CN114853620B - Anilino acetate and synthesis method thereof - Google Patents
Anilino acetate and synthesis method thereof Download PDFInfo
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/18—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
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Abstract
The invention relates to the technical field of organic synthesis, in particular to anilino acetate and a synthesis method thereof. The synthesis method of the anilino acetate takes anilino acetonitrile as a raw material and comprises an amidation reaction step and an alkaline hydrolysis reaction step, wherein alkali liquor is added into a system in the amidation reaction step and the alkaline hydrolysis reaction step, and the alkali liquor in the amidation reaction step and the alkaline hydrolysis reaction step is added in batches. According to the invention, the alkaline solution is added in batches, so that the phenomenon of side reaction increase caused by overhigh concentration of the alkaline solution in the system in the amidation reaction step is avoided, namely, the alkaline solution is added in batches, so that the byproduct in the amidation reaction step is avoided, the content of the byproduct N-methylaniline is reduced, and the purity of the anilino acetate is improved (the content of the N-methylaniline is less than or equal to 0.3 wt%).
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to anilino acetate and a synthesis method thereof.
Background
Anilino acetate is an important intermediate for producing dye indigo, which is mainly used for dyeing denim and can also be used for synthesizing other fine chemicals.
The preparation method of anilino acetate is relatively more. Su Liana Mian Toff, chemistry and technology of intermediates and dyes, discloses the following method: aniline, chloroacetic acid, sodium hydroxide and ferrous sulfate are used as raw materials to react to generate ferrous anilinoacetate precipitate, the ferrous anilinoacetate precipitate is filtered and washed, then is subjected to double decomposition reaction with caustic alkali solution, iron sludge is filtered out to obtain anilinoacetate solution, and then the anilinoacetate solution is concentrated and dried to obtain an anilinoacetate product. However, the method has complex technical process, complicated operation and low yield (70-80%), can generate a large amount of wastewater containing sodium chloride and ferric salt, can generate a large amount of iron mud, and has serious pollution. Thus, the method has been eliminated.
Patent CN10490032B discloses a preparation method of anilino acetate, which takes aniline and hydroxyacetonitrile as raw materials, reacts under the action of a catalyst to generate anilino acetonitrile, separates an oil phase from a water phase, adds aniline and unreacted complete hydroxyacetonitrile to generate anilino acetonitrile, combines organic phase anilino acetonitrile separated by the two steps of reaction, adds alkali to carry out hydrolysis reaction at 100-120 ℃ to generate anilino acetate, releases ammonia, and then cools and solidifies to obtain an anilino acetate product. The method has the defects that when the anilino acetonitrile is synthesized by the primary reaction, the raw material hydroxyacetonitrile is excessive, the primary reaction is incomplete, the aqueous phase is added with aniline for the secondary reaction, the quality of an anilino acetonitrile oil phase obtained by the secondary reaction is poor, and the quality of the anilino acetate can be influenced by directly adding alkali into the oil phase for the alkaline hydrolysis reaction.
The intermediate anilino acetonitrile is used as a raw material to synthesize the anilino acetate by a one-step method, and the anilino acetate is generated by performing a rapid alkaline hydrolysis reaction under the conditions of high concentration alkali liquor and higher temperature, and simultaneously, more byproduct N-methylaniline is generated, so that the quality and the yield of the anilino acetate are affected, and more importantly, the subsequent application of downstream products is greatly affected.
Disclosure of Invention
In view of the above, the present invention aims to provide an anilino acetate and a synthesis method thereof, which are used for solving the technical problem that the content of N-methylbenzene, which is a byproduct of the process for preparing the anilino acetate, is high by adopting the existing method.
In a first aspect, the invention provides a synthesis method of anilino acetate, which takes anilino acetonitrile as a raw material and comprises an amidation reaction step and an alkaline hydrolysis reaction step, wherein alkali liquor is added in a system in the amidation reaction step and the alkaline hydrolysis reaction step, and the alkali liquor in the system in the amidation reaction step and the alkaline hydrolysis reaction step is added in batches.
