Preparation method of 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine

Abstract

The invention provides a preparation method of 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine, and belongs to the technical field of sun-screening agent preparation. The preparation method of the 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine comprises the following steps: carrying out substitution reaction on a compound in a formula I to obtain a compound in a formula II; performing hydrolysis reaction on the compound in the formula II to obtain a compound in a formula III; and carrying out Friedel-Crafts reaction on the compound shown in the formula III and cyanuric chloride to obtain a compound shown in a formula IV. The preparation method comprises the following steps: reacting benzoic acid-3-hydroxyphenyl ester with n-butyl bromide to obtain benzoic acid-3-(butyloxy) phenyl ester, removing benzoyl from the benzoic acid-3-(butyloxy) phenyl ester to obtain 3-(butyloxy) phenol, and reacting 3-(butyloxy) phenol with cyanuric chloride to obtain 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine, so that the yield of 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine is increased, and the yield of 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine is increased. The yield of the 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine is increased, and the production cost of the yield of the 2, 4, 6-tri (4 '-butoxy-2'-hydroxyphenyl)-triazine is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of sunscreen preparation, and particularly relates to a preparation method of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine. Background Art

[0002] In recent years, it has been gradually found that 1,3,5-triazine compounds have attracted wide attention because of their wide ultraviolet absorption range and high absorption rate, and have been widely used in fields such as coatings, plastics, and cosmetics.

[0003] Currently, 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine is generally obtained by reacting cyanuric chloride with resorcinol in the presence of aluminum trichloride to obtain an intermediate product of 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, and then the intermediate product is subjected to an etherification reaction with a haloalkane (BuX) to obtain the target product. The specific reaction formula is as follows:

[0004]

[0005] In the preparation process of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine, when the intermediate product of 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine is subjected to an etherification reaction with a haloalkane (BuX), an overreaction will occur to produce UV-460, that is, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. Its formation process is as follows:

[0006]

[0007] Since 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine has no good selectivity for the screening of solvents, temperature, and base during the etherification reaction, it is prone to overreaction, generating a large amount of UV-460, which is not conducive to the separation and purification of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine, resulting in a very low yield of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine and a high cost. Summary of the Invention

[0008] In view of this, the purpose of the present invention is to provide a preparation method of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine, aiming to improve the yield of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine and reduce the production cost of preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine.

[0009] To achieve the above object, the present invention provides a preparation method of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine, comprising the following steps:

[0010]

[0011] (1) The compound of formula I undergoes a substitution reaction to obtain the compound of formula II;

[0012] (2) The compound of formula II undergoes a hydrolysis reaction to obtain the compound of formula III;

[0013] (3) The compound of formula III and cyanuric chloride undergo a Friedel-Crafts reaction to obtain the compound of formula IV.

[0014] Preferably, the step (1) includes: adding the compound of formula I, bromobutane and a first basic compound to a first solvent for reaction to obtain the compound of formula II.

[0015] Preferably, the step (1) includes:

[0016] Adding the compound of formula I, bromobutane and a first basic compound to a first solvent, heating to 60-110 °C, stirring for reaction for 5-24 h, then filtering, and adding a first separation solvent to the filtrate to obtain a first organic phase;

[0017] Adding a first basic solution to the first organic phase for washing, then separating the layers to obtain a second organic phase;

[0018] Concentrating the second organic phase to obtain the compound of formula II.

[0019] Preferably, the first basic compound is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate;

[0020] The first separation solvent is selected from one of a mixed solvent of ethyl acetate and water, toluene, MTBE;

[0021] The first basic solution is selected from one of sodium hydroxide solution and potassium hydroxide solution;

[0022] The molar ratio of the compound of formula I to the bromobutane and the first basic compound is 1:1.5-2:1.5-2.

[0023] Preferably, the step (2) may include:

[0024] Adding the compound of formula II and a second basic compound to a second solvent for reaction to obtain the compound of formula III.

[0025] Preferably, the step (2) includes:

[0026] Add the compound of formula II and the second basic compound to water, heat up to 80 - 100 °C and stir for reaction for 4 - 9 h;

[0027] After cooling to 10 - 30 °C, add the second solvent and stir for 1 - 4 h to obtain the third organic phase;

[0028] Add the second basic solution to the third organic phase for washing and then separate the layers to obtain the fourth organic phase;

[0029] Concentrate the fourth organic phase to obtain the compound of formula III.

[0030] Preferably, the second basic compound is selected from potassium carbonate, cesium carbonate, cesium hydroxide, sodium hydroxide, potassium hydroxide and their mixtures;

[0031] The second solvent is selected from one or more of toluene, xylene, n - heptane, n - hexane, cyclohexane;

[0032] The second basic solution is selected from one of sodium carbonate solution and sodium bicarbonate solution;

[0033] The molar ratio of the compound of formula II to the second basic compound is 1:2 - 3.

[0034] Preferably, step (3) may include:

[0035] Add the compound of formula III and cyanuric chloride to the fourth solvent to obtain the compound of formula IV.

[0036] Preferably, step (3) may include:

[0037] Add the compound of formula III and cyanuric chloride to the third solvent, stir for 0.5 - 1 h, then add aluminum trichloride, heat up to 80 - 90 °C and stir for reaction for 4 - 12 h;

[0038] After cooling to 10 - 30 °C, add hydrochloric acid and stir for 1 - 4 h to precipitate a solid;

[0039] Add the precipitated solid to the fourth solvent at 60 - 80 °C and dissolve it completely, then cool to 10 - 30 °C to precipitate and obtain the compound of formula IV.

[0040] Preferably, the third solvent is selected from one or more of toluene, xylene, n - heptane, n - hexane, cyclohexane;

[0041] The fourth solvent is selected from one of the mixed solvents of tetrahydrofuran and ethanol, and the mixed solvents of toluene and isopropanol;

[0042] The molar ratio of cyanuric chloride to the compound of formula III and aluminum trichloride is 1:3 - 3.5:3 - 3.5.

[0043] Preferably, before step (1), the following steps are further included:

[0044]

[0045] (4) Resorcinol undergoes an acylation reaction to obtain a compound of formula I.

[0046] Preferably, step (4) includes:

[0047] Dissolve resorcinol and a third basic compound in a fifth solvent, dropwise add benzoyl chloride to the fifth solvent, and stir and react at 0-10 °C for 5-10 h;

[0048] Dropwise add a third basic solution to adjust the pH value of the solution to 9-10, stir for 0.5-2 h, then filter and dry to obtain a compound of formula I.

[0049] Preferably, the third basic compound is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate.

[0050] The fifth solvent is selected from one or more of toluene, xylene, n-heptane, n-hexane, and cyclohexane;

[0051] The molar ratio of resorcinol to benzoyl chloride is 1:1.2-3.

[0052] The present invention provides a preparation method of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine, including the following steps: The compound of formula I undergoes a substitution reaction to obtain a compound of formula II; the compound of formula II undergoes a hydrolysis reaction to obtain a compound of formula III; the compound of formula III and cyanuric chloride undergo a Friedel-Crafts reaction to obtain a compound of formula IV. The present invention reacts benzoic acid 3-hydroxyphenyl ester with n-butyl bromide to obtain benzoic acid 3-(butyloxy)phenyl ester, benzoic acid 3-(butyloxy)phenyl ester is debenzoylated to obtain 3-(butyloxy)phenol, and 3-(butyloxy)phenol reacts with cyanuric chloride to obtain 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine, which improves the yield of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine and reduces the production cost of the yield of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine. Description of the Drawings

[0053] Figure 1 It is the HPLC chromatogram of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine of the present invention. Detailed Embodiments

[0054] The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments in the present invention.

[0055] The present invention provides a preparation method of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-s-triazine, comprising the following steps:

[0056]

[0057] (1) The compound of formula I undergoes a substitution reaction to obtain the compound of formula II;

[0058] (2) The compound of formula II undergoes a hydrolysis reaction to obtain the compound of formula III;

[0059] (3) The compound of formula III and cyanuric chloride undergo a Friedel-Crafts reaction to obtain the compound of formula IV.

[0060] Unless otherwise specified, the present invention has no special requirements for the sources of the raw materials used in the preparation, and commercially available products well-known to those skilled in the art can be used.

[0061] In the present invention, the step (1) may include: adding the compound of formula I, n-butyl bromide and a first basic compound to a first solvent for reaction to obtain the compound of formula II.

[0062] In the present invention, the step (1) may further include:

[0063] Adding the compound of formula I, n-butyl bromide and a first basic compound to a first solvent, heating to 60-110 °C, stirring for reaction for 5-24 h, then filtering, and adding a first separation solvent to the filtrate to obtain a first organic phase;

[0064] Adding a first basic solution to the first organic phase for washing, then separating the layers to obtain a second organic phase;

[0065] Concentrating the second organic phase to obtain the compound of formula II.

