CN102229529B - Preparation method of (methyl) crylic acid phenylethanol ester compounds - Google Patents
Preparation method of (methyl) crylic acid phenylethanol ester compounds Download PDFInfo
- Publication number
- CN102229529B CN102229529B CN2011101209434A CN201110120943A CN102229529B CN 102229529 B CN102229529 B CN 102229529B CN 2011101209434 A CN2011101209434 A CN 2011101209434A CN 201110120943 A CN201110120943 A CN 201110120943A CN 102229529 B CN102229529 B CN 102229529B
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- logical formula
- methyl
- acid
- 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.)
- Active
Links
Abstract
The invention relates to a preparation method of (methyl) crylic acid phenylethanol ester compounds. The targeted compounds are prepared by performing esterification reaction or ester exchange reaction on (methyl) crylic acid (ester) and phenylethanol compounds in the presence of an acid catalyst and a polymerization inhibitor. In the method, the used two reaction raw materials are the common chemical reagents, so highly irritant raw materials are avoided; and the targeted products are obtained through the esterification reaction or the ester exchange reaction, so the method is mild in reaction condition, high in yield, simple and convenient in separation and purification, high in purity of the obtained product and applicable to large-scale industrial production.
Description
Technical field
The present invention relates to organic chemistry filed, be specifically related to a kind of by the method for esterification or transesterification reaction preparation (methyl) crylic acid phenylethanol ester compounds.
Background technology
(methyl) crylic acid phenylethanol ester compounds is the extremely important polymer monomer of a class, and described polymkeric substance is widely used in the aspects such as sizing agent, coating, resin, fiber process, rubber industry, medical material.Due to its good security and compatibility, by hot research be applied to the life medical fields (referring to WO2008/013950A2, WO2009/137525A1 etc.) such as dental material and contact lens.
(methyl) crylic acid phenylethanol ester compounds monomer synthetic responds usually, and speed is slow, low conversion rate, the be heated characteristics of easy polymerization of raw material and product.The synthetic route of bibliographical information is less, and existing report is the method that the low temperature acyl chlorides becomes ester.
The low temperature acyl chlorides becomes the ester method, as document (J.Org.Chem.2005,70,251-260) described, obtain the methacrylic acid phenylglycollic ester with the reaction of methacrylic chloride and phenylethyl alcohol.The dichloromethane solution of phenylethyl alcohol and triethylamine is cooled to 0 ℃, drips wherein methacrylic chloride.Eliminate unnecessary triethylamine with excessive hydrochloric acid solution again, with sodium hydrogen carbonate solution, wash away hydrochloric acid.In the method, the acyl chlorides price is high, unstable, and pungency is strong, in using and storing, personnel and environment is brought to danger and problems, high to processing unit and working condition requirement, the high enterprise of production cost.
Esterification and transesterification reaction are typical balanced reactions, and speed of response is slow usually, and esterification yield is low, need to improve temperature toward contact and promote reaction with the prolongation reaction times.For esterification or the transesterification reaction of (methyl) acrylic compounds, above-mentioned phenomenon is obvious, also very easily is subject to thermopolymerization simultaneously.Therefore, find suitable reaction conditions, suitable raw material, suitable feed way, promote esterification or transesterification reaction and obtain value product and practical production technique very necessary.
Summary of the invention
For overcoming the defect of (methyl) crylic acid phenylethanol ester compounds preparation method in prior art, the purpose of this invention is to provide the preparation method of a kind of (methyl) crylic acid phenylethanol ester compounds.
Described preparation method by general formula (I) and (II) compound prepare target compound by esterification or transesterification reaction;
Described general formula (I) compound is:
Wherein, R
1For H or CH
3R
2For OH, OCH
3, OCH
2CH
3Or OCH (CH
3)
2
Described general formula (II) compound is:
Wherein, R
3For H, OH, alkyl or halogen, the preferred C1-C6 alkyl of described alkyl.
Described preparation method is further comprising the steps:
(1) by general formula (II) compound, acid catalyst, stopper mixes and add organic solvent, is warming up to 50～90 ℃;
(2) drip general formula (I) compound at the described temperature of step (1), and the by product generated except dereaction by atmospheric pressure reflux or underpressure distillation;
(3) dropwising the described temperature of rear maintenance to reaction finishes.
Above-mentioned reaction can adopt the normal experiment means to monitor when complete to raw material reaction to react end, as thin-layer chromatography, gas-chromatography or high performance liquid chromatography etc.
Described acid catalyst is sulfuric acid, phosphoric acid, Phenylsulfonic acid or tosic acid; Described stopper is Resorcinol, p methoxy phenol, Butylated Hydroxytoluene, 4-tert-butyl catechol or 2-Tert. Butyl Hydroquinone.
The consumption of the described acid catalyst of step (1) and general formula (II) compound is mol ratio 0.02～0.4: 1, preferably 0.1～0.3: 1; The consumption of described stopper and general formula (II) compound is mass ratio 0.1～3: 1000, preferably 0.1～1: 1000.
Described organic solvent is selected from benzene,toluene,xylene or hexanaphthene; The consumption of described solvent is every gram general formula (II) compound 3～10mL.
The described time for adding of step (2) is 1～10 hour, preferably 2～5 hours.
Described general formula (I) compound and general formula (II) compound amount are mol ratio 1.0～3.0: 1.
Also comprise post-processing step in above-mentioned any one technical scheme: reaction is down to room temperature by reaction system after finishing, and adds alkaline solution to water to be neutral, and organic phase concentrates to obtain target compound.
The aqueous solution that described alkaline solution is sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus; Concentration is that 0.02g/mL is to saturated.
Described target compound underpressure distillation is purified, and the vacuum tightness of described underpressure distillation is 5-300Pa; Distillation temperature is 50～90 ℃.
Reaction process of the present invention is as follows:
In general formula (I) compound according to R
2Difference, the by product difference that esterification or transesterification reaction produce, carboxylic esterification produces water, transesterification reaction generates corresponding alcohol, the mode of separating determines with the boiling point difference of reacting organic solvent according to by product, if the boiling point of the by-product alcohols that temperature of reaction produces higher than reaction, carry out normal pressure and separate by-product alcohols; If temperature of reaction lower than the boiling point of by-product alcohols, adopts underpressure distillation to remove by product, for guaranteeing esterification, to the positive reaction direction, carry out better, the rate of addition of general formula (I) compound is best suitable with speed that by product is removed.
In method of the present invention, raw material (methyl) vinylformic acid (ester) and target compound (methyl) crylic acid phenylethanol ester compounds are owing to containing active double bond structure, therefore, polymerization very easily occurs in conventional esterification or transesterification reaction form complicated polymerization system, make esterification or transesterification reaction be difficult to carry out, in prior art, with esterification or ester-interchange method, do not prepare (methyl) crylic acid phenylethanol ester compounds.Technical scheme of the present invention adds stopper in esterification or transesterification reaction, and adjust a series of technique means such as temperature of reaction, solvent, material dropping mode, separation and purification operation, when impelling esterification or transesterify to carry out to positive dirction, prevent the generation of polyreaction.That is to say, the parameters such as catalyzer of the present invention, stopper, temperature of reaction, time be all through strict cooperation with control just obtain good and become the ester effect.
Two kinds of reaction raw materials of preparation method of the present invention are all common chemical reagent, and easy being easy to get avoided use strong and stimulating raw material; Obtain target product by esterification or transesterification reaction, the reaction conditions gentleness, yield is higher, and separation and purification is easy, and products therefrom purity is good, is applicable to large-scale industrial production.
Embodiment
Following examples are used for the present invention is described, but are not used for limiting the scope of the invention.
Embodiment 1
The standby 2 phenylethyl alcohol acrylate of acid esters legal system
Add the 10.0Kg phenylethyl alcohol in the 100L reactor, 34.4Kg toluene (4.0mL/g), the 1.62Kg vitriol oil (0.1eq.) and 2.0g p methoxy phenol, stir and obtain light yellow clarification mixed solution, and mixed solution is heated to 70-75 ℃.To dripping 7.07Kg vinylformic acid (1.3eq.) liquid in mixed solution, start to vacuumize simultaneously and make refluxing toluene divide water.Drip vinylformic acid 2 hours, after, be incubated 70～75 ℃ and continue decompression minute water, to reacting completely.Reaction mixture being cooled to room temperature, in mixed solution, dripping saturated aqueous sodium carbonate, is neutral to water; Standing separatory, after organic phase water (20L * 3) washing, use 1.0Kg anhydrous magnesium sulfate drying 4 hours; Suction filtration, toluene for filter cake (1.0L) drip washing, filtrate decompression is revolved to steam and is obtained brown color liquid crude product (vacuum tightness is-0.09MPa that bath temperature is 55 ℃).At 13-20Pa, underpressure distillation under 70～78 ℃ of conditions obtains colourless liquid product: 10.7Kg, yield: 74.3%, and purity (GC):>98.5%.
Embodiment 2
The standby 2 phenylethyl alcohol of acid esters legal system-2-methacrylic ester
Add the 24.0Kg phenylethyl alcohol in the 200L reactor, 82.6Kg toluene (4.0mL/g) the 1.9Kg vitriol oil (0.1eq.) and 2.4g Resorcinol, stir and obtain light yellow clarification mixed solution.This mixed solution is heated to 60-65 ℃, is added dropwise to 22.0Kg methacrylic acid (1.3eq.), start to vacuumize simultaneously and make refluxing toluene divide water, drip 5 hours.Dropwise, be incubated 60～65 ℃ of decompression minute water, to reacting completely.Be cooled to room temperature, in system, be added dropwise to the 0.04g/mL aqueous sodium carbonate, be neutralized to water for neutral; Standing separatory, organic phase water (24L * 3) washing, then use the 2.0Kg anhydrous magnesium sulfate drying 4 hours; Suction filtration, toluene for filter cake (2.0L) drip washing, filtrate decompression is revolved to steam and is obtained brown color liquid crude product (vacuum tightness is-0.09MPa that bath temperature is 55 ℃).At 5-10Pa, and underpressure distillation under 62～68 ℃ of conditions (really obtain colourless liquid product: 26.8Kg, yield: 71.8%, purity (GC) 98.6%.
Embodiment 3
Ester-interchange method prepares 2 phenylethyl alcohol-2-methacrylic ester
Add the 48.9g phenylethyl alcohol in the 500mL reaction flask, 100mL toluene (2.0mL/g) the 7.8g vitriol oil (0.2eq.) and 0.024g Resorcinol, stir and obtain light yellow clarification mixed solution.This mixed solution is heated to 70-75 ℃, slowly is added dropwise to 48.1g methyl methacrylate (1.2eq.), start to vacuumize slow solvent distillation (maintenance distillates speed and rate of addition is basically identical) simultaneously, the dropping process continues 3 hours.Dropwise, be incubated 70～75 ℃ to reacting completely.Benzene feedstock ethanol has residue, mends to be added dropwise to 4.0g methyl methacrylate (0.1eq.), then is incubated 70～75 ℃ and tracks to and react completely.Be cooled to room temperature, in system, add 100mL toluene (2.0mL/g), be added dropwise to the 0.14g/mL aqueous sodium carbonate, be neutralized to water for neutral; Standing separatory, after organic phase water (100mL * 3) washing, then use 10g anhydrous magnesium sulfate drying 4h; After suction filtration, filtrate decompression is revolved steaming (vacuum tightness is-0.09MPa that bath temperature is 55 ℃), obtains liquid product: 56.1g, and yield: 73.8%, purity (GC): 83.4%.
Although above used general explanation, embodiment and experiment, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (1)
1. the preparation method of (methyl) crylic acid phenylethanol ester compounds, is characterized in that, by logical formula I and (II) compound, by esterification or transesterification reaction, prepares target compound;
Described logical formula I compound is:
, wherein, R
1For H or CH
3R
2For OH, OCH
3, OCH
2CH
3Or OCH (CH
3)
2
Described logical formula II compound is:
, wherein, R
3For H; Described preparation method comprises the following steps:
(1) will lead to formula II compound, acid catalyst, stopper mixes and add organic solvent, is warming up to 50～90 ℃; Described acid catalyst is sulfuric acid; Described stopper is Resorcinol, p methoxy phenol, Butylated Hydroxytoluene, 4-tert-butyl catechol or 2-Tert. Butyl Hydroquinone; Described organic solvent is selected from benzene,toluene,xylene or hexanaphthene; The consumption of described acid catalyst and logical formula II compound is mol ratio 0.1～0.3:1; The consumption of described stopper and logical formula II compound is mass ratio 0.1～1:1000; The consumption of described organic solvent is the logical formula II compound 3～10mL of every gram;
(2) drip logical formula I compound at the described temperature of step (1), and remove by underpressure distillation the by product that dereaction generates, described time for adding is 2～5 hours, and described logical formula I compound and logical formula II compound amount are mol ratio 1.0～3.0:1;
(3) dropwising the described temperature of rear maintenance to reaction finishes;
(4) post-processing step: reaction is down to room temperature by reaction system after finishing, and adds alkaline solution to water to be neutral, and organic phase concentrates to obtain target compound, the aqueous solution that described alkaline solution is sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus; Concentration is that 0.02g/mL is extremely saturated, and described target compound underpressure distillation is purified, and the vacuum tightness of described underpressure distillation is 5-300Pa; Distillation temperature is 50～90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101209434A CN102229529B (en) | 2011-05-11 | 2011-05-11 | Preparation method of (methyl) crylic acid phenylethanol ester compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101209434A CN102229529B (en) | 2011-05-11 | 2011-05-11 | Preparation method of (methyl) crylic acid phenylethanol ester compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229529A CN102229529A (en) | 2011-11-02 |
| CN102229529B true CN102229529B (en) | 2013-12-04 |
Family
ID=44842150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101209434A Active CN102229529B (en) | 2011-05-11 | 2011-05-11 | Preparation method of (methyl) crylic acid phenylethanol ester compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229529B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193911B (en) * | 2013-03-14 | 2015-04-08 | 新发药业有限公司 | Amino arene structure unit-containing polyacrylate functionalized polymer and preparation method thereof |
| CN103553920A (en) * | 2013-09-26 | 2014-02-05 | 上海维凯化学品有限公司 | Preparation method of phenoxy benzyl acrylic ester |
| CN110818560A (en) * | 2019-12-02 | 2020-02-21 | 怀化金鑫新材料有限公司 | Preparation method of 4-benzyloxy phenyl ethyl n-decanoate |
| CN112079714A (en) * | 2020-09-22 | 2020-12-15 | 湖北长海新能源科技有限公司 | Preparation method of 2-phenylethyl acrylate |
| CN114315583A (en) * | 2021-12-22 | 2022-04-12 | 红宝丽集团泰兴化学有限公司 | Preparation method and device of acrylate compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208032A (en) * | 1997-08-13 | 1999-02-17 | 中国石化齐鲁石油化工公司 | Preparation of acrylate or higher methyl acrylate |
| CN1733687A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | A (methyl) higher aliphatic acrylate preparation method |
| JP2010095467A (en) * | 2008-10-16 | 2010-04-30 | Toagosei Co Ltd | Method for continuously producing (meth)acrylate |
| CN101723830A (en) * | 2009-12-04 | 2010-06-09 | 广东工业大学 | Method for synthesizing (methyl) acrylate |
| CN101959838A (en) * | 2008-02-27 | 2011-01-26 | 巴斯夫欧洲公司 | Method for the production of (meth)acrylates of C10 alcohol mixtures |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279076C (en) * | 2001-01-11 | 2006-10-11 | Dsmip财产有限公司 | Radiation curable coating composition |
-
2011
- 2011-05-11 CN CN2011101209434A patent/CN102229529B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208032A (en) * | 1997-08-13 | 1999-02-17 | 中国石化齐鲁石油化工公司 | Preparation of acrylate or higher methyl acrylate |
| CN1733687A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | A (methyl) higher aliphatic acrylate preparation method |
| CN101959838A (en) * | 2008-02-27 | 2011-01-26 | 巴斯夫欧洲公司 | Method for the production of (meth)acrylates of C10 alcohol mixtures |
| JP2010095467A (en) * | 2008-10-16 | 2010-04-30 | Toagosei Co Ltd | Method for continuously producing (meth)acrylate |
| CN101723830A (en) * | 2009-12-04 | 2010-06-09 | 广东工业大学 | Method for synthesizing (methyl) acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229529A (en) | 2011-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102229529B (en) | Preparation method of (methyl) crylic acid phenylethanol ester compounds | |
| CN101863763A (en) | Method for catalytically synthesizing isobornyl methacrylate by activated carbon supported stannic chloride | |
| CN109053443A (en) | The bromo- 3- aldehyde radical-phenoxy group of 4-(4-)-benzonitrile synthetic method | |
| CN105130798A (en) | Novel synthetic method for F-acrylic acid and derivative thereof | |
| JP5702048B2 (en) | Method for producing (meth) acrylic acid naphthyl ester | |
| CN104045555B (en) | A kind of preparation method of triglycol dicarboxylic ester | |
| CN104803849A (en) | Synthesizing method of acrylic fluorine-containing ester and derivatives thereof through catalyzed synthesis of solid acid | |
| CN102180843A (en) | Preparation method of 2-(2-amino-4-thiazolyl)-2(Z)-triphenylmethoxy imidoacetic acid | |
| CN102503823B (en) | Synthesis process for fatty acyl citrate compound | |
| CN101735053B (en) | Method for preparing maleic acid diethylene glycol monoethyl ether ester | |
| CN103992294A (en) | Synthesis method of acrylamide type reactive diluent | |
| CN101781205B (en) | Method for synthesizing substitutional crylic acid phenyl ester | |
| CN105732384A (en) | Preparation method of metacrylic acid ester containing fluoro-alcohol | |
| CN103524402A (en) | Preparation method of efficient stable inhibitor | |
| KR101362883B1 (en) | A method for preparing (meth)acrylic acid phenyl ester | |
| CN102531896A (en) | Production method of ethyl trifluoroacetate | |
| CN103588640B (en) | A kind of preparation method of glycol ether dicarboxylic ester | |
| CN101845055B (en) | Method for purifying dichloromethyl phenylsilane by chemical coordination effect | |
| CN101475456B (en) | Method for preparing cyclohexyl formaldehyde by ion liquid catalysis | |
| CN104628678B (en) | A kind of method based on 2-halogen propionyl chloride synthesizing propylene morpholide | |
| CN109694324A (en) | A kind of preparation method of methyl benzoate | |
| CN101723829B (en) | Method for synthesizing acecloguanosine lateral chain | |
| CN104418735A (en) | Preparation method of adamantine monoester | |
| CN102432465A (en) | Method for preparing methyl methacrylate | |
| CN102898456B (en) | O-benzyldiethoxymethylsilane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |