An unusual reduction route of 2,4,6-trinitrobenzoic acid under conditions of aqueous-phase hydrogenation over Pd/Sibunit catalyst

Article abstract of DOI:10.1007/s11172-016-1479-8

For the first time it was established that the catalytic hydrogenation of 2,4,6-trinitrobenzoic acid to 1,3,5-triaminobenzene can proceed via the formation of aromatic hydroxyamines and cyclohexane-1,3,5-trione trioxime. As a result of aqueous-phase hydrogenation of sodium salt of 2,4,6-trinitrobenzoic acid in the presence of 5%Pd/Sibunit catalyst at a temperature of 323 K and pressure of 0.5 MPa, a trioxime in high yield (about 70 %) was obtained. Due to high selectivity to cyclohexane-1,3,5-trione trioxime the catalytic hydrogenation of sodium salt of 2,4,6-trinitrobenzoic acid can be considered as a new method for its synthesis.

Full text of DOI:10.1007/s11172-016-1479-8

Russian Chemical Bulletin, International Edition, Vol. 65, No. 6, pp. 1535—1540, June, 2016
1535
An unusual reduction route of 2,4,6ꢀtrinitrobenzoic acid under conditions
of aqueousꢀphase hydrogenation over Pd/Sibunit catalyst*
R. M. Mironenko,a,b O. B. Belskaya,a,c V. P. Talzi, V. A. Rodionov, S. V. Sysolyatin, and V. A. Likholobov
a
a
d
a,c,e
aInstitute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences,
5
4 ul. Neftezavodskaya, 644040 Omsk, Russian Federation.
Fax: +7 (381 2) 64 6156. Еꢀmail: chꢀmrm@mail.ru
b
Dostoevsky Omsk State University,
5
5a prosp. Mira, 644077 Omsk, Russian Federation.
Fax: +7 (381 2) 22 3641
c
Omsk State Technical University,
1
1 prosp. Mira, 644050 Omsk, Russian Federation.
Fax: +7 (381 2) 65 2698
d
Institute for Problems of Chemical and Energetic Technologies,Siberian Branch of the Russian Academy of Sciences,
1
ul. Sotsialisticheskaya, 659322 Biysk, Altai Krai, Russian Federation.
Fax: +7 (385 4) 30 3043
e
Omsk Scientific Center, Siberian Branch of the Russian Academy of Sciences,
1
5 prosp. K. Marksa, 644024 Omsk, Russian Federation.
Fax: +7 (381 2) 37 1762
For the first time it was established that the catalytic hydrogenation of 2,4,6ꢀtrinitrobenzoic
acid to 1,3,5ꢀtriaminobenzene can proceed via the formation of aromatic hydroxyamines and
cyclohexaneꢀ1,3,5ꢀtrione trioxime. As a result of aqueousꢀphase hydrogenation of sodium salt
of 2,4,6ꢀtrinitrobenzoic acid in the presence of 5%Pd/Sibunit catalyst at a temperature of 323 K
and pressure of 0.5 MPa, a trioxime in high yield (about 70 %) was obtained. Due to high
selectivity to cyclohexaneꢀ1,3,5ꢀtrione trioxime the catalytic hydrogenation of sodium salt of
2
,4,6ꢀtrinitrobenzoic acid can be considered as a new method for its synthesis.
Key words: 2,4,6ꢀtrinitrobenzoic acid, catalytic hydrogenation, palladium catalyst, cycloꢀ
hexaneꢀ1,3,5ꢀtrione trioxime.
Catalytic hydrogenation of aromatic nitro comꢀ
pounds1,2** is one of the most effective synthetic approachꢀ
es to aromatic amines both in laboratory practice and in
ucts.9—12 Moreover, among the most available and promꢀ
ising for processing of trinitro compounds is a product of
TNT oxidation, i.e. 2,4,6ꢀtrinitrobenzoic acid (1a), reꢀ
duction of which can lead to such valuable chemical comꢀ
pounds as 1,3,5ꢀtriaminobenzene (2) and 1,3,5ꢀtrihydrꢀ
3
—8
the industry.
Aromatic amines as well as products of
partial hydrogenation of nitro compounds are valuable inꢀ
termediates for polymers, pharmaceutical drugs, dyes and
1
3—19
oxybenzene (phloroglucinol).
