EP2010625A1 - Antioxydants - Google Patents

Antioxydants

Info

Publication number
EP2010625A1
EP2010625A1 EP07723594A EP07723594A EP2010625A1 EP 2010625 A1 EP2010625 A1 EP 2010625A1 EP 07723594 A EP07723594 A EP 07723594A EP 07723594 A EP07723594 A EP 07723594A EP 2010625 A1 EP2010625 A1 EP 2010625A1
Authority
EP
European Patent Office
Prior art keywords
chain
branched
straight
alkyl
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07723594A
Other languages
German (de)
English (en)
Inventor
Thomas Rudolph
Herwig Buchholz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2010625A1 publication Critical patent/EP2010625A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
    • C07C35/28—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms
    • C07C35/29—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms being a (2.2.1) system
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/742—Organic compounds containing oxygen
    • A23B2/75—Organic compounds containing oxygen with doubly-bound oxygen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/762—Organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/767—Organic compounds containing sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/18—Antioxidants, e.g. antiradicals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
    • C07C49/675—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/683—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/522—Antioxidants; Radical scavengers

Definitions

  • the present invention relates to the use of compounds as antioxidant or for product protection or for pigmentation control, corresponding novel compounds and preparations, as well as corresponding preparation processes for compounds and preparations.
  • a field of application of the compounds according to the invention is, for example, cosmetics.
  • the task of nourishing cosmetics is to preserve the impression of a youthful skin if possible.
  • existing skin damage such as irregular pigmentation or wrinkling
  • Another approach is to protect the skin from environmental influences that lead to permanent damage and thus aging of the skin.
  • the idea is to intervene preventively and thereby delay the aging process.
  • An example of this are UV filters which avoid or at least reduce damage to the skin by absorption of specific wavelength ranges. While with UV filters the damaging event, the UV
  • Radiation shielded from the skin is another way to support the skin's natural defenses or repair mechanisms against the damaging event.
  • the skin has the ability to scavenge radicals generated by external or internal stressors. This ability weakens with increasing age, causing the
  • antioxidants are compounds which are undesirable, due to oxygen effects u.a. Oxidative processes inhibit or prevent changes in the substances to be protected. Areas of use are e.g. in plastics and rubber for
  • antioxidants are effective i.a. phenols substituted by sterically hindering groups
  • Hydroquinones, catechols, aromatics, amines and their metal complexes Hydroquinones, catechols, aromatics, amines and their metal complexes.
  • the effect of the antioxidants, according to Römpp, is usually that they act as scavengers for the free radicals occurring during the autoxidation.
  • the object of the invention is therefore to provide a composition which has a protective action against UV rays and / or exerts a protective effect against oxidative stress on body cells and / or counteracts aging of the skin.
  • a first subject of the present invention is therefore the use of compounds of the formula I.
  • X and Y are each independently selected from the radicals H, C-i- ⁇ -alkyl and the radicals according to the formulas Ia, Ib or Ic
  • Alkyl chains may each be interrupted by oxygen or nitrogen, straight-chain or branched C r to 2 o-alkyl groups, wherein the alkyl chains may each also be interrupted by oxygen or nitrogen, straight-chain or branched C 3 - to C 2 o-alkenyl groups, straight-chain or branched Cr to C ⁇ o-hydroxyalkyl groups, wherein the Hydroxy group may be bonded to a primary or secondary carbon atom of the chain and further the alkyl chains may each be interrupted by oxygen or nitrogen, straight or branched Cr to C 2 o-hydroxyalkoxy groups, wherein the hydroxy group (s) to primary or secondary carbon atoms of the chain and the alkyl chain can also be interrupted by oxygen, straight-chain or branched Cr to C 2 o-alkyl groups, wherein the alkyl chains is functionalized with at least one sulfate, sulfonate, phosphonate, or phosphate group, or
  • R 1 represents a carboxylic, phosphoric or sulfuric acid function which may optionally be esterified with straight-chain or branched C 1 -C 20 -alkyl groups or straight-chain or branched C 3 -C 20 -alkenyl groups, or salts of the compounds of formula I as an antioxidant.
  • R> 1 j: eweils are independently selected from H, straight-chain or branched C r to C 2 o-alkoxy groups, wherein the alkyl chains may each be interrupted by oxygen or nitrogen, straight-chain or branched C 1 to C 20 -alkyl groups, where the alkyl chains may each also be interrupted by oxygen or nitrogen, straight-chain or branched C 3 - to C 2 o-alkenyl groups, straight-chain or branched Cr to C 2 o-hydroxyalkyl groups, wherein the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and further the
  • Alkyl chains may each be interrupted by oxygen or nitrogen, straight-chain or branched Cr to C ⁇ o-hydroxyalkoxy groups, wherein the hydroxy group (s) may be bonded to primary or secondary carbon atoms of the chain and further the
  • Alkyl chain can also be interrupted by oxygen, straight-chain or branched C r to C ⁇ o-alkyl groups, wherein the alkyl chains is functionalized with at least one sulfate, sulfonate, phosphonate, or phosphate group, or
  • R 1 represents a carboxylic, phosphoric or sulfuric acid function is optionally substituted with straight chain or branched Cr to 20 alkyl or linear or branched C 3 - may be esterified to C 2 o-alkenyl, R 2 to R 6 are each independently are selected from H,
  • alkyl chains may each be interrupted by oxygen or nitrogen, straight-chain or branched Cr to C ⁇ o-alkyl groups, wherein the
  • Alkyl chains may be interrupted in each case by oxygen or nitrogen, straight-chain or branched C 1 to C 2 o-dialkylamino groups, straight-chain or branched C 1 to C 2 o trialkylammonium groups, straight-chain or branched C 3 to C 2 o-alkenyl groups, straight-chain or branched C r to C 2 o-hydroxyalkyl groups, where the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chains may each be interrupted by oxygen or nitrogen, straight-chain or branched d- to C 2 o- Hydroxyalkoxy phenomenon, wherein the hydroxy group (s) may be bonded to primary or secondary carbon atoms of the chain and further the alkyl chain may also be interrupted by oxygen, or R 2 to R 6 are each independently a carbon,
  • Phosphoric or sulfuric acid function which may optionally be esterified with straight-chain or branched Cr to 2 o-alkyl groups or straight-chain or branched C 3 - to C 2 o-alkenyl groups, with the proviso that at least one radical from R 2 to R 6 for H or Ci -8- alkyl, or salts of the compounds of formulas M-VIII.
