CA1168266A - Metaphenylenediamines, method for preparing them, dyeing compositions containing them and dyeing process - Google Patents
Metaphenylenediamines, method for preparing them, dyeing compositions containing them and dyeing processInfo
- Publication number
- CA1168266A CA1168266A CA000380936A CA380936A CA1168266A CA 1168266 A CA1168266 A CA 1168266A CA 000380936 A CA000380936 A CA 000380936A CA 380936 A CA380936 A CA 380936A CA 1168266 A CA1168266 A CA 1168266A
- Authority
- CA
- Canada
- Prior art keywords
- fact
- composition according
- composition
- group
- charac
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims abstract description 11
- 238000004043 dyeing Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 108010076876 Keratins Proteins 0.000 claims abstract description 12
- 102000011782 Keratins Human genes 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 25
- -1 alkyl radical Chemical class 0.000 claims description 24
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 239000002453 shampoo Substances 0.000 claims description 17
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 229960001755 resorcinol Drugs 0.000 claims description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 11
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 6
- 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 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 235000006708 antioxidants Nutrition 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000003871 sulfonates Chemical class 0.000 claims description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 3
- HWWIVWKTKZAORO-UHFFFAOYSA-N 3,4-dihydro-2h-1,4-benzoxazin-6-ol Chemical compound O1CCNC2=CC(O)=CC=C21 HWWIVWKTKZAORO-UHFFFAOYSA-N 0.000 claims description 2
- DBFYESDCPWWCHN-UHFFFAOYSA-N 5-amino-2-methylphenol Chemical compound CC1=CC=C(N)C=C1O DBFYESDCPWWCHN-UHFFFAOYSA-N 0.000 claims description 2
- 244000215068 Acacia senegal Species 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 159000000011 group IA salts Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 239000002304 perfume Substances 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 2
- 230000003078 antioxidant effect Effects 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- DUALBABBTLAVTN-UHFFFAOYSA-N 2-methoxyethyl 4-amino-2-hydroxybenzoate Chemical compound COCCOC(=O)C1=CC=C(N)C=C1O DUALBABBTLAVTN-UHFFFAOYSA-N 0.000 claims 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 240000009164 Petroselinum crispum Species 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 229940072056 alginate Drugs 0.000 claims 1
- 235000010443 alginic acid Nutrition 0.000 claims 1
- 229920000615 alginic acid Polymers 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 claims 1
- UMVWJRMJMOPKKM-UHFFFAOYSA-N ethyl n-(3-hydroxy-4-methylphenyl)carbamate Chemical compound CCOC(=O)NC1=CC=C(C)C(O)=C1 UMVWJRMJMOPKKM-UHFFFAOYSA-N 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 claims 1
- 229960004592 isopropanol Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- ODVQLBCSJIDHJL-UHFFFAOYSA-N n-(3-hydroxy-2,4-dimethylphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(C)C(O)=C1C ODVQLBCSJIDHJL-UHFFFAOYSA-N 0.000 claims 1
- 150000002790 naphthalenes Chemical class 0.000 claims 1
- 235000011197 perejil Nutrition 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 36
- 239000000118 hair dye Substances 0.000 abstract description 4
- 238000010953 Ames test Methods 0.000 abstract description 3
- 231100000039 Ames test Toxicity 0.000 abstract description 3
- 239000003471 mutagenic agent Substances 0.000 abstract description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 15
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 14
- ALSTYHKOOCGGFT-UHFFFAOYSA-N cis-oleyl alcohol Natural products CCCCCCCCC=CCCCCCCCCO ALSTYHKOOCGGFT-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 10
- YBGQLTLJONDTAL-UHFFFAOYSA-N [Na].[Na].[Na].[Na].[Na].C=C.C=C Chemical class [Na].[Na].[Na].[Na].[Na].C=C.C=C YBGQLTLJONDTAL-UHFFFAOYSA-N 0.000 description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 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 7
- 229960001484 edetic acid Drugs 0.000 description 7
- 229940035423 ethyl ether Drugs 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 125000006353 oxyethylene group Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- BMJXMAAIWXBKBD-UHFFFAOYSA-N aniline;dihydrochloride Chemical compound Cl.Cl.NC1=CC=CC=C1 BMJXMAAIWXBKBD-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 5
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- 241000640882 Condea Species 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229960005323 phenoxyethanol Drugs 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- BEJQXBXPRXFJDP-UHFFFAOYSA-N 3-(3,3-dihydroxypropoxy)propane-1,1-diol Chemical compound OC(O)CCOCCC(O)O BEJQXBXPRXFJDP-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 206010019030 Hair colour changes Diseases 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 3
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- GFHYFPARONGSCD-UHFFFAOYSA-N n-(2-hydroxy-5-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC([N+]([O-])=O)=CC=C1O GFHYFPARONGSCD-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 2
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- YRLORWPBJZEGBX-UHFFFAOYSA-N 3,4-dihydro-2h-1,4-benzoxazine Chemical compound C1=CC=C2NCCOC2=C1 YRLORWPBJZEGBX-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-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
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- QYSXYAURTRCDJU-UHFFFAOYSA-N 1-(1-hydroxypropoxy)propan-1-ol Chemical compound CCC(O)OC(O)CC QYSXYAURTRCDJU-UHFFFAOYSA-N 0.000 description 1
- SCGFHWXUZPQQPI-UHFFFAOYSA-N 1-(2,4-diaminophenoxy)ethanol;dihydrochloride Chemical compound Cl.Cl.CC(O)OC1=CC=C(N)C=C1N SCGFHWXUZPQQPI-UHFFFAOYSA-N 0.000 description 1
- QQEVHINAIRMBMC-UHFFFAOYSA-N 1-(2-amino-6-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=C(N)C=CC=C1O QQEVHINAIRMBMC-UHFFFAOYSA-N 0.000 description 1
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- GIGNQZIJYUEWTI-UHFFFAOYSA-N 2,3,5-trihydroxytoluene Chemical compound CC1=CC(O)=CC(O)=C1O GIGNQZIJYUEWTI-UHFFFAOYSA-N 0.000 description 1
- LECMBPWEOVZHKN-UHFFFAOYSA-N 2-(2-chloroethoxy)ethanol Chemical compound OCCOCCCl LECMBPWEOVZHKN-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical compound ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- GVBHRNIWBGTNQA-UHFFFAOYSA-N 2-methoxy-4-nitroaniline Chemical compound COC1=CC([N+]([O-])=O)=CC=C1N GVBHRNIWBGTNQA-UHFFFAOYSA-N 0.000 description 1
- YXWXCSITLKQDLA-UHFFFAOYSA-N 2-nitro-6-propan-2-ylaniline Chemical compound CC(C)C1=CC=CC([N+]([O-])=O)=C1N YXWXCSITLKQDLA-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- MHNLKKKLAXLGGC-UHFFFAOYSA-N CC(=O)c1c(N)c(O)ccc1[N+]([O-])=O Chemical compound CC(=O)c1c(N)c(O)ccc1[N+]([O-])=O MHNLKKKLAXLGGC-UHFFFAOYSA-N 0.000 description 1
- 241000557626 Corvus corax Species 0.000 description 1
- 240000009226 Corylus americana Species 0.000 description 1
- 235000001543 Corylus americana Nutrition 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 241000083869 Polyommatus dorylas Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QMJDEXCUIQJLGO-UHFFFAOYSA-N [4-(methylamino)phenyl] hydrogen sulfate Chemical compound CNC1=CC=C(OS(O)(=O)=O)C=C1 QMJDEXCUIQJLGO-UHFFFAOYSA-N 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- XEKAUTDWPYQNFU-UHFFFAOYSA-N chlorane Chemical compound Cl.Cl.Cl XEKAUTDWPYQNFU-UHFFFAOYSA-N 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 239000003581 cosmetic carrier Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229950010286 diolamine Drugs 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QFCGWLMVBQWKLP-UHFFFAOYSA-N ethyl n-(3-hydroxy-4-methoxyphenyl)carbamate Chemical compound CCOC(=O)NC1=CC=C(OC)C(O)=C1 QFCGWLMVBQWKLP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229960002900 methylcellulose Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 230000002352 nonmutagenic effect Effects 0.000 description 1
- PUBSMDUBHLYMIX-UHFFFAOYSA-N phenol;dihydrochloride Chemical compound Cl.Cl.OC1=CC=CC=C1 PUBSMDUBHLYMIX-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
Abstract
L'invention concerne des composés chimiques de formule générale (I): <IMG> (I) formule dans laquelle Z représente ou bien un radical polyhydroxyalkyl dont le groupe alkyl comporte de 3 à 6 atomes de carbone, ledit radical comportant 2 ou 3 groupes hydroxy, ou bien une chaîne alkyl interrompue par au moins un atome d'oxygène et comportant au moins un groupe hydroxyl, ladite chaîne alkyl contenant de 4 à 8 atomes de carbone, ou les sels d'acide correspondants. L'invention à trait également au procédé de préparation de ces composés, à des compositions tinctoriales pour fibres kératiniques les contenant et à un procédé de teinture de cheveux mettant en oeuvre lesdites compositions tinctoriales. Les composés chimiques selon l'invention sont notamment utilisable dans des compositions tinctoriales pour fibres kératiniques et plus particulièrement comme teinture capillaire car non seulement ils possèdent les qualités tinctoriales d'un bon coupleur, mais encore, ils bénéficient d'une bonne innocuité et sont non-mutagènes dans le test d'Ames.The invention relates to chemical compounds of general formula (I): <IMG> (I) formula in which Z represents either a polyhydroxyalkyl radical in which the alkyl group contains from 3 to 6 carbon atoms, said radical comprising 2 or 3 groups hydroxy, or else an alkyl chain interrupted by at least one oxygen atom and comprising at least one hydroxyl group, said alkyl chain containing from 4 to 8 carbon atoms, or the corresponding acid salts. The invention also relates to the process for the preparation of these compounds, to dye compositions for keratin fibers containing them and to a hair dyeing process using said dye compositions. The chemical compounds according to the invention can be used in particular in dye compositions for keratin fibers and more particularly as a hair dye because not only do they have the dye qualities of a good coupler, but also, they benefit from good safety and are not -mutagens in the Ames test.
Description
1 16826~
La présen-te invention a trait ~ de nouvelles meta-phenylènediamines, à leur procede de préparation, a des compo-sitions tinctoriales pour fibres keratiniques les contenant et à un procédé de teinture de cheveux mettant en oeuvre lesdites compositions tinctoriales.
Dans le domaine de la teinture des fibres kérati-niques, telles que les cheveux ou des fourrures, les meta-phenylènediamines jouent un rôle important connu depuis longtemps: elles font partie de la classe des composes couram-ment appeles coupleurs. Les coupleurs, en association avecles paraphénylenediamines ou les paraaminophenols -composés appeles bases d'oxydation-, donnent, en milieu alcalin oxydant, naissance à des indamines, indoanilines ou indophénols colorés.
L'association des métaphénylènediamines avec les paraphenylènediamines, en milieu alcalin oxydant et plus particulièrement en presence d'eau oxygenee, donne naissance à des indamines capables de conferer aux fibres keratiniques des colorations bleues très puissantes. De plus, les meta-phenylènediamines associees aux paraaminophenols donnent, enmilieu alcalin oxydant, des indoanilines qui confèrent aux fibres keratiniques des colorations rouges plus ou moins pourpre. Les métaphénylènediamines jouent donc, en temps que coupleurs, un double rôle en teinture capillaire: apport du bleu et apport du rouge, c'est-à-dire apport de deux couleurs fondamentales indispensables pour obtenir non seulement des noirs et des gris, mais aussi des châtains cendrés ou cuivres.
Malgré son rôle important, cette catégorie de coupleurs se trouve jusqu'ici limitée dans la pratique à un nombre très restreint de composés. Ce nombre trop restreint s'explique par le fait que seuls peuvent être retenus pour la teinture des fibres kératiniques les composés permettant -1- ~
1 lB826~
d'obtenir des teintures de bonne qualité, c'est-~-dire n'évoluant pas dans le temps, en particulier ni à la lumière ni aux intempéries. En outre, lors~u'll s'agit de teintures capillaires, les coupleurs utilises doivent beneficier d'une bonne innocuite et, en particulier, doivent être pratiquement non-mutagènes dans le test d'Ames sur Salmonella Thyphimurium (TA 1538, TA 98, TA 100, TA 1537 et TA 1535, en l'absence ou en presence de S9 MIX (marque de commerce) activite à l'Arochlor 1254 (marque de sommerce)).
La presente invention a donc pour but de decrire de nouveaux composés chimiques susceptibles de constituer des coupleurs metaphénylènediamines utilisables dans des compositions tinctoriales pour fibres kératiniques. Les composés selon l'invention sont particulièrement utilisables en teinture capillaire car non seulement ils possèdent les qualités tinctoriales d'un bon coupleur, mais encore, ils benéficient d'une bonne innocuité et sont non-mutagènes dans le test d'Ames tel que ci-dessus défini. On a déjà propose, dans la demande de brevet français publiee sous le n 2 362 116, des métaphenylènediamines donnant des résultats satisfaisants en teinture capillaire et l'invention vise à decrire d'autres metaphenylènediamines du meme type, ainsi que leur utilisation.
La presente invention a donc pour objet le produit industriel nouveau que constitue un compose chimique de formule generale (I):
OZ
~ H2 (I) formule dans laquelle Z represente ou bien un radical poly-hydroxyalkyl dont le groupe alkyl comporte de 3 à 6 atomes de 1 ~826~
carbone, ledit radical comportant 2 ou 3 groupes hydroxy, ou bien une chalne alkyl interrompue par au moins un atome d'oxy-gène et comportant au moins un groupe hydroxyl, ladite chalne alkyl contenant de 4 à 8 atomes de carbone, ou les sels d'acides correspondants.
De preference, lorsque Z represente une chalne alkyl interrompue par au moins un atome d'oxygène, le (ou les) groupement(s) hydroxyl de la cha~ne alkyl peut (peuvent) se trouver en bout de cha~ne ou non.
La presente invention a egalement pour objet un procéde de preparation des composés de formule (I) ci-dessus définie. Dans ce procédé, on fait agir sur un sel alcalin de l'acétylamino-2 nitro-4 phenol un derive halogene de formule X Z, X étant un halogène et Z ayant les significations précédemment indiquées pour la définition de la formule (I), de façon à condenser le radical Z sur le noyau avec élimina-tion d'un halogénure alcalin, on réduit ensuite le groupe nitro du produit obtenu et, enfin, on désacétyle le produit pour obtenir le composé de formule (I).
Dans un mode préféré de mise en oeuvre, l'halogène X, qui est utilisé, est le chlore et le métal alcalin est le potassium; la reduction du groupe nitro s'effectue en solu-tion alcoolique, au reflux, par le zinc en poudre en presence de chlorure d'ammonium.
La presente invention a egalement pour objet le pro-duit industriel nouveau que constitue une composition tincto-riale pour fibres keratiniques, et en particulier pour che-veux, ladite composition contenant, dans un support cosmeti-quement acceptable, au moins une base d'oxydation, caracteri-see par le fait qu'elle contient, en tant que coupleur, au moins un compose de formule (I) ou un sel ! . - 3 1,16826 ~
The present invention relates to new meta-phenylenediamines, to their process of preparation, to compounds dye positions for keratin fibers containing them and a hair dyeing process using said dye compositions.
In the field of keratin fiber dyeing nics, such as hair or furs, meta phenylenediamines play an important role known since long: they are part of the class of common compounds called couplers. Couplers, in combination with paraphenylenediamines or paraaminophenols - compounds called oxidation bases-, give, in an alkaline medium oxidant, birth to indamines, indoanilines or indophenols colored.
The association of metaphenylenediamines with paraphenylenediamines, in an oxidizing alkaline medium and more particularly in the presence of oxygenated water, gives birth to indamines capable of imparting to keratin fibers very powerful blue colors. In addition, the meta-phenylenediamines associated with paraaminophenols give, in an oxidizing alkaline medium, indoanilines which give the keratin fibers of red colors more or less purple. Metaphenylenediamines therefore play, while couplers, a double role in hair dye: contribution of blue and red, i.e. two colors essential to obtain not only blacks and grays, but also ash browns or coppers.
Despite its important role, this category of couplers is so far limited in practice to one very small number of compounds. This number is too small is explained by the fact that only can be retained for the dyeing of keratin fibers the compounds allowing -1- ~
1 lB826 ~
to get good quality dyes, that is ~ ~
not evolving in time, in particular or in the light nor to bad weather. Also, when ~ u'll be dyes capillaries, the couplers used must have a good innocuity and, in particular, must be practically non-mutagens in the Ames test on Salmonella Thyphimurium (TA 1538, TA 98, TA 100, TA 1537 and TA 1535, in the absence or in the presence of S9 MIX (trademark) activity with Arochlor 1254 (sommerce brand)).
The present invention therefore aims to describe new chemical compounds likely to constitute metaphenylenediamine couplers usable in dye compositions for keratin fibers. The compounds according to the invention are particularly usable in hair dye because not only do they have the dye qualities of a good coupler but still they have good safety and are non-mutagenic in the Ames test as defined above. We have already proposed, in the French patent application published under No. 2,362,116, metaphenylenediamines giving satisfactory results in hair dye and the invention aims to describe other metaphenylenediamines of the same type, as well as their use.
The subject of the present invention is therefore the product new industrial chemical compound of formula general (I):
OZ
~ H2 (I) formula in which Z represents either a poly- radical hydroxyalkyl in which the alkyl group contains from 3 to 6 atoms of 1 ~ 826 ~
carbon, said radical comprising 2 or 3 hydroxy groups, or well an alkyl chain interrupted by at least one oxygen atom gene and comprising at least one hydroxyl group, said chalne alkyl containing 4 to 8 carbon atoms, or the salts of corresponding acids.
Preferably, when Z represents an alkyl chain interrupted by at least one oxygen atom, the (or) hydroxyl group (s) of the alkyl chain can (can) be find at the end of the chain or not.
The present invention also relates to a process for the preparation of the compounds of formula (I) above defined. In this process, an alkaline salt of 2-acetylamino-4-nitro phenol a halogen derivative of formula XZ, X being a halogen and Z having the meanings previously indicated for the definition of formula (I), so as to condense the radical Z on the nucleus with elimination tion of an alkaline halide, then the group is reduced nitro of the product obtained and, finally, the product is deacetylated to obtain the compound of formula (I).
In a preferred embodiment, the halogen X, which is used, is chlorine and the alkali metal is potassium; the reduction of the nitro group is carried out in solu-alcoholic reflux with zinc powder in the presence ammonium chloride.
The present invention also relates to the pro-new industrial duit that constitutes a dye composition for keratin fibers, and in particular for hair want said composition containing, in a cosmetic carrier only acceptable, at least one oxidation base, characteristic see by the fact that it contains, as a coupler, the minus a compound of formula (I) or a salt ! . - 3
2 6 6 d'acide correspondant.
De façon generale, les metaphenylènediamines de formule lI) sont presentes dans la composition tinctoriale selon l'invention dans une proportion comprise entre 0,001 et 2,~5% en poids par rapport au poids total de la composition.
Les metaphenylènediamines selon l'invention peuvent être incorporees dans des compositions tinctoriales avec des bases d'oxydation constituees par:
A - Les paraphénylènediamines de formule generale (II): / R5 ~\
Rl ~ ~ R3 (II) R2 \~
ou les sels d'acide correspondants, formule dans laquelle Rl, R2 et R3 sont identiques ou differents et représentent un atome d'hydrogène, un radical alkyl ayant de 1 à 4 atomes de carbone ou un radical alcoxy ayant de 1 à 2 a-tomes de carbone, R4 et R5 sont identiques ou différents et repré-sentent un atome d'hydrogène, un radical alkyl, hydroxyalkyl, alcoxyalkyl, dans lequel le groupe alcoxy comporte de 1. à
2 atomes de carbone, carbamylalkyl, mésylaminoalkyl, acetyl-aminoalkyl, uréidoalkyl, carbéthoxyaminoalkyl, aminoalkyl, r monoalkylaminoalkyl, dialkylaminoalkyl, pipéridinoalkyl, morpholinoalkyl, les groupes alkyl dans R4 et R5 ayant de 1 à 4 atomes de carbone, ou bien R4 et R5 forment conjointement avec l'atome d'azote auquel ils se rattachent un groupement piperidino ou morpholino, sous reserve que Rl et R3 representent un atome d'hydrogène, lorsque R4 et R5 ne representent pas un d~, '' ,~ , 1 1682~
d'hydrogène.
B - Les paraaminophenols de formule generale (III):
OH
6 (III) ou les sels d'acide correspondants, formule dans laquelle R6 représente un atome d'hydrogène, un radical alkyl comportant de 1 ~ 4 atomes de carbone ou un atome d'halogène comme, par exemple, le chlore ou le brome.
C - Les bases heterocycliques telles que la diamino-2,5 pyridine, la methyl-3 amino-7 benzomorpholine et l'amino-5 indole.
On a constate que l'utilisation des metaphenylène-diamines selon l'invention avec au moins une base d'oxydation visée sous A -, B - et C - ci-dessus permet d'obtenir des compositions tinctoriales conferant aux cheveux des nuances de bonne qualite, resistant bien notamment aux lavages.
De façon genérale, les coupleurs selon ]'invention permettent d'obtenir, avec les paraphenylènediamines, des colorations bleues, plus ou moins riches en vert ou en poupre, et, avec les paraaminophenols, des colorations rouges. Les compositions tinctoriales selon l'invention pourront donc, avantageusement, contenir à la fois des paraphenylènediamines et des paraaminophenols.
On a constate que l'on obtenait des resultats particulièrement interessants en utilisant, dans l'ensemble des composes de formule (I) ou de leurs sels d'acide cor-respondants, le (diamino-2,4)phenyl,~(~'-hydroxyethoxy~
ethylether, notamment sous forme de dichlorhydrate et/ou le (diamino-2,4)phenyl,~,~-dihyd.roxypropylether, notamment sous forme de dichlorhydrate.
Les compositions tinctoriales faisant l'objet de l'invention peuvent contenir, outre le (ou les) coupleur(s) de formule ~I) et la (ou les) base(s) d'oxydation associée(s), les produits suivants pris isolément ou en combinaison:
1) d'autres coupleurs connus, par exemple la resorcine, la méthyl-2 résorcine, le metaaminophénol`, le méthyl-2 amino-5 phénol, le méthyl-2 N-(~-hydroxyéthyl)amino-5 phénol, l'hydroxy-6 benzomorpholine, le dimethyl-2-6 acétyl-amino-3 phénol, le méthyl-2 carbéthoxyamino-5 phénol, le méthoxy-2 carbéthoxyamino-5 phénol, le méthyl-2 uréido-5 phénol et la phényl-l méthyl-3 pyrazolone-5;
2) des orthophénylènediamines et des orthoamino-phénols comportant éventuellement des substituants sur le noyau ou sur les fonctions amine ou encore l'ortho-diphénol, ces produits, par des mécanismes d'oxydation complexes, pouvant conduire à de nouveaux composés colorés, soit par cyclisation sur eux-m~mes, soit par action sur les para-phénylènediamines 2 6 6 corresponding acid.
Generally, metaphenylenediamines of formula III) are present in the dye composition according to the invention in a proportion of between 0.001 and 2, ~ 5% by weight relative to the total weight of the composition.
The metaphenylenediamines according to the invention can be incorporated into dye compositions with oxidation bases constituted by:
A - Paraphenylenediamines of general formula (II): / R5 ~ \
Rl ~ ~ R3 (II) or the corresponding acid salts, formula in which Rl, R2 and R3 are the same or different and represent a hydrogen atom, an alkyl radical having from 1 to 4 atoms of carbon or an alkoxy radical having from 1 to 2 atoms of carbon, R4 and R5 are the same or different and represents feel a hydrogen atom, an alkyl, hydroxyalkyl radical, alkoxyalkyl, in which the alkoxy group comprises from 1. to 2 carbon atoms, carbamylalkyl, mesylaminoalkyl, acetyl-aminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, aminoalkyl, r monoalkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, the alkyl groups in R4 and R5 having 1 with 4 carbon atoms, or else R4 and R5 form jointly with the nitrogen atom to which they are attached a group piperidino or morpholino, provided that Rl and R3 represent a hydrogen atom, when R4 and R5 do not represent a d ~, '' , ~, 1 1682 ~
hydrogen.
B - The paraaminophenols of general formula (III):
OH
6 (III) or the corresponding acid salts, formula in which R6 represents a hydrogen atom, an alkyl radical comprising of 1 ~ 4 carbon atoms or a halogen atom like, for for example, chlorine or bromine.
C - Heterocyclic bases such as diamino-2,5 pyridine, methyl-3 amino-7 benzomorpholine and amino-5 indole.
It has been observed that the use of metaphenylene-diamines according to the invention with at least one oxidation base referred to under A -, B - and C - above makes it possible to obtain dye compositions giving the hair nuances good quality, particularly resistant to washing.
In general, the couplers according to the invention allow to obtain, with paraphenylenediamines, blue colors, more or less rich in green or in dolls, and, with paraaminophenols, red colors. The dye compositions according to the invention may therefore, advantageously, to contain both paraphenylenediamines and paraaminophenols.
We found that we obtained results particularly interesting using, overall compounds of formula (I) or their acid salts respondents, (2,4-diamino) phenyl, ~ (~ '-hydroxyethoxy ~
ethylether, in particular in the form of dihydrochloride and / or the (2,4-diamino) phenyl, ~, ~ -dihyd.roxypropylether, especially under form of dihydrochloride.
The dye compositions which are the subject of the invention may contain, in addition to the coupler (s) of formula ~ I) and the associated oxidation base (s), the following products taken individually or in combination:
1) other known couplers, for example the resorcin, 2-methyl resorcin, metaaminophenol`, 2-methyl-5-amino phenol, 2-methyl N- (~ -hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpholine, dimethyl-2-6 acetyl-3-amino phenol, 2-methyl carbethoxyamino-5 phenol, 2-methoxy-5-carbethoxyamino phenol, 2-methyl ureido-5 phenol and phenyl-1 methyl-3 pyrazolone-5;
2) orthophenylenediamines and orthoamino-phenols optionally containing substituents on the nucleus or amine functions or ortho-diphenol, these products, through complex oxidation mechanisms, which can lead to new colored compounds, either by cyclization on themselves, or by action on the para-phenylenediamines
3) des précurseurs de colorants de la série benzéniquecomportant sur le noyau au moins trois substituants choisis dans le groupe forme par les ~roupements hydroxy, méthoxy ou amino tels que le dichlorhydrate de diamino-2,6 hydroqui-none, le trichlorhydrate de diamino-2,6 N,N-bis-(ethyl)amino-4 phénol, le dichlorhydrate de diamino-2,4 phénol, le trihy-droxy-1,2,4 benzène, le trihydroxy-2,3,5 toluène ou la méthoxy-4 amino-2 N-(~-hydroxyéthyl) aniline: 3) dye precursors of the benzene series comprising on the nucleus at least three selected substituents in the group formed by ~ hydroxy, methoxy groups or amino such as 2,6-diamino hydrochloride dihydrochloride none, diamino 2,6 N hydrochloride, N-bis- (ethyl) amino-4 phenol, 2,4-diamino dihydrochloride phenol, trihy-1,2,4-droxy benzene, 2,3,5-trihydroxy toluene or 4-methoxy 2-amino-N- (~ -hydroxyethyl) aniline:
4) des précurseurs de colorant de la série naphta-lénique tels que l'hydroxy-2 naphtoquinone-1,4 et l'hydroxy-5 naphtoquinone-1,4; 4) dye precursors of the naphtha series lenic such as hydroxy-2 naphthoquinone-1,4 and hydroxy-5 naphthoquinone-1,4;
5) des leucoderivés d'indoanilines ou d'indophénols 1 16~2~6 tels que la dihydroxy-4,4' amino-2 methyl-5 diphenylamine, la dihydroxy-4,4' N-(~-hydroxyéthyl)amino-2 méthyl-5 chloro-2' diphenylamine, la diamino-2,4' hydroxy-4 méthyl-5 diphénylamine, la dihydroxy-2,4 N-(~-méthoxyéthyl)amino-4' diphénylamine, la dihydroxy-2,4 méthyl-5 N-(~-methoxyethyl)-amino-4' diphenylamine; 5) leucoderivates of indoanilines or indophenols 1 16 ~ 2 ~ 6 such as 4,4 'dihydroxy-2-amino-5-methyl diphenylamine, 4,4 'dihydroxy N- (~ -hydroxyethyl) 2-amino-5-methyl 2-chloro-diphenylamine, 2,4-diamino-4-hydroxy-5-methyl diphenylamine, 2,4-dihydroxy N- (~ -methoxyethyl) amino-4 ' diphenylamine, 2,4-dihydroxy-methyl-5 N- (~ -methoxyethyl) -4-amino diphenylamine;
6) des colorants directs et par exemple ceux choisis dans la classe des colorants nitres de la serie benz`enique tels que le N,N-bis-(~-hydroxyethyl)amino-l nitro-3 N'-méthylamino-4 benzène, le N,N-tméthyl, ~-hydroxyéthyl)amino-l nitro-3 N'-(~-hydroxyéthyl)amino-4 benzène, le N,N-(méthyl, ~-hydroxyéthyl)amino 1 nitro-3 N'-méthylamino-4 benzène, le nitro-3 N-(~-hydroxyéthyl)amino-4 anisole, le nitro-3 N-(~-hydroxyéthyl)amino-4 phenol, le (nitro-3 amino-4) phenoxyéthanol, le (nitro-3 N-méthylamino-4) phenoxyethanol, le N-(~-hydroxyethyl)amino-2 nitro-5 anisole.
