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Preparation method of 4,4'-dicarbazolyl biphenyl

A technology of carbazolyl biphenyl and dichlorobiphenyl, applied in organic chemistry and other directions, can solve the problem of low nucleophilic ability of N atom

Pending Publication Date: 2020-04-21
GUANGDONG UNIV OF PETROCHEMICAL TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The main reason is the P-π conjugation between the N atom in carbazole and the benzene ring, which makes the nucleophilic ability of the N atom low, making carbazole a very challenging coupling substrate.

Method used

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  • Preparation method of 4,4'-dicarbazolyl biphenyl
  • Preparation method of 4,4'-dicarbazolyl biphenyl
  • Preparation method of 4,4'-dicarbazolyl biphenyl

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Under an inert gas atmosphere, add a stirring bar to a dry 50 mL Schlenk bottle, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 ° C, and dropwise add methylmagnesium chloride (3.0 M in THF, 2.3mmol, 0.77 mL) (about 1.5 min), stirred and reacted for 15 min after the addition, and transferred to the glove box for later use.

[0026] In the glove box, add 4,4'-dichlorobiphenyl (0.223 g, 1.0 mmol), the complex [2,6-bis(2,4,6-triisopropylphenyl ) phenyl-dicyclohexylphosphine] (allyl- ) palladium(II) chloride (0.86 mg, 0.001 mmol), 2,6-bis(2,4,6-triisopropylphenyl)phenyl-dicyclohexylphosphine (0.68 mg, 0.001 mmol) and 0.13 mL of dodecane (as an internal standard for GC analysis) was dissolved in 1 mL of xylene. At room temperature, the reaction solution in the Schlenk bottle was transferred to a pressure-resistant tube, sealed, and reacted in an oil bath at 145 °C for 3 h. The reaction solution was filtered through silica gel and diatomaceous earth, the fi...

Embodiment 2

[0030]Under an inert gas atmosphere, add a stirring bar to a dry 50 mL Schlenk bottle, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 ° C, and dropwise add methylmagnesium chloride (3.0 M in THF, 2.3mmol, 0.77 mL) (about 1.5 min), stirred and reacted for 15 min after the addition, and transferred to the glove box for later use.

[0031] In the glove box, add Pd(dba) to a pressure tube 2 (1.15 mg, 0.002 mmol), 2,6-bis(2,4,6-triisopropylphenyl)phenyl-dicyclohexylphosphine (2.72 mg, 0.004 mmol) were dissolved in 1 mL xylene, and then at 100 o After heating at C for 2 minutes, cool to room temperature, add 4,4’-dichlorobiphenyl (0.223 g, 1.0 mmol) and 0.13 mL dodecane (as internal standard for GC analysis). At room temperature, the reaction solution in the Schlenk bottle was transferred to a pressure-resistant tube, sealed, and reacted in an oil bath at 145 °C for 12 h. The reaction solution was filtered through silica gel and diatomaceous earth, the filtrate wa...

Embodiment 3

[0033] Under an inert gas atmosphere, add a stirring bar to a dry 50 mL Schlenk bottle, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 ° C, and dropwise add methylmagnesium chloride (3.0 M in THF, 2.3mmol, 0.77 mL) (about 1.5 min), stirred and reacted for 15 min after the addition, and transferred to the glove box for later use.

[0034] In the glove box, add Pd(OAc) to a pressure tube 2 (0.67 mg, 0.003 mmol), 2,6-bis(2,4,6-triisopropylphenyl)phenyl-dicyclohexylphosphine (4.1 mg, 0.006 mmol) and water (0.27 uL, 1.5 mol% , 5.0eq) was dissolved in 1 mL xylene, then in 100 o Heat at C for 3 minutes, cool to room temperature, add 4,4’-dichlorobiphenyl (0.223 g, 1.0 mmol) and 0.13 mL dodecane (as internal standard for GC analysis). At room temperature, the reaction solution in the Schlenk bottle was transferred to a pressure-resistant tube, sealed, and reacted in an oil bath at 145 °C for 12 h. The reaction solution was filtered through silica gel and diatomaceou...

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Abstract

The invention provides a preparation method of 4,4'-dicarbazolyl biphenyl. 4,4'-dichloro biphenyl and carbazole are effectively coupled to generate 4,4'-dicarbazolyl biphenyl under the action of a 2,6-bis(2,4,6-triisopropylphenyl) phenyl-dicyclohexylphosphine coordinated palladium catalyst and an organic magnesium reagent. The method is characterized in that 2,6-bis (2,4,6-triisopropylphenyl) phenyl-dicyclohexylphosphine is used as a supporting ligand of the palladium catalyst.

Description

technical field [0001] The invention relates to the preparation of 4,4'-biscarbazolyl biphenyl by palladium-catalyzed Buchwald-Hartwig coupled amination reaction, which belongs to the field of organic synthesis. Background technique [0002] N-arylcarbazoles are a class of compounds commonly found in drugs, pesticides, and organic optoelectronic materials, among which 4, 4'-dicarbazolylbiphenyl is a key chemical component of OLED devices. The traditional preparation method is the Ullmann reaction catalyzed by copper, but the reaction conditions are harsh, the amount of catalyst is large, the post-treatment is difficult, and the product purity often cannot meet the requirements of optoelectronic materials. At the end of the last century, Buchwald and Hartwig developed a palladium-catalyzed C-N bond coupling reaction, also known as the Buchwald-Hartwig coupling amination reaction, which is widely used in the amination reaction of halogenated aromatic hydrocarbons, but the pall...

Claims

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Application Information

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IPC IPC(8): C07D209/86
CPCC07D209/86
Inventor 施继成周发斌徐天汝
Owner GUANGDONG UNIV OF PETROCHEMICAL TECH
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