US20050043398A1 - Use of chromen-4-one derivatives - Google Patents
Use of chromen-4-one derivatives Download PDFInfo
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- US20050043398A1 US20050043398A1 US10/920,202 US92020204A US2005043398A1 US 20050043398 A1 US20050043398 A1 US 20050043398A1 US 92020204 A US92020204 A US 92020204A US 2005043398 A1 US2005043398 A1 US 2005043398A1
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- BIDCGBIJJHNVIG-UHFFFAOYSA-N CCOC(C(Oc(cc1OC(C(OCC)=O)=O)cc(OC(C(OCC)=O)=C2)c1C2=O)=O)=O Chemical compound CCOC(C(Oc(cc1OC(C(OCC)=O)=O)cc(OC(C(OCC)=O)=C2)c1C2=O)=O)=O BIDCGBIJJHNVIG-UHFFFAOYSA-N 0.000 description 1
- QLJYPGSMODXQON-UHFFFAOYSA-N O=C(O)C1=CC(=O)C2=CC=C(O)C=C2O1 Chemical compound O=C(O)C1=CC(=O)C2=CC=C(O)C=C2O1 QLJYPGSMODXQON-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
- A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
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- A61K31/12—Ketones
- A61K31/122—Ketones having the oxygen directly attached to a ring, e.g. quinones, vitamin K1, anthralin
-
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- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
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- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
- A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline
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Definitions
- the present invention relates to the use of chromen-4-one derivatives for the care, preservation or improvement of the general state of the skin or hair and for prophylaxis against time- and/or light-induced ageing processes of the human skin or human hair and for the prophylaxis and/or treatment of skin diseases.
- the invention furthermore relates to compositions having an effective content of chromen4-one derivatives.
- the present invention relates to cosmetic compositions for prophylaxis against ageing processes in the skin.
- the human skin is subject to certain ageing processes, some of which are attributable to intrinsic processes (chronoageing) and some of which are attributable to exogenous factors (environmental, for example photo-ageing).
- temporary or even lasting changes to the skin picture can occur, such as acne, greasy or dry skin, keratoses, rosaceae, light-sensitive, inflammatory, erythematous, allergic or autoimmune-reactive reactions, such as dermatosis and photodermatosis.
- the exogenous factors include, in particular, sunlight or artificial radiation sources having a comparable spectrum, and compounds which can be formed by the radiation, such as undefined reactive photoproducts, which may also be free-radical or ionic. These factors also include cigarette smoke and the reactive compounds present therein, such as ozone, free radicals, for example the hydroxyl free radical, singlet oxygen and other reactive oxygen or nitrogen compounds which interfere with the natural physiology or morphology of the skin.
- MMPs matrix metalloproteinases
- TIMPs tissue inhibitors of matrix metalloproteinases
- the same factors also act on hair, where damage can likewise occur.
- the hairs become brittle, less elastic and dull.
- the surface structure of the hairs is damaged.
- Cosmetic or dermatological care products having properties which are claimed to counter the processes described or comparable processes or reduce or reverse the harmful consequences thereof are frequently distinguished by the following specific properties—free-radical-scavenging, antioxidative, inflammation-inhibiting or humectant. They prevent or reduce, inter alia, the activity of matrix-degrading enzymes or regulate the new synthesis of collagen, elastin or proteoglycans.
- antioxidants or free-radical scavengers in cosmetic compositions is adequately known per se.
- the use of the antioxidative vitamin E in sunscreen formulations is usual. Nevertheless, the effect achieved is even here well short of the hoped-for effect.
- Vitamin A and vitamin-A derivatives act on the differentiation of epithelial cells and are therefore employed for the prophylaxis and treatment of numerous phenomena which impair the skin state, for example use against acne, psoriasis, senile keratosis, skin discoloration and wrinkles has been described (cf., for example, WO 93/19743 and WO 02/02074).
- the object of the present invention was to provide novel active ingredients which exhibit the effects already mentioned at the outset, are sufficiently oxidation- and photostable and can readily be formulated.
- the compositions prepared therewith should furthermore have as far as possible a low irritation potential for the skin, as far as possible have a positive influence on water binding in the skin, retain or increase skin elasticity and thus promote smoothing of the skin.
- they should preferably create a pleasant skin feeling on application to the skin.
- chromen-2-one derivatives are suitable as active ingredients having the profile described.
- the present invention relates firstly to the use of at least one compound of the formula I or of a composition comprising at least one compound of the formula I, where
- the term “compound of the formula I” basically also includes the salts of the compounds of the formula I.
- the preferred salts include, in particular, alkali metal and alkaline earth metal salts as well as ammonium salts, but in particular sodium and potassium salts.
- the present invention furthermore relates to a composition
- a composition comprising at least one compound of the formula I containing radicals as defined above, and at least one further skin-care ingredient and at least one carrier which is suitable for topical applications.
- Uses which are preferred in accordance with the invention of the compounds of the formula I or of compositions comprising at least one compound of the formula I are, in particular, the use for prophylaxis against time- and/or light-induced ageing processes of the human skin or human hair, in particular for prophylaxis against dry skin, wrinkle formation and/or pigment defects, and/or for the reduction or prevention of the harmful effects of UV rays on the skin, and for prophylaxis against or reduction of skin unevenness, such as wrinkles, fine lines, rough skin or large-pored skin.
- Uses which are preferred in accordance with the invention of the compounds of the formula I or of compositions comprising at least one compound of the formula I are furthermore the use for the prophylaxis and/or prevention of premature skin ageing, in particular for the prophylaxis and/or prevention of light- or ageing-induced wrinkling of the skin, for the reduction of pigmentation and keratosis actinica, and for the prophylaxis and/or treatment of all diseases which are associated with normal skin ageing or light-induced ageing of the skin, and for the prophylaxis and/or treatment of skin diseases which are associated with defective keratinisation relating to differentiation and cell proliferation, in particular for the treatment of acne vulgaris, acne comedonica, polymorphic acne, acne rosaceae, nodular acne, acne conglobata, age-related acne, acne occurring as a side effect, such as acne solaris, medicament-related acne or acne professionalis, for the treatment of other defects of keratinisation, in particular ichthyosis
- the present invention also relates to the use of the compounds of the formula I for the preparation of compositions which are suitable for the above-mentioned uses.
- compositions here are usually either compositions which can be used topically, for example cosmetic or dermatological formulations, or foods or food supplements.
- the compositions comprise a cosmetically or dermatologically or food-suitable carrier and, depending on the desired property profile, optionally further suitable constituents.
- chromen-4-one derivatives of the general formula I in compositions offers, inter alia, protection against damage caused directly or indirectly by UV radiation or by processes caused by reactive compounds, such as, for example, skin ageing, loss of skin moisture, loss of skin elasticity, formation of wrinkles or folds or of pigment defects or senile keratosis.
- the present invention furthermore relates to the use of the above-mentioned compositions for the prevention of undesired changes to the skin picture, such as, for example, acne or greasy skin, keratoses, light-sensitive, inflammatory, erythema tous, allergic or autoimmune-reactive reactions.
- the compounds and compositions according to the invention preferably also serve to calm sensitive and irritated skin, for the preventative regulation of collagen, hyaluronic acid and elastin synthesis, stimulation of DNA synthesis, in particular in the case of deficient or hypoactive skin states, regulation of the transcription and translation of matrix-degrading enzymes, in particular of MMPs, increase in cell regeneration and regeneration of the skin, increase in the skin's own protective and repair mechanisms for DNA, lipids and/or proteins.
- Preferred compounds of the formula I are characterised in that R 3 is H and R 4 is OH, since the action potential of representatives of this class of com-pound is particularly high in the above-mentioned sense. If, in addition, at least one of the radicals R 5 and R 6 is OH, these preferred compounds, in addition to the above-mentioned properties, additionally have an anti-oxidant potential. They can therefore simultaneously function as anti-oxidant in compositions.
- R 5 and R 6 are H.
- the radicals R 3 and R 4 are freely accessible, which, as assumed, is advantageous for interaction with enzymes involved in the effects mentioned.
- radicals R 1 and R 2 are H and the other radical is —C( ⁇ O)—R 7 , —C( ⁇ O)—OR 7 or a straight-chain or branched C 1 - to C 20 -alkyl group.
- compositions are suitable for the treatment of skin, in particular for the treatment of dermatoses, including atopic eczema.
- U.S. Pat No. 6,019,992 discloses cosmetic compositions which comprise 4-chromanone and are suitable for the treatment of aged. dry or wrinkled skin. It is shown here that 4-chromanone promotes cell differentiation and stimulates lipid production in keratinocyte cultures.
- EP-A-1 216 692 discloses the use of 2-methyl-2-( ⁇ -carboxyethyl)chroman derivatives in cosmetic compositions.
- the said compositions are particularly suitable for prophylaxis against ageing processes of skin and hair and for prophylaxis against dry skin, wrinkle formation and pigment defects.
- compositions for topical application which comprise chromone derivatives, such as, for example, chromone, 7-hydroxychromone, 7-methoxychromone, 5,7-dihydroxy-2-methylchromone, 3-methyl-2-butenyloxychromone, 3-acetyl-5,7-dihydroxy-2-methylchromone, 5-hydroxychromone, -n-pentyl 7-methoxychromone-2-carboxylate, n-undecyl 5-methoxychromone-2-carboxylate, 5-hydroxy-7-methoxy-2-methylchromone, 7-methoxychromone-2-carboxylic acid, n-pentylchromone-2-carboxylic acid, 5-methoxychromone and chromone-2-carboxylic acid, are disclosed in Japanese patent application JP 05/301813.
- the chromone derivatives act as skin-tolerated tyrosinase inhibitors which reduce hyperpigmentation of
- Japanese patent application JP 09/188608 discloses the use of substituted chromone derivatives, such as, in particular, 5,7-dihydroxychromones, 7-methoxychromones, 5-hydroxy-7-methoxy-2-methylchromone and 5-hydroxy-2-methylchromone, as active ingredient against grey hair.
- substituted chromone derivatives such as, in particular, 5,7-dihydroxychromones, 7-methoxychromones, 5-hydroxy-7-methoxy-2-methylchromone and 5-hydroxy-2-methylchromone
- a composition against skin ageing comprising chromone derivatives which are substituted in the 2-position by C 1-15 -alkyl and have H, OH or alkoxy substitution in the 7-position, in combination with aminopropanol derivatives is disclosed in JP 10/194919.
- Cosmetic compositions which comprise substituted chromone derivatives, such as, for example, 2-(1-ethylpentyl)chromone, 5,7-dihydroxychromones, 7-methoxychromones, 5-hydroxy-7-methoxy-2-methylchromone and 5-hydroxy-2-methylchromone, and aromatic compounds having a melting point of -10C or above are disclosed in JP 10/114640.
- substituted chromone derivatives such as, for example, 2-(1-ethylpentyl)chromone, 5,7-dihydroxychromones, 7-methoxychromones, 5-hydroxy-7-methoxy-2-methylchromone and 5-hydroxy-2-methylchromone, and aromatic compounds having a melting point of -10C or above are disclosed in JP 10/114640.
- the chromone derivative here simplifies incorporation of the aromatic compound into the cosmetic formulation.
- the compounds of the formula I are typically employed in accordance with the invention in amounts of from 0.01 to 20% by weight, preferably in amounts of from 0.1% by weight to 10% by weight and particularly preferably in amounts of from 1 to 8% by weight.
- the person skilled in the art has absolutely no difficulties in selecting the amount correspondingly depending on the intended action of the composition.
- compositions comprise one or more further antioxidants, where the person skilled in the art has absolutely no difficulties in selecting antioxidants having a suitably fast or time-delayed action.
