Transformation of 1,1-Dichloro-2,2-bis(4-nitrophenyl)ethene in the Reaction with Nitrite Ion in Polar Aprotic Solvents

Article abstract of DOI:10.1134/S107036322001003X

The reaction of 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene with sodium nitrite in polar aprotic solvents has been studied. Products of the reaction have been identified, and effects of different factors, including reactant dissociation and solvation, on the reaction rate constants have been analyzed. Thermodynamic parameters of the reaction have been determined, the multistep process has been simulated by quantum chemical calculations, and a plausible mechanism has been proposed.

Full text of DOI:10.1134/S107036322001003X

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 1, pp. 13–22. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 1, pp. 18–30.
Transformation of 1,1-Dichloro-2,2-bis(4-nitrophenyl)ethene
in the Reaction with Nitrite Ion in Polar Aprotic Solvents
a
a,
E. A. Guzov and V. N. Kazin *
a
Demidov Yaroslavl State University, Yaroslavl, 150003 Russia
*
e-mail: kaz@uniyar.ac.ru
Received June 20, 2019; revised November 28, 2019; accepted December 4, 2019
Abstract—The reaction of 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene with sodium nitrite in polar aprotic solvents
has been studied. Products of the reaction have been identified, and effects of different factors, including reactant
dissociation and solvation, on the reaction rate constants have been analyzed. Thermodynamic parameters of the
reaction have been determined, the multistep process has been simulated by quantum chemical calculations, and
a plausible mechanism has been proposed.
Keywords: 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene, 4,4'-dinitrobenzophenone, nitrite ion, dissociation, solva-
tion, reaction mechanism
DOI: 10.1134/S107036322001003X
The chemistry of chloral and its derivatives, such as
,2-diaryl-1,1,1-trichloroethanes, has been well docu-
mented. These compounds were used as insecticides,
intermediate products in the synthesis of monomers
and ab initio quantum chemical studies [13–15]. Prob-
able paths of the transformation of 1,1-dichloro-2,2-
bis(4-nitrophenyl)ethene to 4,4'-dinitrobezophenone
were proposed in [10, 12] using ab initio calculations.
However, no comprehensive study of the mechanism of
this transformation was performed.
2
[
1, 2], dyes, modifiers, and reagents for organic syn-
thesis [3]. The use of 2,2-diaryl-1,1,1-trichloroethanes
as monomers is limited due to low thermal stability of
polymers obtained therefrom. The transformation of the
trichloroethylidene group of 2,2-diaryl-1,1,1-trichloro-
ethanes into dichloroethenylidene or carbonyl makes
the resulting polymers incombustible, heat resistant, and
self-extinguishing [4].
The present work was aimed at determining the
structure of intermediate and final products (including
by-products) of the reaction of 1,1-dichloro-2,2-bis(4-
nitrophenyl)ethene with nitrite ion in polar aprotic sol-
vents, studying the reaction kinetics with account taken of
dissociation and solvation of the reactants, and simulating
the multistep process by quantum chemical calculations.
Nitro-substituted substrates have attracted some in-
terest due to their high reactivity and diversity of trans-
formation paths. The reactivity of 1,1,1-trichloro-2,2-
bis(nitrophenyl)ethanes toward alkali metal nitrites in
polar aprotic solvents has been studied in [5–12]. It
was found that 1,1,1-trichloro-2,2-bis(4-nitrophenyl)-
ethane reacts with sodium nitrite at 20–70°C to give
only the dehydrochlorination product, 1,1-dichloro-2,2-
bis(4-nitrophenyl)ethene [7]. Raising the temperature
to 80–130°C leads to further transformation of the di-
chloroethene moiety to carbonyl, yielding 96–98% of
The effects of the reactant concentrations, tempera-
ture, and solvent nature on the reaction kinetics were
studied under the following conditions: 1,1-dichloro-2,2-
bis(4-nitrophenyl)ethene concentration [S] = 1–6 mM,
0
sodium nitrite concentration [NaNO ] = 10–100 mM;
2 0
temperature 353–393 K; solvents ethanol, DMF, dimeth-
ylacetamide (DMA), DMSO, N-methylpyrrolidin-2-one
(
NMP), DMF–ethanol (80 : 20, mol %); under these
conditions, the reaction was homogeneous.
4
,4'-dinitrobenzophenone (Scheme 1).
According to the HPLC and GC/MS data, the reac-
tion of 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene with
sodium nitrite gives 4,4'-dinitrobenzophenone as the
major product and is accompanied by accumulation of
The mechanism of dehydrochlorination of 1,1,1-tri-
chloro-2,2-bis(4-nitrophenyl)ethane with sodium nitrite
was identified as E2H on the basis of the results of kinetic
1
3

14
GUZOV, KAZIN
Scheme 1.
