Reactions of 1-nitrocyclohexene with N,N-binucleophiles

Article abstract of DOI:10.1134/S1070363210110113

A modification of 1-nitrocyclohexene synthesis is proposed; its reaction with phenylhydrazine and benzoic acid hydrazide is shown to afford monoadducts, and with hydrazine hydrate, bisaduct. With diphenylguanidine occurs heterocyclization to 1-phenyl-2-N-phenylamino-4,5,6,7-tetrahydrobenzimidazole, whose structure is confirmed by the X-ray diffraction data. The analysis performed for this compound of the electron density distribution function in the crystal made it possible to estimate the charge distribution, π-electrons delocalization nature, and the role of N-H···N, C-H···H-C and C-H···C interactions in the formation of the crystal packing. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210110113

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 11, pp. 2298–2305. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.E. Efremova, M.I. Vakulenko, K.A. Lysenko, I.S. Bushmarinov, L.V. Lapshina, G.A. Berkova, V.M. Berestovitskaya, 2010,
published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 11, pp. 1834–1842.
Reactions of 1-Nitrocyclohexene with N,N-Binucleophiles
I. E. Efremovaa, M. I. Vakulenkoa, K. A. Lysenkob, I. S. Bushmarinovb,
L. V. Lapshinaa, G. A. Berkovaa, and V. M. Berestovitskayaa
a Herzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
b Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow, Russia
Received February 25, 2010
Abstract―A modification of 1-nitrocyclohexene synthesis is proposed; its reaction with phenylhydrazine and
benzoic acid hydrazide is shown to afford monoadducts, and with hydrazine hydrate, bisaduct. With
diphenylguanidine occurs heterocyclization to 1-phenyl-2-N-phenylamino-4,5,6,7-tetrahydrobenzimidazole,
whose structure is confirmed by the X-ray diffraction data. The analysis performed for this compound of the
electron density distribution function in the crystal made it possible to estimate the charge distribution, π-
electrons delocalization nature, and the role of N–H···N, C–H···H–C and C–H···C interactions in the formation
of the crystal packing.
DOI: 10.1134/S1070363210110113
In the chemistry of nitro compounds, which are
successfully utilized as the active building blocks in
the purposeful synthesis of practically important
substances, cyclic conjugated nitroalkenes occupy a
significant place. They are used as effective substrates
for the addition reactions in designing polynuclear
framework systems [1]. In particular, precursors of
biologically active alkaloids [2, 3] and compounds
possessing cytotoxic activity [4] have been obtained on
the basis of 1-nitrocyclohexene.
elimination to form product II quantitatively, whereas
the content of minor diastereomer Ib in the reaction
mixture remained practically unchanged.
The spectral characteristics of the obtained nitro-
alkene II correspond to the published data [7, 8]. In the
1H NMR spectrum of this compound the signal of
olefin proton at 7.27 ppm is present along with the
signals of the methylene protons of the ring. The IR
spectrum contains absorption bands of C=C bond
(1635 cm–1) and the vibrations of the conjugated nitro-
group (1516, 1343, 1334 cm–1).
At the same time the known approaches to the
synthesis of 1-nitrocyclohexene [5, 6] have some
drawbacks in the practical realization. The nitromercura-
tion method [5] requires the use of mercuric chloride,
and the one-pot nitroiodination–dehydrogenation method
[6] recommended for synthesis of the wide variety of
nitroalkenes is not reproduced in the case of 1-
nitrocyclohexene. We have showed that the reaction of
sodium nitrite and iodine with cyclohexene under the
conditions [6] affords nitroalkene in trace amount. The
main product is 2-iodo-1-nitrocyclohexane I (53%)
isolated as 2:1 diastereomeric mixture. The target
nitroalkene II was obtained by dehydrohalogenation of
this diastereomeric mixture with triethylamine in
diethyl ether solution in 37% yield.
We studied reaction of 1-nitrocyclohexene II with a
series of N,N-binucleophiles, the hydrazine derivatives
(phenylhydrazine, benzoic acid hydrazide, and hyd-
razine hydrate) and diphenylguanidine. The examined
nitroalkene II was found to be easily adding these
hydrazine derivatives at room temperature in ethanol.
In the case of phenylhydrazine and benzoic acid
hydrazide the classic Michael adducts formed, 1-nitro-
2-hydrazinocyclohexanes III (47%) and IV (78%).
