WO1995021181A1 - Pseudo-ceramides - Google Patents

Pseudo-ceramides Download PDF

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Publication number
WO1995021181A1
WO1995021181A1 PCT/EP1995/000229 EP9500229W WO9521181A1 WO 1995021181 A1 WO1995021181 A1 WO 1995021181A1 EP 9500229 W EP9500229 W EP 9500229W WO 9521181 A1 WO9521181 A1 WO 9521181A1
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Prior art keywords
radical
carbon atoms
alkyl
formula
pseudoceramides
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PCT/EP1995/000229
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German (de)
French (fr)
Inventor
Hinrich Möller
Rolf Wachter
Peter Busch
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1995021181A1 publication Critical patent/WO1995021181A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/68Sphingolipids, e.g. ceramides, cerebrosides, gangliosides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • C07C233/01Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/17Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/18Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • C07H13/06Fatty acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier 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
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations

Definitions

  • the invention relates to pseudoceramides obtainable by acylation of linear alkyl and / or alkenyl compounds with dicarboxylic acid anhydrides, subsequent conversion of the acylation products into the acid chlorides and condensation with amine compounds, a process for the preparation of the pseudoceramides, skin care products with a content of pseudoceramides and the use of pseudoceramides for the production of skin care products.
  • a balanced water balance in the individual skin layers plays an important role for the elasticity and the appearance of the skin.
  • the amount of bound water is greatest in the dermis and in the boundary layer of the epider near the basement membrane.
  • the skin elasticity is decisively shaped by the collagen fibrils in the dermis, the specific conformation of the collagen being achieved by the incorporation of water molecules.
  • Destruction of the lipid barrier in the stratum corneum (SC), for example by surfactants leads to an increase in transepidermal water loss, which disturbs the aqueous environment of the cells. Since the water bound in the deeper layers of the skin can only be supplied through the body fluid via vessels, but not from the outside, it becomes clear that maintaining the barrier function of the stratum corneum is essential for the overall condition of the skin [cf. SEFriberg et al., CR 23rd CED Congress, Barcelona, 1992, p.29].
  • Ceramides are lipophilic amides of long-chain fatty acids, which are generally derived from sphingosine or phytosphingosine. This class of endogenous fatty substances has gained considerable importance since they have been recognized in the intercellular space between the corneocytes as key components for the structure of the lipid bilayer, ie the permeability barrier, in the stratum corneum of human skin. Ceramides have molecular weights of significantly less than 1000, so that the external site of a cosmetic formulation makes it possible to reach the site of action. The external application of ceramides leads to the restoration of the lipid barrier, which can cause the described disorders of the skin function to be counteracted [cf. R.D. Petersen, Cosm.Toil. 107, 45 (1992)].
  • R a stands for hydrogen or an unsaturated fatty acyl radical
  • z for numbers from 7 to 49
  • A for a hydroxyalkyl
  • Z for a sugar or phosphate radical
  • the object of the invention was therefore to develop new high-performance ceramide-analog structures which are distinguished by the simplest possible synthesis. Another task was to produce the new pseudoceramides based on non-animal raw materials.
  • the invention relates to pseudoceramides of the formula (I)
  • R 1 is a linear alkyl and / or alkenyl radical having 6 to 30 carbon atoms
  • R 2 is hydrogen or an optionally hydroxyl-substituted alkyl radical having 1 to 30 carbon atoms
  • R3 is an oligohydroxyalkyl radical having 4 to 12 carbon atoms and 3 to 10 hydroxyl groups or one Glycosyl radical
  • X for a linear or branched alkylene radical with 1 to 6 carbon atoms
  • Y for oxygen, sulfur or an NR ⁇ radical
  • R 4 for hydrogen or an alkyl radical with 1 to 30 carbon atoms.
  • the pseudoceramides to be used in accordance with the invention strengthen the natural barrier function of the skin, strengthen the skin and protect it from drying out.
  • the substances are modeled on the natural skin lipids, are dermatologically and ecotoxicologically harmless and can be incorporated homogeneously into the oil phase of cosmetic products. They are colored white or ivory-like, odor-free, hydrolysis-resistant in the area of the skin pH and color-stable against atmospheric oxygen.
  • the invention includes the knowledge that the pseudoceramides can be produced on the basis of vegetable fatty alcohols and sugar, ie without the use of undesirable animal raw materials.
  • pseudoceramides of the formula (I) in which R 1 for an alkyl and / or alkenyl radical with 16 to 18 carbon atoms, R 2 for an alkyl or alkenyl radical with 12 to 22 carbon atoms, R 3 for a polyhydroxyalkyl radical 6 carbon atoms and 5 hydroxyl groups or a glucosyl radical, X is an ethylene group and Y is oxygen.
  • the invention further relates to a process for the preparation of pseudoceramides of the formula (I)
  • R 2 and R 3 in turn have the meanings given above.
  • Typical examples of alcohols are the group of fatty alcohols having 6 to 30 carbon atoms.
  • Capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleol alcohol alcohol, linoleyl alcohol alcohol, are exemplified , Elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures as are obtainable, for example, by high-pressure hydrogenation of technical methyl ester fractions.
  • Particularly preferred starting materials are fatty alcohols with 16 to 24 carbon atoms and 0 and / or 1 double bond, such as technical grade fatty alcohol.
  • Typical examples of examples of thiols are the sulfur analogs of the above-mentioned fatty alcohols.
  • amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, eicosylamine, docosylamine, didodecylamine, dioctadecylamine, methyloctadecylamine, docosyloctadecylamine and docosylamine and docosylamine and their docosylamine.
  • the use of amines with 16 to 18 carbon atoms and 0 and 1 double bond is also particularly preferred.
  • dicarboxylic acid anhydrides examples include succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride and oxidic acetic anhydride.
  • Dicarboxylic acid anhydrides of the formula (III) are preferably used in which X represents an alkylene group having 2 to 4 carbon atoms.
  • linear alkyl and / or alkenyl compounds and the dicarboxylic acid anhydrides can usually be used in a molar ratio of 1: 0.9 to 1: 1.1.
  • the free carboxyl group of the acylation products must first be converted into the acid chloride in a manner known per se.
  • Phosphorus trichloride or thionyl chloride are preferably used as chlorine compounds.
  • the acylation products and the chlorine compounds can usually be used in a molar ratio of 1: 0.4 to 1: 2.5.
  • the chlorination is preferably carried out at -10 to 50 ° C. in the absence of water, for example gasoline fractions, toluene, ethyl acetate, tert. Butyl methyl ether or tetrahydrofuran.
  • the acylation products can be reacted with chlorocarbonic acid alkyl esters in an inert solvent to give the mixed anhydrides.
  • the reaction preferably takes place in the presence of an acid scavenger such as triethylamine, tributylamine or sodium or potassium carbonate, the reactants being used in approximately molar amounts at temperatures from -10 to 50, preferably 0 to 10 ° C. After the reaction, it is advisable to filter off the salts formed.
  • an acid scavenger such as triethylamine, tributylamine or sodium or potassium carbonate
  • Suitable polyhydroxyalkalyamines which are reacted with the acid chlorides of the acylation products are N-alkylsorbitylamines and in particular N-alkylglucosylamine of the formula (V)
  • R 2 preferably represents an alkyl radical having 12 to 22 and in particular 16 to 18 carbon atoms.
  • N-alkylglucamines of the formula (VI) are used
  • R 2 preferably represents an alkyl radical having 12 to 22 and in particular 16 to 18 carbon atoms.
  • the N-alkyl glucamines are usually prepared by reductive amination of glucose with fatty amines.
  • the glucosylamines and the glucamines can also be derived, for example, from maltose, fructose or palatinose.
  • Also suitable as further polyhydroxyalkylamines are methylol-substituted alkanolamines, for example 2,2-bis (hydroxymethyl) -2-aminoethanol and 2,2-bis (hydroxymethyl) -3-aminopropanol.
  • the acid chlorides or mixed anhydrides of the acylation products and the polyhydroxyalkylamines and sorbityl or glucosylamines can usually be used in a molar ratio of 1: 0.8 to 1: 2.0.
  • the condensation reaction is preferably carried out at temperatures in the range from 20 to 50 ° C. in the presence of alkaline catalysts, the reaction times typically being 1 to 10 hours.
  • Soda, potash or tertiary araine such as triethylamine can be used as acid scavengers, for example tetrahydrofuran is recommended as a solvent.
