1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.5.3 5 4 ,10 4 ,15 4 ,20 4 -Tetra -t-Butyl-[3,5 2 ] , [5 6 ,7]-Diethano-3 1 ,7 1 -Dioxo-5, 10, 15, 20-
O
164
O
Tetraphenylporphyrin, 71
Following GP III, these substances and amounts are used for
reactions with 100 mg (105 μmol) of porphyrin diethanoic
acid 75: a.: CH2Cl2 (20 mL), Cu(OAc)2·H2O (210 mg, 1.05 mmol,
10 eq); b.: CH2Cl2 (20 mL), C2O2Cl2 (2 ml); CH2Cl2 (20 mL), SnCl4
(1 mL); c.: TFA (5 mL), conc. H2SO4 (1 mL). The product is
isolated by FC over silica with CH2Cl2 and hexanes as eluent
(ratio: 3 : 2). Thus are obtained 67.5 mg (73 μmol) of pure 71
as dark green powder, equiv. to 69.9% yield based on 75.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.36 (s, 2 H, NH), 1.51 (s, 9 H, t-BuH), 1.58 (s, 9 H, t-
BuH), 1.59 (s, 18 H, t-BuH), 3.85 (d, 2 J = 11.4 Hz, 2 H, CH2), 4.37 (d, 2 J = 11.4 Hz, 2 H, CH2),
7.71 (s, 2 H, Ar’H), 7.77 (d, 3 J = 8.3 Hz, 6 H, ArH), 8.04 (d, 3 J = 8.2 Hz, 4 H, ArH), 8.07 (br s, 2 H,
ArH), 8.50 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.60 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.69 (s, 4 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.2, 31.6, 34.9 (two peaks), 53.9, 111.9, 123.0,
124.2, 124.4, 125.6, 127.9, 129.0, 131.7, 132.0, 134.8, 136.1, 137.6, 137.8, 151.3, 151.7,
153.9, 190.1.
N
NH HN
N
71
C 64 H 62 N 4 O 2
M = 919.20 g·mol -1
MS (FAB+, NBA): m/z (%) = 920 (100) [MH] +· .
IR (ATR): 𝜈� [cm -1 ] = 3030, 2953, 2903, 2864, 1691, 1606, 1552, 1525, 1502, 1459, 1393, 1363,
1343, 1247, 1197, 1131, 1108, 1027, 1000, 980, 869, 849, 799, 714.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 351 (36100), 463 (123000), 485 (85600), 584 (10500),
627 (17200), 732 (15800).
EA: C64H62N4O2·H2O. Calc.: C 82.02, H 6.88, N 5.98; found: C 81.75, H 6.80, N 5.84.