CN111995557A - Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with iron (II) porphyrin - Google Patents

Abstract

A kind of method for iron (II) porphyrin catalyzed oxidation of cumene to synthesize cumene hydrogen peroxide, iron (II) porphyrin is dispersed in cumene, and the amount of iron (II) porphyrin is cumene 1× ^10-4 %～1% of the amount of benzene, mol/mol, seal the reaction system, feed the oxidant, heat up to 40～100°C under stirring, keep the set temperature and pressure, and stir the reaction for 3.0～24.0 h, to obtain the cumene solution of cumene hydrogen peroxide, which can be directly used for subsequent reactions. The reaction solution was post-treated to calculate the cumene conversion and cumene hydrogen peroxide selectivity. The invention has the advantages of low reaction temperature, high cumene conversion rate, high cumene hydrogen peroxide selectivity, less by-products, little environmental impact, etc., and the invention has low reaction temperature and high safety factor. The invention provides an efficient, feasible and safe method for synthesizing cumene hydrogen peroxide by catalytic oxidation of cumene.

Description

A kind of method that iron (II) porphyrin catalyzes oxidation of cumene to synthesize cumene hydrogen peroxide

technical field

The invention relates to a method for synthesizing cumene hydrogen peroxide through the catalytic oxidation of cumene by iron (II) porphyrin, and belongs to the field of organic catalysis and fine organic synthesis.

Background technique

The preparation of cumene hydrogen peroxide by oxidation of cumene is an important transformation process in the chemical industry, and its oxidation product cumene hydrogen peroxide is not only the basic raw material for industrial production of phenol and acetone, but also the preparation of epoxy resin by oxidation of propylene in industry. Important oxidant of propane. Globally, 90% of phenol is produced by the decomposition of cumene hydrogen peroxide, which also shows the importance of cumene hydrogen peroxide synthesis in the chemical industry (ACS Sustainable Chemistry & Engineering 2019, 7:7708-7715; Chemical Engineering Science 2018, 177:391-398). At present, the industrial production of cumene hydrogen peroxide mainly uses ^O ₂ or air as the oxidant, and cumene hydrogen peroxide as the initiator. The conversion rate of benzene is about 20%, and the selectivity of cumene hydroperoxide is 90-92% (ACS Sustainable Chemistry & Engineering 2019, 7: 7708-7715; Applied Catalysis A, General 2018, 561: 59-67). The main problems that exist are that the cumene conversion rate is not ideal, the cumene hydrogen peroxide selectivity is not high enough, the reaction temperature is high, and the safety factor is low. Therefore, the highly selective oxidation of cumene to _cumene hydroperoxide using O as the oxidant under mild conditions, especially at lower reaction temperatures, is still a very urgent practical demand in the chemical industry. .

As a model compound of cytochrome P-450, metalloporphyrins are widely used in biomimetic catalysis of various organic synthesis reactions, especially oxidation reactions (ChemSusChem 2019, 12: 684-691; Polyhedron 2019, 163: 144-152; Journal of Catalysis 2019, 369:133-142). Metalloporphyrin has an approximately planar molecular structure, which enables the catalytically active metal center to be exposed to the maximum extent in the catalytic system to play a role. It can show excellent catalytic activity at 1/1,000,000 to 1/100,000 of the molar amount of the substrate. , which can significantly reduce the cost of catalytic reactions, and is one of the preferred catalysts for various catalytic reactions. At the same time, as a catalyst, metalloporphyrin not only has a wide range of selection objects for the central metal, but also has a wide range of control space for the substituents around the metalloporphyrin ring.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of iron (II) porphyrin catalyzed oxidation of cumene efficiently, the method for the highly selective synthesis of cumene hydrogen peroxide, with metalloporphyrin as a catalyzer, catalysis _O2 oxidation of cumene to synthesize cumene hydrogen peroxide will have the advantages of less catalyst dosage, high catalytic efficiency, easy structure adjustment, good biocompatibility, green environmental protection, etc. Synthesis of Cumene Hydroperoxide by Sexual Oxidation.

The technical scheme of the present invention is as follows:

A method of iron (II) porphyrin catalyzed oxidation of cumene to synthesize cumene hydrogen peroxide, the method comprises the following process:

Disperse iron (II) porphyrin in cumene, the amount of iron (II) porphyrin is 1×10 ^-4 %～1% of the amount of cumene, mol/mol, and the reaction system is sealed , introduce the oxidant (0.10～0.50MPa), heat up to 40～100℃ under stirring, keep the set temperature and pressure, stir and react for 3.0～24.0h to obtain the cumene solution of cumene hydrogen peroxide, which is directly carried out Follow-up reaction is used; The reaction solution is after-processed to calculate the cumene conversion rate and the cumene hydrogen peroxide selectivity;

The iron (II) porphyrin is at least one of the compounds shown in formula (I):

Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are each independently: hydrogen, methoxy, ethoxy, methyl, ethyl, phenyl, fluorine, chlorine, bromine, carboxyl, methoxy carbonyl, acetyl, formyl, hydroxyl, amino, methylol, cyano or nitro;

The iron (II) porphyrin is 5,10,15,20-tetrakis (2-carboxyphenyl) porphyrin iron (II), 5,10,15,20-tetrakis (3-carboxyphenyl) porphyrin Iron(II), 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron(II), 5,10,15,20-tetrakis(2,4-dicarboxyphenyl)porphyrin iron (II), 5,10,15,20-tetrakis(2,4,6-tricarboxyphenyl)porphyrin iron(II), 5,10,15,20-tetrakis(2-chlorophenyl)porphyrin Iron(II), 5,10,15,20-tetrakis(3-chlorophenyl)porphyrin iron(II), 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin iron(II) or 5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin iron(II).

Further, the ratio of the amount of iron (II) porphyrin to cumene is 1:1000000-1:100, preferably 1:100000-1:1000.

The reaction temperature is 40-100°C, preferably 60-90°C; the reaction pressure is 0.10-0.50MPa, preferably 0.10-0.20MPa; the reaction time is 3.0-24.0h, preferably 6.0-12.0h; the The stirring rate is 600-1200 rpm, preferably 800-1000 rpm.

The oxidant is oxygen, air or any mixture thereof.

The post-processing method is as follows: after the reaction is completed, add triphenylphosphine PPh ₃ to the reaction solution, and the dosage is 30% to 60% of the amount of cumene, and the reduction is performed by stirring at room temperature (20 to 30° C.) for 40 minutes. Generated peroxide, and then analyze and calculate the conversion rate of cumene and the selectivity of cumene hydrogen peroxide.

The analysis method of the reaction result of the present invention is as follows: after the reaction is completed, add triphenylphosphine (PPh ₃ , the dosage is 30% to 60% of the amount of the cumene substance) into the reaction solution, and the room temperature (20 to 30° C.) Under stirring for 40min, the generated peroxide was reduced, and then the conversion rate of cumene and the selectivity of cumene hydroperoxide were analyzed and calculated. Take acetone as solvent to dilute, take naphthalene as internal standard, carry out gas chromatographic analysis, calculate the conversion rate of cumene and the selectivity of cumene hydrogen peroxide.

The invention uses metalloporphyrin as a catalyst to catalyze molecular oxygen oxidation of cumene to selectively synthesize isopropyl hydrogen peroxide under mild conditions, which not only greatly reduces the reaction temperature, but also significantly improves the selection of cumene hydrogen peroxide It can improve the atomic economy of the process and reduce the emission of environmental pollutants, which is in line with the current chemical industry's realistic demand for "energy saving and emission reduction", and also in line with the current chemical industry's selective catalytic oxidation of cumene under mild conditions. Urgent need for the synthesis of cumene hydroperoxide.

The beneficial effects of the present invention are mainly reflected in: the iron (II) porphyrin catalyzed oxidation of cumene of the present invention is efficient, and the method for synthesizing cumene hydrogen peroxide with high selectivity has the advantages of low reaction temperature and high cumene conversion rate, The cumene hydrogen peroxide has the advantages of high selectivity, few by-products, little environmental impact, etc., and the invention has the advantages of low reaction temperature and high safety factor. Therefore, the present invention provides an efficient, feasible and safe novel method for synthesizing cumene hydrogen peroxide by catalytic oxidation of cumene.

