1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 1<strong>1.1</strong>, 11.9, 12.0, 17.3, 19.3, 23.1, 29.8, 30.8, 48.0, 49.9, 51.6, 51.6, 93.0, 97.1, 104.0, 106.0, 122.5, 128.3, 129.2, 130.5, 131.6, 135.8, 136.1, 136.2, 137.8, 141.6, 145.0, 149.0, 150.8, 155.2, 160.3, 171.4, 173.6, 196.3. MS (FAB+, NBA): m/z = 549 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3395, 2957, 1739, 1708, 1618, 1553, 1498, 1436, 1347, 1260, 1160, 1044, 984, 908, 796, 734, 671. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 413 (73800), 508 (8400), 538 (7800), 610 (6600), 648 (32900). 6.2.2.2 Pyropheophorbide a, 33 142 N NH HN N 33 O C 33 H 34 N 4 O 3 M = 534.65 g·mol -1 O OH In a 250 mL round bottom flask equipped with N2 inlet and reflux condenser, 200 mg (365 μmol) methyl pyropheophorbide a Me- 33 are suspended in a degassed (N2 stream) solvent mixture consistent of MeOH (45 mL), THF (45 mL), water (10 mL) and powdered KOH (2.0 g, exc.). The reaction mixture is then stirred under reflux for 3 h while the suspension turns into a dark green- violet solution which is finally brought to dryness. The crude product is further on taken up in CHCl3 washed with water, 2 M aqueous HCl and water, dried over Na2SO4 and finally chromatographed (Silica, CHCl3 : MeOH = 9 : 1) to furnish 183 mg (343 μmol) of pure 33 as dark purple powder. Yield: 94.0 % based on Me-33. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.71 (s, 1 H, NH), 0.34 (s, 1 H, NH), 1.63 (t, 3 J = 7.6 Hz, 3 H, 8 2 ), 1.79 (d, 3 J = 7.2 Hz, 3 H, 18 1 ), 2.29, 2.66 (2m, 2+2 H, 17 1 & 17 2 ), 3.19 (s, 3 H, 7 1 ), 3.37 (s, 3 H, 2 1 ), 3.58 (s, 3 H, 12 1 ), 3.65 (q, 3 J = 7.6 Hz, 2 H, 8 1 ), 4.28 (m, 1 H, 17), 4.45 (m, 1 H, 18), 5.09, 5.25 (2d, 2 J = 20.0 Hz, 1+1 H, 13 2 ), 6.13 (dd, 2 J = 1.6 Hz, 3 J = 11.6 Hz, 1 H, 3 2 cis), 6.25 (dd, 2 J = 1.6 Hz, 3 J = 17.9 Hz, 1 H, 3 2 trans), 7.96 (dd, 3 J = 11.6 Hz, 3 J = 17.9 Hz, 1 H, 3 1 ), 8.52 (s, 1 H, 20), 9.32 (s, 1 H, 5), 9.43 (s, 1 H, 10). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 11.2, 12.0, 17.4, 19.4, 23.1, 29.7, 31.5, 48.0, 51.6, 93.0, 97.1, 104.0, 106.0, 122.5, 124.1, 128.3, 129.2, 130.4, 131.6, 135.8, 136.0, 136.2, 137.8, 141.3, 144.9, 149.0, 150.7, 155.2, 160.2, 162.7, 171.4, 176.7, 196.4.
MS (FAB+, NBA): m/z = 535 (100) [M] +· . Experimental Section 6 IR (ATR): 𝜈� [cm -1 ] = 3393, 2922, 1691, 1618, 1552, 1497, 1450, 1399, 1345, 1221, 1162, 1123, 1025, 979, 891, 785, 731, 674, 612. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 413 (85200), 508 (9700), 538 (9000), 610 (7700), 668 (37900). 6.2.3 General Procedures (GP’s) GP I: Formation of o-(Cyanomethyl)-Substituted Porphyrin Systems from the Corresponding o-(Bromomethyl) Porphyrin Precursors a. Preparation of Zinc(II) Bromomethyl Porphyrin Complexes The starting material is completely dissolved in CH2Cl2 in an appropriate round bottom flask and a concentrated methanolic solution of an excess (20 eq.) of Zn(OAc)2·2H2O is added. The reaction mixture is then stirred at rt until TLC control shows completion. The time usually ranges in between 2 and 15 h depending on the level of substitution in the parental bromomethyl porphyrin compound. Afterwards, the reaction mixture is transferred into a separatory funnel, washed trice with water, dried over MgSO4 and evaporated to dryness to give the corresponding zinc(II) complexes as pinkish powders. b. Substitution of Bromide by Cyanide and Subsequent Demetallation The dry zinc(II) complex (up to 250 mg) obtained from part a. is placed in a 100 mL ERLENMEYER flask and mixed with a huge excess (50-100 eq.) of powdered KCN. After addition of PEG 400, the suspension is stirred at rt for 24 h. Within that period, the suspension slowly turns into a dark green-purple solution. Afterwards, the reaction mixture is transferred into a separatory funnel, diluted with 100 mL of water and extracted with CH2Cl2 until the aqueous layer becomes colorless. The combined organic extracts are then repeatedly washed with water (at least trice) to get rid of residing cyanide before half-concentrated aqueous HCl is added (100 mL) to the purple solution turning green immediately. After vigorous shaking for several minutes, the organic layer is separated and washed with 2 M aqueous HCl and with water until the organic layer appears purple. Subsequent neutralization by shaking out with a saturated aqueous solution of NaHCO3, washing with water, drying over MgSO4 and evaporation to dryness yields the corresponding free base o- 143
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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 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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3 Discussion and Results (being sup
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3 Discussion and Results other band
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3 Discussion and Results Table 10.
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3 Discussion and Results voltammogr
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3 Discussion and Results 3.2.5 Inhe
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3 Discussion and Results effects 12
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3 Discussion and Results 74 Δθ [m
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3 Discussion and Results 3.2.6.2 10
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3 Discussion and Results vibration
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3 Discussion and Results 3.2.6.4 Sy
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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 90 5 μA -
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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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