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Hydroxylation method of halogenated aromatic compound

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

Active Publication Date: 2017-10-17
HENGYANG NORMAL UNIV
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  • 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

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  • Hydroxylation method of halogenated aromatic compound
  • Hydroxylation method of halogenated aromatic compound
  • Hydroxylation method of halogenated aromatic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1 Preparation of 4-methoxyphenol

[0036]

[0037] In a reaction tube sealed at one end, 234mg p-methoxy iodobenzene (MW=234, 1.0 mmol) was added, and then 280mg KOH (MW=56,5mmol), 14.7mg 6,7-dihydroquinoline-8 were added sequentially (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 gas or nitrogen, the reaction was stirred at 90°C for 24 hours. After the reaction liquid was cooled, 5 ml of 30% hydrochloric acid was added, and then the reaction mixture was extracted three times with 30 ml of ethyl acetate. The extracts were combined, dried, and distilled under reduced pressure. It was separated through a silica gel column (the eluent was petroleum ether: ethyl acetate = 3:1) to obtain 115 mg of 4-methoxyphenol product, 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...

Embodiment 2

[0040] Example 2 Preparation of 4-methoxyphenol

[0041]

[0042] According to the method described in Example 1, the difference is that the base used is NaOH, and 200 mg of NaOH and 4-methoxyiodobenzene (234 mg, 1.0 mmol) are stirred for reaction for 24 hours. 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] Example 3 Preparation of 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) are used to stir and react for 24 hours. 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.

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Abstract

The invention relates to a hydroxylation method of a halogenated aromatic compound. The method takes a 2-pyridone compound as a ligand additive and takes CuI as a catalyst, under existence of a phase-transfer catalyst and a solvent, MOH and the halogenated aromatic compound are subjected to a hydroxylation reaction under mild condition, the reaction yield is high, and an application scope of a substrate is wide. Compared with same types of reactions reported in literature, the reaction condition of the provided method is mild, the yield is high, and the method has good application prospect. the hydroxylation reaction of an iodo aromatic compound can be carried out in an aqueous solution at the temperature of 90 DEG C, and a hydroxylated product with high yield can be obtained, the reaction temperature is averagely reduced by about 30 DEG C by comparing with a report in the literature; the hydroxylation reaction of a brominated aromatic compound can be carried out in the aqueous solution at the temperature of 120 DEG C, and the reaction temperature is averagely reduced by about 20 DEG C by comparing with the report in the literature.

Description

Technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a method for hydroxylation of 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 been industrialized (Lindley, J. Tetrahedron 1984, 40, 1433). However, the traditional Ullman coupling reaction is carried out under high temperature and high polar solvent conditions, and requires equivalent or excessive copper reagents. Therefore, the application of Ullman reaction is greatly restricted (Lindley, J. Tetrahedron 1984). , 40,1433). Palladium catalysts have been used in recent years ((a) Yang, BH; Buchwald, SLJ Organomet. Chem. 1999, 576(1-2), 125-146. (b) Hartwig, JF Angew. Chem., Int. Ed. Engl. 1998, 37, 2046-2067), so that the reaction can be carried out under milder conditions. [0003] However, the use of palladium catalysts still has many limitatio...

Claims

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Application Information

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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
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