Substituted aminobipyridine derivatives, processes for their preparation and use

Abstract

The application provides a substituted amino bipyridine derivative and a preparation method and application thereof, and the structure of the substituted amino bipyridine derivative is shown in formula I, wherein 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 group; and when R1, R2, R3 and R4 are not all 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 remaining groups are independently selected from H or methyl. The substituted amino bipyridine derivative provided by the application is used as a blue dye, has bright color, deep dyeing and comprehensive dyeing fastness after dyeing; the preparation process is simple and convenient for purification, the preparation process is safe, simple, energy-saving, the product quality is stable, the reproducibility is good, the yield is high, and the product is suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of dye synthesis technology, specifically relating to a substituted aminobipyridine derivative, its preparation method, and its application. Background Technology

[0002] Bio-based materials, as an emerging material type, are gradually changing the way traditional materials are used due to their unique advantages in environmental protection, sustainability, and functionality. The raw materials for bio-based materials are derived from renewable resources, such as plants and microorganisms, reducing dependence on fossil resources and contributing to sustainable development. In the production process, bio-based materials typically have lower carbon emissions and energy consumption, helping to reduce environmental pollution and greenhouse gas emissions. Furthermore, bio-based materials are biodegradable, capable of degrading in the natural environment and reducing long-term environmental pollution. With increasingly severe environmental problems, the pollution caused by wastewater from the production of traditional purely chemically synthesized dyes has attracted great attention from dyeing and finishing professionals. Therefore, the demand for bio-based environmentally friendly dyes is growing.

[0003] Indigoidine, or blue pigment, is a bicyclic compound formed by the condensation of two glutamine molecules under the action of indigoidine synthase. It is a bright and harmless natural blue pigment with wide applications, including cosmetics, textile dyeing, and the medical industry. Patent ZL202510301031.9 reports a class of derivatives based on the indigoidine structure, which not only retain the main structure of bio-based materials but also derive substances of different colors. However, the properties and applications of N-polysubstituted indigoidine derivatives, including patent ZL202510301031.9, have not been thoroughly studied. Therefore, how to provide an N-polysubstituted indigoidine derivative compound with excellent dyeing effects has become an urgent problem to be solved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a substituted aminobipyridine derivative, its preparation method, and its applications. The substituted aminobipyridine derivative provided by the present invention, when used as a blue dye, produces a bright, deep, and comprehensive color fastness after dyeing. The preparation method uses indigo as a raw material, is simple, convenient to purify, safe, convenient, and energy-efficient, and produces a product with stable quality, good reproducibility, and high yield, making it suitable for industrial production.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a substituted aminobipyridine derivative, the structure of which is shown in Formula I:

[0007]

[0008] Formula I;

[0009] 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 groups;

[0010] When none of R1, R2, R3, and R4 are methyl groups, at most one of R1, R2, R3, and R4 is H.

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

[0012] The compounds with the above-mentioned specific structures fill the gap in the N-polysubstituted derivative structures of blue dyes. As blue dyes, they have the advantages of bright color, deep color and comprehensive color fastness after dyeing.

[0013] Preferably, R1, R2, R3, and 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.

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

[0015]

[0016]

[0017]

[0018]

[0019]

[0020] .

[0021] Secondly, the present invention provides a method for preparing the substituted aminobipyridine derivatives as described above, the method comprising the following steps:

[0022] The substituted aminobipyridine derivative was obtained by mixing and reacting the blue violet with a derivatizing agent and a phase transfer catalyst.

[0023] The reaction formula is as follows:

[0024]

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

[0026] The above preparation method uses blue azure as raw material and requires only one reaction step to achieve product preparation. The preparation process is simple, purification is convenient, the preparation process is safe, convenient and energy-saving, the product quality is stable, reproducible and has a high yield, making it suitable for industrial production.

[0027] Preferably, the derivatizing reagent comprises any one of C1-C6 alkyl halides, C2-C6 alkenyl halides, C2-C20 alkynyl halides, C3-C6 cycloalkyl halides, C5-C20 aryl halides, C5-C20 heterocyclic halides, C1-C6 alkyl sulfate esters, or C2-C6 alkenyl sulfate esters.

