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CN116375667A - Epoxidation method of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester - Google Patents

Epoxidation method of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester Download PDF

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CN116375667A
CN116375667A CN202310650510.2A CN202310650510A CN116375667A CN 116375667 A CN116375667 A CN 116375667A CN 202310650510 A CN202310650510 A CN 202310650510A CN 116375667 A CN116375667 A CN 116375667A
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cyclohexene
carboxylic acid
catalyst
epoxidation
ylmethyl ester
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高峰
孙琪
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Beijing Mediking Biopharm Co ltd
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Beijing Mediking Biopharm Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

An epoxidation method of 3-cyclohexene-1-methanoic acid-3-cyclohexene-1-methyl ester, which in particular relates to the technical fields of organic synthesis and medicine. According to the method, a novel organic tungsten catalyst is used for catalyzing a diene compound 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-methyl ester to carry out epoxidation to generate 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, a saturated sodium sulfite solution is added into a reaction solution after the reaction is finished to remove excessive hydrogen peroxide, and after the reaction solution is separated and concentrated, most of the catalyst is recovered, the catalyst is distilled under reduced pressure to obtain a product, and the catalyst can be repeatedly used. In the invention, when 3-cyclohexene-1-methanoic acid-3-cyclohexene-1-methyl ester is catalytically oxidized, a novel organic tungsten is adopted as a catalytic method of the catalyst, so that a reaction scheme is optimized, the traditional complex synthesis method is avoided, the atom economy is improved, the recycling times of the reaction catalyst are increased, the loss of products is reduced due to the improvement of the reactivity, and the yield is improved.

