1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.6.7 5 4 , 10 4 , 20 4 -Tri-t-Butyl-[ 3,5 2 ]-Ethano- 3 1 -Oxo- 5 6 -Methyl- 15 4 -Nitro-5,10,15,20-
O
184
Tetraphenylporphyrin, 91
N
NH HN
N
91
C 59 H 55 N 5 O 3
M = 882.10 g·mol -1
NO 2
To accomplish the demetallation, 50 mg (53 μmol) of
copper(II) cycloketo-porphyrin Cu(II)-91 are dissolved in
5 mL of TFA in a 50 mL round bottom flask. Upon addition of
1 mL of conc. H2SO4, the reaction mixture turns orange-
brown immediately and is then stirred at rt for 45 min. After
transferring the reaction mixture into a separatory funnel, it
is washed with water trice, neutralized by shaking with a
saturated aqueous solution of NaHCO3, washed with water
again, dried over MgSO4 and brought to dryness. Final FC
over silica (CH2Cl2 : hexanes = 2 : 1 as eluent) gives 44.9 mg (50.9 μmol) pure 91 as dark
green powder, equiv. to 96 % yield based on Cu(II)-91.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.69 (s, 2 H, NH), 1.16 (s, 3 H, CH3), 1.50 (s, 9 H, t-
BuH), 1.58 (s, 9 H, t-BuH), 4.12 (d, 2 J = 11.8 Hz, 1 H, CH2), 5.48 (d, 2 J = 11.8 Hz, 1 H, CH2), 7.36
(d, 4 J = 1.9 Hz, 1 H, Ar’H), 7.68 (d, 4 J = 1.9 Hz, 1 H, Ar’H), 7.70 (d overlaid, 2 H, ArH), 7.79 (m,
3 H, ArH), 7.90 (d, 3 J = 7.8 Hz, 1 H, ArH), 8.11 (br s, 1 H, Ar’’H), 8.17 (d, 3 J = 7.3 Hz, 1 H, ArH),
8.33 (br s, 1 H, Ar’’H), 8.52 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.57 (br s overlaid, 1 H, Ar’’H), 8.58 (d,
3 J = 4.9 Hz, 1 H, β-H), 8.66 (br s, 1 H, Ar’’H), 8.70 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.81 (d, 3 J = 4.9 Hz,
1 H, β-H), 8.85 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.93 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.97 (s, 1 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.4, 31.4, 31.5, 34.7, 34.9, 53.6, 115.3, 117.9,
119.6, 122.1, 124.0, 124.1, 124.3, 124.6, 125.7, 126.4, 128.4, 130.8 (br), 131.5, 134.3, 134.6,
134.9, 135.2, 136.1, 137.5, 137.8, 138.2, 142.2, 147.9, 148.6, 151.0, 151.4, 152.6, 192.0.
MS (MALDI-TOF, no matrix): m/z (%) = 883 (100) [MH] + .
IR (ATR): 𝜈� [cm -1 ] = 3321, 2963, 2929, 2907, 2867, 1680, 1597, 1558, 1519, 1475, 1397, 1361,
1346, 1263, 1242, 1110, 1015, 986, 967, 871, 849, 816, 799, 744, 727, 716.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 442 (219000), 545 (10600), 588 (9700), 688 (8600).
EA: C59H55N5O3·C6O14·0.5 H2O. Calc.: C 79.88, H 7.22, N 7.17; found: C 79.65, H 7.10, N 7.17.