1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
EA: C65H71BrN4O·0.5 CH2Cl2·0.5 C6H14. Calc.: C 75.50, H 7.31, N 5.14; found: C 75.84, H 7.42, N
4.96.
6.2.6.2 αβ-5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-5 2 -(Cyanomethyl)-15 2 -(Methoxymethyl)-5 6 ,15 6 -
NC
Dimethyl-5,10,15,20-Tetraphenylporphyrin, 83
The synthesis follows GP I, being applied on 80 mg
(79.7 μmol) of bromo- and methoxymethyl porphyrin 82 with
a.: CH2Cl2 (25 mL), Zn(OAc)2·2 H2O (0.35 g, 1.59 mmol,
20 eq.); b.: KCN (0.26 g, 4.0 mmol, 50 eq.), PEG 400 (25 mL).
Final purification is achieved by FC over silica with a mixture
of CH2Cl2 and hexanes (3 : 2 ratio) as eluent to furnish 72 mg
(75.7 μmol) of pure 83 as purple powder, equiv. to 95 % yield
based on 82.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.54 (s, 2 H, NH), 1.64 (s, 18 H, t-BuH), 1.66 (s, 9 H,
t-BuH), 1.67 (s, 9 H, t-BuH), 1.93 (s, 3 H, CH3), 1.98 (s, 3 H, CH3), 2.83 (s, 3 H, OCH3), 3.29 (s,
2 H, CH2CN), 4.01 (s, 2 H, CH2OCH3), 7.59 (s, 1 H, Ar’H), 7.67 (s, 1 H, Ar’H), 7.67 (m, 4 H, ArH),
7.81 (s, 1 H, Ar’H), 7.85 (s, 1 H, Ar’H), 8.21 (m, 4 H, ArH), 8.65 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.74
(d, 3 J = 4.7 Hz, 2 H, β-H), 8.92 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.95 (d, 3 J = 4.7 Hz, 4 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 21.7, 21.9, 23.3, 31.6, 31.7 (two signals), 34.9,
35.0 (two signals), 58.1, 73.4, 115.0, 117.3, 118.2, 120.3, 120.9, 122.4, 123.7, 123.9, 125.4,
126.5, 130-132 (br), 131.6, 134.5, 134.7, 136.7, 138.2, 138.8, 139.2, 139.6, 140.2, 150.7,
151.5, 152.3.
MS (FAB+, NBA): m/z (%) = 950 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3313, 3035, 2962, 2928, 2908, 2867, 1606, 1561, 1504, 1476, 1461, 1397,
1362, 1350, 1266, 1221, 1208, 1187, 1108, 1024, 993, 982, 968, 913, 874, 848, 823, 800, 740.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (394000), 516 (20200), 551 (9600), 692 (7200),
647 (5300).
EA: C66H71N5O·0.5 CH2Cl2·0.5 H2O. Calc.: C 79.73, H 7.34, N 6.99; found: C 79.80, H 7.55, N
6.80.
N
NH HN
N
C66H71N5O M = 950.30 g·mol-1 O
83
179