1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results The intermediates as well as the product were fully characterized and the corresponding data shall be discussed in the following. 114 Br N NH HN N NO 2 a. CN N NH HN N NO 2 b. CO 2 H N NH HN N 88 89 90 Scheme 54. Access to 15 4 -nitro-substituted porphyrin ethanoic acid 90. Applied conditions: a. 1. Zn(OAc)2, CH2Cl2/MeOH, 15 h, rt; 2. KCN, PEG400, 24 h, rt; 3. aq. HCl, CH2Cl2, 10 min, rt; b. HOAc/H2SO4/H2O, 96 h, 95 °C. 3.2.8.2.2 Characterization of 15 4 -Nitro-Substituted Precursor Systems 88, 89 and 90 The behavior of those compounds concerning mass spectrometry is well comparable to the other porphyrin precursor systems as they do not tend to fragment. Thus, the molecular peaks for [M] +· appear always clearly resolved at m/z = 935 (88), m/z = 881 (89) and m/z = 900 (90), respectively. Only in the bromomethyl compound 88, a minor fragment can be detected at m/z = 854 due to the loss of the bromine atom. The NMR spectra show up typical for porphyrins with AB2C substitution pattern with four resonances for the β-pyrrolic protons appearing as doublets with characteristic two-bond couplings around 4.7 Hz. Also within this series of compounds, the alteration of the side chain from bromomethyl over cyanomethyl to carboxymethyl causes significant changes of the spectra. The corresponding regions of the 1 H NMR spectra are depicted in Figure 44. The spectra appear strictly dependent on the size of the altered side chain as the signals of the freely rotatable phenyl rings (10 & 20) are concerned. While for the smallest moiety (-CH2CN in 89), the signals appear as two clear doublets at 7.77 and 8.13 ppm, the slightly larger -CH2Br group in 88 gives rise to a splitting of the resonance signals, but only for the protons in ortho positions in respect of the porphyrin core. For the largest side chain (-CH2CO2H in 90), both resonance sets (for ortho and meta protons) are split into two doublets each as then the two half-spaces above and below the porphyrin plane appear clearly different and so do also the chemical shifts for the corresponding protons. That effect NO 2
Discussion and Results 3 is also visible for the nitrophenyl substituent, although not that pronounced due to the larger distance to the altered side chain, as the signal for the ortho positions around 8.35 ppm becomes broadened. Thus, the behavior of those systems is in good correlation with the previously presented AB3-type systems. Also here can be detected the upfield shift for the signal of the CH2 group in the side chain from about 4.1 ppm in the bromo precursors to about 3.2 ppm for the carboxylic acid derivatives. As also the remainder characterization data, being summarized in the experimental section, is well comparable to those of already discussed precursors it is not further treated here. CH 2Br CH 2CN CH 2CO 2H 9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 δ [ppm] 4.1 3.7 3.3 Figure 44. 1 H NMR spectra of 88 (top), 89 (middle) and 90 (bottom) measured at rt and 400 MHz in CDCl3. Resonances for the nitro-substituted phenyl ring (15) are marked in red, those for the modified phenyl ring (5) in blue. 3.2.8.2.3 Accessing Cycloketo-<strong>Porphyrins</strong> with Nitrogen-Based Functionality in 15 4 Position Thereto nitro-porphyrin ethanoic acid 90 was subjected to the previously described FRIEDEL- CRAFTS acylation protocol using again copper(II) complexes as intermediates (Scheme 55). 96 The reactions went well and furnished the annulated copper(II) complex Cu(II)-91 in 69 % yield as key intermediate which could be demetallated to give free base 91 via standard acidic treatment (paragraph 3.2.2.3, p. 42) in 96 % yield (Scheme 55). Further reaction with an appropriate reducing agent finally provided amino derivative 92 like it is shown in Scheme 56. 88 89 90 115
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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 3.2.3.3.2
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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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Page 76 and 77: 3 Discussion and Results voltammogr
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Page 82 and 83: 3 Discussion and Results 74 Δθ [m
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Page 86 and 87: 3 Discussion and Results vibration
Page 88 and 89: 3 Discussion and Results 3.2.6.4 Sy
Page 90 and 91: 3 Discussion and Results cyanomethy
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Page 126 and 127: 3 Discussion and Results nitro comp
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Page 140 and 141: 4 Summary As the characterization d
Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
Page 144 and 145: 5 Zusammenfassung Da in guten Ausbe
Page 146 and 147: 6 Experimental Section UV/Vis spect
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Page 152 and 153: 6 Experimental Section (cyanomethyl
Page 154 and 155: 6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section 6.2.5.3 5 4
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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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