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

Hydroxylation of Halogenated Aromatic Compounds

A technology of aromatic compounds and hydroxylation, which is applied in the preparation of organic compounds, carbon-based compounds, chemical instruments and methods, etc., can solve the problems of expensive ligands and difficult reactions of substrates, and achieve good application prospects and low prices , the effect of mild reaction conditions

Active Publication Date: 2021-02-12
HENGYANG NORMAL UNIV
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, there are still many limitations in the use of palladium catalysts. For example, substrates containing certain functional groups are difficult to react, palladium reagents and their co-catalyzed ligands are expensive, and at the same time, palladium catalyzes the reaction in a relatively expensive organic solvent. conduct

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
  • Hydroxylation of Halogenated Aromatic Compounds
  • Hydroxylation of Halogenated Aromatic Compounds
  • Hydroxylation of Halogenated Aromatic Compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] The preparation of embodiment 1 4-methoxyphenol

[0036]

[0037] In a sealed reaction tube at one end, add 234mg p-methoxyiodobenzene (MW=234,1.0 mmol), then add 280mg KOH (MW=56,5mmol), 14.7mg 6,7-dihydroquinoline-8 (5H)-ketone (MW = 147, 0.1mmol), 9.5mg CuI (MW = 190, 0.05mmol), 64mg tetrabutylammonium bromide (TBAB) (MW = 320, 0.2mmol) and 1mL water, in argon Under the protection of air or nitrogen, stir the reaction at 90°C for 24 hours. After the reaction liquid is cooled, add 5 ml of 30% hydrochloric acid, then extract the reaction mixture three times with 30 mL of ethyl acetate, combine the extracts, dry, and distill under reduced pressure. Separation on a silica gel column (eluent: petroleum ether: ethyl acetate = 3:1) yielded 115 mg of the product 4-methoxyphenol with a yield of 93%.

[0038]

[0039] 1 H NMR (CDCl 3 )δ6.79(m,4H),5.88(br,1H),3.77(s,3H); 13 C NMR (CDCl 3 ) δ153.5,149.5,116.1,114.9,55.9.

Embodiment 2

[0040] The preparation of embodiment 2 4-methoxyphenol

[0041]

[0042] According to the method described in Example 1, the difference is that the base used is NaOH, NaOH 200mg and 4-methoxyiodobenzene (234mg, 1.0mmol) were stirred and reacted for 24h. The crude product was purified by column chromatography (petroleum ether:ethyl acetate=3:1), yield: 81%;

[0043] 1 H NMR (CDCl 3 )δ6.79(m,4H),5.88(br,1H),3.77(s,3H); 13 C NMR (CDCl 3 ) δ153.5,149.5,116.1,114.9,55.9.

Embodiment 3

[0044] The preparation of embodiment 3 4-methoxyphenol

[0045]

[0046]According to the method described in Example 1, the difference is that the base used is CsOH, and 600 mg of CsOH and 4-methoxyiodobenzene (234 mg, 1.0 mmol) were stirred and reacted for 24 h. The crude product was purified by column chromatography (petroleum ether:ethyl acetate=3:1), yield: 96%;

[0047] 1 H NMR (CDCl 3 )δ6.79(m,4H),5.88(br,1H),3.77(s,3H); 13 C NMR (CDCl 3 ) δ153.5,149.5,116.1,114.9,55.9.

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 for the hydroxylation of halogenated aromatic compounds. In the method, 2-pyridone compound is used as a ligand additive, CuI is used as a catalyst, and in the presence of a phase transfer catalyst and a solvent, MOH and halogenated aromatic compounds can be realized. The hydroxylation reaction of the compound is carried out under mild conditions, and the reaction yield is high, and the applicable range of substrates is wide. Compared with the same type of reactions reported in the literature, the method of the invention has mild reaction conditions, high yield and good application prospects. The hydroxylation reaction of iodoaromatic compounds can be carried out at 90°C in aqueous solution and high-yield hydroxylated products can be obtained, and the reaction temperature can be reduced by about 30°C on average compared with the reports in the literature; The reaction can be carried out at 120 °C, and the reaction temperature can be reduced by about 20 °C on average compared with the reports in the literature.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a hydroxylation method for halogenated aromatic compounds. Background technique [0002] The Ullmann reaction (Ullmann, F. ber Dtsch. Chem. Ges. 1903, 36, 2382.) has been developed for a long time and has achieved industrial production (Lindley, J. Tetrahedron 1984, 40, 1433). However, the traditional Ullmann coupling reaction is carried out under high temperature and highly polar solvent conditions, and requires equivalent or excess copper reagents. Therefore, the application of the Ullmann reaction has been greatly limited (Lindley, J.Tetrahedron 1984 , 40, 1433). Palladium catalysts have been used in recent years ((a) Yang, B.H.; Buchwald, S.L.J. Organomet.Chem.1999, 576(1-2), 125-146. (b) Hartwig, J.F.Angew.Chem., Int. Ed.Engl. 1998,37,2046-2067), so that the reaction can be carried out under milder conditions. [0003] However, there are still many limitations ...

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): C07B41/02C07C41/26C07C43/23C07C37/02C07C39/04C07C39/14C07C39/27C07C39/07C07C39/11C07C39/15C07C45/65C07C47/565C07C49/825C07C201/12C07C205/22C07C51/367C07C65/03C07D213/65
CPCC07B41/02C07C37/02C07C39/04C07C39/07C07C39/11C07C39/14C07C39/15C07C39/27C07C41/26C07C43/23C07C45/65C07C47/565C07C49/825C07C51/367C07C65/03C07C201/12C07C205/22C07D213/65Y02P20/52
Inventor 王德平许志锋张复兴李薇
Owner HENGYANG NORMAL 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