Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Preparation method of spirofluorene acridine intermediate

A technology for spirofluorene acridine and an intermediate is applied in the field of one-pot preparation of spirofluorene acridine, and can solve the problems of complicated separation and purification of intermediate aromatic tertiary alcohols, complicated preparation, expensive raw materials of o-haloaryl reagents, etc. Promotes wide application, simple operation, and environmentally friendly results

Inactive Publication Date: 2011-05-11
NANJING FANGYUAN GLOBAL DISPLAY TECH
View PDF1 Cites 7 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The method overcomes the technical problems of the traditional three-step preparation method of the ortho-halogen aryl reagent, such as expensive raw materials, cumbersome preparation, complicated separation and purification of the intermediate aromatic tertiary alcohol, and the obtained intermediate product and spirofluorenacridine The intermediates are all important organic intermediates with a wide range of uses in organic functional materials. The whole reaction system is simple, the process is simple, the raw materials are cheap and easy to obtain, the yield is high, and it is environmentally friendly.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Preparation method of spirofluorene acridine intermediate
  • Preparation method of spirofluorene acridine intermediate
  • Preparation method of spirofluorene acridine intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1: Synthesis of 10-hydro-spiro[fluorene-9,9'-acridine]

[0038] Take a dry 100 mL two-necked flask, add fluorenone (0.5031 g, 2.79 mmol, 1 equiv), aniline (2.20 mL, 24.1 mmol, 8.64 equiv), aniline hydrochloride (1.11 g, 14.3 mmol, 5.16 equiv) , under anhydrous and anaerobic conditions, heated to 184 ℃ and reacted for 5 hours, polyphosphoric acid (PPA) (3 mL) was added, and the reaction was continued for 20 hours. After the reaction was completed and cooled, the reaction was quenched with an appropriate amount of water, and CH 2 Cl 2 Extracted, combined the organic phases, dried, and rotary-evaporated under reduced pressure to obtain the crude product, which was purified by column chromatography using petroleum ether: dichloromethane 5:1 as the eluent to obtain a yellow powder solid 0.030 g, yield: 2%. GC-MS (EI- m / z ):331 / (M + )

Embodiment 2

[0039] Example 2: Synthesis of 14-hydro-spiro[dibenzo[c,h]acridine-7,9'-fluorene]

[0040] Take a dry 250 mL two-necked flask, add fluorenone (5.024 g, 27.9 mmol, 1 equiv), 1-naphthylamine (3.947 g, 27.6 mmol, 1 equiv), 1-naphthylamine hydrochloride (16.89 g, 94 mmol, 3.37 equiv) under anhydrous and oxygen-free conditions, heated and stirred at 180°C for 6 hours, then added polyphosphoric acid to the reaction system, and continued to react for 20 hours. After the reaction is finished, cool the reaction, add 5% aqueous sodium hydroxide solution and dichloromethane under stirring, extract, dry and rotary evaporate under reduced pressure to obtain the crude product and purify it with petroleum ether: dichloromethane 5:1 column chromatography to obtain 3.6 g of yellow powder, the yield is 30%, the purity is greater than 99%, and the melting point is higher than 300°C.

[0041] GC-MS (EI-m / z): 431 (M + ). 1 H NMR (400 MHz, CDCl 3 ): δ 8.18-8.16 (d, J = 8 Hz, 2H), 7.87-7.8...

Embodiment 3

[0044] Example 3: Synthesis of 2'-bromo-14-hydro-spiro[dibenzo[c,h]acridine-7,9'-fluorene]

[0045] Take a dry 250 mL two-necked flask, add 2-bromofluorenone (5.0 g, 19.3 mmol, 1 equiv), 1-naphthylamine (2.75 g, 19.23 mmol, 1 equiv), 1-naphthylamine hydrochloride ( 13.75 g, 76.8 mmol, 4 equiv) under anhydrous and oxygen-free conditions, heated and stirred at 180°C for 7 hours, then added polyphosphoric acid to the reaction system, and continued to react for 20 hours. After the reaction, cool the reaction, add 5% aqueous sodium hydroxide solution and dichloromethane under stirring, extract, dry and rotary evaporate under reduced pressure to obtain the crude product and purify it with petroleum ether:dichloromethane 7:1 column chromatography to obtain light yellow The powder is 1.62g, the yield is 18%, the purity is greater than 99%, and the melting point is higher than 300°C.

[0046] MALDI-TOF-MS (MALDI- m / z ): 509 / (M + ); 1 HNMR (400 MHz, CDCl 3 , ppm): δ 8.19-8.1...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a preparation method of a spirofluorene acridine intermediate, relating to the fine organic synthesis field and the photoelectric material application field. The spirofluorene acridine material with the structure shown as below is used as an important organic intermediate in the new fields such as the organic electroluminescence, the photovoltaic cell, the organic electrical storage, the organic nonlinear optics and the organic laser. The invention relates to a novel preparation method of spirofluorene acridine monomer, in particular to a two-step tandem reaction adopting the one pot method. The preparation method comprises the following steps: heating arylamine, arylamine hydrochloride and fluorenone or a derivative of fluorenone to fully react and generate open-loop 9,9'-diaryl intermediate product; and (2) adding polyphosphoric acid and arylamine in the reaction tank to close the loop, alkalifying, stirring, filtering, and washing to obtain the high purity product. The preparation method of the spirofluorene acridine intermediate has the following characteristics: (1) the one pot method is adopted for the tandem preparation process, the middle separation step is not required, the raw materials are cheap and accessible, the yield is high, the product is easy to separate and purify; and (2) the method has mass production value and is environmental friendly.

Description

technical field [0001] The invention specifically relates to a one-pot preparation method of spirofluoreneacridine, and relates to the steps and raw materials used in the preparation process of these materials. technical background [0002] Since 1987, the Tang Research Group of the American Kodak Company [Tang, C. W.; Van Slyke, S. A. Appl. Phys. Lett. 1987, 51 , 913.] published thin-film organic electroluminescent devices (Organic Light-emitting Diodes) made of organic fluorescent materials and since then, organic flat-panel displays have become another generation of market-oriented display products after liquid crystal displays. At the same time, other organic electronics and optoelectronic industries, including fields such as organic field effect transistors, organic solar cells, nonlinear optics, biosensing and lasers, and nonlinear optical materials are also moving toward marketization. The advantages of organic and plastic electronics lie in the low cost of material...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07D219/02C07D219/04
Inventor 黄维解令海梁婧赵剑锋孙鹏举常永正欧昌金张二云
Owner NANJING FANGYUAN GLOBAL DISPLAY TECH
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com