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Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone

A technology of cyclopropyldiphenylsulfonium and trifluoromethanesulfonate, which is applied in the field of cyclopropyldiphenylsulfonium trifluoromethanesulfonate, can solve the problems of difficult synthesis, high price, complicated operation, etc. Achieve the effect of solving the difficulty of synthesis

Inactive Publication Date: 2017-04-26
河北桑迪亚医药技术有限责任公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] One of the purposes of the present invention is to provide the application of cyclopropyldiphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent in the preparation of four-membered cyclic ketones, to solve the problem of traditional sulfur ylide reagent cyclopropyldiphenylsulfonium tetrafluoromethanesulfonate The synthesis of borate is difficult, the operation is complicated and the price is expensive.
[0007] Two of purpose of the present invention is to provide a kind of method for preparing four-membered cyclic ketone, to solve the problems such as adopting traditional sulfur ylide reagent cyclopropyl diphenylsulfonium tetrafluoroborate to be expensive

Method used

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  • Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone
  • Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone
  • Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone

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Experimental program
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Effect test

Embodiment 1

[0020] Dissolve 30 g (0.083 mol) of cyclopropyldiphenylsulfonium trifluoromethanesulfonate in 300 mL of anhydrous tetrahydrofuran, cool to -40 ° C, and then add 91 mL of bis(trimethylsilyl ) Potassium Amide; after the dropwise addition, continue to stir for 5 minutes, then add 16.6g (0.083mol) 4-Boc-piperidone to the reaction system at one time, react at -40°C for 20 minutes, naturally warm to room temperature and stir for 3 hours. After the reaction was completed, 300 mL of water was added to quench the reaction, extracted three times with diethyl ether (200 mL×3) and the organic phases were combined, dried with anhydrous sodium sulfate, and concentrated to obtain an oil. Dissolve the obtained oil in 300 mL of toluene, add 7.78 g (0.083 mol) of lithium tetrafluoroborate, react at 80 ° C for 2 h, cool to room temperature, remove toluene under reduced pressure, add 300 mL of water to quench the reaction, and extract three times with ether (200 mL× 3) Combine the organic phases,...

Embodiment 2

[0024] 10g (0.10mol) tetrahydropyrone and 39.6g (0.11mol) cyclopropyldiphenylsulfonium trifluoromethanesulfonate were dissolved in 200mL DMSO, and 11.2g ( 0.20mol) KOH, naturally rose to room temperature and reacted for 8h. After the reaction was completed, 300 mL of saturated ammonium chloride solution was added to quench the reaction, and stirring was continued overnight. Extracted three times with ethyl acetate (150 mL×2) and combined the organic phases, washed the organic phase twice with saturated brine (75 mL×2), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The obtained crude product was separated by a silica gel column to obtain 11.2 g of the product with a yield of 80%.

[0025] The reaction formula of this reaction is as follows:

[0026]

Embodiment 3

[0028] 14g (0.10mol) of p-chlorobenzaldehyde and 35.9g (0.10mol) of cyclopropyldiphenylsulfonium trifluoromethanesulfonate were dissolved in 250mL of anhydrous tetrahydrofuran, and 15.7g (0.14 mol) tetrahydrofuran solution of potassium tert-butoxide. After the dropwise addition, it was naturally raised to room temperature. After continuing to react for 3 hours, 1M tetrafluoroboric acid aqueous solution was added, and stirring was continued at room temperature for 3 hours. After the reaction was completed, 300 mL of diethyl ether was added to the reaction solution to extract the organic phase, and then the organic phase was washed with saturated sodium bicarbonate and saturated brine respectively, and dried with anhydrous sodium sulfate to obtain a crude product. The obtained crude product was separated by a silica gel column to obtain 15.3 g of the product with a yield of 85%.

[0029] The reaction formula of this reaction is as follows:

[0030]

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Abstract

The invention provides a use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as a sulfur ylide reagent and a method for preparation of four-membered cyclic ketone. The cyclopropyl diphenylsulfonium trifluoromethanesulfonate solves the problem that cyclopropyl diphenylsulfonium tetrafluoroborate as the traditional sulfur ylide reagent used in the synthesis of a four-membered cyclic ketone compound from aldehydes or ketones has large synthesis difficulty, complex operation and an expensive price. Under the same reaction conditions, the reactivity of cyclopropyl diphenylsulfonium trifluoromethanesulfonate is comparable to that of cyclopropyl diphenylsulfonium tetrafluoroborate and thus the cyclopropyl diphenylsulfonium trifluoromethanesulfonate can replace cyclopropyl diphenylsulfonium tetrafluoroborate and be used as a novel sulfur ylide reagent.

Description

technical field [0001] The present invention relates to a kind of purposes of cyclopropyl diphenylsulfonium trifluoromethanesulfonate, specifically cyclopropyl diphenylsulfonium trifluoromethanesulfonate is used as sulfur ylide reagent in the preparation of four-membered cyclic ketones Application and a method for preparing four-membered ring ketone. Background technique [0002] Cyclopropylthio ylide reagent is a key reagent for the synthesis of four-membered ring ketones through aldehydes or ketones. In traditional methods, cyclopropyldiphenylsulfonium tetrafluoroborate is usually used as cyclopropylthio ylide reagent, but this Reagents are expensive and not available in large quantities in the market. This is mainly due to the fact that silver tetrafluoroborate is an expensive and highly deliquescent reagent, which makes the synthesis process of cyclopropyldiphenylsulfonium tetrafluoroborate complex and difficult, which limits the use of this reagent in the laboratory. ...

Claims

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Application Information

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IPC IPC(8): C07D221/20C07D311/96C07C45/00C07C45/68C07C49/693C07C49/753C07C49/657
CPCC07D221/20C07C45/00C07C45/68C07D311/96C07C49/693C07C49/753C07C49/657
Inventor 刘海涛杨欣韩玉朝茹庆科何雷夏俊义郎恒元
Owner 河北桑迪亚医药技术有限责任公司
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