CH496780A - Process for the production of water-soluble reactive azo dyes - Google Patents
Process for the production of water-soluble reactive azo dyesInfo
- Publication number
- CH496780A CH496780A CH37569A CH3756966A CH496780A CH 496780 A CH496780 A CH 496780A CH 37569 A CH37569 A CH 37569A CH 3756966 A CH3756966 A CH 3756966A CH 496780 A CH496780 A CH 496780A
- Authority
- CH
- Switzerland
- Prior art keywords
- chlorine
- bromine atom
- water
- sep
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 239000000987 azo dye Substances 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical group O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 claims description 4
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical group NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002790 naphthalenes Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000975 dye Substances 0.000 description 14
- -1 alkyl radicals Chemical class 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZNXSFVXZQBETRJ-UHFFFAOYSA-N (3-aminophenyl)urea Chemical compound NC(=O)NC1=CC=CC(N)=C1 ZNXSFVXZQBETRJ-UHFFFAOYSA-N 0.000 description 1
- GVBHCMNXRKOJRH-UHFFFAOYSA-N 2,4,5,6-tetrachloropyrimidine Chemical compound ClC1=NC(Cl)=C(Cl)C(Cl)=N1 GVBHCMNXRKOJRH-UHFFFAOYSA-N 0.000 description 1
- VHYBUUMUUNCHCK-UHFFFAOYSA-N 2,4,6-tribromo-1,3,5-triazine Chemical compound BrC1=NC(Br)=NC(Br)=N1 VHYBUUMUUNCHCK-UHFFFAOYSA-N 0.000 description 1
- DBVMPHIRIFGWEV-UHFFFAOYSA-N 2,4,6-tribromopyrimidine-5-carbonitrile Chemical compound BrC1=NC(Br)=C(C#N)C(Br)=N1 DBVMPHIRIFGWEV-UHFFFAOYSA-N 0.000 description 1
- IAJCAZVXGKGAQK-UHFFFAOYSA-N 2,4,6-trichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC(Cl)=C(C#N)C(Cl)=N1 IAJCAZVXGKGAQK-UHFFFAOYSA-N 0.000 description 1
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 1
- VSHQQFPDBBHFIH-UHFFFAOYSA-N 2-(3-aminophenyl)-5-methylpyrazol-3-amine Chemical compound N1=C(C)C=C(N)N1C1=CC=CC(N)=C1 VSHQQFPDBBHFIH-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 1
- KNOUFVBOBNEGMH-UHFFFAOYSA-N 3,7-diaminonaphthalene-1,5-disulfonic acid Chemical compound C1=C(N)C=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 KNOUFVBOBNEGMH-UHFFFAOYSA-N 0.000 description 1
- FHXUYFKYRBLZJU-UHFFFAOYSA-N 3-(5-methyl-3-oxo-1h-pyrazol-2-yl)benzenesulfonic acid Chemical compound N1C(C)=CC(=O)N1C1=CC=CC(S(O)(=O)=O)=C1 FHXUYFKYRBLZJU-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- CQENDTFOGHRNFW-UHFFFAOYSA-N 4-(3-methyl-5-oxopyrazol-4-yl)benzenesulfonic acid Chemical compound O=C1N=NC(C)=C1C1=CC=C(S(O)(=O)=O)C=C1 CQENDTFOGHRNFW-UHFFFAOYSA-N 0.000 description 1
- APXZUKPCHGKOTB-UHFFFAOYSA-N 4-methyl-3-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC(S(O)(=O)=O)=CC=C1C APXZUKPCHGKOTB-UHFFFAOYSA-N 0.000 description 1
- JGEJQHNWJUNACW-UHFFFAOYSA-N 5-oxo-1-(3-sulfophenyl)-4h-pyrazole-3-carboxylic acid Chemical compound O=C1CC(C(=O)O)=NN1C1=CC=CC(S(O)(=O)=O)=C1 JGEJQHNWJUNACW-UHFFFAOYSA-N 0.000 description 1
