DE1061927B - Process for the preparation of water-insoluble azo dyes - Google Patents

Description

Method of Making Water-Insoluble Azo DyeQ Item the invention is a process for the preparation of water-insoluble azo dyes, which are suitable for coloring acetyl cellulose in the mass. Individual dyes also draw on cellulose ester fibers, on synthetic polyamide fibers and on Polyvinyl fibers, terephthalic acid ester fibers, preferably dispersing in the presence active compounds and at elevated temperature. Those dyes which are very sparingly soluble or completely insoluble in organic solvents can also be used with success as pigments.

Some of the new dyes are also used to color paints and oils and synthetic resins are suitable. Some dyes also dye wool and natural silk.

The yellow-orange to purple colorations obtained from the suspension on; the above-mentioned fibers are characterized by excellent washing, seawater, Sublimation, perspiration, ironing, heat setting and smoke gas fastness. The lightfastness the dyeing on polyamide fibers is good, that on the other fibers is very good good to excellent.

The spin dyeings have good to very good light, water, washing, Sweat, overdye, alkaline chlorine, sublimation, oxalic acid, dry cleaning, Flue gas, rubbing, ironing, peroxide bleaching and thermosetting fastness.

The new water-insoluble azo dyes correspond to the formula where x is hydrogen, halogen, the methyl, ethyl, methoxy or ethoxy radical, y is hydrogen, halogen, the methyl, ethyl, trifluoromethyl, methoxy, ethoxy or an alkanoylamino radical with at most 18 carbon atoms, R, an alkylene radical having 1 to 4 carbon atoms, R2 is an alkylene radical having 2 to 4 carbon atoms, Z is oxygen or the imino group, R3 is a cycloaliphatic or aromatic radical which is optionally further substituted with the exception of water-solubilizing groups or, if Z is oxygen, then also .an aliphatic radical, V -oxygen or the imino group when Z stands for the imino group, -and only the imino group when Z stands for oxygen, M hydrogen, halogen, the methoxy @, ethoxy, difluoro or trifluoromethyl, Cyano, carbalkoxy or where the symbols R3, Z and V have the meanings given at the beginning, or, if m is the number 2, a single bond, R4 is a mononuclear aromatic, mononuclear heterocyclic mononuclear, mononuclear heterocyclic, optionally substituted by substituents customary in azo dyes, with the exception of water-solubilizing groups - or binuclear heterocyclic radical and m is the number 1 or 2.

The process for their preparation consists in mixing m moles of a diazo compound optionally further substituted by substituents customary in azo dyes, with the exception of water-solubilizing groups, with 1 mole of a tertiary amine of the formula wherein x, y, R1, R2, R3, M, V, m and Z have the abovementioned meaning, combined.

As are diazo compounds free of water-solubilizing groups in particular by nitro groups, acyl groups, halogen atoms, cyano groups and / or Aminobenzenes, aminothiophenes, aminothiazoles substituted by alkylsulfonyl groups, Aminothiodiazoles or aminobenzothiazoles are suitable.

The coupling of the diazo compound with the azo component takes place in an acidic manner, optionally buffered medium.

Compared to the US Pat. No. 2,659,719 and the British Patent 422 873 draw known, next comparable monoazo dyes the monoazo dyes obtainable according to the process are characterized in that their melting points are higher, with the result that the new monoazo dyes on triacetatrayon and polyester fibers provide level dyeing while using the monoazo dyes of the two patent specifications mentioned, stained dyeings on the fibers mentioned receives.

In the following examples, parts are parts by weight and under percentages are to be understood as percentages by weight; the temperatures are in degrees Celsius and the melting points are uncorrected. Example 1 17.5 parts of 1-amino 2-chloro-4-nitrobenzene, 125 parts of water and 42.5 parts of 30% hydrochloric acid mixed, stirred for some time and then by adding a solution of 7 parts of sodium nitrite and 25 parts of water diazotized at 0 °. The resulting diazo solution is 0.5 parts Amidosulfonic acid is added, the mixture is stirred for some time and then filtered. That The filtrate is treated with a solution of 26 parts of the ethyl carbamic acid ester of 1- (N-ethyl-N-ß-hydroxyethyl) -amino-3-methylbenzene, 13 parts of 30% hydrochloric acid and 200 parts of water combined at 0 °, whereupon a Solution of 70 parts of sodium acetate in 100 parts of water is added dropwise. After some Time the clutch is over. The precipitated dye is filtered off and dried him.

The resulting ethyl carbamic acid ester of 1- [4 '- (N-ethyl-N-ß hydroxyethyl) -amino-2'-methyl] -phenylazo-2-chloro-4-nitrobenzene is obtained in good yield. The dye crystallizes from ethanol in beautiful red crystals of 130 °. It dissolves in ethyl acetate with a red color and stains Acetate rayon, triacetate rayon and synthetic polyamide fibers in scarlet red Tones.

Prepare a dyebath from 0.6 parts of the above example available and with the help of Turkish red oil dispersed dye, 6 parts of a fatty alcohol sulfonate and 3000 parts of water. You go at room temperature with 100 parts of acetate rayon in the bath, heats it up within 1 hour to 80 ° and keep it at 80 ° for 1 hour. After this time, the dyeing process is finished. The dyed material is taken out of the bath, rinsed and dried.

To improve the dispersion, the dye can be added before the dyeing process with suitable wetting agents, dispersants or emulsifiers, preferably in Presence of inorganic salts, e.g. B. Glauber's salt, be ground. He can too as an aqueous paste intimately mixed with a dispersant and through suitable Drying can be converted into a dye powder.

If one combines the same amount of the same in a corresponding way Diazo compound with 30 parts of the ethyl carbamic acid ester of 1- (N-ß-cyanoethyl-N-ß-hydroxyethyl) -amino-3-methylbenzene, a red dye with a melting point of 159 ° is obtained.

If one combines the same amount of the same in a corresponding way Diazo compound with 30 parts of the carbonic acid phenyl ester amide of 1- (N- (ethyl-N-ß-aminoethyl) -amino-3-methylbenzene or with 30 parts of the phenylcarbamic acid amide of 1- (N-ethyl-N-ß-aminoethyl) -axnino-3-methylbenzene, this gives two dyes which dissolve in acetone with a red color.

Table 1 describes further valuable monoazo dyes which are obtained in Example 1 by suitable replacement of the diazo and azo components. They correspond to the general formal and are identified in the table by the symbols R4, R and y as well as by their melting point. Table 2 describes further valuable monoazo dyes which are obtained in Example 1 by suitable replacement of the diazo and azo components. They correspond to the general formula (III) and are identified in the table by the symbols R4, R6 and y, by their melting point and / or by the shade of their dyeings in artificial silk. Table 2 Hue of Example R4 y RS F. Colorings in Acetate rayon 10 2-chloro-4-nitrophenyl methyl phenylcarbamic acid ethyl 150 ° red 11 2-chloro-4-methylsulfonylphenyl methyl like 180 ° red 12 4-nitrophenyl methyl like 186 ° scarlet red 13 5-methylsulfonylbenzothiazolyl-2-chloro like 209 ° red 14 4-nitrophenyl hydrogen ethyl 170 ° scarlet red 15 4-nitrophenyl methyl ethyl 173 ° scarlet red 16 4-nitrophenyl hydrogen methyl 184 ° scarlet red 17 2-chloro-4-methylsulfonylphenyl methyl ethyl 133 ° red 18 5-methylsulfonylbenzothiazolyl-2-hydrogen ethyl - red 19 the same. Methyl 2'-cyanoethyl - red 20 the same hydrogen 2'-cyanoethyl - red 21 4-cyanophenyl chlorine phenylcarbamic acid ethyl 193 ° red-orange 22 like. Methyl Ethyl 155 ° like. 23 4-methylsulfonylphenyl hydrogen 2'-cyanoethyl. 116 ° the same. 24 2-chloro-4-methylsulfonylphenyl like. Like. 164 ° like. 25 4-Nitrophenyl the same. The same. 164 ° scarlet fever 26 2-chloro-4-nitrophenyl like the same 170 ° red 27 4-chlorophenyl like. Same. 139 ° yellow 28 4-propionylphenyl like like 145 ° orange 29 4-acetylphenyl like. Like. 154 ° like. 30 4-Dimethylaminosulfonylphenyl like. Same. 158 ° reddish yellow 31 4-cyanophenyl like the same 156 ° red-orange 32 2-cyano-4-nitrophenyl like. Same. 160 ° bluish red 33 2-chloro-4-dimethylaminosulfonyl like. Same. 177 ° red-orange phenyl Example 34 20.5 parts of 1-amino-2-chloro-4-methylsulfonylbenzene, 125 parts of water and 42.5 parts of 30% hydrochloric acid are mixed, stirred for some time and then by adding a solution of 7 parts of sodium nitrite and 25 parts of water diazotized at 0 °. The diazo solution obtained is mixed with 0.5 part of sulfamic acid, stirred for some time and then filtered. The filtrate is combined with a solution of 27 parts of the bisphenylcarbamic acid ester of N, N'-bisphenyl-N, N'-di (2'-hydroxyethyl) ethylenediamine in 250 parts of 80% formic acid at 0 °, whereupon a solution of 70 parts of sodium acetate in 100 parts of water is added dropwise. After a while, the clutch is over. The precipitated dye is filtered off and dried. The resulting disazo dye is obtained in good yield. It dissolves in ethyl acetate with a red color and dyes acetate silk in the mass in scarlet shades.

