CN111943810A - A method for the synergistic catalytic oxidation of cycloalkanes by confined metalloporphyrin manganese(II)/Cu(II) salts - Google Patents

Abstract

A method for the synergistic catalytic oxidation of cycloalkane with confined metalloporphyrin manganese(II)/Cu(II) salt, wherein the confined metalloporphyrin manganese(II) (1× ^10-4 %～0.1%, mol/ mol) and Cu(II) salt (0.01%～10%, mol/mol) are dispersed in cycloalkane, the reaction system is sealed, the temperature is raised to 90～150 ℃ under stirring, the oxidant is introduced, and the set temperature and pressure are maintained, The reaction is stirred for 2.0-24.0 h, and then the reaction solution is post-treated to obtain the products of cycloalkyl alcohol and cycloalkyl ketone. The method of the invention has the advantages of high selectivity of cycloalkyl alcohols and cycloalkyl ketones, low reaction temperature, less by-products, less environmental impact and the like. In addition, the cycloalkyl hydroperoxide content of the present invention is low, and the safety factor is high. The invention provides an efficient, feasible and safe method for the selective catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkyl ketone.

Description

A Confinement Metalloporphyrin Manganese(II)/Cu(II) Salt Synergistic Catalytic Oxidation of Cycloalkanes Methods

technical field

The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by synergistically catalyzing oxidation of cycloalkane with restricted metalloporphyrin manganese(II)/Cu(II) salt, belonging to the field of industrial catalysis and fine organic synthesis.

Background technique

The catalytic oxidation of cycloalkane is a very important transformation process in the chemical industry. Its oxidation products, cycloalkanols and cycloalkanones, are not only important organic solvents, but also important fine chemical intermediates, which are widely used in pesticides, medicines, dyes, surface Synthesis of fine chemical products such as active agents and resins, especially the production of polyamide fibers nylon-6 and nylon-66. At present, the industrial catalytic oxidation of naphthenes mainly uses homogeneous Co ²⁺ or Mn ²⁺ as catalyst and oxygen (O ₂ ) as oxidant at 150℃～170℃. The main problem is that the reaction temperature is high , the substrate conversion rate is low, the target product selectivity is poor, especially the formation of aliphatic diacids is difficult to inhibit (Applied Catalysis A, General 2019, 575: 120-131; Catalysis Communications 2019, 132: 105809). The main causes of the above problems are: (1) The current industrial O ₂ oxidation of cycloalkanes mainly undergoes a disordered radical diffusion process; (2) The oxidation intermediates, cycloalkyl hydroperoxides, take the free radical thermal decomposition path to the target. The conversion of the oxidation product cycloalkanol and cycloalkanone increases the uncontrollability of the reaction system and reduces the selectivity of cycloalkanol and cycloalkaneone. Therefore, the effective control of free radical diffusion in the process of _catalytic oxidation of cycloalkane by O, and the catalytic conversion of cycloalkane hydroperoxide, the intermediate product of the oxidation, will be beneficial to the improvement of the selectivity of cycloalkane catalytic oxidation, and will be the field of cycloalkane catalytic oxidation in industry. This is a process improvement that is very novel and has great application significance.

As a model compound of cytochrome P-450, metalloporphyrins are widely used in various organic synthesis reactions in the field of biomimetic catalysis, especially oxidation reactions (ChemSusChem 2019, 12(3): 684-691; Polyhedron 2019, 163: 144- 152; Journal of Catalysis 2019, 369:133-142). Metalloporphyrin has an approximately planar molecular structure, which enables the metal center with catalytic activity to be exposed to the maximum extent in the catalytic system to play a role. It can show excellent catalytic activity at 1/1000000~1/100000 of the amount of substrate. It can significantly reduce the cost of the catalytic oxidation of cycloalkane C-H bonds, and is one of the preferred catalysts for the catalytic oxidation of cycloalkane C-H bonds. At the same time, as a catalyst, metalloporphyrin not only has a wide range of selective objects for the central metal, but also the substituents around the metalloporphyrin ring have a very wide control space. Therefore, the selection of metalloporphyrin as a catalyst has the advantages of less catalyst dosage, high catalytic efficiency, easy structure adjustment, good biocompatibility, and environmental protection. By adjusting the volume of the substituents around the metalloporphyrin ring and brominating the pyrrole ring, the stability of the metalloporphyrin is improved, and a certain microscopic confinement environment is also constructed. Using confined metalloporphyrins as catalysts can not only achieve efficient dispersion of catalytic active centers, but also provide a certain microscopic confinement environment for chemical reactions, effectively prevent the disordered diffusion of free radicals, and improve the reaction selectivity (Journal of the American Chemical Society 2017, 139: 18590-18597; Inorganic Chemistry 2019, 58: 5145-5153). In addition, Cu(II) can catalyze the decomposition and conversion of cycloalkane oxidation intermediate product cycloalkyl hydroperoxide, prevent its non-selective thermal decomposition conversion, and improve the selectivity of cycloalkane catalytic oxidation (Catalysis Communications 2019, 132: 105809).

