WO2002070610A2 - Novel reactive dyes and the use thereof for dyeing substrates containing nucleophilic groups - Google Patents

Novel reactive dyes and the use thereof for dyeing substrates containing nucleophilic groups Download PDF

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Publication number
WO2002070610A2
WO2002070610A2 PCT/EP2002/002385 EP0202385W WO02070610A2 WO 2002070610 A2 WO2002070610 A2 WO 2002070610A2 EP 0202385 W EP0202385 W EP 0202385W WO 02070610 A2 WO02070610 A2 WO 02070610A2
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WIPO (PCT)
Prior art keywords
groups
reactive dye
group
hair
dyeing
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PCT/EP2002/002385
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French (fr)
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WO2002070610A3 (en
Inventor
Helmut Reichelt
Günther Seybold
Manfred Patsch
Gunter-Rudolf SCHRÖDER
Stevan David Jones
James Charles Dunbar
Colin John Clarke
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BASF SE
Procter and Gamble Co
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BASF SE
Procter and Gamble Co
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Priority to JP2002570639A priority Critical patent/JP2004530001A/en
Priority to DE60205466T priority patent/DE60205466T2/en
Priority to US10/469,600 priority patent/US7108727B2/en
Priority to AU2002308234A priority patent/AU2002308234A1/en
Priority to EP02748331A priority patent/EP1368433B1/en
Priority to AT02748331T priority patent/ATE301692T1/en
Publication of WO2002070610A2 publication Critical patent/WO2002070610A2/en
Publication of WO2002070610A3 publication Critical patent/WO2002070610A3/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/418—Amines containing nitro groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the present invention relates to novel reactive dyes of formula I
  • R 1 to R 9 independently hydrogen, Ci-Cs alkyl, C -Cs alkyl, in which non-adjacent CH 2 groups can be replaced by oxygen atoms, imi- no groups or C ⁇ -C alkylimino groups, and/or CH groups by carbonyl groups, C -C ⁇ alkenyl or -a group containing an active site or the precursor of an active site,
  • radicals R 1 to R 9 are a group which contains an active site or the precursor of an active site.
  • the present invention also relates to the use of the reactive dyes of formula I for dyeing substrates containing nucleophilic. groups.
  • the present invention also relates to compositions containing at least one reactive dye of formula I.
  • the reactive dyes of formula I are usually present in protonized form.
  • the reactive dyes may also exist in the form of their, preferably physiologically acceptable, salts.
  • suitable cations are derived from, in particular, metal or ammonium ions. These primarily include lithium, sodium, or potassium ions or unsubstituted or substituted ammonium cations.
  • Substituted ammonium cations are, for example, monoalkyl, dialkyl, trialkyl, tetraalkyl, or benzyltrialkylamo- nium cations or such cations as are derived from nitrogen-containing five-membered or six-membered saturated heterocyclic com- pounds, such as pyrrolidinium, piperidinium, morpholinium, piper- azinium, or N-alkylpiperazinium cations or their N-monoalkyl or N,N-dialkyl-substituted products.
  • alkyl we generally mean linear or branched C ⁇ -C o . alkyl, which can be substituted by 1 or 2 hydroxyl groups and/or may be interspersed by from 1
  • Ci-Cs alkyl represented by R 1 to R 9 are branched or unbranched alkyl chains , such as methyl , ethyl , n- propyl, i ⁇ opropyl, n-butyl , sec-butyl, isobutyl, tert-butyl, n- pentyl, 1-methylbutyl , 2-methylbutyl , 3-methylbutyl , 2,2-dime- thylpropyl, 1-ethylpropyl , n-hexyl, 1, 1-dimethylpropyl, 1,2-dime- thylpropyl, 1-methylpentyl , 2-methylpentyl , 3-methylpentyl , 4-me- thylpentyl , 1 , 1-dimethylbutyl , 1 , 2-dimethylbutyl , 1 , 3-dimethylbu- tyl, 2 , 2-dimethylbutyl,
  • suitable C -C 8 alkenyl represented by R 1 to R 9 there may be mentioned branched or unbranched alkenyl chains, such as vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-l-butenyl , 2-methyl-2-butenyl , 3-methyl-l-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, or 2-octenyl.
  • branched or unbranched alkenyl chains such as vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-l-butenyl , 2-methyl-2-butenyl , 3-methyl-l-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl,
  • Examples of suitable C 2 -Cs alkyl, in which non-adjacent CH groups can be replaced by oxygen atoms, imino groups, or C ⁇ -C alkylimino groups, and/or CH groups may be replaced by carbonyl groups, as represented by R 1 to R 9 are, eg,
  • R independently denotes hydrogen, methyl, ethyl, n-propyl, iso- propyl, n-butyl , sec-butyl, isobutyl, or tert-butyl .
  • the latter formulas cover, for example, the radicals -CH 2 -0-C (0) -H and -CH 2 -C-(0)-0-H (in each case r is 0), -CH 2 -0-C (0) -CH 3 and - CH -C(0)-0-CH 3 (in each case r is 1) , and -CH 2 -0-C (0) -C 2 H 5 and - CH 2 -C(0)-0-CH 5 (in each case r is 2).
  • radicals R 1 to R 9 when they denote a group containing an active site or the precursor of an active site.
  • a group con- taining an active site or the precursor of an active site is referred to below a "reactive group” .
  • the reactive groups take part in an addition reaction with the relevant groups in the substrate, eg, with the amino or hydroxy groups of hair, this means, for example with reference to the vinyl sulfone site, that the amino or hydroxy groups in the hair are added to the reactive groups as follows: - (hair ) -S0 2 -CH 2 -CH 2 -Nuc (hair )
  • the reactive groups take part in a substitution reaction with the relevant nucleophilic groups (HNuc-) in the substrate, eg, with the amino or hydroxy groups in hair, this means, for example with reference to the chlorotriazine site, that the leaving groups or atoms (eg, in this case chlorine) in the reactive groups are substituted by the amino groups in hair according to the following diagram:
  • radicals R 1 to R 9 as (additively reacting) groups containing the precursor of an active site, are, in par- ticular, -M 1 -S0 -CHQ, where M 1 stands for phenylene or linear or branched Ci-Cs alkene in which non-adjacent CH groups may be replaced by oxygen atoms, imino groups or C 1 -C 4 alkylimino groups.
  • these are CH 2 , (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , CH(CH 3 )CH 2 , CH(CH 3 )CH(CH 3 ) , (CH 2 ) 5 , (CH 2 ) 6 , (CH 2 ) 2 0 (CH 2 ) 2 , (CH 2 ) 3 0 (CH 2 ) 2 , (CH 2 ) 2 0(CH 2 ) 2 0(CH 2 ) 2 , (CH 2 ) 2 NH (CH 2 ) 2 , (CH 2 ) 3 NH (CH 2 ) 2 , (CH 2 ) 2 NH(CH 2 ) 2 NH(CH 2 ) 2 NH(CH 2 ) 2 ,
  • the radical Q stands for a group that is capable of being split off under alkaline reaction conditions, such as chlorine, bromine, C 1 -C 4 alkylsulfonyl, phenyl ⁇ ulf onyl , 0S0 3 H, SS0 3 H, 0P(0) (0H) 2 , C 1 -C 4 alkylsulfonyloxy, phenylsulfonyloxy, C3 . -C 4 alka- noyloxy, C 1 -C 4 dialkylamino or a radical of the formula
  • Z 1 , Z 2 , and Z 3 are the same or different and independently denote C 1 -C 4 alkyl or benzyl, and An ⁇ denotes an equivalent of an anion.
  • Suitable anions include, for example, fluoride, chloride, bromide, iodide, monochloro, dichloro, or trichloroacetate, methane sulfonate, benzene sulfonate or 2- or 4-methylbenzene sulfo- nate .
  • Preferred radicals Q are chlorine, acetate, and SS0 3 H and, more preferably, Q stands for 0S0 3 H.
  • groups containing an active site or the precursor of an active site are, for example, groups of formulas Ila to lie, where U designates either -CH 4 Q, as defined above, or a vinyl group.
  • R 1 to R 9 substitutively reacting reactive groups represented by R 1 to R 9 are halogen-substituted radicals derived from 1 , 3 , 5-triazine, quinoxaline, phthalazine, pyrimidine, pyridazine, or 2-alkylsulfonylbenzthiazol as heterocyclic parent substances.
