Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for preparing alpha-aryl carbonyl compound

A carbonyl compound and arylcarbonyl technology, applied in the field of preparation of α-aryl carbonyl compounds, can solve the problems of inability to contain β hydrogen and narrow substrate range, and achieve the effects of mild reaction conditions, easy preparation and stable substrates

Inactive Publication Date: 2010-06-02
WUHAN UNIV
View PDF6 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in their system, the scope of substrates is narrow, and the α-position of bromoesters and amides cannot contain β-hydrogens and active hydrogens on the amide nitrogen.

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
  • Method for preparing alpha-aryl carbonyl compound
  • Method for preparing alpha-aryl carbonyl compound
  • Method for preparing alpha-aryl carbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1: Reaction of 2-Bromoesters or Amides

[0017] In a reaction system, add phenylboronic acid (243.8mg, 2.0mmol), 2-bromo ester or amide (1.0mmol), Ni(PPh 3 ) 4 (110.8 mg, 0.1 mmol), K 3 PO 4 (849.2 mg, 4.0 mmol), the system was replaced by nitrogen protection, 2 ml of toluene was added, and the reaction was carried out at 60 degrees Celsius for 16 hours. Stop the reaction, add 2 ml of 2M dilute hydrochloric acid to the system, add 5-10 ml of ethyl acetate three times for extraction, combine the organic phases, and dry over anhydrous sodium sulfate. The product 2-phenyl ester or amide was obtained by column chromatography, and the separation yield is shown in Table 1 below.

[0018]

[0019] Table 1 Arylation reaction of phenylboronic acid with 2-bromoester and amide

[0020]

Embodiment 2

[0022] In a reaction system, add substituted phenylboronic acid (2.0mmol), 2-bromo ester or amide (1.0mmol), Ni(PPh 3 ) 4 (110.8 mg, 0.1 mmol), K 3 PO 4 (849.2 mg, 4.0 mmol), the system was replaced by nitrogen protection, 2 ml of toluene was added, and the reaction was carried out at 60 degrees Celsius for 16 hours. Stop the reaction, add 2 ml of 2M dilute hydrochloric acid to the system, add 5-10 ml of ethyl acetate three times for extraction, combine the organic phases, and dry over anhydrous sodium sulfate. The product 2-substituted phenyl ester or amide was obtained by column chromatography, and the separation yield is shown in Table 2 below.

[0023]

[0024] Table 2 Reaction of substituted phenylboronic acids with 2-bromo esters and amides

[0025]

[0026] b The reaction temperature is 80 degrees Celsius

Embodiment 3

[0027] Embodiment 3: the reaction of 2-bromoketone or 2-chloroketone

[0028] In a reaction system, add arylboronic acid (2.0mmol), 2-bromoketone or 2-chloroketone (1.0mmol), Ni(PPh 3 ) 4 (110.8 mg, 0.1 mmol), K 3 PO 4 (1273.8 mg, 6.0 mmol), the system was replaced with nitrogen protection, 2 ml of toluene was added, and the reaction was carried out at 60 degrees Celsius for 16 hours. Stop the reaction, add 2 ml of 2M dilute hydrochloric acid to the system, add 5-10 ml of ethyl acetate three times for extraction, combine the organic phases, and dry over anhydrous sodium sulfate. 2-aryl ketone was obtained by column chromatography. The separation yield is shown in Table 3 below.

[0029]

[0030] Table 3: Nickel-catalyzed arylation of ketones

[0031]

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 relates to a method of preparing Alpha-aryl carbonyl compound. With the catalyst of four triphenylphosphine nickel or acetylacetone nickel ligand, aryl boric acid, Alpha-halogenated carbonyl compound, ligand and additive are dissolved in toluene, and after reaction for 10 to 24 hours in 50 to 100 DEG C, the Alpha-aryl carbonyl compound is obtained, wherein, the ligand is single-toothphosphine ligand or double-tooth phosphine ligand; and the additive is absolute potassium phosphate or tri-potassium phosphate. The invention, which utilizes the catalyst with low cost, stable substrate, easy obtaining and gentle reaction conditions, can not only catalyze arylation of ester, amide and ketone, but also can be compatible with beta hydrogen, thereby greatly expanding the range of the substrate. Moreover, the invention possesses great application potential and can directly constitute the main framework of the steride.

Description

technical field [0001] The present invention relates to a process for the preparation of α-arylcarbonyl compounds. Background technique [0002] The α-arylation of carbonyl compounds is an interesting and challenging reaction. Its α-aryl derivatives are important structural units of many natural products, drugs, and synthetic intermediates. For example, α-aryl carboxylic acid compounds such as Naproxen, flurbiprofen, and diclofenac have anti-inflammatory and analgesic effects. In this field, Buchwald, Hartwig, Gooβen and others have carried out more characteristic research. They all use palladium as a catalyst. Buchwald and Hartwig use the Reformatsky reagents of enol metal salts, enol siloxy ethers of esters or amides generated by carbonyl compounds under the action of strong bases to undergo palladium-catalyzed coupling reactions with halogenated aromatics to generate α-arylated product. From the initial ketones to the derivatives of carbonyl compounds such as nitro co...

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 Patents(China)
IPC IPC(8): C07B41/06C07B41/08C07B41/12C07C69/612C07C233/11C07C49/76B01J31/24B01J31/28
Inventor 雷爱文刘超
Owner WUHAN UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com