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US3669951A - Reactive azo dyestuffs containing a-fluoropyimidinyl group - Google Patents
Reactive azo dyestuffs containing a-fluoropyimidinyl group Download PDF
US3669951A
US3669951A US3669951DA US3669951A US 3669951 A US3669951 A US 3669951A US 3669951D A US3669951D A US 3669951DA US 3669951 A US3669951 A US 3669951A
Reactive dyestuffs of the formula
IN WHICH D is the residue of an organic dyestuff, R is hydrogen or a lower alkyl, R1 is hydrogen or a substituent, R2 is hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl radical, carboxylic acid ester radical, carboxylic acid amide radical, alkyl-sulphone, or arylsulphone; and F is fluoro; and process for the preparation of such dyestuffs. These dyestuffs are particularly useful in dyeing materials containing hydroxyl groups and nitrogen, e.g. regenerated cellulose, wool, silk, synthetic polyamide, and polyurethane which dyeings possess excellent fastness to wet processing and good fastness to washing, milling and potting on wool.
United States Patent Bien et a1.
REACTIVE AZO DYESTUFF S CONTAINING A-FLUOROPYIMIDINYL GROUP Inventors: Hans-Samuel Bien, Burscheid; Erich Klauke, Odenthal-Hahnenberg, both of Germany Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany Filed: Sept. 1, 1967 Appl. No.: 664,943
Foreign Application Priority Data Sept. 10, 1966 Germany ..F 50181 March 25, 1967 Germany ..F 51942 References Cited UNITED STATES PATENTS 10/1965 Benz et a1. ..260/146 7/1966 Andrew et a1. ..260/154 [451 June 13, 1972 Primary E.\'aminer-Floyd D. Higel Attorney-Plumley, Tyner & Sandt ABSTRACT Reactive dyestuffs of the formula in which D is the residue of an organic dyestuff, R is hydrogen or a lower alkyl, R is hydrogen or a substituent, R is hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl radical, carboxylic acid ester radical, carboxylic acid amide radical, alkyl-sulphone, or arylsulphone; and F is fluoro; and process for the preparation of such dyestuffs. These dyestuffs are particularly useful in dyeing materials containing hydroxyl groups and nitrogen, e.g. regenerated cellulose, wool, silk, synthetic polyamide, and polyurethane which dyeings possess excellent fastness to wet processing and good fastness to washing, milling and potting on wool.
24 Claims, No Drawings REACTIVE AZO DYESTUFFS CONTAINING A- FLUOROPYIMIDINYL GROUP The present invention relates to valuable new reactive dyestuffs of the general constitution in this formula D denotes the radical of an organic dyestuif, R is hydrogen or a lower alkyl group, R is hydrogen or a substituent, R means hydrogen, halogen, optionally substituted alkyl, alkenyl, aralkyl or aryl radicals or carboxylic acid ester, carboxylic acid amide, alkyl-sulphone and arylsulphone groups, and F is a fluoro substituent.
In the dyestuffs of the general formula (I) the group N(R) is linked directly to a carbon atom of the pyrimidine ring in the 2- or 4-p0sition. On the other side the group N(R) is linked to an aromatic ring of the dyestuff D either directly or via a further bridge member, such as SO or CO-, as in the case of amide groupings, or via an alkylene group, an alkyleneCO--, an arylene, arylene-SO aryleneCO or a triazine or diazine ring or an arylene-amidosulphonyl group. If such further bridge members contain heterocyclic ring systems, as is the case with triazinyl or pyrimidinyl radicals, these too, may contain reactive atoms or groupings, such as halogen atoms or other substituents of which large numbers are known.
Examples of substituents R in the 5-position of the pyrimidine ring are: halogen, such as Cl, Br and F; alkyl radicals, such as Cl-l and C H substituted alkyl radicals, such as mono, dior trichloroor tribromomethyl, trifluoromethyl radicals; alkenyl radicals, such as vinyl or halovinyl and allyl radicals; NO CN, carboxylic acid, carboxylic acid ester and optionally N-substituted carboxylic acid or sulphonic acid amide groups, sulphonic acid and sulphonic acid ester groups, alkyl sulphonyl, aralkylsulphonyl or arylsulphonyl radicals.
Suitable substituents R in the 6-position of the pyrimidine ring are, for example, halogen, such as Cl, Br and F; alkyl, such as methyl and ethyl radicals; alkenyl, such as vinyl, halovinyl and allyl radicals; and substituted alkyl radicals, such as mono-, dior trichloroor bromo-methyl or trifluoromethyl radicals; carboxylic acid esters, such as the methyl and ethyl esters; carboxylic acid amide groups including the N-substitution products; alkylsulphonyl and arylsulphonyl radicals, such as CH SO C H SO C H SO and pCIC H SO Dyestuffs in which R and R denote hydrogen, halogen and/or alkyl radicals, belong to a preferred group of the compounds according to the invention.
The new dyestuffs may contain the radical once or several times in the molecule. Dyestuffs with l to 2 reactive radicals of this type are preferred for economic reasons.
Suitable pyrimidine rings which contain at least one (reactive) fluoro substituent which can be split off are, for example: 2-fluoro-4-pyrimidinyl-, 2,6-difluoro-4-pyrimidinyl, 2,6-difluor0-5-chloro-4- pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6- difluoro-Smethyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4- pyrimidinyl, 2-fluoro-5methyl-6-chloro-4-pyrimidinyl, 2- fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4- pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2flu0ro-5- methyl-4-pyrimidinyl, 2,5,6-tri-fluoro-4-pyrimidinyl, 5- chloro-6-chloromethyl-2fluoro-4-pyrimidinyl, 2,6-difluor0-5- bromo-4-pyrimidinyl, 2-fluoro-5bromo-6-methyl-4-pyrimidinyl, 2-flu0ro-5brom0-6chloromethyl-4-pyrimidinyl, 2,6- difluoro-Schloromethyl4-pyrimidinyl, 2,6-difluoro-5-nitro-4 pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5- chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5chloro-4-pyrimidinyl, 2fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5- chloro-Z-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2fluoro-4- pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluor0-5- trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-methylsulphonyl-4- pyrimidinyl, 2-fluoro5-phenyl-4-pyrimidinyl, Z-fluoro-S-carbonamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4- pyrimidinyl, 2-fluoro-5bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro6-phenyl-4-pyrimidinyl, 2- fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulphonyl-4-pyrimidinyl, 2-fluoro-5sulphonamido-4-pyrimidinyl, 2- fluoro-5-chloro-6carbomethoxy-4-pyrimidinyl, 2,6-difluoro- 5trifluoromethyl-4-pyrimidinyl.
Among the many possibilities of attaching the radical (II) to D, the direct linkage of the groups N(R) to a carbon atom of a carbocyclic ring of D is preferred. Suitable bridge members of this or another kind, with the inclusion of the group -N( R), are, for example (A standing for the radical of the formula III): NHA, N(CHQ-A, N(C H )A, N(C H A, CONH-A, SO Nl-l-A, CON(CH )A, SO N(CH A as well as the corresponding N-ethyland N- propylamides, HN-CONHA, HNCH CO- Nl-l-A, N(CH )-CH CONHA, HNCH CH NH-A NH-SO (CH NHA, NHCO- (Cl-l Nl-lA, CH NH-CO(CH NHA,
OCH2( (SOaHhm, /1 0,2
as well as the corresponding N-alkyl( 1-5 C)-amides or amines c o Nil-A.
as well as the corresponding N alkyl( 1-3 C)-amides or -amines of the aforesaid compounds.
The new dyestuffs can belong to the most varied classes, for example, to the series of metal-free or metal-containing monoor polyazo dyestuffs; metal-free or metal-containing azaporphin dyestuffs, such as copperor nickel-phthalocyanine dyestuffs; anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone and dibenzanthrone dyestuffs; and of the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzathrone compounds. Within the scope of these classes of dyestuffs, dyestufis of the following general constitutions are particularly valuable, inter alia:
in which E and E represent aromatic, carbocyclic or heterocyclic radicals and, in particular, B is the radical of a carbocyclic diazo component of the benzene or naphthalene series and E is the radical of an enolic or phenolic coupling component, eg a S-pyrazolone, 5- amino-pyrazole, acetoacetic acid arylamide, hydroxynaphthalene or aminonaphthalene; B and E may otherwise contain any substituents customary in azo dyestuffs, including further azo groups; R stands for a CH group or, preferably for a hydrogen atom, and R and R,, independently of one another, stand for hydrogen or halogen groups, such as Cl, Br or F.
Important azo dyestuffs are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-l-phenyl-S- pyrazolone series, the benzcne-azo-aminonaphthalene series, the naphthalene-azo-naphthalene-series, the naphthalene-azol-phenyl-pyrazolone-S series and the stilbene-azo-benzene series, the dyestuffs which contain sulphonic acid groups being again preferred. 1n the case of metal complex azo dyestuffs, the groups attached to the metal complex are preferably in the o-position to the azo group, for example, in the form of 0,0- dihydroxy-, o-hydroxy-o-carboxy-, o-carboxy-d-aminoand o-hydroxy-o-aminoazo groupings. Particularly eminent types of monoazo dyestuffs of the kind obtainable according to the invention are illustrated by the following formulas:
r w om (Soa lm (Vll (Vlll) h h-z SH; (or NlI-alkyl) SOQH HO g y 'm or! wiA/X (SOEHHHM (X1 }(o) denotes that the stated radicals stand in the adjacent (0) position to each other; A stands for the radical of the formula in which R, and R have the same meaning as above;
or in other words, A stands for a 2-fluoropyrimidine-4-yl ring containing a radical R in the 5-position and a radical R in the 6-position, or A stands for a 4-fluoropyrirnidine-2-yl ring containing a radical R, in the 5-position and a radical R in the 6-position; acyl stands for an acyl radical, in particular a lower aliphatic carbonyl or sulphonyl residue having one to five carbon atoms or an aryl carbonyl or aryl sulphonyl residue of the benzene and substituted benzene series; the nuclei drawn with dotted lines indicate that these nuclei may be present or absent.
2. Anthraquinone dyestuffs o Rm in which L and L denote substituents, especially sulphonic acid groups, p denotes an integer from O to 2, R" is a methyl or ethyl group or hydrogen, R and R' independently of one another, are hydrogen or halogen radicals. 3. Phthalocyanine dyestuffs in this formula Pc stands for the radical of a nickelor copper-phthalocyanine, L and L are substituents, especially sulphonic acid groups, r denotes an integer from to 2, q is the number 0 or 1, R is a methyl group or, preferably, hydrogen, R and R' independently of one another, are hydrogen or halogen radicals. The phthalocyanine radical Pc preferably carries as further substituents l 2 sulphonic acid and/or 1 2 sulphonic acid amide groups, such as SO Nl-l SO N-a1kyl, SO N(alkyl) and SO NH(aryl) groups, alkyl" standing for alkyl radicals with one three carbon atoms.
The above compilation of a selection of suitable azo, anthraquinone and azaporphin dyestuffs and of fluoro-substituted pyrimidine rings does not represent a limitation of the general formulas, either with regard to the preparative possibilities of producing such dyestuffs within the scope of the general formula (I), or with regard to the valuable properties of these products in respect of application techniques. The new dyestuffs may otherwise contain any substituents custo mary in dyestuffs, such as sulphonic acid, carboxylic acid groups; sulphonamide and carbonamide groups which may be further substituted on the nitrogen atom of the amide; sulphonic acid ester and carboxylic acid ester groups; alkyl, aralkyl and aryl radicals; alkylamino, aralkylamino, arylamino, acylamino, nitro and cyano groups; halogen atoms such as Cl, Br and F; hydroxy, alkoxy, thioether, azo groupings and the like. The dyestuffs may also contain further groupings capable of fixation, such as monoor dihalo-tn'azinylamino, mono-, dior trihalo-pyrimidinylamino, 2,3-dihalo-quinoxaline-6-carbonyl or -6-sulphonylamino, 1 ,4-dihalophthalazine--carbonylor -6- sulphonylamino, Z-haloor 2- alkylsulphonylor 2-arylsulphonyl-benzothiazole-S-carbonylor -sulphonylamino, alkylsulphonyl-pyrimidinyl, arylsulphonyl-pyrimidinyl, esterified sulphonic acid hydroxy alkylamide and hydroxy alkylsulphone groups, sulphofluoride-, haloalkylamino, acryloylarnino, haloacylamino groups or other reactive groups.
