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1-aryl-2 perluoro or polyfluoro phenyl ethylene and its derirative, its synthesis and application

A technology of polyfluorophenylethylene and its derivatives, which is applied in the fields of chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., and can solve the problem of poor cis-trans selectivity of product olefins, poor cis-trans selectivity of products, and preparation problems. The conditions are high, and it is beneficial to industrial production, the steps are short, and the operation is simple.

Inactive Publication Date: 2004-02-18
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of this reaction is that it is not suitable for those substrates that are sensitive to alkali, and the preparation conditions for those semi-stable ylides are relatively high, and the cis-trans selectivity of the product generated by this reaction is not good
In recent years, great progress has been made in the one-step formation of corresponding phosphorus ylides involving metal carbene ((a) Aggarwal, V.K.; Fulton, J.R.; Sheldon, C.G.Javier de VicenteJ.Am.Chem.Soc., 2003, 125, 6034 -6035.(b) Mirafzl, G.A.; Cheng, G.; Woo, L.K.J.Am.Chem.Soc., 2002, 124, 176.(c) Lebel, Paquet, V.; Int.Ed.2001,40,2887.) But the phosphorus ylide that this method adopts obtains product olefin cis-trans selectivity equally bad (Aggarwal, V.K.; Fulton, J.R.; Sheldon, C.G.Javier deVicente J.Am.Chem.Soc ., 2003, 125, 6034-6035.), and most of the directly used diazo compounds have the potential to explode (a) Chen, Y.; Huang, L.-Y.; Ranada, M.A., Zhang, X.P.J.Org .Chem.67, 2002, 7185-7192.)

Method used

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  • 1-aryl-2 perluoro or polyfluoro phenyl ethylene and its derirative, its synthesis and application
  • 1-aryl-2 perluoro or polyfluoro phenyl ethylene and its derirative, its synthesis and application
  • 1-aryl-2 perluoro or polyfluoro phenyl ethylene and its derirative, its synthesis and application

Examples

Experimental program
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Embodiment 11

[0029] Example 11. Preparation of perfluorobenzaldehyde p-toluenesulfonyl hydrazone by condensation reaction

[0030] Add 9.9 g (50 mmol) of perfluorobenzaldehyde, 9.3 g (50 mmol) of p-toluenesulfonyl hydrazide and 90 ml of absolute ethanol to a 150 ml bottle, and react at room temperature under nitrogen protection for 24 hours. TLC detects that the raw material has reacted. The solvent was removed under pressure and dried under vacuum to obtain 18.2 g, with a yield of 99%. 2. Preparation of perfluorobenzaldehyde p-toluenesulfonylhydrazone sodium salt by hydrogen abstraction reaction of sodium hydride

[0031] Add 3.9 g (10.7 mmol) of perfluorobenzaldehyde p-methylbenzenesulfonyl hydrazide and 120 ml of anhydrous ethyl ether dried with sodium to a 250 ml bottle under ice bath conditions, and slowly add 0.43 g (content 60 % In mineral oil), after 24 hours of reaction at room temperature, anhydrous and oxygen-free filter, washed 3 times with 60 ml of sodium-d...

Embodiment 21

[0033] Example 21. The condensation reaction is the same as that of Example 12. The hydrogen abstraction reaction of sodium hydride is the same as that of Example 13. The preparation of the Wittig reaction 1-p-nitrophenyl-2-perfluorophenylethylene

[0034] Add 230 mg (0.75 mmol) of triphenylarsenic, 3 mg (0.007 mmol) of rhodium acetate dimer, 7 mL of 1,4-dioxane, and 18-crown-6 10 to a 15 mL bottle dried with nitrogen. Mg (0.0375 mmol), 76 mg (0.5 mmol) of p-nitrobenzaldehyde and 290 mg (0.75 mmol) of sodium salt of perfluorobenzaldehyde p-toluenesulfonyl hydrazone. After the addition of the materials, the reaction solution was vigorously stirred at room temperature for ten minutes, and then the reaction solution was immersed in an oil bath at 35°C for 5 hours. After the reaction was quenched by adding 2 ml of water, the reaction was then separated, and the water phase was used 2 ml Extract 2 times with hexyl acetate. Combine the organic phases, dry with ...

Embodiment 31

[0035] Example 31. The combined reaction is the same as in Example 12. The hydrogen abstraction reaction of sodium hydride is the same as in Example 13. The preparation of 1-p-bromophenyl-2-perfluorophenylethylene is catalyzed by the Wittig reaction

[0036] Add 230 mg (0.75 mmol) of triphenylarsenic, 3 mg (0.007 mmol) of rhodium acetate dimer, 7 mL of 1,4-dioxane, and 18-crown-6 10 to a 15 mL bottle dried with nitrogen. Mg (0.0375 mmol), 92 mg (0.5 mmol) of p-bromobenzaldehyde and 290 mg (0.75 mmol) of sodium salt of perfluorobenzaldehyde p-toluenesulfonyl hydrazone. After the addition of the materials, the reaction solution was vigorously stirred at room temperature for ten minutes, and then the reaction solution was immersed in an oil bath at 35°C for 5 hours. After the reaction was quenched by adding 2 ml of water, the reaction was then separated, and the water phase was used 2 ml The ethyl acetate was extracted twice. Combine the organic phases, dry w...

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Abstract

A 1-aryl-2 perfluoro (or polyfluoro) phenylethene and its derivative used as fluoric organic luminescent material or electrically conductive polymer is prepared from perfluoro (or polyfluoro) phenylformaldehyde through condensating with toluenesulfonyl diamine, dehydrogenating by sodium hydride, reacting on phase-transfer catalyst to generate perfluoro (or polyfluoro) phenyldiazo, catalytic decomposing by catalyst to generate metal carbene, capturing it by triphenyl (or trialkyl) arsenic, and condensating reaction on aldehide.

Description

Technical field [0001] The invention relates to the synthesis and application of a 1-aryl-2 perfluoro or polyfluoro phenylethylene and its derivatives. It is based on perfluoro or polyfluorobenzaldehyde as a raw material, through condensation with p-toluenesulfonyl hydrazine to form a hydrazone, and sodium hydride to produce the sodium salt of p-toluenesulfonyl hydrazone of perfluoro or polyfluorobenzaldehyde. In the presence of a transfer catalyst, perfluoro or polyfluorophenyl diazonium is generated on the spot. Under the action of the catalyst, the diazonium compound is catalytically decomposed to form metal carbene and is captured on the spot by triphenyl arsenic or trialkyl arsenic to form arsenic ylide, which then reacts with aldehyde Prepared by condensation reaction. The derivative has some potential industrial applications and can be developed into a new type of fluorine-containing conductive organic polymer and organic light-emitting material. Background technique [00...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/00C07C25/24C07C41/18C07C43/247C07C201/12C07C205/12C07C253/30C07C255/50
Inventor 朱士正祝诗发廖远熹
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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