A 5-substituted amino-5'-acetamido-3,3'-bipyridine derivative, its preparation method and application

Abstract

The present application relates to the technical field of dye synthesis, and specifically discloses a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, its preparation method, and application. The structure of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative is shown in Formula (I); the present application uses N-acetyl indigo as a matrix for modification, introducing different derivative structures at the amino group to obtain the novel bipyridine dye of the present application, namely, a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative. The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative has high color intensity and is applied to fabric dyeing, exhibiting advantages such as comprehensive color fastness, resistance to water washing, acid resistance, sublimation resistance, resistance to wet friction, and excellent performance.

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, a preparation method thereof, and an application thereof. Background Art

[0002] Indigoidine, also known as indigoidine, is a bicyclic substance formed by the condensation of two glutamine molecules under the action of indigo synthase. A bright and harmless natural blue pigment, indigoidine has a wide range of applications, including cosmetics, textile printing and dyeing, and the medical industry. However, indigoidine itself only provides one color, which clearly cannot meet the market demand for natural pigments.

[0003] In the early 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 objectives, the technical solutions adopted in this application are:

[0006] The present application provides a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, the structure of which is shown in formula (I);

[0007]

[0008] Formula (I);

[0009] in,

[0010] A is selected from one of C, S, and P;

[0011] 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;

[0012] 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;

[0013] n is selected from 0, 1 or 2;

[0014] m is selected from 0 or 1.

[0015] 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 for dyeing cotton fabrics, and have good acid resistance, friction resistance, and water washing fastness.

[0016] 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;

[0017] 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.

[0018] 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 fabric.

[0019] 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.

[0020] 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; and the substituted C5~C18 aryl includes halogen-substituted C5~C18 aryl.

[0021] 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.

[0022] 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 substituted by halogen atoms.

[0023] 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. 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.

[0024] The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives include at least one of the following structures:

[0025]

[0026] 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:

[0027] S1, grinding N-acetyl indigo blue and dispersing it in an organic solvent to obtain a suspension;

[0028] 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 hours until no N-acetyl blue is detected by chromatographic analysis, which is determined to be the reaction endpoint, to obtain a reaction product solution;

[0029] S3, adding deionized water to the reaction product solution, cooling and stirring, and performing purification treatment;

[0030] S4. Perform solid-liquid separation on the purified solution in step S3 and dry it to obtain 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives.

[0031] N-acetyl indigo blue is a natural blue pigment obtained through microbial fermentation and belongs to the pyridine heterocyclic reducing dye class. This application uses N-acetyl indigo blue as a precursor for modification, introducing different derivative structures at the amino group to obtain the novel bipyridine dyes described herein, namely 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives. The preparation method for these 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives is safe, simple, energy-efficient, and offers stable product quality and excellent reproducibility.

[0032] The preparation process of the above-mentioned 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives is as follows:

[0033]

[0034] 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 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;

[0035] 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.

[0036] 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.

[0037] 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 groups, and substituted or unsubstituted heterocycles containing halogen or acyl halide groups: 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, and substituted anthraquinone; the substituent of the heterocycle is one of halogen, C1~C3 alkyl, and halogenated C1~C3 alkyl.

[0038] As a preferred embodiment of the preparation method of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives described in the present application, the molar ratio of the N-acetyl indole, the derivatization reagent and the acid binding agent is 1:(1.2~2.2):(1.2~2.2).

[0039] In the technical solution of the present application, the molar ratio of N-acetyl indole, 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.

[0040] 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.

[0041] Preferably, in step S4, the drying temperature is 50-80°C.

[0042] Preferably, in step S4, the solid-liquid separation is performed by suction filtration or centrifugation.

[0043] 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 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;

[0044] The addition amount of the Lewis acid catalyst is 0.1% to 5% of the mass of N-acetyl indigo.

[0045] The present application also provides the use of the above 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives in cotton fabric dyeing.

[0046] 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.

