Arch. Pharm. Chem. Life Sci. 2013, 346, 53–61
Novel meso-Substituted Porphyrin Analogs
59
purified by column chromatograghy (silica gel, chloroform/hex-
ane 1.5:1 as eluent).
4CH), 10.59 (s, 1H, NH); UV–Vis spectrum: (lmax), 423 nm. Anal.
calcd. for C40H30N4O4 (630): C, 76.19; H, 4.76; N, 8.89%. Found: C,
76.20; H, 4.77; N, 8.90%.
5,10,15,20-Mesotetrakis[2-hydroxynaphthayl]-21H,23H-
porphyrin (2a)
5,10,15,20-Tetrabenzyl-21H,23H-porphyrin (2f)
Yield 75.8%; brown crystals; m.p. 1208C; IR (KBr): y/cmꢁ1 ¼ 3419
Yield 73.51%; black crystals; m.p. 1008C; IR (KBr): y/cmꢁ1 ¼ 3394
(NH), 2923 (CH ), 1594 (C C), 1560 (C N); 1H NMR (DMSO-d6) d
(OH), 3235 (NH), 1654 (C C), 1623 (C N); 1H NMR (DMSO-d6) d
–
–
–
–
–
–
–
2
–
(ppm): 2.25 (s, 8H, 4 CH2), 3.89 (s, 1H, NH), 5.24 (d, 1H, 2 pyrrolic
CH), 6.18 (d, 2H, 2 pyrrolic CH), 6.88 (d, 2H, 2 pyrrolic CH), 6.98
(d, 2H, 2 pyrrolic CH), 7.30 (d.d, 8H, Ar–H), 7.43 (d.d, 4H, Ar–H),
7.52 (d.d, 4H, Ar–H), 7.77 (d, 4H, Ar–H), 7.94 (d, 1H, Ar–H), 10.50
(s, 1H, NH); UV–Vis spectrum: (lmax), 420 nm. Anal. calcd. for
C48H38N4 (670): C, 85.94; H, 5.71; N, 8.35%. Found: C, 85.95;
H, 5.71; N, 8.36%.
(ppm): 2.28 (s, 1H, NH), 5.20 (d, 2H, 2 pyrrolic CH), 6.30 (d, 2H, 2
pyrrolic CH), 7.10 (d, 2H, 2 pyrrolic CH), 7.25 (d.d, 4H, Ar–H), 7.37
(d, 4H, Ar–H), 7.41 (d, 4H, Ar–H), 7.46 (d, 2H, 2 pyrrolic CH), 7.66
(d, 4H, Ar–H), 7.77 (d.d, 4H, Ar–H), 7.94 (s, 4H, 4 OH), 8.11 (d, 4H,
Ar–H), 10.10 (s, 1H, NH); UV–Vis spectrum: (lmax), 422 nm. Anal.
calcd. for C60H38N4O4 (878): C, 81.99; H, 4.36; N, 6.37%. Found: C,
82.00; H, 4.38; N, 6.38%.
5,10,15,20-Mesotetrakis[4-N,N-dimethylaminophenyl]-
21H,23H-porphyrin (2g)
Yield 80.10%; deep violet crystals; m.p. >3008C; IR (KBr):
5,10,15,20-Mesotetrakis[3-nitrophenyl]-21H,23H-
porphyrin (2b)
Yield 80%; black crystals; m.p. 1908C; IR (KBr): y/cmꢁ1 ¼ 3396
y/cmꢁ1 ¼ 3409 (NH), 2923 (2CH ), 1602 (C C), 1519 (C N);
(NH), 1660 (C C), 15 277 (C N), 1348–1527 (NO ); 1H NMR
–
–
–
–
–
–
–
–
3
2
1H NMR (DMSO-d6) d (ppm): 3.02 (s, 1H, NH), 3.89 (s, 24H, 4 N-
(CH3)2), 5.3 (d, 2H, 2 pyrrolic CH), 6.2 (d, 2H, 2 pyrrolic CH), 6.44 (d,
2H, 2 pyrrolic CH), 6.51 (d, 2H, 2 pyrrolic CH), 6.94 (d, 8H, Ar–H),
7.27 (d, 8H, Ar–H), 10.22 (s, 1H, NH); UV–Vis spectrum: (lmax),
424 nm. Anal. calcd. for C52H50N8 (786): C, 79.36; H, 4.40;
N, 14.24%. Found: C, 80.00; H, 4.41; N, 14.25%.
(DMSO-d6) d (ppm): 2.28 (s, 1H, NH), 5.2 (d, 2H, 2 pyrrolic CH),
6.22 (d, 2H, 2 pyrrolic CH), 7.10 (d, 2H, 2 pyrrolic CH), 7.45 (d, 2H,
2 pyrrolic CH), 7.95 (s, 4H, Ar–H), 8.10 (d, 4H, Ar–H), 8.70 (d.d, 4H,
Ar–H), 8.97 (d, 4H, Ar–H), 10.60 (s, 1H, NH); 13C NMR (DMSO-d6) d
(ppm): 161.18, 155.89, 147.86, 140.98, 137.78, 136.56, 133.43,
132.23, 129.98, 125.1, 123.37, 122.98, 120.59, 119.96, 103.05;
UV–Vis spectrum: (lmax), 422 nm. Anal. calcd. for C40H26N5O2
(608): C, 66.70; H, 3.30; N, 14.10%. Found: C, 66.70; H, 3.32; N,
14.11%.
5,10,15,20-Mesotetrakis[5-(benzo[d][1,3]dioxolyl)]-
21H,23H-porphyrin (2h)
Yield 73%; black crystals; m.p. 1628C; IR (KBr): y/cmꢁ1 ¼ 3419
(NH), 2923 (CH ), 1596 (C C), 1560 (C N); 1H NMR (DMSO-d6) d
–
–
–
–
5,10,15,20-Mesotetrakis[2-thienyl]-21H,23H-porphyrin (2c)
2
Yield 72%; brown crystals; m.p. 1408C; IR (KBr): y/cmꢁ1 ¼ 3413
(ppm): 3.78 (s, 1H, NH), 5.22 (d, 2H, 2 pyrrolic CH), 5.60 (d, 2H, 2
pyrrolic CH), 5.90 (s, 8H, 4 CH2), 6.34 (s, 2H, Ar–H), 6.67 (d, 2H, 2
pyrrolic CH), 6.78 (d, 2H, 2 pyrrolic CH), 7.10 (d, 2H, Ar–H), 7.35 (d,
2H, Ar–H), 7.49 (d, 2H, Ar–H), 7.62 (d, 2H, Ar–H), 7.95 (s, 1H, Ar–H),
10.44 (s, 1H, NH); UV–Vis spectrum: (lmax), 424 nm. Anal. calcd.
for C52H30N4O8 (838): C, 74.46; H, 3.58; N, 6.68%. Found: C, 74.47;
H, 3.60; N, 6.70%.
1
–
–
–
(NH), 1654 (C N), 1554 (C C); H NMR (DMSO-d ) d (ppm): 2.30 (s,
–
6
1H, NH), 5.75 (d, 2H, 2 pyrrolic CH), 5.89 (d, 2H, 2 pyrrolic CH),
7.10 (d, 2H, 2 pyrrolic CH), 7.45 (d, 2H, 2 pyrrolic CH), 7.72 (d.d,
2H, 4 thiophenic CH), 8.05 (d, 2H, 4 thiophenic CH), 8.20 (d, 2H, 4
thiophenic CH), 10.60 (s, 1H, NH); UV–Vis spectrum: (lmax),
422 nm. Anal. calcd. for C36H22N4S4 (638): C, 67.71; H, 3.45; N,
8.77%. Found: C, 67.74; H, 3.45; N, 8.78%.
