DE102005055577A1 - flavones - Google Patents

Abstract

The present invention relates to new flavones, characterized in that it is a 7,8-dihydroxyflavone derivative according to formula Ia or Ib or a salt thereof, DOLLAR F1 preparations and mixtures containing flavones, their preparation and use.

Description

The The present invention relates to novel flavones, preparations and mixtures containing flavones, their preparation and use.

One Field of application of the compounds according to the invention is for example the cosmetics. The task of caring cosmetics is it, if possible to get the impression of a youthful skin. In principle, stand different ways open to reach this path. So already can existing damage to the Skin, like irregular pigmentation or wrinkling, counterbalanced by covering powders or creams become. Another approach is to protect the skin from environmental factors protect, which leads to permanent damage and thus lead to aging of the skin. So the idea is to intervene preventively and thereby the aging process delay. An example is this the ones already mentioned UV filters, which by absorption of certain wavelength ranges a damage Avoid or at least reduce the skin. While with UV filters the damaging Event, the ultraviolet radiation, shielded from the skin, one tries on another way, the natural ones Defensive or repair mechanisms of the skin against the harmful Support event. After all one follows as a further starting point the with increasing age weakening oneself To balance defensive functions of the skin against damaging influences by substances from the outside supplied which replace this diminishing defense or repair function can. For example, the skin possesses the ability to remove radicals by external or internal stress factors are generated to intercept. This ability weakens decreases with age, thereby increasing the aging process accelerated with age.

A more or less pronounced suntan The skin is in modern society as attractive and as Expression of dynamism and sportiness. In addition to this desired Effect of the sun on the skin occur a number of unwanted Side effects, such as sunburn or premature aging and wrinkling. Of particular importance is the wavelength range from 280 to 400 nm. This range includes UV-B rays with a wavelength between 280 and 320 nm, which results in the formation of a sun erythema play a crucial role, as does UV-A rays, with one wavelength between 320 and 400 nm, which make the skin tan but also age the trigger an erythematous Favor reaction or increase that response in certain people or even phototoxic or photoallergic and irritative reactions trigger can.

skin damage are caused not only by sunlight, but also by other external influences, like Cold or Warmth. Furthermore, the skin is subject to natural aging, causing wrinkles arise and the elasticity of the skin subsides.

A There is further difficulty in the production of cosmetics in that active ingredients incorporated in cosmetic preparations are often not stable and in the preparation damaged can be. The damages can for example, by a reaction with atmospheric oxygen or by the absorption of UV rays are caused. The molecules thus damaged can by their structural change e.g. change their color and / or lose their effectiveness.

One well-known way to treat the problems described consists in Addition of antioxidants to the preparations.

Loud CD Römpp Chemistry Lexicon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 is concerned in the case of antioxidants, compounds that are undesirable, due to oxygen effects et al oxidative processes caused changes in the to be protected Inhibit or prevent substances. Areas of use are e.g. in plastics and rubber for protection against aging; in fats for protection Rancidity, in oils, Livestock feed, petrol and jet fuels for protection against gumming, in transformer and turbine oil against Mud formation, in flavorings against odor deterioration. When Antioxidants are effective i.a. by sterically hindering groups substituted phenols, hydroquinones, catechols and aromatics. Amines and their metal complexes. The effect of antioxidants, according to Römpp is usually that they as radical scavengers for the act in the autoxidation occurring free radicals.

Among the phenols with an antioxidant effect, the polyphenols, which are sometimes present as natural substances, are of particular interest for applications in the pharmaceutical, cosmetic or food sector. For example, the flavonoids or bioflavonoids, which are mainly known as plant dyes, frequently have an antioxidant potential. Effects of the substitution pattern of mono- and dihydoxy flavones are dealt with by K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108. It is observed there that dihydroxyflavones having an OH group adjacent to the keto function or OH groups in the 3'4 'or 6,7 or 7,8 position have antioxidant properties, while other mono- and dihydroxyflavones have in part no antioxidant properties exhibit.

Frequently becomes Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) mentioned as a particularly effective antioxidant (e.g., C. A. Rice-Evans, N.J. Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A.E.M.F. Soffers, I.M.C.M. Rietjens; Free Radical Biology & Medicine 2001, 31 (7), 869-881 the pH dependence the antioxidant effect of Hydoxyflavones. Over the entire pH range Quercetin shows the highest activity of the examined structures.

In WO 02/00214 for the use of certain flavone derivatives for the production of oral drugs for systemic treatment and prophylaxis of UV-induced dermatoses, in particular polymorphic photodermatoses and their subforms and / or unwanted long-term effects of UV irradiation, especially the photoaging, described. Preferred flavone derivatives are especially natural occurring bioflavonoids, such as rutin, naringin, naringenin, hesperidin, Hesperetin, taxifolin, etc. as well as derivatives thereof, such as troxerutin or monoxerutin.

In International patent application WO 00/61095 describes mixtures of polyphenols with vitamins. These mixtures are suitable for use in cosmetic or dermatological compositions and are optimized for trapping free radicals such as hydroxy radicals or peroxides. Particularly preferred is the combination of troxerutin with α-tocopherol succinate and ascorbyl palmitate.

Lots However, these polyphenols are in cosmetically acceptable support materials not soluble or in preparations not storage stable.

It Therefore, there is still a need for skin-friendly antioxidants that are also suitable for use in skin care preparations and to work in a suitable manner in cosmetic preparations to let.

task The invention is therefore to compounds available which applied in cosmetic preparations has a protective effect against oxidative stress on body cells exercise and / or can counteract aging of the skin.

Surprised was found that certain flavones are excellent as Antioxidants on the human skin are suitable.

A first subject of the present invention are therefore compounds of formula I, which are characterized in that it is a 7,8-dihydroxyflavone derivative according to formula Ia or Ib or a salt thereof

Also mixtures which are characterized in that they have at least 2 compounds selected from the compounds according to formula Ia, Ib or Ic or their salts

Contain, are the subject of the present invention.

One Another object of the present invention is accordingly the preferred use of the compounds of the invention is a preparation with antioxidant properties, containing at least one compound of formula I, selected from the compounds according to formula Ia, Ib or Ic, as described above, or an above-described Mixture.

at the salts are preferably those with counterions, which the incorporation of the compounds of formula I in preparations do not hinder. For example, it is preferable when it comes to Alkali metal, alkaline earth metal or ammonium salts. Especially it is preferred according to the invention if the salts are sodium, potassium or ammonium salts, especially triethanolammonium salts.

advantages the compounds of the invention or compositions are in particular the antioxidant Effect and good skin tolerance. additionally the compounds described here are only weakly colored and to lead so not or only slightly to discoloration of the preparations. From Advantage is in particular the special action profile of the invention used Compounds, which are characterized by stability of the compounds in the preparations and antioxidant activity in or on the skin.

Surprised In particular, this effect is due to the in the compounds of the formula I functional groups none or only one very weak antioxidant effect is expected. It is believed that the reason for the activity the compounds of the invention or mixtures on or in the skin, the cleavage of at least one Part of the sulfate groups by skin's own sulfatases.

One The subject of the present invention is due to these properties the use of the compounds according to formula I, as indicated above, as an antioxidant or for the preparation of a preparation with antioxidant properties or for the preparation of preparations, the one protective Exercise and / or against oxidative stress on body cells counteract aging of the skin or to reduce the consequences can contribute to skin aging.

The preparations are usually either a topical application preparations, for example cosmetic, pharmaceutical or dermatological formulations, or foods or dietary supplements. The preparations in this case contain a cosmetically, pharmaceutically or dermatologically or food-suitable carrier and, depending on the desired profile of properties, optionally further suitable ingredients.

The Compounds of the formula I according to the invention are typically present in amounts of 0.01 to 20 wt .-%, preferably in amounts of 0.1 wt .-% to 10 wt .-% and particularly preferably used in amounts of 1 to 8 wt .-%. It prepares the expert no difficulties the quantities dependent to select according to the intended effect of the preparation.

In order to the compounds of the formula I have their positive effect as radical scavengers may develop the skin particularly well, it may be preferred the compounds of formula I penetrate into deeper skin layers allow. There are several possibilities to disposal. First, the compounds of the formula I have a certain lipophilicity that's enough can move around through the outer skin layer to penetrate into epidermal layers. As another option can in the preparation also appropriate means of transport, for example Liposomes, which are intended to transport the compounds of Formula I through the outer layers of the skin enable. After all is also a systemic transport of the compounds of the formula I conceivable. The preparation is then designed, for example, that they are for an oral dose is suitable.

Generally the substances of the formula I act as radical scavengers. Such radicals will be not only generated by sunlight, but under different Conditions formed. Examples are anoxia upstream of the flow of electrons of the cytochrome oxidases and the formation of superoxide radical anions conditionally; inflammation, including the formation of superoxide anions by the Membrane NADPH oxidase associated with the leukocytes, but also with the formation (by Disproportionation in the presence of iron (II) ions) of the hydroxy radicals and other reactive species that are normally involved in the phenomenon of Associated with phagocytosis; as well as lipid autoxidation which is generally initiated by a hydroxyl radical and lipidic alkoxy radicals and hydroperoxides.

It It is believed that preferred compounds of formula I as well Enzyme inhibitors act. They probably inhibit histidine decarboxylase, Protein kinases, elastase, aldose reductase and hyaluronidase, and enable Therefore, the integrity of the matrix of vascular sheaths is maintained to obtain. Furthermore, they probably do not specifically inhibit catechol O-methyltransferase, reducing the amount of available catecholamines and thereby vascular resistance elevated becomes. Further, they inhibit AMP phosphodiesterase, causing the substances have a potential to inhibit platelet aggregation.

by virtue of These properties are suitable compositions of the invention general for immune protection and protection of DNA and RNA. Especially The preparations are thereby suitable for the protection of DNA and RNA oxidative attacks, against radicals and against radiation damage, in particular UV radiation. Another advantage of the preparations according to the invention is the cell protection, especially the protection of Langerhans cells from damage through the above influences. All these uses or the use of the compounds of Formula I for the preparation of corresponding preparations are express also subject of the present invention.

In particular, preferred compositions of the invention are also useful in the treatment of skin diseases associated with a keratinization disorder involving differentiation and cell proliferation, in particular for the treatment of acne vulgaris, acne comedonicá, polymorphic acne, acacia rosaceae, nodular Acne, acne conglobata, age-related acne, acne, such as acne solaris, acne-related acne or acne professionalis, for the treatment of other disorders of keratinization, especially ichthyosis, ichtyosi forms Conditions, Darrier's disease, palmoplantar keratosis, leukoplakia, leukoplastic conditions, dermal and mucosal lichen (buccal) (lichen), for the treatment of other skin diseases associated with a keratinization disorder, and an inflammatory and / or immunoallergic component and in particular of all forms d psoriasis affecting the skin, mucous membranes, and fingers and toenails, and psoriatic rheumatism and skin atopy, such as eczema or respiratory atopy, or even gum hypertrophy, which compounds may also be used in some inflammatory conditions be associated with a disorder of keratinization, for the treatment of all benign or malignant growths of the dermis or epidermis, which may be of viral origin, such as Verruca vulgaris. Veruca plana, epidermodysplasia verruciformis, oral papillomatosis, papillomatosis florida, and proliferations caused by ultraviolet radiation may, in particular epithelioma basocellulare and epithelioma spinocellulare, be used for the treatment of other skin diseases, such as dermatitis bullosa and collagenous diseases, for the treatment of certain ocular diseases, in particular corneal disorders, for the elimination or control of photophysical and senile aging Reduction of pigmentation and keratosis actinica and for the treatment of all diseases associated with normal aging or photodamaging for the prevention or healing of wounds / scars of atrophy of the epidermis and / or dermis caused by locally or systemically applied corticosteroids and all other types of skin atrophy, to prevent or treat disorders of wound healing, to prevent or remedy stretch marks or to promote wound healing, to combat disorders of the Sebum production, such as hyperseborrhea in acne or simple seborrhea, for the control or prevention of cancerous conditions or precancerous conditions, especially promyelocytic leukemia, for the treatment of inflammatory diseases, such as arthritis, for the treatment of all viral diseases of the skin or other areas of the body, for the prevention or treatment of alopecia, for the treatment of skin diseases or diseases of other parts of the body with an immunological component, for the treatment of cardiovascular diseases, such as arteriosclerosis or hypertension, and for insulin-independent diabetes, for the treatment of skin problems caused by UV Radiation can be caused.

The antioxidant effects of the compounds according to formula I can be demonstrated, for example, with the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. 2,2-Diphenyl-1-picrylhydrazyl is a free radical stable in solution. The unpaired electron leads to a strong absorption band at 515 nm, the solution is dark violet in color. In the presence of a radical scavenger, the electron is paired, the absorption disappears, and the staining proceeds stoichiometrically, taking into account the absorbed electrons. The extinction is measured in the photometer. The antiradical property of the substance to be tested is determined by determining the concentration at which 50% of the 2,2-diphenyl-1-picrylhydrazyl used reacted with the radical scavenger. This concentration is expressed as EC ₅₀ , a value which under the given measurement conditions is to be regarded as a substance property. The examined substance is compared with a standard (eg tocopherol). The EC ₅₀ value is a measure of the capacity of each compound to catch radicals. The lower the EC ₅₀ value, the higher the capacity to catch radicals. Another important aspect of the effect of the antioxidants is the time this EC ₅₀ value is reached. This time, measured in minutes, gives the T _EC50 value, which _{tells you} the rate at which these antioxidants capture radicals. For the purpose of these inventions, antioxidants which reach this value within less than 60 minutes are considered to be fast, whereas those which reach the EC ₅₀ value only after more than 120 minutes are considered to be time-delayed.

by virtue of the special nature of the compounds of the invention, the determination of the However, antioxidant properties on a skin model or at least in the presence of skin-specific enzymes which split off sulfate groups, occur.

The antiradical efficiency (AE) (described by C. Sanchez-Moreno, JA Larrauri and F. Saura-Calixto in J. Sci. Food Agric., 1998, 76 (2), 270-276.) Results from the above mentioned quantities according to the following relationship:

A low AE (× 10 ^-3 ) is in the range up to about 10, an average AE is spoken in the range of 10 to 20, and a high AE is present according to the invention at values above 20.

there it can according to the invention in particular be preferred, fast-acting antioxidants with such slower or more time-delayed To combine effect. Here are typical weight ratios the fast-acting antioxidants to time-delayed antioxidants in the range 10: 1 to 1:10, preferably in the range 10: 1 to 1: 1 and for skin-protecting preparations particularly preferably in the range 5: 1 to 2: 1. In other according to the invention also preferred preparations may be in terms of effect optimization however, be beneficial, more time-delayed acting antioxidants are present as fast-acting antioxidants. Typical compositions then show weight ratios the fast-acting antioxidants to time-delayed antioxidants in the range 1: 1 to 1:10, preferably in the range 1: 2 to 1: 8.

The protective effect against oxidative stress or against the action of radicals can thus be further improved if the preparations contain one or more further antioxidants, wherein There is no difficulty for a person skilled in the art to select suitable fast-acting or time-delayed antioxidants.