- TYCNXOAPQGVAQU-UHFFFAOYSA-N 5-oxo-1-(4-sulfophenyl)-4h-pyrazole-3-carboxylic acid Chemical compound O=C1CC(C(=O)O)=NN1C1=CC=C(S(O)(=O)=O)C=C1 TYCNXOAPQGVAQU-UHFFFAOYSA-N 0.000 description 1
- UYJDHSGEGWMTLJ-UHFFFAOYSA-N 7-[[4-amino-2-(carbamoylamino)phenyl]diazenyl]naphthalene-1,3,6-trisulfonic acid Chemical compound NC(=O)NC1=CC(N)=CC=C1N=NC1=CC2=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C=C2C=C1S(O)(=O)=O UYJDHSGEGWMTLJ-UHFFFAOYSA-N 0.000 description 1
- GFPQSWFFPRQEHH-UHFFFAOYSA-N 7-aminonaphthalene-1,3,6-trisulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(N)=CC2=C1S(O)(=O)=O GFPQSWFFPRQEHH-UHFFFAOYSA-N 0.000 description 1
- UBDHSURDYAETAL-UHFFFAOYSA-N 8-aminonaphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 UBDHSURDYAETAL-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PXEUNQLVJORHTM-UHFFFAOYSA-N NC=1C=C(C=CC1S(=O)(=O)O)N1N=C(C=C1N)C Chemical compound NC=1C=C(C=CC1S(=O)(=O)O)N1N=C(C=C1N)C PXEUNQLVJORHTM-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SQYUJKVKVFILNB-UHFFFAOYSA-N methyl 2-amino-4-[(2,5-dichlorophenyl)carbamoyl]benzoate Chemical compound C1=C(N)C(C(=O)OC)=CC=C1C(=O)NC1=CC(Cl)=CC=C1Cl SQYUJKVKVFILNB-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- HGVIAKXYAZRSEG-UHFFFAOYSA-N n-(2,4-dimethylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1C HGVIAKXYAZRSEG-UHFFFAOYSA-N 0.000 description 1
- TVZIWRMELPWPPR-UHFFFAOYSA-N n-(2-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C TVZIWRMELPWPPR-UHFFFAOYSA-N 0.000 description 1
- PEMGGJDINLGTON-UHFFFAOYSA-N n-(3-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(N)=C1 PEMGGJDINLGTON-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- WXWCDTXEKCVRRO-UHFFFAOYSA-N para-Cresidine Chemical compound COC1=CC=C(C)C=C1N WXWCDTXEKCVRRO-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C09B62/523—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 amido or hydroxyalkyl amino sulfonyl group, a quaternised or non-quaternised amino alkyl sulfonyl amido group, or a substituted alkyl amino sulfonyl group, or a halogen alkyl sulfonyl amido or halogen alkyl amino sulfonyl group or a vinyl sulfonylamido or a substituted vinyl sulfonamido group
- C09B62/527—Azo dyes
- C09B62/53—Monoazo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung wasserlöslicher Reaktiv-Azofarbstoffe
Es ist bekannt, zum Färben von hydroxylgruppenhaltigen Fasern, insbesondere Cellulosematerialien wie Baumwolle und Viskose-Reyon, Farbstoffe zu verwenden, welche Halogen-s-triazingruppen aufweisen.
Diese Farbstoffe werden auf den genannten Mate rialien leicht mit guter Nassfestigkeit fixiert, da die Halogen-s-triazingruppe in Gegenwart eines säurebinden- den Mittels, insbesondere bei erhöhten Temperaturen, mit den Hydroxylgruppen des Cellulosemoleküls reagieren kann. Die Farbstoffe werden aus wässriger Flotte oder in Form wässriger Farbpasten aufgebracht; aufgrund einer Nebenreaktion, in welcher die Halogen-striazingruppe mit Wasser reagiert statt mit dem Cellulosemolekül, wird ein Teil des Farbstoffs nicht auf der Faser fixiert.
