Synthesis and properties of [4-(triphenylmethyl)phenoxy]acetic and 3-[4-(triphenylmethyl)phenoxy]propionic acids and their condensation with phthalimide leading to meso-substituted tetrabenzoporphyrins

Article abstract of DOI:10.1134/S1070428009070070

Condensation of 4-(triphenylmethyl)phenol with monochloroacetic and 3-bromopropionic acids gave, respectively, [4-(triphenylmethyl)phenoxy]acetic and 3-[4-(triphenylmethyl)phenoxy]propionic acids which reacted with phthalimide in the presence of zinc acet

Full text of DOI:10.1134/S1070428009070070

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 7, pp. 1024–1030. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © N.E. Galanin, L.A. Yakubov, G.P. Shaposhnikov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 7,
pp. 1037–1043.
Synthesis and Properties of [4-(Triphenylmethyl)phenoxy]acetic
and 3-[4-(Triphenylmethyl)phenoxy]propionic Acids
and Their Condensation with Phthalimide Leading
to meso-Substituted Tetrabenzoporphyrins
N. E. Galanin, L. A. Yakubov, and G. P. Shaposhnikov
Ivanovo State University of Chemical Technology, pr. F. Engel’sa 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
Received April 4, 2008
Abstract—Condensation of 4-(triphenylmethyl)phenol with monochloroacetic and 3-bromopropionic acids
gave, respectively, [4-(triphenylmethyl)phenoxy]acetic and 3-[4-(triphenylmethyl)phenoxy]propionic acids
which reacted with phthalimide in the presence of zinc acetate to produce meso-substituted zinc tetrabenzo-
porphyrins having bulky triphenylmethyl groups in the substituent. The corresponding free ligands were ob-
tained by demetalation of the zinc complexes. Spectral properties of the synthesized compounds were studied.
DOI: 10.1134/S1070428009070070
Unlike phthalocyanine, tetrabenzoporphyrin mole-
cule may be modified via introduction of substituents
into not only isoindole fragments but also meso posi-
tions of the macroring. meso-Substituted tetrabenzo-
porphyrins possess interesting nonlinear optical [1, 2],
acid–base [3], and electrochemical properties [4]. They
may be used in the diagnostics and photodynamic
therapy of cancer [5–7], as well as catalysts [8]. Such
properties of meso-substituted tetrabenzoporphyrins
determine importance of their further detailed studies.
acids, its undoubted merit is that it includes only one
step. Therefore, just the first method was used in the
present work to synthesize meso-substituted tetraben-
zoporphyrins.
An important group of tetrapyrrole macrohetero-
cycles consists of compounds having bulky substit-
uents in their molecules. Phthalocyanines containing
triphenylmethyl groups possess quite valuable prop-
erties from the applied viewpoint [16–18]. However,
we have found no published data on the synthesis and
properties of meso-substituted tetrabenzoporphyrins
having triphenylmethyl groups in the meso substit-
uents, though such derivatives should also be interest-
ing from the viewpoint of practice. Presumably, the
reason is the lack of preparative procedures for the
synthesis of acetic acid derivatives containing triphen-
ylmethyl groups, which could be used as initial com-
pounds for the synthesis of meso-substituted tetraben-
zoporphyrins. Taking the above stated into account, the
present work was aimed at developing procedures for
the preparation of [4-(triphenylmethyl)phenoxy]acetic
acid (I) and 3-[4-(triphenylmethyl)phenoxy]propionic
acid (II) and synthesizing meso-substituted tetrabenzo-
porphyrins via condensation of acids I and II with
phthalimide.
