CN114957028B - Rapid synthesis method of anilino acetate - Google Patents
Rapid synthesis method of anilino acetate Download PDFInfo
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- CN114957028B CN114957028B CN202210599962.8A CN202210599962A CN114957028B CN 114957028 B CN114957028 B CN 114957028B CN 202210599962 A CN202210599962 A CN 202210599962A CN 114957028 B CN114957028 B CN 114957028B
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- BJKZXRGDVGYJTP-UHFFFAOYSA-N anilino acetate Chemical compound CC(=O)ONC1=CC=CC=C1 BJKZXRGDVGYJTP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- KAXCEFLQAYFJKV-UHFFFAOYSA-N 2-anilinoacetonitrile Chemical compound N#CCNC1=CC=CC=C1 KAXCEFLQAYFJKV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000007112 amidation reaction Methods 0.000 claims abstract description 49
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims abstract description 44
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000035484 reaction time Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- JINONCVJYBHUCP-UHFFFAOYSA-M potassium;2-anilinoacetate Chemical compound [K+].[O-]C(=O)CNC1=CC=CC=C1 JINONCVJYBHUCP-UHFFFAOYSA-M 0.000 description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 26
- YEMGQZDWLLBIEY-UHFFFAOYSA-M sodium;2-anilinoacetate Chemical compound [Na+].[O-]C(=O)CNC1=CC=CC=C1 YEMGQZDWLLBIEY-UHFFFAOYSA-M 0.000 description 24
- 239000000047 product Substances 0.000 description 20
- 239000003085 diluting agent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- -1 potassium anilino acetate-sodium anilino acetate Chemical compound 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910021098 KOH—NaOH Inorganic materials 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XAWRLNNYFXMVPC-UHFFFAOYSA-L potassium sodium 2-anilinoacetate Chemical compound N(C1=CC=CC=C1)CC(=O)[O-].[Na+].[K+].N(C1=CC=CC=C1)CC(=O)[O-] XAWRLNNYFXMVPC-UHFFFAOYSA-L 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JFPFMDWCORUHNB-UHFFFAOYSA-N CNC1=CC=CC=C1.[K] Chemical compound CNC1=CC=CC=C1.[K] JFPFMDWCORUHNB-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to a rapid synthesis method of anilino acetate. S1, adding an anilino acetate solution and anilino acetonitrile into alkali liquor, and carrying out amidation reaction; s2, alkaline hydrolysis reaction, namely adding alkaline liquor into the amidation reaction solution, and performing alkaline hydrolysis reaction to obtain anilino acetate. According to the invention, the target product anilino acetate solution is added in the amidation reaction step, so that the reaction system is homogeneous, the miscibility and mass transfer efficiency of the anilino acetonitrile and the alkali liquor are improved, the technical problems of poor contact and lower reaction efficiency caused by layering of the anilino acetonitrile and the alkali liquor are avoided, the amidation reaction time is further shortened, and the equipment utilization rate and the productivity are improved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a rapid synthesis method of anilino acetate.
Background
Anilino acetate is the main raw material for preparing vat dye indigo. At present, the preparation method of anilino acetate is mainly a one-step method, and specifically comprises the following steps: aniline and hydroxyacetonitrile are used as raw materials, aniline and hydroxyacetonitrile are reacted under the action of a catalyst to generate anilino acetonitrile, an oily water phase is separated, aniline and the hydroxyacetonitrile which is not reacted completely are added into the separated water phase to generate the anilino acetonitrile, the anilino acetonitrile which is an organic phase separated in two steps is combined, alkali is added for hydrolysis reaction to generate anilino acetate, ammonia is released, and then the anilino acetate product is obtained through cooling and solidification. However, the preparation of the anilino acetate by the method has the following defects that the raw material hydroxyacetonitrile is excessive and incomplete in reaction in the process of synthesizing the anilino acetonitrile, the quality of the anilino acetonitrile obtained by adding aniline for secondary reaction is poor, and the quality of the anilino acetate can be influenced by directly adding alkali for alkaline hydrolysis.
There is also a process for synthesizing anilinoacetate by two steps, for example, patent document with publication number CN101591256a discloses a process for preparing anilinoacetate by continuous hydrolysis, which comprises melting solid anilinoacetonitrile, continuously adding into an acylation reaction tower, simultaneously adding liquid alkali, carrying out acylation reaction at 39-60 deg.c for 0.5-9h, continuously adding the acylated material into the synthesis reaction tower, controlling the reaction temperature at 70-105 deg.c for 0.5-8h, delivering the material into deamination evaporator, deaminizing and concentrating at 101-110 deg.c, regulating excessive alkali with anilino acetic acid, crystallizing or drying to obtain anilinoacetate. However, the method has extremely poor mass transfer efficiency, long reaction time, high energy consumption and unfavorable improvement of productivity, and has the advantages of higher production cost, low benefit and poor industrial production prospect.
