Method for synthesizing beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in heterogeneous catalysis mode

A dichlorotitanocene, heterogeneous catalysis technology, applied in the preparation of organic compounds, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., to achieve high yield, low dosage, Synthetic low-cost effects

Inactive Publication Date: 2014-11-12
SHAANXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the existing β-aminocarbonyl compound preparation methods, and to provide a method of adding polyaminophenol and titanocene dichloride to the reaction system at the same time to form highly active catalytic species in situ. A method for directly catalyzing ketones, aromatic aldehydes, and aromatic amines to synthesize β-aminocarbonyl compounds under solvent-free conditions, the method is simple in operation, mild in reaction conditions, cheap in catalyst, non-toxic, stable to air and water, high in catalytic activity and reusable

Method used

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  • Method for synthesizing beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in heterogeneous catalysis mode
  • Method for synthesizing beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in heterogeneous catalysis mode
  • Method for synthesizing beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in heterogeneous catalysis mode

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] Taking the preparation of the following formula compound 1,3-diphenyl-3-(phenylamino)-1-propanone as an example, the raw materials used and the preparation method thereof are as follows:

[0013]

[0014] Put 102μL (1.0mmol) of benzaldehyde, 100μL (1.1mmol) of aniline, and 175μL (1.5mmol) of acetophenone in a reaction flask, mix well, then add 24.9mg (0.1mmol) of titanocene dichloride, 10mg of Poly-o-aminophenol with a molecular weight of 30,000 was stirred at 25°C for 7 hours to stop the reaction, and 2 mL of tetrahydrofuran was added to the system, filtered, and the filtrate was separated and purified by column chromatography to obtain a white solid product 1,3-diphenyl-3- (Phenylamino)-1-acetone, its productive rate is 97%, product is characterized by Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and characterization data is: 1 H NMR (400MHz, CDCl 3 )δ: 7.89-7.91 (m, 2H), 7.56 (dd, J 1 = 10.5Hz,J 2 =4.3Hz, 1H), 7.45...

Embodiment 2

[0022] Taking the preparation of the following formula compound 1-(4-methoxyphenyl)-3-(2-methoxyphenyl)-3-(4-chloroanilino)-1-acetone as an example, the raw materials used and its preparation Methods as below:

[0023]

[0024] In Example 1, the benzaldehyde used is replaced with equimolar o-methoxybenzaldehyde, aniline is replaced with equimolar p-chloroaniline, acetophenone is replaced with equimolar p-methoxyacetophenone, and other steps Same as Example 1, obtain yellow solid 1-(4-methoxyphenyl)-3-(2-methoxyphenyl)-3-(4-chloroanilino)-1-propanone, its yield is 95%, the characterization data is: 1 H NMR (400MHz, CDCl 3 )δ: 7.88(d, J=8.8Hz, 2H), 7.26(d, J=7.5Hz, 1H), 7.13(t, J=7.1Hz, 1H), 6.90(d, J=8.8Hz, 2H) , 6.80 (dd, J 1 =16.2Hz,J 2 =8.2Hz, 4H), 6.34(d, J=8.8Hz, 2H), 5.09(d, J=3.5Hz, 1H), 4.73(s, 1H), 3.87(s, 3H), 3.76(s, 3H ), 3.49 (dd, J 1 =15.1Hz,J 2 = 4.2Hz, 1H), 3.06(dd, J 1 =15.1Hz,J 2 = 8.6Hz, 1H); 13 C NMR (101MHz, CDCl3 )δ: 196.5, 162.7, 155.5, 144....

Embodiment 3

[0026] Taking the preparation of the following formula compound 2-methyl-1-phenyl-1-(3-chloroanilino)-3-pentanone as an example, the raw materials used and the preparation method thereof are as follows:

[0027]

[0028] In Example 1, the acetophenone used was replaced with 1.2 mmol 3-pentanone, aniline was replaced with equimolar m-chloroaniline, stirred at 50°C for 7 hours, other steps were the same as in Example 1, and a yellow solid 2- Methyl-1-phenyl-1-(3-chloroanilino)-3-pentanone, the yield is 80%, and the characterization data are: 1 H NMR (400MHz, CDCl 3 )δ: 7.31(d, J=7.3Hz, 1H), 7.28(s, 1H), 7.27(s, 1H), 7.22(m, 2H), 6.94(t, J=8.1Hz, 1H), 6.57( dd, J=13.2, 7.9Hz, 1H), 6.47(t, J=2.1Hz, 1H), 6.36(t, J=9.3Hz, 1H), 5.17(br, 0.25H), 4.47(br, 0.75H ), 4.61(t, J=5.6Hz, 0.75H), 4.46(d, J=5.7Hz, 0.25H), 3.01(m, 1H), 2.20(m, 2H), 1.17(d, J=7.1Hz , 1H), 1.09(d, J=7.0Hz, 2H), 0.91(t, J=7.2Hz, 2H), 0.85(t, J=7.2Hz, 1H); 13 C NMR (101MHz, CDCl 3 )δ: 214.4, 212.2, 147.2, 14...

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Abstract

The invention discloses a method for synthesizing a beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in a heterogeneous catalysis mode. The beta-amidogen carbonyl compound is obtained by making ketone, aromatic aldehyde and aromatic amine to react at the temperature ranging from 25 DEG C to 50 DEG C at the presence of the titanocene dichloride serving as a catalyst and poly-ortho-aminophenol or poly-m-aminophenol. According to the method, the poly-aminophenol and the titanocene dichloride are added to a reaction system at the same time, a catalytic active species with high activity can be formed in situ, operation is simple, no solvent is added, reaction conditions are mild, the catalyst is low in price, nontoxic, stable in air and water, high in catalytic activity and capable of being repeatedly used, products are prone to separation, and the productivity is high. The method has the advantages that cost is low, environmental friendliness is achieved, and atom economy is high. The method has wide application prospects for the beta-amidogen carbonyl compound.

Description

technical field [0001] The invention belongs to the technical field of synthesis of β-aminocarbonyl compounds, and in particular relates to a method for synthesizing β-aminocarbonyl compounds by using titanocene dichloride and polyaminophenol as catalysts. Background technique [0002] β-Aminocarbonyl compounds are key intermediates in the synthesis of drugs and natural products, and are widely used in organic synthesis. β-Aminocarbonyl compounds are also an important class of biologically active substances, which have various biological activities such as antitussive, antibacterial, anti-inflammatory, anticancer, antiviral, sedative, analgesic, antihypertensive, edema inhibitory, and anticoagulant. From the perspectives of environmental protection, energy saving, and atom economy, the direct, efficient and selective construction of β-aminocarbonyl compounds from unactivated aldehydes, amines, and ketones is attractive. However, this direct construction method requires an i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C225/16C07C221/00B01J31/22
Inventor 高子伟朱序阳陈纯张国防张伟强孙华明
Owner SHAANXI NORMAL UNIV
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