Sym met rically Octa-substituted Phthalocyanines
J. Chin. Chem. Soc., Vol. 48, No. 6B, 2001 1195
within 45 min. The re sult ing so lu tion was stirred for 3 hours
at 20 C.The mix ture was con cen trated un der re duced pres-
sure to dis till most of the sol vent. Then 70 mL so lu tion of
H2SO4 (2.5 M) was added dropwise into the ves sel, and the
mix ture was stirred for 30 min. The mix ture was poured into
500 mL dis tilled wa ter and fil tered; the res i due was washed
with dis tilled wa ter un til it be came neu tral. Yield: 17.5 g
tained, the fil trate was deep green.
Preparation of 3,6-ditrimethylethylphthalonitrile (3i)
In a ves sel equipped with a stir rer, a re flux con denser
and a ni tro gen in let tube, 2 g (12.5 mmol) of 3,6-dihydroxy-
phthalonitrile (1), 12 mL of dried dimethyl-formamide
(DMF) and 8.5 g (60 mmol) of an hy drous po tas sium car bon-
ate were charged, fol lowed by heat ing to 60 C in a ni tro gen
at mo sphere. 30 min later, 6.2 g (35 mmol) trimethylethyl bro-
mide was added, fol lowed by heat ing to 90~100 C and stir-
ring for 48 hours. The re sult ing mix ture was poured into 120
mL of dis tilled wa ter and fil tered; no res i due was ob tained,
the fil trate was deep green.
(73%). Mp. 229~230 C. MS (Fig. 2). Anal. C H4N2O2,
8
Calcd.: C, 60.00; H, 2.50; N, 17.50. Found: C, 59.96; H, 2.71;
N, 17.19. MS (Fig. 2).
Prep a ra tion of 3,6-dialkoxyphthalonitrile (3a~3i)21
Prep a ra tion of 3,6-di-s-butoxyphthalonitrile (3b)
In a ves sel equipped with a stir rer, a re flux con denser
and a ni tro gen in let tube, 4 g (25 mmol) of the above-obtained
phthalonitrile (1), 25 mL of dried dimethyl-formamide (DMF)
and17g(120mmol)ofanhydrouspotassiumcarbonatewere
charged, fol lowed by heat ing to 60 C in a ni tro gen at mo-
sphere. 30 min later, 9.4 g (70 mmol) s-butylbromide was
added, fol lowed by heat ing to 80 C and stir ring for 20 hours.
The re sult ing mix ture was poured into 250 mL of dis tilled
waterandfiltered; the res i due was washed with dis tilled wa-
ter un til it be came neu tral. Yield: 5.46 g (80%) Anal. (Ta ble
1). MS (Fig. 3).
Other in ter me di ates were syn the sized with 4.00 g of
3,6-dihydroxyphthalonitrile (1) in the same way, and their re-
spectiveyieldsandelementalanalysisdata are shown in Ta-
ble 1.
Preparation of palladium1,4,8,11,15,18,22,25-octa-
alkoxyphthalocyanine (4a~4j)22
Preparation of palladium1,4,8,11,15,18,22,25-octa-(s-
butoxy)phthalocyanine (4b)
In a ves sel equipped with a stir rer, a re flux con denser
and a nitrogen in let tube, 2.00 g (7.5 mmol) of 3,6-di-s-
butoxyphthalonitrile (b), 20 mL of pentanol, 1.14 g (7.5
mmol) DBU were charged, fol lowed by heat ing to 100~105
Cinanitrogenatmosphere.Atthesametemperature,0.34g
(1.9 mmol) of PdCl2 were added, fol lowed by re ac tion at
100~105 C for 20 hours. Af ter the com ple tion of the re ac-
tion, the re ac tion mix ture was cooled and in sol u ble mat ter
was re moved by fil tra tion. The fil trate was con cen trated un-
derreducedpressuretodistilloffthesolvent.Theresiduewas
purifiedbycolumnchromatographyonsilicagelusingpetro-
leum ether: eth a nol (30:1) as eluent , whereby 0.27 g of the
tar get com pound was ob tained. Yield: 11.60%,1H NMR (Ta-
ble 3). Anal. (Ta ble 2).
Prep a ra tion of 3,6-di-t-butoxyphthalonitrile (3c)
In a ves sel equipped with a stir rer, a re flux con denser
and a ni tro gen in let tube, 4 g (25 mmol) of 3,6-dihydroxy-
phthalonitrile (1), 25 mL of dried dimethyl-formamide (DMF)
and17g(120mmol)ofanhydrouspotassiumcarbonatewere
charged, fol lowed by heat ing to 60 C in a ni tro gen at mo-
sphere. 30 min later, 9.4 g (70 mmol) t-butylbromide was
added, fol lowed by heat ing to 90~100 C and stir ring for 48
hours. The re sult ing mix ture was poured into 250 mL of dis-
tilled wa ter and fil tered; the res i due was washed with dis-
tilled wa ter un til it be came neu tral. Yield: 1.05 g (15.4%)
Anal.(Table1).
Preparation of copper 1,4,8,11,15,18,22,25-octa-(s-
butoxy)phthalocyanine (4j)
Preparationof3,6-di-(2,4-dimethyl-3-pentoxy)-
phthalonitrile (3h)
In a ves sel equipped with a stir rer, a re flux con denser
and a nitrogen in let tube, 2.00 g (7.5 mmol) of 3,6-di-s-
butoxyphthalonitrile (b), 20 mL of pentanol, 1.14 g (7.5
mmol) DBU were charged, fol lowed by heat ing to 100~105
Cinanitrogenatmosphere.Atthesametemperature,0.19g
(1.9 mmol) of CuCl were added, fol lowed by re ac tion at
100~105 C for 20 hours. Af ter the com ple tion of the re ac-
tion, the re ac tion mix ture was cooled and in sol u ble mat ter
was re moved by fil tra tion. The fil trate was con cen trated un-
derreducedpressuretodistilloffthesolvent.Theresiduewas
In a ves sel equipped with a stir rer, a re flux con denser
and a ni tro gen in let tube, 2 g (12.5 mmol) of 3,6-dihydroxy-
phthalonitrile (1), 12 mL of dried dimethyl-formamide (DMF)
and8.5g(60mmol)ofanhydrouspotassiumcarbonatewere
charged, fol lowed by heat ing to 60 C in a ni tro gen at mo-
sphere. 30 min later, 6.2 g (35 mmol) 2,4-dimethyl-3-pentyl
bro mide was added, fol lowed by heat ing to 90~100 C and
stir ring for 48 hours. The re sult ing mix ture was poured into
120 mL of dis tilled wa ter and fil tered; no res i due was ob-