MX2008010584A - Agents for coloring keratin fibers - Google Patents
Agents for coloring keratin fibersInfo
- Publication number
- MX2008010584A MX2008010584A MXMX/A/2008/010584A MX2008010584A MX2008010584A MX 2008010584 A MX2008010584 A MX 2008010584A MX 2008010584 A MX2008010584 A MX 2008010584A MX 2008010584 A MX2008010584 A MX 2008010584A
- Authority
- MX
- Mexico
- Prior art keywords
- ethyl
- group
- phenyl
- amino
- methyl
- Prior art date
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 239000000835 fiber Substances 0.000 title claims abstract description 18
- 102000011782 Keratins Human genes 0.000 title claims abstract description 16
- 108010076876 Keratins Proteins 0.000 title claims abstract description 16
- 238000004040 coloring Methods 0.000 title claims abstract description 13
- 239000000987 azo dye Substances 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 200
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 113
- -1 N-R6 Chemical compound 0.000 claims description 105
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 99
- 239000000975 dye Substances 0.000 claims description 66
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 54
- 210000004209 Hair Anatomy 0.000 claims description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 34
- 125000000623 heterocyclic group Chemical group 0.000 claims description 24
- 239000007800 oxidant agent Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 125000005843 halogen group Chemical group 0.000 claims description 19
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 13
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 13
- 125000005842 heteroatoms Chemical group 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Chemical group 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000001590 oxidative Effects 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 8
- 125000002837 carbocyclic group Chemical group 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 239000000982 direct dye Substances 0.000 claims description 8
- 125000004430 oxygen atoms Chemical group O* 0.000 claims description 8
- 125000004434 sulfur atoms Chemical group 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 238000004043 dyeing Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 125000004001 thioalkyl group Chemical group 0.000 claims description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- RZVHIXYEVGDQDX-UHFFFAOYSA-N Anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims 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 claims description 2
- 239000001000 anthraquinone dye Substances 0.000 claims description 2
- 239000000981 basic dye Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000001005 nitro dye Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 7
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims 3
- 101710021213 crc-2 Proteins 0.000 claims 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 2
- 230000000996 additive Effects 0.000 claims 2
- GAMOILWTJHUYFX-UHFFFAOYSA-N 4-methyl-1$l^{6},2,4-benzothiadiazine 1,1-dioxide Chemical compound C1=CC=C2N(C)C=NS(=O)(=O)C2=C1 GAMOILWTJHUYFX-UHFFFAOYSA-N 0.000 claims 1
- 239000000980 acid dye Substances 0.000 claims 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- PDTFCHSETJBPTR-UHFFFAOYSA-N nitrooxy(phenyl)mercury Chemical compound [O-][N+](=O)O[Hg]C1=CC=CC=C1 PDTFCHSETJBPTR-UHFFFAOYSA-N 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 53
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 15
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000010168 coupling process Methods 0.000 description 12
- 238000005859 coupling reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005956 quaternization reaction Methods 0.000 description 12
- 125000005999 2-bromoethyl group Chemical group 0.000 description 11
- 230000001808 coupling Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 10
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-Methylimidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 9
- VNHIWLRYPBSACZ-UHFFFAOYSA-N N-(2-bromoethyl)-N-ethylaniline Chemical compound BrCCN(CC)C1=CC=CC=C1 VNHIWLRYPBSACZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 7
- 239000002453 shampoo Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 102000014961 Protein Precursors Human genes 0.000 description 5
- 108010078762 Protein Precursors Proteins 0.000 description 5
- 239000000118 hair dye Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- JDRSMPFHFNXQRB-CMTNHCDUSA-N (2R,4S,6R)-2-decoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCCCCCCCO[C@@H]1O[C@H](CO)C(O)[C@H](O)C1O JDRSMPFHFNXQRB-CMTNHCDUSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N Sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006149 azo coupling reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229940073499 decyl glucoside Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229920005615 natural polymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- RAIPHJJURHTUIC-UHFFFAOYSA-N Aminothiazole Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 3
- PGSADBUBUOPOJS-UHFFFAOYSA-N Neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000037308 hair color Effects 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VJHTZTZXOKVQRN-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine Chemical compound NC1=NC=NS1 VJHTZTZXOKVQRN-UHFFFAOYSA-N 0.000 description 2
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical compound NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N 4H-1,2,4-triazol-3-amine Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Trimethylglycine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L disodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001888 polyacrylic acid Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- UVQWEDPLIFNWSH-XFFZJAGNSA-N (4Z)-3-hydroxy-4-(1,3-thiazol-2-ylhydrazinylidene)cyclohexa-2,5-dien-1-one Chemical compound OC1=CC(=O)C=C\C1=N\NC1=NC=CS1 UVQWEDPLIFNWSH-XFFZJAGNSA-N 0.000 description 1
- MLVKRZHLEQPZTP-UHFFFAOYSA-N 1-(3-aminopropylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NCCCN MLVKRZHLEQPZTP-UHFFFAOYSA-N 0.000 description 1
- QDXQAOGNBCOEQX-UHFFFAOYSA-N 1-methylcyclohexa-1,4-diene Chemical compound CC1=CCC=CC1 QDXQAOGNBCOEQX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1H-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 1
- KUWRLKJYNASPQZ-UHFFFAOYSA-N 1H-imidazol-3-ium-2-amine;sulfate Chemical compound OS(O)(=O)=O.NC1=NC=CN1.NC1=NC=CN1 KUWRLKJYNASPQZ-UHFFFAOYSA-N 0.000 description 1
- KXZRECGEDVBJPM-UHFFFAOYSA-N 2,3,4,5-tetrabromophenol Chemical compound OC1=CC(Br)=C(Br)C(Br)=C1Br KXZRECGEDVBJPM-UHFFFAOYSA-N 0.000 description 1
- CINOBFJUMNAUFJ-UHFFFAOYSA-N 2,4-dinitronaphthalen-1-ol;sodium Chemical compound [Na].C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CINOBFJUMNAUFJ-UHFFFAOYSA-N 0.000 description 1
- VPRLWNAMKBZKRR-UHFFFAOYSA-N 2-(4-nitroanilino)ethanol Chemical compound OCCNC1=CC=C([N+]([O-])=O)C=C1 VPRLWNAMKBZKRR-UHFFFAOYSA-N 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N 2-Pentanone Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- NJZCRXQWPNNJNB-UHFFFAOYSA-N 2-[2-nitro-4-(trifluoromethyl)anilino]ethanol Chemical compound OCCNC1=CC=C(C(F)(F)F)C=C1[N+]([O-])=O NJZCRXQWPNNJNB-UHFFFAOYSA-N 0.000 description 1
- ADCWDMYESTYBBN-UHFFFAOYSA-N 2-[N-(2-hydroxyethyl)-3-methyl-4-[(4-nitrophenyl)diazenyl]anilino]ethanol Chemical compound CC1=CC(N(CCO)CCO)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 ADCWDMYESTYBBN-UHFFFAOYSA-N 0.000 description 1
- CYCRZLRIJWDWCM-UHFFFAOYSA-N 2-aminonaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(N)=CC(=O)C2=C1 CYCRZLRIJWDWCM-UHFFFAOYSA-N 0.000 description 1
- IRTLROCMFSDSNF-UHFFFAOYSA-N 2-phenyl-1H-pyrrole Chemical group C1=CNC(C=2C=CC=CC=2)=C1 IRTLROCMFSDSNF-UHFFFAOYSA-N 0.000 description 1
- OXEIXRNCCWLEFR-UHFFFAOYSA-N 3-(pyridin-3-yldiazenyl)pyridine-2,6-diamine Chemical compound NC1=NC(N)=CC=C1N=NC1=CC=CN=C1 OXEIXRNCCWLEFR-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-Aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- JSHLOPGSDZTEGQ-UHFFFAOYSA-N 3-methoxy-4-phenylmethoxybenzaldehyde Chemical compound COC1=CC(C=O)=CC=C1OCC1=CC=CC=C1 JSHLOPGSDZTEGQ-UHFFFAOYSA-N 0.000 description 1
- XYTUTNQRQLAZLK-UHFFFAOYSA-N 4,5-dimethyl-1,3-thiazol-2-amine;hydrochloride Chemical compound Cl.CC=1N=C(N)SC=1C XYTUTNQRQLAZLK-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-Aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- 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 1
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Abstract
The present invention relates to agents for coloring keratin fibers which comprise at least one cationic azodye of the general formula (I). (I)
Description
AGENTS FOR THE COLORATION OF KERATIN FIBERS FIELD OF THE INVENTION
The present invention relates to agents for the coloring of keratin fibers, for example, wool, skins and, in particular, human hair, which comprise cationic azo dyes.
BACKGROUND OF THE INVENTION
For the treatment of the color change of the keratin fibers two coloration methods are usually applied. In the first method, the coloration is obtained with the dyes known as oxidative or permanent using a mixture of various developer substances and coupling substances and an oxidizing agent. If necessary, dyes known as direct (non-oxidative) dyes can be added to this method to cover the result of coloring or to produce special color effects. In the second method only direct dyes are used which are applied to the fibers in a suitable carrier mass. This method is easy to use, exceptionally soft and is characterized by producing little damage to the keratin fibers. The direct dyes used herein must meet various requirements. For example, they must be toxicologically and dermatologically acceptable and must be suitable to obtain colorations of the desired intensity which, among other things, also require adequate solubility in water. In addition, the colorations obtained must have adequate resistance to light, acid fastness and must be resistant to friction.
However, in comparison with oxidative colorations, non-oxidative colorations are generally less durable and provide a less even color. In addition, direct dyes generally can not "lighten" the hair, since many of these are not resistant to the oxidizing agents necessary for rinsing nor to the necessary pH that is equal to or greater than 9. The patents WO 95/01722 A1 and WO 97/20545 A1 describe dyes comprising cationic azo dyes, in which the positive charge is delocalized in the conjugate system. Azo cationic dyes, in which the cationic charge is located in a side chain, are known for synthetic dye fibers, as described in EP 56578 A1, for example. DE 10118271 A1 describes among other cationic disazodiazole derivatives and their use in hair dyes.