The new dyestufis of the formula (I) are obtained by introducing into dyestuffs or dyestuff intermediates, by known methods at least one fluoro-substituted pyrimidine ring linked via an amino group N(R)--. If dyestuff intermediates are used, these are then converted into the desired final dyestuffs in known manner, particularly by a diazotizing, and/or coupling and/or condensing reaction; in the formula (III) R, denotes hydrogen or a substituent and R means hydrogen, halogen, optionally substituted alkyl, alkenyl, aralkyl or aryl radicals, carboxylic acid ester, carboxylic acid amide, alkylsulphone or an arylsulphone group; F stands for a fluorine atom.
(III) The introduction into dyestuffs or dyestuff intermediates, of the radical (111) via an amino group N(R) can be carried out by various methods of preparation. For example, dyestuffs or dyestuff intermediates which contain amino or amide groups and exhibit a reactive hydrogen atom on the nitrogen atom of the amine or amide, can be reacted with compounds of the general formula I X R1 (\N RzlN in which R, and R have the same meaning as above, F stands for a fluoro substituent and X for a radical which can be split off as an anion,
to form dyestuffs of the general formula (I), and, if dyestuff intermediates are used, these can then be converted into the desired final dyestufis in a suitable manner. Among the reactive substituents X which can be split off as anionic radicals, the fluoro substituent is of particular interest. Other radicals which can be split off as anions and are suitable according to circumstances are, for example quaternary ammonium groups, such as -N(CH,-,) and -N( C 14,,
l-leterocyclic pyrimidine compounds of the formula (XIII) which are suitable for the reaction are, for example: 2,4- difluoropyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6- difluoro4-methyl-S-chloropyrimidine, 2,4,6- trifluoropyrimidine, 2,4-difluoropyrimidine-S-ethylsulphone, 2,6-difluoro-4-chloro-pyrimidine, 2,4,5 ,6- tetrafluoropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,6-difluoro-4-methyl-5-bromopyrimidine, 2,4-difluoro-5,6- dichloroor -dibromopyrimidine, 4,6-difluoro-2,5-dichloro- (XIII) or dibromopyrimidine, 2,6-difluoro-4-bromopyrimidine, 2 ,4,6-trifluoro5-bromopyrimidine, 2,4,6-trifluoro-5- chloromethylpyrimidine, 2,4,6-trifluoro5-nitropyrimidine 2,4,6-trifluoro-5-cyanopyrimidine, 2,4,6-trifluoropyrimidine- S-carboxylic acid alkyl esters or -5-carboxylic acid amides, 2,6-difluoro-5-methyl-4-chloropyrimidine, 2,6-difluoro-5- chloropyrimidine, 2,4,6-trifluoro-5-methylpyrimidine, 2,4,5- trifluoro-o-methylpyrimidine, 2,4-difluoro-5-nitro-6- chloropyrimidine, 2,4-difluoro-S-cyanopyrimidine, 2,4- difluoro-S-methyl-pyrimidine, 6-trifluorornethyl-5-chloro-2,4- difluoro-pyrimidine, 6-phenyl-2,4-difluoropyrimidine, 6- trifluoromethyl-2,4-difluoropyrimidine, S-trifluoromethyl- 2,4,6-trifluoropyrimidine, 5-trifluoromethyl-2,4- difluoropyrimidine, 2,4-difluoro-S-nitropyrimidine, 2,4- difluoro-S-trifluoromethyl-pyrimidine, 2,4-difluoro-5-methylsulphonyl-pyrimidine, 2,4-difluoro-5-phenylpyrimidine, 2,4- difluoro-S-carbonamido-pyrimidine, 2,4-difluoro-5-carbomethoxy-pyrimidine, 2,4-difluoro-6-trifluoromethylpyrimidine, 2,4-difluoro-5-bromo-6-trifluoromethylpyrimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4- difluoro-6-carbomethoxy-pyrimidine, 2,4-difluoro-6-phenylpyrimidine, 2,4-difluoro-6-cyanopyrimidine, 2,4,6-trifluoro-5- methylsulphonyl-pyrimidine, 2,4-difluoro-5-chloro6-carbomethoxy-pyrimidine, 2,4-difluoro-5-sulphonamidopyrimidine.
In the condensation reaction with the dyestuffs or dyestuff intermediates containing amino or amide groups, these pyrimidine derivatives can be assumed to react in the 4-position, the radical X being split off. In the general formulas (I), (II) and (1V) to (XII) the pyrimidine ring is therefore presumably and preferably attached via the 4-position to the radical of the dyestufi containing the N(R)- or N(R' )-group.
The fluoro-pyrimidine compounds mentioned above and others which can be used according to the invention are generally readily obtained by reacting the corresponding chloro or bromo compounds with alkali metal fluorides, for example, with potassium fluoride, NaHF- K50 1", SOF AgF or by reacting corresponding OH compounds with SP COF COClF or cyanuric fluoride, or by heating corresponding diazonium tetrafluoroborates.
Particularly preferred for the reaction according to the invention are those reactive components which correspond to the formula A Y R l L N F R 2 N (XIV) in which R and R independently of one another, denote hydrogen or halogen radicals (Cl, Br of F), and Y is a radical which can be split off as an anion, particularly a fluoro substituent.
The reaction of the dyestuffs or dyestuff intennediates containing amino or amide groups with heterocyclic compounds of the formula (XIII) is carried out in accordance with the type of starting compounds used in an organic, aqueous-organic or aqueous medium at temperatures of l C. to 100 C., preferably at 0 to 50 C, in the presence of alkaline condensation agents, such as aqueous alkali metal carbonate or alkali metal hydroxide solutions.
If dyestuff intermediates are used, the condensation products obtained are converted in usual manner into the desired final dyestuffs. This process is primarily interesting for the preparation of azo dyestuffs in that, for example, a diazo and/or coupling component containing a reactive amino or amide group, is first reacted with the reactive component (X- III) or (XIV) and the resultant intermediate subsequently converted by diazotization and/or coupling and/or condensation into an azo dyestuff. In the latter further conversion reactions as are customary in azo dyestufis can subsequently be carried out, for example, acylating, condensing, reducing and metallizing reactions.
Also when preparing other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (XIII) or (XIV) can first be performed with an intermediate, for example, with m-phenylene-diamine or an m-phenylene-diamine-sulphonic acid, and the reaction product obtained can subsequently be further condensed with an anthra-quinone-sulphonic acid halide or with a copperor nickel-phthalocyanine-sulphonic acid halide to form a reactive phthalocyanine dyestuff.
Another variant for the preparation of the new dyestuffs of the formula (I) which is applicable in some cases consists in that in dyestuffs or, in particular, in dyestuff intermediates which contain at least one group of the general formula l R L N (XV) in which R, R, and R have the same meaning as above and Z represents a radical which can be split off as anion, with the exception of a fluoro substituent, Z is exchanged in known manner for a fluoro substituent and, if dyestuff intermediates are used, these are subsequently converted into the desired final dyestuffs. The exchange of one or more substituents Z which can be split off as anions, for example, of Clor Br-atoms, for fluoro substituents can be carried out, for example, in the manner already explained.
As has already been mentioned for some cases, the dyestuffs obtainable by the various methods described above can be subjected to further reactions which are customary for dyestuffs in that, for example, metallizable dyestuffs are treated with metal-yielding agents, especially with chromium, cobalt, copper or nickel salts; dyestuffs containing reducible groups, especially nitro groups, are reduced; dyestuffs containing acylatable groups, especially acylatable amino groups, are acylated; or dyestuffs are subsequently treated with sulphonuting agents, such as chlorosulphonic acid, oleum or SO in chlorinated hydrocarbons, in order to introduce (further) sulphonic acid groups into the products, The lastmentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs. Dyestuffs of the formula (I) which contain sulphonic acid and/or carboxylic acid groups are preferred within the scope of the present invention.
Depending upon the number of reactiveHNR-groupings suitable for the conversion reaction which are present in the dyestuff radical or dyestuff intermediates, one or more groupings of the general formula (II) can be incorporated with the dyestuffs. In the majority of cases the number m 4 will not be exceeded, but it is also possible to aynthetize dyestuffs, especially those of a higher molecular structure, with more than 4, e.g. with up to eight groupings of the formula ll If the dyestuffs produced according to process contain groups forming metal complexes, these can be converted into their metal complex compounds by the action of metal-yielding agents, for example, of copper, nickel, chromium or cobalt salts. They can also be subjected to other conventional conversion reactions, such as diazotizing, coupling acylating and condensing reactions.
The reaction of dyestuffs containing amino groups with reactive components of the formula (XIII) or (XIV) yields groups of particularly preferred dyestuffs, if those amino group-containing starting dyestuffs are used, from which the dyestuffs of the formulas (IV) to (XII) are derived, Le. those containing the grouping N(R')-H or -N( R" )-I-l, instead or the group N(R )A.
In the production of phthalocyaninc dyestuffs it is possible to prepare first a diaminoaryl compound which is mono-condensed with the reaction component (XIII) or (XIV) and subsequently to condense this with, preferably, copperor nickelphthalocyanine-sulphonic acid halides; other amino compounds, such as ammonia, aliphatic amino compounds and/or aromatic amino compounds may be added simultaneously or subsequently. In this Way, there are obtained phtha]ocyanine-, preferably copperor nickel-phthalocyanine-sulphonarnide dyestufis which contain a certain proportion of sulphonarylamide groups carrying the reactive group and, in addition, a certain proportion of non-reactive sulphonamide groups and/or free sulphonic acid groups. Likewise, copperor nickel-phthalocyanine-sulphonic acid-(aminoaryl)-amides which may contain additional, optionally N-substituted sulphonamide groups of different type and free sulphonic acid groups, can be condensed on the amino group of the aminoaryl radical with reactive components (XIII) or (XIV) to form the new dyestuffs (I).
The new dyestuffs are extremely valuable products which are suitable for a great variety of applications. As water-soluble compounds they are primarily of interest for the dyeing of textile materials containing hydroxyl groups and containing nitrogen, especially textile materials of natural and regenerated cellulose, and also of wool, silk, synthetic polyamide and polyurethane fibers. Due to the reactive fluoro substituent or substituents in the pyrimidine ring, the products are particularly well suited as reactive dyestuffs for the dyeing of cellulose materials by the methods which have recently become known for this purpose. The fastness properties obtained, especially the fastness to wet processing, are excellent.
For dyeing cellulose, the dyestuffs are preferably used in an aqueous solution to which compounds of alkaline reaction, such as alkali metal hydroxide or alkali metal carbonate, or compounds which can be converted into substances of alkaline reaction, such as alkali metal bicarbonate, Cl C COONa, can be added. Further auxiliaries may be added to the solution, but these should not react with the dyestufis in an undesirable manner. Additives of this kind are, for example surface-active substances, such as alkylsulphates; substances preventing the migration of the dyestufi; dyeing auxiliaries such as urea; or inert thickening agents, such as oil-in-water emulsions, tragacanth, starch, alginate or methyl cellulose.
The solutions or pastes thus prepared are applied to the material to be dyed, for example, by padding on a foulard (short bath) or by printing, followed by heating for some time at an elevated temperature, preferably 40 to 150 C. Heating can be carried out in a hot flue, in a steaming apparatus, on heated rollers or by introducing the material into heated concentrated salt baths, alone or successively in any sequence.
If a padding liquor or dyebath without alkali is used, the dry material is subsequently passed through a solution of alkaline reaction to which common salt or Glaubers salt has been added. The addition of salt prevents the dyestufi from migrating from the fiber.
For dyeing from a long bath, the material is introduced into an aqueous solution of the dyestuff (liquor ratio l to l 40) at room temperature and dyeing is carried out for 40 to 90 minutes, possibly with an increase of temperature up to 20 90 C., preferably 30 50 C., while adding portions of salt, for example, sodium sulphate, and subsequently of alkali, for example, sodium phosphates, sodium carbonate, NaOH or KOl-I. The chemical reaction between the dyestuff and the fibers takes place during this operation. After chemical fixation, the dyed material is rinsed hot and finally soaped, whereby unfixed residues of the dyestuff are removed. Dyeings of excellent fastness, especially fastness to wet processing and light, are obtained.
