CN108558710B - Preparation method of N, N-dibutyl m-aminophenol - Google Patents
Preparation method of N, N-dibutyl m-aminophenol Download PDFInfo
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
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Abstract
The invention relates to a preparation method of N, N-dibutyl m-aminophenol, which comprises the following steps of 1, carrying out alkylation reaction on sodium m-aminophenol, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the alkylation reaction temperature is 80-200 ℃, and the alkylation reaction time is 2-5 hours, so as to obtain an alkylate solution; 2, mixing the alkylate solution with an alkaline reagent and water for an alkali fusion reaction at the temperature of 200-350 ℃ for 1-3 hours to obtain alkylated sodium phenolate, and then adding water; 3, carrying out acid precipitation reaction on the alkylated sodium phenolate and an acidic reagent for 0.5-3h to obtain a crude product of N, N-dibutyl m-aminophenol; 4 refining to obtain N, N-dibutyl m-aminophenol; the N, N-dibutyl m-aminophenol prepared by the method has high yield and low cost, reduces the types of byproducts and lightens the burden of post-treatment.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation, and particularly relates to a preparation method of N, N-dibutyl m-aminophenol.
Background
N, N-dibutyl m-aminophenol is a key intermediate of pressure-sensitive color former ODB-2. ODB-2 is the most widely used black color former in the world at present, the color forming picture has deep dyeing, good storage stability, simple structure and low price, and the compound can be applied to various pressure-sensitive and heat-sensitive recording papers such as faxes, labels and the like, can be used independently, and can also be used on high-speed faxing paper together with other color formers. The structural formula is as follows:
among them, the purity and cost of N, N-dibutylm-aminophenol are directly related to the quality and yield of ODB-2 products. The traditional synthesis process comprises the steps of firstly carrying out alkali fusion and acid-out reaction on the initial raw material sodium metaaminophenol and sodium hydroxide to obtain meta-aminophenol, and then reacting the meta-aminophenol with an alkylating reagent to obtain N, N-dibutyl meta-aminophenol. The process is as follows:
the preparation method provided by the traditional process has the advantages of complex alkali fusion reaction product, poor selectivity, low target product conversion rate and higher post-treatment difficulty; the phenolic hydroxyl group of the alkylation reaction has certain activity and can participate in the reaction, so that the quality and the yield of the final product are influenced. The overall process flow has low yield and large amount of waste water.
Disclosure of Invention
The invention aims to provide a preparation method of N, N-dibutyl m-aminophenol, which has the advantages of high yield, low cost, small pollution and simple and convenient process.
To achieve the above object, the present invention comprises the steps of,
(1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1 (2-4), and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: (1.5-4), wherein the alkylation reaction temperature is 80-200 ℃, and the alkylation reaction time is 2-5 hours, so as to obtain an alkylate solution;
(2) mixing the alkylate solution obtained in the step (1) with an alkaline reagent and water for alkali fusion reaction, wherein the molar ratio of the raw material sodium metanilic sulfonate in the step (1) to the alkaline reagent in the step (2) is 1 (2-4), and the mass ratio of the water to the alkaline reagent is (0-3): 1, namely, the mass fraction of an alkaline reagent in water is 25-100%, the alkali fusion reaction temperature is 200-350 ℃, the reaction time is 1-3 hours, alkylated sodium phenolate is obtained, then water is added, and the mass ratio of the added water to the sodium metaaminobenzenesulfonate is (1-4): 1;
(3) carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1: (0.5-2), and reacting for 0.5-3h to obtain a crude product of N, N-dibutyl m-aminophenol;
(4) refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
further, the halogenated hydrocarbon includes fluorobutane, chlorobutane, bromobutane or iodobutane.
Further, the acid scavenger comprises magnesium oxide, sodium hydroxide, potassium hydroxide or ammonia water.
Further, the alkaline reagent in the step (2) is one or two of sodium hydroxide and potassium hydroxide.
Further, in the step (3), the acidic reagent includes hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid or trifluoroacetic acid.
Further, in the step (3), when the acid precipitation reaction is finished, adjusting the pH of the solution to 2-7, and continuing the reaction for 0.5-3 hours.
Further, in the step (4), the refining includes water washing, dehydration by heating and drying. 8. The process for the preparation of N, N-dibutyl-m-aminophenol according to claim 1 or 7, characterized in that: the temperature of heating dehydration is 100-250 ℃.
Further, in the step (1), sodium m-aminobenzenesulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent are subjected to alkylation reaction, the sodium aminobenzenesulfonate is firstly dissolved in the solvent, the mass fraction of the sodium m-aminobenzenesulfonate in the solvent is 10% -65%, and then the halogenated hydrocarbon and the acid-binding agent are sequentially added.
Further, the solvent is water.
The invention has the following positive effects:
(1) the invention has high utilization rate of raw materials and reduces the discharge of waste water.
(2) The invention has high yield and low cost, and the yield can be improved to 65 percent from about 45 percent of the traditional process.
(3) The invention reduces the byproduct variety and lightens the burden of post-treatment.
(4) The product prepared by the invention has high purity.
Detailed Description
The invention provides a preparation method of N, N-dibutyl m-aminophenol, which comprises the following steps: the method comprises the steps of taking sodium m-aminobenzenesulfonate as an initial raw material, carrying out alkylation reaction, alkali fusion reaction and acid precipitation reaction, reacting the raw material with an alkylating reagent, then carrying out alkali fusion, and finally reacting with an acidic reagent to obtain a target product.
The synthetic route of the technical scheme is as follows:
all the raw materials of the invention are not particularly limited in source and can be purchased in the market.
The purity of all raw materials is not particularly limited in the present invention, and may be in the purity of raw materials conventionally used in the production of N, N-dibutylbis-m-aminophenol well known to those skilled in the art, and is preferably industrially pure.
Dissolving sodium metanilic sulfonate in a solvent, and then carrying out alkylation reaction with an alkylation reagent under the action of an acid-binding agent; the alkylating agent is halogenated hydrocarbon, including but not limited to one or more of fluorobutane, chlorobutane, bromobutane and iodobutane, and most preferably chlorobutane or bromobutane; the molar ratio of the alkyl reagent halogenated hydrocarbon to the sodium metanilic sulfonate is (2-4): 1, more preferably (2.3 to 3.0): 1; the acid-binding agent for the alkylation reaction comprises one or more of alkali metal oxides and hydroxides such as magnesium oxide, sodium hydroxide and potassium hydroxide, and organic bases such as ammonia water, and most preferably sodium hydroxide or potassium hydroxide; the preferable molar ratio of the alkaline reagent to the sodium metanilic sulfonate is (2-4): 1, more preferably (2.8 to 3.2): 1; the alkylation reaction temperature is preferably 80-200 ℃, and more preferably 100-150 ℃; the alkylation reaction time is preferably 2 to 5 hours, and more preferably 3 to 4 hours. Preferably, the solvent is water or an alcoholic polar solution.
The step (1) of the invention is as follows: (1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1 (2-4), and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: (1.5-4), the alkylation reaction temperature is 80-200 ℃, and the alkylation reaction time is 2-5 hours, so as to obtain the alkylate solution.
Specifically, at room temperature, in order to ensure that the alkylation reaction is stably carried out, the sodium metanilic sulfonate is preferably fully dissolved in the solvent before the reaction; the method for dissolving in the solvent is not particularly limited, and the method can be operated by methods well known to those skilled in the art, preferably, the mass fraction of the sodium metanilino sulfonate in the solvent is 10% -65%, the temperature at room temperature is preferably 20-25 ℃, then the halogenated hydrocarbon and the acid-binding agent are sequentially added and mixed uniformly, and then the alkylation reaction is carried out, wherein the mixing mode is preferably stirring and mixing; the stirring time is preferably 20-30 minutes; the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1 (2-4), and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: (1.5-4), wherein the alkylation reaction temperature is 80-200 ℃, and the alkylation reaction time is 2-5 hours, so as to obtain an alkylate solution; the stirring mode is not particularly limited in the invention, and the stirring mode known to a person skilled in the art can be used; the present invention is not particularly limited to the other conditions for the mixing at room temperature, and the mixing conditions before the alkylation reaction, which are well known to those skilled in the art, may be used.
