CN101565365A - Preparation method of alpha, beta-unsaturated acid - Google Patents
Preparation method of alpha, beta-unsaturated acid Download PDFInfo
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- CN101565365A CN101565365A CNA2008100442730A CN200810044273A CN101565365A CN 101565365 A CN101565365 A CN 101565365A CN A2008100442730 A CNA2008100442730 A CN A2008100442730A CN 200810044273 A CN200810044273 A CN 200810044273A CN 101565365 A CN101565365 A CN 101565365A
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Abstract
A preparation method of alpha, beta-unsaturated acid takes aldehyde compound and 1, 3-dicarboxylic acid as raw materials, takes glacial acetic acid as a solvent and also takes a mixture of concentrated sulfuric acid and the glacial acetic acid as a contact agent, and after heating reaction, the mixture is immerged into ice water to obtain the alpha, beta-unsaturated acid product, wherein a water remover ingredient is added into a reaction system. The preparation method can reduce the viscocity of a paste of the reaction system and is easy to stir to release generated CO2 gas so as to be favorable for reaction balance to move to the product direction, thereby obviously enhancing the yield coefficient of the product, reducing the usage amount of the concentrated sulfuric acid and the pollution of environment and being suitable for production in batches.
Description
Technical field
The present invention relates to a kind of improved α, the preparation method of beta-unsaturated acid.
Background technology
The Chinese patent literature of notification number CN1027756C discloses a kind of with aldehyde compound and 1, the 3-di-carboxylic acid is a raw material, the mixture that with the glacial acetic acid is solvent, the vitriol oil and glacial acetic acid is a contact substance, in 40～70 ℃ of reacting by heating after 0.5～3.5 hour, to obtain said α in the reactant impouring frozen water, beta-unsaturated acid product crystalline deposit.The general formula of this reaction is:
Be raw material with 3-methoxyl group-4-hydroxyl-phenyl aldehyde and propanedioic acid in the document, the average yield that obtains 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID through method for preparing is 72.4%, the highest yield 80.6%.
To discovering of this reaction process, the reaction system in this method reaction process is the semi-solid thing of pasty state, is difficult for stirring the CO that produces in the reaction process
2Gas is difficult for all emitting, and slowed down molecular balance and moved to the direction of required product, and the increase reaction times then easily causes product to decompose, and has increased impurity.On the other hand, if can remove the H that produces in the reaction process
2O then also will help the carrying out of forward reaction, if only depend on the water of the vitriol oil absorption reaction generation that is added obviously undesirable, this also is to cause reactant not reach reason completely all the time.If absorb this reaction water in the mode that strengthens vitriol oil consumption, both uneconomical, also be unfavorable for environmental protection.Particularly when scale operation, its α, the yield of beta-unsaturated acid product is difficult to further raising, and impurity also is difficult for removing.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of improved α, and the preparation method of beta-unsaturated acid is to solve the problem in the above-mentioned preparation process.
α of the present invention, the preparation method of beta-unsaturated acid is based on above-mentioned literature method, be with aldehyde compound and 1 equally, the 3-di-carboxylic acid is a raw material, the mixture that with the glacial acetic acid is solvent, the vitriol oil and glacial acetic acid is a contact substance, after the reacting by heating, get said α, beta-unsaturated acid product in the impouring frozen water.Wherein important innovative approach is that also adding in reactant systems has the water-removal agent composition.Said water-removal agent composition generally can be selected inorganic salts composition commonly used for use, as at least a in anhydrous sodium sulphate commonly used, the anhydrous magnesium sulfate etc., removes in separating with required product after the reaction.
The purpose that adds the water-removal agent composition in reactant systems is to remove the water that dereaction generates in the process at any time for carrying out in reaction, therefore if the consumption of water-removal agent is very few, can influence the effect that dewaters undoubtedly, but also need not too much.Test shows that the consumption of water-removal agent is generally 30%～60% of aldehyde compound weight, scope preferably, and further preferred range can be 40%～50% of aldehyde compound weight.
By behind the aforesaid way adding water-removal agent composition of the present invention, remaining reaction conditioned response and operating method can keep carrying out as the said mode of above-mentioned document in reactive system.For example, aldehyde compound and 1,3-di-carboxylic acid two raw materials in molar ratio 1: after the mode of (1～2.5) is mixed, add said water-removal agent composition and glacial acetic acid solvent, drip a small amount of contact substance (mixing solutions of the vitriol oil and glacial acetic acid), at stirring reaction under 40～70 ℃ the heating condition after 0.5～3.5 hour, in reactant impouring frozen water, get α, the crude product of beta-unsaturated acid product; Further, can obtain this α, the purified product of beta-unsaturated acid with behind the ethyl alcohol recrystallization.
In the above-mentioned preparation method of the present invention, can be further preferred innovative approach also comprises: the vitriol oil in the said contact substance and the volume ratio of glacial acetic acid are with 1: (10～15) and/or, the volume/weight amount ratio of said contact substance and aldehyde compound is (2～3): 1 for well.
By we find that uncannily the inventive method has added the water-removal agent composition (as anhydrous Na in reaction system with the comparative research trial of above-mentioned document
2SO
4) after, the residual content of the aldehyde compound raw material in the reaction system is starkly lower than the reaction system when not adding the water-removal agent composition.Still be the pasty state semisolid although add the whole reaction system that the water-removal agent composition is arranged, the inorganic salts water-removal agent composition of lenticular is (as anhydrous Na
2SO
4) adding can help lowering the viscosity of mashed prod system, be easier to stir and make the CO that is generated
2Emitting of gas, the water that produces in the reaction process can constantly be removed in addition, moves to the direction of required product thereby help molecular balance, and its whole result can make the yield of product obviously improve after being embodied in and adding the water-removal agent composition.
For example, during with method for preparing 3-methoxyl group of the present invention-4-hydroxyl-TRANSCINNAMIC ACID, 3-methoxyl group-4-hydroxyl-phenyl aldehyde and propanedioic acid are mixed by 1: 1～2.5 molar ratios, add the water-removal agent anhydrous Na
2SO
4With the glacial acetic acid solvent, the mixture that drips a small amount of vitriol oil and this solvent is as contact substance.Other reaction conditions and operate same as above, at last 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID finished product, average yield is 78.4%, the highest yield 85.6%.
Embodiment below in conjunction with embodiment is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Embodiment
Embodiment 1
In the exsiccant round-bottomed flask, add raw material 3-methoxyl group-4-hydroxyl-phenyl aldehyde and propanedioic acid (mol ratio is 1: 2) and mix, add the water-removal agent anhydrous Na
2SO
4, add glacial acetic acid, drip by the vitriol oil and glacial acetic acid with volume ratio 1: the contact substance of (10～15) mixing solutions form, the volume/weight amount ratio of contact substance and 3-methoxyl group-4-hydroxyl-phenyl aldehyde is (2～3): 1.Round-bottomed flask is placed 40 ℃ of stirred in water bath reactions 3.5 hours, negate answers mixture to make high-efficient liquid phase analysis, detecting the growing amount of product and the residual content of reactant, is that theoretical growing amount calculates product production rate and reactant surplus ratio with the mole number of 3-methoxyl group-4-hydroxyl-phenyl aldehyde.In reactant impouring frozen water, suction filtration gets 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID crude product, with ethyl alcohol recrystallization, gets elaboration.The bath of ethanol mother liquor, suction filtration gets its crude product.Use ethyl alcohol recrystallization, get its elaboration, merge elaboration twice,, get 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID finished product dry below 60 ℃.Mole number with 3-methoxyl group-4-hydroxyl-phenyl aldehyde is that theoretical growing amount calculates reactant surplus ratio, the average production rate of product and product average yield.
Reference examples 1
In the exsiccant round-bottomed flask, add raw material 3-methoxyl group-4-hydroxyl-phenyl aldehyde and propanedioic acid (mol ratio is 1: 2) and mix, add glacial acetic acid, drip the vitriol oil of same amount and the mixing solutions of glacial acetic acid.Remaining reaction condition and operation are all with embodiment 1.
