Synthesis and spectral properties of unsymmetrical benzoporphyrins containing phenoxy groups or quinoxaline fragments

Article abstract of DOI:10.1134/S1070428007070226

Condensation of phthalimide and 4-tert-butylphthalimide with zinc(II) acetate gave 3-(3-oxo-2,3-dihydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one and 5-tert-butyl-3-(5-tert-butyl-3-oxo-2,3-dihydro-1H-isoindol-1-ylidenemethyl) -1H-isoindol-1-one, resp

Full text of DOI:10.1134/S1070428007070226

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 7, pp. 1080–1086. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © N.E. Galanin, G.P. Shaposhnikov, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 7, pp. 1085–1091.
Synthesis and Spectral Properties
of Unsymmetrical Benzoporphyrins Containing Phenoxy
Groups or Quinoxaline Fragments
N. E. Galanin and G. P. Shaposhnikov
Ivanovo State University of Chemical Technology, pr. F. Engel’sa 7, Ivanovo, 153000 Russia
e-mail: nik-galanin@yandex.ru
Received November 15, 2006
Abstract—Condensation of phthalimide and 4-tert-butylphthalimide with zinc(II) acetate gave 3-(3-oxo-2,3-
dihydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one and 5-tert-butyl-3-(5-tert-butyl-3-oxo-2,3-dihydro-
1
H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one, respectively. Their reactions with 4-phenoxyphthalimide and
quinoxaline-2,3-dicarboximide in the presence of Zn(OAc) led to the formation of zinc complexes of cis-4,4′-
2
diphenoxytetrabenzoporphyrin and cis-di(4-tert-butylbenzo)diquinoxalinoporphyrin. The complexes were
converted into the free bases by treatment with sulfuric acid. Spectral properties of the obtained porphyrin
derivatives were studied.
DOI: 10.1134/S1070428007070226
Porphyrins and their analogs belong to a large class
of macrocyclic tetrapyrrole systems. Scientific and
practical interests in these compounds originate from
the fact that some their derivatives (hemoglobin,
myoglobin, cytochromes, chlorophyll, etc.) are very
important in the nature. Studies on the structure and
properties of natural porphyrins and their synthetic
analogs make it possible to solve some problems
related to photosynthesis, binding and activation of
molecular oxygen, and synthesis of effective models of
enzymatic systems which can find application in tech-
nics, technology, and medicine.
meso positions have been studied to a considerably
lesser extent. Monobenzoporphyrin and its metal com-
plexes (which were detected for the first time in oil
[15] and were then prepared by synthetic methods
[16, 17]) may be regarded as first representatives of
that group of compounds. The procedure proposed in
[17] is based on the Diels–Alder reaction of protopor-
phyrin IX dimethyl ester with dimethyl acetylenedi-
carboxylate, followed by elimination of the angular
methyl group from the adduct. However, this proce-
dure has a limited applicability; therefore, Sapunov
et al. [18] later proposed to obtain unsymmetrical ben-
zoporphyrins by joint condensation of imides derived
from two different ortho-dicarboxylic acids [18].
A drawback of this method is that the reaction gives
a mixture of porphyrins which are often difficult to
separate on a preparative scale. The most reasonable
procedure for the synthesis of unsymmetrical benzo-
porphyrins is likely to be stepwise condensation
[12–14, 19] which was applied by us to obtain (cis-
Benzo-fused derivatives constitute a large group of
synthetic porphyrin analogs. Among these, tetrabenzo-
porphyrin (I) and its metal complexes [1–5], as well as
various meso-aryl-substituted tetrabenzoporphyrins
[
6–11], were studied most thoroughly. The available
information on unsymmetrical tetrabenzoporphyrins is
concerned mainly with meso-aryl-substituted deriva-
tives [12–14], while those having no substituents in the
Scheme 1.
OMe
N
O
PhO
CN
CN
PhO
PhO
+
MeONa, MeOH
H , H O
2
NH
NH
O
VII
VIII
V
1080

SYNTHESIS AND SPECTRAL PROPERTIES OF UNSYMMETRICAL BENZOPORPHYRINS
1081
Scheme 2.
