Preparation method of trifluorostyrene compound

A technology of trifluorostyrene and compounds, applied in the field of new synthesis of trifluorostyrene compounds, which can solve the problems of unfriendly environment, many steps, low reaction selectivity, etc.

Active Publication Date: 2013-10-30
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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Problems solved by technology

However, many synthetic methods of trifluorostyrene compounds reported in the prior art have many reaction steps or need to use highly toxic drugs (such as SbF 5 ), or low yield, or complex operation, or low reaction selectivity and other defects
[0005] In 1988, Heinze and Burton reported that a kind of trifluoroethylene base metal reagent was prepared as raw material with trifluoroethylene bromide or trifluorobromoethylene, and then palladium catalyzed coupling generated the reaction of trifluorostyrene, and the productive rate was higher (J.Org .Chem.1988,53,2714), but the method is complicated to operate and trifluoroiodoethylene or trifluorobromoethylene are expensive reagents
[0006] WO 03051801 reported a coupling reaction of 1,2,2-trifluorozinc reagent prepared from HFC-134a and aryl halide under palladium catalysis, although the yield of trifluorostyrene obtained by this method is relatively high, But there are many steps, need to react at low temperature, use the low butyllithium of safety and unfriendly HFC-134a to the environment, the catalyst consumption height (calculated as zinc chloride is about 1.5mol% or higher; According to iodobenzene Calculated, the dosage is about 1.9mol%) and many other disadvantages
[0007] In 2011, Ogoshi reported on JACS (J.Am.Chem.Soc.2011,133,3256) that the method for coupling tetrafluoroethylene with diphenylzinc reagent was used to generate trifluorostyrene. Dangerous tetrafluoroethylene and expensive diphenylzinc reagents are used
[0008] Chinese patent application CN 102241554 discloses a method for synthesizing trifluorostyrene, but the operation of the method is relatively complicated and the amount of catalyst used is relatively high

Method used

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  • Preparation method of trifluorostyrene compound
  • Preparation method of trifluorostyrene compound
  • Preparation method of trifluorostyrene compound

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Embodiment 1

[0120] Synthesis (I) of 1,2,2-trifluorostyrene: phenylboronic acid (122mg), potassium phosphate (636mg), bis(dibenzylideneacetone) palladium (1.2mg), tri-tert-butylphosphine tetrafluoro Add borate (1.2mg) into a 25ml Schlenk tube, repeat vacuuming, and fill with argon three times; and add 2ml redistilled toluene, 2ml redistilled DMF, 1.4ml deionized water under argon atmosphere, slowly Chlorotrifluoroethylene gas was introduced for 5min (excess). Then tighten the Teflon cock and heat at 80°C for 2h. After cooling, 1 mmol of fluorobenzene was added as an internal standard, and the yield of the fluorine spectrum was >99%. Much higher than the fluorine spectrum yield of about 70% in WO03051801.

[0121] Synthesis (II) of 1,2,2-trifluorostyrene: phenylboronic acid (122mg), potassium phosphate (636mg), bis(dibenzylideneacetone)palladium (1.2mg), tri-tert-butylphosphinetetrafluoro Add borate (1.2mg) into a 25ml Schlenk tube, repeat vacuuming, and fill with argon three times; and ...

Embodiment 2

[0123] Synthesis of 4-tert-butyltrifluorostyrene: 4-tert-butylphenylboronic acid (180 mg), potassium phosphate (636 mg), bis(dibenzylideneacetone) palladium (1.2 mg), tri-tert-butylphosphine tetra Add fluoroborate (1.2mg) into a 25ml Schlenk tube, repeat vacuuming, and fill with argon three times; and add 2ml redistilled DMF, 2ml redistilled toluene, 1.4ml deionized water under argon atmosphere, under stirring Chlorotrifluoroethylene gas was introduced slowly for 5min (excess). Then tighten the Teflon cock and heat at 80°C for 2h. After cooling, the reaction solution was washed three times with deionized water, then the aqueous phase was extracted three times with n-pentane, the organic phases were combined, and dried over anhydrous sodium sulfate. 100-200 mesh silica gel was added to the organic phase, spin-dried, and n-pentane column chromatography gave a colorless liquid with a yield of 94%. 1 H NMR (300.0MHz, CDCl 3 , 298K, TMS) δ7.42 (dd, J = 7.45, 7.40Hz, 4H), 1.33 (s...

Embodiment 3

[0125] Synthesis of 6-methoxy-2-(1,2,2-trifluorovinyl)naphthalene: 6-methoxy 2-naphthaleneboronic acid (202mg), potassium phosphate (636mg), bis(dibenzylidene Acetone) palladium (1.2mg), tri-tert-butylphosphine tetrafluoroborate (1.2mg) were added to a 25ml Schlenk tube, vacuum was repeated, and argon was filled three times; Re-distilled toluene, 1.4ml deionized water, and slowly introduce chlorotrifluoroethylene gas for 5min under stirring. Then tighten the Teflon cock and heat at 80°C for 2h. After cooling, the reaction solution was washed three times with deionized water, then the aqueous phase was extracted three times with n-pentane, the organic phases were combined, and dried over anhydrous sodium sulfate. The organic phase was added with 100-200 mesh silica gel, spin-dried, and subjected to petroleum ether column chromatography, the yield was 82%. 1 H NMR (399.6MHz, CDCl 3 , 298K, TMS) δ7.88(s, 1H), 7.77(d, J=8.7Hz, 1H), 7.76(d, J=8.9Hz, 1H), 7.52(d, J=8.7Hz, 1H), 7...

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Abstract

The invention provides a synthesis method of a trifluorostyrene compound. According to the method provided by the invention, the trifluorostyrene compound can be synthesized from an accessible fluorin containing raw material and various substituted arylboronic acid compounds in an alkali condition by using a phosphine ligand or a multiphosphine ligand and using bis(dibenzylideneacetone)dipalladium as a catalyst. By adopting the method provided by the invention, the fluorine spectrum yield is extremely improved, while the use amount of the catalyst is obviously reduced.

Description

technical field [0001] The invention relates to the field of synthesis; in particular, the invention relates to a new synthesis method of trifluorostyrene compounds. Background technique [0002] Fossil energy resources are currently the main source of energy. However, the proven reserves of oil and coal indicate that in view of the current world consumption rate, it is imperative to find alternative new green and clean energy sources. One of the main purposes of my country's national energy reserves and new energy development. [0003] Hydrogen energy has the advantages of cleanliness and inexhaustibility, and may become an important secondary energy source in the energy arena of the 21st century. Proton exchange membrane fuel cell is a kind of fuel cell that generates electricity and heat by the action of hydrogen-containing fuel and air. It has the characteristics of relatively low temperature and normal pressure, plus it has no chemical hazards to the human body and is h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C22/08C07C25/24C07C17/263C07C43/225C07C43/29C07C41/30C07C49/80C07C47/55C07C45/68C07C211/52C07C209/68C07C69/76C07C67/343C07C255/50C07C253/30C07D319/18C07D307/79
Inventor 徐春发陈盛吕龙沈其龙
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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