CN1680239A - Preparation of pyrogallic acid with pyridine as decarboxylation catalyst of 3,4,5-trihydroxybenzoic acid - Google Patents
Preparation of pyrogallic acid with pyridine as decarboxylation catalyst of 3,4,5-trihydroxybenzoic acid Download PDFInfo
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- CN1680239A CN1680239A CN 200510038249 CN200510038249A CN1680239A CN 1680239 A CN1680239 A CN 1680239A CN 200510038249 CN200510038249 CN 200510038249 CN 200510038249 A CN200510038249 A CN 200510038249A CN 1680239 A CN1680239 A CN 1680239A
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Abstract
Production of pyrogallic acid with pyridine as gallic acid decarboxylation catalyst is carried out by agitating and mixing anhydrous gallic acid with pyridine, refluxing reacting, material forming melt, CO2 bubbles escaping, keeping temperature until bubble not escaping from reacting product, keeping temperature of reacting product, releasing pressure of the atmosphere, distilling out pyridine of reacting product, raising temperature for the reacting product, collecting escaped sublimed product until sublimed product non escaping, grinding the sublimed product, adding chloroform, agitating and washing, dissolving the residual pyridine into chloroform, filtering, drip washing by chloroform, filtering, drying, removing residual chloroform, and obtaining pyrogallic acid. It achieves low boiling point, suitable alkalinity and easy separation.
Description
Technical field
The present invention relates to a kind of method for preparing pyrogallol, relate in particular to a kind of method for preparing pyrogallol with pyridine as gallate decarboxylation accelerant.
Background technology
In 18 end of the centurys, Scheele makes pyrogallol by destructive distillation from gallic acid first.After this, the preparation method is constantly developed, and can be divided into semi-synthesis method and complete synthesizing process two big classes generally.
Semi-synthesis method is to be that raw material carries out decarboxylation with the gallic acid.Be directly to heat destructive distillation at first, this method by product is many, and the product yield is low; After develop into vacuum decompression decarboxylation, solvent decarboxylation and in the decarboxylation of water medium mesohigh.1976 Poland Patent (Pol.87,354, Pol.83,789) propose use N, dinethylformamide is as decarboxylation under the catalyzer normal pressure, thick product is heat-fused in the high boiling point phthalic ester distillation makes with extra care.The Japanese Patent nineties in last century (JP 82,138,753) proposes again to prepare pyrogallol with fermentation method by Weibull or gallic acid.
Aspect complete synthesizing process, representative having is following several: the seventies, proposition lipid acid such as Hurd was raw material, and by catalyzing and condensing cyclisation, acid hydrolysis, pyrogallol is made in last decarboxylation.English Patent (1358700) has reported that with cyclohexanone be raw material, adopts chlorination and catalytic hydrolysis to prepare pyrogallol.Japanese Patent reported once that with cyclohexene be raw material, makes earlier by catalyzed oxidation and hydrolysis and encircles triol, and after the synthetic pyrogallol of catalytic dehydrogenation aromatization.In the seventies, Japan has proposed pyrogallol is isolated in the Resorcinol oxidation from product.The U.S. in the eighties with p-tert-butylphenol bromination, hydrolysis, methoxylation, then take off alkyl and hydrolysis makes product.The mid-80, German Patent propose with 2, and 6-diamino 4-butylphenol is that raw material carries out catalysis, acid hydrolysis prepares pyrogallol.In above-mentioned numerous reports, some method has DEVELOPMENT PROSPECT, but that industrial applications still has some technological problemses to have is to be solved.
The Mallinckrodt company of the major vendor of current external production pyrogallol such as the U.S., the Fuji Chem.Industry company of the HarshwChemical company in Europe, Japan and Dainippon Pharmaceutical company etc. all adopt the semisynthesis of pressurization decarboxylation.In China, traditional pyrogallol preparation technology adopts decompression direct high temperature decarboxylation down.This preparation technology's yield is lower, and quality product is also relatively poor.Domestic in recent years also have the normal pressure of employing catalytic decarboxylation method to prepare pyrogallol, obtains high product yield and better products quality, but all do not report and use which kind of catalyzer.
Summary of the invention
The invention provides that a kind of yield height, energy consumption are low, good product quality, operation are easier prepares the method for pyrogallol as gallate decarboxylation accelerant with pyridine.
The present invention adopts following technical scheme:
A kind ofly prepare the method for pyrogallol as gallate decarboxylation accelerant, comprise following a few step with pyridine:
The first step, be 1 with anhydrous gallic acid and pyridine with mol ratio: (0.1～0.4) mixes, and 130～160 ℃ of following back flow reaction, material becomes molten mass, and a large amount of CO are arranged simultaneously
2Bubble is overflowed, and insulation no bubble in reaction product generates,
In second step, keeping the temperature of reaction product is 130～160 ℃, and the pressure of the residing atmosphere of above-mentioned reaction product is reduced to below the 2kPa gradually from 1 standard atmospheric pressure, thereby distills out the pyridine in the reaction product,
The 3rd step was 160～190 ℃ conditions under to distil at pressure less than 2kPa and temperature with the above-mentioned product of removing behind the pyridine, and collects the flores of overflowing simultaneously, till no flores effusion,
The 4th step, the flores of above-mentioned effusion is ground, the chloroform that adds 4～6 times of weight of flores that are equivalent to overflow, and agitator treating, make remaining pyridine be dissolved in the chloroform, filter, and use chloroform drip washing, it is dry under 40～60 ℃ that the back is done in filter, to remove residual chloroform, obtains pyrogallol.
Principle of the present invention:
Pyrogallol (pyrogallol) has another name called pyrogallol, pyrogallol, 1.Molecular formula: C
6H
6O
3, molecular weight 126.05, structural formula:
Pyrogallol is a kind of multiduty chemical reagent and industrial chemicals, can be used for synthetic medicine, agricultural chemicals, dyestuff, can be used as the auxiliary agent of macromolecular material, photographic developer, thermosensitizing agent and chemical analysis reagent etc.
It is as follows with the pyridine to be that gallate decarboxylation accelerant prepares the pyrogallol reaction process:
The reaction mechanism that carboxylic acid loses carboxylic can be considered as electrophilic substitution, and the organic amine that alkalescence is suitable has katalysis to it.Select pyridine to be based on its chemical structure characteristics as catalyzer, be on its nitrogen-atoms a pair of lone electron can with the carboxylic acid salify, make that the O-H key weakens on the carboxyl, again because phenyl is an electron-withdrawing group, weakened the C-C key between phenyl ring and the carboxyl, dual function has caused the mistake carboxylic.
Pyridine has the function of dissolving gallic acid concurrently as decarboxylation catalyst, and its boiling point is 115 ℃ under the normal pressure, by condensing reflux, makes its Returning reacting system, thereby makes gallic acid be able to complete reaction in decarboxylation procedure.
The present invention obtains following technique effect:
1. with the N that has now reported, N-dimethylformamide catalyzer is compared, and the used catalyzer pyridine of the present invention is a kind of weakly alkaline heterocyclic amine (pK
b=8.75), have that alkalescence is suitable, boiling point lowly is easy to separate, to product quality do not have influence, can be directly by distilling and subsequently washing and needn't use other auxiliary agent can obtain the characteristics of high purity product.
2. the present invention utilizes the katalysis of pyridine to make anhydrous gallic acid decarboxylation, underpressure distillation goes out pyridine then, thereby wash remaining pyridine preparation pyrogallol with chloroform again, have that yield height, energy consumption are low, good product quality, the easier characteristics of operation, technical maturity can be used for suitability for industrialized production.
3. with the product of distillation distillation, pyrogallol can be distilled out and separation of by-products, thereby improve the purity of pyrogallol.
4. the time owing to the pyrogallol distillation, a small amount of pyridine also is blended in wherein, the present invention washs the remaining pyridine of removing in the pyrogallol with chloroform, the good product quality of the pyrogallol of acquisition, and the result can be referring to the product quality analysis data of embodiment back.
5. the chloroform of the present invention's employing is that lower boiling does not fire solvent, is easy to remove from product recovery, can reuse after simple distillation.
Description of drawings
Fig. 1 is the schema of the embodiment of the invention 1.
Embodiment
Embodiment 1:
A kind ofly prepare the method for pyrogallol as gallate decarboxylation accelerant, comprise following a few step with pyridine:
The first step, be 1 with anhydrous gallic acid and pyridine with mol ratio: (0.1～0.4) mixes, and 130～160 ℃ of following back flow reaction, material becomes molten mass, and a large amount of CO are arranged simultaneously
2Bubble is overflowed, and insulation no bubble in reaction product generates,
Wherein, the ratio of the amount of substance of anhydrous gallic acid and pyridine can be 1: 0.15, and 1: 0.18,1: 0.22,1: 0.27,1: 0.33,1: 0.36,1: 0.38, the temperature of back flow reaction can be 135 ℃, 146 ℃, and 153 ℃, 158 ℃; The temperature of insulation is identical with the back flow reaction temperature, is 130～160 ℃;
In second step, keeping the temperature of reaction product is 130～160 ℃, and the pressure of the residing atmosphere of above-mentioned reaction product is reduced to below the 2kPa gradually from 1 standard atmospheric pressure, thereby distills out the pyridine in the reaction product,
In the present embodiment, reactant atmosphere of living in can be vacuumized gradually from normal pressure gradually and reduce to below the 2kPa, thereby make the not segregative pyridine of normal pressure separate;
The 3rd step was 160～190 ℃ conditions under to distil at pressure less than 2kPa and temperature with the above-mentioned product of removing behind the pyridine, and collects the white crystalline flores of overflowing simultaneously, till no flores effusion.
Wherein, pressure can be 1kPa, 0.5kPa, and 0.2kPa, temperature can be 165 ℃, 174 ℃, 182 ℃, 188 ℃,
The 4th step, the flores of above-mentioned effusion is ground, the chloroform that adds 4～6 times of weight of flores that are equivalent to overflow, and agitator treating, make remaining pyridine be dissolved in the chloroform, filter, and use chloroform drip washing, it is dry under 40～60 ℃ that the back is done in filter, to remove residual chloroform, obtains pyrogallol.
Wherein, chloroform weight can be 4.2 times of the flores that is equivalent to overflow, and 4.7,5.1,5.6,5.9 times, drying temperature is 45 ℃, 47 ℃, and 52 ℃, 56 ℃.
Embodiment 2:
Take by weighing the anhydrous gallic acid of 30g and place in the flask that has stirring and prolong, add the 5ml pyridine, under agitation be heated to 155 ℃ of back flow reaction.Material becomes molten mass, and a large amount of CO are arranged simultaneously
2Bubble is overflowed.Insulation reaction generates until no bubble.Earlier with normal pressure, then be decompressed to 2kPa, 155 ℃ steam pyridine.Continue to vacuumize below pressure 2kPa, and slowly be warming up to 175 ℃, product promptly begins distillation.Keep temperature and vacuum tightness constant, till no flores is overflowed.The taking-up product grinds, and drops into to add 70ml chloroform, fully agitator treating in the washing container.After the filtration, use minimum of chloroform drip washing.Filter do the back in vacuum drying oven 55 ℃ remove residual chloroform, product 18g.Yield is 81%, the ratio of pyrogallol product acquisition amount that the product pick-up rate is meant and Theoretical Calculation acquisition amount (weight and molecular formula according to raw material are calculated).
Embodiment 3:
Take by weighing the anhydrous gallic acid of 100g and place in the flask that has stirring and prolong, add the 10ml pyridine, under agitation be heated to 135 ℃ of back flow reaction.Material becomes molten mass, and a large amount of CO are arranged simultaneously
2Bubble is overflowed.Insulation reaction generates until no bubble.Earlier with normal pressure, then be decompressed to 2kPa, 150 ℃ steam pyridine.Continue to vacuumize below pressure 2kPa, and slowly be warming up to 160 ℃, product promptly begins distillation.Keep temperature and vacuum tightness constant, till no flores is overflowed.The taking-up product grinds, and drops into to add 180ml chloroform, fully agitator treating in the washing container.After the filtration, use minimum of chloroform drip washing.Filter do the back in vacuum drying oven 60 ℃ remove residual chloroform, product 59g.Yield is 81%.
Embodiment 4:
Take by weighing the anhydrous gallic acid of 200g and place in the flask that has stirring and prolong, add the 20ml pyridine, under agitation be heated to 140 ℃ of back flow reaction.Material becomes molten mass, and a large amount of CO are arranged simultaneously
2Bubble is overflowed.Insulation reaction generates until no bubble.Earlier with normal pressure, then be decompressed to 2kPa, 145 ℃ steam pyridine.Continue to vacuumize below pressure 2kPa, and slowly be warming up to 180 ℃, product promptly begins distillation.Keep temperature and vacuum tightness constant, till no flores is overflowed.The taking-up product grinds, and drops into to add 500ml chloroform, fully agitator treating in the washing container.After the filtration, use minimum of chloroform drip washing.Filter do the back in vacuum drying oven 50 ℃ remove residual chloroform, product 126g.Yield is 85%.
The product quality analysis data are as follows:
The mass analysis result of laboratory 100g magnitude test products is as follows:
Outward appearance: white crystalline powder
Qualitative test: by
Fusing point: 133-136 ℃
Molten shape: achromatism and clarity
Muriate :≤2ppm
Vitriol :≤5ppm
Weight loss on drying: 0.47%
Ignition residue: 0.0075%
Gallic acid: do not detect
Content (butt): 99.70%
Moisture: 0.44%
Sodium: 0.54ppm (AAS)
Iron: 0.37ppm (AAS)
Other element (ICP, μ g/g):
Al：0.59；Co：0.006；Cr：0.14；Mg：1.49；Mn：0.05；Zn：1.04；
Ba, Be, Ca, Cd, Cu, K, Li, Mo, P, Pb, Sr, Ti, V all do not detect.
Claims (1)
1. one kind prepares the method for pyrogallol with pyridine as gallate decarboxylation accelerant, it is characterized in that comprising following a few step:
The first step, be 1 with anhydrous gallic acid and pyridine with mol ratio: (0.1～0.4) mixes, and 130～160 ℃ of following back flow reaction, material becomes molten mass, and a large amount of CO are arranged simultaneously
2Bubble is overflowed, and insulation no bubble in reaction product is overflowed,
In second step, keeping the temperature of reaction product is 130～160 ℃, and the pressure of the residing atmosphere of above-mentioned reaction product is reduced to below the 2kPa gradually, thereby distills out the pyridine in the reaction product,
The 3rd step rose to 160～190 ℃ with above-mentioned temperature of removing the product behind the pyridine, and collects the flores of overflowing simultaneously, till no flores effusion,
The 4th step, the flores of above-mentioned effusion is ground, the chloroform that adds 4～6 times of weight of flores that are equivalent to overflow, and agitator treating, make remaining pyridine be dissolved in the chloroform, filter, and use chloroform drip washing, it is dry under 40～60 ℃ that the back is done in filter, to remove residual chloroform, obtains pyrogallol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510038249 CN1271026C (en) | 2005-01-26 | 2005-01-26 | Preparation of pyrogallic acid with pyridine as decarboxylation catalyst of 3,4,5-trihydroxybenzoic acid |
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|---|---|---|---|
| CN 200510038249 CN1271026C (en) | 2005-01-26 | 2005-01-26 | Preparation of pyrogallic acid with pyridine as decarboxylation catalyst of 3,4,5-trihydroxybenzoic acid |
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| CN1271026C CN1271026C (en) | 2006-08-23 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475450B (en) * | 2009-02-04 | 2011-07-27 | 南京林业大学 | Method for preparing pyrogallic acid with glyoxaline as gallic acid decarboxylation catalyst |
| CN106220476A (en) * | 2016-08-02 | 2016-12-14 | 遵义市倍缘化工有限责任公司 | A kind of low pressure catalytic prepares the method for pyrogallic acid |
| CN106242949A (en) * | 2016-07-30 | 2016-12-21 | 遵义市倍缘化工有限责任公司 | A kind of method that pyrogallic acid is prepared in high pressure aqueous phase decarboxylation |
| CN106349022A (en) * | 2016-08-02 | 2017-01-25 | 遵义市倍缘化工有限责任公司 | Method using biphasic catalysis to prepare pyrogallic acid under normal pressure |
| CN109534962A (en) * | 2018-12-18 | 2019-03-29 | 湘潭大学 | The method of pyrogallic acid is prepared using organic amine as gallate decarboxylation accelerant |
-
2005
- 2005-01-26 CN CN 200510038249 patent/CN1271026C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475450B (en) * | 2009-02-04 | 2011-07-27 | 南京林业大学 | Method for preparing pyrogallic acid with glyoxaline as gallic acid decarboxylation catalyst |
| CN106242949A (en) * | 2016-07-30 | 2016-12-21 | 遵义市倍缘化工有限责任公司 | A kind of method that pyrogallic acid is prepared in high pressure aqueous phase decarboxylation |
| CN106242949B (en) * | 2016-07-30 | 2019-01-22 | 遵义市倍缘化工有限责任公司 | A kind of method that the decarboxylation of high pressure water phase prepares pyrogallic acid |
| CN106220476A (en) * | 2016-08-02 | 2016-12-14 | 遵义市倍缘化工有限责任公司 | A kind of low pressure catalytic prepares the method for pyrogallic acid |
| CN106349022A (en) * | 2016-08-02 | 2017-01-25 | 遵义市倍缘化工有限责任公司 | Method using biphasic catalysis to prepare pyrogallic acid under normal pressure |
| CN106220476B (en) * | 2016-08-02 | 2018-12-18 | 遵义市倍缘化工有限责任公司 | A kind of method that low pressure catalytic prepares pyrogallic acid |
| CN106349022B (en) * | 2016-08-02 | 2019-03-05 | 遵义市倍缘化工有限责任公司 | A kind of method that normal pressure biphasic catalysis prepares pyrogallic acid |
| CN109534962A (en) * | 2018-12-18 | 2019-03-29 | 湘潭大学 | The method of pyrogallic acid is prepared using organic amine as gallate decarboxylation accelerant |
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