CN112076788A

CN112076788A - Method for oxidizing cycloalkane under concerted catalysis of metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt

Info

Publication number: CN112076788A
Application number: CN202010855198.7A
Authority: CN
Inventors: 沈海民; 郭阿兵; 佘远斌
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2020-08-24
Filing date: 2020-08-24
Publication date: 2020-12-15

Abstract

A method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt comprises the steps of dispersing 1% -10% of PCN-222(Co) and 0.01% -10% of Cu (II) salt (mol/mol) in cycloalkane, sealing a reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant (0.10-2.0 MPa), keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 hours, and carrying out aftertreatment on reaction liquid to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone. The method has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.

Description

Method for oxidizing cycloalkane under concerted catalysis of metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt

Technical Field

The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by synergistically catalyzing and oxidizing cycloalkane with metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt, belonging to the field of industrial catalysis and fine organic synthesis.

Background

Catalytic oxidation of cycloalkane is an important conversion process in chemical industry, and oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important fine chemical intermediates, and are widely applied to synthesis of fine chemical products such as pesticides, medicines, dyes, surfactants, resins and the like, especially production of polyamide fiber nylon-6 and nylon-66. At present, the catalytic oxidation of cycloalkanes is industrially carried out mainly by homogeneous Co²⁺Or Mn²⁺As catalyst, oxygen (O)₂) As an oxidizing agent, at 150 ℃ to 170 ℃, there are major problems of high reaction temperature, low substrate conversion, poor selectivity of the target product, and in particular, difficulty in inhibiting the formation of aliphatic diacids (Applied Catalysis a, General 2019,575: 120-; catalysis Communications 2019,132: 105809). The main sources of the above problems are: (1) at present, O is industrially used₂Oxidized cycloalkanes undergo mainly a disordered radical diffusion history; (2) the intermediate product of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone. Thus, O is effectively controlled₂The free radical diffusion in the process of catalytically oxidizing the cycloalkane and the catalytic conversion of the intermediate product of the oxidation, namely the cycloalkyl hydrogen peroxide, are beneficial to the improvement of the catalytic oxidation selectivity of the cycloalkane, and are novel process improvements in the field of industrial cycloalkane catalytic oxidation and have great application significance.

The metal-organic framework material PCN-222 is a series of porous materials with better chemical stability and thermal stability, is applied to the field of organic catalysis, can realize the high-efficiency dispersion of catalytic active centers, can provide a certain micro-domain environment for chemical reaction, effectively limits the disordered diffusion of free radicals, and improves the reaction selectivity (Angewandte Chemistry International Edition 2012,51, 10307-. In addition, Cu (II) can catalyze the decomposition and conversion of naphthenic base hydrogen peroxide which is an intermediate product of naphthenic hydrocarbon oxidation, limit the non-selective thermal decomposition and conversion of the naphthenic hydrocarbon, and improve the selectivity of catalytic oxidation of the naphthenic hydrocarbon (Catalysis Communications 2019,132: 105809).

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing cycloalkyl alcohol and cycloalkyl ketone by synergistically catalyzing and oxidizing cycloalkane with metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt₂The method for selectively synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the naphthenic hydrocarbon has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, less by-products, small environmental influence and the like, and the method provided by the invention has low content of naphthenic hydroperoxide and high safety coefficient, and is an efficient, feasible and safe method for selectively catalytically oxidizing the naphthenic hydrocarbon to synthesize the naphthenic alcohol and the naphthenic ketone.

The technical scheme of the invention is as follows:

a method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt, said method comprising the following steps:

dispersing metalloporphyrin MOFs PCN-222(Co) and Cu (II) salt into cycloalkane, wherein the mass of the metalloporphyrin MOFs PCN-222(Co) is 1% -10% of the content of the cycloalkane material, and g/mol; the amount of Cu (II) salt is 0.01-10% of that of naphthenic hydrocarbon, mol/mol of the salt is sealed in a reaction system, the temperature is raised to 90-150 ℃ under stirring, an oxidant (0.10-2.0 MPa) is introduced, the set temperature and pressure are kept, the stirring reaction is carried out for 2.0-24.0 h, and then the reaction solution is subjected to post-treatment to obtain the product of naphthenic alcohol and naphthenic ketone;

the metalloporphyrin MOFs PCN-222(Co) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):

the Cu (II) salt is Cu (CH)₃COO)₂，Cu(NO₂)₂，CuSO₄，CuCl₂And hydrates thereof, or a mixture of at least two of the hydrates in any proportion;

the cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.

