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Novel method for efficiently preparing beta-aminoketone by utilizing dimethyl sulfoxide

A technology of aminoketone and acetophenone, which is applied in the field of organic synthetic chemistry, can solve the problems of high toxicity to the human body, and achieve the effect of overcoming the large toxicity of the environment and the human body

Inactive Publication Date: 2017-05-24
ANYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The invention avoids the participation of toxic reagent formaldehyde analogs, and overcomes the disadvantages of greater toxicity to the environment and human body caused by the participation of benzaldehyde analogs compared with traditional methods

Method used

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  • Novel method for efficiently preparing beta-aminoketone by utilizing dimethyl sulfoxide
  • Novel method for efficiently preparing beta-aminoketone by utilizing dimethyl sulfoxide
  • Novel method for efficiently preparing beta-aminoketone by utilizing dimethyl sulfoxide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] In a 50 ml round bottom flask, add 0.1202 g (1.0 mmol) of acetophenone, 0.0075 g (1.1 mmol) of imidazole, 0.0172 g (0.1 mmol) of ruthenium trichloride, 0.0198 g of 1,10-phenanthrene Phenyl (0.1 mmol), 0.7080 g (2.0 mmol) selectfluor, 0.2160 g (2.0 mmol) sodium carbonate, 6.0 milliliters of dimethyl sulfoxide (DMSO), heated at 120 ° C, refluxed for 1 hour until the reaction of acetophenone was complete ( Thin layer chromatography TLC monitoring). The reaction mixture was poured into 20 mL of water, extracted with ethyl acetate (10 mL×3). The organic phases were combined and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate=6 / 1) to obtain 0.2866 g of a white solid, with a yield of 91%. The reaction is shown in the following formula:

[0021]

[0022] Spectral analysis data

[0023] White solid.Mp: 138-140℃; 1 H NMR (400MHz; CDCl 3 ): δ=3.59(t,...

Embodiment 2

[0025] In a 50 ml round bottom flask, add 0.1682 g (1.0 mmol) 3,5-bis(trifluoromethyl)acetophenone, 0.0075 g (1.1 mmol) imidazole, 0.0172 g (0.1 mmol) trichloride Ruthenium, 0.0198 g 1,10-phenanthroline (0.1 mmol), 0.7080 g (2.0 mmol) selectfluor, 0.2160 g (2.0 mmol) sodium carbonate, 6.0 ml dimethyl sulfoxide (DMSO), heating at 120°C , Refluxed for 1 hour until the reaction of 3,5-bis(trifluoromethyl)acetophenone was complete (monitored by TLC). The reaction mixture was poured into 20 mL of water, extracted with ethyl acetate (10 mL×3). The organic phases were combined and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate=5 / 1) to obtain 0.2994 g of a light yellow solid, with a yield of 81%. The reaction is shown in the following formula:

[0026]

[0027] Spectral analysis data

[0028] White solid.Mp: 129-130℃; 1 H NMR (400MHz; CDCl 3 ): δ=3.63(t...

Embodiment 3

[0030] In a 50 ml round bottom flask, add 0.1702 g (1.0 mmol) of β-naphthyl ethyl ketone, 0.0075 g (1.1 mmol) of imidazole, 0.0172 g (0.1 mmol) of ruthenium trichloride, 0.0198 g (0.1 mmol) 1,10-phenanthroline, 0.7080 g (2.0 mmol) selectfluor, 0.2160 g (2.0 mmol) sodium carbonate, 6.0 ml dimethyl sulfoxide (DMSO), heated at 120 ° C, refluxed for 1 hour to β-naphthyl ethyl The ketone reaction was complete (monitored by TLC). The reaction mixture was poured into 20 mL of water, extracted with ethyl acetate (10 mL×3). The organic phases were combined and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate=5 / 1) to obtain 0.3234 g of a light yellow solid, with a yield of 87%. The reaction is shown in the following formula:

[0031]

[0032] Spectral analysis data

[0033] White solid.Mp: 138-138°C; 1 H NMR (400MHz; CDCl 3 ): δ=3.73(t, J=7.6Hz, 2H), 4.34(t, ...

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Abstract

The invention belongs to the technical field of organic synthesis chemistry and discloses a simple and efficient novel method for preparing beta-aminoketone by utilizing a metal salt catalyst, dimethyl sulfoxide used as a one-carbon synthon, and imidazole and ketone derivatives. By utilizing the novel method, a series of beta-aminoketone compounds are prepared. The limitation of preparing the beta-aminoketone compounds at present is overcome; disadvantages of a traditional method that toxic effects on the environment and human bodies are relatively great when a toxic reagent, namely a formaldehyde analogue, participates in reaction are avoided; the low-toxicity dimethyl sulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA) and N-methyl pyrrolidone (NMP) are used as the one-carbon synthons for synthesizing a series of beta-aminoketone for the first time, and a new way for synthesizing the beta-aminoketone compounds is expanded. The method provided by the invention has the advantages of simplicity in operation, high efficiency and easiness of obtaining raw materials, reagents and catalysts; the method is suitable for synthesizing various beta-aminoketone compounds and is suitable for large-scale industrial production.

Description

[0001] Technical field: [0002] The invention belongs to the technical field of organic synthesis chemistry and discloses a new method for preparing β-amino ketone by metal salt catalyzing ketone derivatives, imidazole and one-carbon synthon dimethyl sulfoxide. [0003] Background technique: [0004] Mannich reaction (Mannich reaction, referred to as Mann reaction), also known as amine methylation reaction, is a three-group reaction in which compounds containing active hydrogen condense with formaldehyde and secondary amines or ammonia to form β-amino (carbonyl) compounds Reaction in organic chemistry (Verkade, J.M.M.; van Hemert, L.J.C.; Quaedflieg, P.J.L.M.; Rutjes, F.P.J.T. Chem. Soc. Rev. 37, 29, (2008)). The reaction of general aldimine with α-methylene carbonyl compound is also regarded as Mannich reaction. The product β-amino (carbonyl) compound of the reaction is called "Mannich base", referred to as Mannich base (Mannich, C.; Krosche, W. Arch. Pharm. 250, 674, (1912)...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D231/12
CPCC07D231/12Y02P20/584
Inventor 孙凯杜卫民吕允贺王薪
Owner ANYANG NORMAL UNIV
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