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BORISOV et al.
the mixture was heated to 150°C and kept for 5 h at
that temperature. The mixture was then poured into
200 ml of water under stirring, the resulting suspension
was filtered, the precipitate was washed with water
until neutral washings and dissolved in 100 ml of 10%
aqueous sodium carbonate. The solution was filtered,
the filtrate was acidified with hydrochloric acid to pH
4, and the precipitate was filtered off and washed with
water until the washings no longer contained chloride
ions. This procedure was repeated twice, and the
product was dried at 100°C.
5,8-Dihydroxy-9,10-dioxo-9,10-dihydroanthracene-
2,3-dicarboxylic acid (IV). A 200-ml three-necked
flask equipped with a stirrer was charged with a
ground mixture of 10.1 g (0.092 mol) of hydroquinone,
10.0 g (0.046 mol) of pyromellitic dianhydride, and
14.5 g (0.23 mol) of boric acid, 70 ml of 100% sulfuric
acid was added, and the mixture was thoroughly stirred
and heated for 3 h at 140–150°C. The mixture was
then heated for 3 h at 160–170°C and poured while hot
into 400 ml of water under vigorous stirring. The
mixture was heated to the boiling point and filtered
while hot. The precipitate was treated once more with
400 ml of boiling water, filtered off, treated with 20 ml
of a 1% solution of sodium hydroxide, and filtered off.
The procedure was repeated until the product no longer
dissolved. The filtrates were combined and neutralized
with hydrochloric acid, and the precipitate was filtered
off and washed with water until neutral washings. The
product was dried at 80°C and extracted with glacial
acetic acid in a Soxhlet apparatus over a period of
20 h. The extract was evaporated, and the residue was
dried at 100°C.
The mixture was cooled and poured onto ice, and the
precipitate was filtered off, washed with 5% aqueous
HCl until the absence of sulfate ions, and dried at 100°C.
The yields, melting points, and elemental analyses
of compounds VI–X are given in Table 2.
Metal complexes of substituted tetraanthra-
quinonoporphyrazines (general procedures). a. A
quartz ampule was charged with a mixture of 0.60
mmol of the corresponding substituted 2,3-dicarboxy-
anthraquinone, 4.00 mmol (0.24 g) of urea, 0.18 mmol
of copper(II) (0.036 g) or cobalt(II) acetate (0.038 g),
0.40 mmol (0.02 g) of ammonium chloride, and 0.01
mmol (0.002 g) of ammonium molybdate. The mixture
was slowly (over a period of 1 h) heated to 180°C,
kept for 3 h at that temperature, cooled, ground, trans-
ferred onto a Schott filter, and washed with 5%
aqueous HCl and water until evaporation of a drop of
the filtrate on a glass plate left no solid residue. The
product was dried at 100°C, reprecipitated from
concentrated sulfuric acid, extracted with acetone in a
Soxhlet apparatus over a period of 10 h, and dried at
100°C.
b. A mixture of 0.20 g of thoroughly ground com-
plex XI–XIII and 10 ml of 1% aqueous sodium
hydroxide was heated for 40–50 min on a water bath.
The solution was acidified with hydrochloric acid to
pH 3–4, and the precipitate was filtered off, washed
with water until the washings no longer contained
chloride ions, and dried at 100°C.
The yields, elemental analyses, and electronic
absorption spectra of complexes I–III and XI–XIII are
given in Table 3.
6-Hydroxy-9,10-dioxo-9,10-dihydroanthracene-
2,3-dicarboxylic acid (VIII) and 5,8-dihydroxy-
9,10-dioxo-9,10-dihydroanthracene-2,3-dicar-
boxylic acid (IV) (general procedure). A mixture of
0.20 g of methoxy derivative VI or VII and 10 ml of
1% aqueous sodium hydroxide was ground and heated
for 40–50 min on a water bath. The mixture was
acidified with hydrochloric acid to pH 3–4, and the
precipitate was filtered off, washed with water until the
washings no longer contained chloride ions, and dried
at 100°C.
REFERENCES
1. Borisov, A.V., Maizlish, V.E., and Shaposhnikov, G.P.,
Russ. J. Gen. Chem., 2005, vol. 75, no. 10, p. 1579.
2. The Porphyrin Handbook, Kadish, K.M., Smith, K.M.,
and Guilard, R., Eds., San Diego: Academic, 2003,
vol. 15.
3. Maizlish, V.E. and Shaposhnikov, G.P., Uspekhi khimii
porfirinov (Advances in the Chemistry of Porphyrins),
St. Petersburg: Nauch.-Issled. Inst. Khimii Sankt-Peterb.
Gos. Univ., 2004, vol. 4, p. 327.
5,8-Dimethoxy-9,10-dioxo-6-sulfo-9,10-dihydro-
anthracene-2,3-dicarboxylic acid (X). 5,8-Di-
methoxy-9,10-dioxo-9,10-dihydroanthracene-2,3-dicar-
boxylic acid (VII), 2.00 g (0.07 mol), was added under
stirring to 16 ml of 20% oleum heated to 120–140°C,
and the mixture was kept for 6 h at that temperature.
4. Simon, J. and Andre, J.-J., Molecular Semiconductors.
Photoelectrical Properties and Solar Cells, Berlin:
Springer, 1985.
5. Zhidkie crystally: diskoticheskie mezogeny (Liquid
Crystals: Discotic Mesogens), Usol’tseva, N.V., Ed.,
Ivanovo: Ivanov. Gos. Univ., 2004.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 10 2012