CN101250112A - Method for producing 1-p-methylphenyl ethylamine - Google Patents
Method for producing 1-p-methylphenyl ethylamine Download PDFInfo
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- CN101250112A CN101250112A CNA2008100608134A CN200810060813A CN101250112A CN 101250112 A CN101250112 A CN 101250112A CN A2008100608134 A CNA2008100608134 A CN A2008100608134A CN 200810060813 A CN200810060813 A CN 200810060813A CN 101250112 A CN101250112 A CN 101250112A
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Abstract
The invention relates to a production method of intermediate 1-p-methylphenyl ethylamine, belonging to the medical and chemical technical field, which comprises oximation reaction, catalytic hydrogenation reaction and following treatment or the like. The invention resolves the problems of prior production method of intermediate 1-p-methylphenyl ethylamine which has high demand on device, needs ultrahigh pressure and low safety. The inventive production method of 1-p-methylphenyl ethylamine has cheap and easily accessible material, low cost, high product yield, high product purity, few reaction steps and high safety.
Description
Technical field
The present invention relates to a kind of method of producing chemical intermediate, particularly a kind of method of producing intermediate 1-p-methylphenyl ethamine; Belong to medicine and chemical technology field.
Background technology
1-p-methylphenyl ethamine is the important intermediate of a kind of medicine, agricultural chemicals and dyestuff, it can be synthetic by a lot of methods, but from production cost, the simple and easy degree of technical process, what of reactions steps, raw-material easily purchasing with the factors such as fierce degree of cost and entire reaction course considers that generally many is raw material with the p-methyl aceto phenone, and its preparation method mainly contains following two kinds:
Method one: with the p-methyl aceto phenone is raw material, and itself and ammonium formate reaction are made N-p-methylphenyl ethyl-formamide, gets N-p-methylphenyl ethylamine hydrochloride through acidifying, hydrolysis, and alkaline hydrolysis obtains product again.Its reaction equation is as follows:
Though that this method adopts is cheap, easily purchase, starting material such as lower-cost p-methyl aceto phenone and ammonium formate, this reaction process is loaded down with trivial details, and step is more; Product yield that makes and purity are all lower.
Method two: the employing p-methyl aceto phenone is a raw material, under the condition that ammonia exists, is catalyzer with the Raney's nickel; Obtain product 1-p-methylphenyl ethamine through the high pressure catalytic hydrogenation reaction.Its reaction equation is as follows:
Though this method adopts the starting material of easily purchasing at a low price, reactions steps is few, reaction needed uht conditions harshness, and to the equipment requirements height, security is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of starting material cheap and easy to get, cost is low, product yield and purity height; Reactions steps is few, the method for the production 1-p-methylphenyl ethamine that safety performance is high.
Above-mentioned technical purpose of the present invention is implemented by the following technical programs: a kind of method of the 1-of production p-methylphenyl ethamine, and this method may further comprise the steps:
(1), oximation reaction: as solvent, alkali adds raw material p-methyl aceto phenone and oxammonium hydrochloride or oxammonium sulfate as neutralizing agent, carries out oximation reaction under the condition of 30 ℃～80 ℃ of temperature, obtains oxime compounds (I) behind the oximation reaction with alcohol, water mixed solution;
(2), catalytic hydrogenation reaction: after the above-mentioned oxime compounds that makes (I) process precipitation, washing, drying, with anhydrous methanol as solvent, logical hydrogen carries out catalytic hydrogenation reaction under catalyst action, the logical hydrogen time is 2～6 hours, makes 1-p-methylphenyl ethamine crude product (II) behind the catalytic hydrogenation reaction;
(3), aftertreatment: with the above-mentioned 1-p-methylphenyl ethamine crude product (II) that makes by filtering, distill, add the alkali stirring and segregation, obtain 1-p-methylphenyl ethamine finished product after the drying, wherein the weight ratio of p-methyl aceto phenone and oxammonium hydrochloride or oxammonium sulfate is 1.2～2: 1 in the oximation reaction, the weight ratio of p-methyl aceto phenone and solvent is 1: 2～8, and the mol ratio of p-methyl aceto phenone and neutralizing agent is 1: 1～3; The consumption of every g oxime compounds (I) anhydrous methanol is 3～6ml in the catalytic hydrogenation reaction;
The present invention produces the mixture that solvent used in the method for 1-p-methylphenyl ethamine is an alcohol and water, can keep reaction system is homogeneous system, adopt cheap p-methyl aceto phenone of easily purchasing and oxammonium hydrochloride or oxammonium sulfate as raw material, the compound that generates owing to ketone compounds and azanol effect, general formula all has the C=NOH base, and the oxime that is formed by ketone claims ketoxime; Not adopting rudimentary ether is because oxammonium hydrochloride or oxammonium sulfate are insoluble to rudimentary ether as solvent, is in order to prevent to form the yield and the purity of other ketoxime compounds affect the finished product and do not adopt lower ketones as solvent; And since oxammonium hydrochloride or oxammonium sulfate all have acidity and can produce certain influence environment, the present invention adopts alkali as neutralizing agent, when adding neutralizing agent, temperature will be controlled at below 60 ℃, treats to be warming up to after neutralizing agent adds and refluxes more than 60 ℃ 5～10 minutes.When adding neutralizing agent, the temperature of reactive system automatically heats up because of heat release, therefore temperature is controlled at below 60 ℃, like this can save energy and be convenient to the control reaction, be warming up to reacting completely of refluxing more than 60 ℃ and made in 5～10 minutes.
Because oxime compounds (I) hydrolysis easily obtains original p-methyl aceto phenone, so alcohol, water mixed solvent are removed in distillation earlier behind oximation reaction, water is separated out oxime compounds (I) fast again, in order to prevent its hydrolysis, filters fast, the dry catalyzed reaction of carrying out in the anhydrous methanol solvent.
Preparation method's important feature of 1-p-methylphenyl ethamine of the present invention is that technical process is simple, step is few; The cost of material that adopts is cheap, buys easily to obtain, and entire reaction course is milder, and easy control of reaction conditions is convenient to operation; Adopt the 1-p-methylphenyl ethamine yield and the purity height of above-mentioned prepared, be fit to the suitability for industrialized production of various scales.
In the method for above-mentioned production 1-p-methylphenyl ethamine, alcohol is lower alcohol in the alcohol described in the step (1), the water mixed solution, and lower alcohol is a kind of in ethanol, the methyl alcohol; The weight ratio of rudimentary alcohol and water is 2～10: 1 in the described mixing solutions.The present invention adopts rudimentary alcohol and water to mix solvent as oximation reaction, and wherein lower alcohol is mainly methyl alcohol and ethanol, but considers preferred alcohol from environmental protection, factor such as volatile.
In the method for above-mentioned production 1-p-methylphenyl ethamine, the neutralizing agent described in the step (1) is divided into 3～8 times to be put in the reaction solvent, and neutralizing agent is a kind of in potassium hydroxide, the sodium hydroxide.The neutralizing agent that adopts in the oximation reaction of the present invention is an alkali, the gas because carbonate splits the carbon dioxide off etc. easily, influence the purity and the yield of reaction process and the finished product, used alkali is mainly potassium hydroxide, sodium hydroxide, but considers preferred sodium hydroxide from price.Utilize alkali as neutralizing agent can in and hydrochloric acid in the oxammonium hydrochloride, like this azanol could and the p-methyl aceto phenone generation oxime that reacts because the very fast and heat release of neutralization reaction, so the uncontrollable temperature of reaction of disposable adding is the employing mode of adding repeatedly.
In the method for above-mentioned production 1-p-methylphenyl ethamine, the temperature of the oximation reaction described in the step (1) is 50 ℃～70 ℃.Reaction is incomplete if temperature is too low, the cost of the more increase reaction of the too high energy that not only needs of temperature, and the material phenomenon can appear dashing.
In the method for above-mentioned production 1-p-methylphenyl ethamine, the catalyzer described in the step (2) is a kind of in Raney's nickel, palladium charcoal or the platinum oxide; The weight ratio of described catalyzer and oxime compounds (I) is 0.01～0.08: 1.In catalytic hydrogenation reaction step of the present invention, the activity of such catalysts surface energy improves the activity of reactant, and wherein the Raney's nickel price comparison is cheap, and cost is low, so be preferably W-2 type Raney's nickel.
In the method for above-mentioned production 1-p-methylphenyl ethamine, the pressure in the step (2) during catalytic hydrogenation reaction is 1～2Mpa.Because oxime compounds (I) hydrogenating reduction ratio is easier to, the pressure when leading to hydrogen in the catalytic hydrogenation reaction process of the present invention only needs 1～2Mpa, does not need hyperpressure just can finish catalytic hydrogenation reaction, and low for equipment requirements, security is higher.But pressure is lower than very much 1Mpa, and speed of response is too slow, influences speed of reaction.
In the method for above-mentioned production 1-p-methylphenyl ethamine, as preferably, step (2) catalytic hydrogenation reaction temperature is 50 ℃～80 ℃, and the reaction times is 3～5 hours.Catalytic hydrogenation reaction temperature lower velocity is too slow, and the high impurity of temperature is many, and the time short reaction is incomplete, and the time, long yield did not improve substantially.
In the method for above-mentioned production 1-p-methylphenyl ethamine, the detailed process of aftertreatment is in the step (3): the shortening material that will contain 1-p-methylphenyl ethamine crude product (II) the elimination catalyzer of lowering the temperature, reheat evaporation anhydrous methanol, adding alcohol, water mixed solution remove impurity by distillation then, add alkali stirring and segregation, drying again, underpressure distillation obtains product.
The reaction equation of 1-p-methylphenyl ethamine preparation of the present invention is as follows:
In sum, the present invention's method of producing 1-p-methylphenyl ethamine has the following advantages:
1, the raw material of method employing of the present invention is inexpensive easily purchases, and reactions steps is reasonable, simple, the reaction conditions gentleness, and required equipment requirements is low, and security is fit to the suitability for industrialized production of various scales well.
2, the 1-p-methylphenyl ethamine product yield height that utilizes method of the present invention to produce can reach more than 65%, and the purity of finished product is also high can be reached more than 95%, can be applicable to suitability for industrialized production.
Description of drawings:
Fig. 1 is the gas chromatogram of the 1-p-methylphenyl ethamine produced of the present invention.
Embodiment
Below by specific embodiment also in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
In the 500ml there-necked flask that agitator, thermometer, reflux cooler are housed, drop into raw material 44.5g p-methyl aceto phenone, 27.6 gram oxammonium hydrochloride, mixed solvent 140g ethanol and 10g water.Agitation condition drops into neutralizing agent sodium hydroxide 24g down, divide and thrown for 5 times, controlled temperature is 50～55 ℃, has thrown post-heating to 70 ℃ backflow 5 minutes, after reaction finishes, ethanol is reclaimed in distillation under condition of normal pressure, be cooled to room temperature, add water 320ml, be cooled under the agitation condition below 5 ℃ and filter fast, filter cake obtains oxime compounds 50 ℃ of left and right sides flash bakings, and yield is greater than 95%.
With the above-mentioned oxime compounds that makes, 500ml anhydrous methanol and 4gW-2 type Raney's nickel, put in the pressurized vessel, logical then hydrogen, keep reacting system pressure 1.2～1.3Mpa, 70 ℃ of temperature, about 4 hours of catalytic hydrogenation reaction time, the TLC endpoint detection is reacted the shortening material that obtains containing 1-p-methylphenyl ethamine crude product after finishing.
The shortening material that will the contain 1-p-methylphenyl ethamine crude product elimination catalyzer W-2 type Raney's nickel of lowering the temperature, the heating evaporation anhydrous methanol is recycled, remove impurity by steam distillation after adding the water mixed solution of the ethanol of 35ml and 100ml then, add 25g solid sodium hydroxide stirring and segregation, organic layer solid sodium hydroxide drying again, underpressure distillation obtains product 1-p-methylphenyl ethamine, content is more than 99.5%, and yield reaches more than 75%.
The device that oximation reaction adopts repeats no more with embodiment 1; Drop into raw material 89g p-methyl aceto phenone, 52.1g oxammonium sulfate, mixed solvent 192g ethanol and 60g water.Agitation condition drops into neutralizing agent sodium hydroxide 46g down, divide and thrown for 6 times, controlled temperature is 30～40 ℃, has thrown post-heating to 65 ℃ backflow 8 minutes, after reaction finishes, ethanol is reclaimed in distillation under condition of normal pressure, be cooled to room temperature, add water 480ml, be cooled under the agitation condition below 5 ℃ and filter fast, filter cake obtains oxime compounds 50 ℃ of left and right sides flash bakings, and yield is greater than 95%.
With the above-mentioned oxime compounds that makes, 600ml anhydrous methanol and 2g platinum oxide, put in the pressurized vessel, logical then hydrogen, keep reacting system pressure 1.4～1.6Mpa, 60 ℃ of temperature, about 5 hours of catalytic hydrogenation reaction time, the TLC endpoint detection is reacted the shortening material that obtains containing 1-p-methylphenyl ethamine crude product after finishing.
The shortening material that will the contain 1-p-methylphenyl ethamine crude product elimination catalyst oxidation platinum of lowering the temperature, the heating evaporation anhydrous methanol is recycled, remove impurity by steam distillation after adding the water mixed solution of the ethanol of 50ml and 150ml then, add 35g solid sodium hydroxide stirring and segregation, organic layer solid sodium hydroxide drying again, underpressure distillation obtains product 1-p-methylphenyl ethamine, content is more than 99.5%, and yield reaches more than 75%.
Embodiment 3
The device that oximation reaction adopts repeats no more with embodiment 1; Drop into raw material 92g p-methyl aceto phenone, 54g oxammonium hydrochloride, mixed solvent 185g ethanol and 55g water.Agitation condition drops into neutralizing agent sodium hydroxide 48g down, divide and thrown for 5 times, controlled temperature is 40～45 ℃, has thrown post-heating to 70 ℃ backflow 6 minutes, after reaction finishes, ethanol is reclaimed in distillation under condition of normal pressure, be cooled to room temperature, add water 500ml, be cooled under the agitation condition below 5 ℃ and filter fast, filter cake obtains oxime compounds 50 ℃ of left and right sides flash bakings, and yield works energetically 90%.
With the above-mentioned oxime compounds that makes, 800ml anhydrous methanol and 3g palladium charcoal, put in the pressurized vessel, logical then hydrogen, keep reacting system pressure 1.6～1.8Mpa, 80 ℃ of temperature, about 3 hours of catalytic hydrogenation reaction time, the TLC endpoint detection is reacted the shortening material that obtains containing 1-p-methylphenyl ethamine crude product after finishing.
The shortening material that will the contain 1-p-methylphenyl ethamine crude product elimination catalyst oxidation platinum of lowering the temperature, the heating evaporation anhydrous methanol is recycled, remove impurity by steam distillation after adding the water mixed solution of the ethanol of 100ml and 200ml then, add 32g solid sodium hydroxide stirring and segregation, organic layer solid sodium hydroxide drying again, underpressure distillation obtains product 1-p-methylphenyl ethamine, content is more than 95%, and yield reaches more than 65%.
Embodiment 4
The device that oximation reaction adopts repeats no more with embodiment 1; Drop into raw material 89g p-methyl aceto phenone, 56g oxammonium hydrochloride, mixed solvent 224g ethanol and 20g water.Agitation condition drops into neutralizing agent sodium hydroxide 52g down, divides and has thrown for 8 times, and the process of all the other oximation reactions repeats no more with embodiment 1; Obtain oxime compounds, yield is greater than 99%.
With the above-mentioned oxime compounds that makes, 500g anhydrous methanol and 4gW-2 type Raney's nickel are put in the pressurized vessel, and remaining process repeats no more with embodiment 1; Obtain product 1-p-methylphenyl ethamine, content is more than 97%, and yield reaches more than 80%.
The device that oximation reaction adopts repeats no more with embodiment 1; Drop into raw material 92g p-methyl aceto phenone, 54g oxammonium hydrochloride, mixed solvent 202g ethanol and 58g water.Agitation condition drops into neutralizing agent sodium hydroxide 48g down, divides and has thrown for 6 times, and the process of all the other oximation reactions repeats no more with embodiment 1; Obtain oxime compounds, yield is greater than 99%.
With the above-mentioned oxime compounds that makes, 600g anhydrous methanol and 3gW-2 type Raney's nickel are put in the pressurized vessel, and remaining process repeats no more with embodiment 1; Obtain product 1-p-methylphenyl ethamine, content is more than 97%, and yield reaches more than 75%.
The 1-p-methylphenyl ethamine finished product of above-mentioned system is analyzed by gas-chromatography, wherein gas chromatogram as shown in Figure 1, analytical results is as shown in table 1, the sampler of the gas-chromatography that adopts: the shunting, detector: FID.
Table 1: the 1-p-methylphenyl ethamine finished product stratographic analysis result of system of the present invention
In conjunction with Fig. 1 and table 1 as can be seen: the 1-p-methylphenyl ethamine of system of the present invention is higher by the content of chromatogram ration analysis product.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific embodiments as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (8)
1, a kind of method of producing 1-p-methylphenyl ethamine, this method may further comprise the steps:
(1), oximation reaction: as solvent, alkali adds raw material p-methyl aceto phenone and oxammonium hydrochloride or oxammonium sulfate as neutralizing agent, carries out oximation reaction under the condition of 30 ℃～80 ℃ of temperature, obtains oxime compounds (I) behind the oximation reaction with alcohol, water mixed solution;
(2), catalytic hydrogenation reaction: after the above-mentioned oxime compounds that makes (I) process precipitation, washing, drying, with anhydrous methanol as solvent, logical hydrogen carries out catalytic hydrogenation reaction under catalyst action, the logical hydrogen time is 2～6 hours, makes 1-p-methylphenyl ethamine crude product (II) behind the catalytic hydrogenation reaction;
(3), aftertreatment: with the above-mentioned 1-p-methylphenyl ethamine crude product (II) that makes by filtering, distill, add the alkali stirring and segregation, obtain 1-p-methylphenyl ethamine finished product after the drying, wherein the weight ratio of p-methyl aceto phenone and oxammonium hydrochloride or oxammonium sulfate is 1.2～2: 1 in the oximation reaction, the weight ratio of p-methyl aceto phenone and solvent is 1: 2～8, and the mol ratio of p-methyl aceto phenone and neutralizing agent is 1: 1～3; The consumption of every g oxime compounds (I) anhydrous methanol is 3～6ml in the catalytic hydrogenation reaction;
2, the method for production according to claim 1 1-p-methylphenyl ethamine, it is characterized in that: alcohol is lower alcohol in the alcohol described in the step (1), the water mixed solution, lower alcohol is a kind of in ethanol, the methyl alcohol; The weight ratio of rudimentary alcohol and water is 2～10: 1 in the described mixing solutions.
3, the method for production according to claim 1 1-p-methylphenyl ethamine, it is characterized in that: the neutralizing agent described in the step (1) is divided into 3～8 times to be put in the reaction solvent, and neutralizing agent is a kind of in potassium hydroxide, the sodium hydroxide.
4, according to the method for claim 1 or 2 or 3 described production 1-p-methylphenyl ethamine, it is characterized in that: the temperature of the oximation reaction described in the step (1) is 50 ℃～70 ℃.
5, the method for production according to claim 1 1-p-methylphenyl ethamine is characterized in that: the catalyzer described in the step (2) is a kind of in Raney's nickel, palladium charcoal or the platinum oxide; The weight ratio of described catalyzer and oxime compounds (I) is 0.01～0.08: 1.
6, produce the method for 1-p-methylphenyl ethamine according to claim 1 or 5, it is characterized in that: the pressure in the step (2) during catalytic hydrogenation reaction is 1～2Mpa.
7, the method for production 1-p-methylphenyl ethamine according to claim 1, it is characterized in that: step (2) catalytic hydrogenation reaction temperature is 50 ℃～80 ℃, and the reaction times is 3～5 hours.
8, the method for production 1-p-methylphenyl ethamine according to claim 1, it is characterized in that: the detailed process of aftertreatment is in the step (3): the shortening material that will contain 1-p-methylphenyl ethamine crude product (II) the elimination catalyzer of lowering the temperature, reheat evaporation anhydrous methanol, adding alcohol, water mixed solution remove impurity by distillation then, add alkali stirring and segregation, drying again, underpressure distillation obtains product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921194A (en) * | 2009-06-12 | 2010-12-22 | 中国中化股份有限公司 | Method for preparing 4-chlorobenzhydrylamine |
| CN103159191A (en) * | 2013-03-25 | 2013-06-19 | 浙江圣安化工有限公司 | Preparation method of hydroxylamine salt |
| CN112457204B (en) * | 2020-11-26 | 2022-09-06 | 诚达药业股份有限公司 | Preparation method of S-configuration phenethylamine hydrochloride compound |
-
2008
- 2008-03-18 CN CN2008100608134A patent/CN101250112B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921194A (en) * | 2009-06-12 | 2010-12-22 | 中国中化股份有限公司 | Method for preparing 4-chlorobenzhydrylamine |
| CN103159191A (en) * | 2013-03-25 | 2013-06-19 | 浙江圣安化工有限公司 | Preparation method of hydroxylamine salt |
| CN103159191B (en) * | 2013-03-25 | 2016-04-06 | 浙江圣安化工有限公司 | A kind of preparation method of hydroxylammonium salt |
| CN112457204B (en) * | 2020-11-26 | 2022-09-06 | 诚达药业股份有限公司 | Preparation method of S-configuration phenethylamine hydrochloride compound |
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