1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results irradiation with a halogen lamp. The reaction time was decreased and the yield was raised up to 42 % for 36a and to 58 % for 36b, respectively. Thereby multiple bromination could be effectively suppressed, so that most often the desired products were detected exclusively. Those could easily be separated by FC (SiO2, hexanes). The characterization data being summarized in the experimental section is in full accordance to literature. 91 The conversion of benzylic bromides 36a and 36b into their corresponding methyl benzyl ethers 37a and 37b, which has been essential for the next step, was quantitatively accomplished via SN reaction with sodium methanolate 90 . The subsequent aldehyde formation was achieved by bromine-lithium exchange followed by addition of DMF and final hydrolysis of the semi-acetalic adduct accordant to literature procedures 90 . Thus, the desired arylaldehydes were obtained analytically pure in good yields (65 % for 38a and 75 % for 38b). In order to apply LINDSEY’s method for porphyrin synthesis 29 , both aldehydes were converted into the corresponding dipyrromethanes in advance. The condensation of 38a and 38b with excessive pyrrole under LEWIS acid catalysis (BF3·OEt2) (LINDSEY conditions 36,92 ) furnished analytically pure 39a and 39b after Kugelrohr distillation in 61 % and 64 % yield, respectively. 32 R H O O + 2 N H pyrrole BF 3 ·OEt 2 R O NH HN Scheme 23. Synthesis of dipyrromethanes 39a and 39b under LINDSEY conditions. Subsequent condensation with 4-t-butylbenzaldehyde (and pyrrole) under slightly modified LINDSEY conditions 29,69 provided an effective build-up of o-(methoxymethyl) substituted meso-tetraarylporphyrins of different symmetries being the direct precursors of building blocks 45 - 49 (Scheme 25). The structures of the obtained systems, their symmetries and synthetic details as well as the corresponding isolated yields are summarized in Scheme 24 and Table 3. 38a R = H 38b R = OCH3 39a R = H 39b R = OCH3
m R1 O NH HN 39a R 1 = H 39b R 1 = OCH3 + n H O p N H 1. condensation 2. oxidation R 1 Discussion and Results 3 O N NH HN Scheme 24. General outline for the synthesis of porphyrin systems 40 - 44. Table 3. Synthetic details for the formation of porphyrin systems 40 - 44. Compound m : n : p Condensation with a N R 3 R 2 Oxidant Yield Symmetry b 40 1 : 4 : 3 1. TFA (20mM), 2. NEt3 DDQ 13.6 % bsd. on 39a CS 41 1 : 4 : 3 BF3·OEt2 DDQ 14.2 % bsd. on 39b C2v 42 c 43 c 1 : 1 : 0 1. TFA (20mM), 2. NEt3 DDQ 8.8 % 8.4 % bsd. on 39a 44 1 : 1 : 0 1. TFA (20mM), 2. NEt3 DDQ 20.4 % bsd. on 39b D2h a Used solvents: CHCl3/EtOH with BF3·OEt2 and CH2Cl2 with TFA. TFA had to be neutralized before the oxidant was added. b The positions of the inner-ring amine protons was left unconsidered due to fast tautomerism. c These compounds represent stable atropisomers forming in the same reaction. While 44 formed exclusively under the applied synthetic conditions, 40 and 41 were accompanied by the unfunctionalized 5 4 ,10 4 ,15 4 ,20 4 -tetra-t-butyl-5,10,15,20-tetraphenyl- porphyrin (TTBPP) arising from excessive pyrrole and 4-t-butylbenzaldehyde being easily separated by FC. As 42 and 43 represent atropisomers (αα- and αβ-conformation), they formed in the same reaction as sole and easily separable compounds. The obtained systems represent the direct precursors to the o-(bromomethyl) substituted porphyrin building blocks which had been chosen as starting material. The conversion of the methoxymethyl side chains into bromomethyl functionalities was accomplished by acid catalyzed substitution using hydrobromic acid in quantitative yield in any case. (Scheme 25) As those systems as well as the porphyrin precursors are already known to literature 69 , a further discussion of characterization data is set aside. 40 R 1 = R 2 = R 3 = H 41 R 1 = OCH3, R 2 = R 3 = H 42 R 1 = H, R 2 = CH2OCH3, R 3 = CH3 43 R 1 = H, R 2 = CH3, R 3 = CH2OCH3 44 R 1 = OCH3, R 2 = R 3 = CH2OCH3 C2v C2h 33
Page 1 and 2: Semi-Natural and Synthetic Chiral C
Page 3 and 4: Die vorliegende Arbeit entstand in
Page 5 and 6: Table of Contents 1 Introduction 1
Page 7: n J j-coupling (constant) with n in
Page 10 and 11: 1 Introduction characteristics. For
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Page 14 and 15: 1 Introduction Especially interesti
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Page 20 and 21: 1 Introduction transitions as it is
Page 22 and 23: 1 Introduction 1.2 Photodynamic The
Page 24 and 25: 1 Introduction Certainly, Photofrin
Page 26 and 27: 1 Introduction intact membranes bei
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Page 30 and 31: 2 State of The Art & Aims They were
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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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3 Discussion and Results cyanomethy
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3 Discussion and Results 3.2.6.5 Co
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3 Discussion and Results phenyl sub
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3 Discussion and Results 3.2.6.5.4
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3 Discussion and Results 90 5 μA -
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3 Discussion and Results 3.2.7 Appr
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3 Discussion and Results (75 eq.) w
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3 Discussion and Results 3.2.7.2 Sy
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3 Discussion and Results of rotatio
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3 Discussion and Results Thus, the
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3 Discussion and Results Time-resol
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3 Discussion and Results first redu
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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3 Discussion and Results 3.2.8.1 Us
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3 Discussion and Results With all t
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3 Discussion and Results The interm
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3 Discussion and Results 116 HO 2 C
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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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