SYNTHESIS AND PROPERTIES OF METAL PHTHALOCYANINES
1335
sium hydroxide. The solution was heated to 70 C,
170 g of potassium permanganate (KMnO4) was
added in 2.5-g portions until persistent magenta
color (test on a filter paper), and the mixture was
heated to 90 95 C and stirred for 30 min at that
temperature. Excess KMnO4 was quenched by treat-
ment with ethanol. The hot suspension was filtered,
and the precipitate was washed with hot water (2
30 ml) on a filter. The filtrate was combined with the
washings, evaporated to 1/3 of the initial volume, and
acidified with hydrochloric acid to a weakly acidic
reaction (pH 4 5). After cooling, the precipitate was
filtered off, dried at 90 C to constant weight, and
dissolved in 200 ml of water on heating to 40 50 C.
Mineral salts were precipitated by adding ethanol to
the aqueous solution. The mixture was cooled, and the
precipitate was filtered off and washed with cold
ethanol (3 20 ml). The ethanolic filtrate was evap-
orated on a water bath, and the dry residue was
treated with 1.6 mol of chlorosulfonic acid for 3 h at
130 135 C. The mixture was cooled and poured imto
a saturated solution of sodium chloride. The precip-
itate (light yellow flakes) was filtered off and dried
in a desiccator over concentrated sulfuric acid. Acid
chloride III was extracted into anhydrous acetone, the
extract was evaporated, 100 ml of water was added to
the residue, and the mixture was heated until it
became homogeneous. The solution was evaporated,
and the residue was dried to obtain 8.8 g (27%) of
compound IV as a light yellow substance, which was
soluble in water, methanol, and ethanol. Decomposi-
(2,4,16,18-Tetrasulfophthalocyaninato)cop-
per(II) (VI). A mixture of 0.5 mmol of 3,5-disulfo-
phthalic acid dipotassium salt, 0.5 mmol of phthalic
anhydride, 8 mmol of urea, 0.3 mmol of copper(I)
chloride, and 0.3 mmol of ammonium molybdate was
placed in a vertical test tube and heated for 50 min at
140 145 C, 50 min at 165 170 C, 30 min at 185
190 C, and 120 min at 200 205 C. After cooling, the
mixture was pounded and washed on a filter first with
17% and then with 5% hydrochloric acid until color-
less washings. The residue was dissolved in 0.5%
aqueous sodium hydroxide and filtered. The filtrate
was acidified with dilute hydrochloric acid, and the
precipitate of complex VI was washed with 5%
hydrochloric acid and centrifuged. The washing
centrifugation sequence was repeated several times
until evaporation of a drop of the washings (applied to
a slide) left no solid residue. The product was dried at
90 100 C. Yield 0.175 g (21%). Found, %: C 43.1;
H 1.7; Cu 6.9; S 15.0. C32H16CuN8O12S4. Calculated,
%: C 42.8; H 1.8; Cu 7.1; S 14.3.
(2,4-Disulfophthalocyaninato)copper(II) (VII)
was synthesized as described above for compound VI
from 0.25 mmol of compound IV and 0.75 mmol of
phthalic anhydride. Yield 0.176 g (24%). Found, %:
C 52.7; H 2.1; Cu 8.6; N 14.8; S 9.0. C32H16CuN8
O6S2. Calculated, %: C 52.2; H 2.2; Cu 8.7; N 15.2;
S 8.7.
[2,4,9,11,16,18,23,25-Octakis(diethylaminosul-
fonyl)phthalocyaninato]cobalt(II) (IX). Complex V
was preliminarily converted into octaammonium salt
Va by treatment with aqueous ammonia, evaporation
of the solution on a water bath, and drying of the
residue at 90 100 C. A flask equipped with a sulfuric
acid seal was charged with 1 mmol of octaammonium
salt Va, 10 ml of chlorosulfonic acid was added, and
the mixture was heated for 3 h at 140 C. The mixture
was cooled and poured into a saturated solution of
sodium chloride, cooled with ice. The precipitate was
filtered off, washed with a solution of sodium chloride
until the absence of acidic reaction (Congo Red), and
dried in a desiccator over concentrated sulfuric acid.
Octakis(sulfonyl chloride) VIII was extracted into
acetone, and 24 mmol of diethylamine was added to
the extract. The mixture was kept for 1 h at room
temperature and filtered, the solvent and excess di-
ethylamine were evaporated from the filtrate, and
compound IX was purified by column chromatog-
raphy on silica gel (Silicagel L, 40 100 m) using
1
tion point 210 C. IR spectrum, , cm : 1740 (C=O),
1050 1200, 1200 (S=O). Found, %: C 29.4; H 2.0; S
19.2. C8H6O10S2. Calculated, %: C 29.4; H 1.8;
S 19.6.
(2,4,9,11,16,18,23,25-Octasulfophthalocyanina-
to)cobalt(II) (V). Compound IV, 1 mmol, was
thoroughly mixed with 8 mmol of urea, 0.3 mmol of
cobalt(II) acetate, and 0.03 mmol of ammonium
molybdate. The mixture was transferred into a test
tube which was mounted vertically in an electric
furnace and heated under stirring for 90 min at 140
150 C, 50 min at 170 180 C, 75 min at 190 200 C,
and 120 min at 210 220 C. After cooling, the mixture
was pounded and washed with a mixture of acetic acid
with water (10:3) until weakly colored washings. The
target product was extracted into water, the extract
was evaporated on a water bath, and the dry residue
was washed with acetone until colorless washings and
dried at 90 100 C. Yield 0.045 g (15%). IR spectrum,
1
, cm : 1000 1110 [ (S=O)], 1150 1210 [ as(S=O)]. chloroform methanol (10:1) as eluent. Yield 1.52 g
Found, %: C 32.0; Hs 1.25; Co 5.0; N 9.7; S 20.8.
C32H16CoN8O24S8. Calculated, %: C 31.7; H 1.3; Co
4.8; N 9.2; S 21.1.
(92%). Found, %: C 47.2; H 4.9; Co 4.1; N 13.0;
S 15.6. C64H88CoN16O16S8. Calculated, %: C 46.5;
H 5.3; Co 3.6; N 13.6; S 15.5.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006