1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results cyanomethyl porphyrin system 63 in high isolated yield (95 % based on 62). Upon acidic saponification, the corresponding porphyrin carboxylic acid 64 could be obtained in 85 % yield and provided the basis compound for the FRIEDEL-CRAFTS annulation procedure. Also here, the full characterization of the intermediates is displayed in the experimental section. For brief monitoring of the transformations not only the rising polarity from 62 over 63 to 64 could be used but also MS (for 63: m/z = 823 [M+H] +· and for 64: m/z = 841 [M] +· ) and 1 H NMR data as the methylene group in the side chain underwent the already discussed characteristic shift from 4.31 ppm (62) over 3.42 ppm (63) to 3.35 ppm (64). For the build-up of the exocyclic ketone, 64 was firstly converted into the corresponding copper(II) complex. Then, according to paragraph 3.2.2.2, the carboxylic acid was treated with oxalyl chloride, C2O2Cl2, and tin tetrachloride, SnCl4. Upon acidic demetallation, free base cycloketo-porphyrin 57 was isolated in 65 % yield based on 64 as a dark green powder. 96 Like for 58, the detailed discussion of characterization data will be done later (paragraph 3.2.5.6) while here, only the 1 H NMR spectrum is to be presented (Figure 31). For 57, the splitting pattern for the β-pyrrolic protons again reflects the present C1 symmetry. The signals appear mostly clearly resolved as one singlet (9.16 ppm) and three sets of doublets in between 9.09 and 8.71 ppm ( 3 J ∼ 4.8 Hz). More upfield, the signals for the phenyl substituents are visible but partially show an intense line broadening and strong overlays. Thus, 57 is sharing major spectral characteristics with 53, which is also reflected by the remainder of the resonances apart from the ones arising from the ABCD spin system in the 5-phenyl substituent since that is not present in 53. These signals can be definitely assigned as outstanding doublets of doublets (7.84 and 7.23 ppm) or doublets of triplets (7.56 and 7.50 ppm). The exocyclic methylene group expectedly provides a pair of doublets at 5.63 and 4.23 ppm with geminal couplings of about 11.7 Hz due to diastereotopicity. Like for 53, the t-butyl groups of the system give rise to three well resolved singlets around 1.63 ppm being in full accordance to the system’s C1 symmetry. The inner-ring NH-protons resonate at -1.70 ppm. That is being well comparable to the situation in 53, where the signal is also shifted upfield by of over 1 ppm compared to the precursor. 82
2 7 O 17+18 12+13 8 N NH HN N 9.2 8.8 8.4 8.0 7.6 7.2 CDCl 3 10 2/6 15 2/6 3 2 in 20 2/6 102/6 ,152/6 m-ArH 5 6 3 2 out 5 5 5 4 Discussion and Results 3 1.66 1.63 9 8 7 6 5 4 3 2 1 0 -1 δ [ppm] -3 CDCl 3 5 3 10 4 , 15 4 20 4 Figure 31. 1 H NMR spectrum of 57, 400 MHz, CDCl3, rt. All signals are numbered according to IUPAC recommendations. With these two analogs at hand, it shall now be turned to the relations between those and the parental system 53 and the comparison of those three systems. 1.60 NH 83
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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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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
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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 94 and 95: 3 Discussion and Results phenyl sub
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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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