Beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative and synthesis method thereof

A technology of trifluoromethyl group and synthesis method, which is applied in the field of β-trifluoromethyl-β-hydroxy-substituted cyclohexanone derivatives and the synthesis thereof, can solve the problems of few reports on the synthesis method, low yield and the like, and achieves Good industrial application prospects, high product yield, good adaptability

Active Publication Date: 2019-04-12
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, β-trifluoromethyl-β-hydroxyl substituted cyclohexanone derivatives and their synthetic methods are rarely reported
At present, there are two methods for the construction of this type of compound. The first is the cyclization reaction involving acetone and α, β-unsaturated trifluoromethyl ketone (Wang, X.; Zhao, Y.; Liu, J.Org. Lett.2007,9,1343), only acetone can participate in the reaction in this reaction, and only a β-trifluoromethyl-β-hydroxyl substituted cyclohexanone compound is constructed; the second is trifluoromethyl-modified 1, Cyclization reactions of 3-dicarbonyl compounds and α,β-unsaturated ketones (Russian Chemical Bulletin 1997,46,952-953), 3 examples were reported in this reaction, but the yields were all lower than 30%
Therefore, the research on β-trifluoromethyl-β-hydroxy substituted cyclohexanone derivatives and their synthetic methods is still a challenging research topic

Method used

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  • Beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative and synthesis method thereof
  • Beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative and synthesis method thereof
  • Beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative and synthesis method thereof

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Embodiment 1

[0034] A synthesis method of a β-trifluoromethyl-β-hydroxyl substituted cyclohexanone derivative in this embodiment, the specific synthesis steps are as follows:

[0035] Under a nitrogen atmosphere, in a 25 ml reaction flask equipped with a reflux condenser, add 0.02 mmol cuprous chloride, 0.2 mmol 4-phenylbut-3-en-2-one oxime acetyl ester, 0.2 mmol Cesium pivalate, 0.4 mmol 1,1,1-trifluoro-3-phenylacetone, 2 ml dimethyl sulfoxide, the reaction system was stirred at 80°C for 12 hours, stopped heating and stirring, cooled to room temperature, Add water, ethyl acetate extracts the reaction solution, the ethyl acetate layer is subjected to vacuum rotary evaporation, removes the solvent, then separates and purifies by column chromatography, obtains the target product, and the column chromatography eluent used is that the volume ratio is 5: 1 sherwood oil: ethyl acetate mixed solvent; The productive rate of product is 58%.

Embodiment 2

[0037] A synthesis method of a β-trifluoromethyl-β-hydroxyl substituted cyclohexanone derivative in this embodiment, the specific synthesis steps are as follows:

[0038] Under a nitrogen atmosphere, in a 25 ml reaction flask equipped with a reflux condenser, add 0.02 mmol cuprous chloride, 0.2 mmol 4-phenylbut-3-en-2-one oxime acetyl ester, 0.2 mmol Potassium carbonate, 0.2 mmol 1,1,1-trifluoro-3-phenylacetone, 2 ml dimethyl sulfoxide, the reaction system was stirred at 80°C for 12 hours, stopped heating and stirring, cooled to room temperature, and added water , extract the reaction solution with ethyl acetate, carry out the rotary evaporation of the ethyl acetate layer under reduced pressure, remove the solvent, and then separate and purify by column chromatography to obtain the target product, and the column chromatography eluent used is a volume ratio of 100:1 Petroleum ether: ethyl acetate mixed solvent; The productive rate of product is 22%.

Embodiment 3

[0040] A synthesis method of a β-trifluoromethyl-β-hydroxyl substituted cyclohexanone derivative in this embodiment, the specific synthesis steps are as follows:

[0041] Under a nitrogen atmosphere, in a 25 ml reaction flask equipped with a reflux condenser, add 0.02 mmol of cuprous bromide, 0.2 mmol of 4-phenylbut-3-en-2-one oxime acetyl ester, 0.2 mmol of Cesium pivalate, 0.4 mmol 1,1,1-trifluoro-3-phenylacetone, 2 ml dimethyl sulfoxide, the reaction system was stirred at 80°C for 6 hours, stopped heating and stirring, cooled to room temperature, Add water, ethyl acetate extracts the reaction solution, the ethyl acetate layer is subjected to vacuum rotary evaporation, removes the solvent, and then separates and purifies by column chromatography to obtain the target product, and the column chromatography eluent used is a volume ratio of 10: 1's sherwood oil: ethyl acetate mixed solvent; The productive rate of product is 40%.

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Abstract

The invention belongs to the technical field of organic synthesis and discloses a beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative and a synthesis method thereof. The beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative has a structural formula shown in a first formula. The synthesis method comprises the following steps of: under the conditions of a catalyst, alkali and organic solvent, mixing alpha, beta-unsaturated oxime ester category compounds with trifluoromethyl ketone category compounds, and post-treating reaction product to obtain the beta-trifluoromethyl-beta-hydroxy substituted cyclohexanone derivative. According to the synthesis method, cheap metal copper is used as a catalyst, no ligand is needed, and the used raw materials are cheap andeasy to obtain; the reaction has good adaptability to functional groups, has wide adaptability to substrates, has high product yield, and can be amplified to gram scale production, the operation is simple and safe, the reaction conditions are mild, the method has good industrial application prospect, the obtained product has wide application in the fields of pesticides, medicines and materials.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a β-trifluoromethyl-β-hydroxyl substituted cyclohexanone derivative and a synthesis method thereof. Background technique [0002] In view of the small atomic radius of the fluorine atom, which is close to the hydrogen atom, but has high electronegativity, it is difficult to be polarized. Therefore, when fluorine atoms or fluorine-containing groups are introduced into organic compound molecules, the chemical properties, physical properties and biological activities of the compounds are usually significantly improved. According to statistics, more than 30% of the pesticide or drug molecules sold on the market contain at least one fluorine atom or fluorine-containing group. However, the types of fluorine-containing natural products existing in nature are very limited. In order to meet the urgent needs of people's production and research on the increase in the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/747C07C45/00C07C201/12C07C205/45C07D333/22C07D307/46
CPCC07B2200/07C07C45/00C07C49/747C07C201/12C07C205/45C07D307/46C07D333/22C07C2601/14
Inventor 竺传乐曾浩江焕峰
Owner SOUTH CHINA UNIV OF TECH
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