Synthesis method for biphenyl compounds

A synthesis method and compound technology, which is applied in the field of synthesis of biphenyl compounds, can solve the problems of expensive, unstable ligands, and Pd cannot be recycled, and achieve the effects of low cost, simple recycling, and prevention of agglomeration

Inactive Publication Date: 2014-05-21
SHAOXING UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The present invention aims at the disadvantages of palladium-catalyzed homogeneous coupling reaction of halogenated aromatic hydrocarbons and arylboronic acids in the prior art that expensive and unstable ligands need to be used, Pd cannot be recycled, and a large amount of toxic organic solvents are used, etc., and provides A synthetic method of bipheny

Method used

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  • Synthesis method for biphenyl compounds
  • Synthesis method for biphenyl compounds
  • Synthesis method for biphenyl compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] In a 100mL pressure-resistant reaction tube, add magneton, p-iodotoluene (5mmol), phenylboronic acid (7.5mmol), ZrO 2 -Pd(OAc) 2 Catalyst (280mg, containing 2.8mg palladium acetate, 0.25mol%), K 2 CO 3 (10mmol), water (5mL) and ethanol (15mL). The reaction tube was sealed with a silicone rubber gasket and heated in an oil bath at 100° C. for 0.5 hour. The reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (4 mL×2), ethyl acetate (100 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, anhydrous NaCl 2 SO 4 dried, concentrated under reduced pressure 1 H-NMR detection is determined to be a high-purity coupling product with a yield of 97%, and the structure is as follows:

[0024]

Embodiment 2-5

[0026] In a 100mL pressure-resistant reaction tube, add magnetons, p-iodotoluene (5mmol), phenylboronic acid (7.5mmol), and all the ZrO recovered in Example 1 in sequence. 2 -Pd(OAc) 2 Catalyst, K 2 CO 3 (10mmol), water (5mL) and ethanol (15mL). The reaction tube was sealed with a silicone rubber gasket and heated in an oil bath at 100° C. for 0.5 hour. The reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (4 mL×2), ethyl acetate (100 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, anhydrous NaCl 2 SO 4 dried, concentrated under reduced pressure 1 H-NMR detection confirmed that it was a high-purity coupling product. The recovered catalyst was subjected to repeated experiments, and the results are shown in Table 1.

[0027] Table 1: ZrO 2 ...

Embodiment 6

[0030] In a 10mL pressure-resistant reaction tube, add magneton, p-iodoanisole (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 Catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol%), K 2 CO 3 (2mmol), water (1mL) and ethanol (3mL). The reaction tube was sealed with a silicone rubber gasket and heated in an oil bath at 100° C. for 0.5 hour. The reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, anhydrous NaCl 2 SO 4 Drying, obtaining a high-purity coupling product after concentrating under reduced pressure, the productive rate is 97%. 1 H-NMR detection, the structure is as follows:

[0031]

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Abstract

The invention relates to the field of organic synthesis, and discloses a synthesis method for biphenyl compounds. The method comprises the following steps: in the presence of an inorganic base, in a mixed solvent of ethanol and water, adding arylboronic acid, aryl halide and a heterogeneous catalyst ZrO2-Pd(OAc)2; reacting 30-180 min while the temperature is controlled at 60-120 DEG C; after reaction liquid is cooled to room temperature, filtering the reaction liquid, washing, and recovering the catalyst; adding a NaOH aqueous solution into filtrate, and carrying out extraction, drying and concentration on the obtained product so as to obtain a high-purity biphenyl compound. According to the invention, the heterogeneous catalyst ZrO2-Pd(OAc)2 which is high in catalytic activity and reusable is used for the first time, the quick coupling of aryl halide and arylboronic acid is realized by taking green and non-toxic ethanol and water as solvents under mild conditions, and then excessive arylboronic acid is removed by using the NaOH aqueous solution, so that the high-purity biphenyl compound is obtained. The method is good in catalytic effect, simple in operation, and environment-friendly.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for synthesizing biphenyl compounds. Background technique [0002] Biphenyl compounds are a very important class of compounds, which are widely used in medicine, dyes, advanced functional materials and other fields. The development of green, low-cost and easy-to-operate synthetic methods is a research hotspot in organic synthesis. The Pd-catalyzed coupling reaction of halogenated aromatic hydrocarbons and arylboronic acids—Suzuki reaction is one of the effective methods for the synthesis of biphenyls. The classic Suzuki reaction uses palladium as a catalyst, and in the presence of ligands and bases, halogenated aromatic hydrocarbons and arylboronic acids are coupled in a homogeneous system to obtain biaryl compounds. Although the homogeneous Suzuki reaction has the advantages of high catalytic activity and good reaction selectivity, it has the disadvantages that the cat...

Claims

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Application Information

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IPC IPC(8): C07B37/00C07C15/14C07C1/32C07C43/205C07C41/30C07C255/50C07C253/30C07C49/784C07C45/68C07C25/18C07C17/263C07C47/546
Inventor 冯高峰刘福建
Owner SHAOXING UNIVERSITY
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