CS236694B2 - Manufacturing process of water soluable symetric ar asymetric 1:2-chromiumcomplexe or 1:2-cobaltcomplexe azo-compounds - Google Patents

Abstract

Wasserlösliche, symmetrische oder asymmetrische 1:2-Chromkomplex- und 1:2-Kobaltkomplex-Azoverbindungen von Monoazoverbindungen der allgemeinen Formel (1) oder deren 1:2-Chrom- und 1:2-Kobaltmischkomplexe, worin bedeuten:

• Y₁ ist eine zur Metallkomplexbildung befähigte Gruppe, die
• in ortho-Stellung zur Azobrücke an D gebunden ist;
• Y₂ ist eine zur Mettalkomplexbildung befähigte Gruppe, die an K in ortho-Stellung zur Azogruppe gebunden ist;
• D ist der Rest einer Diazokomponente, an den die nachstehend definierte faserreaktive Gruppe V₁ oder die nachstehend definierte faserreaktive Gruppe V₂ gebunden ist;
• K ist der Rest einer Kupplungskomponente, an den die nachstehend definierte fasserreaktive Gruppe V₁ oder die nachstehend definierte faserreaktive Gruppe V₂ gebunden ist;
• V, ist eine Gruppe der allgemeinen Formel (2a) die an D oder K gebunden ist, in welcher
• R ein Wasserstoffatom oder eine Alkylgruppe von 1 bis 4 C-Atomen ist und
• X eine gegebenenfalls substituierte Aminogruppe oder ggf. verätherte Hydroxygruppe oder eine Thioäthergruppe bedeutet;
• V₂ ist eine Gruppe der allgemeinen Formel (2b) die an D oder K gebunden ist und in welcher W eine direkte Bindung oder eine Gruppe der Formel ist, worin AIk eine niedere Alkylgruppe ist;
• Z ist die Vinyl-, die β-Sulfatoäthyl-, die ß-Thiosulfatoäthyl-, die ß-Chloräthyl- oder die β-Acetoxyäthyl-Gruppe.

Diese neuen Metallkomplex-Azoverbindungen besitzen faserreaktive Farbstoffeigenschaften und färben beispielsweise Cellulosefasermaterialien und Wolle in farbstarken und echten Tönen; sie lassen sich analog bekannten Verfahrensweisen, beispielsweise durch Umsetzung einer entsprechenden metallfreien, die faserreaktive Gruppe V₂ und ebenso eine Aminogruppe enthaltenden Azoverbindung, oder von zwei solcher konstitutionell verschiedenen Azoverbindungen, mit einem chrom- oder kobaltabgebenden Mittel und anschließende Umsetzung mit einer Verbindung der allgemeinen Formel (4) in welcher X die obengenannte Bedeutung hat, herstellen.

Description

The invention relates to a process for the production of water-soluble metal complexes 1: 2 with azo compounds, i.e., the technical field of fiber-reactive complexes of azo dyes with metals.

New, valuable, water-soluble, symmetric and asymmetric chromium complexes 1: 2 and cobalt complexes 1: 2 with monoazo compounds of formula 1 have been found

P - Vf d ~ n = nk - ^v 2.

(1) and their mixed chromium complexes 1: 2 and cobalt 1: 2.

In the case of symmetrical metal complex compounds of 1: 2, two identical metal-free monoazo compounds of general formula 1 are always complexly bound with metal, whereas in asymmetric metal complex compounds of 1: 2 two different monoazo compounds of general formula 1 are always complex bound with metal. The 1: 2 mixed metal complexes of the present invention are mixtures of two different symmetric compounds of one asymmetric 1: 2 chromium complex or cobalt 1: 2 of two different metal-free monoazo compounds of formula 1.

In the above general formula 1, the general symbols have the following meanings:

Y ₍ represents a hydroxy or carboxy group capable of complexing with a metal which is bonded ortho-to k and bridged to residue D,

D represents a radical of a diazo component, to which is bonded further defined group VI reactive towards the fiber or a further defined group V ₂ is reactive toward fiber benzene nucleus which is optionally further substituted with a substituent selected from the group that is formed by sulfo, alkyl having 1 to 4 carbon atoms, C 1 -C 4 alkoxy, nitro, carboxy, sulfamoyl, carbamoyl, C 1 -C 4 alkyl monosubstituted or disubstituted carbamoyl or sulfamoyl, N-phenylcarbamoyl, N-phenylsulfamoyl, -methyl-N-phenylcarbamoyl, N-methyl-N-phenylsulfamoyl, chlorine and bromine, or a naphthalene ring optionally substituted by one or two sulfo groups,

238694

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Y ₂ represents a hydroxyl group capable of forming a metal complex; * -K-Y ₀ means the residue of a coupling component of a naphthol to which a naphthalene core K is defined as a fiber-reactive group VI as defined below or a fiber-reactive group V ₂ as defined below, is an azo group in the ortho position to the Y2 radical and which is optionally still substituted by one or two sulfo groups, or is a 1-phenyl- or 1-naphthylpyrazol-5-on-4-yl radical to which the azo group is attached at the 4-position, and which is substituted at the 3-position by a carbamoyl, C 2 -C 5 alkoxycarbonyl, phenyl, methyl or carboxy group and whose phenyl residue at the 1-position is substituted by a fiber reactive group VI as defined below or a reactive group V 2 as defined below which is optionally further substituted by one or two substituents selected from C1 -C4 alkyl, C1 -C4 alkoxy, chlorine, bromine, C1 -C4 alkanoylamino, carboxy and sulfo and in which the naphthyl radical is in the 1-position is substituted with a further defined V 1 or V 2 group and is optionally further substituted with a sulfo group and one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, (C 1 -C 4) alkanoylamino, carboxy and chloro; or one or two sulfo groups, or is a radical of formula

HIM

I C — CH3 — C — CO — NH — phenyl.

or

HIM

AND

C — CH3

II '—C — CO — NH — naphthyl in which the phenyl residue “phenyl” is substituted with a fiber reactive group V ₁ or V 2 as defined below and optionally is further substituted by one or two substituents selected from the group consisting of an alkyl group of 1 to 2 C 4 -C 4 alkoxy, C 1 -C 4 alkoxy, chloro, carboxy, sulfo, carbamoyl and sulfamoyl, and in which the naphthyl residue "naphthyl" is substituted with a fiber-reactive group V 1 or V 2 as defined below optionally further substituted by a sulfo group and one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro and carboxy, or one or two sulfo groups,

V _T represents a group of formula 2a

which is bound to residue D or K, and wherein

R represents a hydrogen atom or a (C1-C4) alkyl group, such as an ethyl group and in particular a methyl group, and

X represents a group of formula -O-R ¹ · '(2c), -S-R 2 (2d) or

R3 /

—N (2e) \

R-- ‘where

R 1 and R 2 are each C 1 -C 4 alkyl optionally substituted by one or two substituents selected from the group consisting of acetylamino, hydroxy, sulfato, C 1 -C 4 alkoxy, phenyl, naphthyl, and phenyl substituted sulfo, carboxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro, sulfamoyl and / or carbamoyl, naphthyl, naphthyl substituted with sulfo, carboxy, C 1 -C 4 alkyl carbon atoms, C 1 -C 4 alkoxy, chlorine, sulfamoyl and / or carbamoyl, sulfo and carboxy, or phenyl or naphthyl which may be substituted with substituents selected from the group consisting of carboxy, sulfo, alkyl groups C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy, hydroxy and chloro; and

R 3 represents a hydrogen atom or an optionally substituted alkyl group as defined for R 1 or represents alkenyl

group being from two to four carbon atoms, or represents a cyclohexyl radical and is hydrogen or an optionally substituted alkyl group defined for R ^l, or an alkenyl group having 2 to 4 carbon atoms or optionally substituted phenyl or naphthyl radical which is as defined for the symbol R ^L wherein R ³ and R ^{Z |} they may have the same or different meanings, or

R ³ or R 6 together with the nitrogen atom form a heterocyclic ring containing a C 4 -C 7 alkylene radical or 2 or 3 C 1 -C 4 alkylene radicals and 1 or 2 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, such as a morpholine, piperidine or piperazine ring,

V ₂ is a group of formula 2b-W-SOn-Z (2b) which is bonded to the radical D or the radical K, wherein:

W represents a direct bond or a group of formula -NH-, -N-, -CH ₂ - or

Alk is _{-CH2 -CH2} -, where

Alk is C 1 -C 4 alkyl, wherein W is preferably a direct bond;

Z is vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-chloroethyl or β-acetoxyethyl.

The groups V ₁ and V ₂ are preferably not simultaneously simultaneously bonded to the group D or K.

As used herein, "lower" means that the alkyl or alkylene group in the group or compound contains 1 to 4 carbon atoms and the alkenyl group contains 2 to 4 carbon atoms. Lower alkyl groups are preferably ethyl and especially methyl; lower alkoxy groups are preferably ethoxy and especially methoxy.

Substituted lower alkyl groups are, for example, alkyl groups having 1 to 4 carbon atoms which are substituted by one or two substituents selected from the group consisting of acetylamino, hydroxy, sulfato, lower alkoxy, phenyl, naphthyl, and phenyl which is itself substituted with sulfo, carboxy, lower alkyl, lower alkoxy, chlorine, sulfamoyl and / or carbamoyl; furthermore a naphthyl group, which is itself substituted by a sulfo group, a carbothoxy group, a lower alkyl group, a lower alkoxy group, chlorine, a sulfamoyl group and / or a carbonyl group, and in particular a sulfo group and a carboxy group.

A cycloaliphatic group is, for example, a cyclohexyl group. Aryl groups are preferably phenyl and naphthyl. These groups may be substituted, for example, by substituents selected from the group consisting of carboxy, sulfo, lower alkyl, lower alkoxy, hydroxy and chloro.

The groups of formula (2e) are preferably an amino group, furthermore an amino group which is mono- or di-substituted by a lower alkyl group such as ethyl or methyl, furthermore an amino group substituted by a lower alkyl group and a lower carboylalkyl or lower sulfoalkyl group or phenylamino or naphthylamino group; their phenyl naphthyl moieties may still be substituted by methyl, methoxy, chloro, carboxy and / or sulfo, and their nitrogen atoms may still be substituted by lower alkyl.

The groups of formula 2c are preferably lower alkoxy, such as ethoxy, or methoxy or phenoxy, which may be substituted with one or two sulfo groups.

The groups of formula 2d are, for example, lower alkyl mercapto groups.

Radical D is preferably a benzene nucleus which is bonded to the above-defined group _B preferably Y is carboxy and hydroxy group in particular, ortho к azo group and to which is bonded above-defined group V _X or a fiber-reactive group as defined above, V ₂ reactive and which may still be substituted by one substituent selected from the group consisting of sulfo, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, carboxy, sulfamoyl, carbamoyl, carbamoyl or sulfamoyl mono- or disubstituted by C1 -C4 alkyl, N-phenylcarbamoyl, N-phenylsulfamoyl, N-methyl-N-phenylcarbamoyl, N-methyl-N-phenylsulfamoyl, chloro and bromo; preferably with a sulfo group, a methyl group, an ethyl group, a methoxy group, ethoxy, carboxy, and chlorine. Likewise, the radical D is preferably a naphthalene nucleus in which the group Y ₁ located in the ortho-position k to the azo group is a hydroxyl group and to which a group V as defined above is bonded. fiber reactive or fiber reactive group V ₂ as defined above and which is optionally further substituted by one or two sulfo groups, and preferably is substituted. ·

The moiety —K — Y2 is preferably a naphthol moiety to which the above defined group V ₍ fiber-reactive or the above defined V2-reactive group V) is bonded via the residue K and on which the azo group is in the ortho position to a hydroxyl group and in which the naphthalene core K 'is still optionally substituted with' one 'or two sulfo groups, and is preferably substituted.

Further, the —K — Y ₂ radical is preferably a 1-phenyl or 1-naphthylpyrazol-5-one-4-yl radical to which the azo group is attached at the 4-position and which is substituted at the 3-position by a carbamoyl group - lower -alkoxycarbonyl, 'phenyl, methyl' or carboxy, preferably methyl '-' and 'carboxy', and 'its phenyl moiety - - located in the - 1 position is substituted with the same as defined by' fiber-reactive 'group or 'above-defined group in the reactive _2' and a fiber ₇ is s optionally substituted with thee one or two, substituents selected from the group consisting of alkyl 'group having 1 to 4 atoms. atoms · C1 - C4 'carbon' are chlorine, bromine, alkanoylammoskupinou s - ^'1-4: alkyl - CO-, carboxy and sulfo, and Target residue - located in the 1-position is - - as defined above substituted by a group - - V as defined above or a group - V ₂ 'a- is optionally also' substituted with one sulfo group and one substituent selected from the group which is formed 'is a methyl group, an ethyl group, - methoxy, ethoxy ^^^ d Preferably, it is optionally substituted with one or two sulfo groups, and particularly preferably is substituted with C1-4 alkyl, C1-4 alkyl, carboxy and chloro. ; , u ·

Radical -K-Y ₂ is preferably a radical of the formula 'ho'.

_C-CH3

-. Ц, -, —C — CO — NH — phenyl —— ^{; 1} '- · or -.-- 5

HO-1-C-N-C-Co-NH-Naphthyl, ^R '''·' ··· · · Ί ''. H) in which the phenyl radical "phenyl" is substituted ^{by a} silane-reactive group or a fiber-reactive group V9 as defined above and is optionally still - substituted - one. or with two substituents - selected from the group consisting of alkyl having from 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, carboxy, sulfonyl, carbamoyl and saltfamoyl and in which háftylový "residue ^1" naphthyl "'substituted' as defined above, a group V _{- reactive - -vůči vláknům- '- as defined hereinbefore or a group of fibers reaktivní''vůči V2 - -, and optionally also' is ^substituted: with one - sulfo and one-. stibstitueltem-- selected -from the group 'consisting of TERA -methylovou'skupinou - ethylovoú- group · methoxy, eťhoxyskupinoup' and chlorine - carboxy - or is preferably optionally substituted by one or two sulfo groups, and ^o is particularly preferably substituted by them.

The novel metal complexes of the composition 1: 2 and the mixed metal complexes 1: 2 according to the invention may be present in the form of free acid or in the form of their salts, preferably in the form of salts, in particular in the form of alkali salts. metals and alkaline earth metals, preferably of ^them: in the form of salts of sodium, potassium and calcium. These compounds - are - preferably used in the form of alkali - metals to ⁵ - Dyeing - and printing natural or - 'regenerated cell lOžových fiber -' ^materials: - or natural; reseneřováných: · or synthetic polyamide -vláknitých - materials, ⁵ As well as leather. An object of the present invention is a process for the preparation of ^b and - defined compounds of the general formula - wherein: - the compound of the general formula T 1 - - ^;

- ··; · <D-A '-'··> · '(· II)' · '. ^·::. .: - \; . ; . ', in which ^Ί - <· ^su- ·: · -. . s; - -,. ·· -., '

D is as defined above; - - ^; -

A represents an amino group —NH2 - - - - or represents a group of the general formula - (a) - - not- bo (-b) buiShe: -Η-m-· · -; ^;; ; · '. ·; · T: '. 'TT ^; --- _S i; - ·· moderate л ·  . . -i? -: ·· :: · г- Τ: · :: <* no ..,. ·,.  Λ · ϋ '' ..,  · '·' -i .ni · . '/ ·. . :. · С те ^1! · '' · '- λ '^; ττ mol Т'ТТТТ · .- EOU

Ί ^; · Π * 10

in which

R, R ¹ , M and Hal have the meanings given above, in the case of an amine of the formula II in which A is the aforementioned amino group, after diazotization to the diazonium salt, it acts with a compound of the formula III

in which

R 6 ', R ^3' and Y 'have the meanings given above and

B is a hydrogen atom or a group of formula (b ‘) or (c‘) a pin of formula (b) when B is a hydrogen atom.

The above process of the invention can be illustrated in more detail by reacting a compound of formula I or two different compounds of formula 1 in which the radicals D and / or K are always different from each other with a reagent providing chromium or cobalt in. aqueous medium, at a pH between 3.5 and 7.0, preferably between 5.0 and 6.5, at a temperature between 50 and 130 ° C, preferably at a temperature between 80 and 100 ° C, at atmospheric pressure or at elevated pressure in a closed vessel, or with a symmetric or asymmetric 1: 2 chromium complex or a 1: 2 cobalt complex compound or a 1: 2 mixed chromium complex or a 1: 2 mixed cobalt complex compound with metal-azo-azo compounds of formula 3

in which (3)

Y 1, Y 2, R 2 and V 2 have the above meanings and

D is a diazo moiety to which an amino group of the formula —N (R) H, or a group as defined above, is attached, and

K is the rest of the coupling component to which the amino group of the formula -NN (R) H or V2 as defined above is bonded, monoacylated by treatment with quanuric chloride, and the dichloro-s-triazinylamino compound so produced is then reacted with a compound of formula II-X wherein X is as defined above, or slouR, R ^1, M and Hal have the above meanings, a represents an amino group if B is a group of formula (b'j, a represents a group of formula (a) when B is a radical of formula (c *) and A stands for 3 ο ο У '1

* reacting the value of formula 3 as defined above with a compound of formula 4

Cl с.лУх (41 in which

X is as defined above.

The reactions of the compounds of the formula 3 with cyanuric chloride or with the compound of the formula 4 carried out in these processes according to the invention are carried out analogously to known methods of such acylation reactions of amino compounds with chlorotriazine derivatives. These reactions are carried out preferably in the aqueous phase or also in the aqueous-organic phase, for example using acetone, glycol dimethyl ether, glycol ethyl ether, tetrahydrofuran or dioxane, at a temperature between 5 and 80 ° C, preferably between 10 and 60 ° C and at a pH between 2 , 0 and 6.0, preferably between 3.0 and 5.0.

To produce pure symmetrical metal complexes of 1: 2 with azo compounds, a metal-free azo compound of formula 1 or 3 is used in twice the equivalent amount and reacted with a chromium or cobalt-providing agent under the conditions of the above process of the invention. from above, by treatment with cyanuric chloride and a compound of formula Η-X or a compound of formula 4. Alternatively, a 1: 1 chromium complex or a 1: 1 cobalt complex with a monoazo compound of formula 5a or 5b can be reacted

(53)

í 5b)

D, K, V, V2 and R have the meanings given above,

Me ⁽ +) means a cation of chromium or cobalt and ·

A ^(_) represents a colorless anion, such as a chloride or sulfate anion,

Y: j represents a divalent radical capable of complex bonding with a metal, such as a carbonyloxy group and preferably an oxygen atom, which is bonded ortho-to the azo group on the radical D,.

Y4 represents a divalent radical capable of forming a complex bond with a metal, such as a group of the formula —NH— or an oxygen atom that is bonded to the radical K in an ortho position to the azo group, wherein the group Vt is bound to the radical D or K, -N (R) H is bound to the radical D or K, and V2 is a group bonded to a radical D or K, with a metal-free azo compound of the formula obecnéhc 1 or 3, in which D, K, V _b V 2 and R as well as H-Y ₃ and H-Y 4 are identical with the residues D, K, V _b V 2 and R as well as Yt and _Y2, in equivalent amounts analogously to known methods, for example in aqueous or aqueous-organic medium, for example using ethylene glycol dimethyl ether or ethylene glycol monomethyl ether, ethylene glycol diethyl ether or ethylene glycol monoethyl ether, ethylene glycol or polyglycols, at a temperature of between 40 and 105 T, preferably between 80 and 100 ° C, and at a pH of between 4.5 and 9.0, preferably between 6.0 and 8.0, optionally followed above. said ac ylation using a compound containing the same group to group V _b

Asymmetric metal complexes of 1: 2 with the az compounds of the invention can be prepared under the above reaction conditions in pure form or almost in pure form by reacting a 1: 1 chromium complex or a 1: 1 cobalt complex with the monoazo compounds 5a or 5b. with a metal-free compound of formula 1 or 3, the mono-components of the two starting compounds being different from each other, optionally with the following acylation reactions as described above. This reaction of a 1: 1 complex metal compound with a structurally other metal-free azo compound to form an asymmetric 1: 2 complex metal compound with a monoazo compound of the invention can be carried out analogously to known methods, for example in an aqueous or aqueous-organic medium, for example using ethylene glycol dimethyl ether or ethylene glycol monomethyl ether; ethylene glycol diethyl ether or ethylene glycol monoethyl ether, ethylene glycol or polyglycols, at a temperature between 40 and 105 ° C, preferably between 80 and 100 ° C, and at a pH between 4.5 and 9.0, preferably between 6.0 and 8.0.

In order to produce the 1: 2 chromium or 1: 2 cobalt mixed complexes according to the invention, one of the above-mentioned processes according to the invention is reacted by reacting one molar amount of two different metal-free monoazo compounds of formula 1 with chromium or cobalt-providing agents. aqueous medium at a temperature between 40 and 105 ° C, preferably between 80 and 100 ° C and at a pH between 4.5 and 9.0, preferably between 6.0 and 8.0. For example, chromium or cobalt-providing agents are commonly used chromium salts and cobalt salts, such as, in particular, chromium (III) chloride, chromium (II) sulfate, chromium (III) acetate, chromium (III) fluoride and chromium (III) sulfite, as well as cobalt (II) chloride, sulfate, acetate and bicarbonate. According to the invention, mixtures of three different complex metal compounds 1: 2 are obtained, i.e. one symmetrical complex monoazo compound 1: 2 derived from the used metal-free monoazo compound, one symmetrical complex monoazo compound with metal 1: 2 derived from the other metalloo monoazo compound and asymmetric with a metal 1: 2 derived from both structurally different metal-free monoazo compounds.

Complex monoazo compounds with chromium: 1 which serve as starting materials, preferably for asymmetric metal complexes 1: 2 with azo compounds, correspond to the general formulas 5a or 5b and can be prepared by a known process by reacting metal-free monoazo compounds of the formulas 1 and 3 in aqueous water. an organic or organic phase, for example using aliphatic alcohols, polyalcohols or glycol ethers as an organic medium, at a temperature between 80 and 100 ^° C at atmospheric pressure or at elevated pressure in a sealed container with chromium donating agents such as chromium salts, preferably chloride chromium or chromium sulphate.

1: 1 cobalt complexes with monoazo compounds corresponding to formulas 5a and 5b which serve as starting materials and which are preferably used to produce asymmetric cobalt 1: 1 complexes with a monoazo compound can also be prepared in a manner known per se by reacting metal-free monoazo compounds of formula 1 3 in the aqueous or aqueous-organic phase by treatment with cobalt, such as cobalt salts, for example cobalt chloride or cobalt sulfate, in the presence of ammonia, pyridine, C 4 -C 4 alkylenediamines or C 2 -C 4 dialkylene triamines temperature between 0 and 20 ^o C.

1: 2 metal complex compounds of the invention 1: 2 metal complexes according to the invention in which the radical Z is a 1-sulfatoethyl group can also be prepared according to the invention by using the corresponding 1: 2 metal complex compounds or mixed metal complexes as starting materials 1: 2 with monoazo compounds corresponding to the general formulas 1 or 3, in which the radical Z represents an O-hydroxyethyl group, and these compounds are esterified (sulphated) in 95 to 100% sulfuric acid at a temperature between 0 and 20 ° C; by treatment with amidosulfonic acid in pyridine or picoline at a temperature between 50 and 100 ° C. The sulfa-ethylsulfonyl derivatives can optionally be converted to the p-thiosulfatoethylsulfonyl derivatives by treatment with sodium thiosulfate under weakly acidic conditions analogously to known production methods. After esterification or conversion to the thiosulfatoderivatives, the compounds of formula (3) are acylated by the above process of the invention to complex metal compounds of the invention.

As already described in the case of the preparation of the compounds according to the invention, complex metal compounds 1: 1 of the general formulas 5a and 5b are also possible, in which Z stands for [J] - (-) - (-) - (-) and optionally then reacting the compounds of formula 5b with acylated reactions from the outset for the compounds of the invention to form monoazo-metal complexes of formula 5a.

Aromatic amines which can serve as diazo components for the preparation of the monoazo compounds of the general formula 1 or 3 and thus for the production of the metal complexes 1: 2 and mixed metal complexes 1: 2 according to the invention are, for example:

_2-i aminofenols4- -hhddгoyyethulsulfon, and aminophenol-SJ-hydroxyethyl sulfonate, alpha-amin4-4 coiorfono - 5-hhydroxyethyl- sulfone,

2-Aminosensyl-4- unlfotoethulsnifon-6 ´-sulfonic acid,

2-Amino-phenol-4-fluoro-ethylsulfone;

2-aminophenol-vinyl sulfuifone,

-aminophenof-O-β-shenzylene-ethylene, α-amino-α-methylLenol-3-hydroxyethylsulfone,

2-aminosa-methylphosphonol-5-hydroxyethyl · sulfone,

2-aininophenol-4-vinylsulphon-6-sulphonic acid, α-amino-α (N -sulfatoethylsulfonyl) phenol, .alpha.-amino-.alpha. enol, asamino-4-methyl-5 '(N-moteyl-N-sulphatoethylsulfonyl) aminophenol,

2-amino-4-S-uulaateethulsn0fonblbeozoová acid, 4- _ammino-L-S ehiuuulfatoethylsnifonylbenzoová acid, a-amino-4 · vinytsulfonylbonzoová acid, .alpha.-amino-5-S ^ Uf.lfatoethslsnifonylbeozoová acid,

2-aminoOsO3: oSic-sulfo-oxo-benzoic acid, furthermore aromatic amines having a single acylamino group, which can serve, after diazotization and coupling and hydrolysis of acylamino groups, to react with chlorotriazines such as, for example,

4-acetylamino-2-aminophenol,

4-Acetylamino-2-aminophenoi-6-sulfonic acid,

5-acetylamino-4-aminophenol, α-amino-4-acylaminobenzoic acid, α-amino-5-acylaminobenzoic acid.

As coupling components for the production of the monoazo compounds of the general formula 1 or 3 and thus for the production of the metal complexes 1: 2 and mixed metal complexes 1: 2 according to the invention, for example, the coupling components of the naphthol series and aminonaphthol series can be used (e.g. acylaminonaphtholder). a lower alkanolamyloxy group, in particular an acetylamino group, which is hydrolyzed to an amino group after the coupling reaction, and in this form is then reacted according to the invention with quintriazibyldenate, or a group of the above-defined and defined general formula 2a), 1-arylpyrazolone series and 1- ( pyraznloo derivatives (e.g. in the form of their acylamino derivatives, the acylamino group being, for example, a lower aikannyl amino group, in particular an acetylamino group, which is hydrolyzed to an amino group after the coupling reaction and which are then reacted according to the invention with a chlorotriazinyl derivative, or a group of the above and defined formula 2a), acetoacetylarylide series, such as acetoacetylanilide and acetoacetylnaphthylamide series, and their aminoaryl derivatives (e.g. in the form of acylamino derivatives, wherein the acylamino group may be e.g. the reaction hydrolyzes to an amino group which is then reacted according to the invention with a chlorotriazine derivative or a group of the aforementioned and defined general formula 2a) as well as an aminonaphthalene series and aniline series (wherein the coupled amine-naphthalene and aniline derivatives may still contain bound acylamino) the acylamino group, as mentioned above for the other coupling components, is, for example, the lower alkanoylamino group to be hydrolyzed, or the group of formula (2a) as defined above, which are usually used for metal complexes with azo fiber-reactive dyes. Examples of such coupling components are:

b-nafiol 4- -hhydгχyyethylsuifbn _s, b-naphthol-5 --- hddroxyethylsuifon,

1- Baftol-6- / 3-hydroxyoxyethylsulfob,

2-Baftol-O- (4-hydroxyethylsulfonyl)

Nafi-2: 6-ol - hhydroxyethylsuifon NAFL and B: 7-ol - ^ hydгoxyethylsuifon and their 0-sulphate-, / β-thiosulfato-, β-chloro and ₁ ¢ -acetooyythyísulfnn- and vinylsulfon- derivatives,.

1-N-acylamino-S-naphthol-N-disulfonic acid,

1-N-acylamino-β-naphthol-4-disulfonic acid.

acid, · -

2-N-acylamino-8-naphthyl-O-sulfonic acid

2-N-acylamino-8-naphthiol-6-sulfonic acid,

2- (4-acylamino-5-naphthiol-7-sulfonic acid),

2’N-methyNN-acylamino-b-naphthol-6-sulfonic acid

2-N- (4-ethyl-N-acylamine-4-O-naphthalene) -7-sulfonic acid,

3-N-acylamino-2-naphthol-7-sulfonic acid a

3-N-acylamino-2-naphtholol-7-phenylphosphonic acid, wherein the acylamino group in these compounds, as mentioned above, serves for the following hydrolysis and is preferably represented by the acetylamino group or the remainder of the above formula 2a);

1- (S, S-Sulfonylmethylsulfonyl) Kenyl-methyl-pyrazin-O-one,

1- (1'-O-thion-7-thiomethylsulionbiphenyl-3-methylpyrazol-O-nn),

1- (η 5 -Sulfonylmethylsulfonyl) phenyl-3-methylpyrazol-O-nb,

1- (4‘-O ^-thion71faaoethylsulionbiphenyl11Oomethylpyrazin-O-one),

1- (3 ‘- (> - 7 7 -phatoothblsulfnoyl) phenyl-1-carboxypyrazin-O-nb),

1- (4 ‘- 1-thiooslphatoethane 7 lf о n у i) bitches 1-3-methoxycarbonylnylpyrrole-O-nn,

1- (2‘-methoxy-O O -, (- sl at-atoththylsulfonyl) phenyl-1-carbonylpyrazole-Onn),

1- (4'-N-methyl-N-, 3,77-phthaethylsulfonylamino) -phenyl-1-methylpyrazol-O-one,

1- (1'-N-methyl-1'-N-aminobiphenylphenoxy) phenyl-1-methoxycarbonyipyrazol-O-nn;

1- (-α-acylamino) phenyl-1- or -naphthyl-pyrazolo-n-derivatives whose acylamino group serves, as mentioned above, after the coupling reaction for hydrolytic conversion to the amibnyl group or is a residue of the above-defined general formula 2a, such as

1- ^(2-1 sulfonyl 4'-N-acetylamino) feiiyl t-methylpyrazolS-one,

1- (2‘-Sulfo-5‘-N-acyeylphenyl-1-methylpyrazin-O-oo),

1- (4-sulfon-4- (N-acetylamino) phenoxy-1-methoxycarbonylpyrazol-O-one),

1- (2 ‘, ‘‘isisisisis‘ acetylam‘) - acetylamine phospholoyl

-methoxycarbinylpyrazole-Olno,

1- ⁽ 1'-carboxy-4'-acetylamino) pheoyl-31

- N-acetoacetylamino-2-methoxy-5- (3-sulfatoethylsulfonylbenzene), 1-N-acetoacetylamino-2-methoxy-5-methyl-4- / 3-methoxycarbnoylpyrazol-O-one; -thlosulfatoethylsulfonylbenzene, 1 N-acetoacetylamino-3- (N-methyl-N-vinylsulfonylamino) benzene and 1 N-acetoacetylamino-2-methoxy-5- (N-methyl-N- (5-thiosulfatoethylsulfonylamino) benzene, 1 N-acetoacetylamino-4- aminobenzene-3-sulfonic acid, 1 N-acetoacetylamino-3-aminobenzene-4 ... -sulfonic acid, 1 N-acstoacetylamino-4-aminobenzene-2,5-disulfonic acid and

N acetoacetylamino-3-aminobenzene-2,4-disulfonic acid. ·,

Of the symmetric and asymmetric chromium complexes 1: 2a of cobalt 1: 2 with monoazo compounds and their mixed complexes according to the invention, those corresponding to formulas 6, 7 or 8 can be highlighted.

an alkali metal or an alkaline earth metal cation, such as, in particular, a sodium or potassium cation,

Me means a chromium atom or a cobalt atom in which

M ^(+> represents a hydrogen atom or the equivalent of a cation of a monovalent, divalent or trivalent metal, preferably a cation η denotes a number of 0 or 1, preferably 0,

_T is as defined above for formula 2a, wherein R is preferably hydrogen and X is preferably lower alkoxy and particularly preferably amino of formula 2e as defined above, wherein R ³ is hydrogen or lower alkyl, such as especially methyl, and ethyl optionally substituted with carboxy or sulfo; and

R ⁴ is preferably a hydrogen atom or a lower alkyl group such as, in particular, a methyl or ethyl group, which is optionally substituted by a carboxylic acid residue or a sulfonic acid residue or optionally a sulfo group substituted by a phenyl residue, or preferably a phenyl group optionally substituted by one or two substituents selected from the group consisting of sulfo, carboxy, methyl, ethyl, methoxy, ethoxy and chloro, preferably 1 or 2 sulfo, both of which are R ^; and R ⁴ may be the same or different from each other,

V ₂ is as defined above for formula (2b), wherein W 'is preferably a direct bond and Z is preferably a vinyl or β-thio sulfatoethyl group or particularly preferably a St sulfatoethyl group,

_Dt represents a benzene radical in which the carbonyloxy or oxy group is ortho-attached to the azo group and which preferably contains no other substituents in addition to the two groups and the Vj group or is further substituted by methyl, ethyl, methoxy, ethoxy, carboxy, sulfamoyl or a carbamoyl or chlorine or bromine atom, or preferably a sulfo group, or D (represents a naphthalene radical in which the carbonyloxy or oxy group is ortho-attached to the azo group and, in addition to these two groups and V, optionally contains one or two sulfo groups as additional substituents,

Do represents a benzene radical in which the carbonyloxy or oxy group is ortho-attached to the azo group and which, in addition to these two groups and the group V2, contains no further substituents or is further substituted by methyl, ethyl, methoxy, ethoxy, nitro, carboxy, sulfamoyl or carbamoyl or chlorine or bromine, or preferably sulfo, or D2 represents a naphthalene radical in which the carbonyloxy or oxy group is ortho-attached to the azo group. and which in addition to the two groups and the group V ₂ may contain one more sulfo group *

Kt is a naphthalene residue in which the oxy group is ortho-attached to the azyl group and which may contain, in addition to the two groups and the V2 group. yet as another sulfo substituent, or ‘

K is 1-phenyl-. or 1-naphthyl-pyrazol-4,5-ylene, which. is substituted in the 3-position by carbamoyl, lower alkoxycarbonyl, such as methoxycarbonyl and ethoxycarbonyl or phenyl, or preferably methyl or carboxy, and whose phenyl residue in position 1 contains no other substituent besides V2 or is further substituted by 1; 2 substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine and / or one substituent selected from the group consisting of bromine, carboxy and sulfo or one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine, or one sulfo group and whose naphthyl residue in position 1 contains no other substituents besides the group V ₂ or is further substituted by one or two uuo groups, or

K, as the coupling moiety, is an acetoacetylaminobenzene or acetoacetylaminonaphthalene residue, wherein the benzene moiety contains no other substituent besides the group V2 or is further substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine and / or a substituent selected from the group consisting of bromo, carboxy and sulfo or one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro and one sulfo and the naphthyl residue contains no other substituent or is substituted with one or two sulfo groups in addition to V2,

K2 represents a naphthalene radical in which the oxy group is ortho-attached to the azo group and which, in addition to the Vt group, is substituted by one or two sulfo groups, or

K ₂ · I1 represents phenyl- or naphthyl-1-pyrazol-4,5-ylene radical in position 3 is substituted with a carbamoyl group ,. a lower alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, or a phenyl group, or preferably a methyl or carboxy group, and whose phenyl residue in position 1 does not contain

next group at _t no substituent or is led, being substituted with one or two substituents selected from the group which consists of methyl, ethyl, methoxy and ethoxy, and / or one substituent selected from the group consisting of chlorine, carboxy and sulfo, or one a substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chloro and one sulfo group and the naphthyl residue in position 1 contains no other substituent besides Vj or is substituted with one or two sulfo groups next to Vj, or

K ₂ is as the remainder of the coupling component an acetoacetylaminobenzene or acetoacetylaminonaphthalene residue, wherein the benzene moiety in addition to V 1 contains no other substituent or is further substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chloro and / or one carboxy or one sulfo group or one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chloro and one sulfo group, the naphthyl residue of which contains no other substituent besides Vj or is adjacent to V more preferably _T is substituted by one or two sulfo groups.

