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

Abstract

The invention relates to the technical field of chemical synthesis of dyes, in particular to a 5, 5 '-disubstituted amino-3, 3'-dipyridyl derivative as well as a preparation method and application of the 5, 5 '-disubstituted amino-3, 3'-dipyridyl derivative. According to the 5, 5 '-disubstituted amino-3, 3'-dipyridyl derivative and the preparation method thereof, the ornamental blue is used as a parent body for derivatization reaction, different structures are introduced to amino groups, the 5, 5 '-disubstituted amino-3, 3'-dipyridyl derivative is obtained and can be used as a dye, and the dye has relatively high color development intensity, bright color, deep dyeing and comprehensive color fastness. The preparation method of the 5, 5 '-disubstituted amino-3, 3'-dipyridyl derivative is continuous in process step, high in controllability, large in treatment capacity and suitable for large-scale industrial production, the 5, 5 '-disubstituted amino-3, 3'-dipyridyl derivative is applied to fabric dyeing, and the fabric has the advantages of washing resistance, acid resistance, sublimation resistance, wet friction resistance and the like.

Description

Technical Field

[0001] This application relates to the technical field of dye chemical synthesis, and in particular to a 5,5'-disubstituted amino-3,3'-bipyridine derivative, its preparation method and application. Background Art

[0002] Indigoidine, namely indigo blue, is a substance with a bicyclic structure formed by the condensation of two glutamine molecules under the action of indigoidine synthetase. Indigoidine is a stable and brightly colored natural blue pigment with a variety of excellent properties, and its application fields are extensive, including cosmetics, fabric printing and dyeing, and the medical industry.

[0003] However, indigoidine itself can only provide one color, which obviously cannot meet the market demand for natural pigments. There are many dyes such as red and yellow with large market demand at present, such as C.I. Reactive Red 195 and Disperse Deep Red PUD, which are one of the three primary colors. These dyes have been used for a long time, cause large environmental pollution, and are not easily degraded, which is insufficient to meet the requirements of green development. Therefore, researching new bio-based dyes with a variety of rich dyeing effects has become a technical problem that needs to be solved urgently. Summary of the Invention

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

[0005] To achieve the above purpose, the technical solution adopted by this application is:

[0006] This application provides a 5,5'-disubstituted amino-3,3'-bipyridine derivative, which is characterized in that the structural formula of the 5,5'-disubstituted amino-3,3'-bipyridine derivative is shown as (I);

[0007]

[0008]

[0009] Among them, A1 is selected from one of C, S, and P;

[0010] A2 is selected from one of C, S, and P;

[0011] R1 and R2 are independently 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, C2-C20 alkylaryl, substituted C2-C20 alkylaryl, and heterocycles with or without substitution.

[0012] The heterocycle includes one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthraquinone, anthraquinone;

[0013] n and m are selected from 0, 1 or 2;

[0014] w and q are selected from 0 or 1.

[0015] Through a large number of experiments, the inventors of the present application obtained 5,5'-disubstituted amino-3,3'-bipyridine derivatives (without acetyl groups) of the present application. This derivative can be used as a dye, having a high color strength, bright color after dyeing, deep dyeing and comprehensive fastness. And when the 5,5'-disubstituted amino-3,3'-bipyridine derivative is applied to fabric dyeing, the fabric has the advantages of being wash-resistant, acid-resistant, sublimation-resistant, and wet rubbing-resistant.

[0016] As a preferred embodiment of the 5,5'-disubstituted amino-3,3'-bipyridine derivatives described in the present application, the substituted C2-C20 alkyl includes halogenated C2-C20 alkyl; the substituted C2-C20 alkenyl includes halogenated C2-C20 alkenyl; the substituted C2-C20 alkynyl includes halogenated C2-C20 alkynyl; the substituted C3-C20 cycloalkyl includes halogenated C3-C20 cycloalkyl; the substituted C2-C20 alkylaryl includes halogenated C2-C20 alkylaryl.

[0017] Preferably, the halogenated C2-C20 alkyl is a straight-chain or branched-chain alkyl, and the hydrogen atoms on the alkyl are partially or completely substituted by halogen atoms;

[0018] The substituents in the 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 phenanthraquinone, substituted anthraquinone are one of substituting H, halogen, C1-C3 alkyl, halogenated C1-C3 alkyl on the aromatic ring or heterocycle.