OPh
H
N
O
N
PhO
N
N
N
N
O
O
CH (COOH) , Zn(OAc)
2 2 2
+
NH
Zn
O
OPh
VI
V
II
4
,4′-diphenoxytetrabenzoporphyrinato)zinc(II) (II) and
hydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-
one (IX) which was prepared by analogy with com-
pound VI, i.e., by condensation of 4-tert-butylphthal-
imide with zinc(II) acetate (Scheme 3).
[
cis-di(4-tert-butylbenzo)diquinoxalinoporphyrinato]-
zinc(II) (III). Complexes II and III are characterized
by a large dipole moment, and they attract interest
from both theoretical and practical viewpoints. It is
known that structurally related unsymmetrical por-
phyrazines containing both electron-donor and elec-
tron-withdrawing substituents and possessing a high
dipole moment are very promising for use in various
fields of science and technics [20–22].
Scheme 3.
H
N
N
O
O
O
t-Bu
Zn(OAc)2
NH
The starting compounds for the synthesis of por-
phyrin II were phthalimide (IV) and 4-phenoxyphthal-
imide (V). By condensation of phthalimide (IV) with
zinc(II) acetate according to the procedure reported in
O
Bu-t t-Bu
IX
Here, 4-tert-butylphthalimide was selected taking
into account that the presence of tert-butyl groups in
porphyrin molecules endows them with a high solubil-
ity in organic solvents. Furthermore, tert-butyl groups
do not affect the electronic absorption spectra of por-
phyrins to a considerable extent [23]. The structure of
compound IX was confirmed by elemental analysis
and electronic, IR, and H NMR spectroscopy. The
electronic absorption spectrum of IX resembles that of
compound VI [14]. Bis-isoindole IX showed in the
[
14] we obtained 3-(3-oxo-2,3-dihydro-1H-isoindol-1-
ylidenemethyl)-1H-isoindol-1-one (VI). The second
component, 4-phenoxyphthalimide (V), was prepared
by the transformation of 4-phenoxyphthalonitrile (VII)
into 1-alkoxy-3-imino derivative VIII and hydrolysis
of the latter to imide V by treatment with dilute HNO3
(
Scheme 1).
1
The structure of compound V was confirmed by the
1
analytical and spectral data. The H NMR spectrum of
V contained a singlet at δ 10.46 ppm from the NH pro-
ton, a multiplet at δ 7.94–7.68 ppm from three aromat-
ic protons in the isoindole fragment, and a multiplet at
δ 7.35–7.15 ppm from five protons of the phenoxy
group.
1
H NMR spectrum a singlet at δ 10.72 ppm from the
NH proton, signals from six protons of the isoindole
fragments appeared in the region δ 7.44–7.21 ppm,
a singlet at δ 6.48 ppm was assigned to resonance of
the CH proton, and protons in the tert-butyl groups
gave an upfield singlet at δ 1.98 ppm.
By heating compound VI with excess imide V and
malonic acid in the presence of zinc acetate we ob-
tained cis-4,4′-diphenoxytetrabenzoporphyrin complex
II (Scheme 2). Apart from complex II, the reaction
also gave zinc complexes of compound I and tetra-
Scheme 4.
O
N
N
COOH
COOH
N
N
(
4-phenoxybenzo)porphyrin. Complex II was isolated
NH
3
NH
from the reaction mixture by column chromatography.
–2H O
2
In the synthesis of zinc complex III, the first com-
ponent was 5-tert-butyl-3-(5-tert-butyl-3-oxo-2,3-di-
O
X
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 7 2007

1
082
GALANIN, SHAPOSHNIKOV
Scheme 5.
t-Bu
Bu-t
N
N
N
CH (COOH) , Zn(OAc)
2
2
2
IX
+
X
Zn
N
N
N
N
N
III
The second component was quinoxaline-2,3-dicar-
boximide (X). It was prepared by passing dry NH3
through molten quinoxaline-2,3-dicarboxylic acid at
50°C over a period of 10 min (Scheme 4). [cis-Di(4-
(III) was synthesized by reaction of dimer IX with
excess imide X and malonic acid in the presence of
zinc(II) acetate (Scheme 5). As in the synthesis of
complex II, a mixture of zinc complexes of tetra-
(4-tert-butylbenzo)porphyrin and tetraquinoxalinopor-
phyrin and complex III was formed. The latter was
isolated from the product mixture by column chroma-
tography.
