CN113105347B - Environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone - Google Patents
Environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone Download PDFInfo
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- CN113105347B CN113105347B CN202110381823.3A CN202110381823A CN113105347B CN 113105347 B CN113105347 B CN 113105347B CN 202110381823 A CN202110381823 A CN 202110381823A CN 113105347 B CN113105347 B CN 113105347B
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- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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Abstract
The invention relates to the technical field of dye intermediates, in particular to a process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone, which comprises the following steps: adding a certain amount of solvent chlorobenzene into a reaction container, adding a certain amount of 1,4-diaminoanthraquinone leuco body and a catalyst zinc peroxide after detecting that the water content is qualified, heating to 40-50 ℃, stirring and preserving the temperature for 10-20min; stirring and dripping quantitative sulfuryl chloride at the temperature of 40-50 ℃, and preserving heat for 10-60min under the condition after dripping is finished; after the reaction is finished, vacuum pumping is carried out for 30 to 60min, and then soda is added to adjust the pH of the reaction liquid to be nearly neutral; and (5) distilling water vapor to recover the solvent, filtering and washing the materials to obtain the product. The 1,4-diamino-2,3-dichloroanthraquinone synthesis process provided by the invention is added with the catalyst zinc peroxide, so that the reaction temperature can be reduced, the reaction time is shortened, the dosage of sulfuryl chloride is reduced, and the process has positive significance for reducing the cost and reducing the environmental protection pressure.
Description
Technical Field
The invention relates to the technical field of dye intermediates, in particular to an energy-saving and environment-friendly process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone.
Background
1,4-diamino-2,3-dichloroanthraquinone (also called as dichlorodiphenylene) 28, can be used for dyeing and printing fabrics of terylene, diacetate fiber, triacetate fiber, nylon, etc. The dye has good level-dyeing property and poor deep dyeing property, is used for dyeing light colors and dyeing bright red purple of terylene, and is mainly used for dyeing terylene knitted fabrics by a high-temperature high-pressure method or adjusting color and light. The dichlorine can also be used as a dye intermediate to synthesize various dyes and pigment varieties with excellent performance, and is mainly used for synthesizing disperse violet 26 and disperse turquoise blue HBF and S-GL at present.
The Chinese invention patent with the publication number CN102219704A discloses an improved method for synthesizing 1,4-diamino-2,3-dichloroanthraquinone, which uses carbon tetrachloride as a solvent and introduces chlorine to chlorinate 1,4-diaminoanthraquinone leuco to obtain 1,4-diamino-2,3-dichloroanthraquinone. In the method, a highly toxic solvent of carbon tetrachloride is used, chlorine gas is required to be introduced for reaction, and the reaction risk degree is high.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides an environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone, which is more environment-friendly.
The technical scheme for solving the technical problems is as follows:
an environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone comprises the following steps:
(1) Adding a certain amount of solvent chlorobenzene into a reaction container, adding a certain amount of 1,4-diaminoanthraquinone leuco body and a catalyst zinc peroxide after detecting that the water content is qualified, heating to 40-50 ℃, stirring and preserving the temperature for 10-20 min; stirring and dripping quantitative sulfuryl chloride at the temperature of 40-50 ℃, and preserving heat for 10-60 min under the condition after dripping;
(2) After the reaction is finished, vacuum pumping is carried out for 30-60 min, and then soda is added to adjust the pH of the reaction solution to be nearly neutral; distilling the water vapor to recover the solvent, filtering the materials, and washing to obtain a product; the specific reaction structural formula is as follows:
preferably, the molar ratio of 1,4-diaminoanthraquinone leuco body, sulfuryl chloride and zinc peroxide in step (1) is 1:3 to 4:0.01 to 0.1.
Further, in the step (1), the molar ratio of the 4-diaminoanthraquinone leuco body to the sulfuryl chloride to the zinc peroxide is 1:3.0 to 3.2:0.05 to 0.1.
Preferably, the adding mass of the chlorobenzene in the step (1) is 4-10 times of that of 1,4-diaminoanthraquinone leuco body.
Furthermore, the adding mass of the chlorobenzene in the step (1) is 5-6 times of that of 1,4-diaminoanthraquinone leuco body.
Preferably, the vacuum degree of the vacuum pumping in the step (2) is-0.03 to-0.08 MPa.
Preferably, soda ash is added in the step (2) to adjust the pH range of the reaction solution to 7-8.
The Chinese naming of the compound of the invention conflicts with the structural formula, and the structural formula is taken as the standard; except for obvious errors in the formula.
The 1,4-diamino-2,3-dichloroanthraquinone synthesis process provided by the invention is added with the catalyst zinc peroxide, so that the reaction temperature can be reduced, the reaction time is shortened, the dosage of sulfuryl chloride is reduced, and the process has positive significance for reducing the cost and reducing the environmental protection pressure.
Detailed Description
The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.
Example 1:
200g of chlorobenzene was added into a 1000ml flask, and 50g (molecular weight 240.26, 0.208mol) of 1,4-diaminoanthraquinone leuco body and 1g (molecular weight 97.38, 10.3 mmol) of zinc peroxide were added after the water content was detected to be less than 0.1%. After being stirred and mixed evenly, the temperature is increased to 30 to 50 ℃, and the temperature is kept for 10min under the temperature condition. 86g of sulfuryl chloride (with a molecular weight of 134.97 and 0.637mol) is added dropwise at the temperature, and after the dropwise addition is finished, stirring and heat preservation are continued for 30min at the temperature. After the heat preservation is finished, the air is pumped for 0.5 hour under the temperature condition, and the vacuum degree is controlled between-0.03 MPa and-0.08 MPa. After the air pumping is finished, 125g of 20 percent sodium carbonate solution is slowly added, stirred for 10 to 30 minutes, the pH value is controlled to be 7.0 to 8.0, and the neutralization temperature is controlled to be 50 to 65 ℃. After neutralization, 250ml of clean water is added, the temperature is raised, the solvent is distilled and recovered (the distilled water can be added into the materials for continuous distillation, the solvent is used for the next synthesis after further dehydration), and after the solvent is recovered by distillation, the materials are filtered and washed to obtain 62.4g of 1,4-diamino-2,3-dichloroanthraquinone, and the yield is 97.5 percent. The chromatographic content was 96.5%.
Example 2:
250g of chlorobenzene was added into a 1000ml flask, 50g (molecular weight 240.26, 0.208mol) of 1,4-diaminoanthraquinone leuco body and 2g (molecular weight 97.38, 20.6 mmol) of zinc peroxide were added after the water content was detected to be less than 0.1%. After being stirred and mixed evenly, the temperature is raised to 50 to 60 ℃, and the temperature is kept for 20min under the temperature condition. 89g of sulfuryl chloride (with the molecular weight of 134.97 and 0.660 mol) is dropwise added at the temperature, and after the dropwise addition is finished, stirring and heat preservation are continued for 40min at the temperature. After the heat preservation is finished, the air is pumped for 1 hour under the temperature condition, and the vacuum degree is controlled between-0.03 and-0.08 MPa. After the air extraction is finished, 125g of 20 percent sodium carbonate solution is slowly added, stirred and stirred for 10 to 30 minutes, the pH value is controlled to be 7.0 to 8.0, and the neutralization temperature is controlled to be 50 to 65 ℃. After neutralization, 250ml of clean water is added, the temperature is raised, the solvent is distilled and recovered (the distilled water can be added into the material for continuous distillation, the solvent is used for the next batch synthesis after further dehydration), and after the solvent is distilled and recovered, the material is filtered and washed to obtain 1,4-diamino-2,3-dichloroanthraquinone 62.8g, and the yield is 98.1%. The chromatographic content was 97.8%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (7)
1. An environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone is characterized by comprising the following steps:
(1) Adding a certain amount of chlorobenzene solvent into a reaction container, adding a certain amount of 1,4-diaminoanthraquinone leuco body and a catalyst zinc peroxide after detecting that the water content is qualified, heating to 40-50 ℃, stirring and preserving the temperature for 10-20 min; stirring and dripping quantitative sulfuryl chloride at the temperature of 40-50 ℃, and preserving heat for 10-60 min under the condition after dripping;
(2) After the reaction is finished, vacuum pumping is carried out for 30-60 min, and then soda is added to adjust the pH of the reaction solution to be nearly neutral; distilling the water vapor to recover the solvent, filtering and washing the materials to obtain a product; the specific reaction structural formula is as follows:
2. the environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone according to claim 1, wherein the molar ratio of 1,4-diamino anthraquinone leuco body, sulfuryl chloride and zinc peroxide in step (1) is 1:3 to 4:0.01 to 0.1.
3. The environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone according to claim 2, wherein in step (1), the molar ratio of 4-diaminoanthraquinone leuco body, sulfuryl chloride and zinc peroxide is 1: 3.0-3.2: 0.05 to 0.1.
4. The environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone according to claim 1, wherein the mass of chlorobenzene added in the step (1) is 4-10 times of 1,4-diamino anthraquinone leuco body.
5. The environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone according to claim 4, wherein the mass of chlorobenzene added in the step (1) is 5-6 times of 1,4-diamino anthraquinone leuco body.
6. The environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone according to claim 1, wherein the vacuum degree of vacuum pumping in the step (2) is-0.03 to-0.08 Mpa.
7. The environment-friendly and energy-saving process for synthesizing 1,4-diamino-2,3-dichloroanthraquinone according to claim 1, characterized in that soda is added in the step (2) to adjust the pH range of the reaction solution to 7-8.
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