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Electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds

A synthesis method and compound technology, applied in the field of electrochemical catalytic synthesis of α-carbonyl ketones, can solve the problems of increased reaction cost and post-processing complexity, ineffective reaction, and high-concentration organic waste discharge. Achieve high yield, avoid equipment cost and reduce reaction cost

Inactive Publication Date: 2015-01-28
BEIJING UNIV OF TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] (1) Although Torii and Wang Jiangmei used a simple single-chamber electrolytic cell for electrolytic synthesis, the types of α-hydroxy ketones synthesized were limited, and it was necessary to use a complex dual-catalyst system or to regenerate the catalyst by adding an oxidant, which increased the reaction cost and post-processing complexity
[0005] (2) Nishiguchi found that the reaction cannot be carried out effectively in a single-chamber electrolytic cell, and a double-chamber electrolytic cell must be used, while using expensive metallic platinum as an electrode material
Compared with the single-chamber electrolytic cell, the use of the double-chamber electrolytic cell increases the cost of the equipment, increases the energy consumption, and the operation is more complicated
[0006] (3) The reaction solution cannot be recycled, resulting in a large discharge of high-concentration organic waste liquid
[0007] At present, in a single-chamber electrolytic cell, a single catalyst is used, and the preparation method of α-carbonyl ketone, which can be regenerated in situ and the reaction solution can be recycled, has not been reported in the literature at home and abroad.

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0026] Embodiment 1: the electrocatalytic synthesis of 2,3-pentanedione

[0027] In a 400 mL single-chamber electrolytic cell, 100 mmol of 2-hydroxy-3-pentanone was dissolved in 200 mL of NaBr (10 mmol) aqueous solution, and 100 mL of dichloromethane was added. Under stirring at room temperature, with graphite as the anode and iron sheet as the cathode, at 30mA / cm 2 electrolysis at a constant current. When the current efficiency reaches 59%, the electrolysis is stopped, the layers are static, and the dichloromethane in the lower organic phase is removed under normal pressure to obtain 2,3-pentanedione with a yield of 78%.

[0028]

[0029] Yellow-green liquid; bp 110-112°C; 1 H NMR (400MHz, CDCl 3 ): δ1.09(t, 3H, J=7.6Hz), 2.17(s, 3H), 2.44(q, 2H, J=7.6Hz).

Embodiment 2

[0030] Example 2: Electrocatalytic synthesis of 2,3-pentanedione

[0031] As in Example 1, 2,3-pentanedione was synthesized by electrocatalysis using 3-hydroxy-2-pentanone as a raw material, with a yield of 76%.

[0032]

[0033] Yellow-green liquid; bp 110-112°C; 1 H NMR (400MHz, CDCl 3 ): δ1.09(t, 3H, J=7.6Hz), 2.17(s, 3H), 2.44(q, 2H, J=7.6Hz).

Embodiment 3

[0034] Example 3: Electrocatalytic synthesis of 3,4-hexanedione

[0035] As in Example 1, 3,4-hexanedione was electrocatalytically synthesized using propioin as a raw material, with a yield of 85%.

[0036]

[0037] Yellow-green liquid; bp 131°C; 1 H NMR (400MHz, CDCl 3 ): δ1.10(t, 3H, J=7.6Hz), 2.47(q, 2H, J=7.6Hz).

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Abstract

The invention discloses an electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds, and belongs to the technical field of preparation of alpha-carbonyl ketone compounds. The electrochemical catalytic synthesis method comprises the following steps: in a single-chamber electrolytic cell, in a certain amount of electrolyte solution, with alpha-carbonyl ketone as a raw material and halide as a catalyst, performing constant-current electrolysis at a certain temperature and a certain current density to obtain the alpha-carbonyl ketone compounds. Compared with the existing other electrochemical methods for synthesizing the alpha-carbonyl ketone compounds, the electrochemical catalytic synthesis method provided by the invention has the advantages as follows: the single-chamber electrolytic cell and an inexpensive electrode material are used, and an oxidant is regenerated by an electrochemical method; supporting electrolyte is not added, and only a catalytic amount of halide is taken as the catalyst, so that the cost is greatly reduced and the posttreatment is simple; therefore, the electrochemical catalytic synthesis method is more convenient for industrial production.

Description

technical field [0001] The invention relates to an electrochemical catalytic synthesis method of α-carbonyl ketone compounds, belonging to the technical field of preparation of α-carbonyl ketone compounds. Background technique [0002] α-Carbonyl ketones are important solvents, reaction intermediates or chemical reagents. In addition, many α-carbonyl ketones are also widely used as fragrances. For example, 3,4-hexanedione has a buttery aroma, and diacetyl has a creamy aroma. They are widely used in the production of cream, cheese, chocolate, candy, jelly and pudding. Therefore, the efficient use of α-carbonyl ketones Synthesis is in the spotlight. [0003] The electrochemical oxidation of α-hydroxy ketones is one of the ways to synthesize these compounds. Torii (Inokuchi, T.; Matsumoto, S.; Torii, S.J.Org.Chem.1991,56,2416) etc. in sodium bromide and N-oxo-2,2,6,6-tetramethylpiperidinium In the presence of the double catalyst composed, benzil was prepared by constant cur...

Claims

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Application Information

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IPC IPC(8): C25B3/04C25B3/25
Inventor 曾程初李龙吉肖环兰田红玉梁森
Owner BEIJING UNIV OF TECH
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