- At least one further skin-care ingredient is one or more antioxidants and/or vitamins.
- composition to comprise no retinol derivative.
- antioxidants for example amino acids (for example glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example ⁇ -carotene, ⁇ -carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (for example dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and
- antioxidants are likewise suitable for use in the cosmetic compositions 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 Oxynex® AP), natural tocopherols, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (for example Oxynex® K LIQUID), tocopherol extracts from natural sources, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (for example Oxynex® L LIQUID), DL- ⁇ -tocopherol, L-(+)-ascorbyl palmitate, citric acid and lecithin (for example Oxynex® LM) or butylhydroxytoluene (BHT), L-(+)-ascorbyl palmitate and citric acid (for example Oxyn
- compositions according to the invention may comprise vitamins as further ingredients.
- the cosmetic compositions according to the invention preferably comprise vitamins and vitamin derivatives selected from vitamin B, thiamine chloride hydrochloride (vitamin B 1 ), riboflavin (vitamin B 2 ), nicotinamide, vitamin C.
- Vitamins are usually employed here with compounds of the formula I in ratios in the range from 1000:1 to 1:1000, preferably in amounts of from 100:1 to 1:100.
- the polyphenols are of particular interest for applications in the pharmaceutical, cosmetic or nutrition sector.
- the flavonoids or bioflavonoids which are principally known as plant dyes, frequently have an antioxidant potential.
- dihydroxyflavones containing an OH group adjacent to the keto function or OH groups in the 3′,4′- or 6,7- or 7,8-position have antioxidative properties, while other mono- and dihydroxyflavones in some cases do not have antioxidative properties.
- Quercetin (cyanidanol, cyanidenolon 1522, meletin, sophoretin, ericin, 3,3′,4′,5,7-pentahydroxyflavone) is frequently mentioned as a particularly effective antioxidant (for example C. A. Rice-Evans, N. J. Miller, G. Paganga, Trends in Plant Science 1997, 2(4), 152-159). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A. E. M. F. Soffers, I. M. C. M. Rietjens; Free Radical Biology&Medicine 2001, 31(7), 869-881, have investigated the pH dependence of the antioxidant action of hydroxyflavones. Quercetin exhibits the greatest activity amongst the structures investigated over the entire pH range.
- Suitable antioxidants are furthermore compounds of the formula II where R 1 to R 10 may be identical or different and are selected from
- compositions comprising at least one compound of the formula II which is characterised in that at least two adjacent radicals of the radicals R 1 to R 4 are OH and at least two adjacent radicals of the radicals R 5 to R 7 are OH.
- Particularly preferred compositions comprise at least one compound of the formula II. which is characterised in that at least three adjacent radicals of the radicals R 1 to R 4 are OH, preferably with the radicals R 1 to R 3 being OH.
- the compounds of the formula I are able to develop their positive action as free-radical scavengers on the skin particularly well, it may be preferred to allow the compounds of the formula I to penetrate into deeper skin layers.
- the compounds of the formula I can have an adequate lipophilicity in order to be able to penetrate through the outer skin layer into epidermal layers.
- corresponding transport agents for example liposomes, which enable transport of the compounds of the formula I through the outer skin layers may also be provided in the composition.
- systemic transport of the compounds of the formula I is also conceivable.
- the composition is then designed, for example, in such a way that it is suitable for oral administration.
- the compounds of the formula II in encapsulated form, for example as cellulose or chitin capsules, in gelatine or wax matrices or encapsulated with cyclodextrins.
- the preferred compounds of the formula I also act as enzyme inhibitors. They presumably inhibit protein kinases, elastase, aldose reductase and hyaluronidase, and therefore enable the intactness of the basic substance of vascular sheaths to be maintained. Furthermore, they presumably inhibit non-specifically catechol O-methyl transferase, causing the amount of available catecholamine and thus the vascular strength to be increased. Furthermore, they are thought to inhibit AMP phosphodiesterase, giving the substances potential for inhibiting thrombocyte aggregation.
- compositions according to the invention are, in general, suitable for immune protection and for the protection of DNA and RNA.
- the compositions are suitable for the protection of DNA and RNA against oxidative attack, against free radicals and against damage due to radiation, in particular UV radiation.
- a further advantage of the compositions according to the invention is cell protection, in particular protection of Langerhans cells against damage due to the above-mentioned influences. All these uses and the use of the compounds of the formula I for the preparation of compositions which can be employed correspondingly are expressly also a subject-matter of the present invention.
- compositions according to the invention are also suitable for the treatment of skin diseases associated with a defect in keratinisation which affects differentiation and cell proliferation, in particular for the treatment of acne vulgaris, acne comedonica, polymorphic acne, acne rosaceae, nodular acne, acne conglobata, age-induced acne, acne which arises as a side effect, such as acne solaris, medicament-induced acne or acne professionalis, for the treatment of other defects in keratinisation, in particular ichthyosis, ichthyosiform states, Darier's disease, keratosis palmoplantaris, leucoplasia, leucoplasiform states, herpes of the skin and mucous membrane (buccal) (lichen), for the treatment of other skin diseases associated with a defect in keratinisation and which have an inflammatory and/or immunoallergic component and in particular all forms of psoriasis which affect the skin, mucous membranes and fingers and toenails, and ps
- compositions which are particularly preferred in accordance with the invention also comprise UV filters besides the compounds of the formula I.
- the UV-sensitive dibenzoylmethane derivatives are additionally stabilised by the presence of the compounds of the formula I.
- the present invention therefore furthermore relates to the use of the compounds of the formula I for the stabilisation of dibenzoylmethane derivatives in compositions.
- UV filters are suitable for combination with the compounds of the formula I. Particular preference is given to UV filters whose physiological acceptability has already been demonstrated. Both for UVA and UVB filters, there are many proven substances which are known from the specialist literature, for example:
- organic UV filters are generally incorporated into cosmetic formulations in an amount of from 0.5 to 1.0 per cent by weight, preferably 1-8%.
