CN1056635C - Fibre-reactive dyestuffs - Google Patents
Fibre-reactive dyestuffs Download PDFInfo
- Publication number
- CN1056635C CN1056635C CN94105676A CN94105676A CN1056635C CN 1056635 C CN1056635 C CN 1056635C CN 94105676 A CN94105676 A CN 94105676A CN 94105676 A CN94105676 A CN 94105676A CN 1056635 C CN1056635 C CN 1056635C
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- China
- Prior art keywords
- formula
- group
- compound
- alkyl
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 111
- 229920000742 Cotton Polymers 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000004043 dyeing Methods 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 72
- 229910052739 hydrogen Inorganic materials 0.000 claims description 61
- 239000001257 hydrogen Substances 0.000 claims description 60
- 150000002431 hydrogen Chemical class 0.000 claims description 42
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 125000001118 alkylidene group Chemical group 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 238000005859 coupling reaction Methods 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 239000012954 diazonium Substances 0.000 claims description 8
- 150000004699 copper complex Chemical class 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 6
- 150000004700 cobalt complex Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005837 enolization reaction Methods 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 8
- 238000010186 staining Methods 0.000 claims 4
- 230000008520 organization Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- -1 azomethine Chemical compound 0.000 abstract description 19
- 239000000835 fiber Substances 0.000 abstract description 15
- 238000007639 printing Methods 0.000 abstract description 8
- 239000003086 colorant Substances 0.000 abstract description 3
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000010985 leather Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 239000004627 regenerated cellulose Substances 0.000 abstract description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 abstract 1
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 239000002657 fibrous material Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 71
- 239000000047 product Substances 0.000 description 41
- 238000006467 substitution reaction Methods 0.000 description 38
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 34
- 238000000034 method Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 23
- 239000000460 chlorine Substances 0.000 description 22
- 235000017550 sodium carbonate Nutrition 0.000 description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004744 fabric Substances 0.000 description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- VMJNTFXCTXAXTC-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-5-carbonitrile Chemical group C1=C(C#N)C=C2OC(F)(F)OC2=C1 VMJNTFXCTXAXTC-UHFFFAOYSA-N 0.000 description 11
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 238000013459 approach Methods 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000985 reactive dye Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 description 2
- 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 2
- NZDXSXLYLMHYJA-UHFFFAOYSA-M 4-[(1,3-dimethylimidazol-1-ium-2-yl)diazenyl]-n,n-dimethylaniline;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1N=NC1=[N+](C)C=CN1C NZDXSXLYLMHYJA-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KBRLUWNROJMNFW-UHFFFAOYSA-N N,N-diethylethanamine tetramethylazanium Chemical compound C(C)N(CC)CC.C[N+](C)(C)C KBRLUWNROJMNFW-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WVWIRAXBVMPXOX-UHFFFAOYSA-N [C].C1=CN=CN=C1 Chemical group [C].C1=CN=CN=C1 WVWIRAXBVMPXOX-UHFFFAOYSA-N 0.000 description 1
- MYOXMAQGEINAEF-UHFFFAOYSA-N [C].N1=NN=CC=C1 Chemical group [C].N1=NN=CC=C1 MYOXMAQGEINAEF-UHFFFAOYSA-N 0.000 description 1
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000003996 polyglycerol polyricinoleate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention relates to free acid or salt of a fiber reactive compound disclosed in the specification and a mixture thereof. In the formula, FC is a base group of non-metal or metal complex type water solubility azo, formazane, phthalocyanine, azomethine, oxazine, thiazine, phenoxazine or triphenylmethane dye. The base group can contain another fiber reactive base group, and other symbols are limited in the specification. The compound is used for dyeing or printing organic matrix which contains hydroxy or nitrogen. The compound is suitable for substrate, such as leather, raw material which contains natural or synthetic polyamide, or natural or regenerated cellulose, or fiber material which is composed of the raw material. Products which contain cotton or full cotton are preferable. The performance, such as light resistance, moisture resistance, firmness, antioxidation, etc., of obtained dyed colors and printing is good.
Description
The present invention relates to chromophore compound that contains fiber-reactive groups and preparation method thereof.These compounds are suitable for being used as fibre-reactive dyes in any traditional dyeing and printing technology.
More particularly, the invention provides the free acid of formula I compound or the mixture of salt and formula I compound,
In the formula Fc be water-soluble azo no metal or the metal complexes form, first _, the group of phthalocyanine, azomethine, oxazine, thiazine, azophenlyene or triphenylmethane dye, these groups can contain the additional fibers reactive group,
A independently represents 0 or 1 separately,
B is 1 or 2,
X independently represent separately direct key ,-CO-or-SO
2-,
R
1Independent separately expression hydrogen, unsubstituted C
1-4Alkyl or by hydroxyl, halogen ,-SO
3H ,-OSO
3H or-the mono-substituted C of COOH
1-4Alkyl,
Alk independently represents C separately
2-4Alkylidene group;
W is independently expression separately
Alkylidene group
Alkylidene group
Or
M is 0 or 1 in the formula,
B
1Be C
2-6Alkylidene group, have-O-or-NR
1-C
2-6Alkylidene chain is by one or two hydroxyl or by the C of a carboxyl substituted
3-6Alkylidene group,
Or
N is 0,1,2,3 or 4 in the formula,
R
2Be hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H.
Any alkyl, alkenyl, alkynyl or alkylidene group in the specification sheets as not indicating in addition, all are the straight or branched groups.Any that replace by hydroxyl, be connected in the alkyl or alkylidene group on the nitrogen-atoms, this hydroxyl preferably is connected on the carbon atom that directly is not connected on the nitrogen-atoms.Contain in the alkylidene group of two hydroxyls at all, these hydroxyls are connected on the best different carbon atom not adjacent to each other.Having-O-or-NR
1-and be connected in any alkylidene group on the nitrogen-atoms ,-Q-or-NR
1-preferably be connected in not directly with carbon atom that nitrogen-atoms links to each other on.
Any halogen preferentially refers to fluorine, chlorine or bromine; Chlorine or bromine is better, and chlorine is best.
Fc does not preferably have the water soluble group of monoazo metal or that contain metal or disazo dyes, when dyestuff is metal complexes, it preferably first _ 1: 1 copper complex or 1: 2 chromic compound or 1: 2 cobalt complex form, the copper or the nickel complex of phthalocyanine or triphendioxazine dyestuff.
The preferably independent separately direct key of expression of X or-SO
2-.
The preferably independent separately expression C of Alk
2-3Alkylidene group.
R
1Any alkyl of expression preferably contains 1 or 2 carbon atom.
R
1The alkyl of any replacement of expression is C preferably
1-3Alkyl, and wherein preferably contain one be selected from hydroxyl ,-SO
3H ,-OSO
3H or-substituting group of COOH (especially hydroxyl).
All R
1Be R
1aBetter, R wherein
1aIndependent separately expression hydrogen, methyl, ethyl, 2-hydroxyethyl ,-(CH
2) r-SO
3H ,-(CH
2) r-OSO
3H or-(CH
2) q-COOH, wherein r is 1 or 2, and q is 1,2 or 3.
All R
1Be R
1B is better, wherein R
1B independently represents hydrogen, methyl, ethyl or 2-hydroxyethyl separately.Best each R
1All be hydrogen.
All R
2Be R
2aBetter, R wherein
2aIndependent separately expression hydrogen, methyl, methoxyl group ,-COOH or-SO
3H.All R
2Be R
2bR better, wherein
2B independently represent separately hydrogen or-SO
3H.
All B
1Be B
1A is better, wherein B
1A independently represents C separately
2-4Alkylidene group, C
2-3Alkylidene group-O-C
2-3Alkylidene group, C
2-3Alkylidene group
The C that alkylidene group, monohydroxy replace
3-4Alkylidene group,
Or
N in the formula
1Be 0,1,2 or 3.All B
1Be B
1B is better, wherein B
1B independently represents C separately
2-3The C that alkylidene group, monohydroxy replace
3-4Alkylidene group,
Or
N in the formula
2Be 0,1 or 2.
All B
1Be B
1CBest, B wherein
1CIndependent separately expression C
2-3The C that alkylidene group or monohydroxy replace
3-4Alkylidene group.
All W are W
1Better, W wherein
1Independent separately expression
Alkylidene group
Or
Alkylidene group
All W are W
2Better, W
2Independent separately expression
Or
All W are W
3Best, W wherein
3Independent separately expression-NH-B
1C-NH-.
Formula (I) compound that does not have metal or metal complexes form preferably is corresponding to the compound shown in the formula that limits below (1) to (7): compound (1)
DK is the group of benzene type or naphthalene type diazonium composition in the formula,
KK be benzene type, naphthalene type or heterocyclic type coupling composition or can be by the group of the CH-acidic cpd of enolization, Z is
W as above limits in the formula, and b is 1 or 2, and one of them or two group Z pass through
Link on diazonium and/or the coupling composition.Preferably b is 1.In the compound (1): DK is in the group (a) to (h) preferably, and each key that is marked with asterisk all links to each other with azo-group in these groups,
R in the formula
1And R
2Definition the same,
R
3Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, kharophen, benzamido ,-SO
3H or-COR
13,
R
4Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group or-COR
13,
R
13Be-OH ,-OC
1-4Alkyl or-NH
2,
Alk
1Be-C
2-3Alkylidene group,
R
5Be hydrogen ,-SO
3H, C
1-4Alkyl or C
2-4Hydroxyalkyl,
R
50Be hydrogen or-SO
3H,
R
51Be
N is 0,1,2,3 or 4,
P is 0,1 or 2,
Q be 1,2 or 3 and
R is 1 or 2;
KK is (K preferably
1)-(K
7One of) group, wherein be marked with the position of the carbon atom of asterisk for the generation coupling,
R in the formula
1Define the same,
R
6Be hydrogen, C
1-4Alkyl or C
1-4Alkoxyl group and
R
7Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-NHCOC
1-4Alkyl or-NHCONH
2 
R in the formula
1Definition the same,
R
8Be hydrogen, halogen, C
1-4Alkyl or C
1-4Alkoxyl group,
R
9Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H and
R
10Be hydrogen ,-SO
3H or-NR
1-(Z);
R in the formula
11Be-OH or-NH
2,
R
12Be C
1-4Alkyl or-COR
13,
R
13Definition the same,
Q
1Be hydrogen, C
1-4Alkyl or
R
8And R
9Definition the same and
R
14Be hydrogen, halogen, C
1-4Alkyl,
-SO
3H or
R wherein
1The same with a definition, B
3It is divalent bridging group;
Q in the formula
2Be hydrogen, C
1-4Alkyl, C
5-6Cycloalkyl, phenyl or phenyl (C
1-4Alkyl) (wherein each phenyl ring is unsubstituted or is selected from C by 1-3
1-4Alkyl, C
1-4Alkoxyl group, halogen ,-COOH and-SO
3The substituting group of H replaces) ,-COR
13Or quilt-SO
3H ,-OSO
3H or-COR
13Mono-substituted C
1-4Alkyl,
Q
3Be hydrogen ,-CN ,-SO
3H ,-COR
13, C
1-4Alkyl, quilt-OH, halogen ,-CN, C
1-4Alkoxyl group,
,-SO
3H ,-OSO
3H or-NH
2Mono-substituted C
1-4Alkyl ,-SO
2NH
2 Or
R in the formula
15Be hydrogen, C
1-4Alkyl or C
2-4Hydroxyalkyl, and An
_Be non-color development negatively charged ion, Q
4Be hydrogen,
C
1-6Alkyl, C
2-4Alkenyl, C
2-4Alkynyl, C
5-6Cycloalkyl, phenyl or phenyl (C
1-4Alkyl) (wherein each phenyl ring is unsubstituted or is selected from halogen, C by 1-3
1-4Alkyl, C
1-4Alkoxyl group ,-SO
3H ,-COOH and
Substituting group replace), or-C
1-6Alkylidene group-Y, Y is-COOH in the formula ,-COOC
1-4Alkyl ,-SO
3H ,-OSO
3H ,-OH ,-CN, C
1-4Alkoxyl group ,-NH
2Or one can be protonated aliphatic series, cyclic aliphatic, aromatics or heterocyclic amino or quaternary ammonium group,
B
2Be C
2-6Alkylidene group, the C that monohydroxy replaces
3-6Alkylidene group, have between one-O-or-NR
1-C
2-6Alkylidene chain,
-C
1-4Alkylidene group
Or
Alkylidene group or-B
2-NR
1-(Z) be-C
2-4Alkylidene group
And R
1, R
9, R
10And R
13Define the same;
R in the formula
18Be C
1-4Alkyl, phenyl or be selected from halogen, C by 1-3
1-4Alkyl and C
1-4The phenyl that the substituting group of alkoxyl group replaces,
R
1, a and m definition is the same.Compound (2)
R in the formula
6, R
7, R
1It is the same with the Z definition,
T is 2 or 3,
R
6XHas R independently
6A kind of in the implication and
R
7XHas R independently
7A kind of in the implication.
