EP2846765A2 - Phenyl ketone derivatives as self-tanning agents - Google Patents

Abstract

The present invention concerns the use of phenyl ketone derivatives of formula I for use as self-tanning substance or for increasing melanin synthesis, improving melanin transport and/or improving the distribution of melanin in suprabasal layers, as well as preparations containing these phenyl ketone derivatives.

Description

 Phenylketone derivatives as a self-tanner

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.

The trend away from sophisticated paleness to "healthy, sporty brown skin" has been unbroken for years, and people are exposing their skin to sunshine for a tanned complexion that causes pigmentation through melanin formation However, the sunlight also has a damaging effect on the skin, in addition to the acute injury (sunburn) occur

Long-term damage due to excessive exposure to light from the UVB range (wavelength 280-320 nm), such as an increased risk of developing skin cancer. Excessive exposure to UVB and UVA radiation (wavelength: 320-400 nm) produces highly reactive radical species that continue to multiply upon completion of irradiation, resulting in wrinkling and skin aging.

Natural protection against the negative effects of solar radiation is provided by the tanning (pigmentation) of the skin. 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. Depending on the chemical composition of the biochemically formed pigments, a distinction is made between the brownish-black eumelanin and the reddish-yellow pheomelanin. The observed skin tone is determined by the ratio of these two types of melanin.

This formation of pigment originating from the amino acid tyrosine is predominantly initiated by UVB radiation and called "indirect

Their development takes place over several days, the sun tan thus obtained persists for several weeks, in the case of "direct pigmentation", which starts with the sun's rays

predominantly colorless melanin precursors are oxidized by UVA radiation to dark-colored melanin. Since this oxidation is reversible, it leads to a short-lasting tanning of the skin.

An artificial tanning of the skin can be produced externally with the help of make-up and orally by taking carotenoids.

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 chemical structural feature keto or aldehyde groups in the vicinity of alcohol functions and belong predominantly to the substance class of sugars. Particularly commonly used self-tanning substances are 1,3-dihydroxyacetone (DHA), used in an amount of 700 t / a, and erythrulose. 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

completed. The tan thus obtained is not washable and is removed only with the normal Hautabschuppung. However, these color products themselves have no UV-absorbing properties, so when exposed to the sun, an additional

Sunscreen (clothing, hat, UV filter) is required.

In contrast to "tanned" skin, the tanned skin is not protected against sunburn.

There is therefore still a need for dermatologically acceptable skin-dyeing substances which are suitable for use in cosmetic and / or dermatological preparations or medical products and which enhance the natural tanning of the skin by increasing melanin synthesis and at the same time provide better skin protection.

Sun protection, especially against UVB radiation allow.

The object underlying the present invention was therefore to provide new self-tanning substances

improved properties.

Surprisingly, it has now been found that certain

Phenylketone derivatives in excellent manner as

Self-tanning substances are suitable.

For the purposes of the invention, the term 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

Michael addition reacts, as well as a melanogenesis promoter or Propigmentierungswirkstoff, which promotes the natural tanning of the skin.

From EP 1317920 A1 it is known that amino-substituted 2-hydroxybenzophenone derivatives are suitable as self-tanning substances for the artificial tanning of the skin. Further, Ding et al. (Experimental Dermatology 2011, 20, 720-724) that certain acetophenones such as 2,5-dihydroxyacetophenone or 2,6-dihydroxyacetophenone have a skin-lightening effect.

However, the use of phenylketone derivatives as a self-tanner is not known in the art.

A first object of the present invention is therefore the

Use of at least one compound of the formula I

wherein

R1 to R5 are independently H, OH, NH _2, R7, OR7 or O (C = O) R7, and

 R6 and R7 independently represent

-straight-chain or branched C to C ₃₀ -alkyl,

-straight-chain or branched C ₂ - to C ₃ o-alkenyl,

 or a cycloalkyl or cycloalkenyl group having 5 to 8 C atoms, wherein the cycloalkenyl group is not

 an aromatic, as a self-tanning substance.

The compounds of formula I act as biological

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

Use of at least one compound of the formula I as defined above to increase melanin synthesis, improve melanin transport and / or improve the distribution of melanin in suprabasal

Layers. The increase in melanin synthesis can be carried out according to the invention both in the skin and in the hair. Thus, 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. According to the invention, the substances can accordingly be applied to the hair or the scalp.

