1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.4.10 10 4 ,15 4 ,20 4 -Tri-t-Butyl-5,10,15,20-Tetraphenylporphyrin-5 2 -Methanoic Acid, 65
HO 2 C
In 250 mL round bottom flask equipped with reflux
condenser, porphyrin methanoate 60 (300 mg, 357 µmol) is
dissolved in a mixture of THF (10 mL), water (10 mL) and
ethanol (100 mL) containing powdered KOH (2.0 g, ∼5 wt.-%).
Stirring under reflux for 12 h and subsequent addition of
water furnishes crude 65 as fine precipitate which is collected
by filtration and washed with water. Redissolving in CH2Cl2,
neutralization with 2 M aqueous HCl, washing with water and
drying over MgSO4 gives a violet powder being further
purified by FC over silica raising the polarity of the eluent from pure CH2Cl2 to pure ethyl
acetate. Yield: 277 mg (335 µmol) of 65 as purple powder, equiv. to 95% based on 60.
1 H NMR (300 MHz, rt, CDCl3/THF-d8): δ [ppm] = -2.72 (s, 2 H, NH), 1.56 (s, 27 H, t-Bu-H),
7.68 – 7.76 (m, 6+2 H, ArH+Ar’H), 8.08 – 8.11 (m, 6+1 H, ArH+Ar’H), 8.31 (m, 1 H, Ar’H), 8.61
(d, 3 J = 4.7 Hz, 2 H, β-H), 8.77 – 8.81 (m, 6 H, β-H).
13 C NMR (75.5 MHz, rt, CDCl3/THF-d8): δ [ppm] = 31.6, 34.8, 119.1, 119.9, 120.0, 123.5,
128.1, 129.3, 129.8, 130.8, 134.4, 134.6, 135.9, 139.1, 139.3, 142.6, 150.3, 168.7.
MS (FAB+, NBA): m/z (%) = 827 (100) [MH] +· .
IR (ATR): 𝜈� [cm -1 ] = 3316, 3030, 2961, 2868, 1691, 1598, 1471, 1397, 1351, 1297, 984, 799,
721.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (256300), 517 (10000), 552 (5100), 592 (3100),
648 (2500).
N
NH HN
N
65
C 57 H 54 N 4 O 2
M = 827.06 g·mol -1
EA: C57H54N4O2·1.5 H2O. Calc.: C 80.16, H 6.73, N 6.56; found: C 80.41, H 6.62, N 6.37.
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