CA2154528A1 - Water-soluble disazo compounds, a process for their preparation and their use as dyestuffs - Google Patents
Water-soluble disazo compounds, a process for their preparation and their use as dyestuffsInfo
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- CA2154528A1 CA2154528A1 CA 2154528 CA2154528A CA2154528A1 CA 2154528 A1 CA2154528 A1 CA 2154528A1 CA 2154528 CA2154528 CA 2154528 CA 2154528 A CA2154528 A CA 2154528A CA 2154528 A1 CA2154528 A1 CA 2154528A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4411—Azo dyes
- C09B62/4415—Disazo or polyazo dyes
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Abstract
Water-soluble disazo compounds, process for their prep-aration and their use as dyestuffs Water-soluble disazo compounds of the formula (1) shown and defined below are suitable as fiber-reactive dye-stuffs for dyeing material containing hydroxy and/or carboxamide groups, in particular fiber material, such as cellulose fibers, wool and synthetic polyamide.
(1) in which: M is hydrogen or an alkali metal, D1 is a radical of the formula (2a) or (2b) and D2 is a group of the formula (3) (2a) (2b)
(1) in which: M is hydrogen or an alkali metal, D1 is a radical of the formula (2a) or (2b) and D2 is a group of the formula (3) (2a) (2b)
Description
HOECHST A~L~ SELLSCHAFT HOE 94/F 211 Dr.ST/bs Description Water-soluble disazo compounds, process for their preparation and their use as dyestuffs The invention relates to the technical field of fiber-reactive azo dyestuffs.
Disazo dyestuffs with fiber-reactive dyestuff properties which, for example, dye cotton in dark blue to black shades are known from U.S. Patents 4 649 193 and 5 241 057. However, they have deficiencies relating to their u~e; in particular, their tinctorial strength and build-up properties are in need of improvement.
With the present invention, novel disazo compounds with improved properties have been found, which correspond to the formula (1) Dt-N=N,~N= N_D2 ( 1 ) ~03S so3 in which:
M is hydrogen or an alkali metal, such as sodium, potassium or lithium;
Dl is a radical of the formula (2a) or (2b) 215452~
( Y~S2)n~ ( Y~S2)n ~j R2 (S03~)~
(2~) (2b) in which Y i8 vinyl, or i~ ethyl which i8 sub~tituted in the ~-position by a ~ub~tituent which can be elimin-ated by an alkali to form the ~inyl group, n i~ the number 1 or 2, preferably 1, Rl i~ hydrogen, halogen, ~uch ae bromine or chlorine, alkyl having 1 to 4 carbon atoms, ~uch an ethyl and in particular methyl, alkoxy ha~ing 1 to 4 carbon atom~, ~uch a~ ethoxy and in parti-cular methoxy, ~ulfo or carboxy , and i8 prefer-ably hydrogen, alkyl having 1 to 4 carbon atom~
or alkoxy ha~ing 1 to 4 carbon atomn, R2 i~ hydrogen, chlorine, alkyl ha~ing 1 to 4 carbon atoms, such a~ ethyl and in particular methyl, or alkoxy having 1 to 4 carbon atoms, ~uch a~ ethoxy and in particular methoxy, and i~ preferably hydrogen or alkoxy having 1 to 4 carbon atoms, m i~ the number zero, 1 or 2 (and in the cane where m i8 zero, this group i~ hydrogen), and i~ pre-ferably 1 or 2, and M has the abovementioned me~n;ng;
D2 i~ a group of the formula (3) 3~
i (3) N N
R--N ~N~ Q
in which 21S~528 M has the abovementioned meAn; ng, R is hydrogen or alkyl having 1 to 4 carbon atoms, such as methyl and ethyl, and i8 preferably hydrogen, and Q is alkoxy having 1 to 4 carbon atoms, such as methoxy or ethoxy, or is alkoxy having 2 to 4 carbon atoms, such as ethoxy, which is sub-stituted by alkoxy having 1 to 4 carbon atoms, such as methoxy or ethoxy, or is a group of the formula (4) / RA
- N~ (4) RB
in which RA is hydrogen or alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as ethyl and methyl, which can be substituted by alkoxy having 1 to 4 carbon atoms, such as methoxy and ethoxy, and RB has one of the me~n;ngs of RA or the group -NRARB forms the radical of a saturated 5- to 8-membered heterocyclic compound which optionally contains a further hetero group, such as -O- or -NH-, such as, for example, N-morpho-lino, N-piperazino or N-piperidino.
In formula (2a), the group Y-S02-, if n is 1, is pre-ferably bonded to the benzene nucleus in the meta- or para-position relative to the free bond. In formula (2b), the free bond which leads to the azo group is preferably bonded in the ~-position on the naphthalene nucleus.
In the above formulae and also in the following formulae, the individual formula members can have me~n;n~s which are identical to one another or different from one another within the context of their me~n;ng.
Substituents which can be eliminated by an alkali and are in the ~-position of the ethyl group of Y are, for example, halogen atoms, such as bromine and chlorine, ester groups of organic carboxylic and sulfonic acids, such as of alkylcarboxylic acids, optionally substituted benzenecarboxylic acids and optionally substituted ben-zenesulfonic acids, such as the groups alkanoyloxy having 2 to 5 carbon atoms, and of these in particular ace-tyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxyand toluylsulfonyloxy, and furthermore acid ester groups of inorganic acids, such as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), as well as dialkylamino groups with alkyl groups having in each case 1 to 4 carbon atoms, such as dimethylamino and diethylamino. Preferably, Y is vinyl, ~-chloroethyl or particularly preferably ~-sulfatoethyl.
The "sulfo", "carboxy ", "thiosulfato", "phosphato" and "sulfato" groups include both the acid form thereof and the salt form thereof. Accordingly, sulfo groups are groups correspo~;ng to the formula -SO3M, thiosulfato groups are groups correspo~;ng to the formula -S-SO3M, carboxy groups are groups correspo~;ng to the formula -COOM, phosphato groups are groups correspon~;ng to the formula -OPO3M2 and sulfato groups are groups correspon-ding to the formula -OSO3M, in each case where M has the abovementioned me~n;ng.
Groups of the formula (2a) are, for example, 2-(~-sulfatoethylsulfonyl)-phenyl, 3-(~-sulfatoethylsul-fonyl)-phenyl, 4-(~-sulfatoethylsulfonyl)-phenyl, 2-car-boxy -5-(~-sulfatoethylsulfonyl)-phenyl, 2-chloro-3-(sulfatoethylsulfonyl)-phenyl, 2-chloro-4-(~-sulfatoethylsulfonyl)-phenyl, 2-bromo-4-(~-sulfatoethyl-sulfonyl)-phenyl, 4-methoxy-3-(~-sulfatoethylsulfonyl)-phenyl, 4-chloro-3-(~-sulfatoethylsulfonyl)-phenyl, 2-ethoxy-4- or -5-(~-sulfatoethylsulfonyl)-phenyl, 2-methyl-4-(~-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-or -4-(~-sulfatoethylsulfonyl)-phenyl, 2,4-diethoxy-5-(~-sulfatoethyl~ulfonyl)-phenyl, 2,4-dimethoxy-5-(~-~ulfato-ethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(~-sulfatoethyl-~ulfonyl)-phenyl, 2-methoxy-5-methyl-4-(~-sulfatoethyl-sulfonyl)-phenyl, 2- or 3- or 4-(~-thiosulfatoethylsul-fonyl)-phenyl, 2-methoxy-5-(~-thiosulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(~-phosphatoethylsulfonyl)-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl, 2-chloro-4- or -5-(~-chloroethylsulfonyl)-phenyl, 3- or 4-(~-acetoxyethylsul-fonyl)-phenyl,5-(~-sulfatoethyl~ulfonyl)-naphth-2-yl,6-or 7- or 8-(~-sulfatoethyl~ulfonyl)-naphth-2-yl, 6-(~-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl, 6-(~-sulfato-ethylsulfonyl)-8-sulfo-naphth-2-yl, 5-(~-sulfatoethylsul-fonyl)-l-~ulfonaphth-2-yland8-(~-sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl, and of the~e preferably 4-(~-sulf-atoethyl~ulfonyl)-phenyl, 3-(~-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(~- 8ul fatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(~-~ulfatoethyl~ulfonyl)-phenyl, 2-methoxy-5-(~-~ulfatoethylsulfonyl)-phenyl, 4-vinyl-sulfonyl-phenyl, 3-vinyl~ulfonyl-phenyl and2-sulfo-4-(~-sulfatoethyl~ulfonyl)-phenyl.
