CS253816B1 - Process for preparing chlorinated 2-chloromethanesulfonylaminodiphenyl ethers - Google Patents

Abstract

The object of the invention is a method for preparing chlorinated 2-chloromethanesulfonylaminodiphenyl ethers of the general formula where X is Cl or H, with at least one X representing Cl in position 4 or 4'. The object was achieved according to the invention in that the chloromethanesulforylation is carried out without the presence of a catalyst at a temperature of 80 to 160 °C.

Description

The invention relates to a process for the preparation of chlorinated 2-chloromethanesulfonylaminodiphenyl ethers by chloromethanesulfonylation of the corresponding 2-aminodiphenyl ethers without the use of a catalyst.

Those compounds of the formula NHSO _2% CH ₂ Cl wherein X is either Cl or H, where at least one X is Cl in position 4 or 4 ', are being used as follows ohloraci for protecting wool and polyamide textile materials against pests.

The prior art process consisted of chloromethanesulfonylation of the corresponding aminodiphenyl ethers using pyridine as a catalyst in an environment of non-polar organic solvents at 20 ° C. The use of pyridine as a chloromethanesulfonylation catalyst has drawbacks for its known toxic properties and unpleasant odor. Further disadvantages are that the recovery of pyridine, which is used at least in equimolar amounts, is expensive from the aqueous medium after completion of the reaction and does not proceed with a satisfactory yield. This contributes, on the one hand, to increased material costs for the preparation of these amides and, moreover, the non-regenerated part of the pyridine pollutes the waste water.

The above-mentioned disadvantages are overcome by the process according to the invention, characterized in that the reaction is carried out in the absence of catalyst at a temperature of 80 to 160 ° C.

The rate of reaction favorably affects the removal of the hydrogen chloride formed from the reaction mass. This can be achieved either by introducing an inert dry gas into the reaction medium or by carrying out the reaction while boiling the non-polar solvent used.

However, removing hydrogen chloride from the reaction by these methods is not a prerequisite for carrying out the reaction, given that the solubility of hydrogen chloride in organic solvents is very low in the temperature range of 80-160 ° C.

Example 1

Dissolve 25.4 g of 2-amino-4,4'-dichlorodiphenyl ether in 160.0 g of tetrachlorethylene and add, with stirring, to an apparatus equipped with a reflux condenser.

17.9 g of chloromethanesulfonyl chloride, heated to boiling point, i.e. about 121 ° C, where it is maintained for 20 hours. The hydrogen chloride produced by synthesis and the residues in the condenser of uncondensed tetrachlorethylene are absorbed into water. The reaction mixture was then diluted

600.0 g of water, basified with 40% aqueous sodium hydroxide solution for mimosa positive reaction, and after separation, the aqueous phase containing the sodium salt of 2-chloromethanesulfonylamino-4,4'-dichlorodiphenyl ether is filtered with

5.0 g carborafine. The clear solution was acidified to pH 3 with hydrochloric acid. The precipitated amide was filtered off, washed with water until neutral and dried. It is obtained

27.8 g of 100% 2-chloromethanesulfonylamino-4,4'-dichlorodiphenylether, i.e. 75.8% of theory based on the amine employed.

3.2 g of unreacted amine contained in carbon tetrachloride can be returned to the next experiment after dewatering.

Example 2

Distilled 25.4 g of distilled 2-amino-4,4'-dichlorodiphenyl ether are dissolved in 86 g of toluene and 18 g of chloromethanesulfonyl chloride are added at boiling point over 12 hours. After the addition, the reaction mixture was boiled for a further 42 hours. The isolation was carried out as in Example 1.

It is obtained

25.1 g of 100% 2-chloromethanesulfonylamino-4,4'-dichlorodiphenyl ether = 68.5% of the theoretical for the amine used.

Example

25.4 g of 2-amino-4,4'-dichlorodiphenyl ether are dissolved in 150.0 g of 1,2-dichloroethane and added at 20 ° C.

17.9 g of halomethanesulfonyl chloride.

While stirring, it is heated to a boiling apparatus at about 87 ° C and maintained at this temperature for 32 hours. After cooling, the reaction mixture was diluted with water and washed with acidic water-soluble components. Thereafter, the 2-chloromethanesulfonylamino-4,4 ' -dichlorodiphenyl ether is converted into the aqueous phase as sodium salt by the sodium hydroxide solution. Acidification with hydrochloric acid gave, after filtration, 9.8 g of 100% 2-dichloromethanesulfonylamino-4,4'-dichlorodiphenyl ether (26.7% of theory for the amino compound used).

The unreacted aromatic amine dissolved in 1,2-dichloroethane is returned to chloromethanesulfonylation.

Example 4

Distilled 25.4 g of distilled 2-amino-4,4'-dichlorodiphenyl ether are dissolved in 111.0 g of chlorobenzene and added

18.0 g of chloromethanesulfochloride. Heat to 132 ° C and hold for 20 hours. The gaseous isolation and absorbance were carried out as in Example 1.

It is obtained

26.08 g of 100% 2-chloromethanesulfonylamino-4,4'-dichlorodiphenyl ether, which is 71.2% of theory based on the amine used.

Example5

28.85 g of 2-amino-4,2 ', 4'-trichlorodiphenyl ether of technical grade are dissolved in 130,00 g of 1,2-dichlorobenzene, added

17.90 g of chloromethanesulfonyl chloride. The reaction mixture was heated to 160 ° C and maintained at this temperature for 24 hours. The isolation was carried out as in Example 1. It was obtained

28.3 g of 100% 2-chlormetynsulfonylamino-4,2 ', 4 -trichlordifenyléteru ^1, that is 70.5% theory on the amine used.

Example 6

Dissolve 25.4 g of distilled 2-amino-4,4'-dichlorodiphenyl ether in

87.0 g of toluene and added

17.9 g of chloromethanesulfonyl chloride. After addition, dry nitrogen gas was started and the reaction mixture was heated to boiling and maintained at this temperature for 26 hours. The isolation was carried out analogously to Example 1. It was obtained

19.9 g of 100% 2-chloromethanesulfonylamino-4,4'-dichlorodiphenyl ether, i.e. 54.3% of theory per amine used.

Claims (1)

OBJECT OF THE INVENTION A process for the preparation of chlorinated 2-chloromethanesulfonylaminodiphenyl ethers of general formula X NHSO ₂ CH ₂ C where X is Cl or H, where at least one X is Cl in position 4 or 4 'by reaction chloromethanesulfonyl chloride with the appropriate chlorinated 2-aminodifenyléterem in an organic solvent, characterized in that the chlormetansulfonylace carried out without the presence of the catalyst at 80 160 ° C.