NO2
O N
NO2
O N
2
2
NaNO2
H
2
0ꢀ70qC
C
C
Cl
Cl
Cl
Cl
Cl
O N
NaNO2
NO2
2
80ꢀ130qC
O
another product whose concentration does not change
after complete conversion of the substrate. Material bal-
ance experiments (373 K, DMF, [S] = 5 mM, [NaNO ] =
formation of 4,4'-dinitrobenzophenone (yield 95–98%)
and its oxime (<2.5%; Scheme 2).
0
2 0
Increase of the initial sodium nitrite concentration
5
0 mM) showed that 2.5±0.4% of the substrate is con-
from 10 to 100 mM ([S] = 5 mM, 373 K, DMF) is accom-
0
verted to the by-product.
panied by reduction of the apparent reaction rate constant
The reaction of 1-chloro-2,2-bis(4-nitrophenyl)eth-
ene with sodium nitrite in DMF was studied previously
(
kef), which may be due to effect of dissociation of the
reagent. The dissociation of sodium nitrite in DMF was
studied by conductometry, and its dissociation constant
was estimated at K = 9.15×10 at 373 K. The apparent
rate constant showed a correlation with the degree of dis-
sociation (α), which indicated that the reagent dissociation
process directly contributes to the reaction rate:
[
21] using the following reactant concentrations: [S] =
0
3
0 mM, [NaNO ] = 600 mM. The complete conversion
–3
2
0
d
of 1-chloro-2,2-bis(4-nitrophenyl)ethene was achieved
in 0.5–1.0 h at 50°C, and the products were 4,4'-dinitro-
benzophenone (50%), 4,4'-dinitrobenzophenone oxime
(
30%), and 6-nitro-3-(4-nitrophenyl)-2,3-dihydro-1,2-
log k = –3.06 + 1.60 α,
ef
benzoxazole (20%).
r = 0.986, N = 5.
It may be presumed that one of these compounds
is formed in the reaction of 1,1-dichloro-2,2-bis(4-
nitrophenyl)ethene with sodium nitrite. In fact, the
by-product was identified as 4,4'-dinitrobenzophenone
oxime by HPLC and GC/MS using an authentic sample
synthesized according to [22]. By special experiment
we showed that 4,4'-dinitrobenzophenone oxime is not
converted to 4,4'-dinitrobenzophenone in the presence
of sodium nitrite. Thus, the reaction of 1,1-dichloro-2,2-
bis(4-nitrophenyl)ethene with sodium nitrite leads to the
The average true rate constants calculated from
the substrate consumption and product formation
rates with account taken of reagent dissociation were
3
3
−1 −1
(11.25±0.11)×10 and (10.27±0.13)×10 L mol s , re-
spectively. The difference between these values confirms
the formation of 4,4'-dinitrobenzophenone as by-product.
Study of the effect of the substrate concentration ([S] =
0
1
–6 mM, 373 K, DMF, [NaNO ] = 50 mM) gave the
2
average rate constant values consistent with those given
above. The partial reaction orders in the reagent and sub-
strate were estimated as first by the van’t Hoff method.
The reaction kinetics are described by a second-order
equation, and 2 equiv of sodium nitrite is required to
achieve complete conversion of 1,1-dichloro-2,2-bis(4-
nitrophenyl)ethene.
Table 1. Apparent rate constants and thermodynamic param-
eters of the reaction of 1,1-dichloro-2,2-bis(4-nitrophenyl)-
a
ethene with sodium nitrite
3
−1
T, K
k ×10 , L mol s−1 Thermodynamic parameters
ef
3
3
3
3
3
53
0.78
1.56
3.25
7.42
14.83
Ea = 84.11 kJ/mol,
ΔH = 82.76 kJ/mol,
ln A = 22.05,
63
73
83
93
Temperature effect on the rate constant in DMF was
studied, and thermodynamic parameters of the reaction
were determined (Table 1). The negative entropy of ac-
tivation indicates that the rate-limiting step in the trans-
formation of 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene
to 4,4'-dinitrobenzophenone is a bimolecular process.
ΔS298 = –72.53 J mol–1 K–1
a
DMF, [S] = 5 mM, [NaNO ] = 50 mM.
0
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

TRANSFORMATION OF 1,1-DICHLORO-2,2-BIS(4-NITROPHENYL)ETHENE
15
Scheme 2.
O N
NO2
2
O N
NO2
+
2
O
NaNO2
×
C
O N
2
NO2
Cl
Cl
N
OH
Study of the effect of solvent nature showed that no
reaction occurred in protic solvents (e.g., in ethanol).