In the so called cold batch padding process, the subsequent heating of the padded fabric can be saved by storing the fabric at room temperature for some time, for example 2 to 20 hours. In this process there is used a stronger alkali than in the dyeing process from a long bath described above.
Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers, are generally dyed by the dyeing methods customarily used for this purpose in the acid to neutral range, a final increase of the pH value of the dye bath, for example, to pH 6.5 to pH 8.5, being sometimes of advantage.
For example, the dyestuffs are applied to synthetic polyamide fabrics as solutions or, preferably, in dispersed form and subsequently after-treated, optionally together with (preferably smaller amounts) of acid-binding agents, such as sodium carbonate. Particularly advantageous results are achieved with those dyestuffs which are insoluble or only sparingly soluble in water. These are worked up by usual methods and with the addition of the known auxiliaries to form a dyestuff dispersion and are applied in this form in the dye bath and/or padding liquor or in a printing paste. Auxiliaries suitable for this application are, inter alia, compounds which prevent the migration of the dyestufi on the fiber, such as cellulose ethers, alkali metal chlorides and sulphates; wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols; solvents, such as thiodiglycol; and also thickening agents, such as starch, tragacanth, alginate thickening, gum arabic etc.
The after-treatment of the dyeings, impregnations and prints obtained on fabrics of polyamide fibers is preferably carried out at a temperature of 50 to C. for 5 to 60 minutes. In the case where the dyestuffs used contain groupings forming metal complexes, the fastness properties of the dyeings can again sometimes be improved with metalyielding agents, such as copper salts, for example, copper sulphate, or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.
The dyeings which can be obtained with the new dyestuffs are generally characterized by good to very good fastness properties, especially by excellent fastness to wet processing.
Compared with the constitutionally most closely related known reactive dyestuffs containing chloroor bromopyrimidinylamino groups, as are described, for example, in Belgian Patent specifications Nos. 572,973; 573,299 and 578,742, the new products of the formula (I) have essential advantages with regard to application techniques. In comparison with the most closely related trichloropyrimidinyl dyestuffs for example, the new dyestuffs which contain a 2,6- difluoro-S-chloro-pyrimidinylamino or a 2-fluor0-5,6- dichloro-pyrimidinylamino radical, surprisingly, give a better dyestuif yield on cotton and regenerated fibers and are superior with regard to color depth when dyed from a long bath. In contrast to the known chloropyrimidine reactive dyestuffs, the new fluoropyrimidine reactive dyestuffs are also well suited for the so-called cold batch padding process for cotton and regenerated fibers. In the printing process the new dyestufis can be used for rapid fixation. The bond between the fiber and the dyestuffs in an alkaline medium is frequently stronger than with the known dyestuffs.
The new fluoropyrimidine reactive dyestufi's are also superior to the known chloropyrimidine dyestufis in that they yield valuable dyeings of good fastness to washing, milling and potting on wool. Dyeings which are fast to wet processing can also be obtained on silk and synthetic superpolyamide and polyurethane fibers.
EXAMPLE 1 To a solution of 34.7 parts of the sodium salt of 2- aminonaphthalene-4,8-disulphonic acid and 7 parts sodium nitrite in 300 parts of water there are added 28 parts by volume of concentrated hydrochloric acid, while cooling with ice, and the mixture is stirred at 0 10 C. for one-half hour. After removing the excess nitrous acid, 10.7 parts 3-aminotoluene dissolved in 10 parts of concentrated hydrochloric acid and 150 parts of water are added and the coupling is completed by neutralizing the mixture to pH 3 5. The resultant aminoazo dyestuff is salted out, filtered off with suction, washed and then redissolved at pH 7 to parts of water and 200 parts acetone with the addition of a sodium hydroxide solution. 19.2 Parts 2,4,6-trifluoro-5-chloropyrimidine are added dropwise to this solution at 20 30 C. and a pH of 5.5 6 is maintained by means of a 2N sodium carbonate solution. When the reaction is completed, the resultant dyestuff of the presumable formula needles is filtered off with suction, washed with a 2 percent sodium chloride solution and dried in a vacuum at 50 C.
When a cellulose fabric is printed with a printing paste which contains, per kilogram, 15 g of the dyestuff, 100 g urea, 300 ml of water, 500 g of alginate thickening (60 g sodium alginate per kg of thickening) and 20 g sodium carbonate, and which has been made up with water to l kilogram, the fabric is then dried, steamed at 105 C. for 1 minute, rinsed with hot water and soaped at the boil, an intense reddish yellow print of good fastness to washing and light is obtained.
(prepared according to the instructions of German Patent Specification No. 1,117,235 by coupling diazotized 1 mino-8- (benzene-sulphonyloxy)-naphthalene-disulphonic acid-( 3 ,6) in a soda-alkaline medium with the equivalent amount of 2- acetyl-arnino- -hydroxynaphthalene-disulphonic acid-(4,8), conversion of the monoazo compound into the copper complex by oxidative coppering, and hydrolysis of the acetyl and benzene-sulphonyl groups) are dissolved at pH 6 6.5 in 2,500 parts by volume of water at 60 65 C. and mixed at 20 30 C. with 0.12 mole 2,4,6-trillluoro-5- chloropyrimidine.
A pH of 6 6.5 is maintained during the condensation by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out and isolated. When dried, the dyestuff is a dark powder which dissolves in water to give a blue color.
One hundred parts by weight of a cotton fabric are treated on the foulard at room temperature with an aqueous solution containing 2 percent of the dyestuff, g/liter of sodium hydrogen carbonate and 150 g/liter of urea, subjected to intermediate drying, heated at 140 C. for 2 minutes, then rinsed and soaped at the boil. The fabric is dyed in very clear blue shades fast to wet processing.
EXAMPLE 3 Forty six parts of the monoazo dyestuff obtained in analogy with Example 1 by coupling diazotized 2-aminonaphthalene- 4,8-disulphonic acid with S-methylamino-toluene are dissolved at C. in 400 parts of water and lOO parts acetone, and 20 parts 2,4,6-trifluoro-5-chloropyrimidine are added dropwise while maintaining a pH of 6 7 by means of a 2N sodium carbonate solution; the condensation is continued until a sample no longer exhibits a change of color when acidified. The resultant dyestuff which has the presumable formula is salted out, filtered off with suction, washed and dried at 30 C. in a vacuum.
A cotton fabric is impregnated with a solution at 20 25 C, which contains, per liter of liquor, 20 g of the above dyestuff and 0.5 g of a non-ionic wetting agent (e.g. a polyhydroxyethylated oleyl alcohol) as well as 150 g urea and I5 g sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to n moisture content of about 100 percent. Alter nu intcrmctlintc drying at 50 60 C, the fabric is lientcd nt I" t. for 2 minutes, the dyeing so obtained is thoroughly rinsed with hot WillCl" and treated at the boil for 20 minutes with a solution containing, per liter, 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, there is obtained an intense reddish yellow dyeing of good fastness to wet processing, rubbing and light.
In the following Table there are listed the diazo components, coupling components and reactive components linkable to the amino group, from which dyestuffs can be synthetized in analogy with the instructions given in Example I 3, the shades obtained by one of the methods of application described above being likewise stated in the Table.
Abbreviations for the reactive A 2,4,6-trifluoro-5- chloropyrimidine components:
B 2,4,6-trifluoropyrimidine React- Ex. Diazo Coupling ive Shade No. Component Component Component 4 Z-aminonaphthalenel-amino- 4,8-disulphonic acid Z-methoxy-S- A yellow methylbenzene 5 8 yellow 6 l-aminonaphthalenel-amino-3-methylA yellow 3,6-disulphonic acid -benzene 7 B yellow 8 Z-aminonaphthalenel-arnino-3-methylA yellow 5,7-disulphonic acid -benzene 9 B yellow 10 Z-aminonaphthalenel-amino-3-methylA yellow 6,8-disulphonic acid -benzene l l B yellow 12 4-arninoazobenzenel-amino-3-methylA brown- 3,4'-disulphonic acid -benzene yellow 1 3 l-aminobenzene 4sul l-amino-3-methylB brown- -phonic acid l- -benzene yellow aminonaphthalene-6- sulphonic acid 14 2-( 3 '-sulpho-4'- A yellow aminophenyl)-6- methylbenzothiazole- 7-sulphonic acid 1 5 Z-aminonaphthalenel -methylamino-3-B yellow 4,8-disulphonic acid methoxybenzene l6 l-amino-3-acetyl A yellow -aminobenzene l7 aniline A yellow EXAMPLE 18 To a solution of 36.5 parts of the sodium salt of l-amino-B- hydroxynaphthalene-3,o-disulphonic acid in 200 parts of water there are added dropwise at 8 10 C. 20 parts 2,4,6- trifluoro-S-chloropyrirnidine, and a pH of 5.5 6 is maintained by continuous neutralization of the liberated hydrogen fluoride. The reaction is observed by chromatography. The resultant solution of the dyestuff intermediate is poured into 900 parts of water and coupled at a pH of 7 8 and at 0 5 C. with 17.5 parts of diazotized 2- aminobenzene-sulphonic acid dissolved in 200 parts of water. The product is salted out at a final pH of 6.5 with parts sodium chloride, filtered off with suction and washed with a 10 percent sodium chloride solution. Drying is carried out in a vacuum at 30 40 C. The dyestuff forms red small needles.
When a fabric of cotton or regenerated cellulose is dyed or printed with this dyestuff according to one of the processes described in Example I 3, clear bluish red dyeings and prints of good fustncss to wet processing, rubbing and light are obtuined.
Fifty g of a cotton skein are dyed in 1 liter of a dyebath containing 1.5 g of the above dyestuff by adding 50 g sodium chloride in several portions at 20 to 30 C. within 30 minutes, subsequently adding 20 g sodium carbonate and treating the material at the same temperature for 60 minutes. After rinsing, soaping at the boil and drying, a bluish red dyeing of good fastness to wet processing, rubbing and light is obtained.
In the following Table there are listed the shades of further dyestuffs which are synthetized from the likewise specified diazo components, coupling components and reactive components linkable to the amino group in the latter, in analogy with the instructions given in Example 18 or also by reacting the corresponding aminoazo dyestuff with the reactive components, and which can be dyed or printed on to cellulose materials by one of the methods described above:
Abbreviations for reactive components as in Table of Example 27 l-aminobenzenenaphthalene-7- sulphonic acid EXAMPLE 30 To a solution of 21 parts of the sodium salt of 1,3- diaminobenzene-6-sulphonic acid in 100 parts of water there are added with good stirring 20.0 parts 2,4,6-trifluoro-5- chloropyrimidine and the mixture is stirred at 30 C., while continuously neutralizing the liberated hydrofluoric acid React- 20 to pH 6 7, until a sample which is diazotized and coupled DlaZO Coupllng We Shade with l-hydroxynaphthalene-4-sulphonic acid yields a clear component component yellowish red coloration. The resultant dyestuff intermediate is directly diazotized, after the addition of ice, with 7 parts sodium nitrite and 28 parts of concentrated hydrochloric acid 19 l-aminobenzene-Z- l-aminoand subse uentl combined with a reviousl re ared solusulphonic acid 8-hydroxy- 8 red f f th 5 f 1 p 8 naphthalene 3'6 tion 0 p o e lum s 0 enzoy -aminodisulphonic acid hydroxynaphthalene-3,6-disulphomc acid and 12 parts sodi- 2O amimbenlene urn carbonate in 200 parts of water, whereby coupling takes Pg alzff A red place to give the dyestuff of the formula I SO Na HO NH-o C-CuH', disulphomc acid I 21 8 red 22 l-amino-2-carboxyl-arninobenzene-4-sulphonic B-hydroxy- A red N 1 acid naphthalene-3,6- Naoas SOBNa disulphonic acid 23 l-amino-4-methyl- A red benzene-2sulphonic 1 acid 24 l-arnino-3-acetyl- 8 red which is salted out, filtered off with suction, washed and dried l at 30 C. in a vacuum. The dyestuff readily dissolves in sulphonic acid 40 25 1 water to give a red color and yields on cellulose materials by (2'-[4"-sulpho- A red one of the processes described above clear bluish red dyeings p y l' and prints. gli xgigi szg ij In the following Table there are listed the shades and the pH h i acid value of the coupling medium of dyestuffs which are prepared 26 l-amino benz n -2- 2- A ng in analogy with the instructions of Example 30 from a diazo sulphomc and ig z igl g 7 component containing a further, preferably acylatable amino sulghonic acid group, from a coupling component and from a reactive com- 26a l-amino-3-(2'-[4"- Z-amino- A orange ponent linkable with the diazo component. The methods f yl l- 7 described above can be used for dyeing and printing cellulose f;: ,g9: 23 materials with the dyestufls of the Table. )-aminc:be nzene-6- Abbreviations for reactive components as in Table of Examsulphonic acid ple 3 Reactive [ill of Example compocoupling N0. Diaxo component Coupling component nent medium Shade 31 1.3-dimninobeuzonol-mninonaphthaleuo-SJ-disulphouic acid it +5 ()l'aligv.
-l-sulpl10ni dt'lll.
32 7 d0 Q-aminonuphtlmlene3, 6disulphonic acid A i '5 D0.
33 ,do 'l--.iminonnplltlinleno-ti-sulphonit-acid A l v B 4 5 l)o 3t. .do l V V ZN-mothylmnino-8-hydroxy1iaphtlialeno-dsulphoiu aticl A +5 Ul'dngv.
disulpllouic old.
disulpllouiv nvid.
1s EXAMPLE 47 51.6 Parts of the dyestuff of the formula l i N=N NaOgS JNII:
dOgNa is salted out, pressed off, washed and dried in a vacuum at 30 40 C. Fabrics of cellulose materials can be dyed or printed with this dyestuff by one of the methods described above in ruby shades fast to wet processing, rubbing and light.
In the following Table there are listed the heavy metal complexes of further aminoazo dyestuffs and the reactive components linkable to the amino group, as well as the shades of these dyestufis on cellulose materials. The preparation of the aminoazo dyestuffs and their metal complexes and the reaction thereof with the reactive components can be carried out in analogy with the instructions of Example 47.
Abbreviations for reactive components as in Table of Exampie 3 Complex linked heavy metal Reac- Live CORP ponent Examph- No.
Aiainoazo dyestuii Shade Ruby.
Cu D0.
C1 A Greenish grey.
Co B Reddish,
53 Violet.
Complex Reaclinked tire Example heavy com- No. Aniinoazo dyestufi metal ponent Shade 56. 14iniino-2-methylbunzene-4- Cu B Blue.
sulphonic acid l-amino- Iiaphthalami,ti-disulphonit:
lsh Mark.
51L (l-an1ino-Z-t-hlornimnzl-nu h lu Navy sulphonir' (:id 7 -1 bluv.
hydroxy-2-act=tylaminolwnzmw), hydrolysed, 1-
amino-is-hyrlrnxynaphnaphthalenn-4-sul phonic diaminohnnzenwisulphonlr:
zone. 62...... l-amino-S-hydroxynaph- (in A U0- diaminobnnzt-nnt-sulplionic thalt-ne. 63 l-amino-S-hyzlroxynaph- Co A U0- thalcne-i-sulphonlc acid -l-hydroxy-2.6-diaminohenzene-4-sulphonic acid 3-metl1yl-pyrazolone-(5).
EXAMPLE 64 Ninety six Parts (referred to percent goods) of the copper-phthalocyanine tetrasulphochloride freshly prepared in the usual manner by the reaction of chlorosulphonic acid and thionyl chloride with copper-phthalocyanine, or of the isomeric copper-phthalocyanine tetrasulphochloiide synthetized from lsulpho-benzene-3,4-dicarboxylic acid via the corresponding washed filter cake in 500 parts of water and 500 parts of ice, a solution of 50 parts 1,3-diaminobenzene in 500 parts of water is added and the pH is adjusted to 8.5 by means of sodium carbonate. The suspension is stirred at room temperature for 24 hours and the pH is constantly maintained at 8.5 by the con tinuous addition of sodium carbonate. The resultant condensation product is precipitated at pH 1 2 by the addition of sodium chloride, filtered off with suction, washed and then redissolved neutral in 1,000 parts of water. Fifty seven Parts 2,4,6-trifluoro-5-chloropyrimidine are introduced into the.
blue solution with intense stirring, and the mixture is stirred at 20 30 C, while continuously neutralizing to pH 6 by means of a sodium carbonate solution, until free amino groups can no longer be detected. The reactive dyestuff of the formula )n Cu-phtlmlocyanine I so obtained is salted out, washed and dried at 30 40 C in a vacuum. It is a dark-blue powder which dissolves in water to give a blue color and dyes cotton and regenerated cellulose by one of the dyeing or printing processes described above in clear blue shades of good fastness to wet processing, rubbing and light.
lnstead of the 96 parts copper-phthalocyanine tetrasulphochloride, there may be used in a process which is copper-phthalocyanine-tetrasulphonic l acid, are suspended in the form of the moist, thoroughly otherwise the same as in Example 64 87 parts (referred to 100 percent goods) of the copperor nickel-phthalocyanine trisulphochloride obtained by the reaction of chlorosulphonic acid with copperor nickel-phthalocyanine, in the form of the moist filter cake thoroughly washed with ice-water; reactive dyestuffs dyeing in clear blue shades are then likewise obtained.
By working as described in Example 64, but starting from 87 parts copper-phthalocyanine trisulphochloride and replacing the 50 parts of the sodium salt of l,3-diaminobenzene-4- sulphonic acid with 90 parts of the sodium salt of 4,4- diaminodiphenyl-2,2'-disulphonic acid or 90 parts of the sodium salt of 4,4-diamino-stilbene-2,2'-disulphonic acid, there are likewise obtained reactive dyestuffs which dye cellulose materials by one of the methods described above in clear blue shades fast to wet processing, rubbing and light.
If 4',4",4",4"' tetraphenyl-Cu-phthalocyanine is used as starting material, there is obtained, after sulphochlorination, reaction with l,3-phenylene-diamine and acylation with 2,4,6- trifluoro-S-chloropyrimidine, a reactive dyestuff which dyes cellulose materials in the presence of acid-binding agents in clear green shades fast to wet processing and light.
EXAMPLE 65 Sixty three Parts l-amino-4-(4-aminophenyl)-aminoanthraquinone-2,5,S-trisulphonic acid are dissolved in 630 parts of water, the solution is adjusted to pH 6 by means of a sodium hydroxide solution, 18 parts 2,4,6-trifluoro-5- chloropyrirnidine are then added dropwise at C. and a pH of 6 6.5 is maintained by means of a sodium carbonate solution. When the reaction is completed, 7 parts potassium chloride are added, the product is filtered off with suction and washed with a 3 percent potassium chloride solution. The dyestuff which is obtained in the form of blue-green needles is dried in a vacuum at 30 40 C. It presumably has the formula and dyes cotton in greenish blue shades.
EXAMPLE 66 If the procedure described in Example 47 is followed but, instead of the copper-containing amino-monoazo dyestuff there used, the equivalent amount of the chromium complex of the aminoazo dyestuff obtained by coupling diazotized lamino-2-hydroxy-3-chlorobenzene-5-sulphonic acid with l-[3 3 '-aminophenyl) ]-sulphonylimido-sulphonyl-phenyl-3- methyl-pyrazolone-(S) is used as starting material, then a reactive dyestuff is obtained, which dyes cellulose materials by one of the methods described above in yellow-brown shades of good fastness to wet processing, rubbing and light.
EXAMPLE 67 0.1 Mole of the copper complex compound is dissolved in 3,000 parts by volume of water at pH 6 and combined at a temperature of 20 C, while stirring, with 16.8 parts by weight (0.1 mole) 2,4,6-trifluoro-5-chloropyrimidine, a pH of 6 being maintained by means of a 2N potassium carbonate solution. The mixture is stirred until the condensation is completed, the dyestuff is separated by the addition of a little sodium chloride and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained, which dissolves in water to give a green color and dyes cotton by the methods described in Examples 1 3 in green shades.
A cotton fabric is impregnated with a solution at 20 25 C. containing, per liter, 25 g of the above dyestuff and 0.5 g of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol), 150 g urea and 20 g sodium carbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about percent. After an intermediate drying at 50 60 C., the fabric is heated at C. for 2 minutes, the dyeing so obtained is thoroughly rinsed with hot water and treated for 20 minutes at the boil with a solution containing, per liter, 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, there is obtained a green dyeing of good fastness to wet processing, rubbing and light.
Clear green shades of good fastness properties are also obtained on materials of cellulose by one of the other dyeing or printing methods described in Examples 1 to 3, l8 and 30.
EXAMPLE 68 0.1 Mole of the paste of the aminoazo compound of the forrnula which is obtained by coupling the diazonium compound of 6- acetamino-2-arninonaphthalene-4,8-disulphonic acid with 2- hydroxy-naphthalene-3,6-disulphonic acid, hydrolysis and conversion of the monoazo compound into the copper complex, is dissolved in 2,000 parts by volume of water at pH 6.5 and combined with 20 parts by weight 2,4,6-trifluoro-5- chloro-pyrimidine. The reaction mixture is stirred at 20 30 C. until the condensation is completed, the pH of the reaction solution being maintained at 6 7 by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out, isolated and dried in a vacuum.
The dried dyestufi' is a dark powder which dissolves in water to give a violet color and dyes cotton in the presence of alkali in bluish violet shades.
EXAMPLE 69 An aqueous solution of 0.1 Mole of the copper complex of prepared according to the instructions of German Patent Specification Nos. 1,061,460 or 1,085,988, is reacted in the usual manner with 22 parts by weight, 2,4,6-trifluoro-5- chloropyrimidine. A pH of 6 7 is maintained by the addition of sodium carbonate and when the reaction is completed, the dyestuff is isolated by salting out. In the dry state the dyestuff is a dark powder which dissolves in water to give a violet color. Cotton fabric is dyed in violet shades fast to light and wet processing.
EXAMPLE 70 27.5 Pints of the sodium salt of Z-methylamino-S-hydroxynaphthalene-'F-sulphonic acid are dissolved in 150 parts of water, 20 parts 2,4,6-trifluoro--chloropyrimidine are added and the mixture is stirred at 30 C., while continuously neutralizing the hydrogen fluoride formed to pH 6 7 by means of a total of 34 parts by volume of a 16 percent sodium carbonate solution. After a short time, the acylation is completed, the pH is 6 and changes no more.
Thirty Parts sodium bicarbonate are then added, and a diazo suspension from 34 parts of the disodium salt of 2- aminonaphthalene-l ,7-disulphonic acid in 200 parts of water is added dropwise at 20 C. within minutes. The orangewhich is immediately formed, is completely separated, after further stirring for 1 hour, by means of 80 parts sodium chloride, filtered off, washed with a dilute sodium chloride solution and dried at 35 C. in a vacuum. The dyestufi dyes cellulose materials by the methods described above in reddish orange ,shades of very good fastness to wet processing and good fastness to chlorine.
Orange to red reactive dyestuffs are obtained in an analogous manner by acylating the aminonaphthol-sulphonic acids stated in Column 3 of the following Table with 2,4,6- trifluoro-S-chloropyrimidine and coupling the resultant acylamino-naphtholsulphonic acids with the diazo components stated in Column 2.
EXAMPLE 106 SO Na NH:
r N l 20 Is HN F Cl NaOaS is salted out, filtered off, redissolved in 4,000 parts of water at C., filtered and separated from the filtrate in completely pure form by the addition of 400 parts sodium chloride. The dyestuff is dried as usual at C. in a vacuum. lt dyes cellulose materials by one of the methods described above in fast yellowish orange shades.
EXAMPLE 107 A neutral solution of 60 parts of the trisodium salt of the aminoazo dyestuff obtained by coupling diazotized 2- aminonaphthalene-3,6,8-trisulphonic acid with 3- acetylaminoaniline in an acetic acid medium, in 500 parts of water is admixed with 20 parts 2,4,6-trifluoro-5- chloropyrimidine and the mixture is stirred at 30 C. for 1 hour, a pH of 6 being maintained by the continuous addition of a sodium hydroxide solution The acylation product which is partially precipitated is completely separated at pH 7 by the addition of l00 parts sodium chloride and filtered ofi. For purification, the reactive dyestuff so obtained can be redissolved 45 in 2,500 parts of water at 30 C., clarified and separated again Example I Shade on numbci' Dinzo component Animonaphthclsnlphonic acid cotton Z-ethylamino-5-liydroxy-naplitlialene-Wsul phonic acid Orange 2methylamino-5J1ydroxynaphthalene-Wen]phonic acid Z-ethylamino-fi-hydroxynaphthalc11e-7sulph0nic acid Do.
1. (fl-hydroxycthylamina)-5hydroxynaphthalcue-T-sulphonic acicL. Do.
Lamlno-fi-hydroxynaphthalencJ-sulplionic acid D0. 2-arnin0-5-l1ydroxynaphthalene-l,7-disul phonic acid Do. 2-amino-8-l1 ydroxynaphthalene-G-sulphonic acid. Scarlet. 2-an1i11o-8-hydroxynaphthalene-3,6-disulphonic acid D0.
Z-(B-hydroxyethylamino)-5-hydr0xynaphtlialenc-7-sulpli0nic acid. D0, 2-amin0-5-hydroxynaphthalene-7-suiphonic acid.. D0. 2-amino-5-hydroxynaphthalene-l,7-disulphonic ac Do. Z-amino-S-hydroxynaphthalene-fi-sulphonic acid. scarlet. Z-aniino-8-liydi'oxynaphthalene-Iifi-disulphonic acid D0.
.... 2-amino5-hydroxynapl1thalene-7-sulphonic acid. Orange. l-nietliylamin0-5-l1yd1'0xynaplithalcne-T-sulplionic acid Do. 2-amino-8-hydroxynaphthalene-G-sulphonic acid Scarlet. 'Z-methylamino-5-l1ydroxynaphthalene-7-suiphonic acid Orange, 2-(p-hydroxyethylamino) 5-l1ydroxynaphthalene-T-sulplionic acid D0.
- 2-amino-8-hydroxynaphthalene-fi-sulphonic acid. Scarlet.
Z-amindB-hydroxynapl1thalene-3,fi-disulplionic aci D0.
1 'Z-aniino-fi-hydroxynaplithalene-l,7-disulphonic acid Orange. Z-aminonaplitlialene-l-sulphonic acid... l-amino-B-hydroxynaphthalene-3,6-disulphonic acid Bluish red o l-amin0-8-hydroxynaphthalcne-4,G-disulphanic acid Do. 2-aminonuplitlnilcnc-l,fi-disulplionic ucid. l-amino-S-hydroxyimphthaletic-3,6-disulplioliic acid Do. 0 1-1mi110-8-11ydroxynaplithalene4,6-disulphonic acid Do.
1-amino-8-liydroxylmphthalcnn-fi-sulplionic acid. Bluish rcd l-nmi1loci-hydro!mphtlialvne-3.6-disulphonic acid Do. l-innino-s-liydro vnnpthalcnc-t.fi-disulplionic acid. Du.
3. l thnn-m-t,5, laimino-$-l1ydl'oxynnplitlmlcno-dsulphmm acid Du.
m \i .,-nm lmmulphonic acid... lurnino-S-ltnltu'3'miplithalcnc-3.ti-disnl11lmuicacid" l by salting out the filtrate with 350 parts sodium chloride The dyestuff has the formula after filtering ofi, drying at 35 C and grinding, it is a yellow powder which readily dissolves in water to give a yellow color and dyes cellulose fibers by one of the dyeing methods described above in the presence of acid-binding agents in very fast reddish yellow shades. Fast yellow shades are also obtained on wool and polyamide fibers.
Similar dyestuffs are obtained by following the procedure described above but replacing the 60 parts of the sodium salt of 4'-amino-2-acetylamino-phenyl-( 1')'azonaphthalene-( 2 3,6,8-trisu1phonic acid with corresponding amounts of the aminoazo dyestuffs obtained from the amino compounds stated in Column 2 and the coupling components stated in Column 3 in the usual manner by diazotization and coupling in an acetic acid medium, and acylating with 2,4,6-trifluoro5- chloropyrimidine.
Ex. Diazo Coupling Shade on No. component component cotton 108 Z-aminonaphthalene 1-amino3-methyl-6- strongly 1,5-disulphonic methoxybenzene reddish acid yellow 109 l-amino-3-methylyellow benzene 1 l0 l-aminonaphthalenereddish 6-sulphonic acid yellow 1 l l l-amino-3-acetylreddish aminobenzene yellow 1 12 S-aminophenyl-urea reddish yellow 1 13 l-amino-3-hydroxyreddish acetyl aminobenzene yellow 1 14 Z-ziminonaphthalenel-amino-3-methyl-6- strongly 5,7-disulphonic methoxybenzene reddish acid yellow 1 15 l-aminonaphthalenereddish 7-sulphonic acid yellow l 16 l amino 3 acelylreddish aminobenzene yellow 1 17 3-aminophenyl-urea reddish yellow yellow 1 1R l amino ll reddish hydroxyacetylyellow aminobenzene 1 l9 l-aminonaphthalene- 1-amino-3-methyl-6- strongly 3,7 disulphonic methoxybenzene reddish acid yellow 120 l-amino-3-methyl reddish benzene yellow 121 1 -aminonapht.ha1ene l-aminonaphthalenereddish 3,7-disulphonic 6-sulphonic acid yellow acid 122 Z-aminonaphthalene- 1 -amino-3-methy1- reddish 3,6-disulphonic benzene yellow acid 123 l-amino-3-methyl-6- strongly methoxybenzene reddish yellow 124 l-amino-3- acetylaminoreddish benzene yellow 125 3-aminophenyl-urea reddish yellow 126 l-amino-3- hydroxyacetylreddish aminobenzene yellow 127 l-aminonaphthalenereddish 6-sulphonic acid yellow 128 2-aminonaphthalenel-amino-3- 6,8-disulphonic acetylaminoreddish acid benzene yellow 129 1-amino-2- methoxynaphthastrongly lene-6-sulphonic reddish acid yellow 131 Z-aminonaphthalene- 4.8-disulphonic acid 135 2-aminonaphtha1ene- 4,8-disulphonic acid aminonaphthalene- 4.8-disulphonic acid 140 2-aminonaphtha1ene- 3,6,8-trisulphonic acid 145 1-amino3- 146 1-amino3- 160 2-aminonaphthalene- 3,6,8-trisulphonic acid 161 Z-aminonaphthalene- 4,6,8-trisulphonic acid 163 l-aminonaphthalene 2,4,7-trisulphonic acid 165 4-nitro-4-aminostilbene-2,2'-disulphonic acid 1 -aminonaphthalene- 6-sulphonic acid l-aminonaphthalene- 6-sulphonic acid l-aminonaphthalene- 7-su1phonic acid l-amino- 2- methoxynaphthalene-6-sulphonic acid l-methylamino-3- methylbenzene 1-ethy1amino-3- methylbenzene N-methyl-aniline N-ethylaniline N-butyl-aniline aniline 1-amino3- methylbenzene B-aminophenyl-urea l-amino-3- hydroxyacetylaminobenzene l-amino-3- acetylamino-timethoxybenzene acetylamino-6- methylbenzene methane-sulphonylaminobenzene 2,5-dimethoxyaniline 3-methyl-6- methoxy-aniline N-methyl-aniline N-ethyl-aniline N-butyl-aniline N-( B-hydroxyethyl aniline 3-(N-ethylamino toluene 2-aminotoluene 1-amino-2,5 dimethylbenzene 1 -amino-2-methoxybenzene 1 -amino-3-methoxybenzene l-ethylamino3- methoxybenzene 1-aminonaphthalene- -sulphonic acid l-aminonaphthalene- 7-sulphonic acid l-amino3-methylbenzene l-amino-3-acetyl' aminobenzene l-amino-3-methylbenzene l-aminonaphthaleneo-sulphonic acid l-amino-3acetylaminobenzene 3-aminophenyl-urea l-arnino- 3- hydroxyacetylaminobenzene N-methyl-aniline N-ethyl-aniline reddish yellow yellow yellow strongly reddish yellow yellow yellow yellow yellow yellow yellow reddish yellow reddish yellow reddish yellow reddish yellow yellowish orange reddish yellow reddish reddish yellow yellowish orange yellowish orange reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow strongly reddish yellow strongly reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow yellow yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow l 70 N-butyl-anilaniline reddish yellow [7 l N-( B-hydroxyethyl reddish aniline yellow l 7 2 l-( N-ethylamino )-3- reddish methylbenzene yellow 5 173 Aniline-2,5-disul l-aminonaphthalenereddish phonic acid -sulphonic acid yellow I74 l-aminonaphthalenereddish 7-sulphonic acid yellow 17S l-amino-3-methylyellow benzene o 176 l-amino-B-acetylyellow aminobenzene 177 l-amino-2-methoxy-5- reddish methylbenzene yellow I78 l-amino2,5-direddish methoxybenzene yellow l 79 Aniline-2,4-dil-amino-2-methoxyreddish I5 sulphonic acid S-methylbenzene yellow EXAMPLE 1 8O Sixty five Parts of the dyestuff of the formula 20 SO Na l SO Na is salted out, filtered off, washed and dried at 30 40 C. The dyestuff dyes cellulose materials by one of the methods described above in very fast ruby shadesv Dyestuffs with similar properties are obtained in analogy with the method described above from the copper complexes of the azo dyestuffs prepared from the diazo and azo components stated in the following Table EXAMPLE 202 The procedure is as described in Example 30 but the diazotized reactive group-containing intermediate is coupled in a soda-alkaline medium, instead of with 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6- disulphonic acid, with 40 parts of the sodium salt of lacetylamino-8hydroxynaphthalene-3,o-disulphonic acid, and the resultant dyestuff of the formula is isolated in the manner described in Example 30. The watersoluble dyestuff dyes cellulose materials by the pad-steaming or pad-thermofixing method (at 140 C.) in bluish red shades which are white dischargeable and fast to rubbing and light.
EXAMPLE 203 A solution of 19.5 parts of the sodium salt of laminobenzene-4-sulphonic acid and 6.9 parts sodium nitrite in 200 parts of water is poured into a mixture of parts of ice and 28 parts by volume of concentrated hydrochloric acid; the reaction mixture is then stirred for one-half hour at 0 10 C., and the excess nitrous acid is subsequently removed. The diazo suspension so obtained is admixed at 0 10 C. with a cooled and thereby partially crystallized solution of 26.2 parts of the potassium salt of l-aminonaphthalene-8-sulphonic acid in 250 parts of hot water and the strongly acidic coupling mixture is neutralized at 10 20 C. to pH 4 by the careful addition of a sodium hydroxide solution. The coupling is rapidly completed; the aminoazo dyestuff formed is completely salted out with 100 parts sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at 10 C. and pH 6 7. The aqueous solution is mixed dropwise with 20 parts 2,4,6-trifluoro-S-chloropyrimidine and stirred at 20 30 C., while continuously neutralizing the liberated acid to pH 6 7 by means of a sodium carbonate solution. When the aminoazo dyestuff can no longer be detected, the reactive dyestuff of the formula which is partially precipitated, is salted out with 40 parts sodium chloride, filtered off and redissolved in 800 parts of warm D0. (p-hydroxyothylnmino)-5-hydr0xynaplitlialonc-FsulphOnic acir D0. l 0mi1io-Sdn'droxyiiaphtlmlvno-3,6-zlisulpliouic acid t l Violet. H. l-amin0-8-hydroxynaphthalmiv-l,fi-tlisulphonic acid l 7 D0. l-amino-8-hydroxynaphtha]cue-3,6-disulph0nic acid. l D0. 193 .do... l-amillO-B-llytlroxynaphtlialcnel,6(lisulphonic acid 4, Do. 104.. l-hydroxy-2-amino4 acetylaminobnnzenv-G-sulphonic acid... MimiIm-S-hyIlroxynaphthalr-nv-fl, 6 lisulph0nic acid Bluish violet.
l-liydroxy-Z-aminod-acctylaminohvnz0rm6-sulph0ni acid 1 l-ellmxy-fl-llytlrnxynaphLlialtrnn-B, i-rlisulplmnit: acid v 1m.
ydro 9 arninn-tiacet-ylanlinohutizmm--sulplim ttid l-imiino-ls-liydrnxynaphtlmlnnrfl, l-rlisulphonir: acid l l t 7 lm.
Nllwl. Nllu water for purification. After clarification of the solution, the pure dyestuff is separated from the filtrate by the addition of 80 100 parts sodium chloride. After filtering ofi, drying at C. and grinding, there is obtained a yellow powder which readily dissolves in water to give a yellow color and dyes cellulose fibers by one of the dyeing methods described above in the presence of acid-binding agents in yellow shades of very good fastness to wet processing, light and chlorine. Fast yellow dyeings are also obtained on wool and polyamide fibers.
When the procedure described above is followed but, instead of 19.5 parts of the sodium salt of l-aminobenzene-4- sulphonic acid, equivalent amounts of the diazo components stated in the following Table are coupled with laminonaphthalene-8-sulphonic acid, then valuable yellow to brown reactive dyestufi's are likewise obtained after acylation with 2,4,6-trifluoro-S-chloropyrimidine.
EXAMPLE 205 A mixture of the solutions of 65.5 parts each of the chromium 2 1 complex and the cobalt 2 1 complex of the dyestutf of the formula Diazo component Shade on cellulose fibres Strongly reddish yellow.
l-aminobenzenc-2,5-disulphonic acid Reddish yellow. 2-amino-naphthalone-4,8-disulphonic acid 'l-amino-uaphthaleim-5,7-disulphonic acids D l-iuninoamphtlialouo-(LK-disulphonic acid. 7 Do. .HtllliIlO-lIitlllllllillllIl-3,li,R-lll$lll1lllOfilC acid. D0.
a, V V f N-N N11? (l-aminobenzene-2,5-disulphonic acid coupled in an acidic medium with l-amino-naphthalene-6-sulphonic acid) S OaNil S OgND.
(l-aminobenzene-2,5-disulphonic acid coupled in an acidic medium with the technical mixture of l-eminonaphthalene-(S- and -7-sulphonic acid) Ll-:u nino-1mpl|tinflow-2,554risulpllonic acid coupled in an acidic medium with Lumiuo-uaphthalcnc-(i-suiphouic acid) (l amino-naphthalene-2,554risulphonic acid coupled in an acidic medium with l-amino-2-methoxy-5-methylbenzene) EXAMPLE 204 When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g of the dyestuff described in Example 18, 100 g urea, 300 g of water, 500 g of alginate thickening agent g sodium alginate per kilogram thickening agent), 10 g sodium carbonate and 10 g of the sodium salt of 3-nitrobenzene-sulphonic acid and which has been made up with water to l kilogram, the fabric is subsequently subjected l Do.
, YlllOWlSll brown. 7 Orange-brown.
Rcddisli brown.
Violet-tinted brown,
each in 400 parts of water, is stirred with 40 parts 2,4,6- trifluoro-S-chloropyrimidine at 30 40 C. for about 2 hours while maintaining a pH of 6 7. When no more aminoazo dyestuff can be detected by chromatography (Co-complex: blue; Cr-complex: blue-green), the resultant mixture of the two reactive dyestuffs is salted out with potassium chloride, filtered off and dried.
The dyestuff yields on cellulose materials by the pad-dyeing to an intermediate drying and then steamed in a suitable processes or when printed in the presence of acid-binding agents, intense black shades of very good fastness to wet processing and light.
Valuable black dyestuffs are also obtained by proceeding analogously but using a mixture of the chromium 2 l and is filtered ofl', dissolved warm at pH 6 7 in 3000 parts of water, and reprecipitated from the filtered solution by the addition of sodium chloride. After filtering off, drying and pulverizing, there is obtained a yellow powder which is readily Cobalt 2 I 1 Complexes of the following aminoazo dyestuffs: 5 water-soluble and dyes cellulose materials from a long bath at v Cou ling 30 C. or by the cold batch padding process with sodium carcompm'em couplmg compmem PH bonate as acid-binding agent in clear yellow shades fast to l h d 2 4 l h d 8 h 9 washing, rubbing and light.
y roxy- -ammo y roxy- -amino-nap niucbenzene malenedlfidisulphonic lo I Valuable new reactive dyestuffs are also obtained by followacid mg the procedure described above, but replacing the Y y- 9 aminoazo dyestufl'- there used with equivalent amounts of the mtmnalihthzileneJ' aminoazo dyestuffs synthetized from the components stated in sulphonlc acid r the following Table.
u n EXAMPLE 206 l 5 In the Table the term hydrolyzed means that an acylamino group contained in the aminoazo dyestufi was sub- A neutral solution of 53.15 parts of the disodium salt of the sequently hydrolyzed, while the term reduced" indicates that aminoazo dyestufi obtained by coupling diazotized l-amino-4- a nitro group contained in the diazo component is reduced nitrobenzene-Z-sulphonic acid with l-(2'-chloro-5'- after the coupling to the amino group, whereby the desired sulphophenyl)-3-methyl-pflaZ0lOne-( 5 j ygquent 20 aminoazo dyestuff is formed.
pH of Example coupling Shade on No. Diazo co=ponent Azo component medium cellulose 207 l-amino-4-niti'obenzene-2-sulphonic acid 1-(4-sulphophenyl)-3-rnethyl-pyrazolone-(5) 5-6 Yellow. 208 o 1-(4su1phonpheuyl)-3-carboxy-pyrazolone-(S) 5-6 Redgish ye o: 209 i do 1-(3-su1phophenyl)-3-methyl-5-aminopyrazole 6-7 Yellow. 210,. 1-nm1uo-3-acetylaminobenzene-G-sulphonic acid 2 do .4 6-7 D 21L. do l 1-(B-hydroxyethyl)3-methyl-pyraz0lone-(5) -6 211. l 2 molesl-ar n110-3-acetyl-arninobenzene-6-sul- 1 mole bis-pyrazoloue from 4, 4'-bis-hydrazinodihen 5-6 phome acid (hydrolysed). disulphonic acid and acetoacetic ethyl ester) 213 111191; b-tuginfJ-3-zatsetylaminobenzene-6-sulphonic l-(U-sulph0phenyl)-3-carboxy-pyrazolone-(5) 5- ac] 1y ro yse 21 l-amiuo-fi-acetylaminonaphthalene-S, T-disulphonie 1-(4-sulph0phenyl)-3carboxy-pyrazolone-(fi) 5-6 Reddi acid (hydrolysed). yellow. 215 1-an1ino-2-methylbeuzeue-4,G-disulphonic acid 2-acetylarnino-5-naphthol-7-sulphonic acid (hydrolysed) 7-8 Orange. d 2-acetylamino-B-naphthol-6-sulphonic acid (hydrolysed) 7-8 Red. 217 1-amino-2-methylbenzene4,G-disulphonic aci 1fihlorga-aeetylamino-5-naphtho1-7-sulphonie acid (hydro- 7-8 Orange.
yse l 218 l-aminobenzene-2-sulphonic acid l-acetylamino-8-hydroxy-naphthalene-4,6-disulphonic acid 7-8 Red. (hydrolysed) 2-arninonaphthalene-B,6-disulphonic acid do 7-8 Blmghre 220 2-aminonaphthalcue-3,7-disulphonic acid "do 7-8 Do. 221 Z-aminonaphthalene-4,8disulphonic acid- ..d0 s 7-8 Do. 222 2-aminonaphthalene-3,G-disulphonic acid l-atiftglaimngfhydroxynaphthalene-3,6-disulphonic acid 7-8 Do. y r0 yse 223 2-an1inouaphthalene4,8-disulphonic acid 0 1aeftglarningS-hydroxynaphthalene-3,6-disulphonic acid 7-8 Do y 0 yse 224 l-amino-l-methoxybenzene-2-sulphonic acid 2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7- 7-8 Yellowish sulphonic acid (hydrolysed). red. 225 do 2-(N-aeetyl-N-methylamin0)-8hydroxynaphthalene-G-sul- 7-8 Red.
phonic acid (hydrolysed). 226 1-an1inobenzene-2-sulphonic acid 2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene-6- 7-8 Red.
sulphonic acid (hydrolysed). 227 l-aminobenzene-3-sulphonic acid do 7-8 Red. 228 l-aminobenzene-i-sulphonic acid -do 7-8 Red. 229 i 1-amino-4-methylbenzene-2-sulphonic acid do 7-8 Red. 230 1-aniin0-2,4dimethylbenzene-fi-sulphonic acid 2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene-6- 7-8 Red.
sulphonic acid (hydrolysed). 231 do 2-acetylamino-8-hydroxynaphthalene-fi-sulphonic acid 7-8 Red. (hydrolysed). 232 "do 2 acetylamin0-8-hydroxynaphthalene-3,6-disulphonic acid 7-8 Red. (hydrolysed) 233 :i-aminoazobenzene-B,4-disulphonic acid 1-amino-3-acetylaminobenzene 5-6 Yellow- TOW'l'I. 234 do 1-amino-3-hydroxyacetylaminobenzene &6 Do. 235 do l-amino-naphthalene-G-sulphonic acid" 5-6 Do. l. l-amino-naphthalene-7-sulphonic acid l 5-6 Do. 237 l do l-amino-2(4-ami110-2'-sulphophenyl-(1')-azo)-8-hydroxy- 8 Black.
naphthalene-3,fi-disulphonic acid.
1 (-i-positioned nitro group subsequently reduced.) 2 (Ii-positioned acetylamino group subsequently hydrolysed.)
reduction of the nitro group with sodium sulphide, in 300 parts of water is admixed with parts 2,4,6-trifluoror-5- chloropyrimidine, and the mixture is stirred at C. for 1 hour while the liberated acid is continuously neutralized to a pH value of 6.0 by means of a sodium carbonate solution. The precipitated dyestuff of the formula NnOiS EXAMPLE 258 s O Nu F is salted out, filtered off, washed and dried. it dyes cellulose fibers from a long bath or by one of the usual padding methods in the presence of sodium carbonate as acid-binding agent in deep violet-brown shades fast to wet processing and rubbing.
EXAMPLE 239 Fifty two Parts 1-amino4-(4'-N-methylaminomethylanilino)-anthraquinone-2,2'-disulphonic acid are dissolved in 550 parts of water and the solution is adjusted to pH 6 by means of a sodium hydroxide solution. Eighteen Parts 2,4,6-trifluoro-5-chloropyrimidine are then added dropwise at room temperature and a pH of 6 is maintained by means of a 2N sodium carbonate solution. The reaction is observed chromatographically. The reaction product which crystallizes in the form of blue needles is filtered off with suction and the filter residue washed with a 3 percent sodium chloride solution. Clear blue dyeings of good fastness to wet processing and good fastness to light are obtained on cotton.
The dyestufi obtained presumably corresponds to the formula with the diazo compound from 17.5 parts 2-amino-benzenesulphonic acid, with the diazo compound from 20.8 parts 3- chloroaniline-6-sulphonic acid in the presence of 12 parts sodium carbonate at a final pH of 7, then there is obtained a reactive dyestufi" of the formula Example N o. Water-soluble amino-anthraquinone derivative l-amino-4-(4-aminoanilino) l-amino-4-(3-arninoanilino)-anthraquinone-2,4-G-trisulphonic acid l-amino4-(4-aminocyclohcxylamino)-anthraquinone-2,5,8-trisulphonic acid. l-amino-4-(4-N-methylaminomethylanilino)-anthraquinone-2,3-disulphonic acid 1-amino-4-(4'-[4-a1ninobenzoylarninol-anilino)-anthraquinone-2,5,B-trisulphonic acid l-annno-4-(4-[4-aminobenzene-sulphonamidol-anilino)-anthraqulnone-2,5,8-trisulph0nic Shade 1-an1ino-4-(4-N-metliylaminomethylanilino)-anthraquinone-2,6,2-trisulphonic acid Gree'nish blue. l-amino-i-(4-N-methylaminomethylanilino)-anthraqulnone-2,5,8-trisulphonic acid. Do. 1-amino-4-(4-N-methylaminomethylanilino)-anthraquinone-2,8-dlsulphonic acitL anthraquinonc-2,6-disulphonic acid t 1-amino-4(4-aminoanilin0)-anthraquinone-2,5-disulphonic acid.. 1-amino-4-(3-aminoanilino)-anthraquinone-2,6-disulphonic acid" l-aminol-(ii aminoanilino)-anthraquinone-2,5-dlsulphonic acid Do.
l-aminoA-(B-aminoanilino)-anthraquionne2,4-disulphonic acid Somewhat reddish Blue-green. I(greenish blue.
ue. Reddlsh blue.
Clear blue. Blue. Blue-green.
253 l-amino-i-(i"-aminostilbeneamino)-anthraquinone-2,2,2-trisulphonic acid Green.
254 O NH: Clear reddish H blue.
I l SOQH l b NH- EXAMPLE 255 When proceeding according to the instructions of Example 18, but coupling the resultant dyestufi' intermediate, instead of 0 mediates with the stated diazo components, valuable reactive dyestufis with which cellulose materials can be dyed or printed, preferably in the presence of sodium carbonate, in the stated shades:
Cou- Example pling number Diazo component Coupling component pH Shade 256 l-arnino4-n1ethoxybenzene-G-sulphonic acid l-amino-8-hydroxynaphthalcne-3,G-disulphonic acid 7-8 Violet. 257 "do l-amin0-8-hydr0xynaphthalenc-Lfidisulphonic acid 7-8 Reddlish vio at. 258 do l-amino-5-hydroxynaphthalcne,l,7-disulphonic acid 7 Scarlet. l-amino-5-cl1loi'obenzene-2-sulphonic acid d 7 Orange.
l-aminobenzene-3-sulphonic acid t v A 7 D0. l-aminobcnzcne-l sulphonic acid. do 7 D0. .d0 4 t t t t t Z-amin0-8-hydr0xynaphthalene-3,6disulphonic a d 7-8 Scarlet 4-amiuobenzoic acid-(p-sulphoethyl)arnide l-arnino-S-hydroxynaphthalene-8,6-disulphonic acid 7-8 ed. l-amincH-sulphoacetylamino-benzene-6-sulphonic acid "do a 7-8 Violet l-amiuo-3sulphoacetylamina-bcnzeneii-sulphonic acid 2-amino5-hydroxynaphthaleue-l,7-disulphonic acid 7 Orange. 1-=imin(H-Sulphoacctylaminobenzeue 2-amin0-5-hydroxynaphthalene-l,7-disulphonic acid 7 Scarlet. l-zlminobcnzone-QA-disulphouic acid l (5.3methyl-3-amino-5-sulphophenyl)-3-methylpyrazolone- 6 Yellow.
5 r l-muiiromaphtlmlcne-L,S-disulplionic acid "do 6 D0.
EXAMPLE 269 which dyes cellulose materials by one of the usual methods of application with sodium carbonate as acid-binding agent in fast orange shades.
EXAMPLE 270 When the procedure described in Example 206 is followed but, instead of the aminoazo dyestufi' there used, 53.15 parts of the disodium salt of the amino azo dyestufi obtained by coupling diazotized l-amino-4-nitrobenzene-2-sulphonic acid with l 2'-chloro-5 -sulphophenyl )-3-methyl-pyrazolone-( and subsequent reduction of the nitro group with sodium sulphide, are acylated with 2,4,6-trifluoro-5-chloropyrimidine, then a valuable reactive dyestuff is also obtained, with which cellulose materials can be printed in fast yellow shades by the usual dyeing or printed methods.
Similar reactive dyestuffs are obtained, when, instead of the aminoazo dyestuff mentioned above, one of the aminoazo dyestuffs synthetized from the components stated in the following Table is acylated with 2,4,6-trifluoro-5- chloropyrimidine.
Example Diazo Azo Shade component component 27] amino-4-nitrol (2 '-methylyellow benzene-Z-sulphonic 4'-sulphoacid (reduced) phenyl )-3-methylpyrazolone-( 5) 272 l-(2',5'- yellow disulphophenyl )3- methyl-pyrazolone- 273 l-( 2 '-methylyellow 4'-sulpho- 6'-chlorophenyl )3- methyl-pyrazolone- 274 l -amino-4-nitrol-2'.5 yellow benzene-Z-sulphondichloro-4'-sulphoic acid (reduced) phenyl)-3-methylpyrazolone-( 5) 275 l-aminc-3-acetyl l-(2'-methylgreenish arninobenzene-o- 4 '-sulphophenyl) yellow sulphonic acid 3-rnethyl-pyrazo- (hydrolyzed )D lone-( 5) 276 l-4'-sulphogreenish phenyl)-3-methylyellow pyrazolone-(S) 277 l-2'-methylgreenish 4'-sulph0phenyl yellow 3-carboxy-pyrazolone-( 5) 278 l-(2'-chlorogreenish 4'-sulphophenyl yellow 3-carboxypyrazolone-( 5 EXAMPLE 279 Fifty eight Parts of the dyestufi of the fonnula (prepared by coupling diazotized l-hydroxy-2-amino-4- chloro-benzene-5-sulphonic acid with 2-methylamino-8- hydroxynaphthalene--sulphonic acid and coppering the resultant azo dyestuff) are dissolved neutral in 700 parts of water. 20.0 Parts 2,4,6-trifluoro-S-chloro-pyrimidine are added dropwise and the mixture is stirred at 20 30 C., while continuously neutralizing the liberated hydrofluoric acid to pH 6.0 6.5 by means of a sodium carbonate solution, until free amino groups can no longer be detected. The resultant reactive dyestuff of the formula is salted out, filtered off, washed and dried at 30 40 C. The dyestuff dyes cellulose materials by one of the methods described above in very fast violet shades.
Dyestuffs with similar properties are obtained in analogy with the method described above from the copper complexes obtained by simple demethylating or oxidizing coppering of the monoand disazo dyestuffs prepared from the diazo and azo components stated in the following Table COLl Example Diazo component Azo ling shade No. component pH 280 l-hydroxy-Z-amino- Z-amino-B-hydroxy l0 reddish 4-chlorobenzene-5- naphthalene-3,6- violet sulphonic acid disulphonic acid 28l l-amino-8-hydroxy l0 bluish -naphthalene-3,6- violet disulphonic acid 282 Z-amino-naphthal- 2-hydroxy-6-ace- 8-9 reddish ene-4,6,8-trisultylamino-naphthablue phonic acid lene-4-sulphonic (coppered with acid (hydrolyzed) oxidation) 283 l-2-hydroxyl-hydroxy-8-eth- 10 blue -nitronaphthaloxy-naphthaleneene-4-sulphonic 3 ,o-disulphonic acid (reduced) acid 284 l-hydroxy-Z-amino- 2-hydroxy-3-arnino 10 red benzene-4,6-disul- -naphthalenc-5,7- phonic acid disulphonic acid 285 2-amin0-naphthal- 8-9 blue ene-4.8-disulphonic acid (coppered with oxidation) 286 2-aminonaphthalene- 2-hydroxy-3- 8-9 blue 4,6,8-trisulphonic amino-naphthalene acid (coppered -7-sulphonic acid with oxidation) 287 3-methoxy-4-amino- 2-methylamino-5- l0 navy -methyl-azobenhydroxynaphthalblue zene-2',4'-disulene-7-sulphonic phonic acid acid (coppered with demethylation) 288 2-amino-8-hydroxyl l0 -naphtha.lene-3.6- disulphonic acid 289 Z-amino-S-hydroxy l0 -napht.halene l .7- disulphonic acid 290 3-methoxy-4amino- 2-methylamino-5- l0 fi-methyl-azobenzenehydroxynaphthal- 2',5'-disulphonic ene-7-sulphonic acid (coppered with acid demethylation) 291 3-rnethoxy-4-amino-6- 2-amino-8-hydroxy l navy methyLuzobenzene- -naphthalene-3,6- blue 2',5'-disulphonic disulphonic acid ilLhl (cuppcred with rlnnrlhylulinn) -nuphthnlcnc l .7- ("sulphonic acid EXAMPLE 293 62.0 Parts of the trisodium salt of the dyestuff obtained by soda-alkaline coupling of diazotized 4-chloro-2-amino-lhydroxybenzene with l-amino-8-hydroxynaphthalene-3,6- disulphonic acid are mixed in 300 parts of water at 70 80 C. and a pH of 8 9 with 54.2 parts of the 1 l chromium complex of the dyestufi obtained from 6-nitro-l-diazo-2- hydroxynaphthalene-4-sulphonic acid and Z-hydroxynaphthalene. A deep blue solution has formed after 10 minutes.
The mixed complex is acylated within about 1 hour at 30 40 C. and a pH of 6.5 7.5 with parts 2,4,6-trifluoro-5- chloropyrimidine. During this operation the pH value is kept constant by the dropwise addition of a sodium carbonate solution. The acylated dyestuff is separated by means of 20 percent sodium chloride, filtered off with suction and dried at 30 C.
EXAMPLE 294 30.4 Parts 2-amino-8-hydroxynaphthalene-3,-disulphonic acid are dissolved neutral in 300 parts of water, the solution is heated to 60 65 C. and 20 parts 2,4,6-trifluoro-5- chloropyrimidine are added. Forty Parts of a 15 percent sodium carbonate solution are added in the course of one hour so that the pH is 6 6.5. The acylation product is partially precipitated.
A diazonium salt solution freshly prepared from 13.6 parts p-aminobenzyl-sulphonic acid is added dropwise at 0 5 C. to the suspension of the acylation product which has been mixed with 12.5 parts sodium carbonate. After further stirring at ice bath temperature for 5 hours, the product is salted out with sodium chloride, filtered off with suction, washed with a dilute sodium chloride solution and dried at 30 C. in a vacuum drying cabinet. The dyestuff obtained corresponds to NttOaS By proceeding as described above, but acylating, instead of 30.4 parts 2-amino-8-hydroxynaphthalene-3,o-disulphonic acid, 30.4 parts 2-amino-S-hydroxynaphthalene-1,7- disulphonic acid with 2,4,6-trifluoro-S-chloropyrimidine and coupling the reactive group-containing coupling component with diazotizod p-aminobenzyl-sulphonic acid, a reactive dyestuff is obtained which is readily soluble and dyes fabrics containing cellulose fibers in brilliant reddish orange shades.
A cotton or staple fiber fabric is impregnated on a foulard at 20 25 C. with a solution containing, per liter of liquor, 30 g of the dyestuff described in Paragraph 1 of the present Example, g urea and 20 g sodium carbonate, the fabric is squeezed to a moisture content of about 100 percent and the moist fabric is rolled up again. After standing at room temperature for 4 hours, the fabric is rinsed, soaped at the boil in the usual manner and dried. A brilliant scarlet dyeing of good fastness to wet processing and light is obtained.
A cotton or staple fiber fabric is impregnated on a foulard at 20 25 C. with a solution containing, per liter ofliquor, 30 g of the dyestufi" described in Paragraph 1 of the present Example, 100 g urea and 20 g of sodium carbonate, the fabric is squeezed to a moisture content of about 100 percent and steamed at 103 C. for 30 seconds. After rinsing, soaping at the boil and drying, a brilliant scarlet dyeing of good fastness to wet processing and light is likewise obtained.
A cotton fabric is impregnated with a solution at 20 25 C. containing, per liter of liquor, 20 g of the dyestuff obtainable according to Paragraph 1 of the present Example and 0.5 g of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol) as well as 150 g urea and 15 g sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100 percent. After an intermediate drying at 50 60 C., the fabric is heated at 140 C. for 10 minutes and the dyeing so obtained is thoroughly rinsed with hot water and treated at the boil for 10 minutes with a solution containing, per liter 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, there is obtained an intense scarlet dyeing of good fastness to wet processing and light.
When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g of the dyestufi described in Paragraph l of the present Example, 100 g urea, 300 g of water, 500 g of an alginate thickening agent (60 g sodium alginate per kilogram of thickening agent), 10 g sodium carbonate and 10 g of the sodium salt of 3-nitrobenzenesulphonic acid, and which was made up to l kilogram with water, the fabric is subsequently subjected to an intermediate drying and then steamed in a suitable steaming apparatus at 103 C. for 30 seconds, an intense scarlet dyeing of good fastness properties is obtained after rinsing and soaping at the boil.
One hundred Parts of wool are introduced at 40 C. into a bath containing, in 5000 parts of water, 1.5 parts of the dyestuff described in Paragraph 1 of the present Example, as well as 6 parts of 30 percent acetic acid and 0.5 parts of a polyethoxylated stearylamine derivative containing hydroxyl groups. The dyebath is brought to the boil within 30 minutes and dyeing is then performed at the boil for 1 hour. After rinsing and drying, there is obtained a brilliant scarlet dyeing of good fastness to washing, milling and light.
