Synthesis and spectrophotometric study of acidic and complexing properties of 5,15-bis(4'-methoxyphenyl)-10,20-bis(4″-nitrophenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethylporphyn in acetonitrile

Article abstract of DOI:10.1134/S1070363215030196

Abstract 5,15-Bis(4'-methoxyphenyl)-10,20-bis(4″-nitrophenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethylporphyne was synthesized and studied spectrophotometrically in the systems 1,8-diazabicyclo[5.4.0]undec-7-ene-acetonitrile, Zn(OAc)₂-acetoni

Full text of DOI:10.1134/S1070363215030196

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 3, pp. 640–647. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © Yu.B. Ivanova, N.Zh. Mamardashvili, А.V. Glazunov, А.S. Semeikin, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85,
No. 3, pp. 478–485.
Synthesis and Spectrophotometric Study of Acidic
and Complexing Properties of 5,15-Bis(4'-methoxyphenyl)-
10,20-bis(4''-nitrophenyl)-2,8,12,18-tetramethyl-
3,7,13,17-tetraethylporphyn in Acetonitrile
Yu. B. Ivanovaa, N. Zh. Mamardashvilia, А. V. Glazunovb, and А. S. Semeikinb
a Krestov Institute of Solution Chemistry of Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: jjiv@yandex.ru
b Ivanovo State University of Chemical Technology, pr. Sheremetevskii 7, Ivanovo, 153000 Russia
Received October 6, 2014
Abstract—5,15-Bis(4'-methoxyphenyl)-10,20-bis(4''-nitrophenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethyl-
porphyne was synthesized and studied spectrophotometrically in the systems 1,8-diazabicyclo[5.4.0]undec-7-
ene–acetonitrile, Zn(OAc)2–acetonitrile, 1,8-diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile. The orders
of acidity and kinetic activity were obtained for methoxyphenyl alkyl derivatives of porphyrins in these systems.
Keywords: porphyrins, acid-base properties, substituent electronic effects, structure
DOI: 10.1134/S1070363215030196
Scheme 1.
Structural diversity of complex tetrapyrrole com-
pounds originates from the necessity of synthesis of
compounds with predetermined properties [1, 2]. The
introduction of various substituents into the porphyrin
molecule substantially affects the physicochemical
properties of the macrocycle by changing the geometry
of the molecule, its acid-base properties and com-
plexing ability [3–7]. Variation of the number and type
of the substituents in porphyrin allows the regulation
of the required physicochemical properties of the
molecule, in particular, its electronic and steric effects.
R1
R2
R2
Et
Et
Et
Et
NH
N
N
MeO
OMe
Earlier, we have obtained the results of the spectro-
photometric investigation of acidic and complexing
properties of methoxyphenyl alkyl derivatives of
porphyn I, II containing substituents of different
nature [8, 9]. In continuation of these studies, in the
present work we present the results of synthesis and
spectrophotometric study of the acidic and complexing
properties of 5,15-bis(4'-methoxyphenyl)-10,20-bis(4''-
nitrophenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethyl-
porphyn (III) in the systems 1,8-diazabicyclo[5.4.0]-
undec-7-ene–acetonitrile, Zn(OAc)2–acetonitrile, 1,8-
diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile
at 298–318 K (Scheme 1).
HN
R2
R2
R1
I_III
R1 = H, R2 = Me (I); R1 = OMe, R2 = Et (II); R1 = NO2,
R2 = Me (III).
640

SYNTHESIS AND SPECTROPHOTOMETRIC STUDY
641
Scheme 2.
Δ
Me
COOEt
Me
COOEt
Et
Me
Et
HOOC
Me
COOEt
Et
Me
Et
SnCl2, H+
(1) SO2Cl2, Et2O
(2) H2O
I2, KHCO3
MeOH
I
MeOH
N
H
N
H
N
N
COOEt
H
H
Me
Me
COOEt
CHO
Et
Et
MeO
MeO
Me
COOEt
Et
NH
NH
NH
NH
H+
KOH
+
MeOH
(CH2OH)2
N
H
H
H
OMe
Et
Et
COOEt
Me
Me
NO2
Scheme 3.
Me
Me
CHO
Et
Et
(1) H+
N
N
(2) p-chroloanyl
+
MeO
Cu
V
OMe
(3) Cu(OAc)2
N
N
Et
Et
NO2
Me
Me
NO2
NO2
VI
Me
Me
Et
Et
Et
NH
N
H+
MeO
OMe
N
HN
Et
Me
Me
NO2
III
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642
IVANOVA et al.
(a)
А
(b)
А
cDBU × 10–6, mol/L
λ, nm
Fig. 1. Variations in electron absorption spectra (a) and spectrophotometric titration curve (λ = 485 nm) (b) of compound III in the
system 1,8-diazabicyclo[5.4.0]undec-7-ene–acetonitrile, (cporph = 1.01 × 10–5 mol/L; cDBU 0–5.01 × 10–5 mol/L), 298 K.
The spatially distorted porphyrin of the АВАВ type
I was synthesized in total yield of 7.4% (with respect
to dipyrrolylmethane IV) by condensation of 5,5'-un-
Similar reactions for the porphyrin ligands in
system (1) with DBU as a proton acceptor were per-
formed earlier [8–12].
substituted dipyrrolylmethane
V
with 4-nitro-
The two-step character of the curve of spectro-
photometric titration (Fig. 1) is indicative of elimina-
tion of two protons upon the reaction of the ligand with
the DBU molecule [Eq. (1)]:
benzaldehyde in the presence of HBr with subsequent
oxidation of the intermediate porphyrinogene with p-
chroloanyl in THF, its transformation into the copper
complex VII by the action of copper(II) acetate VI and
final demetalation (Schemes 2, 3).
k
H2P ⇄ P2– + 2H+,
(1)
where Н2Р and Р2– are the free base and the doubly
deprotonated forms of porphyrin III respectively.
The results of spectrophotometric investigation of
compound III in the system 1,8-diazabicyclo[5.4.0]-
undec-7-ene–acetonitrile are shown in Fig. 1. The
analysis of the spectra showed that with the increase of
the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) con-
centration the appearance of two sets of spectral curves
was observed in the electronic absorption spectrum,
each being characterized by its own set of isosbestic
points, which is indicative of a two-step process of
deprotonation. The parameters of the spectra of
molecular (without DBU) and the finally formed
doubly deprotonated forms (DBU concentration of 5 ×
10–5 mol/L) for compound III in system (1) are
presented in Table 1.
The combined constant of the two-step acid
ionization was calculated by Eq. (2). Its value for
compound III in the system DBU–CH3CN at 298 K
was log ka = –10.32 with the error of ±3–5%.
log ka = log Ind + nlog cDBU
,
(2)
where ka is the combined constant of acidity; Ind is the
indicator ratio Р2–/Н2Р; cDBU is the analytical value of
the DBU concentration in solution in mol/L, n = 2 is
the number of protons bound by DBU.
Taking into account reaction (1) and the equation of
material balance (3) we find that for the DBU
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SYNTHESIS AND SPECTROPHOTOMETRIC STUDY
643
II
I
III
Fig. 2. Optimized geometry of zinc complexes of compounds I–III (program POLYGRAF, Ver. 3.1).
concentration of ~2.6 × 10–5 mol/L practically all
molecules of III exist in the doubly deprotonated form.
The procedures of calculations are described in [13].
Table 1. Parameters of electron absorption spectra of the
molecular and the doubly deprotonated forms of 5,15-bis(4'-
methoxyphenyl)-10,20-bis(4''-nitrophenyl)-2,8,12,18-tetra-
methyl-3,7,13,17-tetraethylporphyn and its zinc complex in
the systems 1,8-diazabicyclo[5.4.0]undec-7-ene–acetonitrile
(λ1), Zn(OAc)2–acetonitrile (λ2), 1,8-diazabicyclo[5.4.0]undec-
7-ene–Zn(OAc)2–acetonitrile (λ3)
с0 = с(Н2Р) + с(Р2–).
