1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results With all this in mind, a nitro group (-NO2) seemed the subject of choice since it perfectly fit with the abovementioned items and as 4-nitrobenzaldehyde is commercially available. Hence, the first step was to synthesize the appropriate AB2C-type porphyrin system and then convert it into the corresponding nitro-phenylporphyrin carboxylic acid. 3.2.8.2.1 Access to a 15 4 -Nitro-15-Phenyl Derivative of 51 As the targeted system is of trans-AB2C-type (see Scheme 9, p. 9), it was accessible via cross- condensation of 5 4 -tert-butyl-5 2 -(methoxymethyl)-5 6 -methyl-5-phenyldipyrromethane 39a (see Scheme 23, p. 32) and 5 4 -nitro-5-phenyldipyrromethane 85 with 4-tert- butylbenzaldehyde like it is shown in Scheme 52. Necessary 85 was therefore synthesized according to literature procedures 4-nitrobenzaldehyde and pyrrole. 137 112 NH HN O + NO 2 NH HN + 2 H O a.-c. CH 2 Cl 2 O N NH HN 39a 85 86 Scheme 52. Synthesis of AB2C-type porphyrin system 86: a. TFA, 1 h, rt; b. add. NEt3, 5 min, rt; c. add. DDQ, 2 h; rt. During the synthesis, a huge amount of porphyrinoid material was formed consisting of various types of porphyrin systems as the reaction generally proceeds statistically. Attempts to separate individual systems turned out only partially successful. The major part of the obtained material persistently stayed a binary mixture of compounds with negligible difference in Rf values. Those two products were identified by MS, one being of A2B2-type (87, see Scheme 53) arising from the condensation of two fragments of 85 (m/z = 816) and the other being the desired target 86 (m/z = 886). Numerous TLC trials with different binary and ternary eluent mixtures showed that repeated FC might lead to the desired separation but would involve a considerable loss of product. But since the unwanted by-product could not react in the subsequent substitution reaction altering the methoxy substituent in the side chain into a bromide, it was decided to use the obtained material as such. Based on the N NO 2
O 2 N O N NH HN N N NH HN N NO 2 NO 2 HBr/HOAc 12 h, rt Br Discussion and Results 3 experience with analog compounds, the substitution would involve a significant change in polarity so that then a proper separation should be easy to achieve (Scheme 53). And fortunately, exactly that eventuated and targeted compound 88 could be isolated in pure form in excellent 14.9 % overall yield based on dipyrromethane 85. O 2 N N NH HN N N NH HN N almost inseparable easily separable Scheme 53. Substitution of methoxide by bromide within the mixture containing 86 finally leading to separable compounds 87 & 88 following the “purification via conversion”principle. By having 88 in hands, the approved protocols for cyanation and subsequent hydrolysis could be applied (paragraph 3.2.2.1.2, p. 36). Thus, the correspondent zinc(II) complex of 88 was generated 93,96 and reacted with potassium cyanide to give cyanomethyl derivative 89 which was then saponified under acidic conditions 96 to finally yield porphyrin ethanoic acid 90 being the precursor for the annulation procedure. That pathway is shown in Scheme 54. Hence, 90 could be obtained in 80 % overall yield from 88 (87 % for 89 and subsequently 92 % for 90) well in line with the expected stability of the nitro group toward the synthesis conditions. 86 87 88 87 NO 2 NO 2 113
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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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Page 76 and 77: 3 Discussion and Results voltammogr
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Page 80 and 81: 3 Discussion and Results effects 12
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 116 and 117: 3 Discussion and Results The remain
Page 118 and 119: 3 Discussion and Results 3.2.8.1 Us
Page 122 and 123: 3 Discussion and Results The interm
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Page 126 and 127: 3 Discussion and Results nitro comp
Page 128 and 129: 3 Discussion and Results The effect
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Page 132 and 133: 3 Discussion and Results 3.2.9 Pote
Page 134 and 135: 3 Discussion and Results peak at m/
Page 136 and 137: 3 Discussion and Results Table 25.
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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
Page 148 and 149: 6 Experimental Section 6.2 Studied
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Page 154 and 155: 6 Experimental Section 6.2.4 AB3-Ty
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Page 166 and 167: 6 Experimental Section EA: C57H56N4
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6 Experimental Section 6.2.5 A2B2-T
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6 Experimental Section 6.2.5.3 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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