CN114957018A - Preparation method of m-hydroxy-N, N-diethylaniline - Google Patents
Preparation method of m-hydroxy-N, N-diethylaniline Download PDFInfo
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- CN114957018A CN114957018A CN202210688860.3A CN202210688860A CN114957018A CN 114957018 A CN114957018 A CN 114957018A CN 202210688860 A CN202210688860 A CN 202210688860A CN 114957018 A CN114957018 A CN 114957018A
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- mixture
- hydroxy
- diethylaniline
- crude product
- temperature
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- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 44
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000012043 crude product Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 229940018563 3-aminophenol Drugs 0.000 claims abstract description 17
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 235000017550 sodium carbonate Nutrition 0.000 claims description 19
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 11
- 229960003750 ethyl chloride Drugs 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 43
- 239000003513 alkali Substances 0.000 description 28
- 238000005804 alkylation reaction Methods 0.000 description 28
- 230000029936 alkylation Effects 0.000 description 26
- 239000007788 liquid Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000004821 distillation Methods 0.000 description 17
- 238000006386 neutralization reaction Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- MTEVPEXUCYPJOF-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)c1cccc(O)c1.CCN(CC)c1cccc(O)c1 MTEVPEXUCYPJOF-UHFFFAOYSA-N 0.000 description 1
- JCMWSVNNSPUNER-UHFFFAOYSA-N N,O-dimethyltyramine Chemical compound CNCCC1=CC=C(OC)C=C1 JCMWSVNNSPUNER-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- GLXWXYTYBIBBLD-UHFFFAOYSA-M sodium;3-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=CC(S([O-])(=O)=O)=C1 GLXWXYTYBIBBLD-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The application provides a preparation method of m-hydroxy-N, N-diethylaniline, which comprises the following steps: heating and mixing m-aminophenol, halogenated hydrocarbon and water, and reacting to generate a mixture 1 containing a crude product of m-hydroxy-N, N-diethylaniline; slowly mixing the mixture 1 with an acid binding agent to obtain a mixture 2; incubating the mixture 2 at 100 ℃ to 165 ℃; cooling the mixture 2, adjusting the pH value of the mixture 2 to 5.5-6.5, and filtering to obtain a solid, namely a crude product; distilling the crude product to obtain a distillate with the temperature of 165-180 ℃, namely the m-hydroxy-N, N-diethylaniline. The brand new m-hydroxy-N, N-diethylaniline production process provided by the application changes many defects of the old process. The process provided by the application has the advantages of few production steps, short production period, high production efficiency and less three-waste generation.
Description
Technical Field
The invention relates to but is not limited to the field of organic synthesis, in particular to but not limited to a preparation method of m-hydroxy-N, N-diethylaniline.
Background
m-Hydroxy-N, N-diethylaniline (3-Hydroxy-N, N-diethylaniline), also known as m-diethylaminophenol, of the molecular formula: C10H15NO, molecular weight: 165.23. the m-hydroxy-N, N-diethylaniline can be used as an intermediate of basic rose essence, acid peach red, disperse fluorescent series dyes and the like.
In the production method in the prior art, sodium m-aminobenzenesulfonate and chloroethane are used as main raw materials, and after alkylation reaction, intermediate material 3-N, N-diethylbenzene sulfonate (alkylate for short) is obtained through desalination and layering; and performing alkali fusion reaction (the alkali fusion reaction is performed in a medium of potassium hydroxide, sodium hydroxide and liquid alkali), acid precipitation, dehydration and distillation on the alkylate to obtain the product.
The process has the following defects: 1) the production process is long, the steps are many, and the specific reaction steps are as follows: alkylation, dehydration and desalination, alkali fusion, acid precipitation, crude product dehydration, distillation and the like; 2) the three wastes are more and difficult to treat, and the method is characterized in that: the alkali fusion reaction needs a large amount of alkali, and the acid precipitation needs a large amount of acid for neutralization, so that a large amount of mixed salt is generated; the waste water contains phenol organic impurities, and the waste water is difficult to treat; 3) the product quality is unstable, and the alkali fusion reaction is carried out at a high temperature (the highest reaction temperature is 335 ℃), so that the product is easily oxidized, and the product quality greatly fluctuates.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The application provides a novel m-hydroxy-N, N-diethylaniline synthesis process, and a target product is synthesized by one-step reaction; the new process greatly shortens the process route and the synthesis time of the product and improves the production efficiency.
