CH639683A5 - Process for preparing new copper complexes of azo dyes - Google Patents

Description

The present invention relates to a process for the preparation of new copper complexes of azo dyes of the formula I.

(Ul)

S03li

S03H

wherein

Z has the meaning given above and

D 'represents a mono-, di- or trisulfonaphthylene radical.

The coupling component of the formula V used in the dyes (I)

is known from the literature. It is produced by sulfonating 8-amino-l-oxy-6-sulfonaphthalene [DRP 8626 (1896); DRP 108848 (1899); Frdl. 4,567,764; 5,503], which is itself obtained from the l-amino-3,8-disulfonaphthalene by alkaline melting [DRP 4723 (1890); Frdl. 3, 454],

Reactive groups Z are understood to mean those which have one or more reactive groups or removable substituents which, when the dyes are applied to cellulose materials in the presence of acid-binding agents and, if appropriate, under the action of heat with the hydroxyl groups of the cellulose or when applied to superpolyamide fibers such as wool to react with the NH groups of these fibers to form covalent bonds. A large number of such fiber-reactive groups are known from the literature.

Reactive groups suitable according to the invention which contain at least one removable substituent bonded to a heterocyclic or to an aliphatic radical include those which contain at least one reactive substituent bonded to a 5- or 6-membered heterocyclic ring, such as to a monoazine , Diazine, triazine, e.g. B. pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxa-tin or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic rings, such as a quinoline, phthalazine, Cinnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system; the 5- or 6-membered heterocyclic rings which have at least one reactive substituent are therefore preferably those which contain one or more nitrogen atoms and may contain 5 or preferably 6-membered carbocyclic rings fused on.

Examples of reactive substituents on the heterocycle include:

Halogen (Cl, Br or F), ammonium, including hydrazione, sulfonium, sulfonyl, azido (N3), rhodanido, thio, thioether, oxyether, sulfinic acid and sulfonic acid. The following can be mentioned in detail:

Mono- or dihalo-symmetrical-triazinyl residues, e.g. B. 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-propylamino-4-chlorotriazinyl-6-, 2-ß-ox-ethylamino-4-chlorotriazinyl-6-, 2-di-ß-oxäthylamino-4-chlorotri-azinyl-6- and the corresponding sulfuric acid semiesters, 2-di -ethylamino-4-chlorotriazinyl-6-, 2-morpholino- or 2-piperidi-no-4-chlorotriazinyl-6-, 2-cyclohexylamino-4-chloro-triazinyl-6-, 2-arylamino and substituted arylamino-4-chlorotriazinyl -6-, such as 2-phenylamino-4-chlorotriazinyl-6-, 2- (o-, m- or p-carboxy, or sulfophenyl) -amino-4-chlorotriazinyl-6-, 2-alkoxy-4- chlorotriazinyl-6 such as 2-methoxy or ethoxy-4-chlorotriazinyl-6-, 2- (phenylsulfonylmethoxy) -4-chlorotriazinyl-6-, 2-aryloxy and substituted aryloxy-4-chlorotriazinyl-6- such as 2-phenoxy -4-chlorotriazinyl-6-, 2- (p-sulfophenyl) -oxy-4-chlorotriazinyl-6-, 2- (o-, m- or p-methyl- or methoxyphenyl) -oxy-4-triazinyl-6- , 2-alkylmercapto or 2-arylmercapto or 2- (substituted ary l) -mercapto-4-chlorotriazinyl-6, such as 2-ß-hydroxyethyl-mer-capto-4-chlorotriazinyl-6-, 2-phenylmercapto-4-chlorotriazinyl-6-,

3,639,683

2- (4'-Methylphenyl) mercapto-4-chlorotriazinyl-6-, 2- (2 ', 4'-dinotro) phenylmercapto-4-chlorotriazinyl-6-, 2-methyl-4-chlorotri -azinyl-6-, 2-phenyl-4-chlorotriazinyl-6,2- (o-, m-, p-methylphenyl) -amino-4-fluorotriazinyl-6-, (o-, m-, p-Sulfophenyl) amino-4-5 fluorotriazinyl-6-, 2- (2 ', 5'-disulfophenyl) amino-4-fluorotriazonyl-6-, mono-, di- or trihalopyrimidinyl radicals, such as 2,4-dichloropyrimidinyl-6-, 2,4,5-trichloropyrimidinyl-6-, 2,4-di-chloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-i ° mono- -di or -trichloromethyl- or -5-carboalkoxy-pyrimidynyl-6-, 2,6- Dichloropyrimidine-4-carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methylpyrimidine-5-carbonyl-, 2-methyl-4-chloropyrimidine-5-carbonyl-, 2-methylthio-4- fluoropyrimidine-5-carbonyl-, 6-methyl-2,4-dichloropyrimidine-5-carbonyl-, 2,4,6-15 trichloropyrimidine-5-carbonyl-, 2,4-dichloropyrimidine-5-sulfonyl-, 2 -Chloroquinoxaline-3-carbonyl-, 2- or 3-monochloroquinoxali n-6-carbonyl-, 2- or 3-monochloroquinoxaline-6-sulfonyl-, 2,3-dichloroquinoxaline-6-carbonyl-, 2,3-dichloroquinoxaline-6-sul-fonyl-, 1,4-dichlorophthalazin-6 -sulfonyl-or-6-carbonyl-, 2,4-20 dichloroquinazolin-7- or-6-sulfonyl-, or carbonyl-, 2- or 3-or4- (4 ', 5'-dichloropyridazon-6'-yl -l ') - phenylsulfonyl- or carbonyl-, ß- (4', 5 '-Dichlorpyridazon-6' -yl-1 ') -ethylcarbonyl-, N-methyl-N- (2,4-dichlorotriazinyl-6-) -carbamyl-, N-methyl-N- (2-methylamino-4-chlorotriazinyl-6 -) - carbamyl-, N-methyl-N- (2-25 dimethylamino-4-chlorotriazinyl-6 -) - carbamyl-, N -Methyl- or N-ethyl-N- (2,4-dichlorotriazinyl-6 -) - aminoacetyl-, 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 30 chlorine-substituted heterocyclic radicals, including, for example, 2-fluoro-4-pyrimidinyl-, 2,6-difluoro- 4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-5,6-dichloro-4-pyrimidinyl-, 2,6-difluoro-5-methyl-4-pyrimidinyl-, 2,5-difluoro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl-, 35 2- Fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyan-4-pyrimidinyl, 2-fluoro-5-methyl -4-py-rimidinyl-, 2,5,6-trifluoro-4-pyrimidinyl-, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl-, 2,6-difluoro-5-bromo-4- pyrimidinyl-, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl-, 2-fluoro-5-bromo-6-chloro-40 methyl-4-pyrimidinyl-, 2,6-difluoro-5-chloromethyl- 4-pyrimidynyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4 -pyrimidinyl-, 2-fluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-6-chloro-4-pyrimidinyl-, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl-, 6 -Trifluoromethyl-2-fluoro-45 4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-tri-fluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl or -5-methyl-sulfonyl-4-pyrimidinyl-, 2-fluoro-5-carbonamido-4-pyrimidinyl-, 2-fluoro-5-carbomethoxy-4-pyrimidinyl-, 2-fluoro-5-bromo-6-tri- fluororm ethyl-4-pyrimidinyl-, 2-fluoro-6-carbonamido-4-pyrimidi-50 nyl-, 2-fluoro-6-carbomethoxy-4-pyrimidinyl-, 2-fluoro-6-phenyl-4-pyrimidinyl-, 2 -Fluoro-6-cyan-4-pyrimidinyl-, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl-, 2-fluoro-5-sulfonamido-4-pyrimidynyl-, 2-fluoro-5- chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-di-fluoro-5-trifluoromethyl-4-pyrimidinyl; 55 triazine residues containing sulfonyl groups, such as 2,4-bis (phenylsulfonyl) triazinyl-6-, 2- (3'-carboxyphenyl) sulfonyl-4-chlorotriazinyl-6-, 2- (3'-sulfophenyl) sulfonyl-4 -chlorotriazinyl-6-, 2,4-bis- (3'-carboxyphenylsulfonyl) -triazinyl-6-; pyrimidine rings containing sulfonyl groups, such as 2-car-boxymethylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-6-methyl-60 pyrimidinyl-4-, 2-methylsulfonyl-6-ethyl-pyrimidinyl-4-, 2-phenylsulfonyl-5- chloro-6-methyl-pyrimidinyl-, 2,6-bis-methylsulfonyl-pyrimidinyl-4-, 2,6-bis-methyl-sulfonyl-5-chloro-pyrimidinyl-4-, 2,4-bis-methylsulfonyl-pyrimidine -5-sulfonyl-, 2-methylsulfonyl-pyrimidinyl-4-, 2-phenylsulfonyl-pyrimidinyl-4-, 2-trichloro-65 methylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro 6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidynyl-4-, 2-methylsulfonyl -5-chloro-6-chloromethyl-pyrimidinyl-4-.

