A kind of preparation method of oled intermediate material triphenylamine derivatives

A technology of bitriphenylamine and intermediates, which is applied in the field of chemical synthesis, can solve the problems of large amount of catalyst, high reaction temperature and high cost, and achieves the effects of reducing the cost of raw materials, reducing the reaction temperature and mild reaction conditions.

Active Publication Date: 2017-03-29
烟台九目化学股份有限公司
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Problems solved by technology

[0005] In this synthesis method, 4,4'-dibromobiphenyl and 4-nitrodiphenylamine undergo Ullmann coupling reaction and hydrogenation reduction reaction to form the final product, and the reaction temperature in the first step is relatively high (180-190°C). , and the amount of catalyst is relatively large, and the cost is relatively high; the second hydrogenation reaction must be carried out under pressurized conditions, which requires high equipment and is not suitable for industrial production

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  • A kind of preparation method of oled intermediate material triphenylamine derivatives
  • A kind of preparation method of oled intermediate material triphenylamine derivatives
  • A kind of preparation method of oled intermediate material triphenylamine derivatives

Examples

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Effect test

Embodiment 1

[0026] Example 1: Preparation of N4, N4'-bis(4-aminophenyl)-N4, N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (compound 5)

[0027]

[0028] Synthesis of compound 2:

[0029] In a 250ml round bottom flask, add p-bromoaniline (13.8g, 80mmol), cyclohexanone (7.8g, 80mmol), p-toluenesulfonic acid (5.5g, 32mmol), toluene 180ml, under nitrogen protection, heat up to 100°C , stirred for 15h (TLC tracking detection, until the raw material point disappeared). After the reaction was cooled, it was washed with water until pH = 7, concentrated by rotary evaporation to obtain a deep red solid, purified by crystallization with toluene, and dried in vacuo to obtain 18.8 g of a deep red solid with a yield of 93.5%.

[0030] Synthesis of compound 4:

[0031] In a 250ml round bottom flask, add compound 2 (17.6g, 70mmol), compound 3 (10.8g, 32mmol), potassium tert-butoxide (11.2g, 100mmol), tetrakistriphenylphosphine palladium (0.185g, 0.16mmol ), DMF180ml, under the protection of nitrogen, s...

Embodiment 2

[0034] Example 2: Preparation of N4, N4'-bis(4-aminophenyl)-N4,N4'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'- Diamine (Compound 10)

[0035]

[0036] Synthesis of compound 7:

[0037] In a 250ml round bottom flask, add p-bromoaniline (13.8g, 80mmol), 9-fluorenone (14.4g, 80mmol), p-toluenesulfonic acid (5.5g, 32mmol), toluene 180ml, under nitrogen protection, heat up to 100 °C, stirred for 20 h (TLC tracking detection until the raw material point disappeared). After the reaction was cooled, it was washed with water until pH = 7, concentrated by rotary evaporation to obtain a deep red solid, purified by crystallization of toluene, and dried in vacuo to obtain 23.8 g of a deep red solid with a yield of 90%.

[0038] Synthesis of Compound 9:

[0039] In a 250ml round bottom flask, add compound 7 (23.3g, 70mmol), compound 8 (11.6g, 32mmol), potassium tert-butoxide (11.2g, 100mmol), tetrakistriphenylphosphine palladium (0.37g, 0.32mmol ), DMF180ml, under the protection of nit...

Embodiment 3

[0042] Example 3: Preparation of N4, N4'-bis(3-aminophenyl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (compound 15)

[0043]

[0044] Synthesis of Compound 12:

[0045] In a 250ml round bottom flask, add m-bromoaniline (13.8g, 80mmol), cyclohexanone (7.8g, 80mmol), p-toluenesulfonic acid (5.5g, 32mmol), toluene 180ml, under nitrogen protection, heat up to 100°C , stirred for 20h (TLC tracking detection, until the raw material point disappeared). After the reaction was cooled, it was washed with water until pH = 7, concentrated by rotary evaporation to obtain a deep red solid, which was purified by toluene crystallization, and dried in vacuo to obtain 18.5 g of a deep red solid with a yield of 92%.

[0046] Synthesis of Compound 14:

[0047] In a 250ml round bottom flask, add compound 12 (17.6g, 70mmol), compound 13 (10.8g, 32mmol), potassium tert-butoxide (11.2g, 100mmol), tetrakistriphenylphosphine palladium (0.37g, 0.32mmol ), DMF180ml, under the protection of nitro...

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Abstract

The invention relates to a preparation method of an OLED intermediate material terphenylamine derivative. The method includes: taking compound A and 9-fluorenone or cyclohexanone as the raw materials, dissolving the raw materials in a benzene solvent, under the catalysis of p-toluenesulfonic acid, carrying out protective reaction to generate an intermediate product D or an intermediate product E; taking a compound B and the intermediate product D or intermediate product E, dissolving them in an N, N-dimethylformamide solvent, under the catalysis of a palladium catalyst, carrying out Ullmann coupling reaction to generate an intermediate product F or intermediate product G; taking the intermediate product F or intermediate product G, adding it into an acid solution, under acidic conditions, subjecting the intermediate product F or intermediate product G to deprotection reaction so as to generate a target product C. The target product C prepared by the method provided by the invention is mainly used as an OLED organic electroluminescent material intermediate. The preparation method provided by the invention is carried out under normal pressure, and has the advantages of cheap and easily available raw materials, mild reaction conditions, simple operation, high yield and high product purity, thus being suitable for industrial mass production.

Description

technical field [0001] The invention relates to a method for preparing OLED intermediate material terphenylamine derivatives, belonging to the field of chemical synthesis. Background technique [0002] Triphenylamine derivatives have unique physical and chemical properties and are widely used in OPC, OLED and other fields. The most representative of such compounds is N4,N4'-bis(4-aminophenyl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-bis amine. [0003] The preparation method of N4,N4'-bis(4-aminophenyl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine disclosed in the literature is mainly is the following method: [0004] [0005] In this synthesis method, 4,4'-dibromobiphenyl and 4-nitrodiphenylamine undergo Ullmann coupling reaction and hydrogenation reduction reaction to form the final product, and the reaction temperature in the first step is relatively high (180-190°C). , and the amount of catalyst is large, and the cost is high; the second hydrogenation reaction must be...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C209/62C07C211/54
CPCC07C209/62C07C249/02C07C251/20C07C211/54
Inventor 程大兴周美荣邹元明宋思思崔丽莎李特
Owner 烟台九目化学股份有限公司
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