CN108558710A - A kind of preparation method of N, N- dibutyl m-aminophenol - Google Patents
A kind of preparation method of N, N- dibutyl m-aminophenol Download PDFInfo
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- CN108558710A CN108558710A CN201810324557.9A CN201810324557A CN108558710A CN 108558710 A CN108558710 A CN 108558710A CN 201810324557 A CN201810324557 A CN 201810324557A CN 108558710 A CN108558710 A CN 108558710A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- 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
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- 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
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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Abstract
The present invention relates to a kind of N, the preparation method of N dibutyl m-aminophenols, it includes the following steps, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction by 1, alkylated reaction temperature is 80 ~ 200 DEG C, the alkylated reaction time is 2 ~ 5 hours, obtains the solution of alkylates；The solution of alkylates and alkaline reagent, water are mixed progress alkali fusion reaction by 2, and alkali fusion reaction temperature is 200 ~ 350 DEG C, and the reaction time is to obtain alkylated sodium phenolate in 13 hours, then adds water；Alkylated sodium phenolate and acid reagent are carried out acid precipitation reaction by 3, and the reaction time is 0.5h 3h, obtains crude product N, N dibutyl m-aminophenol；4 are refining to obtain N, N dibutyl m-aminophenols；Using N made from the method for the present invention, N dibutyl m-aminophenol high incomes are at low cost, reduce by-product type, alleviate the burden of post-processing.
Description
Technical field
The invention belongs to technical field of chemical material preparation, specifically, it is related to a kind of N, N- dibutyl m-aminophenyls
The preparation method of phenol.
Background technology
N, N- dibutyl m-aminophenol are a kind of key intermediates for pressing temperature-sensitive colour coupler ODB-2.ODB-2 is current
The dyeing of the black color formers being most widely used in the world, quality picture is deep, and storage stability is good, and compound structure is simple,
It is cheap, can be applied in the various pressure electrothermal sensitive recording papers such as fax, label, both can be used alone, can also with other at
Toner is used for high-speed facsimile paper together.Structural formula is:
Wherein, the purity and cost of N, N- dibutyl m-aminophenol, it is directly related with the quality of ODB-2 products and income.
Its traditional synthesis technology is between starting material sodium m-aminobenzene sulfonate elder generation and sodium hydroxide carry out alkali fusion and acid precipitation reaction obtains
Amino-phenol, then N, N- dibutyl m-aminophenols is obtained by the reaction with alkylating reagent.Process is as follows：
The preparation method that traditional handicraft provides, alkali fusion reactor product is complicated, and poor selectivity, target product conversion ratio is low, post-processing
Difficulty is larger；Alkylated reaction phenolic hydroxyl group has certain activity, can participate in reacting, influence the quality and receipts of final products
Rate.Integrated artistic flow yield is relatively low, and wastewater flow rate is big.
Invention content
The object of the present invention is to provide a kind of high income, at low cost, small and simple process the N of pollution, ammonia between N- dibutyl
The preparation method of base phenol.
To achieve the above object, of the invention its includes the following steps,
（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, the sodium m-aminobenzene sulfonate
Molar ratio with halogenated hydrocarbons is 1:（2~4）, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：（1.5-4）, alkyl
It is 80 ~ 200 DEG C to change reaction temperature, and the alkylated reaction time is 2 ~ 5 hours, obtains the solution of alkylates；
（2）By step（1）The solution and alkaline reagent of obtained alkylates, water mixing carry out alkali fusion reaction, the step（1）
Raw material sodium m-aminobenzene sulfonate and step（2）Alkaline reagent molar ratio be 1:（2~4）, the mass ratio of water and alkaline reagent
（0~3）：1, i.e. the mass fraction of alkaline reagent in water is 25%-100%, and alkali fusion reaction temperature is 200 ~ 350 DEG C, the reaction time
Alkylated sodium phenolate was obtained for 1-3 hours, then adds water, amount of water is with sodium m-aminobenzene sulfonate mass ratio（1~4）：
1；
（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction, the alkylated sodium phenolate and acid
Property reagent molar ratio be 1：（0.5~2）, reaction time 0.5h-3h obtains crude product N, N- dibutyl m-aminophenol；
（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain N, N- dibutyl m-aminophenyls
Phenol, structural formula are：
。
Further, the halogenated hydrocarbons includes fluorine butane, chlorobutane, bromobutane or iodobutane.
Further, the acid binding agent includes magnesia, sodium hydroxide, potassium hydroxide or ammonium hydroxide.
Further, step（2）Alkaline reagent be one or both of sodium hydroxide and potassium hydroxide.
Further, step（3）In, the acid reagent includes hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid or trifluoro second
Acid.
Further, step（3）In, at the end of acid precipitation reaction, it is 2 ~ 7 to adjust solution PH, the reaction was continued 0.5 ~ 3h.
Further, step（4）In, described refine includes washing, thermal dehydration and drying.8. according to claim 1 or 7
A kind of preparation method of the N, N- dibutyl m-aminophenol, it is characterised in that：The temperature of the thermal dehydration be 100 ~
250℃。
Further, step（1）In, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated instead
It answers, Sodium p-aminobenzene sulfonat is dissolved in solvent first, the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 10%-65%, then
Sequentially add halogenated hydrocarbons and acid binding agent.
Further, the solvent is water.
Good effect of the present invention is as follows：
（1）The utilization rate of raw material of the present invention is high, reduces discharge of wastewater.
（2）High income of the present invention, at low cost, yield can be improved by 45% or so of traditional handicraft to 65%.
（3）The present invention reduces by-product types, alleviate the burden of post-processing.
（4）Product purity produced by the present invention is high.
Specific implementation mode
The present invention provides a kind of N, the preparation methods of N- dibutyl m-aminophenols：It is with sodium m-aminobenzene sulfonate
Beginning raw material is first reacted with alkylating reagent, is then carried out again through alkylated reaction, alkali fusion reaction and acid precipitation reaction, raw material
Finally target product is obtained by the reaction with acid reagent in alkali fusion.
The synthetic route of above-mentioned technical proposal is as follows：
All raw materials of the present invention, are not particularly limited source, buy on the market.
The purity of all raw materials is not particularly limited in the present invention, with N well known to those skilled in the art, N- dibutyl
Conventional material purity, preferably technical pure in m-aminophenol production.
After the present invention first dissolves sodium m-aminobenzene sulfonate in a solvent, then acted in acid binding agent with alkylating reagent
Lower generation alkylated reaction；The alkylating reagent is halogenated hydrocarbons, including but not limited to fluorine butane, chlorobutane, bromobutane, iodine fourth
One or more of alkane, most preferably chlorobutane or bromobutane；The alkylating reagent halogenated hydrocarbons and sodium m-aminobenzene sulfonate
Molar ratio be（2~4）：1, more preferably（2.3~3.0）：1；The alkylated reaction acid binding agent include but not limited to magnesia,
The organic bases such as the alkali metal oxides such as sodium hydroxide, potassium hydroxide and hydroxide and ammonium hydroxide one of which or several groups
It closes, most preferably sodium hydroxide or potassium hydroxide；The molar ratio of the alkaline reagent and sodium m-aminobenzene sulfonate is preferably（2~
4）：1, more preferably（2.8~3.2）：1；The alkylated reaction temperature is preferably 80 ~ 200 DEG C, more preferably 100 ~ 150 DEG C；
The alkylated reaction time is preferably 2 ~ 5 hours, more preferably 3 ~ 4 hours.Preferably, the solvent is water or alcohols polarity
Solution.
The step of the present invention（1）For：（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated instead
It answers, the molar ratio of the sodium m-aminobenzene sulfonate and halogenated hydrocarbons is 1:（2~4）, the sodium m-aminobenzene sulfonate and acid binding agent
Molar ratio is 1：（1.5-4）, alkylated reaction temperature is 80 ~ 200 DEG C, and the alkylated reaction time is 2 ~ 5 hours, is alkylated
The solution of object.
Specifically, at room temperature, the present invention is to ensure that alkylated reaction is stablized to carry out, preferably before the reaction by m-aminophenyl
Sodium sulfonate is substantially soluble in solvent；The method for being dissolved in solvent is not particularly limited in the present invention, with well known to those skilled in the art
The method of this generic operation, it is preferable that the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 10%-65%, the room temperature
Temperature be preferably 20 ~ 25 DEG C, then sequentially add halogenated hydrocarbons and acid binding agent after mixing, be alkylated reaction, it is described
Mixed mode is preferably stirred；The time of the stirring is preferably 20 ~ 30 minutes；The sodium m-aminobenzene sulfonate and halogen
Molar ratio for hydrocarbon is 1:（2~4）, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：（1.5-4）, alkylation is instead
It is 80 ~ 200 DEG C to answer temperature, and the alkylated reaction time is 2 ~ 5 hours, obtains the solution of alkylates；Side of the present invention to stirring
Formula is not particularly limited, an agitating mode well known to those skilled in the art；The present invention to above-mentioned mixed at room temperature other
Condition is not particularly limited, with the mixing condition before alkylated reaction well known to those skilled in the art.
The step of the present invention（2）For：(2) by step（1）The solution and alkaline reagent of obtained alkylates carry out alkali fusion
Reaction, the step（1）Raw material sodium m-aminobenzene sulfonate and this step（2）Alkaline reagent molar ratio be 1:（2~4）, water
With the mass ratio of alkaline reagent（0~3）：1, that is, the mass fraction of alkaline reagent in water is 25%-100%, alkali fusion reaction temperature
Degree is 200 ~ 350 DEG C, and the reaction time is to obtain alkylated sodium phenolate in 1-3 hours.
Specifically, for the present invention after the completion of abovementioned alkylization is reacted, stratification obtains reaction intermediate（）N, N- bis-
Butyl sodium m-aminobenzene sulfonate.The mode of the stratification is not particularly limited in the present invention, ripe with those skilled in the art
The mode for the stratification known；The condition of the stratification is not particularly limited in the present invention, with people in the art
The condition of stratification known to member；The present invention is obtaining reaction intermediate（）Afterwards, by step（1）Obtained alkylation
The solution and alkaline reagent of object carry out alkali fusion reaction, i.e., react the heating of intermediate, solvent agent and alkaline reagent, obtain anti-
Answer intermediate（）N, N- dibutyl m-aminophenol sodium；The solvent is preferably water, one kind in alcohols isopolarity solvent
Or several, more preferably water；The alkaline reagent is preferably the combination of sodium hydroxide and potassium hydroxide one or two mixture；
The alkali fusion reaction temperature is 200 ~ 350 DEG C, more preferably 220 ~ 300 DEG C；The alkali fusion reaction time is 1 ~ 3 hour.This hair
The bright other conditions for reaction are not particularly limited, the condition reacted with alkali fusion well known to those skilled in the art；This
The mode of heating is not particularly limited in invention, with mode of heating well known to those skilled in the art；The present invention is to reaction
Container is not particularly limited, with the reaction vessel well known to those skilled in the art for alkali fusion reaction.
The step of the present invention（3）For：（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction,
The molar ratio of the alkylated sodium phenolate and acid reagent is 1：（0.5~2）, reaction temperature is 20-100 DEG C, and the reaction time is
0.5-3h obtains crude product N, N- dibutyl m-aminophenol；
Specifically, for the present invention after the completion of above-mentioned alkali fusion reacts, cooling obtains reaction intermediate（）Ammonia between N, N- dibutyl
Base sodium phenate.The mode of the cooling is not particularly limited in the present invention, in a manner of cooling well known to those skilled in the art
；The condition of the cooling is not particularly limited in the present invention, with the condition of cooling well known to those skilled in the art；
The present invention is obtaining reaction intermediate（）Afterwards, it is neutralized with water, acid reagent, i.e. acid precipitation reaction, obtains crude product N, N-
Dibutyl m-aminophenol；The acid reagent is preferably the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid or formic acid, acetic acid, trifluoro second
The mixture of one or both of the organic acids such as acid, more preferably hydrochloric acid and sulfuric acid；The present invention is to the acid precipitation reaction
Temperature is not particularly limited, with the temperature of acid precipitation reaction well known to those skilled in the art, preferably 40 ~ 80 DEG C；This hair
The bright acid precipitation reaction terminal, it is 2 ~ 7 to adjust PH, and it is 6 ~ 7 more preferably to adjust PH.
