DE1079756B - Process for the preparation of water-soluble dyes containing methylol groups - Google Patents

Description

Process for the preparation of water-soluble methylol groups Dyes It has been found that water-soluble dyes containing methylodol groups can be used obtained when anthraquinone or - optionally metal-containing-azo dyes or intermediate products required for the production of these dyes, the reactive ones Contains hydrogen atoms in a weakly acidic to alkaline medium with formaldehyde or formaldehyde-releasing agents and in the case of dye intermediates converts the methylodic compounds obtained into dyes.

The azo and anthraquinone dyes which can be used as starting materials for the process can the reactive hydrogen atoms z. B. in activated methylene or in phenolic hydroxyl or sulfhydryl groups, also in carboxamide, sulfonic acid amide, Urea or triurea groups or in heterocyclic, such as lactam, Contain thiolactam or melamine-like residues. One can implement this Dyes, for example, have the effect that the - possibly still water-moist - Make colored pastes with aqueous alkali or alkali carbonate solution, the dough with an amount of aqueous to be measured according to the number of methyl iodine groups to be introduced Formaldehyde and optionally mixed with sodium carbonate solution and put in the cold stirs until complete implementation. Then the resulting dye will through Addition z. B. precipitated from sodium chloride, filtered and gently dried.

Dye intermediates suitable for the process are all those those, such as the intermediates of azo dyes with phenodic End coupling components, without applying higher temperatures in neutral to weak alkaline medium to be further processed to the dyes. Even in the case of the Intermediate products can be converted to compounds containing methylol groups in a simple manner by dissolving or suspending in water, optionally under Adding alkaline agents, and by stirring with one according to the number of those to be introduced Amount of aqueous formaldehyde solution measured by methylod groups at normal or moderate levels elevated temperatures, so that no condensation occurs, until the end accomplish the implementation. Then the intermediate product containing methylol groups becomes in a weakly alkaline to neutral medium and without the use of higher temperatures the desired dye, for example in the case of an azo component containing methylol groups by reacting with a diazo component of the azo dye. The work-up the reaction mixture can be carried out as described above. Of course you can only such amounts of formaldehyde are reacted with the dye intermediates that their ability to convert to dyes - z. B. with azo components Coupling ability -, still retained.

The water-soluble methylol groups obtained by the process Dyes can be used to dye a wide variety of materials, such as cotton, Use wool, silk and leather. Compared to the corresponding methylod group-free Not only do they not only show a greatly increased absorption capacity for the starting dyes, but also considerably better fastness properties, especially wet fastness properties. The metallizable azo dyes containing methylol groups are more soluble in water and show higher wet fastness properties in both the metalized and the unmetalized state as similar dyes containing hydroxyethyl groups, z..B. of the German patent specification 883 021. The new dyes show a significantly better drawability and a considerably greater color strength than the dyes in German patent specification 878 937

The parts mentioned in the following examples are parts by weight.

Example 1 To a solution of 4 parts of sodium hydroxide and 15.2 parts N- (3-hydroxide) phenylurea in 40 parts are given to $ 0 parts of water 30% aqueous formaldehyde solution is added and the reaction mixture is left for 20 hours Stand at room temperature. The resulting clear yellow liquid becomes a solution of 15.9 parts of anhydrous sodium carbonate in 100 parts of water and then the on Diazo solution prepared in the usual manner from 17.2 parts of 1-aminobenzene-4-sulfonic acid amide added. After the coupling has ended, the dye formed is salted through Add sodium chloride, filter it and dry it at normal temperature, in a vacuum. He dyes wool and cotton in brownish-yellow shades of very good colors Wet fastness properties.

The same dye is obtained if one of those mentioned above is used Amounts of diazotized 1-aminobenzene-4-sulfonic acid amide and N- (3-hydroxy) phenylurea made moncazo dyestuff with 100 parts of water, 16.6 parts of anhydrous Sodium carbonate and 50 parts of 30% aqueous formaldehyde solution are added to the reaction mixture Stir at room temperature for 24 hours and work it up as described above. example 2 40.6 parts of the monoazo dye 1-aminobenzene-4-sulfGnsäureamid are made into paste 2-hydroxynaphthalene-6-sulfonic acid amide with 100 parts of water, sets 100 parts aqueous 30% formaldehyde solution and 10.6 parts of anhydrous sodium carbonate and stir for 24 hours. The resulting dye is, as described in Example 1, obtained from the implementation mix. His block dyeings on cotton are orange and significantly more wet fast than those of the starting dye.

Example 3 The procedure described in Example 1 is used but instead of the diazo solution mentioned there, the customary method of 9.2 parts of 4,4'-diaminodiplienyl prepared tetrazo solution. The dye obtained gives reddish brown on cotton Dyeings with very good wet fastness properties. Example 4 25 parts of 1-amino-4- (4'-ureidophenyl) -aminoanthraquinone-2-sulfonic acid are made into a paste with 100 parts of water. After adding 50 parts of 30% aqueous Formaldehyde solution and of 5.3 parts. anhydrous sodium carbonate is stirred for 24 Hours at normal temperature, the dye gradually dissolving. Of the the resulting methylol group-containing dye is replaced by the one described Work-up won. He dyes wool and cotton in bright blue tones of good wet fastness properties.

A dye with similar properties is obtained if one takes place of the anthraquinone derivative mentioned, 1-amino-4- (4'-carbonamidophenyl) -amiiioanthraquinone = 2 = sulfonic acid used.

Example 5 In one obtained from 19.2 parts of benzidine in a conventional manner Tetrazo solution is left at 10 to 12 ° C. for one hour, a solution of 34.1 Parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and 5.5 parts of sodium carbonate pour in 300 parts of water. During the half-page, which lasts about 12 hours The reaction mixture is coupled by gradually adding dilute sodium carbonate solution brought to a pH of about 5.0 to 5.5. To the suspension of the resulting The diazo solution prepared from 13.7 parts of N- (4-amino) phenylurea is added to the intermediate compound and then the solution of 26 parts of sodium carbonate in 120 parts of water, the Intermediate compound goes into solution. The corresponding diazodisazo dye falls after a short time from, the suspension of which is now the solution of N- (3-hydroxy) phenylurea according to Example 1 added by reacting with formaldehyde compound. After 5 to 6 hours the coupling is finished, whereupon it is worked up as usual.

The dye obtained gives strong dyeings on cotton black shades with very good wet fastness properties.

Example 6 The known method from 10.9 parts of 1-amino-3-hydroxybenzene produced diazonium solution is in a solution of 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 4 parts of sodium hydroxide and 21.2 parts of anhydrous sodium carbonate in 350 parts Stir in water. After the coupling has ended, the resulting dye is precipitated by adding sodium chloride and sucking it off. Then he will share in ZOO a 15% aqueous formaldehyde solution with the addition of 4 parts of sodium hydroxide Stirred for 24 hours at 15 to 20 ° C, then precipitated with sodium chloride, filtered off with suction and dried at ordinary temperature in a vacuum. He dyes cellulose fibers in red-brown; very good wet-fast tones.

Dyes with similar properties are obtained if the following dyes are used instead of the azo dye from 1-amino-3-hydroxybenzene and 2-amino-5-hydroxynaphthalene-7-sulfonic acid: Dye [color HZN - S02 - ``, `N @N (H II f-NH, yellow aC @Y o @ N / SO, H _ Color @ tdff "I color / feces H035 N = N @ OH C-NH2 I. O OGH, OH red I NH-C = NH2 H2NCNH N = N! \ / - \\ / 1I 1I Ö O / #) U / S03H 3 '08H red H, N II / \ NN @ O OH I32N-C = NIi = N = N - @ - OH yellow brown II @_ O S03H OHOH yellow brown HO - @@ N = N @ -CH = CH N = 1V ÖH S03H S03H OC H3 black N H2 Ö il _ NN NH - C-NH2 02N l \ -NNI 1I 0 503H S03H Ö N H2 - blue IC S03H C ", # y 11 / S0 3H O NIi / NH-O = NH2 If SO, HO Example 7 In- the solution of 17.6 parts of the ltriurus salt of the i =] elydroxy-2,4 = methylethylolbenzor. and 21.2 parts of non-ferrous carbonate in 200 parts of water are allowed to flow in inan di6 in a known manner from 27.2 parts of 1-amine acid-4-sulfonic acid amide. After the coupling has ended, the dye is precipitated by adding solid sodium chloride, sucked off and dried at ordinary temperature in a vacuum The dye gives yellow dyeings on wool, rayon and cotton with very good wet fastness properties.