Groups corre~pon~; ng to the formula radical Q are, for example, amino (-NH2), methylamino, ethylamino, propyl-amino, butylamino, isopropylamino, l-methyl-butylamino, 2-methyl-butylamino, dimethylamino, diethylamino, N-methyl-propylamino, N-methyl-butylamino, dipropyl-amino, (~-methoxy-ethyl)-amino, (~-ethoxy-ethyl)-amino, (~-methoxy-propyl)-amino, (~-methoxy-propyl)-amino, piperi-dino, morpholino, methoxy, ethoxy and isopropoxy.
The present invention furthermore relate~ to processes for the preparation of the disazo compounds of the formula (1) according to the invention. The~e comprise diazoti~ing an amino compound of the formula H2N-D2, where D2 has the abovementioned me~n; ng, in a procedure which i~ known per se, for example at -5C to +15C in a 6 21 54~ 2 8 strongly acid a~ueoUQ medium below a pH of 1.5 by means of an alkali metal nitrite, and coupling the resulting diazonium compound with an azo compound of the formula (5) ~03S ~ so3~
where Dl and M have the abo~ementioned meAn;ng, in a procedure known per se, for example at a pH of 5 to 9, preferably 6 to 7.5, and at a temperature of between O
and 15C, preferably between 5 and 10C, or reacting a compound of the formula (6) H2N OH 5031,( U O 3 S N--N--¢ ( 6 ) NH-R
in which Dl, M and R have the abovementioned meAn;ngs with cyanuric fluoride (2,4,6-trifluoro-1,3,5-triazine) at a temperature of between -5C and +20C, preferably between O and 10C, and at a pH of between 4 and 8, preferably between 5 and 7, to give the difluoro-tria-zinylamino-disazo compound and then reacting this with a compound of the formula H-Q, where Q has the abovemen-tioned meAn;ng, at a temperature of between -5C and +20C, preferably between O and 10C, and at a pH of between 5 and 10, preferably between 7 and 9, or reacting a compound of the formula (6) with a compound of the formula (7) 2154~8 r ( 7 ) J~N~ Q
in which Q has the abovementioned meAn;ng at a pH of between 3 and 8, preferably between 5 and 7, and at a temperature of between 5 and 30C, preferably between 10 and 20C.
The starting compounds of the formula (5) are known and can be prepared in the customary manner by reaction of the diazonium salt of the amine of the formula Dl-NH2 with 1-amino-8-naphthol-3,6-disulfonic acid. The com-pounds of the formula (6) are likewise known. They can be prepared, for example, by diazotizing an amino compound of the formula (8) co3~
H2N ~ (8) R-N-~cy I
in which M and R have the abovementioned meAn;ngs and acyl is an AlkAnoyl radical having 2 to 5 carbon atoms, ~uch as the acetyl radical, in a procedure which i8 known per se, such as, for example, at -5C to +15C, and coupling ~he diazotization product to a compound of the formula (5) at a pH of between 5 and 7 . 5 and at a tem-perature of between 5 and 20C, and converting the acylamino group in the disazo compound thus obtained into the free amino group by alkaline hydrolysis at a pH of between 10 and 14, preferably between 11 and 13. In this alkaline hydrolysis reaction, the group Y-SO2- can be converted into the ~-hydroxyethylsulfonyl group in the starting disazo compound, and for this reason a compound correspo~;ng to the formula (5) in which the group Y-SO2- is already the ~-hydroxyethylsulfonyl group can also be used as the starting substance in this proces~
variant. The disazo compound with the ~-hydroxyethylsul-fonyl group which contains amino groups can be converted into the compound of the formula (6), where Y is ~-sulfatoethyl, by means of concentrated sulfuric acid at a temperature of between O and 5C.
The deacylation of the starting compound to give the compound of the formula (6) can also be carried out by first converting the acylamino-disazo compound into the vinylsulfonyl-disazo compound which still contains acylamino groups at a temperature of between O and 20C, preferably between 10 and 15C, and at a pH of between 11 and 13, preferably 12 and 12.5, to form the vinyl group from the existing group Y, and deacylating this compound in an aqueous medium at a pH below 1 and at a temperature of between 90 and 100C.
The ~tarting compounds of the formula H2N-D2 can be prepared analogously to known procedures, such as, for example, by reacting an amine of the formula (9) so3~
H2N ~ ( 9 ) I
NH-R
where R and M have the abovementioned me~n;ng with cyanuric fluoride analogously to the instruction~ in German Offenlegungsschrift 2 746 109 and then reacting the resulting difluorotriazinylamino-sulfoaniline co~pound with a compound of the formula H-Q at a tempera-ture of between O and 20C and a pH of between 6 and 10.
Another possibility for synthesis of the starting 215~528 g compounds of the formula H2N-D2 can comprise reacting a compound of the formula (7) with a compound of the formula (9) in aqueou~ solution or suspen~ion at a temperature of between 5 and 30C, preferably between 10 and 20C, and at a pH of between 4 and 8, preferably between 5 and 7.
The starting compounds of the formula (7) themselves can be prepared, for example, analogously to the instructions of French Patent 1 561 876 or in accordance with J. Org.
Chem. 27, 2509 (1962).
The compounds of the formula (1) prepared according to the invention - called compounds (1) below - are sepa-rated off from the synthesis batches by generally known methods, either by precipitation from the reaction medium by means of electrolytes, such as, for example, sodium chloride and potassium chloride, or by evaporation of the reaction solution, for example by spray drying, in which case a buffer substance can be added to this reaction solution. The compounds (1) have fiber-reactive properties and have very good dyestuff properties. They can therefore be used for dyeing material cont~in;ng hydroxy and/or carboxamide groups, in particular fiber material, and also leather. The solutions obtained during synthesis of the compounds according to the invention can likewi~e also be used for dyeing directly as a liquid preparation, if appropriate after addition of a buffer substance, and if appropriate after concentration.
The present invention therefore also relates to the use of the compounds (1) for dyeing materials cont~;n;ng hydroxy or carboxamide groups and to processes for their use on these substrates. This includes bulk dyeing, for example of films of polyamide, and dyeing by printing.
The material~ are preferably used in the form of fiber materials, in particular as textile fiber materials, such as in the form of woven fabrics or as yarns, ~uch as in the form of hanks and wound packages.
215g528 Naterials contA;ning hydroxy groups are naturally occurring or synthetic materials containing hydroxy groups, such as, $or example, cellulose fiber materials or regenerated products thereof and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton, and also other plant fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are, for example, viscose staple and filament viscose.
Materials containing caLboxa~.ide groups are, for example, synthetic and naturally occurring polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide 6,6, polyamide 6, polyamide 11 and polyamide 4.
The compounds (1) can be applied to and fixed on the substrates mentioned, in particular the fiber materials mentioned, by the use techniques known for water-soluble dyestuffs, in particular for fiber-reactive dyestuffs.
Dyeings with very good color yields and an excellent color build-up at high degrees of fixing are thus obtained with them on cellulose fibers by the exhaust process from a long liquor using the most diverse acid-b;n~;ng agents and if appropriate neutral salts, such as sodium chloride or sodium sulfate. Dyeing is carried out in an aqueous bath at temperatures of between 40 and 105C, if appropriate at temperatures of up to 120C, under pressure and if appropriate in the presence of customary dyeing auxiliaries. A procedure can be followed here in which the material i8 introduced into the warm bath and this is heated gradually to the desired dyeing temperature and the dyeing process is brought to comp-letion at this temperature. If desired, the neutral salts which accelerate exhaustion of the compounds (1) can also be added to the bath only after the actual dyeing tempe-rature has been reached.
Excellent color yields with high degrees of fixing and a very good color build-up are likewise obtained on 2'1~ 8 cellulose fibers by the padding proces~, in which the dye~tuffs can be fixed in the customary manner by batching at room temperature or elevated temperature, for example up to about 60C, by steaming or with dry heat.
Deep prints with a good contour status and a clear white background are likewise obtained by the customary print-ing proce~ses for cellulose fibers, which can be carried out either in one phase, for example by printing with a printing paste comprising sodium carbonate or another acid-b;n~; ng agent and the compound (1) and subsequently ste~;ng at 100 to 103C, or in two pha~es, for example by printing with a neutral or weakly acid printing paste comprising the coloring agent and then fixing either by passing the printed goods through a hot electrolyte-containing alkaline bath or by over-padding with an alkaline electrolyte-containing padding liquor and subsequent batching of thiR treated material or subse-quent steaming or ~ub~equent treatment with dry heat. The appearance of the prints depends only little on the varying fixing condition~. The degrees of fixing obtained with the compounds (1) are very high both in dyeing and in printing.
Hot air of 120 to 200C is used for fixing by means of dry heat by the customary thermofixing procesAes. In addition to the usual steam of 101 to 103C, it is also po~6ible to employ superheated Rteam and presRurized steam having temperatures of up to 160C.
The agents which effect b;n~;ng of the acid and fixing of the compounds (1) to the cellulose fibers are, for example, water-~oluble basic Ralts of the alkali metals and of the alkaline earth metals with inorganic or organic acid~, and also compounds which liberate alkali under the influence of heat. The alkali metal hydroxides and alkali metal ~alts of weak to moderately strong inorganic or organic acids are to be mentioned in par-ticular, the ~odium and pota~ium compound~ preferably 2I5~528 being meant by the alkali metal compounds. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbo-nate, potassium carbonate, 60dium formate, sodium dihy-drogenphosphate, disodium hydrogenphosphate, sodiumtrichloroacetate, ~odium silicate or trisodium phosphate.
By treating the compounds (1) with the acid-b;n~;ng agents, if appropriate under the action of heat, they are bonded chemically to the cellulose fibers; the cellulose dyeings in particular show excellent wet-fastness prop-erties after the customary after-treatment by rinsing to remove non-fixed portions of the compounds (1), especi-ally since such non-fixed portions can easily be washed out because of their good solubility in cold water.
The dyeings on polyurethane and polyamide fibers are usually carried out from an acid medium. Thus, for example, acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate can be added to the dyebath in order to obtain the desired pH.
For the purpose of achieving a usable levelness of the dyeing, addition of customary leveling auxiliaries, such as, for example, based on a reaction product of cyanuric chloride with three times the molar amount of an amino-benzenesulfonic acid and/or an aminonaphthalenesulfonic acid or based on a reaction product of, for example, stearylamine and ethylene oxide, is advisable. As a rule, the material to be dyed is introduced into the bath at a temperature of about 40C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature of between 60 and 98C. However, the dyeings can also be carried out at the boiling point or at temperatures of up to 120C (under pressure).
The dyeings and prints produced with the compounds (1) are distinguished by clear shades. The dyeings and prints 2 1 ~ 4 5 2 8 on cellulose fiber materials in particular furthermore have, as already mentioned, a good depth of color, a good fastness to light and very good wet-fastness properties, such as fastnesses to wA~h; ng, milling, water, salt water, cross-dyeing and perspiration, and moreover good fastness to pleating, fastness to ironing and fastness to rubbing.
The high fixing yields which can be achieved with the dyestuffs according to the invention on cellulose fiber materials, which can be more than 90 % when used in printing processes and pad-dyeing processes, are to be emphasized in particular. Another advantage of the compounds (1) is that the portions which have not been fixed in the printing or dyeing operation can easily be washed out, which means that the operation of w~h;ng the printed or dyed cellulose fiber materials can be carried out with small amounts of wash liquor and, if appro-priate, with an energy-saving temperature program during the washing operation.
The following Examples serve to illustrate the invention.
The parts are parts by weight and the percentage data are percentages by weight, unless noted otherwise. Parts by weight bear the same relation to parts by volume as the kilogram to the liter.
The compounds described by way of their formulae in the Examples are 8hown in the form of the free acid; in general, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and are used for dyeing in the form of their salts. The starting compounds and components mentioned in the form of the free acid in the following Examples~ in particular the Tabular Examples, can like-wise be employed in the synthesis as such or in the form of their salts, preferably alkali metal salts.
The absorption maxima (AmaX) in the visible range stated 2 t51 528 for the dyestuffs according to the invention were deter-mined with the aid of their alkali metal salt~ in aqueous solution. In the Tabular Examples,the AmaX value~ are in parentheses with the color shade data; the wavelength data are in nm.
Example 1 30 parts of trifluorotriazine are constantly added to a neutral aqueous solution of 135 parts of the disazo compound 2-(4'-(~-sulfatoethylsulfonyl-phenyl)-azo-7-(2"-sulfo-5-amino-phenyl)-azo-3,6-disulfo-1-amino-8-hydroxy-naphthalene in 1500 parts of a mixture of water and ice - in the course of about 5 minutes, while stirring vigo-rously and maintA; n; ng a pH of between 5 and 6 by means of aqueous sodium hydroxide solution. The mixture is subsequently stirred for a further 30 minutes, 10.8 parts of ammonium chloride are then added, stirring is con-tinued for a further 4 hours at 0 to 5C and a pH of between 8 and 9, then the mixture is brought to a pH of 6.5 by means of aqueous hydrochloric acid, and the resulting disazo compound according to the invention, of the formula (written in the form of the free acid) _~ N ;N ~5 0, H~ NiN
CH2 . NH~N-~NH2 U~x~ 604nm) is isolated as the alkali metal salt (sodium salt) in the customary manner, for example by spray drying or by salting out with sodium chloride.
The disazo compound according to the invention h~s very good fiber-reactive dyestuff properties and gives dyeings ~15452~
and prints in deep navy blue shade~ with good fastness properties on the materials mentioned in the description, in particular on materials cont~;n;ng cellulose fibers, by the use processes customary for fiber-reactive in industry dyestuffs.
Example 2 30 parts of trifluorotriazine are constantly added to a neutral aqueous solution of 133 parts of the disazo compound 2-(4'-(vinylsulfonyl-phenyl)-azo-7-(2"-sulfo-5-amino-phenyl)-azo-3,6-disulfo-1-amino-8-hydroxy-naphtha-lene in 1500 parts of a mixture of water and ice in the course of about 5 minutes, while maintA;n;ng a pH of between 5 and 6 by means of aqueous sodium hydroxide solution and stirring vigorously. The mixture is subsequently stirred for a further 30 minutes, 13.5 parts of methylammonium chloride are then added, stirring is continued at O to 5C and a pH of between 8 and 9 for a further 4 hours, then the mixture is brought to a pH of 6.5 by means of agueous hydrochloric acid, and the resulting disazo compound according to the invention, of the formula (written in the form of the free acid) H2N OH SO~H
~ N ;N ~S 0, H~l N iN
CH~CH2 NHJ~N~ NH
CH~
~maX = 604 nm) is isolated as the alkali metal salt (sodium salt) in the customary manner, for example by spray drying or by salting out with sodium chloride.
The disazo compound according to the invention ha~ very good fiber-reactive dyestuff properties and gives dyeings 215~528 and prints in deep navy blue shades with good fastness properties on the materials mentioned in the description, in particular on materials containing cellulose fibers, by the use processes customary for fiber-reactive dye-stuffs in industry.
Example 3 A mixture of 140 parts of potassium fluoride and 500 parts of tetrahydrothiophene 1,1-dioxide (=
sulfolane) is heated to 120C in a flask with a distill-ation column and condenser, and a su~penQion of 193 partsof 2,4-dichloro-6-dimethylamino-1,3,5-triazine in 400 parts of sulfolane is slowly added, whilst stirring thoroughly. The mixture is ~ubsequently stirred at 150C
for about a further 4 hours and the 2,4-difluoro-6-dimethylamino-1,3,5-triazine prepared is isolated in a yield of 130 parts by distillation at 94-95C/17 mbar.
