GB2055880A - Reactive dyes, their preparation and use - Google Patents
Reactive dyes, their preparation and use Download PDFInfo
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- GB2055880A GB2055880A GB7922415A GB7922415A GB2055880A GB 2055880 A GB2055880 A GB 2055880A GB 7922415 A GB7922415 A GB 7922415A GB 7922415 A GB7922415 A GB 7922415A GB 2055880 A GB2055880 A GB 2055880A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
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Abstract
Reactive dyes of the formula <IMAGE> in which the phenyl radical A can be substituted by C1-4-alkyl, C1-4-alkoxy, halogen, nitro, carboxyl and sulfo and Z is a substituted or unsubstituted amino group.
Description
SPECIFICATION
Reactive dyes, their preparation and use.
The invention relates to reactive dyes of the formula
in which the phenyl radical A can be substituted by C,~4-alkyl, C,~4-alkoxy, halogen, nitro, carboxyl and sulfo and Z is a substituted or unsubstituted amino group.
Suitable substituents on the phenyl radical A are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy, tert.butoxy, fluorine, chlorine, bromine, nitro, carboxyl and sulfo.
The -NH- bridge member which links the benzoyl radical to the amino-fluoro-s-triazine radical is bonded in the meta- or para-position relative to the -CO- group.
Suitable amino groups Z are: -NH2 and alkylamino, N,N-dialkylamino, cycloalkylamino, N,Ndicycloalkylamino, aralkylamino and arylamino groups, amino groups with mixed substituents, such as
N-alkyl-N-cyclohexylamino and N-alkyl-N-arylamino groups, and also amino groups which contain heterocyclic radicals, which can have further fused carboxycyclic rings, and amino groups in which the amino nitrogen atom is a member of a N-heterocyclic ring, which can contain further hetero-atoms.
The abovementioned alkyl radicals can be straight-chain or branched and low-molecular or highermolecular, alkyl radicals having 1 to 6 carbon atoms being preferred; suitable cycloalkyl, aralkyl and aryl radicals are in particular cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; heterocyclic radicals are in particular furan, thiophen, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzthiazole and benzoxazole radicals; and amino groups in which the amino nitrogen atom is a member of a N-heterocyclic ring are preferably radicals of six-membered N-heterocyclic compounds, which can contain nitrogen, oxygen and sulfur as further hetero-atoms.
The abovementioned alkyl, cycloalkyl, aralkyl and aryl radicals, the heterocyclic radicals and the Nheterocyclic rings can be further substituted, for example by: halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C,~4-alkyl, C,~4-alkoxy, acylamino groups, such as acetylamino, amino groups, such as -NH2, methylamino and ethylamino, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.
Examples of the amino radical Z in formula (1) are: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino, ,B-methoxyethylamino, y-methoxypropylamino, p- ethoxyethylamino, N,N-dimethylamino, N,N-diethylamino, N-methyl-N-phenylamino, N-ethyl-Nphenylamino, P-chloroethylamino, P-cyanoethylamino, y-cyanopropylamino, p-carboxyethyiamino, sulfomethylamino, -sulfoethylamino, p-hydroxyethylamino, N,N-di-P-hydroxyethylamino, y-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino and in particular aromatic amino groups, such as phenylamino, toluidino, xylidino, chloroanilino, anisidino, phenetidino, 2-, 3- and 4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3- and 4 carboxyphenyla mi no, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphth- 1 - yl-amino, 3,6-disulfo-naphth-1 -yl-amino, 3,6,8-trisulfo-naphth-1 -yl-amino and 4,6.8-trisulfo-naphth-.
1 -yl-amino.
Preferred reactive dyes of the formula (1) are those in which the phenyl radical A can be substituted by methyl, methoxy, chlorine, carboxyl and sulfo and Z is as defined under formula (1).
Preferred reactive dyes are in particular those of the formula
in which Z is a substituted or unsubstituted amino group.
Preferred reactive dyes of the formula (2) are those in which Z is -NH2, C 14-alkylamino, N,N-di
C,~4-alkylamino, ethanolamino, N,N-diethanolamino, j5-sulfoethylamino, phenylamino, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl, sulfo, acetylamino, ureido and hydroxyl, naphthylamino, which can be substituted by sulfo, or N-methyl-N-phenylamino, N-ethyl-N-phenylamino or morpholino.
