Nitrogen heterocyclic ring substituted azopyridone dye and preparation method thereof

Abstract

The invention discloses a nitrogen heterocyclic ring substituted azopyridone dye and a preparation method thereof, and belongs to the technical field of fine chemical engineering. The structural general formula of the azopyridone dye is shown in the specification (an azo formula and a hydrazone formula are both established), wherein X1, X2, X3, X4 and X5 are respectively and independently selected from one of nitro, hydrogen, halogen atoms, cyano, methyl, isopropyl and methoxyl; r substituent is selected from one of the following structures; an R substituent group is introduced to the N site of pyridone, so that the problem that the solubility of the azopyridone dye in an organic solvent is relatively low can be effectively solved. The solubility of the azopyridone dye disclosed by the invention in an organic solvent is greater than or equal to 5g / 100g, the dye ensures excellent light and heat resistance stability, the color coordinates meet the standard yellow range, and the azopyridone dye has the feasibility of preparing optical devices and full-color high-stability display materials.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of nitrogen-containing heterocyclic substituted azopyridinone dyes and its preparation method, belong to fine chemical technology field. BACKGROUND

[0002] In the field of photolithography display, micro display, AR, etc., as a key functional material, the performance of color filter determines the resolution, color reproduction and long-term stability of display device. Due to the strong chromophore of azo group and the strong chemical stability of pyridinone ring in the molecular structure, azopyridinone dyes show excellent molar absorption coefficient, light resistance and chemical corrosion resistance in the yellow to orange band range, and have become the core chromophoric component of colorant.

[0003] In the preparation process of color filter, the design and synthesis of dye need to meet the solubility of dye in PGMEA ≥5g / 100g. However, the existing azopyridinone dyes generally have the technical bottleneck of "solubility in PGMEA less than 5g / 100g", and the mass concentration is difficult to break through 5wt%, which cannot meet the application requirements of high color gamut color filter. Through in-depth research, it is found that the core reasons leading to this bottleneck are as follows: First, the aggregation behavior of dye molecules aggravates the dissolution barrier. The molecular structure of azopyridinone contains large π conjugated system, adjacent molecules are easy to form stable dimers or multimers through π-π stacking interaction. At the same time, the hydroxyl group in the molecule is easy to form intermolecular hydrogen bond with the carbonyl group and nitrogen atom of other molecules, which further promotes the formation of aggregate. Therefore, it has been reported that by introducing POSS substituent with stereostructure (CN119119760B) to break the aggregation between molecules and increase the distance between single molecules, the solubility is improved.

[0004] Second, the low solubility caused by the mismatch between the molecular polarity and PGMEA. For example, the existing reports introduce alkyl, alkoxy, ester group (Coloration Technology, 133, 158-164, 2016. Molecules, 2022, 27, 6601.) and hydroxyl group (Coloration Technology, 133, 158-164, 2016.) at the N position of pyridone, the solubility of the synthesized dyes is less than 5g / 100g. This is because the alkyl group is a non-polar group with strong hydrophobicity, which reduces the molecular polarity and makes it difficult to match the polarity of PGMEA; the introduction of alkoxy will shift the electron cloud of O to N atom, weaken the local dipole moment of O atom, and cause the mismatch between the dye molecule and PGMEA; the introduction of ester group will increase the local polarity near the N position of pyridone, causing uneven distribution of the overall polarity of the dye molecule, although it can temporarily combine with the ester group of PGMEA, but it cannot cover the stability of the whole molecule in the solvent. Therefore, the solubility is poor.