- organic UV filters are, for example,
- UV filters are also methoxyflavones corresponding to the earlier German patent application DE 10232595.2.
- Organic UV filters are generally incorporated into cosmetic formulations in an amount of from 0.5 to 20 per cent by weight, preferably 1-15%.
- Conceivable inorganic UV filters are those from the group consisting of titanium dioxides, such as, for example, coated titanium dioxide (for example E usolex® T-2000, Eusolex® T-AQUA), zinc oxides (for example Sachtotec®), iron oxides and also cerium oxides. These inorganic UV filters are generally incorporated into cosmetic compositions in an amount of from 0.5 to 20 per cent by weight, preferably 2-10%.
- Preferred compounds having UV-filtering properties are 3-(4′-methylbenzylidene)-dl-camphor, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethylcyclohexyl salicylate, 2-ethylhexyl 4-(dimethylamino)benzoate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts.
- Optimised compositions may comprise, for example, 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 gives rise to broad-band protection, which can be supplemented by the addition of inorganic UV filters, such as titanium dioxide microparticles.
- UV filters can also be employed in encapsulated form.
- organic UV filters in encapsulated form.
- one or more of the above-mentioned UV filters prefferably be in encapsulated form. It is advantageous here for the capsules to be so small that they cannot be viewed with the naked eye. In order to achieve the above-mentioned effects, it is furthermore necessary for the capsules to be sufficiently stable and the encapsulated active ingredient (UV filter) only to be released to the environment to a small extent, or not at all.
- Suitable capsules can have walls of inorganic or organic polymers.
- U.S. Pat No. 6,242,099 B1 describes the production of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines.
- Capsules which can particularly preferably be employed in accordance with the invention have walls which can be obtained by a sol-gel process, as described in the applications WO 00/09652, WO 00/72806 and WO 00/71084. Preference is again given here to capsules whose walls are built up from silica gel (silica; undefined silicon oxide hydroxide).
- silica gel silica gel
- the production of corresponding capsules is known to the person skilled in the art, for example from the cited patent applications, whose contents expressly also belong to the subject-matter of the present application.
- the capsules are preferably present in compositions according to the invention in amounts which ensure that the encapsulated UV filters are present in the composition in the above-indicated amounts.
- the skin-protecting or skin-care active ingredients can in principle be any active ingredients known to the. person skilled in the art.
- particularly preferred active ingredients are pyrimidinecarboxylic acids and/or aryl oximes.
- Pyrimidinecarboxylic acids occur in halophilic microorganisms and play a role in osmoregulation of these organisms (E. A. Galinski et al., Eur. J. Biochem., 149 (1985) pages 135-139).
- pyrimidinecarboxylic acids particular mention should be made here of ectoine ((S)-1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S,S)-1,4,5,6-tetrahydro-5-hydroxy-2-methyl4-pyrimidinecarboxylic acid) and derivatives thereof.
- ectoine ((S)-1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid)
- hydroxyectoine (S,S)-1,4,5,6-tetrahydro-5-hydroxy-2-methyl4-pyrimidinecarboxylic acid) and derivatives thereof.
- These compounds stabili
- Ectoine and ectoine derivatives can advantageously be used in medicaments.
- hydroxyectoine can be employed for the preparation of a medicament for the treatment of skin diseases.
- Other areas of application of hydroxyectoine and other ectoine derivatives are typically in areas in which, for example, trehalose is used as additive.
- ectoine derivatives, such as hydroxyectoine can be used as protectant in dried yeast and bacteria cells.
- Pharmaceutical products, such as non-glycosylated, pharmaceutically active peptides and proteins, for example t-PA can also be protected with ectoine or its derivatives.
- European patent application EP-A-0 671 161 describes, in particular, that ectoine and hydroxyectoine are employed in cosmetic compositions, such as powders, soaps, surfactant-containing cleansing products, lipsticks, rouge, make-ups, care creams and sunscreen compositions.
- a pyrimidinecarboxylic acid of the following formula II in which 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 of one another, a radical from the group consisting of H, OH, NH 2 and C1-4-alkyl.
- R 1 is a radical H or C 1 -8-alkyl
- R 2 is a radical H or C 1 -4-alkyl
- R 3 , R 4 , R 5 and R 6 are each, independently of one another, a radical from the group consisting of H, OH, NH 2 and C1-4-alkyl.
- R 2 is a methyl or ethyl group
- R 1 or R 5 and R 6 are H.
- compositions according to the invention preferably comprise pyrimidinecarboxylic acids of this type in amounts of up to 15% by weight.
- the pyrimidinecarboxylic acids are preferably employed here in ratios of from 100:1 to 1:100 with respect to the compounds of the formula I, with ratios in the range from 1:10 to 10:1 being particularly preferred.
- compositions which comprise 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are accompanied by inflammation. It is known that compositions of this type can be used, for example, for the therapy of psoriasis, various forms of eczema, irritative and toxic dermatitis, UV dermatitis and further allergic and/or inflammatory diseases of the skin and integumentary appendages.
- compositions according to the invention which, in addition to the compound of the formula I, additionally comprise an aryl oxime, preferably 2-hydroxy-5-methyllaurophenone oxime, exhibit surprising anti-inflammatory suitability.
- the compositions here preferably comprise from 0.01 to 10% by weight of the aryl oxime, it being particularly preferred for the composition to comprise from 0.05 to 5% by weight of aryl oxime.
- compositions are those for external use, for example in the form of a cream, lotion or gel or as a solution which can be sprayed onto the skin.
- Suitable for internal use are administration forms such as capsules, coated tablets, powders, tablet solutions or solutions.
- compositions according to the invention are, for example, solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleansing preparations, oils, aerosols and sprays.
- examples of other use forms are sticks, shampoos and shower compositions. Any desired customary carriers, assistants and, if desired, further active ingredients may be added to the composition.
