Substituted amino dipyridyl derivative as well as preparation method and application thereof

Abstract

The invention provides a substituted amino bipyridine derivative as well as a preparation method and application thereof, the structure of the substituted amino bipyridine derivative is as shown in formula I. In the formula, R1, R2, R3 and R4 are independently selected from any one of H, C1-C6 alkyl, C2-C6 alkenyl, C2-C20 alkynyl, C3-C6 cycloalkyl, C5-C20 aryl or C5-C20 heterocyclic radical; when R1, R2, R3 and R4 are not methyl, no more than one of R1, R2, R3 and R4 is H; and when any one of R1, R2, R3 and R4 is methyl, the rest groups are independently selected from H or methyl. When the substituted amino dipyridyl derivative provided by the invention is used as a blue dye, the dyed blue dye is bright in color, deep in dyeing and comprehensive in dyeing fastness; the preparation process is simple, convenient to purify, safe, simple, convenient and energy-saving, the product quality is stable, the reproducibility is good, the yield is high, and the method is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of dye synthesis, and particularly relates to a substituted amino bipyridine derivative and a preparation method and application thereof. BACKGROUND

[0002] Biobased materials, as a new type of material, are gradually changing the way traditional materials are used due to their unique environmental, sustainable and functional advantages. The raw materials of biobased materials come from renewable resources such as plants and microorganisms, reducing the dependence on fossil resources and helping to achieve sustainable development. In the production process, biobased materials generally have lower carbon emissions and energy consumption, which helps to reduce environmental pollution and greenhouse gas emissions. In addition, biobased materials are biodegradable and can degrade in the natural environment, reducing long-term pollution to the environment. As environmental problems become increasingly serious, the pollution of wastewater generated in the production of traditional pure chemical synthetic dyes has attracted great attention from dyeing and finishing workers. Therefore, the demand for biobased environmentally friendly dyes is also increasing.

[0003] Indigoidine is a substance with a bicyclic structure formed by the condensation of two glutamine molecules under the action of indigoidine synthase. Indigoidine is a natural blue pigment with bright color and no harm, and its application fields are wide, including cosmetics, fabric printing and dyeing, and medical industry. Patent ZL202510301031.9 reports a class of derivatives based on the structure of indigoidine, which not only retains the main structure of biobased materials, but also derives substances with different colors. However, the properties and applications of N-multiple substituted derivatives of indigoidine have not been thoroughly studied by existing technologies including patent ZL202510301031.9. Therefore, how to provide a N-multiple substituted derivative compound based on indigoidine with excellent dyeing effect has become a problem to be solved. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a substituted amino bipyridine derivative and a preparation method and application thereof. The substituted amino bipyridine derivative provided by the present application is used as a blue dye, which has bright color, deep dyeing and overall dyeing fastness after dyeing. The preparation method uses indigoidine as raw material, and the preparation process is simple, convenient for purification, safe, simple, energy-saving, and the product quality is stable, reproducible, high-yield, and suitable for industrial production.

[0005] To achieve the purpose of the present application, the following technical solutions are adopted:

[0006] In a first aspect, the present application provides a substituted amino bipyridine derivative, the structure of which is shown as formula I:

[0007]

[0008] Formula I;

[0009] In the formula, R1, R2, R3, R4 are independently selected from any one of H, C1-C6 alkyl, C2-C6 alkenyl, C2-C20 alkynyl, C3-C6 cycloalkyl, C5-C20 aryl or C5-C20 heterocyclic group;

[0010] and when R1, R2, R3, R4 are all not methyl, no more than one of R1, R2, R3, R4 is H.

[0011] When any one of R1, R2, R3, R4 is methyl, the rest are independently selected from H or methyl.

[0012] The compound of the specific structure fills the blank of the N-polysubstituted derivative structure of indigo, and has the advantages of bright color, deep dyeing and comprehensive dyeing fastness as a blue dye.

[0013] Preferably, R1, R2, R3, R4 are independently selected from any one of H, C1-C6 alkyl, C2-C6 alkenyl, C2-C10 alkynyl, C3-C6 cycloalkyl, C5-C12 aryl or C5-C12 heterocyclic group.

[0014] Preferably, the substituted amino bipyridine derivative is selected from any one of the following structural compounds:

[0015]

[0016]

[0017]

[0018]

[0019]

[0020] .

