CN109704932B - Method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation - Google Patents
Method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation Download PDFInfo
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Abstract
The invention discloses a method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation, which comprises the steps of adding di-tert-butyl-4-methylphenol (BHT) and a supported catalyst into a high-pressure reaction kettle, wherein the conversion rate of the BHT is 100% after the reaction is finished, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is more than 99.2%; adding 2, 6-di-tert-butyl-4-methylcyclohexanone and an auxiliary agent into a high-pressure reaction kettle, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100% after the reaction is finished, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is more than 98.1%. The invention solves the problems of harsh reaction conditions, complex operation, environmental pollution, difficult industrial application and the like in the prior art.
Description
Technical Field
The invention belongs to a green process, and relates to a synthetic method of 2, 6-di-tert-butyl-4-methylcyclohexanol.
Background
2, 6-di-tert-butyl-4-methylcyclohexanol (English: 2,6-Bis-tert-butyl-4-methylcyclohexanol) is mainly used in the field of photography; can be used as a dispersant for color photography; can also be used as a solvent to be applied to the field of dyes; meanwhile, the compound can also be used as a medical intermediate and a pesticide intermediate. At present, the 2, 6-di-tert-butyl-4-methylcyclohexanol is mainly prepared by a kettle type hydrogenation method, di-tert-butyl-4-methylphenol is used as a raw material, and the 2, 6-di-tert-butyl-4-methylcyclohexanol is prepared by hydrogenation in the presence of a catalyst and a solvent, wherein the catalyst used in the preparation process is mainly a noble metal loaded catalyst, and the loaded metal mainly comprises Ru, Rh, Pt, Ni, Pd and the like. Under the process conditions, the 2, 6-di-tert-butyl-4-methylcyclohexanone and the 2, 6-di-tert-butyl-4-methylcyclohexanol have higher selectivity; however, the process conditions are severe, long-time reaction under high temperature and high pressure conditions is required, and hydrogenolysis is easily caused, so that the post-treatment is complicated.
EP0703210B describes the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanol by a one-step process. Adding 0.5-200 wt% of catalyst and a certain amount of di-tert-butyl-4-methylphenol into an autoclave at the same time, and reacting at the reaction temperature of 50-300 ℃, the reaction time of 6-12 h and the reaction pressure of 10-25 MPa to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol with the content of more than 95%.
EP0720981A1 relates to a process for the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanol. Firstly, 100g of di-tert-butyl-4-methylphenol, 500ml of isopropanol and 10g of Raney nickel catalyst are added into an autoclave with the capacity of 1L, the reaction is carried out at the reaction temperature of 100 ℃, the reaction time of 9h and the reaction pressure of 1MPa, and after the reaction is finished, the 2, 6-di-tert-butyl-4-methylcyclohexanone is obtained through the filtration and separation of the catalyst and the reduced pressure distillation of the solvent; then adding 8.6g of lithium aluminum hydride and 200ml of tetrahydrofuran into a four-mouth bottle, slowly dripping the obtained 2, 6-di-tert-butyl-4-methylcyclohexanone under the condition of stirring at 0 ℃, slowly heating to room temperature after dripping is finished, maintaining the room temperature for reaction for 2 hours, adding 40ml of methanol for quenching after the reaction is finished, adding 600ml of ethyl acetate for extraction and concentration, separating and washing an organic phase, and removing the solvent by reduced pressure distillation to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol.
US2505817 and US2574078 relate to a process for the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanone. Adding 10-15% Raney's nickel catalyst (mass ratio) and a certain amount of di-tert-butyl-4-methylphenol into an autoclave, reacting at 160-250 ℃ for 1-2 h and 10-17 MPa to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone.
The method adopts two-step hydrogenation to prepare the 2, 6-di-tert-butyl-4-methylcyclohexanol, effectively improves the conversion rate and the selectivity, has mild reaction conditions, does not cause environmental pollution, and belongs to a green process.
Disclosure of Invention
The invention aims to solve the problems of harsh reaction conditions, complex operation, environmental pollution, difficult industrial application and the like in the prior art, and provides a method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation.
The technical scheme provided by the invention comprises the following steps: the method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation is characterized in that BHT is used as a raw material, two-step catalytic hydrogenation is adopted to prepare 2, 6-di-tert-butyl-4-methylcyclohexanol, and in the first step, di-tert-butyl-4-methylphenol and a catalyst are subjected to hydrogenation treatment to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone; and the second step is to mix the obtained 2, 6-di-tert-butyl-4-methylcyclohexanone with an auxiliary agent and obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol through catalytic hydrogenation treatment.
