CN100569713C - A kind of preparation method of biphenyl compound - Google Patents

Abstract

The invention provides an air-promoted method for preparing biphenyl compounds through the Suzuki cross-coupling reaction of chlorinated aromatic hydrocarbons and arylboronic acids catalyzed by nano palladium generated in situ in polyethylene glycol. The method is characterized in that it does not need to add ligands, phase transfer agents or accelerators, and does not need the protection of inert gases. Under the catalysis of nano-palladium generated in situ in polyethylene glycol, chlorinated aromatic hydrocarbons and arylboronic acids react in a mild manner. Efficient synthesis of biphenyl compounds under these conditions. Under the optimal conditions, the conversion rate of chlorinated aromatics and the separation yield of biphenyl compounds reached 95-100% and 90-99%, respectively.

Description

A kind of preparation method of biphenyl compound

technical field

The invention relates to a method for preparing biphenyl compounds by using Suzuki cross-coupling reaction in the organic synthesis of aromatic compounds.

Background technique

The Suzuki coupling reaction is one of the most efficient methods for forming C-C bonds and plays an important role in organic synthesis. The reaction has the advantages of mild reaction conditions, applicable to a variety of active functional groups, little influence by steric hindrance, high yield, and easy availability of aryl boronic acid. It is widely used in natural products, medicine, pesticides, herbicides, and polymer conduction Materials, synthesis of liquid crystal materials, etc. have a wide range of applications (Chem. Rev. 1995, 95, 2457-2483).

So far, most of the catalytic systems reported in the literature have used ligands or promoters, and mainly used phosphine ligands sensitive to air and moisture. Some of the reaction media are expensive (such as ionic liquids, fluorinated solvents, etc.), and some The toxicity is big (as acetonitrile, 1,4-dioxane etc.), and reaction temperature is generally higher than 80 ℃, is mainly aimed at the cross-coupling reaction (Chem.Commun.2000, 1249-1250, J.Am.Chem.Soc.2000, 122, 9058-9064, Angew.Chem.Int.Ed.2002, 41, 4176-4211, Angew.Chem.Int.Ed.2002, 41, 23, 4500-4503, Chem. Eur. J. 2004, 10, 1789-1797).

In the past two years, the literature has reported that using PEG as the reaction medium, without ligands or accelerators, and at a reaction temperature below 60°C, it has achieved good catalytic activity for the cross-coupling reactions of various bromobenzenes and arylboronic acids. , even some more active chlorobenzenes have also achieved good catalytic effects (J.Org.Chem.2005, 70, 6122-6125, J.Org.Chem.2005, 70, 5409-5412, Tetrahedron 2006 , 62, 9359-9364). However, the air-promoted in situ generated nano-palladium in PEG catalyzed the Suzuki cross-coupling reaction of chlorinated aromatic hydrocarbons and aryl boronic acids to prepare biphenyls has not been reported yet.

The purpose of the present invention is to provide a new catalytic process for preparing biphenyl compounds through the Suzuki cross-coupling reaction of chlorinated aromatic hydrocarbons and aryl boronic acid catalyzed by nano palladium generated in situ in PEG promoted by air.

Contents of the invention

The invention provides a method for preparing biphenyl compounds by the Suzuki cross-coupling reaction of chlorinated aromatics and arylboronic acid in the presence of a solvent and a catalyst. The solvent polyethylene glycol, 0.02-0.05mmol palladium catalyst precursor, 2.0-4.0mmol base, 1.0mmol chlorinated aromatic hydrocarbon, 1.1-2.0mmol aryl boronic acid and 1.0mmol internal standard n-decane were added to a 50ml round-bottomed flask. Stir and react at 30-60°C for 1-5 hours, track the reaction process with gas chromatography, after the reaction, extract the reaction product with 5ml×3 times of ether, combine the organic phases, dry with anhydrous Na ₂ SO ₄ , filter, and concentrate the filtrate , separated by column chromatography, the eluent is ethyl acetate/petroleum ether with a volume ratio of 1/10, to obtain biphenyl compounds with a conversion rate of 95-100% and an isolated yield of 90-99%.

In the above preparation method, the solvent used is polyethylene glycol with an average molecular weight of 200-2000 g/mol.

In the above-mentioned preparation method, the catalyst precursor used is palladium acetate or palladium chloride.

In the above preparation method, the zero-valent nano-palladium particles with catalytic activity are generated in situ in polyethylene glycol, and the polyethylene glycol also functions as a solvent, a reducing agent and a stabilizer.

In the above preparation method, the alkali used is potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, potassium ethylate, sodium ethylate, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium fluoride, cesium fluoride or cesium carbonate.

