CH360146A - Process for the preparation of new monoazo dyes - Google Patents
Process for the preparation of new monoazo dyesInfo
- Publication number
- CH360146A CH360146A CH360146DA CH360146A CH 360146 A CH360146 A CH 360146A CH 360146D A CH360146D A CH 360146DA CH 360146 A CH360146 A CH 360146A
- Authority
- CH
- Switzerland
- Prior art keywords
- methyl
- pyrazolone
- dye
- phenyl
- groups
- Prior art date
Links
- 239000000975 dye Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 13
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000003381 solubilizing effect Effects 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- -1 sulfo-phenylazo Chemical group 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- FTCOWMWIZNVSPP-UHFFFAOYSA-N 2-phenyl-4h-pyrazol-3-one Chemical compound O=C1CC=NN1C1=CC=CC=C1 FTCOWMWIZNVSPP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 2
- 150000008043 acidic salts Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000004753 textile Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- CWJQQASJVVAXKL-UHFFFAOYSA-N 4-(3-Methyl-5-oxo-4,5-dihydro-1H-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1 CWJQQASJVVAXKL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical class O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- BDQJRUBKFFJIIY-UHFFFAOYSA-N 1-(4-methylphenyl)-5-oxo-4h-pyrazole-3-carboxylic acid Chemical compound C1=CC(C)=CC=C1N1C(=O)CC(C(O)=O)=N1 BDQJRUBKFFJIIY-UHFFFAOYSA-N 0.000 description 1
- XAQCYASNAMYTQA-UHFFFAOYSA-N 2,4-diamino-5-methylbenzenesulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=C(N)C=C1N XAQCYASNAMYTQA-UHFFFAOYSA-N 0.000 description 1
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-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
- LUZXGSRCYGQGQF-UHFFFAOYSA-N 2,5-dichloro-4-(5-methyl-3-oxo-1h-pyrazol-2-yl)benzenesulfonic acid Chemical compound N1C(C)=CC(=O)N1C1=CC(Cl)=C(S(O)(=O)=O)C=C1Cl LUZXGSRCYGQGQF-UHFFFAOYSA-N 0.000 description 1
- ZGXJVLAIEZQGHY-UHFFFAOYSA-N 2-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzene-1,4-disulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC(S(O)(=O)=O)=CC=C1S(O)(=O)=O ZGXJVLAIEZQGHY-UHFFFAOYSA-N 0.000 description 1
- QCEWKNJIXJIIDW-UHFFFAOYSA-N 2-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzoic acid Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1C(O)=O QCEWKNJIXJIIDW-UHFFFAOYSA-N 0.000 description 1
- ZAHMVJOIEBCBPB-UHFFFAOYSA-N 3-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzoic acid Chemical compound O=C1CC(C)=NN1C1=CC=CC(C(O)=O)=C1 ZAHMVJOIEBCBPB-UHFFFAOYSA-N 0.000 description 1
- QENFKLWBWWDGLL-UHFFFAOYSA-N 3-chloro-5-methyl-4-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=C(C)C=C(S(O)(=O)=O)C=C1Cl QENFKLWBWWDGLL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CUGBBQWDGCXWNB-UHFFFAOYSA-N 4-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzoic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(C(O)=O)C=C1 CUGBBQWDGCXWNB-UHFFFAOYSA-N 0.000 description 1
- VEFAPHHLYOLHAR-UHFFFAOYSA-N 4-chloro-2-methyl-3-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound ClC1=CC=C(C(=C1N1N=C(CC1=O)C)C)S(=O)(=O)O VEFAPHHLYOLHAR-UHFFFAOYSA-N 0.000 description 1
- GEVZPIMXORJCJN-UHFFFAOYSA-N 4-chloro-2-methyl-5-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound ClC1=C(C=C(C(=C1)C)S(=O)(=O)O)N1N=C(CC1=O)C GEVZPIMXORJCJN-UHFFFAOYSA-N 0.000 description 1
- UWLNKHDLVZEYKQ-UHFFFAOYSA-N 4-chloro-3-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC(S(O)(=O)=O)=CC=C1Cl UWLNKHDLVZEYKQ-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
- FJEIOGWUGJVYOT-UHFFFAOYSA-N 5-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzene-1,3-disulfonic acid Chemical compound CC1=NN(C(C1)=O)C1=CC(=CC(=C1)S(=O)(=O)O)S(=O)(=O)O FJEIOGWUGJVYOT-UHFFFAOYSA-N 0.000 description 1
