Synthesis method of diphenyl ether anthraquinone dye
Through a one-step reaction method, 1,4-dichloroanthraquinone reacts with p-aminobenzene substances under mild conditions to generate high yield and low cost diphenyl ether anthraquinone dyes, solving the problems of poor solubility and insufficient heat and sun resistance in traditional anthraquinone dyes, and achieving dye synthesis suitable for industrial production and high heat and sun resistance applications.
Patent Information
- Application Number
- CN202411750627.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-09-20
- Filing Date
- 2024-12-02
- Publication Date
- 2025-06-06
AI Technical Summary
Traditional anthraquinone dyes have poor solubility and are difficult to synthesize, and are easy to react with the active groups of the main material under light and thermal conditions, resulting in color changes, making it difficult to meet the heat and sun resistance requirements of outdoor display screens and other applications.
A one-step reaction method is adopted, using 1,4-dichloroanthraquinone reacts with p-aminobenzene substances, strong bases and catalysts under mild conditions to form diphenyl ether anthraquinone dye. The reaction conditions are mild and the yield is high, which is suitable for industrial production.
The synthesis of diphenyl ether anthraquinone dyes with high yield and low cost is achieved, and the use of hazardous chemicals is avoided, the safety and environmental protection of the process is improved, and it is suitable for high heat and sun resistance applications such as outdoor display screens.
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Abstract
Description
Technical Field
[0001] The present application belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing diphenyl ether anthraquinone dyes (diphenyl ether anthraquinone dyes). Background Art
[0002] Guest-host liquid crystal refers to a liquid crystal as the main body, and a dichroic dye is added as the guest. Under the action of the electric field, the dichroic dye molecules are arranged along the arrangement of the liquid crystal. Because the dichroic dye absorbs light only in the direction of the long axis of the molecule and hardly absorbs light in the direction of the short axis, when the long axis direction of the dye and the liquid crystal molecule is parallel to the incident light, it appears colorless or light-colored, and when the long axis direction of the dye and the liquid crystal molecule is perpendicular to the incident light, it appears in a dark colored state or dark state. This dimming property of guest-host liquid crystal is widely used in the display field and dimming field. Dichroic dyes are mainly divided into two categories: azo type and anthraquinone type. Azo dyes usually have high order parameters and simple preparation methods. They have the advantages of good solubility, high absorption coefficient, high order and dichroic ratio in liquid crystals. However, compared with anthraquinone dyes, azo dyes have the disadvantages of poor thermal stability and poor light resistance. The application of guest-host liquid crystals in outdoor display screens, building curtain walls, and vehicles requires higher heat and light resistance products for dyes, and anthraquinone dyes are the best choice.
[0003] Traditional anthraquinone dyes usually have disadvantages such as poor solubility and difficulty in synthesis. Among anthraquinone dyes, blue, blue-green or green dyes are indispensable dyes for mixing into black, and usually contain some amino, hydroxyl and other groups. On the one hand, there are many synthesis steps and the operation process is dangerous; on the other hand, these groups are easy to react with the active groups (such as carboxyl) of the main material under light and heat conditions, and the color changes. A synthesis method of a blue anthraquinone dye is reported in the patent document with publication number CN112980212. Its preparation process requires the use of hazardous chemicals 1,5-dihydroxy-4,8-dinitroanthraquinone as a substrate, and the second step uses nitrobenzene as a solvent for the nitro substitution reaction, which has a great risk of explosion. Summary of the invention
[0004] In view of the above-mentioned deficiencies in the prior art, the present application provides a method for synthesizing diphenyl ether anthraquinone dyes which can be reacted in one step, has mild reaction conditions, high synthesis yield, is convenient for post-treatment, and is suitable for industrial production.
[0005] In order to solve the above technical problems, the technical solution adopted in the present application is: a method for synthesizing diphenyl ether anthraquinone dyes, and the corresponding reaction formula is as follows:
[0006]
[0007] Specifically, the synthesis method of the diphenyl ether anthraquinone dye mentioned in the present application comprises the following steps:
[0008] First, the compound 1,4-dichloroanthraquinone, p-aminobenzene, a strong base, and a catalyst are dissolved in an organic solvent;
[0009] Then, under a protective gas environment, at a temperature range of 70 to 120° C., the mixture dissolved in the organic solvent is controlled to react for 8 to 24 hours to obtain a diphenyl ether anthraquinone dye substance.
[0010] Furthermore, the p-aminobenzene substance has a structural formula as shown in the following formula (I):
[0011]
[0012] Wherein, the R group = -C n H 2n+1 , n = 0 to 20; or the R group = -OC n H 2n+1 , n = 1 to 20;
[0013] Or the R group = Where -R 1 =-C n H 2n+1 , n=0~20.
[0014] Furthermore, the n=0-8.
[0015] Furthermore, the n=0-5.
[0016] Furthermore, the organic solvent is selected from at least one of dimethyl ether (DME), cyclopentyl methyl ether (CPME), ethylene oxide (EO), and tetrahydrofuran (THF).
[0017] Furthermore, the organic solvent is selected from at least one of dimethyl ether (DME) and cyclopentyl methyl ether (CPME).
[0018] Furthermore, the organic solvent is selected from dimethyl ether (DME).
[0019] Furthermore, the strong base is selected from one or more of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate.
[0020] Furthermore, the catalyst is selected from one or more of palladium catalyst, zinc catalyst, iron catalyst and sodium catalyst.
[0021] Furthermore, the catalyst is a palladium catalyst, such as Pd 2 (dba) 3 .
[0022] Furthermore, the protective gas is selected from at least one of nitrogen and argon.
[0023] Furthermore, the protective gas is argon.
[0024] Furthermore, the molar ratio of the p-aminobenzene substance to 1,4-dichloroanthraquinone is 2.0-3.0:1.
[0025] Furthermore, the molar ratio of the p-aminobenzene substance to 1,4-dichloroanthraquinone is 2.0-2.7:1.
[0026] Furthermore, the molar ratio of the p-aminobenzene substance to 1,4-dichloroanthraquinone is 2.1-2.5:1.
[0027] Furthermore, the molar ratio of the strong base to 1,4-dichloroanthraquinone is 5.0-20.0:1.
[0028] Furthermore, the molar ratio of the strong base to 1,4-dichloroanthraquinone is 6.0-15.0:1.
[0029] Furthermore, the molar ratio of the strong base to 1,4-dichloroanthraquinone is 6.0-12.0:1.
[0030] Furthermore, the molar ratio of the catalyst to 1,4-dichloroanthraquinone is 0.03-0.1:1.
[0031] Furthermore, the molar ratio of the catalyst to 1,4-dichloroanthraquinone is 0.04-0.06:1.
[0032] Furthermore, the reaction temperature is 80-100° C., and the reaction time is 12-18 hours.
[0033] Advantages and beneficial effects of this application:
[0034] 1. The present application provides a method for synthesizing diphenyl ether anthraquinone dyes, which can obtain the target compound through a one-step reaction. In addition, the raw materials used in the synthesis method are common and easily available, the process operation is simple, the reaction conditions are mild, the purification is easy, the cost is low and it is suitable for industrial production; and the compound is a diphenyl ether anthraquinone dye with a symmetrical structure and has an ideal application prospect.
[0035] 2. The present application provides a method for synthesizing diphenyl ether anthraquinone dyes, in which the reaction process does not use the hazardous chemical 1,5-dihydroxy-4,8-dinitroanthraquinone as a substrate, nor does it use nitrobenzene, which has a great explosion risk, as a solvent for the nitro substitution reaction. Therefore, the entire operation process is safer and more environmentally friendly.
[0036] 3. The synthesis method of diphenyl ether anthraquinone dyes of the present application improves the yield of the final product by setting specific raw materials and specific processes, and the yield can reach more than 54.3%. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 The product prepared in Example 1 of the present application 1 H NMR spectra.
[0038] Figure 2 The product prepared in Example 2 of the present application 1 H NMR spectra.
[0039] Figure 3 The product prepared in Example 3 of the present application 1 H NMR spectra.
[0040] Figure 4 The product prepared in Example 4 of the present application 1 H NMR spectra. DETAILED DESCRIPTION
[0041] The present application can be further described in detail with reference to the following examples; however, the following examples are merely illustrative, and the present application is not limited to these examples.
[0042] Example 1
[0043] In this embodiment, the specific reaction formula is as follows:
[0044]
[0045] The specific preparation process is:
[0046] First, 12.6 g of 1,4-dichloroanthraquinone, 21.4 g of 4-octylaniline, 18.2 g of NaOH and 2.0 g of Pd 2 (dba) 3
[0047] (Tris(dibenzylideneacetone)dipalladium) was dissolved in 200 ml of DME (dimethyl ether);
[0048] Then, under the protection of argon, the mixture was heated and stirred at 80°C for 24 hours. After the reaction was completed, the mixture was poured into water, extracted with ethyl acetate, and the solvent was removed to obtain a crude product, which was first washed with a small amount of petroleum ether and then slurried with methanol to finally obtain 15.2 g of compound with a yield of 54.3%.
[0049] The obtained compounds were tested. 1 H NMR spectra Figure 1 The specific nuclear magnetic resonance test results are as follows:
[0050] 1HNMR (400MHz, DMSO-d 6 ): δ12.26(s,2H),8.39(dd,J=3.4,5.8Hz,2H),7.75
[0051] (dd, J=3.2, 6.0Hz, 2H), 7.47-7.46(m, 2H), 7.25-7.18(m.8H), 2.61(s, 4H), 1.66-1.56(m, 4H), 1.32-1.28(m, 20H), 0.90-0.87(m, 6H); It can be seen from the above test results that the product prepared in Example 1 of the present application is the compound obtained on the right side of the above reaction formula of the present application.
[0052] Example 2
[0053] In this embodiment, the specific reaction formula is as follows:
[0054]
[0055] The specific preparation process is:
[0056] First, 12.6 g of 1,4-dichloroanthraquinone, 24.27 g of 4-pentyloxyaniline, 37.4 g of K2CO3 and 2.0 g of Pd2(dba)3 were dissolved in 200 ml of DMSO (dimethyl sulfoxide);
[0057] Then, under nitrogen protection, the mixture was heated and stirred at 100°C for 12 hours. The mixture was poured into water, extracted with ethyl acetate, and the solvent was removed to obtain a crude product, which was first washed with a small amount of petroleum ether and then slurried with methanol to finally obtain 18.0 g of the compound with a yield of 70.6%.
[0058] The obtained compounds were tested. 1 H NMR spectra Figure 2 The specific NMR test results are as follows: 1H NMR (400MHz, DMSO-d 6 ): δ12.26(s,2H),8.39(dd,J=3.4,5.8Hz,2H),7.75(dd,J=3.2,6.0Hz,2H),7.47-7.46(m,2H ),7.31-7.10(m.8H),3.98(m,4H),1.66-1.56(m,4H),1.32-1.28(m,8H),0.90-0.87(m,6H).
[0059] It can be seen from the above test results that the product prepared in Example 2 of the present application is the compound obtained on the right side of the reaction formula in Example 2 of the present application.
[0060] Example 3
[0061]
[0062] The specific preparation process is:
[0063] First, 12.6 g of 1,4-dichloroanthraquinone, 51.49 g of 4-eicosylaniline, 37.4 g of K2CO3 and 2.0 g of Pd2(dba)3 were dissolved in 200 ml of DMSO (dimethyl sulfoxide);
[0064] Then, under nitrogen protection, the mixture was heated and stirred at 100°C for 12 hours. The mixture was poured into water, extracted with ethyl acetate, and the solvent was removed to obtain a crude product, which was first washed with a small amount of petroleum ether and then slurried with methanol to finally obtain 33.77 g of compound with a yield of 78.4%.
[0065] The obtained compounds were tested. 1 H NMR spectra Figure 3 The specific NMR test results are as follows: 1HNMR (400MHz, DMSO-d 6 ): δ12.26(s,2H),8.29(dd,J=3.4,5.8Hz,2H),7.75(dd,J=3.2,6.0Hz,2H),7.47-7.46(s,2H ),7.31-7.06(m.8H),2.52(m,4H),1.66-1.56(m,4H),1.32-1.28(m,68H),0.90-0.86(m,6H).
[0066] It can be seen from the above test results that the product prepared in Example 3 of the present application is the compound obtained on the right side of the reaction formula in Example 3 of the present application.
[0067] Example 4
[0068]
[0069] The specific preparation process is:
[0070] First, 12.6 g of 1,4-dichloroanthraquinone, 8.47 g of aminobenzene, 37.4 g of K2CO3 and 2.0 g of Pd2(dba)3 were dissolved in 200 ml of DMSO (dimethyl sulfoxide);
[0071] Then, under nitrogen protection, the mixture was heated and stirred at 100°C for 12 hours. The mixture was poured into water, extracted with ethyl acetate, and the solvent was removed to obtain a crude product, which was first washed with a small amount of petroleum ether and then slurried with methanol to finally obtain 14.2 g of compound with a yield of 80%.
[0072] The obtained compounds were tested. 1 H NMR spectra Figure 4 The specific NMR test results are as follows: 1HNMR (400MHz, DMSO-d 6 ): δ12.26(s,2H),8.29(dd,J=3.4,5.8Hz,2H),7.85(dd,J=3.2,6.0Hz,2H),7.51(s,2H),7.40-7.28(m.8H),7.02(m,2H).
[0073] It can be seen from the above test results that the product prepared in Example 4 of the present application is the compound obtained on the right side of the reaction formula in the above Example 4 of the present application.
[0074] First, 12.6 g of 1,4-dichloroanthraquinone, 24.27 g of 4-pentyloxyaniline, 37.4 g of K2CO3 and 2.0 g of Pd2(dba)3 were dissolved in 200 ml of DMSO (dimethyl sulfoxide);
[0075] Then, under nitrogen protection, the mixture was heated and stirred at 100°C for 12 hours. The mixture was poured into water, extracted with ethyl acetate, and the solvent was removed to obtain a crude product, which was first washed with a small amount of petroleum ether and then slurried with methanol to finally obtain 18.0 g of the compound with a yield of 70.6%.
[0076] The obtained compounds were tested. 1 H NMR spectra Figure 2 The specific NMR test results are as follows: 1HNMR (400MHz, DMSO-d 6 ): δ12.26(s,2H),8.39(dd,J=3.4,5.8Hz,2H),7.75(dd,J=3.2,6.0Hz,2H),7.47-7.46(m,2H ),7.31-7.10(m.8H),3.98(m,4H),1.66-1.56(m,4H),1.32-1.28(m,8H),0.90-0.87(m,6H).
[0077] It can be seen from the above test results that the product prepared in Example 2 of the present application is the compound obtained on the right side of the reaction formula in Example 2 of the present application.
Claims
1. A method for synthesizing diphenyl ether anthraquinone dyes, characterized in that: The corresponding reaction formula of the synthesis method is as follows:
2. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 1, characterized in that: The specific preparation process includes: First, the compound 1,4-dichloroanthraquinone, p-aminobenzene, a strong base, and a catalyst are dissolved in an organic solvent; Then, under a protective gas environment, at a temperature range of 70 to 120° C., the mixture dissolved in the organic solvent is controlled to react for 8 to 24 hours to obtain a diphenyl ether anthraquinone dye substance.
3. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 2, characterized in that: The p-aminobenzene substance has a structural formula as shown in the following formula (I): Wherein, the R group = -C n H 2n+1 , n = 0 to 20; or the R group = -OC n H 2n+1 , n = 1 to 20; or The Where -R1=-C n H 2n+1 , n = 0 to 20; The strong base is selected from one or more of sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate; The catalyst is selected from one or more of palladium catalyst, zinc catalyst, iron catalyst and sodium catalyst; the organic solvent is selected from at least one of dimethyl ether, cyclopentyl methyl ether, ethylene oxide and tetrahydrofuran; The protective gas is selected from at least one of nitrogen and argon.
4. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 3, characterized in that: The n is 0 to 8; the catalyst is a palladium catalyst; the organic solvent is selected from at least one of dimethyl ether and cyclopentyl methyl ether; and the protective gas is argon.
5. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 2, characterized in that: The molar ratio of the p-aminobenzene substance to 1,4-dichloroanthraquinone is 2.0-3.0:
1.
6. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 5, characterized in that: The molar ratio of the p-aminobenzene substance to 1,4-dichloroanthraquinone is 2.0-2.7:
1.
7. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 2, characterized in that: The molar ratio of the p-aminobenzene substance to 1,4-dichloroanthraquinone is 2.1-2.5:
1.
8. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 2, characterized in that: The molar ratio of the strong base to the 1,4-dichloroanthraquinone is 5.0-20.0:
1.
9. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 8, characterized in that: The molar ratio of the strong base to the 1,4-dichloroanthraquinone is 6.0-15.0:
1.
10. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 2, characterized in that: The molar ratio of the catalyst to the 1,4-dichloroanthraquinone is 0.03-0.1:
1.
11. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 10, characterized in that: The molar ratio of the catalyst to the 1,4-dichloroanthraquinone is 0.04-0.06:
1.
12. The method for synthesizing diphenyl ether anthraquinone dyes according to claim 2, characterized in that: The reaction temperature is 80-100° C., and the reaction time is 12-18 hours.