CA1101412A - Fibre-reactive azo dyes, process for their manufacture and use thereof - Google Patents
Fibre-reactive azo dyes, process for their manufacture and use thereofInfo
- Publication number
- CA1101412A CA1101412A CA283,714A CA283714A CA1101412A CA 1101412 A CA1101412 A CA 1101412A CA 283714 A CA283714 A CA 283714A CA 1101412 A CA1101412 A CA 1101412A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- amino
- fibre
- carbon atoms
- alkyl
- 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
Links
- 239000000987 azo dye Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- -1 sulphomethyl Chemical group 0.000 claims abstract description 82
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims abstract description 7
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000005840 aryl radicals Chemical class 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000004442 acylamino group Chemical group 0.000 claims abstract description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 230000008878 coupling Effects 0.000 claims description 41
- 238000010168 coupling process Methods 0.000 claims description 41
- 238000005859 coupling reaction Methods 0.000 claims description 41
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 30
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 claims description 28
- 239000007859 condensation product Substances 0.000 claims description 18
- 239000000460 chlorine Chemical group 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Chemical group 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000007858 starting material Substances 0.000 claims description 10
- 238000004043 dyeing Methods 0.000 claims description 9
- 150000001448 anilines Chemical class 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000985 reactive dye Substances 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- FOINSAWEWXUXPQ-UHFFFAOYSA-N 4-acetamido-2-aminobenzenesulfonic acid Chemical compound CC(=O)NC1=CC=C(S(O)(=O)=O)C(N)=C1 FOINSAWEWXUXPQ-UHFFFAOYSA-N 0.000 claims 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 2
- OLCKRGCUQOKQCM-UHFFFAOYSA-N 2-fluoro-1,3,5-triazine Chemical compound FC1=NC=NC=N1 OLCKRGCUQOKQCM-UHFFFAOYSA-N 0.000 claims 1
- 229920003043 Cellulose fiber Polymers 0.000 claims 1
- 239000004753 textile Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000000975 dye Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- 239000000306 component Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 235000017168 chlorine Nutrition 0.000 description 7
- 229940060038 chlorine Drugs 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- UGEHFOSBNBEWMP-UHFFFAOYSA-N 2,3-diaminobenzenesulfonic acid Chemical class NC1=CC=CC(S(O)(=O)=O)=C1N UGEHFOSBNBEWMP-UHFFFAOYSA-N 0.000 description 2
- VOPSFYWMOIKYEM-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C=C1S(O)(=O)=O VOPSFYWMOIKYEM-UHFFFAOYSA-N 0.000 description 2
- KCEIVWKDBLAQKL-UHFFFAOYSA-N 2,5-dichloro-4-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC(Cl)=C(S(O)(=O)=O)C=C1Cl KCEIVWKDBLAQKL-UHFFFAOYSA-N 0.000 description 2
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 2
- YADSWTKOIHUSDX-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(N)=C(S(O)(=O)=O)C=C1S(O)(=O)=O YADSWTKOIHUSDX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XYQYTXDJSYHZAQ-UHFFFAOYSA-N N1=CN=CN=C1.[F] Chemical compound N1=CN=CN=C1.[F] XYQYTXDJSYHZAQ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 2
- 235000019233 fast yellow AB Nutrition 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229960000443 hydrochloric acid Drugs 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- MAZKAODOCXYDCM-UHFFFAOYSA-N tetrazone Chemical group N\N=N\N MAZKAODOCXYDCM-UHFFFAOYSA-N 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- AQIJCINXWBYKIF-UHFFFAOYSA-N 1,3,5-trifluoro-2h-1,2,4-triazine Chemical compound FN1NC(F)=NC(F)=C1 AQIJCINXWBYKIF-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
- 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- VEMGKBUHUTYHHA-UHFFFAOYSA-N 3-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC=CC(S(O)(=O)=O)=C1 VEMGKBUHUTYHHA-UHFFFAOYSA-N 0.000 description 1
- ULUIMLJNTCECJU-UHFFFAOYSA-N 3-amino-4-hydroxybenzenesulfonate;hydron Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1O ULUIMLJNTCECJU-UHFFFAOYSA-N 0.000 description 1
- ZDFCTUISEBJBEQ-UHFFFAOYSA-N 3-amino-4-hydroxynaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=C(O)C(N)=CC(S(O)(=O)=O)=C21 ZDFCTUISEBJBEQ-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
- 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
- NHLAPJMCARJFOG-UHFFFAOYSA-N 3-methyl-1,4-dihydropyrazol-5-one Chemical compound CC1=NNC(=O)C1 NHLAPJMCARJFOG-UHFFFAOYSA-N 0.000 description 1
- AJPUJTAMBSRTEG-UHFFFAOYSA-N 3-methyl-4-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1C AJPUJTAMBSRTEG-UHFFFAOYSA-N 0.000 description 1
- XSFKCGABINPZRK-UHFFFAOYSA-N 4-aminopyrazol-3-one Chemical compound NC1=CN=NC1=O XSFKCGABINPZRK-UHFFFAOYSA-N 0.000 description 1
- NCVJMVPQHKAGHX-UHFFFAOYSA-N 5-amino-2-(3-methyl-5-oxo-4H-pyrazol-1-yl)benzenesulfonic acid Chemical compound NC1=CC(=C(C=C1)N1N=C(CC1=O)C)S(=O)(=O)O NCVJMVPQHKAGHX-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SBEZNUQJZHDWEU-UHFFFAOYSA-L C(=O)([O-])C(O)C(O)C(=O)[O-].[Cu+2].[Na+] Chemical compound C(=O)([O-])C(O)C(O)C(=O)[O-].[Cu+2].[Na+] SBEZNUQJZHDWEU-UHFFFAOYSA-L 0.000 description 1
- 102100038916 Caspase-5 Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101100112336 Homo sapiens CASP5 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100273286 Mus musculus Casp4 gene Proteins 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical group [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001049 brown dye Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009980 pad dyeing Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 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
- C09B62/02—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)
Abstract
ABSTRACT OF THE DISCLOSURE
Fibre-reactive azo dyes of the formula
Fibre-reactive azo dyes of the formula
Description
~1014~;2 The present invention relates to fibre-reactive azo dyes of the formula N - B - (SO3H)n A-N=N ~ ¦
L ~ ~
wherein A is a residue of benzene or naphthalene, Y is methyl, sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen~ n is a positive integer from 1 to 6 and m is 1 or 2, and A and B can contain as further substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and car-boxyl group and halogen atoms, and the phenylamino radical bonded to the s-triazine ring can contain as further substituent at the phenyl nucleus, in addition to and independently of X, an alkyl radical of 1 to 4 carbon atoms, and, if m is 2, 'che substituents R and X of both 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-N(R) radicals can be different and metal complexes of the fibre-reactive azo dyes of the formula (1).
Examples of substituents on the benzene or naphthalene residue A are methyl, ethyl and propyl radicals; methoxy, ~,'' 1 ethoxy, propyloxy and isopropyloxy groups; acetylamino, propionylamino and benzoylamino groups; -NH2~ methylamino and ethylamino groups; and fluorine, chlorine and bromine atoms.
An alkyl radical B is in particular an unsubstituted alkyl radical, for example methyl or ethyl; however, the alkyl radicals can also be further substituted, for example by chlor-ine, hydroxy, cyano and amino.
Preferably B is an aryl radical, in particular a phenyl or naphthyl radical, which, in addition to S03H groups, can contain for example the substituents cited above as examples for the radical A. Suitable values for R as alkyl radicals of 1 to 4 carbon atoms are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
Suitable values for X as alkyl radicals of 1 to 4 carbon atoms are: methyl, ethyl, propyl, isopropyl, butyl~ isobutyl, sec-butyl and tert-butyl, and as alkoxy radicals of 1 to 4 carbon atoms: methoxy, ethoxy, propyloxy, isopropyloxy, butyl-oxy, isobutyloxy, sec-butyloxy and tert-butyloxy. Halogen is to be understood as meaning fluorine, chlorine and bromine.
Possible further substituents in addition to and independ-ently of X which can be present at the phenyl nucleus of the phenyl-al ~ 141Z
~...
amino radical bonded to the s-triazine ring are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl and ~: tert -butyl.
~ .
~; The sulpho groups can be distributed at random among the : :~ radicals A and B.
:~ ~ Preferred fibre-reactive azo dyes are those of the formula (1), wherein m is 1 and the 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-N(R3 radLcal i.s bonded_to the.radiçal A._X iS=~
,-- , ~, ,, _ ~ , , , _ , . . _ ,, . , _ , _ _ _ . ., _ _ . . . _ _ _ _ ~
~rerera~ly methyl, meth_xy, carboxyl or chlorine.
i ~ 1 An important subgroup of fibre-reactive azo dyes of the formula :: ~ (1) consists of those wherein A is a sulphophenyl radical, Y
.~ . is methyl or carboxyl, B is a phenyl or naphthyl radical which ;is unsubstituted or substituted by sulpho and chlorine, R is : hydrogen and m is 1, and X and n are as defined in formula (1).
~ . ~
Useful fibre-reactive azo dyes of the formula (1) are for : example the~fibre-reactive azo dye of the formula . OH SO H
: ~ 1 3 ¢~ 't; '~,rq~C~ ~
~ N SO3H
,. .
and that of the formula i::: ~ .
- ' .
.. . , ' , . ' , ,, , ' .
, ' ~ 4 1 2 OH SO~
C ~lr~ ~ ~ S03 N N / I ~ SO
COOH
.
The dyes of the formula (1) are fibre-reactive since they contain a removable fluorine atom in the s-triazine radical.
By fibre-reactive compounds are meant those compounds which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.
The manufacture of the fibre-reactive azo dyes of the formula (1) consists in reacting a diazotised amino compound of the formula A-NH2 (2), a coupling component of the formula OH
N-~ (3)~
wherein A and B together contain 1 to 6 sulpho groups, .. .... . . .. .
and. A_and/or B..contain a -N(R)H group,.l or.2.e.quival nt.s of 2,4,6-trifluoro-s-triazine of the formula 111~1412 CI-~
~,N
and 1 or 2 equivalents of identical or different aminobenzenes of the formula a ¦ 2 ~ - (5) - X
by coupling and condensation in optional sequence to give a fibre-reactive aæo dye of the formula (1).
The starting material is preferably an aminobenzene of the formula (5), wherein X is methyl, methoxy, carboxyl or chlorine.
In preferred embodiments of the above described process, the starting compounds are compounds of the formulae (2) and (3) wherein only A, but not B, contains a -N(R)H group.
A further preferred embodiment is that wherein the starting materials are compounds of the formula (2), wherein A is a sulphophenyl radical of the formula (3), in which Y is methyl or carboxyl, and B is a phenyl or naphthyl radical which is un-. substituted or substituted by sulpho and chlorine, whilst A
and B together contain 1 to 6 sulpho groups and A or B contains.
a -NH2 group, one equivalent of 2,4,6-trifluoro-s-triaæine of ... .
..
. . .........
the formula (4) and one equivalent of an aminobenzene of the formula (5), wherein X is as defined in formula (1).
Since the sequence in which the above process steps are carried out can vary and some, if appropriate, can be carried out simultaneously, a number of different variants of the process are possible. The starting materials to be used for each partial reaction result from formula (1). In general, the re-action is carried out stepwise in succession and the sequence of the simple reactions of the individual reaction components of:the formulae (2), (3), (4) and (5) can be freely chosen.
