CN100360486C - Method for preparing p-hydroxy-styrene - Google Patents
Method for preparing p-hydroxy-styrene Download PDFInfo
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- CN100360486C CN100360486C CNB2006100422009A CN200610042200A CN100360486C CN 100360486 C CN100360486 C CN 100360486C CN B2006100422009 A CNB2006100422009 A CN B2006100422009A CN 200610042200 A CN200610042200 A CN 200610042200A CN 100360486 C CN100360486 C CN 100360486C
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- hydroxybenzene ethene
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Abstract
The present invention relates to a method for preparing p-hydroxy-styrene, which belongs to the technical field of chemical industry and medicine intermediat synthesis. General reagent of p-hydroxy benzaldehyde, malonic acid and diethylamine as raw materials and a synthesis method of one-step material filling, fixed heating temperature at ordinary pressure and one-step reaction is adopted to prepare the p-hydroxy-styrene. The method of the present invention enhances the reaction yield of the p-hydroxy-styrene, simplifies a mixing working procedure of materials, fixes the reaction temperature, shortens the reaction time, simplifies postprocessing procedures of products, and greatly reduces the preparation cost of the p-hydroxy-styrene.
Description
(1) technical field
The present invention relates to the preparation method of para hydroxybenzene ethene, belong to chemical industry and medicine intermediate synthesis technical field.
(2) background technology
Para hydroxybenzene ethene is a kind of important chemical and medicine intermediate, in all kinds of macromolecular materials and medical building-up process, have comparatively widely and use, as emerging photoresist material technology, the agent of eurymeric chemically amplified photo resist generally adopts the derivative of poly(4-hydroxystyrene) as acid-sensitive resin, containing para hydroxybenzene vinyl polymer photoresist has become the gordian technique of photoengraving 0.11 μ m live width chip, referring to Meng Shiyun, and Li Guangxian, poplar its, Huang Yajiang; " the synthetic and progress that is used for the poly(4-hydroxystyrene) of photo-resist ", chemical progress, 2004,16 (2) 243-249.
Report according to existing literature, para hydroxybenzene ethene and derivative thereof adopt the Wittig prepared in reaction more, in this method, adopt the p-Hydroxybenzaldehyde derivative, as to acetoxyl group phenyl aldehyde etc., at organic alkali such as sodium methylate, or under the effect of potassium tert.-butoxide, with reagent effects such as methyl iodides, generate required product.In this reaction process, preparation technology and employing raw material are comparatively expensive, and it is held at high price, imported raw material is about about 6000 yuan/kilogram, domestic still do not have a special manufacturer production, is subjected to the restriction of material factor, influenced the further application in every field of para hydroxybenzene ethene and derivative thereof.There is the investigator once to propose to take the way of secondary decarboxylation to prepare para hydroxybenzene ethene, but, fails to be accepted by production department owing to reasons such as productive rates.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of novel para hydroxybenzene ethene is provided.
The present invention utilizes propanedioic acid and aldehyde ketone generation nucleophilic addition, products therefrom is easy to take place decarboxylic reaction and synthesizes para hydroxybenzene ethene, isothermal reaction in non-proton property high boiling solvent, adopt solution extraction, the washing reaction liquid of specific pH value then, promptly get required purity para hydroxybenzene ethene after the drying.Reaction equation is as follows:
The present invention is a raw material with common agents p-Hydroxybenzaldehyde and propanedioic acid, in the presence of basic catalyst, in non-proton property polar organic solvent, constant Heating temperature under the normal pressure, adopt once and feed in raw material, the synthetic method of single step reaction prepares para hydroxybenzene ethene, and concrete steps are as follows:
Raw material p-Hydroxybenzaldehyde and propanedioic acid join in the reactor according to 1: 1.5～2.5 mol ratio, again according to p-Hydroxybenzaldehyde: catalyzer is 10～20: 1～2 mol ratio adding basic catalyst, add the organic solvent stirring again and make reactants dissolved, be heated to 110～160 ℃, perhaps be heated to 80～100 ℃ earlier, constant temperature 2-5 hour, be warming up to 110～160 ℃ then, continue to stir, temperature control 5～8 hours is finished reaction.Reaction solution is shifted out reactor, cooling, to slightly acidic, organic extractant extracts with the dilute hydrochloric acid adjust pH; Extraction liquid washs with saturated sodium bicarbonate aqueous solution, perhaps uses with saturated sodium bicarbonate aqueous solution to have the sodium hydroxide of identical pH value or the solution washing of yellow soda ash; Wash with inorganic salt solution again, anhydrous sodium sulfate drying, underpressure distillation gets colorless oil, is product para hydroxybenzene ethene.