  • heterocyclic radicals which may additionally contain additively reacting substituents:
  • Z 4 independently stands for hydrogen , C ⁇ -C 6 alkyl , or phenyl ,
  • Hal denotes fluorine , chlorine , or bromine
  • U 1 denotes hydrogen or nitro
  • U 2 and U 3 independently denote hydrogen or Ci-C ⁇ alkyl, optionally substituted by hydroxy, halogen, cyano, hydroxysulfonyl or a radical of the formula -S0 2 -U, where U has the meaning stated above, and optionally interspersed by 1 or 2 non-adjacent oxygen atoms, imino groups or C 1 -C 4 alkylimino groups, or
  • U 2 and U 3 form, together with the interconnecting nitrogen atom, a pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or N-(C ⁇ -C 4 alkyl )piperazinyl radical, or
  • rings B 1 and B 2 may be monosubstituted or disubsti- tuted by hydroxysulfonyl and/or benzoanellated, and ring B 2 may independently be monosubstituted or disubstituted by chlorine, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyano, carboxyl, acetylamino, hydroxysulfonylmethyl or a radical of the formula CH 2 -S0 2 -U,
  • U and U 2 have the aforementioned meanings and L stands for C 2 -C 6 alkene, optionally ⁇ ubstituted by hydroxy, chlorine, cyano, carboxyl, C 3. -C 4 alkoxy- carbonyl , C 1 -C 4 alkanoyloxy or ⁇ ulfato and optionally inter ⁇ per ⁇ ed by 1 or 2 non-adjacent oxygen atoms, imino groups, or C ⁇ -C 4 alky- limino groups. 5
  • Suitable radicals U 2 and U 3 include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl , hexyl, or 2-methylpentyl .
  • radicals U 2 and U 3 are hydroxy (C 1 -C 4 alkyl) , such as hydroxymethyl , 1-hydroxyethyl-l , 2-hydroxyethyl-l , 1-hy- droxypropyl-1, 2-hydroxypropyl-l, 3-hydroxypropyl-l , 1-hydroxy- propyl-2, 2-hydroxypropyl-2 , 1-hydroxybutyl-l , 2-hydroxybutyl-l , 3-hydroxybutyl-l, 4-hydroxybutyl-l , l-hydroxybutyl-2 , 2-hydroxy-
  • radicals U 2 and U 3 are cyanomethyl , cyanoethyl, 20 cyanopropyl, or cyanobutyl and also hydroxysulfonylmethyl, 2-hy- droxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, or 2- or 4-hy- droxy ⁇ ulfonylbutyl .
  • the radical L is, eg, (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , CH(CH 3 )CH 2 , 25 CH(CH 3 )CH(CH 3 ) , (CH 2 ) 5 , or (CH 2 ) 6 .
  • the radical L may also be, for example, (CH 2 ) 0 (CH 2 ) 2 , (CH 2 ) 3 0(CH 2 ) 2 , (CH 2 ) 2 0(CH 2 ) 2 0(CH 2 ) 2 , (CH 2 ) 2 S (CH 2 ) 2 , (CH 2 ) 3 S (CH 2 ) 2 , (CH 2 ) 2 S(CH 2 ) 2 S(CH 2 ) 2 , (CH 2 ) 2 NH(CH 2 ) 2 , (CH 2 ) 3 NH (CH 2 ) 2 , 30 (CH 2 ) 2 NH(CH 2 ) 2 NH(CH 2 ) 2 ,
  • aliphatic or aromatic sulfonic acid deriva- tives and also the aliphatic sulfonic acid derivatives partially or completely substituted by fluorine are suitable for this purpose.
  • Preferred reactive dyes of the invention are those in which X de- notes N0 2 •
  • Y denotes SR 8 , S0 2 R 9 - or a group that is suitable for use as a leaving group un- der the conditions of nucleophilic, aromatic ⁇ ub ⁇ titution.
  • the pre ⁇ ent invention also relates to the use of the reactive dyes of the invention and to their preferred embodiments for dyeing ⁇ ubstrates containing nucleophilic groups.
  • Such sub ⁇ trate ⁇ comprise, for example, a great variety of grades of cellulose products, such a ⁇ textile ⁇ based on cotton, paper for the production of newspaper ⁇ and magazines, cellulosic material for, say, sanitary purpose ⁇ , and wooden product ⁇ , for exam- pie for the production of furniture, hide ⁇ , such as leather, and animal skins, also human skin, for example when applying temporary tattoos, and human hair.
  • the reactive dyes of the invention and their preferred embodi- ments are preferably used for dyeing substrates containing hydroxy, mercapto, amino, and/or imino groups.
  • the reactive dyes of the invention and their preferred embodiments are u ⁇ ed for dyeing keratinic fiber ⁇ , of which animal or human hair is particularly ⁇ ignificant.
  • the pre ⁇ ent invention al ⁇ o relate ⁇ to compo ⁇ ition ⁇ containing at least one reactive dye of the invention.
  • the reactive dyes of the invention are usually employed in di ⁇ - ⁇ olved form.
  • the reactive dyes are dissolved in an aqueous, cosmetically acceptable medium.
  • the pH varie ⁇ between pH 3 to pH 11, more preferably pH 6 to pH 11. It i ⁇ set to the desired value by mean ⁇ of inorganic or organic ba ⁇ e ⁇ , ⁇ alts of weak acids, or buffers.
  • the reactive dyes are present in said compositions in concentra- tions of from 0.01 to 10 wt%, based on the total weight of the composition.
  • compositions for hair coloration are anion- ic, cationic, non-ionic, or amphoteric surface-active compounds or mixtures thereof .
  • Example ⁇ of surface-active compound are soap ⁇ , alkylbenzene sulfonates, alkyl naphthalene ⁇ ulfonate ⁇ , ⁇ ul- fate ⁇ , fatty alcohol polyglycol ⁇ ulfate ⁇ , and ⁇ ulfonates of fatty alcohols, quarternary ammonium salt ⁇ , ⁇ uch a ⁇ trimethylcetylamo- nium bromide, cetylpyridinium bromide, quaternium 1 to X (INCI) , cocoyltrimethylammonium methylsulfate (INCI) , hydroxyethyl cetyl- dimomium phosphate ⁇ (INCI) , cetyltrimethylammonium chloride, optionally oxyethylenized fatty acid ethanolamides , polyoxyethyle- nized
  • auxiliaries are organic solvents acting as so- lubilizing agents, eg, C 1 -C 4 alcohol such as ethanol and isopro- panol, glycol ⁇ , glycol ether ⁇ , ⁇ uch a ⁇ ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol , or 2-butoxyethanol, and al ⁇ o glycerol .
  • the ⁇ e ⁇ olvent ⁇ are u ⁇ ually present in a con- centration of 0 - 40 wt%, based on the total weight of the composition.
  • thickeners are usually added as auxiliarie ⁇ .
  • Common thick- ener ⁇ are cellulo ⁇ e derivatives, such as methyl, hydroxymethyl , hydroxyethyl, hydroxypropyl , or carboxymethyl cellulose, ⁇ odium alginate, gum arabic, gum xanthan, gum traganth, acrylic acid polymer ⁇ , polyvinylpyrrolidone, poly (vinyl acetate-co-crotonic acid)s, poly (vinyl acetate-co-vinyl pyrrolidone) s, poly (butylvi- nyl ether-co-maleic anhydride) ⁇ , or poly (methylvinyl ether-co-maleic anhydride) ⁇ .
  • Inorganic thickener ⁇ uch a ⁇ bentonite, are al ⁇ o ⁇ uitable.
  • the ⁇ e thickener ⁇ are usually employed in a con- centration of up to 5 wt%, based on the total weight of the composition.
  • Hair-care compositions which are to be used in the form of gels al ⁇ o contain gel-forming substances, such as carbomers (INCI).
  • the compo ⁇ ition ⁇ may additionally contain cationic polymer ⁇ and silicone compounds.
