Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/35—Ketones, e.g. benzophenone
  • A61K8/355—Quinones
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
  • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/002—Dyes with anthracene nucleus not condensed with any other ring containing onium groups
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/16—Amino-anthraquinones
  • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
  • C09B1/207—Dyes with amino groups and with onium groups
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/16—Amino-anthraquinones
  • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
  • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
  • C09B1/262—Dyes with no other substituents than the substituted amino groups
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/16—Amino-anthraquinones
  • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
  • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
  • C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
  • C09B1/285—Dyes with no other substituents than the amino groups
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/16—Amino-anthraquinones
  • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
  • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
  • C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
  • C09B1/325—Dyes with no other substituents than the amino groups
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
  • C09B1/501—Amino-hydroxy-anthraquinones; Ethers and esters thereof containing onium groups
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
  • C09B1/51—N-substituted amino-hydroxy anthraquinone
  • C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
• • 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
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
  • C09B1/51—N-substituted amino-hydroxy anthraquinone
  • C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
  • C09B1/5155—N-alkyl, N-aralkyl or N-cycloalkyl derivatives only amino and hydroxy groups
• • 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
  • C09B62/78—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 with other reactive groups
  • C09B62/80—Anthracene dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/30—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts
  • D06P3/3033—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts using basic dyes

Definitions

• n 2 or 3
• R, R together with the adjacent nitrogen are as previously defined;
• NZ is a heterocyclic radical
• A is an anion
• This invention relates to dye stuffs and to their use in dyeing live human hair with derivatives of anthraquinone.
• the first class has a substitution in the No. 1 position and a second substitution in other positions on the nucleus.
• the second class has a hydroxy group in the No. 4 position and a substitution in the No. l position on the nucleus.
• the third class has a single substitution in the No. 2 position on the nucleus.
• the fourth class has a single substitution in the No. 1 position on the nucleus.
• a process for dyeing of hair and like keratinous materials comprises applying thereto one or more dyestuffs of the formula:
• X 0 NH-Z NHZ l n 1 X 0 X in which one X is an NHZ radical and the other two are hydrogen and Z represents a group of the formula in which R and R are the same or different and represent lower alkyl radicals or together with the adjacent nitrogen represent a saturated mononuclear heterocyclic radical and n is an integer from 2 to 6, or quaternary ammonium salts of such dyestuffs.
• the dyestuffs of Formula 1 in which R and R together with the adjacent nitrogen represent a saturated mononuclear heterocyclic residue and their quaternary ammonium salts are new compounds and as such within the'scope of the invention.
• Especially valuable dyestuffs of Formula 1 are those in which n is 2, 3 or 6 and R and R are each a lower alkyl radical or together with the adjacent nitrogen represent a piperidino or morpholino radical.
• Especially valuable quaternary ammonium salts of such dyestuffs are the bis(methyl methosulphates) and the bis(benzyl chlorides).
• the dyestuffs of Formula 1 and the quaternary ammonium salts dye hair excellently at room temperature, and, because they contain two tertiary or quaternary nitrogen atoms, they possess a high affinity for the hair over the wide pH range of 3 to 10, and especially 4.5 to 9.5, depending upon whether their tertiary or quaternary derivatives are employed.
• the aforesaid dyestuffs are very soluble in water, because of the number of basic groupings they contain, and it is thus possible to obtain aqueous dye solutions Whose concentration may exceed 10%.
• the dyestuffs have the further advantage that the dyeing effects obtained with them are relatively fast to sunlight.
• their fastness is approximately equal to that of standard 4 on the range established by the Association for the Determination of the Fastness of Dyeing Effects and Textile Prints (see Code de Solidite, pub-- lished by the Groupement dEtudes Continental Europeen, 2nd Edition (1958), p. 31), when this standard and the dyeings obtained in accordance with this invention are simultaneously. exposed to sunlight under similar conditions.
• the aforesaid range of standards extends from 1 to 8, 8 representing the greatest degree of fastness.
• Some of the aforesaid dyestuffs are particularly suitable, as they give off no unpleasant odor when used in hair dyeing.
• the present invention provides, as a further feature, hair dyeing compositions containing one or more dyestuffs of Formula 1 or quaternary ammonium salts thereof in an aqueous solution having a pH between 3 and 10, preferably 4.5 and 9.5.
