Preparation method of 2, 4, 6-tri (2-hydroxy-4-n-butoxyphenyl)-1, 3, 5-triazine
2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine was successfully prepared by using trifluoromethylsulfonic acid and ionic liquid catalysis on the basis of 2-hydroxy-4-methoxybenzidine, and mixed with n-butanol with potassium tert-butoxide/DBU, which solved the problems of complex, safety and economical synthesis routes in the prior art, and achieved an efficient, safe and economical synthesis process.
Patent Information
- Application Number
- CN202411657513.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-20
- Publication Date
- 2025-02-25
AI Technical Summary
In the prior art, the synthesis route of 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine has problems such as rare raw materials, complex processes, insufficient safety and economicality, and it is difficult to meet market demand.
2-hydroxy-4-methoxybenzonitrile was used as raw material and reacted under the action of trifluoromethylsulfonic acid and ionic liquid to produce 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine. Then, under the action of mixed alkali with n-butanol with potassium tert-butoxide/DBU, the target product 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine was further generated.
It provides a two-step reaction synthesis route, which has good feasibility, reduces the amount of trifluoromethylsulfonic acid, and adopts a new replacement reaction route, which improves the safety and economy of the process and meets the market's demand for efficient ultraviolet absorbers.
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Abstract
Description
Technical Field
[0001] The invention relates to a method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine, belonging to the technical field of organic synthesis. Background Art
[0002] The ortho-hydroxyl group on the benzene ring in the triazine compound molecule forms an intramolecular hydrogen bond with the nitrogen atom of the triazine ring. When irradiated by ultraviolet rays of a certain wavelength, the hydrogen bond is broken by absorbing energy, and then the light energy is converted into fluorescence, phosphorescence or heat and released in a non-radiative form, and the molecule re-forms an intramolecular hydrogen bond. In this process, the energy provided by UV-B and UV-C irradiation is exactly the energy required for the hydrogen bond to break, so this type of compound is a good new type of ultraviolet absorber. Among the triazine ultraviolet absorbers, the s-triazine ultraviolet absorber is widely used in the market. It has the advantages of high absorption efficiency, high temperature resistance, good compatibility, low color, etc., and can absorb ultraviolet rays of 280-380nm. Therefore, it is of great significance to research and develop s-triazine ultraviolet absorbers.
[0003] At present, the research on anti-ultraviolet has attracted great attention at home and abroad. 2,4,6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3,5-triazine is a highly efficient ultraviolet absorber, mainly used in agricultural polyvinyl chloride film, engineering plastics, latex and varnish coatings. This compound has the characteristics of strong absorption capacity and good antioxidant properties, and can effectively protect materials from damage by ultraviolet rays.
[0004] There are few reports on the synthesis of 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine.
[0005] Cyanuric chloride is reacted with resorcinol by Friedel-Crafts reaction to generate 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, which is then reacted with n-butyl bromide to generate 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine (CN107935952). The chemical reaction equation is as follows:
[0006]
[0007] In view of the shortcomings of the above methods, it is necessary to conduct in-depth research on the synthesis route of 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine to provide a simple, safe, stable and economical process route with easily available raw materials to meet the growing market demand. Summary of the invention
[0008] In order to solve the above technical problems, the present invention discloses a method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine. 2-Hydroxy-4-methoxybenzonitrile is used as a raw material to react under the action of trifluoromethanesulfonic acid and ionic liquid to generate 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine; 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine and n-butanol are reacted under the action of potassium tert-butoxide / DBU mixed base to generate the product 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine.
[0009] The preparation method of 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine of the present invention comprises the following steps:
[0010] A. Mixing 2-hydroxy-4-methoxybenzonitrile, trifluoromethanesulfonic acid and an ionic liquid in an organic solvent to obtain 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine;
[0011] B. Mix 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, potassium tert-butoxide / DBU mixed base and n-butanol in an organic solvent, and react under elevated temperature to obtain the product 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine.
[0012] The reaction equation is shown as follows:
[0013]
[0014] Furthermore, in the above technical solution, in step A, the ionic liquid is 1,3-dimethylimidazolium trifluoromethylsulfonate or 1-ethyl-3-methylimidazolium trifluoromethylsulfonate.
[0015] Furthermore, in the above technical solution, in step A, the organic solvent is selected from chloroform, dichloromethane or dichloroethane.
[0016] Furthermore, in the above technical solution, in step A, the molar ratio of the 2-hydroxy-4-methoxybenzonitrile, trifluoromethanesulfonic acid and ionic liquid is 1:1-1.2:0.05-0.1.
[0017] Furthermore, in the above technical solution, in step B, the organic solvent is selected from cyclopentyl methyl ether, diethoxymethane, dioxane, toluene or xylene.
[0018] Furthermore, in the above technical solution, in step B, the molar ratio of 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, potassium tert-butoxide, DBU and n-butanol is 1:8-10:2-3:5-7.
[0019] The present invention has the following beneficial effects:
[0020] 1. The present invention provides a two-step reaction route with good feasibility; trifluoromethanesulfonic acid and ionic liquid are used for co-catalysis, which reduces the amount of trifluoromethanesulfonic acid used and provides a route reference for synthesizing such compounds.
[0021] 3. The present invention uses n-butanol to directly react with anisole under the action of potassium tert-butoxide / DBU, which has a novel route and provides a new idea for this type of reaction. Specific embodiments
[0022] The present invention will be further described below by specific examples. These embodiments should be understood to be only used to illustrate the present invention and not to limit the scope of protection of the present invention. After reading the content of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent changes and modifications also fall within the scope defined by the claims of the present invention.
[0023] Example 1
[0024] Under nitrogen protection, 15g (0.1mol) of trifluoromethanesulfonic acid, 1.5g (0.006mol) of 1,3-dimethylimidazolium trifluoromethanesulfonate and 30mL of chloroform were mixed, cooled to 0-5°C, 14.9g (0.1mol) of 2-hydroxy-4-methoxybenzonitrile and 90mL of chloroform solution were added dropwise, and after the addition was completed, the temperature was raised to room temperature and reacted for 8 hours. After the reaction was completed, the reaction solution was added to 200mL of water, filtered, and the filter cake was washed with 150mL of water and 150mL of ethanol to obtain the product. Recrystallization from toluene gave 9.7g of 2,4,6-tris (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, with a yield of 65%. HPLC purity was 98.5%. 1 HNMR (400MHz, DMSO-d6): 8.03 (s, 1H), 7.64-7.56 (m, 1H), 7.28 (d, 1H), 7.18 (d, 1H), 3.93 (s, 3H).
[0025] Under nitrogen protection, 4.5 g (0.01 mol) of 2,4,6-tris (2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 10.1 g (0.09 mol) of potassium tert-butoxide, DBU (0.03 mol) and 4.4 g (0.06 mol) of n-butanol were mixed in 50 mL of cyclopentyl methyl ether, heated to 80-85°C for 18 hours, cooled to room temperature, adjusted pH to 6 with 2M hydrochloric acid, filtered, and the product was recrystallized from toluene to obtain 4.3 g of 2,4,6-tris (2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine, with a yield of 75%. Chemical purity was 98.6%. 1 HNMR (400MHz, DMSO-d6): 8.07(s,1H),7.66-7.56(m,1H),7.26(d,1H),7.1 6(d,1H),3.92(t,2H),1.80-1.71(m,2H),1.54-1.43(m,2H),0.97(t,3H).
[0026] Example 2
[0027] Under nitrogen protection, 18g (0.12mol) of trifluoromethanesulfonic acid, 2.6g (0.01mol) of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate and 36mL of chloroform were mixed, cooled to 0-5°C, 14.9g (0.1mol) of 2-hydroxy-4-methoxybenzonitrile and 90mL of chloroform solution were added dropwise, and after the addition was completed, the temperature was raised to room temperature and reacted for 6 hours. After the reaction was completed, the reaction solution was added to 200mL of water, filtered, and the filter cake was washed with 150mL of water and 150mL of ethanol to obtain the product. Recrystallization from toluene gave 9.4g of 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, with a yield of 63%. HPLC purity was 98.3%.
[0028] Under nitrogen protection, 4.5 g (0.01 mol) of 2,4,6-tris (2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 11.2 g (0.1 mol) of potassium tert-butoxide, DBU (0.03 mol) and 5.2 g (0.07 mol) of n-butanol were mixed in 50 mL of ethylene glycol dimethyl ether, heated to 80-85°C for 15 hours, cooled to room temperature, adjusted pH to 5-6 with 2M hydrochloric acid, filtered, and the product was recrystallized from toluene to obtain 4.5 g of 2,4,6-tris (2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine, with a yield of 78%. Chemical purity was 98.5%.
