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Nickelous imine complex with nickel nitrogen double-bond structure and preparation and application of nickelous imine complex

A divalent nickel imine and complex technology, which is applied in the preparation of organic compounds, amino hydroxyl compounds, nickel organic compounds, etc., can solve the problems of few types of catalyzed substrates, harsh reaction conditions, and application limitations, etc., to achieve The effects of high physical and chemical stability and thermal stability, mild reaction conditions, and simple preparation methods

Active Publication Date: 2019-09-06
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, the existing catalysts used in the reverse Malanobidium amination reaction of olefins have disadvantages such as fewer types of substrates that can be catalyzed, harsh reaction conditions, and difficult separation, etc., and their applications are greatly restricted.

Method used

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  • Nickelous imine complex with nickel nitrogen double-bond structure and preparation and application of nickelous imine complex
  • Nickelous imine complex with nickel nitrogen double-bond structure and preparation and application of nickelous imine complex
  • Nickelous imine complex with nickel nitrogen double-bond structure and preparation and application of nickelous imine complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Synthesis of divalent nickel-imine complexes containing phenyldipyridine nickel-nitrogen double bond structure:

[0027]

[0028] At room temperature, the phenylbipyridine ligand C 17 h 14 N 2 (246.3mg, 1.0mmol) of toluene solution was added dropwise to Ni(COD) 2 (220.0mg, 0.80mmol) in tetrahydrofuran solution, stirred at this temperature for 3 hours, then benzene azide PhN 3 (114.2 mg, 0.96 mmol) was added to the reaction system for an additional 3 hours. After the reaction is over, let it stand and filter, and dry the solvent under reduced pressure, and the obtained crude product is subjected to column chromatography separation (petroleum ether / ethyl acetate (v / v)=5:1) to obtain the light yellow target product divalent nickel imine complex C 23 h 19 N 3 Ni (243.9 mg, 77% yield). Elemental analysis theoretical value: C 69.74, H 4.83, N 10.61; experimental value: C 69.68, H 4.93, N 10.55.

[0029] Take 3.0mg compound and carry out thermogravimetric experimen...

Embodiment 2

[0031] Divalent nickel-imine complexes catalyze the reverse Malanobilic amination of styrene:

[0032]

[0033] The nickel imine complex prepared in Example 1 is used as a catalyst to catalyze the reverse Malanobiline amination reaction of olefins: add toluene containing nickel imine complex (0.001 mmol) to styrene (1 mmol) and aniline (1 mmol) solution, the reaction temperature is 25°C, and the reaction time is 60 minutes. After the completion, the concentrated reaction solution is directly separated by silica gel column chromatography, dried until the mass remains constant, and the corresponding amine compound C is obtained. 14 h 15 N, yield 88%, elemental analysis: C 85.24, H 7.66, N 7.10 (theoretical); C85.31, H 7.69, N 7.02 (actual).

Embodiment 3

[0035] Divalent nickel-imine complexes catalyze the reverse Malanobilic amination of styrene:

[0036]

[0037] The nickel imine complex prepared in Example 1 is used as a catalyst to catalyze the anti-Martensio amination reaction of olefins: add nickel imine complex (0.002mmol) to styrene (1mmol) and methylaniline (1mmol) toluene solution, the reaction temperature is 25°C, and the reaction time is 100 minutes. After the end, the concentrated reaction solution is directly separated by silica gel column chromatography, dried until the quality remains unchanged, and the corresponding amine compound C is obtained. 15 h 17 N, yield 97%, elemental analysis: C 85.26, H 8.11, N 6.63 (theoretical); C 85.35, H 8.03, N 6.60 (actual).

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Abstract

The invention relates to a nickelous imine complex with a nickel nitrogen double-bond structure and preparation and application of the nickelous imine complex. The preparation method of the nickelousimine complex comprises the following steps that 1, a phenyldipyridine ligand solution is added into a zero-valent nickel precursor solution for a reaction for 3-5 hours at room temperature; 2, azidobenzene is added for a reaction for 2-5 hours at room temperature, and through aftertreatment, the nickelous imine complex is obtained. The nickelous imine complex is used for catalyzing an anti-Markovnikov hydroamination reaction of styrene to prepare a linear-chain amine compound. Compared with the prior art, the synthesizing technology is simple and green, the selectivity and the yield are high,the nickelous imine complex prepared by using the method has the advantages of stable physicochemical properties, thermal stability and the like, and the nickelous imine complex can show excellent activity and regioselectivity in the reaction of catalyzing the anti-Markovnikov hydroamination reaction of the styrene.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and relates to a divalent nickel-imine complex containing a nickel-nitrogen double bond structure, a preparation method and its application in catalyzing the reverse Malanobidium amination reaction of styrene. Background technique [0002] Linear amine compounds are an important class of fine chemical intermediates, which are widely used in the synthesis of pesticides, medical supplies and functional materials. Therefore, efficient and cheap synthesis methods of such compounds have always been one of the focuses in the field of chemistry research. The traditional synthesis methods mainly include the reduction of nitro or cyano compounds, the Hofmann degradation of amides, and the anti-Martensitic hydroamination reaction of olefins, etc. Among them, the reduction of nitro or cyano compounds, the Hofmann degradation of amides There are many shortcomings in terms of ease of operation, a...

Claims

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Application Information

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IPC IPC(8): C07F15/04B01J31/22C07C209/60C07C211/48C07C211/52C07C213/08C07C217/84
CPCB01J31/1815C07C209/60C07C213/08C07F15/045C07C211/48C07C211/52C07C217/84
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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