Asymmetrically substituted tetra(meso-aryl)porphyrins bearing peripheral 2,6-diisobornylphenol and 2,6-di-tert-butylphenol moieties

Article abstract of DOI:10.1007/s11172-017-1992-4

Asymmetrically substituted tetra(meso-aryl)porphyrins bearing peripheral diisobornyl- phenol and di-tert-butylphenol moieties were synthesized by a mixed aldehyde condensation.

Full text of DOI:10.1007/s11172-017-1992-4

Russian Chemical Bulletin, International Edition, Vol. 66, No.11, pp. 2131—2135, November, 2017
2131
Asymmetrically substituted tetra(mesoꢀaryl)porphyrins bearing
peripheral 2,6ꢀdiisobornylphenol and 2,6ꢀdiꢀtertꢀbutylphenol moieties
D. V. Belykh, T. K. Rocheva, E. V. Buravlev, I. Yu. Chukicheva, and A. V. Kutchin
Institute of Chemistry, Komi Scientific Center, Ural Branch of the Russian Academy of Sciences,
4
8 ul. Pervomaiskaya, 167982 Syktyvkar, Russian Federation.
Fax: +7 (821) 221 8477. Eꢀmail: belykhꢀdv@mail.ru
Asymmetrically substituted tetra(mesoꢀaryl)porphyrins bearing peripheral diisobornylꢀ
phenol and diꢀtertꢀbutylphenol moieties were synthesized by a mixed aldehyde condensation.
Key words: mixed aldehyde condensation, tetra(mesoꢀaryl)porphyrins, 2,6ꢀdiisobornylꢀ
4
ꢀmethylphenol, 2,6ꢀdiꢀtertꢀbutylphenol, hybrid antioxidants.
It is known that antioxidant activity of synthetic pheꢀ
nolic compounds often exceeds those of natural antioxiꢀ
dants. It has been found that phenolic compounds reꢀ
trimethylbicyclo[2.2.1]heptꢀexoꢀ2ꢀyl)benzaldehyde (1) or
3,5ꢀdiꢀtertꢀbutylꢀ4ꢀhydroxybenzaldehyde (2) with benzꢀ
aldehyde (3) (4ꢀmethoxybenzaldehyde (8)) and pyrrole
to synthesize asymmetrically substituted tetra(mesoꢀ
aryl)porphyrins bearing one diisobornylphenol or diꢀtertꢀ
butylphenol group (Scheme 1 and 2).
1
duce the rate of lipid and protein peroxidation and are
promising candidates for treatment of free radicalꢀinduced
diseases.1
—3
They show antihypoxic, hemorheological,
4
—16
and other important biological activities.
Significant
antioxidant activity (AOA) of 2,6ꢀdiꢀtertꢀbutylꢀ4ꢀmethꢀ
ylphenol and 2,6ꢀdiisobornylꢀ4ꢀmethylphenol is attribꢀ
utable to the presence in their structures of the bulky
substituents positioned ortho with respect to the hydroxy
group.17 Lipophilic porphyrin free bases and their metal
complexes are capable of incorporating into the lipid biꢀ
Results and Discussion
It is known18 that a mixed aldehyde condensation of
pyrrole and two different aldehydes gives, in principal,
a set of six porphyrins. By using the excess of one of
aldehyde, the significant simplification of the reaction
mixture is possible. In this case, two porphyrins are preꢀ
dominantly formed, i.e., a symmetrically substituted porꢀ
phyrin derived from the excess aldehyde and an asymꢀ
metrically substituted porphyrin bearing one substituent
derived from the limiting aldehyde. In most cases, the
separation of the mixture of formed porphyrins could be
accomplished. Thus, mixed aldehyde condensation is an
expedient approach to achieve our goals.