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the prior art, the object of the present invention is to provide a method for the synthesis of cycloalkyl alcohols and cycloalkyl ketones through the synergistic catalytic oxidation of cycloalkanes with limited metalloporphyrin manganese(II)/Cu(II) salts. Confinement metalloporphyrin manganese(II)/Cu( _II ) salt combination as binary catalyst to synergistically catalyze O oxidation of cycloalkanes to selectively synthesize cycloalkyl alcohols and cycloalkyl ketones, not only cycloalkyl alcohols and cycloalkyl groups The ketone selectivity is high, the reaction temperature is low, the by-products are few, the environmental impact is small, etc., and the method provided by the invention has the advantages of low cycloalkyl hydroperoxide content and high safety factor, and is an efficient, feasible and safe cyclic alkyl group. A method for the selective catalytic oxidation of alkanes to synthesize cycloalkyl alcohols and cycloalkyl ketones.

The technical scheme of the present invention is as follows:

A method for synthesizing cycloalkanol and cycloalkanone by synergistic catalytic oxidation of cycloalkane with restricted metalloporphyrin manganese(II)/Cu(II) salt, the method comprises the following processes:

Disperse confined metalloporphyrin manganese(II) and Cu(II) salt in cycloalkane, wherein the amount of confined metalloporphyrin manganese(II) is 1×10 of the amount of cycloalkane. ^-4 % to 0.1%, mol/mol; the amount of Cu(II) salt is 0.01% to 10% of the amount of cycloalkane, mol/mol; the reaction system is sealed and heated to 90 to 150°C with stirring , feed the oxidant, keep the set temperature and pressure, stir and react for 2.0-24.0 h, and then the reaction solution is post-treated to obtain the products cycloalkyl alcohol and cycloalkyl ketone;

The restricted metalloporphyrin manganese (II) includes compounds represented by formula (I), formula (II), formula (III), formula (IV) and formula (V):

The Cu(II) salt is one of Cu(CH ₃ COO) ₂ , Cu(NO ₃ ) ₂ , CuSO ₄ , CuCl ₂ and their hydrates or a mixture of at least two in any proportion, preferably anhydrous Cu (CH ₃ COO) ₂ ;

The cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and cyclododecane, or a mixture of at least two of them in any ratio.

Further, the ratio of the amount of the restricted metalloporphyrin manganese (II) to the amount of the cycloalkane is 1:1,000,000 to 1:1,000, preferably 1:100,000 to 1:10,000.

The ratio of the amount of the Cu(II) salt to the amount of the cycloalkane is 1:10000 to 1:10, preferably 1:1000 to 1:50.

The reaction temperature is 90-150°C, preferably 100-130°C; the reaction pressure is 0.10-2.0 MPa, preferably 0.60-1.20 MPa; the stirring speed is 400-800 rpm, preferably 500-700 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 amount is 3% of the amount of the cycloalkane substance, and stir at room temperature (20-30° C.) for 40 minutes to reduce the generated peroxide. The crude product is distilled, rectified at atmospheric pressure and recrystallized to obtain the oxidized product.

The method for analyzing the reaction result of the present invention is as follows: after the reaction is completed, the reaction solution is reduced by triphenylphosphine to generate the peroxide, and then sampling is performed for analysis. Diluted with acetone as the solvent, and used toluene as the internal standard to conduct gas chromatographic analysis to calculate the conversion of cycloalkane, the selectivity of cycloalkyl alcohol, cycloalkyl ketone and peroxide; use benzoic acid as the internal standard to carry out the liquid Chromatographic analysis to calculate the selectivity of aliphatic diacids.

The invention constructs a binary catalytic system with restricted metalloporphyrin manganese(II)/Cu(II) salt, and synergistically catalyzes _O2 oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkyl ketone, which not only effectively inhibits the free radicals in the oxidation process It also realizes the catalytic conversion of the oxidation intermediate product cycloalkyl hydroperoxide, greatly improves the selectivity of the target product cycloalkyl alcohol and cycloalkyl ketone, reduces the generation of by-products, and reduces the amount of environmental pollutants. Emissions, in line with the current chemical industry's realistic needs for "energy saving and emission reduction". The invention not only provides a method for the efficient and selective oxidation of cycloalkane CH bonds to synthesize cycloalkyl alcohols and cycloalkyl ketones, but also selectively catalyzes the oxidation of CH bonds of other hydrocarbons to efficiently prepare alcohols and ketones. It has certain reference value.

The beneficial effects of the present invention are mainly reflected in: the present invention uses limited metalloporphyrin manganese(II)/Cu(II) salts to synergistically catalyze the oxidation of cycloalkanes to synthesize cycloalkanols and cycloalkanes, which have cycloalkanols and cycloalkanes. It has the advantages of high selectivity of base ketone, low reaction temperature, few by-products, and small environmental impact. In addition, the cycloalkyl hydroperoxide content of the present invention is low, and the safety factor is high. The invention provides an efficient, feasible and safe method for the selective catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkyl ketone.

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.

Restricted porphyrin ligands and restricted metalloporphyrin manganese (II) used in the present invention refer to Journal of Organic Chemistry 1967, 32(2): 476-476; Journal of the American Chemical Society 2017, 139(51): 18590 -18597; Synthesized by Russian Journal of General Chemistry 2016, 86(5):1091-1094. The reagents used were all commercially available analytical grades.

Examples 1 to 32 are examples of catalytic oxidation of naphthenes.

Examples 33 to 46 are comparative experimental cases of the catalytic oxidation of naphthenes.

Example 47 is a scale-up experiment for the catalytic oxidation of naphthenes.

Example 1

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.23%, the selectivity of cyclohexanol is 41.35%, the selectivity of cyclohexanone is 54.34%, the selectivity of cyclohexyl hydrogen peroxide is 2.32%, the selectivity of adipic acid is 1.69%, and the selectivity of glutaric acid is 0.30%.

Example 2

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(1-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.05%, the selectivity of cyclohexanol is 40.48%, the selectivity of cyclohexanone is 52.01%, the selectivity of cyclohexyl hydrogen peroxide is 5.30%, the selectivity of adipic acid is 1.96%, and the selectivity of glutaric acid is 0.25%.

Example 3

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0031 g (0.0024 mmol) of 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18 - Manganese octabromoporphyrin (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, seal the reaction kettle, stir and heat up to 120°C, feed oxygen to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.34%, the selectivity of cyclohexanol is 39.11%, the selectivity of cyclohexanone is 53.04%, the selectivity of cyclohexyl hydrogen peroxide is 4.53%, the selectivity of adipic acid is 2.92%, and the selectivity of glutaric acid is 0.40%.

Example 4

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0041 g (0.0024 mmol) of 5,10,15,20-tetrakis(9-phenanthryl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.92%, the selectivity of cyclohexanol is 44.37%, the selectivity of cyclohexanone is 48.02%, the selectivity of cyclohexyl hydrogen peroxide is 3.67%, the selectivity of adipic acid is 3.59%, and the selectivity of glutaric acid is 0.35%.

Example 5

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0043 g (0.0024 mmol) of 5,10,15,20-tetrakis(1-pyrenyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.59%, the selectivity of cyclohexanol is 46.46%, the selectivity of cyclohexanone is 46.08%, the selectivity of cyclohexyl hydrogen peroxide is 4.17%, the selectivity of adipic acid is 2.97%, and the selectivity of glutaric acid is 0.32%.

Example 6

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.4126g (2.200mmol) copper nitrate are dispersed in 16.8320g (200mmol) cyclohexane, seal the reactor, stir and be warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.23%, the selectivity of cyclohexanol is 39.93%, the selectivity of cyclohexanone is 52.29%, the selectivity of cyclohexyl hydrogen peroxide is 5.34%, the selectivity of adipic acid is 2.00%, and the selectivity of glutaric acid is 0.44%.

Example 7

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.2958g (2.200mmol) cupric chloride are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stir and be warming up to 120 ℃, feed oxygen to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.87%, the selectivity of cyclohexanol is 38.45%, the selectivity of cyclohexanone is 50.99%, the selectivity of cyclohexyl hydrogen peroxide is 7.75%, the selectivity of adipic acid is 2.22%, and the selectivity of glutaric acid is 0.59%.

Example 8

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3511g (2.200mmol) copper sulfate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.46%, the selectivity of cyclohexanol is 40.02%, the selectivity of cyclohexanone is 48.98%, the selectivity of cyclohexyl hydroperoxide is 8.32%, the selectivity of adipic acid is 2.23%, and the selectivity of glutaric acid is 0.45%.

Example 9

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 14.0280g (200mmol) cyclopentane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclopentane is 4.71%, the selectivity of cyclopentanol is 9.57%, the selectivity of cyclopentanone is 47.82%, the selectivity of cyclopentyl hydroperoxide is 13.70%, the selectivity of glutaric acid is 27.53%, and the selectivity of succinic acid is 1.38% .

Example 10

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 19.6380g (200mmol) cycloheptane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cycloheptane is 23.14%, the selectivity of cycloheptanol is 11.54%, the selectivity of cycloheptanone is 66.62%, the selectivity of cycloheptyl hydroperoxide is 19.27%, the selectivity of pimelic acid is 2.12%, and the selectivity of adipic acid is 0.45% .

Example 11

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 22.4440g (200mmol) cyclooctane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclooctane was 28.38%, the selectivity of cyclooctanol was 33.05%, the selectivity of cyclooctanone was 51.62%, the selectivity of cyclooctyl hydroperoxide was 13.61%, the selectivity of suberic acid was 1.72%, and no pimelic acid was detected. generate.

Example 12

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 33.6640g (200mmol) cyclododecane, seal the reactor, stir and be warming up to 120 ℃, feed oxygen to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclododecane was 33.47%, the selectivity of cyclododecanol was 19.59%, the selectivity of cyclododecanone was 51.37%, the selectivity of cyclododecyl hydroperoxide was 29.04%, and no dodecanoic acid and undecanoic acid were detected. generate.

Example 13

In a 100 mL stainless steel autoclave with a Teflon liner, add 0.0003 g (0.0002 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 2.11%, the selectivity of cyclohexanol was 28.68%, the selectivity of cyclohexanone was 20.84%, the selectivity of cyclohexyl hydroperoxide was 50.48%, and no adipic acid and glutaric acid were detected.

Example 14

In a 100 mL stainless steel autoclave with a Teflon liner, add 0.0030 g (0.0020 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.02%, the selectivity of cyclohexanol is 41.56%, the selectivity of cyclohexanone is 52.54%, the selectivity of cyclohexyl hydrogen peroxide is 3.10%, the selectivity of adipic acid is 2.38%, and the selectivity of glutaric acid is 0.42%.

Example 15

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0300 g (0.0200 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.24%, the selectivity of cyclohexanol is 41.43%, the selectivity of cyclohexanone is 51.84%, the selectivity of cyclohexyl hydrogen peroxide is 3.87%, the selectivity of adipic acid is 2.43%, and the selectivity of glutaric acid is 0.43%.

Example 16

In a 100 mL stainless steel autoclave with a Teflon liner, 0.2998 g (0.2000 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.42%, the selectivity of cyclohexanol is 39.27%, the selectivity of cyclohexanone is 50.44%, the selectivity of cyclohexyl hydrogen peroxide is 6.79%, the selectivity of adipic acid is 2.77%, and the selectivity of glutaric acid is 0.73%.

Example 17

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.0036g (0.020mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, seal the reactor, stir and be warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.65%, the selectivity of cyclohexanol is 33.37%, the selectivity of cyclohexanone is 38.15%, the selectivity of cyclohexyl hydroperoxide is 19.04%, the selectivity of adipic acid is 8.62%, and the selectivity of glutaric acid is 0.82%.

Example 18

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.0363g (0.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.85%, the selectivity of cyclohexanol is 36.79%, the selectivity of cyclohexanone is 41.50%, the selectivity of cyclohexyl hydroperoxide is 16.49%, the selectivity of adipic acid is 4.66%, and the selectivity of glutaric acid is 0.56%.

Example 19

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.7265g (4.000mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.89%, the selectivity of cyclohexanol is 39.96%, the selectivity of cyclohexanone is 44.91%, the selectivity of cyclohexyl hydrogen peroxide is 10.85%, the selectivity of adipic acid is 3.84%, and the selectivity of glutaric acid is 0.44%.

Example 20

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 3.6326g (20.000mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.53%, the selectivity of cyclohexanol is 33.22%, the selectivity of cyclohexanone is 37.37%, the selectivity of cyclohexyl hydrogen peroxide is 19.90%, the selectivity of adipic acid is 8.08%, and the selectivity of glutaric acid is 1.43%.

Example 21

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 90 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 90° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 0.25%, the formation of cyclohexanol was not detected, the selectivity of cyclohexanone was 19.83%, the selectivity of cyclohexyl hydroperoxide was 80.17%, and the formation of adipic acid and glutaric acid was not detected.

Example 22

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stir and be warming up to 100 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 100° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 0.34%, the formation of cyclohexanol was not detected, the selectivity of cyclohexanone was 26.48%, the selectivity of cyclohexyl hydroperoxide was 73.52%, and the formation of adipic acid and glutaric acid was not detected.

Example 23

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 130 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 130° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 8.91%, the selectivity of cyclohexanol is 37.92%, the selectivity of cyclohexanone is 49.47%, the selectivity of cyclohexyl hydrogen peroxide is 8.08%, the selectivity of adipic acid is 3.93%, and the selectivity of glutaric acid is 0.60%.

Example 24

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 150 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 150° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 11.96%, the selectivity of cyclohexanol is 31.27%, the selectivity of cyclohexanone is 41.31%, the selectivity of cyclohexyl hydroperoxide is 19.10%, the selectivity of adipic acid is 6.34%, and the selectivity of glutaric acid is 1.98%.

Example 25

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stir and be warming up to 120 ℃, feed oxygen to 0.10MPa . The reaction was stirred at 120° C., 0.1 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.51%, the selectivity of cyclohexanol is 31.92%, the selectivity of cyclohexanone is 42.15%, the selectivity of cyclohexyl hydrogen peroxide is 17.19%, the selectivity of adipic acid is 7.38%, and the selectivity of glutaric acid is 1.36%.

Example 26

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 0.60MPa . The reaction was stirred at 120° C., 0.6MPa oxygen pressure, and 600rpm for 8.0h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.95%, the selectivity of cyclohexanol is 40.75%, the selectivity of cyclohexanone is 52.04%, the selectivity of cyclohexyl hydrogen peroxide is 4.09%, the selectivity of adipic acid is 2.27%, and the selectivity of glutaric acid is 0.85%.

Example 27

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.20MPa . The reaction was stirred at 120° C., 1.2MPa oxygen pressure, and 600rpm for 8.0h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.07%, the selectivity of cyclohexanol is 40.42%, the selectivity of cyclohexanone is 50.95%, the selectivity of cyclohexyl hydrogen peroxide is 5.12%, the selectivity of adipic acid is 2.45%, and the selectivity of glutaric acid is 1.06%.

Example 28

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 2.00MPa . The reaction was stirred at 120° C., 2.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.11%, the selectivity of cyclohexanol is 42.67%, the selectivity of cyclohexanone is 50.43%, the selectivity of cyclohexyl hydrogen peroxide is 2.09%, the selectivity of adipic acid is 4.25%, and the selectivity of glutaric acid is 0.56%.

Example 29

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 400 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.48%, the selectivity of cyclohexanol is 39.31%, the selectivity of cyclohexanone is 52.39%, the selectivity of cyclohexyl hydrogen peroxide is 6.09%, the selectivity of adipic acid is 1.77%, and the selectivity of glutaric acid is 0.44%.

Example 30

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 500 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.65%, the selectivity of cyclohexanol is 40.26%, the selectivity of cyclohexanone is 53.01%, the selectivity of cyclohexyl hydrogen peroxide is 4.54%, the selectivity of adipic acid is 1.71%, and the selectivity of glutaric acid is 0.48%.

Example 31

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 700 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.26%, the selectivity of cyclohexanol is 40.96%, the selectivity of cyclohexanone is 53.89%, the selectivity of cyclohexyl hydrogen peroxide is 2.45%, the selectivity of adipic acid is 2.37%, and the selectivity of glutaric acid is 0.33%.

Example 32

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 0.3996g (2.200mmol) copper acetate are dispersed in 16.8320g (200mmol) cyclohexane, sealed reactor, stirring is warming up to 120 ℃, feed oxygen to 1.00MPa . The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 800 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 7.30%, the selectivity of cyclohexanol is 41.36%, the selectivity of cyclohexanone is 54.05%, the selectivity of cyclohexyl hydrogen peroxide is 2.47%, the selectivity of adipic acid is 1.78%, and the selectivity of glutaric acid is 0.34% .

Example 33 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.0021 g (0.0024 mmol) 5,10,15,20-tetrakis(2-naphthyl)porphyrin manganese was dispersed in 16.8320 g (200 mmol) cyclohexyl In alkane, the reaction kettle was sealed, and the temperature was raised to 120 ° C with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.39%, the selectivity of cyclohexanol is 37.54%, the selectivity of cyclohexanone is 42.35%, the selectivity of cyclohexyl hydrogen peroxide is 10.22%, the selectivity of adipic acid is 6.84%, and the selectivity of glutaric acid is 3.05%.

Example 34 (comparative experiment)

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0021 g (0.0024 mmol) 5,10,15,20-tetrakis(1-naphthyl)porphyrin manganese was dispersed in 16.8320 g (200 mmol) cyclohexyl In alkane, the reaction kettle was sealed, and the temperature was raised to 120 ° C with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.20%, the selectivity of cyclohexanol is 34.79%, the selectivity of cyclohexanone is 44.70%, the selectivity of cyclohexyl hydrogen peroxide is 11.16%, the selectivity of adipic acid is 7.84%, and the selectivity of glutaric acid is 1.51%.

Example 35 (comparative experiment)

In a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.0016g (0.0024mmol) 5,10,15,20-tetraphenylporphyrin manganese was dispersed in 16.8320g (200mmol) cyclohexane, sealed The reaction kettle was heated to 120°C with stirring, and oxygen was introduced to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.05%, the selectivity of cyclohexanol is 34.66%, the selectivity of cyclohexanone is 45.80%, the selectivity of cyclohexyl hydrogen peroxide is 8.49%, the selectivity of adipic acid is 9.73%, and the selectivity of glutaric acid is 1.32%.

Example 36 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.0026 g (0.0024 mmol) of 5,10,15,20-tetrakis(9-phenanthrenyl) porphyrin manganese was dispersed in 16.8320 g (200 mmol) of cyclohexyl In alkane, the reaction kettle was sealed, and the temperature was raised to 120 ° C with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.16%, the selectivity of cyclohexanol is 36.13%, the selectivity of cyclohexanone is 45.38%, the selectivity of cyclohexyl hydrogen peroxide is 7.24%, the selectivity of adipic acid is 9.98%, and the selectivity of glutaric acid is 1.27%.

Example 37 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.0028 g (0.0024 mmol) of 5,10,15,20-tetrakis(1-pyreneyl)porphyrin manganese was dispersed in 16.8320 g (200 mmol) of cyclohexyl In alkane, the reaction kettle was sealed, and the temperature was raised to 120 ° C with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.28%, the selectivity of cyclohexanol is 37.13%, the selectivity of cyclohexanone is 41.79%, the selectivity of cyclohexyl hydrogen peroxide is 11.18%, the selectivity of adipic acid is 8.72%, and the selectivity of glutaric acid is 1.18%.

Example 38 (comparative experiment)

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(1-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) was dispersed in 16.8320g (200mmol) cyclohexane, sealed the reaction kettle, stirred and heated to 120°C, and fed oxygen to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.93%, the selectivity of cyclohexanol is 36.12%, the selectivity of cyclohexanone is 39.03%, the selectivity of cyclohexyl hydrogen peroxide is 13.40%, the selectivity of adipic acid is 9.31%, and the selectivity of glutaric acid is 2.14%.

Example 39 (comparative experiment)

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0036 g (0.0024 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) was dispersed in 16.8320g (200mmol) cyclohexane, sealed the reaction kettle, stirred and heated to 120°C, and fed oxygen to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.13%, the selectivity of cyclohexanol is 40.85%, the selectivity of cyclohexanone is 35.63%, the selectivity of cyclohexyl hydrogen peroxide is 12.25%, the selectivity of adipic acid is 9.17%, and the selectivity of glutaric acid is 2.10%.

Example 40 (comparative experiment)

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0031 g (0.0024 mmol) of 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18 - Manganese octabromoporphyrin (II) was dispersed in 16.8320 g (200 mmol) of cyclohexane, the reaction kettle was sealed, the temperature was raised to 120° C. with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 6.02%, the selectivity of cyclohexanol is 34.23%, the selectivity of cyclohexanone is 44.06%, the selectivity of cyclohexyl hydrogen peroxide is 10.26%, the selectivity of adipic acid is 9.10%, and the selectivity of glutaric acid is 2.35%.

Example 41 (comparative experiment)

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0041 g (0.0024 mmol) of 5,10,15,20-tetrakis(9-phenanthryl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) was dispersed in 16.8320g (200mmol) cyclohexane, sealed the reaction kettle, stirred and heated to 120°C, and fed oxygen to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.75%, the selectivity of cyclohexanol is 40.35%, the selectivity of cyclohexanone is 34.43%, the selectivity of cyclohexyl hydrogen peroxide is 12.99%, the selectivity of adipic acid is 9.85%, and the selectivity of glutaric acid is 2.38%.

Example 42 (comparative experiment)

In a 100 mL stainless steel autoclave with a Teflon liner, 0.0043 g (0.0024 mmol) of 5,10,15,20-tetrakis(1-pyrenyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) was dispersed in 16.8320g (200mmol) cyclohexane, sealed the reaction kettle, stirred and heated to 120°C, and fed oxygen to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 5.87%, the selectivity of cyclohexanol is 42.66%, the selectivity of cyclohexanone is 33.50%, the selectivity of cyclohexyl hydrogen peroxide is 12.86%, the selectivity of adipic acid is 9.03%, and the selectivity of glutaric acid is 1.95%.

Example 43 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.3996 g (2.200 mmol) of copper acetate was dispersed in 16.8320 g (200 mmol) of cyclohexane, the reaction kettle was sealed, and the temperature was raised to 120 ° C with stirring, and oxygen was introduced. to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 4.23%, the selectivity of cyclohexanol was 31.42%, the selectivity of cyclohexanone was 23.06%, the selectivity of cyclohexyl hydroperoxide was 45.52%, and no adipic acid and glutaric acid were detected.

Embodiment 44 (comparative experiment)

In a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.4126g (2.200mmol) of copper nitrate was dispersed in 16.8320g (200mmol) of cyclohexane, the reactor was sealed, stirred and heated to 120°C, and oxygen was introduced to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 4.09%, the selectivity of cyclohexanol was 25.67%, the selectivity of cyclohexanone was 20.11%, the selectivity of cyclohexyl hydroperoxide was 54.22%, and no adipic acid and glutaric acid were detected.

Example 45 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.2958 g (2.200 mmol) of cupric chloride was dispersed in 16.8320 g (200 mmol) of cyclohexane, the reactor was sealed, and the temperature was raised to 120° C. Oxygen to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 3.42%, the selectivity of cyclohexanol was 24.21%, the selectivity of cyclohexanone was 18.43%, the selectivity of cyclohexyl hydroperoxide was 57.36%, and no adipic acid and glutaric acid were detected.

Embodiment 46 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.3511 g (2.200 mmol) of copper sulfate was dispersed in 16.8320 g (200 mmol) of cyclohexane, the reactor was sealed, and the temperature was raised to 120 ° C with stirring, and oxygen was introduced. to 1.00MPa. The reaction was stirred at 120° C., 1.0 MPa oxygen pressure, and 600 rpm for 8.0 h. After the reaction was completed, ice water 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 30 min. The resulting reaction mixture was made up to 100 mL using acetone as a solvent. Pipette 10 mL of the obtained solution, and use toluene as the internal standard for gas chromatography analysis; pipette 10 mL of the obtained solution, use benzoic acid as the internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 3.18%, the selectivity of cyclohexanol was 22.64%, the selectivity of cyclohexanone was 18.71%, the selectivity of cyclohexyl hydroperoxide was 58.65%, and no adipic acid and glutaric acid were detected.

Example 47 (scale-up experiment)

In a 1 L stainless steel autoclave with a Teflon liner, 0.0359 g (0.0240 mmol) of 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin manganese (II) and 3.9959g (22.000mmol) copper acetate are dispersed in 168.32g (2mol) cyclohexane, seal the reaction kettle, stir and be warming up to 120 ℃, feed oxygen to 1.00Mpa . The reaction was stirred at 600 rpm for 8.0 h at 120 °C. After the reaction was completed, ice water was cooled to room temperature, 131.15 g (500.00 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. Distillation to recover 156.23g of cyclohexane with a conversion rate of 8.29%; rectification under reduced pressure to obtain 4.98g of cyclohexanol with a selectivity of 41.19% to obtain 6.54g of cyclohexanone with a selectivity of 54.09%, recrystallization to obtain adipic acid 0.18 g, selectivity 1.49%, glutaric acid 0.035 g, selectivity 0.29%.

Claims (8)

1. a method for confined metalloporphyrin manganese (II)/Cu (II) salt synergistic catalytic oxidation of naphthenic hydrocarbon, is characterized in that, described method comprises following process: Disperse confined metalloporphyrin manganese (II) and Cu(II) salt in cycloalkane, wherein the amount of confined metalloporphyrin manganese (II) is 1×10 of the amount of cycloalkane. ^-4 % to 0.1%, mol/mol; the amount of Cu(II) salt is 0.01% to 10% of the amount of cycloalkane, mol/mol; the reaction system is sealed and heated to 90 to 150°C with stirring , feed the oxidant, keep the set temperature and pressure, stir and react for 2.0-24.0 h, and then the reaction solution is post-treated to obtain the products cycloalkyl alcohol and cycloalkyl ketone; The restricted metalloporphyrin manganese (II) includes compounds represented by formula (I), formula (II), formula (III), formula (IV) and formula (V):

The Cu(II) salt is one of Cu(CH ₃ COO) ₂ , Cu(NO ₃ ) ₂ , CuSO ₄ , CuCl ₂ and their hydrates or a mixture of at least two of them in any ratio; The cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and cyclododecane, or a mixture of at least two of them in any ratio. 2. the method for confinement metalloporphyrin manganese (II)/Cu (II) salt synergistic catalysis oxidation cycloalkane as claimed in claim 1, it is characterized in that, described catalyzer is confined metalloporphyrin manganese (II) and a binary combination of Cu(II) salts. 3. the method for confinement metalloporphyrin manganese (II)/Cu (II) salt synergistic catalysis oxidation cycloalkane as described in claim 1 or 2, it is characterized in that, described confinement metalloporphyrin manganese (II) The ratio of the amount of the substance to the amount of the cycloalkane is 1:1000000～1:1000. 4. the method for limited metalloporphyrin manganese (II)/Cu (II) salt synergistic catalytic oxidation of naphthene as described in claim 1 or 2, it is characterized in that, the amount of substance of described Cu (II) salt and The ratio of the amount of naphthenic hydrocarbons is 1:10000 to 1:10. 5 . The method for the synergistic catalytic oxidation of cycloalkane with restricted metalloporphyrin manganese(II)/Cu(II) salt according to claim 1 or 2, wherein the reaction pressure is 0.10-2.0 MPa. 6 . The method for the synergistic catalytic oxidation of cycloparaffin with restricted metalloporphyrin manganese(II)/Cu(II) salt according to claim 1 or 2, wherein the stirring speed is 400-800 rpm. 7. the method for confined metalloporphyrin manganese (II)/Cu (II) salt synergistic catalytic oxidation of naphthene as described in claim 1 or 2, it is characterised in that the oxidant is oxygen, air or any ratio mixture thereof . 8. the method for restricted metalloporphyrin manganese (II)/Cu (II) salt synergistic catalysis oxidation naphthene as described in claim 1 or 2, it is characterised in that the method for described aftertreatment is: after the reaction finishes, Triphenylphosphine PPh ₃ was added to the reaction solution in an amount of 3% of the amount of naphthenic hydrocarbons, and the resulting peroxide was reduced by stirring at room temperature (20-30° C.) for 40 min. The crude product was distilled, subjected to atmospheric rectification and Recrystallization to obtain oxidation products.