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Aryl iodine compounds containing difluoromethylene at the ortho-position and preparing method thereof

A technology of difluoromethylene and aryl iodide, which is applied in the field of organic chemical synthesis, can solve the problems of high price and poor functional group compatibility, and achieve the effects of easy product, mild reaction conditions and high yield

Active Publication Date: 2019-05-21
ZHEJIANG NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of the former is that not only the functional group compatibility is poor, but also the fluorinating reagents used are usually dangerous.
For the latter, the reaction often relies on the use of expensive transition metal catalysts, and some reactions must be carried out under harsh conditions

Method used

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  • Aryl iodine compounds containing difluoromethylene at the ortho-position and preparing method thereof
  • Aryl iodine compounds containing difluoromethylene at the ortho-position and preparing method thereof
  • Aryl iodine compounds containing difluoromethylene at the ortho-position and preparing method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043]

[0044] N 2 Under protection, redistilled dichloromethane (5 mL) was added to a 25 ml reaction tube, then 161 mg (0.5 mmol) of iodobenzene diacetate was added, and then 180 microliters of trimethylsilyl trifluoromethanesulfonate was added (TMSOTf, 1.0mmol), the reaction solution was stirred at room temperature for 5min, and finally 228mg (1.0mmol) of difluoroacetophenone enol silyl ether was added at -78°C, stirred for 5min, and the reaction progress was tracked by thin-layer chromatography. After completion, add saturated sodium bicarbonate solution (3ml) to quench the reaction, slowly warm up to room temperature, then extract with dichloromethane (3mL×3), the organic phase is dried with anhydrous sodium sulfate, concentrated in vacuo, and separated by column chromatography (Rf=0.19, developer: petroleum ether / ethyl acetate=40 / 1, v / v), the obtained product was a colorless oil with a purity of 99.78% and a yield of 83%.

[0045] The target product is characterized ...

Embodiment 2

[0052]

[0053] N 2 Under protection, redistilled dichloromethane (5mL) was added to a 25ml reaction tube, then 178mg (0.5mmol) of para-chloro iodobenzene diacetate was added, and then 180 microliters of trifluoromethanesulfonic acid was added Trimethylsilyl ester (TMSOTf, 1.0mmol), the reaction solution was stirred at room temperature for 5min, and finally 228mg (1.0mmol) of difluoroacetophenone enol silyl ether was added at -78°C, stirred for 5min, and thin-layer chromatography was used to Follow the reaction process, add saturated sodium bicarbonate solution (3ml) after the reaction to quench the reaction, slowly warm up to room temperature, then extract with dichloromethane (3mL×3), the organic phase is dried with anhydrous sodium sulfate, concentrated in vacuo, passed Separation by column chromatography (Rf = 0.20, developing solvent: petroleum ether / ethyl acetate = 40 / 1, v / v), the obtained product was a light yellow solid with a purity greater than 99% and a yield of ...

Embodiment 3

[0061]

[0062] N 2 Under protection, redistilled dichloromethane (5mL) was added to a 25ml reaction tube, then 173mg (0.5mmol) of iodobenzene diacetate substituted by p-cyano group was added, and then 180 microliters of trifluoromethanesulfonate was added Acid trimethylsilyl ester (TMSOTf, 1.0mmol), the reaction solution was stirred at room temperature for 5min, and finally difluoroacetophenone enol siloxane 228mg (1.0mmol) was added at -78°C, stirred for 5min, and thin-layer chromatography After the reaction was completed, saturated sodium bicarbonate solution (3ml) was added to quench the reaction, and the temperature was slowly raised to room temperature, then extracted with dichloromethane (3mL×3), the organic phase was dried with anhydrous sodium sulfate, and concentrated in vacuo. Separation by column chromatography (Rf=0.25, developing solvent: petroleum ether / ethyl acetate=20 / 1, v / v), the obtained product was a light yellow solid with a purity greater than 99% and ...

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Abstract

A method for preparing aryl iodine compounds containing difluoromethylene at the ortho-position is disclosed. The method is characterized in that aryliodine diacetate shown as a structural formula (I)and difluoroacetophenone silyl enol ether shown as a structural formula (II) are subjected to a rearrangement reaction under the existence of trimethylsilyl trifluoromethanesulfonate to obtain the aryl iodine compound containing difluoromethylene, shown as the structural formula (III), wherein R1 is selected from hydrogen, halogen, alkyl, alkoxy, alkoxycarbonyl, halogenated alkyl, halogenated alkoxy, alkoxycarbonyl substituted alkyl, amino substituted alkyl, alkyl substituted with alkoxycarbonyl and amino, cyano or nitro, and Ar is selected from a benzene ring, a naphthalene ring and a thiophene ring. The method has following advantages: mild reaction conditions, good selectivity, a high yield, easy product separation, simple operation, and the like.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis, in particular to a method and compound for preparing aryl iodide compounds containing difluoromethylene groups in the ortho position. Background technique [0002] Difluoromethylene is generally considered to be the bioisostere of oxygen atom, carbonyl and methylene, which has good metabolic stability and high lipophilicity, and the enhancement of lipophilicity is conducive to improving the penetration and penetration of organic molecules. Therefore, compounds containing difluoromethylene functional groups are widely used in the fields of medicine, pesticides, and materials (ChemBioChem2004, 5, 570; Chem. Eur. J. 2017, 23, 14676). [0003] Among these difluoromethylene-containing compounds, difluoromethylene-containing aromatic compounds have attracted much attention because these compounds widely exist in various molecules with important biological activities (Chem. Rev. 2016, 2, 422). ...

Claims

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Application Information

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IPC IPC(8): C07C45/51C07C49/813C07C67/343C07C69/76C07C253/30C07C255/56C07C269/06C07C271/22C07D333/28C07F5/02C07C17/361C07C25/02
Inventor 黄鑫张亚鸽许滢彭勃
Owner ZHEJIANG NORMAL UNIVERSITY
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