1150 H. SATO ET AL.
and bromoalkane (Wako). The dicyano derivatives
(7) could be prepared from commercially available
4,5-dichlorophthalonitrile (Tokyo Kasei) and the phenol
derivatives (6). The target phthalocyanine compounds
(m-CnOPhO)8PcM (1–5) could be synthesized from the
dicyano derivatives (7). The detailed synthetic procedures
are described below for the representative hexadecyloxy
derivatives, (m-C16OPhO)8PcM (M = Co, Ni, Cu, Zn and
H2; 1e, 2e, 3e, 4e and 5e).
chromatography (silica gel, chloroform, Rf = 1.00) to
obtain 0.102 g of green crystal. Yield 50.4%. MALDI-
TOF mass data: see Table S1. UV-vis spectral data: see
Table S2.
2,3,9,10,16,17,23,24-octakis(3-hexadecyloxy-phe-
noxy)phthalocyaninato nickel(II) (2e). A mixture of
4,5-bis(3-hexadecyloxyphenoxy)-1,2-dicyanobenzene
(7e) (0.491 g, 0.619 mmol), 1-hexanol (5 mL), DBU
(2 drops) and NiCl2 (20.0 mg, 1.55 × 10-1 mmol) was
refluxed for 16h. The reaction mixture was poured
into methanol to precipitate the target compound. The
methanolic layer was removed by filtration and then the
resulting precipitate was washed with ethanol, acetone
and ethyl acetate, respectively. The residue was purified
by recrystallization from ethyl acetate and then column
chromatography (silica gel, chloroform, Rf = 1.00) to
obtain 0.410 g of green crystal. Yield 82.1%. MALDI-
TOF mass data: see Table S1. UV-vis spectral data: see
Table S2.
2,3,9,10,16,17,23,24-octakis(3-hexadecyloxy-phe-
noxy)phthalocyaninato copper(II) (3e). A mixture of
4,5-bis(3-hexadecyloxyphenoxy)-1,2-dicyanobenzene
(7e) (0.250 g, 0.320 mmol), 1-hexanol (3 mL), DBU
(8 drops) and CuCl2 (15.0 mg, 0.850 × 10-1 mmol) was
refluxed for 16 h. The reaction mixture was poured
into methanol to precipitate the target compound. The
methanolic layer was removed by filtration and then the
resulting precipitate was washed with ethanol, acetone
and ethyl acetate, respectively. The residue was purified
by recrystallization from ethyl acetate and then column
chromatography (silica gel, chloroform, Rf = 1.00) to
obtain 86.4 mg of green crystal. Yield 33.4%. MALDI-
TOF mass data: see Table S1. UV-vis spectral data: see
Table S2.
2,3,9,10,16,17,23,24-octakis(3-hexadecyloxy-phe-
noxy)phthalocyaninato zinc(II) (4e). A mixture of
4,5-bis(3-hexadecyloxyphenoxy)-1,2-dicyanobenzene
(7e) (0.500 g, 0.634 mmol), 1-octanol (5 mL), DBU
(4 drops) and Zn(OAc)2·2H2O (34.6 mg, 0.158 mmol)
was refluxed for 24 h. The reaction mixture was poured
into methanol to precipitate the target compound. The
methanolic layer was removed by filtration and then
the resulting precipitate was washed with ethanol and
acetone, respectively. The collected solid was purified
by solid-liquid extraction with acetone. The residue was
further purified by column chromatography (silica gel,
CHCl3: tetrahydrofuran = 99:1, Rf = 0.55) to obtain 65.5
mg of green crystal. Yield 12.8%. MALDI-TOF mass
data: see Table S1. UV-vis spectral data: see Table S2.