Basically, within the meaning of the present invention of the

The term "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.

Most preferably 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.

Most preferably, R 7 is methyl, ethyl or propyl, especially methyl. In one possible embodiment, R6 and R7 are identical. Preferably, R6 and R7 are methyl.

The radicals R 1 to R 5 of the compound of the formula I independently of one another are preferably H, OH, NH ₂ , methyl, OCH ₃ or O (C =O) CH ₃ .

In a further preferred embodiment, the radicals R 2 and R 4 are H. Particularly preferably, 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).

The substances are commercially available from Merck Chemicals (Art.

8.04310, la), ABCR GmbH (Art. AB1 17448, Ib), Merck Chemicals (Art.

8.41389, Ic), Alfa Aesar GmbH (Art. A18539, Id), TCI Germany GmbH (Art. T2030, le), Alfa Aesar GmbH (Art. B21624, If), Sigma-Aldrich Chemie (Art. A37804, Ig) and Sigma-Aldrich Chemie (Art. 630594, Ih).

Particular preference is given to the compounds of the formulas Ia, Ib and / or Id.

In general, the compounds of the formula I, as defined above, by a "classic" Friedel-Crafts acylation of a corresponding

Polyphenols (such as resorcinol, phloroglucinol or 1,3-dimethoxybenzene) with an 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

Reaction analogous to H. Muller et al., Angewandte Chemie, International Edition 2010, 49 (11), 2045-49.

Alternatively, the following synthesis is possible: Since the nucleophilic phenolate can also react with CO ₂ as a weak electrophile, 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. By customary derivatization of the functional groups (in particular the phenolic hydroxyl group), further derivatives according to formula I can be obtained. 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.

For the purposes of the present invention is in a

straight-chain or branched alkyl group having 1 to 6 C atoms

For example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, pentyl, isopentyl, 1-, 2- or 3-methylbutyl, 1, 1, 1, 2 or 2.2 Dimethylpropyl, 1-ethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1, 1, 2 or 1, 2,2-trimethylpropyl, 1, 1, 1, 2, 1, 3 -, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1-, 2-, 3- or 4-methylpentyl or hexyl.

 By an 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.

According to the invention, an alkenyl group may have one or more

Double bonds included. A branched or unbranched

Alkenyl group having 2 to 6 C atoms is, for example, allyl, vinyl,

Propenyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, 2-methyl-1- or 2-butenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, 2-methyl-1,3-butadienyl , 2,3-dimethyl-1,3-butadienyl, 1-, 2-, 3- or 4-pentenyl, iso-pentenyl or hexenyl. 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.

A cycloalkyl or cycloalkenyl group in the sense of

present invention 5 to 8 C-atoms. 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

Improve the distribution of melanin in suprabasal layers and / or protect the skin from damaging UV rays.

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. In addition, 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.

So that the compounds of the formula I can develop their positive effect on the skin particularly well, it may be preferable to

 Compounds of formula I, as described above, to penetrate into deeper skin layers. There are several options available. On the one hand, 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. As a further possibility, in 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.

The use according to the invention is preferably non-therapeutic. Another object of the present invention is a preparation containing at least one compound of formula I or their

preferred embodiments as defined above.

The preparations are usually topically applicable preparations, for example cosmetic or cosmetic preparations

dermatological formulations or medical devices. The preparations in this case contain a cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients. Is it pharmaceutical

Preparations, the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients. For the purposes of the present invention, the term 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

Total amount of preparation used. It prepares it

The skilled person no Schwierigketten the quantities depending on the intended effect of the preparation to select accordingly.

Furthermore, 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 Propigmentierungswirkstoff, which promotes the natural tanning of the skin.

Advantageous self-tanning substances which can be used include: 1,3-dihydroxyacetone, glycerolaldehyde,

 Hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2-hydroxy-1,4-naphthoquinone (Lawson). Very particular preference is 1, 3-dihydroxyacetone, erythrulose or a combination thereof.

In principle, 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).

Preferably, 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.

Preparations with self-tanning properties, especially those containing dihydroxyacetone, tend to be used on the

Human skin to malodors, which are probably caused by degradation products of the dihydroxyacetone itself or by products of side reactions and which are perceived by the users sometimes as unpleasant. It has been shown that these malodors contribute Use of formaldehyde scavengers and / or flavonoids are avoided. Therefore, the preparation according to the invention can also

Formaldehydfänger and possibly flavonoids to improve the odor.

The preparation according to the invention which combines a self-tanning substance and a compound of the formula I has opposite one

Self-tanning product without addition of the compound of the formula I the following advantages:

 Acceleration of the tanning reaction,

 - Extension of the tanning reaction due to indirect

 Tanning reaction (UV-free tanning extension),

 - strengthening of the tanning reaction,

 - Avoidance of uneven browning due to clumsy

 Instruct,

 - the tanning achieved is closer to the natural tanning,

 - Improved protection against UV radiation.

The preparations according to the invention can also be used in addition to

Compounds of formula I additionally contain at least one UV filter.

Organic UV filters, called hydrophilic or lipophilic

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,

Camphor derivatives, triazine derivatives, β, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters described in application WO-93/04665.

Further examples of organic filters are given in the patent application EP-A 0 487 404. In the following, the named UV filters are usually named according to the INCI nomenclature. In particular suitable for a combination are:

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.

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.

sold under the name "Dipsal" from the company. Scher, TEA salicylate, z. B. marketed under the name "Neo Heliopan TS" of the Fa. Symrise. β, β-diphenylacrylate derivatives: 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

Name "Uvinul DS-49" from BASF, Benzophenone-5,

Benzophenone-6, e.g. B. marketed under the name "Helisorb 11" by the company Norquay, Benzophenone-8, z. B. sold under the name

"Spectra-Sorb UV-24" from American Cyanamid, Benzophenone-2 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, sold by Merck, Darmstadt under the name Eusolex® 4360. Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. Sold under the name "Mexoryl SD" from the company. Chimex, 4-Methylbenzylidenecamphor, z. B. sold under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. marketed under the name "Mexoryi SL" from the company Chimex, Camphor

benzalkonium methosulfates, e.g. Sold under the name "Mexoryl SO" from the company. Chimex, Terephthalylidenedicamphorsulfonsäure, z. Sold under the name "Mexoryl SX" by Chimex,

Polyacrylamidomethylbenzylidenecamphor sold under the name "Mexoryl SW" from Chimex.

Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B.

sold under the name "Eusolex 232" by the company Merck, disodium phenyl dibenzimidazole tetrasulfonate, z. B. marketed under the name "Neo Heliopan AP" by Fa. Symrise.

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.

sold under the name "Tinosorb M" from BASF.

Triazine derivatives: ethylhexyltriazone, e.g. B. sold under the name "Uvinul T150" from the company. BASF, Diethylhexylbutamidotriazone, z. B.

sold under the name "Uvasorb HEB" from the company Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines or 2,4,6-tris (biphenyl) -1,3, 5-triazines sold as Tinosorb A2B by BASF, 2,2 '- [6- (4-methoxyphenyl) -1, 3,5-triazine-2,4-diyl] bis [5- (2-ethylhexyl) oxy] - phenol, sold as Tinosorb S by BASF, N2, N4-bis [4- [5- (1, 1-dimethylpropyl) -2-benzoxazolyl] phenyl] -N6- (2-ethylhexyl) -1, 3,5-triazine -2,4,6-triamine sold as Uvasorb K 2A from Sigma 3V, or Bis (butylbenzoate) diaminotriazine aminopropyltrisiloxanes (Mexoryl SBS, ^' Chimex).

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.

Piperazine derivatives such as the compound

or the UV filters of the following structures

It is also possible to use UV filters based on polysiloxane copolymers having a random distribution according to the following formula, where e.g. a = 1, 2; b = 58 and c = 2.8 are:

The compounds listed are only examples

specific. Of course, other 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,

 Methylenebis (benzotriazolyl) tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxane, polysilicone-15, 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, 2,4-bis [5-1 ( dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines and mixtures thereof.

These 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.

In this case, both those from the group of titanium dioxides such.

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.

It may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat

Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53 64 described, were treated. In this case, one or more of the following aftertreatment components may be selected: amino acids,

 Beeswax, 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,

 Post-treated micronized titanium dioxides with alumina and

 Silica aftertreatment such as e.g. the product "Microtitanium Dioxide MT 100 SA of Tayca; or the product "Tioveil Fin" from Uniqema,

Aftertreated 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,

Post-treated micronized titanium dioxides with iron oxide and / or

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,

 - Post-treated micronized titanium dioxides with

 Sodium hexameta-phosphates, e.g. the product "Microtitanium

 Dioxide MT 150 W "from the company Tayca.

The treated micronized titanium dioxides used for combination may also be post-treated with:

- octyltrimethoxysilanes; such as. the product Tego Sun T 805 of the Fa.

 Degussa,

 - silica; such as. the product Parsol T-X from DSM,

 Alumina and stearic acid; such as. the product UV-Titan M160 of the company Sachtleben,

 - aluminum and glycerin; such as. the product UV titanium of the Fa.

 Sachtleben

 Aluminum and silicone oils, e.g. the product UV titanium M262 of the Fa.

 Sachtleben,

Sodium hexamethaphosphate and polyvinylpyrrolidone,

 Polydimethylsiloxanes, e.g. the product 70250 Cardre UF Ti02SI3 "from the company Cardre,

 Polydimethylhydrogensiloxanes, e.g. the product Microtitanium

 Dioxide USP Grade Hydrophobia "from Color Techniques.

Furthermore, the combination with the following products may also be advantageous:

- Untreated zinc oxides such. B. the product Z-Cote Fa. BASF

 (Sunsmart), Nanox of the company Elementis

Aftertreated zinc oxides such as the following products:

 • "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with

polymethylhydrogenosiloxane) • Nanogard Zinc Oxide FN from Nanophase Technologies

• "SPD-Z1" from Shin-Etsu (ZnO aftertreated with a

 Silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxanes

 "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);

 Untreated cerium oxide micropigment e.g. with the name "Colloidal Cerium Oxide" from Rhone Poulenc

 • Untreated and / or post-treated iron oxides with the

 Name Nanogar of the Fa. Arnaud.

By way of example, mixtures of various metal oxides, e.g. Titanium dioxide and cerium oxide with and without Nachbenhandlung be used, such. the product Sunveil A of the company Ikeda. In addition, mixtures of alumina, silica and

Silicon aftertreated titanium dioxide, zinc oxide mixtures such. the product UV titanium M261 from Sachtleben be used.

These 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.

By combining one or more of the compounds mentioned with UV filter action, the protective effect against harmful

Effects of UV radiation can be optimized. All mentioned UV filters can also be used in encapsulated form. In particular, it is beneficial to use organic UV filters in

to use encapsulated form. 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. In the described preparations, which contain according to the invention 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. Preferably, the color pigment when used from 0.5 to 5 wt .-% should be skin-colored or brownish. The selection of a corresponding

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.

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. There are many known and proven substances in the literature that can be used as antioxidants, e.g. Amino acids (e.g.

Glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg Urocaninsäure) and their derivatives, peptides such as D, L-carnosine, D-camosine, L-camosine and their derivatives (eg anserine), carotenoids, carotenes (eg a-carotene, ß-carotene, lycopene) and their derivatives, chlorogenic acid and their 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 , y-linoleyl, cholesteryl and glyceryl esters) and their salts,

Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (for example buthionine sulfoximines,

Homocysteine sulfoximine, buthionine sulfone, penta-, hexa-,

Heptathionine sulfoximine) in very low tolerated dosages (e.g., pmol to μηηΙ / kg), further (metal) chelators (e.g., α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-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) and benzoic resin coniferyl benzoate, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid,

Furfurylidenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its

Derivatives (eg ZnO, ZnS0 ₄ ), selenium and its derivatives (eg

Selenethionione), 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

 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) and / or 2- (4-hydroxy-3,5-dimethoxybenzyl ) -malonic acid bis (2-ethylhexyl) ester (eg RonaCare® AP).

Mixtures of 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

natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (eg, Oxynex® L LIQUID), DL-a-tocopherol, L (+) - ascorbyl palmitate, citric acid and lecithin (eg Oxynex® LM ) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex® 2004). Such antioxidants are with the

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.

Among the phenols which can be used according to the invention, the polyphenols, which occur in part as natural substances, are of particular interest for applications in the pharmaceutical, cosmetic or nutritional field. For example, the flavonoids or bioflavonoids, which are mainly known as plant dyes, frequently have an antioxidant potential. With effects of the substitution pattern of mono- and

Dihydroxy flavones deal with K. Lemanska, H. Szymusiak, B.

Tyrakowska, R. Zielinski, I.M.C.M. 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 dihydroxyflavones are partially non-antioxidant

Have properties.

Quercetin (cyanidanol, cyanidolone 1522, meietin,

Sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) as particular

effective antioxidant (e.g., CA. Rice-Evans, N.J. Miller, G.

Paganga, Trends in Plant Science 1997, 2 (4), 152-159). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 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

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 , α-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.

Preferably according to the invention as compatible solute substances selected from the group consisting of Pyrimidincarbonsäuren (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), β-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. In particular, 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

Tradenames RonaCare®Luremine, Ronacare®lsoquercetin,

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,

Tocopherol E acetate, tocopherol hydrogen succinate, vitamin K1, esculin (vitamin P active ingredient), thiamine (vitamin B1), 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-α-tocopherol, tocopherol E acetate , Nicotinic acid, pantothenic acid and biotin. 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. nutritional

Applications are based on the recommended vitamin requirement. The described retinoids are also effective anti-cellulite agents. Another well-known anti-cellulite drug is caffeine.

The present invention also provides a process for

Preparation of a preparation as described above, characterized

in that at least one compound of the formula I is mixed with a carrier suitable for topical applications and optionally with auxiliaries and / or fillers. Suitable excipients and auxiliaries 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. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. Oil-in-water (W / O / W) or O / W / O, a gel, a solid stick, an ointment or even an aerosol. Preference is given to emulsions. 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.

called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing

Cleaning preparations, oils, aerosols, plasters, envelopes, dressings and sprays.

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.

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 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,

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, 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 amide ether sulfates, alkylamido betaines, fatty alcohols,

 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. Other typical cosmetic applications include lipsticks, lip balms, powder, emulsion and wax make-up as well

Sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms include, in particular, emulsions.

Emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of preparation.

The lipid phase can be selected advantageously from the following

Group of substances: - mineral oils, mineral waxes

 - 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

 Fatty alcohols with lower alkanoic acids or with fatty acids;

Silicone oils, such as dimethylpolysiloxanes, diethylpolysiloxanes,

 Diphenylpolysiloxanes and mixed forms thereof.

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

unbranched alcohols of a chain length of 3 to 30 C atoms. Such ester oils can then be advantageously selected from the group

 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 octyldodecylphenyl imitation, oleyl oleate, oleyl erucate,

Erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, eg. B. jojoba oil.

Furthermore, 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

optionally advantageous 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,

Diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g. For example, ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group

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.

In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another

Be part of it. In a preferred embodiment, the preparations to be used contain hydrophilic surfactants. The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.

As 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. For example, 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 ΟΛ / V Emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or are

Isoalkylderivate ago, so the preferred HLB value of such

Emulsifiers also lower or above.

It is advantageous to include the fatty alcohol ethoxylates from the group of

ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols

(Cetearyl alcohols).

It is also advantageous to choose the fatty acid ethoxylates from the following group:

 Polyethylene glycol (20) stearate, polyethyleneglycol (21) stea rat,

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, polyethyleneglycol (15) isostearate,

Polyethylene glycol (16) isostearate, polyethyleneglycol (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 glycol (13) oeate,

Polyethylene glycol (14) oleate, polyethylene glycol (15) oleate,

Polyethylene glycol (16) oleate, polyethylene glycol (17) oleate,

Polyethylene glycol (18) oleate, polyethylene glycol (19) oleate,

Polyethylene glycol (20) oleate.

As the ethoxylated alkyl ether carboxylic acid or its salt, the sodium laureth-11-carboxylate can be advantageously used. As the alkyl ether sulfate, sodium laureth-4 sulfate can be advantageously used. As the ethoxylated cholesterol derivative, polyethylene glycol (3-O) cholesteryl ether can be advantageously used. Also polyethylene glycol (25) soybean oil has been proven. As ethoxylated triglycerides, the polyethylene glycol (60) Evening Primrose Glycerides can advantageously be used (Evening Primrose = evening primrose).

It is furthermore advantageous to use the 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) glycerylcaprat / cprinat,

 Polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate).

It is also beneficial to have the sorbitan esters from the group

 Polyethylene glycol (20) sorbitan monolaurate,

 Polyethylene glycol (20) sorbitan monostearate,

 Polyethylene glycol (20) sorbitan monoisostearate,

 Polyethylene glycol (20) sorbitan monopalmitate,

Polyethylene glycol (20) to choose sorbitan monooleate. As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:

 Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched

Alkan carboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol 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, onoglycerinether saturated and / or unsaturated , branched and / or unbranched alcohols of a

Chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 carbon atoms and sorbitan esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18, carbon atoms.

Particularly advantageous 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 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, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.

It is possible to use as 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

Contains presence of water.

Further preferred embodiments provide 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. If a preparation is formulated as an aerosol, the usual blowing agents are generally used, such as alkanes, fluoroalkanes and chlorofluoroalkanes, preferably alkanes.

Even without further statements, it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments and examples are therefore merely illustrative and in no way limiting in any way

To understand the revelation. The complete disclosure of all applications and publications cited above and below are incorporated by reference into this application.

Other important features and advantages of the invention will become apparent from the dependent claims and from the examples. The examples are intended to illustrate the present invention without limiting its scope.

Examples:

Example 1: Performing a B16V Mouse Melanoma Cell Test

B16V mouse melanoma cells (manufacturer: DSMZ, article number: ACC370) are in RPMI medium (Invitrogen, article no .: 31870), the additional 10% FBS (Fetal Bovine Serum, Invitrogen, article no: 10499044 ), 2 mM L-glutamine (Invitrogen, item no: 25030) and 1 mM sodium pyruvate (Invitrogen, item no: 11360) are added (= modified RPMI medium), transferred to a culture flask and incubated at 37 ° C. and 5% for 72 h. CO ₂ incubated. 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.

After the last incubation period, the medium is aspirated and the cells are washed with 1000 μM D-PBS (Invitrogen, Item No. 14190). The medium is sucked off again. It will be 250μΙ_ HyQtase- Cell

Detachment Solution (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)

taken and converted into a cup (SARSTEDT, Ref. 72.692.005). Subsequently, the cell number is determined. The cells are stained with trypan blue and counted in a Neubauer chamber. The cells are then centrifuged at 3500 g for 1 min. The resulting pellets are photographed and then the supernatant is suctioned off. The pellets are dissolved in 1 ml of 1 N NaOH at 80 ° C. for 1 h and then cooled to RT. Then 200μΙ_ per cup (as quadruple determination) pipetted into a 96 well plate (VWR, Item No. 4100636981) and the absorbance at 405nm wavelength determined (Satire, Tecan). By means of a calibration line, the content of melanin can be determined. As a comparison to the compounds of formula I to be investigated in parallel, each time a sample with dimethyl sulfoxide (DMSO) (0.1%) as

Negative control and a sample with IBMX (200 μητι) tested as a positive control. The following tables give the results of the determination of

 Melanin concentration indicated for the indicated

 Substance dilutions are obtained.

 The results obtained are relative to the negative control with

 Dimethyl sulfoxide (DMSO), whose measured value is set to 100%. IBMX serves as a positive control.

Test 1:

Result Test 1: Ia, Ib and Ic promote melanogenesis in the B16 V mouse melanoma cell test. Test 2:

Result Test 2: Id, le, Ig and Ih promote melanogenesis in the B-16V mouse melanoma cell assay.

Example 2: O / W formulation

 Components / Trade name Source of supply INCI [weight% 1

A

 Marlipal 1618/11 (1) CETEARETH-11 3

Lanette O (2) CETEARYL ALCOHOL 7

Luvitol EHO (3) CETEARY LOCTANOATE 5

Tegosoft TN (4) C12-15 2.5

 benzoates

 Miglyol 812 N (1) CAPRYLIC / CAPRIC 2.5

 TRIGLYCERIDES

 Propyl 4-hydroxybenzoate (5) PROPYLPARABEN 0.05

1 - (2-methoxyp enyl) (6) 1 ethanone (Ib)

B

 1, 2-Propanediol (5) PROPYLENE GLYCOL 4

Methyl 4-hydroxybenzoate (5) METHYLPARABENES 0.15

Water, demineralized AQUA (WATER) ad 100 Water, demineralized 10

Total 100.00

Production method:

 First, 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.

Sources:

 (1) Sasol Germany GmbH (2) Cognis GmbH (3) BASF AG

 (4) Degussa-Goldschmidt AG (5) Merck KGaA / Rona® (6) ABCR

GmbH

Example 3: O / W formulation

Production method: First, 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.

Sources:

 (1) Sasol Germany GmbH (2) Cognis GmbH (3) BASF AG

(4) Degussa-Goldschmidt AG (5) Merck KGaA / Rona® (6) TCI Deutschland GmbH

Example 4: O / W formulation

PHOSPHATE

 Water, demineralized AQUA (WATER) 10.00

1- (2-hydroxy-6-methoxyphenyl) - (8) 0.5 ethanone (Id)

Total 100.00

Production method:

 First, 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.

Sources:

 (1) Degussa-Goldschmidt AG, (2) Cognis GmbH, (3) BASF AG, (4) Sasol Germany GmbH, (5) Merck KGaA / Rona®, (6) Dow Corning, (7) Kuhs GmbH & Co. KG (8) Alfa Aesar GmbH

Example 5: W / O formulation

Production method: First, phase B is dissolved and then it is given to phase A. The pH is adjusted to pH = 6.0 with sodium hydroxide solution or citric acid.

Sources:

 (1) Dow Coming (2) Merck KGaA / Rona®

Example 6: O W anti-aging cream with UV A / B protection

Production method:

 First, 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.

References: (1) Merck KGaA / Rona®, (2) Degussa-Goldschmidt AG, (3) Cognis GmbH, (4) BASF AG, (5) Sasol Germany GmbH, (6) TCI Germany GmbH

Claims

claims

1. Use of at least one compound of the formula

 wherein

R1 to R5 are independently H, OH, NH _2, R7, OR7 or O (C = O) R7, and

 R6 and R7 independently represent

-straight-chain or branched C to C ₃₀ -alkyl,

-straight-chain or branched C ₂ - to C ₃₀ -alkenyl,

 or a cycloalkyi or cycloalkenyl group having 5 to 8 C

Atoms, wherein the cycloalkenyl group is not an aromatic, as a self-tanning substance. 2. Use of at least one compound of the formula I.

 wherein

R1 to R5 are independently H, OH, NH _2, R7, OR7 or O (C = O) R7, and

 R6 and R7 independently represent

-straight-chain or branched C 1 - to C 30 -alkyl, -straight-chain or branched C2 to C3o-alkenyl,

 or a cycloalkyl or cycloalkenyl group having 5 to 8 C

Atoms, wherein the cycloalkenyl group is not an aromatic, to increase melanin synthesis, improve the

 Melanin transports and / or improvement of the distribution of melanin suprabasal layers.

Use according to claim 1 or 2, characterized in that

R6 and R7 independently represent

 -straight-chain or branched d- to Ci2-alkyl, or

 -straight-chain or branched C 2 - to C 12 -alkenyl.

Use according to claim 3, characterized in that R6 and

R7 stand independently for

 -straight-chain or branched C to C6-alkyl, or

 straight-chain or branched C2 to C6 alkenyl.

Use according to claim 4, characterized in that R6 and R7 are methyl.

Use according to one or more of claims 1 to 5, characterized in that the radicals R 1 to R 5 are independently H, OH, NH ₂ , methyl, OCH ₃ or O (C = O) CH ₃ .

7. Use according to one or more of claims 1 to 6,

 characterized in that the radicals R2 and R4 stand for H.

8. Use according to one or more of claims 1 to 7,

characterized in that the compounds of the formula I are selected from the compounds of the formulas Ia to Ih

9. A preparation containing at least one compound of the formula I.

 wherein

R1 to R5 are independently H, OH, NH _2, R7, OR7 or O (C = 0) R7, and

 R6 and R7 independently represent

 straight-chain or branched C 1 to C 30 -alkyl,

-straight-chain or branched C ₂ - to C ₃₀ -alkenyl,

or a cycloalkyl or cycloalkenyl group having 5 to 8 C Atoms, wherein the cycloalkenyl group is not an aromatic.

10. A preparation according to claim 9, characterized in that it contains the compound of formula I in an amount of 0.01 to 10 wt .-%.

11. Preparation according to claim 9 or 10, characterized in that at least one further self-tanning substance is contained.

12. Preparation according to one or more of claims 9 to 11,

 characterized in that in addition at least one UV filter is included.

13. A process for preparing a preparation according to one or more of claims 9 to 12, characterized in that the compound of formula I is mixed with a suitable carrier for topical applications.