5-substituted amino-5 '-acetamido-3, 3'-dipyridyl derivative as well as preparation method and application thereof

Abstract

The invention relates to the technical field of dye synthesis, and particularly discloses a 5-substituted amino-5 '-acetamido-3, 3'-dipyridyl derivative as well as a preparation method and application of the 5-substituted amino-5 '-acetamido-3, 3'-dipyridyl derivative. The structure of the 5-substituted amino-5 '-acetamido-3, 3'-dipyridyl derivative is as shown in a formula (I) in the specification, according to the application, N-acetyl blue is used as a parent for modification, and different derivative structures are introduced to amino groups, so that the novel bipyridine dye, namely the 5-substituted amino-5 '-acetamido-3, 3'-bipyridine derivative, is obtained. The 5-substituted amino-5 '-acetamido-3, 3'-dipyridyl derivative has higher color development intensity, and has the advantages of comprehensive color fastness, water washing resistance, acid resistance, sublimation resistance, wet friction resistance, excellent performance and the like when being applied to fabric dyeing.

Description

Technical Field

[0001] The present application relates to the technical field of dye synthesis, and in particular to a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative and a preparation method and application thereof. Background Art

[0002] Indigoidine is a substance with a double ring structure formed by the condensation of two glutamine molecules under the action of indigo synthase. Indigoidine is a bright and harmless natural blue pigment with a wide range of applications, including cosmetics, textile printing and dyeing, and the medical industry. However, indigoidine itself can only provide one color, which obviously cannot meet the market demand for natural pigments.

[0003] In the previous research process, CN118772055A reported a purification process and application of N-acetyl indigo blue. However, this monoacetylated indigo blue did not significantly change the color of the substance. Summary of the invention

[0004] The purpose of the present application is to overcome the deficiencies of the above-mentioned prior art and to provide a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative and a preparation method and application thereof.

[0005] To achieve the above purpose, the technical solution adopted by this application is: The present application provides a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, the structure of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative is shown in formula (I); Formula (I); in, A is selected from one of C, S, and P; R is selected from C2~C20 alkyl, substituted C2~C20 alkyl, C2~C20 alkenyl, substituted C2~C20 alkenyl, C2~C20 alkynyl, substituted C2~C20 alkynyl, C3~C20 cycloalkyl, substituted C3~C20 cycloalkyl, C5~C20 aryl, substituted C5~C20 aryl, and substituted or unsubstituted heterocycle; The heterocyclic ring includes one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone and anthraquinone; n is selected from 0, 1 or 2; m is selected from 0 or 1.

[0006] The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives provided in the present application have high yield, stable structure and high temperature resistance, high color intensity, can be used as dyes in cotton fabric dyeing, and have good acid resistance, friction resistance, and water washing fastness.

[0007] As a preferred embodiment of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, A is selected from C or S; R is selected from C2~C18 alkyl, substituted C2~C18 alkyl, C2~C18 alkenyl, substituted C2~C18 alkenyl, C2~C18 alkynyl, substituted C2~C18 alkynyl, C3~C18 cycloalkyl, substituted C3~C18 cycloalkyl, C5~C18 aryl, substituted C5~C18 aryl, and substituted heterocycle.

[0008] The present application prefers that the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives of the above structure have higher color intensity, bright colors after dyeing, deep dyeing and comprehensive dyeing fastness; the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives are used as dyes in the dyeing of cotton fabrics to better improve the acid resistance, friction resistance and washing fastness of the fabrics.

[0009] As a preferred embodiment of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the substituted C2~C20 alkyl includes halogen-substituted C2~C20 alkyl; the substituted C2~C20 alkenyl includes halogen-substituted C2~C20 alkenyl; the substituted C2~C20 alkynyl includes halogen-substituted C2~C20 alkynyl; the substituted C3~C20 cycloalkyl includes halogen-substituted C3~C20 cycloalkyl; the substituted C5~C20 aryl includes halogen-substituted C5~C20 aryl; the substituted heterocycle includes a halogen-substituted heterocycle: one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone, and anthraquinone.

[0010] As a preferred embodiment of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the substituted C2~C18 alkyl includes halogen-substituted C2~C18 alkyl; the substituted C2~C18 alkenyl includes halogen-substituted C2~C18 alkenyl; the substituted C2~C18 alkynyl includes halogen-substituted C2~C18 alkynyl; the substituted C3~C18 cycloalkyl includes halogen-substituted C3~C18 cycloalkyl; the substituted C5~C18 aryl includes halogen-substituted C5~C18 aryl.

[0011] And / or, the substituted or unsubstituted heterocyclic ring is one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone and anthraquinone, and the substituent of the heterocyclic ring is one of halogen, C1~C3 alkyl and halogenated C1~C3 alkyl.

[0012] Preferably, the halogenated C2~C20 alkyl group or the halogenated C2~C18 alkyl group is a straight-chain or branched-chain alkyl group, and the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms.

[0013] The alkenyl group is a straight or branched chain group having 3 to 6 carbon atoms and may have a double bond at any position, and the alkynyl group is a straight or branched chain group having 3 to 6 carbon atoms and may have a triple bond at any position.

[0014] The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives include at least one of the following structures:

[0015] The present application also provides a method for preparing the above-mentioned 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps: S1, grinding N-acetyl indigo blue and dispersing it in an organic solvent to obtain a suspension; S2, adding a derivatization reagent and a catalyst to the suspension obtained in step S1, and then adding an acid binding agent, reacting at 40-120° C. for 1-24 h until no N-acetyl blue is detected by chromatographic analysis, which is considered the reaction endpoint, and obtaining a reaction product solution; S3, adding deionized water to the reaction product solution, cooling and stirring, and performing purification treatment; S4, subjecting the purified solution in step S3 to solid-liquid separation and drying to obtain 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives.

[0016] N-acetyl indigo blue is a natural blue pigment obtained by microbial fermentation and belongs to the pyridine heterocyclic reduction dye. The present application uses N-acetyl indigo blue as a parent for modification, and introduces different derivative structures on the amino group to obtain the novel bipyridine dye of the present application, namely, 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives prepared by the above method are safe, simple, energy-saving, and have stable product quality and good reproducibility.

[0017] The preparation process of the above 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives is as follows:

[0018] As a preferred embodiment of the preparation method of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the organic solvent includes one of n-butane, n-hexane, n-pentane, tetrahydrofuran, carbon tetrachloride, dichloromethane, dichloroethane, chloroform, dimethylformamide and dimethylacetamide; preferably, the organic solvent is one of dimethylformamide, dimethylacetamide, tetrahydrofuran and carbon tetrachloride; And / or, the acid binding agent is at least one of triethylamine, trimethylamine, pyridine, N-methylmorpholine, tetramethylethylenediamine, sodium tert-butoxide, potassium carbonate, sodium carbonate and potassium tert-butoxide.

[0019] The present application adopts the above-mentioned type of acid binding agent, which can further promote the completion of the reaction, improve efficiency, and reduce the harm of by-products to the reaction equipment.

[0020] As a preferred embodiment of the preparation method of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the derivatization reagent includes the following structures containing halogen or acyl halide: C2~C20 alkyl, substituted C2~C20 alkyl, C2~C20 alkenyl, substituted C2~C20 alkenyl, C2~C20 alkynyl, substituted C2~C20 alkynyl, C3~C20 cycloalkyl, substituted C3~C20 cycloalkyl, C5~C20 aryl, Substituted C5~C20 aryl, and substituted or unsubstituted heterocycle containing halogen or acyl halide: one of substituted furan, substituted thiophene, substituted pyrrole, substituted thiazole, substituted imidazole, substituted pyridine, substituted piperidine, substituted pyrazine, substituted pyridazine, substituted indole, substituted quinoline, substituted pteridine, substituted acridine, substituted naphthalene, substituted phenanthrene, substituted anthracene, substituted pyrene, substituted naphthoquinone, substituted phenanthrenequinone, substituted anthraquinone; the substituent of the heterocycle is one of halogen, C1~C3 alkyl, halogenated C1~C3 alkyl.

[0021] As a preferred embodiment of the method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the molar ratio of N-acetyl indole, the derivatization reagent and the acid binding agent is 1:(1.2~2.2):(1.2~2.2).

[0022] In the technical solution of the present application, the molar ratio of N-acetyl indigo plant blue, the derivatization reagent and the acid-binding agent is within the above-mentioned range, which can better improve the yield of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and improve the color intensity of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives.

[0023] Preferably, in step S3, the mass ratio of the deionized water to the reaction product solution is (3-5):1, and the temperature is controlled at 0-25°C.

[0024] Preferably, in step S4, the drying temperature is 50-80°C.

[0025] Preferably, in step S4, the solid-liquid separation is performed by suction filtration or centrifugation.

[0026] As a preferred embodiment of the preparation method of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the catalyst is a Lewis acid catalyst, and the Lewis acid catalyst includes one of boron trifluoride, aluminum trichloride, ferric chloride, boron tribromide, aluminum tribromide, and ferric tribromide; The addition amount of the Lewis acid catalyst is 0.1% to 5% of the mass of N-acetyl indigo.

[0027] The present application also provides the use of the above 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives in dyeing cotton fabrics.

[0028] The preparation method of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives of the present application is safe, simple, energy-saving, and has stable product quality, good reproducibility, high yield, and is suitable for industrial production.

[0029] Compared with the prior art, this application has the following beneficial effects: The present application provides a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative and its preparation method and application. The present application uses N-acetyl indigo as a parent for modification, introduces different derivative structures on the amino group, and obtains the novel bipyridine dye of the present application, namely, 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative has a high color intensity. When applied to fabric dyeing, it has the advantages of comprehensive color fastness, water resistance, acid resistance, sublimation resistance, wet friction resistance, and excellent performance; and the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative using the above preparation method has the characteristics of safety, simplicity, energy saving, stable product quality, and good reproducibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is the structural diagram of the target product 1; Figure 2 is the structural diagram of the target product 2; Figure 3 is the structural diagram of the target product 3; Figure 4 is the structural diagram of the target product 4; Figure 5 is the structural diagram of the target product 5; Figure 6is the structural diagram of the target product 6; Figure 7 is the structural diagram of the target product 7; Figure 8 is the structural diagram of the target product 8; Fig. 9 is the structural diagram of the target product 9; Fig.10 is the structural diagram of the target product 10; Fig.11 is the structural diagram of the target product 11; Fig.12 is the structural diagram of the target product 12; Fig.13 is the structural diagram of the target product 13; Fig.14 This is the structural diagram of the target product 14. DETAILED DESCRIPTION

[0031] In order to better illustrate the purpose, technical solutions and advantages of the present application, the present application will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0032] In the following examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified, and the components and raw materials used in each parallel experiment are of the same type.

[0033] The N-acetyl indigo plantain used in the following examples was provided by Nanjing Hegu Life Biotechnology Co., Ltd. Structural identification of the target product: The synthesized product was sent to the Analysis and Testing Center of Nanjing Normal University for testing.

[0034] Example 1: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 10 g of N-acetyl indigo raw material, add 100 g of tetrahydrofuran to a 500 mL three-necked round-bottom flask and fully disperse, drop propionyl chloride and triethylamine to react (the molar ratio of N-acetyl indigo: propionyl chloride: triethylamine is 1:1.2:1.5), add ferric chloride as a catalyst, the addition amount is 0.1% of the mass of N-acetyl indigo, react at 90°C for 6 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 4 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 60°C to obtain the target product 1.

[0035] The structural formula of target product 1 is as follows Figure 1 shown.

[0036] Characterization of target product 1: LC-MS (m / z,%): 349.1 ([M+H] + , 100).

[0037] Example 2: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 5 g of N-acetyl indigo plant raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and fully disperse, drop acryloyl chloride and sodium tert-butoxide (the molar ratio of N-acetyl indigo plant: acryloyl chloride: sodium tert-butoxide is 1:1.2:2.2), add aluminum chloride as a catalyst, the addition amount is 0.1% of the mass of N-acetyl indigo plant, react at 80°C for 10 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 2.

[0038] The structural formula of target product 2 is as follows Figure 2 shown.

[0039] Characterization of target product 2: LC-MS (m / z,%): 346.2 ([M+H] + , 100).

[0040] Example 3: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 5 g of N-acetyl indigo raw material, add 100 g of tetrahydrofuran to a 500 mL three-necked round-bottom flask and fully disperse, drop propioloyl chloride and pyridine (the molar ratio of N-acetyl indigo: propioloyl chloride: pyridine is 1:1.5:2.2), add boron tribromide as a catalyst, the addition amount is 1% of the mass of N-acetyl indigo, react at 90°C for 10 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 3.

[0041] The structural formula of target product 3 is as follows Figure 3 shown.

[0042] Characterization of target product 3: LC-MS (m / z,%): 345.2 ([M+H] + , 100).

[0043] Example 4: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 10 g of N-acetyl indigo blue raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and fully disperse, dropwise add cyclopropylcarbonyl chloride and triethylamine (the molar ratio of N-acetyl indigo blue: cyclopropylcarbonyl chloride: triethylamine is 1:1.4:2.2), add boron trifluoride as a catalyst, the addition amount is 2% of the mass of N-acetyl indigo blue, react at 80°C for 9 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 4.

[0044] The structural formula of target product 4 is as follows Figure 4 shown.

[0045] Characterization of target product 4: LC-MS (m / z,%): 360.1 ([M+H] + , 100).

[0046] Example 5: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 5 g of N-acetyl indigo raw material, add 150 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and fully disperse, drop benzoyl chloride and triethylamine (the molar ratio of N-acetyl indigo: benzoyl chloride: triethylamine is 1:1.2:2.2), add aluminum tribromide as a catalyst, the addition amount is 0.1% of the mass of N-acetyl indigo, react at 90°C for 8 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 5.

[0047] The structural formula of target product 5 is as follows Figure 5 shown.

[0048] Characterization of target product 5: LC-MS (m / z,%): 397.3 ([M+H]+ , 100).

[0049] Example 6: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 10 g of N-acetyl indigo raw material, add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and fully disperse, drop nicotinyl chloride and triethylamine (the molar ratio of N-acetyl indigo: nicotinyl chloride: triethylamine is 1:1.5:2.2), add ferric bromide as a catalyst, the addition amount is 5% of the mass of N-acetyl indigo, react at 90°C for 12 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 70°C to obtain the target product 6.

[0050] The structural formula of target product 6 is as follows Figure 6 shown.

[0051] Characterization of target product 6: LC-MS (m / z,%): 398.1 ([M+H] + , 100).

[0052] Example 7: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 10 g of N-acetyl indigo raw material, add 100 g of tetrahydrofuran to a 500 mL three-necked round-bottom flask and fully disperse, dropwise add quinoline-4-carbonyl chloride and trimethylamine (the molar ratio of N-acetyl indigo: quinoline-4-carbonyl chloride: trimethylamine is 1:1.2:2.2), add aluminum chloride as a catalyst, the addition amount is 2% of the mass of N-acetyl indigo, react at 120°C for 24 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 7.

[0053] The structural formula of target product 7 is as follows Figure 7 shown.

[0054] Characterization of target product 7: LC-MS (m / z,%): 448.4 ([M+H] + , 100).

