DE4303359C2 - Reactive carbazole dyes and process for their preparation - Google Patents
Reactive carbazole dyes and process for their preparationInfo
- Publication number
- DE4303359C2 DE4303359C2 DE19934303359 DE4303359A DE4303359C2 DE 4303359 C2 DE4303359 C2 DE 4303359C2 DE 19934303359 DE19934303359 DE 19934303359 DE 4303359 A DE4303359 A DE 4303359A DE 4303359 C2 DE4303359 C2 DE 4303359C2
- Authority
- DE
- Germany
- Prior art keywords
- diazocarbazole
- dyes
- carbazole
- dyeing
- epoxypropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000975 dye Substances 0.000 title claims description 33
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 10
- 230000008569 process Effects 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- QLNQMJOMDPWNAE-UHFFFAOYSA-N C1=CC=C2C3=CC=CC(=[N+]=[N-])C3=NC2=C1 Chemical compound C1=CC=C2C3=CC=CC(=[N+]=[N-])C3=NC2=C1 QLNQMJOMDPWNAE-UHFFFAOYSA-N 0.000 claims description 14
- VAJIZAPXBKMPRO-UHFFFAOYSA-N 9-(oxiran-2-ylmethyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1CC1CO1 VAJIZAPXBKMPRO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 11
- 238000004043 dyeing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 238000004040 coloring Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 210000002268 wool Anatomy 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006149 azo coupling reaction Methods 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 3
- 150000001716 carbazoles Chemical class 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UUYSTZWIFZYHRM-UHFFFAOYSA-N (9-ethylcarbazol-3-yl)azanium;chloride Chemical compound [Cl-].[NH3+]C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 UUYSTZWIFZYHRM-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- WONHLSYSHMRRGO-UHFFFAOYSA-N 9-ethyl-3-nitrocarbazole Chemical compound [O-][N+](=O)C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 WONHLSYSHMRRGO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- -1 aromatic diazonium ion Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- NDHWRTWVIMXELM-UHFFFAOYSA-N 2-(1-chlorobutyl)oxirane Chemical compound CCCC(Cl)C1CO1 NDHWRTWVIMXELM-UHFFFAOYSA-N 0.000 description 1
- HQOBDLCAOWRBOU-UHFFFAOYSA-N 2-hydroxy-9h-carbazole-1-carboxylic acid Chemical compound C12=CC=CC=C2NC2=C1C=CC(O)=C2C(=O)O HQOBDLCAOWRBOU-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- GAVPOWTXUZVFML-UHFFFAOYSA-M 4-nitrobenzenediazonium;chloride Chemical compound [Cl-].[O-][N+](=O)C1=CC=C([N+]#N)C=C1 GAVPOWTXUZVFML-UHFFFAOYSA-M 0.000 description 1
- GZSUIHUAFPHZSU-UHFFFAOYSA-N 9-ethyl-2,3-dihydro-1h-carbazol-4-one Chemical compound C12=CC=CC=C2N(CC)C2=C1C(=O)CCC2 GZSUIHUAFPHZSU-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- YJKJAYFKPIUBAW-UHFFFAOYSA-N 9h-carbazol-1-amine Chemical compound N1C2=CC=CC=C2C2=C1C(N)=CC=C2 YJKJAYFKPIUBAW-UHFFFAOYSA-N 0.000 description 1
- WTZQJWITZKKMAB-UHFFFAOYSA-N 9h-carbazole-1-sulfonic acid Chemical class C12=CC=CC=C2NC2=C1C=CC=C2S(=O)(=O)O WTZQJWITZKKMAB-UHFFFAOYSA-N 0.000 description 1
- APSDTEHUYIJMPZ-UHFFFAOYSA-N 9h-carbazole;hydrochloride Chemical compound Cl.C1=CC=C2C3=CC=CC=C3NC2=C1 APSDTEHUYIJMPZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- DIUIQJFZKRAGBZ-UHFFFAOYSA-N chetoseminudin A Natural products O=C1C(SSS2)(CO)N(C)C(=O)C32CC2(N4C5=CC=CC=C5C(CC56C(N(C)C(CO)(SS5)C(=O)N6C)=O)=C4)C4=CC=CC=C4NC2N31 DIUIQJFZKRAGBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZKGGQPVDKLXYSU-UHFFFAOYSA-M naphthalene-1-diazonium;chloride Chemical compound [Cl-].C1=CC=C2C([N+]#N)=CC=CC2=C1 ZKGGQPVDKLXYSU-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