  • Another advantageous embodiment consists of working in non-water-miscible solvents and adding the acid scavenger in aqueous solution.
  • the products can then be purified by recrystallization, for example from lower alcohols or column chromatography.
  • recrystallization for example from lower alcohols or column chromatography.
  • the condensation of amine compounds with acid chlorides is known in principle and is described, for example, in EP-A 0 265 818 (CF Stockhausen). Reaction scheme
  • the manufacturing process is characterized by the sequence of the following - exemplary - reactions which are intended to aid in understanding the reaction process:
  • the invention further relates to skin care compositions containing pseudoceramides of the formula (I).
  • the agents according to the invention can contain the pseudoceramides in amounts of 1 to 30, preferably 2 to 10% by weight, based on the agents, and both as “water-in-oil” and “oil-in” Water "emulsions are present; further conventional auxiliaries and additives in amounts of 5 to 95, preferably 10 to 80 wt .-% can also contain his. Furthermore, the formulations can contain water in an amount of up to 99% by weight, preferably 5 to 80% by weight.
  • Suitable carrier oils for this purpose are: mineral oils, vegetable oils, silicone oils, fatty acid esters, dialkyl ethers, fatty alcohols and Guerbet alcohols.
  • emulsifiers which can be used are: sorbitan esters, monoglycerides, polysorbates, polyethylene glycol mono / difatty acid esters, highly ethoxylated fatty acid esters and high molecular weight silicone compounds, such as dimethylpolysiloxanes with an average molecular weight of 10,000 to 50,000.
  • it is also possible to dispense with the addition of emulsifiers since the pseudoceramides according to the invention themselves have dispersing properties.
  • additives can be: preservatives, such as p-hydroxybenzoic acid ester; On oxidants, such as butylated hydroxytoluene, tocopherol; Humectants, such as, for example, glycerol, sorbitol, 2-pyrrolidine-5-carboxylate, dibutyl phthalate, gelatin, polyglycols with an average molecular weight of 200 to 600; Buffers such as lactic acid / TEA or lactic acid / NaOH; mild surfactants, such as alkyl oligoglucosides, fatty alcohol ether sulfates, fatty acid isethionates, taurides and sarcosinates, ether carboxylic acids, sulfosuccinates, protein hydrolysates or fatty acid condensates, sulfotriglycerides, short-chain glucamides; Phospholipids, waxes such as beeswax, ozoce
  • the pseudoceramides can be mixed with conventional ceramides, further pseudo-ceramides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances, whereby liposomes can be formed.
  • the pseudoceramides can be mixed with active substance accelerators, in particular with essential oils, such as, for example, eucalyptol, menthol and the like.
  • the pseudoceramides can finally also be dissolved in squalene or squalane and optionally formulated with the other ingredients mentioned together with volatile or non-volatile silicone compounds as anhydrous or almost anhydrous single-phase systems.
  • squalene or squalane optionally formulated with the other ingredients mentioned together with volatile or non-volatile silicone compounds as anhydrous or almost anhydrous single-phase systems.
  • volatile or non-volatile silicone compounds as anhydrous or almost anhydrous single-phase systems.
  • the pseudoceramides to be used as "synthetic barrier lipids" in the sense of the invention strengthen the natural barrier function of the skin against external stimuli. They improve the firmness, suppleness and elasticity of the skin, increase the moisture content and protect the skin from drying out; at the same time, the finest wrinkles are smoothed out.
  • Another object of the invention therefore relates to the use of pseudoceramides of the formula (I) as "synthetic barrier lipids" for the production of skin care products in which they are present in amounts of 1 to 30, preferably 2 to 10% by weight, based on the means - can be included. Typical examples are skin creams, soft creams, nutritional creams, sunscreen creams, night creams, skin oils, care lotions and body aerosols.
  • Example 1 Succinic acid octadecyl ester-N-octadecylsorbitylamide.
  • Example 1 was repeated using 0.1 mol of succinic acid mono-octadecyl ester and 0.1 mol of N-octadecylsorbitylamine.
  • a colorless wax was obtained which sinters at 45 to 52 ° C and begins to melt at 110 ° C.
  • Example 3 Example 3:
  • Example 1 was repeated using 0.1 mol of N, N-dioctadecylsuccinic acid monoamide and 0.1 mol of 1,1-bishydroxymethyl-2-hydroxyethylamine. A colorless wax was obtained which sintered at 30 to 35 ° C.
  • Succinic acid 9-octadecenyl ester-N-octadecylglucosylamide To the stirred solution of 36.9 g (0.1 mol) of succinic acid 9-octadecenyl ester and 10.1 g (0.1 mol) of triethylamine in 200 ml of THF was added a solution of 10.9 g (-5 0.1 mol) of chloro-carbonic acid ester in 50 ml of THF and the mixture stirred for 1 h at 0 ° C, triethylamine hydrochloride precipitated.

Abstract

The proposal is for novel pseudo-ceramides of the formula (I) in which R1 is a linear alkyl and/or alkenyl radical with 6 to 30 carbon atoms, R2 is hydrogen or a possibly hydroxy-substituted alkyl radical with 1 to 30 carbon atoms, R3 is an oligo-hydroxyalkyl radical with 4 to 12 carbon atoms and 3 to 10 hydroxyl groups or a glycosyl radical, X is a linear or branched alkylene radical with 1 to 6 carbon atoms, Y is oxygen, sulphur or an NR4 radical and R4 is hydrogen or an alkyl radical with 1 to 30 carbon atoms. The substances are suitable as 'synthetic barrier lipids' for the production of skin-care agents.

Description

Pseudoceramide Pseudoceramides
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft Pseudoceramide, erhältlich durch Acy- lierung von linearen Alkyl- und/oder Alkenylverbindungen mit Dicarbonsäureanhydriden, nachfolgende Überführung der Acylie- rungsprodukte in die Säurechloride und Kondensation mit Amin- verbindungen, ein Verfahren zur Herstellung der Pseudocera¬ mide, Hautpflegemittel mit einem Gehalt der Pseudoceramiden sowie die Verwendung der Pseudoceramide zur Herstellung von Hautpflegemitteln.The invention relates to pseudoceramides obtainable by acylation of linear alkyl and / or alkenyl compounds with dicarboxylic acid anhydrides, subsequent conversion of the acylation products into the acid chlorides and condensation with amine compounds, a process for the preparation of the pseudoceramides, skin care products with a content of pseudoceramides and the use of pseudoceramides for the production of skin care products.
Stand de Ter-h iVStand de Ter-h iV
Für die Elastizität und das Aussehen der Haut spielt ein aus¬ balancierter Wasserhaushalt in den einzelnen Hautschichten eine wichtige Rolle. In der Dermis und in der Grenzschicht der Epider is nahe der Basalmembran ist der Gehalt an gebun¬ denem Wasser am größten. Die Hautelastizität wird entschei¬ dend durch die Collagenfibrillen in der Dermis geprägt, wobei die spezifische Konformation des Collagens durch den Einbau von Wassermolekülen erreicht wird. Eine Zerstörung der Lipid- barriere im Stratum Corneum (SC) beispielsweise durch Tenside führt zu einem Anstieg des transepidermalen Wasserverlustes, wodurch die wäßrige Umgebung der Zellen gestört wird. Da das in tieferen Hautschichten gebundene Wasser nur über Gefäße über die Körperflüssigkeit, nicht aber von außen zugeführt werden kann, wird deutlich, daß der Erhalt der Barrierefunk¬ tion des Stratum Corneum essentiell für den Gesamtzustand der Haut ist [vgl. S.E.Friberg et al., C.R. 23. CED-Kongress, Barcelona, 1992, S.29].A balanced water balance in the individual skin layers plays an important role for the elasticity and the appearance of the skin. The amount of bound water is greatest in the dermis and in the boundary layer of the epider near the basement membrane. The skin elasticity is decisively shaped by the collagen fibrils in the dermis, the specific conformation of the collagen being achieved by the incorporation of water molecules. Destruction of the lipid barrier in the stratum corneum (SC), for example by surfactants leads to an increase in transepidermal water loss, which disturbs the aqueous environment of the cells. Since the water bound in the deeper layers of the skin can only be supplied through the body fluid via vessels, but not from the outside, it becomes clear that maintaining the barrier function of the stratum corneum is essential for the overall condition of the skin [cf. SEFriberg et al., CR 23rd CED Congress, Barcelona, 1992, p.29].
