CN105854938B - Loaded by polystyrene type catalyst and its application process in dihydrocoumarin synthesis - Google Patents
Loaded by polystyrene type catalyst and its application process in dihydrocoumarin synthesis Download PDFInfo
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Abstract
Application process the invention discloses loaded by polystyrene type catalyst and its in dihydrocoumarin synthesis, the loaded by polystyrene type catalyst are used for being catalyzed 1 indone synthesizing lactone compound, specifically include following steps：1 indone and organic solvent are added in container, stirring reaction after dropwise addition hydrogenperoxide steam generator and loaded by polystyrene type catalyst, react and separate out catalyst with ethanol after terminating, supernatant liquor is through extraction after reaction solution is centrifuged, washing, dihydrocoumarin is obtained after distillation.It is an advantage of the invention that：Use loaded by polystyrene type catalyst, its preparation method is simple, improves the conversion ratio of 1 indone, improves the atom utilization of reaction, and loaded by polystyrene type catalyst is reused, it is good without spent acid processing, energy-saving and emission-reduction, selectivity, atomic efficiency is high, reaction condition is gentle, the characteristic such as clean environment, is suitable for Industrial Engineering application.
Description
Technical field
A kind of application process the present invention relates to loaded by polystyrene type catalyst and its in dihydrocoumarin synthesis, i.e.,
Using 1- indones as raw material, using hydrogen peroxide as Green Oxidant, application load Fe- sulfonated polystyrenes pass through for catalyst
The method of Baeyer-Villiger oxidation reaction catalysis oxidation, substitutes the tradition side using cumarin as raw material high-temperature high-voltage reaction
Method synthesizing dihydro cumarin, as the organic functional material preparation field such as medicine, spices, dyestuff.
Background technology
Catalyst carrier is also known as carrier, is one of main composition of loaded catalyst.Carrier can make manufactured catalysis
Agent has suitable shape, size and mechanical strength, to meet the operation requirement of industrial reactor；Carrier can make active component point
It is dispersed on carrier surface, obtains higher specific surface area, improves the catalytic efficiency of unit mass active component, and carrier in itself one
As do not have catalytic activity.Conventional catalyst carrier has alumina support, silica-gel carrier, absorbent charcoal carrier and some natural productions
Thing such as float stone, diatomite etc..Loaded catalyst is good often with there is catalytic performance, easily separated the features such as recycling and reusing.
Dihydrocoumarin is critically important chemical intermediate, is widely used in medicine, spices, cosmetics and food additives
Preparation.Natural dihydrocoumarin is present in Melilot.Dihydrocoumarin is as important lactone at many aspects
There is application, available for cream, coconut is modulated, Chinese cassia tree flavor essence also serves as flavouring essence for tobacco, and synthesizing dihydro cumarin has very
Big application prospect.
Natural dihydrocoumarin is present in Melilot.Traditional preparation method is divided into following four：（1）With perfume (or spice)
Legumin is raw material, in the presence of a nickel catalyst, is hydrogenated with and obtains at 160~200 DEG C and under pressurization；（2）Using adjacent chlorobenzene propionic acid as original
Material, hydrolyzed in alkaline aqueous solution, generate o-hydroxy propionic acid, dehydration, closed loop and obtain；（3）Using ortho-aminotoluene as raw material, in salt
Hydrolysis generation ortho-chlorotolu'ene, chlorination, generates adjacent chlorophenylmethyl chlorine in aqueous acid, hydrolyzes, and o-chlorobenzaldehyde is generated, in sodium acetate
With acetic acidreaction in solution, adjacent chlorobenzene acrylic acid is generated, is hydrogenated with, is hydrolyzed in alkaline aqueous solution, generates o-hydroxy propionic acid, is taken off
Water closed loop and obtain；（4）Using ortho-methyl phenol as raw material, with triclosan oxidation phosphorus reaction, again chlorination, at 160~180 DEG C with ethanol
Sodium reacts, and generates cumarin, is finally hydrogenated with and obtains.Prior synthesizing method is complex, and reactions steps are cumbersome, and reaction condition will
Ask high, separation and recovery product is not easy, and yield is undesirable.