Detailed ways

The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

The metalloporphyrins used in the present invention are synthesized with reference to Journal of Materials Chemistry A 2018, 6:17698-17705; Journal of the American Chemical Society 2018, 140:6383-6390. The reagents used were all commercially available analytical grades.

Examples 1 to 47 are examples of catalytic oxidation of cumene.

Examples 48 to 51 are comparative experiments.

Example 52 is an example of a scale-up experiment.

Example 1

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 30.5%, the selectivity of 2-phenyl-2-propanol was 10.5%, the selectivity of acetophenone was 7.0%, the selectivity of cumene hydroperoxide was 82.5%, and no benzoic acid was detected.

Example 2

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(3-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 20.5%, the selectivity of 2-phenyl-2-propanol was 7.0%, the selectivity of acetophenone was 8.6%, the selectivity of cumene hydroperoxide was 84.4%, and no benzoic acid was detected.

Example 3

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(2-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 26.7%, the selectivity of 2-phenyl-2-propanol was 8.8%, the selectivity of acetophenone was 8.5%, the selectivity of cumene hydroperoxide was 82.7%, and the generation of benzoic acid was not detected.

Example 4

In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) 5,10,15,20-tetrakis(2,3,6-trichlorophenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) ) in cumene, the temperature was raised to 80°C with stirring, and oxygen (1.0 atm) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 17.8%, the selectivity of cumene hydroperoxide was 100.0%, and the formation of benzoic acid, 2-phenyl-2-propanol and acetophenone was not detected.

Example 5

In a 25mL pressure reaction tube, 0.0010g (0.001mmol) 5,10,15,20-tetrakis(2,5-dichlorophenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) cumene In the mixture, the temperature was raised to 80°C with stirring, and oxygen (1.0 atm) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 15.1%, the selectivity of 2-phenyl-2-propanol was 3.2%, the selectivity of acetophenone was 4.5%, the selectivity of cumene hydroperoxide was 92.3%, and no benzoic acid was detected.

Example 6

In a 25mL pressure reaction tube, 0.0010g (0.001mmol) 5,10,15,20-tetrakis(2,6-trichlorophenyl)porphyrin porphyrin iron (II) was dispersed in 1.2019g (10mmol) isocyanurate In propylbenzene, the temperature was raised to 80°C with stirring, and oxygen (1.0 atm) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 13.9%, the selectivity of 2-phenyl-2-propanol was 8.2%, the selectivity of acetophenone was 7.0%, the selectivity of cumene hydroperoxide was 84.8%, and no benzoic acid was detected.

Example 7

In a 25mL pressure reaction tube, 0.0008g (0.001mmol) of 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 14.3%, the selectivity of 2-phenyl-2-propanol was 19.4%, the selectivity of acetophenone was 9.3%, the selectivity of cumene hydroperoxide was 71.3%, and no benzoic acid was detected.

Example 8

In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of 5,10,15,20-tetrakis(3-chlorophenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 15.0%, the selectivity of 2-phenyl-2-propanol was 10.9%, the selectivity of acetophenone was 13.2%, the selectivity of cumene hydroperoxide was 75.9%, and the generation of benzoic acid was not detected.

Example 9

In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of 5,10,15,20-tetrakis(2-chlorophenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 7.3%, the selectivity of acetophenone was 8.4%, the selectivity of cumene hydroperoxide was 91.6%, and the formation of benzoic acid and 2-phenyl-2-propanol was not detected.

Example 10

In a 25mL pressure reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-esterylphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene, The temperature was raised to 80° C. with stirring, and oxygen gas (0.20 MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 25.5%, the selectivity of 2-phenyl-2-propanol was 7.0%, the selectivity of acetophenone was 10.8%, the selectivity of cumene hydroperoxide was 82.2%, and no benzoic acid was detected.

Example 11

In a 25mL pressure reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(3-esterylphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene, The temperature was raised to 80° C. with stirring, and oxygen gas (0.20 MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 20.7%, the selectivity of 2-phenyl-2-propanol was 10.4%, the selectivity of acetophenone was 8.4%, the selectivity of cumene hydroperoxide was 81.2%, and the generation of benzoic acid was not detected.

Example 12

In a 25mL pressure reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(2-esterylphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene, The temperature was raised to 80° C. with stirring, and oxygen gas (0.20 MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 23.9%, the selectivity of 2-phenyl-2-propanol was 18.0%, the selectivity of acetophenone was 14.1%, the selectivity of cumene hydroperoxide was 67.9%, and no benzoic acid was detected.

Example 13

In a 25mL pressure reaction tube, 0.0007g (0.001mmol) of 5,10,15,20-tetrakis(4-methylphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene, The temperature was raised to 80° C. with stirring, and oxygen gas (0.20 MPa) was introduced. The reaction was stirred at 800 rpm for 5.0 h at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 8.3%, the selectivity of acetophenone was 7.5%, the selectivity of cumene hydroperoxide was 92.5%, and the formation of benzoic acid and 2-phenyl-2-propanol was not detected.

Example 14

In a 25mL pressure reaction tube, 0.0008g (0.001mmol) of 5,10,15,20-tetrakis(4-cyanophenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene, The temperature was raised to 80° C. with stirring, and oxygen gas (0.20 MPa) was introduced. The reaction was stirred at 800 rpm for 5.0 h at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 5.7%, the selectivity of 2-phenyl-2-propanol was 11.0%, the selectivity of acetophenone was 6.4%, the selectivity of cumene hydroperoxide was 82.6%, and no benzoic acid was detected.

Example 15

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 40°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm for 8.0 h at 40 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. No significant product formation was detected.

Example 16

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 50°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm for 8.0 h at 50 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 9.3%, the selectivity of cumene hydroperoxide was 100%, and the formation of benzoic acid, 2-phenyl-2-propanol and acetophenone was not detected.

Example 17

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 60°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm at 60 °C for 8.0 h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 15.3%, the selectivity of 2-phenyl-2-propanol was 0.1%, the selectivity of acetophenone was 0.1%, the selectivity of cumene hydroperoxide was 99.8%, and the generation of benzoic acid was not detected.

Example 18

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 70°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm at 70 °C for 8.0 h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 23.6%, the selectivity of 2-phenyl-2-propanol was 7.3%, the selectivity of acetophenone was 2.1%, the selectivity of cumene hydroperoxide was 90.6%, and no benzoic acid was detected.

Example 19

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 90°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm at 70 °C for 8.0 h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 36.8%, the selectivity of 2-phenyl-2-propanol was 16.4%, the selectivity of acetophenone was 8.5%, the selectivity of cumene hydroperoxide was 75.1%, and no benzoic acid was detected.

Example 20

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 100°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm for 8.0 h at 100 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 45.5%, the selectivity of 2-phenyl-2-propanol was 18.3%, the selectivity of acetophenone was 9.4%, the selectivity of cumene hydroperoxide was 72.3%, and no benzoic acid was detected.

Example 21

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.10MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 30.5%, the selectivity of 2-phenyl-2-propanol was 15.7%, the selectivity of acetophenone was 6.2%, the selectivity of cumene hydroperoxide was 78.1%, and no benzoic acid was detected.

Example 22

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.30MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 30.8%, the selectivity of 2-phenyl-2-propanol was 7.3%, the selectivity of acetophenone was 8.8%, the selectivity of cumene hydroperoxide was 83.9%, and no benzoic acid was detected.

Example 23

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.40MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 31.1%, the selectivity of 2-phenyl-2-propanol was 5.6%, the selectivity of acetophenone was 10.1%, the selectivity of cumene hydroperoxide was 84.3%, and no benzoic acid was detected.

Example 24

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.50MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 31.5%, the selectivity of 2-phenyl-2-propanol was 4.2%, the selectivity of acetophenone was 10.7%, the selectivity of cumene hydroperoxide was 85.1%, and no benzoic acid was detected.

