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Method for N-arylation of alkane amine

A technology for alkane amine and arylation, which is applied in the field of N-arylation of alkane amine, can solve the problems of expensive ligand, difficult reaction, unfavorable industrial application and the like, and achieves good application prospect, low price and wide base The effect of the scope of application

Inactive Publication Date: 2014-06-04
HENGYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, there are still many limitations in the use of palladium catalysts, such as the difficulty of reacting with substrates containing certain specific functional groups, the expensive price of palladium reagents and their co-catalyzed ligands, etc. At the same time, the use of palladium to catalyze the reaction needs to be carried out in an organic solvent , not conducive to industrial application

Method used

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  • Method for N-arylation of alkane amine
  • Method for N-arylation of alkane amine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Preparation of N-methyl-4-methoxyaniline.

[0037]

[0038] In a reaction tube sealed at one end, add 234mg p-methoxyiodobenzene (MW=234,1.0mmol), then add 168mg KOH (MW=56,3mmol), 16.1mg6,7-dihydroquinoline-8 (5H )-ketoxime (i.e. ligand L) (MW=161,0.1mmol), 9.5mg CuI (MW=190,0.05mmol), 1.0ml30% methylamine aqueous solution (MW=31,9.6mmol), in argon or Under nitrogen protection, stir and react at room temperature (20-25°C) for 18 hours, extract the reaction mixture three times with 25 ml of ethyl acetate, combine and dry the extracts, distill under reduced pressure, and separate through a silica gel column (eluent petroleum ether: acetic acid Ethyl ester=8:1), obtain 133mg product N-methyl-p-methoxyaniline, productive rate 97%.

[0039] The characterization data of this product N-methyl-p-methoxyaniline is:

[0040] 1H NMR (CDCl 3 ,400MHz):δ=6.81(d,J=8.4Hz,2H),6.63(d,J=8.8Hz,2H),3.75(s,3H),2.81(s,3H);13C NMR(CDCl 3,75MHz): δ=152.4, 143.3, 114.9, 113.9, 55.9, 31.8...

Embodiment 2

[0042] Preparation of N-methyl-4-methoxyaniline.

[0043]

[0044] Using K 2 CO 3 420 mg was used as the base. According to the method described in Example 1, 4-methoxyiodobenzene (234 mg, 1.0 mmol) and 1.0 ml of 30% methylamine aqueous solution (MW=31, 9.6 mmol) were stirred at room temperature for 18 h. The crude product was purified by column chromatography (20:1 petroleum ether: ethyl acetate), yield: 47%.

[0045] The characterization data of this product N-methyl-p-methoxyaniline is:

[0046] 1H NMR (CDCl 3 ,400MHz):δ=6.81(d,J=8.4Hz,2H),6.63(d,J=8.8Hz,2H),3.75(s,3H),2.81(s,3H);13C NMR(CDCl 3 ,75MHz): δ=152.4, 143.3, 114.9, 113.9, 55.9, 31.8.

Embodiment 3

[0048] Preparation of N-methyl-4-methoxyaniline.

[0049] Using Cs 2 CO 3 975mg (3mmol) was used as the base. According to the method described in Example 1, 4-methoxyiodobenzene (234mg, 1.0mmol) and 1.0ml of 30% methylamine aqueous solution (MW=31, 9.6mmol) were stirred at room temperature for 18h. The crude product was purified by column chromatography (20:1 petroleum ether: ethyl acetate), yield: 75%.

[0050] The characterization data of this product N-methyl-p-methoxyaniline is:

[0051] 1H NMR (CDCl 3 ,400MHz):δ=6.81(d,J=8.4Hz,2H),6.63(d,J=8.8Hz,2H),3.75(s,3H),2.81(s,3H);13C NMR(CDCl 3 ,75MHz): δ=152.4, 143.3, 114.9, 113.9, 55.9, 31.8.

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Abstract

The invention discloses a method for N-arylation of alkane amine, belonging to the technical field of chemical synthesis. The method comprises a step of making the alkane amine and an aromatic compound have an Ar-X reaction in the presence of a base and a solvent by taking a 2-pyridyl ketoxime compound as an additive and CuI as a catalyst so as to realize the N-arylation of the alkane amine. The method can be used for well promoting the proceeding of an N-arylation reaction, so that the N-arylation reaction between an alkane amine compound and an iodo-aromatic compound in a water liquid can be performed at room temperature, and the N-arylation reaction of a bromo-aromatic compound can be performed at the temperature of 65 DEG C; meanwhile, the 2-pyridyl ketoxime compound can be used for promoting lots of compounds containing various functional groups to have a Ullman coupling reaction, and particularly N-methylaniline and N'N-dimethylaniline compounds can be efficiently synthesized in the water liquid at room temperature, so the method disclosed by the invention has a quite wide substrate application range and a quite good application prospect.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a method for N-arylation of alkane amines. Background technique [0002] After a long period of development, the Ullmann coupling reaction (Ullmann) has achieved industrial production. However, the traditional Ullmann coupling reaction needs to be carried out under the conditions of high temperature and highly polar solvent, and requires an equivalent or excess amount of copper reagent. Therefore, the application of the Ullmann reaction is greatly limited (Lindley, J. Tetrahedron 1984, 40, 1433). In recent years palladium catalysts ((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 in the use of palladium catalysts, such as the difficulty of reacting with substrates co...

Claims

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Application Information

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IPC IPC(8): C07C217/84C07C213/02C07C211/48C07C209/10C07C211/52C07C211/50C07D213/74C07C255/58C07C253/30C07C215/16C07D295/073C07D295/023C07D295/033C07C211/58C07D295/096C07B43/04B01J31/22
Inventor 王德平邝代治张复兴
Owner HENGYANG NORMAL UNIV
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