GB1576237A - Dyestuffs containing the triazine ring their preparation and use - Google Patents

Dyestuffs containing the triazine ring their preparation and use Download PDF

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GB1576237A
GB1576237A GB13852/77A GB1385277A GB1576237A GB 1576237 A GB1576237 A GB 1576237A GB 13852/77 A GB13852/77 A GB 13852/77A GB 1385277 A GB1385277 A GB 1385277A GB 1576237 A GB1576237 A GB 1576237A
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dyestuff
amino
radical
acid
formula
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Sanofi Aventis Deutschland GmbH
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Cassella AG
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    • 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
    • D06P1/382—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 reactive group directly attached to heterocyclic group
    • 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
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring

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Abstract

Dyestuffs of the formula I are prepared by reacting a dyestuff of the formula <IMAGE> in which F denotes the radical of a dyestuff containing at least one -SO3H group, R denotes hydrogen or lower alkyl, X and X' independently of one another denote a substituent which can be removed as an anion, and p denotes 1 or 2, with an amine of the formula <IMAGE> in which alk, Z, V, n and m have the meaning given in Claim 1. The dyes of the formula I can be fixed by various fixing processes with a very good degree of fixing and yield dyeings having high fastnesses, in particular excellent wet fastnesses. <IMAGE>

Description

(54) NEW DYESTUFFS CONTAINING THE TRIAZINE RING, THEIR PREPARATION AND USE (71) We, CASSELLA AKTIENGESELLSCHAFT formerly known as Cassella Farbwerke Mainkur Aktiengesellschaft 526, Hanauer Landstrasse, 6 Frankfurt (Main)-Fechenheim, Germany, a body corporate under the laws of Germany, do hereby declare this invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement:: The invention relates to new, valuable reactive dyestuffs of the formula I
wherein F denotes the radical of a dyestuff which contains at least one-SO3H group, R denotes hydrogen or lower alkyl having l to 4 carbon atoms which optionally may be substituted, X denotes a substituent which can be split off as an anion, p denotes 1 or 2 and A denotes a radical of the formula II
in which alk is a lower alkylene radical having 2-6 C atoms and V' is hydrogen or the radical of an optionally substituted hydrocarbon, Z is a p-halogenoethyl radical or a vinyl radical, m is I or 2 and n is 2 minus m.
Fibre-reactive dyestuffs are to be understood as dyestuffs which are capable of reacting with the hydroxyl groups of cellulose or with the reactive centres of natural or synthetic polyamides with the formation of covalent chemical bonds.
The radical F in formula I can be derived from any known class of dyestuffs; it preferably belongs to the anthraquinone series, the metal-free or metal-containing monoazo or disazo series, the phthalocyanine series, the formazan series or the nitroaryl series. Dyestuffs, according to the invention, in which F is a dyestuff radical of the antraquinone series, the metal-free or metal-containing monoazo or disazo series or the phthalocyanine series are preferred.
F preferably contains two to four sulphonic acid groups.
As already specified, the substituent R is hydrogen or an optionally substituted alkyl group having 1 to 4 C atoms, this can be unbranched or branched. The said alkyl can thus be methyl, ethyl, propyl, isopropyl, n-butyl, 2 - methyl - propyl, sec. - butyl or tert. - butyl. Some specific examples of the substituted alkyl groups which we contemplate are: carboxymethyl, sulphomethyl, sulphoethyl, cyanoethyl, p - chloropropyl, - hydroxyethyl. The methyl radical is the preferred alkyl.
Hydrogen is particularly preferred as R.
Substituents X which can be split off as an anion are especially chlorine, bromine, fluorine, alkylsulphonic having 1 to 4 carbon atoms, preferably methylsulphonyl or ethylsuiphonyl, phenylsulphonyl or the --SO,H radical.
X is preferably a chlorine atom.
The radical of the optionally substituted hydrocarbon V' is especially a methyl group which is optionally substituted by the carboxyl group or the sulphonic acid group or a derivative thereof, or an alkyl radical which has 2-6 C atoms and is optionally substituted by at least one alkoxy group having 1 or 2 C atoms, by a carboxyl or sulphonic acid group or by a halogen atom or a hydroxyl group, or an unsubstituted alkyl radical having 7-20 C atoms, a cyclohexyl radical or a phenyl radical which is optionally substituted by at least one methyl,- ethyl, methoxy, ethoxy, carboxylic acid or sulphonic acid group or by a halogen atom.
The invention relates especially to dyestuffs according to the formulae I and II in which Z represents the p - chloroethyl radical and X represents a halogen atom.
Those dyestuffs in which X represents a chlorine atom, alk represents the ethylene radical, Z represents the p - chloroethyl radical or vinyl radical, and m represents 2 are a particularly preferred group of dyestuffs according to the general formulae I and II.
In the case where m is equal to 2, the two radicals -alk-SO2-Z can be identical or, within the scope of the definitions of alk and Z, can be different.
Dyestuffs in which both radicals -alk-SO2-Z are identical are preferred.
Lower alkylene radicals which can represent alk in A are the ethylene radical, the trimethylene radical, the tetramethylene radical, the pentamethylene radical or the hexamethylene radical as well as their branched isomers. The ethylene radical is preferred.
The following may be mentioned as examples of V': hydrogen, methyl carboxymethyl, carbomethoxymethyl, carboethoxymethyl, sulphomethyl, suphamidomethyl, ethyl, carboxyethyl, sulphoethyl, propyl, p - carboxypropyl, A sulphatoethyl, - ethoxyethyl, - methoxypropyl, y - chloropropyl, y- bromopropyl, butyl, isobutyl, pentyl, hexyl, nonyl, dodecyl, hexadecyl, pentadecyl, cyclohexyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-sulphophenyl, o methylphenyl, p - methoxyphenyl, m - methylphenyl, or p - ethylphenyl. The optionally substituted alkyl radicals which have 14 C atoms are preferred, hydrogen and the methyl radical are particularly preferred.
The reactive dyestuffs of the general formula I are manufactured by reacting a dyestuff of the formula V
in which F, R and p have the meanings indicated above and X and X' independently of one another each denote a substituent which can be split off as an anion, with an amine of the formula Ila
in which alk, Z, V', n and m have the meaning indicated above.
The dyestuffs of the general formula V are manufactured by reacting a dyestuff of the formula III
in which F, R and p have the meaning indicated above, with a reactive derivative of the 1,3,5 - triazine of the formula IV
which i & X and X' independently of one another each denote a substituent which can be split off as an anion.
The manufacture of the dyestuffs V and of the reactive dyestuffs I according to the invention can also be combined advantageously with one another so that a dyestuff of the formula III is first reacted with a reactive derivative of the 1,3,5 triazine of the formula IV to give the dyestuff V and the latter is then reacted, without isolating the dyestuff V, with an amine of the formula IIa to give a reactive dyestuff I according to the invention. The reaction of the dyestuffs of the formula III with the triazine derivatives of the formula IV is appropriately carried out at low temperatures, say between -2 and +10 , preferably between 0 and 5 , with the addition of acid-binding agents, such as sodium hydroxide solution, sodium carbonate or sodium bicarbonate, within a pH range between 1.5 and 9, preferably between 4 and 6.
Water which contains a certain proportion of organic solvents, for example, acetone, is preferably used as the solvent. The reaction can, however, also be carried out in pure water.
.For For the further reaction, with the amines of the formula IIa, of the dyestuffs of formula V which have been obtained in this way, the amines are appropriately employed in the form of a salt, preferably in the form of the hydrochloride. The reaction is carried out at elevated temperature, e.g. at a temperature in the range from 25 to 700C, more preferably 35 to 55 -, with the addition of acid-binding agents, preferably sodium bicarbonate, within a pH range of 2-6.5, preferably 3.5 to 4.5.
If the dyestuff radical F is composed of several components, such as is the case, for example, with azo dyestuffs or formazan dyestuffs, the dyestuffs of the formula I according to the invention can also be obtained by synthesising them in a manner which is in itself known from components of F, of which one, but optionally also two, contain a group of the formula Va
wherein R, X and X' have the meanings indicated above.
Components of this type are obtained by acylating the corresponding components containing a group of the formula IIIa
with a reactive triazine derivative of the formula IV under conditions which correspond to those described above for the corresponding reaction of the dyestuff. The dyestuffs obtained in this way are then reacted, in the manner described above, with an amine of the formula IIa to give a dystuff, according to the invention, corresponding to the formula I.
The amines of the formula IIa in which Z denotes a ,B - halogenoethyl radical are manufactured by reacting an amine which corresponds to the formula IIa and which contains a chlorine atom instead of the -SO2-Z group, with ss hydroxyethylmercaptan in an alkaline medium and subsequently oxidising the resulting thioether with halogen, in solution in a hydrogen halide acid, according to the teachings of German Patent 887,505. Amines of the formula Ila in which Z denotes the vinyl radical can be obtained by eliminating hydrogen chloride from the amines IIa in which Z represents ss - halogenoethyl.
Dyestuffs, according to the invention, of the formula I in which Z denotes vinyl can be obtained in an analogous manner by elimination of hydrogen chloride, for example by treatment with sodium bicarbonate in water at 50-60 C, from dyestuffs, according to the invention, of the formula I in which Z represents ss chloroethyl.
Reactive derivatives of the 1,3,5 - triazine of the formula IV are known The following may be mentioned as examples: trichlorotriazine, tribromotriazihe, trifluorotriazine, trisulphotriazine, tris - methylsulphonyltriazine, tris ethylsulphonyltriazine, tris - phenylsulphonyltrlazine, dichlorofluorotriazine, chloro - disulphotriazine, and chloro - bis - methylsulphonyltriazine.
The following are examples of amines of the formula IIa: ss -(ss - chloroethyl sulphonyl) - ethyl - amine, ss - (ss - bromoethyl - sulphonyl) - ethyl - amine, ss vinylsulphonyl - ethyl - amine, &gamma; - (ss - chlorethyl - sulphonyl) - propyl - amine, &alpha; - (ss - chloroethyl - sulphonyl) - isopropyl - amine, # - (ss - chloroethyl - sulphonyl) - butyl - amine, ss - (ss - chloroethyl - sulphonyl) - isobutyl - amine, # - (ss - chloroethyl - sulphonyl) - pentyl - amine, ss - (ss - chloroethyl sulphonyl) - hexyl - amine, N - methyl - N - /3 - (/3 - chloroethyl - sulphonyl) ethyl - amine, N - ethyl - N - - chloroethyl - sulphonyl) - ethyl - amine, N - propyl - N -ss - -(ss - chloroethyl - sulphonyl) - ethyl - amine, N - butyl - N .ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - pentyl - N - p chloroethyl - sulphonyl) - ethyl - amine, N - hexyl - N .ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - nonyl - N - 8 - chloroethyl. - sulphonyl) ethyl - amine, N - dodecyl - N - ss -(ss - chloroethyl - sulphonyl) -ethyl - amine, N - hexadecyl - N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N octadecyl- N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N carboxymethyl - N - ss - (/3 - bromoethyl - sulphonyl)- ethyl - amine, N sulphatomethyl - N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - ss carboxyethyl - N - &gamma; - (ss - chloroethyl - sulphonyl) - propyl - amine, N - ss suiphatoethyl - N - y - (p - chloroethyl - sulphonyl) - propyl - amine, N - ss - sulphatoethyl - N - - (/3 - chloroethyl - sulphonyl) - butyl - amine, N - ss - ethoxyethyl - N - # - (ss - chloroethyl - sulphonyl) - butyl- amine, N - y - chloropropyl - N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - phenyl N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - p - chlorophenyl - N ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - o - methylphenyl - N - ss (/3 - chloroethyl - sulphonyl) - ethyl - amine, N - p - methoxyphenyl - N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, n - m - sulphophenyl - N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, n - p - sulphophenyl - N - ss - (ss chloroethyl - sulphonyl) - ethyl - amine, bis - [ss - (ss - chloroethyl - sulphonyl) ethyl] - amine, bis - - [ss - - (ss - bromoethyl - sulphonyl) - ethyl] - amine, bis - [y (/3 - chloroethyl - sulphonyl)- propyl] - amine, bis - [ - (ss - chloroethyl sulphonyl) - butyl] - amine and bis - (ss - vinyl - sulphonyl - ethyl) - amine, Amines of low-molecular weight,such as ss - (ss - chloroethyl - sulphonyl) ethyl - amine and its N-methyl derivative, are preferred. Bis - [p - (/3 - chloroethyl - sulphonyl) - ethyl] - amine is particularly preferred.
In the dyestuffs of the formula III which are employed for the manufacture of dyestuffs according to the invention, F represents the radical of a water-soluble dyestuff which carries at least I sulphonic acid group, especially the radical of a monoazo or disazo dyestuff which can be metal-free or metallised, the radical of a derivative of I - amino - anthraquinone or I - anilino - anthraquinone, especially the radical of a 4 - phenylamino - I - amino - anthraquinone - 2 - sulphonic acid derivative or the radical of a sulphophthalocyanine dyestuff, especially a derivative, carrying at least two sulphonic acid groups in the phthalocyanine nucleus, of a phthalocyanine-sulphanilide. or phthalocyanine-sulphalkylamide which has 2-6 C atoms in the alkyl chain, as well as the radicals of formazan or nitroaryl dyestuffs.
An important group of dyestuffs of the formula III is formed by those dyestuffs in which F is the radical of a monoazo or diasazo dyestuff of the formula VIa or VIb D-N=N-(M-N=N-)nK- (VIa) or --DD-N==N--(M--N=N-),K (VIb) or of a metal complex derived therefrom, in which formulae VIa and VIb D represents the radical of a diazo component of the benzene or naphthalene series which is optionally substituted by one or more substituents, especially hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups having 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms, K represent the radical of a coupling component of the benzene, naphthalene, or ketomethylene series which is optionally substituted by one or more substituents, especially hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups having 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms, M represents the radical of a middle component of the benzene or naphthalene series which is optionally substituted by one or more substituents, especially hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups having 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms, n represents the numbers 0 or 1 and D, M and K together contain at least two sulphonic acid groups, preferably 3 to 4 sulphonic acid groups. K is preferably derived from a coupling component of the benzene, naphthalene, pyrazolone, 6 hydroxypyrid - 2 - one or acetoacetic acid arylamide series.
A further valuable group of dyestuffs of the formula III in which p represents 2, contains as F the divalent radical of the formula VIc -D-N=N-( MN=N)K VIc wherein D, K, M and n have the abovementioned meanings, or a metal complex derived therefrom. In the case where n=0, the dyestuffs of the formula III wherein F is a radical of one of the formulae VIa--VIc, can be obtained in a manner which is in itself known by diazotising suitable aromatic amines and coupling with suitable coupling components, either the diazo component or the coupling component or both containing a radical of the formula
or the coupling component containing a radical of the formula
and the acyl group being split off by saponification after coupling.
In order to manufacture disazo dyestuffs of the formula III, that is to say those dyestuffs in which F represents a radical one of the formulae VIaVI,c, n being 1, the diazonium compound of a suitable aromatic amine is first coupled with a suitable middle component.
In principle, middle components are all benzene or naphthalene derivatives which contain an amino group which can be diazotised.
The aminoazo compound which is then present is subsequently diazotised and coupled with a suitable coupling component, either the diazo component in the first coupling or the coupling component in the second coupling or both containing a radical of the formula
and the acyl group being split off by saponification after coupling. The coupling component can also contain a
group instead of the
group.
The aromatic amines which are given in List No. 1 which follows are examples of amines which are suitable as diazo components for the manufacture of dyestuffs of the formula III in which F is a radical of the formula VIa.