  • Acids is. It is particularly preferred according to the invention if the salts are chlorides, bromides or methyl sulfates.
  • the compounds described can according to the invention as active ingredient for topical application or for the preparation of cosmetic or dermatological preparations or for the preparation of
  • Household products are used.
  • product protection means, in particular, the protection of oxidation-sensitive formulation constituents, such as organic or inorganic dyes, antioxidants, vitamins, perfume components,
  • Oil components or matrix components such as emulsifiers, thickeners,
  • Film formers and surfactants are used.
  • the corresponding use is the subject of this application.
  • the subject of the invention is also the use of the compounds for the production of cosmetic, dermatological or pharmaceutical, in particular dermatological, preparations or foods or dietary supplements or for the production of household products.
  • Another object of the present invention are the compounds of formula I 1 as defined above, but wherein the compounds 1, 7,7-trimethyl-3- (4-methyl-benzyl) bicyclo [2.2.1] heptan-2 on and
  • R 1 is, independently of one another, a straight-chain or branched C r to C 20 -alkyl group, where the alkyl chains may each be interrupted by oxygen or nitrogen or by a straight-chain or branched Cr to C 2 o-alkyl group, wherein the alkyl chain is functionalized with at least one sulfate, sulfonate, phosphonate, or phosphate group.
  • Compounds R 1 each represents H or methyl, wherein methyl may also be functionalized with a sulfate, sulfonate, phosphonate, or phosphate group.
  • methyl may also be functionalized with a sulfate, sulfonate, phosphonate, or phosphate group.
  • R 1 is identical in the given formula and is a straight-chain or branched Cr to C 20 - alkyl group, wherein the alkyl chain is functionalized with at least one sulfonate group.
  • R 4 in the compounds according to the invention in each case represents H or C r to C 4 -alkyl, C 1 - to C 4 -dialkylamino or C 1 - to C 4 -trialkylammonium.
  • the at least one compound of the formula I in the use according to the invention is selected from 1, 7,7-trimethyl-3-benzylbicyclo [2.2.1] heptan-2-one, 1, 7,7-trimethyl-3 - (4-methylbenzylidene) bicyclo [2.2.1] heptan-2-ol, 1,7,7-trimethyl-3-benzylidenebicyclo [2.2.1] heptan-2-ol, 1,7,7 -Trimethyl-3- (4-methyl-benzyl) -bicyclo [2.2.1] heptan-2-one, 7,7-dimethyl-3- (4-methyl-benzyl) -2-oxo-bicyclo [2.2.1 ] hept-1-yl] -methanesulfonic acid, 7,7-dimethyl-3-benzyl-2-oxo-bicyclo [2.2.1] hept-1-yl] -methanesulfonic acid, 7,7-dimethyl-3-benzyl-2-oxo-
  • Another subject of the invention are preparations containing at least one compound of the formula I.
  • preparations may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. All compounds or components in the
  • Preparations can be used, are either known and commercially available or can be synthesized by known methods.
  • the preparations are usually either topically applicable preparations, for example cosmetic or dermatological formulations, or foods or dietary supplements or household products.
  • the preparations in this case contain a cosmetically or dermatologically, food-grade or household-suitable carrier and, depending on the desired profile of properties, optionally further suitable ingredients.
  • compositions may be in particular:
  • an antioxidant activity against radicals e.g. by UV light or by thermolytic processes, such as smoking, such as e.g. against the superoxide radical anion or the NO radical, or against reactive oxygen species, e.g. versus
  • preferred compounds combine strong antioxidant activity in combination with high molecular stability
  • preferred compounds of the formula I are suitable as oil components in preparations, preferred compounds of the formula I are suitable for improving galenical properties, such as, for example, the skin sensation, of preparations,
  • preferred compounds of formula I show good solubility and solvent properties, preferably e.g. as a solvent for crystalline components,
  • a preferred group of compounds according to the invention can also cause skin tanning or improve the action of skin-tanning substances, such as dihydroxyacetone,
  • preferred compounds of the formula I are suitable for generating or increasing ("boost" effect) sunscreen factors, such as LSF, SPF, PPD or IPD, or radical protection factors,
  • PEG polyethylene glycol
  • PG polyglycerol
  • PG-containing emulsifiers as mentioned below in this application, or a reduction in the damaging effect of the degradation products of auto-degradable polyethylene glycol (PEG) - or polyglycerol (PG) derivatives, - a stabilizing effect on color, consistency or
  • Properties can also be used for pigmentation control because they can have a whitening effect on skin areas.
  • preferred compounds described herein are colorless or only slightly colored and thus do not or only to a slight extent discolorations of the preparations.
  • preparations containing at least one carrier suitable for cosmetic or dermatological preparations or household products and at least one compound of the above-mentioned are also considered.
  • the preparation contains at least one compound of the formula I
  • Y is selected from the radicals H 1 Ci -8 alkyl or
  • the radicals in the at least one compound of the formula I and the at least one compound of the formula I are identical.
  • the compound of formula I can simultaneously serve as a reservoir for the UV absorption potential of the compound of formula I en. That is, the use of the compounds of formula I thus allows a reduction of the use concentration of UV filters according to formula I The coordination of the use concentrations prepares the expert in this case no difficulties.
  • the compounds of formula I according to the invention typically in amounts of 0.01 to 20 wt .-%, preferably in amounts of 0.1 wt.
  • the compounds according to the invention may be able to develop their positive effect as radical scavengers on the skin particularly well, it may be preferable to allow the compounds according to the invention to penetrate into deeper skin layers.
  • the compounds according to the invention can have sufficient lipophilicity in order to be able to penetrate through the outer skin layer into epidermal layers.
  • appropriate transport means for example liposomes, can be provided in the preparation, which make possible a transport of the compounds according to the invention through the outer skin layers.
  • a systemic transport of the compounds of the invention is conceivable.
  • the preparation is then, for example, designed to be suitable for oral administration.
  • the substances of the formula I act as radical scavengers.
  • Radicals are exogenously generated not only by sunlight, but also by the action of reactive substances, such as ozone, nitrogen oxides (eg cigarette smoke) or heavy metal pollution (eg in the diet).
  • reactive substances such as ozone, nitrogen oxides (eg cigarette smoke) or heavy metal pollution (eg in the diet).
  • anoxia which blocks the flow of electrons upstream of the cytochrome oxidases and causes the formation of superoxide radical ions
  • the compounds or preparations according to the invention are generally suitable for immune protection and for the protection of DNA and RNA.
  • preferred compounds of the present invention are also useful in the treatment of skin diseases associated with a keratinization disorder involving differentiation and cell proliferation, particularly for the treatment of acne vulgaris, acne comedonica, polymorphic acne, rosaceae acne , the nodular acne, the acne conglobata, age-related acne, acne, such as acne solaris, acne-induced acne or acne professionalis, for the treatment of other disorders of keratinization, especially of the ichthyoses, the ichtyosi-forms conditions, of the Darrier disease, the
  • Keratosis palmoplantaris for the treatment of other skin diseases that are related to a disorder of keratinization and have an inflammatory and / or immunoallergic component and especially all Forms of psoriasis affecting the skin, mucous membranes, and fingers and toenails, and psoriatic rheumatism and atopy, such as eczema or respiratory atopy, or even gum hypertrophy, which compounds may also be used in some inflammatory conditions not with one
  • Epithelioma spinocellulare for the treatment of other skin disorders, such as dermatitis bullosa and collagen-related diseases, for the treatment of certain ocular diseases, in particular corneal disorders, for the elimination or control of photodamaging and senile skin aging, for the reduction of pigmentation and keratosis actinica and for the treatment of all diseases associated with normal aging or photodamaging, for the prevention or healing of wounds / scars of atrophy of the epidermis and / or dermis caused by locally or systemically applied corticosteroids and all other types of dermatitis Skin atrophy, for the prevention or treatment of disorders of wound healing, for preventing or eliminating strips of pregnancy or for promoting wound healing, for controlling disorders of TaIg production, such as hyperseborrhea in acne or the simple seborrhoeic, for combating or preventing cancerous conditions or precancerous conditions, in particular promyelocytic leukemia, for the treatment of inflammatory diseases, such as arthritis, for the treatment
  • the antioxidant effects of the compounds according to the invention can be determined, for example, by the methods described in the publication Buenger, J., Ackermann, H., Jentzsch, A., Mehling, A., Pfizner, L 1 Reiffen, K.-A., Schroeder, K.- R., and Wollenweber U., An interlaboratory comparison of methods used to assess antioxidant potentials, Int. J. Cosm. Sci., 28 (2006) pp. 1-12 determined methods. The corresponding method description belongs expressly to the disclosure of the present application.
  • antioxidants Another important aspect of the effect of antioxidants is the time in which they react. This time can be determined, for example, in the DPPH assay as the time until which the EC 50 value is reached and gives the 7 ⁇ E C5 o value, which allows a statement about the speed at which these antioxidants catch radicals. For the purpose of these inventions, antioxidants which reach this value within less than 60 minutes are considered to be fast, those which reach the EC 50 value only after more than 120 minutes have a delayed effect.
  • AE Antiradical Efficiency
  • a low AE (x10 3 ) is in the range up to about 10, an average AE is spoken in the range of 10 to 20, and a high AE is present according to the invention at values above 20.
  • fast-acting antioxidants with those with a slow or delayed action.
  • Typical weight ratios of the fast-acting antioxidants to delayed-acting antioxidants are in the range from 10: 1 to 1:10, preferably in the range from 10: 1 to 1: 1, and for skin-protecting preparations particularly preferably in the range from 5: 1 to
  • compositions indicate weight ratios of the fast-acting antioxidants time-delayed antioxidants in the range 1: 1 to 1:10, preferably in the range 1: 2 to 1: 8.
  • the preparation is therefore a preparation for the protection of body cells against oxidative stress, in particular for reducing skin aging, characterized in that it preferably contains one or more further compounds in addition to the one or more compounds according to formula I. Contains antioxidants.
  • antioxidants e.g. Amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (e.g., urocanic acid) and derivatives thereof, peptides such as D, L-carnosine, D-
  • Carnosine, L-carnosine and their derivatives eg anserine
  • carotenoids eg ⁇ -carotene, ß-carotene, lycopene
  • chlorogenic acid and its derivatives eg dihydrolipoic acid
  • lipoic acid and derivatives thereof eg dihydrolipoic acid
  • aurothioglucose propylthiouracil and other thiols
  • thioredoxin glutathione, cysteine, cystine, cystamine and theirs
  • Glycosyl N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -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,
  • Homocysteine sulfoximine, buthione sulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages eg pmol to ⁇ mol / kg
  • furthermore (metal) chelators eg ⁇ -hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), ⁇ -hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) and coniferyl benzoate of benzoin, rut
  • ZnO, ZnSO 4 zinc and its derivatives
  • selenium and its derivatives eg selenium methionine
  • stilbenes and their derivatives eg stilbene oxide , trans-stilbene oxide.
  • Suitable antioxidants are also described in WO 2006/111233 and WO 2006/111234.
  • Suitable antioxidants are also compounds of the general
  • R 1 can be selected from the group -C (O) CH 3 , -CO 2 R 3 , -C (O) NH 2 and -C (O) N (R 4 ) 2 ,
  • X is O or NH
  • R 2 is linear or branched alkyl having 1 to 30 C atoms
  • R 3 is linear or branched alkyl having 1 to 20 C atoms
  • R 4 are each independently of one another H or linear or branched alkyl having 1 to 8 C atoms,
  • R 5 is linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
  • R 6 denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonate, more preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis- (2-ethylhexyl) ester (for example Oxynex ® ST Liquid) and / or 2- (4-hydroxy-3,5-dimethoxybenzy) - malonic acid-bis (2-ethylhexyl) ester (example RonaCare ® AP).
