1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.6.8 15 4 -Amino-5 4 , 10 4 , 20 4 -Tri-t-Butyl-[ 3,5 2 ]-Ethano- 3 1 -Oxo- 5 6 -Methyl-5,10,15,20-
O
Tetraphenylporphyrin, 92
N
NH HN
N
92
C 59 H 57 N 5 O
M = 852.12 g·mol -1
NH 2
The reduction is carried out in a 100 mL round bottom flask
with reflux condenser by reacting 50 mg (53 μmol) of
copper(II) cycloketo-porphyrin Cu(II)-91 with SnCl2 (initially
100 mg, 0.53 mmol, 10 eq.) in a solvent mixture consistent
of EtOH (20 mL), EtOAc (12 mL) and 2 M aqueous HCl (2 mL).
The reaction mixture is stirred under reflux for 1 h. Then,
the same amount of SnCl2 is added every 30 min while
stirring under reflux conditions is continued. When TLC
control (CH2Cl2 : hexanes = 2 : 1) indicates completion, the
solvents are evaporated. The residue is taken up in a mixture of CH2Cl2 and 6 M aqueous HCl
and transferred into a separatory funnel where the organic layer is separated. The residing
aqueous layer is extracted with CH2Cl2. All organic layers are then combined and washed
with 2 M aqueous HCl and twice with water. After drying of MgSO4, the crude product is
brought to dryness before it is treated analog to GP III part c. with 5 mL of TFA and 1 mL of
conc. H2SO4. Final purification is achieved by FC (silica, CH2Cl2 : hexanes = 2 : 1) yielding
37 mg (43.4 μmol) of pure 92 as greenish powder, equiv. to 81.8 % yield based on Cu(II)-91.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.61 (s, 2 H, NH), 1.17 (s, 3 H, CH3), 1.49 (s, 9 H, t-
BuH), 1.58 (2s, 9+9 H, t-BuH), 4.01 (s br, 2 H, ArNH2), 4.09(d, 2 J = 11.7 Hz, 1 H, CH2), 5.47 (d,
2 J = 11.7 Hz, 1 H, CH2), 7.03 (s br, 2 H, Ar’’H), 7.34 (d, 4 J = 1.7 Hz, 1 H, Ar’H), 7.67 (d,
4 J = 1.7 Hz, 1 H, Ar’H), 7.64-7.83 (m br, 6 H, ArH), 7.90 (d, 3 J = 7.6 Hz, 1 H, ArH), 8.15 (s br,
1 H, Ar’’H), 8.19 (d, 3 J = 7.8 Hz, 1 H, ArH), 8.17 (d, 3 J = 7.3 Hz, 1 H, ArH), 8.33 (br s, 1 H, Ar’’H),
8.62 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.71 (d, 3 J = 4.6 Hz, 1 H, β-H), 8.78 (m, 3 H, β-H), 8.87 (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, 31.4, 31.6, 34.7, 34.8, 53.7, 113.6, 118.9,
122.4, 123.9 (two signals), 124.2, 124.5, 125.8, 126.0, 128.3, 130.6 (br), 131.8, 134.3, 134.6,
135.5 (br), 136.0, 136.4, 137.7, 138.1, 138.6, 142.1, 146.3, 150.7, 151.1, 152.3, 192.2.
MS (MALDI-TOF, no matrix): m/z (%) = 853 (100) [MH] + .
IR (ATR): 𝜈� [cm -1 ] = 3377, 3326, 3029, 2963, 2905, 2869, 1680, 1621, 1553, 1518, 1475, 1396,
1363, 1347, 1263, 1179, 1109, 1022, 986, 966, 870, 852, 840, 801, 728.
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