DE102009007997A1 - New nitrogen-containing compounds useful e.g. as a repellent for resistance and/or deterrence of arthropods e.g. mosquitoes, horseflies fleas, lice, ticks, mites and ants in cosmetic and/or dermatological formulations - Google Patents

Abstract

Nitrogen containing compounds (I), are new. Nitrogen containing compounds of formula (N(R 1>)(C(=O)-R 2>)(CH 2-CH 2-C(=O)-R 3>)) (I), are new. R 1>, R 2>1-20C-alkyl, 2-20C-alkenyl, or saturated or partially or completely unsaturated 3-10C-cycloalkyl (where the ring is optionally bridged with (CH 2) ngroups), where: R 1>and R 2>are optionally further substituted with optionally saturated alkyl, saturated, partially or completely unsaturated cycloalkyl, and/or heteroatoms in different position, and one or two carbon atoms of R 1>and R 2>are optionally substituted by heteroatoms or atom groups of -O-, -N=, -C(O)-, -C(O)O- and/or -C(O)NH; R 3>cyclic or acyclic, esterified monoterpenoid, where the esterified monoterpenoid: is an oxygen-containing terpenoid or its related compound, an oil extract or terpene alcohols comprising nerol, citronellol, geraniol, menthol, p-methan-3,8-diol, isopulegol, perillyl alcohol, hydroxy pinene or borneol, contains two isoprene units, and is based on an essential monoterpene; and n : 1-3. Independent claims are included for: (1) the preparation of (I); (2) a formulation comprising (I); and (3) the preparation of the formulation comprising mixing (I) and optionally further active substance with a carrier. ACTIVITY : Insect Repellent; Arthropodicide; Acaricide. The insect repellent activity of (I) was tested on mice in a glass cage containing 50 female mosquitoes. The results showed that after 2 hours the number of stings on the mice was 0. MECHANISM OF ACTION : None given.

Description

The present invention relates to N-acyl-β-aminospropionic acid derivatives, a process for their preparation, their use as repellents in cosmetic and dermatological formulations for defense and Deterrence of arthropods and corresponding new preparations and their production.

A Variety of mosquitoes, brakes fleas, lice, Bedbugs, as well as ticks and mites, which are part of the arthropod tribe (Arthropods) belong and in the further Course also under the biological sense incorrectly used Generic term insects are addressed, feed themselves from the blood of warm-blooded animals, to which humans count. They drill their skin with their lancing and suction tools Victims until they encounter blood vessels. During ingestion but they vasodilator and anticoagulants, which cause itching, wheals in the host and allergic reactions. Especially In addition, in the tropics and subtropics exists the Danger of infection with pathogens. For example the malaria by the Anopheles mosquito or the yellow fever transmitted through the yellow fever mosquito. Also in temperate regions there is a risk of infection with insect-borne pathogens such as the tick-borne tick-borne encephalitis.

a Protection against harassment by arthropods offer so-called repellents. This is a series of active substances that by their odor repellent to insects and spiders work. These are usually low-volatility Compounds that evaporate slowly on the skin and thus one Incense bell over the skin forming the arthropods markets.

To The common repellents include N, N-diethyl-3-methylbenzamide ("DEET"), which is used against mosquitoes, and sandflies, brakes, fleas, bedbugs, ticks and mites is active. Further, dimethyl phthalate (trade name: palatinol M, DMP) against mosquitoes, lice, ticks and mites used.

Particularly effective is 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (under the trade name IR3535 ^® in Fa. Merck available), which can be used for example against mosquitoes, tsetse flies, ticks and brakes. The suitability of further β-alanine derivatives as insect repellents is described in M. Klier, F. Kuhlow, J. Soc. Cos. Chem., 27, pp. 141-153 (1976) examined.

Of the Of course, the prior art knows a variety various insect protection formulations. Disadvantage of this usual Insect repellent is that the known repellents in their Duration of action are limited and evaporate too quickly again. Often, their defense is not strong enough.

Next Synthetic compounds are also a variety of plant extracts and essential oils, which also have repellent activity exhibit. The best known is citronella oil, which is mainly made from Citronellal and geraniol exist. Other examples are eucalyptus, Lemongrass, peppermint oil, lavender oil, cedar oil, Rapeseed oil, rosemary oil, pennyroyal and cajeput. These However, they have several disadvantages, such as a only low repellent activity, a short effectiveness or side effects such as skin irritation or toxicity.

task Accordingly, the present invention has been a drawback to the prior art Overcome the technology and opportunities too find new substances that are suitable, cosmetic and to provide dermatological insect repellent formulations which show a comparable or stronger effect than the known repellents.

It was surprising and for the expert in none Foreseeable that certain new N-acyl-β-amino-propionic acid esters have excellent activity as a repellent. These new N-acyl-β-amino-propionic acid esters exist formally two active substances, the aminopropionic acid and a monoterpenoid which itself often has low repellent activity having. The covalent linkage of these two units surprisingly led to new and efficient Repellents.

in der die Reste wie folgt definiert sind:
R¹, R² = geradkettiges oder verzweigtes Alkyl mit 1-20 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkenyl mit 2-20 Kohlenstoffatomen, gesättigtes, teilweise oder vollständig ungesättigtes Cycloalkyl mit 3-10 Kohlenstoffatomen, wobei die Ringe jeweils auch mit -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
wobei R¹ und R² gleich oder verschieden sind,
wobei die R¹ und R² mit weiteren gesättigten und/oder ungesättigten Alkyl-, gesättigtes, teilweise oder vollständig ungesättigtes Cycloalkyl- und/oder Heteroatom-Substituenten in verschiedenen Positionen substituiert sein können,
wobei bei den R¹ und R² ein oder zwei Kohlenstoffatome durch die Heteroatome und/oder Atomgruppierungen -O-, -N=,-C(O)-, -C(O)O- und/oder -C(O)NH- ersetzt sein können,
R³ = cyclisches oder acyclisches, verestertes Monoterpenoid.A first subject of the present invention are therefore the compounds of the formula (I)

in which the radicals are defined as follows:
R ¹ , R ² = straight-chain or branched alkyl having 1-20 carbon atoms, straight-chain or branched alkenyl having 2-20 carbon atoms, saturated, partially or completely unsaturated cycloalkyl having 3-10 carbon atoms, the rings also each having - (CH ₂ ) _n groups can be bridged with n = 1 to 3,
where R ¹ and R ^{2 are the} same or different,
where R ¹ and R ² may be substituted with further saturated and / or unsaturated alkyl, saturated, partially or completely unsaturated cycloalkyl and / or heteroatom substituents in various positions,
where R ¹ and R ^{2 have} one or two carbon atoms through the heteroatoms and / or atomic moieties -O-, -N =, - C (O) -, -C (O) O- and / or -C (O) NH - can be replaced,
R ³ = cyclic or acyclic, esterified monoterpenoid.

