GB2103233A - Reactive dyes and their preparation and use - Google Patents
Reactive dyes and their preparation and use Download PDFInfo
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- GB2103233A GB2103233A GB08217705A GB8217705A GB2103233A GB 2103233 A GB2103233 A GB 2103233A GB 08217705 A GB08217705 A GB 08217705A GB 8217705 A GB8217705 A GB 8217705A GB 2103233 A GB2103233 A GB 2103233A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
Abstract
Reactive dyes of the formula <IMAGE> in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine or stilbene series or a colourless alkyl, aralkyl or aryl radical, R is hydrogen or unsubstituted or substituted C1-C4-alkyi and X is chlorine or a radical of the formula NR'-D' in which R' is hydrogen or unsubstituted or substituted C1-C4- alkyl and D' independently of D has the same meaning as D, either D or D' and D and D' being organic dye radicals. The reactive dyes are suitable for dyeing and printing cellulose- containing or nitrogen-containing materials.
Description
SPECIFICATION
Reactive dyes and their preparation and use
A large number of reactive dyes have become known to date. However, their application properties, in particular their applicability for various dyeing processes, frequently leave something to be desired. The object was therefore to find novel reactive dyes which have a wider spectrum of application. It has been found that the novel reactive dyes defined below largely fulfil this object.
The invention thus relates to reactive dyes of the formula
in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine or stilbene series or a colourless alkyl, aralkyl or aryl radical, R is hydrogen or unsubstituted or substituted C1-C4-alkyl and X is chlorine or a radical of the formula -NR'-D' (2) in which R' is hydrogen or unsubstituted or substituted C1-C4-alkyl and D' independently of D has the same meaning as D, either D or D' or D and D' being organic dye radicals.
Important sub-groups of the reactive dyes of the formula (1 ) are
a) reactive dyes of the formula
in which D is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R is as defined under the formula (1);
b) reactive dyes of the formula
in which D is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and D' is a colourless alkyl, aralkyl or aryl radical and R and R' are as defined under the formulae (1) and (2) respectively;
c) reactive dyes of the formula (4) in which D is a colourless alkyl, aralkyl or aryl radical and D' is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R and R' are as defined under the formulae (1) and (2); and
d) reactive dyes of the formula (4) in which D and D' independently of each other in each case are the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R and R' are as defined under the formulae (1) and (2).
Particularly preferred dyes are
e) reactive dyes of the formula
in which D1 is the radical of a diazo component of the benzene or naphthalene series and K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and the reactive radical is bonded to the diazo component or to the coupling component and R is as defined under the formula (1); f) reactive dyes of the formula (3) in which the radical D1 is a 1::1 copper complex monoazo dye of the benzene or naphthalene series and the copper atom is bonded in each case to a metallisable group in the ortho-position relative to the azo bridge and in which R is as defined under the formula (1);
q) reactive dyes of the formula
in which D is the radical of a diazo component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and D' is an unsubstituted or substituted alkyl radical or an unsubstituted or substituted phenyl or naphthyl radical and R and R' are as defined under the formulae (1) and (2) and in which the reactive radical is bonded either to the diazo component or to the coupling component;;
h) reactive dves of the formula
in which D is an unsubstituted or substituted alkyl radical or an unsubstituted or substituted phenyl or naphthyl radical, D1 is the radical of a diazo component of the benzene or naphthalene series and K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and in which the reactive radical is bonded either to the diazo component or to the coupling component and in which R and R' are as defined under the formulae (1) and (2);;
i) reactive dyes of the formula
in which D1 and D2 independently of each other are radicals of diazo components of the benzene or naphthalene series and K and K1 independently of each other are radicals of coupling components of the benzene or naphthalene series or of the heterocyclic series and the reactive radical is bonded independently of each other to D1 or K and to D2 or K1 and R and R' are as defined under the formulae (1) and (2); and
j) reactive dyes of the formula (3) in which D is the radical of an anthraquinone dye and R is as defined under the formula (1).
The reactive dyes of the formulae
are particularly useful dyes.
The radicals D and D' in the formulae (1) and (2), as organic dye radicals, can be substituted in the customary manner, and, in particular, the radicals D and D' contain one or more sulfonic acid groups.
Examples of further substituents on the radicals D and D' as organic dye radicals are alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 to 6 carbon atoms, such as acetylamino and propionylamino, benzoylamino, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, nitro, acetyl, cyano, trifluoromethyl, halogen, such as fluorine, chlorine and bromine, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.
Those reactive dyes, in which D is the radical of an azo dye, contain as substituents, in particular, methyl, ethyl, methoxy, chlorine, amino, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.
An alkyl radical D or D' in the formulae (1) or (2) is a straight-chain or branched alkyl radical which can also be substituted, for example by halogen, hydroxyl or cyano. Examples of D or D' are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, p-hydroxyethyl and - hydroxybutyl.
An aralkyl radical D or D' in the formulae (1) or (2) is for example a phenyl- or naphthyl-C1-C4- alkyl radical which can also be substituted in the aryl nucleus, for example by halogen, such as fluorine, chlorine or bromine, hydroxyl, alkyl, such as methyl or ethyl, alkoxy, such as methoxy or ethoxy, carboxyl and sulfo. Examples of D and D' are benzyl, sulfobenzyl, phenethyl and the naphthylmethylene radical.
An aryl radical D or D' in the formulae (1) or (2) is a radical of the benzene or naphthalene series or of the heterocyclic series and can also be substituted, for example by halogen, such as fluorine, chlorine or bromine, C 1-C4-alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, isobutyl and tert.-butyl, C1-C4-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, C1-C4- alkanoylamino groups, such as acetylamino and propionylamino, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, ureido, carboxyl, sulfomethyl and sulfo.
A C1-C4-alkyl radical R and, independently thereof, also R' in the formula (1) and formula (2) respectively is a straight-chain or branched alkyl radical which can also be substituted, for example by halogen, such as fluorine, chlorine or bromine, hydroxyl or cyano. Examples of R and R' are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl and ,B-hydroxybutyl.
Reactive dyes of the formula (1), in addition to the chloropyrimidine radical, can also contain other reactive radicals in the dye radical D, for example halogenotriazine radicals. Preferred reactive dyes are of the formula
in which D" is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine or stilbene series or a colourless alkyl, aralkyl or aryl radical, R, R, and R2 independently of one another are hydrogen or unsubstituted or substituted C,~4-alkyl, A is a substituted or unsubstituted aliphatic or aromatic bridge member, Y is fluorine or chlorine and X is chlorine or a radical of the formula -NFl'-D' (2) in which R' is hydrogen or unsubstituted or substituted C,~4-alkyl and D', independently of D", has the same meaning as D", either D" or D' or D" and D' being organic dye radicals.
Examples of unsubstituted or substituted C,~4-alkyl R, R, and R2 are the same radicals as mentioned above for R when explaining the formula (1) or formula (2).
The aliphatic or aromatic bridge member A is preferably an alkylene or arylene radical. The expression "aliphatic bridge member" also includes cycloaliphatic radicals.
A can thus be a iong (for example having 10 or more carbon atoms) or relatively short, straightchain or branched alkylene radical, in particular an alkylene radical having 2 to 6 carbon atoms, for example ethylene, propylene, butylene, hexylene or cyclohexylene.
An arylene radical A is for example a naphthylene radical, the radical of a diphenyl or stilbene or in particular a phenylene radical. The radical A can also contain further substituents, for example halogen atoms, such as fluorine, chlorine and bromine, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl and propyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy and isopropoxy, carboxyl or sulfo. A is preferably C26-alkylene or unsubstituted or substituted phenylene.
The ethylene radical, the phenylene radical and the sulfophenylene radical are preferred.
Particularly preferred reactive dyes are of the formula (1 3) in which D" is the radical of a monoazo or disazo dye.
The dyes of the formula (1) are fibre-reactive since they contain at least 1 detachable halogen atom in the pyrimidine radical.
Fibre-reactive compounds are to be understood as meaning compounds which are capable of reacting with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides, to form covalent chemical bonds.
The invention also relates to a process for preparing reactive dyes of the formula (1) which comprises condensing, in any order, a compound of the formula a compound of the formula
and, if appropriate, a compound of the formula
where D, D', R and R' in the formulae (14) and (16) are as defined under the formulae (1) and (2), to give a reactive dye of the formula (1).
If dye intermediates are used as starting materials, reactive dyes of the formula (1) are obtained by condensing a component of the compound of the formula (14) or of the compound of the formula (1 6), in which D or D' are organic dye radicals, and which contains an
group with a compound of the formula (1 5) and then reacting the product obtained with the other component of the dye of the formula (14) or of the formula (16).
The preferred reactive dyes of the formula (3) are prepared by condensing a compound of the formula (14) in which D is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R is as defined under the formula (1) with a compound of the formula (1 5).
The preferred reactive dyes of the formula (4) are prepared by condensing a compound of the formula (14) in which D is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and Ris as defined under the formula (1) with a compound of the formula (15) and then condensing the resulting product with a compound of the formula (16) in which D' is a colourless alkyl, aralkyl or aryl radical and R' is as defined under formula (2).
In a likewise preferred process for preparing reactive dyes of the formula (4), a compound of the formula (14) in which D is a colourless alkyl, aralkyl or aryl radical and Ris as defined under the formula (1) is condensed with a compound of the formula (15) and the resulting product is then condensed with a compound of the formula (16) in which D' is a radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R' is as defined under the formula (2).
In a further preferred process for preparing reactive dyes of the formula (4), a compound of the formula (14) is reacted with the compound of the formula (1 5) and the resulting product is then reacted with the compound of the formula (16), D and D' in the compounds of the formulae (14) and (1 6) independently of each other in each case being radicals of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R and R' independently of each other being as defined under the formulae (1) and (2).
Moreover, those compounds of the formulae (14) and (1 6) are preferably used in which D and D' or D or D' are radicals of monoazo or disazo dyes.
In the process variant described above, in which dye intermediates are used as the starting materials, the dyes of the formula (1) in which D or D' is the radical of an organic dye composed of two or more than two components can be prepared by condensing one component of the dye of the formulae (14) or (1 6), which contain an -NHFl or --NHR' group, with a compound of the formula (1 5) and then reacting the resulting product with the other component(s) of the dye of the formulae (14) or (16), to give a dye of the formula (1).
Examples of such organic dyes composed of two or more than two components are monoazo, disazo, trisazo, tetraazo, metal complex, formazan and azomethine dyes.
The process variant described above is particularly important for the preparation of dyes of the formula (1) in which D is the radical of an azo dye. In these dyes, that part of the azo dye to which the reactive radical is directly bonded can be either the radical or the diazo component or the radical of the coupling component. There are thus two variants of the abovementioned modification of the process.
One of the two variants comprises condensing a diazo component of the dye, which component contains an -NHR or --NHR' group, with a compound of the formula (15), diazotising the resulting condensation product and coupling the diazotisation product onto a coupling component.
The second variant comprises condensing a coupling component of the dye, which component contains an -NHFl or -NH Fl' group, with a compound of the formula (1 5) and coupling a diazotised diazo component onto the condensation product thus obtained.
By this preparation variant it is also possible to prepare reactive dyes of the formula (1 ) which contain two reactive radicals by condensing a diazo component which contains an -NHFl or -NH Fl' group with a compound of the formula (15), further by condensing a coupling component which contains an -NHFl or --NHR' group with a compound of the formula (1 5) and diazotising the condensation product of the diazo component and coupling the diazotisation product onto the
condensation product of the coupling component.
Dyes which contain two or more than two reactive radicals can also be prepared by condensing dyes of the formulae (14) or (1 6) which, in D or D', contain further -NHFl or --NHR' groups with a
corresponding amount of the acylating agent of the formula (15), so that two or more than two
corresponding radicals are introduced into the dye molecule.
A preferred embodiment for preparing reactive dyes of the formula (5) comprises condensing
organic dyes of the formula [K-N=N-D14+NHFl] (17) in which D1 is the radical of a diazo component of the benzene or naphthalene series and K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and
R is as defined under the formula (1) with the compound of the formula (1 5).
In a preferred process for preparing reactive dyes of the formula (3) a monoazo dye of the benzene or naphthalene series, which contains metallisable groups in the ortho-position relative to the azo bridge, is reacted, in any order, with a compound of the formula (1 5) and with copper-donating agents, to give a 1:1 copper complex azo dye.
The preferred reactive dyes of the formula (6) are prepared by reacting a dye of the formula (1 7) in which K, D1 and R are as defined under the formula (17) with a compound of the formula (15) and then reacting the resulting product with a compound of the formula (16) in which D' is an unsubstituted or substituted alkyl radical or an unsubstituted or substituted phenyl or naphthyl radical and R' is as defined in the formula (2), to give a reactive dye of the formula (6).
The likewise preferred reactive dyes of the formula (7) are prepared by condensing a compound of the formula (14) in which D is an unsubstituted or substituted alkyl radical or an unsubstituted or substituted phenyl or naphthyl radical and R is as defined under the formula (1) with the compound of the formula (15) and then reacting the condensation product with a dye of the formula [K-N=N-D1#NHFl'] (18) in which K and D1 are as defined under the formula (17) and R' is as defined under the formula (2), to give a reactive dye of the formula (7).
In a further preferred process for preparing reactive dyes of the formula (8), a dye of the formula (17) is condensed with the compound of the formula (15) and the condensation product is reacted with a dye of the formula [K1-N=N-D24+NHFl'j (19) in which K1, D2 and R' are as defined for K, D1 and R' in the formula (1 8), to give a reactive dye of the formula (8).
The compounds of the formulae (14) and (1 6) and used as starting materials can be substituted in the radicals D and D' as described above. The preferred starting materials are azo dyes of the formulae (17), (18) or (19) in which the radical [K-N=N-D1%or [K1-N=N-D2%can contain as substituents methyl, ethyl, methoxy, chlorine, amino, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo and, in the radical -NHFl or --NHR', R or R' is hydrogen.
The useful reactive dyes of the formulae (9), (10), (1 i) and (12) are prepared by
a) to prepare the reactive dye of the formula (9), condensing the azo dye obtained by coupling diazotised 1 -amino-4-acetylaminobenzene-6-sulfonic acid onto 2-amino-8-hydroxynaphthalene-6- sulfonic acid and subsequent hydrolysis of the acetylamino group with 2,4,6-trichloropyrimidine-5 carbonyl chloride; b) to prepare the reactive dye of the formula (10), condensing the azo dye obtained by coupling diazotised 2-aminonaphthalene-1 5-disulfonic acid onto 3-amino-8-hydroxynaphthalene-6-sulfonic acid with 2,4,6-trichloropyrimidine-5-carbonyl chloride and then reacting the dye formed with aniline3-sulfonic acid;;
c) to prepare the reactive dye of the formula (11), condensing aniline-2-sulfonic acid with 2,4,6trichloropyrimidine-5-carbonyl chloride and reacting the condensation product with the azo dye obtained by coupling diazo.tised 1 -amino-4-acetylaminobenzene-6-sulfonic acid onto 2-amino-8hydroxynaphthalene-6-sulfonic acid and subsequent hydrolysis of the acetylamino group; and
d) to prepare the reactive dye of the formula (12), reacting two equivalents of the azo dye obtained by coupling diazotised 1-amino-4-acetylaminobenzene-6-sulfonic acid onto 2-amino-8hydroxynaphthalene-6-sulfonic acid and subsequent hydrolysis of the acetylamino group with one equivalent of 2,4,6-trichloropyrimidine-5-carbonyl chloride.
Compounds of the formula (15) are condensed with compounds of the formulae (14) or (16) or with components which are diazotisable and/or capable of coupling and contain an --NHR or --NHR' group preferably in an aqueous solution or suspension at a low temperature and at a weakly acid, neutral to weakly alkaline pH value and in such a way that at least one chlorine remains as a detachable radical in the prepared dye of the formula (1). The hydrogen chloride evolved in the condensation is advantageously continuously neutralised by adding aqueous alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates.
Starting materials for preparing reactive dyes of the formula (1) are:
a) Possible dyes of the formulae (14) and (1 6) are, in particular, dyes of the following structural types:
Metal complexes of dyes of the formulae
Preferred metal atoms are Cu (1:1 complex) or Cr and Co (1:2 complexes). Cr and Co complexes can contain the azo compound of the formula indicated above once or twice, i.e. they can be built up symmetrically or asymmetrically with any other ligand groupings.
The fused rings indicated by broken lines represent alternatively possible naphthalene systems.
S03H1-3 / He Cf 4 Alkyl Pc H,-A/kyI SO3 H, -2 (Z C Ho-l ) > 2 or together C4C5-alkylene, uninterrupted or interrupted by N or 0.
In this formula, Pc represents the Cu or Ni phthalocyanine radical, the total number of substituents on the Pc skeleton being 4.
The dyes of the formulae indicated above can be further substituted in the alkyl or aryl radicals, in particular by the substituents mentioned in the explanation of D and D' in the formula (1) and (2) respectively.
