CN106187703B - A kind of preparation method of pyrogallic acid - Google Patents
A kind of preparation method of pyrogallic acid Download PDFInfo
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- CN106187703B CN106187703B CN201610614056.5A CN201610614056A CN106187703B CN 106187703 B CN106187703 B CN 106187703B CN 201610614056 A CN201610614056 A CN 201610614056A CN 106187703 B CN106187703 B CN 106187703B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B3/00—Electrolytic production of organic compounds
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Abstract
The present invention provides a kind of preparation methods of pyrogallic acid, belong to chemical industry manufacture technology field, the present invention uses N, N dimethyl formamides, absolute ethyl alcohol are solvent, and conducting polymer-polypyrrole and oxidant benzene sulfonic acid iron is added, under the action of electric current, react decarboxylize in 50~70 DEG C of temperature, the high income of manufactured product coking gallic acid has the characteristics that low energy consumption, good product quality, easy to operate；And by high temperature evaporation concentration step, the N in coking gallic acid, N dimethyl formamides, polypyrrole and benzene sulfonic acid iron can be effectively removed；So that coking gallic acid purity is made 95% or more.
Description
Technical field
The invention belongs to chemical industry manufacture technology field more particularly to a kind of preparation methods of pyrogallic acid.
Background technology
Pyrogallic acid (Pyrogallol acid), also known as Pyrogallol, pyrogallol, Pyrogallol acid, for white
Acicular crystals, proportion 1.453 (4/4 DEG C), 131~133 DEG C of fusing point, 309 DEG C of boiling point, when slow heating distillation without decomposing,
It easily aoxidizes, soluble easily in water, ethyl alcohol and ether, is insoluble in benzene, dimethylbenzene equal solvent.
Pyrogallic acid is a kind of important fine chemicals, chemical reagent, is widely used in light industry, food, You Jihe
At, synthesis medicine, dyestuff etc. it is industrial in, can be used as developer, heat sensitizer, the auxiliary agent of high molecular material and chemical analysis reagent
Deng.
The preparation of pyrogallic acid mainly has gallic acid decarboxylation method and chemical synthesis.Gallic acid decarboxylation coke
Gallic acid mainly uses Chinese gall or tower that powder hydrolysis gallic acid obtained is drawn to make raw material, the raw cokeability nutgall after decarboxylation
Acid.Gallic acid decarboxylation method mainly has pressurization decarboxylation, decompression decarboxylation, normal pressure catalytic decarboxylation, solvent decarboxylation and decarboxylate of microorganisms etc.
Technique；Chemical synthesis can not also synthesize pyrogallic acid by gallic acid by gallic acid.But it is existing
Technology, the pyrogallic acid yield of output is not high, and purity is inadequate.
Invention content
In order to solve the above technical problems, the present invention provides a kind of preparation method of pyrogallic acid, concrete scheme is：
A kind of preparation method of pyrogallic acid, includes the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：1~3：2~4：
0.1~0.3 ratio mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 5~15% of mixed solution weight；Then it puts
It is placed in tubular reactor container, electric current is continually fed into solution, and mixed solution is heated to 50~70 DEG C, reacts 20min
~3h；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
3) it purifies, obtains pyrogallic acid.
Further, the current strength is 0.1~0.5A.
Further, the concentration is：It is heated to solution boiling, when being concentrated into original 1/5,5 times of amounts of addition
Ethyl alcohol；It is more than repetition " being heated to boiling concentration-addition ethyl alcohol " three times；Then stop that ethyl alcohol is added, be concentrated to give solid.
Further, the concentration is：155~160 DEG C are heated to be concentrated, when being concentrated into the 1/5 of original volume,
5 times of ethyl alcohol are added；Repeat " being heated to 155~160 DEG C of concentrations-addition ethyl alcohol " more than twice；Then 90~100 DEG C are cooled to
Concentration,；Then cool down 90~100 DEG C, continue heating concentration, obtain solid.
Further, after ethyl alcohol is added in last time, solution is centrifuged at a temperature of 50~60 DEG C, obtains
Solution carries out heating concentration again.
Further, the purifying is：By solid as in 3~5 times of chloroformic solution, stirs and heat, temperature is
50~70 DEG C of holding 10min~2h；Then it is separated by filtration to obtain pyrogallic acid.
Further, the chloroform that the pyrogallic acid temperature obtained is 50~70 DEG C elutes.
The beneficial effects of the present invention are：The present invention uses N, and N dimethyl formamides, absolute ethyl alcohol are solvent, and are added
Enter conducting polymer-polypyrrole and oxidant benzene sulfonic acid iron, is reacted under the action of electric current, in 50~70 DEG C of temperature and slough carboxylic
Base, the high income of manufactured product coking gallic acid have the characteristics that low energy consumption, good product quality, easy to operate；And lead to
High temperature evaporation-concentration step is crossed, the N in coking gallic acid, N dimethyl formamides, polypyrrole and benzene sulphur can be effectively removed
Sour iron；So that coking gallic acid purity is made 95% or more.
Specific implementation mode
Be described further below technical scheme of the present invention, but claimed range be not limited to it is described.
Embodiment one
A kind of preparation method of pyrogallic acid is present embodiments provided, is included the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：1：2：0.1 ratio
Example mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 5% of mixed solution weight；It is then placed into tubular reactor container
In, electric current, current strength 0.1A are continually fed into solution；And mixed solution is heated to 50 DEG C, reacts 20minh；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
The concentration is：Solution is heated to concentration of boiling, when being concentrated into original 1/5, the ethyl alcohol of 5 times of amounts is added；Repetition " adds
Heat to boiling concentration-addition ethyl alcohol " three times more than；Last time be added ethyl alcohol after, solution carried out at a temperature of 50 DEG C from
The heart detaches, and obtain solution carries out heating concentration again, is concentrated to give solid；
3) it purifies, by solid as in 3~5 times of chloroformic solution, stirs and heat, temperature is 50 DEG C of holding 10minh；
Then it is separated by filtration to obtain pyrogallic acid first product, then the chloroform for being 50 DEG C with temperature elutes, and obtains pyrogallic acid.
Embodiment two
A kind of preparation method of pyrogallic acid is present embodiments provided, is included the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：3：4：0.3 ratio
Example mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 15% of mixed solution weight；It is then placed into tubular reactor container
In, electric current, current strength 0.5A are continually fed into solution；And mixed solution is heated to 70 DEG C, reacts 3h；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
The concentration is：Solution is heated to concentration of boiling, when being concentrated into original 1/5, the ethyl alcohol of 5 times of amounts is added；Repetition " adds
Heat to boiling concentration-addition ethyl alcohol " three times more than；Last time be added ethyl alcohol after, solution carried out at a temperature of 60 DEG C from
The heart detaches, and obtain solution carries out heating concentration again, is concentrated to give solid；
3) it purifies, by solid as in 3~5 times of chloroformic solution, stirs and heat, temperature is 70 DEG C of holding 2h；Then
It is separated by filtration to obtain pyrogallic acid first product, then the chloroform for being 70 DEG C with temperature elutes, and obtains pyrogallic acid.
Embodiment three
A kind of preparation method of pyrogallic acid is present embodiments provided, is included the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：2：3：0.2 ratio
Example mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 10% of mixed solution weight；It is then placed into tubular reactor container
In, electric current, current strength 0.3A are continually fed into solution；And mixed solution is heated to 60 DEG C, reacts 2h；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
The concentration is：Solution is heated to concentration of boiling, when being concentrated into original 1/5, the ethyl alcohol of 5 times of amounts is added；Repetition " adds
Heat to boiling concentration-addition ethyl alcohol " three times more than；Last time be added ethyl alcohol after, solution carried out at a temperature of 55 DEG C from
The heart detaches, and obtain solution carries out heating concentration again, is concentrated to give solid；
3) it purifies, by solid as in 4 times of chloroformic solution, stirs and heat, temperature is 60 DEG C of holding 1h；Then it crosses
Isolated pyrogallic acid first product is filtered, then the chloroform for being 60 DEG C with temperature elutes, and obtains pyrogallic acid.
Embodiment one
A kind of preparation method of pyrogallic acid is present embodiments provided, is included the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：1：2：0.1 ratio
Example mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 5% of mixed solution weight；It is then placed into tubular reactor container
In, electric current, current strength 0.1A are continually fed into solution；And mixed solution is heated to 50 DEG C, reacts 20minh；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
The concentration is：It is heated to 155 DEG C to be concentrated, when being concentrated into the 1/5 of original volume, 5 times of ethyl alcohol is added；Repeat " heating
To 155 DEG C of concentrations-addition ethyl alcohol " more than twice；Last time be added ethyl alcohol after, solution carried out at a temperature of 55 DEG C from
The heart detaches, and obtain solution carries out being heated to again 90 DEG C of concentrations, is concentrated to give solid.；
3) it purifies, by solid as in 3~5 times of chloroformic solution, stirs and heat, temperature is 50 DEG C of holding 10minh；
Then it is separated by filtration to obtain pyrogallic acid first product, then the chloroform for being 50 DEG C with temperature elutes, and obtains pyrogallic acid.
Embodiment five
A kind of preparation method of pyrogallic acid is present embodiments provided, is included the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：3：4：0.3 ratio
Example mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 15% of mixed solution weight；It is then placed into tubular reactor container
In, electric current, current strength 0.5A are continually fed into solution；And mixed solution is heated to 70 DEG C, reacts 3h；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
The concentration is：It is heated to 155~160 DEG C to be concentrated, when being concentrated into the 1/5 of original volume, 5 times of ethyl alcohol is added；It repeats
" being heated to 160 DEG C of concentrations-addition ethyl alcohol " more than twice；After ethyl alcohol is added in last time, solution is at a temperature of 55 DEG C
It is centrifuged, obtain solution carries out being heated to again 100 DEG C of concentrations, is concentrated to give solid.
3) it purifies, by solid as in 3~5 times of chloroformic solution, stirs and heat, temperature is 70 DEG C of holding 2h；Then
It is separated by filtration to obtain pyrogallic acid first product, then the chloroform for being 70 DEG C with temperature elutes, and obtains pyrogallic acid.
Embodiment six
A kind of preparation method of pyrogallic acid is present embodiments provided, is included the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：2：3：0.2 ratio
Example mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 10% of mixed solution weight；It is then placed into tubular reactor container
In, electric current, current strength 0.3A are continually fed into solution；And mixed solution is heated to 60 DEG C, reacts 2h；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
The concentration is：It is heated to 158 DEG C to be concentrated, when being concentrated into the 1/5 of original volume, 5 times of ethyl alcohol is added；Repeat " heating
To 158 DEG C of concentrations-addition ethyl alcohol " more than twice；Last time be added ethyl alcohol after, solution carried out at a temperature of 55 DEG C from
The heart detaches, and obtain solution carries out being heated to again 95 DEG C of concentrations, is concentrated to give solid.
3) it purifies, by solid as in 4 times of chloroformic solution, stirs and heat, temperature is 60 DEG C of holding 1h；Then it filters
Isolated pyrogallic acid first product, then the chloroform for being 60 DEG C with temperature elute, and obtain pyrogallic acid.
Claims (7)
1. a kind of preparation method of pyrogallic acid, it is characterised in that：Include the following steps：
1) by anhydrous gallic acid and N, N dimethyl formamides, absolute ethyl alcohol, polypyrrole are according to 1：1~3：2~4：0.1~
0.3 ratio mixing, obtains mixed solution；Add the benzene sulfonic acid iron of the 5~15% of mixed solution weight；It is then placed into pipe
In shape reaction vessel, electric current is continually fed into solution, and mixed solution is heated to 50~70 DEG C, reacts 20min~3h；
2) mixed solution is placed in heating container, use is CO 2 gas-shielded, and heating concentration is concentrated to give solid；
3) it purifies, obtains pyrogallic acid.
2. the preparation method of pyrogallic acid as described in claim 1, it is characterised in that：The current strength is 0.1
~0.5A.
3. the preparation method of pyrogallic acid as described in claim 1, it is characterised in that：The concentration is：It is heated to
Solution boils, and when being concentrated into original 1/5, the ethyl alcohol of 5 times of amounts is added；Repeat " being heated to boiling concentration-addition ethyl alcohol " three
More than secondary；Then stop that ethyl alcohol is added, be concentrated to give solid.
4. the preparation method of pyrogallic acid as described in claim 1, it is characterised in that：The concentration is：It is heated to
155~160 DEG C are concentrated, and when being concentrated into the 1/5 of original volume, 5 times of ethyl alcohol are added；Repeat " be heated to 155~160 DEG C it is dense
Contracting-addition ethyl alcohol " is more than twice；Then 90~100 DEG C of concentrations are cooled to, continues heating concentration, obtains solid.
5. the preparation method of pyrogallic acid as described in claim 3 or 4, it is characterised in that：Second is added in last time
After alcohol, solution is centrifuged at a temperature of 50~60 DEG C, and obtain solution carries out heating concentration again.
6. the preparation method of pyrogallic acid as described in claim 1, it is characterised in that：The purifying is：By solid
It is placed in 3~5 times of chloroformic solution, stirs and heats, temperature is 50~70 DEG C of holding 10min~2h；Then it is separated by filtration
To pyrogallic acid.
7. the preparation method of pyrogallic acid as claimed in claim 6, it is characterised in that：Obtained pyrogallic acid is used
The chloroform that temperature is 50~70 DEG C elutes.
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| CN201610614056.5A CN106187703B (en) | 2016-07-30 | 2016-07-30 | A kind of preparation method of pyrogallic acid |
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| CN106187703B true CN106187703B (en) | 2018-09-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001071020A2 (en) * | 2000-03-16 | 2001-09-27 | Board Of Trustees Operating Michigan State University | Biocatalytic synthesis of galloid organics |
| CN101161628A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium |
| CN101475450A (en) * | 2009-02-04 | 2009-07-08 | 南京林业大学 | Method for preparing pyrogallic acid with glyoxaline as gallic acid decarboxylation catalyst |
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2016
- 2016-07-30 CN CN201610614056.5A patent/CN106187703B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001071020A2 (en) * | 2000-03-16 | 2001-09-27 | Board Of Trustees Operating Michigan State University | Biocatalytic synthesis of galloid organics |
| CN101161628A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing gallic acid and pyrogallic acid synchronously by non-catalyzed hydrolysis of tannin-containing biomass in high-temperature liquid water medium |
| CN101475450A (en) * | 2009-02-04 | 2009-07-08 | 南京林业大学 | Method for preparing pyrogallic acid with glyoxaline as gallic acid decarboxylation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 利用电解脱羧(Kolbe)反应的有机合成;李伟善;《广州化工》;19921231;第20卷(第4期);18-21,44页 * |
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