[0005] In summary, in the molecular design of azo pyridone dyes, there is an urgent need for a modification strategy that can precisely regulate the matching of molecular polarity and PGMEA polarity, while inhibiting molecular aggregation without losing dye performance. Heterocyclic substituents such as morpholine, piperidine, piperazine, pyrimidine, pyridine, and imidazole have unique structural advantages - containing polar heteroatoms N or N, O, which can adjust the molecular polarity, and the cyclic structure can provide steric hindrance to inhibit molecular aggregation. While ensuring the compatibility of the conjugated backbone, the problem of low solubility of azo pyridone dyes is solved, which becomes an ideal choice to solve the above technical bottlenecks and lays a solid foundation for the research and application of high-performance colored color filters. SUMMARY

[0006] To solve the above problems, the present application provides an azo pyridone dye with excellent solubility and color within the standard yellow range and a preparation method thereof. The diazo component of the dye contains an aromatic primary amine with a benzene ring desensitizing group or an aromatic primary amine with a benzene ring sensitizing group, and the coupling component is a pyridone substituted with morpholine, imidazole, pyridine, pyrimidine, and piperazine connected by a flexible chain at the N position. The introduction of heterocyclic rings at the N position of the coupling component pyridone can effectively neutralize the rigid backbone of the pyridone ring, thereby enhancing the interaction between the dye molecule and the solvent, while weakening the aggregation between the molecules, thereby improving the solubility of the dye.

[0007] To achieve the above purpose, the present application adopts the following technical scheme: In a first aspect, the present application provides a nitrogen-containing heterocyclic substituted azo pyridone dye with excellent solubility, and the structure general formula of the azo pyridone dye is shown in formula I (both azo and hydrazone are true):

[0008] Formula I In Formula I, X1, X2, X3, X4, X5 are each independently selected from one of nitro, hydrogen, halogen atom, cyano, methyl, isopropyl, methoxy; R is one of I-1, I-2, I-3, I-4, I-5, I-6: ; Wherein, P, Q are each independently selected from one of the following general structures: 、 、 、 、 、 、 、 、 、 、 , -H, -F, -Cl, -Br, -I; Wherein, 0 < m < 22, m is an integer.

[0009] In a second aspect, the present application provides a preparation method of the above azo pyridone dye, comprising the following steps: (1) adding naphthalene disulfonic acid and ethyl acetate into a reaction container, stirring and dissolving at 0-60℃, transferring the solution to an ice bath, adding alkyl nitrite drop by drop, then adding diazonium component into the reaction container in batches to carry out diazotization reaction, after the reaction is completed, filtering to obtain solid diazonium salt; (2) adding I-1-I-6 as coupling component into the reaction container, dissolving with water, then stirring at room temperature, cooling to 0-5℃, adding the solid diazonium salt obtained in step (1) in batches to carry out coupling reaction, and gradually increasing the reaction temperature to room temperature; (3) after the reaction is completed, adding water to precipitate the solid, then adding alkali to the obtained dye mixture to adjust the pH value of the solution to neutral; (4) filtering, washing with water, and column chromatography to obtain the dye.

[0010] Further, the structural formula of the diazonium component is shown in Formula II: .

[0011] Further, the structural formula of the coupling component is shown in Formula III: .

[0012] Further, in step (1), the molar ratio of the diazonium component, naphthalene disulfonic acid and alkyl nitrite is 1:1:1.2-1:1.5:1.5, preferably 1:1:1.5; the naphthalene disulfonic acid is 1,5-naphthalene disulfonic acid, 2,6-naphthalene disulfonic acid or 2,7-naphthalene disulfonic acid, preferably 1,5-naphthalene disulfonic acid; the alkyl nitrite is tert-butyl nitrite, n-butyl nitrite or isoamyl nitrite, preferably tert-butyl nitrite; the diazotization reaction time is 10-40 min.

[0013] Further, in step (2), the volume ratio of the coupling component and water is 1:10-1:100, preferably 1:50; the molar ratio of the coupling component and the diazonium component is 1:1-1.05:1; the coupling reaction time is 2-8 h.

[0014] Further, in step (3), the base is sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide, preferably sodium carbonate.

[0015] Further, in step (3), the pH value of the obtained dye mixture solution is adjusted to 6-7 by adding a base.

[0016] Further, in step (4), the organic solvent used for column chromatography is ethyl acetate-petroleum ether mixed solvent, and the volume ratio of the solvents is ethyl acetate: petroleum ether = 1:5-2:1, preferably ethyl acetate: petroleum ether = 1:1.

[0017] The azopyridone dye has a single absorption peak in the yellow spectral range, a narrow peak shape and a small half-peak width, can accurately absorb light of a specific wavelength, and makes the absorption of the dye in the yellow spectral range more concentrated and efficient. Meanwhile, the molar absorption coefficient of the synthesized dye is high, which is 19000 mol -1 ·cm -1 The above shows that the dye has high brightness and can present bright color in a solvent. The dye has excellent light and heat stability. The color difference of the film sheet prepared from the dye is less than 3 after long-term ultraviolet irradiation under an ultraviolet lamp. The color difference of the film sheet is between 2 and 5 after high-temperature baking at 220℃, which belongs to a small or moderate color difference range. Meanwhile, the solubility of the dye in organic solvents such as PGMEA can reach more than 5 g / 100 g, solving the defect of insufficient solubility of such dyes in organic solvents. The designed dye improves the solubility of the dye while ensuring the light and heat stability, thereby improving the utilization rate of the dye. The color coordinates of the film sheet are plotted in the CIE 1931 coordinate, and the designed dye is in the standard yellow range and close to the edge of the CIE diagram, showing higher brightness and color purity. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 (a) is the UV maximum absorption spectrum of Y-1 in PGMEA.

[0019] Figure 1 (b) is the UV maximum absorption spectrum of Y-2 in PGMEA.

[0020] Figure 1 (c) is the UV maximum absorption spectrum of Y-3 in PGMEA.

[0021] Figure 1 (d) is the UV maximum absorption spectrum of Y-7 in PGMEA.

[0022] Figure 1 (e) is the UV maximum absorption spectrum of Y-10 in PGMEA.

[0023] Figure 2 (a) is the film transmittance spectrum of Y-1 before and after thermal baking.

[0024] Figure 2 (b) is the film transmittance spectrum of Y-2 before and after thermal baking.

[0025] Figure 2 (c) is the film transmittance spectrum of Y-3 before and after thermal baking.

[0026] Figure 2 (d) is the film transmittance spectrum of Y-7 before and after thermal baking.

[0027] Figure 2 (e) is the film transmittance spectrum of Y-10 before and after thermal baking.

[0028] Figure 3 (a) is the film transmittance spectrum of Y-1 before and after light exposure.

[0029] Figure 3 (b) is the film transmittance spectrum of Y-2 before and after light exposure.

[0030] Figure 3 (c) is the film transmittance spectrum of Y-3 before and after light exposure.

[0031] Figure 3 (d) is the film transmittance spectrum of Y-7 before and after light exposure.

[0032] Figure 3 (e) is the film transmittance spectrum of Y-10 before and after light exposure.

[0033] Figure 4Digital photo of dye-based color film.

[0034] Figure 5 Point coordinates of dye-based color film in CIE diagram. DETAILED DESCRIPTION

[0035] The following further describes the present application in conjunction with specific embodiments. The following examples are only a part of the content of the present application and cannot be used as a basis for limiting the present application. Non-essential changes made on the basis of the present application still fall within the scope of the present application.

[0036] The specific structures of the corresponding nitrogen-containing heterocycle-substituted azopyridinone dyes in Examples 1-12 are shown in Table 1.

[0037] Table 1 Structure of nitrogen-containing heterocycle-substituted azopyridinone dyes in Examples 1-12

[0038] Example 1 The method for synthesizing dye Y-1 in this example includes the following steps: (1) Preparation of coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and N-aminopropyl morpholine (14.42 g 0.1 mol) was added to a single-necked flask and stirred and heated to reflux for 18 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the solution changed from colorless to orange yellow, and the morpholino-substituted pyridinone intermediate Z-1 was obtained. The product was extracted with dichloromethane and then subjected to column chromatography with a developing agent of methanol:dichloromethane = 1:10, and the yield was 83%.

[0039] (2) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred, and 100 mL of ethyl acetate was added. The solution was stirred at 50°C until completely dissolved, transferred to an ice bath at 0-5°C, and then 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise, followed by the addition of 4-nitro-2-chloroaniline (0.52 g 3 mmol) in batches for diazotization reaction. After 15 minutes, the 4-nitro-2-chloroaniline solid diazonium salt was obtained by suction filtration.