Example 25

In a 25mL pressure-resistant reaction tube, 0.000009g (0.00001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 12.9%, the selectivity of 2-phenyl-2-propanol was 4.0%, the selectivity of acetophenone was 0.7%, the selectivity of cumene hydroperoxide was 95.3%, and the generation of benzoic acid was not detected.

Example 26

In a 25mL pressure-resistant reaction tube, 0.00009g (0.0001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 22.6%, the selectivity of 2-phenyl-2-propanol was 6.9%, the selectivity of acetophenone was 1.9%, the selectivity of cumene hydroperoxide was 91.2%, and no benzoic acid was detected.

Example 27

In a 25mL pressure-resistant reaction tube, 0.0017g (0.002mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 32.7%, the selectivity of 2-phenyl-2-propanol was 13.3%, the selectivity of acetophenone was 8.4%, the selectivity of cumene hydroperoxide was 78.3%, and no benzoic acid was detected.

Example 28

In a 25mL pressure reaction tube, 0.0043g (0.005mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 34.5%, the selectivity of 2-phenyl-2-propanol was 13.4%, the selectivity of acetophenone was 8.5%, the selectivity of cumene hydroperoxide was 78.1%, and no benzoic acid was detected.

Example 29

In a 25mL pressure-resistant reaction tube, 0.0085g (0.01mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 36.1%, the selectivity of 2-phenyl-2-propanol was 14.6%, the selectivity of acetophenone was 9.9%, the selectivity of cumene hydroperoxide was 75.5%, and no benzoic acid was detected.

Example 30

In a 25mL pressure-resistant reaction tube, 0.0170g (0.02mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 36.5%, the selectivity of 2-phenyl-2-propanol was 16.6%, the selectivity of acetophenone was 10.3%, the selectivity of cumene hydroperoxide was 73.1%, and no benzoic acid was detected.

Example 31

In a 25mL pressure-resistant reaction tube, 0.0426g (0.05mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 37.2%, the selectivity of 2-phenyl-2-propanol was 15.8%, the selectivity of acetophenone was 11.3%, the selectivity of cumene hydroperoxide was 72.9%, and no benzoic acid was detected.

Example 32

In a 25mL pressure-resistant reaction tube, 0.0852g (0.1mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 39.1%, the selectivity of 2-phenyl-2-propanol was 15.6%, the selectivity of acetophenone was 12.2%, the selectivity of cumene hydroperoxide was 72.2%, and the generation of benzoic acid was not detected.

Example 33

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred for 3.0 h at 800 rpm at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 14.3%, the selectivity of 2-phenyl-2-propanol was 1.8%, the selectivity of cumene hydroperoxide was 98.2%, and the formation of benzoic acid and acetophenone was not detected.

Example 34

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 4.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 17.5%, the selectivity of 2-phenyl-2-propanol was 2.7%, the selectivity of acetophenone was 0.6%, the selectivity of cumene hydroperoxide was 96.7%, and no benzoic acid was detected.

Example 35

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800 rpm for 5.0 h at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 21.3%, the selectivity of 2-phenyl-2-propanol was 3.5%, the selectivity of acetophenone was 0.9%, the selectivity of cumene hydroperoxide was 95.6%, and no benzoic acid was detected.

Example 36

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred for 6.0 h at 800 rpm at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 25.9%, the selectivity of 2-phenyl-2-propanol was 7.7%, the selectivity of acetophenone was 2.3%, the selectivity of cumene hydroperoxide was 90.0%, and no benzoic acid was detected.

Example 37

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 7.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 27.8%, the selectivity of 2-phenyl-2-propanol was 9.5%, the selectivity of acetophenone was 5.3%, the selectivity of cumene hydroperoxide was 85.2%, and the generation of benzoic acid was not detected.

Example 38

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 9.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 32.6%, the selectivity of 2-phenyl-2-propanol was 11.3%, the selectivity of acetophenone was 8.1%, the selectivity of cumene hydroperoxide was 80.6%, and no benzoic acid was detected.

Example 39

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 10.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 33.9%, the selectivity of 2-phenyl-2-propanol is 12.8%, the selectivity of acetophenone is 8.0%, the selectivity of cumene hydroperoxide is 79.2%, and the formation of benzoic acid is not detected

Example 40

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C at 800rpm for 11.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 34.5%, the selectivity of 2-phenyl-2-propanol was 13.0%, the selectivity of acetophenone was 8.2%, the selectivity of cumene hydroperoxide was 78.8%, and the formation of benzoic acid was not detected

Example 41

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C at 800rpm for 12.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 36.1%, the selectivity of 2-phenyl-2-propanol was 13.4%, the selectivity of acetophenone was 8.5%, the selectivity of cumene hydroperoxide was 78.1%, and no benzoic acid was detected.

Example 42

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 15.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 36.9%, the selectivity of 2-phenyl-2-propanol was 13.9%, the selectivity of acetophenone was 8.9%, the selectivity of cumene hydroperoxide was 77.2%, and the generation of benzoic acid was not detected.

Example 43

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 20.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 38.1%, the selectivity of 2-phenyl-2-propanol was 14.2%, the selectivity of acetophenone was 8.8%, the selectivity of cumene hydroperoxide was 77.0%, and no benzoic acid was detected.

Example 44

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C at 800rpm for 24.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 41.2%, the selectivity of 2-phenyl-2-propanol was 15.5%, the selectivity of acetophenone was 8.2%, the selectivity of cumene hydroperoxide was 76.3%, and no benzoic acid was detected.

Example 45

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 600 rpm for 8.0 h at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 27.2%, the selectivity of 2-phenyl-2-propanol was 10.4%, the selectivity of acetophenone was 6.5%, the selectivity of cumene hydroperoxide was 83.1%, and no benzoic acid was detected.

Example 46

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. At 80°C, the reaction was stirred at 1000 rpm for 8.0 h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 32.6%, the selectivity of 2-phenyl-2-propanol was 10.6%, the selectivity of acetophenone was 7.3%, the selectivity of cumene hydroperoxide was 82.1%, and no benzoic acid was detected.

Example 47

In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred for 8.0 h at 1200 rpm at 80 °C. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 33.4%, the selectivity of 2-phenyl-2-propanol was 11.2%, the selectivity of acetophenone was 7.5%, the selectivity of cumene hydroperoxide was 81.3%, and no benzoic acid was detected.

Example 48 (comparative experiment)

In a 25 mL pressure-resistant reaction tube, 0.0002 g (0.001 mmol) of iron (II) acetate was dispersed in 1.2019 g (10 mmol) of cumene, and the temperature was raised to 80° C. with stirring, and oxygen (0.20 MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 18.7%, the selectivity of 2-phenyl-2-propanol was 26.5%, the selectivity of acetophenone was 4.8%, the selectivity of cumene hydroperoxide was 68.7%, and no benzoic acid was detected.

Example 49 (comparative experiment)

In a 25 mL pressure-resistant reaction tube, 0.00016 g (0.001 mmol) of iron (II) sulfate was dispersed in 1.2019 g (10 mmol) of cumene, and the temperature was raised to 80° C. with stirring, and oxygen (0.20 MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 13.9%, the selectivity of 2-phenyl-2-propanol was 19.2%, the selectivity of acetophenone was 8.1%, the selectivity of cumene hydroperoxide was 72.7%, and no benzoic acid was detected.

Example 50 (comparative experiment)

In a 25mL pressure reaction tube, 0.0008g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin zinc (II) was dispersed in 1.2019g (10mmol) of cumene and stirred The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 16.5%, the selectivity of 2-phenyl-2-propanol was 2.9%, the selectivity of cumene hydroperoxide was 97.1%, and the formation of benzoic acid and acetophenone was not detected.

Example 51 (comparative experiment)

In a 25mL pressure reaction tube, 0.0008g (0.001mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 1.3115 g (5.00 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made up to 50 mL using acetone as a solvent. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 9.2%, the selectivity of acetophenone was 5.3%, the selectivity of cumene hydroperoxide was 94.7%, and the formation of benzoic acid and 2-phenyl-2-propanol was not detected.

Example 52 (scale-up experiment)

In a 500 mL pressure-resistant reaction tube, 0.0852 g (0.1 mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron (II) was dispersed in 120.19 g (1 mol) of cumene and stirred. The temperature was raised to 80°C, and oxygen (0.20MPa) was introduced. The reaction was stirred at 80°C and 800rpm for 8.0h. After the reaction was completed, it was cooled to room temperature, 131.15 g (500 mmol) of triphenylphosphine (PPh ₃ ) was added to the reaction mixture, and the generated peroxide was reduced by stirring at room temperature for 40 min. Using acetone as a solvent, the resulting reaction mixture was made up to 5000 mL. 10 mL of the obtained solution was pipetted and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 29.8%, the selectivity of 2-phenyl-2-propanol was 10.1%, the selectivity of acetophenone was 7.2%, the selectivity of cumene hydroperoxide was 82.7%, and no benzoic acid was detected.

Claims (6)

1. a method for iron (II) porphyrin catalyzed oxidation of cumene to synthesize cumene hydrogen peroxide, it is characterised in that the method comprises the following process: Disperse iron (II) porphyrin in cumene, the amount of iron (II) porphyrin is 1×10 ^-4 %～1% of the amount of cumene, mol/mol, and the reaction system is sealed , introduce the oxidant, heat up to 40-100 ℃ under stirring, keep the set temperature and pressure, and stir for 3.0-24.0 h to obtain the cumene solution of cumene hydroperoxide, which is directly used in the subsequent reaction; After post-processing, calculate cumene conversion rate and cumene hydrogen peroxide selectivity; The iron (II) porphyrin is at least one of the compounds shown in formula (I):

Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are each independently: hydrogen, methoxy, ethoxy, methyl, ethyl, phenyl, fluorine, chlorine, bromine, carboxyl, methoxy carbonyl, acetyl, formyl, hydroxyl, amino, methylol, cyano or nitro; The iron (II) porphyrin is 5,10,15,20-tetrakis (2-carboxyphenyl) porphyrin iron (II), 5,10,15,20-tetrakis (3-carboxyphenyl) porphyrin Iron(II), 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin iron(II), 5,10,15,20-tetrakis(2,4-dicarboxyphenyl)porphyrin iron (II), 5,10,15,20-tetrakis(2,4,6-tricarboxyphenyl)porphyrin iron(II), 5,10,15,20-tetrakis(2-chlorophenyl)porphyrin Iron(II), 5,10,15,20-tetrakis(3-chlorophenyl)porphyrin iron(II), 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin iron(II) or 5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin iron(II). 2. as claimed in claim 1, iron (II) porphyrin catalyzed oxidation of cumene synthesizes the method for cumene hydrogen peroxide, it is characterised in that the amount of material between described iron (II) porphyrin and cumene The ratio is 1:100000～1:1000. 3. the method for synthesizing cumene hydroperoxide by iron (II) porphyrin catalytic oxidation of cumene as claimed in claim 1 or 2, is characterized in that, described reaction pressure is 0.10～0.50MPa. 4. the method for synthesizing cumene hydroperoxide by iron (II) porphyrin catalyzed oxidation of cumene as claimed in claim 1 or 2, is characterized in that, described stirring speed is 600～1200rpm. 5. the method for synthesizing cumene hydroperoxide by iron (II) porphyrin catalyzed oxidation of cumene as claimed in claim 1 or 2, it is characterised in that the oxidant is oxygen, air or any ratio mixture thereof. 6. as described in claim 1 or 2, the method for the synthesis of cumene hydrogen peroxide by the catalytic oxidation of cumene catalyzed by iron (II) porphyrin, is characterized in that, the method for described aftertreatment is: after the reaction finishes, to the reaction solution Add triphenylphosphine PPh ₃ to the mixture, and the dosage is 30% to 60% of the amount of cumene, stir at room temperature (20 to 30° C.) for 40 minutes to reduce the generated peroxide, and then analyze and calculate the conversion rate of cumene and cumene hydroperoxide selectivity.