CN111187152A - Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid - Google Patents
Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid Download PDFInfo
- Publication number
- CN111187152A CN111187152A CN202010128547.5A CN202010128547A CN111187152A CN 111187152 A CN111187152 A CN 111187152A CN 202010128547 A CN202010128547 A CN 202010128547A CN 111187152 A CN111187152 A CN 111187152A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- reaction
- immobilized ionic
- alkaline
- acetone
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for synthesizing pseudo ionone by catalyzing alkaline immobilized ionic liquid, which takes citral as a raw material, and slowly drops acetone at 40-50 ℃ for reaction under the condition that the alkaline immobilized ionic liquid is used as a catalyst to prepare the pseudo ionone; the carrier used in the alkaline immobilized ionic liquid is a PS material, the PS material is polystyrene, and the alkaline immobilized ionic liquid is one of the following substances:
Description
Technical Field
The invention belongs to the field of organic synthesis of fine chemicals, and particularly relates to a method for synthesizing pseudo ionone under the catalysis of an alkaline immobilized ionic liquid.
Background
The molecular formula of the pseudoionone is C13H20O, the chemical name of which is 6, 10-dimethyl-undecane triene-2-ketone, is a light yellow transparent liquid, is an important chemical intermediate, and can be used for synthesizing fine chemicals such as ionone, vitamin A, vitamin E, β -carotene and the like in chemical production.
The pseudo ionone is prepared by aldol condensation reaction of citral obtained by distillation from some natural product essential oils (such as lemongrass oil and litsea cubeba oil) and acetone under the catalysis of a catalyst.
The aldol condensation reaction for synthesizing the pseudo ionone needs to be carried out under the catalysis of an alkaline catalyst. The production process widely adopted at present is a synthesis method using an aqueous sodium hydroxide solution as a catalyst. Proportionally adding acetone and NaOH aqueous solution into a reactor, slowly dropwise adding citral into a reaction system, and controlling the synthesis reaction temperature and reaction time. After the reaction is finished, standing and layering, and separating out the lower layer alkali liquor. Vacuum distilling to recover acetone, and using CH as reaction liquid3Repeatedly washing the COOH solution to be neutral, and after layering, obtaining an organic phase which is the pseudo ionone crude product.
The problems of using sodium hydroxide aqueous solution as catalyst are: the side reaction is accompanied when the sodium hydroxide aqueous solution is used for catalyzing the reaction, so that the color and luster of the product are poor, and the yield is influenced to a certain extent; the use of the sodium hydroxide aqueous solution can cause severe corrosion to reaction equipment, and the equipment needs to be frequently maintained in an anti-corrosion manner, so that the production cost is increased; in the subsequent treatment process, the washing for removing alkali needs to consume a larger amount of water, and the treatment of sewage also increases the production cost.
Ionic Liquids (Ionic Liquids), also known as Room Temperature Ionic Liquids (Room Temperature Ionic Liquids) or low Temperature molten salts, generally refer to organic salts having a melting point below 100 ℃. Ionic liquids are electrically neutral and have many different properties from conventional organic solvents, due to their complete composition of anions and cations. Such as low melting point, non-volatility, wide range of liquid process, good thermal stability, strong dissolving capacity, adjustable property, difficult combustion, wide electrochemical window and the like. The non-volatility is the most outstanding characteristic of ionic liquid compared with the traditional organic solvent, and people can use the characteristic as a good green solvent to be widely applied. The use of basic ionic liquids for the catalysis of pseudoionones can be found in the method adopted in the published CN 109503490A. The method considers the condition that the ionic liquid catalyst is viscous and causes catalyst loss in multiple circulation reactions, and the condition that the liquid phase catalyst is not suitable for a continuous production mode.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a method for synthesizing pseudo ionone under the catalysis of alkaline immobilized ionic liquid.
The method for synthesizing the pseudo ionone under the catalysis of the alkaline immobilized ionic liquid is characterized in that citral is used as a raw material, and acetone is slowly dropped at 40-50 ℃ to react under the condition that the alkaline immobilized ionic liquid is used as a catalyst, so that the pseudo ionone is prepared; the carrier used in the alkaline immobilized ionic liquid is a PS material, the PS material is polystyrene, and the alkaline immobilized ionic liquid is one of the following substances:
the method for synthesizing the pseudo ionone under the catalysis of the alkaline immobilized ionic liquid is characterized in that the molar ratio of citral to acetone is 1: 4-6, and the dosage of the catalyst is 20-30% of the total weight of the citral and the acetone.
The method for synthesizing the pseudo ionone under the catalysis of the alkaline immobilized ionic liquid is characterized in that the acetone is dropwise added within 2-3h, and after the acetone is dropwise added, the temperature is maintained at 50-60 ℃ for heat preservation reaction for 4-6 h.
The method for synthesizing the pseudo ionone under the catalysis of the alkaline immobilized ionic liquid is characterized in that after the reaction is finished, the catalyst is separated from the reaction liquid through filtration, the reaction liquid is washed for 1-3 times by an acetic acid aqueous solution with the volume fraction of 5-15%, and then the pseudo ionone product is obtained after drying.
The immobilization method comprises the steps of introducing vinyl into a cation framework of the ionic liquid, forming a stable chemical bond through polymerization reaction of double bonds of the vinyl and double bonds of styrene, and immobilizing the ionic liquid on the polystyrene carrier. The polymerization mode does not destroy the alkalinity source of the ionic liquid, so that the ionic liquid still has stronger alkalinity after being immobilized. The reaction of citral with acetone to produce pseudoionone in an alkaline environment is typically a base-catalyzed aldol condensation reaction, and thus an immobilized basic ionic liquid capable of providing strong basicity can have high activity in the reaction.
The beneficial effects obtained by the invention are as follows: the alkaline immobilized ionic liquid catalyst is easy to separate from reaction liquid, avoids the condition of catalyst loss caused in multiple circulating reactions, is also suitable for continuous production of pseudo ionone, and has the advantages of high product yield, purer product and the like in the process of synthesizing the pseudo ionone.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1: preparation of immobilized ionic liquid A
41.1g (0.5 mol) of 1-methylimidazole and 53.5 g (0.5 mol) of vinyl bromide were added to a 150 mL three-necked flask, respectively, and the mixture was stirred at 70 ℃ for reaction for 5 hours, and after the reaction was completed, the mixture was cooled to room temperature to obtain a colorless viscous liquid. After extraction with diethyl ether 20 mL × 3 times, and vacuum drying, 94.5g of 1-vinyl-3-methylimidazolium bromide was obtained as a colorless viscous liquid.
94.5g (0.5 mol) of the brominated 1-vinyl-3-methylimidazole ionic liquid prepared above and 22.0g (0.55 mol) of NaOH powder were charged in a 250 mL three-necked flask, and 100 mL of methylene chloride was stirred at room temperature for 24 hours. After the reaction is finished, NaBr solid and excessive NaOH solid are removed through suction filtration. And (3) distilling the filtrate under reduced pressure to remove dichloromethane to obtain an ionic liquid intermediate [ Vnim ] OH containing vinyl, wherein the mass yield of the intermediate product is 98%.
Weighing 12.6g (0.1 mol) of the intermediate prepared above, dissolving the intermediate with 100 mL of absolute ethyl alcohol, weighing 91.2g (0.3 mol) of styrene, heating and refluxing 1.8 g (11 mmol) of initiator AIBN in a 250 mL three-neck round-bottom flask for reaction, magnetically stirring for 24 h, cooling to room temperature after the reaction is finished to obtain a white solid, filtering out the white solid, grinding the white solid into powder by a grinding mode, washing with absolute ethyl alcohol, performing suction filtration to obtain the white solid in order to remove excessive acidic ionic liquid and styrene monomer, and performing vacuum drying for 12 h to obtain the catalyst immobilized ionic liquid A.