The step (2) of the invention is as follows: (2) performing alkali fusion reaction on the alkylate solution obtained in the step (1) and an alkaline reagent, wherein the molar ratio of the raw material sodium metanilic sulfonate in the step (1) to the alkaline reagent in the step (2) is 1 (2-4), and the mass ratio of water to the alkaline reagent is (0-3): 1, namely, the mass fraction of the alkaline reagent in water is 25-100%, the alkali fusion reaction temperature is 200-350 ℃, and the reaction time is 1-3 hours to obtain the alkylated sodium phenolate.
Specifically, after the alkylation reaction is completed, the reaction intermediate (A) is obtained by standing and layering
) Sodium N, N-dibutylbetanilic acid sulfonate. The standing and layering manner is not particularly limited in the invention, and can be a standing and layering manner well known to those skilled in the art; the conditions for the standing and layering are not particularly limited in the present invention, and the conditions for the standing and layering known to those skilled in the art may be used; the invention obtains a reaction intermediate (
) Then, the solution of alkylate obtained in the step (1) and an alkaline reagent are subjected to an alkali fusion reaction, namely, the intermediate, a solvent and the alkaline reagent are heated to react to obtain a reaction intermediate (1)
) Sodium N, N-dibutyl meta-aminophenol; the solvent is preferably one or more of water, alcohols and other polar solvents, and more preferably water; the alkaline reagent is preferably one or the combination of two mixtures of sodium hydroxide and potassium hydroxide; the alkali fusion reaction temperature is 200-350 ℃, and more preferably 220-300 ℃; the alkali fusion reaction time is 1-3 hours. The present invention is not particularly limited with respect to other conditions of the reaction, and the conditions of the alkali fusion reaction well known to those skilled in the art may be used; the heating method of the present invention is not particularly limited, and may be any heating method known to those skilled in the art; the reaction vessel used in the present invention is not particularly limited, and may be any reaction vessel known to those skilled in the art for use in alkali fusion reactions.
The step (3) of the invention is as follows: (3) carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1: (0.5-2), the reaction temperature is 20-100 ℃, and the reaction time is 0.5-3h, so as to obtain a crude product of N, N-dibutyl m-aminophenol;
specifically, after the alkali fusion reaction is completed, the temperature is reduced to obtain a reaction intermediate (
) Sodium N, N-dibutyl meta-aminophenol. The cooling method is not particularly limited, and the cooling method known to those skilled in the art can be used; the temperature reduction conditions are not particularly limited in the present invention, and the temperature reduction conditions known to those skilled in the art may be used; the invention obtains a reaction intermediate (
) Then, neutralizing with water and an acid reagent, namely carrying out acid precipitation reaction to obtain a crude product of N, N-dibutyl m-aminophenol; the acidic reagent is preferably inorganic acid such as hydrochloric acid, sulfuric acid and nitric acid, or organic acid such as formic acid, acetic acid and trifluoroacetic acid, and is more preferably one or a mixture of two of hydrochloric acid and sulfuric acid; the temperature of the acid precipitation reaction is not particularly limited in the present invention, and the temperature of the acid precipitation reaction known to those skilled in the art may be preferably 40 to 80 ℃; at the end point of the acidification reaction, the PH value is adjusted to be 2-7, and more preferably, the PH value is adjusted to be 6-7.
The step (4) of the invention is as follows: (4) refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
after the reaction is finished, the qualified product of the N, N-dibutyl m-aminophenol is finally obtained by preferably performing water washing, heating dehydration and drying post-treatment. The method of washing with water in the present invention is not particularly limited, and the washing with water known to those skilled in the art may be performed, preferably, washing with hot water; the temperature of the hot water is not particularly limited, and the hot water can be heated in a temperature manner known by a person skilled in the art, and is preferably 40-60 ℃; the number of washing is not particularly limited in the present invention, and the number of washing in such post-reaction treatment well known to those skilled in the art may be used; the heating dehydration method is not particularly limited in the present invention, and the heating dehydration method known to those skilled in the art may be used; the temperature for the heat dehydration is not particularly limited, and the temperature for the heat dehydration in the post-treatment of the compound, which is well known to those skilled in the art, can be used, and the refining temperature is 100-250 ℃, preferably 110-140 ℃; the drying method in the present invention is not particularly limited, and may be drying methods in such post-reaction treatments well known to those skilled in the art, and preferably vacuum drying is employed; the conditions for vacuum drying in the present invention are not particularly limited, and those known to those skilled in the art may be used.
The N, N-dibutyl m-aminophenol prepared by the method is analyzed by Gas Chromatography (GC), the purity of the N, N-dibutyl m-aminophenol prepared by the method is more than or equal to 98 percent, and the reaction yield is more than or equal to 60 percent.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of N, N-dibutyl m-aminophenol provided by the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
The method comprises the following steps of,
(1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1:3, and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: (2) the alkylation reaction temperature is 100 ℃, and the alkylation reaction time is 3 hours, so as to obtain an alkylate solution; the halogenated hydrocarbon is fluorobutane. The acid-binding agent is magnesium oxide.
In the step (1), sodium m-aminobenzenesulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent are subjected to alkylation reaction, the sodium aminobenzenesulfonate is firstly dissolved in the solvent, the mass fraction of the sodium m-aminobenzenesulfonate in the solvent is 40%, and then the halogenated hydrocarbon and the acid-binding agent are sequentially added.
The solvent is water.
(2) Mixing the alkylate solution obtained in the step (1) with an alkaline reagent and water for alkali fusion reaction, wherein the molar ratio of sodium m-sulfanilate (sodium m-sulfanilate is used as a raw material in the step (1)) to the alkaline reagent is 1:3, and the mass ratio of water to the alkaline reagent is (2): 1, obtaining alkylated sodium phenolate by alkali fusion reaction at the temperature of 280 ℃ for 2 hours, and then adding water, wherein the mass ratio of the added water to the sodium metanilic sulfonate (the sodium metanilic sulfonate is used as the raw material in the step (1)) is 3: 1; the alkaline reagent is sodium hydroxide.
(3) Carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1: 1, reacting for 1.5h to obtain crude N, N-dibutyl m-aminophenol; the acidic reagent is nitric acid solution. When the acid precipitation reaction is finished, the pH value of the solution is adjusted to 5, and the reaction is continued for 1.5 h.
(4) Refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
the refining comprises water washing, heating dehydration and drying. The temperature for heating dehydration is 180 ℃. The GC content of the final product N, N-dibutyl m-aminophenol is 99.2 percent, and the yield is 69.3 percent (calculated by the sodium m-aminophenol sulfonate). And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Example 2
The method comprises the following steps of,
(1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1:2, and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1:4, the alkylation reaction temperature is 80 ℃, and the alkylation reaction time is 5 hours, so as to obtain an alkylate solution; the halogenated hydrocarbon is chlorobutane. The acid-binding agent is potassium hydroxide.
In the step (1), sodium m-aminobenzenesulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent are subjected to alkylation reaction, the sodium aminobenzenesulfonate is firstly dissolved in the solvent, the mass fraction of the sodium m-aminobenzenesulfonate in the solvent is 10%, and then the halogenated hydrocarbon and the acid-binding agent are sequentially added.
The solvent is water.
(2) Mixing the alkylate solution obtained in the step (1) with an alkaline reagent and water for alkali fusion reaction, wherein the molar ratio of sodium m-sulfanilate (sodium m-sulfanilate is used as a raw material in the step (1)) to the alkaline reagent is 1:2, and the mass ratio of water to the alkaline reagent is 0.1: 1, obtaining alkylated sodium phenolate by alkali fusion reaction at the temperature of 350 ℃ for 1 hour, and then adding water, wherein the mass ratio of the added water to the sodium metanilic sulfonate (the sodium metanilic sulfonate is used as the raw material in the step (1)) is 1: 1; the alkaline reagent is potassium hydroxide.
(3) Carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1: 0.5, reacting for 3 hours to obtain crude N, N-dibutyl m-aminophenol; the acidic reagent is formic acid solution. When the acid precipitation reaction is finished, the pH value of the solution is adjusted to be 2, and the reaction is continued for 0.5 h.
(4) Refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
the refining comprises water washing, heating dehydration and drying. The temperature for heating dehydration is 100 ℃. The GC content of the final product N, N-dibutyl m-aminophenol is 99 percent, and the yield is 68.8 percent (calculated by the sodium m-aminophenol sulfonate). And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Example 3
The method comprises the following steps of,
(1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1:4, and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: 1.5, the alkylation reaction temperature is 200 ℃, and the alkylation reaction time is 2 hours, so as to obtain an alkylate solution; the halogenated hydrocarbon is iodobutane. The acid-binding agent is ammonia water.
In the step (1), sodium m-aminobenzenesulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent are subjected to alkylation reaction, the sodium aminobenzenesulfonate is firstly dissolved in the solvent, the mass fraction of the sodium m-aminobenzenesulfonate in the solvent is 65%, and then the halogenated hydrocarbon and the acid-binding agent are sequentially added.
The solvent is water.
(2) Mixing the alkylate solution obtained in the step (1) with an alkaline reagent and water for alkali fusion reaction, wherein the molar ratio of sodium m-sulfanilate (sodium m-sulfanilate is used as a raw material in the step (1)) to the alkaline reagent is 1:4, and the mass ratio of water to the alkaline reagent is 3: 1, obtaining alkylated sodium phenolate by alkali fusion reaction at the temperature of 200 ℃ for 3 hours, and then adding water, wherein the mass ratio of the added water to the sodium metanilic sulfonate (the sodium metanilic sulfonate is used as the raw material in the step (1)) is 4: 1; the alkaline reagent is potassium hydroxide.
(3) Carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1:2, reacting for 0.5h to obtain crude N, N-dibutyl m-aminophenol; the acidic reagent is acetic acid or trifluoroacetic acid solution. When the acid precipitation reaction is finished, the pH value of the solution is adjusted to 7, and the reaction is continued for 3 hours.
(4) Refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
the refining comprises water washing, heating dehydration and drying. The temperature for heating dehydration is 250 ℃. The GC content of the final product N, N-dibutyl m-aminophenol is 99 percent, and the yield is 65 percent (calculated by the sodium m-aminophenol sulfonate). And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Example 4
The method comprises the following steps of,
(1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1:3, and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: (2) the alkylation reaction temperature is 100 ℃, and the alkylation reaction time is 3 hours, so as to obtain an alkylate solution; the halogenated hydrocarbon is fluorobutane. The acid-binding agent is magnesium oxide.
In the step (1), sodium m-aminobenzenesulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent are subjected to alkylation reaction, the sodium aminobenzenesulfonate is firstly dissolved in the solvent, the mass fraction of the sodium m-aminobenzenesulfonate in the solvent is 40%, and then the halogenated hydrocarbon and the acid-binding agent are sequentially added.
The solvent is water.
(2) And (2) carrying out alkali fusion reaction on the alkylate solution obtained in the step (1) and an alkaline reagent, wherein the molar ratio of sodium metanilic sulfonate (sodium metanilic sulfonate is used as the raw material in the step (1)) to the alkaline reagent is 1:3, the alkali fusion reaction temperature is 280 ℃, the reaction time is 2 hours, so that alkylated sodium phenolate is obtained, then water is added, and the mass ratio of the added water to the sodium metanilic sulfonate (sodium metanilic sulfonate is used as the raw material in the step (1)) is 3: 1; the alkaline reagent is sodium hydroxide.
(3) Carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1: 1, reacting for 1.5h to obtain crude N, N-dibutyl m-aminophenol; the acidic reagent is nitric acid solution. When the acid precipitation reaction is finished, the pH value of the solution is adjusted to 5, and the reaction is continued for 1.5 h.
(4) Refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
the refining comprises water washing, heating dehydration and drying. The temperature for heating dehydration is 180 ℃. The GC content of the final product N, N-dibutyl m-aminophenol is 99.1 percent, and the yield is 69.2 percent (calculated by the sodium m-aminophenol sulfonate). And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Example 5
(1) Adding 200g of an aqueous solution (47%) of sodium metaaminobenzenesulfonate and 180g of n-butyl bromide into a 1L reaction kettle with a high-pressure pump, closing the reaction kettle, starting stirring, heating to 110 ℃, slowly adding 280g of an aqueous solution (20%) of sodium hydroxide, controlling the dropping speed to ensure that the pH value is 8-9, keeping the temperature for 3 hours after the addition is finished, detecting that the content of a raw material is less than 0.5% by using HP L C, stopping the reaction, cooling, standing and layering to obtain an upper white floccule, wherein the content of the HP L C is 96%, and the content of the raw material is less than 0.3.
(2) Adding 155g of potassium hydroxide, 100g of sodium hydroxide and 200g of water into a reaction kettle of 1L to prepare an alkali liquor, heating to 230 ℃, slowly adding the obtained intermediate, finishing the addition within 2 hours, releasing heat to 300 ℃, keeping the temperature for 2 hours, detecting that the content of the raw material is less than 0.5% by using HP L C, stopping the reaction, cooling, wherein the content of HP L C is 85% and the content of the raw material is less than 0.5%, and in order to avoid caking after cooling and incapability of acid precipitation, adding 500m of L water into the solution for dilution and later use.
(3) Slowly adding hydrochloric acid with the mass fraction of 30% into the reaction kettle, adjusting the pH value to 6-7, standing and layering to obtain an upper-layer black oily substance.
(4) Washing twice, heating at 120 deg.c to dewater, and drying to obtain the final product N, N-dibutyl m-aminophenol with GC content of 98% and yield of 65% (calculated on m-aminophenol sodium sulfonate).
And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Example 6
(1) Adding 200g of an aqueous solution (49%) of sodium m-aminobenzenesulfonate, 135g of n-butyl chloride into a 1L reaction kettle with a high-pressure pump, closing the reaction kettle, starting stirring, heating to 150 ℃, slowly adding 280g of an aqueous solution (20%) of sodium hydroxide, controlling the dropping speed to ensure that the pH value is 8-9, keeping the temperature for 3 hours after the addition is finished, detecting that the content of a raw material is less than 0.5% by using HP L C, stopping the reaction, cooling, standing and layering to obtain an upper white floccule, wherein the content of the HP L C is 95%, and the content of the raw material is less than 0..
(2) Adding 155g of potassium hydroxide, 100g of sodium hydroxide and 200g of water into a reaction kettle of 1L to prepare an alkali liquor, heating to 230 ℃, slowly adding the intermediate, adding the intermediate after 2 hours, discharging heat to 300 ℃, keeping the temperature for 2 hours, detecting that the content of the raw material is less than 0.5% by using HP L C, stopping the reaction, cooling, wherein the content of HP L C is 85% and the content of the raw material is less than 0.5%, and adding 500m of L water into the solution to dilute the solution for later use in order to avoid caking and incapability of acid precipitation after cooling.
(3) Slowly adding 30% hydrochloric acid into the reaction kettle, adjusting the pH value to 5-6, standing and layering to obtain an upper black oily substance;
(4) washing twice, heating at 120 deg.c to dewater and drying to obtain final product N, N-dibutyl m-aminophenol with GC content of 98% and yield of 60% (calculated on m-aminophenol sodium sulfonate).
And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Example 7
(1) Adding 200g of an aqueous solution (50%) of sodium metanilic sulfonate into a 1L reaction kettle with a high-pressure pump, 203g of n-butyl bromide, closing the reaction kettle, starting stirring, heating to 140 ℃, slowly adding 430g of an aqueous solution (20%) of potassium hydroxide, controlling the dropping speed to ensure that the pH value is 8-9, keeping the temperature for 3 hours after the addition is finished, detecting that the content of a raw material is less than 0.5% by using HP L C, stopping the reaction, cooling, standing and layering to obtain an upper white floccule, wherein the content of the HP L C is 97%, and the content of the raw material is less than 0.2%.
(2) Adding 155g of potassium hydroxide, 100g of sodium hydroxide and 200g of water into a reaction kettle of 1L to prepare an alkali liquor, heating to 230 ℃, slowly adding the intermediate, adding the intermediate after 2 hours, discharging heat to 300 ℃, keeping the temperature for 2 hours, detecting that the content of the raw material is less than 0.5% by using HP L C, stopping the reaction, cooling, wherein the content of HP L C is 85% and the content of the raw material is less than 0.5%, and adding 500m of L water into the solution to dilute the solution for later use in order to avoid caking and incapability of acid precipitation after cooling.
(3) Slowly adding 60% sulfuric acid into the reaction kettle, adjusting the pH value to 6-7, standing and layering to obtain an upper black oily substance;
(4) washing twice, heating at 135 deg.c to dewater and drying to obtain the final product N, N-dibutyl m-aminophenol with GC content of 99% and yield of 69% (calculated on m-aminophenol sodium sulfonate).
And (3) inspecting the prepared N, N-dibutyl m-aminophenol according to the internal control standard of an enterprise, wherein the results are all in accordance with the regulations.
Compared with the prior art, the invention has substantive characteristics and remarkable progress:
(1) simple water is used as a solvent, waste acid and waste alkali generated in the process can be recycled, the utilization rate of raw materials is improved, and the discharge of waste water is reduced; (2) the synthesis process provided by the patent comprises the steps of reacting initial raw material sodium metaaminophenol with an alkylating reagent to obtain alkylated sodium sulfonate, and then carrying out alkali fusion and acid precipitation reactions to obtain N, N-dibutyl meta-aminophenol. Because the alkylation reaction activity of the sodium m-aminophenylsulfonate is higher than that of m-aminophenol, the new process has high yield and low cost, and the yield can be improved to 65 percent from about 45 percent of the yield of the traditional process. (3) In the alkylation reaction, the phenolic hydroxyl in the intermediate m-aminophenol in the traditional process can consume part of the alkylation reagent to generate an ether byproduct, and the sodium sulfonate in the raw material, namely the sodium metaaminophenol sulfonate, of the alkylation reaction in the process has no problems, so that the utilization rate of the raw material is improved, the variety of the byproduct is reduced, and the burden of post-treatment is lightened; (4) in the alkali fusion reaction, in the alkali fusion process of the raw material sodium metanilic sulfonate in the traditional process, various byproducts can be generated due to the instability of amino, so that the yield is low, the product purity is only 95 percent, the process provided by the patent avoids the problems, and the obtained final product has the purity of 98 percent and is a qualified product.
The preparation method of the N, N-dibutyl m-aminophenol provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of N, N-dibutyl m-aminophenol is characterized in that: which comprises the following steps of,
(1) carrying out alkylation reaction on sodium metanilic sulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent, wherein the molar ratio of the sodium metanilic sulfonate to the halogenated hydrocarbon is 1 (2-4), and the molar ratio of the sodium metanilic sulfonate to the acid-binding agent is 1: (1.5-4), wherein the alkylation reaction temperature is 80-200 ℃, and the alkylation reaction time is 2-5 hours, so as to obtain an alkylate solution;
(2) mixing the alkylate solution obtained in the step (1) with an alkaline reagent and water for alkali fusion reaction, wherein the molar ratio of the sodium metanilic sulfonate and the alkaline reagent in the step (1) is 1 (2-4), and the mass ratio of the water to the alkaline reagent is (0-3): 1, performing alkali fusion reaction at the temperature of 200-350 ℃ for 1-3 hours to obtain alkylated sodium phenolate, and then adding water, wherein the mass ratio of the added water to the sodium metaaminobenzenesulfonate is (1-4): 1;
(3) carrying out acid precipitation reaction on the alkylated sodium phenolate salt obtained in the step (2) and an acidic reagent, wherein the molar ratio of the alkylated sodium phenolate salt to the acidic reagent is 1: (0.5-2), and reacting for 0.5-3h to obtain a crude product of N, N-dibutyl m-aminophenol;
(4) refining the crude N, N-dibutyl m-aminophenol obtained in the step (3) to obtain N, N-dibutyl m-aminophenol, wherein the structural formula is as follows:
2. the method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: the halogenated hydrocarbon comprises fluorobutane, chlorobutane, bromobutane or iodobutane.
3. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: the acid-binding agent comprises magnesium oxide, sodium hydroxide, potassium hydroxide or ammonia water.
4. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: and (3) the alkaline reagent in the step (2) is one or two of sodium hydroxide and potassium hydroxide.
5. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: in the step (3), the acidic reagent comprises hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid or trifluoroacetic acid.
6. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: in the step (3), when the acid precipitation reaction is finished, adjusting the pH value of the solution to 2-7, and continuing the reaction for 0.5-3 h.
7. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: in the step (4), the refining comprises water washing, heating for dehydration and drying.
8. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 7, wherein: the temperature of heating dehydration is 100-250 ℃.
9. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: in the step (1), sodium m-aminobenzenesulfonate, a solvent, halogenated hydrocarbon and an acid-binding agent are subjected to alkylation reaction, the sodium aminobenzenesulfonate is firstly dissolved in the solvent, the mass fraction of the sodium m-aminobenzenesulfonate in the solvent is 10% -65%, and then the halogenated hydrocarbon and the acid-binding agent are sequentially added.
10. The method for preparing N, N-dibutyl-m-aminophenol as claimed in claim 1, wherein: the solvent is water.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411817A2 (en) * | 1989-08-01 | 1991-02-06 | Sumitomo Chemical Company, Limited | Process for preparing N-alkyl-substituted aminophenols |
| EP0427572A1 (en) * | 1989-11-10 | 1991-05-15 | Sumitomo Chemical Company, Limited | Process for preparing N-alkylaminophenols and N,N-dialkylaminophenols |
| US5486609A (en) * | 1994-03-26 | 1996-01-23 | Basf Aktiengesellschaft | Preparation of carbocylic M-aminohydroxyaromatics |
| US5710335A (en) * | 1995-10-16 | 1998-01-20 | Mitsui Toatsu Chemicals, Inc. | Process for preparing 3-(N,N-disubstituted amino)phenol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411817A2 (en) * | 1989-08-01 | 1991-02-06 | Sumitomo Chemical Company, Limited | Process for preparing N-alkyl-substituted aminophenols |
| EP0427572A1 (en) * | 1989-11-10 | 1991-05-15 | Sumitomo Chemical Company, Limited | Process for preparing N-alkylaminophenols and N,N-dialkylaminophenols |
| US5486609A (en) * | 1994-03-26 | 1996-01-23 | Basf Aktiengesellschaft | Preparation of carbocylic M-aminohydroxyaromatics |
| US5710335A (en) * | 1995-10-16 | 1998-01-20 | Mitsui Toatsu Chemicals, Inc. | Process for preparing 3-(N,N-disubstituted amino)phenol |
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