2
004
I. Az o´ car et al.
1
78 (2.25), 633 (1.08) nm; H NMR (400.13 MHz, CDCl ): 10.31
5
3
(
o-PhH), 7.32 (d, 2H, m-PhH), 4.21 (s, 3H, OCH ), 4.04 (s, 3H, OCH ),
s, 2H, meso), 9.39 (d, 4H, b-H), 9.14 (d, 4H, b-H), 7.83 (m, 4H,
3
3
1
3
2
3.07 (s, 2H, NH). C NMR (100.61 MHz, CDCl ): d 149.2 (Ar-C),
3
1
1
5
47.4 (Ar-C), 134.3 (Ar-C), 127.8 (Ar-C), 118.9 (Ar-C), 110.0 (Ar-C),
31.86 (C-pyrrole), 145.24 (C-pyrrole), 105.38 (meso CH), 56.32 (OCH ),
3
þ
6.28 (OCH ). MS(ESI): m/z 583.6 [M þ H] , calc. 583.6. Anal. calcd.
3
for C H N O : C, 74.21; H, 5.19; N, 9.62. Found: C, 74.34; H, 5.33;
6 30 4 4
3
N, 9.57.
5
3
5
1
,10,15-Tris(3,4-OCH -phenyl) porphyrin (2): (12.2 mg; 34%). Mp .
3
008C; visible spectrum: lmax/nm (CH Cl ): 418 (5.62), 512.7 (4.09),
2
2
1
48.8 (3.75), 586 (3.63), 642 (3.35) nm; H NMR (400.13 MHz, CDCl ):
0.20 (s, 1H, meso), 9.34 (d, 2H, b-H), 9.08 (d, 2H, b-H), 8.96 (d, 2H,
3
b-H), 8.93 (d, 2H, b-H), 7.81 (m, 6H, o-PhH), 7.28 (d, 3H, m-PhH),
.19 (s, 6H, OCH ), 4.18 (s, 3H, OCH ), 4.01 (s, 6H, OCH ), 3.97
4
3
3
3
1
3
(
s, 6H, OCH ), 22.95 (s, 2H, NH). C NMR (100.61 MHz, CDCl ): d
3 3
149.2 (Ar-C), 147.4 (C-pyrrole), 134.6 (Ar-C), 131.6 (C-pyrrole), 130.85
(
(
C-pyrrole), 127.7 (Ar-C), 118.6 (Ar-C), 104.9 (meso CH), 56.42
þ
OCH ), 56.38 (OCH ). MS(ESI): m/z 719.7 [M þ H] , calc. 719.8.
3
3
Anal. calcd. for C H N O : C, 73.52; H, 5.33; N, 7.79. Found: C,
4
4 38 4 6
7
3.47; H, 5.44; N, 7.82.
5,10,15,20-Tetrakis(3,4-OCH -phenyl) porphyrin (3): (10.5 mg; 29%).
Visible spectrum: lmax/nm/(log 1) (CH Cl ): 425 (4.92), 520 (3.71), 557.8
3
2
1
2
(
3.48), 592 (3.25), 651 (3.16) nm; H NMR (400.13 MHz, CDCl3):
.86 (s, 8H, b-H), 7.18 (m, 8H, o-PhH), 7.69 (d, 4H, m-PhH), 3.92 (s, 12H,
8
OCH ), 4.18 (s, 12H, OCH ), 22.80 (s, 2H, NH). C NMR (100.61 MHz,
1
3
3
3
CDCl ): d 149.16 (Ar-C), 135.05 (Ar-C), 127.60 (Ar-C), 118.53 (C-Ar),
3
1
09.73 (C-Ar), 131.24 (C-pyrrole), 147.35 (C-pyrrole), 120.06 (meso-C), 56.32
þ
(OCH ), 56.34 (OCH ). MS (ESI): m/z 855.7 [M þ H] , calc. 855.9. Anal.
3
3
calcd. for C H N O : C, 73.05; H, 5.42; N, 6.55. Found: C, 73.17; H, 5.54;
N, 6.43.
52 46 4 8
RESULTS AND DISCUSSION
The synthesis of the 5,15-disustitued porphyrins occurs by a [2 þ 2] conden-
sation of the respective dipyrromethane with an aldehyde catalyzed by trifluor-
[
12]
oacetic acid.
such as 2,3-dicyano-5,6-dichloro-parabenzoquinone (DDQ) and TCQ or
This reaction gives porphyrinogen, but with oxidizing agents
bubbling with O , the respective porphyrins can be obtained. Scrambling in
2
an acid-catalyzed dipyrromethane–aldehyde condensation is well known, and
it is controlled by the acid catalyst, reagent concentration, reagent stoichiometry,