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Method for synthesizing copper-catalyzed substituted diphenylamine

A copper compound and compound technology are applied in the field of preparation of organic synthesis intermediates substituted diphenylamine, can solve the problems of difficult industrialization, high price, and difficulty in obtaining products, and achieve the effects of low cost, short reaction time, and low solvent toxicity

Inactive Publication Date: 2009-11-04
EAST CHINA UNIV OF SCI & TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although this method has a mild reaction and high yield, a special palladium compound is used in the reaction. This compound is expensive and difficult to obtain, and is sensitive to water and air, so the operation should be carried out under anhydrous and oxygen-free conditions, which gives Industrialization of products poses difficulties

Method used

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  • Method for synthesizing copper-catalyzed substituted diphenylamine
  • Method for synthesizing copper-catalyzed substituted diphenylamine
  • Method for synthesizing copper-catalyzed substituted diphenylamine

Examples

Experimental program
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Effect test

Embodiment 1

[0023] Embodiment 1 4, the synthesis of 4'-dimethyldianiline

[0024] In a 100ml reaction flask, add 2.98g (20.0mmol) of N-(p-methylphenyl)acetamide, 30ml of toluene, and 5.23g (24.0mmol) of p-iodotoluene in sequence, stir and dissolve and add 4.49g (40.0mmol) Potassium tert-butoxide, add 198mg (2.0mmol) cuprous chloride (CuCl) and 792mg (4.0mmol) 1,10-phenanthroline (1,10-phenanthroline) again, heat to 130 ℃ and stir reaction for 10 hours, drop to room temperature, wash the reaction solution with water (30ml×3) to neutrality, and recover the toluene, dissolve the residue in 20ml concentrated hydrochloric acid, reflux for 2 hours, neutralize the reaction solution with NaOH, and then use ethyl acetate (15mL×3 ) extraction, and dried over anhydrous sodium sulfate. The solvent is recovered to obtain the crude product. Ethanol / water recrystallization gave 3.25 g of the product 4,4'-dimethyldiphenylamine, yield: 82.5%. mp: 79-80°C.

Embodiment 2

[0025] The synthesis of embodiment 2 4-methyl-4'-methoxydiphenylamine

[0026] In a 100ml reaction flask, sequentially add 2.98g (20.0mmol) of N-(p-methylphenyl)acetamide, 30ml of xylene, and 5.62g (24.0mmol) of p-methoxyiodobenzene, stir and dissolve, then add 10.65g (40.0mmol) Potassium phosphate trihydrate, then add 381mg (2.0mmol) cuprous iodide (CuI) and 456.8mg (4.0mmol) cyclohexanediamine, heat to 160°C and stir under reflux for 10 hours, then cool to room temperature, water (30ml×3) wash the reaction solution to neutrality, after recovery of xylene, dissolve the residue in 20ml concentrated hydrochloric acid, and after reflux reaction for 2 hours, neutralize the reaction solution with NaOH, then extract with ethyl acetate (15mL×3) , and recover the solvent after drying with anhydrous sodium sulfate to obtain the crude product. Ethanol / water recrystallization gave 3.60 g of the product 4-methyl-4'-methoxydiphenylamine, yield: 84.4%. mp: 82-84°C.

Embodiment 3

[0027] The synthesis of embodiment 3 4-methyldiphenylamine

[0028] In a 100ml reaction flask, add 2.98g (20.0mmol) of N-(p-methylphenyl)acetamide, 30ml of xylene, and 4.90g (24.0mmol) of iodobenzene in sequence, stir and dissolve and add 4.49g (40.0mmol) Potassium tert-butoxide, then add 381mg (2.0mmol) cuprous iodide (CuI) and 961.2mg (4.0mmol) N, N'-dibenzylethylenediamine, heat to 160 ° C and stir under reflux for 10 hours, down to At room temperature, wash the reaction solution with water (30ml×3) to neutrality, recover xylene, dissolve the residue in 20ml concentrated hydrochloric acid, and after reflux reaction for 2 hours, neutralize the reaction solution with NaOH, and then use ethyl acetate (15mL×3 ) extraction, and after drying with anhydrous sodium sulfate, the solvent was recovered to obtain a crude product. After recrystallization, 2.75 g of the product 4-methyldianiline was obtained, yield: 75.1%. mp: 88-89°C.

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Abstract

The invention relates to a method for preparing substituted diphenylamine. The preparation method mainly comprises the following steps: heating a compound shown in a formula II and a compound shown in a formula III in an organic solvent in the presence of a catalytic amount of copper compounds, a nitrogen-containing ligand, and alkali, generating a coupling reaction, and using an acid or alkali for a hydrolysis reaction to obtain a target compound shown in a formula I. Compared with the prior method for preparing the substituted diphenylamine, the preparation method has the advantages of low cost, mild reaction conditions, high yield and easy industrialized production.

Description

technical field [0001] The invention relates to a preparation method of an organic synthesis intermediate substituted for diphenylamine, which belongs to the preparation technology of an organic synthesis intermediate. technical background [0002] Substituted diphenylamine is an essential raw material for the synthesis of substituted triphenylamine and its derivatives, such as important hole transport materials N, N, N', N'-tetrakis(4-methylphenyl)-[1,1'-bi Benzene]-4,4'-diamine is synthesized by the reaction of 4,4'-dimethyldiphenylamine and 4,4'-diiodobiphenyl. As another example, 2-methyl-4-methoxydiphenylamine is an intermediate for synthesizing light and thermosensitive dye 3-diethylamino-6-methyl-7-anilinoalkane. [0003] A patent (US2098039) mentions that aniline is put into a reactor equipped with alumina at a certain speed, and reacted at a high temperature of 450° C. to obtain diphenylamine. This method can only synthesize the diphenylamine of symmetrical substi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C211/55C07C209/00C07C217/92C07C213/02C07C211/56B01J31/28B01J31/30
Inventor 陶晓春霍亚东黄应钊孙杰刘京
Owner EAST CHINA UNIV OF SCI & TECH
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