A kind of preparation method of fluorenyl benzindole derivative containing halogen

Abstract

The invention discloses a preparation method of a halogen-containing fluorenyl benzindole derivative, belonging to the technical field of organic synthesis. It comprises the following steps: (1) bromination reaction; (2) C-C coupling reaction; (3) etherolysis reaction; (4) intramolecular cyclization reaction. The present invention proposes a new method for preparing fluorenyl benzindole compounds for the first time, which is safe, environmentally friendly and efficient; by adopting the method of the present invention, the reaction yield of the prepared fluorenyl benzindole derivatives containing halogen High, the total yield can reach 55-65%, no need to use a large amount of precious metal palladium catalyst, the cost is greatly reduced, the purity is high, the HPLC purity can reach 99.9%, the single impurity is less than 100ppm, no dihalides and isomers, and meet OLED etc. Applications of organic optoelectronic materials.

Description

technical field [0001] The invention relates to a preparation method of a halogen-containing fluorenylbenzindole derivative, belonging to the technical field of organic synthesis. Background technique [0002] In recent years, with the development and application of organic photoelectric materials, fluorenyl benzindole compounds have become an important photoelectric material intermediate, which can be applied to organic electroluminescent materials, organic effect tubes and organic nonlinear optical materials. field of electronics. There are many preparation methods for such compounds, and the traditional preparation methods are mainly as follows: [0003] (1) Korean Doosan Chemical patent WO 2011025282 uses 9,9-dialkylbromofluorene as a raw material, C-C coupling with 2-nitrophenylboronic acid pinacol ester, Cadogan cyclization to obtain fluorenyl benzindole, Due to the selectivity problem in the cyclization process, about 50% isomers appear in the resulting product, and...

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Problems solved by technology

[0005] (2) German Merck's patent WO 2010136109 uses 9,9-dialkylbromofluorene as a raw material to obtain fluorenyl benzindole through C-N coupling with aniline and C-H activation and cyclization of palladium acetate. Due to the cyclization process There is also the selectivity problem in the cyclization reaction process, and a large amount of noble metal catalyst palladium acetate (0.1-0.2 molar weight) needs to be used in the cyclization reaction process, which greatly increases the cost of raw materials, and the obtained fluorenyl benzindole is carrying out bromination reaction There are also brominated isomers and dibrominated products, the purification is difficult, and the obtained products are difficult to meet the requirements of organic optoelectronic materials

[0007] (3) Chinese patent CN 104892487, Japan Idemitsu patent WO 2014208698 and Rohm and Haas patent WO2015046916 all use 9,9-dialkylbromofluorene as raw material, through C-N coupling with o-chloroaniline, palladium acetate C-H activation ring Fluorenyl benzindole is obtained by fluorenyl benzindole, because selectivity problem also exists in this cyclization process, and the obtained fluorenyl benzindole also has brominated isomer and dibrominated product when carrying out bromination reaction simultaneously, It is not easy to purify, and the obtained product is difficult to meet the requirements of organic optoelectronic materials

[0009] With the development of organic optoelectronic materials, the requirements for the purity of raw materials are gradually increasing. At present, the content of dibromo compounds in the products produced by the above-mentioned traditional preparation methods is relatively high, which seriously affects the performance of finished materials.

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