Tetraanthraquinonoporphyrazines: I. Substituted 2,3-dicarboxyanthraquionones

Article abstract of DOI:10.1007/s11176-005-0384-x

New procedures were developed for preparing substituted 2,3-dicarboxyanthraquinones by acylation of arenes with pyromellitic anhydride, followed by intramolecular cyclization of the products. The 2,3-dicarboxyanthraquinones prepared were further modified by oxidation, sulfonation, nitration, and reduction. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11176-005-0384-x

Russian Journal of General Chemistry, Vol. 75, No. 7, 2005, pp. 1151 1156. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005,
pp. 1215 1220.
Original Russian Text Copyright
2005 by Borisov, Maizlish, Shaposhnikov.
Tetraanthraquinonoporphyrazines:
I. Substituted 2,3-Dicarboxyanthraquionones
A. V. Borisov, V. E. Maizlish, and G. P. Shaposhnikov
Ivanovo State University of Chemical Engineering, Ivanovo, Russia
Received December 5, 2003
Abstract New procedures were developed for preparing substituted 2,3-dicarboxyanthraquinones by acyla-
tion of arenes with pyromellitic anhydride, followed by intramolecular cyclization of the products. The 2,3-di-
carboxyanthraquinones prepared were further modified by oxidation, sulfonation, nitration, and reduction.
One of the routes of chemical modification of the
phthalocyanine molecule is annelation at the benzene
rings with the formation of various porphyrazines,
structural analogs of phthalocyanine. Although numer-
ous compounds of this class have been prepared [1
6], complexes containing naphthoquinone rings, tetra-
anthraquinonoporphyrazines, remain poorly studied.
Published data on these compounds mainly concern
metal complexes of unsubstituted (I, R = H, M = VO,
Fe, Co, Zn) [7 10] and 1,4-substituted (I, R = NH2,
OCH3, OH, Cl, CH3; M = Fe, Co, Ni, Mn, Cr, Zn)
tetraanthraquinonoporphyrazines [11 15].
6
7
8
5
O
O
R
1 R
4
3
2
R
N
N
O
O
R
O
O
8
5
8
N
1
4
2
3
3
2
7
6
6
7
M N
N
4
R
1
R
5
N
N
N
2
R 1
3
4 R
O
O
8
5
7
6
I
It should be noted that the most studied are the
properties of octa-1,4-hydroxytetraanthraquinonopor-
phyrazines (tetraquinizarinoporphyrazines) [11 14],
whereas the properties of other derivatives [13] are
virtually unknown. Data on the synthesis and proper-
ties of porphyrazines substituted at other positions of
the anthraquinones fragments are scarce [15], although
these compounds are of certain interest. We believe
that the main factor impeding their study is the lack
of starting compounds for their synthesis.
To fill this gap, we made this study aimed to devel-
op procedures for preparing 2,3-dicarboxyanthraqui-
none and its 5- and 6-substituted derivatives, which
1070-3632/05/7507-1151 2005 Pleiades Publishing, Inc.

