CN111701600A - Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof - Google Patents

Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof Download PDF

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CN111701600A
CN111701600A CN202010628587.6A CN202010628587A CN111701600A CN 111701600 A CN111701600 A CN 111701600A CN 202010628587 A CN202010628587 A CN 202010628587A CN 111701600 A CN111701600 A CN 111701600A
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dimethyladamantane
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CN111701600B (en
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张少平
李培申
王林玉
漆定超
张月成
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Cangzhou Senary Chemical Science Tec Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
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Abstract

The invention relates to the technical field of medicines, and particularly discloses a catalyst for preparing 1-bromo-3, 5-dimethyladamantane and application thereof. The catalyst for preparing the 1-bromo-3, 5-dimethyladamantane is SO4 2‑/ZrO2‑Al2O3‑Pr6O11Wherein, the catalystAl in chemical agent2O3The mass content of (A) is 4.2-6.3%; pr (Pr) of6O11The mass content of (A) is 2.0-2.8%; SO (SO)4 2‑The mass content of (A) is 5.6-13.7%. The catalyst is used in the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane from perhydroacenaphthylene. The catalyst for preparing 1-bromo-3, 5-dimethyladamantane provided by the invention has the advantages that the catalytic activity of the catalyst is high and stable under the combined action of various active components, the catalyst can be recycled, no environmental pollution is caused, the cost can be effectively reduced, and the product yield and purity can be improved.

Description

Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof
Technical Field
The invention relates to the technical field of medicines, in particular to a catalyst for preparing 1-bromo-3, 5-dimethyladamantane and application thereof.
Background
Memantine hydrochloride, chemical name 3, 5-dimethyl-1-amino-adamantane hydrochloride, is a new generation of medicine for improving cognitive function. Currently, cholinesterase inhibitors and memantine hydrochloride are approved for the treatment of alzheimer's disease. Due to different action mechanisms, memantine hydrochloride can be used together with cholinesterase inhibitor to increase curative effect.
1-bromo-3, 5-dimethyladamantane is a key intermediate for preparing memantine hydrochloride, and the preparation method of 1-bromo-3, 5-dimethyladamantane in the prior art comprises the following steps: using perhydroacenaphthene as initial raw material, carrying out rearrangement reaction under the action of catalyst anhydrous aluminium trichloride to obtain 1, 3-dimethyladamantane, and further carrying out bromination reaction with bromine to obtain 1-bromo-3, 5-dimethyladamantane.
However, in the rearrangement reaction process, a large amount of anhydrous aluminum trichloride is needed, and in the subsequent treatment, a large amount of clear water is needed for washing the reaction solution to remove the aluminum trichloride, so that a large amount of aluminum trichloride-containing wastewater is generated, the energy consumption is high, and the environment is seriously polluted.
Therefore, the research on the clean catalyst which is suitable for industrial production and is used for preparing the memantine hydrochloride key intermediate 1-bromo-3, 5-dimethyl adamantane is of great significance.
Disclosure of Invention
Aiming at the technical problems in the existing 1-bromo-3, 5-dimethyl adamantane preparation process, the invention provides a catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a catalyst for preparing 1-bromo-3, 5-dimethyladamantane is SO4 2-/ZrO2-Al2O3-Pr6O11Wherein Al is contained in the catalyst2O3The mass content of (A) is 4.2-6.3%; pr (Pr) of6O11The mass content of (A) is 2.0-2.8%; SO (SO)4 2-The mass content of (A) is 5.6-13.7%.
Compared with the prior art, the catalyst for preparing 1-bromo-3, 5-dimethyladamantane provided by the invention is Al prepared by adopting a coprecipitation impregnation method2O3And Pr6O11Doping modified SO4 2-/ZrO2The solid acid catalyst has high catalytic activity and stable activity under the combined action of a plurality of active components in the obtained catalyst, can be recycled, does not produce environmental pollution, and can effectively reduce the cost.
Further, the preparation method of the catalyst comprises the following steps:
dissolving zirconium oxychloride, aluminum nitrate and praseodymium nitrate in deionized water, adjusting the pH value to 9.5-10.5, carrying out heat preservation reaction, and carrying out suction filtration, washing, drying and grinding treatment to obtain precursor solid powder;
step two, dipping the precursor solid powder in sulfuric acid, drying and calcining to obtain a catalyst SO4 2-/ZrO2-Al2O3-Pr6O11。
Al is prepared by coprecipitation impregnation method2O3And Pr6O11Doping modified SO4 2-/ZrO2The solid acid catalyst improves the catalytic activity and stability.
