CN103626684A - Preparation method of p-aminophenyl-beta-ethoxyl sulphone sulphate - Google Patents
Preparation method of p-aminophenyl-beta-ethoxyl sulphone sulphate Download PDFInfo
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Abstract
The invention discloses a preparation method of p-aminophenyl-beta-ethoxyl sulphone sulphate. The preparation method comprises the following steps of: adding p-aminophenyl and mercaptoethanol into an N, N-dimethyl formamide solvent to dissolve, and adding NaOH to carry out reaction; filtering, distilling under reduced pressure to obtain p-aminophenyl-beta-ethoxyl thioether after reaction; adding the p-aminophenyl-beta-ethoxyl thioether and a catalyst into an oxidization kettle, adding hydrogen peroxide to carry out reaction, and cooling and separating out an oxidized and crystallized material after the reaction; washing the oxidized and crystallized material, adding water and a palladium-carbon catalyst after washing to carry out hydrogenation reaction, thus obtaining an hydrogenation product and water after the reaction; adding pure sulfuric acid to carry out esterification reaction, and crushing the obtained product to obtain the p-aminophenyl-beta-ethoxyl sulphone sulphate. In the preparation method disclosed by the invention, dosage of the adopted hydrogen peroxide and the palladium-carbon catalyst is less, especially, dosage of the palladium-carbon catalyst is greatly reduced, so that production cost is greatly lowered; and moreover, output of three wastes is lower, yield is higher, economical benefits and social benefits are remarkable.
Description
Technical field
The present invention relates to a kind of production method of reactive dyestuffs intermediate, particularly relate to a kind of preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester.
Background technology
At present, the production method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester is to adopt by the raw materials such as Acetanilide, chlorsulfonic acid, Sodium Pyrosulfite, sodium hydroxide, oxyethane, sulfuric acid are synthesized, its synthetic comprising the following steps:
A, sulfonation operation: first the chlorsulfonic acid measuring is added in sulphonation kettle, again the antifebrin measuring is dropped in sulphonation kettle and reacts (chlorsulfonic acid is excessive), sulfonation reaction is thermopositive reaction, during refrigeration, use-10 ℃ of following icy salt solutions, by jacket reactor, lower the temperature, control temperature, reaction is carried out smoothly.In reaction process, have a large amount of hydrogen chloride gas to produce, design adopts level Four water to absorb, the industrial hydrochloric acid of the water-soluble generation of hydrogen chloride gas 30-33%.In the process of feeding intake, temperature is controlled at 45 ℃ of left and right, and charging time is 3h, and a part generates SULPHURYL CHLORIDE, and a part generates Phenylsulfonic acid, and after feeding intake, the Phenylsulfonic acid of generation, under excess chlorine sulfonation, changes into SULPHURYL CHLORIDE.This reaction process is thermo-negative reaction, and sulphonation kettle will keep certain temperature, and sulfonation reaction is carried through to the end.After feeding intake, temperature in the kettle is controlled at 60 ℃ of left and right, keeps 2h, and standing 8h, then drops into sulfonated bodies in hydrolysis kettle, adds a certain amount of water, and excessive chlorsulfonic acid is hydrolyzed, and hydrolysis temperature is controlled at 35 ℃ of left and right.In hydrolytic process, there is equally hydrogen chloride gas to produce, adopt aforesaid method to reclaim.Fully after completion of the reaction, resultant of reaction adds the cooling Precipitation of frozen water, then filtration, centrifuge dehydration, and 4 tons of filtrate (10-15%) ton output, are all recovered to condensation workshop section.