1
8
layer of the cell membranes and inactivating the free
radicals.19 These properties form the basis for the use of
porphyrin scaffolds in treatment of the diseases mediated
by oxidative stress and make the studies in this field very
relevant.20 Introduction of the fragments of the moleꢀ
cules having their own AOA into the porphyrin periphery
noticeably affects the antioxidant activity of these conjuꢀ
1
9,21—23
gates. Thus, it has been found earlier
that symꢀ
metrically substituted tetra(mesoꢀaryl)porphyrins bearing
peripheral diisobornylphenol and diꢀtertꢀbutylphenol
moieties possess antioxidant and antiradical activities.
Moreover, porphyrin macrocycle is able to modify the
overall biological activity of the molecule not only by
changing the reactivity of the phenolic moiety but also by
changing the body distribution of the antioxidant.20
It is interesting to vary the number of terpenephenolic
substituents appended to the porphyrin framework beꢀ
cause it gives possibility to examine the impact of these
fragments into overall AOA of the compound. Conseꢀ
quently, the synthesis of asymmetrically substituted porꢀ
phyrins bearing different number of terpenephenolic subꢀ
stituents is actual. In the present work, we studied a mixed
aldehyde condensation of either 4ꢀhydroxyꢀ3,5ꢀdi(1,7,7ꢀ
Condensation of pyrrole, aldehyde 1, and fourꢀfold
excess of benzaldehyde 3 (with respect to aldehyde 1)
affords a mixture of porphyrins 4—7 (Scheme 1). Unꢀ
fortunately, we failed to separate this mixture due to close
polarity of the formed porphyrins.
Thin layer chromatography indicates that the reacꢀ
tion produces a mixture of four porphyrins. The compoꢀ
sition of the mixture was examined by electrospray ionꢀ
1
ization mass spectrometry, H NMR spectroscopy, and
UV spectroscopy. Mass spectrum of the obtained mixture
shows the peaks of the protonated molecular ions of porꢀ
phyrins 4—7. The UV spectrum contains the Soret band
and the bands characteristic of the tetraꢀmesoꢀsubstituted
1
porphyrin chromophore. H NMR spectrum exhibits
signals characteristic of the porphyrin framework at
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2131—2135, November, 2017.
066ꢀ5285/17/6611ꢀ2131 © 2017 Springer Science+Business Media, Inc.
1

2
132
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017
Belykh et al.
Scheme 1
Conditions: 1) EtCOOH, reflux, 1 h, 2) oxidation
with atmospheric oxygen, 5 days.
Ar =
(1, 5—7),
(2)
the δ 8.64—9.07 range and at δ –2.71 (signals of the H(β)
proton of the pyrrole rings and the NH groups, respecꢀ
tively). Condensation of aldehyde 2, benzaldehyde 3, and
pyrrole carried out under similar conditions gives preꢀ
dominantly tetra(mesoꢀphenyl)porphyrin 4 along with the
nonꢀporphyrin products (see Scheme 1).
Structures of newly synthesized porphyrins 10—13
were established by IR and UV spectroscopy, NMR specꢀ
troscopy, and mass spectrometry. Electrospray ionizaꢀ
tion mass spectra of compounds 10—13 reveal the cluster
+
peaks with m/z one mass unit ([MH] ) and two mass
+
units ([M + 2 H] ) larger than the molecular ion peak.
The probability of successful mixed aldehyde condenꢀ
sation increases by using aldehydes of similar reactivity,
for instance, 4ꢀmethoxybenzaldehyde 8, in the reaction
with pyrrole. Moreover, introduction of the polar group
into phenyl substituents located at the periphery of the
porphyrin core greatly simplifies the separation of the
product mixture. To synthesize porphyrins bearing one
phenol substituent by the mixed aldehyde condensation,
we used an excess of aldehyde 8 with the respect to aldeꢀ
hydes 1 and 2. To minimize the formation of nonꢀporꢀ
phyrin material, the total molar amount of aldehydes used
in the reaction was equal to molar amount of pyrrole
UV spectra of the synthesized porphyrins show the Soret
band and the bands characteristic of the tetraꢀmesoꢀsubꢀ
stituted porphyrin core. IR spectra of porphyrins 10—13
bearing 2,6ꢀdiisobornylphenol and 2,6ꢀdiꢀtertꢀbutylꢀ
phenol fragments exhibit stretching vibrations of the
N—H bonds of the porphyrin framework and the O—H
bonds of the hydroxy groups of the phenol moieties.