In the invention, the term "adding in batches" means that the alkali liquor added in the amidation reaction step and the alkali liquor added in the alkaline hydrolysis reaction step are not added at one time, i.e. the alkali liquor is not added to the whole system at one time in the synthesis process of anilino acetate; and adding excessive alkali liquor into the system not only in the initial stage of the amidation reaction, wherein the unreacted alkali liquor in the amidation reaction step is used as the alkali liquor in the alkaline hydrolysis reaction step for continuous use.
Optionally, the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or sodium hydroxide-potassium hydroxide aqueous solution.
Optionally, in the amidation reaction step, the alkali lye is added at a concentration of 15wt% to 25wt%, preferably 15wt% to 20wt%.
Optionally, in the amidation reaction step, the molar ratio of the alkali in the alkali solution to the anilino acetonitrile is 0.1 to 1.1:1, preferably 0.2 to 0.8:1.
alternatively, the amidation reaction temperature is 35-60 ℃, preferably 38-50 ℃, more preferably 40-45 ℃; the amidation reaction time is 0.5-9h.
Optionally, in the alkaline hydrolysis step, the alkali solution is added at a concentration of 40wt% to 60wt%, preferably 50wt% to 60wt%.
Optionally, the molar ratio of the total amount of alkali in the alkali solution to the anilino acetonitrile in the amidation reaction step and the alkaline hydrolysis reaction step is 1 to 1.1:1, preferably 1.04-1.07:1.
alternatively, the alkaline hydrolysis reaction is carried out at a temperature of 90-110 ℃, preferably 100-105 ℃.
Optionally, the alkaline hydrolysis reaction is followed by evaporation concentration and drying steps.
In another aspect, the invention also provides anilino acetate obtained by the synthesis method.
As described above, the anilino acetate and the synthesis method thereof have the following beneficial effects:
(1) According to the invention, the alkaline solution is added in batches, so that the phenomenon of side reaction increase caused by overhigh concentration of the alkaline solution in the system in the amidation reaction step is avoided, namely, the alkaline solution is added in batches, so that the byproduct of the amidation reaction is avoided, the content of the byproduct N-methylaniline is reduced, and the purity of the anilino acetate is improved (the content of the N-methylaniline is less than or equal to 0.3 wt%).
(2) The invention controls the alkali liquor to be added into the reaction system in a gradient concentration way, and the alkali hydrolysis reaction is added with the high-concentration alkali liquor, so that the carried-in water quantity is reduced, the alkali hydrolysis reaction speed is improved, the production efficiency is improved, the distilled water quantity in the distillation and concentration process is reduced, and the production energy consumption is reduced.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. The term "wt%" as used herein means mass percent unless otherwise specified.
The invention provides a synthesis method of anilino acetate, which takes anilino acetonitrile as a raw material and comprises the steps of amidation reaction, alkaline hydrolysis, evaporation concentration and drying; wherein the temperature of the amidation reaction is 35-60 ℃, and the time of the amidation reaction is 0.5-9h; the temperature of the alkaline hydrolysis reaction is 90-110 ℃;
in the amidation reaction step and the alkaline hydrolysis reaction step, respectively adding 15-25 wt% alkali liquor and 40-60 wt% alkali liquor into the system, wherein the alkali liquor in the amidation reaction step and the alkaline hydrolysis reaction step is added in batches, and the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or sodium hydroxide-potassium hydroxide aqueous solution; the molar ratio of the total amount of alkali in the alkali solution to the anilino acetonitrile in the amidation reaction step and the alkaline hydrolysis reaction step is 1 to 1.1:1, a step of;
in the amidation reaction step, the molar ratio of the alkali in the alkali solution to the anilino acetonitrile is 0.1-1.1:1.