Ceramide stellen liphophile Amide langkettiger Fettsäuren dar, die sich im allgemeinen von Sphingosin bzw. Phytosphin- gosin ableiten. Erhebliche Bedeutung hat diese Klasse von körpereigenen Fettstoffen gewonnen, seitdem man sie im in- terzellären Raum zwischen den Corneozyten als Schlüsselkom¬ ponenten für den Aufbau des Lipid-Bilayers, also der Permea¬ bilitätsbarriere, im Stratum Corneum der menschlichen Haut erkannt hat. Ceramide haben Molekulargewichte von deutlich unter 1000, so daß bei äußerer Zufuhr in einer kosmetischen Formulierung das Erreichen des Wirkortes möglich ist. Die externe Applikation von Ceramiden führt zur Restaurierung der Lipidbarriere, wodurch den geschilderten Störungen der Haut¬ funktion ursächlich entgegengewirkt werden kann [vgl. R.D. Petersen, Cosm.Toil. 107, 45 (1992)].Ceramides are lipophilic amides of long-chain fatty acids, which are generally derived from sphingosine or phytosphingosine. This class of endogenous fatty substances has gained considerable importance since they have been recognized in the intercellular space between the corneocytes as key components for the structure of the lipid bilayer, ie the permeability barrier, in the stratum corneum of human skin. Ceramides have molecular weights of significantly less than 1000, so that the external site of a cosmetic formulation makes it possible to reach the site of action. The external application of ceramides leads to the restoration of the lipid barrier, which can cause the described disorders of the skin function to be counteracted [cf. R.D. Petersen, Cosm.Toil. 107, 45 (1992)].
Dem Einsatz von Ceramiden sind infolge ihrer mangelnden Ver¬ fügbarkeit bislang Grenzen gesetzt. Es hat daher bereits Ver¬ suche gegeben, ceramidanaloge Strukturen, sogenannte "synthe¬ tic barrier lipids (SBL)" oder "Pseudoceramide" zu syntheti¬ sieren und zur Hautpflege einzusetzen [vgl. G.Imokawa et al. J.Soc. Cosmet.Chem. .40., 273 (1989)]. So werden beispielsweise in der Europäischen Offenlegungs- Schriften EP-A 0 277 641 und EP-A 0 227 994 (Kao) Ceramidana- loge der folgenden Struktur vorgeschlagen:So far, the use of ceramides has been limited due to their lack of availability. There have therefore already been attempts to synthesize ceramide-analogous structures, so-called "synthetic barrier lipids (SBL)" or "pseudoceramides" and to use them for skin care [cf. G.Imokawa et al. J. Soc. Cosmet.Chem. .40., 273 (1989)]. For example, the European patent application EP-A 0 277 641 and EP-A 0 227 994 (Kao) propose ceramide analogs of the following structure:
OH CH2CH2OHOH CH2CH 2 OH
I I R-0-CH2-CH-CH2-N-COR' .II R-0-CH 2 -CH-CH 2 -N-COR '.
Aus den Europäischen OffenlegungsSchriften EP-AI 0 482 860 und EP-AI 0 495 624 (Unilever) sind ceramidverwandte Struk¬ turen der folgenden Formel bekannt:Ceramide-related structures of the following formula are known from the European published documents EP-AI 0 482 860 and EP-AI 0 495 624 (Unilever):
0R# R*0R # R *
I II I
R-0-CH2-CH-CH2-NH-CH2-N-C0-(CH2) (CHOR*)aR' .R-0-CH 2 -CH-CH 2 -NH-CH 2 -N-CO- (CH 2 ) (CHOR *) a R '.
Für den Schutz von Haut und Haaren werden in der Europäischen Patentanmeldung EP-A2 0 455 429 (Unilever) ferner Zuckerde¬ rivate der folgenden Zusammensetzung vorgeschlagen:In order to protect skin and hair, sugar derivatives of the following composition are also proposed in European patent application EP-A2 0 455 429 (Unilever):
RbRb
I Ra-O-(CH2)zCO-N-CH2-[Z]I Ra-O- (CH 2 ) z CO-N-CH 2 - [Z]
Hierbei steht Ra für Wasserstoff oder einen ungesättigten Fettacylrest, z für Zahlen von 7 bis 49, A für einen Hydroxy- alkyl- und Z für einen Zucker- oder Phosphatrest.Here, R a stands for hydrogen or an unsaturated fatty acyl radical, z for numbers from 7 to 49, A for a hydroxyalkyl and Z for a sugar or phosphate radical.
Ungeachtet dieser Versuche ist der Erfolg, der sich mit die¬ sen Stoffen erzielen läßt, bislang unbefriedigend; insbesondere wird das Leistungsvermögen natürlicher Ceramide nicht erreicht. Ferner sind die Syntheseseguenzen technisch aufwendig und daher kostspielig, was die Bedeutung der Sub¬ stanzen zusätzlich relativiert.Notwithstanding these attempts, the success which can be achieved with these substances has so far been unsatisfactory; in particular, the performance of natural ceramides is not achieved. Furthermore, the synthesis sequences are technically complex and therefore expensive, which further relativizes the importance of the substances.
Die Aufgabe der Erfindung hat somit darin bestanden, neue leistungsstarke ceramidanaloge Strukturen zu entwickeln, die sich durch eine möglichst einfache Synthese auszeichnen. Eine weitere Aufgabe hat ferner darin bestanden, die neuen Pseudo¬ ceramide auf Basis nicht-tierischer Rohstoffe herzustellen.The object of the invention was therefore to develop new high-performance ceramide-analog structures which are distinguished by the simplest possible synthesis. Another task was to produce the new pseudoceramides based on non-animal raw materials.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind Pseudoceramide der Formel (I),The invention relates to pseudoceramides of the formula (I)
0 0 R2 n n I0 0 R 2 nn I
Ri-Y-C-(X)-C-N-R3 (I)Ri-Y-C- (X) -C-N-R3 (I)
in der R1 für einen linearen Alkyl- und/oder Alkenylrest mit 6 bis 30 Kohlenstoffatomen, R2 für Wasserstoff oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 30 Kohlenstoffatomen, R3 für einen Oligohydroxyalkylrest mit 4 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen oder einen Glycosylrest, X für einen linearen oder verzweigten Alkylenrest mit 1 bis 6 Kohlenstoffatomen, Y für Sauerstoff, Schwefel oder einen NR^-Rest und R4 für Wasserstoff oder ei¬ nen Alkylrest mit 1 bis 30 Kohlenstoffatomen steht. Überraschenderweise wurde gefunden, daß die im Sinne der Er¬ findung einzusetzenden Pseudoceramide die natürliche Barrie¬ refunktion der Haut stärken, die Haut festigen und vor Aus¬ trocknung schützen. Die Stoffe sind den natürlichen Hautli- piden nachempfunden, dermatologisch und ökotoxikologisch un¬ bedenklich und lassen sich homogen in die Ölphase kosmeti¬ scher Mittel einarbeiten. Sie sind weiß bzw. elfenbeinartig gefärbt, geruchsfrei, im Bereich des Haut-pH-Werteε hydro¬ lysebeständig und farbstabil gegen Luftsauerstoff. Die Erfin¬ dung schließt die Erkenntnis ein, daß die Pseudoceramide auf Basis pflanzlicher Fettalkohole und Zucker, also ohne Mit¬ verwendung unerwünschter tierischer Rohstoffe, hergestellt werden können.in which R 1 is a linear alkyl and / or alkenyl radical having 6 to 30 carbon atoms, R 2 is hydrogen or an optionally hydroxyl-substituted alkyl radical having 1 to 30 carbon atoms, R3 is an oligohydroxyalkyl radical having 4 to 12 carbon atoms and 3 to 10 hydroxyl groups or one Glycosyl radical, X for a linear or branched alkylene radical with 1 to 6 carbon atoms, Y for oxygen, sulfur or an NR ^ radical and R 4 for hydrogen or an alkyl radical with 1 to 30 carbon atoms. Surprisingly, it was found that the pseudoceramides to be used in accordance with the invention strengthen the natural barrier function of the skin, strengthen the skin and protect it from drying out. The substances are modeled on the natural skin lipids, are dermatologically and ecotoxicologically harmless and can be incorporated homogeneously into the oil phase of cosmetic products. They are colored white or ivory-like, odor-free, hydrolysis-resistant in the area of the skin pH and color-stable against atmospheric oxygen. The invention includes the knowledge that the pseudoceramides can be produced on the basis of vegetable fatty alcohols and sugar, ie without the use of undesirable animal raw materials.