Up to now, three main methods for the synthesis
of meso-substituted tetrabenzoporphyrins have been
reported. The first of these includes high-temperature
template condensation of substituted acetic acids with
phthalimide or its derivatives in the presence of bi-
valent metal (as a rule, zinc or cadmium) salts or
hydroxides [9, 10]. The second method is based on
direct introduction of substituents into the meso posi-
tions of already generated macroring [11]. Finally, the
third, most advanced approach is based on condensa-
tion of aromatic aldehydes with saturated isoindole de-
rivatives, such as 4,5,6,7-tetrahydroisoindole [12, 13]
or 4,7-dihydroisoindole [14, 15], followed by mild
oxidation of hydrogenated tetrabenzoporphyrins thus
formed. Although the first method is not free from
some serious disadvantages related to thermal instabil-
ity of many substituted phthalimides and arylacetic
Compounds I and II were obtained by condensation
of 4-triphenylmethylphenol (III) with chloroacetic and
1024

SYNTHESIS AND PROPERTIES OF [4-(TRIPHENYLMETHYL)PHENOXY]ACETIC
1025
Scheme 1.
O
COOH
ClCH2COOH
Ph3C
OH
I
O
Ph3C
COOH
BrCH2CH2COOH
III
Ph3C
II
3-bromopropionic acids, respectively, in dimethyl-
formamide in the presence of potassium hydroxide
(Scheme 1). Acids I and II were isolated as colorless
powders which are soluble in benzene, chloroform,
and acetone. Their structure was confirmed by the data
3027 cm–1 correspond to vibrations of C–H bonds in
the benzene rings. The band at 2932 cm–1 was assigned
to C–H vibrations of the methylene group. The car-
boxy group gave rise to carbonyl absorption band at
1699 cm–1, and bands at 1262 and 1159 cm–1 belonged
to stretching vibrations of the ether C–O bonds.
A strong band at 698 cm–1 is typical of bending vibra-
tions of aromatic rings in the triphenylmethyl group.
The IR spectrum of acid II resembled that of com-
1
of elemental analysis and IR and H NMR spectra.
The IR spectrum of I contains an absorption band at
3552 cm–1 due to stretching vibrations of O–H bond
in the carboxy group, absorption bands at 3083 and
8.0
7.0
6.0
5.0
4.0
3.0 δ, ppm
Fig. 1. 1H NMR spectrum of 3-[4-(triphenylmethyl)phenoxy]propionic acid (II) in CDCl3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

GALANIN et al.
1026
Scheme 2.
O
N
N
N
N
O
COOH
Zn(OAc)2
Zn
O
NH
+
Ph3C
O
CPh3
IV
I
V
pound I with the difference that the absorption band at
2939 cm–1 had higher intensity due to the presence of
two methylene groups.
groups of molecule II resonated as two singlets at
δ 2.97 and 2.90 ppm.
We made an attempt to synthesize {tetra-meso-
[4-(triphenylmethyl)phenoxy]tetrabenzoporphyrinato}-
zinc(II) by reaction of phthalimide (IV) with excess
acid I in the presence of zinc(II) oxide. However,
heating of the reactants at 350°C over a period of 2 h
resulted in the formation of a brown melt which did
not contain even traces of the target compound. Rais-
ing the temperature or increasing the reaction time led
to charring. We succeeded in obtaining tetrabenzopor-
phyrins by replacing zinc(II) oxide by acetate. In this
case, the reaction occurred at 310°C and was complete
in 40–50 min (the reaction mixture turned green).
1
In the H NMR spectrum of acid I we observed
a singlet at δ 8.10 ppm due to proton in the carboxy
group, and a 15-proton multiplet was present in the
region δ 7.40–7.11 ppm from aromatic protons in the
triphenylmethyl group. Protons in the para-substituted
benzene ring resonated as doublets of doublets at
δ 7.10–7.05 and 6.79–6.73 ppm, and the singlet at
δ 2.99 ppm was assigned to protons in the methylene
group. The COOH proton signal in the spectrum of
substituted propionic acid II (Fig. 1) was observed in
a stronger field, at δ 8.02 ppm, whereas signals from
15 protons in the triphenylmethyl group and 4 protons
in the phenoxy group were located in the same regions
as in the spectrum of I. Protons in the two methylene
We expected formation of a mixture of zinc com-
plexes of meso-[4-(triphenylmethyl)phenoxy]-substi-
tuted tetrabenzoporphyrins with different numbers of
Scheme 3.