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

[0029] Preferably, the reaction is carried out in an alkaline aqueous solution with a pH of 12-14, such as 12, 12.5, 13, 13.5 or 14, but not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

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

[0031] Preferably, the reaction temperature is 0-25℃, such as 0℃, 5℃, 10℃, 15℃, 20℃ or 25℃, but not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0032] Thirdly, the present invention also provides the application of the substituted aminobipyridine derivatives as described above in fabric dyeing.

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

[0034] This invention provides a substituted aminobipyridine derivative and its preparation method. The derivative, when used as a blue dye, produces a bright, deep, and comprehensive color fastness on fabrics. The preparation method uses indigo as a raw material, and the process is simple, easy to purify, safe, convenient, and energy-saving. The product has stable quality, good reproducibility, and high yield, making it suitable for industrial production. Attached Figure Description

[0035] Figure 1 The image shows cotton fabric dyed with a substituted aminobipyridine derivative dye solution provided in Example 1 of the test cases. Detailed Implementation

[0036] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

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

[0038] The blue pigment used in the following examples was provided by Nanjing Hegu Life Biotechnology Co., Ltd. Product structure identification: The synthesized product was sent to the Analysis and Testing Center of Nanjing Normal University for testing.

[0039] The following examples each provide a substituted aminobipyridine derivative, and the specific preparation methods are as follows:

[0040] Example 1

[0041] 2.5 g of *Gynostemma pentaphyllum* raw material was weighed and added to 50 g of sodium hydroxide aqueous solution with pH 14. The mixture was then thoroughly dispersed in a 100 mL three-necked round-bottom flask. Two equivalents of dimethyl sulfate were added dropwise to initiate the reaction. Tetrabutylammonium bromide was added as a catalyst at 1% of the *Gynostemma pentaphyllum* mass. The reaction was carried out at 10 °C for 0.5 h. After the reaction was complete, the pH was adjusted to neutral, and a solid precipitated. This solid was centrifuged, washed twice with water, dried, and 1.9 g of product Z2 was obtained. LC-MS (m / z): 291.0 ([M+H)) + ).

[0042] Example 2

[0043] Weigh 6 g of *Osmanthus fragrans* raw material and add 80 g of potassium hydroxide aqueous solution with pH 13. Disperse the mixture thoroughly in a 250 mL three-necked round-bottom flask. Add 3.5 equivalents of iodomethane dropwise to initiate the reaction. Add 18-crown-6 as a catalyst at 1% of the *Osmanthus fragrans* mass. React at 0 °C for 1 h. After the reaction is complete, adjust the pH to neutral, precipitate the solid, centrifuge, wash twice with water, dry, and obtain 4.1 g of product Z3. LC-MS (m / z): 305.1 ([M+H)) + ).

[0044] Example 3

[0045] 15 g of *Gynostemma pentaphyllum* raw material was weighed and added to 120 g of sodium hydroxide aqueous solution with pH 12. The mixture was then thoroughly dispersed in a 500 mL three-necked round-bottom flask. 5 equivalents of dimethyl sulfate were added dropwise for the reaction. 18-crown-6 was added as a catalyst at 1% of the *Gynostemma pentaphyllum* mass. The reaction was carried out at 25 °C for 1 h. After the reaction was complete, the pH was adjusted to neutral, and a solid precipitated. This solid was centrifuged, washed twice with water, dried, and 12.3 g of product Z2 was obtained. LC-MS (m / z): 291.0 ([M+H)) + ).

[0046] Example 4

[0047] 10 g of dimethyl phthalic acid raw material was weighed and added to 100 g of sodium hydroxide aqueous solution with pH 12. The mixture was then thoroughly dispersed in a 500 mL three-necked round-bottom flask. Three equivalents of dimethyl sulfate were added dropwise to initiate the reaction. Tetrabutylammonium bromide was added as a catalyst at 1% of the mass of dimethyl phthalic acid. The reaction was carried out at 25 °C for 1 h. After the reaction was complete, the pH was adjusted to neutral, and the precipitated solid was separated by centrifugation, washed twice with water, dried, and 8.3 g of product Z3 was obtained. LC-MS (m / z): 305.1 ([M+H) + ).

