Novel method for preparing aromatic amine through halogenated aromatic hydrocarbon

A technology for halogenated aromatic hydrocarbons and aromatic amines, applied in the field of preparing aromatic amines, can solve the problems of difficult catalyst separation and difficult purification of products, and achieve the effects of wide application range, convenient use and mild reaction conditions

Inactive Publication Date: 2011-07-27
BEIJING INSTITUTE OF TECHNOLOGYGY
View PDF0 Cites 11 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Such as the use of a large number of organophosphorus ligands that are harmful to the environment and expensive Pd catalysts, the product is not easy to be separated by the catalyst, and the purification is difficult, which restricts its application in industrial production to a certain extent.

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
  • Novel method for preparing aromatic amine through halogenated aromatic hydrocarbon
  • Novel method for preparing aromatic amine through halogenated aromatic hydrocarbon
  • Novel method for preparing aromatic amine through halogenated aromatic hydrocarbon

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Add 20ml of dried dimethyl sulfoxide (DMSO) in a 50ml single-mouth bottle, add 3mmol2,4-dinitrochlorobenzene under stirring, then add 8mmol potassium carbonate, 2mmol dimethylamine zinc chloride complex ( [Me 2 NH 2 ] 2 ZnCl 4 ), the mixed solution was stirred and reacted at 60° C. for 10 min. After the reaction was finished, it was cooled, and the reaction solution was dripped dropwise into 80 ml of 2% aqueous sodium hydroxide solution, extracted 3 times with 20 ml of chloroform, washed once with 10 ml of water, dried, and spun The crude product was evaporated, and recrystallized from a mixed solvent of chloroform-n-hexane to obtain N,N-dimethyl-2,4-dinitroaniline (I), with a yield of 96%, Mp 86-88°C.

[0053] The reaction formula of 2,4-dinitrochlorobenzene and dimethylamine zinc chloride complex is:

[0054]

[0055] The spectral data of product (I) is: IR (KBr) v: 3110,1608,1575,1536,1511,1324cm -1 .

Embodiment 2

[0057] Replace 2,4-dinitrochlorobenzene with p-nitrochlorobenzene, increase the reaction temperature to 120°C, and react for 5 hours. Others are the same as in Example 1 to obtain the target compound N,N-dimethyl-4-nitroaniline (II), yield 86%, Mp 163-166°C. The reaction formula of p-nitrochlorobenzene and dimethylamine zinc chloride complex is:

[0058]

[0059] The spectral data of the product (II) are: IR(KBr) v: 3110, 1603, 1531, 1488, 1324, 1117, 822, 752.

Embodiment 3

[0061] Replace 2,4-dinitrochlorobenzene with 2,5-dichloronitrobenzene, raise the reaction temperature to 120°C, react for 1h, and the others are the same as in Example 1 to obtain the target compound 4-chloro-N,N-dichlorobenzene Methyl-2-nitroaniline (III), yield 85%, Mp 55-56°C. The reaction formula of 2,5-dichloronitrobenzene and dimethylamine zinc chloride complex is:

[0062]

[0063] The spectral data of product (III) is: IR (KBr) v: 1608, 1550, 1507, 1456, 1338, 1270, 889cm -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 provides a novel method for preparing an aromatic amine compound through halogenated aromatic hydrocarbon and an organic amine zinc chloride complex compound. A reaction general formula is as shown in a figure in the specification, wherein Ar is aryl and can be selected from 2,4-dinitrophenyl, p-nitrophenyl, 2-nitro-4-chlorphenyl, p-trifluoromethylphenyl, 4-formaldehyde phenyl, 2-pyrimidyl, and the like; X can be selected from F, Cl, Br, I, and the like; R1 and R2 are H, alkyl, aryl or heteroaryl, or R1 and R2 form a ternary to heptatomic naphthenic base together with carbon atoms connected with R1 and R2; reaction media are methylbenzene, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, dioxane, acetone and water; reacted alkalis are cesium carbonate, potassium phosphate, triethylamine, potassium carbonate, sodium (potassium) hydroxide and sodium (potassium) alkoxide; reaction can be implemented through both conventional heating and microwave promotion; and the means of recrystallization or column chromatography is adopted for purification. The invention provides a low-cost non-toxic efficient green method (without ligands) for establishing an aromatic C-N bond.

Description

(1) Technical field [0001] The invention relates to a new method for preparing aromatic amine (English name aromatic amine) through the reaction of halogenated aromatic hydrocarbon and organic amine zinc chloride complex. (2) Background technology [0002] Aromatic amines, as a class of important organic chemicals, can be widely used in the synthesis of compounds such as medicine, pesticides, dyes, spices, liquid crystals, conductive polymers, rubber antioxidants and stabilizers, fibers and plastics (Adv.Syn.Cat ., 2006, 348: 23-39; Angew. Chem. Int. Ed. 2010, 49: 2282-2285.). [0003] Aromatic amine compounds, as a class of important dye intermediates, play an important role in the dye industry. The discovery of aniline violet dye (Chemistry Teaching, 1998, 8: 17.) broke the history that humans can only extract dyes from natural products. In the modern dye industry, aromatic amine dyes are still one of the important branches of dyes. 1:7.), N-hydroxyethyl-N-cyanoethylani...

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): C07B43/04C07C211/52C07C209/10C07C223/06C07C221/00C07D239/42C07D295/073
Inventor 李加荣魏真史大昕张奇
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap