Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for synthesizing chiral ferrocene diphosphine ligand

A technology of a chiral ferrocene and a synthesis method, which is applied to the synthesis field of chiral ferrocene bisphosphine ligands, can solve problems such as inconvenience in operation, and achieve the effects of simplified operation, high quality and meeting the requirements of industrial production.

Inactive Publication Date: 2012-03-07
WUHAN UNIV OF TECH
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In the method reported in the literature (Bull.Chem.Soc.Jpn., 53,1138-1151), ferrocene is used as a raw material through multi-step synthesis, and multiple chromatographic separations and purifications are used in the route, which is inconvenient to operate

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for synthesizing chiral ferrocene diphosphine ligand
  • Method for synthesizing chiral ferrocene diphosphine ligand
  • Method for synthesizing chiral ferrocene diphosphine ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] The synthetic method of bisphosphine ligand is realized through the following steps:

[0067] One) the synthesis of acetylferrocene (II)

[0068] Add 18.6g of ferrocene (I), 14g of aluminum trichloride, and 60ml of petroleum ether into a 250ml three-neck flask connected with mechanical stirring, reflux, and a dropping funnel, and start to slowly add 11ml of acetyl chloride dropwise, within about 30 minutes Drip finished. After reacting at 50°C for 4 hours, the reaction solution was poured into water, the organic layer was separated, the aqueous layer was extracted with the organic solvent dichloromethane, the organic layers were combined, dried, and concentrated to obtain about 21 g of pure acetylferrocene (II). The rate is 92%. The melting point is 83-85°C.

[0069] 1 H NMR (CDCl 3 ): δ4.77(s, 2H), 4.50(s, 2H), 4.21(s, 4H), 2.40(s, 3H); 13 C NMR (CDCl): δ 201.9, 79.0, 72.2, 69.7, 69.4, 27.2.

[0070] Two) the preparation of ferrocene alcohol (III)

[0071] Add ...

Embodiment 2

[0093] The synthetic method of bisphosphine ligand is realized through the following steps:

[0094] One) the synthesis of acetylferrocene (II)

[0095] Add 18.6g of ferrocene (I), 12g of aluminum oxide, and 60ml of dichloromethane into a 250ml three-neck flask connected with mechanical stirring, reflux, and a dropping funnel, and add 21ml of acetyl chloride dropwise within 30 minutes. After reacting at 60°C for 5 hours, pour the reaction solution into 100ml of water, separate the organic layer, extract the aqueous layer with the organic solvent dichloromethane, combine the organic layers, dry, and concentrate to obtain about 21.9g of pure acetylferrocene(II) , yield 96%. The melting point is 83-85°C.

[0096] 1 H NMR (CDCl 3 ): δ4.77(s, 2H), 4.50(s, 2H), 4.21(s, 4H), 2.40(s, 3H); 13 C NMR (CDCl): δ 201.9, 79.0, 72.2, 69.7, 69.4, 27.2.

[0097] Two) the preparation of ferrocene alcohol (III)

[0098] Add 21.9g of acetylferrocene(II), 38ml of methanol, and 2.3g of sodium...

Embodiment 3

[0120] The synthetic method of bisphosphine ligand is realized through the following steps:

[0121] One) the synthesis of acetylferrocene (II)

[0122] Add 18.6g of ferrocene (I), 13.6g of zinc chloride, and 60ml of toluene into a 250ml three-neck flask connected with mechanical stirring, reflux, and a dropping funnel, and slowly add 21ml of acetyl chloride dropwise within 30 minutes. After reacting at 60°C for 5 hours, the reaction solution was poured into 100ml of water, the organic layer was separated, the aqueous layer was extracted with the organic solvent methylene chloride, the organic layers were combined, dried, and concentrated to obtain about 22g of pure acetylferrocene(II). Yield 96.5%. The melting point is 83-85°C.

[0123]1 H NMR (CDCl 3 ): δ4.77(s, 2H), 4.50(s, 2H), 4.21(s, 4H), 2.40(s, 3H); 13 C NMR (CDCl): δ 201.9, 79.0, 72.2, 69.7, 69.4, 27.2.

[0124] Two) the preparation of ferrocene alcohol (III)

[0125] Add 2.28 g of acetylferrocene (II), 4 ml of ...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a method for synthesizing chiral ferrocene diphosphine ligand. The method comprises the following steps: ferrocene as a raw material is prepared into acetylferrocene through aFriedel-Crafts reaction; the acetylferrocene is prepared into N,N-dimethylamine ethyl ferrocene through reduction, esterification and amination; and the N,N-dimethylamine ethyl ferrocene is resolvedby chiral acid to obtain chiral acid salt of R-N,N-dimethylamine ethyl ferrocene; the chiral acid salt of the R-N,N-dimethylamine ethyl ferrocene is analyzed to obtain optical pure R-N,N-dimethylamineethyl ferrocene; the obtained R-N,N-dimethylamine ethyl ferrocene reacts with organic lithium base; dialkyl<1> phosphonium chloride is added to the reactant to obtain 1-S-dialkyl<1> phosphonium-2-R-N,N-dimethylamine ethyl ferrocene; and 1-S-dialkyl<1> phosphonium-2-R-N,N-dimethylamine ethyl ferrocene further reacts with another dialkyl<2> phosphonium to obtain chiral diphosphine ligand 1-S-dialkyl<1> phosphino-2-R-dialkyl<2> phosphino ferrocene. The method simplifies operation, has low production cost, and can be used for industrial production.

Description

technical field [0001] The invention relates to a synthesis method of a chiral ferrocene bisphosphine ligand, which belongs to the technical field of organic chemistry and also belongs to the technical field of medicinal chemistry. Background technique [0002] Chiral ferrocene bisphosphine ligands are important ligands in the preparation of asymmetric catalytic hydrogenation catalysts. It has been widely used in asymmetric hydrogenation and is a model of asymmetric catalytic reactions in industrial applications. Since the 1970s, It has always been the focus of attention and research hotspot in the pharmaceutical industry at home and abroad. In asymmetric catalysis, the commonly used catalyst ligands are diphosphine ligands. Most of the diphosphine ligands are easily oxidized, while the ferrocene bisphosphine ligands are relatively stable and have been widely used in large-scale asymmetric catalysis. in the hydrogenation reaction. [0003] In the method reported in the lit...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07F17/02C07B57/00B01J31/24
CPCC07F17/02
Inventor 申永存徐维赟李学超
Owner WUHAN UNIV OF TECH
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com