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Preparation method of alpha-trifluoromethylthio substituted acetophenone compound

A technology of trifluoromethylthio and acetophenone, which is applied in the preparation of thioether, the formation/introduction of thiol/thioether, organic chemistry, etc. , the use of expensive and other problems, to achieve the effect of simple and convenient preparation method, low cost and high yield

Active Publication Date: 2018-09-25
UPCHEM CHINA
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Solve the problem of using expensive trifluoromethylthiolation reagents in the prior art, which cannot be commercialized and are difficult to synthesize

Method used

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  • Preparation method of alpha-trifluoromethylthio substituted acetophenone compound
  • Preparation method of alpha-trifluoromethylthio substituted acetophenone compound
  • Preparation method of alpha-trifluoromethylthio substituted acetophenone compound

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preparation example Construction

[0060] The present invention is a kind of preparation method of α-trifluoromethylthio substituted acetophenone compound, and the steps comprise:

[0061] Aryl methyl ketone as substrate, sodium trifluoromethanesulfinate as trifluoromethylthio reagent, triphosgene as reaction additive, pyridine as catalyst, dichloroethane as solvent, nitrogen protection mode, 60°C Stir for 12 hours, TLC tracking reaction, after the reaction is fully completed, column chromatography separation to obtain α-trifluoromethylthio substituted acetophenone products, the yield is between 61-85%, its reaction formula is as follows (1):

[0062]

[0063] Wherein, the proportion of aryl methyl ketone, sodium trifluoromethanesulfinate and triphosgene is 1:1.5:1 according to the molar concentration.

[0064] The outstanding innovation of the method of the present invention is that only cheap and green triphosgene is used as a reaction additive and pyridine is used as a catalyst, avoiding the use of trans...

Embodiment 1

[0066] The preparation method of α-trifluoromethylthioacetophenone, its synthetic route is as follows formula (3), carries out according to the following steps:

[0067]

[0068] (1) Add 1.0 mmol of acetophenone, 1.5 mmol of sodium trifluoromethanesulfinate, 1.0 mmol of triphosgene, and 0.1 mmol of pyridine into 3 mL of DCE, under nitrogen protection, and react at 60° C. for 12 hours.

[0069] (2) After the reaction was completed, 5 mL of 5% HCl aqueous solution was added to quench the reaction. Extracted twice with ethyl acetate (10 mL×2), washed once with saturated brine, and evaporated under reduced pressure to remove ethyl acetate. The oily target product was obtained by column chromatography with a yield of 82%.

[0070] The NMR data are as follows:

[0071] Such as figure 1 as shown, 1 H NMR (400MHz, CDCl 3 ):δ=8.08-7.91(m,2H),7.67(t,J=7.3Hz,1H),7.53(t,J=7.9Hz,2H),4.54(s,2H).

[0072] Such as figure 2 as shown, 13 C NMR (101MHz, CDCl 3 ): δ=192.0(s), 134.7(s...

Embodiment 2

[0076] The preparation method of α-trifluoromethylthio-4-methylacetophenone, its synthetic route is as follows formula (4), carries out according to the following steps:

[0077]

[0078] (1) Add 1.0mmol of 4-methylacetophenone, 1.5mmol of sodium trifluoromethanesulfinate, 1.0mmol of triphosgene, and 0.1mmol of pyridine into 3mL of DCE, under nitrogen protection, and react at 60°C for 12 hours .

[0079] (2) After the reaction was completed, 5 mL of 5% HCl aqueous solution was added to quench the reaction. Extracted twice with ethyl acetate (10 mL×2), washed once with saturated brine, and evaporated under reduced pressure to remove ethyl acetate. The oily target product was obtained by column chromatography with a yield of 83%.

[0080] The NMR data are as follows:

[0081] Such as image 3 shown, 1 H NMR (400MHz, CDCl 3 ):δ=7.87(d, J=8.2Hz, 2H), 7.33(d, J=8.2Hz, 2H), 4.52(s, 2H), 2.46(s, 3H).

[0082] Such as Figure 4 shown, 13 C NMR (101MHz, CDCl 3 ):δ=191.6(s)...

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Abstract

The invention discloses a preparation method of an alpha-trifluoromethylthio substituted acetophenone compound. The preparation method comprises the following steps: by taking aryl ketone as a substrate, sodium trifluoromethanesulfinate as a trifluoromethylthio reagent, triphosgene as an additive, pyridine as a catalyst and dichloroethane as a solvent, in the nitrogen protection mode, stirring for12 hours at the temperature of 60 DEG C, performing a TLC tracking reaction, and conducting column chromatography isolation after sufficiently completing the reaction, thereby obtaining the alpha-trifluoromethylthio substituted acetophenone compound. According to the preparation method, the triphosgene is used as the reaction additive, so that using an expensive trifluoromethylthio reagent is avoided, but so far, a method for introducing trifluomethylthio has not been reported, the preparation method is simple and convenient, is low in cost, and is high in yield, a product is directly obtained, without any transition metal catalysis, and therefore, the preparation method is extremely high in practical popularization value.

Description

technical field [0001] The invention belongs to the technical field of chemical preparation, and in particular relates to a preparation method of α-trifluoromethylthio-substituted acetophenone compounds. Background technique [0002] Fluorine is the most abundant element on earth, but there are only a dozen fluorine-containing organic compounds that have been identified in nature, and most of the fluorine-containing organic compounds are synthesized. The introduction of fluorine-containing groups can greatly change the physical, chemical and biological properties of the parent compound, so the introduction of fluorine-containing groups plays an important role in medicine, pesticides, and materials. [0003] Trifluoromethylthio (SCF 3 ) has lipophilicity and electron-withdrawing properties similar to trifluoromethyl, and its introduction into drug molecules can significantly improve the metabolic stability and other biological activities of the parent molecule. A large numbe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B45/06C07C319/14C07C323/22C07C323/56C07D307/46C07D333/18
CPCC07B45/06C07C319/14C07D307/46C07D333/18C07C323/22C07C323/56
Inventor 郭圣荣袁艳琴
Owner UPCHEM CHINA
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