8
So far only few reports describing14—20 catalytic hydroꢀ
genation of the acid 1a were published. It was shown that
hydrogenation of the acid 1a, usually in an organic solvent
and using Pd/C or the Raney Ni catalysts involves decarbꢀ
oxylation and formation of the product 2. Meanwhile,
2,4,6ꢀtriaminobenzoic acid, which is formed upon chemiꢀ
cal or electrochemical reduction of the acid 1a, was not
pesticides. Features of the nitro group reduction in the
course of catalytic hydrogenation of monoꢀ and dinitroareꢀ
nes were thoroughly investigated,4—7 whereas hydrogenaꢀ
tion of aromatic nitro compounds received significantly
less attention. At the same time, catalytic hydrogenation
of trinitroarenes is of high practical value because it can be
utilized for the disposal of explosives. Catalytic hydrogeꢀ
nation of one of the most common explosive agents, nameꢀ
ly, 2,4,6ꢀtrinitrotoluene (ТNТ) can afford 2,4,6ꢀtriaminoꢀ
toluene which is a precursor for a wide range of prodꢀ
2
1—23
found among the hydrogenation products.
Decrease
in selectivity for the compound 2 and catalyst deactivation
resulting apparently from the side reactions of polyꢀ
condensation yielding resinous substances are generally
observed for hydrogenation under atmospheric presꢀ
*
*
Dedicated to the memory of Professor G. V. Plaksin.
* Discovered by M. M. Zaitsev in 1871.
1
9,20
sure.
The published works related to the reduction of
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1535—1540, June, 2016.
066ꢀ5285/16/6506ꢀ1535 © 2016 Springer Science+Business Media, Inc.
1

1
536
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 6, June, 2016
Mironenko et al.
the acid 1a are focused mainly on the search for ortimal
conditions of the selective formation of the compound 2,
whereas they give no information about the intermediate
reduction products. At the same time studying the feaꢀ
tures of hydrogenation of trinitroarenes is important not
only from the theoretical viewpoint, but also is of practical
value for developing the synthetic approaches to the prodꢀ
ucts of partial reduction.2
spectrum was suppressed by the zgpr preꢀsaturation («Bruker»).
С NMR spectra were recorded in a Jꢀmodulation mode
1
3
(
JMOD).35 Quantitative composition of the reaction mixture
1
was estimated from the Н NMR spectroscopy data based on the
integral intensities of the corresponding signals of the individual
components nonꢀoverlapping with the other ones.
Results and Discussion
4—26
The present study is a part of our investigations directed
to elucidation of the transformation routes of the acid 1a
and its sodium salt (1b) during hydrogenation in the presꢀ
ence of Pd/Sibunit catalysts. The synthesis and applicaꢀ
It is known that liquidꢀphase hydrogenation of comꢀ
pound 1a or 1b when performed under mild reaction conꢀ
ditions, generally in an organic solvent or water at a temꢀ
perature of 323—348 K and pressure of 0.5—1.0 MPa on
2
7
tion of such catalysts are widely reported in literature.
15—18
the 5%Pd/C catalysts, selectively yields the product 2.
The choice of the catalysts is motivated by their high effiꢀ
ciency in hydrogenation of various organic compounds
including aromatic nitro compounds. Previuosly,28 using
the NMR technique we found that aqueousꢀphase cataꢀ
lytic hydrogenation of the salt 1b to the compound 2 preꢀ
sents a complex chain of reactions occurring via formaꢀ
tion of intermediates with mixedꢀtype functionalities.
Moreover, as it turned out, the direction of transformaꢀ
tions and consequently the product distribution depend
on the conditions used to prepare Pd/Sibunit catalysts and
to conduct the catalytic hydrogenation.
In the course of hydrogenation only nitro groups are reꢀ
duced, while aromaticity of a benzene ring is not disꢀ
turbed. For three nitro groups to be completely reduced
(
i.e. to convert 1a,b into 2), 9 moles of Н per 1 mole of
2
1
a,b are required. However we have demonstrated that
upon hydrogenation of the salt 1b in an aqueous solution
using the 5%Pd/Sibunit catalyst at a temperature of 323 K
and pressure of 0.5 MPa, the amount of the consumed
hydrogen is 6 moles of Н per 1 mole of 1b, which is
2
noticeably less than the amount of hydrogen required for
the reaction stoichiometry. Initially, the rate of the hydroꢀ
gen consumption reaches a maximum and then gradually
decreases over time (Fig. 1), apparently due to the blockꢀ
age of the active sites of the catalyst by the reaction prodꢀ
ucts. Furthermore, on a hydrogen consumption curve obꢀ
tained a noticeable step is observed the presence of which
might be indicative of the change in the direction of transꢀ
formations proceeding at different rates.