The step of the present invention（4）For：（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain
To N, N- dibutyl m-aminophenols, structural formula is：
。
The present invention, preferably through washing, thermal dehydration and dry post-processing, finally obtains qualification after the completion of above-mentioned reaction
Product N, N- dibutyl m-aminophenol.The mode of the washing is not particularly limited in the present invention, with those skilled in the art
The mode of well known washing, is preferably washed with hot water；The temperature of the hot water is not particularly limited in the present invention, with
The mode of temperature well known to those skilled in the art, preferably 40 ~ 60 DEG C；The present invention does not have the number of the washing
Especially limitation, with the washing times in such post-reaction treatment well known to those skilled in the art；The present invention is for described
Thermal dehydration mode is not particularly limited, in a manner of thermal dehydration well known to those skilled in the art；The present invention for
The temperature of the thermal dehydration is not particularly limited, with the heating in such compound post-processing well known to those skilled in the art
The temperature of dehydration, extraction temperature are 100 ~ 250 DEG C, preferably 110 ~ 140 DEG C；The present invention does not have the mode of the drying
There is special limitation, with the drying mode in such post-reaction treatment well known to those skilled in the art, it is preferred to use vacuum
It is dry；Vacuum drying condition is not particularly limited in the present invention, with vacuum drying condition well known to those skilled in the art
.
To the N that the above method of the present invention is prepared, N- dibutyl m-aminophenols carry out gas-chromatography（GC）Analysis,
Purity >=98% of N prepared by the present invention, N- dibutyl m-aminophenol, reaction yield >=60%.
For a further understanding of the present invention, with reference to embodiment to N provided by the invention, N- dibutyl m-aminophenyls
The preparation method of phenol is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
The present invention includes the following steps,
（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, the sodium m-aminobenzene sulfonate
Molar ratio with halogenated hydrocarbons is 1:3, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：（2）, alkylated reaction temperature
Degree is 100 DEG C, and the alkylated reaction time is 3 hours, obtains the solution of alkylates；The halogenated hydrocarbons is fluorine butane.It is described to tie up
Sour agent is magnesia.
Step（1）In, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, first by ammonia
Base benzene sulfonic acid sodium salt is dissolved in solvent, and the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 40%, then sequentially add halogenated hydrocarbons and
Acid binding agent.
The solvent is water.
（2）By step（1）The solution and alkaline reagent of obtained alkylates, water mixing carry out alkali fusion reaction, between described
Sodium p-aminobenzene sulfonat（Sodium m-aminobenzene sulfonate is step（1）Raw material）Molar ratio with alkaline reagent is 1:3, water is tried with alkalinity
The mass ratio of agent（2）：1, alkali fusion reaction temperature is 280 DEG C, and the reaction time is to obtain alkylated sodium phenolate in 2 hours, then again
Water, amount of water and sodium m-aminobenzene sulfonate is added（Sodium m-aminobenzene sulfonate is step（1）Raw material）Mass ratio is 3：1；It is described
Alkaline reagent selects sodium hydroxide.
（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction, the alkylated sodium phenolate
Molar ratio with acid reagent is 1：1, reaction time 1.5h obtain crude product N, N- dibutyl m-aminophenol；The acid
Property reagent select salpeter solution.At the end of acid precipitation reaction, it is 5 to adjust solution PH, the reaction was continued 1.5h.
（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain N, amino between N- dibutyl
Phenol, structural formula are：
。
Described refine includes washing, thermal dehydration and drying.The temperature of the thermal dehydration is 180 DEG C.Final products N,
N-dibutyl m-aminophenol G/C content 99.2%, yield 69.3%（In terms of sodium m-aminobenzene sulfonate）.By the N of preparation, N-
Dibutyl m-aminophenol is tested according to inner controlling standard of enterprise, as a result meets regulation.
Embodiment 2
The present invention includes the following steps,
（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, the sodium m-aminobenzene sulfonate
Molar ratio with halogenated hydrocarbons is 1:2, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：4, alkylated reaction temperature
It it is 80 DEG C, the alkylated reaction time is 5 hours, obtains the solution of alkylates；The halogenated hydrocarbons is chlorobutane.The acid binding agent
For potassium hydroxide.