BRIEF DESCRIPTION OF THE INVENTION
Surprisingly, it has now been discovered that special cationic azo dyes can stain keratin fibers intensively and durably, or are stable to oxidation and, therefore, can also be used in oxidation coloring systems.
DETAILED DESCRIPTION OF THE INVENTION
Therefore, the present invention provides: (a) an agent for the non-oxidative coloring of keratin fibers, in particular, human hair;
an agent for simultaneously lightening and dyeing keratin fibers, in particular human hair, which in addition to the dye of Formula (I) comprises an oxidizing agent; and an oxidative dye for keratin fibers, in particular human hair, based on at least one oxidation dye precursor; wherein the agents (a), (b) and (c) are characterized by comprising at least one azo dye of the general Formula (I);
wherein X is oxygen, sulfur, N-R3, C-R4; And it is C-R5, nitrogen, N-R6, sulfur or oxygen; Z is C-R7 or nitrogen; provided that the heterocycle of Formula (I) comprises at least two and at most three heteroatoms, wherein the heterocycle has at most one sulfur atom or one oxygen atom; n is an integer from 1 to 6; R1 is hydrogen, a saturated or unsaturated alkyl group (Ci-Ci2), a (CrC ^ -alkyl group substituted by a halogen atom (F, Cl, Br, I), a hydroxyalkyl group (C2-Ci2), an aminoalkyl group (CrC12), a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group;
R2, R4, R5 and R7 can be identical or different and, independently of one another, are hydrogen, a halogen atom (F, Cl, Br, I), a saturated or unsaturated alkyl group (Cr12), an alkyl group (CC ^) substituted by a halogen atom (F, Cl, Br, I), a hydroxyl group, a hydroxyalkyl group (Ci-C 2), an alkoxy group (Ci-C12), a thioalkyl group (CrC12), a cyano group , a nitro group, an amino group, an alkylamino group (CrC12), a dialkylamino group (C1-C12), a carboxylic acid group, a C (0) 0- (CC 2) alkyl group, a phenyl group substituted or not substituted C (0) 0, a substituted or unsubstituted phenyl group or a naphthyl group, a substituted or unsubstituted heteroaryl group; or when Y and Z are C-R5 and C-R7, the radical groups R5 and R7 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; or when X and Y are C-R4 and C-R5, the radical groups R4 and R5 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; R3 and R6 can be identical or different, and independently of each other, they are a saturated or unsaturated (C C12) alkyl group, an alkyl group (CrC12) substituted with a halogen atom (F, Cl, Br, I), a group hydroxyalkyl (C2-C12), an aminoalkyl group (Ci-Ci2), a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; Q + represents a 4- to 6-membered aromatic or non-aromatic heterocyclic quaternary ammonium group, substituted or unsubstituted, which may contain other heteroatoms such as nitrogen, sulfur or oxygen, with the proviso that the cationic heterocycle comprises at most three heteroatoms, where the heterocycle has at most one sulfur atom or one oxygen atom;
or the radical group R1, together with Q +, can form a 5- or 6-membered unsaturated, substituted or unsubstituted cationic heterocyclic ring system; the anion An- is an organic or inorganic acid anion, such as, for example, halogen anions (chloride, bromide, iodide), sulfate, acetate, formate, propionate, lactate, perchlorate, hexafluorophosphate, tetrafluoroborate or tetraphenylborate. Among the aforementioned compounds with the formula (I), those in which Q + represents a 5- to 6-membered aromatic or non-aromatic heterocyclic quaternary ammonium group with the formula (lia a llg) are preferred.
(He) (llf) (llg) in which R is a saturated or unsaturated alkyl group (C ^ C ^), R 'can be hydrogen, a halogen atom (F, Cl, Br, I), a group saturated (unsaturated) alkyl (CrC12), an alkyl group (CrC12) substituted by a halogen atom (F, Cl, Br, I), a hydroxyl group, an alkyl group (CrC12) -hydroxyl, an alkyl group C12), a cyano group, a nitro group, an amino group, an alkylamino group (CrCi2), a dialkylamino group (Ci-C12), a carboxylic acid group, a C (0) 0- (C C12) alkyl group, a substituted or unsubstituted phenyl group C (0) 0, a phenyl group or a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heteroaryl group. Particularly preferred compounds of the general formula (I) are: 1 - [2- (ethyl) {4- [1, 3-thiazol-2-yl-diazyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide; 3-methyl-1 -
[2- (methyl. {4- [1, 3-thiazol-2-yl] zenyl] phenyl} amino} ethyl] -1 H-imidazol-3-nio bromide; 1- [2 - ((2-hydroxyethyl). {4- [1, 3-thiazol-2-ildiazenyl] phenol] .amino) ethyl] -3-methyl-1H -imidazole-3-nio bromide; 1 - [2- (et.l. {3-metl-4- [1, 3-thiazol-2-ildiazenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3 -thromium bromide; 1 -. { 2-[. { 3-chloro-4- [1,3-thiazol-2-ildiazenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H -amidazole-3-n-bromide; 1- [2- (ethyl { 4 - [(4-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3- Nio bromide; 1- [2- (ethyl. {3-methyl-4 - [(4-methyl-1,3-thiazol-2-yl) d-acyl] phenol. amino) -ethyl] -3-methyl-1 H-imidazo bromide; 1 -. { 2-[. { 3-Chloro-4 - [(4-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-n-bromide; 1 - [2- (ethyl { 4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3 -thromium bromide; 1 - [2- (ethyl { 3-methyl-4 - [(5-methyl-1, 3-thiazol-2-yl) diacenyl] phenyl} amino) -etl] -3- methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 3-Chloro-4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] phenol} (ethyl) amino] etl} -3-methyl-1 H-imidazole-3-n-bromide; 1-. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) d-acenyl] -phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(4,5-D-methyl-1,3-thiazol-2-yl) diacell] -3-methylphenyl} (ethyl) -amino] etl} -3-methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 3-Chloro-4 - [(4,5-dimethyl-1,3-thiazol-2-yl) d-acyl] phenyl} (eth) amine] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl { 4 - [(5-nitro-1,3-thiazol-2-yl) diacenyl] phen.l.] Amino) ethyl] -3-methyl-1 H- imidazole-3-bromide; 1-. { 2-[. { 4 - [(4-Chloro-5-n-tho-1, 3-thiazol-2-yl) diacenyl] phenyl} (ethyl) -amino] ethyl} -3-methyl-1 H -amdazole-3-n-bromide; 1 - [2- (ethyl { 4 - [(4-phenyl-1,3-thiazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3- child bromide; 1 -. { 2-[. { 4- [1,3-benzothiazol-2-ildiazenyl] -phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl { 4 - [(6-nitro-1,3-benzothiazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3 child bromide; 1 - [2- (ethyl { 4 - [(4,6-dinitro-1,3-benzothiazol-2-yl) d-acyl] phenyl] -amino) ethyl] -3-methyl-1H -imidazole-3-nio bromide; 1- [2- (ethyl { 4 - [(5,6-dinitro-1,3-benzothiazol-2-yl) d-acenyl] -phenyl} amino) ethyl] -3- methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl. {4- [1 H- [1,3] thiazolo [5,4-f] indazol-6-diallyzenyl] phen.l.] Amino) ethyl] -3 -methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(5-chloro [1,3] thiazolo [5,4-b] pyridin-2-yl) diacenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio
bromide; 1-. { 2- [ethyl (4- { [5- (methoxy) [1, 3] thiazolo [5,4-b] pyridin-2-yl] diacenyl} phenyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (etl { 4- [1, 3-thiazol-2-ildiazenyl] phenyl} amino) ethyl] -2,3-dimethyl-1 H-imidazol-3-nio bromide; 1 - [2- (ethyl { 4 - [(4-methyl-1,3-thiazol-2-yl) d-acyl] phenyl} amino) etl] -2,3-d Methyl-1 H-imidazole-3-n-bromide; 1- [2- (ethyl { 4 - [(5-methyl-1,3-thiazole-2-yl) d-acetyl] phen.l.] Amino) etl] -2.3- dimethyl-1 H-imidazole-3-nio bromide; 1-. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diaclen] phenyl} - (ethylene) amine] ethyl} -2,3-dimethyl-1 H-imidazole-3-nio bromide; 1 - [3- (ethyl. {4- [1, 3-thiazole-2-idol] phenyl] -amino) propyl] -3-methyl-1H-imidazole-3- child bromide; 1 - [2- (ethyl. {4- [1, 3-thiazol-2-yldiazenyl] phenyl} amino) etl] pyridinium bromide; 1 - [2- (ethyl { 4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] -phenyl} amino) ethyl] pyridinium bromide; 1- [2- (ethyl { 4 - [(4-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} amino) ethyl] -pyridinium bromide; 1-. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] phenyl} - (ethyl) amino] -ethyl} pyridinium bromide; 1- [2- (ethyl. {3-methyl-4- [1,3-thiazol-2-yl-diazyl] -phenyl} amino) ethyl] pyridinium bromide; 1-. { 2-[. { 3-chloro-4- [1,3-thiazol-2-ildiazenyl] phenyl} (ethyl) amino] ethyl} pyridinium bromide; 1- [2- (ethyl { 4 - [(5-nitro-1,3-thiazol-2-yl) diacenyl] phenyl] -amino) ethyl] pyridinium bromide; 1- [2- (ethyl { 3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diacenyl] phenyl} amino) -ethyl] pyridinium bromide; 1-. { 2-[. { 3- (dimethylamino) -4- [1,3-thiazol-2-ildiazenyl] phenyl} (ethyl) amino] ethyl} pyridinium bromide; 1-. { 2-[. { 3- (dimethylamino) -4 - [(5-nitro-1,3-thiazol-2-yl) diacenyl] -phenyl} (ethyl) amino] -ethyl} pyridinium bromide; 4- [2- (ethyl. {4- [1, 3-thiazol-2-ildiazenyl] phenyl} amino) ethyl] -4-methylmorpholine-4-nio bromide; 4-. { 2-[. { 4- [1,3-benzothiazol-2-ildiazenyl] phenyl} - (ethyl) amino] ethyl} -4-methylmorpholine-4-nio bromide; 1 - [2- (ethyl. {4- [1, 3-thiazol-2-yl-diazyl] -phenyl} amino) ethyl] -1-methylpiperidinium bromide; 4- [2- (etiI { 4- [1, 3-thiazol-2-ildiazenyl] phenyl} amino) ethyl] -1,1-dimethylpiperazine-1-nio bromide; 1- [2- (ethyl { 4- [1, 3,4-thiadiazol-2-ildiazenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide; 1- [2- (ethyl { 4 - [(5-phenyl] -1,4,4-thiadiazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1H- imidazole-3-nio bromide; 1- [2- (ethyl. {4- [1,4-thiadiazol-2-idiazenyl] phenyl]} amino) -ethyl] pyridinium bromide; 1- [2- (ethyl { 4 - [(5-phenyl-1, 3,4-thiadiazol-2-yl) diacenyl] phenyl} amino) ethyl] -bromidinium bromide; 1- [2- (ethyl { 4- [1, 2,4-thiadiazol-2-
ildiazenil] phenyl} amino) ethyl] -3-methyl-1 H-imidazol-3-nio bromide; 1- [2- (et.l { 4 - [(3-phenyl-1, 2,4-thiadiazol-5-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H -imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(3-chloro-1, 2,4-thiadiazol-5-yl) diacenyl] phenyl} (ethyl) amino] -ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1- [2- (ethyl) {4- [1, 2,4-thiazol-5-idol] phenyl] phenyl] -amino) pyridinium bromide; 1- [2- (ethyl { 4 - [(3-phenyl-1, 2,4-thiadiazol-5-yl) diacenyl] phenyl} amino) ethyl] pyridinium bromide; 2- (ethyl. {4- [1 H-1, 2,4-triazol-5-ildiazenyl] -phenyl} amino) -3-methyl-1 H-imidazol-3-nio bromide; 1- [2- (ethyl { 4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3 child bromide; 1 - [2- (ethyl { 3-methyl-4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole -3-bromide; 1 -. { 2-[. { 3-Chloro-4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl] phenyl} - (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide. The dyes of the formula (I) are present in the dye according to the invention in an amount varying, preferably, from 0.01 to 10% by weight and, in particular, from 0.1 to 8% by weight. To extend the color palette, the dye (a) according to the invention can, in addition to the dyes of the formula (I), also comprise known direct dyes from the group consisting of nitro dyes, azo dyes, anthraquinone dyes, dyes Triphenylmethane and basic dyes or acids and natural direct dyes, alone or mixed together. The dye (b) according to the invention, which comprises an oxidizing agent, preferably hydrogen peroxide, can, in addition to the dyes of the general formula (I), also comprise direct dyes of stable oxidation, such as, for example, 3- (2 ', 6'-diaminopyridyl-3'-azo) pyridine (= 2,6-diamino-3 - ((pyridin-3-yl) azo) pyridine), N, N-di (2-hydroxyethyl) -3-methyl-4 - ((4-nitrophenyl) azo) aniline (Disperse Red 17, CU 1210), 3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenylphenazinium chloride (CU 1050), 4 - (2-thiazolylazo) -resorcinol, 4 - ((4-phenylamino) azo) sodium salt of acid
benzosulfonic (Orange IV), 1 - ((3-aminopropyl) amino) -9,10-anthracenedione (HC Red No. 8), 3 ', 3", 4,5,5', 5", 6,7- octabromophenol sulfonephthalein (blue tetrabromophenol), 1 - ((4-amino-3,5-dimethylene) (2,6-dichlorophenol) methylene) -3,5-d-methyl-4-yl! m -no-2,5-cyclohexadiene-phosphoric acid (1: 1) (basic Blue 77), 3 ', 3", 5') 5" -tetrabromo-m-cresol sulfonephthalein, 2,4-dinitro-1 - Naphthol-7-Sulfonic acid disodium salt (1, Cl 10316), 4- [2'-hydroxy-1'-naphthyl) azo] Sodium salt of benzosulfonic acid (Orange acid 7, CU 5510), 3 ', 6' -dihydroxy-2 ', 4', 5 ', 7'-tetraiodospiro [isobenzofuran-1 (3H), 9' - (9H) xanthene] -3-one disodium salt (acid red 51, CI45430), 6-hydroxy- 5 - ((2-methoxy-5-methyl-4-sulfophenyl) azo) -2-naphthalenesulfonic acid disodium salt (FD &C Red 40, CU 6035), sodium 2,4-dinitro-1-naphthol salt ( Acid yellow 24; CU 0315), 2 ', 4', 5 ', 7'-tetrabromo-4,5,6,7-tetrachloro-3', 6'-dihydroxyspiro (isobenzofuran-1 (3H), 9'- [9H] xanthene] -3-one disodium salt (Acid Red) gone 92; CI45410), 4- (2-hydroxy-1-naphthylazo) -3-methylbenzenesulfonic acid sodium salt (Acid Orange 8, CI15575), 2-amino-1,4-naphthalenedione, dithizone (1,5-diphenylthiocarbazone) ), N - ((2-hydroxyethyl) -2-nitro-4-trifluoromethyl) aniline (HC Yellow 13), N- (2-hydroxyethyl) -4-nitroaniline and 4-chloro-N- (2,3-dihydroxypropyl) ) -2-nitroaniline, 1-methyl-4 - ((methylphenylhydrazono) methyl) pyridinium methylsulfate (Basic Yellow No. 87), 3 - ((4,5-dihydro-3-methyl-5-oxo-1-phenyl) -1 H-pyrazol-4-yl) azo) -N, N, N-trimethylbenzenmonium chloride, 3 - [(3-methyl-5-hydroxy-1-phenyl-1 H -pyrazol-4-yl) azo] -trimethylammonium benzene chloride (Basic Yellow No. 57), 2 - ((4-aminophenyl) azo) -1,3-dimethyl-1 H-imidazole-3-niochloride (Basic Orange No. 31), 1-4 dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1, 2,4-triazolium chloride (Basic red No. 22, CU 1055), 2 - ((4- (dimethylamino) -phenyl) azo) -1, 3-dimethyl-1 H-imidazolium chloride (Basic red No. 51), 1,4-dimethyl-5 - [[4- [methyl (phenylmethyl) amino] -phenyl] azo] -1, 2, 4-triazolium bromide (Basic red No. 46), N, N, N-trimethyl-3-. { [4- (methylamino) -9,10-dioxo-9,10-dihydro-1-anthracenyl] amino} Propanamine-1-methylsulfate, N, N-dimethyl-3-. { [4- (methylamino) -9,10-dioxo-9,10-dihydro-1 -
anthracite] amino} -n-propyl-1-propanaminium chloride and N, N-dimethyl-3-. { [4- (methylamino) -9,10-dioxo-9,10-dihydro-1-anthracenyl] amino} -n-propyl-1-propanaminium bromide. The total content of the additional dyes in the dye according to the invention is from about 0.01 to 15% by weight, in particular from 0.1 to 12% by weight. The oxidation dye (c) according to the invention, which is mixed before application with an oxidizing agent (in particular hydrogen peroxide or its additional compounds) or oxidized by atmospheric oxygen, comprises, in addition to the dyes of the General formula (I), oxidation dye precursors and, if necessary, one or more of the aforementioned additional direct dyes, provided they are stable for the oxidizing agent used. Suitable oxidation dye precursors are developer substances such as aromatic 1,4-diamines, 4-aminophenol derivatives or pyrazole derivatives, coupling agent substances such as aromatic 1,3-diamines, 3-aminophenol derivatives, polyphenols or naphthols. and auto-coupling compounds. The total amount of oxidation dye precursors present in the dye (c) according to the invention is from about 0.01 to 12% by weight, in particular, from about 0.2 to 6% by weight. To increase the color intensity, if necessary, conventional carriers used in cosmetic systems can be added. Suitable compounds are described, for example, in DE 196 18 595 A1, to which reference is made here explicitly. Particularly suitable carriers are, for example, benzyl alcohol, vanillin and isovainillin. For coloring, the dyes described above are applied in a carrier mass of the appropriate color.
The dye (a), (b) or (c), according to the invention, can also comprise all the traditional additives known for these preparations, for example, essential oils, complexing agents, waxes, preservatives, thickeners, antioxidants. , alginates, guar gum, hair care substances, such as, for example, cationic polymers or lanolin derivatives, or anionic, nonionic, amphoteric or cationic surfactants. Preference is given to the use of amphoteric or nonionic surfactants, for example betaine surfactants, propionates and glycinates. The constituents mentioned above are used in the usual amounts for these purposes, for example, the surfactants are used at a concentration of 0.1 to 30% by weight, and the care substances are used at a concentration of 0.1 to 5% by weight. weight. The dye (a), (b) or (c) according to the invention, especially if it is a hair colorant, can be present in the form of powder or granules which are dissolved before application in an aqueous preparation or aqueous, or in the form of an aqueous or aqueous alcoholic solution, a cream, a gel, an emulsion or an aerosol foam, wherein the colorant can be formulated as a single-component or multiple-component preparation, for example, in form of a two-component preparation in which the particular dye derivative of the general Formula (I) is packaged independently of the other constituents and the ready-to-use dye is prepared directly before application by mixing the two components. The dye (a), (b) or (c) according to the invention generally has a pH of about 2 to 11, preferably about 5 to 10. Both the acids and the organic and inorganic bases are suitable for adjusting the pH according to the invention.
Depending on the intended use, the dye according to the invention can be used with one or more synthetic oxidizing agents, for example, hydrogen peroxide or a salt or adduct thereof, as well as persulfates such as sodium persulfate, potassium persulfate or persulfate of ammonium (clarifying, oxidation dyes) or without a synthetic oxidizing agent (non-oxidizing dyes; oxidation by air). In addition, the dye may contain an ammonium carbonate, for example ammonium carbonate or ammonium hydrogen carbonate, or an amino acid or a salt thereof, for example sodium glycinate. If required, the agent for dyeing keratin fibers before application is mixed with an oxidizing agent. Suitable oxidizing agents are, in particular, hydrogen peroxide or its addition compounds on urea, melamine, sodium borate or sodium carbonate in the form of an aqueous solution of 1 to 12% strength, preferably from 3 to 9% . In the case of agents with simultaneous clarification or decolouration, depending on the dye corresponding to the formula (I) used, it is also possible to add persulfates, for example, ammonium persulfate, potassium persulfate or sodium persulfate. The weight ratio between the mass of the color carrier and the oxidizing agent herein is preferably from about 5: 1 to 1: 3, in particular from 1: 1 to 1: 2. Larger amounts of oxidizing agent are used especially at higher concentrations of oxidative dye precursors in the dye, or if greater decolorization of the keratin fibers (especially the hair) is intended at the same time. The dye according to the invention is generally used by applying to the hair a quantity of dye sufficient to dye the hair, of about 30 to 200 grams based on the length of the hair, allowing the dye to act from about 15 to 50 degrees Celsius for about 1 to 60 minutes, preferably 5 to 30 minutes, then thoroughly rinsing the hair with
water and, optionally, washing it with a shampoo or treating it later with a hair conditioning composition to finally dry it. Further, if oxidizing agents are not added to the dye mass, the dye described above may comprise natural or synthetic polymers or modified natural polymers commonly used in cosmetic compositions and, thereby, coloring of the hair occurs and at the same time fix the color Generally, these compositions are known as dye fixative compositions or color setting compositions. Among the synthetic polymers used in cosmetics for this purpose, mention may be made, for example, of polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds, such as polyacrylic acid or polymethacrylic acid, basic polymers of polyacrylic acid esters, polymethylacrylic acid and aminoalcohols. , for example, salts or the quaternization products thereof, polyacrylonitrile, polyvinyl acetates, and copolymers of such compounds, for example, polyvinylpyrrolidone-vinyl acetate; while the natural polymers or modified natural polymers that can be used are, for example, chitosan (deacetylated chitin) or chitosan derivatives. The aforementioned polymers can be present in the dye (a) according to the invention in customary quantities for such agents, in particular in an amount of about 1 to 5% by weight. The pH of the dye fixing composition or of the color according to the invention is preferably from about 4 to 10. The hair dye with the additional fixative is applied in the known and customary manner by moistening the hair with the composition fixing, modeling (styling) the hair in the desired way and, finally, drying it. The dye with cationic azo dyes corresponding to the
Formula (I) allows, among others, a simple and gentle coloring of hair with varying degrees of damage (eg, the recoloration of hair sections that have already been oxidatively colored); the color-carrying mass without oxidizing agent (pure or mixed with an acidic, neutral or basic aqueous diluent) is applied to previously damaged hair sections (eg, the tips), while the mass carrying the color with The oxidizing agent is applied to the hair sections with little or no previous damage (eg, the growth of new hair). The aqueous component used for dilution may comprise the conventional additives mentioned above for solutions, creams, emulsions or gels. This process allows to obtain colorations suitable for the nature of the hair that are characterized by a uniform pairing between the roots and the tips that can not be obtained when conventional oxidative hair dyes are used, since an oxidizing agent is always needed to couple the hair. dye precursors. The dye according to the invention allows a coloration of keratin fibers, in particular of human hair, with a strong intensity and brightness of color, good color uniformity between damaged and undamaged hair (such as, for example , between the ends of the hair and the new hair growth), very good durability (firmness in the wash), hair benefits and variable application options with and without oxidizing agents. The dyes of the formula (I) can be prepared analogously to the processes of preparation, such as, for example, in a one-step process, through the diazotization of 1,3-thiazole-2-amine, 1 H- imidazole-2-amine, 1, 2,4-thiadiazol-5-amine, 1, 3,4-thiadiazol-2-amine, 4H-1, 2,4-triazol-3-amine, or similar and coupling with cationic aniline derivatives, or in a 2 step process through diazotization of 1,3-thiazole-2-amine, 1 H-imidazol-2-amine, 1, 2,4-thiadiazol-5-amine, 1, 3,4-thiadiazol-2-amine,
4H-1, 2,4-triazole-3-amine, or the like, and coupling with bromoalkyl-aniline derivatives, followed by quaternization with heterocycles. Some dyes of Formula (I) are known as textile dyes. The following examples illustrate the object of the invention in more detail without being limited thereto.
Examples
Example 1 :
Example 1 a: 1-f2-r (4-f (4,5-dimethyl-1,3-thiazole-2-ihdiacenyl-phenyl) (ethylaminoletyl-3-methyl-1 H-imidazole-3-nio bromide Step 1: Coupling azo (standard procedure) 2.0 g (12.1 mmol) of 2-amino-4,5-dimethyl-1,3-thiazole hydrochloride are dissolved in a mixture containing 50 ml of acetic acid and 1.8 g of concentrated sulfuric acid while the temperature rises to 30 ° C. The suspension is cooled to 15 ° C. followed by a dropwise addition of 5.8 g (18.1 mmol) of 40% aqueous nitrosylsulfuric acid and stirred for 2 hours. 2.80 g (12.1 mmol) of N- (2-bromoethyl) -N-ethylaniline in a mixture of 15 ml of acetic acid, 1.4 g hydrochloric acid (32%) and 20 g of ice. of diazonium previously prepared to this solution so that the temperature did not exceed 5 ° C. The reaction mixture was stirred further for 1 hour at 5 ° C and then for 2 hours at room temperature. The pH value is adjusted to 4 by adding an appropriate amount of 30% aqueous sodium hydroxide. The resulting precipitate is filtered, washed with water and dried under vacuum at 40 ° C. After recrystallization from methanol / water, 3.02 g (68%) were obtained
in theory) of N- (2-bromoethyl) -4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] -N-ethylaniline as red crystals . H NMR (300 MHz. DMSO): d = 7.76 (d, J = 9.0, 2H, H (3) and H (5) -phenyl); 6.89 (d, J = 9.0, 2H, H (2) and H (6) -phenyl); 3.84 (t, J = 6.9, 2H, CH2); 3.65 (t, J = 6.9, 2H, CH2); 3.58 (q, J = 6.9, 2H, CH2); 2.37 (s, 3H, CH3); 2.32 (s, 3H, CH3); 1.16 (t, J = 6.9, 3H, CH3). Step 2: Quaternization (standard procedure) Dissolve 0.5 g (1.36 mmol) N- (2-bromoethyl) -4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] -N-ethylaniline in 10 mL of acetonitrile followed by the addition of 5.3 g (65 mmol) of 1-methyl-1 H-imidazole. The reaction mixture is heated at 80 ° C overnight. After cooling to room temperature, the precipitate formed is filtered, washed with acetonitrile and dried under vacuum at 40 ° C. 0.49 g (82% in theory) of 1- were obtained. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide as red crystals. 1 H NMR (300 MHz. DIVISO): d = 9.17 (s, 1 H, H (2) -imidazole); 7.85 (s, 1 H, imidazole); 7.74 (d, J = 9.3, 2H, H (3) and H (5) -phenyl); 7.71 (s, 1 H, imidazole); 6.89 (d, J = 9.3, 2H, H (2) and H (6) -phenyl); 4.45 (t, J = 6.0, 2H, CH2); 3.89 (t, J = 6.0, 2H, CH2); 3.83 (s, 3H, N + CH3); 3.44 (q, J = 6.9, 2H, CH2); 2.38 (s, 3H, CH3); 2.32 (s, 3H, CH3); 1.10 (t, J = 6.9, 3H, CH3).
CHN analysis:
(Ci9H25N6S * Br)% C% H% N% S Calculated 50.78 5.61 18.70 7.14 Found 50.80 5.57 18.84 7.27
Example 1b: 1-r 2 - (ethyl (4-1,3-thiazol-2-ildiazeninophenyl) amino) ethyl-3-methyl-1 H-imidazole-3-
Nio bromide Analogously to the procedure described in example 1a, by coupling azo of 2-amino-1,3-thiazole with N- (2-bromoethyl) -N-ethylaniline to give N- (2-bromoethyl) -N ethyl-4- [1, 3-thiazol-2-ildiazenyl] aniline with a yield of 73%, followed by quaternization with 1-methyl-1 H-imidazole to give 1- [2- (ethyl. 4- [1, 3-thiazol-2-ildiazenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide in 68% yield. 1 H NMR (300 MHz. DMSO): d = 9.17 (s, 1 H, H (2) -imidazole); 7.97 (d, J = 4.2, 1 H, H (4) -thiazole); 7.85 (s, 1 H, midazole); ); 7.80 (d, J = 9.0, 2H, H (3) and H (5) -phenyl); 7.72 (d, J = 4.2, 1 H, H (5) -thiazole); 7.71 (s, 1 H, imidazole); 6.91 (d, J = 9.0, 2H, H (2) and H (6) -phenyl); 4.44 (t, J = 6.0, 2H, CH2); 3.91 (t, J = 6.0, 2H, CH2); 3.83 (s, 3H, N + CH3); 3.46 (q, J = 6.9, 2H, CH2); 1.11 (t, J = 6.9, 3H, CH3).
Example 1 c: 1-r2- (ethyl (4-f (5-methyl-1,3-thiazol-2-yl) diacenyn-phenylamino) ethill-3-methyl-1H-imidazol-3-nio bromide Analogously to procedure described in example 1a, by coupling azo of 2-amino-5-methyl-1,3-thiazole with N- (2-bromoethyl) -N-ethylaniline to give N- (2-bromoethyl) -N-ethyl-4 - [( methyl-1,3-thiazol-2-yl) diacenyl] aniline in 81% yield, followed by quaternization with 1-methyl-1 H-imidazole to give 1- [2- (ethyl. 4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide in 96% yield. 1 H NMR (300 MHz. DMSO): d = 9.15 (s, 1 H, H (2) -imidazole); 7.84 (s, 1 H, imidazole); ); 7.76 (d, J = 9.3, 2H, H (3) and H (5) -phen); 7.71 (s, 1 H, imidazole); 7.70 (s, 1 H, H (4) -thiazole); 6.90 (d, J = 9.3, 2H, H (2) and H (6) -phenyl); 4.42 (t, J = 6.0, 2H, CH2); 3.90 (t, J = 6.0, 2H, CH2); 3.83 (s, 3H, N + CH3); 3.45 (q, J = 6.9, 2H, CH2); 2.48 (s, 3H, CH3); 1.11 (t, J = 6.9, 3H, CH3).
Example 1 d: 1-f2-r (4-r (4,5-dimethyl-1,3-thiazol-2-ihdiacenill-3-methylphenyl) (ethyl) aminoletyl-3-methyl-1 H-imidazole-3-nio bromide) analogous to the procedure described in example 1a, by coupling azo hydrochloride of 2-amino-4,5-methyl-1,3-thiazole with N- (2-bromoethyl) -N-ethyl-3-methylaniline to give N - (2-bromoethyl) -4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] -N-ethyl-3-methylaniline in 67% yield, followed by quaternization with 1 -methyl-1 H-imidazole to give 1 -. {2- 2- [ { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] -3-methylphenyl}. ethyl) amino] ethyl.} - 3-methyl-1 H-imidazole-3-nio bromide in 82% yield 1 H NMR (300 MHz. DMSO): d = 9.15 (s, 1 H, H (2 ) -imidazole), 7.84 (s, 1 H, imidazole), 7.71 (s, 1 H, imidazole), 7.65 (d, J = 9.3, 1 H, H (5) -phenyl), 6.72 (d, J = 9.3, 1 H, H (6) -phenyl), 6.67 (s, 1 H, H (2) -phenyl), 4.42 (t, J = 6.0, 2H, CH2), 3.88 (t, J = 6.0, 2H , CH2), 3.83 (s, 3H, N + CH3), 3.43 (q, J = 6.9, 2H, CH2), 2.54 (s, 3H, CH3), 2.37 (s, 3H, CH3); .31 (s, 3H, CH3); 1.10 (t, J = 6.9, 3H, CH3). API-ES MS: 383 G ?? (100)
Example 1 e: 1-r 2 - (ethyl (4-r (6-nitro-1,3-benzothiazole-2-indiacenyl-phenyl) amino) ethyl-3-methyl-1 H-imidazole-3-nio bromide analogous to the procedure described in example 1a, by coupling azo of 6-nitro-1,3-benzothiazol-2-amine with N- (2-bromoethyl) -N-ethylaniline to give
N- (2-bromoethyl) -N-ethyl-4 - [(6-nitro-1,3-benzothiazol-2-yl) diacenyl] -aniline in 45% yield, followed by quaternization with 1-methyl- 1H-imidazole to give 1- [2- (ethyl. {4 - [(6-nitro-1,3-benzothiazol-2-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide with a yield of 41%. 1 H NMR (300 MHz, DMSO): d = 9.25 br (s, 1 H, imidazole), 9.06 (s, 1 H),
8. 32 (d, J = 8.7, 1 H), 8.16 (d, J = 9.0, 1 H), 7.88-7.89 (m, 1 H, imidazole, overlap), 7.88 (d, J = 6.6, 2H, phenyl) , 7.70-7.73 (m, 1 H, imidazole), 6.99 (d, J = 6.6, 2H, phenyl), 4.00-4.49 (m, 4H, 2 x CH2), 3.85 (s, 3H, CH3), 3.50- 3.54 (m, 2H, CH2), 1.13-1.15 (m, 3H CH3).
Example 1f: 1 - (2-r (4-r (4-chloro-5-nitro-1,3-thiazol-2-yl) diacenyl-phenyl-Uethyl) -aminolethyl) -3-methyl-1 H-imidazole-3-nio bromide Step 1: Azo coupling 1.00 g (5.56 mmol) of 4-chloro-5-nitro-1,3-thiazol-2-ylamine is diazotized in a mixture containing 15 ml of concentrated phosphoric acid, 3.2 g of concentrated hydrochloric acid and 0.46 g (6.66 mmol) of sodium nitrate at -10 ° C. The azo coupling was performed by adding the diazonium solution to a mixture of 1.32 g (5.80 mmol) of N- (2-bromoethyl) -N-ethylaniline in 15 ml of acetic acid. After stirring for 4 hours, the resulting precipitate is filtered, washed with water and dried under vacuum at 40 ° C. 1.20 g (51% in theory) of N- (2-bromoethyl) -4 - [(4-chloro-5-nitro-1,3-thiazol-2-yl) diacenyl] -N-ethylaniline was obtained as a powder dark red. 1H NMR (300 MHz. DIVISO): d = 7.79 (d, J = 8.7, 2H, phenyl), 6.96 (d, J = 9.3, 2H, phenyl), 3.92-3.88 (m, 2H, CH2), 3.74- 3.58 (m, 4H, 2 x CH2), 1.13 (t, J = 6.9, 3H, CH3). Step 2: Quaternization 1.20 g (2.86 mmol) of N- (2-bromoethyl) -4 - [(4-chloro-5-nitro-1,3-thiazol-2-yl) diacenyl] -N-ethylaniline are dissolved in 20 ml of acetonitrile followed by the addition of 5.99 g (73.0 mmol) of 1-methyl-1 H-imidazole. The reaction mixture is stirred under reflux for 3 days and allowed to cool to room temperature. The resulting precipitate is filtered, washed with acetonitrile and dried under vacuum at 40 ° C. 0.43 g (30% in theory) of 1 - are obtained. { 2-[. { 4 - [(4-chloro-5-nitro-1,3-thiazol-2-yl) diacenyl] phenol} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide as a red powder
bordeaux 1 H NMR (300 MHz. DMSO): d = 9.22 (s, 1 H, imidazole), 7.86-7.85 (m, 1 H, imidazole), 7.79 (d, J = 9.0, 2H, phenyl), 7.71-7.70 ( m, 1 H, imidazole), 6.95 (d, J = 9.3, 2H, phenyl), 4.45-4.43 (m, 2H, CH2), 3.98-3.96 (m, 2H, CH2), 3.83 (s, 3H, N -CH3), 3.68-3.65 (m, 2H, CH2), 1.12 (t, J = 6.6, 3H, CH3).
Example of 1 a: 1-f2- (ethyl 4-f 1 H-ri 3-lazol-5,4-flindazol-6-ildiazenyl-phenyl amino) ethyl 1 -3-methyl-1 H-imidazole-3-nio bromide Analogously to the process described in example 1f, by coupling azo of 1 H- [1,3] thiazolo [5,4-f] indazol-6-amine with N- (2-bromoethyl) -N-ethylaniline to give N- (2-bromoethyl) -N ethyl-4- [1 H- [1,3] thiazolo [5,4-f] indazol-6-ildiazenyl] aniline with a yield of 56%, followed by quaternization with 1-methyl-1 H-imidazole for give 1- [2- (ethyl. {4- [1 H- [1,3] thiazolo [5,4-f] indazol-6-ildiazenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide with a yield of 49%. 1 H NMR (300 MHz. DMSO): d = 9.22 (s, br, 1 H, imidazole), 8.28 (s, 1 H, NH), 7.88-7.86 (m, 4H, phenyl / imidazole, overlap), 7.76- 7.73 (m, 2H), 6.98 (d, J = 9.0, 2H, phenyl), 4.47-4.44 (m, 2H, CH2), 3.96-3.95 (m, 2H, CH2), 3.84 (s, 3H, N- CH3), 3.52-3.50 (m, 2H, CH2), 1.14 (t, J = 6.0, 3H, CH3). Example 1 h: 1 - (2-f (4-r (5-chloroM.31-thiazolof5.4-blpyridin-2-yl) diacenyl-phenyl} - (ethylamine-1-ethyl) -3-methyl-1H-imidazole-3- nio bromide In a manner analogous to the procedure described in example 1f, by coupling azo of 5-chloro [1,3] thiazolo [5,4-b] pyridin-2-amine with N- (2-bromoethyl) -N- ethylaniline to give N- (2-bromoetyl) -4 - [(E) - (5-chloro [1,3] thiazolo- [5,4-b] pyridin-2-yl) diacenyl] -N-ethylaniline with a yield of 42%, followed by a quaternization with 1-methyl-1 H-
Midazole to give 1-. { 2-[. { 4 - [(5-chloro [1,3] thiazolo [5,4-b] pyridin-2-yl) diacenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-α-dadazol-3-nio bromide with a yield of 10%. 1 H NMR (300 MHz. DIVISO): d = 9.18 (s, 1 H, imidazole), 8.42 (d, J = 8.7, 1 H, pyridylthiazole), 7.88 (d, J = 9.0, 2H, phenyl) ), 7.86-7.84 (m, 1 H, imidazole), 7.71-7.70 (m, 1 H, imidazole), 7.67 (d, J = 8.7, 1 H, pyridylthiazole), 6.99 (d, J = 9, 0.2H, phenyl), 4.47-4.43 (m, 2H, CH2), 3.98-3.95 (m, 2H, CH2), 1.15 (t, 3H, J = 6.6 Hz, CH3).
Example 1 i: 1 - (2-retyl (4- (r 5 - (methyloxy) n. 31-thiazol-5,4-bl-pyridin-2-illdiacenyl) phenyl) aminolethyl) -3-methyl-1 H-imidazole-3-nio bromide Analogously to the procedure described in example 1 a, by coupling azo of 5-methoxy [1, 3] thiazolo [5,4-b] pyridin-2-amine with N- (2-bromoethyl) -N- ethylaniline to give N- (2-bromoethyl) -N-ethyl-4 - [(E) - (5-methoxy [1,3] -thiazolo [5,4-b] pyridn-2-yl) diazinyl] aniline with a yield of 51%, followed by a quaternization with 1-methyl-1 H-imidazole to give 1-. { 2- [ethyl (4- { [5- (methyloxy) [1, 3] thiazolo [5,4-b] pyridin-2-yl] diacenyl} phenyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide with a yield of 15%. 1 H NMR (300 MHz. DMSO): d = 9.20 (s, 1 H, imidazole), 8.30 (d, J = 9.0, 1 H, pyridylthiazole), 7.85-7.82 (m, 3H, imidazole / phenyl, overlap ), 7.71 (s, 1 H), 7.02 (d, J = 8.7, 1 H, pyridylthiazole), 6.96 (d, J = 8.7, 2H, phenyl), 4.46-4.42 (m, 2H, CH2 ), 3.97-3.93 (m, 5H, CH3 + CH2), 3.51-3.49 (m, 2H, CH2), 1.13 (t, J = 6.6, 3H, CH3).
EXAMPLE 1: 1-2 - (ethyl (4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl-1-phenyl) amino) ethyl-3-methyl-1 H-imidazole-3-nio bromide 1: Azo coupling 1.32 g (10 mmol) of 2-amino-1 H-imidazole-hemisulfate is diazotized in
a mixture containing 2 ml of concentrated hydrochloric acid, 2 ml of acetic acid, 12 ml of water and 0.7 g (10 mmol) of sodium nitrate at 5 ° C. The azo coupling is performed by adding 2.3 g (10 mmol) of N- (2-bromoethyl) -N-ethylaniline to the diazonium solution mentioned above. After stirring for 2 hours at room temperature the mixture is poured onto 50 ml of saturated sodium bicarbonate. The resulting precipitate is filtered, washed with water and dried under vacuum at 40 ° C. After chromatography on silica gel with ethyl acetate, 0.6 g (20% theoretical yield) of N- (2-bromoetyl) -N-ethyl-4 - [(E) -1 H -imidazol-2-ildiazenyl] are obtained. Aniline as a brown powder. 1 H NMR (300 Hz. DMSO): d = 12.5 (br s, 1H, NH); 7.76 (d, J = 9.0, 2H, phenyl); 7.2 (s, 2H, imidazole); 6.87 (d, J = 9.0, 2H, phenyl); 3.81 (t, J = 6.9, 2H, CH2); 3.65 (t, J = 6.9, 2H, CH2); 3.55 (q, J = 6.9, 2H, CH2); 1.16 (t, J = 6.9, 3H, CH3). Step 2: Quaternization Dissolve 0.22 g (0.7 mmol) N- (2-bromoethyl) -N-ethyl-4 - [(E) -1 H -imidazol-2-ildiazenyl] aniline in 4.5 ml of acetonitrile followed by the addition of 2.6 g (31.5 mmol) of 1-methyl-1 H-imidazole. The reaction mixture is stirred overnight under reflux and allowed to cool to room temperature. It is diluted with 45 ml of acetone and 20 ml of ethyl acetate. The resulting precipitate is filtered and dried under vacuum at 40 ° C. 0.28 g (85% in theory) are obtained from 1- [2- (ethyl. {4- [1 H -imidazol-2-ildiazenyl] -phenyl]} amino) ethyl] -3-methyl-1 H- imidazole-3-nio bromide as a red powder. Step 3: Alkylation To a solution of 0.12 g (0.30 mmol) of 1- [2- (ethyl. {4- [1 H -midazol-2-yl-diazyl] phenyl]} amino) ethyl] -3-methyl -1 H-imidazole-3-nio bromide in 5 ml of methanol is added 35 mg (0.87 mmol) of sodium hydroxide and 0.45 g (3.5 mmol) of dimethisulfate. The mixture is stirred for three days under reflux. After evaporation of the solvent, the crude product
It is treated with ethyl acetate and acetone. 0.36 g (30% in theory) are obtained from 1- [2- (ethyl { 4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl] phenyl.}. Amino) ethyl] -3 -methyl-1 H-imidazole-3-nio bromide as a red powder. 1 H NMR (300 MHz. DMSO): d = 9.15 (s, 1 H, H (2) -imidazole); 7.91 (d, J = 9.3, 2H, phenyl); 7.84 (s, 1 H, imidazole); 7.78 (s, 2H, H (4) and H (5) imidazole); 7.71 (s, 1 H, imidazole); 7.00 (d, J = 9.3, 2H, phenyl); 4.47 (t, J = 6.6, 2H, CH2); 3.98 (m, 2H, CH2); 3.98 (s, 3H, N-CH3); 3.84 (s, 3H, N + CH3); 3.52 (q, J = 6.6, 2H, CH2); 2.51 (s, 3H, CH3); 1.14 (t, J = 6.6, 3H, CH3). API-ES MS: 324 [M +] (100) Examples 2 to 1 1: Hair colorant
0. 33 g of dye of the formula (I) 5.0 g ethanol 4.0 g decyl glucoside 0.2 g ethylenediaminetetraacetic acid disodium salt ad 100.0 g water, demineralized
If necessary, the coloring solution is adjusted to the pH values indicated in Table 1 by the addition of ammonia. Hair coloring is done by applying a sufficient quantity of dye to dye the hair and distributing it evenly using a brush. After a contact time of 30 minutes at 40 ° C, the hair is rinsed with warm water, washed with a shampoo, rinsed with warm water and then dried. The results of the coloring are summarized in Table 1 below.
Table 1:
Example 12: hair colorant with cationic surfactants
0. 33 g of 1 -. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] phenyl} - (ethyl) amino] ethyl} -3- methyl-1 H-imi "dazol-3-nio bromide (1a) 5.00 g of ethanol 4.00 g cetyltrimethylammonium chloride, 25% in water ad 100.00 g water, demineralized
The pH is adjusted to 9.3 by the addition of 25% ammonium. Hair coloring is done by applying a sufficient quantity of dye to dye the hair and distributing it evenly using a brush. After a contact time of 30 minutes at 40 ° C, the hair (L = 80.6; C = 12.1; h
= 92.1) is rinsed with warm water, washed with shampoo, rinsed again with warm water and then dried. This gives an intensely orange-red tinted lock (L = 43.96, C = 67.24, h = 40.1).
Example 13: the hair dye with amphoteric surface active substances
of 1 -. { 2-[. { 4 - [(4,5-dimethyl-1, 3-thiazol-2-yl) d-acyl] -phenyl} (ethyl) amino) ethyl} -3- methyl-1 H-imidazole-3-nio bromide (2a) 5.00 g ethanol 7.50 g cocoamidopropylbetaine fatty acid ad 100.00 g water, demineralized
The pH is adjusted to 9.1 by the addition of 25% ammonium. Hair coloring is done by applying a sufficient quantity of dye to dye the hair and distributing it evenly using a brush.
After a contact time of 30 minutes at 40 ° C, the hair (L = 80.6; C = 12.1; h = 92.1) is rinsed with warm water, washed with shampoo, rinsed again with warm water and then dried . This gives an intensely orange-red tinted lock (L = 45.07, C = 65.53, h = 41.40).
Examples 14 to 21: hair colorant with oxidizing agent
0. 66 g of dye of the formula (I) as in Table 2 5.0 g ethanol 4.0 g decyl glucoside 0.2 g ethylenediaminetetraacetic acid disodium salt ad 100.0 g water, demineralized
g of the carrier mass of the aforementioned color are mixed with 5 g of a 9% hydrogen peroxide solution. The pH is adjusted to the basic pH values given in Table 2, using 25% ammonia. The hair dye obtained and ready to use is applied to the hair and distributed evenly using a brush. After a contact time of 30 minutes at 40 ° C, the hair is rinsed with warm water, washed with a shampoo, rinsed again with warm water and then dried. The results of the coloring are summarized in Table 2 below.
Table 2:
Examples 22: Dye for hair without oxidizing agent
0. 33 g of dye of the formula (I) as in Table 3 5.0 g of ethanol 4.0 g Decyl glucoside 0.2 g disodium salt of ethylenediaminetetraacetic acid ad 100.0 g water, demineralized
The pH is adjusted to the pH given in Table 3 using 25% ammonia. The ready-to-use hair colorant obtained is applied to natural hair (L = 34.24, C = 14.62, h = 66.7) and evenly distributed using a brush. After a contact time of 30 minutes at 40 ° C, the hair is rinsed with warm water, washed with a shampoo, rinsed again with warm water and then dried. The washing process is repeated five times. The appearance of the colors does not change.
Table 3
Examples 23: Dye for hair with oxidizing agent
0. 66 g of dye of the formula (I) as in Table 4 5.0 g ethanol 4.0 g Decyl glucoside 0.2 g disodium salt of ethylenediaminetetraacetic acid ad 100.0 g water, demineralized
g of the carrier mass of the aforementioned color are mixed with 5 g of a 9% hydrogen peroxide solution. The pH is adjusted to the pH given in Table 4 using 25% ammonia. The ready-to-use hair colorant obtained is applied to natural hair (L = 34.24, C = 14.62, h = 66.7) and evenly distributed using a brush. After a contact time of 30 minutes at 40 ° C, the hair is rinsed with warm water, washed with a shampoo, rinsed again with warm water and then dried. The washing process is repeated five times. The appearance of the colors does not change.