Particularly preferred reactive dyes of the formula (2) are those in which Z is phenylamino, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyi and sulfo.
Valuable representatives of this preferred category are the reactive dyes of the formulae
The process for the preparation of reactive dyes of the formula (1 ) comprises reacting a coupling component of the formula
a diazotised diazo component of the formula
2 ,4,6-trifluoro-s-triazine of the formula
and an amine of the formula H-Z (8) with one another in any order.
A coupling component of the formula (5) in which the phenyl radical A can be substituted by methyl, methoxy, chlorine, carboxyl and sulfo is preferably used.
The reactive dyes of the formula (2) are prepared by reacting a coupling component of the formula
a diazotised diazo component of the formula
2,4,6-trifluoro-s-triazine of the formula (7) and an amine of the formula (8) with one another in any order.
In a preferred embodiment, the amine of the formula (8) which is used is ammonia, a alkylamine, a N,N-di-C,~4-alkylamine, ethanolamine, N,N-diethanolamine, taurine, phenylarnine, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl, sulfo, acetylamino, ureido and
hydroxyl, naphthylamine, which can be substituted by sulfo, or N-methyl-N-phenylamine, N-ethyl-N
phenylamine or morpholine.
The amine of the formula (8) which is used is in particular phenylamine, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl and sulfo.
Since the individual process steps indicated above, i.e. diazotization, coupling and a condensation reaction, can be carried out in different orders and some steps can also be carried out simultaneously if desired, various process variants are possible. The starting materials to be used for each partial reaction can be seen from formula (1). In general, the reaction is carried out in successive steps and the order of the simple reactions between the individual reactants of the formulae (5), (6), (7) and (8) can be freely chosen.
The most important process variants comprise 1. coupling a coupling component of the formula (5) with a diazotised diazo component of the formula (6), subjecting the resulting monoazo compound to a condensation reaction with 2,4,6-trifluoro-s-triazine of the formula (7) and subjecting the primary condensation product to a condensation reaction with an amine of the formula (8).
The last two reaction steps can also be carried out in reverse order, by first subjecting 2,4,6trifluoro-s-triazine to a condensation reaction with an amine of the formula (8) and subjecting the resulting primary condensation product to a condensation reaction with the above-mentioned monoazo compound.
2. subjecting a diazo component of the formula (6) to a condensation reaction with 2,4,6-trifluoro-striazine of the formula (7), subjecting the primary condensation product to a condensation reaction with an amine of the formula (8), diazotising the resulting secondary condensation product and coupling the resulting product with a coupling component of the formula (5).
With this prepared variant also, the condensation reaction with the amine of the formula (8) can be carried out as the final reaction step, as under 1.
The preferred procedure for the preparation of the reactive dye of the formula (3) comprises
diazotising 1 -amino-4-acetylaminobenzene-2-sulfonic acid and coupling the resulting product with 1
hydroxy-7-phenylamino-naphthalene-3,6-disulfonic acid, detaching the acetyl group by saponification, subjecting the resulting intermediate of the formula
to a condensation reaction with cyanuric fluoride and subjecting the resulting primary condensation product to a condensation reaction with o-toluidine.
The preferred procedure for the preparation of the reactive dye of the formula (4) comprises diazotising 1-amino-4-acetyiaminobenzene-2-sulfonic acid and coupling the resulting product with 1 hydroxy-7-(3'-sulfophenylamino)-naphthalene-3-sulfonic acid, detaching the acetyl group by saponification, subjecting the resulting intermediate of the formula
to a condensation reaction with cyanuric fluoride and subjecting the resulting primary condensation product to a condensation reaction with o-toluidine.
The preferred procedure for the preparation of the reactive dye of the formula (13) comprises subjecting 4-aminotoluene-3-sulfonic acid to a condensation reaction with cyanuric fluoride, subjecting the primary condensation product to a condensation reaction with p-phenylenediaminesulfonic acid, diazotising the resulting intermediate of the formula
and coupling the resulting product with 1 -hydroxy-7-(3 '-sulfophenylamino)-naphthalene-3-sulfonic acid.
