The method of hydrogenation of aromatic ketones

 

(57) Abstract:

The invention relates to a method for hydrogenation of aromatic ketones, which are intermediate compounds used in the production of dyes, varnishes, resins. The method of hydrogenation with hydrogen of aromatic ketones number of acetophenone at elevated temperature and atmospheric pressure over pre-treated with a solution of acid Bronsted palladium catalyst is the fact that hydronaut acetophenone concentration (1,12-8,32)10-2mol/l at 40-70oWith the amount of catalyst is 0.16-2.5 g/l, in addition, the catalyst is treated with a solution of acid concentration 0,3610-2KMOL/m3within 30-40 minutes, as acid Bronsted uses sulfuric acid. The technical result is an increase in the yield of aromatic hydrocarbons, reducing the time of hydrogenation. 2 Il. , 1 table.

The invention relates to organic chemistry, and in particular to methods of hydrogenation of aromatic ketones, which are intermediate compounds used in the production of dyes, varnishes, resins, and some pharmaceutical products with high yield and time-limited process.

oC and a pressure of 300 atmospheres. The final products of the reaction were methylcyclohexylamine, ethylcyclohexane. Ethylbenzene yield was 0.3%. The hydrogenation time of 240 minutes. (Barinov N. C. , Mushenko D. C. , Lebedev, E. G. , Balandin, A. A. Liquid-phase hydrogenation of acetophenone on usmievam catalyst under conditions of elevated temperature and pressure. - Alma-ATA: Nauka. - 1967. - S. 130-133).

The disadvantage of this method is the low selectivity with respect to ethylbenzene. In addition, the provision of high-temperature regimes hydrogenation and maintenance of installations, working under pressure, leads to an appreciation of the process.

The closest in technical essence is a way hydrogenation with hydrogen of acetophenone at elevated temperature and atmospheric pressure over pre-treated with a solution of acid Bronsted palladium catalyst. The hydrogenation was subjected to the acetophenone concentration 110-2mol/l palladium catalyst (3% Pd) in an amount of 3 g, prepared from PdCl2the selection of metal from the corresponding salts with subsequent applying it to a previously prepared silica-containing media. The experiments were implemented in C and 1 - phenylethanol and ethylbenzene (60%). (Maria Angeles Aramendia, Victoriano Borau, Cesar Jimenez, Jose Maria Marinas and Maria Eugenia Sempere // Gazzetta Chimica Italiana, 119, 1989, S. 129-130 Published by Societa Chimica Italiana).

The disadvantage of this method is the low selectivity with respect to the output of ethylbenzene, a significant time of hydrogenation, high consumption of catalyst.

The objective of the invention is to increase the yield of aromatic hydrocarbons, reducing the time of hydrogenation through the development of process conditions hydrogenation of aromatic ketones number of acetophenone with different structure, a modified solution of sulfuric acid palladium catalyst.

The technical result of the invention is the selective hydrogenation of aromatic ketones in high yields of the corresponding aromatic hydrocarbons with reduced time of hydrogenation.

This object is achieved in that in the method of hydrogenation with hydrogen of aromatic ketones number of acetophenone at elevated temperature and atmospheric pressure over pre-treated with a solution of acid Bronsted palladium catalyst, according to the invention, hydronaut acetophenone at a concentration of (1.12-8.32)10-2mol/l (0.05 - 0.3 g) and 40-70oC. Kolicina carbon porous media Sibunit is 4%, which meets industrial requirements to the content of the precious metal in the catalyst (no more than 10%). The catalyst is treated with a solution of sulfuric acid concentration 0.3610-2KMOL/m3within 30-40 minutes

Hydrogenation of acetophenone concentration more 8.3210-2mol/l in the presence of a catalyst concentration of less than 0.16 g/l is slow, with little release of hydrocarbons. Hydrogenation of acetophenone concentration less 1.1210-2mol/l leads to the formation of Perevedenovsky reaction products.

When processing of the catalyst with a solution of sulfuric acid concentration is less than 0.3610-2KMOL/m3hydrogenation of aromatic ketones is slow, the yield of aromatic hydrocarbons is small. The use of sulfuric acid concentration more 0.3610-2KMOL/m3for treatment of the catalyst leads to the formation of Perevedenovsky products.

Hydrogenation of acetophenone at a temperature below 40oC is slow, the yield of aromatic hydrocarbons is small. Carrying out the process at temperatures above 70oC leads to the evaporation of the solvent is isopropyl alcohol.

Recovery of aromatic kevany benzene ring, the yield of aromatic hydrocarbons is reduced.