  • Suitable cationic polymers are, for example, polyquaternium 1 to x (INCI) , copolymers of vinyl pyrrolidone/vinyl imidazolium salts (Luviquat® FC, Luviquat® HM; , sold by BASF Aktiengesellschaft, udwigshafen) , copolymer ⁇ of vinyl pyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethyl ⁇ ulfate (Luviquat PQ 11) ; cationic cellulose derivatives (polyquaternium 4 and 10) , acryla- mide copolymers (polyquaternium 7) and cationic guar gum deriva- tive ⁇ , eg
  • auxiliaries are mild antioxidants that do not react with the dyes, penetrating agents, ⁇ eque ⁇ tering agents, buffers, perfume oils, light-stabilizing agent ⁇ (UV-A and UN-B filters) , preservatives, shampoo ⁇ , and active substance ⁇ ⁇ uch a ⁇ (d(+) -pantothenyl alcohol, bi ⁇ abolol and vitamins, eg, vitamins A, C, and E.
  • the compo ⁇ ition ⁇ of the invention can be used in liquid form, usually thickened, as a cream, paste, gel, or any other ⁇ uitable form.
  • the hair colouring compo ⁇ itions of the present invention may, in addition to the dyes discussed herein above include other nonoxi- dative, oxidative and other dye materials.
  • Optional nonoxidative and other dye ⁇ suitable for use in the hair colouring composi- tions and processes according to the present invention include demi-permanent, semi-permanent, temporary and other dyes.
  • ⁇ on-ox- idative dyes as defined herein include the so-called "direct action dyes", metallic dye ⁇ , metal chelate dye ⁇ , fibre reactive dyes, acid dyes, ba ⁇ ic dye ⁇ , non-ionic dye ⁇ , anionic dye ⁇ , ca- tionic dye ⁇ , HC dye ⁇ and other ⁇ ynthetic and natural dyes.
  • Oxidative hair colouring agents to be u ⁇ ed in the compo ⁇ itions herein are typically, but without intending to be limited thereby, oxidative hair colouring agents, consi ⁇ ting e ⁇ sentially of at least two components, which are collectively referred to as dye forming intermediates (or precursor ⁇ ) .
  • Dye forming intermediates can react in the presence of a ⁇ uitable oxidant to form a coloured molecule.
  • the dye forming intermediates u ⁇ ed in oxidative hair colorant ⁇ include: aromatic diamine ⁇ , aminophenols, various heterocycle ⁇ , phenols, naphthols and their various diami- nobenzene or its derivatives.
  • the hair colouring composition ⁇ may al ⁇ o comprise at least one oxidising agent, which may be an inorganic or organic oxidising agent .
  • the oxidising agent is preferably present in the colouring composition at a level of from about 0.01% to about 20%, more preferably from about 0.01% to about 10%, more preferably from about 1% to about 6% by weight of the compo ⁇ ition.
  • a preferred oxidi ⁇ - ing agent for u ⁇ e herein i ⁇ an inorganic peroxygen oxidising agent.
  • a hair-care composition is applied to the hair and allowed to act thereon over a period of from 5 to 50 minutes and preferably from 10 to 30 minutes, after which the hair is rinsed and optionally washed with a conventional shampoo.
  • Dyeing can be accelerated by using the composition in a warm state or by applying heat externally, or intensified if the period of action is not ⁇ hortened.
  • temperatures ranging from 20° to 40°C are used.
  • the reactive dyes of the invention yield level dyeings and cover even white hair well.
  • the dyeing ⁇ how good fa ⁇ tne ⁇ to light, washing, weathering, and abrasion, as external influences.
  • Example 4b 37 g (0.1 mol) of the fluorine compound of Example lb were added to 250 mL of water and 0.2 g of Emulan® EL were added. 11 g (0.12 mol) of thioglycollic acid (sold by Merck KGaA, Darmstadt) were then added and the mixture was set to a pH of 6.5 with sodium hydrogencarbonate. The batch was heated to 40°C and stirring was continued at this temperature over a period of 6 hours. Following cooling, the precipitated product wa ⁇ filtered off and dried in vacuo at 35°C. The yield wa ⁇ 33.9 g.
  • Example 4b 35 g (0.1 mol) of the fluorine compound of Example lb were added to 250 mL of water and 0.2 g of Emulan® EL were added. 11 g (0.12 mol) of thioglycollic acid (sold by Merck KGaA, Darmstadt) were then added and the mixture was set to a pH of 6.5 with sodium hydrogen
  • the pH was set to 5 by the addition of calcium carbonate at from 5° to 10°C.
  • the precipitated calcium sulfate was filtered off, and the filtrate set to pH 4.5 with acetic acid and concentrated to drynes ⁇ at 30°C in the vacuum of a rotary film evaporator. Further drying was carried out at room temperature in a vacuum drying cabinet.
  • the yield of the product of the formula shown above was 20.3 g (HPLC 93.4 % by area).
  • phase II
  • phase II was added to phase II.
  • phase III wa ⁇ added.
  • a bleached skein of human hair (2 g) was treated with 0.5 g of the dyeing creme, which wa ⁇ allowed to act for 20 min.
  • a water- rin ⁇ e followed. There wa ⁇ obtained a hair coloration a ⁇ described in the coloration example.
  • Luviskol® VA 64 ( ⁇ old by BASF Aktiengesellschaft, Ludwig- shafen) , (PVP/VA copolymer (INCI))
  • a bleached skein of human hair (2 g) was treated with 0.5 g of the hair-coloring mousse, which was allowed to act for 15 min, followed by a water rinse.
  • the hair i ⁇ very easy to comb and has a well- groomed appearance.
  • Betain L 7 ( ⁇ old by Goldschmidt AG Degus ⁇ a AG, Du ⁇ - seldorf)
  • a hair-coloring shampoo makes it pos ⁇ ible to clean and dye the hair in one.
  • Aerosil 15g Aerosil (sold by Degu ⁇ sa AG, Dus ⁇ eldorf)
  • Lutrol® F 127 polyethylene glycol, ⁇ old by BASF Aktien- ge ⁇ ell ⁇ chaft, Ludwig ⁇ hafen
  • a bleached skein of human hair (2 g) was treated with 0.5 g of the hair-coloring paste, which wa ⁇ allowed to act for 15 min, followed by a water rinse. There was obtained a hair coloration as described in the coloration example.
  • the dye emulsion base is prepared by a one pot process as follows :
  • fatty alcohol ⁇ and any ethoxylated fatty alcohol ⁇ e.g. ceteareth-25, cetyl, ⁇ tearyl and steareth-2, and allow to melt. Increase agitation.
  • the hydrogen peroxide cream is also prepared similarly using a one pot proce ⁇ .

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Abstract

The present invention relates to novel reactive dyes of formula I, (I), in which the variable independently denote X hydrogen, NO2, or NR?3R4, Y NR5R6, OR7, SR8¿, or SO¿2R?9 or a group suitable as a leaving group under the conditions of nucleophilic, aromatic substitution, R1 to R9 independently hydrogen, C¿1?-C8 alkyl, C2-C8 alkyl, in which non-adjacent CH2 groups can be replaced by oxygen atoms, imino groups, or C1-C4 alkylimino groups, and/or CH2 groups may be replaced by carbonyl groups, C2-C8 alkenyl, or a group containing an active site or the precursor of an active site, with the proviso that at least one group R?1 to R9¿ is present which contains an active site or the precursor of an active site. The present invention also relates to the use of the reactive dyes of Formula I for dyeing substrates containing nucleophilic groups, and to compositions containing at least one reactive dye of formula I.

Description

Novel Reactive Dyes and The Use Thereof for Dyeing Substrates Containing Nucleophilic Groups
Description
The present invention relates to novel reactive dyes of formula I
Figure imgf000002_0001
in which the variables independently denote
X hydrogen, N02, or NR3R4,
Y NR5R6, OR7, SR8, or S02R9 or a group suitable as leaving group under the conditions of nucleophilic, aromatic substitution,
R1 to R9 independently hydrogen, Ci-Cs alkyl, C -Cs alkyl, in which non-adjacent CH2 groups can be replaced by oxygen atoms, imi- no groups or Cχ-C alkylimino groups, and/or CH groups by carbonyl groups, C -Cβ alkenyl or -a group containing an active site or the precursor of an active site,
with the proviso that at least one of the radicals R1 to R9 is a group which contains an active site or the precursor of an active site.
The present invention also relates to the use of the reactive dyes of formula I for dyeing substrates containing nucleophilic. groups.
The present invention also relates to compositions containing at least one reactive dye of formula I.
A large number of reactive dyes has been described for coloring a great variety of substrates. For example, the use of reactive dyes for dyeing nitrogen atom-containing fibers, such as wool, is disclosed in the specifications US 4,066,638, EP 107,614, EP 559,617, DE 3,441,273, and DE 2,154,942. US 4,102,641 relates to the use of dyes containing a halogen triazine radical as fiber-reactive group for dyeing hair.
Furthermore, specification JP 75,025,529 A mentions dye formula- tions for dyeing hair. The reactive dyes used are based on p-sul- fatoethylεulfonylaniline as diazo component and a fiber-reactive radical .
It is now the object of the present invention to provide further reactive dyes which show good interaction properties on the substrates to be dyed and can be applied under a variety of dyeing conditions .
Accordingly, we have found the above reactive dyes of the general formula I .
In instances where R1 to R9 correspond to radicals containing acidic hydrogen atoms, the reactive dyes of formula I are usually present in protonized form. Of course, the reactive dyes may also exist in the form of their, preferably physiologically acceptable, salts.
In the latter case, suitable cations are derived from, in particular, metal or ammonium ions. These primarily include lithium, sodium, or potassium ions or unsubstituted or substituted ammonium cations. Substituted ammonium cations are, for example, monoalkyl, dialkyl, trialkyl, tetraalkyl, or benzyltrialkylamo- nium cations or such cations as are derived from nitrogen-containing five-membered or six-membered saturated heterocyclic com- pounds, such as pyrrolidinium, piperidinium, morpholinium, piper- azinium, or N-alkylpiperazinium cations or their N-monoalkyl or N,N-dialkyl-substituted products. By alkyl we generally mean linear or branched Cι-C o .alkyl, which can be substituted by 1 or 2 hydroxyl groups and/or may be interspersed by from 1 to 4 oxygen atoms in ether-like fashion.
Examples of suitable Ci-Cs alkyl represented by R1 to R9 are branched or unbranched alkyl chains , such as methyl , ethyl , n- propyl, iεopropyl, n-butyl , sec-butyl, isobutyl, tert-butyl, n- pentyl, 1-methylbutyl , 2-methylbutyl , 3-methylbutyl , 2,2-dime- thylpropyl, 1-ethylpropyl , n-hexyl, 1, 1-dimethylpropyl, 1,2-dime- thylpropyl, 1-methylpentyl , 2-methylpentyl , 3-methylpentyl , 4-me- thylpentyl , 1 , 1-dimethylbutyl , 1 , 2-dimethylbutyl , 1 , 3-dimethylbu- tyl, 2 , 2-dimethylbutyl, 2 , 3-dimethylbutyl , 3 , 3-dimethylbutyl , 1-ethylbutyl , 2-ethylbutyl , 1 , 1 , 2-trimethylpropyl , 1,2,2-trime- thylpropyl, 1-ethyl-l-methylpropyl, l-ethyl-2-methylpropyl , n-heptyl, n-octyl, or 2-ethylhexyl .
As examples of suitable C -C8 alkenyl represented by R1 to R9 there may be mentioned branched or unbranched alkenyl chains, such as vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-l-butenyl , 2-methyl-2-butenyl , 3-methyl-l-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, or 2-octenyl.
Examples of suitable C2-Cs alkyl, in which non-adjacent CH groups can be replaced by oxygen atoms, imino groups, or Cχ-C alkylimino groups, and/or CH groups may be replaced by carbonyl groups, as represented by R1 to R9 are, eg,
-(CH2-CH2-0-)pH, -(CH2-CH2-0-)pCH3, - (CH2-CH (CH3) -0-)pH, -(CH2-CH2-NR-)pH, -(CH2-CH2-NR-)PCH3 or - (CH2-CH (CH3) -NR-)pH, where p denotes 1 or 2 , or
-CH2-OC(0)-[(CH2)R]H, -CH2-C (0) -0- [ (CH2) r]H, -CH2-NR-C (0) - [ (CH2) r]H and -CH2-C(0)-NR-[ (CH2)r]H, where r denotes 0, 1, 2, 3, 4, or 5 and
R independently denotes hydrogen, methyl, ethyl, n-propyl, iso- propyl, n-butyl , sec-butyl, isobutyl, or tert-butyl .
The latter formulas cover, for example, the radicals -CH2-0-C (0) -H and -CH2-C-(0)-0-H (in each case r is 0), -CH2-0-C (0) -CH3 and - CH -C(0)-0-CH3 (in each case r is 1) , and -CH2-0-C (0) -C2H5 and - CH2-C(0)-0-CH5 (in each case r is 2).
The following remarks apply to the meaning of radicals R1 to R9 when they denote a group containing an active site or the precursor of an active site. For the sake of simplicity, a group con- taining an active site or the precursor of an active site is referred to below a "reactive group" .
If the reactive groups take part in an addition reaction with the relevant groups in the substrate, eg, with the amino or hydroxy groups of hair, this means, for example with reference to the vinyl sulfone site, that the amino or hydroxy groups in the hair are added to the reactive groups as follows: - (hair ) -S02 -CH2 -CH2 -Nuc (hair )
Figure imgf000005_0001
Figure imgf000005_0002
When, on the other hand, the reactive groups take part in a substitution reaction with the relevant nucleophilic groups (HNuc-) in the substrate, eg, with the amino or hydroxy groups in hair, this means, for example with reference to the chlorotriazine site, that the leaving groups or atoms (eg, in this case chlorine) in the reactive groups are substituted by the amino groups in hair according to the following diagram:
Figure imgf000005_0003
Additively reacting groups represented by R1 to R9 are, for example, acryloyl, monochloroacryloyl, dichloroacryloyl , or trichlo- roacryloyl, monobromoacryloyl , dibromo cryloyl , or tribromoacry- loyl, C0-CC1=CH-C00H, -C0-CH=C-C1-C00H, 2-chloropropionyl , 1, 2-dichloropropionyl , 1 , 2-dibromopropionyl , 3-phenylsulfonylpro- pionyl, 3-methylsulfonylpropionyl , 2-sulfatoethylaminosulfonyl, 2-chloro-2 , 3 , 3-trifluorocyclobutylcarbonyl , 2,2,3, 3-tetrafluoro- cyclobutylcarbonyl, 2,2,3, 3-tetrafluorocyclobutylsulfonyl, 2- (2, 2 , 3 , 3-tetrafluorocyclobutyl) acryloyl , 1- or 2-alkylsulfony- lacryloyl or 1- or 2-arylsulfonylacryloyl , such as 1- or 2-me- thylsulfonylacryloyl .
Examples of suitable radicals R1 to R9, as (additively reacting) groups containing the precursor of an active site, are, in par- ticular, -M1-S0 -CHQ, where M1 stands for phenylene or linear or branched Ci-Cs alkene in which non-adjacent CH groups may be replaced by oxygen atoms, imino groups or C1-C4 alkylimino groups. For example, these are CH2 , (CH2)2, (CH2)3, (CH2)4, CH(CH3)CH2, CH(CH3)CH(CH3) , (CH2)5, (CH2)6, (CH2) 20 (CH2) 2 , (CH2) 30 (CH2) 2 , (CH2)20(CH2)20(CH2)2, (CH2) 2NH (CH2) 2, (CH2) 3NH (CH2) 2, (CH2)2NH(CH2)2NH(CH2)2,
(CH2)2N(CH2)2, (CH2)3N(CH2)2 , or (CH2) 2N(CH2) 2N (CH2) 2
CH3 CH3 CH3 CH3 The radical Q stands for a group that is capable of being split off under alkaline reaction conditions, such as chlorine, bromine, C1-C4 alkylsulfonyl, phenylεulf onyl , 0S03H, SS03H, 0P(0) (0H)2, C1-C4 alkylsulfonyloxy, phenylsulfonyloxy, C3.-C4 alka- noyloxy, C1-C4 dialkylamino or a radical of the formula
Figure imgf000006_0001
where Z1, Z2 , and Z3 are the same or different and independently denote C1-C4 alkyl or benzyl, and An© denotes an equivalent of an anion. Suitable anions include, for example, fluoride, chloride, bromide, iodide, monochloro, dichloro, or trichloroacetate, methane sulfonate, benzene sulfonate or 2- or 4-methylbenzene sulfo- nate .
Preferred radicals Q are chlorine, acetate, and SS03H and, more preferably, Q stands for 0S03H.
An example of a suitable group containing an active site, as represented by R1 to R9, is, in particular, -M1-S02-CH=CH2, in which the variable M1 has the meaning stated above.
Other (additively reacting) groups containing an active site or the precursor of an active site, are, for example, groups of formulas Ila to lie, where U designates either -CH4Q, as defined above, or a vinyl group.
Figure imgf000006_0002
S03H S03H S03H
(Ha) (lib) (lie)
Figure imgf000007_0001
(lid) (He) (Hf) Examples of substitutively reacting reactive groups represented by R1 to R9 are halogen-substituted radicals derived from 1 , 3 , 5-triazine, quinoxaline, phthalazine, pyrimidine, pyridazine, or 2-alkylsulfonylbenzthiazol as heterocyclic parent substances.
Particular mention may be made here of the following heterocyclic radicals which may additionally contain additively reacting substituents:
Figure imgf000007_0002
Figure imgf000008_0001
in which Z4 independently stands for hydrogen , Cι-C6 alkyl , or phenyl ,
Hal denotes fluorine , chlorine , or bromine and
U1 denotes hydrogen or nitro ,
U2 and U3 independently denote hydrogen or Ci-Cε alkyl, optionally substituted by hydroxy, halogen, cyano, hydroxysulfonyl or a radical of the formula -S02-U, where U has the meaning stated above, and optionally interspersed by 1 or 2 non-adjacent oxygen atoms, imino groups or C1-C4 alkylimino groups, or
U2 and U3 form, together with the interconnecting nitrogen atom, a pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or N-(Cι-C4 alkyl )piperazinyl radical, or
U2 denotes a radical of the formula
Figure imgf000008_0002
in which the rings B1 and B2 may be monosubstituted or disubsti- tuted by hydroxysulfonyl and/or benzoanellated, and ring B2 may independently be monosubstituted or disubstituted by chlorine, nitro, C1-C4 alkyl, C1-C4 alkoxy, cyano, carboxyl, acetylamino, hydroxysulfonylmethyl or a radical of the formula CH2-S02-U,
S02-U, NH-CO-U, or NU2-CO-NU2-L-S02-U, in which U and U2 have the aforementioned meanings and L stands for C2-C6 alkene, optionally εubstituted by hydroxy, chlorine, cyano, carboxyl, C3.-C4 alkoxy- carbonyl , C1-C4 alkanoyloxy or εulfato and optionally interεperεed by 1 or 2 non-adjacent oxygen atoms, imino groups, or Cχ-C4 alky- limino groups. 5
Suitable radicals U2 and U3 include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl , hexyl, or 2-methylpentyl .
10 Examples of other radicals U2 and U3 are hydroxy (C1-C4 alkyl) , such as hydroxymethyl , 1-hydroxyethyl-l , 2-hydroxyethyl-l , 1-hy- droxypropyl-1, 2-hydroxypropyl-l, 3-hydroxypropyl-l , 1-hydroxy- propyl-2, 2-hydroxypropyl-2 , 1-hydroxybutyl-l , 2-hydroxybutyl-l , 3-hydroxybutyl-l, 4-hydroxybutyl-l , l-hydroxybutyl-2 , 2-hydroxy-
15 butyl-2, l-hydroxybutyl-3, 2-hydroxybutyl-3 , 1-hydroxy-2-methyl- propyl-3, 2-hydroxy-2-methylpropyl-3 , 3-hydroxy-2-methylpropyl-3 , or 2-hydroxymethylpropyl-2.
Examples of other radicals U2 and U3 are cyanomethyl , cyanoethyl, 20 cyanopropyl, or cyanobutyl and also hydroxysulfonylmethyl, 2-hy- droxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, or 2- or 4-hy- droxyεulfonylbutyl .
The radical L is, eg, (CH2)2, (CH2)3, (CH2)4, CH(CH3)CH2, 25 CH(CH3)CH(CH3) , (CH2)5, or (CH2)6.
The radical L may also be, for example, (CH2) 0 (CH2) 2 , (CH2)30(CH2)2, (CH2)20(CH2)20(CH2)2, (CH2) 2S (CH2) 2 , (CH2) 3S (CH2) 2 , (CH2)2S(CH2)2S(CH2)2, (CH2)2NH(CH2)2, (CH2 ) 3NH (CH2) 2 , 30 (CH2)2NH(CH2)2NH(CH2)2,
(CH2)2N(CH2)2, (CH2)3N(CH2)2, (CH2) 2N (CH2) 2N (CH2 ) 2 ,
35 CH3 CH3 CH3 CH3
(CH2)2N(CH2)2, (CH2)3N(CH2)2, (CH2) 2N (CH2) 2N(CH2) 2,
4 . n0 CHO CHO CHO CHO
(CH2)2N(CH2)2, (CH2)3N(CH2)2 or (CH2) 2N (CH2) 2N (CH2) 2 -
45 CH3C0 CH3C0 CH3CO CH3C0 Y in formula I corresponds to the radicals NR5R6, OR7, SR8, or S0R9 or a group that is suitable as a leaving group under the conditions of nucleophilic, aromatic substitution, the definitions of R5 to R9 being the same as those stated above. In the case of the radical NR5R6, R5 and R6 can be the same or different.
Any of the groups that are known to the person skilled in the art as being suitable therefore, may function as leaving groupε . Thus, for example, aliphatic or aromatic sulfonic acid deriva- tives, and also the aliphatic sulfonic acid derivatives partially or completely substituted by fluorine are suitable for this purpose.
Examples of Y as a suitable group to function as a leaving group under the conditions of nucleophilic, aromatic substitution, are
H3C S 0 F3C 0 F3C CH2 S 0
0 0 0
FqgCi-.4 0
Figure imgf000010_0001
0 0
Figure imgf000010_0002
Mention may also be made here of fluorine, chlorine, bromine, or the group
Figure imgf000010_0003
When Y is equivalent to the substituents S0 -CH=CH2 or S02-C2H4Q
(Y corresponds in such cases to S02R9 where R9 is a vinyl group and the group -C2H4Q respectively) , this should be regarded, for the purposes of the invention, as a group containing an active site or the precursor of an active site. The remaining radicals R1 to R8 can, but need not, be further groups containing an active site or the precursor of an active site.
Preferred reactive dyes of the invention are those in which X de- notes N02 •
Further preferred reactive dyes, also in respect of the aforementioned preferred embodiment, are those in which Y denotes SR8, S02R9- or a group that is suitable for use as a leaving group un- der the conditions of nucleophilic, aromatic εubεtitution.
We particularly claim reactive dyes of formula I and aforementioned preferred embodiment relating to when X denotes N02 , in which Y correspondε to SR8, S02R9, fluorine, chlorine, bromine or a group
Figure imgf000011_0001
fluorine being particularly preferred.
The preεent invention also relates to the use of the reactive dyes of the invention and to their preferred embodiments for dyeing εubstrates containing nucleophilic groups.
Such subεtrateε comprise, for example, a great variety of grades of cellulose products, such aε textileε based on cotton, paper for the production of newspaperε and magazines, cellulosic material for, say, sanitary purposeε, and wooden productε, for exam- pie for the production of furniture, hideε, such as leather, and animal skins, also human skin, for example when applying temporary tattoos, and human hair.
The reactive dyes of the invention and their preferred embodi- ments are preferably used for dyeing substrates containing hydroxy, mercapto, amino, and/or imino groups.
In particular, the reactive dyes of the invention and their preferred embodiments are uεed for dyeing keratinic fiberε, of which animal or human hair is particularly εignificant.
The preεent invention alεo relateε to compoεitionε containing at least one reactive dye of the invention.
The reactive dyes of the invention are usually employed in diε- εolved form. For preferred cosmetic applications the reactive dyes are dissolved in an aqueous, cosmetically acceptable medium. In this aqueous cosmetically acceptable vehicle the pH varieε between pH 3 to pH 11, more preferably pH 6 to pH 11. It iε set to the desired value by meanε of inorganic or organic baεeε, εalts of weak acids, or buffers. By way of example there can be men- tioned ammonia, ammonium, potassium, or sodium carbonate, sodium hydroxide, mono-, di- or tri-ethanolamine, disodium hydrogenphos- phate, sodium citrate, or sodium borate.
The reactive dyes are present in said compositions in concentra- tions of from 0.01 to 10 wt%, based on the total weight of the composition.