O
N
N
N
N
O
Zn(OAc)2
COOH
Zn
NH
+
CPh3
O
Ph3C
O
IV
II
VI
N
N
N
N
Ph3C
O
+
Zn
CPh3
O
VII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

SYNTHESIS AND PROPERTIES OF [4-(TRIPHENYLMETHYL)PHENOXY]ACETIC
1027
D
meso substituents, taking into account that acetate ion
present in the reaction mixture can act as source of
methylene group. However, chromatographic separa-
tion of the reaction mixture gave only unsubstituted
tetrabenzoporphyrinatozinc and one more porphyrin
derivative, the latter being characterized by better
solubility in organic solvents. This product was iden-
tified as {meso-[4-(triphenylmethyl)phenoxy]tetraben-
zoporphyrinato}zinc(II) (V) (Scheme 2). The absence
of tetrabenzoporphyrins with a larger number of meso
substituents may be rationalized in terms of steric hin-
drances. Analogous pattern was observed previously,
e.g., in the reaction of 4-phenylphthalimide with
(naphthalen-1-yl)acetic acid in the presence of zinc
acetate, which also produced only the corresponding
mono-meso-substituted derivative [19].
1.5
1.0
0.5
0.0
1
2
400
500
600
λ, nm
700
800
Fig. 2. Electronic absorption spectra of compounds (1) V
and (2) VIII in benzene.
Likewise, the reaction of phthalimide (IV) with
acid II in the presence of zinc(II) oxide gave no
desired meso-substituted tetrabenzoporphyrin. How-
ever, the reaction performed in the presence of zinc(II)
acetate resulted in the formation of two readily soluble
tetrabenzoporphyrins which were isolated by column
chromatography and identified as {5-[4-(triphenyl-
methyl)phenoxymethyl]tetrabenzoporphyrinato}-
zinc(II) (VI) and {5,15-bis[4-(triphenylmethyl)phen-
oxymethyl]tetrabenzoporphyrinato}zinc(II) (VII)
(Scheme 3). Obviously, the presence of an extra meth-
ylene unit in molecule II reduces steric hindrances
to the formation of meso-substituted tetrabenzopor-
phyrins.
D
1.0
0.5
1
2
0.0
400
500
600
700
λ, nm
We believe that just trans-disubstituted tetrabenzo-
porphyrin VII is formed for steric reasons. Quantum-
chemical calculations (AM1) of compound VII and its
cis-substituted isomer, {5,10-bis[4-(triphenylmethyl)-
phenoxymethyl]tetrabenzoporphyrinato}zinc(II),
showed that the former is more energetically favorable
by 62.13 kJ/mol. In addition, molecule VII is more
planar.
Fig. 3. Electronic absorption spectra of compounds (1) VI
and (2) VII in benzene.
D
1
1.0
0.5
Treatment of compounds V–VII in chloroform with
concentrated hydrochloric acid gave, respectively,
5-[4-(triphenylmethyl)phenoxy]tetrabenzoporphyrin
(VIII), 5-[4-(triphenylmethyl)phenoxymethyl]tetra-
benzoporphyrin (IX), and 5,15-bis[4-(triphenylmethyl)-
phenoxymethyl]tetrabenzoporphyrin (X) which were
isolated and purified by column chromatography.
2
Porphyrins V–X are dark green crystalline sub-
stances which are readily soluble in a number of or-
ganic solvents. Their structure was confirmed by ele-
mental analyses and electronic, vibrational, and NMR
spectra. The electronic absorption spectra of V and
0.0
400
500
600
700
λ, nm
Fig. 4. Electronic absorption spectra of compounds (1) IX
and (2) X in benzene.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

GALANIN et al.
1028
VIII (Fig. 2) are typical of tetrabenzoporphyrins. They
contained a strong Soret band and less intense Q band
in the visible region. In the spectrum of porphyrin VIII
(Fig. 2, curve 2), these bands were split into two com-
ponents due to lower symmetry of the macroring. The
absorption maxima in the spectrum of complex V
(Fig. 2, 1) are slightly displaced to the red region
relative to the corresponding absorption maxima of
unsubstituted zinc tetrabenzoporphyrin [20] (by 4 and
10 nm for the Q band and Soret band, respectively),
which may be due to some deviation of the macroring
from planar structure and its polarization. In fact, in
the spectrum of V we also observed two weak bands in
the region λ 488–460 nm, which can be assigned to
charge transfer from the electron-donating substituent
to the macroring. The relative intensity of the Q band
also slightly increases. In the electronic absorption
spectrum of (tetrabenzoporphyrinato)zinc(II), the in-
tensity ratio of the Soret and Q bands is equal to
1:0.34 [21] against 1:0.49 in the spectrum of complex
V. The red shift of the main absorption maxima in the
spectrum of VIII as compared to its unsubstituted
analog amounts to 4–9 nm, and the charge-transfer
band has its maximum at λ 479 nm.
to bending vibrations of monosubstituted benzene
rings in the triphenylmethyl groups. Porphyrin VIII
showed in the IR spectrum a broadened band at
3244 cm–1 due to stretching vibrations of N–H bonds.
The IR spectral patterns of compounds VI, VII, IX,
and X were essentially similar to those observed for
porphyrins V and VIII.
Four groups of signals may be distinguished in the
1H NMR spectrum of zinc complex V. Two most
downfield singlets appeared due to resonance of three
protons in the meso positions: δ 8.14 (15-H) and
8.07 ppm (10-H, 20-H). Multiplet signal in the region
δ 7.41–7.28 ppm belongs to 16 protons in the fused
benzene rings, while aromatic protons in the triphenyl-
methyl group give rise to a multiplet at δ 7.28–
7.10 ppm. Finally, a doublet of doublets was present
in the upfield region (δ 7.09–6.86 ppm) due to four
protons in the para-substituted phenoxy group. The
1H NMR spectrum of the corresponding free ligand,
porphyrin VIII, resembles the spectrum of complex V,
except for the signal at δ –2.23 ppm (2H, NH). Com-
1
pounds VI and VII displayed in the H NMR spectra
additional signals in the region δ 4.26–4.34 ppm,
which belong to methylene protons in the meso-sub-
stituents. The NH protons in porphyrins IX and X
resonated at δ –2.34 and –2.31 ppm, respectively, in-
dicating the absence of appreciable distortion of planar
structure of their molecules.
The electronic absorption spectra of zinc complexes
VI and VII (Fig. 3) are characterized by insignificant
blue shift of the main maxima relative to those ob-
served in the spectrum of V. However, the positions of
absorption maxima in the spectrum of VI (Fig. 3, 1)
are almost the same as in the spectrum of unsubstituted
(tetrabenzoporphyrinato)zinc, whereas the Soret band
in the spectrum of VII (Fig. 3, 2) is displaced by 6 nm
to longer wavelengths. No charge-transfer bands were
observed in the electronic absorption spectrum of
complex VII.
Thus the condensation of phthalimide with [4-(tri-
phenylmethyl)phenoxy]acetic acid in the presence of
zinc(II) acetate is characterized by high selectivity, and
it yields only the corresponding mono-meso-substi-
tuted tetrabenzoporphyrin complex. The condensation
of phthalimide with 3-[4-(triphenylmethyl)phenoxy]-
propionic acid gives a mixture of mono- and bis-meso-
substituted derivatives, i.e., increase in the number of
methylene groups in the acid component reduces steric
hindrances to the formation of macroheterocycles.
The electronic absorption spectra of free ligands IX
and X (Fig. 4) are fairly similar to the spectrum of
unsubstituted tetrabenzoporphyrin. Unlike monosubsti-
tuted porphyrin IX (Fig. 4, 1), compound X (Fig. 4, 2)
displayed a charge-transfer band with its maximum at
λ 485 nm. In addition, increase in the number of meso-
substituents is accompanied by some decrease in the
degree of splitting of the main absorption bands, which
is characteristic of meso-substituted tetrabenzopor-
phyrins [22].
EXPERIMENTAL
The electronic absorption spectra were measured on
1
a Hitachi UV-2001 spectrophotometer. The H NMR
spectra were recorded from solutions in CDCl3 on
a Bruker WM-250 instrument (250 MHz) using tetra-
methylsilane as internal reference. The IR spectra
(400–4000 cm–1) were obtained on an Avatar 360 FT-
IR spectrometer from samples applied to TlI plates.
