1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.5.7 αβ-5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3,5 2 ],[13,15 2 ]-Diethano-5 6 ,15 6 -Dimethyl-3 1 ,13 1 - O 168 Dioxo-5,10,15,20-Tetraphenylporphyrin, 70 The system is obtained from the same reaction as 69 (paragraph 6.2.5.6) but elutes as first major fraction upon FC. Pure 70 appears as green powder after evaporation of the solvents in 19 mg (20 μmol) yield, equiv. to 14% based on 76. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -0.93 (s, 2 H, NH), <strong>1.1</strong>7 (s, 6 H, CH3), 1.49 (s, 18 H, t- BuH), 1.57 (s, 18 H, t-BuH), 4.10 (d, 2 J = 11.7 Hz, 2 H, CH2), 5.46 (d, 2 J = 12.0 Hz, 2 H, CH2), 7.34 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.64 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 2 H, ArH), 7.67 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.69 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 2 H, ArH), 7.81 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 2 H, ArH), 8.29 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 2 H, ArH), 8.72 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.79 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.87 (s, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.5, 31.4, 31.6, 34.7, 34.9, 53.5, 115.9, 124.2, 124.4, 124.8, 125.6, 128.5, 129.7, 130.4, 134.0, 135.7, 136.9, 137.2, 137.3, 140.9, 141.5, 151.3, 152.6, 192.2. MS (FAB+, NBA): m/z (%) = 947 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3320, 3030, 2953, 2903, 2868, 1671, 1606, 1552, 1513, 1471, 1420, 1397, 1363, 1343, 1266, 1239, 1193, 1150, 1108, 1031, 984, 876, 853, 799, 710. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 455 (178000), 490 (60600), 576 (9720), 622 (19300), 718 (1510). N NH HN N 70 C 66 H 66 N 4 O 2 M = 947.26 g·mol -1 O EA: C66H66N4O2·0.5 CH2Cl2. Calc.: C 80.70, H 6.82, N 5.66; found: C 80.46, H 6.98, N 5.48.
Experimental Section 6 6.2.5.8 αα-5 4 , 10 4 , 15 4 , 20 4 -Tetra-t-Butyl-5 2 ,15 2 -Bis-(Cyanomethyl)-5 6 ,15 6 -Dimethyl- NC 5,10,15,20-Tetraphenylporphyrin, 74 According to GP I, bromomethyl porphyrin 48 (470 mg, 446 μmol) is subjected to the following setup: a.: CH2Cl2 (50 mL), Zn(OAc)2·2 H2O (1.96 g, 8.93 mmol, 20 eq.); b.: KCN (2.18 g, 33.5 mmol, 75 eq.), PEG 400 (75 mL). Final FC over silica with CH2Cl2 as eluent furnishes pure 74 (370 mg, 391 μmol) as a dark purple powder, equiv. to 88 % yield based on 48. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.64 (s, 2 H, NH), 1.60 (s, 18 H, t-BuH), 1.62 (s, 18 H, t-BuH), 1.92 (s, 6 H, CH3), 3.22 (s, 4 H, CH2), 7.62 (d, 4 J = 1.5 Hz, 2 H, Ar’H), 7.75 (d, 3 J = 7.3 Hz, 2 H, ArH), 7.77 (d, 3 J = 7.3 Hz, 2 H, ArH), 7.80 (d, 4 J = 1.5 Hz, 2 H, Ar’H), 8.13 (d, 3 J = 7.3 Hz, 2 H, ArH), 8.15 (d, 3 J = 7.3 Hz, 2 H, ArH), 8.61 (d, 3 J = 4.9 Hz, 4 H, β-H), 8.90 (d, 3 J = 4.9 Hz, 4 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 21.8, 23.2, 31.5, 31.6, 34.9, 35.0, 115.4, 118.1, 120.6, 122.4, 123.7, 123.9, 126.5, 129.7, 131.5, 132.4, 134.5, 134.7, 137.9, 138.5, 140.1, 150.9, 152.5. MS (FAB+, NBA): m/z (%) = 945 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3030, 2953, 2914, 2845, 1737, 1606, 1556, 1467, 1397, 1363, 1239, 1185, 1108, 1061, 1019, 965, 872, 803, 718. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (390000), 516 (19500), 551 (9470), 591 (6610), 648 (6270). N NH HN N 74 C 66 H 68 N 6 M = 945.29 g·mol -1 CN EA: C66H68N6·0.5 H2O. Calc.: C 83.07, H 7.29, N 8.81; found: C 82.91, H 7.32, N 8.53. 169
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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 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 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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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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3 Discussion and Results 116 HO 2 C
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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