Method for synthesizing ph-dicarbonyl-aryl-formic-ether series compounds based on metal-free participation method

A technology of dicarbonyl aryl formate and dicarbonyl aryl formate, which is applied in the field of metal-free preparation of o-dicarbonyl aryl formate series compounds, can solve the problem of low atom utilization and achieve substrate Wide applicability, less by-products, and low cost

Active Publication Date: 2017-04-26
JIAXING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the reaction must use metals such as gold, copper, etc. as metal catalysts
Moreover, using 1-fluoro-4-methyl-1,4-diazabicyclo[2.2.2]octane tetrafluoroborate (Selectfluor) as an oxidizing agent, the atom utilization rate is low, and Selectfluor The by-products after leaving the fluorine also bring a lot of inconvenience to the post-reaction treatment process

Method used

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  • Method for synthesizing ph-dicarbonyl-aryl-formic-ether series compounds based on metal-free participation method
  • Method for synthesizing ph-dicarbonyl-aryl-formic-ether series compounds based on metal-free participation method
  • Method for synthesizing ph-dicarbonyl-aryl-formic-ether series compounds based on metal-free participation method

Examples

Experimental program
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Effect test

Embodiment 1

[0041]

[0042] In the air atmosphere, adopting 1.0 parts by weight of o-phenylethynyl benzoate as a reaction substrate, adding 2.0 parts by weight of tetra-n-butylammonium bromide as a bromine source and 2.0 parts by weight of potassium peroxymonosulfonate as an oxidant , adding an aqueous solution of 1,2-dichloroethane with a volume fraction of 50%, so that the concentration of o-phenylethynyl benzoate is 0.1M. After reacting for 6 hours at a temperature of 60° C., 10 parts by weight of silica gel was added and the mixture was stirred for 0.5 hours. During the reaction, TLC was used to monitor until the reaction was complete. After the reaction, the reaction solution was filtered, the filtrate was extracted with ether, and the organic phase was extracted with anhydrous Na 2 SO 4 After drying and filtering again, the filtrate was distilled to remove the organic solvent and then flash column chromatography to obtain the pure product o-dicarbonyl aryl formate series compoun...

Embodiment 2

[0046]

[0047] In the air atmosphere, 1.0 parts by weight of ethyl 2-phenylethynyl-3-pyridinecarboxylate is used as a reaction substrate, and 2.0 parts by weight of potassium bromide is added as a bromine source and 2.0 parts by weight of potassium peroxymonosulfonate as an oxidant , adding an aqueous solution of 1,2-dichloroethane with a volume fraction of 50%, and the concentration of ethyl 2-phenylethynyl-3-pyridinecarboxylate was 0.1M. After reacting for 8 hours at a temperature of 70° C., 10 parts by weight of silica gel was added and the mixture was stirred for 0.6 hours. During the reaction, TLC was used to monitor until the reaction was complete. After the reaction, the reaction solution was filtered, the filtrate was extracted with ether, and the organic phase was extracted with anhydrous Na 2 SO 4 After drying and filtering again, the filtrate was distilled to remove the organic solvent and then flash column chromatography to obtain the pure product o-dicarbonyl...

Embodiment 3

[0053]

[0054] In the air atmosphere, adopt 1.0 parts by weight of 2-phenylethynyl-cyclohexenecarboxylate reaction substrate, add 2.5 parts by weight of tetra-n-butylammonium bromide as bromine source and 2.5 parts by weight of peroxymonosulfonic acid Potassium is an oxidizing agent, 1,2-dichloroethane aqueous solution with a volume fraction of 50% is added, and the concentration of ethyl 2-phenylethynyl-cyclohexenecarboxylate is 0.1M. After reacting for 9 hours at a temperature of 80° C., 10 parts by weight of silica gel was added and the mixture was stirred for 1 hour. During the reaction, TLC was used to monitor until the reaction was complete. After the reaction, the reaction solution was filtered, the filtrate was extracted with ether, and the organic phase was extracted with anhydrous Na 2 SO 4 After drying and filtering again, the filtrate was distilled to remove the organic solvent and then flash column chromatography to obtain the pure product o-dicarbonyl-aryl f...

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Abstract

The invention discloses a method for synthesizing ph-dicarbonyl-aryl-formic-ether series compounds based on the metal-free participation method, and belongs to the technical field of organic chemistry. The method includes the steps that phalkynyl benzoic ether is used as a reaction substrate, bromide is added to serve as a bromine source, peroxosulfuric acid inorganic salt serves as an oxidizing agent, a solvent is added, the mixture is reacted for 6 hours to 12 hours at the temperature of 60 DEG C to 80 DEG C, then column chromatography silica gel (SiO2) is added, then the mixture continues to be stirred for 0.5 hour to 1 hour, filtering, extracting and drying are carried out, filtering is carried out again, filtering liquid is subjected to pressure reduction distillation, an organic solvent is removed, then rapid column chromatography is carried out, and the ph-dicarbonyl-aryl-formic-ether series compounds are obtained. By means of a reaction, using of a metal catalyst is avoided, the reaction condition is mild, the substrate is wide in applicability, easy and convenient to operate, low in cost, small in by product, high in product purity, convenient to separate and purify and capable of suiting for large-scale preparing.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, in particular to a method for preparing o-dicarbonyl aryl formate series compounds by a metal-free method in which bromide salt is used as a bromine source and peroxysulfuric acid inorganic salt is used for oxidation. Background technique [0002] Ortho-dicarbonyl aryl formate series compounds are very important intermediates in organic synthesis of oxygen heterocycles, which can be used to synthesize some oxygen heterocyclic compounds with broad-spectrum biological activity, as described in the following documents: (a) synthesisofinfluenza virus type B inhibitor, Malpani, Y.; Achary, R.; Kim, S.Y.; Jeong, H.C.; S.Eur.J.Med.Chem.,2013,62,534; (b)synthesis of optically active isochromans,Zhu,T.-Z.;Chen,J.-P.;Xu,M.-H.Chem.Eur . J. 2013, 19, 865. etc. [0003] However, there are very few synthetic methodological studies on it. Traditional method mainly selects 2-(2-nitro-2 aryl ethyl ke...

Claims

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Application Information

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IPC IPC(8): C07B41/06C07C67/343C07C69/76C07D213/803C07D213/80C07C69/757C07D333/22
CPCC07B41/06C07C67/343C07D213/80C07D213/803C07D333/22C07C69/76C07C69/757
Inventor 邱观音生袁斯甜刘晋彪
Owner JIAXING UNIV
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