In the above preparation method, the chlorinated aromatics used are 4-methoxychlorobenzene, 4-acetylchlorobenzene, 4-nitrochlorobenzene, 2-nitrochlorobenzene, 4-hydroxychlorobenzene, 4-chlorobenzene Benzaldehyde, 2-chlorobenzonitrile, 2-chlorobenzoic acid, or 4-trifluoromethylchlorobenzene.

In the above preparation method, the arylboronic acid used is phenylboronic acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylbenzeneboronic acid, 2-methoxyphenylboronic acid, 3-methoxybenzene Boronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethylphenylboronic acid, 4-fluorophenylboronic acid, 3,4-difluorophenylboronic acid, 3,4,5-trifluorophenylboronic acid or 4-chlorophenylboronic acid .

The preparation method of the biphenyl compounds provided by the invention does not use ligands, cosolvents or accelerators, does not require inert gas protection, the reaction medium is environmentally friendly and can be recovered, reacts under mild conditions, and can be in situ in polyethylene glycol The generated nano-palladium acts as a catalyst to efficiently catalyze the cross-coupling reaction of chlorinated aromatic hydrocarbons and arylboronic acids, which has broad application prospects in the synthesis of natural products, medicine, pesticides, herbicides, polymer conductive materials, and liquid crystal materials. .

Detailed ways

Example 1

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), potassium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), phenylboronic acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round-bottomed flask, stirred and reacted at 30°C for 3 hours, and followed by gas chromatography. After the reaction, the reaction product was extracted with ether (5ml×3), the organic phases _were combined, dried over anhydrous _Na2SO4 , filtered and concentrated, and column chromatography was used to obtain biphenyl products. The eluent used for column chromatography was ethyl acetate /petroleum ether (volume ratio: 1/10), the structure of the product was identified by ¹ H NMR and mass spectrometry. GC analysis results showed 100% conversion and 98% yield.

Example 2

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 2-Methylphenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), potassium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 2- Phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 1 hour, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 3

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3-Methylphenylboronic Acid

In air, PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), potassium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 3- Phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 4

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Methylphenylboronic Acid

In air, PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), potassium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 4- Phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 1 hour, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 5

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 2-Methoxyphenylboronic Acid

In air, PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), sodium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 2- Add methoxyphenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 6

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), sodium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 3- Methoxyphenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 7

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Methoxyphenylboronic Acid

In air, PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), sodium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 4- Methoxyphenylboronic acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 8

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Trifluoromethylphenylboronic Acid

In air, PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), sodium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 4- Trifluoromethylphenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added into a 50 ml round bottom flask, stirred and reacted at 60° C. for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 9

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Fluorophenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), potassium tert-butoxide (2.0mmol), 4-methoxychlorobenzene (1.0mmol), Add 4-fluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 3 hours, and track the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 10

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3,4-Difluorophenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), potassium tert-butoxide (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 3,4-Difluorophenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 11

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3,4,5-Trifluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), potassium tert-butoxide (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 3,4,5-Trifluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 12

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Chlorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), potassium tert-butoxide (4.0mmol), 4-methoxychlorobenzene (1.0mmol), Add 4-chlorophenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) into a 50ml round bottom flask, stir and react at 60°C for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 13

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Acetyl Chlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), sodium tert-butoxide (2.0mmol), 4-acetylchlorobenzene (1.0mmol), benzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 30°C for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 14

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), sodium tert-butoxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), benzene Boric acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 15

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Nitrochlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), sodium tert-butoxide (2.0mmol), 2-nitrochlorobenzene (1.0mmol), benzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 16

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Hydroxychlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), sodium tert-butoxide (4.0mmol), 4-hydroxychlorobenzene (1.0mmol), phenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 17

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with Phenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), potassium ethoxide (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50ml round-bottomed flask, stirred and reacted at 30°C for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 18

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with Phenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), potassium ethoxide (4.0mmol), 2-chlorobenzonitrile (1.0mmol), phenylboronic acid ( 2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 19

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and Phenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), potassium ethoxide (2.0mmol), 2-chlorobenzoic acid (1.0mmol), phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50ml round-bottomed flask, stirred and reacted at 60°C for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 20

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), potassium ethylate (4.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), benzene Boric acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 21

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 2-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), sodium ethoxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 2-methyl Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 22

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), sodium ethoxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 3-methyl Add phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 23

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Methylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), sodium ethoxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 4-methyl Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 24

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 2-Methoxyphenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), sodium ethoxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 2-methyl Oxyphenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 25

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3-Methoxyphenylboronic Acid

In air, PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), potassium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 3- Add methoxyphenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 26