- PTNSJOPLNMEOTC-UHFFFAOYSA-N 5-chloro-2-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound ClC=1C=CC(=C(C1)S(=O)(=O)O)N1N=C(CC1=O)C PTNSJOPLNMEOTC-UHFFFAOYSA-N 0.000 description 1
- CTVYMWIPUUEBAY-UHFFFAOYSA-N 5-chloro-2-methyl-4-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound ClC1=CC(=C(C=C1N1N=C(CC1=O)C)C)S(=O)(=O)O CTVYMWIPUUEBAY-UHFFFAOYSA-N 0.000 description 1
- VPFYLXWBWWJMLH-UHFFFAOYSA-N 5-ethoxy-2-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound C(C)OC1=CC(=C(C=C1)N1N=C(CC1=O)C)S(=O)(=O)O VPFYLXWBWWJMLH-UHFFFAOYSA-N 0.000 description 1
- OBKGDFQPZVSSOM-UHFFFAOYSA-N 5-methyl-2-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound CC1=CC(=C(C=C1)N1N=C(CC1=O)C)S(=O)(=O)O OBKGDFQPZVSSOM-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
- IMZSHPUSPMOODC-UHFFFAOYSA-N 5-oxo-1-phenyl-4h-pyrazole-3-carboxylic acid Chemical compound O=C1CC(C(=O)O)=NN1C1=CC=CC=C1 IMZSHPUSPMOODC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- YNWUKJSMSIFJTD-UHFFFAOYSA-N ClC1=C(C=C(C(=C1)Cl)S(=O)(=O)O)N1N=C(CC1=O)C Chemical compound ClC1=C(C=C(C(=C1)Cl)S(=O)(=O)O)N1N=C(CC1=O)C YNWUKJSMSIFJTD-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 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
- C09B62/02—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung von neuen Monoazofarbstoffen Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von neuen Monoazofarbstoffen der Formel
EMI0001.0005
worin der Cyanurrest in m- oder p-Stellung zur Azo- gruppe an den Benzolring X gebunden ist, Y eine Methyl-, eine Carbalkoxy- oder eine Carboxylgruppe bedeutet,
das Molekül mindestens zwei löslich machende Gruppen enthält und die Benzolkerne X und Z auch weitere Substituenten, ausgenommen Hydroxylgruppen, enthalten können, welches dadurch gekennzeichnet ist, dass Cyanurchlorid mit einem m- oder p-Phenylendiamin, das weiter, ausgenommen durch Hydroxyl- oder Aminogruppen, substituiert sein kann, umgesetzt,
das so erhaltene Produkt dia- zotiert und die Diazoniumverbindung mit einem in der 3-Stellung eine Methyl-, Carbalkoxy- oder Carboxyl- gruppe enthaltenden 1-Phenyl-5-pyrazolon, worin der Phenylkern weiter, ausgenommen durch Hydroxyl- oder Aminogruppen, substituiert sein kann, gekuppelt wird,
wobei das Phenylendiamin und die Pyrazolon- kupplungskomponente so gewählt werden, dass der erhaltene Monoazofarbstoff mindestens zwei löslich machende Gruppen enthält.
Als Beispiele geeigneter 5-Pyrazolone, welche gebraucht werden können, seien z. B. erwähnt: 1-(4'-Sulfo-phenyl)-3-methyl-5-pyrazolon, 1-(6'-Chlor-3'-methyl 4'-sulfo-phenyl)-3-me- thyl-5-pyrazolon, 1-(2',5' Dichlor-4'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(2' Methyl-5'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(2'-Chlor-5'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(4'-Chlor-2'-sulfo-phenyl)
-3-methyl- 5-pyrazolon, 1-(2'-Chlor-4'-methyl-5'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(6'-Chlor-4'-sulfo-2'-methyl-phenyl)-3-carb- äthoxy-5-pyrazolon, 1-(6'-Chlor-4'-sulfo-2'-methyl-phenyl)-3-methyl- 5-pyrazolon, 1-(4'-Methyl-2'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(2',5'-disulfo-phenyl)-3-methyl 5-pyrazolon, 1-(4' Äthoxy-2'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(2',
4'-Dichlor-5'-sulfo-phenyl)-3-methyl- 5-pyrazolon, 1-(6'-Chlor-3'-sulfo-2' methyl-phenyl)-3-methyl- 5-pyrazolon, 1-(4'-Sulfo-phenyl)-3-carboxy-5-pyrazolon, 1-(3',5'-Disulfo-phenyl)-3-methyl-5-pyrazolon, 1-(4'-Carboxy-phenyl)-3-methyl-5-pyrazolon, 1-(3'-Carboxy-phenyl)-3 methyl-5-pyrazolon, 1-(2'-Carboxy-phenyl)-3-methyl-5-pyrazolon, 1-Phenyl-3-carboxy-5-pyrazolon und 1-p-Tolyl 3-carboxy-5-pyrazolon.
Als Beispiele der Phenylendiamine, welche in diesem Prozess gebraucht werden können, seien z. B. erwähnt: 2-Sulfo-1,4-phenylen-diamin, 6-Sulfo-1,3-phenylen-diamin und 2,4-Diamino-toluol-5-sulfonsäure. Die Reaktion des Cyanurchlorids mit dem Pheny- len-diamin wird vorzugsweise in einem wässrigen Medium bei einer Temperatur zwischen 0 und 5 C, vorzugsweise in Gegenwart eines säurebindenden Mittels, wie beispielsweise Natriumcarbonat, aus geführt,
welches in einer derartigen Weise zugegeben wird, dass der pH-Wert des Reaktionsgemisches unter 7 bleibt; im allgemeinen ist ein geringer I7berschuss von Cyanurchlorid von bis zu 10 Gewichtsprozent über das molekular äquivalente Gewicht erwünscht. Der Kupplungsschritt wird vorzugsweise bei einer Temperatur unter 5 C, zweckmässig bei 0-5 C, und bei einem so niedrigen pH, wie sich mit einer wirksamen Kupplung vereinbaren lässt, ausgeführt, damit Nebenreaktionen, beispielsweise Hydrolyse der Chloratome, die an den Cyanurrest gebunden blei ben, auf das Mindestmass beschränkt bleiben.
Es ist im allgemeinen vorzuziehen, die Farbstoffe aus dem Medium, in welchem sie gebildet worden sind, bei einem pH von - 6-8 zu isolieren, um die Entfernung des Chloratomes aus dem Cyanurrest zu folge Hydrolyse auf ein Minimum zu reduzieren, und dann die erhaltenen Farbstoffpasten vorzugsweise bei relativ niedrigen Temperaturen, z. B. zwischen 20 und 45 C, und vorzugsweise in Anwesenheit von puffernden Mitteln, welche den pH-Wert von ungefähr 6,5 aufrechterhalten, zu trocknen.
Beispiele solcher Puffersubstanzen sind Mischungen von Di- natriumhydrogenphosphat und Natriumdihydrogen- phosphat oder von Dinatriumhydrogenphosphat und Kaliumdihydrogenphosphat.
Die erfindungsgemäss erhältlichen neuen Farb stoffe sind in Form ihrer Alkalimetallsalze in Wasser löslich und können zum Färben von Seide, Wolle, regeneriertem Protein und Cellulose-Textilmateria- lien, wie z. B. Baumwolle, Leinen und Viskoserayon, Verwendung finden, indem man das Textilmaterial mit einer wässrigen Lösung (welche eine verdickte Druckpaste sein kann) des Farbstoffes in Verbin dung mit einer Behandlung mit einem säurebinden den Mittel, wie z.
B. Natriumhydroxyd, Kalium- phosphat oder Natriumcarbonat, behandelt. Die Be handlung mit dem säurebindenden Mittel kann vor, gleichzeitig oder nach der Behandlung mit dem Farb stoff erfolgen.
Die neuen Farbstoffe können auch für Seide, Wolle, regeneriertes Protein, Polyamid und modifi zierte Polyacrylnitril-Textilmaterialien nach den für diese Textilmaterialien üblichen Färbemethoden ge braucht werden. So kann man aus schwach sauren oder neutralen Färbstofflösungen färben. Die Farb- ,stofflösungen können z. B. Essigsäure, Ameisensäure, Natriumsulfat oder Ammoniumacetat enthalten.
Die Farbstoffe können auch auf Seide, Wolle und regenerierte Protein-Textilmaterialien mit Hilfe der für diese Materialien üblichen Druckverfahren angewendet werden.
Die so erhaltenen, gelben bis orangen Farbtöne besitzen eine sehr hohe Licht und Nassechtheit, ins besondere bei wiederholtem Waschen.
