CN105854938A - Polystyrene supported type catalyst and application method thereof in synthesis of dihydrocoumarin - Google Patents
Polystyrene supported type catalyst and application method thereof in synthesis of dihydrocoumarin Download PDFInfo
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- CN105854938A CN105854938A CN201510380365.6A CN201510380365A CN105854938A CN 105854938 A CN105854938 A CN 105854938A CN 201510380365 A CN201510380365 A CN 201510380365A CN 105854938 A CN105854938 A CN 105854938A
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Abstract
The invention discloses a polystyrene supported type catalyst and an application method thereof in synthesis of dihydrocoumarin; the polystyrene supported type catalyst is used for catalyzing 1-indanone to synthesize a lactone compound and particularly includes the following steps: adding 1-indanone and an organic solvent into a container, dropwise adding a hydrogen peroxide solution and the polystyrene supported type catalyst, and carrying out a stirring reaction, after the reaction is finished, precipitating the catalyst with ethanol, centrifuging the reaction solution, extracting the supernatant, washing, and distillating to obtain dihydrocoumarin. The polystyrene supported type catalyst has the advantages that with use of the polystyrene supported type catalyst, the preparation method is simple, the 1-indanone conversion rate is increased, the atom utilization rate of the reaction is improved, moreover, the polystyrene supported type catalyst is reused, no waste acid is treated, and the polystyrene supported type catalyst has the characteristics of energy saving, emission reduction, good selectivity, high atom efficiency, mild reaction conditions, environmental cleaning and the like, and is suitable for industrial engineering application.
Description
Technical field
The present invention relates to a kind of loaded by polystyrene type catalyst and the application process in dihydrocoumarin synthesizes thereof, i.e. with 1-indone as raw material, with hydrogen peroxide as Green Oxidant, application load Fe-sulfonated polystyrene is the method that catalyst is aoxidized by Baeyer-Villiger oxidation reaction catalysis, substitute the traditional method synthesizing dihydro coumarin being raw material high-temperature high-voltage reaction with coumarin, as organic functional material preparation fields such as medicine, spice, dyestuffs.
Background technology
Catalyst carrier is also called carrier, is one of mainly comprising of loaded catalyst.Carrier can make the catalyst made have suitable shape, size and mechanical strength, to meet the operation requirement of industrial reactor；Carrier can make active component be dispersed on carrier surface, it is thus achieved that higher specific surface area, improves the catalytic efficiency of unit mass active component, and carrier itself does not typically have catalysis activity.Conventional catalyst carrier has alumina support, silica-gel carrier, absorbent charcoal carrier and some natural product such as Pumex, kieselguhr etc..It is good that loaded catalyst often has catalytic performance, the easily separated feature such as can recycle and reuse.
Dihydrocoumarin is critically important chemical intermediate, is widely used in the preparation of medicine, spice, cosmetics and food additive.Natural dihydrocoumarin is present in Herba Meliloti officinalis.Dihydrocoumarin has application as important lactone at a lot of aspects, can be used for modulating butter, Cortex cocois radicis, Cortex Cinnamomi flavor essence, also serves as flavouring essence for tobacco, and synthesizing dihydro coumarin has great application prospect.
Natural dihydrocoumarin is present in Herba Meliloti officinalis.Traditional preparation method is divided into following four: (1) with coumarin as raw material, in the presence of a nickel catalyst, at 160～200 DEG C and add pressure hydrogenation and obtain；(2) with adjacent chlorobenzene propanoic acid as raw material, hydrolyze in alkaline aqueous solution, generate o-hydroxy propanoic acid, dehydration, closed loop and obtain；(3) with ortho-aminotoluene as raw material, in aqueous hydrochloric acid solution, hydrolysis generates ortho-chlorotolu'ene, chlorination, generates adjacent chlorophenylmethyl chlorine, hydrolysis, generate o-chlorobenzaldehyde, with acetic acidreaction in sodium acetate solution, generate adjacent chlorobenzene acrylic acid, hydrogenation, in alkaline aqueous solution hydrolyze, generate o-hydroxy propanoic acid, dehydration closed-loop and obtain；(4) with ortho-methyl phenol as raw material, with triclosan oxidation phosphorus reaction, again chlorination, react with Sodium ethylate at 160～180 DEG C, generate coumarin, finally hydrogenation and obtain.Prior synthesizing method is complex, and reactions steps is loaded down with trivial details, and reaction condition requires height, and separation and recovery product is difficult to, and productivity is undesirable.