The foregoing description 1 that under equal conditions carries out respectively and reference examples 1, the present invention adds the method for water-removal agent composition and aforementioned patent document preparation method's difference with contrast, and test-results is as shown in table 1.
The comparative test result of table 1 embodiment 1 and reference examples 1
| Reactant surplus ratio (w%) | The average production rate of product (w%) | Product average yield (w%) | |
| Reference examples 1 | 23.4 | 85.4 | 73.3 |
| Embodiment 1 | 14.3 | 92.7 | 82.6 |
Embodiment 2
Add raw material p-nitro-benzene formaldehyde and propanedioic acid (mol ratio is 1: 2), add the water-removal agent anhydrous Na
2SO
4, temperature of reaction is about 50 ℃, and the stirring reaction time is 2 hours, and other is operated with embodiment 1.
Reference examples 2
Adding raw material p-nitro-benzene formaldehyde and propanedioic acid (mol ratio is 1: 2) temperature of reaction is 50 ℃, and the stirring reaction time is 2 hours, and other is operated with embodiment 1.
Embodiment 2 that under equal conditions carries out respectively and reference examples 2, the present invention adds the method for water-removal agent composition and aforementioned patent document preparation method's difference with contrast, and test-results is as shown in table 2.
The comparative test result of table 2 embodiment 1 and reference examples 1
| Reactant surplus ratio (w%) | The average production rate of product (w%) | Product average yield (w%) | |
| Reference examples 2 | 31.6 | 65.1 | 53.6 |
| Embodiment 2 | 22.4 | 73.5 | 62.8 |
Claims (7)
1. α, the preparation method of beta-unsaturated acid, with aldehyde compound and 1, the 3-di-carboxylic acid is a raw material, the mixture that with the glacial acetic acid is solvent, the vitriol oil and glacial acetic acid is a contact substance, after the reacting by heating, in the impouring frozen water said α, the beta-unsaturated acid product is characterized in that in reactant systems also adding that the water-removal agent composition is arranged.
2. α as claimed in claim 1, the preparation method of beta-unsaturated acid is characterized in that said water-removal agent composition is the inorganic salts composition.
3. α as claimed in claim 2, the preparation method of beta-unsaturated acid is characterized in that said water-removal agent composition is at least a of anhydrous sodium sulphate, anhydrous slufuric acid magnesium component.
4. as claim 2 or 3 described α, the preparation method of beta-unsaturated acid, the amount that it is characterized in that said water-removal agent composition is 30%～60%% of an aldehyde compound weight.
5. α as claimed in claim 4, the preparation method of beta-unsaturated acid, the amount that it is characterized in that said water-removal agent composition is 40%～50% of an aldehyde compound weight.
6. as the described α of one of claim 1 to 3, the preparation method of beta-unsaturated acid is characterized in that the vitriol oil in the said contact substance and the volume ratio of glacial acetic acid are 1: (10～15).
7. as the described α of one of claim 1 to 3, the preparation method of beta-unsaturated acid is characterized in that the volume/weight amount ratio of said contact substance and aldehyde compound is (2～3): 1.
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| CNA2008100442730A CN101565365A (en) | 2008-04-22 | 2008-04-22 | Preparation method of alpha, beta-unsaturated acid |
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| CNA2008100442730A CN101565365A (en) | 2008-04-22 | 2008-04-22 | Preparation method of alpha, beta-unsaturated acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531814A (en) * | 2011-12-23 | 2012-07-04 | 张文生 | Preparation method for trans-cinnamic acid compound in water insoluble ionic liquid [bmim] PF6 |
-
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- 2008-04-22 CN CNA2008100442730A patent/CN101565365A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531814A (en) * | 2011-12-23 | 2012-07-04 | 张文生 | Preparation method for trans-cinnamic acid compound in water insoluble ionic liquid [bmim] PF6 |
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Application publication date: 20091028 |