WO1999058612A1 - Wasserlösliche monoazoverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbstoffe - Google Patents
Wasserlösliche monoazoverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbstoffe Download PDFInfo
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- WO1999058612A1 WO1999058612A1 PCT/EP1999/002972 EP9902972W WO9958612A1 WO 1999058612 A1 WO1999058612 A1 WO 1999058612A1 EP 9902972 W EP9902972 W EP 9902972W WO 9958612 A1 WO9958612 A1 WO 9958612A1
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- Prior art keywords
- general formula
- carbon atoms
- sulfo
- hydrogen
- group
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- 0 C*c(cc1)cc(nc2*)c1nc2Cl Chemical compound C*c(cc1)cc(nc2*)c1nc2Cl 0.000 description 2
- DTQGEKZIKCPZSO-UHFFFAOYSA-N CC(CC=CC1)C1Cl Chemical compound CC(CC=CC1)C1Cl DTQGEKZIKCPZSO-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
- C09B62/006—Azodyes
- C09B62/008—Monoazo dyes
- C09B62/0085—Monoazo dyes with coupling components containing both hydroxyl and amino groups as directing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
- C09B62/24—Azo dyes
- C09B62/245—Monoazo dyes
-
- 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
- C09B62/4413—Non-metallized monoazo dyes
-
- 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
- C09B62/503—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 the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/51—Monoazo dyes
Definitions
- fiber-reactive azo compounds which contain a ⁇ -carboxy-ethyl-carbonylamino or carboxy-acrylamino group in the sulfonaphthol coupling component.
- dyestuffs for example, they provide red dyeings on cotton, but some properties are unsatisfactory and in some cases have unsatisfactory lightfastness in particular.
- M is hydrogen or an alkali metal such as sodium, potassium or lithium or another colorless salt-forming metal such as the equivalent of an alkaline earth metal such as calcium; m is the number zero or 1 (if m is zero, this group represents hydrogen);
- X is a fiber reactive group or moiety containing a fiber reactive group
- W is alkylene of 1 to 4 carbon atoms, such as methylene, ethylene and n-propylene, or is phenylene which is substituted by 1 or 2 substituents from the group sulfo,
- alkyl of 1 to 4 carbon atoms such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, and chlorine, or is alkylene of 3 to 6 carbon atoms, which can be substituted by a Group -O- or -NH- is interrupted;
- R ° is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, or is phenyl, which can be substituted by sulfo, methyl, ethyl, methoxy, ethoxy or chlorine, preferably hydrogen, methyl or ethyl;
- alk is alkylene of 1 to 4 carbon atoms, such as methylene and ethylene;
- r is the number zero or 1 s is the number zero or 1.
- t is the number zero or 1
- D is phenylene which is substituted by 1 or 2 substituents from the group sulfo,
- Carboxy, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, and chlorine may be substituted, or is naphthylene which is substituted by 1 or 2
- R is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, preferably hydrogen;
- G is the divalent radical of a cycloalkyl of 5 to 8 carbon atoms or bicycloalkyl of 5 to 8 carbon atoms, where the alicyclic radicals can contain an olefinic double bond and / or are interrupted by a hetero group such as -0- or -NH- can be and further by 1 or 2 substituents from the group halogen, such as chlorine and bromine, or alkyl of 1 to 4 carbon atoms, which can be substituted, for example substituted by hydroxy and alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy; if m is 1, the group -SO 3 M is preferably in the 3- or 4-position, particularly preferably in the 3-position, of the 8-hydroxy-naphthalene radical, the group -N (R) -CO-G -COOM is preferably bound in the 1-position of the 8-hydroxy-naphthalene radical, or is in the 4-position, the group -N (R) -CO-
- sulfo groups are groups corresponding to the general formula -SO 3 M, thiosulfato groups corresponding to the general formula -S-S0 3 M, carboxy group groups corresponding to the general formula -COOM,
- G radicals are, for example, the bivalent radical of cyclopentane, cyclohexane, cyclohexene, cycloheptane and cycloheptene, which, as indicated above for G, are substituted by optionally substituted alkyl of 1 to 4 carbon atoms, halogen or alkoxy of 1 to 4 carbon atoms can be, these alicyclic radicals, in particular the cyclohexane and cyclohexene radical, with the aid of an alkylene bridge, such as methylene or ethylene, or an oxygen bridge or an aliphatic bridge with the link -NH- can form the rest of a bicyclus. These residues can exist both in the ice and in the trans form.