(3)
The earlier obtained results of spectrophotometric
titration of compounds I (log ka = –10.41) and II (log ka =
–11.04) in the system 1,8-diazabicyclo[5.4.0]undec-7-
ene–acetonitrile [8, 9] allowed to obtain the following
order of acidity for the processes of deprotonation of
these ligands in the above system: III > I > II.
Forms of
compound III
λ1(log ε)
λ2(log ε)
λ3(log ε)
Н2Р
385 sh (4.84) 485 (5.54) 708 (4.82)
Р2–
–
–
470 (5.19) 616 (4.48)
474 (5.11) 620 (4.49)
The results of calculation of the geometry of
compounds I–III by РМ3 method (program Hyper-
Chem) (Fig. 2) showed that the nitrophenyl groups in
Zn2+P2–, ZnP
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644
IVANOVA et al.
(а)
(b)
А
А
λ, nm
λ, nm
Fig. 3. Variations of electron absorption spectra in the reaction of compound III with zinc acetate in MeCN, 298 K: (a) in the
absence of DBU, [cporph = 4.46 × 10–6 mol/L, c(ZnAc2) = 2.28 × 10–3 mol/L]; (b) in the presence of DBU [cporph = 1.02 × 10–5 mol/L,
c(ZnAc2) = 4.71 × 10–4 mol/L, cDBU = 3 × 10–5 mol/L].
Н2P + [МХ2(Solv)n–2] → МР + 2НХ + (n–2)Solv,
P2– + [МХ2(Solv)n–2] → МР + 2Х– + (n–2)Solv.
(4)
(5)
the phenyl fragments, as well as the methoxyphenyl
groups in the meso-position are turned with respect to
the macrocycle plane at the angle of 70°–85°. The
presence of twelve peripheral substituents leads to
distortion of the macrocycle. The dependence of the
degree of the macrocycle distortion on the acidic
properties of the porphyrin macrocycle was noted in
[9]. Compounds I and II contain, respectively, two and
four electron-donor methoxy groups, which is
manifested in more basic properties of these ligands.
Mutual effect of the nitro and methoxy groups in the
structure of porphyrin III leads to easier acidic
dissociation of this compound than of compounds I, II.
Here, Н2P is the molecule of porphyrin, X is the
acidoligand, Solv is the solvent molecule, n is
coordination number of the metal cation. Changes in
the electronic spectra during the reaction of
coordination of compound III with zinc acetate in
systems Zn(OAc)2–acetonitrile and 1,8-diazabicyclo-
[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile at 298 K
are shown in Fig. 3.
The calculation of kinetic parameters, of the
reaction order with respect to the salt and porphyrin
was performed by routine procedures [8, 11, 12]. The
experiment was repeated at least thrice at three
temperatures. The kinetic parameters for the reaction
of formation of zinc complexes of porphyrins I–III in
the systems Zn(OAc)2–acetonitrile and 1,8-diazabi-
The kinetics of the formation of zinc complexes of
compound III was studied spectrophotometrically in
the systems Zn(OAc)2–acetonitrile and 1,8-diaza-
bicyclo[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile. The
formation of complexes can be represented by Eqs. (4), (5):
Table 2. Kinetic parameters of the reaction of coordination of porphyrins with zinc acetate in the systems Zn(OAc)2–
acetonitrile and 1,8-diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile
[Zn(OAc)2], mol/L Kv × 10–2, L mol–1 s–1 ∆Е, kJ/mol
∆S≠, J mol–1 K–1
Porphyrin
III [Zn(OAc)2–CH3CN]
2.28 × 10–3
4.71 × 10–4
3.13 × 10–3
1.06 × 10–4
5.60 × 10–3
4.71 × 10–4
55
1200
59
13.6
6.4
17
–222
–185
–206
–167
–191
–157
III [Zn(OAc)2–CH3CN–DBU]
I [Zn(OAc)2–CH3CN] [9]
I [Zn(OAc)2–CH3CN–DBU] [9]
II [Zn(OAc)2–CH3CN] [8]
II [Zn(OAc)2–CH3CN–DBU] [8]
1560
53
10
22
1819
12
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SYNTHESIS AND SPECTROPHOTOMETRIC STUDY
645
cyclo[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile
presented in Table 2.