[0019] By using the above preferred groups, the 5,5'-disubstituted amino-3,3'-bipyridine derivatives obtained in the present application have a high color strength. And when it is applied to fabric dyeing, the color is bright, the color fastness is significantly improved, the wash fastness is excellent, it has better sublimation resistance and wet rubbing resistance, and the impact on the environment is also significantly less than that of other dyes.

[0020] Preferably, the 5,5'-disubstituted amino-3,3'-bipyridine derivatives include at least one of the following structures:

[0021]

[0022] The present application provides a method for preparing the above-mentioned 5,5'-disubstituted amino-3,3'-bipyridine derivatives, which comprises the following steps:

[0023] S1. Place indigo powder in a reaction solvent and stir until it reaches a homogeneous state to obtain a suspension;

[0024] S2. Add a derivatizing reagent and a catalyst to the suspension obtained in step S1, then add an acid-binding agent and react until there is no indigo present, and determine the reaction end point to obtain a reaction product solution;

[0025] S3. Add deionized water to the reaction product solution obtained in step S2 and stir for purification;

[0026] S4. Perform solid-liquid separation on the solution after purification treatment, and then dry it to obtain 5,5'-disubstituted amino-3,3'-bipyridine derivatives.

[0027] Indigo is a natural blue pigment obtained by microbial fermentation and belongs to pyridine heterocyclic reduction dyes. In the technical solution of the present application, indigo is used as a raw material and modified with indigo as a parent body, and different derivatized structures are introduced on the amino group to prepare the novel dye of the present application, namely 5,5'-disubstituted amino-3,3'-bipyridine derivatives; the above preparation method is simple, convenient for purification, safe and energy-saving in the preparation process, the product quality is stable, the reproducibility is good, and the yield is high, which is suitable for industrial production.

[0028] The principle of the above method for preparing 5,5'-disubstituted amino-3,3'-bipyridine derivatives (acylation reaction or alkylation reaction of amino groups) is as follows:

[0029]

[0030] As a preferred embodiment of the method for preparing 5,5'-disubstituted amino-3,3'-bipyridine derivatives according to the present application, the solvent includes one of DMF, DMSO, DMA, tetrahydrofuran, carbon tetrachloride, chloroform, dichloromethane, and dichloroethane.

[0031] As a preferred embodiment of the preparation method of the 5,5'-disubstituted amino-3,3'-bipyridine derivatives described in this application, the derivative reagent includes the following structures containing halogen or acyl halide groups: 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 heterocycles containing halogen or acyl halide groups: furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthraquinone, anthraquinone; the substituents of the heterocycle are one of halogen, C1-C3 alkyl, and halogenated C1-C3 alkyl.

[0032] By using the above types of organic solvents and derivative reagents in this application, 5,5'-disubstituted amino-3,3'-bipyridine derivatives can be better generated, which have higher chromogenic intensity. And when the 5,5'-disubstituted amino-3,3'-bipyridine derivatives are applied to fabric dyeing, the obtained fabrics have the advantages of comprehensive dyeing fastness, water washing resistance, acid resistance, sublimation resistance, wet rubbing resistance, etc.

[0033] As a preferred embodiment of the preparation method of the 5,5'-disubstituted amino-3,3'-bipyridine derivatives described in this application, the acid-binding agent includes at least one of triethylamine, triethylenediamine, dimethylamine, trimethylamine, pyridine, N-methylmorpholine, tetramethylethylenediamine, sodium tert-butoxide, and potassium tert-butoxide;

[0034] The catalyst is a Lewis acid type catalyst, and the catalyst includes one of boron trifluoride, aluminum trichloride, iron trichloride, boron tribromide, aluminum tribromide, and iron tribromide;

[0035] The addition amount of the catalyst is 0.1% - 5% of the mass of indigo.

[0036] As a preferred embodiment of the preparation method of the 5,5'-disubstituted amino-3,3'-bipyridine derivatives described in this application, the molar ratio of indigo, derivative reagent, and acid-binding agent is 1:(1.2 - 2.2):(1.2 - 2.2).

