CH615450A5 - Process for preparing fibre-reactive dyes - Google Patents

Abstract

Fibre-reactive dyes of the formula <IMAGE> where A1 is the radical of a sulpho-containing chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series, A2 is an organic radical, B is an alkylene or arylene radical and R1, R2, R3 and R4 are each independently of the others hydrogen or alkyl, are prepared by condensing a dye of the formula <IMAGE> a compound of the formula <IMAGE> an alkylene- or arylene-diamine of the formula <IMAGE> and trifluoro-s-triazine of the formula <IMAGE> with one another in any desired order of the elementary reactions. The dyes obtained are suitable in particular for dyeing and printing cellulose-containing materials and are notable for high reactivity and good bond stability between dye and fibre, which is reflected for example in the good wash fastness.

Description

       

  
 

** WARNING ** beginning of DESC field could overlap end of CLMS **. 

 
EMI3. 1
 wherein Al is the residue of a sulfo group-containing chromophore of the aza series, A2 is an organic residue, B is an alkylene or arylene residue and Rl, R2, R3 and R4 are independently hydrogen or alkyl, characterized in that diazo components or coupling components of the dye of the formula
EMI3. 2nd
 which is an amino group of the formula
EMI3. 3rd
 contain a compound of formula
EMI3. 4th
 or optionally diazo components or coupling components of the compound of formula (4) which are an amino group of the formula
EMI3. 5
 included, with trifluoro-s-triazine of the formula
EMI3. 6
 condensed and the condensation products obtained with the further components of the dye of the formula (3) or 



  the compound of formula (4) and alkylene or arylene diamines of the formula
EMI3. 7
 Coupled and condensed in any sequence to fiber-reactive dyes of the formula (1), where Al, A2, B, Rl, R2, R3 and R4 in the formulas (3), (4), (5), (15) and (16 ) have the meanings given under formula (1). 



   11.  A method according to claim 10, characterized in that the reactions with difluoro or trifluoro-s-triazines are carried out in aqueous solution. 



   The present invention relates to a method for producing fiber-reactive dyes of the formula
EMI3. 8th
 wherein Al is the residue of a chromophore containing sulfo groups, A2 is an organic residue, B is an alkylene or arylene residue and R 1, R 2, R 3 and R 4 are independently hydrogen or alkyl. 



   The remainder of a chromophore, Al, can be the remainder of an anthraquinone, azo, phthalocyanine or nitroaryl series chromophore.  The organic residue A2 can be a colorless residue or also the residue of a chromophore. 



   As colorless radicals A2 come z. B.  considered: alkyl radicals, such as methyl, ethyl, propyl, isopropyl, butyl, methoxyethyl, methoxypropyl, ethoxyethyl, cyanoethyl, hydroxyethyl, cyclohexyl, methylcyclohexyl; Aryl radicals, such as phenyl, optionally substituted by alkyl groups, such as methyl, methyl, propyl, isopropyl, butyl, alkoxy groups, such as methoxy, ethoxy, isopropoxy, ethoxyethoxy, isopropoxypropoxy, acyl groups, such as acetyl, acetylamino or benzoylamino, the ureido, carboxy and Sulfo group and halogen atoms such as chlorine or bromine; Naphthyl, sulfonaphthyl; heterocyclic radicals, such as pyridyl, benzthiazolyl, oxazolyl, thiazolyl, quinolyl.  A2 can also be part of a heterocyclic radical in that A2 and R4 in formula (1) are closed to form a ring, so that the latter is bonded directly to the s-triazine radical via the nitrogen atom to which A2 and R4 are bound. 

  Examples of such heterocyclic radicals are piperidyl and morpholyl.  Above all, A2 is the rest of a chromophore. 



  Like Al, this can be the residue of a chromophore from the anthraquinone, azo, phthalocyanine or nitroaryl series. 



  Furthermore, A2 and Al are preferably identical radicals. 



   The alkylene or arylene radical B is derived from an aliphatic or aromatic diamine.  So B can be a long (e.g. B.  with 10 or more carbon atoms) or shorter, straight-chain or branched alkylene radical; in particular an alkylene radical having 1 to 6 carbon atoms comes into consideration, for. B.  Ethylene, propylene, butylene, hexylene or



  Cyclohexylene.  B is preferably an aromatic radical, e.g. B. 



  a naphthylene radical, the radical of a diphenyl or stilbene or in particular a phenylene radical.  This can contain further substituents, e.g. B.  Halogen atoms, low molecular weight alkyl and alkoxy groups, carboxy and sulfo groups. 



  B is preferably a phenylene radical. 



   For R1, R2, R3 and R4, in addition to hydrogen, alkyl radicals having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl or cyclohexyl, are particularly suitable; preferably Rt, R2, R3 and R4 are hydrogen atoms. 



   Fiber-reactive dyes of the formula (1) in which A2 is the radical of a chromophore and Al, B, Rt, R2, R3 and R4 have the meanings given under formula (1) are preferred. 



   Fiber-reactive dyes of the formula (1) are particularly preferred, in which Al and A2 are identical chromophores of the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenylene radical and Rt, R2, R3 and R4 are each a hydrogen atom. 



   A preferred embodiment of the fiber-reactive dyes of the formula (1), in which A2 is a colorless organic radical, are those of the formula
EMI4. 1
 in which Al and B have the meanings given under formula (1), X is hydrogen, halogen, alkyl, alkoxy, carboxy or sulfo, and the benzene radical D, in addition to X, may contain further substituents, in particular a further sulfonic acid group. 



   Due to the presence of two cleavable fluorine atoms on the two s-triazine rings of the dyes of the formula (1), these are fiber (bi) reactive. 



   Fiber-reactive compounds are to be understood as those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds. 



   The fiber-reactive dyes of the formula (1) are prepared in such a way that a dye of the formula
EMI4. 2nd
 a compound of the formula
EMI4. 3rd
 an alkylene or arylenediamine of the formula
EMI4. 4th
 and trifluoro-s-triazine of the formula
EMI4. 5
 reacted with one another in such a way that a fiber-reactive dye of the formula (1) is formed, the sequence of the partial reactions being freely selectable taking into account the starting compounds to be reacted with one another, and wherein Al, A2, B, Rl, R2, R3 and R4 in the formulas ( 3), (4) and (5) have the meanings given under formula (1). 



   Preference is given to compounds of the formula (4) in which A2 is the radical of a chromophore and R4 is hydrogen or alkyl, and in the rest of the compound compounds of the formulas (3) and (5) 1) have the meanings given, used as starting materials. 

 

   The preferred fiber-reactive dyes of the formula (1), in which Al and A2 are identical chromophores from the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenylene radical and Rt, R2, R3 and R4 are each a hydrogen atom, are prepared by a dye of the formula Al (2) NH2 (7) with trifluoro-s-triazine to a compound of the formula
EMI4. 6
 acylated and condensed in a molar ratio of 2: 1 with a phenylenediamine of the formula H2N-B-NH2 (9). 



   An important process variant for producing the fiber-reactive dyes of the formula (1) is characterized in that a dye of the formula (3), an alkylene or arylenediamine of the formula (5) and trifluoro-s-triazine of the formula (6) are reacted with one another in such a way that that a fiber reactive dye of the formula
EMI4. 7
  arises, the order of the partial reactions taking into account the starting compounds to be reacted can be freely selected, and the dye of formula (10) condensed with a compound of formula (4), wherein Al, A2, B, Rt, R2, R3 and R4 in the formulas (3), (4), (5) and (10) have the meanings given under formula (1). 



   So z. B.  the fiber-reactive dyes of the formula (1), in which Al and A are identical chromophores of the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenylene radical and Rt, R2, R3 and R4 are each a hydrogen atom, by preparing a phenylenediamine Formula (9) in a molar ratio of 1: 2 with trifluoro-s-triazine of the formula (6) to a compound of the formula
EMI5. 1
 condensed and condensed with a dye of formula (7) in a molar ratio of 1: 2. 



   In the process variant described above, according to which a fiber-reactive dye of the formula (10) is condensed with a compound of the formula (4), an aminobenzene of the formula is advantageously used as the compound of the formula (4)
EMI5. 2nd
 wherein X is hydrogen, halogen, alkyl, alkoxy, carboxy or sulfo, and the benzene radical D in addition to X may contain further substituents, in particular a further sulfonic acid group. 



   In another procedure, the fiber-reactive dyes of the formula (2) are obtained by using a dye of the formula
EMI5. 3rd
 with a phenylamino-difluoro-s-triazine of the formula
EMI5. 4th
 condensed. 



   If the dye residue is Al or  A2 is composed of several components (as with azo dyes), then the fiber-reactive dyes of the formula (1) are also available in such a way that they are composed of components Al or  A2 builds up, one of which already contains the fiber-reactive halogen-s-triazine residue. 



