EP0910332A2 - Colorants - Google Patents

Colorants

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Publication number
EP0910332A2
EP0910332A2 EP97931747A EP97931747A EP0910332A2 EP 0910332 A2 EP0910332 A2 EP 0910332A2 EP 97931747 A EP97931747 A EP 97931747A EP 97931747 A EP97931747 A EP 97931747A EP 0910332 A2 EP0910332 A2 EP 0910332A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
ppm
amino
compounds
formula
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.)
Withdrawn
Application number
EP97931747A
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German (de)
English (en)
Inventor
Andreas Joachim Bittner
Astrid Kleen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hans Schwarzkopf and Henkel GmbH
Original Assignee
Hans Schwarzkopf and Henkel GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hans Schwarzkopf and Henkel GmbH filed Critical Hans Schwarzkopf and Henkel GmbH
Publication of EP0910332A2 publication Critical patent/EP0910332A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A61K8/418—Amines containing nitro groups
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B51/00—Nitro or nitroso dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups

Definitions

  • the invention relates to agents for dyeing keratin fibers with special 4-nitroaniline derivatives as direct dyes.
  • direct dyes are also used to dye keratin fibers.
  • these dyes are able to dye the hair directly. Under the application-related boundary conditions (low dyeing temperature and short dyeing time) they result in intense colors with good fastness properties. The dyes diffuse into the fiber during the dyeing process.
  • Nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols are usually used as direct dyes for dyeing keratin fibers.
  • direct dyes for achieving a wide variety of shades, hereinafter referred to as direct pullers, play an important role in hair coloring.
  • These dyes must give the desired color with sufficient intensity during the coloring, the colors obtained must have good light and acid fastness, and they must not tend to color shifts of the original shade under the wearing conditions. Furthermore, they should be dermatologically and toxicologically safe.
  • New direct hair dyes which are more and more demanding with regard to their light fastness, wash fastness and color depth, but also with regard to their toxicological and dermatological properties have to suffice.
  • New direct pullers in the yellow and red areas of the color spectrum are particularly required for special yellow or bordeaux tones.
  • the present invention therefore relates to agents for dyeing keratin fibers which, as a direct dye, are a 4-nitroaniline derivative of the formula (I)
  • R ,, R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfalkyl, Piperidinoalkyl, morpholinoalkyl or a phenyl radical which is optionally substituted in para position with an amino group, these alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R 1 , R 2 , R 3 and R 4 simultaneously represent hydrogen, and the groups -NR, R 2 and / or -NR 3 R 4 can also represent an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, thiomorpholine or a piperazine
  • the compounds of the formula (I) can be prepared by known processes. For this purpose, reference is expressly made to the explanations in the example section.
  • Particularly excellent dyeing properties are shown by compounds of the formula (I) in which the group -NR, R 2 or -NR 3 R 4 is aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, Thiomorpholine or a piperazine ring, which can also carry a further substituent R 8 on the nitrogen atom, where R 8 is a hydrogen atom, a (C, -C 4 ) alkyl, a hydroxy (C 2 -C 3 ) alkyl -, is a (C, - C 4 ) alkoxy- (C 2 -C 3 ) alkyl, an amino (C 2 -C 3 ) alkyl or a 2,3-dihydroxypropyl group.
  • Preferred substituents R 1 to R 7 are, to the extent permitted by the general formula (I), hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-aminoethyl and 2,3-dihydroxypropyl groups, and for R 5 to R 7 halogen atoms.
  • the compounds of formula (I) can be used both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, e.g. the hydrochloride, the sulfate and hydrobromide.
  • inorganic or organic acids e.g. the hydrochloride, the sulfate and hydrobromide.
  • Other acids suitable for salt formation are phosphoric acid and acetic acid, propionic acid, lactic acid and citric acid. The statements made below on the compounds of the formula (I) therefore always include these salts.
  • the hair colorants according to the invention preferably contain the compounds of the formula (I) in an amount of 0.001 to 10% by weight, preferably 0.1 to 5% by weight, based in each case on the total colorant.
  • total colorant is understood to mean the agent that is made available to the user.
  • this agent can either directly or, if the agent additionally contains oxidation dye precursors, after mixing with water or, for example, one aqueous solution of an oxidizing agent can be applied to the hair.
  • the agents according to the invention contain only the compounds of formula (I) as a dye component.
  • the number of available color shades is significantly increased if the agent contains, in addition to the compounds of the formula (I), a further direct dye or an oxidation dye precursor.