Besonders bevorzugt sind Pseudoceramide der Formel (I), in der R1 für einen Alkyl- und/oder Alkenylrest mit 16 bis 18 Kohlenstoffatomen, R2 für einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen, R3 für einen Polyhydroxyalkyl- rest mit 6 Kohlenstoffatomen und 5 Hydroxylgruppen oder einen Glucosylrest, X für eine Ethylengruppe und Y für Sauerstoff steht.Particularly preferred are pseudoceramides of the formula (I) in which R 1 for an alkyl and / or alkenyl radical with 16 to 18 carbon atoms, R 2 for an alkyl or alkenyl radical with 12 to 22 carbon atoms, R 3 for a polyhydroxyalkyl radical 6 carbon atoms and 5 hydroxyl groups or a glucosyl radical, X is an ethylene group and Y is oxygen.
HerstellverfahrenManufacturing process
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung von Pseudoceramiden der Formel (I)The invention further relates to a process for the preparation of pseudoceramides of the formula (I)
0 0 R2 ιt n I0 0 R 2 ιt n I
Ri-Y-C-(X)-C-N-R3 (I) in der R für einen linearen Alkyl- und/oder Alkenylrest mit 6 bis 30 Kohlenstoffatomen, R2 für Wasserstoff oder einen ge¬ gebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 30 Kohlenstoffatomen, R3 für einen Oligohydroxyalkylrest mit 4 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen oder einen Glycosylrest, X für einen linearen oder verzweigten Alkylenrest mit 1 bis 6 Kohlenstoffatomen, Y für Sauerstoff, Schwefel oder einen R4-Rest und R4 für Wasserstoff oder ei¬ nen Alkylrest mit 1 bis 30 Kohlenstoffatomen steht, bei dem manRi-YC- (X) -CNR 3 (I) in which R is a linear alkyl and / or alkenyl radical having 6 to 30 carbon atoms, R 2 is hydrogen or an optionally hydroxy-substituted alkyl radical having 1 to 30 carbon atoms, R 3 is an oligohydroxyalkyl radical having 4 to 12 carbon atoms and 3 to 10 hydroxyl groups or a glycosyl radical, X represents a linear or branched alkylene radical having 1 to 6 carbon atoms, Y represents oxygen, sulfur or an R 4 radical and R 4 represents hydrogen or an alkyl radical having 1 to 30 carbon atoms, in which
a) lineare Alkyl- und/oder AlkenylVerbindungen der Formela) linear alkyl and / or alkenyl compounds of the formula
R1-Y-H (II)R 1 -YH (II)
mit Dicarbonsäureanhydriden der Formel (III),with dicarboxylic acid anhydrides of the formula (III),
COCO
X O (III)X O (III)
COCO
in der R1, X und Y die oben genannten Bedeutungen be¬ sitzen, acyliert,in which R 1 , X and Y have the meanings given above, acylated,
b) die resultierenden Acylierungsprodukte in an sich be¬ kannter Weise mittels Chlorverbindungen in ihre Säure¬ chloride oder gemischten Anhydride überführt undb) the resulting acylation products are converted into their acid chlorides or mixed anhydrides in a manner known per se by means of chlorine compounds, and
c) die resultierenden Säurechloride oder gemischten Anhy¬ dride der Acylierungsprodukte mit Polyhydroxyalkylami- nen, Sorbityl- bzw. Glucosylaminen der Formel (IV) kon¬ densiert,c) the resulting acid chlorides or mixed anhydrides of the acylation products with polyhydroxyalkylami- condensed sorbityl or glucosylamines of the formula (IV),
R2 R 2
I H-N-R3 (IV)I HNR 3 (IV)
wobei R2 und R3 wiederum die oben angegebenen Bedeu¬ tungen besitzen.where R 2 and R 3 in turn have the meanings given above.
Lineare Alkyl- und/oder AlkenylverbindunσenLinear alkyl and / or alkenyl compounds
Im Sinne des erfindungsgemäßen Verfahrens kommen als lineare Alkyl- und/oder AlkenylVerbindungen Alkohole (Y = Sauer¬ stoff), Thiole (Y = Schwefel) oder Amine (Y = NR4) _n Be_ trächt.For the purposes of the process according to the invention thiols (Y = sulfur) or amines (Y = NR 4) are a linear alkyl and / or alkenyl alcohols (Y = Sauer¬ material), _ n _ Be trächt.
Typische Beispiele für Alkohole stellt die Gruppe der Fett¬ alkohole mit 6 bis 30 Kohlenstoffatomen dar. Exemplarisch genannt werden Capronalkyohol, Caprylalkohol, Caprinalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylal- kohol, Stearylalkohol, Oleylalkohol, Elaidylalkohol, Petro- selinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostea- rylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technische Gemische wie sie beispielsweise durch Hochdruckhydreriung von technischen Me¬ thylesterfraktionen erhältlich sind. Als Ausgangsstoffe be¬ sonders bevorzugt sind Fettalkohole mit 16 bis 24 Kohlen¬ stoffatomen und 0 und/oder 1 Doppelbindung wie beispielsweise technischer Taigfettalkohol. Typische Beispiele für Beispiele für Thiole sind die Schwe¬ felanaloga der oben genannten Fettalkohole.Typical examples of alcohols are the group of fatty alcohols having 6 to 30 carbon atoms. Capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleol alcohol alcohol, linoleyl alcohol alcohol, are exemplified , Elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures as are obtainable, for example, by high-pressure hydrogenation of technical methyl ester fractions. Particularly preferred starting materials are fatty alcohols with 16 to 24 carbon atoms and 0 and / or 1 double bond, such as technical grade fatty alcohol. Typical examples of examples of thiols are the sulfur analogs of the above-mentioned fatty alcohols.
Typische Beispiele für A ine sind Octylamin, Decylamin, Dode- cylamin, Tetradecylamin, Hexadecylamin, Octadecylamin, Oleyl- amin, Eicosylamin, Docosylamin, Didodecylamin, Dioctadecyl- amin, Methyloctadecylamin, Docosyloctadecylamin und Docosyl- oleylamin sowie deren technische Gemische. Besonders bevor¬ zugt ist auch wiederum der Einsatz von Aminen mit 16 bis 18 Kohlenstoff tomen und 0 und 1 Doppelbindung.Typical examples of amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, eicosylamine, docosylamine, didodecylamine, dioctadecylamine, methyloctadecylamine, docosyloctadecylamine and docosylamine and docosylamine and their docosylamine. The use of amines with 16 to 18 carbon atoms and 0 and 1 double bond is also particularly preferred.
DicarbonsaureanhydrideDicarboxylic acid anhydrides
Als Dicarbonsaureanhydride kommen beispielsweise Bernstein¬ säureanhydrid, Maleinsäureanhydrid, Glutarsäureanhydrid, Phthalsäureanhydrid und Oxidiessigsäureanhydrid in Betracht. Vorzugsweise werden Dicarbonsaureanhydride der Formel (III) eingesetzt, in der X für eine Alkylengruppe mit 2 bis 4 Koh¬ lenstoffatomen steht.Examples of suitable dicarboxylic acid anhydrides are succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride and oxidic acetic anhydride. Dicarboxylic acid anhydrides of the formula (III) are preferably used in which X represents an alkylene group having 2 to 4 carbon atoms.
Üblicherweise kann man die linearen Alkyl- und/oder Alkenyl- verbindungen und die Dicarbonsaureanhydride im molaren Ver¬ hältnis 1 : 0,9 bis 1 : 1,1 einsetzen. The linear alkyl and / or alkenyl compounds and the dicarboxylic acid anhydrides can usually be used in a molar ratio of 1: 0.9 to 1: 1.1.
