CA1276141C - Fiber-reactive monoazo compounds, process for their preparation and their use as dyes - Google Patents

Abstract

Abstract of the disclosure:

Fiber-reactive monoazo compounds, process for their pre-paration and their use as dyes Monoazo compounds having fiber-reactive dyeing properties which possess as the diazo component an aniline substitu-ted by two fiber-reactive groups of the vinylsulfonyl series and as a coupling component one fiber-reactive group from the aniline, hydroxypyridone, 5-pyrazolone or 5-aminopyrazole series. They are suitable for dyeing carboxamido- and/or hydroxyl-containing materials, in par-ticular fiber materials, such as preferably cellulose fiber materials.

Description

$~
~OECHST AKTIENGESELLSCHAFT HOE ~4/F 271 Dr.ST

F;ber-reactive monoazo compounds, process for th~ir-pre-paration and th~ir use as dyes The ;nvent;on relates to the technical f;eld of f;ber-react;ve dyes.

European Patent Appl;cation No. 0,107,614 d;scloses fiber-reactive azo compounds ~h;ch, however, possess certain defects. For instance~ ;n part;cular the;r level;ng power is lo~ and their steam stabil;ty ;s moderate.

The present invention now prov;des new monoazo compounds tO having improved properties, which conform to the general formula t1) D - N = N - K 51) in which D denotes a radical of the formula (2a) or (2b) and K stands for a radical of the general formula ~3a~, (3b~, ~3c) or t3d):
so2--r (Za) ~-- so21~ tZb~

SO2--~ SO2--Y
p~1 R5 _~ ~R3 ~3a~ R6 OH ~H2 ~N--Q ~3c) _~IN-- Q ~3d) - FN ~N

R~ Rn ~' `
.

- " " ~: ` ''- ` ' ' .

in which Y is a vinyl group of the formula (4 ~ C~2 ~ C~2 ~

;n ~hich X is a substituent ~hich is el;m;natable by alkaL;
~;th the format;on of the v;nyl group;
R1 ;s a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as an ethyl group and in particular a methyl group~ an alkoxy group of 1 ~o 4 carbon atomsr such as an ethoxy group and ;n particular a methoxy group, a sulfo group ~conforming to the general formula -S03M, ;n ~hich M ;s a hydrogen atom or an alkali metal, such as sodium, potassium and lithium, or ~he equivalent of an alkaline earth metal, such as of calcium), a car-boxy group (conforming to the general formula -COOM
~here M is as defined above), 3 carbalkoxy group of Z
to 5 carbon atoms, such as a carbome~hoxy and carbo-ethoxy group, a halogen atom, such as a bromine atomand in particular a chlorine atom, or an alkoxy group of 1 to 4 carbon atoms ~hich is subst;tuted by a hydroxy, acetyloxy, carboxy, carbamoyl or cyano group or by a halogen atom, such as a chlorine or bromine atom;
R~ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, such as an ethyl group and in particular a methyl group, an alkoxy group of 1 to 4 carbon a~oms, such as an ethoxy group and ;n part;cular a ~ethoxy group, a halogen atom, such as a bromine atom and in particular a chlorine atom, a cyano group, a trifluoro-methyl group,or an alkoxy group of 1 to 4 carbon atoms uhich ;s substituted by a hydroxy, acetyloxy, carboxy,.
carbamoyl or cyano group or by a halogen ato~, such as a bromine and in particular a chlorine atom, or R2 is an alkanoylam;no group of 2 to 5 carbon atoms, such as an acetylamino and propionylamino group, ~hich can be substituted by chlorine, bromineO alkoxy of 1 to 4 carbon atoms, phenoxy, phenyl, hydroxy, carboxY

- . : . . . , -, :, : . :
, .. .
`: . . ' ,::

,~ ' :
: . ' or suLfo, such as, for example, a chloroace~yla~;no, chloropropionylamino, phenylacetylam;no or phenoxy-acetylamino group, or R2 is an alkenoylam;no group of 2 to 4 carbon atoms ~hich can be substituted by chlorine~ bromine, carboxy or sulfo, such as, for example, the monoacylam;do radi-cal of maleic acid, an acryloylamino radical or an ~-bromoacryloylamino radical, or R2 is a benzoylamino group which can be substitu~ed in the ben~ene nucleus, for exa~ple by subs~ituen~s from the group consisting of chlorine~ sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon ato~s, nitro and carboxy, or R2 is 3n alkylsulfonyl group of 1 to 4 carbon ato~s,or a phenylsulfonyl group ~hich can be substituted in the benzene nucleus, for example by substituents from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, sulfo and carboxy, or R2 is an alkylsulfonylamino group of 1 to 4 carbon atoms uh;ch can be substituted by hydroxy, sulfato (conforming to the general formula -S03M where M is as defined above), chlorine, bromine or alkoxy of 1 to 4 carbon atoms, such as, for example, a methylsulfonyl-am;no, ethylsulfonylamino, B-chloroethYlsulfonylamino or B-methoxyethylsulfonylamino group, or R2 ;s a phenylsulfonylamino group which can be substi-tuted in the benzene nucleus, for example by substitu-ents from the group consisting of alkyl of 1 to 4 car-bon atoms, alkoxy of 1 to 4 carbon atoms, chlorine,sulfo and carboxy, such as, for example, a p-tosyl-amino group, or R2 is a carbamoyl group which can be monosubstituted or disubstituted at the nitrogen atom by 1 or 2 substi-tuents from the group consisting of alkyl of 1 to4 carbon atoms tsuch as methyl, ethyl~ propyl, isopro-pyl and butyl), substituted alkyl of 1 to 4 carbon atoms - such as alkyl of 1 to 4 carbon atoms ~hich ;s substituted by 1 or 2, preferably 1, substitwent from .~ .
.
:: ' ' - . , .

.

7~

the group consisting of hydroxy, sulfa~o, sulfo, car-boxy chlorine, alkoxy of 1 to 4 carbon atoms, phenyl and subst;tut~d phenyl (such as phenyl ~hich is sub-stituted by substituents from the group consistin~ of chlor;ne, sulfo~ alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and carboxy), for ~x. ~-sul~
fatoethyl, ~-sulfoethyl, ~-hydroxyethyl, phenethyl and ben~yl, - cycloalkyl tsuch as cyclohexyl), phenyl and substituted phenyl (such as phenyl wh;ch is substitu-ted by substituents from the group consisting of chlor-ine, sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and carbo~y, or R2 is a sulfamoyl group which can be monosubstituted or disubstituted at the n;tro~en atom by 1 or 2 sub-stituents from the group consisting of alkyl of 1 to4 carbon a~oms tsuch as methyl, ethyl, propyl, isopro-pyl and butyl), substituted alkyl of 1 ~o 4 carbon atoms - such as alkyl or 1 to ~ carbon atoms which is substitu~ed by 1 or 2~ preferably 1, substituent from the group consisting of hydroxy, sulfato, sulfo, car-boxy, chlorine, alkoxy of 1 to 4 carbon atoms~ phenyl and substituted phenyl tsuch as phenyl ~hich is sub-stituted by substituents from the group consisting of chlorine, sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and carboxyJ, for ex. B-sul-fatoethyl,~ -sulfoethyl, ~-hydroxyethyl, phenethyl and ben~yl, - cycloalkyl (such as cyclohexyl), phenyl and substituted phenyl ~such as phenyl ~hich is substitu- -ted by substituents from the group consisting of chlor-ine, sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1to 4 carbon atoms and carboxy), or R2 is the ure;do group or a ureido group ~hich is monosubstituted or disubstituted at the ter M i r,al nitro-gen atom by 1 or 2 substituents from the ~roup consist-ing of alkyl of 1 to 4 carbon atoms ~such as ~ethyl,ethyl, propyl, isopropyl and butyl), substituted alkyl of 1 to 4 carbon atoms - such as alkyl of 1 to 4 carbon atoms ~hich is subst;tuted by 1 or 2~ prefer-ably 1, substituent from the group consisting of .. .. . . .

.; :
' ' ' ;~' ~ ; :", ' ~ ' :

1. ~ f ~

hydroxy, sulfato, sulfo, carboxy, chlorine, alkoxy of 1 to 4 carbon atoms, phenyl and subs~ituted phenyl tsuch as phenyl wh;ch is substituted by substituents from the group consisting of chlorine, sulfo~ alkyl of S 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and carboxyl), for ex. ~suLfatoethyl, ~ -sulfoethyl~ ~-hydroxyethyl, phenethyl and benzyl, - cycloalkyl (such as cyclohexyl),phenyl and substituted phenyl (such as phenyl which is substituted by subst;tuents from the group consisting of chlor;ne, sulfo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and carboxy), such as, for example, an N-phenylureido group;
R3 is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, which can be substituted, such as by one or two substituents from the group consisting of alkoxy of 1 to 4 carbon atoms, halogen, such as chlorine, cyano, hydroxy, carboxy, sulfo, sulfato, phosphato tconforming to the general formula -OP03M2 where M is as de~;ned above), car-bamoyl, sulfamoyl, N tC1-C4-alkYl)-carbamoyl having a sulfato, phosphato, hydroxy or sulfo group as a sub-stituent in the alkyl radical, N-tC1-C4-alkyl~-sul-famoyl having a sulfato, phosphato, hydroxy or sulfo group as substituent in the alkyl radical, N,N-di-tC1-C4-alkyl)-sulfamoyl having a sulfato~ phosphato, hydroxy or sulfo group as substituent in either or both alkyl radicals, N,N-di-(C1-C4-alkyl)-carbamoyl ha~ing a sulfato, phosphato, hydroxy or sulfo group as substituent in either or both alkyl radicals, phen-oxy, phenyl and substituted phenyl (such as sulfophenyl and carboxyphenyl), or 23 is an alkenyl group of 2 to 5 carbon atoms~ such as a v;nyl and propenyl group, which can be substituted by a carboxy or sulfo group or by a chlorine or bromo ine atom, or is a cycloalkyl radical of 5 to 8 carbon atoms, such as a cyclohexyl radical, and R4 is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atons, ~h;ch can : : . . . . , . .:
. -: -: :
.. .
.' . - : ~ - - . :.
- ,,: .
.
. - ':. . .
.. : '' .. ~,, " :
. ., :.,. ' . ' ' : ' ~ ~7~ f~d -- 6 ~
be subst;tuted, such as by one or two substituents fro~ the group cons;st;ng of alkoxy of 1 to 4 carbon atoms, halogen, such as chlor;ne, cyano, hydroxy, carboxy, sulfo~ sulfato, phosphato, carbamoyl, sul-famoyl, N-(C1-C4-alkyl)-carbamoyl hav;ng a sulfato, phosphato~ hydroxy or sulfo group as a substituent in the alkyl radical, N-~C1-C4-alkyl)-sulfamoyl havin~
a sulfato, phosphato, hydroxy or sulfo group as sub-stituent in the alkyl radical, N,N-di-(C1~C4-alkyl)-sulfamoyl having a sulfa~o, phosphato, hydroxy or sulfo group as substituent in either or both alkyl rad;cals, N,N-di-(C1-C4-alkyl)-carba~oyl having a sul-fato, phosphato, hydroxy or sulfo group as substitu-ent in either or both alkyl radicals, phenoxy, phenyl or substituted phenyl tsuch as sulfophenyl and carboxy-phenyl), or R4 is a cycloalkyl radical of 5 to æ carbon atoms, such as a cyclohexyl radical~ or R4 is a phenyl radical which can be substituted~ such as by 1, 2 or 3, preferably 1 or 29 substituents from the group consisting of alkyl of 1 to ~ carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon ato~s, such as methoxy and ethoxy, halogenO such as chlorine, sulfo, carboxy, sulfomethyL, sulfamoyl, carbamoyl and alkanoylamino of 2 to 5 carbon atoms, or R4 is a naphthyl radical ~hich can be substituted by 1r 2 or 3 sulfo groups and, if desired, by a chlorine atom, an alkoxy group of 1 to 4 carbon atoms, an alkyl group of 1 to 4 carbon atoms, an alkanoyla~ino group of 2 to 5 carbon atoms or a benzoyla~;no group uhich can be substituted by sulfo, or R4 is a heterocyclic radical ~hich can have one or two fused-on carbocyclic rings, it being possible for the carbocyclic rings to be additionally substituted and for the heterocyclic radical to be substituted on the carbon atoms and/or on the heterocyclic atoms by option-ally substituted alkyl groups and/or optionally sub-stituted phenyl radicals, or R3 and R4 together ~ith the nitrogen atom and o~tionally 1 or 2 ,, . ~ :.: , . `
.-. ~.
, . - . : ~
' ' ~ -`: , '~ . - ' ' further he~ero atoms, such as n;~rog~n, oxygen and sulfur atoms, represent a satura~ed heterocyclic radi-cal, such as~ for example, a p;p2ridino, morpho~ino or p;peraz;no radicaL;
R5 ;s a hydrogen atom or preferably an alkyl ~roup of 1 to 4 carbon atomsO such as, ;n part;cular, 3 methyl group, wh;ch can be substi~uted by a sulfo or carboxy group, or ;s a phenyl rad;cal;
R6 is a hydrogen atom~ a sulfo group, a sulfo-substi-tuted alkyl group of 1 to 4 carbon atoms, such as asulfomethyl group, or preferably a carbamoyl or cyano group;
R is a hydrogen atom or preferably an alkyl group of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms~
1~ such as a methyl and propyl group and in part;cular an ethyl group, ~h;ch can be subst;tuted by a sulfato, phosphato, carboxy, hydroxy, or an alkanoylam;no group of 2 to 5 carbon atoms, such as a prop;onylam;no group and in particular an acetylamino group;
R* is a methyl group, a carboxy group, a carbalko~y group of 2 to 5 carbon atoms, such as a carbomethoxy and carobethoxy group, a carbamoyl group,or a phenyl radical which can be substituted by sulfo, carboxy, methyl, ethyl, methoxy, ethoxy and/or chlor;ne;
R" is a methyl group, a carbamoyl group,or a phenyl group uhich can be substi~uted by carboxy, sulfo, methyl, ethyl, methoxy, ethoxy and/or chlorine;
Q ;s a phenyl radical uhich can be substituted, such as, for example, by 1, 2 or 3 substituents selected from 3~ the group consisting of 2 sulfos, 2 carboxys, 3 alkyls of 1 to 4 carbon atoms, such as ethyl and in particu-lar methyl~ 2 alkoxys of 1 to 4 carbon atomsO such as ethoxy and in particular methoxy, 2 chlorines, 1 brom-ine, 1 nitro, 1 amino, 1 alkanoylamino of 2 to 5 car-bon atoms, such as acetylamino, 1 benzoylamino ~hichcan be substituted by sulfo, carboxy and/or chlorine, carbamoyl and sulfamoyl, or is a naphthyl radical which can be substituted by 1, 2 or 3 sulfo groups and option-ally . by an alkyl ~roup of 1 to 4 carbon atoms, such ' . '. . ' ' ' .. ' , ........................................ ' .

~ ~7~

as a methyl group, an alkoxy group of 1 to ~ carbon atoms, such as a me~hoxy group~ a chlorine atom or an alkanoylamino group of 2 to 5 carbon atoms~ such as an acetylamino group.

The ne~ compounds of the formula (1) can be present in acid form. They are preferably present in th~
form of their salts, in par~icular the abovementioned alkali metal and alkaline earth metal salts. They are used, preferably in the form of the alkali metal salts, for dyeing ~in the general sense as including printing~
hydroxy ~containing and/or carboxamido-containing materi-als, ;n particular fiber~materials~

The alkyl, alkenyl and alkylene radicals ~hich have been mentioned for the above moieties can be straight-chain or branched. The heterocyclic radicals which stand for the moiety R4 or can be contained in the moiety R4 are for example an optionally subst;tuted furyl, thiophenyl, pyrazolyl, pyridyl, pyrimidyl, quinolyl, benzimidazolyl, ben20thiazolyl and benzoxazolyl radical.

Amino groups conform;ng to the general formula -NR3R4 are for example the primary amino group itself and the methylamino, ethylamino~ propylamino, isopropylamino, butylamino, hexylamino, ~-methoxyethylamino,~ -methoxy-propylamino~ ~-ethoxyethylamino, W,N-dimethylamino, N,N-diethylamino, N-methyl N-phenylam;no, N-ethylphenyl-amino,~ -chloroethylamino,~ -cyanoethylamino, ~cyano propylamino, ~-carboxyethylamino, sulfomethylaminoD
~-sulfoethylamino, ~-hydroxyethylamino, ~-sulfatoethyl-amino, N,N-di-~-hydroxyethyl)-amino, N,N-di-(B-sulfato-ethyl)-amino~ N,N-di-(B-sulfoethyl)-am;no, ~ -sulfato-n-propylamino, ~,~-disulfato-n-propylamino, N~ sulfato-ethyl)-N-(~-sulfato-n-propyl)-amino, N~ sulfatoethyl)-N-~ disulfato-n-propyl)-amino, N-~~(N-~-sulfatoethyl-carbamoyl)-ethyl~-amino, N-C~ (N-methyl-N-~-sulfatoethyl-carbamoyl)-ethylJ-amino, N-C~-~N,N-di-~sulfatoethyl-carbamoyl)-ethyl~amino, N-t~-sulfatoethyl)-N-Cp-tN- ~-. . : ,' - .

~ ~2'7~
_ 9 _ sulfatoethylcarbamoyL)-ethyl]-amino~ N-(~-sulfatoethYl)-N-C~-~N-methyl-N- ~sulfatoethylcarbamoyl)-ethyl]-amino, N-(~-sulfatoethyl)-~-[~ (N,N-di-~-sulfa~oethylcarbamoyl)-ethyl~-am;no~ ~ -sulfato-n-propylamino, N-(~sulfatoethyl)-N-(~-sulfato-n-propyl)-am;no, ~-hydroxypropylamino, benzylam;no, cyclohexylamino, morpholino, piperidino, piperazino, phenylamino, toluidino, xylidino, chloroan;-lino, anis;dino, phenetidino, 2-sulfoan;lino, 3-sulfoani-l;no, 4-sulfoan;l;noj 2,5-d;sulfoan;l;no, sulfomethyl-anil;no, N-sulfomethylan;lino, 3-carboxyphenylamino, 4-carboxyphenylamino, 2-carboxy-5-sulfophenylam;no, 2-car boxy-4-sulfophenylam;no, 4-sulfonaphth-1-ylamino, 3,6-disulfonaph-1-ylamino, 3,6,8-trisuLfonaphth-1-ylam;no and 4,b,8-trisulfonaphth-1-ylamino group.
The subst;tuent ~h;ch, be;ng elim;natable under alkaline conditions, stands for X in the formula t4) is for example a sulfato group, a thiosulfato group (conforming to the general formula -S-S03M ~here M is as defined above3~ a phosphato group, an alkanoyloxy group of 2 to 5 carbon atoms, such as an acetyloxy group, a benzoyloxy groupO
N,N-dimethyl- or N,N-diethyl-thiocarbosulfide group, a dimethylamino or diethylamino group, a trialkylammonium-hal;de, such as trimethylammonium chloride group, a chlorine, bromine or fluorine atom~ a pyridinium halide, such as a pyridinium chloride group, a trialkylammonium-methosulfate, such as a trimethylammoniummethosulfate group, a pyrimidinium halide group, a dimethyl or diethyl-ammonium chloride group, a p-tosyloxy, dimethylaminosul-fonyloxy, N-methylmethylsulfonamido, methylsulfonyloxy, sulfophenylsulfonyloxy, phenylsulfonyloxy, thiocyanat trichloroacetyloxy, dichloroacetyloxy, monochloroacetyloxy, dimethylaminosulfonyloxy and diethylaminosuLfonyloxy group.
Preferably Y is a vinyl group and in particular a ~-sul-fatoethyl group. The t~o radicals Y can be identical to or different from each other; preferably they are identi-cal to each other.

: ~ ' . . ' ' ' , ' .~ . .

J.~
-- ~0 --Preferably, ;n the compounds of the formula ~ R1 ;s a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a sulfo group, a carboxy group or a chlorine atom. Particularly prefer-ably R1 is a hydrogen atom, a methoxy, ethoxy~ methylor sulfo group or a chlorine a~om, and very particularly preferably R1 is a hydrogen atom, a methoxy group or a chlorine atom.

Preferably, in the compounds of the formula ~1), R2 is a hydrogen atom, a methyl, ethyl, ~ethoxy or ethoxy ~roup or 3 chlorin~ atom, an alkanoylamino group of 2 to 5 car-bon atoms, such as in particular an ace~ylamino group, a methylsulfonylamino, chloromethylsulfonylamino, tri-fluoromethyl, cyano~ methylsulfonyl, ethylsulfonyl, n-butylsulfonyL, N,N-diethylsulfamoyl, N,N-di-n-butylsul famoyl, N,N-di-t~-sulfoethyl)-carbomoyl, N-methyL-N-t~-sulfatoethyl)-carbamoyl, N-methyl-N-t~-sulfatoethyl)-sulfamoyl, N-t~-sulfoethyl)-sulfa~oyl, N-ph~nylsul-famoyl, ureido or N-phenylureido group. Particularly pre-ferably R2 is a methyl, ethyl~ methoxy or ethoxy group, in particular a hydrogen atom, a chlorine atom, an alka-noylamino group of 2 to 5 carbon atoms, such as in parti-cular an acetylamino group, a methylsulfonylamlno,kcyano~ Y
N,N-diethylsulfamoyl, N-methyl-N-t~-sulfatoethyl)-sulfa-moyl, N-t~sulfoethyl)-sulfamoyl, ureido or N-phenylure-ido group. Very particularly preferably R2 is a chlor-ine atom or an acetylamino, ureido or N-phenylureido or -tri~luoromethyl group.
Preference is further given to those compounds in which R3 denote~ a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, in particular an ethyl group, which can be substituted by a sulfo, carboxy, sulfophenyl~ phenyl~
cyano, sulfato or phosphato group, or is an alkenyl group of 2 to 4 carbon atoms, such as the prop-2-en-1-yl group.
Particularly preferably R3 ~tands for a hydrogen atom or an aLkyl group of 1 to 4 carbon atoms, ~hich can be sub-stituted by a sulfo, carboxy, hydroxy, cyano or sulfato . . -.. . . .
... , .. ~. .
' ' : .- : :
.. . . .
, ~ . . .
' ` ' ~' : - ' -:'; :. ' - ` ' ' . ` ` , ~ ` : ' ' ' :

group or by a phenyl or sulfophenyl radical, very par~i-cularly preferably for a hydrogen atom or a ~-hydroxy-ethyl,~ -sulfatoethyl, ~-cyanoethyl~ ethyl, benzyl or sulfobenzyl group.