Step（1）In, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, first by ammonia
Base benzene sulfonic acid sodium salt is dissolved in solvent, and the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 10%, then sequentially add halogenated hydrocarbons and
Acid binding agent.
The solvent is water.
（2）By step（1）The solution and alkaline reagent of obtained alkylates, water mixing carry out alkali fusion reaction, between described
Sodium p-aminobenzene sulfonat（Sodium m-aminobenzene sulfonate is step（1）Raw material）Molar ratio with alkaline reagent is 1:2, water is tried with alkalinity
The mass ratio 0.1 of agent：1, alkali fusion reaction temperature is 350 DEG C, and the reaction time is to obtain alkylated sodium phenolate in 1 hour, then again
Water, amount of water and sodium m-aminobenzene sulfonate is added（Sodium m-aminobenzene sulfonate is step（1）Raw material）Mass ratio is 1：1；It is described
Alkaline reagent selects potassium hydroxide.
（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction, the alkylated sodium phenolate
Molar ratio with acid reagent is 1：0.5, reaction time 3h obtain crude product N, N- dibutyl m-aminophenol；The acid
Property reagent formic acid solution.At the end of acid precipitation reaction, it is 2 to adjust solution PH, the reaction was continued 0.5h.
（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain N, amino between N- dibutyl
Phenol, structural formula are：
。
Described refine includes washing, thermal dehydration and drying.The temperature of the thermal dehydration is 100 DEG C.Final products N, N-
Dibutyl m-aminophenol G/C content 99%, yield 68.8%（In terms of sodium m-aminobenzene sulfonate）.By the N of preparation, N-dibutyl
M-aminophenol is tested according to inner controlling standard of enterprise, as a result meets regulation.
Embodiment 3
The present invention includes the following steps,
（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, the sodium m-aminobenzene sulfonate
Molar ratio with halogenated hydrocarbons is 1:4, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：1.5, alkylated reaction temperature
Degree is 200 DEG C, and the alkylated reaction time is 2 hours, obtains the solution of alkylates；The halogenated hydrocarbons is iodobutane.It is described to tie up
Sour agent is ammonium hydroxide.
Step（1）In, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, first by ammonia
Base benzene sulfonic acid sodium salt is dissolved in solvent, and the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 65%, then sequentially add halogenated hydrocarbons and
Acid binding agent.
The solvent is water.
（2）By step（1）The solution and alkaline reagent of obtained alkylates, water mixing carry out alkali fusion reaction, between described
Sodium p-aminobenzene sulfonat（Sodium m-aminobenzene sulfonate is step（1）Raw material）Molar ratio with alkaline reagent is 1:4, water is tried with alkalinity
The mass ratio 3 of agent：1, alkali fusion reaction temperature is 200 DEG C, and the reaction time is to obtain alkylated sodium phenolate in 3 hours, is then added again
Enter water, amount of water and sodium m-aminobenzene sulfonate（Sodium m-aminobenzene sulfonate is step（1）Raw material）Mass ratio is 4：1；The alkali
Property reagent select potassium hydroxide.
（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction, the alkylated sodium phenolate
Molar ratio with acid reagent is 1：2, reaction time 0.5h obtain crude product N, N- dibutyl m-aminophenol；The acid
Property reagent select acetic acid or trifluoroacetic acid solution.At the end of acid precipitation reaction, it is 7 to adjust solution PH, the reaction was continued 3h.
（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain N, amino between N- dibutyl
Phenol, structural formula are：
。
Described refine includes washing, thermal dehydration and drying.The temperature of the thermal dehydration is 250 DEG C.Final products N, N-
Dibutyl m-aminophenol G/C content 99%, yield 65%（In terms of sodium m-aminobenzene sulfonate）.By the N of preparation, between N-dibutyl
Amino-phenol is tested according to inner controlling standard of enterprise, as a result meets regulation.
Embodiment 4
The present invention includes the following steps,
（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, the sodium m-aminobenzene sulfonate
Molar ratio with halogenated hydrocarbons is 1:3, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：（2）, alkylated reaction temperature
Degree is 100 DEG C, and the alkylated reaction time is 3 hours, obtains the solution of alkylates；The halogenated hydrocarbons is fluorine butane.It is described to tie up
Sour agent is magnesia.
Step（1）In, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, first by ammonia
Base benzene sulfonic acid sodium salt is dissolved in solvent, and the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 40%, then sequentially add halogenated hydrocarbons and
Acid binding agent.
The solvent is water.
（2）By step（1）The solution and alkaline reagent of obtained alkylates carry out alkali fusion reaction, the m-aminophenyl sulphur
Sour sodium（Sodium m-aminobenzene sulfonate is step（1）Raw material）Molar ratio with alkaline reagent is 1:3, alkali fusion reaction temperature is 280
DEG C, the reaction time is to obtain alkylated sodium phenolate in 2 hours, then adds water, amount of water and sodium m-aminobenzene sulfonate（Between ammonia
Base benzene sulfonic acid sodium salt is step（1）Raw material）Mass ratio is 3：1；The alkaline reagent selects sodium hydroxide.
（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction, the alkylated sodium phenolate
Molar ratio with acid reagent is 1：1, reaction time 1.5h obtain crude product N, N- dibutyl m-aminophenol；The acid
Property reagent select salpeter solution.At the end of acid precipitation reaction, it is 5 to adjust solution PH, the reaction was continued 1.5h.
（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain N, amino between N- dibutyl
Phenol, structural formula are：
。
Described refine includes washing, thermal dehydration and drying.The temperature of the thermal dehydration is 180 DEG C.Final products N,
N-dibutyl m-aminophenol G/C content 99.1%, yield 69.2%（In terms of sodium m-aminobenzene sulfonate）.By the N of preparation, N-
Dibutyl m-aminophenol is tested according to inner controlling standard of enterprise, as a result meets regulation.
Embodiment 5
（1）In reaction kettles of the 1L with high-pressure pump, the aqueous solution of 200g sodium m-aminobenzene sulfonates is added（47%）, 180g bromos
Normal butane closes kettle, opens stirring, is warming up to 110 DEG C, is slowly added into the aqueous solution of 280g sodium hydroxides（20%）, control is added dropwise fast
Degree ensures pH value in 8- 9, and heat preservation 3 hours after adding, HPLC detection raw materials are less than 0.5%, stops reaction, cooling standing point
Layer, obtains upper layer White Flocculus, HPLC contents 96%, and raw material is less than 0.3%.
（2）In the reaction kettle of 1L, 155g potassium hydroxide, 100g sodium hydroxides, 200g water is added and is made into lye, is warming up to
230 DEG C, it is slowly added into above-mentioned worth intermediate, is added within 2 hours, exothermic heat of reaction keeps the temperature 2 hours to 300 DEG C, and HPLC detections are former
Material is less than 0.5%, stops reaction, cools down, and HPLC contents 85%, raw material is less than 0.5%, in order to avoid that can lump after cooling, Wu Fajin
Row acid out, into above-mentioned solution plus the dilution of 500mL water is spare.
（3）The hydrochloric acid for being 30% by mass fraction, is slowly added into aforesaid reaction vessel, adjusts pH value in 6- 7, stands and divide
Layer, obtains upper layer dark oil object
（4）Twice of washing, 120 DEG C of thermal dehydrations, dry final products N, N-dibutyl m-aminophenol G/C content
98%, yield 65%（In terms of sodium m-aminobenzene sulfonate）.
By the N of preparation, N-dibutyl m-aminophenol is tested according to inner controlling standard of enterprise, as a result meets rule
It is fixed.
Embodiment 6
（1）In reaction kettles of the 1L with high-pressure pump, the aqueous solution of 200g sodium m-aminobenzene sulfonates is added（49%）, 135g chloros
Normal butane closes kettle, opens stirring, is warming up to 150 DEG C, is slowly added into the aqueous solution of 280g sodium hydroxides（20%）, control is added dropwise fast
Degree ensures pH value in 8- 9, and heat preservation 3 hours after adding, HPLC detection raw materials are less than 0.5%, stops reaction, cooling standing point
Layer, obtains upper layer White Flocculus, HPLC contents 95%, and raw material is less than 0.3%.
