阅读说明：本技术 仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法 (Method for preparing carboxylic ester compound by breaking carbon-carbon bond through oxidation of secondary alcohol compound ) 是由 高爽 王连月 骆慧慧 吕迎 于 2019-11-29 设计创作，主要内容包括：本发明公开一种仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法。该方法将仲醇类化合物、添加剂及氮掺杂的介孔碳负载的单原子催化剂加入到脂肪伯醇溶剂中,放入压力容器中密闭,通入一定压力的氧源气体,氧源气体压力为0.1-1MPa,反应温度为80-150℃,反应后产物为羧酸酯类化合物。本发明采用的氮掺杂介孔碳负载的单原子催化剂,催化剂活性高,反应后产物羧酸酯类化合物分离收率最高达99％,该方法适用范围广,且反应条件容易控制,催化剂可循环使用,后处理简单,适于工业化生产。(The invention discloses a method for preparing carboxylic ester compounds by oxidizing and breaking carbon-carbon bonds of secondary alcohol compounds. The method comprises the steps of adding a secondary alcohol compound, an additive and a nitrogen-doped mesoporous carbon-supported single-atom catalyst into an aliphatic primary alcohol solvent, placing the aliphatic primary alcohol solvent into a pressure container, sealing the pressure container, introducing oxygen source gas with a certain pressure, wherein the pressure of the oxygen source gas is 0.1-1MPa, the reaction temperature is 80-150 ℃, and obtaining a carboxylic ester compound after reaction. The nitrogen-doped mesoporous carbon-loaded monatomic catalyst adopted by the invention has high catalyst activity, the highest separation yield of the carboxylic ester compound after reaction reaches 99%, the method has wide application range, the reaction condition is easy to control, the catalyst can be recycled, the post-treatment is simple, and the method is suitable for industrial production.)

1. The method for preparing the carboxylic ester compound by oxidizing and breaking the carbon-carbon bond of the secondary alcohol compound is characterized in that: adding a secondary alcohol compound, an additive and a nitrogen-doped mesoporous carbon-supported monoatomic catalyst into an aliphatic primary alcohol solvent, placing the aliphatic primary alcohol solvent into a pressure container, sealing the pressure container, introducing oxygen source gas with certain pressure, wherein the pressure of the oxygen source gas is 0.1-1MPa, the reaction temperature is 80-150 ℃, and the product after the reaction is a carboxylic ester compound.

2. The method for preparing the carboxylic ester compound by oxidizing and breaking the carbon-carbon bond of the secondary alcohol compound as claimed in claim 1, wherein the secondary alcohol compound is one or more than two of the following compounds: aromatic secondary alcohols:R₁＝H,2-Me,3-Me,4-Me,2-MeO,3-MeO,4-MeO,4-F,4-Cl,4-Br，4-NO₂,4-CF₃one or more of 4-CN,4-tBu,4-Ph, R₁The number is 1-5;R₂＝H,Me,Ph,OPh,OPh(4-OCH₃) One or more than two of them;

heterocyclic secondary alcohols: one or more of 3- (1-hydroxyethyl) pyridine, 2- (1-hydroxyethyl) pyridine, DL-1- (2-furyl) ethanol and 1- (thiophene-2-yl) -1-ethanol;

secondary alcohols of fats:n is 1-6, or one or more than two.

3. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds according to claim 1 or 2,

the synthetic route is as follows:

R₃h, one or more of C1-C9.

4. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds as claimed in claim 1, wherein the additive is an alkaline inorganic compound comprising one or more of potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate and potassium phosphate.

5. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds according to claim 1, wherein the preparation method of the nitrogen-doped mesoporous carbon-supported monatomic catalyst comprises the following steps: weighing a certain amount of silica sol, adding the silica sol into water, and stirring at room temperature to obtain a mixed solution A; weighing a certain amount of 1, 10-phenanthroline and cobalt acetate, adding the 1, 10-phenanthroline and cobalt acetate into water, stirring at room temperature to obtain a mixed solution B, slowly dropwise adding the solution A into the mixed solution B, stirring the mixture at room temperature for more than 1 hour, then evaporating water in vacuum, drying the obtained solid in vacuum, roasting the solid in a nitrogen atmosphere at 800-900 ℃ for more than 2 hours, soaking the obtained black powder in HF with the mass concentration of 15-30% for more than 24 hours, washing the black powder to be neutral by deionized water, and drying the black powder in an oven at 80-120 ℃ to obtain a target catalyst Co-N-C; wherein the mass content of Co is 0.5-6 wt%, and the mass content of N is 1-5 wt%.

6. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds as claimed in claim 1, wherein the aliphatic primary alcohol solvent is one or more of C1-C10.

7. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds according to claim 1,

the reaction temperature is 80-150 ℃, preferably 130-150 ℃;

the gas pressure is 0.1-1MPa, preferably 0.4 MPa;

the reaction time is 6 to 30 hours, preferably 12 to 24 hours.

8. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds as claimed in claim 1, wherein the oxygen source is one or both of pure oxygen and air.

9. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds as claimed in claim 1 or 4, characterized in that the molar ratio of the addition amount of the additive to the feeding amount of the alcohol reactant is 0.05-0.2, preferably 0.1.

10. The method for preparing carboxylic ester compounds by oxidatively breaking carbon-carbon bonds of secondary alcohol compounds as claimed in claim 1 or 5, characterized in that the molar ratio of the added amount of the catalyst to the fed amount of the alcohol reactant is 0.01-0.05, preferably 0.05.

Technical Field

The invention relates to the technical field of single-atom catalytic oxidation breaking of carbon-carbon bonds, in particular to a method for directly preparing organic carboxylic ester compounds by oxidative breaking of carbon-carbon bonds of secondary alcohol compounds,

background

The organic methyl carboxylate is a very important chemical product and an organic synthesis intermediate, and is widely applied to the fields of food, organic synthesis, paint, spice, cosmetics, medicine, high polymer materials and the like. Thus, esterification reactions are an important class of organic chemical reactions as a general route to the preparation of esters. The secondary alcohol compound is an important organic compound, can be converted to synthesize various organic chemicals, is esterified by oxidative cleavage of carbon-carbon bonds to obtain organic carboxylic ester, and is an effective way for converting and utilizing the secondary alcohol compound.

The traditional synthesis method of organic carboxylic ester is that acid and alcohol are used as raw materials, concentrated sulfuric acid is used as a catalyst, and the organic carboxylic ester is directly synthesized by esterification after long-time heating. Although the concentrated sulfuric acid used as the catalyst has high activity, the method also has more defects: poor selectivity, more side reactions, poor product purity, and severe environmental pollution and equipment corrosion caused by strong acid. The subsequent mild ester synthesis process is usually carried out by first reacting carboxylic acid with highly active acid chloride, or anhydride, and then reacting with alcohol to produce the corresponding ester. These methods, which require oxidation, activation and esterification steps if an ester is first prepared using an aldehyde as a starting material, generally lower the yield of the ester and require a longer reaction time. Subsequently, further efforts have been directed to the direct oxidative esterification of aldehydes to synthesize esters in one step, but such processes often use stoichiometric or excess amounts of oxidizing agents, e.g., manganese dioxide, potassium hydrogen persulfate, peroxides, and although useful, there are significant amounts of toxic and unwanted by-products formed, and aldehydes as substrates are often oxidized from alcohols. In another method for preparing carboxylic ester, the direct oxidation esterification of primary alcohol is used to synthesize ester substance in one step, but the catalyst used in the method is mainly noble metal Au and Pd, and part of the catalyst system is cobalt-based catalyst loaded by carbon material.

At present, no report exists on a route for obtaining organic carboxylic ester from a secondary alcohol compound through oxidative cleavage esterification of a carbon-carbon bond, and the method not only provides a way for preparing the organic carboxylic ester, but also provides a way for converting and utilizing the secondary alcohol compound.

Disclosure of Invention

The invention provides a new route for obtaining organic carboxylic ester from secondary alcohol compounds through oxidation, breaking and esterification of carbon-carbon bonds, the reaction condition of the route is mild, the carboxylic ester is prepared with high efficiency and low cost, the substrate application is wide, and the product yield is high.

