1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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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.
Experimental Section 6 6.2.4.14 10 4 ,15 4 ,20 4 -Tri-t-Butyl-5 2 -(Cyanomethyl)-5,10,15,20-Tetraphenylporphyrin, 63 NC According to GP I, the following amounts are scheduled: bromomethyl porphyrin 62 (101 mg, 115 µmol); a. Zn(OAc)2·2 H2O (505 mg, 2.3 mmol); KCN (375 mg, 5.75 mmol), PEG 400 (25 mL). The product is finally purified by FC over silica with CH2Cl2 and hexanes (ratio 2 : 1) as eluent to yield 90 mg (110 µmol) of 63 as dark violet powder, equiv. to 95% yield based on 62. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.63 (s, 2 H, NH), 1.64 (s, 27 H, t-Bu-H), 3.42 (s, 2 H, CH2), 7.73 (dt, 3 J = 7.6 Hz, 4 J = 1.2 Hz, 1 H, Ar’H), 7.78 (br m, 6+1 H, ArH+Ar’H), 7.87 (dt, 3 J = 8.1 Hz, 4 J = 1.4 Hz, 1 H, Ar’H), 7.98 (d, 3 J = 7.8 Hz, 1 H, Ar’H), 8.18 (br m, 6 H, ArH), 8.66 (d, 3 J = 4.8 Hz, 2 H, β-H), 8.95 (s, 4 H, β-H), 8.96 (d, 3 J = 4.8 Hz, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.8, 31.6, 34.9, 114.9, 117.8, 120.6, 12<strong>1.1</strong>, 123.6, 126.6, 127.5, 129.3, 132.0, 134.3, 134.4, 138.8, 139.0, 141.3, 150.6. MS (FAB+, NBA): m/z (%) = 823 (100) [MH] +· . IR (ATR): 𝜈� [cm -1 ] = 3315, 2962, 2903, 2866, 1558, 1510, 1476, 1397, 1363, 1268, 1220, 1187, 1150, 1109, 1025, 965, 849, 803, 738, 715. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (256300), 516 (9530), 552 (4930), 591 (2850), 647 (2100). N NH HN N 63 C 58 H 55 N 5 M = 822.09 g·mol -1 EA: C58H55N5·H2O. Calc.: C 82.92, H 6.84, N 8.34; found: C 82.67, H 6.79, N 8.19. 159
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Semi-Natural and Synthetic Chiral C
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Die vorliegende Arbeit entstand in
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Table of Contents 1 Introduction 1
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n J j-coupling (constant) with n in
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1 Introduction characteristics. For
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1 Introduction 1.1 Porphyrins - A G
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1 Introduction Especially interesti
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1 Introduction 8 [H] 4 + 4 O H O H
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1 Introduction complexes are usuall
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1 Introduction transitions as it is
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1 Introduction 1.2 Photodynamic The
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1 Introduction Certainly, Photofrin
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1 Introduction intact membranes bei
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1 Introduction components, the limi
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2 State of The Art & Aims They were
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2 State of The Art & Aims 2.2 Aim o
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3 Discussion and Results encapsulat
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3 Discussion and Results diastereot
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3 Discussion and Results 30 E ½ Re
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3 Discussion and Results irradiatio
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3 Discussion and Results 3.2.2.1.2
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3 Discussion and Results Table 4. S
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3 Discussion and Results 3.2.2.3 Ac
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3 Discussion and Results 3.2.3.1 IR
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3 Discussion and Results 3.2.3.2 NM
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3 Discussion and Results Obviously,
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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