1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.5.15 5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-5 2 ,5 6 ,15 2 ,15 6 -Tetrakis-(Cyanomethyl)-5,10,15,20- NC 176 Tetraphenylporphyrin, 78 According to GP I, bromomethyl porphyrin 49 (320 mg, 264 μmol) is subjected to the following setup: a.: CH2Cl2 (50 mL), Zn(OAc)2·2 H2O (<strong>1.1</strong>6 g, 5.29 mmol, 20 eq.); b.: KCN (1.72 g, 26.4 mmol, 100 eq.), PEG 400 (75 mL). Final FC over silica with an eluent mixture of CH2Cl2 and ethyl acetate (10 : 1) furnishes pure 78 (236 mg, 237 μmol) as a dark purple powder, equiv. to 89.7 % yield based on 49. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.62 (s, 2 H, NH), 1.63 (s, 18 H, t-BuH), 1.67 (s, 18 H, t-BuH), 3.29 (s, 8 H, CH2), 7.80 (d, 3 J = 8.3 Hz, 4 H, ArH), 8.00 (s, 4 H, Ar’H), 8.15 (d, 3 J = 8.3 Hz, 4 H, ArH), 8.58 (d, 3 J = 4.8 Hz, 4 H, β-H), 8.98 (d, 3 J = 4.8 Hz, 4 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 23.2, 31.5, 31.6, 34.9, 35.4, 112.5, 117.4, 121.6, 123.9, 124.9, 129.2 (br), 132.5, 133.4 (br), 134.5, 137.4, 137.8, 15<strong>1.1</strong>, 153.9. MS (FAB+, NBA): m/z (%) = 995 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3320, 2962, 2905, 2870, 1610, 1563, 1506, 1476, 1399, 1365, 1352, 1271, 1222, 1210, 1186, 1155, 1111, 1077, 1027, 993, 981, 967, 930, 875, 847, 807, 741, 726. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (423000), 516 (18100), 551 (6300), 593 (5500), 647 (2900). CN N NH HN N NC 78 C 68 H 66 N 8 M = 995.31 g·mol -1 CN EA: C68H66N8·1.5 H2O. Calc.: C 80.60, H 6.76, N 11.06; found: C 80.78, H 6.74, N 11.02.
Experimental Section 6 6.2.5.16 5 4 , 10 4 , 15 4 , 20 4 -Tetra-t-Butyl-5, 10, 15,20-Tetraphenylporphyrin-5 2 , 5 6 , 15 2 , 15 6 - HO 2 C Tetraethanoic Acid, 79 Following GP II, cyanomethyl porphyrin 78 (200 mg, 201 μmol) is brought to reaction in glacial HOAc (20 mL), conc. H2SO4 (20 mL) and water (7 mL). Pure 79, obtained after FC over silica with THF as eluent, appears as a dark purple powder in 157 mg (147 μmol) yield, equiv. to 73 % based on 78. 1 H NMR (400 MHz, rt, THF-d8): δ [ppm] = -2.57 (s, 2 H, NH), 1.60 (s, 18 H, t-BuH), 1.61 (s, 18 H, t-BuH), 3.14 (s, 8 H, CH2), 7.74 (s, 4 H, Ar’H), 7.80 (d, 3 J = 8.3 Hz, 4 H, ArH), 8.14 (d, 3 J = 8.3 Hz, 4 H, ArH), 8.65 (d, 3 J = 4.6 Hz, 4 H, β-H), 8.72 (d, 3 J = 4.8 Hz, 4 H, β-H), 10.93 (br s, 4 H, COOH). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 32.1, 35.6, 40.5, 117.2, 120.9, 124.6, 126.6, 135.5, 137.9, 139.9, 140.5, 151.5, 152.0, 172.5. MS (FAB+, NBA): m/z (%) = 1071 (100) [M] +· , 1025 (18) [M-COOH] +· . IR (ATR): 𝜈� [cm -1 ] = 3320, 3029, 2961, 2906, 2869, 1712, 1604, 1568, 1506, 1475, 1462, 1396, 1364, 1349, 1267, 1221, 1187, 1109, 1006, 991, 982, 986, 910, 887, 801, 737. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 419 (408000), 513 (21900), 547 (9300), 591 (6300), 647 (5200). CO 2 H N NH HN N HO2C 79 C 68 H 70 N 4 O 8 M = 1071.31 g·mol -1 CO 2 H 177
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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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3 Discussion and Results 116 HO 2 C
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3 Discussion and Results nitro comp
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3 Discussion and Results The effect
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3 Discussion and Results 3.2.9 Pote
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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