216 J. Chin. Chem. Soc., Vol. 54, No. 1, 2007
Xu et al.
they lose the 4(C16H25) at the first step.
3-(2,5-Ditertbutylphenoxy)phthalonitrile (3d)
Consequently, the phthalocyanine thermal stability
can be adjusted by modification of the substituents on the
peripheric benzene rings of the phthalocyanine dyes. The
phthalocyanine dyes 4d and 4e, among the synthesized
phthalocyanines, can be considered to be excellent poten-
tial candidates for CD-R dyes.
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, 5 g of 3-nitrophthalnitrile (1), 20
mL of dried DMF and 15 g 2,5-ditertbutylphenol (2d), and
15 g of anhydrous potassium carbonate were charged and
followed by heating to 80 °C and stirring for 2 hours in a ni-
trogen atmosphere. The resulting mixture is poured into
400 mL of distilled water and filtered. The residue was
washed with distilled water until it became neutral, and
then it was recrystallized in methanol. Yield: 3.4 g (35%),
m.p. 143-144 °C.
PREPARATION
Intermediates Synthesis12
3-Phenoxyphthalonitrile (3a)
3-(2,4-Ditertpentylphenoxy)phthalonitrile (3e)
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, 5 g of 3-nitrophthalnitrile (1), 20
mL of dried DMF and 15 g 2,4-ditertpentylphenol (2e), and
15 g of anhydrous potassium carbonate were charged and
followed by heating to 80 °C and stirring for 2 hours in a ni-
trogen atmosphere. The resulting mixture was poured into
400 mL of distilled water and filtered. The residue was
washed with distilled water until it became neutral, and
then it was recrystallized in methanol. Yield: 9.9 g (94%),
m.p. 83-85 °C.
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, 5 g of 3-nitrophthalnitrile (1), 20
mL of dried N,N-dimethylformamide (DMF) and 6 g phe-
nol (2a), 16 g of anhydrous potassium carbonate were
charged and followed by heating to 80 °C and stirring for 2
hours in a nitrogen atmosphere. The resulting mixture is
poured into 400 mL of distilled water and filtered. The
residue was washed with distilled water until it became
neutral, and then it was recrystallized in methanol. Yield: 4
g (63%), m.p. 100~102 °C.
3-(2,4-Dichlorophenoxy)phthalonitrile (3b)
Phthalocyanine Synthesis13
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, 5 g of 3-nitrophthalnitrile (1), 20
mL of dried DMF and 6 g 2,4-dichlorophenol (2b), 16 g of
anhydrous potassium carbonate were charged and followed
by heating to 80 °C and stirring for 4 hours in a nitrogen at-
mosphere. The resulting mixture was poured into 400 mL
of distilled water and filtered. The residue was washed with
distilled water until it became neutral, and then it was re-
crystallized in methanol. Yield: 8.2 g (98%),m.p. 137~139
°C.
Palladium 1,8,15,22-tetra-phenoxyphthalocyanine (4a)
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, a mixture of 2.0 g of 3-phenoxy-
phthalonitrile (3a), 0.4 g of PdCl2, 1.7 g of 1,8-diazabicy-
clo[5.4.0]-7-undecene (DBU) and 30 mL of n-pentanol is
heated under reflux in a nitrogen atmosphere for 5 hours.
Methanol is then added to the resulting reaction solution in
order to precipitate crystals, and the latter were collected by
suction filtration. The precipitation is purified through a
column (silica gel/chloroform), and then 0.5 g (yield 20%)
of a phthalocyanine compound (4a) is obtained.
3-(2,6-Dibromo-4-methylphenoxy)phthalonitrile (3c)
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, 5 g of 3-nitrophthalnitrile (1), 20
mL of dried DMF and 15 g 2,6-dibromo-4-methylphenol
(2c), and 16 g of anhydrous potassium carbonate were
charged and followed by heating to 80 °C and stirring for 2
hours in a nitrogen atmosphere. The resulting mixture was
poured into 400 mL of distilled water and filtered. The resi-
due was washed with distilled water until it became neutral,
and then it was recrystallized in methanol. Yield: 8.7 g
(77%), m.p. 171-173 °C.
Palladium 1,8,15,22-tetra(2,4-dichlorophenoxy)-
phthalocyanine (4b)
In a vessel equipped with a stirrer, a reflux condenser
and a nitrogen inlet tube, a mixture of 2.0 g of 3-(2,4-di-
chlorophenoxy)phthalonitrile (3b), 0.3 g of PdCl2, 1.2 g of
DBU and 15 mL of n-pentanol is heated under reflux in a
nitrogen atmosphere for 5 hours. Methyl alcohol is then
added to the resulting reaction solution in order to precipi-
tate crystals, and the latter were collected by suction filtra-
tion. The precipitation is purified through a column (silica