Examples of starting compounds for the preparation of the reactive dyes of the formula (1 ) are: a) Coupling components of the formula (5)
1 -hydroxy-7-phenylamino-naphthalene-3-sulfonic acid, 1 -hydroxy-7-phenylamino-naphthalene- 3,6-disulfonic acid, 1-hydroxy-7-(3'-sulfophenylamino)-naphthalene-3-sulfonic acid, 1 -hydroxy-7-(4'su Ifophenylamino)-naphthalene-3-su Ironic acid, 1 -hydroxy-7-(4'-carboxyphenylamino)-naphthalene 3 sulfonic acid, 1 -hydroxy-7-(4'methylphenylamino)-naphthalene-3 6-disulfonic acid and 1 -hydroxy-7 (4'-methoxyphenylamino)-naphthalene-3,6-disulfonic acid.
b) Diazo components of the formula (6) 1 ,4-Diaminobenzene-2-sulfonic acid, 1 ,4-diaminobenzene-2,5-disulfonic acid and 1,4diaminobenzene-2,6-disulfonic acid; in some cases the diazo component used is preferably not the diaminobenzenesulfonic acid itself but, instead of this, an amino-acylamino-benzenesulfonic acid, for example 4-acetylamino-aniline-2-sulfonic acid, from which the acetyl group is detached by saponification after the coupling reaction has gone to completion and before the further condensation reaction is carried out. Furthermore, it is also possible to use a nitro-amino compound, for example 4nitro-aniline-2-sulfonic acid, as the diazo component of the formula (6) and, after the coupling reaction, to reduce the nitro group to the amino group with sodium sulfide or sodium hydrosulfide.The diazo components of the formula (6) which contain a 3'- or 4'-aminobenzoylamino group are prepared by acylating a diaminobenzenesulfonic acid with a 3'- or 4'-nitrobenzoyl halide, for example 4-nitrobenzoyl chloride, and subsequently reducing the nitro group to the amino group. Further diazo components of the formula (6): 1 -amino-4-acetylaminobenzene-2-sulfonic acid (saponified), 1 -amino-4-nitrobenzene2-sulfonic acid (reduced), 1 -amino-4-(4'-aminobenzoylamino)-benzene-2,5-disulfonic acid, 1-amino 4-(3'-am inobenzoyla mMo )-benzene-2,5-disu Ifon ic acid, 1 -amino-4-(4'nitrobenzoylamino)-benzene-2sulfonic acid (reduced) and 1 -amino-4-3'-nitrobenzoylamino)-benzene-2-sulfonic acid (reduced).
c) 2,4,6-Trifluoro-s-triazine of the formula (7) (cyanuric fluoride) d) Amines of the formula (8) Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, tert.-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, p-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylaminoaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4-methylaniline, o-, mand p-anisidine, o-, m- and p-phenetidine, 2-methoxy-5-methylaniline, 2-ethoxy-5-methoxyaniline, 4bromoaniline, 3-aminobenzamine, 4-aminophenylsulfamide, 3-trifluoromethylaniline, 3- and 4aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-1 -hydroxy-naphthalene, 1 -amino-4- hydroxy-naphthalene, 1-amino-8-hydroxy-naphthalene, 1 -amino-2-hydroxy-naphthalene, 1-amlno-/- hydroxy-naphthalene, orthanilic acid, metanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid, aniline2,5-disulfonic acid, aniline-3,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid, 4aminophenylmethanesulphonic acid, aniline-N-methanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, p-aminosalicylic acid, 1 -amino-4-carboxy-benzene-3-sulfonic acid,
1 -amino-2-carboxybenzene-5-sulfonic acid, 1 -amino-5-carboxybenzene-2-sulfonic acid, 1-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 1 -naphthylamine-2,4-, -2,5-, -2,7-, -2,8-, -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 2-naphthylamine-1 5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- and -6,8-disulfonic acid, 1 -naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8trisulfonic acid, 2-naphthylamine-1 3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, 3- and 4-aminopyridine, 2-aminobenzthiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, morpholine, piperidine and piperazine.
The diazotisation of the diazo components is as a rule effected by the action of nitrous acid in aqueous/mineral acid solution at a low temperature and the coupling reaction with the coupling components is effected at weakly acid or neutral to weakly alkaline pH values.
The condensation reactions of 2,4,6-trifluoro-s-triazine of the formula (7) with the diazo components of the formula (6) and the amino compounds of the formula (8) are preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acid or neutral to weakly alkaline pH value, so that at least one fluorine atom still remains as a detachable radical in the finished reactive dye of the formula (1). Advantageously, hydrogen fluoride liberated during the condensation reaction is neutralized continuously by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.
The reactive dyes of the formula (1) can be isolated and processed to usable, dry dye preparations.
Isolation is preferably effected at temperatures which are as low as possible, by salting out and filtering.
The dyes filtered off can be dried, if desired after adding extenders and/or buffers, for example after adding a mixture of equal parts of monosodium phosphate and disodium phosphate; preferably, drying is carried out at temperatures which are not too high and under reduced pressure. In certain cases the dry preparations according to the invention can be prepared direct, i.e. without intermediate isolation of the dyes, by spray-drying the entire preparation mixture.
The dyes of the formula (1) are fibre-reactive, since they contain a detachable fluorine atom in the s-triazine radical.
Fibre-reactive compounds are to be understood as meaning those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides with the formation of covalent chemical bonds.
The reactive dyes of the formula (1) are novel. They are distinguished by high reactivity and yield dyeings which have good wet fastness properties and good fastness to light. It should be pointed out in particular that the dyes have good solubility and electrolyte solubility coupled with good exhaustion characteristics and high dye fixation and that the non-fixed portions can be removed easily. The dyeings are dischargeable.
The reactive dyes of the formula tEre suitable for dyeing and prTnting very diverse materials, such as silk, leather, wool, high molecular weight polyamide fibres and high molecular weight
polyamide/urethanes, but especially cellulose-containing materials having a fibrous structure, such as
linen, cellulose, regenerated cellulose and in particular cotton. They are suitable both for the exhaustion
process and for dyeing by the pad dyeing method, according to which the goods are impregnated with
aqueous dye solutions, which if desired can also contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, if necessary under the action of heat.
They are also suitable for printing, especially on cotton, but likewise also for printing nitrogen
containing fibres, for example wool, silk or mixed fabrics containing wool.
It is advisable to subject the dyeings and prints to thorough rinsing with cold and hot water, if
necessary with the addition of an agent which acts as a dispersant and promotes the diffusion of the
non-fixed portions.
The preparation of the monoazo intermediates is not described in every case in the illustrative
examples given below, but is obvious from what has been stated above.
In the following examples parts are by weight and temperatures are in degrees centigrade.
EXAMPLE 1
A solution of 1.0 part of cyanuric fluoride in 3 parts of toluene is allowed to run dropwise in the
course of 5 minutes into an ice-cold, neutral solution of 5.94 parts of the dye of the formula
in 200 parts of water and the pH value of the reaction mixture is kept between 6 and 7 by adding 1 N sodium hydroxide solution dropwise at the same time. After the acylation of the amino group has gone to completion, 1.07 parts of o-toluidine are added to the solution of the difluorotriazine dye, the mixture is warmed to 30 to 350 and the pH value of the solution is kept between 7 and 8 by adding 1 N sodium hydroxide solution dropwise. After the reaction has taken place, the aminofluorotriazine dye is salted out by adding 5% by volume of sodium chloride and filtered off.The dye paste is intimately mixed with a saturated aqueous solution of 1.0 part of disodium hydrnqen phosp.hate.and the mixture is dried in - vacuo at 40 to 500.
The dye thus obtained dyes cotton in reddish-tinged brown shades.
Similar dyes are obtained when equivalent amounts of the amines listed below are used in place of o-toluidine.
Example Amines 2 Ammonia 3 Methylamine 4 Ethanolamine 5 Diethanolamine 6 Taurine 7 n-Butylamine 8 Aniline 9 N-Methylaniline 10 - N-Ethylaniline 11 m-Toluidine 12 p-Toluidine 13 m-Chloroaniline 14 p-Chloroaniline 15 o-Anisidine 16 p-Anisidine 17 pçhenetidine 18 p-Aminobenzoic acid 19 Aniline3-sulfonic acid 20 4-Aminoacetanilide 21 3-Aminophenylurea 22 4-Aminophenylurea 23 Diethylamine 24 Morpholine 25 2-Naphthylamine-Gsulfonic acid 26 4-Aminosalicylic acid Example 27
A dye which dyes cotton in violet-tinged brown shades is obtained by reacting 5.94 parts of the dye of the formula
with cyanuric fluoride and o-toluidine in accordance with the instructions of Example 1.
EXAMPLE 28
A dye which dyes cotton in brown shades is obtained by reacting 6.74 parts of the dye of the formula
with cyanuric fluoride and o-toluidine in accordance with the instructions of Example 1.
A similar dye is obtained when the isomer of the formula
is used as the starting material.
EXAMPLE 29
A solution of 5.0 parts of cyanuric fluoride in 7 parts of toluene is allowed to run dropwise in the course of 5 to 10 minutes into an ice-cold solution of 19.35 parts of 4-(4'-aminobenzoylamino)-1 - aminobenzene-2,5-disulfonic acid in 300 parts of water and the pH value of the reaction mixture is kept between 6 and 7 by adding 1 N sodium hydroxide solution dropwise at the same time. After the acylation of one amino group has gone to completion, a neutral solution of 8.65 parts of metanilic acid in 30 parts of water is added to the solution of the primary condensation product, the mixture is warmed to 30 to 350 and the pH value of the solution is kept between 7 and 8 by adding 1 N sodium hydroxide solution dropwise.The solution of the monofluorotrazine compound is cooled to 0 to 5 and diazotised by adding 25 parts of 2 N sodium nitrite solution and 1 5 parts of 10 N hydrochloric acid. The diazo compound thus obtained is then poured into a neutral solution of 19.75 parts of 1 -hydroxy-7-phenylamino-naphthalene-3,6-disulfonic acid in 200 parts of water, to which 33 parts of sodium bicarbonate have also been added before carrying out the coupling reaction.
The dye formed is salted out with 10% by volume of sodium chloride and filtered off. After mixing with a concentrated, aqueous solution of 2 parts of disodium hydrogen phosphate, the dye paste is dried in vacuo at 450.
The dye thus obtained dyes cotton in brown shades.
A similar dye is obtained when 1 -hydroxy-7-(3'-sulfophenylamino)-naphthalene-3-sulfonic acid is used as the coupling component.
EXAMPLE 30
14 parts of cyanuric fluoride are allowed to run dropwise in the course of 10 minutes into an icecold, neutral solution of 26.8 parts of 1 ,4-phenylenediamine-2,5-disulfonic acid in 300 parts of water, the pH value being kept at 6 to 6.5 by adding 2 N sodium hydroxide solution at the same time. A neutral solution of 1 8 parts of metanilic acid in 60 parts of water is then added to the difluorotriazine compound, the temperature of the reaction mixture is allowed to rise to room temperature and the pH value is kept at 6.5 to 7 with 2 N sodium hydroxide solution.
The mixture is cooled to 0" with ice and diazotised with 35 parts of 10 N hydrochloric acid and 25 parts of 4 N sodium nitrite solution. On coupling with 39.5 parts of 1 -hydroxy-7-(3'-sulfophenylamino)- naphthalene-3-sulfonic acid in the presence of sodium bicarbonate, a dye forms which, after isolation, dyes cotton in brown shades.
EXAMPLE 31
10 parts of cyanuric fluoride are added dropwise in the course of 10 minutes to an ice-cold, neutral solution of 1 8.72 parts of 4-aminotoluene-3-sulfonic acid in 300 parts of water, the pH value being kept between 6 and 7 by adding 1 N sodium hydroxide solution at the same time.
The clear solution of the primary condensation product is then allowed to run in the course of about 10 minutes into an ice-cold, neutral solution of 1 8.8 parts of p-phenylenediaminesulfonic acid in 1 50 parts of water and the pH value is kept between 6 and 7 by adding 1 N sodium hydroxide solution dropwise at the same time.
After the condensation reaction has taken place, 100 parts of ice, 25 parts of 4 N sodium nitrite solution and 25 parts of 10 N hydrochloric acid are added to the resulting solution. The diazo compound which is thus obtained is then poured into a neutral suspension of 39.5 parts of m-sulfophenyl-y-acid in 200 parts of water, to which 40 parts of sodium bicarbonate have also been added prior to the coupling reaction.
After the coupling reaction has ended, the dye is salted out with 10% by volume of sodium chloride and filtered off. The dye paste is intimately mixed with a saturated solution of 5 parts of disodium hydrogen phosphate and dried in vacuo at 40 to 500 C.
The dye thus obtained dyes cotton in brown shades.
EXAMPLE 32
5 parts of cyanuric fluoride are added dropwise in the course of about 10 minutes to an ice-cold, neutral solution of 8.65 parts of orthanilic acid in 200 parts of water, the pH value being kept between 6 and 7 by adding 1 N sodium hydroxide solution at the same time. The primary condensation product which is thus obtained is then poured into an ice-cold, neutral suspension of 1 5.35 parts of 1 -amino-4 (3'-aminobenzoylamino)-benzene-2-sulfonic acid in 100 parts of water and during the second condensation reaction the pH value is kept at 7 to 8 by adding 1 N sodium hydroxide solution dropwise.
The diazotisation is then carried out by adding 50 parts of ice, 12.5 parts of 4 N sodium nitrite solution and 12.5 parts of 10 N hydrochloric acid. The diazo compound which is thus obtained is poured into a neutral suspension of 1 9.75 parts of m-sulfophenyl-y-acid in 100 parts of water, to which 10 parts of sodium bicarbonate have also been added prior to the coupling reaction.
After the coupling reaction has taken place, the dye which has precipitated is filtered off and intimately mixed with a saturated aqueous solution of 2.5 parts of disodium hydrogen phosphate and the mixture is dried in vacuo at 40 to 500 C.
The dye which is thus obtained dyes cotton in brown shades.
DYEING EXAMPLE I
2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the resulting solution so that its liquor pick-up is 75% and then dried.
The fabric is then impregnated with a solution which is at 200 and contains, per litre, 5 grams of sodium hydroxide and 300 grams of sodium chloride and squeezed off to a liquor pick-up of 75% and the dyeing is steamed for 30 seconds at 100 to 101 , rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.
DYEING EXAMPLE II
2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.
The solution is added to 1,900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 400 and after 30 minutes 40 parts of calcined sodium carbonate and a further 60 parts of sodium chloride are added. The temperature is kept at 400 for 30 minutes and the dyeing is then rinsed and soaped for 1 5 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.
Claims (24)
1. A reactive dye of the formula
in which the phenyl radical A can be substituted by Ct~4-alkyl, C14-alkoxy, halogen, nitro, carboxyl or sulfo and Z is a substituted or unsubstituted amino group.
2. A reactive dye according to claim 1, in which the phenyl radical A can be substituted by methyl, methoxy, chlorine, carboxyl or sulfo and Z is as defined in claim 1.
3. A reactive dye according to claim 2, of the formula
in which Z is a substituted or unsubstituted amino group.
4. A reactive dye according to claim 3, in which Z is -NH2, C,~4-alkylamino, N, N-di-C 1-4 alkylamino, ethanolamino, N,N-diethanolamino, p-sulfoethylamino, phenylamino, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl, sulfo, acetjrlamino, ureido and hydroxyl, naphthylamind, which can be substituted by sulfo, or N-methyl-N-phenylamino, N-ethyl-N-phenylamino or morpholino.
5. A reactive dye according to claim 4, in which Z is phenylamino, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl or sulfo.
6. The reactive dye according to claim 5, of the formula
7. The reactive dye according to claim 5, of the formula
8. The reactive dye according to claim 5, of the formula
9. A process for the preparation of a reactive dye of the formula (1) according to claim 1, which comprises reacting a coupling component of the formula
a diazotised diazo component of the formula
2,4,6-trifluoro-s-triazine of the formula
and an amine of the formula H (8) with one another in any order.
10. A process according to claim 9, wherein a coupling component of the formula (5) is used in which the phenyl radical A can be substituted by methyl, methoxy, chlorine, carboxyl or sulfo.
11. A process according to claim 10, which comprises reacting a coupling component of the formula
a diazotised diazo component of the formula
2,4,6-trifluoro-s-triazine of the formula (7) and an amine of the formula (8) with one another in any order.
12. A process according to any of Claims 9 to 11, wherein the amine of the formula (8) which is used in ammonia, a C14-alkylamine;a N,N-di-C,~4-alkylamine, ethanolamine, N,N-di-ethanolamine, taurine, phenylamine, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl, sulfo, acetylamino, ureido or hydroxyl, naphthylamine, which can be substituted by sulfo, or N-methyl-Nphenylamine, N-ethyl-N-phenylamine or morpholine.
13. A process according to claim 12, wherein the amine of the formula (8) which is used is phenylamine, which can be substituted by chlorine, methyl, methoxy, ethoxy, carboxyl or sulfo.
14. A process according to claim 13, for the preparation of the reactive dye of the formula
which comprises diazotising 1 -amino-4-acetylaminobenzene-2-sulfonic acid and coupling the resulting product with 1 -hydroxy-7-phenylamino-naphthalene-3,6-disulfonic acid, detaching the acetyl group by saponification. subjecting the resulting intermediate of the formula
to a condensation reaction with cyanuric fluoride and subjecting the resulting primary condensation product to a condensation reaction with o-toluidine.
1 5. A process according to claim 1 3, for the preparation of the reactive dye of the formula
which comprises diazotising 1 -amino-4-acetylaminobenzene-2-sulfonic acid and coupling the resulting product with 1-hydroxy-7-(3t-sulfophenylamino)-naphthalene-3-sulfonic acid, detaching the acetyl group by saponification, subjecting the resulting intermediate of the formula
to a condensation reaction with cyanuric fluoride and subjecting the resulting primary condensation product to a condensation reaction with o-toluidine.
1 6. A process according to claim 1 3, for the preparation of the reactive dye of the formula
which comprises subjecting 4-aminotoluene-3-sulfonic acid to a condensation reaction with cyanuric fluoride, subjecting the primary condensation product to a condensation reaction with p-phenylenediaminesulfonic acid, diazotising the resulting intermediate of the formula
and coupling the resulting product with 1 -hydroxy-7-(3'-sulfophenylamino)-naphthalene-3-sulfonic acid.
1 7. The reactive dyes obtained according to any one of Examples 1 to 32.
1 8. Processes according to any one of Examples 1 to 32.
1 9. The reactive dyes obtainable according to a process as claimed in any of Claims 9 to 1 6.
20. Processes according to either of the dyeing and printing examples.
21. The use of a reactive dye according to any of Claims 1 to 8, or of a rective dye obtained
according to the process of any of Claims 9 to 1 6 for dyeing or printing.
22. A process for dyeing or printing comprising the use of a reactive dye according to Claim 1.
23. A process according to Claim 22, for dyeing cellulose fibres.
24. A dyeing or printing preparation which contains a reactive dye according to Claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7922415A GB2055880B (en) | 1979-06-27 | 1979-06-27 | Reactive dyes their preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7922415A GB2055880B (en) | 1979-06-27 | 1979-06-27 | Reactive dyes their preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2055880A true GB2055880A (en) | 1981-03-11 |
| GB2055880B GB2055880B (en) | 1983-03-23 |
Family
ID=10506143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7922415A Expired GB2055880B (en) | 1979-06-27 | 1979-06-27 | Reactive dyes their preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2055880B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4703111A (en) * | 1985-05-17 | 1987-10-27 | Marcos Segal | Water-soluble compounds containing one or two (nitrophenylamino)-phenylamino-chlorotriazinylamino groups, the nitrophenylamino being additionally substituted by a fiber-reactive group of the vinylsulfonyl series, suitable as dyestuffs |
| US4988803A (en) * | 1987-07-16 | 1991-01-29 | Bayer Aktiengesellschaft | Fiber reactive azo dyes containing a morpholinyl-, piperazinyl- or piperidnyl- substituted flurotriazinyl radical |
| US5097021A (en) * | 1987-09-25 | 1992-03-17 | Bayer Aktiengesellschaft | Reactive dyestuffs where the reactive radical carries a cyclic nitrogen heterocycle |
| US5569748A (en) * | 1993-07-31 | 1996-10-29 | Hoechst Aktiengesellschaft | 2-amino-8-hydroxy-6-sulfonaphtalene-containing monoazo reactive dyes |
-
1979
- 1979-06-27 GB GB7922415A patent/GB2055880B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4703111A (en) * | 1985-05-17 | 1987-10-27 | Marcos Segal | Water-soluble compounds containing one or two (nitrophenylamino)-phenylamino-chlorotriazinylamino groups, the nitrophenylamino being additionally substituted by a fiber-reactive group of the vinylsulfonyl series, suitable as dyestuffs |
| US4988803A (en) * | 1987-07-16 | 1991-01-29 | Bayer Aktiengesellschaft | Fiber reactive azo dyes containing a morpholinyl-, piperazinyl- or piperidnyl- substituted flurotriazinyl radical |
| US5097021A (en) * | 1987-09-25 | 1992-03-17 | Bayer Aktiengesellschaft | Reactive dyestuffs where the reactive radical carries a cyclic nitrogen heterocycle |
| US5569748A (en) * | 1993-07-31 | 1996-10-29 | Hoechst Aktiengesellschaft | 2-amino-8-hydroxy-6-sulfonaphtalene-containing monoazo reactive dyes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2055880B (en) | 1983-03-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |