1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.6.3 5 2 - (Bromomethyl)- 5 4 , 10 4 , 20- Tri- t - Butyl - 5 6 - Methyl - 15 4 - Nitro -5,10,15,20- Br 180 Tetraphenylporphyrin, 88 N NH HN N 88 C 58 H 56 BrN 5 O 2 M = 935.00 g·mol -1 NO 2 In a 2 L round bottom flask, methoxymethyl dipyrromethane 39a (3.36 g, 10.0 mmol), nitro dipyrromethane 85 (2.67 g, 10.0 mmol) and 4-t-butyl benzaldehyde (3.24 g, 3.35 mL, 20.0 mmol) are dissolved in 1 L of CHCl3. After addition of TFA (1.55 mL, 20 mmol), the reaction mixture is stirred at rt for 60 min. Then, TEA (2.8 mL, 20 mmol) is added followed by addition of DDQ (4.54 g, 20 mmol) to the claret solution and stirring is continued for 2 h. After evaporation of the solvent, the residue is filtered through a silica plug (CH2Cl2 as eluent) and pre-cleaned by FC (silica, CH2Cl2 : hexanes = 3 : 2) to give a binary mixture of porphyrins 86 and 87 (Scheme 53, p. 113). This material is then taken up in 150 mL of CH2Cl2 and HBr (5.4 M in glacial AcOH, 30 mL) is added whereupon the solution turns dark green. The flask is closed by a one-hole stopper with exhaust duct and the reaction mixture is stirred at rt for 12 h. After that, the green solution is transferred into a separatory funnel and repeatedly washed with water until the color changes to purple-red. Then, the solution is neutralized by shaking with a saturated aqueous solution of NaHCO3, washed with water, dried over MgSO4 and evaporated to dryness to give the mixture of porphyrins 87 and 88 (Scheme 53, p. 113) which is separated by FC (silica, CH2Cl2 : hexanes = 3 : 2) to furnish 1.39 g (1.49 mmol) of pure 88 as purple powder, equiv. to 14.9 % yield based on 85. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.65 (s, 2 H, NH), 1.61 (s, 18 H, t-BuH), 1.63 (s, 9 H, t-BuH), 1.89 (s, 3 H, CH3), 4.15 (s, 2 H, CH2), 7.59 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 7.77 (m, 4+1 H, ArH+Ar’H), 8.14 (d, 3 J = 7.6 Hz, 2 H, ArH), 8.18 (d, 3 J = 7.6 Hz, 2 H, ArH), 8.39 (d, 3 J = 6.1 Hz, 2 H, ArH), 8.62 (d, 3 J = 8.8 Hz, 2 H, ArH), 8.69 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.73 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.90 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.96 (d, 3 J = 4.6 Hz, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 21.8, 31.5, 31.6, 33.1, 34.9 (two peaks), 116.2, 116.8, 120.8, 123.8 (two peaks), 124.7, 126.7, 130.2 (br), 130.8 (br), 132.0 (br), 134.5, 134.6, 135.2, 138.2, 138.6, 138.8, 140.0, 147.8, 149.5, 150.8, 152.2. MS (FAB+, NBA): m/z (%) = 935 (100) [M] +· , 854 (15) [M-Br] +· .
Experimental Section 6 IR (ATR): 𝜈� [cm -1 ] = 3320, 2964, 2906, 2869, 1596, 1561, 1518, 1475, 1400, 1363, 1339, 1310, 1268, 1222, 1211, 1187, 1110, 1022, 993, 983, 967, 919, 847, 800, 740. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (367000), 517 (18800), 553 (9000), 593 (5600), 648 (4000). EA: C58H56BrN5O2·2 H2O. Calc.: C 71.74, H 6.23, N 7.21; found: C 71.77, H 6.08, N 6.89. 6.2.6.4 5 4 , 10 4 , 20 4 - Tri - t- Butyl - 5 2 - (Cyanomethyl) - 5 6 -Methyl -15 4 -Nitro-5, 10, 15, 20- NC tetraphenylporphyrin 89 N NH HN N 89 C 59 H 56 N 6 O 2 M = 88<strong>1.1</strong>1 g·mol -1 NO 2 Following GP I, the following chemicals are scheduled to react with bromomethyl porphyrin 88 (180 mg, 193 μmol): a.: CH2Cl2 (25 mL), Zn(OAc)2·2 H2O (0.85 g, 3.87 mmol, 20 eq.); b.: KCN (0.63 g, 9.68 mmol, 50 eq.), PEG 400 (40 mL). Final purification is achieved by FC over silica with a mixture of CH2Cl2 and hexanes (4 : 1 ratio) as eluent to give 148 mg (168 μmol) of pure 89 as purple powder, equiv. to 87 % yield based on 88. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.70 (s, 2 H, NH), 1.60 (s, 18 H, t-BuH), 1.62 (s, 9 H, t-BuH), 1.93 (s, 3 H, CH3), 3.23 (s, 2 H, CH2), 7.63 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 7.77 (d, 3 J = 7.3 Hz 4 H, ArH), 7.80 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 8.13 (d, 3 J = 7.3 Hz, 4 H, ArH), 8.38 (d, 3 J = 8.5 Hz, 2 H, ArH), 8.62 (d, 3 J = 8.7 Hz, 2 H, ArH), 8.63 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.71 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.90 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.94 (d, 3 J = 4.6 Hz, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 21.8, 23.3, 31.5, 31.6, 34.9, 35.0, 115.7, 117.1, 18<strong>1.1</strong>, 121.0, 121.9, 122.4, 123.8, 123.9, 126.5, 130.0 (br), 131.5, 132.3 (br), 134.5, 134.6, 135.2, 137.8, 138.5, 140.1, 147.8, 149.3, 150.9, 152.5. MS (FAB+, NBA): m/z (%) = 881 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3320, 2963, 2905, 2869, 1596, 1559, 1519, 1476, 1400, 1363, 1340, 1312, 1267, 1223, 1209, 1185, 1110, 1022, 993, 982, 968, 920, 851, 800, 738. 181
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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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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 3.2.9 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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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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