List 1: Aniline: o-, m- or p-toluidine; o-, m- or p-anisidine; o-, m- or p - chloroaniline, aniline - 2 - , - 3 - or - 4 - carboxylic acid or aniline - 2 - , -3- or - 4 sulphonic acid; aniline - 2,4 - or -2,5 - dicarboxylic acid or aniline - 2,4- or -2,5 disulphonic acid; 2 - aminophenol - 4 - sulphonic acid; 2 - aminophenol - 4,6 disulphonic acid; 4 - chloro - 2 - aminophenol - 5- or -6 - sulphonic acid; 6 chloro - 2 - aminophenol - 4 - sulphonic acid; 6 - nitro - 2 - aminophenol - 4 sulphonic acid; 4 - nitro - 2 - aminophenol - 6 - sulphonic acid; 3- or 4 acetylamino - aniline - 6 - sulphonic acid; 3- or 4 - benzoylamino - aniline - 6 sulphonic acid; 4 - amino. - 4' - sulpho - benzanilide; 2 - aminoanisole - 4 sulphonic acid; 4 - aminoanisole - 2- or -3 - sulphonic acid; 3 - aminoanisole - 4 sulphonic acid; 6 - chloro - 2 - amino - benzene - sulphonic acid; 5 - nitro - 2 amino - benzene - sulphonic acid; 4 - chloro - 3 - amino - benzene - sulphonic acid; 6 - chloro - 3 - amino - benzene - sulphonic acid; 3 - chloro - 4 - amino benzene - sulphonic acid; 2 - amino - toluene - 4 - sulphonic acid; 2 - amino toluene - 5 - sulphonic acid; 3 - amino - toluene - 6 - sulphonic acid; 4 - amino toluene - 2 - sulphonic acid; 4 - amino - toluene - 3 - sulphonic acid; 5 - chloro 2 - amino - toluene - 3 - sulphonic acid; 3 - chloro - 2 - amino - toluene - 5 sulphonic acid; 2 - chloro - 4 - amino - toluene - 6 - sulphonic acid; 3 - nitro 2 - amino - toluene - 5 - sulphonic acid; 3 - nitro - 4 - amino - toluene - 2 sulphonic acid; 3 - amino - 1,2 - dimethyl - benzene - 4 - sulphonic acid; 4 amino - 1,3 - dimethyl - benzene - 5- sulphonic acid; 4- amino - 1,3 dimethyl - benzene - 6 - sulphonic acid; 4 - chloro - 2 - amino - anisole - 5 sulphonic acid; 4- amino - phenetole - 2- sulphonic acid; 4- amino phenetole - 3 - sulphonic acid; 2 - amino - phenetole - 4 - sulphonic acid; 2 amino - toluene - 3,4 - disulphonic acid; 2 - amino - toluene - 3,5 - disulphonic acid; 4 - amino - 2 - sulpho - 2'- or -4' - methoxy - diphenylamine; 2 - amino diphenyl ether; 2-, 3- or 4 - aminobenzosulphamide; 2 - naphthylamine - 1-, -5-, 6-, -7- or -8 - sulphonic acid; 2 - naphthylamine - 1,5-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- or -6,8 - disulphonic acid; 2 - naphthylamine - 1,5,7-, -3,6,8- or -4,6,8 trisulphonic acid; I - naphthylamine - 2-, -4-, -5-, -6- or -7 - sulphonic acid;I naphthylamine - 3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8-, -5,7- or -6,8 - disulphonic acid; 1 - naphthylamine - 2,3,6-, -3,6,8- or -4,6,8-trisulphonic acid; 2 - amino - 1 - naphthol - 4 - sulphonic acid; 2 - amino - I - naphthol - 7 - suiphonic acid; 1 amino - 2 - naphthol - 4 - suiphonic acid; 4 - nitro - 2 - amino - 1 - naphthol 7 - sulphonic acid and 5 - nitro - I - amino - 2 - naphthol - 4 - sulphonic acid.
In the synthesis of dyestuffs of the formula III in which F is a radical of the formula VIb or VIc, the diamines which are given, for example, in List No. 2 are employed in the form of their monoacyl derivatives.
Acyl groups which can be used are especially lower alkanoyl groups having 1 to 5 C atoms, preferably formyl or acetyl. As indicated above, the acyl groups are split off after coupling, in order to obtain the dyestuffs of the formula III.
List 2: p - Phenylenediamine; 1,4 - phenylenediamine - 2 - sulphonic acid; 1,4 phenylenediamine - 2- carboxylic acid; 1,4 - diamino - naphthalene - 2sulphonic acid; 2,6 - diamino - naphthalene - 8 - sulphonic acid; 2,6 - diamino naphthalene - 4,8 - disulphonic acid; 1,6 - diamino - naphthalene - 4,8 disulphonic acid; m - phenylene - diamine, 1,3 - phenylenediamine - 4 sulphonic acid; 1,3 - phenylene - diamine - 4,6 - disulphonic acid; 1,4 phenylenediamine - 2,6 - disulphonic acid; 1,4- phenylenediamine - 2,5 disulphonic acid; 1,4 - diaminonaphthalene - 6 - sulphonic acid; 4,4' diaminodiphenyl - 3 - sulphonic acid and 4,4' - diaminostilbene - 2,2' - disulphonic acid.
Examples of middle components which can be involved in the synthesis of the radicals VIa to VIc are given in List No. 3 which follows.
List No. 3: Aniline; m - toluidine; 2,5 - dimethyl - aniline or 2,5 - dimethoxy - aniline; m - amino - anisole; m - acetylamino - aniline, m - propionylamino - aniline, m butyrylamino - aniline or m - benzoylamino - aniline; m - amino - phenylurea; 4 - acetamino - 2 - amino - toluene or 4 - acetamino - 2 - amino - anisole; 2 amino - 4 - methyl - anisole; 1 - amino - naphthalene - 6- or -7 - sulphonic acid; 2 - amino - 4 - acetylamino - benzenesulphonic acid; 2 - amino - 5 - naphthol 7 - sulphonic acid; 2 - amino - 8 - naphthol - 6 - sulphonic acid; 2 - (4 aminobenzoyl - amino) - 5 - naphthol - 7 - sulphonic acid; 1 - (4 - amino - 2 sulphophenyl)- 3 - methyl - pyrazol - 5 - one or 1 - (4 - amino - 2sulphophenyl) - 3 - carboxy - pyrazol - 5 - one; and acetoaceto - 3 - sulpho -4 amino - anilide.
Examples of coupling components which are suitable for the manufacture of dyestuffs of the general formula III wherein F denotes a group of the formula VIb, are given in List No. 4 which follows.
List No. 4: 2 - Naphthol; 2 - naphthol - 6-, -7- or 8 - sulphonic acid; 2 - naphthol - 3,6-, 3,7-, -4,8- or -6,8-disulphonic acid; 2 - naphthol - 3,6,8 - trisulphonic acid; 1 naphthol - 4-, -5-, -6- or -8 - sulphonic acid; 1 - naphthol - 3,6-, -3,7-, -3,8- or -4,8disulphonic acid; 1 - naphthol - 3,6-, -3,7-, -3,8- or -4,8- disulphonic acid; 1 naphthol - 3,6,8 - trisulphonic acid; 2 - naphthylamine - 5-, -6- or -7 - sulphonic acid; 2 - naphthylamine - 3,6-, -3,7-, -5,7- or -6,8 - disulphonic acid;I - amino 8 - naphthol - 2,4 - disulphonic acid; 2 - ureido - 5 - naphthol - 7 - sulphonic acid; 1 - (4 - sulphophenyl)- 3 - methyl - pyrazol - 5 - one or 1 - (4 - sulphophenyl)- 3 - carboxy - pyrazol - 5 - one; 1 - (4 - methyl - 2sulphophenyl)- 3 - methyl - pyrazol - 5 - one or 1 - (4 - methyl - 2 sulphophenyl)- 3 - carboxy - pyrazol - 5 - one; 1 - (2,5 - dichloro - 4sulphophenyl) - 3 - methyl - pyrazol - 5 - one or I - (2,5 - dichloro - 4sulphophenyl)- 3 - carboxy - pyrazol - 5 - one; 4 - acetoacetylamino - benzenesulphonic acid; 4 - acetoacetylamino - 3,6 - dimethoxy benzenesulphonic acid; barbituric acid and 6 - hydroxy - 4 - methyl - 3 - sulpho pyrid - 2 - one or 6 - hydroxy - 4 - methyl - 3 - carbonamido - pyrid - 2 - one.
Examples of coupling components which are suitable for the synthesis of dyestuffs of the formula III wherein F is a group of the formula VIa or VIc, are given in List No. 5 which follows.
List No. 5: Aniline; m - toluidine; 2,5 - dimethyl - aniline or 2,5 - dimethoxy - aniline; m - amino - anisole; m - acetylamino - aniline, m - propionylamino - aniline, m butyrylamino - aniline or m - benzoylamino - aniline; m - amino - phenylurea; 4 - acetamino - 2 - amino - toluene or 4 - acetamino - 2 - amino - anisole; 2 amino - 4 - methyl - anisole; 1 - amino - naphthalene - 6-, -7- or -8 - sulphonic acid; 2- amino - 4 - acetylamino - benzenesulphonic acid; 2 - amino - 5 naphthol - 7 - sulphonic acid; 2 - amino - 8 - naphthol - 6 - sulphonic acid; 2 (4 - aminobenzoyl - amino) - 5 - naphthol - 7 - sulphonic acid; 1 - (4 - amino- or 4 - acetylamino) - 2 - sulphophenyl) - 3 - methyl - pyrazol - 5 - one or 1 - (4 amino- or 4 - acetylamino) - 2 - sulphophenyl) - 3 - carboxy - pyrazol - 5 - one; acetoaceto - 3 - sulpho - 4 - amino - anilide; 1 - amino - 8 - naphthol - 3,6- or 4,6 - disulphonic acid; 1 - (3- or 4 - aminobenzoyl) - amino - 8 - naphthol - 3,6or -4,6 - disulphonic acid; 1 - acetylamino - 8 - naphthol - 3,6- or -4,6 disulphonic acid; 2- acetylamino - 5 - naphthol - 7 - sulphonic acid; 2 acetylamino - 8 - naphthol - 6 - sulphonic acid; 1 - (3 - amino or 3 acetylamino - 6 - sulphophenyl) - 3 - methyl- or -3 - carboxy - pyrazol - 5 - one; 2 - acetyl - methylamino or 2 - methylamino - 5 - naphthol - 7 - sulphonic acid; N - methylaniline and N - propyl - m - toluidine.
Disazo dystuffs which carry one or two
groups and which are suitable for the manufacture of reactive dyestuffs according to the invention can also be obtained by tetrazotising an aromatic diamine which contains two primary amino groups and coupling the tetrazo compound thus obtained with 2 molar fractions of a coupling component which contains a
group, for example one of those indicated in List 5, or with 1 molar fraction of each of two different coupling components of this type or with 1 molar fraction of a coupling component of this type and with 1 molar fraction of a coupling component which does not contain a
group, for example one of those indicated in List 4.The following may be mentioned as examples of such aromatic diamines: List No. 6: 3,3' - Dimethoxybenzidine, benzidine - 2,2' - disulphonic acid, benzidine 3,3' - dicarboxylic acid, benzidine - 3,3' - diglycollic acid and 4,4' diaminostilbene - 2,2' - disulphonic acid.
Further disazo dystuffs which carry one or two
groups and which are suitable for the manufacture of reactive dyestuffs according to the invention can be obtained by coupling either 2 molar fractions of a diazotised amine which carries a
group, for example an acyl derivative of one of the amines in List 2, or 1 molar fraction of one of these diazotised amines and 1 molar fraction of a diazotised amine which does not carry a
group, for example one of the amines in List 1, with a coupling component which can undergo coupling in two places, and subsequently saponifying the resulting dyestuffs. If 2 molar fractions of the amines which carry a
group are used, 2 molar fractions of the same amine or 1 molar fraction of each of two different amines can be employed.
Examples of suitable coupling components which can undergo coupling in two places are 1 - amino - 8 - naphthol - 3,6 - or 4,6 - disulphonic acid, resorcinol or 5,5' - dihydroxy - 7,7' - disulpho - 2,2' - dinaphthylurea.
The dyestuffs of the formula III can be obtained in complete analogy with the possible manufacturing methods described above, if instead of the diazo components or coupling components indicated in Lists 2, 3 and 5, compounds are employed which contain a nitro group instead of the
group and if the nitro group of the azo compounds synthesised from these components is reduced to give the amino group. The conditions for this reduction are in themselves known. A reducing agent which is known for this purpose is alkali metal sulphide, which reduces the nitro group in an aqueous medium at temperatures of 40 to 700 without attacking the azo group.
Examples of the radicals F of particularly valuable monoazo and disazo dyestuffs which are suitable for the manufacture of dyestuffs according to the invention, are shown by means of the following formulae, wherein the benzene and naphthalene nuclei can be substituted in accordance with the definitions given for D, M and K and the position of the radical of the formula IIIa is indicated by means of the oDen bond:
The following are examples of diazo components from which particularly valuable monoazo dyestuffs of the formula III can be manufactured: aniline - 2 sulphonic acid; aniline - 2,5 - disulphonic acid; 2 - naphthylamine - 1 - sulphonic acid; 2- naphthylamine - 1,5 - disulphonic acid; 2 - naphthylamine - 4,8 disulphonic acid; 2 - naphthylamine- 3,6,8 - trisulphonic acid; and 2naphthylamine - 4,6,8 - trisulphonic acid.
The following are examples of coupling components from which particular valuable monoazo dyestuffs can be manufactured; I - amino - 8 - naphthol - 3,6 disulphonic acid; 1 - amino - 8 - naphthol - 4,6 - disulphonic acid; 2 - amino 5 - naphthol - 7 - sulphonic acid; 1 - (4 - amino - 2- sulphophenyl)- 3 carboxy - pyrazolone; 1 - (5 - amino - 2 - sulphophenyl) - 3 - carboxy pyrazol - 5 - one; aniline, N - methyl - aniline; 3 - amino - toluene; 3 - amino acetanilide and 3 - aminophenylurea.
The following are examples of particularly valuable monoazo dyestuffs in the formula III:
wherein D, is the 2 - sulphophenyl radical, the 1 - sulpho - 2 - naphthyl radical or the 1,5 - disulpho - 2 - naphthyl radical and the coupling component is substituted by a further sulphonic acid group in the 3- or 4 - position.
wherein D2 is the 2 - sulphophenyl radical, the 2,5 - disulphophenyl or the 1,5 disulpho - 2 - naphthyl radical, the coupling component carries no further substituents and R2 represents hydrogen or methyl.
wherein D3 is the 2 - sulphophenyl radical or the 1 - sulpho - 2 - naphthyl radical and the amino group in the 2 - sulphophenyl nucleus of the coupling component is in the 4- or 5 - position.
wherein D4 is the 2,5 - disulphophenyl radical, the 4,8 - disulpho - 2 - naphthyl radical, the 3,6,8 - trisulpho - 2 - naphthyl radical or the 4,6,8 - trisulpho - 2 naphthyl radical, the coupling component can be substituted in the o-position relative to the azo group by a methyl group, an acetamino group or the urea radical, and R2 represents hydrogen or methyl.
