CN109020915B - Method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid - Google Patents
Method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid Download PDFInfo
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- CN109020915B CN109020915B CN201811096104.1A CN201811096104A CN109020915B CN 109020915 B CN109020915 B CN 109020915B CN 201811096104 A CN201811096104 A CN 201811096104A CN 109020915 B CN109020915 B CN 109020915B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/12—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms condensed with carbocyclic rings or ring systems
Abstract
A method for improving the nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid, the method comprising the steps of: (1) Injecting organic acid anhydride into a reaction kettle, adding 1, 2-diazoxynaphthalene-4-sulfonic acid, and cooling to a certain temperature; (2) Slowly adding a nitrating agent for nitration, carrying out heat preservation reaction, diluting with water after the reaction is finished, standing for crystallization, and filtering to obtain the product. Compared with the prior reaction system, the reaction system of the method has the characteristics of more convenient operation, higher selectivity of the nitration position, more environment-friendly property and the like.
Description
Technical Field
The invention relates to a method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid.
Background
1, 2-diazoxynaphthalene-4-sulfonic acid is an important intermediate for synthesizing 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid, and is widely used for synthesizing acid complex peach red B, acid mordant black R, acid complex salt GGN, acid mordant jujube red BN and other dyes. The traditional process of the compound nitration unit reaction is to use mixed acid consisting of nitric acid and sulfuric acid to carry out nitration on reactants, the method can generate a large amount of acidic wastewater, and serious pollution is caused to water resources and atmosphere, and in addition, the method has low multi-nitration side reaction and regioselectivity, which are difficult problems troubling the industry all the time. In order to improve the reaction yield and reduce the byproducts, researchers have developed various improvement modes based on the original process, including processes of adding an organic solvent, or adding hydrogen peroxide and ferrous sulfate to cooperate with a specific stirring mode, and the like. However, the improved processes still do not depart from the category of sulfuric acid and nitric acid, and the problem of serious pollution of industrial wastes is not fundamentally solved, so that the development and research of the process for preparing 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid by high-selectivity nitration of 1, 2-diazoxynaphthalene-4-sulfonic acid are not interrupted.
Disclosure of Invention
The invention aims to provide a method for improving the nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid, which solves the problems that the existing method can generate a large amount of acidic wastewater, seriously pollutes water resources and atmosphere, has multiple nitration side reactions and low regioselectivity, and has the characteristics of more convenient operation, higher nitration position selectivity and more environment-friendly property.
The technical scheme adopted for achieving the aim is that the method for improving the nitration selectivity of the 1, 2-diazoxynaphthalene-4-sulfonic acid comprises the following steps:
(1) Injecting organic acid anhydride into a reaction kettle, adding 1, 2-diazoxynaphthalene-4-sulfonic acid, and cooling to a certain temperature;
(2) Slowly adding a nitrating reagent to carry out nitration and carrying out heat preservation reaction, adding water to dilute after the reaction is finished, standing for crystallization, and filtering to obtain the product.
The organic acid anhydride is acetic anhydride or propionic anhydride or a mixture of the two.
The ratio of the weight of the organic acid anhydride to the weight of the 1, 2-diazoxynaphthalene-4-sulfonic acid is 1.5: 1-3: 1.
The nitration reaction temperature is 20 o C ~ 30 o And C.
The nitrating agent is a mixture of potassium nitrate and potassium bisulfate in a weight ratio of 1: 1.4.
Advantageous effects
Compared with the prior art, the invention has the following advantages.
The method has the advantages that the reaction conditions of the method do not need concentrated sulfuric acid and concentrated nitric acid, the method is more environment-friendly, the nitration position selectivity is high, the yield is better, the product is easy to purify, and the like.
Detailed Description
A method for increasing the nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid, the method comprising the steps of:
(1) Injecting organic acid anhydride into a reaction kettle, adding 1, 2-diazoxynaphthalene-4-sulfonic acid, and cooling to a certain temperature;
(2) Slowly adding a nitrating agent for nitration, carrying out heat preservation reaction, diluting with water after the reaction is finished, standing for crystallization, and filtering to obtain the product.
The organic acid anhydride is acetic anhydride or propionic anhydride or a mixture of the two.
The ratio of the weight of the organic acid anhydride to the weight of the 1, 2-diazoxynaphthalene-4-sulfonic acid is 1.5: 1-3: 1.
The nitration reaction temperature is 20 o C ~ 30 o And C.
The nitration reagent is a mixture of potassium nitrate and potassium bisulfate in a weight ratio of 1: 1.4.
The invention mainly solves the technical problem of getting rid of a sulfuric acid and nitric acid system completely, and the 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid is synthesized by high-selectivity nitration of 1, 2-diazoxynaphthalene-4-sulfonic acid by a nitration system which is relatively friendly to the environment; the technological conditions are that acid anhydride is used as reaction solvent, potassium nitrate with large cation radius is used as nitrating agent to nitrify raw material, and the product 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid can be obtained with high selectivity.
The reaction formula for synthesizing 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid by high-selectivity nitration of 1, 2-diazoxynaphthalene-4-sulfonic acid is as follows:
in the steps of the invention, after 1, 2-diazoxynaphthalene-4-sulfonic acid is added into acid anhydride, the temperature of the system can rise to a certain extent, and in order to obtain better reaction selectivity, the temperature of the system needs to be reduced to a certain temperature, wherein the temperature is 20 DEG o C ~ 30 o C is between;
in the steps of the invention, 1, 2-diazoxynaphthalene-4-sulfonic acid is added with anhydride, the system is cooled to a certain temperature, then a nitrating agent is slowly added for nitration, the nitrating agent is a mixture of potassium nitrate and potassium bisulfate 1, the reaction is carried out for 45 minutes after the nitrating agent is added, and the product 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid can be separated out after the nitrating agent is added with water for dilution. The content of the 6-nitro product in the crude product is more than 93 percent and far higher than about 80 percent in the traditional process, and the by-product is more environment-friendly.
Example 1
Weighing 50 kg of acetic anhydride, putting the acetic anhydride into a reaction kettle, slowly adding 25 kg of 1, 2-diazoxynaphthalene-4-sulfonic acid, stirring until the acetic anhydride is fully dissolved, cooling to 25 ℃, slowly adding a mixture of 10 kg of potassium nitrate and 14 kg of potassium bisulfate, keeping the temperature for reaction for 45 minutes after the addition is finished, pouring 25 kg of cold water into the reaction liquid, crystallizing, and filtering to obtain 28.5 kg of 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid, wherein the HPLC purity of the product is 93.4%, and the total yield is 95%.
Example 2
Weighing 50 kg of acetic anhydride, putting the acetic anhydride into a reaction kettle, slowly adding 25 kg of 1, 2-diazoxynaphthalene-4-sulfonic acid, stirring until the acetic anhydride is fully dissolved, cooling to 30 ℃, slowly adding a mixture of 10 kg of potassium nitrate and 14 kg of potassium bisulfate, keeping the temperature for reaction for 45 minutes after the addition is finished, pouring 50 kg of cold water into the reaction liquid, crystallizing, and filtering to obtain 26.5 kg of 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid, wherein the HPLC purity of the product is 95.1%, and the total yield is 90%.
Claims (3)
1. A method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid, which is characterized by comprising the following steps:
injecting organic acid anhydride into a reaction kettle, adding 1, 2-diazoxynaphthalene-4-sulfonic acid, and cooling to a certain temperature, wherein the organic acid anhydride is acetic anhydride or propionic anhydride or a mixture of the acetic anhydride and the propionic anhydride;
slowly adding a nitration reagent for nitration and carrying out heat preservation reaction, diluting with water after the reaction is finished, standing for crystallization, and filtering to obtain a product, wherein the nitration reagent is a mixture of potassium nitrate and potassium bisulfate in a weight ratio of 1: 1.4.
2. The method for improving nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid according to claim 1, wherein the ratio of the weight of the organic acid anhydride to the weight of 1, 2-diazoxynaphthalene-4-sulfonic acid is 1.5: 1 to 3: 1.
3. The method for improving the nitration selectivity of 1, 2-diazoxynaphthalene-4-sulfonic acid as claimed in claim 1, wherein the nitration reaction temperature is 20% o C ~ 30 o And C is between.
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| CN102516195B (en) * | 2011-12-09 | 2014-05-07 | 江苏远征化工有限公司 | Production method of 6-nitro-1,2,4-sulfonic acid |
| CN104628670A (en) * | 2014-11-05 | 2015-05-20 | 九江善水科技有限公司 | 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid and preparation method thereof |
| CN104817516A (en) * | 2015-04-19 | 2015-08-05 | 李凤燕 | Method for preparing 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid |
| CN105732536B (en) * | 2016-03-14 | 2017-02-08 | 九江善水科技有限公司 | Solvent nitration method for 1,2-naphthoxydiazo-4-sulfonic acid |
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