the present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
In the invention, the content of the anilino acetonitrile is according to the chemical industry standard of the people's republic of China (HG/T5285-2017): anilino acetonitrile is detected;
the method for detecting the purity of the anilino acetate product is a liquid chromatography method, and comprises the following specific steps: accurately weighing 5mg of potassium anilinoacetate (or sodium anilinoacetate) standard substance, and fixing the volume to 5ml by using methanol-water (the volume ratio of methanol to water is 3:1) to obtain standard liquids with the concentration of 1mg/ml, and then diluting the standard liquids to obtain serial standard diluents with the concentrations of 0.8mg/ml, 0.6mg/ml, 0.4mg/ml, 0.2mg/ml, 0.1mg/ml, 0.05mg/ml and 0.025mg/ml respectively, wherein the peak heights of the serial standard diluents are measured by using a high performance liquid chromatograph, and the chromatographic conditions are as follows: the chromatographic column is a C18 5 μm chromatographic column, a 4.6mm x 250mm stainless steel column; the mobile phase is methanol-water (the volume ratio of the methanol to the water is 3:1), and the flow rate is 0.5ml/min; the detection wavelength is 285nm, and the column temperature is room temperature; in the detection process, setting a methanol-water blank (taking methanol-water with the same sampling amount as the blank and the volume ratio of methanol to water being 3:1), drawing a standard curve by taking the concentration as an abscissa and the peak height as an ordinate (the ordinate is the value obtained by subtracting the peak height of the blank from the peak height of each standard diluent);
adding 100ml of methanol-water (the volume ratio of methanol to water is 3:1) into 5g of pre-weighed sample to be tested (the mass is m), uniformly mixing, taking 1ml of the mixture to be tested to 100ml, obtaining diluent to be tested, taking 1ml of the diluent to be tested, taking the diluent to be tested to 10ml of the diluent to be tested, measuring the peak heights of various series of standard diluents by using a high performance liquid chromatograph, taking the methanol-water (the volume ratio of methanol to water is 3:1) with the same sampling amount as a blank control, and taking the concentration (the concentration is w) of potassium anilino acetate (or sodium anilino acetate) in the diluent to be tested, wherein the concentration (the concentration is w) of the difference value of the peak heights of the diluent to be tested and the blank control on a standard curve;
then according to the formula
Calculating the purity of potassium anilinoacetate (or sodium anilinoacetate), wherein lambda is the purity of potassium anilinoacetate (or sodium anilinoacetate) and the unit is; w is the concentration of potassium anilinoacetate (or sodium anilinoacetate) in the diluent measured according to a standard curve, and the unit is mg/ml; .
In the invention, the method for detecting the content of the N-methylaniline is a liquid chromatography method, and comprises the following specific steps: accurately weighing 1mg of redistilled N-methylaniline, and using methanol to fix the volume to 100ml to obtain standard solution with the concentration of 10 mug/ml; subsequently diluted with methanol to give serial standard dilutions having concentrations of 8. Mu.g/ml, 6. Mu.g/ml, 4. Mu.g/ml, 2. Mu.g/ml, 1. Mu.g/ml, 0.5. Mu.g/ml, 0.25. Mu.g/ml and 0.125. Mu.g/ml, respectively, and peak heights of the individual serial standard dilutions were determined by high performance liquid chromatography under the following chromatographic conditions: the chromatographic column is a C18 5 μm chromatographic column, a 4.6mm x 250mm stainless steel column; the mobile phase is 100% methanol, and the flow rate is 0.7ml/min; the detection wavelength is 243nm, and the column temperature is room temperature; in the detection process, setting a blank (methanol with the same sampling amount is used as the blank), drawing a standard curve by taking the concentration as an abscissa and the peak height as an ordinate (the ordinate is the value obtained by subtracting the peak height of the blank from the peak height of each standard diluent);
adding 50ml of methanol into 5g of pre-weighed samples to be measured (with the mass of m), uniformly mixing, taking 1ml of the mixture to be measured to 100ml, obtaining the diluent to be measured, taking 1ml of the diluent to be measured, using the methanol to be measured to reach 10ml of the volume, obtaining the samples to be measured, measuring the peak heights of various series of standard diluents by using a high performance liquid chromatograph, using the methanol with the same sampling amount as a blank control, and obtaining the concentration (the concentration is w) of N-methylaniline in the diluent to be measured, wherein the concentration corresponding to the difference value of the absorbance of the diluent to be measured and the peak height of the blank control on a standard curve;
then according to the formula
Calculating the concentration content of N-methylaniline, wherein lambda is the concentration content of N-methylaniline, and the unit is; w is the measured dilution obtained according to the standard curveThe concentration of the N-methylaniline is expressed in mug/ml, m is the sampling amount of a sample to be detected, and the unit is g.
In the invention, the yield is according to the formula
Calculating, wherein eta is the yield, m 1 Is the mass of anilino acetate, the unit is g and omega 1 Is the purity of anilino acetate, the unit is M 1 The unit is g/mol which is the molar mass of anilino acetate; m is m 2 The mass of the anilino acetonitrile serving as a raw material is g and omega 2 The unit of the purity of the raw material anilino acetonitrile is M 2 The unit is g/mol of the molar mass of the anilino acetonitrile.
Example 1
The synthesis process of potassium anilinoacetate includes the following steps:
s1, amidation reaction: 85g of 20wt% potassium hydroxide aqueous solution (the molar quantity of potassium hydroxide is about 0.30 mol) is added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and 138g of anilino acetonitrile solid (the molar quantity of the anilino acetonitrile is 1.0 mol) with the purity of 96wt% (detected according to the national chemical industry standard of the people's republic of China (HG/T5285-2017): anilino acetonitrile) is slowly added under stirring, the feeding temperature is controlled to be 40 ℃, the stirring is continued until the anilino acetonitrile is completely melted after the feeding, the amidation reaction temperature is continuously maintained to be 40 ℃, the anilino acetamide is gradually separated out along with the amidation reaction, a white slurry is obtained, and the sample is sampled and detected after 8 hours, the raw material anilino acetonitrile is not detected (detected by liquid chromatography, the same below);
s2, alkaline hydrolysis reaction: after the amidation reaction, 85g of a 50wt% aqueous potassium hydroxide solution (the molar amount of potassium hydroxide is about 0.76mol, i.e., the total molar amount of potassium hydroxide added in the amidation reaction step and the alkaline hydrolysis step is 1.06 mol) was added to the reaction system; slowly heating the system to 105 ℃ to perform alkaline hydrolysis reaction, gradually disappearing the white slurry along with the alkaline hydrolysis reaction to obtain transparent alkaline hydrolysis reaction liquid, releasing a large amount of ammonia gas in the process, and stopping the reaction after no ammonia gas is generated in the alkaline hydrolysis reaction;
s3, evaporating, concentrating and drying: heating to 110 ℃ is continued until part of water is evaporated until ammonia is absent in the solution, then sulfuric acid solution with the concentration of 2.0mol/L is added, the pH value of the system is adjusted to 7.0, and drying is carried out, so as to obtain 191.43g of potassium anilinoacetate product.
The detection shows that the purity of the potassium anilinoacetate product is 98.36 percent, and the content of N-methylaniline in the potassium anilinoacetate product is 0.13 percent (the content detection method is liquid chromatography, and the following steps are adopted); the yield of potassium anilinoacetate was 99.25%.
Example 2
The synthesis process of sodium anilinoacetate includes the following steps:
s1, amidation reaction: 100g of 15wt% sodium hydroxide aqueous solution (the molar quantity of sodium hydroxide is 0.37 mol) is added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilino acetonitrile solid with 96wt% purity (the molar quantity of the anilino acetonitrile is 1.0 mol) is slowly added under stirring, the feeding temperature is controlled to be 42 ℃, the stirring is continued until the anilino acetonitrile is completely melted after the feeding is finished, the amidation reaction temperature is continuously maintained to be 42 ℃, the anilino acetamide is gradually separated out along with the amidation reaction, a white slurry is obtained, and sampling and detection are carried out after 8.5 hours, so that the raw material anilino acetonitrile is not detected;
s2, alkaline hydrolysis reaction: after the completion of the amidation reaction, 62g of an aqueous sodium hydroxide solution (the molar amount of sodium hydroxide is about 0.7mol, i.e., the total molar amount of sodium hydroxide added in the amidation reaction step and the alkaline hydrolysis reaction step is 1.07 mol) having a concentration of 45% by weight was added to the reaction system; slowly heating the system to 107 ℃ to perform alkaline hydrolysis reaction, gradually disappearing the white slurry along with the alkaline hydrolysis reaction to obtain transparent alkaline hydrolysis reaction liquid, releasing a large amount of ammonia gas in the process, and stopping the reaction after no ammonia gas is generated in the alkaline hydrolysis reaction;
s3, evaporating, concentrating and drying: heating to 113 ℃ continuously, evaporating part of water until ammonia is not contained in the sodium anilinoacetate solution, then adding sulfuric acid solution with the concentration of 2.0mol/L, adjusting the pH value of the system to 7.0, and then drying to obtain 174.24g of sodium anilinoacetate product.
The detection shows that the purity of the sodium anilinoacetate product is 98.75%, and the content of N-methylaniline in the sodium anilinoacetate product is 0.21%; the yield of sodium anilinoacetate was 99.13%.
Example 3
The synthesis process of potassium anilino acetate-sodium anilino acetate mixed salt includes the following steps:
s1, amidation reaction: 70g of potassium hydroxide-sodium hydroxide aqueous solution with the total alkali concentration of 25wt% (the total molar quantity of potassium hydroxide and sodium hydroxide is 0.35mol, the molar ratio of potassium hydroxide to sodium hydroxide is 2:1) is added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilino acetonitrile solid with the purity of 96wt% (the molar quantity of the anilino acetonitrile is 1.0 mol) is slowly added under stirring, the feeding temperature is controlled to be 42 ℃, stirring is continued until the anilino acetonitrile is completely melted after the feeding is finished, the amidation reaction temperature is maintained to be 44 ℃, the anilino acetamide is gradually separated out along with the amidation reaction, so that white slurry is obtained, sampling detection is carried out after 7.5 hours, and no raw material anilino acetonitrile is detected;
s2, alkaline hydrolysis reaction: after the amidation reaction, 73g of potassium hydroxide-sodium hydroxide aqueous solution with a total alkali concentration of 50wt% (the total molar amount of potassium hydroxide and sodium hydroxide is 0.72mol, the molar ratio of potassium hydroxide to sodium hydroxide is 2:1, i.e., the total molar amount of total alkali added in the amidation reaction step and the alkaline hydrolysis reaction step is 1.07 mol) is added to the reaction system; slowly heating the system to 105-108 ℃ to perform alkaline hydrolysis reaction, gradually disappearing the white slurry along with the alkaline hydrolysis reaction to obtain transparent alkaline hydrolysis reaction liquid, releasing a large amount of ammonia gas in the process, and stopping the reaction after no ammonia gas is generated in the alkaline hydrolysis reaction;
s3, evaporating, concentrating and drying: continuously heating to 110-114 ℃ to evaporate part of water until ammonia is not contained in the sodium anilinoacetate solution, then adding a sulfuric acid solution with the concentration of 2.0mol/L, adjusting the pH value of the system to 7.0, and then drying to obtain 185.85g of potassium anilinoacetate/sodium anilinoacetate mixed salt product.
Through detection, the purity of the potassium anilino acetate-sodium anilino acetate mixed salt product (namely the total content of potassium anilino acetate and sodium anilino acetate) is 98.75%, and the content of N-methylaniline in the potassium anilino acetate-sodium anilino acetate mixed salt product is 0.24%; the yield of the potassium anilinoacetate-sodium anilinoacetate mixed salt is 99.104%.