B, reduction, condensation operation: by the Sodium Pyrosulfite measuring with dropping in reduction kettle after 800kg water dissolution, burning adjusting PH with base value with 30% is to 7.5-7.8, temperature is down to 10 ℃ of left and right, again SULPHURYL CHLORIDE is slowly added, and arrive 7.5-7.8 by lye pH adjustment value, temperature is controlled between 40-42 ℃, reduction process needs 3h, reduction generates sulphonyl sodium, then sulphonyl sodium is moved in condensation kettle, add a certain amount of oxyethane, be warming up to 65 ℃, sulphonyl sodium, under oxyethane effect, is condensed into sulphonyl alcohol.In reaction process, will constantly add the acid mother liquid in sulfonation workshop section, adjust pH, to 7.5-8, after oxyethane adds, is incubated 2h, the blowing centrifuge dehydration of then lowering the temperature, and the mother liquor of deviating from is weakly alkaline, and a ton product generation is 5 tons, discharge after administering discharged to equalizing tank.
C, esterification step: the sulphonyl alcohol measuring is joined in esterifying kettle, add a certain amount of sulfuric acid to be hydrolyzed, after hydrolysis 2h, finish; Be warming up to 150-170 ℃ and carry out esterification, 2h esterification finishes.Start to heat up dry, crushed after being dried packing, finished product warehouse-in.In hydrolysis esterification, there is acetic acid γ-ray emission, acetic acid gas is caused to Glacial acetic acid recovery tower and reclaim, as byproduct, sell.
Above generating process yield lower (approximately 70% left and right); Raw materials consumption is many, and it consumes as (product per ton need consume raw material T/T): Acetanilide 0.65T/T, chlorsulfonic acid 3T/T, Sodium Pyrosulfite 0.4-0.5T/T, oxyethane 0.3T/T, liquid caustic soda (30%) 1.8T/T, sulfuric acid 0.55T/T.In generative process, produce the refuses such as a large amount of waste hydrochloric acids, Waste Sulfuric Acid, useless acetic acid and high-salt wastewater, as waste hydrochloric acid 8-10T/T, Waste Sulfuric Acid 10-15T/T, useless acetic acid 0.15-0.2T/T, high-salt wastewater 6-8T/T.
The many defects that exist in order to overcome above-mentioned existing generating process, research staff's development research a kind of new p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester production method, refer to application number and be 200910064706.3 patent of invention.Although the disclosed production method of this patent has improved certain yield, its yield is 85% left and right; Adopt the method to produce in the process of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the three wastes of generation are less, but produce product per ton, still can produce three wastes 1-2 ton.And the dioxygen water yield and the palladium carbon catalyst consumption that adopt in production process are all larger, especially the large usage quantity of palladium carbon catalyst, makes its production cost higher, because palladium carbon catalyst price more expensive (4000～6000 yuan of palladium carbon catalyst per kilograms).
Summary of the invention
The technical problem to be solved in the present invention is: in order to overcome application number, be that 200910064706.3 patent of invention is produced the defect that p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester exists, the invention provides a kind of preparation method of new p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, utilize preparation method of the present invention to produce p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the hydrogen peroxide adopting, palladium carbon catalyst consumption is less, especially palladium carbon catalyst consumption greatly reduces, its production cost is reduced greatly, and three wastes output is lower, yield is higher, its yield is up to 92% left and right.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides a kind of preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, described preparation method comprises the following steps:
A, to take p-Nitrophenyl chloride and mercaptoethanol be basic raw material, first two kinds of basic raw materials added in DMF solvent and fully dissolve, mix, and then slowly adds sodium hydroxide, controls sodium hydroxide 3～5h and add; It is 50～80 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 3～5h, after reaction finishes, obtains reaction product; By gained reaction product solids removed by filtration NaC1, obtain filtrate, gained filtrate is carried out to underpressure distillation 1～2h under 60～150mmHg, 120～150 ℃ of conditions, steam moisture and DMF, obtain p-nitrophenyl-beta-hydroxyethyl thioether;
Between described p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1～1.2:1.5～2:1;
B, p-nitrophenyl-beta-hydroxyethyl thioether and tungstate catalysts that step a is obtained add stills for air blowing, under agitation slowly add hydrogen peroxide, add that in the process of hydrogen peroxide, to control temperature be 80～100 ℃, and the lasting joining day of hydrogen peroxide is 2～5h; After hydrogen peroxide adds, at 95～100 ℃, react 1～3h, after reaction finishes, lower the temperature, along with system temperature declines, oxidation material constantly crystallizes out; When temperature is down to below 30 ℃, carry out vacuum filtration, isolate oxidizing and crystallizing material;
Described hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1～1.1:1, and the add-on of tungstate catalysts accounts for 0.1～0.3% of p-nitrophenyl-beta-hydroxyethyl thioether quality;
C, the oxidizing and crystallizing material that step b is obtained carry out repetitive scrubbing with methyl alcohol, remove the impurity in oxidizing and crystallizing material, then adopt deionized water wash to neutral, drain and remove methyl alcohol and deionized water, the oxidizing and crystallizing material after being processed;
In d, the processing rear oxidation crystallization material that obtains at step c, add aqueous solvent and palladium carbon catalyst, mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.3～1.7:0.0005～0.0015, then at 40～110 ℃, hydrogen pressure, be under 1.5～2.5MPa condition, to carry out hydrogenation reaction 3～6h, after finishing, reaction filters, leach catalyzer, obtain hydrogenation products and aqueous solvent;
E, the hydrogenation products that steps d is obtained and aqueous solvent directly add in esterification pot, then add bright sulfur acid, the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1～1.05, stirring is warming up to 100～130 ℃, and under vacuum condition, carry out esterification 2～3h, reaction finishes rear discharging, after products therefrom is pulverized, obtains p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the NaC1 of solids removed by filtration described in step a, is to filter under 40 ℃ of conditions of temperature ﹤.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, tungstate described in step b is sodium wolframate.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the mass percentage concentration of hydrogen peroxide described in step b is 30～34%.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, during vacuum filtration described in step b, vacuum tightness is 0.04～0.06MPa.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the mass percentage concentration of methyl alcohol described in step c is 20～80%.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the catalyzer leaching in steps d, can recycle 2～3 times; The hydrogenation products obtaining does not carry out separated with aqueous solvent.
According to the preparation method of above-mentioned p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, described in step e and under vacuum condition, carry out esterification, its vacuum tightness 0.04～0.09MPa.
The relevant chemical equation of technical solution of the present invention is as follows:
positive beneficial effect of the present invention:
1, utilize technical solution of the present invention to prepare p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, its yield is up to 92% left and right (in prior art, the highest yield is only 85% left and right), and compared with prior art, its yield has obtained larger raising.
2, compared with prior art, the hydrogen peroxide of employing, palladium carbon catalyst consumption have had obvious minimizing, and especially palladium carbon catalyst consumption greatly reduces (compared with prior art, its consumption has reduced by 10 times of left and right); And the palladium carbon catalyst that the present invention adopts can be recycled (in prior art, can only use once, after use once, all destroy) 2～3 times.Due to palladium carbon catalyst expensive (4000～6000 yuan of palladium carbon catalyst per kilograms), therefore, greatly reducing of palladium carbon catalyst consumption, reduces its production cost of the present invention greatly.So the present invention has significant economic benefit.
3, the yield that utilizes technical solution of the present invention to produce product reaches 92% left and right, and yield obviously improves compared with prior art, and raw material consumption reduces, and has improved raw material availability; And by product sodium-chlor is less, spent acid, wastewater flow rate are less, produce product waste water output per ton below 0.8T.Compared with prior art, three waste discharge obviously reduces, and is conducive to environmental protection.Therefore, the present invention has significant social benefit.
4, the present invention utilizes solvent to carry out abundant washing to oxidizing and crystallizing material in process of production, removed the impurity in oxidizing and crystallizing material, thereby reached the object of crystallization material purifying, the consumption of its hydrogenation used catalyst is reduced greatly, and palladium carbon catalyst used can Reusability 2～3 times, has reduced thus cost; And hydrogenation thing needn't carry out the refining means such as crystallization, can directly carry out next step esterification without separation.In esterification process, the isolated water solvent of making hydrogenation capable of circulation is used, and has further reduced the output of waste water.
5, preparation method of the present invention compared with prior art, stablize, production cost is lower, is a kind of process for cleanly preparing of environmental type, is beneficial to large-scale use by work simplification, production.Therefore, the present invention has significant economic benefit and social benefit.
four, embodiment:
Below in conjunction with embodiment, further set forth the present invention, but do not limit content of the present invention.
Embodiment 1:
The preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester of the present invention, this preparation method's detailed step is as follows:
A, first by N; dinethylformamide solvent adds reactor; then add two kinds of basic raw materials of p-Nitrophenyl chloride and mercaptoethanol fully to dissolve, mix; then slowly add sodium hydroxide; controlling sodium hydroxide 4h adds; between p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1.2:1.5:1; It is 70 ± 2 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 4.0h, after reaction finishes, obtains reaction product; Gained reaction product is filtered through filtering basin under 40 ℃ of conditions of temperature ﹤, remove solid NaC1, obtain filtrate, gained filtrate is carried out to underpressure distillation 1.5h under 80～120mmHg, 130～140 ℃ of conditions, steam moisture and N, dinethylformamide, obtains p-nitrophenyl-beta-hydroxyethyl thioether;
B, p-nitrophenyl-beta-hydroxyethyl thioether and sodium tungstate catalyst that step a is obtained add stills for air blowing, under agitation slowly adding mass percentage concentration is 30～34% hydrogen peroxide, hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1:1, and the add-on of sodium tungstate catalyst accounts for 0.2% of p-nitrophenyl-beta-hydroxyethyl thioether quality; Add that in the process of hydrogen peroxide, to control temperature be 90 ± 2 ℃, the lasting joining day of hydrogen peroxide is 3.5h; After hydrogen peroxide adds, at 95～100 ℃, react 2.5h, after reaction finishes, lower the temperature, along with system temperature declines, oxidation material constantly crystallizes out; When temperature is down to below 30 ℃, carry out vacuum filtration, during vacuum filtration, vacuum tightness is 0.04～0.06MPa, isolates oxidizing and crystallizing material;
The methyl alcohol that c, the oxidizing and crystallizing material that step b is obtained are 50-60% by mass percentage concentration carries out repetitive scrubbing, remove the impurity in oxidizing and crystallizing material, then adopt deionized water wash to neutral, drain and remove methyl alcohol and deionized water, the oxidizing and crystallizing material after being processed;
In d, the processing rear oxidation crystallization material that obtains at step c, add aqueous solvent and palladium carbon catalyst, mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.5:0.001, then at 80～90 ℃, hydrogen pressure, be under 1.8～2.0MPa condition, to carry out hydrogenation reaction 4.5h, after finishing, reaction filters, leach catalyzer, obtain hydrogenation products and aqueous solvent;
The catalyzer wherein leaching, can recycle 2～3 times; The hydrogenation products obtaining does not carry out separated with aqueous solvent;
E, the hydrogenation products that steps d is obtained and aqueous solvent directly add in esterification pot, then add bright sulfur acid, the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1, stirring is warming up to 120 ℃, and under vacuum condition, to carry out esterification 2.5h(vacuum tightness be 0.06～0.08MPa), reaction finishes rear discharging, after products therefrom is pulverized, obtains p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester.
Embodiment 2: substantially the same manner as Example 1, difference is:
In step a: control sodium hydroxide 3.5h and add, between p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1.1:1.6:1; It is 75 ± 2 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 3.5h; Gained filtrate is carried out to underpressure distillation 2.0h under 60～90mmHg, 140～150 ℃ of conditions;
In step b: hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1.05:1, and the add-on of sodium tungstate catalyst accounts for 0.3% of p-nitrophenyl-beta-hydroxyethyl thioether quality; Add that in the process of hydrogen peroxide, to control temperature be 80-85 ℃, the lasting joining day of hydrogen peroxide is 4h; After hydrogen peroxide adds, at 95～100 ℃, react 2h;
In step c: the methyl alcohol that the oxidizing and crystallizing material that step b is obtained is 20-30% by mass percentage concentration carries out repetitive scrubbing;
In steps d: the mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.3:0.0007, at 90～100 ℃, hydrogen pressure, be then under 1.5～1.8MPa condition, to carry out hydrogenation reaction 4.0h;
In step e: the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1.05, stir and be warming up to 100 ℃, and under vacuum condition, to carry out esterification 3h(vacuum tightness be 0.08～0.09MPa).
Embodiment 3: substantially the same manner as Example 1, difference is:
In step a: control sodium hydroxide 3h and add, between p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1.15:2.0:1; It is 78-80 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 3h; Gained filtrate is carried out to underpressure distillation 1.5h under 120～150mmHg, 120～130 ℃ of conditions;
In step b: hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1.1:1, and the add-on of sodium tungstate catalyst accounts for 0.1% of p-nitrophenyl-beta-hydroxyethyl thioether quality; Add that in the process of hydrogen peroxide, to control temperature be 95 ± 2 ℃, the lasting joining day of hydrogen peroxide is 5h; After hydrogen peroxide adds, at 95～100 ℃, react 3h;
In step c: the methyl alcohol that the oxidizing and crystallizing material that step b is obtained is 60-70% by mass percentage concentration carries out repetitive scrubbing;
In steps d: the mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.3:0.0005, at 100～110 ℃, hydrogen pressure, be then under 1.5～1.8MPa condition, to carry out hydrogenation reaction 6.0h;
In step e: the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1.02, stir and be warming up to 130 ℃, and under vacuum condition, to carry out esterification 2h(vacuum tightness be 0.05～0.06MPa).
Embodiment 4: substantially the same manner as Example 1, difference is:
In step a: control sodium hydroxide 5h and add, between p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1.2:1.8:1; It is 65-70 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 4.5h; Gained filtrate is carried out to underpressure distillation 1.2h under 100～130mmHg, 120～130 ℃ of conditions;
In step b: hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1.08:1, and the add-on of sodium tungstate catalyst accounts for 0.25% of p-nitrophenyl-beta-hydroxyethyl thioether quality; Add that in the process of hydrogen peroxide, to control temperature be 95-100 ℃, the lasting joining day of hydrogen peroxide is 4.5h; After hydrogen peroxide adds, at 95～100 ℃, react 1.5h;
In step c: the methyl alcohol that the oxidizing and crystallizing material that step b is obtained is 30-40% by mass percentage concentration carries out repetitive scrubbing;
In steps d: the mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.7:0.0015, at 60～80 ℃, hydrogen pressure, be then under 2.0～2.2MPa condition, to carry out hydrogenation reaction 5.0h;
In step e: the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1.04, stir and be warming up to 110 ℃, and under vacuum condition, to carry out esterification 2.8h(vacuum tightness be 0.04～0.06MPa).
Embodiment 5: substantially the same manner as Example 1, difference is:
In step a: control sodium hydroxide 4.5h and add, between p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1:1.5:1; It is 60-65 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 4.8h; Gained filtrate is carried out to underpressure distillation 1.8h under 90～130mmHg, 120～130 ℃ of conditions;
In step b: hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1.05:1, and the add-on of sodium tungstate catalyst accounts for 0.3% of p-nitrophenyl-beta-hydroxyethyl thioether quality; Add that in the process of hydrogen peroxide, to control temperature be 90-95 ℃, the lasting joining day of hydrogen peroxide is 4h; After hydrogen peroxide adds, at 95～100 ℃, react 1h;
In step c: the methyl alcohol that the oxidizing and crystallizing material that step b is obtained is 40-50% by mass percentage concentration carries out repetitive scrubbing;
In steps d: the mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.6:0.0008, at 40～60 ℃, hydrogen pressure, be then under 2.0～2.5MPa condition, to carry out hydrogenation reaction 6.0h;
In step e: the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1.05, stir and be warming up to 120 ℃, and under vacuum condition, to carry out esterification 2h(vacuum tightness be 0.06～0.08MPa).
