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Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone

A technology for nitroacetophenone and aminoacetophenone, which is applied in the field of catalytic synthesis of fine chemicals, can solve the problems of increased cost and high difficulty in product selectivity control, and achieves high application times, low equipment requirements, and simple operation. Effect

Inactive Publication Date: 2016-05-11
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the nitro functional group, benzene ring, and carbonyl group in the m-nitroacetophenone structure may be reduced during the hydrogenation process, and the selectivity of the product is difficult to control.
For example, the commonly used palladium-carbon catalyst can realize the hydrogenation reduction of the nitro functional group in m-nitroacetophenone, but even at room temperature, the carbonyl group will be partially hydrogenated at the same time to obtain by-products such as 3-aminophenethyl alcohol, and then increase Reduced the cost of product separation and purification

Method used

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  • Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone
  • Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone
  • Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] 2.0g m-nitroacetophenone, 0.2gPt / Bi 2 o 3 (Pt content is 0.2wt%), add 10mL of anhydrous methanol into a 50mL batch reactor, replace the gas in the reactor with nitrogen and hydrogen successively for 3-5 times, fill in hydrogen to a pressure of 1.0MPa, and heat up to 70 °C, the stirring speed is 600-800 rpm. If the total pressure drops below 0.5MPa, add hydrogen to the initial pressure. After 4h, the total pressure did not change any more, the stirring was stopped, and it was cooled to room temperature. Centrifuge the reaction mixture, the bottom is a yellow catalyst, and the supernatant is green (if m-nitroacetophenone is not completely converted, the supernatant is yellow-green, and the by-products include nitroso compounds, which are partially hydrogenated products of nitro groups) . Get a small amount of supernatant and adopt gas chromatography analysis, m-nitroacetophenone conversion rate is greater than 99.9%, m-aminoacetophenone selectivity is greater than 99....

Embodiment 2

[0019] 2.0g m-nitroacetophenone, 0.2gPt / Bi 2 o 5 (Pt content is 0.2wt%), add 10mL of absolute ethanol into a 50mL batch reactor, replace the gas in the reactor with nitrogen and hydrogen successively for 3-5 times, fill in hydrogen to a pressure of 0.1MPa, and heat up to 40 °C, the stirring speed is 600-800 rpm. If the total pressure drops, hydrogen is added to the initial pressure. After 10 hours, the total pressure did not change any more, the stirring was stopped, and it was cooled to room temperature. A small amount of supernatant was taken and analyzed by gas chromatography, the conversion rate of m-nitroacetophenone was greater than 99.9%, and the selectivity of m-aminoacetophenone was greater than 99.9%. The product m-aminoacetophenone was obtained after the methanol in the filtrate was removed by rotary evaporation, and the separation yield was 98%.

Embodiment 3

[0021] Add the catalyst recovered in Example 1 and 10 mL of anhydrous methanol into a 50 mL batch reactor, add 2.0 g of m-nitroacetophenone, replace the gas in the reactor with nitrogen and hydrogen successively for 3-5 times, and fill with hydrogen To a pressure of 1.0 MPa, the temperature was raised to 70°C under constant stirring, and the stirring speed was 600-800 rpm. If the total pressure drops, hydrogen is added to the initial pressure. After a certain period of time (see Table 1), the total pressure does not change any more, stop stirring, and cool to room temperature. A small amount of supernatant was taken and analyzed by gas chromatography, the conversion rate of m-nitroacetophenone was greater than 99.9%, and the selectivity of m-aminoacetophenone was greater than 99.9%. According to the above method, the catalyzer is recycled, and the specific results are shown in the following table:

[0022]

[0023] It can be seen from the table that the catalyst still has...

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Abstract

The present invention provides a method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone, according to the method, hydrogen is used as a reducing agent, bismuth-compound-supported Pt is used as a catalyst, and the m-nitroacetophenone is highly-selectively reduced into the m-aminoacetophenone by a batch-type one-step reaction. The method reaction temperature is 30-120 DEG C, the reaction time is 1-20 hours, and the hydrogen partial pressure is 0.05-2.0MPa. The catalyst system can be used for efficiently catalytic hydrogenation of the m-nitroacetophenone, the m-aminoacetophenone yield is high; the hydrogen is used as the reducing agent, a main by-product is water, the method is green and environmentally-friendly; reaction conditions are mild, hydrogenation process equipment requirements are low, operation is simple; product separation and purification are simple, and the number of reusing times of the catalyst is high.

Description

technical field [0001] The present invention relates to a catalytic synthesis method of fine chemicals, specifically a kind of hydrogen as reducing agent, platinum supported by bismuth compound as catalyst, m-nitrobenzene is synthesized by intermittent liquid-phase catalytic selective hydrogenation reaction Highly selective reduction of ethyl ketone to m-aminoacetophenone. Background technique [0002] M-aminoacetophenone is an important pharmaceutical and organic intermediate, and its downstream products have important uses. For example, m-hydroxyacetophenone is an intermediate in the synthesis of adrenaline-mimetic drugs, m-chloroacetophenone can be used to synthesize new and special drugs for bronchiectasis, anti-purpura and other drugs, and 3-acetamidoacetophenone is a synthetic sedative-hypnotics Intermediate of indiplon. [0003] m-nitroacetophenone is relatively cheap and easy to obtain, and m-aminoacetophenone can be prepared by selective reduction. The traditiona...

Claims

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Application Information

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IPC IPC(8): C07C221/00C07C225/22
CPCC07C221/00C07C225/22
Inventor 杜中田孙小万唐洋洋
Owner DALIAN UNIV OF TECH
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