Disclosure of Invention
Accordingly, the present invention is directed to a rapid synthesis method of anilino acetate, which can reduce energy consumption, time and content of N-methylaniline.
The invention provides a synthesis method of anilino acetate, which comprises the following steps:
s1, amidation reaction, namely adding an anilino acetate solution and anilino acetonitrile into alkali liquor, and carrying out amidation reaction;
s2, alkaline hydrolysis reaction, namely adding alkaline liquor into the amidation reaction solution, and performing alkaline hydrolysis reaction to obtain the anilino acetate.
According to the invention, the target product anilino acetate solution is added in the amidation reaction step, so that a reaction system is homogeneous, the miscibility and mass transfer efficiency of the anilino acetonitrile and the alkali liquor are improved, the technical problems of poor contact and lower reaction efficiency caused by layering of the anilino acetonitrile and the alkali liquor are avoided, the amidation reaction time is further shortened, the equipment utilization rate and the yield are improved, and the technical problems of poor contact and lower reaction efficiency caused by layering of the anilino acetonitrile and the alkali liquor in the prior art are solved, and the by-product N-methylaniline is increased due to the need of adding excessive alkali liquor into the system; in addition, the consumption of alkali liquor in the amidation reaction step is reduced, and the energy consumption in the subsequent evaporation concentration and drying process is also reduced.
Optionally, in step S1, the concentration of the alkali liquor is 15wt% to 25wt%.
Optionally, in step S1, the alkali solution is NaOH solution, KOH solution or NaOH-KOH solution.
Optionally, in step S2, the alkali solution is NaOH solution, KOH solution or NaOH-KOH solution.
Optionally, in step S1, the molar ratio of the base to the anilinoacetonitrile is 0.1 to 1:1, preferably 0.3 to 0.6:1.
In the invention, the anilino acetate solution is a solution obtained by alkaline hydrolysis.
Optionally, in step S1, the anilinoacetate has a concentration of 50wt% to 75wt%, preferably 62wt% to 65wt%.
Optionally, in step S1, the molar ratio of anilino acetate to anilino acetonitrile is 0.2 to 1:1, preferably 0.3 to 0.6:1.
Optionally, in step S1, the amidation reaction temperature is 38-45 ℃, preferably 40-43 ℃; the amidation reaction time is 0.5-1h.
Optionally, in step S2, the lye is present in a concentration of 45wt% to 55wt%, preferably 50wt% to 55wt%.
The concentration of the alkali liquor in the alkaline hydrolysis reaction step is increased to 45-55wt%, so that the water content of the system is reduced, and the energy consumption in the subsequent evaporation concentration and drying steps is further reduced.
Optionally, the molar ratio of the total amount of alkali in the alkaline solution to the anilino acetonitrile in the amidation reaction step and the alkaline hydrolysis step is 1-1.1:1.
Optionally, in step S2, the alkaline hydrolysis reaction is performed at a temperature of 100-110 ℃, preferably 100-105 ℃.
Optionally, in step S2, after the alkaline hydrolysis reaction, evaporation concentration and drying steps are further included.
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 comprises the following steps:
s1, amidation reaction, namely adding an anilino acetate solution with the concentration of 50-75wt% and anilino acetonitrile into alkali liquor with the concentration of 18-23wt%, and carrying out amidation reaction for 0.5-1h at the temperature of 38-45 ℃; the alkali liquor is NaOH solution, KOH solution or NaOH-KOH solution; the molar ratio of the alkali to the anilino acetonitrile is 0.1-1:1; the molar ratio of the anilino acetate to the anilino acetonitrile is 0.2-1:1;
s2, alkaline hydrolysis reaction, namely adding alkaline liquor with the concentration of 45-55wt% into the amidation reaction solution, performing alkaline hydrolysis reaction at the temperature of 100-110 ℃, and then evaporating and concentrating to obtain anilino acetate;
the molar ratio of the total amount of alkali in the alkali solution in the amidation reaction step and the alkaline hydrolysis reaction step to the anilino acetonitrile is 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 method for detecting the purity of potassium anilinoacetate (or sodium anilinoacetate) 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 formulaCalculating 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 mg/ml in the measured dilution obtained according to the standard curve.
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 formulaCalculating the content of N-methylaniline potassium, wherein lambda is the content of the concentration of N-methylaniline, and the unit is; w is the concentration of N-methylaniline in the diluent obtained according to a standard curve, the unit is mug/ml, and m is the sampling amount of a sample to be detected, and the unit is g.
Example 1
The synthesis method of the sodium anilinoacetate specifically comprises the following steps:
s1, amidation reaction: 100g of 18wt% KOH solution (the molar amount of KOH is about 0.32 mol) and 80g of 64.30wt% potassium anilinoacetate solution (the molar amount of potassium anilinoacetate is about 0.27mol and the solvent is water) are added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilinoacetonitrile solid (the molar amount of anilinoacetonitrile is 1.0 mol) with the purity of 96wt% (the detection is carried out according to HG/T5285-2017 anilinoacetonitrile, the same applies below) is slowly added under stirring, the feeding temperature is controlled to be 39 ℃, stirring is continued until the anilinoacetonitrile is completely melted after the feeding is completed, the amidation reaction temperature is maintained to be 42 ℃, the reaction material is a homogeneous system, and sampling detection is carried out after 45min, and the raw material anilinoacetonitrile is not detected (liquid chromatography detection, the same applies below);
s2, alkaline hydrolysis reaction: at the end of the amidation reaction, 83g of 50wt% KOH solution (the molar amount of KOH is about 0.74mol, i.e., the total molar amount of KOH 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 104 ℃ to perform alkaline hydrolysis reaction, 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 112 ℃ continuously, evaporating part of water until ammonia is absent in the solution, then adding sulfuric acid solution with the concentration of 2.0mol/L, adjusting the pH of the system to be neutral, and then drying to obtain 243.87g of potassium anilinoacetate product.
The purity of the obtained potassium anilinoacetate product is 98.35 percent through detection, and the content of N-methylaniline in the potassium anilinoacetate product is 0.16 percent; the yield of potassium anilinoacetate (calculated after subtracting potassium anilinoacetate added in the amidation reaction step) was 99.31%;
yield is according to the formulaCalculating, wherein eta is the yield, m 1 The mass of the potassium anilinoacetate is g and omega 1 The purity of the potassium anilinoacetate is expressed as a unit of M 1 The molar mass of the potassium anilinoacetate is expressed in g/mol; m is m 2 The mass of the anilino acetonitrile serving as a raw material is g and omega 2 The purity of the anilino acetonitrile serving as a raw material is expressed as a unit of M 2 The unit is g/mol of the molar mass of the anilino acetonitrile; the following is the same.
Example 2
The synthesis method of the sodium anilinoacetate specifically comprises the following steps:
s1, amidation reaction: 80g of NaOH solution with the concentration of 23wt% (the molar quantity of NaOH is about 0.46 mol) and 90g of sodium anilinoacetate solution with the concentration of 63.20wt% (the molar quantity of sodium anilinoacetate is about 0.33mol and the solvent is water) are added into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, 138g of anilinoacetonitrile solid with the purity of 96wt% (the molar quantity of anilinoacetonitrile is 1.0 mol) is slowly added under stirring, the feeding temperature is controlled to be 38 ℃, stirring is continued until the anilinoacetonitrile is completely melted after the feeding is completed, the amidation reaction temperature is maintained to be 40 ℃, the reaction materials are in a homogeneous system, sampling and detection are carried out after 35min, and the raw material anilinoacetonitrile is not detected;
s2, alkaline hydrolysis reaction: after the amidation reaction, 55g of a 45wt% NaOH solution (the molar amount of sodium hydroxide is about 0.62mol, i.e., the total molar amount of sodium hydroxide added in the amidation reaction step and the alkaline hydrolysis reaction step is 1.08 mol) was added to the reaction system; slowly heating the system to 103 ℃ to perform alkaline hydrolysis reaction, 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 ℃ continuously to evaporate part of water until ammonia is not contained in the solution, then adding sulfuric acid solution with the concentration of 2.0mol/L, adjusting the pH value of the system to be neutral, and then drying to obtain 233.51g of sodium anilinoacetate product.
The purity of the obtained sodium anilinoacetate product is 98.25%, and the content of N-methylaniline in the sodium anilinoacetate product is 0.20%; the yield of potassium anilinoacetate (calculated after subtracting potassium anilinoacetate added in the amidation reaction step) was 99.41%.
Example 3
The synthesis process of potassium anilino acetate-sodium anilino acetate mixed salt includes the following steps:
s1, amidation reaction: 100g of KOH-NaOH solution with the total alkali concentration of 20wt% (the total molar quantity of KOH and NaOH is 0.39mol, the molar ratio of KOH to NaOH is 2:1) and 70g of potassium anilino acetate-sodium anilino acetate mixed salt solution with the total concentration of 64.5wt% (the molar ratio of potassium anilino acetate to sodium anilino acetate is 2:1, the total molar quantity of potassium anilino acetate and sodium anilino acetate is about 0.25mol, and the solvent is water) are 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 anilino acetonitrile is 1.0 mol) is slowly added under stirring, the feeding temperature is controlled to 39 ℃, stirring is continued until the anilino acetonitrile is completely melted, the amidation reaction temperature is maintained to be 41 ℃, sampling and detection is carried out after 40min, and raw materials of the anilino acetonitrile is not detected;
s2, alkaline hydrolysis reaction: after the amidation reaction, 67g of KOH-NaOH solution with a total alkali concentration of 50wt% (the total molar amount of KOH and NaOH is 0.66mol, and the molar ratio of KOH to NaOH is 2:1, i.e., the total molar amount of alkali added in the amidation reaction step and the alkaline hydrolysis reaction step is 1.06 mol) is added into the reaction system; slowly heating the system to 105 ℃ to perform 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: and continuously heating to 113 ℃ 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, regulating the pH value of the system to be neutral, and then drying to obtain 228.87g of potassium anilinoacetate/sodium anilinoacetate mixed salt product.
The purity (namely the total content of potassium anilino acetate and sodium anilino acetate) of the obtained potassium anilino acetate-sodium anilino acetate mixed salt product is 98.44%, and the content of N-methylaniline in the potassium anilino acetate-sodium anilino acetate mixed salt product is 0.16%; the yield of the potassium anilinoacetate-sodium anilinoacetate mixed salt (calculated after subtracting potassium anilinoacetate and sodium anilinoacetate added in the amidation reaction step) was 99.38%.
Comparative example 1
The synthesis process of potassium anilinoacetate includes the following steps:
s1, amidation reaction, namely adding 100g of KOH solution with the concentration of 18wt% (the molar quantity of potassium hydroxide is about 0.32 mol) into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, slowly adding 138g of anilino acetonitrile solid with the purity of 96wt% (the molar quantity of the anilino acetonitrile is 1.0 mol) under stirring, controlling the feeding temperature to be 39 ℃, continuing stirring until the anilino acetonitrile is completely melted after the feeding is finished, continuously maintaining the amidation reaction temperature to be 42 ℃, sampling and detecting after 8 hours, and detecting no anilino acetonitrile as a raw material;
s2, alkaline hydrolysis reaction: after the amidation reaction, 83g of KOH solution (the molar amount of potassium hydroxide is about 0.74mol, i.e., the total molar amount of KOH added in the amidation reaction step and the alkaline hydrolysis step is 1.06 mol) having a concentration of 50% by weight was added to the reaction system; slowly heating the system to 104 ℃ to perform alkaline hydrolysis reaction, 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 112 ℃ continuously, evaporating part of water until ammonia is absent in the solution, then adding sulfuric acid solution with the concentration of 2.0mol/L, adjusting the pH of the system to be neutral, and then drying to obtain 191.69g of potassium anilinoacetate product.
The purity of the obtained potassium anilinoacetate product is 98.26 percent through detection, and the content of N-methylaniline in the potassium anilinoacetate product is 0.21 percent; the yield of potassium anilinoacetate was 99.28%.
Comparative example 2
The synthesis method of the sodium anilinoacetate specifically comprises the following steps:
s1, amidation reaction, namely adding 80g of NaOH solution with the concentration of 23wt% (the molar quantity of potassium hydroxide is about 0.46 mol) into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, slowly adding 138g of anilino acetonitrile solid with the purity of 96wt% (the molar quantity of the anilino acetonitrile is 1.0 mol) under stirring, controlling the feeding temperature to be 39 ℃, continuing stirring until the anilino acetonitrile is completely melted after the feeding is finished, continuously maintaining the amidation reaction temperature to be 42 ℃, sampling and detecting after 7 hours, and not detecting the raw material anilino acetonitrile;
s2, alkaline hydrolysis reaction: at the end of the amidation reaction, 55g of a 45wt% NaOH solution (the molar amount of sodium hydroxide is about 0.62mol, i.e., the total molar amount of KOH added in the amidation reaction step and the alkaline hydrolysis step is 1.08 mol) was added to the reaction system; slowly heating the system to 105 ℃ to perform alkaline hydrolysis reaction, 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 absent in the solution, then adding sulfuric acid solution with the concentration of 2.0mol/L, adjusting the pH of the system to be neutral, and then drying to obtain 173.15g of sodium anilino acetate product.
The purity of the obtained sodium anilinoacetate product is 98.19 percent through detection, and the content of N-methylaniline in the potassium anilinoacetate product is 0.25 percent; the yield of potassium anilinoacetate was 99.16%.
Comparative example 3
A synthesis method of potassium anilinoacetate-sodium anilinoacetate mixed salt specifically comprises the following steps:
s1, amidation reaction, namely adding 100g of KOH-NaOH solution with the total alkali concentration of 20wt% (the total molar quantity of KOH and NaOH is 0.39mol and the molar ratio of KOH to NaOH is 2:1) into a reactor provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, slowly adding 138g of anilino acetonitrile solid with the purity of 96wt% (the molar quantity of the anilino acetonitrile) under stirring, controlling the feeding temperature to be 39 ℃, continuing stirring until the anilino acetonitrile is completely melted after the feeding is finished, maintaining the amidation reaction temperature to be 42 ℃, and sampling and detecting after 7.5 hours along with the amidation reaction, wherein the raw material of the anilino acetonitrile is not detected;
s2, alkaline hydrolysis reaction: after the amidation reaction, 67g of KOH-NaOH solution with a total alkali concentration of 50wt% (the total molar amount of KOH and NaOH is 0.66mol, and the molar ratio of KOH to NaOH is 2:1, i.e., the total molar amount of alkali added in the amidation reaction step and the alkaline hydrolysis reaction step is 1.06 mol) is added into the reaction system; slowly heating the system to 105 ℃ to perform 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: and continuously heating to 111 ℃ to evaporate part of water until ammonia is absent in the solution, then adding a sulfuric acid solution with the concentration of 2.0mol/L, regulating the pH value of the system to be neutral, and then drying to obtain 182.85g of potassium anilino acetate/sodium anilino acetate mixed salt product.
The purity (namely the total content of potassium anilino acetate and sodium anilino acetate) of the obtained potassium anilino acetate-sodium anilino acetate mixed salt product is 98.26%, and the content of N-methylaniline in the potassium anilino acetate-sodium anilino acetate mixed salt product is 0.23%; the yield of the potassium anilinoacetate-sodium anilinoacetate mixed salt is 99.11%.
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 (5)
1. The synthesis method of anilino acetate is characterized by comprising the following steps of:
s1, amidation reaction, namely adding an anilino acetate solution and anilino acetonitrile into alkali liquor with the concentration of 15-25 wt%, wherein the molar ratio of the alkali to the anilino acetonitrile is 0.5-1:1, the molar ratio of the anilino acetate to the anilino acetonitrile is 0.2-1.0:1, and carrying out amidation reaction for 0.5-1h at the temperature of 38-45 ℃; the alkali liquor is NaOH solution, KOH solution or NaOH-KOH solution; the concentration of the anilino acetate solution is 50-75wt%;
s2, alkaline hydrolysis reaction, namely adding alkaline liquor into the amidation reaction solution, and performing alkaline hydrolysis reaction to obtain the anilino acetate, wherein the alkaline liquor is NaOH solution, KOH solution or NaOH-KOH solution.
2. The method according to claim 1, wherein in step S2, the concentration of the lye is 45wt% to 55wt%.
3. The synthesis according to claim 1, wherein the molar ratio of the total amount of base to anilinoacetonitrile in the alkaline solution in the amidation reaction step and the alkaline hydrolysis step is 1-1.1:1.
4. The synthetic method according to claim 1, wherein in step S2, the alkaline hydrolysis reaction is carried out at a temperature of 100-110 ℃.
5. The method according to claim 1, wherein in step S2, the method further comprises evaporating concentration and drying steps after the alkaline hydrolysis reaction.
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| CN104910032A (en) * | 2015-03-20 | 2015-09-16 | 重庆紫光化工股份有限公司 | Preparation method of anilino-acetate |
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| CN1197061A (en) * | 1997-04-23 | 1998-10-28 | 李明威 | N-phenyl-acetate preparing process |
| CN1465625A (en) * | 2002-06-03 | 2004-01-07 | 上海蓝建染化有限公司 | Method for producing indigo |
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