ChlorverbindungenChlorine compounds
Um eine Verknüpfung zwischen den Acylierungsprodukten und den Polyhydroxyalkylaminen herstellen zu können, muß die frei Carboxylgruppe der Acylierungsprodukte zunächst in an sich bekannter Weise in das Säurechlorid überführt werden. Als Chlorverbindungen werden dabei vorzugsweise Phosphortrichlo- rid oder Thionylchlorid eingesetzt. Üblicherweise kann man die Acylierungsprodukte und die Chlorverbindungen im molaren Verhältnis 1 : 0,4 bis 1 : 2,5 einsetzen. Die Chlorierung wird vorzugsweise bei -10 bis 50°C in Abwesenheit von Wasser durchgeführt, als Lösungsmittel kommen beispielsweise Benzin¬ fraktionen, Toluol, Ethylacetat, tert. Butylmethylether oder Tetrahydrofuran in Betracht. Um eine Wärmeabfuhr der stark exothermen Reaktion sicherzustellen, empfiehlt es sich, die Chlorierung zunächst im Eisbad durchzuführen. Nach Abschluß der Reaktion werden die Verunreinigungen, z.B. unterphospho- rige Säure abgeschieden, nichtumgesetztes Chlorierungsmittel abdestilliert oder - wenn es sich nur um geringe Mengen han¬ delt - in der Reaktionsmischung belassen.In order to be able to establish a link between the acylation products and the polyhydroxyalkylamines, the free carboxyl group of the acylation products must first be converted into the acid chloride in a manner known per se. Phosphorus trichloride or thionyl chloride are preferably used as chlorine compounds. The acylation products and the chlorine compounds can usually be used in a molar ratio of 1: 0.4 to 1: 2.5. The chlorination is preferably carried out at -10 to 50 ° C. in the absence of water, for example gasoline fractions, toluene, ethyl acetate, tert. Butyl methyl ether or tetrahydrofuran. To ensure heat dissipation from the highly exothermic reaction, it is advisable to first carry out the chlorination in an ice bath. Upon completion of the reaction, the contaminants, e.g. hypophosphorous acid separated off, unreacted chlorinating agent distilled off or - if it is only a small amount - left in the reaction mixture.
In einer Variante des erfindungsgemäßen Verfahrens können die Acylierungsprodukte mit Chlorkohlensäurealkylestern in einem inerten Lösungsmittel zu den gemischten Anhydriden umgesetzt werden. Die Umsetzung findet vorzugsweise in Gegenwart eines Säurefängers wie Triethylamin, Tributylamin oder Natrium¬ bzw. Kaliumcarbonat statt, wobei die Reaktionspartner in etwa molaren Mengen bei Temperaturen von -10 bis 50, vorzugsweise 0 bis 10°C eingesetzt werden. Im Anschluß an die Umsetzung empfiehlt es sich, gebildete Salze abzufiltrieren. In diesem Zusammenhang sei auf die Veröffentlichung von C.Bersena in J.Org.Chem. J27, 3489 (1962) verwiesen. Für die nachfolgende Reaktion kann entweder die erhaltene Lösung oder aber deren Trockenrückstand eingesetzt werden.In a variant of the process according to the invention, the acylation products can be reacted with chlorocarbonic acid alkyl esters in an inert solvent to give the mixed anhydrides. The reaction preferably takes place in the presence of an acid scavenger such as triethylamine, tributylamine or sodium or potassium carbonate, the reactants being used in approximately molar amounts at temperatures from -10 to 50, preferably 0 to 10 ° C. After the reaction, it is advisable to filter off the salts formed. In this context, reference is made to the publication of C.Bersena in J.Org.Chem. J27, 3489 (1962). Either the solution obtained or its dry residue can be used for the subsequent reaction.
PolvhvdroxyalkylaminePolvhvdroxyalkylamine
Als Polyhydroxyalkalyamine, die mit den Säurechloriden der Acylierungsprodukte zur Reaktion gebracht werden, kommen beispielsweise N-Alkylsorbitylamine und insbesondere N-Alkyl- glucosyla ine der Formel (V) in Betracht,Examples of suitable polyhydroxyalkalyamines which are reacted with the acid chlorides of the acylation products are N-alkylsorbitylamines and in particular N-alkylglucosylamine of the formula (V)
CH2OHCH2OH
I R2 IR 2
CH—O | CH CH-NH (V)CH — O | CH CH-NH (V)
| CH—CH OH | || CH — CH OH | |
OH OHOH OH
in der R2 vorzugsweise für einen Alkylrest mit 12 bis 22 und insbesondere 16 bis 18 Kohlenstoffatomen steht.in which R 2 preferably represents an alkyl radical having 12 to 22 and in particular 16 to 18 carbon atoms.
In einer weiteren bevorzugten Ausführungsform der Erfindung werden N-Alkylglucamine der Formel (VI) eingesetzt,In a further preferred embodiment of the invention, N-alkylglucamines of the formula (VI) are used
OH OH OH R3 OH OH OH R 3
I I I I HOCH2-CH-CH-CH-CH-CH2-NH (VT)I I I I HOCH2-CH-CH-CH-CH-CH2-NH (VT)
II.
OH in der R2 vorzugsweise für einen Alkylrest mit 12 bis 22 und insbesondere 16 bis 18 Kohlenstoffatomen steht. Die N-Alkyl¬ glucamine werden üblicherweise durch reduktive Aminierung von Glucose mit Fettaminen hergestellt. Daneben können sich so¬ wohl die Glucosylamine als auch die Glucamine beispielsweise auch von Maltose, Fructose oder Palatinose ableiten. Als wei¬ tere Polyhydroxyalkylamine kommen ferner auch methylolsubsti- tuierte Alkanolamine, beispielsweise 2,2-Bis(hydroxymethyl)- 2-aminoethanol und 2,2-Bis(hydroxymethyl)-3-aminopropanol in Betracht.OH in which R 2 preferably represents an alkyl radical having 12 to 22 and in particular 16 to 18 carbon atoms. The N-alkyl glucamines are usually prepared by reductive amination of glucose with fatty amines. In addition, the glucosylamines and the glucamines can also be derived, for example, from maltose, fructose or palatinose. Also suitable as further polyhydroxyalkylamines are methylol-substituted alkanolamines, for example 2,2-bis (hydroxymethyl) -2-aminoethanol and 2,2-bis (hydroxymethyl) -3-aminopropanol.
Üblicherweise kann man die Säurechloride bzw. gemischten An¬ hydride der Acylierungsprodukte und die Polyhydroxyalkylamine und Sorbityl- bzw. Glucosylamine im molaren Verhältnis von 1 : 0,8 bis 1 : 2,0 einsetzen. Die Kondensationsreaktion wird vorzugsweise bei Temperaturen im Bereich von 20 bis 50°C in Gegenwart alkalischer Katalysatoren durchgeführt, wobei die Reaktionszeiten typischerweise 1 bis 10 h betragen können. Als Säurefänger können Soda, Pottasche oder tertiäre Araine wie z.B. Triethylamin eingesetzt werden, als Lösungsmittel empfiehlt sich beispielsweise Tetrahydrofuran. Eine weitere vorteilhafte Ausführungsform besteht darin, in nichtwasser- mischbaren Lösungsmitteln zu arbeiten und den Säurefänger in wäßriger Lösung zuzugeben. Im Anschluß können die Produkte durch Umkristallisation beispielsweise aus niederen Alkoholen oder Säulenchromatographie gereinigt werde. Die Kondensation von Aminverbindungen mit Säurechloriden ist grundsätzlich bekannt und wird beispielsweise in der EP-A 0 265 818 (CF Stockhausen) besehrieben. ReaktionsschemaThe acid chlorides or mixed anhydrides of the acylation products and the polyhydroxyalkylamines and sorbityl or glucosylamines can usually be used in a molar ratio of 1: 0.8 to 1: 2.0. The condensation reaction is preferably carried out at temperatures in the range from 20 to 50 ° C. in the presence of alkaline catalysts, the reaction times typically being 1 to 10 hours. Soda, potash or tertiary araine such as triethylamine can be used as acid scavengers, for example tetrahydrofuran is recommended as a solvent. Another advantageous embodiment consists of working in non-water-miscible solvents and adding the acid scavenger in aqueous solution. The products can then be purified by recrystallization, for example from lower alcohols or column chromatography. The condensation of amine compounds with acid chlorides is known in principle and is described, for example, in EP-A 0 265 818 (CF Stockhausen). Reaction scheme
Demzufolge zeichnet sich das Herstellverfahren durch die Ab¬ folge nachstehender - beispielhafter - Reaktionen aus, die dem Verständnis des Reaktionsgeschehens dienlich sein sollen:Accordingly, the manufacturing process is characterized by the sequence of the following - exemplary - reactions which are intended to aid in understanding the reaction process:
0 0 CO " "0 0 CO ""
RiYH + X 0 > RiY-C-fXJ-C-OHRiYH + X 0> RiY-C-fXJ-C-OH
CO - H2OCO - H2O
0 0 + PCI3 > Rlγ-C-(X)-C-Cl0 0 + PCI3> Rlγ-C- (X) -C-Cl
0 0 R2 + R NHR3 " " | > Rlγ-C-(X)-C-N-R3 0 0 R 2 + R NHR 3 "" | > Rlγ-C- (X) -CNR 3
- HC1- HC1
HautpflegemittelSkin care products
Ein weiterer Gegenstand der Erfindung betrifft Hautpflege¬ mittel, enthaltend Pseudoceramide der Formel (I).The invention further relates to skin care compositions containing pseudoceramides of the formula (I).
Die erfindungsgemäßen Mittel können die Pseudoceramide in Mengen von 1 bis 30, vorzugsweise von 2 bis 10 Gew.-% - be¬ zogen auf die Mittel - enthalten und dabei sowohl als "Was- ser-in-öl" als auch "Öl-in-Wasser"-Emulsionen vorliegen; weitere übliche Hilfs- und Zusatzstoffe in Mengen von 5 bis 95, vorzugsweise 10 bis 80 Gew.-% können zudem enthalten sein. Ferner können die Formulierungen Wasser in einer Menge bis zu 99 Gew.-%, vorzugsweise 5 bis 80 Gew.-% aufweisen.The agents according to the invention can contain the pseudoceramides in amounts of 1 to 30, preferably 2 to 10% by weight, based on the agents, and both as "water-in-oil" and "oil-in" Water "emulsions are present; further conventional auxiliaries and additives in amounts of 5 to 95, preferably 10 to 80 wt .-% can also contain his. Furthermore, the formulations can contain water in an amount of up to 99% by weight, preferably 5 to 80% by weight.
Als Trägeröle kommen hierzu beispielsweise in Betracht: Mine¬ ralöle, Pflanzenöle, Siliconöle, Fettsäureester, Dialkyl- ether, Fettalkohole und Guerbetalkohole. Als Emulgatoren kön¬ nen beispielsweise eingesetzt werden: Sorbitanester, Monogly- ceride, Polysorbate, Polyethylenglycolmono/difettsäureester, hochethoxylierte Fettsäureester sowie hochmolekulare Silicon¬ verbindungen, wie z.B. Dimethylpolysiloxane mit einem durch¬ schnittlichen Molekulargewicht von 10.000 bis 50.000. Es je¬ doch auch möglich, auf den Zusatz von Emulgatoren zu verzich¬ ten, da die erfindungsgemäßen Pseudoceramide selbst disper- gierende Eigenschaften aufweisen. Weitere Zusatzstoffe können sein: Konservierungsmittel, wie z.B. p-Hydroxybenzoesäure- ester; An ioxidantien, wie z.B. Butylhydroxytoluol, Tocophe- rol; Feuchthaltemittel, wie z.B. Glycerin, Sorbitol, 2-Pyrro- lidin-5-carboxylat, Dibutylphthalat, Gelatine, Polyglycole mit einem durchschnittlichen Molekulargewicht von 200 bis 600; Puffer, wie z.B. Milchsäure/TEA oder Milchsäure/NaOH; milde Tenside, wie z.B. Alkyloligoglucoside, Fettalkohol- ethersulfate, Fettsäureisethionate, -tauride und -sarcosina- te, Ethercarbonsäuren, Sulfosuccinate, Eiweißhydrolysate bzw. -fettsäurekondensate, Sulfotriglyceride, kurzkettige Glucamide; Phospholipide, Wachse, wie z.B. Bienenwachs, Ozo- keritwachs, Paraffinwachs; Pflanzenextrakte, z.B. von Aloe vera; Verdickungsmittel; Färb- und Parfümstoffe sowie Son¬ nenschutzinittel, wie z.B. ultrafeines Titandioxid oder orga¬ nische Stoffe wie p-Aminobenzoesäure und deren Ester, Ethyl- hexyl-p-methoxyzimtsäureester, 2-Ethoxyethyl-p-methoxyzimt- säureester, Butylmethoxydibenzoylmethan und deren Mischungen. In einer bevorzugten Ausführungsform der Erfindung können die Pseudoceramide mit konventionellen Ceramiden, weiteren Pseu¬ doceramiden, Cholesterin, Cholesterinfettsäureestem, Fett¬ säuren, Triglyceriden, Cerebrosiden, Phospholipiden und ähn¬ lichen Stoffen, abgemischt werden, wobei Liposomen entstehen können.Examples of suitable carrier oils for this purpose are: mineral oils, vegetable oils, silicone oils, fatty acid esters, dialkyl ethers, fatty alcohols and Guerbet alcohols. Examples of emulsifiers which can be used are: sorbitan esters, monoglycerides, polysorbates, polyethylene glycol mono / difatty acid esters, highly ethoxylated fatty acid esters and high molecular weight silicone compounds, such as dimethylpolysiloxanes with an average molecular weight of 10,000 to 50,000. However, it is also possible to dispense with the addition of emulsifiers, since the pseudoceramides according to the invention themselves have dispersing properties. Other additives can be: preservatives, such as p-hydroxybenzoic acid ester; On oxidants, such as butylated hydroxytoluene, tocopherol; Humectants, such as, for example, glycerol, sorbitol, 2-pyrrolidine-5-carboxylate, dibutyl phthalate, gelatin, polyglycols with an average molecular weight of 200 to 600; Buffers such as lactic acid / TEA or lactic acid / NaOH; mild surfactants, such as alkyl oligoglucosides, fatty alcohol ether sulfates, fatty acid isethionates, taurides and sarcosinates, ether carboxylic acids, sulfosuccinates, protein hydrolysates or fatty acid condensates, sulfotriglycerides, short-chain glucamides; Phospholipids, waxes such as beeswax, ozocerite wax, paraffin wax; Plant extracts, for example from aloe vera; Thickeners; Dyes and perfumes and sunscreens, such as ultrafine titanium dioxide or organic substances such as p-aminobenzoic acid and its esters, ethyl-hexyl-p-methoxycinnamic acid ester, 2-ethoxyethyl-p-methoxycinnamic acid ester, butylmethoxydibenzoylmethane and mixtures thereof. In a preferred embodiment of the invention, the pseudoceramides can be mixed with conventional ceramides, further pseudo-ceramides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances, whereby liposomes can be formed.
In einer weiteren bevorzugten Ausführungsform der Erfindung können die Pseudoceramide mit Wirkstoffbeschleunigern, ins¬ besondere mit etherischen Ölen, wie beispielsweise Eucalyp- tol, Menthol und ähnlichen abgemischt werden.In a further preferred embodiment of the invention, the pseudoceramides can be mixed with active substance accelerators, in particular with essential oils, such as, for example, eucalyptol, menthol and the like.
In einer dritten bevorzugten Ausführungsform können die Pseudoceramide schließlich auch in Squalen oder Squalan ge¬ löst und gegebenenfalls mit den anderen genannten Inhalts¬ stoffen zusammen mit flüchtigen oder nichtflüchtigen Sili¬ converbindungen als wasserfreie oder beinahe wasserfreie einphasige Systeme formuliert werden. Weitere Beispiele zu Bestandteilen und typischen Zusammensetzungen können bei¬ spielsweise der WO 90/01323 (Bernstein) entnommen werden.In a third preferred embodiment, the pseudoceramides can finally also be dissolved in squalene or squalane and optionally formulated with the other ingredients mentioned together with volatile or non-volatile silicone compounds as anhydrous or almost anhydrous single-phase systems. Further examples of constituents and typical compositions can be found, for example, in WO 90/01323 (Bernstein).