Important variants of the process are:
1) coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo com-pound, coDdensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine of the ~ormula (4) and condensing the primary conden-:
sation~product thereby obtained with an aminobenzene of theformula (S) to give a fibre-reactive dye of the formula (l);
L ~ ~
wherein A is a residue of benzene or naphthalene, Y is methyl, sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen~ n is a positive integer from 1 to 6 and m is 1 or 2, and A and B can contain as further substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and car-boxyl group and halogen atoms, and the phenylamino radical bonded to the s-triazine ring can contain as further substituent at the phenyl nucleus, in addition to and independently of X, an alkyl radical of 1 to 4 carbon atoms, and, if m is 2, 'che substituents R and X of both 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-N(R) radicals can be different and metal complexes of the fibre-reactive azo dyes of the formula (1).
Examples of substituents on the benzene or naphthalene residue A are methyl, ethyl and propyl radicals; methoxy, ~,'' 1 ethoxy, propyloxy and isopropyloxy groups; acetylamino, propionylamino and benzoylamino groups; -NH2~ methylamino and ethylamino groups; and fluorine, chlorine and bromine atoms.
An alkyl radical B is in particular an unsubstituted alkyl radical, for example methyl or ethyl; however, the alkyl radicals can also be further substituted, for example by chlor-ine, hydroxy, cyano and amino.
Preferably B is an aryl radical, in particular a phenyl or naphthyl radical, which, in addition to S03H groups, can contain for example the substituents cited above as examples for the radical A. Suitable values for R as alkyl radicals of 1 to 4 carbon atoms are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
Suitable values for X as alkyl radicals of 1 to 4 carbon atoms are: methyl, ethyl, propyl, isopropyl, butyl~ isobutyl, sec-butyl and tert-butyl, and as alkoxy radicals of 1 to 4 carbon atoms: methoxy, ethoxy, propyloxy, isopropyloxy, butyl-oxy, isobutyloxy, sec-butyloxy and tert-butyloxy. Halogen is to be understood as meaning fluorine, chlorine and bromine.
Possible further substituents in addition to and independ-ently of X which can be present at the phenyl nucleus of the phenyl-al ~ 141Z
~...
amino radical bonded to the s-triazine ring are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl and ~: tert -butyl.
~ .
~; The sulpho groups can be distributed at random among the : :~ radicals A and B.
:~ ~ Preferred fibre-reactive azo dyes are those of the formula (1), wherein m is 1 and the 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-N(R3 radLcal i.s bonded_to the.radiçal A._X iS=~
,-- , ~, ,, _ ~ , , , _ , . . _ ,, . , _ , _ _ _ . ., _ _ . . . _ _ _ _ ~
~rerera~ly methyl, meth_xy, carboxyl or chlorine.
i ~ 1 An important subgroup of fibre-reactive azo dyes of the formula :: ~ (1) consists of those wherein A is a sulphophenyl radical, Y
.~ . is methyl or carboxyl, B is a phenyl or naphthyl radical which ;is unsubstituted or substituted by sulpho and chlorine, R is : hydrogen and m is 1, and X and n are as defined in formula (1).
~ . ~
Useful fibre-reactive azo dyes of the formula (1) are for : example the~fibre-reactive azo dye of the formula . OH SO H
: ~ 1 3 ¢~ 't; '~,rq~C~ ~
~ N SO3H
,. .
and that of the formula i::: ~ .
- ' .
.. . , ' , . ' , ,, , ' .
, ' ~ 4 1 2 OH SO~
C ~lr~ ~ ~ S03 N N / I ~ SO
COOH
.
The dyes of the formula (1) are fibre-reactive since they contain a removable fluorine atom in the s-triazine radical.
By fibre-reactive compounds are meant those compounds which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.
The manufacture of the fibre-reactive azo dyes of the formula (1) consists in reacting a diazotised amino compound of the formula A-NH2 (2), a coupling component of the formula OH
N-~ (3)~
wherein A and B together contain 1 to 6 sulpho groups, .. .... . . .. .
and. A_and/or B..contain a -N(R)H group,.l or.2.e.quival nt.s of 2,4,6-trifluoro-s-triazine of the formula 111~1412 CI-~
~,N
and 1 or 2 equivalents of identical or different aminobenzenes of the formula a ¦ 2 ~ - (5) - X
by coupling and condensation in optional sequence to give a fibre-reactive aæo dye of the formula (1).
The starting material is preferably an aminobenzene of the formula (5), wherein X is methyl, methoxy, carboxyl or chlorine.
In preferred embodiments of the above described process, the starting compounds are compounds of the formulae (2) and (3) wherein only A, but not B, contains a -N(R)H group.
A further preferred embodiment is that wherein the starting materials are compounds of the formula (2), wherein A is a sulphophenyl radical of the formula (3), in which Y is methyl or carboxyl, and B is a phenyl or naphthyl radical which is un-. substituted or substituted by sulpho and chlorine, whilst A
and B together contain 1 to 6 sulpho groups and A or B contains.
a -NH2 group, one equivalent of 2,4,6-trifluoro-s-triaæine of ... .
..
. . .........
the formula (4) and one equivalent of an aminobenzene of the formula (5), wherein X is as defined in formula (1).
Since the sequence in which the above process steps are carried out can vary and some, if appropriate, can be carried out simultaneously, a number of different variants of the process are possible. The starting materials to be used for each partial reaction result from formula (1). In general, the re-action is carried out stepwise in succession and the sequence of the simple reactions of the individual reaction components of:the formulae (2), (3), (4) and (5) can be freely chosen.
Important variants of the process are:
1) coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo com-pound, coDdensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine of the ~ormula (4) and condensing the primary conden-:
sation~product thereby obtained with an aminobenzene of theformula (S) to give a fibre-reactive dye of the formula (l);
2) condensing a coupling component of the formula (3) with 2;,4,6-tri:fluoro-~1,3,5-triazine of the formula (4), condensing the: primary condensation product thereby obtained with an aminobenzene of the formula (5) and coupling the secondary condensation product with a diazotised amino compound of the formula (2) to give a fibre-reactive azo dye of the formula (1);
3) condensing a coupling component of the formula (3) with :
2,4,6-trifluoro-1,3,5-triazine of the formula (4), coupling .
:
.' . . ~ , .. , . . ~
.
.
11~141Z
the primary condensation thereby obtained with a diazotised amino compound of the formula (2) and condensing the resultant azo compound with an aminobenzene of the formula (5) to give . a fibre-reactive azo dye of the formula (l);
~: 4) condensing an amino compound of the formula (2) with 2,4,6-trifluoro-s-triazine of the formula (4), condensing the :
resultant primary condensation product with an aminobenzene of the formula (5), diazotising the secondary condensation :product and coupling it with a coupling component of the formula :: (3) to give a fibre-reactive azo dye of the formula (1);
5) condensing an amino compound of the formula (2) with .;2,4,6-trifluoro-s-triazine of the formula (4), diazotising the ~:
primary condensation product thereby obtained and coupling it wlth a coupling component of the formula (3) and condensing the;resultant azo compound with an aminobenzene of the formula (S):to~give a fibre-reactive dye of the formula (l);
:6)i: coupling a diazotised amino compound of the formula (2) with~a~coupling component of the formula (3) to give an azo compound~condensing this azo compound with 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula (4) and condensing the resultant diprimary condensation product with 2 equivalents of~an aminobenzene of the formula (5) to give a fibre-bi-reactive azo dye of the formula (l);
i: :
~ ~ ~ 7) coupling a diazotised amino compound of the formula (2) ;
: with:a coupLing component of the formula (3) to give an azo . .
.
llal4~2 compound and condensing this azo compound with 2 equivalents of the primary condensation product of 2,4,6-trifluoro-s-tria-zine of the formula (4) and an aminobenzene of the formula (5) to give a fibre-bireactive azo dye of the ~ormula (1).
Examples of starting materials which can be used for the manu-facture of the fibre-reactive azo dyes o~ the formula (1) are:
Amino compounds of the formula (22 (diazo components) i-aminobenzene-2-, -3- and -4-sulphonic acid, l-aminobenzene-2,4- and -2,5-disulphonic acid, l-amino-4-methylbenzene-2-sulphonic acid, l-amino-3-methylbenzene-6-sulphonic acid, l-amino-6-methylbenzene-3- or -4-sulphonic acid, l-amino-2,4-dimethylbenzene-6-sulphonic acid, l-amino-2-carboxybenzene-4-sulphonic acid, l-amino-4-carboxybenzene-2-sulphonic acid, l-amino-4- or -5-chlorbenzene-2-sulphonic acid, l-amino-6-chlorobenzene-3- or -4-sulphonic acid, l-amino-3,4-dichlorobenzene-6-sulphonic acid, l-amino-2,5-dichlorobenzene-4-sulphonic a~id, l-amino-4-methyl-5-chlorobenzene-2-sulphonic acid, l-amino-5-methyl-4-chlorobenzene-2-sulphonic acid, l-amino-4- or -5-methoxybenzene-2-sulphonic acid, l-amino-6-methoxybenzene-3- or -4-sulphonic acid, l-amino-6-ethoxybenzene-3- or -4-sulphonic a id, l-amino-2,4-dimethoxybenzene-6-sulphonic acid, -. ,.- . -.
l-amino-2,5-dimethoxybenzene-4-sulphonic acid, 1,4-diaminobenzene-2-sulphonic acid, 1,3-diaminobenzene-6-sulphonic acid, 1,4-diaminobenzene-2,5-disulphonic acid, 1,3-diaminobenzene-4,6-disulphonic acid, l-amino-3-acetylaminobenzene-6-sulphonic acid, l-amino-4-acetylaminobenzene-2-sulphonic acid, l-amino-3-acetylamino-4-methylbenzene-6-sulphonic acid, aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulphonic acid, 2-aminonaphthalene-1-, -5- or -6-sulphonic acid, aminonaphthalene-3,6- or -5,7-disulphonic acid, , : : 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulphonic acid, : ~ ;: l-aminonaphthalene-2,5,7-trisulphonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- or 4,6,8-trisulphonic acid, hydroxy-2-aminobenzene-4-sulphonic acid, ~: ~ z ;l-hydroxy-2-aminobenzene-5-sulphonic acid, , l-hydroxy-2-aminobenzene-4,6-disulphonic acid, hyd:roxy-2~-amino-4-acetylaminobenzene-6-sulphonic acid, I-hydroxy-2-amino-6-acetylaminobenzene-4-sulphonic acid, l-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid, , ~ ~
l-hydroxy-2-amino-4-methylsulphonyl-benzene, l-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulphonic acid.
' ~ ~ .
` 1 ~0 14 1 ~
- Coupling components of the formula (3) 3-methyl-5-pyrazolone, 5-pyrazolone-3-carboxylic acid, l-phenyl-3-sulphomethyl-5-pyrazolone, 1-(4'-sulphophenyl)-3-methyl-5-pyraæolone, 1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 1-(3'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(3'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 1-(2',5'-disulphophenyl)-3-methyl-5-pyrazolone, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2'-chloro-4'-sulphophenyl)-3-me~hyl-5-pyrazolone, 1-(2'-chloro-5'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2'-sulpho-4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2'-methyl-4'-sulphophenyl)-3-methyl-5-pyrazolone, . 1-(2'-methyl-4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 1-(6'-chloro-2'-methyl-4'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, 1-(4',8'-disulphonaphthyl[2'])-S-pyrazolone-3-carboxylic acid, 1-(5',7'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, 1-(5',7'-disulphonaphthyl~2'])-5-pyrazolone-3-carboxylic acid, 1-(4',6',8'-trisulphonaphthyl-[2'~)-3-methyl-5-pyrazolone, 1-(4',6',8'-trisulphonaphthyl-[2'])-5-pyrazolone-3-carboxylic acid, 1-(6l-amino-4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, .. ~ ..... .. . . . . , .. ... ~ ., . , .. , . .. ... . . .. . ... . .. _ . .g, . ..