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), potassium hydroxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 4- Methoxyphenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 27

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Trifluoromethylphenylboronic Acid

In air, PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), potassium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 4- Trifluoromethylphenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 28

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Fluorophenylboronic Acid

In air, PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), potassium hydroxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 4- Fluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 29

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3,4-Difluorophenylboronic Acid

In air, PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), sodium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 3, Add 4-difluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 30

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), sodium hydroxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 3, Add 4,5-trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60° C. for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 31

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Chlorophenylboronic Acid

In air, PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), sodium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 4- Chlorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 32

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Methylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), sodium hydroxide (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methyl Add phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 33

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Methoxyphenylboronic Acid

In air, PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), potassium phosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methoxy Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 34

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), potassium phosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-trifluoro Phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 1 hour, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 35

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Fluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), potassium phosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-fluorobenzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 36

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), potassium phosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 3,4, Add 5-trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 37

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 4-Methylphenylboronic Acid

In air, PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), potassium fluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4- Add tolueneboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 38

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 4-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), potassium fluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 4- Methoxyphenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 39

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 4-Trifluoromethylphenylboronic Acid

In air, PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), potassium fluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4- Trifluoromethylphenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 40

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), potassium fluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 3, Add 4,5-trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60° C. for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 41

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 4-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), cesium fluoride (2.0mmol), 2-chlorobenzoic acid (1.0mmol), 4-methyl Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 42

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 4-Methoxyphenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), cesium fluoride (4.0mmol), 2-chlorobenzoic acid (1.0mmol), 4-methyl Oxyphenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 43

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), cesium fluoride (2.0mmol), 2-chlorobenzoic acid (1.0mmol), 4-tris Fluoromethylphenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 44

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 3,4,5-Trifluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), cesium fluoride (4.0mmol), 2-chlorobenzoic acid (1.0mmol), 3,4 , 5-trifluorophenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 45

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 4-Methylphenylboronic Acid

In air, PEG-200 (5.0mmol), Pd(OAc) ₂ (0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 4 - Add methylphenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 93% yield.

Example 46

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 4-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), Pd(OAc) ₂ (0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 4 - Add methoxyphenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 2 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 47

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 4-Fluorophenylboronic Acid

In air, PEG-2000 (1.0mmol), Pd(OAc) ₂ (0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 4 - Fluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 48

Palladium Acetate-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-2000 (2.0mmol), Pd(OAc) ₂ (0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 3 , 4,5-trifluorophenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 92% yield.

Example 49

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), potassium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50ml round-bottomed flask, stirred and reacted at 30°C for 4 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 94% yield.

Example 50

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 2-Methylphenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), potassium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 2-methyl Phenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 51

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3-Methylphenylboronic Acid

In air, PEG-2000 (1.0mmol), palladium chloride (0.02mmol), potassium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 3-methyl Phenylboronic acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 52

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Methylphenylboronic Acid

In air, PEG-2000 (2.0mmol), palladium chloride (0.05mmol), potassium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 4-methyl Phenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 53

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 2-Methoxyphenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), sodium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 2-methoxy Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 93% yield.

Example 54

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), sodium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 3-methoxy Add phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 2 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 55

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Methoxyphenylboronic Acid

In air, PEG-2000 (1.0mmol), palladium chloride (0.02mmol), sodium carbonate (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 4-methoxy Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 56

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), sodium carbonate (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 4-trifluoro Phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 57

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Fluorophenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), potassium tert-butoxide (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 4- Fluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 30° C. for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 58

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3,4-Difluorophenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), potassium tert-butoxide (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 3, Add 4-difluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 2 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 59

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-2000 (1.0mmol), palladium chloride (0.02mmol), potassium tert-butoxide (2.0mmol), 4-methoxychlorobenzene (1.0mmol), 3, Add 4,5-trifluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60° C. for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 60

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Methoxychlorobenzene with 4-Chlorophenylboronic Acid

In air, PEG-2000 (2.0mmol), palladium chloride (0.05mmol), potassium tert-butoxide (4.0mmol), 4-methoxychlorobenzene (1.0mmol), 4- Chlorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added into a 50 ml round bottom flask, stirred and reacted at 60° C. for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 61

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Acetyl Chlorobenzene with Phenylboronic Acid

In air, PEG-200 (5.0mmol), palladium chloride (0.02mmol), sodium tert-butoxide (2.0mmol), 4-acetylchlorobenzene (1.0mmol), phenylboronic acid ( 1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 30°C for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 97% yield.

