DE1254141B - Process for the preparation of alpha-chlorine or alpha-bromo derivatives of saturated aliphatic mono- or dicarboxylic acids - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

UTSCHES

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07c

German class: 12 ο -

Number: 1 254 141

File number: M 47528IV b / 12 ο

Filing date: December 27, 1960

Opened on: November 16, 1967

The invention relates to a process for the preparation of -x-chloro or% -bromo derivatives of saturated aliphatic mono- or dicarboxylic acids, which is characterized in that cyclic or acyclic ketone peroxides with acrylonitrile or a low molecular weight acrylic acid alkyl ester and hydrochloric or hydrobromic acid in the presence of an iron (II) - or copper (I) salt at a temperature between -20 and -f 60 C, preferably between -10 and + 10 ⁰ C, in a medium consisting of aqueous alcohol or aqueous acetone.

If the peroxide has a cyclic structure, the molecule does not break, but occurs z. B. a chlorine derivative of a dicarboxylic acid.

The nitrile or the ester of \ -Chloric acid is obtained, if you cyclopentanone with the nitrile or an ester of acrylic acid in the presence of a Iron (II) - or copper (I) salt converts. If Reacts cyclohexanone hydroperoxide under the same conditions, one obtains the nitrile or the Esters of "v-chlorazelaic acid.

If the hydroperoxide has acyclic structure, cleavage takes place in the reaction according to the invention with the formation of the corresponding -halogen derivative of a saturated fatty acid instead.

In the same way, the methyl hexyl ketone and methyl heptyl ketone peroxides become the corresponding ones Obtained derivatives of α-chlorononanoic or decanoic acid.

If the reaction is carried out in the presence of hydrobromic acid instead of hydrochloric acid, so it runs practically in the same direction and leads to the formation of bromine in place of chlorine derivatives.

The practical implementation of the new method is very simple and consists in that one under Stir the peroxide, which may also be dissolved in an organic solvent (ether or alcohol) is dissolved, added to a mixture which consists of iron (II) or copper (I) salt, an excess of the acrylic acid derivative and the corresponding hydrohalic acid.

The unreacted acrylic acid derivative is completely recovered after completion by distillation.

About 20 to 50 percent by weight of the peroxide will be in halocarboxylic acid derivatives and 30 to 50 percent by weight converted into the corresponding ketone, which is also recovered by distillation can be.

The following examples serve to illustrate the claimed process.

Process for the production of α-chlorine or
% -Bromo derivatives of saturated aliphatic
Mono- or dicarboxylic acids

Applicant:

MONTECATINI Sccietä Generale
per rindustria Mineraria e Chimica,
Milan (Italy)

Representative:

Dipl.-Ing. Dipl.-Chem.

Dr. phil. Dr. techn. J. Reitstötter

and Dr.-Ing. W. Bunte, patent attorneys,

Munich 15, Haydnstr. 5

Named as inventor:

Francesco Minisci,

Ugo Pallini, Milan (Italy)

Claimed priority:
Italy of December 31, 1959 (24 076),
dated January 18, 1960 (24 845)

example 1

g of cyclopentanone peroxide are added to a mixture of 53 g of acrylonitrile, g of cuprous chloride and 6 g of concentrated hydrochloric acid, dissolved in 150 ml of water, with stirring and cooling; the temperature is kept between -5 and 0 ^° C. during this process. The organic layer is then separated off and the acidic components are removed from it by shaking with sodium carbonate solution.

