PL97750B2 - - Google Patents

Description

The subject of the invention is a method of obtaining new hard-to-dissolve styryl dyes in water, but dissolving in both hydrophilic and hydrophobic solvents organic.

The dyes obtained by the process of the invention are represented by the general formula 1, in which A is cyano, an esterified carboxyl group or a N, N-dialkylaminocarboxyl group nylon, B is an aliphatic radical with 1 to 4 carbon atoms, a cyanoalkylene group or an esterified group carboxyalkylene, Xi is a hydrogen or chlorine atom or a methyl, methoxy or ethoxy group low, X2 is hydrogen or X! and X2 together complete a hexagonal aromatic ring, Y is a hydrogen atom or a methyl, methoxy or ethoxy group, R is an alkylene group, and Ri - alkyl group.

The dyes in question differ from the known styryl dyes by the presence of the group / R-COOR —N in a molecule.

^ B It was found that the solubility of the dyes in question in hydrophilic or hydrophobic solvents in organic solvents depends on the length of the carbon chains in the residues R and Ri and in the substitution towards B.

In the method according to the invention, in the first place, the amine of the general formula 2 is transformed, in which the symbols have the meaning given above, w an aldehyde of general formula III in which the symbols have the above given meaning. The aldehyde synthesis is carried out by any known method, preferably the Wills method meyer, by treating the above-mentioned amine at 80 ° C with dimethylformamide in the presence of oxygen phosphorus chloride. After the synthesis of the aldehyde is completed, the reaction mass is diluted with water, while the aldehyde it is separated in the form of an oil, which is separated from the aqueous layer and then, optionally afterwards, is used before drying, condensation with dinitrile of malonic acid or a derivative of cyanoacetic acid.2 97 750 The cyanoacetic acid derivatives used in the process according to the invention are esters of this acid and alcohols holi containing 1-6 carbon atoms or amides of this acid, substituted on the nitrogen with aliphatic residues, containing 1-4 carbon atoms. The condensation process is preferably carried out at reflux temperature on the medium alcohols such as methanol or ethanol in the presence of reducing agents such as piperidine. I get bright yellowing with very good lightfastness and thermal durability within 2-3 to 5 on a five-point scale. The thermal stabilities of these dyes depend on the type of base penetrations contained in the dye molecule. The highest thermal stability have dyes, containing large number of long chain substituents.

These dyes dyes hydrophobic synthetic fibers, mainly polyester, polyamide, acetate polyacrylonitrile and polyacrylonitrile baths from water baths by depletion or padding, drying and fixation as well as solvent baths, the method of padding, drying and reheating.

For dyeing from water baths, the dyes obtained by the method according to the invention are used in the form dispersed powders or suspensions, which are prepared in the same way as powders and suspensions disperse dyes. Baths or suspensions prepared from these powders are very stable and not show the phenomena of agglomeration or loss of dyes even after prolonged heating of the bath at the temperature round of boiling.

For dyeing from solvent baths, these dyes are used in the form of powders, not containing them skimpy dispersants or in the form of solutions with a high concentration of dye up to %. Preparing solutions of such a high concentration from the dyes in question is very possible good solubility of these dyes in organic solvents, reaching in long cases carbon chains in the substituents R, Ri and B 400 g / l.

The invention is illustrated by the following examples, where parts and percentages mean parts and percentages by weight. in.

Example I. To 100 parts of dimethylformamide are added dropwise while stirring at temperature 0-5 ° C 30 parts of phosphorus oxychloride, then 42.1 parts are added to the reaction mass at 10 ° C. 2-methoxy-5-methylaniline-N, N-diacetic acid diisohexyl ester. Everything warms up to temperature temperature 80 ° C and kept under these conditions for 4 hours. The reaction mass is then cooled to temperature 40 ° C and poured into 40 parts of ice water and neutralized with ammonia to the pH = 7-8. Separated in the form In the oil, the aldehyde is separated from the aqueous layer, washed with water and dried at 40-50 ° C. Dried The aldehyde is dissolved in 60 parts of methanol, added to the resulting solution 8 parts of dinitrile acid malonic acid and piperidine in an amount of about 1% in relation to the large amount of reaction mass and heats the whole at a temperature boil within 5 hours. A yellow dye is released from the reaction mass, which is filtered off after cooling the mass, washed with methanol and dried.

By following the method described in Example I, using aromatic amines as starting compounds tics and the malonic or cyanoacetic acid derivatives given in the table below are obtained yellow dyes of general formula 1. By appropriate selection of aromatic amines and malonic acid derivatives or cyanoacetic acid, dyes with different solubilities in organic solvents are obtained different and different thermal stabilities.

Table Example II III "IV V VI ..

VII.

VIII Aromatic amine anilino-N-cyanoethyl-N-acetic acid butyl ester 1-naphthylamino-N, N-diacetic acid diethyl ester 3-Methyl-N-ethylaniline-N-acetic acid methyl ester acid dibutyl ester 2,5-dimethoxyaniline-N, N-diethyl the two hexyl acid ester 2,5-diethoxyaniline-N, N-diacetic N-butylaniline-N-caproic acid butyl ester 3-Chloro-N-ethylaniline-N-acetic acid butyl ester Malonic acid derivative or cyanoacetic acid malonic acid dinitrile hexyl cyanoacetate malonic acid dinitrile N, N-dimethylcyanacetamide malonic acid dinitrile N, N-Dibutylcyanacetamide Malonic acid dinitrile 97 750 3 Patent pending A method of obtaining new styryl dyes of the general formula I, in which A is a group cyano esterified carboxyl group or N, N-dialkylaminocarbonyl group, B is the radical aliphatic with 1-4 carbon atoms, cyanoalkylene group or esterified carboxyalkylene group, Xi represents a hydrogen or chlorine atom or a methyl, methoxy or ethoxy group, X2 is an atom hydrogen or Xx and X2 together form a hexagonal aromatic ring, Y is hydrogen or a methyl, methoxy or ethoxy group, R is an alkylene group, and Rx is an alkyl group, by synthesize aromatic aldehydes by any known method, preferably the Willsmeyer method, by reactions an aromatic amine with dimethylformamide in the presence of phosphorus oxychloride and subsequent condensation to obtain mango aldehyde with malonic acid dinitrile or derivatives of cyanoacetic acid, characterized by t y m that the starting compound in the synthesis of aromatic aldehydes is a compound of general Formula 2, in which the symbols have the above meanings, and as derivatives of cyanoacetic acid in the reaction condensation with the aromatic aldehydes of the general formula III, wherein the symbols have the meanings given above, the esters of cyanoacetic acid and alcohols containing 1-6 atoms are used carbon or amides of this acid, substituted by the nitrogen with aliphatic residues containing 1-4 atoms coal.

NC Jf -C ^ CH ^% N ^ -C00R ' 1 2 pattern 1 X, X, yR-COOR, x2 pattern 2 -0- *: B 2 pattern 3 * \