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Method for preparing linear amine through selective hydroamine methylation of olefin

A technology of hydroamine methyl and linear amine, which is applied in the direction of chemical instruments and methods, condensation/addition reactions to prepare amino compounds, organic compounds/hydrides/coordination complex catalysts, etc., which can solve the difficulty of separation and purification and operation Cost, increase the difficulty and cost of separation and purification, and decrease the yield of amine products, etc., to achieve good industrial application value, high efficiency and selectivity, and avoid post-processing effects

Active Publication Date: 2021-10-29
FUDAN UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the selectivity of the reaction is still low. In addition, the introduction of an excessive amount of air- and water-sensitive and difficult-to-synthesize bulky phosphine ligands not only improves the L / B selectivity, but also promotes the generation of side reactions of olefin hydrogenation. This reduces the yield of amine products, and also increases the difficulty and operating costs for subsequent separation and purification.
In addition, in the reported olefin hydroamine methylation reaction of supported catalysts, the L / B ratio is usually relatively low, which increases the difficulty and cost of separation and purification.
In short, compared with homogeneous catalysts, the reaction efficiency of existing heterogeneous catalytic systems is still low.

Method used

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  • Method for preparing linear amine through selective hydroamine methylation of olefin
  • Method for preparing linear amine through selective hydroamine methylation of olefin
  • Method for preparing linear amine through selective hydroamine methylation of olefin

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Experimental program
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Effect test

Embodiment 1

[0045] Embodiment 1, the preparation of azacyclic carbene metal coordination polymer 1

[0046]

[0047] The synthetic method of the azacyclic carbene rhodium coordination polymer designed by the present invention, its process is as follows:

[0048] Add bis-imidazolium methyl salt ligand (1 mmol) and metal precursor [Rh(COD)Cl] to a 100 mL bottle under nitrogen 2 (1.0mmol), DMF (15mL), stir well at room temperature. Subsequently, 2 mL of LiHMDS (1M solution in THF) was added dropwise to the system, sealed and placed in an oil bath at 80° C. for 24 h of reaction. After the reaction, the system was cooled to room temperature, transferred to a 10mL centrifuge tube for centrifugation, and washed with DMF, deionized water, and methanol in sequence until the filtrate was clear and transparent, and the solid obtained by centrifugation was subjected to Soxhlet extraction with methanol, and vacuum-dried , the corresponding coordination polymer can be obtained. Dark brown solid, ...

Embodiment 2

[0049] Embodiment 2, the preparation of azacyclic carbene metal coordination polymer 2a:

[0050]

[0051] Add bis-imidazolium methyl salt ligand (1 mmol) and metal precursor [Rh(COD)Cl] to a 100 mL bottle under nitrogen 2 (1.0mmol), DMF (15mL), stir well at room temperature. Subsequently, 2 mL of LiHMDS (1M solution in THF) was added dropwise to the system, sealed and placed in an oil bath at 80° C. for 24 h of reaction. After the reaction, the system was cooled to room temperature, transferred to a 10mL centrifuge tube for centrifugation, and washed with DMF, deionized water, and methanol in sequence until the filtrate was clear and transparent, and the solid obtained by centrifugation was extracted by Soxhlet with methanol, and dried in vacuo , the corresponding coordination polymer can be obtained. Dark brown solid, yield 97%; IR(KBr pellet)ν436.72,727.09,744.28,816.01,861.10,923.91,948.90,1058.91,1247.16,1372.27,1471.17,1612.26,1659.753,1950.0726cm -1 .Elementalanal...

Embodiment 3

[0052] Embodiment 3, the preparation of azacyclic carbene metal coordination polymer 2b:

[0053]

[0054] Add bis-imidazolium methyl salt ligand (1 mmol) and metal precursor [Rh(COD)Cl] to a 100 mL bottle under nitrogen 2 (1.0mmol), DMF (15mL), stir well at room temperature. Subsequently, 2 mL of LiHMDS (1M solution in THF) was added dropwise to the system, sealed and placed in an oil bath at 80° C. for 24 h of reaction. After the reaction, the system was cooled to room temperature, transferred to a 10mL centrifuge tube for centrifugation, and washed with DMF, deionized water, and methanol in sequence until the filtrate was clear and transparent, and the solid obtained by centrifugation was extracted by Soxhlet with methanol, and dried in vacuo , the corresponding coordination polymer can be obtained. Dark brown solid, yield 93%; IR(KBr pellet)ν446.63,726.43,747.38,817.65,862.32,924.07,1087.50,1246.70,1372.80,1470.27,1612.15,1663.47,1950.29,2953.95,4cm -1 .Elemental ana...

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Abstract

The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing linear amine through selective hydroamine methylation of olefin. According to the invention, olefin, amine, carbon monoxide or carbon dioxide and hydrogen are used as reaction raw materials, an N-heterocyclic carbene metal coordination polymer is used as a catalyst, analogues of ethers, alcohols and benzene are used as solvents, and reaction is carried out at 80-200 DEG C for 4-24 hours to obtain corresponding linear (L) amine and branched (B) amine products. Compared with the prior art, the method has the advantages that olefin and amine which are cheap and easy to obtain can be used as starting materials, the reaction selectivity L / B value is up to 95 / 5, the yield of amine reaches 98%, the catalyst can be recycled for more than ten times, high-purity linear amine can be obtained without complicated post-treatment and simple filtration, and the method is suitable for large-scale industrial application.

Description

technical field [0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a method for preparing linear amines through selective hydroamine methylation of olefins. Background technique [0002] Amines and their derivatives have broad application prospects in the fields of energy, materials, medicine, environment, and daily chemicals. Therefore, they have a large demand and high prices, and have become the focus of fine chemical industry and chemical research in recent years. The preparation methods of amines in industry mainly include: alkylation of ammonia / amines by alcohols and alkyl halides, reductive amination of aldehydes, reduction of nitriles, etc., but these methods are essentially multi-step synthesis, because alcohols, aldehydes, acids, Nitrile, alkyl halide, etc. are mainly prepared from oil or olefin through multi-step reactions such as hydrolysis, oxidation, hydrogenation, halogenation, and nitrilation. Some of the step...

Claims

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Application Information

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IPC IPC(8): C07C209/60C07C211/48C08G83/00B01J31/22
CPCC07C209/60C08G83/008B01J31/2273B01J2231/32B01J2531/822C07C211/48Y02P20/55Y02P20/584
Inventor 涂涛钱春郑庆舒
Owner FUDAN UNIV
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