Method for synthesizing 4,6-bis(trichloromethyl)-2-p-acetyl biphenyl-1,3,5-triazine

A bis-trichloromethyl and acetyl biphenyl technology, applied in the direction of organic chemistry, can solve the problems of harsh reaction conditions, environmental pollution, cumbersome post-treatment, etc., and achieve the effect of mild reaction conditions, good yield and simple operation

Inactive Publication Date: 2009-05-27

HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY

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Problems solved by technology

There are many ways to oxidize hydrocarbon groups to carbonyl groups, such as the reported Cr(VI) or KMnO 4 , NaBiO 3 /AcOH, RuCl 2 (PPh 3 ) 3 -t -B...

Abstract

The invention discloses a method for preparing a 1, 3, 5-triazine derivative with potential application in the fields such as photo-acid generators, insecticides, medicines, liquid crystal materials and so on, namely a method for synthesizing 4, 6-bistrichloromethyl-2-p-acetylbiphenyl-1, 3, 5-triazine, which comprises the following steps: a liquid crystal intermediate, namely p-ethyl cyanophenyl is taken as a raw material to prepare to obtain an intermediate product 4, 6-bistrichloromethyl-2-p-ethylbiphenyl-1, 3, 5-triazine, and then a target product is obtained through the oxidation. The synthesis method has the characteristics of mild reaction conditions, simple operation, small environmental pollution, safety and validity, and the obtained product can be used for preparing the photo-acid generators, the insecticides, the medicines, the liquid crystal materials and so on.

Application Domain

Organic chemistry

Technology Topic

Liquid crystalTriazine derivative +5

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Experimental program(8)

Example Embodiment

[0019] Example 1

[0020] A method for synthesizing 4,6-bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine is carried out in the following sequence of steps:

[0021] a 1.4,6-Bis-trichloromethyl-2-p-ethylbiphenyl-1,3,5-triazine preparation: add 0.02mol p-ethylbibenzonitrile and 0.05mol trichloroacetonitrile to the four-necked flask. Anhydrous aluminum trichloride 0.004 mol, adding 20.00 mL of 1,2-dichloroethane as solvent, stirring, the ice bath is reduced to 0°C, and dry HCl gas is introduced. After 5 hours, the ice bath is removed and stirred at room temperature for 20 hours. The excess trichloroacetonitrile and 1,2-dichloroethane were evaporated under reduced pressure, and the residue B was subjected to column chromatography to obtain 4.31g of white solid A, namely 0.009mol of 4,6-bistrichloromethyl-2-pair Ethyl biphenyl-1,3,5-triazine, the yield is 44.00%.

[0022] 1 H-NMR(CDCl 3 , 500MHz):

[0023] 1.299(t, 3H, CH 3 ), 2.726(q, 2H, CH 2 ), 7.352(d, 2H, 4 CH), 7.635(d, 2H, 3 CH), 7.812(d, 2H, 2 CH), 8.751(d, 2H, 1 CH)

[0024] b 1.4,6-Bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine preparation: 4.31g white solid A obtained in the previous step and 7.84g 70% tert-butyl hydroperoxide , 0.09g chromium trioxide, 27.00mL dichloromethane, stirred at room temperature for 24h. After the reaction, water was added, the organic phase was separated, dried with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was separated by column chromatography to obtain a white solid product C, namely 4,6-bistrichloromethyl-2-paraacetylated Benzene-1,3,5-triazine was 2.10g, and the yield was 47.37%.

[0025] 1 H-NMR(CDCl 3 , 500MHz),

[0026] 2.683-2.687(d, 3H, CH 3 ), 7.791-2.811(q, 2H, 1 CH), 7.853-7.873 (q, 2H, 2 CH), 8.101-8.121(q, 2H, 3 CH), 8.797(s, 2H, 4 CH)

Example Embodiment

[0027] Example 2

[0028] A method for synthesizing 4,6-bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine is carried out in the following sequence of steps:

[0029] a 2.4,6-Bistrichloromethyl-2-p-ethylbiphenyl-1,3,5-triazine preparation:

[0030] Raw materials: 0.02mol of p-ethylbibenzonitrile, 0.05mol of trichloroacetonitrile, 0.004mol of anhydrous aluminum trichloride, 20.00mL of solvent 1,2-dichloroethane were added to the four-neck flask, stirred, and the ice bath dropped to 0 At ℃, dry HCl gas was continuously introduced, the ice bath was removed after 5 hours, and stirring was performed at room temperature for 24 hours. Excess trichloroacetonitrile and 1,2-dichloroethane were distilled off under reduced pressure, and the residue was subjected to column chromatography to obtain 4.31g of white solid A, namely 0.009mol of 4,6-bistrichloromethyl-2-p-ethyl Biphenyl-1,3,5-triazine.

[0031] b 2.4,6-Bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine preparation: obtained 4.31g white solid A and solvent dichloromethane 22.00mL, 30% H 2 O 2 Mix 18.00mL, stir at room temperature, add dropwise 48% HBr1.30mL, after TLC monitoring shows that the reaction is complete, separate the organic phase, dry with anhydrous magnesium sulfate, evaporate the solvent under reduced pressure, and separate the product by column chromatography to obtain 2.58g. Yield 58.30%.

Example Embodiment

[0032] Example 3

[0033] A method for synthesizing 4,6-bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine is carried out in the following sequence of steps:

[0034] a 3.4,6-Bis-trichloromethyl-2-p-ethylbiphenyl-1,3,5-triazine preparation: add 0.39mol of p-ethylbibenzonitrile and 0.97mol of trichloroacetonitrile into a four-necked flask, Anhydrous aluminum trichloride 0.078mol, add 386.00mL 1,2-dichloroethane as a solvent, stir, the ice bath is reduced to 0°C, dry HCl gas is introduced, the ice bath is removed after 20h, and the mixture is stirred at room temperature for 18h. The excess trichloroacetonitrile and 1,2-dichloroethane were distilled off under reduced pressure, and the residue B was recrystallized from methanol and dichloromethane to obtain a white solid A whose weight was g 1 =49.40g; the crystallization mother liquor is kept at 0℃ for 24h, and the weight is g 2 = 38.10g of white solid A, the yield is 45.93%.

[0035] In this step, the total weight of the white solid A that is 4,6-bistrichloromethyl-2-p-ethylbiphenyl-1,3,5 triazine is obtained g=g 1 +g 2 =87.50g.

[0036] b 3.4,6-Bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine preparation: obtained 87.50g white solid A, 70% tert-butyl hydroperoxide 159.25g, trioxide 1.75g of chromium, 588.00mL of dichloromethane, stirring at room temperature, TLC monitoring until the reaction is complete, add water, separate the organic phase, dry with anhydrous magnesium sulfate, rotary evaporation to remove the solvent to obtain a yellow solid, soak in a small amount of petroleum ether, filter the solid Column chromatography was decolorized to obtain 4,6-bistrichloromethyl-2-p-acetylbiphenyl-1,3,5-triazine, 42.51g of white solid product C, with a yield of 47.24%.

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Classification and recommendation of technical efficacy words

good yield

Method for synthesizing 4,6-bis(trichloromethyl)-2-p-acetyl biphenyl-1,3,5-triazine

A bis-trichloromethyl and acetyl biphenyl technology, applied in the direction of organic chemistry, can solve the problems of harsh reaction conditions, environmental pollution, cumbersome post-treatment, etc., and achieve the effect of mild reaction conditions, good yield and simple operation

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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