1152
BORISOV et al.
can be used as starting compounds for preparing the
corresponding tetraanthaquinonoporphyrazines.
trimethyl-substituted benzenes with aroyl chlorides
[16, 17], followed by intramolecular cyclization and
oxidation of the resulting compounds. We have devel-
oped procedures for preparing benzoyltrimellitic acids
by acylation of arenes of various structures with pyro-
mellitic dianhydride in the presence of AlCl3:
Data are available on preparation of o-dicarboxylic
acids derived from anthraquinone by acylation of
o-xylene with phthalic anhydride [8] and of di- or
R3
O
O
R1,2
O
R3
R2
HOOC
AlCl3
+
O
O
R1
HOOC
COOH
O
O
R1 = H, Cl, CH3; R2 = R3 = H; R2 =
, R1 = R3 = H; R1 = H; R2,3
=
.
The acylation was performed in the presence of a
large excess of the arene (more than 10 mol per mole
of anhydride); the reaction mixture was slowly heated
from 20 C to the boiling point. In the reactions with
biphenyl and naphthalene, we used as the reaction
medium heptane, which is inert under these conditions
and imparts sufficient mobility to the reaction mix-
ture. It should be noted that acylation yields, along
with the desired product (benzoyl-substituted trimellit-
ic acids), also the corresponding 1,3-dibenzoylben-
zene-4,6-dicarboxylic acids. The separation of the
product mixtures is difficult and was not performed in
this study. Benzoyltrimellitic acids containing an
impurity of the corresponding 1,3-dibenzoylbenzene-
4,6-dicarboxylic acids were isolated by treatment of
the reaction mixture with a hot 10% sodium carbonate
solution, followed by acidification of the alkaline
solution to pH 3 4 and filtration to isolate the precip-
itate. Acylation of toluene and chlorobenzene occurs
at the p-position relative to the substituent, but bi-
phenyl is acylated at the m-position relative to the
phenyl group, because at the o- and p-positions the
electron density on the C atoms is appreciably de-
creased relative to unsubstituted benzene [16].
The benzoyltrimellitic acids were converted into
the corresponding 2,3-dicarboxyanthraquinones by
treatment with sulfuric acid monohydrate or oleum.
R3
R3
O
O
R2
R1
R2
R1
HOOC
HOOC
HOOC
HOOC
COOH
O
R1 = H, R2 = R3 =
; R2 = R3 = H; R1 = H, Cl, CH3.
In so doing, we must take into account the possi-
bility of intramolecular cyclization of 1,3-dibenzoyl-
benzene-4,6-dicarboxylic acid impurities into the cor-
responding diquinones, which should be insoluble in
aqueous alkaline solutions. Therefore, isolation and
purification of 2,3-dicarboxyanthraquinone and its
substituted derivatives was performed by repeated dis-
solution of the reaction products in an aqueous alka-
line solution, followed by precipitation of the desired
compounds by acidification of the filtrate.
It is known that intramolecular cyclization of o-(m-
phenyl)benzoylbenzoic acid is accompanied by sulfo-
nation of the phenyl moiety at the p-position [16].
Thus, by intramolecular cyclization of 5-(m-phenyl-
benzoyl)trimellitic acid we obtained 2,3-dicarboxy-6-
(p-sulfophenyl)anthraquinone.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

TETRAANTHRAQUINONOPORPHYRAZINES: I.
1153
SO3H
O
O
HOOC
HOOC
HOOC
HOOC
COOH
O
The presence of electron-withdrawing substituents
in the arene being acylated prevents formation of
o-benzoylbenzoic acids [16]; therefore, the sulfo and
nitro groups were introduced directly into the 2,3-di-
carboxyanthraquinone prepared beforehand. In partic-
ular, 2,3-dicarboxy-6-sulfoanthraquinone was prepared
by sulfonation of 2,3-dicarboxyanthraquinone with
25% oleum:
O
O
HOOC
HOOC
HOOC
SO3H
SO3
HOOC
O
O
2,3-Dicarboxy-5-nitroanthraquinone was prepared
by nitration of 2,3-dicarboxyanthraquinone under
the conditions given in [18] for 1-nitroanthraqui-
none:
O
O
NO2
HOOC
HOOC
HOOC
HNO3, H2SO4
HOOC
O
O
Farberov et al. [17] prepared 2,3,6-tricarboxyanth-
raquinone by acylation of pseudocumene with p-toluyl
chloride, followed by oxidation of the intermediate
with nitric acid and by intramolecular cyclization with
oleum. We prepared this compound by oxidation of
2,3-dicarboxy-6-methylanthraquinone. The character-
istics of the resulting product were fully consistent
with published data [17].
O
O
CH3
HOOC
HOOC
HOOC
COOH
KMnO4
HOOC
O
O
5-Amino-2,3-dicarboxyanthraquinone was prepared
by reduction of 5-nitro-2,3-dicarboxyanthraquinone
under the conditions given in [18] for 5-nitroanthra-
quinone.
O
NH2
O
O
NO2
HOOC
HOOC
HOOC
HOOC
Na2S
O
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

