CN103508908B - Preparation method for 4-amino-3-methylphenol - Google Patents
Preparation method for 4-amino-3-methylphenol Download PDFInfo
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- QGNGOGOOPUYKMC-UHFFFAOYSA-N Cc1cc(O)ccc1N Chemical compound Cc1cc(O)ccc1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- XGCZABZDVJOWTL-UHFFFAOYSA-N Cc1cc(O)ccc1N=O Chemical compound Cc1cc(O)ccc1N=O XGCZABZDVJOWTL-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N Cc1cccc(O)c1 Chemical compound Cc1cccc(O)c1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
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 4-amino-3-methylphenol of high-quality.
Technical background
4-amino-3-methylphenol is fluoran based dyes, plant protection product and the medical necessary intermediate synthesized, and is industrial important raw and processed materials; 4-amino-3-the methylphenol of present high-quality is also for the synthesis of high-end resin and the preparation of carbon fiber.
Preparation method about 4-amino-3-methylphenol roughly can be summarized as three classes.The first kind is raw material with Ortho Nitro Toluene, and completing reaction by reducing and reset, having following various method: (a) electrochemical method, 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 () carries out the method for catalytic reduction in dilute sulphuric acid with hydrogen, 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.3rd class methods are 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 makes its economic worth decline.European patent EP 43520(1982) disclose a kind of method that 4-nitroso-group-3-methylphenol reduces under iron effect in acetic aid medium, this method reductive agent is cheap, and transformation efficiency is high, but in preparation process, the filtering formality of iron oxide residue bothers, and ferric oxide cannot process, and pollutes environment.Chinese patent CN1031526 reports the method adopting SODIUM HYDROSULPHITE sodium reduction 4-nitroso-group-3-methylphenol.All there is following problems in the 4-amino-3-methylphenol adopting above method to obtain: the reductive agent method 1, adopted exists pollutes the problem large, the three wastes are many; 2, because the technique that adopts or reductive agent inevitably exist certain residual in the product, thus have impact on the interior quality of product, cause producing the 4-nitroso-group-3-methylphenol obtained and cannot be used for high-end resin applications.
In order to improve the quality of the inherence of 4-amino-3-methylphenol, the present invention is through repeatedly attempting providing a kind of method preparing high-quality 4-amino-3-methylphenol.
Summary of the invention
The invention provides a kind of preparation method of new high-quality 4-amino-3-methylphenol, while quality of improving the quality of products, reduce environmental pollution, products production is cleaned, environmental protection, make product production in enormous quantities preferably.
A preparation method for 4-amino-3-methylphenol, comprises the steps:
(1) nitrosation reaction: be that raw material prepares 4-nitroso-group-3-methylphenol through nitrosification with m-cresol;
(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 controls at-5 ~ 15 DEG C; 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 that is rear and m-methyl phenol is 0.8 ~ 1.2:1.
Step (1) is that raw material prepares 4-nitroso-group-3-methylphenol through nitrosification with m-cresol: m-methyl phenol and Sodium Nitrite are dissolved in certain density alkaline aqueous solution and obtain reaction solution a, reaction solution a is added drop-wise in the certain density hydrochloric acid prepared in advance at 0 ~ 15 DEG C and obtains reaction solution b, be added dropwise to complete reaction solution b continuation reaction certain hour to have reacted to raw material m-methyl phenol, reaction generates 4-nitroso-group-3-methylphenol.Obtain damp product 4-nitroso-group-3-methylphenol through suction filtration washing after having reacted, next step reaction can be directly used in.
Preferably, in step (2), reduction reaction temperature controls at 20 ~ 40 DEG C, reaction times 2 ~ 8h, and described alcoholic solvent is the one in methyl alcohol, ethanol, Virahol, and the weight ratio of itself and 4-nitroso-group-3-methylphenol is 2 ~ 10:1; Described catalyzer is the one 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, a certain amount of 4-nitroso-group-3-methylphenol and alcohol is dropped in autoclave, then a certain amount of catalyzer is added and promotor obtains reaction solution a1, then 20 ~ 40 DEG C are warming up to, pass into hydrogen reaction 2 ~ 8h and no longer inhale hydrogen to reaction, stopped reaction, reaction solution is removed, Filtration of catalyst, alcoholic solvent in decompression removing reaction solution a1, obtains the crude product 4-amino-3-methylphenol of solid.
Preferably, described organic amine is the one in Monomethylamine, dimethylamine, Trimethylamine 99.
Preferably, in step (3), through alcoholic solvent dissolving, crystallization, filtration, dry 4-amino-3-methylphenol; Solvent temperature is 40 ~ 70 DEG C, 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 DEG C.
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 that 4-amino-3-methylphenol step (2) obtained is put in a certain amount of alcoholic solvent, is warming up to backflow, and then cooling down crystallization, filtration, vacuum drying obtain the 4-amino-3-methylphenol of high-quality; The mixture that the alcohol that described method uses is the more lower boiling organic solvent such as methyl alcohol, ethanol or these alcohol and water, when the alcohol that use is single, the weight ratio of its consumption and 4-amino-3-methylphenol is 2 ~ 4:1; If use alcohol-water mixture, then the ratio of alcohol water is 1 ~ 4:1.
Preferably, the preparation method of 4-amino-3-methylphenol, comprises the steps:
(1) nitrosation reaction: be raw material with m-cresol, take aqueous sodium hydroxide solution as solvent, Sodium Nitrite and hydrochloric acid are nitrosification agent, prepare 4-nitroso-group-3-methylphenol through nitrosation reaction; Nitrosation reaction temperature controls at 3 ~ 10 DEG C; 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 that is 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 controls at 20 ~ 25 DEG C, 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 in methyl alcohol and is warming up to backflow, then through crystallisation by cooling, filtration, dry 4-amino-3-methylphenol highly finished product; The weight ratio of methyl alcohol and 4-amino-3-methylphenol is 2:1; Drying temperature is 40 DEG C.
Present invention process is simple, and product aftertreatment is easy, and environmental pollution is little, 4-amino-3-methylphenol quality product the quality prepared is high, good stability, and obtained product is except may be used for general applications, can also be used 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 to stir at 10 DEG C of temperature, add after 19.4g Sodium Nitrite dissolves completely and be cooled to 3 ~ 10 DEG C, for subsequent use.Get 81.4g 36% HCl (AR) and 58.1g water in four-hole bottle, slowly drip above-mentioned mixing solutions, control temperature is 3 ~ 10 DEG C, finish and be incubated half an hour, reacting liquid filtering obtains red brown solid, and obtain 33.6g 4-nitroso-group-3-methylphenol after oven dry, productive rate is 93.0%.
75g methyl alcohol is added successively in 500ml stainless steel cauldron, 4g 25% ammoniacal liquor, 4-nitroso-group-3-methylphenol 10g and 5% palladium carbon 0.3g, envelope still, nitrogen replacement 3 times, hydrogen is filled with to 0.5Mpa after hydrogen exchange 3 times, control temperature of reaction kettle 20 ~ 25 DEG C of stirring reactions, reaction 2h, question response liquid no longer eats stopped reaction after hydrogen, drive still, reaction solution suction filtration is reclaimed catalyzer, filtrate normal pressure reclaims methyl alcohol and separates out to there being a large amount of solid, stopping steams, be cooled to 10 ~ 15 DEG C, suction filtration product water rinse then vacuum drying obtains 4-amino-3-methylphenol crude product 9g, crude product adds in 20g methyl alcohol and is warming up to backflow, then 10 DEG C of suction filtrations are cooled to, methanol wash 40 DEG C of vacuum-dryings obtain 4-amino-3-methylphenol highly finished product 7.65g, yield is 85%, product HPLC >=99.5%.
Embodiment 2
Water 900kg is sucked in 2000L stainless steel cauldron R1, drop into 96% sodium hydroxide 90kg, exothermic heat of reaction during input sodium hydroxide, R1 chuck leads to icy salt solution and is cooled to 20 ~ 25 DEG C, then drop into 214kg m-cresol at 10 DEG C of temperature stirring reaction 30min to the abundant salify of m-cresol, then add after 146kg Sodium Nitrite dissolves completely and be cooled to 3 ~ 10 DEG C, for subsequent use.In 3000L glassed steel reaction vessels R2, suck 735kg 30% HCl and 440kg water be uniformly mixed, simultaneously chuck leads to icy salt solution and is cooled to 3 ~ 10 DEG C; Ready, the alkali lye containing Sodium Nitrite prepared in R1 is added drop-wise in the hydrochloric acid prepared in R2, time for adding is about 4h and adds, finish and be incubated half an hour, sampling HPLC detects to raw material m-cresol and reacts completely, and blowing, filters and obtains red brown solid, with water rinse 2 times, salt in removing product, obtains 4-nitroso-group-3-methylphenol.Product is not dried and is directly used in next step hydrogenating reduction.
Suck methyl alcohol 1000kg in 2000L stainless steel autoclave, 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 DEG C, start reaction, no longer change to hydrogen pressure, reaction 8h, sampling detection reacts completely to 4-nitroso-group-3-monomethylaniline.Pressure release, reaction solution is removed catalyzer by strainer, decompression steams methyl alcohol, about 600kg is steamed to methyl alcohol, be cooled to 10 DEG C, be discharged in filtering jar, then centrifugally 4-amino-3-methylphenol crude product is obtained, 4-amino-3-methylphenol the crude product obtained is put in the methanol aqueous solution 600kg of 50% concentration again, is warming up to 45 DEG C, insulated and stirred 20min, then 5 ~ 10 DEG C are cooled to, centrifugal, 45 DEG C of fast boiling dryings 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 to stir at 10 DEG C of temperature, add after 24g Sodium Nitrite dissolves completely and be cooled to 5 DEG C, for subsequent use.Get 96g 25% HCl (AR) and 60g water in four-hole bottle, slowly drip above-mentioned mixing solutions, control temperature is 5 DEG C, finish and be incubated half an hour, reacting liquid filtering obtains red brown solid, and obtain 36.6g 4-nitroso-group-3-methylphenol after oven dry, productive rate is 96.2%.
90g ethanol is added successively in 500ml stainless steel cauldron, 0.5g Trimethylamine 99, 4-nitroso-group-3-methylphenol 10g and Raney's nickel 0.1g, envelope still, nitrogen replacement 3 times, hydrogen is filled with to 0.5Mpa after hydrogen exchange 3 times, control temperature of reaction kettle 30 ~ 35 DEG C of stirring reactions, question response liquid no longer eats stopped reaction after hydrogen, drive still, reaction solution suction filtration is reclaimed catalyzer, filtrate normal pressure reclaims ethanol and separates out to there being a large amount of solid, stopping steams, be cooled to 10 ~ 15 DEG C, suction filtration product water rinse then vacuum drying obtains 4-amino-3-methylphenol crude product 9.5g, crude product adds in 50g ethanol and is warming up to backflow, then 10 DEG C of crystallizations are cooled to, suction filtration, washing with alcohol, 50 DEG C 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 to stir at 10 DEG C of temperature, add after 12g Sodium Nitrite dissolves completely and be cooled to 8 DEG C, for subsequent use.Get in the four-hole bottle of 150g 15% HCl (AR), slowly drip above-mentioned mixing solutions, control temperature is 8 DEG C, finish and be incubated half an hour, reacting liquid filtering obtains red brown solid, and obtain 23.2g 4-nitroso-group-3-methylphenol after oven dry, productive rate is 91.3%.
45g Virahol is added successively in 500ml stainless steel cauldron, 0.2g Monomethylamine, 4-nitroso-group-3-methylphenol 10g and palladium aluminium 0.1g, envelope still, nitrogen replacement 3 times, hydrogen is filled with to 0.5Mpa after hydrogen exchange 3 times, control temperature of reaction kettle 20 ~ 25 DEG C of stirring reactions, question response liquid no longer eats stopped reaction after hydrogen, drive still, reaction solution suction filtration is reclaimed catalyzer, filtrate normal pressure reclaims Virahol and separates out to there being a large amount of solid, stopping steams, be cooled to 10 ~ 15 DEG C, suction filtration product water rinse then vacuum drying obtains 4-amino-3-methylphenol crude product 8.7g, crude product adds in 30g methyl alcohol and is warming up to backflow, then 10 DEG C of crystallisation by cooling are cooled to, suction filtration, methanol wash, 60 DEG C of vacuum-dryings obtain 4-amino-3-methylphenol highly finished product 7.65g, yield is 82%, product HPLC >=99.7%.
Claims (5)
1. a preparation method for 4-amino-3-methylphenol, is characterized in that comprising the steps:
(1) nitrosation reaction: be that raw material prepares 4-nitroso-group-3-methylphenol through nitrosification with m-cresol;
(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;
In step (2), reduction reaction temperature controls at 20 ~ 40 DEG C, reaction times 2 ~ 8h, and described alcoholic solvent is the one in methyl alcohol, ethanol, Virahol, and the weight ratio of itself and 4-nitroso-group-3-methylphenol is 2 ~ 10: 1; Described catalyzer is the one in palladium carbon, palladium aluminium, Raney's nickel, and the weight ratio of itself and 4-nitroso-group-3-methylphenol is 0.005 ~ 0.05: 1; Described promotor is ammonia or organic amine, and the weight ratio of itself and 4-nitroso-group-3-methylphenol is 0.01 ~ 0.1: 1.
2. according to the preparation method of the 4-amino-3-methylphenol described in claim 1, it 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 controls at-5 ~ 15 DEG C; 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 that is rear and m-methyl phenol is 0.8 ~ 1.2: 1.
3. the preparation method of 4-amino-3-methylphenol according to claim 2, is characterized in that: described organic amine is the one in Monomethylamine, dimethylamine, Trimethylamine 99.
4. according to the preparation method of the 4-amino-3-methylphenol described in claim 1, it is characterized in that: in step (3), through alcoholic solvent dissolving, crystallization, filtration, dry 4-amino-3-methylphenol; Solvent temperature is 40 ~ 70 DEG C, 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 DEG C;
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.
5., according to the preparation method of the 4-amino-3-methylphenol described in claim 1, it is characterized in that comprising the steps:
(1) nitrosation reaction: be raw material with m-cresol, take aqueous sodium hydroxide solution as solvent, Sodium Nitrite and hydrochloric acid are nitrosification agent, prepare 4-nitroso-group-3-methylphenol through nitrosation reaction; Nitrosation reaction temperature controls at 3 ~ 10 DEG C; 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 that is 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 controls at 20 ~ 25 DEG C, reaction times 2 ~ 8h, and the weight ratio of methyl alcohol and 4-nitroso-group-3-methylphenol is 7.5: 1; The weight ratio of palladium carbon and 4-nitroso-group-3-methylphenol is 0.03: 1; The weight ratio of described ammonia and 4-nitroso-group-3-methylphenol is 0.1: 1;
(3) purifying: 4-amino-3-methylphenol crude product adds in methyl alcohol and is warming up to backflow, then through crystallisation by cooling, filtration, dry 4-amino-3-methylphenol highly finished product; The weight ratio of methyl alcohol and 4-amino-3-methylphenol is 2: 1; Drying temperature is 40 DEG C.
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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 |
| 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 |
| CN109516924B (en) * | 2018-11-14 | 2021-10-29 | 南京工业大学 | Method for preparing m-aminophenol by catalyzing resorcinol |
| CN111072501B (en) * | 2019-12-16 | 2021-06-11 | 岳阳中展科技有限公司 | Production method of 2,4, 6-tri (dimethylamine methyl) phenol |
| 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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| CN1031526A (en) * | 1988-08-08 | 1989-03-08 | 哈尔滨师范大学 | The preparation method of 4-amino-3-methylphenol |
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| CN1031526A (en) * | 1988-08-08 | 1989-03-08 | 哈尔滨师范大学 | The preparation method of 4-amino-3-methylphenol |
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| 从混合间对甲酚制备杀螟硫磷;王元正;《应用化学》;19871231;第4卷(第5期);第91-93页 * |
| 黄宪 等.还原反应.《有机合成化学》.化学工业出版社,1983,608-612. * |
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