CN111662157B - Method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis - Google Patents

Method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis Download PDF

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CN111662157B
CN111662157B CN202010560804.2A CN202010560804A CN111662157B CN 111662157 B CN111662157 B CN 111662157B CN 202010560804 A CN202010560804 A CN 202010560804A CN 111662157 B CN111662157 B CN 111662157B
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butyl
cobalt
autoclave
dmf
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CN111662157A (en
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李扬
孙宁
郝萌
张才林
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Xian Polytechnic University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/75Cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46Iron group metals or copper
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which specifically comprises the following steps: mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, placing into a sealed bottle, flushing the autoclave twice with hydrogen, placing the sealed bottle into the autoclave, pressurizing with hydrogen, placing the autoclave into an aluminum block preheated to 145 ℃, taking out the autoclave, reacting for 12 hours at 135 ℃, cooling, discharging the residual hydrogen, filtering, washing and drying to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol. The 2, 6-di-tert-butyl-4-methylcyclohexanol is directly synthesized by one-step hydrogenation of the 2, 6-di-tert-butyl-4-methylphenol, so that the generation of an intermediate product 2, 6-di-tert-butyl-4-methylcyclohexanone is avoided, and the yield is improved. The method has the advantages of simple operation, low reaction energy consumption, low synthesis cost and environment-friendly technology.

