CA1114811A - Anthraquinone-azo compounds, their preparation and their use as dyestuffs - Google Patents

Abstract

Abstract of the disclosure:
Water-soluble anthraquinon-azo compounds preferably in the form of their salts and written in the form of the free acid having the formula

Description

The present invention relates to new water-s~luble anthraquinone-azo compounds which have, written in the form of the free acid, the general formula (1):
~ 1 2 ~03 (1).
0 N} ~ N=N-K-Z

The new compounds can be in the form of the free acid or in the form of its salts. They are preferably in the form of salts, particularly the alkali metal salts and also the ammonium salt, but particularly in the form of the sodium salts~
The new compounds are used, preferably in the form of their alkali metal salts for dyeing and printing fiber materials.
In the above formula tl), the various formula radicals have the following meanings: the Rls are identical or different, but are not both hydrogen simultaneously and each is a hydrogen atom or a sulfo group; K is the monovalent residue of a coupling compone~nt, preferably belonging to the series of the acetoacetylarylamides, such as acetoacetylanilides and aceto-acetylnaphthylamides, of l-phenylphrazol-5-ones or l-naphthylpyrazol -5-ones which are substituted in the 3-position by lower alkyl, such as methyl, carboxy, carbamoyl, lower carboalkoxy, such as carbomethoxy and carboethoxy, phenyl or phenyl which is substituted by ~Bi -2- ~

.

. ' lower alkyl, lower alkoxy and/or halogen, such as chlorine, or of 1-phenyl-5-aminopyrazoles or 1-naphthyl-5-amino--pyrazoles which are substituted in the 3 position by lower alkyl, such as methyl, carboxy , carbamoyl, lower carbo-alkoxy, such as carbomethoxy and carboe-thoxy, phenyl or phenyl which is substituted by lower alkyl, lower alkoxy and/or halogen, such as chlorine, or belonging to -the series of naphthols, and the carbocyclic aromatic nuclei in the coupling components, where not already indicated above, can~be further substituted by substituents, prefer-ably by 1 to 3 substituents, the substituents preferably belonging to the group comprising lower alkyl) such as methyl and ethyl, lower alkoxy, such as methoxy and ethoxy~
halogen, such as chlorine and bromine, nitro~ carboxy., carboxylic acid amide, carboxylic acid amide which is mono-subst-ituted or disubstituted by lower alkyl, benzyl and/or phenyl, sulfonamide, sulfonamide which is monosubstituted or disubstittlted ~ lower alkyl, benzyl and/or phenyl, lower alkanoylamino, benzoylamino 9 hydroxy , amino, lower alkylsulfonyl, phenylsulfonyl9 lower alkylamino, lower dialkylamino~ lower N-alkyl-N-phenylamino, phenylamino, benzylamino and sul~o, and also to the series of amino-naphthalenes which are optionally substituted on the ~itrogen by alkyl radicals and/or phenyl radicals and are optionally substituted additionally in the aromatic nuclei by 1, 2 or 3, preferably 1 or 2, substituents belonging to the group comprising sul~o~ lower alkyl~ such as methyl and ethyl, lower alkoxy9 such as methoxy and ethoxy, halo gen, such as chlorine and bromine, lower alkanoylamino, :

benzoylamino, amino, lower alkylsulfonyl, phenylsulfonyl, lower alkylamino, lower dialkylamino, lower N-alkyl-N-phenylamino, phenylamino and benzylamino, and also to the series of anilines, including diaminobenzenes which are optionally substituted on the nitrogen by alkyl radi-cals and/or phenyl radicals and are optionally substituted additionally in -the aromatic nuclei by 1~ 2 or 3, prefer-ably 1 or 2, substituents belonging to the group comprising lower alkyl, such as methyl and ethyl, lower alkoxy, such as methoxy and ethoxy, halogen, such as chlorine and bro-mine, lower alkanoylamino, benzoylamino,lower alkylsulfonyl~
phenylsulfonyl, lower alkylamino~ lower dialkylamino, lower - N-aLkyl-N-phenylamino~ phenylamino and benzylamino; Z is a fiber-reactive group which is linked to a carbocyclic aromatic nucleusof the coupling component; and n is the number 1 or 2, preferably 1~ .
Here and in the following text~ the term "lower"
means that the alkyl or aLkylene radicals contained in the groups can have 1 to 4 C atoms.
Z is preferably a group of -the ~ormula (2a)~ ~2b) or (2c~ .
S2 CH2-CH2_Zl (2a) -S02-CH2=CH2 (2b) -N~Y (2c) R

25 in which Zl is the hydroxy group or an inorganic or org anic radical which can be eliminated to form -S02-CH=CH2, R is a hydro~.en atom or alower alkyl group, such as, in particu:Lar~ the methyl or ethyl group, which can . . ~ .

.
~ ~

additionally be substituted by a cyano group, and Y is a fiber-reac-tive radical belonging to the cycloaliphatic, aromatic or heterocyclic series or is a radical belonging to the alipha-tic series, and is thus also a radical of the above formula (2a~ or (2b).
~K~Zn is preferably a radical of the formula (3a), (3b)~ (3c), (3d)~ (3e)~ (3f), (3g)~ (3h)~ (3i), (3j), (3k) or (3m) ' - ,.
CO-CH3~ CO-CH
-CH . ~ 2 ~ CH
CO-NH ~ z CO-N~ ~ z -R3 R~ ~4 R2 (3b) (3a) .
. ~2 R' i / ( R3 ) n l ' ' NH2 ,_ 1 /( R3 ) n ' Zn ~ X R4 Bl ~3c) B2 : (3d) ,. _ OH OH

'' (S03H)m (3f) . --: . ' .

,..................... ~ .
N~ N~
z ~ (3h) t 3g ~ Z

~R ~ R7 (S03H)m t31~ -. . .

~- N ~ N \

. . 5 ~3k) IN-Y ~3m) , in which the formula radicals have the following meanings:
Z has the above, particularly preferred, meaning; n is the number 1 or 29 preferably 1; n' is the number 1 or 2, preferably 1, it being possible for n and n' to be identi-cal or di~ferent from one another; R~ is a hydrogen atom, a lower alkyl group, such as, in particular, a methyl or ethyl group, a lower alkoxy group, such as, in particular, - a methoxy or ethoxy group9 a chlorine or bromine atom or a sulfonic acid group, R3 is a hydrogen atom, a lower alkyl group, such as, in particulara the methyl or ethyl group~
a lower alkoxy group, such as, in particular, the methoxy or ethoxy group, or a chlorine or bromine atom, R4 is a hydrogen atom, a lower alkyl group9 such as, in particular, .

- 7 ~
the methyl or ethyl group, a lower alkoxy group, such as, in particular, the methoxy or ethoxy group, or the sul-~onic acid group, it being possible for R2, R3 and R4 to be identical or different from one another; ~ is a hydro-gen atom, a lower alkyl group, such as, in particular9 ame-thyl or ethyl group, a lower alkoxy group; such as, in particular, a methoxy or ethoxy group, a chlorine or bro-mine atom, a lower alkanoylami.no group, such as an acetyl-amino group, or a sulfonic acid group; Bl is a lower alkyl - 10 group, preferably a methyl group, a carboxyl group or a carbomethoxy or carboethoxy group and B2 is a lower alkyl group, preferably the methyl group, a carbomethoxy or carbo-ethoxy group, a carboxamide group or a phenyl radical which can be substituted by 1 or 2 substituents belonging to the group comprising lower alkyl, lower alkoxy, chlorine, bro-mine and sulfoz it being possible for ~ , R3 and R4 and Bl - and B2, respectively, to be identical or different from one . another; R~ is a hydrogen atom or a lower alkyl radical;
R" is a hydrogen atom, a lower alkyl radical or a phenyl radical which can be substituted by 1 or 2 substituents belonging to the group comprising lower alkyl, lower alk-oxy, chlorine, bromine and s~o, it being possible for R' and R" to be identical or different from one another; m is the number zero, 1 or 2; R5 is a hydrogen atom~ a lower alkyl group, such as a methyl or ethyl group, a lower alk-oxy group, such as a methoxy or ethoxv group, or a chlorine or bromine a-tom, R6 is a hydrogen atom or a lower alkyl group which can be substituted by a hydroxy , cyano, car-boxy., sulfo~ sulfato~ carbomethoxy, carboethoxy or ~L~$~
acetoxy group, R7 is a hydrogen atom or a lower alkyl group which can be substituted by a hydroxy, cyano, carboxy, sulfo, sulfato, carbomethoxy, carboethoxy or acetoxy group, or is a benæyl radical or a phenyl radical which can be substituted by lower alkyl, lower alkoxy, chlorine and/or sulfo; and R'5 is a hydrogen atom, a lower alkyl group, such as the methyl or ethyl group, a lower alkoxy group, such as the methoxy or ethoxy group, a chlorine or bromine atom, a lower alkanoylamino group, such as the acetylamino group, or an amino, ureido, lower alkylsulfonylamino, lower alkyl-amino or lower dialkylamino group, it being possible for R, R2, R5', R5, R6 and R7 to be identical or different ~rom one another. A is a benzene or naphthalene nucleus.
Radicals Zl which can be eliminated from the formula (2a) by the action of alkalis are, for example, a halogen atom, such as a chlorine or bromine atom, the sul-fato, thiosulfato or phosphato group or a lower alkyl-sulfonyloxy group, such as the methylsulfonyloxy or elhylsulfonyloxy group, or a lower dialkylamino group, such as, for example, the dimethylamino or diethylamino group. Radicals Zl which can be eliminated under neutral or acid conditions are, for example, the N-(e-sulfoethyl-amino) or the N~ sulfoethyl)-N-methylamino group, which are prefarably in the form of the sodium potassium or ammonium salt.
The fiber-reactive radical Y is, in particular, a known fiber-reactive acyl radical of a lower halogenoalkane-carboxylic acid, a lower halogenoalkenemonocarboxylic and _ 9 _ halogenoalkenedicarboxylic acid, a nitrohalogenobenzene-sulfonic or nitrohalogenobenzenecarboxylic acid, a halogenocyclobutylcarboxylic or halogenocyclobutenyl-carboxylic acid or a haiogenocyclobutylacrylic or halogeno-5 cyclobutenylacrylic acid or a halogenoethylsulfonylendo-methylenecyclohexanecarboxylic acid, a known fiber-reactive acyl radical o~ a benzo-heterooyclic carboxylic or sulfonic ~cid which is substituted by halogen in the heterocyclic structure, such as a halogenobenzoxazolecarboxylic acid or a halogenobenzthiazolecarboxylic or halogenobenzthiazole-sul~onic acid, and also the fiber-reactive acyl radical c~
an aromatic-heterocyclic carboxylic acid or sulfonic acid, the heterocyclic structure of which preferably contains 2 or 3 nitrogen atoms and is preferably a 6-membered hetero- -cyclic structure, for example the pyridazine, pyridazinone,pyrim:i.dine, phthalazine, quinazoline or quinoxaline radi-cal, wherein the heterocyclic structure is substituted by one or two ~iber-r~active leaving groups, preferably belonging to the group comprising halogen9 such as chlor-ine and fluori~e, lower alkylsulfonyl and sulfo, and canbe substituted by 1, 2 or ~ further substituents, such as, for example, substituents belonging to the group comprising lower alkyl, lower alkoxy, lower carboalkoxy, lower halo--genoalkyl, lower hydroxyalkyl, carboxy , sulfo, aryloxy, aliphatic mercapto, aromatic mercapto, lower alkanoyl, cyano, nitro and primary, secondary and tertiary amino groups having aliphatic, heterocyclic and/or aromatic radi-cals, and also the fiber-reactive radical of a heterocyclic structure havLng 2 or 3 nitrogen atoms, in particular a - ~-membered heterocyclic structure, for example the pyrimi-dine, pyridazine or -tria~ine ring, wherein the heterocyclic structure is substituted by one or two fiber-reactive leav-ing groups, preferably belonging to the group comprising halogen, such as chlorine and fluorine, lower alkylsulfonyl and sulfo, and can be substituted by 1, 2 or 3 Purther sub-- stituents, such as, for example, substituents belonging to the group comprising lower alkyl, lower alko~y, lower carboalkoxy, lower halogenoalkyl, lower hydroxyalkyl, carb oxy., sulfo, aryloxyg aliphatic mercapto, aromatic mercapto, lower alXanoyll cyano, nitro and primary, secondary and tertiary amino groups having alipha-tic, heterocyclic and/or aromatic radicals.
Y can also be a radical of the above formula (2a) in which Zl has the meaning indicated or can be the vinyl-sulfonyl group.
~iber-reactive radicals Y belonging to the formula (2c~ are, for example, the chloroacetyl, bromoacetylg ~-chloropropionylp ~-bromopropionyl, a,~-dichloropropionyl or ~ dibromopropionyl radical, the acyl radical o~ a chloromaleic acid, the ~-sulfa-toethylsulfonyl radical, the acryloyl radical, the ~-chloroacryloyl radical, the ~-bromoacryloyl radical, the a-ch~acry~ylr~cal, the a-bromo-acryloyl radical, the a,~-dichloroacryloyl radical9 the a,~-dibromoacryloyl radical9 the trichloroacryloyl radical, the chlorocrotonyl radical, the propiolyl radical, the 3,5-dinitro-4-chlorobenzenesulfonyl radical, the 3,5-di nitro-4-chlorobenzenecarbonyl radical, the 2,~,3,3-tetra-fluorocyclobutylacryloyl radical, the 2 9 2,3,3-tetrafluoro--.

