Synthesis and Spectral Properties of meso-Nitro-Substituted Octaethylporphyrins and Their Co(II) Complexes

Article abstract of DOI:10.1134/S1070363220100102

Abstract: The reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with sodium nitrite in trifluoroacetic acid produced 5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin, 5,15-dinitro-2,3,7,8,12,13,17,18-octaethylporphyrin, and 5,10,15-trinitro-2,3,7,8,12,13,17,18-octaethylporphyrin. Reactions of octaethylporphyrin, mono-, di-, tri-, and tetranitro-substituted porphyrins coordination to cobalt(II) acetate in a chloroform–methanol mixture were studied. The corresponding Co(II) porphyrinates were obtained and identified. It was shown that, upon dissolution of Co(II) octaethylporphyrinates in dimethylformamide in the presence of NaOH, the Co(II)→Co(III) oxidation occurs in the coordination site of the macrocycle.

Full text of DOI:10.1134/S1070363220100102

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 10, pp. 1878–1883. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 10, pp. 1551–1557.
Synthesis and Spectral Properties of meso-Nitro-Substituted
Octaethylporphyrins and Their Co(II) Complexes
a,
a
a
N. V. Chizhova *, A. I. Rusanov , and N. Zh. Mamardashvili
a
G.A. Krestov Institute of Chemistry of Solutions of the Russian Academy of Sciences, Ivanovo, 153040 Russia
e-mail: nvc@isc-ras.ru
*
Received April 28, 2020; revised April 28, 2020; accepted May 12, 2020
Abstract—The reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with sodium nitrite in trifluoroacetic acid
produced 5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin, 5,15-dinitro-2,3,7,8,12,13,17,18-octaethylporphyrin,
and 5,10,15-trinitro-2,3,7,8,12,13,17,18-octaethylporphyrin. Reactions of octaethylporphyrin, mono-, di-, tri-, and
tetranitro-substituted porphyrins coordination to cobalt(II) acetate in a chloroform–methanol mixture were studied.
The corresponding Co(II) porphyrinates were obtained and identified. It was shown that, upon dissolution of Co(II)
octaethylporphyrinates in dimethylformamide in the presence of NaOH, the Co(II)→Co(III) oxidation occurs in
the coordination site of the macrocycle.
Keywords: octaethylporphyrin, meso-nitro-substituted porphyrins, cobalt complexes, nitration reactions, com-
plexation
DOI: 10.1134/S1070363220100102
Porphyrins and their metal complexes are used as
components of solar cells, agents for photodynamic
therapy of cancer diseases, and sensors for detecting
ions and gaseous substrates of different nature [1].
Selective introducing electron-donor and electron-
acceptor substituents into a porphyrin molecule makes
it possible to create systems with an uneven distribution
of electron density within the tetrapyrrole macrocycle,
which is of interest for creating materials with nonlinear
optical properties or enhanced n-conductivity [2, 3]. The
introduction of nitro groups into porphyrin molecules
makes it possible to obtain compounds with new
properties which are useful from a practical point of view
(for example, good solubility in organic solvents and high
stability of metal complexes in aggressive media). Nitro-
substituted porphyrins may be of interest as objects for
further chemical transformations [4–5].
The nitration of Zn(II) octaethylporphyrinate using
N O in dichloromethane was described earlier [6].
2
4
When treating zinc complexes of nitro-substituted
porphyrins with glacial acetic acid, the corresponding
porphyrin ligands were obtained. para-Nitro-substituted
Scheme 1.
1
878

SYNTHESIS AND SPECTRAL PROPERTIES OF meso-NITRO-SUBSTITUTED OCTAETHYLPORPHYRINS 1879
Scheme 2.
DMF
tetraphenylporphyrins were synthesized under the action
5,10,15,20-Tetranitro-2,3,7,8,12,13,17,18-
of NaNO in trifluoroacetic acid [5].
octaethylporphyrin 5 was synthesized by the procedure
2
[
7]. When octaethylporphyrin reacts with a zinc nitrate
excess in acetic anhydride, Zn(II) 5,10,15,20-tetranitro-
,3,7,8,12,13,17,18-octaethylporphyrinate is first formed.
