DE102012008892A1 - Use of substituted cyclohexanol ether derivatives e.g. as antimicrobial active substance, preferably antibacterial active substance and as anti-acne-, antidandruff-, deodorant- or antiperspirant active substance, and in cosmetic formulation - Google Patents

Abstract

Use of substituted cyclohexanol ether derivatives (I) as an antimicrobial active substance, is claimed. Use of substituted cyclohexanol ether derivatives of formula (I) as an antimicrobial active substance, is claimed. R1-R5 : H, OH, OCOCH 3, O(CH 2CH 2O) nH, halo, 1-20C alkyl (optionally substituted by OH) or 1-20C O-alkyl; n : 1-20; and R6 : 1-20C alkyl (optionally substituted by OH) or -(CH 2CH 2O) nH. Independent claims are also included for: (1) a formulation comprising (I) and at least one carrier; (2) a composition comprising (I) and at least one antioxidant; (3) preparing the formulation, comprising mixing (I) with the carrier; and (4) 4-(2-hydroxy-ethoxy)-cyclohexanol, 2-(4-methoxy-cyclohexyloxy)-ethanol and 2-tert-butyl-4-methoxy-cyclohexanol. [Image] ACTIVITY : Antibacterial; Antiseborrheic; Dermatological. The antibacterial activity of (I) was tested against Candida albicans (strain ATCC 10231). The results showed that 2-cyclohexyloxy-ethanol (2% in water-ethanol mixture) decreased colony forming units from 6x 10 3> to 0. MECHANISM OF ACTION : None given.

Description

The present invention relates to the use of at least one Cyclohexanoletherderivats of formula I as an antimicrobial agent or as an anti-acne, anti-dandruff, deodorant or Antitranspirantwirkstoff, preparations containing these compounds, and specific cyclohexanol ether derivatives.

Microbial contamination is a major problem in our daily lives, for example in connection with cosmetic or pharmaceutical products, foods, surfaces in bathrooms or kitchens or surgical instruments. Usually, preservatives are used to avoid microbial contamination.

Antimicrobial agents, however, are not only necessary as preservatives. Antimicrobial agents also play an important role in many cosmetic applications:
Dandruff is a widespread disorder of the scalp that is usually accompanied by mild to moderate itching. The formation of such common dandruff is not to be understood as a skin disease in the general sense. Dandruff can be caused by scalp disorders, such as those caused by excessive sun exposure, environmental influences from the air or cosmetic hair products. The dandruff in this case caused by an overproduction of horny cells, triggered by tiny inflammatory foci of the scalp, the cause z. B. an increased bacterial colonization with fungi (such as Malassezia furfur or Malassezia globosa) or bacteria. As a result, the incompletely matured horny cells prematurely escape into larger cell aggregates (dandruff). As the outermost layer of the skin becomes thinner due to the loss of skin cells, dandruff leads to an increased sensitivity of the scalp, which manifests itself in itching and redness.

Acne is a skin disorder that manifests itself in inflamed papules, pustules or nodules, caused by increased talk production and keratinization of the skin. The inflammation can be associated with redness, swelling and pressure pain. In addition to genetic predisposition, androgens, comedogenic substances (eg in cosmetics), smoking, stress or excessive colonization of the skin with bacteria may be possible causes of acne formation. Acne can be caused for example by microorganisms such as Propionibacterium acnes, Propionibacterium granulosum or Staphylococcus epidermidis. Propionibacterium acnes is a bacterium that usually populates the skin and feeds on sebum. For example, acne can develop when the number of these bacteria is increased. The presence of bacteria in the follicles leads to inflammatory reactions, which manifest themselves in the form of red nodules or pustules. The production of free fatty acids by the bacteria further promotes the inflammatory reaction in the follicle.

In addition to water and salt, armpit sweat contains many other substances (such as fats, amino acids, sugars, lactic acid, urea, etc.). Freshly formed sweat is odorless; The typical smell of sweat is created only by the action of skin bacteria on the sweat, which decompose it. Examples of such bacteria are Staphylococcus, Corynebacterium or Malassezia. In deodorants, therefore, in addition to odors and antiperspirants usually antimicrobial substances are used to control the bacteria that are involved in the formation of odor.

When antimicrobial substances are used in preparations, their suitability in particular, but also their formability (that is to say solubility, stability, etc.) in the corresponding products (eg shampoos, creams, deodorants) are of great importance. Especially in cosmetics, these properties are essential. For example, it is particularly desirable that the ingredients are present at normal pressure between -5 ° C and 40 ° C in a liquid state.

The aim of the present invention is therefore to provide new ingredients with antimicrobial activity, which have the above-mentioned advantageous properties.

Surprisingly, it has now been found that certain cyclohexanol ether derivatives have the abovementioned properties while at the same time having outstanding antimicrobial activity.

The prior art discloses special cyclohexanol derivatives and their use in cosmetics:
WO 2009/087242 A2 describes the use of trans-4-tert-butyl-cyclohexanol to reduce skin irritation.

WO 94/10117 discloses the use of cyclohexanol derivatives to produce a cooling effect on the skin.

US 2006/0045892 A1 discloses cyclohexanol derivatives for the improvement of the skin appearance by reducing skin redness and skin irritations.

None of the documents discloses cyclohexanol ether derivatives or their antimicrobial use.

worin R1, R2, R3, R4 und R5 unabhängig voneinander stehen für einen Rest ausgewählt aus

• – H, OH, OCOCH₃, O(CH₂CH₂O)_nH, wobei n = 1 bis 20, Halogen,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 20 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 20 C-Atomen,

und worin R6 steht für einen Rest ausgewählt aus

• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 20 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – (CH₂CH₂O)_nH, wobei n = 1 bis 20,

als antimikrobieller Wirkstoff.A first object of the present invention is therefore the use of at least one compound of the formula I.

wherein R1, R2, R3, R4 and R5 independently represent a radical selected from

• - H, OH, OCOCH ₃ , O (CH ₂ CH ₂ O) _n H, where n = 1 to 20, halogen,
• Straight-chain or branched alkyl group having 1 to 20 C atoms, which may be optionally substituted by one or more OH groups,
• Straight-chain or branched O-alkyl group having 1 to 20 C atoms,

and wherein R6 is a radical selected from

• Straight-chain or branched alkyl group having 1 to 20 C atoms, which may be optionally substituted by one or more OH groups,
• - (CH ₂ CH ₂ O) _n H, where n = 1 to 20,

as antimicrobial agent.

According to the invention, an antimicrobial agent is understood as meaning a substance which reduces the growth of microorganisms or kills or inactivates the microorganisms.

The compounds of the formula I according to the invention can be used to inhibit the growth and multiplication of the microorganisms. Microorganisms are understood as meaning, for example, bacteria (gram-positive and gram-negative bacteria), yeasts, fungi or viruses. Examples of microorganisms are microorganisms selected from Staphylococcus, Micrococcus, Escherichia, Enterobacter, Pseudomonas, Bacillus, Salmonella, Serratia, Shigella, Porphyromonas, Prevotella, Wolinella, Campylobacter, Propionibacterium, Streptococcus, Corynebacterium, Treponema, Fusobacterium, Bifidobacterium, Lactobacillus, Actinomyces, Candida , Malassezia, Aspergillus, Herpes simplex 1 and 2.

Specifically, compounds of the present invention are antimicrobially active against Staphylococcus epidermidis, Staphylococcus aureus, Corynebacterium xerosis, Malassezia furfur, Propionibacterium acnes, Pseudomonas aeruginosa, Salmonella enteric, Serratia marcescens, Escherichia coli, Enterobacter gergovia, Aspergillus niger, Aspergillus brasiliensis and Candida albicans.

The antimicrobial compounds of the formula I are distinguished by a good antimicrobial activity, which means that the number of germs in a medium can be reproducibly reduced or the germ multiplication is suppressed (see examples).

The antimicrobial agents of the present invention can be used in a variety of formulations or applications, such as, for example, cosmetic / pharmaceutical formulations, medical devices, foods or household products. Specifically, for example, antimicrobial cleaning products, soaps, disinfectants, dentures or bone cement with antimicrobial activity, dental fillings and dentures, dental and oral care products, personal care products (creams, shampoos, lotions, detergents, deodorants, etc.), toiletries, kitchens and bathroom items, dishwashers or food and beverage trade.

The compounds of formula I can be used advantageously for preservative improvement.

Advantageously, for example, the use of the antimicrobial agents of the invention in dental or oral care products, eg. B. for the treatment or prophylaxis of plaque, tooth decay or bad breath, caused by microorganisms such as Streptococcus sobrinus, Streptococcus mutans, Streptococcus gordonii, Streptococcus salivaris, Streptococcus sanguis, Actinomyces, Lactobacilli, Fusobacterium, Veillonella, Treponema. denticola, Porphyromonas. gingivalis, Bacteroides or Peptostreptococcus.

As multifunctional substances, the compounds of the formula I are suitable for use as antioxidants or odorous fragrances for deodorizing and masking unwanted odors of the ingredients in formulations. In addition, they have excellent solvent properties. They may have moisturizing, astringent, skin cooling, antistatic or hair conditioning properties. The compounds of formula I are useful as skin care additives. These include anti-aging, anti-irritant and anti-inflammatory effects. Unwanted reddening of the skin can thus be reduced. The liquid substances have excellent spreading properties and produce a pleasant skin feel of the formulation. Especially in combination with traditional preservatives, improvements in the preservation result can be achieved. The effect of cosmetic alcohols, such as. As glycols, can be reinforced by the substances. In their combination with active ingredients for influencing the skin color, such. As chemically or biologically acting skin lightening or chemically or biologically acting skin-tanning agents, an efficacy enhancement is possible. In sunscreen formulations, fabrics of the present invention are eminently suitable for increasing protection factors (sun protection factor, UVA protection factors such as PPD [persistent pigment darkening], factors expressing protection against infrared or visible light).

Another object of the present invention is the use of the compounds of formula I as an anti-acne, anti-dandruff, deodorant or antiperspirant active.

In particular, the compounds of the formula I are suitable for the treatment or prophylaxis of acne which is triggered by microorganisms such as Propionibacterium acnes, Propionibacterium granulosum or Staphylococcus epidermidis. Suitable formulations for this are described below.

Furthermore, the use of compounds of the formula I as antidandruff active ingredient is advantageous, both for the treatment and for the prophylaxis. Suitable formulations, for example shampoos, are also described below.

Also advantageous is the use as active ingredient in deodorants or antiperspirants. On the one hand, some of the compounds according to the invention have an inherent odor which can mask unpleasant odors and thus have a deodorizing effect. Another advantage is that the compounds increase the skin moisture and thus have an advantageous effect on the appearance of the skin (eg skin smoothing effect).

The use in deodorants or antiperspirants is furthermore advantageous, since the compounds of the formula I have an antimicrobial action against the bacteria, which are responsible for the decomposition of the perspiration and thus for the formation of the odor. It is particularly advantageous in this case that the compounds can act bacteriostatically or bactericidally depending on the test germ. A bacteriostatic effect is achieved when the proliferation of a bacterium is indeed inhibited, whereby the odor is suppressed, but the bacterium is not killed. As a result, the natural skin flora can be maintained advantageously.

In particular, the compounds of formula I have a bacteriostatic effect against Staphylococcus epidermidis.

Possible formulations for deodorants or antiperspirants are described below.

The use according to the invention of the compounds of the general formula I can be carried out both in the cosmetic sense and in the pharmaceutical sense. A pharmaceutical application is conceivable, for example, in anti-acne agents.

Preferably, the use is cosmetic. Thus, a non-therapeutic use of the o. G. Compounds or their preparations for the prevention of unwanted changes in the appearance of the skin, as occurs in acne possible.

The compounds of formula I have an unexpectedly good antimicrobial activity, as set forth in the examples. Furthermore, the compounds of the formula I are advantageously usable in formulations, since they can be well incorporated into the corresponding formulations due to their good solubilities.

According to the invention, of the compounds of the formula I, all possible ring configuration isomers are included, i. H. both cis and trans isomers are conceivable.

According to the invention, the compounds of the formula I also include compounds in which one or more atoms have been replaced by other isotopes, in particular compounds in which H atoms have been replaced by deuterium (D).

In the compounds of the formula I, R 6 is preferably a radical selected from a straight-chain or branched alkyl group having 1 to 12 C atoms and (CH ₂ CH ₂ O) _n H, where n = 1 to 2.

R 6 particularly preferably represents a radical selected from a straight-chain or branched alkyl group having 1 to 6 C atoms, and (CH ₂ CH ₂ O) _n H, where n = 1 to 2.

Most preferably, R 6 is a radical selected from CH ₃ and CH ₂ CH ₂ OH.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 12 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 12 C-Atomen.

R1 preferably represents a radical selected

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 12 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 12 C atoms.

R1 particularly preferably represents a radical selected from H and straight-chain or branched alkyl group having 1 to 12 C atoms.

Most preferably, R 1 is a radical selected from H and straight-chain or branched alkyl group having 1 to 6 C atoms, particularly preferably a radical selected from H and t-butyl.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 12 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 12 C-Atomen.

R 2 in formula I preferably represents a radical selected from

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 12 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 12 C atoms.

Particularly preferably, R 2 is a radical selected from H and straight-chain or branched alkyl group having 1 to 12 C atoms.

Most preferably, R 2 is a radical selected from H and straight-chain or branched alkyl group having 1 to 6 C atoms, particularly preferably a radical selected from H and t-butyl.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 12 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 12 C-Atomen.

R 3 in formula I preferably represents a radical selected from

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 12 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 12 C atoms.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 6 C-Atomen.

Particularly preferably, R 3 is selected from a radical

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 6 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 6 carbon atoms.

Most preferably, R3 is a radical selected from H, OH, OCH ₂ CH ₂ OH, OCH ₃ and CH ₂ OH.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 12 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 12 C-Atomen.

R4 in formula I preferably represents a radical selected from

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 12 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 12 C atoms.

R4 particularly preferably represents a radical selected from H and straight-chain or branched alkyl group having 1 to 12 C atoms.

Most preferably, R4 is a radical selected from H and straight-chain or branched alkyl group having 1 to 6 C atoms, particularly preferably a radical selected from H and t-butyl. In a most preferred embodiment, R4 is H.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 12 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 12 C-Atomen.

R5 in formula I preferably represents a radical selected from

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 12 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 12 C atoms.

Particularly preferably, R 5 is a radical selected from H and straight-chain or branched alkyl group having 1 to 12 C atoms.

Most preferably, R 5 is a radical selected from H and straight-chain or branched alkyl group having 1 to 6 C atoms, particularly preferably a radical selected from H and t-butyl. In a most preferred embodiment, R5 is H.

• – H, OH, O(CH₂CH₂O)_nH, wobei n = 1 bis 2,
• – geradkettige oder verzweigte Alkylgruppe mit 1 bis 12 C-Atomen, welche optional mit ein oder mehreren OH-Gruppen substituiert sein kann,
• – geradkettige oder verzweigte O-Alkylgruppe mit 1 bis 12 C-Atomen.

In one embodiment, therefore, R1, R2, R3, R4 and R5 independently of one another are selected from a radical

• - H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2,
• Straight-chain or branched alkyl group having 1 to 12 C atoms, which may be optionally substituted by one or more OH groups,
• - straight-chain or branched O-alkyl group having 1 to 12 C atoms.

In a further embodiment, R1, R2, R4 and R5 independently of one another are a radical selected from H and t-butyl.

Particular preference is given to the use of one or more compounds selected from the compounds of the formulas I-1 to I-8:

Very particular preference is given to the use of the compound of the formula I-1, I-2 and / or I-3.

For the purposes of the present invention, a straight-chain or branched alkyl group having 1 to 6 C atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, pentyl, isopentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2- or 1,2,2-trimethylpropyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1, 2 -, 3- or 4-methylpentyl or hexyl.

In the case of an alkyl group having 1 to 12 C atoms, the radicals listed above may, for example, also be heptyl, 1-ethylpentyl, octyl, 1-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

An alkyl group having 1 to 20 C atoms is also understood to mean tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.

Analogously, an O-alkyl group is an alkyl group, as defined above, which is bonded via an oxygen atom to the compound of the formula I.

Halogen is a halogen radical, preferably a radical selected from F, Cl, Br or I.

The compounds of the formula I can be prepared by hydrogenation of corresponding aromatic starting products by methods known to the person skilled in the art with hydrogen and using a suitable Ni, Co, Pt, Pd or Rh catalyst (see, for example, US Pat. Alonso et al, 2008, Tetrahedron 64, 1847-1852 or Bai et al, 2010, Catalysis Communications 12, 212-216 ).

The educts, as well as the other necessary substances in the synthesis are commercially available or accessible by syntheses known to those skilled in the literature. Thereby it is not difficult for the skilled person to select the suitable reaction conditions such as solvent or temperature.

Typically, the reaction takes place at temperatures below 100 ° C and a pressure less than 200 bar, z. B. at 100 bar or 5 bar.

Examples of possible solvents are 2-propanol, ethyl acetate or tetrahydrofuran.

The reaction time is typically several hours, for example 1 to 5 hours.

Another object of the present invention is also a preparation containing at least one compound of formula I, as defined above, and at least one suitable carrier.

The preparation can be either a cosmetic or a pharmaceutical preparation. It is preferably a cosmetic preparation.

Preferred embodiments of the radicals R 1 to R 6 of the compounds of the formula I are defined here as described above.

The preparations are, for example, topically applicable preparations, for example cosmetic or dermatological formulations or medical products. The preparations in this case contain a topically cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients. In the case of pharmaceutical preparations, the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients.

Preparations for use in the mouth contain a carrier which is suitable for these applications.

For the purposes of the present invention, the term agent or formulation is used synonymously in addition to the term preparation.

Topically applicable means according to the invention that the preparation is applied externally and locally, d. H. that the preparation must be suitable, for example, to be applied to the skin can.

The preparations may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

The at least one compound of the formula I is typically present in the preparations according to the invention in amounts of from 0.01 to 20% by weight, preferably in amounts of from 0.05 to 10% by weight, particularly preferably in amounts of 0.1% by weight. -% to 5 wt .-% and most preferably used in amounts of 0.5 to 2 wt .-%, based on the total amount of the preparation. The expert does not have any difficulties in selecting the quantities according to the intended effect of the preparation.

The preparation is preferably a deodorant, an antiperspirant, an anti-dandruff or anti-acne agent or an antibacterial preparation, in particular for dental or oral care.

Anti-acne agents containing the compounds of the invention may be in the form of soaps, cleansers, solutions, suspensions, emulsions, creams, gels, pastes, lotions, powders, oils, sticks or sprays. Other possible ingredients in the formulations are described in detail below.

Anti-dandruff agents containing the compounds of the invention may be in the form of, for example, a shampoo or conditioner which may be applied before or after washing, dyeing or bleaching the hair. Alternatively, a formulation is also possible, in the form of a lotion or a gel for hair styling, for hair treatment or for hair drying, in the form of a hair color, a formulation for perming, or a formulation for hair coloring or bleaching. Such a cosmetic formulation may contain a number of other ingredients, such as surfactants, thickeners, polymers, emollients, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, antifat agents, dyes or pigments that color the formulation or hair, or other ingredients commonly used in hair care products. Further ingredients are described in detail in the following of the application.

For example, deodorants or antiperspirants may be in the form of creams, gels, lotions, emulsions, deodorant sticks, rollers, sprays or pump sprays. The compounds of formula I are usually combined with a carrier material suitable for deodorants or antiperspirants. Examples of suitable carrier materials are glyceryl stearate, aluminum chlorohydrate, propylene glycol, carbomer, glycerol, dicapryl ether, ethanol, glyceryl cocoate, cylomethicone, dimethicone, dipropylene glycol, stearyl alcohol, mineral oil, phenyltrimethicone or sodium stearate.

In the above-mentioned formulations, the compounds of the formula I can advantageously be combined with all other known preservatives or antimicrobial agents. This can advantageously have synergistic effects with the compounds of the formula I result. Examples of such preservatives or antimicrobial agents are anisic acid, alcohol, ammonium benzoate, ammonium propionate, benzoic acid, benzoyl peroxide, bronopol, butylparaben, benzethonium chloride, benzalkonium chloride, 5-bromo-5-nitro-1,3-dioxane, benzyl alcohol, boric acid, benzisothiazolinone, benzotriazole, Benzylhemiformate, benzylparaben, 2-bromo-2-nitropropane-1,3-diol, butylbenzoate, caprylylglycol, chlorphenesin, caprylic / capringlycerides, caprylglycol, camellia sinensis leaf extract, candida bombicola / glucose / methyl rapeseedate, chlorxylenol, chloroacetamide, chlorhexidine, chlorobutanol, Calcium benzoate, calcium paraben, calcium propionate, calcium salicylate, calcium sorbate, captan, chloramine T, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dithyrochloride, chloroacetamine, p-chloro-m-cresol, chlorophene, p-chlorophenol, chlorothymol, climbazole, citrus grandis (grapefruit), fruit extract, Citrus grandis (Grapefruit) seed extract, m-cresol, o-cresol, p-cresol, mixed cresols, Diazolidinyl urea, Dichlorobenzylalcohol, dimethyloxazolidine, DMDM hydantoin, Dimethylhydroxmethylpyrazol, dehydroacetic acid, diazolidinyl urea, DEDM hydantoin, DEDM hydantoin dilaurate, Dibrompropamidindiisothionat, Dimethylolethylenthioharnstoff, Dithiomethylbenzamid, DMDM hydantoins, DMHF, domiphen bromide, 7-Ethylbicyclooxazolidin, ethylparaben, Ethylhexylglycerin, ethanol, ethyl ferulate, farnesol, formaldehyde , Ferulic acid, fumaric acid, glyceryl caprate, glutaral, glycerol formate, glyoxal, hexamidine diisethionate, hexetidine, hexamidine, hexamidine diparaben, 1,2-hexanediol, 1,6-hexanediol, hexamidine paraben, 4-hydroxybenzoic acid, hydroxymethyldioxazabicyclooctane, imidazolidinyl urea, imidiazolidinyl urea NF, isobutyl paraben, isothiazolinone, Iodopropynyl butylcarbamate, isodecylparaben, isopropylcresol, isopropylparaben, isopropylsorbate, potassium sorbate NF FCC, copper nutate, potassium benzoate, potassium ethylparaben, potassium methylparaben, potassium paraben, potassium phenoxide, potassium o-phenylphenate, K aliumpropionate, potassium propylparaben, potassium salicylate, potassium sorbate, methylparaben, methylisothiazolinone, methylchloroisothiazolinone, Methylbenzethonium chloride phenol, methyldibromoglutaronitrile, methenammonium chloride, methylbromoglutaronitrile, 2-methyl-5-cyclohexylpentanol, magnesium benzoate, magnesium propionate, magnesium salicylate, MDM hydantoin, MEA benzoate, MEA o-phenylphenate, MEA salicylate, methylchloristhiazolinone, sodium benzoate NF FCC, sodium caprylate, sodium dehydroacetate, sodium dehydroacetate FCC, Sodium hydroxymethylglycinate, Sodium methylparaben, Sodiumpropylparaben, Sodium iodate, Nimbevine seed oil, Nisin, Sodium benzoate, Sodium butyl paraben, Sodium p-chloro-m-cresol, Sodium ethyl paraben, Sodium formate, Sodium hydroxymethanesulfonate, Sodium isobutyl paraben, Sodium paraben, Sodium phenol sulfonate, Sodium phenoxide, Sodium o-phenyl phenate, Sodium propionate, Sodium propyl paraben, Sodium pyrithione, sodium salicylate, sodium sorbate, ortholphenylphenol, phenoxyethanol, propylparaben, polymethoxybicyclicoxazolidine, pinus pinaster bark extract, poloxamer 188, PVP-iodines, parabens, pircotone olamine, phenethyl alcohol, butadiene lyaminopropyl biguanide, polyquaternium-42, PEG-5 DEDM hydantoin, PEG-15 DEDM hydantoin, PEG-5 hydantoin oleate, PEG-15 DEDM hydantoin stearate, phenethyl alcohol, phenol, phenoxyethyl paraben, phenoxy isopropanol, phenyl benzoate, phenyl mercuric acetate, phenyl mercuric benzoate, phenyl mercuric borate, Phenyl mercury bromide, phenylmercuric chloride, phenylparaben, o-phenylphenol, piroctone oleamines, polyaminopropyl biguanide stearate, propionic acid, propyl benzoate, 1,2-propylene glycol, 1,3-propylene glycol, quaternium-15, quaternium-8, quaternium-14, rosmarinus officinalis leaf extract, sorbic acid NF FCC, selenium disulphin, sorbic acid, salicylic acid, silver borosilicate, silver magnesium aluminum phosphate, triclosan, di-alpha-tocopherol, tocopherol acetate, thimersal, triclocarban, TEA sorbate, thimerosal, usnic acid, undecylenoyl PEG-5 paraben, Vitis vinifera seed extract, tea tree oil, hydrogen peroxide, Zinc pyrithione, zinc oxide, zinc phenolsulphonate or combinations thereof.

The compounds of formula I can also be combined with antibiotics. Any of the known antibiotics, for example beta-lactam, vancomycin, macrolides, tetracyclines, quinolones, fluoroquinolones, nitrated compounds (such as nitroxoline, tilboquinol or nitrofurantoin), aminoglycosides, phenicoles, lincosamides, synergistines, fosfomycin, fusidic acid, oxazolidinones, rifamycins can be used according to the invention , Polymixyne, Gramicidine, Tyrocydine, Glycopeptide, Sulfonamide or Trimethoprime.

The formulations of the invention may also advantageously contain at least one antioxidant.

The protective effect of preparations against oxidative stress or against the action of radicals can be improved if the preparations contain one or more antioxidants, wherein the skilled person has no difficulty in selecting suitable fast or delayed-acting antioxidants.

Likewise, antioxidants can support the stability of the compounds contained in the preparations, in particular the stability of cyclohexanol ethers according to the invention.

In addition to one or more compounds of the formula I, preferred preparations additionally comprise one or more antioxidants for protecting the ethers against autoxidation.

According to the invention, mixtures of at least one compound of the formula I and at least one antioxidant can also be present in the form of a premix, which is incorporated as such into the preparation.

Accordingly, a composition comprising at least one compound of the formula I as defined above and at least one antioxidant are also provided by the present invention. Suitable antioxidants are listed below.

Preferred compositions which may serve as a premix comprise at least one compound of the formula I and at least one antioxidant in a weight ratio of 99.9: 0.1 to 50.0: 50.0.

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, carotenes (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 their Derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthionine sulfones, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μmol (kg / 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, pentasodium ethylenediamine tetramethylene phosphonate 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), and benzylic resin, benzylic acid, rutinic acid and their derivatives, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene , Butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg 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 unabhängig voneinander H oder lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen,
R⁵ H, 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-dimethoxybenzyl)-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 ,
XO or NH,
R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,
R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,
R ⁴ each independently of one another are H or linear or branched alkyl having 1 to 8 C atoms,
R ^{5 is} H, 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, more 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-dimethoxybenzyl) -malonic acid-bis- (2-ethylhexyl) ester (z. B. RonaCare ^® AP).

Mixtures of antioxidants are also suitable for use in the formulations of the invention. Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid, 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 (. eg Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex ^® 2004th). Such antioxidants are used with the compounds of the invention in such compositions usually 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. With effects of the substitution pattern of mono- and dihydroxyflavones deal 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 sometimes have no antioxidant properties ,

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, A. EMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH dependence of the antioxidant activity of hydroxyflavones. Quercetin shows the highest activity of the investigated structures over the entire pH range.

Usually, antioxidants in amounts of up to 5% by weight are incorporated into the formulations.

Oral or dental care formulations may be in the form of, for example, a toothpaste, a mouthwash, a toothpowder, a chewing gum, a troche, a mouthwash, dental floss, dental cement or paint.

Corresponding formulations may contain other conventional ingredients such as humectants, surfactants, structuring agents, gelling agents, abrasives, fluoride sources, desensitizers, flavoring agents, colorants, sweeteners, preservatives, antimicrobials or tartar or tartar agents.

Suitable moisturizers for use in dentifrices are, for example, polyhydric alcohols, such as xylitol, sorbitol, glycerol, propylene glycol or polyethylene glycol. Blends of glycerin and sorbitol are particularly suitable. A humectant helps to ensure that toothpaste formulations do not dry out on contact with air and that the mouthfeel of the cream (soft texture, flowability, sweetness) is pleasant. Typically, these humectants are included in the formulation in amounts of 0-85% by weight, preferably 0-60% by weight.

Suitable surfactants in dentifrices, mouthwashes, etc. are typically water-soluble organic compounds and may be anionic, nonionic, cationic or amphoteric. Preferably, a reasonably stable surfactant should be selected. Anionic surfactants are, for example, water-soluble salts of C _10-18 alkyl sulphates (eg sodium lauryl sulphate), water-soluble salts of C _10-18 ethoxylated alkyl sulphates, water-soluble salts of C _10-18 alkyl sarcosinates, water-soluble salts of sulphonated monoglycerides of C _{10. 18} fatty acids (eg, sodium coconut fatty acid monoglyceride sulfonate), alkylaryl sulfonates (eg, sodium dodecyl benzene sulfonate), and sodium salts of coconut fatty acid amide of N-methyl taurine.

Nonionic surfactants useful in oral care products include the condensation products of alkylene oxide groups with aliphatic or alkylaromatic compounds such as polyethylene oxide condensates of alkylphenols, ethylene oxide / propylene oxide copolymers (available under the name 'Pluronic'), ethylene oxide / ethylene diamine copolymers, ethylene oxide condensates of aliphatic alcohols , long-chain tertiary amine oxides, long-chain tertiary phosphine oxides, long-chain dialkyl sulfoxides and mixtures thereof. Alternatives to this are ethoxylated sorbitan esters, which are available, for example, via ICI under the name "Tween". Cationic surfactants are typically quaternary ammonium compounds having a C _8-18 alkyl chain, such as lauryltrimethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium chloride, di-isobutylphenoxyethoxyethyldimethylbenzylammonium chloride, coconut fatty acid alkyltrimethylammonium nitrite, and cetylpyridinium fluoride. Also suitable are benzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride and tertiary amines having a C _1-18 hydrocarbon group and two (poly) oxyethylene groups.

Amphoteric surfactants are typically aliphatic secondary and tertiary amines wherein the aliphatic radicals may be straight-chain or branched and wherein one of the aliphatic radicals is a C _8-18 group and the other radical contains an anionic hydrophilic group, for example, sulfonate, carboxylate, sulfates , Phosphonate or phosphate.

Normally, the surfactant is incorporated in the oral care formulation in an amount of 0-20% by weight, preferably 0-10% by weight.

Structure formers may be necessary in toothpastes or chewing gum to allow the desired structural properties and desired "mouthfeel". Suitable materials are, for example, natural gums such as gum tragacanth, xanthan gum, karaya gum and gum arabic, algae derivatives such as pearl moss and alginates, smectite such as bentonite or hectorite, carboxyvinyl polymers and water-soluble cellulose derivatives such as hydroxyethyl cellulose and sodium carboxymethyl cellulose. Improved structures can also be achieved if, for example, colloidal magnesium aluminum silicate is used. Typically, the structuring agent is included in an amount of 0-5 wt.%, Preferably 0-3 wt.% In the oral hygiene formulation.

Abrasives should preferably be able to brush and / or polish the teeth without damaging the enamel or dentin. Mostly they are used in toothpastes or toothpowders, but they can also be used in mouthwashes, etc. Suitable abrasives are, for example, silica abrasives such as hydrated silicates or silica gels, especially silica gels (e.g., 'Syloid' available from W.R. Grace and Company). Also suitable are the silica materials available under the name 'Zeodent' from J.M. Huber Corporation, and diatomaceous earth such as 'Celite' available from Johns-Manville Corporation. Alternative abrasives are alumina, insoluble metaphosphates such as insoluble sodium metaphosphate, calcium carbonate, dicalcium phosphate (in dihydrate and anhydrous forms), calcium pyrophosphate, polymethoxylates, and particular particulate curable polymerized resins such as melamine ureas, melamine formaldehydes, urea formaldehydes, melamine urea formaldehydes, crosslinked epoxies, melamines, phenolic resins, high purity celluloses (eg, 'Elcema' available from Degussa AG), and crosslinked polyesters. Typically, abrasives are incorporated in an amount of 0-80% by weight, preferably 0-60% by weight in the oral hygiene formulation.

Suitable fluoride sources are, for example, sodium fluoride, zinc fluoride, potassium fluoride, aluminum fluoride, lithium fluoride, sodium monofluorophosphate, stannous fluoride, ammonium fluoride, ammonium bifluoride and amine fluoride. The fluoride sources are preferably included in suitable amounts to provide about 50 ppm to about 4,000 ppm of fluoride ion in use.

Suitable desensitizing agents include, for example, formaldehyde, potassium nitrate, tripotassium citrate, potassium chloride and strontium chloride, strontium acetate and sodium citrate.

Flavors may be selected, for example, from oils of peppermint, spearmint, cranberry, sassafras and clove. Sweetening agents may also be used, for example, D-tryptophan, saccharin, dextrose, aspartame, levulose, acesulfame, dihydrochalcones and sodium cyclamate. Typically, all of these flavors are contained in amounts of 0-5 wt%, preferably 0-2 wt%. Dyes and pigments can be added to make the formulation more visually attractive. Frequently, titanium dioxide is used to obtain a strong white color.

As described above, the dental and oral care formulations of the invention may also contain one or more other antimicrobial agents. Suitable examples thereof are zinc salts (such as zinc citrate), cetylpyridinium chloride, bis-biguanides (such as chlorhexidine), aliphatic amines, bromochlorophenes, hexachlorophenes, salicylanilides, quaternary ammonium compounds and triclosan. Alternatively, enzymatic systems can be used, e.g. For example, a system containing lactoperoxidase and glucose oxidase can be used to generate antimicrobially effective amounts of hydrogen peroxide in the presence of glucose, water and oxygen.

The formulation may also contain alcohol. This is especially beneficial in mouthwashes.

The preparations according to the invention may also contain, in addition to the compounds of the formula I and the ingredients described above, further ingredients. In the following, further possible ingredients, in particular for cosmetic preparations, are described.

The preparations according to the invention may additionally contain at least one UV filter.

Organic UV filters, so-called hydrophilic or lipophilic sunscreen filters, are effective in the UVA range and / or UVB range and / or IR and / or VIS range (absorber). These substances can be used in particular under cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, triazine derivatives, β, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters described in the application WO-93/04665 be selected. Further examples of organic filters are in the patent application EP-A 0 487 404 specified. In the following, the named UV filters are usually named according to the INCI nomenclature.

In particular suitable for a combination are:
para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. under the name "Escalol 507" from the company. ISP, glyceryl PABA, PEG-25 PABA, z. B. under the name "Uvinul P25" from BASF.

Salicylates: Homosalates are sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. under the name "Neo Heliopan OS" from the Fa. Symrise, Dipropylene glycol salicylate, z. B. under the name "Dipsal" from the company. Scher, TEA salicylate, z. B. under the name "Neo Heliopan TS" of the Fa. Symrise.

β, β-diphenylacrylate derivatives: octocrylenes, e.g. B. under the name "Eusolex ^® OCR" from Merck "," Uvinul N539 "from BASF, Etocrylene, z. B. under the name "Uvinul N35" from BASF.

Benzophenone Derivatives: Benzophenone-1, e.g. B. operated under the name "Uvinul 400"; Benzophenone-2, e.g. B. operated under the name "Uvinul D50"; Benzophenone-3 or oxybenzone, e.g. B. operated under the name "Uvinul M40"; Benzophenone-4, e.g. B. operated under the name "Uvinul MS40"; Benzophenone-9, e.g. B. under the name "Uvinul DS-49" from the company. BASF, Benzophenone-5, Benzophenone-6, z. B. under the name "Helisorb 11" from the company. Norquay, Benzophenone-8, z. Sold under the name "Spectra-Sorb UV-24" by American Cyanamid, Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, marketed by Fa. Merck, Darmstadt under the name Eusolex ^® 4360th

Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. B. under the name "Mexoryl SD" from the company Chimex, 4-Methylbenzylidenecamphor, z. B. under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. under the name "Mexoryl SL" from the company Chimex, Camphor benzalkonium methosulfate, z. B. under the name "Mexoryl SO" from the company. Chimex, Terephthalylidenedicamphorsulfonsäure, z. B. sold under the name "Mexoryl SX" from the Fa Chimex, Polyacrylamidomethylbenzylidenecamphor operated under the name "Mexoryl SW" from the company Chimex.

Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B. under the name "Eusolex 232" from the company Merck, disodium phenyl dibenzimidazole tetrasulfonate, z. B. operated under the name "Neo Heliopan AP" of the Fa. Symrise.

Phenylbenzotriazole derivatives: Drometrizole trisiloxanes, e.g. B. under the name "Silatrizole" from the company. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, z. B. under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B. under the name "Tinosorb M" from BASF.

Triazine derivatives: ethylhexyltriazone, e.g. B. under the name "Uvinul T150" from the Fa. BASF, Diethylhexylbutamidotriazone, z. From the company Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines or 2,4,6-tris (biphenyl) -1, 3,5-triazines sold as Tinosorb A2B by BASF, 2,2 '- [6- (4-methoxyphenyl) -1,3,5-triazine-2,4-diyl] bis [5- (2-ethylhexyl) oxy ] -phenol, sold as Tinosorb S by BASF, N2, N4-bis [4- [5- (1,1-dimethylpropyl) -2-benzoxazolyl] phenyl] -N6- (2-ethylhexyl) -1,3,5 -triazine-2,4,6-triamine sold as Uvasorb K 2A from Sigma 3V.

Anthraniline derivatives: menthyl anthranilate, e.g. B. operated under the name "Neo Heliopan MA" by Fa. Symrise.

Imidazole derivatives: Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate derivatives: Polyorganosiloxanes containing functional benzalmalonate groups, such as. B. polysilicone-15, z. B. sold under the name "Parsol SLX" by Hoffmann LaRoche.

4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

Benzoxazole Derivatives: 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures thereof containing.

oder die UV-Filter der folgenden Strukturen

Piperazine derivatives such as the compound

or the UV filters of the following structures

It is also possible to use UV filters based on polysiloxane copolymers with a random distribution in accordance with the following formula, where z. B. a = 1.2; b = 58 and c = 2.8 are:

The compounds listed in the list are examples only. Of course, other UV filters can be used.

Suitable organic UV-protective substances are preferably selected from the following list: ethylhexyl salicylate, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4- Methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate, methylenebis (benzotriazolyl) tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxane, polysilicone-15, 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, 2, 4-Bis [5-1 (dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines and mixtures thereof.

These organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.

The preparations may contain, in addition to the compounds of the formula I and the optionally organic UV filters, as described above, further inorganic UV filters, so-called particulate UV filters.

These combinations with particulate UV filters are possible both as a powder and as a dispersion or paste of the following types.

In this case, both those from the group of titanium dioxides such. For example, coated titanium dioxide (for. Example Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO, Eusolex ^® T-OLEO), zinc oxides (eg. As Sachtotec® ^®), iron oxides and also cerium and / or zirconium oxides are preferred.

Furthermore, combinations with pigmentary Titandixoxid or zinc oxide are possible, wherein the particle size of these pigments is greater than or equal to 200 nm, for example ^® Hombitan FG or Hombitan ^® FF-Pharma.

It may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53 64 described, were treated. Here, one or more of the following aftertreatment components may be selected: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially Collagen or elastin), alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.

• – unbehandelte Titandioxide wie z. B. die Produkte Microtitanium Dioxide MT 500 B der Fa. Tayca; Titandioxd P25 der Fa. Degussa,
• – Nachbehandelte mikronisierte Titandioxide mit Aluminiumoxid und Siliciumdioxid Nachbehandlung wie z. B. das Produkt „Microtitanium Dioxide MT 100 SA der Tayca; oder das Produkt „Tioveil Fin” der Fa. Uniqema,
• – Nachbehandelte mikronisierte Titandioxide mit Aluminiumoxid und/oder Aluminiumstearate/laurate Nachbehandlung wie z. B. Microtitanium Dioxide MT 100 T der Fa. Tayca, Eusolex T-2000 der Firma Merck,
• – Nachbehandelte mikronisierte Titandioxide mit Eisenoxid und/oder Eisenstearate Nachbehandlung wie z. B. das Produkt „Microtitanium Dioxide MT 100 F” der Fa. Tayca,
• – Nachbehandelte mikronisierte Titandioxide mit Siliciumdioxide, Aluminiumoxid und Silicon Nachbehandlung wie z. B. das Produkt ”Microtitanium Dioxide MT 100 SAS”, der Fa. Tayca,
• – Nachbehandelte mikronisierte Titandioxide mit Natrumhexameta-phosphate, wie z. B. das Produkt ”Microtitanium Dioxide MT 150 W” der Fa. Tayca.

Preferably used particulate UV filters are:

• - untreated titanium dioxides such. The products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,
• Aftertreated micronised titanium dioxides with alumina and silica aftertreatment such. For example, the product "Microtitanium Dioxide MT 100 SA from Tayca; or the product "Tioveil Fin" from Uniqema,
• - Aftertreated micronized titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment such. B. Microtitanium Dioxide MT 100 T from. Tayca, Eusolex T-2000 from Merck,
• - Aftertreated micronized titanium dioxides with iron oxide and / or iron stearates aftertreatment such. B. the product "Microtitanium Dioxide MT 100 F" Fa. Tayca,
• - Aftertreated micronized titanium dioxides with silicas, alumina and silicon aftertreatment such. B. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,
• - Aftertreated micronized titanium dioxides with Natrumhexameta-phosphate, such as. As the product "Microtitanium Dioxide MT 150 W" Fa. Tayca.

• – Octyltrimethoxysilane; wie z. B. das Produkt Tego Sun T 805 der Fa. Degussa,
• – Siliciumdioxid; wie z. B. das Produkt Parsol T-X der Fa. DSM,
• – Aluminiumoxid und Stearinsäure; wie z. B. das Produkt UV-Titan M160 der Fa. Sachtleben,
• – Aluminium und Glycerin; wie z. B. das Produkt UV-Titan der Fa. Sachtleben
• – Aluminium und Silikonölen, wie z. B. das Produkt UV-Titan M262 der Fa. Sachtleben,
• – Natriumhexamethaphosphat und Polyvinylpyrrolidon,
• – Polydimethylsiloxane, wie z. B. das Produkt 70250 Cardre UF TiO2SI3” der Fa. Cardre,
• – Polydimethylhydrogensiloxane, wie z. B. das Produkt Microtitanium Dioxide USP Grade Hydrophobic” der Fa. Color Techniques.

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

• - octyltrimethoxysilanes; such as B. the product Tego Sun T 805 from Degussa,
• - silica; such as B. the product Parsol TX from DSM,
• Alumina and stearic acid; such as B. the product UV titanium M160 Fa. Sachtleben,
• - aluminum and glycerin; such as B. the product UV titanium from Fa. Sachtleben
• - Aluminum and silicone oils, such as. B. the product UV titanium M262 Fa. Sachtleben,
• Sodium hexamethaphosphate and polyvinylpyrrolidone,
• - Polydimethylsiloxane, such as. Example, the product 70250 Cardre UF TiO2SI3 "the Fa. Cardre,
• - Polydimethylhydrogensiloxane, such as. Example, the product Microtitanium Dioxide USP Grade Hydrophobic "from the company Color Techniques.

• – Unbehandelte Zinkoxide wie z. B. das Produkt Z-Cote der Fa. BASF (Sunsmart), Nanox der Fa. Elementis
• – Nachbehandelte Zinkoxide wie z. B. die folgenden Produkte:
• • ”Zinc Oxide CS-5” der Fa. Toshibi (ZnO nachbehandelt mit polymethylhydrogenosiloxane)
• • Nanogard Zinc Oxide FN der Fa. Nanophase Technologies
• • ”SPD-Z1” der Fa Shin-Etsu (ZnO nachbehandelt mit einem Silikongepfropften Acrylpolymer, dispergiert in Cyclodimethylsiloxane
• • ”Escalol Z100” der Fa ISP (Aluminiumoxid nachbehandeltes ZnO dispergiert in einer ethylhexyl methoxycinnamate/PVP-hexadecene/methicone copolymer Mischung)
• • ”Fuji ZNO-SMS-10” der Fa. Fuji Pigment (ZnO nachbehandelt mit Siliciumdioxid und Polymethylsilesquioxan);
• • Unbehandeltes Ceroxide Mikropigment z. B. mit der Bezeichnung ”Colloidal Cerium Oxide” der Fa Rhone Poulenc
• • Unbehandelte und/oder nachbehandelte Eisenoxide mit der Bezeichnung Nanogar der Fa. Arnaud.

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

• - Untreated zinc oxides such. For example, the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis
• - After-treated zinc oxides such. For example, the following products:
• "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with polymethylhydrogenosiloxane)
• • Nanogard Zinc Oxide FN from Nanophase Technologies
• "SPD-Z1" from Shin-Etsu (ZnO post-treated with a silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxanes
• "Escalol Z100" from ISP (alumina aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer blend)
• Fuji ZNO-SMS-10 from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane);
• • untreated ceroxide micropigment z. B. with the name "Colloidal Cerium Oxide" Fa Rhone Poulenc
• • Untreated and / or post-treated iron oxides called Nanogar from Arnaud.

By way of example, mixtures of various metal oxides, such as. As titanium dioxide and cerium oxide are used with and without Nachbenhandlung, such. As the product Sunveil A Fa. Ikeda. In addition, mixtures of alumina, silica and silicon post-treated titanium dioxide, zinc oxide mixtures such. B. the product UV titanium M261 Fa. Sachtleben be used.

These inorganic UV filters are incorporated usually in an amount of 0.1 weight percent to 25 weight percent, preferably 2 wt .-% - 10 wt .-%, in the preparations.

By combining one or more of said compounds with UV filter action, the protective effect against harmful effects of UV radiation can be optimized.

All mentioned UV filters can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form.

In this case, the capsules in preparations to be used according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the above-indicated weight percentages.

In the described preparations, which according to the invention contain at least one compound of the formula I, color pigments may furthermore furthermore be present, the layer structure of the pigments not being limited.

Preferably, the color pigment when used from 0.5 to 5 wt .-% should be skin-colored or brownish. The selection of a corresponding pigment is familiar to the person skilled in the art.

Preferred preparations may also contain at least one other cosmetic active ingredient, for example selected from anti-aging, anti-wrinkle, other anti-dandruff, other anti-acne, anti-cellulite active ingredients, other deodorants, skin lightening agents, self-tanning substances or vitamins.

The preparations may also contain, in addition to the compounds of the formula I, one or more anti-aging active ingredients. Suitable anti-aging active substances, in particular for skin-care preparations, are preferably 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, phosphatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z. B. Compounds that are converted to osmolytes by metabolic steps.

Preferably according to the invention as compatible solute substances selected from the group consisting of Pyrimidincarbonsäuren (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic diphosphoglycerate, N. acetylornithine, trimethylamine N-oxide di-myo-inositol-phosphate (DIP) , cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (firoin), 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.

In particular, ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives.

Additional can be used as anti-aging active ingredients Merck products such. B. 5,7-dihydroxy-2-methylchromone, marketed under the trade name used 5 RonaCare Luremine ^{®, ®} Ronacare isoquercetin, Ronacare ^® tiliroside or Ronacare ^® cyclopeptides.

The preparations may also contain one or more skin-lightening agents or synonymously depigmentation agents or melanogenesis inhibitors. In principle, skin-lightening active ingredients can be all active ingredients known to the person skilled in the art. Examples of compounds having skin-lightening activity are hydroquinone, kojic acid, arbutin, aloesin, niacinamide, azelaic acid, elagic acid, mulberry extract, magnesium ascorbyl phosphate, liquorice root extract, emblica, ascorbic acid or rucinol.

Furthermore, the preparations according to the invention may contain at least one self-tanning substance as further ingredient. Advantageous self-tanning substances which may be used include:
1,3-dihydroxyacetone, glycerolaldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2-hydroxy-1,4-naphthoquinone (Lawson ). Very particular preference is given to 1,3-dihydroxyacetone, erythrulose or their combination. Preferably, the at least one further self-tanning substance in the preparation in an amount of 0.01 to 20 wt .-%, particularly preferably in an amount of 0.5 to 15 wt .-% and most preferably in an amount of 1 to 8 Wt .-%, based on the total amount of the preparation.

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.

The present invention also provides a process for the preparation of a preparation as described above, which comprises mixing at least one compound of the formula I with a suitable carrier and optionally with auxiliaries and / or fillers. Suitable excipients and auxiliaries or fillers are described in detail in the following part.

The said constituents of the preparation can be incorporated in the usual way, by means of techniques which are well known to the person skilled in the art.

The cosmetic and dermatological preparations can be in various forms. So they can z. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. Oil-in-water (W / O / W) or O / W / O, a gel, a solid stick, an ointment or even an aerosol. Preference is given to emulsions. O / W emulsins are especially preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.

As an application form of the preparations to be used z. As: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols, patches, envelopes, dressings and sprays.

Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants, odor improvers.

Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. As animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or mixtures of these substances.

Powders and sprays may contain the usual excipients, for. As lactose, talc, silica, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can additionally the usual volatile, liquefied propellant, z. For example, chlorofluorocarbons, propane / butane or dimethyl ether. Also, compressed air is advantageous to use.

Solutions and emulsions may contain the usual carriers such as solvents, solubilizers and emulsifiers, eg. For example, water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, 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 ,

A preferred solubilizer in general is 2-isopropyl-5-methylcyclohexanecarbonyl-D-alanine methyl ester.

Suspensions may be the usual carriers such as liquid diluents, for. For example, water, ethanol or propylene glycol, suspending, z. For example, ethoxylated isostearyl, Polyoxyethylensorbitester and Polyoxyethylensorbitanester, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar and tragacanth or mixtures of these substances.

Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.

Surfactant-containing cleaning products may contain the usual excipients 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 glycerol fatty acid esters or mixtures of these substances.

Facial and body oils may contain the usual excipients such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.

Further typical cosmetic application forms are also lipsticks, lip balm sticks, powder, emulsion and wax make-up as well as sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms include, in particular, emulsions.

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

• – 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 acid, also natural oils such. Castor oil;
• - Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with alcohols of low C number, z. 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 selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 C atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 C atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 C atoms. Such ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, Erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, eg. B. jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C atoms. The fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

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

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. For example, 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 from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

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

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

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.

For example, O / W emulsifiers are selected as co-emulsifiers, principally from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W Emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers may also be lower or higher.

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

It is also advantageous to choose the fatty acid ethoxylates from the following group:
Polyethylene glycol (20) stearate, 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.

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

It is furthermore advantageous to use the polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol ( 20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate).

It is also convenient to select the sorbitan esters from the group of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) 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 having a chain length of 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 ethers of saturated and / or unsaturated, branched and / or or unbranched alcohols having a chain length of 8 to 24, in particular 12-18 C atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms and sorbitan esters saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a K ettenlänge of 8 to 24, in particular 12-18 C-atoms.

Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl, glyceryl monomyristate, glyceryl, diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol, sorbitan, sorbitan, sorbitan, Sorbitanmonoisooleat, sucrose, cetyl alcohol, stearyl, arachidyl, behenyl, Isobehenylalkohol, selachyl, Chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate or PEG-30 dipolyhydroxystearate.

The preparation may contain cosmetic adjuvants, which are commonly used in this type of preparations, such as. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.

It is possible to use as dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof. Particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerine and sorbitol.

A preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

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

The preparation may also be in the form of an alcoholic gel comprising one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickener, such as silica. The oily-alcoholic gels also contain natural or synthetic oil or wax.

The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.

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

The compounds of the formula I can also be used according to the invention in foods. The other explanations on food apply mutatis mutandis to dietary supplements and functional food.

The foods which can be fortified according to the present invention with one or more compounds of formula I include all materials suitable for consumption by animals or for human consumption, for example vitamins and provitamins thereof, fats, minerals or amino acids ". The food can be solid but also in liquid form, so as a beverage present.

Foods that can be fortified with one or more compounds of formula I according to the present invention are, for example, foods derived from a single natural source (e.g., sugar, unsweetened juice, corn, cereals, corn syrup), mixtures of such Foods (eg, multivitamin preparations, mineral mixtures or sweetened juice) or food preparations (eg, prepared cereals, biscuits, mixed drinks, yoghurt, diet foods, low calorie foods, or animal feed).

The foods which can be enriched according to the present invention with one or more compounds of formula I thus include all edible combinations of carbohydrates, lipids, proteins, inorganic elements, trace elements, vitamins, water or active metabolites of plants and animals.

The foods of the invention enriched with one or more compounds of formula I may be prepared by techniques well known to those skilled in the art.

Another object of the present invention are compounds of formula I-4, I-5 or I-6

These compounds can be prepared as described above by hydrogenation of corresponding aromatic starting materials using a catalyst by methods known to those skilled in the art.

In the following the invention will be explained in more detail by means of examples. The invention can be carried out in the entire claimed range and is not limited to the examples mentioned here.

Examples:

Example 1: Antimicrobial action of I-2

For sample preparation, the test substance I-2 is homogeneously dispersed to 1.0% in a water-ethanol mixture (12% ethanol) (= sample). A suspension of Staphylococcus epidermidis (ATCC 12228) with optical density of 1.0 in CASO broth (Merck 1.05459) 1: 10000 with CASO broth is diluted. 500 μl of microorganism suspension are added to 500 μl of sample and incubated at 35 ° C. for 24 hours or 48 hours. After incubation, the test mixtures are diluted in increments of 10 to -6 and plated out in 0.1 ml each on CASO agar (Merck 1.05458) and incubated at 35 ° C. for 24 h.

To determine the starting bacterial count, 0.1 ml of the bacterial suspension used is plated on CASO agar (Merck 1.05458) and incubated for 24 h at 35 ° C.

Subsequently, the colonies are counted and the germ count per mL compared to the negative control (12% ethanol in water) is determined.
(CFU = colony-forming unit) Result for test substance I-2: test germ Starting bacterial count CFU / mL Final germ count CFU / mL Staphylococcus epidermidis (ATCC 12228) 5.8 × 10 ⁴ 4.0 × 10 ⁴ Result for the negative control: test germ Starting bacterial count CFU / mL Final germ count CFU / mL Staphylococcus epidermidis (ATCC 12228) 5.8 × 10 ⁴ 5.2 × 10 ⁷

Example 2: Antimicrobial effect of I-1

The effect of substance I-1 on the test organisms Staphylococcus aureus, Candida albicans and Aspergillus brasiliensis is investigated. The experiment is carried out on the basis of Example 1, with the incubation period of A. brasiliensis differing from 48 hours. Furthermore, the substance I-1 deviating from 2% incorporated in the water-ethanol mixture. Result for test substance I-1: test germ Starting bacterial count CFU / mL Final germ count CFU / mL Staphylococcus aureus (ATCC 6538) 7.2 × 10 ⁴ 2.5 × 10 ² Candida albicans (ATCC 10231) 6.0 × 10 ³ 0 Aspergillus brasiliensis (ATCC 16404) 8.0 × 10 ² 1.0 × 10 ² Result for the negative control: test germ Starting bacterial count CFU / mL Final germ count CFU / mL Staphylococcus aureus (ATCC 6538) 7.2 × 10 ⁴ 7.2 × 10 ⁷ Candida albicans (ATCC 10231) 6.0 × 10 ³ 5.0 × 10 ⁵ Aspergillus brasiliensis (ATCC 16404) 8.0 × 10 ² 1.2 × 10 ⁴

Example 3: Synthesis of 2- (4-methoxycyclohexyloxy) ethanol (I-5)

30 g of 2- (4-methoxy-phenoxy) -ethanol are dissolved in 100 ml of tetrahydrofuran. Subsequently, 3.0 g of catalyst Rh-C-5% (about 50% water) are added. The hydrogenation is carried out with hydrogen 3.0 at 65 ° C and 5 bar. After complete hydrogenation, the catalyst is separated by filtration. The filtrate is freed from the solvent in vacuo. 25 g of product are obtained in a mixture of cis and trans isomers.

Example 4 :: Synthesis of 2-tert-butyl-4-methoxycyclohexanol (Compound I-6)

1 g of 2-tert-butyl-4-methoxy-phenol are dissolved in 50 ml of ethyl acetate. Subsequently, 1 g of catalyst Rh-C-5% (50% water) is added. The hydrogenation is carried out with hydrogen 3.0 at 40 ° C and 2 bar pressure. After complete hydrogenation, the catalyst is separated by filtration and the solution is concentrated by rotary evaporation. This gives 870 mg of product (cis and trans isomer mixture). Example 5: Antidandruff Shampoo INCI % (w / w) % (w / w) % (w / w) % (w / w) % (w / w) % (w / w) Acrylates / C10-30 Alkyl Acrylate Crosspolymer 1.0 1.0 1.0 1.0 1.0 1.0 propylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 Sodium Lauryl Sulfate (30%) 15.0 15.0 15.0 15.0 15.0 15.0 Sodium Laureth Sulfate (28%) 15.0 15.0 15.0 15.0 15.0 15.0 Cocamidopropyl betaine (35%) 5.0 5.0 5.0 5.0 5.0 5.0 Substance I-1 0.5 0.5 1.0 Substance I-2 0.5 0.75 2.0 Substance I-3 0.5 1.0 Substance I-4 0.5 0.75 Substance I-5 0.5 0.75 2.0 Substance I-6 0.5 1.0 Substance I-7 0.5 0.75 Polyquaternium-10 0.30 0.30 0.30 0.30 0.30 0.30 DMDM Hydantoin (and) Iodopropynyl Butyl Carbamate 0.3 0.3 0.3 0.3 0.3 0.3 Polyquaternium-39 1.0 1.0 1.0 1.0 1.0 1.0 Dimethicone PEG-7 isostearates 0.5 0.5 0.5 0.5 0.5 0.5 Zinc Pyrithione (48%) 2.0 1.0 1.0 0.5 0.5 Fragrance 1.0 1.0 1.0 1.0 1.0 1.0 Dye 0.1 0.1 0.1 0.1 0.1 0.1 Aqua Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Sodium hydroxides qs to pH 6 qs to pH 6 qs to pH 6 qs to pH 6 qs to pH 6 qs to pH 6 Example 6: Antiacne Facial Cleansing Gel INCI % (w / w) % (w / w) % (w / w) % (w / w) % (w / w) % (w / w) Propylene glycol 2.5 2.5 2.5 2.5 2.5 2.5 Dehydroxanthan gum 1.5 1.5 1.5 1.5 1.5 1.5 Cocamidopropyl betaines 10.0 10.0 10.0 10.0 10.0 10.0 Salicylic acid 2.0 0.5 0.5 1.0 Sodium lactate 0.5 1.0 1.0 triclosan 0.2 0.2 1,3.Butylene glycol 3.5 3.5 3.5 3.5 3.5 3.5 Substance I-1 0.5 0.5 1.0 1.0 Substance I-2 0.5 0.75 2.0 Substance I-3 0.5 1.0 Substance I-4 0.5 Substance I-5 0.5 0.75 2.0 Substance I-6 0.5 1.0 Substance I-7 0.5 Menthyl lactate 0.2 0.2 0.2 0.2 0.2 0.2 PEG-40 Hydrogenated Castor Oil 0.5 0.5 0.5 0.5 0.5 0.5 C8-16-decyl glucosides 5.0 5.0 5.0 5.0 5.0 5.0 DMDM Hydantoin (and) Iodopropynyl Butyl Carbamate 0.5 0.5 0.5 0.5 0.5 0.5 Lactose (and) Cellulose (and) Hydroxypropyl Methylcellulose (and) Ultramarine Blue (CI77007) (and) Triclosan 0.4 0.4 0.4 0.4 0.4 0.4 Fragrance 0.5 0.5 0.5 0.5 0.5 0.5 Aqua Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100

Example 7: Antiperspirant Spray (Aerosol)

• a) suspension production

INCI % (w / w) % (w / w) % (w / w) % (w / w) % (w / w) % (w / w) Aluminum Chlorohydrate 35.0 25.0 20.0 10.0 25.0 Ethylhexylglycerin 0.5 0.5 0.5 0.5 0.5 0.5 C12-15 alkyl benzoates 5.0 5.0 5.0 5.0 5.0 5.0 Diasteardimonium hectorite 5.0 5.0 5.0 5.0 5.0 5.0 Silver citrate 0.0015 0.0025 Silver lactate 0.0025 0.0015 propylene carbonates 1.0 1.0 1.0 1.0 1.0 1.0 Substance I-1 1.0 1.5 Substance I-2 0.5 1.0 2.0 1.0 3.5 Substance I-3 2.0 1.5 0.5 1.0 1.0 Substance I-4 1.0 1.5 Substance I-5 0.5 1.0 2.0 1.0 3.5 Substance I-6 2.0 1.5 0.5 1.0 1.0 Substance I-7 1.0 1.5 Fragrance 4.0 4.0 4.0 4.0 4.0 4.0 Cyclopentasiloxane Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100

• b) propellant mixture of propane / isobutane / butane (1/1/1)
• c) Aerosol production takes place by packaging the suspension in an aerosol can together with the propellant gas in the ratio suspension / propellant gas = 20/80.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2009/087242 A2 [0009]
• WO 94/10117 [0010]
• US 2006/0045892 A1 [0011]
• WO 93/04665 [0110]
• EP 0487404A [0110]
• DE 10133202A [0145, 0145]

Cited non-patent literature

• Alonso et al, 2008, Tetrahedron 64, 1847-1852 [0061]
• Bai et al, 2010, Catalysis Communications 12, 212-216 [0061]
• K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108 [0091]
• CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159 [0092]
• K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 [0092]
• Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53 64 [0133]

Claims (17)

Use of at least one compound of the formula I

wherein R ₁ , R ₂ , R ₃ , R 4 and R 5 are independently a radical selected from --H, OH, OCOCH ₃ , O (CH ₂ CH ₂ O) _n H, where n = 1 to 20, halogen, - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may optionally be substituted by one or more OH groups, - straight-chain or branched O-alkyl group having 1 to 20 carbon atoms, and wherein R6 is a radical selected from - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may be optionally substituted with one or more OH groups, - (CH ₂ CH ₂ O) _n H, where n = 1 to 20, as an antimicrobial agent. Use according to claim 1 in cosmetic / pharmaceutical formulations, medical products, foods or household products, in particular in dental or oral care products. Use according to claim 1 or 2 for preservative improvement. Use of at least one compound of the formula I

wherein R ₁ , R ₂ , R ₃ , R 4 and R 5 are independently a radical selected from --H, OH, OCOCH ₃ , O (CH ₂ CH ₂ O) _n H, where n = 1 to 20, halogen, - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may optionally be substituted by one or more OH groups, - straight-chain or branched O-alkyl group having 1 to 20 carbon atoms, and wherein R6 is a radical selected from - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may be optionally substituted with one or more OH groups, - (CH ₂ CH ₂ O) _n H, where n = 1 to 20, as an anti-acne, anti-dandruff, deodorant or antiperspirant active. Use according to one or more of claims 1 to 4, characterized in that R 6 is a radical selected from - straight-chain or branched alkyl group having 1 to 12 C-atoms, - (CH ₂ CH ₂ O) _n H, where n = 1 up to 2. Use according to claim 5, characterized in that R 6 is a radical selected from CH ₃ and CH ₂ CH ₂ OH. Use according to one or more of claims 1 to 6, characterized in that R 1, R _2, R _3, R ₄ and R 5 independently of one another represent a radical selected from --H, OH, O (CH ₂ CH ₂ O) _n H, where n = 1 to 2, - straight-chain or branched alkyl group having 1 to 12 carbon atoms, which may optionally be substituted by one or more OH groups, - straight-chain or branched O-alkyl group having 1 to 12 carbon atoms. Use according to claim 7, characterized in that R 1, R 2, R 4 and R 5 independently of one another represent a radical selected from H and t-butyl. Use according to claim 7 or 8, characterized in that R ₃ is a radical selected from H, OH, OCH ₂ CH ₂ OH, OCH ₃ and CH ₂ OH. Use according to one or more of claims 1 to 9, characterized in that the compound of formula I is a compound selected from the compounds of formulas I-1 to I-8

Preparation containing at least one compound of the formula I.

wherein R ₁ , R ₂ , R ₃ , R 4 and R 5 are independently a radical selected from --H, OH, OCOCH ₃ , O (CH ₂ CH ₂ O) _n H, where n = 1 to 20, halogen, - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may optionally be substituted by one or more OH groups, - straight-chain or branched O-alkyl group having 1 to 20 carbon atoms, and wherein R6 is a radical selected from - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may optionally be substituted by one or more OH groups, - (CH ₂ CH ₂ O) _n H, where n = 1 to 20, and at least one suitable carrier. A preparation according to claim 11, characterized in that the preparation is a deodorant, an antiperspirant, an anti-dandruff or anti-acne agent or an antibacterial preparation, in particular for dental or oral care. Preparation according to claim 11 or 12, characterized in that in addition to the at least one compound of formula I, at least one further preservative and / or antimicrobial agent is included. Preparation according to one or more of claims 11 to 13, characterized in that further at least one antioxidant is contained. Composition containing at least one compound of the formula I.

wherein R ₁ , R ₂ , R ₃ , R 4 and R 5 are independently a radical selected from --H, OH, OCOCH ₃ , O (CH ₂ CH ₂ O) _n H, where n = 1 to 20, halogen, - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may optionally be substituted by one or more OH groups, - straight-chain or branched O-alkyl group having 1 to 20 carbon atoms, and wherein R6 is a radical selected from - straight-chain or branched Alkyl group having 1 to 20 carbon atoms, which may be optionally substituted with one or more OH groups, - (CH ₂ CH ₂ O) _n H, where n = 1 to 20, and at least one antioxidant. Process for the preparation of a preparation according to one or more of Claims 11 to 14, characterized in that the compound of the formula I is mixed with a suitable carrier. Compound of formula I-4, I-5 or I-6