1-Bromo-3,3,3-trifluoro-1-nitropropene: Synthesis and reaction with phenyl azide

Article abstract of DOI:10.1134/S1070428016100018

An improved procedure was developed for the synthesis of 3,3,3-trifluoro-1-nitropropene, and a new representative of gem-bromonitroalkenes, 1-bromo-3,3,3-trifluoro-1-nitropropene, was synthesized therefrom. Its reaction with phenyl azide gave a mixture of two regioisomeric 1,2,3-triazoles, from which pure 5-nitro-1-phenyl-4-(trifluoromethyl)-1H-1,2,3-triazole was isolated.

Full text of DOI:10.1134/S1070428016100018

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 10, pp. 1379–1384. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © N.A. Anisimova, E.K. Slobodchikova, A.A. Kuzhaeva, E.V. Stukan’, I.Yu. Bagryanskaya, V.M. Berestovitskaya, 2016, published in
Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 10, pp. 1391–1396.
1
-Bromo-3,3,3-trifluoro-1-nitropropene:
Synthesis and Reaction with Phenyl Azide
a, b
a
c
a
N. A. Anisimova , E. K. Slobodchikova , A. A. Kuzhaeva , E. V. Stukan’ ,
d, e
a
I. Yu. Bagryanskaya , and V. M. Berestovitskaya
a
Herzen State Pedagogical University of Russia, nab. r. Moiki 48, St. Petersburg, 191186
e-mail: kohrgpu@yandex.ru
b
St. Petersburg State University of Industrial Technologies and Design,
ul. Bol’shaya Morskaya 18, St. Petersburg, 191186 Russia
c
St. Petersburg Mining University, 21 Liniya V.O. 2, St. Petersburg, 199106 Russia
d
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e
Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
Received May 23, 2016
Abstract—An improved procedure was developed for the synthesis of 3,3,3-trifluoro-1-nitropropene, and
a new representative of gem-bromonitroalkenes, 1-bromo-3,3,3-trifluoro-1-nitropropene, was synthesized
therefrom. Its reaction with phenyl azide gave a mixture of two regioisomeric 1,2,3-triazoles, from which pure
5
-nitro-1-phenyl-4-(trifluoromethyl)-1H-1,2,3-triazole was isolated.
DOI: 10.1134/S1070428016100018
Chemistry of functionalized unsaturated nitro com-
pounds is an extensively developing basic research line
in modern organic chemistry [1–3], and conjugated
nitroalkenes are promising synthons and building
blocks for the preparation of various organic com-
pounds, including cyclic structures obtainable via
cycloaddition reactions [4–7]. Introduction of a trihalo-
methyl group into the vicinal position with respect to
the nitro group considerably extends the synthetic
potential of the resulting structures and endows them
with a number of practically important properties. It is
sufficient to note that derivatives of carbo- and hetero-
cyclic systems containing CF , CCl , or CBr group
bioavailability and sensitivity to enzymatic hydrolysis)
and retain natural peptide properties [12]. The known
“fluorine effect” is important in medicinal chemistry
for the design of new peptide-based medicinals
(peptidomimetics).
In comparison to 3,3,3-trifluoro-1-nitropropene, the
synthetic potential of its analog containing a bromine
atom in the geminal position with respect to the nitro
group seems even more promising. Among 3,3,3-tri-
halo-1-bromo-1-nitropropenes, only 1-bromo-3,3,3-tri-
chloro-1-nitropropene and 1,3,3,3-tetrabromo-1-nitro-
propene have been reported so far. 1-Bromo-3,3,3-tri-
chloro-1-nitropropene as the E isomer was synthesized
by halogenation–dehydrohalogenation of the corres-
ponding nitroalkenes [13, 14]. 1,3,3,3-Tetrabromo-1-
nitropropene was recently obtained as a mixture of
Z and E isomers according to a similar procedure [15].
3
3
3
exhibit a broad spectrum of biological activity; in
particular, trifluoromethyl-substituted pyrrole and cy-
clohexene derivatives were found to possess antimicro-
bial and enzymatic activity [8–11].
