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A method for the direct amination of benzyl hydrocarbons of methyl aromatic compounds catalyzed by iron

A technology of methyl aromatic and iron compounds, applied in the direction of organic chemistry, sulfonamide preparation, etc., to achieve the effect of reducing reaction cost, reducing environmental impact, and wide application range

Active Publication Date: 2021-04-02
HENAN AGRICULTURAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method does not require the addition of additional oxidants and ligands

Method used

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  • A method for the direct amination of benzyl hydrocarbons of methyl aromatic compounds catalyzed by iron
  • A method for the direct amination of benzyl hydrocarbons of methyl aromatic compounds catalyzed by iron
  • A method for the direct amination of benzyl hydrocarbons of methyl aromatic compounds catalyzed by iron

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Add 0.0072g ferrous oxalate (0.05mmol), 10mL organic solvent o-dichlorobenzene, 0.053mL toluene (0.5mmol), 0.241g N-fluorobisbenzenesulfonimide (0.75mmol) into a 50mL round bottom flask ), heated to reflux for 24 hours, until the reaction was complete (detected by thin-layer chromatography TLC). The reaction mixture was separated by silica gel column chromatography (eluent: ethyl acetate:petroleum ether=1:6) to obtain 0.1055 g of a white solid with a yield of 54%. The nuclear magnetic resonance spectrum is as follows: figure 1 .

Embodiment 2

[0027] Add 0.0242g ferric oxalate hexahydrate (0.05 mmol), 10 mL organic solvent o-dichlorobenzene, 0.061 mL p-bromotoluene (0.5 mmol), 0.241 g N-fluorobisbenzenesulfonimide ( 0.75 mmol), heated to reflux for 23 hours, until the reaction was complete (detected by thin-layer chromatography TLC). The reaction mixture was separated by silica gel column chromatography (eluent: ethyl acetate:petroleum ether=1:6.5) to obtain 0.1761g of a white solid with a yield of 76%. The nuclear magnetic resonance spectrum is as follows: figure 2 .

Embodiment 3

[0029] Add 0.0242g ferric oxalate hexahydrate (also iron p-toluenesulfonate hexahydrate) (0.05mmol), 10mL organic solvent o-dichlorobenzene, 0.091mL p-tert-butyltoluene (0.5mmol ), 0.241g N-fluorobisbenzenesulfonimide (0.75 mmol), heated to reflux for 6 hours, until the reaction was complete (detected by TLC). The reaction mixture was separated by silica gel column chromatography (eluent: ethyl acetate:petroleum ether=1:8) to obtain 0.1782g of a white solid with a yield of 80%. The nuclear magnetic resonance spectrum is as follows: image 3 .

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Abstract

The invention provides a direct amination of benzyl C-H of a methyl aromatic compound under iron catalysis. The method comprises the following steps: the methyl aromatic compound is used as a raw material, an iron compound is used as a catalyst, o-dichlorobenzene is used as a solvent, a certain amount of NFSI is added, a reaction under heating is performed for 4-28 h, after the reaction is completed, silica gel column chromatography separation is performed, and therefore a benzylamine derivative is obtained. The method provided by the invention realizes the direct amination of the benzyl C-H of a rich, easily-available, environmentally-friendly methyl aromatic compound under catalysis of the iron compound without adding an oxidizing agent and using metal nitrene for the first time, and synthesizes the benzylamine derivative; and the method has the following advantages: the iron catalyst used in the method is cheap, friendly to the environment and non-toxic, does not require the oxidizing agent or a ligand, a toluene derivative and a 8-methylquinoline derivative can be subjected to an amination reaction under catalysis of the same iron catalyst, and the method has a wide range of applications.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, in particular to an iron-catalyzed method for the direct amination of benzyl hydrocarbons of methyl aromatic compounds. Background technique [0002] Many of the best-selling drugs contain benzylamine structural units, and the introduction of a nitrogen atom into the benzyl group of natural products and biologically active small molecular compounds has the potential to drastically alter the biological activity of the compound (J. R. Clark, K. Feng, A. Sookezian, M. C. White, Nature Chem., 10, 583(2018)); In addition, benzylamine can also be used in the preparation of new materials, so the direct amination of cheap and easy-to-obtain methyl aromatic compounds can be achieved in one step It is of great significance to synthesize benzylamine derivatives with high value. Currently, the direct amination of benzylic hydrocarbons can be achieved by metal phenoxides or additional per...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C311/48C07C303/40C07D215/12
CPCC07C311/48C07D215/12
Inventor 鲍峰玉曹远博
Owner HENAN AGRICULTURAL UNIVERSITY