EP1755546A2 - Skin and/or hair products, containing compounds with an isoprenoid structure - Google Patents

Abstract

The invention relates to products for application on the skin or hair, in particular, for increasing skin tanning and melanin synthesis in the skin or hair. In particular, said invention comprises cosmetic or dermatological preparations, containing compounds with an isoprenoid structure. Said preparations are used for inducing and intensifying the tanning mechanisms of the skin, intensifying the hair color and thus increasing the intrinsic protection of the skin or hair.

Description

 Skin and / or hair products containing compounds with an isoprenoid structure

The present invention relates to agents for use on the skin and / or hair, in particular for increasing skin tanning and melanin synthesis in the skin or hair. In particular, the invention comprises cosmetic or dermatological preparations containing compounds with an isopronoid structure. The use of the preparations leads to the induction and intensification of the natural tanning mechanisms of the skin, to the intensification of the hair color and thus also to an increase in skin or hair protection.

The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays with a wavelength that is less than 290 nm (the so-called UVC range) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB range, cause Erythema, a simple sunburn or even more or less severe burns on the skin.

Numerous compounds are known for protecting against UVB radiation, most of which are derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also 2-phenylbenzimidazole.

It is also important to have filter substances available for the range between approximately 320 nm and approximately 400 nm, the so-called UVA range, since their rays can also cause damage. It has been proven that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, which causes the skin to age prematurely, and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be intensified by UV-A radiation.

UVA radiation can also cause skin damage by, among other things, damaging the skin's own keratin or elastin. This reduces the elasticity and water retention capacity of the skin, ie the skin becomes less supple and tends to wrinkle. This type of wrinkling is also known as light-related skin aging. The remarkably high incidence of skin cancer in areas with strong sun Irradiation shows that the genetic information in the cells is apparently also damaged by sunlight.

However, UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products interfere with the skin's metabolism.

Such photochemical reaction products are predominantly radical compounds, e.g. Hydroxyl radicals. Undefined radical photo products, which are created in the skin itself, can also display uncontrolled subsequent reactions due to their high reactivity. Singlet oxygen, a non-radically excited state of the oxygen molecule can also occur under UV radiation, as can short-lived epoxies and many others. Singlet oxygen, for example, is characterized by increased reactivity compared to the triplet oxygen that is normally present (radical ground state). However, there are also excited, reactive (radical) triplet states of the oxygen molecule. Such processes are significantly involved in light-related skin aging (including wrinkling) through oxidative damage to various skin structures.

UV radiation also belongs to ionizing radiation. There is therefore a risk that ionic species can also be formed when exposed to UV, which in turn can then have an oxidative effect on the biochemical processes.

The pigmentation of human skin is essentially caused by the presence of melanin. Melanin and its breakdown products (melanoids), carotene, the degree of blood circulation as well as the nature and thickness of the stratum corneum and other skin layers leave skin tones of practically white (with reduced filling or in the absence of blood vessels) or yellowish over light brown-reddish, bluish to brown different shades and finally appear almost black. The individual skin regions show different depths of color due to different amounts of melanin.

The natural melanin protects the skin from penetrating UV radiation. The number of melanin granules produced in the melanocytes determines whether the skin is light or dark. With strong pigmentation (e.g. in colored people, but also in fair-skinned people after prolonged UV radiation), melanin is also in the stratum spinosum and even in the stratum corneum. It weakens the UV radiation by up to approx. 90% before it reaches the corium.

As characteristic cell organelles, melanocytes contain melanosomes, in which the melanin is formed. When stimulated by UV radiation, among other things, melanin is increasingly formed. This is ultimately transported into the horny layer (comeocytes) via the living layers of the epidermis (keratinocytes) and causes the more or less pronounced brown to brown-black skin color. Melanin is formed as the final stage of an oxidative process in which tyrosine, with the help of the enzyme tyrosinase, is converted into brown to brown-black eumelanins (DHICA and DHI melanin) over several intermediate stages or with the participation of sulfur-containing compounds to reddish pheomelanin. DHICA and DHI melanin are produced via the common intermediate stages dopaquinone and dopachrome. The latter is implemented, partly with the participation of further enzymes, either in indole-5,6-quinone carboxylic acid or in indole-5,6-quinone, from which the two eumelanins mentioned arise. The formation of phaeomelanin occurs among other things via the intermediates dopaquinone and cysteinyldopa.

In addition to various functions of the skin's own melanin, such as "detoxification", binding of toxic substances / pharmaceuticals, etc., the function of "melanin as a natural UV filter to protect against damaging UV rays and the antioxidant function of melanin as protection against reactive oxygen species ( oxidative stress), which can occur due to solar radiation, among other things, very important for the skin, also with regard to homeostasis, avoidance of skin aging, avoidance of sunburn etc. So there should not only be a cosmetic benefit in the sense of increased tanning through the Increased melanin synthesis in the skin after topical application of melanogenesis-increasing compounds also result in additional protection through the various protective functions of melanin.

The object of the present invention is therefore to provide an agent, in particular a cosmetic or dermatological preparation, which enhances the natural tanning of the skin by means of increased melanin synthesis and at the same time leads to an increased protection of the skin. Depending on the sensitivity to light, the following skin types are generally distinguished:

Skin type I never tans, always gets a sunburn. Skin type II hardly tans, easily gets a sunburn. Skin type III tans well on average.

Skin type IV tans lightly and persistently, almost never gets sunburned. Skin type V dark, often almost black skin, never gets sunburned.

The natural shielding of harmful UV radiation is a tangible advantage of natural skin tanning. For several decades, a "healthy" skin color has also been a sign of sporting activity in particular and is therefore considered desirable by a wide range of consumers. Representatives of skin types I and II who want to enjoy such a skin tint are therefore dependent on self-tanning preparations anyway But representatives of skin type III who do not expose themselves too much to the risks of sunbathing and still want to look tanned are grateful target groups for self-tanning preparations.

The easiest way to give your skin a brown hue is to apply appropriately colored make-up or make-up preparations. However, only those parts of the body that are covered by the colored preparations are of course stained. With the help of washable IWake-up preparations, a light skin tint can be achieved (e.g. extracts from fresh green walnut shells, henna). A disadvantage of the make-up is therefore the time-consuming procedure of applying. Another disadvantage is that they rub off heavily on textiles such as shirt collars or blouses. In addition, the different dyes can have different allergenic potency and can even irritate the skin.

The object of the present invention is therefore also to provide preparations which do not have the disadvantages of make-up tanning preparations.

Artificial skin tanning can be achieved by cosmetic or medical means, whereby the following approaches play a role:

By taking carotene supplements regularly, carotene is stored in the subcutaneous fatty tissue, the skin gradually turns orange to yellow-brown. The staining can also be done by chemically changing the horny layer of the skin with so-called self-tanning preparations. The most important active ingredient is dihydroxyacetone (DHA). The skin tanning achieved in this way cannot be washed off and is only removed with the normal desquamation of the skin (after approx. 10-15 days). Dihydroxyacetone can be referred to as ketotriose and reacts as a reducing sugar with the amino acids of the skin or the free amino and imino groups of keratin via a series of intermediates in the sense of a Maillard reaction to brown-colored substances, so-called melanoids, which gel - occasionally also called melanoidins.

A particular disadvantage of tanning with dihydroxyacetone is that, in contrast to "sun-tanned" skin, the skin tanned with it is not protected against sunburn. Another disadvantage of dihydroxyacetone is that it, especially under the influence of ultraviolet radiation, albeit in mostly small amounts, formaldehyde is split off, so there was an urgent need to find ways in which the decomposition of dihydroxyacetone can be effectively countered.

An object of the present invention is to find alternatives to DHA as a self-tanning agent which do not have any disadvantageous properties, as are known from DHA. ^";

Staining by self-tanners takes place without exposure to sunlight. In contrast, so-called "pre-tan products" or "tan promoters" are also offered, which have to be applied before the sun is irradiated. These preparations then turn yellow in the sun, which should lead to a slight brown-yellow coloring of the epidermis, which additionally reinforces the "tan".

Another type of artificial tanning, which is also completely independent of UV light, can be brought about by the hormones which are usually released in the body also as a result of (natural) UV radiation and ultimately stimulate the melanocytes to synthesize melanin. In this context, descendants of proopiomelanocortin (POMC) such as aMSH and synthetic variants (such as NDP) are to be mentioned, some of which have much higher activity than natural aMSH. Although these hormones can in principle cause browning, however, their use in cosmetics is forbidden because they are clearly pharmacologically active substances (hormones) that should not be used widely without medical indication.

To remedy the disadvantages of the prior art was also an object of the present invention.

In addition to skin health and skin care, hair care is an extremely intensively researched area in cosmetics.

Hair is the thread-like, almost universal skin appendage (missing from the palms of the hands, soles of the feet, extended sides of the toes, end of the fingers); distinguished as long hair (the head, beard, armpit, pubic hair = Capilli, Barba, Hirci or Pubes; in men also chest hair), short, bristle hair (Supercilia, Cilia, Vibrissae, Tragi) and wool hair (Lanugo, Velus hair ). The structure of all of these hairs is roughly similar: the central hair mark (from epithelial cells with eosinophilic horny granules = trichohyalin granules), surrounded by the hair cortex (from horny cells; contains pigments) and the cuticle (cuticle pili; coreless epidermal layer) and of layers of the epithelial and connective tissue sheath.

The hair is divided into the hair shaft protruding from the skin and the oblique hair root reaching into the subcutis, the layers of which correspond approximately to those of the epidermis. The thickened lower end of the root, the hair bulb, sits on a vascular connective tissue cone, the hair papilla, protruding into it (both as a hair floor). The onion is in the initial (= anagen) phase, the cyclically repeating hair formation layered onion-like due to the constant new formation of cells due to its layer close to the papilla (matrix), later then closed, bulbous, completely horny (piston hair) and finally, in the end (= telogen) phase, displaced towards the follicle opening by a new hair - starting from a newly formed hair papilla.

