CN101381323B - Method for preparing p-aminobenzoic acid from p-nitrobenzoic acid - Google Patents
Method for preparing p-aminobenzoic acid from p-nitrobenzoic acid Download PDFInfo
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- CN101381323B CN101381323B CN2008101558289A CN200810155828A CN101381323B CN 101381323 B CN101381323 B CN 101381323B CN 2008101558289 A CN2008101558289 A CN 2008101558289A CN 200810155828 A CN200810155828 A CN 200810155828A CN 101381323 B CN101381323 B CN 101381323B
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Abstract
The invention provides a method for preparing para aminobenzoic acid from paranitrobenzoic acid. The paranitrobenzoic acid is directly placed into a microwave reactor, a catalyst is added into the reactor, and hydrogen is introduced; after the microwave reaction, the mixture is subjected to washing, crystallization and drying to obtain the para aminobenzoic acid. The method utilizes the paranitrobenzoic acid as a raw material; compared with the prior method, the purity and yield of the para aminobenzoic acid prepared by a microwave method are apparently improved; and the method has high production efficiency, avoids the disadvantages of multi-step operation, low yield and low purity of the prior method, and has good application prospect in the industry.
Description
Technical field
The present invention relates to a kind of organic acid preparation method, specifically, relate to a kind of preparation method of para-amino benzoic acid.
Background technology
Para-amino benzoic acid (PABA) is a kind of yellow crystal compound, in its water soluble, ethanol and the ether.PABA is a kind of important organic synthesis raw material, and is especially even more important as the effect of medicine intermediate.It is the important intermediate of synthetic non-steroid anti-inflammatory agent felbinac.LY-61017 has strong anti-inflammatory analgesic action and good transdermal performance, and treatment joint disease and myalgia are had characteristics such as quick-acting, efficient and security.In addition; Like synthetic hematinic folic acid (Folie Acid), coagulant-para-amino-methyl-benzoic acid; The narcotic that the various esters of para-amino benzoic acid and verivate thereof are widespread use, it can alleviate several kinds because of red blood corpuscle lack the anaemia cause, viral anaemia, sprue and period of pregnancy illness such as anaemia.In addition, also be used for synthetic treatment rickets, rheumatosis, sacroiliitis, tuberculosis.Be used with penicillium mould or Streptomycin sulphate and can improve bacteriostatic action.Can also be used as sun-screening agent, hair growth agent and modifier.But because this compound industry " three wastes " in producing can't handle, or reason such as equipment corrosion is serious, and influenced output.
For the raw material production para-amino benzoic acid has the high economic added value, is the better approach that p-Nitrobenzenecarboxylic acid carries out deep processing with the p-Nitrobenzenecarboxylic acid.At present mainly by two kinds of working methods, i.e. iron powder reducing method and shortening method.Iron powder reducing method technical maturity, but serious pollution and the equipment corrosion fatal shortcoming that is it.The catalytic hydrogenating reduction method is light to equipment corrosion, and is low in the pollution of the environment, and its yield is also higher.Domestic present industrial process mainly is that iron powder changes reduction method, and the suitability for industrialized production of catalytic hydrogenating reduction method report is less.
Summary of the invention
Technical problem to be solved by this invention provides simple, the free of contamination method that is prepared para-amino benzoic acid by p-Nitrobenzenecarboxylic acid of a kind of technology.
The present invention is based upon on the thought of the synthetic preparation of microwave; Raw material after its characteristics are to utilize microwave method to simple process reacts; Directly prepare p-Nitrobenzenecarboxylic acid after adding nitration oxidation agent and catalyzer, and after the p-Nitrobenzenecarboxylic acid for preparing simply washed s.t., add in the microwave reactor again after the drying; Add oxygenant and catalyzer again, the technical parameter of setting microwave reactor carries out the synthetic para-amino benzoic acid product that obtains of microwave.
Advantages such as it is fast with speed of response for microwave irradiation, side reaction is few, productive rate is high, aftertreatment is simple have obtained using widely in organic synthesis.For the action principle of microwave, two kinds of viewpoint different are arranged: the pyrogenic action that a kind of raising of thinking microwave induced organic synthesis speed or productive rate is microwave with cross heat effect; Another kind of viewpoint is then thought and under microwave action, is existed its unique non-thermal effect.The former thinks that microwave heating is essentially different with traditional heating: the essence of microwave heating is that the dielectric displacement of material or the polarization and this polarization of the different electric charges of material internal do not possess the ability of catching up with alternating electric field rapidly.EM field in the microwave is with several hundred million times of per second even billions of inferior frequency inverted direction; The divertical motion of the moment of dipole in the polarity dielectric medium molecule has little time to catch up with alternating electric field so fast; Cause polarisation hysteresis in electric field, and the electric current that produces of polarization has and differ from the identical phase component of electric field, cause the material internal friction and generate heat; Promptly so-called " internal heating " [chapter is thought rule; Xin Zhong, Huang Deyin. meticulous organic chemical industry prepare handbook (on) II version [M]. Beijing: scientific and technical literature press, 1996:263.].
