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

Abstract

The invention discloses a 1, 6-diamino-dibenzo [a, o] perylene-7, 16-diketone-2, 5-disulfonic acid derivative and a preparation method and application thereof.The preparation method comprises the steps that a vat dye PR177 derivative serves as a parent, a 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative is subjected to Ullmann condensation to form a 4, 4 '-diamino-1, 1'-dianthraquinone-3, 3 '-disulfonic acid derivative, and the 4, 4'-diamino-dibenzo [a, o] perylene-7, 16-diketone-2, 5-disulfonic acid derivative is subjected to Ullmann condensation; the 1, 6-diamino-dibenzo [a, o] perylene-7, 16-diketone-2, 5-disulfonic acid derivative is formed through ring closure of Mecanum reaction, so that the 1, 6-diamino-dibenzo [a, o] perylene-7, 16-diketone-2, 5-disulfonic acid derivative can be directly dyed without using sodium hydrosulfite, compared with soluble vat dye, the 1, 6-diamino-dibenzo [a, o] perylene-7, 16-diketone-2, 5-disulfonic acid derivative can be exposed in air and stably exist The acid dye has excellent dyeing performance, has the advantages of good directness of a reduced dye and good water solubility of an acid dye, and especially has excellent color fastness and exhaustion dyeing rate for wool dyeing.

Description

Technical Field

[0001] The present invention relates to the technical field of dyes, and more specifically to a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative and a preparation method and application thereof. Background Art

[0002] Vat dyes are a type of high-grade dye with numerous varieties, 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 light-fastness, weather-resistant, heat-resistant, solvent-resistant and wash-resistant properties, many varieties of them can be made into organic pigments after special processing and used for coloring paints, plastics, rubber and coatings.

[0003] The molecular structure of vat dyes is relatively large, and they have no affinity for cellulose fibers. They contain two or more carbonyl groups in the molecule and do not contain water-soluble groups, which makes them insoluble in water. This structural characteristic enables 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 dyed after being reduced. Under the action of an alkaline solution of sodium hydrosulfite, the carbonyl group is reduced to an oxygen anion, which makes the dye soluble in the alkaline solution, so that the dye has an affinity for cellulose and dyes the fiber. Then, it is oxidized by air or an oxidant and restored to its original insoluble dye and fixed on the fiber. At present, the most commonly used reducing agent in industrial production is sodium hydrosulfite, whose chemical name is sodium dithionite. Sodium hydrosulfite has the advantages of strong reducing ability, convenient use and bright color. However, sodium hydrosulfite has poor chemical stability. It easily absorbs oxygen and decomposes when exposed to air, and clumps and emits a pungent sour smell. It decomposes rapidly when in contact with water, 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 caused great harm to the environment (Jin Xiaosong, Wang Helan. Dyes and Coloring, 2011, 48(04):18-21+11.). In recent years, people have been studying some new reduction methods to reduce the usage or replace the insurance powder in view of the shortcomings of insurance powder in application, such as large dosage, difficult storage and environmental pollution.

[0005] Soluble vat dyes are mainly sodium sulfate salts of leuco bodies of vat dyes. They are soluble in water and have good directness to fibers. They 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, and the dyeing method is relatively convenient, so soluble vat dyes have development prospects. However, soluble vat dyes are easily affected by moisture and deteriorate when exposed to air, which reduces the dyeing strength and loses solubility.

[0006] Acid dyes are mainly used on wool, silk and polyamide fibers. After being treated with mordants, they can show good light resistance, washing resistance and shrinkage resistance on wool. Acid dyes contain water-soluble groups, such as sulfonic acid groups (-SO3H) and carboxyl groups (-COOH). These groups exist in the form of sodium salts on the dye molecules, making them water-soluble, which makes acid dyes easy to dissolve in water and convenient to use. In addition, these water-soluble groups are also related to the bright color and complete color spectrum of acid dyes, so acid dyes can provide rich color selection and bright color performance during the dyeing process. However, the molecular structure of acid dyes is relatively simple and lacks a long conjugated coherent system, which leads to its low directness, which means that the dyeing ability of acid dyes is weak. Summary of the invention