Further, the ratio of the mass of the metalloporphyrin MOFs PCN-222(Co) to the mass of the naphthenic hydrocarbon substances is 1: 100-1: 10, preferably 1: 25-2: 25.

The mass ratio of the Cu (II) salt to the cycloalkane is 1: 10000-1: 10, preferably 1: 1000-1: 100.

The reaction temperature is 90-150 ℃, and preferably 100-130 ℃; the reaction pressure is 0.10-2.0 MPa, preferably 0.60-1.20 MPa; the stirring speed is 600-1200 rpm, preferably 800-1000 rpm.

The oxidant is oxygen, air or a mixture of oxygen and air in any proportion;

the post-treatment method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution₃And the using amount of the peroxide is 3 percent of the amount of the cyclane, the peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.

The method for analyzing the reaction result comprises the following steps: after the reaction is finished, peroxide generated by the reduction of the reaction liquid by triphenylphosphine is sampled and analyzed. Diluting with acetone as solvent, performing gas chromatography with toluene as internal standard, and calculating conversion rate of cycloalkane and selectivity of cycloalkyl alcohol, cycloalkyl ketone and peroxide; performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid;

in the invention, the metalloporphyrin unit contained in the metalloporphyrin MOFs PCN-222(Co) is at least one of compounds shown in a formula (I), a formula (II) and a formula (III):

the invention constructs a binary catalytic system by using metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt to synergistically catalyze O₂The oxidation of the cycloalkane to synthesize the cycloalkyl alcohol and the cycloalkyl ketone not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the catalytic conversion of the oxidation intermediate product, namely the cycloalkyl hydrogen peroxide, greatly improves the selectivity of the target product, namely the cycloalkyl alcohol and the cycloalkyl ketone, reduces the generation of byproducts, reduces the emission of environmental pollutants, and meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a method for synthesizing naphthenic alcohol and naphthenic ketone by high-efficiency and selective oxidation of naphthenic C-H bonds, but also has certain reference value for preparing alcohols and ketone compounds by selective catalytic oxidation of other hydrocarbon C-H bonds.

The invention has the following beneficial effects: the method for synthesizing the naphthenic alcohol and the naphthenic ketone by the concerted catalytic oxidation of the cycloparaffin by the metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, less byproducts, small environmental influence and the like. In addition, the content of the naphthenic base hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing cycloalkyl alcohol and cycloalkyl ketone by selective catalytic oxidation of cycloalkane.

Detailed Description

The invention will be further illustrated with reference to specific examples, without however being limited thereto.

The metalloporphyrins MOFs PCN-222(Co) used in the invention refer to Angewandte Chemie International Edition 2012,51, 10307-10310; inorganic Chemistry 2018,57,6, 3339-3347; inorganic Chemistry 2019,58: 5145-. All reagents used were commercially available analytical grade.

Examples 1 to 3 are syntheses of the metalloporphyrins MOFs PCN-222 (Co).

Examples 4 to 46 are examples of catalytic oxidation of cycloalkanes.

Examples 47 to 50 are comparative experimental cases.

Examples 51 to 53 are scale-up experimental cases.

Example 1

Synthesis of PCN-222(Co) -m: t (3-COOH) PPCo (II) (0.0847g, 0.1mmol), ZrCl were placed in a 35mL pressure-resistant reaction tube₄(0.1400g,0.6mmol), benzoic acid (5.4000g,44.3mmol) was dissolved in 16.0mL DMF and sonicated for 30min until all dissolved. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, rinsed with DMF and acetone sequentially and transferred to a 10.0mL centrifuge tube, a low-speed centrifuge is used for centrifuging for 5min (3000rpm), the upper layer liquid is poured out, dry DMF is statically extracted (3 × 8.0mL) until the upper layer liquid is clear, dry acetone is extracted (3 × 8.0mL) until the upper layer liquid is clear, the lower layer solid is taken off, and the drying is carried out for 8.0h at 90 ℃ to obtain brick red powder (0.0680g, 44.7% yield).