are
EXPERIMENTAL
Electron absorption spectra were registered on a
Shimadzu UV1800, Hitachi U2000 and Cary 100
Varian spectrophotometers. 1Н NMR spectra were
recorded on a Bruker 500 spectrometer (internal
reference TMS). Spectrophotometric titration with
DBU in acetonitrile was carried out on a Cary 100
Varian spectrophotometer. Kinetic experiments and
treatment of the experimental data were performed by
the known protocols [14, 15]. Acetonitrile of high
degree of purification (<0.03% of water) was used. As
deprotonating agent, DBU was used, whose pKa value
in acetonitrile is 13.2. Zinc acetate of “pure for
analysis” grade was purified by crystallization from
aqueous acetic acid and dried at 380–390 K [16].
The donor-acceptor effect of the substituents in
compounds I–III is manifested upon complexation in
the system 1,8-diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–
acetonitrile as shown by Eq. (5). The rate of formation
of the zinc complexes of porphyrins I–III in system
1,8-diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–aceto-
nitrile decreases in the order II > I > III. Therewith,
the rate of complexation of ligands I–III in the system
1,8-diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–
acetonitrile is 21–34 times higher than in the system
Zn(OAc)2–acetonitrile with molecular forms of
porphyrins. The energies of activation Е≠ of com-
plexation of ligands I–III in the system 1,8-diaza-
bicyclo[5.4.0]undec-7-ene–Zn(OAc)2–acetonitrile are
1.72–2.15 times lower than in the system Zn(OAc)2–
acetonitrile, which is usually ascribed to the absence of
energy expenses for deformation and rupture of the
N−H bonds at the reaction center. However, com-
plexation of ligands I–III in the system Zn(OAc)2–
acetonitrile occurs with approximately equal rates
(Table 2) and virtually does not depend on the
electronic and steric effects of the substituents.
Therefore, the change of the mechanism of
complexation results not only in the increase of the
rate of complexation but also favors manifestation of
the effect of peripheral substituents on the reactivity of
the ligand molecule. More negative values of ∆S≠ in
the system Zn(OAc)2–acetonitrile as compared to the
system 1,8-diazabicyclo[5.4.0]undec-7-ene–Zn(OAc)2–
acetonitrile are consistent with lower rates of forma-
tion of zinc complexes of the studied ligands in the
former system.
5,15-Bis(4'-methoxyphenyl)-10,20-bis(4''-nitro-
phenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethyl-
porphyrin. To the solution of 50.0 g (0.256 mol) of 2-
carbethoxy-4-ethyl-3,5-dimethylpyrrole [17] in 500 mL
of dry ether at cooling (<20°C) 68.5 mL (0.84 mol) of
sulfuryl chloride was gradually added. The mixture
was kept overnight at room temperature, ether was
removed, 400 mL of acetone and 100 mL of water was
added, and the mixture was refluxed for 20 min. To the
obtained solution the solution of 150 g (1.102 mol) of
sodium acetate trihydrate in 200 mL of water was
added, the mixture was refluxed for 2 h, acetone was
removed, the reaction mixture was cooled, filtered, the
precipitate was washed with water, then mixed with
the mixture of 100 mL of ether and 200 mL of water,
and the solution of 70.0 g of Na2CO3 in 200 mL of
water was gradually added. The ethere layer was
separated, water layer was extracted with 50 mL of
ether and acidified with diluted HCl (1 : 5 v/v) to рН =
6. The precipitated product was filtered off, washed
with water, and dried in air at 70°С. Yield 41.2 g
The results of spectrophotometric and kinetic
studies allowed ranking the order of acidity and kinetic
activity for methoxyphenyl alkyl derivatives of
porphyrins in the systems with different pH values of
the reaction medium. The increase in the pH value was
found to enhance the manifestation of the donor-
acceptor effects of the peripheral substituents and to
increase the rate of formation of the zinc complexes
for the series of methoxyphenyl alkyl derivatives of
porphyrin. The obtained results allow determining and
regulating the rates of the processes of complexation of
tetrapyrrole macrocycles by varying pH of the
medium, which should be useful for the synthesis of
complex tetrapyrrole structures and also for
investigation of catalysis of slow chemical reactions.
