Preparation method of substituted secondary aromatic amine compound

A technology for aromatic amines and compounds, which is applied in the field of preparation of secondary aromatic amine compounds, can solve the problems of harsh reaction conditions, high energy consumption, and high risk, and achieve the effects of mild reaction conditions, easy raw materials, and simple operation

Active Publication Date: 2018-08-07
QUFU NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] In short, the current method of synthesizing substituted secondary aromatic amines through the reductive coupling reaction of aromatic nitro compounds is limited to alkanes, alcohols, aldehydes or ketones as reaction raw materials, and most of the reactions use expensive metal reagents or equivalent peroxide oxidants , or higher reaction temperature, or hydrogen as the reducing agent, the reaction conditions are harsh, the energy consumption is high, and the danger is great

Method used

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  • Preparation method of substituted secondary aromatic amine compound
  • Preparation method of substituted secondary aromatic amine compound
  • Preparation method of substituted secondary aromatic amine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057]

[0058] At room temperature, 29.5 mg of nitrobenzene, 18.8 mg of phenol, 10.6 mg of palladium / carbon catalyst (10% content of palladium) and 122.4 mg of sodium formate were successively added into a 15 mL reaction tube, and three times of argon displacement were performed, and then trifluoroacetic acid ( 44.4vL) and 1mL of water, mix well. The reaction was stirred at 110° C. for 14 hours. After the reaction was completed, the palladium / carbon catalyst was filtered out, and the filter cake was washed with ethyl acetate, dried and recycled for reuse. The filtrate was extracted with ethyl acetate, and the extract was concentrated to solvent-free under vacuum (0.08Mpa) to obtain the crude product, which was then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 10:1, and the silica gel column Flash column chromatography obtained 28.7 mg of the secondary aromatic amine product of this example, with a yield of 82%.

[0059] 1 H NMR (...

Embodiment 2

[0061]

[0062] At room temperature, 32.9 mg of p-methylnitrobenzene, 18.8 mg of phenol, 10.6 mg of palladium / carbon catalyst (10% content of palladium) and 122.4 mg of sodium formate were successively added into a 15 mL reaction tube, and three Fluoroacetic acid (44.4vL) and 1mL of water, mix well. The reaction was stirred at 110° C. for 14 hours. After the reaction was completed, the palladium / carbon catalyst was filtered out, and the filter cake was washed with ethyl acetate, dried and recycled for reuse. The filtrate was extracted with ethyl acetate, and the extract was concentrated to solvent-free under vacuum (0.08Mpa) to obtain the crude product, which was then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 10:1, and the silica gel column Flash column chromatography obtained 31.4 mg of the secondary aromatic amine product of this example, with a yield of 83%.

[0063] 1 H NMR (400MHz, CDCl 3 ):7.00(d, J=8.1Hz, 2H), 6.56(d, J...

Embodiment 3

[0065]

[0066] At room temperature, 32.9 mg of m-methylnitrobenzene, 18.8 mg of phenol, 10.6 mg of palladium / carbon catalyst (10% content of palladium) and 122.4 mg of sodium formate were successively added into a 15 mL reaction tube, and three Fluoroacetic acid (44.4vL) and 1mL of water, mix well. The reaction was stirred at 110° C. for 14 hours. After the reaction was completed, the palladium / carbon catalyst was filtered out, and the filter cake was washed with ethyl acetate, dried and recycled for reuse. The filtrate was extracted with ethyl acetate, and the extract was concentrated to solvent-free under vacuum (0.08Mpa) to obtain the crude product, which was then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 10:1, and the silica gel column Flash column chromatography obtained 30.6 mg of the secondary aromatic amine product of this example, with a yield of 81%.

[0067] 1 H NMR (400MHz, CDCl 3 ):7.08(t,J=7.4Hz,2H),6.53(t,J=7.5...

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Abstract

The invention relates to a preparation method of a substituted secondary aromatic amine compound. The preparation method comprises the following steps: based on an equation as shown in the description, wherein R1 is randomly substituted hydrogen atom, aryl, heteroaryl, fluorine, ester, alkoxy, acyloxy, C1-10 alkyl and a naphthenic base; R2 is randomly substituted hydrogen atom, aryl, heteroaryl, ester, alkoxy, acyloxy, alkoxy, a naphthenic base and C1-12 alkyl, a compound shown in a general formula is set as an aromatic nitro-compound, a compound shown in a general formula II is set as phenol,a compound shown in a general formula III is set as the substituted secondary aromatic amine compound, a palladium/carbon catalyst is utilized for catalyzing the aromatic nitro-compound and a phenolcompound to carry out reductive coupling reaction, so that the substituted secondary aromatic amine compound is obtained, alkyl, alcohol, aldehyde or ketone is not used as a reaction raw material anylonger, use of an expensive metal reagent, or equivalent peroxide oxidizing agent or relatively high reaction temperature is avoided, or hydrogen is prevented from being used as a reducing agent, so that reaction conditions are reduced, and reaction security is improved.

Description

1. Technical field [0001] The present invention relates to a kind of preparation method, especially a kind of preparation method of substituted secondary aromatic amine compound. 2. Background technology [0002] Substituted secondary aromatic amine compounds are extremely important organic raw materials, widely used in the fields of dyes, natural products, agricultural chemicals, textile auxiliaries, chelating agents, pharmaceutical intermediates and material chemistry. The synthetic method of existing aromatic amine compound comprises: (1) nucleophilic substitution reaction of amine and halogenated hydrocarbon; (2) N-alkylation reaction of amine and alcohol; (3) reductive coupling reaction of amine and carbonyl compound (4) Buchwald-Hartwig arylation coupling reaction of amine and aryl halide, etc. Aromatic nitro compounds are cheap, stable in nature, easy to store and use, so it is of great application value to develop and utilize aromatic nitro compounds to synthesize a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/36C07C209/60C07C211/45C07C211/46C07C211/47C07C213/08C07C213/02C07C217/84C07C211/52C07C227/04C07C227/18C07C229/60C07C229/56C07C219/34
CPCC07C209/36C07C209/365C07C209/60C07C213/02C07C213/08C07C227/04C07C227/18C07C211/45C07C211/46C07C211/47C07C217/84C07C211/52C07C229/60C07C229/56C07C219/34
Inventor 魏伟杨道山
Owner QUFU NORMAL UNIV
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