- Examples of the radical G are those corresponding to the general formulas (2a), (2b), (2c), (2d) and (2e)
- R 1 is hydrogen, methyl or ethyl
- R 2 is hydrogen, methyl, ethyl or chlorine.
- Residues G are in particular cyclohex-1, 2-ylene, 3-methyl- or 4-methyl-cyclohex-1, 2-ylene, cyclohex-4-en-1, 2-ylene, 7-oxabicyclo (2,2, 1 ) -hept-5-en-2,3-ylene, endo-norbor-5-en-2,3-ylene, 1, 4-dimethyl-cyclohex-4-en-1, 2-ylene, 3-methyl- cyclohex-4-en-1, 2-ylene, methyl-5-norbom-en-2,3-ylene and endo-bicyclo (2,2,2) -oct-5-en-2,3-ylene, respectively in the ice and trans form.
- Fiber-reactive groups X or groupings X which contain a fiber-reactive group are, for example, halogen-substituted s-triazine or pyrimidine groups, where the halogen substituents are fluorine, chlorine or bromine and preferably fluorine or chlorine and the halogen-substituted s-triazine radical can also contain an optionally substituted amino group and the substituents of this amino group can be phenyl, naphthyl or alkyl of 1 to 4 carbon atoms, which in turn contain a fiber-reactive group of the vinylsulfone series, or are, for example, a 2,3-dichlorophenazine- (1, 4) -6- carbonyl radical, where in the event that X is one of these heterocyclic radicals, s is zero and r is 1.
- Examples of X are also fiber-reactive groups of the vinylsulfone series, such as the vinylsulfonyl group or an ethylsulfonyl group which is substituted in the ⁇ -position by an alkali-eliminable substituent.
- Fiber-reactive radicals are, for example, those which have the general formulas (3a), (3b), (3c), (3d), (3e), (3f), (3g), (3h) or (3j)
- Y is vinyl or ethyl which is substituted by an alkali-eliminable substituent, such as chlorine, bromine, sulfato, thiosulfato, phosphato, alkanoyloxy of 2 to 5 carbon atoms, such as acetylox ⁇ , benzoyloxy, sulfobenzoyloxy or p-tolylsulfonyloxy prefers
- an alkali-eliminable substituent such as chlorine, bromine, sulfato, thiosulfato, phosphato, alkanoyloxy of 2 to 5 carbon atoms, such as acetylox ⁇ , benzoyloxy, sulfobenzoyloxy or p-tolylsulfonyloxy prefers
- Ha is each, identical to or different from one another, chlorine, bromine or fluorine, preferably chlorine or fluorine;
- R ⁇ is hydrogen or shark of the above meaning
- RR ° 3 is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxy, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, sulfato, phosphato, carboxy, sulfo or alkoxy of 1 to 4 carbon atoms
- R 4 is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxy, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, sulfato, phosphato, carboxy, sulfo or alkoxy of 1 to 4 carbon atoms, or is an optionally substituted by 1 or 2 methyl cyclohexyl of 5 to 8 carbon atoms or is phenyl which is substituted by 1 or 2 substituents from the group sulfo, carboxy, chlorine, alkyl of 1 to 4 carbon atoms, such as e
- Heterocycle such as piperidino, morpholino or piperazino
- R 5 is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or is phenyl, which can be substituted by chlorine, sulfo, carboxy, methyl, ethyl, methoxy or ethoxy;
- R 6 is a group of the general formula (4a) or (4b)
- ALK is alkylene of 1 to 4 carbon atoms, such as methylene and in particular ethylene or n-propylene, and AR is phenylene, which has 1 or 2 substituents from the group
- Sulfo, carboxy, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, and chlorine, or naphthylene, which is substituted by 1 or 2 sulfo groups can be substituted;
- R 7 is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl, preferred
- R 8 is a group of the general formula (4c) or (4d)
- Alk is alkylene of 2 to 4 carbon atoms, preferably ethylene, E is a group -O- or -NH-, p is the number zero or 1 and q is the number zero or 1, the sum (p + q ) the number is 1.
- Preferred groups corresponding to the general formula X- (W) s - (NR °) r - (alk) t -D-, which is contained in the general formula (1), are in particular groups corresponding to the general formulas (5a), ( 5b), (5c) and (5d)
- Y, M, R ° and m have one of the meanings mentioned above;
- R 9 is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, or halogen, such as chlorine;
- R 10 is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular
- Methyl, or alkoxy of 1 to 4 carbon atoms such as ethoxy and in particular
- R 1 1 is hydrogen, sulfo, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy;
- V is a group of the general formula defined above
- n is the number 1, 2 or 3.
- Residues of the general formulas (5a) and (5b) are, for example, 4- ( ⁇ -sulfatoethylsulfonyl) phenyl, 4-vinylsulfonylphenyl,
- Heterocyclic fiber-reactive radicals corresponding to the general formulas (3a) to (3h) are, for example, 2,4-difluoro-5-chloropyrimidin-6-yl, 2,4-difluoropyrimidin-6-yl, 4,6-difluoro 5-chloro-pyrimidin-2-yl, 4,6-difluoropyrimidin-4-yl and groups of the general formulas (3f), (3g) and (3h), in which R 3 is hydrogen, methyl, ethyl, ⁇ - Hydroxyethyl or ß-sulfoethyl means R 4 is hydrogen, methyl, ethyl, ß-hydroxyethyl, cyclohexyl, phenyl, 2-sulfophenyl,
- R 5 is hydrogen
- R 6 is 4- ( ⁇ -sulfatoethylsulfonyl) phenyl
- formula (5d) which are contained in formula (5d) are, for example, 3- (N-methylamino) methyl-5-sulfo-2,6-dimethylphenyl, 4- (N-methylamino) methyl-3-sulfo -phenyl, 2-aminomethyl-6-sulfo-4-methyl-phenyl and 5-aminomethyl-1 -sulfonaphth-2-yl.
- G has the above-mentioned, particularly preferred meaning and is particularly preferably cyclohex-1, 2-ylene or cyclohex-4-en-1, 2-ylene; the group -NH-CO-G-COOM is in the formula (1B) in the 2- or 3-position bonded to the 8-hydroxy-naphthalene radical;
- X ° -D 1 - is a radical of the general formula (5a) defined above, in which Y is preferably vinyl or ⁇ -sulfatoethyl and R 9 and R 10 are both preferably hydrogen or R 9 is preferably hydrogen and R 10 is preferably methyl Is ethyl, methoxy or ethoxy and the group Y-SO 2 - is bonded in the meta or para position for free binding to the benzene nucleus, or is a group of the general formula (5b) defined above, in which Y is preferably vinyl or is ⁇ -sulfatoethyl, M has the abovementioned meaning and m is the
- R ° is preferably hydrogen, methyl or ethyl.
- the monoazo compounds of the general formula (1) according to the invention can be prepared in various ways, for example by reacting an aminonaphtholsulfonic acid of the general formula (9)
- Such inert organic solvents which can also be used in the reaction of an aminonaphthol of the general formula (9) with an anhydride of the general formula (10) are, for example, dimethyl sulfoxide, dimethylformamide and N-methyl-pyrrolidone.
- a reaction of the aminonaphtholsulphonic acid of the general formula (9) with the anhydrides of the general formula (10) is advantageously carried out by adding the fine-grained or powdered anhydride to an aqueous solution of the aminonaphtholsulphonic acid and thereby having a pH between 2 and 8 , preferably between 4 and 7, and the reaction is carried out at a temperature between 0 and 30 ° C, preferably 0 and 25 ° C.
- the pH can usually be set and maintained using an alkaline compound, such as sodium carbonate and sodium hydrogen carbonate or aqueous sodium hydroxide solution, also with the aid of the corresponding lithium compounds.
- the coupling reaction of a compound of the general formula (1 1) with the diazonium compounds of the amines of the general formula (1 2) or (1 3) takes place in a customary manner in aqueous solution, for example at a temperature between 0 and 25 ° C., preferably between 5 and 20 ° C, and at a pH between 3 and 8, preferably between 4 and 6.5.
- the diazotization of the amino compounds also takes place in a generally customary manner in aqueous solution, for example using sodium nitrite in a strongly acidic, for example hydrochloric or sulfuric, medium at a temperature between -5 ° C. and + 20 ° C. and at a pH of less than 3, preferably less than 2.5.
- the starting compounds which are used to synthesize the compound of the general formula (1) are generally known or can be prepared analogously to known procedures, for example the amino compounds of the general formula (1 2) with X being a heterocyclic radical by reacting an amino compound of the general Formula (1 3) with a
- 3-amino-8-naphthol-6-sulfonic acid 3-methylamino-8-naphthol-6-suifonic acid, 2-amino-8-naphthol-6-sulfonic acid, 3-amino-8-naphthol-4,6-disulfonic acid, 1-amino-8-naphthol-6-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 3-amino-8-naphthol-4-sulfonic acid and 2-amino-8-naphthol-3,6-disulfonic acid, in particular 3-amino-8-naphthol-6-sulfonic acid, 3-methylamino-8-naphthol-6-sulfonic acid and 2-amino-8-naphthol-6-sulfonic acid, preferably 1-amino-8-naphthol-3,6- disulfonic acid, 3-
- Starting compounds of the general formula (10) are, for example, trans- and cis-cyclohexane-1, 2-dicarboxylic acid anhydride, trans- and cis-4-cyclohexene-1, 2-dicarboxylic acid anhydride, trans- and cis-5-norbonen-endo-2 , 3-dicarboxylic acid anhydride, trans- and cis-exo-7-oxabicyclo (2.2.1) hept-5-en-2,3-dicarboxylic acid anhydride, trans- and cis-1, 4-dimethylcyclohex-4-en-1,2 - dicarboxylic acid anhydride, trans- and cis-3-methylcyclohex-4-en-1,2-dicarboxylic acid anhydride, trans- and cis-methyl-5-norbonen-2,3-dicarboxylic acid anhydride and trans- and cis-endo-bicyclo (2.2. 2) oct-5-ene-2,3
- Amines serving as diazo components which have a fiber-reactive group of the vinylsulfone series and which correspond to the general formula (1 2), in which X is a group of the general formula Y-S0 2 - with Y of the abovementioned meaning and which is preferably an amine of the general formula Y-S0 2 -D-NH 2 correspond, for example 4- (ß-sulfatoethylsulfonyl) aniline, 4-vinylsulfonyl-aniline, 3- (ß-sulfatoethylsulfonyl) aniline, 2- (ß-sulfatoethylsulfonyl) aniline, 2-methoxy 5- (ß-sulfatoethylsulfonyl) aniiin, 2-methoxy-5-vinylsulfonyl-aniline, 2-sulfo-4- (ß-sulfatoethylsulfonyl) aniline, 2-methoxy-5-methyl
- Starting compounds corresponding to the general formulas (3a) to (3d) are, for example, 2,4,6-difluoro-5-chloropyrimidine and 2,4,6-trifluoropyrimidine.
- the deposition and isolation of the monoazo compounds of the general formula (1) according to the invention from the aqueous synthesis solutions can be carried out according to generally known methods for water-soluble compounds, for example by precipitation from the reaction medium using an electrolyte, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution itself , for example by spray drying. If the latter type of insulation is chosen, it is often advisable to remove any amounts of sulfate present in the solutions by evaporation as calcium sulfate and separation by filtration before evaporation.
- the monoazo compounds of the general formula (1) according to the invention - hereinafter referred to as compounds (1) - have fiber-reactive properties and have very valuable dye properties. They can therefore be used for dyeing (including printing) materials containing hydroxy groups and / or carbonamide groups.
- the solutions obtained in the synthesis of the compounds (1) if appropriate after adding a buffer substance and if appropriate also after concentration, can be used directly as a liquid preparation for dyeing.
- the present invention therefore also relates to the use of the compounds (1) for dyeing (including printing) hydroxyl- and / or carbonamide-containing materials and processes for their use on these substrates.
- the materials preferably come in the form of
- Fiber materials for use especially in the form of textile fibers, such as
- Materials containing hydroxyl groups are of natural or synthetic origin, such as cellulose fiber materials or their regeneration products and polyvinyl alcohols.
- Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; Regenerated cellulose fibers are, for example, cellulose and viscose rayon.
- Materials containing carbonamide groups are, for example, synthetic and natural 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-1 1 and polyamide-4.
- the fiber materials can also be processed and dyed in mixtures with one another or can contain fiber materials of a different chemical nature, such as polyester fibers. Examples of this are blended fabrics made of cellulose fibers and polyester fibers and of cellulose fibers and polyamide fibers.
- the compounds (1) can be applied and fixed on the substrates mentioned, in particular on the fiber materials mentioned, by the application techniques known for water-soluble, fiber-reactive dyes, for example by dissolving the compound (1) in solution applies to or brings them into the substrate and fixes them on or in this by the action of heat or by the action of an alkaline agent or by both measures.
- staining and fixing methods have been described in numerous publications (for example in European Patent Application Publication No. 0 1 81 585).
- the compounds (1) are suitable both for the exhaust dyeing process and for dyeing according to the pad dyeing process, after which the goods are impregnated with aqueous, optionally containing electrolyte salts of the compounds (1) and the compound (1) in the manner indicated above on the
- Compounds (1) are particularly suitable for use according to the so-called cold residence process, according to which a dye is applied together with the alkaline agents to the fiber material on the pad, on which it is fixed after storage for several hours at room temperature. After fixing, the dyeings and prints obtained are thoroughly rinsed with cold and hot water, if appropriate with the addition of an agent which has a dispersing action and requires diffusion of the unfixed portions.
- the compounds (1) are notable for high reactivity, good fixing power and very good build-up power. They can therefore be used at low dyeing temperatures using the pull-out dyeing process and only require short steaming times with the pad-steam process.
- the degrees of fixation are high and non-fixed portions can be easily washed out, the difference between the degree of exhaustion and the degree of fixation being remarkably small, which is why the soap loss is also very low.
- the compounds (1) are also particularly suitable in the textile printing process, especially on
- Cellulose fiber materials such as cotton, but also for printing fiber material containing carbonamide groups, such as wool and silk or blended fabrics containing wool or silk. They are still very well suited for use in the etching and reserve printing processes.
- the dyeings and prints produced with the compounds (1), in particular also cellulose fiber materials have a high color strength and high binding stability to the fiber both in the acidic and in the alkaline range and also have good light fastness, including very good
- wet light fastness as well as generally good wet fastnesses, such as good wash, water, sea water, over-dyeing and sweat fastnesses, furthermore good pleating fastness, ironing fastness and rubbing fastness.
- Parts by weight relate to parts by volume such as kilograms to liters.
- the absorption maxima ( ⁇ max ) in the visible range specified for the compounds according to the invention were determined on the basis of the alkali metal salts in aqueous solution.
- the ⁇ max values are given in brackets when specifying the color; the wavelength specification refers to nm.
- a solution with a pH of 7 and a temperature of 15 to 20 ° C. of 239 parts of 3-amino-6-sulfo-8-naphthol in 1,500 parts of water are mixed with 1 70 parts of cis-cyclohex-4-ene -1, 2-dicarboxylic anhydride are added, and the reaction mixture is kept at a pH of 6 and a temperature of 0 to 5 ° C. for about five hours.
- Diazonium salt from 41 0 parts of 1-sulfo-6- (ß-sulfatoethylsulfonyl) -2- aminonaphthalene and carries out the coupling reaction at about 15 ° C and a pH between 5.5 and 6.5.
- the synthesis mixture is isolated from the synthesis mixture in the usual way, for example by salting out with sodium chloride or spray drying, as the alkali metal salt. It dyes the fiber materials mentioned in the description, such as cotton, in clear red tones with good fastness properties, from which in particular the light and wash fastness can be emphasized.
- a solution of the lithium acid from 239 parts of 2-amino-6-sulfo-8-naphthol in 2000 parts of water is mixed with 1 75 parts of cis-cyclohex-4- at a pH of 7 and a temperature of 15 to 20 ° C. en-1,2-dicarboxylic anhydride added; the reaction mixture is stirred for a further 3 hours at 15 to 20 ° C. while maintaining a pH of 6 by means of lithium hydroxide and then mixed with a hydrochloric acid diazonium salt suspension prepared in the usual way from 281 parts of 4- ( ⁇ -sulfatoethylsulfonyl) aniline.
- the coupling reaction is carried out at a pH of 4 to 5 and a temperature of 5 to 10 ° C. and the azo compound of the formula (written in the form of the free acid) is then isolated
- a neutral solution of the sodium salt from 31 9 parts of 1-amino-3,6-disulfo-8-naphthol in 4000 parts of ice water is mixed with 1 80 parts of cis-cyclohexane-1,2-dicarboxylic anhydride; the mixture is stirred for about another five hours at a pH of 6 and a temperature of 0 to 5 ° C.
- a neutral solution of 252 parts of 1-sulfo-5-methylamino-2-amino-naphthalene and 71 parts of sodium nitrite in 2500 parts of water at 5 ° C. is slowly and steadily added to a mixture of 2000 parts of ice and 300 parts by volume of concentrated aqueous hydrochloric acid.
- the mixture is stirred for a further hour and excess nitrite is removed under amidosulfonic acid in the customary manner.
- the diazonium salt suspension is then added to the initially prepared batch with the coupling component, and the coupling reaction is carried out for about an hour at a pH of 7 and a temperature of about 20 ° C.
- the mixture is then heated to 40 ° C. and adjusted to a pH of 8; 1,87 parts of 2,4,6-trifluoro-5-chloropyridimine are stirred in continuously with good stirring and maintaining a pH of 8 and a temperature of 40.degree.
- the monoazo compound according to the invention written in the form of the free acid, has the formula HO NH -
- dyes for example, cotton according to the dyeing and printing processes customary in the art for fiber-reactive dyes in strong red tones with good fastness properties, of which the good fastness to light and wash fastness can be emphasized in particular.
- a solution with a pH value of 6.5 of 281 parts of 4- ( ⁇ -sulfatoethylsuifonyD-aniline and 40 parts of sodium fluoride in 3500 parts of ice water are mixed with 1 50 parts of cyanuric fluoride according to the procedure of DE-A 27 with slow addition and thorough stirring 46 1 09.
- 80 parts of 1,3-diaminobenzene-4-sulfonic acid are added to the batch, the pH is adjusted to 6.5 with sodium carbonate and the pH is maintained and the temperature is from 0 to 1 0 ° C continued for about three hours.
- the mixture is then cooled to 0 ° C. and the amino compound obtained is diazotized in a manner known per se using sodium nitrite and concentrated hydrochloric acid.
- the diazonium salt solution obtained is then added to the solution of the coupling component which, according to the present example 2, consists of 31 9 parts of 1-amino-3,6-disulfo-8-naphthol and 1 80 parts of cis-cyclohex-4-en-1,2- dicarboxylic anhydride was prepared.
- the coupling reaction takes place at a pH between 5.5 and 6.5 and a temperature of about 15 ° C.
- the monoazo compound according to the invention is then salted out with sodium chloride and isolated. It shows very good fiber-reactive dye properties and dyes, for example, cotton in bright red tones with good fastness properties.
- a solution of the lithium salt from 239 parts of 2-amino-6-sulfo-8-naphthol in 2000 parts of water is mixed with 1 75 parts of trans-cyclohex-4- at a pH of 7 and a temperature of 15 to 20 ° C. en-1,2-dicarboxylic anhydride added; the reaction mixture is stirred for a further 3 hours at 15 to 20 ° C. while maintaining a pH of 6 by means of lithium hydroxide and then mixed with a hydrochloric acid diazonium salt suspension prepared in the usual way from 281 parts of 4- ( ⁇ -sulfatoethylsulfonyl) aniline.
- the coupling reaction is carried out at a pH of 4 to 5 and a temperature of 5 to 10 ° C. and the azo compound of the formula (written in the form of the free acid) is then isolated
- N N NH - CA iOOH
- Example 66 A pH 6.5 solution of 281 parts of 4- ( ⁇ -)
- the mixture is then cooled to 0 ° C. and the amino compound obtained is diazotized in a manner known per se using sodium nitrite and concentrated hydrochloric acid.
- the diazonium salt solution obtained is then added to the solution of the coupling component which, according to the present example 2, consists of 31 9 parts of 1-amino-3,6-disulfo-8-naphthol and 1 80 parts of trans-cyclohex-4-en-1,2- dicarboxylic anhydride was prepared.
- the coupling reaction takes place at a pH between 5.5 and 6.5 and a temperature of about 15 ° C.
- N N NH - CQ OOOH
- Example 68 A solution of the lithium salt from 239 parts of 2-amino-6-sulfo-8-naphthol in 2000 parts of water is mixed with 1 75 parts of 4-methyl- at a pH of 7 and a temperature of 15 to 20 ° C. trans-cyclohex-4-en-1, 2-dicarboxylic acid anhydride added; the reaction mixture is stirred for a further 3 hours at 15 to 20 ° C. while maintaining a pH of 6 by means of lithium hydroxide and then mixed with a hydrochloric acid diazonium salt suspension prepared in the usual way from 281 parts of 4- ( ⁇ -sulfatoethylsulfonyl) aniline. The coupling reaction is carried out at a pH of 4 to 5 and
- N N NH - CO,
- EXAMPLE 69 A solution with a pH of 6.5 of 281 parts of 4- ( ⁇ -sulfatoethyl-sulfo ⁇ yD-aniline and 40 parts of sodium fluoride in 3500 parts of ice water are mixed with 1 50 parts of cyanuric fluoride according to the procedure described in FIG DE-A 27 46 1 09. After the reaction has taken place, 80 parts of 1,3-diaminobenzene-4-sulfonic acid are added to the batch, and the pH is adjusted to 6.5 with sodium carbonate and while maintaining the pH and a temperature from 0 to 10 ° C for about three hours.
- the mixture is then cooled to 0 ° C. and the amino compound obtained is diazotized in a manner known per se using sodium nitrite and concentrated hydrochloric acid.
- the diazonium salt solution obtained is then added to the solution of the coupling component which, according to the present example 2, consists of 31 9 parts of 1-amino-3,6-disulfo-
- the monoazo compound according to the invention is then salted out with sodium chloride and isolated. It shows very good fiber-reactive dye properties and dyes, for example, cotton in bright red tones with good fastness properties.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9910271-4A BR9910271A (pt) | 1998-05-08 | 1999-05-03 | Composto de monoazo solúveis em água, preparo dos mesmos e uso dos mesmos como corantes |
CA002331309A CA2331309A1 (en) | 1998-05-08 | 1999-05-03 | Water-soluble monoazo compounds, preparation thereof and use thereof as dyes |
JP2000548409A JP2002514676A (ja) | 1998-05-08 | 1999-05-03 | 水溶性モノアゾ染料化合物、その製造法及び染料としての使用 |
EP99920832A EP1075500A1 (de) | 1998-05-08 | 1999-05-03 | Wasserlösliche monoazoverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbstoffe |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1998120543 DE19820543A1 (de) | 1998-05-08 | 1998-05-08 | Wasserlösliche Monoazoverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Farbstoffe |
DE19820543.0 | 1998-05-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999058612A1 true WO1999058612A1 (de) | 1999-11-18 |
Family
ID=7867048
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/002972 WO1999058612A1 (de) | 1998-05-08 | 1999-05-03 | Wasserlösliche monoazoverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbstoffe |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1075500A1 (de) |
JP (1) | JP2002514676A (de) |
BR (1) | BR9910271A (de) |
CA (1) | CA2331309A1 (de) |
DE (1) | DE19820543A1 (de) |
ID (1) | ID26256A (de) |
TR (1) | TR200003223T2 (de) |
WO (1) | WO1999058612A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004504471A (ja) * | 2000-07-22 | 2004-02-12 | ダイスター・テクスティルファルベン・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・ドイッチュラント・コマンデイトゲゼルシャフト | 水溶性繊維反応性染料、その調製およびその使用 |
US7820621B2 (en) | 2000-06-02 | 2010-10-26 | Bracco International B.V. | Compounds for targeting endothelial cells, compositions containing the same and methods for their use |
US8263739B2 (en) | 2000-06-02 | 2012-09-11 | Bracco Suisse Sa | Compounds for targeting endothelial cells, compositions containing the same and methods for their use |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1934123A1 (de) * | 1968-07-08 | 1970-05-21 | Sumitomo Chemical Co | Monoazoverbindungen,Verfahren zu ihrer Herstellung und ihre Verwendung zum Faerben von Textilgut |
DE2033279A1 (en) * | 1970-07-04 | 1972-01-13 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Reactive azo dyes - of the monochlorotriazine series for use of wool, polyamide, polyurethane and cellulose fibres |
DE2755936A1 (de) * | 1977-12-15 | 1979-06-21 | Hoechst Ag | Kupfer-, kobalt- oder chromkomplex- monoazoverbindungen, verfahren zu deren herstellung, ihre verwendung als farbstoffe und mit ihnen gefaerbte fasermaterialien |
EP0078008A2 (de) * | 1981-10-28 | 1983-05-04 | BASF Aktiengesellschaft | Reaktivfarbstoffe |
EP0090114A2 (de) * | 1982-03-26 | 1983-10-05 | Imperial Chemical Industries Plc | Reaktivfarbstoffe |
WO1996024637A1 (de) * | 1995-02-07 | 1996-08-15 | Bayer Aktiengesellschaft | Verfahren zur herstellung von reaktivazofarbstoffen |
-
1998
- 1998-05-08 DE DE1998120543 patent/DE19820543A1/de not_active Withdrawn
-
1999
- 1999-05-03 TR TR2000/03223T patent/TR200003223T2/xx unknown
- 1999-05-03 JP JP2000548409A patent/JP2002514676A/ja not_active Withdrawn
- 1999-05-03 WO PCT/EP1999/002972 patent/WO1999058612A1/de not_active Application Discontinuation
- 1999-05-03 EP EP99920832A patent/EP1075500A1/de not_active Withdrawn
- 1999-05-03 ID IDW20002273A patent/ID26256A/id unknown
- 1999-05-03 BR BR9910271-4A patent/BR9910271A/pt not_active Application Discontinuation
- 1999-05-03 CA CA002331309A patent/CA2331309A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1934123A1 (de) * | 1968-07-08 | 1970-05-21 | Sumitomo Chemical Co | Monoazoverbindungen,Verfahren zu ihrer Herstellung und ihre Verwendung zum Faerben von Textilgut |
US3649615A (en) * | 1968-07-08 | 1972-03-14 | Sumitomo Chemical Co | Phenyl-azo-naphthol dyes |
DE2033279A1 (en) * | 1970-07-04 | 1972-01-13 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Reactive azo dyes - of the monochlorotriazine series for use of wool, polyamide, polyurethane and cellulose fibres |
DE2755936A1 (de) * | 1977-12-15 | 1979-06-21 | Hoechst Ag | Kupfer-, kobalt- oder chromkomplex- monoazoverbindungen, verfahren zu deren herstellung, ihre verwendung als farbstoffe und mit ihnen gefaerbte fasermaterialien |
EP0078008A2 (de) * | 1981-10-28 | 1983-05-04 | BASF Aktiengesellschaft | Reaktivfarbstoffe |
EP0090114A2 (de) * | 1982-03-26 | 1983-10-05 | Imperial Chemical Industries Plc | Reaktivfarbstoffe |
WO1996024637A1 (de) * | 1995-02-07 | 1996-08-15 | Bayer Aktiengesellschaft | Verfahren zur herstellung von reaktivazofarbstoffen |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7820621B2 (en) | 2000-06-02 | 2010-10-26 | Bracco International B.V. | Compounds for targeting endothelial cells, compositions containing the same and methods for their use |
US7884183B2 (en) | 2000-06-02 | 2011-02-08 | Bracco Suisse Sa | Compounds for targeting endothelial cells, compositions containing the same and methods for their use |
US8263739B2 (en) | 2000-06-02 | 2012-09-11 | Bracco Suisse Sa | Compounds for targeting endothelial cells, compositions containing the same and methods for their use |
JP2004504471A (ja) * | 2000-07-22 | 2004-02-12 | ダイスター・テクスティルファルベン・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・ドイッチュラント・コマンデイトゲゼルシャフト | 水溶性繊維反応性染料、その調製およびその使用 |
Also Published As
Publication number | Publication date |
---|---|
DE19820543A1 (de) | 1999-11-11 |
JP2002514676A (ja) | 2002-05-21 |
BR9910271A (pt) | 2001-01-02 |
EP1075500A1 (de) | 2001-02-14 |
TR200003223T2 (tr) | 2001-03-21 |
ID26256A (id) | 2000-12-07 |
CA2331309A1 (en) | 1999-11-18 |
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