A kind of preparation method of substituted secondary aromatic amine compound

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

Active Publication Date: 2021-04-09
QUFU NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] 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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  • A kind of preparation method of substituted secondary aromatic amine compound
  • A kind of preparation method of substituted secondary aromatic amine compound
  • A kind of preparation method of substituted secondary aromatic amine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062]

[0063] 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 in a 15 mL reaction tube, and argon replacement was performed three times, and then trifluoroacetic acid ( 44.4μL) 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 recovered 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%.

[0064] 1 H NMR (400MHz...

Embodiment 2

[0066]

[0067] 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 (44.4μL) and water 1mL, 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 recovered 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%.

[0068] 1 H NMR (400MHz, CDCl 3 ):7.00(d,J=8.1Hz,2H),6.56(d,J=8.1Hz...

Embodiment 3

[0070]

[0071] 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 (44.4μL) and water 1mL, 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 recovered 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%.

[0072] 1 H NMR (400MHz, CDCl 3 ):7.08(t, J=7.4Hz, 2H), 6.53(t, J=7...

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Abstract

A preparation method of a substituted secondary aromatic amine compound, the steps are: based on the following reaction formula: wherein R 1 is an optionally substituted hydrogen atom, aryl, heteroaryl, fluorine, ester, alkoxy, acyloxy, 1‑10 carbon alkyl, cycloalkyl; R 2 For any substituted hydrogen atom, aryl group, heteroaryl group, ester, acyloxy group, alkoxyl group, cycloalkyl group, 1-12 carbon alkyl group, the thing shown in general formula I is set as an aromatic nitro compound, The compound shown in the general formula II is set to phenol, and the compound shown in the general formula III is set to be a substituted secondary aromatic amine compound, and the palladium / carbon catalyst is used to catalyze the reductive coupling reaction between the aromatic nitro compound and the phenol compound to obtain the substituted two Class aromatic amine compounds, no longer use alkanes, alcohols, aldehydes or ketones as reaction raw materials, avoid the use of expensive metal reagents, or equivalent peroxide oxidants, or higher reaction temperature, or hydrogen as a reducing agent, thus reducing the reaction conditions to improve the safety of the reaction.

Description

[0001] 1. Technical field [0002] The invention relates to a preparation method, in particular to a preparation method of a substituted secondary aromatic amine compound. [0003] 2. Background technology [0004] Substituted secondary aromatic amines are extremely important organic raw materials, widely used in dyes, natural products, agrochemicals, 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, and easy to store and use. Therefore, it is of great application value to develop a method for the synthesis of substituted secondary aromatic amine compounds using ...

Claims

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Application Information

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Patent Type & Authority Patents(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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