[0055] Example 8: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 10 g of N-acetyl indigo blue raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and fully disperse, drop n-butyl bromide and potassium carbonate (the molar ratio of N-acetyl indigo blue: n-butyl bromide: potassium carbonate is 1:1.2:2.2), add boron tribromide as a catalyst, the addition amount is 2% of the mass of N-acetyl indigo blue, react at 100°C for 10 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 8.

[0056] The structural formula of target product 8 is as follows Figure 8 shown.

[0057] Characterization of target product 8: LC-MS (m / z,%): 349.2 ([M+H] + , 100).

[0058] Example 9: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 15 g of N-acetyl indigo blue raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and fully disperse, drop chlorocyclohexane and triethylamine (the molar ratio of N-acetyl indigo blue: chlorocyclohexane: triethylamine is 1:1.5:2.2), add aluminum tribromide as a catalyst, the addition amount is 2% of the mass of N-acetyl indigo blue, react at 85°C for 12 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 9.

[0059] The structural formula of target product 9 is as follows Fig. 9 shown.

[0060] Characterization of target product 9: LC-MS (m / z,%): 375.2 ([M+H] + , 100).

[0061] Example 10: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 5 g of N-acetyl indigo blue raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and fully disperse, drop pyridine bromide and triethylamine (the molar ratio of N-acetyl indigo blue: pyridine bromide: triethylamine is 1:1.5:2.2), add ferric bromide as a catalyst, the addition amount is 2% of the mass of N-acetyl indigo blue, react at 100°C for 10 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 10.

[0062] The structural formula of target product 10 is as follows Fig.10 shown.

[0063] Characterization of target product 10: LC-MS (m / z,%): 370.1 ([M+H] + , 100).

[0064] Example 11: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 5 g of N-acetyl indigo raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and fully disperse, drop propylsulfonyl chloride and tetramethylethylenediamine (the molar ratio of N-acetyl indigo: propylsulfonyl chloride: tetramethylethylenediamine is 1:1.2:1.2), add ferric chloride as a catalyst, the addition amount is 3% of the mass of N-acetyl indigo, react at 80°C for 4 hours, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 11.

[0065] The structural formula of target product 11 is as follows Fig.11 shown.

[0066] Characterization of target product 11: LC-MS (m / z,%): 397.1 ([M+H] + , 100).

[0067] Example 12: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 10 g of N-acetyl indigo plant raw material, add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and fully disperse, dropwise add p-toluenesulfonyl chloride and N-methylmorpholine (the molar ratio of N-acetyl indigo: p-toluenesulfonyl chloride: N-methylmorpholine is 1:1.2:2), add aluminum chloride as a catalyst, the addition amount is 3.5% of the mass of N-acetyl indigo, react at 110°C for 9 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 12.

[0068] The structural formula of target product 12 is as follows Fig.12 shown.

[0069] Characterization of target product 12: LC-MS (m / z,%): 447.1 ([M+H] + , 100).

[0070] Example 13: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 6 g of N-acetyl indigo blue raw material, add 200 g of carbon tetrachloride to a 500 mL three-necked round-bottom flask and fully disperse, drop diphenylphosphine chloride and sodium carbonate (the molar ratio of N-acetyl indigo blue: diphenylphosphine chloride: sodium carbonate is 1:1.2:2.2), add ferric chloride as a catalyst, the addition amount is 1.5% of the mass of N-acetyl indigo blue, react at 100°C for 8h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 13.

[0071] The structural formula of target product 13 is as follows Fig.13 shown.

[0072] Characterization of target product 13: LC-MS (m / z, %): 491.1 ([M+H] + , 100).