[0040] (3) Coupling reaction: The intermediate Z-1 (0.83g 3mmol) obtained in step (1) was dissolved in water (100mL), stirred at room temperature until completely dissolved, cooled to 5℃, and the solid diazonium salt obtained in step (2) was added in batches to the coupling component to carry out the coupling reaction. The reaction temperature was gradually increased from 5℃ to room temperature. After 3 hours, water was added to precipitate the solid. Then sodium carbonate was added to the obtained dye mixture to adjust the pH to 6. The mixture was filtered and washed with water until the filtrate was colorless. Yellow dye Y-1 was obtained by column chromatography.

[0041] 1 H NMR (400 MHz, DMSO- d 6) δ 8.10 (m, 1H), 7.36 (dd, J = 8.2, 2.5 Hz, 1H), 7.27 (d, J = 8.1 Hz, 1H), 5.12 (d, J = 0.9 Hz, 1H), 2.02 (m, 3H), 1.25 (d, J =6.9 Hz, 6H). HRMS (ESI, m / z [MH] - calcd for C 14 H 18 The results of N3O3, 276.1426; found, 276.1352, indicate that the synthesized intermediate Z-1 has the correct structure.

[0042] HRMS (ESI, m / z [MH] - calcd for C 20 H 20 The results of finding ClN6O5, 459.1262; found, 459.1189, indicate that the synthesized dye Y-1 has the correct structure.

[0043] Figure 1 (a) is the UV maximum absorption spectrum of azopyridone dye Y-1 in PGMEA.

[0044] Example 2 The method for synthesizing dye Y-2 in this embodiment includes the following steps: (1) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2,6-diisopropylaniline (0.67 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2,6-diisopropylaniline was obtained by filtration.

[0045] (2) Coupling reaction: Dissolve intermediate Z-1 (0.83g 3mmol) in water (100mL), stir until completely dissolved at room temperature, cool to 5℃, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5℃ to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-2 by column chromatography.

[0046] 1 H NMR (400 MHz, DMSO- d 6) δ 7.98 (s, 2H), 3.87 (t, J = 7.5 Hz, 2H), 3.60 (t, J = 4.6 Hz, 4H), 3.35 (s, 2H), 3.07 (p, J = 6.9 Hz, 2H), 2.47 (6H), 2.38(s, 3H), 1.72 (p, J = 7.5 Hz, 2H), 1.13 (d, J = 6.9 Hz, 12H). HRMS (ESI, m / z [MH] - calcd for C 26 H 33 The results N6O5, 509.2591; found, 509.2512 indicate that the synthesized dye Y-2 has the correct structure.

[0047] Figure 1 (b) is the UV maximum absorption spectrum of azopyridone dye Y-2 in PGMEA.

[0048] Example 3 The method for synthesizing dye Y-3 in this embodiment includes the following steps: (1) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-bromo-2,6-diisopropylaniline (0.77 g 3 mmol) was added in batches to carry out the diazotization reaction. After 16 minutes, the solid diazonium salt of 4-bromo-2,6-diisopropylaniline was obtained by filtration.

[0049] (2) Coupling reaction: Dissolve intermediate Z-1 (0.83 g 3 mmol) in water (100 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 6, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-3 by column chromatography.

[0050] 1 H NMR (400 MHz, DMSO- d 6) δ 7.32 (s, 2H), 3.87 (m, 2H), 3.55 (t, J =4.6 Hz, 2H), 3.00 (p, J = 6.9 Hz, 2H), 2.36 (9H), 1.68 (p, J = 7.1 Hz, 2H), 1.10(d, J = 6.9 Hz, 12H). HRMS (ESI, m / z [MH] - calcd for C 26 H 33 The results BrN5O3, 542.1845; found, 542.1769, indicate that the synthesized dye Y-3 has the correct structure.

[0051] Figure 1 (c) is the UV maximum absorption spectrum of azopyridone dye Y-3 in PGMEA.

