CN109896937B

CN109896937B - Synthetic method for preparing 3-methylcyclohexanone from m-cresol

Info

Publication number: CN109896937B
Application number: CN201910205752.4A
Authority: CN
Inventors: 沈月松; 袁东平; 林小强; 曾朝金; 刘尧权
Original assignee: Xiamen Doingcom Chemical Co ltd
Current assignee: Xiamen Doingcom Chemical Co ltd
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2022-06-24
Anticipated expiration: 2039-03-18
Also published as: CN109896937A

Abstract

A synthetic method for preparing 3-methylcyclohexanone from m-cresol. Adding m-cresol and a catalyst into a pressure reaction container, introducing hydrogen for reaction, stopping the reaction when the m-cresol is converted into 3-methylcyclohexanol, cooling a reaction system, and filtering and separating the catalyst to obtain the 3-methylcyclohexanol, wherein the catalyst is Raney nickel of nickel-aluminum alloy; adding 3-methylcyclohexanol into hydrogen peroxide solution for reaction, stopping the reaction when the residual content of 3-methylcyclohexanol in the reaction solution is less than or equal to 1.0%, cooling the reaction system, separating liquid, separating the lower layer from the hydrogen peroxide solution, and separating and rectifying the upper layer from the organic phase to obtain 3-methylcyclohexanone. The m-cresol is simple and easy to obtain, the price of the raw material is relatively low, and the synthesis process is safe and environment-friendly. The reaction in the preparation of 3-methylcyclohexanol by the hydrogenation of m-cresol is carried out in a closed environment, no waste gas and waste water are generated, the conversion rate of raw materials is close to 100 percent, and the molecular utilization rate is high.

Description

Synthetic method for preparing 3-methylcyclohexanone from m-cresol

Technical Field

The invention relates to 3-methylcyclohexanone, in particular to a synthetic method for preparing 3-methylcyclohexanone from m-cresol.

Background

3-methylcyclohexanone is an organic chemical intermediate, can be applied to the synthesis of spices, medicines, fine organic chemicals and the like, and at present, no economical, effective and environment-friendly method for industrially producing 3-methylcyclohexanone exists.

At present, the literature documents of the similar synthesis of methylcyclohexanone are: (1) chinese patent CN108863746A uses light oil in the waste liquid from caprolactam production as raw material, and in a fixed bed reactor, Cu-series catalyst is used to perform catalytic dehydrogenation reaction at a certain temperature, liquid hourly space velocity and reaction pressure, and then the methyl cyclohexanone product is obtained by separation. (2) Chinese patent CN108238884A adds 1-methoxy-4-methyl-6-bromocyclohexane and sulfolane solution into a reaction vessel, raises the temperature of the solution, adds oxalic acid solution to adjust the pH value of the solution, then adds potassium peroxodisulfate, and continues the reaction; and then raising the temperature, adding a potassium chloride solution and phenylmercuric acetate, continuing the reaction, layering the solution, separating an oil layer, washing with a sodium nitrate solution, washing with a caproic acid solution, recrystallizing in a cyclohexanone solution, and dehydrating by using a dehydrating agent to obtain a finished product of 4-methylcyclohexanone.

Disclosure of Invention

The invention aims to provide a synthetic method for preparing 3-methylcyclohexanone from m-cresol, which takes m-cresol as a raw material, obtains high-purity 3-methylcyclohexanone through raney nickel catalytic hydrogenation, hydrogen peroxide oxidation and rectification, has simple process route, safe and stable production process, high yield and higher economic benefit.

The invention comprises the following steps:

1) adding m-cresol and a catalyst into a pressure reaction container, introducing hydrogen for reaction, stopping the reaction when the m-cresol is converted into 3-methylcyclohexanol, cooling a reaction system, and filtering and separating the catalyst to obtain the 3-methylcyclohexanol, wherein the catalyst is Raney nickel of a nickel-aluminum alloy;

in the step 1), the mass percentage of the m-cresol and the catalyst can be 1.5-5.5%, preferably 3-4%; the pressure of the hydrogen can be 1-5 MPa, preferably 2-3 MPa; the reaction temperature can be 110-160 ℃, preferably 130-150 ℃, and the reaction time can be 6-8 h; the Raney nickel of the nickel-aluminum alloy can be nickel with the content accounting for 25-55 percent of the total mass percent of the alloy, and the balance being aluminum; the nickel-aluminum alloy is activated for 3-6 hours at 80-100 ℃ by 15-35% of sodium hydroxide aqueous solution, and can be applied for more than 10 times without reducing the reaction activity.

2) Adding the 3-methylcyclohexanol obtained in the step 1) into a hydrogen peroxide solution for reaction, stopping the reaction when the residual content of the 3-methylcyclohexanol in the reaction solution is less than or equal to 1.0%, cooling the reaction system, separating liquid, separating the lower layer into the hydrogen peroxide solution and the upper layer into a 3-methylcyclohexanone crude product, separating the hydrogen peroxide solution, and rectifying to obtain the 3-methylcyclohexanone.

In the step 2), the molar ratio of the 3-methylcyclohexanol to the hydrogen peroxide solution may be 1: 1.2-1.6, preferably 1: 1.2-1.3; the volume percentage content of the hydrogen peroxide solution can be 20-50%, preferably 30-40%; the reaction temperature can be 60-90 ℃, and the reaction time can be 3-8 h; the total molar yield of the 3-methylcyclohexanone is 85-95 percent, and the content of the 3-methylcyclohexanone is more than or equal to 99 percent;

the synthesis reaction equation of the invention is as follows:

the first step is as follows:

the second step is that:

the m-cresol used as the raw material is simple and easy to obtain, is a byproduct in the industrial production of p-cresol, and has the advantages of relatively low price of the raw material, safe synthetic process and environmental protection. The reaction in the preparation of 3-methylcyclohexanol by m-cresol hydrogenation is carried out in a closed environment, no waste gas and waste water are generated, the conversion rate of raw materials is close to 100 percent, and the molecular utilization rate is high; h in hydrogen peroxide solution used in process of preparing 3-methylcyclohexanone by oxidizing 3-methylcyclohexanol after reaction₂O₂The concentration of the medical disinfectant is reduced to be within 5 percent and is close to the concentration of medical disinfectant, the environment-friendly treatment is simple, the environment pollution is avoided, the whole production process is safe and environment-friendly, and the economic benefit is high.

Detailed Description

The following examples further illustrate the invention.

Example 1

The preparation method of 3-methylcyclohexanone from m-cresol comprises the following steps:

1) 500g of m-cresol was placed in a 1L stainless steel autoclave, and 15g of activated Raney nickel was added and replaced with nitrogen gas.

And (3) heating after stirring, keeping the temperature at 130-150 ℃, introducing hydrogen, keeping the hydrogen pressure at 2-3 MPa, reacting for 7 hours, completely converting m-cresol into 3-methylcyclohexanol, stopping the reaction, cooling, filtering to obtain about 500g of 3-methylcyclohexanol, and storing the filtered Raney nickel in an ethanol solution for recycling.

2) Adding 500g of 3-methylcyclohexanol into a 2L three-neck flask, stirring and heating to 60 ℃, and dripping 360g of hydrogen peroxide solution with the concentration of 50% under a certain condition; and then keeping the reaction temperature at 60-70 ℃ for reaction. Sampling once per hour after reacting for 4 hours, monitoring the reaction condition, stopping the reaction when the content of the 3-methylcyclohexanol in the reaction liquid is less than or equal to 1 percent, cooling, standing for 20min, separating liquid, reserving an upper organic phase, measuring an oxidation value by using hydrogen peroxide after the lower layer reacts, and treating the hydrogen peroxide in a waste liquid pool. Rectifying the upper organic phase (about 5 theoretical plates, the vacuum degree is about 500 Pa) to obtain 430-450 g of 3-methylcyclohexanone product, wherein the GC content is more than or equal to 99.0 percent, and the total yield is 8 percent and 6-90 percent.

Example 2

1) 500g of m-cresol was placed in a 1L stainless steel autoclave, and 20g of activated nickel trinary raney was added and replaced with hydrogen gas.

And (3) heating after stirring, keeping the temperature at 130-140 ℃, introducing hydrogen, keeping the hydrogen pressure at 2-3 MPa, reacting for 6 hours, completely converting m-cresol into 3-methylcyclohexanol, stopping the reaction, cooling, filtering to obtain about 500g of 3-methylcyclohexanol, and storing the filtered Raney nickel in an ethanol solution for recycling.

2) Adding 500g of 3-methylcyclohexanol into a 2L three-neck flask, heating to 70 ℃ under mechanical stirring, and dropwise adding 450g of 40% hydrogen peroxide solution; and then keeping the reaction temperature at 70-80 ℃ for reaction. Sampling once per hour after reacting for 3h, monitoring the reaction condition, stopping the reaction when the content of the 3-methylcyclohexanol in the reaction liquid is less than or equal to 1%, cooling, standing for 20min, separating liquid, retaining an upper organic phase, measuring an oxidation value by using hydrogen peroxide after the lower layer reacts, and treating the hydrogen peroxide in a waste liquid pool. Rectifying the upper organic phase (about 5 theoretical plates, the vacuum degree is about 500 Pa) to obtain 430-460 g of 3-methylcyclohexanone product, wherein the GC content is more than or equal to 99.0 percent, and the total yield is 86-92 percent.

Example 3

1) 500g of m-cresol was placed in a 1L stainless steel autoclave, 25g of activated nickel trinary raney was added, and hydrogen gas was sufficiently replaced.

And (3) heating after stirring, keeping the temperature at 120-130 ℃, introducing hydrogen, keeping the hydrogen pressure at 2-3 MPa, reacting for 5 hours, completely converting m-cresol into 3-methylcyclohexanol, stopping the reaction, cooling, and filtering to obtain about 500g of 3-methylcyclohexanol. The filtered raney nickel is preserved with ethanol solution for reuse.

2) Adding 500g of 3-methylcyclohexanol into a 2L three-neck flask, heating to 70 ℃ under mechanical stirring, and dropwise adding 600g of 30% hydrogen peroxide aqueous solution; and then keeping the reaction temperature at 80-90 ℃ for reaction, sampling once per hour after 6 hours of reaction, monitoring the reaction condition, stopping the reaction when the content of 3-methylcyclohexanol in the reaction liquid is less than or equal to 1%, cooling, standing for 20min, separating liquid, retaining an upper organic phase, measuring an oxidation value by using hydrogen peroxide after the lower layer of reaction, and treating the hydrogen peroxide in a waste liquid pool. Rectifying the upper organic phase (about 5 theoretical plates, vacuum degree about 500 Pa) to obtain 450-480 g of 3-methylcyclohexanone product, wherein GC content is not less than 99.0%, and total yield is 90-94%.

Claims

1. A synthetic method for preparing 3-methylcyclohexanone from m-cresol is characterized by comprising the following steps:

1) adding m-cresol and a catalyst into a pressure reaction container, introducing hydrogen for reaction, stopping the reaction when the m-cresol is converted into 3-methylcyclohexanol, cooling a reaction system, and filtering and separating the catalyst to obtain the 3-methylcyclohexanol, wherein the catalyst is Raney nickel of nickel-aluminum alloy; the mass percentage of the catalyst and the m-cresol is 1.5 to 5.5 percent; the pressure of the hydrogen is 1-5 MPa; the reaction temperature is 110-160 ℃, and the reaction time is 6-8 h; the Raney nickel of the nickel-aluminum alloy is nickel with the content accounting for 25-55% of the total mass of the alloy, and the balance being aluminum;

2) adding the 3-methylcyclohexanol obtained in the step 1) into a hydrogen peroxide solution for reaction, stopping the reaction when the residual content of the 3-methylcyclohexanol in the reaction solution is less than or equal to 1.0%, cooling the reaction system, separating liquid, separating the lower layer into the hydrogen peroxide solution and the upper layer into a 3-methylcyclohexanone crude product, separating the hydrogen peroxide solution, and rectifying to obtain 3-methylcyclohexanone; the molar ratio of the 3-methylcyclohexanol to the hydrogen peroxide solution is 1: 1.2-1.6, and the volume percentage content of the hydrogen peroxide solution is 20% -50%; the reaction temperature is 60-90 ℃, and the reaction time is 3-8 h.

2. The method according to claim 1, wherein in step 1), the mass percentage of the catalyst to m-cresol is 3-4%.

3. The method for synthesizing 3-methylcyclohexanone from m-cresol according to claim 1, wherein in step 1), the pressure of the hydrogen gas is 2 to 3 MPa.

4. The method according to claim 1, wherein the reaction temperature in step 1) is 130-150 ℃.

5. The method for synthesizing 3-methylcyclohexanone from m-cresol according to claim 1, wherein in step 1), the nickel-aluminum alloy is activated by 15-35% sodium hydroxide aqueous solution at 80-100 ℃ for 3-6 h, and is mechanically used for more than 10 times without reducing the reaction activity.

6. The method for synthesizing 3-methylcyclohexanone from m-cresol according to claim 1, wherein in step 2), the molar ratio of 3-methylcyclohexanol to the hydrogen peroxide solution is 1: 1.2 to 1.3.

7. The method according to claim 1, wherein in step 2), the aqueous hydrogen peroxide solution is 30-40% by volume.

8. The process of claim 1, wherein the synthesis reaction equation is as follows:

the first step is as follows:

the second step is that: