CA2331309A1

CA2331309A1 - Water-soluble monoazo compounds, preparation thereof and use thereof as dyes

Info

Publication number: CA2331309A1
Application number: CA002331309A
Authority: CA
Inventors: Jorg Dannheim
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Individual
Priority date: 1998-05-08
Filing date: 1999-05-03
Publication date: 1999-11-18
Also published as: DE19820543A1; ID26256A; EP1075500A1; WO1999058612A1; BR9910271A; JP2002514676A; TR200003223T2

Abstract

The invention relates to a monoazo compound corresponding to the general formula (1), in which X is a fibre-reactive group or a grouping containing a fibre-reactive group; D is phenylene which can be substituted by 1 or 2 substituents from the group sulfo, carboxy, C1-4 alkyl, C1-4 alkoxy and chlorine, or naphthylene which can be substituted by 1 or 2 sulfo groups; G is the bivalent rest of a C5-8 cycloalkyl or C5-8 bicyclo alkyl, whereby the alicyclic rests can contain an olefinic double bond and/or be interrupted by a hetero group and can be substituted by 1 or 2 substituents of the group comprising halogen or C1-4 alkyl which may be substituted; and W, s, R~, r, alk, t, M, m and R have the meanings given in claim 1. The invention also relates to a method for producing said compound and its use for dyeing material containing hydroxy and/or carbonamide groups.

Description

DyStar Textilfarben GmbH & Co. Deutschland KG DYS 1998/D 505 Dr.ST/AP
Description Water-soluble monoazo compounds, preparation thereof and use thereof as dyes U.S. Pat. No. 3,649,615 and European Patent Application No. 0 090 114 disclose fiber-reactive azo compounds containing a ~3-carboxyethyl-carbonylamino or carboxyacrylamino group in the sulfonaphthol coupling component.
Used as dyes, they dye for example cotton in red shades which, however, are not satisfactory in some properties and in some instances have unsatisfactory lightfastnesses in particular.
The present invention now provides monoazo compounds conforming to the hereinbelow indicated and defined general formula (1 ), which have improved properties compared with the known dyes, especially a good lightfastness and good washoff for unfixed portions on the dyed material, and which are particularly notable for their good solubility and padding liquor stability.
Ho i N-~-G
X- (Vlns N (alk)t D- N = N
COOM
R° M03S (S03M)m ( 1 ) r In the formula (1):
M is hydrogen or an alkali metal, such as sodium, potassium or lithium, or some other colorless salt-forming metal, such as the equivalent of an alkaline earth metal, as of calcium;
m is zero or 1 (when m is zero, this group is hydrogen);
X is a fiber-reactive group or a grouping which contains a fiber-reactive group;
W is alkylene of 1 to 4 carbon atoms, such as methylene, ethylene and n-propylene, or is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, and chlorine, or is .~ alkylene of 3 to 6 carbon atoms which is interrupted by an -O- or -NH-group;
R° is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, or is phenyl which may be substituted by sulfo, methyl, ethyl, methoxy, ethoxy or chlorine, preferably is hydrogen, methyl or ethyl;
alk is alkylene of 1 to 4 carbon atoms, such as methylene and ethylene;
r is zero or 1;
s is zero or 1;
t is zero or 1;
D is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, and chlorine, or is naphthalene which may be substituted by 1 or 2 sulfo groups;
R is hydrogen or alkyl of 1 to 4 carbon atoms such as methyl and ethyl, preferably hydrogen;
G is the bivalent radical of a cycloalkyl of 5 to 8 carbon atoms or of a bicycloalkyl of 5 to 8 carbon atoms, it being possible for the alicyclic radicals to contain an olefinic double bond and/or to be interrupted by a hetero group, such as -O- or -NH-, and moreover to be substituted by 1 or 2 substituents selected from the group consisting of halogen, such as chlorine and bromine, or alkyl of 1 to 4 carbon atoms, which may be substituted, for example by hydroxyl and alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy;
when m is 1 the -S03M group is preferably disposed in position 3 or 4, particularly preferably position 3, of the 8-hydroxy-naphthalene radical in which case the -N(R)-CO-G-COOM group is preferably attached in position 1 of the 8-hydroxy-naphthalene radical, or is disposed in position 4, in which case the -N(R)-CO-G-COOM group is attached in position 3 of the 8-hydroxynaphthalene radical, or the -N(R)-CO-G-COOM group is preferably disposed in position 2 or 3 of the 8-hydroxynaphthalene radical when m is zero;
when X is a heterocyclic radical, s is zero and r is 1.

Both in the general formula (1 ) and in the hereinbelow indicated general formulae, the individual elements of the formula, whether they bear identical or different designations; within any one general formula, can have meanings under their definition which are mutually identical or different.
The terms "sulfo", "thiosulfato, "carboxyl", "phosphato" and "sulfato" cover not only the acid form but also the salt form of the respective groups. Accordingly, sulfo groups are groups conforming to the general formula -S03M, thiosulfato groups are groups conforming to the general formula -S-S03M, carboxyl groups are groups conforming to the general formula -COOM, phosphato groups are groups conforming to the general formula -OP03M2 and sulfato groups are groups conforming to the general formula -OS03M, in each of which M is as defined above.
Examples of G are the bivalent radicals of cyclopentane, cyclohexane, cyclohexene, cycloheptane and cycloheptene which may each, as specified above for G, be substituted by substituted or unsubstituted alkyl of 1 to 4 carbon atoms, halogen or alkoxy of 1 to 4 carbon atoms, in which case these alicyclic radicals, especially the cyclohexane and cyclohexene radicals, may with the aid of an alkylene bridge, such as methylene or ethylene, or an oxygen bridge or an aliphatic bridge containing an -NH- member form the radical of a bicycle. These radicals may exist both in the cis and in the trans form.
Examples of G are those conforming to the general formulae (2a), (2b), (2c), (2d) and (2e) R~ H R~ R~
Rz Rz Rz (2a) (2b) (2c) R~ v R, O
Rz Rz (2d) (2e) where R~ is hydrogen, methyl or ethyl, and R2 is hydrogen, methyl, ethyl or chlorine.
J
G radicals are in particular 1,2-cyclohexylene, 3-methyl- or 4-methyl-1,2-cyclohexylene, 1,2-cyclohex-4-enylene, 7-oxabicyclo(2,2,1 )hept-5-en-2, 3-ylene, endo-norbor-5-en-2,3-ylene, 1,4-dimethylcyclohex-4-en-1,2-ylene, 3-methylcyclohex-4-en-1,2-ylene, methyl-5-norbornen-2,3-ylene and endo-bicyclo(2,2,2)oct-5-en-2,3-ylene, each in the cis and the trans form. G is preferably 1,2-cyclohexylene and 1,2-cyclohex-4-enylene.
Fiber-reactive groups X or groupings X which contain a fiber-reactive group are for example halogen-substituted s-triazine or pyrimidine groups in which the halogen substituents are fluorine, chlorine or bromine or preferably fluorine or chlorine and the halogen-substituted s-triazine radical may additionally contain a substituted or unsubstituted amino group and the substituents of this amino group may be phenyl, naphthyl or alkyl of 1 to 4 carbon atoms, which in turn contain a fiber-reactive group of the vinyl sulfone series, or are for example a 2,3-dichloro-1,4-phenazine-6-carbonyl radical, subject to the proviso that when X is one of these heterocyclic radicals, s is zero and r is 1.
Examples of X further include fiber-reactive groups of the vinyl sulfone series, such as vinylsulfonyl or an ethylsulfonyl which is substituted by an alkali-eliminable substituent in the a-position.
Fiber-reactive radicals are for example those which conform to the general formulae (3a), (3b), (3c), (3d), (3e), (3f), (3g), (3h) or (3j) Hal Hal Hal / I Hal / I Hal N ~ N N ~ N NON
Hal Hal (3a) (3b) (3c) Hal N C
Ra ~ ~ N ~ CO--N ~N
CI
Hal (3d) (3e) Hal Hal R3 N N Rs N N
a N~N~ s N~N
R R
(3f) (39) Hal R\ N