Use the main advantage of microwave reactor to have in the organic synthesis: (1) speeds up: owing to used higher temperature of reaction, the reaction times sharply shortened to several minutes from several hours, even the several seconds; (2) productive rate improves: under many situations, the reaction times shortens, and has reduced undesired side reaction to greatest extent; (3) purity is improved: because by product reduces, react cleaner, purification step is simpler; (4) circulation ratio is better: the even microwave field that in the single mold microwave reactor drum of special use, occurs has guaranteed the similar of each experiment operation result; (5) reaction conditions obtains expanding: can realize and reach the conversion or the not readily accessible reaction conditions that under conventional conditions, are difficult for realization.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is following:
A kind ofly prepare the method for para-amino benzoic acid by p-Nitrobenzenecarboxylic acid, this method comprises the steps:
(1) dissolve p-Nitrobenzenecarboxylic acid with alkali lye, preparation quality percentage composition is 5～30% p-Nitrobenzenecarboxylic acid solution;
(2) p-Nitrobenzenecarboxylic acid solution is put into the reaction flask of microwave reactor, adding quality be the catalyzer to nitre phenylformic acid 0.1～5%, feeding hydrogen; Set 150～350 ℃ of temperature of reaction; Reaction pressure 1～5MPa, microwave power are 500～5000W, magnetic agitation reaction 30min～4h;
(2) reaction finishes to obtain para-amino benzoic acid behind back cleaning, the crystallizing and drying.
In the step (1), described alkali lye is sodium hydroxide solution or potassium hydroxide solution.
In the step (1), the quality percentage composition of alkali is 1～20% in the described alkali lye.
In the step (2), described catalyzer is nickel-alumina catalyst or sepiolite nickel-alumina catalyst.
The adding of above-mentioned catalyzer can be quickened the carrying out of building-up reactions, reduces the difficulty of building-up reactions.
Microwave reactor among the present invention is commercially available prod or self design equipment, requires may command microwave power, reaction times, temperature of reaction and pressure.
The present invention is following by the reaction equation that p-Nitrobenzenecarboxylic acid prepares para-amino benzoic acid:
Beneficial effect: it is raw material with the p-Nitrobenzenecarboxylic acid that the present invention proposes a kind of, utilizes microwave method, prepares the method for para-amino benzoic acid through catalyst.The inventive method has been avoided the multistep operation of usual way, the shortcoming that yield is low, purity is not high.The para-amino benzoic acid purity that the present invention makes through microwave method is compared all with traditional method with yield and is significantly improved, and production efficiency is high, and good application prospects is arranged in industry.
Embodiment
Further define the present invention through following embodiment, embodiment is to be the unrestricted the present invention of explanation.Any those of ordinary skill can be understood these embodiments and not limit the present invention in any way in this area, can make suitable modification and without prejudice to essence of the present invention with depart from scope of the present invention.
Employed microwave reactor MARS5 is available from U.S. CME company in following examples.
Embodiment 1:
Get the 1g p-Nitrobenzenecarboxylic acid and be dissolved in (the quality percentage composition of sodium hydroxide is 10%) in the sodium hydroxide solution, be mixed with the quality percentage composition and be 20% p-Nitrobenzenecarboxylic acid solution, put into microwave reactor; Feed hydrogen, and by 2% adding nickel-alumina catalyst to nitre phenylformic acid quality, and put into the magnetic force rotor; 250 ℃ of the temperature of reaction of setting microwave reactor; Reaction pressure 2MPa, microwave power are 1000W, reaction times 1h.Reaction finishes to obtain 0.726g para-amino benzoic acid product behind back cleaning, the crystallizing and drying, and para-amino benzoic acid purity is 94.80%.
Embodiment 2:
Get the 3g p-Nitrobenzenecarboxylic acid and be dissolved in (the quality percentage composition of Pottasium Hydroxide is 1%) in the potassium hydroxide solution, be mixed with the quality percentage composition and be 5% p-Nitrobenzenecarboxylic acid solution, put into microwave reactor; Feed hydrogen, and by 0.1% adding sepiolite nickel-alumina catalyst to nitre phenylformic acid quality, and put into the magnetic force rotor; 150 ℃ of the temperature of reaction of setting microwave reactor; Reaction pressure 1MPa, microwave power are 500W, reaction times 4h.Reaction finishes to obtain 2.216g para-amino benzoic acid product behind back cleaning, the crystallizing and drying, and the purity of para-amino benzoic acid is 94.3%.
Embodiment 3:
Get the 10g p-Nitrobenzenecarboxylic acid and be dissolved in (the quality percentage composition of Pottasium Hydroxide is 20%) in the potassium hydroxide solution, be mixed with the quality percentage composition and be 20% p-Nitrobenzenecarboxylic acid solution, put into microwave reactor; Feed hydrogen; And by 5% of nitre phenylformic acid quality being added nickel-alumina catalyst and adds the magnetic force rotor, 350 ℃ of the temperature of reaction of setting microwave reactor, reaction pressure 5MPa; Microwave power is 5000W, reaction times 30min.Reaction finishes to obtain 7.345g para-amino benzoic acid product behind back cleaning, the crystallizing and drying, and the purity of para-amino benzoic acid is 94.7%.
Embodiment 4:
Get the 1g p-Nitrobenzenecarboxylic acid and be dissolved in (the quality percentage composition of sodium hydroxide is 10%) in the sodium hydroxide solution, be mixed with the quality percentage composition and be 30% p-Nitrobenzenecarboxylic acid solution, put into microwave reactor; Feed hydrogen, and by 2% adding sepiolite nickel-alumina catalyst to nitre phenylformic acid quality, and put into the magnetic force rotor; 300 ℃ of the temperature of reaction of setting microwave reactor; Reaction pressure 3MPa, microwave power are 1500W, reaction times 80min.Reaction finishes to obtain 0.743g para-amino benzoic acid product behind back cleaning, the crystallizing and drying, and the purity of para-amino benzoic acid is 95.1%.
Embodiment 5:
Get the 5g p-Nitrobenzenecarboxylic acid and be dissolved in (the quality percentage composition of Pottasium Hydroxide is 10%) in the potassium hydroxide solution, be mixed with the quality percentage composition and be 15% p-Nitrobenzenecarboxylic acid solution, put into microwave reactor; Feed hydrogen, and by 4% adding nickel-alumina catalyst to nitre phenylformic acid quality, and put into the magnetic force rotor; 200 ℃ of the temperature of reaction of setting microwave reactor; Reaction pressure 2.5MPa, microwave power are 2500W, reaction times 2h.Reaction finishes to obtain 3.652g para-amino benzoic acid product behind back cleaning, the crystallizing and drying, and the purity of para-amino benzoic acid is 95.75%.
Claims (3)
1. one kind prepares the method for para-amino benzoic acid by p-Nitrobenzenecarboxylic acid, it is characterized in that this method comprises the steps:
(1) dissolve p-Nitrobenzenecarboxylic acid with alkali lye, preparation quality percentage composition is 5～30% p-Nitrobenzenecarboxylic acid solution;
(2) p-Nitrobenzenecarboxylic acid solution is put into the reaction flask of microwave reactor, adding quality be the catalyzer to nitre phenylformic acid 0.1～5%, feeding hydrogen; Set 150～350 ℃ of temperature of reaction; Reaction pressure 1～5MPa, microwave power are 500～5000W, magnetic agitation reaction 30min～4h;
(2) reaction finishes to obtain para-amino benzoic acid behind back cleaning, the crystallizing and drying;
Catalyzer described in the step (2) is a nickel-alumina catalyst.
2. according to claim 1ly prepare the method for para-amino benzoic acid, it is characterized in that the alkali lye described in the step (1) is sodium hydroxide solution or potassium hydroxide solution by p-Nitrobenzenecarboxylic acid.
3. according to claim 1 and 2ly prepare the method for para-amino benzoic acid by p-Nitrobenzenecarboxylic acid, the quality percentage composition that it is characterized in that alkali in the alkali lye described in the step (1) is 1～20%.
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| CN2008101558289A CN101381323B (en) | 2008-10-16 | 2008-10-16 | Method for preparing p-aminobenzoic acid from p-nitrobenzoic acid |
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| CN2008101558289A CN101381323B (en) | 2008-10-16 | 2008-10-16 | Method for preparing p-aminobenzoic acid from p-nitrobenzoic acid |
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| CN101381323B true CN101381323B (en) | 2012-02-01 |
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| CN104045574A (en) * | 2014-06-13 | 2014-09-17 | 江苏康恒化工有限公司 | Method for preparing 4-aminobenzoic acid from 4-nitrobenzoic acid by catalytic hydrogenation |
| CN114394909B (en) * | 2021-12-31 | 2024-06-07 | 大连新阳光材料科技有限公司 | Preparation method of p-aminobenzoic acid micropowder |
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Non-Patent Citations (1)
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| 黄文焕等.对氨基苯甲酸合成新工艺的研究.《吉林化工学院学报》.2001,第18卷(第2期), * |
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