3, 3 '-(1, 3-triazole)-sulfonyl-biphenol as well as preparation method and application thereof

Abstract

The invention relates to the technical field of liquid crystal materials, and discloses 3, 3 '-(1, 3-triazole)-sulfonyl-biphenol as well as a preparation method and application thereof.The 3, 3'-(1, 3-triazole)-sulfonyl-biphenol is synthesized by taking 3-chloro-6-methoxybenzenesulfonyl chloride as an initial raw material through an azide acylation reaction, a methyl vinyl formate cyclization reaction, a coupling reaction and a hydrolysis reaction. The invention discloses a novel liquid crystal material 3. Compared with the traditional material, the material prepared by the invention has better conductivity, wear resistance, moisture resistance, cold resistance and the like, and breaks through the technical barrier of liquid crystal material application in the market, and different functional groups are introduced on the biphenol to achieve different application scenes.

Description

Technical Field

[0001] This invention relates to the field of liquid crystal materials technology, and in particular to 3,3'-(1,3-triazole)-sulfonyl-biphenyl, its preparation method and application. Background Technology

[0002] The most widely used synthetic liquid crystal material (LCP) is polymerized biphenyl hydroquinone, an organic polymer material with conductive properties. It is mainly used in the electronics, electrical engineering, and semiconductor fields. With advancements in science and technology, to obtain liquid crystal materials with specific application scenarios and performance requirements, it is necessary to introduce different functional groups onto the biphenyl hydroquinone.

[0003] The technical barrier to introducing other functional groups onto biphenyl is the coupling of aromatic hydrocarbons. The classic aromatic hydrocarbon coupling reaction is the Ubbelohde coupling method, in which halogenated aromatic hydrocarbons are coupled at high temperatures above 150°C under copper powder catalysis. This method has many side reactions, low yield (60%), poor product color, and is difficult to purify.

[0004] In addition, liquid crystal materials prepared from biphenyl in the existing technology cannot be used stably in harsh climates or environments, and are easily damaged in harsh environments.

[0005] Therefore, there is an urgent need for 3,3'-(1,3-triazole)-sulfonyl-biphenyl, its preparation method, and its application to solve the above-mentioned technical problems. Summary of the Invention

[0006] The purpose of this invention is to overcome the technical problems existing in the prior art and to provide 3,3'-(1,3-triazole)-sulfonyl-biphenylhydrazine, its preparation method and application.

[0007] To achieve the above objectives, the present invention is implemented according to the following technical solution:

[0008] 3,3'-(1,3-triazole)-sulfonyl-biphenylhydrazine has the following structural formula: .

[0009] The preparation method of 3,3'-(1,3-triazole)-sulfonyl-biphenylhydrazine includes the following steps: 3,3'-(1,3-triazole)-sulfonyl-biphenyl was synthesized from 3-chloro-6-methoxybenzenesulfonyl chloride via azidoacylation, methyl vinyl formate cyclization, coupling, and hydrolysis.

[0010] Preferably, it includes the following steps: S1, 3-chloro-6-methoxybenzenesulfonyl chloride reacts with sodium azide to generate the intermediate 3-chloro-6-methoxybenzenesulfonyl azide with the following structural formula, denoted as BP015-1; ; The reaction equation is as follows: .

[0011] S2,BP015-1 reacts with methyl vinyl formate to generate intermediate BP015-2 with the following structural formula; ; The reaction equation is as follows: .

[0012] S3,BP015-2 reacts with sodium hydroxide to generate the intermediate BP015-3 with the following structural formula; ; The reaction equation is as follows: .

[0013] S4,BP015-3 reacts with hydrochloric acid to generate the target product 3,3'-(1,3-triazole)-sulfonyl-biphenyldiol, which is denoted as BP015. The reaction equation is as follows: .

[0014] Preferably, step S1 includes the following steps: S1.1, Add water, sodium azide, and dichloromethane to the reaction vessel; S1.2, when the temperature of the reaction vessel reaches -5℃, 3-chloro-6-methoxybenzenesulfonyl chloride is added to carry out the reaction; during the reaction, the temperature inside the reaction vessel is below 0℃; S1.3 After the reaction is complete, the layers are separated. The lower layer product is taken and washed. The lower layer product obtained after washing is a dichloromethane solution containing intermediate BP015-1.

[0015] Preferably, step S2 includes the following steps: S2.1, add a dichloromethane solution containing intermediate BP015-1 and methyl vinylformate to the reaction vessel; S2.2 was reacted at 30°C for 12 hours; after the reaction was complete, the mixture was cooled and water was added. S2.3, allow to stand and separate into layers, then take the lower layer product to obtain a dichloromethane solution containing intermediate BP015-2.

[0016] Preferably, step S3 includes the following steps: S3.1, add a dichloromethane solution containing intermediate BP015-2, a catalyst, and a reducing agent to the reaction vessel; S3.2, When the temperature of the reaction vessel is 40℃, sodium hydroxide is added to carry out the reaction; S3.3 After the reaction is complete, cool down and allow to stand for separation; take the lower layer product and wash it. The lower layer product obtained after washing is a dichloromethane solution containing intermediate BP015-3.

[0017] Preferably, in step S3.1, the catalyst is palladium on carbon and the reducing agent is formic acid.

[0018] Preferably, step S4 includes the following steps: S4.1, add a dichloromethane solution containing intermediate BP015-3, water, hydrochloric acid, and sodium iodide to the reaction vessel; S4.2, When the temperature of the reaction vessel is above 40°C, the reaction is carried out under heat preservation conditions; S4.3 After the reaction is completed at a certain temperature, dichloromethane is recovered, and then the temperature is lowered to allow crystals to precipitate. S4.4, filtration and drying yield the target product BP015.

[0019] The present invention also includes the application of 3,3'-(1,3-triazole)-sulfonyl-biphenyl in liquid crystal materials.

[0020] The 3,3'-(1,3-triazole)-sulfonyl-biphenyl prepared by this invention meets the relevant quality indicators in Table 1.

[0021]

[0022] The liquid crystal material synthesized by thermal polymerization of the modified biphenyl 3,3'-(1,3-triazole)-sulfonyl-biphenyl of the present invention shows improved performance compared with the traditional thermally polymerized biphenyl liquid crystal material, as shown in Table 2 below.

[0023]

[0024] This invention discovers that, under alkaline conditions, using palladium on carbon as a catalyst and adding formic acid as a reducing agent, the coupling of haloaromatics can be achieved in high yield (over 85%) under mild conditions. The process is low-cost, yields high-purity products (chromatographic purity ≥ 99.5%), and meets the requirements of special liquid crystal materials.

[0025] Beneficial effects: (1) The novel liquid crystal material 3,3'-(1,3-triazole)-sulfonyl-biphenyl produced by the present invention introduces different functional groups on the biphenyl to achieve different application scenarios. Compared with traditional materials, the material prepared by the present invention has better conductivity, wear resistance, moisture resistance, cold resistance, etc., breaking the technical barriers to the application of liquid crystal materials in the market (such as the inability to use stably in harsh climates or places).

[0026] (2) In the preparation method of the present invention, the yield and quality of the product are better than those of traditional processes and materials.

[0027] (3) The production process of this invention adopts full automation, which greatly reduces the intensity of manual labor while ensuring more stable product quality compared with traditional chemical production processes. It improves efficiency while reducing energy consumption and raw material consumption. Detailed Implementation

[0028] The present invention will be further described below with reference to specific embodiments. The illustrative embodiments and descriptions herein are used to explain the present invention, but are not intended to limit the present invention.

[0029] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0030] There are no particular restrictions on the purity of any of the raw materials used in this invention; however, it is preferred to use materials with conventional purity levels used in the field.

[0031] All processes in this invention are referred to by abbreviations that are common abbreviations in the field. Each abbreviation is clear and specific in its relevant application area, and those skilled in the art can understand its conventional process steps based on the abbreviation.

