GB2032941A - Anthraquinone-azo compounds, their preparation and their use as dyestuffs - Google Patents

Abstract

The invention provides water- soluble anthraquinone-azo dyestuffs of the general formula <IMAGE> in which R1 represents a hydrogen atom or a sulphonic acid group, and the two R1s are not both hydrogen, K represents the radical of a coupling component and Z represents a fibre- reactive group which is linked to a carbocyclic aromatic nucleus of the coupling component, n being 1 or 2. The compounds may also be in the form of their salts. The compounds, preferably in the form of alkali metal salts, are useful for dyeing and printing fibre materials containing carboxamide groups, e.g. silk, wool and other animal hairs, polyamide and polyurethane fibres, and fibre materials containing hydroxy groups, e.g. cotton, linen and viscose rayon. Green to olive-green, blue and grey dyeings are obtained having good fastness to wet processing and very good fastness to light. The invention also provides intermediates for these dyestuffs in which the Zn group is replaced by an NHR group in which R represents a hydrogen atom or a lower alkyl group or a cyano-lower alkyl group.

Description

SPECIFICATION Anthraquinone-azo compounds, their preparation and their use as dyestuffs The present invention provides a water-soluble anthraquinone-azo compound which, in the form of the free acid, has the general formula

wherein R, represents a hydrogen atom or a sulphonic acid group and the two R, moieties can be the same or different, but are not both hydrogen at the same time; K represents the radical of a coupling component; Z represents a fibre-reactive group which is linked to a carbocyclic aromatic nucleus of the coupling component; and n represents the number 1 or 2, and two Z moieties can be the same or different, or a salt thereof.

A compound of the invention can be in the form of the free acid or in the form af a salt thereof, preferably in the form of a salt, especially an alkali metal salt or the ammonium salt, more especially in the form of the sodium salt.

The compounds may be used, preferably in the form of an alkali metal salt thereof, for dyeing and printing fibre materials.

K represents the radical of a coupling component, preferably belonging to one of the following series: (i) the acetoacetylarylamides, e.g. acetoacetylanilides and acetoacetylnaphthylamides; (ii) 1 -phenylpyrazol-5-ones or 1 -naphthylpyrazol-5-ones which are substituted in the 3-position by a lower alkyl group, e.g. methyl, or by a carboxy group, a carbamoyl group, a lower alkoxy-carbonyl, e.g. methoxycarbonyl and ethoxycarbonyl, group, or by a phenyl group or a phenyl group substituted by one or more of the same or different substituents selected from lower alkyl, lower alkoxy and halogen, e.g. chlorine, (iii) 1 -phenyl-5-aminopyrazoles or 1 -naphthyl-5-aminopyrazoles which are substituted in the 3 position by a lower alkyl group, e.g. methyl, or by a carboxy group, a carbamoyl group, a lower alkoxy-carbonyl, e.g. methoxycarbonyl and ethoxycarbonyl group, or by a phenyl group or a phenyl group substituted by one or more of the same or different substituents selected from lower alkyl, lower alkoxy and halogen, e.g. chlorine; (iv) naphthols, the or each carbocyclic aromatic nucleus in these coupling components (i), (ii), (iii) and (iv), where not already indicated above, being, if desired, further substituted, preferably by 1 to 3 of the same or different substituents, in the or each nucleus, but preferably by a total of 1 to 3 substituents, preferred ones being lower alkyl, e.g. methyl and ethyl; lower alkoxy, e.g. methoxy and ethoxy; halogen, e.g.

chlorine and bromine; nitro; carboxy; carboxylic acid amide; carboxylic acid amide substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; sulphonamide, sulphonamide substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; lower alkanoylamino; benzoylamino; hydroxy; amino; lower alkylsulphonyl; phenylsulphonyl; lower alkylamino; di-lower alkyiamino; lower N-alkyl-N-phenylamino; phenylamino; benzylamino; and sulpho; (v) aminonaphthalenes which are unsubstituted or substituted on the or each nitrogen atom by one or two of the same or different substituents selected from alkyl, e.g. lower alkyl, radicals and phenyl groups and are unsubstituted or substituted in the or each aromatic nucleus by 1, 2 or 3, preferably 1 or 2, of the same or different substituents, preferably by a total of 1 to 3, especially 1 to 2, substituents selected from sulpho; lower alkyl, e.g. methyl and ethyl; lower alkoxy, e.g.

methoxy and ethoxy; halogen, e.g. chlorine and bromine; lower alkanoylamino; benzoylamino; amino; lower alkylsulphonyl; phenylsulphonyl; lower alkylamino; di-lower alkylamino; lower N alkyl-N-phenylamino; phenylamino; and benzylamino; and (vi) anilines, including diaminobenzenes, which are unsubstituted or substituted on the or each nitrogen atom by one or two of the same or different substituents selected from alkyl radicals, e.g.

lower alkyl radicals, and phenyl groups, and are unsubstituted or substituted in the aromatic nucleus by 1, 2 or 3, preferably 1 or 2, of the same or different substituents selected from lower alkyl, e.g. methyl and ethyl; lower alkoxy, e.g. methoxy and ethoxy; halogen, e.g. chlorine and bromine; lower alkanoylamino; benzoylamino; lower alky!sulphonyl; phenylsulphonyl; lower alkylamino; di-lower alkylamino; lower N-alkyl-N-phenylamino; phenylamino; and benzylamino.

Preferably n represented 1.

Here and in the following text, the term "lower" used in connection with aliphatic radicals, e.g.

alkyl groups and moieties, and compounds denotes such radicals and compounds that have 1 to 4 carbon atoms.

Z preferably represents a group of the formula -S02-CH2-cH2-21 (2a) -SO2-CHCH2 (2b) or

in which Z, represents a hydroxy group or an inorganic or organic radical which can be eliminated together with a hydrogen atom on the adjacent carbon to form -S02-CH=CH2, R represents a hydrogen atom or a lower alkyl group, e.g. a methyl or ethyl group, which can, if desired, be substituted by a cyano group, and Y represents a fibre-reactive radical belonging to the cycloaliphatic, aromatic or heterocyclic series or a radical belonging to the aliphatic series, and thus also may represent a radical of the above formula (2a) or (2b).

KZn preferably represents a radical of the formula

in which A represents a phenyl or naphthyl or naphthyl radical; Z has the meaning given above, especially the preferred meaning; n represents 1 or 2 preferably 1; n' represents 1 or 2, preferably 1, and n and n' can be the same or different; R2 represents a hydrogen atom, a lower alkyl group, especially a methyl ethyl group, a lower alkdxv group, especially a methoxy or ethoxy group, a chlorine or bromine atom or a sulphonic acid group; R3 represents a hydrogen atom, a lower alkyl group, especially a methyl or ethyl group, a lower alkoxy group, especially a methoxy or ethoxy group, or a chlorine or bromine atom;; R4 represents a hydrogen atom, a lower alkyl group, especially a methyl or ethyl group, a lower alkoxy group, especially a methoxy or ethoxy group, or the sulphonic acid group, and R2, R3 and R4 can be the same or different; R2, represents a hydrogen atom, a lower alkyl group, especially a methyl or ethyl group, a lower alkoxy group, especially a methoxy or ethoxy group, a chlorine or bromine atom, a lower alkanoylamino group, e.g. an acetylamino group, or a sulphonic acid group; B1 represents a lower alkyl group, preferably a methyl group, a carboxyl group or a methoxycarbonyl or ethoxycarbonyl group;; B2 represents a lower alkyl group, preferably a methyl group, a methoxycarbonyl or ethoxycarbonyl group, a carboxamide group or a phenyl radical which is unsubstituted or substituted by 1 or 2 of the same or different substituents selected from lower alkyl, lower alkoxy, chlorine, bromine and sulpho, and R2,, R3 and R4 and B, and B2, respectively, can be the same or different; R' represents a hydrogen atom or a lower alkyl radical; R" represents a hydrogen atom, a lower alkyl radical or a phenyl radical which is unsubstituted or substituted by 1 or 2 of the same or different substituents selected from lower alkyl, lower alkoxy, chlorine, bromine and sulpho, and R' and R" can be the same or different; m represents zero, 1 or 2; R5 represents a hydrogen atom, a lower alkyl group, e.g. a methyl or ethyl group, a lower alkoxy group, e.g; a methoxy or ethoxy group, or a chlorine or bromine atom, R6 represents a hydrogen atom or a lower alkyl group which is unsubstituted or substituted by a hydroxy, cyano, carboxy, sulpho, sulphato, methoxycarbonyl, ethoxycarbonyl or acetoxy group, R7 represents a hydrogen atom or a lower alkyl group which is unsubstituted or substituted by a hydroxy, cyano, carboxy, sulpho, sulphato, methoxycarbonyl, ethoxycarbonyl or acetoxy group, or represents a benzyl radical or a phenyl radical which is unsubstituted or substituted by one or more of the same or different substituents selected from lower alkyl, lower alkoxy, chlorine and sulpho; and R'5 represents a hydrogen atom, a lower alkyl group, e.g. a methyl or ethyl group, a lower alkoxy group, e.g. a methoxy or ethoxy group, a chlorine or bromine atom, a lower alkanoylamino group, e.g. an acetylamino group, or an amino, ureido, lower alkylsulphonylamino, lower alkylamino or di-lower alkylamino group, and R, R2,, R'sl R5, Re and R, can be the same or different.

Radicals represented by Z, which can be eliminated together with a hydrogen atom from the group of the formula (2a) by the action of alkalis are, for example, a halogen atom, e.g. a chlorine or bromine atom, the sulphato, thiosulphato or phosphato group, or a lower alkylsulphonyloxy group, e.g.

the methylsulphonyloxy or ethylsulphonyloxy group, or a lower dialkylamino group, for example the dimethylamino or diethylamino group. Radicals represented by Z, which can be eliminated together with a hydrogen atom under neutral or acid conditions are, for example, the N-(ss-sulphoethylamino) or the N-(P-sulphoethyl)-N-methylamino group, which are preferably in the form of their sodium, potassium or ammonium salt.

The fibre-reactive radical represented by Y is preferably a known fibre-reactive acyl radical of a lower alkene- or alkyne-carboxylic acid, a lower halogenoalkanecarboxylic acid, a lower halogenoalkenemonocarboxylic or halogenoalkenedicarboxylic acid, a nitrohalogenobenzenesulphonic or nitrohalogenobenzenecarboxylic acid, a halogenocyclobutylcarboxylic or halogenocyclobutenylcarboxylic acid or a halogenocyclobutylacrylic or halogenocyclobutenylacrylic acid or a halogenoethylsulphonylendomethylenecyclohexanecarboxylic acid, a known fibre-reactive acyl radical of a benzoheterocyclic carboxylic or sulphonic acid which is substituted by halogen in the heterocyclic structure, such as a halogenobenzoxazolecarboxylic acid or a halogenobenzthiazolecarboxylic or halogenobenzthiazolesulphonic acid, and also the fibre-reactive acyl radical of an aromatic-heterocyclic carboxylic acid or sulphonic acid, the heterocyclic structure of which preferably contains 2 or 3 nitrogen atoms and is preferably a 6-membered heterocyclic structure, for example the pyridazine, pyridazinone, pyrimidine, phthalazine, quinazoline or quinoxaline radical, wherein the heterocyclic structure is substituted by one or two fibre-reactive leaving groups, preferably belonging to the group comprising halogen, such as chlorine and fluorine, lower alkylsulphonyl and sulpho, and can be substituted by 1, 2 or 3 further substituents, such as, for example, substituents belonging to the group comprising lower alkyl, lower alkoxy, lower carboalkoxy, lower halogenoalkyl, lower hydroxyaikyl, carboxy, sulpho, aryloxy, aliphatic mercapto, aromatic mercapto, lower alkanoyl, cyano, nitro and primary, secondary and tertiary amino groups having aliphatic, heterocyclic and/or aromatic radicals, which can be substituted, and also the fibre-reactive radical of a heterocyclic structure having 2 or 3 nitrogen atoms, in particular a six-membered heterocyclic structure, for example the pyrimidine, pyridazine or triazine ring, wherein the heterocyclic structure is substituted by one or two fibre-reactive leaving groups, preferably belonging to the group comprising halogen, such as chlorine and fluorine, lower alkylsulphonyl and sulpho, and can be substituted by 1, 2 or 3 further substituents, such as, for example, substituents belonging to the group comprising lower alkyl, lower alkoxy, lower carboalkoxy, lower halogenoalkyl, lower hydroxyalkyl, carboxy, sulpho, aryloxy, aliphatic mercapto, aromatic mercapto, lower alkanoyl, cyano, nitro and primary, secondary and tertiary amino groups having aliphatic, heterocyclic and/or aromatic radicals.

Y can also be a radical of the above formula (2a) in which Z1 has the meaning indicated or can be the vinylsulphonyl group.

