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

Novel method for preparing chiral dicarbonyl derivative by catalysis

A technology for catalytic preparation and derivatives, applied in chemical instruments and methods, preparation of organic compounds, chemical/physical processes, etc., can solve problems such as difficult and difficult hydroxyl groups

Inactive Publication Date: 2010-11-10
HANGZHOU NORMAL UNIVERSITY
View PDF0 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Alcohol is used as an alkylating agent, although it has the characteristics of "atom economy" from the perspective of synthesis, but its biggest disadvantage is that it is difficult to leave the hydroxyl group, and generally requires anhydrous conditions and stoichiometric acid
It can be seen that the second method is widely used in the preparation of racemic saturated carbonyl compounds, but it is more difficult for chiral products.

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
  • Novel method for preparing chiral dicarbonyl derivative by catalysis
  • Novel method for preparing chiral dicarbonyl derivative by catalysis
  • Novel method for preparing chiral dicarbonyl derivative by catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067] Dissolve 5.68mmol of cyclohexanediamine tartrate in 75ml of 2N NaOH solution, add 7.6mmol of triethylamine and 55ml of dichloromethane, cool to 0°C, slowly add 38ml of dichloromethane solution with 3.8mmol of TsCl dropwise at room temperature After the reaction was completed, the aqueous phase was extracted with 25ml×3, 2N HCl, and the pH value was adjusted to 9 with 2N NaOH, and the organic phase was extracted with dichloromethane, anhydrous MgSO 4 Dry, and remove the solvent under reduced pressure to obtain a pale yellow solid catalyst a-1 or catalyst a-2 (R 1 =Ts), yield 90%.

[0068] Add 500ml toluene and 0.015mol catalyst in 1L reaction flask a-1 or catalyst a-2 (R 1 = Ts), after stirring and dissolving, add 0.1mol of carboindanone ester and 0.1mol of β-nitrostyrene, stir at room temperature until the reaction is complete, and remove the solvent by rotary evaporation to obtain chiral dicarbonyl derivatives, Yield 80%, e.e value 75%, dr value 2:1.

Embodiment 2

[0070] Dissolve 4.69mmol of diphenylethylenediamine in 30ml of dichloromethane, add 4.5mmol of triethylamine, cool to 0°C, slowly add 10ml of dichloromethane solution in which 4.69mmol of TsCl is dissolved, and complete the reaction at constant temperature until complete. After finishing washing with 10ml×2 water, then wash with 10ml saturated NaCl salt, anhydrous NaCl 2 SO 4 Dry, remove the solvent under reduced pressure to obtain a white or light yellow solid product, and recrystallize with ethyl acetate to obtain the catalyst a-3 or catalyst a-4 (R 1 =Ts), productive rate 94%.

[0071] Add 500ml toluene and 0.01mol catalyst in 1L reaction flask a-3 or catalyst a-4 (R 1 = Ts), after stirring and dissolving, add 0.1mol of carboindanone ester and 0.1mol of β-nitrostyrene, stir at room temperature until the reaction is complete, and remove the solvent by rotary evaporation to obtain chiral dicarbonyl derivatives, The yield was 87%, the e.e. value was 84%, and the dr valu...

Embodiment 3

[0073] Dissolve 3.6mmol of diphenylethylenediamine (or cyclohexanediamine) and 0.3mmol of DMAP in 40ml of dichloromethane, then add 12mmol of triethylamine, cool to 0°C, slowly add 17mmol of TFAA dropwise, and stir at room temperature to complete the reaction After the reaction was completed, it was extracted with 50ml of dichloromethane, washed with 50ml of 2NHCl, 50ml of saturated sodium bicarbonate solution and 50ml of saturated brine, and the organic phase was washed with anhydrous Na 2 SO 4 Dry, remove the solvent under reduced pressure to obtain the catalyst a-1 or catalyst a-2（ or catalyst a-3 or catalyst a-4 ) (R 1 =DMB), yield 85%.

[0074] Add 500ml toluene and 0.012mol catalyst in 1L reaction flask a-1 or catalyst a-2（ or catalyst a-3 or catalyst a-4 ) (R 1 =DMB), after stirring and dissolving, add 0.1mol of carboindanone ester and 0.1mol of β-nitrostyrene, stir at room temperature until the reaction is complete, and remove the solvent by rotary evaporatio...

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 novel method for preparing a chiral dicarbonyl derivative by catalysis, needs to overcome various defects in the conventional method for preparing the chiral dicarbonyl derivative and provides an environment-friendly, economic, efficient and nontoxic method for preparing the chiral dicarbonyl derivative. The method of the invention is characterized in that a chiral diamine derivative is used as a catalyst, the molar ratio of the catalyst to raw materials is 1:10-20 and the target product, namely the chiral dicarbonyl derivative is obtained by performing reaction at the normal pressure and the room temperature in a non-polar solvent; the raw materials are an achiral dicarbonyl derivative and a nitroolefin derivative and the molar ratio of the using amount of the achiral dicarbonyl derivative to the using amount of the nitroolefin derivative is 1:1; the non-polar solvent is toluene; and the catalyst is one of the following catalysts from a to i.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis and synthesis of highly active biological drug intermediates, in particular to a novel catalytic method for preparing chiral biscarbonyl derivatives. The product can be used to asymmetrically synthesize some pharmaceutical intermediates with physiological activity, etc., and has broad industrial application prospects. Background technique [0002] Saturated carbonyl compounds are important intermediates in the pharmaceutical industry, daily chemical industry, agricultural chemical industry, etc., especially the pharmaceutical industry, which has begun to turn to the research of chiral drugs, which requires the provision of chiral drug intermediates. In order to obtain chiral saturated carbonyl compounds, scientists have conducted research and developed a variety of preparation methods. It can be obtained by selective reduction of carbon-carbon double bond, cycloaddition, insertion and ...

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): C07C201/12C07C205/45B01J31/02
Inventor 徐利文姜振钰来国桥杨科芳蒋剑雄
Owner HANGZHOU NORMAL UNIVERSITY
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