CN107253899B - Fluorinated biphenyl liquid crystal monomer and preparation method thereof - Google Patents
Fluorinated biphenyl liquid crystal monomer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3019—Cy-Cy-Ph-Ph
Abstract
The invention belongs to the technical field of liquid crystal material synthesis, and particularly relates to a fluorobiphenyl liquid crystal monomer and a preparation method thereof. The invention avoids the use of halogen substituent reagent, has novel and reasonable synthesis route, high target yield up to more than 95 percent, low production cost and more contribution to industrial production; the synthetic route of the invention has good reference function in the process of synthesizing other biphenyl compounds.
Description
Technical Field
The invention belongs to the technical field of liquid crystal material synthesis, and particularly relates to a fluorobiphenyl liquid crystal monomer and a preparation method thereof.
Background
The usage amount of the fluorobiphenyl liquid crystal monomer is large, and the liquid crystal monomer has the advantages of low viscosity, high resistivity, high response speed, capability of improving the mixed crystal dielectric constant and the like, and is very suitable for liquid crystal display driven by a thin film field effect transistor.
The conventional preparation method for preparing the fluorobiphenyl liquid crystal monomer is disclosed in patent CN101857517A, firstly, a palladium catalyst and a ligand are added into a reactor to be complexed in water for 0.5 hour, then, alkali, a halogenated aromatic ring compound and aryl boric acid are added, and a coupling reaction is carried out for 1-4 hours at 80 ℃ to prepare the biphenyl liquid crystal monomer compound. However, this synthesis method requires halogen substitutes, and the residue of the halogen substitutes will reduce the quality of the mixed crystal and affect the lifetime of the panel.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fluorobiphenyl liquid crystal monomer and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: a fluorinated biphenyl liquid crystal monomer has the following structural formula:
wherein R is1Is C1-C9 straight chain alkyl, R2、R3、R4Each independently is F or C; n is 1, 2 or 3; m is 1 or 2.
The second object of the present invention is to provide a method for preparing the fluorobiphenyl liquid crystal monomer, comprising the steps of:
(1) preparation of intermediate I
Under the protection of inert gas, adding the reactant I into a three-necked bottle, adding dichloromethane and triethylamine, and uniformly stirring; dripping a reactant II at the temperature of 20-30 ℃, preserving heat at the temperature of 20-60 ℃, and carrying out esterification reaction for 2-3h to prepare an intermediate I;
the structural formula of the reactant I is as follows:
the structural formula of the reactant II is as follows:
the structural formula of the intermediate I is as follows:
wherein R is1Is C1-C9 straight chain alkyl, R5Is alkyl or aromatic alkyl; n is 1, 2 or 3; m is 1 or 2;
(2) preparation of the target product
Under the protection of inert gas, adding the intermediate I and the reactant III obtained in the step (1) into a three-necked bottle, adding tert-butyl alcohol and an alkaline substance, and uniformly stirring at the temperature of 30-40 ℃; continuously adding a catalyst and a catalyst ligand, preserving the heat at the temperature of 80-90 ℃, and carrying out coupling reaction for 4-5h to obtain a target product;
the structural formula of the reactant III is as follows:
wherein R is2、R3、R4Each independently F or C.
Further, in the step (1), the molar ratio of the reactant I to the reactant II is 1: 1.1; the weight ratio of the reactant I to dichloromethane is 1: 4; the molar ratio of the reactant I to the triethylamine is 1: 1.2.
further, in the step (2), the molar ratio of the intermediate I to the reactant III is 1: 1.4; the weight ratio of the intermediate I to the tertiary butanol is 1: (8-10); the molar ratio of the intermediate I to the alkaline substance is 1: 3; the molar ratio of the intermediate I to the catalyst is 1: 0.01; the molar ratio of the intermediate I to the catalyst ligand is 1: 0.02.
further, in the step (2), the alkaline substance is potassium phosphate trihydrate, potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide; the catalyst is palladium acetate, palladium chloride or dichlorotriphenylphosphine palladium; the catalyst ligand is XphOS or Pcyb.
Further, the inert gas is nitrogen, helium or argon.
The invention has the beneficial effects that: the invention avoids the use of halogen substituent reagent, has novel and reasonable synthesis route, high target yield up to more than 95 percent, low production cost and more contribution to industrial production; the synthetic route of the invention has good reference function in the process of synthesizing other biphenyl compounds.
Drawings
FIG. 1 shows the results of example 1 of the present invention1An H-NMR spectrum;
FIG. 2 is a mass spectrum of example 1 of the present invention;
FIG. 3 shows the results of example 2 of the present invention1An H-NMR spectrum;
FIG. 4 is a mass spectrum of example 2 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A preparation method of fluorobiphenyl liquid crystal monomer-3, 4-difluoro-4 '- [ (trans; trans) -4' -pentyl- [1,1 '-dicyclohexyl ] -4-yl ] -1, 1' -biphenyl comprises the following steps:
(1) preparation of intermediate I-4- (4' -pentyl-dicyclohexyl ] -4-yl) -phenyl methanesulfonate
Under the protection of nitrogen, 164g (0.5mol) (4' -amyl-dicyclohexyl-4-yl) -phenol, 656g dichloromethane and 60.6g (0.6mol) triethylamine are added into a clean and dry three-neck flask and mechanically stirred until the system is uniform and white and turbid;
gradually dripping 63g (0.55mol) of methanesulfonyl chloride into a clean and dry three-mouth bottle under the protection of nitrogen, controlling the internal temperature to be 25-30 ℃, keeping the temperature for 2h at 25-30 ℃ after dripping, and after reaction, waiting for hydrolysis;
under the protection of nitrogen, 36g of 10 wt% diluted hydrochloric acid is dripped into a clean and dry three-mouth bottle for acidification, stirring is carried out for 30 minutes after dripping is finished, layering is carried out after stirring is finished, an organic phase is washed for 3 times until the organic phase is neutral, a solvent is removed, recrystallization is carried out once, and methane sulfonic acid 4- (4' -pentyl-dicyclohexyl ] -4-yl) -phenyl ester is obtained, wherein the yield is 98%;
(2) preparation of the object, 3, 4-difluoro-4 '- [ (trans; trans) -4' -pentyl- [1,1 '-dicyclohexyl ] -4-yl ] -1, 1' -biphenyl
Under the protection of nitrogen, adding 8.1g (0.02mol) of methanesulfonic acid 4- (4' -amyl-dicyclohexyl ] -4-yl) -phenyl ester, 3.8g (0.024mol) of 3, 4-difluorophenylboronic acid, 16.0g (0.06mol) of potassium phosphate trihydrate and 80g of tert-butyl alcohol into a clean and dry three-neck flask, controlling the internal temperature to be 30-40 ℃, stirring until the system is uniform, and introducing nitrogen for more than 30 minutes to ensure that the air in the system is completely exhausted;
under the protection of nitrogen, adding 0.045g (0.0002mol) of palladium acetate and 0.2g (0.0004mol) of XPhOS into a clean and dry three-necked bottle, heating to about 80 ℃ of the internal temperature, starting heat preservation and reflux, carrying out heat preservation reaction for 4 hours, and after the reaction is finished, waiting for hydrolysis;
under the protection of nitrogen, 44g, 10 wt% of dilute hydrochloric acid and 100g of toluene are dripped into a clean and dry three-neck flask, the temperature is reduced to the internal temperature of less than 30 ℃, the dripping is completed, the stirring is carried out for 10 minutes, and the layering is carried out after the stirring is completed. Extracting the lower water phase with 50g toluene, combining organic phases, washing for 3 times to neutrality, removing the solvent, obtaining yield of 95%, and testing the product after column chromatography and recrystallization1H-NMR and mass spectra, see FIGS. 1 and 2.
Example 2
A method for preparing fluorobiphenyl liquid crystal monomer-4- [ (trans; trans) -4 ' -amyl- [1,1 ' -dicyclohexyl ] -4-yl ] -1,1 ' -biphenyl comprises the following steps:
(1) preparation of intermediate I-4- (4' -pentyl-dicyclohexyl ] -4-yl) -phenyl methanesulfonate
Under the protection of nitrogen, 164g (0.5mol) (4' -amyl-dicyclohexyl-4-yl) -phenol, 656g dichloromethane and 60.6g (0.6mol) triethylamine are added into a clean and dry three-neck flask and mechanically stirred until the system is uniform and white and turbid;
gradually dripping 63g (0.55mol) of methanesulfonyl chloride into a clean and dry three-mouth bottle under the protection of nitrogen, controlling the internal temperature to be 25-30 ℃, keeping the temperature for 2 hours at 25-30 ℃ after dripping, and after reaction, waiting for hydrolysis;
under the protection of nitrogen, 36g of 10 wt% diluted hydrochloric acid is dripped into a clean and dry three-mouth bottle for acidification, stirring is carried out for 30 minutes after dripping is finished, layering is carried out after stirring is finished, an organic phase is washed for 3 times until the organic phase is neutral, a solvent is removed, recrystallization is carried out once, and methane sulfonic acid 4- (4' -pentyl-dicyclohexyl ] -4-yl) -phenyl ester is obtained, wherein the yield is 98%;
(2) preparation of target 4- [ (trans; trans) -4 ' -pentyl- [1,1 ' -dicyclohexyl ] -4-yl ] -1,1 ' -biphenyl