Example 62

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with Phenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), sodium tert-butoxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), phenylboronic acid ( 2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 1 hour, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 63

Palladium Chloride Catalyzed Cross-Coupling Reaction of 2-Nitrochlorobenzene with Phenylboronic Acid

In air, PEG-2000 (1.0mmol), palladium chloride (0.02mmol), sodium tert-butoxide (2.0mmol), 2-nitrochlorobenzene (1.0mmol), phenylboronic acid ( 1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 64

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Hydroxychlorobenzene with Phenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), sodium tert-butoxide (4.0mmol), 4-hydroxychlorobenzene (1.0mmol), phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added into a 50ml round-bottomed flask, stirred and reacted at 60°C for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 65

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with Phenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), potassium ethylate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), phenylboronic acid (1.1mmol) Add the internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 92% yield.

Example 66

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with Phenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), potassium ethoxide (4.0mmol), 2-chlorobenzonitrile (1.0mmol), phenylboronic acid (2.0mmol ) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 67

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and Phenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), potassium ethylate (2.0mmol), 2-chlorobenzoic acid (1.0mmol), phenylboronic acid (1.1mmol) Add the internal standard n-decane (1.0 mmol) into a 50ml round bottom flask, stir and react at 60°C for 3 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 68

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with Phenylboronic Acid

In air, PEG-2000 (2.0mmol), palladium chloride (0.05mmol), potassium ethylate (4.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), phenylboronic acid ( 2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 69

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 2-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), sodium ethoxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 2-methylbenzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 30°C for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 93% yield.

Example 70

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), palladium chloride (0.05mmol), sodium ethoxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 3-methylbenzene Boric acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 71

Palladium Chloride Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Methylphenylboronic Acid

In the air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), sodium ethoxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 4-methylbenzene Add boric acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 72

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 2-Methoxyphenylboronic Acid

In air, PEG-2000 (2.0mmol), palladium chloride (0.05mmol), sodium ethoxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 2-methoxy Phenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 73

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3-Methoxyphenylboronic Acid

In the air, PEG-200 (5.0mmol), palladium chloride (0.02mmol), potassium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 3-methoxy Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 5 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 91% yield.

Example 74

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), potassium hydroxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 4-methoxy Add phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 2 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 75

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), potassium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 4-trifluoro Phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 4 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 76

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Fluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), potassium hydroxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 4-fluorobenzene Boric acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 77

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3,4-Difluorophenylboronic Acid

In air, PEG-200 (5.0mmol), palladium chloride (0.02mmol), sodium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 3,4- Add difluorophenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30° C. for 5 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 78

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), sodium hydroxide (4.0mmol), 4-nitrochlorobenzene (1.0mmol), 3,4, Add 5-trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60° C. for 2 hours, and track the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 79

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Nitrochlorobenzene with 4-Chlorophenylboronic Acid

In the air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), sodium hydroxide (2.0mmol), 4-nitrochlorobenzene (1.0mmol), 4-chlorobenzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 5 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 92% yield.

Example 80

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Methylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), sodium hydroxide (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methylbenzene Boric acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 81

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Methoxyphenylboronic Acid

In the air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), potassium phosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methoxybenzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 30°C for 3 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 93% yield.

Example 82

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), palladium chloride (0.05mmol), potassium phosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-trifluoromethyl Phenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 83

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 4-Fluorophenylboronic Acid

In air, PEG-2000 (1.0mmol), palladium chloride (0.02mmol), potassium phosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-fluorophenylboronic acid ( 1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 84

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Chlorobenzaldehyde with 3,4,5-Trifluorophenylboronic Acid

In air, PEG-2000 (2.0mmol), palladium chloride (0.05mmol), potassium phosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 3,4,5- Trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 85

Palladium Chloride Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 4-Methylphenylboronic Acid

In air, PEG-200 (5.0mmol), palladium chloride (0.02mmol), potassium fluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-methyl Phenylboronic acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round-bottomed flask, stirred and reacted at 30°C for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 94% yield.

Example 86

Palladium Chloride Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 4-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), potassium fluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-methoxy Add phenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 1 hour, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 87

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), potassium fluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-trifluoro Phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) were added into a 50 ml round bottom flask, stirred and reacted at 60° C. for 3 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Example 88

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzonitrile with 3,4,5-Trifluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), potassium fluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 3,4, Add 5-trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60° C. for 2 hours, and track the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 89

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 4-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), cesium fluoride (2.0mmol), 2-chlorobenzoic acid (1.0mmol), 4-methylbenzene Boric acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 30°C for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 98% yield.

Example 90

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 4-Methoxyphenylboronic Acid

In air, PEG-200 (20.0mmol), palladium chloride (0.05mmol), cesium fluoride (4.0mmol), 2-chlorobenzoic acid (1.0mmol), 4-methoxy Phenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 91

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 4-Trifluoromethylphenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), cesium fluoride (2.0mmol), 2-chlorobenzoic acid (1.0mmol), 4-trifluoroform Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 60°C for 4 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 92% yield.

Example 92

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 2-Chlorobenzoic Acid and 3,4,5-Trifluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), cesium fluoride (4.0mmol), 2-chlorobenzoic acid (1.0mmol), 3, 4, 5 - Trifluorophenylboronic acid (2.0 mmol) and internal standard n-decane (1.0 mmol) were added to a 50 ml round bottom flask, stirred and reacted at 60° C. for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 97% yield.

Example 93

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 4-Methylphenylboronic Acid

In air, the following molar ratios of PEG-200 (5.0mmol), palladium chloride (0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 4-methyl Add phenylboronic acid (1.1 mmol) and internal standard n-decane (1.0 mmol) into a 50 ml round bottom flask, stir and react at 30°C for 5 hours, and follow the reaction by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 94% yield.

Example 94

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 4-Methoxyphenylboronic Acid

In air, the following molar ratios of PEG-200 (20.0mmol), palladium chloride (0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 4-methyl Oxyphenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 92% yield.

Example 95

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 4-Fluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (1.0mmol), palladium chloride (0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 4-fluoro Phenylboronic acid (1.1mmol) and internal standard n-decane (1.0mmol) were added into a 50ml round bottom flask, stirred and reacted at 60°C for 4 hours, followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 95% yield.

Example 96

Palladium Chloride-Catalyzed Cross-Coupling Reaction of 4-Trifluoromethylchlorobenzene with 3,4,5-Trifluorophenylboronic Acid

In air, the following molar ratios of PEG-2000 (2.0mmol), palladium chloride (0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethylchlorobenzene (1.0mmol), 3,4 , 5-trifluorophenylboronic acid (2.0mmol) and internal standard n-decane (1.0mmol) were added to a 50ml round bottom flask, stirred and reacted at 60°C for 2 hours, and followed by gas chromatography. The aftertreatment and characterization methods of biphenyl products are the same as in Example 1. GC analysis results showed 100% conversion and 96% yield.

Claims (6)

1. One kind in the presence of solvent and catalyzer, the method for preparing biphenyl compound by the Suzuki cross-coupling reaction of chlorinated aromatic hydrocarbons and aryl boric acid, it is characterized in that this method is in air, successively with 1.0～20.0mmol solvent polyoxyethylene glycol, 0.02～0.05mmol palladium catalyst precursor, 2.0～4.0mmol alkali, 1.0mmol chlorinated aromatic hydrocarbons, 1.1 the mark n-decane adds in the 50ml round-bottomed flask in～2.0mmol aryl boric acid and the 1.0mmol, 30～60 ℃ of stirring reactions 1～5 hour, follow the tracks of with gas-chromatography in the reaction process, after reaction finishes, with 5ml * 3 time extracted with diethyl ether reaction product, merge organic phase, use anhydrous Na ₂SO ₄Drying is filtered, and filtrate concentrates, and uses column chromatography, and elutriant is the ethyl acetate/petroleum ether of volume ratio 1/10, obtain transformation efficiency and be 95～100% and separation yield be 90～99% biphenyl compound.
2. 2. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed solvent is that molecular-weight average is 200～2000 polyoxyethylene glycol.
3. 3. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed palladium catalyst precursor is palladium or Palladous chloride.
4. 4. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed alkali is salt of wormwood, yellow soda ash, potassium tert.-butoxide, sodium tert-butoxide, potassium ethylate, sodium ethylate, potassium hydroxide, sodium hydroxide, potassiumphosphate, Potassium monofluoride, cesium fluoride or cesium carbonate.
5. 5. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed chlorinated aromatic hydrocarbons is a 4-methoxyl group chlorobenzene, 4-ethanoyl chlorobenzene; the 4-nitro-chlorobenzene, 2-nitro-chlorobenzene, 4-hydroxyl chlorobenzene; 4-chlorobenzaldehyde, 2-chlorobenzonitrile, 2-chloro-benzoic acid or 4-trifluoromethyl chlorobenzene.
6. 6. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed aryl boric acid is a phenylo boric acid, the 2-methylphenylboronic acid, the 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-methoxyphenylboronic acid, the 3-methoxyphenylboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethyl phenylo boric acid, the 4-fluorobenzoic boric acid, 3,4-two fluorobenzoic boric acids, 3,4,5-trifluoro-benzene boric acid or 4-chlorobenzene boric acid.