EP2846765A2 - Phenylketon-derivate als selbstbräuner - Google Patents
Phenylketon-derivate als selbstbräunerInfo
- Publication number
- EP2846765A2 EP2846765A2 EP13717950.3A EP13717950A EP2846765A2 EP 2846765 A2 EP2846765 A2 EP 2846765A2 EP 13717950 A EP13717950 A EP 13717950A EP 2846765 A2 EP2846765 A2 EP 2846765A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- branched
- chain
- acid
- derivatives
- straight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
-
- 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
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- 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
-
- 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
- A61Q19/08—Anti-ageing preparations
Definitions
- the present invention relates to the use of phenylketone derivatives of the formula I for use as a self-tanning substance or for increasing melanin synthesis, improving melanin transport and / or improving the distribution of melanin in suprabasal layers, and preparations containing these phenylketone derivatives.
- UVB range wavelength 280-320 nm
- UVA radiation wavelength: 320-400 nm
- 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. Melanin protects the cell nuclei from further irradiation and the resulting negative effects on the cell DNA.
- the brownish-black eumelanin and the reddish-yellow pheomelanin.
- the observed skin tone is determined by the ratio of these two types of melanin.
- An artificial tanning of the skin can be produced externally with the help of make-up and orally by taking carotenoids.
- Self-tanning agents can be reacted with the proteins and amino acids of the horny layer of the skin in the sense of a Maillard reaction or via a Michael addition, whereby polymers which give the skin a brownish hue emerge via a not yet fully elucidated reaction pathway. This reaction is after about 4 to 6 hours
- Sunscreen (clothing, hat, UV filter) is required.
- the tanned skin In contrast to "tanned" skin, the tanned skin is not protected against sunburn.
- the object underlying the present invention was therefore to provide new self-tanning substances
- Self-tanning substances are suitable.
- self-tanning active is used synonymously with self-tanning substance or self-tanning substance.
- This can be either a self-tanner, with the amino acids of the skin in the sense of a Maillard reaction or a
- a first object of the present invention is therefore the
- R6 and R7 independently represent
- Self-tanning substance i. as a melanogenesis promoter or
- Propigmentation agent that promotes the natural tanning of the skin.
- Another object of the present invention is also the
- the increase in melanin synthesis can be carried out according to the invention both in the skin and in the hair.
- the substances according to the invention can be used, for example, to stimulate melanin synthesis in the melanocytes of hair follicles and thus counteract gray / white hair.
- the substances can accordingly be applied to the hair or the scalp.
- compound according to formula I also encompasses the salts of the particular compounds of formula I.
- the preferred salts include, in particular, alkali metals and alkaline earth metal salts, zinc oxides and salts thereof
- Ammonium salts but especially sodium and potassium salts.
- the radical R6 is preferably straight-chain or branched C to C 12 -alkyl, or straight-chain or branched C 2 to C 12 -alkenyl.
- R 6 particularly preferably represents straight-chain or branched C 1 - to C 6 -alkyl, or straight-chain or branched C 2 - to C 6 -alkenyl.
- R6 is methyl, ethyl or propyl, especially methyl.
- the rest R7 preferably represents straight-chain or branched C 2 to C - alkyl, or straight or branched C 2 - to C 12 alkenyl.
- R7 particularly preferably represents straight-chain or branched C to C 6 -alkyl, or straight-chain or branched C 2 to C 6 -alkenyl.
- R 7 is methyl, ethyl or propyl, especially methyl.
- R6 and R7 are identical.
- R6 and R7 are methyl.
- the radicals R 2 and R 4 are H.
- the compound of the formula I is Ia to Ig:
- the compounds of the formulas Ia to Ih are natural and are, for example, in Carissa lanceolata (Natural Product Research (2011), 25 (15), 1388-1395, la), in geranium pelargonium (Journal of Essential Oil Research (2004), 16 (1), 26-28, Ib), in Prunus domestica (Phytochemistry (1977), 16 (5), 614-15, Ic), in Plantago lanceolata (Acta Botanica Gallica (1998), 145 (4), 265-269, Id), in Ammoid pusilla (Journal of Essential Oil Research (2003), 15 (2), 135-138, le), in chestnut flowers (Journal of Agricultural and Food Chemistry (1980), 28 (1), 82-4, Ig) or in Prunus domestica (Phytochemistry (1977), 16 (5), 614-15, Ih).
- Polyphenols such as resorcinol, phloroglucinol or 1,3-dimethoxybenzene
- anhydride or with an acyl chloride under acidic conditions (either in the presence of a Lewis acid such as AICl 3 , ZnCl 2 or a strong acid such as sulfuric acid). It can the
- alkali metal phenolates can be carboxylated according to Kolbe-Schmitt (AS Lindsey, H. Jeskey, Chem. Reviews 1957, 57, 583-620).
- Polyphenols such as resorcinol or phloroglucin are already carboxylated by K 2 CO 3 in aqueous solution.
- Suitable reaction conditions for the corresponding reactions such as, for example, transesterifications or etherifications, can be inferred by the person skilled in the art in a simple manner from the generally available literature on organic reactions.
- alkyl radical having 1 to 12 C atoms is meant in addition to the above listed radicals, for example, heptyl, 1-ethyl-pentyl, octyl, 1-ethyl-hexyl, nonyl, decyl, undecyl and dodecyl.
- An alkyl radical having 1 to 30 C atoms may, in addition to the abovementioned radicals, also be tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or triacontyl.
- an alkenyl group may have one or more
- Alkenyl group having 2 to 6 C atoms is, for example, allyl, vinyl,
- An alkenyl group having 2 to 12 C atoms is additionally understood to mean heptenyl or octenyl, -CgH 17 (nonenyl), -Ci 0 H 19 (decenyl), Undecenyl or dodecenyl.
- An alkenyl group having 2 to 30 carbon atoms further includes, for example, C20H39 or triacontenyl.
- Cycloalkenyl groups contain one or more double bonds. Examples of Cylclalkyl- or
- Cyclyalkenyl groups having 5 to 8 C atoms are cyclopropyl, butyl, pentyl, hexyl, heptyl, octyl, and also cyclopentenyl, hexenyl or hexadienyl.
- Aromatic rings are according to the invention of the term
- Cycloalkenyl does not include.
- the compounds of the formula I can be used in self-tanning products as a self-tanning substance and / or for increasing the melanin synthesis in the skin, for improving melanin transport and / or for
- Compounds of Formula I enhance melanin synthesis and enhance melanin transport from the melanocytes to the keratinocytes. This affects the color of the skin and / or hair and causes a tanning effect.
- the compounds of the invention are also suitable in this context for repigmentation of the affected
- Hautarrealle in vitiligo The compounds of formula I therefore act as biological self-tanning substances that promote the natural tanning of the skin / hair. This has the advantage that thereby at the same time a better skin protection or sun protection, especially against UVB radiation, is made possible.
- the compounds of the formula I have good skin tolerance.
- preferred compounds described here are colorless or only slightly colored and thus do not lead to or only to a small extent Discoloration of the preparations.
- the preferred compounds also have good solubility in cosmetic oils.
- the compounds of the formula I can have sufficient lipophilicity in order to be able to penetrate through the outer skin layer into epidermal layers.
- the preparation and appropriate means of transport for example
- Liposomes be provided which allow a transport of the compounds of formula I through the outer skin layers. Finally, a systemic transport of the compounds of formula I is conceivable.
- the preparation is then, for example, designed to be suitable for oral administration.
- Another object of the present invention is a preparation containing at least one compound of formula I or their
- the preparations are usually topically applicable preparations, for example cosmetic or cosmetic preparations
- compositions or medical devices contain a cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients. Is it pharmaceutical
- the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients.
- agent or formulation is used synonymously in addition to the term preparation.
- Topically applicable means according to the invention that the preparation is applied externally and locally, ie that the preparation must be suitable in order to be applied to the skin, for example.
- the preparations may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods. It is preferably a cosmetic or pharmaceutical preparation; most preferably it is a cosmetic preparation.
- the at least one compound of the formula I is in the
- Preparations according to the invention typically in amounts of 0.01 to 10 wt .-%, preferably in amounts of 0.05 to 10 wt .-%, particularly preferably in amounts of 0.1 wt .-% to 5 wt .-% and completely particularly preferably in amounts of 0.5 to 2 wt .-%, based on the
- preparations according to the invention may contain at least one further self-tanning substance as further ingredient.
- This can be either a self-tanner, with the
- Amino acids of the skin in the sense of a Maillard reaction or via a Michael addition reacts, as well as a melanogenesis promoter or Propigment michswirkstoff, which promotes the natural tanning of the skin.
- Advantageous self-tanning substances which can be used include: 1,3-dihydroxyacetone, glycerolaldehyde,
- propigmentation substances can be all active ingredients known to the person skilled in the art. Examples include glycyrrhetinic acid, melanocyte stimulating hormone (alpha-MSH), peptide analogs, thymidine dinucleotides, L-tyrosine and its esters, bicyclic monoterpeniols (described in Brown et al., Photochemistry and Photobiology B: Biology 63 (2001) 148- 161), palmitic acid or palmitic acid esters (which slow down the natural degradation of tyrosinase described in Ando et al., 2004, Journal of Biological Chemistry 279 (15), 15427-15433), forskolin or also extracts such as Extracts of chasteberry berries (Vitex agnus castus).
- active ingredients include glycyrrhetinic acid, melanocyte stimulating hormone (alpha-MSH), peptide analogs, thymidine dinucleotides, L-tyros
- the at least one further self-tanning substance in the preparation in an amount of 0.01 to 20 wt .-%, particularly preferably in an amount of 0.5 to 15 wt .-% and most preferably in an amount of 1 to 8 Wt .-%, based on the total amount of the preparation.
- the tanning achieved is closer to the natural tanning
- Compounds of formula I additionally contain at least one UV filter.
- Sunscreen filters are effective in the UVA range and / or UVB range and / or IR and / or VIS range (absorber). These substances can be obtained, in particular, from cinnamic acid derivatives, salicylic acid derivatives,
- UV filters are usually named according to the INCI nomenclature. In particular suitable for a combination are:
- PABA para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. sold under the name "Escalol 507" from the company.
- ISP glyceryl PABA, PEG-25 PABA, z. B. sold under the name "Uvinul P25” from the company.
- BASF para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. sold under the name "Escalol 507" from the company.
- ISP glyceryl PABA, PEG-25 PABA, z. B. sold under the name "Uvinul P25” from the company.
- BASF para-aminobenzoic acid and its derivatives: PABA
- Salicylates Homosalates are sold under the name “Eusolex HMS” by Merck; Ethyl hexyl salicylates, e.g. B. sold under the name “Neo Heliopan OS” from the Fa. Symrise, Dipropylene glycol salicylate, z. B.
- octocrylenes e.g. Sold under the name “Eusolex® OCR” from Merck "," Uvinul N539 “from BASF, Etocrylene, z. B. sold under the name "Uvinul N35” from BASF.
- Benzophenone Derivatives Benzophenone-1, e.g. Sold under the name "Uvinul 400"; Benzophenone-2, e.g. Sold under the name “Uvinul D50”; Benzophenone-3 or oxybenzone, e.g. Sold under the name "Uvinul M40”; benzophenone-4, e.g. Sold under the name "Uvinul MS40”; Benzophenone-9, e.g. B. sold under the
- Benzophenone-6 e.g. B. marketed under the name "Helisorb 11" by the company Norquay
- Benzophenone-8 z. B. sold under the name
- benzalkonium methosulfates e.g. Sold under the name "Mexoryl SO” from the company. Chimex, Terephthalylidenedicamphorsulfonklare, z. Sold under the name "Mexoryl SX” by Chimex,
- Phenylbenzimidazole derivatives phenylbenzimidazolesulfonic acid, e.g. B.
- Phenylbenzotriazole derivatives Drometrizole trisiloxanes, e.g. B. marketed under the name “Silatrizole” by the company. Rhodia Chimie,
- Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form e.g. B. marketed under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B.
- Triazine derivatives ethylhexyltriazone, e.g. B. sold under the name "Uvinul T150" from the company. BASF, Diethylhexylbutamidotriazone, z. B.
- Anthraniline derivatives menthyl anthranilate, e.g. B. marketed under the name "Neo Heliopan MA" by Fa. Symrise.
- Imidazole derivatives ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.
- Benzalmalonate Derivatives Polyorganosiloxanes containing functional benzalmalonate groups, e.g. Polysilicone-15, e.g. Sold under the name "Parsol SLX" by Hoffmann LaRoche.
- 4,4-Diarylbutadiene derivatives 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.
- Benzoxazole Derivatives 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures containing this.
- UV ⁇ filters can be used.
- Suitable organic UV-protective substances are preferably to be selected from the following list: ethylhexyl salicylate,
- Phenylbenzimidazolesulfonic acid benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate,
- organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.
- the preparations may contain, in addition to the compounds of the formula I and the optionally organic UV filters, as described above, further inorganic UV filters, so-called particulate UV filters.
- these combinations with particulate UV filters are possible both as a powder and as a dispersion or paste of the following types.
- coated titanium dioxide e.g., Eusolex® T-2000, Eusolex® T-AQUA,
- Eusolex® T-AVO Eusolex® T-OLEO
- zinc oxides e.g., Sachtotec®
- Iron oxides or else cerium oxides and / or zirconium oxides are preferred. Furthermore, combinations with pigmentary titanium dioxide or
- Zinc oxide is possible, the particle size of these pigments being greater than or equal to 200 nm, for example Hombitan® FG or Hombitan® FF-Pharma.
- the preparations may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat
- one or more of the following aftertreatment components may be selected: amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids,
- fatty acids fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially collagen or elastin), alkanolamines, silica, alumina, other metal oxides, Phosphates, such as sodium hexametaphosphate or glycerin.
- Preferably used particulate UV filters are:
- untreated titanium dioxides e.g. the products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,
- Silica aftertreatment such as e.g. the product "Microtitanium Dioxide MT 100 SA of Tayca; or the product “Tioveil Fin” from Uniqema,
- micronised titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment such as e.g. Microtitanium Dioxide MT 100 T from Tayca, Eusolex T-2000 from Merck,
- Iron stearate aftertreatment for example the product "Microtitanium Dioxide MT 100 F” from Tayca, Aftertreated micronised titanium dioxides with silicas,
- Alumina and silicone aftertreatment such as e.g. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,
- the treated micronized titanium dioxides used for combination may also be post-treated with:
- Alumina and stearic acid such as. the product UV-Titan M160 of the company Sachtleben,
- Aluminum and silicone oils e.g. the product UV titanium M262 of the Fa.
- Polydimethylsiloxanes e.g. the product 70250 Cardre UF Ti02SI3 "from the company Cardre,
- Escalol Z100 from ISP (alumina aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer blend)
- Fuji ZNO-SMS-10 from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane);
- mixtures of various metal oxides e.g. Titanium dioxide and cerium oxide with and without Nachbenmaschine be used, such. the product Sunveil A of the company Ikeda.
- inorganic UV filters are incorporated usually in an amount of 0.1 weight percent to 25 weight percent, preferably 2 wt .-% - 10 wt .-%, in the preparations.
- UV filters can also be used in encapsulated form.
- organic UV filters it is beneficial to use organic UV filters in
- the capsules in preparations to be used according to the invention are preferably present in amounts which ensure that the encapsulated UV filters in the abovementioned
- Weight percent ratios are present in the preparation.
- at least one compound of formula I may also continue
- Color pigments may be included, wherein the layer structure of the pigments is not limited.
- the color pigment when used from 0.5 to 5 wt .-% should be skin-colored or brownish.
- Pigments is familiar to the skilled person.
- Preferred preparations may also contain at least one further cosmetic active ingredient, for example selected from
- Antioxidants anti-aging, anti-wrinkle, anti-dandruff, anti-acne, anti-cellulite, deodorants or vitamins.
- antioxidants e.g. Amino acids (e.g.
- imidazoles eg Urocaninklare
- peptides such as D, L-carnosine, D-camosine, L-camosine and their derivatives (eg anserine)
- carotenoids eg a-carotene, ß-carotene, lycopene
- carotenes eg a-carotene, ß-carotene,
- 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 , y-linoleyl, cholesteryl and glyceryl esters
- thiols eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , y-linoleyl, cholesteryl and glyceryl esters
- Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives esters, ethers, peptides, lipids, nucleotides, nucleosides and salts
- sulfoximine compounds for example buthionine sulfoximines
- Heptathionine sulfoximine in very low tolerated dosages (e.g., pmol to ⁇ / kg), further (metal) chelators (e.g., ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), ⁇ -hydroxy acids (e.g.
- Citric acid lactic acid, malic acid), humic acid, bile acid,
- Bile extracts bilirubin, biliverdin, EDTA, EGTA, pentasodium
- ethylenediaminetetramethylene phosphonate and its derivatives unsaturated fatty acids and their derivatives, vitamin C and derivatives (e.g.
- Ascorbyl palmitate magnesium ascorbyl phosphate, ascorbyl acetate
- Tocopherols and derivatives e.g., vitamin E acetate
- vitamin A and derivatives e.g., vitamin A palmitate
- benzoic resin coniferyl benzoate rutinic acid and its derivatives, ⁇ -glycosyl rutin, ferulic acid
- Stilbenes and their derivatives e.g., stilbene oxide, trans-stilbene oxide.
- Suitable antioxidants are also compounds of the formulas A or B. wherein
- 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
- 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 each independently of one another are H or linear or branched alkyl having 1 to 8 C atoms
- R 5 H linear or branched alkyl having 1 to 8 carbon atoms or
- 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) and / or 2- (4-hydroxy-3,5-dimethoxybenzyl ) -malonic acid bis (2-ethylhexyl) ester (eg RonaCare® AP).
- antioxidants are also suitable for use in the cosmetic preparations according to the invention.
- Acquaintances and Commercially available mixtures are, for example, mixtures containing as active ingredients lecithin, L - (+) - ascorbyl palmitate and citric acid, natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and
- Citric acid e.g., Oxynex® K LIQUID
- tocopherol extracts e.g., tocopherol extracts
- L - (+) - ascorbyl palmitate L - (+) - ascorbic acid and citric acid
- DL-a-tocopherol L (+) - ascorbyl palmitate
- citric acid and lecithin eg Oxynex® LM
- BHT butylhydroxytoluene
- L - (+) - ascorbyl palmitate and citric acid eg Oxynex® 2004.
- Compounds of the invention in such compositions usually in weight percent ratios ranging from 1000: 1 to 1: 1000, preferably used 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 mainly known as plant dyes, frequently have an antioxidant potential.
- Quercetin (cyanidanol, cyanidolone 1522, meietin,
- effective antioxidant e.g., CA. Rice-Evans, N.J. Miller, G.
- K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens investigate the pH dependence of the antioxidant activity of hydroxyflavones., Quercetin shows the highest pH across the pH range Activity of the investigated structures.
- Suitable anti-aging ingredients especially for skin care
- Preparations are preferably so-called compatible solutes. These are substances that are involved in the osmoregulation of
- osmolytes Plants or microorganisms are involved 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. As osmolytes are in the sense of the Germans
- Patent application DE-A-10133202 especially substances from the group of polyols, such as myo-inositol, mannitol or sorbitoi and / or understood one or more of the following osmolytically active substances: 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.
- B. Compounds that are converted to osmolytes by metabolic steps.
- compatible solute substances selected from the group consisting of Pyrimidincarbonklaren (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic
- Diphosphoglycerate N. acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), ⁇ -mannosylglycerate (Firoin) , ß- Mannosylglyceramid (Firoin-A) and / or di-mannosyl-di-inositolphosphat (DMIP) or an optical isomer, derivative, for example an acid, a salt or ester of these compounds or combinations thereof used.
- DIP di-oxide di-myo-inositol phosphate
- cDPG cyclic 2,3-diphosphoglycerate
- DGP 1, 1-diglycerol phosphate
- ⁇ -mannosylglycerate Firoin
- ß- Mannosylglyceramid Firoin-A
- ectoine (S) -1,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives. Additional can be used as anti-aging active ingredients Merck products such as 5,7-dihydroxy-2-methyl-chromone, marketed under the
- Ronacare® tiliroside or Ronacare® cyclopeptide 5 can be used.
- the preparations to be used may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamine hydrochloride hydrochloride (vitamin B, riboflavin (vitamin B 2 ), nicotinamide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D2), vitamin E, DL-a-tocopherol,
- Vitamins are usually added to the flavonoid-containing premixes or preparations when applied cosmetically in the range of 0.01% to 5.0% by weight, based on the total weight.
- retinoids are also effective anti-cellulite agents.
- Another well-known anti-cellulite drug is caffeine.
- the present invention also provides a process for
- At least one compound of the formula I is mixed with a carrier suitable for topical applications and optionally with auxiliaries and / or fillers.
- auxiliaries and / or fillers are described in detail in the following part.
- the said constituents of the preparation can be incorporated in the usual way, by means of techniques which are well known to the person skilled in the art.
- the cosmetic and dermatological preparations can be in various forms. So they can z.
- Oil-in-water (W / O / W) or O / W / O a gel, a solid stick, an ointment or even an aerosol.
- O / W emulsins are especially preferred.
- Emulsions, W / O emulsions and O / W emulsions are available in the usual way.
- As an application form of the preparations to be used e.g.
- solutions solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing
- 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, for example 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.
- Sprays may additionally contain the usual volatilized, liquefied propellants, e.g.
- Solutions and emulsions may be the usual carriers such as
- Solvents, solubilizers and emulsifiers e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, XTend 226 (L'Oreal), glycerin fatty acid esters, polyethylene glycols and fatty acid esters of Sorbitans or mixtures of these substances.
- a preferred solubilizer in general is 2-isopropyl-5-methylcyclohexanecarbonyl-D-alanine methyl ester.
- Suspensions may be the usual carriers such as liquid
- Diluent e.g. Water, ethanol or propylene glycol
- Suspending agent e.g. ethoxylated isostearyl alcohols
- 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 the usual carriers 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 diethanolamides vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.
- Facial and body oils may contain the usual carriers 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 are examples of oils and vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.
- Other typical cosmetic applications include lipsticks, lip balms, powder, emulsion and wax make-up as well
- the preferred preparation forms include, in particular, emulsions.
- Emulsions are advantageous and contain z.
- Oils such as triglycerides of capric or caprylic acid, also 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
- Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes,
- the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 C atoms and saturated and / or unsaturated,
- branched and / or unbranched alcohols of a chain length of 3 to 30 C atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or
- ester oils can then be advantageously selected from the group
- 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 contains
- alcohols, diols or polyols of low C number, and their ethers preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, tirionoethyl or monobutyl ether,
- Silica aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from 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 organic solvent.
- the preparations to be used contain hydrophilic surfactants.
- the hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.
- O / W 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, primarily 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 ⁇ / V Emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or are
- Emulsifiers also lower or above.
- Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate,
- Polyethylene glycol (14) isostearate
- polyethyleneglycol (15) isostearate
- Polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, Polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate,
- Polyethylene glycol (20) oleate Polyethylene glycol (20) oleate.
- the sodium laureth-11-carboxylate can be advantageously used.
- the alkyl ether sulfate sodium laureth-4 sulfate can be advantageously used.
- polyethylene glycol (3-O) 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,
- Fatty alcohols having 8 to 30 carbon atoms monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched
- W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate,
- Glyceryl monolaurate glyceryl monocaprinate, glyceryl monocaprylate or PEG-30 dipolyhydroxystearate.
- the preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, such as Thickeners, emollients, moisturizers,
- surfactants such as soaps, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.
- 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 cream or milk and for example fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers
- oily lotions based on natural or synthetic oils and waxes, lanolin,
- Fatty acid esters in particular triglycerides of fatty acids, or oily alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.
- 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.
- the usual blowing agents are generally used, such as alkanes, fluoroalkanes and chlorofluoroalkanes, preferably alkanes.
- Example 1 Performing a B16V Mouse Melanoma Cell Test
- FBS Fetal Bovine Serum, Invitrogen, article no: 10499044
- 2 mM L-glutamine Invitrogen, item no: 25030
- 1 mM sodium pyruvate Invitrogen, item no: 11360
- the medium is separated and the cells are washed with 10mL D-PBS (Dulbecco's Phosphate-Buffered Salines, Invitrogen, Item No. 14190) and then aspirated.
- 1 ml HyQtase-Cell Detachment Solution (Hyclone, article number SV30030.01) is added to the cells. The bottle is swiveled several times and the HyQtase-Cell
- Detachment Solution then removed by aspiration. Then the cells are incubated for 5 min in the incubator at 37 ° C and 5% C0 2 . The cells are taken up in the modified RPMI medium (see above) and the number of cells determined. The cells are stained with trypan blue and counted in a Neubauer chamber. Subsequently, the cells are seeded again in the modified RPMI medium (see above) in a defined cell number of 80,000 cells per well (6-well Clear Plate, TCT, PS (Nunc)).
- the cells are incubated for 24 h at 37 ° C and 5% CO 2 , then the medium is removed. Subsequently, the substance to be examined (see table below) is added in various concentrations.
- the medium is aspirated and the cells are washed with 1000 ⁇ M D-PBS (Invitrogen, Item No. 14190). The medium is sucked off again. It will be 250 ⁇ _ HyQtase- Cell
- Hyclone, Item No. SV30030.01 is added to the cells.
- the 6-well plate is pivoted several times and the HyQtase- Cell Detachment Solution is then removed by suction. Then the cells are incubated for 5 min in the incubator at 37 ° C and 5% CO 2 . Cells are transfected into 1.5mL DPBS (Invitrogen, Item # 14190)
- DMSO Dimethyl sulfoxide
- IBMX serves as a positive control.
- Result Test 2 Id, le, Ig and Ih promote melanogenesis in the B-16V mouse melanoma cell assay.
- phase A is heated to 75 ° C and phase B to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and stirred until a homogeneous mixture is formed.
- phase A is heated to 75 ° C and phase B to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and stirred until a homogeneous mixture is formed.
- phases A and B are heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 ° C was added.
- phase B is dissolved and then it is given to phase A.
- Example 6 O W anti-aging cream with UV A / B protection
- phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized cooled to room temperature.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102012009278A DE102012009278A1 (de) | 2012-05-11 | 2012-05-11 | Phenylketon-Derivate als Selbstbräuner |
PCT/EP2013/001136 WO2013167228A2 (de) | 2012-05-11 | 2013-04-17 | Phenylketon-derivate als selbstbräuner |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2846765A2 true EP2846765A2 (de) | 2015-03-18 |
Family
ID=48143581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13717950.3A Withdrawn EP2846765A2 (de) | 2012-05-11 | 2013-04-17 | Phenylketon-derivate als selbstbräuner |
Country Status (4)
Country | Link |
---|---|
US (2) | US20150182432A1 (de) |
EP (1) | EP2846765A2 (de) |
DE (1) | DE102012009278A1 (de) |
WO (1) | WO2013167228A2 (de) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW197375B (de) | 1990-11-19 | 1993-01-01 | Hayashibara Biochem Lab | |
FR2680683B1 (fr) | 1991-08-29 | 1993-11-12 | Oreal | Composition cosmetique filtrante contenant un polymere filtre a structure hydrocarbonee et une silicone filtre. |
DE10133202A1 (de) | 2001-07-07 | 2003-01-16 | Beiersdorf Ag | Osmolyte enthaltende kosmetische und dermatologische Zubereitungen zur Behandlung und aktiven Prävention trockener Haut und anderer negativer Veränderungen der physiologischen Homöostase der gesunden Haut |
DE10148850A1 (de) * | 2001-10-04 | 2003-04-10 | Henkel Kgaa | Mittel zum Färben von keratinhaltigen Fasern |
FR2833166B1 (fr) | 2001-12-07 | 2004-08-27 | Oreal | Composition autobronzante contenant un derive du 2-hydroxybenzophenone aminosubstitue et un agent autobronzant |
US20050271608A1 (en) * | 2004-06-05 | 2005-12-08 | Gupta Shyam K | Skin whitening compositions based on hydroxyaryl alkyl ketones and their isosteric derivatives |
DE102006004327A1 (de) * | 2006-01-31 | 2007-08-02 | Merck Patent Gmbh | Chromen-4-on-Derivate |
DE102010026776A1 (de) * | 2010-07-10 | 2012-01-12 | Merck Patent Gmbh | Bräunungsverstärker |
-
2012
- 2012-05-11 DE DE102012009278A patent/DE102012009278A1/de not_active Withdrawn
-
2013
- 2013-04-17 US US14/400,751 patent/US20150182432A1/en not_active Abandoned
- 2013-04-17 EP EP13717950.3A patent/EP2846765A2/de not_active Withdrawn
- 2013-04-17 WO PCT/EP2013/001136 patent/WO2013167228A2/de active Application Filing
-
2017
- 2017-07-07 US US15/643,701 patent/US20170304168A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2013167228A2 * |
Also Published As
Publication number | Publication date |
---|---|
DE102012009278A1 (de) | 2013-11-14 |
US20150182432A1 (en) | 2015-07-02 |
WO2013167228A3 (de) | 2014-04-10 |
WO2013167228A2 (de) | 2013-11-14 |
US20170304168A1 (en) | 2017-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2568953B1 (de) | Triazine als reaktionsbeschleuniger | |
WO2011141110A2 (de) | Photostabilisatoren | |
EP2648689B1 (de) | 2-pyrone | |
DE102011115285A1 (de) | Phosphanoxide als Reaktionsbeschleuniger | |
EP2665717B1 (de) | 7-acyloxy-chromen-4-on-derivate und ihre verwendung als selbstbräunungssubstanzen | |
WO2012007095A2 (de) | Bräunungsverstärker und selbstbräunungssubstanzen | |
EP3402576B1 (de) | Noreugenin-glykosid-derivate | |
EP2427443B1 (de) | Zimtsäureascorbate | |
EP2590619A2 (de) | Bräunungsverstärker und selbstbräunungssubstanzen | |
EP2654687A1 (de) | Dihydroxyacetonmonoether | |
EP2709731B1 (de) | Extrakte aus darlingtonia californica | |
EP2846765A2 (de) | Phenylketon-derivate als selbstbräuner | |
EP2775996B1 (de) | Verwendung von propanol- und propenolderivaten als antioxidantien | |
EP2600854B1 (de) | Phenethyl-, phenethylen-, phenetin- und indanonderivate | |
WO2011020536A1 (de) | Glycerinaldehydderivate und deren acetale | |
WO2013020624A1 (de) | Extrakte aus tradescantia virginiana | |
US20150139922A1 (en) | Extracts of darlingtonia californica |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20140924 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20170207 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: A61Q 19/08 20060101ALI20190114BHEP Ipc: A61Q 17/04 20060101ALI20190114BHEP Ipc: A61K 8/97 20170101ALI20190114BHEP Ipc: A61K 8/35 20060101AFI20190114BHEP Ipc: A61Q 19/04 20060101ALI20190114BHEP |
|
INTG | Intention to grant announced |
Effective date: 20190211 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20190622 |