[0048] Example 5

[0049] 25 g of *Gynostemma pentaphyllum* raw material was weighed and added to 140 g of potassium hydroxide aqueous solution with pH 12. The mixture was then thoroughly dispersed in a 500 mL three-necked round-bottom flask. 3.8 equivalents of diethyl sulfate were added dropwise to initiate the reaction. 18-crown-6 was added as a catalyst at 1% of the *Gynostemma pentaphyllum* mass. The reaction was carried out at 0 °C for 0.5 h. After the reaction was complete, the pH was adjusted to neutral, and a solid precipitated. This solid was centrifuged, washed twice with water, dried, and 20.8 g of product Z4 was obtained. LC-MS (m / z): 331.1 ([MH]) - ).

[0050] Example 6

[0051] 16 g of *Gynostemma pentaphyllum* raw material was weighed and added to 90 g of potassium hydroxide aqueous solution with pH 13. The mixture was then thoroughly dispersed in a 500 mL three-necked round-bottom flask. 5 equivalents of bromoethane were added dropwise to initiate the reaction. 18-crown-6 was added as a catalyst at 1% of the *Gynostemma pentaphyllum* mass. The reaction was carried out at 25 °C for 1 h. After the reaction was complete, the pH was adjusted to neutral, the solid precipitated, centrifuged, washed twice with water, dried, and 20.8 g of product Z5 was obtained. LC-MS (m / z): 361.1 ([M+H)) + ).

[0052] Example 7

[0053] 2.5 g of *Gynostemma pentaphyllum* raw material was weighed and added to 50 g of sodium hydroxide aqueous solution with pH 14. The mixture was then thoroughly dispersed in a 120 mL three-necked round-bottom flask. 2.4 equivalents of dimethyl sulfate were added dropwise to initiate the reaction. Tetrabutylammonium bromide was added as a catalyst at 1% of the *Gynostemma pentaphyllum* mass. The reaction was carried out at 10 °C for 0.5 h. After the reaction was complete, the pH was adjusted to neutral, and a solid precipitated. This solid was centrifuged, washed twice with water, dried, and 2.0 g of product Z1 was obtained. LC-MS (m / z): 277.1 ([M+H)) + ).

[0054] Example 8

[0055] Replacing iodomethane with dipropyl sulfate in Example 2, while keeping other conditions unchanged, yielded 3.2 g of product Z6. LC-MS (m / z): 375.2 ([M+H) + ).

[0056] Example 9

[0057] Replacing dimethyl sulfate with dipropyl sulfate in Example 3, while keeping other conditions unchanged, yielded 9.5 g of product Z7. LC-MS (m / z): 417.2 ([M+H]) + ).

[0058] Example 10

[0059] Replacing iodomethane with diisopropyl sulfate in Example 2, while keeping other conditions unchanged, yielded 2.1 g of product Z8. LC-MS (m / z): 375.2 ([M+H) + ).

[0060] Example 11

[0061] Replacing dimethyl sulfate with diisopropyl sulfate in Example 3, while keeping other conditions unchanged, yielded 7.9 g of product Z9. LC-MS (m / z): 417.2 ([M+H]) + ).

[0062] Example 12

[0063] Replacing iodomethane with 2-chlorobutane in Example 2, while keeping other conditions unchanged, yielded 2.8 g of product Z10. LC-MS (m / z): 417.2 ([M+H]) + ).

[0064] Example 13

[0065] Replacing dimethyl sulfate with 2-chlorobutane in Example 3, while keeping other conditions unchanged, yielded 6.8 g of product Z11. LC-MS (m / z): 473.3 ([M+H]) +).

[0066] Example 14

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

[0068] Example 15

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

[0070] Example 16

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

[0072] Example 17

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

[0074] Example 18

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

[0076] Example 19

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

[0078] Example 20

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

[0080] Example 21

[0081] Replacing dimethyl sulfate with 3-chloroquinoline in Example 3, while keeping other conditions unchanged, yielded 7.2 g of product Z19. LC-MS (m / z): 757.2 ([M+H]) + ).

[0082] Example 22

[0083] Replacing iodomethane with 2-chlorobutene in Example 2, while keeping other conditions unchanged, yielded 1.7 g of product Z21. LC-MS (m / z): 413.4 ([M+H]) + ).

[0084] Example 23

[0085] Replacing dimethyl sulfate with 2-chlorobutene in Example 3, while keeping other conditions unchanged, yielded 6.8 g of product Z22. LC-MS (m / z): 465.5 ([M+H]). + ).

[0086] Example 24

[0087] Replacing iodomethane in Example 2 with 2-chloro-3-methylpyridine, while keeping other conditions unchanged, yielded 1.3 g of product Z23. LC-MS (m / z): 522.5 ([M+H]) + ).