Common auxiliaries in compositions for hair coloration are anion- ic, cationic, non-ionic, or amphoteric surface-active compounds or mixtures thereof . Exampleε of surface-active compound are soapε, alkylbenzene sulfonates, alkyl naphthaleneεulfonateε, εul- fateε, fatty alcohol polyglycol εulfateε, and εulfonates of fatty alcohols, quarternary ammonium saltε, εuch aε trimethylcetylamo- nium bromide, cetylpyridinium bromide, quaternium 1 to X (INCI) , cocoyltrimethylammonium methylsulfate (INCI) , hydroxyethyl cetyl- dimomium phosphateε (INCI) , cetyltrimethylammonium chloride, optionally oxyethylenized fatty acid ethanolamides , polyoxyethyle- nized acids, alcohols, and amines, polyglycerolized alcohols, polyoxyethylenized or polyglycerolized alkyl phenols, and also polyoxyethylenized alkyl sulfates. The surface-active compounds are preεent in the compositions of the invention in a concentration of from 0.5 to 40 wt%, based on the total weight the preparation.
Other conventional auxiliaries are organic solvents acting as so- lubilizing agents, eg, C1-C4 alcohol such as ethanol and isopro- panol, glycolε, glycol etherε, εuch aε ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol , or 2-butoxyethanol, and alεo glycerol . Theεe εolventε are uεually present in a con- centration of 0 - 40 wt%, based on the total weight of the composition.
In order to εimplify handling of the compoεitions of the invention, thickeners are usually added as auxiliarieε. Common thick- enerε are celluloεe derivatives, such as methyl, hydroxymethyl , hydroxyethyl, hydroxypropyl , or carboxymethyl cellulose, εodium alginate, gum arabic, gum xanthan, gum traganth, acrylic acid polymerε, polyvinylpyrrolidone, poly (vinyl acetate-co-crotonic acid)s, poly (vinyl acetate-co-vinyl pyrrolidone) s, poly (butylvi- nyl ether-co-maleic anhydride) ε, or poly (methylvinyl ether-co-maleic anhydride) ε. Inorganic thickener, εuch aε bentonite, are alεo εuitable. Theεe thickenerε are usually employed in a con- centration of up to 5 wt%, based on the total weight of the composition.
Hair-care compositions which are to be used in the form of gels alεo contain gel-forming substances, such as carbomers (INCI). To acquire certain care-promoting properties, the compoεitionε may additionally contain cationic polymerε and silicone compounds. Suitable cationic polymers are, for example, polyquaternium 1 to x (INCI) , copolymers of vinyl pyrrolidone/vinyl imidazolium salts (Luviquat® FC, Luviquat® HM; , sold by BASF Aktiengesellschaft, udwigshafen) , copolymerε of vinyl pyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethyl εulfate (Luviquat PQ 11) ; cationic cellulose derivatives (polyquaternium 4 and 10) , acryla- mide copolymers (polyquaternium 7) and cationic guar gum deriva- tiveε, eg, guar hydroxypropyltriminium chloride (INCI). Suitable εilicone compoundε are, for example, alkyl polyεiloxaneε, poly- aryl εiloxaneε, polyarylalkyl siloxanes, polyether siloxaneε, or silicone resinε.
Further conventional auxiliaries are mild antioxidants that do not react with the dyes, penetrating agents, εequeεtering agents, buffers, perfume oils, light-stabilizing agentε (UV-A and UN-B filters) , preservatives, shampooε, and active substanceε εuch aε (d(+) -pantothenyl alcohol, biεabolol and vitamins, eg, vitamins A, C, and E.
The compoεitionε of the invention can be used in liquid form, usually thickened, as a cream, paste, gel, or any other εuitable form.
The hair colouring compoεitions of the present invention may, in addition to the dyes discussed herein above include other nonoxi- dative, oxidative and other dye materials. Optional nonoxidative and other dyeε suitable for use in the hair colouring composi- tions and processes according to the present invention include demi-permanent, semi-permanent, temporary and other dyes. Νon-ox- idative dyes as defined herein include the so-called "direct action dyes", metallic dyeε, metal chelate dyeε, fibre reactive dyes, acid dyes, baεic dyeε, non-ionic dyeε, anionic dyeε, ca- tionic dyeε, HC dyeε and other εynthetic and natural dyes.
Oxidative hair colouring agents to be uεed in the compoεitions herein are typically, but without intending to be limited thereby, oxidative hair colouring agents, consiεting eεsentially of at least two components, which are collectively referred to as dye forming intermediates (or precursorε) . Dye forming intermediates can react in the presence of a εuitable oxidant to form a coloured molecule. The dye forming intermediates uεed in oxidative hair colorantε include: aromatic diamineε, aminophenols, various heterocycleε , phenols, naphthols and their various diami- nobenzene or its derivatives.
The hair colouring compositionε may alεo comprise at least one oxidising agent, which may be an inorganic or organic oxidising agent .
The oxidising agent is preferably present in the colouring composition at a level of from about 0.01% to about 20%, more preferably from about 0.01% to about 10%, more preferably from about 1% to about 6% by weight of the compoεition. A preferred oxidiε- ing agent for uεe herein iε an inorganic peroxygen oxidising agent.
In the preferred application, a hair-care composition is applied to the hair and allowed to act thereon over a period of from 5 to 50 minutes and preferably from 10 to 30 minutes, after which the hair is rinsed and optionally washed with a conventional shampoo.
Dyeing can be accelerated by using the composition in a warm state or by applying heat externally, or intensified if the period of action is not εhortened. Preferably, temperatures ranging from 20° to 40°C are used.
The reactive dyes of the invention yield level dyeings and cover even white hair well. The dyeingε εhow good faεtneεε to light, washing, weathering, and abrasion, as external influences.
Generally reactive dyes, by reason of their different dyeing mode, make it posεible to do without H202 as oxidizing agent in the dyeing procesε. Particularly advantageous is the fact that the shade iε determined by the dye and iε not developed in the hair, which simplifies the preparation of dyestuff blendε and the production of various shades .
Example la:
Production of 2-hydroxyethyl-2 ' -aminoethylsulfone:
245 g (2.4 mol) of 96 % strength sulfuric acid were added to 400 g of ice. 484 g (4 mol) of 2-aminoethyl-2 ' -hydroxyethylsul- fide (produced aε deεcribed in J.R.Lotz, B. P. Block, W.C.Ferne- lius, J. Phys . Chem. , 63 (1959), pp 541) were then added dropwise within a period of 30 minuteε, during which proceεε the temperature roεe to 45°C. 1 g (0.004 mol) of εodium tungstate (sold by Merck KGaA, Darmstadt) and 10 g of citric acid (sold by Merck KGaA, Darmstadt) were then added, and the mixture was adjuεted to pH 4.5 with 20 % strength sodium hydroxide solution and heated to 80°C. 953 g (8.4 mol) of a 30 % strength hydrogen peroxide solu- 5 tion were added dropwise within a period of 3 hourε while the pH waε kept between 4.5 and 5 with 20 % εtrength sodium hydroxide solution.
The peroxide excess was destroyed with sodium sulfite, the solu- 10 tion concentrated in a rotary film evaporator, and there were added, portionwiεe, a total of 1500 mL of ethanol. After each shot of ethanol, the mixture was concentrated, and finally the remaining oil- was caused to crystallize by the addition of 200 mL of methanol. There were obtained 775 g (3.85 mol) of 2-hydroxye- 15 thyl-2 ' -aminoethylsulfone .
Example lb:
Figure imgf000015_0001
25 21 g (0.1 mol) of 1, 5-difluoro-2 , -dinitrobenzene (εold by Clari- ant (Deutschland) GmbH, Frankfurt) and 0.5 g of Emulan® EL (sold by BASF Aktiengesellschaft, Ludwigshafen) were stirred in 30 mL of water and 70 mL of acetone. To this mixture there were added dropwise, at room temperature, 33.1 g (0.1 mol) of 2-hydroxye-
30 thyl-2 '-aminoethylεulfone (produced aε described in Example la) in the form of the sulfate. During this operation, the pH was kept between 6 and 7 by εimultaneouε addition of εodium hydrogen- carbonate. Stirring was continued over a period of 2 hours, and the resulting precipitate was then filtered off. Following dry-
35 ing, there were obtained 112 g of the stated compound. The structure was determined by NMRεpectroscopy. Example lc:
Figure imgf000015_0002
45 27 g (0.08 mol) of the hydroxy compound of Example lb were added to 80 mL of 96 % strength sulfuric acid at from 0° to 5°C. Stirring was continued over a period of two hours at from 0° to 5°C and then for a further 15 hours at room temperature. The reaction mixture was added to 100 mL of ice water such that the temperature did not exceed 5°C . The mixture was heated to room temperature and the product εalted out with 60 g of potaεεium chloride. The product of the above formula was filtered off in vacuo and dried in vacuo at 25°C. There were obtained 39.8 g of the product having a purity of 98.4 % (HPLC % by area) .
Example Id:
Figure imgf000016_0001
20 g (0.04 mol) of the sulfuric acid half-ester of Example 1°C were added to 200 mL of water. The pH was adjusted to from 8.5 to 9, and kept at said value, with solid soda. The batch was then stirred for 2 h at 35°C and for a further 15 h at room temperature. The batch was then set to pH 7 with 20 % strength hydrochloric acid and the precipitated product filtered off. Following vacuum drying at 25°C, there were obtained 22.8 g of a product of the above formula. The purity was 95.4 % (HPLC % by area).
Example 2a:
Figure imgf000016_0002
41 g (0.1 mol) of the ca 73 % strength fluorine compound of Exam- pie lb were added to 250 mL of water to which 0.1 g of Emulan EL had been added. There were then added 14.8 g (0.12 mol) of nicotinic acid (sold by Fluka Chemie AG, Buchs, Switzerland) and the mixture was adjusted to pH 6 to 7 with sodium hydrogencarbonate. The mixture was heated to 60°C over a period of 9 hours, the pH then raised to 7.5, and stirring was continued for a further 8 hourε . The precipitated product of the above formula was filtered off and dried in vacuo at 35°C. The yield was 36.3 g.
Example 2b:
Figure imgf000017_0001
15 g (0.05 mol) of the hydroxy compound of Example 2a were added to 100 mL of 96 % εtrength εulfuric acid at from 0° to 5°C within a period of 30 minuteε . Stirring was continued over a period of two hours at from 0° to 5°C and then for a further 15 hours at room temperature. The reaction mixture was added to 110 mL of ice water such that the temperature did not exceed 5°C . The product of the above formula was filtered off in vacuo and dried in vacuo at 25°C. There were obtained 16.8 g of the product having a purity of 100 % (HPLC % by area) .
Example 3
Figure imgf000017_0002
29.2 g (0.1 mol) of p-aminobenzenesulfatoethyl sulfonate (sold by Sajjan, Mumbai, India) were dissolved in 250 mL of water, the pH being adjusted to 4 with 10 % strength sodium hydroxide solution. There were introduced 0.5 g of Emulan® EL followed by 21 g
(0.1 mol) of 1, 5-difluoro-2, 4-dinitrobenzene. The pH was set to from 6 to 7, and kept at that value, with sodium hydrogencarbonate. Stirring was carried out for 5 hourε at 30°C. The precipitated product of the above formula waε filtered off and dried in vacuo at 35°C. The yield waε 31.0 g.
Example 4a:
Figure imgf000017_0003
37 g (0.1 mol) of the fluorine compound of Example lb were added to 250 mL of water and 0.2 g of Emulan® EL were added. 11 g (0.12 mol) of thioglycollic acid (sold by Merck KGaA, Darmstadt) were then added and the mixture was set to a pH of 6.5 with sodium hydrogencarbonate. The batch was heated to 40°C and stirring was continued at this temperature over a period of 6 hours. Following cooling, the precipitated product waε filtered off and dried in vacuo at 35°C. The yield waε 33.9 g. Example 4b:
10
Figure imgf000018_0001
15.0 g of the hydroxy compound of Example 4a were added to 100 mL of 96 % strength sulfuric acid at from 0° to 5°C and stirred at
20 this temperature over a period of two hours. During the following 17 hour stirring period, the temperature rose to from 20° to 25°C. The reaction mixture was added to 1000 mL of ice water and filtered. The filtrate was salted out with 15 g of potassium chloride, and the product was filtered off and dried in vacuo at 35°C.
25 The yield was 14.4 g of the compound of the formula shown above.
Example 5a:
Figure imgf000018_0002
35 41.0 g (0.1 mol) of the compound of Example lb were added to 250 mL of water and, following the addition of 0.1 g of Emulan EL, suεpended. 9.4 g (0.12 mol) of mercaptoethanol (εold by Merck KGaA, Darmεtadt) were then added and the pH waε εet to from 5.5 to 6 with sodium hydrogencarbonate. Stirring was carried out for
40 5 hours at 35°C, the mixture then cooled to room temperature, and the resulting thioether was filtered off. The oiεt intermediate product (96 g) waε εtirred in 500 mL of water, and 0.3 g of sodium tungεtate (εold by Merck KGaA, Darmεtadt) were added, and the mixture was heated to 80°C. 63 g of 30 % strength hydrogen
45 peroxide solution were added dropwise at this temperature within a period of 3 hours. On cooling to room temperature, the sulfone was salted out with sodium chloride, filtered off, and dried. There were obtained 42.3 g of the compound of the formula shown above (HPLC: 96.7 % by area).
Example 5b:
Figure imgf000019_0001
10.0 g of the hydroxy compound of Example 5a were added to 100 mL of 96 % strength sulfuric acid at from 0° to 5°C within a period of 45 min and εtirred at this temperature over a period of two hours. During the following 17 hour stirring period, the temperature rose to from 20° to 25°C. The reaction mixture waε slowly added to 1000 mL of ice water such that the temperature did not exceed 5°C.
The pH was set to 5 by the addition of calcium carbonate at from 5° to 10°C. The precipitated calcium sulfate was filtered off, and the filtrate set to pH 4.5 with acetic acid and concentrated to drynesε at 30°C in the vacuum of a rotary film evaporator. Further drying was carried out at room temperature in a vacuum drying cabinet. The yield of the product of the formula shown above was 20.3 g (HPLC 93.4 % by area).
Coloration example:
1.25 g of the reactive dye of Example 1°C were disεolved in 25 mL of water and the pH waε adjuεted to 7 with εodiu hydrogenphoε- phate. A bleached skein of human hair (2 g) was immersed in the solution heated to 36°C and the solution allowed to act at this temperature over a period of 20 minutes. The hair was then rinsed with water and dried in air. The hair waε dyed an intense yellow. Under the same conditions, intense yellow hair colorationε were likewiεe obtained uεing the reactive dyeε of the invention de- εcribed in Examples Id, 2b, 3, 4b, and 5b.
Formulation examples:
A) Hair-coloring cream
phase I:
1.5g ceteareth-6 (and) stearyl alcohol (INCI) 1.5g ceteareth-25
6. Og cetearyl octanoate
3. Og cetearyl alcohol
phase II :
2g reactive dye of formula 1°C
2g propylene glycol
84g dest. water
q.s. citric acid/triethanolamine for adjustment to pH 7
q.s. preserving agent
phase III:
q.s. perfume oil
The ingredients were dissolved at 60°C, and phase I was added to phase II. After cooling to 30°C, phase III waε added. A bleached skein of human hair (2 g) was treated with 0.5 g of the dyeing creme, which waε allowed to act for 20 min. A water- rinεe followed. There waε obtained a hair coloration aε described in the coloration example.
B) Hair-coloring lotion
5 g reactive dye of formula lc
1.2 g Natrosol® 250 HR (sold by Aqualon/Hercules Inc. Wilming- ton, Delaware, US-A) , (hydroxyethylcellulose (INCI))
1 g propylene glycol
ad 100 g dest. water
q.s. preserving agent
A bleached skein of human hair (2 g) was treated with 0.5 g of the dyeing lotion, which was allowed to act for 20 min. A water- rinεe followed. There was obtained a hair coloration as described in the coloration example. C) Hair-coloring mousse
2g reactive dye of formula lc
3g Luviskol® VA 64 (εold by BASF Aktiengesellschaft, Ludwig- shafen) , (PVP/VA copolymer (INCI))
_0.45g ceteareth-25 (INCI)
0.10g dimethicone (INCI)
lOg propane/butane
ad lOOg dest. water
q.s. preserving agent
A bleached skein of human hair (2 g) was treated with 0.5 g of the hair-coloring mousse, which was allowed to act for 15 min, followed by a water rinse. In addition to the attainment of intense dyeing, the hair iε very easy to comb and has a well- groomed appearance. There was obtained a hair coloration as described in the coloration example.
D) Hair-coloring shampoo
5g reactive dye of formula lc
40g sodium laurylethersulfate (INCI) (Texapol® N 28;, sold by Henkel KGaA, Dusεeldorf)
lOg Tego® Betain L 7 (εold by Goldschmidt AG Degusεa AG, Duε- seldorf)
(cocamidopropyl betaine (INCI) )
2g Gluatin WQ (wheat germ protein)
ad lOOg dest. water
q.s. preserving agent
q.s. common salt as thickener The use of a hair-coloring shampoo makes it posεible to clean and dye the hair in one. A bleached εkein of human hair (2 g) waε treated with 0.5 g of the hair-coloring shampoo and after 1 min rinsed until no more foaming occurred. There was obtained a hair coloration as described in the coloration example.
E) Coloring paste
2g reactive dye of formula lc
7g titanium (IV) oxide
15g Aerosil (sold by Deguεsa AG, Dusεeldorf)
lOg Lutrol® F 127 (polyethylene glycol, εold by BASF Aktien- geεellεchaft, Ludwigεhafen)
ad lOOg dest. water
q.s. preserving agent
A bleached skein of human hair (2 g) was treated with 0.5 g of the hair-coloring paste, which waε allowed to act for 15 min, followed by a water rinse. There was obtained a hair coloration as described in the coloration example.
F) Hair-coloring shampoo
lOg reactive dye of formula lc
2.20g gum xanthan (Keltrol® T; , sold by Kelco Biopolymers, San Diego, California, US-A)
20. Og sodium laurylethersulfate
2.50g olein diethanolamide
0.10g ' Trilon® B (sold by BASF Aktiengesellschaft, Ludwigεhafen)
ad lOOg deεt. water
q.s. preserving agent
25 g of the coloring paste were mixed with 25 mL of deεt. water, and a bleached εkein of human hair (2 g) waε treated with this coloring shampoo, which waε allowed to act for 20 min. A water- rinse followed. There was obtained a hair coloration as described in the coloration example.
G) Oxidative hair colouring formulation
I. Dye cream emulsion weight % in uεe
q.ε. water
24.75 emulsion base
4.0 reactive dye of formula 3
4.125 30% aqueous ammonium hydroxide
II. Emulsion base weight % in use
q.s. water
1.5 ceteareth 25
2.25 cetyl alcohol
2.25 stearyl alcohol
0.06 sodium benzoate
0.07 phenoxyethanol
0.08 benzyl alcohol
0.02 tetrasodium EDTA
2.0 silicone (DC Q2-8220 from Dow Corning)
III. Hydrogen peroxide emulsion base weight % in use
q.s. water
4.2 ceteareth 25
6.25 cetyl alcohol 6.25 stearyl alcohol
IV. Hydrogen peroxide cream weight % in use
36 hydrogenperoxide emulsion base
17.7 35% hydrogen peroxide
q.s. water
The dye emulsion base is prepared by a one pot process as follows :
1. Add water to vessel. Heat to above the melt temperature of the fatty alcohols with agitation.
2. Add fatty alcoholε and any ethoxylated fatty alcoholε, e.g. ceteareth-25, cetyl, εtearyl and steareth-2, and allow to melt. Increase agitation.
3. Continue mixing with shear.
4. Beginn cooling with shear adding preservativeε at appropriate temperature.
5. During cooling add εilicone with mixing until homogeneous.
6. Cool to room temperature .
The hydrogen peroxide cream is also prepared similarly using a one pot proceεε.
All 3 componentε are thoroughly mixed before application to hair for a 30 minute period, followed by a rinεing with water and dried. A hair colouration as described in- the hair colouration example was obtained.

Claims

Claims
1. A reactive dye of formula I
Figure imgf000025_0001
in which the variables independently denote
X hydrogen, N02 , or NR3R4,
Y NR5R6, OR7, SR8, or S02R9 or a group suitable as leaving group under the conditions of nucleophilic, aromatic sub- εtitution,
R1 to R9 independently hydrogen, Ci-Cs alkyl, C2-Cs alkyl, in which non-adjacent CH2 groupε can be replaced by oxygen atoms, imino groups, or C1-C alkylimino groups, and/or CH2 groupε may be replaced by carbonyl groupε, C -Ce al- kenyl, or a group containing an active site or the precursor of an active εite,
with the proviεo that at leaεt one of the radicalε R1 to R9 iε a group containing an active site or the precursor of an ac- tive site.
2. A reactive dye as defined in claim 1, in which X denotes N02.
3. A reactive dye as defined in claim 1 or claim 2, in which Y denotes SR8, S0R9, or a group that is suitable as a leaving group under the conditions of nucleophilic, aromatic substitution.
4. A reactive dye as defined in claim 1 or claim 2, in which Y denotes SR8, S02R9, fluorine, chlorine, bromine or a group
Figure imgf000025_0002
5. A reactive dye as defined in claim 1 or claim 2, in which Y denotes fluorine.
6. A method of using a reactive dye as defined in any of claims 1 to 5 for dyeing subεtrateε containing nucleophilic groupε.
7. A method of using a reactive dye as defined in claim 6 for dyeing subεtrateε containing hydroxy, mercapto, amino, and/or imino^ groups .
8. A method of uεing a reactive dye as defined in any of claims 1 to 5 for dyeing keratinic fiberε.
9. A method of using a reactive dye as defined in claim 8 for dyeing animal or human hair.
10. A composition whenever containing at least one reactive dye as defined in any of claims 1 to 5.
PCT/EP2002/002385 2001-03-05 2002-03-05 Novel reactive dyes and the use thereof for dyeing substrates containing nucleophilic groups Ceased WO2002070610A2 (en)

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JP2002570639A JP2004530001A (en) 2001-03-05 2002-03-05 A novel reactive dye and its use for dyeing nucleophilic group-containing substrates
DE60205466T DE60205466T2 (en) 2001-03-05 2002-03-05 NEW REACTIVE PURPOSES AND THEIR USE FOR DYING SUBSTRATES WITH NUCLEOPHILIC GROUPS
US10/469,600 US7108727B2 (en) 2001-03-05 2002-03-05 Reactive dyes and the use thereof for dyeing substrates containing nucleophilic groups
AU2002308234A AU2002308234A1 (en) 2001-03-05 2002-03-05 Novel reactive dyes and the use thereof for dyeing substrates containing nucleophilic groups
EP02748331A EP1368433B1 (en) 2001-03-05 2002-03-05 Novel reactive dyes and the use thereof for dyeing substrates containing nucleophilic groups
AT02748331T ATE301692T1 (en) 2001-03-05 2002-03-05 NEW REACTIVE DYES AND THEIR USE FOR COLORING SUBSTRATES WITH NUCLEOPHIL GROUPS

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BE790986A (en) 1971-11-05 1973-05-07 Farwerke Hoechst A G Vormals M REACTIVE MONOAZOIC DYES
US4036825A (en) 1971-11-05 1977-07-19 Hoechst Aktiengesellschaft Monoazo reactive dyestuffs
DE2331518A1 (en) 1972-06-23 1974-01-10 Ciba Geigy Ag NEW COLORS, THEIR PRODUCTION AND USE
CH586739A5 (en) * 1973-10-17 1977-04-15 Hoechst Ag
EP0107614B1 (en) 1982-09-30 1987-10-21 Ciba-Geigy Ag Reactive dyes, their preparation and their use
DE3502991A1 (en) 1984-07-20 1986-01-30 Hoechst Ag, 6230 Frankfurt SUBSTITUTED PHENYLOXETHYL SULPHONES AND METHOD FOR THE PRODUCTION THEREOF
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US4799934A (en) * 1987-10-30 1989-01-24 Clairol Incorporated Sulfur-containing nitroaminobenzene dyes, process and hair dye compositions
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CA2148535A1 (en) * 1994-06-24 1995-12-25 Mu-Ill Lim 5-mercapto-2-nitro paraphenylenediamine compounds and hair dye compositions containing same
DE19712649C1 (en) * 1997-03-26 1998-06-18 Wella Ag Colourant for keratinous fibres based on cyclic oxo-en-di:ol giving intense colour at moderate temperature
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