1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 34 R 1 O N NH HN N 40 R 1 = R 2 = R 3 = H R 3 41 R 1 = OCH3, R 2 = R 3 = H R 2 42 R 1 = H, R 2 = CH2OCH3, R 3 = CH3 43 R 1 = H, R 2 = CH3, R 3 = CH2OCH3 44 R 1 = OCH3, R 2 = R 3 = CH2OCH3 HBr / HOAc CH 2 Cl 2 rt, 6-12 h R 1 Br N NH HN N Scheme 25. Transformation of methoxymethyl porphyrins into bromomethyl porphyrins. Thus, the different starting materials were well accessible in quantities of 1-2 g per run providing a solid basis for further investigations on the setup of novel systems. 3.2.2 Setup of a Synthetic Pathway to Novel Cycloketo-<strong>Porphyrins</strong> Such systems are generally accessible by a FRIEDEL-CRAFTS acylation process like CALLOT et al. have recently shown 76 . In order to obtain structural analogs to the already synthesized cycloamino-porphyrin systems like M-29 (Scheme 18), the bromomethyl groups in 45 - 49 had to be converted into ethanoic acid side chains. Different thinkable approaches therefore were tried and evaluated using mono-functional system 45 as a basis. The results are discussed in the following paragraphs. 3.2.2.1 Developing the Synthesis of a Porphyrin Ethanoic Acid Derivative 3.2.2.<strong>1.1</strong> Evaluating Organometallic Means 45 R 1 = R 2 = R 3 = H A general approach to carboxylic acid derivatives uses organic halides, most often bromides. Those substrates are firstly subjected to an umpolung by generation of organometallic intermediates being further reacted with carbon dioxide. Possible reaction pathways are shown in Scheme 26 on the left. Both reaction pathways were investigated using the zinc(II) complex of 45 as a suitable starting material, in which the central metal is functioning as a R 3 46 R 1 = Br, R 2 = R 3 = H R 2 47 R 1 = H, R 2 = CH2Br, R 3 = CH3 48 R 1 = H, R 2 = CH3, R 3 = CH2Br 49 R 1 = Br, R 2 = R 3 = CH2Br
Discussion and Results 3 kind of “protective group” since the inner ring protons can interfere with the (generated) organometallic reagents. Zinc(II) complex Zn(II)-45 can easily and quantitatively be obtained from free base 45 by metallation under standard conditions (acetate method using CH2Cl2 and methanol as solvents) 93 . δ+ R Br Mg, THF δ− n-BuLi, THF δ− R MgBr δ+ δ− R Li δ+ 1. CO 2 2. H + /H 2 O R 1. CO 2 2. H + /H 2 O O OH N R = N Zn Scheme 26. General approaches to carboxylic acids using organometallics (left) and a suitable porphyrin reactant (right). Firstly, the formation of a porphyrin-GRIGNARD reagent has been tried using different reaction temperatures (-78 °C, rt, reflux) with and without a pre-activation of the magnesium turnings by addition of iodine. After 3 h, CO2 was added at lowered temperature (-50 °C) and the reaction mixture was worked-up under acidic conditions (6 M aqueous HCl) to protonate the potentially formed carboxylate and also to remove the zinc(II) metal center. TLC and MS showed, that no conversion was achieved and the educt was recovered. Changing the reaction time had no influence on that outcome. 75 This made us check the second pathway by reacting the same zinc(II) precursor with n-butyl lithium (as 1.6 M solution in hexanes). Also here reaction times and temperature have been varied and the CO2 addition and work-up were performed in the same way. Unfortunately, in each case, no observable conversion could be detected. 75 N N Zn(II)-45 Hence, the bromomethyl group in Zn(II)-45 seemed to be inert under these reaction conditions. So, one had to think of an alternative route to obtain the desired product. 35
Page 1 and 2: Semi-Natural and Synthetic Chiral C
Page 3 and 4: Die vorliegende Arbeit entstand in
Page 5 and 6: Table of Contents 1 Introduction 1
Page 7: n J j-coupling (constant) with n in
Page 10 and 11: 1 Introduction characteristics. For
Page 12 and 13: 1 Introduction 1.1 Porphyrins - A G
Page 14 and 15: 1 Introduction Especially interesti
Page 16 and 17: 1 Introduction 8 [H] 4 + 4 O H O H
Page 18 and 19: 1 Introduction complexes are usuall
Page 20 and 21: 1 Introduction transitions as it is
Page 22 and 23: 1 Introduction 1.2 Photodynamic The
Page 24 and 25: 1 Introduction Certainly, Photofrin
Page 26 and 27: 1 Introduction intact membranes bei
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Page 30 and 31: 2 State of The Art & Aims They were
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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 3.2.6.5.4
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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 3.2.8.2.7
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3 Discussion and Results 3.2.9 Pote
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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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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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