1154
BORISOV et al.
A characteristic feature of the IR spectra of 2,3-di-
for 12 h. The precipitate thus formed was filtered off,
washed with hot water, and boiled for 30 40 min in
a 10% sodium carbonate solution. The solution was
filtered while hot, and the precipitate was treated as
described above 3 4 times more. The filtrates were
combined, acidified with HCl to pH 3 4, and allowed
to stand for 5 h at 10 15 C. The precipitate thus
formed was filtered off, washed with water to neutral
reaction, and dried at 80 90 C.
carboxyanthraquinone and its substituted derivatives
1
is a strong band in the range 1700 1710 cm , corre-
sponding to carboxy groups [19] and absent in the
spectrum of the unsubstituted anthraquinone.
The compositions of 2,3-dicarboxyanthraquinone
and its derivatives were confirmed by elemental anal-
ysis.
The presence of functional substituents (SO3H and
Cl) in the 2,3-dicarboxyanthraquinone molecule is
also confirmed by chemical transformations. Qualita-
tive reactions with BaCl2 and AgNO3 revealed the
presence of SO24 and Cl ions, respectively, in the
solutions after the breakdown of 2,3-dicarboxy-6-sul-
fo-, 2,3-dicarboxy-6-(p-sulfophenyl), and 2,3-dicar-
boxy-6-chloroanthraquinone with concentrated nitric
acid. The presence of the amino group in 5-amino-2,3-
dicarboxyanthraquinone was confirmed by diazotiza-
tion followed by coupling with a P-salt solution to
obtain a colored compound.
Acylation of naphthalene was performed similarly
to the acylation of biphenyl, with 10.8 g of naphtha-
lene used instead of biphenyl.
2,3-Dicarboxyanthraquinone and its substituted
derivatives (general procedure). A 20.0-ml portion
of sulfuric acid monohydrate (in the case of the chlo-
rine-substituted acylation product, of 16% oleum) was
heated to 130 C, and 5.0 g of appropriate acylation
product was added over a period of 15 min with vig-
orous stirring. Then the mixture was heated to 150 C
and kept at this temperature for 5 h. After cooling, the
mixture was poured with stirring into 200 ml of water.
The precipitate thus formed was filtered off, washed
with water to neutral reaction, and dissolved in a sodi-
um carbonate solution. After acidification with HCl, a
precipitate formed, which was filtered off and washed
with water until the absence of chloride ions in the fil-
trate. The dissolution precipitation cycle was repeated
two times, and the product was dried at 80 90 C.
Our preliminary attemts to obtain from the syn-
thesized compounds substituted tetraanthraquinono-
porphyrazines by template synthesis were successful;
their results will be reported in a separate paper.
EXPERIMENTAL
Acylation of benzene, chlorobenzene, and tolu-
ene (general procedure). A 15.3-g portion of anhyd-
rous AlCl3 was added with vigorous stirring to 10.0 g
of pyromellitic dianhydride and 25 ml of benzene or
its derivative. After stirring for 2 h, the mixture was
gradually heated on a water bath to 75 80 C over a
period of 4 h and kept at this temperature for 10 h.
After cooling, 50 ml of water was added, and the mix-
ture was allowed to stand for 30 min. The resulting
suspension was treated with an excess of a hot 10%
solution of sodium carbonate. The precipitate of alu-
minum hydroxide was filtered off. The aqueous and
organic phases of the filtrate were separated. The
aqueous layer was acidified with HCl to pH 3 4 and
allowed to stand for 5 h at 10 15 C. The precipitate
thus formed was filtered off, washed with water to
neutral reaction, and dried at 80 90 C.
2,3-Dicarboxyanthraquinone. Colorless powder
soluble in chloroform, DMF, aqueous sodium carbo-
nate solution, and hot water. Yield 3.9 g (51%), mp
282 C. Found, %: C 56.7; H 2.2; Cl 10.5. C16H7ClO6.
Calculated, %: C 58.1; H 2.1; Cl 10.7.
2,3-Dicarboxy-6-methylanthraquinone. Colorless
powder soluble in chloroform, DMF, aqueous sodium
carbonate solution, and hot water. Yield 2.8 g (41%),
mp 356 C. Found, %: C 64.7; H 3.4. C17H10O6.
Calculated, %: C 65.8; H 3.3.
2,3-Dicarboxybenzo[ ]anthraquinone.
Light
yellow needles, soluble in chloroform, DMF, aqueous
sodium carbonate solution, and hot water. Yield 3.5 g
(27%), mp 365 C. Found, %: C 68.1; H 3.0.
C20H10O6. Calculated, %: C 69.4; H 2.9.
Acylation of biphenyl. A 10.0-g portion of pyro-
mellitic dianhydride was mixed with 13.0 g of bi-
phenyl and 20 ml of heptane. The mixture was heated
to 50 C, and 15.3 g of anhydrous AlCl3 was added
with stirring. The mixture was refluxed ( 100 C) for
3 h, after which the heptane was distilled off, and the
mixture was heated for an additional 6 h at 120
130 C. After cooling, 50 ml of water and 10 ml of
concentrated HCl were added; the mixture was stirred
2,3-Dicarboxy-6-(p-sulfophenyl)anthraquinone.
A 10-ml portion of sulfuric acid monohydrate was
heated to 130 C. Then 5.0 g of the biphenyl acylation
product was added over a period of 15 min with vig-
orous stirring, and the mixture was heated to 150 C
and kept at this temperature for 5 h. After cooling, the
mixture was poured with stirring into 200 ml of water,
and the precipitate thus formed was filtered off. The
desired product was isolated and purified by the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

TETRAANTHRAQUINONOPORPHYRAZINES: I.
1155
above-described general procedure. The product is
a colorless powder soluble in chloroform, DMF, ace-
tone, aqueous sodium carbonate solution, and hot
water. Yield 6.9 g (81%), mp 267 C. Found, %: C
57.6; H 2.8; S 6.9. C22H12O9S. Calculated, %: C
58.4; H 2.7; S 7.1.
bonate solution, and water. Yield 1.5 g (50%), mp
273 C. Found, %: C 50.5; H 2.2; S 8.2. C16H8O9S.
Calculated, %: C 51.1; H 2.1; S 8.5.
2,3-Dicarboxy-5-aminoanthraquinone. A mixture
of 25 ml of water and 2 g of 2,3-dicarboxy-5-nitro-
anthraquinone was heated to 80 C, after which 5 g of
Na2S was added over a period of 15 min, the temper-
ature was raised to 95 C, and the mixture was kept at
this temperature for 3 h. Then the mixture was cooled,
and the precipitate was filtered off, washed with ice-
cold water to neutral reaction, and dried at 80 90 C.
The product is a yellow powder soluble in DMF, ben-
zene, acetone, concentrated HCl, aqueous sodium car-
bonate solution, and hot water. Yield 1.6 g (87%), mp
287 C. Found, %: C 61.0; H 3.0; N 4.6. C16H9NO6.
Calculated, %: C 61.7; H 2.9; N 4.5.
2,3-Dicarboxy-5-nitroanthraquinone. A 9.0-g por-
tion of 2,3-dicarboxyanthraquinone was added with
stirring to 92.5 ml of sulfuric acid monohydrate. The
mixture was heated to 130 140 C and stirred until the
2,3-dicarboxyanthraquinone fully dissolved (2 3 h).
The solution was cooled to 50 C, and a nitrating mix-
ture consisting of 13.5 ml of concentrated nitric acid
( 1.4) and 11.7 ml of 98% sulfuric acid was added
dropwise over a period of 30 40 min. In so doing,
the temperature rose to 80 C, and within a certain
period 2,3-dicarboxy-5-nitroanthraquinone started to
precipitate. The mixture was heated to 120 130 C,
kept at this temperature for 2 h, and cooled; the pre-
cipitate was filtered off and washed with cold water to
neutral reaction. The target product was purified simi-
larly to the above-described general procedure. The
product is a yellow powder soluble in chloroform,
DMF, aqueous sodium carbonate solution, and hot
water. Yield 7.2 g (69%), mp 292 294 C. Found, %:
C 55.3; H 2.2; N 4.0. C16H7NO8. Calculated, %: C
56.3; H 2.1; N 4.1.
ACKNOWLEDGMENTS
The study was performed within the framework
of Subprogram 203 Chemical Technologies of the
Scientific and Technical Program of the Ministry of
Education of the Russian Federation Scientific Re-
search of Higher School on Priority Lines of Science
and Engineering, grant no. 203.03.02.005.
REFERENCES
2,3,6-Tricarboxyanthraquinone. Potassium hydr-
oxide was added to 2.0 g of 2,3-dicarboxy-6-methyl-
anthraquinone in 80 ml of water to obtain a weakly
alkaline solution. The solution was heated to 90
95 C, and 3.0 g of KMnO4 was added with stiring in
0.5-g portions. Each subsequent portion was added
after decolorization of the previous portion (30
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