It is also important that 3,3,3-trifluoro-1-nitro-
propene was used as a starting material to obtain a new
class of peptidomimetics containing a stereogenic
The present work was aimed at developing a proce-
dure for the synthesis of 1-bromo-3,3,3-trifluoro-1-
nitropropene. As precursor we used 3,3,3-trifluoro-1-
nitropropene (2). It was prepared by condensation of
nitromethane with trifluoroacetaldehyde hydrate
[16] which was synthesized by reduction of ethyl
CH(CF )NH group instead of the natural peptide
3
C(=O)NH moiety, which made it possible to eliminate
some pharmacological drawbacks of peptides (such as
1
379

1
380
ANISIMOVA et al.
trifluoroacetate with sodium tetrahydridoborate [17].
The reaction of trifluoroacetaldehyde hydrate with
nitromethane afforded 1,1,1-trifluoro-3-nitropropan-2-
ol (1) (Scheme 1) We succeeded in improving the
procedures described in [17, 18] by using ethanol as
solvent instead of THF [17] in the synthesis of tri-
fluoroacetaldehyde hydrate and changing the reactant
ratio in the reaction of the latter with nitromethane to
compound 4 in the pure state, since it instantaneously
decomposed at room temperature. Newly synthesized
compounds 3a/3b and 4 are volatile oils and are strong
lachrymators.
Scheme 2.
HB
HB
*
Br2
Br
NO
NO2
F3C
2
F3C
*
1
:1 (instead of 1:2 [18]). As a result, the yield of 1
Br
HA
HA
increased from 47 to 94%. Distillation of 1 over phos-
phoric anhydride afforded (E)-3,3,3-trifluoro-1-nitro-
propene (2) in 76% yield.
2
3
HB
2
-Methylpyridine, Et O
2
NO2
F3C
Scheme 1.
Br
MeNO2
OH
O
OH
4
K CO
2
3
NO2
H O
F3C
OH
2
F3C
H
F3C
The structure of 1–4 was studied by IR, UV, and
1
13
19
1
NMR ( H, C, F) spectroscopy, including hetero-
nuclear HMQC and HMBC NMR techniques. The data
were compared with those reported previously for
structurally related compounds with CCl and CBr
P O
2
5
NO2
F3C
2
3
3
groups [15, 19].
The H and C NMR spectra of 1–4 were con-
sistent with the assumed structures. Nitro alcohol 1
1
-Bromo-3,3,3-trifluoro-1-nitropropene (4) was
1
13
synthesized in two steps (Scheme 2). In the first step,
nitroalkene 2 was treated with molecular bromine at
reduced temperature (–20 to –10°C) for 48 h. Di-
bromide 3 thus formed was isolated as a mixture of
two diastereoisomers 3a and 3b at a ratio of 4:1. In the
second step, isomer mixture 3a/3b was subjected to
dehydrobromination by the action of 2-methylpyridine
in diethyl ether. Bromonitroalkene 4 was obtained as
a concentrated solution in diethyl ether (yield ~80%
1
displayed in the H NMR spectrum two doublets at
δ 4.58 and 4.67 ppm with a geminal coupling constant
2
JHH of 14.10 Hz due to diastereotopic methylene
3
protons on C . The 2-H proton resonated at δ 4.85 ppm
and showed couplings with the methylene protons
3
(
J = 9.50, 2.60 Hz). The signal from the OH proton
1
13
was located as δ 3.25 ppm (br.s). In the H– C HMQC
spectrum of 1 we observed cross-peaks between the
1
according to the H NMR data). We failed to isolate
3
methylene protons and C (δ 74.14 ppm) and between
C
2
2
-H and C (δ 67.75 ppm). The CF carbon signal was
C
3
H′
A
, H″
A
1
13
observed at δ 123.14 ppm. The H– C HMBC spec-
H
B
C
OH
δ
C
, ppm
0.0
3
trum of 1 (Fig. 1) showed correlations of 2-H with C
1
2
1
and C , and of each 3-H proton with C and C .
6
2
2
A A
H′ /C , H″/C
1
2
C
The H NMR spectrum of 2 corresponded to an AB
3
3
C
spin system. The coupling constant J = 13.43 Hz
indicated E configuration of the double C=C bond
3
AB
B
H /C
8
0.0
HB
1
2
H'A
NO
[20]. The H signal appeared downfield (δ 7.10 ppm)
B
F3C
2
relative to H (δ 7.44 ppm) (Fig. 2). The given assign-
3
A
HO
1
1
00.0
20.0
H"
ment of the H and H signals is confirmed by the
A
B
A
1
19
3
corresponding H– F coupling constants, J(H –F) =
.41, J(H –F) = 1.22 Hz. The C signal of 2 was
B
1
4
1
B
H /C
6
A
1
1
1
H′
A
/C , H″
A
/C
C
located in a weaker field (δ 145.48 ppm, J
=
=
C
CH
2
2
1
3
97.26 Hz) than that of C (δ 125.74 ppm, J
C CF
7.06 Hz), and the CF carbon nucleus resonated at
3
5
.0
4.5
4.0
3.5
3.0 δ, ppm
δC 121.12 ppm (JCF = 270.93 Hz).
1
13
Independent evidences in favor of the assigned con-
figuration of 3,3,3-trifluoro-1-nitropropene (2) were
Fig. 1. H– C HMBC spectrum of 1,1,1-trifluoro-3-nitro-
propan-2-ol (1).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

1
-BROMO-3,3,3-TRIFLUORO-1-NITROPROPENE:
1381
obtained by DFT B3PW91/6-311++G(df,p) quantum
chemical calculations of the relative energies of the Z
and E isomers. The E isomer of 2 with the nitro group
lying in the C=C bond plane was found to have the
lowest energy. The energy of the Z isomer was higher
by 26.1 kJ/mol [21]. In addition, the dipole moments
of Z-2 and E-2 were calculated and measured experi-
mentally.
13.43 Hz
1
3.43 Hz
.22 Hz
6
.41 Hz
1
H
A
H
B
Diastereoisomeric dibromide mixture 3a/3b gave
1
13
19
rise to double sets of signals in the H, C and
F
NMR spectra (Fig. 3), the ratio 3a/3b being 4:1 (3a is
the stereoisomer characterized by lower chemical
shifts). The IR spectrum of 3a/3b contained absorption
7
.5
7.4
7.3
7.2
7.1
7.0
δ, ppm
1
–
1
Fig. 2. H NMR spectrum of 3,3,3-trifluoro-1-nitropropene
2) in CDCl
bands at 1581 and 1350 cm due to stretching vibra-
tions of the non-conjugated nitro group. For compar-
ison, stretching vibration bands of the conjugated nitro
groups in 2 and 4 were observed at 1555, 1307 and
(
3
.
product was a mixture of regioisomeric 1,2,3-triazoles
a and 6b at a ratio of 5 : 1 (Scheme 3). Initially
formed dihydrotriazoles 5a and 5b were detected in the
6
–
1
1
567, 1304 cm , respectively.
1
13
1
Analysis of the H and C NMR spectra of com-
reaction mixture by H NMR (5a: δ 5.19 ppm; 5b:
4
-H
pounds 4 and 2 and their analogs containing CCl and
δ5-H 4.64 ppm); they lose HBr during chromatography
3
CBr groups [19, 21] allowed us to assign Z configura-
on silica gel.
3
tion to 4 (trans orientation of the trifluoromethyl and
1
The H NMR spectrum of 6a/6b contained only
signals of aromatic protons in the region δ 7.18–
1
nitro groups). In the H NMR spectrum of 4, the 2-H
proton resonated at δ 7.70 ppm with a coupling con-
7
.68 ppm as three multiplets for each isomer. Protons
3
stant J of 6.46 Hz.
HF
of the benzene ring in 6a resonated in a weaker field
due to effect of the neighboring nitro group (δ 7.50,
7.62, 7.68 ppm); the corresponding signals of 6b were
observed at δ 7.18, 7.25, and 7.36 ppm. Major isomer
6a was isolated in the pure state by chromatography,
and its structure was determined by X-ray analysis.
The ability of bromonitropropene 4 to act as reac-
tive dipolarophile was demonstrated by the formation
of 1,3-dipolar cycloaddition products in the reaction
with phenyl azide. The reaction of 4 with phenyl azide
at room temperature was complete in 14 days, and the
HB
1
2
Br
NO
F3C
2
9
.46 Hz
(a)
3
Br
HA
H
A
3
.97 Hz
(b)
B
H (a)
H
A
B
H (b)
6
.0
5.5
5.0
δ, ppm
1
Fig. 3. H NMR spectrum of diastereoisomer mixture 3a/3b.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

1
382
ANISIMOVA et al.
