Water-soluble phenylazoaminonaphthol sulphonic acid dyestuffs

Abstract

A water-soluble monoazo dyestuff which, in the form of the free acid, corresponds to the formula ##STR1## wherein R.sub.1 denotes alkyl which can be mono-substituted by chlorine, hydroxyl, C.sub.1 to C.sub.4 alkoxy, cyano, phenyl or tolyl, cyclohexyl which can be optionally substituted by C.sub.1 -C.sub.4 alkyl, phenyl, C.sub.1 -C.sub.4 -alkyl phenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl or naphthyl, alkenyl or benzenesulphonyl which can be substituted by fluorine, chlorine, bromine, trifluoromethyl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,R.sub.2 denotes hydrogen, C.sub.1 -C.sub.4 -alkyl which can be substituted by hydroxyl, cyano, formylamino, C.sub.1 -C.sub.4 alkylcarbonylamino or benzoylamino which in turn can be substituted by methyl, chlorine, bromine or trifluoromethyl; cyclohexyl or phenyl which can be substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine, bromine or trifluoromethyl andR.sub.3 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl and a process for the preparation of such water-soluble mono-azo dyestuff. The dyestuffs according to the invention are suitable for dyeing natural and synthetic fibre materials, for example for dyeing wool or polyamide fibres, in level, deep red to violet shades with very good fastness to light, wet processing and perspiration.

Description

The invention relates to water-soluble monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR2## wherein

R.sub.1 denotes optionally substituted alkyl, optionally substituted cyclohexyl, optionally substituted phenyl or naphthyl, alkenyl or optionally substituted benzenesulphonyl,

R.sub.2 denotes hydrogen, optionally substituted C.sub.1 -C.sub.4 -alkyl, cyclohexyl or optionally substituted phenyl and

R.sub.3 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl.

The sulphonic acid group is preferably in the m-position or p-position relative to the hydroxyl group.

Suitable substituents R.sub.1 are C.sub.1 -C.sub.8 -alkyl which is optionally monosubstituted by chlorine, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, cyano, phenyl or tolyl, C.sub.2 -C.sub.4 -alkenyl, cyclohexyl, C.sub.1 -C.sub.4 -alkylcyclohexyl, phenyl, C.sub.1 -C.sub.4 -alkylphenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, naphthyl, trifluoromethylphenyl, naphthyl, trifluoromethyl and benzenesulphonyl which is optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy.

Possible substituents of the alkyl radicals R.sub.2 are, in particular, hydroxyl, cyano, formylamino, C.sub.1 -C.sub.4 -alkylcarbonylamino or benzoylamino which is optionally substituted by methyl, chlorine, bromine or trifluoromethyl. Possible substituents of the phenyl radicals R.sub.2 are C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine, bromine and trifluoromethyl.

Particularly suitable dyestuffs correspond, in the form of the free acid, to the formula ##STR3## wherein R.sub.4 denotes C.sub.1 -C.sub.4 -alkyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, cyanoethyl or phenyl which is optionally substituted by chlorine or methyl.

The dyestuffs of the formula (I) are prepared either by diazotising amines of the formula ##STR4## and coupling the diazotisation products with coupling components of the formula ##STR5## wherein R.sub.1, R.sub.2 and R.sub.3 have the abovementioned meaning.

If R.sub.1 denotes an optionally substituted alkyl group, an alkenyl group or an optionally substituted benzenesulphonyl radical, the dyestuffs of the formula (I) can also be prepared by alkylating, alkenylating or acylating, with optionally substituted benzenesulphonyl chlorides, hydroxyazo dyestuffs of the formula ##STR6## wherein R.sub.2 and R.sub.3 have the abovementioned meaning, the radical R.sub.1 being introduced.

Examples of suitable alkylating agents are C.sub.1 -C.sub.4 -alkyl halides, C.sub.1 -C.sub.4 -dialkyl sulphates, alkylene oxides with 2 to 4 C atoms and acrylonitrile.