1
(71.5%). mp 210–211°С. H NMR (CDCl3), δ, ppm:
9.40 br.s (1H, NH), 4.31 q (2H, J 7.2 Hz, CH2O, Et),
2.74 q (2H, 1J 7.6 Hz, CH2, Et), 2.23 s (3H, CH3), 1.32
t (3H, J 7.2 Hz, CH3, OEt), 1.07 t (3H, 1J 7.6 Hz, CH3,
Et).
2-Iodo-5-carbethoxy-3-ethyl-4-methylpyrrole.
To the solution of 9.0 g (0.04 mol) of 2-carboxy-5-
carbethoxy-3-ethyl-4-methylpyrrole in 100 mL of
methanol, the solution of 12.0 g (0.12 mol) of KHCO3
in 100 mL of water was added, the mixture was heated
to 60°С, and the solution of 10.5 g (0.041 mol) of
iodine and 17.2 g (0.1 mol of KI in 100 mL of water
was gradually added. The mixture was stirred for
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 3 2015

646
IVANOVA et al.
30 min, cooled, the precipitate was filtered off, washed
with water, and dried in air at room temperature. Yield
10.6 g (86.3%). H NMR spectrum (CDCl3) δ, ppm:
9.91 br.s (1H, NH), 4.27 q (2H, J 7.2 Hz, CH2, OEt),
2.32 q (2H, 1J 7.6 Hz, CH2, Et), 2.25 s (3H, CH3), 1.29
t (3H, J 7.2 Hz, CH3, OEt), 0.99 t (3H, 1J 7.6 Hz, CH3, Et).
Compound V was dissolved in 20 mL of methanol,
0.36 g (2.36 mmol) of 4-nitrobenzaldehyde was added,
0.5 mL of HBr was added at stirring in inert
atmosphere, and the mixture was stirred at room
temperature for 2 h. The precipitate of porphyrinogene
was filtered off, dissolved in 20 mL of THF, was
added 0.87 g (3.54 mmol) of p-chloroanyl and 0.5 g
(2.5 mmol) of copper(II) acetate hydrate, 0.6 mL
(4.28 mmol) of triethylamine, the mixture was refluxed
for 0.5 h, and the solvent was removed to dryness. The
residue was dissolved in methylene chloride and
chromatographed on Al2O3 (Brockmann activity grade
III) eluting the first red zone of the copper complex
with methylene chloride. The eluate was evaporated,
the complex was sedimented with methanol, filtered
off, washed with methanol, and dried in air at 70°С.
Yield 0.31 g (26.8%); Rf (silufol) = 0.14 (benzene–
hexane, 1 : 1); UV spectrum (chloroform), λmax, nm
(log ε): 578 (4.20); 435 (5.00).
1
2-Carbethoxy-3-methyl-4-ethylpyrrole. а. 8.0 g
(35.5 mmol) of 5-carboxy-2-carbethoxy-3-methyl-4-
ethylpyrrole was heated on an oil bath at 230°С for 2 h
until evolution of СО2 ceased, then pyrrole was
distilled off in a vacuum of a water-jet pump. Yield
2.9 g (45.1%).