- Preferred assistants originate from the group consisting of preservatives, antioxidants, stabilisers, solubilisers, vitamins, colorants and odour improvers.
- Ointments, pastes, creams and gels may comprise the customary carriers, for example animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide, or mixtures of these substances.
- customary carriers for example 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 comprise the customary carriers, for example lactose, talc, silica, aluminium hydroxide, calcium silicate and polyamide powder, or mixtures of these substances.
- Sprays may additionally comprise the customary propellants, for example chlorofluorocarbons, propane/butane or dimethyl ether.
- Solutions and emulsions may comprise the customary carriers, such as solvents, solubilisers and emulsifiers, for example water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed oil, peanut oil, wheatgerm 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.
- solvents such as solvents, solubilisers and emulsifiers, for example water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed oil, peanut oil, wheatgerm oil
- Suspensions may comprise the customary carriers, such as liquid diluents, for example water, ethanol or propylene glycol, suspending agents, for example ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminium metahydroxide, bentonite, agar-agar and tragacanth, or mixtures of these substances.
- liquid diluents for example water, ethanol or propylene glycol
- suspending agents for example ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminium metahydroxide, bentonite, agar-agar and tragacanth, or mixtures of these substances.
- Soaps may comprise the customary carriers, such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isethionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars, or mixtures of these substances.
- customary carriers such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isethionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars, or mixtures of these substances.
- Surfactant-containing cleansing products may comprise the customary carriers, such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid monoesters, fatty acid protein hydrolysates, isethionates, 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.
- customary carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid monoesters, fatty acid protein hydrolysates, isethionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty
- Face and body oils may comprise the customary carriers, such as synthetic oils, such as fatty acid esters, fatty alcohols, silicone oils, natural oils, such as vegetable oils and oily plant extracts, paraffin oils or 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 plant extracts, paraffin oils or lanolin oils, or mixtures of these substances.
- composition forms according to the invention include, in particular, emulsions.
- Emulsions according to the invention are advantageous and comprise, for example, the said fats, oils, waxes and other fatty. substances, as well as water and an emulsifier, as usually used for a composition of this type.
- the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions is advantageously selected from the group consisting of esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids having a chain length of from 3 to 30 carbon atoms and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of from 3 to 30 carbon atoms, or from the group consisting of esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of from 3 to 30 carbon atoms.
- Ester oils of this type 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, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of esters of this type, for example jojoba oil.
- the oil phase may furthermore advantageously be selected from the group consisting of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, or the group consisting of saturated and unsaturated, branched and unbranched alcohols, and fatty acid triglycerides, specifically the triglycerol esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids having a chain length of from 8 to 24, in particular 12-18, carbon atoms.
- the fatty acid triglycerides may advantageously be selected, for example, from the group consisting of synthetic, semi-synthetic and natural oils, for example olive oil, sunflower oil, soya oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
- any desired mixtures of oil and wax components of this type may also advantageously be employed for the purposes of the present invention. It may also be advantageous to employ waxes, for example cetyl palmitate, as the only lipid component of the oil phase.
- the oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyidodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C 1215 -alkyl benzoate, caprylic/capric acid triglyceride and dicapryl ether.
- Particularly advantageous are mixtures of C 12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C 12-15 -alkyl benzoate and isotridecyl isononanoate, as well as mixtures of C 12-15 -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
- paraffin oil squalane and squalene may advantageously be used for the purposes of the present invention.
- oil phase may also advantageously have a content of cyclic or linear silicone oils or consist entirely of oils of this type, although it is preferred to use an additional content of other oil-phase components in addition to the silicone oil or the silicone oils.
- the silicone oil to be used in accordance with the invention is advantageously cyclomethicone (octamethylcyclotetrasiloxane). However, it is also advantageous for the purposes of the present invention to use other silicone oils, for example hexamethylcyclotrisiloxane, polydimethylsiloxane or poly(methylphenylsiloxane).
- mixtures of cyclomethicone and isotridecyl isononanoate and of cyclomethicone and 2-ethylhexyl isostearate are particularly advantageous.
- the aqueous phase of the compositions according to the invention optionally advantageously comprises alcohols, diols or polyols having a low carbon number, and ethers thereof, 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 alcohols having a low carbon number, for example ethanol, isopropanol, 1,2-propanediol or glycerol, and, in particular, one or more thickeners, which may advantageously be selected from the group consisting of silicon dioxide, aluminium silicates, polysaccharides and derivatives thereof, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from the group consisting of the polyacrylates, preferably a
- mixtures of the above-mentioned solvents are used.
- water may be a further constituent.
- Emulsions according to the invention are advantageous and comprise, for example, the said fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as usually used for a formulation of this type.
- compositions according to the invention comprise hydrophilic surfactants.
- hydrophilic surfactants are preferably selected from the group consisting of the alkylglucosides, acyl lactylates, betaines and coconut amphoacetates.
- alkylglucosides are themselves advantageously selected from the group consisting of the alkylglucosides which are distinguished by the structural formula where R is a branched or unbranched alkyl radical having from 4 to 24 carbon atoms, and where ⁇ overscore (DP) ⁇ denotes a mean degree of glucosylation of up to 2.
- Products which are advantageous according to the invention are those having degrees of glucosylation of 1-2, particularly advantageously of from 1.1 to 1.5, very particularly advantageously of 1.2-1.4, in particular of 1.3.
- the value DP takes into account the fact that alkylglucosides are generally, as a consequence of their preparation, in the form of mixtures of mono- and oligoglucosides.
- Alkylglycosides which are particularly advantageously used for the purposes of the invention are selected from the group consisting of octyl glucopyranoside, nonyl glucopyranoside, decyl glucopyranoside, undecyl glucopyranoside, dodecyl glucopyranoside, tetradecyl glucopyranoside and hexadecyl glucopyranoside.