Le pH des compositions tinctoriales selon l'invention est basique, par exemple compris entre 8 et 11,5. Parmi les agents d'alcalinisation qui peuvent être utilises, on peut mentionner l'ammoniaque, les alkylamines telles que l'éthyl-amine ou la triéthylamine, les alcanolamines telles que la mono, la di ou la tri-ethanolamine, les alkyl-alcanolamines telles que la méthyl-diéthanolamine, les hydroxydes de sodium ou de potassium, les carbonates de sodium, de potassium ou d'ammonium. Parmi les agents d'acidification qui peuvent etre utilises, on peut mentionner l'acide lactique, l'acide acétique, l'acide tartrique et l'acide phosphorique.
Le support cosmetiquement acceptable, qui est associe aux base(s), coupluer(s), et éventuellement colorant(s) direct(s) de la composition peut comprendre, outre de l'eau, des agents tensio-actifs, des solvants organiques, des produits épaississants, des agents anti-oxydants, des agents de "` 11~2fi6 pénétration, des agents moussants, des agen-ts séquestrants, des produits filmogenes, des agents de traitemen-t et des parfums.
On peut ajouter à la composltion selon l'invention des agents tensio-actifs, anioniques, cationiques, non-ioniques, amphotères ou leur mélange. Parmi les agents tensio-actifs particulierement utilisables, on peut mentionner les alkylbenzène-sulfonates, les alkylnaphtalène-sulfonates, les sulfates, ether~sulfates et sulfonates d'alcools gras, les sels d'ammonium quaternaires tels que le bromure de triméthyl-cetylammonium, le bromure de cétyl-pyridinium, les diéthanol-amides d'acides gras, les acides et les alcools polyoxyéthylénés ou polyglyceroles et les alkylphénols polyoxyethylenés ou poly-glycéroles. De préference, les tensio-actifs sont présents dans la composition selon l'invention en une proportion comprise entre 0,5 et 55 % en poids et, avantageusement, entre 4 et 40 %
en poids par rapport au poids total de la composition.
On peut également ajouter, dans la composition selon l'invention, des solvants organiques pour solubiliser des composes qui ne seraient pas suffisamment solubles dans l'eau.
Parmi les solvants que l'on peut avantageusement utiliser, on peut mentionner, a titre d'exemple, l'éthanol, l'isopropanol, la glycerine, des glycols et leurs éthers comme le butoxy-2 éthanol, l'éthylène-glycol, le propyleneglycol, le monoéthyl-éther et le monomethyléther du diéthylèneglycol et des solvants analogues. Les solvants peuvent être avantageusement présents dans la composition en une proportion allant de 1 à 40 ~ en poids et, de préférence, comprise entre 5 et 30 % en poids par rapport au poids total de la composition.
Les produits épaississants, que l'on peut ajouter dans la composition selon l'invention, peuvent avantageusement être pris dans le groupe formé par l'alginate de sodium, la .
1 ~6826~
gomme arabique, les dérives de la cellulose tels que la methyl-cellulose, l'hydroxyethylcellulose, l'hydroxypropylméthyl-cellulose, le sel de sodium de la carboxymethylcellu~ose et les polymères d'acide acrylique; on peut également utiliser des agents epaississants minéraux tels que la bentonite.
De preference, les agents epaississants sont presents en une proportion comprise entre 0,5 et 5 % en poids par rapport au poids total de la composition et, avantageusement, ehtre 0,5 et 3 ~ en poids.
Les agents anti-oxydants, que l'on peut ajouter à
la composition selon l'invention, peuvent avantageusement être pris dans le groupe formé par le sulfite de sodium, l'acide thioglycolique, l'acide mercapto-succinique, le bisulfite de sodium, l'acide ascorbique et l'hydroquinone.
Ces agents anti-oxydants peuvent être présents dans la composition dans une proportion comprise entre 0,05 et 1,5 en poids par rapport au poids total de la composition.
La composition tinctoriale selon l'invention contient, au moment de l'emploi, des agents d'oxydation tels que l'eau oxygénée, le peroxyde d'urée ou des persels, tels que le persulfate d'ammonium.
La composition tinctoriale selon l'invention peut se présenter sous forme de liquide, de crème, de gel, d'aérosol ou sous toute autre forme appropriée, pour réaliser une tein-ture de fibres kératiniques.
La présente invention a également pour objet un procédé de teinture de cheveux, caractérisé par le fait que l'on mélange une composition selon l'invention avec un agent oxydant, qu'on applique alors ledit mélange sur les cheveux, qu'on laisse agir le mélange sur les cheveux pendant un temps compris entre 5 et 45mn , que l'on rince, qu'éventuellement on lave au shampooing et on rince à nouveau, et que l'on 1 16826~
sèche les cheveux.
Pour mieux faire comprendre l'objet de l'invention, on va en décrire maintenant, à titre d'exemples purement illustratifs et non limitatifs, plusieurs modes de mise en oeuvre.
Exemple 1: Preparatio_ du dichlorhydrate de (diamino-2!4) p~ yl ~ hydroxyethoxy) ethylether Le compose prepare a la formule suivante:~
O-CH ~CH -O-CH -CH -OH
, 2HCl Première phase:
OH K
IIICOCH3 ) ~NIICOCH3 Deuxième phase:
OK
~ Cl-CH2-CH2-0-CH2-CH2-OH
O-CH -CH -O-CH -CH -OH
~ HCOCH3 ~ ~82~6 roisième phase:
~-CH2-CH2-O-CH2-CH2-OH
NHCOCH3 - >
O-CH -CH -O-CH -CH -OH
~ NHCOCH3 ~ , HCl Quatrième phase:
O-CH -CH -O-CH -CH -OH
NHcocH3 , HCl O-CH -CH -O-CH -CH -OH
~NH2 ~ , 2HCl Première étape: Préparation du sel de potassium de l'acétyl-amino-2 nitro-4 phénol 2150 ml d'éthanol contenant en solution 1,89 mole (133 g) de potasse à 80 % sont refroidis a -10C; puis on 3 ajoute peu à peu, sous agitation et tout en maintenant la température en dessous de 5C, 1,89 mole (371 g) d'acétylamino-2 nitro-4 phénol. Le sel de potassium précipite. On essore 1 1~8266 le produit, on le lave a l'éthanol et on le sèche sous vide à 50C.
Deuxième étape: Préparation de l'(acétylamino-2 nitro-4) .
phényl ~ '-hydroxyéthoxy) éthylether On introduit 0,5 mole (117 g) du sel de potassium de l'acétylamino-2 nitro-4 phénol dans 500 ml de diméthyl-formamide; puis on ajoute, sous agitation, 0,6 mole (64 ml) de monochlorhydrine de diethylèneglycol. Le melangè est maintenu pendant 8 heures ~ous agitation à une temperature voisine de 100C puis verse dans deux litres d'eau glacee.
Le produit brut est essore; il est lave à l'eau, puis avec une solution sodique normale glacee, et enfin à l'eau. Après sechage sous vide et recristallisation dans l'ethanol, le produit attendu fond à 152C.
L'analyse du produit obtenu donne les résultats suivan-ts:
Analyse Calcule pour C12 H16 N2 6 Trouvé
C% 50,70 50,88 H% 5,67 5,64 N% 9,86 9,74 O% 33,77 33,90 Troisième étape: Preparation du monochlorhydrate d'(acetyl-amino-2 amino-4) phe_yl ~ hydroxyethoxy)_ ethylether On porte au reflux, sous agitation, 400 ml d'ethanol (à 96) additionnés de 75 ml d'eau, 10 g de chlorure d'am-monium et 200 g de zinc en poudre; puis on ajoute, peu à peutout en maintenant l'agitation, 0,32 mole (91 g) d'(acétyl-amino-2 nitro-4) phényl ~ '-hydroxyethoxy) ethylether.
1 1~826~
Apres chaque addition, le milieu reactionnel se decolore tres rapidement. L'addition du dérivé nitré terminée, on maintient le chauffage pendant une dizaine de minutes puis on filtre le milieu réactionnel en recueillant le filtrat dans 30 ml d'éthanol (à 96~) additionnés de 34 ml d'acide chlorhydrique à 36 ~ et préalablement refroidis à l'aide d'un mélange carboglace-éthanol. Le produit attendu cristallise sous forme de chlorhydrate. Il est essoré, lavé avec un peu d'ethanol absolu préalablement refroidi à -10C, puis séché sous vide à 55C.
L'analyse du produit obtenu donne les résultats - suivants:
Analyse calculé pour C12 H18 N2 4' Trouvé
C% .49,57 49,56 H~ 6,58 6,50 N% 9,63 9,48 O~ 22,01 21,83 Cl~ 12,19 12,30 Quatrième étape: Préparation du dichlorhydrate de (diamino-2,4) phenyl ~ '-hydroxyéthoxy) éthyléther On chauffe au reflux, sous agitation, 0,25 mole (70,9 g) de monochlorhydrate d'(acétylamino-2 amino-4) phényl ~-(B'-hydroxyéthoxy) éthyléther dans 210 ml d'éthanol absolu saturé de gaz chlorhydrique. Apres 10 mn de chauffage, la dissolution est totale puis le dichlorhydrate attendu commence à précipiter au bout d'une demi-heure environ. On maintient le chauffage en tout pendant une heure puis on refroidit le milieu réactionnel à 0C. On essore le dichlor-hydrate, le lave avec un peu d'éthanol absolu à 0C puis le 1 ~6~26~
sèche sous vide à 55C. Il fond avec decomposition entre 180 et 185C.
L'analyse du produit obtenu donne les résultats suivants:
.
Analyse calculé pour C10 H16 N2 3'Trouvé
C% 42,12 42,24 H% 6,36 6,39 N~ 9,82 9,73 O% 16,83 17,07 Cl~ 24,87 24,90-24,94 Exemple 2: Preparation du dichlorhydrate de (diamino-2,4) phényl ~ dihydroxypropyléther ~H2 ~ , 2HCl Première phase:
OK
f + ClCH2-CHOH-CH20H
f -CH2 -CHOH-CH20H
~ NHCOCH3 ~' 1 1682~6 Deuxième phase:
ol-CH2-CHOH-CH20H Ol-CH2-CHOH-CH20H
NHCOCH3 ~ ~ -NHCOCH3 NO~ H2 Troisième phase:
O-CH2-CHOH-CH20H Ol-CH2--CHOH--CH20H
HCOCH ~ ~ NH2 I 3 -~
, HCl ~ , 2HCl Première étape: Préparation de l'(acétylamino-2 nitro-4) phenyl ~,~-dihydroxypropyléther On introduit 0,2 mole (46,8 g) de sel de potassium de l'acétylamino-2 nitro-4 phénol dans 100 ml de chloro-l propanediol-2,3 additionnés de 20 ml d'eau. On chauffe le melange pendant 10 heures au bain-marie bouillant. On ajoute 0,1 mole (13,8 g) de carbonate de potassium puis on prolonge le chauffage pendant six heures. Apr~s refroidissement et elimination des sels minéraux par filtration, on ajoute 250 ml d'ethanol (à 96) au filtrat puis on le refroidit pendant une nuit à 0C. Le produit attendu cristallise. On l'essore; on le lave à l'ethanol, puis avec une solution sodique normale, puis à l'eau.
Après deux recristallisations dans l'ethanol et se-chage sous vide à 55C, le produit fond a 142C.
L'analyse du produit obtenu donne les résultats suivants:
1 16~26~
Analyse I Calculé pour Cll H14 2 6 Trouve . .
C% 48,89 48,77 1~ 5,22 5,15 N% 10,37 10,44 O% 35,52 35,32-35,46 Deuxieme etape: Preparation du chlorhydrate d'(acetylamino-2 amino-4) phenyl ~ dihy~r~oxypropylether On porte au reflux, sous agitation, 17 ml d'ethanol (à 96) additionnes de 2,5 ml d'eau, 0,4 g de chlorure d'am-monium et 8 g de zinc en poudre; puis on ajoute, peu à peu tout en maintenant l'agitation, 1,33 x 10 2 mole (3,6 g) d'(acetylamino-2 nitro-4) phenyl ~,~-dihydroxypropylether.
L'addition terminee, le milieu réac-tionnel etant decolore, on filtre ce dernier en recueillant le filtrat dans 1,5 ml d'ethanol (à 96) additionne de 1,5 ml d'acide chlorhydrique à 36 % en refroidissant à l'aide d'un melange ethanol-carboglace. Dans le filtrat refroidi, le produit attenducristallise sous forme de chlorhydrate. Il est essore, lave avec un peu d'ethanol absolu prealablement refroidi, puis seche sous vide à 55C.
L'analyse du produit obtenu donne les resultats suivants:
Analyse Calcule pour Cll H16 N2 4 ~rc~
C% 47,74 47,86 H~ 6,19 6,26 N% 10,12 10,16 O% 23,13 23,08 C1% 12,81 12,90 ~. 16826~
Troisième etape: Preparation du dichlorhydrate de (diamino-2,4 ?
-phényl ~ dihydroxypropylether On introduit 0,195 mole (54 g) du chlorhydrated'(acetylamino-2 amino-4) phényl ~ dihydroxypropyléther dans 270 ml d'éthanol absolu saturé de gaz chlorhydrique et additionnés de 54 ml de solution chlorhydrique 12 N. On chauffe le milieu réactionnel, sous agitation, pendant une heure au voisinage de 100C. On essore le dichlorhydrate attendu, qui est insoluble dans le milieu réactionnel chaud.
Le produit est lavé avec un peu d'éthanol absolu saturé de gaz chlorhydrique puis a l'acetone. Après sechage sous vide à 55C, il fond avec decomposition entre 210 et 215C.
L'analyse du produit obtenu donne les resultats suivants:
Analyse Calcule pour Cg Hl~ N2 3~ 2HCl Trouvé
C% 39~86 39,96 H% 5,95 6,04 N% 10,33 10,28 O% 17,70 17,64 Cl% 26,15 26,23 _emple 3:
On prépare la composition tinctoriale suivante:
Composé de l'exemple 1........................... 2,85 g Paraphénylènediamine............................. 1,08 g Nonylphénol oxyéthyléné à quatre moles d'oxyde d'éthylène vendu sous la dénomination CEMULSOL
NP4 (marque de commerce)~ par la société
RHONE POULENC~>................................. 21 g Nonylphénol oxyéthyléné a neuf moles d'oxyde 1 16~266 d'éthylène vendu sous la dénomination CEMULSOL
NP9 (marque de colNmerc~) par la societe RHONE POULENC................................... 24 c3 Acide oleique..................................... 4 gButoxy-2 éthanol.................................. 3 g Ethanol (à 96)................................... 10 g Sel pentasodique de l'acide diéthylène-triamine-pentaacetique vendu sous la denomi-nation MASQUOL DTPA (marque de commerce)........ 2,5 g Acide thioglycolique.............................. 0,6 gAmmoniaque (à 22B)............................... 10 g Eau... qsp.. ....................................100 g Le pH de la composition est egal à 9,7.