Es muss folglich ein Überschuss an Farbstoff verwendet werden, und die Färbungen oder Drucke müssen mit siedender Seifenlösung sorgfältig gewaschen werden, um nicht umgesetzten Farbstoff zu entfernen.
Durch die Notwendigkeit von überschüssigem Farbstoff und der weiteren Verfahrensstufe wird das Färben oder Drucken teurer, insbesondere wenn dunklere Färbungen erhalten werden sollen.
Ziel vorliegender Erfindung ist ein Verfahren zur Herstellung wasserlöslicher Halogen-s-triazin-Reaktivfarbstoffe, deren Fixierung auf der Faser bemerkenswert hoch ist und bei welchen die Auswaschbehandlungen wesentlich verringert werden können.
Gemäss vorliegender Erfindung werden wasserlösliche Manoazofarbstoffe der Formel
EMI1.1
hergestellt, wobei A den Rest einer Diazokomponente der Benzol- oder Naphthalinreihe, E den Rest eines in para-Stellung kuppelnden Amins der Benzol- oder Naphthalinreihe oder eines 5-Pyrazolons, 5-Aminopyrazols oder Acetoacetarylamids, T einen ein reaktionsfähiges Chlor- oder Bromatom enthaltenden Pyrimidin- oder s-Triazinring, der über ein Stickstoffatom an einen aromatischen Ring von A oder E gebunden ist, R und R' Wasserstoff oder Alkylreste mit bis zu 4 C-Atomen, Z einen a,ss-Alkylenrest mit bis zu 4 C-Atomen und Y ein Chlor- oder Bromatom bedeuten.
Um die Wasserlöslichkeit der Farbstoffe sicherzustellen, sollten die aromatischen Kerne der Reste A und E mindestens eine Sulfonsäuregruppe und vorzugsweise mindestens zwei Sulfonsäuregruppen aufweisen. Die Ringe können ferner andere Substituenten, wie Methyl-, Methoxy- oder Ureidogruppen, Chlor- oder Bromatome, Carboxyl-, Nitro- oder Carboalkoxygruppen mit bis zu 4 C-Atomen in der Alkoxygruppe enthalten.
Der durch T wiedergegebene Pyrimidin- oder s-Triazinring muss in einer der Stellungen 2, 4 und 6 ein Chlor- oder Bromatom enthalten. Pyrimidinkerne sollten ferner in 5-Stellung noch einen elektronegativen Substituenten, z. B. ein Chlor- oder Bromatom oder eine Cyangruppe, aufweisen.
Die neuen Farbstoffe werden erfindungsgemäss erhalten, indem man eine Verbindung der Formel [A-N = N-E] in der einer der Reste A und E ein Stickstoffatom mit azinylierbarem Wasserstoff aufweist, mit einer Verbin- dung der Formel
EMI1.2
<tb> Halogen-T¯N- <SEP> SO,N-Y-Z
<tb> <SEP> R
<tb> in der T' einen ein reaktionsfähiges Chlor- oder Bromatom aufweisenden Pyrimidin- oder s-Triazinring und Halogen ein zweites an T' gebundenes Chlor- oder Bromatom bedeuten, umsetzt.
Die Ausgangsmaterialien können erhalten werden, indem man durch an sich bekannte Kupplungs- und Kondensationsreaktionen folgende Ausgangsmaterialien kombiniert: Einerseits (a) die Diazoniumverbindung eines aromatischen Amins der Formel A-NH2 und (b) ein in para-Stellung kuppelndes Amin der Benzolreihe oder ein 5-Pyrazolon, 5-Aminopyrazol oder Aceto-acetarylamid als Kupplungskomponente, wobei eine der Komponenten (a) und (b) eine Amino- oder monosubstituierte Aminogruppe oder eine nach der Kupplungsreaktion ohne Zerstörung der Azogruppe in eine Aminogruppe überführbare Gruppe, z.