The new synthesis process provided by the application adopts m-aminophenol and chloroethane as main raw materials, and performs one-step alkylation reaction to obtain the product, and has the advantages of short process, less three wastes, high production efficiency, convenient raw material purchase, stable product quality and the like.
The application provides a preparation method of m-hydroxy-N, N-diethylaniline, which comprises the following steps:
heating and mixing m-aminophenol, halogenated hydrocarbon and water, and reacting to generate a mixture 1 containing a crude product of m-hydroxy-N, N-diethylaniline;
slowly mixing the mixture 1 with an acid binding agent to obtain a mixture 2;
incubating the mixture 2 at 100 ℃ to 165 ℃, preferably at 100 ℃ to 155 ℃, more preferably at 120 ℃ to 135 ℃; when a closed vessel is used, the pressure in the reactor at this time may be 1.15MPa to 1.45 MPa.
Cooling the mixture 2, adjusting the pH value of the mixture 2 to 5.5-6.5, and filtering to obtain a solid, namely a crude product;
distilling the crude product to obtain a distillate with the temperature of 165-180 ℃, namely the m-hydroxy-N, N-diethylaniline.
In the method for preparing m-hydroxy-N, N-diethylaniline provided by the application, the halogenated hydrocarbon is selected from any one or more of chloroethane, bromoethane and iodoethane, preferably chloroethane.
In the preparation method of m-hydroxy-N, N-diethylaniline, the mixture 1 and the acid-binding agent are slowly mixed, and the acid-binding agent is slowly added into the mixture 1, so that the acid-binding agent is completely added within 1-4 hours.
In the preparation method of m-hydroxy-N, N-diethylaniline, the acid-binding agent is selected from any one or more of sodium hydroxide, magnesium oxide or soda ash;
in one embodiment provided herein, the acid scavenger is an aqueous sodium hydroxide solution.
In the method for producing m-hydroxy-N, N-diethylaniline provided herein, an alkaline solution selected from either or both of an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution is used for adjusting the pH of the mixture 2;
in one embodiment provided herein, the alkaline solution is added dropwise to adjust the pH of the mixture 2.
In the method for producing m-hydroxy-N, N-diethylaniline provided herein, the heating is carried out by raising the temperature of the mixture of m-aminophenol and a halogenated hydrocarbon with water to 80 to 100 ℃ in a closed container, and then stopping the heating, so that the temperature of the mixture of m-aminophenol, the halogenated hydrocarbon with water is naturally raised to 100 to 165 ℃, preferably to 100 to 155 ℃, more preferably to 120 to 135 ℃ (or is continuously heated to this temperature range);
in one embodiment provided herein, the heating is performed by introducing steam into a jacket of a closed reaction kettle having the jacket, so that the temperature of the mixture of m-aminophenol, halogenated hydrocarbon and water in the reaction kettle is increased to 80 ℃ to 100 ℃ (the mixture may also be heated by other heating methods such as electrical heating), and then stopping introducing the steam, so that the temperature of the mixture of m-aminophenol, halogenated hydrocarbon and water is naturally increased to 100 ℃ to 165 ℃, preferably to 100 ℃ to 155 ℃, and more preferably to 120 ℃ to 135 ℃; meanwhile, the pressure in the closed reaction kettle is increased (the pressure in the closed reaction kettle can be 1.1MPa to 1.45 MPa); when the mixture 2 needs to be cooled, the reaction vessel is depressurized simultaneously.
In one embodiment provided herein, the mixture 2 is incubated for 10 minutes to 60 minutes, preferably 10 minutes to 30 minutes or 30 minutes to 60 minutes.
In the preparation method of m-hydroxy-N, N-diethylaniline provided by the application, the operation pressure when distilling the crude product is-0.085 MPa to-0.095 MPa.
In the method for producing m-hydroxy-N, N-diethylaniline provided herein, the mass ratio of the water, the m-aminophenol and the halogenated hydrocarbon is (2 to 10):1 (1.45 to 2.50);
in one embodiment provided herein, the mass ratio of the acid scavenger to the halogenated hydrocarbon is 2 (1.7 to 5.5);
in one embodiment provided herein, the mass ratio of the acid scavenger to the halogenated hydrocarbon is 2 (4 to 5).
In the preparation method of m-hydroxy-N, N-diethylaniline provided by the application, when the pH value of the mixture 2 is adjusted, the temperature of the mixture 2 is 10-35 ℃;
in one embodiment provided herein, mixture 2 is separated after the pH adjustment, and the resulting solid material is the crude product.