Compound (2) is R wherein preferably
6, R
6XAnd R
7XRespectively the do for oneself compound of hydrogen.
The compound that provides (3) is for based on following no metallic compound (3a) or metal complexes (3b), is preferably 1: 1 copper complex and 1: 2 chromic compound or 1: 2 cobalt complex,
R in the formula
1, Z and m definition is the same, A is
Or
In the formula m and q the definition the same,
R
17Be hydrogen, halogen, nitro, C
1-4Alkyl, C
1-4Alkoxyl group ,-COR
13,-SO
3H or-NHCOCH
3,
R
22Be OH, OCH
3Or NH
2And
R
13Define the same.
In 1: 2 chromic compound or 1: 2 cobalt complex, two azo-compounds can be identical or different, and promptly it is symmetric or asymmetric 1: 2 metal complexes.
Good especially 1: 1 copper complex that is based on compound (3a), wherein A is the group of benzene type diazonium composition, and the group of naphthalene type coupling composition is shown below,
In addition, also have 1: 1 copper complex corresponding to following formula (3c)-(3e):
R wherein
50Be hydrogen or SO
3H,
R
1, Z and r definition is the same;
R in the formula
52Be hydrogen, C
1-4Alkyl or C
1-4Alkoxyl group,
M is 0 or 1, and r is 1 or 2,
M+r is 2 or 3,
R
1, R
2, R
50The same with the Z definition;
D in the formula
3Be
Or
R wherein
29Be hydrogen, COOH or SO
3H,
R
30Be hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group or-O-Alk
1-OR
5, and t, R
5And Alk
1Define the same,
R
1, R
52The same with the Z definition.Compound (4)
D in the formula
1And D
2Independent separately expression contains the group of the diazonium composition of the amino-benzene of sulfo group, sulfonamido or a carboxyl or amino naphthalenes series at least,
Each m is 0 or 1, is 1 but require at least one m,
R
1, Z and n definition is the same.
D
1Be D
1aBetter, D
1aBe formula (ax) or (cx) group,
R in the formula
18Be sulfo group, sulfonamido or-COR
13,
R
19Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-NHCOCH
3Or SO
3H,
R
13, m and p definition is the same,
M+p is 1 or 2.
D
2Be D
2aBetter, D
2aBe formula (dx) group,
R in the formula
4And R
18Define the same, being keyed on the azo-group of asterisk, another free linkage is received on the active group.
Better, (dx) R in the group
182 (azo-group is at 1), and be connected on free linkage on the active group at 4 or 5.Compound (5)
X in the formula
1And X
2In one of be-O-, and another is a carboxyl,
R
20And R
21Independent separately expression hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COR
13Or-NHCO (C
1-4Alkyl),
R
1, R
13, Z and m definition is the same,
P independently represents 0,1 or 2 separately, and
M+2p is 2 at least.Compound (6) and composition thereof
In the formula Q be-O-or-S-,
R
23Independent separately expression hydrogen or-SO
2CH
2CH
2OSO
3H,
M independently represents 0 or 1 separately,
X
3Independent separately expression-SO
2-,-NR
1-,-
*CONR
1-, or-
*SO
2NR
1-, wherein the atom of asterisk is connected on the ring system carbon atom,
Alk
2Independent separately expression C
2-4Alkylidene group, and
R
1Independently represent above-mentioned definition separately with Z,
In a compound (6), two Z are preferably identical.Compound (7) and composition thereof
C is 1,2 or 3 in the formula,
D is 0,1 or 2, but requires c+d to be not more than 3;
Pc is the phthalocyanine base,
Me is copper, nickel, cobalt, iron or aluminium,
R
24And R
25Independent separately expression hydrogen or C
1-6Alkyl, or-NR
24R
25Be can comprise again one-O-or
5 or 6 saturated element heterocycle, wherein R
31Be hydrogen, C
1-4Alkyl, 2-hydroxyethyl or 2-amino-ethyl,
R
26Be hydrogen, halogen, hydroxyl, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H,
A is 0 or 1, X
4Be randomly to contain
Aliphatic series, araliphatic or the heterocyclic bridged group of divalence,
Or-N=N-KK
2, KK in the base
2Be
Or
R
9, R
11, R
12, Q
2,-B
2-,-B
3-and a definition is the same, each carbon atom that indicates asterisk is pointed out coupling position, Q
3A is a hydrogen, CN ,-SO
3H ,-COR
13, C
1-4Alkyl, by hydroxyl, halogen ,-CN, C
1-4Alkoxyl group
,-SO
3H ,-OSO
3H or-NH
2Mono-substituted C
1-4Alkyl ,-SO
2NH
2 
Or
An
_, R wherein
9, R
13, R
15And An
_Define the same.Fiber-reactive groups Z is better corresponding to the group of Za structure,
Z is that Zb is better, and wherein Zb is W
1Equal W
2The Za group.
Z is that Zc is best, and wherein Zc is W
1Equal W
3The Za group.
Formula (1) compound is the compound corresponding to formula (1a)～(1d) preferably: formula (1a) compound
Za definition is the same and be connected in DK in the formula
1Or KK
1On,
DK
1Be (a
1)～(f
1) one of group or group (h
1), the key that wherein indicates asterisk is connected on the azo-group:
P is 0,1 or 2 in the formula, R
3A and R
4A independently represents hydrogen separately, chlorine, methyl, methoxyl group, oxyethyl group or-COOH;
M is 0 or 1 in the formula, and t is 2 or 3, R
5A is a hydrogen, methyl, ethyl ,-SO
3H or 2-hydroxyethyl;
M is 0 or 1 in the formula, and r is 1 or 2, and m+r is 2 or 3;
R in the formula
1b, R
4aThe same with the p definition;
R in the formula
1bThe same with the r definition;
R in the formula
51aBe
Or
R
50, R
1b, a and r definition is the same; KK
1Be (the K that limits below
2a), (K
4a) and (K
5a) shown in one of group or the (K that limits above
3) group:
R in the formula
8aBe hydrogen, chlorine, methyl or methoxy, R
9aBe hydrogen, chlorine, methyl, methoxyl group ,-SO
3H or-COOH, R
10aBe hydrogen ,-SO
3H or
R in the formula
11, R
8aAnd R
9aDefine the same, R
12aBe methyl ,-COOH or-CONH
2, R
14aBe hydrogen, chlorine, methyl, ethyl ,-SO
3H or
Q in the formula
2aBe hydrogen, methyl, ethyl, phenyl ,-COR
13,-CH
2SO
3H or-CH
2OSO
3H, Q
3B is a hydrogen ,-CN ,-SO
3H ,-COR
13, methyl, ethyl ,-CH
2SO
3H or-CH
2NH
2,
Q
4aBe hydrogen,
Methyl, ethyl, cyclohexyl, phenyl or phenyl (C
1-2Alkyl), in the back in two groups, phenyl ring be unsubstituted or by 1 or 2 be selected from chlorine, methyl, methoxyl group ,-SO
3H ,-COOH ,-NH
2With
Substituting group replace, or-C
1-4Inferior
Alkyl-Y
2, B
2aBe-C
2-4Alkylidene group, monohydroxy replaces-C
3-4Alkylidene group-,
-C
1-2Alkylidene group
Or
Alkylidene group or B
2aBe attached thereto
Formation-C together
2-3Alkylidene group
Y
2Be-COOH-SO
3H ,-OSO
3H ,-OH ,-CN, methoxyl group or-NR
27R
28, R
27And R
28Independent separately expression hydrogen, unsubstituted C
1-4Alkyl is by hydroxyl, C
1-4Alkoxyl group ,-COOH ,-SO
3H ,-NH (C
1-4Alkyl) or N (C
1-4Alkyl)
2Mono-substituted C
1-4Alkyl, unsubstituted cyclohexyl is by 1-3 methyl substituted cyclohexyl, phenyl or phenyl (C
1-4Alkyl), wherein each phenyl ring is unsubstituted or is selected from halogen (preferably chlorine), C by 1 or 2
1-4Alkyl, C
1-4Alkoxyl group ,-SO
3H and-substituting group of COOH replaces, perhaps-NR
27R
28Be piperidines, morpholine or a piperazine ring, wherein each ring is unsubstituted or contains 1～3 methyl; Formula (1b) compound,
M+r equals 2 or 3 in the formula,
R
6aBe hydrogen, methyl or methoxy, R
7aBe hydrogen, chlorine, methyl, methoxyl group ,-NHCOCH
3Or-NHCONH
2Formula (1c) compound,
DK in the formula
2Be the formula (a that limits above
1), (b
1) or (c
1) group; Formula (1d) compound,
Sulfo group is at 3 or 4 of naphthalene nucleus in the formula,
DK
3Be formula (a
2) or (c
2) group,
R in the formula
3aAnd R
4aDefine the same,
M+p equals 1 or 2 in the formula.Compound (2) is corresponding to formula (2a) preferably,
R in the formula
7The a definition is the same, and m+r equals 2 or 3.
