Cheap and efficient synthesis method of alpha-hydroxyketone compound

A carbonyl compound and compound technology, which is applied in the field of synthesis of α-hydroxy ketone compounds, can solve the problems of narrow substrate application range and complicated operation, and achieves the effects of wide applicability, simple reaction equipment and less waste discharge.

Active Publication Date: 2015-06-17
QINGDAO RUIJI MEDICAL TECH CO LTD
View PDF2 Cites 11 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are not many reports on the synthesis method directly converted from carbonyl compounds to α-hydroxy ketone compounds, although literature a) B.-C.Chen, P.Zhou, F.A.Davis, E.Ciganek, Organic Reactions; L.E.Overman, Ed. ; John Wiley & Sons, Inc.: New York, 2003, 62, 1; b) G.J. Chuang, W. Wang, E. Lee, T. Ritter, J. Am. Chem. Soc. 2011, 133, 1760; c) Y .-F.Liang, N.Jiao, Angew.Chem.Int.Ed.2014,53,548. The synthesis methods of this type of compounds have been reported in detail, but these methods have great limitations: 1. Substrate The scope of application is narrow; 2. Use expensive and complex palladium as a catalyst or require the use of an equivalent reducing agent; 3. Require more complicated operations

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Cheap and efficient synthesis method of alpha-hydroxyketone compound
  • Cheap and efficient synthesis method of alpha-hydroxyketone compound
  • Cheap and efficient synthesis method of alpha-hydroxyketone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 12

[0036] The preparation of embodiment 12-hydroxyl-1-phenylacetone

[0037]

[0038] a): get a 25mL Schlenk reaction tube, add iodine simple substance (I 2 ) 26mg (0.1mmol) as catalyst, 1-phenylacetone 68mg (0.5mmol), dimethyl sulfoxide (DMSO) 1mL as oxidant, hydroxyl source and solvent, stirred at 60°C for 24 hours. After the reaction was completed, 15 mL of ethyl acetate and 3 mL of brine were added, extracted three times with ethyl acetate, the organic phases were combined, and separated by column chromatography to obtain 54 mg of pure 2-hydroxy-1-phenylacetone with a yield of 72%. (optimal system)

[0039] b): Take a 25mL Schlenk reaction tube, add N-bromosuccinimide (NBS) 18mg (0.1mmol) as a catalyst, 1-phenylacetone 68mg (0.5mmol), dimethyl sulfoxide (DMSO) 1 mL was used as oxidizing agent, hydroxyl source and solvent, and stirred at 60°C for 24 hours. After the reaction was completed, 15 mL of ethyl acetate and 3 mL of brine were added, extracted three times with et...

Embodiment 22

[0076] The preparation of embodiment 22-hydroxyl-1-p-methyl phenylacetone

[0077]

[0078] Get a 25mL Schlenk reaction tube, add iodine simple substance (I 2 ) 26mg (0.1mmol) as catalyst, p-methyl phenylacetone 75mg (0.5mmol), dimethyl sulfoxide (DMSO) 1mL as oxidant, hydroxyl source and solvent, stirred at 60°C for 24 hours. After the reaction, 15 mL of ethyl acetate and 3 mL of brine were added, extracted three times with ethyl acetate, the organic phases were combined, and separated by column chromatography to obtain 62 mg of pure 2-hydroxy-1-p-methylphenylacetone with a yield of 76%.

[0079] 1 H NMR (400MHz, CDCl 3 ):δ7.83(d,J=8.4Hz,2H),7.29(d,J=8.0Hz,2H),5.17-5.10(m,1H),3.86(d,J=8.0Hz,1H),2.42 (s,3H),1.44(d,J=7.2Hz,3H); 13 C NMR (100MHz, CDCl 3 ):δ201.8,144.9,130.6,129.4,128.6,69.0,22.3,21.6ppm; MS(70ev):m / z(%):91.1(50),119.0(100),164.0(M + ,1).

Embodiment 32

[0080] The preparation of embodiment 32-hydroxyl-1-p-methoxyphenylacetone

[0081]

[0082] Get a 25mL Schlenk reaction tube, add iodine simple substance (I 2 ) 26mg (0.1mmol) as catalyst, p-methoxyphenylacetone 83mg (0.5mmol), dimethyl sulfoxide (DMSO) 1mL as oxidant, hydroxyl source and solvent, stirred at 60°C for 24 hours. After the reaction, 15 mL of ethyl acetate and 3 mL of brine were added, extracted three times with ethyl acetate, the organic phases were combined, and separated by column chromatography to obtain 70 mg of pure 2-hydroxy-1-p-methoxyphenylacetone with a yield of 78%.

[0083] 1 H NMR (400MHz, CDCl 3 ): δ7.92(d, J=8.4Hz, 2H), 6.97(d, J=9.2Hz, 2H), 5.14-5.07(m, 1H), 3.91(s, 1H), 3.88(s, 3H) ,1.44(d,J=6.4Hz,3H); 13 C NMR (100MHz, CDCl 3 ):δ200.5,164.0,130.9,125.9,113.9,68.7,55.4,22.4ppm; MS(70ev):m / z(%):77.0(20),135.0(100),180.0(M + ,3).

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention discloses a cheap and efficient synthesis method of an alpha-hydroxyketone compound. The synthesis method is characterized in that a carbonyl compound undergoes an oxidation hydroxylation reaction at 10-120DEG C under normal pressure with iodine simple substance, N-bromosuccimide, copper bromide, bromine simple substance, hydrogen bromide, N-iodosuccimide or hydrogen iodide as a catalyst, sulfoxide as an oxidant, water or sulfoxide as a hydroxy source and sulfoxide, ethyl acetate, N,N-dimethyl formamide, acetonitrile, toluene, 1,4-dioxane, 1,2-dichloroethane, tetrahydrofuran or H2O as a solvent, and converts into the alpha-hydroxyketone compound in a high selectivity manner. Compared with traditional synthesis methods, the method disclosed in the invention has the advantages of simple operation, high yield, simple conditions, easy purification, small waste discharge amount, simple reaction apparatus, and easy industrial production. The method has wide applicability and can be used for synthesizing various alpha-hydroxyketone compounds.

Description

technical field [0001] The invention relates to a method for synthesizing alpha-hydroxy ketone compounds, belonging to the technical field of chemical synthesis. Background technique [0002] α-Hydroxyketone compounds widely exist in biologically active natural products and pharmaceutical intermediates. At the same time, α-hydroxy ketone compounds are widely used synthons in organic synthesis. Hydroxyl is a mild reaction precursor for groups such as double bonds, ester groups, and halogenated hydrocarbons. Heterocyclic compounds can also be derived from α-hydroxy ketone structures. come. Therefore, the α-hydroxyl located at the active site of the molecular structure is an important structural unit, and the introduction of this group has greater research significance. In addition, α-hydroxy ketones can be used as photoinitiators and are widely used in UV-curable coatings. However, there are not many reports on the synthesis method directly converted from carbonyl compounds...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/02C07C45/64C07C49/82C07C49/84C07C49/83C07C49/17C07C49/747C07D307/46C07D333/22C07D213/50
Inventor 焦宁梁雨锋
Owner QINGDAO RUIJI MEDICAL TECH CO LTD
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap