1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.6.2 10 4 ,15 4 ,20 4 -Tri-t-Butyl-5 2 -(Methoxycarbonyl)-5,10,15,20-Tetraphenylporphyrin 76 60 as General Precursor for 57 and 58 To access both model systems, the same precursor porphyrin 60 was used arising from the condensation of methyl 2-formylbenzoate 59 and 4-t-butylbenzaldehyde with pyrrole under LINDSEY conditions (Scheme 42). 96 This approach delivering the desired target in high yield (17.4 % based on 59) was preferred to the corresponding dipyrromethane approach as that only gave 1.8 % of 60 overall. H CO2Me + 3 O H 59 O + 4 NH MeO 2 C N NH HN Scheme 42. Chosen synthesis of precursor porphyrin 60. Conditions: 1. BF3·OEt2, CHCl3, rt, 1 h; 2. add. DDQ, 2 h. Since 60 exhibits a great resemblance to precursors like 45, 50 and 51 previously dealt with, the discussion on characterization data will focus on specialties. The aromatic region of the 1 H NMR spectrum of 60 shows up far more complex as the lacking of the alkyl substituents gives rise to the typical resonance pattern of an ABCD spin system in the 5-substituent. Thus, four signals are observed at 8.39 (dd), 8.15 (dd), 7.86 (dt) and 7.81 (dt) ppm, respectively. The methyl group of the ester provides a singlet at 2.72 ppm strongly shifted upfield compared to the parental aldehyde (3.91 ppm) implying a positioning above the porphyrin core. The ester functionality is also clearly visible in the 13 C NMR spectrum where the carboxylic carbon atom characteristically resonates at 168.2 ppm while the signal for the methyl group is found at 51.4 ppm. By MS only the molecular mass peak was found at m/z = 841 and in the IR spectrum the pronounced carbonyl vibration for the ester was detected at 1735 cm -1 . N 60
N NH HN N MeO 2 C N NH HN N HO 2 C Discussion and Results 3 With 60, we obtained a well suited system for transformation into either 57 or 58. The general reaction outline is depicted in Scheme 43 and discussed in the following paragraphs. HBr/HOAc 1. Zn(OAc) 2 ·2H 2 O 2. LiAlH 4 3. aq. HCl XH 2 C 1. Zn(OAc) 2 ·2H 2 O 2. KCN 3. aq. HCl HOAc/H 2 SO 4 /H 2 O 1. Cu(OAc) 2 ·H 2 O 2. C 2 O 2 Cl 2 3. SnCl 4 4. TFA/H 2 SO 4 61 X = OH 62 X = Br 63 X = CN 64 X = CO2H 57 1. KOH 2. aq. HCl N NH HN N Scheme 43. Synthetic outline for the formation of 57 and 58 from 60. 96 3.2.6.3 Synthesis and Characterization of Six-Membered Ring Analog 58 1. Cu(OAc) 2 ·H 2 O 2. C 2 O 2 Cl 2 3. SnCl 4 4. TFA/H 2 SO 4 Like Scheme 43 displays, the synthesis of 58 was quite straightforward and should be discussed first. The necessary porphyrin methanoic acid precursor 65 was easily obtained from 60 by basic saponification using a solution of KOH in a mixture of THF, ethanol and water. This reaction gave the desired compound in 94 % isolated yield after FC based on 60. The characterization data of 65 only shows minor but significant changes compared to the precursor. E.g. the resonances for the methyl group of the ester are lacking in the recorded NMR spectra. Unfortunately, the acidic proton of the acid moiety cannot be detected due to fast proton-deuteron exchange with the applied solvents. In the IR spectrum, the carbonyl 60 65 58 77
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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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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
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Page 64 and 65: 3 Discussion and Results utilizatio
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Page 76 and 77: 3 Discussion and Results voltammogr
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Page 86 and 87: 3 Discussion and Results vibration
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Page 90 and 91: 3 Discussion and Results cyanomethy
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3 Discussion and Results peak at m/
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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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