  • the colorants according to the invention contain, in addition to the compounds of the formula (I) according to Claim 1, optionally in addition to oxidation dye precursors, in addition to modifying the color shades, at least one further direct dye, e.g. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols.
  • Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, Picramic Acid and Rodol 9 R known compounds and 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro - 1, 2,3,4-tetrahydroquinoxaline, (N-2,3-
  • agents according to the invention in accordance with this embodiment preferably contain the further substantive dye in an amount of 0.01 to 20% by weight, based on the total colorant.
  • the colorants according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
  • naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
  • the agents according to the invention contain, in addition to the compounds corresponding to formula (I) according to Claim 1 and, if desired, substantive dyes and an oxidation dye precursor of the coupler type, at least one oxidation dye precursor of the developer type.
  • Preferred developer components according to the invention are p-phenylenediamine, p-toluylenediamine, p-aminophenol, 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis - (2-hydroxy-ethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, l-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2 - Methylamino-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6, -triaminopyrimidine, 2,4-dihydroxy-5 , 6-diaminopyrimidine, 2-dimethyl__mino-4,5,6-triamino
  • p-toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2-methylamino-4-aminophenol and 2,4,5 are very particularly preferred , 6-tetraaminopyrimidine.
  • Coupler combinations preferred according to the invention are
  • the agents according to the invention contain, in addition to the compounds corresponding to formula (I) according to claim 1 and, if desired, further direct dyes and oxidation dye precursors of the developer type, at least one oxidation dye precursor of the coupler type.
  • Coupler components preferred according to the invention are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m- Phenylenediamine, l-phenyl-3-methyl-pyrazo-lon-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro 6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihy- hydroxy-3,4-diaminopyridine, 3-amino-2-
  • 1,7-dihydroxynaphthalene, m-aminophenol, 2-methylresorcinol, 4-amino-2-hydroxytoluene, 2-amino-4-hydroxyethylamino-anisole and 2,4-diaminophenoxyethanol are particularly preferred.
  • this embodiment also includes the use of multiple coupler components. Coupler combinations preferred according to the invention are
  • Developer components and coupler components are usually used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can preferably be present in the colorant in a molar ratio of 1: 0.5 to 1: 2.
  • the total amount of oxidation dye precursors is usually at most 20 wt .-%, based on the total agent.
  • the substantive or optional direct dyes or the optional oxidation dye precursors each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.
  • Usual formulations for the oxidation coloring agents according to the invention are agents based on water or non-aqueous solvents as well as powders.
  • the substantive dyes of the formula (I) and, if appropriate, further dyes and dye precursors are incorporated into a suitable water-containing carrier.
  • a suitable water-containing carrier for the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, for example shampoos, aerosols or other preparations which are suitable for use on the hair.
  • the colorants according to the invention are preferably adjusted to a pH of 6.5 to 11.5, in particular 9 to 10.
  • the colorants according to the invention can contain all active substances, additives and auxiliaries known in such preparations.
  • the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants can be very particularly preferred.
  • Suitable anionic surfactants in the preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
  • anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
  • glycol or polyglycol ether groups, ether, amide and hydroxyl groups and generally also ester groups can be contained in the molecule.
  • suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,
  • esters of tartaric acid and citric acid with alcohols the additive
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO - or -SO3 ⁇ group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacyl-aminoethyl-hydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known under the
  • Ampholytic surfactants are surface-active compounds which, in addition to a C8-C18-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkylimino dipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-18 acylsarcosine.
  • Nonionic surfactants contain z as a hydrophilic group.
  • Such connections are, for example
  • Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds.
  • Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for.
  • the quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).
  • alkylamidoamines especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid S 18, are particularly notable for their good biodegradability.
  • esterquats such as the dialkylammonium methosulfates and methyl-hydroxyalkyl-dialkoyloxyalkyl-ammonium-ethosulfates sold under the trademark Stepantex, are also very readily biodegradable.
  • the compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.
  • both products with a "normal” homolog distribution and those with a narrowed homolog distribution can be used.
  • “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates.
  • narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.
  • non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride -dimethyloloyl-methylenedilyl-sulfonyl-acrylamide-polymers, acrylamide-sulfonyl-methylenedi- lolamide-copolymerized with acrylamide Dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, II zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chlor
  • Copolymers such as polyacrylic acids, crosslinked polyacrylic acids,
  • Vinyl acetate / crotonic acid copolymers vinylpyrrolidone-vinyl acrylate copolymers
  • Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans,
  • Cellulose derivatives e.g. B. methyl cellulose, hydroxyalkyl cellulose and
  • B. bentonite or fully synthetic hydrocolloids such as e.g.
  • Structurants such as glucose, maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin,
  • Protein hydrolyzates especially elastin, collagen, keratin, milk protein,
  • Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,
  • Anti-dandruff agents such as Piroctone Olamine and Zink Omadine
  • Alkalizing agents such as ammonia, monoethanolamine, 2-amino-2-methylpropanol and 2-amino-2-methyl-propanediol-1,3. other substances for adjusting the pH value,
  • Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
  • Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
  • Fats and waxes such as whale, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
  • Complexing agents such as EDTA, NTA and phosphonic acids, Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether,
  • Pearlescent agents such as ethylene glycol mono- and distearate
  • Blowing agents such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and
  • constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; e.g. emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.
  • the agents according to the invention contain oxidation dye precursors, the oxidative development of the coloring can in principle take place with atmospheric oxygen or an oxidizing agent contained in the agent or added to it immediately before use.
  • a chemical oxidizing agent is used. This is particularly advantageous in cases where, in addition to the coloring, a lightening effect on human hair is desired.
  • Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or alkali borate.
  • the colorant according to the invention is mixed with the preparation of the oxidizing agent, in particular an aqueous H 2 O 2 solution, immediately before use.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment.
  • the application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used.
  • the preparation with the oxidation dye precursors can be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the - if necessary after an intermediate rinse / 3 Oxidation component applied. After a further exposure time of 10 to 20 minutes, rinsing is then carried out and, if desired, re-shampooing.
  • the coloring takes place with atmospheric oxygen. It is advantageous to add an oxidation catalyst to the colorant according to the invention.
  • Suitable oxidation catalysts are metal salts or metal complexes, with transition metals being preferred. Copper, manganese, cobalt, selenium, molybdenum, bismuth and ruthenium compounds are preferred. Copper (II) chloride, sulfate and acetate can be preferred oxidation catalysts.
  • the complexes with ammonia, ethylenediamine, phenanthroline, triphenylphosphine, 1, 2-diphenylphosphinoethane, 1,3-diphenylphosphinopropane or amino acids can be preferred as metal complexes.
  • the enzymes can be used both to produce oxidizing per compounds and to enhance the effect of a small amount of oxidizing agents present.
  • An example of an enzymatic process is the procedure to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.
  • Another object of the invention is the use of 4-nitroanilines of the general formula (I) according to claim 1 for dyeing keratin fibers.
  • the compounds of the general formula (I) can be converted by reducing the 4-nitro group into compounds of the general formula (Ia) in which a 4-amino group is present instead of the 4-nitro group
  • These compounds are oxidation dye precursors with particularly excellent coloring properties, which also have coupler and developer properties.
  • the products of the formula (IV) are hydrolyzed and, if appropriate, converted to the compounds of the general formula (I) by alkylation or oxalkylation.
  • the compounds of the general formula (III) are common chemical raw materials and can be purchased.
  • Suitable phase transfer catalysts are, for example, methyl or benzyl tri (C 6 -
  • compounds of the general formula (I) can be obtained by 5-halo-2-nitranilines of the general formula (V), where R 3 and R 4 have the meaning given above, with amines of the general formula (III ) ⁇ r if appropriate with the addition of phase transfer catalysts to compounds of the general formula (I).
  • This reaction can also optionally be carried out in an autoclave under pressure if the boiling point of the amine is lower than the reaction temperature or the conversion is not complete.
  • the compounds of the formula (IV) ' are hydrolyzed to the compounds of the general formula (V) and, if appropriate, converted to the compounds of the general formula (I) according to the invention by alkylation or oxalkylation.
  • Suitable phase transfer catalysts are, for example, methyl or benzyl tri (C 6 -C 8 ) alkylammonium chloride.
  • This reaction can also optionally be carried out in an autoclave under pressure if the boiling point of the amine is lower than the reaction temperature or the conversion is not complete.
  • Formula (VIII) 'are then with strong bases, for. B. sodium or potassium hydroxide to compounds of the general formula (IX) 'in which R 10 CH 2 CH 2 OH or CH 2 CH 2 CH 2 OH means that with known alkylating or oxyalkylating agents
  • compounds of the general formula (I) according to the invention can be obtained by 3-halo-4-nitranilines of the general formula (VI) with amines of the general formula (purple), where R 1 to R 4 have the meaning given above have, optionally with the addition of phase transfer catalysts to compounds of the general formula (I).
  • the first stage of the above-mentioned processes consists in principle of replacing a halogen substituent with an amine substituent on the phenyl ring.
  • an amine excess of about 40-80% is usually used; the products are obtained in yields of approx. 90% and with a purity of 95-96%.
  • the amine excess is 30% and less, in particular 5 to 10 mol%, based on the amounts of the compound of the formula (II) used, (V ), (VI), (II) 'or (VI)'.
  • the reaction is preferably carried out under a pressure of from 1 to 15 bar, in particular from 1 to 8 bar and very particularly preferably from 1 to 2.5 bar.
  • methyl or benzyl tri (C 6 -C 8 ) alkylammonium chlorides or tetraphenylphosphinium chloride can be used as phase transfer catalysts.
  • hydrochloric acid, sulfuric acid or phosphoric acid are suitable as inorganic acids and acetic acid, propionic acid, lactic acid or citric acid as organic acids.
  • 3-chloropropyl ester (VII) (R_, CH 2 CH 2 CH 2 C1) in compounds of the formula (VIII)
  • R I0 CH 2 CH 2 OH or CH 2 CH 2 CH 2 OH, which react with known alkylating or oxyalkylating agents to give products of the general formula (I), in which R to R 4 are the same as those already given Have meaning, and optionally converted into an inorganic or organic acid in the salt thereof.
  • the compounds produced were characterized by IR or IR (KBr compact) and / or 'H NMR spectra (in D 6 -DMSO). As far as the spectra are given here, only the very strong and strong bands are listed for the IR spectra.
  • s singlet, d doublet, dd doublet from the doublet, t triplet, q quartet, qi quintet, m multiplet, 3 J and 4 J mean the couplings via three and four bonds respectively H 2 , H 3 , H ⁇ H 5 and H 6 represent the hydrogen atoms in positions 2, 3, 4, 5 and 6 of the benzene ring.
  • Stage a) was carried out analogously to Example 1.3.1. Step a) by reacting 5-chloro-2-nitroacetanilide with morpholine.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with ethylamine.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N-ethyl-2-nitro-5-acetaminoaniline with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with «-propylamine.
  • stage b) The preparation in stage b) is carried out analogously to example 1.3.3. Step b) by reaction of N-_7-propyl-2-nitro-5-acetaminoaniline with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with wo-butylamine. Yield: 14.5 g (57.7% of theory) of yellow crystals
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N-wo-butyl-2-nitro-5-acetaminoaniline with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with dimethylamine.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N, N-dimethyl-2-nitro-5-acetaminoaniline with hydrochloric acid. Yield: 18.9 g (100% of theory) of yellow crystals
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with diethylamine.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N, N-DiethyI-2-nitro-5-acetaminoaniline with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with pyrrolidine.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyl) pyrrolidine with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with piperidine.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyI) piperidine with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with azepane.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reacting N- (5-acetylamino-2-nitrophenyl) azepane with hydrochloric acid.
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetaniIid with morpholine.
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyl) mo hoiin with hydrochloric acid. Yield: 19.2 g (95.6% of theory) of yellow crystals
  • Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with piperazine. Yield: 21.5 g (81% of theory) of yellow crystals z9
  • stage b) The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyl) piperazine with hydrochloric acid.
  • Table 1 Compounds of the general formula (I) according to the invention, their absorption maximum and their color.
  • Cream-based colorants
  • Example dye oxidation dye color according to formula (I) vo ⁇ rodukte

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Abstract

Les colorants décrits de fibres kératiniques contiennent, en tant qu'agent colorant montant directement sur la fibre, un dérivé de 4-nitroaniline qui répond à la formule (I) ou un sel physiologiquement admissible de ces composés avec un acide inorganique ou organique. Dans la formule (I), R1, R2, R3 et R4 représentent indépendamment les uns des autres un atome d'hydrogène, un radical alkyle, hydroxyalkyle, alcoxyalkyle, carbamylalkyle, mésylaminoalkyle, acétylaminoalkyle, uréidoalkyle, carbalcoxyaminoalkyle, sulfalkyle, pipéridinoalkyle, morpholinoalkyle ou phényle, le cas échéant para-substitué par un groupe amino, ces groupes alkyle ou alcoxy ayant 1 à 4 atomes de carbone, à condition que les quatre substituants R1, R2, R3 et R4 ne représentent pas tous en même temps hydrogène. Les groupes -NR1R2 et/ou -NR3R4 peuvent également désigner un cycle aziridine, azétidine, pyrrolidine, pipéridine, azépane, azocine, morpholine, thiomorpholine ou pipérazine, qui peut également porter sur l'atome d'azote un autre substituant R8, R8 désignant un atome d'hydrogène, un groupe alkyle (C1-C4), un groupe hydroxyalkyle (C2-C3), un groupe alcoxy-(C1-C4)-alkyle-(C2-C3), un groupe aminoalkyle (C2-C3) ou un groupe 2,3-dihydroxypropyle. Dans la formule R5, R6 et R7 désignent indépendamment les uns des autres un atome d'hydrogène, un atome d'halogène, un radical alkyle (C1-C4), un radical alcoxy (C1-C4), un radical carboxyalkyle, sulfo-alkyl ou hydroxyalkyle (C2-C4). Ces composés permettent d'obtenir des colorations brillantes très solides. Le nombre de nuances peut être encore accru par adjonction d'autres colorants montant directement sur la fibre ou d'autres précurseurs de colorants par oxydation.
EP97931747A 1996-07-03 1997-07-02 Colorants Withdrawn EP0910332A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19626721 1996-07-03
DE19626683 1996-07-03
DE19626721 1996-07-03
DE19626683 1996-07-03
PCT/EP1997/003486 WO1998001105A2 (fr) 1996-07-03 1997-07-02 Colorants

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JP (1) JP2001501915A (fr)
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WO (1) WO1998001105A2 (fr)

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Publication number Priority date Publication date Assignee Title
DE102008063742A1 (de) * 2008-12-18 2010-07-01 *Acri.Tec Gmbh Farbstoff, ophthalmologische Zusammensetzung und ophthalmologische Linse
EP2226065A3 (fr) 2010-03-15 2010-09-29 KPSS-Kao Professional Salon Services GmbH Färbezusammensetzung für Keratinfasern

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US4155934A (en) * 1965-12-03 1979-05-22 L'oreal Hair dye compounds
US3907494A (en) * 1971-10-04 1975-09-23 Therachemie Chem Therapeut Hair dyes based on diamino-nitro-benzene compounds
DE2149467A1 (de) * 1971-10-04 1973-04-12 Therachemie Chem Therapeut Haarfaerbemittel
LU85939A1 (fr) * 1985-06-10 1987-01-13 Oreal Nouvelles metaphenylenediamines nitrees,halogenees en position 6 et leur utilisation en teinture des matieres keratiiques
LU85940A1 (fr) * 1985-06-10 1987-01-13 Oreal Compositions de teinture pour fibres keratiniques a base de metaphenylenediamines halogenes
US4764174A (en) * 1986-01-30 1988-08-16 Helene Curtis, Inc. Nitrophenylenediamine dye composition having improved deposition on human hair and wool
DE4115983A1 (de) * 1991-05-16 1992-11-19 Henkel Kgaa Haarfaerbemittel
US5169403A (en) * 1991-11-01 1992-12-08 Clairol, Inc. Direct dyes having a quaternary center with a long aliphatic chain
DE4404198A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa 2-Fluor-6-nitroaniline

Non-Patent Citations (1)

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Title
See references of WO9801105A2 *

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JP2001501915A (ja) 2001-02-13
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US20010052156A1 (en) 2001-12-20
WO1998001105A3 (fr) 1998-04-09

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