Method for preparing beta-amino-carbonyl compound

A technology for aminocarbonyl compounds, applied in the field of preparation of β-aminocarbonyl compounds, can solve the problems of complex substrates, harsh reaction conditions, and long reaction time in the operation process, and achieve high atom economy, simple operation, and great application potential Effect

Inactive Publication Date: 2013-12-25
SHAANXI NORMAL UNIV +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although this method uses green solvents, the reaction efficiency is greatly improved, but the complex substrates, harsh reaction conditions and expensive catalysts in the operation process also restrict its application.
FeCl 3 Is a simple and cheap catalyst, however, the addition of 20% FeCl 3 Only 58% yield in 18h reaction
Recently, phenylboronic acid (S.V.Goswami, Mol.Diversity, 2013, 17, 33) was found to be an effective Lewis acid catalyst that can effectively catalyze the three-component reaction of aldehydes, ketones, and amines to prepare β-aminocarbonyl compounds. However, the reaction Requires an organic solvent and requires a reaction time of up to 8 hours

Method used

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  • Method for preparing beta-amino-carbonyl compound
  • Method for preparing beta-amino-carbonyl compound
  • Method for preparing beta-amino-carbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Taking the preparation of the following formula compound 1,3-diphenyl-3-(phenylamino)-1-acetone as an example, the raw materials used and the preparation method thereof are as follows:

[0014]

[0015] Put 203uL (2.0mmol) benzaldehyde, 201uL (2.2mmol) aniline, 467uL (4.0mmol) acetophenone, 24.9mg (0.1mmol) titanocene dichloride, 13.8mg (0.1mmol) salicylic acid in the reaction bottle , reacted at room temperature for 1 hour, stopped the reaction, added 2 mL of saturated aqueous sodium bicarbonate solution to the system, extracted three times with 10 mL of ethyl acetate, combined the organic phases, dried with anhydrous sodium sulfate, and separated by column chromatography to obtain a white solid product. Its yield is 97%. The resulting product was characterized by a Bruker Avance superconducting Fourier digital NMR spectrometer, and the characterization data are as follows: 1 H NMR (400MHz, CDCl 3 )δppm: 7.89(m, 2H), 7.55(m, 1H), 7.43(m, 4H), 7.32(dd, J=10.3, 4.7H...

Embodiment 2

[0017] Taking the preparation of the following formula compound 1-phenyl-3-(2-chlorophenyl)-3-(4-methoxyphenylamino)-1-acetone as an example, the raw materials used and the preparation method thereof are as follows:

[0018]

[0019] In Example 1, the benzaldehyde used was replaced with equimolar o-chlorobenzaldehyde, and aniline was replaced with equimolar p-methoxyaniline. The other steps were the same as in Example 1 to prepare a white solid 1-phenyl-3 -(2-chlorophenyl)-3-(4-methoxyanilino)-1-propanone, its productive rate is 79%, and the characterization data are: 1 H NMR (400MHz, CDCl 3 )δppm: 7.95 (d, 2H), 7.68-7.72 (m, 1H), 7.53-7.60 (m, 2H), 7.40-7.47 (m, 2H), 7.22-7.30 (m, 1H), 7.07-7.14 ( m, 1H), 6.58-6.72(m, 4H), 5.28-5.34(m, 1H), 3.74-3.85(m, 1H), 3.69(s, 3H), 3.42-3.54(m, 1H); 13 C NMR (101MHz, CDCl 3 )δppm: 198.32, 152.46, 141.33, 140.56, 136.63, 133.31, 133.02, 128.69, 128.48, 128.44, 128.24, 127.90, 122.62, 114.96, 114.68, 55.51, 54.829, 43.9

Embodiment 3

[0021] Taking the preparation of the following formula compound 2-methyl-1-(4-chlorophenyl)-1-anilino-3-pentanone as an example, the raw materials used and the preparation method thereof are as follows:

[0022]

[0023]In Example 1, the benzaldehyde used is replaced with equimolar p-chlorobenzaldehyde, and acetophenone is replaced with equimolar 3-pentanone. Other steps are the same as in Example 1, and a light yellow solid 2-methyl -1-(4-chlorophenyl)-1-anilino-3-pentanone, the yield is 81%, the cis-trans ratio is 74:26, and the characterization data are: 1 H NMR (400MHz, CDCl 3 )δppm: 7.17(t, J=8.2Hz, 4H), 6.99(t, J=7.5Hz, 2H), 6.57(d, J=7.1Hz, 1H), 6.38(d, J=7.5Hz, 2H) , 4.56(d, J=5.3Hz, 1H), 2.89(m, 1H), 2.27(m, 2H), 1.10(d, J=6.9Hz, 1H), 1.02(d, J=6.9Hz, 3H) , 0.87(t, J=7.1Hz, 3H); 13 C NMR (101MHz, CDCl 3 )δppm:213.88,211.97,145.69,139.36,138.85,131.99,131.93,128.13,128.09,127.82,127.76,127.27,126.96,116.92,116.51,112.66,112.29,76.33,76.02,75.70,59.02,57.63,50.98...

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Abstract

The invention provides a method for preparing a beta-amino-carbonyl compound. Aldehydes, ketones and amines are directly mixed under the condition of synergetic catalysis of titanocene dichloride and a ligand, and react at room temperature to obtain the beta-amino-carbonyl compound, wherein the ligand is salicylic acid or salicylic acid derivatives or structural analogues thereof. According to the method, the catalyst used in the method is low in cost, nontoxic and stable and effective to air and water, the reaction condition is mild, a solvent is not needed, the operation is simple, and the atom economy is high.

Description

technical field [0001] The present invention relates to the preparation method of β-aminocarbonyl compound. Background technique [0002] β-Aminocarbonyl compounds are important structural units of many natural products, drugs, and synthetic intermediates. For example, 1,2-cyclopentanone bis-Mannich bases containing β-aminocarbonyl structural units have strong anti-inflammatory and anti-cancer activities. The Mannich reaction has always been the most basic and important reaction method for the construction of β-aminocarbonyl compounds. The three-component Mannich reaction has high atomic economy, simple operation, and environmental protection, and is the preferred way to prepare β-aminocarbonyl compounds. Many Bronsted acid or Lewis acid catalysts are used to catalyze the preparation of such compounds, such as sulfonic acid compounds, polymer-supported sulfonic acids, heteropolyacids, proline, FeCl 3 , InCl 3 、BiCl 3 、Bi(OTf) 3 , CeCl 3 , CAN, Yb(OPf) 3 , ZrOCl 2 , ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C225/16C07C225/18C07C221/00C07D307/52
Inventor 高子伟吴亚张伟强孙华明陈纯朱序阳
Owner SHAANXI NORMAL UNIV
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