EP1675560A1 - Agents for use on skin and/or hair containing quadruply substituted cyclohexene compounds - Google Patents

Abstract

The invention relates to agents for use on skin or hair, particularly for increasing skin tanning and the synthesis of melanin in skin or hair. The invention contains, in particular, cosmetic or dermatological preparations containing quadruply substituted cyclohexene compounds. The use of the preparations leads to the induction and intensification of the tanning mechanisms of skin, the intensification of hair color and thus also to an intensification of the skin's and hair's protection of itself.

Description

 description

Agents for use on the skin and / or hair containing 4-times substituted cyclohexene compounds

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 encompasses cosmetic or dermatological preparations containing 4-times substituted cyclohexene compounds. The use of the preparations leads to the induction and intensification of the 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 ^■ generally known. While rays with a wavelength shorter 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 thus been proven that U VA radiation damages the elastic and collagen fibers of the connective tissue, which causes the skin to age prematurely, and that it is seen as the cause of numerous phototoxic and photoallergic reactions is. The damaging influence of UVB radiation can be intensified by UV-A radiation.

UVA radiation can also cause skin damage by, inter alia, the skin's own keratin or elastin is damaged. This reduces the elasticity and water retention capacity of the skin, ie the skin becomes less supple and tends to Wrinkling. This type of wrinkling is also called light-induced skin aging ^■. The strikingly high incidence of skin cancer in areas exposed to strong sunlight 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 that arise 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 very significantly involved in light-related skin aging (including wrinkling) due to oxidative damage to various skin structures. UV radiation also belongs to ionizing radiation. There is therefore a risk that ionic species also develop when exposed to UV, which in turn can then oxidatively intervene in the biochemical processes.

The pigmentation of human skin is essentially due to the presence of. Melanin works. Melanin and its breakdown products (melanoids), carotene, the degree of blood circulation and 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 of various 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. with colored people, but also with light skin melanin can also be found 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.

Melanocytes, as a characteristic cell organ, contain rapid 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'V connection of toxic substances / pharrnaka, 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 sun radiation, is very - important for the skin, also in relation to homeostasis, avoidance of skin aging, avoidance of sunburn etc. So there should not only be a cosmetic benefit in terms of increased tanning due to the increased melanin synthesis in the skin after topical application of compounds which increase the melanogenesis, but also provide 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 sunburn, skin type V dark, often almost black skin, never gets sunburn.

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. Of course, only those parts of the body that are covered by the colored preparations are stained. With the help of washable make-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. A further 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 be irritating to 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 chemical modification of the skin's skin layer 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). Hydroxyacetone can be called etotriose and reacts as a reducing sugar with the amino acids of the skin or the free amino and i mino groups of keratin via a series of intermediates in the sense of a Maillard reaction to brown-colored substances, so-called melanoids, which are sometimes also called melanoidins. A particular disadvantage of tanning with dihydroxyacetone is that the skin tanned with it, in contrast to "sun-tanned" skin, is not protected against sunburn.

Another disadvantage of dihydroxyacetone is that it releases formaldehyde, especially under the influence of ultraviolet radiation, even if mostly in small amounts. It has therefore been an urgent need to have 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. In the sun, these preparations then yellow, which should lead to a slight brown-yellow coloring of the epidermis, which additionally reinforces the "tan".

US 5093360 describes cosmetic or pharmaceutical preparations which contain retinal (vitamin A aldehyde) and / or their derivatives. Retinal or its derivatives are used in combination with active agents or as additives in various preparations to remedy dermatological malfunctions. In addition to the treatment of acne, tanning preparations are also mentioned which, in addition to the tanning agents, contain retinal or their derivatives as an additive. There is no indication that retinal or its derivatives alone have an effect on skin tanning. Another type of artificial tanning, which is also completely independent of UV light, can be brought about by the hormones which are also released in the body as a result of (natural) UV radiation and ultimately stimulate the melanocytes to synthesize melanin. Worth mentioning in this context are, for example, descendants of proopiomelanocortin (POMC) like aMSH and synthetic variants (like N DP), some of which have much higher activity than natural aMSH. Although these hormones can generally bring about a tan, their use in cosmetics is forbidden since 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 these hairs is roughly similar: the central hair mark (from epithelial cells with eosinophilic homology - -Trichohyalin-Granuia), surrounded by the hair cortex (from horny cells; contains pigments) and the epidermis (cuticle pili; coreless epidermis layer) as well as layers of the epithelial and connective tissue sheath.

The hair is divided into the hair shaft protruding from the skin and the sloping 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 as a result of constant new formation of cells due to its layer close to the papilla (matrix), later closed, bulbous, whole cornified (piston hair) and is finally, in the final (= telogen) phase, displaced by a new hair - starting from a newly formed hair papilla - towards the follicle opening.

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. As characteristic cell organelles, melanocytes contain 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 melani 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 (vitamin B deficiency anemia), severe endocrinological disorders, e.g. B. in thyroid diseases. acute, febrile diseases, drug side effects, cosmetics, metals.

The coloring of hair, especially of living human hair, with the help of 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 taking place for several years the subject of a new 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 will 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 - either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are used. 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-tetraaminopyrirnidine and their derivatives are usually used as developer components 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-aminopyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, 2-hydroxy-4,5,6-triarninopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components, m-phenylenediamine dehvates, naphthols,. Resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used. Suitable coupler substances are in particular α-naphthol, 1, 5-, 2.7 »and, 7-bihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol,. Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 1- phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4- diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol 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 diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim.

With oxidation dyes intensive dyeings can be achieved with good fastness properties, but the development of the color is generally done 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 can 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 as. B. H ₂ 0 _{2 to be} instructed. In addition, the agents must have no or only a very low sensitization potential.

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 14, 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 a person skilled in the art that an agent, preferably cosmetic or dermatological preparations, contains one or more compounds of the structure

hereinafter referred to as 4-times substituted cyclohexene compounds that solve the problems. With the leftovers

- R1, R2 and / or R5 selected. earth from the group hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, tert-butyl, hydroymethyl, hydroxyethyl, hydroxypropyl, hydroxy and / or carboxylic acid alkyl esters with alkyl radicals selected from methyl, ethyl, propyl or butyl, methyl is preferred ;

- R3 is selected from the group of connection residues of structure (I) to (XIX) with

preferably with n = 1 or 2, R4 = carbonyl oxygen, 6 = methyl and R6 ^' = hydrogen or methyl, (II)

preferably with R4 = carbonyl oxygen, R6 and R7 = methyl, (III)

preferably with R ₄ '= O-glycosyl, R6 and R7 = methyl, (IV)

preferably with R6 and R7 = methyl and R4 = carbonyl oxygen, (V)

preferably with R6 and R7 = methyl, R ₄ = O-glycosyl, (VI)

preferably with n = 1 or 2, R4 = carbonyl oxygen, R6 = methyl and R6 '

Hydrogen or methyl,

(VII)

preferably with n = 1, 2 or 3, R6 = methyl and R6 '= hydrogen or methyl and R = O-glycosyl,

(VIII)

preferably with R6 and R7 = methyl, R4 '= O-glycosyl,

(IX)

preferably with n = 1, 2 or 3, R6 = methyl, R6 '= hydrogen or methyl and

FU - O-glycosyl,

(X)

preferably with R6 and R7 = methyl, n = 0, 1, 2 or 3 and R4 = carbonyl oxygen, (X preferably with R6 and R7 = methyl, n = 0, 1, 2 or 3 and R '= O-glycosyl,

(XII)

preferably with R6 and R7 = methyl and R4 = carbonyl oxygen, (XIII)

preferably with R6 and R7 = methyl and R ₄ '= O-glycosyl, (XIV)

preferably with R6 and R7 = methyl and R4 = carbonyl oxygen, (XV)

preferably with R6 and R7 = methyl and R ₄ ^' = O-glycosyl, (XVI)

preferably with R6 and R7 = methyl, R8 = methyl or hydrogen and R4 =

carbonyl oxygen,

(XVII) preferably with R6 and R7 ^: = methyl I, R8 = methyl or hydrogen and R>'= = 0-glycosyl, (XVIII)

preferably with R6 and R7 = methyl and R4 = carbonyl oxygen or (XIX)

preferably with R6 and R7 = methyl and R ₄ '= O-glycosyl,

R6, R6 \ R7 and / or R8 are selected from the group hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, tert-butyl, hydroymethyl, hydroxyethyl,. Hydroxypropyl, hydroxy and / or carboxylic acid alkyl esters, the alkyl radical being selected from methyl, ethyl, propyl or butyl, preference being given to methyl;

R4 is selected from C arbonyl oxygen, from amino acid residues Ala, S er, 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- (CH ₂ ) _X -OH, N- (CHR9) _X -CH20H, N- (CHR9) _x -OH, N- (CH ₂ ) _x -OCOMe, where each x = 1-10, N-OH, 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-hydroxybenzyl, 1-hydroxyethyl, mercaptomethyl, 2-amino-2-oxoethyl, carboxymethyl, carboxyethyl, 4-aminobutyl, 3 - {[amino (imino ) methyl] amino} propyl-, 3-amino-3-oxopropyl-, hydrogen and _v N-Me, 3-aminopropyl-, ethyl-, 1H-imidazol-4-yl-methyl-, butyl-, propyl-, 4th -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), peptidic 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

- 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 b = 1-6, or R15 O - R13 is selected from methyl, hydroxymethyl hydrogen, prop-2-yl, isobutyl, but-2-yl, pyrrolidin-1, 2-diyl, 1 H -ndol-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-, preferably methyl-, hydroxymethyl- or

Hydrogen, with 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, the 4-times substituted cyclohexene compounds, are ideally suited to bring about increased skin tanning. All compounds of the structures listed above, which the person skilled in the art can do without to be inventive, can choose from the respective groups. 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 "detoxification'V connection of toxic substances / pharmaceuticals. In addition, the function of melanin as a natural UV filter for protection against harmful 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 4-times substituted cyclohexene compounds which increase the melanogenesis according to the invention also result in 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 the natural sun 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), meiasm 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. The invention also relates to the use of the preparations thus produced. To put it simply, the compounds according to the invention comprise ring-shaped hydrocarbon compounds, the ring-shaped structure preferably being composed of 6 carbon atoms and being partially to completely unsaturated and additionally having several, in particular 4, hydrocarbon substituents. The compounds according to the invention are simply referred to as tetrasubstituted cyclohexene compounds. Here 3 substituents are short-chain, preferably consisting of a methyl group (R1, R2 and R5), a further, fourth, substituent (R3), which can also consist of a branched and / or partially to completely unsaturated hydrocarbon compound, comprises 1 to 25 C. -Atoms, but preferably at least 4 and at most 20 C atoms. The end of the “fourth substituent” opposite the annular structure preferably, but not necessarily, has a polar end. It follows that the compound according to the invention has the following general structure:

where R1, R2 and R5 is preferably a methyl radical and R3 in the structures (I) to (XIX) described above represents a C1-C25 radical, preferably a C4-C20 radical, which preferably has a polar group at the opposite end having. Through the most intensive investigations and tests, the 4-times substituted compounds according to the invention could be suitable. Compounds for use on human skin and hair are crystallized out. Three basic building blocks, the cyclohexene ring, are essential. the structure and chain length of the radical R3 and its functional groupings or polarities. All of these findings lead to the compounds according to the invention, which the person skilled in the art can select in accordance with the structure (I) to (XIX) and the respective remaining information. The 4-fold substituted cyclohexene compounds according to the invention are known per se, at least from a synthetic point of view, but are not mentioned in connection with their suitability as agents for use on the skin or hair. The person skilled in the art can select a compound from the group of the compounds listed in claim 1 as required and even combine them with other compounds in order to achieve the effects which are advantageous according to the invention. From the compound structure (I) with the respectively preferred radicals R1, R2, R4, R5, R6 and R6 ^' , the following compounds (IUPAC names) with the structures indicated preferably result: - (3E) -3-methyl-4 - (2,6,6-trimethylcyclohex-1-en-1-yl) but-3-en-2-one

where R1, R2, R5, R6 and R6 'are each methyl radicals, n = 1 and R4 is a carbonyl oxygen,

- N - [(2 £) -1, 2-dimethyl-3- (2,6,6-trimethylcyclohex-1-en-1-yl) prop-2-en-1-ylidenes] -L-alanine

where R1, R2, R5, R6 and R6 'are each methyl radicals, n = 1 and R4 is a radical of

, with R11 = methyl and R10 is a hydroxy radical

(3E, 5 £, 7E) -3,6,7-trimethyl-8- (2,6,6-trimethyl-cyclohex-1-en-1-yl) octa-3,5,7-trien-2-one

where R1, R2, R5, R6 and R6 'are each methyl radicals, n = 2 and R4 is a carbonyl oxygen. W - [(2E, 4E, 6E) -1, 2,5,6-tetramethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-triene- 1 -ylidenes] -L-alanine

where R1, R2, R5, R6 and R6 ^'are each methyl radicals, n = 2 and R4 is a radical of

with R11 = methyl and R10 is a hydroxy radical

- (3E) -4- (2,6,6-trimethylcyclohex-1-en-1-yl) but-3-en-2-one with the structure

in which the rest R3 has the structure (I)

with R1, R2, R5 and R6 as methyl group, n = 1 and R6 '= hydrogen and R4 as carbonyl oxygen.

This (3 lbs) -4- (2,6,6-trimethylcyclohex-1-en-1-yl) but-3-en-2-one is available, for example, from InterBioScreen Moscow.

- (2 £, 3E) -4- (2,6,6-trimethylcyclohex-1-en-1-yl) but-3-en-2-one oxime with the structure

in which the rest R3 has the structure (I)

with R, R2, R5 and R6 as methyl group, n = 1 and R6 '= hydrogen and R4 as N-OH. This (£ 2, £ 3) -4- (2,6,6-trimethylcyclohex-1-en-1-yl) but-3-en-2-one oxime is also available, for example, from InterBioScreen Moscow. The compound structure (II) with the respectively preferred radicals R1, R2, R4, R5, R6 and R7 results, for example, in (3E, 5 £) -6-methyl-8- (2,6,6-trimethylcyclohex-1-ene) -1- yl) octa-3,5-dien-2-one of the structure

in which the radical R3 has the structure (II) and R1, R2, R5, R6 and R7 select a methyl group and R4 as carbonyl oxygen. This 6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-3,5-dien-2-one is available, for example, from InterBioScreen Moscow. Furthermore, the compound structure (II) with the respectively named residues R1, R2, R4, R5, R6 and R7 gives the following preferred compounds (IUPAC names) with the specified structures:

- / V - [(£ 2, £ 4) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-y) idene] - L-alanine

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 is a radical of

structure Methyl and R10 is a hydroxy radical. - ^' Λ / - [(£ 2, £ 4) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-ylidenes ] - L-alanyl-L-alanine

where R1, R2, R5, R6 and R7 each represent methyl radicals and R4 is a radical of the structure

with b = 1.

2 - {[(£ 1, £ 2, £ 4) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-diene-1- ylidene] amino} ethanol

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 is a radical of the structure N- (CH ₂ ) _X - OH with x = 2.

- (£ 2, £ 3, £ 5) -6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-3,5-dien-2-one oxime

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 is a radical of the structure N-OH.

2 - {[(£ 1, £ 2, £ 4) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-diene-1- ylidene] amino} ethyl acetate. ..

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 is a radical of the structure N- (CH ₂ ) _X OCOMe with x = 2.

The following preferred compounds (IUPAC names) with the specified structures result from the connection structure (III): - (£ 2, £ 4) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-yl-D-gluco pyranoside

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 ^'is a radical of the structure -0-R15 with R15 = -Glycosyl

- (2E, 4E) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-yl 4-0-ß-D - glucopyranosyl-D-glucopyranoside

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 'is a radical of the structure -0-R15 with R15 = -1, 4-di-glycosyl.

- (£ 2, £ 4) -1,5-dimethyl-7- (2,6,6-trimethyicyclohex-1-en-1-yl) hepta-2,4-dien-1-yl L-alanyl-L - alaninate

where R1, R2, R5, R6 and R7 each represent methyl radicals and R4 'a radical of the structure

Methyl radical, b = 2 and R14 = H.

The compound 3-methyl-8- (2,6,6-trimethyl-cyclohexyl-1-enyl) -octa-3,5,7-trien-2-one (5) also results, for example, from the compound structure (IV) the structure

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 is a carbonyl oxygen. The production of this species (5, IVa) is described in detail below.

In addition, the compound structure (IV) with the respectively mentioned or preferred radicals R1, R2, R4, R5, R6 and R7 results in the following preferred compounds (IUPAC names) with the structures indicated:

/ V - [(£ 2, £ 4, £ 6) -1,5-dimethyl-7- (2 _I 6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-triene- 1-ylidenes] -L-alanines.

with R1, R2, R5, R6 and R7 each as a methyl radical and R4 is a radical of

structure with R11 = methyl and R10 = hydroxy radical.

- 2 - {[(£ 1, £ 2, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4, 6-trien-1-ylidenes] amino} ethanol with R1, R2, R5, R6 and R7 each as a methyl radical and R4 as a radical of the structure N- (CH ₂ ) _X - 0H with x = 2.

- (2E, 3E, 5E, 7E) -6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-3,5,7-trien-2-one oxime _v

with R1, R2, R5, R6 and R7 each, as a methyl radical and R4 as a radical of the structure N-OH.

- 2 - {[(£ 1, £ 2, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4, 6-trien-1-ylidene] aminσ} ethyl acetate

with R1, R2, R5, R6 and R7 each as a methyl radical and R4 as a radical of the structure N- (CH ₂ ) _X - 0C0Me with x = 2.

From the connection structure (V) with the respectively named or preferred radicals R1, R2, R4, R5, R6 and R7, the following preferred compounds (IUPAC names) with the specified structures result:

- (£ 2, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-trien-1-yl D-giucopyranoside with R1, R2, R5, R6 and R7 each as a methyl radical and R4 ^' as a radical of the structure 0-R15 with R15 = -glucosyl.

- (£ 2, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4, β-trien-1-yl 4-0- α-D-glucopyranosyl-D-glucopyranoside

with R1, R2, R5, R6 and R7 each as a methyl radical and R4 ^' as a radical of the structure 0-R15 with R15 = 1, 4-di-glucosyl.

- (2E, £ 4, £ 6) -1,5-dimethyl-7- (2 _I 6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-trien-1-yl L - a! any! -L-alaninate

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 'is a radical of the O NH R 14

Structure 13 with b = 2, R13 = methyl radical and R14 = H. The connection structure (VI) gives, for example, (2E, 4E) -3-methyl-5- (2,6,6-trimethylcyclohexyl-1-enyl) penta-2,4-dienal (4), characterized by the structure (via)

where R3 corresponds to structure (VI) with n = 1, R4 = carbonyl oxygen and R1, R2, R5, R6 'as methyl radical and R6 = hydrogen. This compound ((4), Via) and the compound shown under ((5), IVa) are prepared according to the following synthesis protocols:

All reactions were carried out with dimmed light in order to limit the P hotodegradation or isomerization. 3- ethyi-5- (2,6,6-trimethyl-cyclohexyl-1-eny -perita-2,4-dienoic acid ethyl ether (2) Sodium hydride (1 g, 0.04 mol) is dispersed in 30 ml of absolute diethyl ether The reaction mixture is cooled with ice and then triethylphosphonoacetate (9 g, 0.04 mol), dissolved in diethyl ether (30 ml), is added dropwise and the mixture is stirred at room temperature for 2 hours β-ionone (5.15 g, 0.0285 mol) dissolved in diethyl ether (15 ml) is added, the reaction solution is stirred overnight, the reaction is quenched with water, the reaction product (2) is extracted with hexane (200 ml) and The organic phase is dried (MgSO ₄ ), filtered and the solvent is removed on a rotary evaporator 6.5 g (2) (92.5%) are obtained as the crude product.

The crude product is used for the next reaction step without further isolation.

3-methyl-5- (2,6,6-trimethyl-cyclohexyl-1-enyl) -penta-2,4-diene-1-ol (3) lithium aluminum hydride (LiAIH _4l 700 mg, 0.019 mol) dissolved in abs. Diethyl ether is cooled to -78 ^q C. (2) (3.2 g, 0.012 mol) is dissolved in diethyl ether (50 ml) and added dropwise to the L iAIH ₄ solution. The mixture is stirred for one hour at the same temperature, then warmed to room temperature and stirred for a further 2 hours. The approach to deactivating the excess LiAIH is then quenched with egg chips. The desired product (3) is extracted with diethyl ether and washed with water. 1 NH ₂ S0 ₄ is used to dissolve the aluminum oxide precipitate. The organic phase is dried (MgS0 ₄ ), filtered and freed from the solvent on a rotary evaporator. 3.0 g (3) (quantitative conversion) are obtained as a crude yield. 3-methyl-5- (2,6,6-trimethyl-cyclohexyl-1-enyl) penta-2,4-dlenal (4)

(3) (3.0 g, 0.013 mol) is dissolved in hexane (100 ml) and oxidized overnight with magnesium oxides (4 g). In the next 24 hours, 4 aliquots of 4 g of magnesium dioxide each are added. The course of the reaction is detected by thin layer chromatography. After complete oxidation to β-lonilidine acetaldehyde (4), the magnesium oxide is removed and washed with dichloromethane. The filtrate is freed from the solvent on a rotary evaporator. Column chromatography gives the desired product (4) in a yield of 85% (cis / trans isomers).

3-Methyl-8- (2,6,6-trimethyl-cyclohexyl-1-enyl) -octa-3,5,7-trien-2-one (5, IVa) β-lonilidine acetaldehyde (4) (2.7 g, 0.012 mol) ^~ wTrd dissolved in acetone (75 ml) and 1 N NaOH (5 ml) was added. The reaction mixture is stirred for 6 hours. The desired product (5) is extracted with hexane and washed with water. The organic phase is dried (MgS0 ₄ ) and the solvent is removed on a rotary evaporator. 3.0 g of the crude cis / trans mixture are obtained as the crude product, which give the desired product by column chromatography (slight gradient 0-10% EA / hexane).

The reference to the manufacturing instructions is: Tanumihardja, SA, J. Labeil., Comp.Radiopharm. 2001, 44, 365-372. From the connection structure (VI) with the respectively mentioned or preferred radicals R1, R2, R4, R5, R6 and R7, the following preferred compounds (IUPAC names) with the specified structures also result:

- Λ / - [(£ 2, £ 4) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-dien-1-ylidenes] - L-alanine

with R1, R2, R5, R6 and R7 each as a methyl radical, n = 1 and R4 is a radical of the structure

with R11 = methyl and R10 = hydroxy radical

2 - {[(£ 1, £ 2, £ 4) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-diene-1 - ylidene] amino} ethanol

with R1, R2, R5, R6 and R6 'as the methyl radical, n = 1 and R4 as the radical of the structure N- (CH ₂ ) _X - OH with x = 2.

- (£ 2, £ 4, £ 6, £ 8, £ 10) -3,4,9,10-tetramethyl ^ 11- (2,6,6-trimethylcyclohex-1-en-1-yl) undeca- 2 , 4,6,8, 10-pentaenal

with R1, R2, R5, R6 and R6 'as methyl radical, n = 2 and R4 as carbonyl oxygen.

N - [(£ 2, £ 4, £ 6, £ 8, £ 10, £ 10) -3,4,9,10-tetramethyl-11- (2,6,6-trimethylcyclohex-1-en-1-yl) undeca -2,4,6,8,10-pentaene-1-ylidene] -L-alanine with R1, R2, R5, R6 and R6 ^' as the methyl radical, n = 2 and R4 as the radical of the structure

R11 = methyl and R10 = hydroxy radical

2 - {[(£ 1, £ 2, £ 4, £ 6, £ 8, £ 10,) -3,4,9,10-tetramethyl-11 - (2,6,6-trimethyIcyclohex-1 -en- ^■ yl) undeca-2,4,6,8,10-pentaene-1-ylidene] amino} ethanol

with R1, R2, R5, R6 and R6 ^' as the methyl radical, n = 2 and R4 radical of the structure N- (CH ₂ ) _x -OH with x = 2.

The connection structure (VII) with the respectively mentioned or preferred radicals R1, R2, R4, R5, R6 and R7 results, for example, in the following preferred compounds (IUPAC names) with the structures indicated:

- i (£ 2, £ 4) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-dien-1-yl L-alanyl- L-alaninates

with R1, R2, R5, R6 and R6 ^' as the methyl radical, n = 1 and R4 ^' as the radical of the structure

(2 £, 4E) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-dien-1-yl D-glucopyranoside

with R1, R2, R5, R6 and R6 'as methyl radical, n = 1 and R4 ^' as radical of structure 0-R15 with R15 = glucosyl.

- (2E, £ 4) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-dien-1-yl 4-OD- g! Ucopyranosyl- D-glucopyranoside

with R1, R2, R5, R6 and R6 'as methyl radical, n = 1 and R4 ^' as radical of structure 0-R15 with R15 = 1, 4-diglucosyl.

(£ 2, £ 4, 8E, £ 10) -3,4,9,10-tetramethyl-11- (2,6,6-trimethylcyclohex-1-en-1-yl) undeca- 2,4,8, 10-tetraen-1-yl L-alanyl-L-alaninate

with R1, R2, R5, R6 and R6 ^' as methyl radical, n = 2 and R4 ^' a radical of

Structure ° ^[ 14 with R13 = methyl radical, b = 2 and R 4 = H.

(2E, 4E, 8E, 10E) -3,4,9,10-tetramethyl-11- (2,6,6-trimethylcyclohex-1-en-1-yl) undeca- 2,4,8,10-tetraene -1-yl D-glucopyranoside

with R1, R2, R5, R6 and R6 'as methyl radical, n = 2 and R4' as radical of structure 0-R15, with R15 = glucosyl.

(£ 2, £ 4, £ 8, £ 10) -3,4,9,10-tetramethyl-11 - (2,6,6-trimethylcyclohex-1-en-1-yl) undeca- 2,4,8 , 10-tetraen-1-yl 4-OD-glucopyranosyl-D-glucopyranoside

with R1, R2, R5, R6 and R6 'as methyl radical, n = 2 and R4' as radical of structure 0-R15 with R15 = 1,4-diglucosyl.

The structure (VIII) gives, for example, (0- [glycosyl] retinol) characterized by the structure where R1, R2, R5, R6 and R7 are each methyl radicals and R4 ^' = glycosidically bound sugar, in particular glucose, ie as the radical of the structure 0-R15 with R15 = glucosyl. See also the reference Int J. Vitamin and Nutrition Research, 62, 4, 1992, 298-302 and EP-A2-440078.

- (O-Glycosyl) retinol

(0-1, 4-diglycosyl) retinol

where R1, R2, R5, R6 and R7 are each methyl radicals and R4 ^' as radical of the structure 0-R15 ^• with R15 = 1, 4-di-glucosyl.

From the connection structure (IX) with the respectively preferred radicals R1, R2, R4, R5, R6 and R7, the following preferred compounds (IUPAC names) with the specified structures result:

(1E, £ 3) -2,3-dimethyl-4- (2,6,6-trimethylcyclohex-1-en-1-yl) buta-1, 3-dien-1-yl D-glucopyranoside with R1, R2, R5, R6 and R6 ^' each methyl residues, n = 1 and R4' as the residue of the structure 0- R15 with R15 = glucosyl.

- (1E, £ 3) -2,3-dimethyl-4- (2,6,6-trimethylcyclohex-1-en-1-yl) buta-1, 3-dien-1-yl 4-0-D- glucopyranosyl-D-glucopyranoside

with R1, R2, R5, R6 and R6 ^' each methyl residues, n = 1 and R4' as the residue of the structure O-R15 with R15 = 1, 4-di-glucosyl.

- (1 E, 3E) -2,3-dimethy! -4- (2,6,6-trimethylcyclohex-1-en-1-yl) buta-1, 3-dien-1-yl-L-alanyl- L-alaninate

with R1, R2, R5, R6 and R6 'each methyl radicals, n = 1 and R4' a radical of

From the connection structure (X) with the respectively preferred radicals R1, R2, R4, R5, R6 and R7, the following preferred compounds (IUPAC names) with the specified structures result:

- (4E) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-enal

with R1, R2, R5 and R7 each methyl residues, n = 0 and R4 as carbonyl oxygen.

Λ / - [(4E) -3-methyl-5- (2,6,6-trimethyl-cyclohex-1-en-1-yl) pent-4-en-1-ylidene] -L-alanine

with R1, R2, R5 and R7 each methyl residues, n = 0 and R4 as the residue of the structure

with R11 = methyl and R10 a hydroxy radical.

2 - {[(1E, 4E) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-ylidenes] amino} ethanol

with R1, R2, R5 and R7 each methyl residues, n = 0 and R4 as the residue of the structure N- (CH ₂ ) _X - OH with x = 2.

- 13,14-dihydroretinal with R1, R2, R5, R6 and R7 each methyl radicals, n = 1 and R4 as carbonyl oxygen.

Λ / - [(4 £, 6E, 8E) -3,7-dimethyl-9- (2,6,6-trimethyl-cyclohex-1-en-1-yl) πona-4,6,8-trien-1 ylidene] -L-alanine

with R1, R2, R5, R6 and R7 each methyl residues, n = 1 and R4 as the residue of the structure

with R11 = methyl and R10 a hydroxy radical

- 2 - {[(1E, 4 £, 6 £, 8E) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-4,6,8- trien-1-ylidenes] amino} ethanol

with R1, R2, R5, R6 and R7 each methyl residues, n = 1 and R4 as the residue of the structure N- (CH ₂ ) _x -OH with x = 2..

From the connection structure (XI) the following preferred connections (IUPAC names) with the specified structures result:

(4E) -3-methyl-5- (2,6,6-trimethylcyc! Ohex-1-en-1-yl) pent-4-en-1-yl D-glucopyranoside with R1, R2, R5 and R7 each methyl residues, n = 0 and R4 ^' as the residue of the structure 0-R15 with R15 = glucosyl.

(4E) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-yl-4-0-ß-D-glucopyrano-syl-D -glucopyranoside

with R1, R2, R5 and R7 each methyl residues, n = 0 and R4 'as the rest of the structure structure 0-R15 with R15 = 1, 4-di-glucosyl.

- (4 £ F) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-yl L-alanyl-L-alaninate

with R1, R2, R5 and R7 each methyl residues, n = 0 and R4 'as residue of the structure a residue O NH O Rι_ ra of structure R13 ^{"" b} with R13 = methyl residue, b = 2 and R14 = H.

0- (L-alanyl-L-alanyl) -13,14-dihydroretinol with R1, R2, R5, R6 and R7 each methyl residues, n = 1 and R4 'a residue of

with R13 = methyl radical, b = 2 and R14 = H.

The following preferred compounds (IUPAC names) with the specified structures result from the compound structure (XII):

- 7,8,9,10,11, 12,13, 14-octahydroretinal

with R1, R2, R5, R6 and R7 each methyl radicals and R4 as carbonyl oxygen.

Λ / - [3,7-dimethyl-9- (2,6,6-trimethyl-cyclohex-1-en-1-yl) nonylidene] -L-alanine

with R1, R2, R5, R6 and R7 each methyl radicals and R4 as the radical of the structure R11 ¹⁰ with R1 = methyl and R10 a hydroxyl radical.

2 - {[(1 U) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nonylidene] amino} ethanol with R1, R2, R5, R6 and R7 each methyl residues and R4 as residue of the structure N- (CH ₂ ) _X - OH with x = 2.

From the connection structure (XIII), the following preferred connections (IUPAC-Nameη) with the specified structures result:

0- (L-alanyi-L-alanyl) -7,8,9, 10,11, 12,13,14-octahydroretinol

with R1, R2, R5, R6 and R7 each methyl radicals and R4 'a radical of

with R13 = methyl radical, b = 2 and R14 = H.

From the connection structure (XIV), the following preferred connections (IUPAC names) with the specified structures result:

- 11,12-dihydroretinal

with R1, R2, R5, R6 and R7 each methyl radicals and R4 as carbonyl oxygen.

- Λ / - [(£ 2, £ 6 f _> 8E) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-2,6,8-triene -1- ylidenes] -L-alanine with R1, R2, R5, R6 and R7 each methyl and R4 as the rest of the structure

with R11 = methyl and R10 a hydroxy radical.

- 2 - {[(1 £, 2E ₍ 6E, 8E) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-2,6,8-triene -1- ylidenes] amino} ethanol

with R1, R2, R5, R6 and R7 each methyl residues and R4 as residue of the structure N- (CH ₂ ) _X - OH with x = 2.

The connection structure (XV) results in the following preferred connection (IUPAC name) with the specified structure:

- 0- (L-alanyl-L-alanyl) -11, 12-dihydroretinol

with R1, R2, R5, R6 and R7 each methyl and R4 ^' as the rest of the

The following preferred compounds (IUPAC names) with the structures given result from the compound structure (XVI): - (8E) -10-methyl-7,10-dihydroretinal with R1, R2, R5, R6, R7 and R8 each methyl radicals and R4 as carbonyl oxygen.

- IV - [(£ 2, £ 4, 7E) -3,6,7-trimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-2,4,7-triene -1- ylidenes] -L-alanines

with R1, R2, R5, R6, R7 and R8 each methyl and R4 as the rest of the structure

R11 = methyl and R10 a hydroxy radical

- 2 - {[(1 £, 2E, 4 £, 7 £) -3,6,7-trimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-2,4 , 7-trien-1-ylidenes] amino} ethanol

with R 1, R2, R5, R6, R7 and R 8 each with methyl residues and R4 as the residue of the structure N- (CH ₂ ) _x -OH with x = 2.

From the connection structure (XVII), the following preferred connection (IUPAC name) with the specified structure results:

- (8 pounds) -O- (L-alanyl-L-alanyl) -10-methyl-7,10-dihydroretinol

nit R1, R2, R5, R6, R7 and R8 each methyl and R4 'as the rest of the

with R13 = methyl radical, b = 2 and R14 = H.

From the connection structure (XVIII), the following preferred connections (IUPAC names) with the specified structures result:

- (5E, 7E) -6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-5,7-dien-2-one

with R1, R2, R5, R6 and R7 each methyl radicals and R4 as carbonyl oxygen.

- / V - [(£ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-ylidenes] - L-alanine

with R1. , R2, R5, R6 and R7 each represent methyl radicals and R4 as the radical of the structure

with R11 = methyl and R10 a hydroxy radical

2 - {[(1E, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-ylidenes ] amino} ethanol

with R1, R2, R5, R6 and R7 each methyl residues and R4 as residue of the structure N- (CH ₂ ) _X QH with x = 2. The following preferred connections (IUPAC names) with the specified structures result from the connection structure (XIX):

(£ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-yl D-glucopyranoside

with R1, R2, R5, R6 and R7 each methyl residues and R4 as the rest of the structure structure O-R15 with R15 = glucosyl.

- (4 £, 6E) -1, 5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-yl 4-O-ß- D-D-glucopyranosyl-D-glucopyranoside

with R1, R2, R5, R6 and R7 each methyl residues and R4 as the rest of the structure structure O-R15 with R15 = 1, 4-di-glucosyl.

- (4E, 6 lbs) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-yl L-alanyl-L- alaninates

with R1, R2, R5, R6 and R7 each methyl and R4 'as the rest of the

with R13 = methyl radical, b = 2 and R14 = H.

All preferred compounds of each compound class I to XIX have already been synthesized and are therefore freely available. The individual manufacturing instructions are given as examples for some representatives. The person skilled in the art can, from his well-known basic understanding of chemistry, apply these manufacturing instructions for all of the compounds disclosed by the structures and compound residues indicated, but can also modify them individually, if necessary, without having any inventive step. Individual other compounds which result in particular from a change in the double bonds from the example compounds, in particular by partial hydrogenation, are of course to be understood in the same way as the compound according to the invention.

The following literature citations for the synthesis of the substances may be mentioned as examples of compounds which are mentioned under structures I to XIX: (VIII): Int. J. Vitamin and Nutrition Research, 62, 4, 1992, 298-302 EP 440078 A2 (XII): Tetrahedron, 52, 47, 1996, 14891-14904 (XVIII): EP 1 199303 A1 JP 10330356 A2 EP 881204 A1 (XIX ): WO 9105754 A2

These compounds according to the invention, the compounds explicitly mentioned and shown being only examples of the respective compounds (I) to (XIX), have proven useful as agents for use on the skin or hair. The compounds lead to an increase in melanin synthesis and are preferably to be 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 even textiles, for example bandages or bath textiles, in order to ensure continuous tanning , favored as an inventive agent. It is advantageous in the case of bandages equipped with the compounds according to the invention that during the wearing time of the bandage, the skin underneath experiences the same brown color as the uncovered skin

It has been shown through intensive research that the compounds according to the invention in topical compositions, in particular cosmetic or dermatological preparations, lead to the induction of pigmentation of the skin. Melanogenesis. is increased, there is more melanin in the skin, the skin becomes brown and the skin's own protection is increased physiologically. 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. To demonstrate the effectiveness of the 4-fold substituted cyclohexene compounds according to the invention, effectiveness tests were carried out in each case. The test for the compound 6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-3,5-dien-2-one is shown as an example. 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 C14 tyrosine incorporation). This results in melanogenesis, i.e. the process of melanin synthesis rises to 157% and 127%, respectively, when the melanocytes are present in the presence of 6-methyl-8- (2,6,6-trimethylcyclohex-1- en-1-yl) octa-3,5-diene Cultivated 2-on (n = 3).

The compounds according to the invention are distinguished, inter alia, by the fact that they induce the formation of skin-specific pigments in the skin, for example after topical application, which. Increase melanin synthesis and in this way produce an increased tan of the skin. They are harmless to health, non-irritating and easy to handle, 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, in particular with regard to homeostasis, the avoidance of Skin aging 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 look faster and better, ^{■ make} the tanning and hair coloring last longer, ^{■ work} better than moisturizing preparations,

^■ better promote skin smoothing,

^■ are characterized by better care effects,

^{■ have} better sensory properties, such as, for example, the 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 4-times substituted cyclohexene compounds is between 0.0001 and 30% by weight, advantageously between 0.01 and 10% by weight, particularly advantageously between 0.02 and 2% by weight, in each case related to a on the total weight of the agents, 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.

For the purposes of the present invention, it is also possible and advantageous 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, perfumes, dyes, emulsifiers, additional active ingredients such as vitamins or proteins, light stabilizers, stabilizers, insect repellents, alcohol, water, salts, antimicrobial, proteolytic or keratolytically active substances, 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, random-Me-beta, gamma-cyclodextrin) , where, according to the chemical properties known to the person skilled in the art, alpha-, beta- or gamma-cyclodextrins are used as encapsulation material. 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 (for example water) are in equilibrium between the specific guest-cyclodextrin complex and the dissociated form, cyclodextrin and. Guest to a certain extent be separated. can. 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 drugs in 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 U bichinon Q10, creatine, creatinine, camitin, biotin, isoflavone, cardiolipin, lipoic acid, 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, camitin, 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 liquorice, licochalcone, in particular licochalcone A, silymarin, silyphos, dexpanthenol, inhibitors of prostaglandin metabolism, in particular cyclooxygenase and leukotriene metabolism, in particular 5-lipoxyenase, but also 5- Lipoxvase 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 the liquorice. - Kojisä-u-re, hydroehinone, arbutin, 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), lipofuscins, nucleic acid oligonucleotides, purines and pyrimidines, NO-releasing substances), whether with or without the influence of UV light.

Cosmetic and dermatological preparations in the form of a sunscreen are particularly preferred. Advantageously, these can additionally include at least one additional U VA filter and / or at least one additional UVB filter and / or contain 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 was 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.).

According to the invention, the cosmetic and dermatological preparations can contain cosmetic auxiliaries as are usually used in such preparations, e.g. Preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation such as alcohols, Polyols, polymers, foam stabilizers, electrolytes, organic solvents, silicone derivatives or moisturizers.

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

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. is available under the name Fucogel®1000 from the company SOLABIA SA. 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 (for example glycine, histidine, tyrosine, phenylalanine, tryptophan) and their derivatives (in particular N-acetyl-tyrosine, N-acetyl-phenylalanine), imidazoles (for example 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, β-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, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilaurylthiodipropionate, distearylthio-dipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) - as well as sulfoxirnine compounds (e.g. Buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathione sulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-unolenic acid, ^' linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A-palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, Nordihydroguajak resin acid, Nordihydroguajaretsäure, trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. ZnO, ZnS0) selenium and its derivatives (e.g. selenomethionine), stilbene and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active ingredients.

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 to 10% by weight, based on the total weight of the composition, preferably 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 use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to 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 waxes Oils such as riglycerides of C apric acid or C aprylic acid, preferably over castor oil; Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with alcohols with a low C number, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids with a low C number 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 carbon atoms, from the group of esters of 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 paimitat, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethyl-2-ethylhexyl palmitate Hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate as well as synthetic, semi-synthetic and natural mixtures of such esters, eg Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of the 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, 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, e.g. 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 can also be advantageous if necessary be waxes, for example cetyl palmitate, to be used as the sole lipid component of the oil phase.

The oil phase is advantageously selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Mixtures of C _12-15 alkyl benzoate and 2-ethylhexyl isostate, mixtures of C _{12 5} alkyl benzoate and isotridecyl isononanoate and mixtures of C _12-15 alkyl benzoate, 2-ethyl hexyl isostearate and isotridecyl isononanoate are particularly advantageous.

Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

The oil phase can advantageously also contain 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 advantageously advantageously contains - alcohols, diols or polyols having a low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or - monobutyl ether, diethylene glycol monomethyl or monoethyl ether and 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 Silicon dioxide, aluminum silicates, polysaccharides or 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 , 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, 1 NCI: octyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl 4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamate acid (l-methoxycinnamate) 4-methoxycinnamate, 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 0 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 commercial in form! available oily or aqueous predispersions are used. 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”), with, for example, a hydrophilic, amphiphilic or hydrophobic character being formed or retained. This surface treatment can consist in the pigments being coated with a thin hydrophilic by methods known per se and / or hydrophobic inorganic and / or organic layer The various surface coatings can also contain water in the sense of the present invention.

Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al ₂ 0 ₃ ), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: Alu ina, CAS no .: 1333-84-2), sodium hexametaphosphate ( NaP0 ₃ ) β, sodium metaphosphate (NaP0 ₃ ) _n , silicon dioxide (Si0 ₂ ) (also: Siiica, CAS No .: 7631-86- 9), or iron oxide (Fe ₂ 0 ₃ ). These inorganic surface coatings can occur 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 dibenzoyl methane derivatives, in particular 4 ~ (tert-butyl) -4'-methoxydibenzoylrnethan (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, in particular 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 is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan AP; • 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 Hydro 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 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also called benzene-1, 4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) is called 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 4- (2-oxo-3-bomylidene) - methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and their 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-Fi 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-Chemicals GmbH; Diethylhexylbutylamidotriazon (INCI: Diethylhexylbutamidotriazone), which is available under the trade name UVASORB HEB from Sigma 3V; ^4,4, 4 "- (1, 3,5-triazine-2,4,6-triyltriimino) -tris-benzoösäure-tris (2-ethylhexyl), 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 For the purposes of the present invention, 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol), which is is available under the trade name Tinosorb® M from CIBA-Chemicals 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 - [( trimethylslyl) 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. B .:

^■ 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) carnpher, 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

^■ and UV filters bound to polymers.

^■ 3- (4- (2,2-bis ethoxycarbonylvinyl) phenoxy) ρropenyl) - methoxysiloxan / dimethylsiloxane - copolymer which is obtainable for example from Hoffmann La Roche 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-bomylid.enme-. Thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) 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 u nder 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, -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- hexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, in each case individually or in any combination with one another.

According to the invention, benzoxazole derivatives such as, in particular, 2,4-bis- [5-1 (dimethylpropyl) benzoxazo) -2-yl- (4-phenyl) -irino] -6- (2-ethyl! Hexyl) - are also particularly advantageous. imino-1, 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'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester or also aminobenzophenoπ, 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 cosmetic To provide 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 generated or natural ultraviolet rays - for example in order to increase natural tanning or to achieve a 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, picking 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 aging, - to intensify the hair color, - to prevent the graying of the Hair and / or to protect the hair from fading due to sunlight, - as shower gel, shampoo, conditioner, hair care treatment, hair conditioner, hair tonic, hair spray, make-up, skin protection, face, cleaning, sun protection: -, nutrient, day - or night cream, gel, or lotion or cleansing preparation.

The compounds according to the invention can likewise be a constituent of a polymer matrix, a skin and / or wound dressing, a plaster, a cloth or pad, a spray or on or in textiles, such as bandages or bath textiles.

The incorporation of the compounds into polymer matrices, such as, for example, polyurethane matrices, is thus possible without 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 applicator 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, parts and percentages are based on the weight and the total amount or on the total weight of the preparations. Examples 1. PIT emulsions

Butylene Glycol Dlcaprylate / Dicaprate 4.00 5.00 Shea Butter 0.50 Butylene Glycol 6.00 Octoxyglycerin 3.00 Glycerin 5.00 3-Methyl-5- (2,6,6-trimethylcyclohex-1 -en- 1 ■ 0.50 1.00 yl) pent-4-en-1-yl D-glucopyranoside 6-methyl-8- (2,6,6-trirnethylcyclohex-1-en-1- 0.2 0.1 yl ) octa-3,5-dien-2-one _v Trisodium EDTA 0.20 0.20 Preservative qsqs ethanol 3.00 Perfume qsqs water ad. 100 ad. 100

6. Hvdrodispersions

10. Speech formulation

14. Pearlescent conditioner shampoo

15. Clear conditioner shampoo

16. Clear light shampoo with volume effect

Claims

claims

1. Means for use on the skin and / or hair, characterized in that the agent has one or more 4-times substituted cyclohexene compounds of the structure

contains, wherein the radicals R1, R2 and / or R5 are selected from the group hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hydroymethyl, hydroxyethyl, hydroxypropyl, hydroxy and / or alkyl carboxylate with alkyl radicals selected from methyl, ethyl, propyl or butyl, R3 is selected from the group of the compound residues of the structure (I) to (XIX) with (I)

(II)

(III)

(IV)

(V) (VI)

(VII)

(VIII)

(IX)

(X)

(XI)

(XII)

(XIII)

(XIV)

(XV)

(XVI)

(XVII)

(XVIII)

(XIX)

R6, R6 ', R7 and / or R8 are selected from the group hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hydroymethyl, hydroxyethyl, hydroxypropyl, hydroxy and / or alkyl carboxylate, the alkyl radical being 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- (CH ₂ ) _x -OH, N- (CHR9) _X -CH20H, N- (CHR9) _x - OH, N- (CH ₂ ) _X - OCOMe, where x = 1 - 10, N-OH, 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-hydroxy-benzyl, 1-hydroxyethyl, mercaptomethyl, 2-amino-2-oxoethyl, carboxymethyl, carboxyethyl, 4-aminobutyl, 3 - {[amino (imino ) methyl] arnino} 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-pyrrolidine-1,2-diyl-, hydroxyethyl- or 2-mercaptoethyl-, R10 is selected from - hydroxy- (-OH), peptide-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

[N ^H with b = 1 - 6, or 2 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

O NH! O Rl4 ra R13 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-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-imidazole-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. Means according to claim 1 for increasing skin tanning and / or melanin synthesis in the skin and / or hair.

3. Composition 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. Means according to one of the preceding claims, characterized in that - R1, R2 _; R5, R6, R7 and / or R8 are methyl radicals, - R4 is carbonyl oxygen and - R3 is selected from the compound radicals o (I) with n = 1 or 2 and R6 ^' = hydrogen or methyl o (II) with R4 = carbonyl oxygen, o (III) with R ₄ ^' = O-glycosyl, o (IV) with R4 = carbonyl oxygen, o (V) with R ^' = O-glycosyl, o (VI) with n = 1 or 2 and R6 ^' = hydrogen or methyl, o (VII) with n = 1, 2 or 3 and R6 ^' = hydrogen or methyl, R ^'' = O-glycosyl, o (VIII) with R ₄ ' = O-glycosyl, o (IX) with n = 1, 2 or 3 and R6 '= hydrogen or methyl, F = O-glycosyl, o (X) with n = 0, 1, 2 or 3 o (Xl) n = 0, 1, 2 or 3 and R ₄ '= ^: O-glycosyl, o (XII), o (XIII) with R ₄ ' = O-glycosyl, o (XIV), o (XV) and R _t ^' = O-glycosyl, o (XVI), o (XVII) FV "O-glycosyl, o (XVIII) and / or o (XIX) R ₄ '= O-glycosyl

6. Agent according to one of the preceding claims, characterized in that one or more 4-times substituted cyclohexene compounds are selected from (I) (3E) -3-methyl-4- (2,6,6-trimethylcyclohex-1- en-1-yl) but-3-en-2-one, Λ / - [(2E) -1, 2-dimethyl-3- (2,6,6-trimethylcyclohex-1-en-1-yl) prop -2-en-1-ylidenes] -L-alanine, (3E, 5E, 7 £) -3,6,7-trimethyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-3,5,7-trien-2-one, Λ / - [(2E, 4 £, 6E) -1, 2,5,6-tetramethyl-7- (2,6,6-trimethylcyclohex-1 - en- 1-yl) hepta-2,4,6-trien-1-ylidenes] -L-alanine, (3E) -4- (2,6,6-trimethylcyclohex-1-en-1-yl) but- 3-en-2-one, (2E, 3E) -4- (2 ₎ 6,6-trimethylcyclohex-1-en-1-yl) but-3-en-2-one oxime, (II) (£ 3 , £ 5) -6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yi) octa-3,5-dien-2-one, Λ / - [(2E, 4E) - 1, 5-dimethyl-7- (2, δ, 6-trimethylcyclohex - 1-en-1-yl) hepta-2,4-dien-1-ylidenes] -L-alanine, N - [(2 £, 4E) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-ylidenes] -L-alanyl-L-alanine, 2 - {[(1U, £ 2, £ 4) -1,5-dimethyl-7- (2.6 , 6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-ylidenes] amino} ethanol, (2E, 3 £, 5E) -6-methyl-8- (2,6,6 -trimethylcyclohex-1-en-1-yl) octa-3,5-dien-2-one oxime, 2 - {[(1 E, 2 £, 4 £) -1, 5-dimethyl-7- (2, 6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-y! Idene] amino} ethyl acetate,. (III) (2 £, 4E) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-yl-D-gluco pyranosjd, (2E, £ 4) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1-yl 4-O-ß -D-glucopyranosyl-D-glucopyranoside, (2E.4E) - 1, 5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4-dien-1- yl L-alanyl- L- alaninate, (IV) 3-Methyl-8- (2 _L 6,6-trimethyl-cyclohexyl-1-enyl) octa-3,5,7-trien-2-one, N- [(2 £, 4 £, 6E ) -1, 5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-triene-1-ylidenes] -L-alanine, 2 - {[ (1 U, 2 lbs, 4E, 6 lbs) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-triene-1- ylidene] amino} ethanol, (2E, 3E, 5E, 7E) -6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-3,5,7-triene-2 -one oxime, 2 - {[(1 £, 2E, 4 £, 6E) -1, 5-dimethyl-7- (2,6,6-trimethylcyclohex-1 -en- 1 -yl) hepta-2,4 , 6-trien-1-ylidenes] amino} ethyl acetate,

(V) (2E, 4E, 6E) -1, 5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-trien-1-yl D -glucopyranqsid, (2 £, 4 £, 6E) -1, 5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-2,4,6-triene-1- yl 4-O-β-D-glucopyranosyl-D-glucopyranoside, (£ 2, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl ) hepta-2,4,6-trien-1-yl L-alanyl-L-alaninate,

(VI) (2E, 4E) -3-methyl-5- (2,6,6-trimethyl-cyclohexyl-1-enyl) penta-2,4-dienal, N- [(2E, 4E) -3, 4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-dien-1-ylidene] -L-alanine, 2 - {[(£ 1, £ 2 , 4E) -3,4-dimethyl-5- (2,6,6-trimethylcyciohex-1-en-1-yl) penta-2,4-dien-1-ylidenes] amino} ethanol, (2 £, 4 £, 6E, £ 8, £ 10) -3,4,9,10-tetramethyl-11- (2,6,6-trimethylcyclohex-1-en-1-yl) undeca-2,4,6,8, 10- pentaenal, A / - [(2E, 4 £, 6E, 8E, 10E) -3,4,9,10-tetramethyl-11 - (2,6,6-trimethylcyclohex-1-en-1-yl) undeca-2,4,6,8,10-pentaen-1-y! idene] -L-alanine, 2- {[(1 E, £ 2, £ 4, £ 6, £ 8, £ 10) -3 , 4,9,10-tetramethyl-11 - (2,6,6-trimethylcyclohex-1-en-1-yl) undeca-2,4,6,8,10-pentaen-1-ylidenes] amino} ethanol,

(VII) l (2E, 4E) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) penta-2,4-dien-1-y) L-alanyl -L-alaninate, (2E, 4E) -3,4-dimethyl-5- (2,6,6-trimethylcyclohex-1 -en-1 - y!) Penta-2,4-dien-1-yl-D -glucopyranoside _r - (- 2E, 4E) -3,4-dimethyl-5-C2,6,6 --- trimethylcyclohex-1 -en-1 -yl) penta-2,4-dien-1 -yl 4 -OD-glucopyranosyl-D-glucopyranoside, (2 £, 4E, 8E, 10E) -3,4,9,10-tetramethyl-11 - (2,6,6-trimethylcyclohex-1-en-1-yl) undeca -2,4,8,10-tetraen-1-yl L-alanyl-L-alaninate, (2E, 4E, £ 8, £ 10) -3,4,9, 10-tetramethyl-1 - (2.6 , 6-trimethylcyclohex-1-en-1-yl) undeca-2,4,8,10-tetraen-1-yl D-glucopyranoside, (2E, 4 £, 8E, 10E) -3,4,9,10 tetramethyl-11- (2,6,6-trimethylcyclohex-1-en-1-yl) undeca-2,4,8,10-tetraen-1-yl 4-OD-glucopyranosyl-D-glucopyranoside,

(VIII) 0- [glycosyl] retinol, (0-1, 4-diglycosyl) retinol,

(IX) (1E, 3E) -2,3-dimethyl-4- (2,6,6-trimethylcyclohex-1-en.-1-yl) buta-1, 3-dien-1-yl D-glucopyranoside, (1E, 3E) -2,3-dimethyl-4- (2,6,6-trimethylcyclohex-1-en-1-yl) buta-1, 3-dien-1-yl 4-0-D-glucopyranosyl -D-glucopyranoside, (1 £, 3E) -2.3- dimethyl-4- (2,6,6-trimethylcyclohex-1-en-1-yl) buta-1, 3-dien-1-yl-L-alanyl-L-alaninate,

(X) (4 £) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-enal, Λ / - [(4 £) -3-methyl- 5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-ylidenes] -L-alaπin, 2- {[(1 £, 4E) -3-methyl-5 - (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-ylidenes] amino} ethanol, 13,14-dihydroretinal, / V - [(£ 4, 6E, £ 8 ) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-4,6,8-trien-1-ylidenes] -L-alanine, 2- {[ (1 £, 4E, 6E, 8 £) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-4,6,8-trien-1-ylidenes ] amino} ethanol,

(XI) (4 £) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-yl D-glucopyranoside, (4 £) -3 -methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-yl-4-0-ß.-D-glucopyrano-syl-D-glucopyranoside, ( 4 pounds) -3-methyl-5- (2,6,6-trimethylcyclohex-1-en-1-yl) pent-4-en-1-yl L-alanyl-L-alaninate, 0- (L-alanyl -L- alanyl) -13, 14-dihydroretinol,

(XII) 7,8,9,10,11, 12,13,14-octahydroretinal, A / - [3,7-dimethyl-9- (2,6,6-trimethylcyciohex-1-en-1-yl) nonylidene] -L-alanine, 2 - {[(1 E) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nonylidene] amino} ethanol,

(XIII) O- (L-alanyl-L-alanyl) -7,8,9,10,11, 12,13,14-octahydroretinol,

(XIV) 11,12-dihydroretinal, A - [(£ 2, £ 6, 8E) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1-en-1-yl) nona-2 , 6,8-trien-1-ylidenes] -L-alanine, 2 - {[(1E, 2 £, 6E, 8E) -3,7-dimethyl-9- (2,6,6-trimethylcyclohex-1- en-1-yl) nona-2,6,8-trien-1-ylidene] amino} ethanol,

(XV) 0- (L-alanyl-L-alanyl) -11, 12-dihydroretinol,

(XVI) (8 £) -10-methyl-7,10-dihydroretinal, V - [(2E, 4E, 7 £) -3,6,7-trimethyl-9- (2,6,6-trimethylcyclohex-1 -en- -y!) nona-2,4,7-trien-t-yiidenej-L-alanine, ^' 2- {[(1E, 2 £, 4E, 7E) -3,6,7-trimethyl-9 - (2,6,6-trimethylcyclohex-1-en-1-yl) nona- 2,4,7-trien-1-ylidenes] amino} ethanol,

(XVII) (8 £) -O- (L-alanyl-L-alanyl) -10-methyl-7,10-dihydroretinol,

(XVIII) (£ 5, £ 7) -6-methyl-8- (2,6,6-trimethylcyclohex-1-en-1-yl) octa-5,7-dien-2-one, Λ - [( 4E, 6 pounds) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-ylidenes] -L-alanine, 2- {[(1 U, £ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-diene-1-yiidenes] amino} ethanol,

(XIX) (£ 4, 6E) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-yl D-glucopyranoside, (£ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-yl 4-O-ß- D-glucopyranosyl-D-glucopyranoside and / or (£ 4, £ 6) -1,5-dimethyl-7- (2,6,6-trimethylcyclohex-1-en-1-yl) hepta-4,6-dien-1-yl L-alanyl-L- alaninate

7. Agent according to one of the preceding claims, characterized in that the content of tetrasubstituted cyclohexene compounds between 0.0001 and 30% by weight, in particular between 0.01 and 10% by weight, particularly advantageously between 0.02 and 2% by weight, based on the total weight of the agent, preferably the cosmetic preparation.

8. Agent according to one of the preceding claims, characterized in that the 4-times substituted cyclohexene compounds are contained in encapsulated form.

9. Means according to claim 8, characterized in that the encapsulation material consists of collagen matrices, cyclic oligosaccharides, alpha-, beta-, HP-beta, random-me-beta or gamma-cyclodextrin, cellulose, gelatin, wax matrices or liposomes ,

10. Composition according to one of claims 1 to 9, characterized in that additionally at least one UVA filter and / or at least one UVB filter and / or at least one inorganic pigment, preferably an inorganic micropigment, is contained

11. A composition according to any one of the preceding claims, characterized in that additionally antioxidants -with a proportion of 0.00 to 1 to 30% by weight ^•, -. More 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 keratolytic effective substances, medicines or other common components of a cosmetic or dermatological formulation are contained.

13. Preparation according to claim 12, characterized in that glycerin is added as a moisturizer in the range of 0.05-30% by weight, particularly preferably 1-10% 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 positively influence 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 , Camitin, 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 on dry skin, especially vitamin C, biotin , Camitin, creatine, propionic acid, green tea extracts, eucalyptus oil, urea and mineral salts, in particular NaCI, marine minerals and osmolytes, - active ingredients for the relief and / or positive influence on irritant skin conditions, in particular sericosides, various extracts of licorice, licochalcone, in particular L icochalcone A, S ilymarin, Silyphos,. Dexpanthenol-- - inhibitors of prostaglandin metabolism, especially cyclooxygenase and leukotriene metabolism, especially 5-lipoxyenase or 5-lipoxvgenase inhibitor protein, FLAP, - pigmentation modulators, especially tyrosine sulfate, dioic acid (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 substances, which 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. Use of the agent according to one of claims 1 to 14 in or as an aqueous system and / or surfactant preparation for cleaning and / or care of the skin and / or hair.

16. Use of a preparation according to one of claims 3. up to 14 as a multiple emulsion, microemulsion, Pickering emulsion or sprayable emulsion.

17. Use of a preparation according to any one of claims 3 to 14 as a presun, a sunscreen or an aftersun formulation.

18. Use of the agent according to one of claims 1 to 14 for topical use on skin and / or hair.

19. Use of the agent according to one of claims 1 to 14 for tanning the skin.

20. Use of the agent according to one of claims 1 to 14 for skin care.

21. Use of the agent according to one of claims 1 to 14 for protecting the skin and / or the hair from damaging UV rays.

22. Use of the agent according to one of claims 1 to 14 to increase melanin synthesis in the skin.

23. Use of the agent according to one of claims 1 to 14 for extending the brown color of the skin.

24. Use of the agent according to one of claims 1 to .14 for protection: the skin against oxidative stress.

25. Use of the agent according to one of claims 1 to 14 for protection: the skin against chronological and light-related skin aging.

26. Use of the agent according to one of claims 1 to 14 for intensifying the hair color.

27. Use of the agent according to one of claims 1 to 14 to prevent graying of the hair and / or to protect the hair from fading due to sunlight.

28. Use of the preparation according to one of claims 3 to 14 as a shower gel, shampoo, conditioner, hair care treatment, hair rinse, hair tonic, hair spray, makeup, skin protection, face, cleaning, sun protection, nutrient, day or night cream, gel, or lotion or cleansing preparation.