The following are examples of individual dyestuffs of the formula III in which F is a radical of a monoazo or disazo dyestuff: 1 - (3' - aminobenzoylamino) - 8 hydroxy - 7 - (2' - sulphophenylazo) - naphthalene - 3,6 - disulphonic acid, 1 (4' - aminobenzoylamino) - 8 - hydroxy - 7,2' - azonaphthalene - 1',3,5',6 tetrasulphonic acid, 1 - amino - 8 - hydroxy - 7,2' - azonaphthalene - 1',4,6 trisulphonic acid, I - (aminoacetylamino) - 8 - hydroxy - 7,2' - azonaphthalene 1',3,5',6 - tetrasulphonic acid, 2 - methylamino - 5 - hydroxy - 6,2' azonaphthalene - 1',5',7 - trisulphonic acid, 2 - amino - 8 - hydroxy - 7,2' azonaphthalene - 1',6 - disulphonic acid, 2 - methylamino - 8 - hydroxy - 7,2' azonaphthalene - 1',6,5' - trisulphonic acid, 2 - amino - 5 - hydroxy - 6 - (2',5' disulphophenylazo) - naphthalene - 7 - sulphonic acid, 2 - methylamino - 5 hydroxy - 6 - (4' - methoxy - 2' - sulphophenylazo) - naphthalene - 7 - sulphonic acid, 1 - amino - 8 - hydroxy - 7 - (2' - sulphophenylazo) - naphthalene - 3,6 disulphonic acid, I - amino - 8- hydroxy - 7 - (4' - chloro - 2' sulphophenylazo) - naphthalene - 4,6 - disulphonic acid, 2 - (4' - amino - 2' methylphenylazo) - naphthalene - 4,8 - disulphonic acid, 2 - (4' - amino - 2' methylphenyl - azo) - naphthalene - 4,6,8 - trisulphonic acid, 2 - (4' - amino 2' - acetylaminophenylazo) - naphthalene - 5,7 - disulphonic acid, 2 - (4' amino - 2' - acetylaminophenylazo) - naphthalene - 3,6,8 - trisulphonic acid, 4 nitro - 4' - (4" - methylaminophenylazo) - stilbene - 2,2' - disulphonic acid, 4 nitro - 4' - (4" - amino - 2" - methyl - 5" - methoxy - phenylazo) - stilbene 2,2' - disulphonic acid, 1 - (2',5' - dichloro - 4' - sulphophenyl) - 3 - methyl - 4 (3" - amino - 6" - sulphophenylazo) - 5 - pyrazolone, I - (4' - sulphophenyl) - 3 carboxy - 4 - (4" - amino - 2" - sulphophenylazo) - 5 - pyrazolone, I - (2' methylphenyl) - 3 - methyl - 4 - (4" - amino - 2" - ,5" - disulphophenylazo) - 5 pyrazolone, 1 - (2' - sulphophenyl) - 3 - methyl - 4 - (3"- amino - 6"sulphophenylazo) - 5 - pyrazolone, 2 - (3' - sulphophenylamino) - 5 - hydroxy 6 - (4' - amino - 2' - sulphophenylazo) - naphthalene - 7 - sulphonic acid, 1 (3' - aminophenyl) - 3 - methyl - 4 - (2",5" - disulphophenylazo) - 5 pyrazolone, 1 - (3' - amino - 6' - sulphophenyl) - 3 - carboxy - 4 - (2' sulphophenylazo)- 5 - pyrazolone, I - (4' - amino - 2' - sulphophenyl - 3 carboxy - 4 - (2' - sulphophenylazo)- 5 - pyrazolone, I - (4' - amino - 2' sulphophenyl) - 3 - carboxy - 4 - [4" - (2"',5"' - disulphophenylazo) - 2" methoxy - 5" - methylphenylazo] - 5 - pyrazolone, the copper complex of 1 amino - 8 - hydroxy - 7 - (2' - hydroxy - 5' - sulphophenylazo) - naphthalene 3,6 - disulphonic acid, the copper complex of 2 - amino - 5 - hydroxy - 6 - (2' hydroxy - 3' - sulpho - 5' - nitrophenylazo) - naphthalene - 7 - sulphonic acid, the copper complex of 2 - amino - 5 - hydroxy - 6 - (2' - hydroxy - 5' sulphophenylazo) - naphthalene - 1,7 - disulphonic acid, the copper complex of 1 - amino - 8 - hydroxy - 7 - (2' - hydroxy - 3' - chloro - 5' - sulphophenylazo) naphthalene - 3,6 - disulphonic acid, the copper complex of 2 - methylamino - 5 hydroxy - 6 - (2' - carboxy - 5' - sulphophenylazo) - naphthalene - 7 - sulphonic acid, 4,4' - bis - (1"- amino - 8"- hydroxy - 3",6" - disulpho - 7"naphthylazo) - 3,3' - dimethoxydiphenyl, 2 - amino - 5 - hydroxy - 6 - 14' (2" - sulphophenyl - azo) - 2' - methoxy - 5' - methylphenylazo] naphthalene - 1,7 - disulphonic acid, 1 - amino - 8 - hydroxy - 2 - (2',5' disulphophenylazo)- 7 - (3' - amino - 6' - sulphophenylazo)- naphthalene 3,6 - disulphonic acid, the copper complex of 1 - amino - 8 - hydroxy - 7 - [4' (2" - sulphophenyl - azo) - 2' - hydroxy - 5' - methylphenylazo] - naphthalene 3,6 - disulphonic acid, the copper complex of 2 - amino - 5 - hydroxy - 6 - [4' (2",5" - disulphophenylazo) - 2' - hydroxy - 5' - methylphenylazo] - naphthalene - 7 - sulphonic acid, the copper complex of 1 - (4' - amino - 2' sulphophenyl) - 3 - carboxy - 4 - [4" - (2"',5"' - disulphophenylazo)- 2" hydroxy - 5" - methylphenylazo] - 5 - pyrazolone, the copper complex of 2 - (4' amino - 3' - sulphoanilino) - 5 - hydroxy - 6 - (2" - carboxyphenylazo)naphthalene - 7 - sulphonic acid, the 2:1 chromium complex of 2 - amino - 6' nitro - 8,2' - dihydroxy - 7,1' - azonaphthalene - 6,4' - disulphonic acid, the 2:1 chromium complex of 2 - amino - 5 - hydroxy - 6 - (2' - carboxyphenylazo) naphthalene - 7 -- sulphonic acid, the 2:1 chromium complex of 1 - amino - 8 hydroxy - 7 - (4' - nitro - 2' - hydroxyphenylazo) - naphthalene - 3,6 disulphonic acid, the 2::1 cobalt complex of 2 - (4' - amino - 3' - sulphoanilino) 5 - hydroxy - 6 (5" - chloro - 2" - hydroxyphenylazo) - naphthalene - 7 sulphonic acid, the copper complex of 2 - amino - 6' - nitro - 2',8 - dihydroxy 1',7 - azonaphthalene - 4',6 - disulphonic acid, the copper complex of 1,6' diamino - 2',8 - dihydroxy - 1',7 - azonaphthalene - 2,4,4' - trisulphonic acid, the copper complex of 6' - amino - 1' - 2 - dihydroxy - 1,2' - azonaphthalene - 3,4' 6,8' - tetrasulphonic acid and the copper complex of I - amino - 1',8 dihydroxy - 2',7 - azonaphthalene - 3,4',6,8' - tetrasulphonic acid.
A further means of manufacturing dyestuffs according to the invention consists in manufacturing monoazo or disazo dyestuffs or optionally metal complexes thereof of the formula V
wherein F is a radical of one of the formulae VIa to VIc indicated above and X and X' have the meanings indicated above, direct by using diazo components and coupling components, one of which, but also, if appropriate, both of which, contain a group of the formula Va
and then reacting them with an amine of the formula IIa, as described above.
The starting materials required for this purpose are obtained by reacting diazo components or coupling components which contain a radical of the formula
with acylating agent of the formula IV.
Diazo components for the direct manufacture of azo dyestuffs of the formula V in which F is a radical of the formula VIb or VIc can be obtained, for example, by acylating the
group in the aromatic amine indicated in List 2 with an acylating agent of the formula IV.
Coupling components for the direct manufacture of azo dyestuffs of the formula V in which F is a radical of the formula VIa or VIc can be obtained, for example, by acylating the
group of a coupling component mentioned in List 5 with an acylating agent of the formula IV.
Chromium, manganese, cobalt nickel and copper are examples of complexforming metals which can be present in radicals of metal-containing monoazo or disazo dyestuffs which represents F. Copper, chromium and cobalt are preferred.
A further important group of dyestuffs of the general formula III is formed by those dyestuffs in which F is the radical of a derivative of 1 - amino anthraquinone or 1 - anilino - anthraquinone, especially the radical of a 4 phenylamino - I - amino - anthraquinone - 2 - sulphonic acid derivative. Suitable aminoanthraquinones contain 2 to 3, preferably 2, amino groups. which can also be substituted by alkyl or aryl.
Alkyl radicals have, in particular, 1 to 4, preferably 1--2, C atoms; phenyl is preferred as an aryl radical. The derivatives of the aminoanthraquinone can be contain 1 or 2 sulphonic acid groups directly in the anthraquinone nucleus and one or two sulphonic acid groups in aromatic substituents which may be present in the anthraquinone nucleus. The group
can be directly linked to the anthraquinone nucleus, but is preferably linked to a substituent in the anthraquinone nucleus.
In a preferred group of anthraquinone dyestuffs, according to the invention, of the formula I, F represents a radical of the formula VII
in which the anthraquinone nucleus can be substituted by a further sulphonic acid group. Z' represents a phenylene radical which carries a radical of the general formula IIIa. The phenylene radical Z' can be substituted by a sulphonic acid group or a carboxylic acid group, so that the dyestuff contains at least two groups which strongly impart solubility in water. Furthermore, the phenylene radical can be substituted by an alkoxy group having 1-3 C atoms, by a halogen atom or by 1-3 alkyl groups having 1-3 C atoms.
The preferred anthraquinone dyestuffs of the general formula III in which F is a radical of the formula VII, are manufactured by a condensation reaction between a diamine of the general formula
or its monoacyl derivative
and an anthraquinone derivative which contains a reactive substituent, for example a Br atom, in the 4-position. In this context, acyl has the meanings indicated above, particularly the meanings which are characterised as preferred.
The following are examples of suitable diamines of the formula
which can also be employed in the form of their acyl derivatives: 2,4 diaminobenzenesulphonic acid, 2,4 - diaminotoluene - 6 - sulphonic acid 2,6 diaminotoluene - 4 - sulphonic acid, 3,5 - diaminobenzenesulphonic acid, 3,5 diamino - 2,4,6 - trimethylbenzenesulphonic acid, p - phenylenediamine, 2,5 diaminobenzenecarboxylic acid, 2,5 - diaminobenzenesulphonic acid and 2,4 diaminobenzenecarboxylic acid.
The following are examples of dyestuffs of the formula III in which F is the radical of a 1 - amino - anthraquinone: 1 - amino - 4 - (3' - amino - 4' sulphoanilino) - anthraquinone - 2 - sulphonic acid, I - amino - 4 - (3 - amino 2',4',6' - trimethyl - 4' - sulphoanilino) - anthraquinone, - 2 - sulphonic acid, I amino - 4 - (4' - amino - 3' - sulphoanilino) - anthraquinone - 2,5 - disulphonic acid and 1 - amino - 5,8 - bis - (4' - methyl - 2' - sulphoanilino) - anthraquinone.
A further important group of dyestuffs of the general formula III is formed by those dyestuffs in which F represents the radical of a sulphophthalocyanine dyestuff, especially a derivative of a phthalocyaninesulphanilide or phthalocyaninesulphalkylamide which has 2-6 C atoms in the alkyl chain and which carries at least 2 sulphonic acid groups in the phthalocyanine nucleus.
A preferred group of phthalocyanine dyestuffs of the general formula III is formed by those dyestuffs in which F represents a radical of the formula VIII
wherein Pc denotes the radical of a metal-containing or metal-free phthalocyanine nucleus, preferably of copper phthalocyanine or nickel phthalocyanine, W denotes -OH and/or -NR'R" wherein R', R" and R"' independently of one another represent hydrogen or alkyl having 1--4 C atoms, k denotes the numbers 2 or 3, p denotes the numbers I or 2 and B denotes a phenylene radical which is optionally substituted by halogen, 1-3 alkyl groups having 1-2 C atoms or by one or two sulphonic acid groups or carboxylic acid groups or denotes an alkylene radical having 2-6 C atoms, e.g. the ethylene radical.
A phenyiene radical which is substituted by 1 sulphonic acid group is particularly preferred, as is the ethylene radical.
The dyestuffs of the formula III in which F represents a radical of the formula VIII are manufactured in a manner which is in itself known by a condensation reaction between a sulphochloride of the formula
wherein Pc, W, k and p have the meanings indicated above, and a diamine of the general formula
or its monoacyl derivative
wherein acyl has the above mentioned meanings, particularly the meanings characterised as preferred.The following are examples of diamines of the formula
which are suitable for the manufacture of the preferred phthalocyanine dyestuffs of the formula III: m - phenylenediamine, p - phenylenediamine, 2,4 diaminobenzenesulphonic acid, 2,5 - diaminobenzenesulphonic acid, 2,5 diaminobenzenecarboxylic acid, 2,5 - diaminobenzene - 1,4 - disulphonic acid, 2,4 - diamino - toluene - 6 - sulphonic acid, ethylenediamine and hexamethylene - diamine.
The following are examples of dyestuffs of the formula III in which F is the radical of a N - substituted phthalocyanine - sulphonamide: 3 - [N - (3 - amino 4 - sulphophenyl) - sulphamyl] - copper - phthalocyanine - 3',3",3"' 3" trisulphonic acid, bis - 4,4' - [N - 3 - amino - 4 - sulphophenyl) - sulphamyl] copper - phthalocyanine - 4",4"' - disulphonic acid, 3 - [N - (4 - amino - 3 sulphophenyl)- sulphamyl] - nickel - phthalocyanine - 3',3",3"' - trisulphonic acid, 3 - [N - (3 - aminophenyl) - sulphamyl] - 3' - sulphamyl - copper phthalocyanine - 3",3"' - disulphonic acid and 3 - (N - p - aminoethyl sulphamyl) - copper - phthalocyanine - 3',3",3"' - trisulphonic acid.
The reactive dyestuffs, according to the invention, of the formula I are outstandingly suitable for dyeing and printing cellulose and cellulose-containing materials. They are distinguished particularly in printing processes by a uniformly high degree of fixing, independently of the nature of the fixing, for example in fixing by steaming or dry heat or by a one-phase or two-phase process. Very good results are also obtained in the various dyeing processes, for example in the exhaustion process or the pad-batch process or the pad-thermofix process.The dyeings and prints obtained have a high brilliance and depth of colour together with very good fastness to light, even in a wet condition, very good fastness to wet processing, such as washing at 600 and at 950, and good fastness in use, such as fastness to sea water, fastness to acid and alkaline perspiration, fastness to chlorinated pool water, fastness to peroxides and fastness to flue gas. The dyestuffs are also distinguished by insensitivity towards atmospheric influences.
Very good results are also obtained when they are used on polyamides, especially wool, in reactive dyeing processes. Besides very good fastness to light, the outstanding fastness to washing and perspiration should be singled out particularly, as well as their excellent build-up capacity.
The temperatures quoted in the examples which follow relate to OC, parts are parts by weight and percentages are percentages by weight.
Example 1 18.5 parts of cyanuric chloride are dissolved in 110 parts of acetone and the mixture is poured onto 250 parts of ice, while stirring vigorously. A solution of 55.3 parts of the dyestuff of the following structure
is run in at 00. 50 parts of 2 normal sodium carbonate solution are then added dropwise, a pH value of 6-6.5 resulting. 36.3 parts of bis - [,B - (p - chloroethyl sulphonyl) - ethyl] - amine hydrochloride are now added in the form of a powder.
The mixture is warmed to 400 in the course of + hour and this temperature is maintained for 3 hours. At the same time, 100 parts of 2 normal sodium carbonate solution are added dropwise at a pH value of 4.(.5. 25 /" strength potassium chloride is added in order to make the product separate out and the mixture is cooled to 2250 whilst stirring and is filtered. About 235 parts of a dyestuff paste are obtained, which is dried at 6065 in vacuo.The reactive dyestuff prepared has the following structure:
The dyestuff employed above, 1 - amino - 8 - hydroxy - 2',7 - azo naphthalene - 1' - 3,5',6 - tetrasulphonic acid, can be obtained as follows: 60.6 parts of 2 - naphthylamine - 1,5 - disulphonic acid are dissolved in 300 parts of water and about 20 ml of 10 normal sodium hydroxide solution by warming to 600 at pH 7-8. A solution of 14 parts of sodium nitrite in 60 parts of water is added thereto. This mixture, warmed to 600, is run into a mixture of 50 parts of 10 normal hydrochloric acid and 500 parts of ice, the intention being to maintain a temperature of 05 during the diazotisation. Stirring is continued for + hour and the excess of nitrous acid which is present is destroyed by adding aminosulphonic acid. The diazo compound separates out as a pale yellowish precipitate. This suspension is run, at 05 , into 72.2 parts of 1 - acetamino - 8 - naphthol - 3,6 disulphonic acid, dissolved to form a neutral solution in 500 parts of water, 200 parts of ice and 17 parts of sodium bicarbonate. The coupling is completed at a pH value of 7.After adding 60 parts of 10 normal sodium hydroxide solution, the mixture is heated at 700 for 3 hours, as a result of which the acetyl group is saponified. 10% strength potassium chloride and 15 /" strength sodium chloride are added to the dyestuff solution to make the saponified dyestuff separate out, the mixture is neutralised with 22 parts of 10 normal hydrochloric acid, cooled to 20- 25 and filtered and the product is washed with 600 parts of sodium chloride solution (density 1.142).Equally valuable dyestuffs according to the invention are obtained if the 2 - naphthylamine - 1,5 - disulphonic acid is replaced by molar quantities of one of the diazo components mentioned in the following list and if the procedure is in other respects as described: 3 - amino - benzene - sulphonic acid, 4- amino - benzene - sulphonic acid, 5 - chloro - 2- amino - benzene sulphonic acid, 6 - chloro - 2 - amino - benzene - sulphonic acid, 5 - nitro - 2 amino - benzene - sulphonic acid, 4 - chloro - 3 - amino - benzene - sulphonic acid, 6 - chloro - 3 - amino - benzene - sulphonic acid, 3 - chloro - 4 - amino benzene - sulphonic acid, 2 - amino - toluene - 4 - sulphonic acid, 2 - amino toluene - 5 - sulphonic acid, 3 - amino - toluene - 6 - sulphonic acid, 4 - amino toluene - 2 - sulphonic acid, 4 - amino - toluene - 3 - sulphonic acid, 5 - chloro 2 - amino - toluene - 3 - sulphonic acid, 3 - chloro - 2 - amino - toluene - 5 sulphonic acid, 6 - chloro - 3 - amino - toluene - 4 - sulphonic acid, 2 - chloro 4 - amino - toluene - 5 - sulphonic acid, 2 - chloro - 4 - amino - toluene - 6 sulphonic acid, 4 - nitro - 2 - amino - toluene - 6 - sulphonic acid, 6 - nitro - 4 amino - toluene - 2 - sulphonic acid, 3 - amino - 1,2 - dimethyl - benzene - 4 sulphonic acid, 4 - amino - 1,3 - dimethyl - benzene - 5 - sulphonic acid, 4 amino - 1,3 - dimethyl - benzene - 6 - sulphonic acid, 2 - amino - anisole - 4 sulphonic acid, 4 - amino - anisole - 2 - sulphonic acid, 4 - amino - anisole - 3 sulphonic acid, 4 - chloro - 2 - amino - anisole - 5 - sulphonic acid, 4 - amino phenetole - 2 - sulphonic acid, 4 - amino - phenetole - 3 - sulphonic acid, 2 amino - phenetole - 4 - sulphonic acid, 4 - amino - benzene - 1,3 - disulphonic acid, 2 - amino - benzene - 1,4 - disulphonic acid, 2 - amino - toluene - 3,4 disulphonic acid, 2 - amino - toluene - 3,5 - disulphonic acid, aniline, 4 amino - toluene, 4 - amino - anisole, 4 - amino - chlorobenzene, 2aminobenzene - sulphonic acid, 2 - naphthylamine - 1 - sulphonic acid, 2 naphthylamine - 5 - sulphonic acid, 2 - naphthylamine - 6 - sulphonic acid, 2 naphthylamine - 7 - sulphonic acid, 2 - naphthylamine - 8 - sulphonic acid, 2 naphthylamine - 1,7 - disulphonic acid, 2 - naphthylamine - 3,6 - disulphonic acid, 2- naphthylamine - 3,7 - disulphonic acid, 2- naphthylamine - 4,7 disulphonic acid, 2 - naphthylamine - 4,8 - disulphonic acid, 2 - naphthylamine 5,7 - disulphonic acid, 2 - naphthylamine - 6,8 - disulphonic acid, 2 naphthylamine - 1,5,7 - trisulphonic acid, 2 - naphthylamine - 3,6,8 - trisulphonic acid, 2 - naphthylamine - 4,6,8 - trisulphonic acid, 1 - naphthylamine - 4sulphonic acid, 1 - naphthylamine - 5 - sulphonic acid, 1 - naphthylamine - 6 sulphonic acid, I - naphthylamine - 7 - sulphonic acid, 1 - naphthylamine - 3,6 disulphonic acid, I - naphthylamine - 3,7 - disulphonic acid, 1 - naphthylamine 3,8 - disulphonic acid, 1 - naphthylamine - 4,6 - disulphonic acid, 1 naphthylamine - 4,7 - disulphonic acid, 1 - naphthylamine - 4,8 - disulphonic acid, 1 - naphthylamine - 5,7 - disulphonic acid, I - naphthylamine - 6,8 disulphonic acid, 1 - naphthylamine - 2,4,6 - trisulphonic acid, I naphthylamine - 3,6,8 - trisulphonic acid and 1 - naphthylamine - 4,6,8 - trisulphonic acid.
Equally valuable dyestuffs according to the invention are obtained if the I acetamino - 8 - naphthol - 3,6 - disulphonic acid employed as the coupling component for the preparation of the starting dyestuff is replaced by molar quantities of the acetyl compound of one of the coupling components mentioned in the following list and if the procedure is in other respects as described above: 1 amino - 8 - naphthol - 4,6 - disulphonic acid, 2 - amino - 8 - naphthol - 6 sulphonic acid, 2 - methyl - amino - 8 - naphthol - 6 - sulphonic acid, 2 carboxymethylamino - 8 - naphthol - 6 - sulphonic acid, 2- p sulphoethylamino - 8 - naphthol - 6 - sulphonic acid, 2 - iso - propylamino - 8 naphthol - 6 - sulphonic acid, 2 - amino - 5 - naphthol - 7 - sulphonic acid, 2 methylamino - 5 - naphthol - 7 - sulphonic acid, 2 - ethylamino - 5 - naphthol 7 - sulphonic acid, 2 - n - butylamino - 5 - naphthol - 7 - sulphonic acid, 1 amino - 8 - naphthol - 4 - sulphonic acid, 2 - amino - 8 - naphthol - 4sulphonic acid and 2 - amino - 8 - naphthol - 3,6 - disulphonic acid.
Preparation of bis - [p - (/3 - chloroethylsulphonyl) - ethyl] - amine: 156 parts of p - hydroxyethylmercaptan, followed by 178.5 parts of bis - (p - chloroethyl) amine hydrochloride (J. Chem. Soc. 1934, 464), are added to a solution of 69 parts of sodium in 1,200 parts by volume of ethyl alcohol, the temperature rising to 40- 50". The mixture is then warmed for 1 hour at 780 and cooled and the sodium chloride which has precipitated is filtered off and the ethyl alcohol is distilled off.
The residue is taken up in 1,000 parts by volume of water and the pH is adjusted to 3 with approximately 90 parts by volume of 37% strength hydrochloric acid. 295 parts of chlorine are then passed in during 90 minutes. The hydrochloride which is precipitated is filtered off and washed with ice water. It can be recrystallised from water. Melting point 2050.
Analysis: Calculated: C 26.5%; H 5.0%; Cl 29.3%; N 3.9%; S 17.70/, Found: C 26.6%; H 5.2%; Cl 29.3%; N 4.1%; S 18.3% If the hydrochloride is stirred with sulphuric acid at room temperature and the product is precipitated by pouring onto ice, the neutral sulphate is obtained.
Melting point 150152 .
Analysis: Calculated: Cl 18.9 M"; N 3.7%; SO4 12.8% Found: Cl 18.9%; N 3.8%; SO4 13.0% Example 2 42.3 parts of the dyestuff 2 - amino- 5 - hydroxy - 6- (2sulphophenylazo) - naphthalene - 7 - sulphonic acid are reacted with 18.5 parts of cyanuric chloride and 36.3 parts of bis - (b - chloroethyl - sulphonyl - ethyl) amine hydrochloride as described in Example 1. 20% strength sodium chloride and 10% strength potassium chloride are added to the neutral solution to make the dyestuff separate out and the mixture is filtered.The resulting paste is dried in vacuo at 5070 . The reactive dyestuff prepared in this way has the following structure:
The starting dyestuff 2 - amino - 5 - hydroxy - 6 - (2 - sulphophenylazo)naphthalene - 7 - sulphonic acid which is required for the preparation of the dyestuff according to the invention can be obtained as follows: 34.4 parts of 2 amino - benzene - sulphonic acid are dissolved in 120 parts of water to form a neutral solution and are diazotised in the usual way. The diazo compound is then run, at 05 , into a mixture of 56.2 parts of 2 - acetamino - 5 - naphthol - 7 sulphonic acid, dissolved in 300 parts of water to form the neutral solution, 25 parts of sodium bicarbonate and 150 parts of ice. The pH value is at first 6.5 and rises to 7.5-7.8 after prolonged stirring.After completion of the coupling, 60 parts of 10 normal sodium hydroxide solution are added and the mixture is warmed to 900 for 2 hours in order to saponify the acetamino group. The alkaline solution of the orange intermediate dyestuff is neutralised with about 22 parts of 10 normal hydrochloric acid, 20% strength sodium chloride and 15% strength potassium chloride are added and the mixture is stirred for some time and filtered.
Equally valuable dyestuffs according to the invention are obtained if the 2 amino - benzenesulphonic acid is replaced by molar quantities of one of the diazo components mentioned in the following list and if the procedure is in other respects as described: 3 - amino - benzene - sulphonic acid, 4- amino - benzene sulphonic acid, 2 - naphthylamine - 1,5 - disulphonic acid, 5 - chloro - 2 amino - benzene - sulphonic acid, 6 - chloro - 2 - amino - benzene - sulphonic acid, 5 - nitro - 2 - amino - benzene - sulphonic acid, 4 - chloro - 3 - amino benzene - sulphonic acid, 6 - chloro - 3 - amino - benzene - sulphonic acid, 3 chloro - 4- amino - benzene - sulphonic acid, 2- amino - toluene - 4sulphonic acid, 2 - amino - toluene - 5 - sulphonic acid, 3 - amino - toluene - 6 sulphonic acid, 4 - amino - toluene - 2 - sulphonic acid, 4 - amino - toluene - 3 sulphonic acid, 5 - chloro - 2 - amino - toluene - 3 - sulphonic acid, 3 - chloro 2 - amino - toluene - 5 - sulphonic acid, 6 - chloro - 3 - amino - toluene - 4 sulphonic acid, 2 - chloro - 4 - amino - toluene - 5 - sulphonic acid, 2 - chloro 4 - amino - toluene - 6 - sulphonic acid, 4 - nitro - 2 - amino - toluene - 6 sulphonic acid, 6 - nitro - 4 - amino - toluene - 2 - sulphonic acid, 3 - amino 1,2 - dimethyl - benzene - 4- sulphonic acid, 4- amino - 1,3 - dimethyl benzene - 5 - sulphonic acid, 4 - amino - 1,3 - dimethyl - benzene - 6 - sulphonic acid, 2 - amino - anisole - 4 - sulphonic acid, 4 - amino - anisole - 2 - sulphonic acid, 4 - amino - anisole - 3 - sulphonic acid, 4 - chloro - 2 - amino - anisole 5 - sulphonic acid, 4 - amino - phenetole - 2 - sulphonic acid, 4 - amino phenetole - 3 - sulphonic acid, 2 - amino - phenetole - 4 - sulphonic acid, 4 amino - benzene - 1,3 - disulphonic acid, 2 - amino - benzene - 1,4 - disulphonic acid, 2 - amino - toluene - 3,4 - disulphonic acid, 2 - amino - toluene - 3,5 disulphonic acid, aniline, 4 - amino - t6luene, 8 - amino - anisole, 4 - amino chloro - benzene, 2 - amino - chlorobenzene, 2 - naphthylamine - 1 - sulphonic acid, 2 - naphthylamine - 5 - sulphonic acid, 2 - naphthylamine - 6 - sulphonic acid, 2 - naphthylamine - 7 - sulphonic acid, 2 - naphthylamine - 8 - sulphonic acid, 2- naphthylamine - 1,7 - disulphonic acid, 2- naphthylamine - 3,6 disulphonic acid, 2 - naphthylamine - 3,7 - disulphonic acid, 2 - naphthylamine 4,7 - disulphonic acid, 2 - naphthylamine - 5,7 - disulphonic acid, 2naphthylamine - 6,8 - disulphonic acid, 2 - naphthylamine - 1,5,7 - trisulphonic acid, 2 - naphthylamine - 3,6,8 - trisulphonic acid and 2 - naphthylamine -4,6,8 trisulphonic acid.
Equally valuable dyestuffs according to the invention are obtained if the 2 acetamino - 5 - naphthol - 7 - sulphonic acid which is employed as the coupling component for the preparation of the starting dyestuff is replaced by molar quantities of the acetyl compound of one of the coupling components mentioned in the following list and if the procedure is in other respects as described above: 1 amino - 8 - naphthol - 4,6 - disulphonic acid, 2 - amino - 8 - naphthol - 6 sulphonic acid, 2- methylamino - 8- naphthol - 6- sulphonic acid, 2carboxymethylamino - 8 - naphthol - 6 - sulphonic acid, 2 - ss sulphoethylamino - 8 - naphthol - 6 - sulphonic acid, 2 - iso - propylamino - 8 naphthol - 6 - sulphonic acid, 1 - amino - 8 - naphthol - 3,5 - disulphonic acid, 2- methylamino - 5 - naphthol - 7- sulphonic acid, 2- ethylamino - 5 naphthol - 7 - sulphonic acid, 2 - n - butylamino - 5 - naphthol - 7 - sulphonic acid, I - amino - 8 - naphthol - 4 - sulphonic acid, 2 - amino - 8 - naphthol - 4 sulphonic acid and 2 - amino - 5 - naphthol - 4,7 - disulphonic acid.
Example 3 Equally valuable dyestuffs according to the invention are obtained if the 36.3 parts of bis - [ss - (ss - chloroethyl - sulphonyl) - ethyl - amine hydrochloride in Example I are replaced by 37.6 g of the corresponding sulphate or by a molar quantity of the hydrochloride of one of the amines mentioned in the following list: ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, ss - (ss - bromoethyl sulphonyl) - ethyl - amine, ss - vinylsulphonyl - ethyl - amine, &gamma; - (ss chloroethyl - sulphonyl) - propyl - amine, &alpha; - (ss - chloro - ethyl - sulphonyl) isopropyl - amine, # - (ss - chloroethyl - sulphonyl) - butyl - amine, ss - (ss - chloroethyl - sulphonyl) - isobutyl - amine, # - (ss - chloroethyl - sulphonyl) pentyl - amine, ss - (/3 - chloroethyl - sulphonyl) - hexyl - amine, N - methyl N - p - chloroethyl - sulphonyl) - ethyl - amine, N - ethyl - N - /3 - (/3 - chloroethyl - sulphonyl - ethyl - amine, N - propyl - N - - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - butyl - N - /3 - (/3 - chloroethyl - sulphonyl) ethyl - amine, N -- pentyl -- N - N-/3-( - chloroethyl - sulphonyl) - ethyl amine, N - hexyl N - /3 (/3 - chloroethyl - sulphonyl) - ethyl - amine, N nonyl - N - /3-(- c hloroethyl - sulphonyl) - ethyl - amine, N - dodecyl - N /3 - (/3 - chloroetyl - sulphonyl) - ethyl - amine, N - hexadecyl - N - ss - (ss - chloroethyl - sulphonyl) - ethyl - amine, N - octadecyl - N- ss- (ss- chloroethyl - sulphonyl) - ethyl - amine, N - carboxymethyl - N - ss - (ss - bromoethyl - sulphonyl) - ethyl - amine, N - sulphatomethyl - N - ss - (ss chloroethyl - sulphonyl) - ethyl - amine, N - ss - carboxyethyl - N - &gamma; - (ss - chloroethyl - sulphonyl) - propyl - amine, N - ss - (sulphatoethyl - N - &gamma; - (ss chloroethyl - sulphonyl) - propyl - amine, N - ss - sulphatoethyl - N - # - (ss chloroethyl - sulphonyl) - butyl - amine, N - ss - ethoxyethyl - N - # - (ss - chloroethyl - sulphonyl) - butyl - amine, N - &gamma;; - chloropropyl - N - ss - (ss chloroethyl - sulphonyl) - ethyl - amine, N - phenyl - N - /3 - (/3 - chloroethyl sulphonyl - ethyl - amine, N - p - chlorophenyl - N - ss - (ss - chloroethyl sulphonyl) - ethyl - amine, N - o - methylphenyl - N - /3 - (/3 - chloroethyl - sulphonyl) - ethyl - amine, N - p - methoxyphenyl - N - /3 - (/3 - chloroethyl - sulphonyl) - ethyl - amine, N - m - sulphophenyl - N - /3 - (/3 - chloroethyl - sulphonyl) - ethyl - amine, N - p - sulphophenyl - N - /3 - (/3 - chloroethyl - sulphonyl) - ethyl - amine, bis - [ss - (ss - chloroethyl - sulphonyl) - ethyl] amine, bis - [ss - (ss - bromoethyl - sulphonyl) - ethyl] - amine, bis - [&gamma; - (ss chloroethyl - sulphonyl) - propyl] - amine, bis - [# - (ss - chloroethyl - sulphonyl) - butyl] - amine and bis - (ss - vinyl - sulphonyl - ethyl) - amine.
Example 4 Equally valuable dyestuffs according to the invention are obtained if the 18.5 parts of cyanuric chloride in Example 2 are replaced by the molar quantity of one of the derivatives of 1,3,5- triazine mentioned in the following list: tribromotriazine, trifluorotriazine, trisulphotriazine, tris - methyl sulphonyltriazine, tris - ethylsulphonyltriazine, tris - phenylsulphonyltriazine, dichlorofluorotriazine, chloro - disulphotriazine and chloro - bis methylsulphonyltriazine.
Example 5 76.6 parts of 2 - naphthylamine - 4,6,8 - trisulphonic acid are dissolved in 250 parts of water to form a neutral solution. 50 parts of 4 normal sodium nitrite solution are added. This mixture is run into a mixture of 50 parts of 10 normal hydrochloric acid and 400 parts of ice. A solution of 21.4 parts of 3 - toluidine in 100 parts of water and 20 parts of 10 normal hydrochloric acid is added, at 0-5 to the suspension of the diazo compound. The pH value is first reduced to 3.5 with 150 parts of 4 normal sodium acetate solution and is then raised to a value of 5.5 with sodium hydroxide solution. After the coupling is complete, the mixture is filtered.