In this paper, the nitration reactions of
,3,7,8,12,13,17,18-octaethylporphyrin 1 at meso-
2
2
positions by the action of NaNO in trifluoroacetic acid
2
When treating a tetranitro-substituted zinc complex with
hydrochloric or trifluoroacetic acids, porphyrin 5 was
obtained.
(
Scheme 1) were studied.
It was shown that when porphyrin 1 is treated with
sodium nitrite in trifluoroacetic acid at room temperature,
-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin 2 and a
Porphyrins usually exhibit their biological and
catalytic properties when present in the composition of
complexes with metals. Of particular interest are cobalt
complexes of porphyrins [8–11]. Cobalt porphyrinates
5
mixture of 5,10- and 5,15-dinitrooctaethylporphyrins
are formed depending on the ratio of reagents and
reaction duration. So, for a molar ratio of 1 : NaNO =
1
2
2
are used in the catalysis of anodic oxidation of SO and
: 5, 5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin
is formed within 5 min. In the mass spectrum of the
2
various hydrocarbons [12]. Cobalt complexes based on
porphyrins are characterized by a low redox potential
mononitro-substituted porphyrin the peak with m/z
5
of the central ion E
(Co2+/Co3+
[12, 13]. The value of this
79.1 corresponding to the molecular ion of compound
)
potential is largely determined by the donor-acceptor
properties of tetrapyrrole ligands and can vary widely.
Cobalt complexes of porphyrins exhibit high biological
activity.
2
(calculated for С Н N O : 579.8) is present. When
3
6
45
5
2
the excess of NaNO is increased to 12-fold and the
reaction duration to 30 min, a mixture of 5,15- and
5
2
,10-dinitrosubstituted octaethylporphyrins is formed.
The mass spectrum of the products contains a peak
with m/z 624.1 corresponding to the molecular ion of
dinitro-substituted octaethylporphyrins (calculated for
С Н N O : 624.8). Isomer separation was performed on
Polygram SILplates. The ratio of 5,15- and 5,10-isomers
was ~ 5 : 1.
Spectral properties of Co(II)-octaethylporphyrin were
studied in [14]. The authors [15] synthesized chloride
and iodide complexes of cobalt Co(III)(Cl)Porph and
Co(III)IPorph. In order to study the effect of meso-nitro
substitution on the formation of cobalt complexes with
octaethylporphyrin derivatives, the coordination reactions
of porphyrins 1–5 with cobalt(II) acetate in a chloroform–
methanol mixture were studied in this paper.
36
44
6
4
By increasing the excess of the nitrating reagent to
5
5
4
0 times and the reaction duration to 3 days,
,10,15-trinitro-2,3,7,8,12,13,17,18-octaethylporphyrin
was obtained with a yield of 68%. Increasing the NaNO2
The study has shown that the reaction of porphyrin
1 complex formation with Со(ОАс) (mole ratio 1 : 10)
2
excess to 60 times and the reaction duration to 5 days
does not lead to exhaustive nitration of the porphyrin 1
meso-positions.
in a boiling chloroform-methanol mixture (1 : 1) for
30 min leads to a mixture of Co(II)- and Co(III)-porphyrins
(Scheme 2). In the course of the chromatographic
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 10 2020

1880
CHIZHOVA et al.
Table 1. Parameters of electronic absorption spectra of Co(II) and Со(III) octaethylporphyrinates
λ, nm (log ε)
Compound
Solvent
band I
551
band II
516
band I
391
1
1
2
3
4
5
1
2
3
-Co(II)а
-Co(II)
-Co(II)
-Co(II)
-Co(II)
-Co(II)
-Co(III)
-Co(III)
-Co(III)
СH Cl
2
2
2
2
2
2
2
СH Cl
550 (4.31)
554 (4.21)
559 (4.18)
569 (4.15)
579 (4.06)
566 (0.211)
–
516 (4.11)
520 (4.09)
526 (4.08)
540 (4.12)
543 (3.97)
537 (0.228)
552 (0.417)
555 (0.362)
391 (5.21)
393 (5.08)
396 (5.01)
404 (4.87)
416 (4.75)
421 (1.17)
423 (1.70)
426 (1.37)
2
СH Cl
2
СH Cl
2
СH Cl
2
СH Cl
2
b
b
b
DMF + NaОН
DMF + NaОН
DMF + NaОН
–
а
Data of [14].
