1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.4.12 10 4 ,15 4 ,20 4 -Tri-t-Butyl-5 2 -(Hydroxymethyl)-5, 10, 15,20-Tetraphenylporphyrin,
HO
61
Firstly, the zinc(II) complex of porphyrin methanoate 60,
Zn(II)-60, is formed by addition of a concentrated methanolic
solution of Zn(OAc)2·2 H2O (1.57 g, 7.1 mmol) to 60 (300 mg,
357 µmol) dissolved in CH2Cl2 (50 mL) in a 100 mL round
bottom flask. This mixture is stirred at rt until TLC control
shows completion. Thereupon, the purple solution is
transferred into a separatory funnel and washed with water
trice, dried over MgSO4 and brought to dryness under high
vacuum. Thus obtained Zn(II)-60 (pinkish powder) is then
transferred into a 100 mL round bottom flask with N2 inlet and dissolved in abs. THF (50 mL)
under inert gas atmosphere. Subsequently, LiAlH4 (135 mg, 3.57 mmol) is added and the
mixture is allowed to react for 30 min at rt, before the reaction is quenched by careful
addition of methanol (10 mL). Upon acidification with 6 M aqueous HCl, the crude product is
extracted with CH2Cl2. The combined organic layers are washed with water, neutralized by
shaking out with a saturated aqueous solution of NaHCO3 and washed with water again.
After drying over MgSO4 and evaporation of the solvent, FC (silica, CH2Cl2 : hexanes = 5 : 3)
yields 252 mg (310 µmol) of pure 61 as purple powder, equiv. to 87 % yield based on 60.
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.71 (s, 2 H, NH), 1.21 (t, 3 J = 5.6 Hz, 1 H, OH), 1.60
(s, 18 H, t-Bu-H), 1.61 (s, 9 H, t-Bu-H), 4.31 (d, 3 J = 5.2 Hz, 2 H, CH2), 7.64 (dt, 3 J = 7.6 Hz,
4 3 3
J = 0.9 Hz, 1 H, Ar’H), 7.75 (m, 6 H, ArH), 7.81 (t, J = 7.6 Hz, 1 H, Ar’H), 7.89 (d, J = 7.7 Hz,
1 H, Ar’H), 8.13 (br m, 7 H, ArH & Ar’H), 8.66 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.88 (m, 6 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.7, 34.9, 63.8, 116.5, 120.4, 120.7, 123.6, 125.7,
126.9, 128.8, 131.2, 131.5, 134.1, 134.4, 138.9, 139.2, 140.3, 142.3, 150.5.
MS (FAB+, NBA): m/z (%) = 813 (100) [MH] +· .
IR (ATR): 𝜈� [cm -1 ] = 3410, 3028, 2960, 2903, 2866, 1809, 1606, 1559, 1505, 1473, 1396, 1362,
1348, 1266, 1193, 1153, 1108, 1023, 993, 981, 967, 881, 849, 801.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (285200), 517 (10400), 552 (5200), 591 (3100),
646 (2000).
N
NH HN
N
61
C 57 H 56 N 4 O
M = 813.08 g·mol -1
157