The way to obtain 1-phenyl-1-(alkyl)phenylacetone

 

(57) Abstract:

The invention relates to a method for producing 1-phenyl-1-(alkyl)phenylacetone, which is an intermediate for obtaining rodenticide preparations 2-(-phenyl--(alkyl)phenylacetyl)indandione-1,3, in particular ethylbenzene(alkyl R = C2H5and izinduna (alkyl R = ISO-C3H7) used for rodent control. The method consists in the interaction of alkyl benzene with 1-chloro-1-phenylacetone in the presence of anhydrous aluminum chloride, followed by exposure of the reaction mixture and isolation of the target product in a known manner, initially charged to the reactor the alkyl benzene and 1-chloro-1-phenylacetone, then with stirring, gradually add anhydrous aluminum chloride so that the temperature of the reaction mixture did not exceed 50oC. Technical result - improving the quality of the target product, simplifying technology.

The invention relates to a method for producing 1-phenyl-1-(alkyl)phenylacetone, which is an intermediate for obtaining rodenticide preparations 2- (- phenyl -- (alkyl)phenylacetyl)-indandione-1,3, in particular ethylbenzene (alkyl R = C2H5and izinduna (alkyl R - ISO-C3H7), premastication, in particular, 1-phenyl-1-(ethyl)phenylacetone (U.S. Pat. Russia N 1037441), taken as a prototype. The method consists in the interaction of 1-chloro-1-phenylacetone with alkylbenzene, in particular, with ethylbenzene in the presence of anhydrous aluminum chloride. Moreover, in the first reactor load anhydrous aluminium chloride and ethylbenzene, then after heating to 60-70oC with stirring, added dropwise 1-chloro-1-phenylacetone, then maintain the reaction mass at 60-65oC for 1 hour.

Then carry out multi-stage selection of the product that is complete distillation of the solvent. The residue is distilled in a vacuum oil pump, collecting the fraction with TKip.174-176oC/2 mm RT.article.

It should be noted that the authors of the present invention, the work done on the study of the composition of the reaction mixture described method using gas-liquid chromatography (GLC).

In the reaction mass after removal of the solvent content of 1-phenyl-1-(ethyl)phenylacetone is 52%. In addition to the target product was detected up to 8% of diphenylacetone and about 40% of other impurities (see comparative example 3).

The presence of diphenylacetone in the reaction mass shows the flow PA and diethylbenzene and further alkylation of benzene with the formation of diphenylacetone. In addition, proceeds adverse reaction of alkylation of diethylbenzene and a number of other adverse reactions.

The reaction of disproportionation of ethylbenzene is also confirmed by literature data (Century, Lipovich, M. F. Polubentseva. Alkylation of aromatic hydrocarbons. M., "Chemistry", 1985).

Similar is the reaction produce 1-phenyl-1-(isopropyl)phenylacetone described in the prototype method. When this reaction mass after removal of the solvent contains about 51% of the main product, 17.5% of diphenylacetone and about 31% of other impurities (see comparative example 4).

Thus, to obtain a higher quality target product required additional vacuum distillation of the reaction mixture after removal of the solvent, which is associated using deep vacuum and complicates the technology during the industrial use of the method.

The task of the invention is improving the quality of the target product by reducing the occurrence of adverse reactions, in particular the reaction of disproportionation of alkyl benzene, and simplify technology.

The method consists in the interaction of alkyl benzene with 1-chloro-1-phenylacetone in Pris is, the ATEM with stirring, gradually add anhydrous aluminum chloride so that the temperature of the reaction mixture did not exceed 50oC. After downloading the entire amount of aluminum chloride, the reaction mass is maintained with stirring and at a temperature of 50-60oC for 1.0 to 1.5 hours. Then carry out multi-stage selection of the product type specified in the prototype.

After extraction of the reaction mixture with alkyl benzene carry out the distillation of the solvent, simultaneously draining the product of the azeotropic distillation of the water with the solvent. Get 1-phenyl-1-(alkyl)phenylacetone with mass fractions of the basic substance ~ 80-85% (according to GC).

Offered the boot sequence of reagents can significantly reduce the occurrence of adverse reactions, including the reaction of disproportionation of alkyl benzene.

The number of diphenylacetone in the reaction mass after removal of the solvent when producing 1-phenyl-1-(ethyl)phenylacetone reduced from 7.7% to 1.6%, other impurities from 40,6 to 13.6% (see examples 1 and 3).

When producing 1-phenyl-1-(isopropyl)phenylacetone number of diphenylacetone reduced from 17.5 to 5.5%, other impurities from 31,3 to 14.8% (see examples 2 and 4). When this mass fraction of the quality of the target product is achieved by changing the boot sequence of reagents and allows the use of 1-phenyl-1-(alkyl)phenylacetone at the stage of obtaining 2- (- phenyl -- (alkyl)phenylacetyl)-indandione to 1.3 without additional vacuum distillation. This greatly simplifies the technology, as it allows you to avoid using in the process a deep vacuum.

Additionally, it is important that the gradual loading of anhydrous aluminum chloride, the temperature of the reaction mixture did not exceed 50oC. At a higher temperature exothermic alkylation reaction proceeds very rapidly, which can lead to severe foaming of the reaction mass, and even ejection from the reactor. At temperatures below 15oC the reaction rate slows to a crawl. It is most expedient to maintain the temperature at loading aluminum chloride from the 30oC to 50oC.

Example 1

Obtain 1-phenyl-1-(ethyl)phenylacetone

In a glass reactor with a capacity of 250 ml, equipped with a stirrer, a reflux condenser, a thermometer, a shirt for hot and cold water, put 127,4 g (1,20 mole) of ethylbenzene and 50.0 g (0,29 mole) 1-chloro-1-phenylacetone. Then under stirring was added in small portions during 1 hour of 52.2 g (0,39 mole) of anhydrous aluminum chloride so that the temperature of the reaction mixture did not exceed 50oC. After all of anhydrous aluminum chloride was added, the reaction mass is maintained at AC who are in a pre-cooled to 4-10oC water so that the temperature of the mass does not exceed 20oC. Then the mass is acidified with 15% hydrochloric acid to pH 1-2, separate the organic layer and the aqueous layer was once extracted with benzene. The organic layers were combined, washed with water, 10% solution of Na2CO3then again with water until the pH of the aqueous layer 6-7. Then the benzene is distilled off at a residual pressure of 80-90 mm RT.article The temperature in the cube at the end of the distillation, solvent 120oC. simultaneous dehydration of the product by azeotropic distillation of water with benzene. Get 69,1 g of 1-phenyl-1-(ethyl)phenylacetone (83% of theoretically possible) in the form of a red-brown oil with a violet fluorescence.

The product is analyzed by means of gas-liquid chromatography. Receive a product with a mass fraction of 1-phenyl-1-(ethyl)phenylacetone 84,8%, diphenylacetone of 1.6%, other impurities of 13.6%.

Then the product without vacuum distillation is used for ethylbenzene.

Example 2.

Obtain 1-phenyl-1-(isopropyl)phenylacetone

Carried out analogously to example 1, except for the used reagents. The reactor is placed 38,5 g (of 0.32 mole) of cumene and 13.5 g (of 0.08 mole) 1-chloro-1-phenylacetone. Then primav is. the so Temperature in the cube at the end of the distillation, solvent 120oC. Obtain 17.9 g of 1-phenyl-1-(isopropyl)phenylacetone (72% of theoretically possible) in the form of a red-brown oil.

The product is analyzed by means of gas-liquid chromatography. Receive a product with a mass fraction of 1-phenyl-1-(isopropyl)phenylacetone 79,8%, diphenylacetone 5.5% and other impurities of 14.8%. Then the product without vacuum distillation is used for izinduna.

Example 3 (comparative)

Obtain 1-phenyl-1-(ethyl)phenylacetone

In a glass reactor with a capacity of 250 ml, equipped with a stirrer, thermometer, reflux condenser, addition funnel, jacketed for hot and cold water, place of 52.2 g (0,39 mole) of anhydrous aluminum chloride and 127,4 g (1,20 mole) of ethylbenzene. The mass is heated with stirring to 60-65oC. Then, with stirring, added dropwise 50.0 g (0,29 mole) 1-chloro-1-phenylacetone. After all 1-chloro-1-phenylacetone added, the reaction mass is maintained at 60-65oC for 1 hour. Then the reaction mass is treated analogously to example 1. After distillation of the benzene receive 66.5 g of 1-phenyl-1-(ethyl)phenylacetone (with 49% of theoretically possible).

is anilation of 51.7%, diphenylacetone of 7.7%, other impurities to 40.6%.

Example 4 (comparative)

Obtain 1-phenyl-1-(isopropyl)phenylacetone

Carried out analogously to example 3, except for the used reagents. The reactor is placed to 18.7 g (of 0.14 mol) of anhydrous aluminum chloride and 43.1 g (of 0.36 mole) of cumene. Then added 15.2 g (of 0.09 mole) 1-chloro-1-phenylacetone. The cumene is distilled at a residual pressure of 50-60 mm RT. Art. Temperature in the cube at the end of the distillation, solvent 120oC. Obtain 20.7 g of 1-phenyl-1-(isopropyl)phenylacetone (47% of theoretically possible).

The product is analyzed by means of gas-liquid chromatography. Receive a product with a mass fraction of 1-phenyl-1-(isopropyl)phenylacetone 51,2%, diphenylacetone of 17.5%, other impurities 31,3%.

Example 5 (comparative)

Obtain 1-phenyl-1-(ethyl)phenylacetone

Carried out analogously to example 1, except the temperature of the reaction mass by adding anhydrous aluminum chloride, which in this case allow up to 60oC. there Is a strong foaming of the reaction mixture with the release from the reactor.

The way to obtain 1-phenyl-1-(alkyl)phenylacetone interaction of alkyl benzene with 1-chloro-1-phenylacetone in product known manner, wherein the first charged to the reactor the alkyl benzene and 1-chloro-1-phenylacetone, then gradually add anhydrous aluminum chloride so that the temperature of the reaction mixture did not exceed 50oC.

 

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