Dihydroxypyridone compound as well as preparation method and application thereof
A dihydroxypyridinone compound was prepared by reacting indigo with an oxidant in an alkaline solution, which solved the problem of the lack of dihydroxy compounds in existing pyridinone compounds. This resulted in high-efficiency dyeing performance and industrial application potential, especially in terms of significant color changes and performance improvements in the dye field.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-23
- Publication Date
- 2026-03-31
AI Technical Summary
In the prior art, pyridone compounds are mainly monocarbonyl compounds, lacking dihydroxy compounds, which limits their application potential in dyes and other fields, especially in terms of significant color changes and performance improvements in dyes.
A dihydroxypyridinone compound was prepared by reacting an indigo agent with an oxidizing agent in an alkaline solution and controlling reaction conditions such as temperature, time, and pH. This compound can then be used as an intermediate for dyes and other applications.
The prepared dihydroxypyridinone compound exhibits excellent dyeing properties, achieving a significant color reversal from deep blue to bright yellow. It also demonstrates superior color strength and color fastness compared to conventional synthetic yellow dyes in textile dyeing, while the reaction conditions are mild and suitable for industrial production.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of organic synthesis technology, and in particular to a dihydroxypyridinone compound, its preparation method, and its application. Background Technology
[0002] Indigoidine (chemical name (5E)3-amino-5-(5-amino-2,6-dioxopyridine-3-yl)pyridine-2,6-dione) is an alkaloid compound with a bicyclic structure formed by the condensation of two molecules of glutamine. As a bright natural blue pigment, its unique aminobispyridine ring skeleton also has great potential for modification. Using indigoidine as a lead to synthesize derivatives can fully explore its value and apply it to different fields.
[0003] Pyridones are an important class of heterocyclic compounds. Due to their unique heterocyclic skeletons, these compounds have a wide range of applications, such as in organic synthesis and drug development. Pyridones are also found in natural products and possess anti-inflammatory and antibacterial biological activities. Currently, chemically synthesized pyridones are mainly monocarbonylpyridones. Previous reports have documented the successful synthesis of dicarbonylpyridones by modifying the structure of natural products. Therefore, this paper provides a method for preparing a dihydroxylated dicarbonylpyridone compound, expanding the variety of pyridone derivatives, especially for its application as a dye, which shows great promise. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides a dihydroxypyridinone compound, its preparation method, and its applications. The dihydroxypyridinone compound provided by this invention exhibits excellent staining effects and, based on its unique chemical structure, holds promise as an intermediate for applications in pharmaceuticals, pesticides, organic synthesis, and other fields.
[0005] To achieve this objective, the present invention adopts the following technical solution:
[0006] In a first aspect, the present invention provides a dihydroxypyridinone compound having the following structure:
[0007] .
[0008] In a second aspect, the present invention provides a method for preparing the dihydroxypyridinone compound according to the first aspect, the method comprising the following steps: mixing a blue violet and an oxidizing agent, and reacting them in the presence of an alkaline solution to obtain the dihydroxypyridinone compound.
[0009] Preferably, the oxidant includes any one or a combination of two of potassium permanganate or hydrogen peroxide.
[0010] Preferably, the molar ratio of the blue pigment to the oxidant is 1:(1-2) (for example, it can be 1:1, 1:1.5, 1:1.6, 1:1.8, 1:2, etc.), and more preferably 1:(1.5-2).
[0011] Preferably, the alkali in the alkaline solution includes any one or a combination of at least two of sodium hydroxide, potassium hydroxide, or potassium tert-butoxide.
[0012] Preferably, the molar ratio of the blue pigment to the alkali is 1:(0.1-1) (for example, it can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.8, 1:1, etc.).
[0013] Preferably, the reaction temperature is 20-35℃ (e.g., 20℃, 25℃, 30℃, 35℃, etc.), more preferably 25-30℃, and the reaction time is 2-8h (e.g., 2h, 4h, 6h, 8h, etc.), more preferably 4-6h.
[0014] Preferably, the reaction further includes a post-processing step: adjusting the pH value of the reaction solution with acid, then separating the solid and liquid, washing and drying the solid to obtain the dihydroxypyridinone compound.
[0015] Preferably, the acid includes any one or a combination of at least two of hydrochloric acid or sulfuric acid.
[0016] Preferably, the pH value is adjusted to a value of 3-7 (e.g., 3, 4, 5, 6, 7, etc.), and more preferably 3-6.
[0017] Preferably, the solid-liquid separation method includes centrifugation and / or filtration.
[0018] Preferably, the solvent used for washing includes water.
[0019] Thirdly, the present invention provides the application of the dihydroxypyridinone compound according to the first aspect as a yellow dye in dyeing.
[0020] Compared with the prior art, the present invention has at least the following beneficial effects:
[0021] (1) This invention provides an oxide product of the downstream product of blue dyeing, hydroxypyridinone, which also has excellent fabric dyeing properties. In addition, given its unique chemical structure, this compound has great potential for derivative development in the fields of pesticides, pharmaceuticals, and organic synthesis. In the future, it is expected to be used as an important intermediate in the research and development of these fields.
[0022] (2) As can be seen from the dyeing effect application examples, the compound provided in this application is yellow. Starting from the blue of indigo, a new product with yellow color and excellent performance is created. It can convert the dark blue indigo raw material into a bright yellow dihydroxypyridinone compound, achieving a significant color reversal. Furthermore, this yellow compound exhibits superior coloring strength and color fastness performance compared to conventional synthetic yellow dyes such as lemon yellow in textile dyeing.
[0023] (3) The preparation method of the dihydroxypyridinone compound provided by the present invention has mild reaction conditions and good reproducibility, and can be applied to the needs of industrial production. Attached Figure Description
[0024] Figure 1 This is the 1H NMR spectrum of a dihydroxypyridinone compound.
[0025] Figure 2 This is the mass spectrum (ESI negative mode) of the dihydroxypyridinone compound.
[0026] Figure 3 This is the mass spectrum (ESI positive mode) of the dihydroxypyridinone compound.
[0027] Figure 4 This is a liquid chromatogram of a dihydroxypyridinone compound.
[0028] Figure 5 This is a staining effect diagram of the dihydroxypyridinone compound used in Example 1. Detailed Implementation
[0029] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.
[0030] Unless otherwise specified, the experimental methods used in the following examples and comparative examples are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.
[0031] The blue pigment used in the examples was provided by Nanjing Hegu Life Biotechnology Co., Ltd., while other reagents and consumables were obtained through market procurement.
[0032] The proton nuclear magnetic resonance (NMR) spectrometry was performed using an Avance II (400 MHz) NMR spectrometer; the mass spectrometry was performed using a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF).
[0033] Reaction yield = (actual mass × content) / 158) / theoretical yield. 158 is the molecular weight of the dihydroxypyridinone compound. The theoretical yield is 1 mol of dihydroxypyridinone compound theoretically produces 2 mol of dihydroxypyridinone compound.
[0034] Product content detection: HPLC was used, and the high-performance liquid chromatography detection method is described below.
[0035] Chromatographic conditions: Mobile phase: gradient elution of methanol and pure water, as shown in the gradient table below:
[0036]
[0037] Wavelength 400 nm, flow rate 1.0 mL / min, sample solution: DMSO, injection volume: 10 μL, column temperature 35℃, run time 20 min. Column: Galasil EF-C18M 4.6 mmid × 250 mm L (SN B06211801).
[0038] Example 1
[0039] This embodiment provides a method for preparing a dihydroxypyridinone compound, comprising the following steps:
[0040] 0.001 mol NaOH was added to a reaction vessel, followed by 50 mL of water and stirring to disperse the mixture. Then, 0.01 mol of chlorin (2.48 g) and 0.015 mol of potassium permanganate were added. The mixture was reacted at 30 °C for 4 h. The pH was then adjusted to 3 using sulfuric acid, and the product precipitated. The product was separated into solid and liquid components by filtration. The solid fraction was washed three times with water, dried, and separated by column chromatography to obtain 2.53 g of dihydroxypyridinone compound, with a yield of 72% and a purity of 90%.
[0041] The NMR data of the obtained dihydroxypyridinone compound are as follows ( Figure 1 ):
[0042] 1 H NMR (400 MHz, DMSO-d6) δ 9.62 (s,1H), 8.09 (s,1H), 7.73 (s,1H), 7.64 (s,1H), 7.41 (s,1H), 6.45 (s,1H).
[0043] The mass spectrometry data of the obtained dihydroxypyridinone compound are as follows ( Figure 2 , 3 ):
[0044] ESI-MS m / z: 157.0 [MH] - , 180.9 [M+Na] + .
[0045] The calculated molecular weight of the product, 158, can be easily deduced from ESI-MS, which is consistent with the molecular weight of the product structure. Furthermore, combined with the NMR data of the parent compound, it can be deduced that δ 9.62 (s, 1H) is the proton signal of the NH group on the ring of the dihydroxypyridinone, and 8.09 (s, 1H) is the proton signal of the olefinic hydrogen in the dihydroxypyridinone. This can confirm the characteristics of the product. The proton of the amino group is consistent with the two peaks at δ 7.73 (s, 1H) and 7.64 (s, 1H). Combined with mass spectrometry, it can be determined that 7.41 (s, 1H) and 6.45 (s, 1H) are the proton signals of the dihydroxy group, thus confirming the structure of the product as dihydroxypyridinone.
[0046] The liquid chromatography data of the obtained dihydroxypyridinone compound are as follows: Figure 4 As shown.
[0047] Example 2
[0048] This embodiment provides a method for preparing a dihydroxypyridinone compound, comprising the following steps:
[0049] 0.01 mol NaOH was added to a reaction vessel, followed by 50 mL of water and stirring to disperse the product. Then, 0.01 mol of chlorine and 0.015 mol of hydrogen peroxide were added. The mixture was reacted at 25 °C for 5 h. The pH was then adjusted to 4 using sulfuric acid, and the product precipitated. The product was separated into solid and liquid components by filtration. The solid fraction was washed three times with water and dried to obtain 2.79 g of dihydroxypyridinone compound, with a yield of 75% and a purity of 85%.
[0050] Example 3
[0051] This embodiment provides a method for preparing a dihydroxypyridinone compound, comprising the following steps:
[0052] 0.002 mol NaOH was added to a reaction vessel, followed by 50 mL of water and stirring to disperse the mixture. Then, 0.01 mol of chlorine and 0.017 mol of potassium permanganate were added. The mixture was reacted at 28 °C for 6 h. The pH was then adjusted to 5 using hydrochloric acid, and the product precipitated. Solid-liquid separation was performed by filtration. The solid fraction was washed three times with water and dried to obtain 2.66 g of dihydroxypyridinone compound, with a yield of 69% and a purity of 82%.
[0053] Example 4
[0054] This embodiment provides a method for preparing a dihydroxypyridinone compound, comprising the following steps:
[0055] 0.001 mol of potassium tert-butoxide was added to a reaction vessel, followed by 100 mL of water and stirring to disperse the mixture. Then, 0.01 mol of chlorpyrifos and 0.02 mol of potassium permanganate were added. The mixture was reacted at 25 °C for 6 h. The pH was then adjusted to 6 using hydrochloric acid, and the product precipitated. Solid-liquid separation was performed by filtration. The solid fraction was washed three times with water and dried to obtain 2.49 g of dihydroxypyridinone compound, with a yield of 67% and a purity of 85%.
[0056] Example 5
[0057] This comparative example provides a method for preparing a dihydroxypyridinone compound, which differs from Example 1 only in that the amount of NaOH is increased to 0.005 mol, while other aspects are the same as in Example 1.
[0058] Results: 1.08 g of dihydroxypyridinone compound was obtained, with a yield of 28% and a purity of 82%.
[0059] Example 6
[0060] This comparative example provides a method for preparing a dihydroxypyridinone compound, which differs from Example 2 only in that 0.015 mol of hydrogen peroxide is replaced with 0.01 mol of potassium permanganate, while other aspects are the same as in Example 2.
[0061] Results: 0.94 g of dihydroxypyridinone compound was obtained, with a yield of 25% and a purity of 84%.
[0062] Example 7
[0063] This comparative example provides a method for preparing a dihydroxypyridinone compound, which differs from Example 3 only in that the reaction time is shortened to 2 hours, while other aspects are the same as in Example 3.
[0064] Results: 0.76 g of dihydroxypyridinone compound was obtained, with a yield of 21% and a purity of 87%.
[0065] Example 8
[0066] This comparative example provides a method for preparing a dihydroxypyridinone compound, which differs from Example 4 only in that the pH is adjusted to 7 with hydrochloric acid, while other aspects are the same as in Example 4.
[0067] Results: Only a small amount of product precipitated, yielding 0.47 g of dihydroxypyridinone compound, with a yield of 12% and a purity of 81%.
[0068] A comparison of Examples 1-4 and Examples 5-8 shows that high concentrations of alkali may damage the substrate, thereby affecting product formation; reducing the amount of oxidant and the reaction time will reduce the reaction yield; and adjusting the pH of the reaction solution to be too high will also reduce the yield.
[0069] Application Example 1
[0070] This application example demonstrates the use of a dihydroxypyridinone compound in staining, including the following steps:
[0071] The dihydroxypyridinone synthesized in the above examples was used to dye cotton fabrics according to the following process: 2% (owf) dihydroxypyridinone compound, 2% (owf) leveling agent, 1L distilled water were added, stirred evenly, and the pH was adjusted to 7. Dyeing was carried out at 25℃ for 10 minutes. After dyeing, the dyed fabric was removed, rinsed with clean water until the wash water was clear, and then dried using a dryer or by air drying. The dyeing effect is as follows. Figure 5 As shown.
[0072] Comparative Application Example 1
[0073] This application example provides an application of curcumin in staining, which differs from Application Example 1 only in that hydroxypyridinone is replaced with curcumin in equal amounts, while other aspects are the same as in Application Example 1.
[0074] The dyed fabrics provided in Case 1 and Comparative Application Example 1 were tested for K / S value, dyeing rate (%), light fastness, water fastness, dry heat fastness, acid spot fastness, and wet rubbing fastness. The K / S value of color depth was determined using a colorimeter; the test for lightfastness was conducted in accordance with GB / T 8427-2019 "Textiles - Tests for Colorfastness to Artificial Light: Xenon Arc"; the test for waterfastness was conducted in accordance with GB / T 5713-2013 "Textiles - Tests for Colorfastness to Water"; the test for dry heatfastness was conducted in accordance with GB / 5718-1997 "Textiles - Tests for Colorfastness to Dry Heat (excluding Hot Pressing)"; the test for acid spotfastness was conducted in accordance with GB / T 5715-2013 "Textiles - Tests for Colorfastness to Acid Spot"; and the test for wet rubbingfastness was conducted in accordance with GB / T 3920-2008 "Textiles - Tests for Colorfastness to Rubbing".
[0075] The test results are shown in Table 1.
[0076] Table 1
[0077]
[0078] As shown in the table, compared with curcumin, the dihydroxypyridinone compound of this invention exhibits more prominent application advantages: its K / S value (10.4) and dyeing rate (92.3%) are higher, which means that the coloring strength and dyeing effect are better; at the same time, all fastness properties are better—the light fastness reaches level 5 (curcumin is level 2-3, and it is easy to fade under light), the water fastness, dry heat fastness, and wet rubbing fastness all reach level 5, and the acid spot fastness also reaches level 4-5. Overall, it is more competitive in terms of coloring ability and stability.
[0079] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.
Claims
1. A bis-hydroxypyridinone compound characterized by, The double-hydroxypyridone compound has the following structure: 。 2. A process for the preparation of a bis-hydroxypyridone compound according to claim 1, characterized in that, The preparation method comprises the following steps: mixing the quinoline blue and the oxidant, reacting in the presence of an alkali solution to obtain the double-hydroxypyridone compound.
3. The production method according to claim 2, characterized by, The oxidant comprises any one or a combination of both of potassium permanganate or hydrogen peroxide.
4. The production method according to claim 2, characterized by, The molar ratio of the quinoline blue and the oxidant is 1:(1-2).
5. The preparation method according to claim 2, characterized in that, The alkali in the alkali solution comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or potassium tert-butoxide.
6. The production method according to claim 5, wherein The molar ratio of the quinoline blue and the alkali is 1:(0.1-1).
7. The preparation method according to claim 2, characterized in that, The temperature of the reaction is 25-30℃, and the time of the reaction is 2-8h.
8. The preparation method according to claim 2, characterized in that, The reaction further comprises a post-treatment step: adding an acid to adjust the pH value of the reaction solution, then solid-liquid separation, washing and drying the solid to obtain the double-hydroxypyridone compound.
9. The production method according to claim 8, characterized by, The acid comprises any one or a combination of at least two of hydrochloric acid or sulfuric acid; the pH value is adjusted to 3-7.
10. Application of the double-hydroxypyridone compound of claim 1 as a yellow dye in dyeing.