Compound (3) is based on no metallic compound (3a preferably
1) or (3b
1) 1: 1 copper complex,
A wherein
1Be
Or
R
17aBe hydrogen, chlorine, bromine, nitro, methyl, methoxyl group ,-SO
3H or-COOH, R
22aBe OH or OCH
3, and m+r equals 2 or 3;
R in the formula
22aDefine the same.
In addition, compound (3) also has corresponding to following general formula (3c preferably
1), (3d
1) and (3e
1) 1: 1 copper complex,
R in the formula
50And R
2aDefine the same, R
52aBe hydrogen, methyl or methoxy, D
3aBe
R in the formula
30aBe hydrogen, methyl or methoxy.Compound (4) is formula (4a) compound preferably,
D in the formula
1a, R
4And R
18Define the same;
Be more preferably following formula (4a) compound: R wherein
4Be hydrogen, R
182 of phenyl, and
4 or 5 of phenyl.Formula (5) compound is R wherein preferably
20And R
21Respectively be R
20aAnd R
21aCompound, and R
20aAnd R
21aIndependent separately expression hydrogen, chlorine, methyl, methoxyl group ,-COOH or-NHCOCH
3
Compound (6) is following compound preferably: wherein Q is-O-, X
3Independent separately expression
Or
R
1Independent separately expression R
1b,
Alk
2Independent separately expression-C
2-3Alkylidene group-,
Z independently represents Za separately.
Better compound (6) is two identical compounds of group that contain Za wherein.
Compound (7) is that wherein Me is copper or nickel and R preferably
24And R
25Respectively be those compounds of hydrogen.
Better compound (7) is following compound: wherein Me is copper or nickel, and c is 2 or 3, and d is 0, R
1Independent separately expression R
1B, Z are Za, R
26Be hydrogen ,-COOH or-SO
3H, and a is 0, or a is 1 and X
4Be-N=N-KK
2, KK wherein
2Be
Q in the formula
2A, Q
3B and-B
2The a-definition is the same.
In addition, good especially situation is in above-mentioned all good no metallic compounds and metal complexes
(1) Za is Zb;
(2) Za is Zc;
(3) Za is Zc, and R
1bBe hydrogen.
When formula I compound is the form of salt, not strict with sulfo group and any carboxyl bonded positively charged ion, can be any non-color development positively charged ion of those routines in the fibre-reactive dyes field, be water miscible but require corresponding salt.These cationic examples have alkali metal cation and ammonium ion unsubstituted and that replace, as lithium, sodium, and potassium, ammonium, one, two, three and tetramethyl-ammonium triethyl ammonium and, two and the triethanol ammonium plasma.
Positively charged ion is alkali metal cation and ammonium ion preferably, and is best with sodium ion.
Can be identical or different in the formula I compound with sulfo group and any carboxyl bonded positively charged ion, for example above-mentioned positively charged ion can be mixed and use, this means that formula I compound can be the mixing salt form.
The present invention further provides the preparation method of formula I compound and composition thereof, comprised making formula II compound or its mixture at Y
3Be-during W-H and 5-cyano group-2,4, the reaction of 6-trichloropyrimidine is perhaps at Y
3When being chlorine and formula III compound (by formula II compound and 1: 1 mol ratio of formula III compound) reaction,
Y in the formula
3Be-W-H or chlorine Fc, X, R
1, Alk, a, b and W definition be the same,
The W definition is the same in the formula.
Y in the formula II compound
3Be-W-H is better.Formula II (Y
3Be-W-H) compound and 5-cyano group-2,4 that the condensation reaction of 6-trichloropyrimidine is suitable for carrying out under the condition of 0-40 ℃ and pH7-9.Usually be reaction medium with water, but when 5-cyano group-2,4, when the 6-trichloropyrimidine was dissolved in organic solvent such as the acetone, it also can use.
In addition, the tetrazo compound of formula (4) also can be by making formula IV compound diazotization and prepare with formula V compound alkaline coupling,
D in the formula
2, R
1, Z, m and n definition is the same,
D in the formula
1, R
1, Z, m and n definition is the same.
Formula I compound can be according to currently known methods, and for example Chang Gui use an alkali metal salt is saltoutd, filtered and dry (when needing vacuum available and improve temperature a little), separates.
According to reaction conditions and separation condition, the formula I compound that obtains be free acid or reasonable be contain one or more above-mentioned cationic salt for example form or or even mixing salt form.Can by ordinary method make its from free acid form change into salt or mixing salt form, perhaps press reverse direction and change, perhaps change the form of another kind of salt into from a kind of salt.
The initial compounds of formula II, III, IV and V or known substance, or can be according to currently known methods by known feedstock production.
Formula I compound and composition thereof can be used as fibre-reactive dyes hydroxyl or nitrogenous organic pollutant is dyeed or stamp.Matrix is leather or the filamentary material that contains following material or be made of described material preferably: natural or synthesizing polyamides, particularly natural or regenerated cellulose is as cotton, viscose fiber and SPUN RAYON YARNS.Best matrix is the textile materials that contains cotton or be made of cotton.
Dyeing or stamp are to carry out according to fibre-reactive dyes field currently known methods commonly used.For formula I compound, in 30-80 ℃ of temperature range, use dip method.
The compounds of this invention can be compatible well with other fibre-reactive dyes; They can use separately, also can be used in combination with the suitable allied fiber chemically-reactive dyes with similar dyeing behavior, these performances comprise common dyefastness for example, by dye vat to dyeing capacity size of fiber or the like.The color fastness that dyes with this binding substances is good, and is comparable to the Color that obtains with homogencous dyes.
From their significant assembly ability, formula I compound has good dye uptake and degree of fixation.There is not that a part of dyestuff of set to take off from the matrix upper punch at an easy rate.Resulting dyeing and stamp show to have the good dry state and the light fastness of hygrometric state, and it is all fine also to have good moisture-proof fastness such as washable, water-fast, sea water resistance and a color fastness to perspiration.They also can anti-oxidantly influence, and for example can resist chloride water, hypo(chlorite)bleaching liquid and contain superoxide or the oxygenizement of the washings of perborate.
Further specify the present invention with following example.All umbers and per-cent all are by weight or volumeter in the example.Temperature is degree centigrade.Example 1
In 18.3 parts in 500 parts of water (0.025 mole) formula B compounds, once add 6.1 parts of (20% is excessive) 5-cyano group-2,4,6-trichloropyrimidine acetone soln at 25 °.Continue to add 20% sodium carbonate solution, make the pH value of the spontaneous reduction of mixture remain on 7-7.5.It is 35 ° that the while heated mixt reaches outlet temperature.After 3-4 hour, TLC proves that this condensation reaction stops.
For reaction product isolated, with gained darker red orange solution be heated to 40 ° and with filter clay stir about 10 minutes.Filter then, in filtrate, add sodium-chlor (about 10% volume) while stirring.Leach thin throw out and in about 50 ° of vacuum-dryings.Dyestuff shown in the following formula of gained is dyed cotton products orange.Moisture-proof fastness ability that dyeing that obtains on cotton products by usual method and stamp show and good light fastness, in addition, they also have antioxygenation.
The preparation of initial compounds B
A) with 9.6 parts of 2-amino naphthalenes-3,6, the 8-trisulfonic acid is dissolved in 60 parts of water of the pH12 that adds 4.3 part of 30% sodium hydroxide solution.In this solution, drip 11 part of 30% hydrochloric acid, obtain a kind of suspension, it is fully stirred.Add after 25 parts of ice, add 6.5 parts of 4N sodium nitrite solutions at 0-5 ° and carry out diazotization reaction.This diazonium salt solution was added in 30 minutes in 3-7 ° the suspension of being made up of in 25 portions of frozen water 3.9 parts of 3-aminophenyl ureas.In the reinforced process, add 22 part of 20% sodium carbonate solution, make pH remain on 5.0.The aminoazo-compound that contains formula A in the red solution that forms.
B) with 30 minutes 5.1 parts of cyanuryl chlorides stirrings are joined in 30 portions of frozen water.In 5 minutes, add a) step gained dye solution then, add 8 part of 20% sodium carbonate solution, carry out condensation reaction at pH6.0.Be added in the reddish orange solution that obtains contain in 50 portions of frozen water 3.3 parts of 1, add 8 part of 30% hydrochloric acid and its pH transferred to 6.0 solution.In 1 hour, the temperature of this reaction mixture slowly is raised to 48-50 °.Simultaneously, adding 20 part of 20% sodium carbonate solution makes mixture pH remain on 6.0.Before this orange dye that separates formation, add 100 parts of sodium-chlor, make its precipitation.So just obtain formula B compound.Example 2-200
According to the similar method of example 1 described method, with suitable initial compounds to form required color development part Fc, the no metallic compound shown in the listed formula I of table 1-11 below can further making.Top at all these tables has all provided the corresponding structure formula, the symbol in the formula as the table defined in.
Example 2-200 compound can be used to the matrix that contains cellulosic fibre or be made of cellulosic fibre according to the dip method of routine or printing technology, especially for the textile materials that is made of cotton yarn, obtains specifying the dyeing and the stamp of tone.Light fastness that dyeing that obtains on cotton products and stamp show and moisture-proof fastness ability, and oxygenizement had resistance.
In table 1 and each table thereafter-divalent group that the W-hurdle limits can be asymmetric diamino group.Usually, the connection between the pyrimidine carbon atom of Yi Bian triazine carbon atom and the other side is by in sequence given.But when the condensation product of pyrimidine compound and diamines was used as initial compounds, according to the preparation method of initial compounds, this connection order also may promptly become pyrimidine/triazine ring mode conversely.
Table 1/ formula (T1) compound
Instance number D
T1.R
1. R
9.-W-
(the position of substitution) 2
H-SO
3H (3)
3 do. H do.
6
H-SO
3H (2)
7
H do. do.8 do. H do.
9
H-SO
3H (3) do. table 1 (continuing) instance number D
T1.R
1. R
9.-W-
(the position of substitution) 10 do. H do.
11
H H
12 do. H SO
3H (3)
13 do. H SO
3H (2)
14
H H
15 do. H H-NHCH
2CH
2NH-16 do. H SO
3H (3)
17
H H do.12 do. CH
3H do.19 do. H SO
3H (2) do. is in last table and later table, and do.=is the same.The dyeing and the stamp that carry out on cotton products with the dyestuff of example 2-19 have greenish-yellow tone.Table 2/ formula (T2) compound
Instance number R
2. R
3. R
4. R
8. R
9. R
10.-W-20 H H-SO
3H H H H-NHCH
2CH
2NH-21 H H do. CH
3-SO
3H CH
3 22 CH
3OCH
3H do. do. OCH
3Do.23 do. CH
3H do. do. do. do.24 H H-SO
3H do. do. do.
25 CH
3OCH
3H-SO
3H H-SO
3H
The dyeing and the stamp that carry out on cotton products with the dyestuff of example 20-25 have greenish-yellow tone.Table 3/ formula (T3) compound
Instance number-W-26
27
28-NHCH
2CH
2NH-29
The dyeing and the stamp that carry out on cotton products with the dyestuff of example 26-29 have greenish-yellow tone.Table 4/ formula (T4) compound
In the end provided the dyeing of separately cotton products being dyed among the hurdle I, wherein a is a green-yellow, and b is yellow.
The position of substitution instance number D
T4. R
12. R
13.-NH-.-W-. I30
CH
3H 5
B31 do. do. H 5
B32
Do. H 4 do. b33 do. do. H 4-NHCH
2CH
2NH-b34 do. do. H 5
B35
Do. H 4 do. b36
Do. H 5 do. b
Table 4 (continuing)
The position of substitution instance number D
T4. R
12. R
13.-NH-.-W-. I37
-COOH-SO
3H 5
A38
Do. 4
A39
Do. 5 do. a40
Do. 4 do. b41 do. do. do. 4-NHCH
2CH
2NH-b
Table 5/ formula (T5) compound
In the end provided the dyeing of separately cotton products being dyed among the hurdle I, wherein a is a green-yellow, and b is yellow.
The position of substitution instance number-W--N=N-. R
2. R
3. R
11. R
12. R
13. R
14. R
15. I42-NHCH
2CH
2NH-4 H 5-SO
3H OH CH
3H 4-SO
3H H b43 do. 4 H do. OH do. Cl do. 5-Cl b44 do. 5 H 4-SO
3H OH COOH CH
3Do. H a45 do. 5 SO
3H do. OH CH
3Cl 5-SO
3H H a46 do. 4 H 5-SO
3H NH
2Do. H 3-SO
3H H b47
5 H 4-SO
3H do. do. H 4-SO
3H H a48 do. 5 H do. OH do. Cl do. H a
Table 5 (continuing)
The position of substitution instance number-W--N=N-. R
2. R
3. R
11. R
12. R
13. R
14. R
15. I49
4 H 5-SO
3H OH CH
3SO
3H 5-SO
3H H b50 do. 4 H do. OH COOH H 4-SO
3H H b51 do. 5 SO
3H 4-SO
3H OH CH
3SO
3H do. H a52
4 H 5-SO
3H NH
2Do. H 3-SO
3H H b53 do. 4 H H do. do. SO
3H 5-SO
3H H b54 do. 4 H 5-SO
3H OH do. Cl do. H b55 do. 5 H 4-SO
3H OH COOH CH
34-SO
3H H a56 do. 5 SO
3H do. OH do. H do. H a57 do. 5 H do. OH CH
3Cl do. H a58
4 H 5-SO
3H OH COOH CH
3Do. H b59 do. 5 H 4-SO3H OH CH
3Cl 5-SO
3H H a60
4 H 5-SO
3H OH do. SO
3H do. H b61
5 H 4-SO
3H OH do. do. do. H a table 6/ formula (T6) compound
In the end provided the tone that presents after separately cotton products being dyeed among the hurdle I, wherein a is a green-yellow, and b is yellow.
The position of substitution the position of substitution instance number-W-.-CONH-.-N=N-R
3R
11R
12R
13R
14I62-NHCH
2CH
2NH-3 ' 3 4-SO
3H OH CH
3-SO
3H 4-SO
3H a63 do. 4 ' 4 3-SO
3H OH do. do. 5-SO
3H b64 do. 3 ' 4 do. NH
2Do. H 4-SO
3H a65
3 ' 4 do. OH do.-SO
3H 5-SO
3H b66 do. 4 ' 3 4-SO
3H OH COOH CH
34-SO
3H a67 do. 4 ' 3 do. OH do. H do. a68
3 ' 4 3-SO
3H OH CH
3Cl do. b69 do. 3 ' 3 4-SO
3H NH
2Do. Cl 5-SO
3H a70 do. 4 ' 4 3-SO
3H OH do.-SO
3H 4-SO
3H b71 do. 4 ' 4 do. OH COOH CH
3Do. b table 7/ formula (T7) compound
Instance number R
3R
4Q
2Q
3Q
4-W-72-SO
3H H CH
3-SO
3H CH
3 
73 do. H do. do. do.
74 do.-SO
3H do.-CONH
2Do.75 do. do. do. do.-CH
2CH
3Do.76 do. H do.-CH
2SO
3H do.-NHCH
2CH
2NH-77 do.-SO
3H do. H do.
78 do. do.-COOH H H do.79 do. H do. H H
80 H H-CH
2SO
3H H CH
3Do.81-SO
3H H do.-CONH
2Do.
82 do. H CH
3H-CH
2CH
2SO
3H
83 do.-SO
3H do. H-(CH
2)
3NHCH
3 
84 do. do. do.-CONH
2-CH
2CH
3 
Table 7 (continuing) instance number R
3R
4Q
2Q
3Q
4-W-85-SO
3H-SO
3H CH
3-CONH
2-CH
2CH
3 
86 do. H do.-CH
2SO
3H H
Various dyestuffs with example 72-86 dye cotton products and stamp, present greenish-yellow tone.
Table 8/ formula (T8) compound
The position of substitution instance number R
4Q
2Q
3Q
4-NH--W-87 H CH
3-CH
2SO
3H H 3
88 H do. do. CH
34 do.89 H do. do.-CH
2CH
33 do.90 H-COOH H H 3 do.91 H CH
3-SO
3H H 3 do.92-SO
3H do.-CH
2SO
3H H 4
93 do. do.-CONH
2-CH
2CH
34 do.94 H do.-CH
2SO
3H do. 3 do.
Table 8 (continuing)
The position of substitution instance number R
4Q
2Q
3Q
4-NH--W-95 H-CH
2SO
3H-CONH
2CH
33
96-SO
3H CH
3H-CH
2CH
2SO
3H 4 do.97 H-CH
2SO
3H-CH
2SO
3H CH
33
98-SO
3H CH
3-CONH
2-CH
2CH
2SO
3H 4
99 H CH
3H-CH
2CH
34
Various dyestuffs with example 87-99 dye cotton products and stamp, present greenish-yellow tone.Table 9/ formula (T9) compound
In the end provided the tone of separately cotton products being dyed among the hurdle I, wherein a is a green-yellow, and b is yellow.
All carbon atoms that are marked with asterisk are connected on the nitrogen-atoms of pyridone in the divalent radical that limits in-B-the hurdle.
D in the table 9
T9Can be the following formula group,
According to R
50And R
51Definition, corresponding group is expressed as DD
1To DD
12Provide DD below
1To DD
12The meaning of each group.DD
1: R
51For
And R
50Be HDD
2: R
51Be do. and R
50Be SO
3HDD
3: R
51For
And R
50Be HDD
4: R
51For
And R
50Be HDD
5: R
51For
And R
50Be SO
3HDD
6: R
51For
And R
50Be HDD
7: R
51For
And R
50Be HDD
8: R
51Be do. and R
50Be SO
3HDD
9: R
51For
And R
50Be HDD
10: R
51For
And R
50Be HDD
11: R
51For
And R
50Be SO
3HDD
12: R
51For
And R
50For H. in addition, D
T9 can be the following formula group,
At DD
13-DD
21In the corresponding group of expression, R
50And R
51Limit as follows: DD
13: R
51For
And R
50Be HDD
14: R
51For
And R
50Be SO
3HDD
15: R
51For
And R
50Be HDD
16: R
51For
And R
50Be H
DD
19: R
51For
And R
50Be SO
3HDD
20: R
51For
And R
50Be SO
3HDD
21: R
51For
And R
50Be H.
Table 9 instance number D
T9Q
2Q
3-B--W-I
102
Do.-CH
2SO
3H
a
105
Do.-CONH
2 
A106
-CH
2SO
3H H
Do. b107
CH
3H-
*CH
2CH
2NH--NHCH
2CH
2NH-b
Table 9 (continuing) instance number D
T9Q
2Q
3-B--W-I108
-CH
2SO
3H-CH
2SO
3H-
*CH
2CH
2NH-
B109
CH
3-CONH
2 A110
Do. H-
*CH
2CH
2NH-
A111
CH
3-CH
2SO
3H
B112
Do.
B113
-CH
2SO
3H-CONH
2 
Do. a114
CH
3-CH
2SO
3H do.-NHCH
2CH
2NH-a
Table 9 (continuing) instance number D
T9Q
2Q
3-B--W-I115
CH
3-CH
2SO
3H
A116
Do.
A117 DD
1CH
3H-
*CH
2CH
2NH--NHCH
2CH
2NH-a118 do. do.-CONH
2 
Do. a119 do. do. H do.
A120 DD
2Do.-CONH
2Do.
A121 do. do.-CH
2SO
3NH-
*CH
2CH
2NH-do. a122 DD
3Do. SO
3H
A123 DD
4Do. H do.
A124 do. do.-CONH
2-
*(CH
2)
3NH-do. a125 DD
5Do.-CH
2SO
3H
Do. a126 DD
6Do.-CONH
2-
*CH
2CH
2NH-do. a127 do. do. H do.
A128 DD
7Do. H do.
A129 DD
8Do.-CONH
2 Do. a130 do. do. H do.-NHCH
2CH
2NH-a
Table 9 (continuing) instance number D
T9Q
2Q
3-B--W-I131 DD
9CH
3-CH
2SO
3H-
*CH
2CH
2NH-
A132 DD
10Do. H do. do. a133 DD
11-CH
2SO
3H-CH
2SO
3H do. do. a134 DD
12Do.-CONH
2 
A135 DD
13CH
3Do. do. a136 do. do. H-
*CH
2CH
2NH-do. a137 DD
14Do.-CH
2SO
3H do.
A138 DD
15Do. H do. do. a139 DD
16Do.-CONH
2 
Do. a140 do. do. H-
*CH
2CH
2NH-do. a141 DD
17Do.-CH
2SO
3H
A142 DD
18Do. H do.
A143 DD
19Do.-CH
2SO
3H-
*CH
2CH
2NH-do. a144 DD
20Do.-CONH
2Do. a145 do. do. H
Do. a146 DD
21Do.-CONH
2Do.-NHCH
2CH
2NH-a
Table 10/ formula (T10) compound
In the end provided the tone of separately cotton products being dyed among the hurdle I, wherein b is yellow, and c is a yellowish-orange, and d is orange.Example the position of substitution m R
6R
7-W-I number-N=N-(the position of substitution) 147 21 (3) H-NHCONH
2 D148 21 (4) H do. do. d 149 11 (3) H do. do. d150 20 H CH
3do. b151 2 1 (4) H do. do. b152 1 1 (3) H do. do. b153 2 1 (3) H H do. b154 2 0 H H do. b155 2 1 (3) CH
3CH
3Do. b156 21 (4) OCH
3H do. b157 21 (3) H-NHCOCH
3Do. c158 11 (3) H do. do. c159 11 (3) H-NHCONH
2 
D160 20 H do. do. d161 21 (4) H do. do. d162 21 (3) H H do. b
Table 10 (continuing) example the position of substitution m R
6R
7-W-I number-N=N-(the position of substitution) 163 21 (3) H-NHCOCH
3 
C164 11 (3) H do. do. c165 20 H do. do. c166 21 (3) H CH
3Do. b167 21 (3) OCH
3H do. b168 21 (3) H-NHCONH
2-NHCH
2CH
2NH-d169 21 (4) H do. do. d170 11 (3) H do. do. d171 21 (3) H CH
3Do. b172 21 (3) H H do. b173 21 (3) H-NHCONH
2 D174 21 (4) H CH
3Do. b175 21 (3) H-NHCONH
2 
d
Table 11/ formula (T11) compound
M example (the position of substitution) R
7-W-number 176 1 (4) CH
3 177 1 (4)-CH
2CH
3Do.178 0 CH
3Do.179 1 (3) do. do.180 1 (4) do.