Description

Method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis
Technical Field
The invention belongs to the technical field of medicine preparation, and particularly relates to a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis.
Background
The 2, 6-di-tert-butyl-4-methylcyclohexanol is mainly applied to the fields of photography, printing and dyeing, medical intermediates and the like. As an intermediate for use as a dispersant in color photographic techniques; as a solvent for use in the printing and dyeing field; meanwhile, the compound can also be used as a medical intermediate and a pesticide intermediate. At present, 2, 6-di-tert-butyl-4-methylcyclohexanol is prepared mainly by kettle hydrogenation, 2, 6-di-tert-butyl-4-methylphenol is used as a raw material, and 2, 6-di-tert-butyl-4-methylcyclohexanol is prepared by hydrogenation in the presence of a supported catalyst and a solvent. The process 2, 6-di-tert-butyl-4-methylcyclohexanol has high selectivity, but has harsh process conditions, needs long-time reaction under high temperature and high pressure conditions, and is easy to cause hydrogenolysis, so that post-treatment is complex. EP0703210B uses a one-step process for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol. Adding 0.5-200% of catalyst (mass ratio) 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 ℃ for 12 hours under the reaction pressure of 10-25 Mpa to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol with the content of more than 95%. European patent EP0720981A1 relates to a process for the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanol. Firstly, adding 100g of di-tert-butyl-4-methylphenol, 500ml of isopropanol and 10g of Raney nickel catalyst into a high-pressure kettle with the capacity of 1L, reacting at the reaction temperature of 100 ℃ for 9 hours under the reaction pressure of 1Mpa, filtering and separating the catalyst after the reaction is finished, and distilling the solvent under reduced pressure to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone; and then reducing the cyclohexanone by lithium aluminum hydride to obtain a cyclohexanol product. U.S. Pat. Nos. 3,3779 and 37,35 relate to a process for the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanone. Adding 10-15% Raney nickel catalyst and a certain amount of di-tert-butyl-4-methylphenol into an autoclave, and reacting for 1-2 hours at 160-250 ℃ under 10-17 Mpa to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone. In the prior art, the method has some technical problems or defects, such as harsh reaction conditions, complex operation, environmental pollution, difficult industrial application and the like, and is particularly important to prepare the 2, 6-di-tert-butyl-4-methylcyclohexanol by selecting a method with mild conditions and good reaction performance.
Disclosure of Invention
The invention aims to provide a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which solves the problems of complex reaction path and harsh reaction conditions in the prior art.
The technical scheme adopted by the invention is that the method for synthesizing the 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The present invention is also characterized in that,
in the step 1, preparing a cobalt-based nano catalyst; the method comprises the following steps:
step 1.1, dissolving cobalt nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 20-30min at 150 ℃, performing condensation reflux reaction, then adding a carrier and DMF into the reaction solution, stirring for 4-5h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
and 1.4, pyrolyzing the powder material in an argon atmosphere at the pyrolysis temperature of 400-1000 ℃ for 2 hours, and cooling to room temperature to obtain the cobalt-based nano catalyst.
In step 1.1, the nitrogen ligand is 1, 4-diazabicyclooctane, triethylenediamine or diethylenediamine.
In the step 1.3, the diameter of the aluminum block is 1cm; when sieving, a 200 mesh screen is used.
In step 1.3, the carrier is SiO 2 、Al 2 O 3 、ZSM-5、TiO 2 Any one of carbon powder and magnesium oxide.
In the step 2, the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol, the cobalt-based nano catalyst and the tert-butanol is 220:28:1550.
the invention has the advantages that,
the 2, 6-di-tert-butyl-4-methylcyclohexanol is directly synthesized by one-step hydrogenation of the 2, 6-di-tert-butyl-4-methylphenol, so that the generation of an intermediate product 2, 6-di-tert-butyl-4-methylcyclohexanone is avoided, and the yield is indirectly improved. The method disclosed by the invention is simple to operate, low in reaction energy consumption, low in synthesis cost, environment-friendly in technology, and capable of repeatedly using the prepared catalyst, and is expected to be applied to the fields of organic synthesis and pharmaceutical chemistry of cyclohexanol synthesized by other phenol hydrogenation.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst, which specifically comprises the following steps:
step 1.1, dissolving cobalt (II) nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the nitrogen ligand is 1, 4-diazabicyclooctane, triethylene diamine or diethylene diamine;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 20-30min at 150 ℃, performing condensation reflux reaction, then adding a carrier and DMF into the reaction solution, stirring for 4-5h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the diameter of the aluminum block is 1cm;
when sieving, a 200-mesh screen is adopted;
the carrier is SiO 2 、Al 2 O 3 、ZSM-5、TiO 2 Any one of carbon powder and magnesium oxide;
step 1.4, pyrolyzing the powder material in argon atmosphere at 400-1000 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the cobalt-based nano catalyst to the tert-butanol is 220:28:1550.
example 1
The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst, which specifically comprises the following steps:
step 1.1, dissolving cobalt (II) nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the nitrogen ligand is 1, 4-diazabicyclooctane;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 20min at 150 ℃, performing condensation reflux reaction, adding a carrier and DMF into the reaction solution, stirring for 4h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the diameter of the aluminum block is 1cm; when sieving, a 200-mesh screen is adopted; the carrier is SiO 2
Step 1.4, pyrolyzing the powder material in argon atmosphere at the pyrolysis temperature of 500 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the cobalt-based nano catalyst to the tert-butanol is 220:28:1550.
example 2
The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst, which specifically comprises the following steps:
step 1.1, dissolving cobalt (II) nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the nitrogen ligand is triethylenediamine;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 25min at 150 ℃, performing condensation reflux reaction, adding a carrier and DMF into the reaction solution, stirring for 4h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the diameter of the aluminum block is 1cm; when sieving, a 200-mesh screen is adopted; the carrier is Al 2 O 3
Step 1.4, pyrolyzing the powder material in argon atmosphere at the pyrolysis temperature of 400 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the cobalt-based nano catalyst to the tert-butanol is 220:28:1550.
example 3
The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst, which specifically comprises the following steps:
step 1.1, dissolving cobalt (II) nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the nitrogen ligand is diethyl diamine;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 30min at 150 ℃, performing condensation reflux reaction, then adding a carrier and DMF into the reaction solution, stirring for 4.5h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the diameter of the aluminum block is 1cm;
when sieving, a 200-mesh screen is adopted; the carrier is ZSM-5;
step 1.4, pyrolyzing the powder material in argon atmosphere at 800 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the cobalt-based nano catalyst to the tert-butanol is 220:28:1550.
example 4
The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst, which specifically comprises the following steps:
step 1.1, dissolving cobalt (II) nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the nitrogen ligand is 1, 4-diazabicyclooctane;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 30min at 150 ℃, performing condensation reflux reaction, adding a carrier and DMF into the reaction solution, stirring for 5h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the diameter of the aluminum block is 1cm; when sieving, a 200-mesh screen is adopted; the carrier is TiO 2
Step 1.4, pyrolyzing the powder material in argon atmosphere at 900 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the cobalt-based nano catalyst to the tert-butanol is 220:28:1550.
example 5
The invention discloses a method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis, which is implemented according to the following steps:
step 1, preparing a cobalt-based nano catalyst, which specifically comprises the following steps:
step 1.1, dissolving cobalt (II) nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the nitrogen ligand is 1, 4-diazabicyclooctane, triethylene diamine or diethylene diamine;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 30min at 150 ℃, performing condensation reflux reaction, adding a carrier and DMF into the reaction solution, stirring for 5h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the diameter of the aluminum block is 1cm;
when sieving, a 200-mesh screen is adopted;
the carrier is magnesium oxide;
step 1.4, pyrolyzing the powder material in argon atmosphere at the pyrolysis temperature of 1000 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol.
The mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the cobalt-based nano catalyst to the tert-butanol is 220:28:1550.