Au moment de l'emploi, on ajoute 100 g d'eau oxygenee à 20 volumes.
Ce melange, applique pendant 25 mn à 28C sur des cheveux naturellement blancs à 90%, leur confère, après rinçage et shampooing, une coloration bleu-noir.
Exemple 4:
On prépare la composition tinctoriale suivante:
Composé de l'exemple 2.......................... 0,0067 g Paraphénylènediamine............................ 0,0027 g Butoxy-2 ethanol................................ 8 g Carboxymethylcellulose.......................... 2 g Laurylsulfate d'ammonium........................ 5 g Acetate d'ammonium.............................. 1 g Propylèneglycol................................. 8 g Sel pentasodique de l'acide diethylène-triamine-pentaacetique vendu sous la denomi-nation MASQUOL DTPA (marque de commerce)...... 2 Acide thioglycolique............................ 0,4 g Ammoniaque (à 22B)............................. 5 g 1 1682~
~au... qsp.. ....................................100 g Le pH de la composition est éyal à 10,1.
Au momen-t de l'emploi, on ajoute 50 g d'eau oxygenée à 20 volumes.
Ce mélange, appliqué pendant 30 mn a 28C sur des cheveux préalablemen-t décolorés au blanc, leur confere, apres ,rinçage et shampooing, une coloration argent clair bleuté.
Exemple 5:
.
On prépare la composition tinctoriale suivante:
Composé de l'exemple 2......................... 0,5~2 g Paraaminophénol................................ 0,218 g Polymere de l'acide acrylique ayant un poids moléculaire cle 2 à 3 millions, vendu sous la dénomination CARBOPOL 934 (marque de com-merce) par la société GOODRICII CHEMICALCO~. 1 J 5 g Ethanol..... ~........................................ 11 g Butoxy-2 ethanol............................... .5 g Bromure de trimé-thylcé-tylammonium............ .1 g Acide éthylène-diamine-tétraacétique vendu sous la dénomination TRILON B (marque de commerce)..................................... .0,1 g Ammoniaque (à 22B)............................ 10 g Acide thio~lycolique........................... .0,2 c~
Eau...qsp........................................... 100 cJ
Le plI de la composition est égal à 10,2.
Au moment cle l'emploi, on a]oute ~0 g d'eau oxygénée à 20 volumes.' Ce mélanc~e, appliqué penclant 25 mn a 2cC sur des cheveux naturellement blancs a 90 ~, leur confere, apres rinçage et shampooing, une coloration rouge sombre.
Exemple 6:
On prépare la composition tinctoriale s~livante:
1 1~8~
Composé d~ l'exemple 1................................. 1,42 g Paraaminophenol........................................ .0,55 g Butoxy-2 ethanol....................................... .8 g Propylèneglycol................... ~.................... .8 g Carboxyméthylcellulose.......................... ....... .2 g Laurylsulfate d'ammonium........................ ....... .5 g Sel pentasodique de l'acide diéthylène-triamine-pentaacétique vendu sous la dénomina-tion MASQUOL DTPA (marque de commerce)........ 2 Y
Acide thioglycolique............................ 0,4 g Ammoniaque (à 22B)............................. 10 g Eau... qsp.. ....................................100 g Le pH de la composition est égal à 10.
Au moment de l'emploi, on ajoute 100 g d'eau oxygénée à 20 volumes.
Ce mélange, appliqué pendant 30 mn à 25C sur des cheveux na-turellement blancs ~ 90 %, leur confere, après rinsage et shampooing, une coloration cuivre rouge.
Exemple 7:
On prépare la composition tinctoriale suivante:
Composé de l'exemple 2........................... 0,271 g Dichlorhydrate de N-~-méthoxyéthylamino-4 aniline.......................................... 0,239 g Nonylphénol oxyéthyléne à quatre moles d'oxyde d'éthylène vendu sous la dénomination CEMULSOL
NP4 (marque de commerce) par la société
RHONE POULENC.................................. 12 g Nonylphénol oxyéthyléné à neuf moles d'oxyde d'éthylène vendu sous la denomination CEMU~.SOL NP9 (marque de commerce)>~ par la societe RHONE POULENC.......................... 15 g Alcool oleique oxyethylené à deux moles d'oxyde d'éthylène............................... 1,5 g 1 16~2~6 Alcool oleique oxyéthyléné à qua-tre moles d'oxyde d'ethyl~ne.............................. ..1,5 g Propylèneglycol................................. ..6 g Acide ethylène-diamine-tétraacetique vendu sous la denomination TRILON B (marque de commerce)...... ~............................... ..0,12 g Ammoniaque (à 22B)............................. .11 g Acide thioglycolique............................ ..0,6~ g Eau... qsp....................................... 100 g Le pH de la composition est egal à 10,4.
Au moment de l'emploi, on ajoute 100 g d'eau oxygenee 20 volumes.
Ce melange, applique pendant 20 mn à 25C sur des cheveux naturellement blancs à 90 ~, leur confère, après rinsage et shampooing, une coloration bleu franc.
Exemple 8:
On prepare la composition tinctoriale suivante:
Compose de l'exemple 1.......................... 0,285 g Dichlorhydrate de dimethyl-2,6 paraphenylène-diamine......................................... 0,209 g Alcool oleique oxyethylene à deux moles d'oxyde d'ethy]ène.............................. 4,5 g Alcool oleique oxyethylene à quatre moles d'oxyde d'ethylène.............................. 4,5 g Amine oleique oxyethylenee à douze moles d'oxyde d'ethylène vendue sous le nom de aETHOMEEN TO12 (marque de commerce) par la societe ARMOUR HESS........................... 4,5 g Diéthanolamides d'acides gras de coprah......... 9 g Propylèneglycol................................. 4 g Butoxy-2 ethanol................................ 8 g Ethanol (à 96)................................. 6 g 1 lS8266 Sel penta~odique de l'acide diethylène-triamine-pentaacetique vendu sous la deno~
mination MASQUOL DTPA (marque de commerce). 2 g Hydroquinone...... ~................................... 0,15 g Solution de bisulfite de sodium (à 35B)........ 1,3 g Ammoniaque (à 22B)............................. 5 g Eau... qsp.. ....................................100 g Le pH de la composition est egal à 10.
Au moment de l'emploi, on ajoute 100 g d'eau oxygenee à 20 volumes.
Ce melange, applique pendant 30 mn à 28C sur des cheveux prealablement decolores au blanc, leur confère, après rinçage et shampooing, une coloration bleu intense legère-ment pourpre.
Exemple 9:
On prepare la composition tinctoriale suivante:
Compose de l'exemple 1.......................... 0,012 g Paraphenylènediamine............................ 0,108 g Dichlorhydrate de dimethyl-2,6 paraphenylène-diamine......................................... 0,0502 g Paraaminophenol................................. 0,155 g Methyl-2 résorcine.............................. 0,19 g Metaaminophenol................................. 0,12 g Phényl-l methyl-3 pyrazolone-5.................. 0,09 g (N-methylamino-3 nitro-4) phenoxyethanol....... 0,2 g Nonylphenol oxyethylene à quatre moles d'oxyde d'ethylène vendu sous la denomination CEMULSOL NP4 (marque de commerce) par la société RHONE POULENC................ ~.............. 12 g Nonylphénol oxyéthyléné à neuf moles d'oxyde d'ethylène vendu sous la denomination CEMULSOL NP9 (marque de commerce)~> par la 1 1~8266 société RHONE POULENC............................. 15 g Alcool oléique oxyéthyléné à deux moles d'oxyde d'éthylène.... -........................ .1,5 g Alcool oléique oxyéthyléné à quatre moles d'oxyde d'éthylène............................. .1,5 g Propylèneglycol................................ .6 g Acide éthylene-diamine-tétraacétique vendu sous la dénomination TRILON B (marque de commerce)..................................... .0,12 g Ammoniaque (à 22s)............................ 11 g Acide mercaptosuccinique............................ .0,2 g Eau...qsp........................................... 100 g Le pH de la composition est égal à 10,4.
Au moment de l'emploi, on ajoute 75 g d'eau oxygénée à 20 volumes.
Ce mélange, appliqué pendant 25 mn à 30C sur des cheveux préalablement décolorés au blanc, leur con~re, après rinçage et shampooing, une coloration sable doré.
Exemple 10:
On prépare la composition tinctoriale suivante:
Composé de l'exemple 2.......................... 0,065 g Paraphenylènediamine............................ 0,2 g Paraaminophenol................................. 0,4 g Sulfate de N-méthylparaaminophénol.............. 0,31 g Méthyl-2 résorcine.............................. 0,3 g Métaaminophénol................................. 0,405 g Méthyl-2 N-~-hydroxyéthylamino-5 phenol......... 0,08 g (N-méthylamino-3 nitro-4) phénoxyethanol........ 0,5 g Alcool oleique oxyethylene à deux moles d'oxyde d'éthyl~ne.............................. 4,5 g Alcool oléique oxyéthyléné à quatre moles d'oxyde d'ethylène.............................. 4,5 g 1 1~826S
Amine oleique oxyethylenee a deux moles dloxyde d'éthylène vendue sous le nom de ETHOMEEN TO12 (marque de commerce)~> par la société aARMOUR HESS)~....................... 4,5 g Diéthanolamides d'acides gras de coprah......... 9 g Propylèneglycol................................. 4 g sutoxy-2 éthanol................................ 8 g Ethanol (à 96)................................. 6 ` g Sel pentasodique de l'acide diéthylène-triamine-pentaacétique vendu sous la dénomi-nation MASQ~OL DTPA (marque de commerce)...... 2 g Hydroquinone.................................... 0,15 g Solution de bisulfite de sodium (à 35B)........ 1,3 g Ammoniaque (à 22B)............................. 8 g Eau... qsp.. ....................................100 Le pH de la composition est égal à 10,5.
Au moment de l'emploi, on ajoute 80 g d'eau oxygenée à 20 volumes.
Ce mélange, appliqué pendant 35 mn à 30C sur des cheveux préalablement décolorés au blond paille, leur ; confère, après rinçage et shampooing, une coloration chatain moyen à reflets cuivrés.
Exemple 11:
On prépare la composition tinctoriale suivante:
Compose de l'exemple 1.......................... 0,52 g Paraphenylènediamine............................ 0,6 g Paraaminophenol................................. 0,8 g Dichlorhydrate de N,N-di-~-hydroxyéthylamino-4 aniline......................................... 1 g Métaaminophénol................................. 0,5 g Résorcine....................................... 1,54 g Nitro-3 amino-4 phénol.......................... 0,6 g 1 16~2~6 Alcool oleique oxyethylené à deux moles d'oxyde d'ethylène............................. .4,5 g Alcool oléique oxyethylené ~ quatre moles d'oxyde d'ethylène............................. .4,5 g Amine oleique oxyéthylenee à douze moles d'oxyde d'éthylane vendu sous le nom de ETHOMEEN TO12 (marque de commerce) par la sociéte ARMOUR HESS.......................... .4,5` g Diethanolamides d'acides gras de coprah........ .9 g Propylèneglycol................................ .4 g Butoxy-2 ethanol............................... .8 g Ethanol (à 96)................................ ..6 g Sel pentasodique de l'acide diethylène-triamine-pentaacetique vendu sous la denomi-nation MASQUOL DTPA (marque de commerce)..... ..2 g Acide thioglycolique........................... ..0,5 g Ammoniaque (à 22B)............................ .10 g Eau... qsp.................................................. 100 g ; Le pH de la composition est egal ~ 10,3.
Au moment de l'emploi, on ajoute 100 g d'eau oxygenee ~ 20 volumes.
Ce melange, applique pendant 30 mn à 28C sur des cheveux decolores au ~lond fonce, leur confère, après rinçage et shampooing, une coloration brune.
Exemple 12:
On prepare la composition tinctoria]e suivante:
Compose de l'exemple 2.......................... 0,04 g Paraphenylènediamine............................ 0,955 g Orthoaminophénol................................ 0,375 g Résorcine....................................... 0,09 g Métaaminophénol................................. 0,155 g Méthyl-2 N-~-hydroxyethylamino-5 phenol......... 1,12 g 1 1 6~2~6 Alcool cétylstearylique vendu sous la deno-mination ~LFOL C16/18 E (marque de com-merce) par la societé CONDEA>~ 19 g 2-octyl dodecanol vendu sous Le nom EUTANOL
G (marque de commerce) par la société
KENKEL........................................ 4,5 g Alcool cétylstéarylique à quinze moles d'oxyde d'éthylène vendu sous le nom de ~(MERGITAL CS 15/E (marque de commerce) par la société KENKEL............................. 2,5 g Laurylsulfate d'ammonium à 30 % de matière active.......................................... 12 g Polymère constitué à base de motifs récurrents de formule ~ ~3 / CH3 6~ CH3 t \ CH 2 3 N \ (CH2) Cl ~ Cl ~3 ............................................. 4 g Alcool benzylique............................... 2 g Ammoniaque (à 22B)............................. 11 g Acide éthylène-diamine-tétraacétique vendu sous la dénomination TRILON ~ (marque de commerce)...................................... 1 g Solution de bisulfite de sodium (d=1,3)......... 1,2 g Eau...qsp........................................... 100 g Ie pH de la composition est égal à 10,2.
Au moment de l'emploi, on ajoute 100 g d'eau oxygénée à 20 volumes.
Ce mélange, appliqué pendant 20 mn à 25C sur des cheveux décolorés au jaune paille, leur con~ère, après rinçage et shampooing, une coloration pourpre noir~
:I L6~2~
Exemple 13:
On prépare la composition tinctoriale suivante:
Composé de l'exemple 1.......................... 0,1 g Paraphénylènediamine............................ 0,31 g Paraaminophénol................................. 0,4 g Sulfate de N-méthylamino-4 phénol............... 0,4 g Résorcine....................................... 0,5 g Métaaminophénol................................. 0,3` g Méthyl-2 N-~-hydroxyéthylamino-5 phénol......... 0,41 g Isopropyl-2 nitro-6 aniline..................... 0,81 g Alcool cétylstéarylique vendu sous la déno-mination ALFOL C16/18 E (marque de commerce) par la société CONDEA......................... 8 g Sulfate cetylstéarylique de sodium vendu sous la dénomination CIRE DE LANETTE E Imarque de commerce) par la société HENKEL........... 0,5 g Huile de ricin éthoxylée vendue sous la dénomination CEMULSOL B (marque de com-merce) par la sociéte RHONE POULENC.......... 1 g Diethanolamide oleique.......................... 1,5 g Sel pentasodique de l'acide diethylène-triamine-pentaacetique vendu sous la deno-mination <~MASQUOL DTPA (marque de commerce). 2,5 g Acide thioglycolique............................ 0,5 g Hydroquinone.................................... 0,15 g Ammoniaque (à 22B)............................. 11 g Eau... qsp.. ....................................100 g Le pH de la composition est egal à 10,4.
Au moment de l'emploi, on ajoute 100 g d'eau oxygenée à 20 volumes.
Ce mélange, appliqué pendant 30 mn a 30C sur des cheveux decolores au blanc, leur confere, apres rinçage 1 1682~6 et shampooing, une coloration cha-tain moyen cuivre.
Exemple 14:
On prepare la composition tinctoriale suivante:
Composé de l'exemple 1......................... 0,0143 g Dichlorhydrate de N-~-methoxyethylamino-4 aniline........................................ 0,0120 g Polymère de l'acide acrylique ayant un poids moléculaire de 2 à 3 millions vendu sous la denomination CARBOPOL 934 (marque de com-merce) par la société GOOPRICH CHEMICAL CO 1,5 g Ethanol (à 96)................................ 11 g Butoxy-2 éthanol............................... ..5 g Bromure de trimethylcétylammonium.............. .1 g Acide éthylène-diamine-tétraacétique vendu sous la dénomination TRILON B (marque de commerce)..................................... ..0,1 g Ammoniaque (à 22B)............................ .10 g Acide thioglycolique........................... ..0,2 g Eau... qsp...................................... 100 g Le p~ de la composition est egal à 10,2.
Au moment de l'emploi, on ajoute 20 g d'eau oxygénée à 20 volumes.
Ce mélange, appliqué pendant 30 mn à 30C sur des cheveux décolores au blanc, leur confère, après rinçage et shampooing, une coloration bleu turquoise clair argente.
Exemple 15:
On prepare la composition tinctoriale suivante:
Compose de l'exemple 1.......................... 0,055 g Paraphenylènediamine............................ 0,058 g Paraaminophenol................................. 0,5 g Resorcine....................................... 0,4 g Métaaminophenol................................. 0,103 g 1 1~82~
Methyl-2 N-~-hydroxyethylamino-5 phenol....... ..0,05 g Nitro-3 N-methylamino-4 N,N-di-~-hydroxy-ethylaniline.................................. ..0,31 g Nonylphenol oxyethyléne a quatre moles d'oxyde d'ethylene vendu sous la denomination REMCOPAL
334 (marque de commerce) par la societé
aGERLAND..................................... .12 g Nonylphenol oxyethyléné à neuf moles d'oxyde d'ethylene vendu sous la denomination REMCOPAL 349 (marque de commerce) par la societé GERLAND............................. .15 g Alcool oléique oxyethylene a deux moles d'oxyde d'ethylene............................ ..1,5 g Alcool oleique oxyethylene à quatre moles d'oxyde d'ethylène............................ ...1,5 g Propylèneglycol............................... ...6 g Solution de bisulfite de sodium (à 35B)...... ...1,2 g Acide ethylène-diamine-tétraacétique vendu sous la dénomination TRILON B (marque de commerce).................................... ...0,12 g Triéthanolamine............................... PII 8,5 Eau... qsp..... ~..................................... .100 g Au moment de l'emploi, on ajoute 70 g d'eau oxygénée a 20 volumes.
Ce melange, applique pendant 25 mn a 28C sur des cheveux decolores au blanc, leur confere, apres rinçage et shampooing, une coloration noisette.
Exemple 16:
On prepare la composition tinctoriale suivante:
Compose de l'exemple 1........................ 1,3 g Paraphenylenediamine.......................... 1,81 g Paraaminophenol............................... 0,8 g ~ 16~266 Dichlorhydrate de (diamino-2,4)phenoxyéthanol 0,2 g Methyl-2 N-~-hydroxyethylamino-5 phenol......... 0,803 y Resorcine....................................... 0,81 g Metaaminophenol................................. 0,9 g Nonylphenol oxyéthyléné à quatre moles d'oxyde d'éthyl~ne vendu sous la denomination CEMULSOL NP4 (marque de commerce~ par la societe RHONE POULENC......................... 21 ` g Nonylphenol oxyethylene à neuf moles d'oxyde d'ethylène vendu sous la denomination CEMULSOL NP9 (marque de commerce) par la societe RHONE POULENC......................... 24 g Acide oleique................................... 4 g Butoxy-2 ethanol................................ 3 g Ethanol (à 96)................................. 10 g Sel pentasodique de l'acide diethylène-triamine pentaacetique vendu sous la denomi-nation MASQUOL DTPA (marque de commerce)...... 2,5 g Acide thioglycolique............................ 0,6 g Ammoniaque (à 22B)............................. 10 g Eau... qsp.. ....................................100 g Le pH de la composition est egal à 9,5.
Au moment de l'emploi, on ajoute 120 g d'eau oxygenee à 20 volumes.
Ce melange, appliqué pendant 25 mn à 28C sur des cheveux décolorés au jaune paille, leur confère, après rincage et shampooing, une coloration noir corbeau.
Exemple 17:
On prépare la composition tinctoriale suivante:
Compose de l'exemple 1......................... 0,252 g Dichlorhydrate de N-~-methoxyethylamino-4 aniline........................................ . 0,6 g ~ 16~266 Dichlorhydrate de dimethyl-2,6 para-phénylènediamine.,............................... 0,2 g Paraaminophenol....... ,.......................... 0,6 g Résorcine....................................... . 0,905 g Métaaminophenol................................. . 0,435 g Methyl-2 N-~-hydroxyéthylamino-5 phénol.......... 0,2 g Hydroxy-6 benzomorpholine........................ 0,435 g Methyl-2 amino-4 nitro-5 phénol.................. 0,703 g Nonylphénol oxyéthyléné a quatre moles d'oxyde d'éthylène vendu sous la denomination CEMULSOL NP4 (marque de commerce) par la société RHONE POULENC.......................... 12 g Nonylphénol oxyéthyléné à neuf moles d'oxyde d'éthylene vendu sous la dénomination CEMULSOL
NP9 (marque de commerce) par la société
RHONE POULENC.................................. 15 g Alcool oléique à deux moles d'oxyde d'éthylène....................................... 1,5 g Alcool oléique à quatre moles d'oxyde d'éthylène............ ~.......................... .1,5 g Propylèneglycol.................................. .6 g Acide éthylène-diamine-tétraacétique vendu sous la dénomination TRILON B (marque de commerce)....................................... .0,12 g Ammoniaque (à 22B).............................. 11 g Acide thioglycolique............................. .0,6 g Eau... qsp.. ....................................100 g Le pH de la composition est égal a 9,9.
Au moment de l'emploi, on ajoute 100 g d'eau oxygénée à 20 volumes,.
Ce mélange, appliqué pendant 30 mn à 30C sur des cheveux naturellement blancs à 90 % leur confère, après 1 ~682~
rinçage et shampooing, une colora-tion chatain clair cuivré.
Exemple 18:
On prepare la composition tinctoriale suivante:
Compose de l'exemple 1........................... 0,306 g Paraphenylènediamine............................. 0,307 g Dichlorhydrate de N-~-méthoxyéthylamino-4 aniline.......................................... 0,15 g Methyl-2 resorcine......................... ~..... 0,405 g Methyl-2 N-~-hydroxyethylamino-5 phenol.......... 0,115 g Dichlorhydrate de (diamino-2,4) phenoxy-ethanol.......................................... 0,106 g Amino-2 nitro-3 phenol........................... 0,203 g Alcool cetylstearylique vendu sous la deno-mination ALFOL C16/18 E (marque de com-merce)~> par la societe <~CONDEA................ 8 g Sulfate cetylstearylique de sodium vendu sous la denomina-tion CIRE DE LANETTE E (marque de commerce) par la soci~ete HENKEL.............. 0,5 g Huile de ricin ethoxylee vendue sous la denomination CEMULSOL B (marque de commerce) par la societe RHONE POULENC>~.................. 1 g Diethanolamide oléique........................... 1,5 g Sel pentasodique de l'acide diéthylène-triamine-pentaacétique vendu sous la denomina-tion <~MASQUOL DTPA (marque de commerce)........ 2,5 g Acide thioglycolique............................. 0,5 g Hydroquinone..................................... 0,15 g Ammoniaque (à 22B).............................. 11 g Eau... qsp........................................ 100 g Le pH de la composition est egal à 10,3.
Au moment de l'emploi, on ajoute 90 g d'eau oxygenee à 20 volumes.
1 16~2~
Ce melange, applique pendant 25 mn à 25C sur des cheveux naturellement blancs ~ 90 %, leur confère, après rinçage et shampooing, une coloration gris an-thracite.
Exemple 19:
On prepare la composition tinctoriale suivante:
Compose de l'exemple 2................. ~........ 1,5 g Compose de l'exemple 1.......................... 0,42 g Paraphényl~nediamine............................ 0,62` g Dichlorhydrate de N,N-di-~-hydroxyethyl-amino-4 aniline................................. 0,42 g Paraaminophenol........................ 0,705 g Resorcine...................................... 0,81 g Methyl-2 N-~-hydroxyethylamino-5 phenol........ 0,21 g Amino-2 nitro-3 phenol......................... 0,61 g Alcool cetylstearylique vendu sous la denomi-nation ALFOL C16/18 E (marque de commerce) par la societe CONDEA........................ 8 g Sulfate cetylstearylique de sodium vendu sous la denomination CIRE DE LANETTE E (marque de commerce) par la societe HENKEL)>............ 0,5 g Huile de ricin ethoxylee vendue sous la denomination CEMULSOL B (marque de com-merce) par la societe RHONE PO~LENC......... 1 g Diethanolamide oleique......................... 1,5 g Sel pentasodique de l'acide diethylène-triamine-pentaacetique vendu sous la denomi-nation MASQUOL DTPA (marque de commerce)..... 2,5 g Acide thioglycolique........................... 0,5 g Hydroquinone................................... 0,15 g Ammoniaque (à 22B)............................ 11 g Eau...qsp...................... 100 g Le pH de la composition est egal à 10,1.
11682~6 Au moment de l'emyloi, on ajoute 100 g d'eau oxygénée à 20 volumes.
Ce melange, applique pendant 20 mn à 28C sur des cheveux naturellement blancs à 90 %, leur confère, apres rincage et shampooing, une coloration brun tres sombre.
Il est blen entendu que les modes de realisation ci-dessus references ne sont aucunement limitatifs et pour-ront donner lieu à toutes modifications desirables, `sans sortir pour cela du cadre de l'invention. 6) direct dyes and for example those chosen in the class of nitro dyes of the benzene series such as N, N-bis- (~ -hydroxyethyl) amino-l nitro-3 N'-4-methylamino benzene, N, N-tmethyl, ~ -hydroxyethyl) amino-l nitro-3 N '- (~ -hydroxyethyl) amino-4 benzene, N, N- (methyl, ~ -hydroxyethyl) amino 1 nitro-3 N'-methylamino-4 benzene, nitro-3 N- (~ -hydroxyethyl) amino-4 anisole, nitro-3 N- (~ -hydroxyethyl) amino-4 phenol, le (nitro-3 amino-4) phenoxyethanol, (3-nitro-N-methylamino-4) phenoxyethanol, N- (~ -hydroxyethyl) 2-amino-5-nitro anisole.
The pH of the dye compositions according to the invention is basic, for example between 8 and 11.5. From alkalizing agents which can be used, one can mention ammonia, alkylamines such as ethyl-amine or triethylamine, alkanolamines such as mono, di or tri-ethanolamine, alkyl alkanolamines such as methyl diethanolamine, hydroxides of sodium or potassium, sodium carbonates, potassium or ammonium. Among the acidifying agents that can be used, we can mention lactic acid, acid acetic, tartaric acid and phosphoric acid.
The cosmetically acceptable carrier, which is combine with base (s), couple (s), and possibly colorant (s) direct (s) of the composition may comprise, in addition to water, surfactants, organic solvents, products thickeners, antioxidants, "` 11 ~ 2fi6 penetration, foaming agents, sequestering agents, film-forming products, treatment agents and perfumes.
We can add to the composition according to the invention surfactants, anionic, cationic, non ionic, amphoteric or a mixture thereof. Among the surfactants particularly useful active ingredients, we can mention the alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfates, ether ~ sulfates and sulfonates of fatty alcohols, quaternary ammonium salts such as trimethyl bromide cetylammonium, cetyl-pyridinium bromide, diethanol-fatty acid amides, polyoxyethylenated acids and alcohols or polyglyceroles and polyoxyethylenated or poly-glycerols. Preferably, the surfactants are present in the composition according to the invention in a proportion included between 0.5 and 55% by weight and, advantageously, between 4 and 40%
by weight relative to the total weight of the composition.
We can also add, in the composition according to the invention, organic solvents for solubilizing compounds which are not sufficiently soluble in water.
Among the solvents which can advantageously be used, there are may mention, by way of example, ethanol, isopropanol, glycerin, glycols and their ethers like butoxy-2 ethanol, ethylene glycol, propylene glycol, monoethyl-ether and the monomethyl ether of diethylene glycol and solvents analogues. Solvents can advantageously be present in the composition in a proportion ranging from 1 to 40 ~ in weight and preferably between 5 and 30% by weight relative to the total weight of the composition.
Thickeners, which can be added in the composition according to the invention, can advantageously be taken from the group consisting of sodium alginate, .
1 ~ 6826 ~
gum arabic, cellulose derivatives such as methyl-cellulose, hydroxyethylcellulose, hydroxypropylmethyl-cellulose, the sodium salt of carboxymethylcellu ~ ose and acrylic acid polymers; we can also use mineral thickening agents such as bentonite.
Preferably, the thickening agents are present in a proportion between 0.5 and 5% by weight relative to the total weight of the composition and, advantageously, be 0.5 and 3 ~ by weight.
Antioxidants, which can be added to the composition according to the invention, can advantageously be taken from the group formed by sodium sulfite, thioglycolic acid, mercapto-succinic acid, sodium bisulfite, ascorbic acid and hydroquinone.
These antioxidants may be present in the composition in a proportion between 0.05 and 1.5 by weight relative to the total weight of the composition.
The dye composition according to the invention contains, at the time of use, oxidizing agents such as as hydrogen peroxide, urea peroxide or persalts, such than ammonium persulfate.
The dye composition according to the invention can be present as a liquid, cream, gel, aerosol or in any other suitable form, to achieve a tint-ture of keratin fibers.
The present invention also relates to a hair dyeing process, characterized in that a composition according to the invention is mixed with an agent oxidant, which is then applied to the hair, let the mixture act on the hair for a while between 5 and 45 minutes, which you rinse, that possibly wash with shampoo and rinse again, and 1,16826 ~
dries the hair.
To better understand the object of the invention, we are going to describe it now, as examples purely illustrative and not limiting, several methods of implementation artwork.
Example 1: Preparatio_ dihydrochloride (diamino-2! 4) p ~ yl ~ hydroxyethoxy) ethylether The compound prepared has the following formula: ~
O-CH ~ CH -O-CH -CH -OH
, 2HCl First phase:
OH K
IIICOCH3) ~ NIICOCH3 Second phase:
OK
~ Cl-CH2-CH2-0-CH2-CH2-OH
O-CH -CH -O-CH -CH -OH
~ HCOCH3 ~ ~ 82 ~ 6 third phase:
~ -CH2-CH2-O-CH2-CH2-OH
NHCOCH3 ->
O-CH -CH -O-CH -CH -OH
~ NHCOCH3 ~, HCl Fourth phase:
O-CH -CH -O-CH -CH -OH
NHcocH3 , HCl O-CH -CH -O-CH -CH -OH
~ NH2 ~, 2HCl First step: Preparation of the potassium salt of acetyl-2-amino-4-nitro phenol 2150 ml of ethanol containing 1.89 mole solution (133 g) of 80% potash are cooled to -10C; then we 3 gradually adds, with stirring and while maintaining the temperature below 5C, 1.89 mole (371 g) of acetylamino-2 4-nitro phenol. The potassium salt precipitates. We wring 1 1 ~ 8266 the product, washed with ethanol and dried under vacuum at 50C.
Second step: Preparation of (acetylamino-2 nitro-4) .
phenyl ~ '-hydroxyethoxy) ethylether 0.5 mole (117 g) of the potassium salt is introduced 2-acetylamino-4-nitro phenol in 500 ml of dimethyl-formamide; then 0.6 mol (64 ml) is added, with stirring diethylene glycol monochlorohydrin. The mixture is maintained for 8 hours ~ or stirring at a temperature close to 100C then pour into two liters of ice water.
The gross product is wrung; it is washed with water, then with a normal iced sodium solution, and finally with water. After vacuum drying and recrystallization from ethanol, expected product melts at 152C.
Analysis of the product obtained gives the results following:
Analysis Calculates for C12 H16 N2 6 Found C% 50.70 50.88 H% 5.67 5.64 N% 9.86 9.74 O% 33.77 33.90 Third step: Preparation of monohydrochloride (acetyl-amino-2 amino-4) phe_yl ~ hydroxyethoxy) _ ethylether 400 ml of ethanol are brought to reflux, with stirring.
(to 96) added with 75 ml of water, 10 g of amm chloride monium and 200 g of zinc powder; then, little by little while maintaining the stirring, 0.32 mole (91 g) of (acetyl-2-amino-4-nitro) phenyl ~ '-hydroxyethoxy) ethylether.
1 1 ~ 826 ~
After each addition, the reaction medium becomes very discolored quickly. The addition of the nitro derivative completed, we maintain heating for ten minutes then we filter the reaction medium, collecting the filtrate in 30 ml ethanol (96 ~) with 34 ml of hydrochloric acid to 36 ~ and previously cooled using a mixture dry ice-ethanol. The expected product crystallizes in the form hydrochloride. It is wrung out, washed with a little ethanol absolute previously cooled to -10C, then dried under vacuum at 55C.
Analysis of the product obtained gives the results - following:
Analysis calculated for C12 H18 N2 4 'Found C% .49.57 49.56 H ~ 6.58 6.50 N% 9.63 9.48 O ~ 22.01 21.83 Cl ~ 12.19 12.30 Fourth step: Preparation of dihydrochloride (diamino-2,4) phenyl ~ '-hydroxyethoxy) ethylether 0.25 mole is heated to reflux, with stirring (70.9 g) (2-acetylamino-4 amino) hydrochloride phenyl ~ - (B'-hydroxyethoxy) ethyl ether in 210 ml of ethanol absolute saturated with hydrochloric gas. After 10 minutes of heating, the dissolution is complete then the expected dihydrochloride begins to precipitate after about half an hour. We maintains the heating for a whole hour then cools the reaction medium to 0C. We wring out the dichlor-hydrate, wash it with a little absolute ethanol at 0C and then 1 ~ 6 ~ 26 ~
vacuum dried at 55C. It melts with decomposition between 180 and 185C.
Analysis of the product obtained gives the results following:
.
Analysis calculated for C10 H16 N2 3'Found C% 42.12 42.24 H% 6.36 6.39 N ~ 9.82 9.73 O% 16.83 17.07 Cl ~ 24.87 24.90-24.94 Example 2 Preparation of 2,4-diamino dihydrochloride phenyl ~ dihydroxypropylether ~ H2 ~, 2HCl First phase:
OK
f + ClCH2-CHOH-CH20H
f -CH2 -CHOH-CH20H
~ NHCOCH3 ~ ' 1 1682 ~ 6 Second phase:
ol-CH2-CHOH-CH20H Ol-CH2-CHOH-CH20H
NHCOCH3 ~ ~ -NHCOCH3 NO ~ H2 Third phase:
O-CH2-CHOH-CH20H Ol-CH2 - CHOH - CH20H
HCOCH ~ ~ NH2 I 3 - ~
, HCl ~, 2HCl First step: Preparation of (acetylamino-2 nitro-4) phenyl ~, ~ -dihydroxypropylether 0.2 mol (46.8 g) of potassium salt is introduced 2-acetylamino-4-nitro phenol in 100 ml of chloro-1 propanediol-2,3 added with 20 ml of water. We heat the mix for 10 hours in a boiling water bath. We add 0.1 mole (13.8 g) of potassium carbonate then extended heating for six hours. After cooling and removal of mineral salts by filtration, 250 ml are added ethanol (96) in the filtrate and then cooled for one night at 0C. The expected product crystallizes. We wring it out; we washed with ethanol, then with a normal sodium solution, then with water.
After two recrystallizations from ethanol and se-vacuum vacuum at 55C, the product melts at 142C.
Analysis of the product obtained gives the results following:
1 16 ~ 26 ~
Analysis I Calculated for Cll H14 2 6 Found . .
C% 48.89 48.77 1 ~ 5.22 5.15 N% 10.37 10.44 O% 35.52 35.32-35.46 Second step: Preparation of hydrochloride (2-acetylamino amino-4) phenyl ~ dihy ~ r ~ oxypropylether 17 ml of ethanol are brought to reflux, with stirring.
(to 96) additions of 2.5 ml of water, 0.4 g of amm chloride monium and 8 g of zinc powder; then we add little by little while maintaining agitation, 1.33 x 10 2 mole (3.6 g) of (acetylamino-2 nitro-4) phenyl ~, ~ -dihydroxypropylether.
The addition completed, the reaction medium being discolored, the latter is filtered by collecting the filtrate in 1.5 ml ethanol (96) adds 1.5 ml of hydrochloric acid to 36% by cooling with an ethanol mixture-dry ice. In the cooled filtrate, the product awaits crystallization in the form of the hydrochloride. It is wrung out, wash with a little pre-cooled absolute ethanol, then vacuum dried at 55C.
Analysis of the product obtained gives the results following:
Analysis Calculates for Cll H16 N2 4 ~ rc ~
C% 47.74 47.86 H ~ 6.19 6.26 N% 10.12 10.16 O% 23.13 23.08 C1% 12.81 12.90 ~. 16826 ~
Third step: Preparation of 2,4-diamino hydrochloride?
-phenyl ~ dihydroxypropylether 0.195 mol (54 g) of the hydrochloride (2-acetylamino-4 amino) phenyl ~ dihydroxypropyl ether is introduced.
in 270 ml of absolute ethanol saturated with hydrochloric gas and added with 54 ml of 12N hydrochloric solution.
heats the reaction medium, with stirring, for one hour near 100C. We drain the dihydrochloride expected, which is insoluble in the hot reaction medium.
The product is washed with a little absolute ethanol saturated with hydrochloric gas then acetone. After vacuum drying at 55C, it melts with decomposition between 210 and 215C.
Analysis of the product obtained gives the results following:
Analysis Calculates for Cg Hl ~ N2 3 ~ 2HCl Found C% 39 ~ 86 39.96 H% 5.95 6.04 N% 10.33 10.28 O% 17.70 17.64 Cl% 26.15 26.23 _ample 3:
The following dye composition is prepared:
Compound of Example 1 ........................... 2.85 g Paraphenylenediamine ............................. 1.08 g Nonylphenol oxyethylenated to four moles of oxide ethylene sold under the name CEMULSOL
NP4 (trademark) ~ by the company RHONE POULENC ~> ................................. 21 g Oxyethylenated nonylphenol has nine moles of oxide 1 16 ~ 266 ethylene sold under the name CEMULSOL
NP9 (colNmerc ~ brand) by the company RHONE POULENC ................................... 24 c3 Oleic acid ..................................... 4 gButoxy-2 ethanol ...... ............................ 3 g Ethanol (96) ................................... 10 g Diethylene pentasodium salt-triamine-pentaacetic sold under the name MASQUOL DTPA nation (trademark) ........ 2.5 g Thioglycolic acid .............................. 0.6 g Ammonia (at 22B) .......... ..................... 10 g Water ... qs .. .................................... 100 g The pH of the composition is equal to 9.7.
At the time of use, add 100 g of water oxygenated to 20 volumes.
This mixture, applied for 25 min at 28C on naturally white hair at 90%, gives them, after rinse and shampoo, blue-black coloring.
Example 4:
The following dye composition is prepared:
Compound of Example 2 .......................... 0.0067 g Paraphenylenediamine ............................ 0.0027 g Butoxy-2 ethanol ................................ 8 g Carboxymethylcellulose .......................... 2 g Ammonium lauryl sulfate ........................ 5 g Ammonium acetate .............................. 1 g Propylene glycol ................................. 8 g Diethylene pentasodium salt-triamine-pentaacetic sold under the name MASQUOL DTPA nation (trademark) ...... 2 Thioglycolic acid ............................ 0.4 g Ammonia (at 22B) ............................. 5 g 1 1682 ~
~ au ... qsp .. .................................... 100 g The pH of the composition is equal to 10.1.
At the time of use, add 50 g of oxygenated water to 20 volumes.
This mixture, applied for 30 min at 28C on hair previously bleached white, gives them, after , rinse and shampoo, a bluish light silver coloring.
Example 5:
.
The following dye composition is prepared:
Compound of Example 2 ......................... 0.5 ~ 2 g Paraaminophenol ................................ 0.218 g Weight acrylic acid polymer molecular key 2 to 3 million, sold under the name CARBOPOL 934 (trade mark merce) by GOODRICII CHEMICALCO ~. 1 J 5 g Ethanol ..... ~ ........................................ 11 g Butoxy-2 ethanol ................................ 5 g Trimé-thylcé-tylammonium bromide ............. 1 g Ethylene-diamine-tetraacetic acid sold under the name TRILON B (brand of trade) ..................................... .0.1 g Ammonia (at 22B) ............................ 10 g Thio ~ lycolic acid ............................ 0.2 c ~
Water ... qs ........................................... 100 cJ
The fold of the composition is equal to 10.2.
At the time of use, we have] ~ 0 g of hydrogen peroxide 20 volumes. ' This mixture, applied for 25 minutes at 2cC on naturally white hair at 90 ~, gives them, after rinse and shampoo, a dark red color.
Example 6:
The tinctorial composition is prepared:
1 1 ~ 8 ~
Composed of Example 1 ................................. 1.42 g Paraaminophenol ........................................ .0.55 g Butoxy-2 ethanol ........................................ 8 g Propylene glycol ................... ~ ..................... 8 g Carboxymethylcellulose .......................... ........ 2 g Ammonium lauryl sulfate ........................ ........ 5 g Diethylene pentasodium salt-triamine-pentaacetic sold under the name tion MASQUOL DTPA (trademark) ........ 2 Y
Thioglycolic acid ............................ 0.4 g Ammonia (at 22B) ............................. 10 g Water ... qs .. .................................... 100 g The pH of the composition is equal to 10.
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture, applied for 30 min at 25C on naturally white hair ~ 90%, gives them after rinse and shampoo, a red copper color.
Example 7:
The following dye composition is prepared:
Compound of Example 2 ........................... 0.271 g N- ~ -methoxyethylamino-4 dihydrochloride aniline .......................................... 0.239 g Oxyethylene nonylphenol with four moles of oxide ethylene sold under the name CEMULSOL
NP4 (trademark) by the company RHONE POULENC .................................. 12 g Nonylphenol oxyethylenated to nine moles of oxide ethylene sold under the name CEMU ~ .SOL NP9 (trademark)> ~ by societe RHONE POULENC .......................... 15 g Oxyethylenated oleic alcohol at two moles ethylene oxide ............................... 1.5 g 1 16 ~ 2 ~ 6 Oxyethylenated oleic alcohol to four moles ethyl oxide ~ ne ............................... 1.5 g Propylene glycol .................................. 6 g Ethylene-diamine-tetraacetic acid sold under the name TRILON B (brand of trade) ...... ~ ................................ 0.12 g Ammonia (at 22B) .............................. 11 g Thioglycolic acid ............................ .,0,6 ~ g Water ... qs ....................................... 100 g The pH of the composition is equal to 10.4.
At the time of use, add 100 g of oxygenated water 20 volumes.
This mixture, applied for 20 min at 25C on hair naturally white at 90 ~, gives them, after rinse and shampoo, a clear blue color.
Example 8:
The following dye composition is prepared:
Compounds of Example 1 .......................... 0.285 g 2,6-dimethyl paraphenylene dihydrochloride diamine ......................................... 0.209 g Two mole oxyethylene oleic alcohol ethylene oxide .............................. 4.5 g Four mole oxyethylene oleic alcohol ethylene oxide .............................. 4.5 g Oxyethylenated oleic amine at twelve moles ethylene oxide sold under the name of aETHOMEEN TO12 (trademark) by the ARMOR HESS ........................... 4.5 g Diethanolamides of coconut fatty acids ......... 9 g Propylene glycol ................................. 4 g Butoxy-2 ethanol ................................ 8 g Ethanol (96%) ................................. 6 g 1 lS8266 Penta ~ odic salt of diethylene acid-triamine-pentaacetic sold under deno ~
MASQUOL DTPA mine (trademark). 2 g Hydroquinone ...... ~ ................................... 0.15 g Sodium bisulfite solution (35B) ........ 1.3 g Ammonia (at 22B) ............................. 5 g Water ... qs .. .................................... 100 g The pH of the composition is equal to 10.
At the time of use, add 100 g of water oxygenated to 20 volumes.
This mixture, applied for 30 min at 28C on hair previously discolored to white, gives them, after rinse and shampoo, a light intense blue coloring-lying purple.
Example 9:
The following dye composition is prepared:
Compounds of Example 1 .......................... 0.012 g Paraphenylenediamine ............................ 0.108 g 2,6-dimethyl paraphenylene dihydrochloride diamine ......................................... 0.0502 g Paraaminophenol ................................. 0.155 g Methyl-2 resorcin .............................. 0.19 g Metaaminophenol ................................. 0.12 g Phenyl-l methyl-3 pyrazolone-5 .................. 0.09 g (N-methylamino-3 nitro-4) phenoxyethanol ....... 0.2 g Four mole nonylphenol oxyethylene of ethylene oxide sold under the name CEMULSOL NP4 (trademark) by the RHONE POULENC ................ ~ .............. 12 g Nine mole oxyethylenated nonylphenol of ethylene oxide sold under the name CEMULSOL NP9 (trademark) ~> by 1 1 ~ 8266 RHONE POULENC ............................. 15 g Two mole oxyethylene oleic alcohol ethylene oxide .... -......................... 1.5 g Four-mole oxyethylenated oleic alcohol ethylene oxide .............................. 1.5 g Propylene glycol ................................ .6 g Ethylene-diamine-tetraacetic acid sold under the name TRILON B (brand of trade) ..................................... 0.12 g Ammonia (at 22s) ............................ 11 g Mercaptosuccinic acid ............................ .0.2 g Water ... qs ........................................... 100 g The pH of the composition is equal to 10.4.
At the time of use, 75 g of hydrogen peroxide are added to 20 volumes.
This mixture, applied for 25 min at 30C on hair previously bleached with white, their con ~ re, after rinsing and shampooing, a golden sand coloring.
Example 10:
The following dye composition is prepared:
Compound of Example 2 .......................... 0.065 g Paraphenylenediamine ............................ 0.2 g Paraaminophenol ................................. 0.4 g N-methylparaaminophenol sulfate .............. 0.31 g 2-methyl resorcin .............................. 0.3 g Metaaminophenol ................................. 0.405 g Methyl-2 N- ~ -hydroxyethylamino-5 phenol ......... 0.08 g (3-N-methylamino-4-nitro) phenoxyethanol ........ 0.5 g Two mole oxyethylene oleic alcohol ethyl oxide ~ ne .............................. 4.5 g Four-mole oxyethylenated oleic alcohol ethylene oxide .............................. 4.5 g 1 1 ~ 826S
Two-mole oxyethylenated oleic amine ethylene oxide sold as ETHOMEEN TO12 (trademark) ~> by aARMOUR HESS) ~ ....................... 4.5 g Diethanolamides of coconut fatty acids ......... 9 g Propylene glycol ................................. 4 g 2-sutoxy ethanol ................................ 8 g Ethanol (96) ................................. 6 `g Diethylene pentasodium salt-triamine-pentaacetic sold under the name MASQ nation ~ OL DTPA (trademark) ...... 2 g Hydroquinone .................................... 0.15 g Sodium bisulfite solution (35B) ........ 1.3 g Ammonia (at 22B) ............................. 8 g Water ... qs .. .................................... 100 The pH of the composition is equal to 10.5.
At the time of use, 80 g of oxygenated water are added to 20 volumes.
This mixture, applied for 35 min at 30C on hair previously bleached with straw blonde, their ; gives, after rinsing and shampooing, a brown color medium with copper highlights.
Example 11:
The following dye composition is prepared:
Compounds of Example 1 .......................... 0.52 g Paraphenylenediamine ............................ 0.6 g Paraaminophenol ................................. 0.8 g N, N-di- ~ -hydroxyethylamino-4 dihydrochloride aniline ......................................... 1 g Metaaminophenol ................................. 0.5 g Resorcinol ....................................... 1.54 g Nitro-3 amino-4 phenol .......................... 0.6 g 1 16 ~ 2 ~ 6 Oxyethylenated oleic alcohol at two moles ethylene oxide ............................. .4.5 g Oxyethylenated oleic alcohol ~ four moles ethylene oxide ............................. .4.5 g Oxyethylated oleic amine at twelve moles ethylane oxide sold as ETHOMEEN TO12 (trademark) by the ARMOR HESS .......................... .4,5` g Diethanolamides of coconut fatty acids ......... 9 g Propylene glycol ................................. 4 g Butoxy-2 ethanol ................................ 8 g Ethanol (96) ................................. 6 g Diethylene pentasodium salt-triamine-pentaacetic sold under the name MASQUOL DTPA nation (trademark) ..... ..2 g Thioglycolic acid ............................ 0.5 g Ammonia (at 22B) ............................. 10 g Water ... some ............................................. ..... 100 g ; The pH of the composition is equal to 10.3.
At the time of use, add 100 g of water oxygenated ~ 20 volumes.
This mixture, applied for 30 min at 28C on discolored hair with ~ dark london, gives them, after rinsing and shampoo, a brown coloring.
Example 12:
The following tinctoria composition is prepared:
Compounds of Example 2 .......................... 0.04 g Paraphenylenediamine ............................ 0.955 g Orthoaminophenol ................................ 0.375 g Resorcin ....................................... 0.09 g Metaaminophenol ................................. 0.155 g Methyl-2 N- ~ -hydroxyethylamino-5 phenol ......... 1.12 g 1 1 6 ~ 2 ~ 6 Cetylstearyl alcohol sold under the deno-mination ~ LFOL C16 / 18 E (trade mark merce) by CONDEA> ~ 19 g 2-octyl dodecanol sold under the name EUTANOL
G (trademark) by the company KENKEL ........................................ 4.5 g Cetylstearyl alcohol at fifteen moles ethylene oxide sold as ~ (MERGITAL CS 15 / E (trademark) by KENKEL ............................. 2.5 g Ammonium lauryl sulfate at 30% material active .......................................... 12 g Polymer made from recurring patterns of formula ~ ~ 3 / CH3 6 ~ CH3 t \ CH 2 3 N \ (CH2) Cl ~ Cl ~ 3 ............................................. 4 g Benzyl alcohol ............................... 2 g Ammonia (at 22B) ............................. 11 g Ethylene-diamine-tetraacetic acid sold under the name TRILON ~ (brand of trade) ...................................... 1 g Sodium bisulfite solution (d = 1.3) ......... 1.2 g Water ... qs ........................................... 100 g Ie pH of the composition is equal to 10.2.
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture, applied for 20 min at 25C on hair discolored to straw yellow, their con ~ era, after rinse and shampoo, a purple black color ~
: I L6 ~ 2 ~
Example 13:
The following dye composition is prepared:
Compound of Example 1 .......................... 0.1 g Paraphenylenediamine ............................ 0.31 g Paraaminophenol ................................. 0.4 g 4-N-methylamino phenol sulfate ............... 0.4 g Resorcin ....................................... 0.5 g Metaaminophenol ................................. 0.3` g Methyl-2 N- ~ -hydroxyethylamino-5 phenol ......... 0.41 g 2-Isopropyl-6-nitro aniline ..................... 0.81 g Cetylstearyl alcohol sold under the name ALFOL C16 / 18 E (trade mark) by CONDEA ......................... 8 g Cetylstearyl sodium sulfate sold under the name CIRE DE LANETTE E Imarque HENKEL ........... 0.5 g Ethoxylated castor oil sold under the name CEMULSOL B (trade mark merce) by RHONE POULENC .......... 1 g Diethanolamide oleic .......................... 1.5 g Diethylene pentasodium salt-triamine-pentaacetic sold under the deno-mination <~ MASQUOL DTPA (trademark). 2.5g Thioglycolic acid ............................ 0.5 g Hydroquinone .................................... 0.15 g Ammonia (at 22B) ............................. 11 g Water ... qs .. .................................... 100 g The pH of the composition is equal to 10.4.
At the time of use, add 100 g of water oxygenated to 20 volumes.
This mixture, applied for 30 min at 30C on hair discolored to white, gives them, after rinsing 1 1682 ~ 6 and shampoo, a medium brown copper color.
Example 14:
The following dye composition is prepared:
Compound of Example 1 ......................... 0.0143 g N- ~ -methoxyethylamino-4 dihydrochloride aniline ........................................ 0.0120 g Weight-heavy acrylic acid polymer molecular from 2 to 3 million sold under the name CARBOPOL 934 (trade mark merce) by GOOPRICH CHEMICAL CO 1.5 g Ethanol (96) ................................ 11 g Butoxy-2 ethanol ................................ 5 g Trimethylketylammonium bromide .............. .1 g Ethylene-diamine-tetraacetic acid sold under the name TRILON B (brand of trade) ..................................... ..0.1 g Ammonia (at 22B) ............................. 10 g Thioglycolic acid ............................ 0.2 g Water ... qs ...................................... 100 g The p of the composition is equal to 10.2.
At the time of use, 20 g of water are added oxygenated to 20 volumes.
This mixture, applied for 30 min at 30C on discolored white hair, gives them, after rinsing and shampoo, a light turquoise blue color.
Example 15:
The following dye composition is prepared:
Compound of Example 1 .......................... 0.055 g Paraphenylenediamine ............................ 0.058 g Paraaminophenol ................................. 0.5 g Resorcin ....................................... 0.4 g Metaaminophenol ................................. 0.103 g 1 1 ~ 82 ~
Methyl-2 N- ~ -hydroxyethylamino-5 phenol ........ 0.05 g Nitro-3 N-methylamino-4 N, N-di- ~ -hydroxy-ethylaniline ................................... 0.31 g Nonylphenol oxyethylene has four moles of oxide ethylene sold under the name REMCOPAL
334 (trademark) by the company AGERLAND ..................................... .12 g Nonylphenol oxyethylenated to nine moles of oxide ethylene sold under the name REMCOPAL 349 (trademark) by the GERLAND company ............................. .15 g Two mole oxyethylene oleic alcohol ethylene oxide ............................. 1.5 g Four mole oxyethylene oleic alcohol ethylene oxide ............................ ... 1.5 g Propylene glycol ............................... ... 6 g Sodium bisulfite solution (35B) ...... ... 1.2 g Ethylene-diamine-tetraacetic acid sold under the name TRILON B (brand of trade) .................................... ... 0.12 g Triethanolamine ............................... PII 8.5 Water ... qs ..... ~ ..................................... .100 g At the time of use, 70 g of water are added oxygenated to 20 volumes.
This mixture, applied for 25 min at 28C on hair discolored to white, gives them, after rinsing and shampoo, a hazelnut color.
Example 16:
The following dye composition is prepared:
Compounds of Example 1 ........................ 1.3 g Paraphenylenediamine .......................... 1.81 g Paraaminophenol ............................... 0.8 g ~ 16 ~ 266 (2,4-diamino) phenoxyethanol dihydrochloride 0.2 g Methyl-2 N- ~ -hydroxyethylamino-5 phenol ......... 0.803 y Resorcin ....................................... 0.81 g Metaaminophenol ................................. 0.9 g Nonylphenol oxyethylenated to four moles of oxide ethyl ~ ne sold under the name CEMULSOL NP4 (trademark ~ by the societe RHONE POULENC ......................... 21 `g Nonylphenol oxyethylene to nine moles of oxide ethylene sold under the name CEMULSOL NP9 (trademark) by the societe RHONE POULENC ......................... 24 g Oleic acid ................................... 4 g Butoxy-2 ethanol ................................ 3 g Ethanol (96) ................................. 10 g Diethylene pentasodium salt-Pentaacetic triamine sold under the name MASQUOL DTPA nation (trademark) ...... 2.5 g Thioglycolic acid ............................ 0.6 g Ammonia (at 22B) ............................. 10 g Water ... qs .. .................................... 100 g The pH of the composition is equal to 9.5.
At the time of use, add 120 g of water oxygenated to 20 volumes.
This mixture, applied for 25 min at 28C on discolored straw yellow hair, gives them, after rinse and shampoo, a raven black color.
Example 17:
The following dye composition is prepared:
Compound of Example 1 ......................... 0.252 g N- ~ -methoxyethylamino-4 dihydrochloride aniline ......................................... 0.6g ~ 16 ~ 266 2,6-dimethyl dihydrochloride phenylenediamine., ............................... 0.2 g Paraaminophenol ......., .......................... 0.6 g Resorcinol ........................................ 0.905 g Metaaminophenol .................................. 0.435 g Methyl-2 N- ~ -hydroxyethylamino-5 phenol .......... 0.2 g Hydroxy-6 benzomorpholine ........................ 0.435 g Methyl-2 amino-4 nitro-5 phenol .................. 0.703 g Four mole oxyethylenated nonylphenol ethylene oxide sold under the name CEMULSOL NP4 (trademark) by the RHONE POULENC .......................... 12 g Nonylphenol oxyethylenated to nine moles of oxide ethylene sold under the name CEMULSOL
NP9 (trademark) by the company RHONE POULENC .................................. 15 g Oleic alcohol with two moles of oxide ethylene ....................................... 1.5 g Oleic alcohol with four moles of oxide ethylene ............ ~ ........................... 1.5 g Propylene glycol .................................. .6 g Ethylene-diamine-tetraacetic acid sold under the name TRILON B (brand of trade) ........................................ 0.12 g Ammonia (at 22B) .............................. 11 g Thioglycolic acid ............................. .0.6 g Water ... qs .. .................................... 100 g The pH of the composition is equal to 9.9.
At the time of use, add 100 g of water oxygenated to 20 volumes ,.
This mixture, applied for 30 min at 30C on 90% naturally white hair gives them, after 1 ~ 682 ~
rinse and shampoo, a light coppery brown color.
Example 18:
The following dye composition is prepared:
Compounds of Example 1 ........................... 0.306 g Paraphenylenediamine ............................. 0.307 g N- ~ -methoxyethylamino-4 dihydrochloride aniline .......................................... 0.15 g Methyl-2 resorcin ......................... ~ ..... 0.405 g Methyl-2 N- ~ -hydroxyethylamino-5 phenol .......... 0.115 g (2,4-diamino) phenoxy dihydrochloride ethanol .......................................... 0.106 g Amino-2 nitro-3 phenol ........................... 0.203 g Cetylstearyl alcohol sold under the deno-ALFOL C16 / 18 E (trade mark merce) ~> by the company <~ CONDEA ................ 8 g Cetylstearyl sodium sulfate sold under the denomination CIRE DE LANETTE E (brand of trade) by the company HENKEL .............. 0.5 g Castor oil ethoxylee sold under the denomination CEMULSOL B (trademark) by the company RHONE POULENC> ~ .................. 1 g Oleic diethanolamide ........................... 1.5 g Diethylene pentasodium salt-triamine-pentaacetic sold under the denomina-tion <~ MASQUOL DTPA (trademark) ........ 2.5 g Thioglycolic acid ............................. 0.5 g Hydroquinone ..................................... 0.15 g Ammonia (at 22B) .............................. 11 g Water ... qs ........................................ 100 g The pH of the composition is equal to 10.3.
At the time of use, add 90 g of water oxygenated to 20 volumes.
1 16 ~ 2 ~
This mixture, applied for 25 min at 25C on naturally white hair ~ 90%, gives them, after rinse and shampoo, an an-thracite gray coloring.
Example 19:
The following dye composition is prepared:
Compounds of Example 2 ................. ~ ........ 1.5 g Compounds of Example 1 .......................... 0.42 g Paraphenyl ~ nediamine ............................ 0.62` g N, N-di- ~ -hydroxyethyl- dihydrochloride 4-amino aniline ................................. 0.42 g Paraaminophenol ........................ 0.705 g Resorcin ...................................... 0.81 g Methyl-2 N- ~ -hydroxyethylamino-5 phenol ........ 0.21 g Amino-2 nitro-3 phenol ......................... 0.61 g Cetylstearyl alcohol sold under the name ALFOL C16 / 18 E nation (trademark) by CONDEA ........................ 8 g Cetylstearyl sodium sulfate sold under the denomination CIRE DE LANETTE E (brand of trade) by the company HENKEL)> ............ 0.5 g Castor oil ethoxylee sold under the denomination CEMULSOL B (trade mark merce) by RHONE PO ~ LENC ......... 1 g Diethanolamide oleic ......................... 1.5 g Diethylene pentasodium salt-triamine-pentaacetic sold under the name MASQUOL DTPA nation (trademark) ..... 2.5 g Thioglycolic acid ........................... 0.5 g Hydroquinone ................................... 0.15 g Ammonia (at 22B) ............................ 11 g Water ... qs ...................... 100 g The pH of the composition is equal to 10.1.
11682 ~ 6 At the time of emyloi, 100 g of water are added oxygenated to 20 volumes.
This mixture, applied for 20 min at 28C on naturally white hair at 90%, gives them, after rinse and shampoo, a very dark brown coloring.
It is clearly understood that the embodiments above references are in no way limiting and for-will give rise to any desirable modifications, `without to go beyond the scope of the invention.
Claims (37)
(I) dans laquelle Z représente ou bien un radical polyhydroxy-alkyl dont le groupe alkyl comporte de 3 à 6 atomes de carbone, ledit radical comportant 2 ou 3 groupes hydroxy, ou bien une chaîne alkyl interrompue par au moins un atome d'oxygène et comportant au moins un groupe hydroxyl, ladite chaîne alkyl contenant de 4 à 8 atomes de carbone, ou les sels d'acide correspondants. 1. Chemical compound of general formula (I):
(I) in which Z represents either a polyhydroxy- radical alkyl in which the alkyl group contains from 3 to 6 carbon atoms, said radical comprising 2 or 3 hydroxy groups, or else a alkyl chain interrupted by at least one oxygen atom and having at least one hydroxyl group, said alkyl chain containing 4 to 8 carbon atoms, or the acid salts correspondents.
par le fait que Z représente un radical .beta.-(.beta.'-hydroxyéthoxy) éthyl. 2. Compound according to claim 1, characterized by the fact that Z represents a .beta .- (. beta .'- hydroxyethoxy) radical ethyl.
par le fait que Z représente un radical .beta.,?-dihydroxypropyl. 3. Compound according to claim 1, characterized by the fact that Z represents a .beta.,? - dihydroxypropyl radical.
(I) dans laquelle Z représente ou bien un radical polyhydroxy-alkyl dont le groupe alkyl comporte de 3 à 6 atomes de carbone, ledit radical comportant 2 ou 3 groupes hydroxy, ou bien une chaîne alkyl interrompue par au moins un atome d'oxygène et comportant au moins un groupe hydroxyl, ladite chaîne alkyl contenant de 4 à 8 atomes de carbone, ou les sels d'acide correspondants, caractérisé par le fait que l'on fait agir sur un sel alcalin de l'acétylamino-2 nitro-4 phénol un dérivé halogéné de formule X - Z, X étant un halogène et Z ayant les significations précitées, pour condenser le radical Z sur le noyau avec élimination d'un halogénure alcalin, on réduit ensuite le groupe nitro du produit obtenu et, enfin, on désacétyle le produit pour obtenir un composé de formule (I). 4. Process for the preparation of the compounds of formula general (I):
(I) in which Z represents either a polyhydroxy- radical alkyl of which the alkyl group contains from 3 to 6 atoms of carbon, said radical comprising 2 or 3 hydroxy groups, or an alkyl chain interrupted by at least one atom of oxygen and comprising at least one hydroxyl group, said alkyl chain containing from 4 to 8 carbon atoms, or the corresponding acid salts, characterized in that act on an alkaline salt of acetylamino-2 nitro-4 phenol a halogenated derivative of formula X - Z, X being a halogen and Z having the abovementioned meanings, for condense the radical Z on the nucleus with elimination of a alkali halide, then the nitro group of the product obtained and, finally, the product is deacetylated to obtain a compound of formula (I).
par le fait que l'halogène X est le chlore et que le métal alcalin du phénate utilisé comme matière première est le potassium. 5. Method according to claim 4, characterized by the fact that halogen X is chlorine and that the metal alkaline phenate used as raw material is the potassium.
(I) dans laquelle z représente ou bien un radical polyhydroxy-alkyl dont le groupe alkyl comporte de 3 à 6 atomes de carbone, ledit radical comportant 2 ou 3 groupes hydroxy, ou bien une chaîne alkyl interrompue par au moins un atome -d'oxygène et comportant au moins un groupe hydroxyl, ladite chaîne alkyl contenant de 4 a 8 atomes de carbone, ou les sels d'acide correspondants. 7. Dye composition for keratin fibers, said composition containing, in a cosmetically support acceptable, at least one oxidation base, characterized by the fact that it contains, as a coupler, at least one compound of formula (I):
(I) in which z represents either a polyhydroxy radical alkyl of which the alkyl group contains from 3 to 6 atoms of carbon, said radical comprising 2 or 3 hydroxy groups, or an alkyl chain interrupted by at least one atom -of oxygen and comprising at least one hydroxyl group, said alkyl chain containing from 4 to 8 carbon atoms, or the salts corresponding acid.
ou les sels d'acide correspondants, formule dans laquelle R1, R2 et R3 sont identiques ou différents et représentent un atome d'hydrogène, un radical alkyl ayant de 1 à 4 atomes de carbone ou un radical alcoxy ayant de 1 à 2 atomes de carbone, R4 et R5 sont identiques ou différents et repré-sentent un atome d'hydrogène, un radical alkyl, hydroxyalkyl, alcoxyalkyl, dans lequel le groupe alcoxy comporte de 1 à
2 atomes de carbone, carbamylalkyl, mésylaminoalkyl. aceéyl-aminoalkyl, uréidoalkyl, carbéthoxyaminoalkyl, aminoalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, pipéridinoalkyl, morpholinoalkyl, les groupes alkyl dans R4 et R5 ayant de 1 à
4 atomes de carbone, ou bien R4 et R5 forment conjointement avec l'atome d'azote auquel ils se rattachent un groupement pipéridino ou morpholino, sous réserve que R1 et R3 repré-sentent un atome d'hydrogène lorsque R4 et R5 ne représentent pas un atome d'hydrogène. 10. Composition according to claim 7, charac-terrified by the fact that it contains, as an oxidation base, at least one paraphenylenediamine of general formula (II):
or the corresponding acid salts, formula in which R1, R2 and R3 are the same or different and represent a hydrogen atom, an alkyl radical having from 1 to 4 atoms of carbon or an alkoxy radical having from 1 to 2 atoms of carbon, R4 and R5 are the same or different and represents feel a hydrogen atom, an alkyl, hydroxyalkyl radical, alkoxyalkyl, in which the alkoxy group comprises from 1 to 2 carbon atoms, carbamylalkyl, mesylaminoalkyl. aceeyl-aminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, aminoalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, the alkyl groups in R4 and R5 having from 1 to 4 carbon atoms, or else R4 and R5 form jointly with the nitrogen atom to which they are attached a group piperidino or morpholino, provided that R1 and R3 represent feel a hydrogen atom when R4 and R5 do not represent not a hydrogen atom.
ou les sels d'acide correspondants, formule dans laquelle R6 représente un atome d'hydrogène, un radical alkyl comportant de 1 à 4 atomes de carbone ou un atome d'halogène. 11. Composition according to claim 7, charac-terrified by the fact that it contains, as an oxidation base, at least one paraaminophenol of general formula (III):
or the corresponding acid salts, formula in which R6 represents a hydrogen atom, an alkyl radical comprising from 1 to 4 carbon atoms or a halogen atom.
d'agent(s) anti-oxydant(s) par rapport au poids total de la composition. 33. Composition according to claim 25 or 32, characterized by the fact that it contains between 0.05 and 1.5%
antioxidant (s) based on the total weight of the composition.
par le fait que l'agent oxydant mélange à la composition est choisi dans le groupe comprenant l'eau oxygénée, le peroxyde d'urée et les persels. 36. Method according to claim 34, characterized by the fact that the oxidizing agent mixed with the composition is chosen from the group comprising hydrogen peroxide, peroxide urea and parsley.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8014661A FR2486075A1 (en) | 1980-07-01 | 1980-07-01 | METHAPHENYLENEDIAMINES AND METHOD FOR THE PRODUCTION THEREOF, TINCTORIAL COMPOSITIONS CONTAINING SAME, AND METHOD FOR DYING THE SAME |
| FR80.14661 | 1980-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168266A true CA1168266A (en) | 1984-05-29 |
Family
ID=9243730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000380936A Expired CA1168266A (en) | 1980-07-01 | 1981-06-30 | Metaphenylenediamines, method for preparing them, dyeing compositions containing them and dyeing process |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5744669A (en) |
| AR (1) | AR227050A1 (en) |
| AT (1) | AT380683B (en) |
| AU (1) | AU543206B2 (en) |
| BE (1) | BE889449A (en) |
| BR (1) | BR8104162A (en) |
| CA (1) | CA1168266A (en) |
| CH (1) | CH650246A5 (en) |
| DE (1) | DE3125705A1 (en) |
| DK (1) | DK150540C (en) |
| ES (2) | ES503491A0 (en) |
| FR (1) | FR2486075A1 (en) |
| GB (1) | GB2078747B (en) |
| IT (1) | IT1144738B (en) |
| MX (1) | MX155064A (en) |
| NL (1) | NL8103150A (en) |
| PT (1) | PT73269B (en) |
| SE (1) | SE460787B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2519251B1 (en) * | 1982-01-05 | 1985-11-22 | Oreal | TINCTORIAL COMPOSITION BASED ON PRECURSORS OF OXIDATION DYES AND N-SUBSTITUTED ORTHONITRANILINES COMPRISING AN ALCANOLAMINE AND SODIUM BISULFITE AND THEIR USE IN DYEING KERATIN FIBERS |
| FR2547300B1 (en) * | 1983-06-13 | 1986-04-18 | Oreal | NOVEL SUBSTITUTED METAAMINOPHENOLS, PROCESS FOR THEIR PREPARATION, TINCTORIAL COMPOSITIONS FOR HAIR CONTAINING THEM AND METHOD FOR DYEING HAIR |
| JPH0825858B2 (en) * | 1991-06-04 | 1996-03-13 | ホーユー株式会社 | Hair dye composition |
| FR2707487B1 (en) † | 1993-07-13 | 1995-09-08 | Oreal | A keratin fiber oxidation dye composition comprising a para-aminophenol, a meta-aminophenol and a metaphenylenediamine, and a dyeing process using such a composition. |
| FR2715296B1 (en) * | 1994-01-24 | 1996-04-12 | Oreal | Keratin fiber oxidation dyeing composition comprising a paraphenylenediamine, a metalphenylenediamine and a para-aminophenol or a meta-aminophenol, and dyeing process using such a composition. |
| FR2720275B1 (en) * | 1994-05-26 | 1996-07-05 | Oreal | Keratin fiber oxidation dyeing composition comprising a paraphenylenediamine derivative and a 6-hydroxy 1,4-benzoxazine, and dyeing process using such a composition. |
| FR2729564B1 (en) * | 1995-01-19 | 1997-02-28 | Oreal | COMPOSITION OF OXIDIZING DYE FOR KERATINIC FIBERS AND DYE PROCESS USING THIS COMPOSITION |
| DE19826456A1 (en) * | 1998-06-13 | 1999-12-16 | Schwarzkopf Gmbh Hans | Novel 3,4-diaminophenol derivatives and their use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1670969A (en) * | 1926-12-13 | 1928-05-22 | Firm Chemical Works Formerly S | 2-amino-4-nitrophenoxypropandiol and process of producing same |
| FR2362116A1 (en) * | 1976-08-20 | 1978-03-17 | Oreal | METAPHENYLENEDIAMINES AND TINCTORIAL COMPOSITIONS CONTAINING THEM |
-
1980
- 1980-07-01 FR FR8014661A patent/FR2486075A1/en active Granted
-
1981
- 1981-06-22 AT AT0274181A patent/AT380683B/en not_active IP Right Cessation
- 1981-06-26 PT PT73269A patent/PT73269B/en not_active IP Right Cessation
- 1981-06-29 ES ES503491A patent/ES503491A0/en active Granted
- 1981-06-29 DK DK287681A patent/DK150540C/en not_active IP Right Cessation
- 1981-06-29 CH CH4277/81A patent/CH650246A5/en not_active IP Right Cessation
- 1981-06-29 AR AR285896A patent/AR227050A1/en active
- 1981-06-30 NL NL8103150A patent/NL8103150A/en not_active Application Discontinuation
- 1981-06-30 GB GB8120127A patent/GB2078747B/en not_active Expired
- 1981-06-30 BE BE0/205266A patent/BE889449A/en not_active IP Right Cessation
- 1981-06-30 BR BR8104162A patent/BR8104162A/en unknown
- 1981-06-30 AU AU72363/81A patent/AU543206B2/en not_active Expired
- 1981-06-30 DE DE3125705A patent/DE3125705A1/en not_active Withdrawn
- 1981-06-30 CA CA000380936A patent/CA1168266A/en not_active Expired
- 1981-06-30 SE SE8104072A patent/SE460787B/en not_active IP Right Cessation
- 1981-06-30 IT IT67905/81A patent/IT1144738B/en active
- 1981-06-30 MX MX188102A patent/MX155064A/en unknown
- 1981-07-01 JP JP56101396A patent/JPS5744669A/en active Pending
- 1981-10-28 ES ES506626A patent/ES8301889A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2078747B (en) | 1986-01-22 |
| DK287681A (en) | 1982-01-02 |
| FR2486075B1 (en) | 1983-03-11 |
| AU543206B2 (en) | 1985-04-04 |
| AU7236381A (en) | 1982-09-16 |
| AT380683B (en) | 1986-06-25 |
| CH650246A5 (en) | 1985-07-15 |
| GB2078747A (en) | 1982-01-13 |
| IT8167905A0 (en) | 1981-06-30 |
| PT73269A (en) | 1981-07-01 |
| ES506626A0 (en) | 1982-12-16 |
| ES8205393A1 (en) | 1982-06-01 |
| BR8104162A (en) | 1982-03-16 |
| ATA274181A (en) | 1985-11-15 |
| ES503491A0 (en) | 1982-06-01 |
| JPS5744669A (en) | 1982-03-13 |
| IT1144738B (en) | 1986-10-29 |
| FR2486075A1 (en) | 1982-01-08 |
| DK150540C (en) | 1988-01-11 |
| DE3125705A1 (en) | 1982-03-18 |
| MX155064A (en) | 1988-01-22 |
| AR227050A1 (en) | 1982-09-15 |
| SE8104072L (en) | 1982-01-02 |
| PT73269B (en) | 1982-09-23 |
| NL8103150A (en) | 1982-02-01 |
| DK150540B (en) | 1987-03-23 |
| ES8301889A1 (en) | 1982-12-16 |
| BE889449A (en) | 1981-12-30 |
| SE460787B (en) | 1989-11-20 |
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