Gewerbliche AnwendbarkeitIndustrial applicability
Die im Sinne der Erfindung als "synthetic barrier lipids" einzusetzenden Pseudoceramide stärken die natürliche Bar¬ rierefunktion der Haut gegenüber äußeren Reizen. Sie verbes¬ sern Festigkeit, Geschmeidigkeit und Elastizität der Haut, steigern den Feuchtigkeitsgehalt und schützen die Haut vor Austrocknung; zugleich werden feinste Falten geglättet. Ein weiterer Gegenstand der Erfindung betrifft daher die Ver¬ wendung von Pseudoceramiden der Formel (I) als "synthetic barrier lipids" zur Herstellung von Hautpflegemitteln, in denen sie in Mengen von 1 bis 30, vorzugsweise 2 bis 10 Gew.-% - bezogen auf die Mittel - enthalten sein können. Ty¬ pische Beispiele sind Hautcremes, Softcremes, Nährcremes, Sonnenschutzcremes, Nachtcremes, Hautöle, Pflegelotionen und Körper-Aerosole.The pseudoceramides to be used as "synthetic barrier lipids" in the sense of the invention strengthen the natural barrier function of the skin against external stimuli. They improve the firmness, suppleness and elasticity of the skin, increase the moisture content and protect the skin from drying out; at the same time, the finest wrinkles are smoothed out. Another object of the invention therefore relates to the use of pseudoceramides of the formula (I) as "synthetic barrier lipids" for the production of skin care products in which they are present in amounts of 1 to 30, preferably 2 to 10% by weight, based on the means - can be included. Typical examples are skin creams, soft creams, nutritional creams, sunscreen creams, night creams, skin oils, care lotions and body aerosols.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
Beispiel 1:Example 1:
Bernsteinsäurebehenylester-N-octadecylglucosylamid. Zu der gerührten Lösung von 42,7 g (0,1 mol) Bernsteinsäuremonobehe- nylester in 150 ml Benzin (Sdp. 65-90°C) wurde bei 20°C eine Lösung von 8,3 g (0,06 mol) Phosphortrichlorid in 30 ml Ben¬ zin gegeben und die Mischung 1 h bei diser Temperatur und 3 h bei 40°C weiter gerührt. Nach dem Absetzen der öligen Phos¬ phorigen Säure wurde vom Rückstand abdekantiert, die Lösung am Rotationsverdampfer eingeengt, der farblose wachsartige Rückstand in 200 ml Tetrahydrofuran gelöst, die Lösung bei 22°C unter Rühren zu einer Lösung von 43,2 g (0,1 mol) N-Oc- tadecylglucosylamin und 10,1 g (0,1) Triethylamin in THF ge¬ tropft. Die entstandene Suspension wurde 5 h bei dieser Tem¬ peratur und 2 h bei 35°C weitergerührt, das gebildete Tri- ethyla inhydrochlorid abfiltriert und die Lösung eingedampft. Es wurden 81,4 g (entsprechend 97 % der Theorie) eines gelb¬ lichen Harzes erhalten. Durch Säulenchromatographie an Kie¬ selgel mit Methylenchlorid/Methanol konnte ein fast farbloser anylsenreiner Feststoff erhalten werden.Behenic acid succinate, N-octadecylglucosylamide. A solution of 8.3 g (0.06 mol) of phosphorus trichloride was added to the stirred solution of 42.7 g (0.1 mol) of succinic acid monobenzoate in 150 ml of gasoline (bp. 65-90 ° C.) at 20 ° C. added to 30 ml of gasoline and the mixture was further stirred for 1 hour at this temperature and for 3 hours at 40 ° C. After the oily phosphoric acid had settled, the residue was decanted off, the solution was concentrated on a rotary evaporator, the colorless waxy residue was dissolved in 200 ml of tetrahydrofuran, and the solution was stirred at 22 ° C. to give a solution of 43.2 g (0.1 mol) of N-ocadadecylglucosylamine and 10.1 g (0.1) of triethylamine in THF. The resulting suspension was stirred for 5 hours at this temperature and for 2 hours at 35 ° C., the triethyl hydrochloride formed was filtered off and the solution was evaporated. 81.4 g (corresponding to 97% of theory) of a yellowish resin were obtained. By column chromatography on silica gel with methylene chloride / methanol, an almost colorless anylsenic solid could be obtained.
Beispiel 2:Example 2:
Bernsteinsäureoctadecylester-N-octadecylsorbitylamid. Bei- spiel 1 wurde unter Einsatz von 0,1 Mol Bensteinsäuremono- octadecylester und 0,1 Mol N-Octadecylsorbitylamin wieder¬ holt. Es wurde ein farbloses Wachs erhalten, das bei 45 bis 52 °C sintert und bei 110°C zu schmelzen beginnt. Beispiel 3:Succinic acid octadecyl ester-N-octadecylsorbitylamide. Example 1 was repeated using 0.1 mol of succinic acid mono-octadecyl ester and 0.1 mol of N-octadecylsorbitylamine. A colorless wax was obtained which sinters at 45 to 52 ° C and begins to melt at 110 ° C. Example 3:
N,N-Dioctadeyl-N'-1,l-bishydro-synιethyl-2-hydroxyethylbern- steinsäurediamid. Beispiel 1 wurde unter Einsatz von 0,1 Mol N,N-Dioctadecylbernsteinsäuremonoamid und 0,1 Mol 1,1-Bishy- droxymethyl-2-hydroxyethylamin wiederholt. Es wurde ein farb¬ loses Wachs erhalten, das bei 30 bis 35°C sintert.N, N-dioctadeyl-N'-1, l-bishydro-synιethyl-2-hydroxyethylbers- oleic acid diamide. Example 1 was repeated using 0.1 mol of N, N-dioctadecylsuccinic acid monoamide and 0.1 mol of 1,1-bishydroxymethyl-2-hydroxyethylamine. A colorless wax was obtained which sintered at 30 to 35 ° C.
Beispiel 4:Example 4:
Bernsteinsäure-9-octadecenylester-N-octadecylglucosylamid. Zu der gerührten Lösung von 36,9 g (0,1 mol) Bernsteinsäure-9- octadecenylester und 10,1 g (0,1 mol) Triethylamin in 200 ml THF wurde bei -5°C eine Lösung von 10,9 g (0,1 mol) Chlor¬ kohlensäureester in 50 ml THF gegeben und die Mischung 1 h bei 0°C weiter gerührt, wobei Triethylaminhydrochlorid aus¬ fiel. Anschließend wurde bei 10°C zu der gerührten Dispersion eine Mischung von 42,2 g (0,1 mol) N-Octadecylglucosylamin in 200 ml THF gegeben, 2 h bei 10°C und 5 h bei 22°C weiter ge¬ rührt. Nach Abfiltrieren des Triethylaminhydrochlorids, Ein¬ dampfen der Lösung, Aufnehmen des öligen Rückstands in Ethyl- acetat. Waschen mit 1 n Salzsäure, 5 Gew.-%iger Natriumbicar- bonatlösung und Wasser, Trocknen und Eindampfen der Lösung wurden 73,4 g (entsprechend 95 % der Theorie) ein gelblichen viskosen Öles erhalten. Succinic acid 9-octadecenyl ester-N-octadecylglucosylamide. To the stirred solution of 36.9 g (0.1 mol) of succinic acid 9-octadecenyl ester and 10.1 g (0.1 mol) of triethylamine in 200 ml of THF was added a solution of 10.9 g (-5 0.1 mol) of chloro-carbonic acid ester in 50 ml of THF and the mixture stirred for 1 h at 0 ° C, triethylamine hydrochloride precipitated. A mixture of 42.2 g (0.1 mol) of N-octadecylglucosylamine in 200 ml of THF was then added to the stirred dispersion at 10 ° C., stirring was continued for 2 hours at 10 ° C. and 5 hours at 22 ° C. After filtering off the triethylamine hydrochloride, evaporating the solution and taking up the oily residue in ethyl acetate. Washing with 1N hydrochloric acid, 5% by weight sodium bicarbonate solution and water, drying and evaporation of the solution gave 73.4 g (corresponding to 95% of theory) of a yellowish viscous oil.

Claims

Patentansprüche claims
1. Pseudoceramide der Formel (I),1. pseudoceramides of the formula (I),
0 0 R2 n n I0 0 R 2 nn I
R1-Y-C-(X)-C-N-R3 (I)R 1 -YC- (X) -CNR 3 (I)
in der R1 für einen linearen Alkyl- und/oder Alkenyl¬ rest mit 6 bis 30 Kohlenstoffatomen, R2 für Wasserstoff oder einen gegebenenfalls hydroxysubstituierten Alkyl¬ rest mit 1 bis 30 Kohlenstoffatomen, R3 für einen Oligo- hydroxyalkylrest mit 4 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen oder einen Glycosylrest, X für einen linearen oder verzweigten Alkylenrest mit 1 bis 6 Kohlenstoffatomen, Y für Sauerstoff, Schwefel oder einen NR4-Rest und R4 für Wasserstoff oder einen Alkylrest mit 1 bis 30 Kohlenstoffatomen steht.in which R 1 is a linear alkyl and / or alkenyl radical having 6 to 30 carbon atoms, R 2 is hydrogen or an optionally hydroxyl-substituted alkyl radical having 1 to 30 carbon atoms, R 3 is an oligo-hydroxyalkyl radical having 4 to 12 carbon atoms and 3 to 10 hydroxyl groups or a glycosyl radical, X represents a linear or branched alkylene radical having 1 to 6 carbon atoms, Y represents oxygen, sulfur or an NR 4 radical and R 4 represents hydrogen or an alkyl radical having 1 to 30 carbon atoms.
2. Pseudoceramide nach Anspruch 1, dadurch gekennzeichnet, daß in Formel (I) R für einen Alkyl- und/oder Alkenyl¬ rest mit 16 bis 18 Kohlenstoffatomen, R2 für Wasserstoff oder eine Methylgruppe, R3 für einen Polyhydroxyalkyl- rest mit 6 Kohlenstoffatomen und 5 Hydroxylgruppen oder einen Glucosylrest, X für eine Ethylengruppe und Y für Sauerstoff steht. 2. pseudoceramides according to claim 1, characterized in that in formula (I) R for an alkyl and / or alkenyl radical having 16 to 18 carbon atoms, R 2 for hydrogen or a methyl group, R 3 for a polyhydroxyalkyl radical with 6 Carbon atoms and 5 hydroxyl groups or a glucosyl radical, X is an ethylene group and Y is oxygen.
3. Verfahren zur Herstellung von Pseudoceramiden der Formel (I)3. Process for the preparation of pseudoceramides of the formula (I)
0 0 R2 n n I0 0 R 2 nn I
R1-Y-C-(X)-C-N-R3 (I)R 1 -YC- (X) -CNR 3 (I)
in der R1 für einen linearen Alkyl- und/oder Alkenyl¬ rest mit 6 bis 30 Kohlenstoffatomen, R2 für Wasserstoff oder einen gegebenenfalls hydroxysubstituierten Alkyl¬ rest mit 1 bis 30 Kohlenstoff tomen, R3 für einen Oligo- hydroxyalkylrest mit 4 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen oder einen Glycosylrest, X für einen linearen oder verzweigten Alkylenrest mit 1 bis 6 Kohlenstoffatomen, Y für Sauerstoff, Schwefel oder einen NR4-Rest und R4 für Wasserstoff oder einen Alkylrest mit 1 bis 30 Kohlenstoffatomen steht, dadurch gekennzeich¬ net, daß manin which R 1 is a linear alkyl and / or alkenyl radical having 6 to 30 carbon atoms, R 2 is hydrogen or an optionally hydroxyl-substituted alkyl radical having 1 to 30 carbon atoms, R 3 is an oligo-hydroxyalkyl radical having 4 to 12 Carbon atoms and 3 to 10 hydroxyl groups or a glycosyl radical, X stands for a linear or branched alkylene radical with 1 to 6 carbon atoms, Y for oxygen, sulfur or an NR 4 radical and R 4 stands for hydrogen or an alkyl radical with 1 to 30 carbon atoms, thereby gekennzeich¬ net that one
a) linearen Alkyl- und/oder AlkenylVerbindungen der Formel (II),a) linear alkyl and / or alkenyl compounds of the formula (II),
Rl-Y-H (II)Rl-Y-H (II)
mit Dicarbonsäureanhydriden der Formel (III),with dicarboxylic acid anhydrides of the formula (III),
COCO
X O (III)X O (III)
CO in der R1, X und Y die oben genannten Bedeutungen besitzen, acyliert,CO in which R 1 , X and Y have the meanings given above, acylated,
b) die resultierenden Acylierungsprodukte in an sich bekannter Weise mittels Chlorverbindungen in ihre Säurechloride bzw. gemischten Anhydride überführt undb) the resulting acylation products are converted into their acid chlorides or mixed anhydrides in a manner known per se by means of chlorine compounds and
c) die resultierenden Säurechloride bzw. gemischten Anhydride der Acylierungsprodukte mit Polyhydroxy- alkylaminen, Sorbityl- bzw. Glucosylaminen der For¬ mel (IV) kondensiert,c) the resulting acid chlorides or mixed anhydrides of the acylation products are condensed with polyhydroxyalkylamines, sorbityl or glucosylamines of the formula (IV),
R2 R 2
II.
H-N-R3 (IV)HNR 3 (IV)
wobei R2 und R3 wiederum die oben angegebenen Bedeu¬ tungen besitzen.where R 2 and R 3 in turn have the meanings given above.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man als AlkylVerbindungen lineare Fettalkohole mit 16 bis 18 Kohlenstoffatomen und 0 und/oder 1 Doppelbindung einsetzt.4. The method according to claim 3, characterized in that linear fatty alcohols having 16 to 18 carbon atoms and 0 and / or 1 double bond are used as alkyl compounds.
5. Verfahren nach den Ansprüchen 3 und 4, dadurch gekenn¬ zeichnet, daß man Dicarbonsaureanhydride der Formel (III) einsetzt, in der X für Alkylengruppen mit 2 bis 4 Kohlenstoffatomen steht. 5. Process according to claims 3 and 4, characterized gekenn¬ characterized in that one uses dicarboxylic acid anhydrides of the formula (III) in which X represents alkylene groups having 2 to 4 carbon atoms.
6. Verfahren nach den Ansprüchen 3 bis 5, dadurch gekenn¬ zeichnet, daß man die AlkylVerbindungen und die Dicar¬ bonsaureanhydride im molaren Verhältnis 1 : 0,9 bis 1 : 1,1 einsetzt.6. The method according to claims 3 to 5, characterized gekenn¬ characterized in that the alkyl compounds and the dicarboxylic acid anhydrides are used in a molar ratio of 1: 0.9 to 1: 1.1.
7. Verfahren nach den Ansprüchen 3 bis 6, dadurch gekenn¬ zeichnet, daß man als Chlorverbindungen Phosphortrichlo- rid, Thionylchlorid oder Chlorkohlensäurealkylester einsetzt.7. The method according to claims 3 to 6, characterized gekenn¬ characterized in that the chlorine compounds used are phosphorus trichloride, thionyl chloride or chlorocarbonate.
8. Verfahren nach den Ansprüchen 3 bis 7, dadurch gekenn¬ zeichnet, daß man die Acylierungsprodukte und die Chlor¬ verbindungen im molaren Verhältnis 1 : 0,8 bis 1 : 2,0 einsetzt.8. Process according to Claims 3 to 7, characterized in that the acylation products and the chlorine compounds are used in a molar ratio of 1: 0.8 to 1: 2.0.
9. Verfahren nach den Ansprüchen 3 bis 8, dadurch gekenn¬ zeichnet, daß man als Polyhydroxyalkylamine Glucosyl¬ amine, Glucamine oder 2,2-Bis(hydroxymethyl)-2-amino- ethanol einsetzt.9. The method according to claims 3 to 8, characterized gekenn¬ characterized in that the polyhydroxyalkylamines used are glucosylamines, glucamines or 2,2-bis (hydroxymethyl) -2-aminoethanol.
10. Verfahren nach den Ansprüchen 3 bis 9, dadurch gekenn¬ zeichnet, daß man die Säurechloride bzw. die gemischten Anhydride der Acylierungsprodukte und die Polyhydroxy¬ alkylamine und Sorbityl- bzw. Glucosylamine im molaren Verhältnis 1 : 0,9 bis 1 : 1,1 einsetzt.10. The method according to claims 3 to 9, characterized gekenn¬ characterized in that the acid chlorides or the mixed anhydrides of the acylation products and the Polyhydroxy¬ alkylamines and sorbityl or glucosylamines in a molar ratio of 1: 0.9 to 1: 1, 1 starts.
11. Hautpflegemittel, enthaltend Pseudoceramide nach An¬ spruch 1. 11. Skin care agent containing pseudoceramides according to claim 1.
12. Verwendung von Pseudoceramiden nach Anspruch 1 als "synthetic barrier lipids" zur Herstellung von Haut¬ pflegemitteln. 12. Use of pseudoceramides according to claim 1 as "synthetic barrier lipids" for the production of skin care products.
PCT/EP1995/000229 1994-02-01 1995-01-23 Pseudo-ceramides WO1995021181A1 (en)

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