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Method for preparing enamine compound by catalyzing phenylacetylene and utilizing hydroamination reaction

A technology of phenylacetylene and hydroamination, which is applied in the field of catalytic chemistry, can solve the problems of low tolerance of functional groups, limited types of amino reagents, and high requirements for reaction conditions, and achieves easy availability of raw materials, high physical and chemical stability and Effects of thermal stability and mild reaction conditions

Active Publication Date: 2019-04-19
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional methods of constructing enamine mainly include condensation reaction, addition reaction, heterocyclic cleavage and imine to prepare enamine, and some special synthetic methods such as Curtius rearrangement, amide α, β elimination reaction and ketoxime reduction Acylation, etc.; these methods have obvious deficiencies: (1) higher requirements for reaction conditions, such as high temperature and pressure or extremely low temperature; (2) low tolerance to different functional groups of reaction materials; (3) amino reagents The types are limited; (4) High requirements on the reaction system, such as absolute anhydrous and oxygen-free, few types of catalysts and high dosage, special ligands, etc.; (5) Restrictions on raw materials, such as single type of raw materials, cumbersome and difficult preparation, etc.
These deficiencies greatly limit the development of enamine chemistry

Method used

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  • Method for preparing enamine compound by catalyzing phenylacetylene and utilizing hydroamination reaction
  • Method for preparing enamine compound by catalyzing phenylacetylene and utilizing hydroamination reaction
  • Method for preparing enamine compound by catalyzing phenylacetylene and utilizing hydroamination reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Example 1: Divalent nickel imine complexes catalyze the hydroamination of phenylacetylene to prepare enamines

[0029]

[0030] Catalyst [CH 2 (C 5 h 4 N) 2 ] Ni=NPh (3.2mg, 0.00001mol), phenylacetylene (1.02g, 0.01mol) and methylphenylamine (1.02g, 0.01mol) and 5mL toluene were added to the reaction tube, and phenylacetylene and methylphenylamine As a raw material, under the action of a divalent nickel imine complex catalyst, hydroamination reaction occurs in the solvent toluene, the reaction temperature is 60°C, and the reaction time is 8h. After the end, the system is extracted with ethyl acetate for 3 times, and the liquid is separated , the organic phase was dried with anhydrous sodium sulfate, then filtered and concentrated, and the concentrated reaction solution was separated by silica gel column chromatography (eluent: dichloromethane: ethyl acetate = 5: 1) to obtain the corresponding enamine compound. The resulting product was subjected to LC-MS to obtai...

Embodiment 2

[0031] Example 2: Divalent nickel imine complexes catalyze the hydroamination of phenylacetylene to prepare enamines

[0032]

[0033] The catalyst [(CH 3 )CH(C 5 h 4 N) 2 ] Ni=NPh (3.3mg, 0.00001mol), phenylacetylene (1.22g, 0.012mol) and methylethylamine (1.02g, 0.01mol) and 8mL toluene were added to the reaction tube, and phenylacetylene and methylethylamine As a raw material, under the action of a divalent nickel imine complex catalyst, hydroamination reaction occurs in the solvent toluene, the reaction temperature is 75°C, and the reaction time is 6h. After the end, the system is extracted with ethyl acetate for 3 times, and the liquid is separated. , the organic phase was dried with anhydrous sodium sulfate, then filtered and concentrated, and the concentrated reaction solution was separated by silica gel column chromatography (eluent: dichloromethane: ethyl acetate = 5: 1) to obtain the corresponding enamine compound. The resulting product was subjected to LC-MS ...

Embodiment 3

[0034] Example 3: Divalent nickel imine complexes catalyze the hydroamination of phenylacetylene to prepare enamines

[0035]

[0036] The catalyst [PhCH(C 5 h 4 N) 2 ] Ni=NPh (4.0mg, 0.00001mol), phenylacetylene (1.53g, 0.015mol) and methyl isopropylamine (1.02g, 0.01mol) and 8mL toluene were added to the reaction tube, and phenylacetylene and methyl isopropyl Base amine is used as raw material, under the action of divalent nickel imine complex catalyst, hydroamination reaction occurs in solvent toluene, the reaction temperature is 100°C, and the reaction time is 12h. After the end, the system is extracted with ethyl acetate for 3 times. Separate the liquid, dry the organic phase with anhydrous sodium sulfate, filter and concentrate, and separate the concentrated reaction solution through silica gel column chromatography (eluent: dichloromethane:ethyl acetate=5:1) to obtain the corresponding enamine compound , LC-MS was performed on the resulting product to obtain 1.522...

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Abstract

The invention provides a method for preparing an enamine compound by catalyzing phenylacetylene and utilizing the hydroamination reaction. The method is characterized by comprising the steps that thephenylacetylene and secondary amine are taken as raw materials, under the effect of a nickelous imine complex catalyst, the hydroamination reaction is conducted in a solvent, after finishing of the reaction and after-treatment, the enamine product is obtained, wherein the molecular formula of the nickelous imine complex catalyst is [R1R2C (C5H4N) 2] Ni=NPh, R1 and R2 are independently selected from H, CH3 and Ph, and arene is the solvent. The catalyst has extremely high catalytic activity and regioselectivity, the synthesizing technology is simple and green, good selectivity and high yield areachieved, the atom economy is good, and production of waste gas, waste water and industrial residues is reduced; the method protects the environment, and is simple in operation and suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, and in particular relates to a method for preparing enamine compounds by catalyzing the hydroamination reaction of phenylacetylene with a divalent nickel imine complex containing pyridine ligands. Background technique [0002] Enamine compounds play an important role in many fields, such as being suitable for the synthesis of various nitrogen-containing heterocyclic derivatives as precursors; they also have special medicinal properties, and exist as key structural units in many natural products and drugs; In addition, enamines are widely used as intermediates in the preparation of chiral amines. The traditional methods of constructing enamine mainly include condensation reaction, addition reaction, heterocyclic cleavage and imine to prepare enamine, and some special synthetic methods such as Curtius rearrangement, amide α, β elimination reaction and ketoxime reduction Acylation, etc....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/60C07C211/48C07C211/55
CPCC07C209/60C07C211/48C07C211/55
Inventor 姚子健樊晓楠云雪静靳永旭高永红邓维
Owner SHANGHAI INST OF TECH
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