The reaction with hydrazine hydrate resulted in the
bisaddition product, 1,2-bis(2-nitrocyclohexyl)hyd-
razine as a mixture of diastereomers Va and Vb (21%).
As a result of the reaction of 1-nitrocyclohexene II
with N,N'-diphenylguanidine carried out under similar
conditions the high-melting crystalline product was
isolated. According to the spectral data, 1- phenyl-2-N-
It should be noted that under these conditions the
major diastereomer Ia showed greater ability to HI
2298

REACTIONS OF 1-NITROCYCLOHEXENE
2299
NO2
H
NO2
H
NO2
NaNO2; I2
6
3
NH2NHX
Et3N
5
4
1
2
N
H
N
H
X
I
I
II
III, IV
X = Ph (III), C(O)Ph (IV)
NHPh
NHPh
HN
Ph
N
NO2
H NHPh
O
N
NO2
7
4
NHPh
NHPh
6
5
NO2
H
NHPh
N
N
N
H
N
NHPh
VI
V
phenylamino-4,5,6,7-tetrahydrobenzimidazole VI formed
in 24% yield. Taking into account the possibility of the
transformations of the 2-substituted nitrocyclohexanes
according to the Nef reaction [9, 10], it is logical to
assume that this interaction occurs via a series of the
consecutive reactions, which include nucleophilic
addition of diphenylguanidine at the multiple bond,
transformation of nitromethine fragment into the car-
bonyl initiated by the action of basic reagent, and the
subsequent heterocyclization according to AdN–E
scheme with the participation of ketone and aniline
groups.
of the hydrazine derivatives III–V. In the spectrum of
compound IV the absorption band at 1627 cm–1 ori-
ginated from the conjugated carbonyl group.
1
The H NMR spectrum of the fused heterocyclic
structure VI contains multiplets of methylene protons
of the cyclohexene fragment (1.70, 2.27 ppm), phenyl
protons (6.65, 7.03, 7.48 ppm), and also a singlet
signal of NH-proton (7.76 ppm). In the IR spectra of ad-
duct VI there are the absorption bands of С=С and С=N
bonds (1595, 1617 cm–1) and of NH-group (3340 cm–1).
The unequivocal confirmation of 1-phenyl-2-N-
phenylamino-4,5,6,7-tetrahydrobenzimidazole VI struc-
ture were obtained by the data of X-ray diffraction
analysis shown in Figs. 1–3 and in Tables 1 and 2; the
atoms numeration corresponds to that in Fig. 1. The
imidazole ring of the molecule is planar with an
insignificant deviation of the C4 atom; the planes of
phenyl ring and aniline fragment are turned relative to
the heterocycle to the different sides (torsion angles
C1N2C17C18 and N2C1N10C11 are 53.79 and –56.97°,
respectively).
The structure of obtained compounds I, III–VI was
established using IR, 1H NMR spectroscopy and X-ray
1
diffraction analysis. The H NMR spectra of the 2-
substituted nitrocyclohexanes I, III–V are similar in
the character of the signals of the cyclohexane ring
protons. In particular, the vicinal constant values of the
methine protons [3J(С1НС2Н) 4.20–5.45 Hz] indicate
the axial-equatorial orientation of the ring substituents
[11]. Unlike the stereohomogeneous compounds III
and IV, the spectra of the products Ia, Ib, Va, and Vb
contain the double set of signals, which testify to the
existence of these substances as mixtures of erythro-
and threo-diastereomers. The absence of the signals of
The high quality of the studied crystals made it
possible to obtain the high-angle data array which
made it possible to analyze the electron density
distribution ρ(r) in the crystal. The deformation
electron density distribution (DED) in the imidazole
ring is close to that expected: the DED maxima are
localized in the region of chemical bonds and lone
electron pairs of the atoms N5 and N10. On the basis of
the topological analysis of ρ(r) within Bader’s “Atoms
in Molecules” theory [12, 13] we obtained atomic
charges [by integration of ρ(r) over the atomic basin],
localized critical points (3, –1) (chemical bonds
1
NH2-group protons is characteristic of the Н NMR
spectrum of the bis-adducts Va and Vb, that along
with the elemental analysis data confirm the structure
assigned to them.
The IR spectra of compounds I, III–V contain the
absorption bands of the non-conjugated nitro-group
(1545–1559, 1370–1371 cm–1). The presence of NH-
groups absorption (3250–3333 cm–1) is characteristic
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 11 2010

2300
EFREMOVA et al.
a
C21
C22
C20
C19
C17
N2
C18
C6
C14
C13
C3
C7
C8
C12
C15
C16
C11
N10
C1
C4
C9
N5
(b)
C3
C4
N2
N5
C1
N10
Fig. 1. (a) General view of compound VI in the representation of atoms by thermal ellipsoids (p 50%). (b) Distribution of
deformation electron density in the imidazole ring plane. Isolines are drawn with the step 0.1 e Å–3, negative values are shown by
dotted line.
indicators) and determined the bond ellipticities (ε)
values (the values which reproduce the bond multi-
plicity). The analysis of nuclear charges showed that
the negative charge in the heterocycle is predominantly
localized on the nitrogen atoms (N2 and N5 atomic
charges are equal to –0.96 and –0.85 e respectively),
and maximum positive charge (+0.96 e) is on the
carbon atom C1. Atomic charges of C3 and C4 are
substantially lower and equal 0.05 and 0.27 e,
respectively. The values ε in the imidazole ring
indicate the considerable electron delocalization with
the minimum value ε 0.12 on the bond N5–C4 and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 11 2010

REACTIONS OF 1-NITROCYCLOHEXENE
2301
C20
C21
(b)
(a)
C7
C19
C22
C3
N2
C1
C6
C18
C17
N2
C1
C13
C14
C4
C3
N5
C12
C11
N10
Н10N
C15
C8
C16
C12 H12
H13A
C13A
C4
N5
C9
C13
N5А
H13
H12A
C12A
C3A
Fig. 2. Centrosymmetrical dimers bonded due to (a) N–H···N and (b) C–H···H–C contacts.
C13
(3, –1)
C12
C1
(3, –1)
(3, –1)
Н13
H12
(3, –1)
(3, –1)
(3, –1)
H13
H12
(3, –1)
(3, –1)
(3, –1)
C12
C13
(3, –1)
(3, –1)
N10
C14
H14
(3, –1)
(3, –1)
C11
Fig. 3. The vectorial field of the electron density gradient of (thin lines), and also bonding ways (thick lines) and interatomic
surfaces (line of average width) in the region of H···H interactions.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 11 2010

2302
EFREMOVA et al.
Table 1. Bond lengths (Å) and valence angles (deg) for
compound VI
Table 2. Main crystallographic data and refinement param-
eters for compound VI
Bond
l, Å
Bond
l, Å
Parameter
Value
C1–N5
C1–N2
C1–N10
N2–C3
1.3214(4)
1.3762(4)
1.3806(4)
1.4000(4)
deg
N2–C17
C3–C4
C4–N5
1.4274(4)
1.3607(5)
1.3938(4)
1.4100(4)
deg
Formula
Molecular mass
T, K
C19H19N3
289.37
100
N10–C11
Crystal system
Space group
Z
Triclinic
P-1
Angle
Angle
N5C1N2
N5C1N10
N2C1N10
C1N2C3
C1N2C17
C3N2C17
C4C3N2
C4C3C6
111.93(3)
125.72(3)
122.26(3)
106.34(3)
125.99(3)
126.50(3)
105.76(3)
126.75(3)
N2C3C6
C3C4N5
C3C4C9
N5C4C9
C1N5C4
C1N10C11
C1N10H10N
C11N10H10N
127.48(3)
110.76(3)
123.35(3)
125.86(3)
105.16(3)
121.69(3)
111.9(6)
116.7(7)
2
a, Å
8.5649(2)
9.2728(2)
9.9162(2)
80.9133(8)
85.8953(8)
72.6459(8)
742.02(3)
1.295
b, Å
c, Å
α, °
β, °
γ, °
V, Å3
dcalc, g cm–3
μ, cm–1
F(000)
2θmax, deg
maximum on the C3–C4 bond (ε 0.44). For comparison,
the value ε for N2–C17 bond is close to zero (0.05). In
spite of considerable pyramidalization of the atom N10
(sum of bond angles at the atom is equal to 350.4°) it is
also involved into the p-density delocalization: the
values of ε for the bonds N10–C1 and N10–C11 are equal
to 0.21 and 0.10, respectively.
0.78
308
110
Number of measured reflections
Number of independent reflections
Number of reflections with I > 2σ(I)
Number of refined parameters
R1
118613
18658
13575
The search for critical points in the region of
intermolecular interactions showed that beside the
strong hydrogen bond [N10···N5A 2.918(1) Å,
N10H10N5A 174°] (Fig. 2) joining molecules into the
dimers, a series of weak interactions C–H···π, C–H···N
and H···H can be identified. All the contacts indicated,
including the N–H···N hydrogen bond, belong to
interactions of the closed shells, as indicated by the
positive value of the local density of electron energy at
the appropriate critical points (3, –1). In order to
evaluate the energy of intermolecular interactions and
of crystalline packing we used the approach we
formerly had developed [14–16] based on the
correlation dependence of interaction energy on the
potential energy density at critical point (3, –1) [17].
The summing up of the energy of all independent
contacts led to the crystalline packing energy equal
21.1 kcal mol–1.
275
0.0406
0.1318
1.084
wR2
GOF
Residual electron density, e Å–3(dmin/dmax
)
0.419/–0.290
Multipole refinement
Number of reflections with I > 3σ(I)
R1, calculated by F
3308
0.0223
Rw, calculated by F
0.0231
GOF
0.8358
Residual electron density, e Å–3(dmin/dmax
)
0.15/–0.192
bonded dimer. During the dimer optimization the
parameters of hydrogen bond did not actually change,
in particular, the distance N5A···N10 is 2.957 Å. The
dimerization energy for this H-bonded dimer is
15.53 kcal mol–1 , i.e., 7.76 kcal mol–1 to one hydrogen
bond. Thus, it is possible to see that the energy of
hydrogen bond in the crystal obtained by us from X-ray
diffraction data is evaluated with the sufficiently high
accuracy.
As would be expected, the main contribution (35%)
to the formation of crystalline packing originates from
the hydrogen bond N10–H10N···N5A, whose energy is
7.5 kcal mol–1. For evaluating the accuracy of this
value we performed the calculation (PBE1PBE/6-
311G**) of the isolated molecule and hydrogen-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 11 2010

REACTIONS OF 1-NITROCYCLOHEXENE
2303
Besides the H-bonded dimer, in this crystal also
exists the centrosymmetrical dimer formed due to
sufficiently unusual directed interactions C–H···H–C
(H12···H13A 2.34 Å, C12H12H13A 178°, H12H13AC13A 61°)
(Fig. 2b). The search for critical points showed that,
although hydrogen atoms bear identical positive
charge, these contacts correspond to bonding
interactions. Moreover, critical point (3, –1) was also
localized for interaction between the hydrogen atoms
H12 (H···H 2.36 Å, C12H12H12A 117°), connected with
the inversion center, and also for the contact C–H···π
(H13···C3A 2.92 Å, C13H13C3A 139°). (Fig. 2b). The
energy of H···H interactions proves to be even higher
than H···C (0.7 kcal mol–1) and equals ~1 kcal mol–1. In
this case the total energy of CH···CH-bonded dimer
reaches 2 kcal mol–1. Thus, it is possible to conclude
that, although the hydrogen bond N–H···N is the most
strong in the crystal, the main contribution to the
crystal lattice energy (75%) is provided by the weak
interactions H···H and H···C. Therefore the directed
design of crystalline materials for the compounds with
a low number of functional groups capable to form
stable supramolecular synthons, is complex and today
actually insoluble problem.
on Silufol UV-254 plates with detecting on a chro-
matoscope.
X-Ray diffraction analysis of compound VI was
performed on a SMART APEX II CCD diffractometer
(MoKα radiation, graphite monochromator, ω-
scanning). The structure was solved by the direct
method and refined by means of full-matrix least-
squares procedure on F2hkl in anisotropic approxima-
tion. In the structure VI the hydrogen atoms were
localized from differential Fourier charts and refined in
isotopic approximation. The main crystallographic data
for structure VI are given in Table 2. All calculations
were performed using WinGX program package [4].
Figure was made by means of SHELXTL PLUS
program [18].
Multipole refinement for the structure VI was
performed within Hansen–Koppens’s formalism [19]
using XD program package [20] with the core and
valence electron density obtained from the wave
functions based on the relativistic solution of the
Dirac–Fock equation. Before refining the C–H and N–
H bond lengths were normalized to standart values
1.08 Å, and 1.03 Å, respectively. Multipole expansions
for oxygen, nitrogen and carbon atoms were limited to
octupole level, for hydrogen atoms, to dipole one. In
the case of hydrogen atom of NH-group we refined the
occupation of hexadecapole H40 for the more correct
description of hydrogen bonds. The refinement was
made by Fhkl. All covalently bound atom pairs satisfied
the Hirschfeld’s criterion on the bond rigidity [21]. The
residual electron density did not exceed 0.15 е Å–3. For
calculation of ν(r) from the X-ray diffraction data we
used approximation within Thomas–Fermi theory [22].
