CN1556093A - Preparation method of gallic acid high grade alxoxide ester - Google Patents
Preparation method of gallic acid high grade alxoxide ester Download PDFInfo
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- CN1556093A CN1556093A CNA2003101128184A CN200310112818A CN1556093A CN 1556093 A CN1556093 A CN 1556093A CN A2003101128184 A CNA2003101128184 A CN A2003101128184A CN 200310112818 A CN200310112818 A CN 200310112818A CN 1556093 A CN1556093 A CN 1556093A
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- gallic acid
- preparation
- ester
- high triacontanol
- solvent
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Abstract
A process for preparing the high-grade alkanol ester for gallic acid, whose chemical formula is (HO)3C6H2COOCnH2n+1, includes catalytic reaction between gallic acid, high-grade alkanol, and solvent at 105-125 deg.C, carrying to resultant vapour out of the reactor by the evaporated solvent, condensing, removing water by millpore ceramic column, returning solvent back to reactor, continuous circulation until reaction is terminated, and recrystallizing.
Description
(technical field)
The present invention relates to general molecular formula and be (HO)
3C
6H
2COOC
nH
2n+1The preparation method, particularly n=8 of gallic acid high triacontanol ester, the preparation method of this gallic acid high triacontanol ester of 10,12,14,16,18,20.
(background technology)
Gallic acid high triacontanol ester is white to the canescence crystalline powder, and molecular formula is:
(HO)
3C
6H
2COOC
nH
2n+1 (n＝8，10，12，14，16，18，20)
Gallic acid high triacontanol ester is a kind of oxyradical eccysis agent and antioxidant.Because this class material has anti-platelet aggregation, vasodilation effect, antioxidant effect is better than Vc, so be promising medicine of a class and good food antioxidant.Wherein more English, the collection of U.S. pharmacopeia of gallic acid dodecane alcohol ester is the food antioxidant that the FDA/WHO approval is used.
The direct esterification legal system is equipped with the chemical equation of gallic acid high triacontanol ester:
The traditional preparation process method of gallic acid high triacontanol ester is to make catalyzer with the vitriol oil, make gallic acid and high triacontanol effect, with benzene (or dimethylbenzene) is solvent (promptly being with aqua), removes the water that generates in the reaction process with boiling the distillation mode, and reaction is carried out to the direction that generates ester.Because the high triacontanol carbon atom quantity is many, gallic acid meltage deficiency therein is so long reaction time, yield are low.Because benzene is the little solvent of a kind of polarity, it makes the band aqua, can not improve the solubleness of gallic acid.The vitriol oil has stronger oxidisability in addition, so equipment corrosion is serious, product colour is dark.
Some recent researchs, the band aqua (dioxane etc.) that adopts more weak catalyzer (tosic acid etc.) of oxidisability and polarity to be fit to, product yield increases, but the key link of obstruction Product industrialization remains the separation problem of the water that generates in the esterification reaction process.U.S. Pat 2595241 discloses the technology of making catalyzer with methylsulfonic acid, and byproduct of reaction reduces, and the purity of this high triacontanol of gained Nutgalls ester improves, but the reaction times reach 30 hours, yield is on the low side (52%).The esterification yield that Japanese Patent (the clear 52-48966 of JP) is made the band aqua with dioxane is higher, but makes dewatering agent with Anhydrous potassium carbonate, and dewatering time is long, and is difficult for the reprocessing cycle use.Above-mentioned technology band water, dehydration and each step of solvent recuperation are intermittently carried out, and complex process, processing condition are difficult to control, unstable product quality, and yield is low, the cost height, so industrial applications is difficult.
(summary of the invention)
The purpose of this invention is to provide a kind of suitable suitability for industrialized production the preparation technology of gallic acid high triacontanol ester, it can carry out esterification critical system-band water, dehydration and each step process of solvent recuperation continuously, improve speed of reaction and product purity, reduce cost.
Technical scheme of the present invention is:
Raw material gallic acid and high triacontanol (n=8,10,12,14,16,18,20) drop into reactor, the solvent dioxane that has added the effect of band water, in the presence of catalyzer, the material heating keeps 105-120 ℃, react under stirring, the water aqua dioxane going along with vapour that reaction generates feeds condenser, and phlegma enters the micropore ceramics adsorption column, and wherein moisture content is adsorbed by micropore ceramics, the dioxane solvent Returning reactor that is not adsorbed, continue circulation and repeat above band water process, esterification 5-14 hour, reaction finished, adding in the reactor purifies makes the crude product dissolving with solvent, separate out crystallization with postcooling, cross the leaching crystallisate, get gallic acid high triacontanol crystalline esters product after the drying.Among the present invention, can regulate the temperature of esterification, promptly be with the water solvent steam output to increase by the flow velocity of controlling phlegma in the ceramic adsorption column, phlegma is accelerated by the speed of adsorption column, the condensing solvent amount of Returning reactor increases, and then temperature of reactor also reduces, vice versa.
The catalyzer that the present invention adopts is Witco 1298 Soft Acid or tosic acid.
Said micropore ceramics post is an aluminum oxide micro-porous adsorption post, can be provided with a plurality of posts, and each post alternately switches and regeneration is used.
Added solvent is benzene or toluene in the material of reaction end back.
The processing of can decolouring of material after reaction finishes.
In sum, the present invention makes gallic acid high triacontanol ester method and has adopted condensation and absorbing process, by band aqua round-robin mode in system, continuously will react the water that generates and take reactor out of, absorption dewaters after the condensation, reaches and removes water generation reaction continuously, the purpose that reaction is carried out to the esterification direction, consequently improved speed of reaction, the reaction times shortens greatly, and general needs 5-10 hour.The band water solvent flows out back Returning reactor automatically from adsorption column, is recycled continuously.In present method, the continuous interaction of each step of band water, dehydration and solvent recuperation of esterification is carried out, and helps realizing sequencing, the digitizing operation of production process, is convenient to the CONTROL PROCESS condition, makes constant product quality.Esterification temperature low (105-125 ℃), by product reduces, and product colour is shallow, and end product purity height, various esters are all more than 99%.Product yield can reach more than 90%.In addition, adaptability to raw material is strong, cost is low.
(embodiment)
Embodiment 1:
The reactor that has stirring, thermometer and heating jacket is connected with the aluminum oxide micropore ceramic tube with condenser successively.
Drop into gallic acid 96g in the reactor, n-Octanol 88g, catalyzer Witco 1298 Soft Acid 28g and band water solvent 1, the 4-dioxane is an amount of, and stirring heating keeps interior temperature 108-110 ℃ of anti-device, esterification 8 hours.In this process, the gaseous state 1 in the reactor, 4-dioxane will reacts the water of generation to be taken out of from reactor head with the steam form, becomes liquid phase through condenser condenses, adsorbs wherein Returning reactor recirculation behind the moisture content by the aluminum oxide micropore ceramic tube.After reaction finishes, behind the solvent during the reactant underpressure distillation is reclaimed, use the toluene heating for dissolving, the solution weight crystallization gets Stabilizer GA 8 148g, and yield is 94%.93-94 ℃ of product fusing point.Through mass spectroscopy molecular weight of product 282.
Embodiment 2:
Device drops into raw material gallic acid 96g, stearyl alcohol 215g with embodiment 1 in the reactor, catalyzer tosic acid 15g, solvent 1, and the 4-dioxane is an amount of, stirring heating, temperature 115-120 ℃ esterification is 14 hours in the retainer.After from reaction mixture, reclaiming solvent, get gallic acid octadecyl ester 373g (yield 92%), fusing point 101-102 ℃ with xylene soluble crude product and recrystallization.Through mass spectroscopy, molecular weight of product is 422.
The various product yields of gallic acid high triacontanol ester of embodiment 3 the inventive method preparation see the following form.
Preface
Acids alcohols catalyzer band water water solvent product yield %
Number
1 gallic acid n-Octanol Witco 1298 Soft Acid 1,4-dioxane Stabilizer GA 8 94
2 gallic acid lauryl alcohol tosic acid 1,4-dioxane Progallin LA 97
3 gallic acid tetradecyl alcohol tosic acid 1,4-dioxane gallic acid 14 esters 94
4 gallic acid hexadecanol tosic acid 1,4-dioxane gallic acid hexadecyl ester 91
5 gallic acid stearyl alcohol tosic acid 1,4-dioxane gallic acid octadecyl ester 92
6 gallic acid eicosanol tosic acid 1,4-dioxane gallic acid 20 esters 93
Claims (5)
1. the preparation method of gallic acid high triacontanol ester, raw material gallic acid and high triacontanol drop into reactor, the solvent dioxane that in the presence of catalyzer, has added the effect of band water, it is characterized in that the material heating keeps 105-120 ℃, under agitation react, the water that reaction generates feeds condenser with the dioxane vapour, phlegma feeds micropore ceramics post adsorption column, wherein moisture content is adsorbed by micropore ceramics, the dioxane solvent Returning reactor that is not adsorbed, continue circulation and repeat above band water process, reaction finishes, and adds solvent in the reactor and makes the crude product dissolving, separates out crystallization with postcooling, cross the leaching crystallisate, get gallic acid high triacontanol crystalline esters product after the drying.
2. according to the preparation method of the gallic acid high triacontanol ester of claim 1, it is characterized in that said catalyzer is a Witco 1298 Soft Acid
3. according to the preparation method of the gallic acid high triacontanol ester of claim 1, it is characterized in that said catalyzer is a tosic acid.
4. according to the preparation method of the gallic acid high triacontanol ester of claim 1 or 2 or 3, it is characterized in that said micropore ceramics post is an aluminum oxide micro-porous adsorption post.
5. according to the preparation method of the gallic acid high triacontanol ester of claim 4, it is characterized in that being provided with a plurality of micropore ceramics posts and alternately switch and regeneration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101128184A CN1556093A (en) | 2003-12-31 | 2003-12-31 | Preparation method of gallic acid high grade alxoxide ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101128184A CN1556093A (en) | 2003-12-31 | 2003-12-31 | Preparation method of gallic acid high grade alxoxide ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643418B (en) * | 2009-09-07 | 2012-05-02 | 湖南先伟实业有限公司 | Preparation method of gallic acid alcohol ester |
| CN102442930A (en) * | 2011-11-02 | 2012-05-09 | 江苏宇翔化工有限公司 | Preparation method of DL-p-methylsulfonylphenyl serine ethyl ester |
| CN107216251A (en) * | 2016-03-21 | 2017-09-29 | 湖南师范大学 | The efficient solvent of one-step synthesis method gallic acid octadecyl ester |
| CN110776972A (en) * | 2019-11-08 | 2020-02-11 | 宝鸡文理学院 | Synthetic ester lubricating oil base oil based on green renewable resources |
-
2003
- 2003-12-31 CN CNA2003101128184A patent/CN1556093A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643418B (en) * | 2009-09-07 | 2012-05-02 | 湖南先伟实业有限公司 | Preparation method of gallic acid alcohol ester |
| CN102442930A (en) * | 2011-11-02 | 2012-05-09 | 江苏宇翔化工有限公司 | Preparation method of DL-p-methylsulfonylphenyl serine ethyl ester |
| CN107216251A (en) * | 2016-03-21 | 2017-09-29 | 湖南师范大学 | The efficient solvent of one-step synthesis method gallic acid octadecyl ester |
| CN110776972A (en) * | 2019-11-08 | 2020-02-11 | 宝鸡文理学院 | Synthetic ester lubricating oil base oil based on green renewable resources |
| CN110776972B (en) * | 2019-11-08 | 2021-10-26 | 宝鸡文理学院 | Synthetic ester lubricating oil base oil based on green renewable resources |
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