Aryl(hetaryl)-containing gem-cyanonitroethenes: Synthesis, structure, and reactions with 2,3-dimethyl-1,3-butadiene

Article abstract of DOI:10.1134/S1070363215080101

Methods of aryl(hetaryl)-substituted gem-cyanonitroethenes preparation are summarized, and the products structure elucidation by means of ¹H, ¹³C NMR, IR, and UV spectroscopy methods is discussed. E-Configuration of the compounds obt

Full text of DOI:10.1134/S1070363215080101

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 8, pp. 1845–1854. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.I. Baichurin, N.I. Aboskalova, E.V. Trukhin, V.M. Berestovitskaya, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85,
No. 8, pp. 1288–1297.
To the 80th Anniversary of B.I. Ionin
Aryl(hetaryl)-Containing gem-Cyanonitroethenes:
Synthesis, Structure, and Reactions
with 2,3-Dimethyl-1,3-butadiene
R. I. Baichurin, N. I. Aboskalova, E. V. Trukhin, and V. M. Berestovitskaya
Herzen State Pedagogical University of Russia, nab. reki Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received May 7, 2015
Abstract—Methods of aryl(hetaryl)-substituted gem-cyanonitroethenes preparation are summarized, and the
1
products structure elucidation by means of H, 13C NMR, IR, and UV spectroscopy methods is discussed. E-
Configuration of the compounds obtained has been proved. Reaction of the studied gem-cyanonitroethenes with
2,3-dimethyl-1,3-butadiene affords the diene synthesis adducts – 6-aryl(hetaryl)-3,4-dimethyl-1-nitro-1-cyano-
3-cyclohexenes .
Keywords: 1-cyano-1-nitroethene, α-nitroacrylonitrile, nitrile of α-nitrocinnamic acid, Diels–Alder reaction
DOI: 10.1134/S1070363215080101
Geminal cyanonitroethenes are synthetically
accessible convenient synthons for preparation of
various organic compounds [1].
synthesized using crude (not purified) nitroacetonitrile
obtained via the reaction of methazonic acid with
thionyl chloride [2] in the absence of any catalytic
agents [16, 18, 19]. Purified nitroacetonitrile has been
introduced in the reactions with furfural, 2-formyl-
thiophene, 2-formylpyrrole, and 1-methyl-2-formyl-
pyrrole [19–21]. The nitroacetonitrile can be purified
via the two methods: fractional distillation under reduced
pressure and column chromatography on silicic acid
[21]. The reaction of the so purified nitroacetonitrile
with heterocyclic aldehydes proceed in anhydrous
ethanol or in an ethanol–diethyl ether mixture at 20°C
without any catalytic agents to give the corresponding
gem-cyanonitroethenes with up to 77% yield.
Aryl(hetaryl)-containing gem-cyanonitroethenes have
been prepared via condensation of the corresponding al-
dehydes with nitroacetonitrile under various condi-
tions: in the presence of methylamine or ethylamine
hydrochlorides and sodium carbonate [2–7], β-alanine
[8], n-propylamine [9], Iran dolomite [10], and on
silica gel [11]. Preparation of nitrile of α-nitrocinnamic
acid and its analogs via alkenylation of nitroaceto-
nitrile with aldehydes in aqueous medium [12], solvent
free conditions [13], in ionic liquids [14a], and under
microwave irradiation [14b] has been reported.
Unfortunately, most of the mentioned papers lack
information about the quality grade of nitroacetonitrile
introduced to the reaction. Most likely, crude
nitroacetonitrile has been initially converted into the
ammonium salt that was acidified afterwards [15];
therefore, synthesis of gem-cyanonitroethenes via the
described procedure requires two additional steps.
We prepared a number of aryl- and hetaryl-sub-
stituted gem-cyanonitroethenes I–VI via condensation
of crude nitroacetonitrile [2] with the corresponding al-
dehydes; the nitroalkenes were isolated in up to 90% yield
(Scheme 1).
Structures of the synthesized 2-aryl(hetaryl)-1-cyano-
1-nitroethenes I–VI were studied by IR, UV, and NMR
spectroscopy methods.
Other studies devoted to the reactions of nitro-
containing methylene compounds with aryl(hetaryl)
aldehydes under acidic catalysis [16–18] have
demonstrated that gem-cyanonitroethenes can be
The value of the olefinic proton chemical shift
served as the main indication of the geometry con-
1845

1846
BAICHURIN et al.
Table 1. 1H NMR spectral parameters of gem-E-cyanonitroethenes I–VI (δ, ppm; J, Hz)
Х
Y
c
d
c
e
b
d
b
1
CN
1
CN
f
a
a
Х
2
3
2
3
HA
I−IV
NO2
HA
NO2
V, VI
Ar, Het
Hc
CH3 (OH)
[HB]
Comp. no.
X
Y
HA
Hb
Hf
He
Hd
I
H
H
8.66 s
8.58 s
8.57 s
8.42 s
8.43 s
8.81 s
–
8.01 d.d
8.01 d
7.59 d.d
3Jb,c 8.24, 3Jc,d 7.45, 4Jb,d 1.20
7.69 t.t
II
MeO
OH
Me2N
O
H
3.94 s
7.06 d
3Jb,c 9.00
–
–
III
IV
V
MeO
4.01 (6.50 s)
7.78 d
7.49 d.d
–
3Je,f 8.24, 4Jb,f 1.83
6.74 d
7.08 d
H
–
3.19 s
7.90 br.d
7.54 d
8.00 d
–
3Jb,c 9.22
–
–
–
–
6.81 d.d
3Jb,c 3.43, 3Jc,d 1.55
–
–
7.93 d
8.04 d
VI
S
–
7.36 d.d
3Jb,c 4.02, 3Jc,d 4.91
Model compound [24]
7.87 d
[7.60 d]
Ph–CHA=CHB–NO2
3JAB 14.0
figuration of the discussed gem-functionalized nitro-
ethenes as assessed by means of H NMR spectro-
shifted downfield compared to that in the model E-
nitroethenes. For example, the chemical shifts of HA
and HB protons were of 7.87 and 7.60 ppm,
1
scopy: in the case of the cis-orientation towards to the
nitro group, the corresponding signal was shifted
downfield (due to the anisotropic effect of the nitro
group [22, 23]) as compared to the trans-orientation case.
1H NMR spectra of the gem-cyanonitroethenes I–
VI recorded in CDCl3 solution confirmed their stereo
homogeneity (Table 1). The chemical shift of the
olefinic proton HA was of 8.42–8.81 ppm, being
1
respectively, in H NMR spectrum of β-nitrostyrene
3
(CDCl3), the coupling constant being of JAB 14.0 Hz
[24]; in the spectrum of nitrile of α-nitrocinnamic acid
I, the chemical shift of HA proton was of 8.66 ppm
leading to the conclusion about E-configuration of
compound I. Similarly, the E-configuration of other
gem-cyanonitroethenes II–VI was confirmed.
Analysis of the long-range spin-spin coupling
constants in H NMR spectra of furan-, thiophene-,
1
Scheme 1.
and pyrrole-based gem-cyanonitroethenes allowed
investigation of their conformational isomerism with
respect to the heterocycle–ethylene fragment single
bond [19]. That approach has been described in view
of elucidation of the conformation of 2-vinylfuran-
(thiophene) and their nitro- and formyl-containing
derivatives. In detail, the coupling constant between
O
H
NO2
HA
R
NO2
CN
EtOH abs.
+
R
CN
I_VI
R = Ph (I), 4-MeOC6H4 (II), 4-HO-3-MeOC6H3 (III), 4-
Me2NC6H4 (IV), 2-furyl (V), 2-thienyl (VI).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

ARYL(HETARYL)-CONTAINING gem-CYANONITROETHENES
1847
Scheme 2.
H
H
H
X
c
d
d
b
a
HA
NO2
HA
NO2
a
c
b
H
H
X
H
NC
NC
s-cis
s-trans
X = O, S, NMe.
the olefinic proton and the Hd proton evidences about
the presence of the s-trans-conformer, and the nonzero
constant between the olefinic proton and the Hc proton
confirms the presence of the s-cis-conformer [25–27].
The both mentioned coupling constants [5J(HAHd) 0.5–
exclusively in the form of the s-trans-conformer in the
(CD3)2CO solution [19].
13
The C NMR spectra of certain representatives of
gem-cyanonitroethenes have been reported earlier [10,
12–14, 28] but the signal assignment has not been
accomplished; complete assignment of the 13C NMR
signals has been performed only for β-(2-methoxy-
carbonylphenyl)-α-nitroacrylonitrile [8].
1.0 and J(HAHc) 0.3–0.5 Hz] were found in the H
NMR spectra (CDCl3) of 1-nitro-2-furyl(thienyl; 1-
cyano-2-furyl(thienyl; 1-methylpyrrolyl)-1-nitroethenes,
thus revealing the coexistence of the s-trans- and s-cis-
conformers and indicating the possibility of free
rotation around the heterocycle–ethylene fragment
ordinary bond (Scheme 2).
5
1
13C NMR spectra of gem-cyanonitroethenes I–VI
recorded in this work (Table 2) contained the signals
of all the carbon atoms present in the structures. In
particular, the signals of the carbon atom adjacent to
the two electron withdrawing nitro and cyano groups
were found to be upfield shifted (116.17–131.09 ppm)
as compared to the carbon atom in β-position with
The example of the thiophene-containing gem-
cyanonitroethene VI showed that replacement of
CDCl3 on the more polar (CD3)2CO shifted the
conformational equilibrium: compound VI existed
Table 2. 13C NMR spectral parameters of gem-E-cyanonitroethenes I–VI (δ, ppm; J, Hz)
Comp.
no.
X
Y
С3
С2
CH3
–
C1
Сa
Сb
Сf
Сc
Сe
Сd
I
H
H
H
148.65 123.33
(1JCH
160.05)
111.03 127.40
(3JC1HA
11.26)
132.34
130.03
135.63
(1JCH
163.10)
(1JCH 161.54)
(1JCH 163.70)
II
MeO
148.19 120.54 56.06
111.86 120.00
(3JC1HA
135.34
115.73
165.98
(1JCH
(1JCH
(1JCH 161.66)
(1JCH 163.38)
158.55)
158.55)
11.10)
III OH
MeO 148.71 120.40 56.45
112.20 120.06 111.57
131.55
147.46 115.83 153.43
(1JCH
(1JCH
(3JC1HA
(1JCH
(1JCH
(1JCH
158.39)
145.69)
11.50)
159.11) 162.94)
164.86)
IV Me2N H
147.92 116.17 40.43
113.59 115.05
(3JC1HA
136.06
112.41
155.38
(1JCH
(1JCH
(1JCH 157.35)
(1JCH 161.18)
156.43)
137.83)
10.86)
V
O
S
–
–
132.99 119.73
(1JCH
163.57)
–
–
110.75 144.75 127.30
–
–
115.42
–
–
151.52
(1JCH
206.87)
(3JC1HA
(1JCH
(1JCH
11.70)
181.47)
180.71)
VI
140.95 120.28
(1JCH
111.14 131.55 140.80
129.91
(1JCH
139.40
(1JCH
(3JC1HA
(1JCH
162.63)
11.50)
173.48)
172.68)
187.86)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

1848
BAICHURIN et al.
δC, ppm
c
d
e
b
1
CN
2
f
a
3
HA
NO2
δН, ppm
Fig. 1. 1H–13C HMQC spectrum of (Е)-1-cyano-1-nitro-2-phenylethene I in CDCl3.
13
respect to the nitro group (132.99–160.04 ppm) {in
contrast to the gem-alkoxycarbonyl(acetyl)nitroethenes
analogs [29, 30]}. That was in line with to the well
known anisotropic effect of cyano group [23].
was observed in the proton-coupled C NMR spectra
of E-gem-cyanonitroethenes I–VI recorded in this
work [3J(HАC1) = 10.86–11.70 Hz].
IR and electronic absorption spectra of compounds
I–VI were similar to the earlier described ones
[19, 31–34] (Table 3).
Validity of the proton and carbon signals
1
assignment in the H and 13C NMR spectra of gem-
cyanonitroethenes I–VI was confirmed by the data of
two-dimensional NMR experiments (HMQC and HMBC).
In detail, the HA olefinic proton (δ = 8.66 ppm) was
correlated with the C3 carbon atom (δ = 148.65 ppm) in
the 1H–13C HMQC spectrum of gem-cyanonitrostyrene
I (Fig. 1). The HMBC data allowed unambiguous
assignment of the signals of hydrogen and carbon
atoms at ortho- and meta-positions of benzene ring and
the C2 atom signal in the case of 2-(4-N,N-dimethyl-
aminophenyl)-1-cyano-1-nitroethene IV basing on the
presence of the corresponding cross-peaks of the HA
proton and the C3 carbon atom (Fig. 2).
The electronic spectroscopy data did not contradict
the conclusion about E-configuration of gem-cyano-
nitroethenes I–VI suggested above based on the NMR
data. Indeed, comparison of the electronic spectra data
for the simplest 2-aryl(hetaryl)-1-nitroethenes [24, 34]
with the data listed in Table 3 indicated that
introduction of the cyano group led to bathochromic
shift of the long-wave absorption band, thus strongly
confirming the existence of gem-cyanonitroethenes I–
VI in the E-form. Let us give a typical example of the
spectral parameters change due to the presence of the
cyano group: 2-(para-dimethylaminophenyl)-1-nitro-
ethene (λmax = 437 nm, ε = 28700 L mol–1 cm–1) and com-
pound IV (λmax = 485 nm, ε = 46300 L mol–1 cm–1) [31].
E-Configuration of one of the gem-cyanonitro-
ethenes, 2-(2-methoxycarbonylphenyl)-1-nitro-1-cyano-
ethene (δHA = 9.49 ppm), stated earlier [8] was addi-
tionally confirmed by the value of the heteronuclear
coupling constant between the HA proton and the
carbon atom of cyano group [3J(HАC1) ≈ 14 Hz]
corresponding to their trans-location. That constant
IR spectrum of the simplest E-gem-cyanonitro-
styrene I contained the absorption bands typical of the
covalently bound conjugated nitro group, νas = 1537 and
νs = 1317 cm–1. However, the spectra of its analogs, E-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

ARYL(HETARYL)-CONTAINING gem-CYANONITROETHENES
1849
δC, ppm
(H3C)2N
H
c
d
e
b
H
H
2
1
f
a
CN
3
H
HA
NO2
δН, ppm
Fig. 2. 1H–13C HMBC spectrum of (Е)-2-(4-N,N-dimethylaminophenyl)-1-cyano-1-nitroethene IV in CDCl3.
II–VI containing electron-donating substituents (such
as methoxy, hydroxyl, or dimethyamino groups) at the
benzene ring or furan (thiophene) components
revealed the spectra similar to that of the model E-2-
aryl(hetaryl)-1-nitroethenes;1 in particular, the recorded
spectra contained no typical bands of the covalently
bound nitro group whereas the extraordinarily strong
bands at 1595–1640 (С=С, С=N+) and 1315–1335,
–1
1300–1305 cm (NOO–) were observed (cf. [19–21,
32, 33]). The spectral features evidenced about high
Table 3. IR and electronic spectra parameters of gem-E-cyanonitroethenes I–VI
ν, cm –1
Comp.
no.
R
λ
max, nmа ε, L mol–1 cm–1
NO2 (NOO–)
1537, 1317
CN
C=C (C=N+)
1618
I
Ph
2225
2230
2225
2230
2225
2225
328
390
390
485
371
375
17000
30000
28500
46300
21500
17900
II
4-MeOC6H4
4-HO-3-MeОС6Н4
4-Me2NC6H4
2-Furyl
(1320, 1305)
(1320, 1305)
(1315, 1300)
(1335, 1305)
(1335, 1305)
(1595, 1640)
(1595, 1620)
(1595, 1640)
(1620)
III
IV
V
VI
2-Thienyl
(1615)
Model compound
(1320, 1298, 1267)
–
(1600)
437
28700
Me N
CH CH NO
2
2
a The absorption bands at λ > 270 nm (EtOH) are given.
1
In the review [25] the absorption bands at 1510–1550 and 1340 cm–1
in IR spectra of furylnitroethenes have been attributed to the
asymmetric and symmetric stretching, respectively, of nitro group.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

1850
BAICHURIN et al.
polarity of the molecules due to the efficient con-
jugation involving p-electrons of nitrogen, oxygen or
sulfur, double carbon-carbon bond, and the nitro group.
methylphenyl)-1-cyano-1-nitroethene and divinyl [the
latter being generated in situ from 3-sulfolene under
the reaction conditions (110°C, 12 h)] have been
described in [13].
O
O
H
N
O
H
N
O
We found that gem-cyanonitroethenes I, II, V, and
VI reacted smoothly with 2,3-dimethyl-1,3-butadiene;
the reactions proceeded in toluene under reflux during
2–9 h in the absence of any catalyst. The func-
tionalized cyclohexenes VII–X were obtained in up to
94% yield.
CN
CN
(Me) N
(Me) N
2
2
R
CH3
The high polarity of E-gem-cyanonitroethenes was
confirmed using the dipole moments method with
nitrile of α-nitrocinnamic acid (μexp, 5.46 D) as an
example; the molecule was completely coplanar, and
the both substituents (nitro and cyano groups)
participated in the conjugation [35].
+
NC
I, II, V, VI
NO2
CH3
H "
B
HA"
H
R
CH3
CH3
5
toluene, Δ, 2_9 h
6
4
3
The X-ray analysis data of α-nitrocinnamic acid
nitrile, its derivatives (ortho- and para-methoxy-
substituted at the benzene ring), and gem-cyano-
nitroethene of ferrocene type available in the literature
have confirmed the molecules E-configuration in the
crystal [7, 28, 36, 37].
1
2
NC
NO2
H '
HB'
A
VII_X
R = Ph (I, VII), 4-MeOC6H4 (II, VIII), 2-furyl (V, IX),
2-thienyl (VI, X).
Nitriles of α-nitrocinnamic acids and their hetero-
analogs have been recognized as highly reactive
species: they easily react with C-, N-, and P-nucleo-
philes [1]. Their reactions with 1,3-dipoles [7, 38–42]
and vinyl ethers [43–45] yielding practically important
cyclic compounds are of the particular interest.
The prepared gem-cyanonitrocyclohexenes were
crystalline solids. Compound VII has been earlier
synthesized via the three-component solvent-free
reaction from benzaldehyde, nitroacetonitrile, and 2,3-
dimethyl-1,3-butadiene (60°C, 5 h) [13].
Due to the presence of the electron-deficient C=C
bond in the molecules of gem-cyanonitroethenes, they
can be used as dienophile components in the Diels–
Alder reactions. However, the information about
preparation of the diene synthesis adducts based on
aryl(hetaryl)-containing cyanonitroethenes has only
appeared recently. The available examples include the
interaction of these nitroalkenes with cyclo-pentadiene
[46]; the reactions have been performed in anhydrous
nitromethane at room temperature during 24 h and
have yielded a mixture of endo(NO2)- and exo(NO2)-
Structure of the products VII–X was confirmed by
IR and H NMR spectroscopy data (Table 4). In
1
particular, the IR spectra contained strong absorption
bands assigned to stretching of non-conjugated nitro
group (νas = 1565–1570 and νs = 1355–1370 cm–1).
Stretching vibrations of the cyano group were not
registered in the IR spectra; that feature of the non-
conjugated gem-nitro nitrile fragment could be
probably explained by the electronic effect of the
neighboring nitro group [52]. Similarly, the cyano
group has been inactive in IR spectrum of
nitroacetonitrile; however, the corresponding band in
the Raman spectrum (2270 cm–1) is strong [19].
1H NMR spectra of cyanonitrocyclohexenes VII–X
contained the signals of all the protons present in the
molecules. In detail, the spectrum of compound X
solution in CDCl3 (Fig. 3) contained a singlet of the
protons of the CH3 groups at the double bond of the
isomers of gem-cyanonitronorbornenes, with
a
predominance of first. Structure of the endo(NO2)-
isomers has been confirmed by NOESY spectroscopy
[46] and X-ray diffraction analysis [47]; the kinetic
[48] and quantum-chemical studies of the reactions
have been performed [49–51].