~iL~

cyclobutylcarbonyl radical, the 2,3,3-trifluorocyclobut - l-enylacryloyl radical, the 3-nitro-4~chlorobenzenesulfonyl radical, the 3-nitro-4-chlorobenzenecarbonyl radical, the ~-chloroethylsulfonylendome-thy:Lenecyclohexanecarbonyl radi-cal and the 3-~-chloroethylsulfonylbenzoyl radical and also the 2-chlorobenzoxazolecarbony:L radical, the 2-chlorobenz-thiazolecarbonyl radical or the 2-chlorobenzthiazole-sulfonyl radical, and also-the six-membered heterocyclic acid radicals (acyl radicals) of ~-(4,5-dichloropyridazin-6-on-1-yl)~propionic acid 7 1,4-dichlorophthalazinecarboxy~c or 1,4-dichlorophthalazines~fonio acid, 2,4-dichloroquin-azoline~box~lic or 2i4-dichloroquinazolinesulfonic acid,

2,3-dichloroquinoxalinecarboxylic or 2,3-dichloroquinoxaline sulfonic acid, 2,6 bismethylsulfonylpyridine-4-carboxylic acid, 3~6-dichloropyridazine-5-carboxylic acid, 2~4-di-chloropyrimidine-6-carboxylic acid, 2,4-dichloropyrimiline-5-carboxylic acid, 2,6-dichloropyrimidine-4-carboxylic or 2,6-dichloropyrimidine-4-sulfonic acid~ 2,6-dibromopyrimi-dine-4-carboxylic or 2~6-dibromopyrimidine-4-sulfonic acid, 2,6-dichloropyrimidine-5-carboxylic or 296-dichloropyrimi-dine-5-s~lfonic acid, 2,6-dibromopyrimidine-5-~arboxylic or 2,6-di~romopyrimldine-5-sulfonic acid~ 2-chlorobenz-thiazole-6-carbox~lic acid and 2-chlorobenzthiazole-6--sulfonic acid, the ~-sulfatoethylsulfonyl radical9 the ~-~hloroethylsulfonyl radical, the ~-phosphatoethylsulfonyl radical, the ~-thiosulfatoethylsulfonyl radical and the vinylsulfonyl radical, and also the des-halogeno radical ?
des sul~o radical or des-alkylsulfonyl radical, as re- -.
levant, of ~-(4,5-dichloropyridazin-6-on l-yl)-propionic . - 12 -acid, 1,4-dichlorophthalazinecarboxylic or 1,4-dichloro-phthalazinesulfonic acid, 2,4-dichloroquinazoli~ecarboxylic or 2,4-dichloroquinazolinesulfonic acid, 2,~-dichloro-quinoxaline carboxylic or ~3-dichloroquinoxalinesulfonic acid, 2-methylsulfonyl-4 chloro-6-methylpyrimidine, 2~ bis-methylsulfonyl-6-methylpyri.midine, 2,4,6-tribromo~
pyrimidine, 2,4,5 9 6-tetrabromopyrimidine 9 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine 3 a 2,4-~ichloropyrimidine-5-sulfonic acid, a 5-nitror-294,6-trichloropyrimidine, a 5-cyano-2,4,6-trichloropyrimidine, 2,6-bis-methylsulfonyl-pyridine 4-carboxylic acid, 2,4-dichloro-5-chloromethyl-6-methylpyrimidine, 2,4-dibromo-5-bromomethyl-6-methyl-pyrimidine, 2 9 4-dichloro~5-bromomethylpyrimidine, 2,4-di-bromo-5-bromomethylpyrimidine, 2,5,6-trichloro-4-methyl-pyrimidine, 2,6-dichloro-4-trichloromethylpyrimidine, 2,4-bi~-~ethylsul~onyl~5-chloro-6-methylpyrimidine, 2,4,6-trimethylsulfonyl-1,3,5-triazine, 2,4-dichloropyrim-idine, 3,6-~ichloropyrimidine, 3,6-dichloropyridazine-5-carboxylic acid, 2,6-dichloro-4-carboethoxypyrimidine, 2~6-dibromo~4-carboethoxypyrimidine~ 2,4,5-trichloro-pyrimidine, 2,4-dichloropyrimidine-6-carbo~ylic acid 9 2,4-dichloropyrimidine-5-carboxylic acid, 2,6-dichloro-.pyrimidine-4-carboxylic acid amide, 2,6-dibromopyrimidine-4-carboxylic acid amide, 2~6-dichloropyrimidine-4-carbox-25 ylic or 2,6 dichloropyrimidine-4-sul~onic acid, 2,6-di-bromopyrimidine-4-carboxylic or 2,6-dibromopyrimidine-4-sulfonic ac:id, 2,6-dichloropyrimidine-5-carboxylic or 2,6-dichloropyrimidine-5-sulfonic acid amide, 2,6-dibromo-pyrimidine-5-carboxylic or 296-dibromopyrimidine-5-sulfonic . 13 - ;
acid amide, 2,6-dichloropyrimidine-5-carboxylic or 2,6-di-chloropyrimidine-5-.q~f ~ c acid, 2,6-dibromopyrimidine-5-carboxylic or 2,6-dibromopyrimidine-5-sul~onic acid, 2,4,5,6-tetrachloropyridazine, 5-bromo-2,4,6-trichloro-pyrimidine, 5-acetyl-2,4,6-trichloropyrimidineg 5-~itro-6-methyl-2,4-dichloropyrimidine, 2,4,6-trichloro-5-bromo-pyrîmidine~ 2~4,5~6-tetraM uoropyrimidine, 4,6-difluoro-5-chloropyrimidine, 2,4,6-trif:Luoro-5-chloropyrimidine, 2,4,5-trifluoropyrimidine, 2,4,6-trichloro-1,3,5-triazine~
~,4,6-trib~omo-1,3,5-triazine, 2,4,6-trifluoro-1,3,5-tri-azine or a 4,6-diflu4ro-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 su~stituted in the 2-position by a radical belonging to 15 the group comprising aryl, such as phenyl 9 lower alkyl, such as methyl or ethyl, aliphatic mercapto, such as lower alkylmercapto, aromatic mercapto, such as arylthio~ for example phen~lthio aliphatic oxy, such as lower alkoxy, aromatic oxy, such as aryloxy, for example phenoxy and 20 naphthoxy, or primary amino, secondary amino and tertia~y amino containing aliphatic, heterocyclic and/or aromatic radicals~ -Radicals of this type, which are li~ked in the 2-position to the triazine nucleus of the 4,6-dihalogeno 25 compound and can be prepared via the corresponding, for ex~ethef~now~ng, compounds by reaction with trihalogeno-triazines, are, for example~the ether radicals of., for example, the ~ollowing aliphatic and aromatic hydroxy compounds: lower thio alcohols, lower alkoxyalkanols~

L

lower alkanols 9 such as methanol, e-thanol 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 a1iphatic and/or aromatic amino groups, which can contain an acylatable amino or hydroxy group, such as the amino radicals of hydroxylamine, hydrazine, s~lfophenylhydrazine, ethanolamines and propanolamines, and also the amino radicals of methylamine, ethylamine, isopropylamine, methoxyethylamine, methoxypropylamine, ~5 dimethylamine~ diethylamine, methylphenylamine, ethyl-phenylamine, chloroethylamine, benzylamine, cyclohexy~.amine, morpholine, piperidine and piperazine and also, preferably~
o~ N,N-bis-~ '-chloroethylsulfonyl)-ethylamine and also of oxygen ether compounds which can also contain an amino group which can be acylated, such as hydroxylamine.
The new compounds of the formula (1) are prepared in a manner according to the invention by diazotizing in a customary manner a l-amino-2-sulfo-4-(4' aminophenyl)-. aminoanthraquinone compound of the general formula (4) I (4 Rl . .

in which Rl 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 ~orm ula (5) ~ ~ (5) O NH ~ ~
~ ~ N (+) in which Rl has the meaning cited, and subsequently coup-ling the diazonium sait of the cation o.~ the formula (5) thus obtained with a coupling component o~ the formula (6) H-K-Zn (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.
~0 m e present in~ention enriches the art with ~ur- -ther valuable dyestuffs, but also enriches it with a new, simple means, which involves little technical outlay, of ~ynthesizlng anthraquinone-azo compounds of the .