The elemental compositions were determined using
a FlashEA 1112 CHNS–O Analyzer.
The IR spectra of compounds V and VIII contained
absorption bands typical of tetrabenzoporphyrins. In
particular, bands in the regions 1650–1420 (C=C,
C=N) and 3087–3044 cm–1 (C–H), as well as at 1244
and 1236 cm–1 (C–O), were present. Strong absorption
bands in the region 703–694 cm–1 should be assigned
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

SYNTHESIS AND PROPERTIES OF [4-(TRIPHENYLMETHYL)PHENOXY]ACETIC
1029
4-(Triphenylmethyl)phenol (III) was synthesized
according to the procedure described in [23].
(2H, 10-H, 20-H), 8.14 s (1H, 15-H). Found, %:
C 81.05; H 4.64; N 5.98. C61H38N4OZn. Calculated, %:
C 80.66; H 4.22; N 6.17.
Acids I and II (general procedure). A mixture of
6.7 g (0.02 mol) of 4-(triphenylmethyl)phenol (III),
0.04 mol of chloroacetic or 3-bromopropionic acid,
and 2.8 g (0.07 mol) of potassium hydroxide in 40 ml
of dimethylformamide was heated fir 6 h under reflux
with stirring. The mixture was cooled, diluted with
100 ml of water, and acidified with hydrochloric acid
to pH 1, and the precipitate was filtered off, washed
with water until neutral washings (pH 7), and dried.
Condensation of phthalimide with 3-[4-(triphen-
ylmethyl)phenoxy]propionic acid (II). A mixture of
1.5 g (10.5 mmol) of phthalimide (IV), 4.0 g
(10 mmol) of acid II, and 3.0 g (13 mmol) of zinc(II)
acetate dihydrate was heated for 1 h at 320°C. The
melt was cooled, ground, and extracted with chloro-
form using a Soxhlet apparatus. The solvent was dis-
tilled off, the residue was dissolved in chloroform, and
the solution was applied to a column charged with
Al2O3 (activity grade II according to Brockmann). The
column was eluted with benzene–chloroform (1:1 by
volume). Two green fractions were collected, from
which we isolated compounds VI and VII.
[4-(Triphenylmethyl)phenoxy]acetic acid (I).
Yield 6.8 g (87%), colorless powder, readily soluble in
benzene, chloroform, and acetone, poorly soluble in
aqueous alkali, and insoluble in water. IR spectrum, ν,
cm–1: 3552, 3450, 3083, 3027, 2932, 1699, 1507, 1488,
{5-[4-(Triphenylmethyl)phenoxymethyl]tetra-
benzoporphyrinato}zinc(II) (VI). Yield 0.22 g (9%),
dark green powder, readily soluble in benzene, chloro-
form, acetone, and dimethylformamide. Electronic ab-
sorption spectrum (benzene), λmax (logε): 626 (4.82),
577 (4.19), 488 (4.31), 457 (4.43), 427 (5.21), 403
(4.60). IR spectrum, ν, cm–1: 3088, 3024, 2938, 1652,
1
1262, 1159, 698. H NMR spectrum, δ, ppm: 2.99 s
(2H, CH2), 6.73–6.79 d (2H, C6H4), 7.05–7.10 d (2H,
C6H4), 7.11–7.40 m (15H, Ph) 8.10 s (1H, COOH).
Found, %: C 81.77; H 5.71. C27H22O3. Calculated, %:
C 82.21; H 5.62.
3-[4-(Triphenylmethyl)phenoxy]propionic acid
(II). Yield 5.9 g (73%), colorless powder, readily sol-
uble in benzene, chloroform, and acetone, poorly sol-
uble in aqueous alkali, and insoluble in water. IR spec-
trum, ν, cm–1: 3544, 3456, 3084, 3027, 2939, 1694,
1
1496, 1411, 701. H NMR spectrum, δ, ppm: 4.24 s
(2H, CH2), 6.84–7.10 d.d (4H, C6H4O), 7.11–7.26 m
(15H, Ph), 7.34–7.51 m (16H, C6H4), 8.12–8.22 m
(3H, meso-H). Found, %: C 80.98; H 5.12; N 5.33.