B. eine Nitro- oder Acetylaminogruppe, aufweisen muss; und andererseits (c) ein Cyanurhalogenid oder ein in 2-, 4- und 6-Stellung Chloroder Bromatome und in 5-Stellung einen elektronegativen Substituenten enthaltendes Pyrimidinderivat und (d) ein Amin der Formel
EMI2.1
Als Beispiel seien folgende Verbindungen angeführt: (a) Diazokomponenten der Formel A-NH2
Anilin- und Naphthylaminsulfonsäuren sowie Substitutionsprodukte davon, wie Orthanilsäure, Anilin-2,5disulfonsäure, 2-Naphthylamin-4,8-disulfonsäure, 2 Naphthylamin-3,6,8-trisulfonsäure, l-Naphthylamin3,8-disulfonsäure, 1-Naphthylamin-3,6,8-trisulfonsäure, m-Phenylendiamin-o-sulfonsäure, p-Phenylendiamin-osulfonsäure und 2,6-Diaminonaphthalin-4,8-disulfon- säure.
(b) Kupplungskomponenten
Aniline und a-Naphthylamine, die nicht-ionische Substituenten, wie Alkyl- oder Alkoxygruppen mit bis zu 4 C-Atomen, Acylamino- und Ureidogruppen, im gleichen Ring wie die Aminogruppe tragen können, sowie die N-G bis C4-alkylsubstituierten Derivate dieser Verbindungen, z. B.
m-Toluidin, 2-Methoxy-5-methylanilin, o-Anisidin, m-Aminoacetanilid, m-Aminophenylharnstoff, l-Naphthylamin-6- und 7-sulfonsäure und N Methylanilin, 5-Pyrazolone mit einem mono- oder bicyclischen aromatischen Substituenten in l-Stellung und einer Methyl-, Carboxyl- oder Carbo-Ci bis C4-alkoxy- gruppe in 3-Stellung des Pyrazolkerns, zum Beispiel 1-(2'-Methyl-5'-sulfophenyl)-3-methyl-5-pyrazolon, 1 (3' - Amino-4'-sulfophenyl)-3-carboxy-5-pyrazolon, 1 (4'-Sulfophenyl)-3-methyl-5-pyrazolon, 1-(3'-Sulfophenyl)-3-methyl-5-pyrazolon, 1-(4'-Sulfophenyl)-3- carboxy-5-pyrazolon, 1-(3'-Sulfophenyl)-3-carboxy-5pyrazolon,
1-(3'- oder 4'-Ainophenyl)-3-carboxy- oder -3-methyl-5-pyrazolon, 1-(4'-Amino-3'-sulfophenyl)-3- methyl- oder -3-carboxy-5-pyrazolon, 1-(1',5'-Disulfonaphth-2'-yl)-3-methyl- oder -3-carboxy-5-pyrazolon, 1-(4',8'-Disulfonaphth-2'-yl)-3-methyl-5-pyrazolon; 5-Aminopyrazole, z. B. l-Aryl-5-aminopyrazole, wie l-Phenyl-3-methyl-5-aminopyrazol, 1-(3'-Aminophenyl)-3-methyl-5-aminopyrazol und 1-(3'-Amino-4'-sulfophenyl)-3-methyl-5-aminopyrazol, und Acetoacetarylamide, z. B.
Acetoacetanilid, Acetoacet-o-toluidid, Acetoacet-m-xylidid, Acetoacetanilid-3- oder -4-sulfonsäure und Aceto-acet-3- oder -4-aminoanilid. (c) Cyanurchlorid, Cyanurbromid, 2,4,5,6-Tetrachlorpyrimidin, 2,4,6 Tribrom-5-cyanpynmidm und 2,4,6-Trichlor-5-cyanpyrimidin. (d) m- und p-Aminobenzolsulfon-ss-chlor äthylamid, m- und p-Ainobenzolsulfon-ss-chlorpropyl- amid, die entsprechenden ss-Brompropylverbindungen und 3- oder 4-Aminobenzol-sulfon-N-(ss,y-dichlorpropylamid).
Die oben genannten Ausgangsmaterialien können auf verschiedene Weise miteinander kombiniert werden; z. B. kann die Diazoniumverbindung zunächst mit der Kupplungskomponente gekuppelt werden unter Bildung einer Monoazoverbindung der Formel [A-N = welche eine Aminogruppe, eine monosubstituierte Aminogruppe oder eine in eine Aminogruppe überführbare Gruppe trägt; im letzteren Fall wird die Monoazoverbindung sodann reduziert oder hydrolysiert unter Bildung der für die spätere Kondensation erforderlichen Amino- oder monosubstituierten Aminogruppe. Die so erhaltene Monoazoverbindung wird dann mit einer durch Kondensation des Cyanurhalogenids oder der Pyrimidinverbindung mit dem Amin (d) erhaltenen Verbindung umgesetzt.
Mit den neuen Farbstoffen lassen sich zahlreiche Textilmaterialien färben oder bedrucken. Die Farbstoffe sind insbesondere wertvolle Reaktivfarbstoffe für Cellulose, mit welcher sie, in Gegenwart von säurebindenden Mitteln, unter hohem Ziehvermögen reagieren.
In dem folgenden Beispiel bedeuten Teile jeweils Gewichtsteile.
Beispiel
Zu einer Suspension von 5,1 Teilen Cyanurchlorid in 25 Teilen Aceton und 100 Teilen Eiswasser wird eine Lösung von 6,8 Teilen 3-Aminobenzolsulfon-ss chloräthylamid in Aceton bei 0 bis 50 unter Rühren und Aufrechterhaltung eines pH-Werts von 6 bis 7 durch Zugabe von 2n-Natriumcarbonatlösung zugegeben. Nach mehrstündigem Rühren wird die Suspension einer neutralen Lösung von 15,25 Teilen des Trinatriumsalzes der 2-(4'-Amino-2'-ureidophenylazo)-naph thalin-3,6,8-trisulfonsäure in 250 Teilen Wasser zugesetzt, und das Gemisch wird bei 40 bis 450 C gerührt unter Aufrechterhaltung eines pH-Werts von 6 bis 7 (durch Zusatz von 2n-Natriumcarbonatlösung). Nach beendeter Umsetzung wird der Farbstoff durch Aussalzen mit Kaliumchlorid isoliert, mit einer Lösung von 60 Teilen Kaliumchlorid in 300 Teilen Wasser gewaschen und getrocknet.
Auf Cellulose erhält man in Gegenwart eines säurebindenden Mittels rötlichgelbe Farbtöne.
Process for the production of water-soluble reactive azo dyes
It is known to use dyes which contain halogen-s-triazine groups for dyeing fibers containing hydroxyl groups, in particular cellulose materials such as cotton and viscose rayon.
These dyes are easily fixed with good wet strength on the materials mentioned, since the halogen-s-triazine group can react with the hydroxyl groups of the cellulose molecule in the presence of an acid-binding agent, especially at elevated temperatures. The dyes are applied from aqueous liquor or in the form of aqueous color pastes; due to a side reaction in which the halostriazine group reacts with water instead of the cellulose molecule, some of the dye is not fixed on the fiber.
An excess of dye must therefore be used and the dyeings or prints must be washed carefully with a boiling soap solution in order to remove any unreacted dye.
The need for excess dye and the further process step make dyeing or printing more expensive, especially when darker colors are to be obtained.
The object of the present invention is a process for the preparation of water-soluble halogen-s-triazine reactive dyes, the fixation of which on the fiber is remarkably high and in which the wash-out treatments can be substantially reduced.
According to the present invention, water-soluble manoazo dyes of the formula
EMI1.1
prepared, where A is the residue of a diazo component of the benzene or naphthalene series, E is the residue of a para-coupling amine of the benzene or naphthalene series or of a 5-pyrazolone, 5-aminopyrazole or acetoacetarylamide, T a containing a reactive chlorine or bromine atom Pyrimidine or s-triazine ring bonded to an aromatic ring of A or E via a nitrogen atom, R and R 'are hydrogen or alkyl radicals with up to 4 carbon atoms, Z is an a, ss-alkylene radical with up to 4 carbon atoms Atoms and Y is a chlorine or bromine atom.
In order to ensure the water solubility of the dyes, the aromatic nuclei of the radicals A and E should have at least one sulfonic acid group and preferably at least two sulfonic acid groups. The rings can also contain other substituents, such as methyl, methoxy or ureido groups, chlorine or bromine atoms, carboxyl, nitro or carboalkoxy groups with up to 4 carbon atoms in the alkoxy group.
The pyrimidine or s-triazine ring represented by T must contain a chlorine or bromine atom in one of the positions 2, 4 and 6. Pyrimidine nuclei should also have an electronegative substituent in the 5-position, e.g. B. a chlorine or bromine atom or a cyano group have.
The new dyes are obtained according to the invention by a compound of the formula [A-N = N-E] in which one of the radicals A and E has a nitrogen atom with hydrogen which can be azinylated, with a compound of the formula
EMI1.2
<tb> Halogen-T¯N- <SEP> SO, N-Y-Z
<tb> <SEP> R
<tb> in which T 'is a pyrimidine or s-triazine ring having a reactive chlorine or bromine atom and halogen is a second chlorine or bromine atom bonded to T'.
The starting materials can be obtained by combining the following starting materials by coupling and condensation reactions known per se: On the one hand (a) the diazonium compound of an aromatic amine of the formula A-NH2 and (b) an amine of the benzene series coupling in the para position or a 5 -Pyrazolone, 5-aminopyrazole or aceto-acetarylamide as coupling component, where one of components (a) and (b) is an amino or monosubstituted amino group or a group which can be converted into an amino group after the coupling reaction without destroying the azo group, e.g.
B. must have a nitro or acetylamino group; and on the other hand (c) a cyanuric halide or a pyrimidine derivative containing chlorine or bromine atoms in the 2-, 4- and 6-position and an electronegative substituent in the 5-position and (d) an amine of the formula
EMI2.1
The following compounds are cited as examples: (a) Diazo components of the formula A-NH2
Aniline and naphthylamine sulfonic acids and substitution products thereof, such as orthanilic acid, aniline-2,5-disulfonic acid, 2-naphthylamine-4,8-disulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, l-naphthylamine3,8-disulfonic acid, 1-naphthylamine 3,6,8-trisulfonic acid, m-phenylenediamine-o-sulfonic acid, p-phenylenediamine-sulfonic acid and 2,6-diaminonaphthalene-4,8-disulfonic acid.
(b) coupling components
Anilines and a-naphthylamines, which can carry nonionic substituents, such as alkyl or alkoxy groups with up to 4 carbon atoms, acylamino and ureido groups, in the same ring as the amino group, as well as the NG to C4-alkyl-substituted derivatives of these compounds, z. B.