[0007] The object of the present invention is to overcome the above-mentioned defects of the prior art, and to provide a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative and a preparation method and application thereof. By connecting a water-soluble group to a vat dye, the dyeing effect of the vat dye can be achieved without reduction, and a 4,4'-diamino-[1,1'-diphenyl]-9,9',10,10'-tetraketone derivative is modified, and the intermediate 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative is closed to synthesize a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative. The problems that the vat dye is easily deteriorated by moisture, the dyeing process is complicated, and the three wastes are seriously polluted are solved, and at the same time, the vat dye has the advantages of good directness and good water solubility of the acid dye, especially the excellent color fastness and exhaustion rate for wool dyeing.

[0008] To achieve the above object, 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, the general structural formula of which is shown in the following 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 at 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 at 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 the mixture is incubated for reaction, and then copper powder is added in a molar ratio of 1:1 to 5:1 to the 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative and the reaction is continued, and then citric acid is added in a molar ratio of 10:1 to 20:1 to the copper powder and citric acid and the reaction is continued. After the reaction is completed, the mixture is filtered while hot, and the filtrate is distilled under reduced pressure, and then dichloromethane is added and filtered 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, cupric chloride, cuprous chloride and copper sulfate.

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

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

[0025] The present invention uses a vat dye PR177 derivative as a matrix, and forms a 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative through Ullmann condensation of a bromoamic acid derivative (1-amino-4-bromoanthraquinone-2-sulfonic acid derivative), and then forms a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative through McMurry reaction. The derivative can be directly dyed without using insurance powder, can be stably exposed to the air compared with soluble vat dyes, and has excellent dyeing performance as an acid dye due to its good planarity. It has the advantages of good directness of vat dyes and good water solubility of acid dyes, and has excellent color fastness and exhaustion rate for wool dyeing in particular.

[0026] The 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative provided by the present invention is brown and has a molar absorption coefficient of up to 15000 L·mol -1 cm -1, water solubility can reach 40.0g / L, the exhaustion rate of dyed wool can reach more than 95%, and the dry and wet friction of level 4 and above can meet the requirements of daily life applications. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

[0030] Figure 4 This is the H NMR spectrum of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid of Example 1 of the present invention.

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

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

[0033] Figure 7 This is the wool dyeing curve of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid of Example 1 of the present 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 DESCRIPTION

[0035] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited in any way.

[0036] Example 1

[0037] The specific synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R1, R2, R3, R4, R5 and R6 are all replaced by 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 comprises the following steps:

[0040] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 40℃ for 30min. After standing, pour out the supernatant as clean as possible. Then add 1-amino-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 50℃ for 4.5h, then add copper powder (2.0g), continue to keep warm for 30min, then add citric acid (1.0g), continue to react for 30min, and filter while hot. The filtrate obtained is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution. After filtering, 7.65g of 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid is obtained, with a yield of 96.4%.

[0041] 2) Add copper powder (1.0 g), anhydrous ethanol (3.0 g), and concentrated sulfuric acid (98%, 3.0 g) to a 100 ml beaker and stir at 40° C. for 30 min. After standing, pour out the supernatant. Then add 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid (3.0 g) and concentrated sulfuric acid (98%, 10.0 g) to the copper powder beaker, keep warm at 55° C. for 30 min, dilute it in an ice-water mixture, 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 2.14 g of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid, with a yield of 75.3%. Figure 1-4 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 -1,585cm -1 ,567cm -1 ,541cm -1 ,487cm -1 .

[0043] Figure 5 is the absorption spectrum of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid, 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 molecules in the solution conform to the Lambert-Beer absorption law.

[0044] Example 2

[0045] The specific synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R3 and R4 are substituted by 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 comprises the following steps:

[0048] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 50℃ for 40min. After standing, pour out the supernatant as clean as possible. Then add 1-amino-4,7-dibromoanthraquinone-2-sulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 40℃ for 4h, then add copper powder (2.0g), continue to keep warm for 40min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution. After filtering, 4,4'-diamino-6,6'-dibromo-1,1'-anthraquinone-3,3'-disulfonic acid is obtained.

[0049] 2) Add copper powder (1.0 g), anhydrous ethanol (3.0 g), and concentrated sulfuric acid (98%, 3.0 g) to a 100 ml beaker and stir at 40°C for 30 min. After standing, pour out the supernatant, then add 4,4'-diamino-6,6'-dibromo-1,1'-dianthraquinone-3,3'-disulfonic acid (3.0 g) and concentrated sulfuric acid (98%, 10.0 g) to the copper powder beaker, keep warm at 55°C for 30 min, dilute it in an ice-water mixture, 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 synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R1 and R2 are substituted by 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 comprises the following steps:

[0054] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 50℃ for 40min. After standing, pour out the supernatant as clean as possible. Then add 1,8-diamino-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 50℃ for 4h, then add copper powder (2.0g), continue to keep warm for 30min, then add citric acid (1.0g), continue to react for 30min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution, stirred and filtered to obtain 4,4',5,5'-tetraamino-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0055] 2) Add copper powder (1.0 g), anhydrous ethanol (3.0 g), and concentrated sulfuric acid (98%, 3.0 g) to a 100 ml beaker and stir at 40°C for 40 min. After standing, pour out the supernatant, then add 4,4',5,5'-tetraamino-1,1'-dianthraquinone-3,3'-disulfonic acid (4.0 g) and concentrated sulfuric acid (98%, 15.0 g) to the copper powder beaker, keep warm at 55°C for 40 min, dilute it in an ice-water mixture, 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 1,6,8,15-tetraamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0056] Example 4

[0057] The specific synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R3 and R4 are substituted by hydroxyl groups 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 comprises the following steps:

[0060] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 50℃ for 40min. After standing, pour out the supernatant as clean as possible. Then add 1-amino-7-hydroxy-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (80.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 60℃ for 4.5h, then add copper powder (2.0g), continue to keep warm for 30min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution. After stirring, filter to obtain 4,4'-diamino-6,6'-dihydroxy-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0061] 2) Add copper powder (1.5 g), anhydrous ethanol (4.5 g), and concentrated sulfuric acid (98%, 4.5 g) to a 100 ml beaker and stir at 50°C for 40 min. After standing, pour out the supernatant, then add 4,4'-diamino-6,6'-dihydroxy-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0 g) and concentrated sulfuric acid (98%, 30.0 g) to the copper powder beaker, keep warm at 50°C for 30 min, dilute it in an ice-water mixture, 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-dihydroxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0062] Example 5

[0063] The specific synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R5 and R6 are substituted by carboxyl groups is as follows:

[0064]

[0065] The preparation method of 1,6-diamino-10,13-dicarboxyl-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid comprises the following steps:

[0066] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 50℃ for 40min. After standing, pour out the supernatant as clean as possible. Then add 1-amino-6-carboxyl-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (80.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 60℃ for 4h, then add copper powder (2.0g), continue to keep warm for 40min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution, stirred and filtered to obtain 4,4'-diamino-7,7'-dicarboxyl-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0067] 2) Add copper powder (2.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 100 ml beaker and stir at 40°C for 40 min. After standing, pour out the supernatant, then add 4,4'-diamino-7,7'-dicarboxyl-1,1'-dianthraquinone-3,3'-disulfonic acid (6.0 g) and concentrated sulfuric acid (98%, 30.0 g) to the copper powder beaker, keep warm at 50°C for 40 min, dilute it in an ice-water mixture, 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-10,13-dicarboxyl-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0068] Example 6

[0069] The specific synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R3 and R4 are substituted by 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 comprises the following steps:

[0072] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 50℃ for 40min. After standing, pour out the supernatant as clean as possible. Then add 1-amino-4-bromoanthraquinone-2,7-disulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 60℃ for 4.5h, then add copper powder (2.0g), continue to keep warm for 30min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution, stirred and filtered to obtain 4,4'-diamino-1,1'-dianthraquinone-3,3',6,6'-tetrasulfonic acid.

[0073] 2) Add copper powder (2.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 100 ml beaker and stir at 50°C for 30 min. After standing, pour out the supernatant. Then add 4,4'-diamino-1,1'-dianthraquinone-3,3',6,6'-tetrasulfonic acid (5.0 g) and concentrated sulfuric acid (98%, 30.0 g) to the copper powder beaker. Keep warm at 50°C for 40 min. Dilute it in an ice-water mixture, 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 synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R3 and R4 are substituted by nitro 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 comprises the following steps:

[0078] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir at 50℃ for 40min. After standing, pour out the supernatant as clean as possible. Then add 1-amino-7-nitro-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 60℃ for 4.5h, then add copper powder (2.0g), continue to keep warm for 40min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution, stirred and filtered to obtain 4,4'-diamino-6,6'-dinitro-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0079] 2) Add copper powder (2.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 100 ml beaker and stir at 40°C for 40 min. After standing, pour out the supernatant, then add 4,4'-diamino-6,6'-dinitro-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0 g) and concentrated sulfuric acid (98%, 30.0 g) to the copper powder beaker, keep warm at 50°C for 40 min, dilute it in an ice-water mixture, 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 synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R3 and R4 are substituted by 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 comprises the following steps:

[0084] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir for 30min at 50℃. After standing, pour out the supernatant as clean as possible. Then add 1-amino-7-methyl-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 50℃ for 4.5h, then add copper powder (2.0g), continue to keep warm for 50min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution, stirred and filtered to obtain 4,4'-diamino-6,6'-dimethyl-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0085] 2) Add copper powder (2.0 g), anhydrous ethanol (6.0 g), and concentrated sulfuric acid (98%, 6.0 g) to a 100 ml beaker and stir at 40°C for 40 min. After standing, pour out the supernatant, then add 4,4'-diamino-6,6'-dimethyl-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0 g) and concentrated sulfuric acid (98%, 30.0 g) to the copper powder beaker, keep warm at 50°C for 40 min, dilute it in an ice-water mixture, 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-dimethyl-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0086] Example 9

[0087] The specific synthesis route of 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid in which R1 and R2 are substituted by methoxy 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 comprises the following steps:

[0090] 1) Add copper powder (4.0g), anhydrous ethanol (6.0g), and concentrated sulfuric acid (98%, 6.0g) to a 500ml three-necked flask and stir for 30min at 40℃. After standing, pour out the supernatant as clean as possible. Then add 1-amino-8-methoxy-4-bromoanthraquinone-2-sulfonic acid (10.0g), DMF (100.0g), and anhydrous methanol (200.0g) to the three-necked flask, keep warm at 50℃ for 4.5h, then add copper powder (2.0g), continue to keep warm for 35min, then add citric acid (1.0g), continue to react for 40min, and filter while hot. The obtained filtrate is distilled under reduced pressure, and DCM (dichloromethane) is added to the distilled solution, stirred and filtered to obtain 4,4'-diamino-5,5'-dimethoxy-1,1'-dianthraquinone-3,3'-disulfonic acid.

[0091] 2) Add copper powder (1.0 g), anhydrous ethanol (3.0 g), and concentrated sulfuric acid (98%, 3.0 g) to a 100 ml beaker and stir at 50°C for 40 min. After standing, pour out the supernatant, then add 4,4'-diamino-5,5'-dimethoxy-1,1'-dianthraquinone-3,3'-disulfonic acid (4.0 g) and concentrated sulfuric acid (98%, 15.0 g) to the copper powder beaker, keep warm at 55°C for 30 min, dilute it in an ice-water mixture, 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-dimethoxy-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid.

[0092] Example 10

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

[0094]

[0095] The preparation method of 1,6-diamino-8,15-dimethylcarbodiyl-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid comprises the following steps:

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

[0097] 2) Add copper powder (1.0 g), anhydrous ethanol (3.0 g), and concentrated sulfuric acid (98%, 3.0 g) to a 100 ml beaker and stir at 50° C. for 40 min. After standing, pour out the supernatant, then add 4,4'-diamino-5,5'-dimethyl-1,1'-dianthraquinone-3,3'-disulfonic acid (5.0 g) and concentrated sulfuric acid (98%, 15.0 g) to the copper powder beaker, keep warm at 55° C. for 40 min, dilute it in an ice-water mixture, 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-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 example was applied to wool dyeing. Figure 7 The wool dyeing curve is shown below. Different chromaticities were used for dyeing, and contrast was made with or without the addition of a fixing agent. The fixing agent was JF-2113. 2g wool sample was used. 0.0250g, 0.0500g, and 0.1000g of the product were taken into a 100mL volumetric flask for dyeing. 40mL of dye solution was taken with a pipette and added to the dyeing tank. The bath ratio was 1:20, and the acidic condition was PH = 4.5. The exhaustion rate of all chromaticities with or without the addition of a fixing agent could reach more than 95%. The dyed wool samples were as follows: Figure 8 The measured color fastnesses are shown in Table 1.

[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 Figure 7-Figure 8 As shown in Table 1, the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative molecules of the present invention are brown, and the molar absorption coefficient can reach 15000 L·mol -1 cm -1 The water solubility can reach 40.0g / L, the exhaustion rate of dyed wool can reach more than 95%, and the dry and wet friction of level 4 and above can meet the requirements of daily life applications.

[0103] The effects of Examples 2 to 10 are the same as those of Example 1.

[0104] In summary, the present invention uses a vat dye PR177 derivative that can present a highly bright and clear red tone and has excellent properties such as weather resistance, heat resistance, light resistance, solvent resistance, chemical resistance, and high tinting power, low toxicity, migration resistance, resistance to plastic molding and paint drying temperature as a matrix, and a 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative is subjected to Ullmann condensation to form a 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonic acid derivative, and then a McMurray reaction is performed to close the ring to form a 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative, so that it can be directly dyed without using insurance powder, and can be stably exposed to the air compared with soluble vat dyes, and because it has good planarity, it also has excellent dyeing performance as an acid dye, and it has the advantages of good directness of vat dyes and good water solubility of acid dyes, especially for wool dyeing, it has excellent color fastness and exhaustion rate.

[0105] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached 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 the following formula (I): 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.

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 as follows:

3. A method for preparing the 1,6-diamino-dibenzo[a,o]perylene-7,16-dione-2,5-disulfonic acid derivative according to any one of claims 1 to 2, characterized in that: The following steps are involved: (1) mixing a copper catalyst, anhydrous ethanol and concentrated sulfuric acid and reacting them at 30° C. to 70° C. for 20 min to 40 min, followed by cooling, filtering and drying to obtain copper powder; (2) mixing the copper powder with a 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative, anhydrous methanol and N,N-dimethylformamide and keeping the mixture at 30° C. to 70° C. for 4.0 h to 6.0 h, then adding the copper powder and keeping the mixture at 30° C. to 70° C. for 0.5 h to 2 h, then adding citric acid and keeping the mixture at 30° C. to 1.0 h, filtering while hot after the reaction is completed, distilling and filtering the obtained filtrate under reduced pressure to obtain a 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 copper powder and concentrated sulfuric acid are mixed at 40°C to 60°C for 20min to 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 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 the mixture is kept warm for reaction. Then, copper powder is added in a molar ratio of 1:1 to 5:1 between the copper powder and the 1-amino-4-bromoanthraquinone-2-sulfonic acid derivative and the mixture is kept warm for reaction. Subsequently, citric acid is added in a molar ratio of 10:1 to 20:1 between the copper powder and the citric acid and the mixture is kept warm for reaction. After the reaction is completed, the mixture is filtered while hot. The obtained filtrate is subjected to reduced pressure distillation, and then dichloromethane is added and filtered 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, copper powder and concentrated sulfuric acid is 1:2:10 to 1:5:

50.

7. The preparation method according to claim 3, characterized in that: The copper catalyst comprises one or more of copper powder, copper acetate, cupric chloride, cuprous chloride and copper sulfate.

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

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