CN111701600B - 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

Info

Publication number
CN111701600B
CN111701600B CN202010628587.6A CN202010628587A CN111701600B CN 111701600 B CN111701600 B CN 111701600B CN 202010628587 A CN202010628587 A CN 202010628587A CN 111701600 B CN111701600 B CN 111701600B
Authority
CN
China
Prior art keywords
catalyst
bromo
reaction
dimethyl adamantane
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010628587.6A
Other languages
Chinese (zh)
Other versions
CN111701600A (en
Inventor
张少平
李培申
王林玉
漆定超
张月成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cangzhou Senary Chemical Science Tec Co ltd
Original Assignee
Cangzhou Senary Chemical Science Tec Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cangzhou Senary Chemical Science Tec Co ltd filed Critical Cangzhou Senary Chemical Science Tec Co ltd
Priority to CN202010628587.6A priority Critical patent/CN111701600B/en
Publication of CN111701600A publication Critical patent/CN111701600A/en
Application granted granted Critical
Publication of CN111701600B publication Critical patent/CN111701600B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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-
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C2603/74—Adamantanes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the technical field of medicines, and particularly discloses a catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof. The catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO 4 2‑ /ZrO 2 ‑Al 2 O 3 ‑Pr 6 O 11 Wherein, al in the catalyst 2 O 3 The mass content of (2) is 4.2-6.3%; pr (Pr) 6 O 11 The mass content of (2.0-2.8 percent); SO (SO) 4 2‑ The mass content of (2) is 5.6-13.7%. The catalyst is used in the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene. The catalyst for preparing 1-bromo-3, 5-dimethyl adamantane provided by the invention has the advantages that through the combined action of various active components, the catalytic activity of the catalyst is high, the activity is stable, the catalyst can be recycled, the environmental pollution is avoided, 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-dimethyl adamantane 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. Because of different action mechanisms, the memantine hydrochloride can be used together with cholinesterase inhibitors to increase the curative effect.
1-bromo-3, 5-dimethyl adamantane is a key intermediate for preparing memantine hydrochloride, and the preparation method of 1-bromo-3, 5-dimethyl adamantane in the prior art comprises the following steps: taking perhydroacenaphthene as a starting material, carrying out rearrangement reaction under the action of anhydrous aluminum trichloride serving as a catalyst to obtain 1, 3-dimethyl adamantane, and further carrying out bromination reaction with bromine to obtain 1-bromo-3, 5-dimethyl adamantane.
However, the process requires a large amount of anhydrous aluminum trichloride during the rearrangement reaction, and a large amount of clean water is required for washing the reaction liquid in the subsequent treatment to remove the aluminum trichloride, thereby generating a large amount of wastewater containing aluminum trichloride, which has high energy consumption and seriously pollutes the environment.
Therefore, it is of great importance to research a clean catalyst for preparing memantine hydrochloride key intermediate 1-bromo-3, 5-dimethyl adamantane, which is suitable for industrial production.
Disclosure of Invention
Aiming at the technical problems existing in the existing preparation process of 1-bromo-3, 5-dimethyl adamantane, the invention provides a catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
a catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Wherein, al in the catalyst 2 O 3 The mass content of (2) is 4.2-6.3%; pr (Pr) 6 O 11 The mass content of (2.0-2.8 percent); SO (SO) 4 2- The mass content of (2) is 5.6-13.7%.
Compared with the prior art, the catalyst for preparing the 1-bromo-3, 5-dimethyl adamantane is prepared by adopting an Al coprecipitation impregnation method 2 O 3 And Pr (Pr) 6 O 11 Doping modified SO 4 2- /ZrO 2 The solid acid catalyst has high catalytic activity and stable activity under the combined action of a plurality of active components, 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, regulating the pH 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, soaking the precursor solid powder in sulfuric acid, drying, and calcining to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 。
Al is prepared by adopting a coprecipitation impregnation method 2 O 3 And Pr (Pr) 6 O 11 Doping modified SO 4 2- /ZrO 2 Solid acid catalysts improve 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 temperature of the drying is 100-120 ℃ and the time is 12-13 h; the calcination temperature is 500-600 ℃ and the calcination time is 2.5-3.5 h.
Further, 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 application of the catalyst in the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene.
The invention also provides a synthesis method of the 1-bromo-3, 5-dimethyl adamantane, which takes perhydroacenaphthene as a raw material, and under the action of the catalyst, the rearrangement reaction is carried out to obtain the 1, 3-dimethyl adamantane, and the bromination reaction is carried out on the obtained 1, 3-dimethyl adamantane to obtain the 1-bromo-3, 5-dimethyl adamantane.
The invention provides a synthesis method of 1-bromo-3, 5-dimethyl adamantane, which uses SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 The catalyst is convenient to recycle, 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.
Further, 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 ℃ and the time is 6-6.5 h, so that 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 solvent containing bromine at the temperature of 0-20 ℃, then the reflux reaction is carried out for 18-20 hours, and the 1-bromo-3, 5-dimethyl adamantane is obtained after separation.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, wherein the catalyst is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Instant Al 2 O 3 And Pr (Pr) 6 O 11 Doping modified SO 4 2- /ZrO 2 A solid acid catalyst, wherein Al in the catalyst 2 O 3 The mass content of (2) is 4.2-6.3%; pr (Pr) 6 O 11 The mass content of (2.0-2.8 percent); SO (SO) 4 2- The mass content of (2) is 5.6-13.7%.
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and the 1-bromo-3, 5-dimethyl adamantane is prepared through the following reaction steps.
Figure BDA0002567558560000031
In the presence of the catalyst, the perhydroacenaphthene undergoes a rearrangement reaction to obtain 1, 3-dimethyl adamantane, and the obtained 1, 3-dimethyl adamantane undergoes a bromination reaction to obtain 1-bromo-3, 5-dimethyl adamantane.
In order to better illustrate the catalyst for preparing 1-bromo-3, 5-dimethyladamantane provided in the examples of the present invention, further illustration is provided below by way of examples.
