CH615937A5 - Process for the preparation of novel dyestuffs for synthetic textile material - Google Patents

Abstract

The dyestuffs of the formula <IMAGE> in which B is a coupling component of the disperse series, which contains a non-acylated or acylated primary or secondary amino group in the o-position to the azo bridge and is free of water-solubilising groups, R is a hydrogen atom, a cycloalkyl group or an optionally substituted alkyl group, and the benzene radical A optionally contains further substituents, are prepared by coupling the diazonium compound of an aniline of the formula <IMAGE> with a coupling component of the disperse series of the formula H-B. The dyestuffs are especially suitable for dyeing and printing fully synthetic textile materials. Dyeing is carried out under conditions in which the dyestuffs are converted by removal of the HOSO3<(-)> group into water-insoluble disperse dyestuffs which are then absorbed as such onto the material to be dyed.

Description

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

Carbamic acid or sulfonic acid or a radical of the formula -CO-NH2, d is a hydrogen atom, a chlorine or bromine atom, a lower alkyl, lower alkoxy, lower alkylthio, phenyl, phenyloxy, phenylthio, lower alkyloxycarbonyl or lower alkylaminocarbonyl group, and R15 and R16 denote alkyl radicals which are optionally interrupted by at least one heteroatom and / or optionally substituted.

10. The method according to claim 9, characterized in that coupling components are used in which d is a hydrogen atom.

11. The method according to claim 9, characterized in that coupling components are used in which Ac is a lower alkyl carbonyl radical.

12. The method according to claim 9, characterized in that coupling components are used in which Ris and R16 denote phenyl-lower alkyl, cyano-lower alkyl, cyanoethoxy-lower alkyl, lower alkylcarbonyloxy-lower alkyl, lower alkoxy-lower alkyl or lower alkyl groups.

13. The method according to claim 4, characterized in that coupling components of the formula

is used, in which the ring B 'can be substituted by halogen atoms, hydroxy, acylamino or lower alkyl groups, and R1 is a lower alkyl radical.

14. The method according to claim 4, characterized in that the coupling component of the formula

is used in which R1 'is a hydrogen atom, an aryl, lower alkoxy or lower alkyl radical.

15. The method according to claim 6, characterized in that the coupling component of the formula

used, in which Re 'and R7' are hydrogen atoms and Re "and R7" are hydrogen atoms or methyl, ethyl, propyl and / or butyl groups.

16. The method according to claim 6, characterized in that the coupling component of the formula

is used in which Rs' is an optionally substituted alkyl group having 1 to 12 carbon atoms, a cyclohexyl radical or an aromatic radical.

17. The method according to claim 2, characterized in that coupling components of the formula

starts in the X 'cyano or carboxamide, C17 hydrogen, alkyl with 1 to 8 carbon atoms, optionally substituted by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to 8 carbon atoms, alkyl, phenyl, optionally substituted by chlorine, methyl, ethyl , p-hydroxyethyl methoxy or ethoxy substituted phenyl, cyclohexyl, benzyl, phenylethyl or N pyrrolidonylalkyl with 2 or 3 carbon atoms in the alkyl radical, R15 hydrogen, alkyl with 1 to 8 carbon atoms, optionally by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to 8 carbon atoms substituted alkyl, R17 and R18 together with the nitrogen the remainder of the pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine, where independently of one another R19 have the same meaning as R17 and R20 have the same meaning as R18.

18. The method according to claim 17, characterized in that one starts from coupling components in which R19 and R20 are hydrogen atoms and X 'is a cyano group.

Hydrophobic synthetic organic material, especially polyester material, is known to be dyed with disperse dyes such as those used, for. B. are described in the Color Index. These are colored organic compounds that are free of water-solubilizing groups, such as sulfonic acid or ammonium groups, and are only soluble in water in traces, and are absorbed onto the material via a molecularly dispersed dissolved phase. For this purpose, the disperse dyes must very much before the actual dyeing process finely ground and stabilized by adding large amounts of dispersants in the aqueous dye bath. During dyeing, the dye is not in solution, but as a dispersion.

This often gives rise to great difficulties in practice, because these dye dispersions are often unstable, the dye crystallizing out, which in turn leads to uneven colorations. In high-temperature dyeing in particular, insufficient dispersion stability becomes noticeable due to filtration phenomena in dense material, for example on packages and in tree dyeing. The dispersants can also be used in large dyeing machines

Foam formation and, since it is mostly toxic, represent a major burden for the wastewater. Difficulties also arise when dyeing mixed fabrics, since water-soluble dyes often do not get along well with the dispersants of disperse dyes.

A process for the preparation of dyes has now been found which makes it possible to circumvent these difficulties by dyeing hydrophobic, synthetic organic material in a weakly acidic, neutral or alkaline solution of the intermediate water-soluble disperse dyes which contain a group which can be split off under the dyeing conditions that carries at least one water-solubilizing group.

The invention therefore provides a process for the preparation of dyes of the formula

where B is a coupling component of the dispersion series which contains a non-acylated or acylated primary or secondary amino group in the o-position to the azo bridge and is free of water-solubilizing groups, R is a hydrogen atom, a cycloalkyl or an optionally substituted alkyl group and the benzene radical A optionally contains further substituents, which is characterized in that the diazonium compound of an aniline of the formula

wherein R and A are the same as above, with a coupling component of the dispersion series of the formula H-B, wherein B is the same as above.

A heterocyclic coupling component or a coupling component from the aniline or aminonaphthalene series is preferably used.

Preferred coupling components are, for. B. those of formula III

wherein R1 is hydrogen, lower alkyl, lower alkoxy, cyano, lower alkoxycarbonyl; Carbomoyl, lower alkoxy-lower alkoxycarbonyl, phenoxy or phenyl group, R2 represents a hydrogen atom, an optionally substituted aliphatic, cycloaliphatic, aromatic or heterocyclic group.

Coupling components of the formula IV are likewise preferred

wherein Ra is a hydrogen atom, a lower alkyl or phenylalkyl group and R4 and R5 are each hydrogen or halogen atoms, lower alkyl, lower alkoxy, nitro, sulfonylamido, N-lower alkylsulfonylamido or N, N-di-lower alkylsulfonylamido groups.