Particularly important azo dyes of the formulae (17), (18) and (19) are the following:
in which K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series, acyl is a low molecular weight aliphatic acyl radical containing at most 3 carbon atoms or an aromatic radical containing at most 8 carbon atoms and R1 is as defined in the explanation of R and R' in the formulae (1) and (2) respectively, and the metal complex azo dyes of the formulae
in which R1 and acyl are as defined above and Me is Cu, Cr or Co.
b) The reactive component of the formula (1 5) is known and is prepared by known methods.
c) The following are examples of the large number of suitable colourless alkyl, aralkyl or aryl components of the formulae (14) and (1 6): ammonia, methyiamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butyiamine, tert.-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, p-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3or 4-acetylaminoaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3nitro-methylaniline, o-, m- and p-anisidine, o-, m- and p-phenetidine, 2-methoxy-5-methylaniline, 2ethoxy-5-methoxyaniline, 4-bromoaniline, 3-aminobenzamine, 4-aminophenylsulfamide, 3trifluoromethylaniline, 3- and 4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-1- hydroxynaphthalene, 1 -amino-4-hydroxynaphthalene, 1 -amino-8-hydroxynaphthalene, 1-amino-2- hydroxynaphthalene, 1 -amino-7-hydroxynaphthalene, orthanilic acid, metanilic acid, sulfanilic acid, 4aminotoluene-3-sulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, 4 aminoanisole-3-sulfonicacid, 4-chloroaniline-2-su Ifonic acid, 2-chloroaniline-5-sulfonic acid, 4acetylaminoaniline-2-sulfonic acid, 5-acetylaminoaniline-2-sulfonic acid, 2,4-dimethylaniline-6sulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid, 4-aminophenylmethanesulfonic acid, aniline-Nmethanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, paminosalicylic acid, 1 -amino-4-carboxybenzene-3-sulfonic acid, 1 -amino-2-carboxybenzene-5- sulfonic acid, 1 -amino-5-carboxybenzene-2-sulfonic acid, 1 -naphthylamine-2-, -3-, -4-, -5-, -6-, -7 and -8-sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 1-naphthylamine- 2,4-, -2,5-, -2,7-, -2,8-, -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and 5,8-disulfonic acid, 2naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7-and -6,8-disulfonic acid, 1naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, 3- and 4-aminopyridine, 2aminobenzothiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, benzylamine, o-, m- or psulfobenzylamine, phenethylamine and 1- or 2-aminomethylnaphthalene.
In the preparation of preferred dyes of the formula (1) in which D or D' is the radical of an azo dye, in particular of a monoazo or disazo dye, the intermediates containing a diazotisable amino group are diazotised as a rule by the action of nitrous acid in aqueous solution containing mineral acid at a low temperature, and the coupling is carried out at weakly acid, neutral to weakly alkaline pH values.
The reactive dyes of the formula (1) are novel and are distinguished by high reactivity and a high degree of fixation.
They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, high molecular weight polyamide fibres and high molecular weight polyurethanes, but especially cellulose-containing materials of fibrous structure, such as linen, wood pulp, regenerated cellulose and, in particular, cotton. They are suitable for use in dyeing by the pad-dyeing method, in which the goods are impregnated with aqueous dye solutions which may also contain salts, and the dyes are fixed, if necessary with the action of heat, after treatment with alkali or in the presence of alkali.
They are also suitable for printing, in particular on cotton, but also for printing nitrogen-containing fibres, for example wool, silk or mixed fabrics containing wool.
It is advisable to rinse the dyeings and prints thoroughly with cold and hot water, if necessary with the addition of an agent which acts as a dispersant and promotes diffusion of the non-fixed portions.
In the following Examples, the parts are by weight and the temperatures are in degrees
Centigrade.
Example 1
8.76 parts of the dye of the formula
are dissolved in 300 parts of water under neutral conditions. A solution of 4.92 parts of 2,4,6trichloropyrimidine-5-carbonyl chloride in 25 parts of acetone is added with vigorous stirring to the solution obtained. The pH of the reaction mixture is maintained at 6.5 to 7 by the dropwise addition of 1 N sodium hydroxide solution. When the acylation is complete, the solution is clarified by filtering, and the dye formed is salted out with sodium chloride. After the filtration, the product is buffered with a concentrated aqueous solution of disodium hydrogen phosphate and dried in vacuo at about 500 C.
The resulting dye of the probable formula
dyes cotton, by the exhaust method and the pad-steam method, in bluish-tinged red shades.
Reaction of the chromophors of the following table, which contain amino groups, with 2,4,6trichloropyrimidine-5-carbonyl chloride according to the instructions of Example 1 leads to further reactive dyes which dye cotton in the shades indicated:
Table 1
greenish-tinged yellow greenish-tinged yellow
golden yellow
orange
scarlet
blue
royal blue
Table 1 (contd.)
greenish-tinged yellow yellow yellow yellow
yellow
yellow
yellow
Table I (contd.)
bluish-tinged red
bluish-tinged red
bluish-tinged red bluish-tinged red bluish-tinged red ruby violet
Table I (contd.)
reddish-tinged blue
blue
blue
navy
greenish blue
navy
turquoise
Table I (contd).
blue brown brown
Example 2
11.06 parts of the dye of the formula
are dissolved in 500 parts of water under neutral conditions. A solution of 5.0 parts of 2,4,6trichloropyrimidine-5-carbonyl chloride in 50 parts of water is added dropwise to the solution obtained, and the pH of the reaction mixture is maintained at 7 by the simultaneous dropwise addition of 1 N sodium hydroxide solution. When the acylation of the amino group is complete, the solution is clarified by filtering, and the dye formed is salted out with 10% by volume of sodium chloride.
After filtering, the dye paste is dissolved in 500 parts of water, and a neutral solution of 3.46 parts of metanilic acid in 50 parts of water is added. The mixture is heated to 40-450 C, and the pH of the reaction mixture is maintained at 7 by the dropwise addition of 1N sodium hydroxide solution.
The dye formed is then salted out with 10% by volume of sodium chloride, filtered off and dried in vacuo at 500 C.
The dye thus obtained probably has the following structure
and dyes cotton in orange shades.
Example 3
A solution of 5.0 parts of 2,4,6-trichloropyrimidine-5-carbonyl chloride in 50 parts of acetone is added to a neutral solution of 3.46 parts of orthanilic acid in 300 parts of water, and the pH of the reaction mixture is maintained at 7 by the dropwise addition of 1 N sodium hydroxide solution. When an amino group is no longer detectable, the solution is clarified by filtering. To dissolve the primary condensation product, a neutral solution of 8.76 parts of the dye of the formula
in 200 parts of water is added, the mixture is slowly heated to 35-400C, and the pH of the reaction mixture is maintained at 7 by the dropwise addition of 1 N sodium hydroxide solution. When the pH value no longer changes, the dye formed is salted out with 10% by volume of sodium chloride, filtered off and dried in vacuo at 500C.
The novel dye probably has the following structure
and dyes cotton in bluish red shades.
Example 4
8.76 parts of the dye of the formula
are dissolved in 300 parts of water under neutral conditions, and 6.68 parts of sodium acetate are added. The solution obtained is cooled down to 50C, and a solution of 4.92 parts of 2,4,6trichloropyrimidine-5-carbonyl chloride in 25 parts of acetone is added. The temperature of the reaction mixture is allowed to rise to room temperature, and the solution obtained is clarified by filtering after about 4 hours. The dye formed is salted out by adding 1 5% by volume of sodium chloride, filtered off and dried in vacuo at about 500 C.
Analysis indicates that the dye probably has the following structure
The product thus obtained dyes cotton in deep bluish red shades.
Example 5
A solution of 5.4 parts of 2,4,6-trichloropyrimidine-5-carbonyl chloride in 50 parts of acetone is added dropwise with thorough stirring at room temperature to a neutral solution of 3.76 parts of 2,4diaminobenzenesulfonic acid in 300 parts of water. The pH of the reaction mixture is maintained at 5 by the simultaneous addition of 1 N sodium hydroxide solution.
The condensation product thus obtained is then diazotised in a customary manner and coupled onto a bicarbonate-alkaline solution of 1-hydroxy-8-benzoylaminonaphthalene-3,6-disulfonic acid. A dye is obtained which dyes cotton in bluish-tinged red shades.
Dyeing Example I
2 parts of the dye obtained in accordance with Example 2 are dissolved with the addition of 0.5 part of sodium m-nitrobenzenesulfonate in 100 parts of water. A cotton fabric is impregnated with the resulting solution in such a way that its weight increases by 75% and then dried.
The fabric is then impregnated with a warm solution at 200C and which contains, per litre, 3 to 10 grams of sodium hydroxide and 250 grams of sodium chloride and is squeezed off to a weight increase of 75%, and the dyeing is steamed at 100 to 101 OC for 30 to 60 seconds, rinsed, soaped for a quarter of an hour in a 0.3% strength boiling solution of an ion-free detergent, rinsed and dried.
Dyeing Example II
2 parts of the dye obtained in accordance with Example 1 are dissolved in 100 parts of water.
This solution is added to 1,900 parts of water at 400 C, 60 to 120 parts of sodium chloride are added, and 100 parts of a cotton fabric are put into this dyebath.
10 to 40 parts of calcined sodium carbonate are added after 30 minutes, and the temperature is maintained at 400C for 30 to 60 minutes. The dyeing is then rinsed and soaped for 1 5 minutes in a 0.3% strength boiling solution of an ion-free detergent, rinsed and dried.
Claims (30)
1. A reactive dye of the formula
in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine or stilbene series or a colourless alkyl, aralkyl or aryl radical, R is hydrogen or unsubstituted or substituted C1-C4-alkyl and X is chlorine or a radical of the formula -N Fl'-D' (2) in which R' is hydrogen or unsubstituted or substituted C1-C4-alkyl and D' independently of D has the same meaning as D, either D or Dt or D and D' being organic dye radicals.
2. A reactive dye according to claim 1 of the formula
in which D is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R is as defined in claim 1.
3. A reactive dye according to claim 1 of the formula
n which D is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye ind D' is a colourless alkyl, aralkyl or aryl radical and R and R' are as defined in claim 1.
4. A reactive dye according to claim 1 of the formula
in which D is a colourless alkyl, aralkyl or aryl radical and D' is the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R and R' are as defined in claim 1.
5. A reactive dye according to claim 1 of the formula
in which D and D' independently of each other in each case are the radical of a monoazo or disazo dye, metal complex azo dye or of an anthraquinone dye and R and R' are as defined in claim 1.
6. A reactive dye according to claim 2 of the formula
in which D1 is the radical of a diazo component of the benzene or naphthalene series and K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and the reactive radical is bonded to the diazo component or to the coupling component and R is as defined in claim 2.
7. A reactive dye according to claim 2, in which the radical D is a 1:1 copper complex monoazo dye of the benzene or naphthalene series and the copper atom is bonded in each case to a metallisable group in the ortho-position relative to the azo bridge and in which R is as defined in claim 2.
8. A reactive dye according to claim 3 of the formula
in which D, is the radical of a diazo component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and D' is an unsubstituted or substituted alkyl radical or an unsubstituted or substituted phenyl or naphthyl radical and R and R' are as defined in claim 3 and in which the reactive radical is bonded either to the diazo component or to the coupling component.
9. A reactive dye according to claim 4 of the formula
in which D is an unsubstituted or substituted alkyl radical or an unsubstituted or substituted phenyl or naphthyl radical, D, is the radical of a diazo component of the benzene or naphthalene series and K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series and in which the reactive radical is bonded either to the diazo component or to the coupling component and in which R and R' are as defined in claim 4.
10. A reactive dye according to claim 5 of the formula
in which D, and D2 independently of each other are radicals of diazo components of the benzene or naphthalene series and K and K, independently of each other are radicals of coupling components of the benzene or naphthalene series or of the heterocyclic series and the reactive radical is bonded independently of each other to D, or K and to D2 or K, and R and R' are as defined in claim 5.
11. A reactive dye according to claim 2, in which D is the radical of an anthraquinone dye and R is as defined in claim 2.
12. A reactive dye according to any one of claims 3, 4 or 5, in which D and D' can contain as substituents C1-C4-alkyl, C1-C4-alkoxy, C,-C,-alkanoylamino, benzoylamino, amino, alkoxycarbonyl, nitro, cyano, acetyl, trifluoromethyl, halogen, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo and R and R' are hydrogen.
13. A reactive dye according to claim 2, in which D can contain as substituents C1-C4-alkyl, C1-C4-a Ikoxy, C,-C,-alkanoylamino, benzoylamino, amino, alkoxycarbonyl, nitro, cyano, acetyl, trifluoromethyl, halogen, sulfamoyl, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo and R is hydrogen.
14. A reactive dye according to claim 6, in which the radical [K-N=N-D1% in formula (5) can contain as substituents methyl, ethyl, methoxy, amino, chlorine, carbamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo and R is hydrogen.
1 5. The reactive dye according to claim 14, of the formula
16. The reactive dye according to claim 8, of the formula
17. The reactive dye according to claim 9, of the formula
18. The reactive dye according to claim 10, of the formula
1 9. A reactive dve according to claim 1, of the formula
in which D" is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine or stilbene series or a colourless alkyl, aralkyl or aryl radical, R, R, and R2 independently of one another are hydrogen or unsubstituted or substituted C,~4-alkyl, A is a substituted or unsubstituted aliphatic or aromatic bridge member, Y is fluorine or chlorine and X is chlorine or a radical of the formula -NFl'-D' (2) in which R' is hydrogen or unsubstituted or substituted C,~4-alkyl and D', independently of D", has the same meaning as D", either D" or D' or D" and D' being organic dye radicals.
20. A reactive dye according to claim 19, in which D" is the radical of a monoazo or disazo dye.
21. A reactive dye according to claim 1 substantially as described with reference to any of the
Examples.
22. A process for preparing reactive dyes of the formula
in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine or stilbene series or a colourless alkyl, aralkyl or aryl radical, R is hydrogen or unsubstituted or substituted C1-C4-alkyl and X is chlorine or a radical of the formula -N Fl'-D' (2) in which R' is hydrogen or unsubstituted or substituted C1-C4-alkyl and D' independently of D has the same meaning as D, either D or D' or D and D' being organic dye radicals, which comprises condensing, in any order, a compound of the formula a compound of the formula
and, if appropriate, a compound of the formula
in which D, D', R and R' in the formulae (14) and (16) are as defined under the formula (1), to give a reactive dye of the formula (1).
23. A process of producing a reactive dye according to claim 22 substantially as described with reference to any of the Examples.
24. A dye when produced by a process claimed in claim 22 or 23.
25. The use of the reactive dye according to claims 1 to 21 or of the reactive dye obtained according to claim 24 for dyeing and printing.
26. A process for dyeing and printing using a dye according to claim 1.
27. A process according to claim 26 for dyeing cellulose fibres.
28. A process for printing and dyeing substantially as described with reference to Dyeing Example
I or II.
29. A dyeing or printing product which contains a dye according to claims 1 to 21 and 24.
30. The material, in particular the textile material, dyed or printed according to claim 26, 27 or28.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4111/81A CH647798A5 (en) | 1981-06-22 | 1981-06-22 | REACTIVE DYES. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2103233A true GB2103233A (en) | 1983-02-16 |
Family
ID=4270012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08217705A Withdrawn GB2103233A (en) | 1981-06-22 | 1982-06-18 | Reactive dyes and their preparation and use |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6010060B2 (en) |
| CH (1) | CH647798A5 (en) |
| DE (1) | DE3222726A1 (en) |
| FR (1) | FR2508053A1 (en) |
| GB (1) | GB2103233A (en) |
| IT (1) | IT1157212B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399674A (en) * | 1992-12-04 | 1995-03-21 | Hoechst Aktiengesellschaft | Dyestuffs containing pyrimidine-carboxylic acid amide radical having fiber-reactive group, processes for their preparation and their use |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2794900B2 (en) * | 1990-05-23 | 1998-09-10 | 松下電器産業株式会社 | Pinch roller device |
| EP0568876B1 (en) | 1992-05-04 | 1996-08-28 | Bayer Ag | Reactive dyes, their preparation and their use |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL128069C (en) * | 1963-03-01 | |||
| FR86540E (en) * | 1963-10-04 | 1966-02-25 | Sandoz Sa | Reactive dyes, their manufacturing process and their applications |
| CH464397A (en) * | 1964-02-28 | 1968-10-31 | Geigy Ag J R | Process for the preparation of reactive dyes |
| FR1546368A (en) * | 1966-12-05 | 1968-11-15 | Bayer Ag | Reactive dyes and process for their manufacture |
| GB1189776A (en) * | 1967-05-16 | 1970-04-29 | Sumitomo Chemical Co | Improvements in or relating to Reactive Dyes and a method for their preparation |
| DE2000925A1 (en) * | 1970-01-09 | 1971-07-15 | Bayer Ag | Phthalocyanine dyes |
-
1981
- 1981-06-22 CH CH4111/81A patent/CH647798A5/en not_active IP Right Cessation
-
1982
- 1982-06-18 IT IT48669/82A patent/IT1157212B/en active
- 1982-06-18 DE DE19823222726 patent/DE3222726A1/en not_active Ceased
- 1982-06-18 GB GB08217705A patent/GB2103233A/en not_active Withdrawn
- 1982-06-21 FR FR8210830A patent/FR2508053A1/en not_active Withdrawn
- 1982-06-22 JP JP57106283A patent/JPS6010060B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399674A (en) * | 1992-12-04 | 1995-03-21 | Hoechst Aktiengesellschaft | Dyestuffs containing pyrimidine-carboxylic acid amide radical having fiber-reactive group, processes for their preparation and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6010060B2 (en) | 1985-03-14 |
| IT1157212B (en) | 1987-02-11 |
| DE3222726A1 (en) | 1983-01-05 |
| IT8248669A0 (en) | 1982-06-18 |
| FR2508053A1 (en) | 1982-12-24 |
| JPS585366A (en) | 1983-01-12 |
| CH647798A5 (en) | 1985-02-15 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |