Phosphoryl Analogs of Salicylic Acid: Synthesis and Analgesic and Anti-Inflammatory Activity

Article abstract of DOI:10.1134/S1070363218090049

The synthetically convenient method of preparation of unexplored phosphoryl analogs of salicylic acid (2-hydroxyphenylphosphonic and 2-hydroxyphenylphosphinic acids) has been developed for the search of novel nonsteroidal anti-inflammatory drugs. It has been shown that 2-hydroxyphenylphosphinic acid is a lowtoxic compound (LD₅₀ 3500 mg/kg) exhibiting analgesic activity significantly higher than both 2-hydroxyphenylphosphonic acid and the reference compound (sodium metamizole).

Full text of DOI:10.1134/S1070363218090049

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 9, pp. 1786–1791. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © V.E. Baulin, I.P. Kalashnikova, Yu.B. Vikharev, E.A. Vikhareva, D.V. Baulin, A.Yu. Tsivadze, 2018, published in Zhurnal Obshchei
Khimii, 2018, Vol. 88, No. 9, pp. 1438–1444.
Dedicated to the 110th anniversary of M.I. Kabachnik’s birth
Phosphoryl Analogs of Salicylic Acid:
Synthesis and Analgesic and Anti-Inflammatory Activity
V. E. Baulina,b*, I. P. Kalashnikovaa, Yu. B. Vikhareva,
E. A. Vikharevaa, D. V. Baulinb, and A. Yu. Tsivadzeb
a Institute of Physiologically Active Compounds, Russian Academy of Sciences,
Severnii pr. 1, Chernogolovka, 142432 Russia
*e-mail: mager1988@gmail.com
b Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow, Russia
Received June 28, 2018
Abstract―The synthetically convenient method of preparation of unexplored phosphoryl analogs of salicylic
acid (2-hydroxyphenylphosphonic and 2-hydroxyphenylphosphinic acids) has been developed for the search of
novel nonsteroidal anti-inflammatory drugs. It has been shown that 2-hydroxyphenylphosphinic acid is a low-
toxic compound (LD50 3500 mg/kg) exhibiting analgesic activity significantly higher than both 2-hyd-
roxyphenylphosphonic acid and the reference compound (sodium metamizole).
Keywords: 2-hydroxyphenylphosphonic acid, 2-hydroxyphenylphosphinic acid, analgesic activity, anti-inflammatory
activity, acute toxicity
DOI: 10.1134/S1070363218090049
The search for novel drugs for efficient treatment of
socially important diseases showing minimal side
effects is among priority directions of the social-
economic development. It is known that derivatives of
salicylic acid exhibit a wide range of physiological
activity [1–11]. 2-Hydroxyphenylphosphonic and 2-hyd-
roxyphenylphosphinic acids and their derivatives are
phosphoryl analogs of salicylic acid in which carbonyl
group is substituted with phosphoryl groups. Con-
sidering significant differences in coordination
properties, polarizability, and spatial structure of phos-
phoryl (sp3-hybridization) and carbonyl (sp2-hybridiza-
tion) groups, physiological activity of the phosphoryl-
containing analogs can differ from that of salicylic acid.
OH
OH
C
OH
O
O
P
O
P
OH
OH
H
HO
HO
(2-Hydroxyphenyl)phosphinic
acid
(2-Hydroxyphenyl)phosphonic
acid
Salicylic acid
Synthesis of 2-hydroxyphenylphosphonic acid is a
difficult task. It has been carried out for the first time via
hydrogenolysis of 2-benzyloxyphenylphosphonic acid
with hydrogen at 40 atm using a palladium catalyst
(yield 16%) [12]. The preparation of this compound
via the reaction of 2-bromophenylphosphonic acid
with aqueous ammonia in the presence of copper(I)
bromide has been described [13]. However, the data on
the solubility and melting point (178–179°С) of the
prepared sample have been significantly different from
these given in [12] (mp 124–127°С). In [14], mono-
anilinium salt of 2-hydroxyphenylphosphonic acid has
been synthesized and characterized for the first time.
In [15], the preparation of 2-hydroxyphenylphosphonic
acid with mp 129.5–130°С has been reported, and the
structure has been confirmed by means of 1Н, 13С, and
1786

PHOSPHORYL ANALOGS OF SALICYLIC ACID
1787
Scheme 1.
OH
O
P
OCH3
O
OCH3
(EtO)2P(O)Cl
HCl, EtOH
20οC
O
O
−78οC
R
P
R
R
Li
OEt
OEt
EtO
EtO
1a, 1b
3a, 3b
2a, 2b
Me3SiCl, NaBr, MeCN
OH
OH
O
EtOH
O
R1
P
P
OH
HO
5a, 5b
R = H (а), Et (b).
OSiMe3
Me3SiO
4a, 4b
31Р NMR spectroscopy. Synthesis and properties of
2-hydroxyphenylphosphinic acid have not been
described earlier.
3a, 3b in concentrated HCl) failed: after 15 min,
evidences of decomposition and characteristic phenol
smell appeared in the reaction mixture. Subsequently
phenol was isolated from the ether extracts of the
reaction mixture. Target acid 5a was prepared through
the trimethylsilyl esters which were obtained using the
reaction of phosphonates 3a, 3b with trimethyl-
bromosilane (TMBS) in acetonitrile under reflux. The
bis(trimethylsilyl) ester of 2-hydroxyphenylphos-
phonic acid 4a was isolated and identified for the first
time (Scheme 1). The reaction of 3a with in situ
generated trimethylbromsilane occurred practically
without the formation of side products; that fact was
the main advantage of the applied method as compared
to the use of trimethyliodosilane [21]. The hydrolysis
of compound 4a with water at room temperature
resulted in compound 5a strongly contaminated with
side products; that fact impeded its isolation and
purification. The alcoholysis of compound 4a with
anhydrous ethanol led to better results. The acid 5b
was prepared similarly without isolation of the
intermediate di(trimethylsilyl) ester 4b (Scheme 1).
The reactions of organolithium and organomagne-
sium compounds with haloanhydrides of phosphorous
acids are widely used for the creation of Ar–P bonds
for the preparation of arylphosphonic and arylphos-
phinic acids [16]. In this study, the derivatives of
2-methoxymethoxyaryllithium 1a, b were used as the
organolithium component; they were synthesized via
direct lithiation of methoxymethyl ethers of the
corresponding phenols with the solution of n-butyl-
lithium in THF–hexane (4–3 : 1) medium [17]. The
obtained solutions of compounds 1a and 1b were
immediately used for the preparation of target
compounds. It was shown that derivative 1a could be
isolated in the crystalline state via filtration or vacuum
removal of the solvent and stored for relatively long
time under dry argon at 8°С. The methoxymethyl ether
2a was prepared via the reaction of equivalent amounts
of compound 1a and diethyl chlorophosphate at
–60±5°С. 2-Diethoxyphosphorylphenol 3a was then
obtained from compound 2a via removal of methoxy-
methyl protection. Compound 3b was prepared using
the same method without the isolation of the
intermediate methoxymethyl derivative 2b (Scheme 1).
It should be noted that compound 3b described as
liquid in Refs. [14, 18–20] was isolated in crystalline
state (mp 41.5–43.5°С) in yield comparable to the
earlier reported.
Diethyl ester of 2-(methoxymethoxy)phenylphos-
phinic acid 6 was formed with good yield during slow
addition of a solution of compound 1a to diethyl
chlorophosphite under strict control of the reagents
ratio and temperature (–78±5°С). The reagents ratio
1 : 1 was found to be optimal. According to 31Р NMR
spectroscopy data, increase in the amount of reagent
1a led to stepwise substitution of two alkoxy groups
(Scheme 2). The acid ester of phosphinic acid 7 was
prepared via the hydrolysis of compound 6 in neutral
The synthesis of 2-hydroxyphenylphosphonic acid
via the conventional method (refluxing of phosphonates
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

1788
BAULIN et al.
Scheme 2.
O
P
OCH3
O
P
O
OCH3
OCH3
H2O, pH 7
23οC
(EtO)2PCl
−78οC
O
Li
OEt
H
EtO
EtO
1a
6
7
HCl, EtOH
23οC
OH
OH
HCl, H2O
23οC
O
O
P
P
H
H
EtO
HO
9
8
aqueous medium at room temperature. The phos-
phorylated phenol 8 was formed via the treatment of
compound 7 with the solution of HCl in ethanol.
Further hydrolysis to obtain the target acid 9 was
carried out using the mixture of concentrated HCl and
ethanol (1:1) (Scheme 2).
compound 9 was 3.8 and 2.3 times stronger than that
of acid 5b and reference compound (sodium metamizole),
respectively (see table). Hence, further investigation of
anti-inflammatory activity was performed only for com-
pound 9. In was shown that acid 9 provided slightly
stronger effect in agar-induced acute inflammation test
in comparison with sodium metamizole. According to
the results of acute toxicity test, compound 9 had LD50
equal to 3500 mg/kg; so, it was found a low-toxic
substance. The therapeutic index of compound 9 is
2.4 times higher than that of sodium metamizole at acetic
acid induced convulsions test and slightly higher at agar-
induced edema test.
Nonsteroidal anti-inflammatory drugs are widely used
to suppress inflammations in organisms. One of the first
well-known drugs of that group is salicylic acid
applied until now. Despite the existence of many of
nonsteroidal analgesic and anti-inflammatory drugs,
the search for novel compounds with lower toxicity
and minimal side effects remains a topical issue. The
data on analgesic and anti-inflammatory activity of the
derivatives of 2-hydroxyphenylphosphonic and 2-hyd-
roxyphenylphosphinic acids have not been given in the
earlier papers. In the present study, the analgesic and
anti-inflammatory activity as well as acute toxicity of com-
pounds 5b and 9 were investigated for the first time.
In summary, compound 9 characterized by low
toxicity and relatively strong analgesic and anti-
inflammatory activity is promising for the search of
novel nonsteroidal anti-inflammatory drugs.
EXPERMENTAL
The obtained results showed that the action of both
compounds led to the dose-depended reducing in
number of mice’s convulsions induced by abdominal
injection of acetic acid. The analgesic effect of
1
The H and 31Р NMR spectra were registered using
a Bruker СХР-200 spectrometer. Melting points were
measured using a Boetius PHMK 05 device.
Analgesic and anti-inflammatory activity and toxicity of compounds 5b, 9, and sodium metamizole
Analgesic activity
Anti-inflammatory activity
LD50,
mg/kg
Compound
ED50, mg/kg
Therapeutic indexa
ED50, mg/kg
Therapeutic indexa
5b
–
70
18
42
–
–
–
9
3500
194.4
80.7
140
165
25.0
20.5
Sodium metamizole
3390
a Therapeutic index = LD50/ED50.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

PHOSPHORYL ANALOGS OF SALICYLIC ACID
1789
Synthesis involving organolithium and phosphorus(III)
compounds were carried out under dry argon. Silicagel
L (100–160 µm) was used for column chromatography.
evaporated off under vacuum; the residue was distilled.
Yield 51.3 g (95.0%), mp 103–105°С (1 mmHg), mp
1
41.4–43.5°С (hexane). Н NMR spectrum (СDСl3), δ,
3
ppm: 1.33 t (6Н, СН3СН2, J = 7.5 Hz), 4.16 m (4Н,
2-Methoxymethoxyphenyllithium (1a). 55.0 mL
of 2.0 M n-butyllithium in hexane was added dropwise
at –30±5°С to a solution of 13.8 g (100 mmol) of
methoxymethyl ether of phenol [10] in 220 mL of THF
freshly distilled over LiAlH4 (the formation of white
precipitate started after 15 min). Then temperature was
increased to ambient, and the mixture was stirred for
2 h. For the isolation of compound 1a in solid state, the
reaction mixture was evaporated under vacuum using a
capillary with dry argon on a water bath at temperature
not exceeding 45°С. Yield 14.1 g (98%). Compound
1a did not decompose during 32 days under dry argon
at 8°С.
СН2СН3), 6.93 m (2Н, ArH), 8.00 m (2Н, ArH), 11.00
s (1Н, OH). 31Р NMR spectrum (СDСl3): δP 22.91
ppm. Found, %: С 52.15; H 6.43; P 13.15. C10H15O4P.
Calculated, %: С 52.18; H 6.57; P 13.46.
