Method for synthesizing 1, 4-diketone compound without catalyst

A technology for diketones and compounds, which is applied in the field of catalyst-free one-step synthesis, can solve the problems of harsh reaction conditions, limited substrate range, and difficulty in obtaining raw materials, and achieves the effects of less side reactions, low cost, and easy availability of raw materials.

Inactive Publication Date: 2015-08-19
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 and difficult to separate products, Complex post-processing, high production costs, 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, ketone compounds carry out direct oxidative coupling through enolization, although this method is currently the most simple and convenient way to synthesize 1,4-diketone compounds, but when different When the ketone compound is subjected to oxidative coupling reaction, self-coupling and cross-coupling of the substrate are easy to occur at the same time, resulting in low yield, complicated product and difficult separation. Therefore, this method is mainly suitable for the same kind of ketone compound through itself Oxidative Coupling Synthesis of Symmetrical 1,4-Diketones

Method used

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  • Method for synthesizing 1, 4-diketone compound without catalyst
  • Method for synthesizing 1, 4-diketone compound without catalyst
  • Method for synthesizing 1, 4-diketone compound without catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1: Reaction of 2-chlorocyclohexanone IIa1 with enol silyl ether Ia1

[0027]

[0028] In a 50mL round-bottomed flask, under stirring, add 2-chlorocyclohexanone IIa1 (10mmol), sodium carbonate (20mmol) and 15mL trifluoroethanol, then slowly enol silyl ether Ia1 (30mmol) through a constant pressure dropping funnel 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-chlorocyclohexanone IIa1, 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, then extracted 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 column chromatography for separation and pur...

Embodiment 2

[0030] Example 2: Reaction of 2-bromocyclohexanone IIa2 with enol silyl ether Ia1

[0031]

[0032] In a 50mL round-bottomed flask, under stirring, add 2-bromocyclohexanone IIa2 (10mmol), sodium carbonate (15mmol) and 15mL trifluoroethanol, then slowly enol silyl ether Ia1 (30mmol) through a constant pressure dropping funnel Drop into a round bottom flask. The reaction mixture was stirred at room temperature for 12 h. After the reaction of 2-bromocyclohexanone IIa2 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, then extracted 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 column chromatography for separation and purifica...

Embodiment 3

[0033] Embodiment 3: 2-bromocyclohexanone IIa2 reacts with enol silyl ether Ia2

[0034]

[0035] In a 50mL round-bottomed flask, under stirring, add 2-bromocyclohexanone IIa2 (10mmol), potassium carbonate (15mmol) and 15mL hexafluoroisopropanol, and then put enol silyl ether Ia2 (30mmol) through constant pressure drop The funnel drips slowly into the round bottom flask. The reaction mixture was stirred at 0°C. After the reaction of 2-bromocyclohexanone IIa2 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 0.5 h, 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 column chromatography for separation and purification t...

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PUM

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Abstract

The invention discloses a method for synthesizing a 1, 4-diketone compound without a catalyst. In the existence of alkali, the corresponding 1, 4-diketone compound is obtained by reacting silyl enol ether and alpha-haloketone by taking perfluoroalkyl alcohol as a solvent. By adopting the method for synthesizing the 1, 4-diketone compound, the raw materials are easily obtained, the cost is low, the reaction conditions are mild, the operation is simple and easy to control, the side reactions are few, the after-treatment is simple, the product yield is relatively high, and the solvent can be recovered and recycled, so that the production cost is greatly saved; the method has good environment protection benefit and economical benefit and is suitable for industrial large-scale production.

Description

technical field [0001] The invention relates to a method for synthesizing 1,4-diketone compounds, in particular to a method for synthesizing 1,4-diketone compounds in one step without a catalyst using alpha-halogenated ketone and enol silicon ether as raw materials. 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 Many nitrogen-containing compounds such as primary amines can synthesize pyrrole or substituted pyrrole; 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 ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07C45/45C07C49/792C07C49/813C07C49/80C07C49/76C07C49/417C07C49/403C07C49/657
Inventor 唐强罗娟
Owner CHONGQING MEDICAL UNIVERSITY
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