b. A mixture of 15.0 g (48.8 mmol) of 2-iodo-3-
ethyl-4-methyl-5-carbethoxypyrrole, 12.5 g (55.4 mmol)
of tin(II) dichloride dihydrate, 0.7 g (4.2 mmol) KI,
and 20 mL of conc. HCl in 150 mL of ethanol was
refluxed for 1 h, poured in water, extracted with ether,
the extract was washed with water, ether was removed,
the residue was distilled in a vacuum of a water-jet
5,15-Bis(4'-methoxyphenyl)-10,20-bis(4''-nitro-
phenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethyl-
porphyn (III). Solution of 0.1 g (0.1 mmol) of copper
complex VI, 1.0 mL (10.9 mmol) of POCl3 and 1 drop
of conc. HCl in 50 mL of CH2Cl2 was refluxed for
0.5 h, cooled, washed with 5% HCl, 5% ammonia and
water, the solution of porphyrin in CH2Cl2 was dried
with Na2SO4 and chromatographed on a short column
with Al2O3 (Brockmann activity grade III) eluting the
first green zone of porphyrin with CH2Cl2. The eluate
was evaporated, the porphyrin sedimented with
methanol, filtered off, washed with methanol, and
dried in air at 70°С. Yield 0.067 g (72.0 %); Rf
(silufol): 0.69 (benzene–methanol, 10 : 1). UV spec-
trum (chloroform), λmax, nm (log ε): 700 (4.01); 605
1
pump. Yield 4.3 g (48.6%). mp 24–25°С. H NMR
spectrum (CCl4), δ, ppm: 9.14 br.s (1H, NH), 6.53 d
(1H, J 3.6 Hz, 5-H), 4.17 q (2H, 1J 7.1 Hz, CH2, OEt),
2.27 q (2H, 2J 7.5 Hz, CH2, Et), 2.23 s (3H, CH3); 1.27
t (3H, 1J 7.1 Hz, CH3, OEt), 1.08 t (3H, 2J 7.5 Hz, CH3, Et).
ms-(4''-Methoxyphenyl)-5,5'-dicarbethoxy-4,4'-
dimethyl-3,3'-diethylpyrrole (IV). The mixture of
3.0 g (16.6 mmol) of 2-carbethoxy-3-methyl-4-ethyl-
pyrrole and 1.0 mL (8.3 mmol) of anisaldehyde was
dissolved in 50 mL of methanol, heated to reflux,
5.0 mL of conc. HCl was added, the reaction mixture
was refluxed for 4 h, cooled, and kept overnight in a
refrigerator. The precipitate was filtered off, washed
with methanol, and dried in air at room temperature.
1
1
Yield 3.6 g (90.2%). H NMR spectrum (CCl4), δ,
(4.00); 554 (4.06); 456 (5.28). H NMR (CDCl3), δ,
ppm: 8.63 d (4H, J 7.5 Hz, 2'',6''-H), 8.49 d (4H, 1J 8.1
Hz, 2',6'-H), 8.18 d (4H, J 7.5 Hz, 3'',5''-H), 7.28 d
ppm: 9.73 br.s (2H, NH), 6.67 d (2H, J 8.1 Hz, 2'',6''-
H), 6.43 d (2H, J 8.1 Hz, 3'',5''-H), 5.33 s (1H, ms-H),
1
1
3.88 q (4H, J 7.1 Hz, CH2, OEt), 3.57 s (3H, OCH3),
(4H, J 8.1 Hz, 3',5'-H), 2.47 br.s (8H, CH2, Et), 1.81
2.27 q (4H, 2J 7.5 Hz, CH2, Et), 2.10 s (6H, CH3), 1.07
t (6H, 1J 7.1 Hz, CH3, OEt), 0.88 t (6H, 2J 7.5 Hz, CH3, Et).
br.s (12H, CH3); 0.50 br.s (12H, CH3, Et).
ACKNOWLEDGMENTS
Copper complex of 5,15-bis(4'-methoxyphenyl)-
10,20-bis(4''-nitrophenyl)-2,8,12,18-tetramethyl-
3,7,13,17-tetraethylporphyn (VI). The mixture of
1.0 g (2.36 mmol) of ms-(4''-methoxyphenyl)-5,5'-
dicarbethoxy-4,4'-dimethyl-3,3'-diethyldipyrrolyl-
methane (IV) and a solution of 1.0 g (17.8 mmol) of
KOH in 6 mL of water was heated at 180°С for 4 h in
a sealed tube, the tube was cooled, opened, the
precipitate of ms-(4'-methoxyphenyl)-4,4'-dimethyl-
3,3'-diethyldipyrropylmethane (V) was filtered off.
This work was performed with the financial support
from Russian Scientific Foundation (agreement no. 14-
23-00204).
REFERENCES
1. Porfiriny: struktura, svoistva, sintez (Porphyrins: Struc-
ture, Properties, Synthesis), Enikolopyan, N.S., Ed.,
Moscow: Nauka, 1985.