, ~ ' . ~ ' ' ~ .

16 i~
type of the ~ormula (1) It is in fact not possible to follow a method of synthesis for the pre-paration of the new compounds of the formula (1) which is analogous to theproce~es known ~rom U S Patent Specifica-tions Nos. 2,108,126 and 2,154,954, because the condensa-tion reaction of l-amino-4-bromoanthraquinone-2~sulfonic . acid with a corresponding aminosulfophenyleneazo compound in the presence o~ copper salts fails, since the amino group in the l-amino-2-sulfophenyl-4-azo or 1-amino-3-sul fophenyl-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 man-ner according to the invention, preferably by coupling the diazonium compound o~ the formula (5) with a coupling com-ponent o~ the formula (7) H K Z2 (,7) in which K has the meaning mentioned above and Z2 is the group of the formula -NHR in which R has the meaning men-tioned above, and subsequently reacting, in a manneranalogous to customary and known process methods, the resulting compound of the formula (8), written in -the for~
of the free acid, O I~H2 SO H

D ~H ~ (8) ~ ' N = N - ~ - NH
: : . R1 . .

in which Rl, R and K have -the meaning mentioned,wi~h a com-pound of the formula (9) which contains tl~e fiber-reactive radical Y and which has the formula (9) Hal--Y (g) wherein Y has thea~ovemen~ioned meaning and Hal is a fluo-rine, chlorine or bromine atom, or with a corresponding acid anhydride containing the radical YO
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), (7g), (7h), (7i), (7j), (7k) or (7m) I H 3 R ~ ~ 3 CO-N~ ~ 2 CO-NH ~ Z2 R3 , 4 l R4 R2 . . (7b) ~7a) .

.

~2 R2 OH ¦ / (R3)nl NH2 _ ¦ / ( 3)n' ~ ¦ Z2 ~T R4 B1 (7c) . B2 (7d) .

' _~ . . OH

z2 ~ Z2 t7e) . 3H)~
. (7f) NH2 ,, ~ . ' .. , ¦SO3H~ 2 ~ - R~ ( 7 h ) (7g) . ~

N-H - ~ N /

` ~SO3~am .` . ~2 (7i~ (7~) R5 . R5 .-N \ . ~ N

R5 - ~ H
. In the formulae (7a) to (7m), Z29 R2~ R3, R~, n', A, R'2, Rg, R', R", R5g ~ and ~ ha~e the meanings indicated above.
m e following are examples of the coupling com-ponents of the general formula (6): N-acetoacety~aniline-

3-~-sulfatoe-thyl sulfone, N-acetoacetylaniline-4-~-sulfato-ethyl sulfone, N-acetoacetylaniline-3-~-chioroethyl sulfone, N-acetoacetylaniline-4-~-chloroe-thyl sulfone, N-aceto-acetyl-2-methoxy-5-~-sulfa-toethylsulfonylaniline, N-aceto-acetyl-2-methoxy 5~vinylsulfonylaniline, N-acetoacetyl-

4-methoxy-3-~-sulfatoethylsulfonylaniline, N-acetoacetyl-2-methoxy-5-methyl-4-~-sulfatoethylsulfonylaniline, N-ace-toacetyl-2-methoxy-5-methyl-4-~-thiosulfatoet~ylsulfonyl-aniline~ N-acetoacetyl-2,5-dimethoxy-4-~-sulfatoethyl-sulfonylaniline, N-acetoacetyl-2,5-dimethoxy-4-~-(methyl-sulfonyloxy)-ethylsulfonylaniline, 1-(4'-~-sulfatoethyl-sulfonylphenyl)-3-methylpyrazol-5-one, 1-(3'-~-sulfato-ethylsulfonylphenyl)-3-carboxypyrazol-5-one, 1-~2'-methoxy-4'-~-sulfatoethylsulfonylphenyl)-3-carboxypyrazol-5-one, 1-(3'-~-sulfatoethyisulfonylphenyl)-3-methyl-5-aminopyra-- zole ? 1- ~4'-~-sulfatoethylsulfonylphenyl)-3-methyl-5-amino-pyrazole, l-(2'-methoxy-5'-~-sulfatoethylsulfonylphenyl)-3-methyl-5-aminopyrazole, 1-(2'-methoxy-5'-methyl-4'-~-sul-fatoethylsulfonylphenyl)-3-methyl-5-aminopyrazole, N-aceto-acetyl-(4-N-~-sulfatoethylsulfonylamino)-aniline, N-aceto-acetyl-(3-N-~-sulfatoethylsulfonylamino)-aniline, N-aceto-. acetyl-(2-methyl-4-N-~-sulfatoethylsulfonylamino)-aniline 9 N-acetoacetyl-(2-methoxy-4-N-~-sulfatoethylsulfonylamino~-aniline, N-acetoacetyl-(4-N-~-sulfatoethylsulfonyl-N-methyl-amino)-aniline, N-acetoacetyl-(3-N-~-sulfatoethylsulfonyl-N-ethylamino)--aniline~ 1-(4'-N-~-sulfatoethylsulfonylamino)-phenyl-3-methylpyrazol-5-one 3 1- (3'-N-~-sulfatoethylsulfon-yl-N-methylamino)-phenyl-3-carbomethoxypyrazol-5-one, 1-(4'-N-vinylsulfonyl-N-methylamino)-phenyl-3~methyl-:: .