-, :.
2,4,6-trifluoro-1,3,5-triazine of the formula (4), coupling .
:
.' . . ~ , .. , . . ~
.
.
11~141Z
the primary condensation thereby obtained with a diazotised amino compound of the formula (2) and condensing the resultant azo compound with an aminobenzene of the formula (5) to give . a fibre-reactive azo dye of the formula (l);
~: 4) condensing an amino compound of the formula (2) with 2,4,6-trifluoro-s-triazine of the formula (4), condensing the :
resultant primary condensation product with an aminobenzene of the formula (5), diazotising the secondary condensation :product and coupling it with a coupling component of the formula :: (3) to give a fibre-reactive azo dye of the formula (1);
5) condensing an amino compound of the formula (2) with .;2,4,6-trifluoro-s-triazine of the formula (4), diazotising the ~:
primary condensation product thereby obtained and coupling it wlth a coupling component of the formula (3) and condensing the;resultant azo compound with an aminobenzene of the formula (S):to~give a fibre-reactive dye of the formula (l);
:6)i: coupling a diazotised amino compound of the formula (2) with~a~coupling component of the formula (3) to give an azo compound~condensing this azo compound with 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula (4) and condensing the resultant diprimary condensation product with 2 equivalents of~an aminobenzene of the formula (5) to give a fibre-bi-reactive azo dye of the formula (l);
i: :
~ ~ ~ 7) coupling a diazotised amino compound of the formula (2) ;
: with:a coupLing component of the formula (3) to give an azo . .
.
llal4~2 compound and condensing this azo compound with 2 equivalents of the primary condensation product of 2,4,6-trifluoro-s-tria-zine of the formula (4) and an aminobenzene of the formula (5) to give a fibre-bireactive azo dye of the ~ormula (1).
Examples of starting materials which can be used for the manu-facture of the fibre-reactive azo dyes o~ the formula (1) are:
Amino compounds of the formula (22 (diazo components) i-aminobenzene-2-, -3- and -4-sulphonic acid, l-aminobenzene-2,4- and -2,5-disulphonic acid, l-amino-4-methylbenzene-2-sulphonic acid, l-amino-3-methylbenzene-6-sulphonic acid, l-amino-6-methylbenzene-3- or -4-sulphonic acid, l-amino-2,4-dimethylbenzene-6-sulphonic acid, l-amino-2-carboxybenzene-4-sulphonic acid, l-amino-4-carboxybenzene-2-sulphonic acid, l-amino-4- or -5-chlorbenzene-2-sulphonic acid, l-amino-6-chlorobenzene-3- or -4-sulphonic acid, l-amino-3,4-dichlorobenzene-6-sulphonic acid, l-amino-2,5-dichlorobenzene-4-sulphonic a~id, l-amino-4-methyl-5-chlorobenzene-2-sulphonic acid, l-amino-5-methyl-4-chlorobenzene-2-sulphonic acid, l-amino-4- or -5-methoxybenzene-2-sulphonic acid, l-amino-6-methoxybenzene-3- or -4-sulphonic acid, l-amino-6-ethoxybenzene-3- or -4-sulphonic a id, l-amino-2,4-dimethoxybenzene-6-sulphonic acid, -. ,.- . -.
l-amino-2,5-dimethoxybenzene-4-sulphonic acid, 1,4-diaminobenzene-2-sulphonic acid, 1,3-diaminobenzene-6-sulphonic acid, 1,4-diaminobenzene-2,5-disulphonic acid, 1,3-diaminobenzene-4,6-disulphonic acid, l-amino-3-acetylaminobenzene-6-sulphonic acid, l-amino-4-acetylaminobenzene-2-sulphonic acid, l-amino-3-acetylamino-4-methylbenzene-6-sulphonic acid, aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulphonic acid, 2-aminonaphthalene-1-, -5- or -6-sulphonic acid, aminonaphthalene-3,6- or -5,7-disulphonic acid, , : : 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulphonic acid, : ~ ;: l-aminonaphthalene-2,5,7-trisulphonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- or 4,6,8-trisulphonic acid, hydroxy-2-aminobenzene-4-sulphonic acid, ~: ~ z ;l-hydroxy-2-aminobenzene-5-sulphonic acid, , l-hydroxy-2-aminobenzene-4,6-disulphonic acid, hyd:roxy-2~-amino-4-acetylaminobenzene-6-sulphonic acid, I-hydroxy-2-amino-6-acetylaminobenzene-4-sulphonic acid, l-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid, , ~ ~
l-hydroxy-2-amino-4-methylsulphonyl-benzene, l-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulphonic acid.
' ~ ~ .
` 1 ~0 14 1 ~
- Coupling components of the formula (3) 3-methyl-5-pyrazolone, 5-pyrazolone-3-carboxylic acid, l-phenyl-3-sulphomethyl-5-pyrazolone, 1-(4'-sulphophenyl)-3-methyl-5-pyraæolone, 1-(4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 1-(3'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(3'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 1-(2',5'-disulphophenyl)-3-methyl-5-pyrazolone, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2'-chloro-4'-sulphophenyl)-3-me~hyl-5-pyrazolone, 1-(2'-chloro-5'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2'-sulpho-4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2'-methyl-4'-sulphophenyl)-3-methyl-5-pyrazolone, . 1-(2'-methyl-4'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 1-(6'-chloro-2'-methyl-4'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, 1-(4',8'-disulphonaphthyl[2'])-S-pyrazolone-3-carboxylic acid, 1-(5',7'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, 1-(5',7'-disulphonaphthyl~2'])-5-pyrazolone-3-carboxylic acid, 1-(4',6',8'-trisulphonaphthyl-[2'~)-3-methyl-5-pyrazolone, 1-(4',6',8'-trisulphonaphthyl-[2'])-5-pyrazolone-3-carboxylic acid, 1-(6l-amino-4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, .. ~ ..... .. . . . . , .. ... ~ ., . , .. , . .. ... . . .. . ... . .. _ . .g, . ..
-, :.
4 1 2 1-(3'- or 4l-aminophenyl)-3-methyl-5-pyrazolone, 1-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid, 1-(4'-amino-2'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(4'-amino-2'-sulphophenyl)-5-pyrazolone-3-carboxylic acid, 2~4,6-Trifluoro-1,3L~triazine (cyanuric fluoride~ of the formula (4~
Aminobenzenes of the formula (5) l-amino-2-methylbenzene, l-amino-2-ethylbenzene, l-amino-2-propylbenzene, l-amino-2-methoxybenzene, l-amino-2-ethoxybenzene, l-amino-2-carboxybenzene, l-amino-2-chlorobenzene, l-amino-2-bromobenzene, l-amino-2-fluorobenzene, l-amino-2,4-dimethylbenzene, l-amino-2,5-dimethylbenzene.
The diazotisation of the amino compounds of the formula (2) is usually effected by treatment with nitrous acid in an aqueous mineral acid solution at low temperature, and the coupling with the coupling components of the formula (3) is carried out at weakly acid or neutral to weakly alkaline pH values.
.. , . .. .. . . . . . . . .. . . ~ . .. .. .... . . .
~ 2 The condensation reactions of the 2,4,6-trifluoro-1,3,5-tria-zine with the amino compounds of the formula (2), the coupling components of the formula (3) and the aminobenzenes of the formula (5) are carried out preferably in aqueous solution or suspension, at low temperature and at weakly acid or neut-ral to weakly alkaline pH values. Advantageously, the hydrogen fluoride set free during the condensation is neutralised con-tinuously by the addition of aqueous alkali hydroxides, carbonates or bicarbonates.
If the benzene or naphthalene residue A contains a complex-forming group in the ortho-position ~o the azo group, for example a hydroxyl or carboxyl group, it is also possible to manufacture metal complexes of the fibre-reactive azo dyes of the formula (1) by treating azo compounds obtained by the above described process with metal donors, before or after the con-densation with fluorine-s-triazine. The copper complexes are of particular interest. They are obtained by treating corres-ponding azo compounds, wherein A is a benzene or naphthalene ra-dic~l which contains a complex-forming group in the ortho-position to the azo group, with copper donors before or, if desired, also after the acylation with the fluorine-1,3,5-triazine.
A suitable method of coppering is not only that described above in which an o,o'-dihydroxyazo compound is used as starting material for the complexing, but also oxidative copper-.. , . . ., . . . .... ., . ,. .. . . , ., . .... .... . ~ , . ... . . ... .. . w 14~l;2 ing, in which the hydroxyl group necessary for the complexing is not introduced into the naphthalene nucleus until during the coppering reaction by simultaneous treatment with an oxi-dant. Instead of a l-hydroxy-2-amino-naphthalene-4,8-disul-phonic acid, the corresponding 2-amino-naphthalene-4,8-disul-phonic acid is used for example in this case as diazo com-ponent.
However, to obtain the copper-complexes of the compounds of the formula (1) it is also possible to use diazo components which contain an alkoxy group instead of a hydroxyl group in the l-position of a naphthalene nucleus, in. particular the methoxy group, which is converted into the hydroxyl group under suitable reaction conditions during the coppering reaction by splitting off the alkyl radical.
As copper donors it is possbile to use for example salts which contain copper as cation, for example copper sulphate and copper acetate. In many cases it is advantageous to use complex copper compounds, for example in the form of copper-am~ine complexes,such as copper tetramminesulphat~ from copper sulphate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain copper bound as a complex, for example complex copper compounds of the alkali salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids, such as of glycine, of lactic acid and, in particular, of tartaric acid, such as sodium copper tartrate. - 14 -... ..
The treatment with the copper donors can be carried out bymethods which are known per se, for example at room temperature, if easily metallisable starting compounds are used, or if simultaneously with the metallising it is necessary to effect dealkylation,by heating to temperatures between 50 and 120C
in an open vessel, for example with reflux cooling or optionally in a closed vessel under pressure, the pH conditions being provided by the nature of the chosen metallising procedure:
for example an acid coppering with coppe`r sulphate and an alkaline coppering with copper tetramminesulphate.If desired, solvents, for example alcohol, dimethyl formamide etc., can also be added during the metallising. In the oxidative coppering, an oxidant, in particular hydrogen peroxide, is added to the reaction mixture, and the reaction is in other respects carried out in the described manner.
The fibre-reactive azo dyes of the formula (l) are distinguished by a pronounced reactivity and a high degree of fixation. They are suitable for dyeing and printing a very wide variety ofma-terials, such as silk, leather, wool, polyamide and polyurethane fibres, and especially cellulosic materials of fibrous structure, such as linen, cellulose, regenerated cellulose, and in parti-cular cotton. They are suitable both for the exhaustion process and for dyeing by the pad-dyeing process, in which the goods are impregnated with aqueous and, if appropriate, also with salt-containing dye solutions, and the dyes are fixed after treatment with alkali or in the presence of alkali, optionally ... ..... . . ..
. . .
.
. . ~ ' ' .
110~12 with the application of heat.
They are also suitable for printing, in particular on cotton, and also for printing nitrogen-containing fibres, for example wool, silk or blends containing wool.