50.1 parts of the dyestuff 2 - (4 - amino - 2 - methyl - phenylazo) naphthalene - 4,6,8 - trisulphonic acid prepared in this way are dissolved in 250 parts of water to form a neutral solution. This neutral solution is added to a suspension, prepared as in Example 1, of cyanuric chloride in acetone and water.
The temperature is kept at -l to 30 by cooling with ice. In the course of the acylation reaction 9 g of bicarbonate are introduced in such a way that the pH remains between 5.5 and 7. When starting dyestuff can no longer be detected in a chromatogram, 36.3 g of bis - [p - (/3 - chloroethyl - sulphonyl) - ethyl] - amine hydrochloride are added in the form of an approximately 50% strength paste and the mixture is warmed to 500. The pH value is kept within the limits of 4.5-6.0 by adding a further 18 g of bicarbonate. The reaction is complete when further alkali is no longer consumed. The resulting dyestuff of the formula:
is precipitated by adding sodium chloride and dried in vacuo at 50-75 .
Similarly valuable reactive dyestuffs are also obtained if the azo dyestuffs which can be obtained from the diazo components and coupling components indicated in the two lists which follow are employed instead of the starting dyestuff employed above, 2 - (4 - amino - 2 - methyl - phenylazo) - naphthalene - 4,6,8 trisulphonic acid, and if the procedure is in other respects as described above.
Diazo components: 2- Naphthylamine - 1,5 - disulphonic acid, 2- naphthylamine - 4,8 disulphonic acid, 2 - naphthylamine - 5,7 - disulphonic acid, 2 - naphthylamine 6,8 - disulphonic acid, 2 - naphthylamine - 1,5,7 - trisulphonic acid, 2 naphthylamine - 3,6,8 - trisulphonic acid and aniline - 2,5 - disulphonic acid.
Coupling components: Aniline, N - methylaniline, 3 - amino - anisole, 3 - amino - toluene, 2 amino - 4 - acetamino - toluene, 2 - amino - 4 - acetamino - anisole, 3 - amino acetanilide, 3 - amino - 4 - methoxy - toluene, 3 - amino - phenylurea, 1 - naphthylamine - 6 - sulphonic acid, 1 - naphthylamine - 7 - sulphonic acid and 1 - naphthylamine - 8 - sulphonic acid.
Example 6 63.1 parts of 1 - [2' - sulpho - 4 - (3,5 - dichlorotriazinyl - amino) - phenyl] 3 - carboxy - 4 - (2 - sulphophenylazo) - pyrazol - 5 - one are dissolved in water at pH 6.8-7.2. 36.3 parts of bis - [,B - (,B - chloroethyl - sulphonyl) - ethyl] amine are added to this solution at about 25 and the mixture is warmed to 35 40". The pH begins to fall. When it has reached a value of about 3.5, it is kept within the range from 3.5 to 4.5 by adding approximately 11 g of sodium carbonate in portions. The reaction is complete after about 3 hours, which can be recognised from the fact that no further alkali is consumed. The pH of the dyestuff solution is now adjusted to 7.0 by adding disodium hydrogen phosphate.The resulting dyestuff of the structure:
can be isolated by salting-out or by spray-drying.
Preparation of the Starting Dyestuff 49.7 parts of the yellow azo dyestuff obtained in accordance with DAS 1,922,940, Example 2, from diazotised 1 - amino - benzene - 2 - sulphonic acid and 1 - (4 - amino - 2 - sulpho - phenyl) - 5 - pyrazolone - 3 - carboxylic acid, are dissolved to form a neutral solution and are reacted at 05 and at pH 6.5 with a suspension of 18.5 parts of cyanuric chloride, prepared in water/acetone by the method of Example 1. Approximately 6 parts of sodium carbonate are added in order to maintain the pH range. The reaction is complete when the dyestuff can no longer be diazotised.
Similar valuable reactive dyestuffs according to the invention are obtained if, instead of the intermediate dyestuff employed above, the condensation products, with cyanuric chloride, of the azodyestuffs which can be obtained from the diazo components and coupling components indicated in the two lists which follow are employed and if the procedure is in other respects as described above.
Diazo components: 3 - Amino - benzene - sulphonic acid, 4 - amino - benzene - sulphonic acid, 5 - chloro - 2 - amino - benzene - sulphonic acid, 2,5 - dichloro - 4 - amino - benzene - sulphonic acid, 2 - amino - toluene - 4 - sulphonic acid, 4 - amino toluene - 3 - sulphonic acid, 2 - amino - anisole - 4 - sulphonic acid, 4 - amino benzene - 1,3 - disulphonic acid, 2 - amino - benzene - 1,4 - disulphonic acid, 2 amino - toluene - 3,5 - disulphonic acid, 2- amino - naphthalene - 1,5 disulphonic acid, 2 - amino - naphthalene - 4,8 - disulphonic acid, 2 - amino 6,8 - disulphonic acid, 2 - amino - naphthalene - 1 - sulphonic acid, and 2 amino - naphthalene - 6 - sulphonic acid.
Coupling components: 1 - (3 - Amino - 6 - sulpho - phenyl) - 3 - methyl - 5 - pyrazolone, 1 - (4 - amino - 3 - sulpho - phenyl) - 3 - methyl - 5 - pyrazolone, I - (4 - amino - 2 sulpho - phenyl) - 3 - methyl - 5 - pyrazolone, 1 - (3 - amino - 6 - sulpho phenyl) - 5 - pyrazolone - 3 - carboxylic acid, 1 - (4 - amino- 3 sulphophenyl) - 5 - pyrazolone - 3 - carboxylic acid, 1 - (3 - amino - 5 - sulpho 6 - methyl - phenyl) - 5 - pyrazolone - 3 - carboxylic acid, I - (2 - methyl - 3 amino - 5 - sulpho - phenyl) - 5 - pyrazolone - 3 - carboxylic acid, 1 - (2 methyl - 3 - amino - 5 - sulpho - phenyl) - 3 - methyl - 5 - pyrazolone, 1 - (3 - amino - 5 - sulpho - 6 - methyl - phenyl) - 3 - methyl - 5 - pyrazolone and I (4 - amino - 2,5 - disulpho - phenyl) - 5 - pyrazolone - 3 - carboxylic acid.
Example 7 50.3 parts of the monoazo dyestuff 1 - (5' - amino - 2' - sulpho - phenylazo) 2 - naphthol - 6,8 - disulphonic acid are first reacted at 05 and at a pH value of 6-6.5, with a suspension of 18.5 parts of cyanuric chloride which has been prepared by dissolving the cyanuric chloride in 100 parts of acetone and precipitating with 250 g of ice, and the product is then reacted, at 30400 and gt a pH value of 4.0--4.5, with 36.3 parts of bis - [,B - (p - chloroethyl - sulphonyl) ethyl] - amine hydrochloride.The resulting orange reactive dyestuff of the formula
is obtained by concentrating the neutral solution to dryness in vacuo at 55W600, or is precipitated with sodium chloride, and is filtered off and dried in vacuo.
The starting dyestuff, 1 - (5 - amino - 2- sulpho - phenylazo)- 2naphthol - 6,8 - disulphonic acid, is obtained by coupling diazotised 2 - amino 4 - acetamino - benzene - sulphonic acid with 2 - naphthol - 6,8 - disulphonic acid and subsequently saponifying the acetyl group with sodium hydroxide solution or hydrochloric acid.
Similar valuable reactive dyestuffs according to the invention are obtained if monoazodyestuffs which contain amino groups and which can be prepared from the diazo components and coupling components in the following text, with subsequent saponification of the acetyl group or reduction of the nitro group, are used as the starting materials and if the procedure is in other respects in accordance with the above instructions.
Diazo components: 2 - Amino - 5 - acetamino - benzene - sulphonic acid, 2 - amino - 4 acetamino - toluene - 5 - sulphonic acid, 2 - amino - 4 - acetamino - toluene 6 - sulphonic acid, 2 - amino - 6 - acetamino - toluene - 4 - sulphonic acid, 5 nitro - 2- amino - benzene - sulphonic acid, 6 - acetamino - 2aminonaphthalene - 4,8 - disulphonic acid, 4 - nitro - 2 - amino - toluene - 6 sulphonic acid, 6 - nitro - 4 - amino - toluene - 2 - sulphonic acid, 6 - nitro - 2 - amino - naphthalene - 8 - sulphonic acid and 6 - nitro - 2- aminonaphthalene - 4,8 - disulphonic acid.
Coupling components: 1 - Naphthol - 3,6 - disulphonic acid, I - naphthol - 3,8 - disulphonic acid, 1 - naphthol - 3,7 - disulphonic acid, 2 - naphthoi - 3,7 - disulphonic acid, 2 - naphthol - 4,8 - disulphonic acid, 1 - naphthol - 3,6,8 - trisulphonic acid, 2 naphthol - 3,6,8 - trisulphonic acid, 2 - amino - naphthalene - 3,6 - disulphonic acid, 2 - amino - naphthalene - 5,7 - disulphonic acid, 1 - (2- or 3- or 4 sulphophenyl) - 3 - methyl - 5 - pyrazolone, 1 - (2 - methyl - 4 - sulphophenyl) 3 - methyl - 5 - pyrazolone, I - (2,5 - dichloro - 4 - sulphophenyl) - 3 - methyl 5 - pyrazolone, 1 - (2,5 - disulphophenyl) - 3 - methyl - 5 - pyrazolone, 1 - (2- or 3- or 4 - sulphophenyl) - 5 - pyrazolone - 3 - carboxylic acid and 1 - (2 - chloro 5 - sulphophenyl) - 5 - pyrazolone - 3 - carboxylic acid.
Example 8 65.1 parts of 1 - dichlorotriazinylamino - 8 - naphthol - 7 - (2 - sulphophenylazo) - naphthalene - 3,6 - disulphonic acid are stirred in 500 parts by volume of water at 40". 36.3 parts of bis - [p - (/3 - chloroethylsulphophenyl) ethyl] - amine hydrochloride are added to the suspension and stirring is continued at 40". The pH value is kept between 3.8 and 4.2 by adding about 17 parts of sodium bicarbonate. The reaction is complete when the pH value has remained constant for about 3 hours. The resulting dyestuff of the formula
is completely in solution. The pH of the solution is adjusted to 7 and the dyestuff is isolated by salting-out or by spray-drying.
Preparation of the Starting Dyestuff 31.9 parts of 1 - amino - 8 - naphthol - 3,6 - disulphonic acid are dissolved in 150 parts by volume of water at 500 and at pH 6. This solution is added in the course of about 90 minutes to a suspension of 20 parts of cyanuric chloride in 80 parts by volume of water and 60 parts by volume of acetone at a temperature of O- 10 and the mixture is stirred until free I - amino - 8 - naphthol - 3,6 disulphonic acid can no longer be detected. In the course of the reaction the pH value falls to about 1.5.The diazo component which has been obtained in the customary manner by diazotising 17.3 parts of aniline - o - sulphonic acid is added to the suspension of the coupling component obtained in this way and the coupling is completed at a pH value of about 6.5. The dyestuff is precipitated by adding 10% strength by volume sodium chloride and is filtered off and washed with 300 parts by volume of 10% strength sodium chloride solution.
Example 9 50.3 parts of the dyestuff 1 - amino - 4 - (3 - amino - 4 - methyl - 5' sulpho - phenyl - amino) - anthraquinone - 2 - sulphonic acid are dissolved in water and the necessary quantity of sodium carbonate to form a neutral solution.
This solution is added at 05 to a suspension of 18.5 parts of cyanuric chloride which has been prepared by dropwise addition of the cyanuric chloride dissolved in 110 parts of acetone to 250 parts of ice. The hydrogen chloride formed in the reaction is neutralised by adding 50 parts of 2 normal sodium carbonate solution dropwise, a pH value of 6-6.5 being produced. 36.3 parts of bis - [p - (,B chloroethyl - sulphonyl) - ethyl] - amine hydrochloride are then added and the mixture is warmed to 30400 and this temperature is maintained for 3 hours. At the same time, the pH value is kept at 4.04.5 by adding 100 parts of 2 normal sodium carbonate solution dropwise.The resulting reactive dyestuff of the formula
is salted-out with sodium chloride, filtered off and dried at 5560 .
Similar valuable dyestuffs according to the invention are obtained if the dyestuffs of the list which follows are employed instead of the starting dyestuff 1 amino - 4 - (3 - amino - 4 - methyl - 5 - sulpho - phenyl - amino) - anthraquinone - 2 - sulphonic acid and if the procedure is in other respects as described above.
Intermediate dyestuffs 1 - Amino - 4 - (3 - amino - 4 - sulpho - phenyl - amino) - anthraquinone 2 - sulphonic acid, I - amino - 4 - (4 - amino - 3 - sulpho - phenyl - amino) anthraquinone - 2 - sulphonic acid, 1 - amino - 4 - (3 - amino - 2 - methyl - 5 sulpho - phenyl - amino) - anthraquinone - 2 - sulphonic acid, 1 - amino - 4 (4 - amino - 2,2' - disulpho - diphenyl-(4')- amino) - anthraquinone - 2sulphonic acid, 1 - amino - 4 - (3 - amino - 4 - methyl - 5 - sulpho - phenyl sulphonyl - phenyl - (3') - amino) - anthraquinone - 2 - sulphonic acid, 1 amino - 4 - (4 - amino - phenyl - amino) - anthraquinone - 2,5 - disulphonic acid and 1 - amino - 4 - (4 amino - 2,2' - disulpho - stilbyl- (4)- amino) - anthraquinone - 2 - sulphonic acid.
Example 10 106.6 parts of the dyestuff 3 - (3 - amino - 4 - sulpho - phenyl - amino sulphonyl) - copper - phthalocyanine - 3',3",3"' - trisulphonic acid are dissolved in water and the necessary quantity of sodium carbonate to form a neutral solution.
This solution is run, at 0-5 , into a suspension of 18.5 parts of cyanuric chloride which has been prepared by dropwise addition of the cyanuric chloride dissolved in 110 parts of acetone to 250 parts of ice. The pH value is kept at 6-6.5 during the reaction by adding 50 ml of 2 normal sodium carbonate solution dropwise. 36.3 parts of bis - [ss - (ss - chloroethylsulphonyl) - ethyl] - amine hydrochloride are added to the resulting intermediate stage and the mixture is warmed at 35-45 for 4 hours, At the same time, the pH value is kept at 4.0-4.5 by adding 100 parts of 2 normal sodium hydroxide solution dropwise. The resulting reactive dyestuff has the following structure:
It is precipitated with sodium chloride, filtered off and dried in vacuo at 5560 .
The dyestuff 3 - (3' - amino - 4' - sulpho - phenyl - amino - sulphonyl) copper - phthalocyanine - 3',3",3"' - trisulphonic acid which serves as the starting material can be prepared by reacting copper phthalocyanine tetrasulphochloride with 2,4 - diamino - benzene - sulphonic acid in the presence of pyridine at pH 5-9.
Similarly valuable dyestuffs according to the invention are obtained if starting dyestuffs are employed which have been prepared with 2,4 - diamino - toluene 6 - sulphonic acid, 2,5 - diamino - benzene - sulphonic acid, 2,6 - diamino - toluene - 4 - sulphonic acid, 4,4' - diamino - diphenyl - 2,2' - disulphonic acid and 3,3' - diamino - 4 - methyl - diphenyl - sulphone - 5 - sulphonic acid instead of 2,4 - diamino - benzene - sulphonic acid and if the reaction with cyanuric chloride and bis - [p - (/3 - chloroethyl - sulphonyl) - ethyl] - amine hydrochloride is carried out in other respects as described above.
Similarly valuable reactive dyestuffs according to the invention are also obtained if corresponding nickel phthalocyanine dyestuffs are used as starting materials instead of copper phthalocyanine dyestuffs.
Example 11 A neutral solution of 48.9 parts of 4 - amino - 4' - (2,6 - dinitro - 4 carboxy - phenyl - amino) - diphenylamine - 2 - sulphonic acid is reacted at 0 5 with a suspension of 18.5 parts of cyanuric chloride which has been obtained by dropwise addition of the cyanuric chloride dissolved in 110 parts of acetone to 250 parts of ice. The pH value is kept at 6.0-6.5 by adding 50 parts of 2 normal sodium hydroxide solution in portions. After the reaction is complete, 36.3 parts of bis [ss - (p - chloroethyl - sulphonyl) - ethyl - amine hydrochloride are added in the form of a powder and the mixture is warmed to 30400 and this temperature is maintained for 3 hours, the pH value being kept at 4.04.5 with 100 parts of 2 normal sodium hydroxide solution.The resulting yellow-brown reactive dyestuff has the following structure:
It is precipitated with sodium chloride, filtered off and dried at 5560 .
The starting dyestuff which is used, 4 - amino - 4' - (2,6 - dinitro - 4 carboxy - phenyl - amino) - diphenylamine - 2 - sulphonic acid can be prepared in the following way: 27.9 parts of 4,4' - diamino - diphenylamine - 2 - sulphonic acid are dissolved in water to form a neutral solution. 24.7 parts of 1 - chloro 2,5 - dinitro - benzene - 4 - carboxylic acid and 8.5 parts of anhydrous sodium acetate are added to the mixture, which is boiled for 5-6 hours at 95-98 and the condensation product is precipitated as the sodium salt.
Example 12 58.1 parts of the copper complex dyestuff prepared by diazotising 2 aminophenol - 4,6 - disulphonic acid and coupling the product with 2 - amino 5 - naphthol - 7 - sulphonic acid, followed by coppering in acetic acid solution, are dissolved in water to form a neutral solution. This dyestuff solution is run, at W5 , into a suspension of 18.5 parts of cyanuric chloride which has been prepared by dissolving the cyanuric chloride in 110 parts of acetone and adding the solution dropwise to 250 parts of ice. The pH value is kept at 4.55.5 during the reaction by adding 50 parts of 2 normal sodium carbonate solution dropwise.Stirring is continued for a further 1-2 hours at 05 until the reaction is complete. 36.5 parts of bis - [p - (/3 - chloroethyl - sulphonyl) - ethyl] - amine hydrochloride are then added and the mixture is warmed to approximately 450 and the pH value is kept at 4.5-5.0 by adding 100 parts of 2 normal sodium carbonate solution in portions. The resulting ruby-red reactive dyestuff corresponds to the following formula:
It is precipitated with sodium chloride, filtered off and dried at 5560 .
Similarly valuable reactive dyestuffs according to the invention are obtained if the copper complex dyestuffs of the dyestuffs prepared from the diazo components and coupling components in the following~text are employed as the starting dyestuffs instead of the copper complex dyestuff from 2 - amino - phenol - 4,6 disulphonic acid and 2 - amino - 5 - naphthol - 7 - sulphonic acid, and if the reactions with cyanuric chloride and bis - [p - (ss - - chloro - ethyl - sulphonyl) ethyl] - amine hydrochloride are carried out in other respects as described above.
Diazo components: 2 - Amino - phenol - 4 - sulphonic acid, 2 - amino - phenol - 5 - sulphonic acid, 6 - nitro - 2 - amino - phenol - 4 - sulphonic acid, 4 - nitro - 2 - amino phenol - 6 - sulp'honic acid, 4 - chloro - 2 - amino - phenol - 6 - sulphonic acid, 2 - amino - 4 - methyl - phenol - 6 - sulphonic acid, 2 - amino - 4 - acetamino phenol - 6 - sulphonic acid, 1 - amino - 2 - naphthol - 4 - sulphonic acid and 6 nitro - 1 - amino - 2 - naphthol - 4 - sulphonic acid.
Coupling components: 1 - Amino - 5 - naphthol - 7 - sulphonic acid, 1 - amino - 8 - naphthol - 4 sulphonic acid, 1 - amino - 8 - naphthol - 6 - sulphonic acid, 2 - (N - methylamino) - 5 - naphthol - 7 - sulphonic acid, 2 - (N - ethylamino) - 5 naphthol - 7 - sulphonic acid, 2 - (N - hydroxyethylamino - 5 - naphthol - 7 sulphonic acid, 2- amino - 8 - naphthol - 6 - sulphonic acid, 2 - (N - methylamino) - 8 - naphthol - 6 - sulphonic acid, 2 - (N - ethylamino) - 8 naphthol - 6 - sulphonic acid, 1 - amino - 8 - naphthol - 3,6 - disulphonic acid, 1 - amino - 8 - naphthol -4,6 - disulphonic acid, 2 - amino - 5 - naphthol - 1,7 disulphonic acid and 2 - amino - 8 - naphthol - 3,6 - disulphonic acid.
Example 13 36.3 parts of bis - [p - (/3 - chloroethyl - sulphonyl)- ethyl] - amine hydrochloride are added, in the form of powder, to a suspension of 79.4 parts of the copper complex of 7 - [6 - (3,5 - dichloro - 2,4,6 - triazinyl - amino) - 2 hydroxy - 4 - sulpho - 1 - naphthyl - azo] - 1 - amino - 8 - hydroxy - naphthalene - 2,4 - disulphonic acid in approximately 800 parts of water at 05 and having a pH value of 6.5. The mixture is warmed to 30400 and this temperature is maintained for 4 hours. At the same time, the pH value is kept at 4.04.5 by adding 100 parts of 2 normal sodium carbonate solution dropwise.The end of the reaction is recognised by the fact that the pH value remains constant at 4.5. The blue reactive dyestuff which is prepared has the following structure:
It is either concentrated by evaporation in vacuo at 5560 or precipitated with sodium chloride.
The copper complex of 7 - [6 - (3,5 - dichloro - 2,4,6 - triazinyl - amino) - 2 - hydroxy - 4 - sulpho - 1 - naphthylazo] - I - amino - 8 - hydroxy naphthalene - 2,4 - disulphonic acid which is used as the starting dyestuff is prepared in the following way: 60.8 parts of 6 - nitro - 1 - diazonio - 4 - sulpho 2 - naphtholate are coupled with 63.8 parts of 1 - amino - 8 - hydroxy naphthalene - 2,4 - disulphonic acid at 0-5 in the presence of sodium carbonate.
In order to reduce the nitro group, a solution of 27.3 parts of sodium sulphide in water is added dropwise to the dyestuff solution at about 4050 and stirring is continued for 1-2 hours. The dyestuff, which contains amino groups, is precipitated with sodium chloride, filtered off and dissolved in about 800 parts of water and the pH of the solution is adjusted to 5-5.3 with acetic acid. 40 parts of copper acetate or 50 parts of copper sulphate are added to the mixture, which is stirred for 5 hours at 2Q--300. The resulting copper complex dyestuff is precipitated with sodium chloride, filtered off and dissolved in 800 parts of water to form a neutral solution.The dyestuff solution is then run, at 05 , into a suspension of 37.0 parts of cyanuric chloride which has been prepared by dropwise addition of the cyanuric chloride dissolved in 200 parts of acetone to 500 parts of ice. Stirring is continued for 1-2 hours at 0-5 , until diazotisable amino groups can no longer be detected.
Similarly valuable reactive dyestuffs according to the invention are obtained if the diazo compounds of the amines which follow are employed instead of 6 nitro - I - diazonio - 4 - sulpho - naphtholate: 4 - nitro - 2 - amino - I hydroxy - naphthalene - 6 - sulphonic acid, 6 - nitro - 2 - amino - phenol - 4 - sulphonic acid and 4 - nitro - 2 - amino - phenol - 6 - sulphonic acid.
Example. 14 36.3 parts of bis - [ss - (ss - chloroethyl - sulphonyl) - ethyl] - amine hydrochloride are added, in the form of powder, to a neutral dyestuff suspension of 82.4 parts of the copper complex of N - (2 - hydroxy - 4 - sulpho - phenyl) - N' :(2 - carboxy - 4 - sulpho - phenyl) - ms - [4 - (3,5 - dichloro - 2,4,6 - triazinyl amino) - 2 - sulphophenyl] - formazan in approximately 800 parts of water, the temperature being about 0-5 . The mixture is then warmed for 4 hours at 30-40 and the pH value is kept at 4.0-4.5 during this time by adding dilute sodium hydroxide solution in portions. When sodium hydroxide solution is no longer required, that is to say when the pH value remains constant, the blue reactive dyestuff which has been prepared is isolated by spray-drying at 5560 or by salting-out.It has the following structure:
The copper complex of N - (2 - hydroxy - 4 - sulpho - phenyl) - N' - (2 carboxy - 4 - sulpho - phenyl) - ms - [4 - (3,5 - dichloro - 2,4,6 - triazinyl amino) - 2 - sulpho - phenyl] - formazan which serves as the starting dyestuff is obtained in the following way: 46.4 parts of 2 - carboxy - phenylhydrazine - 4 sulphonic acid and 48.6 parts of 4 - acetamino - benzaldehyde - 2 - sulphonic acid are subjected to a condensation reaction in aqueous solution and the resulting hydrazone is coupled, in the presence of sodium carbonate and at 0-5 , with the diazo compound of 37.8 parts 1 - amino - 2 - hydroxy - benzene - 4 - sulphonic acid.The formazan which is formed is adjusted with acetic acid to pH 5-5.3 and is converted into the copper complex with copper donors, such as, for example, 40 parts of copper acetate or 50 parts of copper sulphate, by warming at 4500 for 5 hours. This copper complex is precipitated with sodium chloride and is dissolved in approximately 800 ml of water to form a neutral solution. The dyestuff solution is run, at 05 , into a suspension of 37.0 parts of cyanuric chloride which is prepared by dissolving the cyanuric chloride in 200 parts of acetone and precipitating with 500 parts of ice. The mixture is stirred for 1--2 hours at 05 until complete reaction has taken place.
Similarly valuable reactive dyestuffs according to the invention are obtained if formazans are prepared from the hydrazine, aldehyde and diazo components which follow, wherein at least one acetamino group must be present, in the aldehyde component or in the diazo component according to choice, the formazans are converted into the copper complex, the acetamino group is saponified, the dyestuffs are reacted with cyanuric chloride and the procedure is in other respects as indicated above. The components should also be chosen in such a way that at least three sulphonic acid groups are present per dyestuff molecule. If a saponifiable acetamino group is present in each of the aldehyde and diazo components, reactive radicals can be introduced into the dyestuff in two places.
Hydrazine components: 2-Hydroxy - phenylhydrazine, 6 - nitro - 2 - hydroxy - phenyl - hydrazine, 4 - chloro - 2 - carboxy - phenylhydrazine, 5 - nitro - 2 - carboxy - phenylhydrazine, 4 - methoxy - 2 - carboxy - phenylhydrazine, 4 - nitro - 2 hydroxy - 6 - sulpho - phenylhydrazine, 6 - nitro - 2 - hydroxy - 4 - sulpho phenylhydrazine, 2 - carboxy - 5 - sulpho - phenylhydrazine, 2 - hydroxy - 6 - carboxy - 4 - sulpho - phenylhydrazine, 2 - hydroxy - 4,6 - disulpho phenylhydrazine, 2 - hydroxy - 4 - sulpho - naphthylhydrazine and 2 - hydroxy 4,6' - disulpho - naphthyl - 1 - hydrazine.
Aldehyde components: Benzaldehyde, 4 - methyl - benzaldehyde, benzaldehyde - 2 - or 3- or 4 sulphonic acid, benzaldehyde - 2,4 - disulphonic acid, 2- or 3- or 4 - nitro benzaldehyde, 2 - chloro - benzaldehyde - 5 - sulphonic acid, 2- or 3- or 4 acetamino - benzaldehyde, 3 - acetamino - benzaldehyde - 4 - suiphonic acid and 5 - acetamino - benzaldehyde - 2 - sulphonic acid.
Diazo components: I - Amino - 3 - acetamino - 2 - hydroxy - benzene - 5 - sulphonic acid, 1 amino - 5 - acetamino - 2 - hydroxy - benzene - 3 - sulphonic acid, 3 - chloro 1 - amino - 2 - hydroxy - benzene - 5 - sulphonic acid, 5 - nitro - 1 - amino - 2 hydroxy - benzene - 3 - sulphonic acid, 5 - nitro - 1 - amino - 2 - hydroxy benzene - 4 - sulphonic acid and 1 - amino - 2 - hydroxy - benzene - 4,6 disulphonic acid.
Example 15 A suspension of 36.5 parts of bis - [ss - (ss - chloroethyl - sulphonyl) - ethyl] amine hydrochloride is added, at 0--5 0, to a suspension in 800 parts of water of 91.9 parts of the dichloro - triazinyl - amino - phenylene which can be obtained in accordance with German Offenlegungsschrift 2,305,990, Example 31, and the mixture is heated for 3--4 hours at 30400. The hydrogen chloride which is eliminated is neutralised by adding 100 parts of 2 normal sodium hydroxide solution dropwise and the pH value is kept at 4.04.5. The reaction is complete when the pH value remains constant. The blue reactive dyestuff which is obtained is concentrated by evaporation in vacuo at 5560 or is precipitated with sodium chloride. It corresponds to the following formula:
Example 6 An aqueous suspension of 72.6 parts of bis - [ss - (ss - chloroethyl sulphonyl) - ethyl] - amine hydrochloride is run, at 0-5 , into an aqueous suspension of 81.4 parts of the N,N' - bis - (3,5 - dichloro - 2,4,6 - triazinyl) compound of 7 - (5 - amino - 2 - sulpho - phenylazo) - 1 - amino - 8 naphthol - 3,6 - disulphonic acid. The mixture is then warmed to 30-40 , this temperature is maintained for 3-4 hours and, simultaneously, a solution of 100 parts of 2 normal sodium carbonate solution is run in dropwise, in portions, in order to keep the pH value at 4.0-4.5. The reaction is complete when the pH value remanis constant. The bluish-tinged red reactive dyestuff which is obtained is either concentrated by evaporation at 5560 in vacuo or is precipitated with sodium chloride.It has the following structure:
The N,N' - bis - (3,5 - dichloro - 2,4,6 - triazinyl) compound of 7 - (5 - amino - 2 sulpho - phenylazo) - I - amino - 8 - naphthol - 3,6 - disulphonic acid which serves as the starting dyestuff is obtained by the following route: a neutral solution of 37.6 parts of 2,4 - diamino - benzene - sulphonic acid is reacted at a temperature of 05 and a pH value of 6-7 with a suspension of 37.0 parts of cyanuric chloride, and a neutral solution of 63.8 parts of I - amino - 8 - naphthol 3,6 - disulphonic acid is reacted at a temperature of 05 and pH value of 6-7 with a suspension of 37.0 parts of cyanuric chloride.In both cases the pH value of 6-7 is maintained by adding, in each case, 100 parts of 2 normal sodium carbonate solution dropwise. The diazo component, 2 - amino - 5 - (3,5 - dichloro - 2,4,6 triazinyl - amino) - benzene - sulphonic acid is diazotised in hydrochloric acid solution in the customary manner at 05 with sodium nitrite and is then combined with the coupling component, 1 - (3,5 - dichloro - 2,4,6 - triazinyl amino) - 8 - naphthol - 3,6 - disulphonic acid, to give the monoazo dyestuff.
Similarly valuable reactive dyestuffs according to the invention are obtained if, in the preparation of the starting dyestuff, the condensation products, with cyanuric chloride, of the coupling components mentioned in Example I are employed instead of the condensation product of 1 - amino - 8 - naphthol - 3,6 disulphonic acid with cyanuric chloride and if the procedure is in other respects as described above.
Equally valuable dyestuffs according to the invention are obtained if the condensation product of 2,4 - diaminobenzene - sulphonic acid with cyanuric chloride which is employed as the diazo component in the manufacture of the starting dyestuff, is replaced by the corresponding condensation products of cyanuric chloride with 2,5 - diaminobenzenesulphonic acid or 2,5 diaminobenzene - 1,4 - disulphonic acid and if the procedure is in other respects as described above.
Example 17 A neutral solution of 72.8 parts of the copper complex of the dyestuff 6 - amino - l,2',8' - trihydroxy - 2,1' - azo - naphthalene - 3',4,6',8 - tetrasulphonic acid in 400 parts of water is run, at 0--50, into the suspension of 18.5 parts of cyanuric chloride which has been dissolved in 70 parts of warm acetone and added to 300 parts of ice while stirring. The hydrochloric acid which is formed in the reaction is neutralised (pH value 5.5-6.5) by adding 50 parts of 2 normal sodium hydroxide solution dropwise. 36.3 parts of bis - [ss - (ss - chloroethyl - sulphonyl) ethyl] - amine hydrochloride are then added in the form of a powder.The mixture is warmed to 400 in the course of approximately + hour and this temperature is maintained for 3 hours. At the same time, the pH value is kept at 4.0--4.5 by adding 17 g of sodium bicarbonate. The blue reactive dyestuff of the formula
which is obtained is salted-out with sodium chloride, filtered off and dried in vacuo at 60".
The copper complex dyestuff which is used as the starting material is prepared in the following way in accordance with the instructions of German Patent Specification 1,117,235: 81.8 parts of the 0 - benzenesulphonyl ester of I amino - 8 - naphthol - 3,6 - disulphonic acid are diazotised and are coupled with 72.2 parts of 2 - acetamino - 5 - naphthol - 4,8 - disulphonic acid in a medium alkaline with sodium carbonate. The resulting monoazo dyestuff is converted into the copper complex in a known manner by oxidative coppering using copper sulphate and hydrogen peroxide in acetic acid solution and the benzene - sulphonyl group and the acetyl group are then split off by hydrolysis.
Equally valuable dyestuffs according to the invention are obtained if, in the preparation of the starting dyestuff, the diazo component is replaced by molar quantities of the diazo components which follow and if the procedure is in other respects in accordance with the route described above: 1 - amino - 8 - naphthol 4,6 - disulphonic acid 0 - benzenesulphonyl ester, 1 - amino - 8 - naphthol 4,7 - disulphonic acid 0 - benzenesulphonyl ester, 2 - amino - naphthalene 4,8 - disulphonic acid, 2 - amino - 6 - nitro - naphthalene - 4,8 - disulphonic acid, 2 - amino- naphthalene - 4,6,8 - trisulphonic acid, 2 - aminonaphthalene - 6 - sulphonic acid and 2 - amino - naphthalene - 8 - sulphonic acid.
Valuable dyestuffs according to the invention are further obtained if, in the preparation of the starting dyestuff, the coupling component 2 - acetamino - 5 naphthol - 4,8 - disulphonic acid is replaced by molar quantities of the N-acetyl compound of the following coupling components: 2 - amino - 8 - naphthol - 6 sulphonic acid, 2 - amino - 5 - naphthol - 7 - sulphonic acid, 2 - amino - 5 naphthol - 1,7 - disulphonic acid and 2 - amino - 8 - naphthol - 3,6 - disulphonic acid.
Example 18 70.2 parts of the disazo dyestuff 1 - amino - 2 - (4 - sulphophenylazo) - 7 (2 - sulpho - 5 - aminophenylazo) - 8 - naphthol - 3,6 - disulphonic acid are reacted, in the form of a neutral solution at 05 , with a suspension of 18.5 parts of cyanuric chloride which has been dissolved in 110 parts of acetone and reprecipitated using 250 parts of ice. The reaction is carried out at pH 6.06.5, the pH value being maintained by adding 50 parts of 2 normal sodium carbonate solution dropwise. 36.3 parts of bis - [ss - (ss - chloroethyl - sulphonyl) - ethyl] amine hydrochloride are then added in the form of a powder, the mixture is warmed to 30400 and the pH value is kept at 4.04.5 by adding 100 parts of 2 normal sodium carbonate solution dropwise.The resulting dyestuff of the structure.
is isolated by salting-out or by spray-drying.
The disazo dyestuff which serves as the starting material can be prepared in the following way: the diazo compound of 34.6 parts of sulphanilic acid is coupled, in a first stage in an acid medium at pH 24, with 63.8 parts of 1 - amino - 8 naphthol - 3,6 - disulphonic acid, and then in a second stage, in a medium alkaline with sodium carbonate, with the diazo compound of 46.0 parts of 2 - amino - 4 acetamino - benzene - sulp'honic acid. The acetyl group of the disazo dyestuff is saponified by warming at 9-1000 in the presence of excess sodium hydroxide solution.
Similarly valuable dyestuffs according to the invention are obtained if the dyestuffs which follow are employed instead of the disazo dyestuff employed as the starting dyestuff and if the procedure is in other respects as described above: 1 amino - 2 - (2 - sulphophenylazo) - 7 - (2 - sulpho - 5 - aminophenylazo) - 8 naphthol - 3,6 - disulphonic acid, 1 - amino - 2 - (2,4 - disulphophenyl - azo) 7 - (2 - sulpho - 5 - aminophenylazo) - 8 - naphthol - 3,6 - disulphonic acid, 1 amino - 2 - (2,5 - disulphophenylazo) - 7 - (2 - sulpho - 5 - amino - phenylazo) - 8 - naphthol - 3,6 - disulphonic acid, 1 - amino - 2 - (4 - sulphophenylazo) - 7 (2 - sulpho - 4' - aminophenylazo) - 8 - naphthol - 3,6 - disulphonic acid, 1 amino - 2 - (2,5 - disulphophenylazo) - 7 - (2 - sulpho - 4 - aminophenylazo) 8 - naphthol - 3,6 - - disulphonic acid, I - amino - 2 - (2 - sulpho - 4 aminophenylazo) - 7 (4 - sulphophenylazo) - 8 - naphthol - 3,6 - disulphonic acid, I - amino - 2 - (2 - sulpho - 4 - amino - phenylazo)- 7 - (2,5 disulphophenylazo) - 8 - naphthol - 3,6 - disulphonic acid, 1 - amino - 2 - (2,5 disulpho - 4 - aminophenylazo) - 7 - phenylazo - 8 - naphthol - 3,6 - disulphonic acid, 1 - amino - 2 - (2 - sulpho - 5 - amino - phenylazo) - 7 - (4- sulphophenylazo) - 8 - naphthol - 3,6 - disulphonic acid,
1 - amino - 2 - (2 sulpho - 5 - aminophenylazo) - 7 - (2 - sulphophenyl - azo) - 8 - naphthol - 3,6 disulphonic acid and I - amino - 2 - (2 - sulpho - 5 - aminophenylazo) - 7 - (2,5 disulphophenylazo) - 8 - naphthol - 3,6 - disulphonic acid.
Equally valuable dyestuffs according to the invention are obtained if, in the preparation of the abovementioned disazo dyestuffs, the I - amino - 8 naphthol - 3,6 - disulphonic acid is replaced by 1 - amino - 8 - naphthol - 4,6 disulphonic acid and if the procedure is in other respects as described above.
Example 19 36.3 parts of bis - [ss - (ss - chloroethyl - sulphonyl) - ethyl] - amine hydrochloride are added, at 0-5 , to a neutral solution of 80.8 parts of the dichlorotriazinyl compound of an aminoxanthene which is described in German Offenlegungsschrift 2,442,839, Example 7, the mixture is warmed to 3545 and this temperature is maintained for 34 hours.
At the same time, the hydrogen chloride which is formed is neutralised by adding 100 parts of 2 normal sodium hydroxide solution dropwise and in portions, the pH value being kept at 4.5-5.5. The reaction is complete when the pH value remains constant. The blue-violet reactive dyestuff which is prepared has the following structure:
It is concentrated by evaporation in vacuo at 5560 or is precipitated with sodium chloride.
Similarly valuable reactive dyestuffs according to the invention can be obtained if the dichlorotriazinyl or dibromotriazinyl compounds of aminoxanthenes which, in turn, can be prepared in accordance with DOS 2,442,839 from the monoamines: taurine, N - ethyltaurine, aminoacetic acid, diethanolamine, 2- or 3or 4 - amino - benzene - sulphonic acid, 1 - amino - benzene - 2,4- or 2,5 disulphonic acid, 2 - amino - toluene - 4 - sulphonic acid, 3 - amino - toluene 6 - sulphonic acid or 4 - amino - toluene - 2 - sulphonic acid and from the diamines: 1,3 - diamino - benzene - sulphonic acid, 2,5 - diamino - benzene 1,4 - disulphonic acid, 2,4 - diamino - toluene - 6 - sulphonic acid, 2,6 diamino - toluene - 4- sulphonic acid, 4,4' - diamino - diphenyl - 2,2' - disulphonic acid, 4,4' - diaminostilbene - 2,2' - disulphonic acid, 4,4' - diamino diphenylurea - 2,2' - disulphonic acid or 2,6 - diamino - naphthalene - 4,8 disulphonic acid, are employed as the starting dyestuffs. The dyestuffs should contain at least two groups which impart solubility.
Example 20 73.0 parts of the copper complex of the dyestuff 4 - (2 - hydroxy - 5 - nitro 3 - sulpho - phenyl - azo) - 6 - (5 - dichlorotriazinyl - amino - 2 - sulpho - phenyl - azo) - 1,3 - dihydroxybenzene are stirred in 700 parts of water at pH 6.5 and at about 10 . 36.3 parts of bis - [p - (ss - chloroethyl - sulphonyl) - ethyl] amine hydrochloride are added to the mixture. The temperature is then raised to 4550 . When the pH value has fallen to 3.8, 17 parts of sodium bicarbonate are added in the course of 4-5 hours in such a way that the pH value remains between 3.8 and 4.8.When the pH value is constant, it is adjusted to 7.0 with 2 normal sodium hydroxide solution and the resulting dyestuff of the formula
is isolated by salting-out or spray-drying.
The copper complex which is employed as the starting material can be obtained as follows: a diazo compound prepared from 23.4 parts of 4 - nitro - 2 aminophenol - 6 - sulphonic acid is coupled with 11.0 parts of 1,3 - dihydroxy benzene at 05 and at pH 5.5-6.5. This monoazo dyestuff is converted into the copper complex in acetic acid solution by adding 25.0 parts of crystalline copper sulphate. The dyestuff is precipitated by salting-out with sodium chloride and is filtered off and re-dissolved in water. It is then coupled at 515 and with the addition of sodium bicarbonate, with the diazo compound prepared from 23.0 parts of 2 - amino - 5 - acetamino - benzene - sulphonic acid, to give to diazo dyestuff. The latter is heated at 800 with sodium hydroxide solution and the acetyl group is split off.The dyestuff obtained in this way is then reacted, at 05 and at pH 6-6.5, with 18.5 parts of cyanuric chloride.
Similar valuable dyestuffs according to the invention are obtained if the dyestuffs which follow are employed instead of the copper complex dyestuff employed as the starting material: the copper complex of 4 - (2 hydroxy - 5 - sulpho - phenyl - azo) - 6 - (5 - dichlorotriazinylamino - 2sulpho - phenyl - azo) - 1,3 - dihydroxybenzene, the 2:1 chromium complex of 4 (2 - hydroxy - 5 - sulpho - phenyl - azo) - 6 - (4 - dichlorotriazinylamino - 2 sulpho - phenyl - azo) - 1,3 - dihydroxy - benzene, the copper complex of4 - (2 hydroxy - 3 - chloro - 5 - sulpho - phenyl - azo) - 6 - (4 - dichlorotriazinyl amino - 2 - sulpho - phenyl - azo) - 1,3 - dihydroxy - benzene, the 2::1 cobalt complex of 4 - (2 - hydroxy - 6 - nitro - 4 - sulpho - naphthyl - 1 - azo) - 6 - (4 dichlorotriazinylamino - 2,5 - disulpho - phenyl - azo) - 1,3 - dihydroxy - benzene and the copper complex of 4 - (2 - hydroxy - 3,5 - disulpho - phenyl azo) - 6 - (6 - dichlorotriazinylamino - 4,8 - disulpho - naphthyl - 2 - azo) - 1,3 dihydroxy - benzene.
Example 21 Preparation of the Starting Dyestuff: 38.9 parts of the dyestuff obtained by coupling 6 - nitro - 2 - diazo - 1 - hydroxy - benzene - 4 - sulphonic acid and 2 - hydroxy - naphthalene in a medium alkaline with sodium carbonate, are stirred in 200 parts of water at pH 8 and at a temperature of 70--80". 67.9 parts of the chromium complex compound of the azo dyestuff formed from 4 - chloro - 2 - diazo - 1 - hydroxy - benzene - 6 sulphonic acid and 1 - amino - 8 - hydroxy - naphthalene - 3,6 - disulphonic acid, which contains 1 atom of chromium for 1 molecule of dyestuff, are introduced into this suspension, the pH value being kept between 7 and 9 by adding sodium carbonate solution dropwise. After 20 minutes at 7080 , a dark blue solution has formed.The paper chromatogram shows that a single-substance mixed complex has been formed. The mixed complex is acylated with 18.5 parts of cyanuric chloride for one hour at 0 and at pH 6.5-7.5.
Preparation of the Dyestuff According to the Invention: 36.3 parts of bis - [p - (ss - chloroethyl - sulphonyl) - ethyl] - amine hydrochloride are added to the solution of the starting dyestuff obtained in this way and the mixture is warmed to 500 in the course of 30 minutes. This temperature is maintained for 4 hours. During this time the pH value is kept between 5.0 and 5.5 by adding 11.5 parts of sodium carbonate. When the pH value remains constant, it is adjusted to 7.0 with dilute sodium hydroxide solution and the dyestuff of the formula
is isolated by spray-drying.
Example 22 72.6 parts of bis - [P - (/3 - chloroethyl - sulphonyl)- ethyl] - amine hydrochloride are added to a suspension of 115.6 parts of the bis (dichlorotriazinyl) compound of bis - [6 - (5 - amino - 2 - sulpho - phenylazo) 5 - hydroxy - 7 - sulpho - naphthyl - 2] - amine. The batch is warmed to 35400.
The pH value is kept at 4.5-5 by adding 200 parts of 2 normal sodium hydroxide solution in portions. The reaction is complete when the pH value remains constant.
The orange-red reactive dyestuff is then concentrated by evaporation in vacuo at 5560 or is precipitated with sodium chloride. It has the following structure:
The bis - (dichloro - triazinyl) compound of bis - [6 - (5 - amino - 2 - sulpho phenyl - azo) - 5 - hydroxy - 7 - sulpho - 2 - naphthyl] - amine which is used as the starting material is obtained in the following way: 37.6 parts of 2,4 - diamino benzene - sulphonic acid are acylated at 05 and at a pH value of 6-7 with a suspension of 37.0 parts of cyanuric chloride. The resulting 2 - amino - 4 - (3,5 dichloro - 2,4,6 - triazinyl - amino) - benzene - sulphonic acid is diazotised in the usual way and is coupled at W5 while adding 25 parts of sodium bicarbonate.
Similar valuable reactive dyestuffs according to the invention are obtained if 2,5 - diamino - benzene - sulphonic acid is employed instead of 2,4 - diamino benzene - sulphonic acid in the starting dyestuffs which are to be prepared.
In addition, bis - [5 - hydroxy - 7 - sulpho - 2 - naphthyl] - amine can be replaced by the following coupling components: bis - [5 - hydroxy - 7 - sulpho 2 - naphthyl] - urea, bis - [5 - hydroxy - 7 - sulpho - 2 - naphthyl] - thiourea, bis - [8 - hydroxy - 6 - sulpho - 2 - naphthyl] - amine, bis - [8 - hydroxy - 6 sulpho - 2 - naphthyl] - urea or bis - [8 - hydroxy - 6 - sulpho - 2 - naphthyl] thiourea.
Example 23 10 parts of woollen piece goods are introduced at 400C into a dye liquor which contains, in 500 parts of water, 0.1 part of the dyestuff obtained in Example 8, 0.6 part of 30 per cent strength acetic acid, 0.5 part of anhydrous sodium sulphate and 0.2 part of a surface-active auxiliary, and the dye bath is heated to 70"C in the course of 20 minutes. After 30 minutes at 7QOC, the temperature of the dye bath is raised to 98--1000C in the course of 30 minutes and is kept at this temperature for 60 minutes. The dyed material is then rinsed with warm water and then with cold water and is finally dried at 6O700C. A clear red shade which is distinguished by good fastness to light, wet processing and perspiration, is obtained.
Example 24 A fabric composed of mercerised or caustic-shrunk cotton is printed with the following printing ink: 30 g of the dyestuff prepared according to Example 6, 150 g of urea, 340 g of hot water, 450 g of an alginate thickener, 20 g of calcined sodium carbonate and 10 g of the sodium salt of m-nitrobenzenesulphonic acid.
1,000 g After printing and drying, the goods are steamed for approximately 5 minutes at 100--105"C and are rinsed and washed. A strong yellow print with very good fastness to wet processing and light is obtained.
A similar deep print is obtained if the dyestuff is fixed, not by steaming, but by dry heat, for example at 141500C for 5 minutes.
The dyestuff can also be used in a two-phase printing process. In this, the printing ink has the following composition: 30 g of the above dyestuff, 50 g of urea, 460 g of hot water, 450 g of an alginate thickener and 10 g of the sodium salt of m-nitrobenzenesulphonic acid.
1,000 g After printing and drying, the goods are padded with: 30 g of 38 Bé sodium hydroxide solution, 150 g of sodium carbonate, 50 g of potassium carbonate, 100 g of'sodium chloride and water, to give 1,000 ml and are steamed immediately afterwards at 120--1300C for approximately 30 seconds.