Further preferred coupling components used correspond to the formula V.

wherein two radicals Z are groups of the formula -NR6R7 and the other Z is a group of the formulas -NR6R "-OR8 of the -S-Rs, where Rs, R, and R5 each hydrogen, aryl, aralkyl, cycloalkyl or one mean aliphatic radical and Rs and R7 can form a ring containing the amine nitrogen and the radicals -NR6R, can be identical to or different from one another.

In addition, those of the formula VI are preferably used as coupling components

where Ql is a

-N bridge R12 and the other Q independently of one another are an oxygen or sulfur atom or the -N (Rt) bridge, where R12 is lower alkyl or preferably a hydrogen atom, and Rs, Rlo and R11 are optionally substituted hydrocarbon radicals or hydrogen atoms.

Further preferred coupling components correspond to the formula VII

wherein Rls and 14 each independently represent a hydrogen atom, an optionally substituted alkyl, aryl, alkoxy, aryloxy, alkylamino or arylamino radical or an (alkyloxy or aryloxy) carbonyl radical or (alkyloxy or aryloxy) carbonylalkyl radical or a (Aryloxy, arylthio or arylamino) alkyl radical or a styryl radical or aralkyl, thiophenyl or pyridyl radical, and R14 and Rl are optionally interrupted and / or optionally substituted alkyl radicals by at least one heteroatom.

Likewise preferred coupling components correspond to the formula VIII

where Ac is the acyl radical of a lower aliphatic or aromatic carboxylic acid, carbonic acid half-ester, carbamic acid or sulfonic acid or a radical of the formula --CO-NH2-, d is a chlorine or bromine atom, a lower alkyl, lower alkoxy, lower alkylthio, phenyl, phenyloxy, Is phenylthio, lower alkyloxycarbonyl or lower alkylaminocarbonyl group or, preferably, a hydrogen atom, and R12, R15 and R16 are the same as above.

The d-position is preferably bonded to the azo group in the m-position.

In addition, coupling components of the formula XIII are preferably used

in which X 'is cyano or carboxamide, R17 is hydrogen, alkyl having 1 to 8 carbon atoms, alkyl, phenyl, optionally substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having a total of up to 8 carbon atoms phenyl, cyclohexyl, benzyl, phenylethyl or # -N-pyrrolidonylalkyl with 2 or 3 carbon atoms in the alkyl radical, substituted by chlorine, methyl, ethyl, β-hydroxyethyl, methoxy or ethoxy.

R18 is hydrogen, alkyl with 1 to 8 carbon atoms, optionally substituted by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to S carbon atoms, R17 and Ris together with the nitrogen - the remainder of the pyrrolidine, Piperidine, morpholine, piperazine or N methylpiperazine mean, where R19 independently of one another have the same meaning as Rt7 and R20 has the same meaning as R18.

Preferably R19 and R20 are hydrogen atoms and X, a cyano group -The benzene ring A in the diazonium compounds can, for. B. have the following substituents that do not dissociate acidic in water: Chlorine or bromine atoms, methyl, ethyl, nitro, cyano, trifluoromethyl, methyl or iithylsulfonyl, N- (methyl, ethyl, propyl, butyl, cyanoethyl) aminosulfonyl, N, N -Bis (methyl, ethyl, hydroxyethyl) aminosulfonyl, methoxy or ethoxycarbonyl, acetylamino or propionylamino groups.

The radical R in the diazonium compounds is z. B. a hydrogen atom ,. an ethyl, propyl, butyl, benzyl, ss cyanoethyl, ss-hydroxyethyl, ss-chloroethyl or a cyclohexyl group.

The rest of R1. in the coupling components of formula III is.z. B. a hydrogen atom, a methyl, ethyl, propyl, butyl, cyano, methoxy, ethoxy, propoxy, butoxy, phenoxy, p-tolyloxy, phenyl (methyl, ethyl, propyl -Butyl-) oxycarbonyl-, aminocarbonyl-, aminosulfonyl-, N-mono- (methyl, ethyl, propyl, butyl) aminosulfonyl, N-di (methyl-, ethyl-, propyl-, butyl-) aminosulfonyl, N-bis ( hydroxy ethyl) aminosulfonyl group.

The radical R2 is, for example, a radical of the formula

wherein the ring B 'no.ch by chlorine, bromine, nitro, trifluoromethyl, methyl, ethyl, propyl, butyl, methoxy ,.

Ethoxy, propoxy, butoxy, methylsulfonyl, ethylsulfonyl, phenoxysulfonyl, (methyl, ethyl, propyl, butyl) carbonyl, amino, benzoylamino, (methyl, ethyl, propyl, butyl ) -.

sulfonylamino-, aminosulfonyl-, N- (methyl-, ethyl-, propyl-, butyl-) aminosulfonyl, N, N-di- (methyl-, ethyl-, propyl-, butyl) aminosulfonyl-, -CH2-C6H5, - CH2CH2-C6H5, -C6H11, - (CH2) 1-6 -O-CO- (methyl, ethyl, propyl, butyl) - (CH2) 1-3 -NH-CO- (methyl, ethyl, propyl, butyl) - groups can be substituted. Coupling components used with preference correspond to the formula

where R1 is a lower alkyl radical, e.g. denotes a methyl, ethyl, propyl or butyl radical and; the phenyl nucleus B still has a substituent from the group halogen, hydroxy, acylamino or lower alkyl, in particular chlorine or bromine atoms, hydroxy =, lower alkylcarbonylamino, (formylamino, acetylamino, propionylamino, butyrylamino), benzoylamino, methyl, ethyl, propyl , Butyl groups. Coupling components of the formula may also be mentioned

where R1 is a hydrogen atom, an aryl, lower alkoxy or lower alkyl radical, preferably a phenyl, ethoxy and, in particular, methoxy or methyl radical. - - - - - Lower alkyl groups contain 1 to 4 carbon atoms and are e.g. B. methyl, ethyl, propyl, isopropyl and isobutyl radicals, while lower alkoxy groups z. B. methoxy, ethoxy, propoxy or butoxy radicals.