[0021] In a second aspect, the present application provides a preparation method of the substituted amino bipyridine derivative as described above, which comprises the following steps:

[0022] mixing and reacting indigo with a derivative reagent and a phase transfer catalyst to obtain the substituted amino bipyridine derivative;

[0023] The reaction formula is as follows:

[0024]

[0025] Wherein, R1, R2, R3, R4 have the same defined range as described above.

[0026] The preparation method described above uses guan blue as raw material, and can realize product preparation through only one reaction, and has the advantages of simple preparation process, convenient purification, safe and simple preparation process, energy saving, stable product quality, good reproducibility, high yield, and suitability for industrial production.

[0027] Preferably, the derivatizing agent comprises any one of C1-C6 alkyl halide, C2-C6 alkenyl halide, C2-C20 alkynyl halide, C3-C6 cycloalkyl halide, C5-C20 aryl halide, C5-C20 heterocyclyl halide, C1-C6 alkyl sulfate, or C2-C6 alkenyl sulfate.

[0028] Preferably, the phase transfer catalyst comprises any one or a combination of at least two of tetrabutylammonium bromide, tetrabutylammonium chloride, or 18-crown-6.

[0029] Preferably, the reaction is carried out in an alkaline aqueous solution, and the pH of the alkaline aqueous solution is 12-14, for example, 12, 12.5, 13, 13.5, or 14, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable.

[0030] Preferably, the base in the alkaline aqueous solution is sodium hydroxide and / or potassium hydroxide.

[0031] Preferably, the temperature of the reaction is 0-25℃, for example, 0℃, 5℃, 10℃, 15℃, 20℃, or 25℃, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable.

[0032] In a third aspect, the application also provides the use of the substituted aminopyridine derivative as described above in fabric dyeing.

[0033] Compared with the prior art, the application has the following beneficial effects:

[0034] The application provides a substituted aminopyridine derivative and a preparation method thereof. The derivative is used as a blue dye, and after dyeing on a fabric, the color is bright, the dyeing depth is high, and the dyeing fastness is comprehensive. The preparation method uses guan blue as raw material, and has the advantages of simple preparation process, convenient purification, safe and simple preparation process, energy saving, stable product quality, good reproducibility, high yield, and suitability for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is a picture of a cotton fabric dyed with the substituted aminopyridine derivative solution provided in Example 1 in the test example. DETAILED DESCRIPTION

[0036] The technical solutions of the present application will be further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application, and should not be regarded as specific limitation to the present application.

[0037] In the following examples, the experimental methods used are conventional methods, and the materials, reagents, etc. used are commercially available unless otherwise specified.

[0038] The guanlan used in the following examples is provided by Nanjing Huguai Life Biotechnology Co., Ltd. The structure of the product is identified: the synthesized product is sent to the Analysis and Testing Center of Nanjing Normal University for detection.

[0039] The following examples each provide a substituted amino bipyridine derivative, and the preparation method is as follows:

[0040] Example 1

[0041] Take 2.5 g of guanlan raw material, add 50 g of sodium hydroxide aqueous solution with pH of 14, and fully disperse in a 100 mL three-necked round-bottom flask. Add 2 equivalents of dimethyl sulfate for reaction, add tetrabutylammonium bromide as catalyst, and the addition amount is 1% of the mass of guanlan. React at 10℃ for 0.5 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash with water twice, dry, and separate to obtain 1.9 g of product Z2. LC-MS (m / z): 291.0 ([M+H] + ).

[0042] Example 2

[0043] Take 6 g of guanlan raw material, add 80 g of potassium hydroxide aqueous solution with pH of 13, and fully disperse in a 250 mL three-necked round-bottom flask. Add 3.5 equivalents of iodomethane for reaction, and add 18-crown-6 as catalyst, and the addition amount is 1% of the mass of guanlan. React at 0℃ for 1 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash with water twice, dry, and separate to obtain 4.1 g of product Z3. LC-MS (m / z): 305.1 ([M+H] + ).

[0044] Example 3

[0045] Take 15 g of methylene blue raw material, add 120 g of sodium hydroxide aqueous solution with pH of 12, and fully disperse in a 500 mL three-necked round-bottom flask. Add 5 equivalents of dimethyl sulfate dropwise for reaction, add 18-crown-6 as a catalyst, and the addition amount is 1% of the mass of methylene blue. React at 25°C for 1 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash with water twice, dry, and separate to obtain 12.3 g of product Z2. LC-MS (m / z): 291.0 ([M+H] + ).

[0046] Example 4

[0047] Take 10 g of methylene blue raw material, add 100 g of sodium hydroxide aqueous solution with pH of 12, and fully disperse in a 500 mL three-necked round-bottom flask. Add 3 equivalents of dimethyl sulfate dropwise for reaction, add tetrabutylammonium bromide as a catalyst, and the addition amount is 1% of the mass of dimethyl methylene blue. React at 25°C for 1 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash with water twice, dry, and separate to obtain 8.3 g of product Z3. LC-MS (m / z): 305.1 ([M+H] + ).

[0048] Example 5

[0049] Take 25 g of methylene blue raw material, add 140 g of potassium hydroxide aqueous solution with pH of 12, and fully disperse in a 500 mL three-necked round-bottom flask. Add 3.8 equivalents of diethyl sulfate dropwise for reaction, add 18-crown-6 as a catalyst, and the addition amount is 1% of the mass of methylene blue. React at 0°C for 0.5 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash with water twice, dry, and separate to obtain 20.8 g of product Z4. LC-MS (m / z): 331.1 ([M-H] - ).

[0050] Example 6

[0051] Take 16 g of methylene blue raw material, add 90 g of potassium hydroxide aqueous solution with pH of 13, and fully disperse in a 500 mL three-necked round-bottom flask. Add 5 equivalents of bromoethane dropwise for reaction, add 18-crown-6 as a catalyst, and the addition amount is 1% of the mass of methylene blue. React at 25°C for 1 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash with water twice, dry, and separate to obtain 20.8 g of product Z5. LC-MS (m / z): 361.1 ([M+H] + ).

[0052] Example 7

[0053] Take 2.5 g of the blue raw material, add 50 g of sodium hydroxide aqueous solution with pH 14, and fully disperse in a 120 mL three-necked round-bottom flask. Add 2.4 equivalents of dimethyl sulfate for reaction, add tetrabutylammonium bromide as a catalyst, and the addition amount is 1% of the mass of the blue. React at 10°C for 0.5 h. After the reaction is completed, adjust the pH to neutral, precipitate the solid, centrifuge and separate, wash twice with water, dry, and separate 2.0 g of product Z1. LC-MS (m / z): 277.1 ([M+H] + ).

[0054] Example 8

[0055] Replace the methyl iodide of Example 2 with dipropyl sulfate, and the other conditions remain unchanged, to obtain 3.2 g of product Z6. LC-MS (m / z): 375.2 ([M+H] + ).

[0056] Example 9

[0057] Replace the dimethyl sulfate of Example 3 with dipropyl sulfate, and the other conditions remain unchanged, to obtain 9.5 g of product Z7. LC-MS (m / z): 417.2 ([M+H] + ).

[0058] Example 10

[0059] Replace the methyl iodide of Example 2 with diisopropyl sulfate, and the other conditions remain unchanged, to obtain 2.1 g of product Z8. LC-MS (m / z): 375.2 ([M+H] + ).

[0060] Example 11

[0061] Replace the dimethyl sulfate of Example 3 with diisopropyl sulfate, and the other conditions remain unchanged, to obtain 7.9 g of product Z9. LC-MS (m / z): 417.2 ([M+H] + ).

[0062] Example 12

[0063] Replace the methyl iodide of Example 2 with 2-chlorobutane, and the other conditions remain unchanged, to obtain 2.8 g of product Z10. LC-MS (m / z): 417.2 ([M+H] + ).

[0064] Example 13

[0065] Replace the dimethyl sulfate of Example 3 with 2-chlorobutane, and the other conditions remain unchanged, to obtain 6.8 g of product Z11. LC-MS (m / z): 473.3 ([M+H] +).

[0066] Example 14

[0067] Replacing iodomethane of Example 2 with 2-chloropyridine, and keeping other conditions unchanged, 2.9 g of product Z12 was obtained. LC-MS (m / z): 480.1 ([M+H] + ).

[0068] Example 15

[0069] Replacing dimethyl sulfate of Example 3 with 2-chloropyridine, and keeping other conditions unchanged, 8.7 g of product Z13 was obtained. LC-MS (m / z): 557.1 ([M+H] + ).

[0070] Example 16

[0071] Replacing iodomethane of Example 2 with 2-chloro-N-methylpyrrole, and keeping other conditions unchanged, 1.8 g of product Z14 was obtained. LC-MS (m / z): 498.3 ([M+H] + ).

[0072] Example 17

[0073] Replacing dimethyl sulfate of Example 3 with 2-chloro-N-methylpyrrole, and keeping other conditions unchanged, 6.9 g of product Z15 was obtained. LC-MS (m / z): 581.3 ([M+H] + ).

[0074] Example 18

[0075] Replacing iodomethane of Example 2 with 2-chloroindole, and keeping other conditions unchanged, 3.1 g of product Z16 was obtained. LC-MS (m / z): 594.2 ([M+H] + ).

[0076] Example 19

[0077] Replacing dimethyl sulfate of Example 3 with 2-chloroindole, and keeping other conditions unchanged, 7.6 g of product Z17 was obtained. LC-MS (m / z): 709.2 ([M+H] + ).

[0078] Example 20

[0079] Replacing iodomethane of Example 2 with 3-chloroquinoline, and keeping other conditions unchanged, 1.9 g of product Z18 was obtained. LC-MS (m / z): 630.2 ([M+H] + ).

[0080] Example 21

[0081] Instead of dimethyl sulfate of Example 3, 3-chloroquinoline was used, and otherwise the same, to give 7.2 g of product Z19. LC-MS (m / z): 757.2 ([M+H] + ).

[0082] Example 22

[0083] Instead of iodomethane of Example 2, 2-chlorobuten was used, and otherwise the same, to give 1.7 g of product Z21. LC-MS (m / z): 413.4 ([M+H] + ).

[0084] Example 23

[0085] Instead of dimethyl sulfate of Example 3, 2-chlorobuten was used, and otherwise the same, to give 6.8 g of product Z22. LC-MS (m / z): 465.5 ([M+H] + ).

[0086] Example 24

[0087] Instead of iodomethane of Example 2, 2-chloro-3-methylpyridine was used, and otherwise the same, to give 1.3 g of product Z23. LC-MS (m / z): 522.5 ([M+H] + ).

[0088] Example 25

[0089] Instead of dimethyl sulfate of Example 3, 2-chloro-3-methylpyridine was used, and otherwise the same, to give 7.1 g of product Z24. LC-MS (m / z): 613.6 ([M+H] + ).

[0090] Example 26

[0091] Instead of iodomethane of Example 2, 1,3-dimethyl-5-chloropyrrole was used, and otherwise the same, to give 1.8 g of product Z25. LC-MS (m / z): 540.7 ([M+H] + ).

[0092] Example 27

[0093] Instead of dimethyl sulfate of Example 3, 1,3-dimethyl-5-chloropyrrole was used, and otherwise the same, to give 5.7 g of product Z26. LC-MS (m / z): 637.8 ([M+H] + ).

[0094] Example 28

[0095] Using the same reaction conditions as in Example 2, replacing iodomethane with 1- ethyl-2-chloroindole, 1.9 g of product Z27 was obtained. LC-MS (m / z): 678.7 ([M+H] + ).

[0096] Example 29

[0097] Using the same reaction conditions as in Example 3, replacing dimethyl sulfate with 1- ethyl-2-chloroindole, 8.6 g of product Z28 was obtained. LC-MS (m / z): 821.9 ([M+H] + ).

[0098] Example 30

[0099] Using the same reaction conditions as in Example 2, replacing iodomethane with 3-chloro- 8-methylquinoline, 3.1 g of product Z29 was obtained. LC-MS (m / z): 672.7 ([M+H] + ).

[0100] Example 31

[0101] Using the same reaction conditions as in Example 3, replacing dimethyl sulfate with 3- chloro-8-methylquinoline, 7.4 g of product Z30 was obtained. LC-MS (m / z): 813.9 ([M+H] + ).

[0102] Example 32

[0103] Using the same reaction conditions as in Example 1, replacing 2 equivalents of dimethyl sulfate with 1 equivalent of dimethyl sulfate, 1.4 g of product Z0 was obtained. LC-MS (m / z): 263.1 ([M+H] + ).

