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Method for preparing optically active aldehyde or ketone and preparation method of catalyst thereof

An optically active and catalyst technology, which is applied in the preparation of organic compounds, catalysts for physical/chemical processes, and organic chemistry methods, can solve problems such as low hydrogenation efficiency, reduced catalyst conversion frequency, and short catalyst life.

Active Publication Date: 2015-06-24
WANHUA CHEM GRP CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The use of this catalyst can effectively improve product chemistry and stereoselectivity, but there are disadvantages of low hydrogenation efficiency, especially under the condition of high substrate / catalyst, the conversion frequency of the catalyst is significantly reduced, resulting in the need for multiple recycling of the catalyst and complicated process operations , and the catalyst life is short, prone to noble metal coupling deactivation and other disadvantages

Method used

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  • Method for preparing optically active aldehyde or ketone and preparation method of catalyst thereof
  • Method for preparing optically active aldehyde or ketone and preparation method of catalyst thereof
  • Method for preparing optically active aldehyde or ketone and preparation method of catalyst thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Synthesis of Oxalo[(3R,4R)-3,4-Bis(diphenylphosphino)pyrrolidine]diamine

[0079] a) Synthesis of (3S,4S)-1-benzyl-3,4-bis(methylsulfonyloxy)pyrrolidine

[0080] Dissolve 16.0g (3S,4S)-(+)-1-benzyl-3,4-pyrrolidinediol and 23.1ml triethylamine in 50ml dichloromethane, add 12.9ml methanesulfonate dropwise at 0°C Acyl chloride, heated up to room temperature and reacted for 30 minutes, then extracted twice with 30ml deionized water, the organic phase was washed with 300ml of 1mol / L hydrochloric acid solution, and the water phase was separated, and the water phase was washed with 100ml of caustic soda solution, then 60ml of dichloromethane was added, and the liquid was separated Finally, the organic phase was kept, and the solvent was removed under reduced pressure to obtain 25.2 g of solid (3S,4S)-1-benzyl-3,4-bis(methylsulfonyloxy)pyrrolidine.

[0081] b) Synthesis of (3S,4S)-3,4-bis(methylsulfonyloxy)pyrrolidine acetate

[0082] Dissolve 24.0g (3S,4S)-1-benzyl-3,4-bis(m...

Embodiment 2

[0088] Synthesis of oxalo[(3R,4R)-3,4-bis(di-tert-butylphosphino)pyrrolidine]diamine

[0089] a) Synthesis of (3R,4R)-3,4-bis(di-tert-butyl)pyrrolidine hydrochloride

[0090] Dissolve 36.2ml of di-tert-butylphosphine in 50ml of dioxane, add 4.67g of sodium metal, stir for 14 hours, then dissolve the reactant in 170ml of N,N-dimethylformamide, cool to -40°C 15.97g (3S,4S)-3,4-bis(methylsulfonyloxy)pyrrolidine acetate was added to the reaction liquid, and the temperature was raised to room temperature for 24 hours. After the reaction was completed, the solvent was removed under reduced pressure, 200ml of 2mol / L hydrochloric acid solution was added, stirred for 1 hour and then filtered. The filter cake was washed with 100ml of deionized water and 200ml of ether and dried to obtain 16.8g of solid, namely (3R,4R)-3, 4-bis(di-tert-butyl)pyrrolidine hydrochloride.

[0091] b) Synthesis of oxalo[(3R,4R)-3,4-bis(di-tert-butyl)pyrrolidine]diamine

[0092] Dissolve 0.879g (3R,4R)-3,4-...

Embodiment 3

[0094] 100.8mg Rh(CO) 2 acac (about 0.4 mmol) and 277.2 mg of oxalo[(3R,4R)-3,4-bis(diphenylphosphino)pyrrolidine]diamine ligand (about 0.3 mmol) were dissolved in 30 g of toluene under argon atmosphere , stirred at room temperature and normal pressure for 5 hours, and after the solution was clarified, a homogeneous catalyst solution was obtained, and the solvent was removed by distillation under reduced pressure at room temperature (vacuum degree <200Pa) to obtain 378.8 mg of a solid catalyst.

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Abstract

The invention provides a method for preparing optically active aldehyde or ketone by asymmetric hydrogenation and a preparation method of a catalyst thereof. The optically active aldehyde or ketone is prepared by using a homogeneous and optically active double transition metal catalyst and a chiral amino acid cocatalyst through asymmetric hydrogenation of alpha, beta-unsaturated aldehyde or ketone. The reaction pressure (absolute pressure) is 0.1-10MPa, preferably 5-8MPa; the reaction temperature is 25-90 DEG C; the catalyst is prepared from chiral multi-coordination phosphine-containing ligands and transition metals; chiral amino acid added to the reaction system serves as a cocatalyst; and the reaction selectivity is 95-99%, the conversion rate can reach 85-99.9%, and the optical purity of the product is 80-99ee%.

Description

technical field [0001] The invention relates to a method for preparing optically active aldehydes or ketones and catalysts thereof, in particular to a method for preparing optically active aldehydes or ketones, especially D-citronellal, by asymmetric hydrogenation of α, β-unsaturated aldehydes or ketones . Background technique [0002] Optically active aldehyde or ketone compounds are important intermediate compounds with synthetic and medicinal value, and many compounds themselves are important flavor and fragrance components. [0003] European published patent EP0000315 discloses a method for preparing optically active D-citronellal by hydrogenating geranial or neral in the presence of a catalyst complex, which is dissolved in the reaction system and composed of rhodium and hand The chiral phosphine ligand is a simple 2,3-bis(diphenylphosphino)butane ligand. The chemoselectivity and stereoselectivity of this homogeneous system are not high, and the amount of catalyst is r...

Claims

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Application Information

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IPC IPC(8): C07B53/00C07C45/62C07C47/21C07C49/403C07C29/145C07C35/18B01J31/24
Inventor 鲍元野董菁张永振黎源
Owner WANHUA CHEM GRP CO LTD
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