EP3204365A1 - Monoesters et diesters à chaîne longue de 2,5-di(hydroxyméthyl)tétrahydrofurane, leur fabrication et leur utilisation - Google Patents

Monoesters et diesters à chaîne longue de 2,5-di(hydroxyméthyl)tétrahydrofurane, leur fabrication et leur utilisation

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Publication number
EP3204365A1
EP3204365A1 EP15748256.3A EP15748256A EP3204365A1 EP 3204365 A1 EP3204365 A1 EP 3204365A1 EP 15748256 A EP15748256 A EP 15748256A EP 3204365 A1 EP3204365 A1 EP 3204365A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkenyl
branched
acid
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15748256.3A
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German (de)
English (en)
Inventor
Dominik Ohlmann
Markus Dierker
Vanessa PÜTZ
Stefan Busch
Rene Backes
Anne van den WITTENBOER
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BASF SE
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BASF SE
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Publication of EP3204365A1 publication Critical patent/EP3204365A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/20—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
    • A61K31/341—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide not condensed with another ring, e.g. ranitidine, furosemide, bufetolol, muscarine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/22—Heterocyclic compounds, e.g. ascorbic acid, tocopherol or pyrrolidones
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y301/00—Hydrolases acting on ester bonds (3.1)
    • C12Y301/01—Carboxylic ester hydrolases (3.1.1)
    • C12Y301/01003—Triacylglycerol lipase (3.1.1.3)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use

Definitions

  • the present invention relates to novel mono- and diesters of 2,5-di (hydroxymethyl) -tetrahydrofuran, to processes for their preparation by esterification in the presence of tertiary amines or in the presence of enzymatic esterification catalysts and to the use of these mono- and diesters as surface-active compounds, rheology product modifiers and emollients.
  • the invention further relates to cosmetic and pharmaceutical compositions as well as washing, cleaning and dishwashing agents containing these mono- and diesters of 2,5-di (hydroxymethyl) tetrahydrofuran.
  • Surfactants are generally surface-active compounds which reduce the interfacial tension between two phases. Thus, they allow, for example, the better wetting of solid surfaces with a liquid by lowering the surface tension or the formation of dispersions. They are used very widely, for. B. as washing and cleaning active substances in detergents, detergents, cleaning agents and personal care products as well as solubilizers or wetting agents, eg. B. in cosmetics, pharmacy, food industry, material protection, crop protection, etc.
  • emulsifiers are usually surface-active compounds which serve to mix two immiscible liquids, such as water and an oil body to form an emulsion and to stabilize them against segregation.
  • Solubilizers increase the solubility of a substance in a solvent by adding a third substance.
  • mediators which change the dissolution properties of the solvent by homogeneous mixing
  • surfactants which increase the solubility by micelle formation.
  • Emollients are nourishing and hydrating skin care products (eg in the form of ointments, creams and lotions) that moisturize and moisturize the skin. They are used in numerous skin diseases and are usually free of active pharmaceutical ingredients. Some contain moisturizing or binding substances, such as urea or lactic acid.
  • Rheology describes a force acting on a material that causes fluids to flow to avert the pressure of that force. All materials counteract an applied shear force. This resistance is an internal force that is usually tangential to the claimed area. The measurement of this resistance gives the viscosity, a basic value of rheology.
  • Rheological behavior knows two extremes, on the one hand elastic behavior (absolutely rigid solids): The effect of an applied force spontaneously turns into its opposite when it is lifted. The system stores energy and releases it in the sequence. On the other hand, viscous or plastic behavior (ideal Newtonian fluids): any deformation immediately subsides when the applied force is removed.
  • the rheology of flowable systems is of great importance to many areas of technology. To adjust the viscosity behavior of fluid components to the respective application-specific requirements, such. As the provision of a higher viscosity liquid composition, a paste or a gel
  • Theological additives can be incorporated into existing flowable systems. Rheology modifiers in the sense of the invention serve to influence the viscosity of flowable compositions in the desired manner and as consistency regulator, structuring agent, gelling agent, etc.
  • fatty acid esters in general in cosmetic and pharmaceutical products in which they are used, inter alia, as oil bodies and emollients. It is also known to produce esters from fatty alcohols and fatty acids by enzymatic synthesis.
  • lipases to produce fatty acid esters, such as decyl oleate, cetyl ricinoleate, myristyl myristate or decyl cocoate, is described, for example, by Gerissay Hills in Eur. J. Lipid Sci. Technol. 105, 2003, pages 601-607.
  • US 4,826,767 describes the enzymatic synthesis of esters of fatty acids and fatty alcohols in the liquid phase and in vacuo in the presence of an immobilized lipase.
  • EP 2 080 807 A2 describes a process for the enzymatic preparation of carboxylic acid esters, the thorough mixing of the reactants and the discharge of the water of reaction being effected by introducing a gas.
  • WO 2014/056756 describes a three-stage process for enzymatic fatty acid synthesis in which fatty alcohols and fatty acids are reacted in the presence of an enzyme at a temperature in the range of 30 to 50 ° C, the water formed is removed and then the reaction under vacuum at a temperature of 50 to 80 ° C is completed.
  • Enzymatic ester syntheses using 2,5-di (hydroxymethyl) tetrahydrofuran or structurally related diols are not known.
  • 2,5-Di (hydroxymethyl) tetrahydrofuran (IUPAC: [5- (hydroxymethyl) oxolan-2-yl] methanol, also called THF glycol) is commercially available and is used, for example, for the preparation of plasticizers, polymer resins and as a solvent.
  • THF glycol 2,5-Di (hydroxymethyl) tetrahydrofuran
  • R 1 and R 2 are independently selected from C 4 -C 8 -alkyl and C 5 -C 6 -cycloalkyl, where the cycloalkyl radicals are unsubstituted or may be substituted by at least one C 1 -C 10 -alkyl radical.
  • thermoplastic polymers in particular polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • An exemplary embodiment of a diester of 2,5-di (hydroxymethyl) -tetrahydrofuran is not included in this application.
  • the non-prepublished European patent application 13182979.8 describes tetrahydrofuran derivatives of the general formula (F),
  • R 1 and R 2 are independently selected from unbranched and branched C 7 -C 12 -alkyl radicals.
  • thermoplastic polymers in particular polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the object of the present invention is to provide compounds which are advantageously suitable for use as surface-active compounds, rheology modifiers or emollients for various applications. They should be especially suitable to cover a complex range of requirements, as described above.
  • the first object of the invention is compounds of the general formula (I)
  • R 2 is hydrogen and R 1 is unbranched or branched Cs-Css-alkyl or unbranched or branched Cs-Css-alkenyl having 1, 2, 3 or more than 3 double bonds, wherein Cs-Css-alkyl and Cs- Css alkenyl by at least one
  • Hydroxyl group may be substituted and / or may have at least one epoxy group.
  • At least one of the radicals R 1 and R 1 ' is unbranched or branched C 2 -C 12 -alkyl or unbranched or branched Cn-C2i alkenyl having 1, 2 or 3 double bonds, wherein Cn-C2i-alkyl and C11-C21 alkenyl may be substituted by at least one hydroxyl group.
  • the invention furthermore relates to a cosmetic or pharmaceutical composition
  • a cosmetic or pharmaceutical composition comprising at least one compound of the general formula (I) as defined above and below, and at least one cosmetic or pharmaceutical active ingredient and / or adjuvant other than this.
  • Another object of the invention is a washing, cleaning or dishwashing detergent, comprising at least one compound of the general formula (I), as defined above and below, and at least one different surfactant.
  • Another object of the invention is the use of at least one compound of general formula (I), as defined above and hereinafter, as a surface-active compound.
  • the compounds of the general formula (I) are advantageously suitable as surfactants, emulsifiers, solubilizers and foaming agents.
  • suitable and preferred compounds of the general formula (I) are described in more detail below.
  • Another object of the invention is the use of at least one compound of general formula (I), as defined above and below, as rheology modifier. Suitable and preferred compounds of the general formula (I) for use as rheology modifiers are also described in more detail below.
  • Another object of the invention is the use of at least one compound of the general formula (I), as defined above and below, as Emollientien. For use as emollients suitable and preferred compounds of general formula (I) are also described in more detail below.
  • 2,5-di (acyloxymethyl) tetrahydrofuran in the context of the invention cis / trans mixtures of any composition and the pure configuration isomers.
