Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• • 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
  • A61K8/37—Esters of carboxylic acids
• • 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
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
  • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/22—Organic complexes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/24—Phosphines

Definitions

• the present invention relates to a process for the preparation of unsaturated alpha, omega dicarboxylic acids, and alpha, omega dicarboxylic acid diesters, which have an improved absorption in the UV range, in particular in the UV-B range.
• UV sunscreen filter substances pose challenges to the person skilled in the art in terms of formulation; furthermore, skin intolerances of UV sunscreen filter substances are also known.
• unsaturated alpha, omega dicarboxylic acids and alpha, omega dicarboxylic diesters are obtained with the process according to the invention, which have an increased absorption in the UV range, in particular in the UV-B range.
• Unsaturated alpha, omega dicarboxylic acids and / or alpha, omega dicarboxylic acid diesters obtained by the process according to the invention are therefore suitable, in particular in cosmetic preparations, for sun protection.
• the invention relates to a process for the preparation of unsaturated alpha, omega dicarboxylic acids and alpha, omega dicarboxylic acid diesters, which comprises unsaturated carboxylic acids and / or esters of unsaturated carboxylic acids in the presence of the catalyst (1) and / or (2)
• Suitable starting materials for the process according to the invention are mono- or polyunsaturated carboxylic acids having 14 to 24 carbon atoms, which may be optionally branched.
• the double bonds of the carboxylic acids can be present both in ice and in trans configuration.
• Suitable as carboxylic acids are the compounds of the following formula R 1 -COOH, wherein R 1 represents a mono- or polyunsaturated alkyl radical having 13 to 23 carbon atoms.
• R 1 represents a mono- or polyunsaturated alkyl radical having 13 to 23 carbon atoms.
• the polyunsaturated alkyl radical its example, two, three, four, five or six times unsaturated alkyl called.
• the R 1 radical may be cyclic or acyclic, preferably the radical R 1 is aeyclic.
• the R 1 radical may be branched or unbranched, preferred are carboxylic acids having an unbranched radical R 1 . Particular preference is given to carboxylic acids having a noncyclic radical R 1 .
• the short notation for oleic acid is 18: 1 (9). If the double bond is in the trans configuration, this is indicated by the abbreviation "tr.” Thus, the short notation for elaidic acid is 18: 1 (tr9).
• Suitable polyunsaturated carboxylic acids are, for example, linoleic acid [18: 2 (9,12); (9Z, 12Z) - octadeca-9,12-dienoic acid], alpha-linolenic acid [18: 3 (9,12,15); (9Z, 12Z, 15Z) - Octadeca-9,12,15-trienoic acid], gamma-linolenic acid [18: 3 (6,9,12); (6Z, 9Z, 12Z) octadeca-6,9,12-trienoic acid], calendulic acid [18: 3 (8, 10, 12); (8 £, 10 £, 12Z) -Octadeca-8,10,12-trienoic acid], punicic acid [18: 3 (9,11,13); (9Z, ll £, 13Z) -Octadeca-9,11,13-trienoic acid], alpha-eleostearic acid [18: 3 (9,11,13
• esters of the mono- or polyunsaturated carboxylic acids mentioned are also suitable as starting materials.
• Particularly suitable esters are esters of these carboxylic acids with alcohols R 2 -OH, where R 2 is an alkyl radical having 1 to 8 C atoms.
• radicals R 2 are: methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, pentyl, 2,2-dimethylpropyl, 2-methylbutyl, 3-methylbutyl, hexyl , 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, heptyl, and octyl radicals.
• esters of said mono- or polyunsaturated carboxylic acids with glycerol are suitable as starting materials.
• glycerol ester glycerol ester
• glycerol monoesters monoglycerides, monoacylglycerol
• glycerol diesters diglycerides, diacylglycerol
• glycerol triesters triglycerides, triacylglycerol
• the unsaturated carboxylic acids or the esters of the unsaturated carboxylic acids can be present both individually and in mixtures with one another. If exclusively an unsaturated carboxylic acid or the ester of only one unsaturated carboxylic acid is used, a reaction called self-metathesis takes place. If various unsaturated carboxylic acids or esters of various unsaturated carboxylic acids are used, a reaction called cross-metathesis takes place.
• the process according to the invention is carried out in the presence of the catalysts (1) and / or (2).
• Catalyst (1) is the compound of the following structural formula:
• This catalyst is dichloro [l, 3-bis (mesityl) -2-imidazolidinylidenes] - (3-phenyl-1H-inden-1-ylidenes) (tricyclohexylphosphines) ruthenium (II), CAS No. 536724 -67-1. It is commercially available, for example, under the name Neolyst TM M2 from Umicore.
• Catalyst (2) is the compound of the following structural formula:
• This catalyst is [l, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidenes] - [2 - [[(4-methylphenyl) imino] methyl] -4-nitrophenolyl] - [3 -phenyl-1H-inden-1-ylidenes] ruthenium (II) chloride, CAS No. 934538-04-2. It is commercially available, for example, under the name Neolyst TM M41 from Umicore.
• the catalyst according to the invention is preferably used in concentrations of less than or equal to 1000 ppm, in particular in the range from 10 to 1000 ppm, preferably from 20 to 200 ppm.
• the inventive method can at temperatures of 0 to 100 ° C, preferably at
• the process can be dissolved in customary solvents in which the starting materials and the catalyst dissolve, such as, for example: hydrocarbons or alcohols.
• the process can be carried out solvent-free.
• unsaturated alpha, omega dicarboxylic acids and unsaturated alpha, omega dicarboxylic acid diesters and the corresponding unsaturated hydrocarbons are obtained. Separation of the mixture may e.g. carried out by distillation, by fractional crystallization or by extraction.
• the products thus obtained may be subjected to hydrogenation.
• the unsaturated alpha, omega dicarboxylic acids and unsaturated alpha, omega dicarboxylic acid diesters prepared by the process according to the invention are themselves used in cosmetic preparations. Due to their UV-B absorption, they are particularly suitable in sunscreen cosmetic preparations. Examples
• Example Ia was repeated, but the reaction was carried out at 40 ° C for 4 h.
• Example Ia was repeated, but the reaction was carried out at 30 ° C. for 7 h,
• Example 3 The UV-B absorption of the product obtained according to Example 3 and of the product obtained according to Example 4 was measured. Surprisingly, the product obtained according to Example 3 showed a higher absorption in the range of 240 to 280 nm in comparison to the product prepared according to the prior art (Example 4).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dermatology (AREA)
• Crystallography & Structural Chemistry (AREA)
• Emergency Medicine (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Cosmetics (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2008
  • 2008-08-21 EP EP08014838A patent/EP2157076A1/de not_active Withdrawn
• 2009
  • 2009-08-12 EP EP09777826A patent/EP2313361A1/de not_active Withdrawn
  • 2009-08-12 US US13/060,011 patent/US20110171147A1/en not_active Abandoned
  • 2009-08-12 WO PCT/EP2009/005841 patent/WO2010020368A1/de not_active Ceased
  • 2009-08-12 KR KR1020117003801A patent/KR20110044234A/ko not_active Ceased
  • 2009-08-12 CN CN200980132264.XA patent/CN102131763B/zh not_active Expired - Fee Related
  • 2009-08-12 BR BRPI0917520A patent/BRPI0917520B1/pt not_active IP Right Cessation
  • 2009-08-12 JP JP2011523336A patent/JP5653919B2/ja not_active Expired - Fee Related

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