To explain the method of hydrogenation of the investigated number of aromatic ketones described drawings, in which Fig. 1 shows a General scheme for the hydrogenation of acetophenone, Fig. 2 shows an installation for carrying out the hydrogenation process (General view).

The hydrogenation was carried out at the facility, consisting of a reactor with intensive stirring 1, swinging movement which is transmitted from the electric motor 2 via a crank mechanism 3. The reactor 1 thermostatized water supplied from thermostat 4. In the reactor 1 through the fitting 5 is loaded reagents, and through the fitting 6 is hydrogen from a cylinder 7. Measuring the amount of hydrogen produced by the measuring burette 8, which receives water from the surge vessel 9. The reactor 1 was thermostatically to the required temperature. Then through the nozzle 5 into it loaded half the volume of the solvent and the required amount of catalyst. After that, the reactor was flushed three times with hydrogen, gerotziafas, and within hours the catalyst was saturated with hydrogen. After this time in the reactor 1 through the fitting 5 is loaded substrate and the remaining portion of the solvent, the react is. The amount of absorbed hydrogen was recorded by the measuring burette 8.

When the experiment periodically samples were taken and carried out their analysis by gas chromatography.

Example No. 1. Hydrogenation of acetophenone C8H8O.

Brutto-formula of acetophenone C8H8O:

< / BR>
0.05 g of the catalyst is treated with a solution of sulfuric acid concentration 0.3610-2mol/m3within 30 minutes After settling the upper layer is decanted, and the catalyst was washed with the same solvent. The reactor 1 thermostatic at 50oC. Then through the nozzle 5 into him download two-thirds of the volume of solvent and 1.66 g/l (0.05 g) catalyst. After that, the reactor was rinsed three times with hydrogen, sealed, and within hours the catalyst is saturated with hydrogen. After this time in the reactor 1 through the fitting 5 download 5.5510-2mol/l of acetophenone and the rest of the solvent, the reactor was rinsed three times with hydrogen and pressurized, start the engine 2 and carry out the hydrogenation process. The amount of absorbed hydrogen is measured by the measuring burette 8. The hydrogenation time 130 minutes Conversion of acetophenone is 100%. The reaction product is ativan ormula of propiophenone C9H10O

< / BR>
0.05 g of the catalyst is treated with a solution of sulfuric acid concentration 0.3610-2mol/m3within 30 minutes After settling the upper layer is decanted, and the catalyst was washed with the same solvent. The reactor 1 thermostatic at 50oC. Then through the nozzle 5 into him download two-thirds of the volume of solvent and 1.66 g/l (0.05 g) catalyst. After that, the reactor was rinsed three times with hydrogen, sealed, and within hours the catalyst is saturated with hydrogen. After this time in the reactor 1 through the fitting 5 download 4.9710-2mol/l of propiophenone and the rest of the solvent, the reactor was rinsed three times with hydrogen and pressurized, start the engine 2 and carry out the hydrogenation process. The amount of absorbed hydrogen is measured by the measuring burette 8. The hydrogenation time 300 minutes Conversion propiophenone is 97%. The reaction product is propylbenzoyl C9H12.

Example No. 3. hydrogenation butyrophenones, C10H12).

Brutto-formula butyrophenones, C10H12O:

< / BR>
0.05 g of the catalyst is treated with a solution of sulfuric acid concentration 0.3610-2mol/m3within 30 minutes After settling the upper layer decanting load two-thirds of the solvent and 1.66 g/l (0.05 g) catalyst. After that, the reactor was rinsed three times with hydrogen, sealed, and within hours the catalyst is saturated with hydrogen. After this time in the reactor 1 through the fitting 5 download 2.2510-2mol/l butyrophenones, and the rest of the solvent, the reactor was rinsed three times with hydrogen and pressurized, start the engine 2 and carry out the hydrogenation process. The amount of absorbed hydrogen is measured by the measuring burette 8. The hydrogenation time 300 minutes Conversion butyrophenones is 89%. The reaction product is butylbenzoyl C10H14.

Examples of hydrogenation of acetophenone and outputs hydrocarbons are presented in the table.

The proposed method can be widely used both in laboratory conditions and the existing equipment for specific sectors of the pharmaceutical industry, in the production of lacquer and paint products, when they include a stage of selective hydrogenation of aromatic ketones, with a good yield of the corresponding hydrocarbons and reduced process time.

The method of hydrogenation of aromatic ketones number of acetophenone at elevated temperature and atmospheric pressure over pre-treated with a solution of acid Bronsted PA is e/l at 40-70oWith the amount of catalyst is 0.16-2.5 g/l, in addition, the catalyst is treated with a solution of acid concentration 0,3610-2KMOL/m3within 30-40 minutes, as acid Bronsted uses sulfuric acid.

 

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