The compound has a melting point of 72-73C.
48 parts of this difluoro compound are stirred into a solution, at 10C and a pH of 6, of 56 parts of 1,3-diaminobenzene-4-sulfonic acid in 600 parts of water, and the reaction is brought to completion in the course of about 8 hours, while stirring further at 10 to 20C and at a pH of 5 to 7. The 2-(4'-sulfo-3'-amino-phenylamino)-4-fluoro-6-dimethylamino-1,3,5-triazine thus obtainedcan be isolated by salting out or processed further for the preparation of a disazo compound according to the inven-tion without further intermediate isolation.
56.2 parts of 4-(~-sulfatoethylsulfonyl)-aniline are diazotized in a procedure known per se and the diazotiza-tion product is coupled with 63 parts of 1-amino-8-naphthol-3,6-di~ulfonic acid at a pH below 1.5. The diazonium Qalt suspension, prepared in a procedure known per se, of 33 parts of the 2-(4'-sulfo-3'-amino-phenyl-amino)-4-fluoro-6-dimethylamino-1,3,5-triazine described above is added to the monoazo compound solution thus prepared and the coupling reaction is brought to completion in the course of about 4 hours at 10 to 15C
and at a pH of between 5 and 7.
The disazo compound according to the invention, of the formula (written in the form of the free acid) S2 ~ HO S ~ SOJH ~ NiN
l H2 N H~N-~N ( CH3 ) 2 UnUX = 604 nm~
is isolated as the alkali metal salt (sodium salt) in a customary manner by salting out with sodium chloride or by spray drying.
The disazo compound according to the invention has very good fiber-reactive dyestuff properties and gives dyeings and prints in deep navy blue shades with good fastness properties on the materials mentioned in the description, in particular on materials cont~; n; ng cellulose fibers, by the use processes customary for fiber-reactive dye-stuffs in industry.
Example 4 parts of 2,4-difluoro-6-methylamino-1,3,5-triazine (which is prepared in accordance with the instructions of French Patent 1 561 876) are added to a solution, at 0C
and a pH of 6, of 56 parts of 1,3-diaminobenzene-4-sulfonic acid in 600 parts of water, while stirringthoroughly. The mixture is further stirred at 10C and at a pH of between 5 and 7 for about a further 6 hours and the 2-(4'-sulfo-3'-amino-phenylamino)-4-fluoro-6-methyl-amino-1,3,5-triazine thus obtained is reacted with the equivalent amount of the monoazo compound 2-(4'-~-sul-fatoethylsulfonyl-phenyl)-azo-3,6-disulfo-1-amino-8-2~ S4528 hydroxy-naphthalene analogously to the instructions of Example 3, after conversion into the diazonium salt, to give the disazo compound according to the invention of the formula (written in the form of the free acid) 2~H O; 5~5 0, H~ NiN
CH2-CH20SO3H NH--~N-J--NH
~rrUx = 604 nm~
This is isolated as the alkali metal salt (sodium salt) by salting out with sodium chloride or by spray drying.
The disazo compound according to the invention has the same good dyestuff properties a~ the disazo compound of Example 2 according to the invention.
Examples 5 to 16 Further disazo compounds according to the invention, corre8pon~; ng to the formula (A) Dl-N--N~;N----N~3 i (A) R--N ~NJ--Q
are described with the aid of their components in the following Tabular Examples. They can be prepared in the manner according to the invention, for example analo-gously to the abovementioned Examples.from the starting compounds which can be ~een from the formula (A) (the diazo component Dl-NH2, 3,6-di~ulfo-1-amino-8-naphthol, an optionally N-alkyl-substituted 2-sulfo-1,3-phenylene-- - 2 1 545~8 dlamlne, cyanurlc fluorlde and a compound of the formula H-Q~.
They have very good flber-reactlve dyestuff propertles and dye the materlals mentloned ln the descrlptlon, such as, ln partlcular, cellulose flber materlals, ln the color shades stated ln the partlcular Tabular Example (for cotton here) wlth a good depth of color and good fastnesses.
Disazo compound of the formula (A) ExampleRadical D1 Radical R Radical Q Color shade 5 4-(~-sulfato-ethyl- hydrogen methylamino navy blue sulfonyl-phenyl (606) 6 ditto hy~Logendimethylamino navy blue (604) 7 ditto hydrogenethylamino navy blue (605) 8 ditto hydrogenn-propylamino navy blue ~605) 9 ditto hydrogen n-butylamino navy blue (604) ditto hydrogen y-methoxy- navy blue propyl-amino (603) 11 ditto hydrogen diethylamino navy blue (606) 124-(vinylsulfonyl)- methyl amino navy blue phenyl 13 ditto methyldimethylamino navy blue 14 ditto methylethylamino navy blue ditto ethyln-propylamino navy blue 16 ditto methyl~-methoxy- navy blue methyl-amino
Disazo dyestuffs with fiber-reactive dyestuff properties which, for example, dye cotton in dark blue to black shades are known from U.S. Patents 4 649 193 and 5 241 057. However, they have deficiencies relating to their u~e; in particular, their tinctorial strength and build-up properties are in need of improvement.
With the present invention, novel disazo compounds with improved properties have been found, which correspond to the formula (1) Dt-N=N,~N= N_D2 ( 1 ) ~03S so3 in which:
M is hydrogen or an alkali metal, such as sodium, potassium or lithium;
Dl is a radical of the formula (2a) or (2b) 215452~
( Y~S2)n~ ( Y~S2)n ~j R2 (S03~)~
(2~) (2b) in which Y i8 vinyl, or i~ ethyl which i8 sub~tituted in the ~-position by a ~ub~tituent which can be elimin-ated by an alkali to form the ~inyl group, n i~ the number 1 or 2, preferably 1, Rl i~ hydrogen, halogen, ~uch ae bromine or chlorine, alkyl having 1 to 4 carbon atoms, ~uch an ethyl and in particular methyl, alkoxy ha~ing 1 to 4 carbon atom~, ~uch a~ ethoxy and in parti-cular methoxy, ~ulfo or carboxy , and i8 prefer-ably hydrogen, alkyl having 1 to 4 carbon atom~
or alkoxy ha~ing 1 to 4 carbon atomn, R2 i~ hydrogen, chlorine, alkyl ha~ing 1 to 4 carbon atoms, such a~ ethyl and in particular methyl, or alkoxy having 1 to 4 carbon atoms, ~uch a~ ethoxy and in particular methoxy, and i~ preferably hydrogen or alkoxy having 1 to 4 carbon atoms, m i~ the number zero, 1 or 2 (and in the cane where m i8 zero, this group i~ hydrogen), and i~ pre-ferably 1 or 2, and M has the abovementioned me~n;ng;
D2 i~ a group of the formula (3) 3~
i (3) N N
R--N ~N~ Q
in which 21S~528 M has the abovementioned meAn; ng, R is hydrogen or alkyl having 1 to 4 carbon atoms, such as methyl and ethyl, and i8 preferably hydrogen, and Q is alkoxy having 1 to 4 carbon atoms, such as methoxy or ethoxy, or is alkoxy having 2 to 4 carbon atoms, such as ethoxy, which is sub-stituted by alkoxy having 1 to 4 carbon atoms, such as methoxy or ethoxy, or is a group of the formula (4) / RA
- N~ (4) RB
in which RA is hydrogen or alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as ethyl and methyl, which can be substituted by alkoxy having 1 to 4 carbon atoms, such as methoxy and ethoxy, and RB has one of the me~n;ngs of RA or the group -NRARB forms the radical of a saturated 5- to 8-membered heterocyclic compound which optionally contains a further hetero group, such as -O- or -NH-, such as, for example, N-morpho-lino, N-piperazino or N-piperidino.
In formula (2a), the group Y-S02-, if n is 1, is pre-ferably bonded to the benzene nucleus in the meta- or para-position relative to the free bond. In formula (2b), the free bond which leads to the azo group is preferably bonded in the ~-position on the naphthalene nucleus.
In the above formulae and also in the following formulae, the individual formula members can have me~n;n~s which are identical to one another or different from one another within the context of their me~n;ng.
Substituents which can be eliminated by an alkali and are in the ~-position of the ethyl group of Y are, for example, halogen atoms, such as bromine and chlorine, ester groups of organic carboxylic and sulfonic acids, such as of alkylcarboxylic acids, optionally substituted benzenecarboxylic acids and optionally substituted ben-zenesulfonic acids, such as the groups alkanoyloxy having 2 to 5 carbon atoms, and of these in particular ace-tyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxyand toluylsulfonyloxy, and furthermore acid ester groups of inorganic acids, such as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), as well as dialkylamino groups with alkyl groups having in each case 1 to 4 carbon atoms, such as dimethylamino and diethylamino. Preferably, Y is vinyl, ~-chloroethyl or particularly preferably ~-sulfatoethyl.
The "sulfo", "carboxy ", "thiosulfato", "phosphato" and "sulfato" groups include both the acid form thereof and the salt form thereof. Accordingly, sulfo groups are groups correspo~;ng to the formula -SO3M, thiosulfato groups are groups correspo~;ng to the formula -S-SO3M, carboxy groups are groups correspo~;ng to the formula -COOM, phosphato groups are groups correspon~;ng to the formula -OPO3M2 and sulfato groups are groups correspon-ding to the formula -OSO3M, in each case where M has the abovementioned me~n;ng.
Groups of the formula (2a) are, for example, 2-(~-sulfatoethylsulfonyl)-phenyl, 3-(~-sulfatoethylsul-fonyl)-phenyl, 4-(~-sulfatoethylsulfonyl)-phenyl, 2-car-boxy -5-(~-sulfatoethylsulfonyl)-phenyl, 2-chloro-3-(sulfatoethylsulfonyl)-phenyl, 2-chloro-4-(~-sulfatoethylsulfonyl)-phenyl, 2-bromo-4-(~-sulfatoethyl-sulfonyl)-phenyl, 4-methoxy-3-(~-sulfatoethylsulfonyl)-phenyl, 4-chloro-3-(~-sulfatoethylsulfonyl)-phenyl, 2-ethoxy-4- or -5-(~-sulfatoethylsulfonyl)-phenyl, 2-methyl-4-(~-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-or -4-(~-sulfatoethylsulfonyl)-phenyl, 2,4-diethoxy-5-(~-sulfatoethyl~ulfonyl)-phenyl, 2,4-dimethoxy-5-(~-~ulfato-ethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(~-sulfatoethyl-~ulfonyl)-phenyl, 2-methoxy-5-methyl-4-(~-sulfatoethyl-sulfonyl)-phenyl, 2- or 3- or 4-(~-thiosulfatoethylsul-fonyl)-phenyl, 2-methoxy-5-(~-thiosulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(~-phosphatoethylsulfonyl)-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl, 2-chloro-4- or -5-(~-chloroethylsulfonyl)-phenyl, 3- or 4-(~-acetoxyethylsul-fonyl)-phenyl,5-(~-sulfatoethyl~ulfonyl)-naphth-2-yl,6-or 7- or 8-(~-sulfatoethyl~ulfonyl)-naphth-2-yl, 6-(~-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl, 6-(~-sulfato-ethylsulfonyl)-8-sulfo-naphth-2-yl, 5-(~-sulfatoethylsul-fonyl)-l-~ulfonaphth-2-yland8-(~-sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl, and of the~e preferably 4-(~-sulf-atoethyl~ulfonyl)-phenyl, 3-(~-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(~- 8ul fatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(~-~ulfatoethyl~ulfonyl)-phenyl, 2-methoxy-5-(~-~ulfatoethylsulfonyl)-phenyl, 4-vinyl-sulfonyl-phenyl, 3-vinyl~ulfonyl-phenyl and2-sulfo-4-(~-sulfatoethyl~ulfonyl)-phenyl.
Groups corre~pon~; ng to the formula radical Q are, for example, amino (-NH2), methylamino, ethylamino, propyl-amino, butylamino, isopropylamino, l-methyl-butylamino, 2-methyl-butylamino, dimethylamino, diethylamino, N-methyl-propylamino, N-methyl-butylamino, dipropyl-amino, (~-methoxy-ethyl)-amino, (~-ethoxy-ethyl)-amino, (~-methoxy-propyl)-amino, (~-methoxy-propyl)-amino, piperi-dino, morpholino, methoxy, ethoxy and isopropoxy.
The present invention furthermore relate~ to processes for the preparation of the disazo compounds of the formula (1) according to the invention. The~e comprise diazoti~ing an amino compound of the formula H2N-D2, where D2 has the abovementioned me~n; ng, in a procedure which i~ known per se, for example at -5C to +15C in a 6 21 54~ 2 8 strongly acid a~ueoUQ medium below a pH of 1.5 by means of an alkali metal nitrite, and coupling the resulting diazonium compound with an azo compound of the formula (5) ~03S ~ so3~
where Dl and M have the abo~ementioned meAn;ng, in a procedure known per se, for example at a pH of 5 to 9, preferably 6 to 7.5, and at a temperature of between O
and 15C, preferably between 5 and 10C, or reacting a compound of the formula (6) H2N OH 5031,( U O 3 S N--N--¢ ( 6 ) NH-R
in which Dl, M and R have the abovementioned meAn;ngs with cyanuric fluoride (2,4,6-trifluoro-1,3,5-triazine) at a temperature of between -5C and +20C, preferably between O and 10C, and at a pH of between 4 and 8, preferably between 5 and 7, to give the difluoro-tria-zinylamino-disazo compound and then reacting this with a compound of the formula H-Q, where Q has the abovemen-tioned meAn;ng, at a temperature of between -5C and +20C, preferably between O and 10C, and at a pH of between 5 and 10, preferably between 7 and 9, or reacting a compound of the formula (6) with a compound of the formula (7) 2154~8 r ( 7 ) J~N~ Q
in which Q has the abovementioned meAn;ng at a pH of between 3 and 8, preferably between 5 and 7, and at a temperature of between 5 and 30C, preferably between 10 and 20C.
The starting compounds of the formula (5) are known and can be prepared in the customary manner by reaction of the diazonium salt of the amine of the formula Dl-NH2 with 1-amino-8-naphthol-3,6-disulfonic acid. The com-pounds of the formula (6) are likewise known. They can be prepared, for example, by diazotizing an amino compound of the formula (8) co3~
H2N ~ (8) R-N-~cy I
in which M and R have the abovementioned meAn;ngs and acyl is an AlkAnoyl radical having 2 to 5 carbon atoms, ~uch as the acetyl radical, in a procedure which i8 known per se, such as, for example, at -5C to +15C, and coupling ~he diazotization product to a compound of the formula (5) at a pH of between 5 and 7 . 5 and at a tem-perature of between 5 and 20C, and converting the acylamino group in the disazo compound thus obtained into the free amino group by alkaline hydrolysis at a pH of between 10 and 14, preferably between 11 and 13. In this alkaline hydrolysis reaction, the group Y-SO2- can be converted into the ~-hydroxyethylsulfonyl group in the starting disazo compound, and for this reason a compound correspo~;ng to the formula (5) in which the group Y-SO2- is already the ~-hydroxyethylsulfonyl group can also be used as the starting substance in this proces~
variant. The disazo compound with the ~-hydroxyethylsul-fonyl group which contains amino groups can be converted into the compound of the formula (6), where Y is ~-sulfatoethyl, by means of concentrated sulfuric acid at a temperature of between O and 5C.
The deacylation of the starting compound to give the compound of the formula (6) can also be carried out by first converting the acylamino-disazo compound into the vinylsulfonyl-disazo compound which still contains acylamino groups at a temperature of between O and 20C, preferably between 10 and 15C, and at a pH of between 11 and 13, preferably 12 and 12.5, to form the vinyl group from the existing group Y, and deacylating this compound in an aqueous medium at a pH below 1 and at a temperature of between 90 and 100C.