  • antioxidants are also suitable for use in the cosmetic preparations according to the invention.
  • Known and commercial mixtures are, for example, mixtures comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex AP ®) 1 natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) -
  • Ascorbic acid and citric acid for example Oxynex ® K LIQUID
  • DL- ⁇ -tocopherol for example Oxynex ® L LIQUID
  • citric acid and lecithin for example Oxynex ® LM
  • BHT butylhydroxytoluene
  • antioxidants are usually used with compounds of the invention in such compositions in ratios in the range of 1000: 1 to 1: 1000, preferably in amounts of 100: 1 to 1: 100.
  • the preparations according to the invention may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B 1 ), riboflavin (vitamin B 2 ), nicotinamide , Vitamin C (ascorbic acid),
  • Vitamin D 1 ergocalciferol (vitamin D 2 ), vitamin E, DL- ⁇ -tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin Ki, esculin (vitamin P active ingredient), thiamin (vitamin Bi), nicotinic acid (niacin), Pyri - doxin, pyridoxal, pyridoxamine, (vitamin B 6 ), pantothenic acid, biotin, fatty acid and cobalamin (vitamin Bi 2 ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, retinol, vitamin C and its derivatives, DL- ⁇ -tocopherol, tocopherol-E-acetate, nicotinic acid, pantothenic acid and biotin. Vitamins are used with compounds of the invention usually in ratios in the range of 1000: 1 to 1: 1000, preferably in amounts of
  • the compounds of the formula I are not UVB or UVA absorbers with the exception of the compounds of the formula III, IV and VI in which at least three double bonds are in conjugation. Upon irradiation, i. When using these compounds of the formula I according to the invention, at least one further double bond is formed, so that compounds with a UV absorption in the UV-A and / or UV-B range are generated from the compounds of the formula I. That In other words, among the compounds to be used according to the invention there are precursors of UVB filters, UVA filters or UVB + UVA broadband UV filters, which can be used alone or in combination with other UV filters. Other compounds of the formulas III, IV, VI, VII and VIII according to the invention which are likewise preferred
  • UV filters Precursors of UV filters with an absorption maximum in the boundary between the UVB and UVA radiation. As a UVA-II filter, they can therefore advantageously supplement the absorption spectrum of commercially available UVB or UVA-I filters. Usually, one speaks of a UVA-II filter when its absorption maximum in the UVA I I range between 320 nm and 340 nm. Accordingly, UVA-I filters have a maximum between 340 nm and 400 nm.
  • straight-chain or branched Cp to C 2 o-alkoxy groups in particular the long-chain alkoxy functions, such as ethylhexyloxy groups, increase the oil-solubility of the compounds.
  • the preparations according to the invention may also contain poorly or not soluble compounds according to the invention in the preparation matrix.
  • the compounds are preferably dispersed in finely divided form in the cosmetic preparation.
  • Preparations which are particularly preferred according to the invention can also serve as sunscreens and, in addition to the compounds according to the invention, also comprise UV filters.
  • UV-sensitive dibenzoylmethane derivatives and cinnamic acid derivatives are additionally stabilized by the presence of the compounds according to the invention.
  • Another object of the present invention is therefore the use of the compounds of the invention for the stabilization of Dibenzoylmethanderivaten and / or cinnamic acid derivatives in preparations.
  • UV filters are suitable for combination with the compounds according to the invention. Particularly preferred are those UV filters whose physiological harmlessness has already been demonstrated.
  • UVA and UVB filters there are many known and proven substances in the literature, e.g.
  • Benzylidenecamphor derivatives such as 3- (4'-methylbenzylidene) -dl-camphor (for example Eusolex 6300), 3-benzylidenecamphor (for example Mexoryl® SD), polymers of
  • Benzophenones such as 2-hydroxy-4-methoxybenzophenone (e.g., Eusolex®
  • Methoxycinnamic acid esters such as octyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of isomers
  • Neo Heliopan® E 1000 e.g., Neo Heliopan® E 1000
  • Salicylate derivatives such as 2-ethylhexyl salicylate (eg Eusolex® OS), 4-isopropylbenzyl salicylate (eg Megasol®) or 3,3,5-trimethylcyclohexyl salicylate (eg Eusolex® HMS) 1
  • 4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 2-ethylhexyl 4- (dimethylamino) benzoate (e.g., Eusolex® 6007), ethoxylated 4-aminobenzoic acid ethyl ester (e.g., Uvinul® P25),
  • Phenylbenzimidazole sulfonic acids such as 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (eg Eusolex® 232), 2,2- (1,4-phenylene) bisbenzimidazole-4,6-disulfonic acid or salts thereof (eg Neoheliopan® AP) or 2,2- (1,4-phenylene) bisbenzimidazole-6-sulfonic acid;
  • 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester e.g., Eusolex® OCR
  • Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate eg Uvinul® UVA Plus, BASF.
  • UVA Plus Ultraviolet® UVA Plus
  • organic UV filters are usually incorporated in an amount of 0.5 to 10 weight percent, preferably 1-8%, in cosmetic formulations.
  • organic UV filters are e.g. 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1-yl)
  • UV filters are also Methoxyflavone enschend the older German patent application DE-A-10232595.
  • Organic UV filters are usually incorporated in an amount of 0.5 to 20 percent by weight, preferably 1 to 15 wt .-%, in cosmetic formulations.
  • inorganic UV filters are those from the group of titanium dioxides such as coated titanium dioxide (eg Eusolex® T-2000, Eusolex ® T-AQUA, Eusolex ® T-AVO), zinc oxides (eg Sachtotec®), iron oxides or cerium oxides conceivable.
  • These inorganic UV filters are generally used in an amount of 0.5 to 20 percent by weight, preferably 2 to 10 percent by weight.
  • Preferred compounds having UV-filtering properties are 3- (4 '- methylbenzylidene) -dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) - pro-pan-1, 3-dione , 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxy-benzo-phenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4- (dimethylamino) -benzoic acid-2-ethyl- hexyl ester, 2-cyano-3,3-di-phenyl-2-ethylhexyl acrylate, 2-phenyl-benzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts.
