Method for synthesizing 1,4-diketone compound by using 2-halogenated cyclopentanone as raw material

A technology for substituting cyclopentanone and compounds, applied in the field of synthesis 1, which can solve the problems of harsh reaction conditions, limited range of substrates, and difficulty in obtaining raw materials, and achieve the effects of less side reactions, low cost, and easy-to-obtain raw materials

Inactive Publication Date: 2015-09-30
CHONGQING MEDICAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Although there are many methods for synthesizing 1,4-diketone compounds, these methods have certain limitations, such as difficult to obtain raw materials, limited range of substrates, harsh reaction conditions, low yield, complex products and difficult to separate, post-processing, etc. Complex processing, high production cost, etc.
For example: the most commonly used coupling reaction (DeMartino, M.P.; Chen, K.; Baran, P.S. Intermolecular Enolate Heterocoupling: Scope, Mechanism, and Application.J.Am.Chem.Soc. 2008, 130(34), 11546-11560), that is, direct oxidative coupling of ketones through enolization, although this method is currently the most simple and convenient way to synthesize 1,4-diketone compounds, but when different ketones When the compound undergoes oxidative coupling reaction, self-coupling and cross-coupling of the substrate are easy to occur at the same time, resulting in low yield, complex products and difficult separation. Symmetrical 1,4-diketone compounds

Method used

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  • Method for synthesizing 1,4-diketone compound by using 2-halogenated cyclopentanone as raw material
  • Method for synthesizing 1,4-diketone compound by using 2-halogenated cyclopentanone as raw material
  • Method for synthesizing 1,4-diketone compound by using 2-halogenated cyclopentanone as raw material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: Reaction of 2-chlorocyclopentanone Ia with enol silyl ether IIa

[0025]

[0026] In a 50mL round-bottom flask, under stirring, add sodium carbonate (15mmol), 2-chlorocyclopentanone Ia (10mmol) and 15mL trifluoroethanol solvent, then enol silyl ether IIa (30mmol) by constant pressure dropwise The funnel drips slowly into the round bottom flask. The reaction mixture was stirred at room temperature for 12 h. After the reaction of 2-chlorocyclopentanone Ia was monitored by TCL, the trifluoroethanol solvent was recovered by distillation under reduced pressure, and the remaining mixture was added with 15 mL of water and 15 mL of dichloromethane and stirred at room temperature for 0.5 h, and then extracted with dichloromethane. The extract was dried with anhydrous sodium sulfate and concentrated; then the mixed solvent of petroleum ether and ethyl acetate (10:1 by volume) was used as the eluent to carry out separation and purification by silica gel column chrom...

Embodiment 2

[0028] Example 2: Reaction of 2-chlorocyclopentanone Ia with enol silyl ether IIb

[0029]

[0030] In a 50mL round-bottomed flask, add 2-chlorocyclopentanone Ia (10mmol), sodium carbonate (15mmol), and 15mL trifluoroethanol solvent under stirring, then pass enol silyl ether IIb (30mmol) through a constant pressure dropping funnel Slowly drop into a round bottom flask. The reaction mixture was stirred at room temperature for 12 h. After TCL monitored the complete reaction of 2-chlorocyclopentanone Ia, the trifluoroethanol solvent was recovered by distillation under reduced pressure, and the remaining mixture was added with 15 mL of water and 15 mL of difluoromethane and stirred at room temperature for 0.5 h, then extracted with difluoromethane. The extract was dried with anhydrous sodium sulfate and concentrated; then the mixed solvent of petroleum ether and ethyl acetate (volume ratio: 10:1) was used as the eluent to carry out silica gel column chromatography for separation...

Embodiment 3

[0032] Example 3: Reaction of 2-chlorocyclopentanone Ia with enol silyl ether IIc

[0033] In a 50mL round-bottomed flask, under stirring, add 2-chlorocyclopentanone Ia (10mmol), potassium carbonate (20mmol) and 10mL hexafluoroisopropanol, then add enol silyl ether IIc (50mmol) in hexafluoroisopropanol The alcohol solution was slowly dropped into the round bottom flask through the constant pressure dropping funnel. The reaction mixture was stirred at 80° C., and after the reaction of 2-chlorocyclopentanone Ia was monitored by TCL, the hexafluoroisopropanol solvent was recovered by distillation under reduced pressure, and the remaining mixture was added with 15 mL of water and 15 mL of dichloromethane and stirred at room temperature for 1 h, and then Extract with dichloromethane. The extract was dried with anhydrous sodium sulfate and concentrated; then the mixed solvent of petroleum ether and ethyl acetate (volume ratio: 10:1) was used as the eluent to carry out silica gel ...

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Abstract

The invention provides a method for synthesizing 1,4-diketone compound by using 2-halogenated cyclopentanone as a raw material. In the presence of alkali, 2-halogenated cyclopentanone reacts with silyl enol ether in perfluoroalkyl alcohol used as a solvent to obtain a 1,4-diketone compound, wherein perfluoroalkyl alcohol is trifluoroethanol or hexafluoroisopropanol, and the alkali is selected from sodium carbonate, potassium carbonate, sodium trifluoroethanol, triethylamine and pyrrolidine . The synthesis method provided by the invention has advantages as follows: raw materials are easily available; costs are low; reaction conditions are mild; operation is simple and easy to control; there exists less side reaction; post-treatment is simple; product yield is high; and the solvent can be recovered and recycled so as to greatly save production cost. The method has good environmental protection benefit and economic benefit and is suitable for industrial production.

Description

technical field [0001] The invention relates to a preparation method of 1,4-diketone compounds, in particular to a preparation method of using 2-chlorocyclopentanone as a raw material to synthesize 1,4-diketone. Background technique [0002] 1,4-diketone compound is an important synthetic intermediate, through which various carbocyclic and heterocyclic compounds can be synthesized, for example, 1,4-diketone compound can be combined with ammonia, ammonium carbonate, alkyl primary amine It can also synthesize pyrrole or substituted pyrrole from many nitrogen-containing compounds; it can also react with phosphorus pentasulfide to form a thiophene ring; it can synthesize furan under the action of acid; it can synthesize oxime ketone (an intermediate for the synthesis of amino acids). At the same time, many natural products and drug molecules contain 1,4-diketone structures, and some 1,4-diketone compounds can be used as solvents in the organic industry. [0003] Although there ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/45C07C49/792C07C49/813C07C49/84C07C49/657C07C49/395C07C49/417C07C49/67
CPCC07C45/45C07C2601/08C07C2601/14C07C2601/18C07C2602/10C07C49/792C07C49/813C07C49/84C07C49/657C07C49/395C07C49/417C07C49/67
Inventor 唐强罗娟
Owner CHONGQING MEDICAL UNIVERSITY
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