It is advisable to rinse the dyeings and prints thoroughly with cold and hot water, if appropriate with the addition of an agent which acts as a dispersant and promotes the diffusion of non-fixed dye.
In the following Examples, the parts and percentages are by weight.
... .... , ., . ,, , . .. . . . .,,, , . .. , ., . . ~ .
141~
E x a m p 1 e 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0 to 5C in the course of 30 minutes to an aqueous solution containing 65 parts of the trisodium salt of 1-(2'-naphthyl)-3-methyl~4-(5"-aminophenylazo)-pyrazolone-(5)-2",4',8'-tri-sulphonic acid. When the addition is complete, the free amino group of the starting product is no longer detectable. During the entire duration of the dropwise addtition the pH of the solution is kept between 6.5 and 7.5 by the simultaneous addition of 2N sodium hydroxide solution. Then 11 parts of 2-aminotoluene are added, the temperature is slowly raised to 20C and the pH value is kept continously at 7 during the condensation. The dye of the formula ¢! ~ o~ c_~S0~ 3 ~ . CH3 S03 is salted out of the resultant clear solution by sprinkling in potassium chloride, isolated by filtration, dried and ground, giving a yellow dye powder which dyes wool in fast yellow shades.
Further useful dyes with similar colouristic properties are obtained by repeating the procedure of this Example using the aminopyrazolone dyes of column I of Table 1 and carrying out the second condensation with the amines listed in column II.
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Aminobenzenes of the formula (5) l-amino-2-methylbenzene, l-amino-2-ethylbenzene, l-amino-2-propylbenzene, l-amino-2-methoxybenzene, l-amino-2-ethoxybenzene, l-amino-2-carboxybenzene, l-amino-2-chlorobenzene, l-amino-2-bromobenzene, l-amino-2-fluorobenzene, l-amino-2,4-dimethylbenzene, l-amino-2,5-dimethylbenzene.
The diazotisation of the amino compounds of the formula (2) is usually effected by treatment with nitrous acid in an aqueous mineral acid solution at low temperature, and the coupling with the coupling components of the formula (3) is carried out at weakly acid or neutral to weakly alkaline pH values.
.. , . .. .. . . . . . . . .. . . ~ . .. .. .... . . .
~ 2 The condensation reactions of the 2,4,6-trifluoro-1,3,5-tria-zine with the amino compounds of the formula (2), the coupling components of the formula (3) and the aminobenzenes of the formula (5) are carried out preferably in aqueous solution or suspension, at low temperature and at weakly acid or neut-ral to weakly alkaline pH values. Advantageously, the hydrogen fluoride set free during the condensation is neutralised con-tinuously by the addition of aqueous alkali hydroxides, carbonates or bicarbonates.
If the benzene or naphthalene residue A contains a complex-forming group in the ortho-position ~o the azo group, for example a hydroxyl or carboxyl group, it is also possible to manufacture metal complexes of the fibre-reactive azo dyes of the formula (1) by treating azo compounds obtained by the above described process with metal donors, before or after the con-densation with fluorine-s-triazine. The copper complexes are of particular interest. They are obtained by treating corres-ponding azo compounds, wherein A is a benzene or naphthalene ra-dic~l which contains a complex-forming group in the ortho-position to the azo group, with copper donors before or, if desired, also after the acylation with the fluorine-1,3,5-triazine.
A suitable method of coppering is not only that described above in which an o,o'-dihydroxyazo compound is used as starting material for the complexing, but also oxidative copper-.. , . . ., . . . .... ., . ,. .. . . , ., . .... .... . ~ , . ... . . ... .. . w 14~l;2 ing, in which the hydroxyl group necessary for the complexing is not introduced into the naphthalene nucleus until during the coppering reaction by simultaneous treatment with an oxi-dant. Instead of a l-hydroxy-2-amino-naphthalene-4,8-disul-phonic acid, the corresponding 2-amino-naphthalene-4,8-disul-phonic acid is used for example in this case as diazo com-ponent.
However, to obtain the copper-complexes of the compounds of the formula (1) it is also possible to use diazo components which contain an alkoxy group instead of a hydroxyl group in the l-position of a naphthalene nucleus, in. particular the methoxy group, which is converted into the hydroxyl group under suitable reaction conditions during the coppering reaction by splitting off the alkyl radical.
As copper donors it is possbile to use for example salts which contain copper as cation, for example copper sulphate and copper acetate. In many cases it is advantageous to use complex copper compounds, for example in the form of copper-am~ine complexes,such as copper tetramminesulphat~ from copper sulphate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain copper bound as a complex, for example complex copper compounds of the alkali salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids, such as of glycine, of lactic acid and, in particular, of tartaric acid, such as sodium copper tartrate. - 14 -... ..
The treatment with the copper donors can be carried out bymethods which are known per se, for example at room temperature, if easily metallisable starting compounds are used, or if simultaneously with the metallising it is necessary to effect dealkylation,by heating to temperatures between 50 and 120C
in an open vessel, for example with reflux cooling or optionally in a closed vessel under pressure, the pH conditions being provided by the nature of the chosen metallising procedure:
for example an acid coppering with coppe`r sulphate and an alkaline coppering with copper tetramminesulphate.If desired, solvents, for example alcohol, dimethyl formamide etc., can also be added during the metallising. In the oxidative coppering, an oxidant, in particular hydrogen peroxide, is added to the reaction mixture, and the reaction is in other respects carried out in the described manner.
The fibre-reactive azo dyes of the formula (l) are distinguished by a pronounced reactivity and a high degree of fixation. They are suitable for dyeing and printing a very wide variety ofma-terials, such as silk, leather, wool, polyamide and polyurethane fibres, and especially cellulosic materials of fibrous structure, such as linen, cellulose, regenerated cellulose, and in parti-cular cotton. They are suitable both for the exhaustion process and for dyeing by the pad-dyeing process, in which the goods are impregnated with aqueous and, if appropriate, also with salt-containing dye solutions, and the dyes are fixed after treatment with alkali or in the presence of alkali, optionally ... ..... . . ..
. . .
.
. . ~ ' ' .
110~12 with the application of heat.
They are also suitable for printing, in particular on cotton, and also for printing nitrogen-containing fibres, for example wool, silk or blends containing wool.
It is advisable to rinse the dyeings and prints thoroughly with cold and hot water, if appropriate with the addition of an agent which acts as a dispersant and promotes the diffusion of non-fixed dye.
In the following Examples, the parts and percentages are by weight.
... .... , ., . ,, , . .. . . . .,,, , . .. , ., . . ~ .
141~
E x a m p 1 e 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0 to 5C in the course of 30 minutes to an aqueous solution containing 65 parts of the trisodium salt of 1-(2'-naphthyl)-3-methyl~4-(5"-aminophenylazo)-pyrazolone-(5)-2",4',8'-tri-sulphonic acid. When the addition is complete, the free amino group of the starting product is no longer detectable. During the entire duration of the dropwise addtition the pH of the solution is kept between 6.5 and 7.5 by the simultaneous addition of 2N sodium hydroxide solution. Then 11 parts of 2-aminotoluene are added, the temperature is slowly raised to 20C and the pH value is kept continously at 7 during the condensation. The dye of the formula ¢! ~ o~ c_~S0~ 3 ~ . CH3 S03 is salted out of the resultant clear solution by sprinkling in potassium chloride, isolated by filtration, dried and ground, giving a yellow dye powder which dyes wool in fast yellow shades.
Further useful dyes with similar colouristic properties are obtained by repeating the procedure of this Example using the aminopyrazolone dyes of column I of Table 1 and carrying out the second condensation with the amines listed in column II.
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E x a m p 1 e 2 66 parts of the intermediate of the formula H03S 0 - Cu -0 C ~ I ~ N-N ~ ~ 03H
C~l3 NH
obtained by coupling l-hydroxy-2-amino-4-acetylaminobenzene-6-sulphonic acid to 1-(4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, subsequently saponifying the acetylamino group and complexing with a copper donor, are dissolved at 0C and pH
7 in 700 parts of water. This pH value is maintained by further addition of sodium hydroxide solution following the dropwise addition of 14 parts of 2,4,6-trifluoro-1,3,5-triazine. When the condensation is complete (detectable by the absence of free amino groups), 13,3 parts of 1-amino-2-chlorobenzene are added.
The temperature is raised to 35C and the pH is kept at 8.5 with further sodium hydroxide solution. The dye is precipitated with sodium chloride, collected by suction filtration, dried and ground. It dyes cotton in very fast reddish brown shades.
Further brown dyes with similar properties are obtained by con-densing the copper complex dyes of column I of Table 2 with equivalent parts of 2,4,6-trifluoro-1,3,5-triazine and then with the amines listed in column II in accordance with the parti-culars of this Example.
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O O ~ ~ I X r~: Q X rl ~ ~
S~ ~ ~ OCL O O Irl a) c~ ~4 a~ '~:1 'Ql aJ ~ ~, ~J
~J ~ ~ t ~ ~ ~ I I ~ I
~ ~ O~ O ,~ ~ o., ~ ~ o. - U~ o.~ _ I
q~ ~) N u~ N V ~ ~
c~ ~ ~,1 I ~ I ,~ O I ~ O ^ ~ O ^ I ~1 ~:: ~1 - h - $~1 - ~ V - I V - ~ V - ~ ~1 a~ ~1 CL ~ ~~ P~
_~ td ::~ `~ - X
t~ ~ O I II I I I ~ I O ~ `J O
E~ ~o U~
P~
. ~ ~ ~1 p~ ~~ V ~ V
~ I ~ V~r~
o V O V O V O
O td ~ C
N I Q~ I Cl. I Q~
td ~ ~1~ ~ ~) ,_ I
P~ O U~ O ~ O U~
Q ~ I ~ ~ I ~ ~ I
O ~
I ~ 1 ~; O
CL, I N O I N O I N O
. ~ P~
U ~ X ~ ~ X
O, o ~9 0 ,9 U~ O ,9 U~
h I `-- h I `-- h I --' O ~ O ~ 0 ~0 0 N
~_1 I E3 t I E3 ~1 ~ t~
~___ . _ .
.
C~l ~ ~ U~
I U . O ~
e c e ~ ~ 3 ~
~ ~ o a ; ~ ~ 2 e ~ O
~O ~ . ~
H L e ~ Ç~
O ~
~ @.~ x~
o~ ~
__ .~ . r~
-11~141~:
E x a m p 1 e 3 26.8 parts of 1,4-diaminobenzene-2,5-disulphonic acid are dis-solved in 300 parts of water at pH 7 and 0C. With efficient stirring, 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise while simultaneously keeping the pH between 6.5 and 7 by the addition of 2N sodium hydroxide solution and the temperature at 0C by the addition of ice. When 1 equivalent of sodium hydro~ide solution has been consumed, 12.1 parts of l-amino-2-ethylbenzene are tipped in. The temperature is raised to 40C and the pH is kept at 8 with a further equivalent of sodium hydroxide solution. When the condensation is complete, the batch is cooled to 0 to 5C, acidified wi~h 30 parts of concentrated hydrochloric acid,and diazotisation is effected by the dropwise addition of an aqueous solution of 7 parts of sodium nitrite. This suspension of the diazo compound is added to a neutral solution of 29 parts of 1-(2'-chloro-5'-sulpho-phenyl)-3-methyl-5-pyrazolone to which 30 parts of sodium carbonate have been added. When the coupling is complete, the pH is adjusted to 7 and the dye of the formula ¢ ~ ~ IN ~ N=N _ ~ H-C C-NH ~
3 ~C CH2CH3 . . . . . . .
