DE2113298A1 - Reactive dyes - Google Patents

Description

The present invention relates to new reactive dyes of the general formula

CH ₅

? ⁼ ° SC ₇ H
DN = N-CH

where Q and P are hydrogen or a sulfonic acid group, but cannot have the same meaning at the same time, and D is the remainder of a reactive-group-containing aroma-tic-earbocyclic or aromatic-heterocyclic diazo component, in particular the rust of a reactive group-containing diazo component of the benzene series or iienathiazolre iho »

-2 \ r) u

Under. Reactive groups are understood to be those that either directly through addition or by exchanging one, preferably anionic, removable substituents with amino, Amide or hydroxyl groups of natural or synthetic fiber materials under dyeing or printing conditions, preferably in the presence of acid-binding? in particular compounds with an alkaline reaction with the formation of a covalent one Bond react. The reactive groups can be aromatic either directly or via a bridge member with a carbon atom carbocyclic or aromatic-heterocyclic ring in the radical D or the remaining component an azo dye, preferably the remainder of the diazo component represent.

Preferred bridge members are the following:

-N (R) -, _{.-SO 2} N (R) -, -CON (R) -, -N (R) -alkylene-N (R) -,

(lo ₃ H) _o _ ₂

SO ₂ N (R) -alkylene-, -O-alkylene-N (R) -, -NHCONH

/ r-Λ ^ - CON (R) -N (R) CO-alkylene-, - {/ * J , -0-,

/ T \ ^ SOpN (R) -N (R) - </ ~ y ^ά , -N (R) CON (R) -, -alky len-N (R)

where R = hydrogen or C.-C, -alkyl

Lo Λ. I "> 1. '. ^

0 9 07 9/0 9 ö 2

2113238 5

Particularly suitable Ileaktivgruppen which at least one removable substituents on an aromatic heterocyclic one The remainder gebundc3ii contain, inter alia. those that at least one detachable substituent on a 5- or 6-membered aromatic-heterocyclic ring C atom bonded to a -C = H bond contain, for example on a monazine, diasdn or triazine ring, such as a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxaain, sym.-triazine, quinoline, phthalazine, Cinnoline ~, quinazoline or quinoxaline ring or to a thiazole, thiadiazole, loothiazole, benzothiazole or Benzoxazole ring.

The reactive substituents on the heterocycle include, for example, halogen (CI, Br or F) and ammonium including hydrazinium, sulfonium, sulfonyl, azido (N,), rhodanido, thio, thioether, oxyether, sulfinic acid and Sulfonic acid. Examples are to be mentioned in detail Mono- or dihalogen-sym.-triazinyl radical, e.g. 2,4-dichlorotriazinyl-6-, 2-amino-4-chlorotriazinyl ~ 6-, 2-alkylamino-4-chlorotriazinyl ~ 6-, such as 2-methylamino-4-chlorotriazinyl-6-, 2-ethylamino- or 2-propyl-amino-4-chlorotriazinyl-6-, 2-ß-Oxäthylamino-4-chlorotriazinyl-6-, 2-Di-ß-oxäthylamino-4-chlorotriazinyl-6-

Le A 13 626 - 3 -

209839/0982 _{3AD 0RlGlNAL}

and the corresponding sulfuric acid half esters, 2-diethylamino-4-chlorotriaziny1-6-, 2-morpholino- or 2-piperidino-4-chlorotriazinyl-6-, Z-cyclohexyl-amino ^ -ehlortriazinyl-ö-, 2-arylamino- and subst . Arylamino-4-chlorotriaziny1-6-, such as 2-phenylamino-4-chlorotriaziny1-6-, 2- (o-, m- or p-carboxy- or SuJTοphenyl) -amino-4-chlorotriazinyl-6-, 2-alkoxy ^ -chlorotriazinyl-ö-, such as 2-methoxy- or ethoxy-4-chlorotriazinyl-6 ~, 2- (phenylsulfonylmethoxy) -4-chlorotriazinyl-6-, 2-aryloxy and subst. Aryloxy ^ -chlorotriazinyl-δ-, such as 2-phenoxy-4-chlorotriazinyl-6-, 2- (prSulfophenyl) -o3qr-4-chlorotriazinyl-6-, 2- (o-, m- or p-methyl- or methoxyphenyl ) -oxy-4-chlorotriazinyl-6-, 2-alkyl-mercaptro- or 2-aryl-mercapto-or 2- (substituted aryl) -mercapto-4-chlorotriazinyl-6-, such as 2- (β-hydroxyethyl) -mercapto -4-chloro-triazinyl-6-, 2-phenylmercapto-4-chlorotriazinyl-6- _t 2- (4 ^f -methyl-phenyl) -mercapto ^ -chlorotriazinyl-δ-, 2- (2 *, 4'-dinitro ) -phenylmercapto-4-chlorotriazinyl-6-, 2-methyl-4-öhlor- triaainyl-6-, 2-phenyl-4-chlorotriazinyl-6-, mono-, I) i - or trihalopyrimidinyl-reete, such as 2,4-dichloropyriraidinyl-6-, 2,4,5-trichloropyrimidinyl-6-, 2,4-dichloro-5-nitro- or -5-methyl- or -S-carboxymethyl- or -5-carboxy- or - 5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, -di or -trichloromethyl- or -5-carboalkoxy-pyriInidinyl-6-, 2, e-dichloropyrimidine ^ -parbonyl-, 2 , 4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methylpyrimidine-5-carbonyl-, 2-methyl-4-chloropyrimidine-5-carbonyl-, 2-methylthio-4-fl uorpyrimidin -J-oarbdnyl-, 6-methy 1-2,4-dichloropyrimidine-5-carbonyi-, 2,4, δ-trichloropyrimidine-S-carbony1-, 2,4-dichloropyrimidine-5-sulfonyl-, 2-Ch , lorquinoxaline-3-carbonyl-, 2- or 3-monochloroquinoxaline-6-carbonyl-, 2- or 3-monochloro-quinoxaline -6-eulfonyl-, 2, J-dichloroquinoxaline-6-carbony1-, 2,3-dichloroquinoxaline -6-aulfonyl-, 1 ^ -Dichlorphthalazin-S-sulfonyl-

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or -carbonyl-, 2- or 3- or 4- (4 ^f _t 5'-dichloropyridazon-6 "-yl-1") - phenylsulfonyl- or -carbonyl, ß- (4 ', 5'-dichloropyridazon-6 " -yl-1 «) -ethyloarbonyl-, N-methyl ~ N- (2,4-dichlorotriazinyl-6-) ~ carbamy 1-, H-methylin- (2-methylamino-4-chlorotriazinyl-6) - carbamyl -, - K-methyl-N- (2-dimeth.ylamino-4-chlorotriazinyl-6) -carbamyl-, N-methy1- or N-ethy1-N- (2,4-dichlorotriazinyl-6) -aminoacety1- , N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-carbonyl) -aminoacetyl and the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic radicals, among them for example 2-fluoro-4-pyrimidinyl-, 2,6-difluoro-4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidiny1-, 2-chloro-5 »6-dichloro-4-pyrimidinyl-, 2,6-difluoro-S-methyl-1-pyrimidinyl-, 2,5-BLfluoro-6-methyl-4-pyrimidiny1-, 2-fluoro-5-methyl-6-chloro -4-pyriBidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidiny1 _f 2-fluoro-5-cyano-4-pyrimidinyl, 2.5 »6 -Trifluor -4-pyrimidinyl, 5-chloro-6-chloromethy1-2-fluoro-4-pyrimidiny 1,2,6-difluoro-5-bromo-pyrimidiny1, 2-fluoro-S-bromo-o-methyl ^ -pyrimidinyl-2 -Fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-fluoro-5-ii itro-4-pyrimidiny 1,2-fluoro-6 -methy 1-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4-pyriraidinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4- pyrimidinylf 2-fluoro-6-chloro-4-pyrilnidinyl, 6-trifluoromethyl -5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethy1-2-fluoro-4-pyrimidiny 1 »2-fluoro-5-nitro- 4-pyriraidinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or -5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl, 2-fluoro 5-carbomethoxy-4- "pyrimidinyl, 2-fluoro-5-bromo-6-trifluorraethyl-4-pyrimidinyl, 2-fluoro-6-carbonamido -4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2 -Pluor-

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6 ~ phenyl-4-pyrimidinyl, 2-fluoro-6 ~ cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl ~ 2-fluoro-5-sulfonamido-4-pyrimidinyl-2-Μι; ιθΓ-5-οΙι1θΓ-6-οαΓΐ> οηιβΐ1ιο: χ3Γ-4-pyrimidinyl, 2,6-difluoro-5-trifluoromethy1-4-pyrimidiny1; triazine radicals containing sulfonyl groups, such as 2,4-bis- (phenylsulfonyl) -triazinyl-6-, 2- (3'-car "boxyph.enyl) -sulfonyl-4-chlorotriazinyl-6-, 2- (3'-sulfophenyl) - sulfony1-4-chlorotriazinyl-6 ~, 2,4-B is- (3'-carboxy-phenylsulfonyl-1 ^f ) -triazinyl -6 j pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl ~ 6- methyl-pyrimidinyl -4-, 2-methylsulfonyl-6-ethyllyl-pyrimidinyl-4 _ί 2-phenylsulfonyl-5-olor-6-methyl-pyriniidinyl-4j 2 _T 6 -bis-methylsulfonyl-pyrimidinyl-4, -2.6 -Bis-nothylsu] fonyl-S-chloro-pyrimidinyl-4, 2 ^ 4 bis-methyl-sulfonyl-pyrimidine-5-sulfonyl, 2- .Methylsulfonyl-pyrimidinyl-4 »2-phenylsulfonyl-pyrimidinyl-4> 2-methylsulfonylpyrimidinyl-4 , · 2-Phenylsulfony 1-pyrimid.inyl-4, 2-Triohloraethylsulfonylf6-methyl-pyrimidinyl-4 »2-methylsulfonyl-» 5-chloro-6-methyl-pyrimidinyl-4, 2-methyl-sulfonyl-5- bromo-6 "-me thy l-pyrimx dinyl-4 _f- 2-methylsulfony 1-5-chloro-6-ethyl-phrimidinyl-4" 2-methylsulfony l-5-chloro-6-chlorodiethyl-pyrimidinyl-4 “2-methyl sulfone yl-4-chloro-6-methylpyrimidine-5-sulfonyli. 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4 »2,5,6-ü} ris-methylsulfonyl-pyrimidinyl-4 * 2-methylsulfony1-5 _f 6-dimethyl-pyrimidinyl-4, 2-ethylsulfonyl -5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfony1-6-chloro-pyrimidinyl-4 »2,6-bis-methyl-sulfonyl-5-chloropyrimidinyl-4, 2-methylsulfony1-6-earboxy-pyrimidiny1 -4, 2-Methylsulfony1-5-sulfo-pyrimidiny1-4, 2-Methylsulfony1-6-car "bomethoxy-pyrimidinyl-4 _? 2 ~ methylsulphonyl-5-carboxypyrimidinyl" 4 _f 2 ^ methylsulphonyl-S-cyano-6-methoxy -pyrimidinyl-4 »2-methylsulfony1-5-chloro-pyriraidiny1-4, 2-sulfoethylsulfonyl-6-methy1-pyrimidiny1-4, 2-methylsulfony1-5-fcrom-pyrimidinyl-4, 2-phenylsulfonyl-5-chloro-pyriraidinyl -4,

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2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-δ-chloropyrimidine-and -5-carbonyl-2,6-bis- (methylsulfonyl) -pyrimidine-4- or -5-carbonyl -, 2-Ethyl-sulfonyl-e-chloropyximidine-S-carbonyl-, 2,4-BiS- (methylsulfonyl) -pyrimidine-5-sulfonyl-, 2-methylsulfonyl-4-chloro i - 6-ynethylpyrimidine- 5-sulfonyl- or carbonyl-; triazine rings containing ammonium groups, such as 2-trimethylammonium -4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2- (1,1-dimethylhydrazinium) -4-plienylamino - or -4- (o-, m- or p-suifophenyl) - aminotriaziny1-6-, 2- (2-isopropylidene-l, 1-dimetnyl) -hy drazinium-4-phenylamino- or -4- (o- , m- or p-sulfophenyl) -aminotriazinyl-6-, 2-H-aminopyrrolidinium- or 2-N-amino-piperidinium-4-pnenyl-amino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, also 4-phenylamino or 4- (sulfophenylamino) -triaziny1-6 residues, which in the 2-position via a nitrogen _{bond the 1 f} 4-Bie-aea-bicyclo4-2,2,2-4 -octane or that

f-- | I-J Contains 0 »3» 34-octane quaternary bonded, 2-I ^ ridinium-4-phenylamino- or -4- (o-, m, or p-Bulfophenyl) -amino-triazinyl-6- and corresponding 2-QniuiBtriazinyl-6-Eeste, the 4-position by alkylamino, like Methylaoino-, Aethylamino- or ß-Hydroxyäthylamino-, or alkoxy, such as methoxy or ethoxy or aroxy, such as Bienoxy or sulfophenoxy groups are substituted; 2-chlorobenzothiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl-, 2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl-, such as 2-methylsulf onyl- or 2-ethylsulfonyl-benzothiazole-5- or -6-eulfonyl- or -carbonyl-, 2-phenylsulfonyl-benzthiazole-5- or -6-sulfonyl- or -carbonyl- and the corresponding 2-sulfonyl) enBtMazol-5- or -6-carbonyl- or -sulfonyl- containing sulfonyl groups in the fused benzene ring

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Derivatives, 2-chlorobenzox * zol-5- or -6-carbonyl- or sulfonyl-, 2-chlorobenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-1-meth.ylbenzimidazole-5- or-6-carbonyl - or -sulfonyl-, 2-chloro-4-methylthiazole- (i, 3) -5-carbonyl- or -4- or -5-sulfonyl-, N-oxide of 4-chloro- or 4-nitroquinoline-5-carbony 1 ·

Also to be mentioned are reactive groups of the aliphatic series, such as acryloyl, mono, di or trichloroacryloyl, such as -CO-CH = CH-Cl, -CO-CCl = CH ₂ , -CO-GCl = CH-CH ₅ , furthermore -CO-CCl = CH-COOH, -CO-CH = CCl-COOH, ß-chloropropionyl, 3-phenylsulfonylpropionyl, ß-sulfato-ethylaminosulfonyl, vinylsulfonyl, ß-chloroethylsulfonyl, ß-sulfatoethylsulfonyl, ß -Methylsulfony1-äthylsulfonyl-, ß-Phenylsulfonyläthylsulfonyl-, 2-Pluor-2.chlor-3,3-difluorocyclobutane-1-carbony1-, 2,2,3,3-Tetrafluorcyelobutancnrbony1-1- or -sulfonyl-1, ß- (2,2,3,3-Tetrafluorocyclobutyl-1) acryloyl, a- or ß-bromoacryloyl, a- or ß-Allqrl- or -arylsulfonylacryloyl groups, such as a- or ß-methylsulfony1-acryloyl, chloroacetylamino- , ß-chloropropionalamino, a, ß-dichloropropionylamino, a, ß-dibromo-propionylamino, ß-sulfcopropionylamino, ß-pulfony 1-propionylamino ^ groups

In the context of the new dyes, preferred compounds correspond the formulas:

CH,

CH

O D-N = N-CH

(ID SO ₃ H

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has the meaning given,

C = O

-N = Ii-CH

CN-ί / VNH ₂

SO ₃ H

η η ^ = - 0

(III)

stands for a carboxylic acid or sulfonic acid group and X stands for a reactive group, or

(IV)

a removable substituent, M and 1 Signify hydrogen or a substituent, in particular hydrogen, chlorine, bromine, methyl, Methoxy, ethoxy, sulfonic acid, carboxylic acid or acylamino groups

The best Y that can be split off includes, for example, halogen atoms (chlorine, bromine or fluorine), ammonium, including hydrazinium, sulfonium, sulfonyl, azido (N ₃ ), rhodanido, thio, thioether, ocyether, sulfinic acid and sulfonic acid. Other preferred dyes are those of the formula

le A 13 626

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209839/0982

M I

SO ₂ -CH ₂ -CH ₂ Z

wherein M and L have the meaning given, Z

for -OSO ₃ H, -SSO ₅ H, -OPO ₅ H ₂ , or -EG ( ¹¹ I represents, • where R ₁ and R _{2 are} lower Al- 2

denote alkyl, R ₅ denotes a hydrogen atom or a lower alkyl group and m denotes 0 or 1.

The new dyes are obtained when the biazo compound of an amine of the formula D ^ NH ₂ , where D has the above meaning, with at least 1 mole of a coupling component of the formula '

C = O

tu / ° 3 ^Η

(VI) ₀ H.

in which Q and F have the meaning given, combined. The coupling takes place in a weakly acidic, neutral or weakly alkaline medium.

Ie A 13 626 - 10 -

The compounds according to the invention can also be produced in such a way that that one in a dye of the formula

D ₁ -N = N-CH
¹ '// \

0 ^H

Q ^x

where D _{1 represents} the remainder of a diazo component free of reactive groups and Q and P have the abovementioned meaning, introducing a reactive group into remainder D. by conventional methods, for example by condensation or acylation.

The procedure here is to use a dye of the formula

C = O
HNr-WD ₂ -N = N-CH ^ v ^S0 3 ^H (VIII)

R, C ^ g H

in which R ,, Q and P have the abovementioned meaning, W represents a bridge member or a direct bond and D _{2 represents} a divalent aromatic-carbocyclic or aromatic-heterocyclic radical, in particular an optionally substituted phenylene or naphthylene radical, the grouping

-NH

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by condensation with an at least bifunctional reactive component = XY ¹ in which X is the radical of a reactive component and Y ^{1 is} an anionic, removable group, into a radical

-N-X

wherein R, has the meaning given and X represents the remainder of a reactive component, converts

The radicals W are, for example, -CH ₂ -, -SO ₂ -, -CH ₂ CO-NH-, -CH ₂ -CH ₂ -NH-SO ₂ -, -CH ₂ -CH ₂ -N (CH ₅ ) -SO ₂ -, -CH ₂ -CH ₂ -NH-CO-, -CH ₂ -CH ₂ -N (CH ₅ ) CO- are possible. W is preferably a direct bond or —CH ₂ -.

Examples of radicals D ₂ include: phenylene- (1,3) or - (1,4), 2-sulfo-phenylene- (1,3) or - (1,4), 2-carboxy-phenylene- ( 1,4), 2- or 3-carboxy-phenylene-6-methoxy-4-sulfophenylene- (1,3), 5-methoxy-2-sulfophenylene- (1,4), 2-methyl-5 -sulfophenylene- (1,3), 2-chlorophenylene- (1,4), 6-sulfonaphthylene- (1,4), 4,8-disulfonaphthylene- (2,6) - or - (2,5) , 2,2 ^ DiSuIfO-stilben-ylen- (4,4 ') »2,5-disulfo-phenylene- (1,4) or the

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Suitable aceteesigarylides are "for example acetoacetic" acid 4-amino-3,5-disulfoanilide, acetoacetic acid -4-amino 2,5-disulfoanilide.

Amines BHH _2, for example, compounds of the type of formulas IX XXV come into consideration ι

NH-X

X-NH

NH-X

HN
I.
X

XI

XII

CH ₃ O

NH ₂

SO ₃ H

X-HN-CH ₂ CH ₂ -NH-SO ₂

> NH,

XIII SO ^ H

X-HH CH,

XIV

X-NH

CH ₃ -N-CH ₂

SO ₃ H

XVI

XVII

OCH,

-NH,

SO ₉ -NX H

XVIII

X-HN

XIX

X-HN

XX

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X-NH

CH = CH

SO ^ H

XXI

COOH

XXIII

NH,

OCH,

NH ₂

XXII

XXV

in which X stands for a reactive group.

Ale amines

C.

its further connections of the following

Formulas called:

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XXVI
M.

• NIL Y ^N 0 L

XXVII M

SO ₂ -CH ₂ CH ₂ -OSO ₅ H

₂ CH ₂

• KH

2 XXVIII

ρ \ Jllip - VJ- uOiTl

SOo-CHo CH ₀ -S-SO ^ H

XXIX

SO ₂ -CH = CH ₂

XXX

N-SOp-CHp CHp-OSO ^ H

XXXI

öUp «" Ο v> ilp i «

K ₂ XXXII

wherein Y, M, L, R ₁ , R ₂ and R have the meaning given above.

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The following compounds, for example, are also listed as amine D-NH _2:

2-chloro- or 2- fluoro-6-amino-benzothiazole, 2-methylsulfonyl-, 2-ethylsulfonyl-, 2-phenylsulfonyl-, 2- (4-carboxyphenylsulfonyl) -, 2-methylsulfonyl-6-methoxy-7-- ainino-, 2-methylsulfonyl-6-amino-7-sulfonyl, 2-ethylsulfonyl-6-amino- and 2-ethylsulfonyl-6-amino-7-sulfobenzothiazole, 6-amino-2,3-dichloroquinoxaline, 3-araino - (ß-sulfatoäthylsulfony1) -benzene, 3- * Amino-4-methoxy- (ß-sulfatoäthylsulfonyl) -benzene, 4-amino-5-methoxy-2-methyl- (ß-sulfatoäthylsulfonyl) -benzene, 4-amino- (ß-sulfatoethylsulfonyl) -benzene, 3-amino-4-methoxy- (ß-diethylaminoethylsulfonyl) -benzene, 4-amino- (ß-diethylaminoethylsulfonyl) -benzene, N-methyl-N- (ß-sulfato ~ ethylsulfonyl) - phenyldiamine ~ (1,4), 4,5-dichloro- or 4,5-dibroia-1- (4 ^l -aminophenyl) -pyridaz; one- (6), 4,5-dichloro- or 4,5-dibromo -1- (4'-amino- '-sulfoplienyl) -pyridazon- (6), 4,5-Diohlor- or 4,5-dibromo-1- ^(5-amino-t 2 ^t -sulfophenylamino) -pyridazon- ( 6).

Will get the formula VIII are color bodies, one suitable amines ZWD coupling ₂ -NH ₂ wherein Z is a group -NH (R,), or can be converted into such a group radical, in particular a nitro group and W and D ₂ is as defined above have and then converts the group Z into the group -NH (R,) if necessary. Suitable amines are, for example:

5-nitro-2-amino-benzene-sulfonic acid, 2-amino-4-methylaminomethyl-benzene-sulfonic acid, S-Amino ^ -methylaminoBethylbenzenesulfonic acid, 4-nitro-i-amino-benzene, 4-nitro-2-chloro-1-amino-benzene, 6-nitro-2-amino-naphthalene-4,8-disulforic acid, 4-nitro-4'-aminostilbene ~ 2,2'-disulfonic acid, 5-nitro-2-amino-1-carboxy-benzene, T ~ Amino ~ 4 ~ nitro-naphthalene-6- or 7-sulfonic acid, 5 ~ nitro ~ 2-amino-1-methoxy-benzene-sulfonic acid-4, p-f2-amino-4,8 ~ disulfonaphtho- (5,6-4 ', 5') triazolyl- (2x) J-N-methylbenzylamine, 5-nitro-2-amino-1-methoxy-benzene-sulfonic acid-3.

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The reaction of the color bodies of the formula VIII with reactive components XY ¹ in which X is the meaning given and Y ^{1 is} an anionic, removable substituent, takes place in a manner known per se »

For this purpose, suitable reactive components XY ¹ are, for example, the above-mentioned reactive groups X d.en underlie

that is, in general, the halides, especially the chlorides of the acyl components X mentioned. From the large number of compounds available, the following may be mentioned here in extracts: Bubst.-amino-sym.-triazines, such as 2,6-dichloro-4-aminotriazine, 2,6-dichloro-4-methylaminotriazine, 2-6-dichloro-4-ethylaminotriazine, 2,6-dichloro-4-oxethylaminotriazine , 2,6-dichloro-4-phenylaminotriazine, 2,6-dichloro-4- (o-, m ~ or p-sulfophenyl) -aminotriazine, 2,6-dichloro-4- (2 », 5'-, - 2 ', 4 ¹ T * or -3 * »5 ^f disulfophenyl) aminotriazine, dihaloalkoxy and -aryloxy-sym, -triazines, such as 2,6-dichloro-4-methoxytriazine, 2,6-dichloro-4 ethoxytriazine, 2,6-diehlor-4-phenoxytriazine, 2,6-dichloro-4-Co-, m- or p-sulfophenyl) -oxytriazine, dihaloalkylmereapto- and -arylmercapto-sym.triazines, such as 2,6-dichloro -4-ethylmercaptotrizine, 2, e-dichloro ^ -phenylmercaptotriazine, 2,6-dichloro-4- (p-methylphenyl) -mercaptrotriazine; Tetrahalopyrimidines, such as tetrachloro-, tetrabromo- or tetrafluoropyrimidine, 2,4,6-trihalopyrimidines, such as 2,4,6-trichloro-, - tribromo- or trifluoropyrimidine, dihalopyrimidines, such as 2,4-dichloro -, -dibromo- or - difluoropyrimidine; 2,4,6-trichloro-5-nitro- or -5-methyl- or -5-carbomethoxy- or -5-carboethoxy- or -5-carboxymethyl- or -5-mono-, - di- or -trichloromethyl- or -5 ~ carboxy-

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or 5-sulfo- or -5-cyano- or -5-viny1-pyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6-difluoro-4-methyl-5-chloropyrimidine, 2,4-difluoropyrimidine -5-ethyl sulfone, 2,6-difluoro -4-chloropyrimidine, 2,4,6 ~ trifluoro-5-chloropyrimidine, 2,6-difluoro-4-methyl-5-bromopyrimdine, 2,4-difluor-5 , 6-dichloro- or -dibromopyrimidine, 4,6-difluoro-4T5-dichloro- or -dibromopyrimidine, 2,6-difluoro-4-bromopyrimidine, 2,4, β-trifluoro-5-bromopyrimidine, 2,4 »6 -Trifluor ₇ 57chloromethylpyrimidine, 2,4,6-trifluoro-5-nitropyrimidine, 2,4,6-trifluoro-5-cyanopyrimidine, 2 _f 4,6-trifluoro-pyrimidine-5-carboxylic acid alkyl ester or -5-carfeonic acid amide, 2, 6-difluoro-5-methyl-4-clilorpyrimidine, 2,6-difluoro-5-chloropyrimidine, 2,4,6-trifluoro-5-methylpyrimidine, 2 _f 4,5-! Drifluoro-6-methylpyriroidin, 2,4 -Difluoro <-5-nitro-6-clalorpyriinidine, 2,4-difluoro-5-cyano-pyrimidine _f 2,4-difluoro-5-met] iylpyrimidine, δ-trifluoromethyl-S-chloro-2,4-difluoropyrimidine. _f 6-phenyl-2 5 4-difluoropyrimidine, 6-trifluoromethyl-2,4-difluoropyrimidine, 6-trifluoromethyl-2,4-alfluoropyrimidine, 5-trifluoromethyl-2 ₅ 4 ₉ 6-trifluoropyrimidine, 2,4-difluoro-5- aitro-pyrimidine _? 2 ₉ 4-Difluoro-5-trifluoromethylpyrimidine, 2,4-Mfluoro ~ 5-methylsulfonyl-pyrimidine,: 2,4-Difluoro-5-piieny 1-pyrimidine, 2,4-Diflu.or-5 ~ carbonamidopyrimidiiii E ^ - Difluoro-S-carbomethoscy-pyrimidine, 2,4-difluoro-6-trifluorometh ^ 1-pyrimidine, 2,4-difluoro-5-bromo-6-trifluoromethy1-pyrimidine _s 2 ₉ 4-Difluoro-e-carbonamido-pyrimidia, 2,4-Difluoro-6-carbon-1-pyrimidine, 2,4-difluoro-6-carbo-ethoxy-pyriaiidine, 2,4-difluoro-6-pheny1-pyrimidine, 2,4-di-fluoro-6-. cyano-pyrimidine, 2,4,6-irifluoro-5-methylsulfony1-pyrimidine _f 2 , 4-difluoro-5-sulfonamido-pyrimidine, 2,4-difluoro-5-chloro-6-carbomethosy-pyrimidine, 5-trifluoromethyl 2,4-difluoropyriraidine, 2 ^ »dichloropyrimidine-S-carboxylic acid chloride, 2,4, 6-srichloropyrimidine-S-carboxylic acid chloride, 2-methyl

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^ -chloropyrimidine-S-carboxylic acid chloride, 2-chloro-4-methylpyrimidine-5-carboxylic acid chloride, 2,6r-dichloropyrimidine-4-carboxylic acid chloride; Pyrimidine reactive components with separable sulfonyl groups, such as 2-carboxymethylsulfonyl-4-chloropyrimid-yne, 2-methyl sulfony 1 ^ -chloro-δ-methyl pyrimidine, 2,4-bis-methylsulfonyl-6-methylpyrimidine, 2,4-bis -phenylsulfony1-5-chloro-6-methylpyrimidine, 2,4,6-tris-methylsulfonylpyrimidine, 2,6-bis-methylsulfonyl-4,5-dichloride-pyrimidine, 2,4-bis-methylsulfonylprimidine-5-sulfonic acid chloride, 2-methyl -sulfony1-4-chloropyrimidine, 2-phenylsulfony1-4-chloropyrimidine, 2,4-bis-trichloromethylsulfonyl-6-methylpyrimidine, 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine, 2,4-bis-methylsulfony1 -5-bromo-6-methylpyrimidine, 2-methy1-sulfony1-4,5-dichloro-6-methylpyrimidine, 2-methylsulfony1-4,5-dichloro-6-chloromethylpyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimidine -5-sulfonic acid chloride, 2-methylsulfonyl-4-chloro-5-nitro-6-methylpyrimidine, 2,4,5 »6, -Tetramethylsulfony1-pyrimidine, 2-methylsulfonyl-4-chloro-5,6-dimethylpyrimidine, 2- Ethylsulfony1-4,5-dichloro-6-methylpyrimidine, 2-methylsulfony1-4,6-dichloropyrimidine, 2, 4,6, -trismethylsulfony1-5-chloropyrimidine, 2-methylsulfony1-4-chloro-6-car "boxy pyrimidine, 2-methylsulfony 1-4-chloropyrimidine -5-sulfonic acid, 2-methylsulfonyl-4-chloro- 6-carbomethoxypyrimidine, 2-methylsulfonyl-4-chloropyrimidine-5-car "bonic acid, 2-methylsulfonyl-4-chloro-5-cyano-6-methoxypyrimidine, 2-methylsulfony1-4,5-dichloropyrimidine, 4-methylsulfony1-6- chloropyrimidine, 2- SuIfoäthylsulfonyl-4-chloro-6-methy1-pyrimidine, 2-methylsulfonyl-4-chloro-5-bromopyrimidine, 2-methyl-sulfonyl-4-chloro-5-bromo-6-methylpyrimidine, 2,4- Bis-methylsulfony1-5-chloropyrimidine, 2-phenylsulfonyl-4,5-dichloropyrimidine 2, Pheny1-sulfony1-4,5-dichloro-6-methylpyrimidine, 2-carboxymethylsulfony1-4,5-dichloro-6-methylpyrimidine, 2- ( 2 · - or 3 »- or 4 ^f -carboxy-phenylöulfonyl) -4,5-dichloro-6-methylpyri-

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midine, 2,4-bis- (2 ^f - or 3 '- or 4'-carboxyphenylsulfony1) -S-chloro-δ-methy! pyrimidine2-M. Ethy lsulfony 1-6 ~ chloroprimidine-4- or -5-carboxylic acid chloride, 2-ethylsulfony1-6-chloropyrimidine-4- or -5-carbonic acid chloride, 2,6-bis-. 4-methylsulfonyl) -pyrimidine-4-carbonic acid chloride, 2-methylsulfonyl-6-methyl-4-chloro- or -4-bromopyrimidine-5-carl) onic acid chloride or bromide, 2,6-bis- (methylsulfonyl) -4-chloropyrimidine- 5-carboxylic acid chloride; further reactive components of the heterocyclic series with reactive sulfonyl substituents are, for example, 3,6-bis-phenylsulfonylpyridazine, 3-methylsulfonyl-6-chloropyridazine, 3,6-bis-tri- chloro-methylsulfonylpyridazine, 3 ₁ 6-bis-methylsulf onyl-4-methyl-pyridazine, 2,5,6-tris-methylsulfonyl-pyrazine, 2,4-bis-methylsulfonyl-1,3 »5-triazine, 2,4-bis-methylsulfonyl-6- (3 '-sulfophenylamino) -1 , 3,5-triazine, 2,4-bis-methylsulfony 1-6-N-methylanilino-1,3 _f 5-triazine, 2,4-bismethyl sulfony 1-6-trichloroethoxy-1,3,5 »- triazine, 2,4,6-tris-phenylsulphonyl-1,3-5-triazine, 2,4-bis-methylsulphonylquinazoline, 2,4-bis-trichloromethy-1-sulphonylquinoline, 2,4-bis-carboxy-methylsulphony-lquinoline, 2 , 6-Bis ^ methylsulfony lJj-pyridine-4-carboxylic acid chloride and 1- (4'-chlorocarbonylphenyl or 2 * -chlorocarbonylethyl ) -4,5-bis-methyl-1-sulfony 1-pyridazon- (6); 2,4 bis-methylsulfonyl-6-phenoxy-1,3,3-triazine. further herocyclic Röactive components with mobile halogen bind, inter alia 2- or ^ -monochloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or 3-monobromochinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dibromoquinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 1 ^ -dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding

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Bromine compounds, 2,4-dichloroquinazeln-6- or -7-carboxylic acid chloride and the corresponding bromine compounds, 2- or 3- or 4- (4S5 ^l -dichloropyridazon-6 ^l ~ yl-l ') - phenylsulfoa acid chloride or - carboxylic acid chloride and the corresponding bromine compounds, ß- (4 ', fj'-dichloropyridazon-ö'-yl-l ¹ ) -ethylcarboxylic acid chloride, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding bromine compound, N-methyl-N- (2,4 , dichlorotriazinyl-6) -carbamic acid chloride, N-Me thy1-N- (2-chloro-4-methylamino-triazinyl-6) -carbamide acid chloride, N-Me thy1-N- (2 ~ chloro-4-dimethylamino-triaziny1- 6) carbamic acid chloride, N-methyl or N-ethyl-N- (2,4-dichlorotriazinyl-ej-amino-acetyl chloride, N-methyl, N-ethyl or N-hydroxyethyl-N- (2,3- dichloroquinoxaline-6-sulfonyl- or -6-carbonyl) -aminoacetylchloride and the corresponding bromine derivatives, also 2-chlorobenzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-arylsulfonyl or 2-alkyl sulfo nyl-benzthiazole-5- or -6-carboxylic acid chloride or -5- or -o-sulfonic acid chloride, such as 2-methylsulfonyl- or 2-ethylsulfonyl- or 2-phenylsulfonyl-benzthiazole-5- or -6-sulfonic acid chloride or -5- or -6-carboxylic acid chloride and the corresponding! 2-sulfonyl benzothiazole derivatives containing sulfonyl groups in the fused benzene ring 3 1 5-bis-methylsulfonyl-isothiazole-4-carboxylic acid chloride, E-chlorobenzoxazole-S- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives, B- Chlorobenzimidazole-S- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives, 2-01110 ^ 1-13 ^ 1 ^ 1 ^ 6 ^ 1110 ^ 201-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives,

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2-chloro-4-methylthiiazole- (1,3) -5-carboxylic acid chloride or -4- or -5-sulfonic acid chloride, 2-chlorothiazole-4- or -5-sulfonic acid chloride and the corresponding bromine derivatives.

From the series of aliphatic reactive components, the following should be mentioned, for example: acrylic acid chloride, mono-, dioders Trichloroacrylic acid chloride, 3-chloropropionic acid chloride, 3-phenylsulfonyl-propionic acid chloride, 3-methylsulfonyl-propionic acid chloride, 3-ethylsulfonyl-propionic acid chloride, 2-chloroethanesulfochloride, chloromethanesulfonyl chloride, 2-chloroacetyl chloride, 2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid chloride, ß- (2,2,3,3-tetrafluorocyclobutyl-1) acrylic acid chloride, ß- (2,3,3-trifluoro-2-chloro-cyclobutane-1) -carboxylic acid chloride, ß-methyl-sulfonyl-aoryl acid chloride, a-methylsulfonyl-acrylic acid chloride and α-bromoacrylic acid chloride and β-bromoacrylic acid chloride.

Performs the conversion to dyes which are more than one reactive G roup in the radical X or have elsewhere in the dye molecule, these can partially by other groups ", for example, _g amino replaced, which in turn reactive $ 'groups ₅ 25» B. In Form of esterified oxalky groups ₉ may have «,

In principle, the presence of two or more different Eeaktivgruppen in the dye is possible *

The new dyes are suitable for dyeing and printing materials containing hydroxyl groups, such as Textile fiber »- threads and fabrics made of wool, silk, synthetic polyamide and polyurethane fibers and for washable Dyeing and printing of native or regenerated cellulose

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the treatment of cellulosic materials being conventional in the presence of acid-binding agents and, if necessary, by the action of heat according to those known for reactive dyes Procedure takes place.

In the following examples, parts stand for parts by weight. The temperature data are degrees Celsius.

example 1

22 parts of 2-amino-5-nitro-benzene-sulfonic acid-1 are indirect diazotized. The suspension of the diazo compound leaves to a solution of 35 parts of 4-amino-3,5-disulfoacetoacetic anilide and 28 parts of bicarbonate in 150 parts Running in water «The coupling takes place quickly.

25 parts Na ₂ S. 3H ₂ O are dissolved in 300 parts of water and by adding conc. Found hydrochloric acid to pH 10, wherein the addition takes place below the liquid surface · is then heated to 50-6O ⁰ C., and the nitro compound obtained according to paragraph 1. When the reduction is complete, the precipitated sulfur is filtered off and the dye is salted out from the filtrate by adding 20 volumes of sodium chloride and filtered off.

The paste is dissolved in 800 parts of water and, after heating to 45 ° , 28 parts of 2,3-dichloroethinoxaline-6-carboxylic acid chloride are added. The pH value is kept between 6 and 7 by adding 10biger soda solution. After several hours of stirring, the condensation has ended. It is clarified and the dye is separated from the filtrate with 10 volumes of sodium chloride. After suctioning off, drying and grinding , a yellow dye powder is obtained, which is slightly yellow

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Color soluble in water.-Corresponds in the form of the free acid the dye of the formula

Ϊ- / so CH, Ύ _ / V ⁵ C = O C-J N = N-CII κ I. O C-N Il TT O ⁿ

SO ^ H

After one of the following staining examples achieved it gives a clear, greenish yellow of good lightfastness and washfastness on cellulosic materials.

For the production of the coupling component

4-Amino-3,5-disulfo-acetessigsäuz'C! Anilid is as follows procedure:

540 parts of 1,4-diamino-benzene-2,6-disulfonic acid are neutralized with 120 parts by volume of concentrated sodium hydroxide solution (d = 1.5) in 2000 parts by volume of water. Then allowed to 176 parts by volume of diketene dropwise to give by cooling makes sure that the temperature does not rise above 40 ⁰ C. This gives 2700 parts by volume of a clear solution which can be used directly for the coupling. The compound can be separated out by adding 25 vol. Table salt.

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BATH ORIGINAL

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Dye i fj pie le
Printing specification

If you print cotton nettle with a printing paste, dir = per kilogram contains 20 g of the dye, 100 g urea, 300 r.il V / aseer, 500 g alginate thickening (60 g sodium alginate t / k..r thickening) and 10 g soda, and which is precipitated to 1 kg with water, dries, steams for 1 minute at 103 ° g, rinsed with hot water and soaped at the boil, a clear, greenish yellow print of good wet and light fastness is obtained.

Blocking regulation

30 parts of the dye prepared according to Example 1 v / earth ■■ ·: ·· dissolved in 1000 parts of water. With this solution, a cotton fabric is fouladiert and up to a weight loss of 90 cent pressed /. The still moist cotton is treated at 70 ° for 30 minutes in a bath which contains 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate dissolved in 1000 parts of water. The dyeing is then completed in the usual way. A clear greenish-yellow dyeing with excellent wet and light fastness properties is obtained.

Dyeing pre-chri ft

168 ml of 20-25 water are placed in a staining beaker with a content of 300 ml, which is located in a heatable water bath. 0.3 g of the dye obtained according to Example 1 is pasted well with 2 ml of cold water and 30 ml of hot water (70 °) are added; the dye dissolves in the process. The dye solution is added to the water initially charged. and 10 g of cotton yarn kept in constant motion in this dye liquor, within 10 minutes the temperature of the dye liquor is increased to 70-00 _tons . 10 g of water-L e A 13 626 - 25 -

209839/0982 bad or, _QINAL

add free sodium sulfate and continue staining for 30 minutes. Then 4 g of anhydrous sodium carbonate are added to the dye liquor and stains for 60 minutes at 70-80 °. The dyed material is then removed from the dye liquor and the adhering material removed Wringing or pressing the liquor out and rinsing the material first with cold water and then with hot water until the wash liquor is no longer bled. The colored material is then poured into 200 ml of a Liquor containing 0.2 g sodium alkyl sulfate, during 20 Soaped for minutes at boiling temperature, rinsed again and dried at 60-70 ° in a drying cabinet. One receives a greenish yellow color of excellent wash and lightness.

If the procedure given in Example 1 is followed, however, using the procedure given in the table below Diazo and reactive components listed, so you also get valuable reactive dyes. The different The reactivity of the reactive components in the acylation is taken into account by selecting the appropriate temperature, as it is known from literature.

Le A 15 626 - 26 -

For example, a diazo component

Re alct ivkoinponent e

hue

2 3

7th 3 9 O
co ■ io CX) 11 co 12th O co 13th co 14th 15th 16 17th

18th

1-Amino-4-nitroenzene-2-sulfonic acid

Il 11

It ti

1-Amino-2-car'boxy-4-nitro-benzene

It

dd

4-Nitro-4 ¹ -aminostilbene-2,2 "-disulfonic acid

2,4,6-trifluoro-5-chloro-pyrimidine Te trachloropyriraidine

1,4-Di chlorophthalazine-6-carboxylic acid chloride

2-Metliylsulfonyl-'benztliiazol-5- or 6-carboxylic acid chloride

β- (2,2,3,3-tetrafluorocyclobuty1-1) arylic acid chloride

a-3romacry! acid chloride

2,5-bis-diethylsulfony 1-isothiazole-4-carboxylic acid chloride

Cyanuric chloride

2-amino-4,6 dichlorotriazine 2-A2iino-phenyl-4,6-dichlorotriazine 2-methylsulfonyl-4,5-dichloro-6-

Ee thy 1-pyriinidine

2,4,6-trichloropyrimidine-5-car ~ bons acid chloride

green

Il

3 _ (, · <.ι j ^ '- Dichl
propionyl chloride

-G'-yl-i ') -

It

It

2,3-chloride

2,4,6-trifluoro-5-chloro-pyrimidine

2-methylsulfonyl-4,5-dichloro-6-yne thy 1-py rinil din

2,3-dichloroquinoxaline-6-carTDonic acid ΐ yellow chloride

Example diazocomonente

Reactive component

hue

20 21

22 23 24 25

26 27

28

7-sulfonic acid

4-Hitro-4 • -aminostilbene-2,2'-disul-tetrachloropyrimidine fonic acid

¹¹ 2,4,6-Irifluoro-5-chloropyriinidine

-6- or 2,3-dichloroquinoxaline-6-carboxylic acid chloride

2,4,6-trifluoro-5-chloro-pyrimidine
Cyanuric chloride
Tetrachloropyrimidine

yellow

Il

ti it

2-Amino-6-nitro-nε ^ pilttlalin-4,8-disulfonic acid ■

1-Amino-2-methoxy-4-nitro-'benzene-5-sulfonic acid

1-Amino-4-n.itro "benzene

Cyanuric chloride

Il

, 3-dichloro quinoxaline-6-car "bon-

acid chloride

Cyanuric chloride

2- (4'-Sulfophenylamino) -4,6-dichloro-triazine

Il (1 Il Il It

grins. Yellow

4'-nitro-2'-sulfo-4-aminodiphenylamine cyanuric chloride

H Il

! I

Yellow

example J> 2

A solution of 26.8 parts of 1,4-diainino-benzene-2,5-disulfonic acid, neutralized with sodium carbonate, is added aqueous suspension of 875 parts of cyanuric chloride and stir the mixture at a temperature of 0-5, whereby one through Adding a dilute sodium hydroxide solution dropwise keeps the pH value slightly acidic. After the condensation has ended, it is acidified with 30 parts of 30 ^ hydrochloric acid and diazotized with 24.5 Vol. Parts of a 30% sodium nitrite solution. The yellow diazotization obtained is added to an ice-cold 28 parts Sodium hydrogen carbonate-containing solution of 35 parts of 4-amino-3,5-disulfo-acetacetic anilide. After finished Coupling is destroyed with hydrochloric acid, the excess sodium hydrogen carbonate and the dye by salting out and Filtering isolated. The dye paste is made with a mixture from 5 parts of disodium phosphate and 5 parts of monosodium phosphate mixed and dried in vacuo at low temperature. The dye that corresponds to the following formula.

gives clear, green-tinged yellow after one of the dyeing processes mentioned Dyeings of good light and wet fastness.

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In Example 32, the 4-amino-3,5-disulfoacetoacetic acid arylide is replaced through, the appropriate amount of the 4-amino ~ 2.5 ~ disulfo-aeetoacetic acid arylide is also obtained a valuable reactive dye, cotton has a green tint yellow tones.

Example 33

50 parts of 10biges are added to the chlorotriazine dye solution obtained as described in Example 32 Ammonia and keeps the solution for 2 hours at 35 ° · Then becomes the monochlorotriazine dye formed is salted out, isolated and dried. A dye is obtained which dyes cotton in clear, greenish-yellow shades. Replace one Ammonia by equivalent amounts of ethylamine, ethanol or Diethanolamine, this gives dyes with similar properties.

Example 34

24.5 parts of 1-amino-2-methoxy-4- (ß-sulfatoethylsulfonyl) -5-methyl-benzene are indirectly diazotized and alkaline bicarbonate to a solution of 35 parts of 4-amino-3,5-disulfoacetoacetic anilide coupled in 150 parts of water. The dye is isolated by salting out and filtering. He corresponds to the formula

HO ₅ SO-CH ₂ CH ₂ -SO ₂

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This gives strong greenish-yellow tones on cotton Colorations

Example 35

46.3 parts of p- | _2-amino-4,8-disulfonaphtho- (5, 6.4 ·, 5 ') -triazolyl- (2 ^f ) -N-methylbenzylamine are diazotized indirectly. The suspension of the diazo compound is allowed to run into a solution of 35 parts of 4-amino-3,5-disulfo-acetic acid anilide and 28 parts of sodium hydrogen carbonate in 150 parts of water. After coupling is complete, the mixture is heated to 40 ° and 28 parts of 2,3-dichloroquinoxaline-6-carboxylic acid chloride are sprinkled in. The pH value is maintained between 7 and 8 by adding 10% sodium carbonate solution dropwise. The acylated dye is separated off after clarification and salting out isolated. It corresponds to the following formula:

HCUS

CH ₅ -K-CH ₂

OH,

C = O

.N = N-CH

SO ₃ H

0 ^Ά

NH.

SO ₃ H

and dyes a clear yellow on cotton by one of the processes mentioned. If you proceed according to the information this Example, but using the diazo and reactive components listed below, is also obtained valuable reactive dyes.

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Example diazo component *! Reactive components

hue

3-amino ~ 4 ~ methoxy ~ 2,4,6-trifluoro ~ 5-chlorine green,

benzylmethylamine pyrimidine ti Il

4 ~ Amino-benzylmethylamine

Tetrachloropyrimidine

2-Broir aerylic acid chloride

2,4,6-trifluoro-5-chloropyrimidine

Yellow

Example 40

26 parts of finely powdered 2-methylsulfonyl-6-methoxy-7-aminobenzothiazole are concentrated with 28 parts. Hydrochloric acid in a mixture of 250 parts of water and 250 parts of ice stirred. 24.5 parts by volume of 30% sodium nitrate solution are left come in. The mixture is stirred for 1 hour and the diazotization is clarified. The yellow solution runs out into a Yorlax solution 35 parts of 4-amino-3,5-disulfo-acetacetic anilide and 28 parts of sodium hydrogen carbonate in 150 parts of water. After the coupling is complete, the dye is salted out isolated. It corresponds to the following formula:

SO ₂ OH

OCH,

N = N-CH

SO, H

SO, H

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and gives a clear yellow of good light and wet fastness when printed on cotton.

Example 41

The neutral solution of 33.7 g of 4- (2x, 6'-difluoro-5'-chloropyrimidinyl- (4 ') -amino) -anilinesulfonic acid- (2) (calculated as free acid) in 200 ml of water is after dissolving of 7.2 g of sodium nitrite in a mixture of 30 ml of concentrated hydrochloric acid (d = 1.18) and 200 g of ice. It is tracked for 1 hour at ⁰ ° C. before excess nitrite is destroyed with sulfamic acid. A neutral solution of 35.2 g of 4-acetylamino-aniline-disulphonic acid (2.6) (calculated as the free acid) in 150 ml of water and a further 100 g of ice is then added and about 110 g is left in for 1 hour Drip in ml of 10% sodium hydroxide solution at 0 ⁰ G until the pH value * 7 is reached. The coupling is then complete.

The mixture is warmed to room temperature, the precipitation of the dye is completed by introducing 100 g of sodium chloride and, after 1 hour, suctioned off. The dye of the formula which is dried at 50 ^{° C. in vacuo}

CH *

S0, well

CO ' ³

N = N-CH-CO-NII- / -, - "ng

SO ₅ Well

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represents a yellow powder and is identical to the product described in Example 2.

Claims (10)

Claims 1. Reactive dyes of the formula D ^ N = N-CH C-N- / Q P wherein Q and P are hydrogen or a sulfonic acid group, but cannot simultaneously have the same meaning and D is the remainder of an aromatic containing reactive groups -carbocyclic or aromatic-heterocyclic diazo component. 2. reactive dyes of the formula D-N = N-CH wherein D has the meaning given in claim 1. Ie A 15 626 - 34 - 209839/0982 3. Reactive dyes of the formula above A for a hydrogen atom, a carboxylic acid or Sulfonic acid group, and X represents a reactive group, 4 «reactive dyes of the formula CH ₅ . C = O -N = N-CH "/ 1! ■ where L and M are hydrogen or a substituent and Y represent a removable radical, in particular a sulfonyl radical or a halogen atom Le A 13 626 -35 - 209839/0982 5. Reactive dyes of the formula CH ₅ C = O _s ' N = N-CH / ί-κΑ: SO ₂ -CH ₂ CH ₂ Z SO ₃ H where M and L are hydrogen or a substituent, R, hydrogen or lower alkyl, Z is the radical -OSO ^ H, -OPO ₃ H ₂ or -Ήζ ^ß 1 represent, wherein R ₁ and R _{2 are} R ₂ is lower alkyl, and m is 0 or 1. 6. Process for the preparation of reactive dyes of the formula in which Q and P denote hydrogen or a sulfonic acid group, but cannot simultaneously have the same meaning, D denotes the radical of an aromatic carbonylic or aromatic heterocyclic diazo component containing reactive groups, characterized in that amines of the formula Le A 15 626 - 36 - 209Ö39 / 0982 ? 113298 J? I) -NH ₂ in which D has the meaning given, diazotized and with acetoacetic arylides of the formula ^S0 3 ^H C = O CH Il \ v / orin Q and P have the meaning given, coupling, 7. Process for the preparation of dyes of the formula CH, D-N = N-CH CNH- / V ^NH P Il \ / ^ Q P wherein D is the radical of an aromatic carbocyclic containing reactive groups or aromatic-heterooyclic diazo component and P and Q is hydrogen or a Represent sulfonic acid group, but can not have the same meaning at the same time, characterized in that one in dyes of the formula Ie A 13 626 - 37 - 209839/0982 where D .. represents the radical, free of reactive groups, of an aromatic-carbonic or aromatic-heteroechoic diazo component and P and Q have the meaning given, introducing a reactive group _{into the radical D 1.} 8. Process for the preparation of dyes of the formula CH ₅ ? ^{= 0} SO ₃ H XNWD ₂ -N = N- _t ^ / R, C-NH- / VNH fp η \ / * - QP where X is a reactive group, R is hydrogen or a lower alkyl group, W is a direct bond or represents a bridge member, D * represents a divalent aromatic-carboeyclic or aromatic-heteroeyclic Radical 'and P and Q are hydrogen or a sulfonic acid group, however cannot simultaneously have the same meaning, characterized in that dyes of the formula Ie A 13 626 - 38 - 209839/0982 C = O _qn " i bU-, H E, C P Ii \ —z / ' o / - \ Q ι where E ,, W, Dg and P and Q have the meaning given above have with connections X-Y condensed, where X is a reactive group and Y ^{1 is} an anionically removable Best. 9. Use of the dyes of claims 1-5 for dyeing and printing on fiber materials containing hydroxyl or amide groups 10. With the dyes of claims 1-5 or colored printed fiber materials containing hydroxyl or amide groups. Le A 13 626 209839/0982