Scheme 3.
NO2
CF3
O N
2
CF3
Br
a
b
–HBr
–HBr
N
N
N
N
Ph
Ph
N
N
NO2
PhN3
5a
6a
F3C
Br
NO2
CF3
O N
2
CF3
4
Br
N
N
N
N
Ph
Ph
N
N
5
b
6b
2
According to the X-ray diffraction data, the triazole
cule [the distance between O and the centroid of the
benzene ring is 3.164(2) Å].
ring in molecule 6a is planar, and the nitro group lies
almost in the same plane [the corresponding dihedral
angle is 8.2(4)°]. The benzene ring is turned through
a dihedral angle of 74.69(7)° with respect to the
triazole ring plane (Fig. 4). The bond lengths and bond
angles in molecule 6a coincided within 3σ with the
In summary, we have developed a procedure for the
synthesis of previously unknown 1-bromo-3,3,3-tri-
fluoro-1-nitropropene and improved the procedure for
the preparation of its precursor, 3,3,3-trifluoro-1-nitro-
propene. Using the reaction of 1-bromo-3,3,3-trifluoro-
1
corresponding reference values [22]. The geometric
1
-nitropropene with phenyl azide as an example, we
parameters of the triazole ring in 6a are similar to
those of structural analogs found in the Cambridge
Crystallographic Database: 1-(4-methoxyphenyl)-4-
trifluoromethyl)-1H-1,2,3-triazole (CCDC refcode
KIBBUS) [23] and 4-(chloromethyl)-1-(4-me-
have demonstrated the possibility of studying chemical
transformations of this readily volatile and lachry-
matory substance in ether solution without isolation in
the pure state.
(
thoxyphenyl)-5-(4-nitrophenyl)-1H-1,2,3-triazole
EXPERIMENTAL
(
SUMWAZ) [24].
Packing of molecules 6a in crystal is characterized
The spectral studies were performed using the
equipment of the Joint Center at the Faculty of
Chemistry, Herzen State Pedagogical University of
2
by short intermolecular contacts NO ···H
2.63 Å) and C F···FC [C ···F 2.745(3) Å], as well
(O ···H
2
arom
3
3
3
2
6
2
1
13
1
1
13
as by O···π interaction between the O atom and
π-system of the benzene ring of the neighboring mole-
Russia. The H, C–{ H}, and H– C HMBC NMR
spectra were recorded on a Jeol ECX400A spectrom-
1
eter (399.78 MHz for H) using the residual proton and
carbon signals of the deuterated solvent as reference.
The IR spectra were measured on a Shimadzu IR
Prestige-21 spectrometer from solutions in chloroform.
N
N
N
O
N
CF3
The products were isolated by column chromatog-
raphy on Macherey-Nagel L silica gel (140/270 mesh)
at a substrate-to-sorbent weight ratio of about 1:10
using eluotropic solvent series [25]. Silufol UV 254
plates were used for TLC; eluent hexane–acetone
(2:1); spots were visualized by treatment with iodine
vapor or under UV light. The ratios 3a/3b and 5a/5b
O
5
′
C
3
2
N
6
′
N
1
C
F
4
′
1
4
C
N
C
1
C
1
′
C
5
2
C
F
4
N
2
′
1
3
′
C
were determined by H NMR.
C
2
1
O
O
3
F
Trifluorocaetaldehyde hydrate was synthesized
according to modified procedure [17].
Fig. 4. Structure of the molecule of 4-nitro-5-(trifluoro-
methyl)-1-phenyl-1H-1,2,3-triazole (6a) according to the
X-ray diffraction data.
The X-ray analysis of a single crystal of 6a was
performed at the X-Ray Analysis Laboratory, Joint
Chemical Service Center, Vorozhtsov Novosibirsk
Institute of Organic Chemistry, Siberian Branch,
1
Tables containing geometric parameters of molecule 6a are avail-
able from the authors by e-mail.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

1
-BROMO-3,3,3-TRIFLUORO-1-NITROPROPENE:
1383
Russian Academy of Sciences. The data were acquired
at room temperature on a Bruker Kappa APEX dif-
3a: 6.15 (H ), 4.95 (H ); 3b: 6.40 (H ), 5.25 ppm (H ).
