1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.5.6 αβ-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, 69
Using GP III, porphyrin diethanoic acid 76 (146 mg, 140 μmol)
is brought to reaction with: a.: Cu(OAc)2·H2O (280 mg,
1.4 mmol, 10 eq), CH2Cl2 (20 mL); b.: C2O2Cl2 (2 mL), CH2Cl2
(20 mL); SnCl4 (1 mL), CH2Cl2 (20 mL); c.: TFA (5 mL), conc.
H2SO4 (1 mL). The pure product elutes as second major
fraction upon FC over silica using CH2Cl2 and hexanes (ratio:
3 : 2) as eluent. Thus purely yielded 69 in an amount of 77 mg
(81 μmol) appears as green powdery solid, equiv. to 58 %
yield based on 76.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -0.15 (s, 2 H, NH), 1.49 (s, 6 H, CH3), 1.50 (s, 18 H, t-
BuH), 1.58 (2 s, 9+9 H, t-BuH), 4.04 (d, 2 J = 12.0 Hz, 2 H, CH2), 5.16 (d, 2 J = 12.0 Hz, 2 H, CH2),
7.40 (d, 4 J = 2.0 Hz, 2 H, Ar’H), 7.64 (d, 4 J = 2.0 Hz, 2 H, Ar’H), 7.74 (d, 3 J = 8.6 Hz, 2 H, ArH),
7.75 (d, 3 J = 8.6 Hz, 2 H, ArH), 8.00 (d, 3 J = 8.1 Hz, 2 H, ArH), 8.02 (d, 3 J = 8.1 Hz, 2 H, ArH),
8.49 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.64 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.74 (s, 2 H, β-H) ppm.
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, 132.4, 132.5, 133.4, 134.0, 137.0,
137.2, 137.3, 138.0, 142.0, 151.0, 152.4, 152.7, 191.0.
MS (FAB+, NBA): m/z (%) = 947 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3030, 2957, 2903, 2868, 1683, 1606, 1556, 1502, 1478, 1461, 1397, 1363,
1258, 1239, 1197, 1177, 1108, 1046, 1015, 984, 869, 833, 803, 756, 721.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 452 (196000), 469 (130000), 571 (9730), 621 (10600),
733 (13300).
N
NH HN
N
C66H66N4O2 M = 947.26 g·mol-1 O
69
EA: C66H66N4O2·0.5 H2O. Calc.: C 82.90, H 7.06, N 5.86; found: C 83.23, H 6.95, N 5.79.
167