   The procedure is thus such that components of the dye of the formula (3) which are an amino group of the formula
EMI5. 5
 included or  that components of the compound of formula (4) which are an amino group of formula
EMI5. 6
 contain, condensed with trifluoro-s-triazine of the formula (6) and the condensation products obtained are combined with further components and alkylene or arylenediamines of the formula (5) in any order of the partial reactions to give fiber-reactive dyes of the formula (1). 



   This process variant is of particular importance for the production of fiber-reactive dyes of the formula (1), in which Al is an azo dye residue and A2 is an organic residue, which can also be an azo dye residue.  Such azo dyes of the formula (1) are thus also obtained according to the invention by adding diazo components or coupling components of the dye of the formula
EMI5. 7
 which is an amino group of the formula
EMI5. 8th
 contain a compound of formula
EMI5. 9
 or optionally, diazo components or coupling components of the compound of the formula (4) which are an amino group of the formula
EMI5. 10th
 included, with trifluoro-s-triazine of the formula
EMI5. 11
 condensed and the condensation products obtained with the further components of the dye of the formula (3) or 



  the compound of formula (4) and alkylene or arylene diamines of the formula
EMI6. 1
 coupling and condensing in any sequence to fiber-reactive dyes of the formula (1), where Al, A2, B, Rt, R2, R3 and R4 in the formulas (3), (4), (5), (15) and (16 ) have the meanings given under formula (1). 



   Starting materials which contain water-solubilizing groups are preferably used. 



   The reactions of the difluoro or trifluoro-s-triazines with the compounds containing amino groups or  Dyes or their components are expediently carried out using acid-binding agents, such as sodium carbonate or sodium hydroxide, and in organic solvents or at relatively low temperatures in an aqueous agent.  These reactions must be carried out in such a way that one replaceable fluorine atom per s-triazine ring remains in the finished product. 



   The dyes to be reacted with the trifluoro-s-triazines of the formula (6) must, as the formula (1) shows, at least one acylatable amino group of the formula - NHRt or 



  -NHR4, where Rt or  R4 represents hydrogen, alkyl or aryl. 



   The dye compounds of the azo series which contain at least one - NHR group and are used as starting products can be obtained by various processes.  One method is to diazotize an aromatic primary amine and to couple the diazonium compound thus obtained with a coupling component containing an - NHR group. 

  Examples of aromatic primary amines which can be used in this way to obtain aminoazo compounds include: aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, O-, m- and p-chloroaniline, 2,5-dichloroaniline, a- and, 3-naphthylamine, 2,5-dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodiphenyl, 2,3-aniline and -4-carboxylic acids, 2-aminodiphenyl ether , 2-, 3- or 4-aminobenzenesulfonamide, or -sulfomonomethyl- or -ethylamide or -sulfondimethyl- or sulfondi äthylamide, dehydrothio-p-toluidine monosulfonic acid or dehydrothio-p-toluidinedisulfonic acid, aniline-2, -3 and -4-sulfonic acids, aniline -2,4- or -2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3-aminobenzotrifluoride-4-sulfonic acid, 4-chloro-5-methyl-aniline-2sulfonic acid,

   5-chloro-4-methylaniline-2-sulfonic acid, sulfoanthranilic acid, 3-acetylaminoaniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline 2-sulfonic acid, 3,4-dichloroaniline-6-sulfonic acid, 4-methylaniline 2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid and 5-methoxyaniline-2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 2- Naphthylamine-4,8- and -6,8-disulfonic acid, 1-naphthylamine-2-, -4-, -5-, -6- or -7-monosulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-1sulfonic acid, 2-naphthylamine-1,5-, -3,6- and -5,7-disulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, m- and p-nitroaniline, 4-nitroaniline -2-sulfonic acid, 3-nitroaniline-6-sulfonic acid,

   m- or p-aminoacetanilide and 4-amino-2-acetylaminotoluene-5-sulfonic acid.    



   Examples of coupling components which can be used include: 2-amino- and 2-methylamino-5-naphthol-7-sulfonic acid, 2-amino- and 2-methylamino-8-naphthol-6-sulfonic acid, 1 -Amino- and 1-ethylamino-8-naphthol-6-sulfonic acid and corresponding 3,6- and 4,6-disulfonic acids, 1- (3'- or 4'-aminobenzoylamino) -8-naphthol-3,6- and -4,6-disulfonic acid, aniline, o- and m-anisidine, o- and m-toluidine, 2,5-dimethylaniline, 3-aminomethoxytoluene, 2,5-dimethoxyaniline, N-methylaniline, N-ethyl-o-toluidine , N-methyl-m-anisidine, 3-methylamino-4-methoxytoluene, 1- (3'-aminophenyl) -3-methyl-, -carboxy- and -carboethoxy-5-pyrazolone, 1- (4'-amino- phenyl) -3-methyl-,

   -carboxy- and -carboäthoxy5-pyrazolon and 1- (4'-amino-Y-carboxyphenyl) -3-methyl-5-pyrazolone. 



   The aminoazo compounds to be used in the process according to the invention are not restricted to compounds containing only one azo group.  Disazo compounds can be obtained, for example, by tetrazotating an aromatic diamine containing two primary amino groups and coupling the tetrazo compound thus obtained with 2 molar proportions of one of the coupling components defined above or with 1 molar fraction of each of two of the coupling components defined above or with 1 molar fraction of one of the coupling components defined above with 1 mole fraction of a coupling component containing no amino group can be obtained.  Examples of such aromatic diamines are: benzidine, 3,3'-dimethoxybenzidine, benzidine-2,2'-disulfonic acid, benzidine-3,3'-dicarboxylic acid, benzidine-3,3'-diglycolic acid and 4,4'-diaminostilbene-2 , 2'disulfonic acid. 

  Furthermore, disazo or polyazo compounds can be obtained by using primary aromatic amines or diamines containing azo groups. 



  Examples of such primary aromatic amines or diamines containing azo groups are: 4-aminoazobenzene-4-sulfonic acid, 4'-amino-2; methylphenylazo-2-naphthalene-4,8-disulfonic acid, 4-amino-5-methoxy- 2-methyl-4'-nitro-2'-sulfoazobenzene. 



   Instead of starting from -NHR groups, one can also couple a coupling component containing an - NHR group with a diazonium compound containing an - NHR group.  Such diazonium compounds can be obtained by known processes by diazotizing primary or aromatic amines which contain a second amino group or a monosubstituted amino group.  Examples of such primary aromatic amines are: p-phenylenediamin; nin, 1,4-phenylenediamine-2-sulfonic acid, 1,4-phenylenediamine-2-carboxylic acid, 1,4-diaminonaphthalene-2sulfonic acid. 

  Examples of coupling components which can be used in this way are the coupling components listed above and furthermore (3-naphthol, 2-naphthol-6- or -7-sulfonic acid, 2-naphthol-3,6- or -6, 8-disulfonic acid, '-naphthol4-sulfonic acid.    1-phenyl-3-methyl-5-pyrazolone, 1 - (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5! -Dichloro-4;

  ; -Sulfophenyl) -3-methyl-5-pyrazolone, 2-benzoylamino5-naphthol-7-sulfonic acid, 1-benzoylamino-8-naphthol-3,6 or -4,6-disulfonic acid, phenol, p-cresol, acetoacetanilide, acetoacet -2-methoxyaniline-5-sulfonic acid, 3-aminocarbonyl4-methyl-6-hydroxypyridone-2, 1-ethyl-3-cyan or -3-chloro-4-methyl-6-hydroxypyridone-2, 1-ethyl-3 -sulfomethyl-4-methyl-6-hydroxypyridone-2, 2,4,6-triamino-3cyanpyridine, 2- (3'-sulfophenylamino) -4,6-diamino-3 cyanopyridine, 2- (2 hydroxyethylamino) - 3-cyan-4-methyl-6-aminopyridine, 2,6-bis (2'-hydroxyethylamino) -3-cyan4-methylpyridine. 



   Further processes for the preparation of the - NHR group-containing dye compounds of the azo series which can be used in the process according to the invention consist of reducing a nitro group-containing dye or an azo or polyazo compound which contains at least one acylamino group with aqueous acid or aqueous alkali to treat to hydrolyze the acylamino group or groups.  Such azo or polyazo compounds can be obtained from primary aromatic amines and / or coupling components which contain acylamino groups. 

  Examples of such primary aromatic amines are: monoacetylbenzidine, 4-amino-1-acetylaminonaphthalene-6-sulfonic acid, 4-amino-4 -acetylaminodiphenyl-3-sulfonic acid, 4-amino-3-sulfoacetanilide, 3-amino -4-sulfoacetanilide and 4-amino-4 '-acetylaminostilben-3,2idisulfonic acid, and as examples of such coupling components are mentioned: 2-acetylamino-5-naphthol-7-sulfonic acid, 2-N-acetyl N-methylamino-5 -naphthol-7-sulfonic acid, 2-acetylamino and 2-N-acetyl-N-methylamino-8-naphthol-6-sulfonic acids and 1 -acetylamino-8-naphthol-3,6- and -4,6-disulfonic acids. 



