1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.7.2 Synthesis of Bis-Annulated Cycloketo-Porphyrin Systems (BCKPs) As copper(II) complexes turned out to be best suited to access free-base systems after annulation, the obtained porphyrin di-ethanoic acids were firstly converted thereto by application of the acetate method 96,97 . Subsequently, they were transformed into their corresponding acid chlorides by reaction with oxalyl chloride, C2O2Cl2, and finally cyclized using tin tetrachloride, SnCl4, as appropriate FRIEDEL-CRAFTS catalyst. 96 Upon acidic demetallation (TFA : H2SO4 = 5 : 1, rt, 45 min 96 ), five BCKPs were obtained in pure after chromatography (67-71, Scheme 46, p. 93). The corresponding yields for those compounds are summarized in Table 19. Thereby is to be kept in mind that 67 and 68 as well as 69 and 70 arose from one sole reaction each. Table 19. Yields in which BCKPs 67-71 were isolated after the applied annulation protocols based on the corresponding porphyrin di-ethanoic acids 75, 76 and 77 (Scheme 47, p. 94). 96 67 from 77 68 from 77 69 from 76 70 from 76 71 from 75 Overall Yield 51 % 12 % 58 % 14 % 70 % Although the combined yields turned out to be excellent (> 60 %), 68 and 70 were only formed in very low quantities implying some sort of directing effect in the formation of the second exocycle disfavoring a diagonal positioning. Further discussion on that is done in paragraph 3.2.7.7. Firstly, it should be focused on characterization and photophysical data. 3.2.7.3 NMR Spectroscopy As already deducible from introductive Scheme 46, the BCKPs under investigation exhibit quite different symmetry patterns majorly determining their NMR spectroscopic data. While the chiral members of that group are of C2 symmetry (68, 69 and 71), the achiral “meso- forms” appear to be of higher symmetries (Cs for 67 and Ci for 70). These assignments concerning symmetry patterns thereby renounce the appearance of NH-tautomers since those will not be observable at room temperature by NMR. To sustain clarity, the spectra will not be compared to each other on the whole but step-wise focusing on corresponding decisive regions. The complete data is summarized in the experimental section. To start with, it should be concentrated on the assignment of the abovementioned symmetry patterns.
2+12 2+12 2+18 2+18 2+8 7+13 8+12 7+13 8+12 Discussion and Results 3 These can be deduced from the aromatic areas of the corresponding 1 H NMR spectra as well as from the numbers and intensities of the resonances for the t-butyl groups in the 13 C NMR spectra. Extracts of the corresponding spectra are assorted in Figure 38. 7+17 8+18 7+17 8+18 12+18 13+17 5 3 15 3 5 3 15 3 5 3 /5 5 5 3 15 3 5 3 15 3 9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 δ [ppm] 35 34 33 32 31 Figure 38. Comparison of NMR data for BCKPs 67-71 at rt in CDCl3. Left: Aromatic regions of the 1 H NMR spectra (400 MHz), right: zoomed parts of the aliphatic regions of the corresponding 13 C NMR spectra (100.5 MHz). For 1 H NMR, the ortho-positions of the free rotatable phenyl rings are highlighted in red, meta-positions in blue. The remainder signals are numbered according to IUPAC recommendations. As the appearance of the β-pyrrolic positions as one singlet and two doublets ( 3 J ∼ 4.7 Hz) for 2 H each in the 1 H NMR spectra shows, all systems seem to contain pyrrolic units equivalently influenced by distortions implying higher symmetry patterns. Furthermore, most arylic resonances appear rather well resolved indicating higher corresponding rotational barriers as observed for 53. Interestingly, the NMR data of 67 and 69 and of 68 and 70 appear pair wise almost identical although they are derived from different distinct starting geometries. This can be explained by the fact, that they arise from annulations on identical positions, i.e. on 3 and 17 (67 & 69) and on 3 and 13 (68 & 70), respectively. The difference in attacks from above or below being 5 5 15 5 5 5 15 5 5 5 15 5 5 5 15 5 67 68 69 70 71 97
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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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6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section EA: C57H56N4
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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 6.2.5.9 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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