Some documents are had to relate to by using peroxide to improve the productivity of dihydrocoumarin in catalysis oxidation.But, the cost separating and reclaiming is costly, and peroxide is the most serious to the pollution of environment.CN101774990 B illustrates a kind of method preparing dihydrocoumarin without phenol, the method is applied cinnamic acid primary raw material, has first synthesized 1-indone, then with hydrogen peroxide for oxidizer catalytic oxidative synthesis dihydrocoumarin.This method avoid the generation of phenol wastewater in commercial production, but reaction employs peroxide carbamide as catalyst, environment is affected and is unfavorable for the recovery of catalyst.
Along with the development of environmental economy, the shortcoming of said method more and more shows, and mainly shows themselves in that (1) reaction selectivity is the highest, forms substantial amounts of organic by-products refuse, and environmental pollution is serious；(2) energy consumption is big, and peroxide is big to the corrosivity of equipment, and poor stability, has certain risk.In view of the demand of dihydrocoumarin is by increasing, along with the development of environmental economy, traditional production method of dihydrocoumarin does not have sustainable developability, is necessarily replaced by more environment-friendly method.
Summary of the invention
It is an object of the invention to: providing a kind of loaded catalyst and the application process in dihydrocoumarin synthesizes thereof, with hydrogen peroxide as Green Oxidant, not using peroxide is catalyst, reaction condition is gentle, and selectivity is good, and yield is high, produce without spent acid, be suitable for through engineering approaches to convert.
The technical solution of the present invention is: this loaded catalyst be polystyrene is dissolved in a solvent after through concentrated sulphuric acid at room temperature sulfonation, then with ethanol separate out, filter, be dried, obtain sulfonated polystyrene；Then with the upper Fe of infusion process absorption after sulfonated polystyrene being dissolved again3+, filter after precipitation, be dried and prepare loaded by polystyrene type catalyst.
Wherein, described polystyrene is 2:1 with the mol ratio of concentrated sulphuric acid, and reaction temperature is room temperature, and the response time is 24h；Sulfonated polystyrene and Fe3+Mol ratio be 3:1, reaction temperature is room temperature, and the response time is 20h；The solvent of dissolved polystyrene is.
Above-mentioned loaded by polystyrene type catalyst application process in dihydrocoumarin synthesizes is: join in container by 1-indone and organic solvent, stirring reaction after dropping hydrogenperoxide steam generator and loaded by polystyrene type catalyst；Reaction separates out catalyst with ethanol after terminating, and after extracting, wash, distilling, centrifugal for the reactant liquor rear supernatant is obtained dihydrocoumarin；The catalyst separated out is reused after drying.
Wherein, described organic solvent is dichloromethane；Described hydrogenperoxide steam generator mass fraction is 30%；Described hydrogen peroxide and 1-indone mol ratio are 2.5:1；Described loaded by polystyrene type catalyst quality is the 10% of 1-indone；Described reaction temperature is 25-45 DEG C, and the response time is 20h；Described catalyst reuses 3 times after drying.
The inventive method has significant advantage compared with traditional handicraft, main feature has: (1) present invention application hydrogen peroxide is oxidising agent, replacing traditional peracid is oxidant, improves in the utilization rate of oxidant and production process and does not produce acids, generates the water of environmentally safe；(2) the loaded by polystyrene recyclable recycling of type catalyst that prepared by the present invention；(3) present invention uses low concentration hydrogen peroxide to be oxidant, improves safety and the spatter property of industrially prepared reaction；(4) reaction condition of the present invention is gentle, it is not necessary to High Temperature High Pressure can be reacted.
Accompanying drawing explanation
Fig. 1 is that dihydrocoumarin reaction equation is prepared in the catalysis oxidation of 1-indone.
Fig. 2 is the nuclear magnetic spectrogram of dihydrocoumarin.
Detailed description of the invention
Further illustrate the technical solution of the present invention below in conjunction with specific embodiment, these embodiments are not to be construed as the restriction to technical scheme.
Reagent source and detecting instrument model used: polystyrene, industrial goods BASFs-Yang Zi company limited；1-indone, industrial goods, Jiangsu Bao Sheng chemical reagent company limited；Ferric chloride, industrial goods, Aladdin reagent (Shanghai) Co., Ltd.；Sulphuric acid, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group；30% hydrogenperoxide steam generator, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group；Dichloromethane, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group；Ethanol, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group；Gas chromatograph, Shimadzu GC-2014C, Anjelen Sci. & Tech. Inc.
Embodiment 1: the preparation of loaded by polystyrene type catalyst
(1) in three-necked bottle, add 1.0g polystyrene, add 10ml dichloromethane as solvent, be completely dissolved under heated and stirred, be cooled to room temperature；Being subsequently added the concentrated sulphuric acid of 2.5ml98wt% as sulfonated reagent, be stirred at room temperature and carry out sulfonating reaction, the response time is 24h；Product is separated out after terminating by reaction with ethanol, is dried to obtain sulfonated polystyrene after filtration；
(2) take above-mentioned prepared sulfonated polystyrene 1.0g to be placed in three-necked bottle, add 10ml dichloromethane and be completely dissolved, add 0.5gFeCl3, stirring reaction 2h, by infusion process by Fe3+Being supported on sulfonated polystyrene, the response time is 18h；After reaction completely, with ethanol, product is separated out, filter, be dried after washing, obtain the polyphenylacetylene catalyst of load iron ion.
Embodiment 2: add 0.45 g 1-indone, 5 ml dichloromethane, 0.05 g loaded by polystyrene type catalyst in 50 mL there-necked flasks, drips 30wt% hydrogenperoxide steam generator, and hydrogen peroxide and 1-indone mol ratio are 2.5:1, stirring reaction 20h at 45 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 94%, and the productivity of dihydrocoumarin is 85%.
Embodiment 3: in 50 mL there-necked flasks, adds 0.45 g 1-indone, 5 ml dichloromethane, 0.04 g loaded by polystyrene type catalyst, drips 30wt% hydrogenperoxide steam generator, hydrogen peroxide and 1-indone mol ratio 2.5:1, stirring reaction 20h at 45 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 71%, and the productivity of dihydrocoumarin is 66%.
Embodiment 4: in 50 mL there-necked flasks, adds 0.45 g 1-indone, 5 ml dichloromethane, 0.03 g loaded by polystyrene type catalyst, drips 30wt% hydrogenperoxide steam generator, hydrogen peroxide and 1-indone mol ratio 2.5:1, stirring reaction 20h at 45 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 36%, and the productivity of dihydrocoumarin is 25%.
Embodiment 5: in 50 mL there-necked flasks, adds 0.45 g 1-indone, 5 ml dichloromethane, 0.05 g loaded by polystyrene type catalyst, drips 30wt% hydrogenperoxide steam generator, hydrogen peroxide and 1-indone mol ratio 1.5:1, stirring reaction 20h at 45 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 74%, and the productivity of dihydrocoumarin is 65%.
Embodiment 6: in 50 mL there-necked flasks, adds 0.45 g 1-indone, 5 ml dichloromethane, 0.05 g loaded by polystyrene type catalyst, drips 30wt% hydrogenperoxide steam generator, hydrogen peroxide and 1-indone mol ratio 0.5:1, stirring reaction 20h at 45 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 33%, and the productivity of dihydrocoumarin is 19%.
Embodiment 7: in 50 mL there-necked flasks, adds 0.45 g 1-indone, 5 ml dichloromethane, 0.05 g loaded by polystyrene type catalyst, drips 30wt% hydrogenperoxide steam generator, hydrogen peroxide and 1-indone mol ratio 2.5:1, stirring reaction 20h at 35 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 80%, and the productivity of dihydrocoumarin is 72%.
