CN105017000A - Trimethoxybenzoic acid preparation method - Google Patents
Trimethoxybenzoic acid preparation method Download PDFInfo
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- CN105017000A CN105017000A CN201510337536.7A CN201510337536A CN105017000A CN 105017000 A CN105017000 A CN 105017000A CN 201510337536 A CN201510337536 A CN 201510337536A CN 105017000 A CN105017000 A CN 105017000A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Abstract
The present invention discloses a trimethoxybenzoic acid preparation method, which comprises: A, adding 100 parts of Galla chinensis powder, 48-58 parts of water, 80-100 parts of Dimethylsulfate, and 130-140 parts of an alkali liquid to a reaction kettle, carrying out steam heating, controlling the temperature of 75-90 DEG C, stirring, and controlling the PH value of 9.4-10.3; B, after carrying out the reaction for 4-5 h, heating to the temperature of 90-100 DEG C, and adding 11-19 parts of sulfuric acid to carry out acidification; C, carrying out cooling crystallization to obtain a trimethoxybenzoic acid crude product; D, adding 85-110 parts of the trimethoxybenzoic acid crude product obtained in the step C, 900-970 parts of water, 25-40 parts of active carbon and 1-3 parts of EDTA to the reaction kettle to carry out a reaction for 2 h, and controlling the temperature of 100-105 DEG C and the pressure of 0.7-0.9 MPa; and E, adding the mixed liquid obtained in the step D to a centrifuge to carry out solid-liquid separation, and carrying out cooling crystallization on the obtained liquid to obtain the trimethoxybenzoic acid solid. According to the present invention, the purity of the trimethoxybenzoic acid prepared through the method is high, the cost and the production period are less, and the whole production efficiency is improved.
Description
Technical field
The invention belongs to benzoic ether field, be specifically related to the preparation method of trimethoxybenzoic acid.
Background technology
Trimethoxybenzoic acid is also called gallic acid three methyl ether, and usually referred to as TMBA, white crystalline powder, molecular formula is C
10h
120
5, molecular weight 212.2, be mainly the important fine chemical product of raw material production with Chinese gallotanninic acid, Chinese gallotanninic acid is mainly present in Turkey-galls.Be applied to the additive of gourmet food, cigarette, beverage, more extensive in field application such as organic synthesis and medicine, dyestuff, food and light industry especially.In organic synthesis, mainly for the preparation of organic compound such as trimethoxy-benzoyl chloride, syringic acid, TMB classes, at pharmaceutical industry, nervous mainly for the preparation for the treatment of, the anxiolytic Sedoxazin (trimetazidine) of frightened psychosis and neurotic syndromes and have the DE 2051443 of obvious curative effects, novel defense factor enhancement type gastritis and stomach ulcer treatment machine troxipide to behavior disorder of children, treatment heart disease had to the medicines such as gram hat acid of good efficacy, market is boundless.
Current most domestic enterprise adopts produced in conventional processes trimethoxybenzoic acid substantially, namely obtain with Weibull or gallic acid and dimethyl sulfate methylation of ester, mainly comprise the following steps, before this by the obtained gallic acid of Turkey-galls hydrolysis under acid, alkali environment, then methyl-sulfate is added by twice obtained trimethoxybenzoic acid raw product that methylates, then concentrate, obtain fine work trimethoxybenzoic acid by purification step more afterwards.
The main problem of traditional method is: 1, owing to Turkey-galls hydrolysis being obtained gallic acid in traditional technology, gallic acid methylates and obtains fine work trimethoxybenzoic acid is carry out segmentation reaction by two equipment to produce, production efficiency is low, too increases transportation cost, time cost; 2, in traditional methylation reaction, primary first-order equation does not reach purity requirement, so need to methylate for twice, adds cost; 3 and owing to needing in traditional technology to concentrate, can cause the oxidation of constituent part in the process of concentrate drying, the purity of product is not high, and pigment is higher, and production cost is high, and the rate of recovery is low.