639 683

25th

2-methylsulfonyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl-, 2-Me- wherein thylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4-, 2,5,6-tris-methyl-sulfonyl -pyrimidinyl-4-, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-chloro pyrimidinyl-4-, 2,6-bis-methylsulfonyl-5- 5 chloro-pyrimidinyl-4-, 2-methylsulfonyl-6-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-sulfo-pyrimidinyl-4-, 2 -Methylsulfonyl-6-carbomethoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-carboxy-pyrimidinyl-4-, 2-methylsulfonyl-5-cyan-6-methoxy-pyrimidinyl-4-, 2-methylsulfonyl-5- chloro-pyrimidinyl-4-, 2-sulfoethylsulfonyl-6-10 methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloropyrimidinyl-4-, 2-carboxymethylsulfo -nyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-chloro-pyrimidine-4- and -5-carbonyl-, 2,6-bis (methylsulfonyl) -pyrimi-din-4 - or -5-carbonyl-, 2-ethylsulfonyl-6-chloropyrimidine-5- 15 carbonyl-, 2,4-bis (methylsulfonyl) pyrimidine-5-sulfony l-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl or carbonyl; triazine rings containing ammonium groups, such as 2-trimeth-ylammonium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2- (l, l-dimethylhydrazinium) -4-phenyla-20 mino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2- (2-isopropylidene-l, l-dimethyl) -hydrazinium-4-phenylamino-or -4- (o- , m- or p-sulfophenyl) -aminotriazinyl-6-, 2-N-aminopyrrolidinium- or 2-N-aminopiperidinium-4-phenylamino or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl- 6-, furthermore 4-phenylamino or 4- (sulfophenylamino) triazinyl-6 radicals which, in the 2-position, contain 1,4-bis-azabicyclo- [2,2,2] -octane or the l via a nitrogen bond , 2-bis-aza-bicyclo- [0,3,3] octane contain quaternary bound, 2-pyridinium-4-phenylamino- or -4- (o-,

m- or p-sulfophenyl) amino-triazinyl-6 and corresponding 30 2-oniumtriazinyl-6 radicals which are in the 4-position by alkylamino, such as methylamino, ethylamino or β-hydroxyethylamino,

or alkoxy, such as methoxy or alkoxy, or aroxy, such as phenoxy or sulfophenoxy groups; 2-chlorobenzthiazole-5- or 6-carbonyl- or -5- or -6-sulfonyl-, 35 2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -6-carbo-nyl- or -5- or -6-sulfonyl -, such as 2-methylsulfonyl- or 2-ethylsulfonyl-benzothiazole-5- or -6-sulfonyl- or -carbonyl-, 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonyl- or carbonyl- and the corresponding in the condensed benzene ring Sulfo-40 group-containing 2-sulfonylbenzothiazole-5 or -6-carbo-nyl or -sulfonyl derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl- or -sulfonyl-, 2-chlorobenzimidazole-5- or - 6-carbonyl- or sulfonyl-, 2-chloro-l-methylbenzimidazole-5- or -6-carbo-nyl- or sulfonyl-, 2-chloro-4-methylthiazole- (l, 3) -5-carbonyl- 45 or -4- or -5-sulfonyl-, N-oxide of 4-chloro or 4-nitroquinolin-5-carbonyl.

Also to be mentioned are reactive groups of the aliphatic series, such as acryloyl, mono-, di- or trichloracryloyl, such as -CO-CH = CH-Cl, -CO-CCl = CH2, -CO-CCl = CH-CH3, furthermore 50 -CO-CCl = CH-COOH, -CO-CH = CCl-COOH, ß-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, ß-sulfato-ethylaminosulfonyl, vinylsulfonyl, ß-chloroethylsul- fonyl-, ß-sulfatoethylsulfonyl-, ß-methylsulfonyl-ethylsulfonyl-, ß-phenylsulfonylethylsulfonyl-, 2-fluoro-2-chloro-3,3-difluorcy- 55 clobutane-l-carbonyl-, 2,2,3,3- Tetrafluorocyclobutane-carbonyl-l or sulfonyl-1-, ß- (2,2,3,3-tetrafluorocyclobutyl-l) -acryloyl-, a- or ß-bromoacryloyl-, a- or ß-alkyl or arylsulfonylacryl-oyl Group, such as α- or β-methylsulfonylacryloyl.

The metal-free dyes of formula VII 60

D, B, R, Zundn have the meaning given above, are under the conditions of oxidative copper plating [Angew. Chem. 70, 232 (1958)] in the copper complexes of the formula VTII

O-Cu-O

; "V \ nh-45-K | -Z

\ , In

R

(VIII)

S03R

saw

wherein

D, B, R, Z and n have the meaning given above.

The dyes used for the process according to the invention, namely the metal-free dyes of the formula (VII), can be prepared from the diazo compounds of the amines of the formula by the known processes of diazotization, coupling and, if appropriate, reaction with agents introducing Z.

H

D-NH ^

wherein

D has the meaning given above and the hydrogen atom is in the o-position to the NH2 group, and the coupling components of the formula

R

and

S03 II

YH

R

be won.

H

(YII)

65

Suitable diazo components D-NH2 are, for example:

1-amino-4- or 5- or 6- or 7-sulfonaphthalene,

2-amino-5- or 6- or 7- or 8-sulfonaphthalene,

1-amino-3,6- or 3,7- or 4,6- or 4,7-disulfonaphthalene,

2-amino-4,8- or 3,6- or 5,7- or 6,8-disulfonaphthalene, 2-amino-4,6,8- or 3,6,8-trisulfonaphthalene,

1-amino-4-sulfo-benzene,

4-amino-7-sulfo-naphthalene-<l-azo-l> -4-sulfo-benzene,

4-amino-6-sulfonaphthalene <l-azo-l> -2,5-disulfobenzene,

4-amino-6-sulfo-naphthalene-<l-azo-l> -3-sulfo-benzene,

4-amino-6-sulfonaphthalene <l-azo-l> -2-methoxy-5-sulfo-

benzene.

Suitable coupling components

R

S 0 .. H

are for example:

l-oxy-8-amino-4,6-disulfonaphthalene, l-oxy-8- (N-methylaminoacetylamino) -4,6-disulfonaphthalene, l-oxy-8- (N-4'-amino- benzoylamino) -4,6-disulfonaphthalene.

Suitable coupling components

C> -i vir. (r> .., v3 -7

cri /.

y ^^ so3u S 03 Ii are, for example, the condensation products of the compounds

!

so, H

with the corresponding reactive components Y-Z.

Reactive components of the formula Y-Z which are suitable for this purpose are, for example, those on which the aforementioned reactive groups Z are based, that is to say in general the halides, in particular the chlorides, of the acyl components Z mentioned. The following are extracts from the large number of available compounds:

Trihalogen-symmetrical triazines, such as cyanuric chloride and cyanurobromide, dihalogen monoamino and monosubstituted amino-symmetrical triazines, such as 2,6-dichloro-4-amino-triazine, 2,6-dichloro-4-methylaminotriazine, 2.6 -Dichlor-4-ethylamino-triazine, 2,6-dichloro-4-oxethylaminotriazine, 2,6-dichloro-4-phe-nylaminotriazine, 2,6-dichloro-4- (o-, m- or p-sulfophenyl) - ami-notriazine, 2,6-dichloro-4- (2 ', 3'-, -2', 4'-, -3 ', 4'- or-3', 5'-disulfophenyl) aminotriazine, dihalo- alkoxy- and aryloxy-sym.-triazines, such as 2,6-dichloro-4-methoxytriazine, 2,6-dichloro-4-ethoxytriazine, 2,6-dichloro-4-phenoxytriazine, 2,6-dichloro-4- ( o-, m- or p-sulfophenyl) -oxytriazine, dihalo-alkylmercapto and arylmercapto sym.-triazines, such as 2,6-dichloro-4-ethylmercapto-triazine, 2,6-dichloro-4-phenylmercaptotriazine, 2, 6-dichloro-4- (p-methylphenyl) mercaptotriazine, 2,4-difluoro-6- (o-, m-, p-methylphenyl) amino-triazine, 2,4-difluoro-6- (o-, m-p-sulfophenyl) amino-triazine, 2,4-difluoro-6-methoxy-triazine, 2,4-difluoro-6- (2 ', 5'-disulfophenyl) - amino-triazine-2,4-difluoro-6- (6'-sulfo-naphthyl-2 ') amino-triazine, tetrahalopyrimidines, such as te-trachloro-, tetrabromo- or tetrafluoropyrimidine, 2,4,6-trihalogenopyrimidines 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 tri -chloromethyl- or -5-carboxy- or -5-sulfo- or -5-cyano- or -5-vinyl-pyrimidine, 2,4-di-fluoro-6-methylpyrimidine, 2,6-difluoro-4-methyl -5-chloropyrimi-din, 2,4-difluoro-pyrimidine-5-ethylsulfone, 2,6-difluoro-4-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,6-difluoro-4 -methyl-5-bromopyrimidine, 2,4-difluoro-5,6-dichloro- or -dibromopyrimidine, 4,6-difluoro-2,5-dichloro- or -dibromopyrimidine, 2,6-di-fluoro-4 -bromopyrimidine, 2,4,6-trifluoro-5-bromopyrimidine, 2,4,6-trifluoro-5-chloromethylpyrimidine, 2,4,6-trifluoro-5-nitropyrimi-din, 2,4,6-trifluoro-5 -cyanpyrimidine, 2,4,6-trifluoropyrimidine-5-carboxylic acid alkyl ester or -5-carboxamide, 2,6-difluoro-5-methyl-4-chloropyrimidine, 2,6-difluoro-5-chloropyrimidine, 2,4,6- Trifluoro-5-methylpyrimidine, 2,4,5-trifluoro-6-methylpyrimidine, 2,4-difluoro-5-nitro-6-chloropyrimidine, 2,4-difluoro-5-cyanopyrimi-din, 2,4-difluoro 5-methylpyrimidine, 6-trifluoromethyl-5-chloro

639 683

2,4-difluoropyrimidine, 6-phenyl-2,4-difluoropyrimidine-6-trifluoromethyl-2,4-difluoropyrimidine, 5-trifluoromethyl-2,4,6-trifluoropyrimidine, 2,4-difluoro-5- nitro-pyrimidine, 2,4-difluoro-5-trifluoromethyl-pyrimidine, 2,4-difluoro-5-methylsulfonyl-pyrimidine, 2,4-di-fluoro-5-phenyl-pyrimidine, 2,4-difluoro-5- carbonamido-pyrimi-din, 2,4-difluoro-5-carbomethoxy-pyrimidine, 2,4-difluoro-6-tri-fluoromethyl-pyrimidine, 2,4-difluoro-5-bromo-6-trifluoromethyl-py-rimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4-difluoro-6-carbomethoxy-pyrimidine, 2,4-difluoro-6-phenyl-pyrimidine, 2,4-difluoro-6-cyanopyrimidine, 2,4, 6-trifluoro-5-methylsulfoyl-pyrimidine, 2,4-difluoro-5-sulfonamido-pyrimidine, 2,4-difluoro-5-chloro-6-carbomethoxy-pyrimidine, 5-trifluoromethyl-2,4-difluoro pyrimidine, 2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,4,6-trichloropyrimidine-5-carboxylic acid chloride, 2-methyl-4-chloropyrimidine-5-carboxylic acid chloride, 2-chloro-4-methylpyrimidine-5-car- bonic acid chloride, 2,6-dichloropyrimidine-4-carboxylic acid chloride; Pyrimidine reactive components with removable sulfonyl groups, such as 2-carboxymethylsulfonyl-4-chloropyrimidine, 2-methyl-sulfonyl-4-chloro-6-methylpyrimidine, 2,4-bis-methylsulfonyl-6-methylpyrimidine, 2,4-bisphenylsulfonyl -5-chloro-6-methylpyrimidine, 2,4,6-trismethylsulfonylpyrimidine, 2,6-bis-methylsulfonyl-4,5-dichloropyrimidine, 2,4-bis-methylsulfonylpyrimidine-5-sulfonic acid chloride, 2 -Methylsulfonyl-4-chloropyrimidine-2-phenylsulfonyl-4-chloropyrimidine, 2,4-bis-trichloromethylsulfonyl-6-methylpyrimidine, 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine, 2,4 Bis-methylsulfonyl-5-bromo-6-methyl-pyrimidine, 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine, 2-methylsulfonyl-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-tetramethylsulfonyl-pyrimidine, 2-methylsulfonyl-4-chloro -5,6-dimethylpyrimi-din, 2-ethylsulfonyl-4,5-dichloro-6-methylpyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 2,4,6-tri s-methylsulfonyl-5-chloropyrimidine, 2-methylsulfonyl-4-chloro-6-carboxypyrimidine, 2-methylsulfonyl-4-chloropyrimidine-5-sulfonic acid, 2-methylsulfonyl-4-chloro-6-carbomethoxypyrimidine, 2-methylsulfonyl- 4-chloropyrimidine-5-carboxylic acid, 2-methylsulfonyl-4-chloro-5-cy-an-6-methoxypyrimidine, 2-methylsulfonyl-4,5-dichloropyrimidine, 4,6-bis-methylsulfonylpyrimidine, 4-methylsulfonyl- 6-chloropyrimidine, 2-sulfoethylsulfonyl-4-chloro-6-methylpyrimidine, 2-methylsulfonyl-4-chloro-5-bromopyrimidine, 2-methylsulfonyl-4-chloro-5-bromo-6-methylpyrimidine, 2, 4-bis-methylsulfonyl-5-chloropyrimidine, 2-phenylsulfonyl-4,5-dichloropyrimidine, 2-phenylsulfonyl-4,5-dichloro-6-methylpyrimidine, 2-carboxymethylsulfonyl-4,5-dichloro-6- methylpyrimidine, 2- (2'- or 3'- or 4'-carboxyphenylsulfonyl) -4,5-dichloro-6-methylpyrimidine, 2,4-bis- (2'- or 3'- or 4'-carboxyphenylsulfonyl) - 5-chloro-6-methyl-pyrimidine, 2-methylsulfonyl-6-chloropyrimidine-4- or -5-carbonyl chloride, 2-ethylsulfonyl-6-chloropyrimidine-4- or -5-carbonic acid chloride , 2,6-bis (methylsulfonyl) pyrimidine-4-carbonyl chloride, 2-methylsulfonyl-6-methyl-4-chloro or -4-bromo-pyrimidine-5-carboxylic acid chloride or bromide, 2,6- Bis- (methyl-sulfonyl) -4-chloropyrimidine-5-carboxylic acid chloride; further reactive components of the heterocyclic series with reactive sulfonyl substituents are, for example, 3,6-bis-phenylsulfonyl-pyridazine, 3-methylsulfonyl-6-chloropyridazine, 3,6-bis-trichloromethylsulfonylpyridazine, 3,6-bis-methylsulfonyl 4-methylpyrida-tin, 2,5,6-tris-methylsulfonylpyrazine, 2,4-bis-methylsulfonyl-l, 3,5-triazine, 2,4-bis-methylsulfonyl-6- (3'-sulfophenylamino) -l , 3,5-triazine, 2,4-bis-methylsulfonyl-6-N-methylanilino-l, 3,5-triazine, 2,4-bis-methylsulfonyl-6-phenoxy-l, 3,5-triazine, 2 , 4-bis-methylsulfonyl-6-trichloroethoxy-l, 3,5-triazine, 2,4,6-trisphenyl-sulfonyl-l, 3,5-triazine, 2,4-bis-methylsulfonylquinazoline, 2,4-bis trichloromethylsulfonylquinoline, 2,4-bis-carboxymethylsulfonyl-quinoline, 2,6-bis (methylsulfonyl) pyridine-4-carboxylic acid chloride and l- (4'-chlorocarbonylphenyl or 2'-chlorocarbonylethyl) -4,5-bis- - methylsulfonyl-pyridazone- (6); other heterocyclic reactive components with movable halogen include 5

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

639 683

6

rem 2- or 3-monochloroquinoxaline, -6-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or 3-monobromoquinoxaline-6-carboxylic acid bromide or-6-sulfonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or-6-sulfonic acid chloride , 2,3-dibromo-quinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide,

1,4-dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding bromine compounds, 2,4-dichloroquinazoline-6- or -7-carboxylic acid chloride or -7-sulfonic acid chloride and the corresponding bromine compounds, 2- or 3- or 4- (4 ', 5'-dichloropyridazon-6'-yl-1') phenylsulfonic acid chloride or carboxylic acid chloride and the corresponding bromine compounds, β- (4 ', 5'-dichloropyridazon-6'-yl-1') -ethyl-carboxylic acid chloride, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding bromine compounds, N-methyl-N- (2,4-dichlorotriazinyl-6) -carbamic acid chloride, N-methyl-N- (2-chloro-4-methylamino- triazinyl-6) -carbamic acid chloride, N-methyl-N- (2-chloro-4-dimethylamino-triazinyl-6) -carbamic acid chloride, N-methyl or N-ethyl-N- (2,4-dichlorortriazinyl-6) - aminoacetyl chloride, N-methyl, N-ethyl or N-hydroxyethyl-N- (2,3-dichloroquinoxaline-6-sulfonyl- or -6-carbonyl) -aminoacetylchloride and the corresponding bromine derivatives, furthermore 2-chlorobenzene -thiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-arylsulfonyl- or 2-alkylsulfonyl-benzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride, such as 2 -Methylsulfonyl or 2-ethylsulfonyl or 2-phenylsulfonyl-benzothiazole-5-or -6-sulfonic acid chloride or -5- or -6-carboxylic acid chloride and the corresponding 2-sulfonylbenzothiazole derivatives containing sulfonic acid groups in the fused benzene ring,

3.5-bis-methylsulfonyl-isothiazole-4-carboxylic acid chloride, 2-chloro-benzoxazole-5- or -6-carboxylic acid chloride or -sulfonic acid chloride and the corresponding bromine derivatives, 2-chloro-benzimidazole-5- or -6-carboxylic acid chloride or - sulfonic acid chloride and the corresponding bromine derivatives, 2-chloro-l-methylbenzimidazole-5- or -6-carboxylic acid chloride or -sulfonic acid chloride and the corresponding bromine derivatives, 2-chloro-4-methylthiazole- (1,3) -5-carboxylic acid chloride or -4- or -5-sulphonic acid chloride, 2-chlorothiazole-4- or -5-sulphonic 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-, di- or trichloro-acrylic acid chloride, 3-chloropropionic acid chloride, 3-phenylsulfonyl-propionic acid chloride, 3-methylsulfonyl-propionic acid chloride, 3-ethyl sulfo-nylpropionic acid chloride, 3-chloroethane sulfochloride, chloromethane chlorochloride , 2,2,3,3-tetrafluorocyclo-butane-l-carboxylic acid chloride, ß- (2,2,3,3-tetrafluorocyclobutyl-l) -acrylic acid chloride, ß- (2,3,3-trifluoro-2-chlorocyclobutane l) -car-bonic acid chloride, ß-methylsulfonyl-acrylic acid chloride, a-methyl-sulfonyl-acrylic acid chloride and a-bromoacrylic acid chloride and ß-bromoacrylic acid chloride.

If the conversion leads to dyes which have more than one reactive group in the Z radical or elsewhere in the dye molecule, these can be partially replaced by other radicals, for example amino radicals, which in turn are reactive groups, for. B. in the form of esterified oxalkyl groups. In principle, the presence of two or more different reactive groups in the dye is possible.

The new dyestuffs which can be prepared according to the invention are suitable for dyeing and printing hydroxyl or amide group-containing materials, such as textile fibers, threads and fabrics made of wool, silk, synthetic polyamide and polyurethane fibers, and for washing and dyeing and printing native or regenerated cellulose, the treatment of cellulose materials expediently being carried out in the presence of acid-binding agents and, if appropriate, by exposure to heat according to the processes which have become known for reactive dyes.

The formulas given for the dyes are those for the corresponding free acids. The dyes were generally isolated in the form of the alkali salts, in particular the Na salts, and used for dyeing.

example 1

87 g of the tetra-Na salt of the dye 4,7-disulfonaphtha-lin- <l-azo-a2> -l-oxy-8- (N-2 ', 4'-difluoro-5'-chloro pyrimidinyl-6'-amino) -4,6-disulfonaphthalene (the dye is obtained by coupling diazotized l-amino-4,7-disulfonaphthalene to the condensation product from l-oxy-8-amino-4 , 6-disul-fo-naphthalene and 2,4,6-trifluoro-5-chloro-pyrimidine) are stirred in 21 water, 28 g CuSo4.5H20 and 42 gNaAc .3H20 are added and then 250 ml of a 3% solution at room temperature H202 solution dropped in. The color changes from dark red to blue and the oxidatively copper-colored dye partially separates from the solution. The mixture is stirred for a further 1 to 2 hours and the dye is then salted out with 5% by volume of sodium chloride. After isolation, drying and grinding, a dark blue dye powder is obtained which dissolves in water with a blue color. In the form of the free acid, the dye corresponds to the following formula:

Cl

0, H

Printing instructions If cotton nettle is printed with a printing paste containing 20 g per kilogram of the dye shown in Example 1, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g of sodium alginate / kg of thickener) and 10 g of soda, and that with water was dropped to 1 kg, dried, steamed for 1 min at 103 ° C, rinsed with hot water and boiling with soap, so you get a strong, blue print of good wet and light fastness.

Block regulation

30 parts of the dye shown in Example 1 are dissolved in 1000 parts of water. A cotton fabric is padded with this solution and pressed down to a weight loss of 90%. The still moist cotton is treated at 70 ° C for 30 minutes in a belt which contains 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate dissolved in 1000 parts of water. The coloring is then finished in the usual way. A strong, blue color is obtained with excellent wet and light fastness.

Staining instructions 168 ml of water at 20-25 ° C. are placed in a 300 ml staining cup in a heatable water bath. 0.3 g of the dye obtained in Example 1 is well mixed with 2 ml of cold water and 30 ml of hot water (70 ° C.) are added; the dye dissolves. The dye solution is added to the water and 10 g of cotton yarn in this dye liquor is kept in constant motion. Within 10 minutes, the temperature of the dye liquor is increased to 70-80 ° C, 10 g of anhydrous sodium sulfate are added and the dyeing is continued for 30 minutes. Then 4 g of anhydrous sodium carbonate are added to the dyebath and dyeing is carried out for 60 min at 70-80 ° C. The dyed material is then removed from the dyebath and the adhering liquor is removed by wringing or pressing

10th

15

20th

25th

30th

35

40

45

50

55

60

65

sen and rinse the material first with cold water and then with hot water until the wash liquor is no longer bled on. The dyed material is then soaped in 200 ml of a liquor containing 0.2 g of sodium alkyl sulfate for 20 minutes at the boiling point, rinsed again and at 60-70 ° C.

7,639,683

dried in a drying cabinet. A strong blue color is obtained with excellent wash and light fastness.

Likewise valuable dyes are obtained if the procedure of Example 1 is followed, but the diazo and reactive components listed below are used.

example

Diazo component

Reactive component

hue

2nd

l-amino-4,6-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine blue

3rd

l-amino-3,6-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine rot. blue

4th

1-amino-3,6-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine blue

5

2-amino-4,8-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine blue

'6

2-amino-3,6-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine rot. blue

7

2-amino-6,8-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine blue

8th

2-amino-5,7-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine blue

9

l-amino-4,7-disulfonaphthalene

2,4-difluoro-6- (3'-sulfophenylamino) triazine blue

10th

l-amino-4,7-disulfonaphthalene

2,4-difluoro-6- (4'-sulfophenylamino) triazine blue

11

l-amino-4-sulfonaphthalene

2,4-difluoro-6- (2 ', 5'-disulfophenylamino) triazine blue

12

2-amino-5-sulfonaphthalene

2,4-difluoro-6- (2 ', 5'-disulfophenylamino) triazine blue

13

2-amino-4,6,8-trisulfonaphthalene

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

14

l-amino-4-sulfo-benzene

2,4,6-trifluoro-5-chloropyrimidine violet

15

2-amino-3,6,8-trisulfonaphthalene

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

16

4-sulfo-benzene (l-azo-l) 4-amino-7-sulfo-naphthalene

2,4,6-trifluoro-5-chloropyrimidine

M

Claims (4)

639 683 2nd PATENT CLAIMS 1. Process for the preparation of new copper complexes of azo dyes of the formula I. OH !! P ^ <'B2 •> 0aH H03S (I) R ~ S03 H (I) where so3h where D phenylene or naphthylene, optionally substituted by halogen, Q-Q-alkyl, Ci-C4-alkoxy, carboxylic acid, acylamino, sulfonic acid and azo groups B direct bond or divalent bridge member, R hydrogen or Q-CrAlkyl, Z means the rest of a reactive component, the OH group in D is in the o-position to the azo bridge and n is 0 or 1, characterized in that dyes of the formula VII 10 D phenylene or naphthylene, optionally substituted by halogen, Q-Gp-alkyl, Q-C4-alkoxy, carboxylic acid, acylamino, sulfonic acid and azo groups, B direct bond or divalent bridge member R hydrogen or C1-C4-alkyl, 15 Z means the residue of a reactive component, the OH-Grappe in D in o-position to the azo bridge and n stands for 0 or 1, which is characterized in that dyes of the formula VII R 25th L = NK0, n- R S03H S03 H S03II (VII) (VII) S03ïl 30th wherein D, B, R, Zundn have the meaning given above, oxidatively copper. Bivalent bridge members B are for example 35 wherein D, B. R, Zund n have the meaning given above, oxidatively copper. 2. The method according to claim 1, characterized in that n stands for 0. 3. The method according to claim 1, characterized in that n is 0 and Z is a halopyrimidinyl, in particular 2,4-difluoro-5-chloropyrimidinyl-6 or 2,4,5-trichloropyrimidynyl-6 radical , a halotriazinyl, in particular chlorine or fluorotriazinyl radical, a 2,3-dichloroquinoxaline-6-carbonyl radical or a 2-methylsulfonyl-5-chloro-6-methylpyrimidinyl-4 radical. 4. The method according to claim 1, characterized in that new copper complexes of dyes of the formula III -C-CHp-II 2 0 and Examples of acylamino groups are acetylamino, chloroacet-40 ylamino and benzoylamino groups. Preferred new dyes that can be produced according to the invention are the copper complexes of the dyes of the formula II 45 50 KII-Z (II) S03 II SOaH f nq D '~ Nv = X NH-Z S03H wherein Z has the meaning given in claim 1 and D 'represents a mono-, di- or trisulfonaphthylene radical. wherein D and Z have the meaning given above. Further preferred new dyes (XII) which can be prepared according to the invention and those of the formula (II) are those in which 55 Z represents a halopyrimidinyl, in particular 2,4-difluoro-5-chloropyrimidinyl-6 radical, a halotriazinyl, in particular chlorine or fluorotriazinyl radical or a 2,3-dichloroquinoxaline-6-carbonyl radical . Particularly preferred new 60 dyes that can be produced according to the invention are the Cu complexes of the dyes of formula III Oli f HO XH-Z D'-N = X 65