m-toluidine, 2-methoxy-5-methylaniline, o-anisidine, m-aminoacetanilide, m-aminophenylurea, l-naphthylamine-6- and 7-sulfonic acid and N-methylaniline, 5-pyrazolones with a mono- or bicyclic aromatic substituent in l-position and a methyl, carboxyl or carbo-Ci to C4-alkoxy group in the 3-position of the pyrazole nucleus, for example 1- (2'-methyl-5'-sulfophenyl) -3-methyl-5-pyrazolone , 1 (3'-amino-4'-sulfophenyl) -3-carboxy-5-pyrazolone, 1 (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (3'-sulfophenyl) -3-methyl -5-pyrazolone, 1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone, 1- (3'-sulfophenyl) -3-carboxy-5-pyrazolone,
1- (3'- or 4'-amino-phenyl) -3-carboxy- or -3-methyl-5-pyrazolone, 1- (4'-amino-3'-sulfophenyl) -3-methyl- or -3-carboxy -5-pyrazolone, 1- (1 ', 5'-disulfonaphth-2'-yl) -3-methyl- or -3-carboxy-5-pyrazolone, 1- (4', 8'-disulfonaphth-2'- yl) -3-methyl-5-pyrazolone; 5-aminopyrazoles, e.g. B. l-aryl-5-aminopyrazoles, such as l-phenyl-3-methyl-5-aminopyrazole, 1- (3'-aminophenyl) -3-methyl-5-aminopyrazole and 1- (3'-amino-4 ' -sulfophenyl) -3-methyl-5-aminopyrazole, and acetoacetarylamides, e.g. B.
Acetoacetanilide, acetoacet-o-toluidide, acetoacet-m-xylidide, acetoacetanilide-3- or -4-sulfonic acid and aceto-acet-3- or -4-aminoanilide. (c) cyanuric chloride, cyanuric bromide, 2,4,5,6-tetrachloropyrimidine, 2,4,6-tribromo-5-cyanopyrimidine and 2,4,6-trichloro-5-cyanopyrimidine. (d) m- and p-aminobenzenesulfon-ss-chloroethylamide, m- and p-ainobenzenesulfon-ss-chloropropyl amide, the corresponding ss-bromopropyl compounds and 3- or 4-aminobenzene sulfone-N- (ss, y- dichloropropylamide).
The above starting materials can be combined with one another in various ways; z. B. the diazonium compound can first be coupled with the coupling component to form a monoazo compound of the formula [A-N = which carries an amino group, a monosubstituted amino group or a group convertible into an amino group; in the latter case the monoazo compound is then reduced or hydrolyzed to form the amino or monosubstituted amino group required for the subsequent condensation. The monoazo compound thus obtained is then reacted with a compound obtained by condensing the cyanuric halide or the pyrimidine compound with the amine (d).
The new dyes can be used to dye or print numerous textile materials. The dyes are particularly valuable reactive dyes for cellulose, with which they react in the presence of acid-binding agents with high drawability.
In the following example, parts mean parts by weight.
example
To a suspension of 5.1 parts of cyanuric chloride in 25 parts of acetone and 100 parts of ice water, a solution of 6.8 parts of 3-aminobenzenesulfone-ss chloroethylamide in acetone is added at 0 to 50 while stirring and maintaining a pH of 6 to 7 Addition of 2N sodium carbonate solution added. After several hours of stirring, the suspension is added to a neutral solution of 15.25 parts of the trisodium salt of 2- (4'-amino-2'-ureidophenylazo) -naphthalene-3,6,8-trisulfonic acid in 250 parts of water, and the mixture is added is stirred at 40 to 450 C while maintaining a pH of 6 to 7 (by adding 2N sodium carbonate solution). After the reaction has ended, the dye is isolated by salting out with potassium chloride, washed with a solution of 60 parts of potassium chloride in 300 parts of water and dried.
On cellulose, reddish yellow shades are obtained in the presence of an acid-binding agent.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9936568A GB1119529A (en) | 1965-01-08 | 1965-01-08 | New water-soluble reactive monoazo dyestuffs, their preparation and use |
| CH5866A CH481993A (en) | 1965-01-08 | 1966-01-04 | Process for the preparation of water-soluble monoazo reactive dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH496780A true CH496780A (en) | 1970-09-30 |
Family
ID=25683385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH37569A CH496780A (en) | 1965-01-08 | 1966-01-04 | Process for the production of water-soluble reactive azo dyes |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH496780A (en) |
-
1966
- 1966-01-04 CH CH37569A patent/CH496780A/en not_active IP Right Cessation
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