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2. Porfiriny: spektroskopiya, elektrokhimiya, primenenie
(Porphyrins: Spectroscopy, Electrochemistry, Applica-
tion), Enikolopyan, N.S., Ed., Moscow: Nauka, 1987.
3. Uspekhi khimii porfirinov (Progress of Chemistry of
Porphyrins), Golubchikov, O.A., Ed., St. Petersburg:
NII Khimii SPbSU, 1997, vol. 1.
Crystallization As a Form of Self-Organization of
Matter”), Ivanovo, 2014, p. 197.
10. Ivanova, Yu.B., Nam Dao The, Glazunov, A.V.,
Semeykin, A.S., Pukhovskaya, S.G., and Mamar-
dashvili, N.Zh., Russ. J. Gen. Chem., 2014, vol. 84,
no. 1, p. 108. DOI:10.1134/S1070363214010162.
4. Jentzen, W., Simpson, M.C., Hobbs, J.D., Song, X.,
Ema, T., Nelson, N.Y., Medforth, C.J., Smith, K.M.,
and Veyrat, M., J. Am. Chem. Soc., 1995, vol. 117,
p. 11085. DOI: 10.1021/ja00150a008.
5. Gentemann, S., Medforth, C.J.,Forsyth, T.P., Nurco, D.J.,
Smith, K.M., Fajer, J., and Holten, D., J. Am. Chem.
Soc., 1994, vol. 116, p. 7363. DOI: 10.1021/ja00095a046.
6. Regev, A., Galili, T., Medforth, C.J., Smith, K.M.,
Barkigia, K.M., Fajer, J., and Levanon, H., J. Phys.
Chem., 1994, vol. 98, p. 2520. DOI: 10.1021/
j100061a005.
7. Pukhovskaya, S.G., Guseva, L.Zh., Semeikin, A.S., and
Golubchikov, O.A., Jinet. Catal., 2007, vol. 48, no. 2,
p. 190. DOI: 10.1134/S0023158407020024.
8. Ivanova, Yu.B., Mamardashvili, N.Zh., Glazunov, A.V.,
Semeikin, A.S., Russ. J. Gen. Chem., 2014, vol. 84,
no. 7, p. 1404. DOI: 10.1134/S1070363214070287.
9. Ivanova, Yu.B., Glazunov, A.V., Semeikin, A.S., and
Mamardashvili, N.Zh., Proc. VIII Mezhd. konf.
“Kinetika i mekhanizm kristallizatsii. Kristallizatsiya
kak forma samoorganizatsii veshchestva” (VIII Int.
Conf. “Kinetics and Mechanism of Crystallization.
11. Ivanova, Yu.B., Chizhova, N.V., Pukhovskaya, S.G.,
and Mamardashvili, N.Zh., Russ. J. Gen. Chem., 2014,
vol. 84, no. 5, p. 939. DOI: 10.1134/S1070363214050260.
12. Ivanova, Yu.B., Nam Dao The, Chizhova, N.V., and
Mamardashvili, N.Zh., Russ. J. Gen. Chem., 2014,
vol. 84, no. 6, p. 1030. DOI:10.1134/S1070363214060255.
13. Bernshtein, I.Ya., Spektrofotometricheskii analiz v
organicheskoi khimii (Spectrophotometry Analysus in
Organic Chemistry), Leningrad: Khimiya, 1986, p. 202.
14. Ivanova, Yu.B., Sheinin, V.B., and Mamardashvili, N.Zh.,
Russ. J. Gen. Chem., 2007, vol. 77, no. 8, p. 1458. DOI:
10.1134/S1070363207080270.
15. Ivanova, Yu.B., Churakina, Yu.I., and Mamardashvili, N.Zh.,
Russ. J. Gen. Chem., 2008, vol. 78, no. 4, p. 673. DOI:
10.1134/S1070363208040269.
16. Karyakin, Yu.V., Angelov, I.I., Chistye khimicheskie
reaktivy (Pure Chemicals Reactives), Мoscow:
Khimiya, 1974, p. 407.
17. Berezin, M.B., Semeikin, A.S., V’yugin, A.I., and
Krestov, G.A., Russ. Chem. Bull., 1993, vol. 42, no. 3,
p. 449.
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