CN102757343A - Preparation method of vanillin isobutyrate - Google Patents
Preparation method of vanillin isobutyrate Download PDFInfo
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- CN102757343A CN102757343A CN2012102709418A CN201210270941A CN102757343A CN 102757343 A CN102757343 A CN 102757343A CN 2012102709418 A CN2012102709418 A CN 2012102709418A CN 201210270941 A CN201210270941 A CN 201210270941A CN 102757343 A CN102757343 A CN 102757343A
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- isobutyrate
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Abstract
The invention discloses a preparation method of vanillin isobutyrate. The method comprises the following step of: reacting methyl vanillin or ethyl vanillin with isobutyrate at the temperature of 60-120 DEG C by taking an alkali metal salt of low-grade carboxylic acid as a catalyst to obtain isobutyrate of the methyl vanillin or ethyl vanillin, wherein the alkali metal salt of the low-grade carboxylic acid is a potassium salt or sodium salt of formic acid, acetic acid, propionic acid or butyric acid. The method has the advantages of easiness and convenience for operating, no need of using any solvent, short reaction time, simple post-treatment process, high product yield, good quality, short production period, low energy consumption, low cost, low environmental pollution and suitability for large-scale industrial production.
Description
Technical field
The invention belongs to chemical field, relate to a kind of preparation method of chemical.
Background technology
Vanillin food grade,1000.000000ine mesh comprises methyl vanillin (vanillin; 4-hydroxy 3-methoxybenzene formaldehyde) and vanirone (ethyl vanillin; 4-hydroxyl-3-ethoxy-benzaldehyde), be important spices, be widely used in the food such as makeup, perfumed soap, cigarette and candy, cake, beverage.Owing to contain phenolic hydroxyl group in its structure; Easy oxidation discoloration in storage process influences the outward appearance and the quality of product, many at present itself and isobutyryl chloride or isobutyric anhydride is carried out esterification; Generate the vanillin food grade,1000.000000ine mesh isobutyrate, solve this problem with isobutyryl protection phenolic hydroxyl group.
Chinese patent CN98109782.0 discloses a kind of method with vanirone and isobutyric anhydride prepared in reaction Ethylvanillin isobutyrate; Be with after the vanirone fusing, 100 ℃ of following and isobutyric anhydride reactions, after reaction finishes; Elder generation's underpressure distillation removes isopropylformic acid and the intact isobutyric anhydride of unreacted that dereaction generates; Again system is cooled to 90 ℃, adds Virahol, be cooled to 7 ℃ and carry out crystallization.There is following problem in this method: the yield of Ethylvanillin isobutyrate low (77%), aftertreatment technology complicated (isopropylformic acid and isobutyric anhydride are removed in first underpressure distillation, add the Virahol cooling crystallization again), recrystallization temperature lower (7 ℃), energy consumption are higher.
One Chinese patent application 200410099157.0 discloses a kind of method of acid anhydrides method synthesizing methyl vanillin food grade,1000.000000ine mesh isobutyrate; Be to be that solvent, yellow soda ash are room temperature reaction under the condition of catalyzer with toluene with methyl vanillin and isobutyric anhydride; After reaction finishes; Use sodium hydroxide solution and water washing successively, reclaim solvent, underpressure distillation makes the isopropylformic acid vanillin ester again.There is following problem in this method: solvent toxicity is bigger, and the reaction times is grown (about 3 hours), aftertreatment technology complicated (earlier with sodium hydroxide solution and water washing, reclaiming solvent, underpressure distillation again).
Therefore, be necessary the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate is improved, to simplify technology, save time, improve yield, to reduce cost, environmental pollution is little simultaneously.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of acid anhydrides legal system to be equipped with the method for vanillin food grade,1000.000000ine mesh isobutyrate, easy and simple to handlely save time, product yield is high, cost is low, environmental pollution is little.
For achieving the above object, the present invention provides following technical scheme:
The preparation method of vanillin food grade,1000.000000ine mesh isobutyrate is that an alkali metal salt with the low-grade carboxylic acid is a catalyzer, and methyl vanillin or vanirone in 60 ~ 120 ℃ of reactions of temperature, are promptly made the isobutyrate of methyl vanillin or vanirone; Said low-grade carboxylic acid's an alkali metal salt is formic acid, acetate, propionic acid or butyro-sylvite or sodium salt.
Further; The preparation method of methyl vanillin isobutyrate is that an alkali metal salt with the low-grade carboxylic acid is a catalyzer, with methyl vanillin in 60 ~ 120 ℃ of reactions of temperature, after reaction finishes; The reaction solution underpressure distillation is removed isopropylformic acid and the intact isobutyric anhydride of unreacted that dereaction generates; Cut is collected in underpressure distillation again, promptly gets the methyl vanillin isobutyrate.
Further; The preparation method of Ethylvanillin isobutyrate is that an alkali metal salt with the low-grade carboxylic acid is a catalyzer; Vanirone in 60 ~ 120 ℃ of reactions of temperature, after reaction finishes, is added methanol-water or ethanol-water mixed solvent in reaction solution; Separate out crystal under the room temperature, promptly get Ethylvanillin isobutyrate.
Said low-grade carboxylic acid's an alkali metal salt is preferably potassium acetate or sodium acetate, more preferably sodium acetate.
The consumption of said isobutyric anhydride is preferably methyl vanillin or vanirone mole dosage 1.05 ~ 1.3 times, takes all factors into consideration production cost and product yield, more preferably 1.2 ~ 1.3 times of methyl vanillin or vanirone mole dosage.
The consumption of said low-grade carboxylic acid's an alkali metal salt is preferably every mole of methyl vanillin or vanirone adds 4 ~ 8g low-grade carboxylic acid an alkali metal salt; Take all factors into consideration production cost and product yield, more preferably every mole of methyl vanillin or vanirone add 5 ~ 6g low-grade carboxylic acid an alkali metal salt.
The temperature of reaction of said methyl vanillin or vanirone and isobutyric anhydride is preferably 80 ~ 90 ℃.
In the preparation method of Ethylvanillin isobutyrate, preferred, the volume ratio of methyl alcohol or ethanol and water is 1:2 in said methanol-water or the ethanol-water mixed solvent; Preferred, be after reaction finishes, in reaction solution, adding volume ratio is the methanol-water mixed solvent of 1:2.
Beneficial effect of the present invention is: the invention provides a kind of an alkali metal salt with the low-grade carboxylic acid is catalyzer; Under condition of no solvent, employing acid anhydrides legal system is equipped with the method for vanillin food grade,1000.000000ine mesh isobutyrate, and is easy and simple to handle; Do not use toxic solvents, the reaction times short (30 ~ 120 minutes); Aftertreatment technology is simple; Isopropylformic acid and isobutyric anhydride are removed in the reaction product underpressure distillation of methyl vanillin and isobutyric anhydride; Underpressure distillation steams the methyl vanillin isobutyrate and promptly gets again, and reaction product need not used sodium hydroxide solution and water washing, need not reclaim solvent yet; Add methanol-water or ethanol-water mixed solvent in the reaction product of vanirone and isobutyric anhydride; Crystallization at room temperature; Promptly get Ethylvanillin isobutyrate, do not need underpressure distillation to remove isopropylformic acid and isobutyric anhydride, also need not be cooled to low temperature crystallization below 10 ℃; Product yield high (＞83%), quality good (purity is more than 98%), with short production cycle, energy consumption is low, and cost is low, and environmental pollution is little, is fit to large-scale industrialization production.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer, carry out detailed description in the face of the preferred embodiments of the present invention down.
The preparation of embodiment 1 ~ 14, Ethylvanillin isobutyrate
In three neck round-bottomed flasks, add vanirone 16.6g (0.1mol), isobutyric anhydride and catalyzer, reacting by heating; After reaction finished, when question response liquid was reduced to 60 ℃, adding volume ratio was methanol-water or the ethanol-water mixed solvent 45mL of 1:2; Separate out crystal under the room temperature, filter, promptly get Ethylvanillin isobutyrate; White solid, 56 ~ 57 ℃ of fusing points, through high effective liquid chromatography for measuring purity more than 98%.Concrete experiment condition and result see table 1.
The preparation of table 1 Ethylvanillin isobutyrate
The preparation of embodiment 15 ~ 27, methyl vanillin isobutyrate
In three neck round-bottomed flasks, add methyl vanillin 15.2g (0.1mol), isobutyric anhydride and catalyzer, reacting by heating; After reaction finished, isopropylformic acid and isobutyric anhydride were removed in underpressure distillation under 120 ℃ of temperature, pressure 110mmHg condition, again underpressure distillation under 130 ℃ of temperature, pressure 15mmHg condition; Collect cut; Promptly get the methyl vanillin isobutyrate, colourless viscous liquid, refractive index n
20 D=1.5260, be 98.12 ~ 99.55% through high effective liquid chromatography for measuring purity.Concrete experiment condition and result see table 2.
The preparation of table 2 methyl vanillin isobutyrate
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although through invention has been described with reference to the preferred embodiments of the present invention; But those of ordinary skill in the art should be appreciated that and can make various changes to it in form with on the details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (10)
1. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate; It is characterized in that; An alkali metal salt with the low-grade carboxylic acid is a catalyzer, and methyl vanillin or vanirone and isobutyric anhydride in 60 ~ 120 ℃ of reactions of temperature, are promptly made the isobutyrate of methyl vanillin or vanirone; Said low-grade carboxylic acid's an alkali metal salt is formic acid, acetate, propionic acid or butyro-sylvite or sodium salt.
2. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate according to claim 1 is characterized in that, is catalyzer with low-grade carboxylic acid's an alkali metal salt; With methyl vanillin and isobutyric anhydride in 60 ~ 120 ℃ of reactions of temperature; After reaction finishes, the reaction solution underpressure distillation is removed isopropylformic acid and the intact isobutyric anhydride of unreacted that dereaction generates, underpressure distillation again; Collect cut, promptly get the methyl vanillin isobutyrate.
3. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate according to claim 1; It is characterized in that, be catalyzer with low-grade carboxylic acid's an alkali metal salt, with vanirone and isobutyric anhydride in 60 ~ 120 ℃ of reactions of temperature; After reaction finishes; In reaction solution, add methanol-water or ethanol-water mixed solvent, separate out crystal under the room temperature, promptly get Ethylvanillin isobutyrate.
4. according to the preparation method of each described vanillin food grade,1000.000000ine mesh isobutyrate of claim 1 to 3, it is characterized in that said low-grade carboxylic acid's an alkali metal salt is the sylvite or the sodium salt of acetate.
5. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate according to claim 4 is characterized in that, said low-grade carboxylic acid's an alkali metal salt is a sodium acetate.
6. according to the preparation method of each described vanillin food grade,1000.000000ine mesh isobutyrate of claim 1 to 3; It is characterized in that; The consumption of said isobutyric anhydride is methyl vanillin or vanirone mole dosage 1.05 ~ 1.3 times, and the consumption of said low-grade carboxylic acid's an alkali metal salt is an alkali metal salt that every mole of methyl vanillin or vanirone add 4 ~ 8g low-grade carboxylic acid.
7. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate according to claim 6; It is characterized in that; The consumption of said isobutyric anhydride is methyl vanillin or vanirone mole dosage 1.2 ~ 1.3 times, and the consumption of said low-grade carboxylic acid's an alkali metal salt is an alkali metal salt that every mole of methyl vanillin or vanirone add 5 ~ 6g low-grade carboxylic acid.
8. according to the preparation method of each described vanillin food grade,1000.000000ine mesh isobutyrate of claim 1 to 3, it is characterized in that the temperature of reaction of said methyl vanillin or vanirone and isobutyric anhydride is 80 ~ 90 ℃.
9. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate according to claim 3 is characterized in that, the volume ratio of methyl alcohol or ethanol and water is 1:2 in said methanol-water or the ethanol-water mixed solvent.
10. the preparation method of vanillin food grade,1000.000000ine mesh isobutyrate according to claim 9 is characterized in that, after reaction finished, in reaction solution, adding volume ratio was the methanol-water mixed solvent of 1:2.
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| CN2012102709418A CN102757343A (en) | 2012-07-31 | 2012-07-31 | Preparation method of vanillin isobutyrate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125799A (en) * | 2020-10-14 | 2020-12-25 | 重庆欣欣向荣精细化工有限公司 | Production method of vanillin isobutyrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874398A (en) * | 1997-04-10 | 1999-02-23 | Haarmann & Reimer Gmbh | Ethylvanillin isobutyrate |
| BRPI0803375A2 (en) * | 2008-08-11 | 2010-06-15 | Universidade Federal De São Paulo - Unifesp | compounds derived from 4-hydroxy-3-methoxy-benzaldehyde, process for obtaining, pharmaceutical composition, use of one or more compounds |
| CN102321064A (en) * | 2011-07-21 | 2012-01-18 | 南京林业大学 | Vanillin ester condensed 1,3-butanediol and preparation method thereof |
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2012
- 2012-07-31 CN CN2012102709418A patent/CN102757343A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874398A (en) * | 1997-04-10 | 1999-02-23 | Haarmann & Reimer Gmbh | Ethylvanillin isobutyrate |
| BRPI0803375A2 (en) * | 2008-08-11 | 2010-06-15 | Universidade Federal De São Paulo - Unifesp | compounds derived from 4-hydroxy-3-methoxy-benzaldehyde, process for obtaining, pharmaceutical composition, use of one or more compounds |
| CN102321064A (en) * | 2011-07-21 | 2012-01-18 | 南京林业大学 | Vanillin ester condensed 1,3-butanediol and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125799A (en) * | 2020-10-14 | 2020-12-25 | 重庆欣欣向荣精细化工有限公司 | Production method of vanillin isobutyrate |
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Application publication date: 20121031 |