The apparent rate constants in different solvents were
as follows (373 K, [S] = 5 mM, [NaNO ]= 50 mM),
of Pople and Dunning basis sets. We selected the DFT
method since it ensures fairly accurate determination of
the steric structure of molecules and is used to simulate
mechanisms of chemical reactions. The B3LYP hybrid
functional where the exchange energy is calculated us-
ing the Hartree–Fock approximation is considered most
general.
0
2
3
−1 −1
k ×10 , L mol s : 11.03 (N-methylpyrrolidone), 6.31
ef
(
(
dimethylacetamide), 3.25 (DMF), 1.31 (DMSO), 0.61
DMFA–ethanol, 80 : 20). The obtained correlation
between k and the Dimroth–Reichardt parameter sug-
First of all, it was necessary to determine reactive
centers in the initial molecules. The steric structure, con-
formations, and HOMO and LUMO of nitrite ion were
described in detail in [15]. The frontier orbital energies of
the reactants (Table 2) were calculated for their prelimi-
narily optimized (equilibrium) structures with analysis of
Hessian matrices. The data in Table 2 indicate that both re-
actants are soft (the energy difference is larger than 1 eV).
The reactivity of atoms in soft reagents is determined by
the corresponding orbital coefficients. It should be noted
that both reactants are electrophiles (negative LUMO
energy). However, nitrite ion is a weaker electrophile,
and it behaves as a nucleophile in the given system. On
the basis of the obtained data, the transition state (TS)
ef
gests a significant contribution of specific solvation to
the reaction of 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene
with sodium nitrite:
log k = 13.38 – 0.086 E ,
ef
T
r = 0.975, N = 5.
The reaction slows down as the solvating power of
the medium (E ) increases; this means that the initial
T
reactants are solvated better than the transition state.
The above data are necessary for the subsequent quan-
tum chemical simulation and consideration of the reaction
mechanism. The transformation of 1,1-dichloro-2,2-
bis(4-nitrophenyl)ethene into 4,4'-dinitrobenzophenone
by the action of sodium nitrite is a multistep process.
The initial structures, pre-reaction complex, transition
state, and post-reaction complex were optimized for each
elementary step.
4
was simulated for the formation of a bond between the C
5
atom of the substrate and O of nitrite ion (Fig. 1) while
searching for saddle point.
Preliminary calculations showed the possibility of
formation of three transition states with different orienta-
tions of nitrite ion with respect to the substrate molecule.
The transition states were identified by the presence of
one imaginary frequency in the corresponding vibrational
At present, the most popular quantum chemical meth-
ods are those based on the density functional theory (DFT)
(DFT) [16–18] and third-order Møller–Plesset perturba-
tion theory (MP3) [19, 20] and utilizing a wide range
Table 2. Frontier orbital energies of 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene and nitrite ion
Reacting species
,1-Dichloro-2,2-bis(4-nitrophenyl)ethene
Nitrite ion [6]
ELUMO, eV
–3.282
EHOMO, eV
–6.998
|EHOMO – ELUMO|, eV
1
3.716
5.134
–0.751
–5.885
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

16
GUZOV, KAZIN
(a)
(b)
(c)
TS-1
2074.150620
TS-2
TS-3
–2074.150240
–
–2074.152997
Fig. 1. Structures and energies (hartree) of possible transition states in the nucleophilic substitution step.
4
spectrum. Transition state TS3 has the highest energy and
was discarded. The most energetically favorable is TS2.
philic substitution at the vinylic carbon atom. The C –Cl1
bond length increases from 1.744 to 1.828, the charge on
Cl changes from 0.055 to –0.065, and the order of the
C –Cl bond decreases from 1.049 to 0.990. These find-
ings indicate that Cl is a leaving atom. The C ···Cl
distance in the post-reaction complex is 3.434 Å, i.e.,
1
Descend along the intrinsic reaction coordinate (IRC)
toward initial reactants and products was considered,
energies of the pre- and post-reaction complexes were
determined, and energy profile of the nucleophilic sub-
stitution step was constructed (Fig. 2). The orientation
4
1
1
4
1
4
1
there is no bond between C and Cl .