C62H40N4OZn. Calculated, %: C 80.73; H 4.37; N 6.07.
1
1501, 1495, 1263, 1151, 702. H NMR spectrum, δ,
ppm: 2.90 s (2H, 3-H), 2.97 s (2H, 2-H), 6.70–6.74 d
(2H, C6H4), 7.04–7.08 d (2H, C6H4), 7.18–7.33 m
(15H, Ph), 8.02 s (1H, COOH). Found, %: C 83.04;
H 5.88. C28H24O3. Calculated, %: C 82.33; H 5.92.
{5,15-Bis[4-(triphenylmethyl)phenoxymethyl]-
tetrabenzoporphyrinato}zinc(II) (VII). Yield 0.35 g
(11%), dark green powder, readily soluble in benzene,
chloroform, acetone, and dimethylformamide. Elec-
tronic absorption spectrum (benzene), λmax (logε): 626
(4.77), 579 (4.01), 430 (5.23), 405 (4.45). IR spectrum,
ν, cm–1: 3087, 3033, 2954, 1650, 1502, 1420, 700.
1H NMR spectrum, δ, ppm: 4.34 m (4H, CH2), 6.77–
7.09 d.d (8H, C6H4O), 7.10–7.28 m (30H, Ph), 7.34–
7.52 m (16H, C6H4), 8.31 s (2H, meso-H). Found, %:
C 83.98; H 5.01; N 4.12. C88H60N4O2Zn. Calculated,
%: C 83.17; H 4.76; N 4.41.
{5-[4-(Triphenylmethyl)phenoxy]tetrabenzopor-
phyrinato}zinc(II) (V). A mixture of 1.0 g (7 mmol)
of phthalimide (IV), 2 g (5 mmol) of acid I, and 2.5 g
(11 mmol) of zinc(II) acetate dihydrate was heated for
50 min at 310°C. The melt was cooled, ground, and
extracted with chloroform using a Soxhlet apparatus.
The solvent was distilled off, the residue was dissolved
in benzene, and the solution was applied to a column
charged with aluminum oxide (activity grade II ac-
cording to Brockmann). The column was eluted with
benzene–dioxane (20:1 by volume), and a green zone
was collected. Yield 0.37 g (24%), dark green powder,
readily soluble in benzene, chloroform, acetone, and
dimethylformamide. Electronic absorption spectrum
(benzene), λmax (logε): 630 (4.70), 581 (4.03), 487
(4.16), 460 (4.37), 434 (5.02). IR spectrum, ν, cm–1:
Porphyrins VIII–X (general procedure). Zinc
complex V–VII, 0.2 g, was dissolved in 20 ml of
chloroform, 10 ml of concentrated hydrochloric acid
was added, and the mixture was stirred for 24 h at
20°C. The organic phase was separated, washed with
water, 10% aqueous ammonia, and water again until
neutral washings (pH 7). The solvent was removed, the
residue was dissolved in benzene, and the solution was
applied to a column charged with aluminum oxide of
activity grade II according to Brockmann. The column
was eluted with chloroform to collect a green fraction.
1
3087, 3024, 1650, 1507, 1421, 1244, 703. H NMR
spectrum, δ, ppm: 7.09–6.86 d.d (4H, C6H4O), 7.28–
7.10 m (15H, Ph), 7.41–7.28 m (16H, C6H4), 8.07 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

GALANIN et al.
1030
3. Kral, V., Furuta, H., Shreder, K., Lynch, V., and
Sessler, J.L., J. Am. Chem. Soc., 1996, vol. 118, p. 1595.
4. Kobayashi, N., Bull. Chem. Soc. Jpn., 2001, vol. 75, p. 1.
5-[4-(Triphenylmethyl)phenoxy]tetrabenzopor-
phyrin (VIII). Yield 0.16 g (86%), dark green powder,
readily soluble in benzene, chloroform, acetone, and
dimethylformamide. Electronic absorption spectrum
(benzene), λmax (logε): 666 (4.33), 608 (4.43), 565
(4.05), 479 (4.22), 434 (4.98), 420 (4.91). IR spectrum,
ν, cm–1: 3244, 3044, 3025, 1644, 1506, 1420, 1236,
5. Gross, E., Ehrenberg, B., and Johnson, F., Photochem.
Photobiol., 1993, vol. 57, p. 808.
