1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results voltammogram for Cu(II)-53 an additional, not pronounced irreversible process can be detected whose origin is unclear. It might arise from the formation of an instable copper(I) complex. Altogether it can be stated that substances of the here presented synthetic cycloketo- porphyrin type are acclaimed in equal measures to other porphyrin systems concerning their coordination chemistry. In agreement with theory, the indium(III) and zinc(II) complexes show good characteristics in terms of singlet oxygen sensitization with appropriate absorption bands at 658 and 655 nm, respectively, and with extinction coefficients of sufficient values. Especially interesting are the findings on In(III)-53 as such complexes could be applied in terms of a combined photo-radio-therapy. This therapeutic method would comprise tumor imaging and treatment by using one single substance as the complex could also be formed using radioactive indium-111. This radionuclide decays nearly exclusively (99 %) via electron capture with a half-life t½ of 2.8 d to cadmium-111. The emitted γ-radiation can be excellently detected by radiation tubes or scintillation counters providing a good tool to recognize tumorous tissue. Additional in situ irradiation with laser-light concentrated on those areas would then allow a concurrent photodynamic treatment. First investigations with highly charged porphyrin systems also derived from the porphyrin building blocks used within this thesis showed that accumulation and detection in tumor tissue is possible (mice experiments). 70b Investigations concerning such an application of cycloketo-porphyrin systems have been started, but unfortunately, no clear results could be obtained up to now. 3.2.4.2 Reactions Involving the Exocyclic Ketone Moiety In establishing the exocycle by a FRIEDEL-CRAFTS annulation procedure, a ketone is generated on the porphyrin core and therewith a functionality being desirable from a synthesist’s point of view since that should allow a great variety of modifications. Some possible examples gathered in Table 12 have been taken into account and corresponding transformations were subjected to trials according to standard procedures or protocols known to literature. But curiously, in most of the cases the starting material was recovered more or less quantitatively. Sometimes, a conversion could be detected by TLC, but all efforts to isolate and characterize any formed product failed. 68
O N NH HN N N N H N H N Discussion and Results 3 Table 12. Possible reactions of the ketone group in cycloketo-porphyrins with potential reagents. Reaction Reagents acetal formation ethanol; 1,2-dihydroxyethane; trimethyl orthoformate imin/enamine formation piperidine; prolin methyl ester thioketone formation LAWESON’s reagent reductive alkylation organolithium reagents (e.g. BuLi); GRIGNARD reagents reduction lithium aluminum hydride, boron hydrides The low or even inexistent reactivity can be explained by different approaches. One might think that those effects could be due to steric shielding of the ketone, but as computational studies showed, this group is coplanar to the porphyrin so that many possible trajectories are left unhindered (see Figure 14). Thus, it might be due to electronic reasons. As the drawn formulas depict, the ketone group is not only just an aromatic one as it can be also regarded as a vinylogous amide structure or as part of a MICHAEL system conjugated to a diaza- [18]annulene (Scheme 36). The latter approach thereat seems less probable since simple calculation did not hint to it. However, both could lead to a reduced reactivity towards mechanisms involving an attack of a nucleophile. Furthermore, computational studies on higher levels (DFT/MRCI) evolve another explanation since those hint to the presence of a partial radical character on the carbonyl which is considered to cause a reversal in polarity to a certain extent which would doubtless lead to changes in the reactivity towards nucleophiles. 100 Scheme 36. Possible ways to look at the exocyclic ketone in 53: a vinylogous amide (left) or a part of a conjugated MICHAEL system (right). Which explanation finally fits or which influences are really contributing remains unclarified. O 69
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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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Page 30 and 31: 2 State of The Art & Aims They were
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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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