1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.4.16 10 4 ,15 4 ,20 4 -Tri-t-Butyl-[3,5 2 ]-Ethano-3 1 -Oxo-5,10,15,20-Tetraphenylporphyrin,
O
57
The preparation is done according to GP III starting from
porphyrin ethanoic acid 64 (79 mg, 94 µmol). Furthermore:
a.: CH2Cl2 (20 mL), Cu(OAc)2 2 H2O (325 mg, 0.94 mmol); b.:
CH2Cl2 (20 mL), C2O2Cl2 (1 mL); CH2Cl2 (20 mL), SnCl4 (0.7 mL);
c.: TFA (5 mL), conc. H2SO4 (1 mL). Purification is achieved by
FC over silica with CH2Cl2 and hexanes (ratio 1 : 2) as eluent to
furnish 50 mg (61 µmol) of pure 57 as dark green powder,
equiv. to 65 % yield based on 64.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.70 (s, 2 H, NH), 1.59 (s, 9 H, t-Bu-H), 1.60 (s, 9 H, t-
Bu-H), 1.61 (s, 9 H, t-Bu-H), 4.20 (d, 2 J = 11.8 Hz, 1 H, CH2), 5.59 (d, 2 J = 11.8 Hz, 1 H, CH2),
7.19 (dd, 3 J = 7.5 Hz, 4 J = 1.1 Hz, 1 H, ArH), 7.54 (m, 2 H, ArH), 7.81 (br m, 7 H, ArH), 8.00 (d,
3 J = 7.0 Hz, 1 H, ArH), 8.19 (d, 3 J = 7.3 Hz, 1 H, ArH), 8.31 (br s, 2 H, ArH), 8.71 (d, 3 J = 4.7 Hz,
1 H, β-H), 8.76 (d, 3 J = 4.7 Hz, 1 H, β-H), 8.82 (d, 3 J = 4.8 Hz, 1 H, β-H), 8.84 (d, 3 J = 4.8 Hz, 1 H,
β-H), 8.90 (d, 3 J = 4.9 Hz, 1 H, β-H), 9.09 (d, 3 J = 4.9 Hz, 1 H, β-H), 9.16 (s, 1 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.6, 34.9, 52.6, 115.8, 119.5, 121.9, 123.8, 125.3,
126.9, 127.2, 127.9, 129.9, 134.2, 138.1, 138.3, 138.5, 141.0, 141.3, 150.7, 150.8, 151.0,
191.5.
N
NH HN
N
57
C 58 H 54 N 4 O
M = 823.08 g·mol -1
MS (FAB+, NBA): m/z (%) = 823 (100) [MH] +· .
IR (ATR): 𝜈� [cm -1 ] = 3320, 3030, 2961, 2903, 2868, 1725, 1679, 1552, 1502, 1471, 1397, 1363,
1266, 1197, 1158, 1108, 1073, 1023, 984, 965, 911, 849, 802, 729.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 438 (182000), 540 (8200), 584 (7100), 686 (5000).
EA: C58H54N4O·H2O. Calc.: C 82.82, H 6.71, N 6.66; found: C 82.53, H 6.68, N 6.42.
161