Comparative example 1
The synthesis process of potassium anilinoacetate includes the following steps:
135g of 40wt% potassium hydroxide aqueous solution (the molar quantity of potassium hydroxide is about 1.0.8 mol) is added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilino acetonitrile solid with the purity of 96wt% (obtained from an outer package, the molar quantity of the anilino acetonitrile is 1.0 mol) is slowly added under stirring, the stirring is continued until the anilino acetonitrile is completely melted, the temperature is continuously increased to 100-105 ℃ for alkaline hydrolysis reaction, a large amount of ammonia gas is discharged during the alkaline hydrolysis reaction, the reaction is stopped after no ammonia gas is generated, the temperature is continuously increased to 110 ℃ until part of water is evaporated until no ammonia is in potassium anilino acetate solution, 189.33g of potassium anilino acetate product is obtained after drying, and the purity of the potassium anilino acetate product is 93.25% and the content of N-methylaniline in the potassium anilino acetate product is 5.7% after detection; the yield of potassium anilinoacetate was 93.06%.
Comparative example 2
105g of 40wt% sodium hydroxide aqueous solution (the molar quantity of sodium hydroxide is about 1.05 mol) is added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilino acetonitrile solid with the purity of 96wt% (obtained by external packing, the molar quantity of the anilino acetonitrile is 1.0 mol) is slowly added under stirring, stirring is continued until the anilino acetonitrile is completely melted, heating is continued to 103-107 ℃ for alkaline hydrolysis reaction, a large amount of ammonia gas is discharged during the process, the alkaline hydrolysis reaction is stopped after no ammonia gas is generated, heating is continued to 110 ℃ for evaporating part of water until no ammonia is in the sodium anilino acetate solution, 173.15g of sodium anilino acetate product is obtained after drying, and the purity of the potassium anilino acetate product is 93.02% and the content of N-methylaniline in the sodium anilino acetate product is 5.61% through detection; the yield of sodium anilinoacetate was 92.92%.
Comparative example 3
180g of potassium hydroxide-sodium hydroxide aqueous solution with the total alkali concentration of 30wt% (the total molar quantity of potassium hydroxide and sodium hydroxide is 0.1.07mol, the molar ratio of potassium hydroxide to sodium hydroxide is 2:1) is added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilino acetonitrile solid with the purity of 96wt% (obtained by an outer package, the same) is slowly added under stirring (the molar quantity of the anilino acetonitrile is 1.0 mol), the stirring is continued until the anilino acetonitrile is completely melted after the addition, the temperature is continuously increased to 102-106 ℃ for alkaline hydrolysis reaction, a large amount of ammonia gas is discharged during the process, the reaction is stopped after no ammonia gas is generated during the alkaline hydrolysis reaction, the temperature is continuously increased to 110 ℃ until no ammonia is generated in the evaporation part water of the anilino potassium anilino sodium anilino acetate mixed salt solution, 184.84g of the anilino potassium anilino sodium acetate product is obtained after drying, the purity of the mixed salt product is 92.79%, and the content of N-methylaniline in the mixed salt product is 6.03% after detection; the yield of the mixed salt product was 92.79%.
In summary, the invention significantly reduces the content of N-methylaniline in anilino acetate.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (4)
1. The synthesis method of the anilino acetate is characterized by taking anilino acetonitrile as a raw material and comprising an amidation reaction step and an alkaline hydrolysis reaction step, wherein alkali liquor is added into a system in the amidation reaction step and the alkaline hydrolysis reaction step, the alkali liquor in the amidation reaction step and the alkaline hydrolysis reaction step is added in batches, and the molar ratio of the alkali in the alkali liquor to the anilino acetonitrile in the amidation reaction step is 0.2-0.8:1, in the amidation reaction step, the concentration of the added alkali liquor is 15-25 wt%, in the alkaline hydrolysis reaction step, the concentration of the added alkali liquor is 40-60 wt%, and the molar ratio of the total amount of alkali in the alkali liquor in the amidation reaction step and the alkaline hydrolysis reaction step to the anilino acetonitrile is 1-1.1:1, wherein the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or sodium hydroxide-potassium hydroxide aqueous solution.
2. The method according to claim 1, wherein the amidation reaction is carried out at a temperature of 35 to 60 ℃ for a time of 0.5 to 9 hours.
3. The synthetic method of claim 1 wherein the alkaline hydrolysis reaction is carried out at a temperature of 90-110 ℃.
4. The method of claim 1, further comprising the steps of evaporating, concentrating and drying after the alkaline hydrolysis reaction.
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