2
4
The energy of activation of this step is 69.69 kJ/mol,
and the heat effect is –69.24 kJ/mol (exothermic process).
of the nitrite ion with respect to the C –C π-bond of the
substrate in the pre-reaction complex indicates formation
2
4
of a π-complex. In the transition state, the C –C bond
order decreases from 1.665 to 1.235, which corresponds
to π-bond rupture and electron density redistribution in-
volving the nitro groups. This is confirmed by increase of
the negative charge on the oxygen atoms. The presence
of electron-withdrawing nitro groups facilitates nucleo-
In order to elucidate the mechanism of the nucleophilic
substitution step (addition–elimination or elimination–ad-
dition), the dynamics of variation of bond lengths was
considered in detail (Table 3). When the distance between
the reactants changes from 2.820 to 1.768 Å (addition
4
1
of nitrite ion), the C –Cl bond elongates insignificantly
–
–
–
–
–
–
–
2074.15
2074.16
2074.17
2074.18
2074.19
2074.20
2074.21
Ea = 69.69 kJ/mol
2074.179541
–
ǻH = –69.24 kJ/mol
Reaction coordinate
Fig. 2. Energy profile for nucleophilic substitution of chlorine in 1,1-dichloro-2,2-bis(4-nitrophenyl)ethene by nitrite ion.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

TRANSFORMATION OF 1,1-DICHLORO-2,2-BIS(4-NITROPHENYL)ETHENE
17
Table 3. Bond lengths (Å) in the pre- and post-reaction complexes and transition state for the intramolecular elimination step
Bond
Pre-reaction complex
Transition state
1.768
Post-reaction complex
4
5
С –О
2.820
1.744
1.355
1.258
1.341
3.434
1.354
1.586
4
1
С –Cl
1.828
2
4
C –C
1.414
5
3
O –N
1.322
4
1
(
from 1.744 to 1.828 Å) before transition state formation;
transition state, the C –Cl bond elongates from 1.779
to 2.179 Å, and its order decreases from 1.055 to 0.577,
which indicates rupture of that bond. A similar trend is
1
4
i.e., the Cl atom remains bonded to C by that moment.
Further shortening of the bond between the nitrite ion and
C at each step of IRC optimization is characterized by a
4
5
3
observed for the O –N bond which changes from 1.695
to 2.335 Å with simultaneous decrease in order from
0.557 to 0.145. The calculated Hessian matrix contained
significantly higher rate than elimination of chloride ion.
4
Thus, the nucleophilic substitution at C follows the
–
1
a single imaginary frequency (i188.81 cm ).
addition–elimination pathway (Ad -E; Scheme 3). This
N
leads to the formation of 1-chloro-2,2-bis(4-nitrophenyl)-
The rearrangement is accompanied by elimination of
nitrosyl chloride. The energy profile for this process is
shown in Fig. 4. In going to the post-reaction complex, the
C –Cl bonds lengthens from 1.782 to 3.648 Å, and the O –
N3 bond length increases from 1.700 to 2.964 Å, whereas
the Cl1–N3 distance shortens from 3.251 to 2.074 Å
2
4
ethenyl nitrite (2) where the C –C bond order is 1.590
double bond with the electron density shifted to electron-
(
4
5
5
3
4
1
5
withdrawing groups). The orders of the C –O and O –N
bonds are 1.040 and 0.557, respectively, i.e., the electron
density is shifted toward the former.
We then analyzed possible transformation pathways of
(bond formation). The calculated geometric parameters
of the nitrosyl chloride molecule are consistent with
nitrosooxy derivative 2: (1) nucleophilic attack of nitrite
4
1
3
6
3
ion on the C atom, followed by elimination of chloride
published data: Cl –N 2.074 Å (1.960 Å [25]), O –N
6
3
1
ion; (2) attack of the oxygen atom of nitrite ion on the
nitroso nitrogen atom [24] of 2; (3) intramolecular rear-
rangement of intermediate 2. Simulation of pathways (1)
and (2) revealed the absence of maxima on the potential
energy surface (no transition state) as the reactants ap-
proached each other.
1.131 Å (1.160 Å [25]), O N Cl 113.94° (113° [25]).
Further transformation of nitrosyl chloride in the given
system may follow different pathways. In particular, it
can react with sodium nitrite to produce nitrous anhydride
and sodium chloride. Nitrous anhydride is thermally
unstable, and it decomposes to nitrogen oxides. Alterna-
tively, decomposition of nitrosyl chloride at a temperature
exceeding 373 K could produce molecular chlorine and
Figure 3 shows the transition state structure for in-
tramolecular rearrangement of nitrite 2. In going to the
Scheme 3.
z
–
O N
NO2
2
O N
NO2
N
2
Ea = 69.69 kJ/mol
C
ꢀ
C
N
O
O
Cl
Cl
Cl
O
O
Cl
1
O N
2
NO2
ꢀ
Cl
N
C
Cl
O
O
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

18
GUZOV, KAZIN
ꢀ
ɚꢁꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢀEꢁꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢀFꢁ
C11
H8
.179
H6
C2
0.072
–0.116
.146
–0.313
0.006
1
.3471
1
.429
C
0
.262
2
0.577
0
1
.205
C11
1.597
5
O
–
0.402
2
.335
.111
2.474
N3
0
.355
0
.145
.426
0
.135
1
2
O6
0
.333
Fig. 3. Structure of the transition state in the intramolecular elimination of nitrosyl chloride from 1-chloro-2,2-bis(4-nitrophenyl)ethenyl
nitrite (2): (a) interatomic distances, Å; (b) Mulliken charges on atoms; (c) bond orders.