Preference is further g;ven to compounds of the formula (1) ;n ~hich R4 ;s a hydrogen atom or, preferably, an alkyl group of 1 to 4 carbon atoms, ;n part;cular an ethyl group, ~h;ch can be substituted by sulfophenyl~
phenyl, hydroxy, cyancr su~fo, carboxy, suLfato and phosphato groups, preferably is substituted by one of these groups,or isanalkenyl group of 2 to 4 carbon atoms, such as a prop-2-en-1-yl group, or an alkyl group of 1 to 4 carbon atoms~ in particular an ethyl group, ~hich is substituted by an N~ sulfatoethyl)-carbamoyl, N-methyl-N-~-sulfatoethyl)-carbamoyl or N,N-di~(~-sulfatoethyl)-carbamoyl group. Particularly preferably R4 d~notes an alkyl group of 1 to 4 carbon atoms, in part;cular an ethyl group, or a ~-(N-~ sulfatoethylcarbamoyl)-ethyl~
@r(N-methyl-N-~sulfatoethylcarbamoyl)-ethyl or ~ CN,N-di-~B-sulfatoethyl)-carbamoyl~-ethyl group or a propenyl group,or an alkyl group of 1 to 4 carbon atoms, such as an ethyl group, ~hich is substituted by 1 or 2 substitu-ents, preferably one substituent, from the group consist-ing of sulfo, sulfato, hydroxy and sulfophenyl, such asa ~-sulfatopropyl, ~ disulfatopropyl, ~-sulfoethyl,c~-sulfoethyl, ~ -sulfopropyl, ~-sulfopropyl, sulfobenzyl or sulfophenethyl group. Very particularly preferably R4 is an alkyl group of I to 4 carbon atoms, which can be sub-st;tut~d by a hydroxy, sulfo, sulfophenyl or sulfato group.

Preference is similarly given to those compounds in ~hichR* stands for a methyl or carboxy group or a carbometh-oxy or carbethoxy group and R" denotes a methyl group, and similarly to those compounds according to the lnven-t;on in uhich Q stands for a phenyl group ~hich is sub-stituted by 1 or 2 substituents from the group consisting of sulfo, carboxy, methyl~ ethyl, methoxy, ethoxy and rhlorine, one of the substituents preferably being a , 7~

sulfo group, or in ~hich Q stands for a naphthyl radical ~h;ch is subs~ituted by 1, 2 or 3 sulfo groups~

Co~pounds of the general formula (1~,wh;ch conta;n the anilino radical according ~o the general formula ~4a), are a preferred subject-matter of the present invent~on. Of these, preference is given in particular to those azo com-pounds ~hich conform to the general formulae t5a) and (5b) - N ~ N / R3 ~2 ~ ~ ~ ~4 tSa) S2' Y ~2 82 ~ R1 R~
~2 - I ~ \ R4 ~Sb~

;n ~hich Y~ R1, R2, R3 and R4 have the above~entioned~
in particular preferred, ~eanings. Preference is given in particular to those compounds of the general formulae t5a) and t5b) in uhich R~ stands for a hydrogen ato~ and R2 stands for a chlorine atom or for a tri~luoromethyl group and R3 and R~ both represent a ~-sulfatoethyl group. Preference is further given to those compounds according to the invention of the general for~ulae (5a) and ~Sb) ;n wh;ch R1 and R2 both denote a hydrogen atom and R3 stands for an ethyl ~roup and R4 for a 3-sul~o-ben2yl group.

The present invention aLso relates to a process for pre-paring the coMpounds according to the invention nf the general for~ula t1), which comprises diazotizin~ a com-pound of the ~eneral for~ula ~6) D - ~H2 t6) in ~hich D is a radical of the abovementioned and defined . .
. ,, ' ~ . :.... ~
': ' ' '', : ~ , .. . . .
,: ., ,, . , ~:

formula (2a3 or ~2b3 in ~h;ch Y has one of the mean-ings ment;oned ~here or represents a ~ hydroxyethyl gr~up, in convent;onal manner and coupl;ng ~;th a coupling com-ponent of the formula (7~

~ - K ~7) in ~hich K has one of the abovementioned meanings, and if the startin~ ~aterial used is a d;azo component of the formula (6) in ~hich Y stands for a ~-hydroxyethyl group reacting the resultant azo compound of ~h~ generaL for-Qula t8a) or t8b) S02-CH2-C~2-OH SO~ ~ N = ~ _ X
~ K CH2 72 CH2 CH2-CH2.0H
O;~-C}I2oCR2-0}1 0~1 t8a~ (8b) in uhich K ;s as defined above, analogously to kno~n pro-cedures,~ith an acylating or esterifying agent in order to conYert them into azo compounds according to thç inven-tion of the general for~ula (1) in ~h;ch X stands for an acyloxy radical ~hich is eliminatable under alkaline con-ditions, such as for the sulfatD, phosphato, alkanoyloxy, benzoyloxy, aLkylsulfonyloxy or phenylsulfonyloxy radical.

Azo compounds according to the invention ~hich conta;n, bonded to an al;phat;c 0roup in the rad;cal K of coupling component H-K, one tor ~ore) sulfato or phospha~o ~roups can also be prepared ;n a manner accord;ng to the inven-tion by reaeting an azo compound accordin0 to th~ inven-tion ~hich contains one tor more) hydroxy ~roups bonded to one ~or ~ore) aliphatic groups,analo~ously to kno~n procedures ~ith a sulfating or phosphating agent. Herein it is also possible to start fro~ such azo co~pounds which contain in the radical of the formula (2a~ or t2b~ as the ': ` ~- ~ ' ' ' .' ' . . . ; .: . .
:
., ~ , .

~.~'7~

diazo component ~-hydroxyethylsulfonyL groups and at the same time to react both ~he hydroxy groups in ~he coupl~
ing component and the hydroxy groups in ~he d;azo com-ponent into the corresponding sulfato or phosphato groups by means of the sulfating or phosphat;ng agent.

Sulfating agents are kno~n; they are for example concen-trated sulfuric acid and sulfuric acid monohydrate. The sulfat;on is preferably effected by means of concentrated sulfuric acid at a temperature between 0 and 40C or by means of suLfuric acid monohydrate at a temperature bet-ween 5 and 15C.
Phosphating agents are like~ise known; they are phospho-ric ac;d, polyphosphoric acid or mixtures of these acids with phosphorus pen~oxide. The phosphation with these agents is as a rule effected between Z0 and 80C.

Azo compounds according to the invention ~hich contain an alkanoyloxy group bonded to an aliphatic radical, such as, for example, in the radicals of the formulae R~, R3, R4 and R andlor Y, can be prepared in the same way by react-ing a corresponding azo starting compound in ~hich one or more hydroxy groups are present bonded to an aliphatic radical in the diazo and/or coupling component ~ith an acylating agent of an alkanoic acid or aromatic carbo~ylic acid, such as~ for example, acetyl chloride, glacial acetic acid, acetic anhydride or benzoyl chloride.

It is like~ise possible to synthesize azo compounds accor-ding to the invention ~hich contain in the radical K of the coupling component H-K a monoalkylamino or dialkyl-amino group analogously to known procedures by alkylating a corresponding azo starting compound which contains bon-ded a primary amino group or a monoalkylamino group by means of a customary alkylatin~ agent.

If desired, azo compounds according to the invention ~hich have a certain f;ber-reactive group of the formula -S02-Y
vhere Y is as defined at the bes;nning for the formula(1), , ' ' .. ", '': ~ ", .' . " ' '~ ~''.'' .' ,, ' .

can be converted ;nto azo compour~ds accord;ny to the invention having another fiber-reactive groupO such as, for example, by converting azo compounds according to the invention having ~-sulfatoethylsulfonyl groups into ~hose hav;ng vinylsulfonyl groups or into ~-thiosulfato-ethylsulfonyl or dialkylaminoethylsulfonyl groups~ The re~ction conditions used are analogous to the conditions described repeatedly in the literature for the mutual con-version of the reac~ive groups of the vinylsulfonyl lû series.

Coupling components conforming to the general formula t7) ~hich, according to the ;nvention, are used for preparing the ne~ azo compounds of the general formula (1) are for example:
N-ethyl-N-(B-hydroxyethyl)-anil;ne, N-ethyl~N-(B-acetoxy-ethyl)-an;l;ne, 3-acetylam;no-N,N-di-(B-hydroxyethyl)-anil;ne, 3-methyl-N,N-d;-(~-acetoxyethyl)-aniline, 2-methoxy-5-acetylamino-N-t~-acetoxyethyl)-N-benzylaniline, 2û 2-chloro-5-acetylamino-N-(r-phenoxy ~hydroxy-n-propyl~-aniline, 3-ureidoaniline, N-ethyl-N~3'-sulfobenzyl)-aniline, 3-methyl-N-ethyl-N-t~-sulfoethyl~-aniline~ 3-methyl-N,N-di-(hydroxyethyl)-aniline, 3-methyl-6-methoxy-N,N-di-(~-hydroxyethyl)-aniline, 3-acetylaminoaniline, 3-methyl-N-ethyl-N-t~-hydroxyethyl)-aniline, 1-t3'-chloro-phenyl)-3-methylpyrazol-5-one, 1-S2'-chloro-6'~methyl-phenyl)-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 1-(2'-chloro-S'-sulfophenyl)-3-methyl-5-amino-pyrazole, 1-t2'-chloro-4-sulfophenyl)-3-methyl-5-a~ino-pyrazole, acetoacetanilide, 1-t~hydroxyethyl)-4-~ethyl-6-hydroxy-2-pyridone, 1-t~ hydroxyethyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone, 1-t~-hydroxyethyl)-3~carbamoyl-4-methyl-6-hydroxy-2-pyr;done, 1-t~-hydroxyethyl)-4-methyl-6-hydroxy-2-pyridone-3-sulfon~c acid, 1-t~-sulfatoethyl)-4-methyl-6-hydroxy-2-pyridone, 1-~-sulfatoethyl)-3~cyano-4-methyl-6-hydroxy-2-pyridone, 1-t~sulfatoethyl)-3-car-bamoyl-4-methyl-6-hydroxy-2-pyridone, 1~t~-sulfatoethyl)-4-methyl-6-hydroxy-2-pyridone-3-sulfonic acid, 1-t~ sul-fatoethyl)-4-methyl-6-hydroxy-2-pyr;done, :

~ -sulfatoethyl) 3-carbamoyl-4-methyl-6-hydroxy-2-pyr;-done, 1~ sulfatoethyl)-4-methyl-6-hydroxy-~-pyridone-3-sulfonic acid, 1-carboxymethyl-4-me~hyl-6-hydroxy-2-pyri-done, 1-carboxymethyl-3-cyano-4-methyl-6-hydroxy-2-pyri-done~ 1-carbo~ymethyl-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone, 1-carboxymethyl-4-methyl-6-hydroxy-2-pyridone-3-suLfonic acid, 1-t~ carboxyethyl)-4-methyl-6-hydroxy-2-pyridone~ -carboxyethyl)-3-cyano-4-me~hyl-6-hydroxy-2-pyridone, 1-t~-carboxyethyl)-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone~ -carboxyethyl)~4-methyl-6-hydroxy-2-pyridone-2-sulfonic acid, 1-~ ace~ylaminoethyl~-4-methyl-6-hydroxy-2-pyridone, 1-(~acetylaminoethyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone~ 1~B-acetylaminoethyl)-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone, 1-(~-acetyl-am;noethyl)-4-methyl-6-hydroxy-2-pyridone-3-sulfonic acid, ~ acetylaminopropyl)-4-methyl-6-hydroxy-2-pyridone, 1-t~-acetylaminopropyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone, 1-~-acetylaminopropyl)-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone, 1-~-acetylaminopropyl-4-methyl-6-hydroxy-2-pyr;done-3-suLfonic a~;d, 3-am;no~cetanilide-4-sulfonic acid, 3-aminochloroacetanilide-4-sulfonic ac;d~
3-amino~ropionylaminobenzene-4-sulfonic acid, 3-amino-~-chloropropionylaminoben2ene-4-sulfonic acid, 3-am;no-~sulfopropionylaminobenzene-4-sulfonic acid, 3-amino~cryl-oylaminobenzene-4-sulfonic acid, 3-amino-isobutyrylamino-benzene-4-sulfonic acid, 3-amino~X-bromoacryLoyla~ino-benzene-4-sulfonic ac;d, 3-aminophenylacetylaminobenzene-4-sulfonic ac;d, 3-amino~ethoxyacetylaminobenzene-4-sul-fon;c acid, 3-amino~uccinylaminobenzene-4-sulfonic acid, 3-amino-~-carboxyacryloylaminobenzene-4-sulfonic acid, 3-amino~henoxyacetylaminobenzene-4-sulfonic ac;d, 3-amino-benzoylam;nobenzene-4-sulfonic acid, 3-am;no-4'~methyl-benzoylaminobenzene-4-sulfonic acid, 3-amino-3'-chloro-benzoylaminobenzene-4-sulfonic acid~ 3-amino-Z'-methoxy-benzoylaminobenzene-4-sulfonic acid, 3-amino-2'-carboxy~
benzoyLa~inobenzene-4-suLfonic acid, 3-amino-3'-sulfoben-zoylaminobenzene-4-sulfonic acid, 3-amino~ethanesuLfonyl-aminobenzene-4-sulfonic acid, 3-amino~thanesulfonylamino-benzene-4-sulfonic acidO 3-amino-~ hydroxyethylsulfonyl-., :, . :: -.

.
, . . , . : . ~ .
.. . - - . . . . . .

aminobenzene-4-sul~on;c ac;d~ 3-am;no-v;nylsulfonYlam;no-benzene-~-sulfon;c ac;d, 3-am;no-~-sulfatoethylsuLfonylami-no-benzene-4-sulfon;c acid~ 3-am;no-~ bromoethyLsul-fonylam;nobenzene-4-sulfon;c ac;d, 3-am;no-phen~1Sulfonyl-am;nobenzene-4-sulfon;c acid, 3-am;no-p-tosylaminobenzene-4-sulfonic acid, 3-am;~ure;dobenzene-4-sulfon;c ac;d, 3-amino-N'-;sopropylure;dobenzene-4-sulfon;c ac;d, 3-am;no-N'-cyclohexylure;dobenzene-4-sulfon;c ac;d, 3~am;no-N'-phenylure;dobenzene-4-sulfonic acid, 3-amino-N'-t4'-chlorophPnyl)-ureidobenzene-4-sulfon;c ac;d, 3-amlno-N'-~3',4~-dichlorophenyl)-ure;dobenzene-4-sulfonic acid, 1-(2'-sulfophenyl)-3-methylpyrazol-5-one, 1-(3'-sulfophe-nyl)-3-methylpyrazol-5-one, 1-t4'-sulfophenyl)-3-methyl-pyra20l-5-one, 1-(2',4'-disuLfophenyl)-3-methylpyrazol-5-one, 1-(3',5'-disulfophenyl)-3-nethylpyrazol-5-one, 1-~2',5'-disulfophenyl)-3-methylpyrazol-5-one, 1-(2'-chloro~
4'-sulfophenyl)-3-methylpyra~ol-5-one, 1-t2'-chloro 51_ sulfophenyl)-3-methylpyrazol-5-one, 1-~2',5'-dichloro-4'-sulfophenyl)-3-methylpyrazol-5-one, 1-t2'-methyl-4'-sulfo-phenyl)-3-methylpyrazol-5-one~ 2'-methyl-2'-sulfophe-nyl)-3-methylpyrazol-5-one, 1-t2'-methyl-3'-chloro-4i-sulfophenyl~-3-methylpyrazol-5-one, 1-~2',~'-methyl-43 sulfophenyl)-3-methylpyrazol-5-one, 1 ~3'-carboxyphenyl)-3-methylpyrazol-5-one~ 1-(3'-sulfamoylphenyl)-3-methyl-pyrazol-5-one, 1-~4'-sulfamoylphenyl)-3-methylpyrazol-5-one, 1-~6'-sulfonaphth-2'-yl)-3-methylpyrazol-5-one, 1-~4',8'-disulfonaphth-2'-yl)-3-methylpyrazol-5-one, 1-5',7'-disulfonaphth-2'-yl)-3-methylpyrazol-5-oneO 1-t3',6',8'-trisulfonaphth-2'-yl)-3-methylpyrazol-5-one, 3û 1-~4',6',8'-trisulfonaphth-2'-yl)-3-methylpyrazol-5-one, 1-~6'-sulfonaphth-1'-yl)-3-methylpyrazol-5-one, 1-(7'-sulfonaphth-1'-yl)-3-methylpyrazol-5-one.

The diazotization reaction of the starting aniLine com-pounds of the general formula ~6) is generally effected analogously to known procedures through the action of nitrous acid in aqueous mineral solut;ons at t~mperatures below 15C. The coupling of these diazonium salts ~ith the coupl;ng components of the general formula ~7) is ~ ~. .. .
-: .: :
- : . , - ~
'~

:

~arried out ;n the strongly ac;d to neutral p~ range ana-logously to known reaction methods depend;ng on the nature of the coupling component. For instance, the coupling ~ith coupl;ng components ;n ~h;ch K stands for a radical of the formula t3a) or (3d) is as a rule effected at a pH bet~een 1 and 3 and in the case of coupling conpo-nents ;n ~h;ch K stands for a rad;cal of the formula t3b) or (3c) as a rule at pH values between 3 and 7, ;n the case of a coupl;ng range near pH 7 care needing to be taken that pH 7 is not exceeded, in order to avoid damag-ing the fiber-reactive group, although if d;azo components ~hich contain ~ -hydroxyethylsulfonyl groups are used the coupling can also be carried out in the alkal;ne range~
The coupling temperature is as a rule bet~een 10 and 40Cc 1~
The precipitation and ;solation o~ the compounds of the general formula (1) prepared according to the invention from the synthesis solutions can be effected by generally kno~n methods, for example either by precipitating from the reaction ~edium w;th electrolytes~ such as, for example, sodium chloride or potassium chlor;der or by evaporating the reaction solution, for example by spray~
drying, it being possible to add a buffer substance to this reaction solutionr The compounds according to the invention of the general formula (1) have fiber-reactive properties and very good dyeing properties. They can therefore be used for dyeing tincluding printing) hydroxy- containing and/or carboxamido-containing materials~ It is also possible to use the solutions obtained in the synthesis of compounds according to the invention, optionally after addition of 3 buffer substance and optionally after concentration, in dyeing directly as a liquid preparation.
The present invention therefore also relates to the use of the conpounds a~cording to the invention of the ~eneral for~ula t1) for dyeing tincluding printing~ hydroxy-and/or carboxamido-containing materials~ or to processes , , - .

.. . . . . .
.. , . . ~

. . . . .
' - ~. ~:' . . .'' :

for the;r application to these substrates. The materials are preferably used ;n the form of f;ber materials, ;n particular ;n the form of text;le f;bers, such as yarns, ~ound packages and fabr;cs. The procedures used can be analogous to kno~n procedures.

Hydroxy -conta;ning materials are those of the natural or synthetic origin, such as~ for example, cellulose fiber materials or their regenerated products and poly-vinyl alcohols. Cellulose fiber materials are prefer-ably cotton or indeed other vegetable fibers such as linen, hemp~ jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filam~nt viscose.
Carboxamido-conta;ning materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example ~ool and other animal hairs, silk, leather, polyamide-66, polyamide-6, polyamide-11 and polyamide-4.

The compounds according to the invention of the formula (1) can be applied to and fixed on, in accordance ~ith the use according to the invention, the substrates men-tioned, in particular the fiber materials mentioned, usingthe application techniques kno~n for ~ater-soluble dyes, in particular fiber-reactive dyes, for example by applying or incorporating the monoazo compound of the general for-mul3 (1) in dissolved form to or into the substrate and f;xing it thereon or therein, optionally by means of heat and/or by means of an alkaline agentO Such dyeing and fixing methods are extensively described in the literature.

Thus, applied to cellulose fibers from a long liquor by the exhaust method usin all nanner of ac;d-binding agents and optionally neutral salts, such as sodium chloride or sod;um sulfate, they show very good color y;elds and an excellent color buildup. Dyeing is preferably carried " ' , ' . ~ , " ~ ''' ' : , ~ ,. . ..
-' ~

~ ~76~

out ;n an aqueous bath at temperatures be~een 40 and 80C,o~tionally atatempera~ure of up to 120C under pressure, andoptionally ;n the presence of customary dye;ng assistants. Very good color y;elds are obta;ned already at a dyeing tempera~ure of 40C.

A poss;ble procedure ;s to ;ntroduce the material intothe ~arm bath and to raise the bath gradually to the desired dyeing temperature and to complete the dyeing process at that temperature. If des;red, the neutral salts ~hich speed up the exhaust;on of the dye can also be added to the bath only af~er the actual dyeing temperature has been reached.

Using padding me~hods, good coLor yields and good color buildup are likewise obtained on cellulose f;bers~ fixing being effected in conventional manner by leaving the pad-ded cloth to stand at room temperature or elevated tem-perature, for example at up to 60oc, by steaming or by means of dry heat.

The customary printing methods for cellulose fibers can be carried out as one-step processes~ for example by printing ~ith a print paste ~hich contains a compound according to the invention and sod;um bicarbonate or some other acid-bind;ng agent,and subsequently steaming at 100 to 103C~ or as t~o-step processes, for example by printing ~ith a neutral or weakly acid print paste ~h;ch contains a compound according to the invention,and sub-sequently fixing the compound according to the inventioneither by passing the prlnted material through a hot alkali- and electrolyte-containing bath,or by overpadding ~ith an alkaline electrolyte-containing padding liquor and subsequently leaving this overpadded material to stand or steaming or treat;ng it w;th dry heat, producing likewise strong prints with sharp contours and a bri~ht white ground. The outcome of the prints depends only little on varying fixing conditions.

.
: . . . .
, . .. :

.

- . :
.

7~

The agents ~hich have acid binding properties and cause the compound of the formula (1) to be fixed to the cellu-lose fibers are for example water-soluble basic salts of the aLkali metals and alkaline earth metals of organic or ;norganic acids or compounds ~h;ch release alkal; when hot~ They are ;n part;cular the alkali metal hydroxides and alkal; metal salts of ~eak to medium inorganic or organic acids, preferably their sodium and potass~um com-pounds. Such acid-binding agents are for example sodium hydrox;de, potassium hydroxide, sod;um carbonate, sodiu~
b;carbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodiumhydrogenphosphate, sodium tr;chloroacetate~ sodium silicate or trisodium phosphate.

By trèating the compounds according to the invention ~dyes) ~ith the acid-binding agents, optionally under the action of heat, the dyes according to the invention become chemically bonded to the cellulose fiber; in par~icular dyeings on cellulose have after ~he customary aftertreat-men~ of rinsing to remove unfixed dye portions excellent~et fastness properties, in particular since unfixed dye portions are readily ~ashed off.

The dyes on polyurethane or natural or synthetic polyam;de fibers are customarily carried out from an acid medium.
Thus, for example, the dyebath can have added to it acetic acid and/or ammonium sulfate and/or acet;c acid and ammo-n;um acetate in order to maintain the desired pH. To obtain a satisfactory levelness for the dyeing, it is adv;sable to add customary leveling assistants, such as, for example, based on a reaction product of cyanuric chloride ~ith three times the molar amount of an amino-benzenesulfon;c acid and/or of an aminonaphthalenesulfonic acid or based on a reaction product of for example stearyl-anine ~ith ethylene oxide. As a rule, the material to bedyed is introduced into the bath at a temperature of about 40C and is agitated therein for some time, the dyebath is then adjusted to the desired ~eakly acid, pre-ferably ueakly acetic acid, pH, and the actual dyeing is - .~ ' , ~ ' -' : ' .
~, ' .~ ', .
- , ' ~. ' - ~

~ ~7~

carried out at a temperature between 60 and 98C. How-ever, the dyeings can also be carried ou~ at the boil or at temperatures up to 120C ~under pressure)O

S The compounds according to the invention of ~he general formula (1) possess powerful leveling properties ~hen used in dyeing, and the dyeings and prints prepared there-with are as a rule distinguished by high tinctorial strength~
The dyeings and pr;nts possess, ;n part;cular on cellu-lose f;ber mater;als, a very good l;ght fastness and good to very good ~et fastness propert;es, such as, for example, good to very good ~ash fastness propert;es at 60 to 95C, even ;n the presence of perborates, ac;d and alkal;ne fulling, crossdyeing and perspiration fastness properties, good to very good ac;d and alkaline persp;ration fastness properties, a high steam stability, good to very good alkali, acid, ~ater and sea water fastness properties, and also a good pleating fastness, hot press fastness and rub fastness. They also have very good resistance to acid fading when stored mois~ while still containing acetic ac;d.

The process of dyeing on wool is effected here in conven-tional and known manner by subjecting the fiber-reactive compound of the general formula (1) to the exhaustion process w;th pH control, preferably initially from an acid dyebath ~ith a pH of about 3.5 to 5.5, the pH be-ing shifted to~ard the end of the dyeing time into theneutral and if desired ~eakly alkalîne range up to a pH
of 8.5, in order to bring about the full reactive bond between this dye of the formula (1) and the fiber~ in particular if high depths of shade are to be achieved.
At the same time, the dye portion uhich is not reactively bonded is dissolved off.

The procedure described here also applies to preparing dyeings on fiber materials made of other natural ~ . ' ` ` , . : . . . .

. ". : . , ~ 7 ~ ~ 4 polyamides or made of synthetic polyamides and po~yure-thanes. The dyeings are carried out a~ temperatures of 60 to 10QC, kut they can also be carr;ed out ;n sealed dyeing apparatus at temperatures up to 10~C. Since the compounds of the general formula t1) are very read;ly ~ater-soluble, they can also be used with advantage in conventional continuous dyeing methods. The tinctorial strength of the compounds according to the invent;on of the general formula (1) is very higha On fiber materials, ;n particular in the react;ve dye;ng of ~ool, they pro-duce strong fast dyeings. If dye;ng temperatures of 100 to 106C are used~ the exhaustion of the bath is found to be high.

In the case of the dyeings obtainable with the compounds according to ~he invention of the general formula (1) it is possible to dispense ~ith the otherwise customary ammo-niacal aftertreatment of the dyed material. Unl;ke struc-~urally simiLar kno~n dyes, they surprisingly show a very good color buildup, the brilliant hue being retained in deep shades. Moreover, they are highly compatible ~ith other fiber-reactive ~ool dyes~ ~hich make possible a surprisingly level dyeing of the fiber. Similarly, material made of ~ool fibers of different proveniences can be dyed level ~ith the compound according to the invention. To improve the leveling behavior, it is pos-sible, if necessary, to add a customary leveling assistant, such as, for example, N-methyltaurine.

The examples belo~ serve to illustrate the invention~
The parts and percentages are by weight, unless otherwise stated. Parts by ~eight relate to parts by volume as the kilogram relates to the liter.

The compounds described in these examples in the ~orm of formulae are given in the form of the free acids; in general~ they are prepared and ;solated ;n the form of their sodium or potassium salts and are used for dyeing in the form of their salts. The starting compounds and , ' ..................... .

components named in the exampLes below, in particular the tabulated examplesO in form of the free acid can be used as such or in the form of their saltsr preferably alkali metal salts, such as sodium or potassium salts, in the synthesis.

Example 1 ._ a) To prepare 2,5-di- S~-sulfatoethylsulfonyl~-aniline, ~hich is used as the diazo co~ponent in the synthesis of the azo compounds a~cord;ng to the invention, a m;xture of 531 parts of 2-chloro 5-(~ hydroxyethyl-sulfonyl)-n;trobenzene, 236 parts ofthioglycol and 200 parts of water is heated to 25 to 30C; 175 parts of solid potassium carbonate are added at that tempera-ture ~ith st;rring and ~ith oxygen excluded in the course of 3 hours. The reaction batch is then stirred for a further 6 to 8 hours~ until starting material is no longer detectable by thin layer chromatography.
The batch is cooled do~n to 15 to 20C, and the result-ant 2-~-hydroxyethylthio)-5-(~hydroxy-ethylsulfonyl~-nitrobenzene precipitates ;n yello~ crystals. It is isolated by fil~ration, ~ashed with ~ater until neutral and dried.
337 parts of this compound are stirred together with 4 parts of sodium tungstenate dihydrate into 1D00 parts of ~ater, and the batch is brought at 60C to a pH
between 5 and 5.5 with 20X strength aqueous acetic acid~ 117 parts of 30X strength aqueous hydrogen per-oxide solution are added ;n the course of 30 minutes, during ~h;ch the reaction temperature is simultaneously ra;sed to 80C. At ~0 to 90C a further 15Z parts of this hydrogen peroxide solution are added at a uni-for~ rate in the course of a further hour. The result is a clear, virtually colorless solution, ~hich is stirred at 90 to 95C for a further 10 hours. After the batch is cooled down to 10 to 15C, the precip;-tated crystals are filtered off uith suction, ~ashed with ~ater and dried. About 3U7 parts of 2,5~di~
hydroxyethylsulfonyl)-nitrobenzene are obtained.

' :

. .
.

169.5 parts of th;s compound are added ~ith thorough stirr;ng to a ~arm suspension at 85C of 75 parts of iron po~der in 40D parts of water and 1 part of con-centrated aqueous hydrochlor;c acid; dur;ng the addi-S tion, the temperature can be maintained at 85 to 95C~ithout further heating. The batch is stirred at this temperature for a further 30 m;nu~es~ is then brought to pH 8 with sodium hydroxide solution and is then filtered hot ~ith suc~ion. As the filtrate cools do~n, 2,5-di-(~-hydroxyethylsulfonyl)-aniline crystallizes out, isolation yielding about 100 parts thereof.
61.8 parts of this aniline compound are added at about 20C ~ith stirring ~o a mixture of 200 parts of sul-furic acid monohydrate and 25 parts of 65X strength oleum; the stirring is continued for 12 hours. The resultant cLear solution is then slo~ly stirred at a te~perature belo~ 5C into 1000 parts of a 25X strength aqueous potassium chloride solution~ Stirr;ng ;s con-tinued for a further 3 hours, and the prec1pitated pro-duct is then filtered off with suctiong ~ashed with25% strength aqueous potassium chloride solution and dried. The result obeained is a po~der which contains potassium chloride and~ in an amount of about 60X~ 2,5-di-t~-sulfatoethylsulfonyl)~aniline.
25 b~ 200 parts of ice and 5 parts by volume of concentrated sulfuric acid are added to a solution of 45.9 parts (based on 100X pure substance) of the potassium com-pound of the 2,5-di-( ~sulfatoethylsulfonyl)-aniline ;n 400 parts of water~ Diazotization is effec~ed by gradual addition of 10.2 parts by volume of aqueous 5 N sodium nitrite solution in the course of bO minutes.
The batch is further stirred at a temperature beSween O and 3C until diazotization is complete, and then the small excess of nitrite still pr~sent is as usual destroyed ~;th sulfamic acid.
c) This diazonium salt solution has added to ;t at about 5C uith stirring an aqueous sulfuric acid solu~ion of 18.8 parts of 3-chloro-N,N-bis-~B-sulfatoethyl~-aniline in the course of 10 minutes. A pH between 2 . . .
: ~ , ' .~ .
.
, . : ' .
- ' . . ~ . . ' .

~ ~7~
~ 26 -and 2.2 is set ~;th sodium carbona~e or preferab~y, to bind the sulfur;c acid and prec;p;tated as calcium sulfate, calcium carbonate, and the coupl;ng ~i~ture ls ma;ntained at tha~ pH for a further 3 hours~ A
pH of 5.5 is then set ~;th sodiu~ carbonate or pre-~erably ca~cium carbonaee~ and the prec;p;tated calcium sulfate is filtered off ~ith suction. The filtrate has add~d to it ~ith stirring potassium chloride in an amount wh;ch corresponds to 20X by volume of the filt-tO rate, the nixture is s~irred for a further 4 hours,and the precipitated product is filtered off ~ith suc tion flnd dried.

The result obtained is an orange-red po~der ~hich, in addit;on to potasslum chlor;de, contains the compound accord;ng to ~he ;nvent;on of the formula ~2 C~2-0~0 ~ N = ~ H2-~H
Cl ~H2-CH2-0S03H

C~2 ~H2-VS03H
as its potass;um salt. The azo compound according to the in~ention has a ~ax of 479 nm in aqueous solu~lon;
it has very ~ood dyeing properties and ;s very highly su;table for dyeing and printing fiber materials ment;oned in the description, such as, in particular, cellulose fiber naterials, such as cotton. Using the application snd fixing ~ethods custo~ary for f;ber reactive dyes~ the compound produces in a hi~h de~ree of ~;xation strong orange-red dye;n~s and prints hav;n~ good fastness pro-perties, in particular ~et fastness properties, such as, in particular, ~ood ~ash fastness propertles at ~0 to 95C, good alkaline perspiration fastness and fastness to chlorine ~ater, and ~ood perspiration~ ht fastness properties n ': ' ' ' : " ' ' " , ' . ,.
'' '' ,. ' ~ '. ' ~ .
, ~ ~ - ' ' . ' ~ ' - : ~ , ' ' ' ' ~ ' , .' ' ' . .

~7~

Example 2 a~ To prepare 3~4-di-(~ sulfatoethylsul~onyl)-aniline, ~h;ch ;~ used as the d;azo component in the synthes;s of the azo compounds accord;ng to the ;nvent;on, a m;xture of 531 parts of 4-chloro-3-t~hydroxyethylsul-fonyl)-n;trobenzene, 240 parts of th;oglycol and 400 parts of ~ater has added to ;t at 20C 175 parts of sol;d potass;um carbonate with s~;rring and ~ith oxy-gen exc~uded in the course of 3 hours. The reaction batch is then stirred at 25C for a further 12 to 15 hours, until start;ng material is no longer detect-able by thin layer chromatography. The batch is cooled do~n to 10 to 15C, and the resultant 4~ ydroxy ethylthio~-3-t~-hydroxyethylsulfonyl)-nitrobenzene precipitated is isolated by filtration, ~ashed ~ith ~ater until neutral and dried.
307 parts of this compound are stirred together with 4.5 parts of potassium tungstenate into 1200 parts of water, and the batch is brought to a pH between 4.5 and 5 with 2 N aqueous hydrochloric acid and heated to 70 to 75C. 100 parts of 35X strength aqueous hydrogen peroxide solution are gradually added at that temperature in the course of one hour, the batch is then heated to 90 to 95C in the course of 30 minutes and a further 110 parts of this hydrogen peroxide solution are gradually added in the course of 90 minutes. Stirring of the batch ;s cont;nued for 13 to 14 hours at 90 to 95C~ After the batch is cooled do~n to 20 to 25C, the precipitated crystals are fiLtered off with suction, washed ~ith ~ater and dried~ About 325 parts of 3,4-di-~-hydro~yethylsulfonyl)-nitrobenzene are obtained.
111 parts of this compound are added with thorough stirring to a ~arm suspension at 85C of 50 parts of iron powder in 350 parts of ~ater and 1 part of con-centrated aqueous hydrochloric acid; dur;ng the add;-tion, the temperature can be naintained at 85 to 95C
w;thout further heating. The batch ;s stirred at - ~ , .

.
- ;
- : . :
.

~,2t~

this temperature for a further 30 minutes9 is then brought to pH 8 ~;~h eod;um hydrox;de solu~;on and ;s then filtered hot ~i~h suc~;on. As the filtrate cools do~n, 3,4-d;~ hydroxyethylsulfonyl~-aniline crystal-l;zes out, isolation yield;ng about 85 partsthereof.
61.8 parts of th;s an;line co~pound are added at about 20C ~;th st;rr;ng to a ~;xture of 200 parts of sul-furic ac;d ~onohydrate and 25 parts of 65X strength oleum; the stirr;ng ls con~;nued for 12 hours. The resultant clear solution is then slowly s~irred at a temperature belo~ 5C into 1000 parts of a 25X
strength aqueous potassium chloride solution. Stir~
r;n~ ;s cont;nued for a further three hours, and the precipitated product ;s ~hen filtered off ~i~h suction, ~ashed ~;th 25X strength aqueous potassium chloride solut;on and dried~ The result obtained is a po~der ~hich contains potassiun chloride and, in an amount of about 60X, 3,4-di-~-sulfatoethylsulfonyl~-an;l;ne.
b) To prepare the azo compound accord;ng to the inYention by diazotizing and coupling 3,4-di~ sulfatoethyl-sulfonyl~-aniline and 3-chloro-N,N-bis-~-sul~a~oethyl)-aniline, the same procedure as used in sections b~ and c~ of Example 1 is used.
The result obtained is a yello~;sh red po~der ~hich, in addition to potassium chloride, contains the co~pound accord;n~ to the invention of the formula _~ ~cH2-cH2-oso3H

CH2-S02--~ J \1~ ~
l H2 ~fo2 Cl CH2 CH2 0S03H
OSO~ H2 C~2_0so~H

as ;ts potassium salt. The azo compound accordin~ to the ;nvention has a ~ax of 493 nm in aqueous solution;
it has very ~ood dyein9 propert~es and is very h;~hly suitable for dyein~ and printin~ fiber Materia~s mentioned - ~
- ~. ' : '. . . :
, ' : .

~ ~7~
- 29 ~
in the descriptionO such as, in particualar, cellulose fiber materials, such as cotton. Using the application and fixing methods cus~omary for fiber-reactive dyes, the com-pound produces in a h;gh degree of fixation strong yellowish-red dyeings and prints having good fastness properties, inparticular ~et fastness properties, such as, ;n particular, good ~ash fastness propert;es at 60 to 95C, good alkaline perspirat;on fastness, good fastness to chlor;ne ~ater and good persp;ration-l;ght fastness propert;es~
~ O
Example 3 14.5 parts of N-ethyl-N-(3-sulfobenzyl)-anil;ne are added to a solution, prepared as in Example 1b), of the d;azo-n;um compound of Z,5-d;-t~-sulfatoethylsulfonyl)~aniline.
The coupling is complete after about 1 hour at a pH bet-~een 2.5 and 3 and at a temperature bet~een 0 and 3C;
the pH is set and ma;ntained by means of sod;um b;carbo-nate. The azo compound accord;ng to the ;nvention ;s salted out ~;th sod;um chloride and isolated.
The result obtained ;s a yello~ish red po~der ~hich, in addition to sod;um chlor;de, conta;ns the compound accor-ding to the ;nvent;on of the formula l~2 C~2 OS0~ S03H

~ ~ / 2 ~H2 CH2 S3~

as ;ts sod;um salt. The azo compound accord~ng to the ;nvention has a ~max of 493 nm in aqueous solut10n; it has very ~ood dye properties and ;s very hi~hLy suitable for dyeing and pr;nt;ng fiber mater;als menttoned ;n the descript;on, such as, ;n part;cular, cellulose fiber ~aterials, such as cotton. Usin~ the application and fix;ng ~ethods customary for fiber-react;ve dyes~ ;t . . . .
.. : . . . .
, ' ' ~: , . ,', ' . , 3~

produces ~ith a h;gh degree of f;xat;on strong yello~;sh r~d dye;ngs and pr;nts having ~ . gYood fastness prope~ies told for ~he compound accord;ng to the invent;on of Example 1.
s Exam~le 4 14.5 parts of N-ethyl-N-t3-sulfobenzyl)-an;line are 2dded to a solution, prepared as in Example 2b), of the diazo-nium compound of 3,4 d;~ sulfatoethylsulfonyl)-aniline~
1Q The coupling is complete after about 1 hour at a pH bet-~een 2.5 and 3 and at a te~perature bet~een 0 and 3C;
the pH is set and main~ained by ~leans of sodium bicarbo-nate. The a20 compound accordiny to the invention is salted out ~ith sodium chloride and isolated.
The result obtained is a red powder uh;ch, in addition to sodium chloride, contains the compound according to the invention of the formula N = N ~ N /
~CH2 S2 ~ CH2-CH~5 OS0 ~ I2 3 CH2-CH~-OS03H

as its sodium salt. The azo co~pound accordin~ to the invention has a ~ax of 496 nm in aqueous solution; ;t has very good dye properties and is very highly suitable for dyeing and printin~ fiber ~aterials mentioned in the description, such as, in particular, cellulose fiber ~aterials, such as cotton. Using the application and fixing ~ethods customary for fiber-reactive dy~s~ it pro-5 duces ~ith a h~gh degree of fixation strong red dyeingsh js9imi~ar~Od ~astneSS propertie~
co~pound according to the invention of Exa~ple 1.

, .
.

xample 5 14.2 parts of 1-(4 suLfophenyl)-3-carboxy-5-pyrazolone ar~ added to a solution, prepared as in Example 1b), of the diazQn;um compound of 2,5-d;-~ ~sulfatoethylsulfonyl)-aniline. The coupling is complete after one hour at apH betbeen 2~5 and 3 and at a tempera~ure between 0 and 3C; the pH is set and maintained by means of sodium bicarbonate. The azo compound according to the invention is sal~ed out ~ith sodium chloride and isolated~
~0 ~he result obtain~d i~ a yellow po~der ~hich, in addition to sodium shloride, contains ~he compound according to the invention of the for~ula CR2 CH2 S3~ ~H

O-- N = N ~ 1 ~L S03H

COOF~

~H2 CR2 ~S03~

as its sodium sal~O The a~o compound according to the in~ention has a ~max of 389 nm in aqueous solution; it has very good dye properties and is very hi~hly suitable for dyeing and printing fiber ~aterials ~entioned in ~he description, such as, in particular, cellulose fiber materials, such as cotton. Usin~ the application and fixing methods custo~ary for fiber reactive dyes, it pro-duces ~ith a high de~ree of fixation strong yello~dyein~s and prints havinG ~ ~oYd fastness prsperties as told for the co~pound according to the invention of Exa~ple 1.

Example ~
14.2 parts of 1-t4-sulfophenyl)-3-carboxy-5-pyrazolone are 3dded to a ~olut1on, prepared as in ExaMple 2b), of the diazonium compound of 3,4-di-~-su~fatoethylsulfonyl)-aniline. The couplin~ is complete after about 1 hour at a pH bet~een 2~5 and 3 and at a temperature bstween 0 . . .
' ' . ~ .
, , ' ' '. ~ .,' ,, , , ' :
' --'' ' ' ' :: , :

~ . ~

:~ 2~

and 3C; the pH is se~ and ma;ntained by means o~
sod;um b;carbonate. The azo compound accord;n~ to th~
1nvention ~s salted ou~ ~;th sod;um chlor;de and lsolatedO

Thè result obtained ;s a yellow po~der ~h;ch, in ~ddit;on to sod;um chlor;de, conta;ns the compound according to the invent;on of the formula 0~

f ~1~ E= N~ ~o ~3 8H2-S02--~ ~N 3 1 2 12 COO~
OS03~ CH2-~H2-~S3H
as its sod;um sa~. The azo co~pound according to the invention has a ~max of 405 nm in aqueous solution; it has very ~ood dye properties and is very highly suitable for dye;ng and printing fiber ~aterials ~entioned in the description, such as, in particular, cellulose fiber ~aterials~ such as cotton. Using the application and fix;ng ~ethods custo~ary for fiber reactive dyes, i~ pro-duces ~ith a high degree of fixation strong yellow dye-slmllarly ;ngs and prints hav;ng ~ good fastness properties the co~pound according to the invention of Example 1.

Examples 7 to 122 The tabulated examples below describe further azo com-pounds according to the ;n~ention in terms of their diazo-co~ponents tA) or t~ and the radical of the coupling com-ponent -K. ~hey can be prepared in 2 ~anner accordin~ to the invention, for example in accordance ~ith the pro-cedures of the above illustrative embod;~ents, from the dia~o coMponent and the coupling component H-K. They like~ise have very good f;ber-reactive dye properties and are distingu;shed by good applicat;on properties.
Using the application flnd fixin~ ~ethods customary for fiber-reactiYe dyes they produce strong dyeings and prints on the f;ber ~aterials ~ent;oned in the description, such . .. ..

:
.-- . . ~ .
: . :

as, in par~icular, ceLl~lose f;ber materials, ;n the hue indicated in the respect;ve tabulated example there on cotton) hav;ng, in some cases, very good fastness properties.

Said dia7o component (A) is:
2,5-di-(~ sulfatoethylsulfonyl)-aniline;

said diazo component (B) is:
3,4-di-(~-sulfatoethylsulfonyl)-aniline.

., :
. . .

Ex- Dia20 Rad;cal of the Hue ample component co~pling component 7 ~A) 4~ (B-sulfatoethyl)- yellowish amino~-phenyl red 8 (B) ditto ditto 9 (A) 4-~N-Ethyl-N-(B-sulfato- ditto ethyl)-amino]-phenyl (~) ditto d;tto 11 (A) 2-AcetylQmino-4-~bis-(B- red ~ul~atoethyl)~amino~-phenyl 12 (B) ditto red 13 tA) 2-Acetylamino~5-methoxy-4- red [bis-~B-~ulfatoethyl)-amino3 phen~l 14 (B) d;tto red tA) 2-Methylsulfonyl~nido-4-[bis- blu;sh (B-sulfatoethyl)-amino3-phenyl red 16 (B) ditto ditto 17 tA) 2Chlorethylsulionylamido-4- ditto ~bis-(B-sulfatoethyl)-Pmino~
phenyl 18 tB) d;tto d;tto 19 (A) 4-[N tB-cyanoethyl)-~-(B-eul- ditto ~atoethyl)-amino~-phenyl tB) d;tto red 2t tA) 4-[N~(B-Cyanoethyl)-N-(B,y-di- yellowish sulfato-n-propyl)-a~ino3- red phenyl 22 (B) ditto red 23 ~A) 4-~(B-~ul~atoethyl)- yellow;sh I~-benz~ nlno3-phenyl red 24 (~) d;tto red .. . .: .

.. ., . .......... .. :
'' - . ' ' ' , ~
: .. . :, .
', ~'. , '.' .': ~ ' ~ 35 -Ex- Diazo Radical of the ample component coupling component _ Hue ~5 ~A) 4 [~-tB,~-D1~u1fato- yellowish n-propyl) benzylamino]-phenyl red 26 (~) ditto red 27 (A) 2-Tri~luoromethyl-4-[bis~ yellowish sul~atoethyl)-Qmino]-phenyl red 28 (B) ditto ditto 29 (A) 2-C~ano-4-~bis-(B-sulf~to- ditto ethyl)-amino]~phenyl 3 (~) ditto ditto ~1 (A) 2-Meth;ylsul~onyl-4-~bls-(B- yellowish ~ulfatoethyl)-amino]-phenyl ~ed 32 (~) ditto red ~3 (A) 2-Ethylsulfonyl 4 [bis-(B- yellowish sulIatoethyl) amino~ phenyl red 34 (B) ditto red (A) 2-(n-Butyl-~ulfonyl)-4-[bi~- yellowish (B-sul~atoethyl)-amino~-phenyl red 36 (B) dltto red 37 (A) 2-(N,~-Diethyl-sul~amoyl)-4- yellow;sh [bis-(B-suliatoethyl)-amino3- red phenyl 38 (~) ditto red 39 (A) 2-N-Phen;~ ulf~moyl-4-[bis- yellowish (B-sulratoe~hyl)amino~-phenyl red (R) ditto red 41 (A) 2-(N,~-Di-n-butyl~sulfamoyl)-4- yellowish [bls-~3-sul~atoethyl) amino~- red phenyl 42 (B) ditto red 43 (A) 2-[~ Di-(B sul~atoeth~ yellowish auIfamoyl3-4-(diethylamino)- red phenyl 44 (~) ditto red .

-. ' :' ,: '~ . ~

.

A~

Ex- Diazo Radical of the ample component coupl;ng component Hue .
~A) 2-Carb~moyl_4-[bis-(B-sul~a- yellowish toethyl)-~minoJ-phenyl red 46 (~) ditto ditto 47 (A) 2-~,N-Diethyl-carbamoyl-4- ditto [bis-(B-sulfatoethyl)-amino]-phenyl 48 tB) d;tto ditto 49 (A) 2-~,N-Di-n-butyl-carbamoyl-4- ditto [bis-(B-sulfatoethyl)-amino]-phenyl 5 (B) ditto ditto 51 (A) 2-N,N-Di-(B-sul~atoethyl)- yellowish carbamoyl-4-(dieth;srla~n~no)- red phenyl ~2 . (~3) d;tto 53 (A) 2-[~-Methyl-N-(B-sulfatoethyl)- ditto carbamoyl~-4-(diethylamino) ` phen~l -54 (R) d;tto ditto (A) 2-[N-Methyl-~-(B-sul~atoethyl)-sulîamoyl~-4-(diethylamino)-phenyl 56 (R) d;tto d;tto 57 (A) ~-Chlor-4-(B-eul~atoethyl) redd;sh amino-phenyl yellow 58 (~) ditto d;tto 59 (A) 3-Chlor-4-tB,l-disulfato-n- ditto propyl)-amino-phenyl (B? d;tto d;tto 61 (A~ 2-Acetylarllino-5-chlor-4-(B- yellow;sh ~ulisto-n-propyl~-a~ino-phenyl red 62 (~) d;tto d;tto . . ~ ,~, . , ' ""' ' ' . . ': ' ' , , ' - ':' . ,'''' ,,' ' ' :
. .
- ... .

~ ~7~

Ex- Diazo Radical of the Hue ample component coupling component . .

63 (A) 2-Acetylamino~5~chlor-4-(B,l- yello~ish dl3ul~ato-n-prop~l)-amino- red phenyl 64 tB) ditto ditto (A) l-~-(B-Sul~atoethyl)-3-carb yellow ~moyl-4-methyl-6-hydro~y~2-oxo-pyrid-5-yl 66 (~) ditto yellow 67 (A) 1-N-(B-Sul~ato~n-props~ 3- yellow carbamoyl 4-methyl-6-hydroxy 2-oxo-pyrid-5-yl 68 (B) ditto yellow 69 (A) 2-Acetylamino-5-~ulfo-4- reddish amino-phenyl yellow (~m x=
434 nm in ~2) (R) ditto orange in H?0) 71 (A) 4~ (3-sulIobenzyl)-~mino- yello~ish phenyl red 72 ~) ditto ditto 73 ~A) 4-[N-tB-~ul~oethyl)-~-benzyl- ditt~
~minoJ-phenyl 74 (3) d;tto ditto (A) 4~ -sulro-n-propyl)-~- ditto benzylamino]-phenyl 76 (~) . ditto ditto 77 (A) 4 EN- (B-sulfoethyl)-I3~ethyl- ditto amirio~-phenyl 78 (B) ditto . . ditto 79 (A) 4-[N-(y-Sulf'o-n-pro~ ditto ethylaminoJ-phenyl (B) d;tto ditto : - : - ~ . ,- ' .. . . .
-, ~
- ~ . ,. , , .. , : ' - . .
- ~ , ~ ~7~

Ex- Diazo Radical of the Hue ample component coupling component 81 (A) 2-Chlor-4~[biE3~ sulfo-n- yellowish propyl)-~mino] phenyl red 82 tB) ditto ditto 83 (A) 2-Trifluormeth 1-4-[bi~ - ditto ~ul~o-n-pro~yl~-~mino~-phenyl ~4 t~) d;tto ditto (A) 2-Chlor-4-~bi~-(B-~ulfo- ditto ethyl)-Rmino~-phen~l 86 (~) . ditto ditto 87 (A) 2-Trifluormethyl-4-[bis-(B-sulioethyl) amino]-phenyl 88 (~) ditto ditto 89 (A) 2 N-Phenyl-8ul~amoyl-4-[bis-(y-8ulfon-propyl)-amino~-phen~l (~) d;tto ditto 91 (A~ 2-N-Phenyl-sulfamoyl-4 [bi8- ditto (B-sulfoethy1)-Qmino3~phenyl 92 (~) ditto ditto 93 (A) 2-[N-(B Sulfoethyl)~sulfaDloyl~- ditto 4 diethylamino-phen~l 94 (B) ditto ditto .
(A) 4-[N (~-Sulfophenyl)-ethyl- red N-~thyl-amlno]-phen~l 96 (R) ditto red 97 (A) 2~ lor-4-N-(sulfobenz~ yelLo~t am$no-phenyl 98 (~) ditto yeliow 99 (A) l~ Sul~ophenyl)-~-methyl- reddish 5-~ino-pyrazol-4-srl yellow 100 (3) d1tto ditto ., : .

. . .. . .

; .
~ ' ' , , Ex- D;azo RadicaL of the Hue ample component coupling component .

101 (A) 1~(4-Sulfophenyl)-3-methyl- reddish 5-amino-pyrazol-4-yl yellow 102 (~) d;tto ditto 103 (A) 2-chlor-4-[N-(3-sulfobenzyl)- yel~ow;sh N-ethyl amino]-phenyl red 104 t~) d;tto d;tto 105 (A) ~-Ethyl-3-sulfomethyl-4- yellow methyl-2~o~o-6-hydroxy pyrid 5-yl 106 (B) d;tto yellow 107 (A) ~-n-Butyl-3-sulfomethyl-4- yello~
methyl-2-oxo-6 hydroxy-pyrid 5-yl 108 (B) ditto yellow 109 (A) ~-Benz;srl-3-~ulfo~ethyl-4- yellow ~ethyl-2-oxo-6-hydroxy-pgrid-5-yl 110 (~) d;tto yellow f11 (A) 1~ Phe~ylethyl)-3-sulfo- yellow ~ethyl-4-methyl-2-oxo-6-hydro~y-pyrid-5-yl 112 (R) ditto yellow 113 (A) l-~-(B-Sulfatoethyl)-~- yellow eyano-4-~ethyl-2-oxo-6-hydroxy-pyrid-5-yl 114 tB) ditto yellow 115 (A) 1-(4-SulIophengl)-3-carboxy- orange pyrazol-5-on-4-yl t16 (B) :ditto orange 117 (A) 1-(3-Sulfophenyl)-3-Jnethyl- orange pyrazol-5-on-4-yl 118 (~) ditto orange .

.
. ' ' : ': ' - - , . ,: : .
- ... . . .
- ' - ' ` '' ' ' " :.: :.
: ~ . .
~: - ' , ~.~7~

Ex- Diazo Radical of the Hue ample component coupl;ng component _ _ 1 1 9 ( A ) 1- ( 2, 5-D~ sul f ophenyl ) -3- o range methyl-5-amlno~pyrazol-4-srl 120 (~) d;tto orange 129 (A) 1-(2,5-Dichlor-4-Rul~o-phe~ orange n~l )-3-methyl-p~raæol-5-on-4-~l 122 (~) ditto orange .

.

:

.

::

; . ' - ' -- - '. . ," ': ,.~: ,' ', ,, , -- : ~ ~: . . - , . , .. : , - ~ ' - ~ . : . .

Claims (20)

1. A water soluble monoazo compound of the formula (1) D - N = N - K (1) in which D denotes a radical of the formula (2a) or (2b) and K represents a radical of the formula (3a), (3b), (3c) or (3d):

(2a) (2b) (3a) (3b) (3c) (3d) in uhich Y is a vinyl group or a group of the formula (4) - CH2 - CH2 - X (4) in which X denotes a substituent which is eliminat-able by means of sn alkali with formation of the vinyl group;
R1 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a sulfo group, a carboxy group, a carbalkoxy group of 2 to 5 carbon atoms, a halogen atom,or an alkoxy group of 1 to 4 carbon atoms which is substituted by a hydroxy, acetyloxy, car-boxy, carbamoyl or cyano group or by a halogen atom;
R2 is a hydrogen atom, an alkyl group of 1 to 4 car-bon atoms, an alkoxy group of 1 to 4 carbon atoms, a halogen atom, the cyano group, a trifluoromethyl group, an alkoxy group of 1 to 4 carbon atoms which is substituted by a hydroxy, acetyloxy, carboxy, carbamoyl or cyano group or by a halogen atom, or is an alkanoylamino group of 2 to 5 carbon atoms which can be substituted by chlorine, bromine, alkoxy of 1 to 4 carbon atoms, phenoxy, phenyl, hydroxy, car-boxy or sulfo, or is an alke noylamino group of 2 to 4 carbon atoms which can be substituted by chlorine, bromine, carboxy. or sulfo, or is a ben-zoylamino group which can be substituted in the benzene nucleus, or is an alkylsulfonyl group of 1 to 4 carbon atoms,or a phenylsulfonyl group which can be substituted in the benzene nucleus,or is an alkylsulfonylamino group of 1 to 4 carbon atoms which can be substituted by hydroxy, sulfato, chlorine, bromine or alkoxy of 1 to 4 carbon atoms, or is a phenylsulfonylamino group which can be substituted in the benzene nucleus, or is a carba-moyl group which can be monosubstituted or disubsti-tuted at the nitrogen atom by 1 or 2 substituents from the group consisting of alkyl of 1 to 4 carbon atoms, substituted alkyl of 1 to 4 carbon atoms, cycloalkyl, phenyl and substituted phenyl, or is a sulfamoyl group which can be monosubstituted or disubstituted at the nitrogen atom by 1 or 2 substi-tuents from the group consisting of alkyl of 1 to 4 carbon atoms, substituted alkyl of 1 to 4 carbon atoms, cycloalkyl, phenyl and substituted phenyl, or is the ureido group or a ureido group which is monosubstituted or disubstituted at the terminal nitrogen atom by 1 or 2 substituents from the group consisting of alkyl of 1 to 4 carbon atoms, substi-tuted alkyl of 1 to 4 carbon atoms, cycloalkyl, phenyl and substituted phenyl;
R3 is a hydrogen atom,or an alkyl group of 1 to 6 carbon atoms which can be substituted, or is an alkenyl group of 2 to 5 carbon atoms which can be substituted by a carboxy or sulfo group or by a chlorine or bromine atom, or is a cycloalkyl radi-cal of 5 to 8 carbon atoms;
R4 is a hydrogen atom,or an alkyl group of 1 to 6 car-bon atoms which can be substituted, or is an alkenyl group of 2 to 5 carbon atoms which can be substituted by a carboxy or sulfo group or by a chlor-ine or bromine atom, or is a cycloalkyl radical of 5 to 8 carbon atoms,or a phenyl radical which can be substituted,or a naphthyl radical which can be substituted by 1, 2 or 3 sulfo groups and optionally by a chlorine atom, an alkoxy group of 1 to 4 carbon atoms, an alkyl group of 1 to 4 carbon atoms, an alkanoylamino group of 2 to 5 carbon atoms or an optionally sulfo-substituted benzoylamino group, or is a heterocyclic radical which can have one or two fused-on carbocyclic rings, it being possible for the carbocyclic rings to be further substituted and the heterocyclic radical to be substituted at the carbon atoms and/or at the heterocyclic atoms by optionally substituted alkyl groups and/or option-ally substituted phenyl radicals, or R3 and R4 together with the nitrogen atom and optionally 1 or 2 further hetero atoms represent a saturated heterocyclic radical;
R5 is a hydrogen atom, an alkyl group of 1 to 4 car-bon atoms, which can be substituted by a sulfo or carboxyl group, or is a phenyl radical;
R6 is a hydrogen atom, a sulfo group, a sulfo-substi-tuted alkyl group of 1 to 4 carbon atoms, a carba-moyl group or a cyano group;
R is a hydrogen atom,or an alkyl group of 1 to 6 car-bon atoms which can be substituted by a sulfato, phosphato, carboxy, hydroxy or alkanoylamino group of 2 to 5 carbon atoms;
R* is a methyl group, a carboxy group, a carbalkoxy group of 2 to 5 carbon atoms, a carbamoyl group or an optionally sulfo-, carboxy-, methyl-, ethyl-methoxy-, ethoxy- and/or chlorine-substituted phe-nyl radical;
R" is a methyl group, a carbamoyl-group or an option-ally carboxy-, sulfo-, methyl-, ethyl-, methoxy-, ethoxy- and/or chlorine-substituted phenyl group;
Q is a phenyl radical which can be substituted or is a naphthyl radical which can be substituted by 1,

2 or 3 sulfo groups and optionally by an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a chlorine atom or an alkyl-amino group of 2 to 5 carbon atoms.

2. A compound as claimed in claim 1, wherein K denotes a radical of the formula (3a) defined in claim 1.

3. A compound as claimed in claim 2, wherein R1 is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a sulfo group, a carboxy group or a chlorine atom, R2 is a hydrogen atom, a methyl, ethyl, methoxy or ethoxy group or a chlorine atom or an alkanoylamino group of 2 to 5 car-bon atoms, a methylsulfonylamino, chloromethylsulfonyl-amino, trifluoromethyl, cyano, methylsulfonyl, ethyl-sulfonyl, n-butylsulfonyl, N,N-diethyl-sulfamoyl, N,N-di-n-butyl-sulfamoyl, N,N-di-(.beta.-sulfatoethyl)-carbamoyl, N-methyl-N-(.beta.-sulfatoethyl)-carbamoyl, N-methyl-N-(.beta.-sulfatoethyl)-sulfamoyl, N-(.beta.-sulfatoethyl)-sulfamoyl, N-phenylsulfamoyl, ureido or N-phenylureido group, R3 denotes a hydrogen atom,or an alkyl group of 1 to 4 carbon atoms which can be substituted by a sulfo, carboxy, sulfophenyl, phenyl, hydroxy, cyano, sul-fato or phosphato group, or represents an alkenyl group of 2 to 4 carbon atoms, and R4 is a hydrogen atom, or an alkyl group of 1 to 4 carbon atoms which can be substituted by a sulfophenyl, phenyl, hydroxy, cyano, sulfo, carboxy, sulfato or phosphato group, or is an al-kenyl group of 2 to 4 carbon atoms or represents an alkyl group of 1 to 4 carbon atoms which is substituted by a N-(.beta.-sulfatoethyl)-carbamoyl, N-methyl(-N-(.beta.-sulfatoethyl)-carbamoyl or N,N-di-(.beta.-sulfatoethyl)-carbamoyl group.

4. A compound as claimed in claim 2, wherein R1 is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a sulfo group, a carboxy group or a chlorine atom, R2 is a hydrogen atom, a methyl, ethyl, methoxy or ethoxy group or a chlorine atom or an alkanoylamino group of 2 to 5 car-bon atoms, a methylsulfonylamino group, trifluoromethyl, cyano, N,N-diethylsulfamoyl, N-methyl-N-(.beta.-sulfato-ethyl)-sulfamoyl, N-(.beta.-sulfoethyl)-sulfamoyl, ureido-or N-phenylureido group, R3 denotes a hydrogen atom, or an alkyl group of 1 to 4 carbon atoms which can be substituted by a sulfo, carboxy, hydroxy, cyano or sulfato group or by a phonyl or sulfophenyl group, and R4 is an alkyl group of 1 to 4 carbon atoms which can be substituted by 1 or 2 substituents from the group consisting of sulfo, sulfato, hydroxy and sulfophenyl, or is a pro-penyl group or a .beta.-(N-.beta.-sulfatoethylcarbamoyl)-ethyl, B-(N-methyl-N-.beta.-sulfatoethylcarbamoyl)-ethyl or .beta.-[N,N-di-(.beta.-sulfatoethyl)-carbamoyl]-ethyl group.

5. A compound as claimed in claim 1 conforming to the formula (5a) (5a) in which Y, R1, R2, R3 and R4 are as defined in claim 1.

6. A compound as claimed in claim 5, wherein R1, R2, R3 and R4 are as defined in claim 3.

7. A compound as claimed in claim 5, wherein R1, R2, R3 and R4 are as defined in claim 4.

8. A compound as claimed in claim 1 conforming to the formula (5b) (5b) in which Y, R1, R2, R3 and R4 are as defined in claim 1.

9. A compound as claimed in claim 8, wherein R2, R3 and R4 are as defined in claim 3.

10. A compound as claimed in claim 8, wherein R2, R3 and R4 are as defined in claim 4.

11. A compound as claimed in claim 5, wherein R1 stands for a hydrogen atom and R2 stands for a chlorine atom or a trifluoromethyl group and both Y and R3 and R4 each represent a .beta.-sulfatoethyl group.

12. A compound as claimed in claim 8, wherein R2 stands for a chlorine atom or a trifluoromethyl group and both Y and R3 and R4 each represent a .beta.-sulfato-ethyl group.

13. A compound as claimed in claim 5, wherein R1 and R2 both denote a hydrogen atom, R3 stands for an ethyl group and R4 for a 3-sulfobenzyl group.

14. A compound as claimed in claim 8, wherein R2 is a hydrogen atom and R3 stands for an ethyl group and R4.

for a 3-sulfobenzyl group.

15. A compound according to claim 1, 13 or 14, wherein both Y represent a .beta.-sulfatoethyl group.

16. A compound according to claim 5 or 8 wherein both Y represent a .beta.-sulfatoethyl group.

17. A process for preparing the azo compound of the formula (1) mentioned and defined in claim 1, which comprises diazotizing a compound of the formula (6) D - NH2 (6) in which D is a radical of the general formula (2a) or (2b) mentioned in claim 1 in which Y has one of the meanings mentioned there or represents a .beta.-hydroxy-ethyl group, and coupling with a coupling component of the formula (7) H - K (7) in which K has the meaning mentioned in claim 1, and if the starting material used is a diazo component of the formula (6) in which Y stands for a .beta.-hydroxyethyl group reacting the resultant azo compound of the formula (8a) or (8b) (8a) (8b) in which K has the meanings mentioned in claim 1, with an acylating or esterifying agent for conversion into azo compounds of the formula (1) in which X stands for an acyloxy radical which is eliminatable under alkaline conditions.

18. A process for preparing the compounds of the formula (1) mentioned and defined in claim 1 in which the radical K contains one or more sulfato or phosphato groups bonded to one or more aliphatic group(s) and one or both Y represent a .beta.-sulfatoethyl or phosphatoethyl group, which comprises reacting an azo compound conforming to the formula (1) which contains one or more hydroxy group(s) bonded to one or more aliphatic group(s) in the radical K
and, if required, in the radical D, with a sulfating or phosphating agent.

19. A process for dyeing (including printing) a hydroxy- or carboxamido-containing material by applying or incorporating a dye to or into the material and fixing it by means of heat or by means of an acid-binding agent, which comprises employing as the dye a compound of the general formula (1) mentioned and defined in claim 1, or prepared according to a process defined in claim 17 or 18.

20. A process according to claim 19, wherein the hydroxy- or carboxamido-containing material is a fiber material.