[0032] Example 1 3,3'-(1,3-triazole)-sulfonyl-biphenyl and its preparation method, comprising the following steps: I. Azidoylation reaction 1) Fix a 500ml three-necked flask in a chiller, and equip it with a -50 to 50℃ thermometer, mechanical stirrer, and 100ml constant pressure funnel; 2) Add 100g of water to the flask, turn on the stirrer, and continue to add 32.5g of sodium azide. Stir until it is visually dissolved, then add 300g of dichloromethane; 3) Set the chiller temperature to -15℃ and add 120g of 3-chloro-6-methoxybenzenesulfonyl chloride to the constant pressure funnel; 4) When the temperature inside the flask reaches -5°C, begin adding 3-chloro-6-methoxybenzenesulfonyl chloride dropwise. During this process, maintain the temperature inside the flask below 0°C. 5) After adding 3-chloro-6-methoxybenzenesulfonyl, continue stirring for 3 hours. Transfer the reaction solution into a 500 ml separatory funnel and allow it to separate into layers. 6) Separate the lower layer, add 50g of water, and wash once. The lower layer product obtained after washing is the reaction product BP015-1-dichloromethane solution, which can be directly used in the next step of the reaction. The upper layer is sent to the wastewater tank.

[0033] II. Cyclic Reaction 1) Fix a 500ml three-necked flask in a heat-collecting magnetic stirrer, and install a 100℃ thermometer and a reflux condenser. 2) Add the reaction product BP015-1-dichloromethane solution from the previous step to the flask, and then add 42g of methyl vinyl formate; 3) Set the water bath temperature to 50℃, raise it to 30℃, and maintain the temperature at 30℃ for 12 hours. 4) Remove the hot water and replace it with tap water for cooling. When the temperature inside the bottle drops below 25°C, add 50g of water, stir for 15 minutes, and transfer the reaction solution into a 500ml separatory funnel. 5) Let stand for 15 minutes to allow for layering. The lower layer product is the reaction product BP015-2-dichloromethane solution. The lower layer directly enters the next coupling reaction, while the upper layer enters the wastewater tank.

[0034] III. Coupling Reaction 1) Fix a 500ml four-necked flask in a heat-collecting magnetic stirrer, and equip it with a 100℃ thermometer, a reflux condenser, and a 250ml constant pressure funnel. 2) Add the reaction product BP015-2-dichloromethane solution from the previous step to the flask, turn on the stirrer, add 0.5 g of palladium on carbon (Pd / C) and 12.5 g of reducing agent; the reducing agent is formic acid; 3) Set the water bath temperature to 60℃. After heating to 40℃, add 125g of a 20wt% sodium hydroxide aqueous solution to the constant pressure funnel. Begin adding the sodium hydroxide solution dropwise. 4) After adding the 20 wt% sodium hydroxide solution, continue to keep the temperature at 50-60℃ for 30 minutes. 5) Remove the hot water from the water bath and replace it with tap water to cool the flask. When the temperature inside the flask drops below 25°C, transfer the reaction solution into a 500ml separatory funnel. Let it stand for 15 minutes to allow the layers to separate. 6) Separate the lower layer, add 100g of water, wash once. The lower layer product obtained after washing is the reaction product BP015-3-dichloromethane solution, which directly enters the next hydrolysis reaction. The upper layer enters the wastewater tank.

[0035] 7) The molar yield of product BP015-3 was measured and calculated to be >85%, which is 25% higher than that of the traditional coupling method (average 60%).

[0036] IV. Hydrolysis reaction 1) Fix a 1000ml three-necked flask in a heat-collecting magnetic stirrer, and install a 100℃ thermometer and a reflux condenser. 2) Add the product from the previous step, BP015-3-dichloromethane solution, 100g of water, and 76.8g of hydrochloric acid (32% analytical hydrochloric acid) to the flask; 3) Turn on the stirrer and add 0.35g of sodium iodide; 4) Set the water bath temperature to 50℃, raise it to above 40℃, and keep it at that temperature for 10 hours.

[0037] 5) Adjust the water bath temperature to 90℃, start the vacuum pump, adjust the vacuum degree to -0.08~-0.085MPa, and heat up to recover dichloromethane; 6) When the temperature inside the flask reaches 85℃, remove the hot water, add tap water, turn off the vacuum pump, and switch the distillation to reflux. 7) Add 200g of methanol to the flask, set the water bath temperature to 70℃, raise the temperature to 55-60℃, and stir for 1 hour. 8) Change to ice water cooling, keep the temperature inside the flask below 15℃, and maintain the temperature for crystallization for 10 hours.

[0038] 9) Filter using a Buchner funnel, collect the filter cake, and dry it in a hot air circulating oven. Obtain 100g of the target product BP015.

[0039] The 3,3'-(1,3-triazole)-sulfonyl-biphenyl prepared in Example 1 was tested, and its quality indicators met the requirements in Table 1.

