CN106187703A - A kind of preparation method of pyrogallic acid - Google Patents
A kind of preparation method of pyrogallic acid Download PDFInfo
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- CN106187703A CN106187703A CN201610614056.5A CN201610614056A CN106187703A CN 106187703 A CN106187703 A CN 106187703A CN 201610614056 A CN201610614056 A CN 201610614056A CN 106187703 A CN106187703 A CN 106187703A
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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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Abstract
The invention provides the preparation method of a kind of pyrogallic acid, belong to chemical industry manufacture technology field, the present invention uses N, N dimethyl formamide, dehydrated alcohol are solvent, and add conducting polymer-polypyrrole and oxidant benzenesulfonic acid ferrum, under the effect of electric current, the temperature of 50～70 DEG C is reacted decarboxylize, the yield of the product coking gallic acid made is high, has that energy consumption is low, good product quality, a feature such as easy and simple to handle；And by high temperature evaporation concentration step, it is possible to effectively remove N, N dimethyl formamide, polypyrrole and the benzenesulfonic acid ferrum in coking gallic acid；Make to make coking gallic acid purity more than 95%.
Description
Technical field
The invention belongs to chemical industry manufacture technology field, particularly relate to the preparation method of a kind of pyrogallic acid.
Background technology
Pyrogallic acid (Pyrogallol acid), also known as Pyrogallol, 1,2,3,-thrihydroxy-benzene, Pyrogallol acid, for white
Acicular crystals, proportion 1.453 (4/4 DEG C), fusing point 131～133 DEG C, boiling point 309 DEG C, distil when being slowly heated and do not decompose,
Easily aoxidize, soluble in water, ethanol and ether, be 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
Become, synthesize in the industry such as medicine, dyestuff, can be as developing agent, heat sensitizer, the auxiliary agent of macromolecular material and chemical analysis reagent
Deng.
The preparation of pyrogallic acid mainly has gallic acid decarboxylation method and chemical synthesis.Gallic acid decarboxylation Jiao property
Raw material made by the gallic acid that gallic acid mainly uses Galla Chinensis or tower to draw powder hydrolysis to prepare, raw cokeability Galla Turcica (Galla Helepensis) 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 productivity of its output is the highest, and purity is inadequate.
Summary of the invention
For solving above-mentioned technical problem, the invention provides the preparation method of a kind of pyrogallic acid, the specific scheme is that
The preparation method of a kind of pyrogallic acid, comprises the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to 1:1～3:2～4:
The ratio mixing of 0.1～0.3, obtains mixed solution；Add the 5 of mixed solution weight～the benzenesulfonic acid ferrum of 15%；Then put
It is placed in tubular reactor container, solution is continually fed into electric current, and mixed solution is heated to 50～70 DEG C, react 20min
～3h；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
3) purification, obtains pyrogallic acid.
Further, described current intensity is 0.1～0.5A.
Further, described concentration is: is heated to solution boiling, when being concentrated into original 1/5, adds 5 times amount
Ethanol；Repeat " be heated to boiling and concentrate addition ethanol " more than three times；Then stop adding ethanol, be concentrated to give solid.
Further, described concentration is: is heated to 155～160 DEG C and concentrates, when being concentrated into the 1/5 of original volume,
Add 5 times of ethanol；Repeat " be heated to 155～160 DEG C and concentrate addition ethanol " more than twice；Then 90～100 DEG C it are cooled to
Concentrate,；Then cooling 90～100 DEG C, continues heating and concentrates, obtain solid.
Further, after adding ethanol the last time, solution is centrifuged separating at a temperature of 50～60 DEG C, obtains
The heating that carries out again of solution concentrates.
Further, described purification is: by solid as in the chloroformic solution of 3～5 times, stirs and heats, and temperature is
50～70 DEG C keep 10min～2h；Then isolated pyrogallic acid is filtered.
Further, the chloroform drip washing that pyrogallic acid temperature is 50～70 DEG C obtained.
The beneficial effects of the present invention is: the present invention uses N, N dimethyl formamide, dehydrated alcohol to be solvent, and add
Entering conducting polymer-polypyrrole and oxidant benzenesulfonic acid ferrum, under the effect of electric current, in the temperature of 50～70 DEG C, carboxylic is sloughed in reaction
Base, the yield of the product coking gallic acid made is high, has that energy consumption is low, good product quality, a feature such as easy and simple to handle；And lead to
Cross high temperature evaporation-concentration step, it is possible to effectively remove N, N dimethyl formamide, polypyrrole and the benzene sulphur in coking gallic acid
Acid ferrum；Make to make coking gallic acid purity more than 95%.
Detailed description of the invention
Technical scheme is described further below, but claimed scope is not limited to described.
Embodiment one
Present embodiments provide the preparation method of a kind of pyrogallic acid, comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to the ratio of 1:1:2:0.1
Example mixes, and obtains mixed solution；Add mixed solution weight 5% benzenesulfonic acid ferrum；It is then placed into tubular reactor container
In, solution is continually fed into electric current, current intensity is 0.1A；And mixed solution is heated to 50 DEG C, reacts 20minh；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
Described concentration is: is heated to solution to concentration of seething with excitement, when being concentrated into original 1/5, adds the ethanol of 5 times amount；Repeat " to add
Heat concentrates to boiling and adds ethanol " more than three times；Add the last time after ethanol, solution carry out at a temperature of 50 DEG C from
The heart separates, and the heating that carries out again obtaining solution concentrates, and is concentrated to give solid；
3) purification, by solid as in the chloroformic solution of 3～5 times, stirs and heats, and temperature is 50 DEG C and keeps 10minh；
Then filter isolated pyrogallic acid first product, then with the chloroform drip washing that temperature is 50 DEG C, obtain pyrogallic acid.
Embodiment two
Present embodiments provide the preparation method of a kind of pyrogallic acid, comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to the ratio of 1:3:4:0.3
Example mixes, and obtains mixed solution；Add mixed solution weight 15% benzenesulfonic acid ferrum；It is then placed into tubular reactor container
In, solution is continually fed into electric current, current intensity is 0.5A；And mixed solution is heated to 70 DEG C, reacts 3h；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
Described concentration is: is heated to solution to concentration of seething with excitement, when being concentrated into original 1/5, adds the ethanol of 5 times amount；Repeat " to add
Heat concentrates to boiling and adds ethanol " more than three times；Add the last time after ethanol, solution carry out at a temperature of 60 DEG C from
The heart separates, and the heating that carries out again obtaining solution concentrates, and is concentrated to give solid；
3) purification, by solid as in the chloroformic solution of 3～5 times, stirs and heats, and temperature is 70 DEG C and keeps 2h；Then
Filter isolated pyrogallic acid first product, then with the chloroform drip washing that temperature is 70 DEG C, obtain pyrogallic acid.
Embodiment three
Present embodiments provide the preparation method of a kind of pyrogallic acid, comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to the ratio of 1:2:3:0.2
Example mixes, and obtains mixed solution；Add mixed solution weight 10% benzenesulfonic acid ferrum；It is then placed into tubular reactor container
In, solution is continually fed into electric current, current intensity is 0.3A；And mixed solution is heated to 60 DEG C, reacts 2h；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
Described concentration is: is heated to solution to concentration of seething with excitement, when being concentrated into original 1/5, adds the ethanol of 5 times amount；Repeat " to add
Heat concentrates to boiling and adds ethanol " more than three times；Add the last time after ethanol, solution carry out at a temperature of 55 DEG C from
The heart separates, and the heating that carries out again obtaining solution concentrates, and is concentrated to give solid；
3) purification, by solid as in the chloroformic solution of 4 times, stirs and heats, and temperature is 60 DEG C and keeps 1h；Then cross
Filter isolated pyrogallic acid first product, then with the chloroform drip washing that temperature is 60 DEG C, obtain pyrogallic acid.
Embodiment one
Present embodiments provide the preparation method of a kind of pyrogallic acid, comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to the ratio of 1:1:2:0.1
Example mixes, and obtains mixed solution；Add mixed solution weight 5% benzenesulfonic acid ferrum；It is then placed into tubular reactor container
In, solution is continually fed into electric current, current intensity is 0.1A；And mixed solution is heated to 50 DEG C, reacts 20minh；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
Described concentration is: is heated to 155 DEG C and concentrates, and when being concentrated into the 1/5 of original volume, adds 5 times of ethanol；Repeat " heating
Concentrate to 155 DEG C and add ethanol " more than twice；Add the last time after ethanol, solution carry out at a temperature of 55 DEG C from
The heart separate, obtain solution carry out again be heated to 90 DEG C of concentrations, be concentrated to give solid.；
3) purification, by solid as in the chloroformic solution of 3～5 times, stirs and heats, and temperature is 50 DEG C and keeps 10minh；
Then filter isolated pyrogallic acid first product, then with the chloroform drip washing that temperature is 50 DEG C, obtain pyrogallic acid.
Embodiment five
Present embodiments provide the preparation method of a kind of pyrogallic acid, comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to the ratio of 1:3:4:0.3
Example mixes, and obtains mixed solution；Add mixed solution weight 15% benzenesulfonic acid ferrum；It is then placed into tubular reactor container
In, solution is continually fed into electric current, current intensity is 0.5A；And mixed solution is heated to 70 DEG C, reacts 3h；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
Described concentration is: is heated to 155～160 DEG C and concentrates, and when being concentrated into the 1/5 of original volume, adds 5 times of ethanol；Repeat
" it is heated to 160 DEG C and concentrates addition ethanol " more than twice；After adding ethanol the last time, solution is at a temperature of 55 DEG C
Be centrifuged separate, obtain solution carry out again be heated to 100 DEG C of concentrations, be concentrated to give solid.
3) purification, by solid as in the chloroformic solution of 3～5 times, stirs and heats, and temperature is 70 DEG C and keeps 2h；Then
Filter isolated pyrogallic acid first product, then with the chloroform drip washing that temperature is 70 DEG C, obtain pyrogallic acid.
Embodiment six
Present embodiments provide the preparation method of a kind of pyrogallic acid, comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole are according to the ratio of 1:2:3:0.2
Example mixes, and obtains mixed solution；Add mixed solution weight 10% benzenesulfonic acid ferrum；It is then placed into tubular reactor container
In, solution is continually fed into electric current, current intensity is 0.3A；And mixed solution is heated to 60 DEG C, reacts 2h；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
Described concentration is: is heated to 158 DEG C and concentrates, and when being concentrated into the 1/5 of original volume, adds 5 times of ethanol；Repeat " heating
Concentrate to 158 DEG C and add ethanol " more than twice；Add the last time after ethanol, solution carry out at a temperature of 55 DEG C from
The heart separate, obtain solution carry out again be heated to 95 DEG C of concentrations, be concentrated to give solid.
3) purification, by solid as in the chloroformic solution of 4 times, stirs and heats, and temperature is 60 DEG C and keeps 1h；Then filter
Isolated pyrogallic acid first product, then with the chloroform drip washing that temperature is 60 DEG C, obtain pyrogallic acid.
Claims (7)
1. the preparation method of a pyrogallic acid, it is characterised in that: comprise the following steps:
1) by anhydrous gallic acid and N, N dimethyl formamide, dehydrated alcohol, polypyrrole according to 1:1～3:2～4:0.1～
The ratio mixing of 0.3, obtains mixed solution；Add the 5 of mixed solution weight～the benzenesulfonic acid ferrum of 15%；It is then placed into pipe
In shape reaction vessel, solution is continually fed into electric current, and mixed solution is heated to 50～70 DEG C, react 20min～3h；
2) being placed in by mixed solution and add in heat container, with CO 2 gas-shielded, heating concentrates, and is concentrated to give solid；
3) purification, obtains pyrogallic acid.
2. the preparation method of pyrogallic acid as claimed in claim 1, it is characterised in that: described current intensity is 0.1
～0.5A.
3. the preparation method of pyrogallic acid as claimed in claim 1, it is characterised in that: described concentration is: be heated to
Solution seethes with excitement, and when being concentrated into original 1/5, adds the ethanol of 5 times amount；Repeat " be heated to boiling and concentrate addition ethanol " three
More than secondary；Then stop adding ethanol, be concentrated to give solid.
4. the preparation method of pyrogallic acid as claimed in claim 1, it is characterised in that: described concentration is: be heated to
155～160 DEG C concentrate, and when being concentrated into the 1/5 of original volume, add 5 times of ethanol；Repeat " be heated to 155～160 DEG C dense
Contracting adds ethanol " more than twice；Then it is cooled to 90～100 DEG C of concentrations, continues heating and concentrate, obtain solid.
5. the preparation method of the pyrogallic acid as described in claim 3 or 4, it is characterised in that: add second the last time
After alcohol, solution is centrifuged separating at a temperature of 50～60 DEG C, and the heating that carries out again obtaining solution concentrates.
6. the preparation method of pyrogallic acid as claimed in claim 1, it is characterised in that: described purification is: by solid
As in the chloroformic solutions of 3～5 times, stirring and heat, temperature is 50～70 DEG C and keeps 10min～2h；Then filter and separate
To pyrogallic acid.
7. the preparation method of pyrogallic acid as claimed in claim 6, it is characterised in that: the pyrogallic acid obtained is used
Temperature is the chloroform drip washing of 50～70 DEG C.
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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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680296A (en) * | 2018-12-24 | 2019-04-26 | 河北工业大学 | A method of the O-methoxy phenolic group group decomposited with lignin prepares eugenol with additional allyl reaction |
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 |
-
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 |
|---|
| 李伟善: "利用电解脱羧(Kolbe)反应的有机合成", 《广州化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680296A (en) * | 2018-12-24 | 2019-04-26 | 河北工业大学 | A method of the O-methoxy phenolic group group decomposited with lignin prepares eugenol with additional allyl reaction |
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