[0037] As a preferred embodiment of the preparation method of the 5,5'-disubstituted amino-3,3'-bipyridine derivatives described in this application, in the step S2, the reaction temperature is 60 - 120 °C, and the reaction time is 1 - 24 h.

[0038] Preferably, in the step S3, the mass ratio of deionized water to the reaction product solution is (3 - 5):1, and the temperature is controlled at 0 - 25 °C.

[0039] Preferably, in the step S4, the method for solid-liquid separation includes suction filtration or centrifugation.

[0040] The present application also provides an application of the above 5,5'-disubstituted amino-3,3'-bipyridine derivatives in fabric dyeing.

[0041] As a preferred embodiment of the application described in the present application, the fabric includes at least one of cotton, linen, wool, mulberry silk, regenerated fiber and chemical fiber.

[0042] The 5,5'-disubstituted amino-3,3'-bipyridine derivatives prepared in the present application are applied to fabrics such as cotton, linen, wool, mulberry silk, regenerated fiber and chemical fiber for dyeing. After dyeing, the color is bright, the dyeing is deep and the color fastness is comprehensive. A new type of bio-based dye is developed, enriching various dyeing effects.

[0043] Compared with the prior art, the present application has the following beneficial effects:

[0044] The present application provides a 5,5'-disubstituted amino-3,3'-bipyridine derivative, a preparation method and an application thereof. The present application uses guanlan as a parent for modification, and introduces different derivative structures on the amino group to obtain the 5,5'-disubstituted amino-3,3'-bipyridine derivative of the present application, which can be used as a dye. This dye has a high chromogenic intensity, bright color after dyeing, deep dyeing and comprehensive color fastness. The preparation method of the 5,5'-disubstituted amino-3,3'-bipyridine derivative provided by the present application has continuous process steps, strong controllability, large processing capacity, and is suitable for large-scale industrial production; and the 5,5'-disubstituted amino-3,3'-bipyridine derivative is applied to fabric dyeing, and the fabric has the advantages of water washing resistance, acid resistance, sublimation resistance, wet rubbing resistance, etc. Description of the Drawings

[0045] Figure 1 It is the structural formula of the target product 1 in Example 1;

[0046] Figure 2 It is the structural formula of the target product 2 in Example 2;

[0047] Figure 3 It is the structural formula of the target product 3 in Example 3;

[0048] Figure 4 It is the structural formula of the target product 4 in Example 4;

[0049] Figure 5 It is the structural formula of the target product 5 in Example 5;

[0050] Figure 6 It is the structural formula of the target product 6 in Example 6;

[0051] Figure 7 It is the structural formula of the target product 7 in Example 7;

[0052] Figure 8 It is the structural formula of the target product 8 in Example 8;

[0053] Figure 9 It is the structural formula of the target product 9 in Example 9;

[0054] Figure 10 It is the structural formula of the target product 10 in Example 10;

[0055] Figure 11 It is the structural formula of the target product 11 in Example 11;

[0056] Figure 12 It is the structural formula of the target product 12 in Example 12;

[0057] Figure 13 It is the structural formula of the target product 13 in Example 13;

[0058] Figure 14 It is the structural formula of the target product 14 in Example 14;

[0059] Figure 15 It is the structural formula of the target product 15 in Example 15;

[0060] Figure 16 It is the structural formula of the target product 16 in Example 16;

[0061] Figure 17 It is the structural formula of the target product 17 in Example 17;

[0062] Figure 18 It is the structural formula of the target product 18 in Example 18;

[0063] Figure 19 It is the structural formula of the target product 19 in Example 19;

[0064] Figure 20 It is the structural formula of the target product 20 in Example 20;

[0065] Figure 21 It is the structural formula of the target product 21 in Example 21;

[0066] Figure 22 They are the dyed fabric diagrams of Example 1, Example 2, Example 3, and Example 6. Detailed implementation manners

[0067] To better illustrate the purpose, technical solution, and advantages of this application, the following will further illustrate this application in combination with the accompanying drawings and specific embodiments.

[0068] 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.

[0069] The indigo plant used in the following examples was provided by Nanjing Hegu Life Biotechnology Co., Ltd. Structural identification of the product: The synthesized target product was sent to the Analysis and Testing Center of Nanjing Normal University for testing.