Further, in the first step, the temperature of the heat preservation reaction is 25-50 ℃, and the time is 1.5-2.5 h; the drying temperature is 100-120 ℃, and the drying time is 12-13 h.
Further, in the second step, the drying temperature is 100-120 ℃, and the drying time is 12-13 hours; the calcining temperature is 500-600 ℃, and the time is 2.5-3.5 h.
Furthermore, the particle size of the precursor solid powder is 100-200 meshes, and the dipping time is 1.5-2.5 h.
The invention also provides the application of the catalyst in the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane from perhydroacenaphthylene.
The invention also provides a synthesis method of the 1-bromo-3, 5-dimethyl adamantane, which comprises the steps of taking perhydroacenaphthylene as a raw material, carrying out rearrangement reaction under the action of the catalyst to obtain 1, 3-dimethyl adamantane, and carrying out bromination reaction on the obtained 1, 3-dimethyl adamantane to obtain 1-bromo-3, 5-dimethyl adamantane.
The invention provides a synthesis method of 1-bromo-3, 5-dimethyl adamantane, which uses SO4 2-/ZrO2-Al2O3-Pr6O11The catalyst is convenient to recycle, is energy-saving and environment-friendly, and has the characteristics of easy control of operation conditions, simple post-treatment, no environmental pollution and high product yield.
Furthermore, the reaction temperature of the rearrangement reaction is 150-200 ℃ and the time is 5-7 h, so that the rearrangement reaction is ensured to be smoothly carried out.
Further, the reaction temperature of the rearrangement reaction is 160-180 ℃, the time is 6-6.5 hours, and the yield of the 1, 3-dimethyl adamantane is ensured.
Further, in the bromination reaction process, 1, 3-dimethyl adamantane is dropwise added into a bromine-containing solvent at the temperature of 0-20 ℃, and then the mixture is refluxed for 18-20 hours and separated to obtain 1-bromine-3, 5-dimethyl adamantane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a catalyst for preparing 1-bromo-3, 5-dimethyladamantane, wherein the catalyst is SO4 2-/ZrO2-Al2O3-Pr6O11I.e. using Al2O3And Pr6O11Doping modified SO4 2-/ZrO2Solid acid catalyst, wherein Al is present in said catalyst2O3The mass content of (A) is 4.2-6.3%; pr (Pr) of6O11The mass content of (A) is 2.0-2.8%; SO (SO)4 2-The mass content of (A) is 5.6-13.7%.
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane from perhydroacenaphthylene, and the 1-bromo-3, 5-dimethyladamantane is prepared through the following reaction steps.
Figure BDA0002567558560000031
In the presence of the catalyst, perhydroacenaphthylene is subjected to rearrangement reaction to obtain 1, 3-dimethyladamantane, and the obtained 1, 3-dimethyladamantane is subjected to bromination reaction to obtain 1-bromo-3, 5-dimethyladamantane.
To better illustrate the catalysts used in the preparation of 1-bromo-3, 5-dimethyladamantane provided in the examples of the present invention, further examples are provided below.
Example 1
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3-Pr6O11Wherein Al is contained in the catalyst2O3The mass content of (A) is 5%; pr (Pr) of6O11The mass content of (A) is 2.5%; SO (SO)4 2-The mass content of the metal element is 9.8 percent, and the content measurement of the metal element adopts inductively coupled plasma emission spectroscopy (ICP-AES); the sulfate content was determined by thermogravimetry-differential scanning calorimetry (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g and praseodymium nitrate hexahydrate(Pr(NO3)3·6H2O)2.4g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 10, controlling the reaction temperature to be not more than 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 45 ℃ for reaction for 2 hours, then carrying out vacuum filtration, washing a filter cake with deionized water until no chloride ion exists, drying the filter cake at 120 ℃ for 12 hours, and grinding the filter cake into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2h, then carrying out vacuum filtration, drying a filter cake at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain a catalyst SO4 2-/ZrO2-Al2O3-Pr6O11。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3-Pr6O11Stirring and heating to 180 ℃ for reaction for 6h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (57.6g), wherein the yield is 95.7 percent, and the GC purity is 99.7 percent.