R ¹ is preferably selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2- Ethylhexyl, n-decyl, n-dodecyl, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane and n-tetracosane, where R ^{1 is} particularly preferably n-butyl, n-octyl, 2- Ethylhexyl, n-decyl or n-dodecyl.

R ² is preferably selected from the group consisting of methyl, n-propyl, isopropyl, n-pentyl, n-heptyl, 1-ethyl-pentyl, n-nonyl, n-undecyl, where R ^{2 is} particularly preferably selected from Methyl, 1-ethyl-pentyl, n-nonyl and n-undecyl.

The esterified monoterpenoid R ³ is preferably an oxygen-containing terpenoid or a related compound. More preferably, it is formally composed of two isoprene units and is most preferably based on an essential monoterpene. The terpene alcohol on which the esterified monoterpenoid is based can be an oily extract or an oily essence.

According to the invention, N-acyl-β-amino-propionic acid esters of the formula (I) are preferred in which the terpene alcohol R ³ -H on which the esterified monoterpenoid is based is selected from the group consisting of

The preparation of the novel compounds can be carried out according to known methods: Preferably, the preparation of a compound of Formal I in an acid- or base-catalyzed Ver or transesterification between the corresponding Aminopropionsäure or the corresponding Aminopropionsäurealkylester, wherein the alkyl group in Aminopropionsäurealkylester 1 to 8 C Atoms may have and a terpene alcohol R ³ -H.

, wobei die Reste R¹ und R² eine der zuvor angegebenen oder als bevorzugt angegebenen Bedeutungen haben und R³* H oder eine Alkoxygruppe mit 1 bis 8 C-Atomen bedeutet,
mit einem Terpenalkohol R³-H umgesetzt wird.A further subject of the invention is therefore a process for the preparation of compounds of the formula I as defined above, including the preferred embodiments, characterized in that a compound of the formula (II)

where the radicals R ¹ and R ^{2 have} one of the meanings indicated above or as being preferred, and R ³ * denotes H or an alkoxy group having 1 to 8 C atoms,
with a terpene alcohol R ³ -H is reacted.

Particularly preferably, the corresponding ethyl β-amino-propionate is reacted with a terpene alcohol R ³ -H. B-Aminopropionsäureethylester are compounds of formula (II) having substituents R ¹ and R ² , as described above, wherein R ³ * is ethoxy. Preferably, the terpene alcohol R ³ -H is selected from the group consisting of nero, citronellol, geraniol, menthol, p-menthane-3,8-diol, isopulegol, perillyl alcohol, hydroxy-pinen, borneol.

In a very particularly preferred variant of the preparation process, the compounds according to the invention are prepared using the ion exchange resin Amberlyst-15 as catalyst (cf. Synthetic Comm. 2001, 31 (2), 289 ).

This preferred manufacturing method for the new compounds according to the formula is a further subject of the present Invention.

in der die Reste wie folgt definiert sind:
R¹, R² = geradkettiges oder verzweigtes Alkyl mit 1-20 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkenyl mit 2-20 Kohlenstoffatomen, gesättigtes, teilweise oder vollständig ungesättigtes Cycloalkyl mit 3-10 Kohlenstoffatomen, wobei die Ringe jeweils auch mit -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
wobei R¹ und R² gleich oder verschieden sind,
wobei die R¹ und R² mit weiteren gesättigten und/oder ungesättigten Alkyl-, gesättigtes, teilweise oder vollständig ungesättigtes Cycloalkyl- und/oder Heteroatom-Substituenten in verschiedenen Positionen substituiert sein können,
wobei bei den R¹ und R² ein oder zwei Kohlenstoffatome durch die Heteroatome und/oder Atomgruppierungen -O-, -N=,-C(O)-, -C(O)O- und/oder -C(O)NH- ersetzt sein können,
R³ = cyclisches oder acyclisches, verestertes Monoterpenoid als Repellent in kosmetischen und dermatologischen Formulierungen zur Abwehr und/oder Abschreckung von Arthropoden.A third object of the present invention is the use of at least one compound of the formula (I)

in which the radicals are defined as follows:
R ¹ , R ² = straight-chain or branched alkyl having 1-20 carbon atoms, straight-chain or branched alkenyl having 2-20 carbon atoms, saturated, partially or completely unsaturated cycloalkyl having 3-10 carbon atoms, the rings also each having - (CH ₂ ) _n groups can be bridged with n = 1 to 3,
where R ¹ and R ^{2 are the} same or different,
where R ¹ and R ² may be substituted with further saturated and / or unsaturated alkyl, saturated, partially or completely unsaturated cycloalkyl and / or heteroatom substituents in various positions,
where R ¹ and R ^{2 have} one or two carbon atoms through the heteroatoms and / or atomic moieties -O-, -N =, - C (O) -, -C (O) O- and / or -C (O) NH - can be replaced,
R ³ = cyclic or acyclic, esterified monoterpenoid as a repellent in cosmetic and dermatological formulations for the defense and / or deterrence of arthropods.

at the invention to be defended and / or deterring Arthropods are preferably flies and / or crawling Arthropods, Without limitation Generalities include, for example, mosquitoes, Flies, brakes, fleas, bugs, ticks, mites, lice, Ants and cockroaches.

The The principle of deterrence is not on the cosmetic or dermatological prophylaxis of insect bites or bites, but can also be used, for example, in crop protection or in the household be applied.

It has been found that compounds which are particularly suitable for use according to the invention are those compounds in which R ^{1 is} preferably selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-hexyl, n-decyl, n-dodecyl, n-tetradecane, n-hecadecane, n-octadecane, n-eicosane, n -docosan and n-tetracosane, wherein R ^{1 is} particularly preferably n-butyl, n-octyl, 2-ethyl-hexyl, n-decyl or n-dodecyl.

For the use according to the invention, R ^{2 is} preferably selected from the group consisting of methyl, n-propyl, isopropyl, n-pentyl, n-heptyl, 1-ethylpentyl, n-nonyl, n-undecyl, where R ^{2 is} particularly preferably selected is methyl, 1-ethyl-pentyl, n-nonyl and n-undecyl.

Preference according to the invention is given to using N-acyl-β-amino-propionic acid esters of the formula (I) in which the terpene alcohol on which the esterified monoterpenoid is based is selected from the group consisting of

Further preferred combinations of embodiments are in disclosed in the claims.

One Another object of the present invention is the use at least one compound of the formula (I) as a formulation aid in the manufacture of cosmetic or dermatological preparations.

In order to may in preferred embodiments of the present Invention the said compounds as solubilizers, Penetration enhancers and / or effect enhancers serve.

• – die Wirkungsdauer von Repellentien auf der Haut verlängern,
• – Repellentien gegen UV-Strahlung und/oder Hautflüssigkeiten stabilisieren und/oder
• – die Wirkung von Repellentien verstärken und so den Einsatz geringerer Repellent-Mengen in der Formulierung ermöglichen.

Accordingly, the compounds of the formula I used according to the invention as formulation auxiliaries can, for example, assist in insect repellent formulations by

• - prolong the duration of action of repellents on the skin,
• - stabilize and / or repellents against UV radiation and / or skin fluids
• - enhance the effect of repellents, thus allowing the use of lower levels of repellent in the formulation.

Further is also the subject of the present invention the use of Compounds of formula (I) in detergents, for example on the basis of aqueous or aqueous-alcoholic Solutions, or in the form of a detergent, wax, gel, Shampoos, sprays, solid product, emulsion, cream or dispersion.

The Compounds of the invention thus serve to Insects sustainably cleansed of those with the detergent Surfaces that can be hard or soft to drive and keep away.

in der die Reste wie folgt definiert sind:
R¹, R² = geradkettiges oder verzweigtes Alkyl mit 1-20 Kohlenstoffatomen, geradkettiges oder verzweigtes Alkenyl mit 2-20 Kohlenstoffatomen, gesättigtes, teilweise oder vollständig ungesättigtes Cycloalkyl mit 3-10 Kohlenstoffatomen, wobei die Ringe jeweils auch mit -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
wobei R¹ und R² gleich oder verschieden sind,
wobei die R¹ und R² mit weiteren gesättigten und/oder ungesättigten Alkyl, gesättigtes, teilweise oder vollständig ungesättigtes Cycloalyl und/oder Heteroatom-Substituenten in verschiedenen Positionen substituiert sein können,
wobei bei den R¹ und R² ein oder zwei Kohlenstoffatome durch die Heteroatome und/oder Atomgruppierungen -O-, -N=,-C(O)-, -C(O)O- und/oder -C(O)NH- ersetzt sein können,
R³ = cyclisches oder acyclisches, verestertes Monoterpenoid enthalten.A further subject of the present invention are preparations which comprise at least one compound of the formula (I)

in which the radicals are defined as follows:
R ¹ , R ² = straight-chain or branched alkyl having 1-20 carbon atoms, straight-chain or branched alkenyl having 2-20 carbon atoms, saturated, partially or completely unsaturated cycloalkyl having 3-10 carbon atoms, the rings also each having - (CH ₂ ) _n groups can be bridged with n = 1 to 3,
where R ¹ and R ^{2 are the} same or different,
where R ¹ and R ² may be substituted with further saturated and / or unsaturated alkyl, saturated, partially or completely unsaturated cycloalyl and / or heteroatom substituents in various positions,
where R ¹ and R ^{2 have} one or two carbon atoms through the heteroatoms and / or atomic moieties -O-, -N =, - C (O) -, -C (O) O- and / or -C (O) NH - can be replaced,
R ³ = cyclic or acyclic, esterified monoterpenoid included.

The Preparations may be cosmetic, pharmaceutical Be means, medical devices or food.

These Preparations are preferably used as insect repellents.

in the The meaning of the present invention is in addition to the term preparation synonymous, the term mean or formulation used.

According to the invention, preparations are preferred in which R ^{1 is} selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane and n-tetracosane, where R ^{1 is} particularly preferably n- Butyl, n-octyl, 2-ethyl-hexyl, n-decyl or n-dodecyl.

R ² is preferably selected from the group consisting of methyl, n-propyl, isopropyl, n-pentyl, n-heptyl, 1-ethyl-pentyl, n-nonyl, n-undecyl, where R ^{2 is} particularly preferably selected from Methyl, 1-ethyl-pentyl, n-nonyl and n-undecyl.

According to the invention, preparations with N-acyl-.beta.-aminopropionic acid esters in which the terpene alcohol on which the esterified monoterpenoid is based are selected from the group consisting of

In a preferred embodiment of the invention Preparation is the at least one N-acyl-β-amino-propionic acid ester of the formula (I) in an amount of 0.01 to 20 wt .-%, preferably in an amount of 0.1% by weight to 10% by weight and more preferably in an amount of 1.0 to 5.0% by weight. It prepares the expert no difficulty the quantities dependent on it to select according to the intended effect of the preparation.

Be The preparations are usually around topically applicable preparations, for example cosmetic or dermatological formulations. The preparations included in this case a cosmetically or dermatologically suitable carrier and depending on the desired property profile optionally further suitable ingredients. Is it pharmaceutical preparations, so the preparations in this case contain a pharmaceutical compatible carrier and optionally further pharmaceutical Agents. Is it food or dietary supplements, so choose a suitable carrier.

These it is in the preparations to perfumes, so it is in a variant of the invention preferred when in addition to the perfumes or perfume oils and the flavonoids and typical carriers, such as water, Solvents, such as alcohols, oils and possibly emulsifiers no further aids are included.

All Compounds or components used in the preparations can be either known or for sale Acquired or can be synthesized by known methods become.

Further preferred combinations of embodiments are in disclosed in the claims.

