbonitrile I (Schemes 2, 4); and
(3) reaction of preliminarily prepared aminoethenetri-
carbonitrile I with 1,3,5-trisubstituted 2,4-diazapenta-
1,4-dienes (Scheme 3).
a
b
c
C
H
N
The structure of compound IIe was determined by
X-ray analysis (Fig. 2). The geometric parameters of
molecule IIe (bond lengths and bond angles) did not
fall out of the corresponding standard ranges [13]. The
crystalline structure of compound IIe is characterized
by formation of centrosymmetric dimers via strong
intermolecular hydrogen bonds (Fig. 3).
The structure of compounds IIa–IIi was also con-
firmed by the IR, 1H NMR, and mass spectra. Their IR
spectra contained strong absorption bands in the region
3100–3500 cm–1 due to stretching vibrations of the
N–H bonds and bands at 1645–1650 cm–1 due to vibra-
Fig. 3. Intermolecular hydrogen bonds in the crystalline struc-
ture of 2-(3-amino-1,4-diazaspiro[4.5]dec-3-en-2-ylidene)-
malononitrile (IIe).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

THREE-COMPONENT SYNTHESIS OF 2-(5-AMINO-3,4-DIHYDRO-...
573
Table 1. Bond lengths (d) and bond angles (ω) in the mole-
cule of 2-aminoethene-1,1,2-tricarbonitrile (I)
tions of the C=N bonds. Conjugated cyano groups
gave rise to medium-intensity bands in the region
2210–2230 cm–1, and stretching vibrations of the
double C=C bond appeared at 1590–1600 cm–1.
Bond
d, Å
Bond
d, Å
N4–C2
N1≡C3
N2≡C4
N3≡C5
1.326(2)
1.131(3)
1.136(2)
1.138(2)
C2=C1
C2–C3
C1–C4
C1–C5
1.366(2)
1.462(2)
1.421(2)
1.430(2)
Compounds IIa–IIi displayed in the 1H NMR spec-
tra a singlet at δ 12.10–11.40 ppm from the NH proton
in the imidazole ring and a singlet at δ 6.4–6.25 ppm
from the amino group. In the spectrum of IIi, the
amino group protons resonated at δ 5.02 ppm. Signals
from the 2-H proton in the imidazole ring of com-
Angle
ω, deg
Angle
ω, deg
1
C2N4H1
C2N4H2
H1N4H2
N4C2C1
N4C2C3
C1C2C3
118.5(14)0
120.0(19)0
121(2)0.00
127.07(15)
116.27(15)
116.65(14)
C2C1C4
C2C1C5
C4C1C5
N1C3C2
N2C4C1
N3C5C1
120.34(15)
122.94(14)
116.72(15)
178.7(2)00
177.2(2)00
176.56(19)
pounds IIa–IIc appeared in the H NMR spectra as
a doublet of doublets at δ 5.4–5.2 ppm, and the corre-
sponding signal of 2-phenyl derivative IIc was a dou-
blet at δ 6.22 ppm. In the mass spectra of IIa–IIi, the
molecular ion peak had a relative intensity of 15–95%.
From the viewpoint of modern synthetic chemistry,
imidazole ring is built up via heterocyclization proc-
esses [14]. The main reagent for the synthesis of imid-
azoles containing cyano groups is diaminoethylenedi-
carbonitrile [15–17]. This reagent ensures imidazole
ring closure through simultaneous formation of 1–2
and 2–3 bonds. Therefore, the described synthetic ap-
proach to partially hydrogenated aminoimidazoles on
the basis of previously unknown aminotricyanoethyl-
ene I seems to be unusual, for it involves formation of
1–2 and 3–4 (or 1–5 and 2-–3) bonds. It is also inter-
esting that intramolecular heterocyclization of inter-
mediate B results in the formation of five-membered
imidazole heteroring, whereas enamino nitrile frag-
ment typically gives rise to six-membered (pyrimidine)
ring [18–21]. In the examined reactions, the cycliza-
tion involves the C3≡N1 group attached to the same
carbon atom as the amino group rather than that in the
dicyanomethylidene fragment. The observed regio-
selectivity may be rationalized by increased electron
density on the C4 and C5 atoms due to strong n,π-con-
jugation between the amino group and two cyano
groups on C1. On the other hand, the C3≡N1 group
(Fig. 1) is not involved in such conjugation, so that it
is activated toward nucleophilic attack.
gen bond system (Fig. 4) also counts in favor of con-
jugation leading to increase in the electron density on
the C4≡N2 and C5≡N3 cyano groups [22].
We also calculated the charges on atoms in mole-
cule I at the B3LYP/6-311G level using Gaussian 98
software (Table 2). Analogous calculations were per-
formed for ethene-1,1,2-tricarbonitrile (IV) with a view
to elucidate how the presence of amino group affects
charge distribution in the molecule of 2-aminoethene-
1,1,2-tricarbonitrile (I). The results showed that the
negative charges on the N2 and N3 atoms (for atom
numbering, see Fig. 1) in molecule I are larger than
those found for molecule IV, while the negative charge
on N1 in molecule I is lower than that in molecule IV.
Thus participation of just the N2 and N3 atoms in intra-
N1′
N1
N2
N3
N2′
N4
N3′
The X-ray diffraction data (Table 1) support the
above stated. The formally single C2–N4 bond in mole-
cule I is shortened to 1.326(2) Å, while the formally
double C1=C2 bond is extended to 1.366(2) Å; in addi-
tion, the C–CN bonds are nonequivalent (C2–C3 1.462,
C1–C4 1.421, C1–C5 1.430 Å). We believe that the
reason is strong n,π-conjugation in the molecule. One
more evidence is provided by the planar structure of
the amino group (the sum of the bond angles at the N4
atom is 360°). The formation of intermolecular hydro-
Fig. 4. Intermolecular hydrogen bonds in the crystalline struc-
ture of 2-aminoethene-1,1,2-tricarbonitrile (I).
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ERSHOV et al.
574
Table 2. Charges on atoms in the molecules of 2-amino-
ethene-1,1,2-tricarbonitrile (I) and ethene-1,1,2-tricarbo-
nitrile (IV)
2-(4-Amino-2-isopropyl-2,5-dihydro-1H-imida-
zol-5-ylidene)malononitrile (IIa). a. Tetracyanoethyl-
ene, 0.64 g (5 mmol), was dissolved in 5 ml of diox-
ane, 1 g of ammonium acetate and 0.36 g (5 mmol) of
isobutyraldehyde were added, and the mixture was
stirred for 6 h until negative test for tetracyanoethylene
(with hydroquinone). The mixture was diluted with
water, and the precipitate was filtered off, washed with
water and propan-2-ol, and recrystallized from propan-
2-ol. Yield 42%.
Atom
I
IV
Atom
I
IV
C1
C2
C3
C4
+0.004 +0.069
+0.354 +0.054
+0.048 +0.056
+0.026 +0.067
C5
N1
N2
N3
+0.071+ +0.093+
−0.162– −0.177–
−0.196– −0.167–
−0.201– −0.177–
molecular hydrogen bonding (X-ray diffraction data,
Fig. 4) is consistent with the calculated electron den-
sity distribution [22].
b. Compound I, 0.29 g (2.5 mmol), was added
under stirring to a suspension of 0.5 g of ammonium
acetate and 0.18 g (2.5 mmol) of isobutyraldehyde in
5 ml of dioxane. When the reaction was complete
(TLC), the mixture was diluted with water, and the
precipitate was filtered off, washed with water and
propan-2-ol, and recrystallized from propan-2-ol.
Yield 56%.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spec-
trometer from samples dispersed in mineral oil. The
1H NMR spectra were measured on a Bruker AM-500
spectrometer (500.13 MHz) using DMSO-d6 as sol-
vent. The molecular weights were determined from the
mass spectra (electron impact, 70 eV) which were ob-
tained on a Finnigan Mat Incos 50 instrument. X-Ray
diffraction data for single crystals of compounds I and
IIe were acquired on an Enraf–Nonius CAD-4 four-
circle diffractometer (MoKα irradiation, graphite mono-
chromator, ω-scanning). The unit cell parameters were
determined and refined using 25 reflections in the Θ
range from 11 to 20°. The structures were solved, and
the positional and thermal parameters of atoms were
refined, using SHELXL97 software package [23].
Hydrogen atoms were localized by Fourier difference
syntheses, and their positions were refined in isotropic
approximation. The positions and thermal vibration
tensors of non-hydrogen atoms were refined in full-
matrix anisotropic approximation. The progress of re-
actions and the purity of products were monitored by
thin-layer chromatography on Silufol UV-254 plates.
c. Compound I, 0.29 g (2.5 mmol), and Schiff base
IIIa, 0.33 g (1.7 mmol), were dissolved in 5 ml of
dioxane. After 3 h, the mixture was diluted with water,
and the precipitate was filtered off, washed with water
and propan-2-ol, and recrystallized from propan-2-ol.
Yield 63%, mp 202–203°C. IR spectrum, ν, cm–1:
3460, 3280–3100 (NH, NH2); 2225, 2220 (C≡N); 1645
1
(C=N). H NMR spectrum, δ, ppm: 11.40 d (1H, NH),
6.43 s (2H, NH2), 5.21 d.d (1H, 2-H), 2.04 m [1H,
CH(CH3)2], 0.95 d (3H, CH3, J = 6.7 Hz), 0.72 d (3H,
CH3, J = 6.7 Hz). Mass spectrum: m/z 189 (Irel 15%)
[M]+. Found, %: C 57.02; H 5.75; N 37.03. C9H11N5.
Calculated, %: C 57.13; H 5.86; N 37.01. M 189.22.
Compounds IIb–IIi were synthesized in a similar
way.
2-[4-Amino-2-(1-ethylpropyl)-2,5-dihydro-1H-
imidazol-5-ylidene]malononitrile (IIb). Yield 40 (a),
49 (b), 55% (c); mp 209–210°C. IR spectrum, ν, cm–1:
3430, 3280–3100 (NH, NH2); 2225, 2220 (C≡N); 1650
1
(C=N). H NMR spectrum, δ, ppm: 11.42 d (1H, NH),
2-Aminoethene-1,1,2-tricarbonitrile (I). Tetra-
cyanoethylene, 0.64 g (0.005 mol), was added under
stirring to a suspension of 0.97 g of ammonium acetate
in 5 ml of 1,4-dioxane. After 20 min (test with hydro-
quinone, TLC), the mixture was filtered, 0.5 g of
methyl iodide was added to the filtrate, and the solvent
was removed under reduced pressure. The residue was
ground with hexane, and the precipitate was filtered
off. Yield 0.55 g (94%). Yellow crystals of I suitable
for X-ray analysis were grown from a solution in
dioxane. Rhombic crystals, space group Pca21; unit
cell parameters: a = 13.3146(8), b = 5.7488(4), c =
7.1774(6) Å; Z = 4; divergence factor R = 0.032.
6.38 s (2H, NH2), 5.41 d.d (1H, 2-H), 1.62 m [1H,
CH(CH2)2], 1.35 m (2H, CHCH2CH3), 1.10 m (2H,
CHCH2CH3), 0.95 t (3H, CH3, J = 7.3 Hz), 0.85 t (3H,
CH3, J = 7.3 Hz). Mass spectrum: m/z 217 (Irel, 14%)
[M]+. Found, %: C 60.71; H 6.85; N 32.03. C11H15N5.
Calculated, %: C 60.81; H 6.96; N 32.23. M 217.27.
2-[5-Amino-2-(1-ethylpentyl)-2,5-dihydro-1H-
imidazol-5-ylidene]malononitrile (IIc). Yield 36 (a),
42 (b), 57% (c); mp 209–210°C. IR spectrum, ν, cm–1:
3430, 3280–3100 (NH, NH2); 2225, 2220 (C≡N); 1650
1
(C=N). H NMR spectrum, δ, ppm: 11.39 d (1H, NH),
6.39 s (2H, NH2), 5.40 d.d (1H, 2-H), 1.66 m [1H,
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THREE-COMPONENT SYNTHESIS OF 2-(5-AMINO-3,4-DIHYDRO-...
575
CH(CH2)2], 1.4–0.8 m (14H, CH2, CH3). Mass spec-
trum: m/z 245 (Irel 10%) [M]+. Found, %: C 63.59;
H 7.86; N 28.50. C13H19N5. Calculated, %: C 63.65;
H 7.81; N 28.55. M 245.32.
1H NMR spectrum, δ, ppm: 11.35 s (1H, NH), 6.44 s
(2H, NH2), 1.9–1.2 m (9H, CH, CH2), 0.4 d (3H, CH3).
Mass spectrum: m/z 229 (Irel 47%) [M]+. Found, %:
C 62.83; H 6.64; N 30.49. C12H15N5. Calculated, %:
C 62.86; H 6.59; N 30.54. M 229.28.