In a preferred embodiment The present invention is the preparation therefore a preparation for the protection of body cells against oxidative Stress, in particular to reduce skin aging, thereby that they are next to the one or more connections after Formula I preferably contains one or more additional antioxidants.

There are many known and proven substances known from the literature which can be used as antioxidants, eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), Aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteine nsulfoximin, buthionine sulfones, penta, hexa, heptathionine sulfoximine) in very low compatible dosages (eg pmol to μmol / kg), furthermore (metal) chelators, (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids ( eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives ( eg vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, Uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives ( eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ^® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-α-tocopherol, L - (+) -Ascorbylpalmitat, citric acid and lecithin (for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) -. ascorbyl palmitate and citric acid (for example Oxynex ^® 2004) antioxidants are reacted with compounds of formula I in such compositions in ratios in the range from 1000: 1 to 1: 1000, preferably used in amounts of 100: 1 to 1: 100.

The preparations according to the invention may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B ₁ ), riboflavin (vitamin B ₂ ), nicotinamide , Vitamin C (ascorbic acid), Vitamin D, Ergocalciferol (Vitamin D ₂ ), Vitamin E, DL-α-Tocopherol, Tocopherol E-acetate, Tocopherol hydrogen succinate, Vitamin K ₁ , Esculin (Vitamin P active ingredient), Thiamine (Vitamin B ₁ ), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B ₁₂ ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL-α-tocopherol, tocopherol-E-acetate, nicotinic acid, pantothenic acid and biotin. Vitamins are used with compounds of the formula usually in ratios in the range of 1000: 1 to 1: 1000, preferably used in amounts of 100: 1 to 1: 100.

In particular according to the invention preferred preparations contain, in addition to the compounds of the formula I also pure UV filters.

at Use of the dibenzoylmethane derivatives particularly preferred as UV-A filters in combination with the compounds of formula I results additional Advantage: The UV-sensitive Dibenzoylmethanderivate be through the presence of the compounds of formula I additionally stabilized. Another object of the present invention is therefore the Use of the compounds according to formula I for the stabilization of dibenzoylmethane derivatives in preparations.

• – 2-Cyano-3,3-diphenylacrylsäure-2-ethylhexylester (z.B. Eusolex^® OCR),
• – 3,3'-(1,4-Phenylendimethylen)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-ylmethansulfonsäure sowie ihre Salze (z.B. Mexoryl^® SX) und
• – 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxi)-1,3,5-triazin (z.B. Uvinul^® T 150)
• – 2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoesäure hexylester (z.B. Uvinul^®UVA Plus, Fa. BASF).

In principle, all UV filters for a combination with the compounds of the invention come Formula I in question. Particularly preferred are those UV filters whose physiological harmlessness has already been demonstrated. Both for UVA and UVB filters, there are many well-known and proven substances from the literature, eg
Benzylidenecamphor derivatives, such as 3- (4'-methylbenzylidene) -dl-camphor (for example Eusolex ^® 6300), 3-benzylidenecamphor (for example Mexoryl ^® SD), polymers of N - {(2 and 4) - [(2-oxoborn-3- ylidene) methyl] benzyl} acrylamide (for example Mexoryl SW ^®), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (for example Mexoryl SK ^®) or (2-oxoborn-3- ylidene) toluene-4-sulfonic acid (for example Mexoryl SL ^®),
Benzoyl or dibenzoylmethanes, such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (for example Eusolex ^® 9020) or 4-isopropyl dibenzoylmethane (such as Eusolex ^® 8020),
Benzophenones such as 2-hydroxy-4-methoxybenzophenone (for example Eusolex ^® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (for example Uvinul ^® MS-40),
Methoxycinnamate such as octyl methoxycinnamate (for example Eusolex ^® 2292), 4-methoxycinnamate, for example as a mixture of isomers (for example Neo Heliopan E 1000 ^®)
Salicylate derivatives such as 2-ethylhexyl salicylate (for example Eusolex ^® OS), 4-isopropylbenzyl salicylate (for example Megasol ^®) or 3,3,5-trimethylcyclohexyl salicylate (for example Eusolex ^® HMS),
4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester (for example Eusolex ^® 6007), ethoxylated ethyl 4-aminobenzoate (for example Uvinul ^® P25),
Phenylbenzimidazolesulfonic acids, such as 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof (for example Eusolex ^® 232), 2,2- (1,4-phenylene) -bisbenzimidazol-4,6-disulfonic acid and salts thereof ( for example Neoheliopan ^® AP) or 2,2- (1,4-phenylene) -bisbenzimidazol-6-sulfonic acid;
and other substances like

• - 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl (for example Eusolex ^® OCR),
• - 3,3 '- (1,4-phenylenedimethylene) bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-ylmethanesulfonic acid and salts thereof (for example Mexoryl SX ^®) and
• - 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxi) -1,3,5-triazine (for example Uvinul ^® T 150)
• - 2- (4-diethylamino-2-hydroxy-benzoyl) -benzoic acid hexyl ester (Uvinul ^® example UVA Plus, BASF.).

The listed in the list Links are to be considered as examples only. Of course you can too other UV filters are used.

These Organic UV filters are usually in an amount of 0.5 to 10% by weight, preferably 1-8%, in cosmetic formulations incorporated.

• – 2-(2H-Benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol (z.B. Silatrizole^®),
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z.B. Uvasorb^® HEB),
• – α-(Trimethylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy(dimethyl [und ca. 6% methyl[2-[p-[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] und ca. 1,5% methyl[3-[p-[2,2-bis(ethoxycarbonyl)vinyl)phenoxy)propenyl) und 0,1 bis 0,4% (methylhydrogen]silylen]] (n ≈ 60) (CAS-Nr. 207 574-74-1)
• – 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (CAS-Nr. 103 597-45-1)
• – 2,2'-(1,4-Phenylen)bis-(1H-benzimidazol-4,6-disulfonsäure, Mononatriumsalz) (CAS-Nr. 180 898-37-7) und
• – 2,4-bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxyl]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (CAS-Nr. 103 597-45-, 187 393-00-6).
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z.B. Uvasorb^® HEB),

Other suitable organic UV filters are, for example

• 2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) -disiloxanyl) -propyl) -phenol (eg silatrizole ^® ),
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (for example Uvasorb HEB ^®),
• Α- (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl) and about 6% methyl [2- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy] -1-methylenethyl] and about 1.5% methyl [3- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy) propenyl) and 0.1-0.4% (methylhydrogen] silylene]] (n≈60) ( CAS No. 207 574-74-1)
• 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) (CAS No. 103 597-45-1)
• 2,2'- (1,4-phenylene) bis (1H-benzimidazole-4,6-disulfonic acid, monosodium salt) (CAS No. 180 898-37-7) and
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxyl] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (CAS No. 103 597- 45-, 187 393-00-6).
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (for example Uvasorb HEB ^®),

Other suitable UV filters are also Methoxyflavone ensprechend the older German patent application DE 10232595.2 ,

organic UV filters are typically used in an amount of 0.5 to 20% by weight, preferably 1-15%, incorporated into cosmetic formulations.

As inorganic UV filters are those from the group of titanium dioxides such as coated titanium dioxide (eg Eusolex ^® T-2000, Eusolex ^® T-AQUA), zinc oxides (eg Sachtotec ^® ), iron oxides or cerium oxides conceivable. These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 percent by weight, preferably 2-10%, in cosmetic preparations.

preferred Compounds having UV-filtering properties are 3- (4'-methylbenzylidene) dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxyoxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethylcyclohexylsalicylate, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 2-cyano-3,3-di-phenyl-2-ethylhexyl acrylate, 2-phenyl-benzimidazole-5-sulfonic acid and their potassium, sodium and triethanol amine salts.

By Combination of one or more compounds of the formula I with additional UV filters can protect against harmful effects the UV radiation can be optimized.

optimized Compositions can For example, the combination of organic UV filters 4'-methoxy-6-hydroxyflavone with 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione and 3- (4'-methylbenzylidene) dl camphor contain. This combination results in broadband protection, by the addition of inorganic UV filters, such as titanium dioxide microparticles still added can be.

• – Die Hydrophilie der Kapselwand kann unabhängig von der Löslichkeit des UV-Filters eingestellt werden. So können beispielsweise auch hydrophobe UV-Filter in rein wässrige Zubereitungen eingearbeitet werden. Zudem wird der häufig als unangenehm empfundene ölige Eindruck beim Auftragen der hydrophobe UV-Filter enthaltenden Zubereitung unterbunden.
• – Bestimmte UV-Filter, insbesondere Dibenzoylmethanderivate, zeigen in kosmetischen Zubereitungen nur eine verminderte Photostabilität. Durch Verkapselung dieser Filter oder von Verbindungen, die die Photostabilität dieser Filter beeinträchtigen, wie beispielsweise Zimtsäurederivate, kann die Photostabilität der gesamten Zubereitung erhöht werden.
• – In der Literatur wird immer wieder die Hautpenetration durch organische UV-Filter und das damit verbundene Reizpotential beim direkten Auftragen auf die menschliche Haut diskutiert. Durch die hier vorgeschlagene Verkapselung der entsprechenden Substanzen wird dieser Effekt unterbunden.
• – Allgemein können durch Verkapselung einzelner UV-Filter oder anderer Inhaltstoffe Zubereitungsprobleme, die durch Wechselwirkung einzelner Zubereitungsbestandteile untereinander entstehen, wie Kristallisations vorgänge, Ausfällungen und Agglomeratbildung vermieden werden, da die Wechselwirkung unterbunden wird.

All mentioned UV filters can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form. In detail, there are the following advantages:

• - The hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter. For example, hydrophobic UV filters can also be incorporated into purely aqueous preparations. In addition, the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.
• Certain UV filters, in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that affect the photostability of these filters, such as cinnamic acid derivatives, the photostability of the entire formulation can be increased.
• In the literature, the skin penetration through organic UV filters and the associated irritation potential during direct application to the human skin are discussed again and again. The encapsulation of the corresponding substances proposed here prevents this effect.
• - Generally, by encapsulation of individual UV filters or other ingredients preparation problems caused by interaction of individual preparation components with each other, such as crystallization processes, precipitation and agglomeration can be avoided because the interaction is suppressed.

Therefore is it preferred according to the invention if one or more of the above UV filters are encapsulated in Form present. It is advantageous if the capsules so small are they with the naked eye can not be observed. To achieve the o.g. Effects it is still required that the capsules are sufficiently stable and the encapsulated drug (UV filter) not or only to a small extent to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 B1 describe the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use in accordance with the invention have walls which can be obtained by a SolGel process, as described in applications WO 00/09652, WO 00/72806 and WO 00/71084. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.

there the capsules are preferably in preparations according to the invention contained in such quantities, which ensure that the encapsulated UV filters are present in the above-mentioned amounts in the preparation.

The preparations according to the invention can about that addition, more usual skin-friendly or skin-care active ingredients. This can be done in principle all agents known to those skilled in the art.

Especially preferred active ingredients are pyrimidinecarboxylic acids and / or aryloximes.

Pyrimidinecarboxylic acids occur in halophilic microorganisms and play a role in the osmoregulation of these organisms (EA Galinski et al., Eur. J. Biochem., 149 (1985) page 135-139). In particular, ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidincar are among the pyrimidinecarboxylic acids bonsäure) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylic acid and derivatives thereof These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic In particular, they stabilize enzymes against denaturing conditions such as salts, extreme pH, surfactants, urea, guanidinium chloride and other compounds.

Ectoin and ectoine derivatives such as hydroxyectoine may be beneficial in pharmaceuticals be used. In particular, hydroxyectoine for the production a drug used to treat skin diseases become. Other uses of hydroxyectoine and other ectoin derivatives typically in areas where e.g. Trehalose as an additive is used. So can Ectoin derivatives, such as hydroxyectoine, as a protective substance in dried Yeast and bacterial cells find use. Also pharmaceutical Products such as non-glycosylated, pharmaceutically active peptides and proteins e.g. t-PA can protected with Ectoin or its derivatives.

Under The cosmetic applications in particular is the use of Ectoin and ectoin derivatives for the care of aged, dry or call irritated skin. Thus, in the European patent application EP-A-0 671 161 specifically describes that ectoine and hydroxyectoine in cosmetic preparations such as powders, soaps, surfactant-containing Cleansing products, lipsticks, blushes, make-up, skin care creams and sunscreen preparations be used.

worin R¹ ein Rest H oder C1-8-Alkyl, R² ein Rest H oder C1-4-Alkyl und R³, R⁴, R⁵ sowie R⁶ jeweils unabhängig voneinander ein Rest aus der Gruppe H, OH, NH₂ und C1-4-Alkyl sind. Bevorzugt werden Pyrimidincarbonsäuren eingesetzt, bei denen R² eine Methyl- oder eine Ethylgruppe ist und R¹ bzw. R⁵ und R⁶ H sind. Insbesondere bevorzugt werden die Pyrimidincarbonsäuren Ectoin ((S)-1,4,5,6-Tetrahydro-2-methyl-4-pyrimidin-carbonsäure) und Hydroxyectoin ((S, S)-1,4,5,6-Tetrahydro-5-hydroxy-2-methyl-4-pyrimidin-carbonsäure) eingesetzt. Dabei enthalten die erfindungsgemäßen Zubereitungen derartige Pyrimidincarbonsäuren vorzugsweise in Mengen bis zu 15 Gew.-%. Vorzugsweise werden die Pyrimidincarbonsäuren dabei in Verhältnissen von 100:1 bis 1:100 zu den Verbindungen der Formel I eingesetzt, wobei Verhältnisse im Bereich 1:10 bis 10:1 besonders bevorzugt sind.In this case, a pyrimidinecarboxylic acid according to formula II below is preferably used,

wherein R ^{1 is} a radical H or C 1-8 -alkyl, R ^{2 is} a radical H or C 1-4 -alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and C1-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particular preference is given to the pyrimidinecarboxylic acids ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydrocarboxylic acid). 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). The preparations according to the invention contain such pyrimidinecarboxylic acids, preferably in amounts of up to 15% by weight. The pyrimidinecarboxylic acids are preferably used in ratios of 100: 1 to 1: 100 to give the compounds of the formula I, with ratios in the range from 1:10 to 10: 1 being particularly preferred.

Under The aryloxime is preferably 2-hydroxy-5-methyllaurophenone oxime, which also as HMLO, LPO or F5 is used. His suitability for use in cosmetic products, for example, from the Germans Laid-open specification DE-A-41 16 123 known. Preparations containing 2-hydroxy-5-methyllaurophenone oxime Accordingly, are for the treatment of skin diseases, the associated with inflammation, suitable. It is known that such preparations, e.g. to Therapy of psoriasis, different types of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory Diseases of the skin and the appendages can be used can. Preparations according to the invention, in addition to the compound of formula I additionally an aryloxime, preferably Contain 2-hydroxy-5-methyllaurophenonoxim show surprising anti-inflammatory suitability. The preparations contain preferably 0.01 to 10% by weight of the aryloxime, in particular preferred is when the preparation contains 0.05 to 5 wt% aryloxime.

Old Compounds or components used in the preparations can be are either known and commercially available acquirable or can be synthesized by known methods.