Example 1
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Wherein, al in the catalyst 2 O 3 Is 5% by mass; pr (Pr) 6 O 11 The mass content of (2.5 percent); SO (SO) 4 2- The mass content of (2) is 9.8%, and inductively coupled plasma emission spectroscopy (ICP-AES) is adopted for metal element content measurement; sulfate content was determined using thermogravimetric-differential scanning calorimetric analysis (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g and praseodymium nitrate hexahydrate (Pr (NO) 3 ) 3 ·6H 2 O) 2.4g, dissolving in 850ml deionized water, stirring until the solution is clear, slowly dropwise adding 25% ammonia water until the system ph=10, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature for 2h, vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 120 ℃ for 12h, and grinding into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2 hours, vacuum filtering, drying a filter cake at 120 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 3 hours to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Stirring and heating to 180 ℃ for reaction for 6 hours, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing vacuum rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (57.6 g), wherein the yield is 95.7%, and the GC purity is 99.7%.
S2: 50ml of methylene chloride and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 20 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 77.0g of 1-bromo-3, 5-dimethyl adamantane, the yield is 90.3%, and the GC purity is 99.6%.
Example 2
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Wherein the mole ratio of Zr/Al/Pr is 20:2:0.3, and Al in the catalyst is as follows 2 O 3 The mass content of (2) is 4.2%; pr (Pr) 6 O 11 The mass content of (2.1 percent); SO (SO) 4 2- The mass content of (2) is 5.6%, and inductively coupled plasma emission spectroscopy (ICP-AES) is adopted for metal element content measurement; sulfate content was determined using thermogravimetric-differential scanning calorimetric analysis (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g andpraseodymium nitrate hexahydrate (Pr (NO) 3 ) 3 ·6H 2 O) 2.4g, dissolving in 850ml deionized water, stirring until the solution is clear, slowly dropwise adding 25% ammonia water until the system ph=9.5, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature at 25 ℃ for 2.5h, then vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 100 ℃ for 13h, and grinding into 200-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 1.5h, vacuum filtering, drying the filter cake at 100 ℃ for 13h, and finally roasting in a muffle furnace at 500 ℃ for 3.5h to obtain the catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Stirring and heating to 150 ℃ for reaction for 7h, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing vacuum rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (58.1 g), wherein the yield is 96.5%, and the GC purity is 99.8%.
S2: 50ml of methylene chloride and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 18 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 77.3g of 1-bromo-3, 5-dimethyl adamantane, the yield is 90.7%, and the GC purity is 99.7%.
Example 3
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Wherein the mole ratio of Zr/Al/Pr is 20:3:0.4, and Al in the catalyst is as follows 2 O 3 The mass content of (2) is 6.25%; pr (Pr) 6 O 11 The mass content of (2.8 percent); SO (SO) 4 2- The mass content of (2) is 13.7%, and inductively coupled plasma emission spectroscopy (ICP-AES) is adopted for metal element content measurement; sulfate content was determined using thermogravimetric-differential scanning calorimetric analysis (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g and praseodymium nitrate hexahydrate (Pr (NO) 3 ) 3 ·6H 2 O) 2.4g, dissolving in 850ml deionized water, stirring until the solution is clear, slowly dropwise adding 25% ammonia water until the system ph=10.5, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature for 2h, vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 110 ℃ for 12h, and grinding into 100-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2.5h, vacuum filtering, drying the filter cake at 110 ℃ for 12h, and finally roasting in a muffle furnace at 600 ℃ for 2.5h to obtain the catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Stirring and heating to 160 ℃ for reaction for 6.5h, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing reduced pressure rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (58.2 g), wherein the yield is 96.7%, and the GC purity is 99.7%.
S2: 50ml of methylene chloride and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, 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 (about 4.5h after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 19h after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 77.6g of 1-bromo-3, 5-dimethyl adamantane, the yield is 91.0%, and the GC purity is 99.7%.
Example 4
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Wherein the mol ratio of Zr/Al/Pr is 100:12:1.8, and Al in the catalyst is as follows 2 O 3 Is 5% by mass; pr (Pr) 6 O 11 The mass content of (2.5 percent); SO (SO) 4 2- The mass content of (2) is 10%, and inductively coupled plasma emission spectroscopy (ICP-AES) is adopted for metal element content measurement; sulfate content was determined using thermogravimetric-differential scanning calorimetric analysis (TG-DSC).
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g and praseodymium nitrate hexahydrate (Pr (NO) 3 ) 3 ·6H 2 O) 2.4g, dissolving in 850ml deionized water, stirring until the solution is clear, slowly dropwise adding 25% ammonia water until the system ph=10, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature for 2h, vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 120 ℃ for 12h, and grinding into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2 hours, vacuum filtering, drying a filter cake at 120 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 3 hours to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Stirring and heating to 200 ℃ for reaction for 5 hours, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing vacuum rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (57.5 g), wherein the yield is 95.6%, and the GC purity is 99.6%.
S2: 50ml of methylene chloride and 61.4g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 20 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 77.2g of 1-bromo-3, 5-dimethyl adamantane, the yield is 90.5%, and the GC purity is 99.5%.
In order to better illustrate the catalyst for preparing 1-bromo-3, 5-dimethyladamantane provided in the examples of the present invention, further illustration is provided below by way of comparative example.
Comparative example 1
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 。
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g is dissolved in 850ml deionized water, stirred until the solution is clear, and 25% ammonia water is slowly added dropwise until the system ph=10, and the reverse reaction is controlled during the ammonia water adding processThe temperature is not higher than 50 ℃ and the temperature is kept at 45 ℃ for 2 hours, then vacuum filtration is carried out, the filter cake is washed by deionized water until no chloride ions exist, and the filter cake is dried for 12 hours at 120 ℃ and then is ground into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2 hours, vacuum filtering, drying a filter cake at 120 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 3 hours to obtain a catalyst SO 4 2- /ZrO 2 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 Stirring and heating to 200 ℃ for reaction for 10 hours, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing reduced pressure rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (52.6 g), wherein the yield is 81.1%, and the GC purity is 92.5%.
S2: 50ml of methylene chloride 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 20 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 61.7g of 1-bromo-3, 5-dimethyl adamantane, the yield is 85.2%, and the GC purity is 99.5%.
Comparative example 2
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 。
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g, dissolving in 850ml deionized water, stirring until dissolution and clarification, slowly dropwise adding 25% ammonia water until the system ph=10, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature for 2h at 45 ℃, vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 120 ℃ for 12h, and grinding into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2 hours, vacuum filtering, drying a filter cake at 120 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 3 hours to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 Stirring and heating to 150 ℃ for reaction for 10 hours, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing reduced pressure rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (52.9 g), wherein the yield is 81.3%, and the GC purity is 92.2%.
S2: 50ml of methylene chloride 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 20 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 62.9g of 1-bromo-3, 5-dimethyl adamantane, the yield is 86.3%, and the GC purity is 99.0%.
Comparative example 3
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 -La 2 O 3 。
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g and lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O) 2.5g, dissolving in 850ml deionized water, stirring until the solution is clear, slowly dropwise adding 25% ammonia water until the system ph=10, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature for 2h, vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 120 ℃ for 12h, and grinding into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2 hours, vacuum filtering, drying a filter cake at 120 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 3 hours to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -La 2 O 3 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 -La 2 O 3 Stirring and heating to 180 ℃ for reaction for 6 hours, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing vacuum rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (53.8 g), the yield is 83.7%, and the GC purity is 93.3%.
S2: 50ml of methylene chloride and 53.7g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 20 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 65.1g of 1-bromo-3, 5-dimethyl adamantane, the yield is 86.9%, and the GC purity is 99.2%.
Comparative example 4
Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane, which is SO 4 2- /ZrO 2 -Al 2 O 3 -CeO 2 。
The preparation method of the catalyst specifically comprises the following reaction steps:
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) 100.0g, aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) 14.0g and cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) 2.4g, dissolving in 850ml deionized water, stirring until the solution is clear, slowly dropwise adding 25% ammonia water until the system ph=10, controlling the reaction temperature not to exceed 50 ℃ in the process of dropwise adding ammonia water, keeping the temperature for 2h, vacuum filtering, washing a filter cake with deionized water until no chloride ions exist, drying the filter cake at 120 ℃ for 12h, and grinding into 180-mesh powder. Adding the solid powder into 200ml of 2.0mol/L sulfuric acid solution, stirring and soaking for 2 hours, vacuum filtering, drying a filter cake at 120 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 3 hours to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -CeO 2 。
The catalyst is applied to the reaction of synthesizing 1-bromo-3, 5-dimethyl adamantane from perhydroacenaphthene, and specifically comprises the following steps:
s1: 60.0g of perhydroacenaphthene and 5.0g of the catalyst SO are added into a 100mL reaction bottle 4 2- /ZrO 2 -Al 2 O 3 -CeO 2 Stirring and heating to 160 ℃ for reaction for 8.5h, then cooling to below 30 ℃, filtering and recovering the catalyst, and performing reduced pressure rectification (vacuum degree is minus 0.098 to minus 0.1 MPa) on the obtained filtrate in a rectifying tower to obtain 1, 3-dimethyl adamantane (54.2 g), wherein the yield is 84.6%, and the GC purity is 93.6%.
S2: 50ml of methylene chloride and 54.3g of bromine are added into a 500ml reaction bottle, the mixture is stirred and cooled to 0 ℃, then 54.2g 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 (about 5 hours after the dripping is finished), then the temperature is increased to reflux reaction, and the reaction is monitored by gas chromatography until the reaction is finished (about 20 hours after the reaction is finished). After the reaction, the system is cooled to 20 ℃, 100ml of 5% sodium bisulphite aqueous solution is added, stirred, kept stand and separated, the organic phase is washed by water (50 ml multiplied by 2), dried by adding anhydrous sodium sulfate, filtered, concentrated and distilled under reduced pressure to obtain 65.8g of 1-bromo-3, 5-dimethyl adamantane, the yield is 87.2%, and the GC purity is 99.5%.
The catalyst recovered in example 1 and comparative examples 1 to 4 was recycled, and the number of times of recycling and the yield and purity of 1, 3-dimethyladamantane were counted, and the results are shown in Table 1.
TABLE 1
Figure BDA0002567558560000121
From the data, the catalyst for preparing the 1-bromo-3, 5-dimethyl adamantane provided by the invention has the advantages that through the combined action of various active components, the catalytic activity of the catalyst is high, the activity is stable, the catalyst can be recycled, the environmental pollution is avoided, the cost can be effectively reduced, and the product yield and the purity are improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.

Claims (9)

1. A catalyst for preparing 1-bromo-3, 5-dimethyl adamantane is characterized in that the catalyst is SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 Wherein, al in the catalyst 2 O 3 The mass content of the (C) is 4.2-6.3%; pr (Pr) 6 O 11 The mass content of the (B) is 2.0-2.8%; SO (SO) 4 2- The mass content of the (B) is 5.6-13.7%;
the preparation method of the catalyst comprises the following steps:
dissolving zirconium oxychloride, aluminum nitrate and praseodymium nitrate in deionized water, regulating the pH 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, soaking the precursor solid powder in sulfuric acid, drying, and calcining to obtain a catalyst SO 4 2- /ZrO 2 -Al 2 O 3 -Pr 6 O 11 。
2. The catalyst for preparing 1-bromo-3, 5-dimethyladamantane according to claim 1, 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.
3. The catalyst for preparing 1-bromo-3, 5-dimethyladamantane according to claim 1, wherein: in the second step, the temperature of the drying is 100-120 ℃ and the time is 12-13 h; the calcination temperature is 500-600 ℃ and the calcination time is 2.5-3.5 h.
4. The catalyst for preparing 1-bromo-3, 5-dimethyladamantane according to claim 1, wherein: the particle size of the precursor solid powder is 100-200 meshes, and the soaking time is 1.5-2.5 h.
5. Use of a catalyst according to any one of claims 1 to 4 for the preparation of 1-bromo-3, 5-dimethyladamantane in the synthesis of 1-bromo-3, 5-dimethyladamantane from acenaphthene.
6. A synthesis method of 1-bromo-3, 5-dimethyl adamantane is characterized in that: taking perhydroacenaphthene as raw material, carrying out rearrangement reaction under the action of the catalyst of any one of claims 1 to 5 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.
7. The method for synthesizing 1-bromo-3, 5-dimethyladamantane according to claim 6, wherein: the reaction temperature of the rearrangement reaction is 150-200 ℃ and the time is 5-7 h.
8. The method for synthesizing 1-bromo-3, 5-dimethyladamantane according to claim 7, wherein: the reaction temperature of the rearrangement reaction is 160-180 ℃ and the time is 6-6.5 h.
9. The method for synthesizing 1-bromo-3, 5-dimethyladamantane according to claim 6, wherein: in the bromination reaction process, 1, 3-dimethyl adamantane is dropwise added into a bromine-containing solvent at the temperature of 0-20 ℃, then the reflux reaction is carried out for 18-20 h, and the 1-bromo-3, 5-dimethyl adamantane is obtained after separation.
CN202010628587.6A 2020-07-02 2020-07-02 Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof Active CN111701600B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010628587.6A CN111701600B (en) 2020-07-02 2020-07-02 Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010628587.6A CN111701600B (en) 2020-07-02 2020-07-02 Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof

Publications (2)

Publication Number Publication Date
CN111701600A CN111701600A (en) 2020-09-25
CN111701600B true CN111701600B (en) 2023-06-06

Family

ID=72546169

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010628587.6A Active CN111701600B (en) 2020-07-02 2020-07-02 Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof

Country Status (1)

Country Link
CN (1) CN111701600B (en)

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
"固体酸催化异构化反应的研究";王瑞芬;《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》;20061215(第12期);第8页第2.3.3节 *

Also Published As

Publication number Publication date
CN111701600A (en) 2020-09-25

Similar Documents

Publication Publication Date Title
CN101940947B (en) Method for preparing polystyrene resin-immobilized Salon-Co (III) catalyst
CN112624917B (en) Method for producing crotonic acid by catalytic oxidation method
CN101648978A (en) Preparation method of high purity hexaphenoxycyclotriphosphazene
CN112159357B (en) Refining method of caprolactam
CN103896811A (en) Method for preparing 1,6-hexamethylene diurethane through heterogeneous catalysis
CN113368843A (en) Strontium titanate supported palladium catalyst for CL-20 synthesis and preparation application thereof
CN113024351A (en) Production method of isopropanol
CN101961661B (en) Organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and preparation method and application thereof
CN111701600B (en) Catalyst for preparing 1-bromo-3, 5-dimethyl adamantane and application thereof
CN101628909B (en) Method for synthesizing 1,4-dioxane-2-ketone by ethylene glycol
CN112645813B (en) Preparation method of (R) -3-cyclohexene carboxylic acid
CN109320425A (en) A kind of synthetic method of rimantadine hydrochloride
CN101343261B (en) Method for preparing epoxy cyclohexane
CN101205170B (en) Utilization method of solid catalyst for cyclohexanone self-condensation reaction
CN110627743B (en) Method for preparing morpholine and monoethylamine by using N-ethylmorpholine
CN110143871B (en) Preparation method of dicarboxylic acid diol ester
CN101857533B (en) Process for producing methylal by composite solid-acid catalyst
CN110724046A (en) Method for preparing o-methylbenzoic acid and phthalide from phthalic anhydride
CN109499618A (en) A kind of catalyst and the preparation method and application thereof being used to prepare benzoyl formic acid and its ester type compound
CN112724086B (en) Preparation method of 5-amino-4-nitrile-1, 3-diphenylpyrazole
CN110790690A (en) Synthetic method of 3, 4-difluoro-2- ((phenylthio) methyl) benzoic acid
CN112939045B (en) Preparation method of superfine high-purity gamma-alumina
CN113121616A (en) Method for preparing fructose through glucose chemical isomerization
CN104130154A (en) Method for preparing high-purity agomelatine
CN114920635B (en) Preparation method of 4-hydroxy-1-indenone

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant