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N. PEREIRA ET AL.
br s, 2 × NH), 9.30 (2H, s, 2 × CHO), 7.62 (1H, d, J =
7.9, PhBr), 7.28–7.32 (1H, m, PhBr), 7.17–7.21 (2H, m,
PhBr), 6.88 (2H, s), 6.05 (1H, s) 6.04 (2H, s). GC-MS
(EI): m/z 356, calcd. for [M]+ 356.
CH2CH2CO2), -3.40 (2H, br s, 2 × NH). MS (ESI): m/z
667.27 [M + H]+. Anal. calcd. for C36H33BrN4O4·1/2H2O:
C, 64.10; H, 5.08; N, 8.31. Found C, 63.89; H, 4.98; N,
8.35. UV-vis (CH2Cl2): λmax, nm (ε %) 404 (100), 499
(10), 530 (4), 569 (5), 622 (2).
1,9-diformyl-5-phenyldipyrrylmethane (8c). The
dipyrrylmethane 8c was prepared according to the pro-
5-(2-bromophenyl)-13,17-bis(2-methoxycarbonyl-
ethyl)-12,18-dimethyl-porphyrin (11b). Porphyrin 11b
was prepared by reacting dipyrrylmethane dicarboxylic
acid 6 (1.1 mmol) with diformyldipyrrylmethane 8b
(1.3 mmol) by following the procedure used for porphy-
1
cedure described above for 8a (46% yield). H NMR
(400 MHz; CDCl3; Me4Si): δH, ppm 10.07 (2H, br s, 2 ×
NH), 9.25 (2H, s, 2 × CHO), 7.23–7.66 (5H, m, Ph), 6.87
(2H, s), 6.08 (2H, s), 5.57 (1H, s). GC-MS (EI): m/z 278,
calcd. for [M]+ 278.
1
rin 9 (0.044 g, 6% yield). H NMR (400 MHz; CDCl3;
5,15-di(4-bromophenyl)-3,7,13,17-tetra(2-methoxy-
Me4Si): δH, ppm 10.18 (2H, s, meso), 10.09 (1H, s,
meso), 9.32 (2H, d, J = 4.6, beta), 8.85 (2H, d, J = 4.6,
beta), 8.19 (1H, dd, J3 = 6.9, J4 = 2.2, PhBr), 8.04 (1H, dd,
J3 = 7.3, J4 = 1.8, PhBr), 7.66–7.75 (2H, m, PhBr), 4.43
(4H, t, J = 7.6, 2 × CH2CH2CO2), 3.65 (12H, s, 4 × CH3),
3.31 (4H, t, J = 7.7, 2 × CH2CH2CO2), -3.40 (2H, br s,
2 × NH). MS (ESI): m/z 667.33 [M + H]+. Anal. calcd. for
C36H33BrN4O4·3H2O: C, 60.09; H, 5.46; N, 7.79. Found
C, 60.79; H, 5.01; N, 7.31. UV-vis (CH2Cl2): λmax, nm
(ε %) 403 (100), 499 (9), 533 (5), 569 (6), 622 (4).
carbonylethyl)-2,8,12,18-tetramethylporphyrin
(9)
[15]. A mixture of 4-bromobenzaldehyde (0. 320 g, 1.7
mmol) and dipyrrylmethane dicarboxylic acid 6 (0.500
g, 1.2 mmol) in dichloromethane (90 mL) was bubbled
with dry N2 for 15 min. A solution of p-toluenesulfonic
acid (1 g) in methanol (17 mL) was added to the mix-
ture and stirred under N2 for 24 h at room temperature.
A solution of zinc acetate (1 g) in methanol (15 mL) was
added to the mixture, bubbled with air and stirred for a
further 24 h under air at room temperature. The solution
was washed with water and saturated aqueous sodium
bicarbonate, dried over anhydrous sodium sulfate and the
solvent evaporated in vacuo. The residue was chromato-
graphed over silica gel (eluent: dichloromethane/10%
ethyl acetate). To the fractions with the zinc porphyri-
nate dissolved in dichloromethane (30 mL) was added
trifluoroacetic acid (1 mL) and the mixture stirred for
30 min. The solution was washed with water and satu-
rated aqueous sodium bicarbonate, dried over anhydrous
sodium sulfate and the solvent evaporated. The resulting
Zn-free porphyrin was chromatographed over a short
alumina column eluted with dichloromethane and the
solvent evaporated. The porphyrin was recrystallized
from dichloromethane/methanol, isolated and dried in
vacuo (0.24 g, 40% yield.). 1H NMR (400 MHz; CDCl3;
Me4Si): δH, ppm 10.29 (2H, s, meso), 7.94 (4H, d, J =
8.5, PhBr), 7.90 (4H, d, J = 8.0, PhBr), 4.36 (8H, t, J =
7.8, 4 × CH2CH2CO2), 3.66 (12H, s, 4 × CO2CH3), 3.16
(8H, t, J = 7.8, 4 × CH2CH2CO2), 2.54 (12H, s, 4 × CH3),
-2.47 (2H, br s, 2 × NH). MS (ESI): m/z 1021.27 [M +
H]+. Anal. calcd. for C52H52Br2N4O8·6H2O: C, 55.32; H,
5.71; N, 4.96. Found: C, 54.75; H, 4.07; N, 3.91. UV-vis
(CH2Cl2): λmax, nm (ε %) 408 (100), 505 (15), 538 (8),
573 (8), 624 (5).
13,17-bis(2-methoxycarbonylethyl)-12,18-dimethyl-
5-phenylporphyrin (11c). Porphyrin 11c was prepared by
reacting dipyrrylmethane dicarboxylic acid 6 (1.1 mmol)
with diformyldipyrrylmethane 8c (1.3 mmol) by follow-
ing the procedure used for porphyrin 9 (0.018 g, 28%
1
yield). H NMR (400 MHz; CDCl3; Me4Si): δH, ppm
10.18 (2H, s, meso), 10.05 (1H, s, meso), 9.32 (2H, d,
J = 4.6, beta), 9.02 (2H, d, J = 4.6, beta), 8.24–8.27
(2H, m, Ph), 7.78–7.80 (3H, m, Ph), 4.42 (4H, t, J = 7.7,
2 × CH2CH2CO2), 3.66 (6H, s, 2 × CO2CH3), 3.65 (6H,
s, 2 × CH3), 3.31 (4H, t, J = 7.7, 2 × CH2CH2CO2), -3.39
(2H, br s, NH). MS (ESI): m/z 587.40 [M + H]+. Anal.
calcd. for C36H34N4O4: C, 73.70; H, 5.84; N, 9.55. Found
C, 73.23; H, 5.87; N 9.53. UV-vis (CH2Cl2): λmax, nm
(ε %) 401 (100), 498 (10), 530 (4), 569 (5), 621 (2).
5,15-di(4-bromophenyl)-3,7,13,17-tetra(2-hy-
droxycarbonylethyl)-2,8,12,18-tetramethylporphyrin
(10). To porphyrin 9 (50 mg) dissolved in tetrahydrofuran
(30 mL) a solution of potassium hydroxide (250 mg) in
water (1 mL) was added and the mixture was stirred over-
night under N2 at room temperature. The potassium salt
of the porphyrin precipitated, was filtered off, washed
with tetrahydrofuran and dissolved in water. The car-
boxylic acid porphyrin was precipitated by neutralization
of the aqueous solution with acetic acid. The porphyrin
was collected by filtration, washed well with water and
dried in vacuo (0.036 g, 76% yield). 1H NMR (400 MHz;
CDCl3/TFA; Me4Si): δH, ppm 10.55 (2H, s, meso), 8.07
(8H, mL, Ph), 4.06 (8H, t, J = 6.2, 4 × CH2CH2CO2),
2.90 (8H, t, J = 6.2, 4 × CH2CH2CO2), 2.31 (12H, s,
4 × Me(β)), -2.13 (4H, s, 2 × NH). MS (ESI): m/z 965.27
[M + H]+. HRMS (FAB): m/z calcd. for C48H45Br2N4O8
[M + H]+, 963.15987; found 963.16013; ∆ = -0.26 mmu
[M + H]+.
5-(4-bromophenyl)-13,17-bis(2-methoxycarbonyl-
ethyl)-12,18-dimethyl-porphyrin (11a). Porphyrin 11a
was prepared by reacting dipyrrylmethane dicarboxylic
acid 6 (1.1 mmol) with diformyldipyrrylmethane 8a (1.3
mmol) by following the procedure used for porphyrin 9
(0.081 g, 11% yield). 1H NMR (400 MHz; CDCl3; Me4Si):
δH, ppm 10.66 (1H, s, meso), 10.59 (2H, s, meso), 9.33
(2H, d, J = 4.7, beta), 8.86 (2H, d, J = 4.7, beta), 8.33
(2H, d, J = 7.3, PhBr), 8.12 (2H, d, J = 8.2, PhBr), 4.41
(4H, t, J = 7.4, 2 × CH2CH2CO2), 3.65 (6H, s, 2 × CO2
CH3), 3.58 (6H, s, 2 × CH3), 3.20 (4H, t, J = 7.4, 2 ×
5-(4-bromophenyl)-13,17-bis(2-hydroxycarbonyl-
ethyl)-12,18-dimethyl-porphyrin (12a). Porphyrin 12a
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 440–445