6. Brunel, M., Chaput, F., Vinogradov, S.A., Cam-
pagne, B., Canva, M., and Boilot, J.P., Chem. Phys.,
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1
694. H NMR spectrum, δ, ppm: –2.23 s (2H, NH),
6.85–7.10 d.d (4H, C6H4O), 7.11–7.26 m (15H, Ph),
7.29–7.40 m (16H, C6H4), 8.08 s (2H, 10-H, 20-H),
8.13 s (1H, 15-H). Found, %: C 86.12; H 5.22; N 6.11.
C61H40N4O. Calculated, %: C 86.71; H 4.77; N 6.63.
5-[4-(Triphenylmethyl)phenoxymethyl]tetraben-
zoporphyrin (IX). Yield 0.15 g (82%), dark green
powder, readily soluble in benzene, chloroform, ace-
tone, and dimethylformamide. Electronic absorption
spectrum (benzene), λmax (logε): 666 (4.34), 608 (4.48),
601 (4.44), 566 (4.01), 435 (5.08), 420 (4.99), 391
(4.49). IR spectrum, ν, cm–1: 3245, 3026, 2931, 1666,
9. Luk’yanets, E.A., Dashkevich, S.N., and Kobayashi, N.,
Russ. J. Gen. Chem., 1993, vol. 63, p. 985.
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vol. 45, p. 1647.
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Carrol, P.J., and Vinogradov, S.A., J. Org. Chem., 2004,
vol. 69, p. 522.
13. Finikova, O., Cheprakov, A., Beletskaja, I., and Vino-
gradov, S., Chem. Commun., 2001, p. 261.
14. Filatov, M.A., Cheprakov, A.V., and Beletskaya, I.P.,
1
1485, 1476, 703. H NMR spectrum, δ, ppm: –2.34 s
(2H, NH), 4.26 s (2H, CH2), 6.82–7.10 d.d (4H,
C6H4O), 7.12–7.26 m (15H, Ph), 7.33–7.50 m (16H,
C6H4), 8.15–8.21 m (3H, meso-H). Found, %: C 87.67;
H 5.16; N 5.88. C62H42N4O. Calculated, %: C 86.69;
H 4.93; N 6.25.
Eur. J. Org. Chem., 2007, p. 3468.
15. Filatov, M.A., Lebedev, A.Y., Vinogradov, S.A., and
5,15-Bis[4-(triphenylmethyl)phenoxymethyl]-
tetrabenzoporphyrin (X). Yield 0.17 g (88%), dark
green powder, readily soluble in benzene, chloroform,
acetone, and dimethylformamide. Electronic absorp-
tion spectrum (benzene), λmax (logε): 665 (4.34), 620
(4.41), 608 (4.41), 601 (4.39), 571 (4.11), 485 (4.17),
434 (4.97), 421 (4.94), 392 (4.47). IR spectrum, ν,
cm–1: 3244, 3033, 2945, 1652, 1513, 1422, 701.
1H NMR spectrum, δ, ppm: –2.31 s (2H, NH), 4.34 m
(4H, CH2), 6.72–7.08 d.d (8H, C6H4O), 7.12–7.27 m
(30H, Ph), 7.35–7.52 m (16H, C6H4), 8.33 s (2H,
meso-H). Found, %: C 87.11; H 5.24; N 3.99.
C88H62N4O2. Calculated, %: C 87.53; H 5.18; N 4.64.
Cheprakov, A.V., J. Org. Chem., 2008, vol. 73, p. 4175.
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17. George, R.D. and Snow, A.W., Chem. Mater., 1994,
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18. Usolt’seva, N., Bykova, V., Ananjeva, G., Zharniko-
va, N., and Kudrik, E., Mol. Cryst. Liq. Gryst., 2004,
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Gen. Chem., 2003, vol. 73, p. 1309.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009