  • the abovementioned terms furthermore denote all enantiomers in pure form as well as racemic and optically active mixtures of the enantiomers of these compounds.
  • rheology modifier and “rheological modification” are well understood in the context of the present invention.
  • the correspondingly used compounds of the formula (I) are generally suitable for thickening the consistency of liquid compositions in a wide range. Depending on the basic consistency of the liquid compositions, depending on the amount used of the compounds of the general formula (I), it is generally possible to achieve flow properties from low viscosity to solid (in the sense of "no longer flowing”).
  • modifying rheological properties is meant inter alia increasing the viscosity of liquids, improving the thixotropic properties of liquids and gels, solidifying gels and waxes, etc.
  • the compounds of the formula (I) are particularly suitable for modifying the rheological properties of aqueous compositions.
  • solubility improvement is also broadly understood in the context of the present invention in the sense of a solubility improvement. This includes, on the one hand, the stabilization of heterogeneous systems in which the sparingly soluble substance is present as an emulsified or dispersed phase (disperse phase) in a liquid (eg aqueous) medium as a continuous phase. This also includes the stabilization of transition states to homogeneous solutions, such as colloidal solutions, etc., all the way to molecular dispersion solutions. This also includes a solubility improvement in the sense of solubilization, in which the poorly soluble or insoluble substances are converted into solutions which are preferably clear or at most opalescent. Finally, this includes the ability to form so-called "solid solutions”.
  • a low (poor) solubility in the context of this invention means a solubility in a solvent (especially in water) of below 10 g / l, in particular below 1 g / l and especially below 0.1 g / l at 25 ° C and 1013 mbar , Suitable Cs-Css-alkyl groups, Cs-Css-alkyl groups, Cn-C35-alkyl groups, C11-C21-alkyl groups, C5-C23-alkyl groups, Cs-Css-alkenyl groups, Cs-Css-alkenyl groups, Cn-C35-alkenyl groups, Cn -C2i-alkenyl groups and Cs-C23-alkyl groups are each straight-chain and branched alkyl or alkenyl groups.
  • the alkenyl group contains more than one carbon-carbon double bond, these are preferably not vicinal, i. H. not allish.
  • radical R 1 or if the radicals R 1 and R 1 'are alkyl radicals or alkenyl radicals these are preferably derived from natural raw materials, particularly preferably from a renewable raw material.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched Ci i-C2i-alkyl they are preferably selected from n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n Pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, arachinyl, isotridecyl, isostearyl, and their constitutional isomers.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched C 1 -C -alkyl they are preferably selected from the above-mentioned C 1 -C 12 -alkyl radicals, behenyl, lignocerinyl, cerotinyl, Melissinyl, and their constitutional isomers.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched C 8 -C 35 -alkyl they are preferably selected from the above-mentioned C 1 -C 35 -alkyl radicals, n-octyl, 2-ethylhexyl, n Nonyl, n-decyl, and their constitutional isomers.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched C 5 -C 35 -alkyl they are preferably selected from the above-mentioned C 8 -C 35 -alkyl radicals, n-pentyl, n-hexyl, n Heptyl, and their constitutional isomers.
  • Examples are 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxy-decyl, 1-hydroxyheptadecyl, 8,9-bis-hydroxyheptadecyl and 3-hydroxyheptadecyl.
  • radical R 1 or the radicals R 1 and R 1 ' is unbranched or branched Cs-Css-alkyl which is substituted by 1, 2 or 3 hydroxyl groups.
  • radical R 1 or the radicals R 1 and R 1 ' is unbranched or branched Cs-Css-alkyl which is substituted by 1, 2 or 3 hydroxyl groups.
  • radical R 1 or the radicals R 1 and R 1 ' is unbranched or branched C 2 -C 12 -alkyl which is substituted by 1, 2 or 3 hydroxyl groups.
  • radical R 1 is unbranched or branched Cs-Css-alkyl, Cs-Css-alkyl, Cn-Css-alkyl or Cn-C2i-alkyl, has at least one epoxy group, they are preferably derived from the aforementioned Cs Css-alkyl, Cs-Css-alkyl, Cn-Css-alkyl or Cii-C2i-alkyl groups carrying at least one (eg 1, 2, 3, 4 or more than 4) epoxy groups.
  • the radical R 1 is unbranched or branched Cs-Css-alkyl which carries 1, 2, 3 or 4 epoxy groups. In a further preferred embodiment, the radical R 1 is unbranched or branched Cs-Css-alkyl which carries 1, 2, 3 or 4 epoxy groups.
  • the radical R 1 is unbranched or branched C 2 -C 12 -alkyl which carries 1, 2, 3 or 4 epoxy groups.
  • Suitable Cs-Css-alkenyl groups, Cs-Css-alkenyl groups, Cn-C3s-alkenyl groups and Cii-C2i-alkenyl groups are in each case straight-chain and branched alkenyl groups which may be mono-, di-, tri- or more-triunsaturated.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched C 12 -C 12 -alkenyl they are preferably selected from n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-undecenyl Pentadecenyl, n-hexadecenyl, n-heptadecenyl, n-octadecenyl, n-nonadecenyl, n-eicosenyl, linolenyl, eleostearyl and oleyl (9-octadecenyl) and their constitutional isomers.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched Cii-C35 alkenyl they are preferably selected from the above-mentioned led Cn-C2i alkenyl radicals, n-docosenyl, n-tetracosenyl, n-hexacosenyl, and their constitutional isomers.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched C 8 -C 35 alkenyl they are preferably selected from the above-mentioned Ci i-C35 alkenyl radicals n-octenyl, n-nonenyl, n -Decenyl, and their constitution isomers.
  • radical R 1 or when the radicals R 1 and R 1 'are unbranched or branched C 5 -C 35 alkenyl they are preferably selected from the above-mentioned C 8 -C 35 alkenyl radicals, n-pentenyl, n-hexenyl, n -Heptenyl, and their constitutional isomers.
  • the radicals R 1 and R 1 ' which are C 5 -C 35 -alkyl, C 8 -C 35 -alkyl, Cn-C 35 -alkyl, Cn-C 2 -alkyl, C 5 -C -alkenyl, Cs- Css-alkenyl, Cn-C35-alkenyl and Cn-C2i-alkenyl, can be derived from the corresponding carboxylic acids by formal cleavage of the COOH group.
  • the radicals R 1 and R 2 can be derived from pure carboxylic acids or from carboxylic acid mixtures. Preferably, it is industrially available carboxylic acids or carboxylic acid mixtures.
  • R 1 and R 2 are independently derived from fatty acids based on technical fatty acid mixtures.
  • Preferred monocarboxylic acid are naturally occurring fatty acids and fatty acid mixtures. These are present in nature as oils or fats in the form of triglycerides. They can be used for the preparation of the compounds (I) according to the invention in the form of the free fatty acid or a derivative, especially in the form of an acid halide, ester or anhydride.
  • Suitable saturated aliphatic monocarboxylic acids are, for example, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, tuberculostearic acid, arachic acid, behenic acid, etc.
  • Suitable unsaturated monocarboxylic acids have at least one double bond (unsaturation). They can also have 2, 3, 4, 5 or 6 double bonds. The double bonds can each have (E) or (Z) configuration.
  • Preferred monounsaturated carboxylic acids are undecenoic acid (C1 1), dodecenoic acid (C12), tridecenoic acid (C13), tetradecenoic acid (C14), pentadecenoic acid (C15), hexadecenoic acid (C16), heptadecenoic acid (C17), octadecenoic acid (C18), nonadecene acid.
  • the unsaturation can occur at any position in the alkenyl chain.
  • the double bonds can each have (E) or (Z) configuration.
  • linear, monounsaturated carboxylic acids are used. These are preferably selected from n-undecenoic acid (C1 1), n-dodecenoic acid (C12), n-tridecenoic acid (C13), n-tetradecenoic acid (C14), n-pentadecenoic acid (C15), n-hexadecenoic acid (C16), n- Heptadecenoic acid (C17), n-octadecenoic acid (C18), n-nonadecenoic acid (C19), n-eicosenoic acid (C20), n -docosenoic acid (C22), n-tetracenoic acid (C24).
  • the unsaturation can occur at any position in the alkenyl chain.
  • the double bonds can each have (E) or (Z) configuration.
