1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.5.8 αα-5 4 , 10 4 , 15 4 , 20 4 -Tetra-t-Butyl-5 2 ,15 2 -Bis-(Cyanomethyl)-5 6 ,15 6 -Dimethyl-
NC
5,10,15,20-Tetraphenylporphyrin, 74
According to GP I, bromomethyl porphyrin 48 (470 mg,
446 μmol) is subjected to the following setup: a.: CH2Cl2
(50 mL), Zn(OAc)2·2 H2O (1.96 g, 8.93 mmol, 20 eq.); b.: KCN
(2.18 g, 33.5 mmol, 75 eq.), PEG 400 (75 mL). Final FC over
silica with CH2Cl2 as eluent furnishes pure 74 (370 mg,
391 μmol) as a dark purple powder, equiv. to 88 % yield
based on 48.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.64 (s, 2 H, NH), 1.60 (s, 18 H, t-BuH), 1.62 (s, 18 H,
t-BuH), 1.92 (s, 6 H, CH3), 3.22 (s, 4 H, CH2), 7.62 (d, 4 J = 1.5 Hz, 2 H, Ar’H), 7.75 (d, 3 J = 7.3 Hz,
2 H, ArH), 7.77 (d, 3 J = 7.3 Hz, 2 H, ArH), 7.80 (d, 4 J = 1.5 Hz, 2 H, Ar’H), 8.13 (d, 3 J = 7.3 Hz,
2 H, ArH), 8.15 (d, 3 J = 7.3 Hz, 2 H, ArH), 8.61 (d, 3 J = 4.9 Hz, 4 H, β-H), 8.90 (d, 3 J = 4.9 Hz, 4 H,
β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 21.8, 23.2, 31.5, 31.6, 34.9, 35.0, 115.4, 118.1,
120.6, 122.4, 123.7, 123.9, 126.5, 129.7, 131.5, 132.4, 134.5, 134.7, 137.9, 138.5, 140.1,
150.9, 152.5.
MS (FAB+, NBA): m/z (%) = 945 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3030, 2953, 2914, 2845, 1737, 1606, 1556, 1467, 1397, 1363, 1239, 1185,
1108, 1061, 1019, 965, 872, 803, 718.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (390000), 516 (19500), 551 (9470), 591 (6610),
648 (6270).
N
NH HN
N
74
C 66 H 68 N 6
M = 945.29 g·mol -1
CN
EA: C66H68N6·0.5 H2O. Calc.: C 83.07, H 7.29, N 8.81; found: C 82.91, H 7.32, N 8.53.
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