[0070] Example 1: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0071] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0072] Weigh 12g of indigo raw material, add 100g of tetrahydrofuran to a 500mL three-necked round-bottom flask and fully disperse, drop propionyl chloride and triethylamine to react (the molar ratio of indigo: propionyl chloride: triethylamine is 1:2.1:2.1), add ferric chloride as a catalyst, the addition amount is 0.1% of the mass of indigo, react at 90°C for 6h, and obtain a reaction product solution. After the reaction product solution is cooled to room temperature, 4 times the mass of deionized water is added and stirred for purification, and the temperature is controlled at 0-5°C. The solvent is removed by vacuum filtration, and the filter cake is dried in an oven at 60°C to obtain the target product 1.

[0073] The structure of target product 1 is shown in Figure 1 shown.

[0074] Characterization of target product 1: HRMS (m / z, %): 360.11 ([M+H] + ,100). 1 H NMR (400MHz, DMSO-d6) δ11.84(s,1H),9.83(s,1H),9.59(s,1H),1.04(t,3H).

[0075] Example 2: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0076] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0077] Weigh 15g of indigo raw material, add 100g of dimethylformamide to a 500mL three-necked round-bottom flask and fully disperse, add sodium tert-butoxide, then drop acryloyl chloride (the molar ratio of indigo: acryloyl chloride: sodium tert-butoxide is 1:2.2:2.2), add aluminum chloride as a catalyst, the addition amount is 0.1% of the mass of indigo, react at 80°C for 10h, and obtain a reaction product solution. After the reaction product solution is cooled 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 removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 2.

[0078] The structure of target product 2 is shown in Figure 2 shown.

[0079] Characterization of target product 2: HRMS (m / z, %): 357.08 ([M+H] + ,100).

[0080] Example 3: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0081] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0082] Weigh 25g of indigo raw material, add 100g of tetrahydrofuran to a 500mL three-necked round-bottom flask and fully disperse, drop propioloyl chloride and pyridine (the molar ratio of indigo: propioloyl chloride: pyridine is 1:2.2:2.2), add aluminum chloride as a catalyst, the addition amount is 2% of the mass of indigo, react at 90°C for 10h, and obtain a reaction product solution. After the reaction product solution is cooled 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 removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 3.

[0083] The structure of target product 3 is shown in Figure 3 shown.

[0084] Characterization of target product 3: HRMS (m / z, %): 353.04 ([M+H] + ,100).

[0085] Example 4: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0086] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0087] Weigh 15 g of the cyanine raw material, add 100 g of carbon tetrachloride to a 500 mL three-necked round-bottom flask and disperse it fully. Dropwise add cyclopropylcarbonyl chloride and triethylenediamine (the molar ratio of cyanine: cyclopropylcarbonyl chloride: triethylenediamine is 1:2.2:2.2). Add ferric chloride as a catalyst, and the addition amount is 2% of the mass of cyanine. React at 80 °C for 9 h to obtain the reaction product solution. After cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, with the temperature controlled at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 80 °C to obtain the target product 4.

[0088] The structural diagram of the target product 4 is as Figure 4 shown.

[0089] Characterization of the target product 4: HRMS (m / z, %): 385.11 ([M+H] + , 100).

[0090] Example 5. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0091] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, including the following steps:

[0092] Weigh 25 g of the cyanine raw material, add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and disperse it fully. Dropwise add phenylpropionyl chloride and triethylamine (the molar ratio of cyanine: phenylpropionyl chloride: triethylamine is 1:2.2:2.2). Add aluminum trichloride as a catalyst, and the addition amount is 0.1% of the mass of cyanine. React at 90 °C for 8 h to obtain the reaction product solution. After cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, with the temperature controlled at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 80 °C to obtain the target product 5.

[0093] The structural diagram of the target product 5 is as Figure 5 shown.

[0094] Characterization of the target product 5: HRMS (m / z, %): 513.17 ([M+H] + , 100).

[0095] Example 6. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0096] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, including the following steps:

[0097] Weigh 18 g of the cyanine raw material, add 100 g of dichloroethane to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add nicotinoyl chloride and triethylamine (the molar ratio of cyanine:nicotinoyl chloride:triethylamine is 1:2.2:2.2), add ferric chloride as a catalyst, and the addition amount is 5% of the mass of cyanine. React at 90 °C for 12 h to obtain the reaction product solution. After cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 70 °C to obtain the target product 6.