（2）In the reaction kettle of 1L, 155g potassium hydroxide, 100g sodium hydroxides, 200g water is added and is made into lye, is warming up to
230 DEG C, it is slowly added into above-mentioned intermediate, is added within 2 hours, exothermic heat of reaction keeps the temperature 2 hours to 300 DEG C, and HPLC detection raw materials are less than
0.5%, stop reaction, cool down, HPLC contents 85%, raw material is less than 0.5%, in order to avoid that can lump after cooling, can not carry out acid
Analysis, into above-mentioned solution plus the dilution of 500mL water is spare.
（3）30% hydrochloric acid, is slowly added into aforesaid reaction vessel, adjusts pH value in 5- 6, stratification obtains upper layer black
Grease；
（4）Twice of washing, 120 DEG C of thermal dehydrations are dry, obtain final products N, N-dibutyl m-aminophenol G/C content
98%, yield 60%（In terms of sodium m-aminobenzene sulfonate）.
By the N of preparation, N-dibutyl m-aminophenol is tested according to inner controlling standard of enterprise, as a result meets rule
It is fixed.
Embodiment 7
（1）In reaction kettles of the 1L with high-pressure pump, the aqueous solution of 200g sodium m-aminobenzene sulfonates is added（50%）, 203g bromos
Normal butane closes kettle, opens stirring, is warming up to 140 DEG C, is slowly added into the aqueous solution of 430g potassium hydroxide（20%）, control is added dropwise fast
Degree ensures pH value in 8- 9, and heat preservation 3 hours after adding, HPLC detection raw materials are less than 0.5%, stops reaction, cooling standing point
Layer, obtains upper layer White Flocculus, HPLC contents 97%, and raw material is less than 0.2%.
（2）In the reaction kettle of 1L, 155g potassium hydroxide, 100g sodium hydroxides, 200g water is added and is made into lye, is warming up to
230 DEG C, it is slowly added into above-mentioned intermediate, is added within 2 hours, exothermic heat of reaction keeps the temperature 2 hours to 300 DEG C, and HPLC detection raw materials are less than
0.5%, stop reaction, cool down, HPLC contents 85%, raw material is less than 0.5%, in order to avoid that can lump after cooling, can not carry out acid
Analysis, into above-mentioned solution plus the dilution of 500mL water is spare.
（3）The sulfuric acid that mass fraction is 60%, is slowly added into aforesaid reaction vessel, adjusts pH value in 6- 7, stratification,
Obtain upper layer dark oil object；
（4）Twice of washing, 135 DEG C of thermal dehydrations are dry, obtain final products N, N-dibutyl m-aminophenol G/C content
99%, yield 69%（In terms of sodium m-aminobenzene sulfonate）.
By the N of preparation, N-dibutyl m-aminophenol is tested according to inner controlling standard of enterprise, as a result meets rule
It is fixed.
The present invention has substantive distinguishing features and significant progress compared with prior art：
（1）It is solvent to have used simple water, and the spent acid salkali waste generated in technical process can be applied mechanically, and the utilization of raw material is improved
Rate reduces discharge of wastewater；（2）The synthesis technology that this patent provides is that starting material sodium m-aminobenzene sulfonate is first and is alkylated
Alkylated sulfonate sodium is obtained by the reaction in reagent, then carries out alkali fusion and acid precipitation reaction obtains N, N- dibutyl m-aminophenols.By
It is higher than m-aminophenol in sodium m-aminobenzene sulfonate alkylation activity, so new process high income, at low cost, yield is by passing
45% or so of system technique can be improved to 65%.（3）Alkylated reaction, the phenolic hydroxyl group in the intermediate m-aminophenol of traditional handicraft
Partially alkylated reagent can be consumed, generates the by-product of ethers, in this patent technique alkylated reaction raw material sodium m-aminobenzene sulfonate
Sodium sulfonate group such issues that be not present, improve raw material availability, reduce by-product type, alleviate the burden of post-processing；
（4）Alkali fusion reacts, and the raw material sodium m-aminobenzene sulfonate of traditional handicraft is during alkali fusion, since the unstability of amino will produce
A variety of by-products cause yield relatively low, and product purity only has 95%, and the technique that this patent provides avoids the generation of problems, obtains
Final products purity 98% is obtained, is qualified products.