Melanin is responsible for the personal hair color. Melanin is formed in the melanocytes, cells that occur in the hair bulb in association with the keratinocytes of the hair market. Melanocytes contain as characteristic cell organelles Melanosomes, in which the melanin is formed. This is transferred via the long dendrites of the melanocytes into the keratinocytes of the precortical matrix and creates the more or less pronounced blonde to brown-black hair color. Melanin is formed as the final stage of an oxidative process in which tyrosine is converted into brown to brown-black eumelanins (DHICA and DHI melanin) or with the participation of sulfur-containing compounds to reddish pheomelanin with the help of the enzyme tyrosinase. DHICA and DHI melanin are produced via the common intermediate stages dopaquinone and dopachrome. The latter is implemented, partly with the participation of further enzymes, either in indole-5,6-quinone carboxylic acid or in indole-5,6-quinone, from which the two eumelanins mentioned arise. The formation of phaeomelanin occurs among other things via the intermediates dopaquinone and cysteinyldopa. Cysteine is also necessary if the phaeomelanin is to be created for blonde and reddish hair.

Eumelanin is the black-brown pigment. It is mainly about the depth of color of the hair. In brown and black hair it occurs in clearly recognizable granules.

Phaeomelanin is the red pigment. It is responsible for light blonde, blonde and red hair. The structure of this melanin is much finer and smaller. The different hair colors result from the different proportions of the melanin types: • Blond hair contains little eumelanin and a lot of phaeomelanin. • Dark hair contains a lot of eumelanin and little phaeomelanin. • Red hair also has little eumelanin and a lot of phaeomelanin. • All shades of hair in between result from different mixing ratios of the two melanin types.

The pigment formation process can only proceed if sufficient tyrosinase is available. This enzyme is produced less frequently with age. This gradually leads to gray hair. The reason: with little tyrosinase, less and less tyrosine is formed. The production of melanin also decreases. The missing melanin is replaced by the storage of air bubbles. The hair appears gray. This process is usually insidious. It begins at the temples and then extends to the entire hair on the head. Then it hits the beard and eyebrows. Finally, all of the body's hair is gray.

Medically, gray hair is called canities. There are several ways of graying. Premature graying, from the age of 20, is also called Canities praecox.

Symptoms of canities, or symptomatic graying of the hair, can have various causes. These include: • Pernicious anemia (Vitamiπ-B deficiency anemia), • Severe endocrinological disorders, e.g. B. in thyroid disease. • acute, febrile illnesses, • drug side effects, • cosmetics, • metals.

The coloring of hair, especially of living human hair, using natural dyes, as has been known for the dye henna since ancient times, and which has been pushed into the background for years in favor of synthetic dyes, has been the subject of a new one for some years interest. A disadvantage is the red color created by henna.

With increasing age, the melanin production that causes the hair color decreases: the hair becomes gray or white. It is a cosmetic wish of some consumers to reverse this process or to let it run more slowly. For this purpose, the cosmetic industry uses lead acetate in some countries, which is toxic and is therefore prohibited in the European Cosmetics Regulation. This lead acetate is preferably applied to the hair as a solution and remains there for a long time without being washed off.

For dyeing keratin fibers, e.g. B. hair, wool or furs, generally come either direct dyes or oxidation dyes by oxidative coupling of one or more developer components with each other or with one or more coupler components are created for use. Coupler and developer components are also referred to as oxidation dye precursors.

Primary aromatic amines with a further free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl ) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2- Hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. Particularly suitable coupler substances are -naphthol, 1,5-, 2,7- and 1,7-dihydroxy-naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2, 4-diaminophenoxyethanol, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminoph ^"enol, 1, 3-bis (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyiresorcinol and 5-methylresorcinol.

With regard to other conventional dye components, reference is expressly made to the "Dermatology" series, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Cape. 7, pages 248-250 (direct dyes), and chap. 8, pages 264-267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in disk form from the Federal Association of German Industry and Trade Companies for Medicines, Health Products and Personal Care Products, Mannheim ,

With oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color happens in general under the influence of oxidizing agents such. B. H ₂ 0 ₂ , which in some cases can result in damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of

Oxidation dye precursors sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

The object of the present invention is to improve the independent melanin production of the hair, but without coloring agents and in particular oxidizing agents such. B. H ₂ 0 ₂ to be instructed. In addition, the agents must have no or only a very low sensitization potential.

DE 10212865 describes cosmetic or dermatological preparations containing 9-retinal and / or 9-retinal-alkanolamine Schiff base of the structural formula

where R = ROH, branched or unbranched alkanols. The use of preparations containing 9-retinal and / or 9-retinal-alkanolamine Schiff base leads to the induction and intensification of the tanning mechanisms of the skin and to the intensification of the hair color.

It is therefore an object of the present invention to provide alternative agents for tanning the skin or increasing melanin synthesis

It has now surprisingly been found that an agent according to claim 1, in particular cosmetic or dermatological preparations according to one of claims 3 to 15, solves the entire bundle of tasks.

The subclaims relate to advantageous embodiments of the means according to the invention. Furthermore, the invention comprises the use of such agents and the compounds according to the invention as agents for increasing the tan or the melanin synthesis in the skin or hair. It was surprising and unforeseeable for the person skilled in the art that agents for use on the skin and / or hair, in particular cosmetic or dermatological preparations, containing one or more compounds of the structure

hereinafter referred to as compounds with an isoprenoid structure, which solve problems.

The isoprenoid structures are linear carbon compounds which consist of n = 1 to 7, preferably n = 1 to 5 subunits. N = 1 to 2 subunits are particularly preferred. These subunits are composed of 4 (01 to C4) to 6 (01 to 04 and R3, R5) carbon atoms, it being possible for the C-C compounds to be both saturated and unsaturated. This applies in particular to the C-C compounds in line 01 to 04. The C3-R3 and the C4-R5 compounds are preferably saturated. The saturated compounds are also identified below as C == C. Unless otherwise stated, "free carbon binding sites" are occupied by hydrogen. The two ends, Rx and Ry, of the hydrocarbon compounds composed of 1-7 subunits can be both non-polar and polar, but it is preferred that at least one end (Rx or Ry ) has a polar grouping, the residues should therefore be selected as follows:

- n is an integer from 1 to 7 and

- Rx, Ry represent polar and / or non-polar residues with the structure:

Rx, y = carbon single or double bond to R4, R4 ^' and / or R4 "., C = R ₄ , C = O For example for R4 = carbonyl oxygen, Ry = - _^ - *

R4 "are residues of the structure Rr

^R 2 or - R1, R2, R3 and R5 independently of one another preferably represent hydrogen and / or methyl radicals, including propyl, isopropyl, butyl, tert-butyl, hydroymethyl, hydroxyethyl, hydroxypropyl, hydroxy and / or alkyl carboxylates with alkyl radicals selected from methyl, ethyl , Propyl or butyl, are possible residues.

- R4 is selected from carbonyl oxygen, from amino acid residues Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg, Gin, H, Orn, Sar, Hyl, Hyp, Hse or Hey, preferably Ala, Ser or Gly, residues of the structure N-OH, N- (CH ^ OH, N- (CHR9) rCH2OH, NKCHRΘ OH, N- (CH ₂ ) χ-OCOMe , where each x = 1-10, or residues of the structure

- R9 is selected from hydrogen and / or hydroxy,

- R11 is selected from methyl, hydroxymethyl, hydrogen, prop-2-yl, isobutyl, but-2-yl, pyrrolidin-1, 2-diyl, 1 H-indol-3-yl-methyl , Benzyl; 2- (methylthio) ethyl, 4-hydroxy-benzyl, 1-hydroxyethyl, mercaptomethyl, 2-amino-2-oxoethyl, carboxymethyl, carboxyethyl, 4-aminobutyl, 3 - {[amino (imino ) methyl] amino} propyl, 3-amino-3-oxopropyl, hydrogen and N-Me, 3-aminopropyl, ethyl, 1H-imidazol-4-yl-methyl, butyl, propyl, 4- Amino-3-hydroxy-butyl-, 4-hydroxy-pyrrolidin-1, 2-diyl-, hydroxyethyl- or 2-mercaptoethyl-, preferably methyl-, hydroxymethyl- or

Hydrogen, with R4 and R10 = OH then preferably gives the amino acid residues mentioned under R4,

- R10 is selected from hydroxy- (-OH), peptidically N-linked amino acid residues selected from Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg, Gin, H, Orn, Sar, Hyl, Hyp, Hse or Hey, preferably Ala, Ser or Gly, residues of the structure

with b = 1 - 6, or O R12 O ^'

- R12 is selected from mono- to polysaccharides, preferably uniform and / or mixed mono-, di- or trisaccharides, preferably glucose, glycerose, erythrose, threose, ribose, arabinose, lyxose, xylose, allose, altrose, galactose, gulose, idose , Mannose or talose; - R4 'is selected from amino acid residues Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg, Gin, H, Orn, Sar, Hyl, Hyp, Hse, Hey, preferably Ala, Ser or Gly, or residues of the structure

with = 1 - 6, or .R15 O

- R13 is selected from methyl, hydroxymethyl hydrogen, prop-2-yl, isobutyl, but-2-yl, pyrrofidin-1, 2-diyl, 1H-indol-3-yl-methyl, benzyl -; 2- (methylthio) ethyl, 4-hydroxybenzyl, hydroxyethyl, mercaptomethyl, 2-amino-2-oxoethyl, carboxymethyl, carboxyethyl, 4-aminobutyl, 3 - {[amino (imino) methyl] arπino} propyl, 3-amino-3-oxopropyl, hydrogen and N-Me, 3-aminopropyl, ethyl, 1H-imidazol-4-yl-methyl, butyl, propyl, 4-amino -3-hydroxy-butyl-, 4-hydroxy-pyrrolidin-1, 2-diyl-, hydroxyethyl- or 2-mercaptoethyl-, preferably methyl-, hydroxymethyl- or ode r Hydrogen, where R4 ^' =, b = 1 and R14 = H then preferably give the amino acid residues mentioned under R4 ^' ,

- R14 is selected from hydroxy- (-OH), hydrogen (-H) and / or peptidically-O-bound amino acid residues selected from Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr , Cys, Asn, Asp, Glu, Lys, Arg, Gin, H, Orn, Sar, Hyl, Hyp, Hse, Hey, preferably Ala, Ser or Gly,

- R15 is selected from mono- to polysaccharides, preferably uniform and mixed mono-, di- or trisaccharides, preferably glucose, glycerose, erythrose, threose, ribose, arabinose, lyxose, xylose, allose, altrose, galactose, gulose, idose, Mannose or Talose.

The substances with an isoprenoid structure are ideal for bringing about increased tanning of the skin. All compounds of the structures listed above which the person skilled in the art can select from the respective groups have proven suitable. Of course, the person skilled in the art, particularly for cosmetic or dermatological application purposes, will preferably only select those whose tolerability, toxicology or the like are not critical.

The skin's own melanin has various functions, such as, for example, "detoxification'Ybinding of toxic substances / pharmaceuticals. In addition, the function of melanin as a natural UV filter for protection against damaging UV rays and the antioxidant function of melanin as protection against reactive oxygen species (oxidative Stress), which can occur due to solar radiation, among other things, is very important for the skin, also with regard to homeostasis, avoidance of skin aging, avoidance of sunburn, etc. This should not only result in a cosmetic benefit in the sense of increased tanning due to the increased Melanin synthesis in the skin after topical application of compounds with isoprenoid structure which increase the melanogenesis according to the invention, but also provide additional protection through the various protective functions of melanin. The compounds according to the invention are suitable for enhancing the physiological tanning of the skin by means of an increased melanin synthesis and thus also for increasing the skin's own protection. A major advantage is that this physiological tanning is achieved without having to be exposed to natural solar radiation with its damaging influences on the skin or that this is only necessary to a comparatively small extent in order to achieve the desired skin tanning. In addition to increasing tanning, uneven skin pigmentations ("uneven skin tone") are also compensated. The advantage: the complexion appears more uniform, which is particularly desirable for aging skin (age spots), melasma and post-inflammatory hyperpigmentation.

In principle, the topical use of the compounds according to the invention in various, in particular W / O and also O / W formulations and other cosmetic dosage forms is possible and preferred.

The invention therefore preferably relates to cosmetic or dermatological preparations containing compounds according to the invention, as defined above. In addition, however, the agents can also be used in polymer matrices, in a skin and / or wound dressing, a plaster, a cloth or pad, a spray or in a textile.

The subject of the invention is also the use of the thus produced

Application forms and preparations.

The following compounds having structures I to VIII are preferred.

Structure ffl

- \ Specification of E / Z applies: Both the E or Z isomer as well as the isomer mixture.

From the compound structure (I) with the respectively preferred radicals R1, R2, R3 and R4, the following compounds (IUPAC names) with the structures indicated preferably result:

- (2 £ Z) -3J-dimethylocta-2,6-dienal

where R1, R2 and R3 are each methyl radicals, R5 = H, n = 1, C3 == C4, ie double bond between C3 and C4, and R4 is a carbonyl oxygen.

This (2E / -!) - 3,7-dimethylocta-2,6-dienal is available, for example, from Sigma-Aldrich.

Λ / - [(2E Z) -3J-dimethylocta-2,6-dien-1-ylidenes] -L-alanines

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 is a radical of

, with R11 = methyl and R10 is a hydroxy radical;

Λ / - [(1 £ Z, 2 £ Z) -3J-dimethylocta-2,6-dien-1-ylidenes] butan-1-amines

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 = N-alkyl (N-butyl). This compound is prepared according to the following synthesis protocol:

To a solution of water (10 ml), conc. aqueous NH ₃ solution and butylamine (5.5 mmol, 0.55 ml) citral (5 mmol, 0.86 ml) are added. A colorless emulsion is created. Since, after checking the reaction by thin-layer chromatography, no start of reaction can be observed after 2 hours, the solution is mixed with concentrated hydrochloric acid until no further NH ₄ CI precipitate is formed. The acidic reaction solution is stirred for 2d at room temperature. The solution turns yellow / brown. For working up, the reaction mixture is shaken twice with diethyl ether (20 ml each). The combined organic phases are washed (sat. NaCl solution) and dried (Na ₂ S0 ₄ ). The solvents are removed in vacuo. Column chromatography (PE / EE 10: 1) gives the desired product in a yield of 16%.

- (1 -≡XZ, 2E / Z) -3,7-dimethylocta-2,6-dienal oxime

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 is N-OH.

This (1 £ Z, 2B ^) - 3J-dimethylocta-2,6-dienal oxime is available, for example, from ASDI BioSciences.

- 2 - {[(1E2,2S2) -3J-dimethylocta-2,6-dien-1-ylidenes] amino} ethanol

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 is a radical of the structure N- (CH ₂ ) _> rOH, with x = 2.

- 2 - {[(1E2 ', 2E-Z) -3J-dimethy! Octa-2,6-dien-1-ylidenes] amino} ethyl acetate where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 is a radical of the structure N- (CH ₂ ) -OCOMe, with x = 2.

- (2E / Z, 6E Z) -3J, 11-trimethyldodeca-2,6,10-trienal

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 2 and R4 is carbonyl oxygen.

This (2EZ, 6EyZ) -3J, 11-trimethyldodeca-2,6,10-trienal is available, for example, from Sigma-Aldrich.

- N - [(2E / Z, 6E / Z) -3.7, 11-trimethyldodeca-2,6, 10-trien-1-ylidenes] -L-alanines

wherein R1, R2 and R3 are each methyl radicals, R 5 = H, C3 == C4, n = 2 and R4 is a radical of R11 N COR _ιn structure ^1U, with R11 = methyl and R10 is hydroxy,

Λ / - [(1 EZ, 2E Z, 6E Z) -3J, H-trimethyldodeca-2,6,10-trien-1-ylidenes] butan-1-amines

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 2 and R4 is N-alkyl (N-butyl), (1 E / Z, 2E ^, 6E / Z) -3J, 11-trimethyldodeca-2,6J0-trienal oxime

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 2 and R4 = N-OH,

- 2 - {[(1 E Z, 2E Z, 6E2) -3J, 11-trimethyldodeca-2,6,10-trien-1-ylidenes] amino} ethanol

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 2 and R4 is a radical of the structure N- (CH ₂ ) _x -OH, with x = 2.

- 2 - {[(1 E Z, 2E Z, 6E Z) -3J, 11 -trimethyldodeca-2,6,10-trien-1-ylidenes] amino} ethyl acetate

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 2 and R4 is a radical of the structure N- (CH ₂ ) _x -OCOMe with x = 2.

- (3E £, 5EZZ) -6,10-dimethylundeca-3,5,9-trien-2-one

where R1, R2 and R3 are each methyl radicals, R5 = H, C3-C4, n = 1 and R4 is CH-CO-Me.

This (3E Z, 5E / Z) -6,10-dimethylundeca-3,5,9-trien-2-one is available, for example, from the company InterBioScreen Moscow. Ali structure

where R1, R2, R3 each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 'a radical of the O NH Rι <b structure (K- ^' 13 with b = 2, R13 = methyl radical and R14 = H ,

- (2E / Z) -3J-dimethylocta-2,6-dien-1-yl D-glucopyranoside

with R1, R2, R3 each as a methyl radical, R5 = H, C3 == C4, n = 1 and R4 'as a radical of the structure 0-R15 with R15 = -glucosyl.

- (2EZ) -3J-dimethylocta-2,6-dien-1-yl 4-0-D-glucopyranosyl-D-glucopyranoside

with R1, R2, R3 each as a methyl radical, R5 = H, C3 == C4, n = 1 and R4 'as a radical of the structure 0-R15 with R15 = -1, 4-di-glucosyl.

- (2E / Z, 6S £) -3.7, H-trimethyldodeca-2,6,10-trieπ-1-yl L-alanyl-L-alaninate

where R1, R2, R3 each represent methyl radicals, R5 = H, C3 == C4, n = 2 and R4 'a radical of

structure Methyl residue and R14 = H.

- (2E / Z, 6E ^) - 3J, 11-trimethyldodeca-2,6J0-trien-1-yl D-glucopyranoside with R1, R2, R3 each as a methyl radical, R5 = H, C3 == C4, n = 2 and R4 'as a radical of the structure 0-R15 with R15 = -glucosyl.

(2E Z, 6E ^) - 3J, H-trimethyldodeca-2,6J0-trien-1-yl 4-O-D-glucopyranosyl-D-glucopyranoside

OH

with R1, R2, R3 each as a methyl radical, R5 = H, C3 == C4, n = 2 and R4 ^' as a radical of the structure 0-R15 with R15 = -1,4-di-glucosyl.

- (5 £ ^, 9EZ) -6,10,14-trimethylpentadeca-5,9,13-trien-2-one

where R1, R2 and R3 are each methyl radicals R5 = H, C3 == C4, n = 2 and R4 'CH ₂ -CO-Me,

This (5E / Z, 9E / Z) -6J0J4-trimethylpentadeca-5,9J3-trien-2-one is available, for example, from InterBioScreen Moscow.

(5E / Z) -6,10-dimethylundeca-5,9-dien-2-one where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 'CH ₂ -C0-Me,

This (5E / Z) -6,10-dimethylundeca-5,9-dien-2-oπe is for example from the company

InterBioScreen Moscow available.

- (3E ZJ £ XZ) -5,5,8J2-tetramethyltrideca-3,7,11 -trien-2-one

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 'C (MeMe) CH = CHCOMe,

This (3E / 2JE £) -5,5,8J2-tetramethyltrideca-3J, 11-trien-2-one is available, for example, from InterBioScreen Moscow.