Diethyl ester of 2-hydroxy-4-ethylphenylphos-
phonic acid (3b). The solution of compound 1b
prepared from 16.0 mL of 2.0 M solution of n-
butyllithium in hexane and 4.98 g (30.0 mmol) of
methoxymethyl ether of 4-ethylphenol in 50 mL of
anhydrous THF was added dropwise to a solution of
5.6 g (32.0 mmol) of diethyl chlorophosphate in 15 mL
of THF at –60±5°С under stirring. Then temperature
was increased to ambient. The mixture was stirred for
1 h and evaporated under vacuum. 100 mL of saturated
solution of KH2PO4 was added to the residue; the
product was extracted with chloroform (3×35 mL).
The extract was washed with water (2×25 mL) and
dried over Na2SO4. The solvent was evaporated off
under vacuum. The residue was dissolved in 25 mL of
ethanol, then 10 mL of concentrated НСl was added.
The mixture was kept at room temperature for 12 h,
then diluted with 100 mL of water and extracted with
chloroform (3×35 mL). The extract was washed with
water (2×25 mL) and dried over Na2SO4. The solvent
was evaporated off under vacuum; the residue was
distilled. Yield 4.8 g (62.0%), mp 123–125°С
(1 mmHg). 1Н NMR spectrum (СDСl3), δ, ppm: 1.18 t
(6Н, СН3СН2, 3J = 7.5 Hz), 1.18 t (6Н, СН3СН2O, 3J =
7.5 Hz), 4.14 m (4Н, СН2СН3), 6.9 d. d (1Н, ArH, J =
8.2, J = 7.2 Hz), 7.18 d. d (1Н, ArH, J = 8.3, J =
1.9 Hz), 7.27 d. d (1Н, ArH, J = 14.6, J = 1.2 Hz),
10.00 s (1Н, OH). 31Р NMR spectrum (СDСl3): δP
24.07 ppm. Found, %: С 55.65; H 7.30; P 11.75.
C12H19O4P. Calculated, %: С 55.81; H 7.42; P 11.99.
2-Methoxymethoxy-4-ethylphenyllithium (1b) was
prepared similarly.
Diethyl ester of 2-(methoxymethoxy)phenylphos-
phonic acid (2a). A solution of compound 1a prepared
from 110.0 mL of a 3.1 M solution of n-butyllithium in
hexane and 47.5 g (344.0 mmol) of methoxymethyl
ether of phenol in 440 mL of anhydrous THF was
added dropwise to a solution of 12.4 g (80.0 mmol) of
diethyl chlorophosphate in 100 mL of THF at –60±5°С
under stirring. Then temperature was increased to
20±5°С. The mixture was stirred for 1 h and
evaporated under vacuum. 400 mL of saturated
solution of KH2PO4 was added to the residue, and the
product was extracted with chloroform (3×100 mL).
The extract was washed with water (2×100 mL) and
dried over Na2SO4. The solvent was evaporated off
under vacuum. The residue was distilled. Yield 58.3 g
(87.0%), mp 150–152°С (1 mmHg). 1Н NMR spectrum
3
(ССl4), δ, ppm: 1.31 t (6Н, OCH2CH3, J = 7.5 Hz),
4.12 m (4Н, OCH2CH3), 3.48 s (3Н, СН2ОСН3), 5.30 s
(2Н, ОСН2ОСН3), 7.00 m (1Н, ArH), 7.10 m (1Н,
ArH), 7.18 m (1Н, ArH),7.98 m (1Н, ArH). 31Р NMR
spectrum (ССl4): δP 16.69 ppm. Found, %: С 52.20; H
6.77; P 11.13. C12H19O5P. Calculated, %: С 52.55; H
6.98; P 11.29.
Bis(trimethylsilyl) ester of 2-hydroxyphenylphos-
phonic acid (4a). 25.0 g (250.0 mmol) of anhydrous
sodium bromide, 0.2 g (0.6 mmol) of tetrabutylammo-
nium bromide, and 27.2 g (250 mmol) of trimethyl-
chlorosilane were added to a solution of 14.3 g
(62.5 mmol) of compound 3a in 80 mL of anhydrous
acetonitrile. The reaction mixture was refluxed for 6 h;
the precipitate was filtered off; the filtrate was
evaporated; the residue was distilled under vacuum.
Yield 15.0 g (75.5%), mp 97–100°С (1 mmHg). The
substance crystallized during storage, mp 64–68°С. 1Н
NMR spectrum (СDСl3), δ, ppm: 0.05 s (18H, SiCH3),
Diethyl ester of 2-hydroxyphenylphosphonic acid
(3a). 50 mL of concentrated hydrochloric acid was
added to a solution of 66.5 g (244.3 mmol) of
compound 2a in 150 mL of ethanol. The mixture was
kept at room temperature for 12 h; then 200 mL was
added, and the product was extracted with chloroform
(3×100 mL). The extract was washed with water
(2×100 mL) and dried over Na2SO4. The solvent was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

1790
BAULIN et al.
6.64 m (2Н, ArH), 7.16 m (2Н, ArH), 10.30 s (1Н,
OH). 31Р NMR spectrum (СDСl3): δP 4.80 ppm.
Found, %: С 45.15; H7.13; P9.76. C12H23O4PSi2.
Calculated, %: С 45.26; H7.28; P9.73.
distilled. Yield 10.6 g (50.9%), mp 119–120°С
(1 mmHg). Н NMR spectrum (ССl4), δ, ppm: 1.14 t
1
(6H, ОСН2СН3, 3J = 7.5 Hz), 1.72 m (2Н, ОСН2СН3),
1.86 m (2Н, ОСН2СН3), 3.28 s (3Н, OCH2OCH3),
5.00 s (2Н, OCH2OCH3), 6.96 m (1Н, ArH), 7.10 m
(1Н, ArH), 7.20 m (1Н, ArH), 7.86 m (1Н, ArH). 31Р
NMR spectrum (ССl4): δP 148.4 ppm. Found, %: С
55.75; H 7.45; P 11.82. C12H19O4P. Calculated, %: С
55.81; H 7.42; P 11.99.
2-Hydroxyphenylphosphonic acid (5a). A solution
of 1.5 g (4.7 mmol) of ester 4a in 20 mL of anhydrous
ethanol was kept at room temperature for 8 h. Then
activated carbon was added, and the mixture was
refluxed for 0.5 h. Carbon was filtered off; the filtrate
was evaporated. 10 mL of dichloromethane was added
to the residue. The precipitate was filtered off and
dried. Yield 0.8 g (97.8%), mp 129–130°С (СН2Cl2).
1Н NMR spectrum (D2О), δ, ppm: 7.04 m (2Н, ArH),
7.62 m (2Н, ArH), 10.3 s (1Н, OH). 31Р NMR
spectrum (D2О): δP 13.77 ppm. Found, %: С 41.15,
41.10; H 4.00, 3.93; P 17.50, 17.62. C6H7O4P.
Calculated, %: C 41.39; H 4.05; P 17.79.
Ethyl ester of 2-(methoxymethoxy)phenylphos-
phinic acid (7). 25 mL of saturated aqueous solution of
ammonium chloride was added to a solution of 4.5 g
(17.4 mmol) of compound 6 in 15 mL of diethyl ether.
The mixture was stirred for 24 h at room temperature.
Then the organic layer was separated. The aqueous
layer was extracted with diethyl ether (3×10 mL).
Combined ether extracts were dried over Na2SO4.
Ether was removed under vacuum. The residue was
distilled. Yield 72.9 g (72.3%), bp 142–143°С
(1 mmHg), mp 25.6–29.5°С. 1Н NMR spectrum
2-Hydroxyphenyl-4-ethylphosphonic acid (5b).
11.9 g (116.0 mmol) of anhydrous sodium bromide,
0.2 g (0.6 mmol) of tetrabutylammonium bromide, and
12.6 g (116.0 mmol) of trimethylchlorosilane were added
to a solution of 10.3 g (38.7 mmol) of compound 3b in
80 mL of anhydrous acetonitrile. The reaction mixture
was refluxed for 6 h and then filtered. The filtrate was
evaporated. 25 mL of ethanol was added to the residue.