Examples of the fibre-reactive radicals Y of the formula (2c) are Table A: the chloroacetyl, bromoacetyl, -chlornpropionyl, p-bromopropionyl, a,-dichlornprnpionyl or dibromopropionyl radical, the acyl radical of a chloromaleic acid, the /3-sulphatoethylsulphonyl radical, the acryloyl radical, the ,B-chloroacryloyl radical, the ,-bromoacryloyl radical, the a-chloroacryloyl radical, the a-bromoacryloyl radical, the a"B-dichloroacryloyl radical, the a,/3-dibromoacryloyl radical, the trichloroacryloyl radical, the chlorocrotonyl radical, the propiolyl radical, the 3,5-dinitro-4-chlorobenzenesulphonyl radical, the 3,5-dinitro-4-chloro-benzenecarbonyl radical, the 2,2,3,3tetrafluorocyclobutylacryloyl radical, the 2,2,3,3-tetrafluorocyclobutylcarbonyl radical, the 2,3,3 trifluorocyclobut-1-enylacryloyl radical, the 3-nitro-4-chlorobenzenesulfonyl radical, the 3-nitro-4chlorobenzenecarbonyl radical, the ,B-chloroethylsulfonylendomethylenecyclohexanecarbonyl radical and the 3-p-chloroethylsulfonylbenzoyl radical and also the 2-chlorobenzoxazolecarbonyl radical, the 2chlorobenzthiazolecarbonyl radical or the 2-chlorobenzthiazolesulfonyl radical, and also the sixmembered heterocyclic acid radicals (acyl radicals) of P-(4.5-dichloropyridazi n-g-on-l -yl)-propionic acid, 1 ,4-dichlorophthalazinecarboxylic or 1 ,4-dichlorophthalazinesulfonic acid, 2,4dichloroquinazolinecarboxylic or 2,4-dichloroquinazolinesulfonic acid, 2,3-dichloroquinoxalinecarboxylic or 2,3-dichloroquinoxaline sulfonic acid, 2,6-bismethylsulfonylpyridine-4carboxylic acid, 3,6dichloropyridazine-5-carboxylic acid, 2,4-dichloropyrimidine-6-carboxylic acid, 2,4-dichloropyrimidine5-carboxylic acid, 2,6-dichloropyrimidine-4-carboxylic or 2,6-dichloropyrimidine-4-sulfonic acid, 2,6dibromopyrimidine-4-carboxylic or 2,6-dibromopyrimidine-4-sulfonic acid, 2,6-dichloropyrimidine-5carboxylic or 2,6-dichloropyrimidine-5-sulfonic acid, 2,6-dibromopyrimidine-5-carboxylic or 2,6dibromopyrimidine-5-sulfonic acid, 2-chlorobenzthiazole-6-carboxylic acid and 2-chlorobenzthiazole-6sulfonic acid, the s-sulfatoethylsulfonyl radical, the ,B-chloroethylsulfonyl radical, the p- phosphatoethylsuifonyl radical, the p-thiosulfatoethylsulfonyl radical and the vinylsulfonyl radical, and also the des-halogeno radical, des-sulfo radical or des-alkylsulfonyl radical, as relevant, of p-(4,5- dichloropyridazin-6-on-1 -yl)-propionic acid, 1 ,4-dichlorophthalazinecarboxylic or 1,4dichlorophthalazinesulfonic acid, 2,4-dichloroquinazolinecarboxylic or 2,4-dichloroquinazolinesulfonic acid, 2,3-dichloroquinoxaline carboxylic or 2,3-dichloroquinoxalinesulfonic acid, 2-methylsulfonyl-4chloro-6-methyl pyri midine, 2,4-bis-methylsulfonyl-6-methylpyri midine, 2,4,6-tribromopyrimidine, 2,4, 5,6-tetrabromopyrimidine, 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidi ne, a 2,4dichloropyrimidine-5-sulfonic acid, a 5-nitro-2,4,6-trichloropyrimidine, a 5-cyano-2,4,6trichloropyrimidine, 2,6-bis-methylsulfonylpyridine-4-carboxylic acid, 2,4-dichloro-5-chloromethyl-6 methylpyrimidine, 2,4-dibromo-5-bromomethyl-6-methyl-pyrimidine, 2,4-dichloro-5 bromomethylpyri midine, 2,4-di-bromo-5-bromomethylpyrimidine, 2,5,6-trichloro-4-methyl-pyrimidine, 2,6-dichloro-4-trichloromethylpyri midine, 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine, 2,4,6 trimethylsulfonyl-1 3,5-triazine, 2,4-dichloropyrimidine, 3,6-dichloropyrimidine, 3,6-dichloropyridazine5-carboxyli c acid, 2,6-dichloro-4-carboethoxypyrimidi ne, 2 ,6-dibromo-4-carboethoxypyrimidine, 2,4,5trichloropyrimidine, 2,4-dichloropyrimidine-6-carboxylic acid, 2,4-dichloropyrimidine-5-carboxylic acid, 2,6-dichloropyrimidine-4-carboxylic acid amide, 2,6-dibromopyrimidine-4-carboxylic acid amide, 2,6 dichloropyrimidine-4-carboxylic or 2,6-dichloropyrimidine-4-sulfonic acid, 2,6-dibromopyrimidine-4carboxylic or 2,6-dibromopyrimidine-4-sulfonic acid, 2,6-dichloropyrimidine-5-carboxylic or 2,6dichloropyrimidine-5-sulfonic acid amide, 2,6-dibromopyrimidine-5-carboxylic or 2,6dibromopyrimidine-5-sulfonic acid amide, 2,6-dichloropyrimidine-5-carboxylic or dichloropyri midine-5-sulfonic acid, 2,6-dibromopyrimidi ne-5-carboxylic or 2,6-dibromopyrimidine-5sulfonic acid, 2,4,5,6-fetrachlornpyndazine, 5-bromo-2,4,6-trichloropyri midine, 5-acetyl-2,4,6trichloropyri midi ne, 5-nitro-6-methyl-2,4-dichl oropyrimidine, 2,4,6-trichloro-5-bromopyrimidine, 2,4,5,6-tetrafl uoropyrimidine, 4,6-difluoro-5-chloropyrimidi ne, 2,4,6-trifluoro-5-chloropyrimidine, 2,4,5-trifluoropyrimidine, 2,4,6-trichloro-1 ,3,5-triazine, 2,4,6-tribromo-1 ,3,5-triazine; 2,4,6-trifluoro 1 3,5-triazine or a 4,6-difluoro-1 ,3,5-triazine, 4,6-dibromo-1 ,3,5-triazine or 4,6-dichloro-1 ,3,5-triazine, it being possible for these dihalogenotriazines to be additionally substituted in the 2-position by a radical belonging to the group comprising aryl, such as phenyl, lower alkyl, such as methyl or ethyl, aliphatic mercapto, such as lower alkylmercapto, aromatic mercapto, such as arylthio, for example phenylthio, aliphatic oxy, such as lower alkoxy, aromatic oxy, such as aryloxy, for example phenoxy and naphthoxy, or primary amino, secondary amino and tertiary amino containing aliphatic, heterocyclic and/or aromatic radicals.

Radicals of this type, which are linked in the 2-position to the triazine nucleus of the 4,6dihalogeno compound and can be prepared via the corresponding, for example the following, compounds by reaction with trihalogenotriazines, are, for example, the ether radicals of, for example, the following aliphatic and aromatic hydroxy compounds: lower thio alcohols, lower alkoxy-lower alkanols, lower alkanols, such as methanol, ethanol and isopropanol, glycollic acid, phenol, chlorophenols and nitrophenols, phenolcarboxylic and phenolsulfonic acids, naphthols and naphtholsulfonic acids, and, for example, the thioether radicals of, for example, aliphatic and aromatic mercapto compounds, such as thioglycollic acid and thiophenols.Amino groups which can be present in the 2-position of the triazine are, in particular, not only the primary amino group -NH2 but also aliphatic and/or aromatic amino groups, which can contain an acylatable amino or hydroxy group, such as amino radicals of hydroxylamine, hydrazine, sulfophenylhydrazine, ethanolamines and propano!amines, and also the amino radicals of methylamine, ethylamine, isopropylamine, methoxyethylamine, methoxypropylamine, dimethylamine, diethylamine, methylphenylamine, ethylphenylamine, chloroethylamine, benzylamine, cyclohexylamine, morpholine, piperidine and piperazine and also, preferably, of N,N-bis--('-chlornethylsulfonyl)-ethylamine and also of oxygen ether compounds which can also contain an amino group which can be acylated, such as hydroxyamine.

The new compounds of the formula (1) are prepared in a manner according to the invention by diazotizing in a customary manner a 1-amino-2-sulfo-4-(4t-aminophenyl)-aminoanthraquinone compound of the general formula (4)

in which R1 has the meaning mentioned above, by means of an equivalent quantity of sodium nitrite, in the presence of a mineral acid, such as, for example, hydrochloric acid, selectively to give the diazo compound of the general formula (5)

in which R1 has the meaning cited, and subsequently coupling the diazonium salt of the cation of the formula (5) thus obtained with a coupling component of the formula (6) HKZn (6) in which K, Z and n have the meaning mentioned above, but in which Z is not in the ortho-position or para-position in relation to the coupling point.The coupling can be carried out within a pH range from 2 to 9; however, in order to avoid a loss of fiber-reactivity, if the coupling component contains a highly fiber-reactive group as the fiber-reactive group Z, it is preferable to carry out the coupling at a pH value of 2 to 7.5, preferably at a pH value of 3 to 6.5.

The present invention enriches the art with further valuabie dyestuffs, but also enriches it with a new, simple means, which involves little technical outlay, of synthesizing anthraquinone-azo compounds of the type of the formula (1). It is in fact not possible to follow a method of synthesis for the preparation of the new compounds of the formula (1) which is analogous to the processes known from U.S. Patent Specifications Nos. 2,108,126 and 2,154,954, because the condensation reaction of 1 -amino-4-bromoanthraquinone-2-sulfonic acid with a corresponding aminosulfophenyleneazo compound in the presence of copper salts fails, since the amino group in the 1 -amino-2-suifophenyl-4- azo or 1 -amino-3-sulfophenyl-4-azo compounds is not sufficiently nucleophilic for this reaction.

The compounds of the formula (1) wherein Z is the radical of the formula (2c) can also be prepared in a manner according to the invention, preferably by coupling the diazonium compound of the formula (5) with a coupling component of the formula (7) H-K-Z2 (7) in which K has the meaning mentioned above and Z2 is the group of the formulaNHR in which R has the meaning mentioned above, and subsequently reacting, in a manner analogous to customary and known process methods, the resulting compound of the formula (8), written in the form of the free acid,

in which Rr, R and K have the meaning mentioned, with a compound of the formula (9) which contains the fiber-reactive radical Y and which has the formula (9) Hal-Y (9) wherein Y has the above mentioned meaning and Hal is a fluorine, chlorine or bromine atom, or with a corresponding acid anhydride containing the radical Y (Y20).

Coupling components of the above formula (7) which can be employed in the process according to the invention, are preferably the compounds of the formulae (7a), (7b), (7c), (7d), (7e), (7f), (79), (7h), (7i), (7j), (7k) or (7m)

In the formulae (7a) to (7m), Z2, R2, R3, R4, n', A, R2", R5", R', R", R5, Re and R7 have the meanings indicated above.

The following are examples of the coupling components of the general formula (6): N acetoacetylaniline-3-ss-sulfatoethyl sulfone, N-acetoacetylaniline-4-ss-sulfatoethyl sulfone, Nacetoacetylaniline-3-ss-chloroethyl sulfone, N-acetoacetylaniline-4-ss-chloroethyl sulfone, Nacetoacetyl-2-methoxy-5-ss-sulfatoethylsulfonylaniline, N-acetoacetyl-2-methoxy-5vi nylsulfonyla ni line, N-acetoacetyl-4-methoxy-3-ss-sulfatoethylsu Ifonyla ni line, N-acetoacetyl-2methoxy-5-methyl-4-ss-sulfatoethylsulfonylaniline, N-acetoacetyl-2-methoxy-5-methyl-4-ss thiosulfatoethylsulfonylaniline, N-acetoacetyl-2 ,5-di methoxy-4-ss-sulfatoethylsulfonylaniline. Nacetoa cetyl-2,5-di methoxy-4-p-( methylsulfonyloxy)-ethylsulfonyla niline, 1 -(4'-p- sulfatoethylsulfonylphenyl)-3-methylpyrazol-5-one, 1-(3'-ss-sulfatoethylsulfonylphenyl)-3carboxypyrazol-5-one, 1-(2'-methoxy-4'-ss-sulfatoethylsulfonylphenyl)-3-carboxypyrazol-5-one, 1-(3' ,B-su lfatoethylsulfonylphenyl)-3-methyl-5-a mi nopyrazole, 1 -(4'-ss-sulfatoethylsu Ifonylph enyl)-3-methyl5-a minopyrazole, 1 -(2'-methoxy-5'-ss-sulfatoethylsulfonylphenyl)-3-methyl-5-aminopyrazole, 1 -(2'methoxy-5'-methyl-4'-ss-sulfatoethylsulfonylphenyl)-3-methyl-5-aminopyrazole, N-acetoacetyl-(4-N-sssulfatoethylsulfonylamino)-aniline, N-acetoacetyl-(3-N-ss-sulfatoethylsulfonylamino)-aniline, Nacetoacetyl-(2-methyl-4-N-ss-sulfatoethylsulfony ami no)-aniline, N-acetoacetyl-(2-methoxy4-N-ss-sulfatoethylsulfonylamino)-aniline, N-acetoacetyl-(4-N-ss-sulfatoethylsulfonyl-Nmethylamino)-aniline, N-acetoacetyl-(3-N-ss-sulfatoethylsulfonyl-N-ethylami no)-aniline, 1 -(4'-N-,B-sulfatoethylsulfonylami no)-phenyl-3-methylpyrazol-5-one, 1 -(3'-N-ss-sulfatoethylsulfonyl- N-methylamino)-phenyl-3-carbomethoxypyrazaol-5-one, 1 -(4'-N-vinyylsulfonyl-N-methyla mi no)- phenyl-3-methyl-5-aminopyrazole, 1-(3'-ss-sulfatoethylsulfonylamino-6'-methyl)-phenyl 3-carboxypyrazol-5-one, 1-amino-3-(N-ss-sulfatoethylsulfonyl-N-methyl)-aminobenzene, 1-amino-3-(N p-su lfatoethylsulfonyl-N-ethyl)-a minobenzene, 2-(N-/3-su Ifatoethylsulfonyl-N-methyl)-a mino-8 naphthol-6-sulfonic acid, 2-(N-vinylsulfonyl-N-methyl)-amino-8-naphthol-6-sulfonic acid, 2-(N-P- sulfatoethylsulfonyl-N-methyl)-amino-5-naphthol-7-sulfonic acid or 2-(N-vinylsulfonyl)-amino-5 naphthol-7-sulfonic acid.

The following are examples of the coupling components of the general formula (7): 1-N acetoacetylamino-4-aminobenzene, 1 -N-acetoacetylamino-4-N-methyla minobenzene, 1-N acetoacetyla mino-3-methyl-4-a minobenzene, 1 -N-acetoacetylamino-3-methoxy-4-a minobenzene, 1 (3'-aminophenyl)-3-methylpyrazol-5-one, 1 -(4'-aminophenyl)-3-methylpyrazol-5-one, 1 -(3' aminophenyl)-3-carboethoxypyrazol-5-one, 1-(4'-aminophenyl)-3-carboethoxypyrazol-5-one, 1-(3' sulfo-4'-aminophenyl)-3-carboethoxypyrazol-5-one, 1-(3'amino-4'-sulfophenyl)-3 carboethoxypyrazol-5-one, 1-(2',4',6'-trimethyl-3'-amino-5'-sulfophenyl)-3-carboethoxypyrazol-5-one, aniline-N-methanesulfonic acid, o-toluidine, m-toluidine, 2,6-dimethylaniline, 2,5-dimethylaniline, o ethylaniline, m-ethylaniline, o-tert.-butylaniline, m-chloroaniline, o-anisidine, m-anisidine, o phenetidine, m-phenetidine, N-methylaniline, N-ethylaniline, N-ss-hydroxyethylaniline, N-j3- acetoxyethylaniline, N-butylaniline, 4-ss-cyanoethylaniline, N-ss-cyanoethyl-m-toluidine, N-ethyl-mtoluidine, 2-aminohydroquinone dimethyl or diethyl ether, cresidine, m-phenylenediamine, 3-N acetylaminoaniline, 3-ureidoaniline, 3-N-methylsulfonyla minoaniline, 2-methoxy-5-acetylaminoaniline, 1 -aminonaphthalene-6-sulfonic acid, 1 -aminonaphthalene-7-sulfonic acid, 2-methoxy-1 aminonaphthalene-6-sulfonic acid, 2-ethoxy-1 -aminonaphthalene-6-sulfonic acid, 2-amino-8naphthol-6-su Ironic acid, 2-a mino-5-naphthol-7-sulfonic acid, 2-methyla mino-8-naphthol-6-sulfonic acid, 1 -amino-8-naphthol-3,6-disulfonic acid or 1 -amino-8-naphthol-4,6-disulfonic acid.

Compounds of the formula (9) are, for example, chloroacetyl chloride, bromoacetyl chloride, ss- chloropropionyl chloride, -bromoprnpionyl chloride, a,ss-dichloropropionyl chloride, a, dibromopropionyl chloride, chloromaleic anhydride, acre loyal chloride, P-chloroacryloyl chloride, bromoacryloyl chloride, &alpha;;-chloroacryloyl chloride, a-bromoacryloyl chloride, a,ss-dichloroacryloyl chloride, ,ss-dibromoacryloyl chloride, trichloroacryloyl chloride, chlorocrotonyl chloride, propiolyl chloride, 3,5-dinitro-4-chlorobenzenesulfonyl chloride, 3,5-di nitro-4-chlorobenzoyl chloride, 2,2,3,3tetrafluorocyclobutylacryloyl chloride, 3-nitro-4-chlorobenzenesulfonyl chloride, 3-nitro-4chlorobenzoyl chloride, 2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid chloride, sschloroethylsulfonylendomethylenecyclohexa necarboxylic acid chloride, 3-P-chloroethylsulfonylbenzoyl chloride and heterocyclic acid halides and derivatives thereof, such as the 2chlorobenzoxazolecarboxylic acid chlorides, 2-chlorobenzthiazolecarboxylic acid chlorides and 2chlorobenzthiazolesulfonyl chlorides, above all those containing at least two nitrogen atoms as the hetero-atoms of a 6-membered heterocyclic structure, such as, for example, ss-(4,5-dichloropyridazin-6- on-1 -yl)-propionyl chloride, 1 ,4-dichlorophthalazinecarboxylic acid chloride, 1,4dichlorophthalazinesulfonyl chloride, 2,4-dichloroquinazolinecarboxylic acid chloride, 2,4dichloroquinizolinesulfonyl chloride, 2,3-dichloroquinoxalinecarboxylic acid chloride, 2,3dichloroq uinoxalinesulfonyl chloride, 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 2,4-bismethylsulfonyl-6-methylpyrimidine, 2,4,6-tribromopyrimidine, 2,4,5,6-tetrabromopyrimidine, 2 methylsulfonyl-4,5-dichloro-6-methylpyrimidine, 2,4-dich loropyrimidine-5-sulfonic acid, 5-nitro-2,4,6trichloropyrimidine, 5-cyano-2,4,6-trichloropyrimidine, 2,6-bis-methylsulfonylpyridine-4-carboxylic acid chloride, 2,4-dichloro-5-chloromethyl-6-methylpyrimidine, 2,4-dibromo-5-bromomethyl-6methylpyrimidine, 2,4-dichloro-5-bromomethylpyrimidine, 2,4-dibromo-5-bromomethylpyrimidine.

2,5,6-trichloro-4-methylpyrimidine, 2,6-dichloro-4-trichloromethylpyrimidine, 2,4-bis-methylsulfonyl5-chloro-6-methylpyrimidine, 2,4,6-trimethylsulfonyl-1,3,5-triazine, 2,4-dichloropyrimidine, 3,6 dichloropyrimidine, 3,6-dichloropyridazine-5-carboxylic acid chloride, 2,6-dichloro-4carboethoxypyrimidine, 2,6-dibromo-4-carboethoxypyrimidine, 2,4,5-trichloropyrimidine, 2,4dichloropyrimidine-6-carboxylic acid chloride, 2,4-dichloropyri midine-5-carboxylic acid chloride, 2,6dichloropyrimidine-4-carboxylic and 2,6-dichloropyrimidine-4-sulfonic acid amides, 2,6-dichloro-5- carboxylic and 2,6-dichloro-5-sulfonic acid amides, 2,6-dibromopyrimidine-4-carboxylic and 2,6 dibromopyrimidine-4-sulfonic acid amides, 2,6-dibromopyrimidine-5-carboxylic and 2,6dibromopyrimidine-5-sulfonic acid amides, 2,6-dichloropyrimidine-4-sulfonyl chloride, 2,6 dichloropyrimidine-5-sulfonyl chloride, 2,6-dibromopyrimidine-4-sulfonyl chloride, 2,6dibromopyrimidine-5-sulfonyl chloride, 2,4,5,6-tetrachloropyridazine, 5-bromo-2,4,6trichloropyrimidine, 5-acetyl-2,4,6-trichloropyrimidine, 5-nitro-6-methyl-2,4-dichloropyrimidine, 2 chlorobenzthiazole-6-carboxylic acid chloride, 2-chlornbenzthiazole-6-sulfonyl chloride, 5-nitro-6-methyl- 2,4-dibromopyrimidine, 2,4,6-trichloro-5-bromopyrimidine, 2,4,5,6-tetrafluoropyrimidine, 4,6-difluoro5-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,4,5-trifluoropyrimidine, 2,4,6-trichloro-1,3,5- triazine, 2,4,6-tribromo-1 ,3,5-triazine, 2,4,6-trifluoro-1 ,3-5-triazine and the 4,6-dichloro-1,3,5triazines, 4,6-dibromo-1 ,3,5-triazines and 4,6-difluoro-1,3,5-triazines which can be substituted in the 2-position by an aryl or lower alkyl radical, such as the phenyl, methyl or ethyl radical, or by an aliphatic or aromatic thioether or oxygen ether radical of the type cited earlier in the text or, especially, by a primary amino group or by an amino group which is substituted by aliphatic, heterocyclic and/or aromatic radicals.

The compounds of the general formula (6) which are used as the coupling components and in which Z is a fiber-reactive group of the above formula (2c) are known in large numbers from the literature and are prepared by methods described in the literature or by analogous procedures and process conditions, for example by reacting compounds of the general formula (7) with a compound of the general formula (9) in which K, R, Y and Hal have the meaning cited initially, or with a corresponding acid anhydride containing the radical Y. Compounds of theformula (6) in which Z is NRY and Y is the /3- sulfatoethylsulfonyl radical, are also obtained, for example, by reacting a compound of the formula (7) with carbyl sulfate.

The coupling components of the formula (6) in which Z is a fiber-reactive group of the formula (2a) or (2b) are likewise described in a large number of publications and patent specifications, from which their mode of preparation is also known.

Compounds of the general formula (1) containing the fiber-reactive group of the formula (2a) in which Z1 is the sulfato or phosphato group, can be prepared, according to the invention, by converting a compound of the formula (1) which has been obtained by the above procedure and contains the radical of the formula (2a) in which Z, is the hydroxy group, into the corresponding ester by means of a sulphating or phosphating agent analogously to a procedure known in the art. Examples of sulfating agents are concentrated sulfuric acid, sulfuric acid containing sulfur trioxide (oleum), chlorosulfonic acid and amidosulfonic acid. Examples of phosphating agents are concentrated orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid or mixtures of phosphoric acid and phosphorus pentoxide.

The isolation from the reaction batch of the compounds which have been prepared in accordance with the invention is effected by generally known methods, either by precipitation from the reaction medium by means of electrolytes, such as, for example, sodium chloride or potassium chloride, or by evaporating the reaction solution, for example by spray-drying. If the last-mentioned method of dyestuff isolation is selected, it is frequently advisable to eliminate, by precipitation as gypsum and removal by filtration, any quantities of sulfate which may be present in the solutions, before evaporation. In some cases it can also be desirable to use the dyestuff solution, if appropriate after adding buffer substances, directly for tinctorial purposes, as a iiquid preparation.

The new compounds of the formula (1) have proved to be compounds possessing very good dyestuff properties; in particular, as water-soluble dyestuffs, they are excellently suitable for dyeing and printing fibers, containing carboxyamide groups, of both natural and synthetic origin, such as silk, wool and other animal hairs, polyamide fibers and polyurethane fibers. They are particularly advantageously suitable for dyeing wool.

For dyeing and printing the abovementioned fiber materials, they are applied to the fiber material, and are fixed thereon, by the dyeing and printing processes which are known and customary in the art.

Thus, for example, for dyeing wool and polyamide fibers, the new dyestuffs are applied to these fibers from a neutral, or preferably a weakly acid, aqueous dyebath at a constant or virtually constant pH value.

Dyeing is preferably carried out in this procedure at between 40 and 1 200C in the presence of compounds which are customary for such fiber materials in dyebaths and dye liquors, such as, for example, sodium sulfate, ammonium acetate and surface-active compounds, such as quaternary ammonium salts and nonionic wetting agents and dispersing agents. It can prove to be advantageous for the evenness of the resulting dyeings to add jB-N-methylaminoethanesulfonic acid, in the form of its sodium salt. During the dyeing process, the pH value of the dyebath can be altered by adding acids or acid salts or correspondingly alkalis or alkaline salts, in such a way that, for example, the dyeing process begins at a pH value of 4.5 and the pH is raised to 7.5 during the dyeing process.

In addition to dyeing fiber materials containing carboxamide groups, the new dyestuffs, excepting those in which Z, is the N-(P-sulfoethylamino) group or the N-(/3-sulfoethyl)-N-methylamino group, are also very suitable for dyeing and printing fiber materials containing hydroxy groups, in particular natural and regenerated cellulose fibers, such as cotton, linen or viscose rayon.Since the dyestuffs have fiberreactive properties, they are advantageously applied to these fiber materials by dyeing and printing processes which are customary and known for fiber-reactive dyestuffs, and are fixed in a customary manner with the aid of an acid-binding agent, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, disodium phosphate, sodium bicarbonate or water-glass, it being possible to apply these to the fiber materials at room temperature or elevated temperature, for example at temperatures between 20 and 1 800 C, before, during or after the application of the dyestuffs.

The present invention thus also relates to processes for coloring by dyeing and printing fiber materials containing hydroxy groups and synthetic and natural fiber materials containing caroboxamide groups, particularly those of the type mentioned above, by customary and known procedures, using as the dyestuff a compound corresponding to the general formula (1).

The new compounds of the general formula (1) produce green to olive-green, blue and grey dyeings and prints on the fiber materials cited.

The dyeings and prints obtained with the new dyestuffs have very good fastness to wet processing and very good fastness to light. Properties of this type which should be singled out particularly are the very good fastness to washing at various high temperatures in the washing baths, the very good fastness to acid and alkaline perspiration, the fastness to decatizing and milling, the fastness to peroxide bleaching and the fastness to cross-dyeing under acid conditions.

The Examples which follow serve to illustrate the invention. The parts are parts by weight and the percentages reiate to percentages by weight, unless a note is made to the contrary. Parts by weight have the same relation to parts by volume as the kilogram to the liter.

EXAMPLE 1 49 parts of 1-amino-4-(2'-sulfo-4'-aminophenyl)-aminoanthraquinone-2-sulfonic acid are dissolved to give a neutral solution in 500 parts of water containing 24.2 parts of 33% strength aqueous sodium hydroxide solution. 400 parts of ice are then added, followed by 60 parts of 31% strength hydrochloric acid. Diazotization is carried out with 1 7.3 parts of a 40% strength aqueous sodium nitrite solution, which is added dropwise in the course of 10 minutes, while stirring. Stirring is continued for 30 minutes; 40.9 parts of 1-N-acetoactyl-2-methoxy-5-methyl-4-p- sulfatoethylsulfonylaniline are then added and the pH value of the reaction mixture is adjusted to 6.0 with anhydrous sodium carbonate.A green solution is formed, from which the compound of the formula (written in the form of the free acid)

is precipitated by adding sodium chloride. It is excellently suitable for dyeing polyamide fiber materials of natural and synthetic origin and also cellulose fibers. In particular, in an aqueous dyebath containing a little acetic acid and heated to 950C, it dyes wool a strong green, with very good fastness to wet processing and very good fastness to light. Dyeings and prints which have very good fastness to wet processing and good fastness to light, are obtained on cotton or stapie rayon, by customary dyeing and printing processes.

EXAMPLE 2 57 parts of 1 -amino-4-(2',5'-disulfo-4'-aminophenyl)-aminoanThrnquinone-2-sulfonic acid are dissolved at a pH of 6.5 to 7.5 in 500 parts of water by means of 36.3 parts of 33% strength aqueous sodium hydroxide solution. 400 parts of ice, followed by 60 parts of 31% strength hydrochloric acid, are added and T7.3 parts of a 40% strength aqueous sodium nitrite solution are then added dropwise in the course of 10 minutes, while stirring. After stirring for a further 30 minutes, 27.2 parts of 4-Nacetoacetylaminoaniline-2-sulfonic acid are added as the coupling component and the pH value is adjusted to 5.5 to 6.0 with sodium carbonate. After the coupling is complete, the mixture is cooled to 1 OOC and a solution of 20.5 parts of cyanuric chloride in 60 parts by volume of acetone is added.The pH value is kept at 4.5 to 5.0 with sodium carbonate while the mixture is slowly warmed to room temperature. After the acylation reaction is complete, the resulting compound corresponding to the general formula (1) is precipitated by means of sodium chloride. It has the following structure, written in the form of the free acid.

Deep green dyeing and prints with very good fastness to wet processing and good fastness to light are obtained with the compound on cotton or staple rayon, by known dyeing and printing processes, in the presence of alka!i.

EXAMPLE 3 49 parts of 1 -amino-4-(2'-sulfo-4'-a minophenyl)-a minoanthraquinone-2-sulfonic acid are diazotized as described in Example 1.46.2 parts of 1 -(4'-P-sulfatoethylsulfonylphenyl)-3- methylpyrazol-5-one are added to this diazo suspension and the pH value is adjusted to about 6.0 with sodium carbonate. After the coupling reaction is complete, the resulting compound of the formula (written in the form of the free acid)

is salted out with sodium chloride. It is excellently suitable for dyeing cotton by customary dyeing and printing processes and produces grey dyeings and prints with good fastness to wet processing and good fastness to light.

EXAMPLE 4 49 parts of 1-amino-4-(2'-sulfo-4'-aminophenyl)-aminoanthraquinone-2-sulfonic acid are diazotized in accordance with the instructions of Example 1.29.9 parts of 1-(2'-sulfo-4'-aminophenyl)3-carboxypyrazo!-5-one are added to this diazo suspension and the pH value is adjusted to about 6.5 with sodium carbonate. After the coupling is complete, a solution of 32.5 parts of N-(dichlorotriazinyl)aniline-3-sulfonic acid in 1 50 parts by volume of water is run in, the pH value being adjusted to 5.5 to 6.0 with sodium carbonate. The acylation is carried out at 400 C. After the completion of the reaction, the resulting compound of the formula (written in the form of the free acid)

is salted out with sodium chloride. It has very good dyestuff properties and dyes cotton and regenerated cellulose using customary dyeing and printing processes, in grey shades which are fast to wet processing and light.

EXAMPLE 5 49 parts of 1 -amino-4-(2'-sulfo-4'-aminophenyl)-a minoanthraquinone-2-sulfonic acid are diazotized in accordance with the instructions of Example 1. A solution of 13.7 parts of 2-methoxy-5methylaniline and 15 parts of 31% strength hydrochloric acid in 100 parts by volume of water are run into this diazo suspension. In order to carry out the coupling reaction, the pH of this reaction solution is adjusted, by sprinkling in sodium bicarbonate, to a value of 2.5 to 3.0, which is maintained until the coupling reaction is complete.

The mixture is then neutralized with sodium carbonate to a pH value of 7.5 and a solution of the condensation product of 1 9.4 parts of cyanuric chloride with 26.6 parts of aniline-2,5-disulfonic acid in 150 parts by volume of water is then added. The mixture is warmed to 400C and the pH is kept at 6.5 to 6.8 with sodium carbonate. After the acylationis complete, the compound according to the general formula (1), having the formula, written in the form of the free acid,

which has been prepared in this way, is salted out with sodium chloride.The compound has very good dyestuff properties and dyes, for example, cotton fiber materials and regenerated cellulose fiber materials in olive-green shades which are fast to wet processing and light, using dyeing and printing processes which are customary for fiber-reactive dyestuffs.

