1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.6.4 Synthesis of Seven-Membered Ring Analog 57 To synthesize 57 from porphyrin methyl methanoate 59, the problem of the extension of the side chain by one carbon atom had to be solved first. Since the substrate is a carboxylic acid derivative, it was considered to try an ARNDT-EISTERT reaction 134 which would lead directly from 65 to Cu(II)-64 like it is shown in Scheme 44. 80 HO 2 C N NH HN N Arndt-Eistert homologation homologation HO 2 C 65 Cu(II)-64 Scheme 44. Adapted ARNDT-EISTERT homologation. Applied steps: 1. Cu(OAc)2·H2O, 2. C2O2Cl2, 3. CH2N2, 4. Ag(I) catalyst, heat. To protect the inner-ring positions of the porphyrin, copper(II) was inserted before the carbon acid chloride has been generated using oxalyl chloride, C2O2Cl2. After complete evaporation of solvent and chlorinating agent, the obtained red residue was reacted with freshly prepared diazomethane, CH2N2, at lowered temperature (-10 °C). Upon evaporation, water and dioxane were added together with the necessary silver(I) catalyst, Ag2O, which was also freshly prepared. After reacting that mixture under reflux over night, a reddish product was isolated and indentified as metallated methyl ester derivative Cu(II)-59 without any detectable by-products. This approach has thus not been applicable to that kind of system, so that the more complex way depicted in Scheme 43 had to be chosen. This protocol managed the elongation of the side chain by nucleophilic attachment of cyanide like it has already been described for 53 (see paragraph 3.2.2). That necessitated the initial conversion of the carboxylic acid moiety into a good leaving group like our well approved bromo substituted methyl group. Thus, porphyrin methyl methanoate 59 had to be reduced to the corresponding alcohol, hydroxymethyl porphyrin 61, by reaction with lithium aluminum hydride, LiAlH4, in THF. 135 For protective means, the zinc(II) complex was prepared in advance while the metal was removed in the course of the applied work-up. After FC the desired sub-ordinate target 61 was obtained in pure as purple powder (87 % yield based on 59). ARNDT-EISTERT N N Cu N N
HO N NH HN N HBr in HOAc Br N NH HN N Discussion and Results 3 The conversion into the corresponding bromomethyl porphyrin 62 was then achieved by reaction with HBr (5.4 M in glacial acetic acid) in CH2Cl2 for 3 h at rt. Unfortunately, the desired bromomethyl porphyrin could only be gained in 37 % yield since the reaction with the present acetic acid lead to considerable amounts (∼50 % yield) of analog acetoxymethyl porphyrin system 66 (Scheme 45). This side reaction might be avoided if the reaction was conducted with aqueous HBr in dioxane, but as 62 was obtained in sufficient amounts for further experiments, we set optimization studies aside. AcO + N NH HN Scheme 45. Bromination of hydroxymethyl porphyrin 61 leading to products 62 and 66 in an approximate ratio of 5 : 7 in favor of 66. Compounds 61 and 62 were fully characterized. The obtained data can be found in the experimental section while here only a brief overview should be presented. The successful transformation could nicely be proven by MS as that class of substances does not tend to significantly fragment. Starting from ester 60 (m/z = 841 [M] +· ), we obtained 61 (m/z = 813 [M] +· ) and finally bromomethyl derivative 62 (m/z = 876 [M] +· ) showing the characteristic fragment of m/z = 795 [M-Br] +· being typical for all synthesized systems of that kind. 61 62 66 Also unambiguous was the 1 H NMR data. While the side chain being altered only shows one resonance for the methyl ester as singlet at 2.72 ppm (CO2CH3), the one in the reduced species 61 gives two signals: one doublet at 4.31 ppm ( 3 J = 5.2 Hz, CH2OH) and one triplet at 1.21 ppm ( 3 J = 5.6 Hz, CH2OH). In 62, again only one resonance for the CH2Br group is detected at 4.31 ppm as singlet being in the typical region for bromomethyl porphyrins. After having obtained pure 62, the synthetic pathway was back on track and the previously presented procedures for cyanation, hydrolysis and ring-closure could be applied in analogy to the synthesis of 53. 96 The cyanation via the corresponding zinc(II) complex of 62 furnished N 81
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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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Page 40 and 41: 3 Discussion and Results irradiatio
Page 42 and 43: 3 Discussion and Results 34 R 1 O N
Page 44 and 45: 3 Discussion and Results 3.2.2.1.2
Page 46 and 47: 3 Discussion and Results Table 4. S
Page 48 and 49: 3 Discussion and Results 3.2.2.2 FR
Page 50 and 51: 3 Discussion and Results 3.2.2.3 Ac
Page 52 and 53: 3 Discussion and Results 3.2.3.1 IR
Page 54 and 55: 3 Discussion and Results 3.2.3.2 NM
Page 56 and 57: 3 Discussion and Results 3.2.3.3 Va
Page 60 and 61: 3 Discussion and Results Obviously,
Page 62 and 63: 3 Discussion and Results Like Figur
Page 64 and 65: 3 Discussion and Results utilizatio
Page 66 and 67: 3 Discussion and Results has been d
Page 68 and 69: 3 Discussion and Results other TPP
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Page 72 and 73: 3 Discussion and Results other band
Page 74 and 75: 3 Discussion and Results Table 10.
Page 76 and 77: 3 Discussion and Results voltammogr
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Page 80 and 81: 3 Discussion and Results effects 12
Page 82 and 83: 3 Discussion and Results 74 Δθ [m
Page 84 and 85: 3 Discussion and Results 3.2.6.2 10
Page 86 and 87: 3 Discussion and Results vibration
Page 90 and 91: 3 Discussion and Results cyanomethy
Page 92 and 93: 3 Discussion and Results 3.2.6.5 Co
Page 94 and 95: 3 Discussion and Results phenyl sub
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Page 100 and 101: 3 Discussion and Results 3.2.7 Appr
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Page 108 and 109: 3 Discussion and Results Thus, the
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Page 116 and 117: 3 Discussion and Results The remain
Page 118 and 119: 3 Discussion and Results 3.2.8.1 Us
Page 120 and 121: 3 Discussion and Results With all t
Page 122 and 123: 3 Discussion and Results The interm
Page 124 and 125: 3 Discussion and Results 116 HO 2 C
Page 126 and 127: 3 Discussion and Results nitro comp
Page 128 and 129: 3 Discussion and Results The effect
Page 132 and 133: 3 Discussion and Results 3.2.9 Pote
Page 134 and 135: 3 Discussion and Results peak at m/
Page 136 and 137: 3 Discussion and Results Table 25.
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3 Discussion and Results 130
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4 Summary As the characterization d
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5 Zusammenfassung 5 Zusammenfassung
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5 Zusammenfassung Da in guten Ausbe
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6 Experimental Section UV/Vis spect
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6 Experimental Section 6.2 Studied
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6 Experimental Section 13 C NMR (10
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6 Experimental Section (cyanomethyl
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6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section 6.2.4.3 5 4
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6 Experimental Section 6.2.4.11 10
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6 Experimental Section EA: C57H56N4
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6 Experimental Section 6.2.4.15 10
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6 Experimental Section 6.2.5 A2B2-T
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6 Experimental Section 6.2.5.5 αβ
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6 Experimental Section 6.2.5.7 αβ
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6 Experimental Section 6.2.5.9 αα
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6 Experimental Section 6.2.5.11 α
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6 Experimental Section 6.2.5.13 α
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6 Experimental Section 6.2.6 AB2C-T
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section broad signal
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7 References 16 H. Fischer, K. Zeil
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7 References 57 S. Schwartz, K. Abs
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7 References 89 (a) R. C. Fuson, J.
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7 References 131 (a) J. Perdew, Phy
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S. Jasinski, N. Jux, “Investigati
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Ein großer Dank gilt auch den Ange
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Cirruculum vitae Stefan Jasinski Ge
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204 56 57 58 59 60 61 62 63 64 65 6
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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