1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

More documents

Recommendations

Info

6 Experimental Section (cyanomethyl)-substituted tetraarylporphyrin which is finally purified by FC over silica. GP II: Saponification of o-(Cyanomethyl)-Substituted Porphyrin Systems to Porphyrin Ethanoic Acids In a 250 mL round bottom flask equipped with reflux condenser, the o-(cyanomethyl) porphyrin system (up to 300 mg, obtained via GP I) is dissolved in a mixture of glacial AcOH, conc. H2SO4 and water. Under vigorous stirring at 95 °C, the mixture is allowed to react for 80 h. After that, the dark green reaction mixture is poured on ice, whereupon the protonated porphyrin carboxylic acid derivative precipitates completely. The residue is then collected by filtration and washed once with water before it is taken up in CH2Cl2. That solution is shaken out with water trice, washed with a dilute aqueous solution of NaHCO3 and with water. Drying over MgSO4 and removing the solvent furnishes the crude porphyrin ethanoic acids being of adequate purity in most cases. Else, purification is to be achieved by FC over silica. GP III: Accessing Cycloketo-Porphyrin Systems Utilizing FRIEDEL-CRAFTS Chemistry a. Preparation of Copper(II) Porphyrin Carboxylic Acid Complexes In a 250 mL round bottom flask, the free base porphyrin carboxylic acid (e. g. obtained via GP II) is dissolved in CH2Cl2 and acidified with some drops of glacial AcOH. Then a concentrated methanolic solution of an excess (10 eq.) of Cu(OAc)2·H2O is added and the reaction mixture is stirred at rt for 16 h. Afterwards, water is added and the layers are separated. Subsequent washing of the organic layer with water twice, drying over MgSO4 and evaporation to dryness yields the desired copper(II) complexes as cherry-red powders to be used without further purification. b. FRIEDEL-CRAFTS Acylation to Close the Exocyclic Ring In a 100 mL round bottom flask with N2 inlet, the metal complex (Cu(II) or Ni(II)) of an appropriate porphyrin carboxylic acid (up to 200 mg, e.g. obtained from part a.) is dissolved in abs. CH2Cl2 under inert gas atmosphere and under exclusion of water. Then an excess of C2O2Cl2 is added and the flask is closed with a bubble counter as pressure relief valve. After 2 h of stirring at rt, the solvent and the reactant are completely removed under high vacuum utilizing two coupled cooling traps. The residing dry acid chloride is directly redissolved in abs. CH2Cl2 under N2 and exclusion of water again before SnCl4 is added. This mixture is then 144
Experimental Section 6 allowed to react under vigorous stirring for 10 min at rt whereat the brown-red solution turns dark green. Subsequently, the reaction is quenched by careful addition of a saturated aqueous solution of NaHCO3. The biphasic mixture is then transferred into a separatory funnel and repeatedly extracted with CH2Cl2. The combined extracts are furthermore washed with 6 M aqueous HCl, water, a saturated aqueous solution of NaHCO3 and again water, dried over MgSO4 and evaporated to dryness. In most cases, the crude product consists of a mixture of metal complex(es) and the corresponding free base(s) of the annulated porphyrin system and appears as a dark green solid. Out of that mixture, the pure copper(II) or nickel(II) complex(es) can be obtained upon FC whereas the mixture formed of the copper(II) carboxylic acid is used as such for accessing the free system(s). c. Demetallation to Give Free Base Cycloketo-Porphyrin Systems The mixture yielded from part b. consistent of copper(II) complex(es) and free base(s) (up to 200 mg) is taken up in TFA in a 100 mL round bottom flask. Then conc. H2SO4 is added whereupon the reaction mixture turns immediately orange or even red. After 45 min of stirring at rt, water is added and the formed suspension is repeatedly extracted with CH2Cl2. The combined extracts are furthermore washed with water, neutralized with a saturated aqueous solution of NaHCO3 and washed with water again. Drying over MgSO4, evaporation of the solvent and FC over silica furnishes the desired free base porphyrin system(s). 145
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
Page 12 and 13:
1 Introduction 1.1 Porphyrins - A G
Page 14 and 15:
1 Introduction Especially interesti