Experimental
Preparation of a catalyst. Catalyst 5 wt.% Pd/Sibunit was
obtained by hydrolytic precipitation of palladium polyhydroxo
2
9—31
complexes on the surface of the Sibunit carbon material
synthesized in the Department of experimental technologies of
the Institute of Hydrocarbons Processing of the Siberian Branch
(
of RAS, Ssp = 422 m2
g
–1
). Precipitation was followed by the
3
2,33
r/mol (mole 1b)–1 min–1
reduction of palladium by sodium formate.
On precipitaꢀ
tion, NaHCO was used as a precipitant (pH 5.4). No additional
3
treatment of the catalyst with humidity ∼ 50 wt. % was performed.
Catalytic hydrogenation of the salt 1b. The parent acid 1a
0
0
.25
.20
(
98% purity) was obtained by oxidation of TNT according to the
3
4
previously reported procedure. A solution of the salt 1b was
prepared by adding powdered NaHCO (0.59 g) to the carefully
3
stirred aqueous slurry of the acid 1a (2.00 g) until complete
1
5
dissolution of bicarbonate and complete release of CO2. The
salt 1b was hydrogenated in an aqueous solution (2 wt.%, 100 mL)
using 5%Pd/Sibunit (100 mg) in a steel autoclave at a temperaꢀ
ture of 323 K and pressure of 0.5 MPa. The reaction mass was
stirred using a magnetic stirring bar (1400 min–1). The reaction
course was monitored by measuring the volume of hydrogen
consumed over a particular period of time. When the reaction
was completed (i.e. after termination of the hydrogen consumpꢀ
tion) the autoclave was cooled and a sample of the reaction
mixture was taked by a syringe.
0.15
0
0
.10
.05
Analysis of the reaction products. The products of hydrogeꢀ
1
13
nation were analysed by the Н and С NMR techniques. Spectra
were recorded on an «Avanceꢀ400» («Bruker») NMR spectroꢀ
1
2
3
4
N/mol (mole 1b)–1
1
13
meter at Larmor frequency of 400 ( Н) or 100 MHz ( С) in
a pulse mode. Residual proton signals (δH 3.30, quintet) or carbon
nuclei in the methyl group (δC 49.0, septet) of methanolꢀd were
used as internal standards. Signal of water in the 1Н NMR
Fig. 1. Hydrogen consumption curve for the aqueousꢀphase
hydrogenation of the salt 1b over 5%Pd/Sibunit catalyst at
a temperature of 323 K and pressure of 0.5 MPa; r is rate of H2
absorption, N is an amount of consumed H2.
4

Hydrogenation of 2,4,6ꢀtrinitrobenzoic acid
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 6, June, 2016
1537
3
.70
aromatic protons at δ 5.75 corresponds to the product 2,
3
.46
H
3
.22
other signals of lesser intensity in the range of δH 5.8—7.1
are related to aromatic protons in the products of partial
reduction of nitro groups in the salt 1b. Among these
products 1,3,5ꢀtris(hydroxyamino)benzene (3), 3,5ꢀbisꢀ
5
.75
3
.50
(
hydroxyamino)aniline (4) and 5ꢀhydroxyaminoꢀ1,3ꢀdiꢀ
aminobenzene (5) were identified (Table 1). Identificaꢀ
tion of the compounds 3—5, which was not supported by
the spectral information in literature, was confirmed by
CD OD
3
5
.94
5
.90
6
.15
1
13
6
.11
simulating their Н and С NMR spectra using the softꢀ
ware package ACD/Labs. The most intensive peaks in the
6
.32
1
Н NMR spectrum are located in the area characteristic
7
.5
7.0
6.5
6.0
3.5
3.0 δH
of chemical shifts of nonaromatic protons. According to
1
39—41
Fig. 2. Н NMR spectrum of the reaction mixture obtained by
aqueousꢀphase hydrogenation of the salt 1b over 5% Pd/Sibunit
at a temperature of 323 K and pressure of 0.5 MPa (after conꢀ
sumption of 6 mole Н (mole 1b) ). Suppression of signal from
solvent (water) was performed by the zgpr pulse sequence.
the published data
they were attributed to methylene
protons of cyclohexaneꢀ1,3,5ꢀtrione trioxime (6). Three
singlets of equal intensity at δH 3.22, 3.46, and 3.70 corꢀ
respond to the unsymmetrical isomer (1Z)ꢀ6, and a sinꢀ
glet at δH 3.50 corresponds to the symmetrical isomer
–
1
2
(
1E,3E,5E)ꢀ6.
Identification of the compounds 2, 5, and 6 was conꢀ
1
3
1
The reaction products were identified and their conꢀ
tent in the reaction mixture was estimated based on the
NMR spectroscopy data. The efficacy of application of
the NMR technique in analysing the products of hydroꢀ
genation of aromatic trinitrocompounds was reported earꢀ
firmed by the analysis of the С{ H} NMR spectrum of
the reaction mixture recorded in the Jꢀmodulation mode.35
This method enables one to discriminate the carbon
1
13
atoms according to the value of the H— C interaction.
Thus, signals at δ 96.8, and 149.1 are oppositely orientatꢀ
ed and originate from the presence of methine and quaterꢀ
nary carbon atoms in the product 2, respectively (Fig. 3).
Signals having chemical shifts of 94.9, 99.3, 149.0, and
152.7 can be attributed to diamine 5. To the carbon atoms
C
1
8,24,36,37
lier.
The choice of this method is explained mainly
by its high informativity. Moreover, other analytical techꢀ
niques are characterized by either low efficiency or appliꢀ
cation irrelevance. Thus, for example, GC/MS or HPLC
methods should be considered unsuitable for this analytical
task because of low stability of the compounds under invesꢀ
tigation as well as the absence of reference compounds and
published mass spectra for the majority of these compounds.
of trioxime 6 the following signals (δ ) were ascribed:
25.8, 31.0, 35.7 (CH ꢀgroups in (1Z)ꢀ6); 30.4 (CH groups
C
2
2
in (1E,3E,5E)ꢀ6); 154.1, 154.8 (quaternary carbon atoms
of the both isomers of compound 6).
Based on the NMR data on the composition of the
reaction mixture, one may suggest the scheme of transꢀ
formations describing the course of the aqueousꢀphase
1
In the Н NMR spectrum of the reaction mixture (Fig. 2)
signals were detected corresponding not only to aromatic
but also to nonaromatic protons. An intensive signal of
Table 1. Signal assignments in the 1Н NMR spectrum and results of the quantitative assessment of the content of the products of
hydrogenation of the salt 1b in catalyzate
1
Compound
Н NMR spectrum (δ , J/Hz)
Relative content according
to the Н NMR data (%)
Η
1
Experiment (water, methanolꢀd4)
Literature data
2
5.75 (s, 3 Н, H(2), H(4), H(6))
5.52 (s, 3 Н, H(2), H(4), H(6));
1
14
.50 (br.s, 6 H, NH2)a
3
4
6.32 (s, 3 Н, H(2), H(4), H(6))
6.15 (t, 1 Н, H(4), J = 2);
—
—
11
15
6
.11 (d, 2 Н, Н(2), Н(6), J = 2)
5.94 (d, 2 Н, H(4), H(6), J = 2);
.90 (t, 1 Н, H(2), J = 2)
3.70, 3.46, 3.22 (all s, 2 Н each, CH2) 10.81, 10.74, 10.71 (all s, 1 Н each, ОН);
5
—
11
60
9
5
(1Z)ꢀ6
b
3
.50, 3.24, 3.04 (all s, 2 Н each, CH )
2
c
(1E,3E,5E)ꢀ6
3.50 (s, 6 Н, CH2)
3.33 (s, 6 Н, CH2)
a
b
c
See Ref. 38, solvent is CDCl3.
See Ref. 39, solvent is DMSOꢀd6.
See Ref. 40, solvent is DMSO.

1
538
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 6, June, 2016
Mironenko et al.
plained by the selective formation of compound 3 during
hydrogenation of salt 1b and low rate of accumulation of 4
(along the paths 3 → 4 or 6 → 4). The reason can be sought
not only in the catalyst nature and the hydrogenation conꢀ
ditions chosen but also in the substrate nature (the substitꢀ
uent effect). Formation of trioxime 6 resulted from cataꢀ
lytic hydrogenation has not been reported so far. Thus,
when studying hydrogenation of TNT in the presence of
supported platinum or palladium catalysts in the medium
of aliphatic alcohols it was established that the reduction
scheme for 2,4,6ꢀtriaminotoluene presents a complex
chain of consecutive and parallel reactions. The products
of these transformations are only aromatic compounds
bearing nitroꢀ, nitrosoꢀ, hydroxyaminoꢀ and amino groups
3
5.7
31.0
1
54.1
49.1
52.7
25.8
30.4
1
1
54.8
1
HCO3–
149.0
9
9.3
9
4.9
9
6.8
1
60
140
120
100
40
20 δC
Fig. 3. 13С{ H} JMOD NMR spectrum of the reaction mixture
obtained by aqueousꢀphase hydrogenation of the salt 1b over
1
3
6,37,42,43
in different ratios.
Apart from well characterized
5
0
%Pd/Sibunit catalyst at a temperature of 323 K and pressure of
hydrogenation of TNT, there are almost no information
in literature regarding the transformation paths of other
trinitroarenes (including 1a,b) under catalytic hydrogenaꢀ
tion conditions. As cited above, the published articles conꢀ
cerning the reduction of 1a,b deal mainly with optimizing
the conditions of the selective formation of the comꢀ
–
1
.5 MPa (after consumption of 6 mole Н (mole 1b) ).
2
hydrogenation of salt 1b in the presence of Pd/Sibunit
catalyst (Scheme 1). It appears, decarboxylation and reducꢀ
tion of three nitro groups of salt 1b to hydroxyamino groups
is a necessary condition for trioxime 6 to be formed with
1
4—20
pound 2,
while features of the reactions and condiꢀ
tions of the intermediate product formation are not estabꢀ
lished as yet.
–
1
treatment of hydrogen consumed of 6 mole (mole 1b)
.
Such transformation of the salt 1b into compound 3 can in
fact proceed via several steps of sequential reduction of
nitro groups and will be the object of further investigaꢀ
tions. At the same time it is known that the compound 3 is
Trioxime 6 presents a practical interest as it can find
application, e.g. in the synthesis of 1,3,5ꢀtriaminocycloꢀ
4
4
41
hexane, 1,3,5ꢀtrinitrobenzene and 1,3,5ꢀtrinitrosoꢀ
4
5,46
benzene.
A single synthetic procedure to obtain triꢀ
3
9,40
unstable and tautomerizes into more stable trioxime 6.
oxime 6 is known based on oximation of phloroglucinol
4
7
During the further hydrogenation of trioxime 6 aromaticꢀ
ity is restored3 and the compounds 4, 5, and 2 are conseꢀ
quently formed.
with hydroxylamine in the presence of K CO . Based on
2 3
9
results of the present study, catalytic hydrogenation of the
salt 1b can be considered as an alternative approach to
trioxime 6.
1
From the analysis of the Н NMR spectrum (see also
Fig. 2) it follows that the major product of the reaction
under investigation is trioxime 6, the yield of which was
about 70% (isomer mixture with (1Z)ꢀ6 predominating,
see Table 1). Such a high yield of trioxime 6 can be exꢀ
Isolation of the trioxime 6 from the catalyzate fraught
with difficulties, as it crystallizes poorly from an aqueous
solution and has low solubility in organic solvents ,
which prevents the use of extraction. Moreover, aromatic
4
0
47
Scheme 1

Hydrogenation of 2,4,6ꢀtrinitrobenzoic acid
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 6, June, 2016
1539
amines presenting in the reaction mixture have propensity
to polycondensation when contacted with air. However it
12. А. L. Rusanov, L. G. Komarova, D. Yu. Likhachev, S. А.
Shevelev, V. А. Tartakovsky, Russ. Chem. Rev., 2003,
72, 899.aaa
4
0,47
is believed
that in the absence of aromatic byꢀprodꢀ
1
3. M. L. Kastens, J. F. Kaplan, Ind. Eng. Chem., 1950,
2, 402.aaa
ucts in the reaction mixture and on concentrating the soluꢀ
4
tion trioxime 6 can be isolated in quantitative yield.
1
1
1
4. GB Pat. 1106088; Chem. Abstr., 1968, 69, 35731.
5. US Pat. 3678114; Chem. Abstr., 1972, 77, 61517.
6. Y. Chen, D. Zhao, Ranliao Gongye, 2001, 38, 24.
1
13
Thus, using Н and С NMR spectroscopy technique
it was established for the first time that catalytic hydroꢀ
genation of compound 1 affording compound 2 can proꢀ
ceed via the intermediate formation of aromatic hydrꢀ
oxyamines 3—5 and trioxime 6. Violation of aromaticity
of the benzene ring and formation of trioxime 6 in the
course of reduction of trinitroarenes has not been reported
so far. Aqueousꢀphase hydrogenation of the salt 1b using
the 5%Pd/Sibunit catalyst at 323 K and a pressure of
17. Q.ꢀH. Yang, Y.ꢀS. Feng, L. Chen, Zhongguo Yiyao Gongye
Zazhi, 2005, 36, 735.
18. Z.ꢀL. Yao, R.ꢀB. Wang, H.ꢀL. Liu, Yingyong Huagong, 2009,
3
8, 1153.
1
2
9. V. А. Kuz´mina, Yu. Т. Lapina, S. V. Sysolyatin, Polzunovskiy
vestnik [Polzunovsky Vestnik], 2008, No. 3, 129 (in Russian).
0. G. S. Samuelsen, V. L. Garik, G. B. L. Smith, J. Am. Chem.
Soc., 1950, 72, 3872.
0
.5 MPa produces trioxime 6 in a high yield (∼ 70%). The
2
2
1. DE Pat. 102358; Chem. Zentralbl., 1899, 1, 1263.
2. J. Phillips, A. Lowy, Trans. Electrochem. Soc., 1937, 71, 493.
reason can be sought in the catalyst nature, hydrogenation
conditions chosen as well as in the substrate nature
23. R. W. Lewis, O. W. Brown, Trans. Electrochem. Soc., 1943,
84, 135.
(
a substituent effect). Selective formation of the trioxime 6
allows one to consider the catalytic hydrogenation of the
salt 1b as a novel synthetic approach to this compound.
Therefore, further studies will be focused on elucidating
the principles of trioxime 6 formation as well as on search
for conditions which would prevent accumulation of aroꢀ
matic amines in the reaction mixture. It can be expected
that this information can be of use to obtain trioxime 6
with improved selectivity and also to isolate it from the
reaction mixture.
24. K. E. Malterud, J. Prakt. Chem., 1979, 321, 175.
2
2
2
5. Pat. RF No. 2337092; Bull. Izobr. [Bulletin of Inventions],
008, № 30 (in Russian).
6. Pat. RF No. 2396245; Bull. Izobr. [Bulletin of Inventions],
010, № 22 (in Russian).
2
2
7. V. P. Ananikov, L. L. Khemchyan, Yu. V. Ivanova, V. I.
Bukhtiyarov, A. M. Sorokin, I. P. Prosvirin, S. Z. Vatsadze,
A. V. Medved´ko, V. N. Nuriev, A. D. Dilman, V. V. Levin,
I. V. Koptyug, K. V. Kovtunov, V. V. Zhivonitko, V. A.
Likholobov, A. V. Romanenko, P. A. Simonov, V. G. Nenaꢀ
jdenko, O. I. Shmatova, V. M. Muzalevskiy, M. S. Nechaev,
A. F. Asachenko, O. S. Morozov, P. B. Dzhevakov, S. N.
Osipov, D. V. Vorobyeva, M. A. Topchiy, M. A. Zotova,
S. A. Ponomarenko, O. V. Borshchev, Yu. N. Luponosov, A. A.
Rempel, A. A. Valeeva, A. Yu. Stakheev, O. V. Turova, I. S.
Mashkovsky, S. V. Sysolyatin, V. V. Malykhin, G. A. Bukhtiꢀ
yarova, A. O. Terent´ev, I. B. Krylov, Russ. Chem. Rev.,
In the present study the facilities of Omsk Regional
Center of Collective Usage of Siberian Branch of the Rusꢀ
sian Academy of Sciences were used.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 16ꢀ03ꢀ00601).
2
014, 83, 885.
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2
2
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