DE1219608B - Process for the preparation of water-insoluble monoazo dyes - Google Patents

Description

A process for producing water-insoluble monoazo dyes addition to the patent: 1065 112 subject of the main patent 1065 112 discloses a process for producing water-insoluble monoazo dyes, characterized in that 1 mole of the diazo compound optionally substituted from one, however, of water-solubilizing groups free amine of the benzene or naphthalene series or from a 2-aminothiophene or a 2-aminothiazole free of fused rings with 1 mol of a tertiary amine of the general formula n couples p-position to the amino group, where Y is a hydrogen atom or the radical - OCR, n is an integer, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and R 'is a cyanoalkyl radical or a polyfluoroalkyl radical and in which the nucleus A is further substituents with the exception of water-solubilizing groups, and the coupling product is esterified with an acid of the formula RCOOH or one of its functional derivatives when Y is a hydrogen atom.

It has now been found that valuable new water-insoluble monoazo compounds are also obtained if 1 mol of a tertiary amine of the general formula is used wherein the nucleus A can carry further substituents with the exception of water-solubilizing groups and both R are identical or different low molecular weight alkyl radicals which together contain at least one negative substituent and at least one hydroxyl group, in any order a) with 1 mole of the diazo compound from one in 2 -and 6-positions the same or different halogen atoms and optionally 1-amino-4-nitrobenzene containing substituents which are not water-soluble in the 3- and 5-positions and b) with at least 1 mol of an acid having 1 to 5 carbon atoms or a functional derivative thereof esterified. The new monoazo dyes thus obtained have the general formula where x and y are identical or different halogen atoms and both R are identical or different low molecular weight alkyl radicals which together carry at least one negative substituent and at least one - O-acyl radical containing 1 to 5 carbon atoms, and nuclei A and B are represented by groups which do not make water soluble can be further substituted.

Negative substituents on the N-alkyl radicals are, for. B. halogen atoms, nitrile groups or C-acyl groups. T he tertiary amines of the formula (1) may, for. B. in the 2- and / or 5-position _ee§ Benzolkemes # A # .by. Halogen atoms or low molecular weight alkyl, alkoxy or acylamino groups, the hydrogen atoms of which may have been completely or partially replaced by fluorine, be substituted ..

The coupling of the #diazo compound with the 4 azo component follows # orzügsweisb iii acidic medium, with advantage in the presence of acid-binding agents: The eliminated Monoazo dyes are filtered off and washed.

The acylation of the hydroxyl group can be carried out according to processes known per se with functional derivatives of an acid containing 1 to 5 carbon atoms, j # gif älls -i n ---'-- G - eg-en'w'ärt-- - -ein -es- . -acid-binding and / or a diluent that does not affect the reaction- take place. It is often useful to increase the temperature. The monoazo dyes can e.g. B. obtained by concentrating or distilling off the solvent or precipitating from the solvent and filtering. - The new compounds are excellent dyes, e.g. B. for cellulose ester fibers, (z. B. Acetate artificial silk or triacetate artificial silk), polyester fibers, isynthetic polyamide fibers and polyacrylonitrile fibers. Orange to yellowish brown dyeings are obtained which are very fast to light, smoke gas, perspiration, washing and sublimation. A particular advantage of the new dyes is that they can be combined with other dyes for the production of dyeings in fashion shades.

They are advantageously processed into dye preparations ' z. B. by grinding the dried dye mit.Dispergiermittel and optionally fillers or by kneading a dye paste with a dispersant and drying, e.g. B. in a vacuum or by sputtering. This can be used to prepare dye suspensions with which the aforementioned fibers and other hydrophobic fibers, threads and textile materials in general, e.g. B. with the addition of dispersants and other dyeing auxiliaries, preferably dyed in the heat. The drawability can often be improved by mixing two or more of the new dyes . Compared to the closest comparable dyes described in British Patent 813 906 and in U.S. Patent 2,045,324, the dyes which can be prepared according to the process have better lightfastness on polyester fibers . “ The parts mentioned in the examples are parts by weight, the percentages are percentages by weight. The temperatures are given in degrees Celsius.

Example 1 83 parts of 2,6-dichloro-4-nitro-1-aminobenzene are introduced into a nitrosylsulfuric acid prepared from 450 parts of concentrated sulfuric acid and 28.5 parts of sodium nitrite. The mixture is stirred for 4 hours at room temperature, the viscous reaction mass is charged - 1400 parts of water and 2400 parts of ice from and. destroys a small excess of volatile acid with sulfamic acid. To the clear diazo solution is added a solution of 76 parts of N-cyanoethyl-N-oxyäthylanilin - in 50 parts of a 30 0 /, by weight. Hydrochloric acid and 30 parts of ice. There is an instantaneous coupling. The paraffin suspension obtained is — after stirring for 1 hour — diluted with 7000 parts of water, filtered, washed acid-free and dried.

50 parts of the 2,6-dichloro-4-nitro-4 '- (N-cyanoethyl-N-oxyäthylamino) -1, l'-azobenzene obtained in this way together with 200 parts of acetic anhydride for 2 hours to SieLd6, n ", After heating up, small amounts of an impurity are filtered off and the filtrate is then diluted with "750 parts" of ethyl alcohol. When left to stand, the new dye crystallizes out. In the purified state, it melts at 132 to 133 ° in the usual way, e.g. by grinding with a dispersing agent and with sodium sulfate, to a dye preparation with the., acetal synthetic silk and polyterephthalic acid ester fibers in yellowish orange-brown shades with excellent fastness properties, especially with excellent light, smoke, and submersion fastness and wetness ,can.

One prepares z. B. a dyebath of 0.6 parts of the dye thus obtained and dispersed with the help of Turkish red oil, 6 parts of a fatty alcohol sulfonate and 3000 parts of water. Bringing at ZimnIertemperatur 100 parts Acetatkunstseide in the bath - a heated this, within one hour to 800 and holds it for 1 hour at this temperature. After this time, the dyeing process is over. The dyed material is taken out of the bath, rinsed and dried. It is colored in yellowish red-brown tones with excellent real properties.

To improve the dispersibility, the dye can before the dyeing process with suitable wetting agents, dispersants or emulsifiers, preferably in the presence of inorganic salts, e.g. B. sodium sulfate, are ground. It can also be intimately mixed as an aqueous paste with a dispersant and converted into a dye powder by suitable drying. Synthetic polyamide fibers are dyed by the same method at 90 to 100 ', terephthalic acid ester fibers at 120 to 130' under pressure or at 90 to 100 ' in the presence of carriers.

The same dye is obtained if 1- (N-cyanoethyl-N-acetoxyethylamino) benzene used as a coupling component.

A dye with similar properties is obtained if one 1- (N-Cyanäthyl-N-acetoxyäthylamino) -3-methylbenzene used as the coupling component.

Example 2 29.6 parts of 1-amino-2,6-dibromo-4-nitrobenzene are diazotized according to the instructions given in Example 1 , the reaction mass is poured into ice water, the excess of nitrous acid is removed with sulfamic acid and, if necessary, the solution is clarified by filtration. Then, at 0 to 5 ' em * e-cold, a solution of 23.2 parts of 1- (N-cyanoethyl-N-acetoxyethyl-amino) -benzene in 100 parts of glacial acetic acid is allowed to flow in and the mixture is stirred until the coupling reaction has ended. The dye is filtered off, washed acid-free and dried. It melts at 130 to 133 '. Finely dispersed, it can be used to dye acetate silk or polyester fibers. Orange-brown dyeings with excellent fastness properties are obtained.

Claims (1)

Patent claim: A process for producing water monoazo dyes according to Patent 1065 112 d, ABy in daßman1Mol a tertiary amine of the general formula in which the core A can carry further substituents with the exception of water-solubilizing groups and both R are identical or different low molecular weight alkyl radicals which together contain at least one negative substituent and at least one hydroxyl group, in any order a) with 1 mol of the diazo compound from one of water-soluble 1-amino-4-nitrobenzene containing substituents which are free in the 2- and 6-positions, identical or different halogen atoms and optionally in the 3- and 5-positions, and b) with at least 1 mole of 1 to 5 carbon atoms Acid or a functional derivative thereof to form a water-insoluble monoazo dye of the general formula wherein x and y are identical or different halogen atoms, and both R, identical or different low molecular weight alkyl radicals, and at least having along at least one substituent a 1 to 5 carbon atoms - carry 0-acyl group, mean and the nuclei A and B solubilizing by not water-soluble Group can be further substituted, esterified. References considered: British Patent No. 813,906; U.S. Patent No. 2,045,324. A coloring chart was displayed with explanations when the application was made public.