Oxa-Michael addition reaction method to generate o-quinone methides in situ by Sc(III) catalysis of alcohols

An in-situ generation technology of methylene quinone, applied in organic chemistry, preparation of ether by dehydration of hydroxyl-containing compounds, preparation of ether, etc., can solve the problems of high price, rare intermolecular oxa-Michael addition reaction, etc., and achieve easy Separation and purification, simple operation and high reaction yield

Inactive Publication Date: 2019-03-08
NEW MATERIAL INST OF SHANDONG ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the research on o-methylenebenzoquinone has a long history, the conjugate addition reaction of o-methylenebenzoquinone based on heteroatoms still has great defects: based on P, S and N heteroatoms The conjugate addition reaction has been relatively mature, but the intermolecular oxa-Michael addition reaction of alcohols with weaker nucleophilicity is relatively rare. Currently, there is only one case of using an expensive organophosphoric acid catalyst to realize the reaction process.

Method used

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  • Oxa-Michael addition reaction method to generate o-quinone methides in situ by Sc(III) catalysis of alcohols
  • Oxa-Michael addition reaction method to generate o-quinone methides in situ by Sc(III) catalysis of alcohols
  • Oxa-Michael addition reaction method to generate o-quinone methides in situ by Sc(III) catalysis of alcohols

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025]

[0026] Add 2.00 g (10 mmol) of compound I-1, 0.92 g (20 mmol) of compound II-1, and 0.49 g (1 mmol) of solid Sc(OTf) into a 100 mL round bottom flask 3 , and finally 50 mL of dry 1,2-dichloroethane was added, and the resulting mixture was stirred at 40 °C for 6 hours. After the reaction mixture was cooled to room temperature, it was poured into ice water, extracted with 50mL×3 methylene chloride, and the extracted organic phases were combined, washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and remove the solvent to obtain the crude product, which is separated by column chromatography to obtain the pure product of compound III-1. Oily liquid, 2.17g, yield 95%.

Embodiment 2

[0028]

[0029] Add 2.00g (10mmol) compound I-1, 0.92g (20mmol) compound II-1, 0.98g (2mmol) solid Sc(OTf) into a 100mL round bottom flask 3 , and finally 25 mL of dry DMF was added, and the resulting mixture was stirred at 30° C. for 3 hours until the reaction was complete. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL×3 dichloromethane, combined and extracted organic phases, washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and remove the solvent to obtain the crude product, which is separated by column chromatography to obtain the pure product of compound III-1. Oily liquid, 2.23g, yield 98%.

Embodiment 3

[0031]

[0032] Add 2.00g (10mmol) compound I-1, 0.69g (15mmol) compound II-1, 0.12g (0.5mmol) solid Sc(NO 3 ) 3 , and finally 70 mL of dry DMSO was added, and the resulting mixture was stirred vigorously at 50 °C for 5 h. After the reaction mixture was cooled to room temperature, it was poured into water, stirred, extracted with 50mL×3 dichloromethane, combined and extracted organic phases were washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and evaporate the solvent to obtain the crude product, and purify by column chromatography to obtain the pure product of compound III-1. Oily liquid, 2.00g, yield 88%.

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Abstract

The invention provides an oxa-Michael addition reaction method to generate o-quinone methides by Sc(III) catalysis of alcohols. 2-(Hydroxy(phenyl)methyl)phenol compounds and alcohol compounds are catalyzed by Sc(III) to generate o-quinone methides in situ and cause oxa-Michael addition reaction; product yield reaches 88-98%. The method herein is simple to perform; the materials and reagents are simple; the reaction product yield is high; the defect that the traditional methods employ expensive catalysts and have strict conditions is avoided; the product is easy to separate and purify; the method herein is important to the methodological study on o-quinone methides and is important to total synthesis of natural products and discovery of drugs.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a synthesis method for the oxa-Michael addition reaction of Sc(III) catalyzed alcohol compounds to o-methylenebenzoquinone. Background technique [0002] O-methylene quinone compounds are a class of very active and important intermediates, which were discovered by scientists Fries and Kann as early as 1907. These compounds have high chemical activity and are widely used in natural product and medicinal chemistry. For example: Many animals and plants use this compound for their own defense; vitamin E, K with therapeutic effect and some anti-cancer drugs exert their medicinal effects by generating o-methylene quinone in situ in the body and so on. Because o-methylenebenzoquinone compounds are widely used, the research on their preparation methods has always been a focus of attention of organic synthesis experts. Many preparation methods reported in the liter...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C41/09C07C43/178
CPCC07C41/09C07C43/1783C07C43/1786
Inventor 张硕彭丹赵宁李冰于一涛牟秋红张方志王峰李金辉
Owner NEW MATERIAL INST OF SHANDONG ACADEMY OF SCI
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