1
H NMR spectra of compounds 10—13 contain the sigꢀ
nals of the porphyrin core (the H(β) pyrrole protons and
the intracyclic NH protons) and the signals of diisoꢀ
bornylphenol (compounds 10 and 12) and tertꢀbutylꢀ
phenol (compounds 11 and 13) fragments. The integral
intensity ratios of the signals of the protons of the porꢀ
phyrin and phenol fragments indicate the presence of one
phenol substituent in compounds 10 and 11 and two phenol
(
Scheme 2).
Condensation of pyrrole with a 4 : 1 mixture of
4
ꢀmethoxybenzaldehyde 8 and aldehyde 1 produces
1
3
a mixture of porphyrins 9, 10, 12, and 14 (see Scheme 2).
We succeeded in isolation of pure porphyrins 9, 10, and
moieties in compounds 12 and 13. In C NMR spectra,
the carbon atoms of the diisobornyl (compounds 10 and
12) and tertꢀbutyl substituents (compounds 11 and 13)
resonate at δC 10—51 and δC 30—40, respectively. The
positions of these signals ensure the retained structure
of these fragments. The characteristic feature of the
1
2 by chromatographic separation of this mixture on
a column filled with Al O and SiO (see Experimental).
2
3
2
Porphyrin 14 was not isolated in pure state due to close
polarity of products 12 and 14 and low yield of 14. Simiꢀ
lar reaction of pyrrole and a mixture of aldehydes 8 and 2
gives a mixture of porphyrins 9, 11, 13, and 15 (see
Scheme 2). Note that porphyrin 15 was not isolated pure
from this mixture.
1
3
C NMR spectra is the presence of the widened signals
at δC 129—132. According to HSQC and HMBC experiꢀ
ments, these signals belongs to the C(α) and C(β) atoms
1
13
of the pyrrole and pyrrolidene rings. Both H— C HSQC

Tetra(mesoꢀaryl)porphyrins
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017 2133
Scheme 2
Ar =
(1, 10, 12, 14),
(2, 11, 13, 15); Ar´ =
(8—15)
Conditions: 1) EtCOOH, reflux, 1 h, 2) oxidation with atmospheric oxygen, 5 days.
and 1H—13C HMBC NMR spectra of the synthesized
compounds show the crossꢀpeaks between the H(β) of
the pyrrole and pyrrolidene rings and the carbon atom at
δC 129—132.
In summary, the present work describes the mixed
aldehyde condensation of pyrrole with a mixture of either
fil precoated plates. The column chromatography was carried
out with alumina 40/200 μm (pure grade) and silica gel 70/230μ
(
Alfa Aesar). Physicochemical studies of the synthesized comꢀ
pounds were carried out on the equipment of the Center for
Collective Use "Chemistry" of the Institute of Chemistry of the
Komi Scientific Center of the Ural Branch of the Russian Acadꢀ
emy of Sciences.
Synthesis of 4ꢀhydroxyꢀ3,5ꢀdi(1,7,7ꢀtrimethylbicyclo[2.2.1]ꢀ
heptꢀexoꢀ2ꢀyl)benzaldehyde (1) and its spectral properties have
been described earlier.24
3,5ꢀDiꢀtertꢀbutylꢀ4ꢀhydroxybenzaldehyde (2) was syntheꢀ
sized following the known procedure.25
Mixed aldehyde condensation of pyrrole, aldehyde 1, and
benzaldehyde (3). A solution of 4ꢀhydroxyꢀ3,5ꢀdi(1,7,7ꢀtriꢀ
methylbicyclo[2.2.1]heptꢀexoꢀ2ꢀyl)benzaldehyde 1 (0.29 g,
4
2
ꢀhydroxyꢀ3,5ꢀdi(1,7,7ꢀtrimethylbicyclo[2.2.1]heptꢀexoꢀ
ꢀyl)benzaldehyde (1) or 3,5ꢀdiꢀtertꢀbutylꢀ4ꢀhydroxyꢀ
benzaldehyde (2) and benzaldehyde 3 (4ꢀmethoxybenzꢀ
aldehyde 8) to synthesize asymmetrically substituted
tetra(mesoꢀaryl)porphyrins bearing one peripheral phenol
substituent. A series of asymmetrically substituted porꢀ
phyrins bearing the peripheral diisobornylphenol and diꢀ
tertꢀbutylphenol moieties was synthesized. The reaction
conditions were optimized to synthesize tetra(mesoꢀ
aryl)porphyrins bearing one diisobornylphenol or diꢀtertꢀ
butylphenol substituent.
0
.74 mmol), benzaldehyde 3 (0.30 mL, 2.94 mmol), and pyrꢀ
role (0.25 mL, 3.68 mmol) in propionic acid (15 mL) was added
to the refluxing propionic acid (20 mL). The mixture was reꢀ
fluxed for 1 h, cooled down, and kept in air at room temperaꢀ
ture for 5 days. The reaction mixture was diluted with chloroꢀ
form, washed with water until neutral to remove excess propiꢀ
onic acid and other water soluble impurities. The organic layer
Experimental
was dried with anhydrous Na SO and concentrated in vacuo.
2
4
IR spectra were recorded with a Shimadzu IR Prestige 21 K
Fourier transform infrared spectrophotometer in KBr pellets.
UV spectra were obtained with a Shimadzu UVꢀ1700 spectroꢀ
photometer using the 10ꢀmm quarts cells against chloroform in
the reference cell. H and C NMR spectra were recorded on
a Bruker Avance II instrument (working frequencies of 300 and
According to TLC and mass spectrometry, the residue (0.03 g)
is a mixture of porphyrins 4—7. The residue was washed with
hexane to obtain violet fine crystalline powder. UV (CHCl ),
3
λmax/nm (I (%)): 650 (2), 595 (1), 555.0 (2), 518 (4), 422.5
1
13
+
(100). MS (ESI), found: m/z 615.5 [MH] . C44H31N .
4
+
Calculated: 615.3 (porphyrin 4). Found: m/z 903.7 [MH] .
7
5 MHz, respectively) in CDCl . In some cases, the signals
C64H63N O. Calculated: 903.5 (porphyrin 5). Found: m/z
3
4
+
were attributed by using 2D NMR experiments (HSQC and
HMBC). Electrospray ionization (ESI) mass spectrometry was
performed with a Thermo Finnigan LCQ Fleet instrument.
The course of the reaction was monitored by TLC on the Sorbꢀ
1191.7 [MH] . C84H95N O . Calculated: 1191.8 (porphyꢀ
4
2
rins 6 and 7).
Mixed aldehyde condensation of pyrrole, aldehyde 2, and
benzaldehyde (3). A solution of 3,5ꢀdiꢀtertꢀbutylꢀ4ꢀhydroxyꢀ

2
134
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017
Belykh et al.
+
benzaldehyde 2 (0.20 g, 0.85 mmol), benzaldehyde 3 (0.35 mL,
.44 mmol), and pyrrole (0.30 mL, 4.29 mmol) in propionic
(4), 424 (100). MS (ESI), m/z 993.6 [MH] . IR (KBr), ν/cm–1:
3
3599 (OH); 3316 (NH); 2835 (CH ); 2949, 1607 (C=C); 1510,
3
acid (10 mL) was added to the refluxing propionic acid (7 mL).
The mixture was refluxed for 1 h, cooled down, and kept in air
at room temperature for 5 days. The reaction mixture was diꢀ
luted with chloroform, washed with water until neutral to reꢀ
move excess propionic acid and other water soluble impurities.
The organic layer was dried with anhydrous Na SO and conꢀ
1462, 1348, 1248, 1177, 1036, 972, 800, 735.
5,10ꢀBis[3,5ꢀdi(1,7,7ꢀtrimethylbicyclo[2.2.1]heptꢀexoꢀ2ꢀ
yl)ꢀ4ꢀhydroxyphenyl)]ꢀ15,20ꢀbis(4ꢀmethoxyphenyl)porphyrin
(12). Violet fine crystalline powder. R 0.59 (Sorbfil, tetrachloroꢀ
f
1
methane—acetone, 80 : 1). H NMR (CDCl ), δ: –2.69 (br.s,
3
2 H, NH); 0.90 (s, 12 H, C(10,10´)H ); 0.96 (s, 12 H, C(9,9´)H );
2
4
3
3
centrated in vacuo. The residue was washed with ethanol and
separated by column chromatography. The chromatographic
column was packed by the wetꢀloading method with Al O (botꢀ
1.15 (s, 12 H, C(8,8´)H ); 1.41—2.04 (m, 24 H, H(3,3´,4,4´),
3
C(5,5´)H , C(6,6´)H ); 2.30—2.44 (m, 4 H, H(3,3´)); 3.39 (br.t,
2
2
4 H, H(2,2´), J = 8.2 Hz); 4.14 (s, 6 H, C(15,20) ArOCH );
2
3
3
tom layer) and SiO (upper layer) using CCl as a solvent. The
5.24 (s, 2 H, OH); 7.33 (s, 4 H, C(15,20) ArH(3,5)); 8.06
(s, 4 H, C(5,10) ArH(14,16)); 8.16 (d, 4 H, C(15,20) ArH(2,6),
J = 8.2 Hz); 8.79—8.88 (m, 4 H, H(2,3,12,13)); 8.89 (br.s, 4 H,
2
4
products were eluted in a gradient mode with tetrachloroꢀ
methane—acetone, 100 : 1→20 : 1. Compound 4 was isolated in
the yield of 0.062 g (3%). Violet fine crystalline powder. Specꢀ
tral properties of the obtained product are in agreement with
those published earlier.18
H(7,8,17,18)). 1 C NMR (CDCl ), δ: 12.93 (C(10,10´)); 20.37
3
3
(C(9,9´)); 21.47 (C(8,8´)); 27.67 (C(5,5´)); 34.21 (C(3,3´));
40.25 (C(6,6´)); 45.51 (C(4,4´)); 46.39 (C(2,2´)); 48.27 (C(7,7´));
Mixed aldehyde condensation of pyrrole, aldehyde 1, and
50.25 (C(1,1´)); 55.59 (C(15,20) ArOCH ); 112.17 (C(15,20)
3
4
ꢀmethoxybenzaldehyde (8). A solution of 4ꢀhydroxyꢀ3,5ꢀ
di(1,7,7ꢀtrimethylbicyclo[2.2.1]heptꢀexoꢀ2ꢀyl)benzaldehyde 1
0.29 g, 0.74 mmol), 4ꢀmethoxybenzaldehyde 8 (0.36 mL,
.96 mmol), and pyrrole (0.26 mL, 3.75 mmol) in propionic
ArC(3,5)); 119.38 and 120.11 (C(meso)); 121.35 (C(5,10)
ArC(12)); 126.72 (C(5,10) ArC(11,13)); 130.88—132.49 (C(α,β));
132.49 (C(5,10) ArC(14,16)); 134.93 (C(15,20) ArC(4)); 135.55
(C(15,20) ArC(2,6)); 153.82 (C(5,10) ArC(15)); 159.35
(
2
acid (15 mL) was added to the refluxing propionic acid (20 mL).
