1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.4.15 10 4 ,15 4 ,20 4 -Tri-t-Butyl-5,10,15,20-Tetraphenylporphyrin-5 2 -Ethanoic Acid, 64 HO 2 C 160 The synthesis follows GP II, involving cyanomethyl porphyrin 63 (90 mg, 110 µmol), glacial HOAc (10 mL), conc. H2SO4 (10 mL) and water (3 mL). Final FC over silica with CH2Cl2 and ethyl acetate (ratio 9 : 1) gives 79 mg (94 µmol) of pure 64 as purple powder, equiv. to 85 % yield based on 63. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.74 (s, 2 H, NH), 1.54 (s, 18 H, t-Bu-H), 1.61 (s, 9 H, t-Bu-H), 3.35 (s, 2 H, CH2), 7.54 – 7.71 (div m, 6+1 H, ArH+Ar’H), 7.75 (d, 3 J = 8.6 Hz, 2 H, ArH), 8.03 (m, 1 H, Ar’H), 8.06 (d, 3 J = 8.6 Hz, 4 H, ArH), 8.11 (d, 3 J = 7.0 Hz, 1 H, Ar’H), 8.15 (d, 3 J = 8.1 Hz, 1 H, Ar’H), 8.60 (d, 3 J = 4.8 Hz, 2 H, β-H), 8.79 (d, 3 J = 4.8 Hz, 2 H, β-H), 8.83 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.86 (d, 3 J = 4.7 Hz, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 25.6, 31.6, 31.7, 34.7, 39.0, 116.7, 120.3, 120.6, 123.6, 125.5, 128.6, 129.3, 131.4, 134.4, 135.4, 139.0, 139.2, 141.9, 150.4, 150.5, 175.3. MS (FAB+, NBA): m/z (%) = 841 (100) [MH] +· . IR (ATR): 𝜈� [cm -1 ] = 3320, 3028, 2962, 2867, 1691, 1598, 1475, 1398, 1350, 1297, 985, 802, 721. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (257400), 517 (9200), 552 (4900), 592 (3000), 648 (2200). N NH HN N 64 C 58 H 56 N 4 O 2 M = 841.09 g·mol -1 EA: C58H56N4O2·H2O. Calc.: C 79.42, H 6.89, N 6.39; found: C 79.20, H 6.75, N 6.14.
Experimental Section 6 6.2.4.16 10 4 ,15 4 ,20 4 -Tri-t-Butyl-[3,5 2 ]-Ethano-3 1 -Oxo-5,10,15,20-Tetraphenylporphyrin, O 57 The preparation is done according to GP III starting from porphyrin ethanoic acid 64 (79 mg, 94 µmol). Furthermore: a.: CH2Cl2 (20 mL), Cu(OAc)2 2 H2O (325 mg, 0.94 mmol); b.: CH2Cl2 (20 mL), C2O2Cl2 (1 mL); CH2Cl2 (20 mL), SnCl4 (0.7 mL); c.: TFA (5 mL), conc. H2SO4 (1 mL). Purification is achieved by FC over silica with CH2Cl2 and hexanes (ratio 1 : 2) as eluent to furnish 50 mg (61 µmol) of pure 57 as dark green powder, equiv. to 65 % yield based on 64. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.70 (s, 2 H, NH), 1.59 (s, 9 H, t-Bu-H), 1.60 (s, 9 H, t- Bu-H), 1.61 (s, 9 H, t-Bu-H), 4.20 (d, 2 J = 11.8 Hz, 1 H, CH2), 5.59 (d, 2 J = 11.8 Hz, 1 H, CH2), 7.19 (dd, 3 J = 7.5 Hz, 4 J = <strong>1.1</strong> Hz, 1 H, ArH), 7.54 (m, 2 H, ArH), 7.81 (br m, 7 H, ArH), 8.00 (d, 3 J = 7.0 Hz, 1 H, ArH), 8.19 (d, 3 J = 7.3 Hz, 1 H, ArH), 8.31 (br s, 2 H, ArH), 8.71 (d, 3 J = 4.7 Hz, 1 H, β-H), 8.76 (d, 3 J = 4.7 Hz, 1 H, β-H), 8.82 (d, 3 J = 4.8 Hz, 1 H, β-H), 8.84 (d, 3 J = 4.8 Hz, 1 H, β-H), 8.90 (d, 3 J = 4.9 Hz, 1 H, β-H), 9.09 (d, 3 J = 4.9 Hz, 1 H, β-H), 9.16 (s, 1 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.6, 34.9, 52.6, 115.8, 119.5, 121.9, 123.8, 125.3, 126.9, 127.2, 127.9, 129.9, 134.2, 138.1, 138.3, 138.5, 141.0, 141.3, 150.7, 150.8, 151.0, 191.5. N NH HN N 57 C 58 H 54 N 4 O M = 823.08 g·mol -1 MS (FAB+, NBA): m/z (%) = 823 (100) [MH] +· . IR (ATR): 𝜈� [cm -1 ] = 3320, 3030, 2961, 2903, 2868, 1725, 1679, 1552, 1502, 1471, 1397, 1363, 1266, 1197, 1158, 1108, 1073, 1023, 984, 965, 911, 849, 802, 729. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 438 (182000), 540 (8200), 584 (7100), 686 (5000). EA: C58H54N4O·H2O. Calc.: C 82.82, H 6.71, N 6.66; found: C 82.53, H 6.68, N 6.42. 161
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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 34 R 1 O N
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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 3.2.2.2 FR
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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 3.2.3.3 Va
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3 Discussion and Results Obviously,
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3 Discussion and Results Like Figur
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3 Discussion and Results utilizatio
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3 Discussion and Results other TPP
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3 Discussion and Results (being sup
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3 Discussion and Results Table 10.
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3 Discussion and Results voltammogr
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3 Discussion and Results 3.2.5 Inhe
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3 Discussion and Results effects 12
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3 Discussion and Results 74 Δθ [m
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3 Discussion and Results 3.2.6.2 10
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3 Discussion and Results vibration
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3 Discussion and Results 3.2.6.4 Sy
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3 Discussion and Results cyanomethy
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3 Discussion and Results 3.2.6.5 Co
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3 Discussion and Results phenyl sub
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3 Discussion and Results Time-resol
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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