- acyllactylates are themselves advantageously selected from the group consisting of the substances which are distinguished by the structural formula where R 1 is a branched or unbranched alkyl radical having from 1 to 30 carbon atoms, and M + is selected from the group consisting of the alkali metal ions and the group consisting of ammonium ions which are substituted by one or more alkyl and/or one or more hydroxyalkyl radicals, or corresponds to half an equivalent of an alkaline earth metal ion.
- sodium isostearyl lactylate for example the product Pathionic® ISL from the American Ingredients Company, is advantageous.
- the betaines are advantageously selected from the group consisting of the substances which are distinguished by the structural formula where R 2 is a branched or unbranched alkyl radical having from 1 to 30 carbon atoms.
- R 2 is particularly advantageously a branched or unbranched alkyl radical having from 6 to 12 carbon atoms.
- capramidopropylbetaine for example the product Tego® Betain 810 from Th. Goldschmidt AG, is advantageous.
- a coconut amphoacetate which is advantageous for the purposes of the invention is, for example, sodium coconut amphoacetate, as available under the name Miranol® Ultra C 32 from Miranol Chemical Corp.
- compositions according to the invention are advantageously characterised in that the hydrophilic surfactant(s) is (are) present in concentrations of 0.01-20% by weight, preferably 0.05-10% by weight, particularly preferably 0.1-5% by weight, in each case based on the total weight of the composition.
- the cosmetic and dermatological compositions are applied in sufficient amount to the skin and/or hair in the usual manner for cosmetics.
- Cosmetic and dermatological compositions according to the invention may exist in various forms. Thus, they may be, for example, a solution, a water-free composition, an emulsion or microemulsion of the water-in-oil (W/O) or oil-in-water (O/W) type, a multiple emulsion, for example of the water-in-oil-in-water (W/O/W) type, a gel, a solid stick, an ointment or an aerosol. It is also advantageous to administer ectoines in encapsulated form, for example in collagen matrices and other conventional encapsulation materials, for example as cellulose encapsulations, in gelatine, wax matrices or liposomally encapsulated.
- wax matrices as described in DE-A 43 08 282, have proven favourable. Preference is given to emulsions. O/W emulsions are particularly preferred. Emulsions, W/O emulsions and O/W emulsions are obtainable in a conventional manner.
- Emulsifiers that can be used are, for example, the known W/O and O/W emulsifiers. It is advantageous to use further conventional co-emulsifiers in the preferred O/W emulsions according to the invention.
- Co-emulsifiers which are advantageous according to the invention are, for example, O/W emulsifiers, principally from the group consisting of the substances having HLB values of 11-16, very particularly advantageously having HLB values of 14.5-15.5, so long as the O/W emulsifiers have saturated radicals R and R′. If the O/W emulsifiers have unsaturated radicals R and/or R′ or in the case of isoalkyl derivatives, the preferred HLB value of such emulsifiers may also be lower or higher.
- fatty alcohol ethoxylates from the group consisting of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
- Particular preference is given to the following: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), polyethylene glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (1
- An ethoxylated alkyl ether carboxylic acid or salt thereof which can advantageously be used is sodium laureth-11 carboxylate.
- An alkyl ether sulfate which can advantageously be used is sodium laureth-14 sulfate.
- An ethoxylated cholesterol derivative which can advantageously be used is polyethylene glycol (30) cholesteryl ether. Polyethylene glycol (25) soyasterol has also proven successful.
- Ethoxylated triglycerides which can advantageously be used are the polyethylene glycol (60) evening primrose glycerides.
- 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/caprinate, 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/caprinate polyethylene glycol (20) glyceryl oleate
- sorbitan esters from the group consisting 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.
- Optional W/O emulsifiers but ones which may nevertheless be advanta-geous for the purposes of the invention can be the following:
- W/O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate and glyceryl monocaprylate.
- compositions according to the invention are particularly suitable for protecting human skin against ageing processes and against oxidative stress, i.e. against damage by free radicals, as are produced, for example, by sunlight, heat or other influences.
- they. are in the various administration forms usually used for this application.
- they may, in particular, be in the form of a lotion or emulsion, such as in the form of a 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, in the form of solid sticks or may be formulated as an aerosol.
- the composition may comprise cosmetic adjuvants which are usually used in this type of composition, such as, for example, thickeners, softeners, moisturisers, surfactants, emulsifiers, preservatives, antifoams, perfumes, waxes, lanolin, propellants, dyes and/or pigments which colour the composition itself or the skin, and other ingredients usually used in cosmetics.
- cosmetic adjuvants which are usually used in this type of composition, such as, for example, thickeners, softeners, moisturisers, surfactants, emulsifiers, preservatives, antifoams, perfumes, waxes, lanolin, propellants, dyes and/or pigments which colour the composition itself or the skin, and other ingredients usually used in cosmetics.
- the dispersant or solubiliser used can be an oil, wax or other fatty substance, a lower monoalcohol or lower polyol or mixtures thereof.
- Particularly preferred monoalcohols or polyols include ethanol, isopropanol, propylene glycol, glycerol and sorbitol.
- a preferred embodiment of the invention is an emulsion in the form of a protective cream or milk which, apart from the compound(s) according to the invention, comprises, 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.
- a lower alcohol such as ethanol
- a glycerol such as propylene glycol
- a polyol such as glycerol
- composition according to the invention may also be in the form of an alcoholic gel which comprises one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerol, and a thickener, such as siliceous earth.
- the oily-alcoholic gels also comprise 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.
- compositions are formulated as an aerosol
- customary propellants such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.
- the cosmetic composition may also be used to protect the hair against photochemical damage in order to prevent changes of colour shade, bleaching or damage of a mechanical nature.
- a suitable formutation is in the form of a rinse-out shampoo, lotion, gel or emulsion, the composition in question being applied before or after shampooing, before or after colouring or bleaching or before or after permanent waving. It is also possible to select a composition in the form of a lotion or gel for styling or treating the hair, in the form of a lotion or gel for brushing or blow-waving, in the form of a hair lacquer, permanent waving composition, colorant or bleach for the hair.