.
, '. - ' :. " ~ .
1~;14~2 is precipitated by addition of a 1:1 mixture of potassium and sodium chloride, collected by suction filtration, dried and ground, giving a yellow dye powder which dyes cotton in fast reddish yellow shades.
Dyes with similar properties are obtained by condensing 2,4,6-trifluoro-1,3,5-triazine with the diaminobenzenesulphonic acids of column I of Table 3 and subsequently with the amines listed in column II, diazotising the secondary condensation products and coupling the resultant diazonium compounds in accordance with the particulars of this Example with the coupling com-ponents listed in column III.
- - - .....
.
. `
.
.
: ` , .
_ _ , ~
.~ ,_ I ~d I I I I I ~ ~1 o ~ ~ ~ o ~ o P~ :~
1 ~ ~ P~
o o ~, U ~ ,1 C ,~
~ ~ o ~ u~
o ~ o o ~ , ~ ,, , o , ~ ~J ~
O -- -- ~ - N ~ -- ~ O
O I ~ I ,~
~1 O (11 0 ~1 ~1 ~ 1 0 au bO S~
~ o I o ~ I a) o ~
I ~,c o a~ I o o - u~
C).. tJ ~ ~ 3 ~ ~ 01 ~1 N Ll'~ 1 :~I .--1 a) I o o I ~ x ~ ~1 0 t~
-- ~ -- ,~ N - :~ O -- P . N S~
C.) ~ O ~ ~ tl~
'~1 h I .~ o I
Q. N ~ u~
a~ ~
a) N ~) ~U N
N ~: N N ~:
a) rQ a) a) .o 0 ~C
P~ O' ~ ~ O
. ~ O ~
E~ U t~
I I
rl C~l ~ C~l a~ ~ o o o o o .
E~
l l l l l . ~ 1 .,~ ~ I
U~
C`l `J C~
~rl N N N
1~ E~i S~
~rl ~
~ O _ O C~
.~
. ~ ~-~1 I I Q ~ ~
_ .. ___ Z
_ _ ~ U~
H O ~ O
rl I~
~ I O^ I rl C~ ~ ~X
I ~ I ~ O
~1 ~ ~,1:) . .
~J N ~
~ O
~ U ~ ~ ~
O O O
t~
E~ ~ ~
C UU
.,1 0~ 0 ~ .~
.~ U ~ ~
g --lZ
E x a m p 1 e 4 26.B parts of 1,3-diaminobenzene-4,6-disulphonic acid are added to 400 parts of water at pH 7 and, after cooling to 0C, 14 parts of 2,4,6-trifluoro-1,3,4-triazine are added dropwise, while keeping the pH at 7 by adding sodium hydroxide solution. When the condensation is complete, the condensation mixture is acidified with 30 parts of concentrated hydro-chloric acid and diazotisation is effected by adding 7 parts of sodium nitrite. Simultaneously, 32 parts of 1-(2',5'-di-chloro-4'-sulphophenyl)-3-methyl-5-pyrazolone are dissolved in 300 parts of water at pH 8. The diazo suspension is intro-duced into this solution and the pH is kept between 8 and 9 by the addition of sodium hydroxide solution. When the reac-tion components can no longer be detected, 12.3 parts of 1-amino-2-m~thoxybenzene are added dropwise and the temperature is simultaneously raised to 20 to 30C. Meantime, the pH is kept at 8 by the further addition of sodium hydroxide solution.
When the condensation is complete, the dye is salted out and collected by suction filtration. The residue is dried and ground, giving a yellow dyestuff powder. The dye has the formula pl OH
~H-C~ ~c-NH
H03S I ~ N N
Cl CH3 H03S S03H ~?C/ OCH3 F
' : ' ' : :
and it dyes cellulose in very fast greenish yellow shades.
Further dyes are obtained by condensing 2,4,6-trifluoro-1,3,5-triazine with a diaminobenzenesulphonic acid of column ~
of Table 4 in accordance with the above procedure, diazotising the resultant condensation product and coupling it with a coupling component of column II, and finally condensing the azo compound thereby obtained with the amine of column III.
. . . ~
a~
N a~ N ~ N al N
~:: N ~ N N tL) ,C: N ~::
0 1~ N Q~
ra a ~ ~ X ~
O S~O P~ :~ ~ O ~ O
~ oQ ~ .~
C~
U c~v P~
C~l C~3 ~ ~ ~ ~ C~l ~ C~l O O O O O O O O O
a a ~ a a a ~ ~ a e .
~,~ ~ ~, .
o ~ o ~
N P~ ( CJ
I ~d ~ O C~
I O ~ ~) N O~1 a) O ~ ~C
. ~ O
~ ~ O ~ ~ o~,n I
o ~ a) ~ I ~ ~ ~ o ~ ~ ~ o O P~ O U~ I O I u~ O O N u~ 30 t~ p~
N ~ ~1 1 ~1.1:~ U~I N ,~:: td I N
~d ~ O - P P~
S~ N `J ~: ~1 ~1 `;t ~ ~ ~ Lr') P, a~
o ~ ~o o~ ~o I o Q~ o I ~ ~ ~ ~ I rl O ~ ~
~ ~ ~ C~ .C I~ ~O U~ ~ I O U~ ~ ~ ~ o E-l I ~ I JJ ~ I E~ r/ I I r-l ~1 1 1 0 rl r-l --13 U~ U I ~l ~ N 3 0 ~, 0 1 ~ ~ CO ~ C) ~ 1~ ,~: C~ p~ 00 CiJ 0 N
I ~ I ~1 ^ ~ I ~ ~` ~ I ~ ^ ~ I td S c~
I I a~ I ~ I ~ ; I I t~ I I I Ll'~ v I I
U3 ~
N ~ ~D -I I I t N rl N rl N rl N
~ U
a . ' .~ ~ ~I ~0 U ~ V ~0 H ~3 t~
~ ~ O ~ O ~ O ~-rl ~ ~ rl O
I ~ I ~ 1 3 I tl~
~.,1 ^.,~ ^-rl ^ 3 r~l '~:) ~1 ~ ~1 ~1 ~1 U~
.. I
` 1 lQ ~
E x a m p 1 e 5 249.2 parts of 1-(4'-amino-2'-sulphophenyl)-4-(5"-amino-2"-sulphophenylazo)-5-pyrazolone-3-carboxylic acid (prepared by diazotisation of l-amino-3-acetylaminobenzene-6-sulphonic acid, coupling to l-(4'-amino-2'-sulphophenyl)-5-pyrazolone-3-car-boxylic acid and subsequent saponification of the acetylamino group) are dissolved in 1000 parts of water at pH 7 by adding sodium hydroxide solution. After cooling to 0C, 135 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise, while keeping the pH constant by further addition of sodium hydroxide.
When no more free amino groups can be detected, 107.2 parts of l-amino-2-methylbenzene are added dropwise. The temperature is rapidly raised to 40C and the pH is kept at 8 by the further addition of sodium hydroxide solution. The dye of the fonnula ,N ~ N ~ NH C~N\c NH
¢ ~ ~ NH-C C-NH ~ ~ N=N ~ ~ N N
CH N N ~S03H IOOH S03H F CH3 is salted out, filtered off, dried and ground. It is a dry powder which dyes cotton in fast yellow shades.
Further bireactive dyes with similar properties are obtained by condensing the diaminoazo dyes of column I of Table 5 with 2,4,6-trifluoro-1,3,5-triazine and subsequently with the amines listed in column II in accordance with the particulars of this ExampleO
. .
H. O a) O O
¢ I S I
~1.~ ~,Q
I I I
.~ S I
~ ~ ~( N
_ I I
~ ~ rl u~ Cd a~ ~
E~
~
O O O
X
O ~ ,~
,~ N
~ ~ U~
H I I I I al O ~, ~ u~ ~) ,C~ Cd N ~ 0~ 1:
. ~ N ~) N N
. . ~
~1 a~ ~1 U~ ~ ^-rl ~ ~ ~ I O `J ~
r~ O rl ~ ~ I ~
rl O O
I ~ I 1:~ E3 C
E ~
_ _ ~ .
__ ~
1~141Z
E x a m p 1 e 6 26.8 parts of 1,4-diaminobenzene-2,5~disulphonic acid are diazotised and coupled to 26.9 parts of 1-(4'-amino-2'-sul-phophenyl~-3-methyl-5-pyrazolone A suspension of 47.2 parts of the condensation product of 1 equivalent of 2,4,6-trifluoro-1,3,5-triazine and 1 equivalent of 1-amino-2,5-dimethylbenz-ene in 250 parts of water is tipped into a neutral solution of the above intermediate in 500 parts of water. The pH is kept between 7.5 and 8 by the addition of sodium hydroxide solution. The batch is then stirred at room temperature until free amino groups can no longer be detected. The solution is then concentrated and the residue ground, giving a dye of the formula CH so3~ OH ICH3 ~ "N~ ~ N ~ -N~l-C C-NH - ~ ~
~NH-C C-NH~N=N~ J N N ~IJ
CH3 ~C ~ S03H CH3 ' 3 which dyes cotton in reddish yellow shades of excellent fast-ness. Bireactive dyes with similar properties are obtained by condensing the diaminoazo dyes listed in column I of Table 6 in accordance with the particulars of this Example with the primary condensation product of 2,4,6-trifluoro-1,3,5-triazine and the amines of column II.
4~2 __ _ . _ _ ~ a) a) ~ O ~ O
k ~
CN ~`1 ~ C~l l l l l ~0 0~
~ 1 rl a) E
I I a~
, O O O ~
~ 1 rl I rl _ - - ~::
`J ~ O .
I V I I O ~ :~
1` 1` P` ~, e .
'Cl ~ ~ ~ I ~
r~ Xrl .
o O c) t~
O
~d O C~ O O E I
E-~ ,c~ N N
0~ d C~ ~1 O:~ O
~:5 U~
rl Orl Or-l ~ N I
O `l:) N ~ N ~ CN
N I 1~) I t~) I ~ O
t~ Ln ~1 ~ 11 ~ ~1 ,C~
O ^ P~ 0 .-1 ~ ~ C~
Ei o u~ ~ E
~ ~ t .~ 0 N ~--I N :~ N ~ ~ O
~ O J
Q~
0~ 0 ~ O~
~1 0 ~
~ 0-~
~1 ~rl ~rl I ~ I ~
O O
I u~
I c~
c~
_ _ ~
, ,2 Dyeing Procedure I
2 Parts of the dye obtained according to Example 1 are dis-solved in 100 parts of water while adding 0.5 part of sodium m-nitrobenzenesulphonate. A cotton fabric is impregnated with the resultant solution to a liquor pick-up of 75% and then - dried.
The fabric is then impregnated with a warm solution of 20C
which contains, per litre, S g of sodium hydroxide and 300 g of sodium chloride, and squeezed out to a pick-up of 75%. The dyeing is steamed for 30 seconds at 100 to 101C, rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rlnsed and dried.
, Dyeing Proced~re II
2 Parts of the dye obtained according to Example 1 are dis-801ved in 100 parts o~ water. The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added ~nd 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 40QC and 40 parts of calcined~
sodium carbonate and another 60 parts of sodium chloride are ~dded after 30 minutes. The tempera~ure is kept for 30 minutes ~t 40C. The dyeing is rinsed and then soaped for 15 minutes in a 0,3% boiling solution of a non-ionic detergent, rinsed and dried.