Relative intensity.
b
experiment with Co-porphyrins on basic alumina, the
Со(III)→Co(II) reduction occurs with the formation
of Co(II) 2,3,7,8,12,13,17,18-octaethyl porphyrinate 6
substituents, are significantly affected by the geometric
factor (the size of the N H coordination cavity [16]).
4
2
It was shown in [17, 18] that Mn(III)-porphyrins are
reduced to Mn(II) porphyrinates in dimethylformamide
and in DMF solutions in the presence of a solid alkali.
For Co-porphyrins, under similar conditions, the reverse
process is observed—the Co(II)→Co(III) oxidation
[19, 20].
(Table 1).
A mixture of Co(II) and Co(III) porphyrinates
was obtained in the reaction of porphyrin 2 with
Co(OAc) (mole ratio 1 : 20) in a boiling mixture of
2
chloroform–methanol within 4 h. Chromatography of
the obtained compounds on aluminum oxide leads to
the formation of Co(II) 5-nitro-2,3,7,8,12,13,17,18-
octaethylporphyrinate 7. Under similar conditions,
the reaction of 5,15-dinitroporphyrin 3 with cobalt
acetate within 4 h produced Co(II) 5,15-dinitro-
It was shown that Co(II) octaethylporphyrinates
6
, 7 are oxidized to a mixture of Co(II) and Co(III)-
porphyrins in dimethylformamide. At the same time,
complexes 6–8 in DMF solutions in the presence of a
solid alkali form Co(III)-porphyrins (Table 1). So, when
a solution of Co(II) octaethylporphyrinate 6 is kept in
DMF for 24 h at room temperature, a mixture of Co(II)
and Co(III)-porphyrins is formed. In the electronic
absorption spectrum of Co-porphyrins in DMF, the
Soret band is split into two components with maxima
at 394 and 413 nm of approximately the same intensity,
whereas in the long-wave region there are bands at
524 and 554 nm. Under comparable conditions, the degree
of the mononitro-substituted complex 7 conversion to the
oxidized form was ~ 10%.
2,3,7,8,12,13,17,18-octaethylporphyrinate 8 (Scheme 2).
In conditions similar to those of the reaction
with 5,15-dinitrophenol 3, the reaction of porphyrin
trinitrotoluene 4 with Co(OAc) within 40 min
2
produced Co(II) 5,10,15-trinitro-2,3,7.8,12,13,17,18-
octaethylporphyrinate 9. The complex formation
of porphyrin 5 with Со(ОАс)2 (mole ratio
1
: 10) in a chloroform–methanol boiling mixture
occurs within 2 min and leads to the formation of
Co(II) 5,10,15,20-tetranitro-2,3,7,8,12,13,17,18 of
octaethylporphyrinate 10.
When a solution of complex 6 is shaken in DMF
in the presence of solid NaOH for ~45 min, Co(III)
octaethylporphyrinate is formed. The formation time of
oxidized forms of mono- and dinitro-substituted cobalt
octaethylporphyrinates in DMF solution in the presence
of solid NaOH is reduced to 35 and 20 min, respectively.
When Co(II) trinitro-substituted porphyrinate 9 is
dissolved in DMF in the presence of solid NaOH within
~5 min, a compound is formed with maxima in the
electronic absorption spectrum at 664, 627, and 474 nm.
When the resulting compounds are isolated from the
Thus, in the transition from octaethylporphyrin to
its mono- and dinitro-substituted derivatives the time of
formation of the corresponding cobalt porphyrinates in
the chloroform–methanol medium increases, and for tri-
and dinitro-substituted derivatives the time of complex
formation decreases. The reaction of tetrahydrobiopterin
coordination with Со(ОАс) is ~15 times faster than that
2
of the unsubstituted porphyrin. Probably, the coordination
properties of nitro-substituted octaethylporphyrins with
Со(ОАс) , in addition to the electronic influence of
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 10 2020

SYNTHESIS AND SPECTRAL PROPERTIES OF meso-NITRO-SUBSTITUTED OCTAETHYLPORPHYRINS 1881
reaction mixture, partial or complete destruction of the
complexes is observed.
TMS). Mass spectra were obtained using a MALDI TOF
Shimadzu BiotechAxima Confidence mass spectrometer
(
matrix-dihydroxybenzoic acid).