  • Preferred examples of monounsaturated linear carboxylic acids are:
  • Myristoleic acid (IUPAC: (Z) -tetradec-9-enoic acid, C14: 1, [omega] -5)
  • Palmitoleic acid (IUPAC: (Z) -hexadec-9-enoic acid; 16: 1, [omega] -7)
  • Oleic acid (IUPAC: (Z) octadec-9-enoic acid; 18: 1 [omega] -9)
  • Linolenic acid (IUPAC (all-Z) -9,12-octadecadienoic acid; 18: 2 [omega] -6)
  • Gamma-linolenic acid (all-Z) -6,9,12-octadecatrienoic acid; GLA; C18: 3, [omega] -6) eleostearic acids, (Octadeca-9,1 1, 13-trienoic acid; C18: 3), such as alpha-eleostearic acid [(9Z.1 1E, 13E) -9.1 1, 13 -Octadeca-9.1, 13-trienoic oacid]
  • Eicosapentaenoic Acid [(all-Z) -5,8,1,1,14,17-lcosapentaenoic Acid, EPA, C22: 5]
  • six-unsaturated linear carboxylic acids are:
  • Docosahexaenoic acid [(4Z, 7Z, 10Z, 13Z, 16Z, 19Z) docosa-4,7, 10,13,16,19-hexaenoic acid, C 22: 6, cervonic acid, [omega] -3)
  • the radicals R 1 and R 1 ' are unbranched or branched C 1 -C 12 -alkyl or unbranched or branched C 1 -C 12 -alkenyl having 1, 2 or 3 double bonds, where C2i-alkyl and Cn-C2i-alkenyl may be substituted by at least one hydroxyl group.
  • the radical R 1 or the radicals R 1 and R 1 ' are unsubstituted unbranched or branched C 2 -C 12 -alkyl.
  • the radical R 1 or the radicals R 1 and R 1 ' are unbranched or branched C 2 -C 12 -alkyl which is substituted by 1, 2 or 3 hydroxyl groups is.
  • the radical R 1 or the radicals R 1 and R 1 ' are unsubstituted unbranched or branched C 2 -C 20 -alkenyl having 1, 2 or 3 double bonds.
  • the radical R 1 or the radicals R 1 and R 1 ' are unbranched or branched C 2 -C 12 -alkenyl having 1, 2 or 3 double bonds, which is represented by 1, 2 or 3 hydroxyl groups is substituted.
  • the radical R 1 or the radicals R 1 and R 1 ' are unbranched or branched C 2 -C 20 -alkenyl having 1, 2 or 3 double bonds, the 1, 2 , 3 or 4 epoxy groups.
  • R 2 is hydrogen.
  • the radicals R 1 and R 1 ' are n-dodecyl (lauryl), n-tridecyl, n-tetradecyl (myristyl), n-pentadecyl, n-hexadecyl (palmitinyl), n-heptadecyl (Margarinyl) or n-octadecyl (stearyl).
  • 2,5-di (hydroxymethyl) tetrahydrofuran is obtainable by hydrogenation of 2,5-di (hydroxymethyl) furan.
  • 2,5-di (hydroxymethyl) furan can, for. B. starting from fructose by dehydration to 5-hydroxymethylfurfural and subsequent reduction of the formyl group.
  • preparation of the 2,5-di (hydroxymethyl) tetrahydrofuran from biogenic sources starting from corresponding carbohydrates, e.g. As starch, cellulose and sugars possible.
  • the mono- and diesters of 2,5-di (hydroxymethyl) tetrahydrofuran according to the invention can also be prepared via the corresponding mono- and diesters of 2,5-di (hydroxymethyl) furan and these are subsequently subjected to hydrogenation.
  • the starting materials used to prepare the compounds of the general formula (I) originate, at least in part, from a renewable source or are produced from renewable raw materials.
  • renewable sources are understood to mean natural (biogenic) sources and not fossil sources, such as crude oil, natural gas or coal.
  • Renewable compounds have a different 14 C to 12 C isotope ratio than compounds derived from fossil sources such as petroleum.
  • the compounds of general formula (I) thus preferably have a 14 C to 12 C isotope ratio in the range of 0.5x10 "12 to 5x10 " 12 .
  • Another object of the invention is a process for the preparation of compounds of general formula (I)
  • R 2 is hydrogen and R 1 is unbranched or branched Cs-Css-alkyl or unbranched or branched Cs-Css-alkenyl having 1, 2, 3 or more than 3 double bonds, wherein Cs-Css-alkyl and Cs- Css alkenyl by at least one
  • Hydroxyl group may be substituted and / or may have at least one epoxy group in which
  • tertiary amines which are familiar to the person skilled in the art.
  • suitable tertiary amines are: from the group of trialkylamines: trimethylamine, triethylamine, tri-n-propylamine, diethylisopropylamine, diisopropylethylamine and the like;
  • N-cycloalkyl-N, N-dialkylamines dimethylcyclohexylamine and diethylcyclohexylamine;
  • pyridine and quinoline bases from the group of pyridine and quinoline bases: pyridine, ⁇ -, ⁇ - and ⁇ -picoline, quinoline and 4- (dimethylamino) pyridine (DMAP).
  • DMAP dimethylamino pyridine
  • Preferred tertiary amines are trialkylamines and pyridine bases, in particular triethylamine and 4- (dimethylamino) pyridine (DMAP), and mixtures thereof.
  • a trialkylamine preferably selected from trimethylamine, triethylamine, tri-n-propylamine, diethylisopropylamine and diisopropylethylamine is used for the esterification.
  • the trialkylamine is preferably used in a least stoichiometric ratio based on the hydroxyl groups of the 2,5-di- (hydroxymethyl) tetrahydrofuran.
  • the trialkylamine is particularly preferably used in an at least stoichiometric ratio up to a fourfold stoichiometric excess, based on the hydroxyl groups of the 2,5-di (hydroxymethyl) tetrahydrofuran.
  • dimethylaminopyridine for the esterification it is preferred to use dimethylaminopyridine in addition to at least one trialkylamine. It is assumed that dimethylaminopyridine acts as a catalyst.
  • the amount of dimethylaminopyridine used is preferably in a range from 0.01 to 0.5 molar equivalents, particularly preferably from 0.05 to 0.2 molar equivalents, based on 2,5-di (hydroxymethyl) tetrahydrofuran.
  • the esterification in a temperature range of -10 to 75 ° C, preferably 0 to 60 ° C, performed.
  • thermal decomposition of 2,5-di (hydroxymethyl) tetrahydrofuran is avoided, as observed in the processes known in the art in the strongly acidic medium and at elevated temperature.
  • good selectivity with respect to the respective process product is achieved at these low temperatures.
  • the esterification can be carried out at ambient pressure, at reduced or elevated pressure. Preferably, the esterification is carried out at ambient pressure.
  • the esterification may be carried out in the absence or in the presence of an organic solvent.
  • the reaction is carried out in the presence of an inert organic solvent, preferably selected from aliphatic ethers, cyclic ethers, ketones, chlorinated hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatics and mixtures thereof.
  • Suitable solvents are THF, dioxane, methyl tert-butyl ether, diethyl ether, acetone, methyl ethyl ketone, dichloromethane, trichloromethane, carbon tetrachloride, pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes and mixtures thereof.
  • the reaction is carried out in the presence of a substantially anhydrous organic solvent.
  • the alkylation can be carried out in the absence or in the presence of an inert gas under the reaction conditions, such as nitrogen or argon. Preferably, no inert gas is used in the esterification.
  • the ratio of the resulting monoesters to the diesters can be controlled by the stoichiometry of the reactants.
  • the enzymatic esterification catalyst contains at least one enzyme which is selected from hydrolases, preferably lipases, or esterases.
  • the enzyme is particularly preferably selected from lipases from Candida rugosa, Candida antartica, Thermomyces lambiinosa, Rhizomucor miehei or esterase from pig liver.
  • lipases especially lipases from Candida antarctica, especially lipase B from Candida antarctica.
  • the enzymatic esterification catalyst can be used as a cell extract, purified protein solution (homogeneous catalyst) or immobilized (supported) (heterogeneous catalyst).
  • the enzyme is used in immobilized form.
  • the enzymes are preferably bound either adsorptively, ionically or covalently to inorganic or organic carrier particles.
  • organic carriers are those which comprise or consist of polyacrylate, polymethacrylate, polyvinylstyrene, styrene-divinylbenzene copolymers, polypropylene, polyethylene, polyethylene terephthalate, polytetrafluoroethylene (PTFE) and / or other polymers.
  • Acidic or basic ion exchange resins can also be used as support material, for example Duolite A568, Duolite XAD 761, Duolite XAD 1 180, Duolite XAD 7HP, Amberlite IR 120, Amberlite IR 400, Amberlite CG 50, Amberlyst 15 (all products from Rohm and Haas), Lewatit CNP 105 and (products from Lanxess, Leverkusen, Germany).
  • Preferred supports are polypropylene or acrylate. Particularly preferred are the polypropylene carrier Accurel MP1000 or the acrylate carrier Lewatit VP OC 1600.
  • a preferred commercially available enzyme is a preparation of lipase B from Candida antarctica (CAL-B) (Novozyme® 435) immobilized on a polymethacrylate carrier.
  • inorganic supports known from the prior art, oxide and / or ceramic supports can be used.
  • celites, zeolites, silica, controlled pore glass (CPG) or other carriers can be used as inorganic carriers.
  • the carrier used has a particle size distribution in which at least 90% of the particles have a particle size of 0.5 to 5000 ⁇ , preferably from 1 to 2000 ⁇ , more preferably from 10 to 2000 ⁇ , in particular 25 to 2000 ⁇ .
  • the enzymatic esterification process described here is preferably carried out in a reactor containing at least one heterogeneous catalyst.
  • the heterogeneous catalyst is preferably in the form of a fixed bed or is suspended in the reaction mixture.
  • An advantage of the fixed bed is that the supported enzyme does not have to be separated from the product and the carrier particles can not come into contact with an agitator. The particles are better left intact.
  • the disadvantage is that the reactants usually have to be passed several times over such a fixed bed in order to achieve an acceptable reaction conversion. In addition, removal of water of reaction may be more difficult, pressure loss over the packed bed may result, or segregation phenomena may occur.
  • the reaction mixture is usually mixed by means of a stirrer. If this is the case, then the carrier particles are subject a certain mechanical load.
  • a stirrer If this is the case, then the carrier particles are subject a certain mechanical load.
  • An advantage of the slurry reactor is a reaction conversion in one step. It is advantageously possible when using a heterogeneous catalyst, the separation of the reaction product by size exclusion, z. B. using a sieve, with the help of solids by the criterion of particle size can be separated.
  • the screening process may also be a filtration.
  • the size and / or geometry of the openings of the separation medium is based on the smallest particle size to be separated off.
  • a separation can also be carried out sequentially by connecting several different screens and / or filters in series (differing, for example, in the size and / or geometry of the openings of the separation medium). The selection is often based on the fact that a separation takes place as possible without pressure loss.
  • the enzymatic esterification is preferably carried out without addition of an external solvent (here called “solvent-free").
  • ester synthesis reaction water is formed, which leads to an undesirable shift in the reaction equilibrium.
  • the water formed in the reaction is removed by customary methods known to the person skilled in the art.
  • the amount of reaction water discharged is chosen so that the reaction equilibrium is sufficiently shifted with respect to the desired product (ester).
  • the conversion of the starting materials alcohol and acid
  • the desired conversion is generally greater than 80%, preferably greater than 85%, particularly preferably greater than 90%, in particular greater than 92%, in particular greater than 94%, in particular greater than 96%, in particular greater than 98%, in particular greater than 99%, in particular greater than 99 , 2%, in particular greater than 99.4%, in particular greater than 99.6%, in particular greater than 99.7%, in particular greater than 99.8%.
  • One way of quantifying the reaction conversion makes use of the measurement of the acid number, which is a measure of the acid contained in the reaction mixture, which is not converted to the ester. The person skilled in the art is familiar with this measurement.
  • the removal of the water of reaction can take place by the following measures: distillative removal of the water,
  • Suitable stripping or towing gases are z. As air, nitrogen, carbon dioxide, argon or mixtures thereof.
  • Suitable drying agents are, for. As molecular sieves, sodium sulfate, magnesium sulfate or silica gel.
  • reduced pressure based on the normal pressure
  • pressure is meant, for example, pressure in the range of 1 to 1000 mbar.
  • pressure ranges from 5 to 500 mbar, in particular, from 5 to 200 mbar, in particular from 5 to 100 mbar, in particular from 10 to 100 mbar, in particular from 10 to 50 mbar.
  • It is essential that working is carried out at pressures which are smaller at the respective reaction temperature than the vapor pressure of the water of reaction. Since the stability of enzymes is guaranteed only in certain temperature ranges, the reaction temperature must be carefully selected. It is typically 0 to 100 ° C, preferably 20 to 100 ° C, particularly preferably 20 to 90 ° C.
  • the selected reaction temperature causes the vacuum to be applied, if appropriate, for the discharge of the water of reaction.
  • the crude reaction mixtures obtained by the process according to the invention can be subjected to at least one work-up step. These include z. B. neutralization, purification and drying. A purification can be carried out by customary methods known to the person skilled in the art, for. B. by extraction and / or distillation. In general, reaction products are obtained by the process described above, based on the compounds of the general formula (I) contained pure diesters or mixtures of mono- and diesters.
  • a typical reaction product of the preparation of diesters preferably contains from 80 to 100% by weight of diester and from 0 to 20% by weight of monoester, based on the total weight of the compounds (I).
  • a typical reaction product for the preparation of monoesters preferably contains from 40 to 80% by weight of monoester and from 20 to 60% by weight of diester, based on the total weight of the compounds (I).
  • a typical reaction product of the preparation of diesters preferably contains from 69 to 97% by weight of diester
  • a typical reaction product of the preparation of monesters preferably contains from 29 to 77% by weight of monoester
  • the compounds of the general formula (I) are advantageously suitable as surface-active compounds.
  • the compounds of general formula (I) are suitable as surfactants, emulsifiers, solubilizers and foaming agents.
  • Suitable surfactants are preferably compounds of general formula (I) wherein R 2 is hydrogen.
  • Suitable surfactants are preferably compounds of the general formula (I) in which R 2 is hydrogen and R 1 is unbranched or branched Cs-Css-alkyl or unbranched or branched Cs-Css-alkenyl with 1, 2, 3, 4, 5 or 6 double bonds, where Cs-Css-alkyl and Cs-Css-alkenyl may be substituted by 1, 2 or 3 hydroxyl groups and / or may have 1, 2, 3 or 4 epoxy groups.
  • R 2 is hydrogen and R 1 is unbranched or branched Cs-Css-alkyl or unbranched or branched Cs-Css-alkenyl with 1, 2, 3, 4, 5 or 6 double bonds
  • Cs-Css-alkyl and Cs-Css-alkenyl may be substituted by 1, 2 or 3 hydroxyl groups and / or may have 1, 2, 3 or 4 epoxy groups.
  • Particularly suitable surfactants are compounds of the general formula (I) in which R 2 is hydrogen and R 1 is unbranched or branched C 1 -C 17 -alkyl or C 1 -C -alkenyl, unbranched or branched, with 1, 2, 3, 4, 5 or 6 double bonds, where Cn-Ci7-alkyl radical and Cn-Ci7-alkenyl may be substituted by 1, 2 or 3 hydroxyl groups.
  • Suitable surfactants are, in particular, compounds of the general formula (I) in which R 2 is hydrogen and R 1 is unsubstituted, unbranched C 1 -C 13 -alkyl.
  • the aforementioned compounds (I) which are suitable as surfactants are also preferably suitable as foaming agents. They are characterized by a good foaming power, d. H. On the one hand, they can achieve a good height of the base foam, on the other hand, they also have a good foam resistance, especially in hard water. With regard to suitable and preferred foaming agents, reference is made in their entirety to the suitable and preferred surfactants.
  • Suitable solubilizers are preferably compounds of general formula (I), wherein
  • R 2 is hydrogen and R 1 is unbranched or branched C 1 -C 35 -alkyl or unbranched or branched C 5 -C 35 -alkenyl having 1, 2, 3 or more than 3 double bonds, where C 2 -C 5 -alkyl and Cn-C35- Alkenyl by at least a hydroxyl group may be substituted and / or may have at least one epoxy group.
  • solubilizers used are compounds of the general formula (I) in which
  • solubilizers compounds of general formula (I) are used, wherein
  • solubilizers used are compounds of the general formula (I) in which
  • R 1 is straight or branched C 1 -C 35 -alkyl or CJ-C35 straight or branched alkenyl having 1, 2, 3 or more than 3 double bonds, wherein C 12 -C 35 -alkyl and C 20 -C 15 -alkenyl are each represented by at least one hydroxyl group may be substituted, and R 1 'is unbranched or branched Cs-Cn-alkyl or straight or branched C5-Cn-alkenyl having 1, 2 or 3 double bonds, wherein Cs-Cn-alkyl and C0-Cn-alkenyl may each be substituted by at least one hydroxyl group ,
  • solubilizers compounds of general formula (I) are used, wherein
  • R 1 is straight or branched C 1 -C 23 -alkyl or straight or branched C 12 -C 23 -alkenyl having 1, 2, 3, 4, 5 or 6 double bonds, wherein C 1 -C 23 -alkyl and C 1 -C -23-alkenyl are each denoted by 1 , 2 or 3 hydroxyl groups and / or 1, 2, 3 or 4 epoxy groups may have and
  • R 1 ' is unbranched or branched Cs-Cn-alkyl or unbranched or branched C0-Cn-alkenyl having 1 or 2 double bonds, wherein Cs-Cn-alkyl and C0-Cn-alkenyl may each be substituted by 1 or 2 hydroxyl group.
  • solubilizers used are compounds of the general formula (I) in which
  • R 1 is unbranched or branched cis-C2i-alkyl or straight or branched Ci5-C2i-alkenyl having 1, 2, 3 or 4 double bonds, wherein Ci5-C2i-alkyl and cis-C2i-alkenyl each by 1, 2 or 3 Hydroxyl groups may be substituted, and
  • R 1 is unbranched or branched Cs-Cn-alkyl or unbranched or branched C0-Cn-alkenyl having 1 or 2 double bonds, wherein Cs-Cn-alkyl and C0-Cn-alkenyl may each be substituted by 1 or 2 hydroxyl group.
  • the solubilizers used are compounds of the general formula (I) in which
  • R 2 is hydrogen and R 1 is unbranched or branched C 1 -C 35 -alkyl or unbranched or branched C 1 -C 5 5-alkenyl with 1, 2, 3 or more than 3 pelitatien, wherein Cn-C35-alkyl and Cn-C35 alkenyl may be substituted by at least one hydroxyl group and / or may have at least one epoxy group.
  • solubilizers compounds of general formula (I) are used, wherein
  • R 2 is hydrogen and R 1 is straight or branched C 1 -C 23 -alkyl or straight or branched C 1 -C 23 -alkenyl having 1, 2, 3, 4, 5 or 6 double bonds, wherein C 1 -C 23 -alkyl and Cn-C23 alkenyl may be substituted by 1, 2 or 3 hydroxyl groups and / or may have 1, 2, 3 or 4 epoxy groups.
  • solubilizers used are compounds of the general formula (I) in which
  • R 2 is hydrogen and R 1 is unbranched or branched cis-C2i-alkyl or straight or branched cis-C2i-alkenyl having 1, 2, 3 or 4 double bonds, wherein cis-C2i-alkyl and cis-C2i-alkenyl by 1, 2 or 3 hydroxyl groups may be substituted.
  • the compounds of the general formula (I) are advantageously suitable for modifying the rheological properties of aqueous compositions.
  • they may be, for example, cosmetic compositions, pharmaceutical compositions, hygiene products, paints, compositions for the paper industry and the textile industry.
  • the compounds of general formula (I) are preferably suitable for thickening the consistency of surfactant-containing aqueous compositions in a wide range. They act specifically as so-called “micellar thickeners", d. H. surfactant compounds used to increase the viscosity of surfactant-containing formulations. Depending on the basic consistency of the liquid compositions, depending on the amount of copolymer used, as a rule, flow properties can be achieved from low viscosity to solid (in the sense of "no longer flowing").
  • Suitable rheology modifiers are preferably compounds of the general formula (I) in which R 2 is hydrogen and R 1 is unbranched or branched Cs-Css alkenyl having 1, 2, 3 or more than 3 double bonds, wherein Cs-Css alkenyl may be substituted by at least one hydroxyl group and / or having at least one epoxy group can.
  • R 2 is hydrogen and R 1 is unbranched or branched Cs-Css alkenyl having 1, 2, 3, 4, 5 or 6 double bonds, wherein Cs-Css alkenyl by 1, 2 or
  • 3 hydroxyl groups may be substituted and / or 1, 2, 3 or 4 may have epoxy groups.
  • Suitable rheology modifiers are, in particular, compounds of the general formula (I) in which
  • R 2 is hydrogen and R 1 is unbranched or branched Cs-C23 alkenyl having 1, 2, 3 or 4 double bonds, wherein Cs-C23 alkenyl may be substituted by 1, 2 or 3 hydroxyl groups.
  • Suitable emollients are preferably compounds of the general formula (I) in which
  • R 1 'and R 1 and R 1 ' independently of one another are branched Cs-Cu-alkyl or branched Cs-C23-alkenyl having 1, 2 or 3 double bonds.
  • radicals R 1 and R 1 ' are preferably unsubstituted.
  • compositions according to the invention containing at least one additional surfactant
  • the compounds of general formula (I) according to the invention are particularly advantageous for providing formulations, especially cosmetic or pharmaceutical compositions and detergents, cleaners or dishwashing agents which contain at least one surfactant other than the compounds of general formula (I).
  • these are aqueous formulations.
  • the compounds (I) are distinguished in such formulations by at least one of the following properties: a good surface-active action, a good thickening effect even with small amounts used, and good compatibility with other surfactants.
  • Suitable additional surfactants are anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.
  • anionic surfactants are soaps, alkyl sulfonates, alkyl benzene sulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, ether sulfates, glycerol ether sulfates, fatty acid sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates , Mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taur
  • Suitable soaps are z.
  • alkali, alkaline earth and ammonium salts of fatty acids such as potassium stearate.
  • Preferred alkyl sulfates are sulfates of fatty alcohols of the general formula R 3 -O-SO 3 Y 1 , in which R 3 is a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 22 carbon atoms and Y 1 is an alkali metal, the monovalent charge equivalent of an alkaline earth metal, ammonium , Mono-, di-, tri- or tetraalkylammonium, alkanolammonium or glucammonium.
  • Suitable fatty alcohol sulfates will preferably be obtained by sulfation of native fatty alcohols or synthetic oxoalcohols and subsequent neutralization.
  • Typical examples of fatty alcohol sulfates are the sulfation products of caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, behenyl alcohol and elaeostearyl alcohol, and the salts and mixtures thereof.
  • Preferred salts of the fatty alcohol sulfates are the sodium and potassium salts, especially the sodium salts.
  • Preferred mixtures of Fettalkoholsulfa- te are based on technical alcohol mixtures, the z. B. incurred in the high-pressure hydrogenation of technical methyl esters based on fats and oils or in the hydrogenation of aldehydes from the oxo process or in the dimerization of unsaturated fatty alcohols.
  • Typical examples include technical alcohol sulfates based on vegetable raw materials.
  • the olefin sulfonates may be present as alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium or glucammonium salts.
  • the olefinsulfonates are present as sodium salts.
  • the hydrolyzed alpha-olefin sulfonation product ie the alpha-olefin sulfonates, are composed of about 60% by weight of alkanesulfonates and about 40% by weight of hydroxyalkanesulfonates; Of these, about 80 to 85 wt .-% mono- and 15 to 20 wt .-% disulfonates.
  • Preferred methyl ester sulfonates (MES) are obtained by sulfonation of the fatty acid methyl esters of vegetable or animal fats or oils.
  • Preferred are methyl ester sulfonates of vegetable fats and oils, eg. From rapeseed oil, sunflower oil, soybean oil, palm oil, coconut oil, etc.
  • a preferred class of anionic surfactants are the ether sulfates.
  • Ether sulfates alkyl ethersulfates
  • CSA chlorosulfonic acid
  • fatty alcohol ether sulfates of the general formula R 6 O- (CH 2 CH 2 O) m SO 3 Y 2 in which R 6 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, m is from 1 to 10 and Y 2 is from 1 to 10 an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products an average of 1 to 10 and especially 2 to 5 moles of ethylene oxide with caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol , Gadoleylalkohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts.
  • caproic alcohol capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol,
  • the ether sulfates may have both a conventional and a narrow homolog distribution. Particular preference is given to the use of ether sulfates based on adducts of on average 2 to 3 moles of ethylene oxide onto technical C-wu or C12 / 18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • Preferred sarcosinates are sodium lauroyl sarcosinate or sodium stearoyl sarcosinate.
  • Preferred protein fatty acid condensates are wheat based vegetable products.
  • Preferred alkyl phosphates are mono- and Diphosphorklarealkylester.
  • Suitable acylglutamates are compounds of the formula (II)
  • COR 7 is a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and Y 3 and Y 4 are independently hydrogen, an alkali metal, the monovalent charge equivalent of an alkaline earth metal, ammonium, alkylammonium, Alkanolammonium or glucammonium.
  • the preparation of acylglutamates is carried out, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or fatty acid halides.
  • Acylglutamates are commercially available, for example, from BASF SE, Clariant AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP.
  • acylglutamates suitable as component b) are preferably derived from fatty acids having 6 to 22 and particularly preferably 12 to 18 carbon atoms.
  • fatty acids having 6 to 22 and particularly preferably 12 to 18 carbon atoms are used. These include z. B.
  • Nonionic surfactants include, for example:
  • Fatty alcohol polyoxyalkylene esters for example lauryl alcohol polyoxyethyl enacetate,
  • Alkylpolyoxyalkylenether which are derived from low molecular weight Ci-C6 alcohols or C7-C3o-fatty alcohols.
  • the ether component can be derived from ethylene oxide units, propylene oxide units, 1,2-butylene oxide units, 1,4-butylene oxide units and random copolymers and block copolymers thereof. These include in particular fatty alcohol alkoxylates and Oxoalkoholalkoxyla- te, in particular of the type
  • R C 3 -C 30 -alkyl or C 6 -C 30 -alkenyl
  • r and s independently of one another are from 0 to 50, both of which can not stand for 0, such as isotridecyl alcohol and oleyl alcohol polyoxyethylene ethers,
  • Alkylaryl alcohol polyoxyethylene ethers e.g. B. octylphenol polyoxyethylene ethers, - sugar surfactants, preferably alkylpolyglycosides, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, N-alkylgluconamides,
  • alkoxylated animal and / or vegetable fats and / or oils for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates,
  • Glycerol esters such as glycerol monostearate
  • Alkylphenol alkoxylates such as, for example, ethoxylated isooctyl, octyl or nonylphenol, tributylphenol polyoxyethylene ethers,
  • Alkyldimethylphosphine oxides such as, for example, tetradecyldimethylphosphine oxide.
  • a preferred class of nonionic surfactants are the sugar surfactants, especially alkyl (poly) glycosides.
  • alkyl (poly) glycosides is used synonymously with alkyl (oligo) glycosides and is also designated by the abbreviation "APG”.
  • Alkyl glycosides and / or alkyl polyglycosides include both alkyl and alkenyl (poly) glycosides and preferably have the formula R 11 0- [G] p in which R 11 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G stands for a sugar residue with 5 or 6 carbon atoms and p stands for numbers from 1 to 10.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p indicates the degree of polymerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10.
  • the value p is an analytically determined arithmetic size, which is usually a fractional number.
  • Preference is given to using alkyl and / or alkenyl polyglycosides having an average degree of polymerization p of 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl polyglycosides whose degree of polymerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • Suitable amphoteric surfactants are, for.
  • Alkylbetaines alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkylamphodiacetates or dipropionates.
  • cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine, sodium cocamphopropionate or tetradecyldimethylamine oxide can be used.
  • the cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and pyridine and imidazoline derivatives, in particular alkylpyridinium halides.
  • behenyl or cetyltrimethylammonium chloride can be used.
  • esterquats based on quaternary triethanol-methyl-ammonium or quaternary diethanol-dimethyl-ammonium compounds with long hydrocarbon chains in the form of fatty acid esters. These include, for example, bis (acyloxyethyl) hydroxyethylammonium methosulfate.
  • Dehyquart L 80 (INCI: dicocoylethyl hydroxyethyl methosulfate (and) propylene glycol).
  • the compounds of the general formula (I) are preferably suitable for the formulation of cosmetic and pharmaceutical compositions, especially of aqueous cosmetic and pharmaceutical compositions.
  • Another object of the invention is accordingly a cosmetic or pharmaceutical composition containing at least one compound of the general Formula (I), as defined above, and at least one of them different cosmetic or pharmaceutical active ingredient and / or excipient.
  • the cosmetic and pharmaceutical compositions according to the invention preferably contain the compounds of the general formula (I) in an amount of from 0.1 to 50% by weight, particularly preferably from 0.5 to 30% by weight, based on the total weight of the composition.
  • compositions according to the invention preferably comprise as excipient at least one cosmetically or pharmaceutically acceptable carrier.
  • the cosmetically or pharmaceutically acceptable carrier is selected from i) water,
  • water-miscible organic solvents preferably C 2 -C 4 alkanols, in particular ethanol
  • oils iii) oils, fats, waxes,
  • oils, fats and waxes are mineral and synthetic oils, such as.
  • As paraffins and aliphatic hydrocarbons having more than 8 carbon atoms purcellin oil, perhydrosqualene, silicone oils, natural (animal or vegetable) oils and fats, such as. Sunflower oil, coconut oil, palm kernel oil, palm oil, soybean oil, avocado oil, olive oil, sweet almond oil, calophilum oil, castor oil, sesame oil, jojoba oil, karite oil, hopsilo-oil, lanolin and derivatives thereof (eg hydrogenated lanolin and acetylated lanolin ), or waxes, fatty acids, fatty acid esters, such as. B.
  • triglycerides of C6-C3o-fatty acids are z. Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • Such cosmetically acceptable oils, fats and waxes are used especially in skin cosmetic and dermatological compositions.
  • compositions according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical compositions.
  • the compounds of the general formula (I) are suitable for use in a multiplicity of different cosmetic or pharmaceutical compositions on account of the properties described above. They can be used as an active ingredient, as an adjuvant or as a component with a multiple effect.
  • the compounds (I) are z.
  • the compositions are flowable but not too light or viscous to allow optimal application; the ability to provide fluid to the skin or to have a moisturizing effect.
  • the compounds (I) are also preferably suitable as foaming agents in cosmetic compositions, in particular compositions for the care and / or cleaning of the hair.
  • compositions according to the invention are a cleaning agent for the skin and / or the hair.
  • These preferably contain at least one of the compounds of the formula (I) described above with the suitability as surfactants.
  • compositions according to the invention are an agent for the care and / or protection of the skin. These may then contain at least one of the previously described compounds of formula (I) having the suitability as emollients. These may furthermore contain at least one sparingly soluble active substance, eg. Example, a UV filter, and at least one of the previously described compounds of formula (I) having the suitability as a solubilizer.
  • a sparingly soluble active substance eg. Example, a UV filter
  • compositions according to the invention are an agent for decorative cosmetics.
  • Another specific embodiment is skin and hair conditioner containing at least one compound of formula (I). Due to their thickening properties, the compounds of the formula (I) described above are also suitable in particular as additives for hair and skin cosmetics.
  • the compositions according to the invention are in the form of a cream, mousse, milk, lotion, mascara, theatrical color, liquid to solid consistency soap, foam, gel, spray, stick, washing, shower or bath preparation of liquid to gelatinous consistency, eye shadow , Eyeliners, Rouges, Powders or Strips. If desired, liposomes or microspheres can also be used.
  • the cosmetic compositions according to the invention may additionally contain cosmetically and / or dermatologically active active substances and effect substances as well as auxiliaries.
  • the cosmetic compositions according to the invention preferably contain at least one compound of the formula (I) as defined above, at least one carrier c) as defined above and at least one different constituent, which is preferably selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives , Perfume oils, additional thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches, gelling agents, conditioners, tinting agents, tanning agents, dyes, pigments, bodying agents, moisturizers, restockers, collagen, protein hydrolysates, lipids, antioxidants Defoamers, antistatic agents, emollients and plasticizers.
  • the cosmetic agents may contain at least one conventional thickening agent.
  • these include z.
  • polysaccharides and organic layer minerals such as xanthan Gum ® (Kelzan ® Fa. Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (RT Vanderbilt) or Attaclay ® (Engelhardt).
  • Suitable thickening agents are also organic natural thickening agents (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein) and inorganic thickening agents (polysilicic acids, clay minerals such as montmoril lonite, zeolites, silicas).
  • Suitable cosmetically and / or dermatologically active agents are, for.
  • tanning agents As skin and hair pigmentation agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial agents, light filter agents, repellent, hyperemic substances, keratolytic and keratoplastic substances, Antischuppenwirkstof- fe, anti-inflammatory drugs, keratinizing substances, antioxidant or as radical scavengers active substances, skin-moisturizing or moisturizing substances, moisturizing active ingredients, deodorizing agents, sebostatic agents, plant extracts, antiemytics or anti-allergic active substances and mixtures thereof.
  • Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z. Dihydroxyacetone, alloxan and walnut shell extract.
  • Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as.
  • Antimicrobial agents are used to destroy or inhibit their growth microorganisms and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor. These include z.
  • preservatives known in the art such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc.
  • deodorizing substances are, for.
  • Suitable light filtering agents are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are those mentioned above. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide.
  • Suitable repellent agents are compounds capable of preventing or repelling certain animals, particularly insects, from humans. This includes z. B.
  • Suitable hyperemic substances which stimulate the circulation of the skin are, for.
  • essential oils such as mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc.
  • Suitable keratolytic and keratoplastic substances such as salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc.
  • Suitable antidandruff agents are, for.
  • compositions of the invention may contain as cosmetic active ingredient (as well as optionally as adjuvant) at least one cosmetically or pharmaceutically acceptable polymer. These include, in general, anionic, cationic, amphoteric and neutral polymers. In a preferred embodiment, the compositions of the invention are a skin cleanser.
  • Preferred skin cleansing agents are soaps of liquid to gelatinous consistency, such as transparent soaps, luxury soaps, deep soaps, cream soaps, baby soaps, skin soaps, abrasive soaps and syndets, pasty soaps, soft soaps and washing pastes, liquid detergents, shower and bath preparations such as washing lotions, shower baths and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • compositions according to the invention are cosmetic compositions for the care and protection of the skin, nail care preparations or preparations for decorative cosmetics.
  • Suitable skin cosmetic agents are, for.
  • Means for use in decorative cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, rouges, powders, and eyebrow pencils.
  • the compounds of formula (I) can be used in nasal strips for pore cleansing, anti-acne agents, repellents, shaving agents, depilatories, personal care products, foot care products and baby care.
  • the skin care compositions according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, skin lotions and moisturizing lotions.
  • Skin cosmetic and dermatological compositions based on the compounds of the formula (I) described above show advantageous effects.
  • the compounds of the formula (I) can contribute to the moisturization and conditioning of the skin and to the improvement in the feel on the skin. By adding the polymers according to the invention, a significant improvement in the skin compatibility can be achieved in certain formulations.
  • Skin cosmetic and dermatological compositions preferably contain at least one compound of formula (I) in a proportion of about 0.001 to 30 wt .-%, preferably 0.01 to 20 wt .-%, most preferably 0.1 to 12 wt .-%, based on the total weight of the composition.
  • compositions of the invention may be in a form suitable for skin care, such.
  • skin care such as cream, foam, gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion can be applied.
  • the skin cosmetic compositions may contain other active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators, dyes , Salts, thickeners, gelling agents, bodying agents, silicones, humectants, moisturizers and other common additives.
  • active ingredients and auxiliaries customary in skin cosmetics as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators, dyes , Salts,
  • the skin cosmetic and dermatological compositions may additionally contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • the preparation of the cosmetic or dermatological compositions is carried out by customary methods known to the person skilled in the art.
  • the agents according to the invention are a shower gel, a shampoo formulation or a bath preparation.
  • Such formulations comprise at least one compound of general formula (I) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
  • suitable active ingredients and / or adjuvants are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, and thickeners / gelling agents, skin conditioners and humectants.
  • Suitable surfactants are the aforementioned.
  • the agents according to the invention are a hair treatment agent.
  • the invention proper hair treatment agent in the form of a mousse, hair mousse, hair gel, shampoos, hair sprays, hair mousse, top fluids, leveling agent or "hot oil treatments" ago.
  • the hair cosmetic preparations can be applied as (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion or wax.
  • the compounds of the formula (I) according to the invention and those used according to the invention are also suitable for use in modifying the rheological properties in pharmaceutical compositions of any kind.
  • a further subject of the invention is the use of a compound of the formula (I) as defined above as an excipient in pharmacy.
  • Typical pharmaceutical compositions comprise A) at least one compound of formula (I), as defined above,
  • compositions C) optionally at least one further pharmaceutically acceptable excipient other than A) and B).
  • Pharmaceutically acceptable excipients C) are the excipients which are known to be useful in the pharmaceutical, food technology and related fields, in particular those listed in relevant pharmacopoeias (eg DAB, Ph. Eur., BP, NF) and other excipients whose properties are physiological application.
  • Suitable auxiliaries C) may be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators, pigments, quaternaries Ammonium compounds, lipid and superfatting agents, ointment, cream or oil bases, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, additional thickeners, waxes, plasticizers, white oils.
  • An embodiment in this respect is based on expert knowledge.
  • the active ingredients may be mixed or diluted with a suitable excipient.
  • Excipients may be solid, semi-solid or liquid materials which may serve as a vehicle, carrier or medium for the active ingredient.
  • auxiliaries are carried out in the manner known to those skilled in the art.
  • these are aqueous solutions or solubilisates for oral or parenteral administration.
  • the copolymers to be used according to the invention are also suitable for use in oral dosage forms such as tablets, capsules, powders, solutions. Here they can provide the poorly soluble drug with increased bioavailability.
  • emulsions for example fat emulsions, can be used in addition to solubilisates.
  • compositions of the above kind can be obtained by processing the compounds of the formula (I) to be used according to the invention with pharmaceutically active substances by conventional methods and using known and new active substances.
  • the content of at least one compound of the general formula (I) in the pharmaceutical agents is, depending on the active ingredient, in the range of 0.01 to 50 wt .-%, preferably 0.1 to 40 wt .-%, particularly preferably 1 to 30 wt .-%, based on the total weight of the composition.
  • all pharmaceutical active ingredients and prodrugs are suitable for the preparation of the pharmaceutical compositions according to the invention.
  • benzodiazepines include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, platelet aggregation inhibitors, sulfa drugs, anticonvulsants, hormones, immunoglobulins, sera, thyroid medicines, psychotropic drugs, Parkinson's drugs and others Antihyperkinetics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering agents, hepatic therapies, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport proteins, enzyme inhibitors, Emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics,
  • the compounds of the general formula (I) are advantageously suitable for use in detergents and cleaners, in dishwashing detergents and in rinse aids.
  • detergents containing the compounds of general formula (I) include detergents and cleaners, dishwashing detergents such as hand dishwashing detergents or dishwasher detergents, metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, neutral cleaners, alkaline cleaners, Acid cleaners, syringe degreasers, dairy cleaners, large kitchen cleaners, apparatus cleaners in industry, in particular in the chemical industry, cleaners for car washes and also household general purpose cleaners.
  • Another object of the invention are detergents, cleaners and dishwashing detergents containing at least one compound of general formula (I).
  • the compound of the general formula (I) can be used both as a surface-active compound and as a rheology modifier.
  • suitable and preferred compounds (I) for use as a surfactant compound and rheology modifier are fully incorporated herein by reference.
  • the washing, cleaning and dishwashing agent preferably comprises the following constituents: a) at least one compound of the general formula (I); b) at least one builder (also referred to as sequestering agent, builder, complexing agent, chelator, chelating agent or softening agent); c) optionally at least one enzyme; d) optionally at least one bleaching agent; and e) optionally at least one further additive, which is preferably selected from among a) various surfactants, bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tableting aids, disinfesting agents, thickeners, solubilizers, organic solvents, electrolytes, pH adjusters , Perfume carriers, fluorescers, hydrotropes, Anti-redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellent
  • the detergents and cleaners according to the invention preferably comprise: a) at least one compound of the general formula (I): from 0.1 to 20% by weight; b) at least one builder: from 5 to 80% by weight;
  • At least one bleaching agent from 0 to 30% by weight;
  • the percentages by weight relate to the total weight of the washing and cleaning agent.
  • a dishwashing detergent composition according to the invention preferably comprises the following constituents: a) at least one compound of the general formula (I), at least one builder (also referred to as sequestering agent, builder, compliator, chelator, chelating agent or softening agent), optionally at least one enzyme, d) optionally at least a bleach, e1) water, optionally at least one thickener, and optionally at least one further additive, which is preferably selected from a) various surfactants, bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, solubilizers and organic solvents.
  • the dishwashing composition according to the invention preferably contains, based on the total weight of the composition, a) from 0.1 to 50% by weight of at least one compound of the formula (I) according to the invention,
  • the compounds of the formula (I) are suitable for the preparation of aqueous preparations of dietary supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.
  • the compounds of general formula (I) according to the invention can be used in all areas in which a thickening effect in combination with surfactants is necessary.
  • the compounds of the general formula (I) are suitable, the solubility of other components, for. B. other surface-active components, such as anionic surfactants to improve. They thus also contribute positively to the formation of clear surfactant solutions.
  • the compounds of the general formula (I) are also particularly suitable as solubilizers for sparingly soluble substances. Specifically, they are sparingly soluble substances which have a solubility below 10 g / l in water at 25 ° C. and 1013 mbar.
  • Active ingredients for cosmetics, pharmaceuticals, crop protection and material protection ie substances that even in low concentrations already have an effect, eg.
  • a cosmetic effect a pharmacological effect in an organism, a physiological effect in a plant or a pest, etc.
  • formulation and administration are also solid Shape, z. B. as a powder or compact (tablet, etc.) possible, but the transport to the actual site of action, however, comprises the conversion into a liquid, especially aqueous, form.
  • the compounds of general formula (I) are suitable as solubilizers for a variety of sparingly soluble substances.
  • the water-insoluble compositions preferably comprise an aqueous medium as the continuous phase, at least one solubilized or dispersed substance in the continuous phase which has a solubility in water at 25 ° C / 1013 mbar below 10 g / l, especially below 1 g / l and especially below 0.1 g / l, and at least one compound of the general formula (I) according to the invention.
  • aqueous medium for the purposes of the invention comprises water and mixtures of water with organic solvents which are at least partially miscible with water.
  • water-miscible solvents examples include C 3 -C 4 ketones such as acetone and methyl ethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran, C 1 -C 4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert Butanol, polyols and their mono- and dimethyl ethers, such as glycol, propanediol, ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, glycerol, furthermore C2-C3 nitriles, such as acetonitrile and propionitrile, dimethyl sulfoxide, dimethylformamide, formamide, acetamide, Dimethylacetamide, butyrolactone, 2-pyrrolidone and N-methylpyrrolidone.
  • the compounds of general formula (I) are generally suitable as solubilizers for oils, fats and waxes, as described, for. B. previously described as lipophilic carriers for cosmetic and pharmaceutical preparations. This disclosure is hereby incorporated by reference. Furthermore, the compounds of the general formula (I) are suitable as solubilizers for all the aforementioned lipophilic cosmetic and pharmaceutical active ingredients and adjuvants.
  • the compounds of the general formula (I) are furthermore suitable as solubilizers for lipophilic cosmetic and / or pharmaceutical active substances.
  • At least one compound (I) is used to solubilize at least one lipophilic organic UV filter substance.
  • the UV filter substances are substances which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet rays and of absorbing the absorbed energy in the form of longer-wave radiation, eg. B. heat, again.
  • the UV-A and UV-B filters can be used individually or in mixtures.
  • Suitable lipophilic UV filter substances are:
  • PABA p-aminobenzoic acid
  • Typical lipophilic UV filters are:
  • 3-benzylidene camphor or 3-benzylidenenorcampher and derivatives thereof e.g. B. 3- (4-methylbenzylidene) camphor, 3- (4'-trimethylammonium) benzylidenebornan-2-one methylsulfate (Mexoryl SO), 3,3 '- (1, 4-phenylenedimethine) bis (7,7-dimethyl -2-oxo-bicycle- [2.2.1] heptane-1-methanesulfonic acid) and salts (mexoryl SX), 3- (4'-sulfo) benzylidenebornane-2-ones and salts (Mexoryl SL), polymers of N- ⁇ (2 and 4) - [2- oxoborn-3-ylidenes) methyl ⁇ benzyl] acrylamide (Mexoryl SW), 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3-) (1,3,3,3-te
  • Another class of lipophilic compounds which can be solubilized by means of at least one compound of general formula (I) are dyes. They are preferably dyes suitable for cosmetic applications. These include z. Cochineal red A (CI 16255), patent blue V (CI 42051), indigotine (CI 73015), chlorophyllin (CI 75810), quinoline yellow (CI 47005), titanium dioxide (CI 77891), indan-thene blue RS (Cl 69800 ).
  • 2,5-di (hydroxymethyl) tetrahydrofurandipalmitate was carried out according to the procedure described in Example 1 from 2,5-di (hydroxymethyl) tetrahydrofuran (303 mmol, 40.0 g, 1, 0 equiv.), Palmitoyl chloride (605 mmol , 166 g), dimethylaminopyridine (60.48 mmol, 7.40 g) and diisopropylethylamine (605 mmol, 78.2 g).
  • the product obtained contained 88.2% of 2,5-di (hydroxymethyl) tetrahydrofurandipalmitate and 5.1% of 2,5-di (hydroxymethyl) tetrahydrofuran monopalmitate.
  • the respective acid component was tempered with 2,5-di (hydroxymethyl) tetrahydrofuran in a 1 L stirred reactor to 75 ° C and mixed.
  • the esterification reaction was started by adding 1% by weight of commercially available Novozym® 435 (lipase B from Candida antarctica immobilized on a polymethacrylate support).
  • the removal of the resulting reaction water was carried out by a combination of reduced pressure (50 to 10 mbar) and gassing with nitrogen as stripping gas (0 to 1 1 NL / h * kg).
  • the course of the reaction was monitored by means of acid number.
  • the catalyst was separated by filtration from the product. Weighing raw materials: a) 134 g of 2,5-di (hydroxymethyl) tetrahydrofuran,

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Abstract

La présente invention concerne de nouveaux monoesters et diesters de 2,5-di(hydroxyméthyl)tétrahydrofurane, un procédé de fabrication de ceux-ci par estérification en présence d'amine tertiaire ou en présence de catalyseurs d'estérification enzymatiques, ainsi que l'utilisation de ces monoesters et diesters en tant que composés de surface de séparation actifs, modificateurs de rhéologie et émollients. L'invention concerne en outre des moyens cosmétiques et pharmaceutiques ainsi que des produits de lavage, des produits de nettoyage et des liquides vaisselles qui contiennent ces monoesters et diesters de 2,5-di(hydroxyméthyl)tétrahydrofurane.
EP15748256.3A 2014-10-07 2015-08-12 Monoesters et diesters à chaîne longue de 2,5-di(hydroxyméthyl)tétrahydrofurane, leur fabrication et leur utilisation Withdrawn EP3204365A1 (fr)

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RU2732326C2 (ru) 2015-07-22 2020-09-15 Басф Се Способ получения фуран-2,5-дикарбоновой кислоты
JP2018538361A (ja) 2015-11-04 2018-12-27 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ フラン−２，５−ジカルボン酸を調製する方法
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
CN110049754B (zh) * 2016-09-23 2022-12-06 Cj第一制糖株式会社 用于化妆品的脂肪酸乙酯
DE102017008072A1 (de) * 2017-08-28 2019-02-28 Henkel Ag & Co. Kgaa Neue anionische Tenside und Wasch- und Reinigungsmittel, welche diese enthalten
AU2019274628A1 (en) 2018-05-23 2020-11-26 Basf Se A lubricant comprising 2,5-(bishydroxymethyl) tetryhydrofuran dialkanoates
CN111349492B (zh) * 2020-02-28 2021-05-25 浙江糖能科技有限公司 2,5-四氢呋喃二甲醇脂肪酸二酯在柴油添加剂的应用
CN115124494A (zh) * 2021-03-26 2022-09-30 中国科学院宁波材料技术与工程研究所 一种2,5-四氢呋喃二甲醇硫酸根酯类化合物及其制备方法和应用

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