The diene condensations between 1-cyano-1-nitro-
2-(4-cyanophenyl)ethene and 2,3-dimethyl-1,3-buta-
diene (in bulk, 30°C, 10 h) as well as between 2-(4-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

ARYL(HETARYL)-CONTAINING gem-CYANONITROETHENES
Table 4. Spectral parameters of gem-cyanonitrocyclohexenes VII–X
1851
ν, cm–1
δH, ppm (J, Hz)
Comp.
no.
R
NO2
CH3
HA'
HB'
HA''
HB''
2.47 d.d
H
Ar, Het [OCH3]
7.30–7.40 m
VII
Ph
1570, 1360
1.75 s
3.27 d
2.82 d
2.78 m
3.65 d.d
2JA'B' 16.5
2JA''B'' 17.94
3JA''H 11.84, 3JB''H 5.55
2.74 m 2.42 d.d
JA''B'' 18.00
3JA''H 11.90, 3JB''H 5.80
2.78 m 2.46 d.d
2JA''B'' 18.16
3JA''H 12.0, 3JB''H 5.45
2.74 m 2.59 d.d
2JA''B'' 17.33
3JA''H 11.52, 3JB''Н 5.70
VIII
IX
4-МеOC6H4 1565, 1360
1.73 s
1.75 s
3.26 d
2.80 d
6.85d, 7.27d
3Jb,c 8.85
[3.78 s]
3.65 d.d
2JA'B' 17.0
2-Furyl
1565, 1355
1570, 1370
3.27 d
2.82 d
6.30–7.35 m
3.65 d.d
2JA'B' 16.5
X
2-Thienyl
1.74 s
3.24 d
2.84 d
6.98 d (Hc),
7.04 d.d (Hb)
7.27 d (Hd)
3Jb,c 3.68,
4.01 d.d
2JA'B' 16.0
3Jc,d 5.06
ring (δ = 1.74 ppm); the cyclic methylene protons
С2НА' and С2НВ' resonated as an AB-system and were
detected as doublets at 3.24 and 2.84 ppm [2J(HА'НВ') =
16.00 Hz]; the С5НА'', С5НВ'', and С6Н protons of a
three-spin ABX-system were observed at 2.74, 2.59,
and 4.01 ppm, respectively; the protons of thiophene
ring resonated as two doublets (6.98 and 7.27 ppm)
and a doublet of doublets (7.04 ppm).
EXPERIMENTAL
Physico-chemical studies were performed in the
Center for Collective Use of the faculty of chemistry,
Herzen State Pedagogical University of Russia.
1
1
1H, 13C–{1H} NMR, Н–13С HMQC, and Н–13С
HMBC spectra of the solutions in deuterated chloro-
form were registered with a Jeol JNM-ECX400A
spectrometer operating at 399.78 (1H) and 100.53
(13С) MHz. The residual proton signals of the non-
deuterated solvent served as the internal reference. IR
spectra were recorded with a Shimadzu IR-Prestige-21
Fourier spectrometer in the chloroform solution (с =
40 mg mL–1). Electronic absorption spectra of the
ethanolic solutions were recorded using a Shimadzu
UV 2401PC instrument (quarts cell, l = 1.01 mm).
Elemental analysis was performed with a EuroVector
analyzer (EA 3000, the CHN Dual configuration).
Availability of the starting reagents, simplicity of
the procedure, and good yields of the products
suggested that the proposed method was a convenient
approach towards synthesis of gem-cyanonitro-
cyclohexenes.
The new nitro- and cyano-substituted cyclohexenes
obtained in this work are of definite practical interest
in view of the application as synthetic intermediates
for preparation of pharmacologically active com-
pounds. Substituted cyclohexanes and cyclohexenes
have been recognized as the key parts of a number of
practically important compounds or intermediates for
their preparation [53–56]. gem-Cyanonitrocyclo-
hexenes containing pharmacophore furan or thiophene
fragments are of special significance since many
derivatives of these heterocycles (such as furacilin,
furazolidonе, furagin, furosemid, pyrantel, ketotifen,
and others) have been widely used in the medicine
[57].
1-Cyano-1-nitro-2-phenylethene I was prepared as
described in [2] from benzaldehyde and nitroaceto-
nitrile in the presence of MeNH2·HCl and Na2CO3;
other gem-cyanonitroethenes II–VI were synthesized
from crude nitroacetonitrile without any catalyst
[18, 19].
3,4-Dimethyl-1-cyano-1-nitro-6-phenyl-3-cyclo-
hexene (VII). 2,3-Dimethyl-1,3-butadiene (0.33 mL,
0.003 mol) and approximately 0.05 g of hydroquinone
as polymerization inhibitor were added to a suspension
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

1852
BAICHURIN et al.
c
HA"
HB"
b
H
d
a
CH3
CH3
5
S
6
1
4
3
2
NC
NO2
HA' HB'
δ, ppm
Fig. 3. 1H NMR spectrum of 3,4-dimethyl-1-cyano-1-nitro-6-(2-thienyl)-3-cyclohexene X in CDCl3.
of 1-cyano-1-nitro-2-phenylethene
I
(0.174 g,
diene; the reaction mixture was refluxed with toluene
during 2 h. Yield 54%, colorless crystals, mp 93–94°С
(ethanol). Found N, %: 11.53. C13H14N2O3. Calculated N,
%: 11.38.
