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Method for preparing aldehyde by catalyzing internal olefin based on phosphoramidite phosphine ligand

A technology of phosphonamidite and internal olefin, which is applied in the field of preparing aldehydes based on phosphonamidophosphine ligands to catalyze internal olefins, can solve the problems of poor selectivity of aldehydes, ligand inactivation, harsh reaction conditions, etc., to reduce production energy consumption, Increased safety, pressure stabilization effect

Active Publication Date: 2021-06-04
SICHUAN UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, rhodium-catalyzed cyclic olefin hydroformylation reaction conditions are relatively harsh, such as high pressure (8-22MPa), long reaction time (more than 50 hours), and adding some auxiliary catalytic additives and using mixed phosphine ligands , and the conversion rate is low, and the selectivity to aldehydes is poor
[0005] Some studies have pointed out that a catalyst for the hydroformylation reaction of internal olefins and its preparation method and application, the catalyst of the invention is an oil-soluble catalyst, and the catalytic system is a homogeneous catalytic system, but the invention has relatively high reaction temperature and high pressure , and the ligand is easily inactivated at high temperature

Method used

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  • Method for preparing aldehyde by catalyzing internal olefin based on phosphoramidite phosphine ligand
  • Method for preparing aldehyde by catalyzing internal olefin based on phosphoramidite phosphine ligand
  • Method for preparing aldehyde by catalyzing internal olefin based on phosphoramidite phosphine ligand

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Embodiment 1

[0033] The invention provides a kind of method based on phosphinoamidophosphine ligand and rhodium catalyst catalyzed internal olefin to prepare linear valeraldehyde, comprising the following steps:

[0034] The phosphine ligand binaphthol bisindolyl phosphine and the metal rhodium precursor Rh(acac)(CO) 2 Put it into the autoclave with a molar ratio of 2:1, and then add toluene solvent, use the synthesis gas mixed with hydrogen and carbon monoxide at a partial pressure ratio of 1:1 to perform gas replacement operation, and then mix 5g of 2-butene with Rh (acac)(CO) 2 Samples were taken at a molar ratio of 1064 and added to the reactor. Then, under the condition of 1.0MPa (constant pressure) and 80°C, the reaction was stirred for 2h. After the reaction was completed, the product mixed solution was analyzed by gas chromatography, and the ratio of normal structure and isomerism valeraldehyde is as follows:

[0035]

[0036] a the molar ratio of normal aldehyde and isomeric...

Embodiment 2

[0039] The invention provides a kind of method based on phosphinoamidophosphine ligand catalyzed internal olefin linear valeraldehyde, comprising the following steps:

[0040] The phosphine ligand binaphthol bisindolyl phosphine and the metal rhodium precursor Rh(acac)(CO) 2 Add it to the autoclave with a molar ratio of 5:1, then add xylene solvent, use hydrogen and carbon monoxide in a partial pressure ratio of 2:1 to carry out gas replacement operation, and then mix 5g of 2-butene with Rh (acac)(CO) 2Samples were taken at a molar ratio of 975 and added to the kettle. Then, under the condition of 1.0MPa (constant pressure) and 70°C, the reaction was stirred for 6h. After the reaction was completed, the product mixed solution was analyzed by gas chromatography, and the ratio of normal structure and isomerism valeraldehyde is as follows:

[0041]

[0042] a is the molar ratio of normal aldehyde and isomeric aldehyde;

[0043] b is the total yield of valeraldehyde.

Embodiment 3

[0045] The invention provides a method for preparing linear valeraldehyde based on a phosphinoamidophosphine ligand catalyzed by an internal olefin, comprising the following steps:

[0046] Add the phosphine ligand binaphthol bisindolyl phosphine and metal rhodium precursor Rh(COD)(acac) in a molar ratio of 10:1 into the autoclave, then add trimethylbenzene solvent, press hydrogen and carbon monoxide to The mixed synthesis gas with a partial pressure ratio of 0.8:1 was used for replacement gas operation, and then 5 g of 2-butene and Rh(COD)(acac) were sampled at a molar ratio of 2000 and added to the reactor. Then, under the condition of 1.5MPa (constant pressure) and 80°C, the reaction was stirred for 6h. After the reaction was completed, the product mixed solution was analyzed by gas chromatography, and the ratio of normal structure and isomerism valeraldehyde is as follows:

[0047]

[0048]

[0049] a is the molar ratio of normal aldehyde and isomeric aldehyde;

[...

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Abstract

The invention discloses a method for preparing aldehyde by catalyzing internal olefin based on a phosphoramidite phosphine ligand, which comprises the following steps: performing homogeneous reaction on the internal olefin, an organic solvent, a rhodium complex and the phosphine ligand in synthesis gas, thereby efficiently and highly selectively converting the internal olefin into the aldehyde through homogeneous hydroformylation. For example, straight-chain aldehyde can be generated from common internal olefin in a high-selectivity manner, dialdehyde can be generated from cyclic diene in a high-selectivity manner, the whole reaction system is mild in condition, fewer hydrogenation products are generated, the catalyst can be recycled, the production cost is reduced, and the production safety is improved.

Description

technical field [0001] The invention relates to the technical field of organic compound synthesis, in particular to a method for preparing aldehydes from internal olefins catalyzed by phosphinoamidophosphine ligands. Background technique [0002] The hydroformylation reaction refers to the reaction of alkenes or alkynes with synthesis gas (CO+H 2 ) reaction, the product is an aldehyde with one more carbon, which belongs to the atom-economical reaction, and the utilization rate of the atom is 100%. [0003] There are problems of chemoselectivity and regioselectivity in olefin hydroformylation reaction. Chemoselectivity lies in substrate hydrogenation or carbonyl addition, and regioselectivity involves the selectivity of linear and branched chain aldehydes. For the hydroformylation reaction of internal olefins, usually the reactivity is very low, and it is easy to obtain a high proportion of branched chain aldehyde products, but the demand for straight chain aldehydes in actu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/50C07C47/02B01J31/22
CPCC07C45/50B01J31/186B01J2231/321B01J2531/822C07C47/02Y02P20/584
Inventor 郑学丽陈华唐松柏袁茂林李瑞祥付海燕
Owner SICHUAN UNIV
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