Table 4:
The L * C * h * values of color measurement provided in the examples were determined with a Minolta colorimeter, Chromameter II model. The L value is the luminosity (that is, the smaller the L value, the greater the intensity of the color), while the C value is a measure of the saturation ("chroma") (ie, the higher the value C, more saturated is the color). The value h is the color tone angle ("tone"). Unless indicated otherwise, all percentages expressed in the present application are percentages by weight. The dimensions and values described herein are not to be understood
as strictly limited to the exact numerical values detailed. On the contrary, if it is specified in any other way, each dimension is intended to refer to a detailed value and a functionally equivalent range surrounding that value. For example, it is intended that a dimension described as "40 mm" refers to "approximately 40 mm".
Claims (10)
1 . An agent for the non-oxidative coloring of keratin fibers, characterized in that it comprises at least one azo dye of the general formula (I); wherein X is oxygen, sulfur, N-R3, C-R4; And it is C-R5, nitrogen, N-R6, sulfur or oxygen; Z is C-R7 or nitrogen; provided that the heterocycle of Formula (I) comprises at least two and at most three heteroatoms, wherein the heterocycle has at most one sulfur atom or one oxygen atom; n is an integer from 1 to 6; R1 is hydrogen, a saturated or unsaturated alkyl group (CrC2) -, an alkyl group (Cr C12) substituted by a halogen atom, a hydroxyalkyl group (C2-Ci2), an aminoalkyl group (CrC12), a substituted phenyl group or unsubstituted or a substituted or unsubstituted benzyl group; R2, R4, R5 and R7 may be identical or different and, independently of one another, are hydrogen, a halogen atom, a saturated or unsaturated alkyl group (C Ci2), an alkyl group (d-C12) - substituted by an atom halogen, a hydroxyl group, a group hydroxyalkyl (dC ^), an alkoxy group (CrC12), a thioalkyl group (CVC ^), a cyano group, a nitro group, an amino group, an alkylamino group (CC ^), a dialkylamino group (Ci-C12), a carboxylic acid group, a C 1 0-C C 4 alkyl group), a substituted or unsubstituted phenyl group C (0) 0-, a substituted or unsubstituted phenyl group or a naphthyl group, a substituted or unsubstituted heteroaryl group; or when Y and Z are C-R5 and C-R7, the radical groups R5 and R7 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; or when X and Y are C-R4 and C-R5, the radical groups R4 and R5 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; R3 and R6 can be identical or different, and independently of each other, they are a saturated or unsaturated (C1-C12) alkyl group, an alkyl group (CrC2) substituted with a halogen atom (F, Cl, Br, I), a hydroxyalkyl group (C2-C12), an aminoalkyl group (CrCi2), a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; Q + represents a 4- to 6-membered aromatic or non-aromatic heterocyclic quaternary ammonium group, substituted or unsubstituted, which may contain other heteroatoms such as nitrogen, sulfur or oxygen, with the proviso that the cationic heterocycle comprises at most three heteroatoms, where the heterocycle has at most one sulfur atom or one oxygen atom; or the radical group R1, together with Q +, can form an unsaturated, substituted or unsaturated, 5 or 6-membered heterocyclic cationic ring system; An- anion is an organic or inorganic acid anion.
2. An agent for the clarification and simultaneous dyeing of keratin fibers, comprising at least one oxidizing agent, characterized in that it comprises minus one azo dye of the general Formula (I); wherein X is oxygen, sulfur, N-R3, C-R4; And it is C-R5, nitrogen, N-R6, sulfur or oxygen; Z is C-R7 or nitrogen; provided that the heterocycle of Formula (I) comprises at least two and at most three heteroatoms, wherein the heterocycle has at most one sulfur atom or one oxygen atom; n is an integer from 1 to 6; R1 is hydrogen, a saturated or unsaturated alkyl group (CrC ^), an alkyl group (Cr C12) substituted by a halogen atom, a hydroxyalkyl group (C2-C12), an aminoalkyl group. { CrC] 2), a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; R2, R4, R5 and R7 may be identical or different and, independently of one another, are hydrogen, a halogen atom, a saturated or unsaturated alkyl group (Ci-C12), an alkyl group (CrC12) - substituted by a halogen atom , a hydroxyl group, a hydroxyalkyl group (CrC12), an alkoxy group (CrC12), a thioalkyl group (Ci-Ci2), a cyano group, a nitro group, an amino group, an alkylamino group (CrC12), a dialkylamino group (CrC! 2), a carboxylic acid group, a C (0) 0- (CrC12) alkyl group, a substituted or unsubstituted phenyl group C (0) 0-, a substituted or unsubstituted phenyl group or a naphthyl group, a substituted or unsubstituted heteroaryl group; or when Y and Z are C-R5 and C-R7, the radical groups R5 and R7 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; or when X and Y are C-R4 and C-R5, the radical groups R4 and R5 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; R3 and R6 can be identical or different, and independently of each other, they are a saturated or unsaturated alkyl group (CC ^), a (C1-C12) alkyl group substituted with a halogen atom (F, Cl, Br, I), a hydroxyalkyl group (C2-C12), an aminoalkyl group (Cr C12), a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; Q + represents a heterocyclic quaternary ammonium group of 4 to 6 members aromatic or non-aromatic, substituted or unsubstituted, which may contain other heteroatoms such as nitrogen, sulfur or oxygen, with the proviso that the cationic heterocycle comprises at most three heteroatoms, where the heterocycle has at most one sulfur atom or one oxygen atom; or the radical group R1, together with Q +, can form an unsaturated, substituted or unsaturated, 5 or 6-membered heterocyclic cationic ring system; An- anion is an organic or inorganic acid anion.
3. An agent for the oxidative dyeing of keratin fibers based on at least one oxidation dye precursor, characterized in that it comprises at least one azo dye of the general Formula (I); wherein X is oxygen, sulfur, N-R3, C-R4; And it is C-R5, nitrogen, N-R6, sulfur or oxygen; Z is C-R7 or nitrogen; provided that the heterocycle of Formula (I) comprises at least two and at most three heteroatoms, wherein the heterocycle has at most one sulfur atom or one oxygen atom; n is an integer from 1 to 6; R1 is hydrogen, a saturated or unsaturated alkyl group (Ci-C12) -, an alkyl group (d-C12) substituted by a halogen atom, a hydroxyalkyl group (C2-C12), an aminoalkyl group (CrC12), a phenyl group substituted or unsubstituted or a substituted or unsubstituted benzyl group; R2, R4, R5 and R7 can be identical or different and, independently of one another, are hydrogen, a halogen atom, a saturated or unsaturated alkyl group (CrC2), an alkyl group (C, -C12) - substituted by a halogen atom, a hydroxyl group, a hydroxyalkyl group (Ci-C12), an alkoxy group (C12), a thioalkyl group (Cr12), a cyano group, a nitro group, an amino group, an alkylamino group (Ci-C) 2), a dialkylamino group (C, -C, 2), a carboxylic acid group, a C (0) 0- (Ci-C12) alkyl group, a substituted or unsubstituted phenyl group C (0) 0-, a phenyl group substituted or unsubstituted or a naphthyl group, a substituted or unsubstituted heteroaryl group; or when Y and Z are C-R5 and C-R7, the radical groups R5 and R7 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; or when X and Y are C-R4 and C-R5, the radical groups R4 and R5 together with the remaining molecule can form a heterocyclic or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring system; R3 and R6 can be identical or different, and independently of each other, they are a saturated or unsaturated alkyl group (CC ^), an alkyl group (CC ^) substituted with a halogen atom (F, Cl, Br, I), a hydroxyalkyl group (C2-Ci2), an aminoalkyl group (Cr C12), a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; Q + represents a 4- to 6-membered aromatic or non-aromatic heterocyclic quaternary ammonium group, substituted or unsubstituted, which may contain other heteroatoms such as nitrogen, sulfur or oxygen, with the proviso that the cationic heterocycle comprises at most three heteroatoms, where the heterocycle has a maximum of one sulfur atom or one oxygen atom; or the radical group R1, together with Q +, can form an unsaturated, substituted or unsaturated, 5 or 6-membered heterocyclic cationic ring system; An- anion is an organic or inorganic acid anion.
4. An agent according to claim 3, further characterized in that the oxidizing agent is selected from hydrogen peroxide or its additive compounds in urea, melamine, sodium borate or sodium carbonate.
5. An agent according to claim 2, further characterized in that the oxidizing agent is selected from hydrogen peroxide or its additive compounds in urea, melamine, sodium borate or sodium carbonate, as well as persulfates. The agent according to one of claims 1 to 5, further characterized in that in formula (I) Q + represents a heterocyclic quaternary ammonium group of 5 to 6 aromatic or non-aromatic members of the formula (lia a llg) (He) (llf) (llg) in which R is a saturated or unsaturated alkyl group (CrC12), R 'can be hydrogen, a halogen atom, a saturated or unsaturated alkyl group (CrC12), an alkyl group (C1) -C12) substituted by a halogen atom, a hydroxyl group, a hydroxyalkyl group (CrC ^), an alkoxy group (Ci-C12), a cyano group, a nitro group, an amino group, an alkylamino group (CrCi2), a dialkylamino group (Cr C12), a carboxylic acid group, a C (0) 0- (CrC12) alkyl group, a substituted or unsubstituted phenyl (C) 0 group, a substituted or unsubstituted phenyl group or naphthyl group, a substituted or unsubstituted heteroaryl group; 7. The agent as claimed in one of claims 1 to 6, further characterized in that the cationic azo dye of the formula (I) is chosen from 1- [2- (ethyl. {4- [1, 3-thiazol-2-ildiazen N] phenyl} amino) ethyl] -3-methyl-1 H-imidazol-3-nio bromide; 3-methyl-1- [2- (methyl. {4- [1, 3-thiazol-2-yl-diazyl] phenyl} amino) ethyl] -1 H-imidazole-3-nio bromide; 1 - [2 - ((2-hydroxyethyl). {4- [1, 3-thiazol-2-yl-diazyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazol-3-nio bromide; 1 - [2- (ethyl { 3-methyl-4- [1,3-thiazol-2-yl-diazyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazol-3-nio bromide; 1 -. { 2-[. { 3-chloro-4- [1,3-thiazol-2-ildiazenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl { 4 - [(4-methyl-1,3-thiazol-2-yl) d-acenyl] phenyl]. Amino) ethyl] -3-methyl-1 H- Midazole-3-n-bromide; 1 - [2- (ethyl { 3-methyl-4 - [(4-methyl-1,3-thiazol-2-yl) d-acetyl] phen.l.-amino) -eti 1] -3-methylene-1 H -amdazole-3-n-bromide; 1 -. { 2-[. { 3-Chloro-4 - [(4-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} (ethyl) amino] etl} -3-methyl-1 H-imidazole-3-n-bromide; 1 - [2- (ethyl { 4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3 -thromium bromide; 1 - [2- (ethyl { 3-methyl-4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} amino) ethyl] -3-methyl-1 H- imidazole-3-nio bromide; 1 -. { 2-[. { 3-Chloro-4 - [(5-methyl-1,3-thiazol-2-yl) d-acyl] phenyl} (etl) amlno] etl} -3-methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacell] -f in l} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacell] -3-methylene} (ethyl) -amino] ethyl} -3-methyl-1 H -amdazole-3-n-bromide; 1 -. { 2-[. { 3-Chloro-4 - [(4,5-dimethyl-1,3-thiazol-2-yl) diacenyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl { 4 - [(5-nitro-1,3-thiazol-2-yl) d-acyl] phenyl] .amino) etl] -3- methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(4-chloro-5-nitro-1,3-thiazol-2-yl) diacenyl] phenyl} (ethylene) -amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl { 4 - [(4-phenyl-1,3-thiazol-2-yl) diacenyl] phenitol] amino) etl] -3-methyl-1 H-imidazole 3-nio bromide; 1-. { 2-[. { 4- [1,3-benzothiazol-2-ildiazenyl] -phenyl]} (etl) amino] etl} -3-methyl-1 H-imidazole-3-n-bromide; 1 - [2- (ethyl { 4 - [(6-nitro-1,3-benzothiazol-2-yl) d-achenyl] phenyl} amino) etl] -3-methyl-1 H-imidazole-3-n-bromide; 1- [2- (et.l { 4 - [(4,6-dinthro-1, 3-benzothiazol-2-yl) d-acetyl] phenyl] .amino) etl. ] -3-methyl-1 H -amdazole-3-nio bromide; 1 - [2- (et.l { 4 - [(5,6-dinitro-1,3-benzothiazol-2-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl- 1 H-imidazole-3-nio bromide; 1 - [2- (ethyl. {4- [1 H- [1,3] thiazolo [5,4-f] indazole-6- ildiazenil] phenyl} amino) ethyl] -3-methyl-1 H-imidazol-3-nio bromide; 1 -. { 2-[. { 4 - [(5-chloro [1,3] thiazolo [5,4-b] pyridin-2-yl) d-achenyl] phenyl} (ethyl) amino] ethyl} -3-methylene-1 H-i ^ bromide; 1 -. { 2- [et.l (4-. {[[5- (methoxy)] [1, 3] t azzolo [5,4-b] pyridin-2-yl] d! Acl. phenol) amino] etl} -3-methyl-1 H-imidazole-3-n-bromide; 1 - [2- (et.l. {4- [1, 3-tiazol-2-diallylene] phenyl} amino) ethyl] -2,3-dimethyl-1 H-imidazole- 3-nio bromide; 1 - [2- (et.l { 4 - [(4-methyl-1, 3-tiazol-2-yl) diacenyl] phenyl} amino) ethyl] -2,3-dimet L-1 H -amidazol-3-nio bromide; 1 - [2- (et.l { 4 - [(5-methy1-l, 3-thiazol-2-yl) d-acyl] phenyl.}. Amnn) ell] -2 , 3-dimethyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(4,5-Dimethyl-1,3-thiazol-2-yl) diacenyl] phenyl} (etl) amino] etl} -2,3-dimethyl-1 H-imidazole-3-n-bromide; 1- [3- (ethyl. {4- [1, 3-thiazol-2-yl-diazyl] phenol] amino) propyl] -3-methyl-1 H-imidazol-3-nio bromide; 1 - [2- (ethyl. {4- [1, 3-thiazol-2-yldiazenyl] phenyl} amino) ethyl] pyridinium bromide; 1 - [2- (ethyl { 4 - [(5-methyl-1,3-thiazol-2-yl) diacenyl] -phenyl] amyl) etl] pyridinium bromide; 1 - [2- (ethyl { 4 - [(4-methyl-1,3-thiazol-2-yl) diacenyl] phenyl} amino) ethyl] -pyridinium bromide; 1 -. { 2-[. { 4 - [(4,5-Dimethyl-1,3-thiazol-2-yl) diacenyl] -phenyl} (ethyl) amino] -ethyl} pyridinium bromide; 1 - [2- (ethyl. {3-methyl-4- [1, 3-thiazol-2-yl-diazyl] -phenyl} amino) ethyl] pyridinium bromide; 1 -. { 2-[. { 3-chloro-4- [1,3-thiazol-2-ildiazenyl] phenol} (ethyl) amino] ethyl} pyridinium bromide; 1 - [2- (ethyl { 4 - [(5-nitro-1,3-thiazol-2-yl) diacenyl] phenyl} amino) etl] pyridinium bromide; 1 - [2- (ethyl { 3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diacenyl] phenyl} amino) -ethyl] pyridinium bromide; 1 -. { 2-[. { 3- (dimethylamino) -4- [1,3-thiazol-2-ildiazenyl] phenol} (ethyl) amino] ethyl} pyridinium bromide; 1 -. { 2-[. { 3- (dimethylamino) -4 - [(5-nitro-1,3-thiazol-2-yl) diacenii] -phenyl} (ethyl) amino] ethyl} pyridinium bromide; 4- [2- (ethyl. {4- [1, 3-thiazol-2-ildiazenyl] phenyl} amino) ethyl] -4-methylmorpholine-4-nio bromide; 4-. { 2-[. { 4- [1,3-benzothiazol-2-ildiazenyl] phenol} (eth) amino] ethyl} -4-methylmorpholine-4-nio bromide; 1 - [2- (ethyl. {4- [1, 3-thiazol-2-yl-diazyl] -phenyl} amino) ethyl] -1-methylpiperidinium bromide; 4- [2- (ethyl. {4- [1, 3-thiazol-2-yl-diazyl] phenyl]} amino) ethyl] -1,1-dimethylpiperazine-1-ethyl bromide; 1 - [2- (ethyl { 4- [1, 3,4-thiadiazol-2-ildiazenyl] phenyl} amino) ethyl] -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl { 4 - [(5-phenyl-1, 3,4- thiadiazole-2-l) diacell] f in l} amino) ethyl] -3-methyl-1 H -amdazole-3-n-bromide; 1 - [2- (ethyl. {4- [1,4-thiadiazol-2-yldazenyl] phenol] amino) -ethyl] pyridinium bromide; 1- [2- (ethyl { 4 - [(5-phenyl-1, 3,4-thiadiazol-2-yl) diacenyl] phenyl} amino) ethyl] pyridinium bromide; 1 - [2- (ethyl { 4- [1, 2,4-thiadiazol-2-ildiazenyl] phenyl} amino) etl] -3-methyl-1 H-imidazol-3-nio bromide; 1 - [2- (ethyl { 4 - [(3-f-enyl-1,4-thiadiazol-5-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H- imidazole-3-nio bromide; 1 -. { 2-[. { 4 - [(3-chloro-1, 2,4-thiadiazol-5-yl) d-acyl] -phenyl} (ethyl) amino] -ethyl} -3-methyl-1 H-imidazole-3-nio bromide; 1 - [2- (ethyl. {4- [1,4-thiadiazol-5-idiazenyl] phenyl} amino) ethyl] pyridinium bromide; 1 - [2- (ethyl { 4 - [(3-phenyl-1, 2,4-thiadiazol-5-yl) d-acenyl] phenyl} amino) ethyl] pyridinium bromide; 2- (ethyl. {4- [1 H-1, 2,4-triazol-5-ildiazenyl] -phenyl} amino) -3-methyl-1 H-imidazol-3-nio bromide; 1 - [2- (ethyl { 4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl] -phenyl} amino) ethyl] -3-methyl-1 H-imidazole- 3-nio bromide; 1 - [2- (ethyl { 3-methyl-4 - [(1-methyl-1 H-imidazol-2-yl) diacenyl] phenyl] .amino) etl] -3- methyl-1 H-imidazole-3-nio bromide; 1 -. { 2-[. { 3-Chloro-4 - [(1-methyl-1 H-imidazol-2-yl) d-acyl] phenyl} (ethyl) amino] ethyl} -3-methyl-1 H-imidazole-3-nio bromide. The agent as claimed in one of claims 1 to 7, further characterized in that the azo cationic dye of the Formula (I) is present in an amount of 0.01 to 10% by weight. The agent as claimed in any of claims 1 to 8, further characterized in that it also comprises at least one other direct dye selected from the group comprising nitro dyes, azo dyes, anthraquinone dyes, triphenylmethane dyes and basic or acid dyes. 10. The agent claimed in one of claims 1 to 9, further characterized in that it is a hair colorant.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06003344 | 2006-02-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MX2008010584A true MX2008010584A (en) | 2008-10-03 |
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