  • optimized compositions can be the combination of the organic UV filters 4'-methoxy-6-hydroxyflavone with 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione and 3- (4 ' -
  • Methylbenzylidene -dl camphor. This combination results in a broadband protection, which can be supplemented by the addition of inorganic UV filters, such as titanium dioxide microparticles.
  • UV filters and the compounds according to the invention can also be used in encapsulated form.
  • organic UV filters in encapsulated form.
  • hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter or of the compound of the formula I.
  • hydrophobic UV filters or compounds according to the invention can also be incorporated into purely aqueous preparations.
  • the often as unpleasant felt oily impression when applying the hydrophobic UV filter containing preparation prevented.
  • UV filters in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations.
  • Photostability of these filters can increase the photostability of the entire formulation.
  • UV filters or compounds according to the invention are present in encapsulated form. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the o.g. Effects, it is also necessary that the capsules are sufficiently stable and donate the encapsulated active ingredient (UV filter) not or only to a small extent to the environment.
  • Suitable capsules may have walls of inorganic or organic polymers.
  • Capsules which are particularly preferred for use in accordance with the invention have walls which can be obtained by a SolGel process, as described in applications WO 00/09652, WO 00/72806 and WO 00/71084.
  • Capsules whose walls are made of silica gel (silica; undefined silicon oxide hydroxide) are constructed.
  • silica gel silicon; undefined silicon oxide hydroxide
  • the capsules in preparations according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the amounts indicated above.
  • the preparations according to the invention may additionally contain further customary skin-sparing or skin-care active substances.
  • these can be all active ingredients known to the person skilled in the art.
  • Particularly preferred active ingredients are pyrimidinecarboxylic acids and / or
  • Pyrimidinecarboxylic acids are present in halophilic microorganisms and play a role in the osmoregulation of these organisms (EA Galinski et al., EJr. J. Biochem., 149 (1985) pages 135-139).
  • ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid)
  • hydroxyectoine (S 1 S) -1,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids
  • These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents.
  • enzymes against denaturing conditions such as salts, extreme pH, surfactants, urea, guanidinium chloride and other compounds.
  • Ectoine and ectoine derivatives such as hydroxyectoine can be used to advantage in medicines.
  • hydroxyectoine can be used for the manufacture of a medicament for the treatment of skin diseases.
  • Other applications of hydroxyectoins and other ectoine derivatives are typically in areas where, for example Trehalose is used as an additive.
  • ectoine derivatives, such as hydroxyectoine can be used as a protective substance in dried yeast and bacterial cells. Even pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins such as t-PA can be protected with ectoine or its derivatives.
  • European Patent Application EP-A-0 671 161 describes in particular that ectoine and hydroxyectoine are used in cosmetic preparations such as powders, soaps, surfactant-containing cleansing products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.
  • a pyrimidinecarboxylic acid according to the formula below is preferably used,
  • R 1 is a radical H or C 1-8 -alkyl
  • R 2 is a radical H or C 1-4 -alkyl and R 3 ,
  • R 4 , R 5 and R 6 are each independently a radical from the group H, OH, NH 2 and C 1-4 -alkyl.
  • the preparations according to the invention contain such pyrimidinecarboxylic acids, preferably in amounts of up to 15% by weight.
  • the pyrimidine In this case, ratios of 100: 1 to 1: 100 are used for the compounds according to the invention, with ratios in the range from 1:10 to 10: 1 being particularly preferred.
  • 2-hydroxy-5-methyllaurophenone oxime which is also referred to as HMLO, LPO or F5
  • HMLO 2-hydroxy-5-methyllaurophenone oxime
  • LPO 2-hydroxy-5-methyllaurophenone oxime
  • Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which accompany inflammation. It is known that such preparations, e.g. can be used for the treatment of psoriasis, various eczema forms, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages.
  • compositions according to the invention which, in addition to the compound of the formula I, additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising antiinflammatory suitability.
  • the preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.
  • the preparation according to the invention contains at least one self-tanner.
  • flavonoid diosmetin and its glycosides or sulfates can also be used. These compounds can be used in the form of pure substances or plant extracts.
  • diuretic may preferably be used in the form of a chrysanthemum extract.
  • DHA 1, 3-dihydroxyacetone
  • the said self-tanner may be used alone or as a mixture. It is particularly preferred if DHA in the
  • Self-tanner alone leads to accelerated tanning.
  • the corresponding use of the compounds according to the invention for accelerating the tanning effect of self-tanning agents is therefore a further subject matter of the present invention.
  • compositions are either known and commercially available or may be synthesized by known methods.
  • the one or more compounds according to the invention can be incorporated in the usual way into cosmetic or dermatological preparations.
  • Suitable preparations for external use for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin.
  • administration formulas such as capsules, dragees, powders, tablets
  • preparations according to the invention are, for example: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays.
  • Other forms of application include sticks, shampoos and shower baths.
  • the preparation can Any customary carriers, excipients and optionally other active ingredients may be added.
  • Preferable excipients come from the group of preservatives, antioxidants, stabilizers, solubilizers, vitamins, colorants, odor improvers.
  • Ointments, pastes, creams and gels may contain the usual excipients, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites,
  • excipients e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites,
  • Powders and sprays may contain the usual carriers, e.g. Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances.
  • Sprays may additionally contain the usual propellants, e.g. Chlorofluorocarbons, propane / butane or dimethyl ether.
  • Solutions and emulsions may contain the customary carriers such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate,
  • solvents e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate,
  • Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, Polyoxyethylensorbitester and Polyoxyethylensorbitanester, microcrystalline cellulose, Aluminiummeta- hydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.
  • liquid diluents e.g. Water, ethanol or propylene glycol
  • suspending agents e.g. ethoxylated isostearyl alcohols, Polyoxyethylensorbitester and Polyoxyethylensorbitanester
  • microcrystalline cellulose Aluminiummeta- hydroxide
  • bentonite agar-agar and tragacanth or mixtures of these substances.
  • Soaps may contain the usual carriers such as alkali salts of fatty acids, salts of fatty acid halides, fatty acid protein hydrolysates, isothionates, Lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugar or mixtures of these substances.
  • Surfactant-containing cleaning products may include 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, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol - Contain fatty acid esters or mixtures of these substances.
  • excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinate
  • 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.
  • 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.
  • the preferred preparation forms according to the invention include in particular emulsions.
  • Emulsions of the invention are advantageous and contain z.
  • Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil; Fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with alcohols of low C number, for example 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,
  • 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 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of from 3 to 30 carbon atoms, selected from the group consisting of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of from 3 to 30 carbon atoms. atoms.
  • ester oils can then advantageously be selected from the group consisting of 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,
  • 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.
  • oil phase As 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.
  • the oil phase selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethyl hexylcocoat, C 2 -i 5 alkyl benzoate, caprylic-capric acid triglyceride, Dicap- rylether.
  • Particularly advantageous are mixtures of C 2 -i 5 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C 2 -i 5 alkyl benzoate and isotridecyl isononanoate and mixtures of C 2-15 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
  • hydrocarbons paraffin oil, squalane and squalene are to be used advantageously in the context of the present invention.
  • the oil phase can also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils.
  • cyclomethicone octamethylcyclotetrasiloxane
  • silicone oils are also advantageous for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are particularly advantageous.
  • the aqueous phase of the preparations according to the invention advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, Glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g.
  • ethanol isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous the group of polyacrylates, preferably a polyacrylate from the group of the so-called carbopols, for example Carbopols of
  • a mixture of the abovementioned solvents is used.
  • water can be another ingredient.
  • Emulsions of the invention are advantageous and contain z.
  • the preparations according to the invention contain hydrophilic surfactants.
  • hydrophilic surfactants are preferably selected from the group of
  • Alkylglucoside Alkylglucoside, acyllactylates, betaines and cocoamphoacetates.
  • alkylglucosides in turn are advantageously selected from the group of alkylglucosides, which are represented by the structural formula
  • R represents a branched or unbranched alkyl radical having 4 to 24 carbon atoms and wherein DP means a mean Glucosyl michsgrad of up to 2.
  • the value DP represents the degree of glucosidation of the alkylglucosides used in the invention and is defined as
  • P 1 , P 2 , P 3 ... Or pi represent the proportion of products which are mono-, di-trisubstituted ... times glucosylated in weight percentages.
  • the value DP takes into account the fact that alkylglucosides, as a rule, are mixtures of mono- and oligoglucosides. According to the invention, a relatively high content of monoglucosides, typically of the order of 40-70% by weight, is advantageous.
  • Alkylglylcosides used particularly advantageously according to the invention are selected from the group octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecylglucopyranoside. It is also advantageous materials, natural or synthetic raw materials and assistants or to use mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ® 1200 (Henkel KGaA), Oramix NS ® 10 (Seppic).
  • R 1 is a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M + is selected from the group of the alkali metal ions and the group of ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth metal equivalent.
  • sodium is advantageous, for example the product Pathionic ® ISL from the American Ingredients Company.
  • R 2 is a branched or unbranched alkyl radical having 1 to 30 carbon atoms. Particularly advantageously, R 2 is a branched or unbranched alkyl radical having 6 to 12 carbon atoms.
  • Capramidopropylbetaine for example, is advantageous
  • sodium elected cocoamphoacetate invention beneficial as under the name Miranol ® Ultra C32 from Miranol Chemical Corp. is available.
  • the preparations according to the invention are advantageously characterized in that the hydrophilic surfactant or surfactants in concentrations of 0.01-20 wt .-%, preferably 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, respectively based on the total weight of the composition, is present or present.
  • the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • Cosmetic and dermatological preparations according to the invention can be present in various forms. So they can z.
  • Oil-in-water (W / O / W) a gel, a solid stick, an ointment or even an aerosol.
  • active ingredients in encapsulated form for.
  • collagen matrices and other common encapsulating materials e.g. As cellulose encapsulations, in gelatin,
  • Wax matrices or liposomally encapsulated In particular wax matrices as described in DE-OS 43 08 282, have been found to be favorable. Preference is given to emulsions. O / W emulsions are particularly preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way. As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsions according to the invention.
  • suitable co-emulsifiers are, for example, O / W emulsifiers, primarily 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 W emulsifiers have saturated radicals R and R 1 .
  • O / W emulsifiers unsaturated radicals R and / or
  • R 1 or are Isoalkylderivate
  • the preferred HLB value of such emulsifiers may also be lower or higher.
  • fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols). Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15),
  • the sodium laureth-11-carboxylate can be advantageously used.
  • alkyl ether sulfate sodium laureth1-4 sulfate can be used to advantage.
  • polyethylene glycol (30) cholesteryl ether can be advantageously used.
  • polyethylene glycol (25) soybean oil has been proven.
  • the polyethylene glycol ( ⁇ ) Evening Primrose Glycerides can advantageously be used
  • 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).
  • 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
  • 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.
  • W / O emulsifiers can be used:
  • Fatty alcohols containing 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 to 18, carbon atoms,
  • W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate,
  • Lotion or emulsion such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, as solid pins or be assembled as an aerosol.
  • the preparation may contain cosmetic adjuvants which are commonly used in this type of preparation, e.g. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent itself or the skin, and other ingredients commonly used in cosmetics.
  • cosmetic adjuvants which are commonly used in this type of preparation, e.g. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent itself or the skin, and other ingredients commonly used in cosmetics.
  • polyol or mixtures thereof include ethanol, i-propanol, propylene glycol, glycerin and sorbitol.
  • a preferred embodiment of the invention is an emulsion which is present as a protective cream or milk containing, in addition to or compounds of the invention, for example fatty alcohols, fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water ,
  • 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 Glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.
  • the preparation of the invention may also be present as an alcoholic gel containing one or more lower alcohols or polyols, such as
  • Ethanol propylene glycol or glycerin
  • a thickening agent 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.
  • blowing agents are generally used, such as alkanes, fluoroalkanes and
  • the cosmetic preparation may also be used to protect the hair against photochemical damage to prevent changes in hues, discoloration or damage of a mechanical nature.
  • suitable as a packaging Shampoo, lotion, gel or emulsion for rinsing wherein the respective preparation is applied before or after shampooing, before or after dyeing or decolouring or before or after perming.
  • It may also be a preparation as a lotion or gel for styling and conditioning, as a lotion or gel for brushing or laying one
  • the formulation with photoprotective properties may contain, in addition to the compound (s) of the invention, various adjuvants used in this type of mediator, such as surfactants, thickeners, polymers, emollients
  • Agents preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, anti-grease agents, dyes and / or pigments which dye the agent itself or the hair or other ingredients commonly used for hair care.
  • Further objects of the present invention are a process for the preparation of a preparation which is characterized in that at least one compound of the formula I is mixed with a carrier cosmetically or dermatologically or suitable for foodstuffs or household products, and the use of a compound of the formula I for Preparation of a preparation with antioxidant properties.
  • preparations according to the invention can be prepared using techniques which are well known to the person skilled in the art.
  • the mixing may result in dissolution, emulsification or dispersion of the compound of the invention in the carrier.
  • Reactants in the synthesis are commercially available or accessible by syntheses well known to those skilled in the literature.
  • the selection of suitable reaction conditions for their synthesis is standard in the art.
  • the synthesis can also be carried out analogously to the synthesis described in DE 3321679
  • Y is selected from the radicals H, C-i-s-alkyl and
  • Suitable catalysts for the hydrogenation are all common homogeneous and heterogeneous catalysts, particularly preferred as the catalyst is at least one noble metal preferably selected from the elements Pt, Pd and Rh, or a transition metal such as Mo, W, Cr, but especially Fe, Co and Ni, used either singly or in admixture.
  • the catalyst (s) or catalyst mixtures may also be supported on supports such as carbon, activated carbon, aluminum oxide, barium carbonate, barium sulfate, calcium carbonate, Strontium carbonate or diatomaceous earth can be used.
  • the metal may also be used in the form of the Raney compound, for example Raney nickel. If the catalysis is carried out in a homogeneous process, it is preferred if as catalyst one or more complex compounds of said metals, such as
  • Wilkinson catalyst chloro-tris (triphenylphosphine) rhodium
  • Suitable noble metal salts are, for example, palladium acetate, palladium bromide or
  • suitable reducing agents are for example hydrogen, hydrazine, sodium borohydride or formates.
  • a heterogeneous catalyst is used, it being particularly preferred to use as catalyst in the process according to the invention Pd or Pt, preferably on activated carbon supports, for example 5% by weight of Pd or Pt on C.
  • alkenols according to the invention such as the compounds of formulas II, IM and IV, preferably obtained by means of sodium borohydride and the alkanones of the invention, such as the compounds of formulas V, VI and VII, preferably by hydrogenation with elemental hydrogen ,
  • alkenols according to the invention such as the compounds of formulas II, IM and IV, preferably obtained by means of sodium borohydride and the alkanones of the invention, such as the compounds of formulas V, VI and VII, preferably by hydrogenation with elemental hydrogen
  • the hydrogenation is usually carried out at a temperature in the range of 20 - 15O 0 C. Further, the hydrogenation is advantageously carried out at a hydrogen pressure of 1 to 200 bar.
  • Suitable solvents are protic solvents, in particular the conventional protic solvents known to those skilled in the art, such as water, lower alcohols, such as methanol, ethanol and Isopropanol, as well as primary and secondary amines and mixtures of such protic solvents, and it may be particularly preferred if water is used as the solvent.
  • protic solvents such as water, lower alcohols, such as methanol, ethanol and Isopropanol, as well as primary and secondary amines and mixtures of such protic solvents, and it may be particularly preferred if water is used as the solvent.
  • Suitable solvents for this reaction are common aprotic solvents.
  • diethyl ether, tetrahydrofuran, benzene, toluene, acetonitrile, dimethoxyethane, dimethylformamide, dimethyl sulfoxide and N-methyl-pyrrolidone can be used.
  • the hydrogenation is carried out in bulk, i. no additional solvent is required.
  • the workup can be carried out by conventional methods.
  • the catalyst can be filtered off, the filtrate can be freed from the solvent, for. B. by heating at reduced compared to atmospheric pressure and the product thus obtained by conventional methods further purified.
  • reaction products can likewise be carried out by customary methods, for example by recrystallization from a suitable solvent, or by chromatographic methods.
  • compositions for Protection of the skin against the effects of UV rays are exposed to particularly high exposure to UV radiation.
  • the foods which can be fortified according to the present invention with one or more compounds according to the invention include all materials which are 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 liquid, so as a drink).
  • Carrier included.
  • Foodstuffs which can be enriched with one or more compounds according to the invention according to the present invention are, for example, foods derived from a single natural source, such as sugar, unsweetened juice, nectar or puree from a single plant species, such as unsweetened apple juice ( eg a mixture of different types of apple juice), grapefruit juice, orange juice, apple compote, apricot nectar, tomato juice, tomato sauce, tomato puree, etc.
  • Further examples of foods according to the present invention having one or more Compounds of the invention may be enriched in grain or cereals of a single plant species and materials produced from such plant species, such as corn syrup, rye flour, wheat flour or oat bran. Mixtures of such foods are also suitable according to the present invention
  • Invention be enriched with one or more compounds of the invention, for example, multi-vitamin preparations, mineral mixtures or sweetened juice.
  • foods that can be fortified with one or more compounds of the present invention include food preparations such as prepared cereals, biscuits, mixed drinks, foods specially formulated for children, such as yoghurt, diet foods, low calorie foods or animal foods.
  • the foods that can be fortified according to the present invention with one or more compounds according to the invention thus include all edible combinations of carbohydrates, lipids, proteins, inorganic elements, trace elements, vitamins, water or active metabolites of
  • the foods which can be fortified according to the present invention with one or more compounds of the invention are preferably administered orally, e.g. in the form of food,
  • the foods of the present invention fortified with one or more compounds of the present invention can be prepared by techniques well known to those skilled in the art.
  • compounds according to the invention are also suitable as medicament ingredients. They help to support or substitute for natural mechanisms that trap radicals in the body.
  • the compounds of the invention may be partially in their effect with Radical scavengers such as vitamin C compounds of the invention can be used for example for the preventive treatment of inflammation and allergies of the skin and in certain cases for the prevention of certain cancers.
  • compounds of the invention are suitable for the preparation of a
  • drugs for the treatment of inflammation, allergies and irritations, in particular of the skin.
  • drugs can be produced in an action as a vein tonic, as an agent for increasing the strength of blood capillaries, as an inhibitor of cuperose, as an inhibitor of chemical, physical or actinic erythema, as a means for
  • Treating sensitive skin as a decongestant, as a dehydrating agent, as a slimming agent, as an anti-wrinkle agent, as a stimulator of the synthesis of extracellular matrix components, as a tonicityener to improve skin elasticity, and as an acidulant.
  • preferred compounds of the present invention exhibit antiallergic and antiinflammatory and antiirritative effects. They are therefore suitable for the preparation of medicaments for the treatment of inflammation or allergic reactions.
  • the hydrogenation is carried out in methanol at 1 bar hydrogen pressure and room temperature over Pd-C (5% Pd). After hydrogenation, the batch is filtered, the solvent removed in vacuo and the residue taken up in methyl t-butyl ether (MTBE). Subsequently, it is filtered through zeolite A. The solvent is removed in vacuo. The product is obtained as a colorless oil which crystallizes overnight (mixture of diastereomers).
  • a 4% solution of the substance in isopropyl myristate is prepared. 40 ⁇ L of the solution is applied to the roughened surface of 2 plexiglas plates (7.2 x 2.5 cm). A plate was then irradiated in the solar simulator (Atlas CPS +) for 1 h 50 min with cooling. Subsequently, the sample is transferred to a 50mL graduated cylinder and covered with 4OmL isopropanol for extraction in an ultrasonic bath. The sample volume is then filled up to exactly 50 mM and the absorption is measured at 300 nm. An analogously treated unirradiated batch serves as a comparison. The absorption can be through the Irradiation step increased by 22% from 0.094 (dark beginning) to 0.115.
  • the UV spectrum of the compounds according to the invention changes.
  • the irradiation can be carried out using an Atlas Sun Test CPS, xenon lamp with UV special glass filter at a power of 95.69 W / m 2 in the range 290-400 nm.
  • Example 3a Oxidation in UV light in the presence of further antioxidants
  • emulsions comprising compounds according to the invention and beta-carotene, in comparison to those which contain only beta-carotene, show that the absorption of beta-carotene (E max in the range 440-480 nm) is markedly stronger in the samples according to the invention , Consequently, the beta-carotene degradation is reduced in the emulsion according to the invention; the compounds of the invention stabilize the beta-carotene.
  • the radical-reducing effect of the compounds according to the invention can be determined, for example, by methods such as in the publication Buenger, J., Ackermann, H., Jentzsch, A., Mehling, A., Pfizner, I., Reiffen, K.-A., Schroeder, K.-R., and Wollenweber U., An interlaboratory comparison of methods used to assess antioxidant potentials, Int. J. Cosm. Sci., 28 (2006) pp. 1-12.
  • exemplary formulations for cosmetic preparations which contain compounds according to Example 1 or 2.
  • Corresponding preparations can be prepared in the same way with all compounds according to the invention.
  • UV-Pearl, OMC stands for the preparation with the INCI name: Water (for EU: Aqua), Ethylhexyl Methoxycinnamate, Silica, PVP,
  • Chlorphenesin, BHT this formulation is commercially available under the designation Eusolex®UV Pearl TM OMC from Merck KGaA, Darmstadt.
  • the other UV pearls listed in the tables are each assembled analogously, with OMC being replaced by the UV filters specified.

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Abstract

La présente invention concerne l'utilisation de composés de formule (X-Ar-Y), dans laquelle X et Y sont sélectionnés indépendamment parmi les groupes H, alkyle C<SUB>1-8</SUB> et les groupes représentés par les formules (Ia), (Ib) et (Ic), dans lesquelles les groupes sont tels que définis dans la description, en tant qu'antioxydants. L'invention concerne également de nouveaux composés correspondants et de nouvelles préparations correspondantes, ainsi que des procédés de production correspondants de ces composés et de ces préparations.
EP07723594A 2006-04-25 2007-03-26 Antioxydants Withdrawn EP2010625A1 (fr)

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DE102006019043A DE102006019043A1 (de) 2006-04-25 2006-04-25 Antioxidantien
PCT/EP2007/002648 WO2007121818A1 (fr) 2006-04-25 2007-03-26 Antioxydants

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DE102010033138A1 (de) 2010-08-03 2012-02-09 Merck Patent Gmbh Phenethyl-, Phenethylen-, Phenethin- und Indanonderivate
DE102011114780A1 (de) 2011-10-01 2013-04-04 Merck Patent Gmbh Verwendung von Propanol- und Propenolderivaten als Antioxidantien
WO2014096250A1 (fr) * 2012-12-21 2014-06-26 Shell Internationale Research Maatschappij B.V. Compositions de carburant liquide comprenant des composés d'écran solaire organiques
US10021056B2 (en) 2016-09-12 2018-07-10 International Business Machines Corporation Dynamic e-mail chain participant manager
CN110420152B (zh) * 2019-08-20 2022-09-13 中山中研化妆品有限公司 一种清爽温和的双层卸妆液及其制备方法

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LU67061A1 (fr) * 1973-02-19 1974-09-25
LU84264A1 (fr) * 1982-07-08 1984-03-22 Oreal Nouveaux sulfonamides derives du 3-benzylidene camphre et leur application en tant que filtres u.v.,notamment dans des compositions cosmetiques
FR2645150B1 (fr) * 1989-03-31 1994-07-22 Oreal Nouveaux derives de benzyl-cyclanones, leur procede de preparation et compositions cosmetiques et pharmaceutiques les contenant

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