(6E Z) -3J, 11-trimethyldodeca-6,10-dienal

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 'CH2-CH (Me) -CH ₂ CHO,

This (6E Z) -3J, H-trimethyldodeca-6,10-dienal is available, for example, from LKT Laboratories Inc., USA.

- (2E / Z, 6EZ) -7,11-dimethyldodeca-2,6,10-trienoic acid where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 'CH ₂ CH = CHCOOH,

This (2E / Z, 6E / Z) -7,11-dimethyldodeca-2,6,10-trienoic acid is available, for example, from InterBioScreen, Moscow.

- (3E Z, 8E Z) -2,9,13-trimethyltetradeca-3,8,12-triene-5-one

where R1, R2 and R3 are each methyl radicals, R5 = H, C3 == C4, n = 1 and R4 'CH ₂ COCH = CH-CH (Me) (Me),

This (3E / Z, 8E / Z) -2,9,13-trimethyltetradeca-3,8J2-trien-5-one is available, for example, from InterBioScreen, Moscow.

Structure (III.

, ^ From the compound structure (III) with the respectively preferred radicals R1, R2, R3, R5 and R4, the compounds (IUPAC names) with the structures given below preferably result:

(2E / Z, 4E / Z) -3J-dimethyl-octa-2,4,6-trienal

where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 is a carbonyl oxygen,

- Λ / - [(2E Z, 4E / 2) -3J-dimethylocta-2,4,6-trien-1-ylidenes] -L-alanines where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1, Ry = C ==

R4 and R4 are a remainder of with R11 = methyl and R10

Is hydroxy;

Λ / - [(1 E ^, 2E / Z, 4E / Z) -3J-dimethyl-octa-2,4,6-trien-1-ylidene] butan-1-amine

where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 is N-alkyl (N-butyl),

- (1 E / Z, 2EZ, 4E Z) -3J-dimethylocta-2,4,6-trienal oxime where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 N-

OH is

- 2 - {[(1E / Z, 2E Z, 4E ^ Z) -3J-dimethylocta-2,4,6-trien-1-ylidenes] amino} ethanol where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 is a radical of the structure N- (CH ₂ ) _x -OH, with x = 2.

- 2 - {[(1U / 2.2EZ, 4 £ Z) -3J-dimethylocta-2,4,6-trien-1-ylidenes] amino} ethyl acetate

where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 is a radical of the structure N- (CH ₂ ) χ-OCOMe, with x = 2.

- (2E / Z, 4E / Z, 6E / Z, 8E / Z) -3,7,11-trimethyldodeca-2,4,6,8,10-pentaenal where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 is carbonyl oxygen,

Λ / - [(2E Z, 4E / ^, 6EZ, 8E Z) -3J, 11-trimethyldodeca-2,4,6,8J0-pentaen-1-ylidenes] -L-alanines where R1, R2 and R3 each represent methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4

Rest of the structure , with R11 = methyl and R10 is a hydroxy radical, Λ / - [(1E Z, 2E Z, 4EZZ, 6EZ, 8E Z) -3J, 11-trimethyldodeca-2,4,6,8,10-pentaen-1-ylidenes] butan-1-amines where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 is N-alkyl (N-butyl),

(1 E / Z, 2E / Z, 4E / Z, 6E / Z, 8E /-.)- 3J, 11 -trimethyldodeca-2,4,6,8,10-pentaenal oxime where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 is N-OH,

2 - {[(1 B2,2E ^, 4EZ, 6E2,8E ^ Z) -3J, H-trimethyldodeca-2,4,6,8,10-ρentaen-1-ylidenes] amino} ethanol where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 is a radical of the structure N- (CH ₂ ) χ-OH, with x = 2.

2 - {[(1E, 2E / Z, 4E Z, 6E / Z, 8E / Z) -3J, 11-trimethyldodeca-2,4,6,8J 0-pentaen-1-ylidene] amino} ethyl acetate

where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 is a radical of the structure N- (CH ₂ ) χ-OCOMe, with x = 2.

- (3E Z, 5B2JEZ) -6,10-dimethylundeca-3,5J, 9-tetraen-2-one where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 is CH-CO-Me,

Structure (IV)

^

where R1, R2, R3 each methyl residues, R5 = H, C1 == C2, C3 == cA n = 1, Ry = C-

R4 ^' and R4 ^{' are} a residue of the structure with b = 2, R13 = methyl radical and R14 = H.

(2E / Z, 4E / Z) -3J-dimethylocta-2,4,6-trien-1-yl D-glucopyranoside OH

with R1, R2, R3 each as a methyl radical, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 ^' as a radical of the structure 0-R15 with R15 = -glucosyl.

- (2E / Z, 4E Z) -3,7-dimethylocta-2,4,6-trien-1-yl 4-0-D-glucopyranosyl-D-glucopyranoside

with R1, R2, R3 each as a methyl radical, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 'as a radical of the structure 0-R15 with R15 = -1, 4-di-glucosyl.

- (2E Z, 4E / Z, 6E Z, 8EZ) -3J, 11-trimethyldodeca-2,4,6,8J 0-pentaen-1-yl L-alanyl-L-alaninate

where R1, R2, R3 each represent methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 ^'

Rest of the structure with b = 2, R13 = methyl radical and R14 = H. trimethyldodeca-2,4,6,8J0-pentaen-1-yl glucopyranoside

with R1, R2, R3 each as a methyl radical, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 ^' as a radical of the structure 0-R15 with R15 = -glucosyl.

(2E2,4E ^, 6E Z, 8E Z) -3J, H-trimethyldodeca-2,4,6,8,10-pentaen-1-yl 4-0-D-glucopyranosyl-D-glucopyranoside OH

with R1, R2, R3 each as a methyl radical, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 'as a radical of the structure O-Rl 5 with R15 = -1, 4-di-glucosyl.

(5EXZJE / Z, 9E / Z, 11 EZ) -6, 10, 14-trimethylpentadeca-5J, 9, 11, 13-pentaen-2-one where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 2 and R4 'CH2CO-alkyl, preferably methyl,

- (5E / Z, 7E / Z) -6,10-dimethylundeca-5J, 9-trien-2-one where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 'CH ₂ -CO-Me,

- (3 £ ^ JE Z, 9EZ) -5,5,8J2-tetramethyltrideca-3J, 9, H-tetraen-2-one

where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 'C (MeMe) CH = CHCOMe,

- (6E Z, 8E Z) -3J, 11-trimethyldodeca-6,8J0-trienal where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 'CH2-CH (Me) -CH ₂ CHO,

(2E Z, 6S2.8E Z) -7, H-dimethyldodeca-2,6,8J0-tetraenoic acid where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 'CH ₂ CH = CHCOOH,

(3E Z, 8EXZ, 10EZ) -2,9J3-trimethyltetradeca-3,8,10,12-tetraen-5-one

where R1, R2 and R3 are each methyl radicals, R5 = H, C1 == C2, C3 == C4, n = 1 and R4 'CH ₂ COCH = CH-CH (Me) (Me),

Structure (V)

where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 1 and R4 is a radical

, with R11 = methyl and R10 is a hydroxy radical

(1 E Z, 2EZZ) -2-methyl-6-methyleneocta-2J-dienal oxime

, N-OH where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 1 and R4 is N-OH

Λ / -t (1E Z, 2E Z) -2-methyl-6-methyleneocta-2J-dien-1-ylidenes] butan-1-amines where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 1 and R4 is N-alkyl (N-butyl);

- 2 - {[(1 EZ, 2E Z) -2-methyl-6-methyleneocta-2J-dien-1-ylidenes] amino} ethyl acetate where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 1 and R4 is a radical of the structure N- (CH ₂ ) χ-OCOMe, with x = 2.

- (2E Z, 6E ^) - 2,6-dimethyl-10-methylenedodeca-2,6, H-trienal where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 2 and R4 is carbonyl oxygen,

This (2E Z, 6E Z) -2,6-dimethyl-10-methylenedodeca-2,6, H-trienal is available, for example, from SynChem, Kassel, Germany.

- Λ / - [(2E2.6E Z) -2,6-dimethyl-10-methylenedodeca-2,6, H-trien-1-ylidenes] -L-alanines where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 2 and R4 is a radical

the structure , with R11 = methyl and R10 is a hydroxy radical

(1E Z, 2EyZ, 6EZ) -2,6-dimethyl-10-methylenedodeca-2,6, H-trienal oxime where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 2 and R4 is N-OH

- Λ / - [(1EZ, 2E> Z, 6E Z) -2,6-dimethyl-10-methylenedodeca-2,6,11-trien-1-ylidenes] butan-1-amines where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 2 and R4 is N-alkyl (N-butyl);

- 2 - {[(1E Z, 2E Z, 6E Z) -2,6-dimethyl-10-methylenedodeca-2,6,11-trien-1-ylideπe] amino} ethyl acetate

where R3 is a proton and R5 is a methyl radical, C3 == C4, n = 2 and R4 is a radical of the structure N- (CH ₂ ) χ-OCOMe, with x = 2.

Structure (VI)

where R3 each protons, R5 methyl residues, C3 == C4, n = 1 and R4 'a residue of

(2E / Z) -2-methyl-6-methyleneocta-2J-dien-1-yl D-glucopyranoside

with R3 as a proton and R5 as a methyl radical, C3 == C4, n = 1 and R4 'as a radical of the structure 0-R15 with R15 = -glucosyl.