- the composition having light-protection properties may comprise various adjuvants used in this type of composition, such as surfactants, thickeners, polymers, softeners, preservatives, foam stabilisers, electrolytes, organic solvents, silicone derivatives, oils, waxes, antigrease agents, dyes and/or pigments which colour the composition itself or. the hair, or other ingredients usually used for hair care.
- adjuvants used in this type of composition such as surfactants, thickeners, polymers, softeners, preservatives, foam stabilisers, electrolytes, organic solvents, silicone derivatives, oils, waxes, antigrease agents, dyes and/or pigments which colour the composition itself or. the hair, or other ingredients usually used for hair care.
- the present invention furthermore relates to a process for the preparation of a composition which is characterised in that at least-one compound of the formula I containing radicals as described above is mixed with a cosmetically or dermatologically or food-suitable carrier, and to the use of a compound of the formula I for the preparation of a composition.
- compositions according to the invention can be prepared here with the aid of techniques which are well known to the person skilled in the art.
- the mixing can result in dissolution, emulsification or dispersal of the compound of the formula I in the carrier.
- the compound of the formula I is prepared by cyclisation of a correspondingly substituted o-hydroxyacetophenone using an anhydride or using an acyl chloride under basic conditions.
- the acyl protecting groups can subsequently be removed.
- the reaction here can be carried out analogously to Kelly, T; Kim M. H.; J. Org. Chem . 1992, 57, 1593-97.
- the free hydroxyl groups are acylated, followed by a Baker-Venkatamaran rear-rangement under basic conditions with subsequent ring closure under acidic conditions.
- Corresponding reactions, adaptation of which to the compounds desired here presents absolutely no problems to the person skilled in the art, are disclosed in the patent application WO 2002/060889.
- compounds of the formula I can have a stabilising effect on the composition.
- the latter are thus also stable for longer and do not change their appearance.
- the effectiveness of the ingredients, for example vitamins is retained even in the case of application over extended periods or extended storage. This is, inter alia, particularly advantageous in the case of compositions for protecting the skin against the effect of UV rays since these cosmetics are exposed to particularly high stresses by UV radiation.
- the foods which can be enriched with one or more compounds of the formula I in accordance with the present invention include all materials which are suitable for consumption by animals or consumption by humans, for example vitamins and provitamins thereof, fats, minerals or amino acids.
- the foods may be solid, but also liquid, i.e. in the form of a beverage).
- the present invention accordingly furthermore relates to the use of a compound of the formula I as food additive for human or animal nutrition, and to compositions which are foods or food supplements and comprise corresponding excipients.
- Foods which can be enriched with one or more compounds of the formula I in accordance with the present invention are, for example, also foods which originate from a single natural source, such as, for example, sugar, unsweetened juice, squash or puree of a single plant species, such as, for example, unsweetened apple juice (for example also a mixture of different. types of apple juice), grapefruit juice, orange juice, apple compote, apricot squash, tomato juice, tomato sauce, tomato puree, etc.
- Further examples of foods which can be enriched with one.or more compounds of the formula I in accordance with the present invention are corn or cereals from a single plant species and materials produced from plant species of this type, such as, for example, cereal syrup, rye flour, wheat flour or oat bran.
- Mixtures of foods of this type are also suitable for being enriched with one or more compounds of the formula I in accordance with the present invention, for example multivitamin preparations, mineral mixtures or sweetened juice.
- foods which can be enriched with one or more compounds of the formula I in accordance with the present invention mention may be made of food compositions, for example prepared cereals, biscuits, mixed drinks, foods prepared especially for children, such as yoghurt, diet foods, low-calorie foods or animal feeds.
- the foods which can be enriched with one or more compounds of the formula I in accordance with the present invention thus include all edible combinations of carbohydrates, lipids, proteins, inorganic elements, trace elements, vitamins, water or active metabolites of plants and animals.
- the foods which can be enriched with one or more compounds of the formula I in accordance with the present invention are preferably administered orally, for example in the form of meals, pills, tablets, capsules, powders, syrup, solutions or suspensions.
- the foods according to the invention enriched with one or more compounds of the formula I can be prepared with the aid of techniques which are well known to the person skilled in the art.
- compounds of the formula I are also suitable as medicament ingredients.
- Compounds of the formula I can be used, for example, for preventative treatment of inflammation and allergies of the skin and in certain cases for preventing certain types of cancer.
- Compounds of the formula I are particularly suitable for the preparation of a medicament for the treatment of inflammation, allergies and irritation, in particular of the skin.
- medicaments which act as a vein tonic, as cuperose inhibitor, as chemical, physical or actinic erythema inhibitor, as agent for the treatment of sensitive skin, as decongestant, as desiccant, as slimming agent, as anti-wrinkle agent, as stimulator for the synthesis of components of the extracellular matrix, as strengthening agent for improving skin elasticity, and as anti-ageing agent.
- compounds of the formula I which are preferred in this connection exhibit antiallergic and antiinflammatory and antiirritative actions. They are therefore suitable for the preparation of medicaments for the treatment of inflammation or allergic reactions.
- Recrystallisation is carried out from a mixture of toluene and methanol.
- 2-Ethoxycarbonyl-7-hydroxychromone (14.5 g, 62 mmol) is initially introduced dissolved in ethanol (400 ml) at 50° C., and sodium carbonate (20 g, 190 mmol) dissolved in deionised H 2 O (200 ml) is added dropwise. The mixture is refluxed at 80° C. for 3 hours with stirring. After cooling, the mixture is acidified using 2N HCl. The precipitated white solid is filtered off with suction, washed until neutral and dried.
- the ester is obtained by esterification of the acid from Example 2 using 1-ethylhexyl alcohol.
- Ethyl 7-hydroxychromen-4-one-2-carboxylate (2 g, 8.538 mmol) and granulated and dried calcium chloride (1 g, 9.01 mmol) are initially introduced, and ethanol (absolute, 40 ml) is added.
- Sodium borohydride (1.33 g, 35.157 mmol) is subsequently added in portions with ice cooling.
- the reaction mixture is stirred at RT for 2 hours, then again cooled using an ice bath, and sodium borohydride (0.45 g, 11.895 mmol) is again added.
- the mixture is stirred overnight at RT.
- the ethanol is subsequently removed in a rotary evaporator (bath temperature: 50° C.), 60 ml of deionised water are carefully added to the residue, and the suspension is acidified dropwise using 2N HCl. About 100 g of ice are subsequently added to the solution, and the mixture is stirred for half an hour, during which a white solid precipitates, which is filtered off with suction and dried at 45° C. in a vacuum drying cabinet. 1.1 g of white solid. Yield: 67%
- the apparatus is allowed to cool to room temperature, the dark-brown suspension is added to about 200 ml of ice-water, 200 ml of CH 2 Cl 2 are added, and the mixture is extracted.
- the aqueous phase is extracted by shaking a further 2 ⁇ with 50 ml of CH 2 Cl 2 , and the black org. phases are combined and washed 2 ⁇ with 50 ml of deionised water, 3 ⁇ with 2 molar HCl (pyridine-free) and 1 ⁇ with saturated NaCl solution, leaving a clear black-brown org. phase, which is dried using Na 2 SO 4 .
- the ester is obtained by esterification of the acid from Example 4 using 1-ethylhexyl alcohol.
- 2,4,6-Trihydroxyacetophenone dissolved in acetic anhydride is initially introduced, and sodium acetate is added.
- the suspension is refluxed with stirring for 10 hours.
- the reaction mixture is subsequently poured into about 300 ml of ice-water and extracted 2 ⁇ with ethyl acetate (EA), and the org. phases are combined and washed 3 ⁇ with deionised H 2 O.
- the solution which remains is washed further with Na 2 HCO 3 solution.
- the organic phase is dried over Na 2 SO 4 , filtered and evaporated in a rotary evaporator.
- 2,4,6-Trihydroxyacetophenone (5 g, 26.3 mmol) is added to 90 ml of toluene, and 14 g of potassium carbonate dissolved in 70 ml of deionised water and 1 g of tetra-n-butylammonium hydrogensulfate are added to the solution.
- 2-Ethylhexanoyl chloride (20.5 ml, 119.7 mmol) is added dropwise to the two-phase mixture over the course of 10 minutes with vigorous stirring. The two-phase mixture is subsequently heated at 70° C. for 5 hours with stirring.
- the upper dark-red organic phase is subsequently separated off, the aqueous phase is extracted by shaking twice with dichloromethane, and the organic phases are combined, washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated to dryness in a Rotavapor (bath temperature: 50° C.).
- the filtrate is evaporated again, and 100 ml of heptane are added to the distillation residue, whereupon a solid precipitates, which is filtered off via a suction filter.
- m(K tot.): 3.92 g are 52.3% of the theoretical yield, based on the amount of 2,4,6-trihydroxyacetophenone used.
- the reaction mixture is introduced into 60 ml of deionised water, acidified using dilute HCl and extracted with 150 ml of EA.
- the aqueous phase is extracted a further 2 ⁇ with EA.
- the combined org. phases are extracted by shaking 2 ⁇ with 150 ml. of deionised water and 1 ⁇ with saturated NaCl solution, dried using Na sulfate and filtered, and the solvent is stripped off.
- reaction mixture is cooled using an ice bath and introduced into 50 ml of ice-water, EA is added, the mixture is filtered through Celite, the aqueous phase is separated off and extracted again with a little EA, and the org. phases are combined, washed 4 ⁇ with about 20 ml of deionised H 2 O each time and 1 ⁇ with sat. NaCl solution until neutral, dried using Na 2 SO 4 , filtered and evaporated in a rotary evaporator.
- Human keratinocytes of the cell line NCTC R13 are pre-cultivated for 24 hours at 37° C. in a 5% CO 2 atmosphere with DMEM culture medium (Life Technologies). The cells are treated with LU for 24 hours, and the culture medium is then removed. A fresh culture medium containing the inflammation-triggering active ingredient phorbol myristate acetate (PMA; 0.1 g/ml) and LU is added. After incubation for 24 hours, the culture medium is collected.and analysed. By means of an ELISA DE0100 kit (R&D Systems), the release is used in order to investigate the release of the inflammation marker prostaglandin E2 (PGE2) (Table). TABLE PGE2 release from human keratinocytes Control Neg.
- PMA phorbol myristate acetate
- HA hyaluronic acid
- BSA serum albumen
- 5,7-Dihydroxy-2-methylchromen-4-one in the doses investigated exhibits clear inhibition of hyaluronidase activity. 50% inhibition (IC 50 ) is achieved at about 20 mM of 5,7-dihydroxy-2-methylchromen-4-one.
- Formulations for cosmetic compositions comprising compounds according to Examples 1-3 are shown by way of example below.
- the INCl names of the commercially available compounds are also shown.
- UV-Pearl, OMC stands for the composition having the INCl name: Water (for EU: Aqua), Ethylhexyl Methoxycinnamate, Silica, PVP, Chlorphenesin, BHT; this composition is commercially available under the name Eusolex®UV PearlTM OMC from Merck KGaA, Darmstadt.
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Also Published As
Publication number | Publication date |
---|---|
US9044409B2 (en) | 2015-06-02 |
JP4850397B2 (ja) | 2012-01-11 |
ES2475516T3 (es) | 2014-07-10 |
JP2005060398A (ja) | 2005-03-10 |
EP1508327B1 (de) | 2014-05-07 |
US20080027133A1 (en) | 2008-01-31 |
EP1508327A1 (de) | 2005-02-23 |
DE10337863A1 (de) | 2005-03-17 |
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