SU1456407A1 - Method of producing diacetone acrylamide - Google Patents

Abstract

The invention relates to amides of carboxylic acids, in particular to the preparation of diacetone acrylamide, which can be used in the manufacture of plastics, dyes, emulsions for treating skin and wood. The goal is to increase the yield of the product, increase its purity and simplify the process. Obtaining the target product lead from Acrylonitrile and acetone in the presence of conc. The mixture of reagents is carried out at 20-25 C for 30-40 minutes. The mixture is heated to a further 45–50 ° C for 3.5–4 h and neutralized with an aqueous solution of ammonia. The intermediate product is precipitated with methyl ethyl ketone with a ratio of the reaction mixture and methyl ethyl ketone 1: (1.5-3.0) at O -. Preferably, the product is precipitated after partially neutralizing the reaction mixture with gaseous ammonia. The yield is increased to BO - 82% (at the stage of isolation). 1 hp f-ly. "

Description

one

The invention relates to organic chemistry, namely to a method for producing N (1,1-dimethyl-3-oxobutyl) acrylamide or diacetone acrylamide, which can be used as a starting component in the manufacture of plastics, dyes, lubricant compositions, emulsions, CPU processing of leather and wood, as well as film photographic materials.

The aim of the invention is to increase yield and improve quality, and to simplify the process.

Example 1. A mixture of 58.0 cm of acrylonitrile and 130 cm of acetone is added with stirring to 100 cm of 96% sulfuric acid over 30 minutes.

after which the temperature is raised to 50t, stirring is continued es, e 4 h and cooled to. 333.1 g of reaction mixture containing 52% of intermediate product and 4.4% of acrylamide are obtained. The resulting mass is cooled to 0 ° C and 622.8 cm of methyl ethyl ketone are introduced with slow stirring, stirring is continued for 1 hour and then left to stand for 4 hours.

The falling crystals of the intermediate product are filtered, washed with methyl ethyl ketone and dried. 41.1 cm of water are added to 125 6 g of crystalline substance, 290 cm of toluene are added and mixed at 25 ° C with 135.5 cm of water, 290 cm of toluene are added and

mixed at 25 ° C with 135.5 cm of aqueous ammonia, stirred for another 0.5 h (pH 7-8 on indicator paper). The aqueous layer was separated, and the organic was dried with 25 g of activated alumina for 6 hours. The dried and clarified solution was cooled to 0 ° C and 492-6 cm of petroleum ether was introduced with slow stirring. The precipitated crystals are separated, dried, and 63.93 g of diacetone acrylamide are obtained. The yield of diacetone acrylamide is 4.2.76% for acrylonitrile, so pl. 56.5-57 C.

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43.5% for acrylonitrile m. Pl. 56.5- 57 C.

Example 4. In 100 g of the reaction mixture obtained analogously to example 1, 3.5 g of ammonia gas was introduced up to a sulfuric acid concentration of 50%. To the obtained partially neutralized mixture at 10 ° C is poured 200 cm of methyl ethyl ketone. The crystals of the intermediate product are filtered off, washed from impurities with methyl ethyl ketone and dried. Get 42,6.g intermediate product, yield on

Example 2. To the 100 cm3 of the 96% 15% separation stage of which is sulfuric acid is added with stirring 82%. The resultant intermediate is converted to diacetone acrylamide according to example 1, Diacetone-acrylamide yield

Sewing a mixture of 58 cm of acrylonitrile and 130 cm of acetone for 40 minutes, after which the temperature is raised to 50 ° C. Stirring is continued 2o t-pl.

(20.87 g) for acrylonitrile 46.5%,

56.5-57 ° C.

It is kept for another 4 hours and cooled to 20 ° C. 333.1 g of the reaction mixture are obtained, containing 46.5% of intermediate product and 5.9% acrylamide.

Example 5. In 100 g of the reaction mixture, obtained analogously to example 1, ammonia gas was introduced to a concentration of sulfuric acid.

n ° r -ic49 May% While stirring and the temperature The mass obtained is cooled to about 25 ° C. A, at 625 cm, while stirring, 625 cm of methyl methane are introduced under stirring.

methyl ethyl ketone, stirring forketone. lasts 1 hour and then left to stand

for 4 h. Inserted crystals filter - crystals of intermediate product

washed, washed with pure methyl ethyl JQ filtered off, washed from primatone and dried. This gives 108.2 g of a crystalline product, which is converted into diacetone acrylamide according to Example 1. The yield of diacetone acrylamide is 40.9% (61.15 g) per starting acylo-nitrile, m.p. 56-57 C.

Example 3. To 100 g of the reaction mixture, obtained similarly with pure methyl ethyl ketone, and dried, 40.5 g of intermediate product are obtained. The isolated semiproduct is converted to diacetone acrylamide according to Example 1. The yield of diacetone acrylamide (19 5 g) of acryponitrile is 43.4%, t. square 56.5 C.

Example 6. A mixture of 58.0 cm of acrylonitrile and 138.6 cm of acetone at 20 ° C over 20 minutes is added with stirring to 120, 1 cm of 96% sulfuric acid, after which the temperature is raised to 50 ° C, and stirring is continued 4 more hours and cooled to 45. 377.48 g of a reaction mixture are obtained. The resulting mass is cooled before and with slow stirring 937.8 cm of methyl ethyl ketone is introduced. Obtain 120.00 g of intermediate pro40

measure 1 is added with stirring at a temperature of 373 cm of methyl ethyl ketone, stirred for 1 hour and left to stand for 4 hours. The crystals of the intermediate product are filtered, washed with methyl ethyl ketone and dried. To 36.7 g of the intermediate product are added 12.1 cm of water, 84.8 cm of toluene and mixed at 30 ° C with 40 cm of 25% aqueous ammonia, stirred for another 0.5 h (pH 7-8 according to indicator Dukt, which is transformed into diacetate paper). The aqueous layer is separated, and nacrylamide, according to organic, is dried with 10 g of 66.63 g of activated diacetone acrylamide. You. Alumina bath for 6 hours; 45.5% stroke on the source acryponitrile; The drained and clarified solution is cooled. Pl. 56.5 56.7 C.

: -:, .- -: -; g „-: Je-r; GaPm-gd-ga

lamida The output of diacetone acrylamide 30 minutes, then raise

43.5% for acrylonitrile m. Pl. 56.5- 57 C.

Example 4. In 100 g of the reaction mixture obtained analogously to example 1, 3.5 g of ammonia gas was introduced up to a sulfuric acid concentration of 50%. To the obtained partially neutralized mixture at 10 ° C is poured 200 cm of methyl ethyl ketone. The crystals of the intermediate product are filtered off, washed from impurities with methyl ethyl ketone and dried. Get 42,6.g intermediate product, yield on

Schut in diacetoneacrylamide according to example 1, The output of diacetoneacrylamide

t pl

(20.87 g) for acrylonitrile 46.5%,

56.5-57 ° C.

Example 5. In 100 g of the reaction mixture, obtained analogously to example 1, ammonia gas was introduced to a concentration of sulfuric acid.

Qfiltered, washed from primase with pure methyl ethyl ketone and dried. 40.5 g of intermediate product are obtained. The isolated semiproduct is converted to diacetone acrylamide according to Example 1. The yield of diacetone acrylamide (19 5 g) of acryponitrile is 43.4%, t. square 56.5 C.

Example 6. A mixture of 58.0 cm of acrylonitrile and 138.6 cm of acetone at 20 ° C over 20 minutes is added with stirring to 120, 1 cm of 96% sulfuric acid, after which the temperature is raised to 50 ° C, and stirring is continued 4 more hours and cooled to 45. 377.48 g of a reaction mixture are obtained. The resulting mass is cooled before and with slow stirring 937.8 cm of methyl ethyl ketone is introduced. Obtain 120.00 g of intermediate pro0

The drug that is converted to diaceto nacrylamide, according to the diacetone-acrylamide amide 66.63 g. You. 45.5% stroke on the source acryponitrile; m.p. 56.5 56.7 C.

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temperature is up to 50 ° C, stirring is continued for another 4 hours, cooled to 0 ° C. Obtain 346.34 g of the reaction mixture, into which 5.88 g of ammonia gas is introduced to a sulfuric acid content of 49 ppm. To the obtained partially neutralized mixture is poured at 10.44 cm of methyl ethyl ketone. The intermediate crystals are filtered, washed with methyl ethyl ketone and mixed with impurities. 142.3 g of intermediate are obtained, which are converted to diaceton acrylamide according to example 1, after which 68.86 g of dia-cetonacrylamide are added. Exit 47%, so pl. 56-57 C.

Example 8. To 96.06 cm of 96% sulfuric acid are added with stirring 58 cm of acrylonitrile and 20 126 cm of acetone at 20 ° C over 60 minutes, after which the temperature is raised to. Stirring is continued for another 4 hours and cooled to 10 ° C. To the resulting reaction mixture, 1606.2 cm of methyl ethyl ketone is added. The precipitation is separated, washed and receive 108.3 g of intermediate product, which according to example 1

initial reagents up to 20-25 ° C and mixing time 30-60 minutes. The step of isolating the intermediate compound, followed by purification from impurities and conversion, upon neutralization, to diacetone acrylamide allows to obtain high quality diacetone acrylamide: colorless, free from polymeric materials and acrylamide. The yield in the isolation step is 65-70%. An increase in the yield of the intermediate product at the stage of its completion up to 80-82% is achieved by partially neutralizing the sulfuric acid with gaseous ammonia before precipitation with methyl ethyl ketone.

Claims (2)

1. A method of producing diacetone-acrylamide by reacting acrylonitrile with acetone in the presence of concentrated sulfuric acid, comprising 25 mixing the reactants, heating, neutralizing the reaction mixture with an aqueous solution of ammonia, followed by isolating the product with extraction, characterized in that 15 converted to diacetonacrylamide. Nowadays, the increase in product yield is 52.9 g of pure thiacetone acrylamide, 36.1% yield, i.e. . 56-57 ° C. Example 9. To 100 g of the reaction mixture obtained according to Example 8, cooled to 15 ° C, 149 cm of methyl ketone were introduced with stirring. 76.0 g of intermediate product are obtained, which is converted to diacetone acrylamide according to Example 1. You divide 11.56 g of diacetone acrylamide, yield 25.5%, m.p. 56.2-56.3 p. An increase in the yield of the intermediate compound to 73-75% in its synthesis based on acrylonitrile and acetone according to the proposed method is achieved by reducing the mixing temperature. 35 40 45 To achieve its purity and simplification, the initial reagents are displaced at 20–25 ° C for 30–40 min with further aging at 45–50 ° C for 3.5–4 h, after which the intermediate product is precipitated with methyl ethyl ketone at a mass ratio reaction mixture: methyl ethyl ketone, equal to 1: (1.5-3.0), and temperature 0-5 C. 2. A method according to claim 1, characterized in that the intermediate product is precipitated after partially neutralizing the reaction mixture with gaseous ammonia. initial reagents up to 20-25 ° C and mixing time 30-60 minutes. The step of isolating the intermediate compound, followed by purification from impurities and conversion, upon neutralization, to diacetone acrylamide allows to obtain high quality diacetone acrylamide: colorless, free from polymeric materials and acrylamide. The yield in the isolation step is 65-70%. An increase in the yield of the intermediate product at the stage of its completion up to 80-82% is achieved by partially neutralizing the sulfuric acid with gaseous ammonia before precipitation with methyl ethyl ketone. Invention Formula 1. A method of producing diacetone acrylamide by reacting acrylonitrile with acetone in the presence of concentrated sulfuric acid, comprising mixing the reactants, heating, neutralizing the reaction mixture with an aqueous solution of ammonia, followed by separating the product with extraction, characterized in that "The goal of increasing product yield To achieve its purity and simplification, the initial reagents are displaced at 20–25 ° C for 30–40 min with further aging at 45–50 ° C for 3.5–4 h, after which the intermediate product is precipitated with methyl ethyl ketone at a mass ratio reaction mixture: methyl ethyl ketone, equal to 1: (1.5-3.0), and temperature 0-5 C. 2. A method according to claim 1, characterized in that the intermediate product is precipitated after partially neutralizing the reaction mixture with gaseous ammonia.