   Examples of dye compounds of the anthraquinone series which can be used as starting products in the process according to the invention are: anthraquinone compounds which have a group of the formula -NHR defined above to an alkylamino or arylamino group which is itself bonded to the a position of the anthraquinone nucleus , contain. 

  Examples of such anthraquinone compounds are: 1-amino-4- (4'-aminoaniline) anthraquinone-2,3'-disulfonic acid and the corresponding 2,3 ', 5-, 2,3', 6- and 2,3 7-trisulfonic acids, 1-amino-4- (4 "-amino-4'-benzoylaminoaniline) -anthraquinone-2,3'-disulfonic acid and the corresponding -2,3 ', 5-trisulfonic acid, 1-amino 4, [4 '- (4 "-aminophenylazo) -anilino] -anthraquinone-2,2i', 5-trisulfonic acid, 1-amino-4- (4; -amino-3'-carboxy-anilino) -anthraquinone-2,5-disulfonic acid , 1 -Amino-4- (3;

  ; -aminoanilino) -anthraquinone-2,4 ', 5-trisulfonic acid and the corresponding 2,4'-disulfonic acid 1-amino-4- [4' (4 "-aminophenyl) -anilinoj-anthrachlnon-2,31,, 5 - trisulfonic acid, 1-amino-4- (4'-methylamino) -anilino-anthraquinone-2,3'-disulfonic acid and the corresponding 2,3 ', 5-trisulfonic acid, 1-amino-4- (4'-n- butylamino) anilinoanthraquinone-2,3'-disulfonic acid, 1-amino-4- (4-methylamino-3'-carboxyanilino) -anthrachlnone-2 sulfonic acid, 1-amino-4- (3'-ss-hydroxyethylamino) - anilinoanthraquinone- 2,5-disulfonic acid, 1- (4'-amino-anilino) -anthraquinone-2,3'-disulfonic acid and 1-amino 4- (4-amino-2? -Methoxyanilino) -anthraquinone-2,3'-disulfonic acid . 



   Such dye compounds of the anthraquinone series can even from anthraquinone compounds which contain a halogen atom or a nitro group bonded to the corresponding a-position of the anthraquinone nucleus, or from the leuco derivative of a 1,4-dihydroxy, diamino or aminohydroxyanthraquinone by reacting the corresponding anthraquinone compound at least a molar proportion of an aliphatic or aromatic diamine can be obtained. 



   Dye compounds of the phthalocyanine series which can be used in the process according to the invention are preferably metal-containing phthalocyanines, such as copper phthalocyanines, which contain at least one water-solubilizing group, such as a sulfonic acid group, and at least one group of the formula - NHR, as defined above.    The NHR group or groups can be bonded directly or via a divalent bridge to the benzene rings of the phthalocyanine nucleus, for example via a -phenylene, -CO-phenylene, -SOz-phenylene, -NH-phenylene-, -S-phenylene, -O-phenylene, -CH2S-phenylene-, -CH2O phenylene-, -CH2-phenylene-, -SCH2-phenylene-, - SO2CH2- phenylene-, -SO2NR1-phenylene-, -CH2-,

   -SO2NR1-arylene-,
NRtCO-phenylene, -NR tSO2-phenylene-, - SO2O-phenylene-, - CH2-, - CHNRt-phenylene-, - CHNH-CO-phenylene, - SO2NRt -alkylene-, - CH2NRt -alkylene-, - CONRt -Phenylene-, -CONR1-arylene-, -SO? - or a -CO-bridge.     In the above-mentioned divalent bridge members, R 1 is hydrogen, alkyl or cycloalkyl, arylene is a divalent aromatic, optionally z. B.  radical substituted by halogen, alkyl or alkoxy, in which the terminal bonds can be bound to identical or different nuclei, and alkylene a divalent aliphatic radical which can include heteroatoms, such as nitrogen, in the atomic chain, for example the radical - CH2CH2 - NH - CH2CH2 -.    



   Examples of such divalent aromatic radicals, which are denoted by arylene, are: aromatic nuclei, for example a benzene, naphthalene, acridine and carbazole nucleus, which can carry further substituents, and radicals of the formula
EMI7. 1
 in which the benzene rings can carry further substituents and - D- denotes a bridging group, for example -CH = CH-, -NH-, -S-, -O-, -SOz-, -NO = N-, -N = N- , -NH-CO-NH-CO-NH-, -O-CHICHO- or
EMI7. 2nd

The following may be mentioned as special examples of dye compounds of the phthalocyanine series which can be used in the process according to the invention:

  : Copper phthalocyanine-4-N- (4-amino-3-sulfophenyl) sulfonamide-4'4 ", 4" '- trisulfonic acid, cobalt phthalocyanine-4,41-di-N- (4'-amino-4'-sulfophenyl ) -carbon-amide-4 ", 4" '- dicarboxylic acid and copper-4- (4'-amino-3'sulfobenzoyl) phthalocyanine. 



   Mixtures of aminophthalocyanines can also be used.  For example, a mixture of approximately equal parts of copper phthalocyanine-N- (4-amino-3-sulfophenyl) sulfonamide trisulfonic acid and copper phthalocyanine-N- (4-amino-3-sulfophenyl) sulfonamide disulfonic acid can be used. 



   The aminophthalocyanines containing a sulfonic acid can be obtained either by sulfonation of known phthalocyanines containing primary or secondary amino groups or by synthesis from mixtures of phthalic acid derivatives and sulfonated phthalic acid derivatives.  As a sulfonating agent, for example, oleum, e.g. B.  a 20% solution of sulfur trioxide in sulfuric acid. 

  They can also be obtained by heating suitable derivatives of sulfonated phthalic acid and substituted phthalic acids together by the generally known methods, for example by heating a mixture of 4-sulfophthalic anhydride and 4-p-nitrobenzoylphthalic anhydride, urea, copper (II) chloride and ammonium molybdate in together o-dichlorobenzene at around 150ob.     Phthalocyanines can also be prepared by sulfonation of the corresponding primary and secondary amines or by reacting a primary (or secondary N-alkyl or cycloalkyl) nitroaniline with a phthalocyanine which contains chloromethyl and sulfonic acid or carboxylic acid groups, which are used as starting materials. 

  Furthermore, such aminophthalocyanines can also be prepared by reacting a phthalocyanine which contains chlorosulfonyl groups with a monoacetylalkylenediamine or an amino-nbenzylacetamide in the presence of water and treating the product thus obtained (which contains both sulfonamide and sulfonic acid groups) with aqueous alkali for the hydrolysis of the acetylamino group are, or by reacting a phthalocyanine containing chloromethyl and sulfonic acid or carboxylic acid groups with a monoacetylalkylenediamine and treating the product thus obtained with aqueous alkali to hydrolyze the acetylamino groups. 

  In addition, direct sulfonation or by heating a mixture of suitable carboxy or sulfophthalic acid derivatives with substituted phthalic acid derivatives, for example by heating the anhydrides with urea and a catalyst, in an organic solvent and reducing the resulting nitrophthalocyanine sulfone or carboxylic acid or hydrolysis of the acylaminophthalocyanine sulfone thus obtained - or -carboxylic acid, or by reacting a phthalocyanine compound which contains carboxylic acid chloride groups with a diaminobenzenesulfonic or carboxylic acid, an aminobenzenesulfonic acid or an aminobenzoic acid which also contains a nitro group and reducing the nitro compound thus obtained, or finally by reacting a phthalocyanine compound which Contains carboxylic acid chloride groups,

   with an N-aminobenzylacetamide and subsequent hydrolysis of the product thus obtained with aqueous alkali. 



   Dye compounds of the nitro series which can be used in the process according to the invention are preferably those of the formula
EMI8. 1
 where D is a naphthalene or benzene nucleus, which may be further substituted, the nitrogen atom N is ortho to the nitro group, Z is hydrogen or an optionally substituted hydrocarbon radical and Q is hydrogen or an organic radical bonded to the nitrogen by a carbon atom, and wherein Q and Z are not both hydrogen, and Q is on Z when Z is a hydrocarbon residue or may be attached to D ortho to the nitrogen atom N to form a heterocyclic ring, and which is at least one group of the formula -NHR as defined above , contain. 



   The compounds of the following classes are mentioned as special examples of dye compounds which contain at least one - NHR group and which can be used as starting products in the process according to the invention: 1.  Monoazo compounds of the formula
EMI8. 2nd
 wherein Dl is an at most bicyclic aryl radical free of azo and - NHR groups and the - NHR group is preferably attached to the 6-, 7- or 8-position of the naphthalene nucleus, and which is a sulfonic acid group in the 5 or 6-position of the naphthalene nucleus can contain. 



     Dt can mean a radical of the naphthalene or benzene series which contains no azo substituents, for example a stilbene, diphenyl, benzthiazoylphenyl or diphenylamine radical.  In this class, the related dyes should also be noted, in which the -NHR group, instead of being bound to the naphthalene nucleus, is bound to a benzoylamino or anilino group bonded to the 6-, 7 or 8-position of the naphthalene nucleus. 



   Particularly valuable starting dyes are those in which Dt is a sulfonated phenyl or naphthyl radical, in particular those which contain an -SOsH group ortho to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms, such as chlorine, alkyl radicals, such as methyl, acylamino groups, such as acetylamino, and alkoxy radicals, such as methoxy. 



   2nd  Diazo compounds of the formula (22), in which Dt denotes a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the - NHR group and, if desired, by sulfonic acid, as in class 1. 



   3rd  Monoazo compounds of the formula
EMI8. 3rd
 wherein Dt is an at most bicyclic aryl radical, as described in class 1 and preferably a disulfonaphthyl or stilbene radical, and the benzene nucleus can contain further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid and acylamino groups. 



   4th  Mono- or disazo compounds of the formula
EMI8. 4th
 wherein Dt is an arylene radical, such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series, or preferably an at most bicyclic arylene radical of the benzene or naphthalene series and K is the radical of a naphtholsulfonic acid or the radical of an enolized or enolizable ketomethylene compound (such as an acetoacetarylide or a pyrazole) the OH group in the ortho position to the azo group.    Dt is preferably a residue of the benzene series which contains a sulfonic acid group. 

 

   5.  Mono- or disazo compounds of the formula Di-N = N-K2-NHR (23), in which Dt is a radical of the types defined for Dt in classes 1 and 2 above and K2 is the radical of an enolizable keto methylene compound (such as an acetoacetarylide or a 5 Pyrazolone) with the OH group ortho to the azo group. 



   6.  The metal complex compounds, e.g. B.  the copper, chromium and cobalt complexes, the dyes of the formulas (22) and (23), in which Dt, K and K2 have the meanings given in each case and furthermore a metallizable group (for example a hydroxyl, lower alkoxy or carboxylic acid group) in ortho position to the azo group in Dt is present. 



   7.  Anthraquinone compounds of the formula
EMI9. 1
 wherein the anthraquinone nucleus can contain an additional sulfonic acid group in the 5-, 6-, 7- or 8-position and Z represents a bridge member, which is preferably a divalent radical of the benzene series, for example a phenylene, diphenylene or 4.4t stilbene - or azobenzene residue.  Preferably Z 'should contain a sulfonic acid group for each benzene ring present. 



   8th.  Phthalocyanine compounds of the formula
EMI9. 2nd
 wherein Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, n-OH and / or - NH2, Z 'is a bridge member, preferably an aliphatic, cycloaliphatic or aromatic bridge, and n and m are each 1, 2 or 3 and may be the same or different, provided that n + m is not greater than 4. 



   9.  Nitro dyes of the formula
EMI9. 3rd
 where V and B are monocyclic aryl nuclei and the nitro group in V is ortho to the NH group. 



   The starting dyes in the dye classes mentioned are, for example, the following: In class 1: 6-amino-1-hydroxy-2- (2 -sulfophenylazo) -naphthalene-3-sulfonic acid, 6-methylamino-1 -hydroxy-2- (4 - acetylamino-2 sulfophenylazo) -naphthalene-3-sulfonic acid, 8-amino-1-hydroxy-2- (2'-sulfophenylazo) naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2- (4'- chloro-2'-sulfophenylazo) naphthalene-3,5-disulfonic acid, 7-amino-2- (2 ', 5'-disulfophenylazo) -1-hydroxynaphthalene-3-sulfonic acid, 7-methylamino-2- (2-sulfophenylazo) -1-hydroxynaphthalene-3 -sulfonic acid, 7-methylamino-2- (4'-methoxy-2 -sulfophenylazo) 1 -hydroxy-naphthalen-3 -sulfonic acid, 8- (3'-aminobenzoylamino) - 1 -hydroxy-2- (2'-sulfo phenylazo) -naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2,2'-azonaphthalene-1 ', 3,5', 6tetrasulfonic acid,

   8-amino-1-hydroxy-2,2-azonaphthalene-1, 3,5'-trisulfonic acid, 6-amino-hydroxy-2,2'azonaphthalene-1 ', 3,5'-trisulfonic acid, 6-methylamino 1-hydroxy-2,2-azonaphthalene-1,3,5-trisulfonic acid, 7-amino-1-hydroxy-2,2-azonaphthalene1 ', 3-disulfonic acid, 8-amino-1-hydroxy-2- (4' -hydroxy-3'-carboxyphenylazo) -naphthalene-3,6-disulfonic acid, 6-amino-1-hydroxy-2- (4'-hydroxy-3'-carboxyphenylazo) -naphthalene-3,5-disulfonic acid. 



  In class 2: 8-amino-1-hydroxy-2- [4 '- (2' -sulfophenylazo) -2'-methoxy5'-methylphenylazo] -naphthalene-3, 6-disulfonic acid, 8-amino-1-hydroxy- 2- [4 '- (4! -Methoxyphenylazo) -2 carboxy-phenylazo] -naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2- [4' - (2 "-hydroxy-3", 6 "disulfo-1" -naphthylazo) -2'-carboxyphenylazo] naphthalene-3,6-disulfonic acid, 4,4'-bis (8 "-amino-1'-hydroxy-3", 6'-disulfo-2 "naphthylazo) -3,3'-dimethoxydiphenyl, 6-amino-1-hydroxy-2- [4 - (2-sulfophenylazo) -2 - methoxy-5'-methylphenylazo] naphthalene-3,5-disulfonic acid. 



  In class 3: 2- (4'-amino-2'-methylphenylazo) -naphthalene4,8-disulfonic acid, 2 - (4'-amino-2 -acetylaminophenylazo) -naphthalene-5,7-disulfonic acid, 4-nitro-4 '- (4 "-methylaminophenylazo) -stilbene-2,2'-disulfonic acid, 4-nitro-4' - (4 '-amino-2-methyl-5'-methoxyphenylazo) -stilbene-2,2'-disulfonic acid, 4- Amino-4 '- (4 "-methoxyphenylazo) -stilbene, 2,2'-disulfonic acid, 4-amino-2-methylazobenzene-2, 5-disulfonic acid. 



  In class 4: 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4 (3 "-amino-6" -sulfophenylazo) -5-pyrazolone, 1 - (4'-sulfophenyl) -3-carboxy-4- (4-amino-2-sulfophenylazo) -5-pyrazolone, 1- (2'-methyl-5'-sulfophenyl) -3-methyl-4- (4 amino-2 "sulfophenylazo) - 5-pyrazolone, 1 - (2sulfophenyl) -3-methyl-4- (3-amino6 -sulfophenylazo) -5-pyrazolone, 4-amino-4 '- (3'-methyl-1 "-phenyl-4'-pyrazole 5 "-onylazo) -stilbene-2,2-disulfonic acid, 4-amino-4 '- (2- -hydroxy-3 -' 6 '-disulfo-1- -naphthyl-azo) -stilbene-2,2' -disulfonic acid, 8-acetylamino-1-hydroxy-2- (3-amino-6 -sulfophenylazo) -naphthalene-3,6-disulfonic acid, 7- (3'-sulfophenylamino) -1-hydroxy-2- (4-amino -2-carboxyphenylazo) -naphthalene-3-sulfonic acid, 8-phenylamino-1-hydroxy-2- (4-amino-2-sulfophenylazo) -naphthalene-3,6-disulfonic acid,

   6-acetylamino-1-hydroxy-2- (5- -amino-2 '-sulfophenylazo) -naphthalene-3-sulfonic acid.   



  In Class 5: 1 - (3'-aminophenyl) -3-methyl-4- (2 ', 5'-disulfophenylazo) -5-pyrazolone, 1- (3'-aminophenyl) -3-carboxy-4- (2 '-carboxy-4'sulfophenylazo) -5 -pyrazolone, 4-amino-4' - [3 "-methyl-4 '- (2"', 5 "'- disulfophenylazo)
1 "-pyrazole-5" -onyl] -stilbene-2,2'-disulfonic acid,
1- (3'-aminophenyl) -3-carboxy-4- [4 "- (2" ', 5 "' - disulfo phenylazo) -2" methoxy-5'-methylphenylazo] -5-pyrazolone.    



  In class 6: the copper complex of 8-amino-1-hydroxy-2- (2'-hydroxy-5 "-sulfophenylazo) -naphthalene-3,6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2- (2'-Hydroxy-5'-sulfophenylazo) naphthalene-3-sulfonic acid, the copper complex of 6-amino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) naphthalene-3,5-disulfonic acid , the copper complex of 8-amino-1-hydroxy-2- (2'-hydroxy-3'-chloro-5'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, the copper complex of 6-methylamino-1-hydroxy- 2- (2'-carboxy-5'-sulfophenylazo) naphthalene-3-sulfonic acid, the copper complex of 8-amino-1-hydroxy-2- [4'- (2 "-sulfophenylazo) -2'-methoxy-5 '-methyl phenylazo] -naphthalene-3, 6-disulfonic acid,

   the copper complex of 6-amino-1-hydroxy-2- [4'- (2, 5 "-disulfophenylazo) -2'-methoxy-5'methylphenylazo] -naphthalene-3,5-disulfonic acid, the copper complex of 1- (3'-amino-4'-sulfophenyl) -3-methyl-4-l4 "- (2" ', 5' 'disulfophenyl-azo) -2 "-methoxy-5" -methylphenylazo] pyrazolone, the copper complex of 7- (4'-amino-3'-sulfoanilino) - 1-hydroxy-2- [4 "- (2" ', 5 "' - disulfophenylazo) -2" methoxy-5 "-methylphenylazo] naphthalene -3-sulfonic acid, the copper complex of 6- (4'-amino-3'sulfoanilino) -1-hydroxy-2- (2 "-carboxyphenylazo) -naphthalene-3-sulfonic acid, the 1,2-chromium complex of 7-amino -6'-nitro-1,2'- dihydroxy-2,1'-azonaphthalene-3,4'-disulfonic acid,

   the 1,2-chromium complex of 6-amino-1-hydroxy-2- (2'-carboxyphenylazo) -naphthalene-3 -sulfonic acid, the 1,2-chromium complex of 8-amino-1-hydroxy-2- (4 ' -nitro- 2 -hydroxyphenylazo) -naphthalene-3, 6-disulfonic acid, the 1,2-cobalt complex of 6- (4'-amino-3'-sulfoanilino) -1-hydroxy-2- (5 "-chloro-2 "hydroxyphenylazo) -naphthalene-3 -sulfonic acid, the 1,2-chromium complex of 1- (3'-amino-4'-sulfophenyl) -3-methyl-4- (2" -hydroxy-4 "sulfo-1" - naphthylazo) -5-pyrazolone, the 1,2-chromium complex of 7- (4'-sulfoanilino) -
1-hydroxy-2- (4 "-amino-2" -carboxyphenylazo) naphthalene-3-sulfonic acid,

   the 1,2-chromium complex of 1- (3'-aminophenyl) -3-methyl- 4- (4 "-nitro-2" -carboxyphenylazo) -5-pyrazolone. 



  In class 7:
1-amino-4- (3'-amino-4'-sulfoanilino) anthraquinone-2-sulfonic acid, 1-amino-4- (4'-amino-3'-sulfoanilino) anthraquinone-2, 5-disulfonic acid, 1- Amino-4- [4 '- (4 "-amino-3'-sulfophenyl) anilino] -anthraquinone-2,5-disulfonic acid, 1-Amino-4- [4" - (4 "-amino-2" -sulfophenylazo ) anilino] -anthraquinone-2,5-disulfonic acid, 1-amino-4- (4'-methylamino-3'-sulfoanlino) anthraquinone-2-sulfonic acid. 



  In class 8: 3- (3'-amino-4'-sulfophenyl) sulfamyl copper, phthalocyanine-tri-3 sulfonic acid, di-4- (3'-amino-4'-sulfophenyl) sulfamyl copper refphthalocyanine di-4-sulfonic acid , 3- (3'-Aminophenylsulfamyl) -3-sulfamyl copper phthalocyanine-di-3-sulfonic acid. 



  In class 9: 4-amino-2'-nitro-diphenylamine-3,4'-disulfonic acid. 



   The new dyes can be isolated and processed into usable, dry dye preparations.  The isolation is preferably carried out at the lowest possible temperatures by salting out and filtering.  The filtered dyes can optionally after adding couping agents and / or buffering agents, e.g. B.  after adding a mixture of equal parts of mono- and disodium phosphate, dried; drying is preferably carried out at temperatures which are not too high and under reduced pressure.  In certain cases, the dry preparations according to the invention can be dried directly by atomization drying of the entire preparation mixture, ie.  H.  Manufacture without intermediate insulation of the dyes. 



   The dyes are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyurethanes, but in particular cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton.  They are particularly suitable for dyeing by the exhaust process from a long liquor, from alkaline, if necessary strongly saline, aqueous bath and after the pad dyeing process, after which the goods are impregnated with aqueous and, if appropriate, also saline dye solutions, and the dyes after an alkali treatment or in the presence of alkali, optionally fixed under the action of heat. 



   The dyes are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. B.  of blended fabrics containing wool, silk or wool. 



   The dyes are distinguished by a high reactivity, so that dyeings can be obtained at a lower temperature or with a shorter fixing time than is usually used for comparable dyes. 



   Further advantageous properties are: good drawing power and thus a high degree of fixation, good binding stability between dye and fiber, as well as good washability of the non-fixed portions and good build-up capacity.  The dyeings and prints obtained are very strong in color and have good light fastness and very good wet fastness properties, such as. B.  good fastness to washing. 

 

   In order to improve the wet fastness, it is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if appropriate with the addition of a dispersing agent and promoting the diffusion of the unfixed portions. 



   In the following examples, the parts mean parts by weight, the percentages by weight, unless stated otherwise, and the temperatures are given in degrees Celsius.  The same relationship exists between parts by weight and parts by volume as between grams and cubic centimeters.      



   Example 1 30.5 parts of the dye of the formula
EMI11. 1
 are in 600 vol. Parts of water dissolved and condensed with 7 parts of 2,4,6-trifluoro-1,3,5-triazine.  If no more diazotizable amino groups can be detected, the dye solution is added at 0 to 5 @ and a pH of 4.5 with an aqueous solution which contains 3.1 parts of 2,4-diaminotoluene.  the pe value of the reaction mixture is now increased to 7.5 by adding sodium carbonate and the temperature is slowly increased to 25.  After the condensation has ended, the dye of the formula
EMI11. 2nd
 after adding buffer salts, precipitated with sodium chloride, filtered, washed and dried.  It is an orange powder and dyes cotton in golden yellow tones. 



   Further dyes with similar properties are obtained if the aminoazo dyes listed in the table below with equivalent parts of 2,4,6 trifluoro-1,3,5-triazine and immediately thereafter with the diamines listed in the table as described in Example 1 condensed. 



   Amino dye diamine hue
cotton
1 1- (2'-chloro-5'-sulfophenyl) -3-methyl-4- (4 "-amino-2", 5 "disulfophenylazo) -pyrazolone-5 1,4-phenylenediamine yellow
2 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4- (3 "-amino-6" -sulfophenylazo) -pyrazolone-5 2,4-diamino-toluene yellow
3 2-amino-6- (2'-sulfophenylazo) -5-naphthol-7-sulfonic acid 1,4-phenylenediamine orange
4 2-amino-6- (4'-methoxy-2'-sulfophenylazo) -5-naphthol-7 sulfonic acid 2,4-diamino-toluene scarlet
5 2-Methylamino-6- (4'-ethoxy-2'-sulfophenylazo) -5-naphthol-7-sulfonic acid 2,4-diamino-toluene scarlet
6 2-Amino-7- (4'-ethoxy-2'-sulfophenylazo) -8-naphthol-6-sulfonic acid 1,4-phenylenediamine red
7 <RTI

    ID = 11.12> 1- (4'-aminobenzoylamino) -7- (2'-sulfophenylazo) -8-naphthol-3,6-disulfonic acid 1,4-phenylenediamine red
8 1-Amino-4- (2 ', 4', 6'-trimethyl-3'-sulfo-5'-aminophenylamino) anthrachino-2-sulfonic acid 2,4-diamino-toluene blue
9 2- (4'-amino-2'-acetylaminophenylazo) naphthalene-4,6,8 trisulfonic acid 1,3-diaminopropane yellow 10 2-amino-5- (4 ', 6', 8'-trisulfonaphth-2- ylazo) benzoic acid 1,3-diamino-4-chlorobenzene yellow 11 1- (3'-aminobenzoylamino) -7- (4 "-methyl-2" -sulfophenylazo) - 4,4'-diaminodiphenyl
8-naphthol-3,6-disulfonic acid 2,2'-disulfonic acid red 12 1- (3'-aminobenzoylamino) -7- (2 "-sulfophenylazo) -8- 4,4'-diaminostilbene naphthol-4,6-disulfonic acid 2,2'-disulfonic acid red 13 1- (4'-aminobenzoylamino) -7- (1 ", 5" -disulfonaphth-2 "-ylazo) - 8-naphthol-3,6-disulfonic acid 1,3-diamino-4 -methylbenzene red 14 <RTI

    ID = 11.15> 1- (4'-aminobenzoylamino) -7- (5 ", 7" -disulfonaphth-2 "-ylazo) - bluish
8-naphthol-3,6-disulfonic acid 1,2-diaminoethane red 15 1-amino-7- (1'-hydroxy-4 ', 8'-disulfonaphth-2'-ylazo) -8 4,4'-diaminodiphenyl naphthol -3,6-disulfonic acid,

   Cu complex urea-2,2'-disulfonic acid blue 16 1-amino-4- (4 ', 8'-disulfonaphth-2'-ylazo) -2-methoxy-5- 2,6-diaminonaphthalene methylbenzene 4.8- disulfonic acid yellow
Aminoazo Dye Diamine Hue
Cotton 17 1-amino-4- (5 ', 7'-disulfonaphth-2'-ylazo) -3-methylbenzene - 1,4-phenylenediamine yellow 18 2-amino-6- (4'-acetylamino-2'-sulfophenylazo ) -5-naphthol-7-sulfonic acid 2,4-diaminotoluene scarlet 19 1- (5 ', 7'-disulfonaphth-2'-yl) -3-methyl-4- (3H-amino-6N-sulfophenylazo) pyrazole -5-one 1,3-phenylenediamine yellow 20 1-ethyl-3- (4'-amino-2 ', 5'-disulfophenylazo) -4-methyl-5-aminocarbonyl-6-hydroxypyridon-2 1,6-diaminohexane yellow 21 3- (3 '-amino-6' -sulfophenylazo) -4-sulfomethyl-5-aminocarbonyl-2,6-dihydroxypyridine 4,4'-diaminodiphenyl ether

   yellow 22 2-amino-6- (2'-hydroxy-3 '', 5 -disulfophenylazo) -5-naphthol-7-sulfonic acid, Cu complex 2,4-diaminotoluene violet 23 1-amino-7- (2 ' -hydroxy-6 '-amino-4' -sulfonaphth-1 '-ylazo) naphthol-2,4-disulfonic acid, Cu complex 2,4-diaminotoluene blue 24 l-amino-o- (1', 5 ', 7 '-trisulfonaphth-2'-ylazo) -5-naphthol-7-sulfonic acid 1,4-phenylenediamine orange 25 1 -Amino-4- (6', 8 '-disulfonaphth-2' -ylazo) -naphthalene-6- 4 , 4'-diaminodiphenyl sulfonic acid 2,2'-disulfonic acid yellow 26 1-amino-4- (2 ', 5'-disulfophenylazo) -naphthalene-7-sulfonic acid piperazine yellow 27 1-amino-7- (2'-hydroxy- 5'-amino-3'-sulfophenylazo) -8 naphthol-2,4-disulfonic acid,

   Cu complex 2,4-diaminotoluene blue 28 1- (4 ', 8'-disulfonaphth-2'-yl) -3-methyl-4- (3 "-amino-6" -sulfophenylazo) -pyrazol-5-one 2,4-diaminotoluene yellow
Example 2
30.5 parts of the dye of the formula
EMI12.1
 are dissolved in 600 parts by volume of water and condensed with 7.4 parts of 2,4,6-trifluoro-1,3,5-triazine at 0 to 20 and at a pn value of 4.5 according to the preceding examples.



  After the acylation has ended, 130 parts by volume of an aqueous solution which contains 10.5 parts of 1,3-diaminobenzene-4-sulfonic acid (Na salt) are added to the dye solution, and the temperature is then allowed to rise to 200. the pH of the reaction solution is kept at 4.5 with sodium carbonate solution. When the reaction has ended, the dye is precipitated with sodium chloride, filtered and, while still moist, dissolved in 1500 parts by volume of water at a pn value of 5.5.



  After renewed condensation with 7.4 parts of 2,4,6-trifluoro1,3,5-triazine at 0 to 20 and a p-value of 4.5, 5.4 parts of 2-methyl-aniline are added to the reaction mixture.



  By dropping sodium carbonate solution, the pH is kept at 7.5 during the condensation and the temperature is raised to 200. After the reaction has ended, the dye becomes the formula
EMI12.2
 after adding buffer salts, precipitated with sodium chloride, filtered and washed. After drying, it is an orange powder and dyes cotton in golden yellow tones.

 

   If instead of 2-methylaniline equivalent amounts of ammonia, methylamine, N-methylpropylamine, cyclohexylamine, 4-methoxyaniline, 4-acetylaminoaniline, 4 aminobenzoic acid, 2-chloroaniline, aniline-3-sulfonic acid, aniline-4-sulfonic acid, 2-amino- 5-sulfobenzoic acid, 1-naphthylamine-5-sulfonic acid or 1-naphthylamine-4,7-disulfonic acid also gives valuable dyes that dye cotton in golden yellow shades.



   Further dyes are obtained if, according to the information in the example, the chromophores listed in the table below
EMI13.1
 the diamines
EMI13.2
 and the amines
EMI13.3
 condensed in the order given with 2,4,6-trifluoro-1,3,5-triazine.
EMI13.4


 <tb> 1 <SEP> V <SEP> III <SEP> iv <SEP> v
 <tb> <SEP> H <SEP> R2 <SEP> R3 <SEP> hue <SEP> on
 <tb> <SEP> / <SEP> I <SEP> hue <SEP> on
 <tb> A1N-R <SEP> H-N-B-N-H <SEP> A2 <SEP> R4 <SEP> cotton
 <tb>
1 2- (4 - amino-2'-acetyl-1,4-diaminobenzene-2- 3-sulfophenyl-H yellow aminophenylazo) -naphthalenesulfonic acid
4,8-disulfonic acid
2 2- (4'-amino-2'-acetyl-1,4-diaminobenzene-2-4-sulfo-3-H yellow aminophenylazo) -naphthalenesulfonic acid methylphenyl
4,8-disulfonic acid
3 2- (4'-amino-2'-acetyl-1,3-diamino-4- 4-sulfophenyl H yellow aminophenylazo) naphtaline methylbenzene
4,8-disulfonic acid
4th

   1,4-dimethyl-3-sulfomethyl-5- 1,3-diaminobenzene- -H -CH3 yellow (5'-amino-2'-sulfophenylazo) -6- 4-sulfonic acid hydroxy-pyridone- (2)
5 1,4-dimethyl-3-sulfomethyl-5- 1,3-diaminobenzene- -C2H4OH -C2H4OH yellow (5'-amino-2'-sulfophenylazo) -6- 4-sulfonic acid hydroxy-pyridone- (2)
6 1,4-dimethyl-3-sulfomethyl-5- 1,3-diaminobenzene- -H -H yellow (5'-amino-2'-sulfophenylazo) -6- 4-sulfonic acid hydroxy-pyridone- (2)
7 1,4-dimethyl-3-sulfomethyl-5- 1,4-diaminobenzene-phenyl- -CH3 yellow (5'-amino-2'-sulfophenylazo) -6- 2-sulfonic acid hydroxy-pyridone- (2)
8 1,4-dimethyl-3-sulfomethyl-5- 1,4-diaminobenzene-CH2CH2-0-CH2CH2- yellow (5'-amino-2'-sulfophenylazo) -6- 2-sulfonic acid hydroxy-pyridone- (2)
9 1, 4-dimethyl-3-sulfomethyl-5- 1,4-diaminobenzene - (CH2) s yellow

     (5'-amino-2'-sulfophenylazo) -6- 2-sulfonic acid hydroxy-pyridone- (2) 10 2,4,6-trihydroxy-5- (4'-amino-2 ', 5'- 1,3 -Diaminobenzene- 3-sulfophenyl H yellow disulfophenylazo) -pyrimidine 4-sulfonic acid 11 1- (3'-sulfophenyl) -4- (4 "-amino-2" - 1,3-diaminobenzene-4-methyl-3-sulfophenyl H yellow sulfophenylazo) -pyrazol-5-one-3- 4-sulfonic acid carboxylic acid 12 1- (3'-sulfophenyl) -4- (4 "-amino-2" - 1,3-diaminobenzene- -CH2CH2CH2OCH H yellow sulfophenylazo) - pyrazol-5-one-3- 4-sulfonic acid carboxylic acid 13 1- (3'-sulfophenyl) -4- (4 "-amino-2" - 1,3-diaminobenzene- -H -H yellow sulfophenylazo) -pyrazole-5 -on-3- 4-sulfonic acid carboxylic acid 14 1- (4'-amino-2'-sulfophenyl) -3-methyl-4- 1,3-diaminobenzene-4-carboxyphenyl -H yellow (4 "-methyl-2" -sulfophenylazo) -