[0040] The liquid crystal material synthesized by thermal polymerization of 3,3'-(1,3-triazole)-sulfonyl-biphenyl prepared in Example 1 was tested, and the data in Table 3 were obtained.

[0041]

[0042] Comparative Example 1 The traditional Ubbelohde coupling method—high-temperature coupling of halogenated aromatic hydrocarbons under copper powder catalysis—was used. The product molar yield was 60%, and the chromatographic purity was >98%.

[0043] The coupling reaction in the embodiments of the present invention uses palladium on carbon as a catalyst and formic acid as a reducing agent, with a product molar yield >85% and chromatographic purity >99.5%.

[0044] Therefore, it can be concluded that, compared with the traditional process, the product molar yield and chromatographic purity of the present invention are superior to those of the traditional process.

[0045] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. 3,3'-(1,3-triazole)-sulfonyl-biphenyl, characterized in that, It has the following structural formula: 。 2. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiphenol according to claim 1, characterized in that, Includes the following steps: 3,3'-(1,3-triazole)-sulfonyl-biphenyl was synthesized from 3-chloro-6-methoxybenzenesulfonyl chloride via azidoacylation, methyl vinyl formate cyclization, coupling, and hydrolysis.

3. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiphenol according to claim 2, characterized in that: Includes the following steps: S1, 3-chloro-6-methoxybenzenesulfonyl chloride reacts with sodium azide to generate the intermediate 3-chloro-6-methoxybenzenesulfonyl azide with the following structural formula, denoted as BP015-1; ； S2,BP015-1 reacts with methyl vinyl formate to generate intermediate BP015-2 with the following structural formula; ； S3,BP015-2 reacts with sodium hydroxide to generate the intermediate BP015-3 with the following structural formula; ； S4,BP015-3 reacts with hydrochloric acid to generate the target product 3,3'-(1,3-triazole)-sulfonyl-biphenyl, which is designated as BP015.

4. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiol according to claim 3, characterized in that: Step S1 includes the following steps: S1.1, Add water, sodium azide, and dichloromethane to the reaction vessel; S1.2, when the temperature of the reaction vessel reaches -5℃, 3-chloro-6-methoxybenzenesulfonyl chloride is added to carry out the reaction; during the reaction, the temperature inside the reaction vessel is below 0℃; S1.3 After the reaction is complete, the layers are separated. The lower layer product is taken and washed. The lower layer product obtained after washing is a dichloromethane solution containing intermediate BP015-1.

5. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiphenol according to claim 3, characterized in that: Step S2 includes the following steps: S2.1, add a dichloromethane solution containing intermediate BP015-1 and methyl vinylformate to the reaction vessel; S2.2 was reacted at 30°C for 12 hours; after the reaction was complete, the mixture was cooled and water was added. S2.3, allow to stand and separate into layers, then take the lower layer product to obtain a dichloromethane solution containing intermediate BP015-2.

6. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiphenol according to claim 3, characterized in that: Step S3 includes the following steps: S3.1, add a dichloromethane solution containing intermediate BP015-2, a catalyst, and a reducing agent to the reaction vessel; S3.2, When the temperature of the reaction vessel is 40℃, sodium hydroxide is added to carry out the reaction; S3.3 After the reaction is complete, cool down and allow to stand for separation; take the lower layer product and wash it. The lower layer product obtained after washing is a dichloromethane solution containing intermediate BP015-3.

7. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiol according to claim 6, characterized in that: In step S3.1, the catalyst is palladium on carbon and the reducing agent is formic acid.

8. The method for preparing 3,3'-(1,3-triazole)-sulfonyl-biphenyldiphenol according to claim 3, characterized in that: Step S4 includes the following steps: S4.1, add a dichloromethane solution containing intermediate BP015-3, water, hydrochloric acid, and sodium iodide to the reaction vessel; S4.2, When the temperature of the reaction vessel is above 40°C, the reaction is carried out under heat preservation conditions; S4.3 After the reaction is completed at a certain temperature, dichloromethane is recovered, and then the temperature is lowered to allow crystals to precipitate. S4.4, filtration and drying yield the target product BP015.

9. The application of 3,3'-(1,3-triazole)-sulfonyl-biphenyl in liquid crystal materials according to claim 1.

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