The mixture was refluxed for 1 h, cooled down, and kept in air
at room temperature for 5 days. The mixture was diluted with
chloroform and washed with water until neutral to remove exꢀ
cess propionic acid and other water soluble impurities. The
(C(15,20) ArC(1)). UV (CHCl ), λmax/nm (I (%)): 650 (5),
3
595 (5), 557 (7), 519 (9), 425 (100). MS (ESI), m/z 1252.6
+
–1
[M + 2 H] . IR (KBr), ν/cm : 3595 (OH); 3318 (NH); 2874
(CH ); 2953, 1605 (C=C); 1510, 1460, 1350, 1248, 1175, 1036,
3
974, 802, 737.
organic layer was dried with anhydrous Na SO and concenꢀ
Mixed aldehyde condensation of pyrrole, aldehyde 2, and
4ꢀmethoxybenzaldehyde (8). A solution of 3,5ꢀdiꢀtertꢀbutylꢀ4ꢀ
hydroxybenzaldehyde 2 (0.20 g, 0.85 mmol), 4ꢀmethoxybenzꢀ
aldehyde 8 (0.41 mL, 3.37 mmol), and pyrrole (0.29 mL,
4.22 mmol) in propionic acid (10 mL) was added to the refluxꢀ
ing propionic acid (7 mL). The mixture was refluxed for 1 h,
cooled down, and kept in air for 5 days. The reaction mixture
was diluted with chloroform and washed with water until neuꢀ
2
4
trated in vacuo. According to TLC and mass spectrometry, the
residue is a mixture of porphyrins 9, 10, 12, and 14. The resiꢀ
due was washed with hexane and separated by column chromaꢀ
tography as described above using the column loaded with Al O
2
3
and SiO2 (successive elution with hexane and chloroform).
Purification gives 0.013 g (2%) of the target product 10, 0.027 g
(
0
12%) of porphyrin 9, 0.006 g (0.65%) of porphyrin 12, and
.005 g of the mixture of 12 and 14.
Tetrakis(mesoꢀmethoxyphenyl)porphyrin (9). R 0.13 (Sorbꢀ
tral. The organic layer was dried with anhydrous Na SO and
2 4
concentrated in vacuo. According to TLC and mass spectroꢀ
metry, the residue is a mixture of porphyrins 9, 11, 13, and 15.
The residue was washed with hexane and separated by column
chromatography as described above using the column loaded
f
fil, tetrachloromethane—acetone, 80 : 1). Spectral properties
of the obtained product are in agreement with those published
2
6
earlier.
ꢀ[3,5ꢀDi(1,7,7ꢀtrimethylbicyclo[2.2.1]heptꢀexoꢀ2ꢀyl)ꢀ4ꢀ
hydroxyphenyl)]ꢀ10,15,20ꢀtris(4ꢀmethoxyphenyl)porphyrin (10).
5
with Al O and SiO (elution with tetrachloromethane—acetone).
2 3 2
Purification gives 0.014 g (2%) of the target product 11, 0.02 g
(8%) of porphyrin 9, 0.006 g (0.76%) of porphyrin 13, and
0.005 g of the mixture of 13 and 15.
Violet fine crystalline powder. R 0.36 (Sorbfil, tetrachloroꢀ
f
1
methane—acetone, 80 : 1). H NMR (CDCl ), δ: –2.69 (br.s,
3
2
1
H, NH); 0.89 (s, 6 H, C(10,10´)H ); 0.96 (s, 6 H, C(9,9´)H );
5ꢀ(3,5ꢀDiꢀtertꢀbutylꢀ4ꢀhydroxyphenyl)ꢀ10,15,20ꢀtris(4ꢀ
methoxyphenyl)porphyrin (11). Violet fine crystalline powder.
3
3
.15 (s, 6 H, C(8,8´)H ); 1.41—2.04 (m, 12 H, H(3,3´,4,4´),
3
1
C(5,5´)H , C(6,6´)H ); 2.29—2.43 (m, 2 H, H(3,3´)); 3.39 (br.t,
R 0.57 (Sorbfil, tetrachloromethane—acetone, 80 : 1). H NMR
2
2
f
2
5
8
H, H(2,2´), J = 8.2 Hz); 4.13 (s, 9 H, C(10,15,20) ArOCH );
.24 (s, 1 H, OH); 7.32 (d, 6 H, C(10,15,20) ArH(3,5), J = 8.2 Hz);
.06 (s, 2 H, C(5) ArH(14,16)); 8.16 (d, 6 H, C(10,15,20)
(CDCl ), δ: –2.67 (br.s, 2 H, NH); 1.68 (s, 18 H, C(5)
3
3
ArC(CH ) ); 4.14 (s, 9 H, C(10,15,20) ArOCH ); 5.59
3
3
3
(s, 1 H, OH); 7.33 (d, 6 H, C(10,15,20) ArH(3,5), J = 8.2 Hz);
8.09 (br.s, 2 H, C(5) ArH(2,6)); 8.17 (d, 6 H, C(10,15,20)
ArH(2,6), J = 8.2 Hz); 8.90 (br.s, 6 H, H(12,13,17,18)); 8.91
(d, 2 H, H(2,8), J = 4.6 Hz); 8.95 (d, 2 H, H(3,7), J = 4.6 Hz).