Above-mentioned non-proton property polar organic solvent is selected from N, dinethylformamide or dimethyl sulfoxide (DMSO).The not strict qualification of the consumption of organic solvent is advisable can make reactants dissolved.
Above-mentioned basic catalyst is selected from diethylamine, dialkylamine compounds such as Pyrrolidine or piperidines.
Above-mentioned reaction solution uses the dilute hydrochloric acid adjust pH to the preferred pH=4 of slightly acidic～6.
Above-mentioned organic extractant is selected from the polar solvent that can not dissolve each other with water, and is concrete as ethyl acetate, methylene dichloride or chloroform etc.
Above-mentioned inorganic salt solution is saturated sodium-chlor, Repone K or aqueous sodium persulfate solution.Adopting saturated inorganic salt solution washing, is under the situation that as far as possible reduces product loss, removes a small amount of sodium bicarbonate that exists in the system, prepares for further drying, distillation, and inorganic salt should be chemically stable inorganic salt.
Can adopt protection of inert gas in the above-mentioned reaction process, rare gas element generally is selected from nitrogen or argon gas.
Also can take azeotropic water removing in the above-mentioned reaction process, with further raising productive rate.
Extraction liquid adopts the saturated sodium bicarbonate aqueous solution washing in the method for the present invention, not only effectively prevent product para hydroxybenzene ethene (product para hydroxybenzene ethene has certain solubleness in neutral water) soluble in water, high boiling point reaction solvent soluble in water, unreacted acid propanedioic acid and other impurity can also be transferred to aqueous phase and discard.Washings can also adopt other inorganic base substances soluble in water such as sodium hydroxide, yellow soda ash etc. water-soluble except that taking the saturated sodium bicarbonate aqueous solution, is made into the system that has identical pH value with saturated sodium bicarbonate aqueous solution, can reach same effect.
The preparation method of para hydroxybenzene ethene of the present invention, in order to obtain productive rate preferably, should note the following aspects:
1. organic solvent is preferably selected the bigger non-protonic solvent of polarity, and as N, dinethylformamide, dimethyl sulfoxide (DMSO) etc. can make solvent soluble in water and remove in last handling process, thereby make the product purification process simple and easy to do.Organic solvent preferably has higher boiling point and better chemical stability, because temperature reaches 110 ℃ and promptly has product to generate in building-up process, but can obtain productive rate preferably at (about 150 ℃) under the higher relatively temperature.Temperature is controlled at about 150 ℃, and the minor fluctuations of temperature is to the productive rate and the not influence of quality of product, and this will help the control in the suitability for industrialized production.Because of the water in the reaction system can make molecular balance to being unfavorable for that the direction that improves productive rate moves, therefore generally will be with after the organic solvent drying of using, distillation or underpressure distillation deoxygenation dewater, and preserve stand-by under inert atmosphere.Must notice that the oxygen scavenger of choosing that dewaters can not react with organic solvent self.
2. para hydroxybenzene ethene is unstable in air and other oxidative environments, therefore can adopt protection of inert gas in reaction process, and general optional nitrogen of rare gas element or argon gas can improve productive rate 5%-10%.
3. adopt this law to prepare para hydroxybenzene ethene, chemical reaction is a reversing process, and the existence of water is unfavorable for the raising of productive rate, and can constantly produce water in reaction process, therefore can take the way of azeotropic water removing further to improve productive rate in reaction process.
4. this preparation feedback can carry out in two steps, promptly at first is warmed up to a certain degree, and reaction is carried out, and generates the compound p-Coumaric Acid, and the decarboxylation that heats up then obtains final product.But take this kind method to increase the reaction times, it is also not obvious to improve productive rate.
5. in the product last handling process, adopt dilute hydrochloric acid to regulate adjust pH to the slightly acidic process, actually introduce excessive relatively water, and the solvent that reaction is adopted and water can be arbitrarily than dissolving each other, thereby product para hydroxybenzene ethylene moiety is separated out from system.
6. anhydrous sodium sulfate drying is because product para hydroxybenzene ethene is unstable in air and other oxidative environments, as early as possible with product treatment Cheng Chunpin, preserves so that seal in processes such as distillation.
The present invention adopts " one pot " prepared in reaction para hydroxybenzene ethene in the liquid-phase system under the steady temperature heating condition, raw material is cheap and easy to get, and preparation manipulation is simple, last handling process is simple, product yield height, steady quality, parameter is convenient to control, and flow process is short, and energy consumption is low.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:
Raw material p-Hydroxybenzaldehyde 0.61 gram, propanedioic acid 1.04 grams join round-bottomed flask, add 3mL solvent N, dinethylformamide, stirring and dissolving, add basic catalyst diethylamine 0.1mL again, be heated to 150 ℃, the reaction system color by light yellow add gradually be deep to orange red, temperature control 6 hours is finished reaction.Reaction solution is shifted out reactor, in ice-water bath, use dilute hydrochloric acid adjust pH to 4, there is light grey oily matter to separate out, ethyl acetate extraction, saturated sodium bicarbonate aqueous solution washed twice, saturated sodium-chloride water solution washed twice, anhydrous sodium sulfate drying, underpressure distillation gets colorless oil, is product para hydroxybenzene ethene.Productive rate 72%.
Embodiment 2:
As described in embodiment 1, different is to take the nitrogen protection measure in reaction process, productive rate 78%.Improve 6% than embodiment 1 productive rate.
Embodiment 3:
Raw material p-Hydroxybenzaldehyde 1.22 grams, propanedioic acid 2.08 grams join round-bottomed flask, add 6mL solvent N, dinethylformamide, stirring and dissolving, add basic catalyst quadrol 0.2mL again, be warming up to 90 ℃, kept temperature 3 hours, be heated to 150 ℃, temperature control 6 hours is finished reaction.Reaction solution is shifted out reactor, in ice-water bath, use dilute hydrochloric acid adjust pH to 4, there is light yellow oil to separate out, ethyl acetate extraction, saturated sodium bicarbonate aqueous solution washed twice, saturated sodium-chloride water solution washed twice, anhydrous sodium sulfate drying, underpressure distillation gets colorless oil, is product para hydroxybenzene ethene.Productive rate 69%.
Embodiment 4:
As described in embodiment 1, different is that organic solvent is a dimethyl sulfoxide (DMSO), and basic catalyst is a diethylamine, dichloromethane extraction, with washing twice, saturated again potassium chloride solution washed twice with the aqueous sodium hydroxide washes that saturated sodium bicarbonate aqueous solution has an identical pH value.
Comparative Examples 1:
Raw material p-Hydroxybenzaldehyde 1.22 grams, propanedioic acid 2.08 grams join round-bottomed flask, add 6mL solvent N, dinethylformamide, stirring and dissolving, add basic catalyst quadrol 0.2mL again, be warming up to 65 ℃, kept temperature 3 hours, be heated to 150 ℃, temperature control 6 hours is finished reaction.Reaction solution is shifted out reactor, in ice-water bath, use dilute hydrochloric acid adjust pH to 4, there is oily matter to separate out, ethyl acetate extraction, saturated sodium bicarbonate aqueous solution washed twice, saturated sodium-chloride water solution washed twice, anhydrous sodium sulfate drying, underpressure distillation gets colorless oil, is product para hydroxybenzene ethene.Productive rate 48%.
In the operation of this Comparative Examples, be 65 ℃ owing to heat temperature control for the first time, reaction may reach the generation of other side reactions not too fully, though cause this Comparative Examples close with embodiment 3 methods, productive rate reduces to 48%.
Comparative Examples 2:
Raw material p-Hydroxybenzaldehyde 0.61 gram, propanedioic acid 1.04 grams join round-bottomed flask, add 3mL organic solvent pyridine, stirring and dissolving, add basic catalyst quadrol 0.1mL again, be warming up to 65 ℃, kept temperature 3 hours, be heated to 120 ℃, temperature control 6 hours is finished reaction.Reaction solution is shifted out reactor, in ice-water bath, use dilute hydrochloric acid adjust pH to 4, there is oily matter to separate out, ethyl acetate extraction, saturated sodium bicarbonate aqueous solution washed twice, saturated sodium-chloride water solution washed twice, anhydrous sodium sulfate drying, underpressure distillation gets colorless oil, is product para hydroxybenzene ethene.Productive rate 34%.
In this Comparative Examples, the change of organic solvent and control temperature reduction for the second time though there is product to produce, cause productive rate further to reduce, and illustrate that optimum temps should be about 150 ℃.
Claims (5)
1. the preparation method of a para hydroxybenzene ethene; with p-Hydroxybenzaldehyde and propanedioic acid is raw material, is under the catalyzer with the diethylamine, in non-proton property polar organic solvent; under the normal pressure under the steady temperature heating condition; adopt once and feed in raw material, the synthetic method of single step reaction prepares para hydroxybenzene ethene, adopts protection of inert gas in the reaction process; take azeotropic water removing; described non-proton property polar organic solvent is selected from N, dinethylformamide or dimethyl sulfoxide (DMSO)
Concrete steps are as follows:
Raw material p-Hydroxybenzaldehyde and propanedioic acid join in the reactor according to 1: 1.5～2.0 mol ratio, again according to p-Hydroxybenzaldehyde: catalyzer is 10～20: 1～2 mol ratio adding diethylamine catalyzer, add the organic solvent stirring again and make reactants dissolved, be heated to 150～160 ℃, perhaps be heated to 80～100 ℃ earlier, constant temperature 2-5 hour, be warming up to 150～160 ℃ then; Continue to stir, temperature control 5～8 hours is finished reaction; Reaction solution is shifted out reactor, cooling, to slightly acidic, organic extractant extracts with the dilute hydrochloric acid adjust pH; Extraction liquid washs with saturated sodium bicarbonate aqueous solution, perhaps uses with saturated sodium bicarbonate aqueous solution to have the sodium hydroxide of identical pH value or the solution washing of yellow soda ash; Wash with inorganic salt solution again, anhydrous sodium sulfate drying, underpressure distillation gets colorless oil, is product para hydroxybenzene ethene.
2. the preparation method of para hydroxybenzene ethene as claimed in claim 1 is characterized in that, described reaction solution uses the dilute hydrochloric acid adjust pH to pH=4～6.
3. the preparation method of para hydroxybenzene ethene as claimed in claim 1 is characterized in that, described organic extractant is selected from ethyl acetate, methylene dichloride or chloroform.
4. the preparation method of para hydroxybenzene ethene as claimed in claim 1 is characterized in that, described inorganic salt solution is saturated sodium-chlor, Repone K or aqueous sodium persulfate solution.
5. the preparation method of para hydroxybenzene ethene as claimed in claim 1 is characterized in that, described rare gas element is selected from nitrogen or argon gas.
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| CN108658731B (en) * | 2018-06-01 | 2022-05-06 | 巨野现代精细化工有限公司 | Synthetic method of p-hydroxystyrene |
| CN108640819A (en) * | 2018-06-12 | 2018-10-12 | 上海博栋化学科技有限公司 | A kind of method of one pot process hydroxy styrenes class compound |
| CN114773191A (en) * | 2022-04-29 | 2022-07-22 | 四川东材科技集团成都新材料有限公司 | Method for preparing p-acetoxystyrene by one-pot method |
| 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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| Title |
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| 丙二酸发生羟醛缩合时的二次脱羧反应. 彭啸等.云南大学学报，第26卷第3期. 2004 * |
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