Page 16 and 17:
1 Introduction 8 [H] 4 + 4 O H O H
Page 18 and 19:
1 Introduction complexes are usuall
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
Page 28 and 29:
1 Introduction components, the limi
Page 30 and 31:
2 State of The Art & Aims They were
Page 32 and 33:
2 State of The Art & Aims 2.2 Aim o
Page 34 and 35:
3 Discussion and Results encapsulat
Page 36 and 37:
3 Discussion and Results diastereot
Page 38 and 39:
3 Discussion and Results 30 E ½ Re
Page 40 and 41:
3 Discussion and Results irradiatio
Page 42 and 43:
3 Discussion and Results 34 R 1 O N
Page 44 and 45:
3 Discussion and Results 3.2.2.1.2
Page 46 and 47:
3 Discussion and Results Table 4. S
Page 48 and 49:
3 Discussion and Results 3.2.2.2 FR
Page 50 and 51:
3 Discussion and Results 3.2.2.3 Ac
Page 52 and 53:
3 Discussion and Results 3.2.3.1 IR
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
Page 58 and 59:
Page 60 and 61:
3 Discussion and Results Obviously,
Page 62 and 63:
3 Discussion and Results Like Figur
Page 64 and 65:
3 Discussion and Results utilizatio
Page 66 and 67:
3 Discussion and Results has been d
Page 68 and 69:
3 Discussion and Results other TPP
Page 70 and 71:
3 Discussion and Results (being sup
Page 72 and 73:
3 Discussion and Results other band
Page 74 and 75:
3 Discussion and Results Table 10.
Page 76 and 77:
3 Discussion and Results voltammogr
Page 78 and 79:
3 Discussion and Results 3.2.5 Inhe
Page 80 and 81:
3 Discussion and Results effects 12
Page 82 and 83:
3 Discussion and Results 74 Δθ [m
Page 84 and 85:
3 Discussion and Results 3.2.6.2 10
Page 86 and 87:
3 Discussion and Results vibration
Page 88 and 89:
3 Discussion and Results 3.2.6.4 Sy
Page 90 and 91:
3 Discussion and Results cyanomethy
Page 92 and 93:
3 Discussion and Results 3.2.6.5 Co
Page 94 and 95:
3 Discussion and Results phenyl sub
Page 96 and 97:
Page 98 and 99:
3 Discussion and Results 90 5 μA -
Page 100 and 101:
3 Discussion and Results 3.2.7 Appr
Page 102 and 103: 3 Discussion and Results (75 eq.) w
Page 104 and 105: 3 Discussion and Results 3.2.7.2 Sy
Page 106 and 107: 3 Discussion and Results of rotatio
Page 108 and 109: 3 Discussion and Results Thus, the
Page 110 and 111: 3 Discussion and Results Time-resol
Page 112 and 113: 3 Discussion and Results first redu
Page 114 and 115: 3 Discussion and Results correspond
Page 116 and 117: 3 Discussion and Results The remain
Page 118 and 119: 3 Discussion and Results 3.2.8.1 Us
Page 120 and 121: 3 Discussion and Results With all t
Page 122 and 123: 3 Discussion and Results The interm
Page 124 and 125: 3 Discussion and Results 116 HO 2 C
Page 126 and 127: 3 Discussion and Results nitro comp
Page 128 and 129: 3 Discussion and Results The effect
Page 130 and 131: 3 Discussion and Results 3.2.8.2.7
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.
Page 138 and 139: 3 Discussion and Results 130
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
Page 150 and 151: 6 Experimental Section 13 C NMR (10
Page 154 and 155: 6 Experimental Section 6.2.4 AB3-Ty
Page 156 and 157: 6 Experimental Section 6.2.4.3 5 4
Page 164 and 165: 6 Experimental Section 6.2.4.11 10
Page 166 and 167: 6 Experimental Section EA: C57H56N4
Page 168 and 169: 6 Experimental Section 6.2.4.15 10
Page 170 and 171: 6 Experimental Section 6.2.5 A2B2-T
Page 174 and 175: 6 Experimental Section 6.2.5.5 αβ
Page 176 and 177: 6 Experimental Section 6.2.5.7 αβ
Page 178 and 179: 6 Experimental Section 6.2.5.9 αα
Page 180 and 181: 6 Experimental Section 6.2.5.11 α
Page 182 and 183: 6 Experimental Section 6.2.5.13 α
Page 186 and 187: 6 Experimental Section 6.2.6 AB2C-T
Page 190 and 191: 6 Experimental Section UV/Vis (CH2C
Page 194 and 195: 6 Experimental Section UV/Vis (CH2C
Page 196 and 197: 6 Experimental Section broad signal
Page 198 and 199: 7 References 16 H. Fischer, K. Zeil
Page 200 and 201: 7 References 57 S. Schwartz, K. Abs
Page 202 and 203:
7 References 89 (a) R. C. Fuson, J.
Page 204 and 205:
7 References 131 (a) J. Perdew, Phy
Page 206 and 207:
S. Jasinski, N. Jux, “Investigati
Page 208 and 209:
Ein großer Dank gilt auch den Ange
Page 210 and 211:
Cirruculum vitae Stefan Jasinski Ge
Page 212 and 213:
204 56 57 58 59 60 61 62 63 64 65 6
show all

1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?