1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.8.1 Using Bis-Functional Compounds to Approach a Modified Form of 53 First investigations were starting off from symmetrically substituted bis-o-(methoxymethyl) substituted porphyrin 43 whose substituents lie on trans-standing phenyl rings in αβ- conformation in respect of the porphyrin plane. The dissymmetric functionalization was tried on the di-ether (from 43) and on the di-bromo stage (from 48) like it is shown in Scheme 51. 110 O N NH HN N O 82 N NH HN N HBr/HOAc (50 eq) 1. Zn(OAc) 2 2. KCN (50 eq) 3. aq. HCl O N NH HN N 42 N NH HN Br N HBr/HOAc N × NH HN CN N O HBr/HOAc (exc.) Br Br Br 1. Zn(OAc) 2 2. KCN (10 eq) 3. aq. HCl Scheme 51. Dissymmetric functionalization of 42 to give cyanomethyl precursors 83 and 84. The mono-bromination of 42 gave satisfactory yields around 30 % besides traces of educt and fully brominated byproduct 47. The following cyanation via the corresponding zinc(II) complex gave pure 83 in 95 % yield. In contrast, the mono-cyanation of 47 was unsuccessful as only traces of 84 were observed besides large educt amounts and some fully cyanated 47 × 83 84 CN
Discussion and Results 3 porphyrin. So it was tried to obtain 84 from 83 by treatment with HBr in glacial acetic acid. Also this approach turned out to be unsuccessful as the initially formed traces of product reacted further to give a mixture of educt 83 and presumably partially hydrolyzed derivatives. That product mixture was not purified as the full hydrolysis was targeted anyway. Subsequently, both 83 and the mixture obtained from its tried bromination were subjected to the set up conditions for nitrile hydrolysis. Unfortunately, this led to an immediate rupture of the applied porphyrin systems as the initially green acidic solutions turned black within a couple of minutes. Due to that, the reactions were immediately quenched and the residing materials were analyzed. But there was no porphyrinoid material left which was very surprising and not at all expected. Although side reactions have been taken into consideration before, e.g. the formation of hydroxymethyl or acetoxymethyl derivatives from 83, up to now, no plausible reasons for that drastic failures were found since the other porphyrin systems under investigation endured these conditions without any considerable decomposition and also since systems 83 has been formed under acidic conditions. Thus, that kind of approach was rejected and it was turned to the set up of AB2C-type porphyrin systems. Therefore, the characterization data for compounds 82 and 83 will not be discussed here but is summarized in the experimental section. 3.2.8.2 Approaching a Modified Form of 53 via AB2C Type Porphyrin Precursors To access a suitable system of the principle architecture displayed in Scheme 50, a corresponding functionality –X had to be chosen fulfilling the following requirements: • X, being already present in the parental aldehyde, should be (strongly) electron withdrawing to allow the formation of a stable dipyrromethane not scrambling under the conditions of porphyrin synthesis • X (or at least a protected form thereof) should be able to endure the conditions of the subsequent modifications necessary for the formation of the exocycle • X should represent (or be convertible into) a functionality easily coupleable to groups present in polypeptides or on functional surfaces like e.g. amines or carboxylic acids, if possible without needing to utilize special linkers 111
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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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Page 82 and 83: 3 Discussion and Results 74 Δθ [m
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Page 86 and 87: 3 Discussion and Results vibration
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Page 90 and 91: 3 Discussion and Results cyanomethy
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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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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 6.2.5.3 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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