DE1061924B - Process for the preparation of water-insoluble monoazo dyes - Google Patents

Description

Process for the preparation of water-insoluble monoazo dyes Subject the invention is a process for the preparation of water-insoluble monoazo dyes, which are based on cellulose ester fibers (e.g. acetate rayon), synthetic polyamide fibers, Pull up polyvinyl fibers and terephthalic acid ester fibers in yellow to orange tones and their colorations are characterized by excellent washfastness. Contain Groups which enable the monoazo dyes to form metal complexes can be used by post-treating the dyeings with metal-releasing agents, their washfastness properties still improve. Some of the new dyes are also used for coloring paints, Oils, synthetic resins or synthetic fibers in the mass are suitable. Some dyes also dye wool and natural silk. The procedure for their preparation consists in that one mole of the diazo compound from an optionally further substituted 1-aminophenyl-4-carbamic acid ester with 1 mole of one in the ortho or para position mononuclear ones coupling to the oxy group, free of carboxylic acid and sulfonic acid groups aromatic oxy compound combined.

Another embodiment of the process consists in adding 1 mole of an aminomonoazo compound of the composition where R is the radical of a mononuclear aromatic oxy compound coupled in ortho or para position to the oxy group and free of carboxylic acid and sulfonic acid groups, and the nucleus A can carry any substituents customary in azo dyes with the exception of water-solubilizing groups, with 1 mol of a chloroformic acid ester.

The new water-insoluble monoazo dyes have the composition wherein R and A have the abovementioned meaning and R, denotes the remainder of an alcohol or oxybenzene.

As coupling in ortho- or para-position to the oxy group, of carboxylic acid and mononuclear aromatic oxy compounds which are free from sulfonic acid groups are suitable z. B. optionally by halogen, alkyl, alkoxy, amino, alkylamino, dialkylamino, Acylamino or sulfonylamino substituted oxybenzenes.

The radical of an alcohol denoted by R1 in formula (II) or Oxybenzene can, in particular, be the radical of a branched or unbranched, optionally Aliphatic groups containing hydroxyl groups, ether groups and / or secondary amino groups Alcohol having 1 to 6 carbon atoms, one through aryl, aryloxy, or a hetero ring substituted aliphatic alcohol with a total of no more than 11 carbon atoms and one optionally by halogen atoms and / or methyl, methoxy, ethoxy, Represent dimethylamino or diethylamino substituted oxybenzene.

The core A bonded in the 1,4-position can, by definition, contain further have customary substituents in azo dyes, e.g. B. halogen atoms, hydroxy, Methyl, methoxy, ethoxy, nitro, alkylsulfonyl and / or alkylaminosulfonyl groups.

The coupling of the diazo compound with the azo component after the first Embodiment of the method can be in acidic, alkaline or neutral medium take place.

The 1-aminophenyl-4-carbamic acid esters used as starting materials can be obtained, for example, by reducing nitro compounds of the composition wherein R, and A have the abovementioned meaning, or by partial hydrolysis of acylamino compounds of the general formula in which R1 and A likewise have the abovementioned meaning, are prepared. The reaction of the aminomonoazo compounds (I) with the chloroformic acid esters according to the second embodiment of the process is advantageously carried out in solution (e.g. in an inert organic solvent) or in a very fine aqueous suspension, preferably in the presence of a proton acceptor, the reaction temperature depending on execution can vary within wide limits.

If the resulting monoazo dye contains a free amino group, so this can then be carried out by acylation with an optionally substituted one aliphatic carboxylic acid or a functional derivative thereof or with a further moles of a chloroformic acid ester are reacted. Isolation of the Dyes are made by one of the usual basic operations such as filtration or concentration of the solvent or precipitation from the solvent by a suitable means.

The dyes are in suspension on acetate rayon, triacetate rayon and synthetic polyamide where R2 is hydrogen or a lower branched or unbranched alkyl radical, R3 is H, OH, alkoxy, dialkylamino or a lower alkyl radical, R4 is an acyl radical having between 1 and 18 carbon atoms and n is an integer between 0 and 5.