Summary of the invention
Object of the present invention is providing a kind of preparation method of trimethoxybenzoic acid, prepares the cost increase caused, inefficient problem to solve multistage reaction in prior art.
For achieving the above object, technical scheme of the present invention is as follows: a kind of preparation method of trimethoxybenzoic acid, comprises following steps:
A. be 100 parts of Chinese Galls by mass fraction, 48-~ 58 part water, 80-~ 100 part methyl-sulfate, 130-~ 140 part alkali lye adds in reactor, pass through steam heating, control temperature is 75 ~ 90 DEG C, and stirs, and controlling pH value is 9.4 ~ 10.310;
B., after steps A reaction 4 ~ 5h, temperature is risen to 90-~ 100 DEG C, adds 11-~ 19 part sulfuric acid and carry out acidifying;
C. step B is reacted gained acidification reaction liquid and carry out crystallisation by cooling, obtain trimethoxybenzoic acid raw product;
D. 85-~ 110 part step C gained trimethoxybenzoic acid raw product, 900-~ 970 part water, 25-~ 40 part gac and a 1-~ 3 part EDTA are added in reactor and react, control temperature is between 100 ~ 105 DEG C, pressure is 0.7-~ 0.9MPa, and the reaction times is 2h;
E. added in whizzer by step D gained mixed solution and carry out solid-liquid separation, gained liquid carries out crystallisation by cooling, obtains trimethoxybenzoic acid solid;
F. step e gained trimethoxybenzoic acid solid is carried out heat drying in a vacuum, be then packaged to be fine work trimethoxybenzoic acid.
Mainly Chinese gallotanninic acid is there is in Turkey-galls, first add a certain proportion of pure water in a kettle., liquid caustic soda, methyl-sulfate, Weibull is first hydrolyzed into trihydroxybenzoic acid (i.e. gallic acid) under alkaline environment, then by the methylation reaction of methyl-sulfate, the hydrogen ion on hydroxyl in trihydroxybenzoic acid is replaced into methyl.Mainly gallic acid is produced from Turkey-galls in this programme, to with gallic acid produce trimethoxybenzoic acid be all carry out in same reactor, utilize the feature that Chinese tannin acid activity is strong, reaction is accelerated, substantially reduces the whole production cycle, material heated time is short, react more complete, material not easily produces side reaction, and the organic impurity content therefore in product is low, the purity of product is improved, and appearance luster is significantly better than existing handicraft product.In the process, temperature should control between 80 ~ 85 DEG C, if lower than 80 DEG C, methyl-sulfate can resolve into a large amount of methyl alcohol, methylation reaction stops, make it cannot complete normal methylation reaction, cause product-free to be produced, when temperature is more than 85 DEG C, methyl-sulfate major part under high-temperature alkaline condition produces methyl sodium salt, cause product yield sharply to reduce, product purity decreases, and product is defective.And PH controls 10, when lower than 9.4 time, chemical bond ~ CH
3be difficult to generate, finally can not form chemical products, if PH is higher than 10.3, reaction counter movement, final formation water and other neutralized reaction product, same product-free generates, and not only causes raw-material waste also to cause the generation of environmental pollution hidden danger.When after reaction 4 ~ 5h, respectively react completely, temperature raises gradually, when reaching 95 DEG C, starting to add sulfuric acid and carrying out acidification reaction, by carboxyl in trimethylbenzoic acid salt ~ R ion exchange on hydrogen ion, obtain trimethylbenzoic acid.Then carry out solid-liquid separation and purification by whizzer, obtain the trimethoxybenzoic acid that purity is high.The trimethoxybenzoic acid purity that present method obtains is higher, and cost and production cycle, less integral production efficiency improved
Further, in steps A, the ratio of Chinese Gall, water, methyl-sulfate, alkali lye 1:0.53:0.9:1.35 in mass ratio adds reaction kettle for reaction, and the trimethoxybenzoic acid purity that Chinese Gall, water, methyl-sulfate and alkali lye are produced according to above-mentioned mass ratio can reach 99%.
