CN109485550A - The method for preparing styrene derivative with ionic liquid - Google Patents
The method for preparing styrene derivative with ionic liquid Download PDFInfo
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- CN109485550A CN109485550A CN201811361150.XA CN201811361150A CN109485550A CN 109485550 A CN109485550 A CN 109485550A CN 201811361150 A CN201811361150 A CN 201811361150A CN 109485550 A CN109485550 A CN 109485550A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
- C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to chemical industry and medicine intermediate synthesis technical fields, are related to a kind of method for preparing styrene derivative with ionic liquid.For this method using ionic liquid as solvent, catalytic reaction is high-efficient.Ionic liquid can repeatedly use, and save industrial production cost, and help to solve the environmental problem that conventional solvent generates.
Description
Technical field
The invention belongs to chemical industry and medicine intermediate synthesis technical field, it is related to a kind of preparing styrene with ionic liquid and spreading out
The method of biology.In particular to a kind of method for preparing styrene derivative with solion.
Background technique
Styrene derivative is one of medicine, the important intermediate in materials synthesis.In all kinds of high molecular materials and medicine
There are relatively broad application, such as 4-Vinyl phenol in synthesis process, in emerging photolithographic techniques, eurymeric chemical amplification is anti-
Erosion agent generally uses the derivative of poly(4-hydroxystyrene) as acid-sensitive resin, and the photoresist of based high molecular containing 4-Vinyl phenol is
As the key technology of 0.11 μm of line width chip of photoengraving, referring to Meng Shiyun, Li Guangxian, Yang Qi, Huang Yajiang；" for photic anti-
Lose the synthesis and its progress of the poly(4-hydroxystyrene) of agent ", chemical progress, 2004,16 (2) 243-249.
4-Vinyl phenol and its derivative mostly use Wittig reaction to prepare, in this method, using parahydroxyben-zaldehyde
Derivative, such as to acetoxyl group benzaldehyde, under the action of organic alkali such as sodium methoxide or potassium tert-butoxide, with iodomethane
Equal reagents effect, generates required product.In the reaction process, preparation process and use raw material costly, make its price
High, the country there is no special producer to produce, and is restricted by material factor, affects 4-Vinyl phenol and its derivative exists
Every field is further applied.
Ionic liquid due to its unique physicochemical properties and good substrate compatibility and catalyst stability,
It is widely used in the fields such as extraction and separation, organic synthesis and catalysis.
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of novel styrene derivative.This method with
For ionic liquid as solvent, catalytic reaction is high-efficient.Ionic liquid can repeatedly use, and save industrial production cost,
And help to solve the environmental problem that conventional solvent generates.
Summary of the invention
The present invention provides a kind of preparation method of styrene derivative, comprising:
In the presence of ionic liquid, reaction obtains Formula II compound for formula III compound and malonic acid；Formula II compound exists
In the presence of ionic liquid, reaction obtains compound of formula I；
Wherein, the R is selected from F, Cl, Br, cyano, nitro, C1-4 alkyl, C1-4 alkoxy or hydroxyl.
In some embodiments of the invention, the ionic liquid is as solvent or catalyst.
In some embodiments of the invention, the ionic liquid is selected from N- butyl-N- methyl piperidine bromide, N- fourth
Bis- (fluoroform sulphonyl) inferior amine salts of base-N- methyl piperidine, N- butyl-N- crassitude bromide, N- butyl-N- methylpyrrole
Bis- (fluoroform sulphonyl) inferior amine salts of alkane, tributyhnethylammonium chloride, bis- (fluoroform sulphonyl) inferior amine salts of tributyl-methyl phosphonium ammonium,
Tributyhnethylammonium chloride, N- methoxy ethyl-N- methyl diethyl ammonium tetrafluoroborate or its mixing, preferably are selected from N- butyl-
Bis- (fluoroform sulphonyl) inferior amine salts of N- methyl piperidine bromide, N- butyl-N- methyl piperidine, N- butyl-N- crassitude bromine
Bis- (fluoroform sulphonyl) inferior amine salts of salt, N- butyl-N- crassitude or its mixing, more preferably from N- butyl-N- methyl piperazine
Pyridine bromide, N- butyl-N- crassitude bromide, tributyhnethylammonium chloride or its mixing.
In some embodiments of the invention, the dosage (with unit of weight gram g calculating) of the ionic liquid is formula III
The 1-20 times of amount (with unit of weight gram g calculating) of compound, preferably 2-15 times is measured, and is more preferably measured from 2-10 times.Alternatively, in this hair
In bright some embodiments, the dosage of the ionic liquid be formula III compound 1,1.5,2,2.5,3,3.5,4,4.5,
5,5.5,6,6.5,7,7.5,8,8.5,9,9.5 or 10 times of amounts.
In some embodiments of the invention, the ratio between amount of substance of the formula III compound and malonic acid is selected from 1:1
~5,1:1~2.5 preferably are selected from, more preferably from 1:1~1.5.Alternatively, in some embodiments of the invention, the formula III
It closes the ratio between amount of substance of object and malonic acid and is selected from 1:1,1:1.5,1:2,1:2.5,1:3,1:3.5,1:4,1:4.5 or 1:5.
In some embodiments of the invention, in the formula III compound and malonic acid preparation formula II chemical procedure,
Reaction temperature is selected from 10-60 DEG C, 20~50 DEG C preferably is selected from, more preferably from 30~50 DEG C.
In some embodiments of the invention, in the Formula II preparation of compounds of formula Compound I step, reaction temperature choosing
From 80-200 DEG C, 100~180 DEG C preferably are selected from, more preferably from 120~160 DEG C.
In some embodiments of the invention, in the formula III preparation of compounds of formula II chemical procedure, the reaction time
Selected from 1~6 hour, it preferably is selected from 2~4 hours, most preferably from 3 hours.
In some embodiments of the invention, in the Formula II preparation of compounds of formula Compound I step, reaction time choosing
From 2~8 hours, it preferably is selected from 4~6 hours, most preferably from 5 hours.
In some embodiments of the invention, reacted by formula III preparation of compounds of formula II compound and by Formula II chemical combination
Object preparation of compounds of formula I is one pot reaction.The one pot reaction refers to that the reaction of formula III preparation of compounds of formula II compound terminates
Afterwards, without post-processing, the reaction by Formula II preparation of compounds of formula Compound I is directly carried out.
In some embodiments of the invention, the R group of the formula III compound, Formula II compound or compound of formula I
It is connected to phenyl ring contraposition.
In some embodiments of the invention, the formula III compound is selected from para hydroxybenzene acetaldehyde, to C1-4 alkoxy
Phenylacetaldehyde；The Formula II compound is selected from p-Coumaric Acid, to C1-4 alkoxy benzene acrylic acid；The compound of formula I choosing
From 4-Vinyl phenol, to C1-4 alkoxystyrene.
After the present invention uses ionic liquid as reaction dissolvent, reaction yield is improved.Ionic liquid, which can be repeated several times, to be made
With, saving industrial production cost, and help to solve the environmental problem that conventional solvent generates.
Specific embodiment
The present invention will be elaborated by following embodiment, be only as embodiment it is explanatory and be not intended to limitation this
The range of invention.
Embodiment 1
122.1g (1mol) parahydroxyben-zaldehyde and 104.1g (1mol) malonic acid, ionic liquid is added in 1000mL reaction flask
500g chlorination N- butyl-N- methyl piperidine bromide, 4g (0.1mol) sodium hydroxide react 3 hours at 40-50 DEG C, reheat
It is reacted 5 hours to 160 degree, drops to room temperature after the reaction was completed, directly extracted with ethyl acetate 500mLx3, brine It, concentration
Obtain product 4-Vinyl phenol 119.2g, yield 99.3%.
Embodiment 2
140.6g (1mol) p-chlorobenzaldehyde and 125.5g (1.2mol) malonic acid, ionic liquid is added in 1000mL reaction flask
Bis- (fluoroform sulphonyl) inferior amine salts of 500g N- butyl-N- methyl piperidine, 4g (0.1mol) sodium hydroxide are anti-at 40-50 DEG C
It answers 3 hours, is heated to 160 degree and reacts 5 hours, drop to room temperature after the reaction was completed, directly extracted with ethyl acetate 500mLx3,
Brine It is concentrated to get product p-chlorostyrene 137.2g, yield 99.0%.
Embodiment 3
131.1g (1mol) is added to cyanobenzaldehyde and 135.2g (1.3mol) malonic acid, ionic liquid in 1000mL reaction flask
Body 400g N- butyl-N- crassitude bromide, 4g (0.1mol) sodium hydroxide react 3 hours at 40-50 DEG C, reheat
It is reacted 5 hours to 160 degree, drops to room temperature after the reaction was completed, directly extracted with ethyl acetate 500mLx3, brine It, concentration
Product is obtained to cyano styrene 127.2g, yield 98.5%.
Embodiment 4
151.0g (1mol) paranitrobenzaldehyde and 145.6g (1.4mol) malonic acid, ionic liquid is added in 1000mL reaction flask
Bis- (fluoroform sulphonyl) inferior amine salts of body 400g N- butyl-N- crassitude, 4g (0.1mol) sodium hydroxide, at 40-50 DEG C
Lower reaction 3 hours is heated to 160 degree and reacts 5 hours, drop to room temperature after the reaction was completed, directly extracted with ethyl acetate 500mLx3
It takes, brine It, is concentrated to get product p-nitrophenyl ethylene 146.5g, yield 98.2%.
Embodiment 5
120.1g (1mol) p-tolyl aldehyde and 114.4g (1.1mol) malonic acid, ionic liquid is added in 1000mL reaction flask
Body 400g tributyhnethylammonium chloride, 4g (0.1mol) sodium hydroxide react 3 hours at 40-50 DEG C, are heated to 150 degree
Reaction 5 hours, drops to room temperature after the reaction was completed, is directly extracted with ethyl acetate 500mLx3, and brine It is concentrated to get production
Product p-methylstyrene 117.2g, yield 99.1%.
Embodiment 6
136.1g (1mol) P-methoxybenzal-dehyde and 114.4g (1.1mol) malonic acid, ion is added in 1000mL reaction flask
Bis- (fluoroform sulphonyl) inferior amine salts of liquid 600g tributyl-methyl phosphonium ammonium, 4g (0.1mol) sodium hydroxide react at 40-50 DEG C
It 3 hours, is heated to 160 degree and reacts 5 hours, drop to room temperature after the reaction was completed, directly extracted with ethyl acetate 500mL x3, food
Salt water washing is concentrated to get product to methoxy styrene 130.8g, yield 97.5%.
Embodiment 7
122.1g (1mol) parahydroxyben-zaldehyde and 104.1g (1mol) malonic acid, 500mL bis- is added in 1000mL reaction flask
Chloromethanes, 4g (0.1mol) sodium hydroxide react 3 hours under reflux conditions.After the reaction was completed, product is concentrated, removes two
500mL toluene is added in chloromethanes, then reacts 5 hours under reflux conditions, drops to room temperature after the reaction was completed.Product is concentrated, is added
Enter ethyl acetate and the extraction of saturated common salt water stratification, brine It is concentrated to get product 4-Vinyl phenol 75.1g, yield
62.5%.
Embodiment 8
122.1g (1mol) parahydroxyben-zaldehyde and 104.1g (1mol) malonic acid, 500mL first is added in 1000mL reaction flask
Benzene, 4g (0.1mol) sodium hydroxide react 3 hours under the conditions of 50~60 DEG C, then react 5 hours under reflux conditions, reaction
Room temperature is dropped to after the completion, product is concentrated, ethyl acetate and the extraction of saturated common salt water stratification is added, and brine It is concentrated to give
To product 4-Vinyl phenol 63.1g, yield 53.2%.
Claims (10)
1. a kind of preparation method of styrene derivative includes:
In the presence of ionic liquid, reaction obtains Formula II compound for formula III compound and malonic acid；Formula II compound is in ion
In the presence of liquid, reaction obtains compound of formula I；
Wherein, the R is selected from F, Cl, Br, cyano, nitro, C1-4 alkyl, C1-4 alkoxy or hydroxyl.
2. preparation method as described in claim 1, the ionic liquid is as solvent or catalyst.
3. preparation method as described in claim 1, the ionic liquid is selected from N- butyl-N- methyl piperidine bromide, N- butyl-
Bis- (fluoroform sulphonyl) inferior amine salts of N- methyl piperidine, N- butyl-N- crassitude bromide, N- butyl-N- crassitude
Bis- (fluoroform sulphonyl) inferior amine salts, tributyhnethylammonium chloride, tributyl-methyl phosphonium ammonium bis- (fluoroform sulphonyl) inferior amine salts, three
Butyl methyl ammonium chloride, N- methoxy ethyl-N- methyl diethyl ammonium tetrafluoroborate or its mixing.
4. preparation method as described in claim 1, the dosage of the ionic liquid is that 1-20 times of formula III compound is measured.
5. the ratio between amount of substance of preparation method as described in claim 1, the formula III compound and malonic acid is selected from 1:1
~5.
6. in preparation method as described in claim 1, the formula III compound and malonic acid preparation formula II chemical procedure,
Reaction temperature is selected from 10-60 DEG C.
7. preparation method as described in claim 1, in the Formula II preparation of compounds of formula Compound I step, reaction temperature choosing
From 80-200 DEG C.
8. preparation method as described in claim 1 is reacted by formula III preparation of compounds of formula II compound and by Formula II compound
Preparation of compounds of formula I is one pot reaction.
9. preparation method as described in claim 1, the R group of the formula III compound, Formula II compound or compound of formula I
It is connected to phenyl ring contraposition.
10. preparation method as described in claim 1, the formula III compound is selected from para hydroxybenzene acetaldehyde, to C1-4 alkoxy
Phenylacetaldehyde；The Formula II compound is selected from p-Coumaric Acid, to C1-4 alkoxy benzene acrylic acid；The compound of formula I choosing
From 4-Vinyl phenol, to C1-4 alkoxystyrene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751808A (en) * | 2022-04-29 | 2022-07-15 | 四川东材科技集团成都新材料有限公司 | Method for synthesizing p-hydroxystyrene by azeotropic one-pot method |
-
2018
- 2018-11-15 CN CN201811361150.XA patent/CN109485550B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| LIU, DAJIANG等: "N-Heterocyclic Carbene Promoted Decarboxylation of Lignin-Derived Aromatic Acids", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| YOGESH O. SHARMA等: "CO2 absorbing cost-effective ionic liquid for synthesis of commercially important alpha cyanoacrylic acids: A safe process for activation of cyanoacetic acid", 《GREEN CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751808A (en) * | 2022-04-29 | 2022-07-15 | 四川东材科技集团成都新材料有限公司 | Method for synthesizing p-hydroxystyrene by azeotropic one-pot method |
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Denomination of invention: Preparation of styrene derivatives from ionic liquids Effective date of registration: 20220629 Granted publication date: 20220104 Pledgee: Ningbo Tianjin Enterprise Service Co.,Ltd. Pledgor: NINGBO WEIXIN NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2022330001154 |
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Date of cancellation: 20230614 Granted publication date: 20220104 Pledgee: Ningbo Tianjin Enterprise Service Co.,Ltd. Pledgor: NINGBO WEIXIN NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2022330001154 |