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Magnesium assisted nickel catalyzed multi-fluoro aromatic hydrocarbon monoarylation method

A technology of polyfluoroaromatics and nickel catalysis, which is applied in chemical instruments and methods, preparation of carbon-based compounds, preparation of organic compounds, etc., can solve problems such as difficult to achieve high-efficiency monoarylation of polyfluoroaromatics and harsh reaction conditions, and achieve Effects of high industrial production prospects, easy post-processing, high economic value and social value

Inactive Publication Date: 2016-12-07
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] The technical problem to be solved by the present invention is to overcome the difficulties that the existing arylation methods are difficult to realize the efficient monoarylation of polyfluoroaromatics and the reaction conditions are harsh, and to provide a simple operation, low cost, mild reaction conditions, polyfluoroaromatic monoarylation A method with high selectivity and high yield

Method used

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  • Magnesium assisted nickel catalyzed multi-fluoro aromatic hydrocarbon monoarylation method
  • Magnesium assisted nickel catalyzed multi-fluoro aromatic hydrocarbon monoarylation method
  • Magnesium assisted nickel catalyzed multi-fluoro aromatic hydrocarbon monoarylation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Synthesis of 2-methyl-5-(2′,3′,5′,6′-tetrafluorophenyl)thiophene with the following structural formula

[0044]

[0045] 1. Under anhydrous and oxygen-free conditions, dissolve 360mg (2.4mmol) of 1,2,4,5-tetrafluorobenzene in 1mL of tetrahydrofuran, then add 1mL of 2mol / L tetrahydrofuran solution of isopropylmagnesium chloride, and stir the reaction at room temperature After 12 hours, 3 mL of 1,4-dioxane, 0.6 mL of ethylene glycol dimethyl ether and 26.4 mg (0.10 mmol) of 18-crown-6 were added to the reaction solution, and stirring was continued at room temperature for 30 minutes.

[0046] 2. Under anhydrous and oxygen-free conditions, add 20.6g (0.08mmol) bis(1,5-cyclooctadiene) nickel, 77mg (0.1mmol ) Bis(2-bis(3,5-dimethyl-4-methoxyphenyl)phosphine)phenyl ether, stirred at room temperature for 30 minutes.

[0047] 3. Under anhydrous and oxygen-free conditions, mix the reaction solution obtained in step 1 and step 2, and add 224mg (1.0mmol) 2-methyl-5-iodothiophen...

Embodiment 2

[0049] Synthesis of 4-(2′,3′,5′,6′-tetrafluorophenyl)acetophenone with the following structural formula

[0050]

[0051] In step 2 of Example 1, bis(2-bis(3,5-dimethyl-4-methoxyphenyl)phosphine) phenyl ether was mixed with equimolar bis(2-bis(2-naphthyl) ) phosphine) phenyl ether replacement, in step 3, 2-methyl-5-iodothiophene is replaced with equimolar p-acetylphenyl trifluoromethanesulfonate, the reaction temperature is reduced to 10 ° C, other steps and implementation Same as Example 1, 4-(2′,3′,5′,6′-tetrafluorophenyl)acetophenone was obtained, the yield was 85%, and the structural characterization data was: 1 H NMR (400MHz, CDCl 3 ): δ8.08 (d, J = 8.4Hz, 2H), 7.58 (d, J = 8.0Hz, 2H), 7.15-7.10 (m, 1H), 2.66 (s, 3H).

Embodiment 3

[0053] Synthesis of 2,3,5,6-tetrafluoro-1,1'-biphenyl with the following structural formula

[0054]

[0055] In step 3 of Example 1, 2-methyl-5-iodothiophene was replaced with equimolar phenyl triflate, and the reaction temperature was raised to 40°C. Other steps were the same as in Example 1 to obtain 2 ,3,5,6-Tetrafluoro-1,1′-biphenyl, the yield is 91%, and the structural characterization data are: 1 H NMR (400MHz, CDCl 3 ):δ7.54-7.44(m,5H),7.13-7.01(m,1H);

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Abstract

The invention discloses a magnesium assisted nickel catalyzed multi-fluoro aromatic hydrocarbon monoarylation method. The method realizes cross coupling of multi-fluoro aromatic hydrocarbon and aryl halide or aryl sulfonate by adopting a compound formed by a nickel source and a diphosphine ligand as a catalyst. The coupling method has the advantages of high controllability, high monoarylation product proportion reaching 99% or above, good function group tolerance, wide substrate applicability, and realization of the yield of 80-96%. Compared with methods adopting previous catalysis catalysts (palladium system and copper system), the method adopting a brand new nickel catalysis system has the advantages of realization of cross coupling under mild conditions, excellent selectivity, low price, simplicity in operation, easiness in post-treatment, small pollution, and high social values and industrial promotion prospect.

Description

technical field [0001] The invention belongs to the technical field of arylation of polyfluoroaromatic hydrocarbons, and in particular relates to a method for selective monoarylation of polyfluoroaromatic hydrocarbons. Background technique [0002] Coupling reaction is one of the most effective means to prepare polyfluorinated biaromatic compounds. Since Takashi Sakai reported palladium-catalyzed cross-coupling of polyfluorophenylboronic acid and aryl halides to prepare polyfluorobiaryls in 2005 (TakashiSakai.Org.Lett.2005,7,4915), palladium-based cross-coupling reactions have been obtained developed rapidly. In particular, direct cross-coupling using polyfluoroaromatics as raw materials has been developed rapidly. (J.Am.Chem.Soc.2006, 128, 8574; Org.Lett.2009, 11, 3346; Org.Lett.2010, 12, 2116; J.Am.Chem.Soc.2010, 132, 16377; Org. .Lett.2011,13,276; J.FluorineChem.2013,151,50; Appl.Organometal.Chem.2014,28,180; Tetrahedron.Lett.2015,56,123), the relevant chemical reactio...

Claims

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Application Information

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IPC IPC(8): C07B37/04C07D333/12C07C45/68C07C49/813C07C17/263C07C25/18C07C25/22C07C41/30C07C43/225C07C43/174C07C253/30C07C255/52C07C67/343C07C69/76C07F7/08
CPCC07B37/04C07C17/263C07C25/18C07C25/22C07C41/30C07C43/174C07C43/225C07C45/68C07C49/813C07C67/343C07C69/76C07C253/30C07C255/52C07D333/12C07F7/081
Inventor 黄治炎王俊亚
Owner SHAANXI NORMAL UNIV
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