Suitable acylating agents are benzenesulphonic acid halides which are optionally substituted by fluorine, chlorine, bromine, methyl, ethyl or trifluoromethyl.

The dyestuffs according to the invention are suitable for dyeing natural and synthetic fibre materials, for example for dyeing wool or polyamide fibres, in level, deep red to violet shades with very good fastness to light, wet processing and perspiration. Depending on the substituents R.sub.1, R.sub.2 or R.sub.3, they can be particularly suitable for dyeing polyamide fibres. For example, it is possible to prepare dyestuffs which are absorbed well onto polyamide fibres even from a neutral to weakly acid dyebath, but also to prepare those which are taken up quantitatively by the fibre only from a weakly to more strongly acid dyebath. In the same manner, their ease of combination with yellow and blue acid dyestuffs can be advantageously influenced. Polyamide fibres are understood, in particular, as those consisting of synthetic polyamides, such as .epsilon.-polycaprolactam or condensation products of adipic acid and hexamethylenediamine.

EXAMPLE 1

19.1 g of 2-amino-5-methoxy-benzotrifluoride are dissolved in 350 ml of water and 30 ml of concentrated hydrochloric acid, the solution is cooled to 0.degree. C. and the amine is diazotised with a solution of 6.9 g of sodium nitrite in 50 ml of water. After destroying excess nitrous acid with amidosulphonic acid, the diazonium salt solution is added to a solution, cooled to 5.degree. C., of 24.2 g of 6-amino-4-hydroxynaphthalene-2-sulphonic acid in 300 ml of dimethylformamide. The coupling is rapidly completed in the strongly acid medium. The mixture is subsequently stirred at room temperature for 2 hours. The reaction product is then filtered off and dried. 38 g of a red powder of the formula ##STR7## which dyes polyamide fibres and wool in a clear red from an aqueous solution, are obtained.

EXAMPLE 2

43 g of the dyestuff of the formula ##STR8## obtained by coupling diazotised 2-amino-5-hydroxybenzotrifluoride with 6-amino-4-hydroxynaphthalene-2-sulphonic acid, are dissolved in a mixture of 250 ml of water, 250 ml of isopropanol and 40 ml of 10% strength sodium hydroxide solution, and 10 g of propylene oxide are added in the course of 2 hours, whilst stirring. The temperature is kept at 50.degree. C. during the addition of the propylene oxide. When the reaction has ended, which can be established by thin layer chromatography, 500 ml of water and then 70 g of sodium chloride are added, the mixture is cooled to room temperature, whilst stirring, and the dyestuff is filtered off. It has the formula ##STR9## and dyes polyamide fibres in a clear red from an aqueous solution.

EXAMPLE 3

43 g of the dyestuff of the formula ##STR10## are dissolved in 800 ml of water and 40 ml of 10% strength sodium hydroxide solution. 23 g of benzenesulphonyl chloride are added dropwise at room temperature in the course of 2 hours, whilst stirring thoroughly. The pH is kept at 8-9, if necessary by further addition of 10% strength sodium hydroxide solution. When the starting dyestuff can no longer be seen in the thin layer chromatogram, 80 g of sodium chloride are added, the mixture is further stirred for some time and the reaction product is then filtered off. After drying, 51 g of a red dyestuff of the formula ##STR11## which dyes polyamide fibres in a clear red, are obtained.

EXAMPLE 4

0.1 g of the dyestuff obtained according to Example 1 are dissolved in 100 ml of hot water. 5 ml of ammonium acetate solution are added and the mixture is diluted with cold water to a volume of 500 ml. 10 g of polyamide fibre material are introduced into this dyebath, the dyebath is heated to the boil in the course of 20 minutes, 4 ml of 10% strength acetic acid are added and the bath is kept at the boiling point for 1 hour. Thereafter, the dyed polyamide is removed from the dyebath, rinsed thoroughly with hot water and dried at 70.degree.-80.degree. C. A clear red dyeing is obtained.

If the diazo and coupling components listed in Table 1 are used, further valuable water-soluble dyestuffs which dye polyamide in red shades from a weakly acid or neutral bath are obtained by the process indicated in Example 1:

Table 1__________________________________________________________________________Example Diazo component Coupling component__________________________________________________________________________5 2-Amino-5-ethoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid6 2-Amino-5-propoxybenzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid7 2-Amino-5-isopropoxy-benzo- 2-Amino-8-hydroxy- trifluoride naphthalene-6- sulphonic acid8 2-Amino-5-butoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid9 2-Amino-5-(2-methylpropyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid10 2-Amino-5-(1-methylpropyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid11 2-Amino-5-tert.-butoxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid12 2-Amino-5-pentyloxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid13 2-Amino-5-(3-methyl-butyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid14 2-Amino-5-allyloxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid15 2-Amino-5-crotyloxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid16 2-Amino-5-methallyloxy-benzo- 2-Amino-8-hydroxy- trifluoride naphthalene-6- sulphonic acid17 2-Amino-5-(2-chloroethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid18 2-Amino-5-(2-methoxyethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid19 2-Amino-5-(2-butoxyethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid20 2-Amino-5-(2-cyanoethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid21 2-Amino-5-(4-cyanobutyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid22 2-Amino-5-trifluoromethoxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid23 2-Amino-5-(2-hydroxyethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic-acid24 2-Amino-5-(2-hydroxybutyl) 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid25 2-Amino-5-(2-methyl-2-hydroxy- 2-Amino-8-hydroxy- propyl)-oxy-benzotrifluoride naphthalene-6- sulphonic acid26 2-Amino-5-(2-phenylethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid27 2-Amino-5-cyclohexyloxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid28 2-Amino-5-(4-methylcyclohexyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene6- sulphonic acid29 2-Amino-5-phenoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-6- sulphonic acid30 2-Amino-5-(4-methylphenyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid31 2-Amino-5-(2-methylphenyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid32 2-Amino-5-(4-chlorophenyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid33 2-Amino-5-(3-chlorophenyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene6- sulphonic acid34 2-Amino-5-(2-chlorophenyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-6- sulphonic acid35 2-Amino-5-(3-bromophenyl)-oxy- 2-Amino8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid36 2-Amino-5-(3-trifluoromethyl- 2-Amino-8-hydroxy- phenyl)-oxy-benzotrifluoride npahthalene-6- sulphonic acid37 2-Amino-5-methoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-5- sulphonic acid38 2-Amino-5-ethoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-5- sulphonic acid39 2-Amino-5-butoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-5- sulphonic acid40 2-Amino-5-(2-methoxyethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-5- sulphonic acid41 2-Amino-5-(2-hydroxyethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-5- sulphonic acid42 2-Amino-5-(2-cyanoethyl)-oxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-5- sulphonic acid43 2-Amino-5-trifluoromethoxy- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-5- sulphonic acid44 2-Amino-5-(2-phenylethyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-5- sulphonic acid45 2-Amino-5-phenoxy-benzotri- 2-Amino-8-hydroxy- fluoride naphthalene-5- sulphonic acid46 2-Amino-5-(4-chlorophenyl)- 2-Amino-8-hydroxy- oxy-benzotrifluoride naphthalene-5- sulphonic acid47 2-Amino-5-(3-trifluoromethyl- 2-Amino-8-hydroxy- phenyl)-oxy-benzotrifluoride naphthalene-5- sulphonic acid48 2-Amino-5-methoxy-benzotri- 2-Methylamino-8- fluoride hydroxynaphthalene- 6-sulphonic acid49 2-Amino-5-isopropoxy-benzo- 2-Methylamino-8- trifluoride hydroxynaphthalene- 6-sulphonic acid50 2-Amino-5-butoxy-benzotri- 2-Methylamino-8- fluoride hydroxynaphthalene- 6-sulphonic acid51 2-Amino-5-phenoxy-benzotri- 2-Methylamino-8- fluoride hydroxynaphthalene- 6-sulphonic acid52 2-Amino-5-(4-chlorophenyl)- 2-Methylamino-8- oxy-benzotrifluoride hydroxynaphthalene- 6-sulfonic acid53 2-Amino-5-methoxy-benzotri- 2-Dimethylamino-8- fluoride hydroxy-naphthalene- 6-sulphonic acid54 2-Amino-5-phenoxy-benzotri- 6-Dimethylamino-8- fluoride hydroxy-naphthalene- 6-sulphonic acid55 2-Amino-5-isopropoxy-benzo- 2-Phenylamino-8- trifluoride hydroxy-naphthalene- 6-sulphonic acid56 2-Amino-5-phenoxy-benzotri- 2-Phenylamino-8- fluoride hydroxy-naphthalene- 6-sulphonic acid57 2-Amino-5-cyclohexyloxy-benzo- 2-Phenylamino-8- trifluoride hydroxy-naphthalene- 6-sulfonic acid58 2-Amino-5-methoxy-benzotri- 2-.beta.-Hydroxyethyl- fluoride amino-8-hydroxy- naphthalene-6- sulphonic acid59 2-Amino-5-phenoxy-benzotri- 2-.beta.-Hydroxyethyl- fluoride amino-8-hydroxy- naphthalene-6- sulfonic acid60 2-Amino-5-methoxy-benzotri- 2-Butylamino-8- fluoride hydroxy-naphthalene- 6-sulphonic acid61 2-Amino-5-butoxy-benzotri- 2-Butylamino-8- fluoride hydroxy-naphthalene- 6-sulphonic acid62 2-Amino-5-phenoxy-benzotri- 2-Butylamino-8- fluoride hydroxy-naphthalene- 6-sulphonic acid63 2-Amino-5-(4-chlorophenyl)- 2-Butylamino-8- oxy-benzotrifluoride hydroxy-naphthalene- 6-sulphonic acid64 2-Amino-5-methoxy-benzotri- 2-Cyclohexylamino- fluoride 8-hydroxy-naphtha- lene-6-sulphonic acid65 2-Amino-5-phenoxy-benzotri- 2-Cyclohexylamino- fluoride 8-hydroxy-naphtha- lene-6-sulphonic acid66 2-Amino-5-(4-chlorophenyl)- 2-Cyclohexylamino- oxy-benzotrifluoride 8-hydroxy-naphtha- lene-6-sulfonic acid67 2-Amino-5-methoxy-benzotri- 2-(2,4-Dimethyl- fluoride phenyl)-amino-8- hydroxy-nahthalene- 6-sulphonic acid68 2-Amino-5-phenoxy-benzotri- 2-(2,4-Dimethyl- fluoride phenyl)-amino-8- hydroxy-naphthalene- 6-sulphonic acid69 2-Amino-5-(2-hydroxyethyl)- 2-(2,4-Dimethyl- oxy-benzotrifluoride phenyl)-amino-8- hydroxy-naphthalene- 6-sulphonic acid70 2-Amino-5-(4-tert.-butyl- 2-Amino-8-hydroxy- phenyl)-oxy-benzotrifluoride npahthalene-6- sulphonic acid71 2-Amino-5-(4-methylmercapto- 2-Amino-8-hydroxy- phenyl)-oxy-benzotrifluoride naphthalene-6- sulphonic acid72 2-Amino-5-(1-naphthyloxy)- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid73 2-Amino-5-(2-naphthyloxy)- 2-Amino-8-hydroxy- benzotrifluoride naphthalene-6- sulphonic acid__________________________________________________________________________

Table 2 gives further dyestuffs which dye polyamide in red shades and which have been obtained by alkylating or acylating the dyestuff of the formula ##STR12## on the OH group of the benzene ring, using the alkylating or acylating agents indicated in the Table.

Table 2______________________________________Example Alkylating or acylating agent______________________________________74 Dimethyl sulphate75 Diethyl sulphate76 4-Methylbenzenesulphonic acid methyl ester77 Ethylene oxide78 Propylene oxide79 1,2-Butylene oxide80 Styrene oxide81 2-Chloroethanol82 Benzyl chloride83 Acrylonitrile84 Phenethyl bromide85 Allyl bromide86 4-Methyl-benzenesulphonyl chloride87 2-Methylbenzenesulphonyl chloride88 3-Methylbenzenesulphonyl chloride89 4-Ethylbenzenesulphonyl chloride90 4-Chlorobenzenesulphonyl chloride91 4-Bromobenzenesulphonyl chloride92 4-Fluorobenzenesulphonyl cholride93 3-Trifluoromethylbenzenesulphonyl chloride94 4-Methoxybenzenesulphonyl chloride95 2,4-Dichlorobenzenesulphonyl chloride96 4-Isopropylbenzenesulphonyl chloride97 4-tert.-Butylbenzenesulphonyl chloride98 4-Butoxybenzenesulphonyl chloride______________________________________

Claims

1. A water-soluble monoazo dyestuff which, in the form of the free acid, corresponds to the formula ##STR13## wherein R.sub.1 denotes alkyl alkyl mono-substituted by chlorine, hydroxyl, C.sub.1 to C.sub.4 alkoxy, cyano, phenyl or tolyl, cyclohexyl cyclohexyl substituted by C.sub.1 -C.sub.4 -alkyl, phenyl C.sub.1 -C.sub.4 -alkyl phenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl or napthyl, alkenyl or benzenesulphonyl benzenesulphonyl substituted by fluorine, chlorine, bromine, trifluoromethyl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,

R.sub.2 denotes hydrogen, C.sub.1 -C.sub.4 -alkyl C.sub.1 -C.sub.4 -alkyl substituted by hydroxyl, cyano, formylamino, C.sub.1 -C.sub.4 alkylcarbonylamino or benzoylamino, C.sub.1 -C.sub.4 -alkyl- carbonylamino or benzoylamino; substituted by methyl, chlorine, bromine or trifluoromethyl; cyclohexyl or phenyl, cyclohexyl or phenyl substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine, bromine, or trifluoromethyl and

R.sub.3 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl.

2. An azo dyestuff according to claim 1, wherein the sulphonic acid group is in the m-position or p-position relative to the hydroxyl group.

3. An azo dyestuff according to claim 1, wherein

R.sub.1 denotes C.sub.1 -C.sub.8 -alkyl, C.sub.1 -C.sub.8 -alkyl monosubstituted by chlorine, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, cyano, phenyl or tolyl, C.sub.2 -C.sub.4 -alkenyl, cyclohexyl, C.sub.1 -C.sub.4 -alkylcyclohexyl, phenyl, C.sub.1 -C.sub.4 -alkylphenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, naphthyl, trifluoromethyl or benzenesulphonyl or benzenesulphonyl substituted by fluorine, chlorine, bromine, trifluoromethyl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,

R.sub.2 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkyl substituted by hydroxyl, cyano, formylamino, C.sub.1 -C.sub.4 -alkylcarbonylamino or benzoylamino, C.sub.1 -C.sub.4 -alkylcarbonylamino or benzoylamine; substituted by methyl, chlorine, bromine or trifluoromethyl, or phenyl or phenyl substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine, bromine or trifluoromethyl and

R.sub.3 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl.

4. An azo dyestuff according to claim 1 which, in the form of the free acid, corresponds to the formula ##STR14## wherein R.sub.4 denotes C.sub.1 -C.sub.4 -alkyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, cyanoethyl or phenyl or phenyl substituted by chlorine or methyl.