Claims (2)

1. the method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by cobalt catalysis is characterized by comprising the following steps:
step 1, preparing a cobalt-based nano catalyst; the method comprises the following steps:
step 1.1, dissolving cobalt nitrate hexahydrate and a nitrogen ligand in DMF together, and stirring for 5min at 150 ℃ to obtain a mixed solution a;
the mass ratio of cobalt nitrate hexahydrate to nitrogen ligand to DMF is 444.5:395.2:1417.5;
the nitrogen ligand is 1, 4-diazabicyclooctane, triethylene diamine or diethylene diamine;
step 1.2, dissolving propylene glycol methyl ether acetate PMA in DMF, and stirring for 5min at 150 ℃ to obtain a mixed solution b;
the mass ratio of PMA to DMF is 1.16:9.45;
step 1.3, uniformly mixing the mixed solution a and the mixed solution b, adding an aluminum block, stirring for 20-30min at 150 ℃, performing condensation reflux reaction, then adding a carrier and DMF into the reaction solution, stirring for 4-5h at 150 ℃, standing, sealing for 20h at 150 ℃ to slowly evaporate DMF and enable a cobalt-CP template to grow, cooling the material to room temperature after the solvent is completely dried, grinding, and sieving to obtain a powder material;
the mass ratio of the mixed solution a to the mixed solution b to the aluminum block to the carrier to the DMF is 22.57:10.61:27:1.2:14.17;
the carrier is SiO 2 、Al 2 O 3 、ZSM-5、TiO 2 Any one of carbon powder and magnesium oxide;
the diameter of the aluminum block is 1cm;
step 1.4, pyrolyzing the powder material in argon atmosphere at 400-1000 ℃ for 2 hours, and cooling to room temperature to obtain a cobalt-based nano catalyst;
step 2, mixing 2, 6-di-tert-butyl-4-methylphenol, cobalt-based nano catalyst and tert-butanol, putting the mixture into a sealed bottle, flushing the autoclave twice with 30atm hydrogen, putting the sealed bottle into the autoclave, pressurizing with 50atm hydrogen, putting the autoclave into an aluminum block preheated to 145 ℃ for 30min, taking out the autoclave, reacting for 12h at 135 ℃, cooling the autoclave to room temperature, discharging the residual hydrogen, taking out the sealed bottle from the autoclave, filtering out solid matters, fully washing the solid matters with ethyl acetate, and drying for 24h to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol;
in the step 2, the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol, the cobalt-based nano catalyst and the tert-butanol is 220:28:1550.
2. the method for synthesizing 2, 6-di-tert-butyl-4-methylcyclohexanol by using cobalt as defined in claim 1, wherein in the step 1.3, a 200 mesh screen is used for sieving.
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