CN101781205A - Method for synthesizing substitutional crylic acid phenyl ester - Google Patents
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Abstract
The invention relates to the field of chemosynthesis, in particular relating to a method for synthesizing substitutional crylic acid phenyl ester. The method comprises: substitutional crylic acid and one of phosphorus trichloride, phosphorus oxychloride, and thionyl chloride or phosphorus pentachloride are subjected to substitution to generate acryloyl chloride, and then the acryloyl chloride and the substituted phenol are subjected to an ester exchange reaction to generate substituted crylic acid phenyl ester. The method does not need to use a catalyst; the reaction can effectively control the generation of polymerization, and has high reaction yield; and the product is easy to separate and purify, the product purity is higher than 99%, and the invention has wide industry application prospect.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind of method of synthesizing substitutional crylic acid phenyl ester.
Background technology
Substitutional crylic acid phenyl ester is widely used in industrial circles such as coating, tackiness agent, printing ink because of active high, characteristics such as dilution capacity is strong, low toxicity, low irritant.At present, industrial main use transesterification reaction synthesizing substitutional crylic acid phenyl ester crude product utilizes the method for rectifying to purify.
CN1321102C discloses the reaction unit that uses reaction-distillation coupling operation, and by-product carbinol and methyl methacrylate evaporation are shifted out system, carries out the transesterification reaction synthesize methyl acrylic acid phenenyl ester of methyl methacrylate and phenols simultaneously.This method is carried out in fact in two steps, and the first step generates methyl methacrylate by methyl alcohol and methacrylic acid-respons, and this step reaction needs make catalyzer with strong acid, and esterification is reversible reaction, and the transformation efficiency of reactant is limited; Second step was carried out transesterification reaction by methyl methacrylate and phenol, and transesterification reaction also is reversible reaction usually, and the transformation efficiency of reactant is limited, and the reaction conversion ratio that particularly generates phenyl ester is lower.This causes by the transformation efficiency and the yield of methacrylic acid-respons system phenyl methacrylate lower, and two steps all must be used rectifying separation, complicated operation, and separation costs height.
CN101289388.A discloses the synthetic method of another kind of substitutional crylic acid phenyl ester.By acid anhydrides and substitutional crylic acid reaction, generate the acid anhydrides and the sour mixture that are used for synthetic target product, remove disacidify by the distillatory method, use phenols and anhydride reaction then, form the phenols acrylic compound.This production method adopts two-step approach, and it is more to generate by product in process of production equally, need just can obtain the high product of purity through rectifying separation repeatedly.Production cost height in the practical application has limited in industrial application.
Summary of the invention
The present invention is directed to the deficiency that transformation efficiency and product purity are low and be difficult to purify, a kind of new synthesizing substitutional crylic acid phenyl ester method is provided.Described method reaction conversion ratio is easy to separate and purify with product yield height, product.
In order to realize the foregoing invention purpose, the invention provides following technical scheme:
A kind of composite structure is suc as formula the method for compound shown in the I,
Compound shown in the substitution reaction production IV takes place in one of compound shown in the formula II and phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride, compound shown in the formula IV again with the generation of compound shown in formula III transesterification reaction generating structure suc as formula compound shown in the I.
R wherein
1Be hydrogen or alkyl, alkoxyl group, halogen, amido, amino, nitro, R
2, R
3, R
4, R
5And R
6Be hydrogen or alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, nitro.
When R1 was hydrogen, compound shown in the formula II was a vinylformic acid; Work as R
2, R
3, R
4, R
5And R
6During for hydrogen, compound shown in the formula III is a phenol, works as R
1, R
2, R
3, R
4, R
5And R
6When being hydrogen, compound shown in the formula I is a phenyl acrylate;
When R1 was not hydrogen, compound shown in the formula II was a substitutional crylic acid; Work as R
2, R
3, R
4, R
5And R
6One of when being not hydrogen, compound shown in the formula III is a fortified phenol, works as R
1, R
2, R
3, R
4, R
5And R
6One of when being not hydrogen, compound shown in the formula I is a substitutional crylic acid phenyl ester.
In order to simplify, compound is referred to as substitutional crylic acid phenyl ester shown in the following description Chinese style I, and compound is referred to as substitutional crylic acid shown in the formula II, and compound is referred to as fortified phenol shown in the formula III.
As preferably, the method for the invention, carry out in two steps:
Step 1: one of phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride are mixed with the substitutional crylic acid shown in the formula (II), be heated to boiling postcooling to 30～70 ℃, reaction 5-30min places 0.5-4h under the room temperature.Add stopper, get corresponding product cut after the distillation and get shown in the formula (IV) and replace acrylate chloride.