[0066] In the present invention, the step (2) may include:

[0067] Adding the compound of formula II and a second basic compound to a second solvent for reaction to obtain the compound of formula III.

[0068] In the present invention, the step (2) may further include:

[0069] Adding the compound of formula II and a second basic compound to water, heating to 80-100 °C, stirring for reaction for 4-9 h;

[0070] Cooling to 10-30 °C, then adding a second solvent and stirring for 1-4 h to obtain a third organic phase;

[0071] Adding a second basic solution to the third organic phase for washing, then separating the layers to obtain a fourth organic phase;

[0072] Concentrate the fourth organic phase to obtain the compound of formula III.

[0073] In the present invention, step (3) may include:

[0074] Add the compound of formula III and cyanuric chloride to a third solvent, stir for 0.5 - 1 h, then add aluminum trichloride and raise the temperature to 80 - 90 °C and stir for reaction for 4 - 12 h;

[0075] After cooling to 10 - 30 °C, add hydrochloric acid and stir for 1 - 4 h to precipitate a solid;

[0076] Add the precipitated solid to a fourth solvent at 60 - 80 °C and dissolve it completely, then cool to 10 - 30 °C to precipitate and obtain the compound of formula IV.

[0077] In the present invention, the first basic compound is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate;

[0078] In the present invention, the first separation solvent is selected from one of a mixed solvent of ethyl acetate and water, toluene, and MTBE;

[0079] In the present invention, the first basic solution is selected from one of a sodium hydroxide solution and a potassium hydroxide solution;

[0080] In the present invention, the molar ratio of the compound of formula I to the n-butyl bromide and the first basic compound is 1:1.5 - 2:1.5 - 2.

[0081] In the present invention, the second basic compound is selected from potassium carbonate, cesium carbonate, cesium hydroxide, sodium hydroxide, potassium hydroxide, and mixtures thereof;

[0082] In the present invention, the second solvent is selected from one or more of toluene, xylene, n-heptane, n-hexane, and cyclohexane;

[0083] In the present invention, the third solvent is selected from one or more of toluene, xylene, n-heptane, n-hexane, and cyclohexane;

[0084] In the present invention, the second basic solution is selected from one of a sodium carbonate solution and a sodium bicarbonate solution.

[0085] In the present invention, the molar ratio of the compound of formula II to the second basic compound is 1:2 - 3.

[0086] In the present invention, the third solvent is selected from one or more of toluene, xylene, n-heptane, n-hexane, and cyclohexane;

[0087] In the present invention, the fourth solvent is selected from one of a mixed solvent of tetrahydrofuran and ethanol and a mixed solvent of toluene and isopropanol;

[0088] In the present invention, the molar ratio of cyanuric chloride, the compound of formula III, and aluminum trichloride is 1:3 to 3.5:3 to 3.5.

[0089] In the present invention, before step (1), it further includes:

[0090]

[0091] (4) Resorcinol undergoes an acylation reaction to obtain the compound of formula I.

[0092] In the present invention, step (4) includes:

[0093] Dissolve resorcinol and a third basic compound in a fifth solvent, add benzoyl chloride dropwise to the fifth solvent, and stir and react at 0 - 10°C for 5 - 10 h;

[0094] Adjust the pH value of the solution to 9 - 10 by dropwise adding a third basic solution, stir for 0.5 - 2 h, then filter and dry to obtain the compound of formula I.

[0095] In the present invention, the third basic compound is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate.

[0096] In the present invention, the fifth solvent is selected from one or more of toluene, xylene, n - heptane, n - hexane, and cyclohexane;

[0097] In the present invention, the molar ratio of resorcinol to benzoyl chloride is 1:1.2 to 3.

[0098] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the examples in the present invention.

[0099] Example 1

[0100] 1) Add resorcinol (10 g, 0.0908 mol), n - heptane (20 mL), water (50 mL), and sodium bicarbonate (22.9 g, 0.2724 mol) to a 250 mL three - necked flask; add benzoyl chloride (19.1 g, 0.1362 mol) dropwise, and stir at 0°C for 7 hours; after the reaction is completed, add 22% aqueous sodium carbonate solution to adjust the pH value to 9, stir for 1 hour, then filter the system and dry to obtain 15.5 g of white solid 3 - hydroxyphenyl benzoate, with a purity of 96.5% and a yield of 80.2%.

[0101] 2) Add the benzoic acid-3-hydroxyphenyl ester (15 g, 0.07 mol) prepared in the previous step, DMF (75 mL), and potassium carbonate (14.5 g, 0.105 mol) to a 250 mL three-necked flask. Then add n-butyl bromide (12.47 g, 0.091 mol). Heat the mixture to 110 °C and stir for 24 h. Filter the mixture. Add ethyl acetate and water to the filtrate, separate the organic phase. Wash the organic phase with 10% aqueous sodium hydroxide solution, separate the layers, and concentrate to remove ethyl acetate to obtain 14 g of crude benzoic acid-3-(butyloxy)phenyl ester. (Purity 94.0%, yield 75%).

[0102] 3) Add the benzoic acid-3-(butyloxy)phenyl ester (10 g, 0.037 mol) prepared in the previous step and water (20 mL) to a 100 mL three-necked flask. Then add lithium hydroxide (3.6 g, 0.15 mol). Heat the mixture to 100 °C and stir for 9 h. Slowly cool the mixture to 30 °C, add 5 times the amount of toluene, stir for 1 h, and then let it stand to separate the layers. Wash the organic phase with aqueous potassium carbonate solution once again, and concentrate to remove toluene to obtain 5.2 g of 3-(butyloxy)phenol (95.4%, yield 85%).

[0103] 4) Add the 3-(butyloxy)phenol (5 g, 0.03 mol) and cyanuric chloride (1.84 g, 0.01 mol) prepared in the previous step to a 100 mL three-necked flask. Then add toluene (18 mL). Stir for 1 h and then add aluminum trichloride (4 g, 0.03 mol). Heat the mixture to 90 °C and stir for 6 h. Slowly cool the mixture to 30 °C, add 20% hydrochloric acid to quench the reaction. Stir for 1 h, and then a solid will precipitate in the system. Filter to obtain a pale yellow crude product. Dissolve the crude product in 2.5 g of tetrahydrofuran and 10.0 g of ethanol by heating to 70 °C until clear, and then cool to 10 °C. A large amount of solid will precipitate. Filter to obtain 4.1 g of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine (98.4%, yield 72%).

[0104] Example 2

[0105] 1) Add resorcinol (10 g, 0.0908 mol), n-heptane (20 mL), water (50 mL), and sodium carbonate (28.9 g, 0.2724 mol) to a 250 mL three-necked flask. Dropwise add benzoyl chloride (19.1 g, 0.1362 mol) and stir at 10 °C for 10 h. After the reaction is completed, add 22% aqueous sodium carbonate solution to adjust the pH value to 10. Stir for 2 h, then filter the system and dry to obtain 15.5 g of white solid benzoic acid-3-hydroxyphenyl ester with a purity of 96.3% and a yield of 81.3%.

[0106] 2) Add benzoic acid-3-hydroxyphenyl ester (15 g, 0.07 mol), acetonitrile (75 mL), and potassium carbonate (14.5 g, 0.105 mol) to a 250 mL three-necked flask. Then add n-butyl bromide (12.47 g, 0.091 mol). Heat the mixture to 70 °C and stir for 8 h. Filter the mixture. Add toluene to the filtrate, separate the organic phase, wash the organic phase with 10% aqueous potassium hydroxide solution, separate the layers, and concentrate to remove toluene to obtain 14 g of crude benzoic acid-3-(butyloxy)phenyl ester. (Purity 94.6%, yield 76.1%).

[0107] 3) Add benzoic acid-3-(butyloxy)phenyl ester (10 g, 0.037 mol) and water (20 mL) to a 100 mL three-necked flask. Then add sodium hydroxide (6 g, 0.15 mol). Heat the mixture to 80 °C and stir for 6 h. Slowly cool the mixture to 10 °C, add 5 times the amount of n-heptane, stir for 4 h, and then let it stand to separate the layers. Wash the organic phase with aqueous potassium hydroxide solution once again, and concentrate to remove n-heptane to obtain 5.2 g of 3-(butyloxy)phenol (95.6%, yield 85.4%).

[0108] 4) Add 3-(butyloxy)phenol (5 g, 0.03 mol) and cyanuric chloride (1.84 g, 0.01 mol) to a 100 mL three-necked flask. Then add n-heptane (18 mL). Stir for 0.5 h and then add aluminum chloride (3 g, 0.02 mol). Heat the mixture to 80 °C and stir for 12 h. Slowly cool the mixture to 20 °C, quench with 20% hydrochloric acid, stir for 4 h, and then a solid will precipitate in the system. Filter to obtain a pale yellow crude product. Dissolve the crude product in 2.5 g of tetrahydrofuran and 10.0 g of ethanol by heating to 80 °C until clear, then cool to 30 °C, and a large amount of solid will precipitate. Filter to obtain 4.1 g of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine (98.3%, yield 69%).

[0109] Example 3

[0110] 1) Add resorcinol (10 g, 0.0908 mol), toluene (20 mL), water (50 mL), and sodium carbonate (28.9 g, 0.2724 mol) to a 250 mL three-necked flask. Dropwise add benzoyl chloride (19.1 g, 0.1362 mol) and stir at 5 °C for 5 h. After the reaction is completed, dropwise add 22% aqueous sodium carbonate solution to adjust the pH to 9, stir for 0.5 h, then filter the system and dry to obtain 15.5 g of white solid benzoic acid-3-hydroxyphenyl ester (purity 96.8%, yield 81.8%).

[0111] 2) Add the benzoic acid 3-hydroxyphenyl ester (15 g, 0.07 mol), DMF (75 mL) and potassium carbonate (14.5 g, 0.105 mol) prepared in the previous step to a 250 mL three-necked flask. Then add n-butyl bromide (12.47 g, 0.091 mol). Heat the mixture to 95 °C and stir for 15 h. Filter the mixture. Add methyl tert-butyl ether (MTBE) to the filtrate, separate the organic phase, wash the organic phase with 10% aqueous sodium hydroxide solution, separate the layers, and concentrate to remove MTBE to obtain 14 g of crude benzoic acid 3-(butyloxy)phenyl ester. (Purity 93.2%, yield 74.1%).

[0112] 3) Add the benzoic acid 3-(butyloxy)phenyl ester (10 g, 0.037 mol) and water (20 mL) prepared in the previous step to a 100 mL three-necked flask. Then add potassium hydroxide (8.4 g, 0.15 mol). Heat the mixture to 90 °C and stir for 4 h. Slowly cool the mixture to 20 °C, add 5 times the amount of toluene, stir for 2 h, and then let it stand for liquid separation. Wash the organic phase with aqueous potassium carbonate solution once again, and concentrate to remove toluene to obtain 5.2 g of 3-(butyloxy)phenol (94.6%, yield 83.4%).

[0113] 4) Add the 3-(butyloxy)phenol (5 g, 0.03 mol) and cyanuric chloride (1.84 g, 0.01 mol) prepared in the previous step to a 100 mL three-necked flask. Then add chlorobenzene (18 mL). After stirring for 1 h, add aluminum trichloride (4 g, 0.03 mol). Heat the mixture to 95 °C and stir for 9 h. Slowly cool the mixture to 10 °C, add 20% hydrochloric acid to quench the reaction, stir for 2 h, and a solid will precipitate in the system. Filter to obtain a pale yellow crude product. Dissolve the crude product in 2.5 g of tetrahydrofuran and 10.0 g of ethanol by heating to 75 °C until clear, then cool to 20 °C, and a large amount of solid will precipitate. Filter to obtain 4.1 g of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine (98.2%, yield 73.4%).

[0114] Thus, in the present invention, benzoic acid 3-(butyloxy)phenyl ester is obtained by the reaction of benzoic acid 3-hydroxyphenyl ester with n-butyl bromide, 3-(butyloxy)phenol is obtained by removing the benzoyl group from benzoic acid 3-(butyloxy)phenyl ester, and 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine is obtained by the reaction of 3-(butyloxy)phenol with cyanuric chloride, which improves the yield of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine and reduces the production cost of 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-1,3,5-triazine.

[0115] In the synthetic route of the present invention, benzoic acid 3-hydroxyphenyl ester, benzoic acid 3-(butyloxy)phenyl ester, and 3-(butyloxy)phenol are easily purified and separated, and the quality is easy to control, such that the product purity of 2,4,6-tris(4'-butyloxy-2'-hydroxyphenyl)-s-triazine is above 98.0%, and the product quality of 2,4,6-tris(4'-butyloxy-2'-hydroxyphenyl)-s-triazine is easy to control. In the step of synthesizing benzoic acid 3-hydroxyphenyl ester in the present invention, the selectivity of resorcinol is controlled through a two-phase reaction, such that benzoyl chloride only reacts with one hydroxyl group on resorcinol, so as to control that there is only one active site in the reaction for synthesizing benzoic acid 3-(butyloxy)phenyl ester, and the selectivity of the reaction step for synthesizing benzoic acid 3-(butyloxy)phenyl ester is good, and the yield can reach more than 80%; in the reaction step of removing the benzoyl protecting group from benzoic acid 3-(butyloxy)phenyl ester to obtain 3-(butyloxy)phenol in the present invention, the yield can reach more than 85%. Through 4 synthetic steps in the present invention, the total yield of 2,4,6-tris(4'-butyloxy-2'-hydroxyphenyl)-s-triazine is increased to about 37%.

