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DE20108704U1 - 1,3-dihydroxybenzene derivatives and dyes for these containing keratin fibers - Google Patents

1,3-dihydroxybenzene derivatives and dyes for these containing keratin fibers

Info

Publication number
DE20108704U1
DE20108704U1 DE20108704U DE20108704U DE20108704U1 DE 20108704 U1 DE20108704 U1 DE 20108704U1 DE 20108704 U DE20108704 U DE 20108704U DE 20108704 U DE20108704 U DE 20108704U DE 20108704 U1 DE20108704 U1 DE 20108704U1
Authority
DE
Germany
Prior art keywords
group
amino
diamino
benzene
phenol
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 - Lifetime
Application number
DE20108704U
Other languages
German (de)
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.)
Procter and Gamble Deutschland GmbH
Original Assignee
Wella 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 Wella GmbH filed Critical Wella GmbH
Priority to DE20108704U priority Critical patent/DE20108704U1/en
Publication of DE20108704U1 publication Critical patent/DE20108704U1/en
Priority to AT02711818T priority patent/ATE297389T1/en
Priority to AU2002231759A priority patent/AU2002231759B2/en
Priority to EP02711818A priority patent/EP1392673B1/en
Priority to DE50203353T priority patent/DE50203353D1/en
Priority to MXPA03008699A priority patent/MXPA03008699A/en
Priority to CNB028095456A priority patent/CN100349886C/en
Priority to ES02711818T priority patent/ES2241999T3/en
Priority to JP2003500080A priority patent/JP2004519524A/en
Priority to US10/416,048 priority patent/US7125428B2/en
Priority to PCT/EP2002/000850 priority patent/WO2002096901A2/en
Priority to BR0205398-5A priority patent/BR0205398A/en
Priority to CA002445647A priority patent/CA2445647A1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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
    • 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
    • A61K8/415—Aminophenols
    • 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
    • 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
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4986—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with sulfur as the only hetero atom
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/20—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/16—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/24—Halogenated derivatives
    • C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
    • C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms
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    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/42—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms with nitro or nitroso radicals directly attached to ring carbon atoms

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Description

• *• *

BeschreibungDescription

1,3-Dihydroxybenzol-Derivate sowie diese Verbindungen enthaltende Färbemittel für Keratinfasern1,3-Dihydroxybenzene derivatives and dyes for keratin fibres containing these compounds

Die Erfindung betrifft neue m-Dihydroxybenzol-Derivate sowie diese Verbindungen enthaltende Mittel zum oxidativen Färben von Keratinfasern. The invention relates to novel m-dihydroxybenzene derivatives and agents containing these compounds for the oxidative dyeing of keratin fibers.

Auf dem Gebiet der Färbung von Keratinfasern, insbesondere der Haarfärbung, haben Oxidationsfarbstoffe eine wesentliche Bedeutung erlangt. Die Färbung entsteht hierbei durch Reaktion bestimmter Entwicklersubstanzen mit bestimmten Kupplersubstanzen in Gegenwart eines geeigneten Oxidationsmittels. Als Entwicklersubstanzen werden hierbei insbesondere 2,5-Diaminotoluol, 2,5-Diaminophenylethylalkohol, p-Aminophenol, 1,4-Diaminobenzol und 4,5-Diamino-1-(2-hydroxyethyl)-pyrazol eingesetzt, während als Kupplersubstanzen beispielsweise Resorcin, 2-Methyl-resorcin, 1-Naphthol, 3-Aminophenol, m-Phenylendiamin, 2-Amino-4-(2'-hydroxyethyl)amino-anisol, 1,3-Diamino-4-(2'-hydroxyethoxy)benzol und 2,4-Diamino-5-fluor-toluol zu nennen sind.Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring. The coloring is created by the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. The developer substances used in particular are 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol, 1,4-diaminobenzene and 4,5-diamino-1-(2-hydroxyethyl)pyrazole, while the coupler substances used are, for example, resorcinol, 2-methylresorcinol, 1-naphthol, 3-aminophenol, m-phenylenediamine, 2-amino-4-(2'-hydroxyethyl)aminoanisole, 1,3-diamino-4-(2'-hydroxyethoxy)benzene and 2,4-diamino-5-fluorotoluene.

An Oxidationsfarbstoffe, die zur Färbung menschlicher Haare verwendet werden, werden neben der Färbung in der gewünschten Intensität zahlreiche zusätzliche Anforderungen gestellt. So müssen die Farbstoffe in toxikologischer und dermatologischer Hinsicht unbedenklich sein und die erzielten Haarfärbungen eine gute Lichtechtheit, Dauerwellechtheit, Säureechtheit und Reibeechtheit aufweisen. Auf jeden Fall aber müssen solche Färbungen ohne Einwirkung von Licht, Reibung und chemischenOxidation dyes used to dye human hair must meet numerous additional requirements in addition to the desired intensity. The dyes must be toxicologically and dermatologically safe and the hair dyes produced must have good lightfastness, perm fastness, acid fastness and rubbing fastness. In any case, such dyes must be applied without the effects of light, rubbing and chemicals.

Mitteln über einen Zeitraum von mindestens 4 bis 6 Wochen stabil bleiben. Außerdem ist es erforderlich, dass durch Kombination geeigneter Entwicklersubstanzen und Kupplersubstanzen eine breite Palette verschiedener Farbnuancen erzeugt werden kann.Agents must remain stable over a period of at least 4 to 6 weeks. It is also necessary that a wide range of different colour nuances can be produced by combining suitable developer substances and coupler substances.

Obwohl eine Vielzahl von Kupplersubstanzen bekannt, ist es mit den derzeit bekannten Färbemitteln nicht möglich, die an ein Färbemittel gestellten Anforderungen in jeder Hinsicht zu erfüllen. Es besteht daher weiterhin ein Bedürfnis nach neuen Kupplersubstanzen, welche die vorgenannten Anforderung in besonderem Masse erfüllen.Although a large number of coupling substances are known, it is not possible to meet all the requirements placed on a dye in every respect using the currently known dyes. There is therefore still a need for new coupling substances which meet the above requirements to a particularly high degree.

E wurde numehr gefunden, dass bestimmte 1,3-Dihydroxy-benzol-Derivate gemäß der allgemeinen Formel (I) die an Kupplersubstanzen gestellten Anforderungen in besonders hohem Masse erfüllen und mit den meisten bekannten Entwicklersubstanzen farbstarke Farbnuancen erhalten werden, welche außerordentlich lichtecht und waschecht sind.It has now been found that certain 1,3-dihydroxybenzene derivatives according to the general formula (I) meet the requirements placed on coupler substances to a particularly high degree and that, with most known developer substances, strong color nuances are obtained which are extraordinarily lightfast and washfast.

Gegenstand der vorliegende Erfindung ist daher ein Mittel zur Färbung von Keratinfasem, wie zum Beispiel Wolle, Pelzen, Federn oder Haaren und insbesondere menschlichern Haaren, auf der Basis einer Entwicklersubstanz-Kupplersubstanz-Kombination, welches dadurch gekennzeichnet ist, dass es mindestens ein 1,3-Dihydroxybenzol-Derivat der Formel (I) oder dessen physiologisch verträgliche, wasserlösliche Salze enthält,The present invention therefore relates to an agent for coloring keratin fibers, such as wool, fur, feathers or hair and in particular human hair, based on a developer substance-coupler substance combination, which is characterized in that it contains at least one 1,3-dihydroxybenzene derivative of the formula (I) or its physiologically acceptable, water-soluble salts,

(I)(I)

worinwherein

R1 gleich einer substituierten Pyridylgruppe, einer Pyrimidylgruppe, einem Rest der Formel,R1 is a substituted pyridyl group, a pyrimidyl group, a radical of the formula,

R2 R3R2 R3

oder einem Rest der Formelor a remainder of the formula

R7R7

X2 X2

(III) ist;(III) is;

wobei R2, R3, R4, R5 und R6 unabhängig voneinander Wasserstoff, ein Halogenatom (F, Cl, Br, J), eine Cyanogruppe, eine Hydroxygruppe, eine CrC4-Alkoxygruppe, eine C1-C4-Hydroxyalkoxygruppe, eine CrC6-Alkylgruppe, eine C1-C4-Alkylthioethergruppe, eine Mercaptogruppe, eine Nitrogruppe, eine Aminogruppe, eine C1-C4-Alkylaminogruppe, eine Hydroxy^-CJalkylaminogruppe, eine Di(C1-C4)alkylaminogruppe, eine Di(hydroxy(CrC4)alkyl)aminogruppe, eine (Dihydroxy(C3-C4)alkyl)-aminogruppe, eine (Hydroxy(CrC4)alkyl)-CrC4-alkylaminogruppe, eine Trifluormethangruppe eine -C(O)H-Gruppe, eine -C(O)CH3-Gruppe, eine -C(O)CF3-Gruppe, eine -Si(CH3)3-Gruppe, eine CrC4-Hydroxyalkylgruppe oder eine C2-C4-Dihydroxyalkylgruppe darstellen, oder zwei nebeneinanderliegende Reste R2 bis R6 eine -O-CH2-O-Brücke bilden; X1 gleich Schwefel, Stickstoff, Sauerstoff, C-R9 oder N-R8 ist; X2 gleich Schwefel, Stickstoff, Sauerstoff, C-R10 oder N-R8 ist X3 gleich Schwefel, Stickstoff, Sauerstoff, C-R11 oder N-R8 ist;where R2, R3, R4, R5 and R6 independently of one another represent hydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxy group, a C r C 4 alkoxy group, a C 1 -C 4 hydroxyalkoxy group, a C r C 6 alkyl group, a C 1 -C 4 alkylthioether group, a mercapto group, a nitro group, an amino group, a C 1 -C 4 alkylamino group, a hydroxy^-CJalkylamino group, a di(C 1 -C 4 )alkylamino group, a di(hydroxy(C r C 4 )alkyl)amino group, a (dihydroxy(C 3 -C 4 )alkyl)amino group, a (hydroxy(C r C 4 )alkyl)-C r C 4 alkylamino group, a trifluoromethane group, a -C(O)H group, a -C(O)CH 3 group, a -C(O)CF 3 group, a -Si(CH 3 ) 3 group, a C r C 4 hydroxyalkyl group or a C 2 -C 4 dihydroxyalkyl group, or two adjacent radicals R2 to R6 form an -O-CH2-O- bridge; X1 is sulfur, nitrogen, oxygen, C-R9 or N-R8; X2 is sulfur, nitrogen, oxygen, C-R10 or N-R8; X3 is sulfur, nitrogen, oxygen, C-R11 or N-R8;

R7, R9, R10 und R11 unabhängig voneinander gleich Wasserstoff, einem Halogenatom (F, Cl, Br, J), einer Cyanogruppe, einer C1-C4-Alkoxygruppe, einer C^Ce-Alkylgruppe, einer CrC4-Alkylthioethergruppe, einer Mercaptogruppe, einer Nitrogruppe, einer Aminogruppe, einer C^C^AIkylaminogruppe, einer Di(C1-C4)-alkylaminogruppe, einer Di(CrC4-hydroxyalkyl)aminogruppe, einer C^C^Hydroxyalkylaminogruppe, einer Trifluormethangruppe einer -C(O)CH3-Gruppe, einer -C(O)CF3-Gruppe, einer -Si(CH3)3-Gruppe, einer C^C^Hydroxyalkylgruppe oder einer C3-C4-Dihydroxyalkylgruppe sind; und R8 gleich Wasserstoff, einer CrC6-Alkylgruppe, einer C2-C4-Hydroxyalkylgruppe, einer Phenylgruppe oder einer Acetylgruppe ist; unter der Bedingung, dass mindestens einer und maximal zwei der Reste X1 bis X3 gleich C-R9, C-R10 oder C-R11 sind und maximal einer der Reste X1 bis X3 gleich Schwefel, Sauerstoff oder N-R8 ist.R7, R9, R10 and R11 are independently hydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a C 1 -C 4 alkoxy group, a C^Ce alkyl group, a C r C 4 alkylthioether group, a mercapto group, a nitro group, an amino group, a C^C^alkylamino group, a di(C 1 -C 4 )alkylamino group, a di(C r C 4 hydroxyalkyl)amino group, a C^C^hydroxyalkylamino group, a trifluoromethane group, a -C(O)CH 3 group, a -C(O)CF 3 group, a -Si(CH 3 ) 3 group, a C^C^hydroxyalkyl group or a C 3 -C 4 dihydroxyalkyl group; and R8 is hydrogen, a C r C 6 alkyl group, a C 2 -C 4 hydroxyalkyl group, a phenyl group or an acetyl group; with the proviso that at least one and a maximum of two of the radicals X1 to X3 are C-R9, C-R10 or C-R11 and a maximum of one of the radicals X1 to X3 is sulfur, oxygen or N-R8.

Als Verbindungen der Formel (I) können beispielweise genannt werden: 1,3-Dihydroxy-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(1-methyl-1 H-pyrrol-2-yl)-benzol, 1,3-Dihydroxy-5-(pyrrol-2-yl)benzol, 1,3-Dihydroxy-5-(furan-2-yl)-benzol, 1,3-Dihydroxy-5-(3-amino-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(3-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(3-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(3-nitro-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(4-amino-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(4-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(4-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(4-nitro-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(5-nitro-thiophen-2-yl)-benzol,1,3-Dihydroxy-5-(5-amino-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(5-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(5-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(5-nitro-thiophen-2-yl)-Examples of compounds of formula (I) which may be mentioned are: 1,3-dihydroxy-5-(thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(1-methyl-1H-pyrrole-2- yl)-benzene, 1,3-dihydroxy-5-(pyrrol-2-yl)benzene, 1,3-dihydroxy-5-(furan-2-yl)-benzene, 1,3-dihydroxy-5-(3 -amino-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(3-chloro-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(3-methyl-thiophen-2 -yl)-benzene, 1,3-dihydroxy-5-(3-nitro-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(4-amino-thiophen-2-yl)-benzene, 1,3-Dihydroxy-5-(4-chloro-thiophen-2-yl)-benzene, 1,3-Dihydroxy-5-(4-methyl-thiophen-2-yl)-benzene, 1,3-Dihydroxy- 5-(4-nitro-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(5-nitro-thiophen-2-yl)-benzene,1,3-dihydroxy-5-(5-amino -thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(5-chloro-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(5-methyl-thiophen-2-yl )-benzene, 1,3-dihydroxy-5-(5-nitro-thiophen-2-yl)-

benzol, 1,3,5-Trihydroxy-5-(thiophen-2-yl)-benzol, 1,2,3-Trihydroxy-5-(thiophen-2-yl)-benzol, 1,3,6-Trihydroxy-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-methyl-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-methyl-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-6-methyl-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-chlor-5-(thiophen-2-yl)-benzol, 1 ,S-Dihydroxy-S-chlor-ö-(thiophen-2-yl)-benzol, I.S-Dihydroxy-e-chlor-ö-ithiophen^-yO-benzol, 1,3-Dihydroxy-2-methoxy-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-methoxy-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-6-methoxy-5-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(1-methyl-1 H-pyrrol-2-yl)-benzol, 1,3-Dihydroxy-2-(pyrrol-2-yl)benzol, 1,3-Dihydroxy-2-(furan-2-yl)-benzol, 1,3-Dihydroxy-2-(3-amino-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(3-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(3-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(3-nitro-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(4-amino-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(4-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(4-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(4-nitro-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(5-nitro-thiophen-2-yl)-benzol,1,3-Dihydroxy-2-(5-amino-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(5-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(5-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-(5-nitro-thiophen-2-yl)-benzol, 1,3,5-Trihydroxy-2-(thiophen-2-yl)-benzol, 1,2,3-Trihydroxy-2-(thiophen-2-yl)-benzol, 1,3,6-Trihydroxy-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-methyl-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-methyl-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-6-methyl-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-chlor-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-chlor-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-6-chlor-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-2-methoxy-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-methoxy-2-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-6-methoxy-2-(thiophen-benzene, 1,3,5-trihydroxy-5-(thiophen-2-yl)-benzene, 1,2,3-trihydroxy-5-(thiophen-2-yl)-benzene, 1,3,6-trihydroxy- 5-(thiophen-2-yl)-benzene, 1,3-dihydroxy-2-methyl-5-(thiophen-2-yl)-benzene, 1,3-dihydroxy-5-methyl-5-(thiophen-2 -yl)-benzene, 1,3-dihydroxy-6-methyl-5-(thiophen-2-yl)-benzene, 1,3-dihydroxy-2-chloro-5-(thiophen-2-yl)-benzene, 1,S-Dihydroxy-S-chloro-ö-(thiophen-2-yl)-benzene, I.S-Dihydroxy-e-chloro-ö-ithiophen^-yO-benzene, 1,3-Dihydroxy-2-methoxy-5-(thiophen-2-yl)-benzene, 1,3-dihydroxy-5-methoxy-5-(thiophen-2-yl)-benzene, 1,3-dihydroxy- 6-methoxy-5-(thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(1-methyl-1H- pyrrol-2-yl)-benzene, 1,3-dihydroxy-2-(pyrrol-2-yl)-benzene, 1,3-dihydroxy-2-(furan-2-yl)-benzene, 1,3-dihydroxy- 2-(3-amino-thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(3-chloro-thiophen-2-yl)-benzene, 1,3-Dihydroxy-2-(3-methyl-thiophen-2-yl)-benzene, 1,3-Dihydroxy-2-(3-nitro-thiophen-2-yl)-benzene, 1,3-Dihydroxy- 2-(4-amino-thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(4-chloro-thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(4-methyl -thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(4-nitro-thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(5-nitro-thiophen-2-yl). )-benzene, 1,3-dihydroxy-2-(5-amino-thiophen-2-yl)-benzene, 1,3-dihydroxy-2-(5-chloro-thiophen-2-yl)-benzene, 1,3-Dihydroxy-2-(5-methyl-thiophen-2-yl)-benzene, 1,3-Dihydroxy-2-(5-nitro-thiophen-2-yl)-benzene, 1,3,5- Trihydroxy-2-(thiophen-2-yl)-benzene, 1,2,3-trihydroxy-2-(thiophen-2-yl)-benzene, 1,3,6-trihydroxy-2-(thiophen-2-yl )-benzene, 1,3-dihydroxy-2-methyl-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy-5-methyl-2-(thiophen-2-yl)-benzene, 1, 3-Dihydroxy-6-methyl-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy-2-chloro-2-(thiophen-2-yl)-benzene, 1,3-Dihydroxy-5-chloro-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy-6-chloro-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy- 2-methoxy-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy-5-methoxy-2-(thiophen-2-yl)-benzene, 1,3-dihydroxy-6-methoxy-2- (thiophene-

• ft ··· · · · ft• ft ··· · · · ft

•••ft ft ft··· · · ft•••ft ft ft··· · · ft

I »ft·· ft·»» ftI »ft·· ft·»» ft

»•••ft ·· *·· ·· · ft ·»•••ft ·· *·· ·· · ft ·

2-yl)-benzol, 1,3-Dihydroxy-4-(pyridin-2-yl)-benzol, 1,3-Dihydroxy-4-(pyrimidin-2-yl)-benzol, 1,3-Dihydroxy-4-(5-methyl-pyridin-2-yl)-benzol, 5-(2,4-Dihydroxy-phenyl)-nicotinonitril, 1,3-Dihydroxy-4-(5-nitro-pyridin-2-yl)-benzol, 1,3-Dihydroxy-4-(thiophen-3-yl)-benzol, 4'-Methyl-biphenyl-2,4-diol, Biphenyl-2,4,4>-triol> Biphenyl-2,4,3'-triol, 41-Fluoro-biphenyl-2,4-diol, 1,3-Dihydroxy-4-(4-methyl-thiophen-3-yl)-benzol, 2',4'-Dihydroxy-biphenyl-4-carbonitril, 1,3-Dihydroxy-4-(2-Chloro-thiophen-3-yl)-benzol, 1-(2',4'-Dihydroxy-biphenyl-3-yl)-ethanon, 1,3-Dihydroxy-4-benzo[1,3]-dioxol-5-ylbenzol, 4'-Nitro-biphenyl-2,4-diol, 2'-Nitro-biphenyl-2,4-diol, 4-(5-Nitrothiophen-2-yl)-benzol, 4'-Trifluormethyl-biphenyl-2,4-diol, 2',4'-Dinnethylbiphenyl-2,4-diol, 3'-Methoxy-biphenyl-2,4-diol, 4'-Chloro-biphenyl-2,4-diol, 1,3-Dihydroxy-5-(pyridin-2-yl)-benzol, 1,3-Dihydroxy-5-(pyrimidin-2-yl)-benzol, 1,3-Dihydroxy-5-(thiophen-3-yl)-benzol, 5-Thiophen-2-ylbenzol, 1,3-Dihydroxy-(5-thiazol-2-yl)-benzol, 4'-Methyl-biphenyl-3,5-diol, 1,3-Dihydroxy-5-(5-methyl-pyridin-2-yl)-benzol, Biphenyl-S.ö^'-triol, Biphenyl-S.o.S'-triol, 4'-Fluoro-biphenyl-3,5-diol, 1,3-Dihydroxy-5-(4-methyl-thiophen-3-yl)-benzol, 3',5'-Dihydroxy-biphenyl-4-carbonitril, 1,3-Dihydroxy-5-(2-chlor-thiophen-3-yl)-benzol, 1 -(3',5'-Dihydroxybiphenyl-3-yl)-ethanon, 4'-Nitro-biphenyl-3,5-diol, 2'-Nitro-biphenyl-3,5-diol, 4'-Trifluormethyl-biphenyl-3,5-diol, 2',4'-Dimethyl-biphenyl-3,5-diol, 3'-Methoxy-biphenyl-3,5-diol, 4'-Chloro-biphenyl-3,5-diol, 1,3-Dihydroxy-5-(5-Nitro-pyridin-2-yl)-benzol, 4'-Methylsulfanyl-biphenyl-3,5-diol, 2"-Chlor-4'-nitro-biphenyl-3,5-diol, 4'-Methylsulfanyl-biphenyl-2,4-diol und 1,3-Dihydroxy-4-(thiazol-2-yl)-benzol sowie deren physiologisch verträglichen Salze.2-yl)-benzene, 1,3-dihydroxy-4-(pyridin-2-yl)-benzene, 1,3-dihydroxy-4-(pyrimidin-2-yl)-benzene, 1,3-dihydroxy-4 -(5-methyl-pyridin-2-yl)-benzene, 5-(2,4-dihydroxy-phenyl)-nicotinonitrile, 1,3-dihydroxy-4-(5-nitro-pyridin-2-yl)-benzene , 1,3-Dihydroxy-4-(thiophen-3-yl)-benzene, 4'-methyl-biphenyl-2,4-diol, biphenyl-2,4,4 > -triol > biphenyl-2,4,3 '-triol, 4 1 -fluoro-biphenyl-2,4-diol, 1,3-dihydroxy-4-(4-methyl-thiophen-3-yl)-benzene, 2',4'-Dihydroxy-biphenyl-4-carbonitrile, 1,3-Dihydroxy-4-(2-Chloro-thiophen-3-yl)-benzene, 1-(2',4'-Dihydroxy-biphenyl-3 -yl)-ethanone, 1,3-dihydroxy-4-benzo[1,3]-dioxol-5-ylbenzene, 4'-nitro-biphenyl-2,4-diol, 2'-nitro-biphenyl-2,4 -diol, 4-(5-nitrothiophen-2-yl)-benzene, 4'-trifluoromethyl-biphenyl-2,4-diol, 2',4'-dinnethylbiphenyl-2,4-diol, 3'-methoxy-biphenyl -2,4-diol, 4'-chloro-biphenyl-2,4-diol, 1,3-dihydroxy-5-(pyridin-2-yl)-benzene, 1,3-Dihydroxy-5-(pyrimidin-2-yl)-benzene, 1,3-dihydroxy-5-(thiophen-3-yl)-benzene, 5-thiophen-2-ylbenzene, 1,3-dihydroxy- (5-thiazol-2-yl)-benzene, 4'-methyl-biphenyl-3,5-diol, 1,3-dihydroxy-5-(5-methyl-pyridin-2-yl)-benzene, biphenyl-S .ö^'-triol, biphenyl-SoS'-triol, 4'-fluoro-biphenyl-3,5-diol, 1,3-dihydroxy-5-(4-methyl-thiophen-3-yl)-benzene, 3 ',5'-Dihydroxy-biphenyl-4-carbonitrile, 1,3-dihydroxy-5-(2-chloro-thiophen-3-yl)-benzene, 1 -(3',5'-Dihydroxybiphenyl-3-yl)-ethanone, 4'-nitro-biphenyl-3,5-diol, 2'-nitro-biphenyl-3,5-diol, 4'-trifluoromethyl-biphenyl- 3,5-diol, 2',4'-dimethyl-biphenyl-3,5-diol, 3'-methoxy-biphenyl-3,5-diol, 4'-chloro-biphenyl-3,5-diol, 1, 3-Dihydroxy-5-(5-Nitropyridin-2-yl)-benzene, 4'-Methylsulfanyl-biphenyl-3,5-diol, 2"-Chloro-4'-nitro-biphenyl-3,5-diol , 4'-methylsulfanyl-biphenyl-2,4-diol and 1,3-dihydroxy-4-(thiazol-2-yl)-benzene and their physiologically tolerated salts.

Bevorzugt sind Verbindungen der Formel (I) in denen gilt:Preferred are compounds of formula (I) in which:

(i) &KHgr;2 ist gleich C-R10 und &KHgr;1 ist gleich Schwefel und X3 ist gleich C-R11 beziehungsweise X1 ist gleich C-R9 und X3 ist gleich Schwefel; oder (ii) X2 ist gleich C-R10 und X1 ist gleich Schwefel und X3 ist gleich C-R11 beziehungsweise X1 ist gleich C-R9 und X3 ist gleich Schwefel und mindestens einer der Reste R9 bis R11 ist gleich Wasserstoff.(i) &KHgr;2 is C-R10 and &KHgr;1 is sulfur and X3 is C-R11 or X1 is C-R9 and X3 is sulfur; or (ii) X2 is C-R10 and X1 is sulfur and X3 is C-R11 or X1 is C-R9 and X3 is sulfur and at least one of the radicals R9 to R11 is hydrogen.

Besonders bevorzugt sind die folgenden Verbindungen der Formel (I): 1,3-Dihydroxy-4-(thiophen-2-yl)-benzol, 1,3-Dihydroxy-4-(5-nitro-thiophen-2-yl)-benzol, 1,3-Dihydroxy-4-(3-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(5-chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(3-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-4-(thiophen-3-yl)-benzol und 1,3-Dihydroxy-5-(thiophen-3-yl)-benzol sowie deren physiologisch verträglichen Salze.The following compounds of formula (I) are particularly preferred: 1,3-dihydroxy-4-(thiophen-2-yl)benzene, 1,3-dihydroxy-4-(5-nitro-thiophen-2-yl)benzene, 1,3-dihydroxy-4-(3-methyl-thiophen-2-yl)benzene, 1,3-dihydroxy-5-(5-chloro-thiophen-2-yl)benzene, 1,3-dihydroxy-5-(3-methyl-thiophen-2-yl)benzene, 1,3-dihydroxy-4-(thiophen-3-yl)benzene and 1,3-dihydroxy-5-(thiophen-3-yl)benzene and their physiologically acceptable salts.

Die Verbindungen der Formel (I) können in dem Färbemittel sowohl als freie Base als auch in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Basen, wie zum Beispiel Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat oder Tetrabutylammoniumhydroxid, eingesetzt werden.The compounds of formula (I) can be used in the dye both as free base and in the form of their physiologically acceptable salts with inorganic or organic bases, such as sodium hydroxide, potassium hydroxide, sodium carbonate or tetrabutylammonium hydroxide.

Die 1,3-Dihydroxy-benzol-Derivate der Formel (I) sind in dem erfindungsgemäßen Färbemittel in einer Gesamtmenge von etwa 0,005 bis 20 Gewichtsprozent enthalten, wobei eine Menge von etwa 0,01 bis 5 Gewichtsprozent und insbesondere 0,1 bis 2,5 Gewichtsprozent bevorzugt ist.The 1,3-dihydroxybenzene derivatives of the formula (I) are contained in the colorant according to the invention in a total amount of about 0.005 to 20 percent by weight, with an amount of about 0.01 to 5 percent by weight and in particular 0.1 to 2.5 percent by weight being preferred.

Als Entwicklersubstanzen kommen vorzugsweise 1,4-Diaminobenzol (p-Phenylendiamin), 1,4-Diamino-2-methyl-benzol (p-Toluylendiamin),The preferred developer substances are 1,4-diaminobenzene (p-phenylenediamine), 1,4-diamino-2-methylbenzene (p-toluenediamine),

1 ^-Diamino^.e-dimethyl-benzol, 1 ^-Diamino-S.S-diethyl-benzol, 1 ^-Diamino^.S-dimethyl-benzol, 1 ^-Diamino^.S-dimethyl-benzol, 2-ChIoM ,4-diaminobenzol, 1,4-Diamino-2-(thiophen-2-yl)benzol, 1,4-Diamino-2-(thiophen-3-yl)benzol, 1,4-Diamino-2-(pyridin-3-yl)benzol, 2,5-Diaminobiphenyl, 1,4-Diamino-2-methoxymethyl-benzol, 1,4-Diamino-2-aminomethyl-benzol, 1 ^-Diamino^-hydroxymethyl-benzol, 1,4-Diamino-2-(2-hydroxyethoxy)-benzol, 2-(2-(Acetylamino)ethoxy)-1,4-diamino-benzol, 4-Phenylamino-anilin, 4-Dimethylamino-anilin, 4-Diethylamino-anilin, 4-Dipropylamino-anilin, 4-[Ethyl(2-hydroxyethyl)-amino]-anilin, 4-[Di(2-hydroxyethyl)amino]-anilin, 4-[Di(2-hydroxyethyl)-amino]-2-methyl-anilin, 4-[(2-Methoxyethyl)amino]-anilin, 4-[(3-Hydroxypropyl)amino]-anilin, 4-[(2,3-Dihydroxypropyl)amino]-anilin, 1,4-Diamino-2-(1 -hydroxyethyl)-benzol, 1,4-Diamino-2-(2-hydroxyethyl)-benzol, 1,4-Diamino-2-(1-methylethyl)-benzol, 1,3-Bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, 1,4-Bis[(4-aminophenyl)amino]-butan, 1,8-Bis(2,5-diaminophenoxy)-3,6-dioxaoctan, 4-Amino-phenol, 4-Amino-3-methyl-phenol, 4-Amino-3-(hydroxymethyl)-phenol, 4-Amino-3-fluorphenol, 4-Methylamino-phenol, 4-Amino-2-(aminomethyl)-phenol, 4-Amino-2-(hydroxymethyl)-phenol, 4-Amino-2-fluor-phenol, 4-Amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-Amino-2-methyl-phenol, 4-Amino-2-(methoxymethyl)-phenol, 4-Amino-2-(2-hydroxyethyl)-phenol, 5-Amino-salicylsäure, 2,5-Diamino-pyridin, 2,4,5,6-Tetraamino-pyrimidin, 2,5,6-Triamino-4-(1 H)-pyrimidon, 4,5-Diamino-1-(2-hydroxyethyl)-1 H-pyrazol, 4,5-Diamino-1-(1-methylethyl)-1 H-pyrazol, 4,5-Diamino-1-[(4-methylphenyl)methyl]-1 H-pyrazol, 1 -[^-ChlorphenyOmethylH.S-diamino-1 H-pyrazol, 4,5-Diamino-1-methyl-1 H-pyrazol, 2-Amino-phenol, 2-Amino-6-methyl-phenol, 2-Amino-5-methyl-phenol und 1,2,4-Trihydroxy-benzol in Betracht.1^-Diamino^.e-dimethyl-benzene, 1^-Diamino^.S-diethyl-benzene, 1^-Diamino^.S-dimethyl-benzene, 1^-Diamino^.S-dimethyl-benzene, 2-ChIoM ,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene, 1,4-diamino-2-(thiophen-3-yl)benzene, 1,4-diamino-2-(pyridine- 3-yl)benzene, 2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethyl-benzene, 1,4-diamino-2-aminomethyl-benzene, 1^-diamino^-hydroxymethyl-benzene, 1,4- Diamino-2-(2-hydroxyethoxy)-benzene, 2-(2-(Acetylamino)ethoxy)-1,4-diamino-benzene, 4-phenylamino-aniline, 4-dimethylamino-aniline, 4-diethylamino-aniline, 4-dipropylamino-aniline, 4-[Ethyl(2- hydroxyethyl)-amino]-aniline, 4-[di(2-hydroxyethyl)-amino]-aniline, 4-[di(2-hydroxyethyl)-amino]-2-methyl-aniline, 4-[(2-methoxyethyl)amino ]-aniline, 4-[(3-hydroxypropyl)amino]-aniline, 4-[(2,3-dihydroxypropyl)amino]-aniline, 1,4-diamino-2-(1-hydroxyethyl)-benzene, 1, 4-diamino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 1,3-Bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, 1,4-Bis[(4-aminophenyl)amino]-butane, 1,8-Bis(2,5-diaminophenoxy )-3,6-dioxaoctane, 4-amino-phenol, 4-amino-3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol, 4-amino-3-fluorophenol, 4-methylamino-phenol, 4-Amino-2-(aminomethyl)-phenol, 4-amino-2-(hydroxymethyl)-phenol, 4-amino-2-fluoro-phenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl -phenol, 4-amino-2-methyl-phenol, 4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 5-amino-salicylic acid, 2,5-Diamino-pyridine, 2,4,5,6-Tetraamino-pyrimidine, 2,5,6-Triamino-4-(1H)-pyrimidone, 4,5-Diamino-1-(2-hydroxyethyl) -1 H-pyrazole, 4,5-diamino-1-(1-methylethyl)-1 H-pyrazole, 4,5-diamino-1-[(4-methylphenyl)methyl]-1 H-pyrazole, 1 -[ ^-ChlorphenyOmethylH.S-diamino-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 2-amino-phenol, 2-amino-6-methyl-phenol, 2-amino-5- methyl-phenol and 1,2,4-trihydroxy-benzene into consideration.

Weiterhin kann das erfindungsgemäße Färbemittel zusätzlich zu den Verbindungen der Formel (I) noch weitere bekannte Kupplersubstanzen, beispielsweise N-(3-Dimethylamino-phenyl)-hamstoff, 2,6-Diamino-pyridin, 2-Amino-4-[(2-hydroxyethyl)amino]-anisol, 2,4-Diamino-1-fluor-5-methylbenzol, 2,4-Diamino-1 -methoxy-5-methyl-benzol, 2,4-Diamino-1 -ethoxy-5-methyl-benzol, 2,4-Diamino-1-(2-hydroxyethoxy)-5-methyl-benzol, 2,4-Di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzol, 2,3-Diamino-6-methoxy-pyridin, 3-Amino-6-methoxy-2-(methylamino)-pyridin, 2,6-Diamino-3,5-dimethoxy-pyridin, 3,5-Diamino-2,6-dimethoxy-pyridin, 1,3-Diamino-benzol, 2,4-Diamino-1-(2-hydroxyethoxy)-benzol, 1,3-Diamino-4-(2,3-dihydroxypropoxy)-benzol, 1,3-Diamino-4-(3-hydroxypropoxy)-benzol, 1,3-Diamino-4-(2-methoxyethoxy)-benzol, 2,4-Diamino-1,5-di(2-hydroxyethoxy)-benzol, 1 -(2-Aminoethoxy)-2,4-diamino-benzol, 2-Amino-1-(2-hydroxyethoxy)-4-methylamino-benzol, 2,4-Diaminophenoxy-essigsäure, 3-[Di(2-hydroxyethyl)amino]-anilin, 4-Amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzol, 5-Methyl-2-(1-methylethyl)-phenol, 3-[(2-Hydroxyethyl)amino]-anilin, 3-[(2-Aminoethyl)amino]-anilin, 1,3-Di(2,4-diaminophenoxy)-propan, Di(2,4-diaminophenoxy)-methan, 1,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis(2-hydroxyethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethylamino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2-methyl-phenol, 5-Amino-4-methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2-methyl-phenol, 3-Amino-2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino-2-methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)-amino]-acetamid, 5-[(2-Hydroxyethyl)amino]-4-methoxy-2-methyl-phenol, 5-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-Methoxyethyl)amino]-phenol, 5-Amino-2-ethyl-phenol,Furthermore, the colorant according to the invention can contain, in addition to the compounds of formula (I), other known coupler substances, for example N-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1,3-diamino-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 1,3-diamino-4-(2,3-dihydroxypropoxy)-benzene, 1,3-diamino-4-(3-hydroxypropoxy)-benzene, 1,3-diamino-4-(2-methoxyethoxyeth oxy)-benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diamino-benzene, 2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 3-[di(2-hydroxyethyl)amino]-aniline, 2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-Methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane, di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis(2 -hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol, 5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichloro-phenol, 5-amino -2,4-dichloro-phenol, 3-amino-2-methyl-phenol, 3-Amino-2-chloro-6-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)-amino]-acetamide, 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methyl-phenol, 5-[(2-hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-phenol, [(2-Methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol,

5-Amino-2-methoxy-phenol, 2-(4-Amino-2-hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)-amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 2-Amino-3-hydroxy-pyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 5-Amino-4-chlor-2-methyl-phenol, 1-Naphthol, 2-Methyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol-acetat, 1,3-Dihydroxybenzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1,3-dihydroxy-benzol, 1 ^-Dichlor-S^-dihydroxy^-methyl-benzol, 1,5-Dichlor-2,4-dihydroxybenzol, 1,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy-phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1,3-benzodioxol, 6-Brom-1-hydroxy-3,4-methylendioxy-benzol, 3,4-Diamino-benzoesäure, 3,4-Dihydro-6-hydroxy-1,4(2H)-benzoxazin, 6-Amino-3,4-dihydro-1,4(2H)-benzoxazin, 3-Methyl-1-phenyl-5-pyrazolon, 5,6-Dihydroxy-indol, 5,6-Dihydroxy-indolin, 5-Hydroxy-indol, 6-Hydroxy-indol, 7-Hydroxy-indol und 2,3-lndolindion, enthalten.5-Amino-2-methoxy-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol, 5-[(3-hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-dihydroxypropyl )-amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 5-Amino-4-chloro-2-methyl-phenol, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2, 7-Dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 1^-dichloro-S^-dihydroxy^-methyl-benzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene , 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl- 1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole and 2,3-indolindione.

Die Kupplersubstanzen und Entwicklersubstanzen können in dem erfindungsgemäßen Färbemittel jeweils einzeln oder im Gemisch miteinander enthalten sein, wobei die Gesamtmenge an Kupplersubstanzen und Entwicklersubstanzen in dem erfindungsgemäßen Färbemittel (bezogen auf die Gesamtmenge des Färbemittels) jeweils etwa 0,005 bis 20 Gewichtsprozent, vorzugsweise etwa 0,01 bis 5 Gewichtsprozent und insbesondere 0,1 bis 2,5 Gewichtsprozent, beträgt.The coupler substances and developer substances can be contained in the colorant according to the invention individually or in a mixture with one another, the total amount of coupler substances and developer substances in the colorant according to the invention (based on the total amount of the colorant) being in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 5 percent by weight and in particular 0.1 to 2.5 percent by weight.

Die Gesamtmenge der in dem hier beschriebenen Färbemittel enthaltenen Entwicklersubstanz-Kupplersubstanz-Kombination beträgt vorzugsweise etwa 0,01 bis 20 Gewichtsprozent, wobei eine Menge von etwa 0,02 bisThe total amount of the developer substance-coupler substance combination contained in the colorant described here is preferably about 0.01 to 20 percent by weight, with an amount of about 0.02 to

10 Gewichtsprozent und insbesondere 0,2 bis 6 Gewichtsprozent besonders bevorzugt ist. Die Entwicklersubstanzen und Kupplersubstanzen werden im allgemeinen in etwa äquimolaren Mengen eingesetzt; es ist jedoch nicht nachteilig, wenn die Entwicklersubstanzen diesbezüglich in einem gewissen Überschuß oder Unterschuß vorhanden sind.10% by weight and in particular 0.2 to 6% by weight is particularly preferred. The developer substances and coupler substances are generally used in approximately equimolar amounts; however, it is not disadvantageous if the developer substances are present in a certain excess or deficiency in this respect.

Weiterhin kann das erfindungsgemäße Färbemittel zusätzlich andere Farbkomponenten, beispielsweise 6-Amino-2-methylphenol und 2-Amino-5-methylphenol, sowie ferner übliche direktziehende Farbstoffe aus der Gruppe der sauren oder basischen Farbstoffe, der Triphenylmethanfarbstoffe, der aromatischen Nitrofarbstoffe, der Azofarbstoffe und der Dispersionsfarbstoffe, enthalten. Die erfindungsgemäßem Färbemittel können diese Farbkomponenten in einer Menge von etwa 0,1 bis 4 Gewichtsprozent enthalten.Furthermore, the colorant according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, as well as conventional direct dyes from the group of acidic or basic dyes, triphenylmethane dyes, aromatic nitro dyes, azo dyes and disperse dyes. The colorants according to the invention can contain these color components in an amount of about 0.1 to 4 percent by weight.

Selbstverständlich können die zusätzlichen Kupplersubstanzen sowie die Entwicklersubstanzen und die anderen Farbkomponenten, sofern es Basen sind, auch in Form der physiologisch verträglichen Salze mit organischen oder anorganischen Säuren, wie beispielsweise Salzsäure oder Schwefelsäure, beziehungsweise - sofern sie aromatische OH-Gruppen besitzen - in Form der Salze mit Basen, zum Beispiel als Alkaliphenolate, eingesetzt werden.Of course, the additional coupler substances as well as the developer substances and the other color components, if they are bases, can also be used in the form of physiologically acceptable salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or - if they have aromatic OH groups - in the form of salts with bases, for example as alkali phenolates.

Darüber hinaus können in den Färbemitteln, falls diese zur Färbung von Haaren verwendet werden sollen, noch weitere übliche kosmetische Zusätze, beispielsweise Antioxidantien wie Ascorbinsäure, Thioglykol-In addition, if the dyes are to be used to colour hair, they may contain other common cosmetic additives, such as antioxidants such as ascorbic acid, thioglycolic acid,

säure oder Natriumsulfit, sowie Parfümöle, Komplexbildner, Netzmittel, Emulgatoren, Verdicker und Pflegestoffe enthalten sein.acid or sodium sulphite, as well as perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances.

Die Zubereitungsform des erfindungsgemäßen Färbemittels kann beispielsweise eine Lösung, insbesondere eine wässrige oder wässrigalkoholische Lösung sein. Die besonders bevorzugten Zubereitungsformen sind jedoch eine Creme, ein Gel oder eine Emulsion. Ihre Zusammensetzung stellt eine Mischung der Farbstoffkomponenten mit den für solche Zubereitungen üblichen Zusätzen dar.The preparation form of the colorant according to the invention can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution. The particularly preferred preparation forms, however, are a cream, a gel or an emulsion. Their composition represents a mixture of the dye components with the additives customary for such preparations.

Übliche Zusätze in Lösungen, Cremes, Emulsionen oder Gelen sind zum Beispiel Lösungsmittel wie Wasser, niedere aliphatische Alkohole, beispielsweise Ethanol, Propanol oder Isopropanol, Glycerin oder Glykole wie 1,2-Propylenglykol, weiterhin Netzmittel oder Emulgatoren aus den Klassen der anionischen, kationischen, amphoteren oder nichtionogenen oberflächenaktiven Substanzen wie zum Beispiel Fettalkoholsulfate, oxethylierte Fettalkoholsulfate, Alkylsulfonate, Alkylbenzolsulfonate, Alkyltrimethylammoniumsalze, Alkylbetaine, oxethylierte Fettalkohole, oxethylierte Nonylphenole, Fettsäurealkanolamide und oxethylierte Fettsäureester ferner Verdicker wie höhere Fettalkohole, Stärke, Cellulosederivate, Petrolatum, Paraffinöl und Fettsäuren, sowie außerdem Pflegestoffe wie kationische Harze, Lanolinderivate, Cholesterin, Pantothensäure und Betain. Die erwähnten Bestandteile werden in den für solche Zwecke üblichen Mengen verwendet, zum Beispiel die Netzmittel und Emulgatoren in Konzentrationen von etwa 0,5 bis 30 Gewichtsprozent, die Verdicker in einer Menge von etwa 0,1 bis 30 Gewichtsprozent und die Pflegestoffe in einer Konzentration von etwa 0,1 bis 5 Gewichtsprozent.Common additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerin or glycols such as 1,2-propylene glycol, as well as wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, oxyethylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkyl betaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides and oxyethylated fatty acid esters, as well as thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, as well as care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The components mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 30 percent by weight and the care substances in a concentration of about 0.1 to 5 percent by weight.

• ··

Je nach Zusammensetzung kann das erfindungsgemäiie Färbemittel schwach sauer, neutral oder alkalisch reagieren. Insbesondere weist es einen pH-Wert von 6,5 bis 11,5 auf, wobei die basische Einstellung vorzugsweise mit Ammoniak erfolgt. Es können aber auch organische Amine, zum Beispiel Monoethanolamin und Triethanolamin, oder auch anorganische Basen wie Natriumhydroxid und Kaliumhydroxid Verwendung finden. Für eine pH-Einstellung im sauren Bereich kommen anorganische oder organische Säuren, zum Beispiel Phosphorsäure, Essigsäure, Zitronensäure oder Weinsäure, in Betracht.Depending on the composition, the colorant according to the invention can react in a slightly acidic, neutral or alkaline manner. In particular, it has a pH value of 6.5 to 11.5, with the basic adjustment preferably being carried out with ammonia. However, organic amines, for example monoethanolamine and triethanolamine, or inorganic bases such as sodium hydroxide and potassium hydroxide can also be used. Inorganic or organic acids, for example phosphoric acid, acetic acid, citric acid or tartaric acid, can be used for pH adjustment in the acidic range.

Für die Anwendung zur oxidativen Färbung von Haaren vermischt man das vorstehend beschriebene Färbemittel unmittelbar vor dem Gebrauch mit einem Oxidationsmittel und trägt eine für die Haarfärbebehandlung ausreichende Menge, je nach Haarfülle, im allgemeinen etwa 60 bis Gramm, dieses Gemisches auf das Haar auf.For use in the oxidative coloring of hair, the dye described above is mixed with an oxidizing agent immediately before use and a sufficient amount of this mixture for the hair coloring treatment, depending on the thickness of the hair, generally about 60 to 100 grams, is applied to the hair.

Als Oxidationsmittel zur Entwicklung der Haarfärbung kommen hauptsächlich Wasserstoffperoxid oder dessen Additionsverbindungen an Harnstoff, Melamin, Natriumborat oder Natriumcarbonat in Form einer 3-bis 12prozentigen, vorzugsweise 6prozentigen, wässrigen Lösung, aber auch Luftsauerstoff in Betracht. Wird eine 6prozentige Wasserstoffperoxid-Lösung als Oxidationsmittel verwendet, so beträgt das Gewichtsverhältnis zwischen Haarfärbemittel und Oxidationsmittel 5:1 bis 1:2, vorzugeweise jedoch 1:1. Größere Mengen an Oxidationsmittel werden vor allem bei höheren Farbstoffkonzentrationen im Haarfärbemittel, oder wenn gleichzeitig eine stärkere Bleichung des Haares beabsichtigt ist, verwendet. Man läßt das Gemisch bei 15 bis 50 GradThe oxidizing agents used to develop hair color are mainly hydrogen peroxide or its addition compounds with urea, melamine, sodium borate or sodium carbonate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5:1 to 1:2, but preferably 1:1. Larger amounts of oxidizing agent are used above all when the dye concentration in the hair dye is higher, or when a stronger bleaching of the hair is intended at the same time. The mixture is left to ferment at 15 to 50 degrees.

Celsius etwa 10 bis 45 Minuten lang, vorzugsweise 30 Minuten lang, auf das Haar einwirken, spült sodann das Haar mit Wasser aus und trocknet es. Gegebenenfalls wird im Anschluß an diese Spülung mit einem Shampoo gewaschen und eventuell mit einer schwachen organischen Säure, wie zum Beispiel Zitronensäure oder Weinsäure, nachgespült. Anschließend wird das Haar getrocknet.Celsius for about 10 to 45 minutes, preferably 30 minutes, then rinse the hair with water and dry it. If necessary, wash with a shampoo after this rinse and possibly rinse with a weak organic acid, such as citric acid or tartaric acid. Then dry the hair.

Das erfindungsgemäße Färbemittel mit einem Gehalt an 1,3-Dihydroxybenzol-Derivaten der Formel (I) als Kupplersubstanz ermöglicht Färbungen mit ausgezeichneter Farbechtheit, insbesondere was die Lichtechtheit, Waschechtheit und Reibeechtheit anbetrifft. Hinsichtlich der färberischen Eigenschaften bietet das erfindungsgemäße Färbemittel je nach Art und Zusammensetzung der Farbkomponenten eine breite Palette verschiedener Farbnuancen, welche sich von blonden über braune, purpurne, violette bis hin zu blauen und schwarzen Farbtönen erstreckt. Hierbei zeichnen sich die Farbtöne durch ihre besondere Farbintensität aus. Die sehr guten färberischen Eigenschaften des Färbemittels gemäß der vorliegenden Anmeldung zeigen sich weiterhin darin, dass dieses Mittel insbesondere auch eine Anfärbung von ergrauten, chemisch nicht vorgeschädigten Haaren problemlos und mit guter Deckkraft ermöglicht.The dye according to the invention containing 1,3-dihydroxybenzene derivatives of formula (I) as a coupler substance enables dyeing with excellent color fastness, particularly with regard to light fastness, wash fastness and rubbing fastness. In terms of coloring properties, the dye according to the invention offers a wide range of different color nuances, depending on the type and composition of the color components, ranging from blonde to brown, purple, violet to blue and black shades. The shades are characterized by their particular color intensity. The very good coloring properties of the dye according to the present application are also shown in the fact that this agent also enables graying hair that has not been chemically damaged without any problems and with good coverage.

Die Herstellung der erfindungsgemäßen 1,3-Dihydroxy-benzol-Derivate der Formel (I) kann unter Verwendung von bekannten Syntheseverfahren erfolgen. Die Synthese der erfindungsgemäßen Verbindungen kann beispielsweise durch eine Palladium(O) katalysierte Kupplung eines substituierten Benzols der Formel (II) mit einer Verbindung der Formel RI-Rd und anschließende Abspaltung der Schutzgruppe erfolgen;The preparation of the 1,3-dihydroxybenzene derivatives of the formula (I) according to the invention can be carried out using known synthesis processes. The synthesis of the compounds according to the invention can be carried out, for example, by a palladium(O)-catalyzed coupling of a substituted benzene of the formula (II) with a compound of the formula RI-Rd and subsequent removal of the protective group;

♦ · ft··♦ · ft··

RaORAO

(II) wobei(II) where

Rb die Bedeutung Halogen (F, Cl, Br, J) und Rd die Bedeutung B(OH)2 hat, beziehungsweise Rb die Bedeutung B(OH)2 und Rd die Bedeutung Halogen (F, Cl, Br, J) hat;Rb is halogen (F, Cl, Br, I) and Rd is B(OH) 2 , or Rb is B(OH) 2 and Rd is halogen (F, Cl, Br, I);

Ra für eine Schutzgruppe steht, wie sie zum Beispiel in dem Kapitel „Protective Groups" in Organic Synthesis, Kapitel 3, Wiley lnterscience, 1991 beschrieben wird; und
R1 die in Formel (I) genannte Bedeutung hat.Ra represents a protecting group, as described, for example, in the chapter "Protective Groups" in Organic Synthesis, Chapter 3, Wiley lnterscience, 1991; and
R1 has the meaning given in formula (I).

Die 1,3-Dihydroxy-benzol-Derivate der Formel (I) sind gut in Wasser löslich und ermöglichen Färbungen mit ausgezeichneter Farbintensität und Farbechtheit, insbesondere was die Lichtechtheit, Waschechtheit und Reibeechtheit anbetrifft. Sie weisen weiterhin eine ausgezeichnete Lagerstabilität, insbesondere als Bestandteil der hier beschriebenen Oxidationsfärbemitteln, auf.The 1,3-dihydroxybenzene derivatives of formula (I) are readily soluble in water and enable dyeings with excellent color intensity and color fastness, particularly with regard to light fastness, wash fastness and rubbing fastness. They also have excellent storage stability, particularly as a component of the oxidation dyes described here.

Ein weiterer Gegenstand der vorliegenden Erfindung sind daher neue 1,3-Dihydroxy-benzol-Derivate der Formel (I), in denen R1 nicht gleich Phenyl oder Hydroxyphenyl ist.A further object of the present invention are therefore novel 1,3-dihydroxybenzene derivatives of the formula (I) in which R1 is not phenyl or hydroxyphenyl.

Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf zu beschränken.The following examples are intended to illustrate the subject matter of the invention in more detail without limiting it thereto.

16 Beispiele16 Examples

Beispiel 1: Synthese von 1,3-Dihydroxy-benzolen (Allgemeine Synthesevorschrift) Example 1 : Synthesis of 1,3-dihydroxybenzenes (general synthesis procedure)

A. Synthese von 2-[2-Brom-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]-tetrahydro-2H-pyranA. Synthesis of 2-[2-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]-tetrahydro-2H-pyran

Zu einer Lösung von 9,5 g (40 mmol) 4-Brom-1,3-dihydroxybenzol und 5 g (20 mmol) Toluol-4-sulfonsäure-Pyridinsalz in 50 ml Dichlormethan werden unter Argon 9 g (105 mmol) 3,4-Dihydro-2-H-pyran getropft. Das Reaktionsgemisch wird 18 Stunden lang gerührt. Anschließend wird die Reaktionsmischung in 100 ml Essigsäureethylester gegossen, die organische Phase mit verdünnter Natronlauge extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestilliert und der Rückstand an Kieselgel mit Petrolether/ Essigsäureethylester (7:1) gereinigt.9 g (105 mmol) of 3,4-dihydro-2-H-pyran are added dropwise to a solution of 9.5 g (40 mmol) of 4-bromo-1,3-dihydroxybenzene and 5 g (20 mmol) of toluene-4-sulfonic acid pyridine salt in 50 ml of dichloromethane under argon. The reaction mixture is stirred for 18 hours. The reaction mixture is then poured into 100 ml of ethyl acetate, the organic phase is extracted with dilute sodium hydroxide solution and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether/ethyl acetate (7:1).

Es werden 9,5 g (54% der Theorie) 2-[2-Brom-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran erhalten.9.5 g (54% of theory) of 2-[2-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran are obtained.

B. Synthese von 2- [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyranB. Synthesis of 2-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy ]-tetrahydro-2H-pyran

Eine Mischung von 5,5 g (154 mmol) 2-[2-Brom-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran aus Stufe A, 9 g (355 mmol) 4,4,5,5,4\4\5\5l-Octamethyl-[2,2]bi[[1,3,2]dioxaborinanyl], 1,5 g (2,2 mmol) Dichloro(1,1'-bis(diphenyl-phosphino)ferrocene)palladium (PdCI2(dppf)) und 6,2 g (63,2 mmol) Kaliumacetat wird unter Argon mitA mixture of 5.5 g (154 mmol) of 2-[2-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran from step A, 9 g (355 mmol) of 4,4,5,5,4\4\5\5 l -octamethyl-[2,2]bi[[1,3,2]dioxaborinanyl], 1.5 g (2.2 mmol) of dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (PdCl 2 (dppf)) and 6.2 g (63.2 mmol) of potassium acetate is treated under argon with

• *• *

210 ml entgastem Dioxan versetzt. Das Gemisch wird 24 Stunden lang bei 80 0C gerührt, sodann auf Wasser gegossen und mit Essigsäureethylester extrahiert. Die organische Phase wird anschließend mit einer gesättigten wässerigen Kochsalz-Lösung gewaschen, über Natriumsulfat getrocknet und nach Filtration eingeengt. Das erhaltene Rohprodukt wird an desaktiviertem Kieselgel mit einem Gradienten von Hexan (100%) über Hexan/Essigsäureethylester (9:1 bis 3:2) gereinigt. Es werden 4,70 g (77% der Theorie) 2- [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]- tetrahydro-2H-pyran erhalten.210 ml of degassed dioxane are added. The mixture is stirred for 24 hours at 80 ° C, then poured into water and extracted with ethyl acetate. The organic phase is then washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate and concentrated after filtration. The crude product obtained is purified on deactivated silica gel with a gradient of hexane (100%) over hexane/ethyl acetate (9:1 to 3:2). 4.70 g (77% of theory) of 2-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran are obtained.

C. Synthese der 1,3-Dihydroxy-benzole der Formel (I) 0,09 g (0,2 mmol) 2- [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran aus Stufe B und 0,4 mmol des entsprechenden Bromderivates werden unter Argon in 10 ml 1,2-Dimethoxyethan gelöst. Anschließend werden 0,01 g (0,005 mmol) Tetrakis-(triphenylphosphin)-palladium und 0,26 ml 2N Kaliumcarbonat-Lösung zugegeben und die Reaktionsmischung auf 80 0C erwärmt. Nach Beendigung der Reaktion wird die Reaktionsmischung in 10 ml Essigsäureethylester gegossen, die organische Phase mit verdünnter Natronlauge extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestiliiert und der Rückstand an Kieselgel mit Petrolether/Essigsäureethylester (9:1) gereinigt. C. Synthesis of the 1,3-dihydroxybenzenes of the formula (I) 0.09 g (0.2 mmol) of 2-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran from step B and 0.4 mmol of the corresponding bromine derivative are dissolved in 10 ml of 1,2-dimethoxyethane under argon. Then 0.01 g (0.005 mmol) of tetrakis(triphenylphosphine)palladium and 0.26 ml of 2N potassium carbonate solution are added and the reaction mixture is heated to 80 0 C. After the reaction has ended, the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with dilute sodium hydroxide solution and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether/ethyl acetate (9:1).

• m • m

• · · ·♦• · · ·♦

1818

a. 1,3-Dihydroxy-4-(thiophenyl-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-thiophen Massenspektrum: MH+ 192(100) a. 1,3-Dihydroxy-4-(thiophenyl-2-yl)-benzene Bromine derivative used: 2-bromo-thiophene Mass spectrum: MH+ 192(100)

b. 1,3-Dihydroxy-4-(5-nitro-thiophen-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-5-nitro-thiophen Massenspektrum: MH+ 237(100) b. 1,3-Dihydroxy-4-(5-nitro-thiophen-2-yl)-benzene Bromine derivative used : 2-bromo-5-nitro-thiophene Mass spectrum: MH+ 237(100)

c. 1,3-Dihydroxy-4-(3-methyl-thiophen-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-3-methyl-thiophen Massenspektrum: MH+ 206(100) c. 1,3-Dihydroxy-4-(3-methyl-thiophen-2-yl)-benzene Bromine derivative used: 2-bromo-3-methyl-thiophene Mass spectrum: MH+ 206(100)

d. 1,3-Dihydroxy-4-(pyridin-2-yl)-benzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-pyridin Massenspektrum: MH+ 188(100) d. 1,3-Dihydroxy-4-(pyridin-2-yl)-benzene hydrochloride Bromine derivative used: 2-bromo-pyridine Mass spectrum: MH+ 188(100)

e. 1,3-Dihydroxy-4-(pyrimidin-2-yl)-benzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-pyrimidin Massenspektrum: MH+ 189(100) e. 1,3-Dihydroxy-4-(pyrimidin-2-yl)-benzene hydrochloride Bromine derivative used: 2-bromo-pyrimidine Mass spectrum: MH+ 189(100)

f. 1 ,S-Dihydroxy^-tS-methyl-pyridin^-yQ-benzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-5-methyl-pyridin Massenspektrum: MH+ 188(100) f. 1 ,S-Dihydroxy^-tS-methyl-pyridine^-yQ-benzene hydrochloride Bromine derivative used: 2-bromo-5-methyl-pyridine Mass spectrum: MH+ 188(100)

g. 5-(2,4-Dihydroxy-phenyl)-nicotinonitril-Hydrochlorid Verwendetes Bromderivat: 3-Brom-5-methyl-pyridin Massenspektrum: MH+ 213(100) g. 5-(2,4-Dihydroxy-phenyl)-nicotinonitrile hydrochloride Bromine derivative used: 3-bromo-5-methyl-pyridine Mass spectrum: MH+ 213(100)

h. 1 ,S-Dihydroxy^^S-nitro-pyridin^-yQ-benzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-5-nitro-pyridin h. 1,S-dihydroxy^^S-nitro-pyridine^-yQ-benzene hydrochloride Bromine derivative used: 2-bromo-5-nitro-pyridine

Massenspektrum: MH+ 233 (100)Mass spectrum: MH+ 233 (100)

i. 1,3-Dihydroxy-4-(thiophen-3-yl-)benzol Verwendetes Bromderivat: 3-Brom-thiophen Massenspektrum: MH+ 193(100) i. 1,3-Dihydroxy-4-(thiophen-3-yl-)benzene Bromine derivative used: 3-bromo-thiophene Mass spectrum: MH+ 193(100)

1919

j. 4'-Methyl-biphenyl-2,4-diolj. 4'-Methyl-biphenyl-2,4-diol

Verwendetes Bromderivat: 4-Brom-toluol Massenspektrum: MH+ 201 (100)Bromine derivative used: 4-bromo-toluene Mass spectrum: MH+ 201 (100)

k. Biphenyl-2,4,4'-triolk. Biphenyl-2,4,4'-triol

Verwendetes Bromderivat: 4-Brom-phenol Massenspektrum: MH+ 203(100)Bromine derivative used: 4-bromo-phenol Mass spectrum: MH+ 203(100)

I. Biphenyl-2,4,3'-triolI. Biphenyl-2,4,3'-triol

Verwendetes Bromderivat: 3-Brom-phenol Massenspektrum: MH+ 203(100)Bromine derivative used: 3-bromo-phenol Mass spectrum: MH+ 203(100)

m. 4'-Fluoro-biphenyl-2,4-diolm. 4'-Fluoro-biphenyl-2,4-diol

Verwendetes Bromderivat: 4-Brom-fluorbenzol Massenspektrum: MH+ 205(100)Bromine derivative used: 4-bromo-fluorobenzene Mass spectrum: MH+ 205(100)

n. 1,3-Dihydroxy-4-(4-methyl-thiophen-3-yl)-benzol Verwendetes Bromderivat: 3-Brom-4-methyl-thiophen Massenspektrum: MH+ 207 (100) n. 1,3-Dihydroxy-4-(4-methyl-thiophen-3-yl)-benzene Bromine derivative used: 3-bromo-4-methyl-thiophene Mass spectrum: MH+ 207 (100)

o. 2',4'-Dihydroxy-biphenyl-4-carbonitril Verwendetes Bromderivat: 4-Brom-benzonitril Massenspektrum: MH+ 206(100) o. 2',4'-Dihydroxy-biphenyl-4-carbonitrile Bromine derivative used: 4-bromo-benzonitrile Mass spectrum: MH+ 206(100)

p. 1,3-Dihydroxy-4-(2-chlor-thiophen-3-yl)-benzol Verwendetes Bromderivat: 3-Brom-2-chlor-thiophen Massenspektrum: MH+ 227(100) p. 1,3-Dihydroxy-4-(2-chloro-thiophen-3-yl)-benzene Bromine derivative used: 3-bromo-2-chloro-thiophene Mass spectrum: MH+ 227(100)

q. 1 -(2',4'-Dihydroxy-biphenyl-3-yl)-ethanon Verwendetes Bromderivat: 3-Brom-acetophenon Massenspektrum: MH+ 229(100) q. 1 -(2',4'-Dihydroxy-biphenyl-3-yl)-ethanone Bromine derivative used: 3-bromo-acetophenone Mass spectrum: MH+ 229(100)

r. 1,3-Dihydroxy-4-(benzo[1,3]dioxol-5-yl)-benzol Verwendetes Bromderivat: 5-Brom-1,3-methylendioxy-benzol Massenspektrum: MH+ 231 (100) r. 1,3-Dihydroxy-4-(benzo[1,3]dioxol-5-yl)-benzene Bromine derivative used : 5-bromo-1,3-methylenedioxy-benzene Mass spectrum: MH+ 231 (100)

• ··

s. 4'-Nitro-biphenyl-2,4-diol Verwendetes Bromderivat: 4-Brom-nitrobenzol Massenspektrum: MH+ 232 (100) s. 4'-Nitro-biphenyl-2,4-diol Bromine derivative used: 4-bromo-nitrobenzene Mass spectrum: MH+ 232 (100)

t. 2'-Nitro-biphenyl-2,4-diol Verwendetes Bromderivat 2-Brom-nitrobenzol Massenspektrum: MH+ 232 (100) t. 2'-Nitro-biphenyl-2,4-diol Bromine derivative used 2-bromo-nitrobenzene Mass spectrum: MH+ 232 (100)

u. 4'-Trifluormethyl-biphenyl-2,4-diol Verwendetes Bromderivat: 4-Brom-trifluortoluol Massenspektrum: MH+ 255(100) u. 4'-Trifluoromethyl-biphenyl-2,4-diol Bromine derivative used: 4-bromo-trifluorotoluene Mass spectrum: MH+ 255(100)

v. 2',4'-Dimethyl-biphenyl-2,4-diol Verwendetes Bromderivat: 2-Brom-5-methyl-toluol Massenspektrum: MH+ 215(100) v. 2',4'-Dimethyl-biphenyl-2,4-diol Bromine derivative used: 2-bromo-5-methyl-toluene Mass spectrum: MH+ 215(100)

w. 3'-Methoxy-biphenyl-2,4-diol Verwendetes Bromderivat: 5-Brom-anisol Massenspektrum: MH+ 217(100) w. 3'-Methoxy-biphenyl-2,4-diol Bromine derivative used: 5-bromo-anisole Mass spectrum: MH+ 217(100)

x. 4'-Chlor-biphenyl-2,4-diol Verwendetes Bromderivat: 4-Brom-chlorbenzol Massenspektrum: MH+ 221 (100) x. 4'-Chloro-biphenyl-2,4-diol Bromine derivative used: 4-bromo-chlorobenzene Mass spectrum: MH+ 221 (100)

y. 4'-Methylsulfanyl-biphenyl-2,4-diol Verwendetes Bromderivat: 4-methylsulfanyl-brombenzol Massenspektrum: MH+ 233(100) y. 4'-Methylsulfanyl-biphenyl-2,4-diol Bromine derivative used: 4-methylsulfanyl-bromobenzene Mass spectrum: MH+ 233(100)

z. 1,3-Dihydroxy-4-(thiazol-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-thiazol Massenspektrum: MH+ 94(100) e.g. 1,3-dihydroxy-4-(thiazol-2-yl)-benzene Bromine derivative used: 2-bromo-thiazole Mass spectrum: MH+ 94(100)

Beispiel 2; Synthese von 1,3-Dihydroxy-benzolen (Allgemeine Synthesevorschrift) Example 2; Synthesis of 1,3-dihydroxybenzenes (general synthesis procedure)

A. Synthese von 2-[3-Brom-5-(tetrahydro-2H-pyran-2-yloxy)phenoxyltetrahydro-2H-pyranA. Synthesis of 2-[3-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxyltetrahydro-2H-pyran

Zu einer Lösung von 9,5 g (40 mmol) 5-Brom-1,3-dihydroxybenzol und 5 g (20 mmol) Toluol-4-sulfonsäure-Pyridinsalz in 50 ml Dichlormethan wird unter Argon 9 g (105 mmol) 3,4-Dihydro-2-H-pyran getropft. Das Reaktionsgemisch wird 18 Stunden lang gerührt. Anschließend wird die Reaktionsmischung in 100 ml Essigsäureethylester gegossen, die organische Phase mit verdünnter Natronlauge extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestilliert und der Rückstand an Kieselgel mit Petrolether/ Essigsäureethylester (7:1) gereinigt.9 g (105 mmol) of 3,4-dihydro-2-H-pyran are added dropwise to a solution of 9.5 g (40 mmol) of 5-bromo-1,3-dihydroxybenzene and 5 g (20 mmol) of toluene-4-sulfonic acid pyridine salt in 50 ml of dichloromethane under argon. The reaction mixture is stirred for 18 hours. The reaction mixture is then poured into 100 ml of ethyl acetate, the organic phase is extracted with dilute sodium hydroxide solution and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether/ethyl acetate (7:1).

Es werden 9,5 g (54% der Theorie) 2-[3-Brom-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran erhalten.9.5 g (54% of theory) of 2-[3-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran are obtained.

B. Synthese von 2- [3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran Eine Mischung von 5,5 g (154 mmol) 2-[3-Brom-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran aus Stufe A, 9 g (355 mmol) 4,4,5,5,4',^,ö'^'-Octamethyl-^^'lbi^i.S.^dioxaborinanyl], 1,5 g (2,2 mmol) Dichloro(1,1'-bis(diphenyl-phosphino)ferrocene)palladium (PdCI2(dppf)) und 6,2 g (63,2 mmol) Kaliumacetat wird unter Argon mit 210 ml entgastem Dioxan versetzt. Das Gemisch wird 24 Stunden lang bei 80 0C gerührt, sodann auf Wasser gegossen und mit Essigsäureethylester extrahiert. Die organische Phase wird anschließend mit einer gesättigten wässerigen Kochsalz-Lösung gewaschen, über Natriumsulfat B. Synthesis of 2-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]-tetrahydro-2H-pyran A mixture of 5.5 g (154 mmol) of 2-[3-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran from step A, 9 g (355 mmol) of 4,4,5,5,4',^,ö'^'-octamethyl-^^'lbi^iS^dioxaborinanyl], 1.5 g (2.2 mmol) of dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (PdCl 2 (dppf)) and 6.2 g (63.2 mmol) of potassium acetate is under argon with 210 ml of degassed dioxane. The mixture is stirred for 24 hours at 80 0 C, then poured into water and extracted with ethyl acetate. The organic phase is then washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate

getrocknet und nach Filtration eingeengt. Das erhaltene Rohprodukt wird an desaktiviertem Kieselgel mit einem Gradienten von Hexan (100%) über Hexan/Essigsäureethylester (9:1 bis 3:2) gereinigt.dried and concentrated after filtration. The crude product obtained is purified on deactivated silica gel with a gradient of hexane (100%) via hexane/ethyl acetate (9:1 to 3:2).

Es werden 4,70 g (77% der Theorie) 2- [3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]- tetrahydro-2H-pyran erhalten.4.70 g (77% of theory) of 2-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran are obtained.

C. Synthese der 1,3-Dihydroxy-benzole der Formel (I) 0,09 g (0,2 mmol) 2- [3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran aus Stufe B und 0,4 mmol des entsprechenden Bromderivates werden unter Argon in 10 ml 1,2-Dimethoxyethan gelöst. Anschließend werden 0,01 g (0,005 mmol) Tetrakis-(triphenylphosphin)-palladium und 0,26 ml 2N Kaliumcarbonat-Lösung zugegeben und die Reaktionsmischung auf 80 0C erwärmt. Nach Beendigung der Reaktion wird die Reaktionsmischung in 10 ml Essigsäureethylester gegossen, die organische Phase mit verdünnter Natronlauge extrahiert und sodann mit Magnesiumsulfat getrocknet. Das Lösungsmittel wird am Rotationsverdampfer abdestilliert und der Rückstand an Kieselgel mit Petrolether/Essigsäureethylester (9:1) gereinigt. C. Synthesis of the 1,3-dihydroxybenzenes of the formula (I) 0.09 g (0.2 mmol) of 2-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yl-oxy)phenoxy]-tetrahydro-2H-pyran from step B and 0.4 mmol of the corresponding bromine derivative are dissolved in 10 ml of 1,2-dimethoxyethane under argon. Then 0.01 g (0.005 mmol) of tetrakis(triphenylphosphine)palladium and 0.26 ml of 2N potassium carbonate solution are added and the reaction mixture is heated to 80 0 C. After the reaction has ended, the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with dilute sodium hydroxide solution and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether/ethyl acetate (9:1).

a. 1,3-Dihydroxy-5-(pyridin-2-yl)-benzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-pyridin
Massenspektrum: MH+ 188(100) a. 1,3-Dihydroxy-5-(pyridin-2-yl)-benzene hydrochloride Bromine derivative used : 2-bromo-pyridine
Mass spectrum: MH+ 188(100)

b. 1,3-Dihydroxy-5-(pyrimidin-2-yl)-benzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-pyrimidin Massenspektrum: MH+ 189(100) b. 1,3-Dihydroxy-5-(pyrimidin-2-yl)-benzene hydrochloride Bromine derivative used: 2-bromo-pyrimidine Mass spectrum: MH+ 189(100)

2323

c. 1,3-Dihydroxy-5-(thiophen-3-yl-)benzol Verwendetes Bromderivat: 3-Brom-thiophen Massenspektrum: MH+ 193(100) c. 1,3-Dihydroxy-5-(thiophen-3-yl-)benzene Bromine derivative used: 3-bromo-thiophene Mass spectrum: MH+ 193(100)

d. 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-thiophen Massenspektrum: MH+ 192(100) d. 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzene Bromine derivative used: 2-bromo-thiophene Mass spectrum: MH+ 192(100)

e. 1,3-Dihydroxy-5-(thiazol-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-thiazol Massenspektrum: MH+ 94(100) e. 1,3-Dihydroxy-5-(thiazol-2-yl)-benzene Bromine derivative used: 2-bromo-thiazole Mass spectrum: MH+ 94(100)

f. 4'-Methyl-biphenyl-2,4-diol Verwendetes Bromderivat: 4-Brom-toluol Massenspektrum: MH+ 201 (100) f. 4'-methyl-biphenyl-2,4-diol Bromine derivative used: 4-bromo-toluene Mass spectrum: MH+ 201 (100)

g. 1 ,S-Dihydroxy^^S-methyl-pyridin^-yiybenzol-Hydrochlorid Verwendetes Bromderivat: 2-Brom-5-methyl-pyridin Massenspektrum: MH+ 188(100) g. 1,S-Dihydroxy^^S-methyl-pyridine^-yiybenzene hydrochloride Bromine derivative used: 2-bromo-5-methyl-pyridine Mass spectrum: MH+ 188(100)

h. Biphenyl-3,5,4'-triol Verwendetes Bromderivat: 4-Brom-phenol Massenspektrum: MH+ 203(100) h. Biphenyl-3,5,4'-triol Bromine derivative used: 4-bromo-phenol Mass spectrum: MH+ 203(100)

i. Biphenyl-3,5,3'-triol Verwendetes Bromderivat: 3-Brom-phenol Massenspektrum: MH+ 203(100) i. Biphenyl-3,5,3'-triol Bromine derivative used: 3-bromo-phenol Mass spectrum: MH+ 203(100)

j. 4'-Fluoro-biphenyl-3,5-diol Verwendetes Bromderivat: 4-Brom-fluorbenzol Massenspektrum: MH+ 205(100) j. 4'-Fluoro-biphenyl-3,5-diol Bromine derivative used: 4-bromo-fluorobenzene Mass spectrum: MH+ 205(100)

k. 1,3-Dihydroxy-5-(3-methyl-thiophen-2-yl)-benzol Verwendetes Bromderivat: 2-Brom-3-methyl-thiophen Massenspektrum: MH+ 206(100) k. 1,3-Dihydroxy-5-(3-methyl-thiophen-2-yl)-benzene Bromine derivative used: 2-bromo-3-methyl-thiophene Mass spectrum: MH+ 206(100)

I. 1,3-Dihydroxy-5-(4-methyl-thiophen-3-yl)-benzolI. 1,3-Dihydroxy-5-(4-methyl-thiophen-3-yl)-benzene

Verwendetes Bromderivat: 3-Brom-4-methyl-thiophenBromine derivative used: 3-bromo-4-methyl-thiophene

Massenspektrum: MH+ 207(100)Mass spectrum: MH+ 207(100)

m. 3',5'-Dihydroxy-biphenyl-4-carbonitril Verwendetes Bromderivat: 4-Brom-benzonitril Massenspektrum: MH+ 206(100) m. 3',5'-Dihydroxy-biphenyl-4-carbonitrile Bromine derivative used: 4-bromo-benzonitrile Mass spectrum: MH+ 206(100)

n. 1,3-Dihydroxy-5-(2-chlor-thiophen-3-yl)-benzol Verwendetes Bromderivat: 3-Brom-2-chlor-thiophen n. 1,3-Dihydroxy-5-(2-chloro-thiophen-3-yl)-benzene Bromine derivative used: 3-bromo-2-chloro-thiophene

Massenspektrum: MH+ 227 (100)Mass spectrum: MH+ 227 (100)

o. 1 -(2',4'-Dihydroxy-biphenyl-3-yl)-ethanono. 1 -(2',4'-Dihydroxy-biphenyl-3-yl)-ethanone

Verwendetes Bromderivat: 3-Brom-acetophenonBromine derivative used: 3-bromo-acetophenone

Massenspektrum: MH+ 229(100)Mass spectrum: MH+ 229(100)

p. 1,3-Dihydroxy-4-(benzo[1,3]dioxol-5-yl)-benzol Verwendetes Bromderivat: 5-Brom-1,3-methylendioxy-benzol p. 1,3-Dihydroxy-4-(benzo[1,3]dioxol-5-yl)-benzene Bromine derivative used : 5-bromo-1,3-methylenedioxy-benzene

Massenspektrum: MH+ 231 (100)Mass spectrum: MH+ 231 (100)

q. 4'-Nitro-biphenyl-2,4-diolq. 4'-Nitro-biphenyl-2,4-diol

Verwendetes Bromderivat: 4-Brom-nitrobenzol Massenspektrum: MH+ 232(100)Bromine derivative used: 4-bromo-nitrobenzene Mass spectrum: MH+ 232(100)

r. 2'-Nitro-biphenyl-2,4-diolr. 2'-Nitro-biphenyl-2,4-diol

Verwendetes Bromderivat: 2-Brom-nitrobenzol Massenspektrum: MH+ 232(100)Bromine derivative used: 2-bromo-nitrobenzene Mass spectrum: MH+ 232(100)

s. 1,3-Dihydroxy-5-(5-nitro-thiophen-2-yl)-benzolsee 1,3-Dihydroxy-5-(5-nitro-thiophen-2-yl)-benzene

Verwendetes Bromderivat: 2-Brom-5-nitro-thiophenBromine derivative used: 2-bromo-5-nitro-thiophene

Massenspektrum: MH+ 237 (100)Mass spectrum: MH+ 237 (100)

t. 4'-Trifluormethyl-biphenyl-3,5-diol Verwendetes Bromderivat: 4-Brom-trifluortoluol Massenspektrum: MH+ 255 (100) t. 4'-Trifluoromethyl-biphenyl-3,5-diol Bromine derivative used: 4-bromo-trifluorotoluene Mass spectrum: MH+ 255 (100)

• ··

2525

u. 2',4'-Dimethyl-biphenyl-3,5-diol Verwendetes Bromderivat: 2-Brom-5-methyl-toluol Massenspektrum: MH+ 215(100) and 2',4'-dimethyl-biphenyl-3,5-diol Bromine derivative used: 2-bromo-5-methyl-toluene Mass spectrum: MH+ 215(100)

v. 3'-Methoxy-biphenyl-2,4-diolv. 3'-Methoxy-biphenyl-2,4-diol

Verwendetes Bromderivat: 5-Brom-anisol Massenspektrum: MH+ 217(100)Bromine derivative used: 5-bromo-anisole Mass spectrum: MH+ 217(100)

w. 4'-Chlor-biphenyl-2,4-diolw. 4'-chloro-biphenyl-2,4-diol

Verwendetes Bromderivat: 4-Brom-chlorbenzol Massenspektrum: MH+ 221 (100) x.4'-Methylsulfanyl-biphenyl-2,4-diol Verwendetes Bromderivat: 4-methylsulfanyl-brombenzol Massenspektrum: MH+ 233(100)Bromine derivative used: 4-bromo-chlorobenzene Mass spectrum: MH+ 221 (100) x.4'-methylsulfanyl-biphenyl-2,4-diol Bromine derivative used : 4-methylsulfanyl-bromobenzene Mass spectrum: MH+ 233(100)

y. 2'-Chlor-4'-nitro-biphenyl-3,5-diol Verwendetes Bromderivat: 4-Brom-3-chlor-nitrobenzol Massenspektrum: MH+ 266(100) y. 2'-Chloro-4'-nitro-biphenyl-3,5-diol Bromine derivative used: 4-bromo-3-chloro-nitrobenzene Mass spectrum: MH+ 266(100)

Beispiele 3 bis 53: Examples 3 to 53: HaarfärbemittelHair dye

Es werden Haarfärbelösungen der folgenden Zusammensetzung hergestellt:Hair dye solutions of the following composition are produced:

1,25 mmol1.25 mmol

1,25 mmol1.25 mmol

1,0g1.0g

1,0g1.0g

1,0 g1.0g

0,3 g0.3g

ad 100,0 gto 100.0 g

Kupplersubstanz der Formel (I) gemäß TabelleCoupler substance of formula (I) according to Table

Entwicklersubstanz gemäß TabelleDeveloper substance according to table

Kaliumoleat (8prozentige wässrige Lösung)Potassium oleate (8% aqueous solution)

Ammoniak (22prozentige wässrige Lösung)Ammonia (22% aqueous solution)

EthanolEthanol

AscorbinsäureAscorbic acid

WasserWater

50 g der vorstehenden Färbelösung werden unmittelbar vor der Anwendung mit 50 g einer 6prozentigen wässrigen Wasserstoffperoxidlösung vermischt. Anschließend wird das Gemisch auf gebleichte Haare aufgetragen. Nach einer Einwirkungszeit von 30 Minuten bei 40 0C wird das Haar mit Wasser gespült, mit einem handelsüblichen Shampoo gewaschen und getrocknet. Die resultierenden Färbungen sind in Tabelle 1 zusammengefaßt.Immediately before use, 50 g of the above dye solution are mixed with 50 g of a 6% aqueous hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 0 C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 1.

Tabelle 1Table 1 ■■ KupplersubstanzCoupler substance I.I. II.II. 2,5-2.5- III.III. IV.IV. KupplerMatchmaker 1,4-Di-1,4-Di- Diamino-Diamino- 2,5-Diamino-2,5-Diamino- 4,5-Diamino-1-4,5-Diamino-1- BeispielExample substanzsubstance amino-amino toluol-toluene- phenyl-phenyl (2-hydroxy-(2-hydroxy- Nr.No. der Formelthe formula benzolbenzene sulfatsulfate ethanol-ethanol ethyl)-pyrazol-ethyl)-pyrazole- (I)(I) dunkeldark sulfatsulfate sulfatsulfate dunkeldark braunbrown dunkelbraundark brown purpurpurple braunbrown mittelmedium gemäßaccording to braunbrown blondblond mittelblondmedium blonde purpurpurple 3.3. Beispiel 1a Example 1a mittelmedium gemäßaccording to braunbrown blondblond mittelblondmedium blonde purpurpurple 4.4. Beispiel 1b Example 1b hellblondlight blonde gemäßaccording to mittelmedium hellblondlight blonde hellpurpurlight purple 5.5. Beispiel 1cExample 1c blondblond hellblondlight blonde gemäßaccording to mittelmedium hellblondlight blonde hellpurpurlight purple 6.6. Beispiel 1d Example 1d blondblond gemäßaccording to 7.7. Beispiel 1e Example 1e

8.8th. gemäß
Beispiel 1faccording to
Example 1f mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 9.9. gemäß
Beispiel 1gaccording to
Example 1g mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 10.10. gemäß
Beispiel 1haccording to
Example 1h mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 11.11. gemäß
Beispiel 1iaccording to
Example 1i mittel
blondmedium
blond blondblond blondblond hellpurpurlight purple 12.12. gemäß
Beispiel 1jaccording to
Example 1j mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 13.13. gemäß
Beispiel 1 kaccording to
Example 1 k mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 14.14. gemäß
Beispiel 11according to
Example 11 braun-
purpurbrown-
purple hellbraun-
purpurlight brown-
purple hellbraun-
purpurlight brown-
purple purpurpurple 15.15. gemäß
Beispiel 1maccording to
Example 1m mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 16.16. gemäß
Beispiel 1naccording to
Example 1n mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 17.17. gemäß
Beispiel 1oaccording to
Example 1o mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 18.18. gemäß
Beispiel 1paccording to
Example 1p mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 19.19. gemäß
Beispiel 1qaccording to
Example 1q mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 20.20. gemäß
Beispiel 1 raccording to
Example 1 r mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple

21.21. gemäß
Beispiel 1saccording to
Example 1s mittel
blondmedium
blond blondblond IblondIblond hellpurpurlight purple 22.22. gemäß
Beispiel 1taccording to
Example 1t mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 23.23. gemäß
Beispiel 1uaccording to
Example 1u mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 24.24. gemäß
Beispiel 1vaccording to
Example 1v mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 25.25. gemäß
Beispiel 1waccording to
Example 1w mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 26.26. gemäß
Beispiel 1xaccording to
Example 1x mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 27.27. gemäß
Beispiel 1yaccording to
Example 1y mittel
blondmedium
blond hellblondlight blonde hellblondlight blonde hellpurpurlight purple 28.28. gemäß
Beispiel 1zaccording to
Example 1z grauGray hellblauLight Blue hellblauLight Blue violettviolet 29.29. gemäß
Beispiel 2aaccording to
Example 2a blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 30.30. gemäß
Beispiel 2baccording to
Example 2b blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 31.31. gemäß
Beispiel 2caccording to
Example 2c blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 32.32. gemäß
Beispiel 2daccording to
Example 2d blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 33.33. gemäß
Beispiel 2eaccording to
Example 2e blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange

34.34. gemäß
Beispiel 2faccording to
Example 2f blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 35.35. gemäß
Beispiel 2gaccording to
Example 2g blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 36.36. gemäß
Beispiel 2haccording to
Example 2h blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 37.37. gemäß
Beispiel 2iaccording to
Example 2i blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 38.38. gemäß
Beispiel 2jaccording to
Example 2j blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 39.39. gemäß
Beispiel 2kaccording to
Example 2k blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 40.40. gemäß
Beispiel 2!according to
Example 2! blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 41.41. gemäß
Beispiel 2maccording to
Example 2m blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 42.42. gemäß
Beispiel 2naccording to
Example 2n blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 43.43. gemäß
Beispiel 2oaccording to
Example 2o blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 44.44. gemäß
Beispiel 2paccording to
Example 2p blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 45.45. gemäß
Beispiel 2qaccording to
Example 2q blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 46.46. gemäß
Beispiel 2raccording to
Example 2r blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange

47.47. gemäß
Beispiel 2saccording to
Example 2s blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 48.48. gemäß
Beispiel 2taccording to
Example 2t blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 49.49. gemäß
Beispiel 2uaccording to
Example 2u blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 50.50. gemäß
Beispiel 2vaccording to
Example 2v blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 51.51. gemäß
Beispiel 2waccording to
Example 2w blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 52.52. gemäß
Beispiel 2xaccording to
Example 2x blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange 53.53. gemäß
Beispiel 2yaccording to
Example 2y blondblond hellblondlight blonde hellblondlight blonde hellorangelight orange

Beispiel 54 bis 63: Example 54 to 63: HaarfärbemittelHair dye

Es werden Haarfärbelösungen der folgenden Zusammensetzung hergestellt:Hair dye solutions of the following composition are produced:

Xg 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzolXg 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzene

(Kupplersubstanz K1) (Coupling substance K1)

U g Entwicklersubstanz E8 bis E15 gemäß Tabelle 2U g developer substance E8 to E15 according to Table 2

Y g Kupplersubstanz K11 bis K33 gemäß Tabelle 4Y g coupler substance K1 1 to K33 according to Table 4

Z g direktziehender Farbstoff D2 bis D3 gemäß TabelleZ g direct dye D2 to D3 according to table

10,0 g Kaliumoleat (8prozentige wässrige Lösung)10.0 g potassium oleate (8% aqueous solution)

10,0 g Ammoniak (22prozentige wässrige Lösung)10.0 g ammonia (22% aqueous solution)

10,0 g Ethanol10.0 g ethanol

0,3 g Ascorbinsäure0.3 g ascorbic acid

ad 100,0 g Wasserad 100.0 g water

30 g der vorstehenden Färbelösung werden unmittelbar vor der Anwendung mit 30 g einer 6prozentigen wässrigen Wasserstoffperoxidlösung vermischt. Anschließend wird das Gemisch auf gebleichte Haare aufgetragen. Nach einer Einwirkungszeit von 30 Minuten bei 40 0C wird das Haar mit Wasser gespült, mit einem handelsüblichen Shampoo gewaschen und getrocknet. Die Färbeergebnisse sind in Tabelle 5 zusammengefasst.Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% aqueous hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 0 C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The dyeing results are summarized in Table 5.

Beispiel 64 bis 69: Example 64 to 69: HaarfärbemittelHair dye

Es werden cremeförmige Farbträgermassen der folgenden Zusammensetzung hergestellt:Cream-like color carrier masses of the following composition are produced:

Xg 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzolXg 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzene

(Kupplersubstanz K1) (Coupling substance K1)

U g Entwicklersubstanz E8 bis E15 gemäß Tabelle 2 Y g Kupplersubstanz K11 bis K33 gemäss Tabelle 4 Z g direktziehender Farbstoff D2 bis D3 gemäss Tabelle 3 15,0 g Cetylalkohol
0,3 g Ascorbinsäure
3,5 g Natriumlaurylalkoholdiglycolethersulfat, 28prozentigeU g developer substance E8 to E15 according to Table 2 Y g coupler substance K1 1 to K33 according to Table 4 Z g direct dye D2 to D3 according to Table 3 15.0 g cetyl alcohol
0.3 g ascorbic acid
3.5 g sodium lauryl alcohol diglycol ether sulfate, 28 percent

wässrige Lösungaqueous solution

3,0 g Ammoniak, 22prozentige wässrige Lösung 0,3 g Natriumsulfit, wasserfrei
ad 100,0 g Wasser3.0 g ammonia, 22% aqueous solution 0.3 g sodium sulphite, anhydrous
ad 100.0 g water

30 g der vorstehenden Färbecreme werden unmittelbar vor der Anwendung mit 30 g einer 6prozentigen Wasserstoffperoxidlösung vermischt. Anschließend wird das Gemisch auf das Haar aufgetragen. Nach einer Einwirkzeit von 30 Minuten bei 40 0C wird das Haar mit Wasser gespült, mit einem handelsüblichen Shampoo gewaschen und getrocknet. Die Färbeergebnisse sind in Tabelle 6 zusammengefasst.Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to the hair. After a contact time of 30 minutes at 40 0 C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The coloring results are summarized in Table 6.

TabelleTable 2:2: EntwicklersubstanzenDeveloper substances E8E8 1,4-Diaminobenzol 1,4 -Diaminobenzene E9E9 2,5-Diamino-phenylethanol-sulfat2,5-diamino-phenylethanol sulfate E10E10 3-Methyl-4-amino-phenol3-methyl-4-aminophenol E11E11 4-Amino-2-aminomethyl-phenol-dihydrochlorid4-Amino-2-aminomethylphenol dihydrochloride E12E12 4-Amino-phenol4-Aminophenol E13E13 N,N-Bis(2'-hydroxyethyl)-p-phenylendiamin-sulfatN,N-Bis(2'-hydroxyethyl)-p-phenylenediamine sulfate E14E14 4,5-Diamino-1-(2'-hydroxyethyl)-pyrazol-sulfat4,5-Diamino-1-(2'-hydroxyethyl)-pyrazole sulfate E15E15 2,5-Diaminotoluol-sulfat2,5-Diaminotoluene sulfate

TabelleTable 3:3: Direktziehende FarbstoffeDirect dyes D2D2 6-Chlor-2-ethylamino-4-nitro-phenol6-Chloro-2-ethylamino-4-nitro-phenol D3D3 2-Amino-6-chlor-4-nitro-phenol2-Amino-6-chloro-4-nitrophenol

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TabelleTable 4:4: KupplersubstanzenCouplers K1K1 1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzol1,3-Dihydroxy-5-(thiophenyl-2-yl)-benzene K12K12 2-Amino-4-(2'-hydroxyethyl)amino-anisol-sulfat2-Amino-4-(2'-hydroxyethyl)aminoanisole sulfate K13K13 1,3-Diamino-4-(2'-hydroxyethoxy)benzol-sulfat1,3-Diamino-4-(2'-hydroxyethoxy)benzene sulfate K18K18 N-(3-Dimethylamino)phenylharnstoffN-(3-Dimethylamino)phenylurea K19K19 1,3-Bis(2,4-Diaminophenoxy)propan-tetrahydrochlorid1,3-Bis(2,4-diaminophenoxy)propane tetrahydrochloride K21K21 3-Amino-phenol3-Aminophenol K22K22 5-Amino-2-methyl-phenol5-Amino-2-methylphenol K23K23 S-Amino^-chlor-e-methyl-phenolS-Amino^-chloro-e-methyl-phenol K24K24 5-Amino-4-fluor-2-methyl-phenol-sulfat5-Amino-4-fluoro-2-methylphenol sulfate K25K25 1-Naphthol1-Naphthol K26K26 1 -Acetoxy-2-methyl-naphthalin1 -Acetoxy-2-methyl-naphthalene K31K31 1,3-Dihydroxy-benzol1,3-Dihydroxybenzene K32K32 2-Methyl-1,3-dihydroxy-benzol2-methyl-1,3-dihydroxybenzene K33K33 1 -Chlor-2,4-dihydroxy-benzol1-Chloro-2,4-dihydroxybenzene

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3434

Tabelle 5: Haarfärbemittel Table 5: Hair dyes

Beispiel Nr.Example No. 5454 5555 5656 5757 5858 5959 (Farbstoffmenge in Gramm)(Amount of dye in grams) 0,100.10 0,100.10 0,130.13 0,150.15 0,200.20 0,100.10 FarbstoffeDyes K1K1 0,300.30 0,250.25 0,300.30 E8E8 0,250.25 0,300.30 0,250.25 E9E9 E15E15 0,160.16 0,160.16 K12K12 0,050.05 0,150.15 0,150.15 K12K12 0,100.10 K13K13 0,150.15 K18K18 0,050.05 0,100.10 0,150.15 0,150.15 0,150.15 K19K19 K13K13 0,050.05 0,050.05 K31K31 0,100.10 K32K32 0,050.05 K33K33 0,050.05 K21K21 0,050.05 0,100.10 0,100.10 0,100.10 K22K22 blondblond blondblond blondblond blondblond blondblond blondblond K23K23 FärbeergebnisDyeing result

3535

Tabelle 5 (Fortsetzung)Table 5 (continued)

Beispiel Nr.Example No. 6060 6161 6262 6363 0,200.20 0,200.20 0,200.20 0,200.20 FarbstoffeDyes (Farbstoffmenge in Gramm)(Amount of dye in grams) K1K1 0,150.15 0,200.20 0,200.20 0,180.18 E8E8 0,300.30 E15E15 0,300.30 E10E10 0,300.30 E11E11 0,300.30 E12E12 E14E14 0,300.30 0,300.30 0,300.30 0,350.35 K25K25 rotbraunreddish brown rotbraunreddish brown rotbraunreddish brown rotbraunreddish brown K26K26 FärbeergebnisDyeing result

3636

Tabelle 6: Haarfärbemittel Table 6: Hair dyes

Beispiel Nr.Example No. 6464 6565 6666 6767 6868 6969 (Farbstoffmenge in Gramm)(Amount of dye in grams) 1,101.10 1,101.10 0,600.60 0,200.20 0,400.40 0,400.40 FarbstoffeDyes K1K1 1,501.50 1,601.60 0,700.70 E8E8 1,801.80 0,700.70 0,700.70 E13E13 E15E15 0,600.60 0,700.70 1,501.50 1,251.25 0,180.18 0,180.18 0,180.18 K12K12 0,600.60 0,200.20 K13K13 K31K31 0,100.10 0,100.10 0,100.10 D3D3 0,050.05 0,100.10 0,100.10 0,100.10 D2D2 schwarzblack schwarzblack schwarzblack braunbrown braunbrown braunbrown K23K23 FärbeergebnisDyeing result

Alle in der vorliegenden Anmeldung enthaltenen Prozentangaben stellen soweit nicht anders angegeben Gewichtsprozente dar.All percentages contained in this application are by weight unless otherwise stated.

Claims (11)

1. Mittel zur Färbung von Keratinfasern auf der Basis einer Entwicklersubstanz-Kupplersubstanz-Kombination, dadurch gekennzeichnet, dass es mindestens ein 1,3-Dihydroxybenzol-Derivat der Formel (I) oder dessen physiologisch verträgliches, wasserlösliches Salz enthält,


worin
R1 gleich einer substituierten Pyridylgruppe, einer Pyrimidylgruppe, einem Rest der Formel,


oder einem Rest der Formel


wobei R2, R3, R4, R5 und R6 unabhängig voneinander Wasserstoff, ein Halogenatom (F, Cl, Br, J), eine Cyanogruppe, eine Hydroxygruppe, eine C1-C4-Alkoxygruppe, eine C1-C4-Hydroxyalkoxygruppe, eine C1-C6 -Alkylgruppe, eine C1-C4-Alkylthioethergruppe, eine Mercaptogruppe, eine Nitrogruppe, eine Aminogruppe, eine C1-C4-Alkylaminogruppe, eine Hydroxy(C1-C4)alkylaminogruppe, eine Di(C1-C4)alkylaminogruppe, eine Di(hydroxy(C1-C4)alkyl)aminogruppe, eine (Dihydroxy(C3-C4)alkyl)- aminogruppe, eine (Hydroxy(C1-C4)alkyl)-C1-C4 alkylaminogruppe, eine Trifluormethangruppe eine -C(O)H-Gruppe, eine -C(O)CH3-Gruppe, eine -C(O)CF3-Gruppe, eine -Si(CH3)3-Gruppe, eine C1-C4-Hydroxyalkylgruppe oder eine C2-C4-Dihydroxyalkylgruppe darstellen, oder zwei nebeneinanderliegende Reste R2 bis R6 eine -O-CH2-O-Brücke bilden;
X1 gleich Schwefel, Stickstoff, Sauerstoff, C-R9 oder N-R8 ist;
X2 gleich Schwefel, Stickstoff, Sauerstoff, C-R10 oder N-R8 ist
X3 gleich Schwefel, Stickstoff, Sauerstoff, C-R11 oder N-R8 ist;
R7, R9, R10 und R11 unabhängig voneinander gleich Wasserstoff, einem Halogenatom (F, C1, Br, J), einer Cyanogruppe, einer C1-C4 Alkoxygruppe, einer C1-C6-Alkylgruppe, einer C1-C4-Alkylthioethergruppe, einer Mercaptogruppe, einer Nitrogruppe, einer Aminogruppe, einer C1-C4-Alkylaminogruppe, einer Di(C1-C4)-alkylaminogruppe, einer Di(C1-C4-hydroxyalkyl)aminogruppe, einer C1-C4 -Hydroxyalkylaminogruppe, einer Trifluormethangruppe einer -C(O)CH3-Gruppe, einer -C(O)CF3-Gruppe, einer -Si(CH3)3-Gruppe, einer C1-C4 -Hydroxyalkylgruppe oder einer C3-C4-Dihydroxyalkylgruppe sind; und
R8 gleich Wasserstoff, einer C1-C6-Alkylgruppe, einer C2-C4 -Hydroxyalkylgruppe, einer Phenylgruppe oder einer Acetylgruppe ist;
unter der Bedingung, dass mindestens einer und maximal zwei der Reste X1 bis X3 gleich C-R9, C-R10 oder C-R11 sind und maximal einer der Reste X1 bis X3 gleich Schwefel, Sauerstoff oder N-R8 ist. 1. Agent for coloring keratin fibers based on a developer substance-coupler substance combination, characterized in that it contains at least one 1,3-dihydroxybenzene derivative of the formula (I) or its physiologically acceptable, water-soluble salt,


wherein
R1 is a substituted pyridyl group, a pyrimidyl group, a radical of the formula,


or a remainder of the formula


where R2, R3, R4, R5 and R6 independently of one another represent hydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxy group, a C 1 -C 4 alkoxy group, a C 1 -C 4 hydroxyalkoxy group, a C 1 -C 6 alkyl group, a C 1 -C 4 alkylthioether group, a mercapto group, a nitro group, an amino group, a C 1 -C 4 alkylamino group, a hydroxy(C 1 -C 4 )alkylamino group, a di(C 1 -C 4 )alkylamino group, a di(hydroxy(C 1 -C 4 )alkyl)amino group, a (dihydroxy(C 3 -C 4 )alkyl)amino group, a (hydroxy(C 1 -C 4 )alkyl)-C 1 -C 4 alkylamino group, a trifluoromethane group, a -C(O)H group, a -C(O)CH 3 group, a -C(O)CF 3 group, a -Si(CH 3 ) 3 group, a C 1 -C 4 hydroxyalkyl group or a C 2 -C 4 dihydroxyalkyl group, or two adjacent radicals R2 to R6 form an -O-CH 2 -O- bridge;
X1 is sulfur, nitrogen, oxygen, C-R9 or N-R8;
X2 is sulphur, nitrogen, oxygen, C-R10 or N-R8
X3 is sulfur, nitrogen, oxygen, C-R11 or N-R8;
R7, R9, R10 and R11 are independently hydrogen, a halogen atom (F, C1, Br, I), a cyano group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, a C 1 -C 4 alkylthioether group, a mercapto group, a nitro group, an amino group, a C 1 -C 4 alkylamino group, a di(C 1 -C 4 )alkylamino group, a di(C 1 -C 4 hydroxyalkyl)amino group, a C 1 -C 4 hydroxyalkylamino group, a trifluoromethane group, a -C(O)CH 3 group, a -C(O)CF 3 group, a -Si(CH 3 ) 3 group, a C 1 -C 4 hydroxyalkyl group or a C 3 -C 4 dihydroxyalkyl group; and
R8 is hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 4 hydroxyalkyl group, a phenyl group or an acetyl group;
provided that at least one and a maximum of two of the radicals X1 to X3 are C-R9, C-R10 or C-R11 and a maximum of one of the radicals X1 to X3 is sulfur, oxygen or N-R8. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, dass es ausgewählt ist aus Verbindungen der Formel (I) bei denen gilt (i) X2 ist gleich C-R10 und X1 ist gleich Schwefel und X3 ist gleich C-R11 beziehungsweise X1 ist gleich C-R9 und X3 ist gleich Schwefel; oder (ii) X2 ist gleich C-R10 und X1 ist gleich Schwefel und X3 ist gleich C-R11 beziehungsweise X1 ist gleich C-R9 und X3 ist gleich Schwefel und mindestens einer der Reste R9 bis R11 ist gleich Wasserstoff. 2. Agent according to claim 1, characterized in that it is selected from compounds of formula (I) in which (i) X2 is C-R10 and X1 is sulfur and X3 is C-R11 or X1 is C-R9 and X3 is sulfur; or (ii) X2 is C-R10 and X1 is sulfur and X3 is C-R11 or X1 is C-R9 and X3 is sulfur and at least one of the radicals R9 to R11 is hydrogen. 3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es ausgewählt ist aus der Gruppe bestehend aus 1,3-Dihydroxy-4-(thiophen- 2-yl)-benzol, 1,3-Dihydroxy-4-(5-nitro-thiophen-2-yl)-benzol, 1,3-Dihydroxy-4-(3-methyl-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(5- chlor-thiophen-2-yl)-benzol, 1,3-Dihydroxy-5-(3-methyl-thiophen-2-yl)- benzol, 1,3-Dihydroxy-4-(thiophen-3-yl)-benzol und 1,3-Dihydroxy-5- (thiophen-3-yl)-benzol sowie deren physiologisch verträglichen Salze. 3. Agent according to claim 1 or 2, characterized in that it is selected from the group consisting of 1,3-dihydroxy-4-(thiophen-2-yl)-benzene, 1,3-dihydroxy-4-(5-nitro-thiophen-2-yl)-benzene, 1,3-dihydroxy-4-(3-methyl-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(5-chloro-thiophen-2-yl)-benzene, 1,3-dihydroxy-5-(3-methyl-thiophen-2-yl)-benzene, 1,3-dihydroxy-4-(thiophen-3-yl)-benzene and 1,3-dihydroxy-5-(thiophen-3-yl)-benzene and their physiologically acceptable salts. 4. Mittel nach einem der Ansprüche 1 bis 3 dadurch gekennzeichnet, dass das 1,3-Dihydroxybenzol der Formel (I) in einer Menge von 0,005 bis 20 Gewichtsprozent enthalten ist. 4. Agent according to one of claims 1 to 3, characterized in that the 1,3-dihydroxybenzene of the formula (I) is contained in an amount of 0.005 to 20 percent by weight. 5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Entwicklersubstanz ausgewählt ist aus der Gruppe bestehend aus 1,4-Diaminobenzol, 1,4-Diamino-2-methyl-benzol, 1,4-Diamino-2,6- dimethyl-benzol, 1,4-Diamino-3,5-diethyl-benzol, 1,4-Diamino-2,5- dimethyl-benzol, 1,4-Diamino-2,3-dimethyl-benzol, 2-Chlor-1,4- diaminobenzol, 1,4-Diamino-2-(thiophen-2-yl)benzol, 1,4-Diamino-2- (thiophen-3-yl)benzol, 1,4-Diamino-2-(pyridin-3-yl)benzol, 2,5-Diaminobiphenyl, 1,4-Diamino-2-methoxymethyl-benzol, 1,4-Diamino-2-aminomethyl-benzol, 1,4-Diamino-2-hydroxymethyl-benzol, 1,4-Diamino-2-(2- hydroxyethoxy)-benzol, 2-(2-(Acetylamino)ethoxy)-1,4-diamino-benzol, 4-Phenylamino-anilin, 4-Dimethylamino-anilin, 4-Diethylamino-anilin, 4-Dipropylamino-anilin, 4-[Ethyl(2-hydroxyethyl)amino]-anilin, 4-[Di(2- hydroxyethyl)amino]-anilin, 4-[Di(2-hydroxyethyl)amino]-2-methyl-anilin, 4-[(2-Methoxyethyl)amino]-anilin, 4-[(3-Hydroxypropyl)amino]-anilin, 4-[(2,3-Dihydroxypropyl)amino]-anilin, 1,4-Diamino-2-(1-hydroxyethyl)- benzol, 1,4-Diamino-2-(2-hydroxyethyl)-benzol, 1,4-Diamino-2-(1- methylethyl)-benzol, 1,3-Bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2- propanol, 1,4-Bis[(4-Aminophenyl)amino]-butan, 1,8-Bis(2,5- diaminophenoxy)-3,6-dioxaoctan, 4-Amino-phenol, 4-Amino-3-methylphenol, 4-Amino-3-(hydroxymethyl)-phenol, 4-Amino-3-fluor-phenol, 4-Methylamino-phenol, 4-Amino-2-(aminomethyl)-phenol, 4-Amino-2- (hydroxymethyl)-phenol, 4-Amino-2-fluor-phenol, 4-Amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-Amino-2-methyl-phenol, 4-Amino-2- (methoxymethyl)-phenol, 4-Amino-2-(2-hydroxyethyl)-phenol, 5-Aminosalicylsäure, 2,5-Diamino-pyridin, 2,4,5,6-Tetraamino-pyrlmidin, 2,5,6-Triamino-4-(1 H)-pyrimidon, 4,5-Diamino-1-(2-hydroxyethyl)-1 Hpyrazol, 4,5-Diamino-1-(1-methylethyl)-1 H-pyrazol, 4,5-Diamino-1-[(4- methylphenyl)methyl]-1 H-pyrazol, 1-[(4-Chlorphenyl)methylj-4, 5-diamino- 1 H-pyrazol, 4,5-Diamino-1-methyl-1 H-pyrazol, 2-Amino-phenol, 2-Amino- 6-methyl-phenol, 2-Amino-5-methyl-phenol und 1,2,4-Trihydroxy-benzol. 5. Agent according to one of claims 1 to 4, characterized in that the developer substance is selected from the group consisting of 1,4-diaminobenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene, 1,4-diamino-2-(thiophen-3-yl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethylbenzene, 1,4-Diamino-2-aminomethyl-benzol, 1,4-Diamino-2-hydroxymethyl-benzol, 1,4-Diamino-2-(2- hydroxyethoxy)-benzol, 2-(2-(Acetylamino)ethoxy)-1,4-diamino-benzol, 4-Phenylamino-anilin, 4-Dimethylamino-anilin, 4-Diethylamino-anilin, 4-Dipropylamino-anilin, 4-[Ethyl(2-hydroxyethyl)amino]-anilin, 4-[Di(2- hydroxyethyl)amino]-anilin, 4-[Di(2-hydroxyethyl)amino]-2-methyl-anilin, 4-[(2-Methoxyethyl)amino]-anilin, 4-[(3-Hydroxypropyl)amino]-anilin, 4-[(2,3-Dihydroxypropyl)amino]-anilin, 1,4-Diamino-2-(1-hydroxyethyl)- benzol, 1,4-Diamino-2-(2-hydroxyethyl)-benzol, 1,4-Diamino-2-(1- methylethyl)-benzol, 1,3-Bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2- propanol, 1,4-Bis[(4-Aminophenyl)amino]-butan, 1,8-Bis(2,5- diaminophenoxy)-3,6-dioxaoctan, 4-Amino-phenol, 4-Amino-3-methylphenol, 4-Amino-3-(hydroxymethyl)-phenol, 4-Amino-3-fluor-phenol, 4-Methylamino-phenol, 4-Amino-2-(aminomethyl)-phenol, 4-Amino-2- (hydroxymethyl)-phenol, 4-Amino-2-fluor-phenol, 4-Amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-Amino-2-methyl-phenol, 4-Amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 5-aminosalicylic acid, 2,5-diaminopyridine, 2,4,5,6-tetraaminopyrlmidine, 2,5,6-triamino-4-(1H)-pyrimidone, 4,5-diamino-1-(2-hydroxyethyl)-1Hpyr azole, 4,5-diamino-1-(1-methylethyl)-1 H-pyrazole, 4,5-diamino-1-[(4-methylphenyl)methyl]-1 H-pyrazole, 1-[(4-chlorophenyl)methylj-4, 5-diamino-1 H-pyrazole, 4,5-diamino-1-methyl-1 H-pyrazole, 2-amino-phenol, 2-amino-6- methyl-phenol, 2-amino-5-methyl-phenol and 1,2,4-trihydroxybenzene. 6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es zusätzlich zu den Verbindungen der Formel (I) noch weitere bekannte Kupplersubstanzen aus der Gruppe bestehend aus N-(3-Dimethylamino-phenyl)-harnstoff, 2,6-Diamino-pyridin, 2-Amino-4-[(2- hydroxyethyl)amino]-anisol, 2,4-Diamino-1-fluor-5-methyl-benzol, 2,4-Diamino-1-methoxy-5-methyl-benzol, 2,4-Diamino-1-ethoxy-5-methylbenzol, 2,4-Diamino-1-(2-hydroxyethoxy)-5-methyl-benzol, 2,4-Di[(2- hydroxyethyl)amino]-1,5-dimethoxy-benzol, 2,3-Diamino-6-methoxypyridin, 3-Amino-6-methoxy-2-(methylamino)-pyridin, 2, 6-Diamino-3,5- dimethoxy-pyridin, 3, 5-Diamino-2,6-dimethoxy-pyridin, 1,3-Diaminobenzol, 2,4-Diamino-1-(2-hydroxyethoxy)-benzol, 1,3-Diamino-4-(2,3- dihydroxypropoxy)-benzol, 1,3-Diamino-4-(3-hydroxypropoxy)-benzol, 1,3-Diamino-4-(2-methoxyethoxy)-benzol, 2,4-Diamino-1,5-di(2- hydroxyethoxy)-benzol, 1-(2-Aminoethoxy)-2,4-diamino-benzol, 2-Amino- 1-(2-hydroxyethoxy)-4-methylamino-benzol, 2,4-Diaminophenoxyessigsäure, 3-[Di(2-hydroxyethyl)amino]-anilin, 4-Amino-2-di[(2- hydroxyethyl)amino]-1-ethoxy-benzol, 5-Methyl-2-(1-methylethyl)-phenol, 3-[(2-Hydroxyethyl)amino]-anilin, 3-[(2-Aminoethyl)amino]-anilin, 1,3-Di(2,4-diaminophenoxy)-propan, Di(2,4-diaminophenoxy)-methan, 1,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis(2-hydroxyethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethylamino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2-methyl-phenol, 5-Amino-4- methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2-methyl-phenol, 3-Amino- 2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino-2-methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)- amino]-acetamid, 5-[(2-Hydroxyethyl)amino]-4-methoxy-2-methyl-phenol, 5-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]- phenol, 3-[(2-Methoxyethyl)amino]-phenol, 5-Amino-2-ethyl-phenol, 5-Amino-2-methoxy-phenol, 2-(4-Amino-2-hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)- amino]-2-methyl-phenol, 3-[(2-Hydroxyethyt)amino]-2-methyl-phenol, 2-Amino-3-hydroxy-pyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 5-Amino-4- chior-2-methyl-phenol, 1-Naphthol, 2-Methyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol-acetat, 1,3-Dihydroxybenzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1,3-dihydroxy-benzol, 1,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1,5-Dichlor-2,4-dihydroxybenzol, 1,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy-phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1,3-benzodioxol, 6-Brom-1-hydroxy-3,4-methylendioxy-benzol, 3,4-Diamino-benzoesäure, 3,4-Dihydro-6-hydroxy-1,4(2H)-benzoxazin, 6-Amino-3,4-dihydro-1,4(2H)- benzoxazin, 3-Methyl-1-phenyl-5-pyrazolon, 5,6-Dihydroxy-indol, 5,6-Dihydroxy-indolin, 5-Hydroxy-indol, 6-Hydroxy-indol, 7-Hydroxy-indol und 2,3-Indolindion enthält. 6. Agent according to one of claims 1 to 5, characterized in that in addition to the compounds of formula (I) there are also further known coupling substances from the group consisting of N-(3-dimethylamino-phenyl)-urea, 2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, 2,4-diamino-1-fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)-pyridine, 2, 6-diamino-3,5-dimethoxy-pyridine, 3, 5-diamino-2,6-dimethoxy-pyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 1,3-diamino-4-(2,3-dihydroxypropoxy)-benzene, 1,3-diamino-4-(3-hydroxypropoxy)-benz ol, 1,3-diamino-4-(2-methoxyethoxy)-benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diamino-benzene, 2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxyacetic acid, 3-[ Di(2-hydroxyethyl)amino]-aniline, 4-amino-2-di[(2- hydroxyethyl)amino]-1-ethoxy-benzene, 5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane, di(2,4-diaminophenoxy)-methane, dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol, 5-amino-4-ethoxy-2-methyl-phenol 3 -Amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-Amino-2-methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)- amino]-acetamid, 5-[(2-Hydroxyethyl)amino]-4-methoxy-2-methyl-phenol, 5-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]- phenol, 3-[(2-Methoxyethyl)amino]-phenol, 5-Amino-2-ethyl-phenol, 5-Amino-2-methoxy-phenol, 2-(4-Amino-2-hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)- amino]-2-methyl-phenol, 3-[(2-Hydroxyethyt)amino]-2-methyl-phenol, 2-Amino-3-hydroxy-pyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 5-Amino-4- chior-2-methyl-phenol, 1-Naphthol, 2-Methyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol-acetat, 1,3-Dihydroxybenzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1,3-dihydroxy-benzol, 1,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1,5-Dichlor-2,4-dihydroxybenzol, 1,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy-phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-M ethyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole and 2,3-indolindione. 7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Entwicklersubstanzen und Kupplersubstanzen, bezogen auf die Gesamtmenge des Färbemittels, jeweils in einer Gesamtmenge von 0,005 bis 20 Gewichtsprozent enthalten sind. 7. Agent according to one of claims 1 to 6, characterized in that the developer substances and coupler substances, based on the total amount of the colorant, are each contained in a total amount of 0.005 to 20 percent by weight. 8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es zusätzlich mindestens einen direktziehenden Farbstoff enthält. 8. Agent according to one of claims 1 to 7, characterized in that it additionally contains at least one direct dye. 9. Mittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es einen pH-Wert von 6, 5 bis 11, 5 aufweist. 9. Agent according to one of claims 1 to 8, characterized in that it has a pH value of 6.5 to 11.5. 10. Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass es ein Haarfärbemittel ist. 10. Agent according to one of claims 1 to 9, characterized in that it is a hair dye. 11. 1,3-Dihydroxybenzol-Derivat der Formel (I) oder dessen physiologisch verträgliches, wasserlösliches Salz,


worin
R1 gleich einer substituierten Pyridylgruppe, einer Pyrimidylgruppe, einem Rest der Formel,


oder einem Rest der Formel


wobei R2, R3, R4, R5 und R6 unabhängig voneinander Wasserstoff, ein Halogenatom (F, Cl, Br, J), eine Cyanogruppe, eine Hydroxygruppe, eine C1-C4-Alkoxygruppe, eine C1-C4-Hydroxyalkoxygruppe, eine C1-C5 -Alkylgruppe, eine C1-C4-Alkylthioethergruppe, eine Mercaptogruppe, eine Nitrogruppe, eine Aminogruppe, eine C1-C4-Alkylaminogruppe, eine Hydroxy(C1-C4)alkylaminogruppe, eine Di(C1-C4)alkylaminogruppe, eine Di(hydroxy(C1-C4)alkyl)aminogruppe, eine (Dihydroxy(C3-C4)alkyl)- aminogruppe, eine (Hydroxy(C1-C4)alkyl)-C1-C4-alkylaminogruppe, eine Trifluormethangruppe eine -C(O)H-Gruppe, eine -C(O)CH3-Gruppe, eine -C(O)CF3-Gruppe, eine -Si(CH3)3-Gruppe, eine C1-C4-Hydroxyalkylgwppe oder eine C2-C4-Dihydroxyalkylgruppe darstellen, oder zwei nebeneinanderliegende Reste R2 bis R6 eine -O-CH2-O-Brücke bilden;
X1 gleich Schwefel, Stickstoff, Sauerstoff, C-R9 oder N-R8 ist;
X2 gleich Schwefel, Stickstoff, Sauerstoff, C-R10 oder N-R8 ist
X3 gleich Schwefel, Stickstoff, Sauerstoff, C-R11 oder N-R8 ist;
R7, R9, R10 und R11 unabhängig voneinander gleich Wasserstoff, einem Halogenatom (F, Cl, Br, J), einer Cyanogruppe, einer C1-C4-Alkoxygruppe, einer C1-C5-Alkylgruppe, einer C1-C4-Alkylthioethergruppe, einer Mercaptogruppe, einer Nitrogruppe, einer Aminogruppe, einer C1-C4-Alkylaminogruppe, einer Di(C1-C4)-alkylaminogruppe, einer Di(C1-C4 hydroxyalkyl)aminogruppe, einer C1-C4 -Hydroxyalkylaminogruppe, einer Trifluormethangruppe einer -C(O)CH3-Gruppe, einer -C(O)CF3-Gruppe, einer -Si(CH3)3-Gruppe, einer C1-C4 -Hydroxyalkylgruppe oder einer C3-C4-Dihydroxyalkylgruppe sind; und
R8 gleich Wasserstoff, einer C1-C5-Alkylgruppe, einer C2-C4 -Hydroxyalkylgruppe, einer Phenylgruppe oder einer Acetylgruppe ist;
unter der Bedingung, dass mindestens einer und maximal zwei der Reste X1 bis X3 gleich C-R9, C-R10 oder C-R11 sind und maximal einer der Reste X1 bis X3 gleich Schwefel, Sauerstoff oder N-R8 ist und R1 nicht gleich einem Phenylrest oder einem Hydroxyphenylrest ist. 11. 1,3-Dihydroxybenzene derivative of formula (I) or its physiologically acceptable, water-soluble salt,


wherein
R1 is a substituted pyridyl group, a pyrimidyl group, a radical of the formula,


or a remainder of the formula


where R2, R3, R4, R5 and R6 independently of one another represent hydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxy group, a C 1 -C 4 alkoxy group, a C 1 -C 4 hydroxyalkoxy group, a C 1 -C 5 alkyl group, a C 1 -C 4 alkylthioether group, a mercapto group, a nitro group, an amino group, a C 1 -C 4 alkylamino group, a hydroxy(C 1 -C 4 )alkylamino group, a di(C 1 -C 4 )alkylamino group, a di(hydroxy(C 1 -C 4 )alkyl)amino group, a (dihydroxy(C 3 -C 4 )alkyl)amino group, a (hydroxy(C 1 -C 4 )alkyl)-C 1 -C 4 -alkylamino group, a trifluoromethane group, a -C(O)H group, a -C(O)CH 3 group, a -C(O)CF 3 group, a -Si(CH 3 ) 3 group, a C 1 -C 4 hydroxyalkyl group or a C 2 -C 4 dihydroxyalkyl group, or two adjacent radicals R2 to R6 form an -O-CH 2 -O- bridge;
X1 is sulfur, nitrogen, oxygen, C-R9 or N-R8;
X2 is sulphur, nitrogen, oxygen, C-R10 or N-R8
X3 is sulfur, nitrogen, oxygen, C-R11 or N-R8;
R7, R9, R10 and R11 are independently hydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a C 1 -C 4 alkoxy group, a C 1 -C 5 alkyl group, a C 1 -C 4 alkylthioether group, a mercapto group, a nitro group, an amino group, a C 1 -C 4 alkylamino group, a di(C 1 -C 4 )alkylamino group, a di(C 1 -C 4 hydroxyalkyl)amino group, a C 1 -C 4 hydroxyalkylamino group, a trifluoromethane group, a -C(O)CH 3 group, a -C(O)CF 3 group, a -Si(CH 3 ) 3 group, a C 1 -C 4 hydroxyalkyl group or a C 3 -C 4 dihydroxyalkyl group; and
R8 is hydrogen, a C 1 -C 5 alkyl group, a C 2 -C 4 hydroxyalkyl group, a phenyl group or an acetyl group;
provided that at least one and a maximum of two of the radicals X1 to X3 are C-R9, C-R10 or C-R11 and a maximum of one of the radicals X1 to X3 is sulfur, oxygen or N-R8 and R1 is not a phenyl radical or a hydroxyphenyl radical.
DE20108704U 2001-05-25 2001-05-25 1,3-dihydroxybenzene derivatives and dyes for these containing keratin fibers Expired - Lifetime DE20108704U1 (en)

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DE20108704U DE20108704U1 (en) 2001-05-25 2001-05-25 1,3-dihydroxybenzene derivatives and dyes for these containing keratin fibers
CA002445647A CA2445647A1 (en) 2001-05-25 2002-01-28 1,3-dihydroxybenzene derivatives and colorants containing said compounds
CNB028095456A CN100349886C (en) 2001-05-25 2002-01-28 1,3-Dihydroxybenzene derivatives and dyes containing these compounds
JP2003500080A JP2004519524A (en) 2001-05-25 2002-01-28 1,3-dihydroxybenzene-derivatives and dyes containing these compounds
EP02711818A EP1392673B1 (en) 2001-05-25 2002-01-28 1,3-dihydroxybenzene derivatives and colorants containing said compounds
DE50203353T DE50203353D1 (en) 2001-05-25 2002-01-28 1,3-DIHYDROXYBENZOLE DERIVATIVES AND STAINERS CONTAINING THESE COMPOUNDS
MXPA03008699A MXPA03008699A (en) 2001-05-25 2002-01-28 1,3-dihydroxybenzene derivatives and colorants containing said compounds.
AT02711818T ATE297389T1 (en) 2001-05-25 2002-01-28 1,3-DIHYDROXYBENZENE DERIVATIVES AND DYES CONTAINING THESE COMPOUNDS
ES02711818T ES2241999T3 (en) 2001-05-25 2002-01-28 DERIVATIVES OF 1,3-DIHYDROXIBENCEN AND PRODUCTS FOR THE DYING OF FIBERS THAT CONTAIN THEM.
AU2002231759A AU2002231759B2 (en) 2001-05-25 2002-01-28 1,3-dihydroxybenzene derivatives and colorants containing said compounds
US10/416,048 US7125428B2 (en) 2001-05-25 2002-01-28 1,3-Dihydroxybenzene derivatives and colorants containing said compounds
PCT/EP2002/000850 WO2002096901A2 (en) 2001-05-25 2002-01-28 1,3-dihydroxybenzene derivatives and colorants containing said compounds
BR0205398-5A BR0205398A (en) 2001-05-25 2002-01-28 1,3-Dihydroxybenzene derivatives and dyeing agents containing these compounds

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002057243A1 (en) * 2001-01-18 2002-07-25 Wella Aktiengesellschaft Novel 1,4-diamino-2-(thiazol-2-yl)benzene derivatives and dyes containing said compounds
WO2004052316A3 (en) * 2002-12-12 2004-12-23 Unilever Plc Novel skin lightening agents, compositions and methods

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002057243A1 (en) * 2001-01-18 2002-07-25 Wella Aktiengesellschaft Novel 1,4-diamino-2-(thiazol-2-yl)benzene derivatives and dyes containing said compounds
US6875873B2 (en) 2001-01-18 2005-04-05 Wella Aktiengesellschaft 1,4-Diamino-2-(thiazol-2-yl)benzene derivatives, and dyes containing said compounds
WO2004052316A3 (en) * 2002-12-12 2004-12-23 Unilever Plc Novel skin lightening agents, compositions and methods

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