By acidifying the alkaline-aqueous solution, an oil layer is obtained, which by decanting separated, dried by heating under reduced pressure and acidified with sulfuric acid Methyl alcohol is dissolved. The solution is refluxed for 3 hours, then the excess Removed methanol, neutralized the sulfuric acid with sodium bicarbonate solution and the residue at distilled under reduced pressure. After a pre-run at 70 to 80 ° C / 0.4mm go to 100 to 115 ° C / 0.4mm 11.6 g of the methyl ester of α-chlorinated acid (yield 18 percent by weight calculated on peroxide) over. By saponification of the x-chlorofluoric acid methyl

709 688/424

i 254 141

ester with concentrated hydrochloric acid, the free acid is kept in quantitative yield (melting point = 98 to 99 ° C.). The organic layer obtained at the beginning of the example does not become 50.25 g (bp = 77 ° C.) converted acrylonitrile and 8.73 g of cyclopentanone (boiling point = 130 ° C.) were recovered by distillation.

Example 2

20 g of methyl ethyl ketone peroxide dissolved in 15 ml of ethyl ether are added with stirring and cooling to a mixture consisting of 40 g of acrylonitrile, 25 g of cuprous chloride, 4 g of concentrated hydrochloric acid and 150 ml of water. The reaction temperature is kept between -10 and + 5 ° C. When the addition is complete, the organic layer is separated off and fractionally distilled; at 160 ° C./760 mm, 4.8 g -v-chlorovaleric acid nitrile pass over. By hydrolysis with concentrated hydrochloric acid to obtain 5.4 g of Λ-chlorovaleric acid (Kp. = 220-222 ⁰ C) Yield = 21 percent by weight, calculated on the peroxide.

Example 3

A g of 40 acrylonitrile, 25 g of cuprous chloride, 5 g of hydrochloric acid and 150 ml of water existing mixture is added a solution of 24 g Diäthylketonperoxyd in 20 ml ethyl ether added with stirring and cooling to about 0 ⁰ C. When the reaction has ended, the organic layer is separated off, excess acrylonitrile is distilled off and the residue is refluxed with concentrated hydrochloric acid. By distilling the saponification product, 5.4 g of Λ-chlorovaleric acid (boiling point = 220 to 222 ° C.) are obtained. Yield = 20 percent by weight, calculated on the peroxide.

Example 4

A mixture of 50 g of acrylonitrile, 25 g of cuprous chloride and 6 g of hydrochloric acid in 150 ml of water 25 g of methylhexyl ketone peroxide were added. During the addition, the mixture is stirred and brought to 0 Chilled to 5 ° C. The organic layer is then separated off and the acrylonitrile is removed by distillation; the residue is refluxed with concentrated hydrochloric acid. The Product is distilled under reduced pressure; at 115 to 118 ° C / 0.6 mm it becomes 8.3 g Ä-Chlorononanoic acid obtained. Yield = 28 percent by weight.

Example 5

40 g of methyl heptyl ketone peroxide dissolved in 30 ml of ethyl ether are added to a mixture of 45 g of acrylonitrile, 33 g of cuprous chloride and 6 g of hydrochloric acid with stirring and cooling (-5 to ^{0 ° C.).} When the addition is complete, the organic layer is separated off and excess acrylonitrile is removed therefrom. The residue is heated under reflux with concentrated hydrochloric acid and the product obtained is distilled under reduced pressure; 11.2 g of α-chlorodecanoic acid are obtained at a temperature between 115 and 120 ° C./0.5 mm. Yield = 24 percent by weight.

Example 6

50 g of methyl ethyl ketone peroxide are added to a mixture of 50 g of acrylonitrile, 140 g of ferrous sulfate decahydrate and 30 g of hydrobromic acid in 130 ml of water. The mixture is stirred and cooled to -10 ^{to 0 ° C. during this process.} The organic layer is separated off, excess acrylonitrile is distilled off and the residue is heated to boiling temperature with concentrated hydrochloric acid. Distillation of the reaction mixture gives 18.7 g of Λ-bromovaleric acid at 84 to 87 ° C. / 0.6 mm. Yield = 22 percent by weight.

Example 7

One consisting of 80 g of acrylonitrile, 120 g of ferrous sulfate and 10 g of concentrated hydrochloric acid in 200 ml of water Mixture, while stirring and cooling, 50 g of methyl ethyl ketone peroxide in 30 ml of ethyl ether added. The procedure is as in Example 2 and 13.5 g% -chloro valeric acid is obtained. Yield = 21 percent by weight.