The radical R3 in formula IV usually stands for a hydrogen atom, a methyl, ethyl, propyl, butyl, benzyl, phenylethyl, hydroxyethyl or cyanoethyl group The radicals R4 and R5 in formula IV mean, for. B. each independently of one another hydrogen atoms, chlorine or bromine atoms, methyl, ethyl, propyl; Butyl, ethoxy, propoxy, butoxy, nitro, aminosulfonyl, N (methyl, ethyl, propyl, hydroxyethyl) aminosulfonyl, N, N-bis (methyl, ethyl, propyl, butyl -, hydroxyethyl) aminosulfonyl, methyl or ethylsulfonyl, (methoxy, ethoxy) sulfonyl groups.

Examples of the radicals R6, R7 and R8 occurring in the coupling components of the formula (V) include e.g. Methyl, ethyl, propyl, isopropyl, butyl, sec-butyln-pentyl, and octyl radicals, which are interrupted by oxygen atoms and replaced by hydroxy, carboxyl, carbalkoxy (with 2- 6 carbon atoms), such as (methyl, ethyl, propyl, butyl) oxycarbonyl, alkoxy (with 1-8 carbon atoms, such as methoxy, ethoxy, propoxy -; - butoxyv ,.

Hexyloxy or pentyloxy, phenoxy, acyloxy (with 1-10 carbon atoms), optionally with halogen atoms, such as chlorine, bromine, fluorine atoms, propoxy, butoxy, methyl, ethyl, propyl, butyl, B -Hydroxyäthyl-, Äthoxycarbonyl-, Methoxycarbonyl-, Propoxycarbonyl- or Butoxycarbonylgruppen substituted phenyl groups or benzyl, or phenethyl, or cyclohexyl groups can be substituted or the radicals Re and R7 together to form a piperidine, pyrrolidine, morpholine, piperazine or Methylpiperazine ring are linked.

As acyl radicals, for. B. fatty acid residues with up to 5 carbon atoms such as formyl, acetyl, propionyl, butyl residues; Alkylcarbamyl radicals with up to 5 carbon atoms, such as methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, or butylaminocarbonyl radicals; Alkyloxycarbonyl radicals with up to 5 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl radicals; Phenylcarbamyl or phenoxycarbonyl radicals, benzoyl, phenoxyacetyl, chloroacetyl or phenylacetyl radicals in question.

Preferred coupling components of the formula (V) are those of the formula XI

in which R6 and R7E are hydrogen atoms and R6 and R7 are hydrogen atoms or methyl, ethyl, propyl and / or butyl groups, as well as those of the formula XII

wherein R5 'is a methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, phenyl, toluyl, chlorophenyl, or acetamidophenyl group.

The radicals Re, Rio and Rii contained in the coupling components of the formula VI are z. B. optionally by hydroxyl or cyano groups, lower alkoxy groups, lower alkanoyloxy groups or straight-chain or branched alkyl groups with up to 8 carbon atoms substituted by primary, secondary or tertiary amino groups, or cyclohexyl groups, benzyl groups and optionally by halogen atoms, nitro groups, acetyl groups, benzoyl groups, cyano groups, Lower alkyl groups, lower alkoxy groups, trifluoromethyl groups, lower alkylsulphonyl groups, phenoxysulphonyl groups, lower alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower alkoxycarbonyl groups, lower alkoxy lower alkoxycarbonyl groups, benzoylamino groups, acetylamino groups, substituted phenyl radicals. The radical R12 is a lower alkyl group or, preferably, a hydrogen atom.

In the coupling components of the formula VI, there are preferably 2 radicals Q — NRi2 bridges, in which case Qt and Qs are each usually one

-R12 -N bridge.

Coupling components in which Re, Rio and R11 have the meaning given above are particularly preferably used.

The radicals -CO-Ru and -CO-Rr4 in the coupling components of the formula VII can be identical to or different from one another.

The radicals -CO-Rl3 and -CO-R14 and the radical AC in the coupling components of the formula VIII represent unsubstituted or substituted fatty acid radicals such as formyl, acetyl, propionyl, butyryl, l-methylbutyryl, hexanoyl, crotonyl , Octanoyl, decanoyl, dodecanoyl, hexadecanoyl, palmityl or stearyl radical, also a glycol or methyl mercaptoacetic acid radical, chloroacetyl, α, ß-dibromo or dichloropropionyl, ss-bromopropionyl, 4-chlorobutyryl, cyanoacetyl Acetoacetyl, ethoxyacetyl, bromoacetyl, 2-phenylbutyryl, 4-benzoyl-butyryl, 4-phenyl-butyryl, cyclohexane butyryl, 2-bromostearyl, ll-bromundecanoyl, palmitoyl, glycoyl and 3- and 4-hydroxybutyryl radicals.

The radicals -CO-R13, -CO-Rz4 and Ac can also be used: The half-esterified dicarboxylic acid residues of the general formula (aryloxy- or lower alkoxy) -CO- (CH2) m ~ 1-CO-, where m = 1-9. Examples include: B. the methoxycarbonylcarbonyl radical, the C2H5-O-CO- (CH2) 4-CO radical and the p-CH-CoH4-O-CO-CH2CH2-CO radical. Half-esterified acyl residues of oxalic acid, such as the residues of the formulas CH3-O-CO-CO-, C4He-O-CO-CO-, p-C1-CsH4-O-CO-CO, o-CH3-CssH4-O-CO- CO-, p-CHsC6H4O-CO-CO- and p-C2Hs- O-CGH4-O-CO-CO-, the radicals of cycloaliphatic carboxylic acids, such as the cyclohexane carbonyl, methylcyclohexane carbonyl and dimethylcyclohexane carbonyl radical; the residues of araliphatic carboxylic acids, such as phenylacetyl, ss phenylpropionyl, phenoxyacetyl, (p-nitro, p-acetyl, o-butoxycarbonyl, o-methoxy, p-butoxy, p-methyl, p- Bromine 3,5-dichloro, p-itthyl-, p-chloro) phenoxyacetyl-, phenoxypropionyl-, phenoxybutyryl, phenoxythioacetyl, 3,5-dichlorophenylthioacetyl, p-methoxycarbonylphenylmercaptoacetyl, a-phenylmercapto-propionyl-, y- (p -nitrorylphenyl , Phenylaminoacetyl, p-chlorophenylaminoacetyl, m itthylphenylaminoacetyl, N-morpholinoacetyl, styrylcarbonyl and the cinnamylcarbonyl radical; the radicals of aromatic carboxylic acids, such as benzoyl, methylbenzoyl, p-chlorobenzoyl, p-nitrobenzoyl, 3,5-nitrobenzoyl Methoxybenzoyl, 4-phenoxybenzoyl, 4-phenylbenzoyl, 4-phenylmercapto-benzoyl, 4-phenylazobenzoyl, a-naphthoyl and the ss-naphthoyl radical; and the radicals of heterocyclic carboxylic acids, such as furoyl, nicotinyl, thiophene-2carbonyl or pyridine-3- or -4-carbonyl radical.

The acyl radicals -CO-R19, -CO-R14 and Ac can also be derived from alkyl or aryl half esters of carbonic acid, and R13 and R14 then represent C1-Cs-alkoxy- or optionally substituted phenoxy groups, such as. B. for methoxy, ethoxy, n-propyloxy, isopropyloxy, p-chloro ethoxy, ss-methoxyethoxy, n-butoxy, isobutoxy and hexyloxy groups, also phenoxy, chlorophenoxy, bromophenoxy, nitrophenoxy -, Carbäthoxyphenoxy-, Methoxyphenoxy-, Methylphenoxy- or Äthylphenoxyrest.

The acyl radicals -CORi3, -COR14 and Ac can also be derived from alkyl, cycloalkyl or aryl carbamic acids and heterocyclic carbamic acids, and R13 and R14 then stand for C1-Cs-alkylamino, cyclohexylamino or optionally substituted phenylamino groups, such as. B.

Methylamino, ethylamino, propylamino, butylamino, octylamino, cyclohexylamino, phenylamino, (chlorine, bromine, methyl, methoxy, ethoxy, nitro, trifluoromethyl, methoxycarbonyl or ethoxycarbonyl) phenylamino , Dimethylphenylamino, naphthylamino, 3-pyridylamino, 3-tetramethylene sulfonamino, furfurylamino or thiophenamino groups.

The groups Ru and Rlss can be hydrogen atoms or lower, i.e. H. Alkyl groups containing 1 to 4, preferably 2 to 4 carbon atoms, such as methyl, ethyl, n-propyl or n-butyl groups, which can be interrupted by one or two oxygen atoms and / or substituted in the usual way. Possible substituents are: Halogen atoms, preferably fluorine, chlorine or bromine atoms, phenyl, lower alkoxy, lower alkylcarbonyloxy, lower alkylcarbonylamino, benzoyloxy, benzoylamino (the benzoyl groups being substituted by chlorine, bromine, 4-methyl, ethyl, methoxy and ethoxy groups can), cyano, hydroxy, phenoxy, phenylcarbonyl, phenylsulfonyloxy, phenoxycarbonyl, phenylthio (where the phenyl groups can each be substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy groups), lower alkylsulfonyl, lower alkoxycarbonyloxy, phenoxycarbonyloxy, and phenoxycarbonyloxy -, aminocarbonyl, mono-lower alkylaminocarbonyl, di-lower alkylaminocarbonyl, lower alkylcarbonyl, succinimido, phthalimido lower alkoxycarbonyl, Cinnamoyl, thiophene carbonyl, pyridine carbonyl, phenoxy.

alkylcarbonyloxy, phenylaminoalkylcarbonyloxy, (lower alkoxy or phenyloxy2carbonylalkylcarbonyl (oxy or amino) groups.

Suitable groups R> 3 and / or R16 are e.g. B. those of formulas CH2CH2Cl, CH2CH2Br, CHCl-CH2Cl, CH2CH2CN, CH2-CH (OH) -CHiCl, CH2CssHs, CH2CH2C6H5, CH2CH20Hw CH2-CH2-O-CH3, CH2-CH2-O-C4H9, -C4H8-O- C4H9, -CH2 CH2-O-CH2-CH2-OCHs, -CH2CH2-O-CH2CH2-OH, CH2CH2-O-CH2CH2-OCOCHs - (CH2) 1,2 or 3 CO-O- (CH3, C2H5, C3H7, C4H9, C6H5) - (CH2) 1,2 or 3 CO-NH- (CH3, C2H5, C3H7, C4H9, C6H5) -CH2-CH2-O-COCH2Cl, -CH2CH2-O-CO-CHBr-CH2Br, -CH2 -CH- (OCOCHs) -CH2-O-CssHs -CH2-CH2-O-CO-CH = CH2, -CH2-CH (OCOCH3) -CH2 OCOCHs, - (CH2) 1-3-O-CO (H, CH3, C2H5, C3H7, C4H9) - (CH2) 1-3-NH-CO (H, CH3, C2H5, C3H9, C4H9) - (CH2) 1-3-O-CO (C6H5, C6H4Cl, C6H4Br, C6H4OCH3, C6H4CH3) - (CH2) 1-3-0-CO-O (CH3, C2H5, C3H7, C4H9) - (CHi) HO-CO-O- (CoHs, CoH4CI, CsH4Br, CoH40CH3, CoH4CH3) - (CH2) i -3-O-CO-NH (CH3, C2H5, C3H7, C4Hs) - (CH2) 1-3-O-CO-NH (C6H5, C6H4CI, CoH40CHS, CssH4CH3) -CH2CH2-O-CH2-O-CoHs and -CH2CH2-O-CO-CH2-CssHs.

The radical Ac can not only have the meanings given for -CO-Rr2 and -CO-R13, it can also represent an alkylsulphonyl or benzenesulphonyl group, such as. B.

a methane, ethane, butane, propane, benzene, p-toluene, p-bromotoluene or p-nitrobenzenesulfonyl group.

Suitable coupling components are, for. B. the amines of the formulas

wherein cl denotes a hydrogen atom, an optionally substituted lower alkyl, cycloalkyl or lower alkoxy group or a benzene radical and ci denotes a lower alkyl or benzene radical.

The following coupling components are listed as examples: 3 - (ss-Chlorpropionylamino) -N, N-diethylaniline 3-acetamino-N, N-dibenzylaniline 3-acetamino-6-methoxy-N, N-bis- (ss-hydroxyethyl) aniline 3-acetamino-N, N-diethylaniline 3-acetamino-N, N-bis- (ss, ss-acetoxyethyl) -aniline 3-acetamino-N, N-bis- (ss, ss-cyanoethyl) aniline 3-acetamino-N-ethyl-N-ss-cyanoethylaniline 3-acetamino-6-methoxy-N, N-bis- (ss-cyanoethyl) -aniline 3-formylamino-N, N-diethylaniline 3-propionylamino-N-ethyl-N- (ss-acetoxyethyl) -aniline 3-acetylamino-N-ethyl-N- (ss-acetoxyethyl) -aniline 3-chloroacetyl-N, N-diethylaniline 3-acetamino-N, N -bis- (P-cyanoethoxyethyl) -aniline 3-acetamino-6-methoxy-N- (ss-cyanoäthoxyäthyl) -aniline 3-acetamino-6-methoxy-N- (ss-acetoxyethyl) -N- (ss-cyano- ethoxyethyl) aniline 3,5-bis (acet-ylamino-N- (ss-cyanoethyl) -N-ethyl-aniline - (obtainable by reacting 3,5-diacetamido-aniline with acrylonitrile and then diethyl sulfate) 2.5 -Bis (acetylamino) -N, N-bis- (ss-acetoxyethyl) -aniline 3-methanesulfonylamino-N, N-bis- (ss-acetoxyäthyl) -aniline 2-ethylamino-3-cyano-4,6-diamino- pyridine 2-Cyclohexylamino-3-aminocarbonyl-4,6-diaminopyridine 2-phenoxy-3-cyano-4,6-diamino-pyridine (the last coupling components are obtained by reacting 2-bromo-3-cyano-4,6-diamino pyridine and ethylamine, cyclohexylamino or phenol / phenol / potassium carbonate, and in the case of the aminocarbonyl compound, subsequent heating in sulfuric acid, accessible).

2-diethylamino -3-cyano-4-methyl-6- (ss-hydroxyethylamino) -pyridine 2,6-bis (ss-hydroxyethylamino) -3-cyano-4-methyl-pyridine.

The coupling can be carried out in a manner known per se, preferably in an acidic medium, if appropriate in the presence of sodium acetate or similar buffer substances or catalysts which influence the coupling rate, such as. B. dimethylformamide, pyridine, respectively. its salts, are made.

The new dyes produced by the process according to the invention are excellently suited for printing and in particular for dyeing semi-synthetic or, preferably, fully synthetic materials, in particular textile fibers.

Materials such as polyacrylonitrile and copolymers of acrylonitrile and other vinyl compounds, such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, and acrylonitrile block copolymers, polyurethanes, synthetic polyamides such as poly (hexamethylene) may be mentioned as substrates adipic acid amide) or polyamide 6.6, poly (w-caprolactam) or polyamide 6, poly (hexamethylene sebacic acid amide) or polyamide 6.10, and poly (II-amino-undecanoic acid) or polyamide 11, preferably cellulose tri-u. 2l / S-acetate and especially aromatic polyesters, such as those made from terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, and copolymers made from terephthalic and isophthalic acid with ethylene glycol and optionally 1,4-dimethylolcyclohexane.

These materials can be present in a wide variety of processing forms, such as webs, knitted fabrics, woven fabrics, yarns or fibers.

These materials are dyed with the dyes prepared according to the invention under conditions such that the dyes of the formula

split as follows

This creates a water-insoluble disperse dye which, as such, is absorbed onto the material.

This is done by dyeing the material at an elevated temperature, for example at 80 to 1300 C, optionally under pressure in a weakly acidic, neutral or alkaline bath at a pH of about 3 to 8, preferably 5 to 7; if necessary, buffers such as disodium phosphate are added to this dyebath; The method has the advantage that it is extremely easy to use. Both the dyeing and the printing process can be carried out according to the customary working methods, and apart from the new dye derivatives, no unusual substances, no disproportionately large amounts of auxiliaries and no special equipment are required.

Compared to the usual disperse dyeing, this process brings some of the decisive advantages already mentioned at the beginning, namely that the dyes do not have to be present as a dispersion and therefore the complicated grinding problems of disperse dyes are eliminated. There is also no need for dispersants that are usually toxic to waste water; This also eliminates the problems of foaming in large dyeing machines.

In the examples below, the parts are parts by weight, unless otherwise stated, the percentages are percentages by weight, and the temperatures are given in degrees Celsius. The ratio between parts by weight and parts by volume is the same as that between grams and milliliters.

example 1

0.1 mol of l-aminophenyl-4- (ss-hydroxyethyl sulfone) are concentrated at 100 ° C. in 30 ml. Entered sulfuric acid and stirred overnight at room temperature until completely dissolved. Now a minimal amount of ice is poured out so that the temperature remains at 0 C. After filtration, the sharply squeezed paste is suspended in 350 ml of ice water, with 0.15 mol of hydrochloric acid conc. added and titrimetrically diazotized at 0-50 ° C. with 4N sodium nitrate solution. Half an hour is diazotized at 0-50 ° C with a slight excess of nitrite. Nitrite consumption between 0.085-0.09 mol. After the excess nitrite has been destroyed with sulfamic acid solution, the amount of the finely powdered coupling component 3-acetamino-N, N-diethylaniline corresponding to the nitrite consumption is sprinkled. After stirring for two hours in an ice bath, sodium acetate is used to blunt. After a further 4 hours, the dye of the above formula is salted out with brine and filtered.

After drying in vacuo at 600 ° C., 21 g of an orange powder are obtained. The dye is clearly soluble in water, so it does not have to be ground and dispersed. When dyed at pH 5 and 1000, it provides a brilliant orange-red color on polyester fibers that is good fast to light, rubbing, perspiration and sublimation.

The following dyes can be produced in an analogous manner:

N - N to nuance on eO3SC2H4SO2 N (C2H5) polyester fibers NHC-CssHs 0 orange CH2FC3Hs eO3SO-C2H4SO2 9N <N 2 NH C2H4OH - orange NHC-CHs 0 C2H4CN eo3So-C2H4S02 NN N 3-hued C2H40 eOsSOCeH4SO- (CJ "" "(CPH5) 2.

scarlet NHC-CHs 0

Br Nuance on polyester fibers 5 eO3SOC2H4SO2 to polyester fibers Br NHC-CH5 tinged orange 0 SO2C2H40SOae 02N {N = N4N (C2Hd2 6 O2NN = NN (CslIs) 2 red-tinged violet NHC-CH3 0 NO2 7 O2NHi N = 7 red \ r / \ f - reddish blue NHC-CHs SO2C2H40SO3 II 0 OCHs nN = NC \> N (C2H6) 2 8 N = NN (C2H3) orange SO2C2H40SO39 NHC-CH3 0 809SO-CzH4-SONH- "0 C'a" '' selfish orange 9 NHC II 0 CH3 1 N (C2 e03soC2H4-SO2-NN = N H5) 2 10 yellowish orange NHC-CH3 II 0 903So-C2H4-S02-N <3> N <N (C2H5) 2 ll yellowish orange C2H4CN NHC-CH3 0 NOCH8 red 12 e00-C2H4-S02 red CI SO2NHCH3 OCH3 13 809SOCzH4S02 - N = i \ - -N (C2HS) 2 red NHCOCH3

OC2Hs shade on polyester fibers 14 eO3SOC2H4SO2 NN 9N (C2Hs) 2 NHCOCHs red OCHs 15 Oo3SoC2H4So2N <3N-N4N (C2H5) yellow-tinged red OH3 NHCOCHs Ci 16 eO3SOC2H5 NH5) NCO3 NCO3 NH2N 2N orangebraN </ <C2NH 2 17 eO3SOCiH4SO2NH &num; yy yellowish yellowish red CN NHCOCH3 eossoc2H4so2NH <N = NN (c2H6) 2 18 035003452-233 (C2H5) a yellowish red CF3 NHCOCHs eO3SOC2H4SO2NHN = NN (C2H5) 19 to / to / orange cl 80 NHCOeCH3NZH NHCOCHs NHC2Hs 21 eO3SOC2H4SO2M / NN orange -SOaOCoHs NHC2H4OH 22 eo3SoC2H4S02 <3Nw o2NHcsH7 orange NHC2H6 eO3SOC2H4SO3 N = N 23 orange SO2C2Hs

NHC2Hs nuance on polyester fibers 24 vN = N -S02N (CH3) 2 orange SO2NHc2H4osose <> SO2N (CHs) 2 orange NHCOCH3 25 eO3SOC2H4SO2N = NN (C2H5) 2 yellowish red NHCOCHs NH 2COCH3 (c2H4oN = c2H4so24N = NN C2H40H) e yellowish red NHCOCH3 NHCOCH8 27 eO3SOC2H4SO2N = NN (CH2C6H5) yellowish red NHCOCH3 The dyes of the formula were obtained in the same way

in which the symbols have the meaning given in the table below.

No. R n X d Z R6 R7 shade Polyester fibers

28 - 1 HH HOLE CH2CeH5 CH2CeHs orange 29 - 1 HH NOCH, C2H40H C2H40H orange '30 - 1 HH COCH3 CH2CHCHrOH C2H orange OH, 31 - 1 HH COCH3 C2H40COCHs C2H4OCQCH3 yellowish hole C2H4C1 33 - 1 HH HOLE C2H4C1 orange C2H40CHs C2H5 orange 34 - 1 HH HOLES C2H4OSO2C6H5 C2H5 orange 35 CH3 2 HH COCH3 C2H40COCH3 C2H5 yellowish orange 36 H 2 Cl H COCHs C2H4COOCHs C2H8 orange 37 H 2 HH HOLES CH C2H40CONHC6HsCH C2-H5 orange 39 1 1 HH HOLE C2H40CO- C2H5: orange. "Nr.R n X d Z R6 R7 shade on Polyester fibers

40 HC (CHs) 2 2 HH NOCH8 c8H C2H5 yellowish orange 41 C2H40H 2 C1 H HOLES C8H C2H5 orange 42 <,> 2 HH COCHs 08H5 C2H8 orange 43 - 1 HH COC2H4C1 C2H5 CiH5 orange 44 - 1 HH COCH-CH2Br 08H5 C2H5 orange 45 - 1 HH COCH = CH2 GeH5 GeH orange 46 - 1 HH COCOOC2H5 GeH GeH orange 47 - 1 HH CO (CH2) 4COGeH5 GeH5 GeH5 orange 0 48 - 1 HH coy> Gell GeH5 orange 49 - 1 HH COCH2GeH5 GeH5 Gell5 orange 50 - 1 HHC> GeH5 C2H5 orange N 51 - 1 HH COOC2H5 02H8 C2H5 orange 52 - 1 HH CONHC6H3 Gell5 GeH5 orange 53 - 1 HH SOLCH9 GeHs GeH5 red 54 - 1 HH SO20CH3 GeHs C2H red 55 - 1 HH SO20C1 GeH5 GeHs red No. n X d Z R7 R8 shade Polyester fibers

56 1 HH COCHs C2H4-C6Hs C8lls orange 57 1 HH LOCHS CsH4-OCO-CsH3 C2Hs orange 58 1 HH LOCHS C2H4-O-CO-CsH7 CsIio orange 59 1 HH COCHs GeH0 CH2CHJCN orange 60 1 HH COCHs C2. C2 orange 61 1 HH NOCH, CH2-C8H5 CH2CH20CN orange 62 1 HH COCHs C2H4-CH2CH2CN C2H4-O-CO-CH3 orange 63 1 HH COCHs C2H4-O-CO-CHs CH2CH2CN orange 64 1 H OH8 COCHs CH5 Gell5 orange 65 1 HH SO2C4Hs CaHs OiHs red 66 1 H Cl COCHs GeHs 02H5 orange 67 1 H COOCHs LOCHS Css C8Hs orange 68 1 HH COCHs CH2C1 H-CH20CHs OH3 orange OH Example 2

0.1 mol of l-aminophenyl-4 (β-oxaethylsulfone) are concentrated in 30 ml at 100 ° C. Entered sulfuric acid and stirred overnight at room temperature until completely dissolved.

A minimal amount of ice is now poured out, with the temperature remaining at 0 C. The precipitation of the sulfatoester can be improved by saturation with salt. After filtration, the sharply squeezed paste is homogenized in 400 ml of ice water, with 0.15 mol conc.

Hydrochloric acid is added and the mixture is titrimetrically diazotized at 0-50 ° C. with 4N sodium nitrite. The mixture is then stirred for half an hour at the same temperature with a slight excess of nitrite. After destroying the excess nitrite, with 0.4 moles of sodium acetate buffered.

An amount of coupling component (1-3-5 phenyl-methyl-iminopyrazole) corresponding to the nitrite consumption is dissolved with 1 equivalent of hydrochloric acid in 150 ml of water and poured into the diazo solution at ice temperature. The coupling takes place momentarily. After stirring overnight, the dye of the formula given above is salted out with brine and filtered.

When dried, 50 g of a light yellow dye are present.

With DH values between 4 and 7 Polvester under HT conditions it colors in greenish yellow tones. Any dispersant can be dispensed with for coloring.

The dyeings are distinguished by their excellent light, sublimation, rub and wash fastness. In analog Way, the following dyes can be made: Table 1 No. Nuance on Polyester fibers ~

Cl 1 eO3SO-C2H4-SO4lN = NX CHs yellow H2N N GeH5, - OH3, 2 eosso-c2H4so2-NHt N = N 11 v) N greenish yellow H2N N greenish yellow GeH5 Ol 3 eO3SOC2H4S02-NH {$ uN = N yellow / \ / H2N N GeHs CaH5 eO3SOGeH4SO2 4 N = N OH3 + -N = N - 7 - greenish yellow N GeH5 CH3 N = N '-.

5 eOsS-OCeH4-Sc.n GeH5 CffHs NO2 No. Nuance on Polyester fibers

NH2 CN 6 OsS-ooH-SO2N = NNIIGeH yellowish orange NH2 Cl NH2 CN 7 eO3S-O-GeH4-SO <N = NNN \ w orange N NH2 NHGeH5 NO2 N 8 eOsS-O-C2H4-SO24N = NS /> NHC6H5 scarlet N NHC2Hs Cl OH8 9 eO3S-OC2H4-SO2-N N = N OH5 Cl X golden yellow.

GeH5 H 10 8095-0-CtHr I -S02N - (- NeN-- IICHs N golden yellow CN X H2N-N GeH5 Ooss-o-c2H4-sorN <f N = N golden yellow 11 $ - N golden yellow OF8 H2NN GeH5 Cl 12 eOSS + C2H4-SO2-Nt 11 N Nv s golden yellow GeH5 BOsS-O-C2H4SOe - NtN - CHs 13 H2NN / N H2N IN greenish yellow CH2 H20 OH2 H2C i 2 The dyes described below are obtained in an analogous manner.Table 2

No. R n X R1 R2 Nuance on Polyester fibers

1 CH8 2 Cl CH3 CoHs - yellow 2 CH (CHs) 2 2 H CH3 GeH5 greenish yellow f 3 C2H40H 2 H OH3 GeH5 greenish yellow 4 C2H4CN 2. H CH3 GeH8 greenish yellow 5? 2> H OH3 GeHs greenish yellow 6 1: H CH (CHs) 2 CeHs greenish yellow 7 - 1 H OCHs C6Hs- yellow 8 - 1 H OGeH5 OoHs yellow - 1 H GeH - -GeHs yellow 10 - 1 H OONH2, -. C6H5. greenish yellow 11 H 2 H OH3 H greenish yellow, 2, 12 H 2 H oHs C2H40H greenish yellow 13 H 2 H CHs 9 C2H4CN greenish yellow 14 H 2 H OHO CH2GeH5 greenish yellow OH is: 1 H 0H3 CH2CH-CH20C6Hs greenish yellow 16 - 1 H OH8 CH2CHCcH6 greenish yellow ski7 OH t 17 - 1 H OH <) greenish yellow 18 - 1 H CR8 {X> greenish yellow 19 - 1 H OH5 too greenish yellow SO20CHs 20 2 I -H CHs (} C2Hs greenish yellow No. R n X R1 R2 Nuance Polyester fibers

21-1 H CHs C $) greenish yellow NHCOCHs 22-1 H CR8) greenish yellow OH The dyes of the formula given in Table 3 below are likewise obtained in an analogous manner.

Table 3

No. R n X R6 R7 R8 Nuance on Polyester fibers

1 H 2 Cl H O8H5 H orange 2 CR8 2 H GeH4OH OoH5 GeHs golden yellow 3 CH (CHs) e 2 H C2H40CHs oHs C2H40CHs golden yellow 4 - 1 H OH8 9 OH8 golden yellow HOLES 5 - 1 H C2H4CN Q C2H4CN golden yellow Cl 6 1 H Ge 'H4CN 9 C2H 4Cl golden yellow CEL 7 - 1 H CH (CHs) 2 CH (CHs) s CH (CHs) 2 golden yellow

Claims (18)

