5,10,15,20-TETRAKIS(4-HYDROXYPHENYL)-21H,23H-PORPHINE

Porphyrin H2(p-OCOMe)TPP (0.50 g, 0.59 mmol) was combined with EtOH (1 mL), H2O (3 mL), and concentrated HCl (1 mL), and stirred at reflux for 1 h. After cooling to room temperature, the mixture was diluted with H2O (25 mL), neutralized with 5percent NaOH until the color of the green solution turned dark red and pH was 7.5. The mixturewas stirred vigorously for 1 h, ethyl acetatewas added, and the mixture stirred for 1 h. The organic layer was separated, washed twice with water, dried over anhydrous MgSO4, and concentrated to give 0.40 g (100percent) 4: Rf ¼ 0.31 (2:1 toluene:ethyl acetate); (1) 560 mol of pyrrole and 560 mol of benzaldehyde were mixed to prepare a mixed solution, alternate;(2) In a 2000L titanium high pressure polymerization reactor 1 with mechanically stirred and electrically heated jacket with distillation device on top, solvent E consisting of 840L propionic acid and 560L cyclohexane was added, and the concentration of oxygen in the gas phase from the bottom of the polymerization reactor 1 where N2 is bubbled into the top of the reactor condenser was less than 1percent, then, the polymerization reactor 1 was started to heat the jacket switch, the liquid in the polymerization reactor 1 was heated to reflux, maintaining the polymerization reactor 1 pressure 5.0 atm, at the same time, the mixed solution prepared in step (1) was added dropwise from the top of the polymerization reactor 1 in a dropwise manner, and the molar concentration of pyrrole in the reaction liquid was maintained at less than 0.1 mol/L during the dropwise addition. The water produced by the reaction was removed from the system through the distillation device at the top of the polymerization reactor 1, condensed, and then separated by the liquid-liquid layering device 4, and the upper oil phase was recycled back to the reaction system. The reflux ratio of the distillation column was constantly adjusted so that the water concentration in the polymerization reactor 1 was always lower than 0.05percent.After the addition, the reaction was continued at the same time, and the reaction was stopped after 15 minutes. At the end of the reaction, the reaction temperature was 157.1°C. At this point, the polymerization reactor 1 is maintained at a pressure of 5 atm, air was passed into the oxidation reaction, oxidation reaction time was 22 minutes, during the reaction, the oxygen concentration in the exhaust gas was strictly controlled to be less than 2percent by adjusting the amount of passed air. After completion of the oxidation reaction, left to cool slowly. When the temperature of the liquid in the polymerization reactor 1 drops to room temperature, it was filtered through the filter washing device 2 to obtain the filtrate and filter cake, and the filtrate was subjected to rectification and dehydration in the solvent recovery column 3 of the polymerization reaction to recover the solvent, the recovered solvent is collected to be recycled back to the system for continued use, and the residue of the tower reactor is discharged out of the system. The filtered cake was repeatedly washed with hot water and filtered until the filtrate was colorless. The filter cake was then washed repeatedly with methanol and filtered until the filtered waste water was colorless. The filter cake washed with methanol was the product TPP, after vacuum drying at 80°C51.4of 98.7percent. The process flow is the same as that of embodiment 9, the difference being: (1) 630 mol of pyrrole and 600 mol of p-hydroxybenzaldehyde are added; (2) The reaction time in the polymerization reactor was 28 minutes, the reaction pressure was 3 atm, the reaction temperature was 132.9°C at the end of the reaction, and the water concentration in the polymerization reactor was controlled to be always lower than 0.04percent; (3) The gas introduced into the oxidation reactor is air and the reaction time is 60 minutes; According to this method, the final solid was vacuum dried at 80°C to obtain product TPP 72.0 kg. The product TPP had a synthetic yield of 55.1percent and a purity of 99.2percent based on the reactant pyridine.4-hydroxy-benzaldehyde (14.7 g, 120 mmol) was dissolved in 300 mL of propionic acid, and the resulting solution was heated to reflux under NTo a 1 L Erlenmeyer flask was added pyrrole (2.32 ml, 33.49 mmol), 4-hydroxybenzaldehyde (5 ml, 35 mmol) and 1 L of CHCl3, and the mixture was stirred at room temperature for 30 minutes. BF3OEt2 (Boron Trifluoride Diethyl Ether, 1.17 ml, 9.21 mmol) was added and stirred at room temperature for 1 hour, then DDQ (2, 3-Dichloro-5, 6-dicyano-1, 4-benzoquinone, 5.70 g, 25.12 mmol ) And the mixture is stirred for 1 hour. After confirming TLC and filtration under reduced pressure, the solvent was removed from the resulting solution under reduced pressure, separated by column chromatography, and washed with cold ethanol to give the product (yield: 15percent).General procedure: A solution of 3-hydroxybenzaldehyde (8.8 g, 72 mmol) in propionic acid (300 mL) was brought to reflux. Pyrrole (5 mL, 72 mmol) was added quickly. The resulting mixture was refluxing during additional 1.5 h. After that 200 mL of propionic acid was evaporated. Cooled to room temperature residue was neutralized with saturated solution of NaHCO6.1 g of benzaldehyde was dissolved in 110 mL of propionic acid a, 6 mL of dimethylsulfoxide (DMSO) was added and the mixture was mechanically stirred and heated to 128 ° C. The freshly distilled 3.5 mL pyrrole was added dropwise to 10 mL of propionic acid b mixture, 1 drop per second, heated to 141 ° C, reflux 2 hours, hot filter, propionic acid filter cake 2 times to get blue solid 5, 10, 15, 20-tetrakis(4-hydroxyphenyl)porphyrin crude, drystand by; 10 g of the dried crude product was placed in a 100 mL round bottom flask and 20 mL of absolute ethanol was added to reflux. The solution was heated for 15 min and heated for 1.5 h. The ice was cooled for 1.5 h, filtered and washed twice with ethanol (4-hydroxyphenyl) porphyrin 0.6172 g, the final yield of 7.27percent 5, 10, 15, 20-tetrakis(4-hydroxyphenyl)porphyrinwas obtained by solidification, solid loading and acetone as eluant on silica gel column (200 mesh).General procedure: Corresponding aldehyde precursors (5.4 mmol) was dissolved in propionic acid (54.65) and the solution was heated to 140°C. A freshly distilled pyrrole (5.4 mmol) was slowly added and refluxed for 1 h. Under hot condition 55 ml of anhydrous alcohol was added and the solution was transferred into beaker cooled to room temperature and kept 1 h at −5°C. Filtered the solution to obtain blue powder and dried. A solution of Zn(OAc)