5-aminopyrazole, 1-(3'-~-sulfatoe-thylsulfonylamino-6'-meth-yl)-phenyl-3-carboxypyrazol 5-one, 1-amino-3-(N-~-sulfato-ethylsulfonyl-N-methyl)-aminobenzene, l-amino-3-(N-~-sulf-atoethylsulfonyl-N-ethyl)-aminobenzene, 2-(N-~-sulfatoethyl-sulfonyl-N-methyl)-amino-8-naphthol-6-sulfonic acid, 2-(N-vinylsulfonyl-N-methyl)-amino-8-naphthol-6-sulfonic acidj 2-(N-~-sulfatoethylsulfonyl-N-methyl)-amino-5 naphth-ol-7-sulfonic acid or 2-(N-vinylsul~onyl)--amino-5-naphthol-7-sulfonic acid. .
m e following are examples of the coupling com ponents of the general formula (7): l-N-acetoacetylamino 4~aminobenzene, 1-N~acetoacetylamino-4-N-methylaminoben-zene, l-N-acetoacetylamino-3-methyl-4-aminobenzene, l-N-ace~cetylamino-3-methoxy-4-aminobenzene, 1-(3'-amino-phenyl)-3-methylpyrazol-5-one, 1-~4'-aminophenyl)-3-methyl-pyrazol-5-one, 1-(3'-aminophenyl)-3 carboethoxypyrazol-5-one 9 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',49,6i-trimethyl-3'-amino-5'-sulfophenyl)-3-carbo-ethoxypyrazol-5-one 9 aniline-N-methanesul~onic acid~ -o-toluidine, m-toluidine, 2,6-dimethylaniline 9 2,5-dimethyl-aniline~ o-ethylaniline, m-ethyIaniline, o-tert~-butyl-aniline, m-chloroaniline, o-anisidine, m-anisidine, o-phenetidine, m-phenetidine, N-methylaniline, N-ethyl-aniline, N-~-hydroxyethylaniline, N-~-acetoxyethylaniline, N-butylanlline, 4-~-cyanoethylaniline, N-~-cyanoethyl m-toluidine, N-ethyl-m-toluidine, 2-aminohydroquinone dimethyl or diethyl ether, cresidine, m-phenylenediamine~

.

.
~ 21 -3-N-acetylamlnoaniline, 3-ureidoaniline, 3-N-me-thylsul~onyl-aminoaniline, 2-me-thoxy-5-acetylaminoaniline, l-amino-naph-thalene-6-sulfonic acid, 1-aminonaphthalene-7-sul~onic acid, 2 methoxy-1-aminonaphthalene-6-sulfonic acid, 2-eth-oxy-1-aminonaphthalene-6-sulfonlc acid, 2-amino-8-naphthol-

6-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, . 2-methylamino-8-naphthol-6-sulfonic acid, 1-amino-8-naph-' thol-3,6-disulfonic acid or 1-amino-8-naph-thol-4,6-disul-; fonic acid.
Compo~nds'of -the formula (9) are, for example, chloroacetyl chloride, bromoacetyl chloride, ~ chloro-propionyl chloride, ~-b'romopropionyl chloride, ,~-di-chloropropionyl chloride, a,~-dibromopropionyl chloride, chloromaieic anhydride J acryloyl chloride, ~-chloroacryl-15 oyl chloride, ~-bromoacryloyl chloride, ~-chloroacryloyl chloride, a-bromoacryloyl chloride9 a,~-dichloroacryloyl '. chloride, a,~-dibromoacryloyl chloride, trichloroacryloyl - ~. chloride~ c~lorocrotonyl chloride, propiolyl chloride, ~,5-dinitro-4-chlorobenzenesulfonyl chloride, 3,5-dinitro 4-chlorobenzoyl chloride, 2 9 2,3,3-tetrafluorocyclobutyl-acryloyl chloride, 3-nitro-4-chlorobenzenesul~onyl chlor-ide, 3 nitro-4-chlorobenzoyl chloride, 2~2~3,3-tetrafluoro-cyclobutane-1-carboxylic acid chloridej ~-chloroethyl-sulfonylendomethylenecyclohexanecarboxylic acid chloride, 25 3-~-chlor.oethylsul~onylbenzoyl chloride and heterocyclic acid halides and derivatives thereof, such as the 2-chloro-benzoxazolecarboxylic acid chlorides, 2-chlorobenzthiazole-carboxylic acid chlori~s and 2-chlorobenzthiazolesulfonyl chlorides, above a~lthosec~al~rgatle~ two nitrogen atoms : .

as the hetero-atoms of a 6-membered heterocyclic structure, such as, for exampleJ ~-(4,5-dichloropyridazin-6-on l-yl) propionyl chlorideg- 1,4-dichlorophthalazinecarboxylic acid chloride 9 1,4-dichlorophthalazinesulfonyl chloride, 2,4-di-chloroquinazolinecarboxylic acid chloride, 2,4-dichloro-quinazolinesulfonyl chloride, 2 9 3-dichloroquinoxaline-. carboxylic acid chloride, 2,3-dichloroquinoxalinesulfonyl c~loride, 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 294-b.~-methylsulfonyl-6-methylpyrimidine, 2,4,6-tribromo-pyrimidine, 2,4,5,6-tetrabromopyrimidine, 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine 9 2,4-dichloropyrimidine-5-sul~onic acid, 5-nitro-2,4,6--trichloropyridimine, 5-cyano-2,4,6-.trichlor.opyrimidine, 2,6-bis-methylsulfonyl-pyridine-4-carboxylic acid chloride, 2,4-dichloro-5-chloro-methyl-6-methyliyrimidine, 294-dibromo-5-bromomethyl-6-methylpyrimidine, 2,4-dichloro-5-bromomethylpyrimidi:!e, 2,4-dibromo-5-bromomethylpyrimidine, 2,5,6-trichloro-4-methylpyri~idine, 2,6-dichloro-4-trichloromethylpyrimi-dineg 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine, 20 2,4,6-trimethylsul~onyl-1,3,5-triazine, 2,4-dichloropyrimi-dineS 3,6-dichloropyrimidine, 3,6-dichloropyridazine-5-carboxylic acid chlorlde,. 2,6-dichloro-4-carboetho~y-pyrimidine, 2,6-dibromo-4-carboethoxypyrimidine, 2,4,5-tri-chloropyrimidine, 214-dichloropyrimidine-6-carboxylic acid chloride, 2,4-dichloropyrimidine-5-carboxylic acid chlor ide, 2,6-dichloropyrimidine-4-carboxylic and 2,6-dichloro-pyrimidine-4-sulfonic acid amides7 2,6-dichloro-5-car-boxylic and 2~6-dichloro-5-sulfonic acid amides, 2,6-di-bromopyrimidine-4-carboxyiic and 2,6-dibromopyrimidine-. .

. - 23 -4-sulfonic acid amides, 2,6-d.ibromopyrimidine-5-carboxyllc and 2~6-dibromopyrimidine-5-sulfonic acid amides, 2,6-di-chloropyrimidine-4-sulfonyl chloride, 2,6~dichloropyrimi-dine-5-sulfonyl chloride, 2,6-dibromopyrimidine-4-sulfonyl chloride, 2,6-dibromopyrimidine-5-sulfonyl chloride, 2,4,.5,6-tetrachloropyridazlne, 5-bromo-2,4,6-trichloro-. pyrimidine, 5-acetyl-2,4,6-trichloropyrimidine, 5-nitro-6-methyl-2,4-dichloropyrimidine, 2-chlorobenzthiazole-6-carboxylic acid chloride, 2-chlorobenzthiazole-6-sul-fonyi chloride, 5-nitro-6-methyl-2,4-dibromopyrimidine, 2,4,6-trichloro-5-bromopyrimidine, 2,4,5,6-tetra~luoro-pyrimidine, 4,6-difluoro-5-chloropyrimidine, 2~4,6-tri-fluoro-5-chloropyrimidine, 2,4,5~trifluoropyrimidine, 2,4,6-trichloro-1,3,5-triazine, 2,4,6-tribromo-19 3~5-tri- -azine, 2,4,6-tri~luoro-1,3,5-triazine and the 4,6-dichloro-1,3,.5-triazines,.4,6-dibromo-1,3,5-triazines and 496 di-fluoro-1,3,5-triazines which can be substituted in the 2-position by an.~ryl 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 or9 especially, by a primary amino group or by an amino group which is substituted by aliphatic, heterocyclic and/or aromatic radicals.
m e compounds o~ 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 ~rom the literature. and are prepared by meth-ods described in the literature or by analogous procedures and process conditions~ ~or example by reacting compounds .

- 24 ~

of the general formula (7) wi-th 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 the formula (6) in which Y is the ~-sulfatoethylsulfonyl radical, are also obtained, ~or example, by reac-ting a compound of the formula

(7) with carbyl sulfate.
The coupling component~ of the formula (6) in which Z is a fiber-reactive group of the formula (Za) or (2b) are likewise descri~ed 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 fi-ber-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 Z1 is the hydroxy group, into the corresponding ester by means of a sulfating or phosphating agent analogously to a procedure known in the art. Examples of sulfating agents are concentrated sul-furic acid, sulfuric acid containing sulfur trioxide (oleum), chlorosulfonic acid and amidosulfonic acid. Ex-amples of phosphating agents are concentrated orthophospho-ric acid, pyrophosphoric acid, polyphosphoric acid or mix~tures of phosphoric acid and phosphorus pentoxide.
The isolation from the reaction batch of the com-poundswhich have been prepared in accordance with the .. , :

~ 25 -invention is effected by genera~ly known methods, eitherby precipita-tion from the reaction medium by means of electrolytes, such as, for example, sodium chloride or potassium chloride, or by evaporating the reaction solu-5 tion, 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 re~oval by filtration, any quantities o~ sulfate which may be present in the solu-tions, before evaporation.
10 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 liquid preparation.
.-The new compounds of the formula (1) have proved to be compounds possessing very good dyestu.ff properties; in 15 particular, as water-soluble dyestuffs, they are excellently suitable for dyeing and printing fibers~containing car~ox-amide groups9 of both natural and synthetic origin, such as silk, wool a~d oth_r animal hairs, polyamide fibers and polyurethane ~ibersO They are.particularly advantage-20 ously suitable for dyeing wool.
For dyelng and printing the abovementioned fibermaterials,.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, 25 for dyeing wool and polyamide fibers9 the new dyestuffs are applied to these fibers from a neutral, or pre~erably a weakly acid, aqueous dyebath at a constant or virtually con-stant pH value~ Dyeing is preferably carried out in this ~edureat between 40 and 120C in the presence of compounds .
.

.

~ L~ 3~ L
_ 26 --which are customary for such fiber ma-terials in dyebaths and dye liquors J such as 9 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 ~-N-methyl-aminoethanesulfonic acid, in the form of its sodium salt.
During the dyelng process, the pH value of the dyebath can be altered by adding acids or ac.id salts or correspondingly ' 10 alkalis or~alkaline salts, in such a way that, for example, the dyeing process begins a-t 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 15 which Zl is the N~ sulfoethylamino) group or the N-~-sul-foethyl~ N-methylamino group, are also very suitable for dyeing and printing fiber materials containlng hydroxy groups, in pQrticular natural and regenerated cellulose fibers, such as cotton, ' linen or viscose rayon~
Since the dyestuffs have fiber-reactive 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 man-ner with the aid of an acid-binding agent, such as sodium 25 hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, disodium phosphate~ sodium bicarbonate or water-glass, it be mg possible to apply these to the fiber materials at room temperature or elevated temperature, for example at temperatur-e between 20 and 180C, before, ' ' ~` 27 during or after the application o~ the dyestuffs.
The present invention thus also relates to processes for coloring by dyeing and printin,g fiber materials containing hydroxy groups and syntheti~ and natural fiber materials contain- , 5 .ing carboxamide 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).
e new compounds of the general formula (i) pro-duce green~to olive-green, blue and grey dyeings and prints on the fiber materials citedO
The dyeings and prints obtained with the new dye-stuffs have very good fas,tness to wet processing and very good fastness to light. Properties of this type which lS should be singled out particularly are the very good fast-~ess '~;o washing at various high temperatures in the washing baths, the very good fastness to acid and alkaline p~rspiration, the fastness to decatizing and milling, the fastness to peroxide bleaching and the ~ast-ness to cross-dyeing under acid conditions~
m e Examples which follow serve to i,llustrate the invention. The parts are parts by weight and the per-centages relate to percentages by weight, u,nless a note is made to the ~ontrary.- Parts by weight have the same ~ 25 relation ~o parts by volume as the kilogram to the liter~
~a~ , .. . .
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 ~ - 2~ --of 33 % str~ngth aqueous sodium hydroxide solution. 400 parts of ice are then added, followed by 60 parts of 31%
strength hydrochloric acid. Diazo-tization is carried ' out with 1703 parts of a 40% strength aqueous sodium nit-rite solution, which is added dropwise in the course of 10 minutes, while stirring. Stirring is continued for 30 mlnutes; 40.9 parts of 1-N-acetoactyl-2-methoxy-5-methyl-4-~-sulfatoethylsulfonylaniline are then added and the pH
value of the reaction mix-ture 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) " - . ' . ' O NH
3 IH3 OC~3 O NH ~ N=N-CH-C-NH ~
~ o ~LSO2-CH2-CH2-OSO3H
3 ' ' CH
- ~ , . - , - .
is precipitated by adding sodium chloride. It is excel-' 15 lently 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 95C, it dyes wool a strong green, with very good fastness to wet processing and very ~0 good fastness to lightD Dyeings and prints which have ~ery good fastness to wet processing and good fastness to light, are obtained on cotton or staple rayon, by customary dyeing and printing processes.
.

$~
. ~ 29 -Example 2 57 par-ts of 1-amino-4-(2',5'-disulfo-4'-amino-- - phenyl)-amin3anthraqu.inone-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 17.3 parts of a 40%
strength aqueous sodium nitrite solutisn are then added dropwise in the.course of 10 mi.nutes, while stirring.
After stirring for a further 30 minutes, 27.2 parts of - 4-N-acetoacetylaminoaniline-2~sulfonic acid are added as the coupling component and the pH value is adjusted to 5.5 to 6.0 with sodium.carbonateO After the coupling is complete, the mlxture is cooled to 10C and a solution of 20.5 parts of.cyanuric chloride in.60 parts by volume of acetone is added. me pH ~alue is kept at 4~5 to 5.0 with sodium carbonate while the mixture is slowly warmed q:. 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 ~he form of the free acid ~1~3 ~ CH Cl O NH~ N=N-CH-~-NH~

-S03H . so3~ Cl .

' , ' ' ` 30 ~
Deep~ green dyeing and prints w:ith very good fast-ness to wet processing and good fastness to light are obtained with the`compound on cotton o:r staple rayon, by known dyeing and printing processes, in thepreser.ceofal~
Exam~le ~
49 parts of 1-amino-4-~2~-sulfo-4'-aminophenyl)-aminoanthraquinone-2-sulfonic acid are diazotized as des~
cribed in Example 1. 46.2 parts of 1-(4'-~-sulfato-ethylsulfonylphenyl)-3-methylpyrazol~5-one are addéd 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 (writ--ten in the form of the free acid) .
o NH

N~N--~ ~ S2 C~{2-cH2-os~3H

S03H ~CH3 .
~ , is salted out with sodium chloride. It is excellently suitable for dyeing cotton by customary dyeing and print-ing processes and produces grey dyeings and prints with good fastness to wet processing and good fastness to ligh.t.

49 parts of 1-amino-4 (2t-sulfo~4'-aminophenyl~-aminoanthra~uinone-2-sulfonic acid are diazotized in accordance wi-th the instructions o~ Example 1. ?9~9 parts of 1-(2'-s~lfo-4'-aminophenyl)-3-carboxypyrazol-5-one .

~ .

are added to~this dia20 suspension and -the pH value is adjusted to about 6.5 with sodium carbona-te A~ter the ~` coupling is complete, a solution of 32.5 par-ts of N-(di-chlorotriazinyl)-aniline-3-sulfonic acid in 150 parts by volume of water is run in, the pH value being adjusted to 505 to 6.0 with sodium carbonate, The acylation is car-ried out at 40C. - A~ter the comple-tion of the reaction, the resulting compound of the formula (written in the form of the free acid) ~

~ S03H S03H NH

100 ; NH~ N=N~
.~N
S03H COOH ' Cl .. . . ..
is salted out with sodium chlorïde. It has very good dyestuff pro~perties and dyes cotton and regenerated cel-lulose using customary dye-ing and printing processes, in grey shades which arè fast to wet processing and light.
Exam~le 5 49 parts of 1-amino-4-(2'-sulfo-4'-aminophenyl~-aminoanthraquinone-2-sulfonic acid are diazotized in accord-ance with the instructions of Example 1. A solution of 13.7 parts of 2-methoxy-5-methylaniline and 15 parts of 31% strength hydrochloric acid in 100 ~arts by volume o~
water are r~n into this diazo suspension. In order to carry out the coupling reaction, the pH of this reac-tion solution is adjusted, by sprinkling in sodium , - 32 -bicarbonate; to a ~e of 2.5 to 3.0, which is maintained until the coupling reac-tion is complete.
The mixture is then neutralized with sodium carbon-ate to a pH value of 7.5 and a solution of the condensatlon product of 1~.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. m e mixture is warmed to 40C and the pH is kept at 6.5 to 6.8 with sodium carbonate. After the acylation is complete, the compound according to the general formula (1), having the formula, written in -the form of the free acid, ' O NH2 CU3 =~

03H CH3 ~ NN

.. . . . . .
SO3~
which has been prepared in this way, is salted out with sodium chloride. m e compound has very good dyestuff - 15 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 dyestuf~s.
Exam~le 6 49 parts of l~amino-4-(3'-sulfo-4'-aminophenyl~-aminoanthraquinone-2-sulfonic acid are dissolved to a neu-tral solution in 500 parts of water by means of 24.2 parts ` - 33 ~
of 33 % strength aqueous sodium hydroxide solution. 400 parts of ice are added,- followed by 60 parts of 31%
strength hydrochloric acid, and 17.3 parts of a 40%
strength aqueous sodium nitrite solution are then added 5 dropwise in the course of 10 minutes. The diazo sus-pension is stirred for a further period of 30 minutes and Q solution.of 12~1 parts of 2,5-dimethylaniline in 15 parts of 31% strength hy~rochloric acid and lOO.parts by volume of water are then added; the pH value of the coupling mix-ture 15 ad3usted -to 208 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 a-bromoacryloyl chloride are added drop-wise to the solution; the acylation reaction is kept at a .15 .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;
~t has the formula, written in the form of the free acid, 3 ~H

0 NH ~ N=N ~ H-C-C --~H2 - I Br-. CH3 and has very valuable dyestuff.properties~ For example, in an aqueous bath containing a little acetic acid, at a . temperature of about 98C~ it dyes wool in g~een shades : . .

which have very good ~astness to wet p:rocessing and good fastness to light.
Examples 7 to 20 m e compounds according to the general formula (l~
which are listed in the following Examples and which also have good dyestuff properties :in respec-t of tinctorial . properties and also in respect of their fastness proper-- ties and which dye, for example, wool in the color shades indicated in the Table, are obtained if the procedure f`ol-lowed is analogous to that described in one of the abo~eExamples,:but employing, as the s-tarting compounds, the corresponding 1-amino-4-(4'-aminosulfophenyl)-aminoan-thraquinone-2-sulfonic acid con~pound and coupling component containing the fiber-reactive group or the corresponding coupling component containing the amino groups and the corresponding fiber-reactive acylating agent.

Ex- Compound ac ording to formula (1) Color ample _ on wool O NH
CO green O NH ~--N=N--CH ~S02-CH2~CH2 OS03H.

. 3 OC~13

8 ~S03H NH2 oii~e-~11~ N=N ~1 ~5 green \~ 2~C~I2-.

-- 35 -- .
~
- ~ - O - Nlr ~I~N=N-CN ~ Cl12-cNz-cl greer O NH

C~ $N--~ SO -CH=CN2 o~Live ' ' ' ' :' ' .
- - - - .
11 0 pH2 . -N-CI13 , grey COOCN~ ' 5o2-cll2-cH2-oso3R

.
12 O, S~H2 :

~N=N
50 H ' 3 ~SO3~ o 50 11 O NH ~ N=N~ NR ~ ~ F olive OOH SO- N ~

~ ~ .

.

~--r~ O~--N=N--~--N~lC7;~1rC~ ~ll~e--green S038 . N~,N

.

lN ~ N=N ~ Nll C0-CH=CH2 olive--green ..

~31~ir SO3H lcH2-cN olive-green O NEI~N=N~ N 2~N~I_ 311 N ~ N
Cl IS2 - ~ 2 CH~
~ ` 0503H
. . -- .
. - ,- . . .
P ~7H

.N=N ~N N B
03B ~ 2 olive-green Cl 1B . .~

r~ N N--~ --N~ o-cN=cN2 ~rey--green 03~1 .
, ' .

~ 19 : .

Cl~o ~ ~r~ N-Io2-cll2 navy-blue -O Mil ~N=N~ blue SO3}l H035 S03H Cl . ' , ' ," ' '' , ',,' .
. ' , ' ', ~ . .

' '' ~ , .... .

'- , "'' .

.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AM EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A water-soluble anthraquinone-azo compound which has in the form of the free acid the formula in which both R1s are sulfo or one R1 is hydrogen and the other one is sulfo, K is the monovalent residue of a coupling component, Z is a fiber-reactive group bound to a carbocyclic aromatic nucleus of the coupling component, and n is 1 or 2.

2. A compound according to claim 1, wherein Z is vinyl-sulfonyl or a group of the formula in which Z1 is hydroxy or an inorganic or organic radical which can be eliminated to give the group -SO2-CH=CH2.

3. A compound according to claim 1 or 2, wherein K, as the radical of a coupling component, is the monovalent residue of acetoacetylanilide or acetoacetylnaphthylamide which are unsubstituted or substituted in the carbocyclic aromatic nuclei by 1, 2 or 3 substituents selected from the group of lower alkyl, lower alkoxy, halogen, nitro, carboxy, carboxyllo acid amide, carb-oxylic acid amide monosubstituted or disubstituted by lower alkyl, benzyl and/or phenyl, sulfonamide, sulfonamide monosubstituted or disubstituted by lower alkyl, benzyl and/or phenyl, lower alkanoylamino, ben-zoylamino, hydroxy, amino, lower alkylsulfonyl, phenyl-sulfonyl, lower alkylamino, lower dialkylamino, lower N-alkyl-N-phenylamino, phenylamino, benzylamino and sulfo.

4. A compound according to claim 1 or 2, wherein K, as the radical of a coupling component, is the monovalent residue of 1-phenyl 5-pyrazolone or 1-naphthyl-5-pyra-zolone which are unsubstituted or substituted in the 3-position by lower alkyl, carboxy, carbamoyl, lower carboalkoxy, phenyl or phenyl substituted by lower alkyl, lower alkoxy and/or halogen, and of which the phenyl or naphthyl bound to the 1-position is unsubsti-tuted or substituted by 1, 2 or 3 substituents selected from the group of lower alkyl, lower alkoxy, halogen, nitro, carboxy, carboxylic acid amide, carboxylic acid amide monosubstituted or disubstituted by lower alkyl, benzyl and/or phenyl, sulfonamide, sulfonamide monosub-stituted or disubstituted by lower alkyl, benzyl and/or phenyl, lower alkanoylamino, benzoylamino, hydroxy, amino, lower alkylsulfonyl, phenylsulfonyl, lower al-kylamino, lower dialkylamino, lower N-alkyl-N-phenyl-amino, phenylamino, benzylamino and sulfo.

5. A compound according to claim 1 or 2, wherein K, as the radical of a coupling component, it the monovalent residue of 1-phenyl-5-aminopyrazole or 1-naphthyl-5-aminopyrazole which are unsubstituted or substituted in the 3-position by lower alkyl, carboxy, carbamoyl, lower carboalkoxy, phenyl or phenyl substituted by lower alkyl, lower alkoxy and/or halogen, and of which the phenyl or naphthyl bound to the 1-position is un-substituted or substituted by 1, 2 or 3 substituents selected from the group of lower alkyl, lower alkoxy, halogen, nitro, carboxy, carboxylic acid amide, carb-oxylic acid amide monosubstituted or disubstituted by lower alkyl, benzyl and/or phenyl, sulfonamide, sulfonamide monosubstituted or disubstituted by lower alkyl, benzyl and/or phenyl, lower alkanoylamino, benzoylamino, hydroxy, amino, lower alkylsulfonyl, phenylsulfonyl, lower alkylamino, lower dialkylamino, lower N-alkyl-N-phenylamino, phenylamino, benzylamino and sulfo.

6. A compound according to claim 1 or 2, wherein K, as the radical of a coupling component, is the monovalent residue of naphthol which is unsubstituted or substi-tuted by 1, 2 or 3 substituents selected from the group of lower alkyl, lower alkoxy, halogen, nitro, carboxy, carboxylic acid amide, carboxylic acid amide monosubstituted or disubstituted by lower alkyl, benzyl and/or phenyl, sulfonamide, sulfonamide mono-substituted or disubstituted by lower alkyl, benzyl and/or phenyl, lower alkanoylamino, benzoylamino, hydroxy, amino, lower alkylsulfonyl, phenylsulfonyl, lower alkylamino, lower dialkylamino, lower N-alkyl-N-phenylamino, phenylamino, benzylamino and sulfo.

7. A compound according to claim 1 or 2, wherein K, as the radical of a coupling component, is the monovalent residue of aminonaphthalene which is unsubstituted or substituted on the nitrogen atom by lower alkyl and/or phenyl and unsubstituted or substituted in the naph-thalene nucleus by 1 or 2 substituents selected from the group of sulfo, lower alkyl, lower alkoxy, halo-gen, lower alkanoylamino, benzoylamino, amino, lower alkylsulfonyl, phenylsulfonyl, lower alkylamino, lower dialkylamino, lower N-alkyl-N-phenylamino, phenylamino and benzylamino.

8. A compound according to claim 1 or 2, wherein K, as the radical of a coupling component, is the monovalent residue of aniline which is unsubstituted or substituted on the nitrogen atom by lower alkyl and/or phenyl, and unsubstituted or substituted in the benzene nucleus by 1 or 2 substituents selected from the group of lower alkyl, lower alkoxy, halogen, lower alkanoylamino, benzoylamino, lower alkylsulfonyl, phenylsulfonyl, low-er alkylamino, lower dialkylamino, lower N-alkyl-N-phenylamino, phenylamino, benzylamino.

9. A process for the preparation of a compound according .
to claim 1 which comprises diazotizing a 1-amino-2-sulfo-4-(4'-aminophenyl)-aminoanthraquinone compound of the formula in which R1 is defined as in claim 1, selectively by means of an equivalent quantity of sodium nitrite in the presence of a mineral acid to give the diazo com-pound of the formula in which R1 is defined as in claim 1, and the coupling said diazonium salt obtained with a coupling component of the formula H-K-Zn in which K, Z and n are defined in claim 1, but in which Z is not in the ortho-position or para-position in relation to the coupling point.

10. Modification of the process according to claim 9, wherein the diazonium compound of the formula defined in claim 9, is coupled with a coupling compo-nent of the formula wherein K is defined in claim 1 and Z2 is the group -NHR in which R is hydrogen or lower alkyl, and the resulting compound of the formula, written in the form of the free acid, in which R1, R and K are defined as above, is reacted with a compound of the formula Hal - Y
wherein Y is a fiber-reactive radical belonging to the aliphatic, cycloaliphatic, heterocyclic and aromatic series and Hal is a halogen atom, or with a correspond-ing anhydride containing the radical Y.

11. A process for coloring a fiber material containing hydroxy groups or containing carbonamide groups by applying a dyestuff on said fiber material be conven-tional dyeing and printing processes and fixing it thereon by conventional methods, the improvement consisting of using as a dyestuff a compound accord-.
ing to claim 1.

12. A fiber material containing hydroxy groups or con-taining carbonamide groups which had been colored with a compound of claim 1.