Step 2: the fortified phenol shown in the formula (III) is dissolved in solvent or is heated to be not less than the fortified phenol melting temperature (Tm), add step 1 synthetic again and replace acrylate chloride, at 40-75 ℃ of reaction 1-36h.
Two-step approach building-up reactions formula is as follows:
As selection, the method for the invention also can be finished in a step, and concrete steps are:
One of phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride are mixed with substitutional crylic acid and the stopper shown in the formula (II), be heated to 40-75 ℃, add the fortified phenol shown in the formula (III) then, reaction 1-36h.
The one-step synthesis reaction formula is as follows:
Preferably, substitutional crylic acid shown in the formula (II) and phosphorus trichloride or phosphorus oxychloride amount of substance ratio are about 6: 1-6.
Preferably, substitutional crylic acid shown in the formula (II) and thionyl chloride amount of substance ratio are about 4: 1-4.
Preferably, substitutional crylic acid shown in the formula (II) and phosphorus pentachloride amount of substance ratio are about 4: 1-4.
Preferably, stopper comprises cuprous chloride and Resorcinol in the step 1, and consumption is 0.5～15% of fortified phenol and a described substitutional crylic acid gross weight.
Preferably, at room temperature place 0.5-4h behind the reaction 5-30min in the step 1.
Preferably, during two-step approach was synthetic, described fortified phenol amount of substance was 5-15 with the amount of substance ratio of described substitutional crylic acid acyl chlorides: 10.
More preferably, organic solvent described in the step 2 was aromatic hydrocarbons, aryl alkyl ethers, chlorinated aromatic hydrocarbons, pyridine, dimethyl sulfoxide (DMSO) during two-step approach was synthetic, more preferably pyridine, toluene, dimethylbenzene.
Preferably, the synthetic described fortified phenol amount of substance of single stage method is 5-15 with the amount of substance ratio of described substitutional crylic acid: 10.
The two step synthesis methods of describing in embodiment are: in the stirred reactor of band condensing reflux, add quantitative substitutional crylic acid and phosphorus trichloride or phosphorus oxychloride or thionyl chloride or or phosphorus pentachloride, be heated to the boiling postcooling, leave standstill behind the reaction certain hour, add stopper, a certain boiling range cut is got in distillation, get intermediate product and replace acrylate chloride, this product can be through the gas chromatography mass spectrometry analysis.In the stirred reactor of band condensing reflux, add certain amount of solvent and fortified phenol then, perhaps keep temperature of reactor to be not less than and add quantitative fortified phenol under the fortified phenol fusing point condition, quantitatively add reaction intermediate and replace acrylate chloride, reaction 1-36h can obtain the thick product of target product substitutional crylic acid phenyl ester.After recrystallization or normal pressure or rectification under vacuum, get final product the substitutional crylic acid phenyl ester of purifying.
The one-step synthesis of describing in embodiment is: add quantitative substitutional crylic acid and micro-stopper and phosphorus trichloride or phosphorus oxychloride or thionyl chloride or phosphorus pentachloride in the stirred reactor of band condensing reflux, add quantitative fortified phenol, reaction 1-36h can obtain the thick product of target product substitutional crylic acid phenyl ester.After recrystallization or normal pressure or rectification under vacuum, get final product the substitutional crylic acid phenyl ester of purifying.
The method of the invention synthesizing substitutional crylic acid phenyl ester, product purity＞99%, single impurity concentration＜0.3%.Productive rate＞75% of the synthetic target product of single stage method, productive rate＞85% of the synthetic target product of two-step approach.
Compared with prior art, the invention has the advantages that:
1) do not use catalyzer, solvent is not used in preferred scheme reaction;
2) reaction yield height, the easily separated purification of product;
3) the effectively generation of controlled polymerization reaction of reaction, the product purity height.
Embodiment
The invention discloses a kind of method of synthesizing substitutional crylic acid phenyl ester, those skilled in the art can use for reference this paper content, suitably improve processing parameter and realize.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they all are regarded as being included in the present invention.
Two-step approach synthesis method of the present invention specifically describes as follows:
1) the synthetic acrylate chloride that replaces of the first step.This is reflected in the stirred reactor of being with condensing reflux and carries out, and reactions steps is: add structure suc as formula the substitutional crylic acid shown in (II) and phosphorus trichloride or phosphorus oxychloride in reactor, the two amount of substance ratio is about 6: 1-6; Perhaps add structure suc as formula substitutional crylic acid and the thionyl chloride shown in (II), the two amount of substance ratio is about 4: 1-4; Perhaps add structure suc as formula substitutional crylic acid and the phosphorus pentachloride shown in (II), the two amount of substance ratio is about 4: 1-4, be heated to boiling and be cooled to 30～70 ℃ again, reaction 5-30min,, place 0.5-4h. under the room temperature, in flask, add micro-stopper, air distillation or underpressure distillation are got corresponding product cut and are obtained replacing acrylate chloride (IV).
2) synthetic corresponding substitutional crylic acid phenyl ester of second step.This is reflected in the stirred reactor of being with condensing reflux and carries out, and reactions steps is: add fortified phenol and a certain amount of solvent with general formula of molecular structure (III) in reactor, be heated to 40-75 ℃; Or solubilizing agent not, be heated to be not less than the fortified phenol solvent temperature after, add again and replace acrylate chloride (IV), the amount of substance ratio that replaces acrylate chloride (IV) and fortified phenol (III) is 10: 5-15.React 1-36h down at 40-75 ℃, can obtain the thick product of target product substitutional crylic acid phenyl ester.After recrystallization or normal pressure or rectification under vacuum, get final product substitutional crylic acid phenyl ester, synthetic target product productive rate is more than 85%.
Single stage method synthesis method of the present invention specifically describes as follows:
This is reflected in the stirred reactor of being with condensing reflux and carries out, the fortified phenol and the micro-stopper that add substitutional crylic acid with general formula of molecular structure (II) and phosphorus trichloride or phosphorus oxychloride or thionyl chloride or phosphorus pentachloride in the reactor and have general formula of molecular structure (III), the two amount of substance ratio of substitutional crylic acid and phosphorus trichloride is about 6: 1-6; Or the two amount of substance ratio of substitutional crylic acid and thionyl chloride is about 4: 1-4; Or the two amount of substance ratio of substitutional crylic acid and phosphorus pentachloride is about 4: 1-4, be heated to 40-75 ℃, and add fortified phenol (III) then, the amount of substance of fortified phenol (III) and substitutional crylic acid (II) is than being 5-15: 10.Reaction 1-36h can obtain the thick product of target product substitutional crylic acid phenyl ester.After recrystallization or normal pressure or rectification under vacuum, get final product substitutional crylic acid phenyl ester.Synthetic target product productive rate is more than 75%.
The substitutional crylic acid phenyl ester of the method for the invention preparation is through gas chromatographic analysis product purity＞99%, single impurity concentration＜0.3%.
The invention will be further described for following examples, but can not be interpreted as limiting the scope of the invention.
Embodiment 1
In having the 100ml flask of magnetic agitation and condensing reflux, add 30ml methacrylic acid and 10ml phosphorus trichloride and 0.05g stopper cuprous chloride, be heated to boiling, be cooled to 60～70 ℃ then, reaction 15min, place 2h under the room temperature, 90-105 ℃ of cut got in air distillation, and the gas chromatography mass spectrometry analysis is a methacrylic chloride.In having the 100ml flask of magnetic agitation and condensing reflux, add 1.5g phenol and 10ml pyridine, add the methacrylic chloride that 8ml makes, react 12h down 45 ℃ (the temperature positive and negative deviation is no more than 1 ℃), can obtain the thick product of target product phenyl methacrylate.After rectification under vacuum, get final product the phenyl methacrylate (I) of purity＞99% and single impurity concentration＜0.3%, the yield of target product phenyl methacrylate is 88%.
Embodiment 2
Add 170ml methacrylic acid and 60ml phosphorus trichloride and 0.1 gram stopper cuprous chloride in having the 500ml flask of magnetic agitation and condensing reflux, be heated to boiling, be cooled to 60～70 ℃ then, reaction 15min places 2h under the room temperature.40-50 ℃ of cut got in underpressure distillation, and the gas chromatography mass spectrometry analysis is the methacrylic isoxazolecarboxylic acid.In having the 500ml flask of magnetic agitation and condensing reflux, add the methacrylic chloride that 100ml phenol and 100ml reaction make, react 12h down, can obtain the thick product of target product phenyl methacrylate 45 ℃ (the temperature positive and negative deviation is no more than 1 ℃).After rectification under vacuum, get final product the phenyl methacrylate (I) of purity＞99% and single impurity concentration＜0.3%, the yield of target product phenyl methacrylate is 90%.
