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Aryl iodine compound containing carboxydifluoromethylene at ortho-position and preparation method thereof

A technology of carboxydifluoromethylene 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 separation, mild reaction conditions, and cheap and easy-to-obtain raw materials

Active Publication Date: 2019-05-31
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 compound containing carboxydifluoromethylene at ortho-position and preparation method thereof
  • Aryl iodine compound containing carboxydifluoromethylene at ortho-position and preparation method thereof
  • Aryl iodine compound containing carboxydifluoromethylene at ortho-position and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046]

[0047] 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 220mg (1.0mmol) of pentafluoroacetone enol silicon ether was added at -78°C, stirred for 5min, then warmed to -50°C and reacted for 2h, using a thin The reaction process was tracked by 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 vacuum After concentration, it was dissolved in KOH (560mg) in tetrahydrofuran / water (1:1) solution, reacted at room temperature for 12h, adjusted the pH value ...

Embodiment 2

[0055]

[0056] N 2 Under protection, redistilled dichloromethane (5 mL) was added to a 25 ml reaction tube, then 168 mg (0.5 mmol) of iodobenzene p-methyldiacetate was added, and then 180 microliters of trimethyl trifluoromethanesulfonate was added base silicon ester (TMSOTf, 1.0mmol), the reaction solution was stirred at room temperature for 5min, and finally 220mg (1.0mmol) of pentafluoroacetophenone enol siloxane was added at -78°C, stirred for 5min, then heated to -50°C and React for 2h, track the reaction progress with thin layer chromatography, add saturated sodium bicarbonate solution (3ml) to quench the reaction after the reaction is over, slowly warm up to room temperature, then extract with dichloromethane (3mL×3), the organic phase is washed with anhydrous Dry over sodium sulfate, concentrate in vacuo and dissolve in KOH (560mg) in tetrahydrofuran / water (1:1) solution, react at room temperature for 12h, adjust the pH value to 2-3 with dilute hydrochloric acid af...

Embodiment 3

[0064]

[0065] N 2 Under protection, redistilled dichloromethane (5 mL) was added to a 25 ml reaction tube, then 189 mg (0.5 mmol) of iodobenzene p-tert-butyldiacetate was added, and then 180 microliters of trifluoromethanesulfonate tri Methyl silicon ester (TMSOTf, 1.0mmol), the reaction solution was stirred at room temperature for 5min, and finally 220mg (1.0mmol) of pentafluoroacetophenone enol silicon ether was added at -78°C, stirred for 5min, and then heated to -50°C And react for 2h, track the reaction process with thin-layer chromatography, add saturated sodium bicarbonate solution (3ml) to quench the reaction after the end of the reaction, slowly warm up to room temperature, then extract with dichloromethane (3mL × 3), the organic phase with Dry over sodium sulfate, dissolve in KOH (560mg) in tetrahydrofuran / water (1:1) solution after vacuum concentration, react at room temperature for 12h, adjust the pH value to 2-3 with dilute hydrochloric acid after the reactio...

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Abstract

The invention discloses a preparation method of an aryl iodine compound containing carboxydifluoromethylene at ortho-position. The preparation method is characterized by including: at the presence oftrimethylsilyl trifluoromethanesulfonate, allowing aryl iodine diacetate shown as a structural formula (I) and pentafluoroacetone enol silicon ether shown as a structural formula (II) to be in rearrangement reaction, and hydrolyzing under strong base to obtain the aryl iodine compound containing methylene difluoroacetate and shown as a structural formula (III), wherein R1 is selected from hydrogen, halogen, alkyl, alkoxy, carbalkoxy, halogenated alkyl, halogenated alkoxy, carbalkoxy substituted alkyl, amino substituted alkyl, carbalkoxy and amino substituted alkyl, cyano or nitro, and Ar is selected from benzene ring, naphthalene ring and thiophene ring. The preparation method has the advantages of being mild in reaction condition, high in selectivity and yield, easy-to-separate in productand simple in operation.

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 carboxydifluoromethylene 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,...

Claims

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Application Information

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IPC IPC(8): C07C51/093C07C51/00C07C57/58C07C59/64C07D333/28C07C17/363C07C25/13
Inventor 彭勃何佳妮张其峰李东阳詹娅玲王明慧
Owner ZHEJIANG NORMAL UNIVERSITY
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