| 摘要 |
<p>#CMT# #/CMT# Cationic dissymmetrical diazo compounds (I), their resonance forms, acid addition salts an acid and/or their solvates are new. #CMT# : #/CMT# Cationic dissymmetrical diazo compounds of formula (I) (where electroneutrality of (I) is ensured by one or more anions (An)), their resonance forms, acid addition salts an acid and/or their solvates are new. R3X or 1-16C alkyl (optionally substituted, and optionally interrupted by one or more heteroatoms or groups containing heteroatoms (preferably O, N, S, -CO and/or -SO2)); X : OH, 1-4C alkoxy, 2-4C (poly)hydroxyalkoxy, RO-CO-, RCO-O-, R-CO-, amino (optionally substituted by one or two radicals 1-4C alkyl (optionally carrying OH), where the two alkyl radicals with N optionally form T), alkylcarbonylamino (RCO-NR1-), aminocarbonyl ((R1)2N-CO), ureido (N(R1)2-CO-NR1), aminosulfonyl ((R1)2N-SO2), alkylsulfonylamino (RSO2-NR1-), alkylsulfinyl (R-SO-), alkylsulfonyl (R-SO2-), nitro, CN, halo (Cl or F), HS- or RS; R2X, 1-16C alkyl (optionally substituted by HS, 1-4C thioalkyl, 1-4C alkylsulfinyl or 1-4C alkylsulfonyl, and optionally interrupted by one or more heteroatoms or groups containing heteroatoms (preferably O, N, S, -CO and/or -SO2)), substituted aryl or 1-4C arylalkyl (optionally substituted); e, m1 : 0-4; T : 5-7 membered optionally aromatic heterocycle (containing 1-3 (preferably 1-2) heteroatoms N (preferred), O or S); W1H, halo (Br, Cl or F (preferably Cl or F)), NR5R6, OR7, -NR4-Ph-NR5R), -NR4-Ph-OR7, -O-Ph-OR7 or -O-Ph-NR5R6; R4, R71-20C (preferably 1-16C) alkyl, 1-3C aralkyl, phenyl (all optionally substituted) or H; either R5, R61-20C (preferably 1-16C) alkyl, 1-3C aralkyl, phenyl (all optionally substituted), H or R-CO-; or NR5R6T; or R5 + R6 + C (of aromatic cycle adjacent to that to which -NR5R6 is attached) : 5-6 membered saturated heterocycle; Ph : optionally substituted phenyl; L : optionally cationic bond; R : 1-4C alkyl; and R1 : H or R. Provided that when e is 2, then two adjacent R2 together forms with carbon atom to which they are attached a 5-6 (preferably 6) membered secondary cycle (optionally substituted by 1-4C alkyl, 1-4C alkoxy, 2-4C (poly)hydroxyalkoxy or amino (optionally substituted by 1-4C alkyl (optionally carrying OH)). Provided that when m1 is 2, then two adjacent R3 together forms with carbon atom to which they are attached a 6 membered secondary cycle (optionally substituted by OH, 1-4C alkyl, 1-4C alkoxy, 2-4C (poly)hydroxyalkoxy or amino (optionally substituted by 1-4C alkyl (optionally carrying OH)). Provided that when e and m1 is lower than 4 the carbon atoms of unsubstituted heterocycle carry a hydrogen atom. Independent claims are also included for: (1) a tinctorial composition (A) comprising (I), in a medium for the dyeing of keratinous fibers, as direct dye; (2) a process of dyeing keratinous fiber comprising contacting (A) with the dry or wet fibers to obtain the desired effect; and (3) a device with several compartments, comprising a first compartment comprising (A) and a second compartment containing an oxidizing composition. #CMT#[Image]#/CMT# #CMT#USE : #/CMT# (I) are useful for dyeing of keratinous fibers (claimed). #CMT#ORGANIC CHEMISTRY : #/CMT# Preparation: No general preparation given. Preferred Composition: (A) comprises (I) at 0.001-20 (0.01-10) wt.%. (A) further comprises an additional direct dye, an oxidation base optionally associated with a coupler. (A) further comprises an oxidizing agent. Preferred Components: The additional direct dye is cationic or non-ionic dye, nitrated benzene dyes, azo dyes, azomethinic dyes, methinic dyes, tetraazapenthamethinic dyes, anthraquinonic dyes, naphtoquinonic dyes, benzoquinonic dyes, phenotiazinic indigoid dyes, xanthenic dyes, phenanthridinic dyes, phthalocyanine, triarylmethane derivatives and/or natural dyes. The oxidation base is p-phenylenediamines, bis-phenylalkylenediamines, o-aminophenols, p-aminophenols or heterocyclic bases. The coupler is m-aminophenols, m-phenylenediamines, m-diphenols, naphthols and/or heterocyclic couplers or their acid addition salts. #CMT#DEFINITIONS : #/CMT# Preferred Definitions: Either R5, R6H, methylcarbonyl, ethylcarbonyl, propylcarbonyl, methyl, ethyl, hydroxyethyl, 2-methoxyethyl, phenyl (optionally substituted by OH), 1-2C alkoxy or amino (optionally substituted 1-4C alkyl (optionally carrying hydroxyl)); or NR5R6piperidine 2-(2-hydroxyethylpiperidine), 4-(aminomethyl)piperidine, 4-(2-hydroxy ethyl) piperidine, 4-(dimethylamino)piperidine, piperazine, 1-methylpiperazine, 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-hydroxyethylethoxy piperazine, homopiperazine, 1-methyl 1,4-perhydrodiazepine, pyrrole, 1,4-dimethylpyrrole, 1-methyl-4-ethylpyrrole or 1-methyl-4 propylpyrrole; or CR5R6saturated 5-6 membered heterocycle; L : 1-2C alkyl (optionally substituted and optionally interrupted by one 3-7 membered optionally saturated, optionally aromatic heterocycle (optionally fused), O, N, S, -CO- and/or -SO2-) (where L is cationic); and An : Cl, Br, Fl, I, OH, sulfate, hydrogenosulfate, 1-6C alkylsulfate (methylsulfate or ethylsulfate) or (hydrogeno)carbonates, carboxylic acid salts (formate, acetate, citrate, tartrate or oxalate), methylsulfonate, 4-toluylsulfonate or mesylate. Provided that L is not N, nitro, nitroso or peroxo. #CMT#SPECIFIC COMPOUNDS : #/CMT# 25 Compounds (I) are specifically claimed e.g. 1-{2[2-(4-dimethylamino-phenylazo)]-pyridinium}-heptyl-7-{3[2-(4-dimethylamino-phenylazo)]-pyridinium} cation of formula (Ia). #CMT#EXAMPLE : #/CMT# A mixture 1-(6-chloro-hexyl)-2-(4-dimethylamino-phenylazo)-pyridinium chloride (0.95 g), dimethyl-[4-(pyridin-3-ylazo)-phenyl]-amine (0.45 g), potassium iodide (0.05 g) and dimethyl formamide (15 ml) was stirred at 100[deg]c for 22 hours. The reaction mixture was further worked up to give 2-(4-dimethylamino-phenylazo)-1-{6-[3-(4-dimethylamino-phenylazo)-pyridinium-1-yl]-hexyl}-pyridinium chloride.</p> |