[0052] Example 4 The method for synthesizing dye Y-4 in this embodiment includes the following steps: (1) Preparation of the coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and 3-amino-6-isopropylpyridine (13.62 g 0.1 mol) was added to a single-necked flask and stirred and heated under reflux for 20 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the solution changed from colorless to orange-yellow, yielding the pyridyl-substituted pyridinone intermediate Z-2. The product was extracted with dichloromethane and then subjected to column chromatography with methanol:dichloromethane = 1:12 as the developing solvent, yielding 85%.

[0053] (2) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2-chloroaniline (0.52 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2-chloroaniline was obtained by filtration.

[0054] (3) Coupling reaction: Dissolve intermediate Z-2 (0.81 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (2) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water after 5 hours to precipitate the solid, then add sodium carbonate to the obtained dye mixture, adjust the pH to 6, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-4 by column chromatography.

[0055] 1 H NMR (400 MHz, DMSO- d 6) δ 8.10 (m, 1H), 7.36 (dd, J = 8.2, 2.5 Hz, 1H), 7.27 (d, J = 8.1 Hz, 1H), 5.12 (d, J = 0.9 Hz, 1H), 2.02 (m, 3H), 1.25 (d, J =6.9 Hz, 6H). HRMS (ESI, m / z [MH] - calcd for C 15 H 14 The results of N3O2, 268.1164; found, 268.1089, indicate that the synthesized intermediate Z-2 has the correct structure.

[0056] 1 H NMR (400 MHz, Chloroform- d ) δ 8.43 (d, J = 2.5 Hz, 1H), 8.38 (d, J =2.4 Hz, 1H), 8.28 (dd, J = 9.1, 2.4 Hz, 1H), 7.96 (d, J = 9.1 Hz, 1H), 7.55 (dd, J = 8.3 Hz, 2.5 Hz, 1H), 7.41 (d, J = 8.3 Hz, 1H), 3.23 (p, J = 6.9 Hz, 1H), 2.75(s, 3H), 1.38 (d, J = 6.9 Hz, 6H). HRMS (ESI, m / z [MH] - calcd for C 21 H 16 The results of finding ClN6O4, 451.1000, and finding 451.0928 indicate that the synthesized dye Y-4 has the correct structure.

[0057] Example 5 The method for synthesizing dye Y-5 in this embodiment includes the following steps: (1) Preparation of the coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and 1-(3-aminopropyl)imidazolium (12.52 g 0.1 mol) was added to a single-necked flask and stirred and heated under reflux for 16 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the solution turned orange-yellow, yielding the imidazolyl-substituted pyridinone intermediate Z-3. The product was extracted with dichloromethane and then subjected to column chromatography with methanol:dichloromethane = 1:8 as the developing solvent, yielding 81%.

[0058] (2) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2-chloroaniline (0.52 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2-chloroaniline was obtained by filtration.

[0059] (3) Coupling reaction: Dissolve intermediate Z-3 (0.77 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-5 by column chromatography.

[0060] HRMS (ESI, m / z [MH] - calcd for C 13 H 13 The results of N4O2, 257.1117; found, 257.1052, indicate that the synthesized intermediate Z-3 has the correct structure.

[0061] HRMS (ESI, m / z [MH] - calcd for C 19 H 16 The results of finding ClN7O4, 440.0952, and finding, 440.1001 indicate that the synthesized dye Y-5 has the correct structure.

[0062] Example 6 The method for synthesizing dye Y-6 in this embodiment includes the following steps: (1) Preparation of the coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and 1-(3-aminopropyl)-4-methylpiperazine (15.73 g 0.1 mol) was added to a single-necked flask and stirred and heated under reflux for 18 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the solution turned orange-yellow, yielding the piperazine-substituted pyridinone intermediate Z-4. The product was extracted with dichloromethane and then subjected to column chromatography with methanol:dichloromethane = 1:12 as the developing solvent, yielding 79%.

[0063] (2) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2-chloroaniline (0.52 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2-chloroaniline was obtained by filtration.

[0064] (3) Coupling reaction: Dissolve intermediate Z-4 ​​(0.87 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-6 by column chromatography.

[0065] HRMS (ESI, m / z [MH] - calcd for C 15 H 21 The results of N4O2, 289.1743; found, 289.1667, indicate that the synthesized intermediate Z-4 ​​has the correct structure.

[0066] HRMS (ESI, m / z [MH] - calcd for C 21 H 23 The results of finding ClN7O4, 472.1578; found, 472.1612, indicate that the synthesized dye Y-6 has the correct structure.

[0067] Example 7 The method for synthesizing dye Y-7 in this embodiment includes the following steps: (1) Preparation of the coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and 5-aminopyrimidine (9.51 g 0.1 mol) was added to a single-necked flask and stirred and heated under reflux for 15 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, a yellow solution was obtained, yielding the pyrimidinyl-substituted pyridinone intermediate Z-5. The product was extracted with dichloromethane and then subjected to column chromatography with methanol:dichloromethane = 1:12 as the developing solvent, yielding 77%.

[0068] (2) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2,6-diisopropylaniline (0.67 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2,6-diisopropylaniline was obtained by filtration.

[0069] (3) Coupling reaction: Dissolve intermediate Z-5 (0.68 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-7 by column chromatography.

[0070] HRMS (ESI, m / z [MH] - calcd for C 11 The results of H7N4O2, 227.0647; found, 227.0632, indicate that the synthesized intermediate Z-5 has the correct structure.

[0071] HRMS (ESI, m / z [MH] - calcd for C 23 H 22 The results N7O4, 460.1812; found, 460.1849. indicate that the synthesized dye Y-7 has the correct structure.

[0072] Figure 1 (d) is the UV maximum absorption spectrum of azopyridone dye Y-7 in PGMEA.

[0073] Example 8 The method for synthesizing dye Y-8 in this embodiment includes the following steps: (1) Preparation of the coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and 3-(piperidin-1-yl)propyl-1-amine (14.22 g 0.1 mol) was added to a single-necked flask and stirred and heated under reflux for 18 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, a yellow solution was obtained, yielding the piperidinyl-substituted pyridinone intermediate Z-6. The product was extracted with dichloromethane and then subjected to column chromatography with methanol:dichloromethane = 1:10 as the developing solvent, yielding 75%.

[0074] (2) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2-chloroaniline (0.52 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2-chloroaniline was obtained by filtration.

[0075] (3) Coupling reaction: Dissolve intermediate Z-6 (0.83 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-8 by column chromatography.

[0076] HRMS (ESI, m / z [MH] - calcd for C 15 H 20 The results N3O2, 274.1634; found, 274.1532. indicate that the synthesized intermediate Z-6 has the correct structure.

[0077] HRMS (ESI, m / z [MH] - calcd for C 21 H 22 The results of ClN6O4, 458.1469; found, 458.1510, indicate that the synthesized dye Y-8 has the correct structure.

[0078] Example 9 The method for synthesizing dye Y-9 in this embodiment includes the following steps: (1) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-methoxy-2,6-diisopropylaniline (0.62 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-methoxy-2,6-diisopropylaniline was obtained by filtration.

[0079] (2) Coupling reaction: Dissolve intermediate Z-1 (0.83 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-9 by column chromatography.

[0080] HRMS (ESI, m / z [MH] - calcd for C 27 H 36 The results N5O4, 494.2846; found, 494.2837 indicate that the synthesized dye Y-9 has the correct structure.

[0081] Example 10 The method for synthesizing dye Y-10 in this embodiment includes the following steps: (1) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2-isopropylaniline (0.62 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2-isopropylaniline was obtained by filtration.

[0082] (2) Coupling reaction: Dissolve intermediate Z-1 (0.83 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-10 by column chromatography.

[0083] HRMS (ESI, m / z [MH] - calcd for C 23 H 27 The results N6O5, 467.2121; found, 467.2148. indicate that the synthesized dye Y-10 has the correct structure.

[0084] Example 11 The method for synthesizing dye Y-11 in this embodiment includes the following steps: (1) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2-cyano-6-bromoaniline (0.73 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2-cyano-6-bromoaniline was obtained by filtration.

[0085] (2) Coupling reaction: The intermediate Z-1 (0.83 g 3 mmol) was dissolved in water (150 mL), stirred at room temperature until completely dissolved, cooled to 5 °C, and the solid diazonium salt obtained in step (1) was added in batches to the coupling component to carry out the coupling reaction. The reaction temperature was gradually increased from 5 °C to room temperature. After 4 hours, water was added to precipitate the solid. Then sodium carbonate was added to the obtained dye mixture to adjust the pH to 7. The mixture was filtered and washed with water until the filtrate was colorless. The yellow dye Y-11 was obtained by column chromatography.

[0086] HRMS (ESI, m / z [MH] - calcd for C 21 H 19 The results BrN7O5, 529.0709; found, 529.0714. indicate that the synthesized dye Y-11 has the correct structure.

[0087] Example 12 The method for synthesizing dye Y-12 in this embodiment includes the following steps: (1) Diazotization reaction: 1,5-naphthalenedisulfonic acid (0.86 g 3 mmol) was placed in a 250 mL beaker and stirred. 100 mL of ethyl acetate was added and stirred at 55 °C until completely dissolved. The solution was transferred to an ice bath at 0~5 °C and 90% tert-butyl nitrite (0.52 g 4.5 mmol) was added dropwise. Then 4-nitro-2,6-dimethylaniline (0.50 g 3 mmol) was added in batches to carry out the diazotization reaction. After 20 minutes, the solid diazonium salt of 4-nitro-2,6-dimethylaniline was obtained by filtration.

[0088] (2) Coupling reaction: Dissolve intermediate Z-1 (0.83 g 3 mmol) in water (150 mL), stir until completely dissolved at room temperature, cool to 5 °C, add the solid diazonium salt obtained in step (1) to the coupling component in batches to carry out the coupling reaction, gradually increase the reaction temperature from 5 °C to room temperature, add water to precipitate the solid after 4 hours, then add sodium carbonate to the obtained dye mixture, adjust the pH to 7, filter and wash with water until the filtrate is colorless, and obtain yellow dye Y-12 by column chromatography.

[0089] HRMS (ESI, m / z ) [M-H] - calcd for C 22 H 25 N6O5, 454.1965; found, 454.1977.

[0090] Example 13 Five dyes Y-1, Y-2, Y-3, Y-7 and Y-10 were selected as representatives to prepare dye resins, and the dyes were tested for ultraviolet maximum absorption spectrum, solubility, film light stability and film thermal stability.

[0091] The dyes, acrylic resins and PGMEA were proportionally prepared into dye resin solutions, which were spin-coated on glass slices to prepare resin slices. The ultraviolet maximum absorption wavelength, molar absorption coefficient, solubility and transmittance of the dye resins in the solutions were shown in Table 2; the values of the prepared dye resins before and after thermal baking and the calculated color difference were shown in Table 3; the resin slices of the prepared dye resins before and after light irradiation and the calculated color difference were shown in Table 4; the transmittance spectrum of the films of the prepared dye resins before and after thermal baking and light irradiation were shown in Figure 2 and Figure 3 ; the color digital photos of the prepared dye resins were shown in Figure 4 ; and the CIE point coordinates of the prepared dye resins were shown in Figure 5 .

[0092] The calculation formula of the color difference value was as follows:

[0093] Wherein, L1, a1 and b1 were the initial color values of the film, and L2, a2 and b2 were the color values of the film after light irradiation or baking.

[0094] Table 2 Performance of five dyes in solvent PGMEA

[0095] Table 3 Color values of five dye resins before and after baking

[0096] Table 4 Color values of five dye resins before and after light irradiation

[0097] According to the ultraviolet maximum absorption wavelength of the representative dyes provided in Table 1 in the solvent PGMEA, it could be seen that the synthesized dyes were all in the yellow spectral range, and the molar absorption coefficient of the dyes was 19000~39000 L·mol-1 ·cm -1 , indicating that the dye has high brightness. By testing the solubility of the dye, it is found that the solubility of the synthesized dye is >5 g / 100 g, indicating that the introduction of heterocyclic substituents at the N position of pyridone has a good effect on improving the solubility of the dye. This is because the introduced heterocyclic substituents contain heteroatoms N or O, which have higher electronegativity than C, so that the heterocyclic region forms a local dipole moment, and the heteroatom N is a strong hydrogen bond acceptor, which can form hydrogen bond combination with PGMEA, which is beneficial to improve the solubility of the dye. The color difference data of 5 dye resins before and after baking in Table 2 is less than 3 or between 3-6, indicating that the azo pyridone dye has good thermal stability, and the color difference before and after baking is small or moderate, and the color change is small. The color difference data of the dye resins before and after light in Table 3 is less than 2, indicating that the azo pyridone dye molecule has good light stability, and the color difference data before and after light is less than 3, which belongs to the range of small color difference, and the color change is invisible to the naked eye.

[0098] Figure 4 The digital photos corresponding to the five dye resins can be seen that the prepared dye resins have bright chroma and high transmittance, and the school emblem of Dalian University of Technology can be clearly seen.

[0099] Figure 5 The point coordinates of the five dye resins in the CIE diagram can be seen that the five dye resins are located in the standard yellow region.

[0100] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A nitrogen-containing heterocyclic substituted azopyridone dye, characterized in that, The general structural formula of the azopyridone dye is shown in Formula I: Formula I In Formula I, X1, X2, X3, X4, and X5 are each independently selected from one of nitro, hydrogen, halogen atom, cyano, methyl, isopropyl, and methoxy. R is one of I-1, I-2, I-3, I-4, I-5, and I-6: ； Wherein, P and Q are independently selected from one of the following structural formulas: 、 、 、 、 、 、 、 、 、 、 、-H、-F、-Cl、-Br、-I; Where 0 < m < 22, and m is an integer.

2. A method for preparing a nitrogen-containing heterocyclic substituted azopyridone dye as described in claim 1, characterized in that, Includes the following steps: (1) Add naphthalenebissulfonic acid and ethyl acetate to the reaction vessel, stir and dissolve at 0~60℃, transfer the solution to an ice bath, add alkyl nitrite dropwise, and then add the diazonium component in batches to the reaction vessel for diazotization reaction. After the reaction is completed, filter to obtain solid diazonium salt. (2) I-1~I-6 are added to the reaction vessel as coupling components, dissolved in water and stirred at room temperature. After cooling to 0~5℃, the solid diazonium salt obtained in step (1) is added in batches to carry out the coupling reaction. The reaction is gradually raised to room temperature. (3) After the reaction is complete, water is added to precipitate the solid, and then alkali is added to the obtained dye mixture to adjust the pH value of the solution to neutral. (4) The dye is obtained by filtration, washing with water and column chromatography.

3. The preparation method according to claim 2, characterized in that, The structural formula of the diazo component is shown in Formula II: 。 4. The preparation method according to claim 2, characterized in that, The structural formula of the coupling component is shown in Figure III: 。 5. The preparation method according to claim 2, characterized in that, In step (1), the molar ratio of the diazo component, naphthalene disulfonic acid, and alkyl nitrite is 1:1:1.2 to 1:1.5:1.5; the naphthalene disulfonic acid is 1,5-naphthalene disulfonic acid, 2,6-naphthalene disulfonic acid, or 2,7-naphthalene disulfonic acid; the alkyl nitrite is tert-butyl nitrite, n-butyl nitrite, or isoamyl nitrite; and the diazotization reaction time is 10 to 40 minutes.

6. The preparation method according to claim 2, characterized in that, In step (2), the volume ratio of the coupling component to water is 1:10 to 1:100; the molar ratio of the coupling component to the diazo component is 1:1 to 1.05:1; and the coupling reaction time is 2 to 8 hours.

7. The preparation method according to claim 2, characterized in that, In step (3), the alkali is sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide.

8. The preparation method according to claim 2, characterized in that, In step (4), the organic solvent used for column chromatography is a mixture of ethyl acetate and petroleum ether, and the volume ratio of the solvent used is ethyl acetate: petroleum ether = 1:5~2:1.

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