Embodiment 8: in 50 mL there-necked flasks, adds 0.45 g 1-indone, 5 ml dichloromethane, 0.05 g loaded by polystyrene type catalyst, drips 30wt% hydrogenperoxide steam generator, hydrogen peroxide and 1-indone mol ratio 2.5:1, stirring reaction 20h at 25 DEG C；Catalyst is separated out after terminating by reaction with ethanol, and reactant liquor 5ml ethyl acetate extracts 3 times, isolates organic facies；The sodium bicarbonate solution taking 2ml mass concentration 5% washs organic facies 3 times, then with deionized water, organic facies is washed to neutrality；Aqueous phase regulation to alkalescence and is extracted with ethyl acetate by the sodium bicarbonate solution with 5%, is merged with organic facies by acetic acid ethyl acetate extract, rotary evaporation in vacuo, removes solvent, circulation of qi promoting analysis of hplc of going forward side by side of weighing；The conversion ratio of 1-indone is 70%, and dihydrocoumarin productivity is 61%.
Claims (4)
1. loaded by polystyrene type catalyst, is characterized in that: this loaded catalyst be polystyrene is dissolved in a solvent after through concentrated sulphuric acid at room temperature sulfonation, then with ethanol separate out, filter, be dried, obtain sulfonated polystyrene；Then with the upper Fe of infusion process absorption after sulfonated polystyrene being dissolved again3+, filter after precipitation, be dried and prepare loaded by polystyrene type catalyst.
Loaded by polystyrene type catalyst the most according to claim 1, is characterized in that: described polystyrene is 2:1 with the mol ratio of concentrated sulphuric acid, and reaction temperature is room temperature, and the response time is 24h；Sulfonated polystyrene and Fe3+Mol ratio be 3:1, reaction temperature is room temperature, and the response time is 20h；The solvent of dissolved polystyrene is dichloromethane.
3. loaded by polystyrene type catalyst application process in dihydrocoumarin synthesizes, is characterized in that this application process is: join in container by 1-indone and organic solvent, stirring reaction after dropping hydrogenperoxide steam generator and loaded by polystyrene type catalyst；Reaction separates out catalyst with ethanol after terminating, and after extracting, wash, distilling, centrifugal for the reactant liquor rear supernatant is obtained dihydrocoumarin；The catalyst separated out is reused after drying.
The loaded by polystyrene type catalyst the most according to claim 3 application process in dihydrocoumarin synthesizes, is characterized in that: described organic solvent is dichloromethane；Described hydrogenperoxide steam generator mass fraction is 30%；Described hydrogen peroxide and 1-indone mol ratio are 2.5:1；Described loaded by polystyrene type catalyst quality is the 10% of 1-indone；Described reaction temperature is 25 ~ 45 DEG C, and the response time is 20h；Described catalyst reuses 3 times after drying.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142705A (en) * | 2020-09-10 | 2020-12-29 | 浙江工业大学 | Method for synthesizing cromolyn sodium key intermediate 7-hydroxy-4-methylcoumarin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774990A (en) * | 2010-02-09 | 2010-07-14 | 上海应用技术学院 | Method for preparing dihydrocoumarin without phenol |
| CN102989509A (en) * | 2012-12-18 | 2013-03-27 | 天津工业大学 | Catalyst of sulfonated polystyrene grafted polytetrafluoroethylene fiber metal complex and preparation method thereof |
| CN103721746A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工股份有限公司 | Composite catalyst used for industrial wastewater treatment via electrolytic oxidation, and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774990A (en) * | 2010-02-09 | 2010-07-14 | 上海应用技术学院 | Method for preparing dihydrocoumarin without phenol |
| CN103721746A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工股份有限公司 | Composite catalyst used for industrial wastewater treatment via electrolytic oxidation, and preparation method thereof |
| CN102989509A (en) * | 2012-12-18 | 2013-03-27 | 天津工业大学 | Catalyst of sulfonated polystyrene grafted polytetrafluoroethylene fiber metal complex and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 谢斌 等: "聚苯乙烯负载三氯化铁催化制备碳水化合物O-异亚丙基衍生物的改良方法", 《中国药物化学杂志》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142705A (en) * | 2020-09-10 | 2020-12-29 | 浙江工业大学 | Method for synthesizing cromolyn sodium key intermediate 7-hydroxy-4-methylcoumarin |
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