[0088] Example 25

[0089] Replacing dimethyl sulfate in Example 3 with 2-chloro-3-methylpyridine, while keeping other conditions unchanged, yielded 7.1 g of product Z24. LC-MS (m / z): 613.6 ([M+H]) + ).

[0090] Example 26

[0091] Replacing iodomethane in Example 2 with 1,3-dimethyl-5-chloropyrrole, while keeping other conditions unchanged, yielded 1.8 g of product Z25. LC-MS (m / z): 540.7 ([M+H]) + ).

[0092] Example 27

[0093] Replacing dimethyl sulfate in Example 3 with 1,3-dimethyl-5-chloropyrrole, while keeping other conditions unchanged, yielded 5.7 g of product Z26. LC-MS (m / z): 637.8 ([M+H)) + ).

[0094] Example 28

[0095] Replacing iodomethane in Example 2 with 1-ethyl-2-chloroindole, while keeping other conditions unchanged, yielded 1.9 g of product Z27. LC-MS (m / z): 678.7 ([M+H]) + ).

[0096] Example 29

[0097] Replacing dimethyl sulfate in Example 3 with 1-ethyl-2-chloroindole, while keeping other conditions unchanged, yielded 8.6 g of product Z28. LC-MS (m / z): 821.9 ([M+H]) + ).

[0098] Example 30

[0099] Replacing iodomethane in Example 2 with 3-chloro-8-methylquinoline, while keeping other conditions unchanged, yielded 3.1 g of product Z29. LC-MS (m / z): 672.7 ([M+H]) + ).

[0100] Example 31

[0101] Replacing dimethyl sulfate in Example 3 with 3-chloro-8-methylquinoline, while keeping other conditions unchanged, yielded 7.4 g of product Z30. LC-MS (m / z): 813.9 ([M+H]) + ).

[0102] Example 32

[0103] Replacing 2 equivalents of dimethyl sulfate in Example 1 with 1 equivalent of dimethyl sulfate, while keeping other conditions unchanged, yielded 1.4 g of product Z0. LC-MS (m / z): 263.1 ([M+H]) + ).

[0104] Similar reaction conditions to Examples 1-32 above were used, but the derivatizing reagent and catalyst were changed. The structure of the derivatizing reagent corresponds to different substituents. The catalyst does not change the structure of the reaction product. The prepared substituted aminobipyridine derivatives are shown in the table below.

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] Test Example 1: Staining Test

[0112] The following tests illustrate the application of the substituted aminobipyridine derivatives prepared in this invention in staining.

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

[0114] Replace 2% (owf) of aminobipyridine derivatives, reduce with 2 times the amount of sodium hydrosulfite, adjust pH to 5 with 0.5 mL / L citric acid, stain at 25℃ for 10 min, bath ratio 1:30.

[0115] After dyeing is completed, remove the dyed fabric sample, wash and dry it. Figure 1 The cotton fabrics dyed with the substituted aminobipyridine derivative dye solution provided in Example 1 are, from left to right, dyed once, dyed twice, dyed three times, and dyed four times.

[0116] The color depth (K / S), light fastness, water fastness, dry heat fastness, acid stain fastness, and wet rubbing fastness of fabric samples obtained by dyeing the synthesized substituted aminobipyridine derivatives were determined.

[0117] Color depth was measured using a colorimeter; lightfastness was tested according to GB / T 8427-2019 "Textiles - Tests for Color Fastness to Artificial Light: Xenon Arc"; waterfastness was tested according to GB / T 5713-2013 "Textiles - Tests for Color Fastness to Water"; dry heatfastness was tested according to GB / 5718-1997 "Textiles - Tests for Color Fastness to Dry Heat (excluding hot pressing)"; acid spotfastness was tested according to GB / T 5715-2013 "Textiles - Tests for Color Fastness to Acid Spots"; and wet rubbingfastness was tested according to GB / T 3920-2008 "Textiles - Tests for Color Fastness to Rubbing".

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

[0119] Table 1

[0120]

[0121]

[0122] It can be seen that the substituted aminobipyridine derivatives provided by the present invention can dye cotton fabrics with a K / S value of over 10. The color fastness to water, dry heat, acid spots, light, and wet rubbing all reach level 5, demonstrating excellent technical performance.