nitrogen(II) oxide. Potentiometric titration of the reac-
tion mixture showed the presence of chloride ions (70%
of the theoretical amount) after complete conversion of
possibility of subsequent nucleophilic attack of the second
nitrite ion. However, no transition state (maximum on the
PES) was localized for the interaction between the nitrite
1
,1-dichloro-2,2-bis(4-nitrophenyl)ethene.
4
oxygen atom and C of 3. It was found that the attack
Thus, the results of quantum chemical calculations
of nitrite ion leads to the formation of a four-membered
–
1
suggest that compound 2 decomposes via intramolecu-
lar elimination of nitrosyl chloride with the formation
of 2,2-bis(4-nitrophenyl)ethen-1-one (3) as shown in
Scheme 4. This reaction is similar to the Boord reaction
of β-halo ethers.
cyclic transition state (Fig. 5; i558.15 cm ).
It is known that unsubstituted ketene reacts with nu-
cleophiles at the carbonyl carbon atom. Nitrite ion is an
ambident nucleophile capable of reacting at both nitro-
gen and oxygen atoms. In our case, mutual approach of
the reactants involves interaction between the nitrogen
Optimization of the structure of 3 showed that it
corresponds to a minimum on the PES (no imaginary
frequencies were present in the corresponding Hessian
matrix). The described rearrangement of 1-chloro-2,2-
bis(4-nitrophenyl)ethenyl nitrite (2) gives rise to a
cumulated π-bond system (C=C=O), which implies the
4
atom of nitrite ion and carbonyl carbon atom (C ) of the
substrate. This interaction is facilitated by electrostatic
3
4
attraction (Mulliken charges on the N and C atoms are
–0.323 and +0.344, respectively) which stabilizes the
transition state where the distance between N and C4
3
Scheme 4.
z
O N
NO2
O N
2
NO2
2
Ea = 36.23 kJ/mol
C
N
C
Cl
O
O
Cl
O
N
O
2
O N
NO2
2
Cl
C
O
N
O
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

TRANSFORMATION OF 1,1-DICHLORO-2,2-BIS(4-NITROPHENYL)ETHENE
19
–
–
–
–
–
–
–
1613.82
1613.83
1613.84
1613.85
1613.86
1613.87
1613.88
Ea = 36.23 kJ/mol
ǻH = –29.88 kJ/mol
Reaction coordinate
Fig. 4. Energy profile for the intramolecular elimination of nitrosyl chloride from 1-chloro-2,2-bis(4-nitrophenyl)ethenyl nitrite (2).
3
4
shortens from 3.023 to 2.733 Å (Fig. 5). The N –C bond
order increases to 0.183, indicating a weak interaction.
However, this interaction does not lead to the appearance
of an energy maximum on the PES, but considerably
facilitates interaction between the nitrite oxygen atom
solution of calcium hydroxide (precipitation of calcium
carbonate).
This transformation is characterized by an energy
barrier of 200.95 kJ/mol; therefore, it is a limiting step of
the reaction. The heat effect is 68.40 kJ/mol (endothermic
process). The mechanism of this step is addition–elimi-
2
and C (bond order 0.393).
The energy profile for the nucleophilic substitution
step in the reaction of 3 with nitrite ion is shown in
Fig. 6. In the pre-reaction complex, the nitrite ion is ori-
nation (Ad E; Scheme 5). Carbanion 4 is stabilized by
N
aprotic solvent and electron-withdrawing effect of the
nitro groups, so that the negative charge is delocalized
over the conjugated π-system. We failed to localize any
transition state for the attack of the nitrite nitrogen atom
2
4
6
2
ented toward the π-C =C bond. The O –C bond shortens
from 3.262 to 1.825 Å simultaneously with the elonga-
2
2
4
on C of ketene 3.