Die im folgenden Beispiel angegebenen Teile und Prozente sind Gewichtsteile und Gewichtsprozente. <I>Beispiel</I> 17,6 Teile 1,3-Phenylen-d'iamin-4-sulfonsäure werden in 200 Teilen Wasser gelöst und mit Na- triumcarbonat neutralisiert, und die Lösung wird zu einer Suspension von 9,3 Teilen Cyanurchlorid in 400 Teilen eines Gemisches von Eis und Wasser ge geben. Das Gemisch wird 30 Minuten lang gerührt und dann neutralisiert durch Zugabe von 23 Teilen.
10 % iger wässriger Natriumcarbonatlösung. Darauf werden 25 Teile 2n Natriumnitrit und 10 Teile kon zentrierte Salzsäure zugesetzt, und das Gemisch wird gerührt, bis die Diazotierung vollständig ist.
16,7 Teile 1-(4'-Sulfo-phenyl)-3-methyl-5-pyr- azolon werden in 200 Teilen Wasser gelöst durch Zugabe von Natriumcarbonat, so dass sich eine neu trale Lösung ergibt. 25 Teile kristallines Natrium acetat werden zugesetzt, und die Lösung wird auf eine Temperatur zwischen 0 und 5 C gekühlt.
Darauf wird die Lösung der Diazoverbindung zu gegeben, und das Gemisch wird 21/2 Stunden lang gerührt. Um den Farbstoff auszufällen, wird Koch salz zugegeben, und das Gemisch wird filtriert und der Rückstand auf dem Filter gründlich mit 4,2 Teilen wasserfreiem Dinatriumhydrogenphosphat und 7,6 Teilen wasserfreiem Kaliumdihydrogenphosphat gemischt und dann bei 30 C getrocknet.
Der so erhaltene Farbstoff ist ein grünlichgelber Feststoff, der in Wasser grünlichgelbe Lösungen er gibt. Wenn er mittels der oben beschriebenen Ver fahren auf Textilmaterialien aufgebracht wird, liefert er leuchtend grünlichgelbe Farbtöne, die ausgezeich nete Echtheit gegen wiederholtes Waschen und gegen Licht besitzen.
Process for the preparation of new monoazo dyes The present invention relates to a process for the preparation of new monoazo dyes of the formula
EMI0001.0005
where the cyanuric radical is bonded to the benzene ring X in the m or p position to the azo group, Y denotes a methyl, a carbalkoxy or a carboxyl group,
the molecule contains at least two solubilizing groups and the benzene nuclei X and Z can also contain further substituents, except for hydroxyl groups, which is characterized in that cyanuric chloride with an m- or p-phenylenediamine, which is further, except for hydroxyl or amino groups, can be substituted, implemented,
the product thus obtained is diazotized and the diazonium compound is substituted with a 1-phenyl-5-pyrazolone which contains a methyl, carbalkoxy or carboxyl group in the 3-position and in which the phenyl nucleus is further substituted with the exception of hydroxyl or amino groups can, is coupled,
the phenylenediamine and the pyrazolone coupling component being chosen so that the monoazo dye obtained contains at least two solubilizing groups.
Examples of suitable 5-pyrazolones which can be used are e.g. B. Mentioned: 1- (4'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (6'-chloro-3'-methyl 4'-sulfo-phenyl) -3-methyl-5 -pyrazolone, 1- (2 ', 5' dichloro-4'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (2 'methyl-5'-sulfo-phenyl) -3-methyl- 5- pyrazolone, 1- (2'-chloro-5'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (4'-chloro-2'-sulfo-phenyl)
-3-methyl-5-pyrazolone, 1- (2'-chloro-4'-methyl-5'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (6'-chloro-4'-sulfo -2'-methyl-phenyl) -3-carb-ethoxy-5-pyrazolone, 1- (6'-chloro-4'-sulfo-2'-methyl-phenyl) -3-methyl-5-pyrazolone, 1- (4'-methyl-2'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-disulfo-phenyl) -3-methyl 5-pyrazolone, 1- (4' ethoxy- 2'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (2 ',
4'-dichloro-5'-sulfo-phenyl) -3-methyl-5-pyrazolone, 1- (6'-chloro-3'-sulfo-2 'methyl-phenyl) -3-methyl-5-pyrazolone, 1 - (4'-sulfo-phenyl) -3-carboxy-5-pyrazolone, 1- (3 ', 5'-disulfo-phenyl) -3-methyl-5-pyrazolone, 1- (4'-carboxy-phenyl) -3-methyl-5-pyrazolone, 1- (3'-carboxy-phenyl) -3 methyl-5-pyrazolone, 1- (2'-carboxy-phenyl) -3-methyl-5-pyrazolone, 1-phenyl- 3-carboxy-5-pyrazolone and 1-p-tolyl 3-carboxy-5-pyrazolone.
Examples of the phenylenediamines that can be used in this process are e.g. B. mentioned: 2-sulfo-1,4-phenylene-diamine, 6-sulfo-1,3-phenylene-diamine and 2,4-diamino-toluene-5-sulfonic acid. The reaction of the cyanuric chloride with the phenylenediamine is preferably carried out in an aqueous medium at a temperature between 0 and 5 C, preferably in the presence of an acid-binding agent such as sodium carbonate,
which is added in such a way that the pH of the reaction mixture remains below 7; In general, a slight excess of cyanuric chloride of up to 10 percent by weight over the molecular equivalent weight is desirable. The coupling step is preferably carried out at a temperature below 5 C, expediently at 0-5 C, and at a pH as low as can be reconciled with an effective coupling, in order to prevent side reactions, for example hydrolysis of the chlorine atoms which are bound to the cyanuric radical practice, remain limited to the minimum.
It is generally preferable to isolate the dyes from the medium in which they were formed at a pH of -6-8 in order to minimize the removal of the chlorine atom from the cyanuric residue following hydrolysis, and then the obtained dye pastes preferably at relatively low temperatures, e.g. B. between 20 and 45 ° C, and preferably in the presence of buffering agents which maintain the pH of about 6.5 to dry.
Examples of such buffer substances are mixtures of disodium hydrogen phosphate and sodium dihydrogen phosphate or of disodium hydrogen phosphate and potassium dihydrogen phosphate.
The novel dyes obtainable according to the invention are soluble in water in the form of their alkali metal salts and can be used for dyeing silk, wool, regenerated protein and cellulose textile materials, such as. As cotton, linen and viscose rayon, find use by the textile material with an aqueous solution (which can be a thickened printing paste) of the dye in connec tion with a treatment with an acid-binding agent, such as.
B. sodium hydroxide, potassium phosphate or sodium carbonate treated. The treatment with the acid-binding agent can take place before, at the same time or after the treatment with the dye.
The new dyes can also be used for silk, wool, regenerated protein, polyamide and modified polyacrylonitrile textile materials by the dyeing methods customary for these textile materials. So you can dye from weakly acidic or neutral dye solutions. The dye, substance solutions can, for. B. acetic acid, formic acid, sodium sulfate or ammonium acetate.
The dyes can also be applied to silk, wool and regenerated protein textile materials using the printing processes customary for these materials.
The yellow to orange color shades obtained in this way have a very high level of light and wet fastness, especially when washed repeatedly.
The parts and percentages given in the following example are parts and percentages by weight. <I> Example </I> 17.6 parts of 1,3-phenylen-d'iamine-4-sulfonic acid are dissolved in 200 parts of water and neutralized with sodium carbonate, and the solution becomes a suspension of 9.3 parts Give cyanuric chloride in 400 parts of a mixture of ice and water. The mixture is stirred for 30 minutes and then neutralized by adding 23 parts.
10% aqueous sodium carbonate solution. Then 25 parts of 2N sodium nitrite and 10 parts of concentrated hydrochloric acid are added and the mixture is stirred until the diazotization is complete.
16.7 parts of 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone are dissolved in 200 parts of water by adding sodium carbonate, so that a neutral solution results. 25 parts of crystalline sodium acetate are added and the solution is cooled to a temperature between 0 and 5 ° C.
The solution of the diazo compound is then added and the mixture is stirred for 21/2 hours. To precipitate the dye, sodium chloride is added and the mixture is filtered and the residue on the filter mixed thoroughly with 4.2 parts of anhydrous disodium hydrogen phosphate and 7.6 parts of anhydrous potassium dihydrogen phosphate and then dried at 30 ° C.
The dye obtained in this way is a greenish-yellow solid which gives greenish-yellow solutions in water. When it is applied to textile materials by means of the method described above, it delivers bright greenish-yellow shades that have excellent fastness to repeated washing and to light.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB360146X | 1955-11-25 | ||
| GB191156X | 1956-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH360146A true CH360146A (en) | 1962-02-15 |
Family
ID=26253862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH360146D CH360146A (en) | 1955-11-25 | 1956-11-26 | Process for the preparation of new monoazo dyes |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH360146A (en) |
-
1956
- 1956-11-26 CH CH360146D patent/CH360146A/en unknown
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