Typically, the catalyst is Ru/Al 2 O 3 ，Rh/Al 2 O 3 ，Pd/C，Ni/SO 2 ，Pt/Al 2 O 3 Any one of them or a mixture thereof.
The reaction temperature of the first step reaction is 120-180 ℃.
The reaction pressure of the first step reaction is 1 MPa-10 MPa.
The reaction time of the first step reaction is 1-6 h.
The auxiliary agent is a protic solvent.
The protic solvent is any one or mixture of water, ethanol, formic acid, acetic acid and ethylamine.
The dosage of the auxiliary agent is 5-20% of the mass of the 2, 6-di-tert-butyl-4-methylcyclohexanone.
The reaction temperature of the second step of reaction is 160-200 ℃, and the pressure is 5-10 MPa
The reaction time of the second step reaction is 1-4 h.
The invention has the beneficial effects that:
(1) the 2, 6-di-tert-butyl-4-methylcyclohexanol is prepared by two-step hydrogenation, has the advantages of low reaction temperature, low reaction pressure, short reaction time, high catalytic activity and the like, effectively inhibits the generation of byproducts, and is easy to separate from products after reaction;
(2) the invention uses the supported metal catalyst, belongs to the green environmental protection technology, and has no harm to the environment basically;
(3) in the invention, the supported metal catalyst is used for catalytic hydrogenation, the conversion rate of BHT is 100%, the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is more than 99.2%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanol is more than 98.1%.
Detailed Description
The following examples were carried out according to the following protocols.
(1) Adding di-tert-butyl-4-methylphenol and a supported catalyst into a high-pressure reaction kettle according to a certain proportion, firstly testing leakage of nitrogen, respectively replacing 3 times with nitrogen and hydrogen after ensuring no gas leakage, then filling hydrogen for pressurizing, starting heating under the condition of certain hydrogen pressure, controlling the reaction temperature to be 120-180 ℃, the reaction pressure to be 1-6 MPa and the reaction time to be 1-6 h, and sampling, detecting and analyzing after the reaction is finished to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanone.
(2) Adding the material obtained in the step (1) and an auxiliary agent into a high-pressure reaction kettle according to a certain proportion, firstly performing leakage test, ensuring that the material is not leaked, then respectively replacing the material by nitrogen and hydrogen for 3 times, then filling hydrogen and pressurizing, starting to heat under the condition of certain hydrogen pressure, controlling the reaction temperature to be 160-200 ℃, the reaction pressure to be 5-10 MPa, and the reaction time to be 1-4 h, and sampling, detecting and analyzing after the reaction is finished to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol.
Example 1
100g of di-tert-butyl-4-methylphenol and 5g of Ru/Al with the content of 5% 2 O 3 Simultaneously adding a load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage by using nitrogen, ensuring that the metal catalyst is not leaked, then respectively replacing the metal catalyst by using nitrogen and hydrogen for 3 times, then refilling hydrogen, pressurizing to 4MPa, heating to 140 ℃, starting the reaction, maintaining the reaction for 1h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100 percent, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.7 percent; continuously adding 10g of water into the reaction kettle, performing nitrogen leakage test, ensuring no gas leakage, replacing with nitrogen and hydrogen respectively for 3 times, then refilling hydrogen, pressurizing to 4MPa, heating to 200 ℃, starting reaction, and maintaining the reactionAfter 1h, the temperature is reduced, and sampling detection and analysis show that the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.2 percent.
Example 2
100g of di-tert-butyl-4-methylphenol and 5g of Rh/Al with the content of 5 percent 2 O 3 Simultaneously adding a load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage of nitrogen, ensuring no leakage, then respectively replacing 3 times with nitrogen and hydrogen, then refilling hydrogen, pressurizing to 3MPa, heating to 130 ℃ to start reaction, maintaining the reaction for 1h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.6%; and (2) continuously adding 15g of ethanol into the reaction kettle, carrying out nitrogen leakage test, replacing the mixture for 3 times by nitrogen and hydrogen respectively after ensuring no gas leakage, then refilling hydrogen, pressurizing to 5MPa, heating to 180 ℃, starting the reaction, maintaining the reaction for 1h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100%, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.8%.
Example 3
100g of di-tert-butyl-4-methylphenol and 5g of Ni/SO with the content of 5% 2 Simultaneously adding a load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage of nitrogen, ensuring no leakage, then respectively replacing 3 times with nitrogen and hydrogen, then refilling hydrogen, pressurizing to 5MPa, heating to 150 ℃, starting reaction, maintaining the reaction for 2h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.3%; continuously adding 10g of acetic acid into the reaction kettle, carrying out nitrogen leakage test, ensuring no gas leakage, replacing 3 times with nitrogen and hydrogen respectively, then refilling hydrogen, pressurizing to 5MPa, heating to 190 ℃ to start reaction, maintaining the reaction for 2h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100%, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.4%.
Example 4
100g of di-tert-butyl-4-methylphenol and 5g of Pt/Al with the content of 5% 2 O 3 Simultaneously adding the load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage by using nitrogen, ensuring that gas is not leaked, and then respectively adding the load type metal catalyst into the high-pressure reaction kettleReplacing 3 times by nitrogen and hydrogen respectively, then refilling hydrogen and pressurizing to 6MPa, heating to 150 ℃ to start reaction, maintaining the reaction for 3 hours, cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.4%; continuously adding 10g of ethylamine into the reaction kettle, carrying out nitrogen leakage test, ensuring that the reaction is airtight, replacing the obtained product by nitrogen and hydrogen respectively for 3 times, then filling hydrogen into the reaction kettle, pressurizing the obtained product to 6MPa, heating the obtained product to 170 ℃ to start reaction, maintaining the reaction for 3 hours, cooling the obtained product, and carrying out sampling detection and analysis, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.5 percent.
Example 5
Adding 100g of di-tert-butyl-4-methylphenol and 5g of Pd/C supported metal catalyst with the content of 5% into a high-pressure reaction kettle simultaneously, testing leakage of nitrogen firstly, replacing 3 times with nitrogen and hydrogen respectively after ensuring no leakage, then refilling hydrogen again, pressurizing to 6MPa, heating to 140 ℃ for starting reaction, maintaining the reaction for 5 hours, cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.2%; and (2) continuously adding 20g of ethanol into the reaction kettle, performing nitrogen leakage test, replacing the mixture for 3 times by nitrogen and hydrogen respectively after ensuring no gas leakage, then refilling hydrogen, pressurizing to 6MPa, heating to 160 ℃, starting the reaction, maintaining the reaction for 4 hours, cooling, sampling, detecting and analyzing, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.1 percent.
Example 6
100g of di-tert-butyl-4-methylphenol and 5g of Ru/Al with the content of 5% 2 O 3 Simultaneously adding a load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage of nitrogen, ensuring no leakage, then respectively replacing 3 times with nitrogen and hydrogen, then refilling hydrogen, pressurizing to 3MPa, heating to 120 ℃ to start reaction, maintaining the reaction for 2h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.7%; continuously adding 20g of formic acid into the reaction kettle, performing nitrogen leakage test, ensuring no leakage, replacing with nitrogen and hydrogen respectively for 3 times, then refilling hydrogen, pressurizing to 5MPa, heating to 190 ℃ to start reaction, and maintaining the reaction for 3hAnd then cooling, sampling, detecting and analyzing, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.6 percent.
Example 7
100g of di-tert-butyl-4-methylphenol and 5g of Rh/Al with the content of 5 percent 2 O 3 Simultaneously adding a load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage by using nitrogen, ensuring that the metal catalyst is not leaked, then respectively replacing the metal catalyst by using nitrogen and hydrogen for 3 times, then refilling hydrogen, pressurizing to 2MPa, heating to 150 ℃, starting the reaction, maintaining the reaction for 1.5h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100 percent, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.6 percent; continuously adding 10g of ethylamine into the reaction kettle, carrying out nitrogen leakage test, replacing 3 times with nitrogen and hydrogen respectively after ensuring no gas leakage, then refilling hydrogen, pressurizing to 7MPa, heating to 200 ℃ to start reaction, maintaining the reaction for 2h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100%, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.7%.
Example 8
100g of di-tert-butyl-4-methylphenol and 5g of Ni/SO with the content of 5% 2 Simultaneously adding a load type metal catalyst into a high-pressure reaction kettle, firstly testing leakage by using nitrogen, ensuring that the metal catalyst is not leaked, then respectively replacing the metal catalyst by using nitrogen and hydrogen for 3 times, then refilling hydrogen, pressurizing to 5MPa, heating to 140 ℃ to start reaction, maintaining the reaction for 2.5h, then cooling, sampling, detecting and analyzing, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanone is 99.5%; continuously adding 10g of formic acid into the reaction kettle, carrying out nitrogen leakage test, replacing 3 times with nitrogen and hydrogen respectively after ensuring no gas leakage, then refilling hydrogen, pressurizing to 6MPa, heating to 180 ℃ to start reaction, keeping the reaction for 3 hours, cooling, sampling, detecting and analyzing, wherein the conversion rate of the 2, 6-di-tert-butyl-4-methylcyclohexanone is 100%, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 98.2%.
Claims (6)
1. A method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation is characterized in that BHT is used as a raw material, two-step catalytic hydrogenation is adopted to prepare 2, 6-di-tert-butyl-4-methylcyclohexanol,the first step is that di-tert-butyl-4-methylphenol and a catalyst are subjected to hydrotreating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone; mixing the obtained 2, 6-di-tert-butyl-4-methylcyclohexanone with an auxiliary agent, and carrying out catalytic hydrogenation treatment to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol; the auxiliary agent is a protic solvent, and the protic solvent is any one or a mixture of water, ethanol, formic acid, acetic acid and ethylamine; the dosage of the auxiliary agent is 5-20% of the mass of the 2, 6-di-tert-butyl-4-methylcyclohexanone; the catalyst is Pd/C, Ni/SiO 2 ，Pt/Al 2 O 3 Any one of them or a mixture thereof.
2. The method according to claim 1, wherein the reaction temperature of the first reaction step is 120 to 180 ℃.
3. The method according to claim 1, wherein the reaction pressure in the first reaction stage is 1MPa to 10 MPa.
4. The method of claim 1, wherein the reaction time of the first step is 1 to 6 hours.
5. The method according to claim 1, wherein the reaction temperature of the second reaction is 160 ℃ to 200 ℃ and the pressure is 5MPa to 10 MPa.
6. The method of claim 1, wherein the reaction time of the second step reaction is 1 to 4 hours.
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| US2505817A (en) * | 1945-05-28 | 1950-05-02 | Gulf Research Development Co | Hydrogenated polyalkylated phenols |
| US2574078A (en) * | 1945-05-28 | 1951-11-06 | Gulf Research Development Co | Hydrogenated polyalkylated phenols |
| US4551564A (en) * | 1983-10-22 | 1985-11-05 | Chemische Werke Huels, Ag | Process for the production of 2- and 4-tert-butylcyclohexanols with high proportions of cis-isomers by catalytic-hydrogenation of the corresponding tert-butylphenols |
| EP0703210A1 (en) * | 1994-09-20 | 1996-03-27 | Fuji Photo Film Co., Ltd. | Process for producing 2,6-di-tert-alkylcyclohexanol |
| EP0720981A1 (en) * | 1995-01-05 | 1996-07-10 | Fuji Photo Film Co., Ltd. | Cyclohexyloxycarbonylacetohydrazides and method for producing 1H-1,2,4-triazoles using the hydrazides |
| CN1188098A (en) * | 1997-01-17 | 1998-07-22 | 住友化学工业株式会社 | Processes for preparing 4-tert.-butylcyclohexanol and 4-tert-butylcyclohexyl acetate |
| WO2002048079A2 (en) * | 2000-12-11 | 2002-06-20 | Haarmann & Reimer Gmbh | Method for producing cis-2-tert-butylcyclohexanol |
| CN103193638A (en) * | 2012-01-06 | 2013-07-10 | 南昌洋浦天然香料香精有限公司 | Synthetic method of perfume o-tert-butylcyclohexyl acetate |
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- 2017-10-25 CN CN201711005490.4A patent/CN109704932B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2505817A (en) * | 1945-05-28 | 1950-05-02 | Gulf Research Development Co | Hydrogenated polyalkylated phenols |
| US2574078A (en) * | 1945-05-28 | 1951-11-06 | Gulf Research Development Co | Hydrogenated polyalkylated phenols |
| US4551564A (en) * | 1983-10-22 | 1985-11-05 | Chemische Werke Huels, Ag | Process for the production of 2- and 4-tert-butylcyclohexanols with high proportions of cis-isomers by catalytic-hydrogenation of the corresponding tert-butylphenols |
| EP0703210A1 (en) * | 1994-09-20 | 1996-03-27 | Fuji Photo Film Co., Ltd. | Process for producing 2,6-di-tert-alkylcyclohexanol |
| EP0720981A1 (en) * | 1995-01-05 | 1996-07-10 | Fuji Photo Film Co., Ltd. | Cyclohexyloxycarbonylacetohydrazides and method for producing 1H-1,2,4-triazoles using the hydrazides |
| CN1188098A (en) * | 1997-01-17 | 1998-07-22 | 住友化学工业株式会社 | Processes for preparing 4-tert.-butylcyclohexanol and 4-tert-butylcyclohexyl acetate |
| WO2002048079A2 (en) * | 2000-12-11 | 2002-06-20 | Haarmann & Reimer Gmbh | Method for producing cis-2-tert-butylcyclohexanol |
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