POrPHyrIn Hexamer WItH a trIPHenylene COre unIt
643
(m, 42H), 6.79 (t, J = 3.2 Hz, 12H), 4.12–4.04 (m, 60H),
1.88–1.65 (m, 96H), 1.51 (t, J = 12.4 Hz, 12H), 1.22 (m,
132H), 0.91 (d, J = 8.4 Hz, 144H). MS (MALDI-TOF):
m/z 7508 [M + H]+. UV-vis (THF): , nm (log ε, M-1.cm-1)
420 (6.56). Anal. calcd. for C462H582N30O36: C, 73.87; H,
7.65; N, 5.59. Found: C, 73.57; H, 7.70; N, 5.57.
phase was extracted, washed with water and dried over
Na2SO4. After evaporation, the residue was washed with
MeOH and dried under vacuum to give porphyrin 1 as a
dark reddish purple solid (1.10 g, 1.19 mmol, 99%). mp
1
284 °C. H NMR (300 MHz, CDCl3): δ, ppm 10.22 (s,
1H), 9.33 (d, J = 6.4 Hz, 2H), 9.15 (d, J = 6.4 Hz, 2H),
9.06 (d, J = 6.8 Hz, 2H), 8.84 (d, J = 6.4 Hz, 2H), 8.56
(d, J = 10.8 Hz, 2H), 8.36 (d, J = 10.4 Hz, 2H), 7.41 (d,
J = 2.8 Hz, 4H), 6.91 (t, J = 3.2 Hz, 2H), 4.17 (t, J = 8.8
Hz, 8H), 1.89 (m, 4H), 1.78 (q, J = 8.8 Hz, 8H), 0.99 (d,
J = 8.8 Hz, 24H), -3.02 (br s, 2H). MS (MALDI-TOF):
m/z 927 [M + H]+.
H2PA. 4-acetamidophenyldipyrromethane (6.01 g,
21.5 mmol), dipyrromethane (2.12 g, 14.3 mmol), and
3,5-di-isoamyloxybenzaldehyde (10.11 g, 35.8 mmol)
were dissolved in 2.15 L of dry CHCl3. Trifluoroacetic
acid (3.6 mL) was added, and the mixture was stirred for
3 h in the dark. p-chloranil was added, and the mixture
was stirred for additional 14 h. The reaction mixture was
quenched by addition of 64 mL of triethylamine and the
solvent was evaporated. Flash column chromatography on
silica gel with CHCl3/ethyl acetate (30/1 = v/v) as the elu-
ent afforded H2PA as a dark reddish brown solid (830 mg,
0.88 mmol, 6%). mp 128 °C. 1H NMR (300 MHz, CDCl3):
δ, ppm 10.19 (s, 1H), 9.31 (d, J = 6.0 Hz, 2H), 9.12 (d, J =
6.0 Hz, 2H), 9.01 (d, J = 6.4 Hz, 2H), 8.86 (d, J = 6.4 Hz,
2H), 8.14 (d, J = 11.2 Hz, 2H), 7.86 (d, J = 11.2 Hz, 2H),
7.48 (br s, 1H), 7.39 (d, J = 2.8 Hz, 4H), 6.90 (t, J = 2.8
Hz, 2H), 4.16 (t, J = 8.8 Hz, 8H), 2.35 (s, 3H), 1.87 (m,
4H), 1.78 (q, J = 8.8 Hz, 8H), 0.98 (d, J = 8.4 Hz, 24H),
-3.04 (br s, 2H). 13C NMR (75 MHz, CDCl3): δ, ppm
168.47, 158.43, 143.48, 138.53, 137.57, 134.99, 131.51,
131.24, 130.79, 119.75, 119.55, 117.83, 114.47, 104.72,
101.01, 66.76, 38.14, 25.13, 24.87, 22.66. MS (MALDI-
TOF): m/z 941 [M + H]+. UV-vis (THF): , nm (log ε, M-1.
cm-1) 414 (5.62). Anal. calcd. for C60H69N5O5: C, 76.65;
H, 7.40; N, 7.45. Found: C, 76.36; H, 7.41; N, 7.37.
ZnPA. To a solution of H2PA (100 mg, 0.106 mmol)
dissolved in CHCl3 (40 mL) was added a solution of
zinc acetate (150 mg) in MeOH (5 mL) and the solution
was stirred at 50 °C for 1 h. After cooling, the reaction
mixture was washed with water twice, dried over anhy-
drous Na2SO4, and then the solvent was evaporated. The
product was purified over silica gel column using CHCl3
as eluent to afford ZnPA as a pink solid (102 mg, 0.102
mmol, 96%). mp 155 °C. 1H NMR (300 MHz, CDCl3): δ,
ppm 10.24 (s, 1H), 9.39 (d, J = 6.0 Hz, 2H), 9.20 (d, J =
6.0 Hz, 2H), 9.09 (d, J = 6.4 Hz, 2H), 8.93 (d, J = 6.4 Hz,
2H), 8.10 (d, J = 11.2 Hz, 2H), 7.62 (d, J = 11.2 Hz, 2H),
7.40 (d, J = 4.0 Hz, 4H), 7.35 (br s, 1H), 6.89 (t, J = 6.89
Hz, 2H), 4.15 (t, J = 9.2 Hz, 8H), 2.04 (s, 3H), 1.90–1.83
(m, 4H), 1.76 (q, J = 8.8 Hz, 8H), 0.97 (d, J = 8.8 Hz,
24H). MS (MALDI-TOF): m/z 1004 [M + H]+. UV-vis
(CHCl3): , nm (log ε, M-1.cm-1) 420 (5.82). Anal. calcd.
for C60H67N5O5Zn: C, 71.81; H, 6.73; N, 6.98. Found: C,
71.30; H, 6.81; N, 6.98.
Porphyrin 2. H2PA (820 mg, 0.87 mmol) was dis-
solved in a mixture of EtOH (260 mL) and conc. HCl
solution (175 mL) and refluxed at 80 °C for 17 h. After
cooling, the reaction mixture was poured onto water,
and the organic layer was extracted with CHCl3, washed
with aqueous NaHCO3, dried over anhydrous Na2SO4
and evaporated. Flash column chromatography on silica
gel with CHCl3 as the eluent afforded porphyrin 2 as a
dark reddish brown solid (697 mg, 0.78 mmol, 89%). mp
1
124 °C. H NMR (300 MHz, CDCl3): δ, ppm 10.15 (s,
1H), 9.30 (d, J = 6.4 Hz, 2H), 9.11 (d, J = 6.0 Hz, 2H),
9.00 (d, J = 6.4 Hz, 2H), 8.94 (d, J = 6.8 Hz, 2H), 7.97
(d, J = 11.2 Hz, 2H), 7.39 (d, J = 3.2 Hz, 4H), 7.05 (d,
J = 11.2 Hz, 2H), 6.89 (t, J = 3.2 Hz, 2H), 4.16 (t, J = 8.8
Hz, 8H), 4.02 (br s, 2H), 1.90 (m, 4H), 1.77 (q, J = 8.8
Hz, 8H), 0.98 (d, J = 8.8 Hz, 24H), -3.02 (br s, 2H). MS
(MALDI-TOF): m/z 899 [M + H]+.
Porphyrin 3. A solution of THF containing 4-di-
methylaminopyridine (DMAP, 408 mg, 3.34 mmol),
1-hydroxybenzotriazole (HOBt, 450 mg, 3.34 mmol)
and 6-bromohexanoic acid (651 mg, 3.34 mmol) was
treated with 1-ethyl-3-(3-dimethylaminopropyl)-carbo-
diimide hydrochloride (EDC, 640 mg, 3.34 mmol) under
nitrogen at 0 °C. The mixture was stirred at 0 °C for 1 h.
Porphyrin 2 (300 mg, 0.334 mmol) was added to the
mixture and stirred at 0 °C for 30 min. The mixture was
then stirred at room temperature overnight. The mixture
was concentrated in vacuo and poured onto a 2% HCl
aqueous solution and extracted with CHCl3. The organic
layer was washed with saturated NaHCO3 aqueous solu-
tion, dried over anhydrous Na2SO4 and evaporated the
solvent. Flash column chromatography on silica gel with
CHCl3 as the eluent afforded porphyrin 3 as a dark red-
dish brown solid (327 mg, 0.30 mmol, 91%). mp 112 °C.
1H NMR (300 MHz, CDCl3): δ, ppm 10.19 (s, 1H), 9.31
(d, J = 6.0 Hz, 2H), 9.12 (d, J = 6.0 Hz, 2H), 9.01 (d, J =
6.4 Hz, 2H), 8.86 (d, J = 6.4 Hz, 2H), 8.15 (d, J = 11.2
Hz, 2H), 7.89 (d, J = 11.2 Hz, 2H), 7.45 (br s, 1H), 7.39
(d, J = 2.8 Hz, 4H), 6.89 (t, J = 2.8 Hz, 2H), 4.16 (t, J =
8.8 Hz, 8H), 3.50 (t, J = 8.8 Hz, 2H), 2.55 (t, J = 10.0 Hz,
2H), 1.99 (m, 2H), 1.87 (m, 6H), 1.77 (q, J = 8.8 Hz, 8H),
0.97 (d, J = 8.8 Hz, 24H), -3.04 (br s, 2H). MS (MALDI-
TOF): m/z 1075 [M + H]+.
Porphyrin 1. A mixture of H2PE (1.14 g, 1.21 mmol)
in 700 mL of THF/ethanol (1/1 = v/v) and 70 mL of 2 M
KOH aqueous solution was refluxed (80 °C) under an
atmospheric pressure of nitrogen for 1 h. After cooling,
the solvents were evaporated to dryness and then added
300 mL of water and 300 mL of CHCl3. After neutral-
ization (pH 7) with dilute HCl aqueous solution, organic
Porphyrin 4. A solution of THF containing 4-di-
methylaminopyridine (DMAP, 340 mg, 2.78 mmol),
Copyright © 2011 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2011; 15: 643–651