Example 2

Synthesis of PCN-222(Co) -p: t (4-COOH) PPCo (II) (0.0847g, 0.1mmol), ZrCl were placed in a 35mL pressure-resistant reaction tube₄(0.1400g,0.6mmol), benzoic acid (5.4000g,44.3mmol) was dissolved in 16.0mL DMF and sonicated for 30min until all dissolved. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, rinsed with DMF and acetone sequentially and then transferred to a 10.0mL centrifuge tube, a low-speed centrifuge is used for centrifuging for 5min (3000rpm), the upper layer liquid is poured out, and DMF is dried and is statically extracted (3 × 8.0mL) to the upper layerThe supernatant was clarified, dry acetone leached (3X 8.0mL) to a clear supernatant, the solid from the lower layer was dried at 90 ℃ for 8.0h to give a brick-red powder (0.0690g, 45.3% yield).

Example 3

Synthesis of PCN-222(Co) -d: in a 35mL pressure-resistant reaction tube, [ T (4- (4-COOH) P) PPCo (II) ]] (0.1152g,0.1mmol)，ZrCl₄(0.1400g,0.6mmol), benzoic acid (5.4000g,44.3mmol) was dissolved in 16.0mL DMF and sonicated for 30min until all dissolved. The mixture is put into an electric heating constant temperature air blast drying oven to be stood still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, rinsed with DMF and acetone sequentially and transferred to a 10.0mL centrifuge tube, a low-speed centrifuge is used for centrifuging for 5min (3000rpm), the upper layer liquid is poured out, dry DMF is statically extracted (3 × 8.0mL) until the upper layer liquid is clear, dry acetone is extracted (3 × 8.0mL) until the upper layer liquid is clear, the lower layer solid is taken off, and the dry DMF is dried for 8.0h at 90 ℃ to obtain brick red powder (0.0660g, 43.4% yield).

Example 4

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (2 mg,0.01mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.96%, cyclohexanol selectivity 50.4%, cyclohexanone selectivity 36.1%, cyclohexyl hydroperoxide selectivity 9.8%, adipic acid selectivity 3.7%, and no formation of glutaric acid was detected.

Example 5

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (8 mg,0.04mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 5.24%, the cyclohexanol selectivity was 49.2%, the cyclohexanone selectivity was 37.7%, the cyclohexyl hydroperoxide selectivity was 10.1%, the adipic acid selectivity was 3.0%, and the formation of glutaric acid was not detected.

Example 6

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.79%, the cyclohexanol selectivity is 48.5%, the cyclohexanone selectivity is 37.8%, the cyclohexyl hydroperoxide selectivity is 5.5%, the adipic acid selectivity is 7.2%, and the glutaric acid selectivity is 1%.

Example 7

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (16mg,0.08mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. At 120 deg.CStirring and reacting at 800rpm for 8.0h under the oxygen pressure of 1.0 MPa. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.71%, cyclohexanol selectivity 46.7%, cyclohexanone selectivity 36.4%, cyclohexyl hydroperoxide selectivity 10.5%, adipic acid selectivity 6.4%, and no formation of glutaric acid was detected.

Example 8

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (20mg,0.10mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 5.68%, the cyclohexanol selectivity was 50.7%, the cyclohexanone selectivity was 36.2%, the cyclohexyl hydroperoxide selectivity was 8.5%, the adipic acid selectivity was 4.6%, and the formation of glutaric acid was not detected.

Example 9

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(3.6mg,0.018mg/mmol) was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ while stirring, and oxygen was introduced thereinto to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.65%, cyclohexanol selectivity 51.4%, cyclohexanone selectivity 33.6%, cyclohexyl hydroperoxide selectivity 8.4%, adipic acid selectivity 6.6%, and no formation of glutaric acid was detected.

Example 10

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(50mg,0.250mg/mmol) was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.86%, cyclohexanol selectivity 48.2%, cyclohexanone selectivity 37.4%, cyclohexyl hydroperoxide selectivity 7.7%, adipic acid selectivity 6.7%, and no formation of glutaric acid was detected.

Example 11

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(100mg,0.500mg/mmol) was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Remove 10mLCarrying out gas phase chromatographic analysis on the obtained solution by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.51%, cyclohexanol selectivity 49.6%, cyclohexanone selectivity 38.3%, cyclohexyl hydroperoxide selectivity 5.8%, adipic acid selectivity 6.3%, and no formation of glutaric acid was detected.

Example 12

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(200mg,1.000mg/mmol) was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.85 percent, the cyclohexanol selectivity is 48.8 percent, the cyclohexanone selectivity is 37.8 percent, the cyclohexyl hydroperoxide selectivity is 6.8 percent, the adipic acid selectivity is 6.6 percent, and the glutaric acid is not generated.

Example 13

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(300mg,1.500mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Conversion of cyclohexane6.23 percent, 49.6 percent of cyclohexanol selectivity, 36.3 percent of cyclohexanone selectivity, 7.8 percent of cyclohexyl hydroperoxide selectivity and 6.3 percent of adipic acid selectivity, and the generation of glutaric acid is not detected.

Example 14

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(600mg,2.000mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is removed, toluene is taken as an internal standard, and gas chromatography analysis is carried out; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.43%, cyclohexanol selectivity 49.9%, cyclohexanone selectivity 37.1%, cyclohexyl hydroperoxide selectivity 6.8%, adipic acid selectivity 6.2%, glutaric acid selectivity.

Example 15

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(800mg,4.000mg/mmol) was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.21%, cyclohexanol selectivity 48.2%, cyclohexanone selectivity 39.1%, cyclohexyl hydroperoxide selectivity 6.3%, adipic acid selectivity 6.4%, no glutaric acid formation detectedAnd (4) obtaining.

Example 16

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(3669mg,18.345mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion was 6.12%, cyclohexanol selectivity was 47.6%, cyclohexanone selectivity was 40.4%, cyclohexyl hydroperoxide selectivity was 5.4%, adipic acid selectivity was 6.6%, and glutaric acid formation was not detected.

Example 17

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 90 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 90 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.52%, cyclohexanol selectivity 25.6%, cyclohexanone selectivity 26.2%, cyclohexyl hydroperoxide selectivity 48.2%, no diacid formation was detected.

Example 18

In a 100mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -m (14mg, 0).07mg/mmol),Cu(OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 100 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh3) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 30min to reduce the formed peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.58%, cyclohexanol selectivity 47.2%, cyclohexanone selectivity 34.5%, cyclohexyl hydroperoxide selectivity 18.3%, no diacid formation was detected.

Example 19

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 125 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 125 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.58%, cyclohexanol selectivity 39.4%, cyclohexanone selectivity 46.7%, cyclohexyl hydroperoxide selectivity 6.9%, adipic acid selectivity 6.0%, glutaric acid selectivity 1.0%.

Example 20

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. At 130 ℃ and 1.0MPa oxygen pressure,the reaction was stirred at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.58%, cyclohexanol selectivity 36.8%, cyclohexanone selectivity 53.4%, cyclohexyl hydroperoxide selectivity 1.0%, adipic acid selectivity 7.4%, glutaric acid selectivity 1.4%.

Example 21

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 135 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 135 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 10.72%, the cyclohexanol selectivity is 29.2%, the cyclohexanone selectivity is 56.8%, the cyclohexyl hydroperoxide selectivity is 1.0%, the adipic acid selectivity is 10.4%, and the glutaric acid selectivity is 2.6%.

Example 22

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 140 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 140 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) Stirring at room temperatureThe generated peroxide was reduced for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate 12.88%, cyclohexanol selectivity 25.3%, cyclohexanone selectivity 56.6%, cyclohexyl hydroperoxide selectivity 0.8%, adipic acid selectivity 12.3%, glutaric acid selectivity 5.0%.

Example 23

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 145 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 145 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 15.64%, cyclohexanol selectivity 23.2%, cyclohexanone selectivity 49.4%, cyclohexyl hydroperoxide selectivity 0.6%, adipic acid selectivity 18.8%, glutaric acid selectivity 8.0%.