Embodiment 3
Add 80ml methacrylic acid and 170ml thionyl chloride and 0.15 gram hydroquinone of polymerization retarder in having the 500ml flask of magnetic agitation and condensing reflux, be heated to 60～70 ℃, backflow phenomenon occurs, reaction 6h postcooling is to room temperature.Underpressure distillation, steaming front-end volatiles is thionyl chloride, with its recovery (reusable edible), back distilled cut is methacrylic chloride through the gas chromatography mass spectrometry analysis.In having the 500ml flask of magnetic agitation and condensing reflux, add the methacrylic chloride that 100ml orthoxenol and 100ml reaction make.React 12h down 45 ℃ (the temperature positive and negative deviation is no more than 1 ℃), can obtain the thick product of the adjacent phenyl phenyl ester of target product methacrylic acid.After rectification under vacuum, get final product the adjacent phenyl phenyl ester (I) of methacrylic acid of purity＞99% and single impurity concentration＜0.3%, the yield of the adjacent phenyl phenyl ester of target product methacrylic acid is 85%.
Embodiment 4
Add 170ml methacrylic acid and 60ml phosphorus oxychloride and 0.1 gram stopper cuprous chloride in having the 500ml flask of magnetic agitation and condensing reflux, be heated to boiling, be cooled to 60～70 ℃ then, reaction 15min places 2h under the room temperature.40-50 ℃ of cut got in underpressure distillation, and the gas chromatography mass spectrometry analysis is a methacrylic chloride.In having the 500ml flask of magnetic agitation and condensing reflux, add 2 of 100ml, 4, the 100ml methacrylic chloride that 6-tribromophenol and reaction make, react 12h down 45 ℃ (the temperature positive and negative deviation is no more than 1 ℃), can obtain target product 2,4, the thick product of 6-methacrylic acid tribromophenyl.Through recrystallization get final product purity＞99% and single impurity concentration＜0.3% 2,4,6-methacrylic acid tribromophenyl (I), target product 2,4, the yield of 6-methacrylic acid tribromophenyl is 89%.
Embodiment 5
Add 170ml vinylformic acid and 60ml phosphorus oxychloride and micro-stopper in having the 500ml flask of magnetic agitation and condensing reflux, be heated to boiling, be cooled to 60～70 ℃ then, reaction 15min places 2h under the room temperature.40-50 ℃ of cut got in underpressure distillation, and the gas chromatography mass spectrometry analysis is the vinylformic acid acyl chlorides.In having the 500ml flask of magnetic agitation and condensing reflux, add the 100ml vinylformic acid acyl chlorides that 100ml p bromophenol and reaction make, react 12h down, can obtain the thick product of target product vinylformic acid bromobenzene ester 45 ℃ (the temperature positive and negative deviation is no more than 1 ℃).After rectification under vacuum, get final product the vinylformic acid bromobenzene ester (I) of purity＞99% and single impurity concentration＜0.3%, the yield of target product vinylformic acid bromobenzene ester is 92%.
Embodiment 6
In having the 500ml flask of magnetic agitation and condensing reflux, add 120ml methacrylic acid and 40ml phosphorus trichloride, be heated to 75 ℃, add 120ml phenol then, reaction 16h, be cooled to room temperature, get supernatant liquid, after rectification under vacuum distillates front-end volatiles, the gas chromatography mass spectrometry analysis for get final product the phenyl methacrylate crude product.After rectification under vacuum, get final product the phenyl methacrylate (I) of purity＞99% and single impurity concentration＜0.3%, the yield of target product phenyl methacrylate is 76%.
Embodiment 7
In having the 500ml flask of magnetic agitation and condensing reflux, add 120ml vinylformic acid and 40ml phosphorus trichloride and 0.5 gram stopper cuprous chloride, be heated to 65 ℃, add 120ml phenol, reaction 16h, be cooled to room temperature, get supernatant liquid, after rectification under vacuum distillates front-end volatiles, get final product phenyl acrylate.After rectification under vacuum, get final product the phenyl acrylate (I) of purity＞99% and single impurity concentration＜0.3%, the yield of target product phenyl acrylate is 79%.
Embodiment 8
In having the 500ml flask of magnetic agitation and condensing reflux, add 80ml vinylformic acid and 170ml thionyl chloride and 0.3 gram stopper cuprous chloride, be heated to 65 ℃, add 80ml 2 then, 4, the 6-tribromophenol, reaction 16h is cooled to room temperature, underpressure distillation, steaming front-end volatiles is thionyl chloride, and with its recovery (reusable edible), back distilled cut gas chromatography mass spectrometry analysis is for being thick product 2,4,6-vinylformic acid tribromophenyl.After rectification under vacuum, get final product purity＞99%, and single impurity concentration＜0.3% 2,4,6-vinylformic acid tribromophenyl (I), target product 2,4, the yield of 6-vinylformic acid tribromophenyl is 88%.
Method of the present invention and use is described by embodiment, and the related personnel obviously can change or suitably change and combination methods and applications as herein described in not breaking away from content of the present invention, spirit and scope, as with the R in the compound shown in the formula II
1Group is with other alkyl, alkoxyl group, halogen, amido, amino, the acid of nitro instead of propylene or methacrylic acid, or with the R of compound shown in the formula III
2, R
3, R
4, R
5And R
6Group substitutes phenol, tribromophenol, orthoxenol with other alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, nitro, these are replaced does not all influence the reaction generation, can generate compound shown in the formula I of corresponding replacement, these similarly replace and change apparent to those skilled in the art, and they all are regarded as being included in the present invention.
Claims (11)
1. a composite structure is suc as formula the method for compound shown in the I,
It is characterized in that, compound shown in the substitution reaction production IV takes place in one of compound shown in the formula II and phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride, compound shown in the formula IV again with the generation of compound shown in formula III transesterification reaction generating structure suc as formula compound shown in the I; R wherein
1Be hydrogen or alkyl, alkoxyl group, halogen, amido, amino, nitro, R
2, R
3, R
4, R
5And R
6Be hydrogen or alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, nitro.
2. method according to claim 1 is characterized in that, carries out in two steps:
Step 1: with one of phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride and compound shown in the formula (II), be heated to boiling postcooling to 30～70 ℃, reaction 5-30min adds stopper, gets corresponding product cut after the distillation and gets the compound shown in the formula (IV);
Step 2: compound shown in the formula (III) is dissolved in organic solvent or is heated to the melting temperature (Tm) of compound shown in the formula of being not less than (III), add the compound shown in the step 1 synthetic formula (IV) again, at 40-75 ℃ of reaction 1-36h.
3. method according to claim 1 is characterized in that, concrete steps are:
One of phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride are mixed with compound shown in the formula (II) and stopper, be heated to 40-75 ℃, add compound shown in the formula (III) then, reaction 1-36h.
4. according to claim 2 or 3 described methods, it is characterized in that compound shown in the formula (II) is about 6 with phosphorus trichloride or phosphorus oxychloride amount of substance ratio: 1-6.
5. according to claim 2 or 3 described methods, it is characterized in that compound shown in the formula (II) is about 4 with thionyl chloride amount of substance ratio: 1-4.
6. according to claim 2 or 3 described methods, it is characterized in that compound shown in the formula (II) is about 4 with phosphorus pentachloride amount of substance ratio: 1-4.
7. according to claim 2 or 3 described methods, it is characterized in that described stopper is cuprous chloride or Resorcinol, consumption is 0.5～15% of a compound gross weight shown in compound shown in the formula (II) and the formula (III).
8. method according to claim 2 is characterized in that, at room temperature places 0.5-4h behind the reaction 5-30min in the step 1.
9. method according to claim 2 is characterized in that organic solvent described in the step 2 is aromatic hydrocarbons, aryl alkyl ethers, chlorinated aromatic hydrocarbons, pyridine, dimethyl sulfoxide (DMSO), is preferably pyridine, toluene or dimethylbenzene.
10. method according to claim 2 is characterized in that, compound amount of substance shown in the formula (III) is 5-15 with the amount of substance ratio of compound shown in the formula IV: 10.
11. method according to claim 3 is characterized in that, the amount of substance of compound shown in compound amount of substance shown in the formula (III) and the formula (II) is than being 5-15: 10.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993371A (en) * | 2010-12-01 | 2011-03-30 | 长春工业大学 | Preparation method of allyl acrylate |
| CN104592005A (en) * | 2015-01-07 | 2015-05-06 | 上海应用技术学院 | Method of preparing acryloyl chloride by virtue of continuous method |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1747924A (en) * | 2003-02-07 | 2006-03-15 | 三菱丽阳株式会社 | Process for producing methacrylic ester |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1747924A (en) * | 2003-02-07 | 2006-03-15 | 三菱丽阳株式会社 | Process for producing methacrylic ester |
Non-Patent Citations (1)
| Title |
|---|
| 《化学工业与工程》 19980531 张鹏等 2，4，6－三溴丙烯酸苯酯的合成 23-24，26，35 1－11 第15卷, 第2期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993371A (en) * | 2010-12-01 | 2011-03-30 | 长春工业大学 | Preparation method of allyl acrylate |
| CN101993371B (en) * | 2010-12-01 | 2013-07-31 | 长春工业大学 | Preparation method of allyl acrylate |
| CN104592005A (en) * | 2015-01-07 | 2015-05-06 | 上海应用技术学院 | Method of preparing acryloyl chloride by virtue of continuous method |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
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