[0029] Example 3
[0030] Under nitrogen protection, 15 g (0.1 mol) of trifluoromethanesulfonic acid, 1.3 g (0.005 mol) of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate and 30 mL of dichloroethane were mixed, cooled to 0-5 ° C, 14.9 g (0.1 mol) of 2-hydroxy-4-methoxybenzonitrile and 90 mL of chloroform solution were added dropwise, and the temperature was raised to room temperature for reaction for 10 hours. After the reaction was completed, the reaction solution was added to 200 mL of water, filtered, and the filter cake was washed with 150 mL of water and 150 mL of ethanol to obtain the product. Recrystallization from toluene gave 2,4,6-tris (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 9.1 g, with a yield of 61%.
[0031] Under nitrogen protection, 4.5g (0.01mol) of 2,4,6-tris (2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 9.0g (0.08mol) of potassium tert-butoxide and 5.2g (0.07mol) of n-butanol were mixed in 50mL of dioxane, heated to 80-85°C for 17 hours, cooled to room temperature, adjusted pH to 5-6 with 2M hydrochloric acid, filtered, and the product was recrystallized from toluene to obtain 3.2g of 2,4,6-tris (2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine, with a yield of 56% and a HPLC purity of 98.2%. Under the same conditions, DBU (0.03mol) was added to react to obtain 4.7g of the product, with a yield of 82% and a HPLC purity of 98.4%.
[0032] Example 4
[0033] Under nitrogen protection, 18g (0.12mol) of trifluoromethanesulfonic acid, 1.2g (0.005mol) of 1,3-dimethylimidazolium trifluoromethanesulfonate and 30mL of dichloromethane were mixed, cooled to 0-5°C, 14.9g (0.1mol) of 2-hydroxy-4-methoxybenzonitrile and 90mL of chloroform solution were added dropwise, and the temperature was raised to room temperature for reaction for 8 hours. After the reaction was completed, the reaction solution was added to 200mL of water, filtered, and the filter cake was washed with 150mL of water and 150mL of ethanol to obtain the product. The product was recrystallized with toluene to obtain 9.4g of 2,4,6-tris (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, with a yield of 63%. HPLC purity was 98.5%.
[0034] Under nitrogen protection, 4.5 g (0.01 mol) of 2,4,6-tris (2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 9.0 g (0.08 mol) of potassium tert-butoxide, DBU (0.03 mol) and 4.4 g (0.06 mol) of n-butanol were mixed in 50 mL of cyclopentyl methyl ether, heated to 80-85 ° C, reacted for 20 hours, cooled to room temperature, adjusted pH to 5-6 with 2M hydrochloric acid, filtered, and the product was recrystallized from toluene to obtain 4.2 g of 2,4,6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3,5-triazine, with a yield of 73% and a HPLC purity of 98.3%.
[0035] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
Claims
1. A method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine, characterized in that: The steps include: A. Mixing 2-hydroxy-4-methoxybenzonitrile, trifluoromethanesulfonic acid and an ionic liquid in an organic solvent to obtain 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine; B. Mix 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, potassium tert-butoxide / DBU mixed base and n-butanol in an organic solvent, and react under elevated temperature to obtain the product 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine.
2. The method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine according to claim 1, characterized in that: In step A, the ionic liquid is 1,3-dimethylimidazolium trifluoromethylsulfonate or 1-ethyl-3-methylimidazolium trifluoromethylsulfonate.
3. The method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine according to claim 1, characterized in that: In step A, the organic solvent is selected from chloroform, dichloromethane or dichloroethane.
4. The method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine according to claim 1, characterized in that: In step A, the molar ratio of 2-hydroxy-4-methoxybenzonitrile, trifluoromethanesulfonic acid and ionic liquid is 1:1-1.2:0.05-0.
1.
5. The method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine according to claim 1, characterized in that: In step B, the organic solvent is selected from cyclopentyl methyl ether, diethoxymethane, dioxane, toluene or xylene.
6. The method for preparing 2,4,6-tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-triazine according to claim 1, characterized in that: In step B, the molar ratio of 2,4,6-tris(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, potassium tert-butoxide, DBU and n-butanol is 1:8-10:2-3:5-7.