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Q. Raffy et al. / Tetrahedron Letters 49 (2008) 1865–1869
Notes
NH amide); 8.21 (d, 2H, J = 8.4 Hz, H13); 8.16 (d, 6H,
J = 4.5 Hz, H17); 8.05 (d, 2H, J = 8.4 Hz, H12); 7.31 (d,
1H, J = 8.6 Hz, H10); 6.91 (dd, 1H, J1 = 8.6 Hz,
J2 = 2.4 Hz, H20); 6.84 (d, 1H, J = 2.4 Hz, H40); 4.77 (s,
2H, O–CH2–); 3.69 (t, 1H, J = 8.4 Hz, H170); 2.91 (br t,
2H, J = 3.5 Hz, H60); 2.32 (br dd, 1H, J1 = 13.3 Hz,
J2 = 2.7 Hz, H110); 2.2–2.0 (m, 2H, H90, H160); 2.0–1.78
(m, 2H, H150, H70); 1.75–1.60 (m, 1H, H120); 1.59–0.97
(m, 7H, H160, H150, H110, H70, H120, H80, H140); 0.80 (s,
3H, H180); ꢁ2.87 (s, 2H, NH pyrr.). 13C NMR (75 MHz,
CDCl3, 300 K) d 167.1 (NHC@O); 155.0 (C30); 150.0
(Cq); 149.9 (Cq); 148.3 (C2, C18); 138.7 (Cq); 137.9 (Cq);
137.0 (Cq); 135.1 (C13); 134.8 (C100); 131.0 (br, C pyrr.);
129.3 (C3, C17); 126.9 (C10); 120.9 (Cq); 118.5 (C12);
117.4 (Cq); 117.1 (Cq); 114.9 (C40); 112.3 (C20); 81.7
(C170); 67.9 (O–CH2–); 49.9 (C140); 43.9 (C90); 43.2 (C130);
38.6 (C80); 36.6 (C160); 30.5 (C120); 29.8 (C60); 27.0 (C70);
26.3 (C110); 23.1 (C150); 11.0 (C180). UV–vis (CH2Cl2):
kmax 418, 514, 549, 590, 651 nm. Anal. Calcd for
C61H52N8O3ꢃ3MeOH: C, 73.82; H, 6.20; N, 10.76. Found:
C, 73.95; H, 6.06; N 10.24. HR-MS (MALDI-MS) m/z
calcd: 945.42705 [M+H]+ for C61H52O3, found: 945.42351.
All the new compounds described in this work gave sat-
isfactory spectrometric data (1H NMR, 13C NMR, MS)
and consistent high-resolution mass spectrometry data.
The chemical shifts are given in ppm versus TMS. The
usual nomenclature of steroids has been used for carbon
and proton numbering.
5,10,15-Tris(4-pyridyl)-20-(4-nitrophenyl)porphyrin 1
1H NMR (250 MHz, CDCl3, 300 K): d 9.07 (dd, 6H,
J1 = 4.5 Hz, J2 = 1.6 Hz, H2, H18); 8.88 (s, 4H, H15,
H16); 8.87 (d, 2H, J = 5.0 Hz, H7); 8.82 (d, 2H,
J = 5.0 Hz, H8); 8.67 (dd, 2H, J1 = 6.6 Hz, J2 = 2.0 Hz,
H13); 8.40 (dd, 2H, J1 = 6.6 Hz, J2 = 2.0 Hz, H12); 8.14
(dd, 6H, J1 = 4.5 Hz, J2 = 1.6 Hz, H3, H17); ꢁ2.90 (s, 2H,
NH pyrr.) UV–vis (CH2Cl2/MeOH 97:3): kmax 419, 515,
549, 589, 643 nm. MS (MALDI-MS) m/z [M+H]+ 663.22.
5,10,15-Tris(4-pyridyl)-20-(4-aminophenyl)porphyrin 2
1H NMR (250 MHz, CDCl3, 300 K): d 9.04 (dd, 6H,
J1 = 5.7 Hz, J2 = 1.5 Hz, H2, H18); 9.03 (d, 2H,
J = 4.9 Hz, H8); 8.84 (s, 4H, H15, H16); 8.81 (d, 2H,
J = 4.9 Hz, H7); 8.16 (dd, 6H, J1 = 5.7 Hz, J2 = 1.5 Hz,
H3, H17); 7.98 (d, J = 8.3 Hz, 2H, H12); 7.08 (d, 2H,
J = 8.3 Hz, H13); 4.09 (br s, 2H, NH2); ꢁ2.85 (s, 2H,
NH pyrr.) UV–vis (CH2Cl2/MeOH 97:3): kmax 420, 517,
553, 591, 650 nm. HR-MS (MALDI-MS) m/z calcd:
633.25115 [M+H]+ for C41H28N8, found: 633.25097.
5,10,15-Tris(4-N-methylpyridiniumyl)-20-(4-(3-O-
amidoxymethylestradiol))porphyrin
1H NMR (360 MHz, MeOD, 300 K): d 9.39 (d, 6H,
J = 6.1 Hz, H2, H18); 9.26–9.00 (m, 8H, H7, H8, H15,
H16); 8.96 (d, 6H, J = 6.1 Hz, H3, H17); 8.22 (d, 2H,
J = 8.5 Hz, H13); 8.16 (d, 2H, H12); 7.23 (d, 1H,
J = 8.3 Hz, H10); 6.92 (dd, 1H, J1 = 8.3 Hz, J2 = 2.4 Hz,
H20); 6.86 (d, 1H, J = 2.4 Hz, H40); 3.54 (t, 1H,
J = 9.0 Hz, H170); 2.87 (m, 2H, H60); 2.24 (br d, 1H,H110);
2.08–1.78 (m, 5H, H90, H160, H70, H110); 0.74 (s, 3H,
3-O-Carboxymethylestradiol 4
1
1H NMR (300 MHz, MeOD, 300 K): d 7.12 (d, 1H,
J = 8,6 Hz, H10); 6.64 (dd, 1H, J1 = 8.6 Hz, J2 = 2.6 Hz,
H20); 6.58 (d, 1H, J = 2.6 Hz, H40); 4.52 (s, 2H, O–CH2–);
3.62 (t, 1H, J = 8,5 Hz, H170), 2.75 (m, 2H, H60); 2.24 (br
H180). H NMR (360 MHz, DMSO, 300 K): d 4.84 (s, 2H,
O–CH2–); 4.71 (s, 9H, N+–CH3); 0.70 (s, 3H, H180). UV–
vis (MeOH): kmax 429.5, 522, 561, 591, 657 nm. MS
(MALDI-MS) m/z [M+H]+ 990.45; HR-MS (ESI-MS)
m/z calcd: 329.82812 for [M/3]+; found: 329.8283.
d, 1H, J11 –11 = 13.0 Hz, H110), 2.12–1.96 (m, 1H, H90);
0
0
1.92 (d, 1H, J16 –16 = 12 Hz, H160); 1.81 (m, 1H, H70);
1.64 (m, 1H, H120); 1.57–1.00 (m, 8H, H150, H70, H80,
H110, H120, H140, H160); 0.73 (s, 3H, H180). 13C NMR
(75 MHz, MeOD, 300 K) d 172.8 (–COOH); 157.1 (C30);
139.0 (C50); 134.6 (C100); 127.3 (C10); 115.6 (C40); 113.0
(C20); 82.4 (C170); 65.8 (O–CH2–); 51.2 (C140); 45.2 (C90);
44.3 (C130); 40.2 (C80); 37.9 (C160); 30.73 (C120); 30.67
(C60); 28.4 (C70); 27.5 (C110); 24.0 (C150); 11.8 (C180). HR-
MS (ESI-MS) m/z calcd: 353.1729 [M+H]+ for C20H26O4
found: 353.1729. Anal. Calcd for C20H26O4ꢃ1/3H2O: C,
71.40; H, 7.99. Found: C, 71.37; H, 7.83.
0
0
Iron(III) 5,10,15-tris(4-N-methylpyridiniumyl)-20-(4-(3-O-
amidoxymethylestradiol))porphyrin 6
UV–vis (citrate–phosphate buffer, pH 4.4): kmax (log(e))
428 (4.7), 523 (3.7), 572 (3.4), 659 (3.1) nm. HR-MS
(MALDI-MS) m/z calcd: 1043.40540 for C64H59FeN8O3;
found: 1043.40503.
References and notes
1. Letondor, C.; Ward, T. R. Chem. Biochem. 2006, 7, 1845–
1852.
2. Qi, D.; Tan, C.-M.; Haring, D.; Distefano, M. D. Chem. Rev. 2001,
101, 3081–3111.
5,10,15-Tris(4-pyridyl)-20-(4-(3-O-
amidoxymethylestradiol))porphyrin 5
3. Ricoux, R.; Lukowska, E.; Pezzotti, F.; Mahy, J.-P. Eur. J. Biochem.
2004, 271, 1277–1283.
4. Bertucci, C.; Botteghi, C.; Giunta, D.; Marchetti, M.; Paganelli, S.
Adv. Synth. Catal. 2002, 344, 556–562.
1H NMR (300 MHz, CDCl3, 300 K): d 9.06 (d, 6H,
J = 4,5 Hz, H18); 8.95 (d, 2H, J = 4.8 Hz, H8); 8.86 (s,
2H, H15–H16); 8.83 (d, 2H, J = 4,8 Hz, H7); 8.74 (s, 1H,