1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.5.9 αα - 5 4 , 10 4 , 15 4 , 20 4 - Tetra - t - Butyl - 5 6 , 15 6 - Dimethyl - 5 , 10 , 15 , 20 -
HO 2 C
170
Tetraphenylporphyrin-5 2 ,15 2 -Diethanoic Acid, 77
Following GP II, cyanomethyl porphyrin 74 (350 mg,
370 μmol) is brought to reaction in glacial HOAc (20 mL),
conc. H2SO4 (20 mL) and water (7 mL). Pure 77, obtained
after FC over silica with toluene and THF as eluents
(ratio: 9 : 1), appears as a dark purple powder in 302 mg
(307 μmol) yield, equiv. to 83 % based on 74.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.86 (s, 2 H, NH), 1.48 (s, 18 H, t-BuH), 1.58 (s, 18 H,
t-BuH), 1.80 (s, 6 H, CH3), 3.09 (s, 4 H, CH2), 7.39 (d, 3 J = 7.8 Hz, 2 H, ArH), 7.48 (d, 4 J = 1.5 Hz,
2 H, Ar’H), 7.50 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.58 (d, 3 J = 7.8 Hz, 2 H, ArH), 7.79 (d, 3 J = 7.8 Hz,
2 H, ArH), 7.89 (d, 3 J = 7.3 Hz, 2 H, ArH), 8.47 (d, 3 J = 4.6 Hz, 4 H, β-H), 8.57 (d, 3 J = 4.6 Hz, 4 H,
β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 21.9, 29.7, 31.5, 31.6, 34.7 (two peaks), 39.8,
116.4, 119.7, 123.4 (two peaks), 124.3, 125.4, 128.7, 130.1, 131.2, 134.4, 135.0, 138.8,
138.9, 150.2, 151.4, 177.6.
MS (FAB+, NBA): m/z (%) = 983 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3296, 3026, 2957, 2907, 2868, 1741, 1714, 1606, 1563, 1505, 1475, 1397,
1363, 1289, 1270, 1224, 1189, 1135, 1023, 969, 923, 876, 803, 741, 729.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (354000), 516 (19000), 551 (9650), 593 (7930),
647 (6110) nm.
N
NH HN
N
77
C 66 H 70 N 4 O 4
M = 983.29 g·mol -1
CO 2 H
EA: C64H66N4O4·H2O. Calc.: C 79.17, H 7.25, N 5.60; found: C 78.88, H 7.00, N 5.43.