Method for preparing 2, 4, 6-tri [(1, 1-biphenyl)-4-yl]-1, 3, 5-triazine
Preparation of 2,4,6-tri[(1,1-biphenyl)-4-yl]-1,3,5-triazine by catalyzing a 4-cyanobiphenyl reaction in an organic solvent using triflatesulphonic acid in an organic solvent , solve the problems of high cost and long operating time in the prior art, realize efficient preparation under mild conditions, and reduce waste liquid emissions and manufacturing costs.
Patent Information
- Application Number
- CN202411289802.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-14
- Publication Date
- 2024-12-17
AI Technical Summary
In the existing preparation of 2,4,6-triphenyl[(1,1-biphenyl)-4-yl]-1,3,5-triazine, the use of Pd(0) catalyst leads to high cost, 4-link Benzoyl chloride is costly and has a long process operation time, which makes it unsuitable for industrial production and product purification.
2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-tris The reaction conditions are mild, trichloromethane is used as the solvent, the catalyst molar ratio is 1:1.6-2.4, the reaction temperature is 30-70°C, the reaction time is 20-24 hours, and the pH is adjusted and filtered and dried.
One-step synthesis is achieved, with short production time and reduced waste liquid emissions and manufacturing costs. Trifluoromethanesulfonic acid is safe and efficient as a catalyst, with high yields, and is suitable for industrial production.
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Figure BDA0005044179960000021
Abstract
Description
Technical Field
[0001] The invention belongs to the field of organic chemistry, and specifically relates to a method for preparing 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine. Background Art
[0002] Ultraviolet rays can be divided into three types according to their wavelength: long-wave ultraviolet rays (320-400nm, UVA), medium-wave ultraviolet rays (280-320nm, UVB) and short-wave ultraviolet rays (200-280nm, UVC). The first two are more harmful to human skin, causing tanning, sunburn, and even skin cancer. Sunscreen cosmetics are widely favored by consumers because they can protect the human body from damage caused by ultraviolet radiation.
[0003] 2,4,6-Tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine is a new type of triazine UV absorber with a larger molecular structure, good UV absorption performance, and strong absorption of both UVA and UVB. It is a type of triazine UV absorber currently allowed for use by the US FDA, the European Union, and Japan.
[0004] Patent US16349704 discloses a method for preparing 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine. The method uses 2,4,6-tris(4-bromophenyl)-1,3,5-triazine to carry out Suzuki coupling with phenylboric acid in the presence of Pd(0) catalyst to prepare 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine. The use of Pd(0) catalyst results in high cost, which is not conducive to industrial production.
[0005] US06225467 discloses a preparation method, in which 4-biphenylnitrile is used as a raw material and 1,2-dichlorobenzene is used as a solvent to react in the presence of 4-biphenylcarbonyl chloride, thionyl chloride, aluminum chloride and ammonium chloride to obtain a crude product of 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine, and then the crude product is purified by sublimation to obtain a finished product; the method uses 4-biphenylcarbonyl chloride at a high cost; the process uses a large amount of inorganic salts to make the content of the prepared crude product low; the product reported in the patent is refined by a sublimation method, which has a long operation time and a large product loss, and is not suitable for the purification of a large amount of products. Summary of the invention
[0006] The object of the present invention is to provide a novel method for preparing triazine ultraviolet absorber 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine.
[0007] In some embodiments, a method for preparing 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine of the present invention comprises polymerizing 4-cyanobiphenyl in an organic solvent via a trifluoromethanesulfonic acid catalytic reaction.
[0008] The reaction formula is as follows:
[0009]
[0010] Furthermore, in the method of the present invention, the volume mass (ml / g) ratio of the organic solvent to 4-cyanobiphenyl is 5 to 10, and the organic solvent is one or two of chloroform, dichloromethane or toluene, more preferably chloroform, and its amount is 5 to 10 times the mass volume of 4-cyanobiphenyl (i.e. chloroform / 4-cyanobiphenyl ml / g).
[0011] Furthermore, in the method of the present invention, the molar ratio of 4-cyanobiphenyl to trifluoromethanesulfonic acid is 1:(1.6-2.4).
[0012] Furthermore, in the method of the present invention, the catalytic reaction has a reaction temperature of 30 to 70° C. and a reaction time of 20 to 24 hours.
[0013] Furthermore, the method of the present invention further comprises concentrating the reaction product, adding sodium hydroxide solution to adjust the pH to 5-7, filtering, and washing the filter cake by pulping with a solvent.
[0014] Preferably, in the method of the present invention, the solvent is selected from methanol, ethanol, isopropanol, n-butanol, tert-butanol, amyl alcohol, acetone and ethyl acetate, more preferably methanol, ethanol or ethyl acetate.
[0015] Furthermore, in the method of the present invention, the drying temperature is 30-80°C.
[0016] In some specific embodiments, a method for preparing 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine of the present invention comprises dissolving 4-cyanobiphenyl in chloroform, dropping a catalyst trifluoromethanesulfonic acid, heating to 30 to 70° C., catalyzing the reaction for 20 to 24 hours, and after the reaction is completed, concentrating to remove the chloroform, adding a sodium hydroxide aqueous solution to adjust the pH to 5 to 7, filtering, washing the filter cake with a solvent by pulping, filtering, and drying the filter cake.
[0017] Preferably, in the above method of the present invention, the volume mass ratio of chloroform to 4-cyanobiphenyl is 5-10 ml / g; the molar ratio of 4-cyanobiphenyl to trifluoromethanesulfonic acid is 1:(1.6-2.4).
[0018] Preferably, in the above method of the present invention, the pulping washing solvent is selected from methanol, ethanol, isopropanol, n-butanol, tert-butanol, amyl alcohol, acetone and ethyl acetate, more preferably methanol, ethanol or ethyl acetate; the drying temperature is 30-80°C.
[0019] Compared with the prior art, the present invention has the following advantages:
[0020] 1. Use a one-step method to synthesize 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine, with short production time, mild reaction conditions and convenient process operation;
[0021] 2. Chloroform can be recycled, which reduces waste liquid discharge and reduces manufacturing costs;
[0022] 3. Using trifluoromethanesulfonic acid as a catalyst has high safety and high yield.
[0023] In summary, the method of the present invention uses 4-cyanobiphenyl as a raw material, and polymerizes to prepare 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine under the condition of super acid trifluoromethanesulfonic acid as a catalyst. The reaction conditions of all steps are mild and easy to operate, and the method has significant social and economic benefits. DETAILED DESCRIPTION
[0024] The following examples are representative and are used to further illustrate and understand the essence of the present invention, but are not intended to limit the scope of the present invention. Any simple modifications and adaptations within the spirit and essence of the present invention belong to the protection scope of the present invention.
[0025] Example 1 Preparation of 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine
[0026] 100 ml of chloroform and 20 g of 4-cyanobiphenyl were added to a 250 ml three-necked flask, 30 g of trifluoromethanesulfonic acid was dripped into the reaction flask, and after the dripping was completed, the mixture was stirred for 15 min and then heated to 30-70° C. for reaction for 22 h; after the reaction was completed, the mixture was cooled and then transferred to a concentration flask to remove the chloroform. After the concentration was completed, an aqueous sodium hydroxide solution was added to the reaction flask to adjust the pH to 5-7, stirred for 1-2 h, filtered, and the filter cake was pulped and filtered with ethanol, and the pulping and filtering were repeated once, with 100 ml of ethanol used each time. The filter cake was dried in a drying oven and the temperature was controlled at 30-80° C. to obtain 17.2 g of the target product with a molar yield of 86.0% and a purity of 98.33%.
