1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 445 (183000), 546 (11300), 592 (9900), 692 (9100).
EA: C59H57N5O·EtOAc. Calc.: C 80.48, H 6.97, N 7.45; found: C 80.16, H 6.85, N 7.53.
6.2.6.9 15 4 -Amino-15 4 -N-(t-Butoxycarbonyl)-5 4 , 10 4 , 20 4 -Tri-t-Butyl-[ 3,5 2 ]-Ethano- 3 1 -
O
186
Oxo-5 6 -Methyl-5,10,15,20-Tetraphenylporphyrin, 93
N
NH HN
N
93
C 64 H 65 N 5 O 3
M = 952.23 g·mol -1
O
NH
O
In a 100 mL round bottom flask, amino cycloketo-porphyrin
92 (25 mg, 29.3 µmol) is dissolved in CHCl3 (10 mL). Then,
19 mg (88 µmol, 3 eq.) of di-t-butyl di-carbonate dissolved in
MeOH (2 mL) and TEA (1 mL) are added and the reaction
mixture is stirred at rt for 24 h. After that, the reaction
mixture is transferred into a separatory funnel and washed
with water, a saturated aqueous solution of NH4Cl and water
again. After drying over MgSO4 and evaporation of the
solvent, FC (silica, CH2Cl2) furnishes pure 93 as dark green
powder. Yield: 18.8 mg (19.7 µmol) equiv. to 67.2 % based on 92.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.65 (s, 2 H, NH), 1.16 (s, 3 H, CH3), 1.49 (s, 9 H, t-
BuH), 1.58 (2s, 9+9 H, t-BuH), 1.62 (s, 9 H, BOC), 4.09 (d, 2 J = 11.7 Hz, 1 H, CH2), 5.47 (d,
2 J = 11.7 Hz, 1 H, CH2), 6.82 (s, 1 H, NHBOC), 7.34 (d, 4 J = 1.7 Hz, 1 H, Ar’H), 7.67 (d,
4 J = 1.7 Hz, 1 H, Ar’H), 7.57-7.86 (m’s overlaid, 8 H, ArH/Ar’’H), 7.90 (d, 3 J = 7.6 Hz, 1 H, ArH),
8.18 (d, 3 J = 7.6 Hz, 1 H, ArH), 8.30 (br m, 2 H, ArH), 8.62 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.64 (d,
3 J = 4.8 Hz, 1 H, β-H), 8.70 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.77 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.79 (d,
3 J = 4.8 Hz, 1 H, β-H), 8.88 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.95 (s, 1 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.5, 28.4, 31.4, 31.6, 34.7, 34.9, 53.7, 81.0,
114.1, 116.9, 119.1, 121.2, 123.9, 124.2, 124.5, 125.8, 126.1, 128.3, 134.3, 134.6, 134.9,
135.2, 136.2, 137.7, 138.0, 138.4, 138.5, 142.1, 150.8, 151.2, 152.3, 153.1, 192.2.
MS (FAB+, NBA): m/z (%) = 952 (100) [M] +· , 850 (60) [M-Boc] +· .
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 443 (172000), 545 (8600), 588 (7100), 689 (6800).