Process for the rapid preparation of an acid black 172 intermediate

Abstract

The present application relates to a kind of fast preparation method of acid black 172 intermediate, which comprises the following steps: (1) 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid is dissolved in organic solvent to obtain diazonium salt solution;(2) diazonium salt solution is punched into reaction kettle, while adding 2-naphthol sodium powder and crown ether catalyst, stirring under certain temperature and pressure;And (3) collect reaction solution, cool crystallization, filter to obtain acid black 172 intermediate.The preparation method proposed in the present application has the advantages of fast reaction rate, short reaction time, and the yield and selectivity of product are improved to more than 95%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a rapid preparation method of an acid black 172 intermediate. BACKGROUND

[0002] Acid dyes are widely used for dyeing and direct printing of wool, polyamide, silk and blended fabrics thereof. With the popularization of digital printing process, this type of dye is also widely used in the production of digital printing ink, and the applicable fabrics include wool, nylon, polyamide and silk materials.

[0003] As a key intermediate of acid black 172, acid black 172 intermediate (HHDN) is usually prepared by diazo coupling reaction of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid (HNSD) suspension and 2-naphthol sodium aqueous solution in a batch reactor, and the reaction process is shown in formula 1.

[0004]

[0005] Formula 1: synthesis route of acid black 172 intermediate

[0006] Since HNSD has low solubility in water, the reaction is a solid-liquid phase reaction, and the reaction rate is limited by the interfacial mass transfer rate. The current industrial production process is to obtain HHDN after reacting at 40-60℃ for 3-6 hours, and the yield is about 83%.

[0007] Chinese patent CN201911403784.1 discloses a method for synthesizing acid black 172 intermediate by diazo coupling reaction of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid (HNSD) and 2-naphthol sodium aqueous solution. The method needs to react at 45℃ for 4h to prepare acid black 172 intermediate. In another synthesis method disclosed in Chinese patent application CN202111545008.2, 3h of reaction time is also required.

[0008] Therefore, the existing preparation method of acid black 172 intermediate has not solved the defects of long reaction time and poor product selectivity.

[0009] In view of the defects of the existing preparation method of acid black 172 intermediate, the present application is based on the rich practical experience and professional knowledge in designing and manufacturing such products for many years, and cooperates with the application of theory, actively researches and innovates, and finally creates the present application with practical value after continuous research, design, and repeated trial and improvement. SUMMARY

[0010] The main purpose of the present application is to overcome the defects of the existing preparation method of acid black 172 intermediate, and to provide a new rapid preparation method of acid black 172 intermediate, and the technical problem to be solved is to reduce the reaction time and improve the selectivity and yield of the reaction product.

[0011] Another purpose of the present application is to provide a catalyst in the preparation method of acid black 172 intermediate, so as to improve the reaction rate of the preparation method of acid black 172 intermediate.

[0012] The purpose of the present application and the technical problem thereof are realized by adopting the following technical scheme. According to the rapid preparation method of acid black 172 intermediate provided by the present application, the preparation method comprises the step of dissolving the reactant 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid into an organic solvent to prepare a diazonium salt solution.

[0013] The purpose of the present application and the technical problem thereof can be further realized by adopting the following technical measures.

[0014] The rapid preparation method of acid black 172 intermediate, wherein the mass percentage of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid and organic solvent is 1:0.5-2.

[0015] The rapid preparation method of acid black 172 intermediate, wherein the mass percentage of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid and organic solvent is 1:0.5-1.

[0016] The rapid preparation method of acid black 172 intermediate, wherein the organic solvent is selected from one or more combinations of DMF, dichloroethane and ethylene glycol.

[0017] The rapid preparation method of acid black 172 intermediate, further comprising the following steps:

[0018] The diazonium salt solution is injected into the reaction kettle, and 2-naphthol sodium powder and crown ether catalyst are added into the reaction kettle at the same time, then the reaction kettle is heated, and the above reactants are stirred, and the reaction is carried out at a reaction temperature of 30-70℃ for 5-30 minutes.

[0019] The rapid preparation method of acid black 172 intermediate, wherein the molar ratio of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid to 2-naphthol sodium is 1:1-1.3, and preferably the molar ratio of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid to 2-naphthol sodium is 1:1-1.1.

[0020] The fast preparation method of the Acid Black 172 intermediate, wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6.

[0021] The fast preparation method of the Acid Black 172 intermediate, wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6.

[0022] The fast preparation method of the Acid Black 172 intermediate, wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6.

[0023] The fast preparation method of the Acid Black 172 intermediate, wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6.

[0024] The fast preparation method of the Acid Black 172 intermediate, wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6.

[0025] The fast preparation method of the Acid Black 172 intermediate, wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6.

[0026] (1) 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid is dissolved in an organic solvent at a ratio of 1:0.5-2 wt% to obtain a diazonium salt solution;

[0027] (2) The diazonium salt solution is poured into a reaction kettle, and 2-naphthol sodium powder and a crown ether catalyst are added, and the reaction is carried out by heating and stirring, wherein the molar ratio of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid to 2-naphthol sodium is 1:1-1.3, the crown ether catalyst is added in an amount of 0.1-1 wt% of the total mass of the reactants, the reaction temperature is 30-70℃, and the reaction time is 5-30 min;

[0028] (3) The reaction liquid is cooled and crystallized, and then filtered to obtain the Acid Black 172 intermediate, and the mother liquor is concentrated and recycled.

[0029] Via the above, the present application is about a fast preparation method of Acid Black 172 intermediate, which comprises the following steps: (1) dissolving 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid in an organic solvent to obtain a diazonium salt solution; (2) pouring the diazonium salt solution into a reaction kettle, while adding 2-naphthol sodium powder and crown ether catalyst, stirring and reacting under certain temperature and pressure; and (3) collecting the reaction liquid, cooling and crystallizing, and filtering to obtain the Acid Black 172 intermediate. The preparation method has the advantages of fast reaction rate, short reaction time, and product yield and selectivity increased to more than 95%.

[0030] Through the above technical solution, the fast preparation method of Acid Black 172 intermediate has at least the following advantages:

[0031] Firstly, the crown ether catalyst in the present application forms an intermediate dissolved in an organic solvent with 2-naphthol sodium solid, thereby improving the overall reaction rate.

[0032] Secondly, the reaction time of the present application is shortened to within 30 minutes.

[0033] Thirdly, the product yield and selectivity of the present application are increased to more than 95%.

[0034] In summary, the fast preparation method of Acid Black 172 intermediate has many advantages and practical values as described above, and there is no similar design published or used in similar methods, which is innovative. It has great progress in technology and produces good and practical effects. Compared with the existing preparation method of Acid Black 172 intermediate, it has improved many functions, so it is more suitable for practical use.

[0035] The above description is only a summary of the technical solution of the present application. In order to better understand the technical means of the present application and to implement the content of the specification, the following will describe the preferred embodiments of the present application in detail. DETAILED DESCRIPTION

[0036] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined invention purpose, the following will describe the fast preparation method of Acid Black 172 intermediate according to the present application in detail with reference to the preferred embodiments.

[0037] Example 1

[0038] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 20g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 40°C, stirring, reaction for 20min. The reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, and then crystallization, suction filtration and drying were carried out to obtain the intermediate of Acid Black 172, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 95.5%, and the selectivity was 95.5%.

[0039] Example 2

[0040] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 30g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 40°C, stirring, reaction for 20min. The reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, and then crystallization, suction filtration and drying were carried out to obtain the intermediate of Acid Black 172, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 95.6%, and the selectivity was 95.6%.

[0041] Example 3

[0042] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 20g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 60°C, stirring, reaction for 20min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, and then crystallization, suction filtration and drying were carried out to obtain the intermediate of Acid Black 172, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 96%, and the selectivity was 96%.

[0043] Example 4

[0044] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 20g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 30°C, stirring, reaction for 20min; the reaction liquid at the reactor outlet was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, suction filtered, and dried to obtain the Acid Black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 95.5%, and the selectivity was 95.5%.

[0045] Example 5

[0046] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 20g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 30°C, stirring, reaction for 20min; the reaction liquid at the reactor outlet was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, suction filtered, and dried to obtain the Acid Black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 95.5%, and the selectivity was 95.5%.

[0047] Example 6

[0048] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 20g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 30°C, stirring, reaction for 20min; the reaction liquid at the reactor outlet was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, suction filtered, and dried to obtain the Acid Black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 95.5%, and the selectivity was 95.5%.

[0049] Example 7

[0050] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 25g of ethylene glycol, 12g (0.072mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 50°C, stirring, reaction for 30min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, suction filtered and dried to obtain the Acid Black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 96.2%, and the selectivity was 96.2%.

[0051] Example 8

[0052] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 25g of ethylene glycol, 12g (0.072mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 50°C, stirring, reaction for 30min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, suction filtered and dried to obtain the Acid Black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 96.2%, and the selectivity was 96.2%.

[0053] Example 9

[0054] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 25g of ethylene glycol, 12g (0.072mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 50°C, stirring, reaction for 30min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, suction filtered and dried to obtain the Acid Black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product Acid Black 172 intermediate was 96.2%, and the selectivity was 96.2%.

[0055] Example 10

[0056] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 25g of dichloroethane, 12g (0.072mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 65°C, stirring, reaction for 30min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, filtered and dried to obtain the acid black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product acid black 172 intermediate was 96.1%, and the selectivity was 96.1%.

[0057] Example 11

[0058] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 25g of dichloroethane, 12g (0.072mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 65°C, stirring, reaction for 30min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, filtered and dried to obtain the acid black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product acid black 172 intermediate was 96.1%, and the selectivity was 96.1%.

[0059] Comparative Example 1

[0060] First, the water phase preparation process is used as a comparative example to illustrate the advancement of the present method.

[0061] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was dissolved in 25g of dichloroethane, 12g (0.072mol) of 2-naphthol sodium powder and 0.1g of 15-crown-5 were added, the reaction temperature was controlled at 65°C, stirring, reaction for 30min; the reaction liquid at the outlet of the reactor was collected, and the liquid phase composition was analyzed by HPLC; the finished liquid was cooled to 20°C, crystallized, filtered and dried to obtain the acid black 172 intermediate, and the mother liquor was concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid was 100%, the yield of the product acid black 172 intermediate was 96.1%, and the selectivity was 96.1%.

[0062] Comparative Example 2

[0063] Secondly, with the method itself as a comparative example, the importance of crown ether catalyst is explained. The following comparative example is equivalent to example 1 except that no crown ether catalyst is added.

[0064] In a 100ml three-necked flask, 19.6g (0.066mol) of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid is dissolved in 20g of ethylene glycol, 11g (0.066mol) of 2-naphthol sodium powder is added, the reaction temperature is controlled at 40°C, and the reaction is stirred for 20min; the reaction liquid at the outlet of the reactor is collected, and the liquid phase composition is analyzed by HPLC; the liquid is cooled to 20°C for crystallization, suction filtration, and drying to obtain the intermediate of Acid Black 172, and the mother liquor is concentrated and recycled. The conversion rate of 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid is 80%, the yield of the intermediate of Acid Black 172 is 72%, and the selectivity is 90%.

[0065] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed methods and technical contents to obtain equivalent embodiments with equivalent changes, without departing from the technical solution of the present application. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1. A process for the rapid preparation of an Acid Black 172 intermediate, characterized in that, The preparation method comprises the following steps: (1) dissolving the reactant 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid in an organic solvent to form a diazonium salt solution; (2) injecting the diazonium salt solution into a reaction kettle, adding 2-naphthol sodium powder and a crown ether catalyst into the reaction kettle, then heating and stirring the reaction kettle, and reacting for 5-30 minutes at a reaction temperature of 30-70 DEG C; wherein the crown ether catalyst is selected from one or a combination of 15-crown-5 and 18-crown-6, and the addition amount of the crown ether catalyst accounts for 0.1-1wt% of the total mass of the reactants; (3) cooling the reaction liquid to 0-20 DEG C, standing for crystallization, and then performing suction filtration to obtain the intermediate of Acid Black 172; wherein the organic solvent is selected from one or a combination of DMF, dichloroethane and ethylene glycol.

2. A process for the rapid preparation of Acid Black 172 intermediate according to claim 1, wherein, The mass percentage of the 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid and the organic solvent is 1:0.5-2.

3. The process for the fast preparation of Acid Black 172 intermediate according to claim 1, wherein, The mass percentage of the 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid and the organic solvent is 1:0.5-1.

4. The process for the rapid preparation of Acid Black 172 intermediate according to claim 1, wherein, The molar ratio of the 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid to 2-naphthol sodium is 1:1-1.

3.

5. The process for the rapid preparation of Acid Black 172 intermediate according to claim 1, wherein, The molar ratio of the 6-nitro-1-diazo-2-hydroxy-4-naphthalenesulfonic acid to 2-naphthol sodium is 1:1-1.

1.

6. The process for the rapid preparation of Acid Black 172 intermediate according to claim 1, wherein, The reaction temperature is 40-60 DEG C, and the reaction time is 10-20 minutes.

7. The process for the rapid preparation of Acid Black 172 intermediate according to claim 6, wherein, The addition amount of the crown ether catalyst accounts for 0.2-0.4wt% of the total mass of the reactants.

8. The process for the rapid preparation of Acid Black 172 intermediate according to claim 1, wherein, The crown ether catalyst is 15-crown-5.

9. The process for the rapid preparation of Acid Black 172 intermediate according to claim 1, wherein, The crown ether catalyst is 18-crown-6.

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