The ~tarting compounds of the formula H2N-D2 can be prepared analogously to known procedures, such as, for example, by reacting an amine of the formula (9) so3~
H2N ~ ( 9 ) I
NH-R
where R and M have the abovementioned me~n;ng with cyanuric fluoride analogously to the instruction~ in German Offenlegungsschrift 2 746 109 and then reacting the resulting difluorotriazinylamino-sulfoaniline co~pound with a compound of the formula H-Q at a tempera-ture of between O and 20C and a pH of between 6 and 10.
Another possibility for synthesis of the starting 215~528 g compounds of the formula H2N-D2 can comprise reacting a compound of the formula (7) with a compound of the formula (9) in aqueou~ solution or suspen~ion at a temperature of between 5 and 30C, preferably between 10 and 20C, and at a pH of between 4 and 8, preferably between 5 and 7.
The starting compounds of the formula (7) themselves can be prepared, for example, analogously to the instructions of French Patent 1 561 876 or in accordance with J. Org.
Chem. 27, 2509 (1962).
The compounds of the formula (1) prepared according to the invention - called compounds (1) below - are sepa-rated off from the synthesis batches by generally known methods, either by precipitation from the reaction medium by means of electrolytes, such as, for example, sodium chloride and potassium chloride, or by evaporation of the reaction solution, for example by spray drying, in which case a buffer substance can be added to this reaction solution. The compounds (1) have fiber-reactive properties and have very good dyestuff properties. They can therefore be used for dyeing material cont~in;ng hydroxy and/or carboxamide groups, in particular fiber material, and also leather. The solutions obtained during synthesis of the compounds according to the invention can likewi~e also be used for dyeing directly as a liquid preparation, if appropriate after addition of a buffer substance, and if appropriate after concentration.
The present invention therefore also relates to the use of the compounds (1) for dyeing materials cont~;n;ng hydroxy or carboxamide groups and to processes for their use on these substrates. This includes bulk dyeing, for example of films of polyamide, and dyeing by printing.
The material~ are preferably used in the form of fiber materials, in particular as textile fiber materials, such as in the form of woven fabrics or as yarns, ~uch as in the form of hanks and wound packages.
215g528 Naterials contA;ning hydroxy groups are naturally occurring or synthetic materials containing hydroxy groups, such as, $or example, cellulose fiber materials or regenerated products thereof and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton, and also other plant fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are, for example, viscose staple and filament viscose.
Materials containing caLboxa~.ide groups are, for example, synthetic and naturally occurring polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide 6,6, polyamide 6, polyamide 11 and polyamide 4.
The compounds (1) can be applied to and fixed on the substrates mentioned, in particular the fiber materials mentioned, by the use techniques known for water-soluble dyestuffs, in particular for fiber-reactive dyestuffs.
Dyeings with very good color yields and an excellent color build-up at high degrees of fixing are thus obtained with them on cellulose fibers by the exhaust process from a long liquor using the most diverse acid-b;n~;ng agents and if appropriate neutral salts, such as sodium chloride or sodium sulfate. Dyeing is carried out in an aqueous bath at temperatures of between 40 and 105C, if appropriate at temperatures of up to 120C, under pressure and if appropriate in the presence of customary dyeing auxiliaries. A procedure can be followed here in which the material i8 introduced into the warm bath and this is heated gradually to the desired dyeing temperature and the dyeing process is brought to comp-letion at this temperature. If desired, the neutral salts which accelerate exhaustion of the compounds (1) can also be added to the bath only after the actual dyeing tempe-rature has been reached.
Excellent color yields with high degrees of fixing and a very good color build-up are likewise obtained on 2'1~ 8 cellulose fibers by the padding proces~, in which the dye~tuffs can be fixed in the customary manner by batching at room temperature or elevated temperature, for example up to about 60C, by steaming or with dry heat.
Deep prints with a good contour status and a clear white background are likewise obtained by the customary print-ing proce~ses for cellulose fibers, which can be carried out either in one phase, for example by printing with a printing paste comprising sodium carbonate or another acid-b;n~; ng agent and the compound (1) and subsequently ste~;ng at 100 to 103C, or in two pha~es, for example by printing with a neutral or weakly acid printing paste comprising the coloring agent and then fixing either by passing the printed goods through a hot electrolyte-containing alkaline bath or by over-padding with an alkaline electrolyte-containing padding liquor and subsequent batching of thiR treated material or subse-quent steaming or ~ub~equent treatment with dry heat. The appearance of the prints depends only little on the varying fixing condition~. The degrees of fixing obtained with the compounds (1) are very high both in dyeing and in printing.
Hot air of 120 to 200C is used for fixing by means of dry heat by the customary thermofixing procesAes. In addition to the usual steam of 101 to 103C, it is also po~6ible to employ superheated Rteam and presRurized steam having temperatures of up to 160C.
The agents which effect b;n~;ng of the acid and fixing of the compounds (1) to the cellulose fibers are, for example, water-~oluble basic Ralts of the alkali metals and of the alkaline earth metals with inorganic or organic acid~, and also compounds which liberate alkali under the influence of heat. The alkali metal hydroxides and alkali metal ~alts of weak to moderately strong inorganic or organic acids are to be mentioned in par-ticular, the ~odium and pota~ium compound~ preferably 2I5~528 being meant by the alkali metal compounds. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbo-nate, potassium carbonate, 60dium formate, sodium dihy-drogenphosphate, disodium hydrogenphosphate, sodiumtrichloroacetate, ~odium silicate or trisodium phosphate.
By treating the compounds (1) with the acid-b;n~;ng agents, if appropriate under the action of heat, they are bonded chemically to the cellulose fibers; the cellulose dyeings in particular show excellent wet-fastness prop-erties after the customary after-treatment by rinsing to remove non-fixed portions of the compounds (1), especi-ally since such non-fixed portions can easily be washed out because of their good solubility in cold water.
The dyeings on polyurethane and polyamide fibers are usually carried out from an acid medium. Thus, for example, acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate can be added to the dyebath in order to obtain the desired pH.
For the purpose of achieving a usable levelness of the dyeing, addition of customary leveling auxiliaries, such as, for example, based on a reaction product of cyanuric chloride with three times the molar amount of an amino-benzenesulfonic acid and/or an aminonaphthalenesulfonic acid or based on a reaction product of, for example, stearylamine and ethylene oxide, is advisable. As a rule, the material to be dyed is introduced into the bath at a temperature of about 40C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature of between 60 and 98C. However, the dyeings can also be carried out at the boiling point or at temperatures of up to 120C (under pressure).
The dyeings and prints produced with the compounds (1) are distinguished by clear shades. The dyeings and prints 2 1 ~ 4 5 2 8 on cellulose fiber materials in particular furthermore have, as already mentioned, a good depth of color, a good fastness to light and very good wet-fastness properties, such as fastnesses to wA~h; ng, milling, water, salt water, cross-dyeing and perspiration, and moreover good fastness to pleating, fastness to ironing and fastness to rubbing.
The high fixing yields which can be achieved with the dyestuffs according to the invention on cellulose fiber materials, which can be more than 90 % when used in printing processes and pad-dyeing processes, are to be emphasized in particular. Another advantage of the compounds (1) is that the portions which have not been fixed in the printing or dyeing operation can easily be washed out, which means that the operation of w~h;ng the printed or dyed cellulose fiber materials can be carried out with small amounts of wash liquor and, if appro-priate, with an energy-saving temperature program during the washing operation.
The following Examples serve to illustrate the invention.
The parts are parts by weight and the percentage data are percentages by weight, unless noted otherwise. Parts by weight bear the same relation to parts by volume as the kilogram to the liter.
The compounds described by way of their formulae in the Examples are 8hown in the form of the free acid; in general, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and are used for dyeing in the form of their salts. The starting compounds and components mentioned in the form of the free acid in the following Examples~ in particular the Tabular Examples, can like-wise be employed in the synthesis as such or in the form of their salts, preferably alkali metal salts.
The absorption maxima (AmaX) in the visible range stated 2 t51 528 for the dyestuffs according to the invention were deter-mined with the aid of their alkali metal salt~ in aqueous solution. In the Tabular Examples,the AmaX value~ are in parentheses with the color shade data; the wavelength data are in nm.
Example 1 30 parts of trifluorotriazine are constantly added to a neutral aqueous solution of 135 parts of the disazo compound 2-(4'-(~-sulfatoethylsulfonyl-phenyl)-azo-7-(2"-sulfo-5-amino-phenyl)-azo-3,6-disulfo-1-amino-8-hydroxy-naphthalene in 1500 parts of a mixture of water and ice - in the course of about 5 minutes, while stirring vigo-rously and maintA; n; ng a pH of between 5 and 6 by means of aqueous sodium hydroxide solution. The mixture is subsequently stirred for a further 30 minutes, 10.8 parts of ammonium chloride are then added, stirring is con-tinued for a further 4 hours at 0 to 5C and a pH of between 8 and 9, then the mixture is brought to a pH of 6.5 by means of aqueous hydrochloric acid, and the resulting disazo compound according to the invention, of the formula (written in the form of the free acid) _~ N ;N ~5 0, H~ NiN
CH2 . NH~N-~NH2 U~x~ 604nm) is isolated as the alkali metal salt (sodium salt) in the customary manner, for example by spray drying or by salting out with sodium chloride.
The disazo compound according to the invention h~s very good fiber-reactive dyestuff properties and gives dyeings ~15452~
and prints in deep navy blue shade~ with good fastness properties on the materials mentioned in the description, in particular on materials cont~;n;ng cellulose fibers, by the use processes customary for fiber-reactive in industry dyestuffs.
Example 2 30 parts of trifluorotriazine are constantly added to a neutral aqueous solution of 133 parts of the disazo compound 2-(4'-(vinylsulfonyl-phenyl)-azo-7-(2"-sulfo-5-amino-phenyl)-azo-3,6-disulfo-1-amino-8-hydroxy-naphtha-lene in 1500 parts of a mixture of water and ice in the course of about 5 minutes, while maintA;n;ng a pH of between 5 and 6 by means of aqueous sodium hydroxide solution and stirring vigorously. The mixture is subsequently stirred for a further 30 minutes, 13.5 parts of methylammonium chloride are then added, stirring is continued at O to 5C and a pH of between 8 and 9 for a further 4 hours, then the mixture is brought to a pH of 6.5 by means of agueous hydrochloric acid, and the resulting disazo compound according to the invention, of the formula (written in the form of the free acid) H2N OH SO~H
~ N ;N ~S 0, H~l N iN
CH~CH2 NHJ~N~ NH
CH~
~maX = 604 nm) is isolated as the alkali metal salt (sodium salt) in the customary manner, for example by spray drying or by salting out with sodium chloride.
The disazo compound according to the invention ha~ very good fiber-reactive dyestuff properties and gives dyeings 215~528 and prints in deep navy blue shades with good fastness properties on the materials mentioned in the description, in particular on materials containing cellulose fibers, by the use processes customary for fiber-reactive dye-stuffs in industry.
Example 3 A mixture of 140 parts of potassium fluoride and 500 parts of tetrahydrothiophene 1,1-dioxide (=
sulfolane) is heated to 120C in a flask with a distill-ation column and condenser, and a su~penQion of 193 partsof 2,4-dichloro-6-dimethylamino-1,3,5-triazine in 400 parts of sulfolane is slowly added, whilst stirring thoroughly. The mixture is ~ubsequently stirred at 150C
for about a further 4 hours and the 2,4-difluoro-6-dimethylamino-1,3,5-triazine prepared is isolated in a yield of 130 parts by distillation at 94-95C/17 mbar.
The compound has a melting point of 72-73C.
48 parts of this difluoro compound are stirred into a solution, at 10C and a pH of 6, of 56 parts of 1,3-diaminobenzene-4-sulfonic acid in 600 parts of water, and the reaction is brought to completion in the course of about 8 hours, while stirring further at 10 to 20C and at a pH of 5 to 7. The 2-(4'-sulfo-3'-amino-phenylamino)-4-fluoro-6-dimethylamino-1,3,5-triazine thus obtainedcan be isolated by salting out or processed further for the preparation of a disazo compound according to the inven-tion without further intermediate isolation.
56.2 parts of 4-(~-sulfatoethylsulfonyl)-aniline are diazotized in a procedure known per se and the diazotiza-tion product is coupled with 63 parts of 1-amino-8-naphthol-3,6-di~ulfonic acid at a pH below 1.5. The diazonium Qalt suspension, prepared in a procedure known per se, of 33 parts of the 2-(4'-sulfo-3'-amino-phenyl-amino)-4-fluoro-6-dimethylamino-1,3,5-triazine described above is added to the monoazo compound solution thus prepared and the coupling reaction is brought to completion in the course of about 4 hours at 10 to 15C
and at a pH of between 5 and 7.
The disazo compound according to the invention, of the formula (written in the form of the free acid) S2 ~ HO S ~ SOJH ~ NiN
l H2 N H~N-~N ( CH3 ) 2 UnUX = 604 nm~
is isolated as the alkali metal salt (sodium salt) in a customary manner by salting out with sodium chloride or by spray drying.
The disazo compound according to the invention has very good fiber-reactive dyestuff properties and gives dyeings and prints in deep navy blue shades with good fastness properties on the materials mentioned in the description, in particular on materials cont~; n; ng cellulose fibers, by the use processes customary for fiber-reactive dye-stuffs in industry.
Example 4 parts of 2,4-difluoro-6-methylamino-1,3,5-triazine (which is prepared in accordance with the instructions of French Patent 1 561 876) are added to a solution, at 0C
and a pH of 6, of 56 parts of 1,3-diaminobenzene-4-sulfonic acid in 600 parts of water, while stirringthoroughly. The mixture is further stirred at 10C and at a pH of between 5 and 7 for about a further 6 hours and the 2-(4'-sulfo-3'-amino-phenylamino)-4-fluoro-6-methyl-amino-1,3,5-triazine thus obtained is reacted with the equivalent amount of the monoazo compound 2-(4'-~-sul-fatoethylsulfonyl-phenyl)-azo-3,6-disulfo-1-amino-8-2~ S4528 hydroxy-naphthalene analogously to the instructions of Example 3, after conversion into the diazonium salt, to give the disazo compound according to the invention of the formula (written in the form of the free acid) 2~H O; 5~5 0, H~ NiN
CH2-CH20SO3H NH--~N-J--NH
~rrUx = 604 nm~
This is isolated as the alkali metal salt (sodium salt) by salting out with sodium chloride or by spray drying.
The disazo compound according to the invention has the same good dyestuff properties a~ the disazo compound of Example 2 according to the invention.
Examples 5 to 16 Further disazo compounds according to the invention, corre8pon~; ng to the formula (A) Dl-N--N~;N----N~3 i (A) R--N ~NJ--Q
are described with the aid of their components in the following Tabular Examples. They can be prepared in the manner according to the invention, for example analo-gously to the abovementioned Examples.from the starting compounds which can be ~een from the formula (A) (the diazo component Dl-NH2, 3,6-di~ulfo-1-amino-8-naphthol, an optionally N-alkyl-substituted 2-sulfo-1,3-phenylene-- - 2 1 545~8 dlamlne, cyanurlc fluorlde and a compound of the formula H-Q~.
They have very good flber-reactlve dyestuff propertles and dye the materlals mentloned ln the descrlptlon, such as, ln partlcular, cellulose flber materlals, ln the color shades stated ln the partlcular Tabular Example (for cotton here) wlth a good depth of color and good fastnesses.
Disazo compound of the formula (A) ExampleRadical D1 Radical R Radical Q Color shade 5 4-(~-sulfato-ethyl- hydrogen methylamino navy blue sulfonyl-phenyl (606) 6 ditto hy~Logendimethylamino navy blue (604) 7 ditto hydrogenethylamino navy blue (605) 8 ditto hydrogenn-propylamino navy blue ~605) 9 ditto hydrogen n-butylamino navy blue (604) ditto hydrogen y-methoxy- navy blue propyl-amino (603) 11 ditto hydrogen diethylamino navy blue (606) 124-(vinylsulfonyl)- methyl amino navy blue phenyl 13 ditto methyldimethylamino navy blue 14 ditto methylethylamino navy blue ditto ethyln-propylamino navy blue 16 ditto methyl~-methoxy- navy blue methyl-amino
Claims (9)
1. A disazo compound of the formula (1) (1) in which:
M is hydrogen or an alkali metal;
D1 is a radical of the formula (2a) or (2b) (2a) (2b) in which Y is vinyl, or is ethyl which is substituted in the .beta.-position by a substituent which is eliminated by an alkali to form the vinyl group, n is the number 1 or 2, R1 is hydrogen, halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo or carboxy , R2 is hydrogen, chlorine, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, m is the number zero, 1 or 2 (and in the case where m is zero, this group is hydrogen) and M has the abovementioned meaning;
D2 is a group of the formula (3) (3) in which M has the abovementioned meaning, R is hydrogen or alkyl having 1 to 4 carbon atoms and Q is alkoxy having 1 to 4 carbon atoms or alkoxy having 2 to 4 carbon atoms which is substituted by alkoxy having 1 to 4 carbon atoms, or is a group of the formula (4) ( 4 ) in which RA is hydrogen or alkyl having 1 to 6 carbon atoms, which can be substituted by alkoxy having 1 to 4 carbon atoms, and RB has one of the meanings of RA, or the group -NRARB forms the radical of a satu-rated five- to eight-membered heterocyclic com-pound which optionally contains a further hetero group.
M is hydrogen or an alkali metal;
D1 is a radical of the formula (2a) or (2b) (2a) (2b) in which Y is vinyl, or is ethyl which is substituted in the .beta.-position by a substituent which is eliminated by an alkali to form the vinyl group, n is the number 1 or 2, R1 is hydrogen, halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo or carboxy , R2 is hydrogen, chlorine, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, m is the number zero, 1 or 2 (and in the case where m is zero, this group is hydrogen) and M has the abovementioned meaning;
D2 is a group of the formula (3) (3) in which M has the abovementioned meaning, R is hydrogen or alkyl having 1 to 4 carbon atoms and Q is alkoxy having 1 to 4 carbon atoms or alkoxy having 2 to 4 carbon atoms which is substituted by alkoxy having 1 to 4 carbon atoms, or is a group of the formula (4) ( 4 ) in which RA is hydrogen or alkyl having 1 to 6 carbon atoms, which can be substituted by alkoxy having 1 to 4 carbon atoms, and RB has one of the meanings of RA, or the group -NRARB forms the radical of a satu-rated five- to eight-membered heterocyclic com-pound which optionally contains a further hetero group.
2. A disazo compound as claimed in claim 1, in which n is the number 1.
3. A disazo compound as claimed in claim 1 or 2, in which R is hydrogen.
4. A disazo compound as claimed in at least one of claims 1 to 3, in which D1 is a group of the formula (2) in which R1 and R2 are each hydrogen, n is the number 1 and the group Y- SO2 - is bonded to the benzene nucleus in the para-position relative to the azo group.
5. A disazo compound as claimed in at least one of claims 1 to 4, in which Q is an amino group of the formula -NRARB having the meaning given in claim 1.
6. A disazo compound as claimed in at least one of claims 1 to 5, in which RA is hydrogen and RB is alkyl having 1 to 4 carbon atoms.
7. A process for the preparation of a disazo compound of the formula (1) as claimed in claim 1, which comprises diazotizing an amino compound of the formula H2N-D2, where D2 has the meaning given in claim 1, and coupling the resulting diazonium com-pound with an azo compound of the formula (5) ( 5 ) where D1 and M have the meaning given in claim 1, or reacting a compound of the formula (6) (6) in which D1, M and R have the meanings given in claim 1 with cyanuric fluoride (2,4,6-trifluoro-1,3,5-triazine) at a temperature of between -5°C and +20°C and at a pH of between 4 and 8 to give the difluoro-triazinylamino-disazo compound and then reacting this with a compound of the formula H-Q, where Q has the abovementioned meaning, at a tem-perature of between -5°C and +20°C and at a pH of between 5 and 10, or reacting a compound of the formula (6) with a compound of the formula (7) ( 7 ) in which Q has the meaning given in claim 1 at a pH
of between 3 and 8 and at a temperature of between 5 and 20°C.
of between 3 and 8 and at a temperature of between 5 and 20°C.
8. The use of a disazo compound as claimed in claim 1 or of a disazo compound prepared as claimed in claim 7 for dyeing (including printing) material contain-ing hydroxy and/or carboxamide groups, in parti-cular fiber material.
9. A process for dyeing (including printing) material containing hydroxy and/or carboxamide groups, in particular fiber material, in which a dyestuff is applied to the material and the dyestuff is fixed on the material by means of heat or with the aid of an agent having an alkaline action or by means of both measures, which comprises employing a disazo com-pound as claimed in claim 1 or a disazo compound prepared as claimed in claim 7 as the dyestuff.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4426322.8 | 1994-07-25 | ||
| DE19944426322 DE4426322A1 (en) | 1994-07-25 | 1994-07-25 | Water-soluble disazo compounds, processes for their preparation and their use as dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2154528A1 true CA2154528A1 (en) | 1996-01-26 |
Family
ID=6524096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2154528 Abandoned CA2154528A1 (en) | 1994-07-25 | 1995-07-24 | Water-soluble disazo compounds, a process for their preparation and their use as dyestuffs |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0694589A1 (en) |
| JP (1) | JPH08109338A (en) |
| BR (1) | BR9503422A (en) |
| CA (1) | CA2154528A1 (en) |
| DE (1) | DE4426322A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1670866A1 (en) | 1967-05-11 | 1971-03-11 | Bayer Ag | Fluorotriazine compounds |
| JPS56155250A (en) * | 1980-04-10 | 1981-12-01 | Nippon Kayaku Co Ltd | Reactive dis-azo compound, production thereof and dyeing method employing the same |
| DE3019936A1 (en) | 1980-05-24 | 1981-12-03 | Hoechst Ag, 6000 Frankfurt | WATER-SOLUBLE COLORED COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| US5241057A (en) * | 1982-01-15 | 1993-08-31 | Bayer Aktiengesellshaft | Amino disazo dyestuffs containing a fluoropyrimidinyl or a fluorotriazinyl reactive group |
| DE3201114A1 (en) * | 1982-01-15 | 1983-07-28 | Bayer Ag, 5090 Leverkusen | DISAZOREACTIVE DYES |
| US5214057A (en) | 1984-12-14 | 1993-05-25 | Novo Nordisk A/S | N-substituted azaheterocyclic carboxylic acids |
| DE3513261A1 (en) * | 1985-04-13 | 1986-10-23 | Bayer Ag, 5090 Leverkusen | DISAZOREACTIVE DYES |
| JPH0751681B2 (en) * | 1986-10-20 | 1995-06-05 | 三菱化学株式会社 | Water-soluble disazo dye |
-
1994
- 1994-07-25 DE DE19944426322 patent/DE4426322A1/en not_active Withdrawn
-
1995
- 1995-07-14 EP EP95111066A patent/EP0694589A1/en not_active Withdrawn
- 1995-07-21 JP JP18603095A patent/JPH08109338A/en not_active Withdrawn
- 1995-07-24 CA CA 2154528 patent/CA2154528A1/en not_active Abandoned
- 1995-07-24 BR BR9503422A patent/BR9503422A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE4426322A1 (en) | 1996-02-01 |
| EP0694589A1 (en) | 1996-01-31 |
| JPH08109338A (en) | 1996-04-30 |
| BR9503422A (en) | 1996-06-04 |
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