5,10,15,20-Mesotetrakis[3-(4-oxo-4H-chromenyl]-
21H,23H-porphyrin (2i)
Yield 79.32%; deep blackish red crystals; m.p. 2308C; IR (KBr):
5,10,15,20-Mesotetrakis[4-chloro-2-nitrophenyl]-
21H,23H-porphyrin (2d)
Yield 81%; deep reddish brown powder; m.p. >3008C; IR (KBr):
y/cmꢁ1 ¼ 3409 (NH), 1690 (C O), 1612 (C C), 1554 (C N); H NMR
1
–
–
–
–
–
–
y/cmꢁ1 ¼ 3419 (NH), 1602 (C C), 1509 (C N), 819 (C–Cl); H NMR
(DMSO-d6) d (ppm): 2.28 (s, 1H, NH), 5.62 (d, 2H, 2 pyrrolic CH),
5.81 (d, 2H, 2 pyrrolic CH), 6.59 (d, 2H, 2 pyrrolic CH), 7.09 (d, 2H,
2 pyrrolic CH), 7.46 (d, 4H, Ar–H), 7.61 (d, 4H, Ar–H), 7.76 (d.d, 4H,
Ar–H), 7.95 (s, 4H, 4 CH), 8.09 (d.d, 4H, Ar–H), 10.59 (s, 1H, NH). 13C
NMR (DMSO-d6) d (ppm): 177.49, 157.55, 149.33, 147.16, 138.49,
135.0, 133.65, 129.48, 125.30, 123.55, 122.99, 119.95, 117.08,
115.90; UV–Vis spectrum: (lmax), 424 nm. Anal. calcd. for
C56H30N4O8 (868): C, 77.42; H, 3.45; N, 6.45%. Found: C, 77.44;
H, 3.50; N, 6.45%.
1
–
–
–
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(DMSO-d6) d (ppm): 2.28 (s, 1H, NH), 6.64 (d, 1H, 2 pyrrolic CH),
6.84 (d, 2H, 2 pyrrolic CH), 6.95 (d, 2H, 2 pyrrolic CH), 7.10 (d, 2H,
2 pyrrolic CH), 7.46 (d, 2H, Ar–H), 7.78 (d, 4H, Ar–H), 7.90 (s, 4H,
Ar–H), 10.55 (s, 1H, NH); 13C NMR (DMSO-d6) d (ppm): 161.23,
146.29, 136.43, 134.62, 134.37, 131.33, 128.61, 125.0, 124.16,
122.97, 120.36, 103.34; UV–Vis spectrum: (lmax), 428 nm. Anal.
calcd. for C44H22N8O8Cl4 (932.51): C, 56.65; H, 2.36; N, 12.01%.
Found: C, 56.57; H, 2.35; N, 12.01%.
5,10,15,20-Mesotetrakis[5-methyl-2-furfuryl]-21H,23H-
porphyrin (2e)
10,15,20-Mesotetrakis[phenylethylene]-21H,23H-
porphyrin (2j)
Yield 72%; deep brown crystals; m.p. 1708C; IR (KBr):
Yield 82%; brown powder; m.p. >3008C; IR (KBr): y/cmꢁ1 ¼ 3429
y/cmꢁ1 ¼ 3419 (NH), 2919 (CH ), 1612 (C C), 1563 (C N);
(NH), 3052 ( CH), 1612 (C N), 1554 (C C); 1H NMR (DMSO-d6) d
–
–
–
–
–
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3
1H NMR (DMSO-d6) d (ppm): 2.28 (s, 12H, 4 CH3), 3.83 (s, 1H, NH),
5.90 (d, 2H, 2 pyrrolic CH), 6.38 (d, 4H, 4CH), 6.62 (d, 2H, 2 pyrrolic
CH), 6.98 (d, 2H, 2 pyrrolic CH), 7.11 (d, 21H, 4 CH), 7.48 (d, 2H,
(ppm): 2.3 (s, 1H, NH), 5.41 (d, 2H, 2 pyrrolic CH), 5.65 (d, 2H, 2
pyrrolic CH), 5.90 (d, 2H, 2 pyrrolic CH), 6.12 (d, 2H, 2 pyrrolic
CH), 6.65 (s, 1H, CH), 6.85 (s, 1H, CH), 7.01–7.54 (m, 20H, Ar–H),
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