Application of sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst in asymmetric hydrogenation reaction

A technology of chiral catalysts and ionic liquids, applied in the field of chemistry and chemical engineering, can solve the problems of reduced catalytic efficiency, non-conformity with green chemistry, waste of resources, etc., and achieve the effects of reduced negative effects, high stability, and low loss

Active Publication Date: 2020-07-10
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although ionic liquids have achieved some successful applications in asymmetric hydrogenation reactions for the separation of chiral catalysts, a problem that is difficult to reconcile has also emerged, that is, in order to inhibit the loss of catalysts, a large amount of solvent ionic liquids are usually used in catalytic reactions. In order to fully dissolve and immobilize the chiral catalyst (140–5000 times that of the metal catalyst (mol / mol), equivalent to 15–2100% of the substrate, mol%), this neither meets the requirements of green chemistry nor lead to waste of resources
Moreover, the application of a large amount of solvent ionic liquids also makes the negative effects of trace impurities that are difficult to remove in ionic liquids on metal catalysts (such as catalyst poisoning) become more significant, resulting in a reduction in catalytic efficiency.

Method used

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  • Application of sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst in asymmetric hydrogenation reaction
  • Application of sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst in asymmetric hydrogenation reaction
  • Application of sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst in asymmetric hydrogenation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Asymmetric Hydrogenation Catalyzed by Catalyst 1a-1 / Methyl Acetoacetate / Methanol System

[0036] Catalyst 1a-1 is Ru(Br) 2 (S-BINAP-(SO 3 A) 2 )(A=[Ph(OCH 2 CH 2 ) 16 IMCH 3 ] + ,m=16,l=0,R 1 =Ph,R 2 = CH 3 ). Under an argon atmosphere, add catalyst 1a-1, methyl acetoacetate and methanol into the autoclave, the molar ratio of catalyst 1a-1 and methyl acetoacetate is 1:1000, then at 60°C, 4.0MPa hydrogen pressure The reaction was carried out for 20 hours. After the reaction, methanol was removed under reduced pressure, and n-hexane was added for extraction. The upper organic phase was analyzed by gas chromatography (lipodex A25m×0.25mm chiral capillary column), the conversion rate of the substrate was 100%, and the ee (S) value was 98.4 %; The initial TOF value of the reaction measured by the pressure drop method is 2914h -1 ; The catalyst phase of the lower floor continues to add methyl acetoacetate and methyl alcohol after the two-phase separation, and carr...

Embodiment 2

[0038] Asymmetric Hydrogenation Catalyzed by Catalyst 1a-2 / Methyl Acetoacetate / Methanol System

[0039] Catalyst 1a-2 is Ru(Br) 2 (S-BINAP-(SO 3 A) 2 )(A=[Ph(OCH 2 CH 2 ) 70 IMCH 3 ] + ,m=16,l=0,R 1 =Ph, R 2 = CH 3 ). Under argon atmosphere, add catalyst 1a-2, methyl acetoacetate and methanol into the autoclave, the molar ratio of catalyst 1a-2 and methyl acetoacetate is 1:1000, and then at 60°C, 4.0MPa hydrogen pressure The reaction was carried out for 20 hours. After the reaction, the methanol was removed under reduced pressure, and n-heptane was added for extraction. The upper organic phase was analyzed by gas chromatography (lipodex A25m×0.25mm chiral capillary column), the conversion rate of the substrate was 100%, and the ee (S) value 98.2%; The initial TOF value of the reaction measured by the pressure drop method is 2868h -1 ; The catalyst phase of the lower floor continues to add methyl acetoacetate and methyl alcohol after the two-phase separation, and ca...

Embodiment 3

[0041] Asymmetric Hydrogenation Catalyzed by Catalyst 1a-3 / Methyl Acetoacetate / Methanol System

[0042] Catalyst 1a-3 is Ru(Br) 2 (S-BINAP-(SO 3 A) 2 )(A=[n-C 12 h 25 (OCH 2 CH 2 ) 16 IMCH 3 ] + ,m=16,l=0,R 1 = n-C 12 h 25 , R 2 =CH 3 ). Under argon atmosphere, add catalyst 1a-3, methyl acetoacetate and methanol into the autoclave, the molar ratio of catalyst 1a-3 and methyl acetoacetate is 1:10000, and then at 80°C, 4.0MPa hydrogen pressure The reaction was carried out for 72 hours. After the reaction, methanol was removed under reduced pressure, and n-heptane was added for extraction. The upper organic phase was analyzed by gas chromatography (lipodex A 25m×0.25mm chiral capillary column), the substrate conversion rate was 95%, ee(S) Value 96.0%.

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Abstract

The invention relates to a phosphine ligand and polyether functionalized ionic liquid integrated chiral catalyst and application thereof in asymmetric catalytic hydrogenation reaction. In an asymmetric hydrogenation reaction, the dual functions of the chiral catalyst and the solvent ionic liquid can be exerted at the same time only by a catalytic amount of phosphine ligand and ionic liquid integrated catalyst; according to the method, the chiral catalyst is recycled and circulated, so that the solvent ionic liquid does not need to be additionally added, the negative effect of the solvent ionicliquid is reduced to the maximum extent, efficient, green and economical utilization of the ionic liquid is realized, and the problem that a large amount of solvent ionic liquid is needed for recycling the chiral catalyst in the prior art is solved.

Description

technical field [0001] The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for applying a chiral catalyst integrating sulfonated BINAP and polyether functionalized ionic liquid to an asymmetric catalytic hydrogenation reaction. Background technique [0002] In the past few decades, the homogeneous asymmetric catalytic hydrogenation reaction has become the most promising method for obtaining fine chemicals such as chiral drugs, pesticides and fragrances due to its high catalytic activity, good stereoselectivity and mild reaction conditions. One of the most efficient and atom-economical means. However, for a long time, the difficult separation of chiral noble metal catalysts (mainly chiral phosphine ligand-metal complexes) from hydrogenation products has limited their large-scale industrial application. Therefore, the development of recoverable and recyclable chiral catalysts has been a research focus in the field of h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C67/31C07C69/675C07C69/732C07B53/00
CPCB01J31/2471C07C67/31C07B53/00B01J31/0298B01J2231/643B01J2523/821B01J2531/0216B01J31/0284B01J31/0285C07C69/675C07C69/732Y02P20/54Y02P20/584
Inventor 金欣王凡朱琳李淑梅
Owner QINGDAO UNIV OF SCI & TECH
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