Method for preparing 1,3-diphenylbut-2-ene-1-one

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing 1,3-diphenylbut-2-2ene-1-one (dypnone) from acetophenone in the presence of cation-exchange polymerizing sulfoacid resin in H+-form as a catalyst at temperature 80-160°C. The process can be carried out in the presence of nonpolar aliphatic hydrocarbon solvent. Acetophenone fraction isolating in the process for the combined preparing propylene oxide and styrene can be used as acetophenone. Method provides selectivity is 84-98.8% by dypnone in consumption of catalyst 3.0-3.4% of acetophenone mass.

EFFECT: improved preparing method.

3 cl, 1 tbl, 8 ex

 

The invention relates to the petrochemical industry, specifically to a method for producing 1,3 diphenylbuta-2-EN-1-it (dinona), which finds application as plasticizers or perfume bases and other

A method of obtaining dypnone of acetophenone in the presence of polyphosphoric acid at a temperature of 30÷150° (U.S. Patent No. 2769842, publ. 06.11.1956 year).

Use in the process of getting dypnone polyphosphoric acid as a catalyst leading to increased consumption - 2,2÷2.5 kg/kg of acetophenone.

Closest to the proposed technical solution on a set of attributes is a method for dypnone (U.S. Patent No. 3023245, publ. 27.02.1962). Deipnon obtained from acetophenone in periodic reactor mixing for 2÷12 hours at a temperature of 125÷200°in the presence of an acid catalyst based on natural or synthetic aluminosilicates containing from 7 to 15% of the mass. aluminum. The process can be used a solvent from the group of nonpolar hydrocarbons. Conversion of acetophenone as described in examples 35÷63%, the selectivity for diphone - 57,7÷88,7%.

The disadvantage of this method is the increased consumption of a catalyst comprising 5÷25% of the mass. by weight of acetophenone.

The objective of the invention is to reduce the consumption of produce is RA in the process of getting dypnone from acetophenone.

The problem is solved by a method of obtaining 1,3 diphenyl-but-2-EN-1-it (dinona) from acetophenones raw materials in the presence of a catalyst at a temperature of 80÷160°With, at the same time as the catalyst is used cation-exchange polymerization sulfoxylate resin in H-form.

There is the possibility of conducting the process in the presence of non-polar aliphatic hydrocarbon solvent and used as acetophenazine raw materials acetophenone fractions generated during the joint production of propylene oxide and styrene.

As the cation polymerization sulfoxylates resin in the H form can be used domestic sulfonic cation KU-2, KU-3 AND KU-4, corresponding to the requirements of THE 6-07-493-95 "ion-exchange Resin cation marks KU-2-8, KU-2-8 M", SMC-2 ("encyclopedia of polymers". Volume 1, Moscow, 1972, str-1000) or their foreign equivalents.

The process is carried out in a periodic reactor mixing at a temperature of 80÷160°possibly in the presence of non-polar aliphatic hydrocarbon solvent normal or isomeric structures, such as hexane, heptane, octane, Nanan, decane, undecane, and others

The implementation of the method of obtaining dypnone is illustrated by the following examples.

Example 1

In a three-neck flask equipped mech is technical mixing device, reflux condenser and inlet for inert gas, loaded 30.0 g of acetophenone, after which the contents of the flask heated in a stream of nitrogen with stirring to 110°C, after which the flask is added 4.0 g of cation exchanger KSM-2, previously dried in vacuum (residual pressure of 15 mm Hg) at a temperature of 100°C.

The process is carried out at a temperature of 110°without distillation of the formed water for 60 minutes, taking samples of the reaction mixture every 15 minutes.

The content of acetophenone and diplona in the reaction mixture is determined by means of gas-liquid chromatography.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 2

The process is conducted as in example 1 for 120 minutes, changing the amount of cation exchanger KSM-2 to 1.0,

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 3

The process is conducted according to example 2 for 60 minutes, changing the temperature to 148°C.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 4

In a three-neck flask equipped with a mechanical mixing device, a downward fridge and inlet for inert gas, loaded 30.0 g of acetophenone and 17.0 g of n-nonane, after which the contents of the flask heated in a stream of nitrogen with stirring to 150°With, the village is e what in the flask was added 1.0 g of cation exchanger KSM-2, previously dried in vacuum (residual pressure of 15 mm Hg) at a temperature of 100°C.

The process is carried out at a temperature of 150°With continuous distillation of the solvent and water formed in the course of 90 minutes.