(2 £ XZ) -2-methyl-6-methyleneocta-2J-dien-1-yl 4-O-D-glucopyranosyl-D-glucopyranoside

with R3 as proton and R5 as methyl radical, C3 == C4, n = 1 and R4 'as radical of structure 0-R15 with R15 = -1, 4-di-glucosyl. - (2E Z, 6E Z) -2,6-dimethyl-10-methylenedodeca-2,6, H-trien-1-yl L-alanyl-L-alaninate

where R3 each protons, R5 methyl residues, C3 == C4, n = 2 and R4 'a residue of

- (2E Z, 6EZ) -2,6-dimethyl-10-methylenedodeca-2,6, H-trien-1-yl D-glucopyranoside

with R3 as proton and R5 as methyl radical, C3 == C4, n = 2 and R4 'as radical of structure 0-R15 with R15 = -glucosyl. - (2E Z, 6EZ) -2,6-dimethyl-10-methylenedodeca-2,6,11-trien-1-yl 4-0-D-glucopyranosyl-D-glucopyranoside

with R3 as the proton and R5 as the methyl radical, C3 == C4, n = 2 and R4 ^' as the radical of the structure 0-R15 with R15 = -1, 4-di-glucosyl.

- (5E Z, 9 £ Z) -5,9-dimethyl-13-methylenepentadeca-5,9,14-trien-2-one

with R3 as protons and R5 as methyl radicals, C3 == C4, n = 2 and R4 ^'is CH ₂ -CO- Me,

- (5E / Z) -5-methyl-9-methyleneundeca-5,10-dien-2-one

with R3 as protons and R5 as methyl radicals, C3 == C4, n = 1 and R4 'is CH ₂ -CO- Me,

Structure (VII)

preferably with n = 1 or 2, Rx = C == R4 "with R4" = and Ry = C == R4, R4 = carbonyl oxygen or N-OH ,. R3 and R5 are methyl or hydrogen and between C1 and C2 as well as C3 and C4 there is a double bond, R4 is preferably carbonyl oxygen and N-OH, the following applies to the double bond isomers when E / Z is given: E or Z alone Isomer, as is the mixture of isomers.

From the compound structure (VII) with the respectively preferred radicals R3, R5 and R4, the following compounds (IUPAC names) with the structures indicated preferably result:

- (2E / Z, 4E / Z) -2-methyl-6-methyleneocta-2,4J-trienal where R3 is a proton and R5 is a methyl radical, n = 1 and R4 is carbonyl oxygen.

Λ / - [(2B2,4E / 2) -2-methyl-6-methyleneocta-2,4J-trien-1-ylidene] -L-alanine

where R3 is a proton and R5 is a methyl radical, n = 1 and R4 is a radical of

, with R11 = methyl and R10 is a hydroxy radical

- (/ Z, 2E / Z, 4E / £) -2-methyl-6-methyleneocta-2,4J-trienal oxime N-OH where R3 is a proton and R5 is a methyl radical, n = 1 and R4 N-OH is.

Λ / - [(1 EZ, 2E / Z, 4EZ) -2-methyl-6-methyleneocta-2,4J-trien-1-ylidenes] butan-1-amines where R3 is a proton and R5 is a methyl radical, n = 1 and R4 is N-alkyl (N-butyl);

- 2- {I (1 EZ, 2E Z, 4E Z) -2-methyl-6-methyleneocta-2,4J-triene-1-ylidenes] amino} ethyl acetate where R3 is a proton and R5 is a methyl radical, n = 1 and R4, n = 2 is a radical of the structure N- (CH ₂ ) _x -OCOMe, with x = 2.

- (2E Z, 4EZ, 6EÄ, 8E Z) -2,6-dimethyl-10-methylenedodeca-2,4,6,8, H-pentaenal where R3 is a proton and R5 is a methyl radical, n = 2 and R4 is carbonyl oxygen.

Λ / - [(2EZ, 4E Z, 6E Z, 8E Z) -2,6-dimethyl-10-methylenedodeca-2,4,6,8, H-pentaen-1-ylidenes] -L-alanine S OOH

where R3 is a proton and R5 is a methyl radical, n = 2 and R4 is a radical of

structure , with R11 = methyl and R10 is a hydroxy radical

- (1E2T, 2 £> Z, 4e2 ', 6ez, 8-≡ Z) -2,6-dimethyl-10-methylenedodeca-2,4,6,8,11-pentaenal oxime where R3 is a proton and R5 is a methyl radical, n = 2 and R4 is N-OH

- Λ / - [(1 £ Z, 2EZ, 4EZ, 6E ^, 8E ^) - 2,6-dimethyl-10-methylenedodeca-2,4,6,8, H-pentaen-1-ylidenejbutane-1-amine where R3 is a proton and R5 is a methyl radical, n = 2 and R4 is N-alkyl (N-butyl);

- 2 - {[(1E Z, 2EZ, 4EZ, 6EZ, 8E2) -2,6-dimethyl-10-methylenedodeca-2,4,6,8,11-pentaen-1-ylidene] amino} ethyl acetate

where R3 is a proton and R5 is a methyl radical, n = 2 and R4, n = 2 is a radical of the structure N- (CH ₂ ) x-OCOMe, with x = 2.

Structure (VII I.

(2E Z, 4E Z) -2-methyl-6-methyleneocta-2,4J-trien-1-yl L-alanyl-L-alaninate

where R3 each protons, R5 methyl residues, n = 1 and R4 ^' a residue of

structure with b = 2, R13 = methyl radical and R1 = H.

(2E / Z, 4E) -2-methyl-6-methyleneocta-2,4J-trien-1-yl D-glucopyranoside

with R3 as proton and R5 as methyl radical, n = 1 and R4 ^' as radical of structure O-: R15 with R15 = -glucosyl. ,

(2E Z, 4E / 2) -2-methyl-6-methyleneocta-2,4J-trien-1-yl 4-O-D-glucopyranosyl-D-glucopyranoside

with R3 as a proton and R5 as a methyl radical, n = 1 and R4 'as a radical of the structure O-R15 with R15 = -1, 4-di-glucosyl. - (2E Z, 4E Z:, 6E Z, 8EZ) -2,6-dimethyl-10-methylenedodeca-2,4,6,8,11-pentaen-1-yl L-alanyl-L-alaninate

where R3 each protons, R5 methyl residues, n = 2 and R4 'a residue of

- (2E2.4E Z, 6E Z, 8E Z) -2,6-dimethyl-10-methylenedodeca-2,4,6,8, H-pentaen-1-yl D-glucopyranoside

with R3 as a proton and R5 as a methyl radical .... = 2 and R4 ^' as a radical of the structure O-R15 with R15 = -glucosyl.

- (2E / Z, 4E2.6E Z, 8E Z) -2,6-dimethyl-10-methylenedodeca-2,4,6,8, H-pentaen-1-yl 4-0- D-glucopyranosyl-D- glucopyranoside

with R3 as a proton and R5 as a methyl radical, n = 2 and R4 'as a radical of the structure O-R15 with R15 = -1, 4-di-glucosyl. - (5E ZJE / Z, 9E / Z, H £ Z) -5,9-dimethyl-13-methylenepentadeca-5J, 9, H, 14-pentaen-2- one

with R3 as protons and R5 as methyl radicals, n = 2 and R4 ^'is CH2CO-alkyl, preferably methyl,

- (5E / Z, 7E / Z) -5-methyl-9-methyleneundeca-5J, 10-trien-2-one

with R3 as protons and R5 as methyl radicals, n = 1 and R4 'is CH ₂ -CO-Me,

The following compounds have proven to be combination partners, i.e. in addition to the compounds with isoprenoid structure in the agents according to the invention, which, in combination with the isoprenoid structure compounds, show synergistic effects, both in terms of the tanning effect and in relation to the enodgenic self-protection.

From the group of the terpenoids is phytoene, 7J ', 8.8 \ 11.11', 12.12'-octahydro-ψ, ψ-carotene, the structure

prefers.

Also preferred is Phytofluen, 7,7 ', 8,8', H, 12-hexahydro-ψ,,-carotene, of the structure

Another preferred compound is ζ-carotene, 7J ', 8,8'-tetrahydro-ψ, ψ-carotene, the

structure

Compounds which are selected from the group neurosporin, 7,8-dihydro-ψ, ψ-carotene, of the structure, are preferably used as further combination compounds

.

Lycopene, ψ, ψ-carotenes,

ß-carotene, ß, ß-carotene, the structure,

Squalene, (6E, 10E, 14E, 18E) -2,6, 10,15,19,23-hexamethyltetracosa-2,6, 10,14,18,22-hexaene,

Variabilin, (5Z) -5 - [(6E, 10E) -13- (3-furyl) -2,6, 10-trimethyltrideca-6, 10-dien-1-ylidenes] -4-hydroxy-3-methylfuran 2 (5rτ) -one,

Phytanoic acid, (3 7f?, 11R) -3J, 11, 15-tetramethylhexadecanoic acid Phytol, (2E, 7R, HR) -3J, H, 15-tetramethylhexadec-2-en-1-ol, the structure

Efficacy tests were carried out to demonstrate the effectiveness of the isoprenoid structure compounds according to the invention.

A melanogenesis assay was carried out after 3 days of incubation of primary normal human melanocytes with test substance versus control. The numbers given in the table indicate the melanogenesis rates based on the untreated control (= 100%) (measured as ¹⁴ C-tyrosine incorporation). It follows that the melanogenesis, ie the process of melanin synthesis, increases to 217%, 128% and 121%, respectively, if the melanocytes are present in the presence of (2E Z, 6E / Z) -3J, H-trimethyldodeca-2,6, 10-trienally cultivated (n = 3).

A melanogenesis assay was carried out after 3 days of incubation of primary normal human melanocytes with test substance versus control. The numbers given in the table indicate the melanogenesis rates based on the untreated control (= 100%) (measured as ¹⁴ C-tyrosine incorporation). It follows that the melanogenesis, ie the process of melanin synthesis, increases to 135% and 113%, respectively, when the melanocytes are present in the presence of the Λ / - [(1 EZ, 2E Z) -3J-dimethylocta- 2,6-diene- 1-ylidenes] butan-1-amines are cultivated (n = 2).

A melanogenesis assay was carried out after 3 days of incubation of primary normal human melanocytes with test substance versus control. The numbers given in the table indicate the melanogenesis rates based on the untreated control (= 100%) (measured as ¹⁴ C-tyrosine incorporation). This means that melanogenesis, ie the process of melanin synthesis to 137% or 127% increases if the melanocytes are cultivated in the presence of (2E Z) -3J-dimethylocta-2,6-dienal (n = 2-6).

A melanogenesis assay was carried out after 3 days of incubation of primary normal human melanocytes with test substance versus control. The numbers given in the table indicate the melanogenesis rates based on the untreated control (= 100%) (measured as ¹⁴ C-tyrosine incorporation). It follows that the melanogenesis, ie the process of melanin synthesis, increases to 131%, 130% and 117%, respectively, if the melanocytes are present in the presence of (1EZ, 2E / Σ) -3,7-dimethylocta-2,6-dienal oximes are cultivated (n = 2).

These compounds according to the invention, the compounds explicitly named and shown only examples of the respective compounds of the

Structures (I) to (VIII) have proven themselves as agents for use on the skin or hair. The connections lead to an increase in

Melanin synthesis and are preferably used as sole additives or as a mixture in cosmetic or dermatological preparations. In addition to the use of the agent as a cosmetic or dermatological preparation, there is also a polymer matrix, a skin and / or wound dressing, a plaster, a cloth or

Pad, a spray, a pen or textiles, such as bandages or

Bathing textiles, in order to ensure continuous tanning, are preferred as agents according to the invention. It is advantageous in the case of bandages equipped with the compounds according to the invention that the skin underneath undergoes the same brown color as the uncovered skin while the bandage is being worn.

It has been shown through intensive research that the compounds according to the invention are in topical compositions, in particular cosmetic or dermatological preparations, lead to the induction of skin pigmentation. Melanogenesis is increased, there is more melanin in the skin, the skin becomes brown and the skin's own protection is physiologically increased. Even when applied topically to hair, the compounds according to the invention, in suitable preparations, lead to an intensification of the hair color, with which natural graying of the hair can also be avoided and even reversed.

The activation of the skin's own tanning and the intensification of hair coloring can of course be done with and without the involvement of UV light.

The compounds according to the invention are characterized inter alia by also in that they induce the formation of skin's own pigments in the skin, for example after topical application, increase the melanin synthesis and in this way produce an increased tan of the skin. They are harmless to health, non-irritating and easy to use, and the resulting shade naturally corresponds to that of the natural, healthy skin color. The tan obtained is - since it corresponds to the natural tanning - lightfast and not washable. The agents according to the invention also surprisingly intensify the tanning of already tanned skin and moreover delay the bleaching of tanned skin. Another advantage of the present invention results from the protective properties of natural melanin formed in the skin. In addition to various other functions of the skin's own melanin (such as "detoxification" or binding of toxic substances and / or pharmaceuticals, etc.), these functions of melanin are also very important for the skin, i.a. regarding homeostasis, skin aging prevention and the like:

Melanin acts as a natural UV filter to protect against damaging UV rays and also as an antioxidant to protect against reactive oxygen species (oxidative stress), which can occur, among other things, from sun exposure.

Thus, when used according to the invention, for example after topical application, there is not only a cosmetic benefit in the sense of increased tanning due to the increased melanin synthesis in the skin, but also an additional benefit due to the various protective benefits of melanin. The agents according to the invention, cosmetic or dermatological preparations, induce the formation of skin and hair-specific pigments in the skin and hair, intensify the existing natural and / or artificial tanning of the skin, compensate for inconsistent pigmentation of the skin, intensify the natural hair color and leave the tanning and hair coloring last longer. In all respects, the formulations according to the invention are extremely satisfactory preparations which are distinguished by a uniform coloring effect. It was not foreseeable for the person skilled in the art that the formulations according to the invention are easier to formulate, give the skin and hair a natural appearance faster and better, make the tanning and hair coloring last longer, work better than moisturizing preparations, better promote smoothing of the skin , ■ are characterized by better care, have better sensory properties, such as spreadability on the skin and hair or the ability to be absorbed into the skin, and ■ would offer better / risk-free protection of the skin and hair (against UV radiation) than the cosmetic preparations of the prior art. In addition, the formulations according to the invention surprisingly have no hormonal effects.

The content of the isoprenoid structure compounds is between 0.0001 and 30% by weight, advantageously between 0.001 and 10% by weight, particularly advantageously between 0.02 and 2% by weight, in each case based on the total weight of the compositions, preferably the cosmetic preparations.

As a cosmetic and / or dermatological formulation according to the invention, these can be composed as usual and serve in particular for the treatment and care of the skin and / or hair, as a make-up product in decorative cosmetics or as a sunscreen or so-called pre- or after-sun preparation. Correspondingly, depending on their structure, the formulations according to the invention can be used, for example, as skin protection cream, face cream, cleansing milk, sunscreen lotion, nutrient cream, day or night cream, etc. It is also possible and advantageous for the purposes of the present invention to insert the compounds according to the invention into aqueous systems or surfactant preparations for cleaning and care of the skin and hair. This includes shower gels, shampoos but also conditioners, hair care treatments, hair rinses, hair tonics, sprays etc.

It is of course known to the person skilled in the art that sophisticated cosmetic compositions are usually inconceivable without the customary auxiliaries and additives. These include, for example, consistency agents, fillers, perfume, dyes, emulsifiers, additional active ingredients such as vitamins or proteins, light stabilizers, stabilizers, insect repellents, alcohol, water, salts, antimicrobial, proteolytically or keratolytically active substances, preservatives, bactericides, substances for preventing the Foaming, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes or other common components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents, silicone derivatives or moisturizers etc. It is also advantageous to present the compound or compounds according to the invention in encapsulated form, for example in collagen matrices and other customary encapsulation materials, such as, for example, cyclic oligosaccharides (in particular alpha, beta, HP-beta, ra dom-Me-beta, gamma- Cyciodextrin), said corresponding alpha- the chemical known to ^'those skilled properties of the compounds according to the invention, beta- or gamma-cyclodextrins be used as Verkapselungsmatrial. Furthermore, it may be advantageous to present the compounds according to the invention or their mixtures in the form of cellulose encapsulations, in gelatin, wax matrices or encapsulated in liposomes. When encapsulated with cyclodextrins, it is assumed that the cyclodextrin skeletons act as the host molecule and the active ingredient according to the invention acts as the guest molecule. For the preparation, cyclodextrins are dissolved in water and the active ingredient according to the invention is added. The molecular adduct then precipitates as a solid and can be subjected to the usual cleaning and preparation steps. It is known that cyclodextrin-guest complexes in an appropriate solvent (eg water) are in equilibrium between the specific guest-cyclodextrin complex and the dissociated form, with cyclodextrin and guest too can be separated to a certain extent. Such balance systems are also advantageous in the sense of the present invention.

Mutatis mutandis, corresponding requirements apply to the formulation of medical preparations.

Medical topical compositions in the sense of the present invention generally contain one or more medicaments in an effective concentration. For the sake of simplicity, reference is made to the legal provisions of the Federal Republic of Germany (e.g. cosmetics regulation, food and drug law) for a clear distinction between cosmetic and medical use and corresponding products.

It is also advantageous to add the compound (s) according to the invention as an additive to preparations which already contain other active ingredients for other purposes.

It was surprisingly found in the present invention that the formulations according to the invention are also particularly suitable for combinations with active ingredients which have a positive effect on the condition of the skin. It has been shown that active ingredients to positively influence the aging skin, which reduce the appearance of wrinkles or existing wrinkles. So especially in combination with bioquinones, especially ubiquinone Q10, creatine, Kreinin, carnitine, biotin, isoflavone, cardiolipin, lipoic acid, liponamide, folic acid and its derivatives, niacin and its derivatives, anti freezing proteins, hop and hop malt extracts. Promoting agents for the restructuring of the connective tissue, such as isoflavonoids and isoflavonoid-containing plant extracts such as soybean and clover extracts, can also be used very well in the formulations according to the invention. It also shows that the formulations are particularly suitable, active ingredients to support skin functions in dry skin, such as vitamin C, biotin, carnitine, creatine, propionic acid, green tea extracts, eucalyptus oil, urea and mineral salts such as. B. NaCI, marine minerals and osmolytes such. B. taurine, inositol, betaine, quaternary ammonium compounds to use. In a similar way, the incorporation of active ingredients to alleviate or positively influence irritative skin conditions has proven to be advantageous, be it with sensitive skin in general or with skin irritated by noxious substances (UV light, chemicals). Active substances such as sericosides, various extracts of licorice, licochalcone, in particular are to be mentioned here Licochalcone A, sily arin, silyphos, dexpanthenol, inhibitors of prostaglandin metabolism, in particular cyclooxygenase and leukotriene metabolism, in particular 5-lipoxyenase, but also 5-lipoxvgenase inhibitor protein, FLAP. The incorporation of pigmentation modulators also proved to be advantageous. Active substances are to be mentioned here which reduce the pigmentation of the skin and thus lead to a cosmetically desired lightening of the skin and / or reduce the appearance of age spots and / or lighten existing age spots. Examples include tyrosine sulfate, dioic acid (8-hexadecen-1, 16-dicarboxylic acid as well as lipoic acid and liponamide, various extracts of licorice. Kojic acid, hydroquinone, arbutin, alpha-arbutin, deoxyarbutin, fruit acids, especially alpha-hydroxy acids (AHAs) , Bearberry (Uvae ursi), ursolic acid, ascorbic acid, green tea extracts, aminoguanidine, pyridoxamine. In the same way, the formulations according to the invention proved to be excellent combination partners for other active ingredients which bring about an intensified or faster tanning of the skin (Advanced Glycation End Products (AGE) , ipofuscine, nucleic acid oligonucleotides, purines and pyrimidines, NO-releasing substances), be it with or without the influence of UV light.

