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Preparation method of six-membered aryl lactone or six-membered aryl lactam compound

A technology of aryl lactam and aryl lactone, applied in the direction of organic chemistry and the like, can solve the problems of lack of synthesis method, lack of preparation method of six-membered aryl lactone or six-membered aryl lactam compound, unfriendly environment, etc. , to achieve the effect of high atom utilization, high yield and suitable solvent

Active Publication Date: 2020-08-07
HARBIN INST OF TECH SHENZHEN GRADUATE SCHOOL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This electrolysis method provides a halogen source by oxidizing cheap sodium bromide, without the participation of transition metals, and can be realized at room temperature, but the electrochemical conditions usually require a large amount of electrolyte, which is very unfriendly to the environment.
[0004] Due to the importance of the aryl lactone / lactam structure, although its synthesis method has been improved, it is difficult for general, cheap, green reaction conditions without transition metal participation, especially at room temperature to convert sp2 carbon-hydrogen bonds to C-O The crafting method of the / N key is still lacking
[0005] Therefore, prior art still lacks the preparation method of a kind of high-yield six-membered aryl lactone or six-membered aryl-lactam compound

Method used

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  • Preparation method of six-membered aryl lactone or six-membered aryl lactam compound
  • Preparation method of six-membered aryl lactone or six-membered aryl lactam compound
  • Preparation method of six-membered aryl lactone or six-membered aryl lactam compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] (1) Add 0.36mmol cesium iodide (CsI) and 0.3mmol 2-phenylbenzoic acid into a 25mL reaction tube, add 0.6mmol MPO (4,4-dimethyl-1,2-dioxolane-3,5-dione) and 3mL of o-dichloroethane, the molar ratio of cesium iodide to MPO is 0.6:1; use a vacuum pump to remove the gas in the reaction tube and solvent, and fill it with nitrogen, repeat the operation three times, and then place the reaction tube at a temperature of 420-430nm In the stirrer irradiated by the blue light of the band LED, the reaction is detected with a thin-layer chromatography (TLC) plate until the reaction of the raw materials is complete;

[0033] (2) Add 10mL of ethyl acetate (EA) and 10mL of water, extract the liquid with a 60mL separating funnel, extract the aqueous phase with EA three times (3*10mL), combine the organic phase and wash once with 10mL of saturated brine, collect The organic phase was dried with anhydrous sodium sulfate;

[0034] (3) Remove sodium sulfate by filtration, and the organic ph...

Embodiment 2

[0042](1) Add 0.36mmol cesium iodide (CsI) and 0.3mmol N-methoxy-1,1'-biphenyl-2-amide into a 25 mL reaction tube, add 0.6mmol MPO (4,4-dimethyl- 1,2-dioxolane-3,5-dione) and 3mL o-dichloroethane, use a vacuum pump to remove the gas in the reaction tube and solvent, and fill it with nitrogen, repeat the operation three times, and then place the reaction tube in the 420-430nm band In the stirrer irradiated by LED blue light, use a thin layer chromatography (TLC) plate to detect the reaction until the reaction of the raw materials is complete;

[0043] (2) Add 10mL of ethyl acetate (EA) and 10mL of water, extract the liquid with a 60mL separating funnel, extract the aqueous phase with EA three times (3*10mL), combine the organic phase and wash once with 10mL of saturated brine, collect The organic phase was dried with anhydrous sodium sulfate;

[0044] (3) Sodium sulfate was removed by filtration, and the organic phase was removed by a rotary evaporator to obtain a crude produc...

Embodiment 3

[0052] This example only describes the difference from Example 1, the solvent in the step (1) is different, specifically dichloromethane, and the yield of the crude product is 80%.

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Abstract

The invention discloses a preparation method of a six-membered aryl lactone or six-membered aryl lactam compound. Specifically, an oxygen-halogen bond can be prepared by utilizing cyclic diacyl peroxide and halogenated salt under an illumination condition, and the oxygen-halogen bond is prone to homolysis under an illumination condition to form an active free radical, so the six-membered aryl lactone or six-membered aryl lactam compound is prepared. The method can be completed at room temperature; participation of transition metal is not needed; a combination of the cyclic diacyl peroxide andthe halogen salt serves as a precursor of a high-activity halogen source; the method has the advantages of easiness in preparation, good thermal stability, good thermal safety and the like; the methodis simple in synthesis process and high in yield, so the use amount of halide for reactions with synthesis value is reduced, and the purposes of environmental protection and green chemistry are better achieved.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry synthesis, and it relates to a preparation method of a ring-forming compound, in particular to a preparation method of a six-membered aryl lactone or a six-membered aryl lactam compound. Background technique [0002] Six-membered aromatic lactone or its lactam compound is an important part of organic compounds, not only widely exists in various natural products and drugs with antibacterial and anticancer activities, but also an important structure of some organic functional materials such as dyes unit. In the past, the direct chemical conversion of aromatic ring C-H bonds involving transition metals to construct C-N / O bonds was considered to be an effective method for functionalizing double bonds. For example, Wang Xisheng's research group at the University of Science and Technology of China used transition metal palladium (Pd) as a catalyst to realize the lactonization process of biary...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D311/80C07D221/12
CPCC07D311/80C07D221/12
Inventor 史雷昌登虎赵戎
Owner HARBIN INST OF TECH SHENZHEN GRADUATE SCHOOL
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