Above to a kind of N provided by the present invention, the preparation method of N-dibutyl m-aminophenol has carried out detailed Jie
It continues.Used herein specifically principle and implementation of the present invention are described for a example, the explanation of above example
It is merely used to help understand the method and its core concept of the present invention.It should be pointed out that coming for those skilled in the art
It says, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It also falls within the protection scope of the claims of the present invention.
Claims (10)
1. the preparation method of a kind of N, N- dibutyl m-aminophenol, it is characterised in that：It includes the following steps,
（1）Sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, the sodium m-aminobenzene sulfonate
Molar ratio with halogenated hydrocarbons is 1:（2~4）, the molar ratio of the sodium m-aminobenzene sulfonate and acid binding agent is 1：（1.5-4）, alkyl
It is 80 ~ 200 DEG C to change reaction temperature, and the alkylated reaction time is 2 ~ 5 hours, obtains the solution of alkylates；
（2）By step（1）The solution and alkaline reagent of obtained alkylates, water mixing carry out alkali fusion reaction, step（1）Between
The molar ratio of Sodium p-aminobenzene sulfonat and alkaline reagent is 1:（2~4）, the mass ratio of water and alkaline reagent（0~3）：1, alkali fusion reaction
Temperature is 200 ~ 350 DEG C, and the reaction time is to obtain alkylated sodium phenolate in 1-3 hours, then adds water, amount of water and ammonia
Base benzene sulfonic acid sodium salt mass ratio is（1~4）：1；
（3）By step（2）Alkylated sodium phenolate and acid reagent carry out acid precipitation reaction, the alkylated sodium phenolate and acid
Property reagent molar ratio be 1：（0.5~2）, reaction time 0.5h-3h obtains crude product N, N- dibutyl m-aminophenol；
（4）By step（3）Crude product N, N- dibutyl m-aminophenol refined, obtain N, N- dibutyl m-aminophenyls
Phenol, structural formula are：
。
2. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：The halogen
Include fluorine butane, chlorobutane, bromobutane or iodobutane for hydrocarbon.
3. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：It is described to tie up
Sour agent includes magnesia, sodium hydroxide, potassium hydroxide or ammonium hydroxide.
4. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：Step
（2）Alkaline reagent be one or both of sodium hydroxide and potassium hydroxide.
5. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：Step
（3）In, the acid reagent includes hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid or trifluoroacetic acid.
6. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：Step
（3）In, at the end of acid precipitation reaction, it is 2 ~ 7 to adjust solution PH, the reaction was continued 0.5 ~ 3h.
7. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：Step
（4）In, described refine includes washing, thermal dehydration and drying.
8. the preparation method of a kind of N according to claim 1 or claim 7, N- dibutyl m-aminophenol, it is characterised in that：Institute
The temperature for stating thermal dehydration is 100 ~ 250 DEG C.
9. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：Step
（1）In, sodium m-aminobenzene sulfonate, solvent, halogenated hydrocarbons and acid binding agent are alkylated reaction, it is first that Sodium p-aminobenzene sulfonat is molten
In solvent, the mass fraction of sodium m-aminobenzene sulfonate in a solvent is 10%-65%, then sequentially adds halogenated hydrocarbons and acid binding agent.
10. the preparation method of a kind of N according to claim 1, N- dibutyl m-aminophenol, it is characterised in that：It is described
Solvent is water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102439A (en) * | 2023-04-12 | 2023-05-12 | 山东默锐科技有限公司 | Preparation process of 4-dibutylamino keto acid alkylation reaction intermediate product |
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 |
-
2018
- 2018-04-12 CN CN201810324557.9A patent/CN108558710B/en active Active
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102439A (en) * | 2023-04-12 | 2023-05-12 | 山东默锐科技有限公司 | Preparation process of 4-dibutylamino keto acid alkylation reaction intermediate product |
| CN116102439B (en) * | 2023-04-12 | 2023-11-24 | 山东默锐科技有限公司 | Preparation process of 4-dibutylamino keto acid alkylation reaction intermediate product |
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