tion of the C –C bond from 1.339 to 1.517 Å. Further
6
2
approach of O to C to a distance of 1.402 Å leads to
Thus, according to the results of quantum chemical
simulation, the transformation of 1,1-dichloro-
2,2-bis(4-nitrophenyl)ethene to 4,4'-dinitrobenzo-
phenone involves a series of consecutive steps (Scheme 6):
(1) nucleophilic substitution of chlorine at the vinylic
carbon atom by nitrite ion via addition–elimination
4
5
elimination of the C –O fragment (carbon monoxide
molecule) and formation of carbanion 4. Carbon(II)
oxide is then oxidized to carbon dioxide. The formation
of carbon dioxide was confirmed experimentally by pass-
ing the gaseous phase from the reaction zone through a
ꢀ
ɚꢁꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢀEꢁꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢀFꢁꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂꢂ
H1
C2
H2
O6
C2
0.393
O6
1.017
1
.097
1
.804
O5
C4
N3
N3
C4
O7
O7
0.183
O5
1.620
Fig. 5. Structure of the transition state in the nucleophilic substitution in 2,2-bis(4-nitrophenyl)ethen-1-one (3) by nitrite ion:
(a) interatomic distances, Å; (b) Mulliken charges on atoms; (c) bond orders.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

20
GUZOV, KAZIN
Scheme 5.
z ꢀ
O N
NO2
2
O N
NO2
2
Ea = 200 kJ/mol
O
O
C
O
3
N
O
C
N
O
O
O N
NO2
2
O
N
O C
O
4
mechanism (Ad -E); (2) intramolecular syn-elimination
of nitrosyl chloride from 1-chloro-2,2-bis(4-nitrophenyl)-
isolation step or in the course of HPLC analysis of the
reaction mixture (eluent acetonitrile–water, 70 : 30).
Decomposition of the solvation shell formed by aprotic
solvent molecules, in particular by the action of protons,
induces barrierless transformation of intermediate 4 to
N
ethenyl nitrate; and (3) nucleophilic substitution (Ad -E)
N
2
by the second nitrite ion at the C carbon atom with
elimination of carbon monoxide molecule through a
four-membered cyclic transition state. The latter reaction
is the rate-determining step.
4
,4′-dinitrobenzophenone 5.
EXPERIMENTAL
1,1-Dichloro-2,2-bis(4-nitrophenyl)ethene and 4,4'-di-
nitrobenzophenone were synthesized according to known
Finally, the transformation of carbanionic intermedi-
ate 4 to 4,4'-dinitrobenzophenone is promoted by change
of the solvent, e.g., due to addition of water during the
–
–
–
–
–
–
–
–
–
–
1228.94
1228.95
1228.96
1228.97
1228.98
1228.99
1229.00
1229.01
1229.02
1229.03
Ea = 200.95 kJ/mol
ǻH = 68.40 kJ/mol
Reaction coordinate
Fig. 6. Energy profile for the reaction of 2,2-bis(4-nitrophenyl)ethen-1-one (3) with nitrite ion.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

TRANSFORMATION OF 1,1-DICHLORO-2,2-BIS(4-NITROPHENYL)ETHENE
21
Scheme 6.
O N
NO2
O N
2
NO2
O N
2
NO2
2
ꢀ
ONO
ꢀ
ꢀ
Cl
ꢀONCl
Ea = 29.88 kJ/mol
C
C
N
C
O
Ea = 69.24 kJ/mol
Cl
Cl
Cl
O
O
1
2
3
ꢀ
–CO ONO
Ea = 200.95 kJ/mol
ꢀ
O N
NO2
2
O N
NO2
2
H+
HNO
ꢀ
O
N
O
O
5
4
procedures [8]. 4,4'-Dinitrobenzophenone oxime was
prepared as described in [22].
compound to be analyzed); split ratio 1 : 30, injection
volume 1 μL; ion source and interface temperature 150°C;
electron impact, 70 eV. The IR spectra were recorded on
a Perkin Elmer Spectrum 65 FT-IR instrument equipped
with an UATR accessory. The H NMR spectra were mea-
sured on a Bruker DRX500 SF-500 spectrometer from
The kinetic study was carried out using a glass reactor
equipped with a stirrer, reflux condenser, thermometer,
and capillary (for bubbling nitrogen). The reactor was
charged with an appropriate solvent and 1,1-dichloro-2,2-
bis(4-nitrophenyl)ethene, and the mixture was adjusted
to a required temperature with an accuracy of ±0.5°C. A
required amount of sodium nitrite was added with stir-
ring, and samples of the mixture were withdrawn during
the reaction. The samples were cooled and analyzed by
HPLC.
1
solutions in DMSO-d ‒CCl containing tetramethylsilane
6
4
as internal standard.
4,4'-Dinitrobenzophenone. mp 192–194°C. IR spec-
–
1
trum, ν, cm : 1532 (NO , asym.), 1352 (NO , sym.), 1676
2
2
1
(C=O). H NMR spectrum, δ, ppm: 8.43 m and 8.07 m
(8H, H ). Mass spectrum, m/z (I , %): 272 (47.18)
arom
rel
+
+
+
[
1
1
M] , 242 (5.79) [M – NO] , 226 (3.37) [M – NO ] ,
2
80 (5.34) [M – 2NO ] , 150 (100) [M – C H NO ,] ,
20 (24.48) [M – C H NO – NO] , 104 (21.59)
The concentrations of 1,1-dichloro-2,2-bis(4-nitro-
phenyl)ethene and 4,4'-dinitrobenzophenone were de-
termined using a Perkin Elmer high-performance liquid
chromatograph equipped with a UV detector; 150×4.6-
mm column packed with C , pore size 100 Å, temperature
+
+
2 6 4 2
+
6
4
2
+
[
M – C H NO – NO ] , 92 (19.76) [M – CO – C H NO –
6 4 2 2 6 4 2
+
NO] , 76 (10.13) [C H ].
6
4
18
3
0°C, eluent H O–MeCN (30 : 70), flow rate 0.8 mL/min,
4,4'-Dinitrobenzophenone oxime. mp 194–196°C.
2
–
1
detection at λ 254 nm, injection volume 10 μL; 1,1,1-tri-
chloro-2,2-bis(4-chloro-3-nitrophenyl)ethane was used
as internal standard; retention times of 4,4'-dinitroben-
zophenone and 1,1-dichloro-2,2-bis(4-nitrophenyl)-
ethene 4.27 and 8.9 min, respectively.
IR spectrum, ν, cm : 1340, 1520 (NO ); 1655 (C=N),
2
1
3200 (O–H). H NMR spectrum, δ, ppm: 7.59 m (2H,
Harom), 7.66 m (2H, Harom), 8.18 m (2H, Harom), 8.33 m
(2H, Harom), 12.0 s (1H, OH). Mass spectrum, m/z (I ,
rel
+
+
%): 271 (25.1) [M – O] , 254 (78.2) [M – O – OH] , 224
+
+
(
1
99.9) [M – OH – NO ] , 179 (73.9) [M – O – 2NO ] ,
GC/MS analyses were carried out with a Perkin Elmer
Clarus 680 gas chromatograph coupled with a Clarus
SQ 8T mass-selective detector; ELITE-5ms capillary
column, 30 m×0.25 mm, film thickness 0.25 μm; carrier
gas helium, flow rate 1 mL/min; injector temperature
2
2
+
49 (58.2) [M – O – Ar-NO ] , 103 (71.6) [M – O –
2
+
Ar-NO – NO ] , 76 (81.16) [Ar].
2
2
The spectral characteristics of 4,4'-dinitrobenzophe-
none [23, 26] and 4,4'-dinitrobenzophenone oxime [22]
were consistent with published data.
2
80°C, oven temperature 200–220°C (depending on the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

2
2
GUZOV, KAZIN
nikova, N.G., and Plakhtinskii, V.V., Izv. Vyssh. Uchebn.
Quantum chemical calculations at the DFT B3LYP/6-
1G++(d,p) level of theory were performed using FireFly
.2 software [27]. Solvation effects were taken into ac-
3
8
Zaved., Khim. Khim. Tekhnol., 2009, vol. 52, no. 8, p. 16.
13. Kazin, V.N., Kuzhin, M.B., Sirik, A.V., and Guzov, E.A.,
Russ. J. Org. Chem., 2016, vol. 52, no. 9, p. 1277.
https://doi.org/10.1134/S1070428016090049
14. Kazin, V.N., Kuzhin, M.B., Sibrikov, S.G., Sirik, A.V.,
Guzov, E.A., and Plakhtinskii, V.V., Russ. J. Gen. Chem.,
2017, vol. 87, no. 3, p 381.
https://doi.org/10.1134/S1070363217030033
15. Guzov, E.A., Kazin, V.N., and Zhukova, A.A., Russ. J.
Gen. Chem., 2018, vol. 88, no. 10, p. 2044.
count in terms of the PCM-D model [28] including such
solvent parameters as solvation radius and dielectric
permittivity at 373 K. The calculated structures were
visualized using Chemcraft package [29]. Stationary
points on the potential energy surfaces were identified
as minima by the lack of imaginary frequencies in the
corresponding Hessian matrix, and as transition states,
by the presence of one imaginary frequency.
https://doi.org/10.1134/S1070363218100031
6. Schlüter, M. and Sham, L.J., Phys. Today, 1982, vol. 35,
no. 2, p. 36.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
REFERENCES
1
1
1
https://doi.org/10.1063/1.2914933
7. Koch, W. and Holthausen, M.C., A Chemist’s Guide to
Density Functional Theory, Toronto: Willey-VCH, 2001,
p. 293.
1
2
3
4
5
. Rusanov,A.L., Keshtov, M.L., Kirillov,A.A., Kireev,V.V.,
Keshtova, S.V., and Petrovskii, P.V., Polym. Sci., Ser. B,
000, vol. 42, nos. 11–12, p. 314.
. Keshtov,M.L.,Rusanov,A.L.,Kireev,V.V.,Keshtova,S.V.,
2
8. Kon, V., Usp. Fiz. Nauk, 2002, vol. 172, no. 3, p. 336.
Petrovskii, P.V., and Kirillov, A.A., Polym. Sci., Ser. A,
19. Pople, J.A., Binkley, J.S., and Seeger, R., Int. J. Quantum
Chem., 1976, vol. 10, no. S10, p. 1.
2
001, vol. 43, no. 6, p. 588.
. Batanero, B., Ramirez-Moreno, M., and Barba, F.,
Tetrahedron Lett., 2016, vol. 57, p. 2290.
https://doi.org/10.1016/j.tetlet.2016.04.046
. Rusanov, A.L., Keshtov, M.L., Keshtova, S.V., Petro-
vskii, P.V., and Kundina, Y.F., Polym. Sci., Ser. B, 2000,
vol. 41, nos. 11–12, p. 301.
. Kazin,V.N.,Sibrikov,S.G.,Kopeikin,V.V.,Mironov,G.S.,
Rusanov, A.L., and Kazakova, G.V., USSR Inventor’s
Certificate no. 1606507, 1990; Byull. Izobret., 1990,
no. 42.
https://doi.org/10.1002/qua.560100802
20. Pople, J.A., Seeger, R., and Krishnan, R., Int. J. Quantum
Chem., 1977, vol. 12, no. S11, p. 149.
https://doi.org/10.1002/qua.560120820
2
1. Kazin, V.N., Sibrikov, S.G., Sapozhnikova, N.G., and
Orlova, T.N., Bashk. Khim. Zh., 2008, vol. 15, no. 3, p. 61.
2. US Patent no. 5879657A, 1999.
2
23. Suzuki, H. and Murashima, T., J. Chem. Soc., Perkin
Trans. 1, 1994, vol. 1, no. 7, p. 903.
6
7
8
. Kazin, V.N., Sibrikov, S.G., Kopeikin, V.V., and Miro-
nov, G.S., Zh. Org. Khim., 1991, vol. 27, no. 2, p. 380.
. Sibrikov, S.G., Kazin, V.N., and Kopeikin, V.V., Zh. Org.
Khim., 1994, vol. 30, no. 7, p. 1080.
. Sibrikov,S.G.,Kazin,V.N.,Kopeikin,V.V.,andOrlova,T.N.,
Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 1995,
vol. 38, no. 6, p. 32.
https://doi.org/10.1039/p19940000903
4. Broxton, T.J., Muir, D.M., and Parker, A.J., J. Org. Chem.,
2
1
975, vol. 40, no. 22, p. 3230.
https://doi.org/10.1021/jo00910a015
5. Holleman, A.F. and Wiberg, E., Inorganic Chemistry, San
Diego: Academic, 2001.
6. Jarczewski, A., Schroeder, G., and Dworniczak, M., J. Chem.
Soc., Perkin Trans. 2. 1986, p. 55.
2
2
9
. Sibrikov, S.G., Sapozhnikova, N.G., Savinskii, N.G.,
Mironov, G.S., and Kazin, V.N., Khim. Tekhnol., 2003,
no. 6, p. 13.
https://doi.org/10.1039/p29860000055
1
0. Kazin, V.N., Savinskii, N.G., Sibrikov, S.G., Sapozh-
nikova, N.G., and Yablonskii, O.P., Izv. Vyssh. Uchebn.
Zaved., Khim. Khim. Tekhnol., 2004, vol. 47, no. 6, p. 28.
27. Granovsky, A.A., Firefly version 8.2.
http://classic.chem.msu.su/gran/firefly/index.html.
28. Marenich, A.V., Cramer, C.J., and Truhlar, D.G., J. Phys.
Chem. B, 2009, vol. 113, no. 18, p. 6378.
https://doi.org/10.1021/jp810292n
11. Savinskii, N.G., Sapozhnikova, N.G., Sibrikov, S.G., and
Kazin, V.N., Izv. Vyssh. Uchebn. Zaved., Khim. Khim.
Tekhnol., 2003, vol. 46, no. 5, p. 26.
29. Andrienko, G.A., Chemcraft v.1.6.
1
2. Kazin, V.N., Sibrikov, S.G., Podaruev, S.O., Sapozh-
http://www.chemcraftprog.com.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020