Method for synthesizing alpha-alkynyl substituted ether compounds

A technology to replace ethers and compounds, applied in the field of organic synthetic chemistry, can solve the problems of complex synthesis of hypervalent iodine, achieve good compatibility, simple and easy synthesis method, and wide range of biological activities

Active Publication Date: 2018-01-09
NANJING UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But the synthesis of hypervalent iodine is more complicated (Z.-F.Cheng, Y.-S.Feng, C.Rong, T.Xu, P.-F.Wang, J.Xu, J.-J.Dai and H. -J. Xu, Green Chem., 2016, 18, 4185)

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  • Method for synthesizing alpha-alkynyl substituted ether compounds
  • Method for synthesizing alpha-alkynyl substituted ether compounds
  • Method for synthesizing alpha-alkynyl substituted ether compounds

Examples

Experimental program
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Effect test

experiment example 1

[0026] Synthesis of 2-(phenylethynyl)tetrahydrofuran

[0027] In a reaction vessel, iodobenzene (10.0mmol), DBU (3.66g, 24mmol, 2.4equiv), Pd(PPh 4 ) 3 (288mg, 0.26mmol, 2.5mol%) was dissolved in 12ml of DMSO to form solution a, then propiolic acid (840mg, 12mmol, 1.2equiv) was dissolved in 12ml of DMSO to form solution b, and finally solution b was slowly was added dropwise to solution a, stirred and reacted at room temperature for 12 hours. After the reaction, add 25ml of ethyl acetate to the reaction solution, extract with saturated sodium bicarbonate solution, adjust the pH of the collected water layer to 2.0 with 1mol / L hydrochloric acid, and finally extract the organic matter with dichloromethane. layer, separated the organic phase and used anhydrous sodium sulfate to remove water, and after drying, removed the solvent by distillation under reduced pressure to obtain a crude product, and separated the crude product by column chromatography to obtain a phenylpropiolic a...

experiment example 2

[0030] Synthesis of 2-((4-chlorophenyl)ethynyl)tetrahydrofuran

[0031] In a reaction vessel, p-chloroiodobenzene (10.0mmol), DBU (3.66g, 24mmol, 2.4equiv), Pd(PPh 4 )3 (288mg, 0.26mmol, 2.5mol%) was dissolved in 12ml of DMSO to form solution a, then propiolic acid (840mg, 12mmol, 1.2equiv) was dissolved in 12ml of DMSO to form solution b, and finally solution b was slowly was added dropwise to solution a, stirred and reacted at room temperature for 12 hours. After the reaction, add 25ml of ethyl acetate to the reaction solution, extract with saturated sodium bicarbonate solution, adjust the pH of the collected water layer to 2.0 with 1mol / L hydrochloric acid, and finally extract the organic matter with dichloromethane. layer, separated the organic phase and used anhydrous sodium sulfate to remove water, and after drying, used vacuum distillation to remove the solvent to obtain a crude product, and separated the crude product by column chromatography to obtain p-chlorophenylp...

experiment example 3

[0034] Synthesis of 2-((4-methylphenyl)ethynyl)tetrahydrofuran

[0035] In a reaction vessel, p-methyliodobenzene (10.0mmol), DBU (3.66g, 24mmol, 2.4equiv), Pd(PPh 4 ) 3 (288mg, 0.26mmol, 2.5mol%) was dissolved in 12ml of DMSO to form solution a, then propiolic acid (840mg, 12mmol, 1.2equiv) was dissolved in 12ml of DMSO to form solution b, and finally solution b was slowly was added dropwise to solution a, stirred and reacted at room temperature for 12 hours. After the reaction, add 25ml of ethyl acetate to the reaction solution, extract with saturated sodium bicarbonate solution, adjust the pH of the collected water layer to 2.0 with 1mol / L hydrochloric acid, and finally extract the organic matter with dichloromethane. layer, separated the organic phase and used anhydrous sodium sulfate to remove water, and after drying, used vacuum distillation to remove the solvent to obtain a crude product, and separated the crude product by column chromatography to obtain p-tolylpropio...

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Abstract

The invention discloses a method for preparing alpha-alkynyl substituted ether compounds. The method comprises the following steps: taking propiolic acid as a raw material, and synthesizing substituted phenylpropiolic acid under conditions of substituted iodobenzene, 1,8-diazabicyclo[5.4.0]undec-7-ene, (beta-4)-platinu and dimethyl sulfoxide; taking substituted phenylpropiolic acid and p-bromophenol as raw materials, and synthesizing p-bromophenyl substituted phenylpropiolic acid ester under the conditions of 4-dimethylaminopyridine and N,N'-Dicyclohexylcarbodiimide; and performing an alkynylation reaction on the p-bromophenyl substituted phenylpropiolic acid ester in participation of tert-butyl hydroperoxide, cesium carbonate and tetrahydrofuran, and finally synthesizing alpha-alkynyl substituted ether products. According to the method disclosed by the invention, simple and readily available acetylene esters serve as an alkynylation reagent, and the target products, namely alpha-alkynyl substituted ether compounds, are synthesized in a green and environmental-friendly manner under mild conditions. The compounds play an important role in construction of multiple medical intermediates and bio-active structures.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and in particular relates to a method for synthesizing α-alkynyl substituted ether compounds. Background technique [0002] The α-alkynyl substituted ether compounds are important heterocyclic compounds. The ether structure exists in many pharmaceutically active molecules and is widely used in the fields of materials chemistry, medicinal chemistry, and dyes. More than 20% of the top 200 small-molecule drugs contain at least one α-substituted ether moiety, so finding new ways to synthesize α-alkynyl substituted ethers is important for the discovery of bioactive agents. At present, the main methods for synthesizing α-alkynyl substituted ether compounds are as follows: [0003] In 1996, the Fuchs research group reported the use of alkynyl trifluoromethylsulfonyl as an alkynylation reagent and epoxy ethers to synthesize 2-alkynyl epoxy ethers under the action of peroxides (J.Gong...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/06C07D307/10
Inventor 姜超亚斯赵树芳
Owner NANJING UNIV OF SCI & TECH
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