0.001 mol) in 3.3 mL of toluene. The reaction mixture
was refluxed during 3 h. After cooling, the solvent and
excess of 2,3-dimethyl-1,3-butadiene were removed;
the residue was treated with ethanol. Yield 0.192 g
(75%), colorless crystals, mp 90–92°С (ethanol) (mp
98–100°C (Et2O) [13]). Found, %: C 70.34, 70.48; H
6.31, 6.38; N 10.79. C15H16N2O2. Calculated: С 70.31;
Н 6.25; N 10.94.
3,4-Dimethyl-1-cyano-1-nitro-6-(2-thienyl)-3-
cyclohexene (X) was prepared similarly from 1-cyano-
1-nitro-2-(2-thienyl)ethene VI and 2,3-dimethyl-1,3-
butadiene; the reaction mixture was refluxed with
toluene during 4 h. Yield 83%, colorless crystals, mp
122–124°С (ethanol). 13С–{1H} NMR spectrum (CDCl3),
δС, ppm: 18.52, 18.56, 38.34, 42.04, 43.18, 90.85,
113.45, 120.32, 126.00, 126.63, 127.05, 127.27, 137.60.
Found, %: C 59.77; H 5.29; N 10.48. C13H14N2SO2.
Calculated, %: С 59.54; Н 5.34; N 10.68.
3,4-Dimethyl-6-(4-methoxyphenyl)-1-cyano-1-
nitro-3-cyclohexene (VIII) was prepared similarly
from 2-(4-methoxyphenyl)-1-cyano-1-nitroethene II
and 2,3-dimethyl-1,3-butadiene; the reaction mixture
was refluxed with toluene during 9 h. Yield 94%,
colorless crystals, mp 108–110°С (ethanol). Found N,
%: 9.63. C16H17N2O3. Calculated N, %: 9.79.
ACKNOWLEDGMENTS
This work was financially supported by the
Ministry of Education and Science of Russian
Federation in the frame of the basic part of
governmental task.
3,4-Dimethyl-6-(2-furyl)-1-cyano-1-nitro-3-cyclo-
hexene (IX) was prepared similarly from 1-cyano-1-
nitro-2-(2-furyl)ethene V and 2,3-dimethyl-1,3-buta-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

ARYL(HETARYL)-CONTAINING gem-CYANONITROETHENES
1853
USSR, 1972, vol. 8, no. 6, p. 1349.
REFERENCES
19. Shadrin, V.Yu., Candidate Sci. (Chem.) Dissertation,
1. Berestovitskaya, V.M., Baichurin, R.I., and Aboskalo-
Leningrad, 1987.
va, N.I., Sopryazhennye nitroeteny, geminal’no
20. Sokolova L.N., Polyanskaya, A.S., Aboskalova, N.I.,
Demireva, Z.I., and Pyatnitskaya, I.A., Sb. Nauchn.
Dokl., XXX Gertsenovskie chteniya, Leningrad, 1977, p. 59.
21. Polyanskaya, A.S., Perekalin, V.V., Aboskalova, N.I.,
Demireva, Z.I., Sokolova L.N., and Abdulkina, Z.A.,
Zh. Org. Khim., 1979, vol. 15, no. 10, p. 2057.
22. Perekalin, V.V., Sopova, A.S., and Lipina, E.S.,
Nepredel’nye nitrosoedineniya (Unsaturated Nitro-
compounds), Leningrad: Khimiya, 1982.
23. Ionin, B.I., Ershov, B.A., and Kol’tsov, A.I., YaMR-
spektroskopiya v organicheskoi khimii (NMR Spec-
troscopy in Organic Chemistry), Leningrad: Khimiya,
1983.
24. Aboskalova, N.I., Smirnova, N.N., Kataeva, O.N.,
Baichurin, R.I., Fel’gendler, A.V., Berkova, G.A., and
Berestovitskaya, V.M., Russ. J. Gen. Chem., 2008,
vol. 78, no. 9, p. 1711. DOI: 10.1134/S1070363208090120.
25. Karakhanov, R.A., Kelarev, V.I., and Polivin, Yu.N.,
Russ. Chem. Rev., 1993, vol. 62, no. 2, p. 169. DOI:
10.1070/RC1993v062n02ABEH000011.
26. Arcoria, A., Bottino, F., and Sciotto, D., J. Heterocycl.
Chem., 1977, vol. 14, no. 8, p. 1353. DOI: 10.1002/
jhet.5570140811.
27. Parr, W.J.E., Wasylishen, R.E., and Schaefer, T., Can.
J. Chem., 1976, vol. 54, no. 20, p. 3216. DOI: 10.1139/
v76-459.
aktivirovannye slozhnoefirnoi, tsiano-,
i
atsil’noi
gruppami (Conjugated Nitroethenes Geminally
Activated by the Ester, Cyano, and Acyl Groups), St.
Petersburg: Asterion, 2014.
2. Ried, W., and Köhler, E., Lieb. Ann., 1956, vol. 598,
no. 2, p. 145. DOI: 10.1002/jlac.19565980207.
3. Acheson, R.M., Dearnaley, D.P., Plunkett, A.O., and
Porter, V.C., J. Chem. Soc. (Resumed), 1963, p. 2085.
DOI: 10.1039/JR9630002085.
4. Dore, J.C., and Viel, C., Chim. Therapeutica, 1973,
vol. 8, no. 1, p. 80.
5. Metchkov, T., and Demireva, Z., Z. Chem., 1985,
vol. 25, no. 5, p. 169. DOI: 10.1002/zfch.19850250504.
6. Mechkov, Ts.D., and Demireva, Z.I., J. Org. Chem.
USSR, 1985, vol. 21, no. 9, p. 1724.
7. Benhaoua, H., Piet, J.C., Danion-Bougot, R.D., Toupet, L.,
and Carrie, R., Bull. Soc. Chim. Fr., 1987, no. 2, p. 325.
8. Troschütz, R., and Grün, L., Archiv Pharm., 1993,
vol. 326, no. 11, p. 857. DOI: 10.1002/
ardp.19933261104.
9. Jasiński, R., Kwiatkowska, M., and Barański, A.,
Czasopismo Techniczne. Chemie, 2006, vol. 103, no. 4,
p. 41.
10. Tamaddon, F., Tayefi, M., Hosseini, E., and Zare, E.,
J. Mol. Catal. (A), 2013, vol. 366, p. 36. DOI: 10.1016/
j.molcata. 2012.08.027.
28. Nishiwaki, N., Tomoko, N., Tanaka, C., Nakashima, F.,
Inoue, Y., Asaka, N., Tohda, Y., and Ariga, M., J. Org.
Chem., 1999, vol. 64, no. 6, p. 2160. DOI: 10.1021/
jo9818879.
29. Baichurin, R.I., Baichurina, L.V., Aboskalova, N.I., and
Berestovitskaya, V.M., Russ. J. Gen. Chem., 2013,
vol. 83, no. 9, p. 1764. DOI: 10.1134/S1070363213090223.
11. Brillon, D., and Sauve, G., J. Org. Chem., 1992, vol. 57,
no. 6, p. 1838. DOI: 10.1021/jo00032a042.
12. Amantini, D., Fringuelli, F., Piermatti, O., Pizzo, F., and
Vaccaro, L., Green Chem., 2001, vol. 3, no. 5, p. 229.
DOI: 10.1039/B105522B.
13. Frinquelli, F., Girotti, R., Piermatti, O., Pizzo, F., and
Yaccaro, L., Org. Lett., 2006, vol. 8, no. 25, p. 5741.
DOI: 10.1021/ol062253o.
30. Marçot, B., Rabaron, A., and Viel, C., Can. J. Chem.,
1981, vol. 59, no. 8, p. 1224. DOI: 10.1139/v81-179.
14. (a) Boguszewska-Czubara, A, Łapczuk-Krygier, A.,
Rykała, K., Biernasiuk, A., Wnorowski, A, Popiołek, Ł.,
Maziarka, A., Hordyjewska, A., Jasiński, R., J. Enzyme
Inhibition and Medicinal Chemistry, in press.
DOI: 10.3109/14756366.2015.1070264. (b) Velizadeh, H.,
Mamaghani, M., and Badrian, A., Synth. Comm., 2005,
vol. 35, no. 6, p. 785. DOI: 10.1081/SCC-200050942.
15. Steinkopf, W., and Bohrmann, L., Ber., 1908, vol. 41,
no. 1, p. 1044. DOI: 10.1002/cber.190804101207.
16. Aboskalova, N.I., Candidate Sci. (Chem.) Dissertation,
Leningrad, 1971.
17. Polyanskaya, A.S., Perekalin, V.V., Aboskalova, N.I.,
and Sokolova L.N., USSR Author’s Certificate 335246
(1972); Bull. Izobret., 1972, no. 13.
18. Aboskalova, N.I., Polyanskaya, A.S., Perekalin, V.V.,
Demireva, Z.I., and Sokolova, L.N., J. Org. Chem.
31. Paperno, T.Ya., Perekalin, V.V., and Sopova, A.S.,
J. Appl. Spectr., 1973, vol. 19, no. 4, p. 1299. DOI:
10.1007/BF00604072.
32. Paperno, T.Ya., and Perekalin, V.V., Infrakrasnye
spektry nitrosoedinenii (IR Spectra of Nitrocompounds),
Leningrad: LGPI, 1974.
33. Ptichkina, I.P., Paperno, T.Ya., Demireva, Z.I.,
Aboskalova, N.I., and Shadrin, V.Yu., Mezhvuz. sb.
nauch. trudov “Metody sinteza, stroenie i khimicheskie
prevrashcheniya
nitrosoedinenii”
(Methods
of
Synthesis, Structure, and Chemical Reactions of
Nitrocompounds), Leningrad, 1980, p. 61.
34. Pozdnyakov, V.P., and Shadrin, V.Yu., Mezhvuz. sb.
nauch. trudov “Metody sinteza, stroenie i khimicheskie
prevrashcheniya
nitrosoedinenii”
(Methods
of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015

1854
BAICHURIN et al.
46. Jasiński, R., Rzyman, M., and Barański, A., Coll.
Synthesis, Structure, and Chemical reactions of
Czech. Chem. Comm., 2010, vol. 75, no. 9, p. 919. DOI:
Nitrocompounds), Leningrad, 1989, p. 105.
10.1135/cccc2009562.
35. Demireva, Z.I., Polyanskaya, A.S., Mladenov, I., and
Perekalin, V.V., Zh. Org. Khim., 1976, vol. 12, no. 6,
p. 1192.
47. Łapczuk-Krygier, A., Ponikiewski, Ł., and Jasiński, R.,
Cryst. Rep., 2014, vol. 59, no. 7, p. 961. DOI: 10.1134/
S1063774514070128.
36. Nesterov, V.N., Kislyi, V.P., Timofeeva, T.V., Anti-
pin, M.Yu., and Semenov, V.V., Acta Cryst., Sect. C,
2000, vol. 56, no. 3, p. e107. DOI: 10.1107/
S0108270100001864.
48. Jasiński, R., Kwiatkowska, M., and Barański, A.,
Monatsh. Chem. Chem. Monthly, 2012, vol. 143, no. 6,
p. 895. DOI: 10.1007/s00706-012-0735-3.
49. Jasiński, R., Kwiatkowska, M., and Barański, A.,
J. Mol. Struct. (THEOCHEM), 2009, vol. 910, nos. 1–3,
p. 80. DOI: 10.1016/j.theochem.2009.06.018.
37. Laus, G., Schottenberger, H., Schuler, N., Wurst, K.,
and Herber, R.H. J. Chem. Soc., Perkin Trans. 2, 2002,
no. 8, p. 1445. DOI: 10.1039/B203395J.
50. Jasiński, R., and Barański, A., J. Mol. Struct.
(THEOCHEM), 2010, vol. 949, no. 1–3, p. 8. DOI:
10.1016/j.theochem. 2010.02.023.
38. Amantini, D., Fringuelli, F. Piermatti, O., Pizzo, F.,
Zunino, E., and Vaccaro, L., J. Org. Chem., 2005,
vol. 70, no. 16, p. 6526. DOI: 10.1021/jo0507845.
51. Jasiński, R., Michorczyk, P., Jasińska, E., Koifman, O.I.,
and Barański, A., Izv. Vuzov. Ser. Khim i Khim.
Tekhnol., 2011, vol. 54, no. 5, p. 89.
39. Fringuelli, F., Lanari, D., Pizzo, F., and Vaccaro, L.,
Eur. J. Org. Chem., 2008, no. 23, p. 3928. DOI:
10.1002/ejoc.200800142.
52. Bellamy, L.J., The Infrared Spectra of Complex
Molecules, London: Methuen & Co., Ltd., 1958.
40. Piet, J.C., Le Hetet, G., Cailleux, P., Benhaona, H., and
Carrie, R., Bull. Soc. Chim. Belg., 1996, vol. 105, no. 1,
p. 33. DOI: 10.1002/bscb.19961050107.
53. Anisimova, N.A., and Berestovitskaya, V.M., Funk-
tsionalizirovannye nitroalkeny v reaktsiyakh dienovogo
sinteza i 1,3-dipolyarnogo tsikloprisoedineniya (Func-
tionalized Nitroalkenes in Reactions of the Diene
Synthesis and 1,3-Dipolar Cycloaddition), St.
Petersburg: Asterion, 2008.
41. Nosachev, S.B., Shchurova, N.A., and Tyrkov, A.G.,
Russ. J. Org. Chem., 2011, vol. 47, no. 4, p. 577. DOI:
10.1134/S107042801104018X.
42. Nosachev, S.B., Del’netskaya, K.A., Solov’ev, N.A.,
and Tyrkov, A.G., Russ. J. Org. Chem., 2010, vol. 46,
no. 9, p. 1427. DOI: 10.1134/S1070428010090319.
54. Nicolaou, K.C., Snyder, S.A., Montagnon, T., and
Vassilikogiannakis, G., Angew. Chemie Int. Ed., 2002,
vol. 41, no. 10, p. 1668. DOI: 10.1002/1521-3773
(20020517)41:10<1668::AID-ANIE1668>3.0.CO;2-Z.
43. Fringuelli, F., Matteucci, M., Piermatti, O., Pizzo, F.,
and Burla, M.C., J. Org. Сhem., 2001, vol. 66, no. 13,
p. 4661. DOI: 10.1021/jo010182v.
55. Mackay, E. G., and Sherburn, M.S., Synthesis, 2015,
44. Bellachioma, G., Castrica, L., Fringuelli, F., Pizzo, F.,
and Vaccaro, L., Green Chem., 2008, vol. 10, no. 3,
p. 327. DOI: 10.1039/B712858D.
vol. 47, no. 1, p. 1. DOI: 10.1055/s-0034-1378676.
56. Maltsev, O.V., Beletskaya, I.P., and Zlotin, S.G., Russ.
Chem. Rev., 2011, vol. 80, no. 11, p. 1067. DOI:
10.1070/RC2011v080n11ABEH004249.
45. Jasiński, R., Kubik, M, Łapczuk-Krygier, A., Kącka, A.,
Dresler, E., and Boguszewska-Czubara, A., Reac. Kinet.
Mech. Cat., 2014, vol. 113, no. 2, p. 333. DOI: 10.1007/
s11144-014-0753-8.
57. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: RIA “Novaya Volna,” 2012.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015