Example 2: preparation of immobilized ionic liquid B
A250 mL three-necked flask was charged with 55.6g (0.5 mol) of N-vinylpyrrolidone, 22.0g (0.55 mol) of NaOH powder, and 100 mL of methylene chloride, and stirred at room temperature for 24 hours. After the reaction is finished, excessive NaOH solid is removed through suction filtration. And (3) distilling the filtrate under reduced pressure to remove dichloromethane to obtain an intermediate [ Vnmp ] OH ionic liquid, wherein the mass yield of the intermediate product is 99%.
12.8 g (0.1 mol) of the intermediate prepared above was weighed and dissolved in 100 mL of absolute ethanol, 91.2g (0.3 mol) of styrene and 1.8 g (11 mmol) of AIBN were added to a 250 mL three-necked round-bottomed flask and heated under reflux, the mixture was magnetically stirred for 24 hours, after completion of the reaction, the mixture was cooled to room temperature to obtain a white solid, which was filtered off, ground into powder by a grinding method and washed with absolute ethanol, and the white solid was filtered off by suction filtration to remove excess acidic ionic liquid and styrene monomer, and dried under vacuum for 12 hours to obtain catalyst-immobilized ionic liquid B.
Example 3: preparation of immobilized ionic liquid C
In a 150 mL three-necked flask, 50.6g (0.5 mol) of triethylamine and 53.5 g (0.5 mol) of vinyl bromide were added, respectively, and the mixture was stirred at 70 ℃ for reaction for 5 hours, and after completion of the reaction, the mixture was cooled to room temperature to obtain a colorless viscous liquid. After 20 mL of this solution was extracted with diethyl ether and then dried in vacuo, 104.1g of N, N, N-triethylethylene bromide was obtained as a colorless viscous liquid.
104.1g (0.5 mol) of the brominated N, N, N-triethylethylene prepared above, 22.0g (0.55 mol) of NaOH powder, and 100 mL of methylene chloride were placed in a 250 mL three-necked flask, and stirred at room temperature for 24 hours. After the reaction is finished, NaBr solid and excessive NaOH solid are removed through suction filtration. And (3) distilling the filtrate under reduced pressure to remove dichloromethane to obtain an ionic liquid intermediate [ Vtea ] OH containing vinyl, wherein the mass yield of the intermediate product is 95%.
14.5g (0.1 mol) of the intermediate prepared above is weighed and dissolved by 100 mL of absolute ethyl alcohol, 91.2g (0.3 mol) of styrene and 1.8 g (11 mmol) of initiator AIBN are weighed and heated in a 250 mL three-neck round-bottom flask for reflux reaction, magnetic stirring is carried out for 24 h, after the reaction is finished, the reaction is cooled to room temperature to obtain white solid, the white solid is filtered out, the white solid is ground into powder by a grinding mode and washed by absolute ethyl alcohol, the white solid is obtained by suction filtration for removing excessive acidic ionic liquid and styrene monomer, and the catalyst immobilized ionic liquid C is obtained after vacuum drying for 12 h.
Example 4:
6.08g (0.04 mol) of citral and 3.54g of immobilized ionic liquid A were charged into a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and stirred, and acetone was added dropwise at an addition rate of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating the immobilized ionic liquid A in the reaction system in a filtering mode, washing the immobilized ionic liquid A with ethyl acetate, drying, and recovering for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid A is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 71.31% by using a gas chromatography.
Example 5:
6.08g (0.04 mol) of citral and 3.54g of immobilized ionic liquid B were added to a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and the mixture was stirred, and acetone was added dropwise at an amount of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating out the immobilized ionic liquid B in the reaction system in a filtering mode, washing and drying the immobilized ionic liquid B by using ethyl acetate, and recycling the ionic liquid B for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid B is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the conversion rate of the citral is 76.28% by using a gas chromatography.
Example 6:
6.08g (0.04 mol) of citral and 3.54g of immobilized ionic liquid C were added to a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating out the immobilized ionic liquid C in the reaction system in a filtering mode, washing and drying the immobilized ionic liquid C by using ethyl acetate, and recycling the ionic liquid C for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid C is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 83.63% by using gas chromatography.
Example 7:
6.08g (0.04 mol) of citral and 3.07g of immobilized ionic liquid A were added to a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 9.28g (0.16 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating the immobilized ionic liquid A in the reaction system in a filtering mode, washing the immobilized ionic liquid A with ethyl acetate, drying, and recovering for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid A is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 66.52% by using a gas chromatography.
Example 8:
6.08g (0.04 mol) of citral and 4.00 g of immobilized ionic liquid A were added to a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 13.92g (0.24 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating the immobilized ionic liquid A in the reaction system in a filtering mode, washing the immobilized ionic liquid A with ethyl acetate, drying, and recovering for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid A is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 84.16% by using a gas chromatography.
Example 9:
6.08g (0.04 mol) of citral and 3.07g of immobilized ionic liquid C were added to a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 9.28g (0.16 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating out the immobilized ionic liquid C in the reaction system in a filtering mode, washing and drying the immobilized ionic liquid C by using ethyl acetate, and recycling the ionic liquid C for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid C is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 76.81% by using a gas chromatography.
Example 10:
6.08g (0.04 mol) of citral and 4.00 g of immobilized ionic liquid C were added to a 50mL three-necked flask, the temperature of the system was raised to 50 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 13.92g (0.24 mol) at a rate of 30 seconds per drop. After the addition of acetone was completed, the reaction was incubated at 50 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating out the immobilized ionic liquid C in the reaction system in a filtering mode, washing and drying the immobilized ionic liquid C by using ethyl acetate, and recycling the ionic liquid C for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid C is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 89.67% by using gas chromatography.
Example 11:
6.08g (0.04 mol) of citral and 3.54g of immobilized ionic liquid A were charged into a 50mL three-necked flask, the temperature of the system was raised to 60 ℃ and stirred, and acetone was added dropwise at an addition rate of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone, the reaction was incubated at 60 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating the immobilized ionic liquid A in the reaction system in a filtering mode, washing the immobilized ionic liquid A with ethyl acetate, drying, and recovering for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid A is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 73.22% by using a gas chromatography.
Example 12:
6.08g (0.04 mol) of citral and 3.54g of immobilized ionic liquid C were added to a 50mL three-necked flask, the temperature of the system was raised to 60 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone, the reaction was incubated at 60 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating out the immobilized ionic liquid C in the reaction system in a filtering mode, washing and drying the immobilized ionic liquid C by using ethyl acetate, and recycling the ionic liquid C for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid C is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 86.91% by using gas chromatography.
Example 13:
6.08g (0.04 mol) of citral and 5.31 g of immobilized ionic liquid A were charged into a 50mL three-necked flask, the temperature of the system was raised to 60 ℃ and stirred, and acetone was added dropwise at an addition rate of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone, the reaction was incubated at 60 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating the immobilized ionic liquid A in the reaction system in a filtering mode, washing the immobilized ionic liquid A with ethyl acetate, drying, and recovering for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid A is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 74.37% by using a gas chromatography.
Example 14:
6.08g (0.04 mol) of citral and 5.31 g of immobilized ionic liquid C were added to a 50mL three-necked flask, the temperature of the system was raised to 60 ℃ and the mixture was stirred, acetone was added dropwise at an amount of 11.62g (0.20 mol) at a rate of 30 seconds per drop. After the addition of acetone, the reaction was incubated at 60 ℃ for 5 h. After the reaction is finished, cooling the reaction system to room temperature, separating out the immobilized ionic liquid C in the reaction system in a filtering mode, washing and drying the immobilized ionic liquid C by using ethyl acetate, and recycling the ionic liquid C for next repeated use. And (3) filtering the reaction solution from which the immobilized ionic liquid C is removed, washing the reaction solution for 2 times by using an acetic acid aqueous solution with the volume fraction of 10% (the dosage of the acetic acid aqueous solution for each washing is 30 mL), and performing rotary evaporation to remove residual water and acetic acid to obtain a crude product of the pseudo ionone, wherein the citral conversion rate is 86.53% by using a gas chromatography.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (4)
1. A method for synthesizing pseudo ionone by catalyzing alkaline immobilized ionic liquid is characterized in that citral is used as a raw material, and acetone is slowly dripped at 40-50 ℃ under the condition that the alkaline immobilized ionic liquid is used as a catalyst to react to prepare the pseudo ionone; the carrier used in the alkaline immobilized ionic liquid is a PS material, the PS material is polystyrene, and the alkaline immobilized ionic liquid is one of the following substances:
2. the method for synthesizing pseudo ionone by catalysis of alkaline immobilized ionic liquid according to claim 1, wherein the molar ratio of citral to acetone is 1: 4-6, and the amount of the catalyst is 20-30% of the total weight of citral and acetone.
3. The method for synthesizing pseudo-ionone under catalysis of alkaline immobilized ionic liquid according to claim 1, wherein the acetone is dropwise added within 2-3h, and after the acetone is dropwise added, the temperature is maintained at 50-60 ℃ for reaction for 4-6 h.
4. The method for synthesizing pseudo ionone under the catalysis of alkaline immobilized ionic liquid according to claim 1, wherein after the reaction is finished, the catalyst is separated from the reaction solution by filtration, and the reaction solution is washed for 1-3 times by an acetic acid aqueous solution with volume fraction of 5-15% and then dried to obtain the pseudo ionone product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010128547.5A CN111187152B (en) | 2020-02-28 | 2020-02-28 | Method for synthesizing pseudoionone by catalyzing alkaline immobilized ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010128547.5A CN111187152B (en) | 2020-02-28 | 2020-02-28 | Method for synthesizing pseudoionone by catalyzing alkaline immobilized ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111187152A true CN111187152A (en) | 2020-05-22 |
| CN111187152B CN111187152B (en) | 2022-07-15 |
Family
ID=70704914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010128547.5A Active CN111187152B (en) | 2020-02-28 | 2020-02-28 | Method for synthesizing pseudoionone by catalyzing alkaline immobilized ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111187152B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698284A (en) * | 2021-09-02 | 2021-11-26 | 上海万香日化有限公司 | Synthesis method of pseudo ionone |
| WO2022104581A1 (en) * | 2020-11-18 | 2022-05-27 | 厦门金达威维生素有限公司 | Method for continuously synthesizing pseudoionone |
| CN116332854A (en) * | 2023-03-21 | 2023-06-27 | 浙江昂利泰制药有限公司 | Preparation method of benzylidene hydantoin |
| CN116332854B (en) * | 2023-03-21 | 2024-09-24 | 浙江昂利泰制药有限公司 | Preparation method of benzylidene hydantoin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562041A (en) * | 2015-12-16 | 2016-05-11 | 广州百花香料股份有限公司 | Preparation method of solid alkali catalyst and reaction method for catalytic synthesis of ionone fragrance intermediate by solid alkali catalyst |
| CN107670678A (en) * | 2017-10-19 | 2018-02-09 | 万华化学集团股份有限公司 | A kind of solid base catalyst and preparation method thereof and its method for being used to prepare pseudo ionone |
| CN109503490A (en) * | 2018-10-30 | 2019-03-22 | 浙江工业大学 | A kind of ionic-liquid catalyst and the preparation method and application thereof |
-
2020
- 2020-02-28 CN CN202010128547.5A patent/CN111187152B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562041A (en) * | 2015-12-16 | 2016-05-11 | 广州百花香料股份有限公司 | Preparation method of solid alkali catalyst and reaction method for catalytic synthesis of ionone fragrance intermediate by solid alkali catalyst |
| CN107670678A (en) * | 2017-10-19 | 2018-02-09 | 万华化学集团股份有限公司 | A kind of solid base catalyst and preparation method thereof and its method for being used to prepare pseudo ionone |
| CN109503490A (en) * | 2018-10-30 | 2019-03-22 | 浙江工业大学 | A kind of ionic-liquid catalyst and the preparation method and application thereof |
Non-Patent Citations (7)
| Title |
|---|
| IULIANA COTA，等: "Alanine-supported protic ionic liquids as efficient catalysts for aldol condensation reactions", 《COMPTES RENDUS CHIMIE》 * |
| SHIFENG JIANG,等: "One-Step Synthesis of Methyl Acrylate Using Methyl Acetate with Formaldehyde in a Fluidized Bed Reactor", 《IND. ENG. CHEM. RES.》 * |
| SIMON DOHERTY，等: "An efficient Cu(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase catalyst for asymmetric carbon–carbon bond formation", 《GREEN CHEM.》 * |
| SÒNIA ABELLÓ,等: "Supported choline hydroxide (ionic liquid) as heterogeneous catalyst for aldol condensation reactions", 《CHEM.COMMUN.》 * |
| 汪多仁: "《绿色增塑剂》", 31 October 2011, 科学技术文献出版社 * |
| 王结祥，等: "聚苯乙烯树脂催化羟醛缩合研究进展", 《化工进展》 * |
| 赵文善，等: "聚苯乙烯负载L-脯氨酸的制备及对不对称Aldol反应的催化性能", 《河南省化学会2010年学术年会论文摘要集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022104581A1 (en) * | 2020-11-18 | 2022-05-27 | 厦门金达威维生素有限公司 | Method for continuously synthesizing pseudoionone |
| CN113698284A (en) * | 2021-09-02 | 2021-11-26 | 上海万香日化有限公司 | Synthesis method of pseudo ionone |
| CN113698284B (en) * | 2021-09-02 | 2023-12-12 | 上海万香日化有限公司 | Synthesis method of pseudo ionone |
| CN116332854A (en) * | 2023-03-21 | 2023-06-27 | 浙江昂利泰制药有限公司 | Preparation method of benzylidene hydantoin |
| CN116332854B (en) * | 2023-03-21 | 2024-09-24 | 浙江昂利泰制药有限公司 | Preparation method of benzylidene hydantoin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111187152B (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101522656B (en) | Process for preparing nebivolol | |
| CN111187152B (en) | Method for synthesizing pseudoionone by catalyzing alkaline immobilized ionic liquid | |
| CN109485568B (en) | Preparation method of high-optical indoxacarb intermediate | |
| WO2006092433A1 (en) | Diarylphenoxy aluminum compounds | |
| CN108558794A (en) | A kind of preparation method for reacting synthesis light-sensitive compound according to Claisen-Schmidt | |
| CN104559286B (en) | A kind of triphenylamine-boron fluoride complexing dimethyl pyrrole methine derivative organic dyestuff and preparation method thereof | |
| CN102516139A (en) | Synthesis method of phenyl sulfide compound | |
| Bhar et al. | Pinacol coupling of aromatic aldehydes and ketones.. An improved method in an aqueous medium | |
| CN109305912B (en) | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde | |
| CN116803988A (en) | Synthesis method of isobutylidene hydantoin | |
| CN102040572A (en) | Production method of benzofuranone | |
| CN101434613B (en) | Process for synthesizing Al-salicylic aldehyde acylhydrazone complexes | |
| CN113461564A (en) | 4, 4' -dihydroxy-diazobenzophenone and preparation method thereof | |
| CN108546232B (en) | Preparation method of mono-substituted or di-substituted benzoate compound | |
| CN102276421B (en) | Method for preparing 2-substituted-2-adamantane alcohol compound | |
| CN111233698A (en) | Polymerizable asymmetric azobenzene and preparation method thereof | |
| CN116514646B (en) | Preparation method of phenylpyruvic acid | |
| CN110963907B (en) | Green synthesis of 2, 2-dialkoxy acetophenone derivative | |
| CN109912515B (en) | Preparation method of rosuvastatin calcium | |
| CN115850207B (en) | Biphenyl derivative photoinitiator and preparation method and application thereof | |
| US2834813A (en) | Synthesis of vitamin a | |
| CN115850993B (en) | Chiral amphiphilic near-infrared aza-BODIPY dye and preparation method thereof | |
| CN1800126A (en) | Para phenyl phenol preparation method | |
| CN112574007B (en) | Novel cyclohexylimine ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F | |
| CN116730811B (en) | Preparation method of synthetic chiral camphor type beta-diketone |
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 |