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Geminal difluoro bicyclohexyl liquid crystal material and synthesis method of intermediate of material

A technology of bicyclohexane and liquid crystal materials, applied in the direction of liquid crystal materials, organic chemical methods, chemical instruments and methods, etc., can solve the problems of cumbersome preparation process and high cost of raw materials, and achieve simple process, low cost of synthesis process and high yield Effect

Active Publication Date: 2019-04-19
NANJING UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] However, the preparation method provided by it has certain limitations, and the cost of raw materials is relatively high, and the preparation process is relatively cumbersome.

Method used

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  • Geminal difluoro bicyclohexyl liquid crystal material and synthesis method of intermediate of material
  • Geminal difluoro bicyclohexyl liquid crystal material and synthesis method of intermediate of material
  • Geminal difluoro bicyclohexyl liquid crystal material and synthesis method of intermediate of material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053]

[0054] Take a 2L three-necked round-bottom flask, a water separator, and a reflux condenser, and add magnetons and difluorochloroacetic acid (64g, 493mmol, 1.3eq.). Add n-hexane (1L), add compound 1 (69g, 379mmol, 1eq.) dropwise at room temperature, raise the temperature to 90°C and reflux to separate water. After 18 h, the reaction was completed, cooled to room temperature, and water (500 mL) was added using 1N NaOH (aq .) Adjust Ph=7. Separate the layers, extract with EA (ethyl acetate), wash the organic phase with water and saturated brine successively, and dry over anhydrous sodium sulfate. Spin-dried to obtain compound 2 (colorless liquid, 89 g, yield 80%). 1 H NMR (500MHz, Chloroform-d) δ5.90-5.80 (m, 1H), 5.55 (dtd, J = 15.3, 6.8, 1.4Hz, 1H), 4.76 (d, J = 6.7Hz, 2H), 1.95 ( dddd, J=15.1, 11.2, 6.8, 3.5Hz, 1H), 1.81-1.71(m, 4H), 1.31(h, J=7.0Hz, 2H), 1.20-1.05(m, 5H), 0.95-0.83( m,5H). 19 F NMR (376MHz, Chlorof orm-d): δ–63.85(s, 1F). 13C NMR (101MHz, C...

Embodiment 2

[0057]

[0058] Take a 2L three-neck round bottom flask, reflux the condenser, add zinc powder (59g, 909mmol, 3eq.) and magneton. Under nitrogen protection, anhydrous acetonitrile (1 L) and TMSCl (66 g, 606 mmol, 2 eq.) were added. Compound 2 (89g, 303mmol, 1eq.) was added dropwise at room temperature, and the temperature was raised to reflux at 120°C. After 72h, the reaction was completed, and the insoluble matter was removed by filtration. Spin dry, add 6N HCl (aq.) (600mL) and stir for 1h, extract with EA; spin dry, add 2N NaOH (aq.) to adjust pH=14, Et 2 O extraction; 6N HCl (aq.) was used again to adjust pH=1, and EA extracted. The organic phase was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. Spin-dried to obtain compound 3 (black liquid, 51 g, yield 65%). 1 H NMR (400MHz, Chloroform-d) δ8.71 (s, 1H), 5.69 (dt, J = 17.0, 10.1Hz, 1H), 5.37-5.12 (m, 2H), 2.64 (dddd, J = 22.1, 12.2 ,10.0,4.2Hz,1H),1.86(dt,J=13.0,3.1Hz,...

Embodiment 3

[0061]

[0062] Take a 500mL round-bottom flask, add magneton and compound 3 (12.9g, 49.6mmol, 1eq.). Under nitrogen protection, DCM (248mL) and DMF (1.1g, 14.9mmol, 0.3eq.) were added, oxalyl chloride (9.4g, 74.4mmol, 1.5eq.) was added dropwise at 0°C, and stirred at room temperature for 13h. After the reaction is completed, spin dry and vacuumize.

[0063] Nitromethylhydroxylamine hydrochloride (7.3g, 74.4mmol, 1.5eq.) and magnetons were added to the above system. Under nitrogen protection, DCM (300 mL) was added, triethylamine (15.0 g, 148.8 mmol, 3 eq.) was added dropwise at 0° C., stirred at room temperature for 2 h, and the reaction was completed. Water (150 mL) was added to quench the reaction. Extract with DCM (dichloromethane), wash the organic phase with water and saturated brine successively, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=50:1) gave compound 5 (pale yellow liquid, 13.8 g, 92%). 1 H NMR (400MHz, Chloroform-d) δ5.71 (dt, J ...

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Abstract

The invention belongs to the technical field of organic synthesis and particularly relates to a geminal difluoro bicyclohexyl liquid crystal material and a synthesis method of an intermediate of the material. The synthesis method of the geminal difluoro bicyclohexyl liquid crystal material comprises the following steps that 1, a compound 1 and chlorodifluoroacetic acid are esterified to obtain a compound 2; 2, the compound 2 is rearranged to obtain a compound 3; 3, the compound 3 is subjected to carbonyl addition-elimination to obtain a compound 6; 4, the compound 6 is bromized to obtain a compound 11; 5, the compound 11 is intramolecularly alkylated to obtain a compound 12; 6, the compound 12 is subjected to carbonyl reduction to obtain the compound, namely the geminal difluoro bicyclohexyl liquid crystal material. According to the material, starting with simple commercial raw materials, a common reagent and simple operation are used for completing synthesis of the geminal difluoro bicyclohexyl liquid crystal material, and a possible synthesis route is provided for the geminal difluoro bicyclohexyl liquid crystal material.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a synthetic method of gem-difluorobicyclohexane liquid crystal material and its intermediate. Background technique [0002] In 1888, the Austrian botanist F. Reinitzer first discovered the liquid crystal phenomenon. After nearly a century of exploration and research by scientists, a liquid crystal display panel was developed and successfully applied to industrialization. Liquid crystal material is an important part of liquid crystal display panel. [0003] Gem difluorobicyclohexane liquid crystal material (1,4-trans; 4,4'-anti; 4',1'-trans)-2,2-difluoro-4,4'-dipropyl-1,1'-bi (cyclohexane), the Chinese name is (1,4-trans; 4,4'-trans; 4',1'-trans)-2,2-difluoro-4,4'isopropyl-1, 1'-bicyclohexane, the existing invention patent and production process are developed by Japan OrganoScience.Lcd and Chiracol Co.Lcd. [0004] Chinese patent CN102822129A discloses a novel cyclohe...

Claims

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Application Information

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IPC IPC(8): C09K19/30C07C67/08C07C69/63C07C51/09C07C57/56C07C45/00C07C45/63C07C49/23C07C45/67C07C49/467C07C17/35C07C23/18
CPCC09K19/3003C07C17/35C07C23/18C07C45/00C07C45/63C07C45/67C07C49/23C07C49/467C07C51/09C07C57/56C07C67/08C07C69/63C07C2601/14C07B2200/07C09K2019/3004
Inventor 姚祝军魏军强
Owner NANJING UNIV
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