| 55.1% |
Stage #1: pyrrole; 4-fluorobenzaldehyde With propionic acid In cyclohexane at 158.2℃; for 0.15h;
Stage #2: In cyclohexane for 0.5h; Reflux; |
12.1-12.4 Example 1
General procedure: (1) Prepare 560mol of pyrrole and 560mol of benzaldehyde into a mixed solution and set aside;(2) In a 2000L high-pressure titanium polymerization reactor 1 with a mechanical stirring and electric heating jacket and a distillation device on the top, add a solvent E consisting of 840L of propionic acid and 560L of cyclohexane,From the bottom of the polymerization reactor 1, N2 is bubbled to the oxygen concentration in the gas phase of the reactor top condenser outlet to be lower than 1%, and then the electrical heating jacket switch of the polymerization reactor 1 is started to heat the liquid in the polymerization reactor 1 to reflux. , Maintaining the pressure of the polymerization reactor 1 at 5.0atm, while adding the mixed solution prepared in step (1) from the top of the polymerization reactor 1 by dropwise addition, the molar concentration of pyrrole in the reaction solution is always kept lower than 0.1mol during the dropwise addition / L.The water produced by the reaction is removed from the system through a distillation device at the top of the polymerization reactor, and after condensing, it is delaminated by a liquid-liquid layering device 8 to circulate the upper oil phase back into the reaction system. The reflux ratio of the distillation column was continuously adjusted so that the water concentration in the polymerization reactor 1 was always lower than 0.05%. After the dropwise 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. Then slowly cool it down. When the temperature in the polymerization reactor 1 drops to normal temperature, the reactants in the polymerization reactor 1 are filtered through the filtering and washing device 2 to obtain a filtrate and a crude TPP filter cake. The mass of the crude TPP filter cake is 54.8 kg. According to gas chromatography analysis, the amount of pyrrole remaining in the polymerization reaction system was 55.2 mol. The filtrate can be distilled into the polymerization solvent recovery tank 3 for distillation, and the solvent and unreacted pyrrole can be recovered. The recovered solvent and pyrrole are collected for recycling to the polymerization reactor 1 and continued to be used. The residue of the distillation kettle is discharged outside the system. deal with.(3) Add 54.8 kg of crude TPP filter cake obtained by centrifugal filtration to a 2000L oxidation reactor 4 with mechanical stirring and electric heating jacket, with condensation reflux at the top and gas distributor at the bottom, and simultaneously add 1400 kg of propylene into the kettle Acid, and simultaneously introducing nitrogen gas to replace the gas phase space in the oxidation reactor 4 to a tail oxygen concentration of less than 3%. Then, the switch of the electric heating jacket is started to heat the liquid in the oxidation reactor 4. When the liquid in the oxidation reactor 4 is heated to reflux, air is passed through to carry out the oxidation reaction. The oxidation reaction time is 22 minutes. During the reaction, the oxygen concentration in the tail gas is strictly controlled by adjusting the amount of the air to be passed to less than 3%. After the oxidation reaction was completed, it was left to cool slowly. When the temperature of the liquid in the oxidation reactor 4 is reduced to normal temperature, it is put into a filtering and washing device 5 for filtration to obtain a filtrate and a solid. The filtrate is dehydrated through an oxidation reaction solvent recovery tower 6 and dehydrated and recovered to obtain propionic acid, and the recovered propionic acid is collected. After that, it is ready to be used in the recycle and oxidation reactor 4 and the residue of the tower kettle is discharged out of the system. The filtrate can also be directly recycled to the oxidation reactor 4 without any treatment and continued to be used. The solid obtained by filtration was repeatedly washed with hot water and then filtered until the filtrate was colorless. Then repeatedly wash with methanol and then filter until the filtered wastewater is freecolor. The solid washed with methanol is the product TPP, and 46.0 kg of a tetraphenylporphine product is obtained after drying in a drying device 7 under vacuum at 80 ° C.The yield of the product TPP based on the pyrrole of the reactant was 59.3%, and the purity was 99.2%. |
| 40% |
With acetic acid In propionic acid at 110℃; for 3h; Inert atmosphere; |
|
| 36% |
With nitrobenzene In propionic acid for 0.166667h; Microwave irradiation; Heating; |
|
| 27% |
With propionic acid for 0.5h; Reflux; |
2.1.3. Synthetic procedure used for preparation of H2TXPP
General procedure: Adler method has been employed using direct condensation reactionof equimolar amounts of freshly distilled pyrrole (20 mmol) and4-halobenzaldehyde; halo = fluoro, chloro, bromo and iodo(20 mmol) added to propionic acid (20 ml) and heated to a refluxingtemperature. The solutions were allowed to reflux and put on constantstirring for about 30 min. The reaction mixture was allowed to cool atroom temperature (30 °C). Later reaction mixtures were filtered andthe residues were washed with methanol until the filtrate wascolourless. The courses of reaction were monitored and purity of thesecorresponding compounds has been achieved by column chromatographyon a basic alumina. However CHCl3was used as eluent in all cases.Compounds were re-crystallized from CHCl3 on vacuum further subjectedto various spectroscopic studies. |
| 20% |
Stage #1: pyrrole; 4-fluorobenzaldehyde With Tulsion-63 resin; Triethyl orthoacetate In dichloromethane at 20℃; for 17h;
Stage #2: With chloranil In dichloromethane for 2h; Heating; |
|
| 20% |
With propionic acid for 0.5h; Reflux; |
|
| 11% |
With air; chloroacetic acid In xylene for 1.5h; Heating; |
|
| 6% |
In water at 199.84℃; for 0.166667h; Microwave irradiation; Green chemistry; |
|
|
With propionic acid for 30h; Heating; |
|
|
With trifluoroacetic acid In dichloromethane; water for 2h; |
|
|
Stage #1: pyrrole; 4-fluorobenzaldehyde With boron trifluoride In dichloromethane for 4h; Inert atmosphere; Reflux;
Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane |
|
|
Stage #1: pyrrole; 4-fluorobenzaldehyde With trifluoroacetic acid In dichloromethane for 1h; Darkness; Inert atmosphere;
Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 1h; Inert atmosphere; |
|
|
With oxygen; trifluoroacetic acid In 5,5-dimethyl-1,3-cyclohexadiene Heating; |
2.1. Synthesis of H2P-4C6H4F
H2P-4C6H4F was synthesized by condensation of fluorinesubstitutedbenzaldehyde with pyrrole in boiling xylene in the presence of trifluoroacetic acid as a catalyst and using atmospheric oxygen as an oxidizing agent for porphyrinogen. The synthesis is described elsewhere in the literature [17-19] and some details can be found in the Supplementary Information. |
|
With propionic acid at 145℃; for 2h; Inert atmosphere; Darkness; |
2.2. Syntheses of porphyrins
General procedure: Tetraphenylporphyrin (TPP), tetrakis(2-chlorophenyl)porphyrin (T(2-Cl)PP), tetrakis(3-chlorophenyl)porphyrin (T(3-Cl)PP), tetrakis(4-chlorophenyl)porphyrin (T(4-Cl)PP), tetrakis(4-fluorophenyl)porphyrin (T(4-F)PP), tetrakis(4-methylphenyl)porphyrin (T(4 CH3)PP), tetrakis(4-methoxyphenyl)porphyrin (T(4 OCH3)PP), tetrakis(naphthalen-2-yl)porphyrin (T(2-Na.)P) and tetrakis(4-methoxycarbonylphenyl)porphyrin (T(4 COOCH3)PP) were synthesizedthrough condensation of the corresponding aromatic aldehydewith freshly distilled pyrrole in propionic acid according to the Adler-Longo method after some modifications (Eq. 1 in Scheme 1) [74-76].In the synthesis process, aromatic aldehyde (100 mmol) was dissolved inpropionic acid (300 mL) with stirring at the room temperature under theatmosphere of nitrogen. Then, the resultant solution was heated torefluxing (145 C), and freshly distilled pyrrole (100 mmol) was addeddropwise. After stirring and refluxing for 2.0 h under the protection oftin foil from ambient light, the resultant reaction mixture was cooled toroom temperature and kept standing at room temperature for 24.0 h.The collected precipitate from suction filtration was suspended inmethanol (200 mL) with stirring at room temperature for 6.0 h andwashed with methanol (2 × 100 mL) successively. At last, silica columnchromatography was employed for further purification using themixture of cyclohexane and dichloromethane as eluent (Vcyclohexane :Vdichloromethane = 6 : 1). All the obtained porphyrins were dried at 75 C for12.0 h under reduced pressure and characterized through FT-IR, 1HNMR, 13C NMR and ESI-MS. Details could be seen in the ElectronicSupplementary Information. |
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