If a liquor having a higher content of sodium hydroxide (5100 g/l) is used, the dyestuff can also be fixed by the cold pad-batch method, that is to say by padding and storing the printed goods at room temperature for 3-5 hours. The socalled wet developing process is also possible using a liquor of the same composition. In this case, the dyestuff is fixed in 5-10 seconds by the development liquor which is heated to 95-1050C.
Example 25 30 parts of the dyestuff prepared according to Example 1 are dissolved in 1,000 parts of water. A cotton fabric is padded with this solution, squeezed out to give a liquor pick-up of 80 /" and dried. It is then treated at 700 C, for 30 minutes, in a bath which contains 250 parts of calcined sodium sulphate and 30 parts of 38 Bé sodium hydroxide solution dissolved in 1,000 parts of water. The dyeing is then stored for 4 hours and is finished in the customary manner. A clear, bluish-tinged red dyeing with excellent fastness to wet processing and light is obtained.
Example 26 168 ml of water at 250C are initially placed in a dye beaker with a capacity of 300 ml, which is placed in a water bath which can be heated. 0.3 g of the dyestuff obtained according to Example 1 is made into a smooth paste with 2 ml of cold water and 30 ml of hot water (700 C) are added; in the course thereof the dyestuff dissolves. The dyestuff solution is added to the water which was initially taken and 10 g of cotton yarn are continually agitated in this dye liquor. The temperature of the dye liquor is raised to 7(r--800C in the course of 10 minutes, 20 g of sodium chloride and 6 g of sodium carbonate are added and dyeing is carried out for 60 minutes. The liquor adhering is then removed by squeezing out and the material is rinsed with cold and hot water. The dyed material is then soaped for 20 minutes at the boil, rinsed again and dried. A clear red dyeing with outstanding fastness to washing and light and good stability against the action of chlorine, is obtained.
WHAT WE CLAIM IS: 1. A reactive dyestuff of the formula I
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (41)

**WARNING** start of CLMS field may overlap end of DESC **. A similar deep print is obtained if the dyestuff is fixed, not by steaming, but by dry heat, for example at 141500C for 5 minutes. The dyestuff can also be used in a two-phase printing process. In this, the printing ink has the following composition: 30 g of the above dyestuff, 50 g of urea, 460 g of hot water, 450 g of an alginate thickener and 10 g of the sodium salt of m-nitrobenzenesulphonic acid.
1,000 g After printing and drying, the goods are padded with:
30 g of 38 Bé sodium hydroxide solution,
150 g of sodium carbonate,
50 g of potassium carbonate,
100 g of'sodium chloride and water, to give 1,000 ml and are steamed immediately afterwards at 120--1300C for approximately 30 seconds.
If a liquor having a higher content of sodium hydroxide (5100 g/l) is used, the dyestuff can also be fixed by the cold pad-batch method, that is to say by padding and storing the printed goods at room temperature for 3-5 hours. The socalled wet developing process is also possible using a liquor of the same composition. In this case, the dyestuff is fixed in 5-10 seconds by the development liquor which is heated to 95-1050C.
Example 25
30 parts of the dyestuff prepared according to Example 1 are dissolved in 1,000 parts of water. A cotton fabric is padded with this solution, squeezed out to give a liquor pick-up of 80 /" and dried. It is then treated at 700 C, for 30 minutes, in a bath which contains 250 parts of calcined sodium sulphate and 30 parts of 38 Bé sodium hydroxide solution dissolved in 1,000 parts of water. The dyeing is then stored for 4 hours and is finished in the customary manner. A clear, bluish-tinged red dyeing with excellent fastness to wet processing and light is obtained.
Example 26
168 ml of water at 250C are initially placed in a dye beaker with a capacity of 300 ml, which is placed in a water bath which can be heated. 0.3 g of the dyestuff obtained according to Example 1 is made into a smooth paste with 2 ml of cold water and 30 ml of hot water (700 C) are added; in the course thereof the dyestuff dissolves. The dyestuff solution is added to the water which was initially taken and 10 g of cotton yarn are continually agitated in this dye liquor. The temperature of the dye liquor is raised to 7(r--800C in the course of 10 minutes, 20 g of sodium chloride and 6 g of sodium carbonate are added and dyeing is carried out for 60 minutes. The liquor adhering is then removed by squeezing out and the material is rinsed with cold and hot water.The dyed material is then soaped for 20 minutes at the boil, rinsed again and dried. A clear red dyeing with outstanding fastness to washing and light and good stability against the action of chlorine, is obtained.
WHAT WE CLAIM IS: 1. A reactive dyestuff of the formula I
wherein F denotes the radical of a dyestuff which contains at least one -SO3H group, R denotes hydrogen or lower alkyl having 1 to 4 carbon atoms which optionally may be substituted. X denotes a substituent which can be split off as an anion, p denotes 1 or 2 and A denotes a radical of the formula II
in which alk is a lower alkylene radical having 2-6 C atoms and V' is hydrogen or the radical of an optionally substituted hydrocarbon, Z is a A-halogenoethyl radical or a vinyl radical, m is 1 or 2 and n is 2 minus m.
2. A reactive dyestuff as claimed in Claim 1 wherein F is a radical of a metalfree or metal containing monoazo or disazo dyestuff which contains at least one --SO,H group; a radical of a derivative of 1 - amino - anthraquinone or 1 anilino - anthraquinone; a radical of a sulphophthalocyanine dyestuff; or a radical of a formazan or nitroaryl dyestuff.
3. A reactive dyestuff as claimed in Claim 2 wherein F is a radical of a metalfree or metal containing monoazo or disazo dyestuff which contains at least one -SO3H group.
4. A reactive dyestuff as claimed in Claim 3 wherein F is a radical of a monoazo or disazo dyestuff of the formula VIa, VIb or VIc D-N=N-(M-N=N-)nK- (VIa) --DD-N==N-( M--N=NN-),K (VIb) -D-N=N-(M-N=N-)nK- (VIc) or of a metal complex derived therefrom, in which formulae VIa, VIb and VIc, D represents the radical of a diazo component of the benzene or naphthalene series which is optionally substituted by at least one substituent, K represents the radical of a coupling component of the benzene, naphthalene or ketomethylene series which is optionally substituted by at least one substituent, M represents the radical of a middle component of the benzene or naphthalene series which is optionally substituted by at least one substituent, n represents the numbers 0 or 1 and D, M and K together contain at least two sulphonic acid groups.
5. A reactive dyestuff as claimed in Claim 4 wherein each said at least one substituent is: hydroxyl; amino in the case of the radical K but not in the case of radical D or M; methyl; ethyl; methoxy or ethoxy; optionally substituted alkanoylamino having 2-4 C atoms; optionally substituted benzoylamino; or halogen.
6. A reactive dyestuff as claimed in Claim 4 or Claim 5 wherein D, M and K together contain three or four sulphonic acid groups.
7. A reactive dyestuff as claimed in any of Claims 4 to 6 wherein K represents the radical of a coupling component of the benzene, naphthalene, pyrazolone, 6 hydroxypyrid - 2 - one or acetoacetic acid arylamide series.
8. A reactive dyestuff as claimed in Claim 1 or Claim 2, characterised in that F is a radical of a derivative of 1 - amino - anthraquinone or 1 - anilino anthraquinone.
9. A reactive dyestuff as claimed in Claim 8 wherein F is a radical of an anthraquinone dyestuff of the general formula VII
wherein Z' represents a phenylene radical, the anthraquinone nucleus and/or the phenylene radical being optionally substituted by a further 50311 group, and the phenylene radical being optionally substituted by a carboxyl group, an alkoxy group having 1-3 C atoms, a halogen atom or by 1-3 alkyl groups each having 1-3 C atoms.
10. A reactive dyestuff as claimed in Claim 1 or Claim 2, wherein F is a radical of a sulphophthalocyanine dyestuff.
11. A reactive dyestuff as claimed in Claim 10 wherein F is a radical of a phthalocyanine dyestuff of the general formula VIII
wherein Pc represents the radical of a metal-containing or metal-free phthalocyanine, W represents hydroxyl and/or NR'R", and each of R', R", and R"' which may be the same or different, is hydrogen or alkyl having 14 C atoms, B denotes a phenylene radical optionally substituted by halogen or 1-3 alkyl groups having 1-2 C atoms, or by one or two sulphonic acid groups or carboxylic acid groups, or denotes an alkylene radical having 2-6 C atoms k denotes 2 or 3 and p denotes 1 or 2.
12. A reactive dyestuff. as claimed in Claim 11 wherein the metal-containing phthalocyanine is copper or nickel phthalocyanine.
13. A reactive dyestuff as claimed in Claim 11 or Claim 12 wherein B is phenyl substituted by a sulphonic acid group.
14. A reactive dyestuff as claimed in Claim 11 wherein F is a derivative of a phthalocyaninesulphanilide or phthalocyaninesulphalkylamide which has 2-6 C atoms in the alkyl chain and carries at least two sulphonic acid groups in the phthalocyanine nucleus.
15. A reactive dyestuff as claimed in any of the preceding claims wherein R denotes hydrogen or alkyl which has I to 4 C atoms and is optionally substituted by -COOH or -SO3H, or denotes cyanoethyl or hydroxyethyl.
16. A reactive dyestuff as claimed in any of the preceding claims wherein R is hydrogen or methyl.
17. A reactive dyestuff as claimed in any of the preceding claims according to Claims I to 11, claims wherein X represents fluorine, chlorine, bromine, alkylsulphonyl having 1 to 4 C atoms, phenylsulphonyl or the --SO,H radical.
18. A reactive dyestuff as claimed in Claim 17 wherein X represents chlorine.
19. A reactive dyestuff as claimed in any of the preceding claims wherein, in A as defined in general formula II, alk denotes methylene, ethylene, or a straight or branched chain isomer of a polymethylene radical having 3 to 6 C atoms.
20. A reactive dyestuff as claimed in Claim 19, wherein alk denotes an ethylene radical.
21. A reactive dyestuff as claimed in any of the preceding claims wherein, in A as defined in general formula II, V' is a methyl group optionally substituted by carboxyl or a sulphonic acid group or a derivative thereof, or is an alkyl radical which has 2--6 C atoms and is optionally substituted by at least one alkoxy group having 1 or 2 C atoms, a carboxyl or sulphonic acid, group, halogen atom or hydroxyl group, or is an unsubstitued alkyl radical having 7-20 C atoms, a cyclohexyl radical or a phenyl radical optionally substituted by at least one methyl, ethyl, methoxy, ethoxy, carboxylic acid or sulphonic acid group or halogen atom.
22. A reactive dyestuff as claimed in Claim 21 wherein V' denotes hydrogen or an optionally substituted alkyl radical having 1 to 4 C atoms.
23. A reactive dyestuff as claimed in Claim 22 wherein V'denotes hydrogen or methyl.
24. A reactive dyestuff as claimed in any of Claim 1 to 17, or Claim 19 or 20 when dependent on any of Claims 1 to 17, or any of Claims 21 to 23 when dependent on any of Claims 1 to 17 or on Claim 19 or 20, wherein Z is /3 chloroethyl or vinyl and X represents chlorine or bromine.
25. A reactive dyestuff as claimed in any of the preceding claims wherein X is chlorine, alk is ethylene, Z is ,B - chloroethyl or vinyl and m represents the number 2.
26. A process for the preparation of a reactive dyestuff bf the formula I as defined in any of the preceding claims wherein a dyestuff of the formula V
wherein F, R and p each have the same meaning as defined above in formula I and X and X', which are the same or different, each have the meaning as defined above for X in formula I, is reacted with an amine of the formula IIa
wherein alk, Z, V', n and m have same meaning as defined above in formula I.
27. A process as claimed in Claim 26 wherein the reaction is carried out at a temperature in the range from 25 to 700C, and in an aqueous medium at a pH value in the range from 2 to 6.5.
28. A process as claimed in Claim 27 wherein the reaction is carried out at a temperature of from 35 to 550C and at a pH value of from 3.5 to 4.5.
29. A process as claimed in any of Claims 26 to 28 which includes the preliminary step of reacting a dyestuff of the formula III
in which F, R and p have the same meaning as defined above in formula V, with a reactive derivative of a 1,3,5 - triazine of the formula IV
in which X and X' have the same meaning as defined above in formula V, so as to produce a dyestuff of the general formula V.
30. A process as claimed in any of Claims 26 to 29 which includes the preliminary step of reacting a first dyestuff component which contains a radical of the formula Va
in which R, X and X' have the same meaning as defined above in formula V, with a second dyestuff component which optionally contains a radical of the formula Va as defined above, so as to produce a dyestuff of the formula V as defined above.
31. A process as claimed in any of Claims 26 to 28 and 30, wherein in formula V, F is a radical of a metal-free or metal-containing monoazo or disazo dyestuff, which process includes the preliminary step of reacting a diazo component and a coupling component, at least one of which contains a group of the formula Va, so as to produce said compound of formula V.
32. A method of dyeing or printing a cellulose, natural or synthetic polyamide substrate or a material containing a said substrate using a dyestuff wherein said dyestuff is a reactive dyestuff as claimed in any of Claims 1 to 25.
33. A dyestuff which has the formula
34. A dyestuff which has the formula
35. A dyestuff which has the formula
36. A dyestuff which has the formula
37. A reactive dyestuff according to Claim I substantially as described hereinbefore with particular reference to any of the specific embodiments illustrated in any of Examples I to 22.
38. A process for the preparation of a reactive dyestuff according to Claim 26 substantially as described hereinbefore with particular reference to any of the specific embodiments illustrated in any of Examples I to 22.
39. A reactive dyestuff when prepared by a process according to any of Claims 26 to 31 or Claim 39.
40. A method of dyeing or printing a cellulose, natural or synthetic polyamide substrate or a material containing a said substrate according to Claim 32 substantially as described hereinbefore with particular reference to any of the specific embodiments illustrated in any of Examples 23 to 26.
41. A cellulose, natural or synthetic polyamide substrate or a material containing a said substrate when dyed or printed by a method as claimed in Claim 32 or Claim 40.
GB13852/77A 1976-04-03 1977-04-01 Dyestuffs containing the triazine ring their preparation and use Expired GB1576237A (en)

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US4908436A (en) * 1983-10-26 1990-03-13 Ciba-Geigy Corporation Fibre-reactive azo dyes containing vinylsulfonyl groups and further aliphatic fibre-reactive radicals
US4754023A (en) * 1983-11-09 1988-06-28 Ciba-Geigy Corporation Reactive dyestuffs comprising a triazine moiety and a vinylsulfonyl moiety both being linked by a substituted alkylene bridge member
US4782140A (en) * 1984-04-05 1988-11-01 Ciba-Giegy Corporation Triazinyl reactive dyes containing additional fiber reactive groups bound through the sulfonylalkylaminoalkylamino bridge
US4801694A (en) * 1984-10-15 1989-01-31 Ciba-Geigy Corporation Triazinyl reactive dyestuffs in which triazinyl group is further substituted with a beta-chloroethylsulfonyl- or vinylsulfonylbutyrylamino moiety
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WO2013182349A1 (en) * 2012-06-05 2013-12-12 Huntsman Advanced Materials (Switzerland) Gmbh Reactive dyes, their preparation and their use
US9346958B2 (en) 2012-06-05 2016-05-24 Huntsman International Llc Reactive dyes, their preparation and their use
CN114981005A (en) * 2020-01-29 2022-08-30 亨斯迈先进材料（瑞士）有限公司 Functionalized particles
WO2021219556A1 (en) 2020-04-27 2021-11-04 Huntsman Advanced Materials (Switzerland) Gmbh Mixtures of reactive dyes and their use for the dyeing or printing of textile fibre materials
WO2023144005A1 (en) 2022-01-25 2023-08-03 Huntsman Advanced Materials (Switzerland) Gmbh Isomeric mixture of reactive dyes and their use for the dyeing or printing of textile fibre materials
CN116814090A (en) * 2023-06-11 2023-09-29 水木聚力接枝纺织新技术(深圳)有限公司 Water-soluble diacryloyl amino C acid dye and synthesis method and application thereof

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JPS52121039A (en) 1977-10-12
IT1075683B (en) 1985-04-22
DE2614550A1 (en) 1977-10-27
CH622818A5 (en) 1981-04-30
JPS603109B2 (en) 1985-01-25
DE2614550C3 (en) 1981-06-25
BR7702070A (en) 1977-11-08
ES457444A1 (en) 1978-03-01
FR2346418B1 (en) 1980-05-09
NL7703274A (en) 1977-10-05
BE853181A (en) 1977-10-03
DE2614550B2 (en) 1980-07-10
CA1087172A (en) 1980-10-07
FR2346418A1 (en) 1977-10-28
IN145278B (en) 1978-09-23

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PE20 Patent expired after termination of 20 years

Effective date: 19970331