CN103508908A - Preparation method for 4-amino-3-methylphenol - Google Patents
Preparation method for 4-amino-3-methylphenol Download PDFInfo
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Abstract
The invention relates to a preparation method for 4-amino-3-methylphenol. M-cresol is used as a raw material and subjected to nitrosation reaction, hydrogenation reduction reaction and purification to prepare high-quality 4-amino-3-methylphenol. The preparation method is simple in process, simple and convenient in product after-treatment and low in environmental pollution, and can obtain 4-amino-3-methylphenol which is higher in product quality and better in stability than 4-amino-3-methylphenol prepared by other methods; the obtained product can be used for preparation of high-end resin, beside common purposes; the preparation method provided by the invention is an industrially practicable better preparation method.
Description
Technical field
The present invention relates to a kind of preparation method of chemical intermediate, especially relate to a kind of preparation method of high-quality 4-amino-3-methylphenol.
Technical background
4-amino-3-methylphenol is Material of Fluoran dyestuff, plant protection product and the synthetic necessary intermediate of medicine, is industrial important raw and processed materials; Now high-quality 4-amino-3-methylphenol is also for the preparation of the synthetic and carbon fiber of high-end resin.
Preparation method about 4-amino-3-methylphenol roughly can be summarized as three classes.The first kind is to be raw material with Ortho Nitro Toluene, by reducing and having reset reaction, has following the whole bag of tricks: (a) electrochemical method, and this method negative electrode adopts poisonous mercury salt, and productive rate is low; (b) aluminium-aqueous solutions of organic acids, this method products obtained therefrom purity is low, and cost is high; (c) in dilute sulphuric acid, with hydrogen, carry out the method for catalytic reduction, this method catalyzer adopts the precious metals such as platinum, rhodium, palladium; Long reaction time, productive rate is low.Equations of The Second Kind preparation method is azo-compound reduction method and 4-nitro-3-methylphenol reduction method, and the main drawback of this reduction method is that raw material is rare, and synthetic route is long.The 3rd class methods are to be dissolved in ammoniacal liquor with 4-nitroso-group-3-methylphenol, and reduce under hydrogen sulfide effect, and this preparation method is simple, and productive rate is high, but hydrogen sulfide is poisonous, and expensive safety prevention measure declines its economic worth.European patent EP 43520(1982) a kind of method that 4-nitroso-group-3-methylphenol reduces under iron effect in acetic aid medium is disclosed, this method reductive agent is cheap, and transformation efficiency is high, but the filtering formality of iron oxide residue trouble in preparation process, and ferric oxide cannot process, pollute environment.Chinese patent CN1031526 has reported the method that adopts SODIUM HYDROSULPHITE sodium reduction 4-nitroso-group-3-methylphenol.Adopt 4-amino-3-methylphenol that above method obtains all to have following problems: the reductive agent method 1, adopting exists the problems large, that the three wastes are many of polluting; 2, because the technique adopting or reductive agent inevitably can exist certain residually in product, thereby affected the interior quality of product, causing producing the 4-nitroso-group-3-methylphenol obtaining cannot be for high-end resin purposes.
In order to improve the inherent quality of 4-amino-3-methylphenol, the present invention is through repeatedly attempting providing a kind of method of preparing high-quality 4-amino-3-methylphenol.
Summary of the invention
The preparation method who the invention provides a kind of new high-quality 4-amino-3-methylphenol reduces environmental pollution in the quality of improving the quality of products, and makes that products production cleans, environmental protection, makes product production in enormous quantities preferably.
A preparation method for 4-amino-3-methylphenol, comprises the steps:
(1) nitrosation reaction: the m-cresol of take prepares 4-nitroso-group-3-methylphenol through nitrosification as raw material;
(2) reduction reaction: 4-nitroso-group-3-methylphenol, in alcoholic solvent, obtains 4-amino-3-methylphenol crude product by hydrogenating reduction under catalyzer and promotor effect;
(3) purifying: 4-amino-3-methylphenol crude product carries out purification process through alcoholic solvent and obtains 4-amino-3-methylphenol highly finished product.
Synthetic route of the present invention is as follows:
Preferably, in step (1), take aqueous sodium hydroxide solution as solvent, Sodium Nitrite and hydrochloric acid are nitrosification agent, and nitrosation reaction temperature is controlled at-5～15 ℃; The weight ratio of described m-methyl phenol, sodium hydroxide, Sodium Nitrite is 1:0.35～0.45:0.6～0.8, and the concentration of described hydrochloric acid is 15～36%, and hydrochloric acid folding hundred weight ratio rear and m-methyl phenol is 0.8～1.2:1.
Step (1) be take m-cresol and through nitrosification, is prepared 4-nitroso-group-3-methylphenol as raw material: m-methyl phenol and Sodium Nitrite are dissolved in and in certain density alkaline aqueous solution, obtain reaction solution a, reaction solution a obtains reaction solution b in 0～15 ℃ is added drop-wise to the certain density hydrochloric acid preparing in advance, be added dropwise to complete reaction solution b continuation reaction certain hour to stock yard methylphenol and reacted, reaction generates 4-nitroso-group-3-methylphenol.After having reacted, through suction filtration, washing obtains damp product 4-nitroso-group-3-methylphenol, can be directly used in next step reaction.
Preferably, in step (2), reduction reaction temperature is controlled at 20～40 ℃, reaction times 2～8h, and described alcoholic solvent is a kind of in methyl alcohol, ethanol, Virahol, the weight ratio of itself and 4-nitroso-group-3-methylphenol is 2～10:1; Described catalyzer is a kind of in palladium carbon, palladium aluminium, Raney's nickel, and it is 0.005～0.05:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol; Described promotor is ammonia or organic amine, and it is 0.01～0.1:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol.
In step (2), 4-nitroso-group-3-methylphenol obtains 4-amino-3-methylphenol by hydrogenating reduction, in autoclave, drop into a certain amount of 4-nitroso-group-3-methylphenol and alcohol, then add a certain amount of catalyzer and promotor to obtain reaction solution a1, then be warming up to 20～40 ℃, pass into hydrogen reaction 2～8h and no longer inhale hydrogen to reacting, stopped reaction, reaction solution is removed, remove by filter catalyzer, the alcoholic solvent in reaction solution a1 is removed in decompression, obtains crude product 4-amino-3-methylphenol of solid.
Preferably, described organic amine is a kind of in Monomethylamine, dimethylamine, Trimethylamine 99.
Preferably, in step (3), through alcoholic solvent dissolving, crystallization, filtration, dry 4-amino-3-methylphenol that to obtain; Solvent temperature is 40～70 ℃, and described alcoholic solvent is low-boiling point alcohol or alcohol solution, and the weight ratio of alcoholic solvent and 4-amino-3-methylphenol is 1～4:1; In alcohol solution, the ratio of water and 4-amino-3-methylphenol is 0.5～1.5:1; Drying temperature is 30～60 ℃.
Preferably, described low-boiling point alcohol is methyl alcohol or ethanol, and described alcohol solution is methanol aqueous solution or aqueous ethanolic solution; The weight ratio of low-boiling point alcohol and 4-amino-3-methylphenol is 2～4:1, and the weight ratio of alcohol solution and 4-amino-3-methylphenol is 1～4:1.
Step (3) is put in a certain amount of alcoholic solvent for 4-amino-3-methylphenol that step (2) is obtained, and is warming up to backflow, and then cooling down crystallization, filtration, vacuum drying obtain high-quality 4-amino-3-methylphenol; The mixture that the alcohol that described method is used is the more lower boiling organic solvents such as methyl alcohol, ethanol or these alcohol and water, when using single alcohol, the weight ratio of its consumption and 4-amino-3-methylphenol is 2～4:1; If what use is alcohol-water mixture, the ratio of alcohol water is 1～4:1.
Preferably, the preparation method of 4-amino-3-methylphenol, comprises the steps:
(1) nitrosation reaction: take m-cresol as raw material, take aqueous sodium hydroxide solution as solvent, Sodium Nitrite and hydrochloric acid are nitrosification agent, prepares 4-nitroso-group-3-methylphenol through nitrosation reaction; Nitrosation reaction temperature is controlled at 3～10 ℃; The weight ratio of described m-methyl phenol, sodium hydroxide, Sodium Nitrite is 1:0.39:0.68, and the concentration of described hydrochloric acid is 36%, and hydrochloric acid folding hundred weight ratio rear and m-methyl phenol is 1.03:1;
(2) reduction reaction: 4-nitroso-group-3-methylphenol, in methyl alcohol, obtains 4-amino-3-methylphenol crude product by hydrogenating reduction under palladium carbon and ammonia effect; Reduction reaction temperature is controlled at 20～25 ℃, reaction times 2～8h, and the weight ratio of methyl alcohol and 4-nitroso-group-3-methylphenol is 7.5:1; Palladium carbon is 0.03:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol; Described ammonia is 0.1:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol;
(3) purifying: 4-amino-3-methylphenol crude product adds and is warming up to backflow in methyl alcohol, then through crystallisation by cooling, filtration, dry 4-amino-3-methylphenol highly finished product that to obtain; The weight ratio of methyl alcohol and 4-amino-3-methylphenol is 2:1; Drying temperature is 40 ℃.
Technique of the present invention is simple, and product aftertreatment is easy, and environmental pollution is little, 4-amino-3-methylphenol quality product the quality preparing is high, good stability, and the product making is except can be for general applications, can also, for the preparation of high-end resin, be a kind of method of applicable preparation of industrialization.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
Get 11.2g sodium hydrate solid, 120ml water and 28.5g m-cresol and stir at 10 ℃ of temperature, be cooled to 3～10 ℃ after adding 19.4g Sodium Nitrite to dissolve completely, standby.Get 81.4g 36% HCl (AR) and 58.1g water in four-hole bottle, slowly drip above-mentioned mixing solutions, controlling temperature is 3～10 ℃, finish and be incubated half an hour, reacting liquid filtering obtains sorrel solid, obtains 33.6g 4-nitroso-group-3-methylphenol after oven dry, and productive rate is 93.0%.
In 500ml stainless steel cauldron, add successively 75g methyl alcohol, 4g 25% ammoniacal liquor, 4-nitroso-group-3-methylphenol 10g and 5% palladium carbon 0.3g, envelope still, nitrogen replacement 3 times, after hydrogen exchange 3 times, be filled with hydrogen to 0.5Mpa, control 20～25 ℃ of stirring reactions of temperature of reaction kettle, reaction 2h, question response liquid is no longer eaten stopped reaction after hydrogen, drive still, reaction solution suction filtration is reclaimed to catalyzer, filtrate normal pressure reclaims methyl alcohol to there being a large amount of solids to separate out, stop steaming, be cooled to 10～15 ℃, suction filtration product with water rinse then vacuum drying obtain 4-amino-3-methylphenol crude product 9g, crude product adds in 20g methyl alcohol and is warming up to backflow, then be cooled to 10 ℃ of suction filtrations, 40 ℃ of vacuum-dryings of methanol wash obtain 4-amino-3-methylphenol highly finished product 7.65g, yield is 85%, product HPLC >=99.5%.
Embodiment 2
In 2000L stainless steel cauldron R1, suck water 900kg, drop into 96% sodium hydroxide 90kg, exothermic heat of reaction while dropping into sodium hydroxide, the logical icy salt solution of R1 chuck is cooled to 20～25 ℃, then drop into 214kg m-cresol at 10 ℃ of temperature stirring reaction 30min to the abundant salify of m-cresol, then after adding 146kg Sodium Nitrite to dissolve completely, be cooled to 3～10 ℃, standby.In 3000L glassed steel reaction vessels R2, suck 735kg 30% HCl and 440kg water and be uniformly mixed, the logical icy salt solution of chuck is cooled to 3～10 ℃ simultaneously; Ready, the alkali lye that contains Sodium Nitrite preparing in R1 is added drop-wise in the hydrochloric acid preparing in R2, the about 4h of time for adding adds, finish and be incubated half an hour, sampling HPLC detects to stock yard cresylol and reacts completely, and blowing, filters and obtains sorrel solid, with water rinse 2 times, remove the salt in product, obtain 4-nitroso-group-3-methylphenol.Product is not dried and is directly used in next step hydrogenating reduction.
In 2000L stainless steel autoclave, suck methyl alcohol 1000kg, pass into liquefied ammonia 5kg, 4-nitroso-group-3-methylphenol 240kg, drop into 5% palladium carbon 2kg, envelope still, nitrogen replacement 3 times, hydrogen exchange 3 times, reactor hydrogen pressure keeps 0.1～0.2Mpa, then be warming up to 20～25 ℃, start reaction, no longer change to hydrogen pressure, reaction 8h, sampling detects to 4-nitroso-group-3-monomethylaniline and reacts completely.Pressure release, reaction solution is removed to catalyzer by strainer, decompression steams methyl alcohol, steam about 600kg to methyl alcohol, be cooled to 10 ℃, be discharged in filtering jar, then centrifugal 4-amino-3-methylphenol crude product that obtains, 4-amino-3-methylphenol the crude product obtaining is put in the methanol aqueous solution 600kg of 50% concentration again, be warming up to 45 ℃, insulated and stirred 20min, then be cooled to 5～10 ℃, centrifugal, 45 ℃ of fast boilings are dried and obtain 4-amino-3-methylphenol highly finished product 99.4kg, and yield is 80.5%, product HPLC >=99.7%.
Embodiment 3
Get 13.5g sodium hydrate solid, 120ml water and 30g m-cresol and stir at 10 ℃ of temperature, be cooled to 5 ℃ after adding 24g Sodium Nitrite to dissolve completely, standby.Get 96g 25% HCl (AR) and 60g water in four-hole bottle, slowly drip above-mentioned mixing solutions, controlling temperature is 5 ℃, finish and be incubated half an hour, reacting liquid filtering obtains sorrel solid, obtains 36.6g 4-nitroso-group-3-methylphenol after oven dry, and productive rate is 96.2%.
In 500ml stainless steel cauldron, add successively 90g ethanol, 0.5g Trimethylamine 99, 4-nitroso-group-3-methylphenol 10g and Raney's nickel 0.1g, envelope still, nitrogen replacement 3 times, after hydrogen exchange 3 times, be filled with hydrogen to 0.5Mpa, control 30～35 ℃ of stirring reactions of temperature of reaction kettle, question response liquid is no longer eaten stopped reaction after hydrogen, drive still, reaction solution suction filtration is reclaimed to catalyzer, filtrate normal pressure reclaims ethanol to there being a large amount of solids to separate out, stop steaming, be cooled to 10～15 ℃, suction filtration product with water rinse then vacuum drying obtain 4-amino-3-methylphenol crude product 9.5g, crude product adds in 50g ethanol and is warming up to backflow, then be cooled to 10 ℃ of crystallizations, suction filtration, washing with alcohol, 50 ℃ of vacuum-dryings obtain 4-amino-3-methylphenol highly finished product 7.91g, yield is 88.1%, product HPLC >=99.3%.
Embodiment 4
Get 7.2g sodium hydrate solid, 100ml water and 20g m-cresol and stir at 10 ℃ of temperature, be cooled to 8 ℃ after adding 12g Sodium Nitrite to dissolve completely, standby.Get in the four-hole bottle of 150g 15% HCl (AR), slowly drip above-mentioned mixing solutions, controlling temperature is 8 ℃, finishes and is incubated half an hour, and reacting liquid filtering obtains sorrel solid, obtains 23.2g 4-nitroso-group-3-methylphenol after oven dry, and productive rate is 91.3%.
In 500ml stainless steel cauldron, add successively 45g Virahol, 0.2g Monomethylamine, 4-nitroso-group-3-methylphenol 10g and palladium aluminium 0.1g, envelope still, nitrogen replacement 3 times, after hydrogen exchange 3 times, be filled with hydrogen to 0.5Mpa, control 20～25 ℃ of stirring reactions of temperature of reaction kettle, question response liquid is no longer eaten stopped reaction after hydrogen, drive still, reaction solution suction filtration is reclaimed to catalyzer, filtrate normal pressure reclaims Virahol to there being a large amount of solids to separate out, stop steaming, be cooled to 10～15 ℃, suction filtration product with water rinse then vacuum drying obtain 4-amino-3-methylphenol crude product 8.7g, crude product adds in 30g methyl alcohol and is warming up to backflow, then be cooled to 10 ℃ of crystallisation by cooling, suction filtration, methanol wash, 60 ℃ of vacuum-dryings obtain 4-amino-3-methylphenol highly finished product 7.65g, yield is 82%, product HPLC >=99.7%.
Claims (7)
1. a preparation method for 4-amino-3-methylphenol, is characterized in that comprising the steps:
(1) nitrosation reaction: the m-cresol of take prepares 4-nitroso-group-3-methylphenol through nitrosification as raw material;
(2) reduction reaction: 4-nitroso-group-3-methylphenol, in alcoholic solvent, obtains 4-amino-3-methylphenol crude product by hydrogenating reduction under catalyzer and promotor effect;
(3) purifying: 4-amino-3-methylphenol crude product carries out purification process through alcoholic solvent and obtains 4-amino-3-methylphenol highly finished product.
2. the preparation method of 4-amino-3-methylphenol according to claim 1, is characterized in that: in step (1), take aqueous sodium hydroxide solution as solvent, Sodium Nitrite and hydrochloric acid are nitrosification agent, and nitrosation reaction temperature is controlled at-5～15 ℃; The weight ratio of described m-methyl phenol, sodium hydroxide, Sodium Nitrite is 1:0.35～0.45:0.6～0.8, and the concentration of described hydrochloric acid is 15～36%, and hydrochloric acid folding hundred weight ratio rear and m-methyl phenol is 0.8～1.2:1.
3. the preparation method of 4-amino-3-methylphenol according to claim 1, it is characterized in that: in step (2), reduction reaction temperature is controlled at 20～40 ℃, reaction times 2～8h, described alcoholic solvent is a kind of in methyl alcohol, ethanol, Virahol, and the weight ratio of itself and 4-nitroso-group-3-methylphenol is 2～10:1; Described catalyzer is a kind of in palladium carbon, palladium aluminium, Raney's nickel, and it is 0.005～0.05:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol; Described promotor is ammonia or organic amine, and it is 0.01～0.1:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol.
4. the preparation method of 4-amino-3-methylphenol according to claim 3, is characterized in that: described organic amine is a kind of in Monomethylamine, dimethylamine, Trimethylamine 99.
5. the preparation method of 4-amino-3-methylphenol according to claim 1, is characterized in that: in step (3), through alcoholic solvent dissolving, crystallization, filtration, dry 4-amino-3-methylphenol that to obtain; Solvent temperature is 40～70 ℃, and described alcoholic solvent is low-boiling point alcohol or alcohol solution, and the weight ratio of itself and 4-amino-3-methylphenol is 1～4:1; In alcohol solution, the weight ratio of water and 4-amino-3-methylphenol is 0.5～1.5:1; Drying temperature is 30～60 ℃.
6. the preparation method of 4-amino-3-methylphenol according to claim 5, is characterized in that: described low-boiling point alcohol is methyl alcohol or ethanol, and described alcohol solution is methanol aqueous solution or aqueous ethanolic solution; The weight ratio of low-boiling point alcohol and 4-amino-3-methylphenol is 2～4:1, and the weight ratio of alcohol solution and 4-amino-3-methylphenol is 1～4:1.
7. the preparation method of 4-amino-3-methylphenol according to claim 1, is characterized in that comprising the steps:
(1) nitrosation reaction: take m-cresol as raw material, take aqueous sodium hydroxide solution as solvent, Sodium Nitrite and hydrochloric acid are nitrosification agent, prepares 4-nitroso-group-3-methylphenol through nitrosation reaction; Nitrosation reaction temperature is controlled at 3～10 ℃; The weight ratio of described m-methyl phenol, sodium hydroxide, Sodium Nitrite is 1:0.39:0.68, and the concentration of described hydrochloric acid is 36%, and hydrochloric acid folding hundred weight ratio rear and m-methyl phenol is 1.03:1;
(2) reduction reaction: 4-nitroso-group-3-methylphenol, in methyl alcohol, obtains 4-amino-3-methylphenol crude product by hydrogenating reduction under palladium carbon and ammonia effect; Reduction reaction temperature is controlled at 20～25 ℃, reaction times 2～8h, and the weight ratio of methyl alcohol and 4-nitroso-group-3-methylphenol is 7.5:1; Palladium carbon is 0.03:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol; Described ammonia is 0.1:1 with the ratio of the weight of 4-nitroso-group-3-methylphenol;
(3) purifying: 4-amino-3-methylphenol crude product adds and is warming up to backflow in methyl alcohol, then through crystallisation by cooling, filtration, dry 4-amino-3-methylphenol highly finished product that to obtain; The weight ratio of methyl alcohol and 4-amino-3-methylphenol is 2:1; Drying temperature is 40 ℃.
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| CN108863818A (en) * | 2018-06-28 | 2018-11-23 | 江苏新瑞药业有限公司 | A kind of synthetic method of pair of amino metacresol |
| CN109180501A (en) * | 2018-08-01 | 2019-01-11 | 青岛泰玛新材料科技有限公司 | A kind of synthetic method of 4,4 '-diaminodiphenyl ethers |
| CN109516924A (en) * | 2018-11-14 | 2019-03-26 | 南京工业大学 | Method for preparing m-aminophenol by catalyzing resorcinol |
| CN111072501A (en) * | 2019-12-16 | 2020-04-28 | 岳阳中展科技有限公司 | Production method of 2,4, 6-tri (dimethylamine methyl) phenol |
| CN113735721A (en) * | 2021-10-09 | 2021-12-03 | 上海昕凯医药科技有限公司 | Method for synthesizing 3-ethylamino-4-methylphenol |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108863818A (en) * | 2018-06-28 | 2018-11-23 | 江苏新瑞药业有限公司 | A kind of synthetic method of pair of amino metacresol |
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| CN109180501B (en) * | 2018-08-01 | 2021-03-16 | 青岛泰玛新材料科技有限公司 | Synthetic method of 4, 4' -diaminodiphenyl ether |
| CN109516924A (en) * | 2018-11-14 | 2019-03-26 | 南京工业大学 | Method for preparing m-aminophenol by catalyzing resorcinol |
| CN109516924B (en) * | 2018-11-14 | 2021-10-29 | 南京工业大学 | Method for preparing m-aminophenol by catalyzing resorcinol |
| CN111072501A (en) * | 2019-12-16 | 2020-04-28 | 岳阳中展科技有限公司 | Production method of 2,4, 6-tri (dimethylamine methyl) phenol |
| CN113735721A (en) * | 2021-10-09 | 2021-12-03 | 上海昕凯医药科技有限公司 | Method for synthesizing 3-ethylamino-4-methylphenol |
| CN113735721B (en) * | 2021-10-09 | 2023-09-29 | 上海昕凯医药科技有限公司 | Method for synthesizing 3-ethylamino-4-methylphenol |
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