[0104] Using the same reaction conditions as in Examples 1-32, the reaction reagent and catalyst were changed. The structure of the reagent corresponds to different substituents. The catalyst does not change the structure of the reaction product. The prepared substituted aminopyridine derivatives are shown in the following table.

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] Test Example 1 Dyeing Test

[0112] The application of the prepared substituted aminobipyridine derivatives in dyeing is illustrated by tests as follows.

[0113] The substituted aminobipyridine derivatives synthesized in the above examples are used to dye cotton textiles according to the following process:

[0114] The substituted aminobipyridine derivative 2% (o.w.f), 2 times of sodium hydrosulfite, 0.5 mL / L of citric acid is adjusted to pH 5, and dyed at 25°C for 10 min, with a bath ratio of 1:30.

[0115] After the dyeing is completed, the dyed fabric sample is taken out, washed, and dried Figure 1 The cotton fabric dyed with the dye liquor of the substituted aminobipyridine derivative provided in Example 1 from left to right is dyed once, dyed twice, dyed thrice, and dyed four times, respectively).

[0116] The fabric sample dyed twice with the synthesized substituted aminobipyridine derivative is subjected to determination of color depth (K / S), fastness to light color, fastness to water color, fastness to dry heat color, fastness to acid spot color, and fastness to wet rubbing color, wherein:

[0117] The color depth is determined using a colorimeter; the fastness to light color is determined by referring to GB / T 8427-2019 Textiles - Color fastness tests - Color fastness to artificial light: Xenon arc; the fastness to water color is determined by referring to GB / T 5713-2013 Textiles - Color fastness tests - Color fastness to water; the fastness to dry heat color is determined by referring to GB / 5718-1997 Textiles - Color fastness tests - Color fastness to dry heat (except for heat pressing); the fastness to acid spot color is determined by referring to GB / T 5715-2013 Textiles - Color fastness tests - Color fastness to acid spot; and the fastness to wet rubbing color is determined by referring to GB / T 3920-2008 Textiles - Color fastness tests - Color fastness to rubbing.

[0118] The properties of the dye are tested according to the standard, and the test results are recorded in Table 1 below.

[0119] Table 1

[0120]

[0121]

[0122] It can be found that the substituted aminobipyridine derivative provided by the application can be used to dye cotton fabric, the K / S value of which reaches 10 or more, and the water color fastness, dry heat color fastness, acid spot color fastness, light color fastness and wet rubbing color fastness all reach level 5, thus having excellent technical effects.

[0123] Test Example 2: Solubility test

[0124] The effect of the substituted aminobipyridine derivative prepared by the application is illustrated by the solubility test.

[0125] Step 1: Preparation of supersaturated solution (ensure that the solvent reaches the solubility limit)

[0126] A fixed volume of solvent is accurately taken by a pipette and injected into a dry conical flask with a stopper;

[0127] The conical flask is placed in a constant temperature water bath, and the temperature is kept constant for 30 min (so that the temperature of the solvent stabilizes at the set value);

[0128] The test solute is gradually added by an analytical balance: a small amount (0.1 g) is added each time, and the stopper is immediately tightened after addition, and the magnetic stirring is started (the speed is uniform);

[0129] Stir for 15 min, and observe whether the solute is completely dissolved (no visible particles with the naked eye); if it is completely dissolved, repeat the "add solute-stir" step;

[0130] If there are still undissolved precipitates (visible with the naked eye, or solid at the bottom after standing) after the added solute is stirred for 30 min, it indicates that the solution has reached a supersaturated state (at this time, the solvent has dissolved the maximum amount of solute).

[0131] Step 2: Standing and clarification (to avoid interference of undissolved solute)

[0132] Stop stirring, and continue to leave the conical flask in the constant temperature water bath for 30 min;

[0133] Let the undissolved solid particles fully settle to the bottom of the flask, and ensure that the upper layer of the solution is a saturated clear solution (if there are still suspended particles, the standing time needs to be extended or the solution needs to be centrifuged).

[0134] Step 3: Sampling and quantitative analysis (calculate solubility)

[0135] A clean evaporating dish is placed in an oven (105°C) in advance and dried to a constant weight, and the mass is weighed after cooling (recorded as m1, accurate to 0.1 mg) by an analytical balance;

[0136] A dry pipette is used to accurately suck the upper layer of the clear saturated solution, and slowly inject it into the evaporating dish with a constant weight;

[0137] Put the evaporating dish on the water bath to evaporate slowly (avoid the solute splash), and then put it into the oven at 105 DEG C to dry until the constant weight (two times the mass difference is less than or equal to 0.1 mg), and then measure the total mass (recorded as m2) after cooling;

[0138] Calculation:

[0139] (1) the mass of solute in the solution = m2-m1 (recorded as m solute);

[0140] (2) solubility (mg / 1L solvent) = (m solute / V solvent) x 100.

[0141] The solubility of the product of the application and the product of the prior art (the compound is selected from CN120230032A) is tested and compared.

[0142] The test results are shown in Table 2.

[0143] Table 2

[0144]

[0145]

[0146]

[0147] It can be found that the substituted aminobipyridine derivative provided by the application has higher solubility, and the solubility of compounds Z0-Z13 in ethanol and ethyl acetate is more than 10 mg / L, which is obviously better than the prior art, and when used as a dye, it can be more uniformly dispersed, and has excellent technical effect.

[0148] The applicant declares that the substituted aminobipyridine derivative of the application and the preparation method and application thereof are illustrated by the above examples, but the application is not limited to the above examples, that is, it does not mean that the application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the application, equivalent replacement of each raw material of the product of the application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the application.

[0149] The preferred embodiments of the application are described in detail above, but the application is not limited to the specific details in the above embodiments, and various simple modifications can be made to the technical solutions of the application within the technical concept of the application, and these simple modifications all belong to the protection scope of the application.

[0150] It should be further noted that various specific technical features described in the above specific embodiments can be combined in any suitable manner, and in order to avoid unnecessary repetition, the present application will not describe various possible combinations again.

Claims

1. A substituted aminobipyridine derivative, characterized in that, The substituted aminobipyridine derivative has a structure as shown in formula I: ； Formula I; R1, R2, R3, R4 are independently selected from any one of H, C1-C6 alkyl, C2-C6 alkenyl, C2-C20 alkynyl, C3-C6 cycloalkyl, C5-C20 aryl or C5-C20 heterocyclic group; and when R1, R2, R3, R4 are all not methyl, no more than one of R1, R2, R3, R4 is H; when any one of R1, R2, R3, R4 is methyl, the rest are independently selected from H or methyl.

2. The substituted aminobipyridine derivative according to claim 1, characterized in that, R1, R2, R3, R4 are independently selected from any one of H, C1-C6 alkyl, C2-C6 alkenyl, C2-C10 alkynyl, C3-C6 cycloalkyl, C5-C12 aryl or C5-C12 heterocyclic group.

3. The substituted aminobipyridine derivative according to claim 1, wherein The substituted aminobipyridine derivative is selected from any one of the following compounds: ； ； ； 。 4. A method of preparing the substituted aminobipyridine derivative according to any one of claims 1 to 3, characterized in that, The preparation method comprises the following steps: mixing and reacting the chrysamine with a derivatizing agent and a phase transfer catalyst to obtain the substituted aminobipyridine derivative; The reaction formula is as follows: ； R1, R2, R3, R4 have the same defined range as any one of claims 1-3.

5. The method for preparing substituted aminobipyridine derivatives according to claim 4, characterized in that, The derivatizing agent comprises any one of C1-C6 alkyl halide, C2-C6 alkenyl halide, C2-C20 alkynyl halide, C3-C6 cycloalkyl halide, C5-C20 aryl halide, C5-C20 heterocyclic halide, C1-C6 alkyl sulfate or C2-C6 alkenyl sulfate.

6. The method for preparing substituted aminobipyridine derivatives according to claim 4, characterized in that, The phase transfer catalyst comprises any one or a combination of at least two of tetrabutylammonium bromide, tetrabutylammonium chloride or 18-crown-6 ether.

7. The method for preparing substituted aminobipyridine derivatives according to claim 4, characterized in that, The reaction is carried out in an alkaline aqueous solution, and the pH of the alkaline aqueous solution is 12-14.

8. The method for preparing substituted aminobipyridine derivatives according to claim 4, characterized in that, The base in the alkaline aqueous solution is sodium hydroxide and / or potassium hydroxide.

9. The method for preparing substituted aminobipyridine derivatives according to claim 4, characterized in that, The temperature of the reaction is 0-25℃.

10. Use of the substituted aminobipyridine derivative according to any one of claims 1-3 in fabric dyeing.

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