There are some documents to be related to the yield by improving dihydrocoumarin using peroxide in catalysis oxidation.But
It is that the cost for separating and reclaiming is costly, pollution of the peroxide to environment is more serious.Illustrated in CN101774990 B
A kind of method that no phenol prepares dihydrocoumarin, cinnamic acid primary raw material is applied in this method, synthesized 1- indones first, then with
Hydrogen peroxide is oxidizer catalytic oxidative synthesis dihydrocoumarin.This method avoid the generation of phenol wastewater in industrial production, but
Peroxide urea has been used in reaction as catalyst, environment is affected and is unfavorable for the recovery of catalyst.
More and more show, be mainly shown as with the development of environmental economy, the shortcomings that the above method：（1）Reaction choosing
Selecting property is not high, forms substantial amounts of organic by-products waste, and environmental pollution is serious；（2）Energy consumption is big, corrosion of the peroxide to equipment
Property is big, and stability is poor, has certain risk.In view of the demand of dihydrocoumarin will be increasing, with environmental economy
Development, traditional production method of dihydrocoumarin does not have sustainable developability, inevitable to be taken by more environment-friendly method
Generation.
The content of the invention
It is an object of the invention to：A kind of loaded catalyst and its application side in dihydrocoumarin synthesis are provided
Method, it is catalyst without using peroxide using hydrogen peroxide as Green Oxidant, reaction condition is gentle, good, the yield of selectivity
Height, no spent acid produce, and are suitable for engineering to convert.
The present invention technical solution be：The loaded catalyst is through dense sulphur after polystyrene is dissolved in a solvent
Sour sulfonation at room temperature, then separated out with ethanol, filter, dry, obtain sulfonated polystyrene；Then it is sulfonated polystyrene is molten again
Upper Fe is adsorbed with infusion process after solution3+, filtered after precipitation, dry obtained loaded by polystyrene type catalyst.
Wherein, the mol ratio of described polystyrene and the concentrated sulfuric acid is 2:1, reaction temperature is room temperature, and the reaction time is
24h；Sulfonated polystyrene and Fe3+Mol ratio be 3:1, reaction temperature is room temperature, reaction time 20h；Dissolved polystyrene
Solvent be.
Above-mentioned loaded by polystyrene type catalyst dihydrocoumarin synthesis in application process be：By 1- indones and organic
Solvent is added in container, and stirring reaction after hydrogenperoxide steam generator and loaded by polystyrene type catalyst is added dropwise；After reaction terminates
Catalyst is separated out with ethanol, supernatant liquor obtains dihydrocoumarin after extracting, wash, distill after reaction solution is centrifuged；Separate out
Catalyst dry after reuse.
Wherein, described organic solvent is dichloromethane；The hydrogenperoxide steam generator mass fraction is 30%；The peroxide
It is 2.5 to change hydrogen with 1- indones mol ratio:1；The loaded by polystyrene type catalyst quality is the 10% of 1- indones；The reaction
Temperature is 25-45 DEG C, reaction time 20h；Described catalyst reuses 3 times after drying.
The inventive method has the advantages of notable compared with traditional handicraft, and main feature has：（1）The present invention applies peroxidating
Hydrogen is oxidising agent, is oxidant instead of traditional peracid, improve oxidant utilization rate and production process in do not produce acid
Class, generate environmentally safe water；（2）The recyclable recycling of loaded by polystyrene type catalyst prepared by the present invention；
（3）The present invention is oxidant using low concentration hydrogen peroxide, improves the security and spatter property of industrially prepared reaction；（4）This
Invention reaction condition is gentle, it is not necessary to which HTHP can react.
Brief description of the drawings
Fig. 1 is that 1- indone catalysis oxidations prepare dihydrocoumarin reaction equation.
Fig. 2 is the nuclear magnetic spectrogram of dihydrocoumarin.
Embodiment
With reference to specific embodiment further illustrate the present invention technical solution, these embodiments it is not intended that
It is the limitation to technical scheme.
Reagent source and detecting instrument model used：Polystyrene, industrial goods BASF-Yangtze Co., Ltd；1- indones,
Industrial goods, Jiangsu Bao Sheng chemical reagent Co., Ltd；Ferric trichloride, industrial goods, Aladdin reagent（Shanghai）Co., Ltd；Sulphur
Acid, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group；30% hydrogenperoxide steam generator, SILVER REAGENT, Chinese medicines group chemical reagent have
Limit company；Dichloromethane, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group；Ethanol, SILVER REAGENT, Chinese medicines group chemical reagent
Co., Ltd；Gas chromatograph, Shimadzu GC-2014C, Anjelen Sci. ＆ Tech. Inc.
Embodiment 1：The preparation of loaded by polystyrene type catalyst
（1）1.0g polystyrene is added in three-necked bottle, 10ml dichloromethane is added as solvent, under heating stirring
It is completely dissolved, is cooled to room temperature；The 2.5ml98wt% concentrated sulfuric acid is then added as sulfonated reagent, be stirred at room temperature into
Row sulfonating reaction, reaction time 24h；Reaction is separated out product with ethanol after terminating, and sulfonated polyphenyl second is dried to obtain after filtering
Alkene；
（2）Take above-mentioned obtained sulfonated polystyrene 1.0g to be placed in three-necked bottle, add 10ml dichloromethane it is completely molten
Solution, adds 0.5gFeCl3, stirring reaction 2h, by infusion process by Fe3+It is supported on sulfonated polystyrene, the reaction time is
18h；After reaction completely, product is separated out with ethanol, filtered, is dried after washing, obtains loading the polystyrene catalysis of iron ion
Agent.
Embodiment 2：0.45 g 1- indones, 5 ml dichloromethane, 0.05 g polyphenyl second are added in 50 mL three-necked flasks
Alkene loaded catalyst, is added dropwise 30wt% hydrogenperoxide steam generators, and hydrogen peroxide is 2.5 with 1- indones mol ratio:1, stirred at 45 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 94%, two
The yield of hydrogen cumarin is 85%.
Embodiment 3：In 50 mL three-necked flasks, 0.45 g 1- indones, 5 ml dichloromethane, 0.04 g polyphenyl are added
Ethene loaded catalyst, 30wt% hydrogenperoxide steam generators, hydrogen peroxide and 1- indones mol ratio 2.5 is added dropwise:1, stirred at 45 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 71%, two
The yield of hydrogen cumarin is 66%.
Embodiment 4：In 50 mL three-necked flasks, 0.45 g 1- indones, 5 ml dichloromethane, 0.03 g polyphenyl are added
Ethene loaded catalyst, 30wt% hydrogenperoxide steam generators, hydrogen peroxide and 1- indones mol ratio 2.5 is added dropwise:1, stirred at 45 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 36%, two
The yield of hydrogen cumarin is 25%.
Embodiment 5：In 50 mL three-necked flasks, 0.45 g 1- indones, 5 ml dichloromethane, 0.05 g polyphenyl are added
Ethene loaded catalyst, 30wt% hydrogenperoxide steam generators, hydrogen peroxide and 1- indones mol ratio 1.5 is added dropwise:1, stirred at 45 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 74%, two
The yield of hydrogen cumarin is 65%.
Embodiment 6：In 50 mL three-necked flasks, 0.45 g 1- indones, 5 ml dichloromethane, 0.05 g polyphenyl are added
Ethene loaded catalyst, 30wt% hydrogenperoxide steam generators, hydrogen peroxide and 1- indones mol ratio 0.5 is added dropwise:1, stirred at 45 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 33%, two
The yield of hydrogen cumarin is 19%.
Embodiment 7：In 50 mL three-necked flasks, 0.45 g 1- indones, 5 ml dichloromethane, 0.05 g polyphenyl are added
Ethene loaded catalyst, 30wt% hydrogenperoxide steam generators, hydrogen peroxide and 1- indones mol ratio 2.5 is added dropwise:1, stirred at 35 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 80%, two
The yield of hydrogen cumarin is 72%.
Embodiment 8：In 50 mL three-necked flasks, 0.45 g 1- indones, 5 ml dichloromethane, 0.05 g polyphenyl are added
Ethene loaded catalyst, 30wt% hydrogenperoxide steam generators, hydrogen peroxide and 1- indones mol ratio 2.5 is added dropwise:1, stirred at 25 DEG C
Mix reaction 20h；Reaction is separated out catalyst with ethanol after terminating, and reaction solution is extracted 3 times with 5ml ethyl acetate, is isolated organic
Phase；Take the sodium bicarbonate solution of 2ml mass concentrations 5% to wash organic phase 3 times, then be washed to organic phase with deionized water
Property；Aqueous phase is adjusted to alkalescent and is extracted with ethyl acetate with 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract with having
Machine mutually merges, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing；The conversion ratio of 1- indones is 70%, two
Hydrogen cumarin yield is 61%.
Claims (4)
1. loaded by polystyrene type catalyst, it is characterized in that：The loaded catalyst is after polystyrene is dissolved in a solvent
Separate out, filter through concentrated sulfuric acid sulfonation at room temperature, then with ethanol, dry, obtain sulfonated polystyrene；Then by sulfonated polystyrene
Upper Fe is adsorbed with infusion process after dissolving again3+, filtered after precipitation, dry obtained loaded by polystyrene type catalyst.
2. loaded by polystyrene type catalyst according to claim 1, it is characterized in that：Described polystyrene and the concentrated sulfuric acid
Mol ratio be 2:1, reaction temperature is room temperature, reaction time 24h；Sulfonated polystyrene and Fe3+Mol ratio be 3:
1, reaction temperature is room temperature, reaction time 20h；The solvent of dissolved polystyrene is dichloromethane.
3. a kind of application process of loaded by polystyrene type catalyst as claimed in claim 1 in dihydrocoumarin synthesis,
It is characterized in that the application process is：1- indones and organic solvent are added in container, hydrogenperoxide steam generator and polyphenyl second is added dropwise
Stirring reaction after alkene loaded catalyst；React and separate out catalyst with ethanol after terminating, supernatant liquor passes through after reaction solution is centrifuged
Dihydrocoumarin is obtained after extraction, washing, distillation；The catalyst of precipitation is reused after drying.
4. application process of the loaded by polystyrene type catalyst according to claim 3 in dihydrocoumarin synthesis, its
It is characterized in：Described organic solvent is dichloromethane；The hydrogenperoxide steam generator mass fraction is 30%；The hydrogen peroxide with
1- indones mol ratio is 2.5:1；The loaded by polystyrene type catalyst quality is the 10% of 1- indones；The reaction temperature is
25 ~ 45 DEG C, reaction time 20h；Described catalyst reuses 3 times after drying.
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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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- 2015-07-02 CN CN201510380365.6A patent/CN105854938B/en active Active
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 |
|---|
| 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;谢斌 等;《中国药物化学杂志》;20080430;第18卷(第2期);第109-110页 * |
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Effective date of registration: 20200924 Address after: 244000 No. 1688, north section of Taishan Avenue, Tongling Economic Development Zone, Anhui Province Patentee after: Anhui Weixiang New Material Co., Ltd Patentee after: NANJING University OF SCIENCE AND TECHNOLOGY Address before: 211600 Huaian City, Jiangsu province Jinhu County Beizhen Industrial Zone No. 6 Patentee before: JIANGSU XINHUAI RIVER PHARMTECH Co.,Ltd. Patentee before: NANJING University OF SCIENCE AND TECHNOLOGY |