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WO2009030372A1 - Dérivés de dha bifonctionnels - Google Patents

Dérivés de dha bifonctionnels Download PDF

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Publication number
WO2009030372A1
WO2009030372A1 PCT/EP2008/006853 EP2008006853W WO2009030372A1 WO 2009030372 A1 WO2009030372 A1 WO 2009030372A1 EP 2008006853 W EP2008006853 W EP 2008006853W WO 2009030372 A1 WO2009030372 A1 WO 2009030372A1
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WO
WIPO (PCT)
Prior art keywords
dioxan
ethyl
carbon atoms
phenyl
dihydroxyacetone
Prior art date
Application number
PCT/EP2008/006853
Other languages
German (de)
English (en)
Inventor
Philipp Buehle
Thomas Rudolph
Herwig Buchholz
Original Assignee
Merck Patent Gmbh
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Filing date
Publication date
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Publication of WO2009030372A1 publication Critical patent/WO2009030372A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/04—Preparations for care of the skin for chemically tanning the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/20—Spiro-condensed systems
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to selected bifunctional dihydroxyacetone derivatives, preparations containing bifunctional dihydroxyacetone derivatives of the formula (I) or dimeric compounds of the formula (II) and their use as self-tanning substance or hair dye.
  • the epidermis contains in its lowest layer, the basal layer, in addition to the basal cells, individual pigment-forming cells, the melanocytes. UV light in these cells stimulates the production of melanin, which is transported to the keratinocytes (horny cells) where it becomes visible as a brown skin color.
  • This pigmentation which is caused by the amino acid tyrosine, is primarily initiated by UVB radiation and is termed "indirect pigmentation.” Its development takes place over several days, and the sun tan thus obtained persists for several weeks.
  • Pigmentation which starts with sun exposure, predominantly colorless melanin precursors are oxidized by UVA radiation to dark colored melanin, and as this oxidation is reversible, it results in only a brief skin tanning.
  • An artificial tanning of the skin can be produced externally with the help of make-up and orally by taking carotenoids.
  • the artificial tanning of the skin Far more popular, however, is the artificial tanning of the skin, which can be achieved by applying so-called self-tanner.
  • These compounds have as a chemical structural feature keto or aldehyde groups in the vicinity of alcohol functions. These ketols or aldols belong predominantly to the substance class of sugars.
  • the compounds can be reacted with the proteins and amino acids of the horny layer of the skin in the manner of a Maillard reaction, whereby polymers which give the skin a brownish hue are formed via a reaction pathway that has not yet been fully elucidated. This reaction is completed in about 4 to 6 hours. The tan thus obtained is not washable and is removed only with the normal Hautabschuppung.
  • Self-tanning substance is 1, 3-dihydroxyacetone (DHA). This is a water-soluble crystalline solid which is not stable under neutral to basic conditions. This instability is also associated with the development of cosmetically undesirable off-odors.
  • DHA 1, 3-dihydroxyacetone
  • EP 0 796 838 B1 describes cosmetic or dermatological compositions containing an open-chain precursor of the dihydroxyacetone.
  • WO 99/43667 discloses cyclic 1,3-dioxanes which liberate alcohols and function as "pro-perfumes”.
  • R1, R2 identical or different, consisting for example of H, methyl, ethyl, alkyl, phenyl, aryl wherein the [1, 3] -dioxan-5-one compounds (on the left side of the reaction equation), the starting materials for the Synthesis of Dihydroxyacetonderivaten with UV filter properties represent.
  • the object of the present invention is therefore to provide alternative substances which have a tanning action on the skin and on hair.
  • self-tanning substances should be provided which are stable under neutral to basic conditions.
  • development of cosmetically undesirable off-odors should be avoided by the use of more stable derivatives.
  • R 1 and R 2 are the same or different
  • Carbon atoms can be substituted
  • R is selected from H, straight-chain or branched alkyl having 1 to 20 carbon atoms
  • R 3 ' is H or -CH 2 OH and wherein R 3 is H.
  • the compounds of the formula (I) or (II), as described above, are formally condensation products of dihydroxyacetone or of a -CH 2 OH-substituted dihydroxyacetone (ie the erythrulose) with a carboxylic acid and an alcohol.
  • the compounds of formula (I) or (II) are characterized by the fact that they gain stability with increasing ambient pH while other self-tanning agents such as DHA or erythrulose lose stability with increasing pH.
  • the compounds of the formula (I) or (II) therefore offer the advantage of being usable in pH ranges in which other self-tanning agents are already subject to decomposition.
  • Decomposition which can also lead to loss of active substance and skin irritation.
  • Their coloring or tanning effect can only in selected compounds, in particular in compounds of formula (II), by molecular cleavage under physiological acid conditions (eg after skin application, pH of the skin about 5), by enzymes or by amino groups in the sense of Maillard Reaction catalyzed to occur.
  • dihydroxyacetone ortho-ethyl acetate is capable of this.
  • the tanning mechanism can be explained by first forming an imine with free amino groups of the stratum corneum and the free keto group of the compounds of formula (I), which then forms an alpha-amino aldehyde under proton transfer and water addition (Amadori rearrangement). This then enters the further reaction steps for Bräungungsretress (Maillard reaction) with the stratum corneum.
  • the compounds of the formula (I) or (II) are substituents as defined above or with preferred substituents as described above or below are oil-soluble self-tanning substances brings advantages over other water-soluble self-tanning substances such as DHA.
  • inventive self-tanning substances dissolved in the oil phase and not the water phase are thus more stable to oxidative or hydrolytic degradation.
  • a combination of the oil-soluble self-tanning substances of the invention with other water-soluble self-tanning substances such as DHA results in synergistic effects on the tanning result on the skin.
  • Another object of the invention is therefore also the use of a compound of formula (I)
  • hair dye wherein the radicals are defined as follows: XO, S or NR,
  • R 1 and R 2 are the same or different, •
  • Carbon atoms can be substituted
  • R is selected from H, straight-chain or branched alkyl having 1 to 20 carbon atoms
  • R 3 ' is H or -CH 2 OH and wherein R 3 is H.
  • the compounds of the formula (I) or (II) have, in addition to a self-tanning component, at least one second active ingredient which is released in the tanning reaction and which leads to a significant added benefit of the substance used. Therefore, the compounds of formula (I) in the present specification are also referred to as bifunctional derivatives of dihydroxyacetone. Compounds of the formula (II) are also referred to as the dimer derivative of the bifunctional derivatives of the dihydroxyacetone of the formula (I). Furthermore, the compounds of the formula (I) or (II), in particular of the formula (I), are relatively easy to prepare. Very particular preference is given to using the compounds of the formula (I) and their compounds described as being preferred as self-tanning substances for skin and hair or skin or hair.
  • self-tanner is used synonymously in the context of this invention as a self-tanning substance or self-tanning substance.
  • R 1 (II) is produced in the cleavage of the compounds (I) and / or usually a carboxylic acid R 1 -COOH, from R 2, a compound R formed 2 -XH Alternatively, in the postulated tanning mechanism. also the carboxylic acid derivatives R 1 -C (O) -XR 2 arise.
  • active ingredients may have, for example, the following effects: preserving action (eg acetic acid, para-hydroxybenzoic acid ester, benzoic acid, salicylic acid, sorbic acid), preserving or cooling action (eg ethanol), regulation of the water content of the skin / moisturizers (eg lactic acid, pyrrolidonecarboxylic acid, Amino acids), "immediate lifting effect” (eg dimethylethanolamine), “natural cell protection effect” (eg ectoine).
  • preserving action eg acetic acid, para-hydroxybenzoic acid ester, benzoic acid, salicylic acid, sorbic acid
  • preserving or cooling action eg ethanol
  • regulation of the water content of the skin / moisturizers eg lactic acid, pyrrolidonecarboxylic acid, Amino acids
  • immediateate lifting effect eg dimethylethanolamine
  • natural cell protection effect eg ectoine
  • moisturizers other known releasable active substances are all known substances which are also used as moisturizers, moisturizers, UV filters (for example ethylhexyl methoxycinnamate, octrocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl
  • UV filters for example ethylhexyl methoxycinnamate, octrocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl
  • Salicylates preservatives, dyes, self-tanning agents, tanning agents, skin whiteners, peptides, anti-aging agents (e.g., creatine, creatinine), drugs, fragrances, etc.
  • NMF Natural Moisturizing Factor
  • Lactic acid / sodium lactate, 7% urea and also a neutral Carbohydrate mixture, glucosamine and uric acid see Fey, Otte, Dictionary of Cosmetics, 3rd edition, 1991.
  • the radical X in the bifunctional derivatives of the dihydroxyacetone of the formula (I) preferably has the meaning O.
  • the radical X in the compounds of the formula (II) preferably has the meaning O.
  • the radical R 3 is preferably H.
  • Carbon atoms in this case comprises alkyl and alkenyl groups having 1-20 C atoms, it being understood that an alkenyl group can be present only from 2 carbon atoms.
  • the straight-chain or branched alkyl group having 1-20 carbon atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, isobutyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1-, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, 1-ethyl-pentyl, octyl, 1-ethyl-hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl , Octadecyl, nonadecyl or eicosyl.
  • a straight-chain or branched alkenyl having 2 to 20 C atoms, wherein several double bonds may also be present is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, iso-butenyl, furthermore 4-pentenyl, iso-pentenyl, hexenyl , Heptenyl, octenyl, -C 9 Hi 7 , -Ci 0 Hig to -C20H39; preferably vinyl.
  • the described alkyl or alkenyl groups may be substituted with further saturated and / or unsaturated alkyl groups of 1-8 carbon atoms, OR, NR 2 , saturated, partially or fully unsaturated cycloalkyl of 3-7 carbon atoms substituted by OH or Oalkyl of 1-8 carbon atoms ,
  • the substituted alkyl or alkenyl group is dimethylaminoethyl, 2- (4-methoxyphenyl) vinyl or 1-hydroxyethyl.
  • Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl,
  • These cycloalkyl groups may be substituted with further saturated and / or unsaturated alkyl groups of 1-8 carbon atoms, OR, NR 2 , saturated, partially or fully unsaturated cycloalkyl of 3-7 carbon atoms substituted by OH or Oalkyl of 1-8 carbon atoms.
  • the substituted cycloalkyl of 3-7 carbon atoms is 2-hydroxyphenyl.
  • the substituents R 1 and / or R 2 are independently selected from the group -H, where R 2 may not be H, - (CH 2 ) oCH 3 , - (CH 2 ) n NH 2 , -
  • n is an integer and selected from the range 1 to 20, preferably 1, 2 or 3 wherein 0 and p are independently an integer and selected from the range 0 to 20, preferably 0, 1 or 2, wherein Ph is phenyl, Ar is an unsubstituted or substituted
  • Phenyl group, wherein the substituted phenyl group may be substituted by OR or NR 2 , wherein R is selected from H, straight-chain or branched alkyl having 1 to 20
  • the substituent R 1 of the compounds of formula (I) or (II) is selected from the group of branched or straight-chain, saturated or unsaturated alkyl having 1 to 20 carbon atoms, wherein the saturated
  • the alkyl group may be substituted by OH, and the unsaturated alkyl group may be preferably substituted with phenyl substituted by Oalkyl, and saturated, partially or fully unsaturated cycloalkyl having 3-7
  • the substituent R 1 is very particularly preferably selected from the group straight-chain or branched alkyl group having 1-20 carbon atoms, -CHOH-CH 3 , pyrrolidonecarboxylic acid radical, ecto-carboxylic acid radical, 2 -hydroxy-phenyl or (4-methoxyphenyl) -vinyl.
  • the substituent R 2 of the compounds of the formula (I) or (II) is particularly preferably selected from the group of a physiologically and / or dermatologically tolerated alcohol R 2 -OH or a physiologically and / or dermatologically tolerated aminoalcohol R 2 -OH, where the R 2 is a branched or straight-chain alkyl having 1-20 carbon atoms, which may be substituted by NR 2 , wherein R has one of the meanings given above.
  • the substituent R 2 of the bifunctional derivative of the DHA of the formula (I) is selected from the group consisting of branched or straight-chain alkyl having 1-20 C atoms and dimethylaminoethyl, preferably R 2 but an unsubstituted branched or straight chain alkyl group of 1-20 carbon atoms.
  • DHA-ortho-ethyl-ectoine DHA-ortho-ethyl-pyrrolidone carbonate
  • a particularly particularly preferred self-tanning substance which dyes skin and hair is dihydroxyacetone-ortho-ethyl acetate.
  • the substance has the very positive quality of a cosmetic oil that allows direct application as a pure substance. This is a decisive advantage for use as a hair dye.
  • the compound of the formula (I) for the use according to the invention is preferably selected from the group consisting of dihydroxyacetone-ortho-ethyl acetate, dihydroxyacetone-ortho- (2-dimethylamino) -ethyl acetate, dihydroxyacetone-ortho-ethyl-lactate, dihydroxyacetone-ortho-ethyl-ectoine and dihydroxyacetone-ortho-ethyl-pyrrolidone carbonate.
  • the compounds of the formula (I) or formula (II) can be easily synthesized under mild conditions. The compounds are isolated in good yields.
  • substituents X, R 1 and R 2 correspond to a previously given definition, in particular correspond to a substituent of the described individual compounds of said lists.
  • the person skilled in the art of synthetic chemistry is able to determine the substituents R 1 , R 2 and X from the disclosed individual compounds, so that this reaction equation is a disclosure for the synthesis of all the listed individual compounds.
  • the preferred conditions for the preparation of the dimeric compounds are 6 to 48 hours and 50 to 100 ° C.
  • Another object of the present invention is the use of the compound according to formula (I) and / or formula (II), as indicated above, for the preparation of a preparation, in particular a cosmetic or a dermatological preparation, preferably for artificial tanning and / or or browning of the skin or the coloring of the hair.
  • the use of the compound of the formula (I) and / or the formula (II) as a UV filter, as a preservative, for lifting the skin as well as for the preparation of a cosmetic and / or dermatological preparation with light protection properties is possible.
  • the preparations are usually topically applicable preparations, for example cosmetic or dermatological formulations.
  • the preparations in this case contain a cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients.
  • the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients. If it is a dietary supplement, then a suitable carrier is to be selected.
  • the preparations are perfumes
  • agent or formulation is used synonymously in addition to the term preparation. All compounds or components that can be used in the formulations are either known and commercially available or can be synthesized by known methods.
  • the invention also provides a process for preparing a preparation as described above, wherein at least one compound of the formula (I) or at least one compound of the formula (II) is mixed with a carrier suitable for topical applications.
  • Suitable carriers are described in detail in the following part.
  • the at least one bifunctional derivative of the dihydroxyacetone of the formula (I) or the at least one dimeric bifunctional derivative of the dihydroxyacetone of the formula (II) having the defined substituents or preferred individual compounds in the preparations according to the invention is typically in amounts of from 0.01 to 10 % By weight, preferably in amounts of from 0.1% by weight to 5% by weight and more preferably in amounts of from 0.5 to 2% by weight.
  • the expert does not have any difficulties in selecting the quantities according to the intended effect of the preparation.
  • pigments may furthermore also be present, the layer structure of the pigments not being limited.
  • the color pigment should be skin colored or brownish at a level of from 0.5 to 5% by weight.
  • the selection of a corresponding pigment is familiar to the person skilled in the art.
  • advantageous color pigments are titanium dioxide, mica, iron oxides (eg Fe 2 O 3 , Fe 3 O 4 , FeO (OH)) and / or tin oxide.
  • Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list.
  • the Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971.
  • 3rd layer substrate pigments z. Mica / metal oxide
  • pearlescent pigments are, for example, pulverulent pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide, and Bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is z. For example, listed under the CIN 77163 luster pigment.
  • pearlescent pigment types based on mica / metal oxide are also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide:
  • pearlescent pigments available from Merck under the trade names Timiron®, Colorona®, Dichrona®, Xirona® or Ronastar®.
  • pearlescent pigments which are advantageous in the context of the present invention are obtainable in numerous ways known per se.
  • other substrates except mica can be coated with other metal oxides such.
  • silica and the like As silica and the like.
  • pearlescent pigments which under the Use of SiO 2 are produced.
  • Such pigments which may also have additional gonichromatic effects are, for. B. under the trade name Sicopearl Fantastico available from BASF.
  • Particularly suitable pigments in premixes are, for example, Ronastar® Silver or Colorona® Bronze.
  • the preparation according to the invention may preferably also contain formaldehyde scavengers and optionally flavonoids for improving the odor.
  • the formaldehyde scavenger is selected from the group consisting of alkali metal, alkaline earth metal or ammonium bisulfite.
  • DHA Plus is a product blend containing sodium bisulfite, equivalent to Na 2 S 2 O 5 or INCI: sodium disulfite, for the masking, elimination or neutralization of formaldehyde.
  • the addition of sodium bisulfite in finished formulations significantly reduces or eliminates the unpleasant odor.
  • DHA Plus is distributed by Merck, Darmstadt.
  • the flavonoid optionally present in the preparation according to the invention additionally acts as a stabilizer for the self-tanner or self-tanning substances and / or reduces or avoids or improves storage-dependent off-odors, which can also be caused by additives or auxiliaries.
  • flavonoid in which one or more phenolic hydroxy groups are blocked by etherification or esterification.
  • hydroxyethyl-substituted flavonoids such as preferably troxerutin, troxequercetin, troxeisoquercetin or troxeluteolin
  • flavonoid sulfates or flavonoid phosphates such as preferably rutosulfates
  • Particularly preferred in the context of the use according to the invention are rutin sulfate and troxerutin. Very particularly preferred is the use of troxerutin.
  • the preferred flavonoids have a non-positively charged FlavangrundMech. It is believed that these flavonoids complex metal ions such as Fe 2 VCu 2+ , thus contributing to autooxidation events
  • DHA Rapid is a product mixture containing dihydroxyacetone and troxerutin, Merck, Darmstadt.
  • the preparation according to the invention may preferably also contain other active substances, such as, for example, repellents, in particular insect repellents, UV filters, flavone derivatives, chromone derivatives, aryloximes and parabens.
  • repellents in particular insect repellents
  • UV filters flavone derivatives
  • chromone derivatives chromone derivatives
  • parabens parabens
  • repellent agents belong to the classes of amides, alcohols, esters and ethers.
  • Repellents are usually the following
  • Preferred repellents are selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl-amino) -propionic acid ethyl ester, dimethyl phthalate, butopyronoxyl, 2,3 ) 4,5-bis (2-butylene) -tetrahydro- 2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, N- (2-ethylhexyl) -8,9,10-trinorborn-5-ene-2,3-dicarboximide, Dimethylcarbate, di-n-propyl isocine chomeronate, (R) -p-mentha-i, 8-diol, 2-ethylhexane-1,3-diol, N-octyl-bi-cyclohepetane-di
  • Bayer or mixtures thereof, and it is particularly preferably selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl- amino) - propionic acid ethyl ester, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures thereof.
  • Parabens are 4-hydroxybenzoic acid esters which are used in free form or as sodium salts for the preservation of preparations in the field of food, cosmetics and pharmaceuticals.
  • the effect of the esters is directly proportional to the chain length of the alkyl radical, but conversely the solubility decreases with increasing chain length.
  • the esters are largely pH independent and operate in a pH range of 3.0-8.0.
  • the antimicrobial mechanism of action is based on damage. the microbial membranes by the surface activity of the PHB esters as well as on the protein denaturation. In addition, interactions with coenzymes occur. The effect is directed against fungi, yeasts and bacteria.
  • the preservative The most important parabens are methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate and butyl 4-hydroxybenzoate.
  • 2-hydroxy-5-methyllaurophenone oxime which is also referred to as HMLO, LPO or F5
  • HMLO 2-hydroxy-5-methyllaurophenone oxime
  • LPO 2-hydroxy-5-methyllaurophenone oxime
  • Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases associated with inflammation. It is known that such preparations, e.g. can be used for the treatment of psoriasis, various eczema forms, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages.
  • compositions according to the invention which, in addition to the compound (s) mentioned, additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising anti-inflammatory suitability.
  • the preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.
  • flavone derivatives are flavonoids and coumaranones.
  • Chromone derivatives are preferably understood to mean certain chromene-2-one derivatives which are suitable as active ingredients for the preventive treatment of human skin and hair according to aging processes and damaging environmental influences. At the same time, they show a low irritation potential for the skin, influencing the water binding in the skin positively, maintain or increase the elasticity of the skin and thus promote a smoothing of the skin. These compounds preferably correspond to the following formula
  • R 1 and R 2 may be the same or different and are selected from
  • R 3 is H or straight-chain or branched C 1 - to C 20 -alkyl groups
  • R 4 is H or OR 8 ,
  • R 5 and R 6 may be the same or different and are selected from
  • R 7 is H, straight or branched Cr to C 2 o-alkyl groups, a polyhydroxy compound, such as preferably an ascorbic acid residue or glycosidic residues and
  • the proportion of one or more compounds selected from chromone derivatives and coumaranones in a preparation is preferably from
  • the protective effect of preparations against oxidative stress or against the action of radicals can be improved if the preparations contain one or more antioxidants, wherein the skilled person has no difficulty in selecting suitable fast or delayed-acting antioxidants.
  • the preparation is a preparation for protecting body cells against oxidative stress, in particular for reducing skin aging, characterized in that it contains, in addition to the self-tanning substances of the formula (I) or (II), the optional flavonoids and optionally containing other ingredients, one or more antioxidants.
  • antioxidants e.g. Amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (e.g., urocanic acid) and derivatives thereof, peptides such as D, L-camosine, D-carnosine, L-carnosine, and the like
  • Derivatives eg, anserine
  • carotenoids eg, carotenoids
  • carotenes eg, ⁇ -carotene, ⁇ -carotene, lycopene
  • chlorogenic acid and its derivatives lipoic acid and its derivatives (eg, dihydrolipoic acid), aurothioglucose, propylthiouracil, and other thiols (eg, thioredoxin, glutathione , Cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their De
  • Vitamin A palmitate and coniferyl benzoate of benzoin, rutinic acid and derivatives thereof, ⁇ -glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO 4 ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).
  • benzoin rutinic acid and derivatives thereof, ⁇ -glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone,
  • Suitable antioxidants are also compounds of the formulas A or B.
  • R 1 can be selected from the group -C (O) CH 3 , -CO 2 R 3 , -C (O) NH 2 and -C (O) N (R 4 ) 2 ,
  • X is O or NH 1 '
  • R 2 is linear or branched alkyl having 1 to 30 C atoms
  • R 3 is linear or branched alkyl having 1 to 20 C atoms
  • R 4 are each independently of one another H or linear or branched alkyl having 1 to 8 C atoms
  • R 5 is linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
  • R 6 denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, more preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester (eg
  • Oxynex ® ST Liquid Liquid
  • 2- (4-hydroxy-3,5-dimethoxybenzy) - malonic acid bis- (2-ethylhexyl) ester example RonaCare ® AP
  • antioxidants are also suitable for use in the cosmetic preparations according to the invention.
  • Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example
  • Oxynex ® L LIQUID DL- ⁇ -tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (for example Oxynex ® LM) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (for example Oxynex ® 2004)
  • Such antioxidants are used with the compounds of the invention in such compositions usually in weight percent ratios in the range of 1000: 1 to 1: 1000, preferably in weight percent ratios of 100: 1 to 1: 100.
  • the polyphenols which occur in part as natural substances, are of particular interest for applications in the pharmaceutical, cosmetic or nutritional field.
  • the flavonoids or bioflavonoids which are known mainly as plant dyes, frequently have an antioxidant potential. Effects of the substitution pattern of mono- and dihydoxy flavones are dealt with by K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108. It is observed there that dihydroxyflavones having an OH group adjacent to the keto function or OH groups in the 3'4 'or 6,7 or 7,8 position have antioxidant properties while other mono- and Dihydroxyflavone partially have no antioxidant properties.
  • Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) is often cited as a particularly effective antioxidant (eg, CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159).
  • K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A.E.M.F. Soffers and I.M.C.M. Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH dependence of the antioxidant activity of hydroxyflavones, and quercetin shows the highest activity of the investigated structures over the entire pH range.
  • Suitable antioxidants are furthermore compounds of the formula (C)
  • R 1 to R 10 may be the same or different and are selected from H
  • Hydroxy group may be bonded to a primary or secondary carbon atom of the chain and further the alkyl chain may also be interrupted by oxygen, and / or
  • the preparations to be used may contain vitamins as further ingredients.
  • vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B 2 ), nicotinic acid amide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D 2 ), vitamin E, DL- ⁇ -tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin Ki, esculin (vitamin P active ingredient), thiamine (vitamin B 1 ), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B 6 ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B 12 ), particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL - ⁇
  • Preferred preparations can also serve for sunscreen and then contain, in addition to the bifunctional DHA derivatives of the formula (I) or the dimers of the formula (M) and optionally other ingredients, UV filters.
  • UV filters are suitable for combination with the DHA derivatives to be used according to the invention. Particular preference is given to such UV Filters whose physiological safety has already been proven. Both for UVA and UVB filters, there are many well-known and proven substances from the literature, eg
  • Benzylidenecamphor derivatives such as 3- (4'-methylbenzylidene) -dl-camphor (for example Eusolex 6300), 3-benzylidenecamphor (for example Mexoryl® SD) 1 polymers of N - ⁇ (2 and 4) - [(2-3- oxobom yliden) methyl] benzyl ⁇ -acrylamide (eg Mexoryl® SW), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (eg Mexoryl® SK) or (2-oxoborn-3-yl) yliden) toluene-4-sulfonic acid (eg Mexoryl® SL),
  • Benzoyl or dibenzoylmethanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (e.g., Eusolex® 9020) or 4-isopropyldibenzoylmethane (e.g., Eusolex® 8020),
  • Benzophenones such as 2-hydroxy-4-methoxybenzophenone (e.g., Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (e.g., Uvinul® MS-40),
  • Methoxycinnamate such as octyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl A-methoxycinnamate, e.g. as a mixture of isomers (e.g., Neo Heliopan® E 1000),
  • Salicylate derivatives such as 2-ethylhexyl salicylate (eg Eusolex® OS), 4-isopropylbenzyl salicylate (eg Megasol®) or 3,3,5-trimethylcyclohexyl salicylate (eg Eusolex® HMS) 1
  • 4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 2-ethylhexyl 4- (dimethylamino) benzoate (e.g., Eusolex® 6007), ethoxylated 4-aminobenzoic acid ethyl ester (e.g., Uvinul® P25),
  • Phenylbenzimidazole sulfonic acids such as 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (eg Eusolex® 232), 2,2- (1,4-phenylene) bisbenzimidazole-4,6-disulfonic acid or salts thereof (eg Neoheliopan® AP) or 2,2- (1,4-phenylene) bisbenzimidazole-6-sulfonic acid;
  • UV filters are also Methoxyflavone en Kunststoffend the German patent application DE-A-10232595.
  • Organic UV filters are usually incorporated in formulations in an amount of 0.5 to 20 percent by weight, preferably 1 to 15 percent by weight.
  • preparations with light protection properties also contain inorganic UV filters.
  • Conceivable inorganic UV filters are those from the group of titanium dioxides, such as coated titanium dioxide (for example Eusolex® T-2000, Eusolex ® T-AQUA, Eusolex® T-AVO), zinc oxides (eg Sachtotec®), iron oxides or even cerium oxides are conceivable.
  • These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 percent by weight, preferably 2 to 10 wt .-%, in cosmetic preparations.
  • Preferred compounds having UV-filtering properties are 3- (4 '- methylbenzylidene) -dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) -Pro-pan-1, 3-dione , 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxy-benzophenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4- (dimethylamino) -benzoic acid 2-ethyl-hexyl-ester, 2-cyano 3,3-di-phenyl-2-ethylhexyl acrylate, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts.
  • UV filters can also be used in encapsulated form.
  • organic UV filters in encapsulated form.
  • hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter.
  • hydrophobic UV filters can also be incorporated into purely aqueous preparations.
  • the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.
  • Certain UV filters in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations.
  • these filters or compounds that affect the photostability of these filters such as cinnamic acid derivatives, the photostability of the entire formulation can be increased.
  • UV filters it is preferred if one or more of the above-mentioned UV filters are present in encapsulated form. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the o.g. Effects it is still necessary that the capsules are sufficiently stable and donate the encapsulated active ingredient (UV filter) not or only to a small extent to the environment.
  • Suitable capsules may have walls of inorganic or organic polymers.
  • US Pat. No. 6,242,099 B1 describes the preparation of suitable capsules having walls made of chitin, chitin derivatives or polyhydroxylated polyamines.
  • Particularly preferred capsules have walls which can be obtained by a SolGel process as described in applications WO 00/09652, WO 00/72806 and WO 00/71084.
  • capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred.
  • the production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.
  • the capsules in preparations to be used according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the above-indicated weight percentages.
  • the preparations to be used according to the invention may additionally contain further customary skin-friendly or skin-care active substances.
  • these can be all active ingredients known to the person skilled in the art.
  • Particularly preferred active ingredients are, for example, also so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. suitable Osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors.
  • osmolytes are understood as meaning, in particular, substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below: taurine, choline, betaine, Phosphorylcholine, glycerophosphorylcholine, glutamine, glycine, ⁇ -alanine, glutamate, aspartate, proline, and taurine.
  • polyols such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below: taurine, choline, betaine, Phosphorylcholine, glycerophosphorylcholine, glutamine, glycine, ⁇ -alanine, glutamate, aspartate, proline, and taurine.
  • Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z.
  • solute substances are selected from the group consisting of pyrimidinecarboxylic acids (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic diphosphoglycerate, N.-
  • Acetylomithine trimethylamine N-oxide di-myo 1 inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), ⁇ -mannosylglycerate (firoin), ⁇ -mannosylglyceramide ( Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, for example an acid, a salt or ester of these compounds or combinations thereof.
  • DIP dimethylamine N-oxide di-myo 1 inositol phosphate
  • cDPG cyclic 2,3-diphosphoglycerate
  • DGP 1, 1-diglycerol phosphate
  • ⁇ -mannosylglycerate firoin
  • Firoin-A ⁇ -mannosylglyceramide
  • DMIP di-mannosyl
  • ectoine (S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S 1 S) -1, 4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives.
  • These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents. In particular, they stabilize enzymes against denaturing conditions such as salts, extreme pH, surfactants, urea, guanidinium chloride and other compounds.
  • Ectoine and ectoine derivatives such as hydroxyectoine can be used to advantage in medicines.
  • hydroxyectoine can be used for the manufacture of a medicament for the treatment of skin diseases.
  • Other fields of use of hydroxyectoine and other ectoin derivatives are typically in areas in which, for example, trehalose is used as an additive.
  • ectoine derivatives, such as hydroxyectoine can be used as a protective substance in dried yeast and bacterial cells.
  • Pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins such as t-PA can be protected with ectoine or its derivatives.
  • European Patent Application EP-A-0 671 161 describes in particular that ectoine and hydroxyectoine are used in cosmetic preparations such as powders, soaps, surfactant-containing cleansing products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.
  • a pyrimidinecarboxylic acid according to the following formula is preferably used,
  • R 1 is a radical H or C 1-8 -alkyl
  • R 2 is a radical H or C 1-4 -alkyl
  • R 3 , R 4 , R 5 and R 6 are each independently a radical from the group H, OH, NH 2 and C1-4 alkyl.
  • Preference is given to using pyrimidinecarboxylic acids in which R 2 is a methyl or an ethyl group and R 1 or R 5 and R 6 are H.
  • the pyrimidinecarboxylic acids ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidine-carboxylic acid) and hydroxyectoine ((S, S) -1, 4,5,6-tetrahydro-) 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid).
  • the preparations to be used according to the invention preferably contain such pyrimidinecarboxylic acids in amounts of up to 15% by weight.
  • the compatible solutes are selected from di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), ß-mannosylglycerate (Firoin ),
  • Mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP), ectoine, hydroxyectoine or mixtures thereof.
  • aryl oximes also preferably used is preferably 2-hydroxy-5-methyllaurophenonoxim, which is also referred to as HMLO, LPO or F5 used. Its suitability for use in cosmetic products is known for example from the German patent application DE-A-41 16 123. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are associated with inflammation.
  • compositions according to the invention which additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show anti-inflammatory suitability.
  • the preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.
  • preparations according to the invention may contain at least one self-tanner as further ingredient.
  • DHA 1, 3-dihydroxyacetone
  • bifunctional dihydroxyacetone derivatives of the formula (I) and the dimeric compounds of the formula (II) and optionally further active compounds can be incorporated in the customary manner, for example by mixing, into cosmetic or dermatological preparations.
  • Suitable preparations for external use for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin.
  • administration formulas such as capsules, dragees, powders, tablet solutions or solutions are suitable.
  • AIs application of the preparations to be used are, for example: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays.
  • Preferred forms of application are also shampoos, sun baths and shower baths, which are also known as so-called "spray tanning, airbrush tanning or sun showers" from commercial self-tanning studios.
  • Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants, odor improvers.
  • Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.
  • excipients suitable for topical administration e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.
  • Powders and sprays may contain the usual carriers, e.g. Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances.
  • Sprays may additionally contain the usual volatilized, liquefied propellants, e.g. Chlorofluorocarbons, propane / butane or dimethyl ether. Also, compressed air is advantageous to use.
  • Solutions and emulsions may contain the usual excipients such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butylglycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerin fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances contain.
  • solvents e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butylglycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, g
  • Suspensions may contain the customary carriers such as liquid diluents, for example water, ethanol or propylene glycol, suspending agents, for example ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.
  • Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.
  • Surfactant-containing cleaning products may contain the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.
  • excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid
  • Facial and body oils may contain the usual excipients such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.
  • synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.
  • the preferred preparation forms include, in particular, emulsions.
  • Emulsions are advantageous and contain z.
  • the lipid phase can advantageously be selected from the following substance group: mineral oils, mineral waxes
  • Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
  • Fats, waxes and other natural and synthetic fats preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with
  • Alkanoic acids of low C number or with fatty acids such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
  • oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the sense of the present invention is advantageously selected from
  • ester oils can then advantageously be selected from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. jojoba oil.
  • the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms.
  • the fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
  • the aqueous phase of the preparations to be used advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C-number alcohols, eg.
  • ethanol isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous aüs the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • carbopols for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • mixtures of the abovementioned solvents are used.
  • alcoholic solvents water can be another ingredient.
  • Emulsions are advantageous and contain z.
  • the preparations to be used contain hydrophilic surfactants.
  • the hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and coco amphoacetates.
  • the cosmetic and dermatological preparations can be in various forms. So they can z.
  • Oil-in-water (W / O / W) a gel, a solid stick, an ointment or even an aerosol.
  • Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g.
  • wax matrices As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-A-43 08 282, have been found to be favorable. Preference is given to emulsions. ONSI emulsins are especially preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.
  • emulsifiers for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.
  • O / W emulsifiers are selected as co-emulsifiers, principally from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W Emulsifiers have saturated radicals R and R 1 . If the O / W emulsifiers have unsaturated radicals R and / or R 1 , or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers may also be lower or higher.
  • fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
  • Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), polyethylene.
  • fatty acid ethoxylates of the following group: polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20 ) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene
  • the sodium laureth-11-carboxylate can be advantageously used.
  • the alkyl ether sulfate sodium laureth-4 sulfate can be advantageously used.
  • polyethylene glycol (30) cholesteryl ether can be advantageously used.
  • polyethylene glycol (25) soybean oil has been proven.
  • polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20) glyceryl oleate,
  • sorbitan esters from the group consisting of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate,
  • W / O emulsifiers can be used:
  • W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate,
  • Sorbitan monocaprylate sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, isobehenyl alcohol, Selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate.
  • compositions which are preferred according to the invention are also suitable for protecting human skin against aging processes as well as against oxidative stress, i. against damage by radicals, as e.g. be generated by sunlight, heat or other influences. It is present in various dosage forms commonly used for this application. Thus, it can be used in particular as a lotion or emulsion, such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, as solid pens or be formulated as an aerosol.
  • a lotion or emulsion such as cream or milk (O / W, W / O, O / W / O, W / O / W)
  • oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions as solid pens or be formulated as an aerosol.
  • the preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, e.g. Thickeners, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent or the skin, and others commonly used in cosmetics ingredients.
  • cosmetic adjuvants which are commonly used in this type of preparations, e.g. Thickeners, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent or the skin, and others commonly used in cosmetics ingredients.
  • dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof.
  • Particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerine and sorbitol.
  • a preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.
  • the preparation may also be in the form of an alcoholic gel comprising one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickener, such as silica.
  • the oily-alcoholic gels also contain natural or synthetic oil or wax.
  • the solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.
  • blowing agents are generally used, such as alkanes, fluoroalkanes and chlorofluoroalkanes, preferably alkanes.
  • the preparations to be used can be prepared using techniques that are well known to the person skilled in the art.
  • compositions as described above may contain or comprise, consist essentially of or consist of the necessary or optional ingredients.
  • the ortho-ester fragment to be coupled is added as trialkyloxy ortho-ester and stirred for 6-48 hrs. At 50-100 0 C Subsequently, the purification is carried out by distillation and / or crystallization.
  • Dihydroxyacetone is added to a solution of catalytic amounts of (+/-) - camphor 10-sulfonic acid and stirred at 50-100 0 C for 6-48 hours in the to be coupled ortho ester fragment. Subsequently, the purification is carried out by distillation and / or crystallization.
  • NMR data of 2-ethoxy-2-methyl- ⁇ .33dioxan-5-one The NMR spectra were measured on a Bruker DPX spectrometer ( 1 H: 250 MHz, 13 C: 62.9 MHz ).
  • DHA-OEA 2-ethoxy-2-methyl- [1,3] dioxan-5-one
  • the Lab values of the solution are measured by UV-Vis spectrometer (Varian Cary-100) and with DHA / lysine (90 mg / 146 mg) and erythrulose / lysine (120 mg / 146 mg) in the liquid / c / n model compared.
  • a 1/10 mixture of the DHA / lysine solution with ethylene glycol is prepared and also compared with Erythrulose by Lab.
  • the mixture is closed for four days and allowed to stand at room temperature and in daylight.
  • the hair is filtered through a pleated filter, washed with water and then dried in air.
  • the mixture is closed for four days and allowed to stand at room temperature and in daylight.
  • the hair is filtered through a pleated filter, washed with water and then dried in air.
  • the mixture is sealed for four days and at room temperature
  • the hair is filtered through a pleated filter, washed with water and then dried in air.
  • the hair is filtered through a pleated filter, washed with water and then dried in air.
  • Experiment 1 shows that after pretreatment of the hair with NaOH and hair coloring in the experiment shown a barely perceptible color change of the hair is observed.
  • experiment 4 i. without pretreatment of the hair and with addition of water in pure DHA-OEA, in the visual assessment of several test persons, a clearly visible color change of the hair is observed.
  • Strands of blonde bleached hair are prepared by soaking a portion of the strands for about 15 minutes in 10% ammonia solution, another portion of the strands are soaked in 0.1 N NaOH for about 15 minutes and another portion of the strands becomes soaked in pure water. Of the soaked strands of hair, each half over the H exertluftfön (about 120 0 C) dried. Subsequently, the individual differently pretreated hair strands, each wet or dry placed on slides.
  • the respective strands of hair on the slides are wetted with pure DHA-OEA.
  • Another slide is placed with the rough side over the tress, pressed firmly and left for two days at room temperature and daylight.
  • Experiment 5 shows that DHA-OEA shows strong staining after pretreatment of hair with wet ammonia on wet hair after visual assessment of several subjects. After pretreatment of the hair with NaOH on damp hair and on hair hair which has not been pretreated, a color change is also observed after visual assessment of several test persons.
  • Formulation Example 1a O / W Tanning Cream
  • Tego Care 150 GLYCERYL STEARATE, 8.00 STEARETH-25, CETETH-20,
  • Probiol L 05018 (Empty (7) AQUA, ALCOHOL DENATE, 5.00 liposomes) LELCITHIN, GLYCERINE,
  • phase A and B are heated to 80 0 C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 0 C added.
  • Tego Care 150 GLYCERYL STEARATE, 8.00 STEARETH-25, CETETH-20,
  • Probiol L 05018 (Empty (7) AQUA, ALCOHOL DENATE, 5.00 tiposomes) LELCITHIN, GLYCERINE,
  • phase A and B are heated to 80 0 C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 0 C added.
  • Rhodicare S (7) XANTHAN GUM 0.20
  • Probiol L 05018 (Empty (8) AQUA, ALCOHOL DENATE, 5.00 liposomes) LECITHIN, GLYCERINE,
  • phases A and B are mixed separately and heated to 75 ° C. Thereafter, phase C is added to phase B and added to phase A with stirring. It is homogenized. It is then cooled with stirring and the phases D and E at 40 ° C was added.
  • Rhodicare S (7) XANTHAN GUM 0.20
  • Probiol L 05018 (Empty (8) AQUA, ALCOHOL DENATE 5.00 liposomes) LECITHIN, GLYCERINE, DISODIUM PHOSPHATE
  • phase A and B are mixed separately and heated to 75 0 C. Thereafter, phase C is added to phase B and added to phase A with stirring. It is homogenized. Then it is cooled with stirring and the phases D and E at 40 0 C added.
  • Formulation Example 5a mild transparent W / O tanning lotion
  • phase B is dissolved and then it is given to phase A.
  • the pH is with
  • phase B is dissolved and then it is given to phase A.
  • phase B the magnesium sulfate heptahydrate is dissolved in the water of phase B. Then the remaining components of phase B are added. Phase B is slowly added to Phase A with stirring. It is quickly stirred for a further 2 minutes and homogenized.
  • the Natrosol is added to the vortex of vigorously stirred Phase B water.
  • the rate of addition must be slow enough to allow the particles to separate and to have their surface moistened individually, but should be fast enough to minimize the viscosity of the aqueous phase during polymer addition.
  • the dihydroxyacetone ortho-ethyl acetate is dissolved in the water of phase A and the remaining ingredients are added with stirring. Phases A and B are added together and homogenized.
  • the Natrosol is added to the vortex of vigorously stirred Phase B water.
  • the rate of addition must be slow enough to allow the particles to separate and to have their surface moistened individually, but should be fast enough to minimize the viscosity of the aqueous phase during polymer addition.
  • the dihydroxyacetone-ortho- (2-dimethylamino) ethyl-acetate is dissolved in the water of phase A and the remaining ingredients are added with stirring. Phases A and B are added together and homogenized.
  • Formulation example 8a aqueous-alcoholic tanning lotion for pump sprays
  • the dihydroxyacetone ortho-ethyl acetate is dissolved in the water and the remaining ingredients are added with stirring.
  • Formulation example 8b aqueous-alcoholic tanning lotion for pump sprays
  • Phase B is released and added to Phase A.
  • Phases C and D are added successively with stirring. It is homogenized.
  • Phase B is released and added to Phase A.
  • Phase C is gradually submerged
  • DIHYDROXYACETONE 2.00 water, demineralized AQUA (WATER) 10.00
  • phase A and B are mixed separately and heated to 80 0 C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 0 C added.
  • phase A and B are mixed separately and heated to 80 0 C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 0 C added.
  • the phases A and B are mixed separately and heated to 80 0 C. After that will
  • phase A and B are heated separately to 75 0 C. Thereafter, Phase A is slowly added to Phase B with stirring. At 60 ° C, phase C is added to A / B and it is homogenized. It is then cooled to 40 0 C and the phase D is added successively.

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Abstract

L'invention concerne des dérivés de dihydroxyacétone bifonctionnels choisis, des préparations contenant des dérivés de dihydroxyacétone bifonctionnels, représentées par la formule (I), ou des composés dimères représentés par la formule (II), ainsi que leur utilisation en tant que substance autobronzante ou colorant capillaire.
PCT/EP2008/006853 2007-09-03 2008-08-20 Dérivés de dha bifonctionnels WO2009030372A1 (fr)

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DE102007041854.1 2007-09-03
DE200710041854 DE102007041854A1 (de) 2007-09-03 2007-09-03 Bifunktionelle DHA-Derivate

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WO2013083225A1 (fr) * 2011-12-08 2013-06-13 Merck Patent Gmbh Dérivés du glucuronolactone comme substances auto-bronzantes
WO2018183450A1 (fr) * 2017-03-31 2018-10-04 L'oreal Compositions pour bénéfices à court et long terme pour réduire au minimum les rides et les ridules

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WO1999043667A1 (fr) * 1998-02-24 1999-09-02 The Procter & Gamble Company Nouveaux pro-parfums cycliques ayant des taux variables de liberation de l'alcool de substance brute de fragrance
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013083225A1 (fr) * 2011-12-08 2013-06-13 Merck Patent Gmbh Dérivés du glucuronolactone comme substances auto-bronzantes
US9649268B2 (en) 2011-12-08 2017-05-16 Merck Patent Gmbh Glucuronolactone derivatives as self-tanning substances
WO2018183450A1 (fr) * 2017-03-31 2018-10-04 L'oreal Compositions pour bénéfices à court et long terme pour réduire au minimum les rides et les ridules
US10098832B1 (en) 2017-03-31 2018-10-16 L'oreal Compositions for short and long term benefits for minimizing wrinkles and fine lines
KR20190118188A (ko) * 2017-03-31 2019-10-17 로레알 주름 및 잔주름을 최소화하기 위한 단기간 및 장기간 이익을 위한 조성물
CN110913830A (zh) * 2017-03-31 2020-03-24 欧莱雅 对减少皱纹和细纹具有短期和长期益处的组合物
KR102323690B1 (ko) 2017-03-31 2021-11-09 로레알 주름 및 잔주름을 최소화하기 위한 단기간 및 장기간 이익을 위한 조성물
CN110913830B (zh) * 2017-03-31 2023-02-03 欧莱雅 对减少皱纹和细纹具有短期和长期益处的组合物

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