Cosmetic and dermatological preparations in the form of a sunscreen are particularly preferred. These can advantageously additionally contain at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably an inorganic micropigment.

Surprisingly, cosmetic and dermatological preparations according to the invention are able to prolong the natural tanning process.

It is also astonishing that cosmetic and dermatological formulations according to the invention are able to serve for the treatment of hypopigmentation (vitiligo, uneven pigmentation in aging skin, etc.).

Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property that, after application or distribution on the skin surface, the release of moisture from the horny layer (also to reduce transepidermal water loss (TEWL) and / or to positively influence the hydration of the horny layer.

Advantageous moisturizers for the purposes of the present invention are, for example, glycerin, lactic acid, pyrrolidone carboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available.

Glycerin can be used as a moisturizer in the sense of the present application in the range of 0.05-30% by weight, particularly preferably 1-10%.

The respective amounts of cosmetic or dermatological auxiliaries and carriers and perfume can be easily determined by a person skilled in the art, depending on the type of product, by simply trying them out.

An additional content of antioxidants in the preparations according to the invention is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

It is therefore advantageous to add antioxidants to the preparations according to the invention. The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, phenylalanine, tryptophan) and their derivatives (in particular N-acetyl-tyrosine, N-acetyl-phenylalanine), imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, J3-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, Lipoic acid and its derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, Butyl and lauryl, palmitoyl, oleyl, linoleyl, choiesteryl and glyceryl esters) and their salts, dilauryithiodipropionate, distearylthio dipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts ) and sulfoximine compounds (e.g. but hionin- sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferin) , -Hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg ^ -linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyfpalmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (especially vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, - glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajakarzarzäure, nordihydrog uajaretic acid, trihydroxybutyropheπoπ, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnS0 ₄ ) selenium and its derivatives (eg selenium methionine), stilbene and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the Derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances mentioned.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the compositions the preparation. If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the formulation. If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.

Cosmetic or dermatological formulations in the sense of the present invention can preferably contain, in addition to one or more oil phases, one or more water phases and, for example, in the form of W / O-, O / W-, W / O / W- or O / W / O- Emulsions are present. Such emulsions can preferably also be a microemulsion, a Pickering emulsion or a sprayable emulsion. In addition, the formulations according to the invention can also advantageously be in the form of oil-free preparations, such as gels, or as anhydrous preparations.

The formulations according to the invention can furthermore advantageously also contain dihydroxyacetone or nut extracts as well as other substances which are intended to maintain or produce the tan or to additionally reinforce them.

The lipid phase of the emulsions according to the invention can advantageously be selected from the following group of substances: mineral oils, mineral wax oils, such as triglycerides of capric or caprylic acid, but preferably castor oil; Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with low C alcohols, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids; benzoates; Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms, from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C -atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isonoylyl stearate, iso-nonylisononanoate, 2-ethyl-2-ethylhexyl, ethyl-2-ethylhexyl 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic, semisynthetic and natural mixtures of such esters, for example jojoba oil. Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 - 18 carbon atoms. The fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, 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 can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

The oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C ₂ -i ₅ -alky! Benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Particularly advantageous are mixtures of Cι ₂ i5-alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C ₁₂ .ι ₅ -alkyl and isotridecyl isononanoate and mixtures of C ₂ -i ₅ alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene are advantageously used in the context of the present invention.

The oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane). Mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.

The aqueous phase of the preparations according to the invention optionally advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether , Diethylenglykolmonomethyl- or -monoethylether and similar products, furthermore alcohols of low C number, for example Ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides and their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination.

UV filter substances can also be added to the preparation according to the invention.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: octocrylene), 2-ethylhexyl-2-hydroxybenzoate (2- Ethyl hexyl salicylate, octyl salicylate, INCI: octyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexy! -4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamate isopentyl ester methoxy cinnamate, INCI: isoamyl p-methoxycinnamate). Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (Ti0 ₂ ), zinc (ZnO), iron (e.g. Fe ₂ 0 ₃ ), zirconium (Zr0 ₂ ), silicon ( Si0 ₂ ), manganese (e.g. MnO), aluminum (Al ₂ O ₃ ), cerium (e.g. Ce ₂ 0 ₃ ), mixed oxides of the corresponding metals as well as mixtures of such oxides and the sulfate of barium (BaS0 ₄ ). For the purposes of the present invention, the pigments can also advantageously be used in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions. According to the invention, the pigments can advantageously be surface-treated ("coated"), for example, a hydrophilic, amphiphilic or hydrophobic character should be formed or maintained. This surface treatment can consist in that the pigments are prepared using a thin hydrophilic and The various surface coatings can also contain water for the purposes of the present invention. Inorganic surface coatings for the purposes of the present invention can consist of aluminum oxide (Al ₂ O ₃ ), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaP0 ₃ ) ₆ , sodium metaphosphate (NaP0 ₃ ) n, silicon dioxide (Si0 ₂ ) (also: silica, CAS no .: 7631 -86-9), or iron oxide (Fe ₂ 0 ₃ ) These inorganic surface coatings can be used alone, in combination and / or in combination with organic coating materials. Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials. Zinc oxide particles and predispersions of zinc oxide particles suitable according to the invention are available under the following trade names from the listed companies:

Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available under the following trade names from the companies listed: Advantageous UV-A filter substances for the purposes of the present invention are di-benzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ^® 1789 and is sold by Merck under the trade name Eusolex® 9020. Advantageous further UV filter substances in the sense of the present invention are sulfonated, water-soluble UV filters, such as. For example: • phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene 1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis sodium salt with the INCI name bisimidazylate (CAS no .: 180898-37-7), which, for example, under the Trade name Neo Heliopan AP is available from Haarmann &Reimer; • Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which, for example, under the Trade name Eusolex 232 is available from Merck or under Neo Heliopan Hydra from Haarmann &Reimer; • 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene)) bis- (7,7-dimethyl-2- oxo-bicyclo- [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 0-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also called benzene-1, 4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher Sulfonic Acid (CAS. -No .: 90457-82-2) and is available for example under the trade name Mexoryl SX from Chimex; • Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and its salts.

Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, i.e. Filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, such as. B.

• 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: Aniso Triazine), which is available under the trade name Tinosorb® S from CIBA-Ohemialen GmbH; Diethylhexylbutylamidotriazon (INCI: Diethylhexyibutamidotriazone), which is available under the trade name UVASORB HEB from Sigma 3V;

• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), also: 2,4,6-tris [anilino - (p-carbo-2'-ethyl-1'-hexyloxy)] - 1, 3,5-triazine (INCI: Ethylhexyl Triazone), which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150. An advantageous broadband filter In the context of the present invention is also the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol), which under the Trade name Tinosorb® M is available from CIBA-Ohemialen GmbH.

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1, 3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS no .: 155633-54-8) with the INCI name Drometrizole Trisiloxane, which is available under the trade name Mexoryl® XL from Chimex.

The other UV filter substances can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances in the sense of the present invention are e.g. For example: ■ 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;

■ 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;

■ Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone »As well as UV filters bound to polymers.

3- (4- (2,2-bis-ethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer which is available, for example, from Hoffmann La Röche under the trade name Parsol® SLX. Advantageous water-soluble filter substances are e.g. B .:

Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bomylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their

Salts.

A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) from BASF under the name Uvinul ^® N 539th

Particularly advantageous preparations within the meaning of the present invention, which are distinguished by a high or very high UV-A and / or UV-B protection, preferably contain further UV-A and in addition to the filter substance (s) according to the invention / or broadband filter, in particular dibenzoylmethane derivatives [for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane], phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethyl- hexyIoxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, in each case individually or in any combination with one another.

Benzoxazole derivatives such as, in particular, 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1 are also particularly advantageous according to the invention , 3,5-triazine with the CAS No. 288254-16-0, which is available, for example, under the trade name Uvasorb® K2A, and hydroxybenzophenones such as, in particular, the 2- (4'-diethylamine-2'-hydoxybenzoyl) benzoate or else Aminobenzophenone, which is available under the Uvinul A Plus.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, each based on the total weight of the preparations to kos - To provide metallic preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair.

The formulations according to the invention can advantageously, although not necessarily, also be used in combination with UV radiation - be it with artificially produced or natural ultraviolet rays - for example in order to increase natural tanning or to achieve particularly long-lasting tanning.

For use, the cosmetic and dermatological formulations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

According to the detailed explanations, the use of the agent according to the invention, in particular a cosmetic and / or dermatological preparation, is preferred - as an aqueous system and / or surfactant preparation for cleaning and care of the skin and / or hair, - as a multiple emulsion, microemulsion, pickering emulsion or sprayable emulsion, as a presun, a sunscreen or an aftersun formulation, - for topical use on skin and / or hair, - for tanning the skin, - for skin care, - for protecting the skin and / or hair from damaging UV rays, - to increase the melanin synthesis in the skin, - to prolong the brown color of the skin, - to protect the skin from oxidative stress, - to protect the skin from chronological and light-related skin aging, - to intensify the hair color, - to prevent it graying of the hair and / or to protect the hair from fading due to sunlight, - as a shower gel, shampoo, condition er, hair care regimen, hair conditioner, hair tonic, hair spray, make-up, skin protection, face, cleaning, sun protection, nutritional, day or night cream, gel or lotion or cleansing preparation. The compounds according to the invention can likewise be part of a polymer matrix, a skin and / or wound dressing, a plaster, a cloth or pad, a spray or applied to or in textiles such as bandages or bathing textiles.

The incorporation of the compounds into polymer matrices, such as, for example, polyurethane matrices, is thus possible without any problems. Similar to the known active ingredient release, the compounds can be released from the matrix to the skin or the hair and enable their advantageous properties there. In a plaster application or applied to textiles, bandages or the like, the compounds can penetrate the skin and bring about the desired protection, care or tanning effect.

Application as a spray is preferred since the compounds only have to be mixed with suitable aerosols or gases.

Unless otherwise stated, all quantities, proportions and percentages are based on the weight and the total quantity or on the total weight of the preparations.

Examples

PIT emulsions

3. O / W cream

6. Hvdrodispersions

8. W / O cream

9. W / O / W cream

10. Spray formulation

13. Hair conditioner

14. Pearlescent conditioner shampoo

15. Clear conditioner shampoo

16. Clear light shampoo with volume effect

Claims

claims

1. Agent for use on the skin and / or hair, characterized in that the agent has one or more compounds with an isoprenoid structure

contains, where the CC compounds between C ^ C ₂ , C ₃ , C ₄ , R ₃ and R ₅ can be both saturated and unsaturated,

n is an integer from 1 to 7 and the radicals - Rx and Ry independently of one another represent carbon with single or double-bonded radicals R4, R4 ^' and / or R4 ^" ,

- R4 "are selected from compounds of the structure Ri-

^R2 or -,

R1, R2, R3 and / or R5 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hydroymethyl, hydroxyethyl, hydroxypropyl, hydroxy and / or alkyl carboxylates with alkyl radicals selected from methyl, Ethyl, propyl or butyl, - R4 is selected from - carbonyl oxygen, - amino acid residues Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg , Gin, H, Orn, Sar, Hyl, Hyp, Hse or Hey, - residues of the structure N-OH, N- (CH ₂ ) _x -OH, N- (CHR9) _X -CH20H, N- (CHR9) _x -OH, N- (CH ₂ ) _x -OCOMe, where each x = 1-10, or - residues of the structure

R9 is selected from hydrogen and / or hydroxy,

R11 is selected from methyl, hydroxymethyl, hydrogen, prop-2-yl, isobutyl, but-2-yl, pyrrolidin-1, 2-diyl, 1H-indol-3-yl-methyl, benzyl -; 2- (methylthio) ethyl, 4-hydroxybenzyl, 1-hydroxyethyl, mercaptomethyl, 2-amino-2-oxoethyl, carboxymethyl, carboxyethyl, 4-aminobutyl, 3 - {[amino (imino ) methyl] amino} propyl, 3-amino-3-oxopropyl, hydrogen and N-Me, 3-aminopropyl, ethyl, 1H-imidazol-4-yl-methyl, butyl, propyl, 4- Amino-3-hydroxy-butyl, 4-hydroxy-pyrrolidin-1, 2-diyl, hydroxyethyl, or 2-mercaptoethyl, R10 is selected from - hydroxy- (-OH), - peptidically N-linked amino acid residues selected from Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg, Gin, H, Orn, Sar, Hyl, Hyp, Hse or hey, remnants of the structure

with b = 1 - 6, or O, R12 O ^'

R12 is selected from mono- to polysaccharides, preferably uniform and / or mixed mono-, di- or trisaccharides, preferably glucose, glycerose, erythrose, threose, ribose, arabinose, lyxose, xylose, allose, altrose, galactose, gulose, idose, Mannose or talose; R4 ^'is selected from Amino acid residues Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg, Gin, H, Orn, Sar, Hyl, Hyp, Hse, Hey or remnants of the structure

with b = 1 - 6, or, R15 O

R13 is selected from methyl, hydroxymethyl hydrogen, prop-2-yl, isobutyl, but-2-yl, pyrrolidin-1, 2-diyl, 1H-indol-3-yl-methyl, benzyl; 2- (methylthio) ethyl, 4-hydroxybenzyl, 1-hydroxyethyl, mercaptomethyl, 2-amino-2-oxoethyl, carboxymethyl, carboxyethyl, 4-aminobutyl, 3 - {[amino (imino ) methyl] amino} propyl, 3-amino-3-oxopropyl, hydrogen and N-Me, 3-aminopropyl, ethyl, 1 H-imidazol-4-yl-methyl, butyl, propyl, 4 -Amino-; 3-hydroxy-butyl-, 4-hydroxy-pyrrolidin-1, 2-diyl-, hydroxyethyl- and / or 2-mercaptoethyl-, - R14 is selected from hydroxy- (-OH), hydrogen (- H) and / or peptidically O-linked amino acid residues selected from Ala, Ser, Gly, Val, Leu, lle, Pro, Trp, Phe, Met Tyr, Thr, Cys, Asn, Asp, Glu, Lys, Arg, Gin, H , Orn, Sar, Hyl, Hyp, Hse, Hey, preferably Ala, Ser or Gly and

- R15 is selected from mono- to polysaccharides, preferably uniform and mixed mono-, di- or trisaccharides, preferably glucose, glycerose, erythrose, threose, ribose, arabinose, lyxose, xylose, allose, altrose, galactose, gulose, idose, mannose or Talose.

2. Composition according to claim 1 for increasing skin tanning and / or melanin synthesis in the skin and / or hair.

3. Agent according to claim 1 or 2, characterized in that the agent is a cosmetic and / or dermatological preparation, a polymer matrix, a skin and / or wound dressing, a plaster, a cloth or pad, a spray or a textile.

4. Agent according to claim 3, characterized in that the agent is a cosmetic and / or dermatological preparation.

5. Agent according to one of the preceding claims, characterized in that R1, R2, R3 and / or R5 are methyl radicals and / or hydrogen.

6. Agent according to one of the preceding claims, characterized in that the compounds are selected from compounds of structure I to VIII

VI:

preferably 0.05-20% by weight, in particular 0.1-10% by weight, based on the total weight of the agent, preferably a cosmetic preparation.

12. Cosmetic and / or dermatological preparation according to one of claims 3 to 11, characterized in that in addition preservatives, bactericides, perfumes, substances for preventing foaming, dyes, fillers, pigments which have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes, alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents, silicone derivatives, moisturizers, vitamins, proteins, light stabilizers, stabilizers, insect repellents, water, salts, antimicrobial, proteolytic or keratolytically active substances , Medication or other common components of a cosmetic or dermatological formulation are included.

13. Preparation according to claim 12, characterized in that glycerin is added as a moisturizer in the range from 0.05 to 30% by weight, particularly preferably 1 to 10% by weight, based on the total mass of the preparation.

14. Cosmetic and / or dermatological preparation according to one of claims 3 to 13 in combinations with - active substances which have a positive influence on the condition of the skin, in particular active substances for positively influencing the aging skin, in particular in combination with bioquinones, in particular ubiquinone Q10, creatine, creatinine , Carnitine, biotin, isoflavone, cardiolipin, lipoic acid, anti-freezing proteins, hop and hop-malt extracts, - promoting agents for restructuring the connective tissue, especially isoflavonoids, - active ingredients to support skin functions in dry skin, especially vitamin C, biotin , Carnitine, creatine, propionic acid, green tea extracts, eucalyptus oil, urea and mineral salts, in particular NaCI, sea minerals and osmolytes, - active ingredients for the relief and / or positive influence of irritative skin conditions, in particular sericosides, various extracts of Licorice, Licochalcone, in particular Licochalcone A, Silymarin, Silyphos, Dexpanthenol, - inhibitors of prostaglandin metabolism, in particular cyclooxygenase and leukotriene metabolism, especially 5-lipoxyenase or 5-lipoxvgenase inhibitor protein, FLAP, modulators of pigmentation sulfate, especially tyrosinic acid sulfate, especially 8-Hexadecen-1, 16-dicarboxylic acid), lipoic acid, liponamide, various extracts of liquorice, kojic acid, hydroquinone, arbutin, fruit acids, especially alpha-hydroxy acids (AHAs), bearberry (Uvae ursi), ursolic acid, ascorbic acid. Green tea extracts, aminoguanidine, pyridoxamine and / or active ingredients that bring about an intensified or faster tanning of the skin, in particular advanced glycation end products (AGE), lipofuscins, nucleic acid oligonucleotides, purines, pyrimidines, NO-releasing substances.

15. Cosmetic and / or dermatological preparation according to one of claims 3 to 14 in combinations with one or more compounds selected from the group phytoene, phytofluene, ζ-carotene, neurosporin, lycopene, ß-carotene, squalene, variabilin, phytanic acid and / or phytol.

16. Use of the agent according to one of claims 1 to 15 in or as an aqueous system and / or surfactant preparation for cleaning and / or care of the skin and / or hair.

17. Use of a preparation according to one of claims 3 to 15 as a multiple emulsion, microemulsion, Pickering emulsion or sprayable emulsion.

18. Use of a preparation according to one of claims 3 to 15 as a presun, a sunscreen or an aftersun formulation.

19. Use of the agent according to one of claims 1 to 15 for topical use on skin and / or hair.

20. Use of the agent according to one of claims 1 to 15 for tanning the skin.

21. Use of the agent according to one of claims 1 to 15 for skin care.

22. Use of the agent according to any one of claims 1 to 15 for protecting the skin and / or hair from damaging UV rays.

23. Use of the agent according to one of claims 1 to 15 to increase melanin synthesis in the skin.

24. Use of the agent according to one of claims 1 to 15 to prolong the brown color of the skin.

25. Use of the agent according to any one of claims 1 to 15 to reduce uneven pigmentation of the skin, in particular age spots, melasma, freckles and vitiligo.

26. Use of the agent according to one of claims 1 to 15 for protecting the skin from oxidative stress.

27. Use of the agent according to one of claims 1 to 15 for protecting the skin against chronological and light-related skin aging and / or against UV-related acute damage, such as e.g. the sunburn.

28. Use of the agent according to one of claims 1 to 15 for intensifying the hair color.

29. Use of the agent according to one of claims 1 to 15 to prevent graying of the hair and / or to protect the hair from fading due to sunlight.

Use of the preparation according to one of claims 3 to 15 as a shower gel, shampoo, conditioner, hair care regimen, hair rinse, hair tonic, hair spray, makeup, skin protection, face, cleaning, sun protection, nutritional, day or night cream, gel, or lotion or cleansing preparation.