Description

Epoxidation method of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester
Technical Field
The invention relates to the technical field of organic synthesis and medicine, in particular to a chemical catalytic method for olefin double bond epoxidation.
Background
The 3, 4-epoxy cyclohexylmethyl-3, 4-epoxy cyclohexylformate is an intermediate of epoxy resin, and can be used for coating food packaging materials, and can also be used for light modeling, manufacturing medical models, electronic material intermediates, automobile priming paint and high-voltage cables. The conventional synthesis process is catalyzed by organic peroxy acids such as m-chloroperoxybenzoic acid, peracetic acid or DDO.
However, the conventional process has problems such as low utilization rate of peroxy acid atoms, increased difficulty in separation and purification of products, and adverse environmental impact caused by the discharge of waste (liquid). The above problems not only increase the cost, but also bring unavoidable disasters to people and the environment. Thus, critical steps in the process need to be improved and optimized.
Disclosure of Invention
Therefore, the invention provides an epoxidation method of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-methyl ester, which aims to solve the problems of low purity, difficult separation and the like when the existing organic peroxyacid is used as a catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
according to one aspect of the present invention there is provided a process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester, said process comprising:
dissolving an organic tungsten catalyst MDK and 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-yl methyl ester in 1, 2-dichloroethane, stirring, and then dropwise adding hydrogen peroxide;
heating in an oil bath, controlling the reaction temperature, and performing an epoxidation reaction;
adding saturated sodium sulfite solution into the reacted solution to remove hydrogen peroxide, separating liquid, concentrating, filtering, and distilling under reduced pressure to obtain the 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate product.
Further, the preparation method of the organic tungsten catalyst MDK comprises the following steps: tungstic acid and H were added to a three-necked flask 2 0 2 Stirring in water bath to colorless clear solution, filtering while hot, cooling to room temperature, and adding 85% H 3 PO 4 Stirring at room temperature, and dripping chloroform solution of cetyl pyridine bromide into the solutionAnd (3) after the liquid is added dropwise, stirring, separating the liquid, adding anhydrous sodium sulfate into an organic layer for drying, and evaporating the solvent to obtain the catalyst intermediate.
A flask with stirring, thermometer and condenser was charged with catalyst intermediate (1 eq) using 30% H 2 0 2 After the solution was clarified, the solution was stirred at room temperature. Dissolving dioctadecyl dimethyl chloride in tert-butyl alcohol according to (2 eq), vigorously stirring the mixed solution to form white flocculent suspended matters, filtering the suspended matters, washing the suspended matters with water, and vacuum drying the suspended matters to obtain the organic tungsten catalyst MDK; [ (C) 18 H 37 ) 2 (CH 3 ) 2 N] 3 (PO 4 ){WO(O 2 ) 2 } 2 {WO(O 2 ) 2 (H 2 O)}。
Further, the mass fraction of the hydrogen peroxide is 30%.
Further, the molar ratio of the hydrogen peroxide to the 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester is 2-3: 1.
further, the volume ratio of the 1, 2-dichloroethane to the 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester is 2-5:1.
Further, the temperature of the hydrogen peroxide is 50-80 ℃ during dropwise adding.
Further, the temperature of the cyclization reaction is 50-70 ℃ and the reaction time is 1.5-3h.
According to another aspect of the present invention there is provided a process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester, obtainable by the process of any one of claims 1 to 6.
The invention has the following advantages:
in the invention, when 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-methyl ester is catalyzed and epoxidized, the novel organic tungsten with high activity is used as a catalyst, so that the reaction scheme is optimized, and the selectivity of the reaction is greatly improved. The catalyst has high activity on olefin epoxidation and good selectivity; and the preparation is simple and is easy for mass production. The cyclic use times of the reaction catalyst can reach more than 20 times, and the activity of the novel catalyst is not obviously reduced after the novel catalyst is circulated. And the selectivity is greatly improved, so that the loss of products is reduced, and the yield is improved.
The invention uses hydrogen peroxide to replace organic peroxy acid for oxidation reaction, greatly improves the operation safety, reduces the synthesis cost and has low reaction risk coefficient. Reduces the problems of environmental pollution, post-treatment difficulty, operation danger and the like caused by the discharge of waste (liquid). The optimized reaction scheme has the advantages of improved yield, reduced cost and environmental friendliness, and meets the requirements of green modern production.
Drawings
FIG. 1 is a gas spectrum of the product of example 2.
FIG. 2 is a gas spectrum of the product of example 3.
FIG. 3 is a gas spectrum of the product of example 4.
Description of the embodiments
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The concentration of hydrogen peroxide and phosphoric acid refers to mass fraction unless otherwise specified.
Example 1
Into a three-necked flask, 25.0g of tungstic acid and 350ml of 27.5% H were charged 2 0 2 Stirring in water bath at 60deg.C to obtain colorless clear solution, filtering while hot, cooling to room temperature, and adding 85% H 3 PO 4 2.88g, stirring for 30min at room temperature, adding 17.0g of cetylpyridinium bromide chloroform solution dropwise to the solution, stirring for 30min after the dropwise addition, separating the solution, adding anhydrous sodium sulfate into an organic layer, drying, and evaporating the solvent to obtain a catalyst intermediate.
A flask with stirring, thermometer and condenser was charged with catalyst intermediate (2.5 g,0.85 mmol) using 48mL of 30% H 2 0 2 The solution is dissolved and the mixture is stirred,after the solution was clear, the solution was stirred at room temperature for 4h. Dioctadecyl dimethyl chloride (1 g,1.7 mmol) was dissolved in 25ml t-butanol, the mixed solution was vigorously stirred at 45 ℃ for 4h, white flocculent suspension appeared, which was filtered, then washed with a large amount of water (100 ml of 45 ℃ warm water), and dried in vacuo to give novel tungsten catalyst MDK, white powder, 1.1g of green product, 75% yield.
Example 2
The present experiment provides a process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester:
to a 1000mL three-necked flask was added 4g of a novel organic tungsten catalyst MDK (1.57 mmol), 60mL of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester (about 260 mmol), 0.5g of EDTA, and 150mL of 1, 2-dichloroethane were dissolved, 65mL of 30% hydrogen peroxide (molar ratio of hydrogen peroxide to 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester about 2.3) was slowly added dropwise with stirring at 50℃and the system temperature at the time of dropwise addition was controlled to 50-80℃and the temperature was raised to 60℃after the completion of dropwise addition. The reaction was stirred at this temperature for 2h. After the reaction is finished, removing hydrogen peroxide from the reaction solution, separating the solution, concentrating the solution, recovering most of the catalyst, and distilling the reaction solution under reduced pressure to obtain a product. The yield was 98.3% and the purity (GC) was greater than 98%.
Example 3
The present experiment provides a process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester:
to a 500mL three-necked flask was added 2g of an organic tungsten catalyst MDK (0.78 mmol), 30 mL of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester (about 130 mmol), 0.25g of EDTA, 75mL of 1, 2-dichloroethane were dissolved, 37mL of 30% hydrogen peroxide (molar ratio of hydrogen peroxide to 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester: about 2.3) was slowly added dropwise with stirring at 50℃under control of the system temperature at 50-80℃and the temperature was raised to 60℃after the completion of the dropwise addition. The reaction was stirred at this temperature for 2h. After the reaction is finished, removing hydrogen peroxide from the reaction solution, separating the solution, concentrating the solution, recovering most of the catalyst, and distilling the reaction solution under reduced pressure to obtain a product. The yield was 98.8% and the purity (GC) was greater than 99%.
Example 4
The present experiment provides a process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester:
to a 100mL three-necked flask was added 0.4g of the recovered organic tungsten catalyst MDK (0.157 mmol), 6mL of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester (about 26 mmol), 50mg of EDTA, and 15mL of 1, 2-dichloroethane were dissolved, 6.5mL of 30% hydrogen peroxide (molar ratio of hydrogen peroxide to 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester: about 2.3) was slowly added dropwise with stirring at 50℃under control of the system temperature at 50-80℃and the temperature was raised to 60℃after the completion of the dropwise addition. The reaction was stirred at this temperature for 2h. After the reaction is finished, removing hydrogen peroxide from the reaction solution, separating the solution, concentrating the solution, recovering most of the catalyst, and distilling the reaction solution under reduced pressure to obtain a product. The yield was 98.1% and the purity (GC) was greater than 99.5%.
As can be seen from this example, no significant decrease in catalyst activity occurred after recycling.

Claims (7)

1. A process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester, said process comprising the steps of:
dissolving an organic tungsten catalyst MDK and 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-yl methyl ester in 1, 2-dichloroethane, stirring, and then dropwise adding hydrogen peroxide;
heating in an oil bath, controlling the reaction temperature, and performing an epoxidation reaction;
adding saturated sodium sulfite solution into the reacted solution to remove hydrogen peroxide, and separating, concentrating, filtering and distilling under reduced pressure to obtain the 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate product.
2. The method for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester according to claim 1, wherein the mass fraction of the hydrogen peroxide solution is 30%.
3. The method for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester according to claim 1, wherein the molar ratio of the hydrogen peroxide solution to the 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester is 2-3: 1.
4. the method for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester according to claim 1, characterized in that the volume ratio of 1, 2-dichloroethane to 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester is 2-5: 1.
5. the method for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester according to claim 1, wherein the temperature is 50-80 ℃ when hydrogen peroxide is added dropwise.
6. The process for the epoxidation of 3-cyclohexene-1-carboxylic acid-3-cyclohexen-1-ylmethyl ester according to claim 1, characterized in that the temperature of the cyclization reaction is 50-70℃and the reaction time is 1.5-3h.
7.3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, characterized in that it is obtainable by a process according to any one of claims 1 to 6.
CN202310650510.2A 2023-06-04 2023-06-04 Epoxidation method of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester Pending CN116375667A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010168330A (en) * 2009-01-26 2010-08-05 Showa Denko Kk Method for producing epoxy compound
CN101959872A (en) * 2008-02-28 2011-01-26 昭和电工株式会社 The manufacture method of epoxy compounds
WO2013133009A1 (en) * 2012-03-07 2013-09-12 国立大学法人東京大学 Method for producing tungsten peroxide compound, and method for producing epoxy compound
CN104998689A (en) * 2015-06-29 2015-10-28 湖北大学 Anion resin-carried peroxyphosphotungstic acid, its preparation method and use, and epoxycycloparaffin synthesis method
WO2018097150A1 (en) * 2016-11-24 2018-05-31 帝人ファーマ株式会社 Epoxy compound production method
CN110479374A (en) * 2019-09-20 2019-11-22 济南大学 A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane
CN113880790A (en) * 2021-11-12 2022-01-04 泉州师范学院 Phase transfer catalytic synthesis method of 3, 4-epoxy cyclohexyl methyl-3 ',4' -epoxy cyclohexyl formic ether

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101959872A (en) * 2008-02-28 2011-01-26 昭和电工株式会社 The manufacture method of epoxy compounds
JP2010168330A (en) * 2009-01-26 2010-08-05 Showa Denko Kk Method for producing epoxy compound
WO2013133009A1 (en) * 2012-03-07 2013-09-12 国立大学法人東京大学 Method for producing tungsten peroxide compound, and method for producing epoxy compound
CN104998689A (en) * 2015-06-29 2015-10-28 湖北大学 Anion resin-carried peroxyphosphotungstic acid, its preparation method and use, and epoxycycloparaffin synthesis method
WO2018097150A1 (en) * 2016-11-24 2018-05-31 帝人ファーマ株式会社 Epoxy compound production method
CN110479374A (en) * 2019-09-20 2019-11-22 济南大学 A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane
CN113880790A (en) * 2021-11-12 2022-01-04 泉州师范学院 Phase transfer catalytic synthesis method of 3, 4-epoxy cyclohexyl methyl-3 ',4' -epoxy cyclohexyl formic ether

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