Is used as a diazo component instead of 1-aminobenzene-4-sulfonic acid amide N- (4-Amino) -phenylurea, the result is a dye which is based on cellulose fibers gives very good wet-fast brownish-yellow colorations. Example 8 For a solution of 4 parts of sodium chloride and 9.4 parts of phenol in 10 parts of water are used to set 20 parts 30% strength aqueous formaldehyde solution is added and the reaction mixture is left to stand for 24 hours. The resulting clear yellow liquid becomes a solution of 15.9 parts anhydrous Sodium carbonate in 100 parts of water and then in a known manner from 24.2 parts 1-Amino-3,4-dichlorobenzene-5-sulfonic acid prepared diazo solution was added. To At the end of the coupling, the dye formed is salted by adding sodium chloride off, filtered it and dried at ordinary temperature in a vacuum. He colors Wool, rayon and cotton in bright reddish yellow tones with very good wet fastness properties.

If 1-amino-2-carboxylic acid is used instead of aminodichlorobenzenesulfonic acid as a diazo component, a dye is obtained whose orange-red coloration are also excellent wetfast on wool and cotton. Example 9 Diazotization is carried out 17.3 parts of 1-aminobenzene-4-sulfonic acid in a known manner and the aqueous solution is stirred Solution of the diazonium salt in a solution of 28.2 parts of 2-Ureida-5-hydroxynaphthalene-7-sulphonic acid, 4 parts of sodium hydroxide and 21.2 parts of anhydrous sodium carbonate in 350 parts Water a. When the coupling is complete, the dye is added by adding sodium chloride deposited. It is filtered off with suction to a mixture of 200 parts of 151% aqueous Formaldehyde solution and 4 parts of sodium hydroxide and added for about 24 hours stirred at 15 to 20 ° C. The dye is then precipitated by adding sodium chloride off, sucks it off and dries it in a vacuum at ordinary temperature. His Red-violet dyeings on cellulose fibers have very good wet fastness properties.

If 1-ureido-8-hydroxynaphthalene-3,6-disulfonic acid is used as the azo component, in this way a dye is obtained which gives bluish violet, very true colorations. Example 10 17.2 parts of 1-aminobenzo @ l-4-sulfonic acid amide are diazotized in a known manner Manner and stir the aqueous solution of the diazonium salt in a solution of 28.2 parts 2-ureido-5-hydroxynaphthalene-7-sulfonic acid, 4 parts sodium hydroxide and 21.2 parts anhydrous sodium carbonate in 350 parts of water. When the clutch is finished, so the dye is deposited by adding sodium chloride. It is filtered and together with 40 parts of 30% strength aqueous formaldehyde solution and 6 parts of anhydrous Sodium carbonate stirred for 12 hours. It is then filtered off and dried for 5 hours at 50 ° C under reduced pressure. The resulting dye yields on cotton very real red colorations.

Example 11 20 parts of the compound are dissolved in 80 parts of water and, after the addition of 50 parts of 30% aqueous formaldehyde solution and 5.4 parts of anhydrous sodium carbonate, stirred for 24 hours at room temperature. After the work-up described above, a dye is obtained which dyes wool and cotton in green shades with good wet fastness properties. The starting dye is obtained by reacting 1 mole of leuco-1,4-diaminoanthraquinone with 2 moles of p-phenylenediamine, sulfating the reaction product and allowing sodium cyanate to act on its aqueous solution. Example 12 A solution of 23.5 parts of 1-hydroxy-2-amino-4-cyclohexyl-6-nitrobenzene and 7 parts of sodium nitrite in 150 parts of water is slowly added dropwise, with stirring, to a mixture of 80 parts of ice and 14 parts of concentrated hydrochloric acid . The diazotization is complete after one hour. A pH value of 6 is set by adding about 5 parts of sodium bicarbonate. The suspension obtained is then introduced into a solution of 27 parts of 1- (3-sulfonic acid amidophenyl) pyrazolone- (5) -3-carboxamide and 8 parts of sodium hydroxide in 120 parts of water. A pn value of 9 to 10 is then set with 5 to 7 parts of an approximately 26% strength aqueous ammonia solution and the mixture is stirred for 20 hours. The azo dye formed is filtered off with suction and stirred together with 50 parts of a 30% strength aqueous formaldehyde solution, 100 parts of water and 8 parts of sodium hydroxide for 24 hours at room temperature. The resulting methylol group-containing dye is deposited with saturated aqueous sodium chloride solution and dried at 50 ° C. under reduced pressure.

The dye is a red-brown powder that turns purple-red on wool Results in dyeings of good fastness properties.

If the dyeings produced therewith are treated by known methods. with chromium-releasing agents, e.g. B. with potassium chromate in acetic acid solution one also has violet-red dyeings of good fastness properties.

Example 13 A mixture. from 60 parts of water, 80 parts of 30% aqueous formaldehyde solution, 36 parts of sodium carbonate and 38; 2 Parts of the dye which are diazotized by coupling 17.3 parts of 1-aminobenzene-2-sulfonic acid obtained with 23 parts of 2- (2-Hydroxybenzylidenamno) -4,6-diamino-1,3,5-triazine, stirs 24 hours at room temperature. The reaction product is then separated out Addition of sodium chloride, filtered and the residue was washed with dilute Sodium chloride solution until the washing solution reacts neutral. The dye obtained is dried under reduced pressure at 45 ° C. It dyes cotton in a reddish yellow Shades of good wet fastness.

Dyes with similar properties are obtained by replacing of 1-aminobenzene-2-sulfonic acid 17.3 parts of 1-amino # benzene-3-sulfonic acid, 17.3 parts 1-aminobenzene-4-sulfonic acid or 25.3 parts of 1-aminobenzene-2,5-disulfonic acid are used.

The 2- (2-Hydroxyb-enzylidenamino) -4,6-diamino-1,3,5-triazine can be z. B. prepare as follows A mixture of 42 parts of melamine, 45 parts of salicylaldehyde and 500 parts of N-methylpyrrolidine is heated to 1601 ° C. until the 2- (2-hydroxybenzylideneamino) -4,6-diamino-1,3 , S-triazine has completely deposited from the reaction solution. The mixture is then poured into 500 parts of methanol, the reaction product is filtered off and purified by boiling with water. EXAMPLE 14 To a mixture of 23 parts of 2- (2-hydroxybenzylideneamino) -4,6-diamino-1,3,5-triazine, 60 parts of 40% aqueous formaldehyde solution and 50 parts of water are added as much dilute aqueous sodium hydrogen carbonate solution as until a pH of -8 is reached, and the mixture is stirred for a further 24 hours at room temperature. A diazo solution prepared in a known manner from 17.3 parts of 1-aminobenzoi-2-sulfonic acid is then allowed to flow in, and it is worked up as in Example 1. The same dye as in Example 13 is obtained. Example 15 An aqueous solution of 28.1 parts of 2- (4-aminophenylsulfonylamino) -4,6-diamino-1,3,5-triazine is dianotized in a known manner and mixed with a solution combined of 30.4 parts of 1-hydroxynaphthalene-3,6-disulfonic acid, 6 parts of sodium carbonate and 30 parts of sodium acetate in 120 parts of water. The mixture is stirred for 24 hours, then 50 parts of an aqueous 30% formaldehyde solution and enough sodium hydrogen carbonate are added until a pH of 8.5 is reached, and the mixture is heated to 95 ° C. for 30 minutes while stirring. "The resulting dye is deposited after cooling by adding sodium chloride and dried under reduced pressure at 45 ° C. It dyes cotton in orange-red shades with good wet fastness.

The 2- (4-aminophenylsulfonylamino) -4,6-diamino 1,3,5-triazine can be z. B. by reacting melamine with 4-nitrobenzenesulfonic acid chloride in pyridine at 60 to 70 ' C and subsequent reduction of the resulting nitro compound.

Dyes with similar properties are obtained in the same way from dianotated 2- (4-aminophenylsulfonylamino) -4,6-diamino-1,3,5-triazine and the azo components in the following table: Azo component hue-of the coloring - on cotton 1- (2,6-dichloro-4-sulfophenyl) - 3-methylpyrazolone- (5) ........ yellow 1-hydroxynaphtha; liri-5 = sul'fön. = - acid .., ....................: scarlet fever 1-hydroxynaphthalene-4-sulfone acid ........................ scarlet fever 2-hydroxynaphthalene-6-sulfone acid ..................._ .. -Orange red 1-hydroxynaphthalene-3,8-di- sulfonic acid .................. orange red 1,8-dihydroxynaphthalene-3,6-di- sulfonic acid .................. bluish red 2,3-dihydroxynaphthalene 6-sulfonic acid ................ brown 1- (2-chloro-5-sulfophenyl) - 3-methylpyrazolone- (5) ........ greenish yellow 2-acetylamino-5-hydroxy naphthalene-7-sulfonic acid ...... orange 1-acetylamino-8-hydroxy naphthalene-4,6-disulfonic acid ... bluish-tinted red 2-phenylamino-5-hydroxy naphthalene-7-sulfonic acid ...... red 1-benzoylamino-8-hydroxy naphthalene-3,6-disulfonic acid ... bluish-tinted red Example 16 A mixture of 11.6 parts of the dye of the formula 64 parts of 30% aqueous formaldehyde solution, 5.4 parts of sodium carbonate and 3V parts of water are stirred for 24 hours at room temperature. After working up as in Example 1, a dye is obtained which dyes cotton in reddish-tinged blue shades of good wet and light fastness.

The anthraquinone dye used is obtained, for. B. by reacting 1-amino-4-bromoanthraquinone-2-sulfonic acid with 2- (4-aminobenzo-sulfonylamino) -4,6-diamino-1,3,5-triazine. Example 17 To a mixture of 53.1 parts of the dye which can be obtained by coupling 30.3 parts of dianotated 2-aminonaphthalene-6,8-disulfonic acid with 21.8 parts of 2 - (4 - hydroxyphenylamino) -4; 6-diamino -1,3,5-triazine is obtained, 50 parts of water and 22.5 parts of 40% aqueous formaldehyde solution are added. Sodium carbonate as much as necessary until a pH of 9 is reached, the mixture is heated to 95 ° C. with stirring for 25 minutes and worked up as in Example 1. A color - substance is obtained; which dyes cotton in reddish yellow tones of good wetness. The 2- (4-hydroxyphenylamine) -4,6-diarnino-1,3,5-triazine can be z. B. after the procedure. U.S. Patent 2,393-755.

Claims (1)

PATENT CLAIM: Process for the production of water-soluble methylol groups Dyes, characterized in that anthraquinone- and optionally metal-containing - azo dyes or intermediate products required for the manufacture of these dyes, which contain reactive hydrogen atoms, in weakly acidic to alkaline Medium treated with formaldehyde or formaldehyde-releasing agents and in the event the intermediate dye products convert the methylol compounds obtained into dyes implements. Publications considered: German Patent Specifications No. 878 937, 883 021. Two staining tables are laid out when the application is announced been.