Example 24

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 150 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 150 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed and subjected to gas chromatography with toluene as an internal standardPerforming phase chromatographic analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 17.78%, the cyclohexanol selectivity is 16.8%, the cyclohexanone selectivity is 46.5%, the cyclohexyl hydroperoxide selectivity is 0.2%, the adipic acid selectivity is 28.1%, and the glutaric acid selectivity is 8.4%.

Example 25

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 0.1 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.1MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. No significant product was detected.

Example 26

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 0.4 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.4MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.63%, cyclohexanol selectivity 36.4%, cyclohexanone selectivity 36.3%, cyclohexyl hydroperoxide selectivity 20.2%, adipic acid selectivity 6.1%, glutaric acid selectivity 1.0%.

Example 27

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 0.6 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.6MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion was 6.64%, cyclohexanol selectivity was 28.4%, cyclohexanone selectivity was 49.3%, cyclohexyl hydroperoxide selectivity was 18.4%, adipic acid selectivity was 3.9%, and glutaric acid formation was not detected.

Example 28

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 0.8 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 0.8MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 8.28%, the cyclohexanol selectivity is 43.7%, the cyclohexanone selectivity is 49.3%, the cyclohexyl hydroperoxide selectivity is 0.8%, the adipic acid selectivity is 5.2%, and the glutaric acid selectivity is 1.0%.

Example 29

In a 100mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -m (14 mg),0.07mg/mmol),Cu(OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.2 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.42%, cyclohexanol selectivity 36.5%, cyclohexanone selectivity 54.5%, cyclohexyl hydroperoxide selectivity 0.4%, adipic acid selectivity 6.9%, glutaric acid selectivity 1.7%.

Example 30

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.6 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.6MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.49%, cyclohexanol selectivity 37.6%, cyclohexanone selectivity 53.4%, cyclohexyl hydroperoxide selectivity 0.3%, adipic acid selectivity 7.4%, glutaric acid selectivity 1.3%.

Example 31

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.8 MPa.The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.8MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.40%, cyclohexanol selectivity 36.7%, cyclohexanone selectivity 54.3%, cyclohexyl hydroperoxide selectivity 0.5%, adipic acid selectivity 7.5%, glutaric acid selectivity 1.0%.

Example 32

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 2.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 2.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.38%, cyclohexanol selectivity 35.9%, cyclohexanone selectivity 55.1%, cyclohexyl hydroperoxide selectivity 0.6%, adipic acid selectivity 7.1%, glutaric acid selectivity 1.3%.

Example 33

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 600rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PP) was added to the reaction mixtureh₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.62%, cyclohexanol selectivity 39.7%, cyclohexanone selectivity 54.8%, cyclohexyl hydroperoxide selectivity 0.6%, adipic acid selectivity 4.3%, glutaric acid selectivity 0.6%.

Example 34

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 130 ℃ under 1.0MPa oxygen pressure at 1000rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.45%, cyclohexanol selectivity 37.0%, cyclohexanone selectivity 54.6%, cyclohexyl hydroperoxide selectivity 0.4%, adipic acid selectivity 7.1%, glutaric acid selectivity 0.9%.

Example 35

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 1200rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed,taking methylbenzene as an internal standard, and carrying out gas-phase chromatographic analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.40%, cyclohexanol selectivity 36.2%, cyclohexanone selectivity 56.4%, cyclohexyl hydroperoxide selectivity 0.2%, adipic acid selectivity 6.3%, glutaric acid selectivity 0.9%.

Example 36

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 2.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.32%, cyclohexanol selectivity 36.6%, cyclohexanone selectivity 24.4%, cyclohexyl hydroperoxide selectivity 38.4%, adipic acid selectivity 0.6%, no formation of glutaric acid was detected.

Example 37

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 6.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of the cyclohexane is 6.85 percent,the selectivity of cyclohexanol was 41.9%, the selectivity of cyclohexanone was 43.4%, the selectivity of cyclohexyl hydroperoxide was 7.4%, the selectivity of adipic acid was 6.6%, and the selectivity of glutaric acid was 0.7%.

Example 38

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 12.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 11.85%, the cyclohexanol selectivity is 36.9%, the cyclohexanone selectivity is 41.4%, the cyclohexyl hydroperoxide selectivity is 0.2%, the adipic acid selectivity is 17.2%, and the glutaric acid selectivity is 4.3%.