2-(5-Amino-2-phenyl-2,5-dihydro-1H-imidazol-
5-ylidene)malononitrile (IId). Yield 40 (a), 59% (b);
mp 208–209°C. IR spectrum, ν, cm–1: 3450, 3330–
3100 (NH, NH2); 2230, 2210 (C≡N); 1650 (C=N).
1H NMR spectrum, δ, ppm: 12.10 d (1H, NH), 7.81 d
(2H, o-H, J = 7.4 Hz), 7.41 t (2H, m-H, J = 7.4 Hz),
7.28 t (1H, p-H, J = 7.4 Hz), 6.22 d (1H, 2-H), 5.05 s
(2H, NH2). Mass spectrum: m/z 223 (Irel 50%) [M]+.
Found, %: C 64.52; H 4.13; N 31.31. C12H9N5. Cal-
culated, %: C 64.56; H 4.06; N 31.37. M 223.24.
2-(3-Amino-1,4-diazaspiro[4.11]hexadec-3-en-
2-ylidene)malononitrile (IIi). Yield 49 (a), 52% (b);
mp 205–206°C. IR spectrum, ν, cm–1: 3500, 3400,
3280–3100 (NH, NH2); 2225, 2210 (C≡N); 1645
1
(C=N). H NMR spectrum, δ, ppm: 11.51 s (1H, NH),
6.25 s (2H, NH2), 1.7–1.25 m (22H, CH2). Mass spec-
trum, m/z 299 (Irel 24%) [M]+. Found, %: C 68.02;
H 8.50; N 23.30. C17H25N5. Calculated, %: C 68.19;
H 8.42; N 23.39. M 299.41.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-97015).
2-(3-Amino-1,4-diazaspiro[4.5]dec-3-en-2-
ylidene)malononitrile (IIe). Yield 62 (a), 72% (b);
mp 198–199°C. IR spectrum, ν, cm–1: 3440, 3280–
3100 (NH, NH2); 2225, 2210 (C≡N); 1645 (C=N).
1H NMR spectrum, δ, ppm: 11.41 s (1H, NH), 6.25 s
(2H, NH2), 1.8–1.2 m (10H, CH2). Mass spectrum:
m/z 215 (Irel 52%) [M]+. Found, %: C 61.23; H 5.93;
N 32.47. C11H13N5. Calculated, %: C 61.38; H 6.09;
N 32.54. M 215.26. Crystallographic data: a =
20.7450(7), b = 5.822(1), c = 20.852(1) Å; β =
116.10(1)°; Z = 8; space group C12/c1; divergence
factor R = 0.051.
REFERENCES
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2-(3-Amino-8-methyl-1,4-diazaspiro[4.5]dec-3-
en-2-ylidene)malononitrile (IIf). Yield 65 (a), 80%
(b); mp 196–197°C. IR spectrum, ν, cm–1: 3460, 3280–
3100 (NH, NH2); 2235, 2200 (C≡N); 1665 (C=N).
1H NMR spectrum, δ, ppm: 11.45 s (1H, NH), 6.34 s
(2H, NH2), 1.9–1.2 m (9H, CH, CH2), 0.90 d (3H,
CH3, J = 6.8 Hz). Mass spectrum: m/z 229 (Irel 45%)
[M]+. Found, %: C 62.86; H 6.69; N 30.43. C12H15N5.
Calculated, %: C 62.86; H 6.59; N 30.54. M 229.28.
2-(3-Amino-8-phenyl-1,4-diazaspiro[4.5]dec-3-
en-2-ylidene)malononitrile (IIg). Yield 54 (a), 66%
(b); mp 208–209°C. IR spectrum, ν, cm–1: 3500, 3400,
3280–3100 (NH, NH2); 2225, 2200 (C≡N); 1650
1
(C=N). H NMR spectrum, δ, ppm: 11.53 s (1H, NH),
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11.53 s (1H, NH), 7.30 t (2H, m-H, J = 7.4 Hz), 7.24 d
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6.43 s (2H, NH2), 2.63 m (1H, 2-H), 2.1–1.35 m (8H,
CH2). Mass spectrum: m/z 291 (Irel 95%) [M]+. Found,
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C 70.08; H 5.88; N 24.04. M 291.36.
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3100 (NH, NH2); 2225, 2210 (C≡N); 1645 (C=N).
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