1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.5.5 αβ - 5 4 , 10 4 , 15 4 , 20 4 - Tetra - t - Butyl - 5 6 ,15 6 - Dimethyl - 5, 10, 15, 20 - HO 2 C 166 Tetraphenylporphyrin-5 2 ,15 2 -Diethanoic Acid, 76 Following GP II, 200 mg (212 μmol) of cyanomethyl porphyrin 73 are reacted in glacial HOAc (15 mL), conc. H2SO4 (15 mL) and water (5 mL). Pure 76 appears in an amount of 177 mg (0.180 μmol) as dark violet powder, equiv. to 85 % yield based on 73, after purification by FC over silica using toluene and THF (ratio 19 : 1) as eluent. 1 H NMR (400 MHz, 40 °C, THF-d8): δ [ppm] = -2.62 (s, 2 H, NH), 1.52 (s, 36 H, t-BuH), 1.70 (s, 6 H, CH3), 3.14 (s, 4 H, CH2), 7.46 (s, 2 H, Ar’H), 7.56 (s, 2 H, Ar’H), 7.67 (d, 3 J = 8.1 Hz, 4 H, ArH), 8.04 (d, 3 J = 7.8 Hz, 4 H, ArH), 8.58 (d, 3 J = 4.6 Hz, 4 H, β-H), 8.70 (d, 3 J = 4.6 Hz, 4 H, β- H), 10.0 (br s, 2 H, COOH). 13 C NMR (100.5 MHz, 40 °C, THF-d8): δ [ppm] = 22.4, 32.1, 35.4 (two peaks), 40.5, 117.8, 120.4, 124.3, 125.2, 125.7, 13<strong>1.1</strong>, 131.9, 135.2, 137.0, 139.5, 140.0, 140.1, 151.3, 151.9, 173.0. MS (FAB+, NBA): m/z (%) = 945 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3200, 3034, 2957, 2903, 2868, 1741, 1710, 1606, 1563, 1505, 1475, 1397, 1363, 1270, 1220, 1189, 1135, 1112, 1023, 965, 923, 876, 799, 741, 729. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (334000), 517 (13900), 550 (4970), 591 (3700), 647 (2680). N NH HN N C66H70N4O4 M = 983.29 g·mol-1 HO2C 76 EA: C66H70N4O4·0.5 H2O. Calc.: C 79.89, H 7.21, N 5.65; found: C 79.83, H 7.28, N 5.45.
Experimental Section 6 6.2.5.6 αβ-5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3,5 2 ],[15 2 ,17]-Diethano-5 6 ,15 6 -Dimethyl-3 1 ,17 1 - O Dioxo-5,10,15,20-Tetraphenylporphyrin, 69 Using GP III, porphyrin diethanoic acid 76 (146 mg, 140 μmol) is brought to reaction with: a.: Cu(OAc)2·H2O (280 mg, 1.4 mmol, 10 eq), CH2Cl2 (20 mL); b.: C2O2Cl2 (2 mL), CH2Cl2 (20 mL); SnCl4 (1 mL), CH2Cl2 (20 mL); c.: TFA (5 mL), conc. H2SO4 (1 mL). The pure product elutes as second major fraction upon FC over silica using CH2Cl2 and hexanes (ratio: 3 : 2) as eluent. Thus purely yielded 69 in an amount of 77 mg (81 μmol) appears as green powdery solid, equiv. to 58 % yield based on 76. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -0.15 (s, 2 H, NH), 1.49 (s, 6 H, CH3), 1.50 (s, 18 H, t- BuH), 1.58 (2 s, 9+9 H, t-BuH), 4.04 (d, 2 J = 12.0 Hz, 2 H, CH2), 5.16 (d, 2 J = 12.0 Hz, 2 H, CH2), 7.40 (d, 4 J = 2.0 Hz, 2 H, Ar’H), 7.64 (d, 4 J = 2.0 Hz, 2 H, Ar’H), 7.74 (d, 3 J = 8.6 Hz, 2 H, ArH), 7.75 (d, 3 J = 8.6 Hz, 2 H, ArH), 8.00 (d, 3 J = 8.1 Hz, 2 H, ArH), 8.02 (d, 3 J = 8.1 Hz, 2 H, ArH), 8.49 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.64 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.74 (s, 2 H, β-H) ppm. 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.6, 31.4, 31.5, 31.6, 34.7, 34.8, 34.9, 53.2, 115.9, 117.7, 124.2, 124.7 (two peaks), 126.6, 128.4, 132.4, 132.5, 133.4, 134.0, 137.0, 137.2, 137.3, 138.0, 142.0, 151.0, 152.4, 152.7, 191.0. MS (FAB+, NBA): m/z (%) = 947 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3030, 2957, 2903, 2868, 1683, 1606, 1556, 1502, 1478, 1461, 1397, 1363, 1258, 1239, 1197, 1177, 1108, 1046, 1015, 984, 869, 833, 803, 756, 721. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 452 (196000), 469 (130000), 571 (9730), 621 (10600), 733 (13300). N NH HN N C66H66N4O2 M = 947.26 g·mol-1 O 69 EA: C66H66N4O2·0.5 H2O. Calc.: C 82.90, H 7.06, N 5.86; found: C 83.23, H 6.95, N 5.79. 167
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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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3 Discussion and Results of rotatio
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3 Discussion and Results Thus, the
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3 Discussion and Results Time-resol
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3 Discussion and Results first redu
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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3 Discussion and Results 3.2.8.1 Us
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3 Discussion and Results With all t
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3 Discussion and Results The interm
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Page 198 and 199: 7 References 16 H. Fischer, K. Zeil
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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