[0027] Example 2 Preparation of 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine
[0028] 320 ml of chloroform and 40 g of 4-cyanobiphenyl were added to a 500 ml three-necked flask, 66.9 g of trifluoromethanesulfonic acid was dripped into the reaction flask, and the mixture was stirred for 15 min after the dripping was completed, and then the temperature was raised to 30-70° C. for reaction for 24 h; the temperature was lowered after the reaction was completed, and the mixture was transferred to a concentration flask to remove the chloroform. After the concentration was completed, an aqueous sodium hydroxide solution was added to the reaction flask to adjust the pH to 5-7, stirred for 1-2 h, and filtered. The filter cake was pulped and filtered twice with ethanol, with 200 ml of ethanol used each time. The filter cake was dried in a drying oven, and the temperature was controlled at 30-80° C. to obtain 34.9 g of the target product with a molar yield of 87.2% and a purity of 98.32%.
[0029] Example 3 Preparation of 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine
[0030] 200 ml of toluene and 20 g of 4-cyanobiphenyl were added to a 250 ml three-necked flask, and 27.3 g of trifluoromethanesulfonic acid was dripped into the reaction flask. After the dripping was completed, the mixture was stirred for 20 min and then heated to 50-70° C. for reaction for 22 h. After the reaction was completed, the mixture was cooled and then transferred to a concentration flask to remove the solvent. After the concentration was completed, a sodium hydroxide aqueous solution was added to the reaction flask to adjust the pH to 5-7, stirred for 1-2 h, and filtered. The filter cake was pulped and filtered twice with 100 ml of ethyl acetate, and the filter cake was dried in a drying oven at a temperature of 30-80° C. to obtain 16.9 g of the target product with a molar yield of 84.5% and a purity of 97.93%.
[0031] Example 4 Preparation of 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine
[0032] 100 ml of dichloromethane and 20 g of 4-cyanobiphenyl were added to a 250 ml three-necked flask, and 28.8 g of trifluoromethanesulfonic acid was dripped into the reaction flask. After the dripping was completed, the mixture was stirred for 20 min and then heated to 30-50° C. for reaction for 22 h. After the reaction was completed, the mixture was cooled and then transferred to a concentration flask to remove the solvent. After the concentration was completed, an aqueous sodium hydroxide solution was added to the reaction flask to adjust the pH to 5-7, stirred for 1-2 h, and filtered. The filter cake was pulped and filtered twice with 150 ml of methanol, and the filter cake was dried in a drying oven at a temperature of 30-80° C. to obtain 16.8 g of the target product with a molar yield of 84.1% and a purity of 98.03%.
Claims
1. A method for preparing 2,4,6-tris[(1,1-biphenyl)-4-yl]-1,3,5-triazine, comprising: It is obtained by polymerizing 4-cyanobiphenyl in an organic solvent via a trifluoromethanesulfonic acid catalytic reaction.
2. The method according to claim 1, wherein the volume mass ratio of the organic solvent to 4-cyanobiphenyl is 5 to 10 ml / g.
3. The method according to claim 1 or 2, wherein the organic solvent is selected from one or both of chloroform, toluene and dichloromethane.
4. The method according to claim 1, wherein the molar ratio of 4-cyanobiphenyl to trifluoromethanesulfonic acid is 1:(1.6-2.4).
5. The method according to claim 1, wherein the reaction temperature of the catalytic reaction is 30 to 70°C.
6. The method according to claim 1, wherein the catalytic reaction has a reaction time of 20 to 24 hours.
7. The method according to claim 1, further comprising concentrating the reaction product, adding sodium hydroxide solution to adjust the pH to 5-7, filtering, and washing the filter cake with a solvent.
8. The method of claim 7, wherein the solvent is selected from the group consisting of methanol, ethanol, isopropanol, n-butanol, tert-butanol, amyl alcohol, acetone and ethyl acetate.
9. The method according to claim 8, wherein the solvent is methanol, ethanol or ethyl acetate.
10. The method according to claim 7, wherein the drying temperature is 30-80°C.