A 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative, and a preparation method and application thereof

Abstract

This invention discloses a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative, its preparation method, and its application. Using a vat dye derivative PR177 as the parent material, a 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative is formed by the Ullmann condensation of a 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative. This derivative is then cyclically closed via the McMurray reaction to form the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative. This allows for direct dyeing without the use of sodium hydrosulfite. Compared to soluble vat dyes, it is stable when exposed to air. Furthermore, due to its good planarity, it exhibits excellent dyeing performance as an acid dye. It combines the advantages of good directness of vat dyes and good water solubility of acid dyes, especially showing excellent color fastness and exhaustion rate in wool dyeing.

Description

Technical Field

[0001] This invention relates to the field of dye technology, and more specifically, to a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative, its preparation method, and its application. Background Technology

[0002] Vat dyes are a class of high-grade dyes with numerous varieties, a complete color spectrum, bright colors, and excellent fastness. They are widely used in the printing and dyeing of cotton, wool, silk, linen, synthetic fibers, and their blended and interwoven fabrics. Because vat dyes have excellent lightfastness, weather resistance, heat resistance, solvent resistance, and wash resistance, many varieties can be specially processed into organic pigments for coloring paints, plastics, rubber, and coatings.

[0003] Vat dyes have a relatively large molecular structure, no affinity for cellulose fibers, and contain two or more carbonyl groups and no water-soluble groups, making them insoluble in water. This structural characteristic allows vat dyes to bind to fibers through specific chemical forces during the dyeing process, forming a strong dyeing effect with good planarity.

[0004] Vat dyes are a type of dye that can only be applied after reduction. Under the action of sodium hydrosulfite in an alkaline solution, the carbonyl group is reduced to an oxygen anion, making the dye soluble in the alkaline solution. This allows the dye to have an affinity for cellulose and dye the fiber. Then, after oxidation by air or an oxidizing agent, it returns to its original insoluble state and is fixed on the fiber. Currently, the most commonly used reducing agent in industrial production is sodium hydrosulfite, chemically known as sodium dithionite. Sodium hydrosulfite has the advantages of strong reducing ability, convenient use, and bright color. However, sodium hydrosulfite has poor chemical stability. When exposed to air, it easily absorbs oxygen and decomposes, clumps, and emits a pungent acidic smell. When in contact with water, it decomposes rapidly, releasing a large amount of heat and flammable hydrogen and hydrogen sulfide gases, causing violent combustion. At the same time, the sulfates and sulfites produced by the decomposition of sodium hydrosulfite have a significant impact on the environment (Jin Xiaosong, Wang Helan. Dyes and Dyeing, 2011, 48(04):18-21+11.). In response to the drawbacks of sodium hydrosulfite, such as large usage, difficulty in storage, and environmental pollution, people have been researching new reduction methods in recent years to reduce its usage or replace sodium hydrosulfite.

[0005] Soluble vat dyes are mainly sodium sulfate salts of the leuco form of vat dyes. They are soluble in water and have good directness to fibers, and can dye cellulose, protein and some chemical fibers (Zhu Zhengfa. Shanghai Dyes, 2020, 48(4):18-24.). The fastness of soluble vat dyes can reach the level of the corresponding parent vat dyes. In addition, the dyeing method is relatively convenient, so soluble vat dyes have a promising future. However, soluble vat dyes are easily exposed to air and deteriorate due to moisture, which reduces the dyeing strength and causes them to lose their solubility.

[0006] Acid dyes are mainly used on wool, silk, and polyamide fibers. After mordant treatment, they exhibit good lightfastness, wash fastness, and shrinkage fastness on wool. Acid dyes contain water-soluble groups, such as sulfonic acid groups (-SO3H) and carboxyl groups (-COOH), which exist as sodium salts on the dye molecule, giving them good water solubility. This makes acid dyes easy to dissolve in water, facilitating their use. Furthermore, these water-soluble groups are also related to the bright colors and wide color spectrum of acid dyes, allowing for a rich selection of colors and vibrant color expression during dyeing. However, the molecular structure of acid dyes is relatively simple, lacking a long conjugated coherent system, resulting in lower directness and meaning weaker dyeing power. Summary of the Invention

[0007] The purpose of this invention is to overcome the above-mentioned defects in the prior art and provide a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative, its preparation method, and its application. By attaching a water-soluble group to a vat dye, the dyeing effect of the vat dye can be achieved without reduction. The 4,4'-diamino-[1,1'-dibenzo]-9,9',10,10'-tetraone derivative is modified, and the intermediate 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative is cyclically closed to synthesize the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative. This not only solves the problems of vat dyes being easily affected by moisture and deteriorating, the cumbersome dyeing process, and serious pollution from waste, but also has the advantages of good directness of vat dyes and good water solubility of acid dyes. In particular, it has excellent color fastness and exhaustion rate for wool dyeing.

[0008] To achieve the above objectives, the technical solution of the present invention is as follows:

[0009] A 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative has the general structural formula shown in formula (I):

[0010]

[0011] Among them, R1, R2, R3, R4, R5, and R6 are each independently selected from -H, -F, -Cl, -Br, -NH2, -OH, -COOH, -SO3H, -NO2, -C n H 2n+1 , -OCnH 2n+1 or -OOCCnH 2n+1 , where 0 < n < 21, n is an integer, and R1 is the same as R2, R3 is the same as R4, and R5 is the same as R6.

[0012] Optionally, the structural formula of the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative is as follows:

[0013]

[0014] The present invention also discloses a preparation method of the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative as described above, comprising the following steps:

[0015]

[0016] (1) Mix a copper catalyst, absolute ethanol, and concentrated sulfuric acid, and react under the condition of 30°C to 70°C for 20 min to 40 min, and then obtain copper powder after cooling, filtering, and drying;

[0017] (2) Mix the copper powder with a 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative, absolute methanol, and N,N-dimethylformamide, keep the temperature at 30°C to 70°C for 4.0 h to 6.0 h, add the copper powder again and keep the temperature for 0.5 h to 2 h, then add citric acid and keep the temperature for 0.5 h to 1.0 h. After the reaction is completed, filter while it is hot. The obtained filtrate is subjected to vacuum distillation and filtration to obtain a 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative;

[0018] (3) Mix the 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative, the copper powder, and concentrated sulfuric acid under the condition of 40°C to 60°C for 20 min to 50 min, and purify to obtain the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative.

[0019] Optionally, in step (1), the molar ratio of the copper catalyst, absolute ethanol, and concentrated sulfuric acid is 2:2:1 to 1:5:5.

[0020] Optionally, in step (2), the copper powder is mixed with 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative, anhydrous methanol and N,N-dimethylformamide in a molar ratio of 3:1:250:50 to 2:1:250:50 and kept at a constant temperature. Then, copper powder is added in a molar ratio of 1:1 to 5:1 to 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative and kept at a constant temperature. Subsequently, citric acid is added in a molar ratio of 10:1 to 20:1 to 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative and kept at a constant temperature. After the reaction is completed, the mixture is filtered while hot. The filtrate is distilled under reduced pressure and then filtered with dichloromethane to obtain 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative.

[0021] Optionally, in step (3), the molar ratio of the 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative, copper powder, and concentrated sulfuric acid is 1:2:10 to 1:5:50.

[0022] Optionally, the copper catalyst includes one or more of copper powder, copper acetate, copper chloride, cuprous chloride, and copper sulfate.

[0023] The present invention also discloses the application of the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative as described above, or the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative prepared by the preparation method described above, in dyes.

[0024] Implementing the embodiments of the present invention will have the following beneficial effects:

[0025] This invention uses a derivative of the vat dye PR177 as the parent material. A bromoamino acid derivative (1-amino-4-bromoanthraquinone-2-sulfonic acid derivative) is condensed by Ullmann to form a 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative. This is then followed by a McMurry reaction to form a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative. This allows for direct dyeing without the use of sodium hydrosulfite. Compared to soluble vat dyes, it is stable when exposed to air. Furthermore, due to its good planarity, it exhibits excellent dyeing performance as an acid dye. It combines the advantages of the directness of vat dyes and the water solubility of acid dyes, especially showing excellent color fastness and exhaustion rate in wool dyeing.

[0026] The 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative provided by this invention is brown in color and has a molar absorptivity of up to 15000 L·mol⁻¹. -1 ·cm -1It has a water solubility of up to 40.0 g / L, and the exhaustion rate of dyed wool can reach over 95%. It has a dry and wet friction rating of 4 or higher, meeting the requirements of daily life applications. Attached Figure Description

[0027] Figure 1 This is a structural diagram of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid from Example 1 of the present invention.

[0028] Figure 2 The liquid chromatogram of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid from Example 1 of the present invention is shown.

[0029] Figure 3 This is the mass spectrum of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid from Example 1 of the present invention.

[0030] Figure 4 The image shows the 1H NMR spectrum of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid from Example 1 of this invention.

[0031] Figure 5 The absorption spectrum of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in Example 1 of the present invention is shown.

[0032] Figure 6 This is the standard working curve of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid from Example 1 of the present invention.

[0033] Figure 7 The dyeing curve of wool with 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is shown in Example 1 of this invention.

[0034] Figure 8 This is a picture of wool dyed with 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid according to Example 1 of the present invention. Detailed Implementation

[0035] The present invention will be further described below with reference to specific embodiments, but this does not limit the present invention in any way.

[0036] Example 1

[0037] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-diketone-2,5-disulfonic acid, in which R1, R2, R3, R4, R5, and R6 are all substituted with hydrogen atoms, is as follows:

[0038]

[0039] The preparation method of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0040] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 40 °C for 30 min. After standing, pour off the supernatant, removing as much of the supernatant as possible. Then add 1-amino-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 50 °C for 4.5 h. Then add copper powder (2.0 g) and continue incubation for 30 min. Then add citric acid (1.0 g) and continue the reaction for 30 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution and filter to obtain 7.65 g of 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid, with a yield of 96.4%.

[0041] 2) Add copper powder (1.0g), anhydrous ethanol (3.0g), and concentrated sulfuric acid (98%, 3.0g) to a 100ml beaker and stir at 40℃ for 30min. After standing, pour off the supernatant. Then add 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid (3.0g) and concentrated sulfuric acid (98%, 10.0g) to the copper powder beaker and keep warm at 55℃ for 30min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol, filter, and precipitate with dichloromethane to obtain 2.14g of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid, with a yield of 75.3%. Figure 1-4 As shown.

[0042] FT-IR (KBr, cm -1 ):3407cm -1 1663cm -1 1617cm -1 1558cm -1 1537cm -1 1189cm -1 1096cm -1 1069cm -1 1045cm -1 1025cm -1 771cm -1 662cm -1 634cm -1 602cm -1585cm -1 567cm -1 541cm -1 487cm -1 .

[0043] Figure 5 The absorption spectrum of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is shown. Figure 6 The standard working curve of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid shows that the dye molecule obeys Beer-Lambert absorption law in solution.

[0044] Example 2

[0045] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid, in which R3 and R4 are substituted with bromine atoms, is as follows:

[0046]

[0047] The preparation method of 1,6-diamino-9,14-dibromo-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0048] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 40 min. After standing, pour off the supernatant, removing as much as possible. Then add 1-amino-4,7-dibromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 40 °C for 4 h. Then add copper powder (2.0 g) and continue incubation for 40 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution and filter to obtain 4,4'-diamino-6,6'-dibromo-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0049] 2) Add copper powder (1.0g), anhydrous ethanol (3.0g), and concentrated sulfuric acid (98%, 3.0g) to a 100ml beaker and stir at 40℃ for 30min. After standing, pour off the supernatant. Then add 4,4'-diamino-6,6'-dibromo-1,1'-dianthraquinone-3,3'-disulfonic acid (3.0g) and concentrated sulfuric acid (98%, 10.0g) to the beaker containing the copper powder. Keep warm at 55℃ for 30min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol, filter, and precipitate with dichloromethane to obtain 1,6-diamino-9,14-dibromo-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0050] Example 3

[0051] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-diketone-2,5-disulfonic acid, in which R1 and R2 are substituted with amino groups, is as follows:

[0052]

[0053] The preparation method of 1,6,8,15-tetraamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0054] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 40 min. After standing, pour off the supernatant, removing as much as possible. Then add 1,8-diamino-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 50 °C for 4 h. Then add copper powder (2.0 g) and continue incubation for 30 min. Then add citric acid (1.0 g) and continue the reaction for 30 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4',5,5'-tetraamino-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0055] 2) Add copper powder (1.0g), anhydrous ethanol (3.0g), and concentrated sulfuric acid (98%, 3.0g) to a 100ml beaker and stir at 40℃ for 40min. After standing, pour off the supernatant. Then add 4,4',5,5'-tetraamino-1,1'-dianthraquinone-3,3'-disulfonic acid (4.0g) and concentrated sulfuric acid (98%, 15.0g) to the beaker containing the copper powder. Keep warm at 55℃ for 40min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol. After filtration, precipitate with dichloromethane to obtain 1,6,8,15-tetraamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0056] Example 4

[0057] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid with hydroxyl substitutions for R3 and R4 is as follows:

[0058]

[0059] The preparation method of 1,6-diamino-9,14-dihydroxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0060] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 40 min. After standing, pour off the supernatant, removing as much of the supernatant as possible. Then add 1-amino-7-hydroxy-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (80.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 60 °C for 4.5 h. Then add copper powder (2.0 g) and continue incubation for 30 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-6,6'-dihydroxy-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0061] 2) Add copper powder (1.5g), anhydrous ethanol (4.5g), and concentrated sulfuric acid (98%, 4.5g) to a 100ml beaker and stir at 50℃ for 40min. After standing, pour off the supernatant. Then add 4,4'-diamino-6,6'-dihydroxy-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0g) and concentrated sulfuric acid (98%, 30.0g) to the beaker containing the copper powder. Keep warm at 50℃ for 30min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol. After filtration, precipitate with dichloromethane to obtain 1,6-diamino-9,14-dihydroxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0062] Example 5

[0063] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-diketone-2,5-disulfonic acid with R5 and R6 substituted with carboxyl groups is as follows:

[0064]

[0065] The preparation method of 1,6-diamino-10,13-dicarboxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0066] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 40 min. After standing, pour off the supernatant, removing as much of the supernatant as possible. Then add 1-amino-6-carboxy-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (80.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 60 °C for 4 h. Then add copper powder (2.0 g) and continue incubation for 40 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-7,7'-dicarboxy-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0067] 2) Add copper powder (2.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 100ml beaker and stir at 40℃ for 40min. After standing, pour off the supernatant. Then add 4,4'-diamino-7,7'-dicarboxy-1,1'-dianthraquinone-3,3'-disulfonic acid (6.0g) and concentrated sulfuric acid (98%, 30.0g) to the beaker containing the copper powder. Keep warm at 50℃ for 40min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol. After filtration, precipitate with dichloromethane to obtain 1,6-diamino10,13-dicarboxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0068] Example 6

[0069] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-diketone-2,5-disulfonic acid, in which R3 and R4 are substituted with sulfonic acid groups, is as follows:

[0070]

[0071] The preparation method of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5,9,14-tetrasulfonic acid is as follows:

[0072] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 40 min. After standing, pour off the supernatant, removing as much of the supernatant as possible. Then add 1-amino-4-bromoanthraquinone-2,7-disulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 60 °C for 4.5 h. Then add copper powder (2.0 g) and continue incubation for 30 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-1,1'-dianthraquinone-3,3',6,6'-tetrasulfonic acid.

[0073] 2) Add copper powder (2.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 100ml beaker and stir at 50℃ for 30min. After standing, pour off the supernatant. Then add 4,4'-diamino-1,1'-dianthraquinone-3,3',6,6'-tetrasulfonic acid (5.0g) and concentrated sulfuric acid (98%, 30.0g) to the beaker containing the copper powder. Keep warm at 50℃ for 40min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol, filter, and precipitate with dichloromethane to obtain 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5,9,14-tetrasulfonic acid.

[0074] Example 7

[0075] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-diketone-2,5-disulfonic acid with nitro-substituted R3 and R4 is as follows:

[0076]

[0077] The preparation method of 1,6-diamino-9,14-dinitro-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0078] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 40 min. After standing, pour off the supernatant, removing as much as possible. Then add 1-amino-7-nitro-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 60 °C for 4.5 h. Then add copper powder (2.0 g) and continue incubation for 40 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-6,6'-dinitro-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0079] 2) Add copper powder (2.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 100ml beaker and stir at 40℃ for 40min. After standing, pour off the supernatant. Then add 4,4'-diamino-6,6'-dinitro-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0g) and concentrated sulfuric acid (98%, 30.0g) to the beaker containing the copper powder. Keep warm at 50℃ for 40min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol, filter, and precipitate with dichloromethane to obtain 1,6-diamino-9,16-dinitro-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0080] Example 8

[0081] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-diketone-2,5-disulfonic acid with R3 and R4 substituted with methyl groups is as follows:

[0082]

[0083] The preparation method of 1,6-diamino-9,14-dimethyl-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0084] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 30 min. After standing, pour off the supernatant, removing as much of the supernatant as possible. Then add 1-amino-7-methyl-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 50 °C for 4.5 h. Then add copper powder (2.0 g) and continue incubation for 50 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-6,6'-dimethyl-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0085] 2) Add copper powder (2.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 100ml beaker and stir at 40℃ for 40min. After standing, pour off the supernatant. Then add 4,4'-diamino-6,6'-dimethyl-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0g) and concentrated sulfuric acid (98%, 30.0g) to the beaker containing the copper powder. Keep warm at 50℃ for 40min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol. After filtration, precipitate with dichloromethane to obtain 1,6-diamino-9,14-dimethyl-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0086] Example 9

[0087] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid, in which R1 and R2 are substituted with methoxy groups, is as follows:

[0088]

[0089] The preparation method of 1,6-diamino-8,15-dimethoxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0090] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 40 °C for 30 min. After standing, pour off the supernatant, removing as much as possible. Then add 1-amino-8-methoxy-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and incubate at 50 °C for 4.5 h. Then add copper powder (2.0 g) and continue incubation for 35 min. Then add citric acid (1.0 g) and continue the reaction for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-5,5'-dimethoxy-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0091] 2) Add copper powder (1.0g), anhydrous ethanol (3.0g), and concentrated sulfuric acid (98%, 3.0g) to a 100ml beaker and stir at 50℃ for 40min. After standing, pour off the supernatant. Then add 4,4'-diamino-5,5'-dimethoxy-1,1'-dianthraquinone-3,3'-disulfonic acid (4.0g) and concentrated sulfuric acid (98%, 15.0g) to the beaker containing the copper powder. Keep warm at 55℃ for 30min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol. After filtration, precipitate with dichloromethane to obtain 1,6-diamino-8,15-dimethoxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0092] Example 10

[0093] The specific synthetic route for 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid, in which R1 and R2 are substituted with methyl ester groups, is as follows:

[0094]

[0095] The preparation method of 1,6-diamino-8,15-dimethyl ester-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid is as follows:

[0096] 1) Add copper powder (4.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 500 ml three-necked flask and stir at 50 °C for 30 min. After standing, pour off the supernatant, removing as much as possible. Then add 1-amino-8-methyl ester-4-bromoanthraquinone-2-sulfonic acid (10.0 g), DMF (100.0 g), and anhydrous methanol (200.0 g) to the three-necked flask and keep at 50 °C for 4.5 h. Then add copper powder (2.0 g) and continue to keep at 50 °C for 50 min. Then add citric acid (1.0 g) and continue to react for 40 min. Filter while hot. Distill the filtrate under reduced pressure. Add DCM (dichloromethane) to the distilled solution, stir, and filter to obtain 4,4'-diamino-5,5'-dimethyl ester-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0097] 2) Add copper powder (1.0g), anhydrous ethanol (3.0g), and concentrated sulfuric acid (98%, 3.0g) to a 100ml beaker and stir at 50℃ for 40min. After standing, pour off the supernatant. Then add 4,4'-diamino-5,5'-dimethyl ester-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0g) and concentrated sulfuric acid (98%, 15.0g) to the beaker containing the copper powder. Keep warm at 55℃ for 40min. Dilute it in an ice-water mixture and adjust the pH to about 7 with NaOH solution. Dissolve the filtered solid with DMF and anhydrous methanol, filter, and precipitate with dichloromethane to obtain 1,6-diamino-8,15-dimethyl ester-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0098] Example 11 (Dye Application)

[0099] The 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid prepared in the examples was applied to wool dyeing. Figure 7 To establish the wool dyeing curve, dyeing was performed at different color levels, with comparisons made with and without a fixing agent (JF-2113). For 2g wool fabric samples, 0.0250g, 0.0500g, and 0.1000g of the product were taken and diluted to 100mL volumetric flasks for dyeing. 40mL of dye solution was added to the dye bath using a pipette, with a liquor ratio of 1:20 and acidic conditions (pH 4.5). The exhaustion rate for all color levels, with and without the fixing agent, reached over 95%. The dyed wool samples are shown below. Figure 8 As shown in Table 1, the measured color fastness values ​​are as follows.

[0100] Table 1. Color fastness results of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in wool dyeing.

[0101]

[0102] according to Figures 7-8 As shown in Table 1, the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivatives of this invention are brown in color and have a molar absorptivity of up to 15000 L·mol⁻¹. -1 ·cm -1 Its water solubility can reach 40.0g / L, and the exhaustion rate of dyed wool can reach over 95%. It meets the requirements of daily life applications with dry and wet friction levels of 4 and above.

[0103] Examples 2-10 all have the same effect as Example 1.

[0104] In summary, this invention uses the PR177 derivative of a vat dye as the base, which can present a highly bright and clear red tone and has excellent properties such as weather resistance, heat resistance, light resistance, solvent resistance, and chemical resistance, as well as excellent characteristics such as high tinting strength, low toxicity, migration resistance, and resistance to plastic molding and coating drying temperatures. The PR177 derivative is formed by the Ullmann condensation of a 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative to form a 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative, followed by a McMurray reaction to form a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative. This allows for direct dyeing without the use of sodium hydrosulfite. Compared with soluble vat dyes, it can remain stable in air. Furthermore, due to its good planarity, it also exhibits excellent dyeing performance as an acid dye. It combines the advantages of the good directness of vat dyes and the good water solubility of acid dyes, especially showing excellent color fastness and exhaustion rate in wool dyeing.

[0105] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative, characterized in that, The general structural formula is shown in equation (I) below: （I） Wherein, R1, R2, R3, R4, R5, and R6 are each independently selected from -H, -F, -Cl, -Br, -NH2, -OH, -COOH, -SO3H, -NO2, -C n H 2n+1 , -OCnH 2n+1 or -OOCCnH 2n+1 , where 0 < n < 21, n is an integer, and R1 is the same as R2, R3 is the same as R4, and R5 is the same as R6.

2. The 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative according to claim 1, characterized in that, The structural formula of the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative is shown below: 。 3. A method for preparing the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative as described in any one of claims 1-2, characterized in that, Includes the following steps: (1) The copper catalyst, anhydrous ethanol and concentrated sulfuric acid are mixed and reacted at 30℃~70℃ for 20min~40min, and then cooled, filtered and dried to obtain activated copper powder; the copper catalyst includes one or more of copper powder, copper acetate, copper chloride, cuprous chloride and copper sulfate. (2) The activated copper powder was mixed with 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative, anhydrous methanol and N,N-dimethylformamide and reacted at 30℃~70℃ for 4.0h~6.0h. Then the activated copper powder was added and reacted at 30℃~70℃ for 0.5h~2h. Citric acid was then added and reacted at 30℃~70℃ for 0.5h~1.0h. After the reaction was completed, the mixture was filtered while hot. The filtrate was distilled under reduced pressure and filtered to obtain 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative. (3) The 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative, the activated copper powder and concentrated sulfuric acid were mixed at 40℃~60℃ for 20min~50min and purified to obtain the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative.

4. The preparation method according to claim 3, characterized in that, In step (1), the molar ratio of the copper catalyst, anhydrous ethanol and concentrated sulfuric acid is 2:2:1 to 1:5:

5.

5. The preparation method according to claim 3, characterized in that, In step (2), the activated copper powder is mixed with 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative, anhydrous methanol and N,N-dimethylformamide in a molar ratio of 3:1:250:50 to 2:1:250:50 and kept at a constant temperature. Then, activated copper powder is added to the mixture in a molar ratio of 1:1 to 5:1 to 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative and kept at a constant temperature. Subsequently, citric acid is added to the mixture in a molar ratio of 10:1 to 20:1 to 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative and kept at a constant temperature. After the reaction is completed, the mixture is filtered while hot. The filtrate is then distilled under reduced pressure and filtered with dichloromethane to obtain 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative.

6. The preparation method according to claim 3, characterized in that, In step (3), the molar ratio of the 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative, the activated copper powder, and concentrated sulfuric acid is 1:2:10 to 1:5:

50.

7. The use of a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative as described in any one of claims 1-2, or a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative prepared by the preparation method described in any one of claims 3-6, in dyes.

Images