Synthesized porphyrins and their complexes with
Co(II) were identified by electronic absorption and H
1
5-Nitro-2,3,7,8,12,13,17,18-octaethylporphyrin
NMR spectroscopy, and also by mass spectrometry.
Successive increase in the number of nitro groups in the
meso-positions of Co(II) octaethylporphyrinates leads to a
shift of the bands in the electronic absorption spectrum to
the long-wave region. During the Co(II) porphyrinates →
Co(III) oxidation, a bathochromic shift of the bands is
also observed (Table 1).
(2). To 0.04 g (0.0748 mmol) of porphyrin 1 in 3 mL
of trifluoroacetic acid, 0.026 g (0.374 mmol) of NaNO2
was added and mixed at room temperature for 5 min.
Chloroform and water were added to the reaction
mixture. The organic layer was separated, washed with
water, a NaHCO solution, again with water, then dried
3
with Na SO , and evaporated to a minimal volume. The
2
4
residue was chromatographed on aluminum oxide with
a hexane–dichloromethane (1 : 1) mixture and then with
dichloromethane. Yield 0.034 g (0.0586 mmol, 78%).
Co(II) octaethylporphyrinate exhibits paramagnetic
7
properties (configuration 3d ) [9]. This leads to the fact
1
that in the H NMR spectrum of compound 6, the signals
EAS (СH Cl ), λ, nm (log ε): 624 (3.67), 571 (3.74),
of the meso- and β-protons are broadened and shifted in
a weak field by 19.65, 4.77, and 4.20 ppm, respectively,
compared with the parent porphyrin 1. The signals of
the meso-protons of mono-, di - and trisubstituted Co(II)
porphyrinates appear in a weak field of ~24–30 ppm.
2
2
1
5
37 (3.88), 502 (4.05), 396 (5.08). H NMR spectrum, δ,
ppm: 10.25 s (2H) and 10.10 s (1H, meso-H), 4.11–4.02 m
12H) and 3.75 s (4H, CH ), 1.93–1.85 m (18H) and
(
2
1
.69–1.60 m (6H, CH ), –3.85 s and –3.95 s (2H, NH).
3
+
Mass spectrum, m/z (I , %): 579.1 (98) [M] (calculated
rel
Thus, 5-mononitro-2,3,7,8,12,13,17,18-octa-
ethylporphyrin, 5,15-dinitro-2,3,7,8,12,13,17,18-octa-
ethylporphyrin, and 5,10,15-trinitro-2,3,7,8,12,13,17,18-
octaethylporphyrin were synthesized and identified.
Reactions of coordination of octaethylporphyrin and its
mono-, di-, tri-, and tetranitro-substituted derivatives to
Co(II) acetate in a chloroform–methanol mixture were
studied. The corresponding cobalt(II) porphyrinates were
obtained and identified. It was shown that when Co(II)
octaethylporphyrinates are dissolved in DMF in the
presence of solid NaOH, the Co(II)→Co(III) oxidation
is observed.
for С Н N O : 579.8).
3
6
45
5
2
5
,15-Dinitro-2,3,7,8,12,13,17,18-octaethyl-
porphyrin (3). To 0.04 g (0.0748 mmol) of porphyrin 1
in 3 mL of trifluoroacetic acid, 0.062 g (0.898 mmol) of
NaNO was added and mixed at room temperature for
2
3
0 min. Chloroform and water were added to the reaction
mixture. The organic layer was separated, washed with
water, a NaHCO solution, again with water, then dried
3
with Na SO and evaporated to a minimal volume.
2
4
The residue was chromatographed on aluminum oxide
with dichloromethane, and then with chloroform. The
yield of a mixture of 5,15- and 5,10-dinitro-substituted
isomers is 0.03 g (0.048 mmol, 65%). Isomer separation
was performed on Polygram SIL plates (eluent—
dichloromethane–hexane 1 : 3, then 1 : 1). Yield 0.023 g
(0.0368 mmol, 50%). EAS (CH Cl ), λ, nm (log ε): 629
(3.96), 578 (4.04), 538 (4.10), 507 (4.24), 381 (4.99). H
NMRspectrum, δ, ppm:10.34s(2H,meso-H), 4.71–4.64m
(8H) and 4.10–4.03 m (8H, CH2), 1.94–1.88 m (12H)
EXPERIMENTAL
In the work commercial 2,3,7,8,12,13,17,18-
octaethylporphyrin 1 (Porphychem), chemically-pure
grade trifluoroacetic acid (Acros), aluminum oxide
2
2
1
(
Merck), DMF, CH Cl and СНCl , and pure grade
2
2
3
sodium nitrite were used. Glacial acetic acid was obtained
by freezing out pure-grade acetic acid. Chemically-
pure grade Co(OAc) was recrystallized from glacial
acetic acid, dried at 80°C for 1 h. 5,10,15,20-Tetranitro-
and 1.70–1.64 m (12H, CH ), –3.36 s (2H, NH). Mass
2
3
+
spectrum, m/z (I , %): 624.1 (96) [M] (calculated for
rel
2,3,7,8,12,13,17,18-octaethylporphyrin 5 was synthesized
С Н N O : 624.8).
3
6
44
6
4
according to the known procedure [7].
5
,10,15-Trinitro-2,3,7,8,12,13,17,18-octaethyl-
Control over the complex formation reactions of
porphyrin (4). To 0.04 g (0.0748 mmol) of porphyrin 1
in 3 mL of trifluoroacetic acid, 0.257 g (3.73 mmol) of
octaethylporphyrins with Со(ОАс) was carried out by the
2
spectrophotometric method. Electronic absorption spectra
were recorded on a Cary-100 (Varian) spectrophotometer
at room temperature. H NMR spectra were recorded on a
NaNO was added and mixed at room temperature for
3 days. When the reaction was completed, chloroform
and water were added. The organic layer was separated,
2
1
Bruker AV III-500 device in CDCl (internal standard—
washed with water, a NaHCO solution, again with water,
3
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 10 2020

1882
CHIZHOVA et al.
and dried with Na SO . The solvent was evaporated to
a minimal volume and chromatographed on aluminum
oxide with chloroform. Yield 0.031 g (0.0463 mmol,
Co(II) 5,10,15,20-tetranitro-2,3,7,8,12,13,17,18-
octaethylporphyrinate (10) was prepared similarly
from 0.025 g (0.035 mmol) of porphyrin 5 and 0.062 g
2
4
6
1%). EAS (CH Cl ), λ, nm (log ε): 637 (3.33), 589
(0.35 mmol) of Co(OAc) ; reaction duration—2 min.
Yield 0.025 g (0.0311 mmol, 89%). H NMR spectrum,
2
2
2
1
1
(
3.64), 540 (3.79), 513 (4.01), 385 (4.99). H NMR
spectrum, δ, ppm: 10.08 s (1H, meso-H), 3.96–3.92 m
4H), 3.59–3.57 m (4H), 3.56–3.53 m (8H, CH ),
δ, ppm: 5.68 br. s (16H, β-CH ), 2.36 br. s (24H, β-CH ).
2
3
+
(
Mass spectrum, m/z (I , %): 770.9 (76) [M] (calculated
2
rel
1
.81–1.77 m (6H), 1.55–1.50 m (6H), 1.49–1.45 m
for C Н N О Со: 771.7).
3
6
40
8
8
(
6H), 1.43–1.40 m (6H, CH ), –3.86 s (2H, NH). Mass
3
FUNDING
+
spectrum, m/z (I , %): 671.6 (97) [M + 2H] (calculated
rel
The work was supported by the Russian science Foundation
project no. 19-73-20079) using the equipment of the collective
use center of the Zelinsky Institute of organic chemistry of the
Russian Academy of Sciences.
for С Н N O : 669.9).
36
43
7
6
(
Co(II) 2,3,7,8,12,13,17,18-octaethylporphyrinate
(6). A mixture of 0.025 g (0.0467 mmol) of porphyrin 1
and 0.083 g (0.467 mmol) of Со(ОАс) was dissolved
2
in 30 mL of an 1 : 1 chloroform–methanol mixture. The
reaction mixture was boiled for 30 min, then cooled,
washed with water, dried with Na SO , and evaporated.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
2
4
The residue was chromatographed on aluminum oxide
REFERENCES
with dichloromethane. Yield 0.024 g (0.0408 mmol,
1
1. Lu-Lin, Li. and Wei-Guang Diau, E., Chem. Soc.
Rev., 2013, vol. 42, no. 1, p. 291.
8
7%). H NMR spectrum, δ, ppm: 29.60 br. s (4H,
meso-H), 8.82 br. s (16H, β-CH ), 6.15 br. s (24H, β-CH ).
2
3
https://doi.org/10.1039/C2CS35257E
+
Mass spectrum, m/z (I , %): 591.3 (98) [M] (calculated
rel
2
. Zdanovich, S.A., Mamardashvili, N.Z., and Golub-
chikov, O.A., Russ. J. Org. Chem., 1996, vol. 32, no. 5,
p. 756.
for С Н N Co: 591.7).
36
44
4
Co(II) 5-nitro-2,3,7,8,12,13,17,18-octaethyl-
porphyrinate (7) was prepared similarly from 0.025 g
3. Stuzhin, P.A., Goryachev, M.Yu., Ivanova, S.S.,
Nazarova, A., Pimkov, I., and Koifman, O.I., J. Porph.
Phthal., 2013, vol. 17, p. 905.
(0.0431 mmol) of porphyrin 2 and 0.15 g (0.862 mmol)
of Co(OAc) ; reaction duration 4 h. Yield 0.022 g
2
1
https://doi.org/10.1142/S1088424613500892
(
0.0346 mmol, 80%). H NMR spectrum, δ, ppm:
4
. Lyubimtsev, A., Semeikin, A., Zhglova, N., Sheinin, V.,
Rulikova, O., and Syrbu, S., Makrogeterotsikly, 2018,
vol. 11, no. 1, p. 103.
3
9
6
6
0.8 br. s (2H, meso-H), 24.3 br. C (1H, meso-H),
.50 br. s, and 8.42 br. s (16H, β-CH ); 8.10 br. s, 6.25 br. s,
2
.16 br. s (24H, β-CH ). Mass spectrum, m/z (I , %):
3
rel
https://doi.org/10.6060/mhc171151l
+
36.1 (88) [M] (calculated for С Н N О Co: 636.7).
3
6
43
5
2
5
. Luguya, R., Jaquinod, L., Fronczek, F.R., Graca, M.,
Vicente, H., and Smith, K.M., Tetrahedron, 2004,
vol. 60, p. 2757.
Co(II) 5,15-dinitro-2,3,7,8,12,13,17,18-octaethyl-
porphyrinate (8) was prepared similarly from 0.02 g
0.032 mmol) of porphyrin 3 and 0.114 g (0.64 mmol)
(
https://doi.org/10.1016/j.tet.2004.01.080
of Co(OAc) ; reaction duration 4 h. Yield 0.018 g
6. Gong, L.Ch. and Dolphin, D., Can. J. Chem., 1985,
vol. 63, no. 2, p. 401.
2
1
(0.0264 mmol, 80%). H NMR spectrum, δ, ppm: 28. 75
https://doi.org/10.1139/v85-066
br. s (2H, meso-H), 8.80 br. s (16H, β-CH ), 6.05 br. s
2
7
. Watanabe, E., Nichimura, S., Ogoshi, H., and Yoshida, Z.,
Tetrahedron, 1975, vol. 31, nos. 11–12, p. 1385.
https://doi.org/10.1016/0040-4020(75)87068-2
. Chizhova, N.V., Kumeev, R.S., and Mamar-
dashvili, N.Z., Russ. J. Inorg. Chem., 2013, vol. 58,
no. 6, p. 740.
(
24H, β-CH ). Mass spectrum, m/z (I , %): 681.2 (74)
3 rel
+
[M] (calculated for C Н N О Со: 681.7).
3
6
42
6
4
Co(II) 5,10,15-trinitro-2,3,7,8,12,13,17,18-octa-
ethylporphyrinate (9) was prepared similarly from
.025 g (0.0373 mmol) of porphyrin 4 and 0.132 g
8
0
(
0.746 mmol) of Co(OAc) ; reaction duration 40 min.
2
https://doi.org/10.1134/S0036023613060089
1
Yield 0.025 g (0.0316 mmol, 85%). H NMR spectrum,
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δ, ppm: 28.30 br. s (1H, meso-H), 5.90 br. s (4H, β-CH2),
5
.32 br. s (12H, β-CH ), 3.70–3.35 m (24H, β-CH ). Mass
2 3
+
spectrum, m/z (I , %): 726.3 (82) [M] (calculated for
rel
C Н N О Со: 726.7).
36
41
7
6
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 10 2020

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