The one or more compounds of the formula I can be described in the usual Way incorporated into cosmetic or dermatological preparations become. Suitable preparations for external use, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin. For one internal use are administration formulas such as capsules, dragees, Powder, tablet solutions or solutions suitable.

When Use of the preparations according to the invention are e.g. called: solutions, Suspensions, emulsions, PIT emulsions, pastes, ointments, gels, Creams, lotions, powders, soaps, surfactant-containing cleansing preparations, oils, aerosols and sprays. Other applications are e.g. Sticks, shampoos and shower rooms. The preparation can any usual Carriers, Additives and optionally other active ingredients may be added.

preferable Excipients come from the group of preservatives, antioxidants, Stabilizers, solubilizers, Vitamins, colorants, Odor.

Anoint, Pastes, creams and gels can the usual excipients contained, e.g. animal and vegetable fats, waxes, paraffins, Strength, Tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, Talc and zinc oxide or mixtures of these substances.

powder and sprays can the usual excipients contained, e.g. Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can also use the usual Propellant, e.g. Chlorofluorocarbons, propane / butane or Dimethyl ether.

Solutions and Emulsions can the usual excipients like solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, Ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed, Peanut oil, Corn oil, Olive oil, castor oil and sesame oil, Glycerinfettsäureester, Polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances.

suspensions can the usual excipients like liquid Diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soap can the usual excipients like alkali salts of fatty acids, Salts of fatty acid monoesters, fatty acid protein, Isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerin, sugar or mixtures of these substances.

surfactant Cleaning products can the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein, Isothionates, imidazolinium derivatives, methyltaurates, sarcosinates, Fettsäureamidethersulfate, Alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, Lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures thereof Contain substances.

facial and body oils can be the usual excipients like synthetic oils such as fatty acid esters, fatty alcohols, Silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or Mixtures of these substances included.

Further typical cosmetic applications are also lipsticks, lip balms, Mascara, eye liner, eye shadow, blush, powder, emulsion and wax make up and sunscreen, pre-sun and after-sun preparations.

To the preferred forms of preparation according to the invention belong especially emulsions.

Inventive emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as usually for one such type of preparation is used.

• – Mineralöle, Mineralwachse
• – Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z. B. Rizinusöl;
• – Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z.B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;
• – Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.

The lipid phase can advantageously be selected from the following substance group:

• - mineral oils, mineral waxes
• - Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
• Fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with lower C-number alcohols, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower C-number alkanoic acids or with fatty acids;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of Emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then chosen advantageous are from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, Isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, Isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, Erucyl oleate, erucyl erucate and synthetic, semisynthetic and natural Mixtures of such esters, e.g. B. jojoba oil.

Further can the oil phase chosen favorably are from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ether, the group of saturated or unsaturated, branched or unbranched alcohols, as well as the fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C atoms. The fatty acid triglycerides may be, for example chosen favorably are selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil, and the like more.

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention. It may also be advantageous if Waxes, for example cetyl palmitate, as the sole lipid component the oil phase use.

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 triglyceride, dicapryl ether.

Particularly advantageous are mixtures of C _12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _12-15 -alkyl benzoate and isotridecyl isononanoate and mixtures of C _12-15 -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

From The hydrocarbons are paraffin oil, squalane and squalene advantageous to be used in the sense of the present invention.

Advantageous can also the oil phase furthermore have a content of cyclic or linear silicone oils or completely from such oils but it is preferred, except the silicone oil or the silicone oils An additional Content of other oil phase components to use.

Advantageous Cyclomethicone (Octamethylcyclotetrasiloxan) is used as a silicone oil to be used according to the invention. But also other silicone oils are advantageous for the purposes of the present invention to use for example, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Especially also advantageous are mixtures of cyclomethicone and isotridecyl isononanoate, from cyclomethicone and 2-ethylhexyl isostearate.

The aqueous Phase of the preparations according to the invention contains optionally advantageous alcohols, diols or polyols lower C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower alcohols C number, z. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickening agents, which or which chosen favorably can be from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropyl methylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

Especially Mixtures of the abovementioned solvents are used. For alcoholic solvents Water can be another ingredient.

Inventive emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as usually for one such type of formulation is used.

In a preferred embodiment contain the preparations according to the invention hydrophilic surfactants.

The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.

auszeichnen, wobei R einen verzweigten oder unverzweigten Alkylrest mit 4 bis 24 Kohlenstoffatomen darstellt und wobei DP einen mittleren Glucosylierungsgrad von bis zu 2 bedeutet.The alkylglucosides in turn are advantageously selected from the group of alkylglucosides, which are represented by the structural formula

wherein R represents a branched or unbranched alkyl radical having 4 to 24 carbon atoms and wherein DP means a mean Glucosylierungsgrad of up to 2.

The value DP represents the degree of glucosidation of the alkylglucosides used in the invention and is defined as

In this case, p ₁ , p ₂ , p ₃ ... Or p _{i represent} the proportion of the products which are mono-, di-trisubstituted-glucosylated in weight percentages. According to the invention, products having degrees of glucosylation of 1-2, in particular advantageously of 1, 1 to 1.5, most preferably selected from 1.2 to 1.4, in particular from 1.3.

Of the Value DP carries account for the fact that alkylglucosides are manufactured in usually represent mixtures of mono- and oligoglucosides. According to the invention advantageous is a relatively high content of monoglucosides, typically in of the order of magnitude from 40 to 70% by weight.

Particularly according to the invention Advantageously used alkyl glycosides are selected from the group octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, Undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecyl glucopyranoside.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic).

auszeichnen, wobei R¹ einen verzweigten oder unverzweigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet und M⁺ aus der Gruppe der Alkaliionen sowie der Gruppe der mit einer oder mehreren Alkyl- und/oder mit einer oder mehreren Hydroxyalkylresten substituierten Ammoniumionen gewählt wird bzw. dem halben Äquivalent eines Erdalkalions entspricht.In turn, the acyl lactylates are advantageously selected from the group of substances which are defined by the structural formula

in which R ^{1 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of the alkali metal ions and the group of ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth metal equivalent.

For example, sodium is advantageous, for example the product Pathionic ^® ISL from the American Ingredients Company.

auszeichnen, wobei R² einen verzweigten oder unverzeigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet.The betaines are advantageously selected from the group of substances which are defined by the structural formula

characterized in that R ^{2 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms.

Particularly advantageously, R ^{2 is} a branched or unbranched alkyl radical having 6 to 12 carbon atoms.

It is advantageous for example capramidopropylbetaine, for example the product Tego ^® betaine 810 from Th. Goldschmidt AG.

, Sodium, for example, selected as inventively advantageous cocoamphoacetate as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The preparations according to the invention are advantageously characterized in that the one or more hydrophilic Surfactants in concentrations of 0.01-20% by weight, preferably 0.05-10 Wt .-%, particularly preferably 0.1-5 wt .-%, each based on the Total weight of the composition, whether present or present.

To Application are the cosmetic and dermatological according to the invention Preparations in the for Cosmetics usual Applied to the skin and / or hair in sufficient quantity.

Cosmetic according to the invention and dermatological preparations can come in different forms available. So can they z. A solution, an anhydrous preparation, emulsion or microemulsion from Type water-in-oil (W / O) or oil-in-water type (O / W), a multiple emulsion, for example of the water-in-oil-in-water type (W / O / W), a gel, a solid stick, an ointment or even an aerosol represent. It is also beneficial to Ectoine in encapsulated form to give, for. In collagen matrices and other common ones Encapsulating materials, e.g. B. as Celluloseverkapselungen, in Gelatin, wax matrices or liposomally encapsulated. Especially Wax matrices as described in DE-OS 43 08 282, have been considered favorable exposed. Preference is given to emulsions. Become O / W emulsifiers particularly preferred. Emulsions, W / O emulsions and O / W emulsions are in usual Way available.

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsion according to the invention to use.

According to the invention advantageous are selected as co-emulsifiers, for example, O / W emulsifiers, mainly from the group of substances with HLB values of 11-16, especially advantageous with HLB values of 14.5-15.5, provided the O / W emulsifiers saturated Radicals R and R 'have. Do the O / W emulsifiers have unsaturated Radicals R and / or R ', or are Isoalkylderivate, so the preferred HLB value such emulsifiers are also lower or higher.

It is advantageous, the fatty alcohol ethoxylates from the group of ethoxylated Stearyl alcohol, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols) to choose. Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), Polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (Steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), Polyethylene glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), Polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (Isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), Polyethylene glycol (14) isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (Isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16), Polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (Isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), Polyethylene glycol (20) isostearyl ether (isosteareth-20), polyethylene glycol (13) cetyl ether (Ceteth-13), polyethylene glycol (14) cetyl ether (Ceteth-14), polyethylene glycol (15) cetyl ether (Ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether (Ceteth-17), polyethylene glycol (18) cetyl ether (ceteth-18), polyethylene glycol (19) cetyl ether (Ceteth-19), polyethylene glycol (20) cetyl ether (Ceteth-20), polyethylene glycol (13) isocetyl ether (Isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14), Polyethylene glycol (15) isocetyl ether (Isoceteth-15), polyethylene glycol (16) isocetyl ether (Isoceteth-16), polyethylene glycol (17) isocetyl ether (isoceteth-17), Polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (Isoceteth-19), polyethylene glycol (20) isocetyl ether (Isoceteth-20), Polyethylene glycol (12) oleyl ether (Oleth-12), polyethylene glycol (13) oleyl ether (Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15), polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), Polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (Ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth-16), Polyethylene glycol (17) cetyl stearyl ether (ceteareth-17), polyethylene glycol (18) cetyl stearyl ether (Ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (Ceteareth-19), Polyethylene glycol (20) cetylstearyl ether (Ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates of the following group:
Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol ( 14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, Polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate,

When ethoxylated alkyl ether carboxylic acid or its salt may advantageously be the sodium laureth-11-carboxylate be used. As alkyl ether sulfate sodium Laureth1-4sulfat be used advantageously. As an ethoxylated cholesterol derivative Advantageously, polyethylene glycol (30) cholesteryl ether may be used become. Also polyethylene glycol (25) soybean oil has been proven. When ethoxylated triglycerides can Advantageously, the polyethylene glycol (60) Evening Primrose Glycerides be used (Evening Primrose = evening primrose).

Farther is advantageous, the Polyethylenglycolglycerinfettsäureester from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, Polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, Polyethylene glycol (6) glyceryl caprate / cprinate, polyethylene glycol (20) glyceryl oleate, Polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoat to choose.

It is also cheap the sorbitan esters from the group polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, Polyethylene glycol (20) to choose sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be set:
Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C-atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ether of saturated and / or unsaturated, branched and or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms and sorbitan esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a Ke length of 8 to 24, in particular 12-18 C atoms.

Especially advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, Glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, Diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, Propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, Sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate, Sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, Behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, Polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, Glyceryl monocaprinate, glyceryl monocaprylate.

According to the invention preferred Preparations are particularly suitable for protecting human skin Aging processes as well as oxidative stress, i. against damage by radicals, as e.g. by sunlight, heat or other influences be generated. She lies in different, for this Application usually used dosage forms. So she can especially as Lotion or emulsion, such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, be present as solid pins or formulated as an aerosol.

The Preparation may contain cosmetic adjuvants present in this Type of preparations usually can be used, e.g. Thickening agents, softening agents, Humectant, surface-active Agents, emulsifiers, preservatives, antifoaming agents, Perfumes, waxes, lanolin, propellants, dyes and / or pigments, which dye the agent itself or the skin, and others in cosmetics usually used ingredients.

you can as dispersing or solubilizing an oil, wax or other fats, a low monoalcohol or a lower polyol or mixtures use of it. To the particularly preferred monoalcohols or Count polyols Ethanol, i-propanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment The invention is an emulsion which is used as a protective cream or milk present and except the compound or compounds of the formula I, for example fatty alcohols, Fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

Further preferred embodiments make oily Lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily-alcoholic lotions based on a Low alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerin, and oils, waxes and fatty acid esters, like triglycerides of fatty acids, represents.

The inventive preparation may also be present as an alcoholic gel containing one or more Lower alcohols or polyols, such as ethanol, propylene glycol or Glycerol, and a thickener such as silica. The oily-alcoholic Gels contain as well natural or synthetic oil or Wax.

The solid pens are made of natural or synthetic waxes and oils, Fatty alcohols, fatty acids, Fettsäureestern, Lanolin and other fatty substances.

is a preparation prepared as an aerosol, is used in the Usually the usual Propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes.

The Cosmetic preparation can also protect the hair against photochemical damage used to change of shades, a discoloration or damage mechanical nature. In this case, it is suitable a formulation as a shampoo, lotion, gel or emulsion for rinsing, wherein the respective preparation before or after shampooing, before or after dyeing or decolorizing or before or after the permanent wave is applied. It can also a preparation as a lotion or gel for styling and treating, as a lotion or gel for brushing or laying a water wave, as a hair coat, permanent wave, dyeing or bleach for the hair chosen become. The preparation with light protection properties can except the or the compounds of the formula I different, in this type of medium adjuvants used, such as surfactants, active agents, thickeners, Polymers, emollients, preservatives, foam stabilizers, Electrolytes, organic solvents, Silicone derivatives, oils, waxes, Antifettmittel, dyes and / or pigments containing the agent itself or dye your hair or others for Hair care usually used ingredients.

Further objects The present invention relates to a process for the preparation of a Preparation, which is characterized in that at least a compound of the formula I with radicals as described above one cosmetically, pharmaceutically or dermatologically or for food suitable carrier is mixed, and the use of a compound of formula I for the preparation of a preparation with antioxidant properties.

The preparations according to the invention can In doing so, they are manufactured using techniques that are familiar to those skilled in the art well known.

The Mixing can be a solving, Emulsifying or dispersing the compound according to formula I in the carrier for Episode.

In a preferred according to the invention Process is the compound of formula I or the above-described Mixture prepared in a process wherein 7,8-dihydroxyflavone is used as a starting material.

there the preparation is preferably carried out by esterification of said 7,8-Dihydroxyflavone with sulfur trioxide-pyridine complex in the weak Alkaline.

The Starting material 7,8-dihydroxyflavone or in an alternative according to the invention method to be used also directly the compounds of the invention can be prepared by reacting a 2-hydroxyacetophenone compound with a Lithium compound and then with a keto compound.

For example can according to M. Cushman and D. Nagarathnam in: Tetrahedron Letters, 31, 6497-6500, 1990 and M.Cushman; D. Nagarathnam; Journal of Organic Chemistry, 56, 4884-4887, 1991 with a large excess of lithium bis (trimethylsilyl) amide under homogeneous reaction conditions, the phenolic hydroxyl groups be deprotonated to produce the lithium enolate of the corresponding ketone. Subsequently the carbon atom of the lithium enolate can be regioselectively treated with a Acylated aroyl chloride so as to directly obtain a β-diketone intermediate, which subsequently is cyclized in acidic medium. A disadvantage of this method is however the big surplus at the Lithium base, which is difficult even with several purification steps Removable, as well as the high price of lithium base.

Therefore it is particularly preferred a method according to the International To carry out patent application WO 00/60889. In this invention preferred Procedure is the ratio the molar equivalents of lithium compound to the functional groups to be metalated the 2-hydroxyacetophenone compound is selected in the range 1 to 1.2.

Surprisingly was found that aforementioned relationship a complete Metallization of all hydroxyl groups and the carbonyl group of 2-hydroxyacetophenone Connection allowed. Less than a ratio of 1 would become one incomplete Lead metalation and thus a big one Number of unwanted By-products. A relationship of more than 1.2, on the other hand, means the use of a larger amount the usually not cheap lithium compounds and entrainment of lithium compounds in all subsequent series, in particular purification steps.

Preferably, the lithium compound is selected from inorganic lithium compounds because they are inexpensive and readily available in large quantities. Furthermore, they offer the advantage that they are slightly or not at all soluble in organic solvents, so that they have to be treated under heterogeneous conditions can be easily filtered from the reaction mixture when they are used in excess.

In a preferred embodiment the method according to the invention is The relationship of lithium compound to the functional groups to be metalated the 2-hydroxyacetophenone compound exactly 1 amounts to. This ensures that no possibly dissolved lithium compounds as Impurities in the final product occur, as these are usually not by purification steps, such as recrystallization from the intermediate and end products can be removed.

advantageously, the metallation is carried out in an ethereal solvent, since this is the metallation reaction by its polarity Training supported by Li-solvaten, reducing the basicity of the lithium base is increased.

wobei R¹ und R² je nach Zielmolekül unabhängig voneinander für Hydroxy- bzw. Sulfat-Gruppen stehen oder Gruppen darstellen, die sich durch chemische Modifikationen, wie beispielsweise Abspaltung von Schutzgruppen, Oxidation oder Reduktion, in Gruppen mit den oben genannten Bedeutungen überführen lassen.The 2-hydroxyacetophenone used in the process according to the invention preferably has the following structure:

wherein R ¹ and R ² independently of one another represent hydroxyl or sulfate groups or represent groups which can be converted by chemical modifications, such as removal of protective groups, oxidation or reduction, into groups having the abovementioned meanings.

wobei R^y eine Halogenid-, Alkoxyl- oder Ester-Gruppe bedeuten kann.The keto compound for carrying out the process according to the invention preferably has the following structure:

where R ^{y is} a halide, alkoxyl or ester group.

Preferably the hydroxyl groups of the 2-hydroxyacetophenone compound are unprotected. With that elaborate reactions for applying and removing protective groups avoided, so that the reaction is particularly simple.

In the case of the keto compounds R ^{y is} chloride, ie the compound is an acid chloride, an alkoxyl group, ie the compound is an ester, or an ester group, ie the compound is an acid anhydride. Depending on the substrate used, the use of different groups also permits the variation and exact choice of the reaction time. For example, the reaction time when using an acid chloride or an acid anhydride is between 2-6 hours, most often between 4-5 hours. When using an ester or using silylated protecting groups, the reaction time is more than 8 hours, usually more than 10, but often also about 16-20 hours.

First, will the 2-hydroxyacetophenone compound preferably with the ketone and a lithium compound in dry THF at low temperatures condensed (-78 ° C to -50 ° C) and gives a stable diketone intermediate. At temperatures of more than -50 ° C extends the reaction either no longer or too fast, i. with unwanted By-products or decomposition of the starting material so that the Range of -78 ° C to -50 ° C is preferred. Subsequently the diketone is cyclized under acidic conditions at 95-100 ° C, to give a flavone derivative.

As lithium bases which are used in a process according to the invention, the lithium bases listed below are particularly suitable:
LiNH ₂ , LiN (CH ₃ ) ₂ , LiN (C ₂ H ₅ ) ₂ , LiNCH (CH ₃ ) ₂ (LDA), Me ₃ Cli, PhCH ₂ Li, Ph ₂ CHLi, Ph ₃ CLi, LiCN, LiC (NO ₃ ) ₃ , LiC (CN) ₃ , LiN (C ₆ H ₁₁ ) ₂ , LiN (CH ₂ ) ₂ , LiCH ₃ , LiC ₂ H ₅ , LiCH (CH ₃ ) ₂ , LiC ₄ H ₉ , LiCH ₂ CH ( CH ₃ ) ₂ , LiC ₆ H ₁₃ , LiPh, LiCH ₃ COCHCOCH ₃ , LiCIO, LiCIO ₄ , LiIO ₄ , Li ₂ O, LiOH, LiOCH ₃ , LiOC ₂ H ₅ , LiOC ₄ H ₉ , LiOPh, LiOOCOPh, lithium enolates general formula LiOCR = CR ' ₂ , where R and R' is an aliphatic or aromatic radical, LiOSi (CH ₃ ) ₃ , Li (Si (CH ₃ ) ₃ ) ₂ , Li ₂ CO ₃ , lithium 2,2,6 , 6-tetramethylpiperidine (LiTMP).

As described above, including the purely inorganic lithium compounds or those lithium compounds whose mostly organic radical via inorganic Atoms (O, N, Si) is bonded to the lithium atom, more preferably.

When solvent for the execution the metallization reaction is preferred as described above an ethereal solvent, for example, diethyl ether, tetrahydrofuran (THF), dibutyl ether. Other polar solvents, however, such as methyl ethyl ketone and the like can also be used but also apolare depending on the hydroxyacetophenone used Solvent, such as. n-hexane, heptane, benzene, toluene etc.

It It has also been found that compounds of formula I stabilizing can act on preparations. When used in corresponding products, these therefore remain also longer stable and change her appearance is not. In particular, even with longer lasting Application or longer Storage the effectiveness of the ingredients, e.g. Vitamins, received. This is among other things particularly advantageous in compositions to protect the skin against the effects of UV rays, as these cosmetics are particularly high levels of exposure to UV radiation.

The positive effects of compounds of formula I give their particular suitability for use in cosmetic or pharmaceutical Preparations.

As well positive are the properties of compounds of the formula I. to evaluate for a use in food or as a dietary supplement or as "functional food. "The others exported to food Explanations apply mutatis mutandis to dietary supplements and for "functional food ".

The Foods which according to the present invention with one or a plurality of compounds of formula I can be enriched include all materials for the consumption by animals or for are suitable for consumption by humans, for example vitamins and provitamins thereof, fats, minerals or amino acids. "(The Foods can be firm but also fluid, as a drink are available).

Further objects Accordingly, the use of a Compound according to formula I as a food additive for the human or animal nutrition and preparations containing food or dietary supplements are and appropriate carriers contain.

Food, those according to the present invention with one or more compounds The formula I can be enriched, for example, also Foods that come from a single natural source, such as e.g. Sugar, unsweetened juice, Nectar or puree from a single plant species, e.g. unsweetened apple juice (for example a mixture of different types of apple juice), grapefruit juice, orange juice, Apple compote, apricot nectar, tomato juice, tomato sauce, tomato puree, etc. Further examples of Foods which according to the present invention with one or several compounds of formula I can be enriched, are Grain or cereal of a single plant species and materials that be prepared from such plant species, e.g. Corn syrup, Rye flour, wheat flour or oat bran. Also mixtures of such Foods are suitable to according to the present invention enriched with one or more compounds of formula I to be, for example, multivitamin preparations, mineral mixtures or sweetened juice. As other examples of foods that after the present invention with one or more compounds of Formula I can be enriched Food preparations, for example prepared cereals, pastries, mixed drinks, especially for Children prepared foods, such as yoghurt, diet foods, low-calorie foods or animal feeds, called.

The Foods which according to the present invention with one or a plurality of compounds of formula I can be enriched include thus all edible Combinations of carbohydrates, lipids, proteins, inorganic Elements, trace elements, vitamins, water or active metabolites of Plants and animals.

The Foods which according to the present invention with one or can be enriched in several compounds of formula I are preferably administered orally, e.g. in the form of food, pills, Tablets, capsules, powders, syrups, solutions or suspensions.

The enriched with one or more compounds of the formula I. food according to the invention can be made with the help of techniques well suited to the skilled person are known.

By their action as antioxidant or as radical scavenger are suitable Compounds of formula I also as a drug ingredient. They have a supporting effect or substituting to natural Mechanisms that trap radicals in the body. The connections of the formula I can partially compared in their effect with radical scavengers such as vitamin C. become. Compounds of the formula I can be used, for example, for preventive purposes Treatments of inflammation and allergies of the skin as well as in certain cases to prevent certain Cancers are used. In particular, compounds are suitable of the formula I for the manufacture of a medicament for the treatment of inflammation, Allergies and irritations, especially the skin. Furthermore, medicines can are produced in an action as a vein tonic, as an agent to increase the firmness of blood capillaries, as an inhibitor of cuperose, as an inhibitor of chemical, physical or actinic erythema, as a means of treating sensitive skin, as a decongestant, as a dehydrating agent, as a means of fattening, as anti-wrinkle agents, as stimulators the synthesis of components of the extracellular matrix, as fortifying Skin elasticity improving agent and anti-aging agent. Next in this context, preferred compounds of the Formula I antiallergic and antiinflammatory and antiirritative Effects. They are therefore suitable for the production of medicines for the treatment of inflammation or allergic reactions.

in the The invention will be explained in more detail below with reference to examples. the Invention is executable throughout the claimed range and not limited to the examples given here.

Examples

Example 1 Preparation of sulfates of 7,8-dihydroxyflavone

Execution:

40 ml of water are initially charged at RT with a few drops of pyridine. 0.75 g of 7,8-dihydroxyflavone and 10 mg of ascorbic acid are added. 0.5 ml of NaOH is added to this suspension (pH = 12.3). Now 0.95 g of sulfur trioxide-pyridine complex is added as a solid. The pH slowly fades and is maintained at between 8.2 and 9 by adding NaOH (32%) until stable. It is stirred for 30 min at RT and then the reaction solution is concentrated to about 10ml. By addition of 50 ml of methanol at 50 ° C, Na ₂ SO _{4 is} precipitated. After stirring with a little additional Na ₂ SO ₄ and charcoal, the solution is filtered off, concentrated to dryness and the residue is dried.

Yield: 1.15g mixture of the 3 possible Schwefelsäureester according to HPLC. (Merck Hitachi LaChrom HPLC (Interface D-7000, DAD L-7455, Column Oven L-7360, Autosampler L-200, Pump L-7100), Column = Chromolith Performance RP-18e, at 260nm: 4 main peaks at 3.1min (8%), at 4,9min (29%) and at 5.4min (47%), as well as at 5,6min with 9% = 7,8-dihydroxyflavone)

Separation of sulfates:

The Separation of the individual sulfates can be carried out with a Büchi Sepacore (UV photometer C-635, Fraction collector C-660, pump C-605, pump manager C-615) with chromolith PrepRod RP-18e column (Merck KGaA).

Example 2: Preparations

in the The following are exemplary formulations for cosmetic preparations indicated containing compounds of Examples 1-3. Otherwise are the INCI names of the commercial compounds indicated.

UV-Pearl, OMC stands for the preparation with the INCI name:
Water (for EU: Aqua), ethylhexyl methoxycinnamate, silica, PVP, chlorphenesin, BHT; this composition is commercially available under the name Eusolex ^® UV Pearl ^TM OMC from Merck KGaA, Darmstadt.

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

Tabelle 2: O/W-Emulsionen, Zahlen in Gew.-%

Tabelle 2 (Fortsetzung)

Tabelle 2 (Fortsetzung)

Tabelle 3: Gele, Zahlen in Gew.-%

Tabelle 3 (Fortsetzung)

Tabelle 3 (Fortsetzung)

Tabelle 3 (Fortsetzung)

The other UV pearls listed in the tables are each assembled analogously, with OMC being replaced by the specified UV filters. TABLE 1 W / O emulsions (numbers in% by weight)

Table 1 (continued)

Table 1 (continued)

Table 2: O / W emulsions, figures in% by weight

Table 2 (continued)

Table 2 (continued)

Table 3: Gels, numbers in wt%

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Claims (15)

Compound of formula I, characterized in that it is a 7,8-dihydroxyflavone derivative according to formula Ia or Ib or a salt thereof

Mixture, characterized in that there are at least 2 compounds selected from the compounds of formula Ia, Ib or Ic or salts thereof

contains. Preparation with antioxidant properties, containing a carrier and at least one compound of the formula I selected from the compounds according to formula Ia, Ib or Ic, according to claim 2 or a mixture according to claim Second Preparation according to claim 3 containing at least a compound of formula I, characterized in that the preparations one or more compounds of formula I in an amount of 0.01 to 20% by weight, preferably in an amount of 0.1 to 10% by weight contains. Preparation according to at least one of the preceding claims for the protection of body cells against oxidative stress, in particular for reducing skin aging, characterized in that it preferably one or more further antioxidants and / or vitamins, preferably selected from vitamin A palmitate, vitamin C and its Derivatives, DL-α-tocopherol, tocopherol-E-acetate, nicotinic acid, Pan tothensäure and biotin. Preparation according to at least one of the preceding Claims, wherein the preparation in addition to the at least one compound according to Formula I contains one or more UV filters, which are preferably selected from the group consisting of 3- (4'-methylbenzylidene) dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethylcyclohexylsalicylate, 4- (dimethylamino) benzoic acid 2-ethylhexylester, 2-Cyano-3,3-di-phenylacrylic acid 2-ethylhexyl ester, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts. Preparation according to at least one of the preceding Claims, characterized in that the preparation is a foodstuff or a dietary supplement is and one for Food suitable carrier and optionally other dietary supplements. Preparation according to at least one of the preceding Claims, characterized in that the preparation comprises a pharmaceutical, dermatological or cosmetic applications. Process for the preparation of a preparation by this in that at least one compound of the formula I is selected from the compounds according to formula Ia, Ib or Ic, according to claim 2 or a mixture according to claim 2 with a pharmaceutical, cosmetic or dermatological or suitable for food carrier is mixed. Use of at least one compound of the formula I selected from the compounds according to formula Ia, Ib or Ic according to claim 2 or a mixture according to claim 2 for the preparation of a preparation with antioxidant properties. Use of at least one compound of the formula I selected from the compounds according to formula Ia, Ib or Ic according to claim 2 or a mixture according to claim 2 for the preparation of preparations which have a protective effect against oxidative stress on body cells exercise and / or an aging of the skin counteract or for the reduction can contribute to the consequences of skin aging Use of at least one compound of the formula I selected from the compounds according to formula Ia, Ib or Ic according to claim 2 or a mixture according to claim 2 as an antioxidant. Use of at least one compound of the formula I selected from the compounds according to formula Ia, Ib or Ic according to claim 2 or a mixture according to claim 2 as a food additive for the Human or animal nutrition. Process for the preparation of a compound of the formula I selected from the compounds according to formula Ia, Ib or Ic according to claim 2 or a mixture according to claim 2, characterized in that 7,8-dihydroxyflavone as starting material is used. Process for the preparation of a compound of the formula I selected from the compounds according to formula Ia, Ib or Ic according to claim 2 or a mixture according to claim 2, characterized in that the preparation by reaction one or more 2-hydroxyacetophenone compounds having a Lithium compound and then with a keto compound.