A
B
A
B
1
1
3
1
C NMR spectrum, δ , ppm, 3a: 121.70 q (C ,
C
2
2
1
fractometer (MoK radiation, graphite monochromator,
JCF = 279.23 Hz), 44.28 q (C , J = 33.23, J
=
α
CF
CH
3
1
CCD detector, 2θmax = 52.0°) from a 0.30×0.30×0.04-
162.45 Hz), 73.23 d (C , J = 180.59 Hz); 3b:
CH
1
1
2 2
mm single crystal; C H F N O ; monoclinic crystal
126.00 q (C , J = 277.96 Hz), 47.20 q (C , J
=
9
5
3
4
2
CF
CF
3
1
19
system, space group Pc; unit cell parameters: a =
1.4132(6), b = 5.2817(2), c = 9.1242(5) Å; β =
32.59 Hz), 78.89 d (C , J = 177.30 Hz). F NMR
CH
1
spectrum, δ , ppm: –65.00 s (3a), –68.80 s (3b).
F
3
111.517(2)°; V = 511.69(4) Å ; Z = 2; d = 1.676 g×
calc
Elemental analysis of 3a/3b could not be obtained
because of its high volatility.
–
3
–1
cm ; μ = 0.158 mm . Intensities of 1878 independent
reflections were measured. A correction for absorption
was applied using SADABS (transmission 0.68–0.75)
1
-Bromo-3,3,3-trifluoro-1-nitropropene (4). A so-
lution of 13.34 g (0.143 mol, 14 mL) of 2-methyl-
pyridine in 20 mL of diethyl ether was added dropwise
with vigorous stirring at room temperature to a solu-
tion of 43.16 g (0.143 mol) of isomer mixture 3a/3b in
[
(
26]. The structure was solved by the direct method
SHELXS-97) [27] and was refined in anisotropic ap-
proximation (isotropic for hydrogen atoms) (SHELXL-
7) [27]. The positions of hydrogen atoms were
9
5
4
0 mL of diethyl ether. The mixture was stirred for
0 min, ~20 mL of water was added, and the mixture
calculated on the basis of geometry considerations and
were refined according to the riding model. Final
was stirred for 30 min more. The organic layer was
separated and dried over magnesium sulfate. The
solvent was partially (~8–10 mL) removed on a rotary
divergence factors: wR = 0.1049 for all 1878 inde-
2
pendent reflections, R = 0.0436 for 1836 reflections
with F > 4σ(F); goodness of fit S = 1.13; 163 vari-
ables. The CIF file containing complete data set for
structure 6a was deposited to the Cambridge Crystallo-
graphic Data Centre (CCDC entry no. 1472942).
evaporator to obtain 32.17 g of a solution containing
1
~
80% ( H NMR) of 4 as a yellow–green volatile oil
(
strong lachrymator) which decomposed at room
temperature (after complete removal of the solvent,
1
,1,1-Trifluoro-3-nitropropan-2-ol (1). A mixture
the residue instantaneously warmed up and became
of 46.15 g (0.239 mol) of a 60% aqueous solution of
trifluoroacetaldehyde hydrate, 14.58 g (0.239 mol,
–1
charred), R 0.51. IR spectrum, ν, cm : 1567, 1304
f
(
NO ); 1650 (C=C). UV spectrum (EtOH): λ 230 nm.
2
1
2.8 mL) of nitromethane, and 1.99 g (0.019 mol) of
1
3
H NMR spectrum (CDCl ): δ 7.70 ppm, q ( J
=
=
3
HF
sodium carbonate was vigorously stirred at 60°C until
it became orange. The mixture was kept for 5 h at that
temperature and treated with diethyl ether (2×50 mL).
