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A method for synthesizing aromatic primary amines in a circulating aqueous phase system

A technology of aromatic primary amines and circulating water, applied in the chemical field, can solve problems such as non-circularity, and achieve the effects of improving environmental friendliness, process economy, and easy separation and purification

Active Publication Date: 2016-08-17
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, some of these reactions require the use of non-commercially available catalysts and ligands, and some require the use of large amounts of phase transfer catalysts, and most of the catalytic systems used in these reactions are not cyclic

Method used

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  • A method for synthesizing aromatic primary amines in a circulating aqueous phase system

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Experimental program
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Embodiment 1

[0026] Embodiment 1: the synthesis of 4-methoxyaniline

[0027] 187mg (1mmol) 4-bromoanisole, 1mL ammonia water (25-28%, 13.3mmol), 8mg (0.1mmol) CuO, 58mg (0.2mmol) EDTA, 112mg (2mmol) KOH, 1mL H 2 Add O into a 10mL reaction tube, seal it, and react at 100°C for 12h. After the reaction stopped, extracted with ethyl acetate, 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 98 mg of 4-methoxyaniline, with a yield of 80% .

[0028] 1 H NMR (300MHz, CDCl 3 )δ6.75(d,J=7.8Hz,2H),6.65(d,J=8.2Hz,2H),3.75(s,3H),3.37(brs,2H). 13 C NMR (75MHz, CDCl 3 )δ: 153.0, 140.2, 116.6, 115.1, 56.1. ESI-MS: m / z=124[M+H] + .

Embodiment 2

[0029] Embodiment 2: the synthesis of p-nitroaniline

[0030] 202mg (1mmol) 4-nitrobromobenzene, 1mL ammonia water (25-28%, 13.3mmol), 6mg (0.1mmol) Cu, 79mg (0.2mmol) diethylenetriaminepentaacetic acid, 80mg (2mmol) NaOH, 1mL h 2 Add O into a 10mL reaction tube, seal it, and react at 100°C for 2h. After the reaction stopped, it was extracted with ethyl acetate, 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-methoxyaniline, with a yield of 44%. .

[0031] 1 H NMR (300MHz, DMSO) δ8.05(d, J=8.9Hz, 2H), 6.62(d, J=8.9Hz, 2H), 4.39(s, 2H). 13 CNMR (75MHz, CDCl 3 )δ: 156.3, 136.3, 127.0, 113.0.MS (EI + ):m / z=138[M + ].

Embodiment 3

[0032] Embodiment 3: the synthesis of 4-methylaniline

[0033] 170mg (1mmol) 4-bromotoluene, 1mL ammonia water (25-28%, 13.3mmol), 28mg (0.2mmol) Cu 2 O, 67 mg (0.2 mmol) EDTA disodium salt, 112 mg (2 mmol) KOH, 1 mL H 2 Add O into a 10mL reaction tube, seal it, and react at 130°C for 12h. After the reaction stopped, it was extracted with ethyl acetate, 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 80%.

[0034] 282mg (1mmol) 4-iodotoluene, 1mL ammonia water (25-28%, 13.3mmol), 8mg (0.1mmol) CuO, 79mg (0.2mmol) diethylenetriaminepentaacetic acid, 112mg (2mmol) KOH, 1mL H 2 Add O into a 10mL reaction tube, seal it, and react at 100°C for 6h. After the reaction stopped, it was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and...

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Abstract

The invention discloses a method for synthesizing an aromatic primary amine in a circulating water phase system. According to the method, an aryl halide and ammonia water are taken as raw materials, water is taken as a solvent, a carbonate, a fluoride, a phosphate or a hydroxide of an alkali metal or an alkaline-earth metal or a compound which can be converted to a corresponding alkali in water is taken as the alkali, polyamine carboxylic acid and a salt type compound thereof are taken as ligands, and a copper source catalyst is adopted for catalyzing the formation of the aromatic primary amine from the aryl halide and the ammonia water. According to the method disclosed by the invention, the water is used as the solvent, any phase transfer of the catalyst is not required, and the catalyst, the ligands and the reaction solvent, namely the water, can be recycled, so that the environment-friendly property of reaction is effectively improved, the method is more in line with requirements of green chemical development, a substrate particularly has a wide range of applications, and the method further has broad prospects in the aspects of preparation of natural products, medicaments and pesticides.

Description

Technical field: [0001] The invention relates to the technical field of chemistry, in particular to a method for synthesizing primary aromatic amines in a recyclable aqueous phase system. Background technique: [0002] Aromatic primary amines are an important intermediate in organic synthesis, and are also important intermediates in the manufacturing process of agricultural chemicals, dyes, medicines and other chemical materials, and are widely used in pesticides, medicine and material science ((a)K. Weissermel, H.J. Arpe, Industry Organic Chemistry, Wiley-VCH, Weinheim, 1997; (b) S.A. Lawrence, Amines: Synthesis Properties, and Application, Cambridge University Press, Cambridge, 2004; (c) G. Evano, N. Blanchard, M. Toumi, Chem. Rev., 108 (2008) 3054-3131; (d) Y. Aubin, C. Fischmeister, C. M. Thomas, J.-L. Renaud, Chem. Soc. Rev., 39 (2010) 4130 -4145.). Therefore, how to prepare aromatic primary amines more conveniently and quickly has aroused widespread attention. [00...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B43/04C07D213/73C07C209/10C07C211/51C07C211/52C07C211/45C07C211/46C07C211/47C07C213/02C07C217/84C07C221/00C07C225/22C07C227/08C07C229/60C07C231/12C07C237/30
Inventor 朱新海杨波廖礼豪曾永亨万一千
Owner SUN YAT SEN UNIV
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