1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.5.3 5 4 ,10 4 ,15 4 ,20 4 -Tetra -t-Butyl-[3,5 2 ] , [5 6 ,7]-Diethano-3 1 ,7 1 -Dioxo-5, 10, 15, 20- O 164 O Tetraphenylporphyrin, 71 Following GP III, these substances and amounts are used for reactions with 100 mg (105 μmol) of porphyrin diethanoic acid 75: a.: CH2Cl2 (20 mL), Cu(OAc)2·H2O (210 mg, 1.05 mmol, 10 eq); b.: CH2Cl2 (20 mL), C2O2Cl2 (2 ml); CH2Cl2 (20 mL), SnCl4 (1 mL); c.: TFA (5 mL), conc. H2SO4 (1 mL). The product is isolated by FC over silica with CH2Cl2 and hexanes as eluent (ratio: 3 : 2). Thus are obtained 67.5 mg (73 μmol) of pure 71 as dark green powder, equiv. to 69.9% yield based on 75. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.36 (s, 2 H, NH), 1.51 (s, 9 H, t-BuH), 1.58 (s, 9 H, t- BuH), 1.59 (s, 18 H, t-BuH), 3.85 (d, 2 J = 11.4 Hz, 2 H, CH2), 4.37 (d, 2 J = 11.4 Hz, 2 H, CH2), 7.71 (s, 2 H, Ar’H), 7.77 (d, 3 J = 8.3 Hz, 6 H, ArH), 8.04 (d, 3 J = 8.2 Hz, 4 H, ArH), 8.07 (br s, 2 H, ArH), 8.50 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.60 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.69 (s, 4 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.2, 31.6, 34.9 (two peaks), 53.9, 111.9, 123.0, 124.2, 124.4, 125.6, 127.9, 129.0, 131.7, 132.0, 134.8, 136.1, 137.6, 137.8, 151.3, 151.7, 153.9, 190.1. N NH HN N 71 C 64 H 62 N 4 O 2 M = 919.20 g·mol -1 MS (FAB+, NBA): m/z (%) = 920 (100) [MH] +· . IR (ATR): 𝜈� [cm -1 ] = 3030, 2953, 2903, 2864, 1691, 1606, 1552, 1525, 1502, 1459, 1393, 1363, 1343, 1247, 1197, 1131, 1108, 1027, 1000, 980, 869, 849, 799, 714. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 351 (36100), 463 (123000), 485 (85600), 584 (10500), 627 (17200), 732 (15800). EA: C64H62N4O2·H2O. Calc.: C 82.02, H 6.88, N 5.98; found: C 81.75, H 6.80, N 5.84.
Experimental Section 6 6.2.5.4 αβ-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, 73 According to GP I, the following chemicals are reacted with 350 mg (0.332 mmol) of bromomethyl porphyrin 47: a.: Zn(OAc)2·2 H2O (1.46 g, 6.64 mmol, 20 eq), CH2Cl2 (50 mL); b.: KCN (1.62 g, 24.9 mmol, 75 eq), PEG 400 (50 mL). Upon FC over silica with CH2Cl2 and hexanes (ratio 2 : 1) as eluent mixture, pure 73 (298 mg, 0.316 mmol) is obtained as purple powder, equiv. to 95 % yield based on 47. 1 H NMR (400 MHz, 30 °C, CDCl3/THF-d8): δ [ppm] = -2.66 (s, 2 H, NH), 1.51 (s, 18 H, t-BuH), 1.54 (s, 18 H, t-BuH), 1.84 (s, 6 H, CH3), 3.15 (s, 4 H, CH2), 7.57 (d, 4 J = 1.5 Hz, 2 H, Ar’H), 7.68 (m, 6 H, ArH), 7.74 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 8.04 (m, 6 H, ArH), 8.52 (d, 3 J = 4.6 Hz, 4 H, β-H), 8.79 (d, 3 J = 4.9 Hz, 4 H, β-H). 13 C NMR (100.5 MHz, 30 °C, CDCl3/THF-d8): δ [ppm] = 22.2, 23.6, 32.0, 32.1, 35.4, 35.6, 116.1, 118.3, 121.2, 123.1, 124.4, 127.0, 130.3, 132.6, 132.9, 135.2, 138.7, 139.3, 140.7, 151.5, 153.1. MS (FAB+, NBA): m/z (%) = 945 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3312, 3034, 2957, 2906, 2868, 1722, 1610, 1559, 1505, 1463, 1397, 1363, 1343, 1270, 1208, 1185, 1108, 1023, 965, 872, 849, 799, 737. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (356000), 516 (19100), 551 (8490), 591 (6170), 648 (5380). N NH HN N NC 73 C 66 H 68 N 6 M = 945.29 g·mol -1 EA: C66H68N6·0.5 H2O·0.5 C6H14. Calc.: C 83.09, H 7.68, N 8.43; found: C 83.09, H 7.71, N 8.10. 165
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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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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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