181 1 (4)-CH
2CH
3Do.182 0 do. do.183 0 CH
3Do.184 1 (3)-CH
2CH
3Do.185 1 (4) CH
3-NHCH
2CH
2NH-186 1 (3) do. do.187 0 do. do.188 1 (4) do.
189 1 (4) do.
190 1 (3)-CH
2CH
3Do.191 0 CH
3 192 1 (3) H
193 1 (4) H do.
Table 11 (continuing)
M example (the position of substitution) R
7-W-number 194 1 (3)-NHCOCH
3-NH (CH
2)
3NH-195 1 (3) do.
196 1 (3)-NHCONH
2Do.197 1 (4) do. do.198 1 (3) H do.199 1 (3)-NHCONH
2 200 1 (3) do.-NH (CH
2)
3NH-
Dyestuff with example 176-200 dyes and stamp to cotton products respectively, presents orange.Example 201
Dyestuff shown in 15.6 parts of (0.02mol) following formulas is dissolved in the water of 300 parts of pH8.5-9.
Add small amount of hydrochloric acid and transfer pH to 6.0.Under 10-15 ° and agitation condition, in this solution, add 3.9 parts of (0.02mol+5%) cyanuryl chlorides, and be 5.5-6.5 by adding sodium hydroxide solution maintenance pH.Afterreaction was finished in about 1 hour.
In this reaction mixture (0.02mol), add 1.6 parts of (0.02mol+10%) 1.Carry out condensation at 40-50 °, add sodium hydroxide solution pH is remained on 5.5-6.5.Afterreaction was finished in about 2 hours.
In the thin dye suspensions (0.02mol) that obtains, add 4.6 parts of (0.02mol+10%) 5-cyano group-2,4, the 6-trichloropyrimidine.React with pH8.5-9.0 at 15-20 °.Isolate dyestuff by the saltouing of routine, filtration and drying means corresponding to following formula,
It dyes blueness with cotton products.The color of these cotton products has high fast light and moisture resistance properties, and can antioxygenation.Example 202-291
According to example 201 described similar approach, make required color development part Fc with suitable initial compounds, further make the containing metal compound of the listed formula I of following table 12-17.Provide the corresponding structure formula at the top of each table, the symbol in the formula limits in table.
Adopt conventional dip method or printing technology, the metal complexes of example 202-291 will contain cellulosic fibre or the matrix (especially cotton-spinning fabric) that is made of cellulosic fibre is dyed specified tone.So dyeing and the stamp on the cotton products that form has high fast light or moisture resistance properties, and can antioxygenation.
Table 12/ formula (T12) compound
Instance number D
T12R
52-W-202
CH
3-NHCH
2CH
2NH-203 do. do.
204 do. do.
205
H
206
H do.207
CH
3 
208
Do. 209 do. H
Table 12 (continuing) instance number D
T12R
52-W-210
H
211 do. CH
3-NHCH
2CH
2NH-212
Do.
The various dyestuffs of example 202-214 are dyed blueness with cotton products.Table 13/ formula (T13) compound
Table 13
The position of substitution instance number R
2R
29R
52-NH--W-q (the position of substitution) 215 H H H 4-NHCH
2CH
2NH-2 (3,6) 216 2-OCH
33-SO
3H CH
35
2 (3,8) 217 H do. H, 5 do. 3 (3,6,8), 218 2-OCH
3H CH
34
Do.219 2-CH
3H H 5 do. 2 (4,6) 220 H 2-SO
3H H 4-NH (CH
2)
3NH-2 (3,8) 221 H do. H 4
Do.222 H do. CH
35 do. 2 (3,6) 223 H do. H, 4 do. 3 (3,6,8), 224 2-OCR
33-SO
3H H 5 do. do.225 do. do. H 5
Do.226 do. do. H 5-NHCH
2CH
2The dyestuff of NH-do. example 215-226 is dyed blueness with cotton products.
Table 14/ formula (T14) compound
Table 14
The position of substitution instance number SO
3H R
17R
1-W-227 4 H H
228 4 H CH
3Do.229 6 H H do.230 4 6-Cl H do.231 4 do CH
3Do.232 6 4-Cl H do.233 4 6-COOH H do.234 4 6-SO
3H H do.235 4 do. CH
3Do.236 4 H H
237 6 H H do.238,6 4-CH
3H do.239 4 6-Cl H do.240 4 6-SO
3H H do.241 4 do. H-NHCH
2CH
2NH-242 4 H H do.243 4 6-NO
2H do.244 4 6-Cl H do.245 6 4-Cl H do.246 4 H H-NH (CH
2)
3NH-247 4 6-Cl H do.248 4 6-SO
3H H do.249 4 do. H
250 4 do. H
The dyestuff of example 227-250 is dyed Ruby red with cotton products.
Table 15/ formula (T15) compound
Instance number-W-251-NHCH
2CH
2NH-252
253-NH (CH
2)
3NH-254
255
256
The dyestuff of example 251-256 is dyed mazarine with cotton products.Table 16/ formula (T16) compound
Last hurdle I has provided cotton products colour tone separately in the table, and wherein g is a Ruby red, and h is a purple.
Table 16
The position of substitution instance number R
50-NH--W-r (the position of substitution) I257 5-SO
3H 3-NHCH
2CH
2NH-1 (6) g258 do. 3
Do. g259 3-SO
3H 5 do. do. g260 do. 5
Do. g261 5-SO
3H 3 do. do. g262 do. 3
Do. g263 H 4 do. 2 (6,8) h264 H 4
Do. h265 H 5 do. do. h266 H 4-NHCH
2CH
2NH-do. h267 H 4-NH (CH
2)
3NH-do. h268 H 4
Do. h table 17, formula (T17) compound
Table 17
P the position of substitution m instance number the position of substitution X
1X
2-NH-(the position of substitution) R
20R
21-W-269 2 (3 ', 5 ')-O--COOH 40 2-SO
3H H-NHCH
2CH
2NH-270 do. do. do. 40 do. H
271 do. do. do., 40 do. H
272 do. do. do., 40 3-SO
3H do.273 do. do. do. 40 do. H
274 1 (4 ')-COOH--O-, 31 (5) H H-NHCH
2CH
2NH-275 do. do. do. 3 do. H H-NH (CH
2)
3NH-276 do. do. do. 3 do. H H
277 do. do. do., 3 do. H H
278 do. do. do., 3 do. 3-SO
3H H do.279 1 (5 ') do. do. 3 do. 2-Cl H do.280 do. do. do. 3 do. 2-Cl 5-Cl do.281 do. do. do. 3 do. 2-SO
3H H do.
Table 17 (continuing)
P the position of substitution m instance number the position of substitution X
1X
2-NH-(the position of substitution) R
20R
23-W-282 1 (5 ')-COOH-O-31 (5) 3-SO
3H H
283 do. do. do., 3 do. 4-SO
3H H do.284 do. do. do. 3 do. 4-CH
3H-NHCH
2CH
2NH-285 do. do. do. 3 do. 4-OCH
3H do.286 do. do. do. 3 do. 3-CH
34-Cl
287 1 (4 ')-O--COOH-, 31 (5) 2-CH
3H
288 1 (5 ') do. do., 51 (3) H H do.289 do. do. do., 5 do. 2-CH
3H
290 do. do. do., 5 do. 4-SO
3H H-NHCH
2CH
2The dyestuff of NH-291 do. do. do. 31 (5) H H do. example 269-291 is dyed blueness with cotton products.Example 292
45.3 parts are dissolved in 700 parts of water according to the monoazo-dyes shown in the following formula of currently known methods preparation,
Descend with 30 minutes toward wherein adding 18.5 parts of solid cyanuryl chlorides at 20-25 °.Stir the mixture at pH6.0-6.5, until no longer detecting free amine group.Then, add 11.1 parts of 1, reaction mixture was stirred 2 hours, add rare sodium carbonate solution simultaneously and keep pH7.0.Add sodium-chlor, make condensation product saltout out, filter.The wet mashed prod that obtains is dissolved in 900 parts of water.In this solution, add 24.9 parts of 5-cyano group-2,4, the 6-trichloropyrimidine, and 0-5 ° of stirring 2 hours.Make pH remain on 8-9 by adding rare sodium carbonate solution in the reaction process.Make the gained dye precipitated with sodium-chlor, separate.It is corresponding to following structural formula
This dyestuff is the garnet powder after the drying, presents redness when it is water-soluble, cotton products can be dyed scarlet.These colors that dye have good fast light and moisture resistance properties, and can antioxygenation.Example 293-319
According to example 292 described similar approach,, can make other formulas I compound with suitable initial compounds.They are corresponding to structural formula (T18)
Symbol wherein provides definition in the following Table 18.The color that dyes on cotton products with the dyestuff of example 293-319 has good fast light and moisture resistance properties, and can antioxygenation.
In the end provided the dyeing on each comfortable cotton products among the hurdle I, wherein d is orange, and k is a scarlet.Table 18/ formula (T18) examples of compounds R
3R
4-W-I293 OC
2H
5H
K294 OCH
3SO
3H do. k295-OC
2H
4OH H do. k296 OCH
3H
K297 do. SO
3H do. k298-OC
2H
4OH H do. k299 OCH
3H-NHCH
2CH
3NH-k
Table 18 (continuing) instance number R
3R
4-W-I300 OCH
3SO
3H-NHCH
2CH
2NH-k301 OC
2H
5H do. k302-OC
2H
4OH H do. k303 OCH
3H-NH (CH
2)
3NH-k304 do. SO
3H do. k305-OC
2H
4OH H do. k306 OC
2H5 H
K307 OCH
3H
K308 do. SO
3H do. k309-OC
2H
4OH H do. k310-OC
2H
4OC
2H
4OH H do. k311 do. H-NHCH
2CH
2NH-k312 do. H-NH (CH
2)
3NH-k313 do. H
K314 do. H
K315 CH
3SO
3H do. d316 do. do.
D317 do. do.-NHCH
2CH
2NH-d318 do. do.
