1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.4.3 5 4 , 10 4 , 15 4 , 20 4 -Tetra-t-Butyl-5 6 -Methyl-5, 10, 15, 20-Tetraphenylporphyrin-5 2 - HO 2 C 148 Ethanoic Acid, 51 According to GP II, 176 mg (197 µmol) of cyanomethyl porphyrin 50 are reacted in a mixture of 15 mL of glacial HOAc, 15 mL of H2SO4 and 5 mL of water. Purification is achieved by FC over silica with toluene and THF (ratio 19 : 1) as eluent. Yield: 147 mg (161 µmol) of 51 as purple powder, equiv. to 82 % based on 50. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.73 (s, 2 H, NH), 1.54 (s, 27 H, t-BuH), 1.59 (s, 9 H, t-BuH), 1.81 (s, 3 H, CH3), 3.24 (s, 2 H, CH2), 7.49 (s, 2 H, Ar’H), 7.76 (m, 6 H, ArH), 8.08 (m, 6 H, ArH), 8.59 (d, 3 J = 4.1 Hz, 2 H, β-H), 8.77 (d, 3 J = 4.1 Hz, 2 H, β-H), 8.83 (s, 4 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 23.2, 31.5, 31.6, 34.7, 34.8, 115.1, 116.3, 119.9, 123.5, 123.9, 124.0, 125.2, 134.5, 135.1, 139.0, 139.4, 150.3, 150.5, 151.2, 176.2. MS (FAB+, NBA): m/z (%) = 910 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3431, 3107, 2961, 2898, 2866, 1713, 1623, 1557, 1504, 1472, 1396, 1363, 1267, 1184, 1108, 1023, 967, 849, 802, 738. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (313600), 516 (13400), 551 (7300), 592 (4700), 647 (3400). N NH HN N 51 C 63 H 66 N 4 O 2 M = 911.22 g·mol -1 EA: C63H66N4O2·H2O. Calc.: C 81.43, H 7.38, N 6.03; found: C 81.39, H 7.34, N 5.88.
Experimental Section 6 6.2.4.4 5 4 , 10 4 , 15 4 , 20 4 -Tetra-t-Butyl-[ 3,5 2 ]-Ethano- 5 6 -Methyl- 3 1 -Oxo-5, 10, 15, 20- O Tetraphenylporphyrin, 53 The synthesis follows GP III. Scheduled amounts: porphyrin ethanoic acid 51 (100 mg, 110 µmol); a.: CH2Cl2 (30 mL), Cu(OAc)2·2 H2O (380 mg, <strong>1.1</strong> mmol, 10 eq.); b.: CH2Cl2 (50 mL), C2O2Cl2 (2 mL); CH2Cl2 (30 mL), SnCl4 (1.0 mL, 8.54 mmol); c.: TFA (10 mL), conc. H2SO4 (2 mL). The product is finally purified by FC over silica with CH2Cl2 and hexanes (ratio 1 : 2) as eluent. Yield: 58 mg (65 µmol) of 53 as dark green-purple powder, equiv. to 59.1 % based on 51. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.62 (s, 2 H, NH), <strong>1.1</strong>7 (s, 3 H, CH3), 1.50 (s, 9 H, t- BuH), 1.58 (s, 18 H, t-BuH), 1.59 (s, 9 H, t-BuH), 4.11 (d, 2 J = 11.3 Hz, 1 H, CH2), 5.49 (d, 2 J = 11.7 Hz, 1 H, CH2), 7.35 (d, 4 J = 1.7 Hz, 1 H, Ar’H), 7.68 (d, 4 J = 1.7 Hz, 1 H, Ar’H), 7.69-8.32 (div m’s, 12 H, ArH), 8.63 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.67 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.74 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.79 (m, 4 H, β-H), 8.89 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.96 (s, 1 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.5, 31.4, 31.6, 34.7, 34.8, 34.9, 53.7, 114.0, 119.0, 122.0, 123.8, 123.9, 124.0, 124.2, 124.6, 125.8, 126.1, 128.3, 134.3, 134.7, 136.1, 137.7, 138.1, 138.5, 138.6, 142.1, 150.8, 150.9, 151.2, 152.3, 192.4. MS (FAB+, NBA): m/z (%) = 893 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3316, 3029, 2957, 2903, 2868, 1683, 1606, 1552, 1498, 1475, 1393, 1363, 1351, 1262, 1239, 1197, 1154, 1108, 1019, 984, 965, 869, 850, 799, 718. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 442 (223000), 543 (11300), 587 (9000), 626 (4100), 689 (9000). N NH HN N 53 C 63 H 64 N 4 O M = 893.21 g·mol -1 EA: C63H64N4O·2 H2O. Calc.: C 81.43, H 7.38, N 6.03; found: C 81.26, H 7.54, N 5.74. 149
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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 has been d
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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 other band
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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 90 5 μA -
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3 Discussion and Results 3.2.7 Appr
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3 Discussion and Results (75 eq.) w
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3 Discussion and Results 3.2.7.2 Sy
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Page 196 and 197: 6 Experimental Section broad signal
Page 198 and 199: 7 References 16 H. Fischer, K. Zeil
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S. Jasinski, N. Jux, “Investigati
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Ein großer Dank gilt auch den Ange
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Cirruculum vitae Stefan Jasinski Ge
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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