1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.5.10 αα-5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3,5 2 ],[15 2 ,17]-Diethano-5 6 ,15 6 -Dimethyl-3 1 ,17 1 -
O
Dioxo-5,10,15,20-Tetraphenylporphyrin, 67
Utilizing GP III, the following substances and amounts are
reacted with porphyrin diethanoic acid 77 (246 mg,
250 μmol): a.: Cu(OAc)2·H2O (500 mg, 2.50 mmol), CH2Cl2
(50 mL); b.: C2O2Cl2 (2.5 mL), CH2Cl2 (30 mL); SnCl4 (1.5 mL),
CH2Cl2 (30 mL); c.: TFA (10 mL), conc. H2SO4 (2 mL). Final FC
over silica with CH2Cl2 and hexanes as eluent (ratio: 3 : 1)
furnishes pure 67 eluting as second major fraction. The
product appears as green-violet crystalline solid in 121 mg
(128 μmol) yield, equiv. to 51 % based on 77.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -0.17 (s, 2 H, NH), 1.48 (s, 6 H, CH3), 1.49 (s, 18 H, t-
BuH), 1.57 (s, 18 H, t-BuH), 4.03 (d, 2 J = 12.0 Hz, 2 H, CH2), 5.15 (d, 2 J = 11.7 Hz, 2 H, CH2),
7.39 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.62 (d, 4 J = 2.0 Hz, 2 H, Ar’H), 7.73 (d, 3 J = 8.6 Hz, 2 H, ArH),
7.74 (d, 3 J = 8.3 Hz, 2 H, ArH), 7.99 (d, 3 J = 8.1 Hz, 2 H, ArH), 8.01 (d, 3 J = 8.1 Hz, 2 H, ArH),
8.47 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.62 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.72 (s, 2 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.6, 31.4, 31.5, 31.6, 34.7, 34.8, 34.9, 53.2,
115.9, 117.7, 124.2, 124.7 (two peaks), 126.6, 128.4, 132.5, 134.0, 137.0, 137.2, 137.9,
142.0, 151.0, 152.4, 152.7, 191.0.
MS (FAB+, NBA): m/z (%) = 947 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3034, 2957, 2926, 2903, 2876, 1687, 1606, 1556, 1502, 1475, 1397, 1363,
1258, 1197, 1177, 1108, 1015, 984, 872, 803, 721.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 455 (175000), 491 (58900), 576 (9960), 622 (19100),
718 (15000).
N
NH HN
N
C66H66N4O2 M = 947.26 g·mol-1 O
67
EA: C66H66N4O2·1.5 H2O. Calc.: C 81.36, H 7.14, N 5.75; found: C 81.76, H 7.05, N 5.58.
171