[0098] The structural diagram of the target product 6 is as Figure 6 shown.

[0099] Characterization of the target product 6: HRMS (m / z, %): 459.1 ([M + H] + , 100).

[0100] Example 7. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0101] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, including the following steps:

[0102] Weigh 15 g of the cyanine raw material, add 100 g of tetrahydrofuran to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add quinoline-4-carbonyl chloride and pyridine (the molar ratio of cyanine:quinoline-4-carbonyl chloride:pyridine is 1:2.2:2.2), add aluminum trichloride as a catalyst, and the addition amount is 2% of the mass of cyanine. React at 120 °C for 24 h to obtain the reaction product solution. After cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 7.

[0103] The structural diagram of the target product 7 is as Figure 7 shown.

[0104] Characterization of the target product 7: HRMS (m / z, %): 560.14 ([M + H] + , 100).

[0105] Example 8. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0106] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, including the following steps:

[0107] Weigh 15 g of the cyanine raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add n-butyl bromide and triethylamine (the molar ratio of cyanine: n-butyl bromide: triethylamine is 1:2.2:2.2), add aluminum trichloride as a catalyst, and the addition amount is 0.5% of the mass of the cyanine. React at 100 °C for 10 h to obtain a reaction product solution. After cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 8.

[0108] The structural diagram of the target product 8 is as Figure 8 shown.

[0109] Characterization of the target product 8: HRMS (m / z, %): 361.18 ([M+H] + , 100).

[0110] Example 9. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0111] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, which includes the following steps:

[0112] Weigh 25 g of the cyanine raw material, add 100 g of DMSO to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add cyclopentyl chloride and dimethylamine (the molar ratio of cyanine: cyclopentyl chloride: dimethylamine is 1:2.2:2.2), add aluminum trichloride as a catalyst, and the addition amount is 5% of the mass of the cyanine. React at 85 °C for 12 h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 9.

[0113] The structural diagram of the target product 9 is as Figure 9 shown.

[0114] Characterization of the target product 9: HRMS (m / z, %): 385.18 ([M+H] + , 100).

[0115] Example 10. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0116] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, which includes the following steps:

[0117] Weigh 15 g of the cyanine raw material, add 100 g of dimethylformamide to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add bromoethylbenzene and triethylamine (the molar ratio of cyanine: bromoethylbenzene: triethylamine is 1:2.2:2.2), add aluminum trichloride as a catalyst, and the addition amount is 0.5% of the mass of cyanine. React at 100 °C for 10 h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 10.

[0118] The structural diagram of the target product 10 is as Figure 10 shown.

[0119] Characterization of the target product 10: HRMS (m / z, %): 457.18 ([M + H] + , 100).

[0120] Example 11. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0121] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, which includes the following steps:

[0122] Weigh 25 g of the cyanine raw material, add 100 g of dichloromethane to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Add sodium tert-butoxide, and then dropwise add 2-bromopyridine (the molar ratio of cyanine: 2-bromopyridine: sodium tert-butoxide is 1:2.2:2.2), add aluminum trichloride as a catalyst, and the addition amount is 1.5% of the mass of cyanine. React at 105 °C for 12 h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0 - 5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 11.

[0123] The structural diagram of the target product 11 is as Figure 11 shown.

[0124] Characterization of the target product 11: HRMS (m / z, %): 403.11 ([M + H] + , 100).

[0125] Example 12. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0126] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, which includes the following steps:

[0127] Weigh 25g of indigo raw material, add 100g of dimethylacetamide to a 500mL three-necked round-bottom flask and fully disperse, add sodium tert-butoxide, then drop 4-bromoindole (the molar ratio of indigo: 4-bromoindole: sodium tert-butoxide is 1:2.2:2.2), add aluminum chloride as a catalyst, the addition amount is 2.5% of the mass of indigo, react at 115°C for 7h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 12.

[0128] The structure of target product 12 is shown in Figure 12 shown.

[0129] Characterization of target product 12: HRMS (m / z, %): 557.67 ([M+H] + ,100).