-
- 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
- C09B41/00—Special methods of performing the coupling reaction
- C09B41/001—Special methods of performing the coupling reaction characterised by the coupling medium
-
- 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
- C09B62/54—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 epoxy or halohydrin group
- C09B62/58—Azo dyes
- C09B62/585—Monoazo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Coloring (AREA)
- Indole Compounds (AREA)
Description
Die Erfindung betrifft reaktive Diazofarbstoffe auf der Basis von Carbazolverbindungen sowie ein Verfahren zu deren Herstellung.The invention relates to reactive diazo dyes on the Base of carbazole compounds as well as a process their manufacture.
Im großtechnischen Maßstab werden verschiedenste Diazofarbstoffe hergestellt, in deren Molekülaufbau sich ein Carbazolringsystem befindet. Dazu zählen Küpenfarbstoffe ebenso wie direktziehende Farbstoffe. Das stickstoffhaltige Ringsystem des Carbozols kann während der Farbstoffsynthese durch Cyclisierung entstehen (Chrzaszcz, R.; Pielichowski J.; Polaczek J.; Popielarz, R.; "Barwniki karbazolowe", Zeszyty Naukowe Nr. 2, Zeszyt 17, 1986, Monographie).The most varied are on an industrial scale Diazo dyes produced in their molecular structure there is a carbazole ring system. These include Vat dyes as well as direct dyes. The nitrogen-containing ring system of carbozole can during dye synthesis through cyclization arise (Chrzaszcz, R .; Pielichowski J .; Polaczek J .; Popielarz, R .; "Barwniki karbazolowe", Zeszyty Naukowe No. 2, Zeszyt 17, 1986, monograph).
Carbazol kann aber auch selbst als Ausgangssubstanz zur Herstellung von Diazofarbstoffen verwendet werden, wie es z. B. aus den Schriften DE-PS 26 03 836; DE-OS 31 40 716 oder DE-OS 23 38 089 bekannt ist.Carbazole can also itself as a starting substance Production of diazo dyes are used, such as it z. B. from the documents DE-PS 26 03 836; DE-OS 31 40 716 or DE-OS 23 38 089 is known.
Die Synthese der Diazofarbstoffe des Carbazols kann sowohl durch Diazotierung eines Aminocarbazols und anschließende Kupplungsreaktion mit einer geeigneten aromatischen Verbindung als auch durch eine entsprechende elektrophile Substitution des Carbazols durch aromatisches Diazoniumion erfolgen.The synthesis of the diazo dyes of carbazole can both by diazotization of an aminocarbazole and subsequent coupling reaction with a suitable one aromatic compound as well by one corresponding electrophilic substitution of the carbazole by aromatic diazonium ion.
Carbazolderivate, wie Sulfocarbazole, Hydroxycarbazolsäure oder deren Amide werden in dieser Reaktion vorwiegend als Kupplungskomponente eingesetzt. Bekannt ist auch die direkte Kupplungsreaktion von Carbazol, bzw. seinen 9-Alkylderivaten mit Diazochloriden.Carbazole derivatives, such as sulfocarbazoles, Hydroxycarbazoleic acid or its amides are in this Reaction mainly used as a coupling component. The direct coupling reaction of is also known Carbazol, or its 9-alkyl derivatives with Diazochloriden.
Nachteil dieser Farbstoffe ist ihre mangelnde Reaktivität, wodurch sie zum Färben von synthetischen oder natürlichen Fasern oder von polymeren Werkstoffen nur sehr beschränkt einsetzbar sind.The disadvantage of these dyes is their lack Reactivity, causing them to dye synthetic or natural fibers or of polymeric materials can only be used to a very limited extent.
Da jedoch die Herstellung der Diazofarbstoffe des Carbazols zur Bildung intensiver Farbtöne führt, die mittels anderer Aromaten nicht annähernd erzielt werden können, ist es Aufgabe der Erfindung Diazocarbazolfarbstoffe in der Weise chemisch zu verändern, daß sie bei unveränderter Farbintensität gegenüber den zu färbenden Stoffen erhöhte Reaktivitäten aufweisen.However, since the production of the diazo dyes Carbazols leads to the formation of intense shades that cannot be nearly achieved with other aromatics can, it is an object of the invention Diazocarbazole dyes chemically in such a way change that with unchanged color intensity increased compared to the fabrics to be dyed Show reactivities.
Die Lösung der Aufgabe erfolgt durch reaktivierte Diazocarbazolfarbstoffe gemäß Anspruch 1, die nach einem Verfahren gemäß den Ansprüchen 2 bis 4 hergestellt werden können und gemäß den Ansprüchen 5 bis 10 zum farbechten Färben von natürlichen oder synthetischen Fasern verwendet werden können.The task is solved by reactivated Diazocarbazole dyes according to claim 1, which according to a method according to claims 2 to 4 can be produced and according to claims 5 up to 10 for colourfast dyeing of natural or synthetic fibers can be used.
Versuche haben nun gezeigt, daß aus einem in 9-Stellung, also am Stickstoffatom, mit einer 2,3-Epoxypropylgruppe substituierten Carbazol in einfacher Weise Diazofarbstoffe hergestellt werden können, die sowohl besonders gute Färbeeigenschaften gegenüber natürlichen Fasern, wie z. B. Wolle, als auch gegenüber synthetischen Fasern, beispielsweise aus Polyamid oder Polyester, aber auch beim Färben von polymeren Werkstoffen aufweisen.Experiments have now shown that from one in 9-position, i.e. on the nitrogen atom, with a 2,3-epoxypropyl group substituted carbazole in simple diazo dyes are produced can have both particularly good coloring properties against natural fibers, such as B. wool, as well compared to synthetic fibers, for example Polyamide or polyester, but also when dyeing have polymeric materials.
In den Untersuchungen erwiesen sich diese Farbstoffe als waschecht, lichtecht und, da die Färbung mit einer chemischen Reaktion der Epoxygruppen verknüpft ist, als gesundheitlich unbedenklich und nicht allergen.These dyes were found in the investigations as washable, lightfast and, because the coloring with a chemical reaction of the epoxy groups is linked as harmless to health and not allergenic.
Das zur Herstellung der erfindungsgemäßen Farbstoffe benötigte 9-(2,3-Epoxypropyl)-carbazol kann durch Umsetzung von Carbazol mit Epichlorhydrin in wäßriger alkalischer Lösung evtl. in Gegenwart eines Katalysators, insbesondere eines quartären Ammoniumsalzes, wie z. B. Triethylbenzylammoniumchlorid, bei einer Temperatur von 0 bis 65°C gewonnen werden. Geeignete Synthesemethoden sind z. B. aus CS-B 192 960 oder Inaki, Yoshiaki; Sheylani, Golnar; Takemoto, Kiichi; Technol. Rep. Osaka Univ., 25 (1230-1253), 249-52 (1975) "Functional monomers and polymers. XXI. Synthesis and polymerization of epoxy compounds containing carbazol and indol" bekannt.That for the production of the dyes according to the invention required 9- (2,3-epoxypropyl) carbazole can by Reaction of carbazole with epichlorohydrin in aqueous alkaline solution possibly in the presence of a Catalyst, especially a quaternary Ammonium salt, such as. B. Triethylbenzylammonium chloride, at a temperature of 0 to 65 ° C can be obtained. Suitable synthetic methods are z. B. from CS-B 192 960 or Inaki, Yoshiaki; Sheylani, Golnar; Takemoto, Kiichi; Technol. Rep. Osaka Univ., 25 (1230-1253), 249-52 (1975) "Functional monomers and polymers. XXI. Synthesis and polymerization of epoxy compounds containing carbazole and indole ".
Die anschließende Diazotierung kann nach einem Verfahren erfolgen, das in der polnischen Patentanmeldung P 281 309 zur Herstellung entsprechender Farbstoffe aus 9-Ethylcarbazol und geeigneten, als Chlorsalze vorliegenden, Diazoniumionen offenbart ist. The subsequent diazotization can be carried out after a Procedures are carried out in the Polish Patent application P 281 309 for production corresponding dyes from 9-ethylcarbazole and suitable diazonium ions present as chlorine salts is disclosed.
Dieses hat den Vorteil, daß die eigentliche Kupplungsreaktion ohne vorherige Isolierung des Diazoniumsalzes in der gleichen Reaktionslösung erfolgen kann. Die Bildung des Farbstoffs erfolgt dann in einem Gemisch, das sowohl ein organisches Lösungsmittel als auch Wasser und starke anorganische Säuren enthält. Als organisches Lösungsmittel werden bevorzugt Ether, insbesondere Tetrahydrofuran, verwendet. Wie aus der Literatur bekannt, wird die eigentliche Kupplungsreaktion mit einem Aryldiazoniumion bei einem pH-Wert von ungefähr 6 bei einer Temperatur von -5 bis 10°C unter Rühren innerhalb von 1 bis 4 Stunden durchgeführt.This has the advantage that the actual Coupling reaction without prior isolation of the Diazonium salt in the same reaction solution can be done. The dye is then formed in a mixture that is both an organic Solvents as well as water and strong inorganic Contains acids. As an organic solvent preferably ethers, especially tetrahydrofuran, used. As is known from the literature, the actual coupling reaction with a Aryldiazonium ion at a pH of around 6 a temperature of -5 to 10 ° C with stirring performed within 1 to 4 hours.
Zur näheren Veranschaulichung der Erfindung werden im folgenden Beispiele gegeben:To illustrate the invention in more detail given the following examples:
In einem Reaktionskolben, ausgestattet mit einem Rührer, einem Rückflußkühler und einem Thermometer, werden 5 g (0,03 Mol) Carbazol, 10 ml Wasser, 1 g Triethylbenzylammoniumchlorid (TEBA) und eine Mischung aus 10 ml Propylepichlorhydrin und 10 ml Hexan gegeben.In a reaction flask equipped with a Stirrer, a reflux condenser and a thermometer, 5 g (0.03 mol) of carbazole, 10 ml of water, 1 g Triethylbenzylammonium chloride (TEBA) and a mixture added from 10 ml propylepichlorohydrin and 10 ml hexane.
In diese Mischung werden nun unter intensivem Rühren 20 ml 45%ige Natronlauge so langsam zugetropft, daß die Temperatur 50°C nicht übersteigt. Das so erhaltene Reaktionsgemisch wird auf etwa die gleiche Menge Wasser gegeben. Die sich nach dem Vermischen abscheidende organische Phase wird verworfen und der sich aus der Wasserphase abscheidende Niederschlag aus rohem 9-(2,3-Epoxypropyl)-carbazol abfiltriert. Das erhaltene Rohprodukt (5,6 g) wird aus einem Lösungsmittelgemisch bestehend aus 10 Vol.-Teilen Methanol und 10 Vol.-Teilen Aceton umkristallisiert.20 ml of this mixture are now stirred vigorously 45% sodium hydroxide solution was added dropwise so slowly that the Temperature does not exceed 50 ° C. The so obtained Reaction mixture is made up of about the same amount of water given. The one that separates after mixing organic phase is discarded and resulting from the Water phase separating precipitate from crude Filtered 9- (2,3-epoxypropyl) carbazole. The received Crude product (5.6 g) is made from a mixed solvent consisting of 10 parts by volume of methanol and 10 parts by volume Acetone recrystallized.
Es wird ein Produkt mit einer Schmelztemperatur von
107°C in einer Ausbeute von 70% erhalten. Das 1H-NMR
Spektrum des erhaltenen Produktes:
8H (Carbazolringsystem) 8,2-7,0 ppm: 2H (CH2-Gruppe)
4,8-4,2 ppm; 1H-3,4-3,2 ppm; 2H (Oxiransystem)
2,9-2,4 ppm.A product with a melting temperature of 107 ° C. is obtained in a yield of 70%. The 1H-NMR spectrum of the product obtained:
8H (carbazole ring system) 8.2-7.0 ppm: 2H (CH 2 group) 4.8-4.2 ppm; 1H-3.4-3.2 ppm; 2H (oxirane system) 2.9-2.4 ppm.
Zu 0,39 g (0,0022 Mol) p-Bromanilin werden 0,7 ml konzentrierte Salzsäure und 3 ml Wasser gegeben. Die Mischung wird vorsichtig unter Rühren erwärmt und dann wieder auf 0°C abgekühlt. Danach werden langsam 0,17 g Natriumnitrit in 1,5 ml Wasser eingerührt, wobei die Temperatur des Reaktionsgemisches unter 5°C gehalten wird. Nach beendeter Diazotierung wird das Gemisch 20 Minuten lang gerührt und mit Natronlauge auf pH = 6 gebracht. Anschließend werden 0,5 g (0,022 Mol) 9-(2,3-Epoxypropyl)-carbazol in 10 ml Tetrahydrofuran hinzugegeben. Das Reaktionsgemisch wird bei 0 bis 5°C 2 Stunden lang gerührt und dann noch weitere 4 Stunden lang nachgerührt, wobei die Temperatur bis auf Raumtemperatur ansteigen darf. Nach dem Abdampfen des Lösungsmittels wird in das Reaktionsgemisch Methylenchlorid gegeben, die organische Phase mit Wasser gewaschen, und danach das Lösungsmittel entfernt. Es werden 0,65 g homogenes (HPLC) Produkt mit rotbrauner Farbe erhalten, dessen Lösung in Tetrahydrofuran eine orange Farbe aufweist. Das Absorptionsmaximum im Ultraviolett liegt für den enthaltenen Farbstoff bei 470 nm. Dieser Farbstoff eignet sich zur Färbung von Polyamid- und Wollfasern.0.7 ml of 0.39 g (0.0022 mol) of p-bromoaniline are added concentrated hydrochloric acid and 3 ml of water. The Mixture is gently heated with stirring and then cooled again to 0 ° C. Then slowly 0.17 g Sodium nitrite stirred in 1.5 ml of water, the Temperature of the reaction mixture kept below 5 ° C. becomes. After the diazotization has ended, the mixture Stirred for 20 minutes and to pH = 6 with sodium hydroxide solution brought. Then 0.5 g (0.022 mol) 9- (2,3-Epoxypropyl) carbazole in 10 ml tetrahydrofuran added. The reaction mixture is at 0 to 5 ° C. Stirred for 2 hours and then another 4 hours long stirred, the temperature up to Room temperature may rise. After evaporating the Solvent is added to the reaction mixture Given methylene chloride, the organic phase with Washed water, and then the solvent away. There are 0.65 g of homogeneous (HPLC) product get reddish brown color, the solution in Tetrahydrofuran has an orange color. The Absorption maximum in the ultraviolet is for the contained dye at 470 nm. This dye is suitable for dyeing polyamide and wool fibers.
Die Kupplungsreaktion wird auf gleiche Weise wie im Beispiel 1 durchgeführt, wobei zur Reaktion 0,5 g 9(2,3-Epoxypropyl)-carbazol, das nach dem in Bsp. 1a angegebenen Verfahren hergestellt worden ist, und 0,33 g 1-Naphthylamin (0,022 Mol), in Gegenwart von 0,6 ml konzentrierter Salzsäure und 0,17 g Natriumnitrit eingesetzt werden.The coupling reaction is carried out in the same way as in Example 1 carried out, for the reaction 0.5 g 9 (2,3-epoxypropyl) carbazole, which according to the in Example 1a specified method has been prepared, and 0.33 g of 1-naphthylamine (0.022 mol) in the presence of 0.6 ml of concentrated hydrochloric acid and 0.17 g Sodium nitrite can be used.
Es werden 0,6 g eines homogenen (CHPLC) Farbstoffs erhalten, der in Tetrahydrofuran eine orangenrote Farbe besitzt. Das Absorptionsmaximum im Ultraviolett liegt bei 455 nm. Der Farbstoff eignet sich zur Färbung von Polyvinylchlorid.There are 0.6 g of a homogeneous (CHPLC) dye obtained, which has an orange-red color in tetrahydrofuran has. The absorption maximum is in the ultraviolet at 455 nm. The dye is suitable for coloring Polyvinyl chloride.
Die Kupplungsreaktion wird, wie im Beispiel 1b beschrieben, durchgeführt, wobei 0,5 g 9-(2,3-Epoxypropyl)-carbazol (0,022 Mol), das nach dem in Beispiel 1a beschriebenen Verfahren hergestellt worden ist, und 0,31 g p-Nitroanilin (0,0022 Mol), 0,7 ml konzentrierte Salzsäure und 0,17 g Natriumnitrit (0,025 Mol) verwendet werden.The coupling reaction is carried out as in Example 1b described, carried out, wherein 0.5 g 9- (2,3-Epoxypropyl) carbazole (0.022 mol), which after the method described in Example 1a and 0.31 g of p-nitroaniline (0.0022 mol), 0.7 ml concentrated hydrochloric acid and 0.17 g sodium nitrite (0.025 mol) can be used.
Die Reaktion wird in einem Gemisch, bestehend aus 20 ml Methylenchlorid und 20 ml Wasser, sowie einer geringen Menge Mersolan als Emulsionsbildner, durchgeführt. (Methylenchlorid kann durch die gleiche Menge Tetrahydrofuran ersetzt werden.)The reaction is carried out in a mixture consisting of 20 ml Methylene chloride and 20 ml of water, as well as a low one Amount of Mersolan as an emulsifier. (Methylene chloride can by the same amount Tetrahydrofuran.)
Es wird ein orangegelber Farbstoff mit einer Schmelztemperatur von 40 bis 44°C erhalten. Auch in Tetrahydrofuran weist er eine orangegelbe Farbe auf.It becomes an orange-yellow dye with a Get melting temperature of 40 to 44 ° C. Also in Tetrahydrofuran has an orange-yellow color.
Das Absorptionsmaximum im Ultraviolett liegt bei 425 nm. Der Farbstoff eignet sich zur Färbung von Epoxidharzen und Polyesterfasern.The absorption maximum in the ultraviolet is included 425 nm. The dye is suitable for coloring Epoxy resins and polyester fibers.
In 230 ml Eisessig werden bei Raumtemperatur 20 g 9-Ethylcarbazol gelöst. Danach werden in diese Lösung unter Rühren innerhalb von 1,5 Stunden 4,7 ml konzentrierte Salpetersäure (d = 1,5 g/ml) eingetropft. Dieses Gemisch wird 2 Stunden nachgerührt. Der ausgefallene Niederschlag wird abfiltriert und bis zur neutralen Reaktion mit Wasser gewaschen. Es werden 17,5 g 9-Ethyl-3-nitrocarbazol erhalten. Hiervon werden 7,25 g 9-Ethyl-3-nitrocarbazol in 125 ml Eisessig bei einer Temperatur von 95°C gelöst. Zu dieser Lösung werden 7,5 g Eisen und 1 ml Wasser gegeben. Die erhaltene Mischung wird im kochenden Wasserbad innerhalb von 20 Minuten intensiv gerührt, abgekühlt und mit 60 ml konzentrierter Salzsäure versetzt. Nach dem Filtrieren wird das Filtrat in 300 ml 15%ige Salzsäure eingegossen. Um das 9-Ethyl-3-aminocarbazolhydrochlorid gewinnen zu können, wird die Lösung auf 200 ml eingedampft und abgekühlt. Es werden 2,8 g Hydrochlorid erhalten. Die Kupplung wird, wie in Beispiel 1 beschrieben, durchgeführt, wobei zur Reaktion 0,5 g 9(2,3-Epoxypropyl)-carbazol (0,022 Mol), das in Beispiel 1a hergestellt worden ist, 0,55 g 9-Ethyl-3-aminocarbazolhydrochlorid (0,022 Mol), 0,7 ml konzentrierte Salzsäure und 0,17 g Natriumnitrit (0,025 Mol) verwendet werden.20 g at room temperature in 230 ml of glacial acetic acid 9-ethyl carbazole dissolved. After that, in this solution 4.7 ml with stirring within 1.5 hours concentrated nitric acid (d = 1.5 g / ml) added dropwise. This mixture is stirred for 2 hours. The precipitate is filtered off and until neutral reaction washed with water. There are 17.5 g Obtained 9-ethyl-3-nitrocarbazole. Of this 7.25 g of 9-ethyl-3-nitrocarbazole in 125 ml of glacial acetic acid a temperature of 95 ° C solved. About this solution 7.5 g of iron and 1 ml of water are added. The obtained mixture is in a boiling water bath intensively stirred within 20 minutes, cooled and mixed with 60 ml of concentrated hydrochloric acid. To after filtration, the filtrate in 300 ml of 15% Poured in hydrochloric acid. To do that 9-Ethyl-3-aminocarbazole hydrochloride recover can, the solution is evaporated to 200 ml and cooled. 2.8 g of hydrochloride are obtained. The Coupling is, as described in example 1, carried out, with the reaction 0.5 g 9 (2,3-epoxypropyl) carbazole (0.022 mol), which in Example 1a was made, 0.55 g 9-ethyl-3-aminocarbazole hydrochloride (0.022 mol), 0.7 ml concentrated hydrochloric acid and 0.17 g sodium nitrite (0.025 mol) can be used.
Es werden 0,85 g eines braunen Diazofarbstoffs erhalten, der in einer Tetrahydrofuranlösung eine rote Farbe aufweist. Die UV-Absorptionskurve zeigt kein deutliches Maximum.There are 0.85 g of a brown diazo dye obtained, the red in a tetrahydrofuran solution Has color. The UV absorption curve shows none clear maximum.
Claims (12)
- a) Carbazol mit Epichlorhydrin in alkalischem Medium in Gegenwart eines quartären Ammoniumsalzes als Katalysator bei 0 bis 65°C zum 9-(2,3-Epoxypropyl)-carbazol umgesetzt wird, und
- b) die Kupplungsreaktion mit einem substituierten Aryldiazoniumion in einem Gemisch, das sowohl ein organisches Lösungsmittel als auch Wasser und eine starke Säure enthält, bei Temperaturen von -5 bis 10°C durchgeführt wird.
- a) reacting carbazole with epichlorohydrin in an alkaline medium in the presence of a quaternary ammonium salt as a catalyst at 0 to 65 ° C. to give 9- (2,3-epoxypropyl) carbazole, and
- b) the coupling reaction with a substituted aryldiazonium ion in a mixture containing both an organic solvent and water and a strong acid is carried out at temperatures from -5 to 10 ° C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL29468292A PL169333B1 (en) | 1992-05-26 | 1992-05-26 | Reactive carbazole dyes and method of obtaining them |
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| Publication Number | Publication Date |
|---|---|
| DE4303359A1 DE4303359A1 (en) | 1993-12-02 |
| DE4303359C2 true DE4303359C2 (en) | 2002-06-20 |
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ID=20057661
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|---|---|---|---|
| DE19934303359 Expired - Fee Related DE4303359C2 (en) | 1992-05-26 | 1993-02-05 | Reactive carbazole dyes and process for their preparation |
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| DE (1) | DE4303359C2 (en) |
| PL (1) | PL169333B1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2212755A1 (en) * | 1972-03-16 | 1973-09-20 | Cassella Farbwerke Mainkur Ag | HYDRO-INSOLUBLE MONOAZO DYES AND PROCESS FOR THEIR MANUFACTURING |
| DE2338089A1 (en) * | 1973-07-27 | 1975-02-06 | Cassella Farbwerke Mainkur Ag | Water-insol. mono-azo dyes free from ionogenic gps - used for dyeing synthetic hydrophobic materials |
| DE2603836C3 (en) * | 1976-02-02 | 1980-09-04 | Cassella Ag, 6000 Frankfurt | Process for the production of azo dyes |
| DE3140716A1 (en) * | 1981-10-14 | 1983-04-28 | Cassella Ag, 6000 Frankfurt | METHOD FOR THE PRODUCTION OF AZO DYES BY DIAZOTATION AND COUPLING |
| JPH0415656A (en) * | 1990-05-09 | 1992-01-21 | Nippon Shizai Kk | Laminate type electrophotographic sensitive body |
| EP0499090A1 (en) * | 1991-02-15 | 1992-08-19 | Hoechst Mitsubishi Kasei Co., Ltd. | Process for dyeing polyester and polyester-contaning textile materials |
| EP0661351B1 (en) * | 1994-01-03 | 1999-11-10 | DyStar Textilfarben GmbH & Co. Deutschland KG | Monoazocarbazol dyestuffs |
-
1992
- 1992-05-26 PL PL29468292A patent/PL169333B1/en unknown
-
1993
- 1993-02-05 DE DE19934303359 patent/DE4303359C2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2212755A1 (en) * | 1972-03-16 | 1973-09-20 | Cassella Farbwerke Mainkur Ag | HYDRO-INSOLUBLE MONOAZO DYES AND PROCESS FOR THEIR MANUFACTURING |
| DE2338089A1 (en) * | 1973-07-27 | 1975-02-06 | Cassella Farbwerke Mainkur Ag | Water-insol. mono-azo dyes free from ionogenic gps - used for dyeing synthetic hydrophobic materials |
| DE2603836C3 (en) * | 1976-02-02 | 1980-09-04 | Cassella Ag, 6000 Frankfurt | Process for the production of azo dyes |
| DE3140716A1 (en) * | 1981-10-14 | 1983-04-28 | Cassella Ag, 6000 Frankfurt | METHOD FOR THE PRODUCTION OF AZO DYES BY DIAZOTATION AND COUPLING |
| JPH0415656A (en) * | 1990-05-09 | 1992-01-21 | Nippon Shizai Kk | Laminate type electrophotographic sensitive body |
| EP0499090A1 (en) * | 1991-02-15 | 1992-08-19 | Hoechst Mitsubishi Kasei Co., Ltd. | Process for dyeing polyester and polyester-contaning textile materials |
| EP0661351B1 (en) * | 1994-01-03 | 1999-11-10 | DyStar Textilfarben GmbH & Co. Deutschland KG | Monoazocarbazol dyestuffs |
Also Published As
| Publication number | Publication date |
|---|---|
| PL169333B1 (en) | 1996-07-31 |
| DE4303359A1 (en) | 1993-12-02 |
| PL294682A1 (en) | 1993-11-29 |
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