Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
• • 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
  • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
  • A61K8/585—Organosilicon compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage

Definitions

• the present invention relates to hydroxybenzophenone UV absorbers, to the preparation of these compounds, to the use of these compounds for protecting human and animal skin and hair from the harmful effects of UV radiation, and to their use in cosmetic and pharmaceutical formulations.
• the problem of the present invention is therefore to find organic UV filters or mixtures of UV filters that have good solubility in solvents that are suitable for cosmetic formulations.
• UV absorber compositions comprising selected silylated benzophenone derivatives have such properties.
• the present invention therefore refers to hydroxyphenylbenzophenone derivatives of formula
• Ri and R 2 independently from each other are hydrogen; d-C 2 oalkyl; C 2 -C 2 oalkenyl; C 3 - C 2 ocycloalkyl; C 3 -Ciocycloalkenyl; or R 1 and R 2 together with the linking nitrogen atom form a 5- 6-membered heterocyclic ring; R 3 , R 4 and R 5 independently from each other are CrC 4 alkyl; Ci-C 4 alkoxy or a radical of
• R 6 is Ci-C 4 alkyl
• A is a straight-chain or branched C 3 -C 6 alkylene, which is optionally interrupted by one or more *-O-*, or *-O-(CO)-* groups; and m is 0; or anumber from 1 to 5.
• CrC 2 oalkyl denotes a linear or branched, unsubstituted or substituted alkyl group such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, cyclohexyl, n-decyl, n-dodecyl, n- octadecyl, eicosyl, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N 1 N- diethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-tert-butylphenethyl, p-tert-octyl- phenoxyethyl, 3-(2,4-di-tert-amylphenoxy)-propyl, ethoxycarbonyl
• C 2 -C 2 oalkenyl is for example allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n- penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec- 2-enyl or n-octadec-4-enyl.
• C 3 -Ci 0 cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl and preferably cyclohexyl.
• These radicals may besubstituted, for example by one or more or equal or different Ci-C 4 alkyl radicals, preferably by methyl, and/or hydroxy. If cycloalkyl radicals are substituted by one or more radicals, they are preferably substituted by one, two or four, preferably by one or two equal or radicals.
• C 3 -Ciocycloalkenyl is for example cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl, cycloocentyl, cyclononenyl or cyclodecenyl and preferably cyclohexenyl.
• These radicals may be substituted with one or more equal or different Ci-C 4 alkyl radical, preferably with methyl, and/or hydroxy.
• cycloalkenyl radicals are substituted with one or more radicals they are preferably substituted with one, two, three or four, preferably with one or two equal or different radicals.
• Hydroxy substituted CrC 5 alkyl groups are for example hydroxymehtyl, hydroxyethyl, hydroxypropyl, hydroxybutyl or hydroxypentyl.
• C-i-Cealkylene is for example methylene, ethylene, propylene, butylenes or hexylene.
• the alklyene radicals may optionally be substituted by one or more CrC 5 alkyl radicals.
• R 1 and R 2 are heterocyclic radicals, these comprise one, two, three or four equal or different ring hetero atoms. Special preference is given to heterocycles which contain one, two or three, especially one or two, identical or different hetero atoms.
• the heterocycles may be mono- or poly-cyclic, for example mono-, bi- or tri-cyclic. They are preferably mono- or bi- cyclic, especially monocyclic.
• the rings preferably contain 5, 6 or 7 ring members.
• Examples of monocyclic and bicyclic heterocyclic systems from which radicals occurring in the compounds of formula (1 ) may be derived are, for example, pyrrole, furan, thiophene, imidazole, pyrazole, 1 ,2,3-triazole, 1 ,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, thiopyran, 1 ,4-dioxane, 1 ,2-oxazine, 1 ,3-oxazine, 1 ,4-oxazine, indole, benzothiophene, benzofuran, pyrrolidine, piperidine, piperazine, morpholine and thiomorpholine.
• Ri and R 2 are preferably CrC 2 oalkyl, more preferably Cr C 5 alkyl and most preferably Ri and R 2 in formula (1 ) have the same definition
• A is preferably C 3 -C 6 alkylene; or (d-C 5 alky- lene)-O-(CO)-(CrC 5 )alkylene.
• m is preferably 0.
• R 3 and R 4 in formula (1 ) are preferably a radical of formula (1 a) *— o— Si-R 6 ; wherein
• R 6 R 6 is Ci-C 6 alkyl.
• R 3 and R 4 are a radical of formula (1a) *-O-Si-R 6 ;
• R 6 is Ci-C 5 alkyl
• A is Csalkylene; and m is 0.
• the compounds of formula (1 ) may be prepared by a manner known per se.
• Ri and R 2 R3, R 4 and R 5 , A and m are defined as in formula (1 ).
• Another preparation route comprises hydrosilylation of the unsaturated ester of benzophenone carboxylic acid e.g. Allylesters using known Catalyst (Pt, Cu) and corresponding hydrosiloxane.
• the reaction is usually carried out at a temperature from 25 to 200°C. Generally a solvent is not necessary for this reaction. If a solvent is used however, preferably the solvents as used in the working examples are preferred.
• the reaction time is usually from 0.5 to 20 h.
• Ri and R 2 are defined as in formula (1 ).
• the compounds of the formula (1 ) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds are preferably used in dissolved form.
• the cosmetic formulations or pharmaceutical compositions according to the present invention may additionally contain one or more than one further conventional UV filter.
• the cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, al- coholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments.
• the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
• water- and oil-containing emulsions e.g.
• the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, espec- ially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further
• the cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes, organosubstituted super-fatting agents, surfactant consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as spf enhancers.
• additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes, organosubstituted super-fatting agents, surfactant consistency regulators/thickeners and rheology
• Cosmetic or pharmaceutical formulations are ingredients in a wide variety of cosmetic preparations. The following preparations are of special interest:
• skin-care preparations e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes; or skin emulsions, multi-emulsions or skin oils
• bath preparations e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts
• cosmetic personal care preparations e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams
• lip-care preparations e.g.
• nail-care preparations such as nail varnish, nail varnish removers, nail hardeners or cuticle removers
• foot-care preparations e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations
• - light-protective preparations such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations
• skin-tanning preparations e.g. self-tanning creams
• depigmenting preparations e.g.
• preparations for bleaching the skin or skin-lightening preparations e.g. - insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; hair-removal preparations in chemical form (depilation), e.g.
• hair-removing powders liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair- removing preparations in gel form or aerosol foams
• shaving preparations e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions
• fragrance preparations e.g. fragrances (eau de Cologne, eau de toilette, eau de perfume, perfume de toilette, perfume), perfume oils or perfume creams
• cosmetic hair-treatment preparations e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g.
• pretreatment preparations hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per- oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.
• Presentation forms e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per- oxide solutions, lightening shampoos, bleaching creams, bleaching
• liquid preparations as a W/O, O/W, 0/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, - in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
• a spray spray with propellent gas or pump-action spray
• aerosol in the form of a foam, or in the form of a paste.
• cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams.
• light-protective preparations such as sun milks, lotions, creams, oils, sunblocks or tropicals
• pretanning preparations or after-sun preparations also skin-tanning preparations, for example self-tanning creams.
• sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray are particularly interested.
• hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair- straightening preparations, liquid hair-setting preparations, hair foams and hairsprays.
• hair-washing preparations in the form of shampoos.
• a shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.
• compositions are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.
• the cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.
• reaction mass is worked off after evaporation with column chromatography (silicagel 60/toluene: acedic acid ethyl ester).
• the solubility in Cyclomethicone at RT is > 20 %.
• 26g of the compound of formula and 58.8g of the compound of formula (101 a) are mixed together with 200ml propyl acetate.
• the mixture is concentrated to a volumn of about 100ml with the rotating evaporator and
• Examples B1 to B3 are water silicone formulations wherein the compound of formula (102) is used as silicone soluble UV-A filter.
• Examples B4 to B6 are water silicone formulations wherein the compound of formula (103) is used as silicone soluble UV-A filter.

Landscapes

• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Dermatology (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Cosmetics (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=36010871

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (2)

Citations (7)

Family Cites Families (10)

• 2007
  • 2007-02-06 WO PCT/EP2007/051117 patent/WO2007090832A1/en not_active Ceased
  • 2007-02-06 ES ES07726317.6T patent/ES2584204T3/es active Active
  • 2007-02-06 JP JP2008553748A patent/JP5294877B2/ja not_active Expired - Fee Related
  • 2007-02-06 EP EP07726317.6A patent/EP1981895B1/en active Active
  • 2007-02-06 US US12/223,686 patent/US7999128B2/en not_active Expired - Fee Related
  • 2007-02-07 GB GB0702326A patent/GB2435041A/en not_active Withdrawn

Patent Citations (7)

Also Published As

Similar Documents

Legal Events