2,3,9,10,16,17,23,24-octakis(3-hexadecyloxy-phe-
noxy)phthalocyanine (5e). A mixture of 4,5-bis(3-
hexadecyloxyphenoxy)-1,2-dicyanobenzene(7e)(0.400g,
0.505 mmol), 1-hexanol (5 mL) and DBU (4 drops)
was refluxed for 24 h. The reaction mixture was poured
into methanol to precipitate the target compound. The
methanolic layer was removed by filtration and then the
resulting precipitate was washed with ethanol, acetone
3-hexadecyloxyphenol (6e). A mixture of resorcinol
(2.00 g, 18.2 mmol), cetylbromide (5.50 g, 18.2 mmol),
K2CO3 (5.00 g) and dry N,N-dimethylformamide
(30 mL) was stirred at 100 °C for 3 h. The reaction
mixture was extracted with chloroform and washed
with water. The organic layer was dried over Na2SO4
and evaporated in vacuum. The crude product was
recrystallized from ethanol to remove the crystalline
by-product, 1,3-dihexadecyloxybenzene. The precipitate
was removed by filtration. The filtrate was evaporated
in vacuum and purified by column chromatography (silica
gel, CHCl3, Rf = 0.30) to obtain 2.33 g of white power.
Yield 38.3%, mp 63.9 °C. IR (KBr): n, cm-1 3451 (-OH),
1
2918 (-CH2-). H NMR (CDCl3; TMS): d, ppm 0.88
(3H, t, J = 6.9 Hz, -CH3), 1.26 (24H, s, -CH2CH2CH3),
1.40–1.47 (2H, m, -CH2CH2CH3), 1.72–1.79 (2H, m,
-OCH2CH2-), 3.92 (2H, t, J = 6.7 Hz, -OCH2CH2-), 6.40–
6.42 (2H, m, Ar-H), 6.47–6.49 (1H, m, Ar-H), 7.1 (1H, t,
J = 8.5, Ar-H).
4,5-bis(3-hexadecyloxyphenoxy)-1,2-dicyano-
benzene (7e). A mixture of 3-hexadecyloxyphenol (6e)
(1.87 g, 5.59 mmol), 4,5-dichloro-1,2-dicyanobenzene
(0.50 g, 2.54 mmol), K2CO3 (5.00 g) and N,N-
dimethylacetamide (14 mL) was stirred at 120 °C for 2 h.
The reaction mixture was extracted with chloroform
and washed with water. The organic layer was dried
over Na2SO4 and evaporated in vacuum. The residue
was purified by column chromatography (silica gel,
chloroform, Rf = 0.70) and recrystallization from
ethanol to obtain 1.45 g of white powder. Yield 72.1%,
mp 73.2 °C. IR (KBr): n, cm-1 2917, 2851 (-CH2-), 2240
(-CN). 1H NMR (CDCl3; TMS): d, ppm 0.88 (6H, t, J =
6.8 Hz, -CH3), 1.26 (48H, s, -CH2CH2CH3), 1.79 (4H,
t, J = 7.4 Hz, -OCH2CH2-), 3.94 (4H, t, J = 6.7 Hz,
-OCH2CH2-), 6.60–6.64 (4H, m, Ar-O-Ar-H), 6.80–6.82
(2H, m, Ar-O-Ar-H), 7.20 (2H, m, Ar-O-Ar-H), 7.32 (2H,
t, J = 8.2 Hz, CN-Ar-H).
2,3,9,10,16,17,23,24-octakis(3-hexadecyloxy-phe-
noxy)phthalocyaninato cobalt(II) (1e). A mixture of
4,5-bis(3-hexadecyloxyphenoxy)-1,2-dicyanobenzene
(7e) (0.200 g, 0.252 mmol), 1-hexanol (3 mL), DBU
(8 drops) and CoCl2·6H2O (6.31 mg, 2.65 × 10-2 mmol)
was refluxed for 16 h. The reaction mixture was poured
into methanol to precipitate the target compound. The
methanolic layer was removed by filtration and then the
resulting precipitate was washed with ethanol, acetone
and ethyl acetate, respectively. The residue was purified
by recrystallization from ethyl acetate and then column
Copyright © 2012 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2012; 16: 1150–1158