Example 39

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 16.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate 12.64%, cyclohexanol selectivity 24.8%, cyclohexanone selectivity 42.4%, cyclohexyl hydroperoxide selectivity 0.2%, adipic acid selectivity 26.4%, glutaric acid selectivity 6.2%.

Example 40

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 24.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 14.84%, cyclohexanol selectivity 22.3%, cyclohexanone selectivity 32.5%, cyclohexyl hydroperoxide selectivity 0.2%, adipic acid selectivity 33.1%, glutaric acid selectivity 11.9%.

EXAMPLE 41

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -p (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 130 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 9.68%, the cyclohexanol selectivity is 34.5%, the cyclohexanone selectivity is 56.3%, the cyclohexyl hydroperoxide selectivity is 0.4%, the adipic acid selectivity is 8.2%, and the glutaric acid selectivity is 0.6%.

Example 42

In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner containerA MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.92%, cyclohexanol selectivity 37.6%, cyclohexanone selectivity 53.8%, cyclohexyl hydroperoxide selectivity 0.4%, adipic acid selectivity 7.4%, glutaric acid selectivity 0.8%.

Example 43

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 14.0280g (200mmol) of cyclopentane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclopentane was 4.13%, the selectivity for cyclopentanol was 16.5%, the selectivity for cyclopentanone was 70.2%, the selectivity for cyclopentyl hydroperoxide was 10.3%, the selectivity for glutaric acid was 2.6%, and the selectivity for succinic acid was 0.4%.

Example 44

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 19.6540g (200mmol) of cycloheptane, the reaction vessel was sealed, and the temperature was raised by stirringOxygen was introduced at 120 ℃ to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 19.9 percent, the selectivity of cycloheptanol is 18.1 percent, the selectivity of cycloheptanone is 62.4 percent, the selectivity of cycloheptyl hydroperoxide is 11.5 percent, the selectivity of pimelic acid is 6.8 percent, and the selectivity of adipic acid is 1.2 percent.

Example 45

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 22.4400g (200mmol) of cyclooctane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. 22.8 percent of cyclooctane conversion rate, 32.6 percent of cyclooctanol selectivity, 53.5 percent of cyclooctanone selectivity, 10.7 percent of cyclooctyl hydrogen peroxide selectivity, 3.0 percent of octanedioic acid selectivity and 0.2 percent of pimelic acid selectivity.

Example 46

In a 100mL stainless steel autoclave having a Teflon liner, MOF PCN-222(Co) -m (14mg,0.07mg/mmol), Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 19.6540g (200mmol) cyclododecane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water1.3115g (5.00mmol) of triphenylphosphine (PPh) were added₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion of cyclododecane was 25.9%, the selectivity for cyclododecanol was 20.1%, the selectivity for cyclododecanone was 58.5%, and the selectivity for cyclododecyl hydroperoxide was 21.4%, and no formation of aliphatic diacid was detected.

Example 47 (comparative experiment)

In a 100mL stainless steel autoclave with a Teflon liner, the MOF PCN-222(Co) -m (14mg,0.07mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the autoclave was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.58%, cyclohexanol selectivity 36.3%, cyclohexanone selectivity 48.4%, cyclohexyl hydroperoxide selectivity 3.3%, adipic acid selectivity 10.1%, glutaric acid selectivity 1.9%.

Example 48 (comparative experiment)

In a 100mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -p (14mg,0.07mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the autoclave was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed,taking methylbenzene as an internal standard, and carrying out gas chromatography analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.46%, cyclohexanol selectivity 37.4%, cyclohexanone selectivity 47.3%, cyclohexyl hydroperoxide selectivity 3.1%, adipic acid selectivity 10.3%, glutaric acid selectivity 1.9%.

Example 49 (comparative experiment)

In a 100mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -d (14mg,0.07mg/mmol) was dispersed in 16.8320g (200mmol) cyclohexane, the autoclave was sealed, stirred and heated to 130 deg.C, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.86%, cyclohexanol selectivity 38.3%, cyclohexanone selectivity 45.3%, cyclohexyl hydroperoxide selectivity 2.1%, adipic acid selectivity 12.3%, glutaric acid selectivity 2.0%.

Example 50 (comparative experiment)

In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, Cu (OAc)₂(400mg,2mg/mmol) was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) Stirring at room temperature for 30min to reduce the generated peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is removed, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.45%, cyclohexanol selectivity 29.6%, cyclohexanone selectionThe performance was 24.8%, the cyclohexyl hydroperoxide selectivity was 45.6%, and no diacid formation was detected.

Example 51 (amplification experiment)

In a 1000mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -m (140mg,0.07mg/mmol), Cu (OAc)₂(4000mg,2mg/mmol) was dispersed in 168.320g (2000mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 130 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 13.115 g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The reaction mixture was made to 1000mL using acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.48%, cyclohexanol selectivity 35.1%, cyclohexanone selectivity 56.4%, cyclohexyl hydroperoxide selectivity 1.6%, adipic acid selectivity 6.3%, glutaric acid selectivity 0.6%.

Example 52 (amplification experiment)

In a 1000mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -p (140mg,0.07mg/mmol), Cu (OAc)₂(4000mg,2mg/mmol) was dispersed in 168.320g (2000mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 130 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 13.115 g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The reaction mixture was made to 1000mL using acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.61%, cyclohexanol selectivity 34.2%, cyclohexanone selectivity 58.4%, cyclohexyl hydroperoxide selectivity 1.1%, adipic acid selectivity 5.9%, glutaric acid selectivity 0.4%.

Example 53 (amplification experiment)

In a 1000mL stainless steel autoclave with a Teflon liner, MOF PCN-222(Co) -d (140mg,0.07mg/mmol), Cu (OAc)₂(4000mg,2mg/mmol) was dispersed in 168.320g (2000mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 130 ℃ and 1.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, ice water was cooled to room temperature, and 13.115 g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture₃) The resulting peroxide was reduced by stirring at room temperature for 30 min. The reaction mixture was made to 1000mL using acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 9.84%, cyclohexanol selectivity 38.3%, cyclohexanone selectivity 54.4%, cyclohexyl hydroperoxide selectivity 0.3%, adipic acid selectivity 6.3%, glutaric acid selectivity 0.7%.

Claims

1. A method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt, characterized in that it comprises the following steps:

dispersing metalloporphyrin MOFs PCN-222(Co) and Cu (II) salt into cycloalkane, wherein the mass of the metalloporphyrin MOFs PCN-222(Co) is 1% -10% of the content of the cycloalkane material, and g/mol; the amount of Cu (II) salt substance is 0.01-10% of the amount of cycloalkane substance, mol/mol; sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction solution to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;

the above-mentionedThe Cu (II) salt is Cu (CH)₃COO)₂，Cu(NO₂)₂，CuSO₄，CuCl₂And hydrates thereof, or a mixture of at least two of the hydrates in any proportion;

2. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-222(Co)/cu (ii) salts according to claim 1, wherein the catalyst is a binary combination of metalloporphyrin MOFs PCN-222(Co) and cu (ii) salts.

3. The method for the concerted catalytic oxidation of cycloalkanes by metalloporphyrin MOFs PCN-222(Co)/cu (ii) salts according to claim 1 or 2, wherein the ratio of the mass of metalloporphyrin MOFs PCN-222(Co) to the amount of cycloalkanes is 1: 100 to 1: 10.

4. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-222(Co)/Cu (II) salt according to claim 1 or 2, wherein the mass ratio of Cu (II) salt to cycloalkanes is 1: 10000 to 1: 10.

5. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-222(Co)/Cu (II) salts according to claim 1 or 2, wherein the reaction pressure is 0.10-2.0 MPa.

6. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-222(Co)/Cu (II) salts according to claim 1 or 2, wherein the stirring speed is 600-1200 rpm.

7. The process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin salts, MOFs PCN-222(Co)/cu (ii), according to claim 1 or 2, wherein said oxidant is oxygen, air or a mixture thereof in any proportion.

8. The metalloporphyrin PCN-222(Co)/Cu (II) salt Co-catalyzed oxidation method of cycloalkanes according to claim 1, wherein said post-treatment method is: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution₃And the using amount is 3 percent of the amount of the cyclane substance, the peroxide generated by reduction is stirred for 40min at room temperature, and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.