S2: 50ml of dichloromethane and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 57.6g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 5 hours), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 20 hours). After the reaction, the temperature of the system is reduced to 20 ℃, 5% sodium bisulfite aqueous solution 100ml is added, stirring, standing and liquid separation are carried out, the organic phase is washed by water (50ml multiplied by 2), anhydrous sodium sulfate is added for drying, filtration, concentration and reduced pressure distillation are carried out, 77.0g of 1-bromo-3, 5-dimethyl adamantane is obtained, the yield is 90.3%, and the GC purity is 99.6%.
Example 2
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3-Pr6O11Wherein the molar ratio of Zr/Al/Pr is 20:2:0.3, and Al in the catalyst2O3The mass content of (A) is 4.2%; pr (Pr) of6O11The mass content of (A) is 2.1%; SO (SO)4 2-The mass content of the metal element is 5.6 percent, and the content measurement of the metal element adopts inductively coupled plasma emission spectroscopy (ICP-AES); the sulfate content was determined by thermogravimetry-differential scanning calorimetry (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g and praseodymium nitrate hexahydrate (Pr (NO)3)3·6H2O)2.4g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 9.5, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 25 ℃ for reaction for 2.5h, then carrying out vacuum filtration, washing a filter cake by the deionized water until no chloride ion exists, drying the filter cake at 100 ℃ for 13h, and grinding the filter cake into 200-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 1.5h, then carrying out vacuum filtration, drying a filter cake at 100 ℃ for 13h, and finally roasting in a muffle furnace at 500 ℃ for 3.5h to obtain a catalyst SO4 2-/ZrO2-Al2O3-Pr6O11。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3-Pr6O11Stirring and heating to 150 ℃ for reaction for 7h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (58.1g), wherein the yield is 96.5 percent and the GC purity is 99.8 percent.
S2: 50ml of dichloromethane and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 58.1g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 5 h), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 18 h). After the reaction, the temperature of the system is reduced to 20 ℃, 5% sodium bisulfite aqueous solution 100ml is added, stirring, standing and liquid separation are carried out, the organic phase is washed by water (50ml multiplied by 2), anhydrous sodium sulfate is added for drying, filtration, concentration and reduced pressure distillation are carried out, 77.3g of 1-bromo-3, 5-dimethyl adamantane is obtained, the yield is 90.7%, and the GC purity is 99.7%.
Example 3
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3-Pr6O11Wherein the molar ratio of Zr/Al/Pr is 20:3:0.4, and Al in the catalyst2O3The mass content of (A) is 6.25%; pr (Pr) of6O11The mass content of (A) is 2.8%; SO (SO)4 2-The mass content of the metal element is 13.7 percent, and the content measurement of the metal element adopts inductively coupled plasma emission spectroscopy (ICP-AES); the sulfate content was determined by thermogravimetry-differential scanning calorimetry (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g and praseodymium nitrate hexahydrate (Pr (NO)3)3·6H2O)2.4g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 10.5, controlling the reaction temperature to be not more than 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 50 ℃ for reaction for 2 hours, then carrying out vacuum filtration, washing a filter cake by using the deionized water until no chloride ion exists, drying the filter cake at 110 ℃ for 12 hours, and grinding the filter cake into 100-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2.5h, then carrying out vacuum filtration, drying a filter cake at 110 ℃ for 12h, and finally roasting in a muffle furnace at 600 ℃ for 2.5h to obtain a catalyst SO4 2-/ZrO2-Al2O3-Pr6O11。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3-Pr6O11Stirring and heating to 160 ℃ for reaction for 6.5h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (58.2g), wherein the yield is 96.7 percent and the GC purity is 99.7 percent.
S2: 50ml of dichloromethane and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 58.2g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 4.5 h), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 19 h). After the reaction, the temperature of the system is reduced to 20 ℃, 5% sodium bisulfite aqueous solution 100ml is added, stirring, standing and liquid separation are carried out, the organic phase is washed by water (50ml multiplied by 2), anhydrous sodium sulfate is added for drying, filtration, concentration and reduced pressure distillation are carried out, and 77.6g of 1-bromo-3, 5-dimethyl adamantane is obtained, the yield is 91.0%, and the GC purity is 99.7%.
Example 4
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3-Pr6O11Wherein the molar ratio of Zr/Al/Pr is 100:12:1.8, and Al in the catalyst2O3The mass content of (A) is 5%; pr (Pr) of6O11The mass content of (A) is 2.5%; SO (SO)4 2-The mass content of the metal element is 10 percent, and the content measurement of the metal element adopts inductively coupled plasma emission spectroscopy (ICP-AES); the sulfate content was determined by thermogravimetry-differential scanning calorimetry (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g and praseodymium nitrate hexahydrate (Pr (NO)3)3·6H2O)2.4g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 10, controlling the reaction temperature to be not more than 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 45 ℃ for reaction for 2 hours, then carrying out vacuum filtration, washing a filter cake with deionized water until no chloride ion exists, drying the filter cake at 120 ℃ for 12 hours, and grinding the filter cake into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2h, then carrying out vacuum filtration, drying a filter cake at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain a catalyst SO4 2-/ZrO2-Al2O3-Pr6O11。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3-Pr6O11Stirring and heating to 200 ℃ for reaction for 5h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (57.5g), wherein the yield is 95.6 percent, and the GC purity is 99.6 percent.
S2: 50ml of dichloromethane and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 57.5g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 5 h), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 20 h). After the reaction, the system was cooled to 20 ℃, 5% aqueous sodium bisulfite solution 100ml was added, stirred, allowed to stand, separated, the organic phase was washed with water (50ml × 2), dried with anhydrous sodium sulfate, filtered, concentrated, and distilled under reduced pressure to obtain 77.2g of 1-bromo-3, 5-dimethyladamantane, yield 90.5%, and GC purity 99.5%.
To better illustrate the catalysts used to prepare 1-bromo-3, 5-dimethyladamantane provided in the examples of the present invention, further examples are provided below by way of comparative examples.
Comparative example 1
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2。
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O)100.0g of the filtrate is dissolved in 850ml of deionized water, the mixture is stirred until the mixture is dissolved and clarified, 25% ammonia water is slowly dripped until the pH value of the system is 10, the reaction temperature is controlled not to exceed 50 ℃ in the process of dripping the ammonia water, the mixture is kept at 45 ℃ for reaction for 2 hours, then the mixture is subjected to vacuum filtration, a filter cake is washed by the deionized water until no chloride ion exists, and the filter cake is dried at 120 ℃ for 12 hours and then ground into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2h, then carrying out vacuum filtration, drying a filter cake at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain a catalyst SO4 2-/ZrO2。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2Stirring and heating to 200 ℃ for reaction for 10h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (52.6g), wherein the yield is 81.1 percent, and the GC purity is 92.5 percent.
S2: 50ml of dichloromethane and 52.0g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 52.6g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 5 h), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 20 h). After the reaction, the system was cooled to 20 ℃, 5% aqueous sodium bisulfite solution 100ml was added, and the mixture was stirred, allowed to stand, separated, washed with water (50ml × 2), dried with anhydrous sodium sulfate, filtered, concentrated, and distilled under reduced pressure to obtain 61.7g of 1-bromo-3, 5-dimethyladamantane, with a yield of 85.2% and a GC purity of 99.5%.
Comparative example 2
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3。
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 10, controlling the reaction temperature to be not more than 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 45 ℃ for reaction for 2 hours, then carrying out vacuum filtration, washing a filter cake with deionized water until no chloride ion exists, drying the filter cake at 120 ℃ for 12 hours, and grinding the filter cake into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2h, then carrying out vacuum filtration, drying a filter cake at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain a catalyst SO4 2-/ZrO2-Al2O3。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3Stirring and heating to 150 ℃ for reaction for 10h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (52.9g), wherein the yield is 81.3 percent, and the GC purity is 92.2 percent.
S2: 50ml of dichloromethane and 52.2g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 52.9g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 5 h), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 20 h). After the reaction, the temperature of the system was reduced to 20 ℃, 5% sodium bisulfite aqueous solution 100ml was added, stirring, standing, liquid separation, washing the organic phase with water (50ml × 2), adding anhydrous sodium sulfate, drying, filtering, concentrating, and vacuum distilling to obtain 62.9g of 1-bromo-3, 5-dimethyladamantane, yield 86.3%, and GC purity 99.0%.
Comparative example 3
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3-La2O3。
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g and lanthanum nitrate hexahydrate (La (NO)3)3·6H2O)2.5g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 10, controlling the reaction temperature to be not more than 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 45 ℃ for reaction for 2 hours, then carrying out vacuum filtration, washing a filter cake with deionized water until no chloride ion exists, drying the filter cake at 120 ℃ for 12 hours, and grinding the filter cake into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2h, then carrying out vacuum filtration, drying a filter cake at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain a catalyst SO4 2-/ZrO2-Al2O3-La2O3。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3-La2O3Stirring and heating to 180 deg.C for 6h, cooling to below 30 deg.C, and filteringThe catalyst was recovered by filtration, and the obtained filtrate was subjected to rectification under reduced pressure (vacuum degree of-0.098 to-0.1 MPa) in a rectifying column to give 1, 3-dimethyladamantane (53.8g), yield 83.7%, GC purity 93.3%.
S2: 50ml of dichloromethane and 53.7g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 53.8g of the obtained 1, 3-dimethyl adamantane is slowly dripped into the reaction bottle, the reaction temperature is controlled to be lower than 20 ℃ in the dripping process (the dripping is finished within about 5 hours), then the temperature is raised to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (the reaction is finished within about 20 hours). After the reaction, the temperature of the system was reduced to 20 ℃, 5% sodium bisulfite aqueous solution 100ml was added, stirring, standing, liquid separation, washing the organic phase with water (50ml × 2), adding anhydrous sodium sulfate, drying, filtering, concentrating, and vacuum distilling to obtain 1-bromo-3, 5-dimethyladamantane 65.1g, yield 86.9%, and GC purity 99.2%.
Comparative example 4
A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO4 2-/ZrO2-Al2O3-CeO2。
The preparation method of the catalyst specifically comprises the following reaction steps:
taking zirconium oxychloride octahydrate (ZrOCl)2·8H2O100.0 g, aluminum nitrate nonahydrate (Al (NO)3)3·9H2O)14.0g and cerium nitrate hexahydrate (Ce (NO)3)3·6H2O)2.4g, dissolving in 850ml of deionized water, stirring until the solution is dissolved and clarified, slowly dropwise adding 25% ammonia water until the pH value of the system is 10, controlling the reaction temperature to be not more than 50 ℃ in the process of dropwise adding the ammonia water, keeping the temperature at 45 ℃ for reaction for 2 hours, then carrying out vacuum filtration, washing a filter cake with deionized water until no chloride ion exists, drying the filter cake at 120 ℃ for 12 hours, and grinding the filter cake into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2h, then carrying out vacuum filtration, drying a filter cake at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 3h to obtain a catalyst SO4 2-/ZrO2-Al2O3-CeO2。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyladamantane by perhydroacenaphthylene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the above catalyst SO were added to a 100mL reaction flask4 2-/ZrO2-Al2O3-CeO2Stirring and heating to 160 ℃ for reaction for 8.5h, then cooling to below 30 ℃, filtering and recovering the catalyst, and carrying out reduced pressure rectification on the obtained filtrate in a rectifying tower (the vacuum degree is-0.098-0.1 MPa) to obtain 1, 3-dimethyl adamantane (54.2g), wherein the yield is 84.6 percent, and the GC purity is 93.6 percent.
S2: adding 50ml of dichloromethane and 54.3g of bromine into a 500ml reaction bottle, stirring and cooling to 0 ℃, then slowly dropwise adding 54.2g of the obtained 1, 3-dimethyl adamantane into the reaction bottle, controlling the reaction temperature to be lower than 20 ℃ in the dropwise adding process (the dropwise adding is finished within about 5 h), then heating to reflux reaction, and monitoring the reaction by using gas chromatography until the reaction is finished (the reaction is finished within about 20 h). After the reaction, the temperature of the system is reduced to 20 ℃, 5% sodium bisulfite aqueous solution 100ml is added, stirring, standing and liquid separation are carried out, the organic phase is washed by water (50ml multiplied by 2), anhydrous sodium sulfate is added for drying, filtration, concentration and reduced pressure distillation are carried out, 65.8g of 1-bromo-3, 5-dimethyl adamantane is obtained, the yield is 87.2%, and the GC purity is 99.5%.
The catalysts recovered in example 1 and comparative examples 1 to 4 were recycled, and the number of cycles and the yield and purity of 1, 3-dimethyladamantane were counted, and the results are shown in table 1.
TABLE 1
Figure BDA0002567558560000121
According to the data, the catalyst for preparing the 1-bromo-3, 5-dimethyladamantane provided by the invention has the advantages that the catalytic activity of the catalyst is high and stable through the combined action of various active components, the catalyst can be recycled, no environmental pollution is generated, the cost can be effectively reduced, and the product yield and the purity are improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A catalyst for preparing 1-bromo-3, 5-dimethyladamantane, characterized in that the catalyst is SO4 2-/ZrO2-Al2O3-Pr6O11Wherein Al is contained in the catalyst2O3The mass content of (A) is 4.2-6.3%; pr (Pr) of6O11The mass content of (A) is 2.0-2.8%; SO (SO)4 2-The mass content of (A) is 5.6-13.7%.
2. The catalyst for the preparation of 1-bromo-3, 5-dimethyladamantane according to claim 1, wherein the method of preparation of the catalyst comprises the steps of:
dissolving zirconium oxychloride, aluminum nitrate and praseodymium nitrate in deionized water, adjusting the pH value to 9.5-10.5, carrying out heat preservation reaction, and carrying out suction filtration, washing, drying and grinding treatment to obtain precursor solid powder;
step two, dipping the precursor solid powder in sulfuric acid, drying and calcining to obtain a catalyst SO4 2-/ZrO2-Al2O3-Pr6O11。
3. The catalyst for the preparation of 1-bromo-3, 5-dimethyladamantane according to claim 2, wherein: in the first step, the temperature of the heat preservation reaction is 25-50 ℃, and the time is 1.5-2.5 h; the drying temperature is 100-120 ℃, and the drying time is 12-13 h.
4. The catalyst for the preparation of 1-bromo-3, 5-dimethyladamantane according to claim 2, wherein: in the second step, the drying temperature is 100-120 ℃, and the drying time is 12-13 h; the calcining temperature is 500-600 ℃, and the time is 2.5-3.5 h.
5. The catalyst for the preparation of 1-bromo-3, 5-dimethyladamantane according to claim 2, wherein: the particle size of the precursor solid powder is 100-200 meshes, and the dipping time is 1.5-2.5 h.
6. Use of the catalyst for the preparation of 1-bromo-3, 5-dimethyladamantane according to any one of claims 1 to 5 in the synthesis of 1-bromo-3, 5-dimethyladamantane from perhydroacenaphthylene.
7. A synthetic method of 1-bromo-3, 5-dimethyladamantane is characterized by comprising the following steps: using perhydroacenaphthylene as raw material, under the action of catalyst described in any one of claims 1-5 making rearrangement reaction to obtain 1, 3-dimethyl adamantane, then making bromination reaction on the obtained 1, 3-dimethyl adamantane to obtain 1-bromo-3, 5-dimethyl adamantane.
8. The method of synthesizing 1-bromo-3, 5-dimethyladamantane according to claim 7, wherein: the reaction temperature of the rearrangement reaction is 150-200 ℃, and the time is 5-7 h.
9. The method of synthesizing 1-bromo-3, 5-dimethyladamantane of claim 8, wherein: the reaction temperature of the rearrangement reaction is 160-180 ℃, and the time is 6-6.5 h.
10. The method of synthesizing 1-bromo-3, 5-dimethyladamantane according to claim 7, wherein: in the bromination reaction process, 1, 3-dimethyl adamantane is dropwise added into a bromine-containing solvent at the temperature of 0-20 ℃, and then the mixture is refluxed for 18-20 hours and separated to obtain 1-bromine-3, 5-dimethyl adamantane.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418387A (en) * 1965-12-28 1968-12-24 Ceskoslovenska Akademie Ved Process for the production of adamantane
JPH026855A (en) * 1987-10-05 1990-01-11 Kawasaki Steel Corp Production of 1,3-dimethyladamantane, catalyst for production thereof and production of the same catalyst
JP2005120025A (en) * 2003-10-17 2005-05-12 Idemitsu Kosan Co Ltd Method for producing adamanatanes
CN102921399A (en) * 2012-10-30 2013-02-13 陕西启源科技发展有限责任公司 Method for preparing solid catalyst
CN104592034A (en) * 2015-01-28 2015-05-06 中钢集团鞍山热能研究院有限公司 Synthetic method of 1, 3-diamidophenyl-5, 7-dimethyl adamantane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418387A (en) * 1965-12-28 1968-12-24 Ceskoslovenska Akademie Ved Process for the production of adamantane
JPH026855A (en) * 1987-10-05 1990-01-11 Kawasaki Steel Corp Production of 1,3-dimethyladamantane, catalyst for production thereof and production of the same catalyst
JP2005120025A (en) * 2003-10-17 2005-05-12 Idemitsu Kosan Co Ltd Method for producing adamanatanes
CN102921399A (en) * 2012-10-30 2013-02-13 陕西启源科技发展有限责任公司 Method for preparing solid catalyst
CN104592034A (en) * 2015-01-28 2015-05-06 中钢集团鞍山热能研究院有限公司 Synthetic method of 1, 3-diamidophenyl-5, 7-dimethyl adamantane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王瑞芬: ""固体酸催化异构化反应的研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 *

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