In the preparation method of m-hydroxy-N, N-diethylaniline provided by the application, the mixture 1 is transferred and operated among different containers under the protection of inert atmosphere gas;
in one embodiment provided herein, the inert atmosphere gas is selected from an inert gas or nitrogen.
The brand new m-hydroxy-N, N-diethylaniline production process provided by the application changes many defects of the old process. The old process has the defects of multiple production steps, long production route, large amount of acid and alkali, production of a large amount of waste salt and waste water, low production efficiency and the like. The new process provided by the application has the advantages of few production steps, short production period, high production efficiency and less three-waste generation.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the application. Other advantages of the present application may be realized and attained by the invention in its aspects as described in the specification.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application are described in detail below. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
Example 1
1) 1080kg of water, 365kg of m-aminophenol and 620kg of chloroethane are added into an alkylation kettle, after the feeding is finished, all feeding valves are closed, stirring and steam heating are started, when the temperature of the materials is raised to 90-95 ℃, the steam is stopped, the temperature of the materials in the alkylation kettle naturally rises to about 120 ℃, the pressure is about 1.45MPa, 25 wt.% of liquid alkali (sodium hydroxide aqueous solution) is slowly added into the kettle by using a pressure pump, the adding amount of the liquid alkali is about 700kg, the feeding time is about 2.0 hours, the liquid alkali is slowly dripped, after the liquid alkali is added, the temperature is 125-135 ℃, the pressure is 1.35-1.45 MPa, the temperature is kept for 1 hour, the sampling and the end point measuring are carried out, and when the peak area of the raw material content is less than or equal to 0.5% (chromatogram) is taken as the end point of the reaction.
Slowly opening a vent valve, discharging the pressure in the alkylation kettle to normal pressure, keeping the temperature of materials in the alkylation kettle at about 90 ℃, and transferring the materials in the alkylation kettle to a neutralization kettle under the nitrogen atmosphere.
2) Starting a neutralization kettle for stirring, opening a jacket of the neutralization kettle for cooling by cooling water, starting to dropwise add 20 wt.% of sodium carbonate aqueous solution when the temperature of materials in the kettle is reduced to 25-35 ℃, keeping the temperature of the materials below 35 ℃ all the time in the process of dropwise adding the sodium carbonate, stopping dropwise adding the sodium carbonate when the pH value of a material medium is 6-6.5, continuing to stir for 30 minutes, and preparing for filter pressing. After the above-mentioned materials are centrifugally separated, the mother liquor is undergone the process of waste water treatment, and the filter cake (crude product) is undergone the process of distillation.
3) Putting the crude product into a distillation kettle, starting a vacuum pump, reducing the vacuum degree in the distillation kettle to-0.095 MPa, starting a jacket for heat conducting oil to heat, and receiving the distillate at 165-180 ℃ to obtain the product of m-hydroxy-N, N-diethylaniline.
4) 528.5kg of m-hydroxy-N, N-diethylaniline is prepared, and the total yield is 95.4%; the product purity (HPLC or GC) is more than or equal to 99.2 percent, and the freezing point is more than or equal to 72.0 ℃.
Example 2
1) Adding 1080kg of water, 365kg of m-aminophenol and 630kg of chloroethane into an alkylation kettle, after the feeding is finished, closing all feeding valves, starting stirring and heating steam, when the temperature of the materials is raised to 85-90 ℃, stopping the steam, naturally raising the temperature of the materials in the alkylation kettle to about 125-130 ℃, controlling the pressure to be about 1.35MPa, starting to slowly add 25 wt.% of liquid alkali (sodium hydroxide aqueous solution) into the kettle by using a pressure pump, controlling the adding amount of the liquid alkali to be about 700kg, controlling the feeding time to be about 2.5 hours, slowly dropwise adding the liquid alkali, controlling the temperature to be about 135 ℃ after the liquid alkali is added, controlling the pressure to be 1.25-1.30 MPa, carrying out heat preservation reaction for 1 hour, sampling and measuring the end point, and controlling the peak area (chromatogram) of the raw material content to be less than or equal to 0.5 percent to be the end point of the reaction.
Slowly opening a vent valve, discharging the pressure in the alkylation kettle to normal pressure, keeping the temperature of materials in the alkylation kettle at about 90 ℃, and transferring the materials in the alkylation kettle to a neutralization kettle under the nitrogen atmosphere.