By this approach, the kinetic energy density g(r) can
Thus, as a result of this study a modification of the
synthesis method of 1-nitrocyclohexene is developed.
It is shown that the reaction of the latter with hydrazine
derivatives affords the products of mono- or bis-
addition, while the reaction with the diphenylguanidine
yields a binuclear system containing fused cyclohexene
and imidazole rings, 1-phenyl-2-N-penylamino-
4,5,6,7-tetrahydrobenzimidazole.
We
per-formed
analysis of the function of the electron density
distribution for this compound in the crystal by the
method of X-ray diffraction that allowed to estimate
the charge distribution, the nature of p-electrons
delocalization, and the role of interactions N–H···N,
C–H···H–C and C–H···C in the crystalline packing
formation.
be taken from the equation: g(r) = 3/10(3π2)2/3[ρ(r)]5/3
+
(1/72)|∇ρ(r)|2/ρ(r) + 1/6∇2ρ(r) in combination with the
local virial theorem [22]: 2g(r) + ν(r) = 1/4∇2ρ(r),
which provides a possibility to calculate both the
potential energy and local energy densities he(r). The
search for critical points (3, –1) and calculating
topological characteristics ρ(r), including he(r), g(r)
and ν(r), was performed with use of WINXPRO
program [23].
EXPERIMENTAL
1
The Н, 13С, HMQC NMR spectra were registered
on a Jeol ECX400A spectrometer at operating
frequencies 100.52 (13С) and 399.78 (1Н) MHz,
respectively, in DMSO-d6 using the signals of the
residual protonated solvent as reference signals. The
IR spectrum was taken on a Shimadzu IR-21 Prestige
Fourier-spectrometer from KBr. The elemental
analysis was performed on a Eurovector EA3028
analyzer. The reaction progress was monitored by TLC
Quantum-chemical calculations were made with the
Gaussian 03 package [24]. The standard values of
maximal force and mean-square shifting 4.5×10–4 and
1.8×10–3 аu, respectively, were used as convergence
criteria. Topological analysis of the wave function was
carried out using AIMAll program package [25].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 11 2010

2304
EFREMOVA et al.
1-Nitro-2-iodocyclohexane (Iа, Ib) (diastereo-
4.40, 3J(С2НС3НА) 8.90, 3J(С2НС3НВ) 8.17, 3J(C2HNH)
3
3
meric mixture, а:b = 2:1). To a solution of 13.24 g
(196 mmol) of sodium nitrite and 8.05 ml (144 mmol)
of ethylene glycol in 20 ml of water was added a
solution of 4.86 ml (48 mmol) of cyclohexene in 150 ml
of ethyl acetate. The mixture was cooled to 0°C, then
18.3 g (72 mmol) of iodine was added. The reaction
mixture was stirred at room temperature for 96 h under
nitrogen. The organic layer was separated, washed
with saturated solution of sodium thiosulfate, dried
over anhydrous magnesium sulfate, and concentrated
in a reduced pressure. Yield 6.49 g (53%), yellow oil,
bp 110–112°С (3 mm Hg). IR spectrum, ν, cm–1
(CHCl3): 1557, 1370 (NO2). 1Н NMR spectrum
(DMSO-d6), δ, ppm: diastereomer Iа, 1.38 m (2Н,
С5Н2), 1.95 m (2Н, С4Н2), 2.31 m (2Н, С3Н2), 2.53 m
6.50 Hz], 4.38 d.d [1H, NH, JNHN’H 2.00, J(C2HNH)
3
6.50 Hz], 4.45 d.d.d [1Н, С1Н, J(С1НС2Н) 4.40,
3
3J(С1НС6НА) 11.30, J(С1НС6НB) 9.98 Hz], 6.71 d
3
(1H, N'H, JNHN'H 2.00 Hz), 6.51, 6.65, 6.98 m (5H,
С6Н5). Found, %: С 61.56; H 7.41; N 17.89.
C12H16N3O2. Calculated, %: C 61.26; H 7.28; N 17.86.
1-Nitro-2-(N'-benzoylhydrazino)cyclohexane (IV).
To 1 g (8 mmol) of 1-nitrocyclohexene II was added
the boiling solution of 1.09 g (8 mmol) of benzoic acid
hydrazide in 21 ml of ethanol–water mixture (2:1). The
reaction mixture was cooled to room temperature, kept
for 24 h, and concentrated on a Petri dish. The
precipitate was filtered off, washed with ethanol, and
dried in air. Yield 1.64 g (78%), mp 132–135°С
(ethanol–water, 1:1). IR spectrum, ν, cm–1 (KBr):
1559, 1381 (NO2), 1607 (C=C), 1627 (C=O), 3312
3
(2Н, С6Н2), 4.40 d.d.d [1Н, С2Н, J(С1НС2Н) 4.28,
3J(С2НС3НА) 10.36, 3J(С2НС3НВ) 7.60 Hz], 4.62 d.t [1Н,
1
3
3
3
С1Н, J(С1НС2Н) 4.28, J(С1НС6НА) = J(С1НС6НВ)
10.70 Hz]; diastereomer Ib: 1.38 m (2Н, С5Н2), 1.95 m
(2Н, С4Н2), 2.42 m (2Н, С3Н2), 2.46 m (2Н, С6Н2),
(NH). Н NMR spectrum (DMSO-d6), δ, ppm: 1.63 m
(4Н, С4Н2, С5Н2), 1.68 m (2Н, С3Н2), 2.14 m (2Н,
С6Н2), 3.33 m (1Н, С2Н), 4.58 m (1Н, С1Н), 5.30 m
(1H, NH), 7.40–7.74 m (5H, Ph), 9.86 м (1H, N'H).
Found, %: N 16.29. C13H17N3O3. Calculated, %: N
15.97.
3.63 d.t [1Н, С2Н, J(С1НС2Н) 4.28, J(С2НС3НА) =
3J(С2НС3НВ) 10.00 Hz], 4.02 d.d.d [1Н, С1Н,
3J(С1НС2Н) 4.28, 3J(С1НС6НА) 9.40, 3J(С1НС6НВ)
7.85 Hz]. Mass spectrum, [М] + (m/z): 255.
3
3
1,2-Bis(2-nitrocyclohexyl)hydrazine (Vа, Vb). To
1 g (8 mmol) of 1-nitrocyclohexene II was added the
boiling solution of 0.78 ml (16 mmol) of hydrazine
hydrate in 14 ml of ethanol–water mixture (1:1). The
reaction mixture was cooled to room temperature, kept
for 48 h, the precipitate was filtered off, and dried in
air. Yield 0.21 g (21%) (diastereomers mixture, а:b =
1:1), mp 102–104°С (ethanol). IR spectrum, ν, cm–1
(KBr): 1545, 1379 (NO2), 3250 (NH). 1Н NMR
spectrum (DMSO-d6), δ, ppm: diastereomer Vа, 1.00–
1.30 m (8Н, 2С4Н2, 2С5Н2), 1.50–2.10 m (8Н, 2С3Н2,
2С6Н2), 2.83 d.d.t [2Н, 2С2Н, 3J(С1НС2Н) 5.11,
1-Nitrocyclohexene (II). To a solution of 5 g
(19.6 mmol) of 2-iodo-1-nitrocyclohexane I in 35 ml
of diethyl ether was added a solution of 2.46 ml
(17.6 mmol) of triethylamine in 15 ml of diethyl ether.
The reaction mixture was stirred at room temperature
for 24 h and filtered. The filtrate was washed with
water to pH 7, dried over anhydrous magnesium
sulfate, and concentrated in a reduced pressure. The
residue was purified by flash chromatography (eluent–
hexane). Yield 0.92 g (37%), Rf 0.69. IR spectrum, ν,
1
cm–1 (CHCl3): 1334, 1516 (NO2), 1635 (С=С). Н
3
3J(С2НС3Н2) 9.54, J(С2НNН) 5.76 Hz], 3.84 d [2H,
NMR spectrum (DMSO-d6), δ, ppm: 1.55 m (2Н,
С4Н2), 1.70 m (2Н, С5Н2), 2.30 m (2Н, С3Н2), 2.47 m
(2Н, С6Н2), 7.27 m (1Н, С2Н).
2NH, 3J(C2HNH) 5.76 Hz), 4.37 d.t [2Н, 2С1Н,
3J(С1НС2Н) 5.11, 3J(С1НС6Н2) 13.87 Hz]; diastereomer
Vb: 1.00–1.30 m (8Н, 2С4Н2, 2С5Н2), 1.50–2.10 m
(8Н, 2С3Н2, 2С6Н2), 2.79 d.d.t [2Н, 2С2Н, 3J(С1НС2Н)
1-Nitro-2-phenylhydrazinocyclohexane (III). To
0.63 g (5 mmol) of 1-nitrocyclohexene II was added a
solution of 1.1 g (10 mmol) of phenylhydrazine in 2 ml
of ethanol–water mixture (1:1). The reaction mixture
was kept for 24 h at room temperature. The precipitate
was filtered off and dried in air. Yield 0.55 g (47%),
mp 109–111С (decomp., ethanol) (115С [26]). IR
spectrum, ν, cm–1 (KBr): 1546, 1375 (NO2), 1605
3
3
5.45, J(С2НС3Н2) 9.13, J(С2НNН) 6.64 Hz], 3.82 d
[2H, 2NH, J(C2HNH) 6.64 Hz], 4.33 d.t [2Н, 2С1Н,
3
3J(С1НС2Н) 5.45, J(С1НС6Н2) 13.14 Hz]. Found, %:
3
С 50.31; H 7.53; N 19.38. C12H22N4O4. Calculated, %:
C 50.34; H 7.74; N 19.57.
1-Phenyl-2-phenylamino-4,5,6,7-tetrahydrobenz-
imidazole (VI). To 1.12 g (8.8 mmol) of 1-nitro-
cyclohexene II was added the boiling solution of
1.86 g (8.8 mmol) of N,N’-diphenylguanidine in 28 ml
1
(C=C), 3333 (NH). Н NMR spectrum (DMSO-d6), δ,
ppm: 1.25 m (4Н, С4Н2, С5Н2), 1.70 m (2Н, С3Н2),
2.15 m (2Н, С6Н2), 3.05 d.d.d.d [1Н, С2Н, 3J(С1НС2Н)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 11 2010

REACTIONS OF 1-NITROCYCLOHEXENE
2305
14. Lyssenko, K.A., Korlyukov, A.A., and Antipin M.Yu.,
of ethanol–water mixture (1:1). The reaction mixture
was cooled to room temperature and kept for 24 h. The
precipitate was filtered off and dried in air. Yield
0.71 g (24%), mp 204–206°С (benzene). IR spectrum,
ν, cm–1 (KBr): 1595 (С=С), 1617 (С=N), 3340 (NH).
1Н NMR spectrum (DMSO-d6), δ, ppm: 1.70 m (6Н,
С4Н2, С5Н2, С6Н2), 2.27 m (2Н, С7Н2), 6.65 m, 7.03–
7.48 m (10Н, Ph), 7.76 s (1Н, NH). Found, %: С
79.08; H 6.67; N 14.52. C19H19N3. Calculated, %: C
78.86; H 6.62; N 14.52.
Mendeleev. Commun., 2005, p. 90.
15. Lyssenko, K.A., Korlyukov, A.A., Golovanov, D.G.,
Ketkov, S.Yu., and Antipin, M.Yu., J. Phys. Chem. A,
2006, vol. 110, p. 6545.
16. Lyssenko, K.A., Barzilovich, P.Yu., Nelyubina, Yu.V.,
Astafiev, E.A., Antipin, M.Yu., and Aldoshin, S.M., Izv.
Ross. Akad. Nauk, Ser. Khim., 2009, no. 1, p. 31.
17. Espinosa, E., Alkorta, I., Rozas, I., Elguero, J., and
Molins, E., Chem. Phys. Letts., 2001, vol. 336, p. 457.
18. Sheldrick, G.M. SHELXTL v. 5.10, Structure
Determination Software Suit, Bruker AXS: Madison,
Wisconsin, USA.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (project no. 10-03-
00578-а) and by the President of Russian Federation
(grant no. MD-237.2010.3).
19. Hansen, N.K. and Koppens, P., Acta Crystallogr. A,
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Volkov, A., Gatti, C., Mallinson, P.R., Farrugia, L.J.,
Su, Z., and Hansen, N.K., XD-A Computer Program
Package for Multipole Refinement and Topological
Analysis of Charge Densities from Diffraction Data,
2003.
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