Example 8

40 g of methyl ethyl ketone peroxide are added to a mixture consisting of 50 g of cuprous chloride, 80 g of methyl acrylate and 8 g of hydrochloric acid in 200 ml of water. The temperature is kept at -10 and -5 ° C. The organic layer thus formed is fractionally distilled. At 160 ⁰ C will retain 13.6 g oc-Chlorvaleriansäuremethylester. Yield = 20 percent by weight.

Example9

First a solution of hydrogen peroxide in ether is prepared by adding a 30% aqueous solution Hydroperoxide solution extracted with ether. There is no need to fear an explosion.

98 g of cyclohexanone are dissolved in 36 g of an ethereal solution thus obtained, and the mixture is dissolved for 24 hours kept at room temperature. After the ether has been removed, the residue (200 ecm) reacts used.

The cyclohexanone peroxide obtained and 106 g of acrylonitrile are added simultaneously within 30 minutes with stirring to a mixture consisting of 63 g of cuprous chloride, 36 g of hydrochloric acid and 350 g of water. The temperature is thereby maintained by external cooling with ice to ⁰ -5 C. When the addition is complete, the mixture is brought back to room temperature and the oily layer separated while acrylonitrile is recovered from the aqueous layer.

The acidic portion is extracted from the organic layer by treatment with sodium bicarbonate solution; the neutral part consists essentially of cyclohexanone. When acidifying the alkaline solution an acid mixture precipitates, which is separated off, dried, then with 150 ecm of sulfuric acid-containing methyl alcohol heated to boiling and then distilled. After a preliminary run at 90 to 108 ° C / 16 mm the methyl ester of α-chlorazelaic acid passes between 110 and 130 ° C./0.8 mm. Yield = 45 percent by weight.

Example 10

The peroxide produced from 98 g of cyclohexanone as in the previous example is simultaneously with 385 g of butyl acrylate with stirring in the course of 40 minutes one of 200 ml of water and 140 ml of an existing mixture of acetone in which 70 g of hydrochloric acid and 63 g of copper (I) chloride are dissolved,

set; the temperature is kept at -5 ° C.

The mixture is then brought back to room temperature and the acetone is distilled off. The organic layer is drawn off and from it the acidic part, essentially of which is cyclohexanone and butyl acrylate existing neutral portion by treatment with a sodium carbonate solution separated. The acidic part is esterified by boiling with methyl alcohol containing sulfuric acid, then distilled off. After a first run at 100 and 118 ° C / 16 mm, the butyl ester of -chlorazelaic acid goes (110 g) between 130 and 145 ° C / 0.6 mm across.

Example 11

65 g of cyclohexanone peroxide are added with stirring to a solution consisting of 120 g of ferrous sulfate heptahydrate and 270 ml of concentrated hydrochloric acid in 170 ml of water. At the same time, 83 g of acrylonitrile are added and the temperature is kept ^{at -5 to 0 ° C. by external cooling.} The addition is completed in 45 minutes.

If one proceeds as in Example 1, g of the methyl ester of α-chlorazelaic acid are obtained. Bp. _{0> 8} = 125 ⁰ C. Yield = 47 percent by weight.

Claims (1)

Claim: Process for the preparation of ^ -Chlor- or (X-bromo derivatives of saturated aliphatic mono- or dicarboxylic acids, characterized in that cyclic or acyclic ketone peroxides with acrylonitrile or a low molecular weight acrylic acid alkyl ester and hydrochloric or hydrobromic acid in the presence of an iron (II) or copper (I) salt, preferably cuprous chloride or ferrous sulfate at a temperature between -20 and + 6O ⁰ C, preferably between -10 and + 10 ° C, is reacted in an existing water, aqueous alcohol or aqueous acetone medium.