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

A kind of method of synthesizing triarylamine

A technology of triarylamine and diarylamine, which is applied in the field of synthesizing triarylamine compounds with ionic iron complexes, can solve the problems of unstable catalytic performance, easy deliquescence of ferric chloride, and inconvenient operation, so as to save raw material cost and cost Low, conducive to the effect of industrial production

Active Publication Date: 2016-02-03
HUAWEI TEHCHNOLOGIES CO LTD
View PDF4 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method is the first time that iron-based catalysts are used in the synthesis of triarylamines, which is a great improvement to the synthetic methods reported in the previous literature, but this method also has obvious disadvantages, mainly including: (1) ferrous chloride is extremely easy to Oxidation, ferric chloride is very easy to deliquescence, inconvenient to operate, and the purity of these iron salts is often mixed with a very small amount of other metals (such as copper) due to their commercial sources, resulting in unstable catalytic performance; (2) Need Adding a large amount of lithium bromide, in terms of the amount of substances, the amount of lithium bromide reached 4.0 times the amount of brominated aromatic hydrocarbons; (3) The reaction substrate is limited to brominated aromatic hydrocarbons, which has obvious price advantages and diversity, and has more commercial application prospects Chlorinated aromatic hydrocarbons not covered

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Embodiment 1: In the presence of lithium bromide, with the molecular formula [(ArNCH 2 CH 2 NAr)CH][FeCl 4 ] of ionic iron (Ⅲ) complexes (wherein Ar=3,5-di-[C(CH 3 ) 3 ]-2-(OH)-C 6 h 2 ) as a catalyst to synthesize triarylamine through the reaction of diphenylamine, ethylmagnesium bromide and p-methoxybromobenzene.

[0023] Under anhydrous and oxygen-free conditions, in an inert gas atmosphere (N 2 ), diphenylamine (0.1859 g, 1.1 mmol), diethyl ether (2.0 ml), ethylmagnesium bromide (0.99 ml, 1.1 mmol) were successively added into the reaction vessel, and the reaction was stirred at 40°C for 2 hours. Drain the solvent diethyl ether, and sequentially mix the catalyst (0.0021 g, 0.3% mmol), lithium bromide (0.0086 g, 0.1 mmol), xylene (4.0 ml) and p-methoxybromobenzene (125 μl, 1 mmol) It was added to the reaction vessel, and stirred and reacted at 140° C. for 12 hours. After cooling, the reaction was terminated with deionized water, and the yield of the product a...

Embodiment 2

[0025] Embodiment 2: In the presence of lithium bromide, with the molecular formula [(ArNCH 2 CH 2 NAr)CH][FeCl 4 ] of ionic iron (Ⅲ) complexes (wherein Ar=3,5-di-[C(CH 3 ) 3 ]-2-(OH)-C 6 h 2 ) as a catalyst to synthesize triarylamine through the reaction of diphenylamine, ethylmagnesium bromide and o-methylbromobenzene.

[0026] Under anhydrous and oxygen-free conditions, in an inert gas atmosphere (Ar), diphenylamine (0.1859 g, 1.1 mmol), tetrahydrofuran (2.0 mL), ethylmagnesium bromide (0.99 mL, 1.1 mmol) were added sequentially Into a reaction vessel, the reaction was stirred at 25 °C for 3 hours. The solvent tetrahydrofuran was drained, and the catalyst (0.0021 g, 0.3% mmol), lithium bromide (0.0086 g, 0.1 mmol), toluene (4.0 ml) and o-methylbromobenzene (120 μl, 1 mmol) were added to the In the reaction vessel, the reaction was stirred at 120° C. for 48 hours. After cooling, the reaction was terminated with deionized water, and the yield of the product was analyzed...

Embodiment 3

[0028] Embodiment 3: In the presence of lithium bromide, with the molecular formula [(ArNCH 2 CH 2 NAr)CH][FeCl 4 ] of ionic iron (Ⅲ) complexes (wherein Ar=3,5-di-[C(CH 3 ) 3 ]-2-(OH)-C 6 h 2 ) as a catalyst to synthesize triarylamine through the reaction of diphenylamine, ethylmagnesium bromide and m-methylbromobenzene.

[0029] Under anhydrous and oxygen-free conditions, in an inert gas atmosphere (Ar), diphenylamine (0.1859 g, 1.1 mmol), diethyl ether (2.0 mL), ethylmagnesium bromide (0.99 mL, 1.1 mmol) were added sequentially Transfer to a reaction container, and react at 40°C for 2 hours while stirring. Drain the solvent diethyl ether, add catalyst (0.0021 g, 0.3% mmol), lithium bromide (0.0086 g, 0.1 mmol), toluene (4.0 ml) and m-methylbromobenzene (121 μl, 1 mmol) to In the reaction vessel, the reaction was stirred at 130° C. for 18 hours. After cooling, the reaction was terminated with deionized water, and the yield of the product was analyzed by gas chromatogr...

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 discloses a method for synthesizing triarylamine, that is, an ionic iron (Ⅲ) complex with the molecular formula [(ArNCH2CH2NAr)CH][FeCl4] (wherein Ar=3,5-bis-[C(CH3)3 ]-2-(OH)-C6H2) as a catalyst, in the presence of lithium bromide, diarylamine, ethylmagnesium bromide, brominated aromatic hydrocarbon or chlorinated aromatic hydrocarbon were used as raw materials to synthesize triarylamine. The method for constructing triarylamine provided by the present invention is to use the ionic iron (Ⅲ) complex with definite structure and air stability as the catalyst, which overcomes the catalyst brought by the direct use of ferrous chloride or ferric chloride as the catalyst Unfavorable factors such as easy oxidation or deliquescence, and heterometallic interference; secondly, the method provided by the present invention introduces cheap and easy-to-get chlorinated aromatics into this synthesis method for the first time, and the consumption of catalyst and lithium bromide is only halogenated aromatics Compared with the synthetic methods reported in the literature, it has higher catalytic efficiency and wider substrate applicability.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a method for synthesizing triarylamine compounds with ionic iron (III) complexes containing bisphenol functionalized imidazoline cations. Background technique [0002] As a popular hole-transporting material, triarylamine compounds have been widely used in many fields such as organic photoconductors, organic light-emitting diodes, organic / polymer solar cells, and photochromic materials (see: ShirotaY., J. Mater. Chem., 2005, 15, 75). [0003] At present, the aryl amination of halogenated hydrocarbons catalyzed by transition metal catalysts is a commonly used method for the synthesis of triarylamines, such as Buchwald? Hartwig reaction and Ullmann reaction (see: 1. Surry, D.S., Buchwald, S.L., Chem.Sci., 2011,2,27;②Monnier,F.,Taillefer,M., Angew. Chem. Int. Ed., 2009, 48, 6954. ③ Rauws, T.R.M., Maes, B.U.W., Chem. Soc. Rev., 2012, 41, 2463). However, these synt...

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 Patents(China)
IPC IPC(8): C07C211/54C07C211/56C07C209/10C07C217/84C07C213/02C07D213/74B01J31/02
Inventor 孙宏枚解存飞夏崇亮吴钰锋
Owner HUAWEI TEHCHNOLOGIES CO LTD
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