Under the protection of nitrogen, adding 8.1g (0.02mol) of methanesulfonic acid 4- (4' -amyl-dicyclohexyl ] -4-yl) -phenyl ester, 3.4g (0.024mol) of phenylboronic acid, 16.0g (0.06mol) of potassium phosphate trihydrate and 80g of tert-butyl alcohol into a clean and dry three-neck flask, controlling the internal temperature to be 30-40 ℃, stirring until the system is uniform, and introducing nitrogen for more than 30 minutes to ensure that the air in the system is completely exhausted;
under the protection of nitrogen, adding 0.045g (0.0002mol) of palladium acetate and 0.2g (0.0004mol) of XPhOS into a clean and dry three-necked bottle, heating to about 80 ℃ of the internal temperature, starting heat preservation and reflux, carrying out heat preservation reaction for 4 hours, and after the reaction is finished, waiting for hydrolysis;
under the protection of nitrogen, 44g, 10 wt% of dilute hydrochloric acid and 100g of toluene are dripped into a clean and dry three-neck flask, the temperature is reduced to the internal temperature of less than 30 ℃, the dripping is completed, the stirring is carried out for 10 minutes, and the layering is carried out after the stirring is completed. Extracting the lower water phase with 50g toluene, combining organic phases, washing for 3 times to neutrality, removing the solvent, obtaining the yield of 96%, and testing the product after column chromatography and recrystallization1H-NMR and mass spectra, see FIGS. 3 and 4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (1)
1. A preparation method of fluorobiphenyl liquid crystal monomer-3, 4-difluoro-4 '- [ (trans; trans) -4' -pentyl- [1,1 '-dicyclohexyl ] -4-yl ] -1, 1' -biphenyl is characterized by comprising the following steps:
(1) preparation of intermediate I-4- (4' -pentyl-dicyclohexyl ] -4-yl) -phenyl methanesulfonate
Under the protection of nitrogen, 164g of (4' -amyl-dicyclohexyl-4-yl) -phenol, 656g of dichloromethane and 60.6g of triethylamine are added into a clean and dry three-neck flask, and the mixture is mechanically stirred until the system is uniform and white and turbid;
gradually dripping 63g of methanesulfonyl chloride into a clean and dry three-mouth bottle under the protection of nitrogen, controlling the internal temperature to be 25-30 ℃, preserving the temperature for 2h at 25-30 ℃ after dripping, and after reaction, waiting for hydrolysis;
under the protection of nitrogen, 36g of 10 wt% diluted hydrochloric acid is dripped into a clean and dry three-mouth bottle for acidification, stirring is carried out for 30 minutes after dripping is finished, layering is carried out after stirring is finished, an organic phase is washed for 3 times until the organic phase is neutral, a solvent is removed, recrystallization is carried out once, and methane sulfonic acid 4- (4' -pentyl-dicyclohexyl ] -4-yl) -phenyl ester is obtained, wherein the yield is 98%;
(2) preparation of the object, 3, 4-difluoro-4 '- [ (trans; trans) -4' -pentyl- [1,1 '-dicyclohexyl ] -4-yl ] -1, 1' -biphenyl
Under the protection of nitrogen, adding 8.1g of methanesulfonic acid 4- (4' -amyl-dicyclohexyl ] -4-yl) -phenyl ester, 3.8g of 3, 4-difluorophenylboronic acid, 16.0g of potassium phosphate trihydrate and 80g of tert-butyl alcohol into a clean and dry three-necked bottle, controlling the internal temperature to be 30-40 ℃, stirring until the system is uniform, and introducing nitrogen for more than 30 minutes to ensure that air in the system is completely exhausted;
under the protection of nitrogen, adding 0.045g of palladium acetate and 0.2g of XPhOS into a clean and dry three-necked bottle, heating to about 80 ℃ of the internal temperature, starting heat preservation and reflux, preserving heat for reaction for 4 hours, and after the reaction is finished, waiting for hydrolysis;
under the protection of nitrogen, dropwise adding 44g, 10 wt% of dilute hydrochloric acid and 100g of toluene into a clean and dry three-neck flask, cooling to an internal temperature of less than 30 ℃, stirring for 10 minutes after dropwise adding, and layering after stirring; the lower aqueous phase was extracted with 50g of toluene, the combined organic phases were washed 3 times with water to neutrality, the solvent was removed, and the yield was 95%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102660298A (en) * | 2012-05-16 | 2012-09-12 | 河北迈尔斯通电子材料有限公司 | Mixed liquid crystal material for electric meter of smart grid |
| CN104152156A (en) * | 2014-07-22 | 2014-11-19 | 北京大学 | N-phase liquid crystal material for STN (super twisted nematic) |
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| US20120132855A1 (en) * | 2010-11-26 | 2012-05-31 | Semiconductor Energy Laboratory Co., Ltd. | Liquid crystal composition and liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660298A (en) * | 2012-05-16 | 2012-09-12 | 河北迈尔斯通电子材料有限公司 | Mixed liquid crystal material for electric meter of smart grid |
| CN104152156A (en) * | 2014-07-22 | 2014-11-19 | 北京大学 | N-phase liquid crystal material for STN (super twisted nematic) |
Non-Patent Citations (1)
| Title |
|---|
| 钯催化芳基亚磺酸钠脱SO2合成联苯类化合物的研究;刘清江;《中国优秀硕士学位论文全文数据库工程科技I辑》;20121015;第8-9页 * |
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