[0073] Example 14: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and preparation methods thereof This embodiment provides a method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, comprising the following steps: Weigh 4 g of N-acetyl indigo blue raw material, add 100 g of carbon tetrachloride to a 500 mL three-necked round-bottom flask and fully disperse, dropwise add dicyclohexylphosphinoyl chloride and potassium tert-butoxide (the molar ratio of N-acetyl indigo blue: dicyclohexylphosphinoyl chloride: potassium tert-butoxide is 1:1.2:2), add boron tribromide as a catalyst, the addition amount is 2.5% of the mass of N-acetyl indigo blue, react at 90°C for 10 h, and obtain a reaction product solution. After the reaction product solution cools to room temperature, add 5 times the mass of deionized water and stir to purify, and the temperature is controlled at 0-5°C. Vacuum filtration is used to remove the solvent, and the filter cake is dried in an oven at 80°C to obtain the target product 14.

[0074] The structural formula of target product 14 is as follows Fig.14 shown.

[0075] Characterization of target product 14: LC-MS (m / z,%): 503.2 ([M+H] + , 100).

[0076] The reaction conditions are similar to those of Examples 1 to 14 above, but the derivatization reagent and catalyst are changed. The structure of the derivatization reagent corresponds to different substituents. The catalyst does not change the structure of the product of the reaction.

[0077] The prepared 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives are shown in Table 1.

[0078] Table 1 Test example: Application of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives in dyeing The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives obtained in the above example are used to dye cotton textiles according to the following process: 5-Substituted amino-5'-acetylamino-3,3'-bipyridine derivatives 2% (owf), reduced with 2 times hydrosulfite, adjusted to pH 5 with 0.5 mL / L citric acid, dyed at 25℃ for 10 min, bath ratio 1:30.

[0079] After dyeing, take out the dyed fabric sample, wash it, dry it, and use the Lambert-Beer law to solve the K / S value of the dye.

[0080] The various properties of the dye were tested according to the standards, and the test results were recorded in Table 2 below.

[0081] Table 2 The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives of Examples 1 to 14 and different numbers can dye cotton fabrics, and their K / S values ​​reach more than 10, the dyeing rate reaches more than 80%, and the color fastness to washing, color fastness to sublimation, color fastness to acid spots, color fastness to sunlight, and color fastness to wet rubbing all reach level 4. Compared with the K / S value of N-acetyl blue of 9.2 and the dyeing rate of 84.8%, the derivatives of the present invention have better dyeing effect.

[0082] Based on the existing N-acetyl indigo plant, the present application obtains 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives through a chemical synthesis method. The derivatives have stable color, are resistant to high and low temperatures under acidic conditions, and have a very broad application range and application prospects for industrial production.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application rather than to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, ordinary technicians in this field should understand that the technical solution of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present application.

Claims

1. A 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, characterized in that: The structure of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative is shown in formula (I); Formula (I); in, A is selected from one of C, S, and P; R is selected from C2~C20 alkyl, substituted C2~C20 alkyl, C2~C20 alkenyl, substituted C2~C20 alkenyl, C2~C20 alkynyl, substituted C2~C20 alkynyl, C3~C20 cycloalkyl, substituted C3~C20 cycloalkyl, C5~C20 aryl, substituted C5~C20 aryl, and substituted or unsubstituted heterocycle; The heterocyclic ring includes one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone and anthraquinone; n is selected from 0, 1 or 2; m is selected from 0 or 1.

2. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative according to claim 1, characterized in that: A is selected from C or S; R is selected from C2~C18 alkyl, substituted C2~C18 alkyl, C2~C18 alkenyl, substituted C2~C18 alkenyl, C2~C18 alkynyl, substituted C2~C18 alkynyl, C3~C18 cycloalkyl, substituted C3~C18 cycloalkyl, C5~C18 aryl, substituted C5~C18 aryl, and substituted heterocycle.

3. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative according to claim 1, characterized in that: The substituted C2~C20 alkyl includes halogen-substituted C2~C20 alkyl; the substituted C2~C20 alkenyl includes halogen-substituted C2~C20 alkenyl; the substituted C2~C20 alkynyl includes halogen-substituted C2~C20 alkynyl; the substituted C3~C20 cycloalkyl includes halogen-substituted C3~C20 cycloalkyl; the substituted C5~C20 aryl includes halogen-substituted C5~C20 aryl; the substituted heterocycle includes halogen-substituted heterocycle: one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone and anthraquinone.

4. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative according to claim 2, characterized in that: Substituted C2~C18 alkyl includes halogen-substituted C2~C18 alkyl; substituted C2~C18 alkenyl includes halogen-substituted C2~C18 alkenyl; substituted C2~C18 alkynyl includes halogen-substituted C2~C18 alkynyl; substituted C3~C18 cycloalkyl includes halogen-substituted C3~C18 cycloalkyl; substituted C5~C18 aryl includes halogen-substituted C5~C18 aryl; And / or, the substituted or unsubstituted heterocyclic ring is one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone and anthraquinone, and the substituent of the heterocyclic ring is one of halogen, C1~C3 alkyl and halogenated C1~C3 alkyl.

5. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative according to claim 1, characterized in that: The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives include at least one of the following structures: 。 6. The method for preparing a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, grinding N-acetyl indigo blue and dispersing it in an organic solvent to obtain a suspension; S2, adding a derivatization reagent and a catalyst to the suspension obtained in step S1, and then adding an acid binding agent, reacting at 40-120° C. for 1-24 h until no N-acetyl blue is detected by chromatographic analysis, which is considered the reaction endpoint, and obtaining a reaction product solution; S3, adding deionized water to the reaction product solution, cooling and stirring, and performing purification treatment; S4, subjecting the purified solution in step S3 to solid-liquid separation and drying to obtain 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives.

7. The preparation method according to claim 6, characterized in that: The organic solvent comprises one of n-butane, n-hexane, n-pentane, tetrahydrofuran, carbon tetrachloride, dichloromethane, dichloroethane, chloroform, dimethylformamide and dimethylacetamide; and / or, the acid binding agent is at least one of triethylamine, trimethylamine, pyridine, N-methylmorpholine, tetramethylethylenediamine, sodium tert-butoxide, potassium carbonate, sodium carbonate and potassium tert-butoxide; And / or, the derivatization reagent includes the following structures containing halogen or acyl halide: C2~C20 alkyl, substituted C2~C20 alkyl, C2~C20 alkenyl, substituted C2~C20 alkenyl, C2~C20 alkynyl, substituted C2~C20 alkynyl, C3~C20 cycloalkyl, substituted C3~C20 cycloalkyl, C5~C20 aryl, substituted C5~C20 aryl, and substituted or unsubstituted heterocyclic ring containing halogen or acyl halide: substituted furan, substituted thiophene, substituted pyrrole, substituted thiazole, substituted imidazole, substituted pyridine, substituted piperidine, substituted pyrazine, substituted pyridazine, substituted indole, substituted quinoline, substituted pteridine, substituted acridine, substituted naphthalene, substituted phenanthrene, substituted anthracene, substituted pyrene, substituted naphthoquinone, substituted phenanthrenequinone, substituted anthraquinone; the substituent of the heterocyclic ring is one of halogen, C1~C3 alkyl, and halogenated C1~C3 alkyl.

8. The preparation method according to claim 6, characterized in that: The molar ratio of the N-acetyl indigo plantarum, the derivatizing agent and the acid-binding agent is 1:(1.2-2.2):(1.2-2.2).

9. The preparation method according to claim 6, characterized in that: The catalyst is a Lewis acid catalyst, and the Lewis acid catalyst includes one of boron trifluoride, aluminum trichloride, ferric chloride, boron tribromide, aluminum tribromide, and ferric tribromide; The addition amount of the Lewis acid catalyst is 0.1% to 5% of the mass of N-acetyl indigo.

10. Use of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives according to any one of claims 1 to 5 in dyeing cotton fabrics.

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