D319 do. H do. d example 320
In the mixture of 10 parts of water and 20 parts of ice, 5 parts of cyanuryl chlorides are stirred into unit for uniform suspension.The neutral solution that adds the pH7 of tetra-na salt in 160 parts of water of 30 parts of following formula dyestuffs in this suspension,
Under 5 ° and pH5.5-6.0 condition, stir, up to no longer detecting free amine group.At pH6.5-7.0 temperature slowly is raised to 15 °, adds 3.25 parts of 1 then.Adding hydrochloric acid makes pH remain on 6.0.Mixture reacts completely after this section period 50 ° of heating 3 hours.Add 70 parts of sodium-chlor again, filter this red suspension.With 500 part of 20% sodium chloride solution filter wash cake.The gained mashed prod is placed 500 parts of water, add 4.5 parts of 5-cyano group-2,4, the 6-trichloropyrimidine.Stirred 12 hours at 20 °,, add 80 parts of sodium-chlor then until reacting completely.The dyestuff that obtains is precipitated and filter; It is corresponding to following structural formula:
After this dyestuff drying is the garnet powder, shows red when water-soluble, and it is blue red that the cotton products that dye are.The total fastness ability of the color that dyes on cotton products is fine.Example 321-416
With the similar approach described in the example 320,, also made listed other formula I compound among the following table 19-22 with suitable initial compounds.At the top of each table, provided the corresponding structure formula, symbol wherein provides definition in showing below.Dyestuff dip method routinely with example 321-416 can be with cellulosic fibre, especially cotton products dyeing.The all colours that dyes all is blue red, and fastness is strong.
Table 19/ formula (T19) compound
Example m SO
3The H base-W-the position of substitution 321 01
322 01
323 11,5 do.324,13,6 do.325 01
326 11,5 do.327 0 1-NHCH
2CH
2NH-328 11,5 do.329,14,8 do.330 0 1-NH (CH
2)
3NH-331 11,5 do.332 01
333 11,5 do.334 13,6 do.335,14,8 do.336 01
337 14,8
Table 20/ formula (T20) compound
Example m (SO
3H gets R
3R
4Subrogate for-W-number and put) 338 1 (2) H H
339 do. 5-SO
3H H do.340 do. do. 4-CH
3Do.341 do. do. 4-OCH
3Do.342 do. H 4-CH
3Do.343 do. H 4-OCH
3Do.344 do. 4-SO
3H H do.345 do. H H
346 do. H 4-OCH
3Do.347 do. 5-SO
3H H do.348 do. H 4-CH
3 349 do. H 4-OCH
3Do.350 do. H H do.351 do. 5-SO
3H H do.352 do. 4-SO
3H H do.353 0 2-COOH H do.354 0 3-COOH H do.355 0 4-COOH H do.356 1 (2) 5-SO
3H 4-OCH
3 357 do. H H do.358 do. H 4-CH
3Do.
Table 20 (continuing) example m (SO
3H gets R
3R
4Subrogate for-W-number and put) 359 1 (2) H 4-OCH
3 
360 do. 4-SO
3H H do.361 0 3-COOH H do.362 1 (2) H H
363 do. 5-SO
3H H do.364 do. do. 4-CH
3Do.365 do. 4-SO
3H H do.366 0 2-COOH H do.367 0 3-COOH H do.368 0 4-COOH H do.369 1 (2) H H-NHCH
2CH
2NH-370 do. H 4-OCH
3Do.371 0 2-COOH H do.372 1 (2) 5-SO
3H H-NH (CH
2)
3NH-table 21/ formula (T21) compound
Example
-W-R
16Number 373-NHCH
2CH
2NH-methyl 374 do. ethyls 375 do. phenyl
Table 21 (continuing) instance number-W-R
16376
Phenyl 377 do. methyl 378 do. ethyls 379
Methyl 380 do. phenyl 381
Do.382 do. ethyl 383
Methyl 384-NH (CH
2)
3NH-phenyl table 22/ formula (T22) compound
Table 22
The position of substitution the position of substitution instance number D
T22SO
3H-NH--W-385
3 3-NHCH
2CH
2NH-386 do. 34 do.387 do. 33
388 do. 33
389 do. 33
390 do. 33
391 do., 43 do.392
34 do.393 do., 43 do.394 do., 33 do.395
34 do.396 do., 33 do.397 do., 44 do.398 do. 33
Table 22 (continuing)
The position of substitution the position of substitution instance number D
T22SO
3H-NH--W-399
34
400 do., 3 3-NHCH
2CH
2NH-401 do. 33
402 do. 34
403
33
404 do. 34
405 do., 44 do.406
34 do.407 do., 3 3-NHCH
2CH
2NH-408
33 do.409 do., 43 do.410 do. 34
411 do. 33
412
34 do. tables 22 (continuing)
The position of substitution the position of substitution instance number D
T22SO
3H-NH--W-413
34
414
33 do.415 do., 4 4-NH (CH
2)
3NH-416 do. 34
Example 417
212 parts of cyanuryl chlorides were stirred 45 minutes in 560 parts of ice and 200 parts of water.Toward wherein adding by 190 part 2 in 920 parts of water and 112 part of 30% sodium hydroxide solution, the solution that 4-diaminobenzene-1-sulfonic acid constitutes stirs this mixture 6 hours under the ice bath cooling.Subsequently with this white suspension indirect diazotization.
, press currently known methods therebetween with 140 parts of 4-benzaminic acid diazotization, and under the acid-reaction condition with 320 parts of 1-amino-8-hydroxyl naphthalene-3, the coupling of 6-disulfonic acid.In this red suspension, add above-mentioned diazo solution, carry out alkaline coupling.
In the blue solution that obtains, add 120 parts of 1.Condensation reaction was carried out 2 hours.Use sodium-chlor (25% volume) that reaction mixture is saltoutd then, filter.Blue filter cake is dissolved in again in the water of 10 times of amounts.
In two hours, add in this aqueous solution and in 350 parts of water and 150 parts of ice, stir 175 parts of 5-cyano group-2,4 of 45 minutes, the suspension of 6-trichloropyrimidine.The pH of this reaction mixture was kept 3 hours 9.Add sodium-chlor (10% body x is long-pending) and make products therefrom saltout out, filter, filter cake is 40 ° of vacuum-dryings.This dyestuff has following structural formula,
According to example 417 described similar approach, with suitable initial compounds, can make other formula I compound, they are corresponding to compound shown in the formula (T23),
Symbol in the formula provides definition in the following Table 23.Adopt conventional dip method, this example 418-456 dyestuff is dyed navy with cellulosic fibre, particularly cotton products.These dyeing have good various conventional fastness ability.
Table 23/ formula (T23) examples of compounds R
3R
4The position of substitution R
5-W-
-NH-418 4-SO
3H H 5 SO
3H
419 3-COOH H 4 do. do.420 4-COOH H 4 COOH do.421 do. H 4 SO
2H
422 3-SO
3H H 5 do. do.423 5-COOH 2-Cl 4 do. do.424 do. do. 5 do. do.425 do. do. 4 COOH do.426 3-COOH H 5 SO
3H do.427 4-SO
3H H 4 COOH do.428 2-5O
3H 4-Cl 4 do. do.429 4-SO
3H H 4 SO
2H do.430 2-SO
3H 4-Cl 4 do. do.431 4-SO
3H H 5 do. do.432 2-SO
3H 4-Cl 5 do. do.433 5-COOH 2-Cl 5 do.
434 4-COOH H 5 do. do.435 4-SO
3H H 5 do. do.436 3-COOH H 5 do. do.437 3-COOH H 4 do. do.438 3-SO
3H H 4 do. do.439 do. H 4 COOH do.440 do. H 5 SO
3H -NHCH
2CH
2NH-441 5-COOH 2-Cl 5 do. do.442 5-SO
3H do. 5 do. do.443 3-COOH H 5 do. do.444 2-SO
3H 4-Cl 5 do. -NH(CH
2)
3NH-
Table 23 (continuing) instance number R
3R
4The position of substitution R
5-W-
-NH-445 5-SO
3H 2-Cl 4 SO
3H-NH (CH
2)
3NH-446 4-COOH H 4 COOH
447 5-SO
3H 2-Cl 5 SO
3H do.448 4-COOH H 5 do. do.449 5-COOH 2-Cl 5 do. do.450 3-COOH H 4 COOH
451 3-SO
3H H 4 do. do.452 do. H 5 SO
3H do.453 5-COOH 2-Cl 4 COOH do.454 4-COOH H 5 SO
3H
455 5-SO
3H 2-Cl 4 COOH do.456 2-SO
3H 4-Cl 4 do. do. examples 457
65.9 parts of following formula dyestuffs by the currently known methods preparation are dissolved in 1200 parts of water.At 20-25 ° with adding 37 parts of solid cyanuryl chlorides in 30 minutes.By add dilute sodium carbonate solution continuously in mixture, maintenance pH is 6.0-6.5, stirs 1 hour.Add 22.2 parts of 1, stirred 2 hours, add dilute sodium carbonate solution simultaneously, keep pH7.0 at 40-50 °.Make condensation product saltout out with sodium-chlor, filter.The gained mashed prod is dissolved in 1400 parts of water.Add 49.5 parts of 5-cyano group-2,4 in this solution, the 6-trichloropyrimidine stirred 2 hours at 5-10 °.Adding dilute sodium carbonate solution in reaction process makes pH remain on 8-9.Add sodium-chlor the gained dye salt is separated out, separate.It is corresponding to following structural formula, and dry back is a black powder, is mazarine after water-soluble.This dyestuff is dyed mazarine with cotton products.This dyeing has good fast light and moisture-proof fastness.
Example 458-472
Can make other formula 1 compound according to example 457 described similar approach.They are corresponding to structural formula (T24).
Symbol in the formula provides definition in the following Table 24.The dyestuff of example 458-472 is dyed mazarine with cotton products.These dyeing have good fast light and moisture resistance properties.Table 24/ formula (T24) examples of compounds m R
1-W-number 458 1 H-NHCH
2CH
2NH-459 1 H-NH (CH
2)
3NH-460 1 H
461 1 H
462 1 H
463 0-SO
2CH
2CH
2OSO
3H do.464 0 do.-NHCH
2CH
2NH-465 0 do.-NH (CH
2)
3NH-466 0 do.
467 0 do.
468 1 do. do.469,1 do.
470 1 do.-NHCH
2CH
2NH-471 1 do.-NH (CH
2)
3NH-472 1 do.