The following examples show how the present process works can be executed. Parts are parts by weight and percentages are percentages by weight to be understood, the temperatures are given in degrees Celsius, and the melting points are uncorrected.

Example 1 27.4 parts of the hydrochloride of 1-aminophenyl-4-carbamic acid (3'-methoxy) butyl ester are finely powdered and in the presence of 150 parts of water and 23 parts of 30% Hydrochloric acid with a solution of 7 parts of sodium nitrite and 50 parts of water at 0 ° dianotiert. The diazo solution obtained is in the usual .Weise with a solution of 15.5 parts of 1-oxy-3-acetyl-aminobenzene in 300 parts of pyridine, in the presence of 11 parts of calcium hydroxide, combined at 3 to 5 °. After a while it becomes acidic. The precipitated dye is filtered off and dried. The resulting 1- (2'-acetylamino-4'-oxy) -phenylazophenyl-4-carbamic acid (3 "-methoxy) -butyl ester is obtained in good yield. The dye crystallizes from alcohol or ethyl acetate in beautiful yellow-orange needles with a temperature of 208 to 209 °. It dissolves in ethyl acetate greenish yellow, in concentrated sulfuric acid with orange color and dyes acetate silk, Triacetate rayon and synthetic polyamide fibers in yellow tones of exquisite Fastness to washing and sea water. The colors are also etchable and sublimable and lightfast. You can get dyes with similar properties if you the 1-oxy-3-acetylaminobenzene of the example by 1-oxy-3-trifluoroacetylaminobenzene, 1-oxy-3-monochloroacetylaminobenzene, 1-oxy-3-trichloroacetylaminobenzene, 1-oxy-3-oxyacetylaminobenzene, 1-oxy-3 butyrylaminobenzene, 1-oxy-3-isobutyrylaminobenzene, 1-oxy-3-crotonylaminobenzene, 1-oxy-3-methoxyacetylaminobenzene, 1-oxy-3- (3'-methoxy) -propionylaminobenzene, 1- Oxy - 3 - (4 '- methoxy) - butyrylaminobenzene, 1- Oxy-3 - (3' - oxy) - propionylaminobenzene, 1- Oxy - 3 - (4 '- oxy) fibers dyed, preferably in the presence of dispersing active compounds and at elevated temperature. You stand out particularly characterized by excellent washfastness. By mixing two or more dyes the composition (II) can be the draw power of the dyes in individual Cases still improve. Individual dyes are also very suitable for dyeing of acetyl cellulose in the mass with excellent wash, sublimation and lightfastness.

The new water-insoluble monoazo dyes have compared to the closest comparable monoazo dyes known from U.S. Patent 2366034 the advantage that their dyeings on acetate rayon have better seawater fastness exhibit.

The dyeing of acetyl cellulose from aqueous suspension or in the mass of particularly suitable water-insoluble monoazo dyes correspond to the Composition butyrylaminobenzene, 1-oxy-3-hexanoylaminobenzene, 1-oxy-3-dodecanoylaminobenzene, 1-oxy-3-tetradecanoylaminobenzene, 1-oxy-3-hexadecanoylaminobenzene, 1-oxy-3-octadecanoylaminobenzene, 1-oxy-3-phenylacetylaminobenzene, 1-oxy-3-benzoylaminobenzene, 1-oxy-3-hexahydrobenzoylaminobenzene, 1-oxy-3-methylsulfonylaminobenzene, 1-oxy-3-monoethylaminobenzene, 1-oxy-3-diethylaminobenzene or 1-oxy-3- [N- (4'-methyl) -phenylsulfonyl-N-methyl] -aminobenzene.

A dye bath is prepared from 0.6 parts of this with the help of Turkish red oil dispersed dye, 6 parts of a fatty alcohol sulfonate and 3000 parts of water. 100 parts of acetate rayon are added to the bath at room temperature and the mixture is warmed this within 1 hour to 80 ° and holds it for 1 hour at 80 °. After this Time the dyeing process is finished. The dyed material is taken out of the bath; washes it and dries it.

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 also as an aqueous paste intimately mixed with a dispersant and through suitable Drying can be converted into a dye powder.

The 1-aminophenyl-4-caxbamic acid (3'-methoxy) butyl ester used in this example is new and can be synthesized as follows: 100 parts water, 16 parts crystallized sodium acetate and 15 parts of 1-acetylamino-4-aminobenzene will be good mixed and cooled to 0 °. It is added dropwise to the reaction mixture with thorough stirring 18 parts of chloroformic acid (3-methoxy) butyl ester. When the reaction is over, the precipitate is filtered off, washed and dried. You get so the 1-acetylaminophenyl-4-carbanylic acid (3'-methoxy) butyl ester in good yield; it can still be purified by recrystallization from dilute alcohol and then melts at 128 °. 28 parts of the compound thus obtained are combined with 150 parts 10% hydrochloric acid boiled under reflux, a clear violet-tinged solution arises. As soon as the reaction has ended, the mixture is cooled and isolated the resulting chlorohydrate of 1-amino-phenyl-4-carbamic acid (3'-methoxy) butyl ester by Failure by any suitable means, e.g. B. acetone, or by evaporation under reduced pressure. The yield is very good.

Example 2 26.4 parts of the chlorohydrate of the 1-aminophenyl-4-carbamic acid phenyl ester are finely powdered and dianotized according to the instructions in Example 1 at 0 °. the obtained diazo solution is in the usual way with a solution of 11 parts of 1-oxy-4-methylbenzene, 15 parts of 30% sodium hydroxide solution and 25 parts of soda in 200 parts of water at 3 to 5 ° united. After a short time, the resulting monoazo dye is filtered off, Washed alkali-free with water and dried. 1- (2'-Oxy-5'-methyl) -phenylazophenyl-4-carbamic acid phenyl ester is obtained in good yield. The dye can be recrystallized from alcohol, whereby glossy orange leaves with a temperature of 186 to 187 °. It dissolves in ethyl acetate with greenish yellow, in concentrated sulfuric acid with orange color and colors synthetic polyamide fibers in yellow tones with excellent wash and sea water fastness. It also has excellent drawability on polyamide fibers; those with it The dyeings obtained are characterized by excellent washing, seawater, ironing and fastness to sublimation.

The 1-aminophenyl-4-carbamic acid phenyl ester used in this example is new and can be synthesized as follows: 100 parts water, 16 parts crystallized sodium acetate and 15 parts of 1-acetylamino-4-aminobenzene will be good mixed and cooled to 0 °. It is added dropwise to the reaction mixture with thorough stirring 19 parts of phenyl chloroformate. When the reaction is complete, filter the precipitate is washed and dried. The 1-acetylaminophenyl-4-carbamic acid phenyl ester is obtained in this way in good yield; it can be cleaned by dissolving it from alcohol and it will melt then at 190 °.

27 parts of this compound are mixed with 150 parts of 10% hydrochloric acid and 150 parts of ethyl alcohol refluxed until hydrolysis is complete. The reaction mixture is then cooled and the resulting chlorohydrate is isolated of the 1-aminophenyl-4-carbamic acid phenyl ester by precipitation with a suitable one Means, e.g. B. acetone, or by evaporation under reduced pressure. The yield is very good. Dyes with similar properties are obtained by using this Chlorohydrate of the 1-aminophenyl-4-carbamic acid phenyl ester by the chlorohydrate a 1-aminophenyl-4-carbamic acid alkylphenyl-; -alkoxyphenyl-, -benzyl-, -phenylethyl- or -morpholinoäthylesters replaced. Example 3 27.4 parts of the hydrochloride des 1-Aminophenyl-4-carbamic acid (3'-methoxy) -butyl ester are according to the information of the Example 1 dianotated. The diazo solution obtained is in the usual way with 11 Parts of 1-oxy-3-aminobenzene combined in dilute hydrochloric acid. After the clutch to the monoazo dye was completed by adding sodium acetate this filtered off, washed and dried.

35 parts of the dye thus obtained are at 100 ° with 100 parts Acetic anhydride digested; it is evaporated in vacuo and the dye is crystallized optionally from ethyl acetate at (F. 187 °). It dissolves in ethyl acetate with yellow and in concentrated sulfuric acid with a golden yellow color and dyes acetate silk and synthetic polyamide fibers in yellow tones with good fastness properties. . Example 4 27.4 parts of the hydrochloride of 1-aminophenyl-4-carbamic acid (3'-methoxy) butyl ester are finely powdered and dianotized according to the instructions in Example 1 at 0 °. the The diazo solution obtained is conventionally mixed with a solution of 26 parts of 1-oxy-3-decanoylaminobenzene combined in 300 parts of pyridine in the presence of 11 parts of calcium hydroxide at 3 to 5 °. After some time it is acidified, whereupon the precipitated dye is filtered off and is dried. The 1- (2'-decanoylamino-4'-oxy) phenylazophenyl-4-carbamic acid (3 "methoxy) butyl ester is obtained in good yield. The dye can be dissolved from alcohol, it melts then at 155 °. It dissolves in ethyl acetate with a greenish yellow color and stains Acetate artificial silk in the mass in yellow tones of excellent fastness to washing and over-dyeing. The dyeings are also smoke gas, peroxide bleach and highly lightfast.

Example 5 25.8 parts of 1-amino-2-methylsulfonylphenyl-4-carbamic acid ethyl ester, from 143 to 144 ° F., are finely powdered and in 152 parts of an 8% hydrochloric acid hot dissolved. The red solution obtained is cooled to 0 ° with thorough stirring and mixed with a solution of 7 parts of sodium nitrite and 50 parts of water. The received Diazo solution is filtered if necessary and in the usual way with a solution of 11.4 parts of 1-oxy-2-methylbenzene in 250 parts of water, 4 parts of sodium hydroxide and 15 parts of sodium carbonate combined at 3 to 5 °. After the coupling is completed the precipitated dye is separated off, washed neutral and dried. You get 1- (4'-Oxy-3'-methyl) -phenylazo-2-methylsulfonylphenyl-4-carbamic acid ethyl ester in good yield. The dye can be redissolved from diluted alcohol or ethyl acetate it then melts at 203 °. It dissolves in ethyl acetate with a greenish yellow; in concentrated sulfuric acid with orange color and dyes acetate rayon, triacetate rayon and synthetic polyamide fibers in yellow tones with excellent wash and sea water fastness. The colors are also etchable, resistant to sublimation, light and extremely easy to iron.

100 parts of acetyl cellulose are mixed with 300 parts of reading medium (930 /, acetone, 70 /, methanol), mixed briefly and left to swell overnight.

0.5 parts of the dye obtained are shaken simply by shaking dissolved in 85 parts of the solvent and added to the acetyl cellulose solution. The mixture is in an open vessel. Stirred until 60 parts of the solvent have evaporated.

The colored mass is now in the usual way in the spinning pot pressed and spun. The skeins obtained are ready for use.

The 1-amino-2-methylsulfonylphenyl-4-carbamic acid ethyl ester used in this example is new and can be obtained as follows: 18.6 parts 1,4-diamino-2-methylsulfonylbenzene are dissolved in 60 parts of anhydrous pyridine. With good external cooling and vigorous stirring, 11 parts of ethyl chloroformate are added dropwise so that the The temperature of the reaction mixture does not exceed + 10 °. After entering, stir one more 2 hours at room temperature and then 8 hours at 60 to 70 °. Now is the reaction ended; one lets cool to room temperature and carries under good Stir in a mixture consisting of 60 parts of water and 60 parts of ice. By The precipitated compound is acidified with hydrochloric acid and filtered off from the pyridine severed. Wash well with water and crystallizes out diluted alcohol several times. It then melts at 143 to 144 °.

The 1,4-diamino-2-methylsulfonylbenzene mentioned above can be prepared from 1-amino-2-methylsulfonyl-4-nitrobenzene can be obtained in good yield by one of the customary reduction methods.

Example 6 22.7 parts of 2'-oxy-5'-methyl-4-amino-1,1'-azobenzene become dissolved in 150 parts of anhydrous pyridine. With good external cooling and violent Stirring, 11.5 parts of ethyl chloroformate are added dropwise, so that the temperature of the mixture does not exceed + 20 °. Once everything has been entered, you can still stir 2 hours at room temperature and then 8 hours at 70 °. As soon as no starting product is more detectable, it is allowed to cool to 20 ° and diluted with a mixture, consisting of 250 parts of water and 200 parts of ice. By acidifying with hydrochloric acid the precipitated dye is converted into a filterable form. He is cut off abundantly washed out with water and dried. The 1- (2'-oxy-5'-methyl) -phenylazophenyl-4-carbamic acid ethyl ester is obtained in good yield. The dye can be recrystallized from alcohol or ethyl acetate and then melts at 155 °. It dissolves in ethyl acetate with a greenish yellow, in concentrated sulfuric acid with a red-orange color and dyes acetate silk and synthetic polyamide fibers in yellow shades with good washfastness. The colorations are also etchable and resistant to sublimation.

The table below describes other valuable disperse dyes which can be prepared by one of the specified processes. They correspond to the composition The meanings of R, R5, x and y are given in the correspondingly labeled columns. Another column contains the melting points of the new disperse dyes, and the last column lists the shades of the dyeings on acetate rayon, synthetic polyamide fibers and polyester fibers. Hue of Colorations on Bei- RX y R F. Acetate rayon game and synthetic Polyamide fibers 7 3-methoxybutyl HH 2'-oxy-5'-acetylaxninophenyl 174 ° greenish yellow 8 like. HH 2'-Oxy-4'-acetylamino- 208 ° like. 5'-methylphenyl 9 like. HH 4'-oxyphenyl 116 ° like. 10 the same. HH 4'-Oxy-5'-acetylaminophenyl 190 ° desgl. 11 desgl. HH 2'-oxy-5'-methylphenyl 128 ° desgl. 12 phenyl HH 2'-oxy-5'-tert-butylphenyl 166 ° desgl. 13 desgl. HH 4'-Oxy-5'-methylphenyl 187 ° desgl. 14 2-phenoxyethyl HH 2'-oxy-5'-tert-butylphenyl 194 ° desgl. 15 the same. HH 2'-Oxy-5'-methylphenyl 1710 the same. 16 desgl. HH 4'-Oxy-5'-methylphenyl 162 ° desgl. 17 2- (2'-methoxy) - HH 4'-oxyphenyl 108 ° desgl. ethoxyethyl 18 desgl. HH 4'-Oxy-5'-acetylaminophenyl 167 ° desgl. 19 ethyl HH 2 ', 4'-dioxyphenyl 130 ° desgl. Decomp. 20 like. HH 2'-Oxy-5'-methylphenyl 154 ° like. 21 ethyl HH 4'-oxy-5'-carbomethoxyphenyl 163 ° desgl. 22 2-ethoxyethyl HH 2'-oxy-5'-methylphenyl 122 ° desgl. 23.Methyl HH 2'-Oxy-5'-methylphenyl 166 ° desgl. 24 n-butyl HH 2'-oxy-5'-methylphenyl 127 ° desgl. 25 ethyl HH 4'-oxy-5'-methylphenyl 97 ° desgl. 26 2-ethoxyethyl HH 2'-oxy-S'-chlorophenyl 1210 desgl. 27 ethyl HH 2'-oxy-3'-carbäthoxyamino- 174 ° desgl. 5'-methylphenyl 28 Cyclohexyl HH 2'-Oxy-5'-methylphenyl 155 ° yellow 29 the same. HH 2'-acetylamino-4'-oxyphenyl 226 ° the same. 30 ethyl 2-chloro H desgl. 255 ° desgl. 31 like. 2-methoxy 5-methyl like.> 320 ° like. Hue of Colorations on At- Rb xy R F. Acetate rayon game and synthetic Polyamide fibers 32 ethyl. 2-methyl-H 2'-acetylamino-4'-oxyphenyl 265 ° yellow sulfonyl 33 the same. 2-Nitro H the same. 248 ° the same. 34 2-oxyethyl HH 2'-acetylamino-4'-oxyphenyl 228 ° desgl. 35 Allyl HH the same. 248 ° the same. 36 the same. HH 2'-Oxy-5'-xnethylphenyl 158 ° the same. 37 3-methoxybutyl HH 2'-amino-4'-oxyphenyl 133 ° desgl. 38 the same. HH 2'-propionylamino-4'-oxyphenyl 168 ° the same. 39 the same. HH 2 '- (4 "-Methyl) -phenylsulfonyl- 92 ° the same. amino-4'-oxyphenyl 40 2- (2'-methoxy) - HH 2'-acetylamino-4'-oxyphenyl 180 ° desgl. ethoxyethyl 41 ethyl 2-oxy H 2'-oxy-5'-methylphenyl> 300 ° desgl. 42 Phenyl HH 2'-Oxy-5'-isoamylphenyl 137 ° desgl. 43 the same. HH 2'-Oxy-5'-phenylphenyl 1510 the same. 44 3-Methoxybutyl HH 4'-Oxy-5'-aminophenyl 144 ° desgl. 45 like. HH 2 ', 4'-dioxyphenyl 157 ° like. 46 ethyl HH 4'-oxy-5'-isonitrosomethyl- 1610 desgl. phenyl 47 Phenyl HH 4'-Oxyphenyl> 300 ° desgl. 48 like. HH 2'-acetylamino-4'-oxyphenyl> 300 ° like. 49 2-Äthoxyäthyl HH desgl. 207 ° desgl. 50 ethyl 2-methyl- H 2'-oxy-5'methylphenyl 235 ° desgl. sulfonyl 51 phenyl HH 2'-oxy-5'-isooctylphenyl 124 ° desgl. 52 the same. HH 2'-Oxy-5'-cyclohexylphenyl 112 ° desgl. 53 2-phenoxyethyl HH 2 ', 4'-dioxyphenyl 168 ° desgl. 54 the same. HH 2'-acetylamino-4'-oxyphenyl 212 ° the same. 55 phenyl HH 2 ', 4'-dioxyphenyl> 300 ° desgl. 56 the same. HH 3'-Acetylamino-4'-oxyphenyl 1110 the same. 57 ethyl HH 2'-oxy-5'-tert-butylphenyl 135 ° desgl. 58 phenyl HH 2'-oxy-5'-acetylaminophenyl 196 ° desgl. 59 ethyl HH 2'-acetylamino-4'-oxyphenyl 240 ° desgl.

Claims (1)

PATENT CLAIM: A process for the preparation of water-insoluble monoazo dyes, characterized in that 1 mol of the diazo compound is obtained from an optionally further substituted 1-aminophenyl-4-carbamic acid ester with 1 mol of a carboxylic acid and sulfonic acid group coupling in ortho or para position to the oxy group, mononuclear aromatic oxy compound or that 1 mole of an aminomonoazo compound of the composition where R is the radical of a mononuclear aromatic oxy compound which is coupled in ortho or para position to the oxy group and is free of carboxylic acid and sulfonic acid groups and the nucleus A can carry any substituents customary in azo dyes with the exception of water-solubilizing groups, with 1 mol of a chloroformic acid ester implements. Documents considered: French Patent No. 801899; U.S. Patent Nos. 2,040,473, 2,366,034. When the application was made public, an explanatory staining table was displayed.