To dye acetate rayon in bulk, proceed as follows: 100 parts of acetyl cellulose are made in 300 parts of a solvent mixture 93% acetone and 7% methanol were added. The mass is mixed for a short time and lets them swell overnight. 0.5 part of the monoazo dye obtainable according to Example 10 by simply shaking in 85 parts of the same solvent mixture solved. The solution of the acetyl cellulose solution is added and the mixture is stirred in an open vessel until 60 parts of the solvent have evaporated. The colored mass is then pressed into the spinning pot in the usual way and spun. The threads obtained are colored scarlet; the colorations stand out good fastness properties.

EXAMPLE 35 7.5 parts of sodium nitrite are converted into 60 parts of 98% at 60 ° Sulfuric acid entered. The nitrosylsulfuric acid obtained is cooled and diluted at 10 ° with 140 parts of glacial acetic acid. 45.6 parts of 2-amino-5-methylsulfonylbenzothiazole are now carried one, destroyed after about 2 hours the excess nitrite and combined by adding of urea at 5 ° the resulting diazo solution with a solution of 27 parts of the Bisphenylcarbamic acid ester of N, N'-bisphenyl-N, N'-di- (2'-hydroxyethyl) ethylenediamine in 100 parts of glacial acetic acid. After a while, the coupling is over. After working up a red dye is obtained which; recrystallized from ethyl alcohol, at 112 ° melts and acetate silk in the mass in brilliant red tones with excellent Dyes fastness properties.

If one combines the same amount of the same in a corresponding way Diazo compound with 42 parts of the bisphenylcarbamic acid ester of N, N-di- (2'-hydroxyethyl) aminobenzene, this gives a red dye with a melting point of 110 ° and an acetone solubility of 80 g / liter. He dyes acetate silk in bulk in very real and brilliant colors red tones.

Claims (1)

Claim: Process for the preparation of water-insoluble azo dyes, characterized in that m mol of a diazo compound optionally further substituted by substituents customary in azo dyes, with the exception of water-solubilizing groups, is mixed with 1 mol of a tertiary amine of the formula wherein x is hydrogen, halogen, the methyl, ethyl, methoxy or ethoxy radical, y is hydrogen, halogen, the methyl, ethyl, trifluoromethyl, methoxy, ethoxy or an alkanoylamino radical with at most 18 atoms, R is an alkylene radical with 1 to 4 carbon atoms, R, an alkylene radical with 2 to 4 carbon atoms, Z is oxygen or the imino group, R3 is an optionally further substituted cycloaliphatic or aromatic radical with the exception of water-solubilizing groups or, if Z is oxygen, then also one aliphatic radical, V oxygen or the imino group when Z stands for the imino group, and only the imino group when Z stands for oxygen, M hydrogen, ralogen, the methoxy, ethoxy, difluoro or trifluoromethyl, cyano, carbalkoxy radical or where R3, Z and V have the abovementioned meaning, or, if m is the number t, then a single bond and m is the number 1 or 2, combined. Documents considered: ÜSA. Patent No. 2,659,719; British Patent No. 422 843. A coloring table with explanatory notes was displayed when the application was published.