[0116] Although the above embodiments have described the present invention in detail, they are only a part rather than all of the embodiments of the present invention. People can also obtain other embodiments according to these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine, characterized in that: The following steps are involved: (1) The compound of formula I is subjected to a substitution reaction to obtain a compound of formula II; (2) the compound of formula II is subjected to a hydrolysis reaction to obtain a compound of formula III; (3) The compound of formula III is reacted with cyanuric chloride through Friedel-Crafts reaction to obtain the compound of formula IV.

2. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 1, characterized in that: The step (1) comprises: Add the compound of formula I, n-butyl bromide and the first basic compound to the first solvent, raise the temperature to 60-110° C., stir and react for 5-24 hours, filter, and add the first separation solvent to the filtrate to obtain a first organic phase; Adding the first alkaline solution to the first organic phase, washing, and then separating to obtain a second organic phase; The second organic phase is concentrated to obtain the compound of formula II.

3. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 2, characterized in that: The first alkaline compound is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate and potassium bicarbonate; The first separation solvent is selected from a mixed solvent of ethyl acetate and water, toluene, and MTBE; The first alkaline solution is selected from one of a sodium hydroxide solution and a potassium hydroxide solution; The molar ratio of the compound of formula I to the n-butyl bromide and the first basic compound is 1:1.5-2:1.5-2.

4. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to any one of claims 1 to 3, characterized in that: The step (2) comprises: Add the compound of formula II and the second basic compound into water, raise the temperature to 80-100°C, stir and react for 4-9h; After cooling to 10-30°C, add the second solvent and stir for 1-4 hours to obtain a third organic phase; Add the second alkaline solution to the third organic phase, wash it, and then separate the phases to obtain a fourth organic phase; The fourth organic phase is concentrated to obtain the compound of formula III.

5. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 4, characterized in that: The second alkaline compound is selected from potassium carbonate, cesium carbonate, cesium hydroxide, sodium hydroxide, potassium hydroxide and mixtures thereof; The second solvent is selected from one or more of toluene, xylene, n-heptane, n-hexane, and cyclohexane; The second alkaline solution is selected from one of a sodium carbonate solution and a sodium bicarbonate solution; The molar ratio of the compound of formula II to the second basic compound is 1:2-3.

6. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 4, characterized in that: The step (3) comprises: Add the compound of formula III and cyanuric chloride to the third solvent, stir for 0.5 to 1 hour, add aluminum chloride, heat to 80 to 90° C., stir and react for 4 to 12 hours; After cooling to 10-30°C, add hydrochloric acid and stir for 1-4 hours to precipitate solid; The precipitated solid is added to the fourth solvent at 60-80°C and completely dissolved, then cooled to 10-30°C to precipitate the compound of formula IV.

7. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 6, characterized in that: The third solvent is selected from one or more of toluene, chlorobenzene, xylene, n-heptane, n-hexane, and cyclohexane; The fourth solvent is selected from one of a mixed solvent of tetrahydrofuran and ethanol, and a mixed solvent of toluene and isopropanol; The molar ratio of the cyanuric chloride to the compound of formula III and the aluminum chloride is 1:3-3.5:3-3.

5.

8. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to any one of claims 5 to 7, characterized in that: Before step (1), the method further includes: (4) Resorcinol is subjected to acylation reaction to obtain the compound of formula I.

9. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 8, characterized in that: The step (4) comprises: Dissolve resorcinol and the third alkaline compound in a fifth solvent, add benzoyl chloride dropwise to the fifth solvent, and stir and react at 0 to 10° C. for 5 to 10 hours; The third alkaline solution is added dropwise to adjust the pH value of the solution to 9-10, and the mixture is stirred for 0.5-2 hours, filtered, and dried to obtain a compound of formula I.

10. The method for preparing 2,4,6-tris(4'-butoxy-2'-hydroxyphenyl)-triazine according to claim 9, characterized in that: The third alkaline compound is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate. The fifth solvent is selected from one or more of toluene, xylene, n-heptane, n-hexane, and cyclohexane; The molar ratio of the resorcinol to the benzoyl chloride is 1:1.2-3.

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