   4-sulfonic acid pyrazol-5-one 15 1- (2 ', 5'-disulfophenyl) -3-methyl-4- 1,4-diaminobenzene- - (CH2) 2CH3 -CH3 yellow (5 "-amino-2" - sulfophenylazo) - 2-sulfonic acid pyrazol-5-one 16 l- (2 ', 5'-disulfophenyl) -3-methyl-4- 1,4-diaminobenzene-3-sulfophenyl-H yellow (5 "-amino-2" -sulfophenylazo) - 2-sulfonic acid pyrazol-5-one 17 1- (2 ', 5'-disulfophenyl) -3-methyl-4- 1,3-diaminobenzene-2-methoxyphenyl-H yellow (5 "-amino-2 "-sulfophenylazo) - 4-sulfonic acid pyrazol-5-one 18 4-amino-2-acetylaminoazo-1,3-phenylenediamine-4-sulfophenyl-H yellow benzene-2 ', 5'-disulfonic acid 4'-sulfonic acid
I II III IV V 19 2- (4 '- [4 "-aminophenylazo] phenylazo) - 1,3-phenylenediamine-3-sulfophenyl-H orange naphthalene-4,6,8-trisulfonic acid 4'-sulfonic acid 20 2- Amino-6- (2'-sulfophenylazo) -5- 1,3-phenylenediamine -H-C2H40H orange naphthol-7-sulfonic acid 4'-sulfonic acid 21 2-Amino-6- (2'-sulfophenylazo) -5-1 , 3-phenylenediamine

   -H -H orange naphthol-7-sulfonic acid 4'-sulfonic acid 22 2-amino-6- (1 ', 5'-disulfonaphth-2- 1,4-phenylenediamine-3-sulfophenyl-H orange ylazo) -5-naphthol -7-sulfonic acid 2-sulfonic acid 23 2-amino-6- (4'-methoxy-2'-sulfo-1,4-phenylenediamine-3-sulfophenyl-H scarlet phenylazo) -5-naphthol-7-sulfonic acid 2-sulfonic acid 24 1- (3'-aminobenzoylamino) -7- (2 "-sulfo- 1,3-phenylenediamine-2-methylphenyl H red phenylazo) -8-naphthol-4,6-disulfonic acid 4-sulfonic acid 25 1- (4 ' -Aminobenzoylamino) -7- (2 "-sulfo- 1,3-phenylenediamine -CHs -CH3 red phenylazo) -8-naphthol-3,6-disulfonic acid 4-sulfonic acid 26 1- (4'-aminobenzoylamino) -7- (2 "-sulfo- 1,4-phenylenediamine-3-sulfophenyl-H red

     phenylazo) - 8-naphthol-3,6-disulfonic acid 2-sulfonic acid 27 1-amino-7- (2'-hydroxy-5'-amino-3'-1,3-phenylenediamine-phenyl-H reddish sulfophenylazo) -8 -naphthol-2,4- 4-sulfonic acid blue disulfonic acid, Cu complex 28 1-amino-7- (1'-hydroxy-4 ', 8'-disulfo- 1,3-phenylenediamine -H -H blue naphth- 2-ylazo) -8-naphthol-3,6- 4-sulfonic acid disulfonic acid, Cu complex 29 1-amino-7- (2'-hydroxy-6'-amino-4'-1,3-phenylenediamine -HH blue sulfonaphth-1'-ylazo) -8-naphthol-2,4- 4-sulfonic acid disulfonic acid, Cu complex 30 1-amino-7- (2'-hydroxy-6'-amino-4'- 1,3- Phenylenediamine-3-sulfophenyl-H blue sulfonaphth-1 '-ylazo) -8-naphthol-2,4- 4-sulfonic acid disulfonic acid,

   Cu complex 31 1-amino-4- (4'-aminophenylamino) - 1,3-phenylenediamine-3-sulfophenyl-H blue anthraquinone-2,3'-disulfonic acid 4-sulfonic acid 32 1-amino-4- (3 ' -aminophenylamino) - 1,3-phenylenediamine-4-sulfophenyl- -H blue anthraquinone-2,4'-disulfonic acid -disulfonic acid 4-sulfonic acid 33 1-amino-4- (3-amino-2,4,6-tfimethyl- 1,3-phenylenediamine-3-sulfophenyl- -H blue phenylamino) -anthraquinone-2,5 '- 4-sulfonic acid disulfonic acid
EMI14.1


 <tb> <SEP> (SO3H) 2 <SEP> 7 <SEP> 1,3-phenylenediamine <SEP> -H <SEP> -H <SEP> turquoise
 <tb> 34 <SEP> 3.3 ', 3.3 "" (CuPc); (S02NHC2HJNH <SEP> 4-sulfonic acid <SEP> blue
 <tb> <SEP> (SO2NHC2H4NH2) n <SEP> 3
 <tb>
Example 3
8.65 parts of 2-aminobenzenesulfonic acid are dissolved in water with the addition of sodium hydroxide solution at pH 7.

  5 parts of sodium bicarbonate are added to the solution obtained, the mixture is cooled to 0 ″ and then 7.4 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise.



  After the condensation has ended, an aqueous solution of 10.5 parts of the sodium salt of 1,4-phenylenediamine-2sulfonic acid is added and the condensation is carried out at 5 to 10o, the hydrogen fluoride formed during the condensation being continuously neutralized by the dropwise addition of 2N sodium hydroxide solution. When the condensation has ended, the mixture is cooled again to 0 ″ and another 7 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at a pH of 6 to 7. Finally, an aqueous solution of 25.4 Share the dye of the formula
EMI14.2
 added, the solution warmed to 20 and the hydrogen fluoride released during the condensation was continuously neutralized by adding sodium hydroxide solution.

  After the condensation has ended, the dye is precipitated by adding sodium chloride, filtered off and dried after the addition of buffer salts. It dyes cotton in real yellow tones.



   A dye with very similar properties can be obtained by replacing 1,4-phenylenediamine-2-sulfonic acid with the same amount of 1,3-phenylenediamine-4-sulfonic acid.



   Further valuable dyes are obtained if, instead of the aminoazo dye specified, the chromophores containing amino groups listed in Example 2 and in the table below there are used. The nuances that can be achieved on cellulose fibers are also evident from the information in Example 2.



   Example 4 14.3 parts of the dye of the formula
EMI15.1
 are dissolved in water, cooled to 0 ° and 4.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise, the pe value of the reaction mixture being kept at 6 by simultaneous addition of sodium hydroxide solution. Thereafter, an aqueous solution of 6.3 parts of 1,3-phenylenediamine-4sulfonic acid sodium salt is added and the mixture is stirred at 5 to 10 'and a pH of 6.5 until the condensation has ended. The reaction mixture is then cooled again to 00 and 4.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise again at pH 6 to 6.5. Finally, 17.5 parts of the amino group-containing dye of the formula
EMI15.2
 added as an aqueous solution.

  The mixture is heated to 20 to 250 and the hydrogen fluoride liberated in the condensation is continuously neutralized by adding sodium carbonate solution at a p-value of 7. The green dye solution is precipitated as sodium salt by adding sodium chloride, filtered off and dried. It dyes cotton in wet-green shades.



   If, instead of the specified anthraquinone dye, an equivalent amount of the blue copper complex of 1-amino-7- (2'-hydroxy-6'-amino-4'-sulfonaphth-1-ylazo) -8-naphthol-2,4-disulfonic acid is used, this also gives a green dye.



   Coloring examples
A. 20 parts of the yellow dye of Example 1 are dissolved in 1000 parts by volume of water. A cotton fabric is padded with this dye solution and then squeezed to an 80% liquor intake. After intermediate drying at 50O, the dyeing is treated with a solution of 200 parts of sodium chloride and 10 parts by volume of 30% sodium hydroxide solution in 1000 parts by volume of water and then steamed at 100o for 15 seconds. After rinsing, a strong, washable, greenish yellow color is obtained.



   You get an approximately equally strong color if you store for 2 minutes at room temperature instead of steaming.



   B. 3 parts of the blue dye, Table No. 8, are dissolved in 100 parts of water. With this solution, a cotton cloth is padded at ordinary temperature and then dried at 50O. The colored piece obtained is then immersed in a 30O warm solution of 250 parts of sodium chloride and 30 parts by volume of 30% sodium hydroxide solution in 1000 parts by volume of water for 10 seconds, then rinsed with cold and hot water. The result is a strong, washable and lightfast blue color.



   C. A cotton fabric is impregnated with a solution of 25 parts of the orange dye, Table No. 3, 20 parts of sodium carbonate and 30 parts of sodium sulfate in 1000 parts by volume of water and squeezed to a 70% weight gain. The impregnated fabric is now stored in a moist state at 25o for 4 hours, then rinsed well. The result is a real orange color.



   D. 1 part of the reddish yellow dye, Table No. 1, and 30 parts of table salt are dissolved in 1000 parts by volume of water. In this bath, one enters at 40O with 50 parts of moistened cotton fabric and dyes for 30 minutes while constantly moving the material to be dyed, with another 30 parts of table salt being added after 15 minutes of dyeing. Then add 20 parts of anhydrous sodium carbonate and dye for a further 60 minutes at 40O. The dyeing obtained is rinsed cold and hot, spun off and dried. A strong golden yellow color with excellent fastness properties is obtained.



   E. A padding liquor is prepared from 3 parts of the dye, Table No. 8, 10 parts of urea, 5 parts of sodium bicarbonate and 82 parts of water. This padding liquor is used to impregnate and squeeze a fabric made of mercerized cotton, which is then heated to 1600 for 60 seconds.

 

  A brilliant blue color is obtained after rinsing.



   Print example
50 parts of the dye, Table No. 2, are sprinkled into and dissolved in a printing paste thickener consisting of 730 parts of a 3% aqueous alginate solution, 200 parts of urea and 19 parts of sodium bicarbonate. A cotton fabric is printed with this printing paste and then dried. The pressure is fixed at 100 by steaming for two minutes and then washed out. A strong greenish yellow print is obtained.



   Instead of steaming, the print can be fixed with the same color yield by immersing it in a bath containing 250 parts of table salt and 30 parts of 30% sodium hydroxide solution in 1000 parts of water at 90 ° for 10 seconds.


    

Claims (11)

PATENT CLAIMS 1. Process for the production of fiber-reactive dyes of the formula EMI1.1 wherein Ao is the residue of a sulfo-containing chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series, A2 is an organic radical, B is an alkylene or arylene radical and R1, R2, R3 and R4 are independently hydrogen or alkyl, characterized in that a dye of the formula EMI1.2 a compound of the formula EMI1.3 an alkylene or arylenediamine of the formula EMI1.4 and trifluoro-s-triazine of the formula EMI1.5 condensed in any sequence to a fiber-reactive dye of the formula (1), where Al, A2, B, Rl, R2, R3 and R4 in the formulas (3), (4) and (5) have the meanings given under formula (1) to have. 2. The method according to claim 1, characterized in that VW bonds of the formula (4), in which A2 is the residue of a chromophore of the anthraquinone, azo, phthalocyanine or nitroaryl series and R4 is hydrogen or alkyl, and in the rest compounds of the formulas (3 ) and (5), wherein A1, R1, B, R2 and R3 have the meanings given in claim 1, used as starting materials. 3. The method according to claim 2, for the production of fiber-reactive dyes of the formula (1), wherein Al and A2 are the same chromophores from the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenylene radical and Rl, R2, R3 and R4 each have a hydrogen atom is characterized in that a phenylenediamine of formula (9) in a molar ratio of 1: 2 with trifluoro-s-triazine of formula (6) to a compound of formula EMI1.6 condensed and this condensed with a dye of the formula A @ (2) -NH2 (7) in a molar ratio of 1: 2 4th A process according to claim 2 for the production of fiber-reactive dyes of the formula (1), in which Al and A2 are identical chromophores from the anthraquinone, azo, phthalocyanine or nitroaryl series, B is a phenylene radical and Rl, R2, R3 and R4 are each a hydrogen atom , characterized in that a dye of the formula A @ (2) -NH2 (7) with trifluoro-s-triazine to a compound of the formula EMI1.7 condensed and condensed in a molar ratio of 2: 1 with a phenylenediamine of the formula H2NI3-NH2 (9). 5. The method according to claim 4 for the preparation of the fiber-reactive dye of the formula EMI 1.8 characterized in that the dye of the formula EMI2.1 condensed with trifluoro-s-triazine and the condensation product obtained condensed with 2,4-diaminotoluene in a molar ratio of 2: 1. 6. The method according to claim 1, for the preparation of fiber-reactive dyes of the formula (1), characterized in that a dye of the formula (3), an alkylene or arylenediamine of the formula (5) and trifluoro-s-triazine of the formula ( 6) in any order to a fiber-reactive dye of the formula EMI2.2 reacted, and the dye of formula (10) with a compound of formula (4) condensed. 7. The method according to claim 6, characterized in that the compound of the formula (4) is an aminobenzene of the formula EMI2.3 wherein X is hydrogen, halogen, alkyl, alkoxy, carboxy or sulfo, and the benzene radical D in addition to X may contain other substituents, in particular another sulfonic acid group. 8. The method according to claim 1 for the production of fiber-reactive dyes of the formula EMI2.4 wherein Al and B have the meanings given in claim 1, X is hydrogen, halogen, alkyl, alkoxy, carboxy or sulfo, and the benzene radical D in addition to X may contain further substituents, in particular a further sulfonic acid group, characterized in that trifluoro-s triazine of the formula (6) with a dye of the formula (3) and an alkylene or arylenediamine of the formula H2N-B-NH2 (9) to give a dye of the formula EMI2.5 condensed that trifluoro-s-triazine of the formula (6) with an aminobenzene of the formula EMI2.6 to a phenylamino-difluoro-s-triazine of the formula EMI2.7 condensed, and that one condenses the dye of formula (13) with the phenylamino-difluoro-s-triazine of formula (14). 9. The method according to any one of claims 1 to 8, characterized in that the reactions with difluoro- or trifluoro-s-triazines are carried out in aqueous solution. 10. Process for the preparation of fiber-reactive dyes of the formula EMI3.1 wherein Al is the residue of a sulfo group-containing chromophore of the aza series, A2 is an organic residue, B is an alkylene or arylene residue and Rl, R2, R3 and R4 are independently hydrogen or alkyl, characterized in that diazo components or coupling components of the dye of the formula EMI3.2 which is an amino group of the formula EMI3.3 contain a compound of formula EMI3.4 or optionally diazo components or coupling components of the compound of formula (4) which are an amino group of the formula EMI3.5 included, with trifluoro-s-triazine of the formula EMI3.6 condensed and the condensation products obtained with the further components of the dye of the formula (3) or the compound of formula (4) and alkylene or arylene diamines of the formula EMI3.7 Coupled and condensed in any sequence to fiber-reactive dyes of the formula (1), where Al, A2, B, Rl, R2, R3 and R4 in the formulas (3), (4), (5), (15) and (16 ) have the meanings given under formula (1). 11. The method according to claim 10, characterized in that the reactions with difluoro or trifluoro-s-triazines are carried out in aqueous solution. The present invention relates to a method for producing fiber-reactive dyes of the formula EMI3.8 wherein Al is the residue of a chromophore containing sulfo groups, A2 is an organic residue, B is an alkylene or arylene residue and R 1, R 2, R 3 and R 4 are independently hydrogen or alkyl. The remainder of a chromophore, Al, can be the remainder of an anthraquinone, azo, phthalocyanine or nitroaryl series chromophore. The organic residue A2 can be a colorless residue or also the residue of a chromophore. The colorless residues A2 are e.g. considered: alkyl radicals, such as methyl, ethyl, propyl, isopropyl, butyl, methoxyethyl, methoxypropyl, ethoxyethyl, cyanoethyl, hydroxyethyl, cyclohexyl, methylcyclohexyl; Aryl radicals, such as phenyl, optionally substituted by alkyl groups, such as methyl, methyl, propyl, isopropyl, butyl, alkoxy groups, such as methoxy, ethoxy, isopropoxy, ethoxyethoxy, isopropoxypropoxy, acyl groups, such as acetyl, acetylamino or benzoylamino, the ureido, carboxy and Sulfo group and halogen atoms such as chlorine or bromine; Naphthyl, sulfonaphthyl; heterocyclic radicals, such as pyridyl, benzthiazolyl, oxazolyl, thiazolyl, quinolyl. A2 can also be part of a heterocyclic radical in that A2 and R4 in formula (1) are closed to form a ring, so that the latter is bonded directly to the s-triazine radical via the nitrogen atom to which A2 and R4 are bound. Examples of such heterocyclic radicals are piperidyl and morpholyl. Above all, A2 is the rest of a chromophore. Like Al, this can be the residue of a chromophore from the anthraquinone, azo, phthalocyanine or nitroaryl series. Furthermore, A2 and Al are preferably identical radicals. The alkylene or arylene radical B is derived from an aliphatic or aromatic diamine. Thus B can be a long (e.g. with 10 or more carbon atoms) or shorter, straight-chain or branched alkylene radical; in particular an alkylene radical with 1 to 6 carbon atoms comes into consideration, e.g. Ethylene, propylene, butylene, hexylene or ** WARNING ** End of CLMS field could overlap beginning of DESC **.