(3h) (3J) where:
Y is vinyl or is ethyl which is substituted by an alkali-eliminable substituent, for example by chlorine, bromine, sulfato, thiosulfato, phosphato, alkanoyloxy of to 5 carbon atoms, such as acetyloxy, benzoyloxy, sulfobenzoyloxy or p-toluylsulfonlyoxy, and is preferably vinyl, ~3-chloroethyl or ~-sulfatoethyl;
Hal is in each case, which may have meanings identical or different from one another, chlorine, bromine or fluorine, preferably chlorine or fluorine;
R°' is hydrogen or Hal as defined above;
R3 is hydrogen or alkyl of 1 to 4 carbon atoms, which may be substituted by hydroxyl, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, sulfato, phosphato, carboxyl, sulfo or alkoxy of 1 to 4 carbon atoms;
R4 is hydrogen or alkyl of 1 to 4 carbon atoms, which may be substituted by hydroxyl, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, sulfato, phosphato, carboxyl, sulfo or alkoxy of 1 to 4 carbon atoms, or is an unsubstituted or methyl-monosubstituted or -disubstituted cyclohexyl of 5 to 8 carbon atoms or is phenyl which may be substituted by 1 or 2 substituents selecfed from the group consisting of sulfo, carboxyl, chlorine, alkyl of 1 to carbon atoms, such as ethyl and especially methyl, and alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, or is naphthyl which may be substituted by sulfo, or R3 and R4 combine to form an alkylene of 5 to 8 carbon atoms or an -O- or -NH-interrupted alkylene of 4 to 6 carbon atoms or with the nitrogen atom to form the radical of a saturated heterocycle, for example piperidino, morpholino or piperazino;
R5 is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or phenyl, which can be substituted by chlorine, sulfo, carboxyl, methyl, ethyl, methoxy or ethoxy;
R6 is a group of the general formula (4a) or (4b) (4a) (4b) where Y is as defined above, ALK is alkylene of 1 to 4 carbon atoms, such as methylene and especially ethylene or n-propylene, and AR is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, and chlorine, or is naphthylene which may be substituted by 1 or 2 sulfo groups, R~ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl, preferably hydrogen, R$ is a group of the general formula (4c) or (4d) Y-S02-Alk-E-Alk- Y-S02-(Alk)p-E-(Alk)q-(4c) (4d) where Y is as defined above, Alk is alkylene of 2 to 4 carbon atoms, preferably ethylene, E is an -O- or -NH- group, p is zero or 1, and q ; is zero or 1, subject to the proviso that their sum (p + q) is 1.
Preferred groups conforming to the general formula X-(VAS (NR°); (alk);
D-, which is contained in the general formula (1), are especially groups conforming to the general formulae (5a), (5b), (5c) and (5d) (MO3S)m / \

R~0 Y - SOz (5a) (5b) / \
V - N '~ (MO3S)m \ /
Ro R» V - N - (CH2)n R
(5c) (5d) where:
Y, M, R° and m are each as defined above;
R9 is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, or halogen, such as chlorine;
R~~ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy;
R~ ~ is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy;
V is a group of the hereinabove named and defined general formula (3a), (3b), (3c), (3d), (3e), (3f), (3g) or (3h);
n is1,2or3.

Examples of radicals of the general formula (5a) and (5b) are 4-([3-sulfato-ethylsulfonyl)phenyl, 4-vinylsulfonylphenyl, 3-([i-sulfatoethylsulfonyl)-phenyl, 2-([i-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-([i-sulfatoethyl-sulfonyl)phenyl, 2-methoxy-5-vinylsulfonylphenyl, 2-sulfo-4-([i-sulfato-ethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-([i-sulfatoethylsulfonyl)phenyl, 2,5-dimethoxy-4-([3-sulfatoethylsulfonyl)phenyl, 5-([3-sulfatoethylsulfonyl)-naphth-2-yl, 6-([3-sulfatoethylsulfonyl)naphth-2-yl, 8-([3-sulfatoethyl-sulfonyl)naphth-2-yl, 1-sulfo-6-([i-sulfatoethylsulfonyl)naphth-2-yl, 6-sulfo-8-([i-sulfatoethylsulfonyl)naphth-2-yl, 4-([i-chloroethylsulfonyl)phenyl, 2-methoxy-4-([i-sulfatoethylsulfonyl)phenyl, 4-methoxy-3-([i-sulfatoethyl-sulfonyl)phenyl, 2-carboxy-4-([i-sulfatoethylsulfonyl)phenyl, 4-([i-thiosulfato-ethylsulfonyl)phenyl, 4-(~-phosphatoethylsulfonyl)phenyl and 4-(~-acetyloxyethylsulfonyl)phenyl.
Examples of heterocyclic fiber-reactive radicals conforming to the general formulae (3a) to (3h) are 2,4-difluoro-5-chloropyrimidin-6-yl, 2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-5-chloropyrimidin-2-yl, 4,6-difluoropyrimidin-4-yl and also groups of the general formula (3f), (3g) and (3h) where R3 is hydrogen, methyl, ethyl, [i-hydroxyethyl or [3-sulfoethyl, R4 is hydrogen, methyl, ethyl, [i-hydroxyethyl, cyclohexyl, phenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2-carboxyphenyl, 1-naphthyl, 1-sulfo-2-naphthyl, or 1,5-disulfo-2-naphthyl or the group R3R4N-is morpholino, R5 is hydrogen, R6 is 4-([i-sulfatoethylsulfonyl)phenyl, 3-(~-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-([3-sulfatoethylsulfonyl)-phenyl, 4-vinylsulfonylphenyl, 3-vinylsulfonylphenyl, 2-methoxy-5-([3-sulfatoethylsulfonyl)phenyl, 2,5-dimethoxy-4-([i-sulfatoethylsulfonyl)-phenyl, 2-methyl-4-([3-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-([i-sulfatoethylsulfonyl)phenyl, ~i-([i'-sulfatoethylsulfonyl)ethyl or y-([i'-sulfatoethylsulfonyl)propyl, R~ is hydrogen and R$ is ~3-[[i'-([3"-chloroethylsulfonyl)ethoxy]ethyl.
Examples of radicals of the general formula (6) (6) R~ ~

which are contained in the formula (5c) are 1,4-phenylene 1,3-phenylene, 2-sulfo-1,4-phenylene, 4-sulfo-1,3-phenylene, 4,6-disulfo-1,3-phenylene, 2,5-disulfo-1,4-phenylene, ~-methyl-1,4-phenylene, 4-methyl-1,3-phenylene, 4-sulfo-6-methyl-1,3-phenylene and 4-sulfo-6-methoxy-1,3-phenylene.
Examples of radicals of the general formula (7) (MOsS)m ( 7 ) - N (CHZ)n R
which are contained in the formula (5d), are 3-(N-methylamino)methyl-5-sulfo-2,6-dimethylphenyl, 4-(N-methylamino)methyl-3-sulfophenyl, 2-aminomethyl-6-sulfo-4-methylphenyl and 5-aminomethyl-1-sulfonaphth-2-yl.
Of the monoazo compounds of the general formula (1 ) according to the invention, emphasis must be given especially to those which conform to the general formulae (1A) and (1 B) HO NH-CO-G-COOM
Xo_D~ / I \ ~1A) \ /

HO
X~ - D~ / \

\ /
MOsS
where:
M is as defined above;
G has the abovementioned, particularly preferred meaning and is particularly preferably 1,2-cyclohexylene or 1,2-cyclohex-4-enylene; the -NH-CO-G-COOM group in the formula (1 B) is attached in position 2 or 3 of the 8-hydroxynaphthalene radical;
X°-D~- is a radical of the hereinabove defined general formula (5a) where Y is preferably vinyl or ~3-sulfatoethyl and R9 and R1° are both preferably hydrogen 5 or R9 is preferably hydrogen and R~° is preferably methyl, ethyl, methoxy or ethoxy and the Y-S02- group is attached meta or para relative to the free bond of the benzene nucleus, or is a group of the hereinabove defined general formula (5b) where Y is preferably vinyl or ~-sulfatoethyl, M is as defined above and m is 1, or is a group of the hereinabove defined general 10 formula (5c) or (5d) where R9 is preferably hydrogen, R~ ~ is preferably hydrogen or sulfo, V is preferably a radical of the general formula (3a), (3b), (3g) or (3h) of the hereinabove indicated, particularly preferred, meaning and R° is preferably hydrogen, methyl or ethyl.
The monoazo compounds of the general formula (1) according to the invention are preparable in various ways, for example by reacting an aminonaphtholsulfonic acid of the general formula (9) R
N-H (9) M03S (J03M)m where M, m and R are each as defined above, with an anhydride of the general formula (10) C~
G O (10) ~ C~
O
where G is as defined above, in aqueous suspension or in an organic reaction-inert solvent or in a mixture of such a solvent with water and then coupling the resulting compound of the general formula (11) R O
V-C-G
(11) COOM
M03S (SO3M )m where M, m, R and G are each as defined above, with a conventionally prepared diazonium salt compound of an amino compound of the general formula (12) X- (W)S N (alk)t D NHZ