EXAMPLE 295 28.9 Parts 2-amino-l-methylbenzene-3,5-disulphonic acid (monosodium salt) are diazotized and the diazo compound is coupled with 13.7 g l-amino-2-methoxy-5-methylbenzene in a weakly acidic medium. The resultant monoazo dyestufi is isolated and subsequently diazotized, or also immediately diazotized in solution without isolation, and coupled alkaline with 25.3 parts 2'methylamino-S-hydroxynaphthalene-7- sulphonic acid. The disazo dyestuff obtained is salted out by the addition of sodium chloride, filtered ofi" with sucuon, and the isolated product is metallized with about 50 parts of crystalline copper sulphate, 40 parts diethanolamine, 50 parts ammonia (d 0.88) at 95 100 C. within 5 hours. The dyestufi is isolated from the coppering solution by the addition of salt and careful acidification.
The coppered amino-disazo dyestuff is then acylated in an aqueous solution at pH 6 7 and a temperature of 20 30 C. with 20 parts 2,4,6-trifluoro-5-chloropyrimidine, the pH value being kept within the stated range by the addition of sodium carbonate. When the acylation is completed, the dyestuff is isolated with sodium chloride and dried at 35 C. In the form of the free sulphonic acid the dyestuff corresponds to the for mula COUPLING COMPONENT 2-amino-5-hydroxynaphthalen e-l ,7-disulphonic amin-8-hydroXynaphthalene-3 ,6-disulphonic acid.
The resultant dyestuffs have a blue color.
acid 2- EXAMPLE 296 0. l Mole 4-ureido-2-arninol -hydroxybenzene-5sulphonic acid is diazotized and coupled soda-alkaline with 0.1 mole lamino-8-hydroxynaphthalene-2,4-disulphonic acid. The coupling solution is adjusted to a content of 2 moles/liter with caustic soda and then boiled under reflux for 3 hours to hydrolyze the ureido group. After cooling, the mixture is neutralized with hydrochloric acid. The dyestuff is metallized by the addition of 25 parts copper sulphate and 100 parts of a 2N sodium hydroxide solution at 45 C. and a pH value of 4 6 and, after 30 minutes, acylated at pH 6 7 and temperatures of 30 C. with 0.l mole 2,4,6-trifluoro-5- chloropyrimidine. The resultant dyestufi of the formula is salted out. A blue dyeing is obtained on cotton.
EXAMPLE 297 A neutral paste of copper-phthalocyanine-S,3',3"- trisulphonic acid chloride, prepared from 600 g of technical 96 percent copper-phthalocyanine, is stirred with a little water, adjusted to 4 liters and reacted at a pH of 3.5 60.0 with 216 g N-methyl-N-(4'-amino-2'-sulphobenzyl)-amine,
initially at 0 3 C. and finally at 20 35 C., with the addition of 300 ml (=295 g) pyridine, and the pyridine is subsequently distilled of? from the resultant solution of copperphthalocyanine-disulphonic acid-monosulphonic acid-(3'- sulpho-4-methyl-aminornethyhanilide) at pH 9.0 with steam. The solution is brought to 20 30 C and 300 g 2,4,6- trifluoro-S-chloro-pyrimidine are added dropwise in portions in the course of l to 2 hours, while maintaining a pH of 6 7 by the addition of a dilute sodium hydroxide solution. At the same time, the reaction mixture is diluted with water, as required, to such an extent that the dyestufi always remains dissolved.
There are obtained 10 liters of dyestuff solution which is separated from the excess acylating agent, adjusted to pH 7.0 by the addition of acetic acid and reprecipitated by adding 2.5 liters of a concentrated sodium chloride solution with stirring.
After filtering off with suction and drying at 30 C, there is obtained a clear turquoise-blue dyestuff which is fixed on cotton from a soda-alkaline solution at 40 60 C. with a very good yield and fastness to washing.
lf the NiPc-3,3,3"-trisulphonic acid chloride is used as starting material, then a turquoise blue is obtained which is only slightly more greenish and has equally valuable properties.
EXAMPLE 298 0.1 Mole of the aminoazo dyestuff of the formula prepared according to the instructions of German Patent specification No. 1,115,865 (application F 27466 IVb/22 a) by coupling the diazonium compound from 2- aminonaphthalene-4,B-disulphonic acid with laminonaphthalene-6-sulphonic acid, further diazotizing the resultant aminoazo dyestuff, coupling with the equivalent amount of 2,5-diaminonapthalene-4,8disulphonic acid and conversion into the aminotriazole are dissolved in 1,000 parts by volume of water at pH 6 and mixed at a temperature of 20 30 C, while stirring, with 21 parts 2,4,6-trifluoro-5- chloropyrimidine. The hydrofluoric acid which is slowly liberated is neutralized by means of a sodium carbonate solution until the reaction is completed. The dyestufi is subsequently separated by the addition of sodium chloride, isolated and dried at about 50 C. in a vacuum. It is a yellow powder which dissolves in water to give a yellow color.
EXAMPLE 299 38.9 Parts of the dyestuff obtained by soda-alkaline coupling from 6 nitro-Z-diazo-l-hydroxybenzene-4-sulphonic acid and 2-hydroxynaphthalene are stirred in 200 parts of water at pH 8 and a temperature of 70 C. This suspension is admixed with 67.9 parts of the chromium complex compound (containing i chromium atom per dyestufi molecule) of the azo dyestuff obtained from 4 chloro-2-diazo' l-hydroxybenzene o-sulphonic acid and l-amino-8-hydroxynaphthalene-3,6-disulphonic acid, the pH being kept between 7 and 9 by the dropwise addition of a sodium carbonate solution. A dark-blue solution has formed afier 20 minutes at 70 80 C. The paper chromatogram shows that a uniform mixed complex has formed. The mixed complex is acylated within l hour at 40 C. and pH 6.5 7.5 with 22.0
parts 2,4,6-trifluoro-S-chloropyrirnidine, the pH being kept within the stated range by the dropwise addition of a sodium carbonate solution. The acylated dyestufiis salted out with 20 percent potassium chloride, filtered off and dried at 30 C. A dark powder is obtained which dissolves in water to give a blue-grey color.
In the form of the pentasodium salt the dyestufi' corresponds to the formula it dyes cotton by the methods described in Examples 1 3 in grey to black shades.
Valuable dyestufis can also be obtained in the manner described in the present Example from the starting components stated in the following Table. For the preparation of these dyestuffs the azo dyestuffs carrying the reactive group in the 2 1 mixed complex was always used as 1 l chromium complex.
Example l:l chromium metal free shade on No. complex dyestufi" cotton 300 4-nitro-2-aminol 4-nitro-2-aminol black hydroxybenzene-6 hydroxybenzene sulphonic acid Zhydroxynaphthall-amino-8-hydroxyene naphthalene-3,6- disulphonic acid 30l black 302 black 303 4-nitro-2 aminolblack hydroxybenzene Z-hydroxynaphthalene-fi-sulphonic acid 304 black 305 4-nit.ro-2-amino-lnavy blue hydroxybenzene l-hydroxynaphthalene-4-sulphonic acid 306 6-nitro-2-amino-lblack hydroxybenzene-4- sulphonic acid 2 -hydroxynaphthalene 307 4-nitro-2-aminol black hydroxybenzene l-acetylamino-7- hydroxynaphthalene 308 6-nitrol-amino-2- black hydroxynaphthalene- 4-sulphonic acid 2-hydroxynaphthalene 309 4-nitro-2-aminol- 4-nitro-2-amino- 1 black hydroxybenzene-6- hydroxynaphthalene sulphonic acid 6-sulphonic acid l-amino-8-hydroxy- 2-hydroxynaphthalene naphthalene-4,6- disulphonic acid 310 4-chloro-2-amino-l- 4-nitro2-amino-lbluehydroxybenzene-6- hydroxybenzene black sulphonic acid 2-hydroxynaphthalene l-nmino-8-hydroxynaphthalene-3.6- disulphonic acid "41 l blueblack 312 4-chloro-2-aminol hydroxybenzene-6- sulphonic acid l-amino-8-hydroxynaphthalene-3,6- disulphonic acid blueblack 4-nitro-2-amino- I hydroxybenzene Z-hydroxynaphthalene- 6-sulphonic acid 4-chloro-2-amino l hydroxybenzene Z-hydroxynaphthalene 4-nitro-2aminol hydroxybenzene l-acetylamino-B- hydroxynaphthalene- 3,6-disulphonic acid 4-nitro-2-aminol hydroxybenzene l-amino-8-hydroxynaphthalene-2,4- disulphonic acid 6-nitrol -amino-2- hydroxynaphthalene- 4-sulphonic acid 2-hydroxynaphthalene Z-aminobenzenel navy blue blue navy blue blueblack E carboxylic acid-S- green sulphonic acid l-phenyl-3-methyl-5- pyrazolone 6-nitrol -amino-2 black hydroxynaphthalene- 4-sulphonic acid 2-hydroxynaphthalene 4-chloro-2-amino-lviolet hydroxybenzene l-( 4 '-sulphophenyl 3-methyl-5-pyrazolone reddish blue 4-chloro-2-aminol hydroxybenzene Z-hydroxynaphthalene- 6-sulphonic acid 5-nitro-2-aminol black hydroxybenzene Z-hydroxynaphthalene- 6-sulphonic acid 4-nitro-2-amino-lblack hydroxybenzene 2-hydroxynaphthalene- 8-sulphonic acid 4-nitro-2-aminol hydroxybenzene l-hydroxynaphthalene- S-sulphonic acid 6-nitro-4-chlorol hydroxybenzene l'hydroxynaphthalene- 5-sulphonic acid black black EXAMPLE 325 8.2 Parts l-amino-4-[3'-amino-anilino]-anthraquinone-2- sulphonic acid are dissolved in a mixture of 160 parts of water and parts dioxan with the addition of L05 parts sodium carbonate. 3.8 Parts 2,4,6-trifluoro-5-chloropyrimidine are added dropwise at 0 C. and a pH of 6 6.5 is maintained by the addition of a 2N sodium carbonate solution. When the acylation is completed, the dyestuff is salted out at 20 C. with 5 parts sodium chloride and the crystalline product is filtered off with suction, washed with a 2 percent sodium chloride solution and dried in a vacuum at 30 C.
The dyestuff dyes wool in blue shades very fast to wet processing.
2. A reactive dyestuff of claim 1 wherein said dyestuff D contains at least one sulfonic acid group, and said group is bonded to an aromatic carbocyclic carbon atom of D directly or via a bridge member which is methylene or ethyLene.
3. A reactive dyestuff of Claim 1 having the formula
4. A reactive dyestuff of claim 1 having the formula
5. A reactive dyestuff of claim 1 having the formula
6. A reactive dyestuff of claim 1 having the formula
US3669951A 1966-09-10 1967-09-01 Reactive azo dyestuffs containing a-fluoropyimidinyl group Expired - Lifetime US3669951A (en)
DEF0050181 1966-09-10
DE1967F0051942 DE1644204C3 (en) 1966-09-10 1967-03-25
US3669951A true US3669951A (en) 1972-06-13
ID=25977412
US3669951A Expired - Lifetime US3669951A (en) 1966-09-10 1967-09-01 Reactive azo dyestuffs containing a-fluoropyimidinyl group
US (1) US3669951A (en)
JP (1) JPS4930502B1 (en)
BE (1) BE703598A (en)
DE (2) DE1644171A1 (en)
DK (1) DK128168B (en)
ES (1) ES344891A1 (en)
FI (1) FI44650C (en)
FR (1) FR1563661A (en)
GB (1) GB1169254A (en)
NL (1) NL150839B (en)
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FI44650C (en) 1971-12-10 grant
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DE1644204C3 (en) 1978-06-01 grant
BE703598A (en) 1968-03-07 grant
NL6712369A (en) 1968-03-11 application
JPS4930502B1 (en) 1974-08-13 grant
DE1644204A1 (en) 1972-03-16 application
DK128168B (en) 1974-03-11 grant
NL150839B (en) 1976-09-15 application
US2892671A (en) 1959-06-30 Coloring process