A kind of method that catalyzes the hydroamination reaction of cyclohexylacetylene to prepare enamine compounds

An acetylene hydrogen amine and cyclohexyl technology, applied in the field of catalytic chemistry, can solve the problems of low tolerance of functional groups, limited development of enamine chemistry, limited types of amino reagents, etc., and achieves excellent high yield, simple and green synthesis process, Excellent selective effect

Active Publication Date: 2022-05-13
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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  • A kind of method that catalyzes the hydroamination reaction of cyclohexylacetylene to prepare enamine compounds
  • A kind of method that catalyzes the hydroamination reaction of cyclohexylacetylene to prepare enamine compounds
  • A kind of method that catalyzes the hydroamination reaction of cyclohexylacetylene to prepare enamine compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1: Divalent palladium imine complex catalyzes the hydroamination of cyclohexylacetylene to prepare enamine

[0032]

[0033] A method for preparing enamine compounds by catalyzing cyclohexylacetylene hydroamination reaction, the specific steps are:

[0034] Catalyst [CH shown in formula (I) 2 (C 5 h 4 N) 2 ]Pd=NPh (3.7mg, 0.00001mol), cyclohexylacetylene (1.08g, 0.01mol) and methylphenylamine (1.02g, 0.01mol) and 6mL toluene were added to the reaction tube, under the catalysis of the catalyst, the ring Hydroamination reaction of hexylacetylene and secondary amine in toluene, the reaction temperature is 60°C, the reaction time is 8h, after the end, extract the system with 20mL ethyl acetate and 10mL water, separate the liquid, add 5mL ethyl acetate to the obtained organic phase Extract with 5mL water twice, separate liquid, combine organic phase, carry out drying with anhydrous sodium sulfate, then filter and concentrate, reaction solution is through silic...

Embodiment 2

[0035] Example 2: Divalent palladium imine complex catalyzes the hydroamination of cyclohexylacetylene to prepare enamine

[0036]

[0037] A method for preparing enamine compounds by catalyzing cyclohexylacetylene hydroamination reaction, the specific steps are:

[0038] Catalyst [CH shown in formula (I) 2 (C 5 h 4 N) 2 ]Pd=NPh (3.7mg, 0.00001mol), cyclohexylacetylene (1.29g, 0.012mol) and methylethylamine (1.02g, 0.01mol) and 8mL toluene were added to the reaction tube, under the catalysis of the catalyst, the ring Hexylacetylene and secondary amine undergo hydroamination reaction in toluene, the reaction temperature is 75°C, and the reaction time is 6h. After the end, the system is extracted with 20mL ethyl acetate and 10mL water, and the obtained organic phase is added with 5mL ethyl acetate Extract with 5mL water twice, separate liquid, combine organic phase, carry out drying with anhydrous sodium sulfate, then filter and concentrate, reaction solution is through s...

Embodiment 3

[0039] Example 3: Divalent palladium imine complex catalyzes the hydroamination of cyclohexylacetylene to prepare enamine

[0040]

[0041] A method for preparing enamine compounds by catalyzing cyclohexylacetylene hydroamination reaction, the specific steps are:

[0042] The catalyst shown in formula (I) [(CH 3 )CH(C 5 h 4 N) 2 ]Pd=NPh (7.6mg, 0.00002mol), cyclohexylacetylene (1.62g, 0.015mol) and methyl isopropylamine (1.02g, 0.01mol) and 10mL toluene were added to the reaction tube, under the catalysis of the catalyst, Cyclohexylacetylene and secondary amines undergo hydroamination reaction in toluene, the reaction temperature is 100°C, and the reaction time is 12h. After the completion, the system is extracted with 20mL ethyl acetate and 10mL water, and the obtained organic phase is added with 5mL ethyl acetate The ester was extracted twice with 5 mL of water, separated, and the organic phases were combined, dried with anhydrous sodium sulfate, filtered and concentr...

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PUM

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Abstract

The invention provides a method for preparing enamine compounds by catalyzing the hydroamination reaction of cyclohexylacetylene, which is characterized in that, under the catalysis of the catalyst, cyclohexylacetylene and secondary amine undergo hydroamination reaction in a solvent , to obtain enamine compounds; the molecular formula of the catalyst is [R 1 R 2 C(C 5 h 4 N) 2 ] Pd=NPh, wherein, R 1 and R 2 independently selected from H, CH 3 and Ph, the solvent is an aromatic hydrocarbon, the reaction temperature is 60-100°C, and the reaction time is 6-12h. The invention has mild reaction conditions, high catalytic efficiency, high atom economy, low cost, easy separation of products, no large amount of waste residue, and is 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 cyclohexylacetylene hydroamination reaction with divalent palladium imine complexes 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 Patents(China)
IPC IPC(8): C07C211/48C07C211/25C07C211/55C07C209/68
Inventor 姚子健樊晓楠靳永旭云雪静高永红邓维
Owner SHANGHAI INST OF TECH
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