Compound 4
10,20-bis(4-butoxyphenyl)-5,15-diamide-zinc(II)porphyrin
From: Control over differentiation of a metastable supramolecular assembly in one and two dimensions
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
Synthesis of S3 To a solution of compound S1 (293 mg, 0.221 mmol), S2 (504 mg, 0.540 mmol), Na2CO3 (135 mg, 1.28 mmol) in DMF (45 mL), EtOH (5 mL), and H2O (5 mL) mixed solvent, Pd(PPh3)4 (20.4 mg, 0.018 mmol) was added under Ar atmosphere. The solution was stirred at 100 °C for 24 h, cooled to room temperature, and diluted with CHCl3. The mixture was washed with water and dried over MgSO4 anhydrous. The solvent was evaporated, and the solid residue was purified through column chromatography (silica gel, CHCl3:acetone = 10:1). After evaporating the solvent in vacuo, the residue was dissolved in THF (120 mL). To this solution, TBAF (1 M THF solution, 700 μL) was added, and the mixture was stirred for 1 h at room temperature. The solution was diluted with EtOAc, then washed with water and dried over Na2SO4 anhydrous. The solvent was evaporated, and the solid residue was purified through column chromatography (silica gel, chloroform:acetone = 5:1) and SEC (Bio-Beads SX-1, DCM) to provide S3 as a purple solid (283 mg, yield: 59 %). 1H NMR (CDCl3, 298 K) δ 0.80-0.87 (18H, m, CH3-), 1.13-1.28 (96H, m, CH3-(CH2)8- CH2-CH2-CH2-O-), 1.40-1.46 (12H, m, CH3-(CH2)8-CH2-CH2-CH2-O-), 1.69-1.83 (12H, m, CH3-(CH2)8-CH2-CH2-CH2-O-), 2.31-2.34 (4H, m, -NH-CH2-CH2-CH2-O-), 3.82-3.85 (4H, m, -NH-CH2-CH2-CH2-O-), 3.98-4.07 (12H, m, CH3-(CH2)8-CH2-CH2-CH2-O-), 4.42-4.44 (4H, m, -NH-CH2-CH2-CH2-O-), 5.32 (2H, s, HO-), 6.69 (2H, t, J = 5.2 Hz, - NH-CH2-CH2-CH2-O-), 7.06 (4H, s, C6H2), 7.20-7.29 (8H, m, C6H4), 8.03 (4H, d, J = 8.8 Hz, C6H4), 8.08 (4H, d, J = 8.8 Hz, C6H4), 8.90 (4H, d, J = 4.8 Hz, β-pyrrole), 8.92 (4H, d, J = 4.8 Hz, β-pyrrole).; 13C NMR (CDCl3, 298 K), δ 14.07, 22.61, 22.66, 26.09, 29.19, 29.26, 29.37, 29.56, 29.65, 29.71, 30.31, 31.83, 31.89, 38.56, 67.06, 69.43, 73.53, 105.67, 112.46, 113.55, 120.22, 120.58, 129.29, 131.50, 131.66, 134.91, 135.48, 135.55, 135.65, 141.24, 150.11, 150.24, 153.61, 158.07, 167.75.; MALDI-TOF mass (dithranol): calcd. for C136H194N6O12Zn: 2168.41; found: 2168.97.; Elemental Analysis: calcd. for C136H194N6O12Zn(CHCl3)0.4 (%): C, 73.86; H, 8.83; N, 3.79; O, 8.66; Zn, 2.95: found: C, 73.79; H, 8.88; N, 3.73.
Synthesis of 4: To a solution of compound S3 (21.4 mg, 9.85 μmol), n-butanol (3 μL, 32.8 μmol), and PPh3 (11.3 mg, 43.1 μmol) in THF (0.25 mL), 1.9 M toluene solution of diisopropyl azodicarboxylate (16 μL, 30.4 μmol) was added at 0 °C under Ar atmosphere. The solution was stirred at 40 °C overnight, cooled to room temperature, and diluted with EtOAc. The mixture was washed with brine and dried over Na2SO4 anhydrous. The solvent was evaporated, and the solid residue was purified through column chromatography (silica gel, CHCl3:acetone = 19:1) to provide 4 as a purple solid (19.4 mg, yield: 86 %). m.p. = 184-186 °C; 1H NMR (CDCl3, 298 K) δ 0.81-0.87 (18H, m, CH3-), 1.08-1.28 (102H, m, CH3-CH2-CH2-CH2-O-, CH3-(CH2)8-CH2-CH2-CH2-O-), 1.40-1.47 (12H, m, CH3-(CH2)8-CH2-CH2-CH2-O-), 1.63-1.83 (16H, m, CH3-CH2-CH2-CH2-O-, CH3-(CH2)8-CH2-CH2-CH2-O-), 1.94-2.01 (4H, m, CH3-CH2-CH2-CH2-O-), 2.26-2.29 (4H, m, -NHCH2-CH2-CH2-O-), 3.78-3.83 (4H, m, -NH-CH2-CH2-CH2-O-), 3.97-4.05 (12H, m, CH3- (CH2)8-CH2-CH2-CH2-O-), 4.21-4.28 (4H, m, CH3-CH2-CH2-CH2-O-), 4.39-4.42 (4H, m, -NH-CH2-CH2-CH2-O-), 6.65 (2H, t, J = 4.8 Hz, -NH-CH2-CH2-CH2-O-), 6.98 (4H, s, C6H2), 7.25-7.29 (8H, m, C6H4), 8.09 (4H, d, J = 8.4 Hz, C6H4), 8.12 (4H, d, J = 8.4 Hz, C6H4), 8.93 (4H, d, J = 4.8 Hz, β-pyrrole), 8.97 (4H, d, J = 4.8 Hz, β-pyrrole).; 13C NMR (CDCl3, 298 K), δ 14.01, 14.08, 19.45, 22.63, 22.67, 26.09, 29.16, 29.27, 29.37, 29.39, 29.56, 29.59, 29.66, 29.72, 30.32, 31.61, 31.84, 31.91, 39.56, 67.27, 67.98, 69.42, 105.64, 112.52, 112.54, 120.40, 120.89, 129.55, 131.73, 131.96, 135.02, 135.38, 135.48, 135.82, 141.18, 150.38, 150.53, 153.12, 158.20, 158.82, 167.45.; MALDI-TOF mass (dithranol): calcd. for C144H210N6O12Zn: 2280.53; found: 2280.85.; Elemental Analysis: calcd. for C144H210N6O12Zn (%): C, 75.77; H, 9.27; N, 3.68; O, 8.41; Zn, 2.86 : found: C, 75.76; H, 9.32; N, 3.76.
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319534614
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