PATENT CLAIMS 1. Process for the preparation of colorants of the formula where B is a coupling component of the dispersion series which contains a non-acylated or acylated primary or secondary amino group in the o-position to the azo bridge and is free from water-solubilizing groups, R is a hydrogen atom, a cycloalkyl or an optionally substituted alkyl group, and the benzene radical A optionally contains further substituents, characterized in that the diazonium compound of an aniline of the formula wherein R and A are the same as above, with a coupling component of the dispersion series of the formula H-B, wherein B is the same as above. 2. The method according to claim 1, characterized in that a heterocyclic coupling component is used. 3. The method according to claim 1, characterized in that a coupling component of the aniline or aminonaphthalene series is used. 4. The method according to claim 2, characterized in that the coupling component of the formula used in which R1 is a hydrogen atom, a lower alkyl, lower alkoxy, cyano, lower alkoxycarbonyl, carbamoyl, lower alkoxy-lower alkoxycarbonyl, phenoxy or phenyl group, R2 is a hydrogen atom, an optionally substituted aliphatic, cycloaliphatic, aromatic or heterocyclic group . 5. The method according to claim 3, characterized in that the coupling component of the formula is used where Rs is a hydrogen atom, a lower alkyl or phenylalkyl group and R4 and R5 are each hydrogen or halogen atoms, lower alkyl, lower alkoxy, nitro, sulfonylamido, N-lower alkylsulfonylamido or N, N-di-lower alkylsulfonylamido groups. 6. The method according to claim 2, characterized in that the coupling component of the formula used in which two radicals Z are groups of the formula -NRGR7 and the other Z is a group of the formulas -NR6R7, -ORs or -S-R8, where Ro, R7 and Rs are each hydrogen, aryl, aralkyl, cycloalkyl or an aliphatic radical and R6 and R7 can form a ring containing the amine nitrogen and the radicals -NRoR7 can be identical to or different from one another. 7. The method according to claim 2, characterized in that the coupling components of the formula used, where Q1 is a -N bridge R12 and the other Q, independently of one another, denote an oxygen or sulfur atom or the -N (Rt2) bridge, where R12 is hydrogen or a lower alkyl group, and Rs, Rlo and Rll are optionally substituted hydrocarbon radicals or hydrogen atoms. 8. The method according to claim 3, characterized in that coupling components of the formula used, in which Rts and R14 are each independently a hydrogen atom, an optionally substituted alkyl, aryl, alkoxy, aryloxy, alkylamino or arylamino radical or an (alkyloxy or aryloxy) carbonyl radical or alkyloxy or aryloxy) carbonylalkyl radical or a ( Aryloxy, arylthio or arylamino) alkyl radical or a styryl radical or aralkyl, thiophenyl or pyridyl radical, and R15 and R16 are optionally substituted and / or interrupted by at least one heteroatom. 9. The method according to claim 3, characterized in that the coupling components of the formula used, in which Ac is the acyl radical of a lower aliphatic or aromatic carboxylic acid, carbonic acid half ester, carbamic acid or sulfonic acid or a radical of the formula -CO-NH2, d is a hydrogen atom, a chlorine or bromine atom, a lower alkyl, lower alkoxy, lower alkylthio, phenyl -, phenyloxy, phenylthio, lower alkyloxycarbonyl or lower alkylaminocarbonyl group, and R15 and R16 are optionally substituted and / or interrupted by at least one heteroatom. 10. The method according to claim 9, characterized in that coupling components are used in which d is a hydrogen atom. 11. The method according to claim 9, characterized in that coupling components are used in which Ac is a lower alkyl carbonyl radical. 12. The method according to claim 9, characterized in that coupling components are used in which Ris and R16 denote phenyl-lower alkyl, cyano-lower alkyl, cyanoethoxy-lower alkyl, lower alkylcarbonyloxy-lower alkyl, lower alkoxy-lower alkyl or lower alkyl groups. 13. The method according to claim 4, characterized in that coupling components of the formula is used, in which the ring B 'can be substituted by halogen atoms, hydroxy, acylamino or lower alkyl groups, and R1 is a lower alkyl radical. 14. The method according to claim 4, characterized in that the coupling component of the formula is used in which R1 'is a hydrogen atom, an aryl, lower alkoxy or lower alkyl radical. 15. The method according to claim 6, characterized in that the coupling component of the formula used, in which Re 'and R7' are hydrogen atoms and Re "and R7" are hydrogen atoms or methyl, ethyl, propyl and / or butyl groups. 16. The method according to claim 6, characterized in that the coupling component of the formula is used in which Rs' is an optionally substituted alkyl group having 1 to 12 carbon atoms, a cyclohexyl radical or an aromatic radical. 17. The method according to claim 2, characterized in that coupling components of the formula starts in the X 'cyano or carboxamide, C17 hydrogen, alkyl with 1 to 8 carbon atoms, optionally substituted by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to 8 carbon atoms, alkyl, phenyl, optionally substituted by chlorine, methyl, ethyl , p-hydroxyethyl methoxy or ethoxy substituted phenyl, cyclohexyl, benzyl, phenylethyl or N pyrrolidonylalkyl with 2 or 3 carbon atoms in the alkyl radical, R15 hydrogen, alkyl with 1 to 8 carbon atoms, optionally by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to 8 carbon atoms substituted alkyl, R17 and R18 together with the nitrogen the remainder of the pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine, where independently of one another R19 have the same meaning as R17 and R20 have the same meaning as R18. 18. The method according to claim 17, characterized in that one starts from coupling components in which R19 and R20 are hydrogen atoms and X 'is a cyano group. Hydrophobic synthetic organic material, especially polyester material, is known to be dyed with disperse dyes such as those used, for. B. are described in the Color Index. These are colored organic compounds that are free of water-solubilizing groups, such as sulfonic acid or ammonium groups, and are only soluble in water in traces, and are absorbed onto the material via a molecularly dispersed dissolved phase. For this purpose, the disperse dyes must very much before the actual dyeing process finely ground and stabilized by adding large amounts of dispersants in the aqueous dye bath. During dyeing, the dye is not in solution, but as a dispersion. This often gives rise to great difficulties in practice, because these dye dispersions are often unstable, the dye crystallizing out, which in turn leads to uneven colorations. In high-temperature dyeing in particular, insufficient dispersion stability becomes noticeable due to filtration phenomena in dense material, for example on packages and in tree dyeing. The dispersants can also be used in large dyeing machines ** WARNING ** End of CLMS field could overlap beginning of DESC **.