[0123] Test Example 2: Solubility Test

[0124] The effects of the substituted aminobipyridine derivatives prepared in this invention will be illustrated below through solubility tests.

[0125] Step 1: Prepare a supersaturated solution (ensure the solvent reaches its solubility limit).

[0126] Accurately transfer a fixed volume of solvent using a pipette and inject it into a dry, stoppered conical flask;

[0127] Place the conical flask in a constant temperature water bath and keep it at that temperature for 30 minutes (to allow the solvent temperature to stabilize at the set value).

[0128] Add the solute to be tested gradually using an analytical balance: add a small amount (0.1g) each time, and immediately tighten the stopper after adding, and turn on the magnetic stirrer (at a constant rate).

[0129] Stir for 15 minutes and observe whether the solute has completely dissolved (no visible particles); if it has completely dissolved, repeat the "add solute-stir" step.

[0130] If there is still undissolved precipitate (visible to the naked eye, or solid at the bottom after standing) after stirring for 30 minutes after adding solute, 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: Let stand and clarify (to avoid interference from undissolved solutes)

[0132] Stop stirring and leave the conical flask in the constant temperature water bath for 30 minutes;

[0133] Allow undissolved solid particles to settle to the bottom of the bottle, ensuring that the upper layer solution is a saturated and clear solution (if there are still suspended particles, the settling time needs to be extended or centrifuged).

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

[0135] Dry the clean evaporating dish in an oven (105℃) until constant weight, and weigh it using an analytical balance after cooling (record as m1, accurate to 0.1mg).

[0136] Accurately aspirate the clear, saturated solution from the top layer using a dry pipette and slowly inject it into a pre-weighed evaporating dish.

[0137] Place the evaporating dish on a water bath and slowly evaporate it to dryness (avoid splashing of the solute), then place it in a 105℃ oven to dry to constant weight (the difference between two weighings should be ≤0.1mg), and weigh the total mass after cooling (recorded as m2).

[0138] calculate:

[0139] (1) Mass of solute in the solution taken = m2 – m1 (denoted as m_solute);

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

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

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

[0143] Table 2

[0144]

[0145]

[0146]

[0147] It can be observed that the substituted aminobipyridine derivatives provided by this invention have significantly higher solubility. The solubility of compounds Z0-Z13 in ethanol and ethyl acetate both exceed 10 mg / L, which is significantly better than the prior art. When used as dyes, they can be dispersed more uniformly and have excellent technical effects.

[0148] The applicant declares that this invention illustrates the substituted aminobipyridine derivatives, their preparation methods, and applications through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

[0149] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0150] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

Claims

1. A substituted aminobipyridine derivative, characterized in that, The structure of the substituted aminobipyridine derivative is shown in Formula I: ； Formula I; In the formula, R1, R2, R3, and R4 are independently selected from H or C1~C6 alkyl groups; When none of R1, R2, R3, and R4 are methyl groups, at most one of R1, R2, R3, and R4 is H. When any one of R1, R2, R3, and R4 is methyl, the remaining groups are independently selected from H or methyl.

2. A substituted aminobipyridine derivative, characterized in that, The substituted aminobipyridine derivatives are selected from any one of the following structural compounds: 。 3. A method for preparing a substituted aminobipyridine derivative according to claim 1, characterized in that, The preparation method includes the following steps: The substituted aminobipyridine derivative was obtained by mixing and reacting the blue violet with a derivatizing agent and a phase transfer catalyst. The reaction formula is as follows: ； Wherein, R1, R2, R3, and R4 have the same scope as in claim 1; The phase transfer catalyst comprises any one or a combination of at least two of tetrabutylammonium bromide, tetrabutylammonium chloride, or 18-crown ether-6; The reaction is carried out in an alkaline aqueous solution with a pH of 12-14. The reaction temperature is 0-25℃.

4. The method for preparing substituted aminobipyridine derivatives according to claim 3, characterized in that, The derivatizing reagent includes any one of C1-C6 alkyl halides or C1-C6 alkyl sulfate esters.

5. The method for preparing substituted aminobipyridine derivatives according to claim 3, characterized in that, The alkali in the alkaline aqueous solution is sodium hydroxide and / or potassium hydroxide.

6. The use of a substituted aminobipyridine derivative according to claim 1 or 2 in fabric dyeing.

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