[0047] Compared with the prior art, this application has the following beneficial effects:

[0048] The present application provides a 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, its preparation method, and application. This application utilizes N-acetyl indigo as a precursor for modification, introducing different derivative structures at the amino group to obtain the novel bipyridine dyes of the present application, namely, 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives. 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives have high color intensity and, when applied to fabric dyeing, exhibit advantages such as comprehensive color fastness, resistance to washing, acid resistance, sublimation resistance, and resistance to wet friction, all with excellent performance. Furthermore, the preparation method of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives is safe, simple, energy-efficient, and has stable product quality and good reproducibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 is the structural diagram of target product 1;

[0050] Figure 2 is the structural diagram of target product 2;

[0051] Figure 3 is the structural diagram of target product 3;

[0052] Figure 4 is the structural diagram of target product 4;

[0053] Figure 5 is the structural diagram of target product 5;

[0054] Figure 6 is the structural diagram of the target product 6;

[0055] Figure 7 is the structural diagram of target product 7;

[0056] Figure 8 is the structural diagram of the target product 8;

[0057] Figure 9 is the structural diagram of the target product 9;

[0058] Figure 10 is the structural diagram of the target product 10;

[0059] Figure 11 is the structural diagram of the target product 11;

[0060] Figure 12 is the structural diagram of the target product 12;

[0061] Figure 13 is the structural diagram of the target product 13;

[0062] Figure 14 This is the structural diagram of the target product 14. DETAILED DESCRIPTION

[0063] In order to better illustrate the purpose, technical solutions and advantages of this application, this application will be further described below with reference to the accompanying drawings and specific embodiments.

[0064] 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 all the same.

[0065] The N-acetyl indigo 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.

[0066] Example 1: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0067] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0068] Weigh 10 g of N-acetyl isocyanate (N-acetyl isocyanate) and add 100 g of tetrahydrofuran to a 500 mL three-necked round-bottom flask to thoroughly disperse the mixture. Propionyl chloride and triethylamine were then added dropwise to react (the molar ratio of N-acetyl isocyanate: propionyl chloride: triethylamine was 1:1.2:1.5). Ferric chloride was added as a catalyst at a concentration of 0.1% of the mass of N-acetyl isocyanate. The reaction was continued at 90°C for 6 h to obtain a reaction product solution. After cooling to room temperature, the solution was purified by adding four times the mass of deionized water with stirring, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 60°C to obtain the desired product 1.

[0069] The structural formula of target product 1 is as follows Figure 1 shown.

[0070] Characterization of target product 1: LC-MS (m / z,%): 349.1 ([M+H] + , 100).

[0071] Example 2: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0072] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0073] Weigh 5 g of N-acetyl cyanide (ACI) and add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask to thoroughly disperse the mixture. Acryloyl chloride and sodium tert-butoxide (the molar ratio of N-acetyl cyanide: ACI: Sodium tert-butoxide was 1:1.2:2.2) were then added dropwise. Aluminum trichloride (0.1% by weight of N-acetyl cyanide) was added as a catalyst. The mixture was reacted at 80°C for 10 h to obtain a reaction product solution. After the reaction solution cooled to room temperature, 5 times the mass of deionized water was added and purified with stirring. The temperature was maintained between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 90°C to obtain the desired product 2.

[0074] The structural formula of target product 2 is as follows Figure 2 shown.

[0075] Characterization of target product 2: LC-MS (m / z,%): 346.2 ([M+H] + , 100).

[0076] Example 3: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0077] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0078] 5 g of N-acetyl isocyanate (N-acetyl isocyanate) was weighed and thoroughly dispersed in 100 g of tetrahydrofuran in a 500 mL three-necked round-bottom flask. Propioyl chloride and pyridine (the molar ratio of N-acetyl isocyanate: propioyl chloride: pyridine was 1:1.5:2.2) were added dropwise. Boron tribromide (1% of the mass of N-acetyl isocyanate) was added as a catalyst. The reaction was continued at 90°C for 10 h to obtain a reaction product solution. After the reaction solution cooled to room temperature, 5 times the mass of deionized water was added and stirred for purification, with the temperature controlled between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 90°C to obtain the desired product 3.

[0079] The structural formula of target product 3 is as follows Figure 3 shown.

[0080] Characterization of target product 3: LC-MS (m / z,%): 345.2 ([M+H] + , 100).

[0081] Example 4: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0082] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0083] Weigh 10 g of N-acetyl isocyanate (N-acetyl isocyanate) and add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask to thoroughly disperse the mixture. Cyclopropylcarbonyl chloride and triethylamine (the molar ratio of N-acetyl isocyanate: cyclopropylcarbonyl chloride: triethylamine is 1:1.4:2.2) are then added dropwise. Boron trifluoride (2% of the mass of N-acetyl isocyanate) is added as a catalyst. The reaction is incubated at 80°C for 9 h to obtain a reaction product solution. After the reaction solution cools to room temperature, 5 times the mass of deionized water is added and stirred for purification, maintaining the temperature between 0 and 5°C. The solvent is removed by vacuum filtration, and the filter cake is dried in an oven at 80°C to obtain the desired product 4.

[0084] The structural formula of target product 4 is as follows Figure 4 shown.

[0085] Characterization of target product 4: LC-MS (m / z,%): 360.1 ([M+H] + , 100).

[0086] Example 5: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0087] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0088] 5 g of N-acetyl isocyanate (N-acetyl isocyanate) was weighed and thoroughly dispersed in a 500 mL three-necked round-bottom flask with 150 g of dimethylacetamide. Benzoyl chloride and triethylamine (the molar ratio of N-acetyl isocyanate:benzoyl chloride:triethylamine was 1:1.2:2.2) were then added dropwise. Aluminum tribromide (0.1% of the mass of N-acetyl isocyanate) was added as a catalyst. The reaction was incubated at 90°C for 8 h to obtain a reaction product solution. After cooling to room temperature, the solution was purified by stirring with 5 times the mass of deionized water, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 5.

[0089] The structural formula of target product 5 is as follows Figure 5 shown.

[0090] Characterization of target product 5: LC-MS (m / z,%): 397.3 ([M+H] + , 100).

[0091] Example 6: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0092] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0093] Weigh 10 g of N-acetyl cyanide (N-acetyl cyanide) and add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask to thoroughly disperse the mixture. Nicotinoyl chloride and triethylamine (molar ratio of N-acetyl cyanide: nicotinyl chloride: triethylamine: 1:1.5:2.2) were then added dropwise. Iron tribromide (5% by weight of N-acetyl cyanide) was added as a catalyst. The reaction was incubated at 90°C for 12 h to obtain a reaction product solution. After the reaction solution cooled to room temperature, 5 times the weight of deionized water was added and stirred for purification, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 70°C to obtain the desired product 6.

[0094] The structural formula of target product 6 is as follows Figure 6 shown.

[0095] Characterization of target product 6: LC-MS (m / z,%): 398.1 ([M+H] + , 100).

[0096] Example 7: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0097] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0098] Weigh 10 g of N-acetyl cyanide (N-acetyl cyanide) and add 100 g of tetrahydrofuran to a 500 mL three-necked round-bottom flask to thoroughly disperse the mixture. Then, dropwise add quinoline-4-carbonyl chloride and trimethylamine (the molar ratio of N-acetyl cyanide:quinoline-4-carbonyl chloride:trimethylamine is 1:1.2:2.2). Aluminum trichloride (2% of the mass of N-acetyl cyanide) is added as a catalyst. The reaction is continued at 120°C for 24 h to obtain a reaction product solution. After the reaction solution cools to room temperature, it is purified by stirring with 5 times the mass of deionized water, maintaining the temperature between 0 and 5°C. The solvent is removed by vacuum filtration, and the filter cake is dried in an oven at 90°C to obtain the desired product 7.

[0099] The structural formula of target product 7 is as follows Figure 7 shown.

[0100] Characterization of target product 7: LC-MS (m / z,%): 448.4 ([M+H] + , 100).

[0101] Example 8: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0102] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0103] Weigh 10 g of N-acetyl isocyanate (N-acetyl isocyanate) and add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask, thoroughly dispersing the mixture. Then, n-butane bromide and potassium carbonate (the molar ratio of N-acetyl isocyanate: n-butane bromide: potassium carbonate is 1:1.2:2.2) were added dropwise. Boron tribromide (2% of the mass of N-acetyl isocyanate) was added as a catalyst. The reaction was continued at 100°C for 10 h to obtain a reaction product solution. After cooling to room temperature, the solution was purified by stirring with 5 times the mass of deionized water, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 8.

[0104] The structural formula of target product 8 is as follows Figure 8 shown.

[0105] Characterization of target product 8: LC-MS (m / z,%): 349.2 ([M+H] + , 100).

[0106] Example 9: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0107] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0108] Weigh 15 g of N-acetyl isocyanate (N-acetyl isocyanate) and add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask to thoroughly disperse the mixture. Then, dropwise add chlorocyclohexane and triethylamine (the molar ratio of N-acetyl isocyanate: chlorocyclohexane: triethylamine is 1:1.5:2.2). Aluminum tribromide (2% of the mass of N-acetyl isocyanate) is added as a catalyst. The reaction is continued at 85°C for 12 h to obtain a reaction product solution. After cooling to room temperature, the solution is purified by stirring with 5 times the mass of deionized water, maintaining the temperature between 0 and 5°C. The solvent is removed by vacuum filtration, and the filter cake is dried in an oven at 80°C to obtain the desired product 9.

[0109] The structural formula of target product 9 is as follows Figure 9 shown.

[0110] Characterization of target product 9: LC-MS (m / z,%): 375.2 ([M+H] + , 100).

[0111] Example 10: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0112] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0113] 5 g of N-acetyl isocyanate (N-acetyl isocyanate) was weighed and thoroughly dispersed in 100 g of dimethylformamide in a 500 mL three-necked round-bottom flask. Pyridine bromide and triethylamine (the molar ratio of N-acetyl isocyanate: pyridine bromide: triethylamine was 1:1.5:2.2) were added dropwise. Iron tribromide (2% of the mass of N-acetyl isocyanate) was added as a catalyst. The reaction was continued at 100°C for 10 h to obtain a reaction product solution. After the reaction solution cooled to room temperature, 5 times the mass of deionized water was added and stirred for purification, with the temperature controlled between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 10.

[0114] The structural formula of target product 10 is as follows Figure 10 shown.

[0115] Characterization of target product 10: LC-MS (m / z,%): 370.1 ([M+H] + , 100).

[0116] Example 11: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0117] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0118] 5 g of N-acetyl indigo blue (N-acetyl indigo blue) was weighed and thoroughly dispersed in 100 g of dimethylformamide in a 500 mL three-necked round-bottom flask. Propylsulfonyl chloride and tetramethylethylenediamine (the molar ratio of N-acetyl indigo blue:propylsulfonyl chloride:tetramethylethylenediamine was 1:1.2:1.2) were then added dropwise. Ferric chloride was added as a catalyst at a concentration of 3% of the mass of N-acetyl indigo blue. The reaction was incubated at 80°C for 4 h to obtain a reaction product solution. After the reaction solution cooled to room temperature, 5 times the mass of deionized water was added and stirred for purification, with the temperature controlled between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 11.

[0119] The structural formula of target product 11 is as follows Figure 11 shown.

[0120] Characterization of target product 11: LC-MS (m / z,%): 397.1 ([M+H] + , 100).

[0121] Example 12: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0122] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0123] Weigh 10 g of N-acetyl cyanide (N-acetyl cyanide) and add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and thoroughly disperse the mixture. Then, p-toluenesulfonyl chloride and N-methylmorpholine (the molar ratio of N-acetyl cyanide: p-toluenesulfonyl chloride: N-methylmorpholine was 1:1.2:2) were added dropwise. Aluminum trichloride (3.5% by weight of N-acetyl cyanide) was added as a catalyst. The reaction was continued at 110°C for 9 h to obtain a reaction product solution. After cooling to room temperature, the solution was purified by stirring with 5 times the weight of deionized water, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 12.

[0124] The structural formula of target product 12 is as follows Figure 12 shown.

[0125] Characterization of target product 12: LC-MS (m / z,%): 447.1 ([M+H] + , 100).

[0126] Example 13: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0127] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0128] 6 g of N-acetyl cyanide (N-acetyl cyanide) raw material was weighed and thoroughly dispersed in a 500 mL three-necked round-bottom flask with 200 g of carbon tetrachloride. Diphenylphosphinyl chloride and sodium carbonate (the molar ratio of N-acetyl cyanide: diphenylphosphinyl chloride: sodium carbonate was 1:1.2:2.2) were then added dropwise. Ferric chloride was added as a catalyst at a concentration of 1.5% of the mass of N-acetyl cyanide. The reaction was incubated at 100°C for 8 h to obtain a reaction product solution. After cooling to room temperature, the solution was purified by stirring with 5 times the mass of deionized water, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 13.

[0129] The structural formula of target product 13 is as follows Figure 13 shown.

[0130] Characterization of target product 13: LC-MS (m / z,%): 491.1 ([M+H] +, 100).

[0131] Example 14: 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives and their preparation methods

[0132] This embodiment provides a method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives, comprising the following steps:

[0133] 4 g of N-acetyl cyanide (N-acetyl cyanide) raw material was weighed and thoroughly dispersed in a 500 mL three-necked round-bottom flask with 100 g of carbon tetrachloride. Dicyclohexylphosphinyl chloride and potassium tert-butoxide (the molar ratio of N-acetyl cyanide: dicyclohexylphosphinyl chloride: potassium tert-butoxide was 1:1.2:2) were then added dropwise. Boron tribromide (2.5% by weight of N-acetyl cyanide) was added as a catalyst. The reaction was incubated at 90°C for 10 h to obtain a reaction product solution. After cooling to room temperature, the solution was purified by stirring with 5 times the weight of deionized water, maintaining the temperature between 0 and 5°C. The solvent was removed by vacuum filtration, and the filter cake was dried in an oven at 80°C to obtain the desired product 14.

[0134] The structural formula of target product 14 is as follows Figure 14 shown.

[0135] Characterization of target product 14: LC-MS (m / z,%): 503.2 ([M+H] + , 100).

[0136] Similar reaction conditions were used as in Examples 1 to 14 above, with the derivatization reagent and catalyst used being varied. The structure of the derivatization reagent corresponded to the different substituents. The catalyst did not alter the structure of the reaction product.

[0137] The prepared 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives are shown in Table 1.

[0138] Table 1

[0139]

[0140] Test example: Application of 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives in dyeing

[0141] 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:

[0142] 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°C for 10 min, bath ratio 1:30.

[0143] 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.

[0144] The various properties of the dye were tested according to the standards, and the test results were recorded in Table 2 below.

[0145] Table 2

[0146]

[0147] The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives of Examples 1 to 14 and their different numberings were capable of dyeing cotton fabrics, with K / S values exceeding 10, dye uptake exceeding 80%, and color fastness to washing, sublimation, acid staining, sunlight, and wet rubbing all reaching Level 4. Compared to N-acetyl blue, which has a K / S value of 9.2 and a dye uptake of 84.8%, the derivatives of the present invention exhibited superior dyeing effects.

[0148] Based on the existing N-acetyl indole, this application obtains 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives through a chemical synthesis method. The derivatives have stable color, are temperature-resistant under acidic conditions, and are resistant to high and low temperatures. They have a very broad range of applications and application prospects for industrial production.

[0149] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended 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, those skilled in the art should understand that the technical solutions of the present application may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivative, characterized in that: The 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives include at least one of the following structures: 。 2. The method for preparing 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives according to claim 1, 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 hours until no N-acetyl blue is detected by chromatographic analysis, which is determined to be the reaction endpoint, to obtain a reaction product solution; S3, adding deionized water to the reaction product solution, cooling and stirring, and performing purification treatment; S4. Perform solid-liquid separation on the purified solution in step S3 and dry it to obtain 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives.

3. The preparation method according to claim 2, wherein The organic solvent is 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.

4. The preparation method according to claim 2, wherein The molar ratio of the N-acetyl indigo blue, the derivatization reagent and the acid-binding agent is 1:(1.2-2.2):(1.2-2.2).

5. The preparation method according to claim 2, wherein The catalyst is a Lewis acid catalyst, and the Lewis acid catalyst is one of boron trifluoride, aluminum trichloride, ferric trichloride, 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.

6. Use of the 5-substituted amino-5'-acetylamino-3,3'-bipyridine derivatives according to claim 1 in dyeing cotton fabrics.

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