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

Immobilized chiral phosphoric acid catalyst and preparation method thereof

A phosphoric acid catalyst, chiral technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc. Easy to purify, easy to prepare, easy to operate

Inactive Publication Date: 2013-04-03
CHANGSHU INSTITUTE OF TECHNOLOGY
View PDF7 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The heteropolyacid-supported chiral organic small molecule catalyst has obtained relatively good enantioselectivity and product yield in the direct Aldol reaction, but the use of the heteropolyacid-supported chiral organic small molecule catalyst has certain limitations. , the chiral organic small molecules that need to be supported are basic, while another large class of chiral phosphoric acid catalysts that have developed rapidly and are widely used in recent years are difficult to support on heteropolyacids.

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
  • Immobilized chiral phosphoric acid catalyst and preparation method thereof
  • Immobilized chiral phosphoric acid catalyst and preparation method thereof
  • Immobilized chiral phosphoric acid catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] The synthesis of the chiral binaphthol (formula II) that the polystyrene resin containing amino group of embodiment 1 is immobilized

[0023] Obtained by reference method (Xiao-Wu Yang, Jian-Heng Sheng, Chao-Shan Da etc. J. Org. Chem., 2000, 65(2), 295-296). Infrared spectrum IR (KBr) of compound (formula II): 3344, 2827, 1644, 1626, 1570, 1308, 1270, 1245cm -1 . We have carried out infrared spectrometry respectively to compound C, polystyrene resin and resin-linked chiral binaphthol (formula II), and find out by comparison, after resin and compound C condensation, carboxyl peak 3589, 1672cm -1 , and resin amino peak 3535cm -1 disappear while at 3344, 1644, 1570, 1245cm -1 The characteristic absorption peaks of amides appear at 1308 and 1270cm -1 It shows the existence of phenolic hydroxyl group, which proves that BINOL has been bonded to the resin. The immobilized amount of chiral binaphthol on polystyrene resin was calculated to be 0.4mmol / g.

Embodiment 2

[0024] The synthesis of the chiral phosphoric acid (formula I) that the polystyrene resin of embodiment 2 is immobilized

[0025] Take a 50mL dry three-necked bottle, under the protection of argon, add 6 grams of polystyrene resin immobilized chiral binaphthol (formula II) and 20mL CH 2 Cl 2 , cooled to 0°C, followed by dropwise addition of POCl 3 (3.6mL, 39.2mmol), Et 3 N (8.2 mL, 58.8 mmol), after the dropwise addition, stirred at room temperature for 4-6 hours. Cool the system to 0°C, slowly add water (1mL) dropwise, filter the solid with suction, wash with DMF, CH 2 Cl 2 , 1N HCl aqueous solution and methanol wash 2 times, vacuum-dry to constant weight, obtain the chiral phosphoric acid (formula I) of target product polystyrene resin immobilization, quality is 6.15 grams, calculate chiral phosphoric acid on polystyrene resin The solid loading capacity is 0.4mmol / g.

[0026] Infrared spectrum IR (KBr) of compound (formula I): 3397, 3344, 2827, 1735, 1644, 1626, 1570, ...

Embodiment 3

[0028] Example 3 (Comparative Example) Unsupported chiral phosphoric acid (formula III) catalyzes the asymmetric Friedel-Crafts reaction of indole and sulfonimide

[0029]

[0030] Take a 50mL dry three-necked bottle, under argon protection, dissolve imine E (2.5mmol) and unsupported chiral phosphoric acid catalyst (formula III) (0.25mmol) in toluene (10mL), and stir at room temperature for 30 minutes, then cooled to -50°C and stirred for 10 minutes, and added indole D (12.5mmol) at -50°C. After TLC tracking imine E raw material disappeared, add 10% NaHCO 3 The reaction was quenched with aqueous solution (30mL), extracted with ethyl acetate (50mL), the organic layer was washed with water (30mL) and saturated brine (30mL) respectively, and anhydrous Na 2 SO 4 After drying, the solvent was removed under reduced pressure, and column chromatography (AcOEt:PE=1:3) gave the target product F as a white solid with a yield of 81% and an ee value equal to zero. 1 H NMR (300MHz, CD...

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 discloses an immobilized chiral phosphoric acid catalyst and a preparation method thereof. A structural formula of the catalyst is as Formula I as shown in the specification; a carrier PS (polystyrene) is aminomethylated polystyrene. HCl, 1%DVB, and an amido substitution value is 1.0mmol / g, and the catalyst is in a chiral binaphthol structure, i.e. BINOL (binaphthol) can be in an R configuration or an S configuration. The preparation method of the catalyst comprises the following steps of a) synthesizing aminomethylated polystyrene immobilized chiral binaphthol, and b) allowing immobilized chiral binaphthol to react with POCl3 when Et3N exists, and obtaining polystyrene immobilized chiral phosphoric acid (Formula I). The heterogeneous catalyst can be prepared easily, the treatment operation after reaction is simple, the catalyst (Formula I) is applied to an asymmetric Friedel-Crafts alkylation reaction, the chemical yield of a product can reach 85%, and the enantiomeric selectivity ee value can reach 91%.

Description

technical field [0001] The invention relates to a chiral phosphoric acid catalyst and a preparation method thereof, in particular to an immobilized chiral phosphoric acid catalyst and a preparation method thereof. Background technique [0002] In recent years, people's demand for single-enantiomer chiral compounds is huge and increasing year by year. This demand is mainly reflected in the fields of medicine, pesticides and fine chemicals. In 2000, the global sales of chiral drugs was 133 billion US dollars, and it was increasing at an annual rate of 8%. Since 2000, asymmetric organic small molecule catalysts represented by proline and chiral phosphoric acid have developed rapidly, becoming the third important type of asymmetric synthetic catalysts after transition metal catalysts and biological enzyme catalysts. Compared with traditional transition metal catalysts and biological enzyme catalysts, organic small molecule catalysts have remarkable characteristics such as simpl...

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
IPC IPC(8): B01J31/06C08F112/08C08F8/40C07D209/14
Inventor 汪权何帅
Owner CHANGSHU INSTITUTE OF TECHNOLOGY
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