~d ~rl ~d~rl~rl ~rl ~d I I I
H ~ ~ E3 1~ .~ ~ .-1 ~ .~ ~:) ~`I ~1 a O
~ ~ ~ ~ 0 ~ ~ _ rl ~ ~ a~ a Ei ~: ~ v ~ ~ V
~; o td ~ v N ~ N ~
E ~ ~: ~ v ~ ~ Q) u ~ u ~ v O I I ~ I ~ ~ ,0 td C~rl t~ o .~ o o ~ o O O C
~ U ~ O
o E~ :: q ~ ~ ~ 6 o E3 t: 6 P.
~D ~ o, ~ ~ ~ ~ ~ t:L ~ ~O
. .. _ . .. . .. . .. _ . . .
o~ O_I C~ ~ ~ U~
~ ~ ~ ~ ,~
l , . _ _. .... ~ ~
11~31~12 ~ . , . .
o ~
o ~ o o o ~ rQ ~
~ c~ ~d ~ td E
., o C~
...
o a~ o Q)O ~ O ~ O a ~ o ~
'l 1' E N E N E N E N E N
C ~d td ~q a)I Q~ I C~ I a~ I c ~ ,n ~ rQ~ ~ ~ .
.~A _ _ I
S
~U~
I ~ S S
~( ~C~ P-~ I O ~ O C~
".~ S 1~ ~ ~
I t~I ~ ~0 ~0 I ~
,' - E ~ ~ ~ o ~ o ~ o p, ~p~ N u~ N
_ ^~ ~ O I ~ I td - I a~ o<1~ N -`J ^ S .D .
8 oc - ~ ~ ~ ~ ~
U
.,,~ ~ .,..... .... .
S
_I - 4 N- t:: - ~ -- V -~D S tl~ ~ O ~ S ~ O `;t O
t~ ~ ~ '' E `--C
~1 0 ~ I O
O ~ I N ~I E
a~
P. o a) -1 c,. ~1 g o U~
N _I ~ ~ ~ H
H p~ ~ ..
C~, . O J ~ I
, ,, O .~ td NN ~ N ~ rC t~
. ~ ~d U ~
O ~ p~rl U O ~ O~rl O O O
~ O ~C.J p U ~ O
o N E ~ ~E ~; E C E~ Q~
~d ~ ~ ~ U~ Otd O ~d ,1 I ~ l ~,1 1 ~ I .~ I
~ ~ ~ ~C ~ Q. ~ ~ ~ u~
.
r~ o~ ~ O ,~
~1 ~ ~ C~
.
E x a m p 1 e 2 66 parts of the intermediate of the formula H03S 0 - Cu -0 C ~ I ~ N-N ~ ~ 03H
C~l3 NH
obtained by coupling l-hydroxy-2-amino-4-acetylaminobenzene-6-sulphonic acid to 1-(4',8'-disulphonaphthyl[2'])-3-methyl-5-pyrazolone, subsequently saponifying the acetylamino group and complexing with a copper donor, are dissolved at 0C and pH
7 in 700 parts of water. This pH value is maintained by further addition of sodium hydroxide solution following the dropwise addition of 14 parts of 2,4,6-trifluoro-1,3,5-triazine. When the condensation is complete (detectable by the absence of free amino groups), 13,3 parts of 1-amino-2-chlorobenzene are added.
The temperature is raised to 35C and the pH is kept at 8.5 with further sodium hydroxide solution. The dye is precipitated with sodium chloride, collected by suction filtration, dried and ground. It dyes cotton in very fast reddish brown shades.
Further brown dyes with similar properties are obtained by con-densing the copper complex dyes of column I of Table 2 with equivalent parts of 2,4,6-trifluoro-1,3,5-triazine and then with the amines listed in column II in accordance with the parti-culars of this Example.
41~
_ ~ ~ , , ,Q
o o ~ o h O P~ .--1 0 C ~ ~ U
~ l l l l l l _~ h O ~
~1 ~1 O O ~ O Q) O ~J O al o ~
~ ~D E3 a) E3 N E N Ei N ~ N ~3 N
~1 Ia~I~ Ia~Ia) Ia) Ia N~--I ,CI-1 ,~~1 ~ ~1 ~ r-l . ' __ _ I I
~J ~ O
P~ N I
C ~tll tY) .LI ~ ~ _~ aJ h O X~\ X ~ ~ ~_ :~ h X
I r~ 1 0 1 ~ p~, J t~ ~1 C~
I E~ I u o ~ E~
O~_ O ~1 O~ I O
~- ~I v , ~
~ ~ I~ I tO O~ V O O O ~ I
a) ~ I N ~ C O
1:~ ~ o c,.~/ ~
O rC `' ~--'~ h ~ 1 N --1 0 ~' R~ C4 Q~ X ~ N
Ei ~3 O a) o Q) O C~ O O ~ C~
O O ~ ~ I X r~: Q X rl ~ ~
S~ ~ ~ OCL O O Irl a) c~ ~4 a~ '~:1 'Ql aJ ~ ~, ~J
~J ~ ~ t ~ ~ ~ I I ~ I
~ ~ O~ O ,~ ~ o., ~ ~ o. - U~ o.~ _ I
q~ ~) N u~ N V ~ ~
c~ ~ ~,1 I ~ I ,~ O I ~ O ^ ~ O ^ I ~1 ~:: ~1 - h - $~1 - ~ V - I V - ~ V - ~ ~1 a~ ~1 CL ~ ~~ P~
_~ td ::~ `~ - X
t~ ~ O I II I I I ~ I O ~ `J O
E~ ~o U~
P~
. ~ ~ ~1 p~ ~~ V ~ V
~ I ~ V~r~
o V O V O V O
O td ~ C
N I Q~ I Cl. I Q~
td ~ ~1~ ~ ~) ,_ I
P~ O U~ O ~ O U~
Q ~ I ~ ~ I ~ ~ I
O ~
I ~ 1 ~; O
CL, I N O I N O I N O
. ~ P~
U ~ X ~ ~ X
O, o ~9 0 ,9 U~ O ,9 U~
h I `-- h I `-- h I --' O ~ O ~ 0 ~0 0 N
~_1 I E3 t I E3 ~1 ~ t~
~___ . _ .
.
C~l ~ ~ U~
I U . O ~
e c e ~ ~ 3 ~
~ ~ o a ; ~ ~ 2 e ~ O
~O ~ . ~
H L e ~ Ç~
O ~
~ @.~ x~
o~ ~
__ .~ . r~
-11~141~:
E x a m p 1 e 3 26.8 parts of 1,4-diaminobenzene-2,5-disulphonic acid are dis-solved in 300 parts of water at pH 7 and 0C. With efficient stirring, 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise while simultaneously keeping the pH between 6.5 and 7 by the addition of 2N sodium hydroxide solution and the temperature at 0C by the addition of ice. When 1 equivalent of sodium hydro~ide solution has been consumed, 12.1 parts of l-amino-2-ethylbenzene are tipped in. The temperature is raised to 40C and the pH is kept at 8 with a further equivalent of sodium hydroxide solution. When the condensation is complete, the batch is cooled to 0 to 5C, acidified wi~h 30 parts of concentrated hydrochloric acid,and diazotisation is effected by the dropwise addition of an aqueous solution of 7 parts of sodium nitrite. This suspension of the diazo compound is added to a neutral solution of 29 parts of 1-(2'-chloro-5'-sulpho-phenyl)-3-methyl-5-pyrazolone to which 30 parts of sodium carbonate have been added. When the coupling is complete, the pH is adjusted to 7 and the dye of the formula ¢ ~ ~ IN ~ N=N _ ~ H-C C-NH ~
3 ~C CH2CH3 . . . . . . .
.
, '. - ' :. " ~ .
1~;14~2 is precipitated by addition of a 1:1 mixture of potassium and sodium chloride, collected by suction filtration, dried and ground, giving a yellow dye powder which dyes cotton in fast reddish yellow shades.
Dyes with similar properties are obtained by condensing 2,4,6-trifluoro-1,3,5-triazine with the diaminobenzenesulphonic acids of column I of Table 3 and subsequently with the amines listed in column II, diazotising the secondary condensation products and coupling the resultant diazonium compounds in accordance with the particulars of this Example with the coupling com-ponents listed in column III.
- - - .....
.
. `
.
.
: ` , .
_ _ , ~
.~ ,_ I ~d I I I I I ~ ~1 o ~ ~ ~ o ~ o P~ :~
1 ~ ~ P~
o o ~, U ~ ,1 C ,~
~ ~ o ~ u~
o ~ o o ~ , ~ ,, , o , ~ ~J ~
O -- -- ~ - N ~ -- ~ O
O I ~ I ,~
~1 O (11 0 ~1 ~1 ~ 1 0 au bO S~
~ o I o ~ I a) o ~
I ~,c o a~ I o o - u~
C).. tJ ~ ~ 3 ~ ~ 01 ~1 N Ll'~ 1 :~I .--1 a) I o o I ~ x ~ ~1 0 t~
-- ~ -- ,~ N - :~ O -- P . N S~
C.) ~ O ~ ~ tl~
'~1 h I .~ o I
Q. N ~ u~
a~ ~
a) N ~) ~U N
N ~: N N ~:
a) rQ a) a) .o 0 ~C
P~ O' ~ ~ O
. ~ O ~
E~ U t~
I I
rl C~l ~ C~l a~ ~ o o o o o .
E~
l l l l l . ~ 1 .,~ ~ I
U~
C`l `J C~
~rl N N N
1~ E~i S~
~rl ~
~ O _ O C~
.~
. ~ ~-~1 I I Q ~ ~
_ .. ___ Z
_ _ ~ U~
H O ~ O
rl I~
~ I O^ I rl C~ ~ ~X
I ~ I ~ O
~1 ~ ~,1:) . .
~J N ~
~ O
~ U ~ ~ ~
O O O
t~
E~ ~ ~
C UU
.,1 0~ 0 ~ .~
.~ U ~ ~
g --lZ
E x a m p 1 e 4 26.B parts of 1,3-diaminobenzene-4,6-disulphonic acid are added to 400 parts of water at pH 7 and, after cooling to 0C, 14 parts of 2,4,6-trifluoro-1,3,4-triazine are added dropwise, while keeping the pH at 7 by adding sodium hydroxide solution. When the condensation is complete, the condensation mixture is acidified with 30 parts of concentrated hydro-chloric acid and diazotisation is effected by adding 7 parts of sodium nitrite. Simultaneously, 32 parts of 1-(2',5'-di-chloro-4'-sulphophenyl)-3-methyl-5-pyrazolone are dissolved in 300 parts of water at pH 8. The diazo suspension is intro-duced into this solution and the pH is kept between 8 and 9 by the addition of sodium hydroxide solution. When the reac-tion components can no longer be detected, 12.3 parts of 1-amino-2-m~thoxybenzene are added dropwise and the temperature is simultaneously raised to 20 to 30C. Meantime, the pH is kept at 8 by the further addition of sodium hydroxide solution.
When the condensation is complete, the dye is salted out and collected by suction filtration. The residue is dried and ground, giving a yellow dyestuff powder. The dye has the formula pl OH
~H-C~ ~c-NH
H03S I ~ N N
Cl CH3 H03S S03H ~?C/ OCH3 F
' : ' ' : :
and it dyes cellulose in very fast greenish yellow shades.
Further dyes are obtained by condensing 2,4,6-trifluoro-1,3,5-triazine with a diaminobenzenesulphonic acid of column ~
of Table 4 in accordance with the above procedure, diazotising the resultant condensation product and coupling it with a coupling component of column II, and finally condensing the azo compound thereby obtained with the amine of column III.
. . . ~
a~
N a~ N ~ N al N
~:: N ~ N N tL) ,C: N ~::
0 1~ N Q~
ra a ~ ~ X ~
O S~O P~ :~ ~ O ~ O
~ oQ ~ .~
C~
U c~v P~
C~l C~3 ~ ~ ~ ~ C~l ~ C~l O O O O O O O O O
a a ~ a a a ~ ~ a e .
~,~ ~ ~, .
o ~ o ~
N P~ ( CJ
I ~d ~ O C~
I O ~ ~) N O~1 a) O ~ ~C
. ~ O
~ ~ O ~ ~ o~,n I
o ~ a) ~ I ~ ~ ~ o ~ ~ ~ o O P~ O U~ I O I u~ O O N u~ 30 t~ p~
N ~ ~1 1 ~1.1:~ U~I N ,~:: td I N
~d ~ O - P P~
S~ N `J ~: ~1 ~1 `;t ~ ~ ~ Lr') P, a~
o ~ ~o o~ ~o I o Q~ o I ~ ~ ~ ~ I rl O ~ ~
~ ~ ~ C~ .C I~ ~O U~ ~ I O U~ ~ ~ ~ o E-l I ~ I JJ ~ I E~ r/ I I r-l ~1 1 1 0 rl r-l --13 U~ U I ~l ~ N 3 0 ~, 0 1 ~ ~ CO ~ C) ~ 1~ ,~: C~ p~ 00 CiJ 0 N
I ~ I ~1 ^ ~ I ~ ~` ~ I ~ ^ ~ I td S c~
I I a~ I ~ I ~ ; I I t~ I I I Ll'~ v I I
U3 ~
N ~ ~D -I I I t N rl N rl N rl N
~ U
a . ' .~ ~ ~I ~0 U ~ V ~0 H ~3 t~
~ ~ O ~ O ~ O ~-rl ~ ~ rl O
I ~ I ~ 1 3 I tl~
~.,1 ^.,~ ^-rl ^ 3 r~l '~:) ~1 ~ ~1 ~1 ~1 U~
.. I
` 1 lQ ~
E x a m p 1 e 5 249.2 parts of 1-(4'-amino-2'-sulphophenyl)-4-(5"-amino-2"-sulphophenylazo)-5-pyrazolone-3-carboxylic acid (prepared by diazotisation of l-amino-3-acetylaminobenzene-6-sulphonic acid, coupling to l-(4'-amino-2'-sulphophenyl)-5-pyrazolone-3-car-boxylic acid and subsequent saponification of the acetylamino group) are dissolved in 1000 parts of water at pH 7 by adding sodium hydroxide solution. After cooling to 0C, 135 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise, while keeping the pH constant by further addition of sodium hydroxide.
When no more free amino groups can be detected, 107.2 parts of l-amino-2-methylbenzene are added dropwise. The temperature is rapidly raised to 40C and the pH is kept at 8 by the further addition of sodium hydroxide solution. The dye of the fonnula ,N ~ N ~ NH C~N\c NH
¢ ~ ~ NH-C C-NH ~ ~ N=N ~ ~ N N
CH N N ~S03H IOOH S03H F CH3 is salted out, filtered off, dried and ground. It is a dry powder which dyes cotton in fast yellow shades.
Further bireactive dyes with similar properties are obtained by condensing the diaminoazo dyes of column I of Table 5 with 2,4,6-trifluoro-1,3,5-triazine and subsequently with the amines listed in column II in accordance with the particulars of this ExampleO
. .
H. O a) O O
¢ I S I
~1.~ ~,Q
I I I
.~ S I
~ ~ ~( N
_ I I
~ ~ rl u~ Cd a~ ~
E~
~
O O O
X
O ~ ,~
,~ N
~ ~ U~
H I I I I al O ~, ~ u~ ~) ,C~ Cd N ~ 0~ 1:
. ~ N ~) N N
. . ~
~1 a~ ~1 U~ ~ ^-rl ~ ~ ~ I O `J ~
r~ O rl ~ ~ I ~
rl O O
I ~ I 1:~ E3 C
E ~
_ _ ~ .
__ ~
1~141Z
E x a m p 1 e 6 26.8 parts of 1,4-diaminobenzene-2,5~disulphonic acid are diazotised and coupled to 26.9 parts of 1-(4'-amino-2'-sul-phophenyl~-3-methyl-5-pyrazolone A suspension of 47.2 parts of the condensation product of 1 equivalent of 2,4,6-trifluoro-1,3,5-triazine and 1 equivalent of 1-amino-2,5-dimethylbenz-ene in 250 parts of water is tipped into a neutral solution of the above intermediate in 500 parts of water. The pH is kept between 7.5 and 8 by the addition of sodium hydroxide solution. The batch is then stirred at room temperature until free amino groups can no longer be detected. The solution is then concentrated and the residue ground, giving a dye of the formula CH so3~ OH ICH3 ~ "N~ ~ N ~ -N~l-C C-NH - ~ ~
~NH-C C-NH~N=N~ J N N ~IJ
CH3 ~C ~ S03H CH3 ' 3 which dyes cotton in reddish yellow shades of excellent fast-ness. Bireactive dyes with similar properties are obtained by condensing the diaminoazo dyes listed in column I of Table 6 in accordance with the particulars of this Example with the primary condensation product of 2,4,6-trifluoro-1,3,5-triazine and the amines of column II.
4~2 __ _ . _ _ ~ a) a) ~ O ~ O
k ~
CN ~`1 ~ C~l l l l l ~0 0~
~ 1 rl a) E
I I a~
, O O O ~
~ 1 rl I rl _ - - ~::
`J ~ O .
I V I I O ~ :~
1` 1` P` ~, e .
'Cl ~ ~ ~ I ~
r~ Xrl .
o O c) t~
O
~d O C~ O O E I
E-~ ,c~ N N
0~ d C~ ~1 O:~ O
~:5 U~
rl Orl Or-l ~ N I
O `l:) N ~ N ~ CN
N I 1~) I t~) I ~ O
t~ Ln ~1 ~ 11 ~ ~1 ,C~
O ^ P~ 0 .-1 ~ ~ C~
Ei o u~ ~ E
~ ~ t .~ 0 N ~--I N :~ N ~ ~ O
~ O J
Q~
0~ 0 ~ O~
~1 0 ~
~ 0-~
~1 ~rl ~rl I ~ I ~
O O
I u~
I c~
c~
_ _ ~
, ,2 Dyeing Procedure I
2 Parts of the dye obtained according to Example 1 are dis-solved in 100 parts of water while adding 0.5 part of sodium m-nitrobenzenesulphonate. A cotton fabric is impregnated with the resultant solution to a liquor pick-up of 75% and then - dried.
The fabric is then impregnated with a warm solution of 20C
which contains, per litre, S g of sodium hydroxide and 300 g of sodium chloride, and squeezed out to a pick-up of 75%. The dyeing is steamed for 30 seconds at 100 to 101C, rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rlnsed and dried.
, Dyeing Proced~re II
2 Parts of the dye obtained according to Example 1 are dis-801ved in 100 parts o~ water. The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added ~nd 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 40QC and 40 parts of calcined~
sodium carbonate and another 60 parts of sodium chloride are ~dded after 30 minutes. The tempera~ure is kept for 30 minutes ~t 40C. The dyeing is rinsed and then soaped for 15 minutes in a 0,3% boiling solution of a non-ionic detergent, rinsed and dried.
Claims
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1 Fibre-reactive azo dyes of the formula (1), wherein A is a residue of benzene or naphthalene, Y is methyl, sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen, n is a positive integer from 1 to 6 and m is 1 or 2, and A and B can contain as further substi-tuents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and carboxyl group and halogen atoms, and the phenylamino radical bonded to the s-triazine ring can contain as further substituent at the phenyl nucleus, in addition to and independently of X, an alkyl radical of 1 to 4 carbon atoms, and, if m is 2, the substituents R and X of both 2-fluoro-4-(2'-X-phenyl amino)-s-triazin-6-yl-N(R) radicals can be different, and metal complexes of the fibre-reactive azo dyes of the formula (1).
2. Fibre-reactive azo dyes according to claim 1 wherein X is methyl, methoxy, carboxy or chlorine.
3. Fibre-reactive azo dyes according to claim 1 wherein m is 1 and the 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-N(R) radical is bonded to the residue A.
4. Fibre-reactive azo dyes according to claim 1 wherein A is a sulphophenyl radical, Y is methyl or carboxy, B is a phenyl or naphthyl radical which is unsubstituted or substituted by sulpho and chlorine, R is hydrogen and m is 1, and X and n are as defined in claim 1.
5. The fibre-reactive azo dye of the formula 6. The fibre-reactive azo dye of the formula 7. A process for the manufacture of fibre-reactive azo dyes of the formula (1), wherein A is a benzene or naphthalene residue, Y is methyl sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen, n is a positive integer from 1 to 6 and m is 1 or 2, and A and B can contain further as substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and carboxyl group and halogen atoms, and the phenylamino radical bonded to the s-triazine ring can contain as further substituent at the phenyl nucleus, in addition to and independently of X, an alkyl radical of 1 to 4 carbon atoms, and, if m is 2, the substituents R and X of both 2-fluoro-4-(2'-X-phenyl amino)-s-triazin-6-yl-N(R) radicals can be different, which process comprises reacting a diazotised amino compound of the formula A - NH2 (2), a coupling component of the formula (3), wherein A and B together contain 1 to 6 sulpho groups, and A and/or B contain a -N(R)H group, one or two equivalents of 2,4,6-trifluoro-1,3,5-triazine of the formula (4), and one or two equivalents of identical or different amino-benzenes of the formula (5), by coupling and condensation, in optional sequence, to give a fibre-reactive azo dye of the formula (1), and optionally treating the azo compounds so obtained with metal donors before or after the condensation with fluoro-s-triazine.
8. A process according to claim 7 wherein the starting materials are aminobenzenes of the formula (5), in which X is methyl, methoxy, carboxyl or chlorine.
9. A process according to claim 7 wherein the starting materials are compounds of the formula (2) and (3), in which only A, but not B, contains a -N(R)H group.
10. A process according to claim 7 wherein the starting materials are compounds of the formula (2), in which A is a sulphophenyl radical, compounds of the formula (3), in which Y is methyl or carboxy and B is a phenyl or naphthyl radical which is unsubstituted or substituted by sulpho and chlorine, and A and B together contain 1 to 6 sulpho groups and A or B
contains a -NH2 group, one equivalent of 2,4,6-trifluoro-s-triazine of the formula (4) and one equivalent of an aminobenzene of the formula (5), wherein X is as defined in claim 7.
11. A process according to claim 7, 8 or 9, which comprises coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo compound, condensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and condensing the resultant primary conden-sation product with an aminobenzene of the formula (5) to give a fibre-reactive azo dye of the formula (1).
12. A process according to claim 7, 8 or 9, which com-prises condensing an amino compound of the formula (2) with 2,4,6-trifluoro-s-triazine of the formula (4), condensing the primary condensation product thereby obtained with an amino-benzene of the formula (5), diazotising the secondary conden-sation product and coupling it with a coupling component of the formula (3) to give a fibre-reactive azo dye of the formula (1).
13. A process according to claim 7, 8 or 9, which com-prises condensing an amino compound of the formula (2) with 2,4,6-trifluoro-s-triazine of the formula (4), diazotising the primary condensation product thereby obtained and coupling it with a coupling component of the formula (3) and condensing the resultant azo compound with an aminobenzene of the formula (5) to give a fibre-reactive dye of the formula (1).
14. A process according to claim 7, 8 or 9 which comprises coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo compound, condensing this azo compound with two equivalents of 2,4,6-tri-fluoro-s-triazine of the formula (4) and condensing the resultant diprimary condensation product with two equivalents of an amino-benzene of the formula (5) to give a fibre-bireactive azo dye of the formula (1).
15. A process according to claim 7, 8 or 9 which comprises coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo compound and condensing this azo compound with two equivalents of the primary condensation product of 2,4,6-trifluoro-s-triazine of the formula (4) and an aminobenzene of the formula (5) to give a fibre-bi-reactive azo dye of the formula (1).
16. A process according to claim 10 which comprises coup-ling diazotised 1-amino-3-acetylaminobenzene-6-sulphonic acid with 1-(4',8'-disulphonaphthyl[2']-3-methyl-5-pyrazolone, con-densing the resultant azo compound with 2,4,6-trifluoro-s-tria-zine after saponification of the acetyl group, and condensing the primary condensation product with 2-aminotoluene to give a fibre-reactive azo dye of the formula 11. A process according to claim 10 which comprises coup-ling diazotised 1-amino-3-acetylaminobenzene-6-sulphonic acid with 1-(4',6',8'-trisulphonaphthyl[2']-5-pyrazolone-3-carboxylic acid, condensing the resultant azo compound with 2,4,6-trifluoro-1,3,5-triazine after saponification of the acetyl group, and con-densing the primary condensation product with 2-amino-toluene to give a fibre-reactive azo dye of the formula 18. A process for dyeing and printing which comprises the use of the azo dyes according to claim 1.
19. A process according to claim 18 for dyeing cellulose fibres.
20. The dyed or printed textile material obtained accord-ing to claim 18 or 19.
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1 Fibre-reactive azo dyes of the formula (1), wherein A is a residue of benzene or naphthalene, Y is methyl, sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen, n is a positive integer from 1 to 6 and m is 1 or 2, and A and B can contain as further substi-tuents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and carboxyl group and halogen atoms, and the phenylamino radical bonded to the s-triazine ring can contain as further substituent at the phenyl nucleus, in addition to and independently of X, an alkyl radical of 1 to 4 carbon atoms, and, if m is 2, the substituents R and X of both 2-fluoro-4-(2'-X-phenyl amino)-s-triazin-6-yl-N(R) radicals can be different, and metal complexes of the fibre-reactive azo dyes of the formula (1).
2. Fibre-reactive azo dyes according to claim 1 wherein X is methyl, methoxy, carboxy or chlorine.
3. Fibre-reactive azo dyes according to claim 1 wherein m is 1 and the 2-fluoro-4-(2'-X-phenylamino)-s-triazin-6-yl-N(R) radical is bonded to the residue A.
4. Fibre-reactive azo dyes according to claim 1 wherein A is a sulphophenyl radical, Y is methyl or carboxy, B is a phenyl or naphthyl radical which is unsubstituted or substituted by sulpho and chlorine, R is hydrogen and m is 1, and X and n are as defined in claim 1.
5. The fibre-reactive azo dye of the formula 6. The fibre-reactive azo dye of the formula 7. A process for the manufacture of fibre-reactive azo dyes of the formula (1), wherein A is a benzene or naphthalene residue, Y is methyl sulphomethyl, carboxyl or carbamoyl, B is hydrogen, an alkyl or aryl radical, R is hydrogen or alkyl of 1 to 4 carbon atoms, X is alkyl or alkoxy of 1 to 4 carbon atoms, carboxyl or halogen, n is a positive integer from 1 to 6 and m is 1 or 2, and A and B can contain further as substituents alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, acylamino groups of 1 to 6 carbon atoms, amino groups, the ureido, hydroxyl and carboxyl group and halogen atoms, and the phenylamino radical bonded to the s-triazine ring can contain as further substituent at the phenyl nucleus, in addition to and independently of X, an alkyl radical of 1 to 4 carbon atoms, and, if m is 2, the substituents R and X of both 2-fluoro-4-(2'-X-phenyl amino)-s-triazin-6-yl-N(R) radicals can be different, which process comprises reacting a diazotised amino compound of the formula A - NH2 (2), a coupling component of the formula (3), wherein A and B together contain 1 to 6 sulpho groups, and A and/or B contain a -N(R)H group, one or two equivalents of 2,4,6-trifluoro-1,3,5-triazine of the formula (4), and one or two equivalents of identical or different amino-benzenes of the formula (5), by coupling and condensation, in optional sequence, to give a fibre-reactive azo dye of the formula (1), and optionally treating the azo compounds so obtained with metal donors before or after the condensation with fluoro-s-triazine.
8. A process according to claim 7 wherein the starting materials are aminobenzenes of the formula (5), in which X is methyl, methoxy, carboxyl or chlorine.
9. A process according to claim 7 wherein the starting materials are compounds of the formula (2) and (3), in which only A, but not B, contains a -N(R)H group.
10. A process according to claim 7 wherein the starting materials are compounds of the formula (2), in which A is a sulphophenyl radical, compounds of the formula (3), in which Y is methyl or carboxy and B is a phenyl or naphthyl radical which is unsubstituted or substituted by sulpho and chlorine, and A and B together contain 1 to 6 sulpho groups and A or B
contains a -NH2 group, one equivalent of 2,4,6-trifluoro-s-triazine of the formula (4) and one equivalent of an aminobenzene of the formula (5), wherein X is as defined in claim 7.
11. A process according to claim 7, 8 or 9, which comprises coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo compound, condensing this azo compound with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and condensing the resultant primary conden-sation product with an aminobenzene of the formula (5) to give a fibre-reactive azo dye of the formula (1).
12. A process according to claim 7, 8 or 9, which com-prises condensing an amino compound of the formula (2) with 2,4,6-trifluoro-s-triazine of the formula (4), condensing the primary condensation product thereby obtained with an amino-benzene of the formula (5), diazotising the secondary conden-sation product and coupling it with a coupling component of the formula (3) to give a fibre-reactive azo dye of the formula (1).
13. A process according to claim 7, 8 or 9, which com-prises condensing an amino compound of the formula (2) with 2,4,6-trifluoro-s-triazine of the formula (4), diazotising the primary condensation product thereby obtained and coupling it with a coupling component of the formula (3) and condensing the resultant azo compound with an aminobenzene of the formula (5) to give a fibre-reactive dye of the formula (1).
14. A process according to claim 7, 8 or 9 which comprises coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo compound, condensing this azo compound with two equivalents of 2,4,6-tri-fluoro-s-triazine of the formula (4) and condensing the resultant diprimary condensation product with two equivalents of an amino-benzene of the formula (5) to give a fibre-bireactive azo dye of the formula (1).
15. A process according to claim 7, 8 or 9 which comprises coupling a diazotised amino compound of the formula (2) with a coupling component of the formula (3) to give an azo compound and condensing this azo compound with two equivalents of the primary condensation product of 2,4,6-trifluoro-s-triazine of the formula (4) and an aminobenzene of the formula (5) to give a fibre-bi-reactive azo dye of the formula (1).
16. A process according to claim 10 which comprises coup-ling diazotised 1-amino-3-acetylaminobenzene-6-sulphonic acid with 1-(4',8'-disulphonaphthyl[2']-3-methyl-5-pyrazolone, con-densing the resultant azo compound with 2,4,6-trifluoro-s-tria-zine after saponification of the acetyl group, and condensing the primary condensation product with 2-aminotoluene to give a fibre-reactive azo dye of the formula 11. A process according to claim 10 which comprises coup-ling diazotised 1-amino-3-acetylaminobenzene-6-sulphonic acid with 1-(4',6',8'-trisulphonaphthyl[2']-5-pyrazolone-3-carboxylic acid, condensing the resultant azo compound with 2,4,6-trifluoro-1,3,5-triazine after saponification of the acetyl group, and con-densing the primary condensation product with 2-amino-toluene to give a fibre-reactive azo dye of the formula 18. A process for dyeing and printing which comprises the use of the azo dyes according to claim 1.
19. A process according to claim 18 for dyeing cellulose fibres.
20. The dyed or printed textile material obtained accord-ing to claim 18 or 19.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU75515 | 1976-08-02 | ||
| LU75515A LU75515A1 (en) | 1976-08-02 | 1976-08-02 | |
| LU77654A LU77654A1 (en) | 1977-06-29 | 1977-06-29 | FIBER-REACTIVE AZO DYES, THEIR PRODUCTION AND USE |
| LU776,554 | 1977-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1101412A true CA1101412A (en) | 1981-05-19 |
Family
ID=26640209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,714A Expired CA1101412A (en) | 1976-08-02 | 1977-07-29 | Fibre-reactive azo dyes, process for their manufacture and use thereof |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5322527A (en) |
| CA (1) | CA1101412A (en) |
| CH (1) | CH634093A5 (en) |
| CS (1) | CS190346B2 (en) |
| DE (1) | DE2734679C2 (en) |
| FR (1) | FR2360642A1 (en) |
| GB (1) | GB1554080A (en) |
| IT (1) | IT1091752B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3477802D1 (en) * | 1983-06-10 | 1989-05-24 | Ciba Geigy Ag | Reactive dyes, their preparation and their use |
| DE3466555D1 (en) * | 1983-06-17 | 1987-11-05 | Ciba Geigy Ag | Reactive dyes, their preparation and their use |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH438533A (en) * | 1963-07-10 | 1967-06-30 | Geigy Ag J R | Process for the preparation of reactive azo dyes |
| DE1644208C3 (en) * | 1967-04-19 | 1978-06-01 | Bayer Ag, 5090 Leverkusen | Reactive dyes |
| CH554402A (en) * | 1969-07-11 | 1974-09-30 | Ciba Geigy Ag | PROCESS FOR THE PRODUCTION OF FIBER REACTIVE COLORS. |
| BE757602A (en) * | 1969-10-17 | 1971-04-16 | Geigy Ag J R | REAGENT COLORANTS AND THEIR PREPARATION |
| DE2114158A1 (en) * | 1971-03-24 | 1972-09-28 | Bayer Ag | Reactive dyes |
| CH614729A5 (en) * | 1974-04-18 | 1979-12-14 | Ciba Geigy Ag |
-
1977
- 1977-07-28 CH CH934577A patent/CH634093A5/en not_active IP Right Cessation
- 1977-07-29 IT IT5050177A patent/IT1091752B/en active
- 1977-07-29 CA CA283,714A patent/CA1101412A/en not_active Expired
- 1977-07-29 CS CS503877A patent/CS190346B2/en unknown
- 1977-08-01 FR FR7723671A patent/FR2360642A1/en active Granted
- 1977-08-01 DE DE19772734679 patent/DE2734679C2/en not_active Expired
- 1977-08-02 JP JP9290877A patent/JPS5322527A/en active Pending
- 1977-08-02 GB GB3228377A patent/GB1554080A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2734679C2 (en) | 1984-03-08 |
| CS190346B2 (en) | 1979-05-31 |
| FR2360642B1 (en) | 1980-04-18 |
| JPS5322527A (en) | 1978-03-02 |
| GB1554080A (en) | 1979-10-17 |
| CH634093A5 (en) | 1983-01-14 |
| FR2360642A1 (en) | 1978-03-03 |
| IT1091752B (en) | 1985-07-06 |
| DE2734679A1 (en) | 1978-02-09 |
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