1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
EA: C57H56N4O·0.5 H2O. Calc.: C 83.28, H 6.99, N 6.81; found: C 83.43, H 6.99, N 6.82.
6.2.4.13 5 2 -(Bromomethyl)-10 4 ,15 4 ,20 4 -Tri-t-Butyl-5,10,15,20-Tetraphenylporphyrin, 62
Br
158
In a 100 mL round bottom flask, hydroxymethyl porphyrin 61
(252 mg, 310 µmol) is dissolved in CH2Cl2 (50 mL) and HBr
(5.4 M in glacial acetic acid, 10 mL) is added. The flask is
closed by a one-hole stopper with exhaust duct and the
reaction mixture, now appearing dark-green, is stirred at rt
for 3 h. Then water is added and the biphasic mixture is
transferred in to a separatory funnel where the organic layer
is separated and washed with water repeatedly until it
appears purple. Subsequent neutralization with a saturated
aqueous solution of NaHCO3, washing with water, drying over MgSO4 and evaporation to
dryness furnishes the crude product which is purified by FC (silica, CH2Cl2 : hexanes = 2 : 1) to
yield 101 mg (115 µmol) of pure 62 as violet powder, equiv. to 37% yield based on 61.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.59 (s, 2 H, NH), 1.65 (s, 27 H, t-Bu-H), 4.31 (s, 2 H,
CH2), 7.64 (dt, 3 J = 7.6 Hz, 4 J = 1.4 Hz, 1 H, Ar’H), 7.80 (br m, 6+1 H, ArH+Ar’H), 7.92 (dd,
3 J = 8.1 Hz, 4 J = 1.0 Hz, 1 H, Ar’H), 8.13 (dd, 3 J = 7.6 Hz, 4 J = 1.0 Hz, 1 H, Ar’H), 8.21 (m, 6 H,
ArH), 8.73 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.97 (m, 6 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.6, 31.8, 34.9, 115.7, 120.4, 120.8, 123.6, 126.5,
129.1, 129.7, 131.4, 134.5, 139.0, 139.2, 139.3, 141.6, 150.5.
MS (FAB+, NBA): m/z (%) = 876 (100) [MH] +· , 795 (40) [M-Br] +· .
IR (ATR): 𝜈� [cm -1 ] = 3318, 3028, 2962, 2867, 2360, 1474, 1396, 1363, 1349, 1267, 1220, 1108,
1023, 967, 801, 736.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (303800), 515 (12100), 551 (6000), 590 (3800),
646 (3200).
N
NH HN
N
62
C 57 H 55 BrN 4
M = 875.98 g·mol -1
EA: C57H55BrN4·CH2Cl2. Calc.: C 75.19, H 6.15, N 6.10; found: C 75.01, H 6.11, N 5.99.