1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.4.11 10 4 , 15 4 , 20 4 - Tri - t - Butyl - [ 3,5 2 ] - Methano - 3 1 - Oxo - 5 , 10 , 15 , 20 - O 156 Tetraphenylporphyrin, 58 According to GP III, the following substances and chemicals are reacted with porphyrin methanoic acid 65 (100 mg, 121 µmol): a.: CH2Cl2 (50 mL), Cu(OAc)2·2 H2O (418 mg, 1.21 mmol); b.: CH2Cl2 (30 mL), C2O2Cl2 (2 mL); CH2Cl2 (30 mL), SnCl4 (1 mL); c.: TFA (5 mL), conc. H2SO4 (1 mL). After FC over silica, eluting with CH2Cl2 and hexanes (ratio 1 : 2), 60 mg (74 µmol) of pure 58 are obtained as a dark green powder, equiv. to 61.2 % yield based on 65. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -0.55 (s, 2 H, NH), 1.56 (s, 9 H, t-Bu-H), 1.58 (s, 18 H, t-Bu-H), 7.44 (t, 3 J = 7.3 Hz, 1 H, Ar‘H), 7.72 (m, 6+1 H, ArH+Ar’H), 8.00 (m, 6 H, ArH), 8.29 (d, 3 J = 7.9 Hz, 1 H, ArH), 8.47 (dd, 3 J = 7.7 Hz, 4 J = <strong>1.1</strong> Hz, 1 H, Ar’H), 8.50 (d, 3 J = 4.8 Hz, 1 H, β- H), 8.56 (m, 2 H, β-H), 8.62 (m, 2 H, β-H), 9.24 (m, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.7, 34.9, 110.5, 118.2, 121.0, 123.2, 123.9, 126.3, 127.4, 129.3, 133.2, 134.1, 134.4, 134.5, 136.5, 137.5, 138.0, 138.3, 151.0, 15<strong>1.1</strong>, 192.0. MS (FAB+, NBA): m/z (%) = 809 (100) [MH] +· . IR (ATR): 𝜈� [cm -1 ] = 3300, 3065, 3030, 2961, 2903, 2868, 2247, 1725, 1648, 1590, 1556, 1525, 1505, 1463, 1397, 1363, 1293, 1279, 1216, 1197, 1162, 1108, 1023, 984, 965, 911, 849, 802, 730. N NH HN N 58 C 57 H 52 N 4 O M = 809.05 g·mol -1 UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 332 (24900), 395 (35500), 465 (99500), 533 (3000), 579 (5000), 644 (7700), 745 (9300). EA: C57H52N4O·H2O. Calc.: C 81.01, H 6.68, N 6.63; found: C 80.85, H 6.61, N 6.40.
Experimental Section 6 6.2.4.12 10 4 ,15 4 ,20 4 -Tri-t-Butyl-5 2 -(Hydroxymethyl)-5, 10, 15,20-Tetraphenylporphyrin, HO 61 Firstly, the zinc(II) complex of porphyrin methanoate 60, Zn(II)-60, is formed by addition of a concentrated methanolic solution of Zn(OAc)2·2 H2O (1.57 g, 7.1 mmol) to 60 (300 mg, 357 µmol) dissolved in CH2Cl2 (50 mL) in a 100 mL round bottom flask. This mixture is stirred at rt until TLC control shows completion. Thereupon, the purple solution is transferred into a separatory funnel and washed with water trice, dried over MgSO4 and brought to dryness under high vacuum. Thus obtained Zn(II)-60 (pinkish powder) is then transferred into a 100 mL round bottom flask with N2 inlet and dissolved in abs. THF (50 mL) under inert gas atmosphere. Subsequently, LiAlH4 (135 mg, 3.57 mmol) is added and the mixture is allowed to react for 30 min at rt, before the reaction is quenched by careful addition of methanol (10 mL). Upon acidification with 6 M aqueous HCl, the crude product is extracted with CH2Cl2. The combined organic layers are washed with water, neutralized by shaking out with a saturated aqueous solution of NaHCO3 and washed with water again. After drying over MgSO4 and evaporation of the solvent, FC (silica, CH2Cl2 : hexanes = 5 : 3) yields 252 mg (310 µmol) of pure 61 as purple powder, equiv. to 87 % yield based on 60. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.71 (s, 2 H, NH), 1.21 (t, 3 J = 5.6 Hz, 1 H, OH), 1.60 (s, 18 H, t-Bu-H), 1.61 (s, 9 H, t-Bu-H), 4.31 (d, 3 J = 5.2 Hz, 2 H, CH2), 7.64 (dt, 3 J = 7.6 Hz, 4 3 3 J = 0.9 Hz, 1 H, Ar’H), 7.75 (m, 6 H, ArH), 7.81 (t, J = 7.6 Hz, 1 H, Ar’H), 7.89 (d, J = 7.7 Hz, 1 H, Ar’H), 8.13 (br m, 7 H, ArH & Ar’H), 8.66 (d, 3 J = 4.7 Hz, 2 H, β-H), 8.88 (m, 6 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 31.7, 34.9, 63.8, 116.5, 120.4, 120.7, 123.6, 125.7, 126.9, 128.8, 131.2, 131.5, 134.1, 134.4, 138.9, 139.2, 140.3, 142.3, 150.5. MS (FAB+, NBA): m/z (%) = 813 (100) [MH] +· . IR (ATR): 𝜈� [cm -1 ] = 3410, 3028, 2960, 2903, 2866, 1809, 1606, 1559, 1505, 1473, 1396, 1362, 1348, 1266, 1193, 1153, 1108, 1023, 993, 981, 967, 881, 849, 801. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 420 (285200), 517 (10400), 552 (5200), 591 (3100), 646 (2000). N NH HN N 61 C 57 H 56 N 4 O M = 813.08 g·mol -1 157
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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 74 Δθ [m
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3 Discussion and Results vibration
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3 Discussion and Results cyanomethy
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3 Discussion and Results Time-resol
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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