Y. You et al. / Bioorg. Med. Chem. 13 (2005) 5968–5980
5977
CDCl3): d 1.43 (6H, t, J = 7.2 Hz), 1.56 (12H, d,
J = 6.8 Hz), 3.23–3.34 (2H, m), 4.43 (4H, q,
J = 6.8 Hz), 4.93 (4H, s), 7.36 (4H, d, J = 8.4 Hz), 7.67
(4H, d, J = 8.0 Hz), 8.17 (4H, d, J = 8.0 Hz), 8.19 (4H,
d, J = 8.4 Hz), 8.68 (2H, d, J = 4.4 Hz), 8.72 (2H, d,
J = 4.4 Hz), 9.68 (2H, s), 9.72 (2H, s); 13C NMR
(75 MHz, 1:1 CDCl3/DMSO-d6): d 14.44, 24.40, 34.29,
61.73, 65.93, 111.04, 113.91, 125.68, 133.44, 134.42,
134.54, 134.78, 135.00, 135.34, 135.52, 135.65, 138.82,
148.03, 148.12, 148.78, 156.67, 158.19, 169.16; High
Resolution Q-TOF MS: m/z 937.3388 (calcd for
C58H52N2O6S2+H, 937.3345).
d, J = 7.5 Hz), 8.60 (2H, s), 8.66 (2H, s), 9.70 (2H, s),
9.76 (2H, s), 10.08 (2H, s); High Resolution ESI MS:
m/z 885.2299 (calcd for C52H40N2O8S2+H, 885.2316).
4.2.35. General method for the preparation of diethyl 5,20-
diaryl-10,15-bis(4-carboxylatomethoxyphenyl)-21,23-dithia-
porphyrins (3–11). Compounds 3–11 were prepared, as
described for the preparation of 4.
4.2.36. 5,20-Bis(4-chlorophenyl)-10,15-bis(4-carboxylato-
methoxyphenyl)-21,23-dithiaporphyrin (4). Core-modi-
fied porphyrin 36 (0.13 g, 0.14 mmol) was dissolved in
20 mL THF and 10 mL of 1 M aqueous NaOH was add-
ed. The resulting solution was stirred at ambient temper-
ature for 15 h. The solution was acidified by the addition
of 4.3 mL acetic acid. The reaction mixture was diluted
with 100 mL H2O and the products were extracted with
EtOAc (3· 100 mL). The combined organic extracts
were dried over MgSO4 and concentrated. The crude
product was washed with several portions of hexanes/
MeOH to give 0.11 g (90%) of 4 as a purple solid. Mp:
4.2.31. Diethyl 5,20-di(biphenyl)-10,15-bis(4-carboxylato-
methoxyphenyl)-21,23-dithiaporphyrin (40). Yield: 87%;
1
mp: 122–124 ꢁC; H NMR (500 MHz, CDCl3): d 1.42
(6H, t, J = 7.0 Hz), 4.42 (4H, q, J = 7.0 Hz), 4.93 (4H,
s), 7.38 (4H, d, J = 7.5 Hz), 7.49 (2H, t, J = 7.5 Hz), 7.61
(4H, t, J = 7.5 Hz), 7.93 (4H, d, J = 7.0 Hz), 8.06 (4H, d,
J = 7.5 Hz), 8.20 (4H, d, J = 8.0 Hz), 8.33 (4H, d,
J = 7.5 Hz), 8.71 (2H, d, J = 4.5 Hz), 8.76 (2H, d,
J = 4.5 Hz), 9.71 (2H, s), 9.78 (2H, s); High Resolution
ESI MS: m/z 1005.3010 (calcd for C64H48N2O6S2+H,
1005.3027).
1
210–212 ꢁC: H NMR (400 MHz, 1:1 CDCl3/CD3OD):
d 4.93 (4H, s), 7.40 (4H, d, J = 8.4 Hz), 7.80 (4H, d,
J = 7.6 Hz), 8.12–8.21 (8H, m), 8.65 (2H, d,
J = 4.0 Hz), 8.71 (2H, d, J = 4.4 Hz), 9.66 (2H, s), 9.75
(2H, s); 13C NMR (75 MHz, DMSO-d6): 65.65, 114.17,
128.09, 132.74, 134.46, 134.54, 134.62, 135.04, 135.20,
135.48, 135.60, 135.78, 136.14, 139.80, 147.75, 148.59,
156.60, 157.10, 158.57, 171.57; High Resolution Q-
TOF MS: m/z 865.1021 (calcd for C48H30Cl2N2O6S2+H,
865.1000); Anal. Calcd for C48H30Cl2N2O6S2: C, 66.59;
H, 3.49; N, 3.24. Found: C, 66.99; H, 3.82; N, 2.94.
4.2.32. Diethyl 5-phenyl-20-(4-fluorophenyl)-10,15-bis(4-
carboxylatomethoxyphenyl)-21,23-dithiaporphyrin (50).
Yield: 81%; mp: 145–147 ꢁC; 1H NMR (500 MHz,
CDCl3): d 1.43 (6H, t, J = 7.2 Hz), 4.43 (4H, q,
J = 6.8 Hz), 4.93 (4H, s), 7.37 (4H, d, J = 8.4 Hz), 7.52
(2H, t, J = 8.4 Hz), 7.79–7.86 (3H, m), 8.18 (4H, d,
J = 8.4 Hz), 8.18–8.28 (4H, m), 8.65 (1H, d, J = 4.4 Hz),
8.67–8.72 (3H, m), 9.63 (1H, d, J = 5.2 Hz), 9.68 (1H, d,
J = 5.2 Hz), 9.70 (2H, s); 13C NMR (75 MHz, CDCl3): d
14.37, 61.68, 64.46, 65.82, 110.97, 113.87, 114.59 (d,
J = 22), 127.52, 128.15, 133.83, 134.24, 134.73, 135.11,
135.47, 141.25, 147.81, 148.18, 156.70, 158.17, 162.97,
(d, J = 320), 169.06; High Resolution Q-TOF MS:
871.2320 (calcd for C52H39FN2O6S2+H, 871.2312).
4.2.37. 5,20-Bis(4-trifluoromethylphenyl)-10,15-bis(4-carb-
oxylatomethoxyphenyl)-21,23-dithiaporphyrin (5). Yield:
1
92%; mp: 220–222 ꢁC; H NMR (400 MHz, DMSO-d6):
d 4.90 (4H, s), 7.38 (4H, d, J = 8.4 Hz), 8.05 (8H, t,
J = 6.3 Hz), 8.36 (4H, d, J = 7.6 Hz), 8.58 (2H, d,
J = 4.4 Hz), 8.69 (2H, d, J = 4.4 Hz), 9.62 (2H, s), 9.76
(2 H, s); High Resolution Q-TOF MS: m/z 933.1529 (calcd
for C50H30F6N2O6S2+H, 933.1528); Anal. Calcd for
C50H30F6N2O6S2: C, 64.37; H, 3.24; N, 3.00. Found: C,
64.20; H, 3.02; N, 2.96.
4.2.33. Diethyl 5-phenyl-20-(4-trifluoromethylphenyl)-10,15-
bis(4-carboxylatomethoxyphenyl)-21,23-dithiaporphyrin (51).
Yield: 87%; mp: 125–127 ꢁC; 1H NMR (400 MHz,
CDCl3): d 1.44 (6H, t, J = 6.8 Hz), 4.44 (4H, q, J =
6.8 Hz), 4.93 (4H, s), 7.38 (4H, d, J = 4.0 Hz), 7.79–7.89
(3H, m), 8.09 (2H, d, J = 8.0 Hz), 8.18 (4H, d, J =
8.0 Hz), 8.23–8.29 (2H, m), 8.37 (2H, d, J = 8.4 Hz),
8.62 (1H, d, J = 4.4 Hz), 8.68–8.76 (3H, m), 9.59 (1H, d,
J = 5.2 Hz), 9.70 (1H, d, J = 4.8 Hz), 9.73 (2H, s); 13C
NMR (75 MHz, CDCl3): d 14.43, 61.74, 65.88, 113.96,
124.55, 127.62, 128.27, 131.65, 134.02, 134.09, 134.31,
134.44, 134.73, 134.86, 135.08, 135.55, 135.71, 135.80,
135.91, 141.23, 145.10, 147.51, 147.76, 148.33, 148.52,
155.97, 156.82, 158.29, 169.10; High Resolution Q-TOF
MS: m/z 921.2308 (calcd for C53H39F3N2O6S2+H,
921.2280).
4.2.38. 5,20-Bis(4-methoxyphenyl)-10,15-bis(4-carboxy-
latomethoxyphenyl)-21,23-dithiaporphyrin (7). Yield:
80%; mp: >300 ꢁC; 1H NMR (400 MHz, 1:1 CDCl3/
CD3OD): d 4.06 (6H, s), 4.89 (4H, s), 7.33 (4H, d,
J = 8.4 Hz), 7.37 (4H, d, J = 8.4 Hz), 8.09 (4H, d,
J = 6.8 Hz), 8.11 (4H, d, J = 6.4 Hz), 8.62 (4H, s), 9.67
(4H, s); High Resolution ESI MS: m/z 857.1994 (calcd
for C50H36N2O8S2+H, 857.1986); Anal. Calcd for
C50H36N2O8S2: C, 70.08; H, 4.23; N, 3.27. Found: C,
70.23; H, 4.00; N, 3.24.
4.2.39. 5,20-Bis(4-dimethylaminophenyl)-10,15-bis(4-carb-
oxylatomethoxyphenyl)-21,23-dithiaporphyrin (8). Yield:
86%; mp: >300 ꢁC; 1H NMR (400 MHz, 1:1 CDCl3/
CD3OD): d 3.28 (12H, s), 4.91 (4H, s), 7.21 (4H, d,
J = 8.4 Hz), 7.41 (4H, d, J = 6.8 Hz), 8.10 (8H, t,
J = 7.6 Hz), 8.52 (2H, d, J = 4.0 Hz), 8.62 (2H, d,
J = 4.0 Hz), 9.57 (2H, s), 9.65 (2H, s); 13C NMR
(75 MHz, 1:1 CDCl3/CD3OD): d 29.02, 64.87, 110.95,
4.2.34. Diethyl 5,20-bis(4-hydroxyphenyl)-10,15-bis(4-
carboxylatomethoxyphenyl)-21,23-dithiaporphyrin (41).
Yield: 84%; mp: 172–174 ꢁC; 1H NMR (500 MHz,
DMSO-d6): d 1.31 (6H, t, J = 6.5 Hz), 4.30 (4H, q,
J = 7.0 Hz), 5.09 (4H, s), 7.28 (4H, d, J = 7.5 Hz), 7.44
(4H, d, J = 7.5 Hz), 8.06 (4H, d, J = 8.0 Hz), 8.17 (4H,