The metal complexes of formula 7 are asymmetric metal complexes of 1: 2 with the monoazo compounds of the invention. Complex compounds with metals of formula 6 and formula 8 are symmetric metal complexes of 1: 2 with monoazo compounds according to the invention, provided that the radicals V _b V-2, n, D _t and K 2 or D ₂ and K ₂ are respectively in the same metal complex compound have the same meaning. However, these compounds represent asymmetric metal complexes of 1: 2 with monoazo compounds when one or more pairs of these residues have different meanings from each other.

In particular, both symmetrical and asymmetric 1: 2 chromium and cobolt 1: 2 complexes of the metal-free monoazo compounds of the general formulas 9, 10, 11, 12, 13 or 14 should be emphasized.

Italy (11)

ÍA

HIM

OH

HO-C-CH 1 N = H-C in which

Yt is carboxy or preferably hydroxy,

M, R, X and Z have the above-mentioned, particularly preferred meanings, m is 0 or 1 (and when m = 0 is hydrogen), p is 1 or 2,

R 5 represents a carbamoyl group, a lower alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, preferably a methyl group or a carboxylic acid residue,

R ⁶ represents a hydrogen atom, a lower alkyl group, a sulfo group or a chlorine atom,

R 7 represents a hydrogen atom, a lower alkyl group, a sulfo group or a chlorine atom and

R ⁸ represents a hydrogen atom or a lower alkyl group, wherein R 6, R ⁷ and R 8 may also be the same or different, and the lower alkyl group is preferably an ethyl group and in particular a methyl group.

Further, the symmetrical and asymmetric chromium complexes of 1: 2 and cobalt complexes of 1: 2 with monoazo compounds of the metal-free monoazo compounds of formulas 15, 16, 17, 18, 19 or 20 can be highlighted from the metal complexes of the invention

^(15> tscLMi (16 7

From ό ΰίΗ

in which

M, R, X, Z, R ⁵ , R ^G , R ⁷ , R ⁸ , Y _{b and} m have the above-mentioned particularly preferred meanings,

R ⁹ represents a hydrogen atom, a nitro group or a halogen atom such as bromine and preferably a chlorine atom,

R ^{, f)} represents a hydrogen atom, an acetylamino group or a benzoylamino group,

R ^u is hydrogen, sulfo, acetylamino or benzoylamino, lower alkyl group such as ethyl and especially methyl or chlorine atom, and R is ^H, R ⁷ and R ⁸ may be mutually the same or different meanings, and q is an integer of the first

Among the 1: 2 complex metal compounds of the invention, the asymmetric 1: 2 cobalt chromium 1: 2 complexes with the mono azo compounds of the invention, two metal-free monoazo compounds of formulas 9 to 14 or two metal-free monoazo compounds of formulas 15 to 20 or one metal-gray monoazo compounds of formulas 9 to 14 and one monoazo compound of formulas 15 to 20.

The separation and isolation of the 1: 2 metal complex compounds and the 1: 2 metal complex complex compounds produced by the process of the invention from the reaction solutions can be carried out by generally known methods, such as either precipitation from the reaction medium using electrolytes such as chloride, sodium or chloride. % of potassium potassium, by evaporating the reaction solution, for example by spray drying, a buffering agent may be added to the reaction solution.

1: 2 Metal Complex Compounds 1: 2 metal complexes of the invention are fiber reactive and have very good dye properties. They can therefore be used for dyeing and printing hydroxyl- and / or carboxamido-containing materials. Solutions resulting from the synthesis of the compounds according to the invention may also be used, optionally after addition of a buffer and optionally after concentration, which is supplied directly as a liquid dye preparation for dyeing.

The invention therefore also relates to the use of the compounds according to the invention for dyeing and printing hydroxyl and / or carboxamido-containing materials, preferably in the form of fibrous materials, in particular in the form of textile fibers, such as yarns, windings and fabrics. . It is possible to proceed analogously to the known processes by applying the 1: 2 metal complexes of the invention with the 1: 2 metal complexes in dissolved form to the substrate or impregnating the substrate and then fixing it on or in the material, optionally under the effect of heat and / or optionally under the action of an alkaline active agent.

Materials containing hydroxyl groups are materials of natural or synthetic origin, such as cellulose fiber materials or regenerated cellulose materials and polyvinyl alcohols. (The cellulosic fibrous materials are preferably cotton, but also other vegetable fibers such as flax, hemp, jute, and frame fibers. The regenerated cellulosic fibers are, for example, viscose staple and viscose rayon.

Materials containing carboxamido groups are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal fibers, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The compounds produced by the process of the invention can be applied and fixed to said substrates, in particular to said fibrous materials, by application techniques known for complex dyes with water-soluble metals, in particular for water-soluble and fiber-reactive dyes. Such dyeing and fixing procedures are described in the literature in numerous places.

By docking or short bath pulling process, a good dye and good color composition is obtained on cellulose fibers, and the dye can be fixed in a conventional manner by dwelling at room temperature or at elevated temperature, for example up to about 60 ° (by steaming or dry heat). .

The compounds of the invention are preferably used for conventional cellulose fiber printing processes which can be carried out in a single phase, for example in the presence of sodium bicarbonate or other acid binding agents in a printing paste, followed by steaming the printed article at temperatures of 100-103 °. for example, by printing with a neutral or weakly acidic ink and then fixing the dye either by guiding the printed article through an electrolyte-containing hot alkaline bath, or by overprinting the printed article with an electrolyte-containing alkaline float followed by dwelling of the treated material or steaming or dry heat. Intensive prints with good contour status and clear white pool and excellent dye yield, which is almost quantitative. influenced by changing fixation conditions.

For dry heat fusion according to the usual thermofixation procedures, hot air at a temperature of 120 to 200 degrees (elsia) is used. In addition to the usual water vapor at a temperature of 101 to 103 ° (superheated steam and pressure steam at temperatures up to · 160 ° (.

The acid binding agents and agents for fixing the 1: 2 metal complexes with the 1: 2 metal complexes of the invention on cellulosic fibers are, for example, water-soluble alkali metal bases as well as alkaline earth metal with inorganic or organic acids or hot compounds they release alkali. Particular mention should be made of alkali metal hydroxides and alkali metal salts derived from mild to moderate inorganic or organic acids, with sodium and potassium compounds being preferred. Such acid binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium phosphate, aqueous phosphate, sodium trichloroacetate, water glass or sodium phosphate.

By treating the compounds according to the invention, optionally under the action of heat, with the acid binding agents, the compounds according to the invention, optionally under the effect of heat, chemically bind the compounds of the invention (dyes) to cellulose fibers. In particular, prints on cellulose or regenerated cellulose exhibit excellent wet stability after the usual post-rinse treatment to remove unfixed dye fractions, and moreover, unfixed dye fractions can be easily washed out due to their good solubility in cold water.

The dyeing of polyurethane fibers or natural or synthetic polyamide fibers is usually carried out from an acid medium. Thus, for example, acetic acid and / or ammonium sulfate and / or acetic acid and ammonium acetate or sodium acetate can be added to the dyeing bath to achieve the desired pH. It is recommended to add conventional leveling aids such as those based on the reaction product of cyanuric chloride with a triple molar amount of aminobenzenesulfonic acid and / or aminonaphthalenesulfonic acid or based on the reaction product, for example, stearylamine with ethylene oxide, in order to achieve a useful color uniformity. Generally, the material to be dyed is introduced at a temperature of about 40 ° (into the bath, where it is kept in motion for some time, the dyebath is then adjusted to the desired slightly acidic pH, preferably by the addition of acetic acid, and the dyeing is carried out at temperatures 98 ^C C.

The dyeing can also be carried out at the boiling point of the dyeing bath or at temperatures up to 120 ° C (under pressure).

The dyeings and prints obtained with the 1: 2a metal complexes with the 1: 2 metal complexes of the invention are characterized by very high dye yields. Accordingly, the compounds of the present invention provide color-intensive dyeing, the hues obtained by the dyes of the present invention being in a very wide range of colors depending on the chemical structure of the two metal-free monoazo compounds corresponding to Formula 1 or the selected combination. the dyes according to the invention consist.

Thus, the color shades obtained with the colorant according to the invention can vary from reddish yellow to violet and between green, olive, brown to gray.

Colorings and prints have very good fastnesses, such as manufacturing stability and durability. Particularly for dyeing and printing on cellulosic fibrous materials, good to very good light and wet fastnesses, such as various underwear fastenings such as 60 degrees Celsius or 95 ° C, acid and alkaline wash strength, water fastness and in seawater, acidic coloring, alkaline and acidic perspiration, pleating, ironing and abrasion.

Also of interest is the use of the 1: 2a metal complexes of the 1: 2 mixed metal complexes of the invention for dyeing wool using fiber reactivity. In particular, non-felting or low-felting wool can also be dyed [cf. for example, H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3, eds. (1972), pp. 295-299, in particular the wool treated by the so-called Hercosette procedure (p. 298); J. Soc. Dyers and Colorists 1972, 93-99, and 1975, 33-34] with very good constancy.

The dyeing of the wool is carried out by a conventional and known dyeing method by applying the fiber-reactive compound preferably by extraction from an acidic aqueous dye bath, preferably first at a pH of from about 3.5 to 5.5 and at the end of the dyeing time the pH is shifted to a pH range of neutral and possibly weakly alkaline, up to a pH of 8.5, in order to achieve a complete reactive bond between the dye and the fiber, which is virtually quantitative, especially when the desired high saturation is achieved.

The method described herein also applies to dyeing fibrous materials from other natural polyamides or from synthetic polyamides and polyurethanes. The dyeing is carried out at temperatures from 60 to 100 Έ, but can also be carried out in closed dyeing equipment at temperatures up to 106 ° C. Since the water solubility of the compounds of the invention is very good, they can also be used advantageously in conventional continuous dyeing processes. When using dyeing temperatures of 100 to 106 degrees Celsius, a high degree of bath exhaustion can be observed. The coloring shows a very good color composition. It is also possible to uniformly dye wool fibers of various provenance with the compounds according to the invention. Optionally, a conventional leveling agent such as N-methyltaurine can optionally be added to improve the leveling effects.

In the case of dyeing achieved by the compounds according to the invention with practically quantitative color fixation, it is generally possible to dispense with the usual additional treatment with ammonia on the dyeed article.

Using conventional fiber affinity dye compositions, the compounds of the invention also provide uniform dyeings on wool with a non-felting or low-felting finish. In addition to the high light fastnesses of these wool dyes, very good wet fastnesses, in particular excellent alkaline sweat stability and very good fastness to the linen at 60 [deg.] C., even high dyeing densities, should be emphasized.

The following examples serve to illustrate the invention. Parts are parts by weight, percentages are percentages by weight unless otherwise indicated. Parts by weight are parts by weight as kg: liter.

The compounds described in the following examples of the formulas are given in the form of free acids. Generally, these compounds are produced and isolated in the form of their sodium or potassium salts and used in the form of these salts for dyeing. Likewise, the starting compounds and components mentioned in the following examples, in particular in the table below, can be used in the reaction in the form of the free acid as such or in the form of its salts, preferably in the form of alkali metal salts such as sodium or potassium salts. .

Example 1

29.7 parts of 2-aminophenol-4- (3-sulfatoethylsulfone) was stirred in 150 parts of water after addition of 25 parts of aqueous 31% hydrochloric acid for 3 hours. 50 parts of ice are then added and 20 parts by volume of aqueous 5N sodium nitrite solution are slowly added dropwise for diazotization. After a positive reaction to the nitrites, the reaction mixture was stirred for 30 minutes at a temperature of 10-15 ° C, and then a slight excess of nitrite was decomposed with a small amount of amidosulfonic acid. To this diazonium salt solution was added 52.4 parts of 2- [3 [-chloro-5 - (3'-sulfophenylamino) -s-triazinyl] amino-5-naphthol-7-sulfonic acid as an aqueous suspension. The pH of the coupling mixture was adjusted to 6.8-7.2 by addition of sodium carbonate and maintained until the coupling reaction was complete.

In order to convert the metal-free azo compound so produced to a 1: 2 chromium complex, to this coupling solution is added three parts of chromium acetate corresponding to 2.6 parts of chromium and 13.6 parts of crystalline sodium acetate until the complexing with chromium is complete. The reaction mixture is heated to 95-100 ° C. The resulting dark blue solution is filtered and the chromium-azo compound complex of the invention is isolated from the clear filtrate in a conventional manner, for example by evaporation or spray drying. A black powder is obtained which, in addition to the inorganic salts of the electrolyte, contains a sodium salt of the compound of the formula

Í-J

This compound has very good dye properties and is well suited for dyeing and especially for printing cellulosic fibrous materials using the application and fixation methods customary for fiber-reactive dyes. Depending on the amount of this complex chromium compound used according to the invention, a reddish-gray to black coloring or printing with very good light fastness and very good wet fastness is obtained. It is particularly advantageous to note that, when printing cellulosic fibrous materials, the compound of the invention is almost quantitatively fixed to the fiber, so that the waste water produced during printing contains only minor amounts of this dye.

Example 2 ·

In order to produce the cobalt complex 1: 2 with the azo compound of the invention, the data contained in Example 1 is followed, but instead of chromium acetate, as many parts of cobalt (II) carbonate corresponding to 2.95 parts of cobalt are used in the metallization reaction. Mp 75-80 ° C. A dark bordeaux color solution of the compound of the invention is obtained. This compound is isolated from the above solution after filtration by evaporation or spray drying, the clear filtrate as its sodium salt together with the inorganic salts of the electrolyte as a dark brown powder.

This compound, represented in free acid form, has the formula u ο ϋ · J · i

CH 2 CH 2 OSO ₃ H

and, due to its good dye properties on cellulosic fibrous materials, the application and fixation methods customary for fiber-reactive dyes, intense, reddish-brown coloring and reddish-brown prints with good fastness. Especially when printing using this complex cobalt 1: 2 compound with the azo compound of the invention, near quantitative yields are achieved in fiber fixation.

Example 3

29.7 parts of 2-aminophenol-5 -? - sulfatoethylsulfone are stirred in 150 parts of water after adding 25 parts of 31% aqueous hydrochloric acid for 3 hours. Then 50 parts of ice are added and the diazotization reaction is carried out by slowly dropping 20 parts by volume of aqueous 5N sodium nitrite solution. When the reaction to the nitrites is positive, the reaction mixture is stirred for about 30 minutes at a temperature of 10-15 ° C and then the excess nitrite is decomposed in the usual manner. To the diazonium salt solution thus obtained was added as an aqueous suspension 47.2 parts of 2- (3'-chloro-5'N-ethylsNs-phenylamino-s-triazinyl) amino-8-naphthols-6-sulfonic acid and adjusted to pH 7 by addition of sodium carbonate. 0 to 7.2 and maintained at this value until the coupling reaction is complete.

To produce the chromium complex compound of the invention, so many parts of chromium acetate corresponding to 2.6 parts of chromium and 13.6 parts of crystalline sodium acetate are added to this azo compound solution. This reaction (chromium introduction is carried out at a pressure of 3 to 5 bar and at a temperature of 125 to 130 DEG C. A black solution is obtained which, after filtration, affords a clear filtrate. The compound of the invention is isolated by evaporation or spray drying as This powder contains, in addition to the inorganic salts of the electrolyte, a sodium salt of a compound of the formula

(-i (t) H, which has very good dye properties and on cellulosic fibrous materials, provides gray-to-black coloring and gray-to-black prints with very good fastness using application and fixation methods applicable to fiber-reactive dyes In this compound according to the invention, it is necessary to emphasize the near-quantitative fixation in cotton printing, and on a machine-washable wool, in particular by the so-called Hercosette process, it provides a chromium 1: 2 complex with a monoazo compound according to the invention used amount of reddish-gray to black coloring with very good fastness to light and excellent wet fastness.

Example 1 a d 4 ''.

In order to produce a 1: 2 chromium complex with the monoazo compound of the present invention, the process described in Example 3 is followed, but the 38.3 part of the 2- (3'-chloro-5'-methoxy-) coupling component used therein is replaced. S-rlazinyl] amino-8-naphthol-6-sulfonic acid After the introduction of chromium, a black colored solution is obtained which, after clarification by filtration, is spray-dried or evaporated to give a black powder which contains sodium salt in addition to inorganic electrolyte salts. compounds of formula

CHžCHžOSOOi.

which has very good fiber-reactive dye properties and provides, for example, on cellulosic fibrous materials in the presence of alkali, for example, the printing processes customary for fiber-reactive dyes, gray to black prints with very good fastness to use and high dye yield.

Example 5

A neutral solution of 31.3 parts of 2-aminophenol-4- (3-thiosulfaaoethylsulfone) in 150 parts of water is mixed with 20 parts of a 5N aqueous sodium nitrite solution and allowed to flow slowly to 50 parts of ice and 32 parts of 31% hydrochloric acid. Once a positive reaction to the nitrites is found, the reaction mixture is stirred for a further 30 minutes at 10-15 ° C and then the excess nitrite is decomposed with a small amount of amido sulfonic acid. To conduct the coupling reaction, 58.4 parts of 1- [3 '- (3'-chloro-5' - (2 '', 5 '' - disulf of enyl) amino) - was added to this solution of the diazonium salt as an aqueous solution. s-tl: (amino-amino) phenyl-3-carboxypyrazol-5-one. The pH of the coupling mixture was adjusted to 6.5 by addition of sodium carbonate and maintained until the reaction was complete.

Then, as many parts of chromium acetate as 2.6 parts of chromium and 13.6 parts of crystalline sodium acetate are added, the chromium complex forms at 95-100 ° C. Upon completion of this reaction (introduction of the chromate, the orange-red solution is filtered and the compound of the invention is isolated by evaporation or spray-drying) to give a brown powder which contains, in addition to the electrolyte salts, the sodium salt of the compound of formula

S0žCH2CH £S30 ₃ H

COOH

N = N

COOH

SO2CH2CH2CH3O3

This compound exhibits very good dyeing properties and provides orange cellulosic dyes, in particular prints, with very good fastnesses on cellulosic fibrous materials, such as cotton, using conventional application and fixation methods used for fiber-reactive dyes, especially in printing. in light and with very good wet fastness as well as very good fixation yield.

Example 6

19.9 parts of 2-aminophenol-4-vinylsulfone are dissolved in 150 parts of water with 32 parts of 31% hydrochloric acid. To this solution is added 50 parts of ice and diazotization is carried out in the usual manner using 20 parts by volume of 5% aqueous sodium nitrite solution. In the case of a positive reaction to the nitrites, the reaction mixture is stirred for a further 30 minutes at 10 to 15 ^° C, the excess nitrite is decomposed and an aqueous suspension of 43.5 parts of 1- (3 '* - chloro-5'-amino-) is added for coupling. s-triazinyl] amino-8-naphthol-3,6-disulfonic acid, the pH was adjusted to 6.8-7.2 by addition of sodium carbonate and maintained at this value until the coupling reaction was complete.

Then, as many parts of chromium acetate as 2.6 parts of chromium and 13.6 parts of crystalline sodium acetate are added, the chromating mixture is heated to 90-95 ° C. After completion of the metallization reaction, a blue-black solution is obtained, which is filtered.

The complex chromium compound of the invention is isolated by spray drying. A black powder is obtained which, in addition to the electrolyte salts, contains the sodium salt of the compound of the formula

This compound has very good fiber-reactive dye properties and provides, in particular in printing on cellulosic fibrous materials such as cotton, in the presence of alkali black prints with high light fastness and high wet fastness and with very good fixation yield.

ó J

4ϋ

Example * 7 ·

24.6 parts of 2-amino-4-acetylamino-phenol-G-sulfonic acid in 150 parts of water are stirred with the addition of 32 parts of concentrated hydrochloric acid for 2 hours. Then add 50 parts ice and then slowly 20 parts by volume 5N aqueous sodium nitrite solution. To the suspension of the palzonium salt obtained after the diazotization reaction is added

25.2 parts L-notto - 5-, 6 ^J -hydroxyethylsulfonu and 100 parts of ice. The pH is adjusted to 12 with concentrated sodium hydroxide and maintained at this value until the coupling reaction is complete. The solution was then heated at reflux for 3 hours at the same pH to hydrolyze the acetylamino group. The reaction mixture was then cooled to 20 ° C and the azo compound was separated with concentrated hydrochloric acid. The product is obtained by filtration, drying and grinding. In order to esterify the β-hydroxyethylsulfonyl group, this azo compound is added under stirring to a quadruple amount of 100% sulfuric acid at 20 ° C and the reaction mixture is stirred at that temperature for 6 hours. Thereafter, the reaction mixture is stirred into ice-water, maintaining the temperature at 10 ° C, neutralized with calcium carbonate to pH 1.3, and then with sodium carbonate to pH 6.5.

The reaction mixture is heated to 65 ° C, the precipitated calcium sulfate is filtered off, potassium chloride is added to the filtrate and the precipitated monoester derivative of sulfuric acid is filtered off. This filter residue is dissolved in 400 parts of water and a suspension of 32.5 parts of Ni (3 ', 5 ^, -dichloro-s-triazinyl) aniline-2-sulfonic acid in 150 parts of water and 50 parts of ice is added. The pH of the coupling mixture was adjusted to 5.5-6.0 with sodium carbonate and maintained at this value until the reaction was complete.

Then, as many parts of chromium acetate as 2.6 parts of chromium and 13.6 parts of crystalline sodium acetate are added, the chromating mixture is heated to 95 ° C until completion of the reaction. The solution thus obtained is clarified and the chromium 1: 2 complex with the monoazo compound of the invention is isolated by conventional evaporation. A black powder is obtained which, in addition to the electrolyte salts, contains an alkali metal salt, predominantly sodium salt, of the compound of formula

WHOSE

This compound has very good fiber-reactive dye properties as a dye and provides reddish-gray prints with very good fastness to light and very good wetness, especially when printing on cellulosic fibrous materials such as cotton, by application and fixing methods customary for fiber-reactive dyes. stability with good fixation yield.

Example 8

In order to produce a 1: 2 chromium complex complex according to the invention, both metal-free monoazo compounds are first synthesized.

Monoazo Compound A:

29.7 parts of 2-aminophenol-4 &apos; -sulfonyl-ethylsulfone are diazotized in a conventional manner in aqueous hydrochloric acid by treatment with sodium nitrite, for example according to the data contained in Example 1. To the diazonium salt solution obtained is added

52.4 parts of 2- [3‘-chloro-5‘- (3'-sulfophenylamino) -2-b 9 4

-? - triazinyl] -? -? -? - 8-naphthol-6-sulfonic acid in the form of an aqueous suspension.

The coupling reaction is carried out at a pH of 6.8 to 7.2. This pH was adjusted with sodium carbonate and also maintained with sodium carbonate. The azo compound thus produced has the following formula, shown in free acid form:

Monoa.product B

37.7 parts of 2-aminophenol- [5sulfatoethylsulfone-6-sulfonic acid] is diazotized in an aqueous solution of hydrochloric acid in sodium nitrite in the usual manner. To the diazonium salt solution obtained was added 52.4 parts of 2 as an aqueous suspension

- [3-chloro-5- ^t s (2 "of sulfone-phenylamino) -s-triazinyl] amino-5-naphthol-7-sulfonic acid.

Here again, the pH is maintained at pH 6.8 to 7.2 with sodium carbonate during the coupling reaction. The monoazo compound thus produced has the following formula B as the free acid

Production of a 1: 2 chromium complex complex according to the invention:

The solutions of the monoazo compounds A and B thus produced are mixed with each other and as many parts of chromium acetate as 5.2 parts of chromium and 27.5 parts of crystalline sodium acetate are added. To perform the chromation reaction, the reaction mixture is heated to 95 ° C, then filtered and the clear filtrate is spray dried. The 1: 2 chromium complex of the invention isolated in the form of a sodium salt in addition to the electrolyte salts consists of a symmetric 1: 2 mono complex with monoazo A, a symmetric 1: 2 mono complex with monoazo B and an asymmetric chromium 1: 2 with monoazo compounds A .

This 1: 2 chromium complex complex of the invention is a black powder which provides on cellulosic fibrous materials, such as cotton, using the application and fixation methods customary for fiber-reactive dyes in the presence of alkali, gray to black and gray to black. black prints with very good wet fastness and very good fastness to light. Particularly in the case of prints, this 1: 2 chromium complex complex achieves excellent fixation yields.

Example 9

In order to produce a 1: 2 chromium compound complex according to the invention, the two metal-free monoazo compounds are first prepared separately.

Monoazo Compound C:

29.7 parts of 2-aminophenol-4- _i -sulfaacethylsulfone are diazotized in a conventional manner. The solution of the diazonium salt was mixed with an aqueous suspension of 39.7 parts of 2- (3'-chloro-5'-ethoxy-4-thiazolyl)] - [4- (4-methyl-3-naphthol-6-)] for coupling. The pH of the coupling mixture is maintained at 6.8 to 7.0 throughout the reaction, and the azo compound thus produced has the following formula C, shown in free acid form.

Monoazo compound D:

24.6 parts of 2-amino-4-acetylaminophenol-6-sulfonic acid is diazotized according to the data described in Example 6. To this diazonium salt suspension is added 28.2 parts of 1- (4 '- / 3-hydroxyethylsulphonyl) f. enyl-3-methylpyrazol-5-one. The coupling reaction is carried out at pH 10 which has been adjusted and maintained with sodium carbonate. The pH was then adjusted to 12 by addition of concentrated sodium hydroxide and the reaction mixture was heated to reflux. The pH is then adjusted to pH 10 with concentrated hydrochloric acid

1.5 and in this way the monoazo compound is eliminated. The product dried after filtration is mixed into a quadruple mass of 100% sulfuric acid at 15-20 ° C. The reaction mixture was further stirred to obtain a quantitative yield of sulfation and then added to the ice / water mixture. The calcium carbonate was adjusted to pH 1.3 and then sodium carbonate to pH 6.5. The reaction mixture was heated to 65 ° C and the resulting calcium sulfate was filtered off. The filtrate was evaporated to dryness and the resulting monoazo compound dissolved. in 400 parts water. To this solution was added a suspension of 19.5 parts of 1,3-dichloro-5-ethoxy-s-triazine in 50 parts of water. The pH was adjusted to 5.5-6.0 with sodium carbonate and maintained at this value until the acylation reaction was complete. The monoazo thus produced has the following formula D, shown in free acid form

Production of a 1: 2 chromium complex complex according to the invention

The solutions of the monoazo compounds C and D thus produced are mixed with each other and as many parts of chromium acetate as 5.2 parts of chromium and 27.5 parts of crystalline sodium acetate are added. In the chromation reaction, the reaction mixture is heated to 95 ° C, then the mixture is filtered and the filtrate is spray dried. The 1: 2 chromium complex of the invention isolated with sodium salt electrolyte salts consists of a symmetric 1: 2 mono-chromium complex C, a symmetric 1: 2 mono-chromium complex D and an asymmetric chromium 1: 2 complex with the monoazo compounds C and D .

This 1: 2 chromium blend complex of the invention is applied to the materials described herein, particularly cellulosic fibrous materials, such as cotton, using the application and fixation methods customary in the art for fiber-reactive dyes, dark brown dyes and dark brown prints. with very good fastness to light and very good wet fastness with almost quantitative fixation yield.

Example 10

To prepare the asymmetric cobalt complex 1: 2 according to the invention, both starting azo compounds are first synthesized.

Monoazo Compound E:

29.7 parts of 2-aminophenol-4- (3-allylethylsulfone) is diazotized as described in Example 1. To this diazonium salt solution is added an aqueous suspension of 57.1 parts of 1-N-ace2366 M toacetyl-4-N ' - [3'-chloro-5'- (2'-methyl-4'-sulfo-enylamino) -s-triazinyl] diaminobenzene-3-sulfonic acid and the pH is maintained at 6.5 throughout the coupling reaction.

Cobalt complex 1: 1 with monoazo compound F:

The solution of monoazo compound B of Example 8 was transferred under a nitrogen atmosphere and a solution of as many parts of crystalline cobalt sulfate as 2.95 parts of cobalt in 100 parts of water was added. The pH of this solution was adjusted slowly to 7.2 with 2N aqueous sodium carbonate solution and the temperature was maintained at 10 ° C by external cooling. The reaction mixture was then stirred for a further 45 minutes.

Production of asymmetric cobalt 1: 2 complex according to the invention:

The solution of monoazo compound E is added to the solution of the cobalt complex with monoazo compound F. While maintaining the pH between 6.8 and 7.2, the reaction mixture is slowly heated to 60 cc and this temperature is maintained until the metallization reaction is complete.

The reaction mixture was then filtered and evaporated to dryness. A dark yellow powder is obtained which, in addition to the inorganic salts of the electrolyte, contains a sodium salt of the compound of the formula

CH ₂ CH ₂ SO _{3 3} h

CO-NH N = N-C

ΐ oCzHs

This compound exhibits very good dye properties and provides, for example, reddish-yellow coloring (reddish yellow prints) with very good light fastness and wet fastness when printing cellulosic fibrous materials using conventional fixation methods in the presence of alkali. Fixation yield is almost quantitative.

Example 11

21.7 parts of 2-amlnofeno - 4- _it 'Miydroxyethylsulfonu is diazotized in a known manner, for example analogously to the details given in Example 6. Then, an aqueous solution

37.9 ddlu of 1- (2,5‘-disulfo-4‘-aminooenyl) -3-kaaboxypyrazol-5-one. The pH of the coupling mixture was maintained at 6.5 with sodium carbonate until the reaction was complete. The acid is then adjusted to pH 1.5 with sodium chloride to precipitate the monoazo compound, filtered off, dried and added to a mixture of 300 parts by volume of methylglycohi, 50 parts of water and as many parts of crystalline chromium chloride as possible. 5.2 parts of chrome. The chromating mixture is heated to 105 ° C until the chromating reaction is complete. The solvents are then distilled off under reduced pressure and the chromium complex thus produced 1: 1 is dried. This complex is then heated in 200 parts by volume of pyridine together with 40 parts of amidosulfonic acid until complete sulfation at 50 ° C. The bulk of the solvent is then distilled off under reduced pressure. The residue was taken up in ice water and dissolved at pH 6.0 by addition of sodium carbonate. To this solution is added

11.5 parts of 5S-dichloro-N-ethylamino-s-triazine and the pH is maintained at 5.5 to 6.0 and the temperature is maintained at about 40 ° C until complete acylation with sodium carbonate.

To the 1: 1 chromium complex solution thus prepared, a solution of the monoazo compound A of Example 8 was added.

In #.

It is heated while maintaining the pH at 6.0 by adding sodium carbonate to a temperature of 90 degrees Celsius and maintaining the temperature at this pH.

Then. the asymmetric 1: 2 asymmetric chromium complex compound of the present invention is filtered and isolated

in a conventional manner, for example by evaporation or spray drying, in the form of its alkali metal salt, such as the sodium salt. This 1: 2 chromium complex according to the invention has very good dyeing properties and provides brown to dark brown coloring with very good fastnesses by application and fixation methods customary in the art on the materials mentioned in the description, in particular cellulose fiber materials, in the presence of alkali. in light and with very good wet fastnesses with very good fixation yield, especially during printing.

Example 12

To prepare the asymmetric chromium complex 1: 2 according to the invention, both starting azo compounds are first prepared separately.

1: 1 chromium complex with monoazo compound G:

24.5 parts of 1-aminobenzene-3-S-hydroxyethylsulfone-6-carboxylic acid are diazotized in a conventional manner. To this diazonium salt solution was added 27.2 parts of 1- (N-acetoacetylamino) -3-aminobenzene-4-sulfonic acid and the pH was adjusted to 6.0-6.5.

After completion of the coupling reaction, the resulting monoazo compound is precipitated with hydrochloric acid at 50 ° C, filtered off, dried and ground. This compound is mixed into 300 parts by volume of methyl glycol and as many parts of chromium chloride are added as they are

5.2 parts of chrome. The reaction mixture is heated to reflux until the chromation is complete. Thereafter, the solvent was distilled off under reduced pressure and the 1: 1 chromium monoazo complex remaining as a residue was isolated and dried, and then, together with 40 parts of amidosulfonic acid, were sulfated in 200 parts by volume of pyridine at 50 ° C. Then, most of the solvent was distilled off under reduced pressure, the residue was taken up in ice-water and dissolved at pH 6.0 by addition of sodium carbonate. To this solution was added 19 parts of cyanuric chloride and the pH was maintained between 4.5 and 5.0 and the temperature at 15 ° C until quantitative sulfation was achieved. After completion of the acylation reaction, a solution of 17.3 parts of aniline-3-sulfonic acid in 50 parts of water was added to the reaction mixture. In this second acylation reaction, the reaction mixture is heated to 80 ° C at a constant pH of 6.8. A 1: 1 chromium complex with the monoazo compound G is formed

COOti но-с-СН ίΫ-Ν = Ν-0 γ со-нн_ ^

S0b

AND

CH 2 CH 2 OSO ₃ H

(G)

Monoazo compound H

A neutral solution of 34.8 parts manufactured in conventional manner 2-amino-4- (3 ^{<-chloro-5'-methoxy-s-triazinyl)} aminofeiiol-5-sulfonic acid in 300 parts of water are treated with 20 parts by volume of 5N aqueous sodium sodium nitrite and the resulting mixture is mixed into a mixture of 100 parts ice and 35 parts 31% hydrochloric acid. The reaction mixture was further stirred for 60 minutes and then the excess nitrous acid was quenched with amidosulfonic acid. Then, a solution of 44.1 parts of 2- [N-methyl-N- (8sulfethoxyethylsulfonyl) -8-aminonaphthol-6-sulfonic acid in water is added for coupling, the pH is adjusted to 6.8 and maintained until until the coupling reaction is complete. _

SO ₅ CH 2 CH 2 OSO ₃ H

CO-NH n = n - c

N-SO ^ CH ^ CH ^ OSO ^ (-)

H ^<r>

AND

Production of the asymmetric chromium 1:: 2 complex according to the invention:

The two solutions of chromium complex 1: 1 with monoazo compound G and monoazo compound H are mixed with each other and heated to 98 ° C after adjusting the pH to 6.5. This temperature is maintained until the chromium complex formation is 1: 2 as well as the pH is maintained at 6.8 by addition of sodium carbonate. Then the reaction mixture was filtered and the filtrate was evaporated.

As an olive green powder which still contains inorganic salts of the electrolyte, the asymmetric chromium complex 1: 2 according to the invention of the following formula is obtained in the form of its sodium salt.

This compound has very good fiber-reactive dye properties as a dye and, for example, when printing on cellulosic fibrous materials, it provides green dyeing with very good fastness to light and very good wet fastness to face good fixation yield when printed on cellulosic fibrous materials.

Example 13

To prepare the asymmetric chromium complex 1: 2 with the monoazo compound of the invention, both starting azo compounds are first prepared separately.

1: 1 chromium complex with monoazo compound J:

oa

To an aqueous solution of the diazonium salt of 29.7 parts of 2-aminophenol-4-, 6'-sulfatoethylsulfone was added 23.9 parts of 2-amino-5-naphthol-7-sulfonic acid and the pH was adjusted to 7.0. The reaction mixture is stirred at this pH and at a temperature of 15 to 20 ^° C until the coupling reaction is complete and the resulting monoazo compound is isolated by evaporation. The dry powder is then mixed into 300 parts by volume of diglycol and as many parts of crystalline chromium chloride as 5.2 parts of chromium are added and the reaction mixture is heated to 110 ° C with stirring until the complex formation is complete. After cooling to room temperature, 500 parts of water are added, the mixture is filtered until clear, and the pH is adjusted to 6.0.

Monoazo Compound K:

18.9 parts of 1- (4'-aminophenyl) -3-methylpyrazol-5-one are added to an aqueous solution of the diazonium salt of 37.7 parts of 2-artiinophenol-4- (1-sulfatoethylsulfone-6sulfonic acid). The pH of the coupling mixture was adjusted to 6.5. The reaction mixture is further stirred until completion of the coupling reaction at said pH and at a temperature of 15 to 20 ° C. The produced monoazo compound, represented in free acid form, has the following formula K

(К)

Production of the asymmetric chromium 1:: 2 complex according to the invention:

The mixture of the two solutions of the chromium complex 1: 1 with monoazo compound J and monoazo compound K is slowly heated to 60 ° C with stirring while maintaining a pH of 6.5 and further stirred at this temperature and pH until the chromium complex formation is complete. The resulting 1: 2 chromium complex is salted out at pH 2.0 and, after isolation, dissolved in 500 parts of water with neutralization. 36.9 parts of cyanuric chloride are then added and the acylation reaction is carried out with stirring at pH 3.5-4.0 and at 20 ° C. Thereafter, the reaction solution is clarified by filtration and 34.6 parts of amine-3-sulfonic acid are added to the filtrate. In order to carry out this second acylation reaction, the reaction mixture is adjusted to a pH of 6.6 to 6.8 and at this pH maintained constant at about 20 ° C, stirred, then heated to 50 ° C and it is further stirred at this temperature and at a pH of 6.7 to no longer change in pT. The 1: 2 asymmetric chromium complex thus produced according to the invention is isolated by salting out.

A dark brown powder is obtained which, in addition to the electrolyte salt (predominantly sodium chloride), contains the sodium salt of the compound of formula

3 6 3 9 1

This compound has very good fiber-reactive dye properties and, for example, provides brown dyeing with good light fastness and very good wet fastness with very good fixation yield, for example, by the printing methods customary for fiber reactive dyes on cellulose fibers.

Examples 14 to 33

The following examples summarized in the table describe further symmetrical 1: 2 metal complexes with the monoazo compounds of the invention by means of their components, i.e. the monoazo therein and the co-complexing metal therein. These compounds can be prepared from the corresponding cobalt or chromium-providing compounds (salts) and monoazo component (diazo and coupling components, chlorotriazine derivatives) components by the process of the invention, such as some of the process variants described in Examples 1 to above. 7. The compounds of the invention are preferably isolated in the form of their alkali metal salts, such as sodium or potassium salts, and provided on the materials described herein, particularly on cellulosic fibrous materials, such as cotton, using application and fixation methods which are common in the technique for fiber-reactive dyes, color-intensive dyeing and prints with good to very good fastnesses to light and wet fastnesses at high fixation yields and in the color shade shown in each of the examples in the table .

Table Example Symmetric Complex of 1: 2 Metal-Free Compound of Formula Metal Color Shade Complex

orange

yellow

OH HIM Her. Sat -N = N- O you HOjS ^ 1

ch ^ ch ^ ax ^ h

Cr gray

-t J £

example 1: 2 symmetric metal-free compound of the formula a metal forming a complex color shade Q17 1 НЮ-С-СНъ i, a HOaS ΰ T Ir IPN-C-CO-NH4 к Г N-C 17 and ÍVH-. j АЛ сн ₂ What reddish yellow r · 'f C U jΝ ~ α · Η <Μ £ $ <} Ρ ^CH 2 ° ^N

OH

Ho ₂ p

HIM

N = N

Cr gray

NH n ^ n

C and _N> -NH-CH "COOH

HIM

N = N

HO «S

What a claret

OH

HQ3

COOH

ΟΗ] 1--0 NH _. AND,. - , X Ач O J Г ^Hi v T soc SO.H

. . Cr gray

CH 2 CH 2 Cl 2 SO 2 H

As a brown example, a symmetrical 1: 2 metal-free complex compound of the metal forming a complex

HIM

HO.S

№N

HO »S

AND

color shade orange brown reddish gray reddish gray yellow example symmetric complex 1: 2 metal-free compounds of the formula metal forming a complex

COOH

COOCfi ^

NH-CH ₂ CH ₂ SO ₃ H

SC _from Hc color shade orange reddish yellow yellow yellow example symmetric complex 1: 2 metal-free compounds of formula metal forming complex color shade

Cr violet

gray yellow

Examples34 to 48

The following examples summarized in the table describe further mixed cobalt 1: 2 chromium complexes 1: 2 according to the invention with their components, i.e. both metal-free monoazo compounds and complexing metal. These compounds consist of both symmetrical cobalt 1: 2 or chromium 1: 2 complexes with the monoazo compounds of the aforementioned metal-free monoazo compounds of the invention and asymmetric cobalt 1: 2 or chromium 1: 2 complexes with the monoazo compounds of the two metal-free monoazo compounds of the invention. mixtures of both of the two metal-free mono-starting compounds and the corresponding metal-providing compound (salt) by the process of the invention, such as one of the process variants described in Examples 8 or 9 above. alkali metals, such as in the form of sodium salts, and also exhibit very good fiber-reactive dye properties.

On the materials described herein, such as, in particular, cellulosic fibrous materials, such as cotton, these compounds, using the application and fixation methods customary in the art for fiber-reactive dyes, provide color-intensive dyeing and prints with good to very good fastnesses to fibers. light and wet fastnesses at high fixation yields and in the color shade shown in each example table for dyeing cotton.

3 ti 6 9 4 ³⁷ , ³⁸ f

Table

example mixed metal complex 1: 2 corresponding to formula 1 with ... complexing metal color shade the metal-free azo compound of example ... a metal-free azo compound of Example No. ... 34 12, compound G 13, N- (2-m-sulphenyenylamino-4-chloro-s-triazin-6-yl) derivative of compound К What yellow 35 13, N- (2-m-sulfo-enylamino-4-chloro-s-triazin-6-yl) derivative of compound К 14 What yellow 36 15 Dec 16 Cr Brown 37 16 17 Cr Brown 38 18 19 Dec Cr gray 39 16 20 May Cr gray 40 14 22nd Cr orange 41 22nd 24 Cr Brown 42 18 27 Mar: What Brown 43 26 28 What reddish yellow 44 16 30 Cr green 45 14 22nd What reddish yellow 46 19 Dec 33 Cr olive 47 33 27 Mar: Cr reddish yellow 48 33 30 What yellow

Examples 49 to 58

The following examples summarized in the table describe further asymmetric 1: 2 cobalt 1: 2 cobalt complexes with the monoazo compounds of the invention by means of their components, i.e. the 1: 1 chromium cobalt or 1: 1 cobalt complex with the monoazo compound. its free acids, and the metal-free monoazo compounds. These compounds can be prepared from these starting compounds by the process of the invention, such as according to one of the process variants described in Examples 10-13 above. The compounds are preferably isolated in the form of their alkali metal salts, such as sodium or potassium salts, and also exhibit very good fiber-reactive dye properties. They provide color-intensive dyeing and prints with good to very good fastness, and high yield fixation in a color shade that is provided on the materials described in the description, such as, in particular, cellulosic fibrous materials, such as cotton, using conventional application and fixation methods. for cotton dyeing is given in each example table.

Table

example asymmetric metal complex 1: 1 kovuprostou colored corresponds to formula 1 s ... monoazolouče- shade 1: 1 metal complex with azo compound of formula. example.

and

= N ho ₃ s

Cfi

I ‘

CH 2 OSO 4 H

brown green brown brown asymmetric metal complex 1: 1 corresponding to formula 1 s ...

1: 1 metal complex with azo compound of formula.

an example of a colorless monoazo-color shade from the example # '

h) to _, - ч ——— M - '- ^- ₍

CHr cit ~~ ct

Brown

Brown

(r;

Brown

CH _Z OSO ₃ I1 SO3H yellow asymmetric metal complex 1: 1 corresponding to formula 1 s. . .

1: 1 metal complex with azo compound of formula.

a colorless monoazo-color shade of Example no.

example f \

-O '<

-n = n-c ί

WHAT

NUO

No-Cl-Ц

Η

Cl yellow so ₃ H

Claims (13)

A process for the production of water-soluble symmetrical or asymmetric 1: 2-chromium-complex or 1: 2-cobalt-complex azo compounds derived from the monoazo compounds of general formula 1 (1) as well as their mixed metal complexes 1: 2, wherein: Y 1 represents a hydroxy or carboxy group capable of forming a complex with a metal which is bonded ortho-to the a-bridging residue D, D is a benzene ring optionally substituted by a substituent selected from the group consisting of a sulfo group, an alkyl group of 1 to 4, as the diazo moiety to which the filament-reactive group V ₁ or the filament-reactive group V 2 defined below is bound. carbon atoms, C 1 -C 4 alkoxy, nitro, carboxy, sulfamoyl, The invention is based on a carbamoyf group, a C 1 -C 4 alkyl group, a monosubstituted or disubstituted carbamoyl group or a sulfamoyl group, an N-phenylcarbamoyl group, an N-phenylsulfamoyl group, an N-methyl-N-phenylcarbamoyl group, an N-methyl-N-phenyl group. .famoyl, chlorine and bromine, or a naphthalene ring optionally substituted by one or two sulfo groups, Y ₂ represents a hydroxyl group capable of forming a metal complex; -K-Y ₇ means as the remainder of the coupling component a naphthol residue to which a naphthalene core K is bound by a fiber reactive group as defined below or a fiber reactive group V ₂ as defined below; wherein the azo group is ortho-to Y2 and which is optionally still substituted with one or two sulfo groups, or is a 1-phenyl- or 1-naphthylpyrazol-5-on-4-yl radical to which the azo group is attached at the 4-position and which in position 3 is substituted by carbamoyl, C2 -C5 alkoxycarbonyl, phenyl, methyl or carboxy and whose phenyl residue at position 1 is substituted by a fiber reactive group VI as defined below or by a group V- 2 which is optionally reactive with a fiber and which is optionally still substituted by one or two substituents selected from e is a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine, bromine, C 1 -C 4 alkanoylamino group, an alkyl group, a carboxy group and a sulfo group, and whose naphthyl residue is in the position 1 is substituted with a further defined group V ₁ or V 2 and is optionally further substituted with a sulfo group and one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, C 1 -C 4 alkanoylamino, carboxy and chloro or one or two sulfo groups, or is a radical of formula HIM C — CH3 II — C — CO — NH — phenyl or HIM I c — CH ₃ II '—C — CO — NH — naphthyl in which the phenyl radical “phenyl” is substituted with a fiber-reactive V2 or a V2 defined below and optionally is further substituted with one or two substituents selected from the group consisting of C 1 -C 4, C 1 -C 4 alkoxy, chloro, carboxy, sulfo, carbamoyl and sulfamoyl, and in which the naphthyl residue "naphthyl" is substituted with a fiber-reactive group defined as V 1 or V 2, and which is optionally further substituted by a sulfo group and one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro and carboxy, or one or two sulfo groups, Vt is a group of formula (2a) which is bound to D or K, and wherein R is hydrogen or C 1 -C 4 alkyl; X represents a group of the general formula R 4 is -O-R ¹ , (2c), -S-R- (2d), or -N. \ R3 (2e) where, R 1 and R 2 are each C 1 -C 4 alkyl optionally substituted by one or two substituents selected from the group consisting of acetylamino, hydroxy, sulfato, C 1 -C 4 alkoxy, phenyl, naphthyl, and phenyl substituted sulfo, carboxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro, sulfamoyl and / or carbamoyl, and naphthyl, substituted with sulfo, carboxy, C 1 -C 4 alkyl, alkoxy C 1-4 alkyl, chloro, sulfamoyl and / or carbamoyl, sulfo and carboxy, or phenyl or naphthyl which may be substituted with substituents selected from the group consisting of carboxy, sulfo, C 1 -C 4 alkyl 4 carbon atoms, and (C 1 -C 4) alkoxy, hydroxy and chloro; R3 is hydrogen or an optionally substituted allyl group defined for R ^l, or an alkenyl group having two to four carbon atoms, or represents cyclohexyl; R4 is hydrogen or an optionally substituted alkyl group as defined for R 1 or is alkenyl with 2 to 4 carbon atoms or optionally substituted phenyl or naphthyl radical which is as defined for Rl, wherein R ³ and R 4 may have identical or different meanings or R 3 or R 4 together with the nitrogen atom form a heierocyclic ring containing a C 4 -C 7 alkylene radical or 2 or 3 C 1 -C 4 alkylene radicals and 1 or 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, V 2 is a group of formula 2b - (2b) which is bonded to the radical D or to the remainder K, wherein <? W represents a direct bond or a group of the formula --N.H--, --N--, --CH2 - or. _ I · ' Alk -> CH ₂ —CH ₂ -, where Alk represents an alkyl group having 1 to 4 carbon atoms, Z is vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-chloroethyl or β an acetoxyethyl group, characterized in that the compound of the formula II is reacted D — A (II) wherein D is as defined above and A represents an amino group -NH ₂ or represents a group of formula (a) or (b) in which R, R ¹ , M and Hal have the meanings given above, in the case of an amine of the formula II in which A is the aforementioned amino group, after diazotization to the diazonium salt, it acts with a compound of the formula III В represents a hydrogen atom or a group of the general formula (b ‘) or (d ') in which R ^2, R ³ and Y have the above meanings and wherein Haí H and l —— R, R ¹ , M and Hal are as defined above, wherein A is an amino group when B is a group of formula (bj, A is a group of formula (a) when B is a group of formula *) [bj, when B is hydrogen, either the starting compound being used in the form of a complex with chromium or cobalt, or the resulting compound is converted by treatment with a chromium salt or cobalt to the corresponding complex. 2. A process according to claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form complexes with the monoazo compounds of formula 1. wherein D is a benzene moiety wherein the Yt group is ortho-bonded to k azo is a carboxy or hydroxy group, to which is attached a group V ₍ fiber reactive as defined in point 1 or a fiber reactive group ₂ as defined in point 1) and optionally further substituted by one substituent selected from the group consisting of sulfo, alkyl C 1 -C 4 alkoxy, C 1 -C 4 alkoxy, nitro, carboxy, sulfamoyl, carbamoyl, carbamoyl or sulfamoyl mono- or disubstituted with C 1 -C 4 alkyl, N-phenylcarbamoyl , N-phenylsulfamoyl, N-methyl-N-phenylcarbamoyl N-methyl-N-phenylsulfamoyl, chloro and bromo. 3. A process according to claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form complexes with the monoazo compounds of formula 1 wherein D is a benzene nucleus having a Y ₍ ortho-bonded) group. to the azo group is a hydroxy group, to which is attached a fiber reactive group Vj as defined in point 1 or a fiber reactive group V ₂ as defined in point 1, and which is optionally still substituted by substituents selected from the group consisting of sulfo, methyl, ethyl, methoxy, ethoxy, carboxy and chlorine, or wherein D is a naphthalene nucleus, wherein the Y group bonded ortho to the azo group is a hydroxy group and to which a fiber reactive group V 1 or V 2 is bonded and as defined in 1 and optionally substituted with one or two sulfo groups. 4. A method according to claim 1, characterized in that starting from the corresponding compounds of the formulas II and III to form complexes with the monoazo compounds of the formula 1, wherein -K-Y ₂ is a naphthol radical to which is bonded a group Vt or the fiber-reactive group V2 defined in item 1, bound to the remainder of K, and in which the azo group is ortho-to the hydroxy group and in which the naphthalene core K is still optionally substituted with one or two sulfo groups. , г 5. A process according to claim 1, wherein the corresponding compounds of the formulas II and III are used as starting materials to form complexes with the monoazo compounds of the formula I, in which Κ-Υ> is 1-phenyl or 1-naphthylpyrazole. A -5-on-4-yl radical to which the azo group is attached at the 4-position and which is substituted at the 3-position by carbamoyl, C 1 -C 4 alkoxycarbonyl, phenyl, methyl or carboxy and whose phenyl the residue in position 1 is substituted with V or fiber reactive group V2 as defined in point 1 and is optionally further substituted by one or two substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy 4 carbon atoms, chlorine, bromine, C1 -C4 alkanoylamino, carboxy and sulfo, and the like wherein the naphthyl residue in position 1 is substituted with V 1 or V 2 as defined in point 1 and is optionally further substituted with one sulfo group and one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, C 1 -C 4 alkanoylamino alkyl moieties, carboxy and chlorine or one or two sulfo groups. 6. A method according to claim 1, characterized in that starting from the corresponding compounds of the formulas II and III to form complexes with the monoazo compounds of the formula 1, wherein -K-Y ₂ is a radical of formula HIM IC-CH-3 II '—C — CO — NH — phenyl or HIM C — CH3 II —C — CO — NH — naphthyl in which the phenyl radical “phenyl” is substituted by a fiber reactive group Vt or V2 as defined in point 1 and is optionally further substituted by one or two substituents selected from the group consisting of up to 4 carbon atoms, C 1 -C 4 alkoxy, chlorine, carboxy, sulfo, carbamoyl and sulfamoyl, and in which the naphthyl residue "naphthyl" is · substituted with a fiber-reactive -V 1 or V 2 group as defined in 1 and it is optionally further substituted with one sulfo group and one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro and carboxy, or one or two sulfo groups. 7. A process as claimed in claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form complexes with monoazo compounds of formula I wherein X is C1 -C4 alkoxy, phenoxy which is: optionally substituted with one or two sulfo groups, amino, further mono or disubstituted with C 1 -C 4 alkyl or amino substituted with one C 1 -C 4 alkyl and one C 2 -C 5 alkoxycarbonyl C 1 -C 4 -sulfonyl or C 1 -C 4 sulfonyl, furthermore phenylamino or naphthylamino, the phenyl and n-phenyl groups of which may still be substituted by methyl, methoxy, chloro, carboxy and / or sulfo and their nitrogen atom may be substituted by C 1 -alkyl; up to 4 carbon atoms. 8. A process according to claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form compounds of formulas 6, 7 or 8 in which: M ⁽ +) represents a hydrogen atom or an equivalent of a cation of a monovalent or divalent metal, Me is chromium or cobalt, n is 0 or 1, Vt is as defined in point 1 of the defined group of formula 2a, wherein R is hydrogen and X is the amino group in point 1 of formula 2e, wherein R ³ is hydrogen or C 1 -C 4 alkyl optionally substituted and R4 represents a hydrogen atom or a C1-C4 alkyl group optionally substituted by a carboxylic acid or sulfonic acid residue or an optionally substituted phenyl group, or a phenyl group optionally substituted by one or two substituents selected from the group consisting of sulfo, carboxy, methyl, ethyl, methoxy, ethoxy and chlorine, both • · radicals R ³ and R may be same as each other »or different from each other, - ·. V ₂ has the meaning defined in point 1 of the defined group of formula 2b, D | means a benzene radical in which the carbonyloxy or oxy group is ortho-attached to the azo group and which, in addition to the two groups and the group V | it contains no further substituent or is still substituted by a sulfo, methyl, ethyl, methoxy, ethoxy, carboxy, sulfamoyl or carbamoyl or chlorine or bromine atom, or Dt represents a naphthalene radical in which the carbonyloxy or oxy group is bound in ortho position to the azo group and in addition to the two groups and the group V (optionally containing one or two sulfo groups as additional substituents, D2 is a benzene radical in which the carbonyloxy or oxy group is bonded in ortho-position to the azo group and which in addition to these two groups and the group V ₂ contains no further substituents or is further substituted with methyl, ethyl, methoxy, ethoxy, nitro, a carboxyl ' or sulfamoyl or carbamoyl or chlorine or bromine or sulfo, or D2 represents a naphthalene residue in which the carbonyloxy or oxy group is ortho-attached to the azo group and which may contain one additional sulfo group in addition to the two groups and the V2 group , Kt is a naphthalene radical in which the oxy group is bonded in ortho-position to the azo group and which in addition to these two groups and the group V ₂ may contain as further substituents, sulfo, or Kt represents a residue of 1-phenyl- or 1-naphthyl-pyrazol-4,5-ylene which is substituted in the 3-position by carbamoyl, C 2 -C 5 alkoxycarbonyl, phenyl, methyl or carboxy and whose phenyl residue in position 1 there is no other substituent besides V2 or is still substituted by 1 or 2 substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine and / or one substituent selected from the group consisting of bromine, carboxy and sulfo, or One substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine or one sulfo group, and whose naphthyl residue in position 1 contains no other substituents besides the group V ₂ or is further substituted by one or two sulfo groups, or K | · represents a radical of a coupling component being acetoacetylaminobenzenu * alkyl radical or acetoacetylaminonaftalenu, where the benzene radical does not contain in addition to the group V ₂ is no more substituenťnebo further substituted with one or two substituents selected from. methyl, ethyl, methoxy, ethoxy and chloro and / or one substituent selected from bromo, carboxy and sulfo or one substituent selected from methyl, ethyl, methoxy, ethoxy and chloro and one sulfo and one and a sulfo group; the residue contains no other substituent besides the group V ₂ or is still substituted by one or two sulfo groups, K-2 represents a naphthalene radical in which the oxy group is ortho-attached to the azo group and which is substituted by one or two sulfo groups in addition to the Vt group, or K ₂ represents a 1-phenyl- or 1-naphthyl-pyrazol-4,5-ylene radical which is substituted in the 3-position by carbamoyl, C 2 -C 5 alkoxycarbonyl, phenyl, methyl or carboxy and whose phenyl radical in position 1, there is no other substituent besides V, or is substituted with one or two substituents selected from the group consisting of methyl, ethyl, methoxy and ethoxy and / or one substituent selected from the group consisting of chlorine, carboxy and sulfo or one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chloro and one sulfo and whose naphthyl residue in position 1 contains no other substituent besides the group V [or is additionally substituted next to the group Vj, or two sulfo groups, or K ₂ is as the remainder of the capping component an acetoacetylaminobenzene or acetoacetylaminonaphthalene residue, wherein the benzezene moiety in addition to the group V _A contains no other substituent or is further substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chloro and / or one carboxy or one sulfo group or one substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chloro and one sulfo group, the naphthyl residue of which contains no other substituent besides Vj or Vt is still substituted with one or two sulfo groups. 9. A process according to claims 1 and 8, wherein the corresponding compounds of the formulas II and III are used as starting materials to form complexes with the monoazo compounds of formula 1, wherein n is 0. 10. A process according to claim 1 or 8, wherein the corresponding compounds of formulas II and III are used as starting materials to form complexes with monoazo compounds of formula 1, wherein M ⁽ + & lt ^; + &gt; represents sodium or potassium ion or calcium ion equivalent). . 11. A process according to claim 1 or 8, characterized in that the corresponding compounds of the formulas II and III are used as starting materials to form complexes with the monoazo compounds of the formula I, in which Vx is the group 2a of the formula 2a. which R represents a hydrogen atom and X represents an alkoxy group having 1 to 4 carbon atoms. 12. A process according to claim 1 or 8, wherein the corresponding compounds of formulas II and III are used as starting materials to form complexes with monoazo compounds of formula 8 wherein n is zero, Vx is the group 2a described in 1 wherein R is hydrogen and X is amino or phenylamino or N-methyl- or N-ethylphenylamino or phenylamino substituted with one or two sulfo groups, V ₂ is the group of formula 2b mentioned and defined in point 1, D ₂ · refers to the benzene radical in which the oxy group is bonded in ortho-position to the azo group and which in addition to this oxy group and the group V ₂ does not contain any further substituent "or more substituted with one sulfo group as an additional substituent, K ₂ is a naphthalene radical in which the oxy bonded in the ortho position to the azo group and which, in addition to the group V, is substituted once more or d and M ⁽ + and Me have the meanings given in point 8). 13. The method of claims 1 to 12, characterized in that starting from the corresponding compounds of the formulas II and III to form complexes with the monoazo compounds of the formula 1 wherein V ₂ represents vinylsulfonylovou group or a β-sulfatoethylsulfonylovou group.