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Green water-phase synthesis method of primary arylamine

A green technology for aromatic primary amines, applied in the field of color-water phase synthesis of aromatic primary amines, can solve environmental pollution and other problems, achieve simple operation, solve pollution problems, and broad application prospects

Inactive Publication Date: 2012-07-11
SUN YAT SEN UNIV
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Problems solved by technology

However, even the reported aqueous-phase copper-catalyzed synthesis of primary aromatic amines requires the use of nitrogen-containing compounds as ligands, and some compounds that can decompose amines are used as phase transfer catalysts, which pollute the environment to a certain extent.
At present, there are few reports on the synthesis methods of primary aromatic amines that basically meet the requirements of the development of green chemistry. The most representative article is the method of using glucosamine as a ligand to catalyze the formation of primary aromatic amines from aromatic halides and ammonia water in 2011 ( Thakur, K.G.; Ganapathy, D.; Sekar, G., d-Glucosamine as a green ligand for copper catalyzed synthesis of primary aryl amines from aryl halides and ammonia. Chemical Communications 2011, 47(17), 5076-5078.), But this system also uses an organic solvent - acetone, which only solves the green problem of the ligand

Method used

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  • Green water-phase synthesis method of primary arylamine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Embodiment 1: the synthesis of 4-methoxyaniline

[0023] 187mg (1mmol) 4-bromoanisole, 150uL (2mmol) ammonia water, 25mg (0.1mmol) CuSO 4 ·5H 2 O, 90mg (0.5mmol) fructose, 138mg (1mmol) K 2 CO 3 , 1.5g PEG-400, 1mL H 2 Add O into a 10mL reaction tube, seal it, and react at 110°C for 8h. After the reaction stopped, extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, the filtrate was distilled under reduced pressure, separated and purified by silica gel column chromatography to obtain 98 mg of 4-methoxyaniline, the yield 80%.

[0024] 234mg (1mmol) 4-iodoanisole, 650uL (8mmol) ammonia water, 6.4mg (0.1mmol) Cu, 171mg starch, 138mg (1mmol) K 2 CO 3 , 1g PEG-300, 1mL H 2Add O into a 10mL reaction tube, seal it, and react at 90°C for 10h. After the reaction stopped, extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, the f...

Embodiment 2

[0027] Embodiment 2: the synthesis of 4-methylaniline

[0028] 171mg (1mmol) 4-bromotoluene, 950uL (12mmol) ammonia water, 16mg (0.2mmol) CuO, 144mg (0.8mmol) glucose, 28mg (0.5mmol) KOH, 1g PEG-300, 1mL H 2 O was added to a 10mL reaction tube, sealed, and reacted at 90°C for 18h. After the reaction stopped, it was extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure, separated and purified by silica gel column chromatography to obtain 80 mg of 4-methylaniline with a yield of 75 %.

[0029] With 218mg (1mmol) 4-iodotoluene, 1500uL (20mmol) ammonia water, 28.6mg (0.2mmol) Cu 2 O, 144mg (0.8mmol) fructose, 28mg (0.5mmol) KOH, 1g PEG-200, 1.5mL H 2 O was added to a 10mL reaction tube, sealed, and reacted at 80°C for 15h. After the reaction stopped, it was extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous...

Embodiment 3

[0031] Embodiment 3: the synthesis of 4-ethylaniline

[0032] With 185mg (1mmol) 4-bromoethylbenzene, 400uL (5mmol) ammonia water, 12mg (0.05mmol) Cu(NO 3 ) 2 ·3H 2 O, 103mg (0.3mmol) sucrose, 978mg (3mmol) Cs 2 CO 3 , 1.5g PEG-1000, 0.5mL H 2 Add O into a 10mL reaction tube, seal it, and react at 130°C for 14h. After the reaction stopped, it was extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure, separated and purified by silica gel column chromatography to obtain 60 mg of 4-ethylaniline with a yield of 50 %.

[0033] MS (ESI + ): m / z: 122 ([M+H] + ); 1 H NMR (300MHz, CDCl 3 )δ7.09-7.01(m, 2H), 6.71-6.64(m, 2H), 3.55(brs, 2H), 2.61(q, J=7.6Hz, 2H), 1.27(t, J=7.6Hz, 3H ). 13 C NMR (75MHz, CDCl 3 )δ144.3, 134.6, 128.8, 115.5, 28.4, 16.5.

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Abstract

The invention provides a rapid, simple and convenient synthesis method of primary arylamine which is implemented in a water phase, utilizes a green ligand, and completely satisfies the requirements of green development. An aryl halide and ammonia water are used as raw materials, water is used as a solvent, and the carbonates, fluorides, phosphates and hydroxides of alkaline metals or alkaline-earth metals are used as alkali and the temperature condition is 50-150 DEG C. The synthesis method is characterized in that primary amine is formed by catalyzing an aromatic halide or a nitrogenous heterocyclic aromatic halide and the ammonia water in a green system in which a copper source catalyst is used, a carbohydrate is used as a ligand, and polyethylene glycol is taken as a surfactant. The synthesis method of primary arylamine provided by the invention has the advantages of being simple in operation, simple in products, easy in separation of products, green and environment-friendly, etc. Compared with similar reactions reported in research papers, the synthesis method meets the requirements of green chemical development since all used solvents and reagents are green and environment-friendly; the problem of pollution is solved from the source; and a wide application prospect is achieved in the aspect of high-throughput preparation of natural products, medicines and pesticides.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, in particular to a method for synthesizing aromatic primary amines by using aryl halides and ammonia water under the condition of 50-130°C and copper catalysis, using sugar compounds as ligands, water as solvent, and green aqueous phase synthesis A method for aromatic primary amines. technical background [0002] Aromatic primary amines are important intermediates in the synthesis of drugs, materials, fine chemicals, etc., and have broad application prospects in medicine and organic synthesis industries ((a) Ley S.V., Thomas A.W.Modern synthetic methods for copper-mediated C(aryl) -O, C(aryl)-N, and C(aryl)-S bond formation. Angewandte Chemie, International Edition, 2003, 42: 5400-5449. (b) Schlummer B., Scholz U. Palladium-catalyzed C-N and C-O coupling—A practical guide from an industrial vantage point. Advanced Synthesis & Catalysis, 2004, 346:1599-1626). [0003] Taking ammonia as...

Claims

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Application Information

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IPC IPC(8): C07C209/10
Inventor 万一千黄漫娜朱新海王磊磊
Owner SUN YAT SEN UNIV
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