The content of acetophenone and diplona in the reaction mixture is determined by means of gas-liquid chromatography.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 5

In a three-neck flask equipped with a mechanical mixing device, a nozzle Dean-stark and inlet for inert gas, loaded 100.0 g of acetophenone and 70.0 g of n-octane, after which the contents of the flask heated in a stream of nitrogen with stirring to 135°C, after which the flask is added 3.0 g of cation exchanger KSM-2, previously dried in vacuum (residual pressure of 15 mm Hg) at a temperature of 100°C.

The process is carried out at a temperature of 135°and With continuous distillation of the formed water for 90 minutes.

The content of acetophenone and diplona in the reaction mixture is determined by means of gas-liquid chromatography.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 6

In a three-neck flask equipped with a mechanical mixing device, a nozzle Dean-stark and inlet for inert gas, loaded 100.0 g of acetophenone and 70.0 g of n-grams is the Ksan, then the contents of the flask heated in a stream of nitrogen with stirring to 86°C, after which the flask is added 3.0 g of cation exchanger KSM-2, previously dried in vacuum (residual pressure of 15 mm Hg) at a temperature of 100°C.

The process is carried out at a temperature of 86°and With continuous distillation of the formed water for 330 minutes.

The content of acetophenone and diplona in the reaction mixture is determined by means of gas-liquid chromatography.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 7

In a three-neck flask equipped with a mechanical mixing device, a downward fridge and inlet for inert gas, loaded 150,0 g industrial acetophenone fractions generated during the joint production of styrene and propylene oxide and containing: acetophenone 78,382 wt. -%, methylphenylcarbinol 7,580 wt. -%, the benzaldehyde, benzyl alcohol, phenol, styrene, heavy residue - other. Next is loaded 50.0 g of n-nonane, after which the contents of the flask heated in a stream of nitrogen with stirring to 150°C, after which the flask is added 4.0 g of cation exchanger KSM-2, previously dried in vacuum (residual pressure of 15 mm Hg) at a temperature of 100°C.

The process is carried out at a temperature of 150°With continuous distillation of the solvent within 120 minutes./p>

The content of acetophenone and diplona in the reaction mixture is determined by means of gas-liquid chromatography.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Example 8

In a three-neck flask equipped with a mechanical stirring device, reflux condenser and inlet for inert gas, loaded 30.0 g of acetophenone, after which the contents of the flask heated in a stream of nitrogen with stirring to 110°C, after which the flask is added 4.0 g of cation exchange resin KU-2, previously dried in vacuum (residual pressure of 15 mm Hg) at a temperature of 100°C.

The process is carried out at a temperature of 110°without distillation of the formed water for 120 minutes, taking samples of the reaction mixture every 30 minutes.

The content of acetophenone and diplona in the reaction mixture is determined by means of gas-liquid chromatography.

Data for the conversion of acetophenone and selectivity dypnone shown in the table.

Received deipnon stands out from the reaction mixture by vacuum distillation. Boiling point dypnone 213°at a residual pressure of 30 mm Hg

The mass of the catalyst by weight ACF, %
# exampleTemperature, °Weight ACF, gThe mass of catalyst, gTime, minutesConversion ACF, %Selectivity for dypnone, mol%.
111030,04,013,31514.4V93,2±1,0
30to 19.9
4522,0
6023,1
211030,01,03,312023,594,8
314830,01,03,36023,992,0
415030,01,03,39043,788,4
51351003,03,09041,084,2
6861003,0 3,033028,293,7
7150117,6*4,03,412029,398,8
811030,04,013,33020,887,6±1,0
6024,6
9025,1
12025,2
Note: * - part of acetophenone faction.

1. The method of obtaining 1,3-diphenylbuta-2-EN-1-it (dinona) from acetophenones raw materials in the presence of a catalyst at a temperature of 80-160°C, characterized in that the catalyst used cation-exchange polymerization sulfoxylate resin in H-form.

2. The method of obtaining 1,3-diphenylbuta-2-EN-1-it (dinona) according to claim 1, characterized in that the process is carried out in the presence of non-polar aliphatic hydrocarbon process is Italia.

3. The method of obtaining 1,3-diphenylbuta-2-EN-1-it (dinona) according to claims 1 and 2, characterized in that as acetophenazine raw materials use acetophenone fraction generated during the joint production of propylene oxide and styrene.



 

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing 1,3-diphenylbut-2-2ene-1-one (dypnone) from acetophenone in the presence of cation-exchange polymerizing sulfoacid resin in H+-form as a catalyst at temperature 80-160°C. The process can be carried out in the presence of nonpolar aliphatic hydrocarbon solvent. Acetophenone fraction isolating in the process for the combined preparing propylene oxide and styrene can be used as acetophenone. Method provides selectivity is 84-98.8% by dypnone in consumption of catalyst 3.0-3.4% of acetophenone mass.

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1 tbl, 10 ex

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