• compositions may comprise only dyestuffis of 5 melts at 157 C.
• compositions may be very readily Prepared by w Examp 1e g; b1?(methyimorpholmlumethylammo) qumone]d1methosulphate CllSSlV1Ilg in water one or more dyestuffs of Formula 1 or quaternary ammonium salts thereof optionally mixed E H with other dyes and adjusting the pH to the desired value 0 NH-CHz-CHr-N within the range 3 to 10.
• these dyeing solutions various products usually employed in the cosmetics field, such as wetting and dispersing 2(S0rGHr) agents, emollients, and perfumes.
• compositions of the invention may be applied to I the hair in the usual manner, preferably at room temper- 0 NH-CIL-Clih-N ature.
• concentration of the dye may vary within wide HrCL/II limits, depending upon the depth of dyeing aimed at.
• the dyestuffs of Formula 1 may be obtained from This product is readily obtained from the correspondquinizarin or 1,5 or 1,8-dichloroanthraquinone by the acing base by the action of methylsulphate, using toluene as tion of a diamine of the formula: solvent, under reflux in the usual way. On recrystallization from methanol, it melts with decomposition at 240- 245 c. NHz-(CHzh-N Analysis.-Calculated: N percent, 7.82. Found: N per- (2) cent 7.77-7.60.
• n, R and R' are as hereinbefore defined.
• Examp 1e of PIS (fl'morpholmo' y am1no)anthraqurnone The tertiary anuno anthraqulnone derivatives thus obtained may be quaternized very readily in the usual man- CHFCH' ner with a quaternizing agent such as methylsulphate or o NH-cm-om-N 0 an alkyl or benzyl halide, in the presence or absence of H GHrCQ, an appropriate solvent such as toluene.
• a quaternizing agent such as methylsulphate or o NH-cm-om-N 0 an alkyl or benzyl halide
• Example VI Preparation of [1,4-bis (methylmorpholiniumaminohexyl anthraquinone] dimethosulphate C Hr-C H: 0 Nil-(0H2)
• This product is obtained from the above-described cor- CHPCH responding tertiary base by quaternization under reflux Y CHz-CgHs with methylsulphate in toluene. It is very hygroscopic and is therefore immediately employed without purification.
• This product is obtained in the usual way from the cOr- Water to 100 cc. responding base by the action of methylsulphate.
• This solution when applied under the same conditions recrystallized from alcohol, it melts at ZOO-201 C. with as in the foregoing example, gives an intense blue shade decomposition. to grey hair.
• Example XV The following mixture is prepared:
• Example XDC The following mixture is prepared:
• Example XXI The following mixture is prepared:
• This solution is applied to hair for 15 minutes in accordance with the above examples and colors it azure blue.
• Example XXIV The following mixture is prepared:
• Example XXV-Preparation of 1.4-(p-dimethylaminophenyl) amine anthraquinone This product is obtained on heating for 12 hours at 90 C. a mixture of leucoquinizarine, and excess of N,N-dimethyl-p-phenylenediamine, boric acid and water. At the end of the reaction, and before the passage of a current of air in order to oxidize the formed leuco derivative, the product is dried, then by washing the crude product thus obtained with alcohol, the excess N,N-dimethyl-p-phenylene diamine is eliminated. The crude product thus obtained is purified and recrystallized in chlorobenzene melting at 275 C.
• Example XXVL-Preparation of bis-methyl[l,4-p-trimethylanalinium)amino anthraquinone] sulphate This product is obtained starting with 1,4(p-dimethylaminophenyl)amino anthraquinone by reaction with methyl sulphate for 1 hour at 80 C. in solution in nitrobenzene. The corresponding quaternary is precipitated and can be isolated by drying. The product obtained decomposes at 286-288 C.
• Example XXVII.Preparation of 1.5-(p-dimethylaminophenyD-amino anthraquinone A mixture of 28.5 g. of 1,5-dichloroanthraquinone and 110 g. of N,N-dimethyl-p-phenylene-diamine are heated for hours at 100 C. They are cooled to 50 C. and dried. The crude product obtained is purified by washing with boiling water, and recrystallized in a chloroform-benzene mixture.
• Example XXVIII Preparation of bis-methyl-[1,5-(ptrimethylaniline)-amino anthraquinone] sulphate This product is obtained by reacting 1,5-(p-dimethylaminophenyl) amino anthraquinone with methyl sulfate for 1 hour at refiuxtemperature in a toluene solution. The corresponding quaternary is dried.
• Example XXX-Preparation of bis-methyl [l-p-trimethylaniline)-4 (p aminoethylrnorpholinium) amino anthraquinone] sulphate This product is obtained by quaternization of liaminol-p-dirnethylamino-phenyl) -4-B-morpholinoethyl)] anthraquinone, with the help of methyl sulphate, in a chloroform solution.
• Example XXXI The following mixture is prepared:
• n is from 2 to 6 and R and R' are the same or different and each represents a lower alkyl group, for example, methyl or ethyl, or together with the adjacent nitrogen atom represent a saturated mononuclear heterocyclic radical, especially a morpholino or piperidino radical, and their acid addition and quaternary ammonium salts, have high aflinity for keratinic fibres over a very wide pH range.
• the invention accordingly provides compositions for the dyeing of hair comprising a dyestutf of Formula 3 or an acid addition or quaternary ammonium salt thereof.
• dyestuffs of Formula 3 those in which R and R together with the adjacent nitrogen represent a saturated mononuclear heterocyclic radical are novel per se and as such within the scope of the invention.
• tertiary amino group in a dyestutr' of Formula 3 When the tertiary amino group in a dyestutr' of Formula 3 is quaternized, it has preferably the following formula:
• R represents a lower alkyl radical especially methyl
• A represents an anion such as a halogen or, especially, a methosulphate ion.
• dyestuffs of Formula 3 there may be mentioned the following substances: l-(B-diethylaminoethylamino)-4-hydroxyanthraquinone; 1 ('y diethylaminopropylamino) 4 hydroxyanthraquinone; l-(fl-morpholinoethylamino) 4 hydroxyanthraquinone; 1-(7- piperidinopropylamino) 4 hydroxyanthraquinone, and their acid addition and quaternary ammonium salts.
• the dyestufls of Formula 3 have the advantage that they are highly water-soluble over a very wide pH interval, e.g. from 3 to 9, and that they have solubilities reaching about 8%. In addition, they have great aflinity for hair and are very resistant to light. They withstand perfectly the presence of ingredients ordinarily incorporated in dyeing solutions, and such ingredients, especially wetting agents, may be added to the compositions of the invention.
• dyeing solutions which contain only compounds possessing morpholino or piperidino radicals do not have an unpleasant odor, unlike dyeing solutions containing other anthraquinone dyestuffs of similar formula.
• the dyes of Formula 3 also have the advantage that they can be mixed without difliculty with other dyestuffs generally employed in hair dyeing, for example nitro derivatives of the benzene series and other anthraquinone dyestulfs.
• compositions of the invention are readily prepared by simple dissolution in water of one or more of the dyestuffs of Formula 3, in the presence or absence of other dyestuffs, and, where necessary or desirable, introducing into the solution other ingredients generally employed in such compositions such as emollients, perfumes and especially wetting agents.
• the dyestuff concentration may vary within wide limits and its precise value will depend upon the result desired.
• Hair-dyeing with the compositions of the invention is carried out in the usual way by applying the dye solution, preferably at normal temperature, to the hair until it is dyed.
• the compounds of Formula 3 may be prepared from 1,4-dihydroxyanthraquinone, also known as quinizarine, by the action of an N,N-dialkylalkylenediamine of the formula:
• the quaternization of the tertiary amino compounds thus obtained is carried out in the usual way by reaction with a quaternizing agent, such as methyl sulphate or an alkyl halide, in the presence or absence of an appropriate solvent.
• a quaternizing agent such as methyl sulphate or an alkyl halide
• Example XXXIV Example XXXV (4 hydroxyanthraquinonyl 1 aminoethyDmethylmorpholinium methosulphate is readily obtained from the base described in Example XXXIV by the action of methyl sulphate, using toluene as solvent and refluxing the mixture in the usual way.
• the product obtained melts with decomposition between 200 and 205 C. Analysis shows a nitrogen content of 5.73%, compared with a calculated content of 5.75%.
• Example XXXVI 1 ('y piperidinopropyl)amino 4 hydroxyanthraquinone is obtained by refluxing for seven hours with stirring a mixture of 0.15 g./mol. of quinizarine and 0.15 g./mol. of aminopropylpiperidine in 200 cc. of toluene. After evaporation of the solvent, the product is recrystallized a number of times from hexane and then from alcohol, and then melts at about C. and analyses as follows:
• Example XXXV II For the preparation of (4-hydroxyanthraquinonyl-1- aminopropyl)-methylpiperidinium methosulphate, methyl sulphate is reacted with the corresponding base described in Example XXXVI using benzene as solvent with refluxing in the usual way. The product obtained melts with decomposition at a temperature of -163 C.
• Example XL The following mixture is prepared:
• Example XLI The following mixture is prepared:
• composition dyes hair a violet color comparable with that obtained in Examples XXXVIII to XL when used as described in Example XXXVIII.
• the new dyestuffs of the invention have the formula:
• n is from 2 to 6 and R and R each represents a lower alkyl group, or together with the adjacent nitrogen represents a saturated mononuclear heterocyclic radical, and their acid addition and quaternary ammonium salts.
• R and R may be identical or different, and may be, for example, methyl, ethyl or propyl groups, or R and R, together with the adjacent nitrogen, may represent morpholino or piperidino radicals. It is preferred that R and R represent ethyl radicals or, together with the adjacent nitrogen, represent a morpholino radical, and n is 2 or 3.
• the group attached to the anthraquinone nucleus has preferably the following formula:
• R represents a lower alkyl radical, especially methyl
• A represents an anion, such as a halide or especially a methosulphate ion.
• anthraquinone derivatives falling within the scope of the present invention, there may be mentioned, inter alia, the following compounds: Z-(fl-diethylaminoethylamino)anthraquinone; 2 ('y diethylaminopropylamino)anthraquinone; and 2 ([3 morpholinoethylamino)anthraquinone; and their acid addition and quaternary ammonium salts.
• the dyestuffs of Formula 4 and their quaternary ammonium derivatives are very suitable as dyestuffs for dyeing hair, especially at ordinary temperatures.
• These dyestuffs have, owing to the presence of the tertiary or quaternary amino function, high affinity for hair over a very wide pH range, e.g. of 4.5 to 9, depending upon whether the tertiary or quaternary deriva tives are employed while, in addition, they possess good solubility in water.
• the dyeings obtained with these dyestuffs have, the additional advantage of being resistant to sunlight. Finally, the dyestuffs are fully compatible with the adjuvants gen erally present in dyeing solutions.
• the dyeings obtained on hair with the dyestuffs of the invention are generally yellow or golden-yellow. This is a considerable advantage because mixtures of the dyestuffs of Formula 4 with the red to blue-green dyestuffs, described in this application, can be used to obtain an interesting range of natural shades.
• compositions for dyeing hair which comprise a dyestuff of Formula 4 or acid addition or quaternary ammonium salt thereof.
• the compositions are generally in the form of aqueous solutions of pH 4.5 to 9 which are very easily prepared by simple dissolution in water of one or more of the new dyestuffs, with or without other dyestuffs.
• the solutions may also contain, where necessary, the adjuvants generally employed in compositions for dyeing hair, e.g. emollients, and perfumes, and especially wetting agents.
• the dyestuffs concentration in the dyeing solutions may vary within wide limits and the precise concentration chosen depends upon the result aimed at.
• Hair dyeing with the new compositions is carried out in the usual manner by applying them to the hair for an appropriate time, preferably at normal temperature.
• the new dyestuffs may be prepared by reacting, for example, B-chloro (or B-bromo)anthraquinone with an alkylenediamine of the formula R Hz 2)nN in which n, R and R are as hereinbefore defined, in the presence of pyridine.
• the quaternization of the tertiary anthraquinone derivatives thus obtained can be very simply carried out by reacting a quaternizing agent, such 15 as methyl sulphate or an alkyl halide, with the anthraquinone derivative containing the tertiary amino group, in the presence or absence of an appropriate solvent.
• Example XLIV-Preparation of 2-(B-diethylamin0ethy1) aminoanthraquinone A mixture of ,B-chloroanthraquinone (0.1 g. mol.) and N,N-diethylethylenediamine (0.4 g. mol.) in 50 cc. of pyridine is heated for 8 hours at 100-104 C. After cooling and evaporation of the excess pyridine, the crude product obtained is recrystallized from hexane. The desired product is thus obtained and melts at 122 C.
• Example XLV.Preparation of (Z-anthraquinonylaminoethyl)diethylmethylammonium methosulphate The tertiary amino dyestuff described in Example XLIV is reacted with methyl sulphate in the presence of benzene under reflux. After cooling, the desired quaternary ammonium salt precipitates as a yellow powder. It melts with decomposition at a temperature of 194- 196 C.
• Example XLV-I Preparation of Z-(y-dimethylaminO- propyl) aminoanthraquinone
• Example XLVIII Preparation of Z-(fl-morpholinoethyl) aminoanthraquinone
• Example XLIV Preparation of Z-(fl-morpholinoethyl) aminoanthraquinone
• Example XLIX.-Preparation of (2-anthraquinonylaminoethyl)-methylmorpholinium methosulphate This product is obtained from the tertiary amino dyestutf described in Example XLVIII, dissolved in chlorobenzene, by the action of methyl sulphate at an elevated temperature. After purification by recrystallization from hexane, the desired product is obtained, M.P. 228230 C. (dec.).
• Example L The following mixture is prepared:
• This solution is applied to blond hair and left in contact therewith for 10 to 15 minutes at ambient temperature, and the hair is then abundantly rinsed with water and dried. An intense golden tint is thus obtained.
• This solution when applied in the same way to white hair, colors it a light gold-blond.
• anthraquinone compositions have been proposed for dyeing hair. These have a disadvantage in that their alkaline aqueous solution on standing produces a disagreeable odor. It has been found in a surprising manner that the anthraquinone derivatives characterized by the following formula in which n is a whole number between 2 and 6 inclusive, R represents a lower alkyl radical, NZ represents a heterocyclic radical such that the morpholine or piperidine residue and A is an anion, such as a halide or methylsulfate, do not possess this disadvantage. Since these compositions have moreover dyeing properties which are quite remarkable and yield shades that are resistant to sunlight, they are very advantageous for use in the cosmetic field.
• compositions are generally used in the form of solutions for dyeing hair, it is very important, both for the persons whose hair is being dyed and for the personnel of the beauty salon, that the treatment takes place without releasing bad odors.
• the present invention therefore envisages as a new article of manufacture the new chemical compositions of the above Formula 5.
• Another object of the invention is to provide hair dyeing compositions characterized by the fact that they contain one or more compositions of the above general Formula 5.
• compositions which fall within the scope of the present invention the following are particularly advantageous: 1 methyl [I-anthraquinonylaminoethyl)- methylmorpholinium] sulfate and l-methyl [(L-anthraquinonylaminopropyl)-methyl-piperidine] sulfate.
• compositions according to the invention are obtained from derivatives having a corresponding tertiary amine function.
• the latter may be prepared from l-chloroanthraquinone by condensation using heat in the presence of mixture of copper acetate and potassium acetate with an alkaline diamine having the formula in which n and NZ have the same significance as in the general Formula 5, given above.
• quaternization of these tertiary anthraquinonic derivatives may be easily accomplished using a quaternizing agent such as methyl sulfate or an alkyl halide in the presence of an appropriate salt.
• the dyeing solutions according to the invention are prepared by simply dissolving in water one or more compositions having the general Formula given above in the presence or in the absence of other coloring agents and by then introducing into the solution conventional ingredients such as dispersing agents, emollients, perfume, etc.
• the concentration of the dyes may be varied within broad limits and their choice is a function of the result sought.
• the hair is colored by means of the solutions according to the invention in the usual manner by applying it preferably at room temperature to the hair for the length of time required.
• the pH of the solution used may vary within broad limits and is preferably between 4.5 and 9.5.
• the dyes according to the invention generally yield reddish colors.
• the 1(fl-morpholino-ethyl) amino anthraquinone is prepared by heating to reflux for 7 hours under agitation a mixture of 0.2 mole of l-chloro-anthraquinone and 0.8 mole of fl-amino-ethylmorpholine in solution with 240 cc. of isobutanol in the presence of 1.2 grams of potassium acetate and 0.1 gram of copper acetate.
• the corresponding quaternary composition is prepared by treating it with methyl sulfate in toluene at 80.
• the product is obtained with a yield of 94% and melts with decomposition at 214-217".
• I-(y-piperidine-propyl)-amino-anthraquinone is prepared by earring to reflux at 7 hours a mixture of 0.05 mole of a-chloro-anthraquinone and 0.2 mol of v-aminopropyl-piperidine and 60 cc. of toluene in the presence of 5 grams of potassium acetate and 0.3 gram of copper acetate.
• this base is reacted with cold methyl sulfate in toluene in the customary manner.
• Example LVI The following mixture is prepared:
• a process for dyeing live human hair which comprises applying thereto a compound selected from the group consisting of a dyestulf of the formula:
• n1 is an integer of 2, 3 or 6 and R and R together with the adjacent nitrogen is morpholino.
• composition for dyeing live human hair comprising a compound selected from the group consisting of a dyestutr' of the formula:
• X is a --NH-Z and the other two are hydrogen and in which NH--Z is selected from the group consisting of NN dimethyl paraphenylene diamine and in which R and R are selected from the group consisting of lower alkyl or together with the adjacent nitrogen morpholine or piperidine; and n is an integer from 2 to 6, in an aqueous solution having a pH between 3 and 10.
• composition of claim 9 having a pH between 4.5 and 9.5.
• composition as claimed in claim 9 which also contains a wetting agent.
• composition of claim 9 in which the dyestutf is one in which R and R, together with the adjacent nitrogen is morpholino and in which n is an integer of from 2 to 3.
• composition of claim 9 in which R and R together with the adjacent nitrogen is piperidino and in which n is an integer of from 2 to 3.
• a composition for dyeing live human hair which comprises an aqueous solution having a pH of 3 to 9 and a compound selected from the group consisting of the dyestutf of the formula:
• n is an integer from 2 to 6 and in which the group is selected from the group consisting of lower dialkyl amine, morpholino and piperidino.
• composition of claim 14 wherein said dyestufi is the quaternary ammonium salt of Z-(B-diethylaminoethylamino)anthraquinone.
• composition of claim 14 wherein said dyestuff is 2-('y-diethylaminopropylamino)anthraquinone.
• composition of claim 14 wherein said dyestufi is Z-(fi-morpholinoethylamino) anthraquinone.
• a process for dyeing live human hair which comprises applying thereto dyeing amounts of the quaternary ammonium salt of a dyestufi of the formula:
• n is an integer from 2 to 6 inclusive
• R is lower alkyl
• NZ is selected from the group consisting of morpholino and piperidino
• A is selected from the group consisting of halogen and methylsulphate.
• a dyeing composition comprising an aqueous solution containing dyeing amounts of the quarternary ammonium salt of a dyestuff of the formula in which n is an integer from 2 to 6 inclusive, R is lower alkyl, and NZ is selected from the group consisting of morpholino and piperidino and A is selected from the group consisting of halogen and methylsulfate having a pH of 4.5 to 9.5.
• composition of claim 21, wherein said salt is methyl [(1 anthraquinonylaminoethyl) methyl-morpholinium].
• composition of claim 21, wherein said salt is methyl [(1 anthraquinonylaminopropyl) methylpiperidino].

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Citations (8)

• 0
  • NL NL131931D patent/NL131931C/xx active
  • BE BE639298D patent/BE639298A/xx unknown
  • NL NL299891D patent/NL299891A/xx unknown
  • GB GB1053300D patent/GB1053300A/en active Active
• 1963
  • 1963-10-29 DE DE1794385*CA patent/DE1794385C3/de not_active Expired
  • 1963-10-29 DE DE1794384*CA patent/DE1794384C3/de not_active Expired
  • 1963-10-29 DE DE1492065A patent/DE1492065C3/de not_active Expired
  • 1963-10-29 CH CH1326063A patent/CH434573A/fr unknown
• 1964
  • 1964-01-04 DE DE1794332A patent/DE1794332C3/de not_active Expired
• 1967
  • 1967-05-19 US US639915A patent/US3467483A/en not_active Expired - Lifetime
• 1970
  • 1970-01-16 NL NL7000658A patent/NL7000658A/xx unknown
  • 1970-01-16 NL NL7000660A patent/NL7000660A/xx unknown

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