Preparation method of substituted butyrate derivatives

A technology of derivatives and butyric acid is applied in the field of preparation of substituted butyrate derivatives, which can solve the problems of low thermodynamic efficiency, large substrate restriction, and many steps.

Active Publication Date: 2020-07-03
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to provide a class of three-carbon structural unit with the defects and deficiencies of the prior art, the method of introducing a three-carbon structural unit into a compound is complex, has many steps, low thermodynamic efficiency, and is greatly restricted by the substrate. Preparation method of substituted butyrate derivatives

Method used

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  • Preparation method of substituted butyrate derivatives
  • Preparation method of substituted butyrate derivatives
  • Preparation method of substituted butyrate derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078]

[0079] Add Hans ester Et-HE (0.8mmol), Ru (bpy) to the reaction tube equipped with a magnetic stirrer 3 Cl 2 ·6H 2 O (0.004mmol) and p-thiocresol (0.08mmol). The reaction tube was capped, and after the nitrogen had been replaced three times, 4-fluorostyrene (0.4 mmol), ethyl diazoacetate (0.8 mmol) and anhydrous dichloromethane (2.0 mL, 0.2 M) were injected into the reaction tube with a micro syringe. Then place the reaction tube at a distance of about 15 cm from a 50W blue light source for illumination and stirring. The reaction was carried out at 25° C. for 12 hours until the diazo was completely consumed (monitored by TLC). After removing the solvent by rotary evaporation under reduced pressure, the crude product was obtained. The crude product was purified by silica gel column chromatography to obtain the corresponding product (petroleum ether:ethyl acetate=30:1), the total yield: 87%.

[0080] 1 H NMR (500MHz, CDCl 3 )δ7.16–7.10(m,2H),6.99–6.93(m,2H),4....

Embodiment 2

[0082]

[0083] Add Hans ester Et-HE (0.8mmol), Ru (bpy) to the reaction tube equipped with a magnetic stirrer 3 Cl 2 ·6H 2 O (0.004mmol) and p-thiocresol (0.08mmol). Cover the reaction tube, replace the nitrogen three times, inject 4-trifluoromethylstyrene (0.4mmol), ethyl diazoacetate (0.8mmol) and anhydrous dichloromethane (2.0mL, 0.2M ). Then place the reaction tube at a distance of about 15 cm from a 50W blue light source for illumination and stirring. The reaction was carried out at 25° C. for 12 hours until the diazo was completely consumed (monitored by TLC). After removing the solvent by rotary evaporation under reduced pressure, the crude product was obtained. The crude product was purified by silica gel column chromatography to obtain the corresponding product (petroleum ether:ethyl acetate=30:1), the total yield: 81%.

[0084] 1 H NMR (400MHz, CDCl 3 )δ7.55(d, J=8.0Hz, 2H), 7.31(d, J=8.0Hz, 2H), 4.15(q, J=7.1Hz, 2H), 2.73(t, J=7.7Hz, 2H) ,2.34(t,J=7.4Hz...

Embodiment 3

[0086]

[0087] Add Hans ester Et-HE (0.8mmol), Ru (bpy) to the reaction tube equipped with a magnetic stirrer 3 Cl 2 ·6H 2 O (0.004mmol) and p-thiocresol (0.08mmol). The reaction tube was capped, and after the nitrogen had been replaced three times, 4-cyanostyrene (0.4 mmol), ethyl diazoacetate (0.8 mmol) and anhydrous dichloromethane (2.0 mL, 0.2 M) were injected into the reaction tube with a micro syringe. Then place the reaction tube at a distance of about 15 cm from a 50W blue light source for illumination and stirring. The reaction was carried out at 25° C. for 12 hours until the diazo was completely consumed (monitored by TLC). After removing the solvent by rotary evaporation under reduced pressure, the crude product was obtained. The crude product was purified by silica gel column chromatography to obtain the corresponding product (petroleum ether:ethyl acetate=25:1), the total yield: 86%.

[0088] 1 H NMR (400MHz, CDCl 3 )δ7.59(d, J=7.9Hz, 2H), 7.30(d, J=7.9...

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Abstract

The invention discloses a preparation method of substituted butyrate derivatives. The method specifically comprises the following steps: by taking compounds shown in a formula 1, a formula 2 and a formula 3 as raw materials, carrying out an illumination reaction process in the presence of a photocatalyst and a hydrogen transfer catalyst to obtain a target compound shown in a formula I through one-step reaction. The invention discloses a free radical-mediated olefin bifunctional reaction without a cyclopropanation intermediate. The reaction can realize a product which can be obtained through cyclopropanation and cyclopropane ring opening processes traditionally in one step. Meanwhile, the preparation method of the compound is simple, uses cheap and easily available compounds as raw materials, and has the beneficial effects of one-step synthesis, mild reaction conditions, fast reaction, low cost, less generated waste, simple and safe operation, high atom economy, high selectivity, extremely wide substrate applicability, high yield and the like.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, more specifically, to a preparation method of a class of substituted butyrate derivatives. Background technique [0002] The cyclopropanation reaction of diazo and alkenes is a well-known organic reaction, and its reaction products can be widely used as three-carbon synthons in the synthesis of natural products, biological activities and drugs. With the development of cyclopropane ring-opening reactions, cyclopropane products, especially donor-acceptor cyclopropanes, play an increasingly important role in introducing functionalized three-carbon structural units into the corresponding products. However, although the traditional cyclopropanation and cyclopropane ring-opening process has the advantages of wide application, it is a multi-step process after all, with low thermodynamic efficiency and will be affected by the limitation of substrates in each distribution reaction. [0003] The...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/00C07C69/65C07D213/55C07D277/30C07D209/48C07C69/708C07C69/42C07D295/15C07F5/04C07F7/18C07C69/612C07C69/608
CPCC07C67/00C07D209/48C07D213/55C07D277/30C07D295/15C07F5/04C07F7/1892C07C69/65C07C69/708C07C69/42C07C69/612C07C69/608
Inventor 胡文浩刘耿鑫刘俊文邱晃
Owner SUN YAT SEN UNIV
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