Example 473 (is pressed currently known methods with the copper phthalocyanine chlorosulphonation with 25.7 parts of (0.025mol) dyestuffs, then with 1,3-diaminobenzene-4-sulfonic acid reaction makes, and on average contains 2.5 sulfonic groups and 1 sulfonamido in each molecule approximately) be dissolved in the water of 200 parts of pH6.5-7.0.Add after 150 parts of ice, add 4.6 parts of cyanuryl chlorides, stirred two hours at pH6.0-6.5 at 0-5 °.Add 2.8 parts of 1 then, after 1 hour, make temperature in two hours, be raised to 30-35 °, add 20% sodium carbonate solution pH is transferred to 7.5-8.0 0-5 ° of stirring.To separate out also with 70 parts of sodium chloride salts, filtering reaction product be dissolved in 250 parts of water again.Add 6.3 parts of 5-cyano group 2,4 at 0-5 °, the 6-trichloropyrimidine stirred the mixture under this temperature 3 hours.By adding yellow soda ash pH is remained on 8-8.5 simultaneously.After condensation reaction is finished, mixture is saltoutd with 45 parts of sodium-chlor.Suction filtration goes out sedimentary dyestuff and 35 ° of dryings.The dyestuff that obtains is corresponding to following structural formula,
It dyes cellulosic fibre, especially cotton products bright-coloured dark green.These dyeing have good light fastness and fabulous moisture-proof fastness ability.Example 474
According to example 473 described methods, with 25.7 parts of copper phthalocyaine dye carbon of nickel phthalocyanine dye carbon (i.e. 25.5 parts (0.025mol)) replacement of equivalent.Obtain corresponding (NiPc) dyestuff (its structural formula is similar to the formula that example 473 is given), it dyes blue-greenish colour with cotton products.This dyeing has good fastness ability.Example 475-480
According to being similar to example 473 and 474 described methods, can make the other phthalocyanine pigment.They are corresponding to following structural formula,
The definition of the symbol in the formula provides in the following Table 25.In the end provided the tone of separately cotton products being dyed among the hurdle I, wherein e is bright dark green, and f is a blue-greenish colour.These dyeing have good fastness ability.Table 25/ formula (T25) compound
The position of substitution instance number Me c d R-NH--W-I475 Cu 30 H 3
E476 Cu 21 H 3 do. e477 Cu 12 4-SO
3H 3 do. e478 Cu 21 2-COOH H do. e479 Ni 21 H 3 do. f480 Ni 12 4-SO
3H 3
F example 481
25.5 parts of dyestuffs (press currently known methods with the nickel phthalocyanine chlorosulphonation, then with 1,3-diaminobenzene-4-sulfonic acid reaction makes, and on average contains 2.5 sulfonic groups and 1 sulfonamido in each molecule approximately) are stirred with 1.8 parts of Sodium Nitrites in 150 parts of water.This solution is chilled to 0-2 °, is added drop-wise in 100 parts of mixture of ice and water and 12 part of 30% hydrochloric acid.Then the gained diazonium salt suspension is added to by in the solution that 5.9 parts of 1-(3 '-methylamino propyl group)-6-hydroxy-4-methyl pyridone-(2) constitute in 300 parts of ice/water, maintains the temperature at 0-5 ° simultaneously.In the coupled reaction process, make mixture pH remain on 9-9.5 by adding 30% sodium hydroxide solution.By being similar to the method described in the example 473, make gained green solution priority and cyanuryl chloride, 1 and 5-cyano group-2,4, the reaction of 6-trichloropyrimidine obtains the dyestuff shown in the following formula,
By example 473 described similar approach it is separated.This dyestuff is dyed emerald green with cellulosic fibre, especially cotton products.These dyeing have high light fastness and fabulous moisture-proof fastness.Example 482-519
Can make the other phthalocyanine pigment according to example 481 described similar approach.They have following structural formula,
Symbol in the formula provides definition in the table 26 and 27 below.
The dyestuff of example 482-519 is dyed green with cotton, and when using nickel phthalocyanine, color is more bright-coloured.These dyeing have well fast light and moisture-proof fastness.
Table 26/ formula (T26) examples of compounds
Me R Q
3-B
2-NR
1--W-number 482 Cu SO
3H H
483 Ni H H do. do.484 Ni H-CONH
2Do. do.485 Ni SO
3H H-(CH
2)
3NH-do.486 Cu do. H-CH
2CH
2NH-do.487 Ni do. H do.
488 Ni do.-CONH
2-(CH
2)
3NH-do.489 Ni do. H do. do.490 Ni do. H
Do.491 Ni do. H do.
492 Cu H H do. do.493 Ni SO
3H-CONH
2Do. do.494 Ni do. H-CH
2CH
2NH-do.495 Ni SO
3H H
496 Cu H-CONH
2Do.-NHCH
2CH
2NH-497 Ni SO
3H H do.
498 Ni do. H-(CH
2)
3NH--NH (CH
2)
3NH-
Table 27/ formula (T27) compound
The position of substitution example
Me R R
11R
12R
9-NH--W-number 499 Cu SO
3H OH CH
3H 5
500 Ni do. OH do. H, 5 do.501 Ni do. NH
2Do. H 5 do.502 Ni H OH do. 2-SO
3H 5 do.503 Ni SO
3H OH-COOH H 4 do.504 Cu do. OH CH
3H 5
505 Ni do. OH do. 2-SO
3H 5 do.506 Ni do. OH do. H 4 do.507 Cu do. OH-COOH H 5 do.508 Ni H OH CH
32-SO
3H 5 do.509 Ni H OH do. do. 5
510 Ni SO
3H OH do. H 4 do.511 Cu do. OH do. 2-SO
3H 5 do.512 Ni do. NH
2Do. 5 do.513 Ni do. OH do. do. 4
514 Cu do. OH do. H 5
515 Ni H OH-COOH H 5-NHCH
2CH
2NH-516 Cu H OH CH
3H 4 do.517 Ni SO
3H OH do. H 5 do.518 Ni do. NH
2Do. H 4 do.519 Ni do. OH do. 2-SO
3H 5-NH (CH
2)
3NH-example 520
According to example 481 described similar approach, with suitable initial compounds, can make and isolate the dyestuff shown in the following formula,
It dyes bright-coloured green with cotton products.The color that is dyed has good fast light and moisture-proof fastness.
According to described method, can obtain the sodium-salt form of example 1-520 dyestuff.According to different reaction/separation conditions, or by currently known methods this sodium salt is reacted, also can obtain their free acid form or other salt form, for example those contain one or more above-mentioned cationic salt.
The application of explanation The compounds of this invention in the example below.Application example A
The dyestuff of 0.3 part of example 1 is dissolved in 300 parts of softening waters, adds 15 parts of saltcake (baking).Dye vat is heated to 40 °, adds 10 parts of cotton fabrics of bleaching then.40 ° keep 30 minutes after, in cylinder, add 6 parts of yellow soda ash (baking) in batches, added once every 10 minutes, added amount is followed successively by 0.2,0.6,1.2 and last 4.0 parts.In adding the process of yellow soda ash, temperature remains on 40 °.Dyed again 1 hour at 40 ° then.
The cotton fabric that will dye is with cold flowing water rinsing 3 minutes, the flowing water rinsing of reusable heat afterwards 3 minutes then.Fabric boiling washing after in containing 500 parts of softening waters of 0.25 part of commercially available anion active washing composition, will dying 15 minutes.After mobile hot water rinsing 3 minutes and centrifugal treating, the fabric that dyed is dry in about 70 ° desiccator cabinet.The orange fast light and moisture-proof fastness that shows of the cotton fabric that obtains, and can antioxygenation.Application example B
In the dye vat that fills 300 parts of softening waters, add 10 parts of saltcake (baking), 10 parts of cotton fabrics (bleaching).In 10 minutes, dye vat is heated to 40 °, adds the dyestuff of 0.5 part of example 1.Add 3 parts of baked yellow soda ash at 40 ° after keeping 30 minutes again, continued again to dye 45 minutes at 40 °.
The method that the fabric that dyed provides by application example A is successively used cold flow water and hot-fluid water rinse, and boiling washing.After rinsing and the drying, the cotton fabric that obtains orange has the same good fastness ability of pointing out with application example 1.Application example C
Method described in the application example A is done some change, use the dyestuff of 0.3 part of example 481, only with 2 parts of baked yellow soda ash and once adding, the yellow soda ash that the total amount that replacement adds is 6 parts in batches.40 ° of starting temperatures are brought up to 60 °, and the dyeing course of back carried out 1 hour at 60 °.In others, adopt the described method of application example A similarly.The cotton fabric dyeing process that obtains is bright-coloured green, and pile-on properties is good, and shows good light fastness.Application example D
The dyestuff of 2.5 parts of examples 473 is dissolved in 2000 parts of water.Add 100 parts of cotton fabrics, in 10 minutes, the dye vat temperature is brought up to 80 °.Add 100 parts of baked saltcake, add 20 parts of baked yellow soda ash after 30 minutes.Continue dyeing 1 hour at 80 °.Then, the fabric that dyed with flowing cold water and the rinsing of mobile hot water and boiling washing successively of the method that provides according to application example A.After rinsing and the drying, the dyeing on the cotton fabric is bright-coloured dark green, has good fastness ability.
Similarly, the mixture of the dyestuff of all the other examples or the dyestuff of enumerating can be used for according to the described method of application example A-D cotton products being dyeed.Application example E
With the printing paste with following ingredients routinely printing method with cotton fabric printing:
The dyestuff of 40 parts of examples 1
100 parts of urea
350 parts of water
50 part of 4% sodiun alginate thickening material
10 parts of sodium bicarbonates
1000 parts.
With the fabric drying behind the stamp and in 102-104 ° steam fixation 4-8 minute, according to the described method of application example A with it with cold water, reusable heat water rinse and boiling washing, and dry.The orange stamp that obtains has good various conventional fastness ability.
Similarly, the mixture of the dyestuff of example 2-520 or the dyestuff the enumerated method that can provide according to application example E is with the cotton products stamp.The fastness ability that all stamps that obtain all show.
Claims (5)
1. the mixture of the free acid of compound or salt shown in the formula I or formula I compound is with the application in dyeing of hydroxyl or nitrogenous organic substrate or the stamp, comprise with the no metal of formula I or metallic compound or its mixture and being used on this matrix as staining agent or stamp agent
Fc is the water-soluble azo of no metal or metal complexes form, the group of phthalocyanine, oxazine dye in the formula,
A independently represents 0 or 1 separately,
B is 1 or 2,
X independently represent separately direct key ,-CO-or-SO
2-,
R1 independently represents hydrogen separately, does not replace C
1-4Alkyl or by hydroxyl, halogen ,-SO
3H ,-OSO
3H or-the mono-substituted C of COOH
1-4Alkyl,
Alk independently represents C separately
2-4Alkylidene group;
W is independently expression separately
Alkylidene group
Alkylidene group
Or
M is 0 or 1 in the formula,
B
1Be C
2-6Alkylidene group, have-O-or-NR
1-C
2-6Alkylidene chain is by one or two hydroxyl or by the C of a carboxyl substituted
3-6Alkylidene group,
Or
N is 0,1,2,3 or 4 in the formula,
R
2Be hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H.
2. according to the application of claim 1, matrix wherein is the organization material that contains cotton or be made of cotton.
3. according to the application of claim 1, used staining agent or stamp agent are no metallic compound (1),
DK relates to the group of the diazonium composition of benzene or naphthalene in the formula,
KK relate to benzene, naphthalene or heterocyclic coupling composition group or can be by the group of the CH-acidic cpd of enolization,
Z is
Wherein b is 1, and this moment, Z passed through
Be bonded on diazonium or the coupling composition.
4. according to the application of claim 1, used staining agent or stamp agent are the free acid or the salt of no metallic compound (2),
Z is in the formula
T is 2 or 3,
R
6Be hydrogen, C
1-4Alkyl or C
1-4Alkoxyl group,
R
7Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-NHCOC
1-4Alkyl or-NHCONH
2,
R
6XHas R independently
6One of definition and
R
7XHas R independently
7One of definition.
5. according to the application of claim 1, used staining agent or stamp agent are no metallic compound (3a) or metal complexes (3b),
Z is in the formula
A is
Or
M independently represents 0 or 1 separately,
Q is 1,2 or 3,
R
17Be hydrogen, halogen, nitro, C
1-4Alkyl, C
1-4Alkoxyl group ,-COR
13,-SO
3H or-NHCOCH
3,
R
22Be OH, OCH
3Or NH
2And
R
13Be OH ,-OC
1-4Alkyl or NH
2, this metal complexes is free acid form or salt form, and is 1: 1 copper complex or a kind of symmetric or asymmetric 1: 2 chromic compound or 1: 2 cobalt complex.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3918653A DE3918653C2 (en) | 1988-06-14 | 1989-06-08 | Chromophore compound with heterocyclic reactive residue |
| GB8913469A GB2219804B (en) | 1988-06-14 | 1989-06-12 | Fibre-reactive dyestuffs |
| FR898907841A FR2632651B1 (en) | 1988-06-14 | 1989-06-12 | NOVEL TRIAZINIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS REACTIVE DYES |
| PT90839A PT90839B (en) | 1988-06-14 | 1989-06-12 | PROCESS FOR THE PREPARATION OF REACTIVE COLORS |
| CH2190/89A CH678186A5 (en) | 1988-06-14 | 1989-06-12 | |
| AT0144389A AT398978B (en) | 1988-06-14 | 1989-06-13 | CHROMOPHORIC COMPOUNDS WITH HETEROCYCLIC REACTIVE REMAIN, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR DYING OR PRINTING |
| EG28889A EG19298A (en) | 1988-06-14 | 1989-06-13 | Fibre-reactive dyestuffs |
| IT8948077A IT1231922B (en) | 1988-06-14 | 1989-06-13 | TRIAZINIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS REACTIVE DYES |
| JP1148516A JP2641943B2 (en) | 1988-06-14 | 1989-06-13 | Fiber reactive dye |
| ZA894538A ZA894538B (en) | 1988-06-14 | 1989-06-14 | Fibre-reactive dyestuffs |
| ES8902091A ES2016026A6 (en) | 1988-06-14 | 1989-06-14 | Reactive dyes with cyanodihalopyrimidyl and chlorotriazinyl groups |
| CN94105676A CN1056635C (en) | 1988-06-14 | 1994-05-13 | Fibre-reactive dyestuffs |
| HK134294A HK134294A (en) | 1988-06-14 | 1994-12-01 | Fibre-reactive dyestuffs |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3820149 | 1988-06-14 | ||
| CN94105676A CN1056635C (en) | 1988-06-14 | 1994-05-13 | Fibre-reactive dyestuffs |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109292 Division CN1028372C (en) | 1988-10-20 | 1989-12-14 | Fibre-reactive dyestuffs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1098121A CN1098121A (en) | 1995-02-01 |
| CN1056635C true CN1056635C (en) | 2000-09-20 |
Family
ID=36829953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94105676A Expired - Fee Related CN1056635C (en) | 1988-06-14 | 1994-05-13 | Fibre-reactive dyestuffs |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JP2641943B2 (en) |
| CN (1) | CN1056635C (en) |
| AT (1) | AT398978B (en) |
| CH (1) | CH678186A5 (en) |
| DE (1) | DE3918653C2 (en) |
| EG (1) | EG19298A (en) |
| ES (1) | ES2016026A6 (en) |
| FR (1) | FR2632651B1 (en) |
| GB (1) | GB2219804B (en) |
| HK (1) | HK134294A (en) |
| IT (1) | IT1231922B (en) |
| PT (1) | PT90839B (en) |
| ZA (1) | ZA894538B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9303266A (en) * | 1992-08-14 | 1994-03-08 | Sandoz Ag | COMPOUNDS AND THEIR SALTS OR MIXTURES OF FAIS COMPOUNDS OR SALTS, PROCESSES FOR THEIR PREPARATION, AND PROCESS FOR DYING OR STAMPING OF AN ORGANIC SUBSTRATE |
| DE4331386B4 (en) * | 1992-09-17 | 2006-02-16 | Clariant Finance (Bvi) Ltd. | Fiber-reactive monoazo dyes |
| GB2271776B (en) * | 1992-10-12 | 1996-01-17 | Sandoz Ltd | Fibre-reactive AZO dyestuffs |
| DE4304242A1 (en) * | 1993-02-12 | 1994-08-18 | Sandoz Ag | Phthalocyanine reactive dyes |
| DE19529853A1 (en) * | 1995-08-14 | 1997-02-20 | Bayer Ag | Aluminum phthalocyanine reactive dyes |
| DE19530198A1 (en) * | 1995-08-17 | 1997-02-20 | Sandoz Ag | Asymmetric triphendioxazine reactive dyes |
| DE19911195A1 (en) * | 1999-03-13 | 2000-09-14 | Clariant Gmbh | Water-soluble red acid dyes, their production and use |
| DE19911536A1 (en) | 1999-03-16 | 2000-09-21 | Clariant Gmbh | Red acid dyes for inkjet printing and paper coloring |
| WO2001072907A1 (en) * | 2000-03-28 | 2001-10-04 | Clariant International Ltd. | Composition for printing recording materials |
| BR0215015A (en) | 2001-12-19 | 2004-11-09 | Clariant Finance Bvi Ltd | Mono azo acid dyes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4007164A (en) * | 1968-03-19 | 1977-02-08 | Bayer Aktiengesellschaft | Azo dyestuffs containing 6-fluoro-pyrimidinyl 4-reactive group |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3362948A (en) * | 1961-05-19 | 1968-01-09 | Ici Ltd | Monoazo dyestuffs containing both triazine and pyrimidine groups |
| CH441563A (en) * | 1964-10-12 | 1967-08-15 | Sandoz Ag | Process for the production of reactive dyes |
| GB1247186A (en) * | 1968-02-27 | 1971-09-22 | Ici Ltd | New reactive dyestuffs |
| GB1250487A (en) * | 1968-05-30 | 1971-10-20 | ||
| GB1320921A (en) * | 1970-03-02 | 1973-06-20 | Ici Ltd | Fibre-reactive dyestuffs |
| GB1384749A (en) * | 1972-09-06 | 1975-02-19 | Ici Ltd | Reactive dyestuffs |
| GB1492414A (en) * | 1975-07-02 | 1977-11-16 | Ici Ltd | Fibre reactive monoazo dyes |
| DE2603670A1 (en) * | 1976-01-31 | 1977-08-04 | Bayer Ag | REACTIVE COLORS |
| DE2607028A1 (en) * | 1976-02-20 | 1977-08-25 | Bayer Ag | REACTIVE COLORS |
| DE2706417A1 (en) * | 1976-02-27 | 1977-09-01 | Sandoz Ag | MONOAZO COMPOUNDS CONTAIN A PYRIMIDINE REMAIN |
| DE2749597C2 (en) * | 1977-11-05 | 1986-04-24 | Bayer Ag, 5090 Leverkusen | Metal complex reactive dyes |
| DE3545555A1 (en) * | 1984-12-31 | 1986-07-10 | Sandoz-Patent-GmbH, 7850 Lörrach | Fibre-reactive monoazo compounds |
-
1989
- 1989-06-08 DE DE3918653A patent/DE3918653C2/en not_active Expired - Fee Related
- 1989-06-12 FR FR898907841A patent/FR2632651B1/en not_active Expired - Lifetime
- 1989-06-12 GB GB8913469A patent/GB2219804B/en not_active Expired - Lifetime
- 1989-06-12 CH CH2190/89A patent/CH678186A5/de not_active IP Right Cessation
- 1989-06-12 PT PT90839A patent/PT90839B/en not_active IP Right Cessation
- 1989-06-13 JP JP1148516A patent/JP2641943B2/en not_active Expired - Fee Related
- 1989-06-13 EG EG28889A patent/EG19298A/en active
- 1989-06-13 AT AT0144389A patent/AT398978B/en not_active IP Right Cessation
- 1989-06-13 IT IT8948077A patent/IT1231922B/en active
- 1989-06-14 ZA ZA894538A patent/ZA894538B/en unknown
- 1989-06-14 ES ES8902091A patent/ES2016026A6/en not_active Expired - Lifetime
-
1994
- 1994-05-13 CN CN94105676A patent/CN1056635C/en not_active Expired - Fee Related
- 1994-12-01 HK HK134294A patent/HK134294A/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4007164A (en) * | 1968-03-19 | 1977-02-08 | Bayer Aktiengesellschaft | Azo dyestuffs containing 6-fluoro-pyrimidinyl 4-reactive group |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2641943B2 (en) | 1997-08-20 |
| GB2219804B (en) | 1992-04-01 |
| ES2016026A6 (en) | 1990-10-01 |
| IT1231922B (en) | 1992-01-15 |
| GB8913469D0 (en) | 1989-08-02 |
| HK134294A (en) | 1994-12-09 |
| EG19298A (en) | 1996-02-29 |
| PT90839A (en) | 1989-12-29 |
| DE3918653A1 (en) | 1989-12-21 |
| JPH0234667A (en) | 1990-02-05 |
| DE3918653C2 (en) | 2003-01-16 |
| GB2219804A (en) | 1989-12-20 |
| CN1098121A (en) | 1995-02-01 |
| FR2632651B1 (en) | 1990-11-30 |
| PT90839B (en) | 1994-12-30 |
| AT398978B (en) | 1995-02-27 |
| ZA894538B (en) | 1991-02-27 |
| ATA144389A (en) | 1994-07-15 |
| FR2632651A1 (en) | 1989-12-15 |
| CH678186A5 (en) | 1991-08-15 |
| IT8948077A0 (en) | 1989-06-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: The British Virgin Islands Applicant after: Krairi Anter Finanace (BVI) Co., Ltd. Address before: Basel, Switzerland Applicant before: Sandoz Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SANDOZ CO., LTD. TO: CLERIDES ANTROBUS FINANCE(BVI)LTD. |
|
| CI01 | Publication of corrected invention patent application |
Correction item: Denomination of Invention Correct: Reactive dyes False: Reactive dyes Number: 5 Page: 70 Volume: 11 |
|
| ERR | Gazette correction |
Free format text: CORRECT: INVENTION NAME; FROM: FIBER REACTION DYE TO: FIBER REACTIVE DYES |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |