CN111072527A - Preparation method of dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene - Google Patents
Preparation method of dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene Download PDFInfo
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- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
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Abstract
The invention discloses a preparation method of a dye intermediate 3- (β -hydroxyethyl sulfone) -nitrobenzene, which comprises the following steps of S1, obtaining m-nitrobenzenesulfonyl chloride by performing chlorosulfonation reaction on nitrobenzene and chlorosulfonic acid, S2, reducing the m-nitrobenzenesulfonyl chloride by using sodium metabisulfite, adjusting the pH value of a reaction solution to be 7.4-7.7 in the reaction process, adding sodium chloride after the reaction is finished, and salting out to obtain a reduction product, wherein the molar ratio of the sodium metabisulfite to the m-nitrobenzenesulfonyl chloride to the sodium chloride is (0.68-0.685) 1 (0.54-0.58), S3, adding ethylene oxide and sodium phosphate into the reduction product, controlling the pH value to be 7-7.5, reacting to obtain the 3- (β -hydroxyethyl sulfone) -nitrobenzene, wherein the molar ratio of the reduction product to the ethylene oxide to the sodium phosphate is 1 (0.52-0.63) 0.00.12.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene.
Background
In recent years, the field of the Chinese dye industry has continued to develop rapidly, and the yield of Chinese dyes has been in the first place in the world, accounting for about sixty percent of the total share in the world, and is the most important production country and supply region of intermediates.
The 3- (β -hydroxyethyl sulfonyl) -nitrobenzene is an important dye intermediate and has wide market application, the prior 3- (β -hydroxyethyl sulfonyl) -nitrobenzene is mainly prepared by taking nitrobenzene as a raw material in the production and carrying out chlorosulfonation, sulfonyl chloride reduction and condensation reaction, wherein in the chlorosulfonation step, a large amount of chlorosulfonic acid is required to participate in the reaction in order to improve the yield, a large amount of sulfuric acid wastewater is generated, the sulfuric acid wastewater is difficult to recover and corrodes equipment, in the condensation step, ethylene oxide or chloroethanol is adopted as a condensation agent, and the ethylene oxide or chloroethanol is easy to hydrolyze at high temperature, so that the purity and the yield of the condensation product are low, and the cost is increased by using excessive condensation agent;
in conclusion, the existing synthesis method of 3- (β -hydroxyethyl sulfone) -nitrobenzene has the disadvantages of low product yield, environmental pollution and poor environmental protection.
Disclosure of Invention
Aiming at least one defect or improvement requirement in the prior art, the invention provides a preparation method of a dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene, which introduces thionyl chloride in a chlorosulfonation process link to accelerate the rate of sulfonation reaction, stabilize the reaction, have high sulfonation reaction efficiency and fewer side reactions, can effectively improve the yield of sulfonation reaction and reduce the generation of byproducts, thereby not only improving the product quality, but also reducing the wastewater discharge and reducing the material consumption to achieve the effect of environmental protection, and in a sub-reduction process link, industrial salt is added in a reaction product to achieve good salting-out effect and large crystal precipitation, and sodium phosphate is added in a condensation process link as a buffering agent to stabilize the pH value, inhibit the hydrolysis of ethylene oxide, improve the purity and yield of a condensation product, reduce the usage amount of ethylene oxide and reduce the cost.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a dye intermediate 3- (β -hydroxyethyl sulfone) -nitrobenzene, comprising the steps of:
s1: carrying out chlorosulfonation reaction on nitrobenzene and chlorosulfonic acid to obtain m-nitrobenzenesulfonyl chloride;
s2: reducing the m-nitrobenzenesulfonyl chloride by using sodium metabisulfite, and adjusting the pH value of a reaction solution to 7.4-7.7 by using liquid alkali in the reaction process; after the reaction is finished, adding sodium chloride, and salting out to obtain a reduction product; wherein, the molar ratio of the sodium pyrosulfite, the m-nitrobenzenesulfonyl chloride and the sodium chloride (0.68-0.685) is as follows: 1: (0.54-0.58);
and S3, adding ethylene oxide and sodium phosphate into the reduction product, controlling the pH value to be 7-7.5, and reacting to obtain the 3- (β -hydroxyethyl sulfone) -nitrobenzene, wherein the molar ratio of the reduction product to the ethylene oxide to the sodium phosphate is 1 (0.52-0.63): 0.00.12.
Preferably, in the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene, in the step S1, thionyl chloride is added in the chlorosulfonation reaction of nitrobenzene and chlorosulfonic acid, and the molar ratio of nitrobenzene, chlorosulfonic acid and thionyl chloride is (0.57-0.6):1 (0.48-0.50).
Preferably, in the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene, in step S2, the molar ratio of the sodium metabisulfite to the m-nitrobenzenesulfonyl chloride to the sodium chloride is 0.685: 1: 0.55.
Preferably, in the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene, in step S3, the molar ratio of the reduction product, ethylene oxide and sodium phosphate is 1: 0.625: 0.0012.
Preferably, the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene comprises the following steps in step S2:
(1) adjusting the pH value of a sodium metabisulfite solution to 7.4-7.7 by using liquid caustic soda, and adding m-nitrobenzenesulfonyl chloride; in the adding process, the pH value of the mixed solution is maintained to be 7.4-7.7 through liquid alkali, and the temperature is controlled to be 25-28 ℃; after the m-nitrobenzenesulfonyl chloride is added, stirring and reacting for 1-2 hours at the temperature of 25-28 ℃ under a heat preservation condition;
(2) adding sodium chloride after the heat preservation is finished, stirring for 0.5-1 hour, and obtaining a reduction product through salting out;
(3) and carrying out filter pressing treatment on the reduction product, and controlling the water content of the reduction product to be below 5%.
Preferably, the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene comprises the following steps in step S3:
(1) adding the reduction product into a condensation kettle, vacuumizing, introducing inert gas, heating to 70-80 ℃, and adding sodium phosphate;
(2) adding ethylene oxide, and adding acid to adjust the pH value to 7-7.5 in the adding process; after the addition of ethylene oxide, the reaction is carried out at 70-80 ℃ for 3-4 hours.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene provided by the invention has the advantages that in the sub-reduction process link, industrial salt is added into a reaction product, the salting-out effect is good, the precipitated crystal is large, in the condensation process link, sodium phosphate is added as a buffering agent, the pH value is stabilized, the hydrolysis of ethylene oxide is inhibited, the purity and the yield of a condensation product are improved, the use amount of the ethylene oxide is reduced, and the cost is reduced.
(2) According to the preparation method of the dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene, thionyl chloride is introduced to a chlorosulfonation process link for chlorosulfonation, so that the rate of sulfonation reaction is accelerated, the reaction is stable, the sulfonation reaction efficiency is high, side reactions are few, the yield of sulfonation reaction can be effectively improved, the generation of byproducts is reduced, the product quality is improved, the wastewater discharge is reduced, the material consumption is reduced, and the effect of environmental protection is achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene, which comprises the following steps:
s1: carrying out chlorosulfonation reaction on nitrobenzene and chlorosulfonic acid to obtain m-nitrobenzenesulfonyl chloride, and adding thionyl chloride in the reaction process; wherein the mol ratio of nitrobenzene, chlorosulfonic acid and thionyl chloride is (0.57-0.6) to 1 (0.48-0.50);
the chlorosulfonyl acylation of thionyl chloride is introduced by the original simple sulfonation of chlorosulfonic acid, so that the sulfonation reaction rate is accelerated, the reaction is stable, the sulfonation reaction efficiency is high, and the side reaction is less; the method can effectively improve the yield of sulfonation reaction, reduce the generation of byproducts, improve the product quality, reduce the discharge amount of wastewater, reduce the material consumption and achieve the effect of environmental protection. After the thionyl chloride is added, the yield of the sulfonated product is improved by at least 7 percent.
S2: reducing the m-nitrobenzenesulfonyl chloride by using sodium metabisulfite, and adjusting the pH value of a reaction solution to 7.4-7.7 by using liquid alkali in the reaction process; after the reaction is finished, adding sodium chloride, and salting out to obtain a reduction product; wherein, the molar ratio of the sodium pyrosulfite, the m-nitrobenzenesulfonyl chloride and the sodium chloride (0.68-0.685) is as follows: 1: (0.54-0.58);
industrial salt is added into the reaction product, the salting-out effect is good, the precipitated crystal is large, and the product yield is improved by at least 5%.
S3, adding ethylene oxide and sodium phosphate into the reduction product, controlling the pH value to be 7-7.5, and reacting to obtain 3- (β -hydroxyethyl sulfone) -nitrobenzene, wherein the molar ratio of the reduction product to the ethylene oxide to the sodium phosphate is 1 (0.52-0.63): 0.00.12;
according to the invention, sodium phosphate is added as a buffering agent, the pH value is stabilized, hydrolysis of ethylene oxide is inhibited, and the purity and yield of condensation products are improved, and experimental data show that the product yield is improved by more than 8%; and the usage amount of the ethylene oxide is reduced, and the cost is reduced.
The preparation of 3- (β -hydroxyethyl sulfone) -nitrobenzene provided by the present invention is described in detail below with reference to the examples.
Example 1
First, chlorosulfonation process link
(1) Adding metered chlorosulfonic acid into a low-temperature sulfonation pot at one time, starting stirring, adding quantitative nitrobenzene in a trickle state at the temperature of less than or equal to 30 ℃, controlling the feeding time to be 0.5-1 hour, maintaining for 2 hours after the feeding is finished, and controlling the temperature to be 25-35 ℃;
(2) transferring the low-temperature sulfonated material into a high-temperature sulfonation pot, heating to 60 ℃, maintaining for 1 hour, and adding thionyl chloride; wherein, the mol ratio of nitrobenzene to chlorosulfonic acid to thionyl chloride is nitrobenzene: chlorosulfonic acid: 0.57:1:0.48 of thionyl chloride; after adding thionyl chloride, controlling the temperature at 60 ℃; the dropping time of the thionyl chloride is controlled to be about 2-3 hours, after the thionyl chloride is added, steam is started to heat, and the heating process is carried out for 2-3 hours; as the reaction is exothermic, trace steam is firstly used for heating to about 85 ℃, then the temperature is naturally raised to about 105 ℃, the temperature is kept at 103-107 ℃ for 4-6 hours to obtain the m-nitrobenzenesulfonyl chloride, and the end point of the reaction is sampled and determined.
Second, inferior reduction process link
(1) Adding a certain amount of water into a reaction kettle, adding 150kg of sodium metabisulfite, and stirring to dissolve the sodium metabisulfite; adding 30% liquid alkali into the trickle for neutralization, controlling the temperature to be 25-28 ℃, and detecting the PH to be 7.4-7.7, namely completing the neutralization;
(2) adding 15kg of m-nitrobenzenesulfonyl chloride, neutralizing the PH value to 7.4-7.7 by using 30% liquid alkali, continuously adding the m-nitrobenzenesulfonyl chloride, and repeating the steps until the calculated amount of the m-nitrobenzenesulfonyl chloride is completely added, wherein the addition is about 2-3 hours, the PH value is strictly controlled to be 7.4-7.7 by using 30% liquid alkali in the feeding process, and the reaction temperature is 25-28 ℃; after all the materials are added, controlling the pH value to be 7.4-7.7 and the temperature to be 25 ℃, stirring, preserving heat and reacting for 1 hour;
(3) after the heat preservation is finished, adding weighed refined salt (sodium chloride), stirring for 0.5 hour, and salting out to obtain m-nitrobenzenesulfinic acid; wherein the molar ratio of the sodium metabisulfite, the m-nitrobenzenesulfonyl chloride and the industrial salt is sodium metabisulfite: m-nitrobenzenesulfonyl chloride: commercial salt 0.68: 1: 0.54;
(4) pressing the salting-out product to a filter press by adopting compressed air, closing a filter pressing feeding valve on a reaction pot after the filter press finishes feeding, opening an emptying valve, opening a compressed air inlet valve, blowing the material for 0.5-1 hour until no filtrate flows out, and drying and discharging; the lower the water content of the material, the better, the sampling analysis should be below 5%.
Thirdly, condensation reaction link
(1) Adding the reduction product m-nitrobenzenesulfinic acid into a condensation pot, sealing the pot, vacuumizing (negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 70 ℃, starting a material circulating pump, and adding a certain amount of sodium phosphate;
(2) replacing the ethylene oxide feeding pipe with nitrogen to prevent blockage; beginning to add metered ethylene oxide, simultaneously opening a dilute acid feed valve, controlling the pH value to be 7-7.5 in the ethylene oxide adding process, and not allowing partial acid or partial alkali; controlling the temperature at 75 ℃; the addition time of ethylene oxide was 3 hours; wherein, the mass molar ratio of m-nitrobenzenesulfinic acid, ethylene oxide and sodium phosphate is m-nitrobenzenesulfinic acid: ethylene oxide: sodium phosphate 1: 0.52: 0.0012;
(3) after the ethylene oxide is added, the temperature is raised to 70 ℃, the PH value is always maintained in alkalescent environment, the reaction is carried out for 3 hours, 3- (β -hydroxyethyl sulfone) -nitrobenzene is obtained, sampling analysis is carried out, and the material is discharged when the temperature of the circulating water is reduced to 30 ℃ after the material is qualified.
Example 2
First, chlorosulfonation process link
(1) Adding metered chlorosulfonic acid into a low-temperature sulfonation pot at one time, starting stirring, adding quantitative nitrobenzene in a trickle state at the temperature of less than or equal to 30 ℃, controlling the feeding time to be 0.5-1 hour, maintaining for 2 hours after the feeding is finished, and controlling the temperature to be 25-35 ℃;
(2) transferring the low-temperature sulfonated material into a high-temperature sulfonation pot, heating to 60 ℃, maintaining for 1 hour, and adding thionyl chloride; wherein, the mol ratio of nitrobenzene to chlorosulfonic acid to thionyl chloride is nitrobenzene: chlorosulfonic acid: 0.58:1: 0.50; after adding thionyl chloride, controlling the temperature at 60 ℃; the dropping time of the thionyl chloride is controlled to be about 2-3 hours, after the thionyl chloride is added, steam is started to heat, and the heating process is carried out for 2-3 hours; as the reaction is exothermic, trace steam is firstly used for heating to about 85 ℃, then the temperature is naturally raised to about 105 ℃, the temperature is kept at 103-107 ℃ for 4-6 hours to obtain the m-nitrobenzenesulfonyl chloride, and the end point of the reaction is sampled and determined.
Second, inferior reduction process link
(1) Adding a certain amount of water into a reaction kettle, adding 150kg of sodium metabisulfite, and stirring to dissolve the sodium metabisulfite; adding 30% liquid alkali into the trickle for neutralization, controlling the temperature to be 25-28 ℃, and detecting the PH to be 7.4-7.7, namely completing the neutralization;
(2) adding 15kg of m-nitrobenzenesulfonyl chloride, neutralizing the PH value to 7.4-7.7 by using 30% liquid alkali, continuously adding the m-nitrobenzenesulfonyl chloride, and repeating the steps until the calculated amount of the m-nitrobenzenesulfonyl chloride is completely added, wherein the addition is about 2-3 hours, the PH value is strictly controlled to be 7.4-7.7 by using 30% liquid alkali in the feeding process, and the reaction temperature is 25-28 ℃; after all the materials are added, controlling the pH value to be 7.4-7.7 and the temperature to be 26 ℃, stirring, preserving heat and reacting for 1.5 hours;
(3) after the heat preservation is finished, adding weighed refined salt (sodium chloride), stirring for 0.6 hour, and salting out to obtain m-nitrobenzenesulfinic acid; wherein the molar ratio of the sodium metabisulfite, the m-nitrobenzenesulfonyl chloride and the industrial salt is sodium metabisulfite: m-nitrobenzenesulfonyl chloride: industrial salt 0.685: 1: 0.54;
(4) pressing the salting-out product to a filter press by adopting compressed air, closing a filter pressing feeding valve on a reaction pot after the filter press finishes feeding, opening an emptying valve, opening a compressed air inlet valve, blowing the material for 0.5-1 hour until no filtrate flows out, and drying and discharging; the lower the water content of the material, the better, the sampling analysis should be below 5%.
Thirdly, condensation reaction link
(1) Adding the reduction product m-nitrobenzenesulfinic acid into a condensation pot, sealing the pot, vacuumizing (negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 75 ℃, starting a material circulating pump, and adding a certain amount of sodium phosphate;
(2) replacing the ethylene oxide feeding pipe with nitrogen to prevent blockage; beginning to add metered ethylene oxide, simultaneously opening a dilute acid feed valve, controlling the pH value to be 7-7.5 in the ethylene oxide adding process, and not allowing partial acid or partial alkali; controlling the temperature at 75 ℃; the addition time of ethylene oxide was 3 hours; wherein, the mass molar ratio of m-nitrobenzenesulfinic acid, ethylene oxide and sodium phosphate is m-nitrobenzenesulfinic acid: ethylene oxide: sodium phosphate 1: 0.55: 0.0012;
(3) after the ethylene oxide is added, the temperature is raised to 75 ℃, the PH value is always maintained in alkalescent environment, the reaction is carried out for 3.5 hours, and 3- (β -hydroxyethyl sulfone) -nitrobenzene is obtained, and sampling analysis is carried out, after the product is qualified, the circulating water is boiled and the temperature is reduced to 30 ℃, and then the product is discharged.
Example 3
First, chlorosulfonation process link
(1) Adding metered chlorosulfonic acid into a low-temperature sulfonation pot at one time, starting stirring, adding quantitative nitrobenzene in a trickle state at the temperature of less than or equal to 30 ℃, controlling the feeding time to be 0.5-1 hour, maintaining for 2 hours after the feeding is finished, and controlling the temperature to be 25-35 ℃;
(2) transferring the low-temperature sulfonated material into a high-temperature sulfonation pot, heating to 60 ℃, maintaining for 1 hour, and adding thionyl chloride; wherein, the mol ratio of nitrobenzene to chlorosulfonic acid to thionyl chloride is nitrobenzene: chlorosulfonic acid: 0.59:1: 0.49; after adding thionyl chloride, controlling the temperature at 60 ℃; the dropping time of the thionyl chloride is controlled to be about 2-3 hours, after the thionyl chloride is added, steam is started to heat, and the heating process is carried out for 2-3 hours; as the reaction is exothermic, trace steam is firstly used for heating to about 85 ℃, then the temperature is naturally raised to about 105 ℃, the temperature is kept at 103-107 ℃ for 4-6 hours to obtain the m-nitrobenzenesulfonyl chloride, and the end point of the reaction is sampled and determined.
Second, inferior reduction process link
(1) Adding a certain amount of water into a reaction kettle, adding 150kg of sodium metabisulfite, and stirring to dissolve the sodium metabisulfite; adding 30% liquid alkali into the trickle for neutralization, controlling the temperature to be 25-28 ℃, and detecting the PH to be 7.4-7.7, namely completing the neutralization;
(2) adding 15kg of m-nitrobenzenesulfonyl chloride, neutralizing the PH value to 7.4-7.7 by using 30% liquid alkali, continuously adding the m-nitrobenzenesulfonyl chloride, and repeating the steps until the calculated amount of the m-nitrobenzenesulfonyl chloride is completely added, wherein the addition is about 2-3 hours, the PH value is strictly controlled to be 7.4-7.7 by using 30% liquid alkali in the feeding process, and the reaction temperature is 25-28 ℃; after all the materials are added, controlling the pH value to be 7.4-7.7 and the temperature to be 27 ℃, stirring, preserving heat and reacting for 2 hours;
(3) after the heat preservation is finished, adding weighed refined salt (sodium chloride), stirring for 0.8 hour, and salting out to obtain m-nitrobenzenesulfinic acid; wherein the molar ratio of the sodium metabisulfite, the m-nitrobenzenesulfonyl chloride and the industrial salt is sodium metabisulfite: m-nitrobenzenesulfonyl chloride: industrial salt 0.685: 1: 0.55;
(4) pressing the salting-out product to a filter press by adopting compressed air, closing a filter pressing feeding valve on a reaction pot after the filter press finishes feeding, opening an emptying valve, opening a compressed air inlet valve, blowing the material for 0.5-1 hour until no filtrate flows out, and drying and discharging; the lower the water content of the material, the better, the sampling analysis should be below 5%.
Thirdly, condensation reaction link
(1) Adding the reduction product m-nitrobenzenesulfinic acid into a condensation pot, sealing the pot, vacuumizing (negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 80 ℃, starting a material circulating pump, and adding a certain amount of sodium phosphate;
(2) replacing the ethylene oxide feeding pipe with nitrogen to prevent blockage; beginning to add metered ethylene oxide, simultaneously opening a dilute acid feed valve, controlling the pH value to be 7-7.5 in the ethylene oxide adding process, and not allowing partial acid or partial alkali; controlling the temperature at 75 ℃; the addition time of ethylene oxide was 3 hours; wherein, the mass molar ratio of m-nitrobenzenesulfinic acid, ethylene oxide and sodium phosphate is m-nitrobenzenesulfinic acid: ethylene oxide: sodium phosphate 1: 0.60: 0.0012;
(3) after the ethylene oxide is added, the temperature is raised to 80 ℃, the PH value is always maintained in alkalescent environment, the reaction is carried out for 4 hours, 3- (β -hydroxyethyl sulfone) -nitrobenzene is obtained, sampling analysis is carried out, and the material is discharged when the temperature of the circulating water is reduced to 30 ℃ after the material is qualified.
Example 4
First, chlorosulfonation process link
(1) Adding metered chlorosulfonic acid into a low-temperature sulfonation pot at one time, starting stirring, adding quantitative nitrobenzene in a trickle state at the temperature of less than or equal to 30 ℃, controlling the feeding time to be 0.5-1 hour, maintaining for 2 hours after the feeding is finished, and controlling the temperature to be 25-35 ℃;
(2) transferring the low-temperature sulfonated material into a high-temperature sulfonation pot, heating to 60 ℃, maintaining for 1 hour, and adding thionyl chloride; wherein, the mol ratio of nitrobenzene to chlorosulfonic acid to thionyl chloride is nitrobenzene: chlorosulfonic acid: 0.6:1:0.50 of thionyl chloride; after adding thionyl chloride, controlling the temperature at 60 ℃; the dropping time of the thionyl chloride is controlled to be about 2-3 hours, after the thionyl chloride is added, steam is started to heat, and the heating process is carried out for 2-3 hours; as the reaction is exothermic, trace steam is firstly used for heating to about 85 ℃, then the temperature is naturally raised to about 105 ℃, the temperature is kept at 103-107 ℃ for 4-6 hours to obtain the m-nitrobenzenesulfonyl chloride, and the end point of the reaction is sampled and determined.
Second, inferior reduction process link
(1) Adding a certain amount of water into a reaction kettle, adding 150kg of sodium metabisulfite, and stirring to dissolve the sodium metabisulfite; adding 30% liquid alkali into the trickle for neutralization, controlling the temperature to be 25-28 ℃, and detecting the PH to be 7.4-7.7, namely completing the neutralization;
(2) adding 15kg of m-nitrobenzenesulfonyl chloride, neutralizing the PH value to 7.4-7.7 by using 30% liquid alkali, continuously adding the m-nitrobenzenesulfonyl chloride, and repeating the steps until the calculated amount of the m-nitrobenzenesulfonyl chloride is completely added, wherein the addition is about 2-3 hours, the PH value is strictly controlled to be 7.4-7.7 by using 30% liquid alkali in the feeding process, and the reaction temperature is 25-28 ℃; after all the materials are added, controlling the pH value to be 7.4-7.7 and the temperature to be 28 ℃, stirring, preserving heat and reacting for 1.5 hours;
(3) after the heat preservation is finished, adding weighed refined salt (sodium chloride), stirring for 1 hour, and salting out to obtain m-nitrobenzenesulfinic acid; wherein the molar ratio of the sodium metabisulfite, the m-nitrobenzenesulfonyl chloride and the industrial salt is sodium metabisulfite: m-nitrobenzenesulfonyl chloride: commercial salt 0.68: 1: 0.56;
(4) pressing the salting-out product to a filter press by adopting compressed air, closing a filter pressing feeding valve on a reaction pot after the filter press finishes feeding, opening an emptying valve, opening a compressed air inlet valve, blowing the material for 0.5-1 hour until no filtrate flows out, and drying and discharging; the lower the water content of the material, the better, the sampling analysis should be below 5%.
Thirdly, condensation reaction link
(1) Adding the reduction product m-nitrobenzenesulfinic acid into a condensation pot, sealing the pot, vacuumizing (negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 70 ℃, starting a material circulating pump, and adding a certain amount of sodium phosphate;
(2) replacing the ethylene oxide feeding pipe with nitrogen to prevent blockage; beginning to add metered ethylene oxide, simultaneously opening a dilute acid feed valve, controlling the pH value to be 7-7.5 in the ethylene oxide adding process, and not allowing partial acid or partial alkali; controlling the temperature at 75 ℃; the addition time of ethylene oxide was 3 hours; wherein, the mass molar ratio of m-nitrobenzenesulfinic acid, ethylene oxide and sodium phosphate is m-nitrobenzenesulfinic acid: ethylene oxide: sodium phosphate 1: 0.63: 0.0012;
(3) after the ethylene oxide is added, the temperature is raised to 70 ℃, the PH value is always maintained in alkalescent environment, the reaction is carried out for 3 hours, 3- (β -hydroxyethyl sulfone) -nitrobenzene is obtained, sampling analysis is carried out, and the material is discharged when the temperature of the circulating water is reduced to 30 ℃ after the material is qualified.
Example 5
First, chlorosulfonation process link
(1) Adding metered chlorosulfonic acid into a low-temperature sulfonation pot at one time, starting stirring, adding quantitative nitrobenzene in a trickle state at the temperature of less than or equal to 30 ℃, controlling the feeding time to be 0.5-1 hour, maintaining for 2 hours after the feeding is finished, and controlling the temperature to be 25-35 ℃;
(2) transferring the low-temperature sulfonated material into a high-temperature sulfonation pot, heating to 60 ℃, maintaining for 1 hour, and adding thionyl chloride; wherein, the mol ratio of nitrobenzene to chlorosulfonic acid to thionyl chloride is nitrobenzene: chlorosulfonic acid: 0.58:1: 0.48; after adding thionyl chloride, controlling the temperature at 60 ℃; the dropping time of the thionyl chloride is controlled to be about 2-3 hours, after the thionyl chloride is added, steam is started to heat, and the heating process is carried out for 2-3 hours; as the reaction is exothermic, trace steam is firstly used for heating to about 85 ℃, then the temperature is naturally raised to about 105 ℃, the temperature is kept at 103-107 ℃ for 4-6 hours to obtain the m-nitrobenzenesulfonyl chloride, and the end point of the reaction is sampled and determined.
Second, inferior reduction process link
(1) Adding a certain amount of water into a reaction kettle, adding 150kg of sodium metabisulfite, and stirring to dissolve the sodium metabisulfite; adding 30% liquid alkali into the trickle for neutralization, controlling the temperature to be 25-28 ℃, and detecting the PH to be 7.4-7.7, namely completing the neutralization;
(2) adding 15kg of m-nitrobenzenesulfonyl chloride, neutralizing the PH value to 7.4-7.7 by using 30% liquid alkali, continuously adding the m-nitrobenzenesulfonyl chloride, and repeating the steps until the calculated amount of the m-nitrobenzenesulfonyl chloride is completely added, wherein the addition is about 2-3 hours, the PH value is strictly controlled to be 7.4-7.7 by using 30% liquid alkali in the feeding process, and the reaction temperature is 25-28 ℃; after all the materials are added, controlling the pH value to be 7.4-7.7 and the temperature to be 28 ℃, stirring, preserving heat and reacting for 1 hour;
(3) after the heat preservation is finished, adding weighed refined salt (sodium chloride), stirring for 0.5 hour, and salting out to obtain m-nitrobenzenesulfinic acid; wherein the molar ratio of the sodium metabisulfite, the m-nitrobenzenesulfonyl chloride and the industrial salt is sodium metabisulfite: m-nitrobenzenesulfonyl chloride: commercial salt 0.68: 1: 0.58;
(4) pressing the salting-out product to a filter press by adopting compressed air, closing a filter pressing feeding valve on a reaction pot after the filter press finishes feeding, opening an emptying valve, opening a compressed air inlet valve, blowing the material for 0.5-1 hour until no filtrate flows out, and drying and discharging; the lower the water content of the material, the better, the sampling analysis should be below 5%.
Thirdly, condensation reaction link
(1) Adding the reduction product m-nitrobenzenesulfinic acid into a condensation pot, sealing the pot, vacuumizing (negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 70 ℃, starting a material circulating pump, and adding a certain amount of sodium phosphate;
(2) replacing the ethylene oxide feeding pipe with nitrogen to prevent blockage; beginning to add metered ethylene oxide, simultaneously opening a dilute acid feed valve, controlling the pH value to be 7-7.5 in the ethylene oxide adding process, and not allowing partial acid or partial alkali; controlling the temperature at 75 ℃; the addition time of ethylene oxide was 3 hours; wherein, the mass molar ratio of m-nitrobenzenesulfinic acid, ethylene oxide and sodium phosphate is m-nitrobenzenesulfinic acid: ethylene oxide: sodium phosphate 1: 0.625: 0.0012;
(3) after the ethylene oxide is added, the temperature is raised to 70 ℃, the PH value is always maintained in alkalescent environment, the reaction is carried out for 3 hours, 3- (β -hydroxyethyl sulfone) -nitrobenzene is obtained, sampling analysis is carried out, and the material is discharged when the temperature of the circulating water is reduced to 30 ℃ after the material is qualified.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of a dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene is characterized by comprising the following steps:
s1: carrying out chlorosulfonation reaction on nitrobenzene and chlorosulfonic acid to obtain m-nitrobenzenesulfonyl chloride;
s2: reducing the m-nitrobenzenesulfonyl chloride by using sodium metabisulfite, and adjusting the pH value of a reaction liquid to 7.4-7.7 in the reaction process; after the reaction is finished, adding sodium chloride, and salting out to obtain a reduction product; wherein, the molar ratio of the sodium pyrosulfite, the m-nitrobenzenesulfonyl chloride and the sodium chloride (0.68-0.685) is as follows: 1: (0.54-0.58);
and S3, adding ethylene oxide and sodium phosphate into the reduction product, controlling the pH value to be 7-7.5, and reacting to obtain the 3- (β -hydroxyethyl sulfone) -nitrobenzene, wherein the molar ratio of the reduction product to the ethylene oxide to the sodium phosphate is 1 (0.52-0.63): 0.00.12.
2. The process for preparing 3- (β -hydroxyethyl sulfone) -nitrobenzene as a dye intermediate according to claim 1, wherein in step S1, thionyl chloride is added during the chlorosulfonation of nitrobenzene and chlorosulfonic acid, and the molar ratio of nitrobenzene, chlorosulfonic acid, thionyl chloride is (0.57-0.6):1 (0.48-0.50).
3. The method for preparing 3- (β -hydroxyethyl sulfone) -nitrobenzene as dye intermediate in claim 1, wherein the molar ratio of sodium metabisulfite, m-nitrobenzenesulfonyl chloride and sodium chloride is 0.685: 1: 0.55 in step S2.
4. The method for preparing 3- (β -hydroxyethyl sulfone) -nitrobenzene as the dye intermediate in claim 1, wherein the molar ratio of the reduction product, ethylene oxide and sodium phosphate is 1: 0.625: 0.0012 in step S3.
5. The method for preparing 3- (β -hydroxyethyl sulfone) -nitrobenzene as dye intermediate in claim 3, wherein step S2 comprises:
(1) adjusting the pH value of a sodium metabisulfite solution to 7.4-7.7 by using liquid caustic soda, and adding m-nitrobenzenesulfonyl chloride; in the adding process, the pH value of the mixed solution is maintained to be 7.4-7.7 through liquid alkali, and the temperature is controlled to be 25-28 ℃; after the m-nitrobenzenesulfonyl chloride is added, stirring and reacting for 1-2 hours at the temperature of 25-28 ℃ under a heat preservation condition;
(2) adding sodium chloride after the heat preservation is finished, stirring for 0.5-1 hour, and obtaining a reduction product through salting out;
(3) and carrying out filter pressing treatment on the reduction product, and controlling the water content of the reduction product to be below 5%.
6. The method for preparing 3- (β -hydroxyethyl sulfone) -nitrobenzene as dye intermediate according to claim 4, wherein step S3 comprises:
(1) adding the reduction product into a condensation kettle, vacuumizing, introducing inert gas, heating to 70-80 ℃, and adding sodium phosphate;
(2) adding ethylene oxide, and adding acid to adjust the pH value to 7-7.5 in the adding process; after the addition of ethylene oxide, the reaction is carried out at 70-80 ℃ for 3-4 hours.
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