S. Wu et al. / Bioorg. Med. Chem. 14 (2006) 2956–2965
2963
4
di(4-pyridyl)-porphyrin (23). 3,3 -Diethyl-4,4 -dimethyl-
.6.7. 2,8,12,18-Tetraethyl-3,7,13,17-tetramethyl-5,15-
0
0
Section 4.6 described and porphyrin 5 was obtained in
34 mg (87.0%). H NMR (DMSO-d , 300 MHz):
0
1
6
2
,2 -dipyrrylmethane (21) (460 mg, 2 mmol) and pyri-
ꢀ2.97 (s, 2H), 2.06 (t, J = 7.1 Hz, 6H), 4.65 (m, 6H),
5.15 (d, J = 7.2 Hz, 4H), 8.60 (t, J = 6.9 Hz, 2H), 9.09
(s, 4H), 9.35 (d, J = 6 Hz, 2H), 9.52 (d, J = 5.7 Hz,
2H), 9.91 (d, J = 3.6 Hz, 4H), 10.0 (s, 2H); UV–vis
(DMF): kmax (nm, log e) = 422 (5.47), 516 (4.25), 552
(3.74), 592 (3.65), 651 (3.81); SIMS HRMS for
dine-4-carbaldehyde (190 lL, 2 mmol) were mixed in
00 mL of CH Cl /C H OH (95:5). The reaction mix-
ture was treated and purified according to procedure
5
2
2
2
5
in Section 4.2. The desired porphyrin 23 was obtained
in a yield of 18.4% (116 mg). H NMR (CDCl3,
1
+
3
00 MHz): ꢀ2.52 (s, 2H), 1.76 (m, 12H), 2.52 (s, 12H),
C H N (M ꢀ2I): found 550.2834, calcd 550.2839.
3
6
34
6
4
.0 (d, J = 7.2 Hz, 8H), 8.05 (d, J = 5.1 Hz, 4H), 8.99
(
d, J = 4.2 Hz, 4H), 10.23 (s, 2H); UV–vis (CHCl ): kmax
4.6.13. 5,15-Di(3-pyridyl)-porphyrin (30). Dipyrrome-
thane 28 (1.46 g, 10 mmol) and pyridine-3-carbaldehyde
(0.95 mL, 10 mmol) were reacted. After reaction, the
mixture was treated and separated according to proce-
3
(
nm, log e) = 408 (5.16), 508 (4.13), 542 (3.80), 576
+
3.88), 627 (3.51); ESI HRMS for C H N (M+H) :
(
found 633.3708, calcd 633.3700.
4
2
44
6
dure in Section 4.5 and porphyrin 30 was obtained in
a yield of 2.5% (58 mg). H NMR (CDCl , 300 MHz):
1
4
.6.8. 2,8,12,18-Tetraethyl-3,7,13,17-tetramethyl-5,15-
2
3
5
di(N-methyl-pyridium-4-yl)-porphyrin (10) . Porphyrin
3 (40 mg, 63.3 lmol) and methyl iodide (2 mL) were
ꢀ3.17 (s, 2H), 7.83 (m, 2H), 8.58 (m, 2H), 9.06
2
(m,6H), 9.48 (d, J = 4.2 Hz, 4H), 9.52 (s, 2 H), 10.41
(nm, log e) = 407 (5.42),
max
mixed. After reaction, the reaction mixture was treated
as per procedure 4.5 described to yield 94.5% (55 mg)
of porphyrin 10. Fully characterized data were reported
(s, 2H); UV–vis (CHCl ): k
3
503 (4.16), 536 (3.83), 574 (3.78), 628 (3.60); ESI HRMS
for C H N (M+H) : found 465.1833, calcd 465.1827.
+
3
0
20
6
2
5
in our previous paper.
4
.6.14. 5,15-Di(pyridium-3-yl)-porphyrin (6). Porphyrin
1
5
4
.6.9. 5,15-Bisphenyl-10,20-di(3-pyridyl)-porphyrin (19) .
Pyrrole (4 mL, 57.2 mmol), pyridine-3-carbaldehyde
2.74 mL, 28.6 mmol), and benzaldehyde (2.91 mL,
8.6 mmol) were mixed and crude the product was
purified according to procedure in Section 4.2 to yield
6 mg (1.23%) of porphyrin 19. H NMR (CDCl3,
00 MHz): ꢀ2.79 (s, 2H), 7.70 (m, 8H), 8.21 (d,
30 (30 mg, 64.7 lmol) and 3 mL of methyl iodide were
mixed. After reaction, the crude was treated and purified
according to procedure in Section 4.6 described. Por-
(
2
1
phyrin 6 was obtained in a yield of 90.7% (44 mg). H
NMR (DMSO-d , 300 MHz): ꢀ3.41 (s, 2H), 4.70 (s,
6
1
7
3
6H), 8.63 (s, 2H), 9.30 (s, 4H), 9.45 (s, 2H), 9.52 (s,
2H), 9.84 (s, 4H), 10.07 (m, 4H), 10.82 (s, 2H); UV–vis
(DMF): kmax (nm, log e) = 408 (5.57), 502 (4.37), 536
(3.95), 574 (3.88), 628 (3.68); ESI MS for C H N
6
J = 6 Hz, 4H), 8.51 (d, J = 7.5 Hz, 2H), 8.79 (d,
J = 4.8 Hz, 4H), 8.91 (d, J = 4.8 Hz, 4H), 9.04 (t,
J = 2.4 Hz, 2H), 9.47 (s, 2H).
3
2
26
+
[(M ꢀ2I)/2]: found 247.4, calcd 274.1; SIMS HRMS
+
for C H N (M ꢀ2I–CH ): found 479.1978, calcd
3
2
26
6
3
4
.6.10. 5,15-Bisphenyl-10,20-di(N-methyl-pyridium-3-yl)-
479.1979.
1
5
porphyrin (4) . Porphyrin 19 (30 mg, 48.7 lmol) and
methyl iodide (2 mL) were mixed. After reaction, the
crude product was treated and purified according to
4.6.15. 2,8,12,18-Tetraethyl-3,7,13,17-tetramethyl-5,15-
0
0
di(3-pyridyl)-porphyrin (24). 3,3 -Diethyl-4,4 -dimethyl-
0
procedure in Section 4.6 to yield 92.7% (41 mg) of por-
2,2 -dipyrrylmethane (21) (460 mg, 2 mmol) and
pyridine-3-carbaldehyde (190 lL, 2 mmol) were mixed
1
phyrin 4. H NMR (DMSO-d , 300 MHz): ꢀ3.02 (s,
6
2
H), 4.65 (s, 6H), 7.88 (t, J = 8.6 Hz, 6H), 8.21 (d,
in 500 mL CH Cl /C H OH (95:5). After reaction, the
2
2
2
5
J = 5.4 Hz, 4H), 8.58 (t, J = 6.9 Hz, 2H), 8.94 (d,
J = 3.9 Hz, 4H), 9.09 (s, 4H), 9.37 (s, 2H), 9.50 (d,
J = 5.7 Hz, 2H), 10.0 (d, J = 6 Hz, 2H).
mixture was treated and purified according to procedure
in Section 4.3. Purified porphyrin 24 was obtained in
1
135 mg (21.4%). H NMR (CDCl , 300 MHz): ꢀ2.28
3
(s, 2H), 1.77 (m, 12H), 2.66 (m, 12H), 4.23 (m, 8H),
4
(
2
.6.11. 5,15-Diethyl-di(3-pyridyl)-porphyrin (20). Pyrrole
4 mL, 57.2 mmol), pyridine-4-carbaldehyde (2.74 mL,
8.6 mmol), and propionaldehyde (2.08 mL, 28.6 mmol)
7.93 (s, 2H), 8.55 (s, 2H), 9.28 (d, J = 4.2 Hz, 2H),
9.57 (d, J = 6.6 Hz, 2H), 10.46 (s, 2H); UV–vis (CHCl3):
kmax (nm, log e) = 409 (5.25), 508 (4.19), 542 (3.81), 576
+
were mixed. After reaction, the mixture was treated and
purified according to procedure 4.1 to yield 62 mg
(3.86), 626 (3.48); ESI HRMS for C H N (M+H) :
4
2
44
6
found 633.3708, calcd 633.3700.
1
1.09%) of porphyrin 20. H NMR (CDCl , 300 MHz):
(
3
ꢀ
2.73 (s, 2H), 2.11 (t, J = 7.5 Hz, 6H), 5.01 (m, 4H),
.74 (m, 2H), 8.47 (d, J = 6 Hz, 2H), 8.87 (d,
J = 4.8 Hz, 4H), 9.05 (t, J = 2.4 Hz, 2H), 9.46 (t,
J = 7.2 Hz, 6H); UV–vis (CHCl ): k (nm, log
4.6.16. 2,8,12,18-Tetraethyl-3,7,13,17-tetramethyl-5,15-
di(N-methyl-pyridium-3-yl)-porphyrin (11). Porphyrin
24 (50 mg, 79.1 lmol) and 3 mL of methyl iodide were
mixed. After reaction, the mixture was treated and puri-
fied according to procedure in Section 4.6. Compound
7
3
max
e) = 418 (5.51), 516 (4.19). 552 (3.93), 592 (3.70), 651
+
3.81); ESI HRMS for C H N (M+H) : found
1
(
11 was obtained in a yield of 97.4% (71 mg). H NMR
3
4
28
6
5
21.2454, calcd 521.2448.
(DMSO-d6, 300 MHz): ꢀ2.56 (s, 2H), 1.76 (t,
J = 7.4 Hz, 12H), 3.40 (s, 12H), 4.11 (d, J = 7.5 Hz,
8H), 4.72 (s, 6H), 8.64 (t, J = 7.4 Hz, 2H), 9.49 (t,
J = 7.4 Hz, 2H), 9.57 (d, J = 6.0 Hz, 2H), 9.93 (d,
J = 10.2 Hz, 2H), 10.40 (s, 2H); UV–vis (DMF): kmax
(nm, log e) = 412 (5.03), 509 (4.15), 542 (3.97), 576
4
.6.12. 5,15-Diethyl-di(N-methyl-pyridium-3-yl)-porphy-
rin (5). Porphyrin 20 (25 mg, 48.1 lmol) and 2 mL of
methyl iodide were mixed. After reaction, the mixture
was treated and purified according to procedure in