ArH(2,6), J = 8.2 Hz); 8.84 (d, 2 H, H(3,7), J = 4.6 Hz); 8.86
(
1
d, 2 H, H(2,8), J = 4.6 Hz); 8.89 (br.s, 6 H, H(12,13,17,18)).
3
C NMR (CDCl ), δ: 12.93 (C(10,10´)); 20.37 (C(9,9´)); 21.48
3
1
3
(
C(8,8´)); 27.65 (C(5,5´)); 34.24 (C(3,3´)); 40.26 (C(6,6´));
C NMR (CDCl ), δ: 30.69 (C(5) ArC(CH ) )); 34.59 (C(5)
3 3 3
4
5
1
5.49 (C(4,4´)); 46.39 (C(2,2´)); 48.26 (C(7,7´)); 50.25 (C(1,1´));
ArC(CH ) ); 55.61 (C(10,15,20) ArOCH ); 112.20
3
3
3
5.59 (C(10,15,20) ArOCH ); 112.19 (C(10,15,20) ArC(3,5));
(C(10,15,20) ArC(3,5)); 119.45 and 119.61 (C(meso)); 129.66—
131.80 (C(α,β)); 132.12 (C(5) ArC(2,6)); 134.05 (C(10,15,20)
ArC(4)); 134.83 (C(5) ArC(4)); 135.58 (C(10,15,20) ArC(2,6));
3
19.52 and 119.60 (C(meso)); 121.33 (C(5) ArC(12)); 126.72
(
(C5) ArC(11,13)); 130.26—131.75 (C(α,β)); 132.45 (C(5)
ArC(14,16)); 134.78 (C(10,15,20) ArC(4)); 135.54 (C(10,15,20)
ArC(2,6)); 153.86 (C(5) ArC(15)); 159.34 (C(10,15,20) ArC(1)).
153.61 (C(5) ArC(1)); 159.40 (C(10,15,20) ArC(1)). UV (CHCl ),
3
λmax/nm (I (%)): 651 (1), 593 (1), 557 (3), 519 (4), 424 (100).
+
–1
UV (CHCl ), λmax/nm (I (%)): 651 (1), 595 (1), 557 (3), 520
MS (ESI), m/z 833.5 [MH] . IR (KBr), ν/cm : 3630 (OH);
3

Tetra(mesoꢀaryl)porphyrins
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017 2135
3
1
316 (NH); 2835 (CH ); 2957, 1607 (C=C); 1508, 1468, 1437,
246, 1177, 1034, 972, 802, 735.
10. Pat. RF 2351321, Bull. Izobtret. [Invention Bull.], 2009, No. 6
(in Russian).
3
5
,10ꢀBis(3,5ꢀdiꢀtertꢀbutylꢀ4ꢀhydroxyphenyl)ꢀ15,20ꢀbis(4ꢀ
11. N. M. Émanuel´, L. M. Dronova, N. P. Konovalova, Z. K.
Maizus, I. P. Skibida, Dokl. Akad. Nauk SSSR, 1963, 152,
481 (in Russian).
methoxyphenyl)porphyrin (13). Violet fine crystalline powder.