The mixture was kept for 18 h at room temperature and
then evaporated under vacuum. 30 mL of СН2Cl2 was
added to the residue. The formed precipitate was
filtered off after 10 h. Yield 6.25 g (80.0%), mp 115–
3
(ССl4), δ, ppm: 1.34 t (3H, OCH2CH3, J = 7.0 Hz),
3.78 m (2H, OCH2CH3), 3.38 s (3H, OCH2OCH3),
5.20 s (2H, OCH2OCH3), 7.10 m (2Н, ArH), 7.21 m
1
(1Н, ArH), 7.50 d (1Н, PH, J = 577.5 Hz). 31Р NMR
spectrum (ССl4): δP 18.63 ppm. Found, %: С 52.43; H
6.45; P 13.42. C10H15O4P. Calculated, %: С 52.18; H
6.57; P 13.46.
Ethyl ester of 2-hydroxyphenylphosphinic acid (8).
A solution of 2.6 g (11.3 mmol) of compound 7 in
25 mL of saturated solution of hydrogen chloride in
anhydrous ethanol was kept for 24 h at room
temperature. Then the solvent was distilled off. The
residue was recrystallized from benzene–hexane
1
117°С (СН2Cl2). Н NMR spectrum (D2О, рН 5), δ,
ppm: 1.18 m (3Н, СН2СН3), 3.41 m (3Н, СН2СН3),
7.05 m (2Н, ArH), 7.62 m (2Н, ArH). 31Р NMR
spectrum (D2О, рН 5): δP 12.29 ppm. Found, %: С
47.47; H 5.43; P 15.16. C8H11O4P. Calculated, %: С
47.53; H 5.48; P 15.31.
1
mixture. Yield 1.9 g (74.0%), mp 83–85°С. Н NMR
3
spectrum (ССl4), δ, ppm: 1.32 t (3H, OCH2CH3, J =
7.0 Hz), 3.74 m (2H, OCH2CH3), 7.12 m (2Н, ArH),
7.24 m (1Н, ArH), 7.54 d (1Н, PH, 1J = 579.5 Hz). 31Р
NMR spectrum (ССl4): δP 17.83 ppm. Found, %: С
51.43; H 5.85; P 16.42. C8H11O3P. Calculated, %: С
51.62; H 5.96; P 16.64.
Diethyl ester of 2-(methoxymethoxy)phenylphos-
phinic acid (6). A solution of ortho-methoxy-
phenyllithium obtained form 72.0 mL of 1.4 M
solution of n-butyllithium in hexane and 13.8 g
(100.0 mmol) of methoxymethyl ether of phenol in
220 mL of anhydrous THF was added dropwise to a
solution of 12.4 g (80.0 mmol) of diethyl chlorophos-
phite in 100 mL of THF at –60+5°С under stirring.
The mixture was stirred for 1 h at 20°С. Then the
solvent was removed under vacuum. 200 mL of
anhydrous pentane was added to the residue; the
mixture was kept overnight. The precipitate was
filtered off and washed with pentane (2×75 mL). The
filtrate was evaporated under vacuum; the residue was
2-Hydroxyphenylphosphinic acid (9). 20 mL of
concentrated hydrochloric acid was added to a solution
of 3.7 g (16.0 mmol) of ester 8 in 20 mL of ethanol.
The mixture was kept at 20°С for one day and then
evaporated under vacuum. 10 mL of anhydrous
acetonitrile was added to the residue; the precipitate
was filtered off and dried. Yield 1.8 g (71%), mp 143–
1
144°С. Н NMR spectrum (СDСl3), δ, ppm: 6.92 m
1
(2Н, ArH), 7.66 d (1Н, PH, J = 694.5 Hz), 7.73 m
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

PHOSPHORYL ANALOGS OF SALICYLIC ACID
(2Н, ArH), 10.68 s (1Н, OH). 31Р NMR spectrum
1791
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(СDСl3): δP 19.70 ppm. Found, %: С 45.45; Н 4.55; Р
19.49. C6H7O3P. Calculated, %: С 45.58; H 4.46; P 19.59.
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All applicable international, national, and/or
institutional guidelines for the care and use of animals
were followed.
ACKNOWLEDGMENTS
This work was financially supported by the
Ministry of Science and Education of the Russian
Federation in the framework of the assignment for
2018 (no. 0090-2017-0024) and the Programs of
Presidium of RAS nos. 34 and no. 38.
CONFLICT OF INTERESTS
No conflict of interests was declared by the authors.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018