Embodiment 6: substantially the same manner as Example 1, difference is:
In step a: control sodium hydroxide 5h and add, between p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1.2:2:1; It is 50-60 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 5h; Gained filtrate is carried out to underpressure distillation 1.0h under 100～150mmHg, 120～150 ℃ of conditions;
In step b: hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1.05:1, and the add-on of sodium tungstate catalyst accounts for 0.2% of p-nitrophenyl-beta-hydroxyethyl thioether quality; Add that in the process of hydrogen peroxide, to control temperature be 90-95 ℃, the lasting joining day of hydrogen peroxide is 4h; After hydrogen peroxide adds, at 95～100 ℃, react 2.5h;
In step c: the methyl alcohol that the oxidizing and crystallizing material that step b is obtained is 70-80% by mass percentage concentration carries out repetitive scrubbing;
In steps d: the mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.5:0.0007, at 100～110 ℃, hydrogen pressure, be then under 1.5～1.8MPa condition, to carry out hydrogenation reaction 3.0h;
In step e: the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1.05, stir and be warming up to 100 ℃, and under vacuum condition, to carry out esterification 3h(vacuum tightness be 0.08～0.09MPa).
Claims (8)
1. a preparation method for p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, is characterized in that, described preparation method comprises the following steps:
A, to take p-Nitrophenyl chloride and mercaptoethanol be basic raw material, first two kinds of basic raw materials added in DMF solvent and fully dissolve, mix, and then slowly adds sodium hydroxide, controls sodium hydroxide 3～5h and add; It is 50～80 ℃ that sodium hydroxide adds rear control temperature, under this temperature condition, reacts 3～5h, after reaction finishes, obtains reaction product; By gained reaction product solids removed by filtration NaC1, obtain filtrate, gained filtrate is carried out to underpressure distillation 1～2h under 60～150mmHg, 120～150 ℃ of conditions, steam moisture and DMF, obtain p-nitrophenyl-beta-hydroxyethyl thioether;
Between described p-Nitrophenyl chloride, mercaptoethanol, DMF and sodium hydroxide, the mol ratio of add-on is 1:1～1.2:1.5～2:1;
B, p-nitrophenyl-beta-hydroxyethyl thioether and tungstate catalysts that step a is obtained add stills for air blowing, under agitation slowly add hydrogen peroxide, add that in the process of hydrogen peroxide, to control temperature be 80～100 ℃, and the lasting joining day of hydrogen peroxide is 2～5h; After hydrogen peroxide adds, at 95～100 ℃, react 1～3h, after reaction finishes, lower the temperature, along with system temperature declines, oxidation material constantly crystallizes out; When temperature is down to below 30 ℃, carry out vacuum filtration, isolate oxidizing and crystallizing material;
Described hydrogen peroxide and the p-nitrophenyl-beta-hydroxyethyl thioether mol ratio between the two is 1～1.1:1, and the add-on of tungstate catalysts accounts for 0.1～0.3% of p-nitrophenyl-beta-hydroxyethyl thioether quality;
C, the oxidizing and crystallizing material that step b is obtained carry out repetitive scrubbing with methyl alcohol, remove the impurity in oxidizing and crystallizing material, then adopt deionized water wash to neutral, drain and remove methyl alcohol and deionized water, the oxidizing and crystallizing material after being processed;
In d, the processing rear oxidation crystallization material that obtains at step c, add aqueous solvent and palladium carbon catalyst, mass ratio between described oxidizing and crystallizing material, water and palladium carbon catalyst three is 1:1.3～1.7:0.0005～0.0015, then at 40～110 ℃, hydrogen pressure, be under 1.5～2.5MPa condition, to carry out hydrogenation reaction 3～6h, after finishing, reaction filters, leach catalyzer, obtain hydrogenation products and aqueous solvent;
E, the hydrogenation products that steps d is obtained and aqueous solvent directly add in esterification pot, then add bright sulfur acid, the acid of hydrogenation products and bright sulfur between the two the mol ratio of add-on be 1:1～1.05, stirring is warming up to 100～130 ℃, and under vacuum condition, carry out esterification 2～3h, reaction finishes rear discharging, after products therefrom is pulverized, obtains p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester.
2. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: the NaC1 of solids removed by filtration described in step a is to filter under 40 ℃ of conditions of temperature ﹤.
3. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: tungstate described in step b is sodium wolframate.
4. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: the mass percentage concentration of hydrogen peroxide described in step b is 30～34%.
5. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: during vacuum filtration described in step b, vacuum tightness is 0.04～0.06MPa.
6. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: the mass percentage concentration of methyl alcohol described in step c is 20～80%.
7. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: the catalyzer leaching in steps d, can recycle 2～3 times; The hydrogenation products obtaining does not carry out separated with aqueous solvent.
8. the preparation method of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that: described in step e and under vacuum condition, carry out esterification, its vacuum tightness 0.04～0.09MPa.
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Cited By (6)
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| CN106518736A (en) * | 2016-10-11 | 2017-03-22 | 浙江劲光实业股份有限公司 | Preparation method of 4-(beta-hydroxyethyl sulfone sulfate)-1,3-phenylenediamine and degreased product thereof |
| CN108329241A (en) * | 2018-04-12 | 2018-07-27 | 重庆华邦胜凯制药有限公司 | A kind of preparation method of dapsone |
| CN111018753A (en) * | 2019-12-18 | 2020-04-17 | 荆门市丽康源纺织科技有限公司 | Para-ester synthesis process for recycling acetic acid |
| CN111056981A (en) * | 2019-12-18 | 2020-04-24 | 荆门市丽康源纺织科技有限公司 | Para-ester synthesis method and para-ester |
| CN113999136A (en) * | 2021-12-07 | 2022-02-01 | 山东第一医科大学(山东省医学科学院) | Rheum officinale amide derivative, preparation method and application thereof, and liver cancer inhibitor specifically expressed by RECQL4 |
| CN115108951A (en) * | 2022-07-07 | 2022-09-27 | 广东众和高新科技股份公司 | P-nitrophenyl-beta-hydroxyethyl sulfide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106518736A (en) * | 2016-10-11 | 2017-03-22 | 浙江劲光实业股份有限公司 | Preparation method of 4-(beta-hydroxyethyl sulfone sulfate)-1,3-phenylenediamine and degreased product thereof |
| CN108329241A (en) * | 2018-04-12 | 2018-07-27 | 重庆华邦胜凯制药有限公司 | A kind of preparation method of dapsone |
| CN111018753A (en) * | 2019-12-18 | 2020-04-17 | 荆门市丽康源纺织科技有限公司 | Para-ester synthesis process for recycling acetic acid |
| CN111056981A (en) * | 2019-12-18 | 2020-04-24 | 荆门市丽康源纺织科技有限公司 | Para-ester synthesis method and para-ester |
| CN113999136A (en) * | 2021-12-07 | 2022-02-01 | 山东第一医科大学(山东省医学科学院) | Rheum officinale amide derivative, preparation method and application thereof, and liver cancer inhibitor specifically expressed by RECQL4 |
| CN113999136B (en) * | 2021-12-07 | 2023-08-04 | 山东第一医科大学(山东省医学科学院) | Rhein derivative, preparation method and application thereof, and liver cancer inhibitor specifically expressed by RECQL4 |
| CN115108951A (en) * | 2022-07-07 | 2022-09-27 | 广东众和高新科技股份公司 | P-nitrophenyl-beta-hydroxyethyl sulfide and preparation method thereof |
| CN115108951B (en) * | 2022-07-07 | 2023-11-28 | 广东众和高新科技股份公司 | P-nitrophenyl-beta-hydroxyethyl thioether and preparation method thereof |
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