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CN-122010797-A - 3,3' - (2-Methyl-6-methyl formate benzenesulfonyl) -biphenol and preparation method and application thereof

CN122010797ACN 122010797 ACN122010797 ACN 122010797ACN-122010797-A

Abstract

The invention relates to 3,3'- (2-methyl-6-methyl formate benzenesulfonyl) -biphenol, a preparation method and application thereof, wherein the 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol has the following structural formula: . According to the invention, different functional groups are introduced into the biphenol to obtain a new material, and compared with the traditional biphenol material, the biphenol material has better conductivity, wear resistance, moisture resistance, cold resistance and the like, and can meet different application scene requirements when being used as a liquid crystal material.

Inventors

  • LIN GUANGDE
  • DING AIHUA

Assignees

  • 凯密斯特(河南)医药有限公司

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1.3,3' - (2-Methyl-6-carboxylic acid methyl ester benzenesulfonyl) -biphenol characterized by the following structural formula: 。
  2. 2. A process for the preparation of 3,3' - (2-methyl-6-methanoate benzenesulfonyl) -biphenol based on claim 1, comprising the steps of: 1) Methyl salicylic acid reacts with methanol to obtain methyl salicylate; 2) Methyl salicylate reacts with dimethylamine thiocarbonyl chloride and potassium hydroxide to obtain 3-methyl-2-dimethylamino thiocarbonyl methyl benzoate; 3) The 3-methyl-2-dimethylamino formyl thiomethyl benzoate is subjected to intramolecular trans-position reaction to obtain 3-methyl-2-dimethylamino formyl thiomethyl benzoate; 4) 3-methyl-2-dimethylamino formyl thio benzoic acid methyl ester reacts with chlorine and water to obtain 2-methyl-6-methyl formate benzenesulfonyl chloride; 5) 2-methyl-6-methyl formate benzenesulfonyl chloride reacts with p-chloroanisole to obtain 2-methyl-6-methyl benzoate-4 '-chloro-6' -methoxy sulfone; 6) 2-methyl-6-methyl benzoate-4 '-chloro-6' -methoxy sulfone and sodium hydroxide react in the presence of a reducing agent and a palladium-carbon catalyst to obtain an intermediate BP013-6 with the following structural formula; 7) Intermediate BP013-6 reacts with hydrochloric acid to obtain a target product BP013.
  3. 3. The method for preparing 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol according to claim 2, wherein step 1) comprises the steps of: 11 Methyl salicylic acid is dissolved by methanol, sulfuric acid is added for reaction, and the reaction temperature is controlled to be 50-70 ℃; 12 After the reaction of the step 11), standing and layering reactants, transferring an upper layer liquid, and adding sodium bicarbonate solution for reaction; and 13, after the reaction in the step 12) is completed, standing and layering reactants, and reserving the lower layer to obtain methyl salicylate.
  4. 4. The method for preparing 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol according to claim 2, wherein step 2) comprises the steps of: 21 Methyl salicylate and potassium hydroxide solution are added into the dimethylamino thioacyl chloride acetone solution, and the reaction temperature is controlled to be not higher than 0 ℃; 22 After the reaction of the step 21), adding water, crystallizing, and carrying out solid-liquid separation to obtain a 3-methyl-2-dimethylamino thioformyl methyl benzoate crude product; 23 Heating and dissolving the crude product of the dimethylamino-thioformyl methyl benzoate with methanol, cooling and crystallizing, separating solid from liquid to obtain a filter cake, and drying the filter cake to obtain the dimethylamino-thioformyl methyl benzoate.
  5. 5. The method for preparing 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol according to claim 2, wherein step 3) comprises the steps of: 31 Dissolving the dimethylamino thioformyl methyl benzoate with dodecane, and carrying out heat preservation reaction for 6h at 200 ℃ under the protection of nitrogen; 32 After the reaction of step 31) is completed, standing for layering, and taking the lower layer to obtain the 3-methyl-2-dimethylamino formyl thio methyl benzoate.
  6. 6. The method for preparing 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol according to claim 2, wherein step 4) comprises the steps of: 41 3-methyl-2-dimethylamino formyl thio benzoic acid methyl ester is mixed with dichloromethane and water, chlorine is introduced, and the reaction temperature is controlled to be not higher than 0 ℃; 42 After the reaction of step 41) is completed, the temperature is raised to 20 ℃, the mixture is stood for layering, the lower layer is washed by adding water, and the lower layer is reserved after layering to obtain the 2-methyl-6-methyl formate benzenesulfonyl chloride.
  7. 7. The method for preparing 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol according to claim 2, wherein step 5) comprises the steps of: 51 Dissolving p-chloroanisole in dichloromethane, adding aluminum trichloride, adding 2-methyl-6-methyl formate benzenesulfonyl chloride under the protection of nitrogen, and controlling the reaction temperature to be not higher than 0 ℃; 52 After the reaction of the step 51) is completed, adding water and hydrochloric acid, and controlling the reaction temperature to be 10-20 ℃; 53 After the reaction of step 52) is completed, standing for layering, adding water into the lower layer for washing, and retaining the lower layer after layering to obtain a methylene dichloride solution of 2-methyl-6-methyl benzoate-4 '-chloro-6' -methoxy sulfone.
  8. 8. The method for preparing 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol according to claim 7, wherein step 6) comprises the steps of: 61 Adding palladium-carbon and sodium hydroxide solution into methylene dichloride solution of 2-methyl-6-methyl benzoate-4 '-chloro-6' -methoxy sulfone, adding a reducing agent which is formic acid under the protection of nitrogen, and controlling the reaction temperature to be 35-40 ℃; 62 Cooling the reactant to below 30 ℃, carrying out solid-liquid separation to obtain filtrate, and adding water into the filtrate for washing to obtain a dichloromethane solution of an intermediate BP 013-6.
  9. 9. The method for preparing 3,3' - (2-methyl-6-methanolate benzenesulfonyl) -biphenol according to claim 8, wherein step 7) comprises the steps of: 71 Adding sodium iodide, water and hydrochloric acid into dichloromethane solution of intermediate BP013-6, and controlling the reaction temperature to be 30-50 ℃; 72 After the reaction of step 71) is completed, the temperature is reduced to below 30 ℃, the mixture is stood for layering, the lower layer is washed by adding water, the mixture is concentrated under reduced pressure, ethanol is added for heating and dissolving, cooling crystallization is carried out, a filter cake is obtained through solid-liquid separation, and BP013 is obtained after the filter cake is dried.
  10. 10. Use of 3,3' - (2-methyl-6-methanoate benzenesulfonyl) -biphenol in liquid crystal materials based on claim 1.

Description

3,3' - (2-Methyl-6-methyl formate benzenesulfonyl) -biphenol and preparation method and application thereof Technical Field The invention relates to 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol and a preparation method and application thereof, belonging to the technical field of new materials. Background The most widely applied synthetic liquid crystal material (LCP) is polymerized biphenol, is an organic polymer material with conductive performance, and is mainly applied to the fields of electronics, electrics and semiconductors. However, the liquid crystal materials disclosed at present have defects in the aspects of conductivity, wear resistance, moisture resistance and cold resistance, and cannot meet the application requirements of severe environments. With advances in science and technology, there is a need to obtain liquid crystal materials for special scene applications and special performance requirements. In addition, in developing a new liquid crystal material, it is necessary to introduce different functional groups on the biphenol. While the technical barrier for introducing other functional groups on the biphenol is the coupling of aromatic hydrocarbons. The classical arene coupling reaction is a black-type coupling method, namely, halogenated arene is coupled under the catalysis of copper powder at a high temperature of more than 150 ℃. The method has the advantages of more side reactions, low yield (60%), poor product color and luster and difficult purification. Disclosure of Invention The invention firstly provides 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol, which has the following structural formula: 。 further, the preparation method of the 3,3' - (2-methyl-6-methyl formate benzenesulfonyl) -biphenol comprises the following steps: 1) Methyl salicylic acid reacts with methanol to obtain methyl salicylate; 2) Methyl salicylate reacts with dimethylamine thiocarbonyl chloride and potassium hydroxide to obtain 3-methyl-2-dimethylamino thiocarbonyl methyl benzoate; 3) The 3-methyl-2-dimethylamino formyl thiomethyl benzoate is subjected to intramolecular trans-position reaction to obtain 3-methyl-2-dimethylamino formyl thiomethyl benzoate; 4) 3-methyl-2-dimethylamino formyl thio benzoic acid methyl ester reacts with chlorine and water to obtain 2-methyl-6-methyl formate benzenesulfonyl chloride; 5) 2-methyl-6-methyl formate benzenesulfonyl chloride reacts with p-chloroanisole to obtain 2-methyl-6-methyl benzoate-4 '-chloro-6' -methoxy sulfone; 6) 2-methyl-6-methyl benzoate-4 '-chloro-6' -methoxy sulfone and sodium hydroxide react in the presence of a reducing agent and a palladium-carbon catalyst to obtain an intermediate BP013-6; 7) Intermediate BP013-6 reacts with hydrochloric acid to obtain a target product BP013. Further, step 1) comprises the steps of: 11 Methyl salicylic acid is dissolved by methanol, sulfuric acid is added for reaction, and the reaction temperature is controlled to be 50-70 ℃; 12 After the reaction of the step 11), standing and layering reactants, transferring an upper layer liquid, and adding sodium bicarbonate solution for reaction; and 13, after the reaction in the step 12) is completed, standing and layering reactants, and reserving the lower layer to obtain methyl salicylate. Further, step 2) comprises the steps of: 21 Methyl salicylate and potassium hydroxide solution are added into the dimethylamino thioacyl chloride acetone solution, and the reaction temperature is controlled to be not higher than 0 ℃; 22 After the reaction of the step 21), adding water, crystallizing, and carrying out solid-liquid separation to obtain a 3-methyl-2-dimethylamino thioformyl methyl benzoate crude product; 23 Heating and dissolving the crude product of the dimethylamino-thioformyl methyl benzoate with methanol, cooling and crystallizing, separating solid from liquid to obtain a filter cake, and drying the filter cake to obtain the dimethylamino-thioformyl methyl benzoate. Further, step 3) comprises the steps of: 31 Dissolving the dimethylamino thioformyl methyl benzoate with dodecane, and carrying out heat preservation reaction for 6h at 200 ℃ under the protection of nitrogen; 32 After the reaction of step 31) is completed, standing for layering, and taking the lower layer to obtain the 3-methyl-2-dimethylamino formyl thio methyl benzoate. Further, step 4) comprises the steps of: 41 3-methyl-2-dimethylamino formyl thio benzoic acid methyl ester is mixed with dichloromethane and water, chlorine is introduced, and the reaction temperature is controlled to be not higher than 0 ℃; 42 After the reaction of step 41) is completed, the temperature is raised to 20 ℃, the mixture is stood for layering, the lower layer is washed by adding water, and the lower layer is reserved after layering to obtain the 2-methyl-6-methyl formate benzenesulfonyl chloride. Further, step 5) comprises the steps of: 51 Dissolving p-chloroanisole in dichloromethane, adding aluminum