DE1419762A1 - Process for the production of azo dyes - Google Patents

Description

Process for the preparation of azo dyes It has been found that valuable new azo dyes are obtained if seylating agents which contain the remainder of the general formula give off, where R denotes an alkyl radical, an aralkyl radical, a cycloalkyl radical, an aryl radical or a heterocyclic radical, with azo dyes or for the preparation of azo dyes suitable intermediates which carry at least one acylatable amino group, to β-sulfonylpropionamide derivatives and in the case of the use of the intermediates the reaction products are completed in the usual way to form azo dyes.

Acylatable amino groups are preferably primary, but also secondary amino groups into consideration. Acyl end means that the rest of the general Give formula I are, for example, the corresponding ß-sulfonylpropionic acid halides, like the chlorides or the bromides, or the corresponding ß-sulfonylpropionic anhydridea The radical R in the general formula I expediently stands for a low molecular weight Alkyirest, for example for a methyl, ethyl or propyl radical, or for a benzyl radical, or preferably an optionally substituted aryl radical, for example for a naphthyl-1-residue, for a naphthyl-2-residue, for a 4-methylphenyl radical, for a 4-methoxyphenyl radical or for a 4-nitrophenyl radical.

The new dyes correspond to the general formula where A denotes the radical of an azo dye optionally bearing one or more sulfonic acid groups, R 'represents a hydrogen atom or an advantageously low molecular weight alkyl radical, R has the meaning given above and n represents an integer greater than or equal to 1, preferably stands for one of the numbers 1 and 2. The new process is of particular technical interest for the production of monoazo dyes.

Those used as starting materials for the production of the new dyes Azo dyes or intermediates suitable for the production of azo dyes must contain at least one acylatable amino group, but they can also contain two or have more than one acylatable amino group.

Intermediate substances suitable for the production of azo dyes are not only coupling components and diazo components, but also in diazo components transferable compounds, for example compounds that instead of the to be added primary Amino group contain a formylamino group or a nitro group. The mentioned Intermediate materials are in the usual manner by coupling or, if necessary after conversion into diazo components, by diazotization @ and coupling to azo dyes completed.

Azo dyes which are in the diazo component and / or in the coupling component corresponding part of the molecule containing acylatable amino groups are customary Way obtainable by coupling diazo components with coupling components, wherein at least one of the components is an acylatable amino group or an acylatable amino group Amino group convertible group, e.g. a formylamino group or a nitro group, must contain, which converted into an acylatable amino group after the coupling will.

Diazo components, apart from the diazotizable amino group, at least contain another acylatable amino group are, for example, 1,3-diaminobenzene-4-sulfonic acid, 1,4-di-aminobenzene-3 ° sulfonic acid, 1,4-diaminobenzene and 1,4-diamino-3-nitrobenzene.

As compounds which can be converted into diazo components, the acylatable Amino groups are, for example, 1-amino-4-nitrobenzene, 1-Aminoa3®nitrobenzene, Called 1-amino-4-formylaminobenzene or 1-amino-3-formylaminobenzene.

Coupling components containing at least one acylatable amino group are included, for example, aminohydroxybenzenes, di- or Polyaminobenzenes, Aminohydroxynaphthalenes, Dun or polyaminonaphthalenes, aminophenylmethylpyrazolones and the N-alkylm,, N ary1-9 NV aralkyl and N-cycloalkyl derivatives of these compounds as well as the corresponding sulfonic acids, sulfonic acid amides and, sulfone o The mentioned Compounds can have further substituents such as alkyln, aralkyl, Aryl, carboxyl, carboxylic acid, carboxamide =, carboxylic acid ester, arylamino, Carry nitro groups and / or halogen atoms.

The acylating agents that release the remainder of the general formula I, can be derived from various ß-sulfonylpropionic acids, for example from ß-methylsulfonpropionic acid, ß-benzylsulfonpropionic acid or advantageous of an optionally substituted ß-phenylsulfonpropionic acid from these Acid halides or acid anhydrides are usually available from carboxylic acids with the aforementioned azo dyes or suitable for the production of azo dyes Intermediates in aqueous solution or slurry or in organic solvents, such as formamide, dimethylformamide or N-methylpyrrolidone or in aqueous mixtures with organic solvents and / or diluents at lower or slightly higher levels Temperature, advantageously in the presence of acid-binding agents such as sodium carbonate, Sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium acetate, Potassium acetate, sodium hydroxide, potassium hydroxide, and / or organic nitrogen® hold Bases, e.g. triethylamine or pyridine, reacted. The new dyes can be used for Dyeing and / or printing of structures such as foils, films and textiles, e.g. Fibers, Threads, flakes, woven and knitted fabrics made from a wide variety of fiber-forming materials Kind, for example made of wool, silk, synthetic linear polyamides or polyurethanes or serve from paper. Those obtainable according to the invention are particularly suitable Dyes are excellent for dyeing and / or printing textiles from native and / or regenerated cellulose. One then obtains the customary for reactive dyes Methods dyeings and prints with very good fastness properties, in particular excellent wet, draw and rub fastness. When printing cellulose textiles the new dyes are distinguished by the methods customary for reactive dyes due to the particularly easy washability of the unfixed dye components the end.

a The parts and percentages given in the examples are, unless otherwise stated, weight units. The parts of the room relate to the parts by weight like the liter to the kilogram measured under normal conditions.

Example 1 In a mixture of 21.4 parts of ßm-phenylsulfonpropionic acid and 10 parts of dimethylformamide are carried at 50 ° C. in 1/4 hour with stirring 13 Divide thionyl chloride into small proportions. After about 1/2 The formation of each acid chloride is complete within 1 hour. To the solution of the acid chloride 13.8 parts of 4-nitroaniline are then added and the mixture is stirred at 60 ° C. for 3 stalls. Then the mixture is diluted with 300 parts of ice water and the precipitate is filtered off with suction, washed with water and dried. About 30 parts of a yellowish one are obtained in this way Crystal powder,. that as a crude product at 1580C (after recrystallization Methanol at 1630C) melts.

30 parts of the 4-nitro-B-phenylsulfonpropionic anilide thus obtained are in 2000 parts by volume of methanol using 0.2 parts of platinum oxide at 800C and below hydrogenated at a pressure of 60 atmospheres. After the hydrogenation is complete erbfiltered by the catalyst and the methanol solution to 1/10 of the original Confined in volume. The colorless crystals that separate out are filtered off with suction. The 4-amino-B-phenylsulfonpropionic acid anilide obtained in a yield of about 25 parts melts at 1480C. In the form of the hydrochloride, the compound is very dilute soluble in aqueous hydrochloric acid.

15.2 parts of the amino compound thus obtained are in a mixture from 500 parts of ice water and 17.5 parts by volume of concentrated aqueous hydrochloric acid dissolved and diazotized with 16 parts of a 23% strength aqueous solution of sodium nitrite. This diazo solution is added to a solution of 11.2 parts of 1-Hydroxynaphthalin®4®sulfonic acid in 200 parts of water, with the addition of about 90 parts by volume of a 10% aqueous sodium carbonate solution, the reaction of the mixture at a pH of approximately 7 is held.

After about 3 to 100 hours of stirring, the coupling is complete. The resulting red dye is made by adding about 50 to 150 parts of sodium chloride Bus salted and then vacuumed and dried. With that in a yield of about 25 to 30 parts of the resulting dye are obtained according to the method for reactive dyes customary dyeing processes on cotton red dyeings with very good wet fastness properties.

Further azo dyes are obtained by combining the diazo components mentioned in the table below and obtainable as explained above with the coupling components mentioned by diazotization and coupling. The dye 2 dyes fabrics made of polycaprolactam and the dyes 3 to 21 dye textiles made of cotton according to the dyeing processes customary for reactive dyes in the shades given in the table. Diazo component, coupling component, color shade 2 o_V \ # S02-CH2-CH2-C0-NH ® NH2 1-phenyl-3 ° methyl-yellow pyrazolone- (5) 3 @@ 1 m (30Sulfophenyl y- yellow 3-methylpyrazolone- (5) 1- (4-sulfophenyl) - yellow 3-methylpyrazolone- (5) 5 @@ 1- (2-methyl = 4 = sulfome yellow phenyl) m3 ° methyl0 pyrazolone- (5) 6 @@ 1- (2-chloro-5®sulfo- yellow phenyl) -3.®methyl- pyrazolone- (5) Diazo component, coupling component, color shade 7 @@ So 2-CH2-CH2-C0-NH o` NH2 1- (6-chloro-2-methyl-yellow 4-sulfophenyl) -3- methylpyrazolone- (5) 8 ° 1- (2,6-dichloro-4-yellow sulfophenyl) -3- methylpyrazolone- (5) 2-hydroxynaphthalene red 3,6-disulfonic acid 10 '° 1-hydroxynaphthalene red 5-sulfonic acid 11 "1-hydroxynaphthalene red 3,8-di-sulfonic acid j (12 "1-Benzoylamino-8-- blue- hydroxyaaphthalene-pricked 3,6-disulfonic acid red 13 @ # 1, -acetylamino-8- blue- hydroxynaphthalene-pricked 3,6-disulfonic acid red ; @ 14 to 1 = denzoylamino-8- blue- - hydroxynaphthalene pricked 4,6-disulfonic acid red 15 n 2-acetylamino-5-red hydroxyns; phthalene 7-sulfonic acid 16 @ ® S02-CH2-CF2-C0-NH 1-hydroxynaphthalene red V Nx2 4-sulfonic acid v 17 "1- (2-chloro-5-sulfo yellow - phenyl) -3-methyl- pyrazolone- (5th 18 CH 30 ® % So 2-CH2-CH2-CO-NH2 1-Hydroxy- red - naphthalene-4- sulfonic acid Diazo component, coupling component, color shade 19 CH 3, O J E S02-CH2-CH2-CO-NH F @a NH2 1-hydroxynaphthalene red 4-sulfonic acid 20 j \ SO 2 @ CH2 @ QH2 @ C0-NH / @ \ NH2 1-N, N-Di-ß-hydroxy-yellow ethylamino-3-methyl- benzene 21 "monoazo dye 'the blue . formula OH IH = N P % N02 w 0 H035 so 3H EXAMPLE 22 To a solution of 20 parts of 2-amino-5-hydrozynaphthalene-7-aulfonic acid in 300 parts of water is added, with good nutrition at room temperature, doho at about 15 bin 300®, a solution of the type used in Example t, Abaatz 1t specified wines from 21.4 parts of O-phenylaulfonpropionic acid available. chloride in dimethylformamide and keeps the reaction of the solution at a pH value of about 5 to 6. As soon as no more diasotable compound is naohweiebar in the solution, -iet the reaction is over, about 10 to 15 minutes of stirring at 20 to 300C 'required. A 17 parts of 1-aminobenzene-4-sulfonic acid, prepared as usual, is then added to the coupling solution thus kept and the reaction of the solution is maintained by adding dilute aqueous sodium carbonate solution at a p value of approximately -7. The dye is then salted out with sodium chloride and then filtered off with suction and dried. The dye obtained in a yield of about 70 parts as a red powder dyes cotton by the dyeing processes customary for reactive dyes in red shades with very good wet fastness properties. Further monoazo dyes are obtained by combining the diazo components mentioned in the table below with the coupling components mentioned and obtainable in the manner explained above by diazotization and coupling. These dyes produce dyeings and prints in the shades given in the table on cellulose fabric using the methods customary for reactive dyes. Diazen component . Coupling component color 23_v NH2 OH. Red 1 503H H03S s O-CH2-CH2_So2 ' i OH NH-CO- CH2-CH2-S02-e 24 y, 2 > I n - purple X HO S So 3H OH HH -CO-CH2-CH2-S02 /% .? C. 25 HO 3S- & NH2 \ @ i - violet H035 r @ 503H EXAMPLE 26 23 parts of 1-acetylamino-4-aminobenzene-3-sulphonic acid are diazotized in the usual way, coupled with 22.4 parts of 1-hydroxynaphthalene = 4-sulphonic acid, with the addition of 50 parts of 35% aqueous hydrochloric acid and excess sodium chloride The dye obtained is precipitated and, after filtering, it is stirred in the form of an aqueous paste together with 1000 parts by volume of a 10% aqueous sodium hydroxide solution for one hour at 90 to 10000o. Then enough aqueous hydrochloric acid is added to the reaction mixture. In addition, the reaction of the mixture shows a p. Value of about 4., and the deposited precipitate is filtered off. The filter material is made into a paste as an aqueous paste with 500 parts by volume of water. This dough is then mixed at room temperature with a solution of the acid chlorides obtained in the manner specified in Example 1 as 21.4 parts of fä-phenylsulfonpropionic acid in dimethylformamide and in small portions with so much saturated aqueous The sodium acetate solution is stirred up so that the reaction of the reaction mixture shows a P. value of about 5. After about 4 to 5 hours, the dye formed is precipitated with excess sodium chloride, filtered, washed with dilute aqueous sodium chloride solution and dried. About 50 to 100 parts of a red dye are obtained which, according to the dyeing processes customary for reactive dyes, dyes Baümwölle in clear red shades of excellent water-fastness properties.

Claims (1)

A process for the preparation of azo dyes, characterized in that acylating agents which contain the remainder of the general formula give off, where R is an alkyl radical, an aralkyl radical Cycloalkyl.restg is an aryl radical or a heterocyclic radical Rest. Means with azo dyes or for the production of Azo dyes suitable intermediates that contain at least one bear ae-yl iable amino group, to ß-sulfonylpropi onsäureamid- derfvaten implements and in the case of the use of intermediate substances the reaction products in the usual way zii azo dyes vol: l stands 1 gt,