R 0.70 (Sorbfil, tetrachloromethane—acetone, 80 : 1). H NMR
1
f
(
CDCl ), δ: –2.65 (br.s, 2 H, NH); 1.67 (s, 36 H, C(5,10)
12. A. V. Kolesnikov, Ross. Med.ꢀBiol. Vestn. im. Akad. I. P.
Pavlova [Russ. MedicoꢀBiological Bull. named after Acadeꢀ
mician I. P. Pavlov], 2012, No. 3, 158 (in Russian).
13. F. S. Zarudii, G. Z. Gil´mutdinov, R. F. Zarudii, M. A.
Myshkin, F. B. Gershanov, T. A. Novikov, Pharm. Chem.
J., 2001, 35, 162.
14. O. S. Frankfurt, L. P. Lipchina, T. V. Bunto, N. M. Émanuel´,
Bull. Eksp. Biologii i Meditsiny [Bull. Exp. Biol. Med.], 1967,
64, 882 (in Russian).
15. R. F. Zarudii, V. A. Myshkin, F. S. Zarudii, A. F. Ismagiloꢀ
va, V. A. Davydova, Eksperim. i Klin. Farmakologiya [Exp.
Clin. Pharmacol.], 1998, 61, No. 5, 21 (in Russian).
16. Pat. RF 2240103, Bull. Izobtret. [Invention Bull.], 2004, No. 5
(in Russian).
17. E. B. Men´shchikova, N. K. Zenkov, V. Z. Lankin, I. A.
Bondar´, N. F. Krugovykh, V. A. Trufakin, Okislitel´nyi
stress. Prooksidanty i antioksidanty [Oxidative Stress. Proꢀ
oxidants and Antioxidants], Slovo, Moscow, 2006, 553 pp.
(in Russian).
3
Ar—C(CH ) ); 4.14 (s, 6 H, C(15,20) ArOCH ); 5.58 (s, 2 H,
3
3
3
OH); 7.33 (d, 4 H, C(15,20) ArH(3,5), J = 8.2 Hz); 8.08 (br.s,
H, C(5,10) ArH(2,6)); 8.18 (d, 4 H, C(15,20) ArH(2,6),
4
J = 8.2 Hz); 8.89 (br.s, 2 H, H(17,18)); 8.90 (d, 2 H, H(2,13),
J = 4.6); 8.95 (d, 2 H, H(3,12), J = 4.6 Hz); 8.98 (br.s, 2 H,
H(7,8)). 1 C NMR (CDCl ), δ: 30.69 (C(5,10) ArC(CH ) ));
3
1
1
3
3
3 3
4.59 (C(5,10) ArC(CH ) ); 55.61 (C(15,20) ArOCH );
3 3 3
12.18 (C(15,20) ArC(3,5)); 119.33 and 121.44 (C(meso));
29.75—131.70 (C(α,β)); 131.97 (C(5,10) ArC(2,6)); 134.03
(
C(15,20) ArC(4)); 134.88 (C(5,10) ArC(4)); 135.55 (C(15,20)
ArC(2,6)); 153.57 (C(5,10) ArC(1)); 159.37 (C(15,20) ArC(1)).
UV (CHCl ), λ /nm (I (%)): 651 (2), 595 (2), 558 (3), 520 (4),
3
max
+
–1
4
3
1
25 (100). MS (ESI), m/z 931.6 [MH] . IR (KBr), ν/cm :
636 (OH); 3318 (NH); 2840 (CH ); 2957, 1607 (C=C); 1508,
3
466, 1435, 1244, 1177, 1034, 974, 802, 735.
This work was financially supported by the Russian
Science Foundation (Project No. 16ꢀ13ꢀ10367).
1
8. K. A. Askarov, B. D. Berezin, R. P. Evstigneeva, N. S.
Enikolopyan, G. V. Kirillova, O. I. Koifman, A. F. Mironov,
G. V. Ponomarev, A. S. Semeikin, O. G. Khelevina, K. V.
Yatsimirskii, Porfiriny: struktura, svoistva, sintez [Porphyꢀ
rins: Structure, Porperties, Synthesis], Nauka, Moscow,
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in revised form October 2, 2017