Further, step B acidification reaction control temperature 70 ~ 75 DEG C, PH controls 1 ~ 2.In acidization, if temperature is lower than 70 DEG C, reaction cannot be carried out, and is easily burnt by strong acid higher than 75 DEG C of trimethylbenzoic acids then generated.This reaction is carried out under strong acid environment, and PH is strict controlled in 1 ~ 2.
Further, the concentration of alkali lye described in steps A is 30%, is controlled by concentration of lye 30%, and speed of response is faster, and trimethoxybenzoic acid purity is higher.
Further, the mass ratio of trimethoxybenzoic acid raw product, water, gac and EDTA described in described D is 1:9.1:0.3:0.31, and the trimethoxybenzoic acid purity produced according to above-mentioned mass ratio can reach 99%.
Embodiment
Below by embodiment, the present invention is further detailed explanation:
Embodiment 1:
The invention provides a kind of preparation method of trimethoxybenzoic acid, comprise following steps:
A. 100 parts of Chinese Galls, 55 parts of water, 90 parts of methyl-sulfates, 135 parts of alkali lye are added in reactor, then by steam heating, control temperature of reaction 85 DEG C, stir with glass stick in reaction process, controlling pH value is 10, and wherein the concentration of alkali lye is 30%;
B. after steps A reacts 4 hours, temperature is risen to 95 DEG C, adding mass fraction is that 14 parts of sulfuric acid carry out acidifying, and wherein during acidifying, temperature controls at 75 DEG C, and pH value is 2;
C. step B is reacted gained acidification reaction liquid and carry out crystallisation by cooling, obtain trimethoxybenzoic acid raw product;
D. 100 parts of step C gained trimethoxybenzoic acid raw product, 910 parts of water, 30 parts of gacs and 1 part of EDTA added in reactor and react, it is 105 DEG C that temperature of reaction controls, and reaction pressure is 0.8MPa, and the reaction times is 2h;
E. added in whizzer by step D gained mixed solution and carry out solid-liquid separation, gained liquid carries out crystallisation by cooling, obtains trimethoxybenzoic acid solid;
F. step e gained trimethoxybenzoic acid solid is carried out heat drying under vacuum conditions, then dried crystal is carried out being packaged to be fine work trimethoxybenzoic acid.
Embodiment 2:
The invention provides a kind of preparation method of trimethoxybenzoic acid, comprise following steps:
A. 100 parts of Chinese Galls, 48 parts of water, 80 parts of methyl-sulfates, 130 parts of alkali lye are added in reactor, then by steam heating, control temperature of reaction 75 DEG C, stir with glass stick in reaction process, controlling pH value is 9.4, and wherein the concentration of alkali lye is 30%;
B. after steps A reacts 4 hours, temperature is risen to 90 DEG C, adding mass fraction is that 11 parts of sulfuric acid carry out acidifying, and wherein during acidifying, temperature controls at 75 DEG C, and pH value is 2;
C. step B is reacted gained acidification reaction liquid and carry out crystallisation by cooling, obtain trimethoxybenzoic acid raw product;
D. 100 parts of step C gained trimethoxybenzoic acid raw product, 900 parts of water, 25 parts of gacs and 1 part of EDTA added in reactor and react, it is 100 DEG C that temperature of reaction controls, and reaction pressure is 0.7MPa, and the reaction times is 2h;
E. added in whizzer by step D gained mixed solution and carry out solid-liquid separation, gained liquid carries out crystallisation by cooling, obtains trimethoxybenzoic acid solid;
F. step e gained trimethoxybenzoic acid solid is carried out heat drying under vacuum conditions, then dried crystal is carried out being packaged to be fine work trimethoxybenzoic acid.
Embodiment 3:
The invention provides a kind of preparation method of trimethoxybenzoic acid, comprise following steps:
A. 100 parts of Chinese Galls, 58 parts of water, 100 parts of methyl-sulfates, 140 parts of alkali lye are added in reactor, then by steam heating, control temperature of reaction 90 DEG C, stir with glass stick in reaction process, controlling pH value is 10.3, and wherein the concentration of alkali lye is 30%;
B. after steps A reacts 4 hours, temperature is risen to 100 DEG C, adding mass fraction is that 19 parts of sulfuric acid carry out acidifying, and wherein during acidifying, temperature controls at 75 DEG C, and pH value is 2;
C. step B is reacted gained acidification reaction liquid and carry out crystallisation by cooling, obtain trimethoxybenzoic acid raw product;
D. 110 parts of step C gained trimethoxybenzoic acid raw product, 970 parts of water, 40 parts of gacs and 3 parts of EDTA added in reactor and react, it is 105 DEG C that temperature of reaction controls, and reaction pressure is 0.9MPa, and the reaction times is 2h;
E. added in whizzer by step D gained mixed solution and carry out solid-liquid separation, gained liquid carries out crystallisation by cooling, obtains trimethoxybenzoic acid solid;
F. step e gained trimethoxybenzoic acid solid is carried out heat drying under vacuum conditions, then dried crystal is carried out being packaged to be fine work trimethoxybenzoic acid.
The above trimethoxybenzoic acid is 3,4,5-trimethoxybenzoic acid.
Following table is embodiment 1, embodiment 2 and embodiment 3 contrast with traditional trimethoxybenzoic acid preparation method experimental data:
| Preparation method | Trimethoxybenzoic acid purity | Equal in quality production cost | Pigment | Reaction required time |
| Embodiment 1 | 99.8％ | 89 yuan | Low | Short |
| Embodiment 2 | 98.9％ | 78 yuan | Low | Shorter |
| Embodiment 3 | 97％ | 96 yuan | Lower | Shorter |
| Traditional method | 74％ | 113 yuan | High | Longer |
As above show data can find out, the trimethoxybenzoic acid purity that embodiment 1, embodiment 2 and embodiment 3 obtains is high, and cost is low, and pigment is low and the reaction times is short, and production efficiency is high.
Above-described is only embodiments of the invention, and in scheme, the general knowledge such as known characteristic does not do too much description at this.It should be pointed out that for a person skilled in the art, under the premise of not departing from the present invention, can also make some distortion and improvement, these also should be considered as protection scope of the present invention, and these all can not affect effect of the invention process and practical applicability.The protection domain that this application claims should be as the criterion with the content of its claim, and the embodiment in specification sheets etc. record the content that may be used for explaining claim.
Claims (5)
1. a preparation method for trimethoxybenzoic acid, is characterized in that, comprises following steps:
A. be 100 parts of Chinese Galls by mass fraction, 48 ~ 58 parts of water, 80 ~ 100 parts of methyl-sulfates, 130 ~ 140 parts of alkali lye add in reactor, by steam heating, control temperature is 75 ~ 90 DEG C, and stirs, and controlling pH value is 9.4 ~ 10.3;
B., after steps A reaction 4 ~ 5h, temperature is risen to 90 ~ 100 DEG C, add 11 ~ 19 parts of sulfuric acid and carry out acidifying;
C. step B is reacted gained acidification reaction liquid and carry out crystallisation by cooling, obtain trimethoxybenzoic acid raw product;
D. 85 ~ 110 parts of step C gained trimethoxybenzoic acid raw product, 900 ~ 970 parts of water, 25 ~ 40 parts of gacs and 1 ~ 3 part of EDTA added in reactor and react, control temperature is between 100 ~ 105 DEG C, and pressure is 0.7 ~ 0.9MPa, and the reaction times is 2h;
E. added in whizzer by step D gained mixed solution and carry out solid-liquid separation, gained liquid carries out crystallisation by cooling, obtains trimethoxybenzoic acid solid;
F. step e gained trimethoxybenzoic acid solid is carried out heat drying in a vacuum, be then packaged to be fine work trimethoxybenzoic acid.
2. the preparation method of trimethoxybenzoic acid according to claim 1, is characterized in that, in steps A, the ratio of Chinese Gall, pure water, methyl-sulfate, alkali lye 1:0.53:0.9:1.35 in mass ratio adds reaction kettle for reaction.
3. the preparation method of trimethoxybenzoic acid according to claim 2, is characterized in that, step B acidification reaction control temperature 70 ~ 75 DEG C, and PH controls 1 ~ 2.
4. the preparation method of trimethoxybenzoic acid as claimed in claim 1 or 2, it is characterized in that, the concentration of alkali lye described in steps A is 30%.
5. the preparation method of trimethoxybenzoic acid as claimed in claim 1 or 2, it is characterized in that, the mass ratio of trimethoxybenzoic acid raw product, water, gac and EDTA described in described D is 1:9.1:0.3:0.31.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510337536.7A CN105017000A (en) | 2015-06-17 | 2015-06-17 | Trimethoxybenzoic acid preparation method |
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| CN201510337536.7A CN105017000A (en) | 2015-06-17 | 2015-06-17 | Trimethoxybenzoic acid preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848393A (en) * | 2020-06-17 | 2020-10-30 | 遵义市倍缘化工有限责任公司 | Method for treating wastewater from production of gallic acid and propyl gallate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051353A (en) * | 1990-10-13 | 1991-05-15 | 上海大众制药厂 | Direct method preparation 3,4, the 5-tri-methoxybenzoate |
| CN1314337A (en) * | 2001-02-21 | 2001-09-26 | 罗伟 | Method for producing 3,4,5 trimethoxybenzoic acid |
| CN102690196A (en) * | 2011-04-15 | 2012-09-26 | 竹山县天新医药化工有限责任公司 | Preparation and purification method of 3,4,5-trimethoxybenzoic acid |
| CN103265434A (en) * | 2013-06-09 | 2013-08-28 | 湖南洪江棓雅生物科技有限公司 | Production technology of 3,4,5-trimethoxybenzoic acid methyl ester |
-
2015
- 2015-06-17 CN CN201510337536.7A patent/CN105017000A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051353A (en) * | 1990-10-13 | 1991-05-15 | 上海大众制药厂 | Direct method preparation 3,4, the 5-tri-methoxybenzoate |
| CN1314337A (en) * | 2001-02-21 | 2001-09-26 | 罗伟 | Method for producing 3,4,5 trimethoxybenzoic acid |
| CN102690196A (en) * | 2011-04-15 | 2012-09-26 | 竹山县天新医药化工有限责任公司 | Preparation and purification method of 3,4,5-trimethoxybenzoic acid |
| CN103265434A (en) * | 2013-06-09 | 2013-08-28 | 湖南洪江棓雅生物科技有限公司 | Production technology of 3,4,5-trimethoxybenzoic acid methyl ester |
Non-Patent Citations (3)
| Title |
|---|
| 徐浩等: "2, 3, 4 - 三甲氧基苯甲酸的合成研究", 《林产化学与工业》 * |
| 毕良武等: "塔拉粉直接法制备3,4,5-三甲氧基", 《林产化学与工业》 * |
| 马莎等: "直接法制备三甲氧基苯甲酸甲酚小试报告", 《林产化工通讯》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848393A (en) * | 2020-06-17 | 2020-10-30 | 遵义市倍缘化工有限责任公司 | Method for treating wastewater from production of gallic acid and propyl gallate |
| CN111848393B (en) * | 2020-06-17 | 2023-06-06 | 遵义市倍缘化工有限责任公司 | Treatment method of wastewater from gallic acid and propyl gallate production |
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