2
tert-butylbenzo)diquinoxalinoporphyrinato]zinc(II)
D
1
0
0
0
0
.6
2
Insofar as (tetrabenzoporphyrinato)zinc(II) and
(
tetraquinoxalinoporphyrinato)zinc(II) are poorly sol-
.4
.2
.0
uble in most organic solvents, in both cases only
a mixture of two porphyrin complexes was separated
by chromatography. Molecules II and III are more
polar than zinc complexes of tetra(4-tert-butylbenzo)-
porphyrin and tetra(4-phenoxybenzo)porphyrin, and
they contain two rather than four solubilizing substit-
uents; therefore, their chromatographic mobility is con-
siderably lower than that of the corresponding tetra-
substituted compounds, and their isolation involves no
difficulties. Reprecipitation of complexes II and III
from concentrated sulfuric acid gave metal-free cis-
4
00
500
600
700
λ, nm
Fig. 1. Electronic absorption spectra of (1) zinc complex II
and (2) free ligand XI in chloroform.
4
,4′-diphenoxytetrabenzoporphyrin (XI) and cis-di-
D
1
2
quinoxalinodi(4-tert-butylbenzo)porphyrin (XII)
which were purified by column chromatography. Com-
plexes II and III and ligands XI and XII are dark
green crystalline substances that are readily soluble in
a number of organic solvents. Their structure was
proved by the analytical data and electronic and
0
0
0
.8
1
.4
.0
H NMR spectra.
The electronic absorption spectra of complexes II
and III are shown in Figs. 1 and 2; the spectral patterns
are typical of tetrabenzoporphyrin metal complexes:
a strong Soret band and less intense Q band are pres-
ent. However, unsymmetrical structure of the porphy-
rin macroring strongly affects the character and posi-
tion of the main absorption bands. In addition, the
spectral properties largely depend on the nature of
4
00
500
600
700
λ, nm
Fig. 2. Electronic absorption spectra of (1) zinc complex III
and (2) free ligand XII in chloroform.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 7 2007

SYNTHESIS AND SPECTRAL PROPERTIES OF UNSYMMETRICAL BENZOPORPHYRINS
1083
(a)
molecular fragments. The Soret band in the spectrum
of complex II (Fig. 1) is insignificantly displaced (by
2
nm) to the blue region relative to the corresponding
band in the spectrum of (tetrabenzoporphyrinato)-
zinc(II) [5]. On the other hand, the Soret band was
strongly broadened, which may be due to superposition
of intramolecular charge-transfer band and the pres-
ence of isomers with different positions of the phenoxy
groups, whose spectral parameters may be different.
The Q band is slightly displaced red (Δλ = 3 nm) due
to substituent effects and polarization of the molecule.
The spectrum of complex II also contained a weak ab-
sorption band at λ 646 nm which was not observed in
the spectrum of (tetrabenzoporphyrinato)zinc(II). We
believe that this band also originates from intramolec-
ular charge transfer.
(
b)
The electronic absorption spectrum of complex III
Fig. 2) is more similar to the spectrum of (tetrabenzo-
(
porphyrinato)zinc(II) [5]. A small red shift of the Q
band (Δλ = 5 nm) should be noted, while the position
of the Soret band is the same as in the spectrum of (tet-
rabenzoporphyrinato)zinc(II). A weak charge-transfer
band at λ 492 nm was also present in the spectrum of
complex III.
More considerable differences were observed in the
Fig. 3. Structures of molecules (a) XI and (b) XII according
spectra of metal-free compounds XI and XII (Figs. 1,
to AM1 calculations.
2
). As in the spectrum of tetrabenzoporphyrin, the
Soret band of XI and XII is split into two components,
but the splitting is less pronounced, presumably due to
reduced molecular orbital symmetry. The bands are
broadened and displaced toward longer wavelengths.
The shift is insignificant for porphyrin XI (Fig. 1): it
amounts to 4–5 nm relative to tetrabenzoporphyrin
was strongly broadened, and its short-wave component
was displaced to longer wavelengths. In the spectrum
of tetra(4-tert-butylbenzo)porphyrin [23], the maxi-
mum of the short-wave component of the Q band is
located at λ 607 nm, whereas the corresponding maxi-
mum in the spectrum of XII appears at λ 649 nm.
Presumably, this is the result of strong polarization of
molecule XII and extension of the conjugation system
due to fusion of pyrazine rings.
[
24]; while in the spectrum of compound XII (Fig. 2)
the difference in the position of the Soret band reaches
5–47 nm. These findings may be rationalized in terms
4
of a larger dipole moment of molecule XII compared
to XI and the effect of additional ring fusion. In the
spectrum of XI we observed a shoulder at λ 476 nm,
which is likely to correspond to charge transfer.
1
The H NMR spectrum of complex II contains
three groups of signals. Four meso-protons resonate as
three singlets in the most downfield region, at δ 10.22,
.81, and 9.64 ppm; these protons are magnetically
9
As concerns absorption in the Q-region, porphyrin
XI displayed a charge-transfer band with its maximum
at λ 713 nm in addition to two absorption bands typical
of all tetrabenzoporphyrins. Analogous bands are also
observed in the spectra of unsymmetrical porphyra-
zines characterized by a high dipole moment [25].
A charge-transfer band (λmax 714 nm) was also dis-
tinguished in the electronic absorption spectrum of
compound XII. The Q band in the spectrum of XII
nonequivalent due to unsymmetrical structure of mole-
cule II. A multiplet in the region δ 7.85–7.65 ppm
corresponds to resonance of 14 protons in the isoindole
fragments, and 10 protons in the phenoxy groups give
a multiplet at δ 7.43–7.18 ppm. The spectral pattern
becomes more complicated in going to complex III.
The meso-protons give a multiplet at δ 11.33–
11.11 ppm. Signals from eight protons in the benzene
rings appear as a multiplet in the δ region 10.05–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 7 2007

1
9
084
GALANIN, SHAPOSHNIKOV
.76 ppm, and protons in the isoindole fragments
(IX). A mixture of 3 g of 4-tert-butylphthalimide and
6 g of zinc(II) acetate dihydrate was heated to 250°C
and was kept for 20 min at that temperature. The mix-
ture was cooled, ground, washed in succession with
a 10% solution of sodium hydroxide, water, 10% hy-
drochloric acid, and water again (to pH 7), and dried.
The product (a red powder) was dissolved in chloro-
form, and the solution was subjected to column chro-
matography on aluminum oxide (activity grade II)
using chloroform as eluent. Yield 0.8 g (29%), dark red
powder, mp 246–247°C. Compound IX is readily
soluble in acetone, pyridine, DMF, acetic acid, and
chloroform and insoluble in water. Electronic absorp-
resonated as a six-proton multiplet at δ 8.48–8.35 ppm.
In the upfield region, a singlet at δ 1.84 ppm is ob-
served due to 18 protons in the tert-butyl groups.
Metal-free porphyrins XI and XII showed in the
H NMR spectra upfield signals from the intracyclic
1
NH protons. In the spectrum of XI, the NH signal is
a broadened singlet at δ –2.94 ppm, and compound XII
gives two singlets at δ –1.9 and –2.2 ppm owing to
unsymmetrical structure of molecule XII and probably
distortion of planar structure due to high dipole mo-
ment. We performed AM1 semiempirical quantum-
chemical calculations of the structure of molecules XI
and XII (Fig. 3). It is seen that the macroring in
molecule XI is planar and that molecule XII strongly
deviates from planar structure; obviously, this factor
largely determines the spectral properties of the latter.
tion spectrum (CHCl ), λmax, nm: 358, 516, 552. IR
3
–
1
spectrum, ν, cm : 3274 (N–H), 2970 (C–H), 1720
1
(
(
C=O). H NMR spectrum (CDCl ), δ, ppm: 10.72 s
3
1H), 7.44–7.21 m (6H), 6.48 s (1H), 1.98 s (18H).
Thus we have synthesized unsymmetrical benzo-
porphyrins containing electron-donor or electron-with-
drawing substituents and examined their spectral
properties.
Found, %: C 78.20; H 7.95; N 6.20. C25
culated, %: C 77.68; H 6.78; N 6.51.
H N O . Cal-
26 2 2
Quinoxaline-2,3-dicarboximide (X). Dry gaseous
ammonia was passed over a period of 10 min through
5
2
1
g of quinoxaline-2,3-dicarboxylic acid heated to
50°C. The melt was cooled, ground, and dissolved in
00 ml of a 10% solution of sodium carbonate, and the
EXPERIMENTAL
The electronic absorption spectra were measured on
a Hitachi UV-2000 spectrophotometer. The IR spectra
solution was extracted with diethyl ether (3×50 ml).
The extracts were combined and evaporated. Yield
3.6 g (79%), white powder. The product is readily
soluble in water, dilute acids and alkalies, DMF, and
–1
(
3
400–4000 cm ) were recorded in KBr on an Avatar
1
60 FT-IR spectrometer. The H NMR spectra were
obtained on a Bruker WM-400 instrument (400 MHz)
using HMDS as internal reference.
acetone. Found, %: N 20.80. C10
H N O . Calculated,
5 3 2
%
: N 21.10.
4
-Phenoxyphthalonitrile (VII) was synthesized
2
(3) 2(3)
according to the procedure reported in [26], and 4-tert-
butylphthalimide was prepared as described in [27].
(
2
,7 -Diphenoxytetrabenzoporphyrinato)-
zinc(II) (II). A mixture of 0.3 g of compound VI, 0.6 g
of imide V, 1 g of malonic acid, and 0.5 g of zinc(II)
acetate dihydrate was heated for 30 min at 250°C and
for 30 min at 320°C. The melt was cooled, ground, and
dissolved in chloroform, and the solution was sub-
jected to column chromatography on aluminum oxide
of activity grade II using chloroform as eluent. The
second green fraction was collected, and the solvent
was removed. Yield 0.11 g (13%), dark green powder.
The complex is readily soluble in benzene, chloroform,
DMSO, and DMF, and insoluble in water. Electronic
absorption spectrum (CHCl ), λ , nm (D/Dmax):
4
-Phenoxyphthalimide (V). 4-Phenoxyphthalo-
nitrile (VII), 3 g, was added to a solution of sodium
methoxide prepared from 0.2 g of metallic sodium and
0 ml of methanol, and the mixture was stirred for 2 h
at 20°C. The resulting solution of 3-methoxy-1H-iso-
indol-1-imine (VIII) was added to 200 ml of 5% nitric
acid. After 30 min, the precipitate was filtered off,
washed with water, and dried. Yield 3.4 g (93%), white
powder, mp 112–113°C. The product is readily soluble
in DMF, DMSO, and acetone and sparingly soluble in
hot water. IR spectrum, ν, cm : 3200 (N–H), 2936
C–H), 1762 (C=O), 1043 (C–O). H NMR spectrum
CDCl ), δ, ppm: 10.46 s (1H), 7.94–7.68 m (3H),
.35–7.15 m (5H). Found, %: N 5.7. C H NO . Cal-
5
–
1
3
max
1
1
(
(
7
6
46 sh, 628 (0.37), 578 (0.14), 427 (1.00). H NMR
3
spectrum (DMSO-d ), δ, ppm: 10.22 s (1H), 9.81 s
6
14 9 3
(
(
2H), 9.64 s (1H), 7.85–7.65 m (14H), 7.43–7.18 m
10H). Found, %: C 77.20; H 3.85; N 7.15.
culated, %: N 5.8.
5
-tert-Butyl-3-(5-tert-butyl-3-oxo-2,3-dihydro-
C H N O Zn. Calculated, %: C 76.04; H 3.72;
48 28 4 2
1
H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one
N 7.39.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 7 2007

SYNTHESIS AND SPECTRAL PROPERTIES OF UNSYMMETRICAL BENZOPORPHYRINS
1085
2
(3) 2(3)
2
,7 -Diphenoxytetrabenzoporphyrin (XI).
powder readily soluble in benzene, chloroform,
A 0.05-g portion of complex II was dissolved in 10 ml
of concentrated sulfuric acid, and the solution was kept
for 30 min at 20°C and poured into 50 ml of water. The
precipitate was filtered off, washed in succession with
water, 10% aqueous ammonia, and water again (to
pH 7), dried, and dissolved in chloroform, and the
solution was subjected to column chromatography on
alumi-num oxide of activity grade II using chloroform
as eluent. A green fraction was collected and evaporat-
ed. Yield 0.03 g (70%), dark green powder. The prod-
uct is readily soluble in benzene, chloroform, DMSO,
and DMF and insoluble in water. Electronic absorption
DMSO, and DMF and insoluble in water. Electronic
absorption spectrum (CHCl ), λmax, nm (D/Dmax): 714
3
(0.15), 666 (0.26), 649 (0.25), 476 (1.00), 465 (0.90),
1
435 sh. H NMR spectrum (DMSO-d ), δ, ppm: 11.41–
6
11.28 m (4H), 9.98–9.75 m (8H), 8.31–8.18 m (6H),
1.86 s (18H), –1.9 s (1H), –2.2 s (1H). Found, %:
C 81.25; H 4.46; N 14.88. C H N . Calculated, %:
4
8
28
8
C 80.43; H 3.94; N 15.63.
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1
2
. Helberger, J.H., Rubai, A., and Helver, D.E., Justus
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3
1
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(
0.30), 609 (0.32), 434 (1.00), 419 (0.93). H NMR
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6
3
4
. Remy, D.E., Tetrahedron Lett., 1983, vol. 24, p. 1451.
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(
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48
30
4
2
Calculated, %: C 82.98; H 4.35; N 8.06.
2
(3) 2(3)
(
2
,7 -Di-tert-butyldibenzo[a,g]diquinoxalino-
5
6
7
. Kopranenkov, V.N., Makarova, E.A., and Luk’ya-
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[
2,3-l:2′,3′-q]porphyrinato)zinc(II) (III). A mixture
of 0.3 g of compound IX, 0.5 g of imide X, 1 g of
malonic acid, and 0.5 g of zinc(II) acetate dihydrate
was heated for 1 h at 260°C and for 30 min at 330°C.
The melt was cooled, ground, and dissolved in ben-
zene, and the solution was applied to a column charged
with aluminum oxide of activity grade II. The column
was eluted with benzene to collect the second green
fraction. Removal of the solvent gave 0.09 g (15%) of
complex III as a dark green powder readily soluble in
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,
3
1
0. Finikova, O., Cheprakov, A., Beletskaja, I., and Vino-
nm (D/Dmax): 631 (0.40), 584 (0.12), 492 (0.13), 457
gradov, S., Chem. Commun., 2001, p. 261.
1
(
0.23), 429 (1.00). H NMR spectrum (DMSO-d ), δ,
6
11. Finikova, O., Cheprakov, A., Carroll, P., Dalosto, S., and
ppm: 11.33–11.11 m (4H), 10.05–9.76 m (8H), 8.48–
.35 m (6H), 1.84 s (18H). Found, %: C 73.30; H 5.35;
N 13.95. C H N Zn. Calculated, %: C 72.96; H 4.59;
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8
1
1
1
1
1
1
1
2. Galanin, N.E., Kudrik, E.V., and Shaposhnikov, G.P.,
48
26
8
Russ. J. Gen. Chem., 2000, vol. 70, p. 1292.
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0
.025 g (76%) of compound XII as a dark green
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