EXAMPLE 6 49 parts of 1-amino-4-(3'-sulfo-4'-aminophenyl)-aminoanthraquinone-2-sulfonic acid are dissolved to a neutral solution in 500 parts of water by means of 24.2 parts of 33% strength aqueous sodium hydroxide solution. 400 parts of ice are added, followed by 60 parts of 31% strength hydrochloric acid, and 1 7.3 parts of a 40% strength aqueous sodium nitrite solution are then added dropwise in the course of 10 minutes. The diazo suspension is stirred for a further period of 30 minutes and a solution of 12.1 parts of 2,5-dimethylaniline in 15 parts of 31% strength hydrochloric acid and 100 parts by volume of water are then added; the pH value of the coupling mixture is adjusted to 2.8 to 3.2 with sodium bicarbonate and is kept thereat until the end of the reaction.Sodium carbonate is then added until a pH of 6.5 is reached and 18.7 parts of cr-bromoacryloyl chloride are added dropwise to the solution; the acylation reaction is kept at a pH value of about 6.5 by simultaneously sprinkling in sodium carbonate.

The end product according to the general formula (1) is precipitated from the solution with sodium chloride; it has the formula, written in the form of the free acid,

and has very valuable dyestuff properties. For example, in an aqueous bath containing a little acetic acid, at a temperature of about 980C, it dyes wool in green shades which have very good fastness to wet processing and good fastness to light.

EXAMPLES 7 TO 20 The compounds according to the general formula (1) which are listed in the following Examples and which also have good dyestuff properties in respect of tinctorial properties and also in respect of their fastness properties and which dye, for example, wool in the color shades indicated in the Table, are obtained if the procedure followed is analogous to that described in one of the above Examples, but employing, as the starting compounds, the corresponding 1-amino-4-(4'-aminosulfophenyl)- aminoanthraquinone-2-sulfonic acid compound and coupling component containing the fiber-reactive group or the corresponding coupling component containing the amino groups and the corresponding fiber-reactive acylating agent.

Example Compound according to formula (1) Color on wool O NH2 CH CO i3 7 < | 3 S02-CH2-CH2 OS03 green o NHN=N-CH CO-NH S03H SOCH3 O INHI 8 OEH < 3N=N t N=N NH2 olive-green S03H Thi[2cn2 CH2-os03H SO H 3 3 O NH 9T'I'1'"" Ca CC4~NYN~C -cn2-cX2-cl green o H CO-NH O NH 10 503)1 503)1 10 0 NsN t 4So2-CN=CN2 olive SO H 0 t82 11 < 503N QN grey o NH < NH got-CN3 503H COOCH3 SO2CH2-CH2-OsO3N NH2 13 'I o NH Y 12 " , , t2 N N olive o NN 5.03)1 13soH oII ;;03X 13 N--N NHWN=Niss N N grey-olive I SOH 503H OCH3

o NH 14 503)1 N 4 < < D NxN wH-COnCl olive-green 503N tR NH-Co-CHCH2 olive-green > n , olive-green NH-CO-CHCH2

Example Compound according to formula (1) Color on wool

0 1, NH2 Is N-L3-8 503H C1J(2-CN olive-green O N89 N2 v NH wNN 503H Cl 02 CM g2 CM (Co5203H ( QȮ $2 503)1 2M5 5D3H .NN 3/ le '503)1 Cl 0t Nh grey-gre NB-CO-CHoCH2 SO jH \ 503)1 0)12 19 N=N e 503)1 NN C1N3 N 2 C1)12 navy-blue 503)1 5035 0503R NH 20 < 5035 HO N > zW mwblue 1,,iN NW 803)1 5035 5035 Cl

Claims (27)

1. A compound of the general formula

wherein R1 represents a hydrogen atom or a sulphonic acid group and the two R7 moieties can be the same or different, but are not both hydrogen at the same time; K represents the radical of a coupling component; Z represents a fibre-reactive group which is linked to a carbocyclic aromatic nucleus of the coupling component; and n represents the number 1 or 2, and two Z moieties can be the same or different, or a salt thereof.

2. A compound as claimed in claim 1, wherein K represents the acetoacetylanilide or acetoacetylnaphthylamide radical which is unsubstituted or substituted, in the carbocyclic aromatic nucleus or nuclei, by in total 1 , 2 or 3 of the same or different substituents selected from lower alkyl; lower alkoxy; halogen; nitro; carboxy; carboxylic acid amide; carboxylic acid amide which is substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; sulphonamide; sulphonamide which is substituted by one or two of the same or different substituents selected froth lower alkyl, benzyl and phenyl; formylamino; alkanoylamino having 1 to 4 carbon atoms in the alkyl moiety; benzoylamino; hydroxy; amino; lower alkylsulphonyl; phenylsulphonyl; lower alkylamino; di-lower alkylamino; lower N-alkyl-N-phenylamino; phenylamino; benzylamino and sulpho.

3. A compound as claimed in claim 1, wherein K represents the radical of 1 -phenyl-5-pyrazolone or 1 -naphthyl-5-pyrozolone which are substituted, in the 3-position, by lower alkyl, carboxy, carbamoyl, alkoxycarbonyl in which the alkoxy moiety has 1 to 4 carbon atoms, phenyl or phenyl which is substituted by one or more of the same or different substituents selected from lower alkyl, lower alkoxy and halogen, and of which the phenyl or naphthyl radical located in the 1-position is unsubstituted or substituted by 1, 2 or 3 of the same or different substituents selected from lower alkyl; lower alkoxy; halogen; nitro; carboxy; carboxylic acid amide; carboxylic acid amide which is substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; sulphonamide; sulphonamide which is substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; formylamino. alkanoylamino having 1 to 4 carbon atoms in the alkyl moiety; benzoylamino; hydroxy; amino; lower alkylsulphonyl; phenylsulphonyl; lower alkylamino; dilower alkylamino; lower N-alkyl-N-phenylamino; phenylamino; benzylamino and sulpho.

4. A compound as claimed in claim 1 , wherein K represents the radical of 1-phenyl-5- aminopyrazole or 1-naphthyl-5-aminopyrazole which are substituted, in the 3-position, by lower alkyl, carboxy, carbamoyl, alkoxycarboyl having 1 to 4 carbon atoms in the alkoxy moiety, phenyl or phenyl which is substituted by one or more of the same or different substituents selected from lower alkyl, lower alkoxy and halogen, and of which the phenyl or naphthyl radical located in the 1-position is unsubstituted or substituted by 1,2 or 3 of the same or different substituents selected from lower alkyl; lower alkoxy; halogen; nitro; carboxy; carboxylic acid amide; carboxylic acid amide which is substituted by one or two of the same or different substituents selected frbm lower alkyl, benzyl and phenyl; sulphonamide; sulphonamide which is substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; formylamino; alkanoylamino having 1 to 4 carbon atoms in the alkyl moiety; benzoylamino; hydroxy; amino; lower alkylsulphonyl; phenylsulphonyl; lower alkylamino; di-lower alkylamino; lower N-alkyl-N-phenylamino; phenylamino; benzylamino and sulpho.

5. A compound as claimed in claim 1, wherein K represents the naphthol radical which is unsubstituted or substituted by 1,2 or 3 of the same or different substituents selected from lower alkyl; lower alkoxy; halogen; nitro; carboxy; carboxylic acid amide; carboxylic acid amide which is substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; sulphonamide; sulphonamide which is substituted by one or two of the same or different substituents selected from lower alkyl, benzyl and phenyl; formylamino; alkanoylamino having 1 to 4 carbon atoms in the alkyl moiety; benzoylamino; hydroxy; amino; lower alkylsulphonyl; phenylsulphonyl; lower alkylamino; di-lower alkylamino; lower N-alkyl-N-phenylamino; phenylamino; benzylamino and sulpho.

6. A compound as claimed in claim 1, wherein K represents the radical of an aminonaphthalene which is unsubstituted or substituted on the nitrogen atom by one or two of the same or different substituents selected from lower alkyl and phenyl, and which is unsubstituted or substituted in the naphthalene nucleus by 1 or 2 of the same or different substituents selected from sulpho, lower alkyl, lower alkoxy, halogen, formylamino, alkanoylamino having 1 to 4 carbon atoms in the alkyl moiety, benzoylamino, amino, lower alkylsulphonyl, phenylsulphonyl, lower alkylamino, di-lower alkylamino, lower N-alkyl-N-phenylamino, phenylamino and benzylamino.

7. A compound as claimed in claim 1, wherein K represents the radical aniline which is unsubstituted or substituted on the nitrogen atom by one or two of the same or different substituents selected from lower alkyl and phenyl, and of which the benzene nucleus is unsubstituted or substituted by 1 or 2 of the same or different substituents selected from lower alkyl, lower alkoxy, halogen, formylamino, alkanoylamino having 1 to 4 carbon atoms in the alkyl moiety, benzoylamino, lower alkylsulphonyl, phenylsulphonyl, lower alkylamino, di-lower alkylamino, lower N-alkyl-N-phenylamino, phenylamino and benzylamino.

8. A compound as claimed in claim 1, in which K--Z, represents a radical of the formula

in which A represents a phenyl or naphthyl radical, n' represents 1 or2, R2 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a chlorine or bromine atom or a sulphonic acid group, R3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine or bromine atom, R4 represents a hydrogen atom or a lower alkyl, lower alkoxy or sulphonic acid group, R2, represents a hydrogen atom, a lower alkyl, lower alkoxy or lower alkanoylamino group, a chlorine or bromine atom or a sulphonic acid group, B, represents a lower alkyl, carboxy, methoxycarbonyl or ethoxycarbonyl group, B2 represents a lower alkyl, methoxycarbonyl, ethoxycarbonyl or carboxamide group or a phenyl radical which is unsubstituted or substituted by one or two of the same or different substituents selected from lower alkyl, lower alkoxy, chlorine, bromine and sulpho, R' represents a hydrogen atom or a lower alkyl radical, R" represents a hydrogen atom, a lower alkyl radical or a phenyl radical which is unsubstituted or substituted by one or two of the same or different substituents selected from lower alkyl, lower alkoxy.

chlorine, bromine and sulpho, m represents 0, 1 or 2, R6 represents a hydrogen atom, a lower alkyl or lower alkoxy group or a chlorine or bromine atom, Re represents a hydrogen atom or a lower alkyl group which is unsubstituted or substituted by a hydroxy, cyano, carboxy, sulpho, sulphato, methoxycarbonyl, ethoxycarbonyl or acetoxy group, R represents a hydrogen atom or a lower alkyl group which is unsubstituted or substituted by a hydroxy, cyano, carboxy, sulpho, sulphato, methoxycarbonyl, ethoxycarbonyl or acetoxy group, or represents a benzyl radical or a phenyl radical which is unsubstituted or substituted by one or more of the same or different substituents selected from lower alkyl, lower alkoxy, chlorine and sulpho; and R'' represents a hydrogen atom, a lower alkyl or lower alkoxy or lower alkanoamino group, a chlorine or bromine atom or an amino, ureido, lower alkylsulphonylamino, lower alkylamino or di-lower alkylamino group.

9. A compound as claimed in claim 8, in which n' represents 1.

10. A compound as claimed in any one of claims 1 to 9, in which Z represents a group of the formula -SO2-CH2-CH2-Z1 (2a) -S02-cH=CH2 (2b) or

in which Z represents a hydroxy group or an inorganic radical which can be eliminated together with a hydrogen atom on the adjacent carbon atom to form -S02-CH=CH2, R represents a hydrogen atom or a lower alkyl group or a cyano-substituted lower alkyl group, and Y represents a fibre-reactive radical of the cycloaliphatic, aromatic or heterocyclic series or a radical of the aliphatic series.

11. A compound as claimed in claim 10, wherein Y represents a group of the formula 2a or 2b.

12. A compound as claimed in claim 10, wherein Y has any one of the meanings given in Table A herein.

13. A compound as claimed in claim 10 or claim 11, wherein Z1 represents a halogen atom or a sulphato, thiosulphato, phosphato, lower alkylsulphonyloxy, di-lower alkylamino, N-(,B- sulphoethylamino) or N-(4-sulphoethyl)-N-methylamino group.

14. A compound as claimed in claim 1, which is shown in any one of Examples 1 to 20 herein.

1 5. A compound as claimed in any one of claims 1 to 14, which is in the form of a salt.

16. A compound as claimed in claim 15, which is an alkali metal or ammonium salt.

1 7. A compound as claimed in claim 16, which is a sodium salt.

18. A process for the preparation of a compound claimed in claim 1, which comprises (1) selectively diazotizing a compound of the general formula

in which R, has the meaning given in claim 1, or a salt thereof, by means of a substantially equivalent quantity of sodium nitrite in the presence of a mineral acid to give the diazo compound of the general formula

in which R, has the meaning given above, and coupling the diazonium salt of the formula 5 with (a) a coupling component of the general formula HKZn (6) in which K, Z and n have the meanings given in claim 1, but in which Z is not in the ortho-position or para-position in relation to the coupling point, or a salt thereof, or (b) a coupling component of the general formula H-K-Z2 (7) wherein K has the meaning given in claim 1 and Z2 represents a group of the general formula -NHR where R represents a hydrogen atom or a lower alkyl or cyano-lower alkyl group, or a salt thereof, and in the case of (b) reacting the resulting compound which, written in the form of the free acid, has the general formula

in which R1, R and K have the meanings given above, with a compound which contains the fibre reactive radical Y and has the general formula Hal-V (9) wherein Y represents a fibre-reactive radical belonging to the aliphatic, cycloaliphatic, heterocyclic or aromatic series and Hal represents a halogen atom, or with an acid anhydride containing the radical represented by Y, or (2) sulphating or phosphating a compound claimed in claim 1 in which Z represents a group of the formula -SO2CH2H2-OH or a salt thereof.

1 9. A process as claimed in claim 18, carried out substantially as described in any one of Examples 1 to 20 herein.

20. A compound as claimed in claim 1, whenever prepared by a process as claimed in claim 18 or claim 19.

21. A dyestuff preparation which comprises a compound claimed in any one of claims 1 to 1 7 and 20 and a suitable carrier.

22. A compound as claimed in any one of claims 1 to 1 7 and 20, for use for dyeing and printing fibre materials containing hydroxy groups or containing carboxamide groups.

23. A process for dyeing and printing fibre materials containing hydroxy groups of containing carboxamide groups, which comprises applying a compound as claimed in any one of claims 1 to 1 7 and 20 or a preparation as claimed in claim 21 to the material and fixing the compound thereon.

24. Fibre materials which contain hydroxy groups or contain carboxamide groups and which have been coloured with a compound as claimed in any one of claims 1 to 1 7 and 20 or a preparation as claimed in claim 21.

25. A compound of the general formula

in which R has the meaning given in claim 1, and the two R1 moieties can be the same or different; K has the meaning given in any one of claims 1 to 7; and R has the meaning given in claim 10; or a salt thereof.

26. A compound as claimed in claim 25, which is described in Example 6 herein.

27. A compound as claimed in claim 25, which is the intermediate for the compound described in any one of Examples 11 to 20 herein.