The combined extracts were dried over magnesium
sulfate and evaporated on a rotary evaporator, and the
residue was distilled at 85–86°C (18 mm) to obtain
13
6
(
3
.46 Hz). C NMR spectrum (CDCl ), δ , ppm: 138.0
3
C
1
3
2
1
2
C , J = 7.22 Hz), 125.53 (C , J = 174.04, J
CF CH CF
3
1
19
8.98 Hz), 120.63 (C , J = 271.57). F NMR spec-
CF
trum (CDCl ): δ –61.0 ppm. All spectra were recorded
3
F
from solutions containing a small amount of diethyl
ether. Elemental analysis of 4 could not be obtained
because of its high volatility and instability.
3
5.72 g (94%) of 1 as an orange oil, R 0.70; published
f
data [18]: bp 84°C (17 mm), yield 47%. IR spectrum,
–
1
4-Nitro-5-(trifluoromethyl)-1-phenyl-1H-1,2,3-
triazole (6a) and 5-nitro-4-(trifluoromethyl)-1-
phenyl-1H-1,2,3-triazole (6b). Phenyl azide, 0.6 g
ν, cm : 3603 (OH), 1568, 1384 (NO ).
2
3
,3,3-Trifluoro-1-nitropropene (2). Compound 1,
3
0
5.72 g (0.225 mol) was distilled over P O (36.35 g,
.256 mol) under atmospheric pressure. Yield 24.11 g
2
5
(
5 mmol), was added to a diethyl ether solution con-
taining ~1.0 g (4.5 mmol) of compound 4, and the
mixture was kept for 14 days at 20°C. The precipitate,
(
76%), yellow–green liquid (strong lachrymator),
bp 85–88°C; published data [17]: bp 89–90°C, yield
0
5
.37 g (32%) of a mixture of 6a and 6b at a ratio of
–
1
6
1
8%. IR spectrum (CHCl ), ν, cm : 1680 (C=C),
555, 1307 (NO2).
1
3
:1, was filtered off. H NMR spectrum (CDCl ), δ,
3
ppm: 7.18 m, 7.29 m, 7.36 m, 7.50 m, 7.64 m, 7.68 m.
1
2
,3-Dibromo-1,1,1-trifluoro-3-nitropropane
According to the H NMR data, the filtrate contained
(
3a/3b). A mixture of 25.00 g (0.177 mol) of alkene 2
dihydrotriazoles 5a and 5b at a ratio of 3:2 [δ 5.19 m
(1H, 4-H), 4.64 m (1H, 5-H)] and triazoles 6a and 6b.
The filtrate was evaporated, and the residue was
subjected to silica gel chromatography. Elution with
hexane gave 0.51 g (44%) of a mixture of 6a and 6b at
a ratio of 6:1. After repeated chromatography on silica
and 28.32 g (0.177 mol) of bromine was kept for 48 h
at –20°C and poured into a Petri dish. Evaporation of
unreacted bromine gave 43.16 g (81%) of a mixture of
diastereoisomers 3a and 3b at a ratio of 4:1 ( H NMR)
as a highly volatile liquid. H NMR spectrum, δ, ppm:
1
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

1
384
ANISIMOVA et al.
gel with hexane as eluent, from the second eluate
Lysenko, K.A., Smirnov, A.N., Egorov, Ts.A., and
Rogozhin, E.A., Eurasian Patent no. 015364, 2011.
11. Menezes, F.G. and Zucco, H.G., Quim. Nova, 2010,
portion (~100 mL) we isolated 0.29 g (25%) of 6a with
–
1
mp 93–95°C. IR spectrum, ν, cm : 1547, 1386 (NO ).
2
1
vol. 33, p. 2233.
H NMR spectrum (CDCl ), δ, ppm: 7.50 m, 7.64 m,
3
7
.68 m (C H ). Found, %: C 41.82, 41.85; H 1.93,
12. Molteni, M., Volonterio, A., and Zanda, M., Org. Lett.,
6
5
2
003, vol. 5, p. 3887.
1
.97; N 21.67, 21.71. C H F N O . Calculated, %:
9 5 3 4 2
C 41.86; H 1.94; N 21.71.
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This study was performed under financial support
by the Ministry of Education of the Russian Federation
in the framework of the base part of state assignment.
The authors thank the staff of the Joint Chemical
Service Center (Siberian Branch, Russian Academy of
Sciences) for performing the X-ray analysis.
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