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Heterogeneous catalyst for catalyzing asymmetric Aldol reaction and preparation method thereof

A heterogeneous catalyst and asymmetric technology, which is applied in catalytic reactions, preparation of organic compounds, physical/chemical process catalysts, etc., can solve problems such as complex operation, difficult mass transfer of multiphase reactions, and harsh experimental conditions. The effect of mild reaction conditions, simple preparation process and controllable structure

Inactive Publication Date: 2016-04-20
BEIJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Such as Doyaguez et al. (J.Org.Chem., 2007,72:9353-9356) have synthesized a kind of heterogeneous catalyst MCM41-Pro (C) by convergent method, but the synthetic operation step of convergent method is more loaded down with trivial details, and required reagent uses large
Dhar et al. (Proc.Inndian.Acad.Sci.Chem.Sci.2003,115,365-372) synthesized the MCM-41 grafted L-proline catalyst by covalent linkage method for catalyzing the reaction between aromatic aldehyde and acetone However, due to the difficulty of mass transfer in heterogeneous reactions, the catalytic activity and stereoselectivity of the catalyst are lower than those of homogeneous catalysts.
Patent CN103447085A uses sulfhydryl-modified SBA-15 as a carrier, and hydroxyproline derivatives as active centers to obtain heterogeneous acid-base bifunctional catalysts through covalent reactions, and is applied to Aldol-Michael asymmetric series reactions, but the method The experimental conditions are relatively harsh and the operation is complicated
Therefore, the heterogeneous catalyst experimental condition that above-mentioned method forms is harsh, and catalyst is unstable

Method used

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  • Heterogeneous catalyst for catalyzing asymmetric Aldol reaction and preparation method thereof
  • Heterogeneous catalyst for catalyzing asymmetric Aldol reaction and preparation method thereof
  • Heterogeneous catalyst for catalyzing asymmetric Aldol reaction and preparation method thereof

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Effect test

Embodiment 1

[0030] The heterogeneous catalyst in the present invention is that the bipyridyl proline derivative is immobilized on the metal-modified dual-model mesoporous silica nanometer material carrier. The metal-modified dual-model mesoporous silicon oxide nanomaterial carrier has mesopores with a diameter of 2-4nm and spherical particle stacking pores with a diameter of 10-30nm. The silicon oxide nanomaterial itself is a spherical particle of 40-100nm, and the spherical particle has mesopores of 2-4nm. When a large number of silicon oxide nanomaterials accumulate with each other, a stacking hole will appear, and the diameter of the stacking hole is 10-30nm. Wherein, the molecular structural formula of bipyridyl proline derivative is

[0031]

[0032] Where R stands for H, L-proline, N-Cbz-prolinamide, 3-CH 3 C 6 h 4 CO,(CH 3 ) 3 CO,CH 3 One of a kind in CO.

Embodiment 2

[0034] This embodiment provides a method for preparing a heterogeneous catalyst for catalytic asymmetric Aldol reaction in Example 1, comprising the following steps:

[0035] Step 1. Prepare dual-model mesoporous silicon oxide nanomaterials.

[0036] Step 2, preparing a metal-modified dual-model mesoporous silica nanomaterial carrier, including the following sub-steps:

[0037] Step 21, drying the dual-model mesoporous silica nanomaterial;

[0038] Step 22, mixing the dried mesoporous silica nanomaterial with a methanol solution of metal acetate and stirring to react, so that metal elements are immobilized on the mesoporous silica nanomaterial;

[0039] Step 23, evaporating the solvent, and vacuum drying;

[0040] Step 24, washing with water and methanol for several times, and drying to obtain the metal-modified dual-model mesoporous silica nanomaterial carrier, the metal is bonded to the silicon hydroxyl group on the surface of the silica nanomaterial, and is uniformly dist...

Embodiment 3

[0062] Step 1: Preparation of dual-model mesoporous silica nanomaterials

[0063] Dissolve 2.81g of octadecyltrimethylammonium bromide in 104g of distilled water, stir until dissolved, pipette 8mL of ethyl orthosilicate into the solution, add 2.6ml of ammonia water with a mass fraction of 25%, stir until white lumps are produced shaped gel, filtered, washed, dried, and the obtained white powder was heated to 550° C. for 5 hours and calcined to obtain a dual-model mesoporous silica nanomaterial with a diameter of 4 nm in the primary channel and a diameter of 30 nm in the secondary channel structure.

[0064] Here, the primary pores refer to the mesoporous pores on the spherical particles of the silicon oxide nanomaterials, and the secondary pores refer to the spherical particle accumulation pores generated by the particles of the silicon oxide nanomaterials stacked on each other.

[0065] Step 2: Preparation of metallic nickel-modified dual-model mesoporous silica nanomaterial ...

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Abstract

The invention discloses a heterogeneous catalyst for catalyzing an asymmetric Aldol reaction, and comprises immobilization of a dipyridine proline derivative onto a metal modified bimodal mesoporous silicon oxide nano-material carrier. The invention discloses a preparation method of the heterogeneous catalyst. The preparation method comprises the following steps: preparing a bimodal mesoporous silicon oxide nano-material, preparing the metal modified bimodal mesoporous silicon oxide nano-material carrier, and immobilizing the dipyridine proline derivative. The immobilization of the dipyridine proline derivative and metal of the metal modified bimodal mesoporous silicon oxide nano-material carrier is carried out by coordination, so that the preparation technology is simple, cost is low, the structure of the catalyst is controllable, and the reaction condition is mild; the catalyst can be recycled and recovered, and is easy to separate.

Description

technical field [0001] The invention relates to the field of chemical catalysts, in particular to a heterogeneous catalyst for catalyzing asymmetric Aldol reaction and a preparation method thereof. Background technique [0002] In recent years, the direct asymmetric Aldol reaction (aldol condensation reaction) catalyzed by proline and its derivatives has the advantages of atom economy, high enantioselectivity, mild reaction conditions, simple operation, and less pollution. It is an important means of bonding and is an indispensable reaction in asymmetric organic synthesis and drug synthesis. However, there are still shortcomings such as a large amount of catalyst used, difficult to recycle and unable to be reused. [0003] At present, many workers are studying the reaction of proline and its derivatives using acid-base groups, loading them on mesoporous materials, and then performing catalytic reactions. Such as Doyaguez et al. (J.Org.Chem., 2007,72:9353-9356) have synthes...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C201/12C07C205/45
CPCB01J31/184B01J2231/4205B01J2531/0275B01J2531/16B01J2531/26B01J2531/847C07B2200/07C07C201/12C07C205/45Y02P20/50Y02P20/584
Inventor 唐志云孙继红白诗扬赵洪武武霞
Owner BEIJING UNIV OF TECH
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