The technical scheme adopted by the invention is as follows:

a method for preparing carboxylic ester compounds by oxidizing and breaking carbon-carbon bonds of secondary alcohol compounds comprises the following steps: adding a secondary alcohol compound, an additive and a nitrogen-doped mesoporous carbon-supported monoatomic catalyst into an aliphatic primary alcohol solvent, placing the aliphatic primary alcohol solvent into a pressure container, sealing the pressure container, introducing oxygen source gas with certain pressure, wherein the pressure of the oxygen source gas is 0.1-1MPa, the reaction temperature is 80-150 ℃, and the product after the reaction is a carboxylic ester compound.

The secondary alcohol compound is one or more than two of the following compounds:

aromatic secondary alcohols:r1 is one or more of H,2-Me,3-Me,4-Me,2-MeO,3-MeO,4-MeO,4-F,4-Cl,4-Br,4-NO2,4-CF3,4-CN,4-tBu,4-Ph, R₁The number is 1-5;one or more of R2 ═ H, Me, Ph, OPh and OPh (4-OCH 3);

heterocyclic secondary alcohols: one or more of 3- (1-hydroxyethyl) pyridine, 2- (1-hydroxyethyl) pyridine, DL-1- (2-furyl) ethanol and 1- (thiophene-2-yl) -1-ethanol;

secondary alcohols of fats:n is 1-6, or one or more than two.

The synthetic route is as follows:

R₃＝H,C1-C9

the additive is an alkaline inorganic compound and comprises one or more of potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate and potassium phosphate.

The preparation method of the nitrogen-doped mesoporous carbon-supported monatomic catalyst comprises the following steps: weighing a certain amount of silica sol, adding the silica sol into water, and stirring at room temperature to obtain a mixed solution A; weighing a certain amount of 1, 10-phenanthroline and cobalt acetate, adding the 1, 10-phenanthroline and cobalt acetate into water, stirring at room temperature to obtain a mixed solution B, slowly dropwise adding the solution A into the mixed solution B, stirring the mixture at room temperature for more than 1 hour, then evaporating water in vacuum, drying the obtained solid in vacuum, roasting the solid in a nitrogen atmosphere at 800-900 ℃ for more than 2 hours, soaking the obtained black powder in HF with the mass concentration of 15-30% for more than 24 hours, finally washing the black powder to be neutral by deionized water, and drying the black powder in an oven at 80-120 ℃ to obtain the target catalyst Co-N-C. Wherein the mass content of Co is 0.5-6 wt%, and the mass content of N is 1-5 wt%.

The aliphatic primary alcohol solvent is one or more of C1-C10.

The reaction temperature is 80-150 ℃, and the preferable reaction temperature is 130-150 ℃;

the gas pressure is 0.1-1MPa, and the preferable reaction gas pressure is 0.4 MPa;

the reaction time is 6-30h, and the preferable reaction time is 12-24 h.

The oxygen source is one or two of pure oxygen or air.

The molar ratio of the additive to the alcoholic reactant charge is 0.05-0.2, preferably 0.1.

The molar ratio of the added amount of the catalyst to the fed amount of the alcohol reactant is 0.01-0.05, and preferably 0.05. Compared with the existing preparation method of the organic carboxylic ester compound, the preparation method has the following advantages:

the catalyst is a heterogeneous catalyst and is easy to recycle

Wide substrate range, and is suitable for various secondary alcohol compounds

The selectivity of the product carboxylic ester is high, and the by-product is less.

The nitrogen-doped mesoporous carbon-loaded monatomic catalyst adopted by the invention has high catalyst activity, the highest separation yield of the carboxylic ester compound after reaction reaches 99%, the method has wide application range, the reaction condition is easy to control, the catalyst can be recycled, the post-treatment is simple, and the method is suitable for industrial production.

Detailed Description

In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.

The preparation method of the nitrogen-doped mesoporous carbon-supported monatomic catalyst comprises the following steps: weighing 5.0g of silica sol, adding the silica sol into 100ml of water, and stirring at room temperature to obtain a mixed solution A; weighing 0.6g of 1, 10-phenanthroline and cobalt acetate, adding into 50ml of water, stirring at room temperature to obtain a mixed solution B, slowly dropwise adding the solution A into the mixed solution B, stirring the mixture at room temperature for 2 hours, then evaporating water in vacuum, drying the obtained solid in vacuum, roasting at 800 ℃ for 2 hours in a nitrogen atmosphere, soaking the obtained black powder in 20% HF for 24 hours, finally washing with deionized water to be neutral, and drying in an oven at 80 ℃ to obtain the target catalyst Co-N-C. Wherein the mass content of Co is 2.3 wt%, and the mass content of N is 3.2 wt%.

Example 1

Mixing Co-N-C (5 mol% relative to the starting material), 1-phenylethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.

Example 2

Adding Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), KOH (20 mol%) and 4mL of methanol into a 25mL pressure kettle with a polytetrafluoroethylene lining in sequence, sealing the reaction kettle, filling oxygen to 0.4MPa, putting the reaction kettle into an oil bath at 130 ℃, stirring and reacting for 12 hours at the rotating speed of 400 ℃, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate by the gas chromatography internal standard method shown in Table 1.

Example 3

Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), Na₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.

Example 4

Adding Co-N-C (5 mol%), 1-Phenyl ethanol (1mmol), Cs₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.

Example 5

Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K₃PO₄(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.

Example 6

Mixing Co-N-C (5 mol%), 1- (2-methylphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (2-methylphenyl) -1-ethanol and a product 2-methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 7

Mixing Co-N-C (5 mol%), 1- (3-methylphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is put into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, and after the reaction is finished, the reaction kettle is cooled to the temperature ofAt room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, the qualitative product is detected by gas chromatography-mass spectrometry, and the yield of the substrate 1- (3-methylphenyl) -1-ethanol and the product 3-methyl benzoate is quantified by the gas chromatography internal standard method and is shown in table 1.

Example 8

Mixing Co-N-C (5 mol%), 1- (4-methylphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (4-methylphenyl) -1-ethanol and a product 4-methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 8

Mixing Co-N-C (5 mol%), 1- (2-methoxyphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (2-methoxyphenyl) -1-ethanol and a product 2-methoxy methyl benzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 9

Mixing Co-N-C (5 mol%), 1- (3-methoxyphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (3-methoxyphenyl) -1-ethanol and a product 3-methoxy methyl benzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 10

Mixing Co-N-C (5 mol%), 1- (4-methoxyphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (4-methoxyphenyl) -1-ethanol and a product 4-methoxy methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 11

Mixing Co-N-C (5 mol%), 1- (4-fluorophenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL of pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-fluorophenyl) -1-ethanol and a product 4-methyl fluorobenzoate is quantified by the gas chromatography internal standard method and shown in Table 1.

Example 12

Mixing Co-N-C (5 mol%), 1- (4-chlorophenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-chlorphenyl) -1-ethanol and a product 4-methyl chlorobenzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 13

Mixing Co-N-C (5 mol%), 1- (4-bromophenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) 4mL of methanol was sequentially added to a 25mL polytetrafluoroethylene-lined autoclave, which was then closed and chargedAnd (3) introducing oxygen to 0.4MPa, putting the reaction kettle into an oil bath at the temperature of 130 ℃, stirring and reacting for 12h at the rotating speed of 400 ℃, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the yield of the substrate 1- (4-chlorphenyl) -1-ethanol and the product 4-methyl bromobenzoate by the gas chromatography internal standard method in table 1.

Example 14

Mixing Co-N-C (5 mol%), 1- (4-nitrophenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL of pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-nitrophenyl) -1-ethanol and a product 4-methyl nitrobenzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 15

Mixing Co-N-C (5 mol%), 1- (4-trifluoromethylphenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-trifluoromethylphenyl) -1-ethanol and a product 4-trifluoromethylbenzoic acid methyl ester is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 16

Mixing Co-N-C (5 mol%), 1- (4-cyanophenyl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, and a gas chromatography-mass spectrometry detection qualitative product, a gas phaseThe yields of substrate 1- (4-cyanophenyl) -1-ethanol and product methyl 4-cyanobenzoate were quantified by internal standard chromatography as shown in Table 1.

Example 17

Mixing Co-N-C (5 mol%), 1- (4-biphenyl) ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (4-biphenyl) ethanol and a product 4-biphenyl methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 18

Mixing Co-N-C (5 mol%), 1-phenylpropanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1-phenylpropanol and a product methyl benzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 19

Mixing Co-N-C (5 mol%), diphenylethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate, namely the diphenylethanol, and a product, namely the methyl benzoate, is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 20

Mixing Co-N-C (5 mol%), 2-phenoxy-1-phenylethanol (1mmol), K₂CO₃(20 mol%) 4mL of methanol was added to 25mL of polytetrafluoro-ethyleneThe method comprises the steps of sealing a reaction kettle with an ethylene lining in the pressure kettle, filling oxygen to 0.4MPa, putting the reaction kettle into an oil bath at 130 ℃, stirring and reacting for 12 hours at the rotating speed of 400 ℃, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting and determining a qualitative product by gas chromatography-mass spectrometry, wherein the yield of a substrate 2-phenoxy-1-phenyl ethanol and a product methyl benzoate is quantified by a gas chromatography internal standard method and shown in table 1.

Example 21

Mixing Co-N-C (5 mol%), 2- (4-methoxy) phenoxy-1-phenylethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 2- (4-methoxy) phenoxy-1-phenyl ethanol and a product methyl benzoate is quantified by a gas chromatography internal standard method and shown in Table 1.

Example 22

Mixing Co-N-C (5 mol%), 3- (1-hydroxyethyl) pyridine (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, the qualitative products are detected by gas chromatography-mass spectrometry, and the yield of the substrate 3- (1-hydroxyethyl) pyridine and the product 3-methyl picolinate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 23

Mixing Co-N-C (5 mol%), 2- (1-hydroxyethyl) pyridine (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, the internal standard biphenyl (60mg) is added, and the gas chromatography-mass spectrometry is carried outThe yields of the substrate 2- (1-hydroxyethyl) pyridine and the product 2-picolinic acid methyl ester were determined qualitatively and quantitatively by gas chromatography internal standard method and are shown in Table 1.

Example 24

Mixing Co-N-C (5 mol%), DL-1- (2-furyl) ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 2- (1-hydroxyethyl) pyridine and a product 2-methyl furoate is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 25

Mixing Co-N-C (5 mol%), 1- (thiophene-2-yl) -1-ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 2- (1-hydroxyethyl) pyridine and a product thiophene-2-methyl carboxylate is quantified by a gas chromatography internal standard method and is shown in Table 1.

Example 25

Mixing Co-N-C (5 mol%), 2-hexanol (1mmol), K₂CO₃(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is put into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, the gas chromatography-mass spectrometry is used for detecting qualitative products, and the yield of the substrate 2-hexanol and the product methyl valerate is quantified by the gas chromatography internal standard method and is shown in Table 1.

Example 26

Mixing Co-N-C (5 mol%), 2-octanol (1mmol), K₂CO₃(20 mol%) 4mL of methanol was added to 25mL of polyThe method comprises the following steps of (1) sealing a reaction kettle in a tetrafluoroethylene-lined pressure kettle, filling oxygen to 0.4MPa, putting the reaction kettle into a 130 ℃ oil bath, stirring and reacting for 12 hours at the rotating speed of 400, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the yield of a substrate 2-octanol and a product methyl heptanoate by a gas chromatography internal standard method, wherein the yield is shown in table 1.

Example 27

Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of ethanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product ethyl benzoate are quantified by the gas chromatography internal standard method and are shown in Table 1.

Example 28

Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K₂CO₃(20 mol%) and 4mL of butanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product butyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.

Example 29

Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K₂CO₃(20 mol%) adding 4mL of octanol into a 25mL pressure kettle with a polytetrafluoroethylene lining in sequence, sealing the reaction kettle, charging oxygen to 0.4MPa, putting the reaction kettle into an oil bath at 150 ℃, stirring and reacting at 400 rotation speed for 12h, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying a substrate 1-phenylethanol conversion by a gas chromatography internal standard methodThe yield and the yield of the product octyl benzoate are shown in Table 1.