[0130] Example 13: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0131] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0132] Weigh 15g of indigo raw material, add 100g of dimethylformamide to a 500mL three-necked round-bottom flask and fully disperse, drop propylsulfonic anhydride and tetramethylethylenediamine (the molar ratio of indigo: propylsulfonic anhydride: tetramethylethylenediamine is 1:1.2:2.2), add ferric chloride as a catalyst, the addition amount is 3% of the mass of indigo, react at 80°C for 4h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 13.

[0133] The structure of target product 13 is shown in Figure 13 shown.

[0134] Characterization of target product 13: HRMS (m / z, %): 461.07 ([M+H] + ,100).

[0135] Example 14: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and a preparation method thereof

[0136] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0137] Weigh 20 g of the indigo raw material, add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add benzenesulfonyl chloride and N-methylmorpholine (the molar ratio of indigo:benzenesulfonyl chloride:N-methylmorpholine is 1:2.2:2.2), add aluminum trichloride as a catalyst, and the addition amount is 3.5% of the indigo mass. React at 110 °C for 9 h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0-5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 14.

[0138] The structural diagram of the target product 14 is as Figure 14 shown.

[0139] Characterization of the target product 14: HRMS (m / z, %): 612.13 ([M+H] + , 100).

[0140] Example 15. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0141] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, including the following steps:

[0142] Weigh 20 g of the indigo raw material, add 100 g of dimethylacetamide to a 500 mL three-necked round-bottom flask and disperse it thoroughly. Dropwise add pyridine-2-sulfonyl chloride and tetramethylethylenediamine (the molar ratio of indigo:pyridine-2-sulfonyl chloride:tetramethylethylenediamine is 1:2.2:2.2), add ferric chloride as a catalyst, and the addition amount is 0.5% of the indigo mass. React at 110 °C for 17 h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir for purification, and control the temperature at 0-5 °C. Vacuum filter to remove the solvent, and dry the filter cake in an oven at 90 °C to obtain the target product 15.

[0143] The structural diagram of the target product 15 is as Figure 15 shown.

[0144] Characterization of the target product 15: HRMS (m / z, %): 531.03 ([M+H] + , 100).

[0145] Example 16. A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0146] This example provides a preparation method of a 5,5'-disubstituted amino-3,3'-bipyridine derivative, including the following steps:

[0147] Weigh 20g of indigo raw material, add 100g of carbon tetrachloride to a 500mL three-necked round-bottom flask and fully disperse, add sodium tert-butoxide, then drop quinoline-8-sulfonyl chloride (the molar ratio of indigo: quinoline-8-sulfonyl chloride: sodium tert-butoxide is 1:2.2:2.2), add ferric bromide as a catalyst, the addition amount is 2.5% of the mass of indigo, react at 120°C for 20h, and obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration is performed to remove the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 16.

[0148] The structure of target product 16 is shown in Figure 16 shown.

[0149] Characterization of target product 16: HRMS (m / z, %): 631.06 ([M+H] + ,100).

[0150] Example 17: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0151] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0152] Weigh 20g of indigo raw material, add 100g of carbon tetrachloride to a 500mL three-necked round-bottom flask and fully disperse, drop diphenylphosphine chloride and triethylamine (the molar ratio of indigo: diphenylphosphine chloride: triethylamine is 1:2.2:2.2), add boron trifluoride as a catalyst, the addition amount is 2.5% of the mass of indigo, react at 100°C for 10h, and obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 17.

[0153] The structure of target product 17 is shown in Figure 17 shown.

[0154] Characterization of target product 17: HRMS (m / z, %): 649.13 ([M+H] + ,100).

[0155] Example 18: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0156] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0157] Weigh 20g of indigo raw material, add 100g of carbon tetrachloride to a 500mL three-necked round-bottom flask and fully disperse, drop dicyclohexylphosphinoyl chloride and triethylamine (the molar ratio of indigo: dicyclohexylphosphinoyl chloride: triethylamine is 1:2.2:2.2), add boron tribromide as a catalyst, the addition amount is 2.5% of the mass of indigo, react at 100°C for 10h to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration is performed to remove the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 18.

[0158] The structure of target product 18 is shown in Figure 18 shown.

[0159] Characterization of target product 18: HRMS (m / z, %): 673.32 ([M+H] + ,100).

[0160] Example 19: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0161] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0162] Weigh 20g of indigo raw material, add 100g of carbon tetrachloride to a 500mL three-necked round-bottom flask and fully disperse, then add butyryl chloride to the suspension, add triethylamine (the molar ratio of indigo: butyryl chloride: triethylamine is 1:1.2:2.2), add aluminum tribromide as a catalyst, the addition amount is 0.5% of the mass of indigo, react at 80°C for 2h; then add n-butane bromide (the molar ratio of indigo: n-butane bromide is 1:1.2) to obtain a reaction product solution; after cooling the reaction product solution 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 performed to remove the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 19.

[0163] The structure of target product 19 is shown in Figure 19 shown.

[0164] Characterization of target product 19: HRMS (m / z, %): 375.16 ([M+H] + ,100).

[0165] Example 20: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0166] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0167] Weigh 20g of indigo blue raw material, add 100g of chloroform to a 500mL three-necked round-bottom flask and fully disperse, then add butylsulfonyl chloride to the suspension, add triethylamine (the molar ratio of indigo blue: butylsulfonyl chloride: triethylamine is 1:1.2:2.2), add boron tribromide as a catalyst, the addition amount is 1.5% of the mass of indigo blue, react at 90°C for 2h; then add butyryl chloride (the molar ratio of indigo blue: butyryl chloride is 1:1.2) to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 20.

[0168] The structure of the target product 20 is shown in Figure 20 shown.

[0169] Characterization of target product 20: HRMS (m / z, %): 425.11 ([M+H] + ,100).

[0170] Example 21: A 5,5'-disubstituted amino-3,3'-bipyridine derivative and its preparation method

[0171] This embodiment provides a method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative, comprising the following steps:

[0172] Weigh 20g of indigo raw material, add 100g of carbon tetrachloride to a 500mL three-necked round-bottom flask and fully disperse, then add butylsulfonyl chloride to the suspension, add triethylamine (the molar ratio of indigo: butylsulfonyl chloride: triethylamine is 1:1.2:2.2), add boron trifluoride as a catalyst, the addition amount is 0.5% of the mass of indigo, react at 80°C for 2h; then add bromobutylene (the molar ratio of indigo: bromobutylene is 1:1.2) to obtain a reaction product solution; after cooling the reaction product solution to room temperature, add 5 times the mass of deionized water and stir to purify, and control the temperature at 0-5°C. Vacuum filtration removes the solvent, and the filter cake is dried in an oven at 90°C to obtain the target product 21.

[0173] The structure of the target product 21 is shown in Figure 21 shown.

[0174] Characterization of target product 21: HRMS (m / z, %): 409.11 ([M+H] + ,100).

[0175] Using reaction conditions similar to those in the above example, only the added reagent components were changed, and the prepared 5,5'-disubstituted amino-3,3'-bipyridine derivatives were shown in Table 1.

[0176] Table 1

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] Test Example, Application of 5,5'-disubstituted amino-3,3'-bipyridine derivatives in dyeing

[0245] Dye the cotton fabric with the 5,5'-disubstituted amino-3,3'-bipyridine derivatives obtained in the above examples according to the following process:

[0246] 2% (o.w.f) of 5,5'-disubstituted amino-3,3'-bipyridine derivatives, reduce with 2 times of sodium dithionite, adjust to pH 5 with 0.5 mL / L of citric acid, dye at 25 °C for 10 min, and the bath ratio is 1:30.

[0247] After the dyeing is completed, take out the dyed fabric sample, wash it, dry it, and solve the K / S value of the dye using the Lambert-Beer law.

[0248] Test the various properties of the dye according to the standards, and record the test results in Table 2 below.

[0249] Table 2

[0250]

[0251]

[0252] The 5,5'-disubstituted amino-3,3'-bipyridine derivatives of Examples 1 to 18 and Compounds 1 to 692 obtained by the above construction can dye cotton fabrics. Compared with the K / S value of indigo blue being 9.1, the K / S value of the derivatives of the present invention reaches more than 10, the dyeing rate reaches more than 80%, and the color fastness to washing, sublimation, acid spot, sunlight, and wet rubbing all reach Grade 4. Since it is impossible to list them all, the 5,5'-disubstituted amino-3,3'-bipyridine derivatives with the remaining unmentioned numbers also have the above similar dyeing effects and are all within the protection scope of this application.

[0253] Among them, the results of cotton fabrics dyed with the 5,5'-disubstituted amino-3,3'-bipyridine derivatives of Example 1, Example 2, Example 3, and Example 6 as dyes at different concentrations (1 g / L, 1.5 g / L, 2 g / L, 3 g / L, 4 g / L) are as Figure 19 shown, having the advantages of bright color, uniform color, etc., and presenting a red effect different from indigo blue.

[0254] Based on the existing indigo blue, this application obtains a 5,5'-disubstituted amino-3,3'-bipyridine derivative through a chemical synthesis method, with stable color, temperature resistance under acidic conditions, high and low temperature resistance, and has a very broad application range and application prospects for industrial production.

[0255] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application rather than to limit the protection scope of this application. Although this application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of this application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of this application.

Claims

1. A 5,5'-disubstituted amino-3,3'-bipyridine derivative, characterized in that: The structural formula of the 5,5'-disubstituted amino-3,3'-bipyridine derivative is shown in (I); Wherein, A1 is selected from one of C, S, and P; A2 is selected from one of C, S and P; R1 and R2 are independently 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, C2-C20 alkylaryl, substituted C2-C20 alkylaryl, and substituted or unsubstituted heterocyclic ring; 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, m are selected from 0, 1 or 2; w and q are selected from 0 or 1.

2. The 5,5'-disubstituted amino-3,3'-bipyridine derivative according to claim 1, characterized in that: The substituent is one of halogen, C1-C3 alkyl, and halogenated C1-C3 alkyl on the aromatic ring or heterocyclic ring.

3. The 5,5'-disubstituted amino-3,3'-bipyridine derivative according to claim 1, characterized in that: The 5,5'-disubstituted amino-3,3'-bipyridine derivatives include at least one of the following structures:

4. A method for preparing a 5,5'-disubstituted amino-3,3'-bipyridine derivative according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Place the indigo plant in a reaction solvent and stir until it is uniform 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 to react until no blue is present, which is considered the reaction endpoint, to obtain a reaction product solution; S3, adding deionized water to the reaction product solution obtained in step S2 and stirring to perform purification treatment; S4. The purified solution is subjected to solid-liquid separation, and then dried to obtain 5,5'-disubstituted amino-3,3'-bipyridine derivatives.

5. The method for preparing 5,5'-disubstituted amino-3,3'-bipyridine derivatives according to claim 4, characterized in that: The solvent includes one of DMF, DMSO, DMA, tetrahydrofuran, carbon tetrachloride, chloroform, dichloromethane and dichloroethane.

6. The method for preparing 5,5'-disubstituted amino-3,3'-bipyridine derivatives according to claim 4, characterized in that: 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: one of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, piperidine, pyrazine, pyridazine, indole, quinoline, pteridine, acridine, naphthalene, phenanthrene, anthracene, pyrene, naphthoquinone, phenanthrenequinone, and anthraquinone; the substituent of the heterocyclic ring is one of halogen, C1-C3 alkyl, and halogenated C1-C3 alkyl.

7. The method for preparing 5,5'-disubstituted amino-3,3'-bipyridine derivatives according to claim 4, characterized in that: The acid binding agent comprises at least one of triethylamine, triethylenediamine, dimethylamine, trimethylamine, pyridine, N-methylmorpholine, tetramethylethylenediamine, sodium tert-butoxide, and potassium tert-butoxide; The catalyst is a Lewis acid catalyst, and the catalyst includes one of boron trifluoride, aluminum trichloride, ferric chloride, boron tribromide, aluminum tribromide, and ferric tribromide; The added amount of the catalyst is 0.1% to 5% of the blue mass.

8. The method for preparing 5,5'-disubstituted amino-3,3'-bipyridine derivatives according to claim 4, characterized in that: The molar ratio of the indigo plant, the derivatizing agent and the acid-binding agent is 1:(1.2-2.2):(1.2-2.2); In step S2, the reaction temperature is 60 to 120° C., and the reaction time is 1 to 24 hours.

9. Use of the 5,5'-disubstituted amino-3,3'-bipyridine derivatives according to any one of claims 1 to 3 in fabric dyeing.

10. The use according to claim 9, characterized in that The fabric comprises at least one of cotton, linen, wool, mulberry silk, regenerated fiber and chemical fiber.

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