2) Starting a neutralization kettle for stirring, opening a jacket of the neutralization kettle for cooling water, starting to dropwise add 20 wt.% of sodium carbonate aqueous solution when the temperature of materials in the kettle is reduced to 30-35 ℃, keeping the temperature of the materials below 35 ℃ all the time in the process of dropwise adding the sodium carbonate, stopping dropwise adding the sodium carbonate when the pH value of a material medium is 6-6.5, and continuing stirring for 30 minutes to prepare for filter pressing. After the above-mentioned materials are centrifugally separated, the mother liquor is undergone the process of waste water treatment, and the filter cake (crude product) is undergone the process of distillation.
3) And putting the crude product into a distillation kettle, starting a vacuum pump, reducing the vacuum degree in the distillation kettle to-0.095 MPa, starting jacket heat conduction oil for heating, and receiving the distillate at 165-180 ℃ to obtain the m-hydroxy-N, N-diethylaniline product.
4) 519kg of m-hydroxy-N, N-diethylaniline is prepared, and the total yield is 93.7 percent; the product purity (HPLC or GC) is more than or equal to 99.0 percent, and the freezing point is more than or equal to 72.0 ℃.
Example 3
1) Adding 900kg of water, 365kg of m-aminophenol and 610kg of chloroethane into an alkylation kettle, after the materials are fed, closing all feeding valves, starting stirring and heating steam, when the materials are heated to 85-90 ℃, stopping steam, naturally raising the temperature of the materials in the alkylation kettle to about 115-120 ℃, keeping the pressure at about 1.3MPa, slowly adding 25 wt.% of liquid alkali (sodium hydroxide aqueous solution) into the kettle by using a pressure pump, keeping the addition amount of the liquid alkali at about 660kg, slowly adding the liquid alkali within about 2.0 hours after the feeding time is about 2.0 hours, keeping the temperature at 120-125 ℃ after the liquid alkali is added, keeping the temperature for about 60 minutes after the liquid alkali is added, sampling and measuring the end point, and taking (chromatogram) as the reaction end point when the peak area of the content of the raw materials is less than or equal to 0.5 percent.
Slowly opening a vent valve, discharging the pressure in the alkylation kettle to normal pressure, keeping the temperature of materials in the alkylation kettle at about 90 ℃, and transferring the materials in the alkylation kettle to a neutralization kettle under the nitrogen atmosphere.
2) Starting a neutralization kettle for stirring, opening a jacket of the neutralization kettle for cooling water, starting to dropwise add 20 wt.% of sodium carbonate aqueous solution when the temperature of materials in the kettle is reduced to 30-35 ℃, keeping the temperature of the materials below 35 ℃ all the time in the process of dropwise adding the sodium carbonate, stopping dropwise adding the sodium carbonate when the pH value of a material medium is 5.5-6.0, continuing to stir for 30 minutes, and preparing for filter pressing. After the above-mentioned materials are centrifugally separated, the mother liquor is undergone the process of waste water treatment, and the filter cake (crude product) is undergone the process of distillation.
3) Putting the crude product into a distillation kettle, starting a vacuum pump, reducing the vacuum degree in the distillation kettle to-0.095 MPa, starting jacket heat conduction oil for heating, and receiving the distillate at 165-180 ℃ to obtain the product.
4) 515.5kg of m-hydroxy-N, N-diethylaniline is prepared, and the total yield is 93.05%; the product purity (HPLC or GC) is more than or equal to 98.8 percent, and the freezing point is more than or equal to 71.8 ℃.
Example 4
1) Adding 900kg of water, 365kg of m-aminophenol and 600kg of chloroethane into an alkylation kettle, closing all feeding valves after the feeding is finished, starting stirring and heating steam, stopping the steam when the temperature of the materials is raised to 85-95 ℃, naturally raising the temperature of the materials in the alkylation kettle to about 120-125 ℃, keeping the pressure at about 1.1-1.15 MPa, slowly adding 25 wt.% of liquid alkali (sodium hydroxide aqueous solution) into the kettle by using a pressure pump, keeping the addition of the liquid alkali at about 600kg, slowly adding the liquid alkali about 2.5 hours after the feeding is finished, keeping the temperature at 120-125 ℃, keeping the pressure at 1.2-1.25 MPa, reacting for 50 minutes, sampling and measuring the end point, and taking the reaction when the peak area of the content of the raw materials is less than or equal to 0.5%.
Slowly opening a vent valve, discharging the pressure in the alkylation kettle to normal pressure, keeping the temperature of materials in the alkylation kettle at about 90 ℃, and transferring the materials in the alkylation kettle to a neutralization kettle under the nitrogen atmosphere.
2) Starting a neutralization kettle for stirring, opening a jacket of the neutralization kettle for cooling water, starting to dropwise add 20 wt.% of sodium carbonate aqueous solution when the temperature of materials in the kettle is reduced to 20-25 ℃, keeping the temperature of the materials below 30 ℃ all the time in the process of dropwise adding the sodium carbonate, stopping dropwise adding the sodium carbonate when the pH value of a material medium is 5.5-6.5, continuing to stir for 30 minutes, and preparing for filter pressing. After the above-mentioned materials are centrifugally separated, the mother liquor is undergone the process of waste water treatment, and the filter cake (crude product) is undergone the process of distillation.
3) Putting the crude product into a distillation kettle, starting a vacuum pump, reducing the vacuum degree in the distillation kettle to-0.095 MPa, starting jacket heat conduction oil for heating, and receiving the distillate at 165-180 ℃ to obtain the product.
4) 510kg of m-hydroxy-N, N-diethylaniline is prepared, and the total yield is 92.1%; the product purity (HPLC or GC) is more than or equal to 98.5 percent, and the freezing point is more than or equal to 71.5 ℃.
Example 5
1) Adding 900kg of water, 365kg of m-aminophenol and 580kg of chloroethane into an alkylation kettle, after the materials are fed, closing all feeding valves, starting stirring and heating steam, when the materials are heated to 85-90 ℃, stopping steam, naturally raising the temperature of the materials in the alkylation kettle to about 120-125 ℃, keeping the pressure at about 1.3MPa, slowly adding 25 wt.% of liquid alkali (sodium hydroxide aqueous solution) into the kettle by using a pressure pump, keeping the addition amount of the liquid alkali at about 590kg, slowly adding the liquid alkali for about 2.0 hours, keeping the temperature at 130-135 ℃ after the liquid alkali is added, keeping the pressure at 1.2-1.25 MPa, keeping the temperature for 1 hour, sampling and measuring the end point, and taking (chromatogram) as the reaction end point when the peak area of the content of the raw materials is less than or equal to 0.5% (chromatogram).
The vent valve is opened slowly, after the pressure in the alkylation kettle is released to normal pressure, the temperature of the materials in the alkylation kettle is about 90 ℃, and then the materials in the alkylation kettle are transferred to the neutralization kettle under the nitrogen atmosphere.
2) Starting a neutralization kettle for stirring, opening a jacket of the neutralization kettle for cooling water, starting to dropwise add 20 wt.% of sodium carbonate aqueous solution when the temperature of materials in the kettle is reduced to 20-25 ℃, keeping the temperature of the materials below 25 ℃ all the time in the process of dropwise adding the sodium carbonate, stopping dropwise adding the sodium carbonate when the pH value of a material medium is 5.5-6.0, continuing to stir for 30 minutes, and preparing for filter pressing. After the above-mentioned materials are centrifugally separated, the mother liquor is undergone the process of waste water treatment, and the filter cake (crude product) is undergone the process of distillation.
3) Putting the crude product into a distillation kettle, starting a vacuum pump, reducing the vacuum degree in the distillation kettle to-0.095 MPa, starting jacket heat conduction oil for heating, and receiving the distillate at 165-180 ℃ to obtain the product.
4) 500kg of m-hydroxy-N, N-diethylaniline is prepared, and the total yield is 90.25%; the product purity (HPLC or GC) is more than or equal to 98.0 percent, and the freezing point is more than or equal to 71.0 ℃.
Claims (10)
1. A preparation method of m-hydroxy-N, N-diethylaniline comprises the following steps:
heating and mixing m-aminophenol, halogenated hydrocarbon and water, and reacting to generate a mixture 1 containing a crude product of m-hydroxy-N, N-diethylaniline;
slowly mixing the mixture 1 with an acid binding agent to obtain a mixture 2;
incubating the mixture 2 at 100 ℃ to 165 ℃, preferably at 100 ℃ to 155 ℃, more preferably at 120 ℃ to 135 ℃;
cooling the mixture 2, adjusting the pH value of the mixture 2 to 5.5-6.5, and filtering to obtain a solid, namely a crude product;
distilling the crude product to obtain a distillate with the temperature of 165-180 ℃, namely the m-hydroxy-N, N-diethylaniline.
2. The method for producing m-hydroxy-N, N-diethylaniline according to claim 1 wherein the halogenated hydrocarbon is selected from any one or more of ethyl chloride, ethyl bromide and ethyl iodide, preferably ethyl chloride.
3. The method for preparing m-hydroxy-N, N-diethylaniline according to claim 1, wherein said mixing said mixture 1 with an acid-binding agent is carried out slowly, and said acid-binding agent is added to said mixture 1 slowly, so that the addition of the acid-binding agent is completed within 1 to 4 hours.
4. The method for preparing m-hydroxy-N, N-diethylaniline according to claim 3, wherein said acid scavenger is selected from any one or more of sodium hydroxide, magnesium oxide or soda ash;
optionally, the acid scavenger is an aqueous sodium hydroxide solution.
5. The method for producing m-hydroxy-N, N-diethylaniline according to any one of claims 1 to 4, wherein an alkaline solution selected from any one or both of an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution is used for adjusting the pH of the mixture 2;
optionally, the alkaline solution is added dropwise to adjust the pH of the mixture 2.
6. The process for the preparation of m-hydroxy-N, N-diethylaniline according to any one of claims 1 to 4, wherein the heating is such that the temperature of the mixture of m-aminophenol and a halogenated hydrocarbon with water is raised to 80 to 100 ℃ in a closed vessel, after which the heating is stopped, so that the temperature of the mixture of m-aminophenol, a halogenated hydrocarbon with water is naturally raised to 100 to 165 ℃, preferably to 100 to 155 ℃, more preferably to 120 to 135 ℃;
optionally, the mixture 2 is incubated for 10 to 60 minutes, preferably 10 to 30 minutes or 30 to 60 minutes.
7. The process for producing m-hydroxy-N, N-diethylaniline according to any one of claims 1 to 4, wherein the operating pressure at which the crude product is distilled is from-0.085 MPa to-0.095 MPa.
8. The method for producing m-hydroxy-N, N-diethylaniline according to any one of claims 1 to 4, wherein the mass ratio of said water, said m-aminophenol and said halogenated hydrocarbon is (2 to 10):1 (1.45 to 2.50);
optionally, the mass ratio of the acid scavenger to the halogenated hydrocarbon is 2 (1.7 to 5.5).
9. The method for producing m-hydroxy-N, N-diethylaniline according to any one of claims 1 to 4, wherein the temperature of mixture 2 is 10 ℃ to 35 ℃ when the pH of mixture 2 is adjusted;
optionally, the mixture 2 is separated after the pH adjustment, and the solid material obtained is the crude product.
10. The method for producing m-hydroxy-N, N-diethylaniline according to any one of claims 1 to 4, wherein the mixture 1 is transferred under an inert atmosphere gas atmosphere while being transferred between different containers;
optionally, the inert atmosphere gas is selected from an inert gas or nitrogen.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5202485A (en) * | 1989-11-10 | 1993-04-13 | Sumitomo Chemical Co., Ltd. | Process for preparing N-alkylaminophenols |
| CN103012164A (en) * | 2012-12-26 | 2013-04-03 | 上海安诺芳胺化学品有限公司 | Method for continuously producing m-diethylaminophenol through channelization |
| CN104860834A (en) * | 2015-04-16 | 2015-08-26 | 南通恒盛精细化工有限公司 | Preparation method of disperse fluorescent dye intermediate 4-(N,N-diethylamino)salicylaldehyde |
| CN105001666A (en) * | 2015-07-20 | 2015-10-28 | 福州大学 | Asymmetric near-infrared squaraine dye, preparation method thereof and application thereof |
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2022
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|---|---|---|---|---|
| US5202485A (en) * | 1989-11-10 | 1993-04-13 | Sumitomo Chemical Co., Ltd. | Process for preparing N-alkylaminophenols |
| CN103012164A (en) * | 2012-12-26 | 2013-04-03 | 上海安诺芳胺化学品有限公司 | Method for continuously producing m-diethylaminophenol through channelization |
| CN104860834A (en) * | 2015-04-16 | 2015-08-26 | 南通恒盛精细化工有限公司 | Preparation method of disperse fluorescent dye intermediate 4-(N,N-diethylamino)salicylaldehyde |
| CN105001666A (en) * | 2015-07-20 | 2015-10-28 | 福州大学 | Asymmetric near-infrared squaraine dye, preparation method thereof and application thereof |
Non-Patent Citations (1)
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| 戈乔华等: "2-(5-甲基-1, 3, 4-噁二唑-2-基)-6-二乙氨基荧烷的合成", 浙江工业大学学报, vol. 34, no. 5, pages 498 - 501 * |
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