(12) R
r where X, W, R°, alk, D, r, s and t are each as defined above. In the case of the synthesis of monoazo compounds according to the invention where X is a heterocyclic fiber-reactive group, they can be prepared by initially coupling the diazonium salt of a compound of the general formula (13) H-N(R°)-D-NH2 (13) where D and R° are each as defined above, with a compound of the general formula (11) and then reacting the resulting monoazo compound conforming to the general formula (14) HO i O
N-~-G
H-N(R~)-D-N=N ~ I I (14) COOM
M03S (S03M)m where the individual elements of the formula are each as defined above, with a compound of the general formula Hal-X, where Hal is as defined above and X is a radical of the general formula (3a) to (3h), or in the case of the synthesis of a compound of the general formula (1) where X is a radical of the general formula (3f) to (3h), reacting a compound of the general formula (14) with 2,4,6-trihalogeno-1,3,5-triazine; such as 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) or 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) and reacting the resulting dihalotriazinylaminoazo compound with an amine of the general formula R3R4NH or R5R6NH or R~R$NH
where R3, R4, R5, R6, R7 and Ra are each as defined above. These reactions with the halo-pyri~nidine and -triazine compounds with the amino compounds and aminoazo compounds, respectively, likewise take place in aqueous solution or suspension, optionally in the presence of an inert organic solvent. Such inert organic solvents, which can also be used in the reaction of an aminonaphthol of the general formula (9) with an anhydride of the general formula (10), are for example dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone.
A reaction of the aminonaphtholsulfonic acid of the general formula (9) with the anhydrides of the general formula (10) is advantageously effected by adding the finely granular or pulverulent anhyride to an aqueous solution of the aminonaphtholsulfonic acid while maintaining a pH between 2 and 8, preferably between 4 and 7, and conducting the reaction at a temperature between 0 and 30°C, preferably 0 and 25°C. The pH can usually be set and maintained by means of an alkaline compound, such as sodium carbonate or sodium bicarbonate or aqueous sodium hydroxide solution, likewise with the aid of the corresponding lithium compounds.
The coupling reaction of a compound of the general formula (11 ) with the diazonium compounds of the amines of the general formula (12) or (13) is effected in a conventional manner in aqueous solution, for example at a temperature between and 25°C, preferably between 5 and 20°C, and at a pH of between 3 and 8, preferably between 4 and 6.5. The diazotization of the amino compounds is likewise carried out in a generally conventional manner in aqueous solution, for example by means of sodium nitrite in strongly acidic, for example hydrochloric acid or sulfuric acid, medium at a temperature between -5°C and +20°C and at a pH
of less than 3, preferably less than 2.5.
The starting compounds used for synthesizing the compound of the general formula (1) are generally known or preparable analogously to known procedures, for example the amino compounds of the general formula (12) where X is a heterocyclic radical by reacting an amino compound of the general formula (13) with a compound of the general formula Hal-X of the abovementioned definition in aqueous solution or suspension, optionally in the presence of an inert organic solvent, the reaction taking place at a temperature between 0 and 70°C and a pH between 3 and 8 depending on the reactivity of the starting components, especially on the reactivity of the halogen-substituted heterocyclic compounds. These reactions are incidentally familiar to the person skilled in the art and open to variation in a skilled manner in order that a satisfactory synthesis may be obtained.
The reactiorL of the amino compounds of the general formulae R3R4NH, R5R6NH
and R~R8NH with an above-identified dihalo-s-triazinylaminoazo compound generally takes place at a temperature of between 10 and 60°C and at a pH of between 3 and 9, these reaction conditions depending strongly on the structure and basicity of the amines. These reaction variants and conditions too are familiar to the skilled person from the literature and from his or her technical knowledge.
Starting compounds of the general formula (9) are for example 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid, 3-amino-8-naphthol-6-sulfonic acid, 3-methylamino-8-naphthol-6-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 3-amino-8-naphthol-4,6-disulfonic acid, 1-amino-8-naphthol-6-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 3-amino-8-naphthol-4-sulfonic acid and 2-amino-8-naphthol-3,6-disulfonic acid, in particular 3-amino-8-naphthol-6-sulfonic acid, 3-methylamino-8-naphthol-6-sulfonic acid and 2-amino-8-naphthol-6-sulfonic acid, preferably 1-amino-8-naphthol-3,6-disulfonic acid, 3-amino-8-naphthol-6-sulfonic acid, 3-methylamino-8-naphthol-6-sulfonic acid and 2-amino-8-naphthol-sulfonic acid.
Starting compounds of the general formula (10) are for example trans- and cis-cyclohexane-1,2-dicarboxylic anhydride, trans- and cis-4-cyclohexene-1,2-dicarboxylic anhydride, trans- and cis-5-norbonene-endo-2,3-dicarboxylic anhydride, trans- and cis-exo-7-oxabicyclo(2.2.1 )hept-5-ene-2,3-dicarboxylic anhydride, trans-and cis-1,4-dimethylcyclohex-4-ene-1,2-dicarboxylic anhydride, trans- and cis-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, trans- and cis-methyl-5-norbonene-2,3-dicarboxylic anhydride and trans- and cis-endo-bicyclo(2.2.2)oct-ene-2,3-dicarboxylic anhydride.
Useful diazo component amines which possess a fiber-reactive group of the vinyl sulfone series and which conform to the general formula (12) where X is a group of the general formula Y-S02- where Y is as defined above and which preferably correspond to an amine of the general formula Y-S02-D-NH2 are for example 4-(a-sulfatoethylsulfonyl)aniline, 4-vinylsulfonylaniline, 3-(~-sulfatoethylsulfonyl)aniline, 2-(~3-sulfatoethyl-sulfonyl)aniline, 2-methoxy-5-(~3-sulfatoethylsulfonyl)aniline, 2-methoxy-5-vinylsulfonylaniline, 2-sulfo-4-(~-sulfatoethylsulfonyl)aniline, 2-methoxy-5-methyl-4-(~i-sulfatoethylsulfonyl)aniline, 2,5-dimethoxy-4-(~-sulfatoethyl-sulfonyl)aniline, 5-(~3-sulfatoethylsulfonyl)-2-aminonaphthalene, 6-([3-sulfatoethylsulfonyl)-2-aminonaphthalene, 8-([3-sulfatoethylsulfonyl)-2-aminonaphthalene, 1-sulfo-6-([3-sulfatoethylsulfonyl)-aminonaphtl~alene, 6-sulfo-8-([3-sulfatoethylsulfonyl)-2-aminonaphthalene, 4-([3-chloroethyl-sulfonyl)aniline, 2-methoxy-4-([3-sulfatoethylsulfonyl)aniline, 4-([i-sulfato-ethylsulfonyl)-N-ethylaniline, 4-([3-sulfatoethylsulfonyl)benzylamine, 4-methoxy-3-([i-sulfatoethylsulfonyl)aniline, 2-carboxy-4-(~3-sulfatoethyl-sulfonyl)aniline, 4-([3-thiosulfatoethylsulfonyl)aniline, 4-([3-phosphato-ethylsulfonyl)aniline and 4-([3-acetoxyethylsulfonyl)aniline.
Examples of starting compounds of the general formula (13) are 1,4-diaminobenzene, 1,3-diaminobenzene, 2-sulfo-1,4-diaminobenzene, 4-sulfo-1,3-diaminobenzene, 4,6-disulfo-1,3-diaminobenzene, 2,5-disulfo-1,4-diaminobenzene, 2-methyl-1,4-diaminobenzene, 4-methyl-1,3-diaminobenzene, 4-sulfo-6-methyl-1,3-diaminobenzene and 4-sulfo-6-methoxy-1,3-diaminobenzene and also 3-sulfo-2,6-dimethyl-5-[(N-methylamino)methyl]aniline, 2-sulfo-4-methyl-6-aminoethylaniline, 3-sulfo-4-[(N-methylamino)methyl]aniline and 1-sulfo-5-aminomethyl-2-amino-naphthalene.
Examples of starting compounds conforming to the general formulae (3a) to (3d) are 2,4,6-difluoro-5-chloropyrimidine and 2,4,6-trifluoropyrimidine.
The separation and isolation from their aqueous synthesis solutions of the monoazo compounds of the general formula (1 ) according to the invention can be effected by generally known methods for water-soluble compounds, for example by precipitating from the reaction medium by means of an electrolyte, for example sodium chloride or potassium chloride, or by evaporating the reaction solution itself, for example by spray drying. If the last-mentioned form of isolation is chosen, it is frequently advisable, prior to the evaporating, to remove any sulfate in the solutions by precipitation as calcium sulfate and collection by filtration.
The monoazo compounds of the general formula (1) according to the invention -hereinafter referred to as compounds (1) - have fiber-reactive properties and possess very useful dye properties. They can therefore be used for dyeing (which includes printing) hydroxyl-containing and/or carboxamido-containing materials. For this, the solutions obtained in the synthesis of the compounds (1) can be used for dyeing directly as liquid formulation, optionally after addition of a buffer substance and optionally after concentrating.

The present invention therefore also provides for the use of the compounds (1 ) for dyeing (which includes printing) hydroxyl- and/or carboxamido-containing materials or, to be mope precise, for processes for their application to these substrates. The materials are preferably employed in the form of fiber materials, especially in the 5 form of textile fibers, such as yarns, packages and fabrics. It is possible to proceed analogously to known procedures for this.
Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols.
10 Cellulose fiber materials are preferably cotton but also other vegetable fibers, such as linen, hemp, jute and ramie fibers. Examples of regenerated cellulose fibers are staple viscose and filament viscose.
Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other 15 animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The fiber materials can also be processed and dyed in blends with each or one another or may include fiber materials of a different chemical nature, such as polyester fibers. Examples of this are blend fabrics of cellulose fibers and polyester fibers and also of cellulose fibers and polyamide fibers.
The compounds (1 ), in accordance with the use of the invention, can be applied to and fixed on the substrates mentioned, especially the fiber materials mentioned, by the techniques known for water-soluble, fiber-reactive dyes, for example by applying said compound (1) in dissolved form to the substrate or incorporating it therein and fixing it thereon or therein by the action of heat or by the action of an alkali or by both measures. Such dyeing and fixing methods have been extensively described in the literature (for example in European Patent Application Publication No. 0 181 585).
Thus, said compounds (1) are suitable not only for the exhaust dyeing process but also for dyeing by the pad-dyeing process, whereby the material is impregnated with aqueous, optionally electrolyte salt-containing solutions of the compounds (1) and the compound (1 ) is fixed on the material in the abovementioned manner. The compounds (1) are particularly useful in the cold pad-batch processes, whereby a dye is applied to the fiber material on a pad-mangle together with the alkali and thereafter is fixed by storing at room temperature for several hours. After fixing, the dyeings and prints obtained are thoroughly rinsed with cold and hot water, optionally in the presence of an agent which has a dispersing action and promotes the diffusion of the unfixed portions.

The compounds (1) are notable for high reactivity, good fixing capability and very good build-up capability. They can therefore be used by the exhaust dyeing process at low temperatures and require only short steaming times in pad-steam processes.
The degrees of fixation are high, and unfixed portions are easily washed off, the difference between the degree of exhaustion and the degree of fixation being remarkably small, which is why the loss on soaping is also very small. The compounds (1 ) are also particularly useful for application in textile printing processes, especially on cellulose fiber materials, such as cotton, but also for printing carboxamido-containing fiber material, for example wool and silk or blend fabrics comprising wool or silk. They are further very useful for application in the discharge printing and resist printing processes.
The dyeings and prints prepared with the compounds (1) have (especially on cellulose fiber materials) a high color strength and a high fiber-dye bond stability both in the acidic and in the alkaline range, also good lightfastness, including a very good wet lightfastness, and generally good wetfastnesses, such as wash, water, seawater, cross dyeing and perspiration fastnesses, and also good fastness to pleating, hot pressing and crocking.
The examples hereinbelow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kilogram relates to the liter.
The compounds described in the examples in terms of a formula are indicated in the form of the free acids; in general, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used for dyeing in the form of their salts. The starting compounds and components mentioned in the form of the free acid in the examples hereinbelow, especially the table examples, can similarly be used in the synthesis as such or in the form of their salts, preferably alkali metal salts The absorption maxima (7~max) reported in the visible range for the compounds of the invention were determined in aqueous solution on their alkali metal salts. In the table examples, the Amax values are given in brackets next to the reported hue; the reported wavelength is in nm.

Example 1 A pH 7 solution at 15 to 20°C of 239 parts of 3-amino-6-sulfo-8-naphthol in 1500 parts of water is admixed with 170 parts of cis-cyclohex-4-ene-1,2-dicarboxylic anhydride, and the reaction batch is maintained at pH 6 and 0 to 5°C
for about five hours. A conventionally prepared solution of the diazonium salt of 410 parts of 6-sulfo-8-(~3-sulfatoethylsulfonyl)-2-amino-naphthalene is then added; the coupling reaction takes place at a pH of 5 to 6 and at about 15°C.
The novel monoazo compound of the formula (written in the form of the free acid) O - CHz - CHZ - SOZ OH
HOOC
S03H / I \ N = N / ( \
\ / \ / NH-CO

(~max - 495 nm) is isolated in a conventional manner as alkali metal salt by salting out with sodium chloride or by spray drying. It possesses very good fiber-reactive dye properties and dyes the fiber materials mentioned in the description part, for example cotton, by the dyeing and printing processes customary in the art, in bright orange shades having good fastness properties, of which emphasis can be given to the light- and washfastnesses in particular.
Example 2 A pH 6 to 7 solution of 319 parts of 1-amino-3,6-disulfo-8-naphthol in 4000 parts of ice-water is admixed with 180 parts of cis-cyclohex-4-ene-1,2-dicarboxylic anhydride;
the reaction takes place at pH 6 and 0 to 5°C for about five hours. A
conventionally prepared solution of the diazonium salt of 410 parts of 1-sulfo-6-(~i-sulfatoethylsulfonyl)-2-aminonaphthalene is then added, and the coupling reaction is carried out at about 15°C and a pH between 5.5 and 6.5.
The synthesized novel monoazo compound of the formula (written in the form of the free acid) / ~ \ N=N / I \
\ / \ /

(~max = 534 nm) is isolated from the synthesis batch in the form of an alkali metal salt in a conventional manner, for example by salting out with sodium chloride or spray drying. It dyes the fiber materials mentioned in the description part, for example cotton, in bright red shades having good fastness properties, of which the light- and washfastnesses can be emphasized in particular.
Example 3 A pH 7 solution at 15 to 20°C of the lithium salt of 239 parts of 2-amino-6-sulfo-8-naphthol in 2000 parts of water is admixed with 175 parts of cis-cyclohex-4-ene-1,2-dicarboxylic anhydride; the reaction batch is additionally stirred for about 3 hours at 15 to 20°C while a pH of 6 is maintained by means of lithium hydroxide and then admixed with a conventionally prepared hydrochloric acid diazonium salt suspension of 281 parts of 4-(~i-sulfatoethylsulfonyl)aniline. The coupling reaction is carried out at pH 4 to 5 and a temperature of 5 to 10°C, and then the novel azo compound of the formula (written in the form of the free acid) OH
N=N / I \ NH-CO OOH
S02 \ \

(~max = 493 nm) is isolated by spray drying at pH 5.5. It has very good fiber-reactive dye properties and dyes for example cotton by the dyeing and printing processes customary in the art for fiber-reactive dyes in strong orange shades having good fastness properties, for example good lightfastnesses.
Example 4 A neutral solution of the sodium salt of 319 parts of 1-amino-3,6-disulfo-8-naphthol in 4000 parts of ice-water is admixed with 180 parts of cis-cyclohexane-1,2-dicarboxylic anhydride; the batch is subsequently stirred for about a further five hours at pH 6 and 0 to 5°C.
In a separate batch, a neutral solution of 252 parts of 1-sulfo-5-methylamino-aminonaphthalene and 71 parts of sodium nitrite in 2500 parts of water at 5°C is gradually and continuously added with thorough stirring to a mixture of 2000 parts of ice and 300 parts by volume of concentrated aqueous hydrochloric acid.
Stirring is continued for an hour, and excess nitrite is removed with amidosulfuric acid in a conventional manner. The diazonium salt suspension is then added to the initially prepared batch of the coupling component, and the coupling reaction is carried out in the course of about one hour at pH 7 and a temperature of about 20°C.
The batch is then heated to 40°C and adjusted to pH 8; 187 parts of 2,4,6-trifluoro-5-chloropyridimine are continuously added with thorough stirring whilst maintaining a pH of 8 at a temperature of 40°C.
Following a reaction time of about one hour, the solution is adjusted to pH
7.5, and after the reaction solution has cooled down, the monoazo compound of the invention is salted out by means of sodium chloride. The monoazo compound of the invention has, written in the form of the free acid, the formula SO., HO NH - CO OOH
F N=N / I \ H
\ /

CI ~ NH - CH2 -N
F
~~max = 537 nm) and dyes for example cotton by the dyeing and printing processes customary in the art for fiber-reactive dyes in deep red shades having good fastness properties, of which the good light and washfastnesses may be emphasized in particular.
5 Example 5 239 parts of 3-amino-6-sulfo-8-naphthol and 170 parts of cis-cyclohex-4-ene-1,2-dicarboxylic anhydride are reacted with one another according to the directions of Example 1. The coupling component obtained is then coupled in an analogous manner at pH 5 and about 15°C with the diazonium salt of 311 parts of 2-methoxy-5-10 (~i-sulfatoethylsulfonyl)aniline, and the resulting inventive monoazo compound of the formula (written in the form of the free acid) / I N-N / I \
\ \ / NH-CO COOH

15 (~max = 492 nm) is isolated in a conventional manner. It dyes the fiber materials mentioned in the description part, especially cotton, by the dyeing and printing processes customary in the art for fiber-reactive dyes in brilliant orange shades having good fastness 20 properties.
Example 6 A pH 6.5 solution of 281 parts of 4-((i-sulfatoethylsulfonyl)aniline and 40 parts of sodium fluoride in 3500 parts of ice-water is reacted with 150 parts of cyanuric fluoride according to the procedure of DE-A 27 46 109 by gradual addition and thorough stirring. After the reaction has taken place, the batch is admixed with 180 parts of 1,3-diaminobenzene-4-sulfonic acid, adjusted to pH 6.5 with sodium carbonate and further stirred for about three hours whilst maintaining the pH
and a temperature of 0 to 10°C.

The batch is then cooled down to 0°C, and the amino compound obtained is diazotized in a conventional manner by means of sodium nitrite and concentrated hydrochloric.acid. The diazonium salt solution obtained is then added to the solution of the coupling component prepared from 319 parts of 1-amino-3,6-disulfo-8-naphthol and 180 parts of cis-cyclohex-4-ene-1,2-dicarboxylic anhydride according to the present Example 2. The coupling reaction takes place at a pH between 5.5 and 6.5 and a temperature of about 15°C.
The resulting synthesis solution with the novel monoazo compound of the formula (written in the form of the free acid) F

N~ N /
NH-~ ~ NH \ ~ N = N / \
N
\ /
/ ~ H03S S03H

(~max = 516 nm) is buffered to pH 7 with a mixture of secondary and primary sodium hydrogen phosphate; the monoazo compound of the invention is then salted out with sodium chloride and isolated. It has very good fiber-reactive dye properties and dyes for example cotton in strong red shades having good fastness properties.
Examples 7 to 64 The table examples hereinbelow describe further novel monoazo compounds conforming to the general formula (A) H

X~-D~ N=N / ~ 2 I (A) -+-N-CO-G
H03S 4 Rp COOH

in terms of their components. They can be prepared according to one of the procedures of the invention, for example analogously to one of the above examples, using the starting compounds evident from the respective table example in conjunction with the general formula (A) such as the diazo compound X°-D~-NH2 or the diamine H2N-D~-NH2 and the halogen-substituted heterocyclic compound X°-Hal, the aminonaphthol sulfonic acid compound and the cyclic anhydride conforming to the general formula (10). They possess very good fiber-reactive dye properties and dye the materials mentioned in the description part, especially cellulose fiber materials, such as cotton, in the hue reported in the respective table example (for cotton) in high color strength and with good fastnesses.

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W CO CO Cfl Example 65 A pH 7 solution at 15 to 20°C of the lithium salt of 239 parts of 2-amino-6-sulfo ~-naphthol in 2000 parts of water is admixed with 175 parts of trans-cyclohex-4-ene-1,2-dicarboxylic anhydride; the reaction batch is 5 additionally stirred for about 3 hours at 15 to 20°C while a pH of 6 is maintained by means of lithium hydroxide and then admixed with a conventionally prepared hydrochloric acid diazonium salt suspension of 281 parts of 4-(~3-sulfatoethylsulfonyl)aniline. The coupling reaction is carried out at pH 4 to 5 and a temperature of 5 to 10°C, and then the novel 10 azo compound of the formula (written in the form of the free acid) OH
/ ~ N=N / I \ NH-CO OOH
S02 \ \

(~max = 493 nm) is isolated by spray drying at pH 5.5. It has very good fiber-reactive dye properties and dyes for example cotton by the dyeing and printing processes customary in the art for fiber-reactive dyes in strong orange shades having good fastness properties, for example good lighttastnesses.
Example 66 A pH 6.5 solution of 281 parts of 4-(~i-sulfatoethylsulfonyl)aniline and 40 parts of sodium fluoride in 3500 parts of ice-water is reacted with 150 parts of cyanuric fluoride according to the procedure of DE-A 27 46 109 by gradual addition and thorough stirring. After the reaction has taken place, the batch is admixed with 180 parts of 1,3-diaminobenzene-4-sulfonic acid, adjusted to pH 6.5 with sodium carbonate and further stirred for about three hours whilst maintaining the pH and a temperature of 0 to 10°C.
The batch is then cooled down to 0°C, and the amino compound obtained is diazotized in a conventional manner by means of sodium nitrite and concentrated hydrochloric acid. The diazonium salt solution obtained is then added to the solution of the coupling component prepared from 319 parts of 1-amino-3,6-disulfo-8-naphthol and 180 parts of trans-cyclohex-4-ene-1,2-dicarboxylic anhydride according to the present Example 2. The coupling reaction takes place at a pH between 5.5 and 6.5 and a temp2rature of about 15°C.
The resulting synthesis solution with the novel monoazo compound of the formula (written in the form of the free acid) F

NH N~ J--NH \ ~ N=N / \
N

(~max = 516 nm) is buffered to pH 7 with a mixture of secondary and primary sodium hydrogen phosphate; the monoazo compound of the invention is then salted out with sodium chloride and isolated. It has very good fiber-reactive dye properties and dyes for example cotton in strong red shades having good fastness properties.
Example 67 239 parts of 3-amino-6-sulfo-8-naphthol and 170 parts of trans-cyclohex-4-ene-1,2-dicarboxylic anhydride are reacted with one another according to the directions of Example 1. The coupling component obtained is then coupled in an analogous manner at pH 5 and about 15°C with the diazonium salt of 311 parts of 2-methoxy-5-(~i-sulfatoethylsulfonyl)aniline, and the resulting inventive monoazo compound of the formula (written in the form of the free acid) /;~ N=N / I \
\ \ / NH-CO OOH

~~2 (~max = 492 nm) is isolated in a conventional manner. It dyes the fiber materials mentioned in the description part, especially cotton, by the dyeing and printing processes customary in the art for fiber-reactive dyes in brilliant orange shades having good fastness properties.
Example 68 A pH 7 solution at 15 to 20°C of the lithium salt of 239 parts of 2-amino-6-sulfo-8-naphthol in 2000 parts of water is admixed with 175 parts of 4-methyl-trans-cyclohex-4-ene-1,2-dicarboxylic anhydride; the reaction batch is additionally stirred for about 3 hours at 15 to 20°C while a pH of 6 is maintained by means of lithium hydroxide and then admixed with a conventionally prepared hydrochloric acid diazonium salt suspension of 281 parts of 4-(~i-sulfatoethylsulfonyl)aniline. The coupling reaction is carried out at pH 4 to 5 and a temperature of 5 to 10°C, and then the novel azo compound of the formula (written in the form of the free acid) OH
/ ~ N = N / I \ NH - CO OOH
SOZ \ \

(~max = 493 nm) is isolated by spray drying at pH 5.5. It has very good fiber-reactive dye properties and dyes for example cotton by the dyeing and printing processes customary in the art for fiber-reactive dyes in strong orange shades having good fastness properties, for example good lightfastnesses.
Example 69 A pH 6.5 solution of 281 parts of 4-(~i-sulfatoethylsulfonyl)aniline and 40 parts of sodium fluoride in 3500 parts of ice-water is reacted with 150 parts of cyanuric fluoride according to the procedure of DE-A 27 46 109 by gradual addition and thorough stirring. After the reaction has taken place, the batch is admixed with 180 parts of 1,3-diaminobenzene-4-sulfonic acid, adjusted to pH 6.5 with sodium carbonate and further stirred for about three hours whilst maintaining the pH and a temperature of 0 to 10°C.
The batch is then cooled down to 0°C, and the amino compound obtained is diazotized in a conventional manner by means of sodium nitrite and concentrated hydrochloric acid. The diazonium salt solution obtained is then added to the solution of the coupling component prepared from 319 parts of 1-amino-3,6-disulfo-8-naphthol and 180 parts of 4-methyl-trans-cyclohex-4-ene-1,2-dicarboxylic anhydride according to the present Example 2. The coupling reaction takes place at a pH between 5.5 and 6.5 and a temperature of about 15°C.
The resulting synthesis solution with the novel monoazo compound of the formula (written in the form of the free acid) F

N~ N
NH--~ ~ NH \ ~ N = N / \
N
\ /

(~max = 516 nm) is buffered to pH 7 with a mixture of secondary and primary sodium hydrogen phosphate; the monoazo compound of the invention is then salted out with sodium chloride and isolated. It has very good fiber-reactive dye properties and dyes for example cotton in strong red shades having good~fastness properties.
Example 70 239 parts of 3-amino-6-sulfo-8-naphthol and 170 parts of 4-methyl-trans-cyclohex-4-ene-1,2-dicarboxylic anhydride are reacted with one another according to the directions of Example 1. The coupling component obtained is then coupled in an analogous manner at pH 5 and about 15°C
with the diazonium salt of 311 parts of 2-methoxy-5-(~-sulfatoethylsulfonyl)aniline, and the resulting inventive monoazo compound of the formula (written in the form of the free acid) / I N-N / I \
\ \ / NH-CO OOH

~~2 (~max = 492 nm) is isolated in a conventional manner. It dyes the fiber materials mentioned in the description part, especially cotton, by the dyeing and printing processes customary in the art for fiber-reactive dyes in brilliant orange shades having good fastness properties.

Claims

What is claimed is:

1. A monoazo compound conforming to the general formula (1) where:
M is hydrogen or an alkali metal or some other colorless salt-forming metal;
m is zero or 1 (when m is zero, this group is hydrogen);
X is a fiber-reactive group or a grouping which contains a fiber-reactive group;
W is alkylene of 1 to 4 carbon atoms, or is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and chlorine, or is alkylene of 3 to 6 carbon atoms which is interrupted by an -O- or -NH-group;
R° is hydrogen or alkyl of 1 to 4 carbon atoms or is phenyl which may be substituted by sulfo, methyl, ethyl, methoxy, ethoxy or chlorine;
alk is alkylene of 1 to 4 carbon atoms;
r is zero or 1;
s is zero or 1;
t is zero or 1;
D is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and chlorine, or is naphthylene which may be substituted by 1 or 2 sulfo groups;
R is hydrogen or alkyl of 1 to 4 carbon atoms;
G is the bivalent radical of a cycloalkyl of 5 to 8 carbon atoms or of a bicycloalkyl of 5 to 8 carbon atoms, it being possible for the alicyclic radicals to contain an olefinic double bond and/or to be interrupted by a hetero group and moreover to be substituted by 1 or 2 substituents selected from the group consisting of halogen or alkyl of 1 to 4 carbon atoms, which may be substituted;
when X is a heterocyclic radical, s is zero and r is 1.

2. A monoazo compound as claimed in claim 1, conforming to the general formula (1B) where:
M and G are each as defined in claim 1, the -NH-CO-G-COOM group is attached in position 2 or 3 of the 8-hydroxynaphthalene radical, and X0-D1- is a radical of the general formula (5a) or (5b) where M is hydrogen or an alkali metal, Y is vinyl or is ethyl which contains an alkali-eliminable substituent in the .beta.-position, m is zero or 1, R9 is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen, and R10 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.

3. A monoazo compound as claimed in claim 1, conforming to the general formula (1B) where M and G are each as defined in claim 1, the -NH-CO-G-COOM
group is attached in position 2 or 3 of the 8-hydroxy-naphthalene radical, and X0-D1- is a radical of the general formula (5c) or (5d) where M is hydrogen or an alkali metal, m is zero or 1, R0 is hydrogen, methyl or ethyl, R9 is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen, R11 is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, n is 1, 2 or 3, and V is a group of the general formula (3a), (3b), (3g) or (3h) where Hal is chlorine or fluorine, R5 is hydrogen or alkyl of 1 to 4 carbon atoms or phenyl, which can be substituted by chlorine, sulfo, carboxyl, methyl, ethyl, methoxy or ethoxy;
R6 is a group of the general formula (4a) or (4b) (4a) (4b) where Y is vinyl or is ethyl which contains an alkali-eliminable substituent in the .beta.-position, ALK is alkylene of 1 to 4 carbon atoms, and AR is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms and chlorine, or is naphthylene which may be substituted by 1 or 2 sulfo groups, R7 is hydrogen or alkyl of 1 to 4 carbon atoms, R8 is a group of the general formula (4c) or (4d) Y-SO2-Alk-E-Alk- Y-SO2-(Alk)p-E-(Alk)q-(4c) (4d) where Y is as defined above, Alk is alkylene of 2 to 4 carbon atoms, E~ is an -O- or -NH- group, p is zero or 1, and q is zero or 1, subject to the proviso that their sum (p + q) is 1.

4. A monoazo compound as claimed in claim 3, wherein V is a radical of the general formula (3g) where Hal is as defined therein, R5 is hydrogen and R6 is a radical of the therein mentioned and defined general formula (4b).

5. A monoazo compound as claimed in claim 1, wherein X is a radical of the general formula (3g) where Hal is chlorine or fluorine, R5 is alkyl of 1 to 4 carbon atoms or phenyl, which may be substituted by chlorine, sulfo, carboxyl, methyl, ethyl, methoxy or ethoxy, and R6 is a group of the general formula (4a) or (4b) (4a) (4b) where Y is vinyl or is ethyl which contains an alkali-eliminable substituent in the .beta.-position, ALK is alkylene of 1 to 4 carbon atoms, and AR is phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxyl, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms and chlorine, or is naphthylene which may be substituted by 1 or 2 sulfo groups.

6. A monoazo compound as claimed in at least one of claims 1 to 5, wherein G is a radical of the general formula (2a), (2b), (2c), (2d) or (2e) where R1 is hydrogen, methyl or ethyl, and R2 is hydrogen, methyl, ethyl or chlorine.

7. A monoazo compound as claimed in at least one of claims 1 to 5, wherein G is 1,2-cyclohexylene or 1,2-cyclohex-4-enylene.

8. A monoazo compound as claimed in claim 1, wherein X is a radical of the formula Y-SO2- or contains a radical of the formula Y-SO2- and Y is vinyl, .beta.-sulfatoethyl or .beta.-chloroethyl.

9. A process for preparing a monoazo compound of the general formula (1) mentioned and defined in claim 1, which comprises reacting an aminonaphtholsulfonic acid of the general formula (9) where M, m and R are each as defined in claim 1, with an anhydride of the general formula (10) where G is as defined in claim 1, in aqueous suspension or in an organic reaction-inert solvent or in a mixture of such a solvent with water and then reacting the resulting compound of the general formula (11) where M, m, R and G are each as defined in claim 1, with a diazonium salt compound of an amino compound of the general formula (12) where X, W, R0, alk, D, r, s and t are each as defined in claim 1, or in the case of the synthesis of a monoazo compound (1) where X is a heterocyclic fiber-reactive group, initially coupling the diazonium salt of a compound of the general formula (13) H-N(R°)-D-NH2 (13) where D and R° are each as defined in claim 1, with a compound of the general formula (11) and then reacting the resulting monoazo compound conforming to the general formula (14) where the individual elements of the formula are each as defined in claim 1, with a compound of the general formula Hal-X, where Hal is as defined in claim 1 and X is a radical of the general formula (3a) to (3h), or in the case of the synthesis of a compound of the general formula (1) where X is a radical of the general formula (3f) to (3h), reacting a compound of the general formula (14) with 2,4,6-trihalo-1,3,5-triazine and reacting the resulting dihalotriazinylaminoazo compound with an amine of the general formula R3R4NH or R5R6NH or R7R8NH where R3, R4, R5, R6, R7 and R8 are each as defined above.

10. The use of a monoazo compound as claimed in claim 1 or of a monoazo compound prepared according to claim 9, for dyeing hydroxyl- and/or carboxamido-containing material, especially fiber material.