1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.4.4 5 4 , 10 4 , 15 4 , 20 4 -Tetra-t-Butyl-[ 3,5 2 ]-Ethano- 5 6 -Methyl- 3 1 -Oxo-5, 10, 15, 20-
O
Tetraphenylporphyrin, 53
The synthesis follows GP III. Scheduled amounts: porphyrin
ethanoic acid 51 (100 mg, 110 µmol); a.: CH2Cl2 (30 mL),
Cu(OAc)2·2 H2O (380 mg, 1.1 mmol, 10 eq.); b.: CH2Cl2
(50 mL), C2O2Cl2 (2 mL); CH2Cl2 (30 mL), SnCl4 (1.0 mL,
8.54 mmol); c.: TFA (10 mL), conc. H2SO4 (2 mL). The product
is finally purified by FC over silica with CH2Cl2 and hexanes
(ratio 1 : 2) as eluent. Yield: 58 mg (65 µmol) of 53 as dark
green-purple powder, equiv. to 59.1 % based on 51.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.62 (s, 2 H, NH), 1.17 (s, 3 H, CH3), 1.50 (s, 9 H, t-
BuH), 1.58 (s, 18 H, t-BuH), 1.59 (s, 9 H, t-BuH), 4.11 (d, 2 J = 11.3 Hz, 1 H, CH2), 5.49 (d,
2 J = 11.7 Hz, 1 H, CH2), 7.35 (d, 4 J = 1.7 Hz, 1 H, Ar’H), 7.68 (d, 4 J = 1.7 Hz, 1 H, Ar’H), 7.69-8.32
(div m’s, 12 H, ArH), 8.63 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.67 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.74 (d,
3 J = 4.9 Hz, 1 H, β-H), 8.79 (m, 4 H, β-H), 8.89 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.96 (s, 1 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.5, 31.4, 31.6, 34.7, 34.8, 34.9, 53.7, 114.0,
119.0, 122.0, 123.8, 123.9, 124.0, 124.2, 124.6, 125.8, 126.1, 128.3, 134.3, 134.7, 136.1,
137.7, 138.1, 138.5, 138.6, 142.1, 150.8, 150.9, 151.2, 152.3, 192.4.
MS (FAB+, NBA): m/z (%) = 893 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3316, 3029, 2957, 2903, 2868, 1683, 1606, 1552, 1498, 1475, 1393, 1363,
1351, 1262, 1239, 1197, 1154, 1108, 1019, 984, 965, 869, 850, 799, 718.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 442 (223000), 543 (11300), 587 (9000), 626 (4100),
689 (9000).
N
NH HN
N
53
C 63 H 64 N 4 O
M = 893.21 g·mol -1
EA: C63H64N4O·2 H2O. Calc.: C 81.43, H 7.38, N 6.03; found: C 81.26, H 7.54, N 5.74.
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