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Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction

A technology of thiocarboxylic acid and catalyzed phenolic acyl, which is applied in the field of preparation of phenolic ester by catalyzed phenolic acylation reaction under visible light, achieving the effects of mild reaction conditions, strong applicability, and high yield

Active Publication Date: 2018-06-22
长治学院
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Visible light-promoted acylation of phenol has not been reported so far. Traditional methods for preparing esters often require the use of sensitive acylating reagents such as acid chlorides or anhydrides, and it is difficult to specifically use them when both alcoholic and phenolic hydroxyl groups exist in the substrate. The phenolic hydroxyl group with poor nucleophilicity undergoes esterification while the alcoholic hydroxyl group is not affected

Method used

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  • Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction
  • Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction
  • Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Add 1.0 mmol of aromatic thiocarboxylic acid substrates (such as Dissolve in 5mL of acetonitrile, add 0.01mmol of terpyridine hexahydrate ruthenium dichloride and 0.1mmol of potassium carbonate to the reaction system, stir for three hours in an open environment at room temperature under the irradiation of a 45W fluorescent lamp, then add 0.5mmol of phenolic base things (such as 1.0mmol triethylamine and 0.1mmol N, N-lutidine, after stirring for 10 minutes, pour the reaction mixture into 10mL water, extract four times with 10mL ethyl acetate, combine the organic phases and wash with 15mL saturated brine, After the organic phase was dried over anhydrous sodium sulfate, the organic solvent was removed by rotary evaporation, and the crude product was purified through a section of silica gel chromatography (n-hexane:ethyl acetate=20:1-5:1) about 10 cm long to obtain the corresponding Phenol ester compound 3, compound 5, compound 7 and compound 12.

[0019] Spectral data ...

Embodiment 2

[0080] 1.0mmol aliphatic thiocarboxylic acid substrate (such as and 0.5mmol phenolic substrate (such as Dissolve in 5mL of acetonitrile, add 0.01mmol hexahydrate terpyridyl ruthenium dichloride and 1.0mmol potassium carbonate to the reaction system, stir for 3-6 hours under sunlight in an open environment at room temperature, then pour the reaction mixture into Extract four times with 10 mL of ethyl acetate in 10 mL of water, combine the organic phases and wash with 15 mL of saturated brine, dry the organic phase with anhydrous sodium sulfate, remove the organic solvent by rotary evaporation, and pass the crude product through a silica gel chromatography column about 10 cm long (n-hexane:ethyl acetate=20:1) for purification, the corresponding phenolic ester compound 9 and compound 11 will be obtained.

[0081] Spectral data are as follows:

[0082]

[0083] 4-bromophenyl acetate 9a

[0084] Compound 9a was obtained with a yield of 56%, a total of 60.2 mg, as a colorles...

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Abstract

The invention discloses a preparation method for synthesis of phenolic ester through a thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction. Thiocarboxylic acid compounds andphenol compounds are subjected to a site specific reaction under certain conditions to produce phenolic ester compounds, wherein the certain conditions are as follows: under the conditions of normaltemperature, normal pressure and visible light, K2CO3 is used as an alkaline catalyst, terpyridyl ruthenium dichloride hexahydrate is used as a photosensitizer and acetonitrile is used as a reaction solvent. Synthesis of phenolic ester under catalysis of visible light is realized, thiocarboxylic acid is used as an acylation reagent, and the site specific phenol esterification reaction is realizedefficiently under mild conditions of normal temperature, normal pressure and visible light. The method has mild reaction conditions, large substrate functional group tolerance, high applicability andhigh yield, and an efficient, reliable and economical preparation method is provided for synthesis of phenolic ester.

Description

technical field [0001] The invention relates to the technical field of organic synthesis methods, in particular to a preparation method for synthesizing phenolic esters through visible light catalyzed phenol acylation reaction mediated by thiocarboxylic acid. Background technique [0002] The ester bond is an important structural unit in the academic fields of organic chemistry, medicinal chemistry, and applied chemical engineering. The known ester bond construction methods mainly use various electrophilic activating reagents such as DCC, DEAD / Ph 3 P, Ph 3 P / NBS, Me 2 NSO 2 Cl / DMAP, Ph 3 PO / (FSO 2 ) 2 O et al. However, the use of the above reagents often brings problems such as long reaction time, cumbersome operation, harsh reaction conditions, toxicity and hazards, etc. Therefore, it is of great scientific significance to explore novel methods of esterification under mild conditions. [0003] The organic synthesis reaction catalyzed by visible light is the use of su...

Claims

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Application Information

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IPC IPC(8): C07C67/08C07C69/78C07C69/83C07C69/92C07C69/618C07C69/773C07C69/157C07C69/16C07C69/24C07C69/614C07C69/616C07C69/612C07C69/75C07C69/73C07C201/12C07C205/57C07C205/43C07J1/00C07C253/30C07C255/57
CPCC07C67/08C07C201/12C07C253/30C07J1/0066C07C69/78C07C69/92C07C69/618C07C69/157C07C69/16C07C69/24C07C69/614C07C69/616C07C69/612C07C69/75C07C69/73C07C205/57C07C205/43C07C255/57
Inventor 史莉莉谭海波王浩申婧翔王晓霞苏静周成勇
Owner 长治学院
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