In the described preparations and mixtures which contain according to the invention at least one N-acyl-β-amino-propionic acid ester of the formula (I), pigments may furthermore also be present, wherein the layer structure of the pigments is not limited.

The inventive preparation can about In addition, preferably also contain further active ingredients, such as Example further repellents, UV filters, aryloximes and parabens.

The Most repellent agents belong to the substance classes of Amides, alcohols, esters and ethers. Repellents should usually meet the following conditions: you are allowed do not evaporate too quickly and do not penetrate the skin. she may neither be primarily irritating to the chew nor They also have a sensitizing effect and should not be toxic be. Their effectiveness must also be under the action of skin fluid and / or UV radiation.

Preferred repellents which can be combined with at least one compound of the formula (I) are selected from N, N-diethyl-3-methylbenzamide, ethyl 3- (acetyl-butyl-amino) -propionate, dimethyl phthalate, butopyronoxyl, 2,3 , 4,5-bis (2-butylene) -tetrahydro-2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, N- (2-ethylhexyl) -8 , 9,10-trinorborn-5-ene-2,3-dicarboximide, dimethyl carbate, di-n-propyl isocine chomeronate, (R) -p-mentha-1,8-diol, 2-ethylhexane-1,3-diol, N -octyl-bi-cyclohepetendiecarboximid, piperonyl butoxide, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) -piperidine (Bayrepel ^®; Bayer.), or mixtures thereof, wherein it is particularly preferably selected from N, N-diethyl 3-methylbenzamide, 3- (acetyl-butylamino) -propionic acid ethyl ester, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) -piperidine or mixtures thereof.

parabens are 4-hydroxybenzoic acid esters which are in free form or as sodium salts for the preservation of preparations in the field food, cosmetics and medicines. The effect of the esters is directly proportional to the chain length however, the solubility decreases with the alkyl radical increasing chain length. As non-dissociating compounds the esters are largely pH-independent and act in a pH range of 3.0-8.0. The antimicrobial mechanism of action is due to damage to the microbial membranes the surface activity of PHB esters as well protein denaturation. In addition, interactions occur with coenzymes on. The effect is directed against fungi, yeasts and Bacteria. The most important preservatives are parabens Methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, 4-hydroxybenzoic acid propyl ester, 4-hydroxybenzoic acid butyl ester.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products, for example, from the German patent application DE 41 16 123 known. Compositions according to the invention which, in addition to the compound (s) mentioned, additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising anti-inflammatory suitability. The preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.

The protective effect of preparations for example for the use against oxidative stress or against the action of Radicals can be improved if the preparations have an or contain several antioxidants, wherein the expert no Difficulty prepares suitable fast or delayed to select effective antioxidants.

In an embodiment is therefore in the preparation to a preparation for the protection of body cells against oxidative Stress, in particular to reduce skin aging, thereby characterized in that they include one or more of the other ingredients contains several antioxidants.

There are many known and proven substances in the literature that can be used as antioxidants, e.g. For example, amino acids (eg, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their Derivatives (eg anserine), carotenoids, caroline (eg α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic 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, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinsulfoximine, buthionine sulfones , Penta-, hexa-, heptathionine sulfoximine) in very poor compatibility doses (eg. Pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, milk acid, malic acid), humic acid, bile acids, biliary 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 benzylic resin, benzylic acid, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylated hydroxyanisole, 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 (e.g. Stilbene oxide, trans-stilbene oxide).

worin
R¹ aus der Gruppe -C(O)CH₃, -CO₂R³, -C(O)NH₂ und -C(O)N(R⁴)₂ ausgewählt werden kann,
X O oder NH,
R² lineares oder verzweigtes Alkyl mit 1 bis 30 C-Atomen,
R³ lineares oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
R⁴ jeweils ungabhängig voneinander H oder lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen,
R⁵ lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen oder lineares oder verzweigtes Alkoxy mit 1 bis 8 C-Atomen und
R⁶ lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen bedeutet, vorzugsweise Derivate der 2-(4-Hydroxy-3,5-dimethoxybenzyliden)-malonsäure und/oder 2-(4-Hydroxy-3,5-dimethoxybenzyl)-malonsäure, besonders bevorzugt 2-(4-Hydroxy-3,5-dimethoxybenzyliden)-malonsäure-bis-(2-ethylhexyl)ester (z. B. Oxynex^® ST Liquid) und/oder 2-(4-Hydroxy-3,5-dimethoxybenzy)-malonsäure-bis-(2-ethylhexyl)ester (z. B. RonaCare^® AP).Suitable antioxidants are also compounds of the formulas A or B.

wherein
R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,
X is O or NH,
R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,
R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,
R ^{4 are} each independently of one another H or linear or branched alkyl having 1 to 8 C atoms,
R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
R ⁶ denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethylhexyl) ester (z. B. Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3, 5-dimethoxybenzy) malonic acid-bis (2-ethylhexyl) ester (z. B. RonaCare ^® AP).

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercial mixtures are, for example, mixtures 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 - (+) - ascorbyl palmitate, citric acid and lecithin (. for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) -. ascorbyl palmitate and citric acid (for example Oxynex ^® 2004 Such antioxidants are usually employed with the compounds of the invention in such compositions in weight percent ratios in the range of 1000: 1 to 1: 1000, preferably in weight percent ratios of 100: 1 to 1: 100.

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

Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) is frequently cited as a particularly effective antioxidant (eg. CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159 ). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH-dependence of the antioxidant effect of hydroxyflavones. Quercetin shows the highest activity of the investigated structures over the entire pH range.

wobei
R¹ bis R¹⁰ gleich oder verschieden sein können und ausgewählt sind aus

• – H
• – OR¹¹
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
• – wobei alle OR¹¹ unabhängig voneinander stehen für
• – OH
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkyloxygruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenyloxygruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkoxygruppen, wobei die Hydroxygruppe(n) an ein primäre oder sekundäre Kohlenstoffatome der Kette gebunden sein können und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkyloxygruppen und/oder C₃- bis C₁₂-Cycloalkenyloxygruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können und/oder,
• – Mono- und/oder Oligoglycosylreste, mit der Maßgabe, dass mindestens 4 Reste aus R¹ bis R⁷ stehen für OH und dass im Molekül mindestens 2 Paare benachbarter Gruppen -OH vorliegen,
• – oder R², R⁵ und R⁶ für OH und die Reste R¹, R³, R⁴ und R^7-10 für H stehen, wie sie in der Deutschen Patentanmeldung DE-A-102 44 282 beschrieben sind.

Suitable antioxidants are furthermore compounds of the formula (C)

in which
R ¹ to R ^{10 may be the} same or different and are selected from

• - H
• - OR ¹¹
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ to C ₂₀ hydroxyalkyl groups, where the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3,
• Where all OR ^{11 are} independent of each other
• - OH
• Straight-chain or branched C ₁ -C ₂₀ -alkyloxy groups,
• Straight-chain or branched C ₃ - to C ₂₀ -alkenyloxy groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkoxy groups, where the hydroxy group (s) may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3 and / or
• Mono- and / or oligoglycosyl radicals, with the proviso that at least 4 radicals from R ¹ to R ⁷ are OH and that at least 2 pairs of adjacent groups -OH are present in the molecule,
• Or R ² , R ⁵ and R ^{6 are} OH and the radicals R ¹ , R ³ , R ⁴ and R ^{7-10 are} H, as described in the German patent application DE-A-102 44 282 are described.

The preparations to be used may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, 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 ), particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL-α Tocopherol, tocopherol E acetate, nicotinic acid, pantothenic acid and biotin. Vitamins are usually added to the flavonoid-containing premixes or preparations when applied cosmetically in the range of 0.01% to 5.0% by weight, based on the total weight. Nutritional physiology applications are based on the recommended vitamin requirement.

preferred Preparations may also serve and contain the sunscreen then in addition to α-amino acid derivatives and the sparingly soluble Substances and possibly other ingredients as well UV filter.

• – 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 are suitable for combination with the α-amino acid derivatives to be used according to the invention. Particularly preferred are those UV filters whose physiological harmlessness has already been demonstrated. For both UVA and UVB filters, there are many well-known and proven substances from the literature, for. B.
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 (e.g., Mex oryl ^® 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 (z. B. Mexoryl SL ^®),
Benzoyl or Dibenzoylmethae such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (z. B. Eusolex ^® 9020) or 4-isopropyldibenzoylmethane (z. B. Eusolex ^® 8020 )
Benzophenones such as 2-hydroxy-4-methoxybenzophenone (z. B. Eusolex ^® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (eg. As Uvinul ^® MS-40),
Methoxycinnamate such as octyl methoxycinnamate (for. Example Eusolex ^® 2292), isopentyl 4-methoxycinnamate, z. B. as a mixture of isomers (eg., Neo Heliopan ^® E 1000),
Salicylate derivatives such as 2-ethylhexyl salicylate (for. Example Eusolex ^® OS), 4-isopropylbenzyl (z. B. ^® Megasol) or 3,3,5-trimethylcyclohexyl (z. B. Eusolex ^® HMS),
4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester (z. B. Eusolex ^® 6007), ethoxylated ethyl 4-aminobenzoate (z. B. Uvinul ^® P25),
Phenylbenzimidazolesulfonic acids, such as 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and Triethanolaminsaize (z. B. Eusolex ^® 232), 2,2- (1,4-phenylene) -bisbenzimidazol-4,6-disulfonic acid or their salts (. 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 (for example Mexoryl SX ^®) and.
• - 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxi) -1,3,5-triazine (. For example Uvinul ^® T 150)
• - benzoic acid 2- (4-diethylamino-2-hydroxy-benzoyl) benzoate (. For example Uvinul ^® UVA Plus, BASF.).

The Listed compounds are only examples specific. Of course, others can UV filters are used.

• – 2-(2H-Benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol (z. B. Silatrizole^®, Drometrizole, Trisiloxane, Mexoryl® XL),
• – 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-Dimethylathyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z. B. Uvasorb^® HEB) oder
• – 2,4-Bis-[4-[5-(1,1-dimethyl-oropyl)benzoxazol-2-yl]phenylimino]-6-[(2-ethylhexyl)imino]-1,3,5-triazin.

Other suitable organic UV filters are z. B.

• 2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol (e.g. B. Silatrizole ^®, Drometrizole, trisiloxane, Mexoryl® XL)
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (z. B. 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 to 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-dimethyl-ethyl) -aminocarbonyl) -phenyl-amino] -1,3,5-triazine-2,4-diyl) -diimino] bis (benzoic acid 2-ethylhexyl ester) (z. B. Uvasorb HEB ^®) or
• - 2,4-bis [4- [5- (1,1-dimethyl-oropyl) benzoxazol-2-yl] phenylimino] -6 - [(2-ethylhexyl) imino] -1,3,5-triazine.

Other suitable UV filters are also Methoxyflavone ensprechend the German patent application DE-A-10232595 ,

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

In order to ensure optimized UV protection, it is further preferred if preparations with light protection properties also contain inorganic UV filters. As inorganic UV filters are those from the group of titanium dioxides such. For example, coated titanium dioxide (for. Example Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO), zinc oxides (eg. As Sachtotec® ^®), iron oxides and also cerium. These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 weight percent, preferably 2-10 wt .-%, 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-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 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 of said compounds with UV filtering effect can be protective against harmful Effects of UV radiation can be optimized.

• – 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 Kristallisationsvorgänge, 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 is 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 prevented.

Therefore It is preferable if one or more of the above UV filters present in encapsulated form. It is advantageous if the Capsules are so small that they are not visible to the naked eye can be observed. To achieve the o. G. effects It is also necessary that the capsules are sufficiently stable and the encapsulated drug (UV filter) not or only slightly Giving circumference to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 51 describe the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use have walls which are produced by a SolGel process, as described in applications WO 00/09652 . WO 00/72806 and WO 00/71084 described can be obtained. 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 to be used in accordance with the invention Preparations are preferably contained in such quantities, which ensure that the encapsulated UV filters in the above weight percent ratios present in the preparation.

The can be used according to the invention preparations In addition, other usual skin-friendly or contain skin-care agents. This can be done in principle all agents known to those skilled in the art.

Particularly preferred active ingredients, in particular for skin-care preparations, are, for example, also so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes are also in the German patent application DE-A-10133202 described osmolytes. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids, and in each case their precursors. As osmolytes in the sense of the German patent application DE-A-10133202 especially substances from the group of polyols, such as myo-inositol, mannitol or sorbitol and / or one or more of the following osmolytically active substances understood: taurine, choline, betaine, phosphorylcholine, Glycerophosphorylcholine, glutamine, glycine, α-alanine, glutamate , Aspartate, proline, and taurine. Precursors of these substances are, for example, glucose, glucose polymers, phosohatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z. B. Compounds that are converted to osmolytes by metabolic steps.

Preferably according to the invention as compatible solute substances selected from the group consisting of Pyrimidincarbonsäuren (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic di phosphoglycerate, N. acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (Firoin) , β-Mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, e.g. As an acid, a salt or ester of these compounds or combinations thereof.

there Among the pyrimidinecarboxylic acids are especially ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives. The inventively used Preparations such Pyrimidincarbonsäuren preferably in amounts up to 15% by weight.

Especially it is preferred if the compatible solutes selected are di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (Firoin), β-mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP), ectoine, hydroxyectoine or mixtures thereof.

Further can the preparations of the invention at least one self-tanner as another ingredient contain.

When Advantageous self-tanner may include Glycerol aldehyde, hydroxymethylglyoxal, γ-dialdehyde, Erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (Juglone), 2-hydroxy-1,4-naphthoquinone (Lawson), 1,3-dihydroxyacetone.

The Compounds of formula (I) and optionally further active ingredients can be done in the usual way, for example by Mix, incorporated into preparations.

Suitable are preparations for an external Application, for example as a cream, lotion, gel, or as a solution, which can be sprayed on the skin. For an internal application are dosage forms such as capsules, Dragees, powders, tablet solutions or solutions suitable.

When Application form of the preparations to be used are, for. B. called: Solutions, suspensions, emulsions, PIT emulsions, pastes, Ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleansing preparations, oils, Aerosols and sprays. Preferred embodiments are also shampoos, Sunbathing and shower baths.

preferred Excipients come from the group of preservatives, stabilizers, Solubilizers, colorants, odor improvers.

Anoint, Pastes, creams and gels can be the usual carriers included, for. B. animal and vegetable fats, waxes, paraffins, Starch, tragacanth, cellulose derivatives, polyethylene glycols, Silicones, bentonites, silicic acid, talc and zinc oxide or Mixtures of these substances.

powder and sprays can be the usual carriers included, for. Lactose, talc, silicic acid, aluminum hydroxide, Calcium silicate and polyamide powder or mixtures of these substances. Sprays can also use the usual volatile, liquefied propellant, z. As chlorofluorocarbons, propane / butane or dimethyl ether, contain. Also, compressed air is advantageous to use.

solutions and emulsions may be the usual carriers such as solvents, solubilizers and emulsifiers, z. As water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, Benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, especially cottonseed oil, peanut oil, corn oil, Olive oil, castor oil and sesame oil, glycerol fatty acid esters, Polyethylene glycols and fatty acid esters of sorbitan or Mixtures of these substances included.

suspensions can the usual carriers like liquid diluents, e.g. As water, ethanol or Propylene glycol, suspending agent, e.g. B. 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 carriers like Alkali salts of fatty acids, salts of fatty acid monoesters, Fatty acid protein hydrolysates, isothionates, lanolin, Fatty alcohol, vegetable oils, plant extracts, glycerin, sugar or mixtures of these substances.

surfactant Cleaning products can be the usual carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, Fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, Methyl taurates, sarcosinates, fatty acid amide ether sulfates, Alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated Glycerin fatty acid esters or mixtures of these substances.

facial and body oils can be the usual Carriers such as synthetic oils such as fatty acid esters, fatty alcohols, Silicone oils, natural oils such as vegetable oils and oily extracts, paraffin oils, Lanolin oils or mixtures of these substances.

Further typical cosmetic applications are also lipsticks, lip balms, Powder, emulsion and wax-hook up, as well as sunscreen, pre-sun and after-sun preparations.

To the preferred preparation forms belong in particular also emulsions.

emulsions are advantageous and contain z. As mentioned fats, oils, Waxes and other fatty substances, as well as water and an emulsifier, as he usually does for such a 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 fats, preferably esters of fatty acids with lower C-number alcohols, e.g. With isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously chosen from 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 be chosen favorably 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 as well as synthetic, semi-synthetic and natural mixtures such esters, e.g. B. jojoba oil.

Further the oil phase can be chosen advantageously from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group the saturated or unsaturated, branched or unbranched alcohols, and 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 be chosen advantageously 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 more.

Also any mixtures of such oil and wax components are advantageous to use in the context of the present invention. It may also be advantageous to use waxes, for example Cetyl palmitate, as the sole lipid component of the oil phase use.

If appropriate, the aqueous phase of the preparations to be used advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides and their derivatives, for. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate the group of so-called carbopols, for example Carbopols of types 980, 981, 1382, 2984, 5984, in each case individually or in combination.

Especially Mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another Be part of it.

emulsions are advantageous and contain z. As mentioned fats, oils, Waxes and other fatty substances, as well as water and an emulsifier, as he usually does for such a type of Formulation is used.

The preparations can be in various forms. So they can z. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. Oil-in-water (W / O / W), a gel, a solid stick, an ointment or even an aerosol represent. It is also advantageous to present Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g. As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices like those in the DE-A-43 08 282 have been described, have turned out to be favorable. Preference is given to emulsions. O / W emulsins are especially preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.

When Emulsifiers, for example, the well-known W / O and O / W emulsifiers are used. It is beneficial to more usual Co-Emulgatorer. in the preferred O / W emulsions.

Advantageous For example, O / W emulsifiers are chosen as coemulsifiers. primarily from the group of substances with HLB values of 11-16, especially advantageous with HLE values of 14.5-15.5, if the O / W emulsifiers have saturated radicals R and R '. Do the O / W emulsifiers unsaturated radicals R and / or R 'on, or are Isoalkylderivate, the preferred HLB value of such emulsifiers also lower or above lie.

It is advantageous, the fatty alcohol ethoxylates from the group of ethoxylated Stearyl alcohol, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols) to choose.

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 can Advantageously, the sodium laureth-11-carboxylate can be used. When Alkyl ether sulfate can be advantageously used sodium laureth 1-4 sulfate become. As the ethoxylated cholesterol derivative, polyethylene glycol (30) may advantageously be cholesteryl ether be used. Also, polyethylene glycol (25) sojasterol has become proven. As 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 (cocoate) 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 used:
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 K ettenlänge 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.

The Preparation may contain cosmetic adjuvants present in this Type of preparations commonly used, such as z. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, Foaming agents, perfumes, waxes, lanolin, propellants, Dyes and / or pigments containing the agent itself or the Dye skin, and others in cosmetics usually used ingredients.

you may be an oil as a dispersing or solubilizing agent, Wax or other fat, a low mono alcohol or a lower polyol or mixtures thereof. To the particularly preferred monoalcohols or polyols Ethanol, i-propanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment of the invention is an emulsion, which is present as a protective cream or milk and, 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 provide oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, especially triglycerides of fatty acids, or oily-alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerol, and oils, Waxes and fatty acid esters, such as triglycerides of fatty acids, represents.

The Preparation may also be present as an alcoholic gel containing a or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickening agent such as silica. The oily-alcoholic gels also contain natural or synthetic oil or wax.

The Solid pens are made of natural or synthetic Waxing and oiling, fatty alcohols, fatty acids, fatty acid esters, 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, preferably alkanes.

The Preparations to be used can with the help of Techniques well known to those skilled in the art.

The Preparations as described above, may be mentioned contain necessary or optional ingredients or comprise, consist essentially of, or consist of.

Even without further statements, it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments and examples are therefore to be considered as merely illustrative, in no way limiting, disclosure. The complete disclosure of old applications and publications listed above and below are introduced by reference into this application.

The in the following examples of the invention The subject matter is merely illustrative and narrow present invention in no way in any way. Furthermore is the described invention throughout the claimed range executable. All compounds or components that are in The preparations can be used either known and commercially available or can be synthesized by known methods.

example 1

Synthesis of 3- (acetylbutylamino) -propionic acid 2-isopropyl-5-methylcyclohexyl ester

• ¹H-NMR (CDCl₃) δ 4.67 (m, 1H), 3.56 (t, J = 7.0 Hz, 2H), 3.27 (dd, J = 8.1, 7.3 Hz, 2H), 2.59 (m, 2H), 2.05 (d, 3H), 2.01-1.92 (m, 1H), 1.87-1.76 (m, 1H), 1.72-1.62 (m, 2H), 1.60-1.45 (m, 3H), 1.44-1.22 (m, 3H), 1.12-0.85 (m, 12H), 0.75 (t, J = 7.0 Hz, 3H)
• ¹³C-NMR (CDCl₃) δ 171.8, 170.3, 74.4, 49.5, 47.0, 42.3, 40.9, 34.2, 33.2, 31.2, 26.3, 23.5, 21.9, 21.4, 20.7, 20.0, 16.4, 13.7
• APCI MS (m/z) 326 (M+H)⁺

A mixture of 10.0 mL of 3- (acetylbutylamino) -propionic acid ethyl ester (46.5 mmol), 10.9 g of L-menthol (69.7 mmol) and 800 mg of the catalyst Amberlyst-15 in 40 mL of toluene is placed in a 3-neck round bottom flask , which is equipped with a distillation bridge to remove the ethanol, heated to 140 ° C under a nitrogen atmosphere. After completion of the reaction, the catalyst is filtered off, the filtrate is concentrated and chromatographed on silica gel with a mixture of petroleum ether: MTBE (7: 3). This gives 6.4 g of 3- (acetylbutylamino) -propionic acid 2-iospropyl-5-methyl-cyclohexyl ester as a colorless oil.

• ¹ H-NMR _(CDCl3) δ 4.67 (m, 1H), 3:56 (t, J = 7.0 Hz, 2H), 3.27 (dd, J = 8.1, 7.3 Hz, 2H), 2:59 (m, 2H), 2:05 (d, 3H), 2.01-1.92 (m, 1H), 1.87-1.76 (m, 1H), 1.72-1.62 (m, 2H), 1.60-1.45 (m, 3H), 1.44-1.22 (m, 3H) , 1.12-0.85 (m, 12H), 0.75 (t, J = 7.0 Hz, 3H)
• ¹³ C-NMR _(CDCl3) δ 171.8, 170.3, 74.4, 49.5, 47.0, 42.3, 40.9, 34.2, 33.2, 31.2, 26.3, 23.5, 21.9, 21.4, 20.7, 20.0, 16.4, 13.7
• APCI MS (m / z) 326 (M + H) ⁺

Example 2

Synthesis of 3- (acetylbutylamino) -propionic acid (R) -3,7-dimethyl-oct-6-nyl-ester

• ¹H-NMR (CDCl₃) δ 5.08 (m, 1H), 4.11 (m, 2H), 3.57 (dd, J = 7.1, 6.9 Hz, 2H), 3.28 (m, 2H), 2.60 (t, J = 7.1 Hz, 2H), 2.06 (d, 3H), 1.98 (m, 1H), 1.68 (m, 3H), 1.60 (m, 3H), 1.60-1.40 (m, 5H), 1.37-1.29 (m, 3H), 1.27-1.13 (m, 1H), 0.92 (m, 6H)
• EI MS (m/z) 325 (M)⁺

Analogously to Example 1, ethyl 3- (acetylbutylamino) propionate is reacted with beta-citronellol in the presence of the catalyst Amberlyst-15 and worked up accordingly. 3- (acetylbutylamino) -propionic acid (R) -3,7-dimethyl-oct-6-enyl ester is obtained as a slightly yellowish oil.

• ¹ H-NMR _(CDCl3) δ 5:08 (m, 1H), 4.11 (m, 2H), 3:57 (dd, J = 7.1, 6.9 Hz, 2H), 3.28 (m, 2H), 2.60 (t, J = 7.1Hz, 2H), 2.06 (d, 3H), 1.98 (m, 1H), 1.68 (m, 3H), 1.60 (m, 3H), 1.60-1.40 (m, 5H), 1.37-1.29 (m, 3H ), 1.27-1.13 (m, 1H), 0.92 (m, 6H)
• EI MS (m / z) 325 (M) ⁺

Example 3

Insect repellent test

Of the Try using hairless mice as a bite target performed for female Aedes aegypti.

Materials and procedures

4-6 Day old female Aedes aegypti from a laboratory colony that has been around Hatched in 1992 (origin of the strain: ORSTOM / WHO strain Bora-Bora). The females have no 24 hours before the trial Received blood meal. The target objects for the bites are hairless mice in a net-like cylinder cage be kept with protection for their eyes. The product is used in an amount of 0.5 g per mouse.

Then The mouse is placed in a glass cage (50 cm × 50 cm × 50 cm) cm) containing about 50 female mosquitoes. For The duration of 10 minutes will be the number of bites and landings recorded (cumulative data).

Of the Attempt will be stopped each time more than 5 bites occur. The same procedure is done every 2 hours (or every hour depending the result of the previous assessment) with a new sentence repeated by insects.

Of the Try running for up to 8 hours if the product then it is still effective.

• F = Formulierung in Ethanol mit 10% v/v an dem jeweils angegebenen Wirkstoff:
• A = 3-(Acetylbutylamino)-propionsäure-ethylester (IR3535^®)
• B = Menthol
• C = Citronellol
• D = 3-(Acetylbutylamino)-propionsäure-2-iospropyl-5-methyl-cyclohexylester
• E = 3-(Acetylbutylamino)-propionsäure-(R)-3,7-dimethyl-oct-6-enylester
• S = Anzahl der Stiche
• L = Anzahl der Landungen
• Wdg. = Wiederholung
• stop = der Versuch wird abgebrochen, wenn mehr als 5 Stiche auftreten

Tabelle 1 Anzahl der Stiche und Landungen

3 repetitions are performed on 3 mice each, ie 9 individual tests are performed per formulation product. Table 1 shows the results of all tests.

• F = Formulation in ethanol with 10% v / v of the respective active ingredient indicated:
• A = 3- (Acetylbutylamino) -propionic acid ethyl ester (IR3535 ^®)
• B = menthol
• C = citronellol
• D = 3- (acetylbutylamino) -propionic acid-2-iospropyl-5-methylcyclohexyl ester
• E = 3- (acetylbutylamino) -propionic acid (R) -3,7-dimethyl-oct-6-enyl ester
• S = number of stitches
• L = number of landings
• Wdg. = Repetition
• stop = the attempt is aborted if more than 5 stitches occur

Table 1 Number of stitches and landings

All Repellents other than menthol show the same efficacy.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 4116123 [0049]
• - DE 10244282 A [0057]
• - DE 10232595 A [0063]
• - US 624209951 [0070]
• WO 00/09652 [0070]
• WO 00/72806 [0070]
• WO 00/71084 [0070]
• - DE 10133202 A [0073, 0073]
• - DE 4308282 A [0100]

Cited non-patent literature

• M. Klier, F. Kuhlow, J. Soc. Cos. Chem., 27, pp. 141-153 (1976) [0005]
• - Synthetic Comm. 2001, 31 (2), 289 [0018]
• K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108 [0055]
• CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159 [0056]
• - K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 [0056]

Claims (17)

Compounds of the formula (I)

in which the radicals are defined as follows: R ¹ , R ² = straight-chain or branched alkyl having 1-20 carbon atoms, straight-chain or branched alkenyl having 2-20 carbon atoms, saturated, partially or completely unsaturated cycloalkyl having 3-10 carbon atoms, where Each ring can also be bridged with - (CH ₂ ) _n groups with n = 1 to 3, where R ¹ and R ^{2 are} identical or different, where R ¹ and R ^{2 are} further saturated and / or unsaturated alkyl, saturated, partially or fully unsaturated cycloalkyl and / or heteroatom substituents may be substituted in different positions, wherein in the R ¹ and R ² one or two carbon atoms through the heteroatoms and / or atomic groups -O-, -N =, -C (O) -, -C (O) O- and / or -C (O) NH- can be replaced, R ³ = cyclic or acyclic, esterified monoterpenoid. Compounds according to claim 1, characterized that the esterified monoterpenoid is an oxygen-containing terpenoid or a related compound. Compounds according to claim 1 or 2, characterized that the esterified monoterpenoid formally consists of two isoprene units consists. Compounds according to one or more of the claims 1 to 3, characterized in that the esterified monoterpenoid based on an essential monoterpene. Compounds according to one or more of the claims 1 to 4, characterized in that the esterified monoterpenoid is an oily extract. Compounds according to one or more of Claims 1 to 5, characterized in that the terpene alcohol on which the esterified monoterpenoid is based is selected from the group consisting of

Process for the preparation of compounds of the formula I according to one or more of Claims 1 to 6, characterized in that a compound of the formula (II)

where R ¹ and R ^{2 are} each as defined in any of claims 1 to 6 and R ^{3 is} H or an alkoxy group containing 1 to 8 carbon atoms, reacted with a terpene alcohol R ³ -H, R ^{3 being} a Meaning according to one of claims 1 to 6 has. A method according to claim 7, characterized in that a compound of formula (II), wherein R ³ * is ethoxy, is reacted in an acid- or base-catalyzed transesterification. Use of the compounds according to one or more of claims 1 to 6 as a repellent in cosmetic and / or dermatological formulations for defense and / or deterrence of arthropods. Use of the compounds according to one or more of claims 1 to 6 as a formulation aid the production of cosmetic or dermatological preparations. Use of compounds according to one or more of Claims 1 to 6 in cleansing compositions or in the form of a detergent, wax, gel, shampoo, spray, solid product, emulsion, cream or dispersion. Preparation containing at least one compound the formal (I) according to one or more of claims 1 until 6. Preparation according to claim 12, characterized in that that they selected at least one other active substance from UV filters, flavone derivatives, chromone derivatives, aryloximes and parabens. Preparation according to claim 12 or 13, characterized that they have one or more other antioxidants and / or vitamins contains. Preparation according to one or more of the claims 12 to 14, characterized in that at least one further Insect repellent is included. Process for the preparation of a preparation according to at least one of claims 12 to 15, characterized that at least one compound of the formula (I) and optionally further Active substances with a cosmetically or dermatologically suitable Carriers are mixed. Use of a preparation after at least one of claims 12 to 15 for topical application or to Application on a surface.