WO2015078554A1

WO2015078554A1 - Mixtures of creatine or creatinine and glucuronolactones

Info

Publication number: WO2015078554A1
Application number: PCT/EP2014/002952
Authority: WO
Inventors: Christophe Carola; Marcus Brunner
Original assignee: Merck Patent Gmbh
Priority date: 2013-11-26
Filing date: 2014-11-04
Publication date: 2015-06-04

Abstract

The invention relates to mixtures of creatine or creatinine and glucuronolactone derivatives as well as to the use thereof in preparations, in particular in preparations for modifying the skin tone.

Description

CREATINE OR CREATININE MIXTURES WITH GLUCURONOLACTONES

The present invention relates to mixtures of creatine or creatinine with Glucuronolactonderivaten of formula I, as described below, and their use in preparations, in particular in formulations for changing the hue of the skin.

Glucuronolactone derivatives of the formula I are in part from the

Publication WO 2012/010242 or WO 2013/083225 known. The compounds of formula I, as described below, and / or their salts, tautomers, stereoisomers and / or solvates, including mixtures thereof in all ratios, are self-tanning substances or act as tanning enhancers for dihydroxyacetone or for a mixture of self-tanning substances containing dihydroxyacetone or they for coloring keratin-containing fibers, in particular animal or human hair, suitable.

Because of these properties, the compounds of formula I, as described below, are capable of increasing the hue of the skin

to modulate, in particular in combination with dihydroxyacetone, the hue obtained in tanning with dihydroxyacetone or by the mixture or preparation containing dihydroxyacetone, or they may also act as a contrast reducing agent.

However, it has been found that the pH of some

Preparations too strong in the acidic area shifts. If such a preparation, for example, applied to the skin, it is perceived as unpleasant on the skin.

The present invention is concerned with the task of improving the skin feel of preparations containing at least one

Glucuronolactone derivative of the formula I and / or a salt, tautomer, Stereoisomer and / or solvate or mixtures thereof in all

Conditions included.

This object is solved by the independent claims.

It has surprisingly been found that by the combination of creatine and / or creatinine, in particular of creatine, with at least one compound of formula I or a salt, tautomer, stereoisomer and / or solvate, as described below, the pH of a

Preparation containing the substances listed above, is 3.5 to 5 and such a preparation is perceived as pleasant. Without wishing to be bound by theory, creatine and / or creatinine, in particular creatine, is capable of the at least one compound of formula I, as described below, in a preparation

stabilize.

This effect can now be achieved by a mixture of creatine and / or creatinine with at least one compound of formula I or a salt, tautomer, stereoisomer and / or solvate, as described below, in which this mixture is used to prepare a preparation. Alternatively, said individual components may be added without prior mixing of a preparation to achieve the effect described. A first subject of the invention is a mixture of creatine and / or creatinine r formula I.

wherein R ¹ and R ^{2 are} each independently

H aryl,

a straight-chain or branched alkyl group having 1 to 30 carbon atoms, which may be substituted by aryl, or

a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, containing one or more double bonds which may be substituted by aryl, where R ¹ and R ^{2 may} together also form an unsubstituted or substituted five-membered ring, the

a) by at least one straight-chain or branched alkyl group having 1 to 30 carbon atoms and / or

b) by at least one aryl group having 6 to 12 C atoms and / or c) by at least one straight-chain or branched alkenyl group having 2 to 30 C atoms containing one or more double bonds

may be substituted

wherein the alkyl group having 1 to 30 carbon atoms and / or the alkenyl group having 1 to 30 carbon atoms may be substituted with aryl, and / or the

Aryl group having 6 to 12 carbon atoms by alkyl, OH, OAlkyl, NH ₂₎ NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) -OAikyl be substituted can

R ³ denotes H, a straight-chain or branched alkyl group having 1 to 30 C atoms or -C (O) R ⁵ ,

R ^{4 is} H or OR ⁶ ,

R ^{5 represents} a straight-chain or branched alkyl group having 1 to 30 C atoms or

an aryl group having 6 to 12 C atoms, where the aryl group having 6 to 12 C atoms is alkyl, vinyl, OH, O-alkyl, NH ₂₎ NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC ( O) alkyl and / or C (O) OAlkyl, or a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group with 6 up to 12 C-atoms by alkyl, OH, Oalkyl, NH ₂₎ NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) O alkyl may be substituted, and

R ⁶ denotes H or a straight-chain or branched alkyl group having 1 to 30 C atoms,

in which

Aryl is an aryl group having 6 to 12 C atoms, which is optionally substituted by alkyl, OH, OAlkyl, NH ₂ , NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl or C (O) -OAlkyl may be substituted, and

Alkyl denotes a straight-chain or branched alkyl group having 1 to 30 C atoms,

wherein the compounds of formula I, if structurally possible, may be in an open-chain form or in a furanoid or pyranoid lactone and / or lactol form and / or their salts, tautomers, stereoisomers and / or solvates, including mixtures thereof in all ratios.

Another object of the invention is the use of creatine and / or creatinine for the stabilization of at least one compound of formula I,

in a preparation,

wherein R ¹ and R ^{2 are} each independently

H

aryl,

a straight-chain or branched alkenyl group having 2 to 30 C atoms, containing one or more double bonds which may be substituted by aryl, wherein R ¹ and R ² together may also form an unsubstituted or substituted five-membered ring, the

b) by at least one aryl group having 6 to 12 carbon atoms and / or c) by at least one straight-chain or branched alkenyl group having 2 to 30 carbon atoms containing one or more double bonds may be substituted,

Aryl group having 6 to 12 carbon atoms by alkyl, OH, OAlkyl, NH ₂ , NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) -OAikyl be substituted can

R ^{4 is} H or OR ⁶ ,

an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms by alkyl, vinyl, OH, OAlkyl, NH ₂ , NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O ) Alkyl or C (O) OAlkyl, or a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group with 6 to 12 carbon atoms by alkyl, OH, O-alkyl, NH _2, NHalkyl, N (alkyl) _2, C (O) alkyl, OC (O) alkyl and / or C (O) OAIkyl may be substituted and

in which Aryl is an aryl group having 6 to 12 C atoms, which is optionally substituted by alkyl, OH, OAlkyl, NH _2> NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl or C (O) -OAlkyl may be substituted, and

Alkyl denotes a straight-chain or branched alkyl group having 1 to 30 C atoms,

Another object of the invention is the use of creatine and / or creatinine to improve the skin feel of a preparation containing at least one compound of formula I.

wherein R ¹ and R ^{2 are} each independently

H

aryl,

b) by at least one aryl group having 6 to 12 carbon atoms and / or c) by at least one straight-chain or branched alkenyl group having 2 to 30 carbon atoms containing one or more double bonds

may be substituted

wherein the alkyl group having 1 to 30 carbon atoms and / or the alkenyl group having 1 to 30 carbon atoms may be substituted with aryl and / or the

Aryl group having 6 to 12 carbon atoms by alkyl, OH, OAlkyl, NH ₂ , NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) -OAikyl be substituted R ³ H may be a straight-chain or branched alkyl group having 1 to 30 C atoms or -C (O) R ⁵ ,

R ^{4 is} H or OR ⁶ ,

an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms by alkyl, vinyl, OH, OAlkyl, NH ₂ , NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O ) Alkyl or C (O) OAlkyl, or a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group with 6 to 12 C atoms may be substituted by alkyl, OH, OAlkyl, NH ₂ , NHalkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) OAlkyl and

in which

Alkyl denotes a straight-chain or branched alkyl group having 1 to 30 C atoms,

where the compounds of formula I, if structurally possible, in an open-chain form or in a furanoid or pyranoid lactone and / or Lactolform and / or their salts, tautomers, stereoisomers and / or solvates, including mixtures thereof in all ratios. The term skin according to the invention also includes the scalp.

Among solvates of the compounds are deposits of inert

Understood solvent molecules to the compounds that form due to their mutual attraction. Solvates are e.g. Mono or dihydrate or alcoholates.

The salts of the compounds of the formula I as described above are preferably pharmaceutically or cosmetically acceptable. A base of formula I can with an acid in the associated

Acid addition salt can be converted, for example, by reacting equivalent amounts of the base and the acid in an inert

Solvents such as ethanol and subsequent evaporation. Particularly suitable acids for this reaction are those which yield physiologically acceptable salts.

On the other hand, compounds of formula I can be converted with bases (e.g., sodium or potassium hydroxide or carbonate) into the corresponding metal, especially alkali metal or alkaline earth metal, or into the corresponding ammonium salts.

Tautomers are molecules with the same molecular formula whose atoms are linked differently, which rapidly change into each other due to the migration of individual atoms or groups of atoms. H. the two isomers are in rapid chemical equilibrium.

Stereoisomers are molecules that have the same bond of the atoms and functional groups in a different spatial structure exhibit. Typical examples of stereoisomers are enantiomers and diastereomers.

Enantiomers are molecules that behave like mirror images and can not be converted into each other by twisting bonds. Mixtures of enantiomers in the ratio 1: 1 are referred to as racemates.

Diastereomers are all stereoisomeric molecules that do not behave like mirror images.

Formula 1-1 visualizes the diastereomers of formula I based on α-D - (+) - glucuronic acid 3,6-lactone and β-D - (+) - glucuronic acid 3,6-lactone:

wherein R ¹ , R ² , R ³ and R ⁴ have the meaning given above.

Preference is given to the compounds of the formula I as described above or described below as being preferred, including

used or stabilized stereoisomeric forms. Particular preference is given to using or stabilizing the compounds of the formula I- ¹ , where R ¹ , R ² , R ³ and R ⁴ have the meaning given above or below. Correspondingly, accordingly, the stereochemistry of the formula 1-1 given for the compounds of the formulas (1) to (29) mentioned below is accordingly preferred.

A straight-chain or branched alkyl group having 1 to 10 C atoms is, for example, methyl, ethyl, / isopropyl, propyl, butyl, sec-butyl or tert-butyl, pentyl, 1-, 2- or 3-methylbutyl, 1,1 -, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl. A straight-chain or branched alkyl group having 1 to 30 carbon atoms comprises the previously described group of straight-chain or straight chain alkyl groups

branched alkyl group having 1 to 10 C atoms and undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl, heptadecanyl, octadecanyl, nonadecanyl, eicosanyl, heneicosanyl, docosanyl,

Tricosanyl, tetracosanyl, pentacosanyl, hexacosanyl, heptacosanyl, octacosanyl, nonacosanyl and triacontanyl. The term "alkyl" as used herein means a straight-chain or branched alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably methyl, ethyl, isopropyl, n -propyl or n-butyl "O-Alkyl" is known to the person skilled in the art and denotes a straight-chain or branched alkoxy group having 1 to 30 C atoms. The names are derivable from the names of the alkyl group in which the suffix -oxygen is appended. The alkoxy group OMethyl is, for example, methyloxy.

The term "NHalkyl" means a monoalkylated amino group wherein the alkyl group may be straight-chain or branched and has 1 to 30 carbon atoms The term "N (alkyl) ₂ " accordingly denotes a

Dialkylamino group, wherein the alkyl group is independently

may be straight or branched and have 1 to 30 carbon atoms. The term "C (O) alkyl" denotes a -C (= O) alkyl group, wherein alkyl has the meaning given above. The term "OC (O) alkyl" refers to an -OC (= O) alkyl group, wherein alkyl has the meaning given above.

The term "C (O) Oalkyl" denotes a -C (= O) -O-alkyl group, wherein alkyl has the meaning given above.

A straight-chain or branched alkenyl having 2 to 30 C atoms, wherein several double bonds may also be present, is, for example, ethenyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso-pentenyl, Hexenyl, heptenyl, octenyl, -C9H17, -C10H19 to -C30H49; preferably ethenyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, 4-pentenyl, iso-pentenyl, hexenyl or decenyl. Particularly preferred alkenyl groups are ethenyl, 2- or 3-butenyl. An aryl group having 6 to 12 C atoms means phenyl, naphthyl,

Anthracenyl or phenanthryl which may be substituted by alkyl, OH, Oalkyl, NH ₂₎ NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) -alkyl or C (O) -Oalkyl. Preferably, the aryl group is unsubstituted or substituted by alkyl, OH, OAlkyl, NH ₂ , NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) -alkyl or C (O) -OAlkyl substituted phenyl.

In the mixtures according to the invention or in the inventive use of creatine and / or creatinine, compounds of the formula I or of the formula 1-1 are preferably used / stabilized in which R ¹ and R ^{2 are} H or

R ¹ and R ² together form a five-membered ring,

which may be substituted by at least one straight-chain or branched alkyl group having 1 to 10 C atoms;

and / or by at least one straight-chain or branched one

Alkenyl group having 1 to 10 carbon atoms containing one or more

Double bonds may be substituted by at least one

Phenyl group may be substituted, wherein the phenyl group by alkyl, OH, Oalkyl, C (O) alkyl, OC (O) alkyl and / or C (O) -OAlkyl may be substituted;

and / or may be substituted by a phenyl group, wherein the

Phenyl group may be substituted by alkyl, OH, OAlkyl, C (O) alkyl, O-C (O) alkyl and / or C (O) -OAlkyl,

R ^{3 is} H or -C (O) R ⁵ ,

R ^{4 is} H and

R ^{5 represents} a straight-chain or branched alkyl group having 1 to 12 C atoms or

an aryl group having 6 to 12 C atoms, wherein the aryl group having 6 to 12 C-atoms by alkyl, vinyl, OH, OAlkyl, NH ₂₎ NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O ) Alkyl and / or C (O) OAlkyl or a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 C atoms may be substituted by alkyl, OH, OAlkyl, NH ₂ , NHalkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) OAlkyl

and

Alkyl is a straight-chain or branched alkyl group having 1 to 12 C atoms.

In the mixtures according to the invention or in the use according to the invention of creatine and / or creatinine, compounds of the formula I or of the formula 1-1 are particularly preferably used / stabilized in which

R and R ^{2 are} H or

R ¹ and R ² together form a five-membered ring,

which is substituted by at least one straight-chain or branched alkyl group having 1 to 10 C atoms;

and / or by at least one straight-chain or branched one

Alkenyl group having 1 to 10 carbon atoms containing one or more

Double bonds substituted by at least one phenyl group wherein the phenyl group may in turn be substituted by alkyl, OH, OAlkyl, C (O) alkyl, OC (O) alkyl and / or C (O) -OAlkyl; and / or is substituted by a phenyl group, where the phenyl group may be substituted by alkyl, OH, OAlkyl, C (O) alkyl, OC (O) alkyl and / or C (O) -OAlkyl,

R ^{3 is} H or -C (O) R ⁵ ,

R ^{4 is} H and

an aryl group having 6 to 12 C atoms, wherein the aryl group having 6 to 12 C-atoms by alkyl, vinyl, OH, OAlkyl, NH ₂ , NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O ) Alkyl and / or C (O) OAlkyl or a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 C atoms can be substituted by alkyl, OH, OAlkyl, NH ₂ , NHalkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl and / or C (O) OAlkyl

and

Alkyl is a straight-chain or branched alkyl group having 1 to 12 C atoms.

In the mixtures according to the invention or in the use according to the invention of creatine and / or creatinine, compounds of the formula I or of the formula 1-1 are very particularly preferred

used / stabilized, which correspond to the formulas (1) to (29):

used / stabilized, which correspond to the formulas (1), (2), (3) and (9), as described above.

In the mixture according to the invention can also be two or more

Compounds of formula I or the formula 1-1, as described above or described as being preferred, be contained.

In a preferred embodiment of the invention, the

inventive mixture creatine.

A very particularly preferred mixture according to the invention consists of creatine and a compound of the formula (1), (2), (3) or (9).

In a preferred embodiment of the invention, creatine is used for stabilization. In a very preferred

Embodiment of the invention, creatine stabilizes a compound of formula (1), (2), (3) or (9) in a preparation. The compounds of the formula I, 1-1, (1) to (29) are in part commercially available or can be prepared by processes which are described in

WO 2012/010242 or WO 2013/083225 are described, whose content in this regard expressly also belongs to the disclosure of the present application.

The formation of the five-membered ring is formed, for example, by (Lewis) -acid-catalyzed reaction of the corresponding glucuronolactone, in which R ¹ and R ² signify OH, with acetone.

For compounds of the formula I or 1-1 in which R ^{4 is} H and R ^{3 is} -C (O) R ⁵ , compounds of the formula I or 1-1 are corresponding to starting materials in which R ^{4 is} H and R ^{3 is} OH where R ¹ and R ^{2 are} a ben:

The introduction of the substituent R ³ = -C (O) R ⁵ to the

Starting compounds, as described above, carried by a

Esterification. The starting materials are reacted when using the Schotten-Baumann reaction with an acid chloride R ⁵ -C (= O) -CI, wherein R ^{5 has} a meaning mentioned above or as preferred. The esterification is usually carried out in the presence of bases such as triethylamine or pyridine. In the so-called unicorn variant, dimethylaminopyridine is added in addition to activation. In addition to the use of the acid chlorides, as described above, it is also possible to use acid bromides or anhydrides or active esters of the acid

R ⁵ -C (= O) -OH can be used, wherein R ^{5 has} a meaning mentioned above or as preferred. Suitable reaction conditions for esterifications with the aid of active esters are described in Esterification: Methods, Reactions, and Applications, Author: Prof. Dr. med. Junzo Otera, Wiley-VCH Verlag GmbH & Co. KGaA, ISBN 9783527304905, described,

in particular in Chapter 1, the content of which is expressly also part of the disclosure of the present application.

Another object of the invention are also preparations containing creatine and / or creatinine and at least one compound of formula I or of formula 1-1 and / or their salts, tautomers,

Stereoisomers and / or solvates, including mixtures thereof in all proportions, as described above or described as being preferred or corresponding to the formulas (1) to (29).

Another object of the invention are also preparations containing the inventive mixture of creatine and / or creatinine with one or more compounds of the formula I or the formula 1-1 and / or their salts, tautomers, stereoisomers and / or solvates, including mixtures thereof in all proportions as described above or described as preferred or according to the formulas (1) to (29).

Another object of the invention is also the use of a mixture of creatine and / or creatinine with a compound of formula I, as described above or described as preferred, in cosmetic, pharmaceutical or dermatological preparations or

Medical devices.

The preparations are preferably topically applicable preparations, for example cosmetic or cosmetic preparations

dermatological formulations, pharmaceutical preparations or medical devices. The preparations in this case contain a cosmetically or dermatologically suitable carrier and, as appropriate

desired property profile optionally further suitable ingredients. In the case of pharmaceutical preparations, the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients. If it is a medical device, then a compatible carrier for the medical device is selected.

Topically applicable means for the purposes of the invention that the preparation is applied externally and locally, i. that the preparation must be suitable, for example, to be applied to the skin can.

For the purposes of the present invention, the term agent or formulation is used synonymously in addition to the term preparation.

The preparations may comprise or contain, consist essentially of or consist of the stated necessary or optional ingredients. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

Further preferred combinations of embodiments are disclosed in the claims.

According to the invention, cosmetic or dermatological preparations or medical products are preferred. According to the invention, cosmetic preparations or medical products are particularly preferred.

According to the invention, cosmetic preparations are very particularly preferred. The preparation preferably contains creatine and / or creatinine and the compound (s) of the formula I or 1-1, as described above, in a molar ratio of 3: 1 to 0.4: 1, preferably in a molar ratio of 2: 1 up to 0.8: 1. If creatine and creatinine are used together, the total amount for the molar ratio is decisive. The same applies to several compounds of the formula I or of the formula 1-1 in relation to creatine and / or creatinine.

Another object of the invention is therefore the preparation as described above or described as preferred, wherein creatine and / or creatinine and the compound (s) of the formula I, as described above or described as preferred, in a molar ratio of 3: 1 to 0.4: 1 are present in the preparation.

Due to the effect that creatine and / or creatinine achieve / achieve, the preparations according to the invention have a pH which is 3.5 to 5, preferably 4 to 5, more preferably 4.

Preferably, the preparation contains the at least one compound of formula I or 1-1, as described above or described as preferred, in an amount of 0.01 to 20 wt .-%, particularly preferably in an amount of 0.5 to 15 wt .-% and most preferably in an amount of 1 to 8 wt .-%, based on the total amount of the preparation.

The preparation according to the invention preferably contains, as before

described at least one more self-tanning substance. Another object of the invention is therefore the preparation, as described above or described as preferred, wherein at least one further self-tanning substance is included.

Suitable self-tanning substances are dihydroxyacetone,

Glycerol aldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2-hydroxy-1,4-naphthoquinone (Lawson), or a mixture thereof Links. Erythrulose and dihydroxyacetone are particularly preferably used. Erythrulose or dihydroxyacetone is particularly preferably used. Most preferably, dihydroxyacetone is preferred. The principle of staining to form melanoid is that

basic dyeing principle of the self-tanning substances, as described above, which react in the sense of a Maillard reaction or via a Michael addition. The preparation according to the invention preferably contains, as before

described, in addition to the above-described self-tanning substances or alternatively described self-tanning substances, at least one further active ingredient as "biologically active

Tanning substance "in which it effects an increase in melanin synthesis, an improvement in melanin transport and / or an improvement in the distribution of melanin in suprabasal layers Such" biologically active self-tanning substances "are published in WO 2012/097857. Representative of this class of compounds is the substance hexadecanoic acid 5-hydroxy-2-methyl-4-oxo-4H-chromen-7-yl ester, which is marketed under the name RonaCare® Bronzyl ™ by Merck, Darmstadt.

Substances with a similar active principle are Symrise's SymBronze® 1659 (microalgae extract), MelanoBronze (Acetyl Tyrosine, Vitex agnus-castus extract) from Mibelle, Melatime ™ (Butylene Glycol, Palmitoyl Tripeptide-40) from Lipotec, Melactiva ™ (maltodextrin, Mucuna pruriens seed extract) from Lucas Meyer Cosmetics, Unipertan® (butylene glycol, acetyl tyrosine, hydrolyzed vegetable protein, riboflavin) from Induchem or Phototan® (sorbitol, ornithine HCl, tyrosine, arginine, HCI, silica) from Laboratoire Serobiologique.

Preferably, the preparation contains at least dihydroxyacetone in an amount of 0.01 to 20 wt .-%, particularly preferably in an amount of 0.5 to 15 wt .-% and most preferably in an amount of 1 to 8 wt .-%, based on the total amount of the preparation.

Preparations with self-tanning properties, especially those containing dihydroxyacetone, tend to be used on the

Human skin to malodors, which are probably caused by degradation products of dihydroxyacetone itself or by products of side reactions, and the users are sometimes perceived as unpleasant. It has been found that these off-odors are avoided when using formaldehyde scavengers and / or flavonoids. Therefore, the preparation according to the invention containing at least one compound of formula I or 1-1, as described above or described as preferred, and the individual compounds and at least one self-tanner, preferably also formaldehyde scavenger, and optionally flavonoids to improve the odor.

Preferably, the formaldehyde scavenger is selected from the group consisting of alkali metal, alkaline earth metal or ammonium metabisulfite. Particularly preferred is a preparation containing in combination DHA Plus. DHA Plus is a product blend containing sodium metabisulfite, equivalent to Na ₂ S ₂ O ₅ or INCI: sodium disulfite, for masking, elimination or neutralization of formaldehyde. The addition of

Sodium metabisulfite in finished formulations significantly reduces or eliminates the unpleasant odor. DHA Plus is distributed by Merck, Darmstadt.

As described above, flavonoids can be used to improve the

Smell and optionally be included for tanning. Preferably, it is a flavonoid in which one or more phenolic hydroxy groups are blocked by etherification or esterification. For example, have hydroxyethyl-substituted Flavonoids, such as preferably troxerutin, troxequercetin, troxeisoquercetin or troxeluteolin, and flavonoid sulphates or

Flavonoid phosphates, such as preferably rutin sulfates, proved to be particularly suitable flavonoids. Particularly preferred flavonoids are rutin sulfate and troxerutin.

If a contrast reduction is to be achieved, then the

Preparation according to the invention, as described above, in addition to the optional "classic" self-tanning substances described above, no "biologically active self-tanning substances", but at least one further active ingredient which inhibits the biochemical melanin formation. The union of chemically tanning preparations, with

melanogenesis inhibiting substances already causes

hyperpigmented skin areas lose their high melanin concentrations and the hue generated by the colorant on the skin surface is widely spread.

For combination, melanogenesis inhibitors such as e.g.

Hydroquinone, niacinamide, arbutin, alpha-arbutin, beta-arbutin, deoxy-arbutin, vitamin C, ascorbyl palmitate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, azelaic acid, potassium 4-methoxysalicylate, trans-4- (aminomethyl) cyclohexane carboxylic acid (Tranexamic acid),

Licorice extract, ascorbyl glucoside, 3-O-ethyl ascorbyl ether, 2-O-ethyl ascorbyl ether, kojic acid, kojisuredipalmitate, resorcinol, glutathione, cysteine, mulberry extract, hydrogen peroxide, zinc peroxide, sodium peroxide, benzoyl peroxide, glucosamine, aloesin, oleic acid 4-isopropyl-catechol, Emblica, glycolic acid, ellagic acid, ferulic acid, resveratrol, oxyresveratrol, quercetin, kaempferol,

Bile acid, hesperidin, p-coumaric acid, epicatechingallate,

Epigallocatechin gallate, α-hydroxycarboxylic acids (e.g., lactic acid,

Salicylic acid, malic acid), α-tocopherol, (E) -3- (4-methoxy-phenyl) -acrylic acid (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro -furan-2-yl) -2-hydroxyethyl ester or 1- [4- (1,1-dimethylethyl) phenyl] -3- (4- methoxyphenyl) -1,3-propanediol. Preferred melanogenesis inhibitors are ascorbic acid and its derivatives, niacinamide, emblica, ellagic acid, mulberry extract, kojic acid, liquorice root extract, rucinol,

Hydroquinone, azelaic acid, arbutin, magnesium ascorbyl phosphate (E) -3- (4-methoxy-phenyl) -acrylic acid (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5 dihydro-furan-2-yl) -2-hydroxyethyl ester or 1- [4- (1,1-dimethylethyl) phenyl] -3- (4-methoxyphenyl) -1,3-propanediol.

The formulations may preferably contain excipients, such as cosmetic oils (e.g., Caprylic / Capric Triglycerides, C12-15 alkyl benzoates, isopropyl myristate, arylalkyl benzoates, e.g.

Phenethylbenzoate (X-Tend 226) or Cosmacol brand Olole components such as dimyristyl tartrate, tri C14-C15 alkyl citrate, C12-C13 alkyl lactate, tridecyl salicylate, C12-C13 alkyl octanoate, C12-C13 alkyl maleate, C12-C13 alkyl citrate , C12-C13 alkyl tartrates), or polar protic auxiliaries (eg propylene glycol, glycerol, isopropanol, ethanol) or so-called.

Solubilizers (e.g., butylphthalimides, isopropylphthalimides,

Dimethylisosorbide). Very particularly preferred cosmetic oils are C12-C13 alkyl lactates, commercially available as Cosmacol ELI and

Phenethylbenzoate, commercially available as X-Tend 226.

The invention also provides a process for the preparation of a preparation as described above, wherein at least one compound according to formula I or 1-1, as described above or described as preferred, mixed with at least one carrier suitable for cosmetic, pharmaceutical, dermatological preparations and, where appropriate, with other excipients or fillers, as well

optionally mixed with other active ingredients, for example the aforementioned self-tanning substances. is

Dihydroxyacetone are added, then added last as dihydroxyacetone and mixed. Suitable excipients and active or auxiliary substances have already been described in detail previously or in the following part. The described preparations may furthermore also contain color pigments, the layer structure of the pigments not being limited. Preferably, the color pigment when used from 0.5 to 5 wt .-% should be skin-colored or brownish. The selection of a corresponding

Pigments is familiar to the skilled person.

The preparations described may also contain hydrophilic or lipophilic sunscreen filters that are effective in the UVA range and / or UVB range and / or IR and / or VIS range (absorber). These substances can in particular under

Cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives,

Triazinderivaten, β, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters, which are described in the application WO -93 / 04665 be selected. Further examples of organic filters are given in patent application EP-A 0 487 404 and WO2009 / 077356.

Suitable organic UV-protective substances are preferably to be selected from the following list:

para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. sold under the name "Escalol 507" from the company. ISP, glyceryl PABA, PEG-25 PABA, z. B. sold under the name "Uvinul P25" from the company. BASF.

Salicylates: homosalates sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. sold under the name "Neo Heliopan OS" from the Fa. Symrise, Dipropylene glycol salicylate, z. B. sold under the name "Dipsal" from the company. Scher, TEA salicylates, z. B. marketed under the name "Neo Heliopan TS" of the Fa. Symrise. β, β-diphenylacrylate derivatives: octocrylenes, e.g. B. sold under the name "Eusolex® OCR" from Merck, "Uvinui N539" from BASF, Etocrylene, for example, sold under the name "Uvinui N35" from BASF Further, for example, Methoxycrylen, sold under the name Solastay S1 from the company Hallstar.

Benzophenone Derivatives: Benzophenone-1, e.g. Sold under the name "Uvinui 400"; Benzophenone-2, e.g. Sold under the name "Uvinui D50"; Benzophenone-3 or oxybenzone, e.g. Sold under the name "Uvinui M40"; benzophenone-4, e.g. Sold under the name "Uvinui MS40"; Benzophenone-9, e.g. B. sold under the

Name "Uvinui DS-49" from BASF, Benzophenone-5, Benzophenone-6, z. B. marketed under the name "Helisorb 11" from the Fa.

Norquay, Benzophenone-8, e.g. Sold under the name "SpectraSorb UV-24" by American Cyanamid, benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, sold by Merck, Darmstadt under the name Eusolex® 4360. Benzylidene camphor derivatives: 3-Benzylidenecamphor, z. Sold under the name "Mexoryl SD" from the company. Chimex, 4-Methylbenzylidene- camphor, z. B. sold under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. sold under the name "Mexoryl SL" from the company. Chimex, Camphor benzalkonium methosulfate, z. Sold under the name "Mexoryl SO" from the company Chimex,

Terephthalylidenedicamphorsulfonic acid, e.g. Sold under the name "Mexoryl SX" from the company Chimex, polyacrylamidomethylbenzylidene camphor under the name "Mexoryl SW" from the company. Chimex. Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B.

sold under the name "Eusolex 232" by Merck, disodium phenyl dibenzimidazole tetrasulfonate, e.g. B. marketed under the name "Neo Heliopan AP" by Fa. Symrise.

Phenylbenzotriazole derivatives: Drometrizole trisiloxanes, e.g. Sold under the name "Silatrizole" by the company. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, for. B. marketed under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B. marketed under the name "Tinosorb M" from BASF.

Triazine derivatives: ethylhexyltriazone, e.g. B. sold under the name "Uvinul T150" from the company. BASF, Diethylhexylbutamidotriazone, z. B.

marketed under the name "Uvasorb HEB" by the company Sigma 3V.

Further triazine derivatives are exemplified by 2,4,6-tris (diisobutyl 4'-aminobenzalmalonates) -s-triazines, or 2,4,6-tris (biphenyl) -1, 3,5-triazines, butyl 4 - ({4 - {[4- (butoxycarbonyl) phenyl] amino} -6 - [(3- {1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -1, 3.5 -triazin-2-yl} amino) benzoate sold under the name Mexoryl SBS. Structure of Mexoryl SBS:

and bis-ethylhexyloxyphenol methoxyphenyl triazines, eg sold under the name Tinosorb S by BASF. Anthraniline derivatives: menthyl anthranilate, e.g. B. marketed under the name "Neo Heliopan MA" by Fa. Symrise.

Imidazole derivatives: ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate Derivatives: Polyorganosiloxanes containing functional benzalmalonate groups, e.g. Polysilicone-15, e.g. Sold under the name "Parsol SLX" by Hoffmann LaRoche.

4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

Benzoxazole derivatives: 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures containing this.

Pi erazine derivatives such as the compound

or the UV filters of the following structures

Preferably, it may also be combined with UV filters based on polysiloxane copolymers having a random distribution according to the following formula, e.g. a = 1, 2; b = 58 and c = 2.8 are:

These organic UV filters are usually incorporated in formulations in an amount of from 0.01 percent by weight to 20 percent by weight, preferably 1 percent by weight to 10 percent by weight. The preparations may also contain inorganic UV filters, so-called particulate UV filters. These combinations with particulate UV filters are possible both as a powder and as a dispersion or paste.

In this case, both those from the group of titanium dioxides such.

coated titanium dioxide (for example Eusolex ^® T-2000, Eusolex ^® T-AQUA,

Eusolex ^® T-AVO, Eusolex ^® T-OLEO), zinc oxides (for example Sachtotec® ^®),

Iron oxides or else cerium oxides and / or zirconium oxides are preferred.

It may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat

Cosmetics & Toiletries, 1990, 05, 53-64. This may include one or more of the following

Aftertreatment components can be selected: amino acids,

Beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially collagen or elastin), alkanolamines, silica, alumina, other metal oxides, Phosphates, such as sodium hexametaphosphate or glycerin.

These inorganic UV filters are usually incorporated in the formulations in an amount of from 0.1 percent by weight to 25 percent by weight, preferably 2 percent by weight to 10 percent by weight.

By combining one or more of the compounds mentioned with UV filter action, the protective effect against harmful

Effects of UV radiation can be optimized. All mentioned UV filters can also be used in encapsulated form. In particular, it is beneficial to use organic UV filters in

to use encapsulated form. Preferred preparations may also comprise at least one further cosmetic active ingredient, for example selected from

Antioxidants, anti-aging, anti-wrinkle, anti-dandruff, anti-acne, deodorant, anti-cellulite, skin lightening or vitamins.

The protective effect against oxidative stress or against the action of free radicals can be improved if the agents or preparations according to the invention contain one or more antioxidants, wherein the expert does not encounter any difficulties in selecting suitable fast or delayed-acting antioxidants.

There are many known and proven substances in the literature that can be used as antioxidants, e.g. Amino acids (e.g.

Glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and salts thereof,

Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (for example buthionine sulfoximines,

Homocysteine sulfoximine, buthionine sulfone, penta-, hexa-, heptathionin sulfoximine) in very low tolerated dosages (eg pmol to μητιοΙ / kg), also (metal) chelators, (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), cc-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, Bile acids, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate,

Magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (eg, vitamin A palmitate), as well as benzoic acid coniferyl benzoate, rutinic acid and its derivatives, cc-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine .

Butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide , trans-stilbene oxide).

Suitable antioxidants are also compounds of the general

Formulas A or B

wherein

R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,

X is O or NH,

R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,

R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,

R ⁴ each independently of one another are H or linear or branched alkyl having 1 to 8 C atoms, R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and

R ⁶ denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis- (2-ethylhexyl) ester (for example Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3,5 dimethoxybenzy ) malonic acid-bis (2-ethylhexyl) ester (example RonaCare ^® AP).

Mixtures of antioxidants are also suitable for use in the compositions or preparations according to the invention. Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ^® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-tocopherol c, L - (+) - ascorbyl palmitate, citric acid and lecithin (for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) -. ascorbyl palmitate and citric acid (for example Oxynex ^® 2004) antioxidants are reacted with compounds of formula I in such compositions is typically in ratios ranging from 1000: 1 to 1: 1000, preferably used in amounts of 100: 1 to 1: 100.

Suitable anti-aging agents, especially for skin care

Preparations are preferably so-called compatible solutes.

Preferably, as compatible solute substances are selected from the group consisting of Pyrimidincarbonsäuren (such as ectoine and

Hydroxyectoine), proline, betaine, glutamine, cyclic diphosphoglycerate, N-acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), β-mannosylglycerate (firoin), β-mannosylglyceramide (firoin-A) or / and dimannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, eg an acid, a salt or ester of these compounds or

Combinations used.

Additional anti-aging agents Merck products such as 5,7-dihydroxy-2-methyl-chromone, marketed under the trade name RonaCare®l_uremine, or the commercial products RonaCare®lsoquercetin, RonaCare®Tilirosid or RonaCare®Cyclopeptide 5 can be used.

The preparations to be used may be further ingredients

Contain vitamins.

Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B ₂ ),

Nicotinic acid amide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D ₂ ), vitamin E, DL-α-tocopherol, tocopherol E acetate, tocopherol hydrogen succinate, vitamin Esculin (vitamin P active ingredient), thiamin (vitamin Bi ), Nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B ₁₂ ), particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL-a- Tocopherol, tocopherol-E-acetate, nicotinic acid,

Pantothenic acid and biotin. Vitamins are usually added to the flavonoid-containing premixes or preparations when applied cosmetically in the range of 0.01% to 5.0% by weight, based on the total weight.

The described retinoids are also effective anti-cellulite agents. Another well-known anti-cellulite drug is caffeine. Furthermore, compounds of the invention can be combined with all active ingredients and excipients, as they are systematically listed in WO2009 / 098139. In particular, these substances belong to those listed therein

"Moisturizers and Humectants", "Desquamating Agents", "Agents for Improving the Barrier Function", "Depigmenting Agents", "Antioxidants", "Dermo-relaxing or dermo-decontracting agents", "Antiglycation agents", "Agents for stimulating the synthesis of dermal and / or epidermal macromolecules and / or for

"Agents for stimulating fibroblast or keratinocyte proliferation and / or keratinocyte differentiation", "Agents for promoting the maturation of the horny envelope", "NO-synthase inhibitors", "Peripheral benzodiazepine receptor (PBR) antagonists", "Agents for increasing the activity of the sebaceous glands "," Agents for stimulating the energy metabolism of cells "," Tensioning agents "," Fat-reducing agents "," Sliming agents "," Agents for promoting the cutaneous microcirculation "," Calmatives or anti-irritants " , "Sebo-regulating or anti-seborrhoic agents", "Astringents", "Cicatrizing agents", "Anti-inflammatory agents", "Anti-acne agents". The content of WO 2009/098139 expressly also belongs to the disclosure content of the present application.

The said constituents of the preparation can be incorporated in the usual way, by means of techniques which are well known to the person skilled in the art. Suitable preparations for external use, for example as a cream or milk (OW, W / O, O / W / O, W / OW), as a lotion or emulsion, in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions can be sprayed onto the skin. They can be present as solid pens or be packaged as aerosol.

As an application form of the preparations to be used are preferably mentioned: solutions, suspensions, emulsions, PIT emulsions, pastes, Ointments, gels, creams, lotions, powders, soaps, surfactant-based cleansing preparations, oils, aerosol patches, envelopes, bandages and sprays.

Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants, odor improvers.

Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth,

Cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.

Powders and sprays may contain the usual carriers, e.g. Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays may additionally contain the usual volatilized, liquefied propellants, e.g.

Chlorofluorocarbons, propane / butane or dimethyl ether. Also, compressed air is advantageous to use. Solutions and emulsions may contain the usual excipients such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 3-butylglycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerin fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan or mixtures thereof Contain substances.

A preferred solubilizer in general is 2-isopropyl-5-methylcyclohexanecarbonyl-D-alanine methyl ester.

Suspensions may be the customary carriers such as liquid diluents, for example water, ethanol or propylene glycol, suspending agents, for example ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances. Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances. Surfactant-containing cleaning products may include the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid monoesters, fatty acid hydrolysates, isothionates, imidazolinium derivatives, methyltauate, sarcosinates, fatty acid amide ether sulfates, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated Glycerine fatty acid esters or mixtures of these substances.

Facial and body oils may contain the usual carriers such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as

Vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.

Other typical cosmetic applications include lipsticks, lip balms, powder, emulsion and wax make-up as well

Sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms include, in particular, emulsions. Emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of preparation. The lipid phase can advantageously be selected from the following substance group:

- mineral oils, mineral waxes

- Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;

Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids;

Silicone oils, such as dimethylpolysiloxanes, diethylpolysiloxanes,

Diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated,

branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or

unbranched alcohols of a chain length of 3 to 30 carbon atoms.

The aqueous phase of the preparations to be used contains

optionally advantageous alcohols, diols or polyols of low carbon number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl- or -monobutylether, diethylene glycol monomethyl or -monoethylether and analogous products, furthermore low C-number alcohols, e.g. As ethanol, isopropanol, 1, 2-propanediol,

Glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group Silica, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, respectively individually or in combination.

The preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, e.g.

Thickeners, emollients, moisturizers,

surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics. Even without further explanation it is assumed that a

One skilled in the art can make the most of the above description. The preferred embodiments and examples are therefore merely illustrative and in no way limiting in any way

To understand the revelation. The complete disclosure of all applications and publications cited above and below are incorporated by reference into this application. The weight percentages of the individual ingredients in the formulations of the examples are expressly intended to disclose the description and may therefore be used as features.

Other important features and advantages of the invention will become apparent from the dependent claims and from the examples.

It is understood that the features mentioned above and those yet to be explained not only in the combination specified, but also in other combinations or in Uniquely usable without the scope of the present

To leave invention.

Preferred embodiments of the invention are illustrated in the examples and will be explained in more detail in the following description, without limiting the scope of the present invention.

Example 1 :

Glucuronolactone of the formula (1) or glucuronolactone acetonide of the formula (2) are mixed with creatine or creatinine. After 24 hours, the pH is found to be 4 for creatine and 5 for creatinine. This pH remains unchanged for at least 8 weeks.

Execution:

There will be each

- 100 mg glucuronolactone + 85 mg (= 1eq) creatine

- 100 mg glucuronolactone + 64 mg (= 1 eq) creatinine

- 100 mg glucuronolactone

placed in a 25 ml Erlenmeyer and dissolved with 10 ml of deionized water on the magnetic stirrer. From these solutions, the pH is measured directly with the device Portamess Type 911 XpH Knick. The error of the measurement is measured at values of 0.2 to 0.3

The results are listed in Table 1.

Table 1 :

Procedure with glucuronolactone acetonide:

There will be each

- 500 mg glucuronolactone acetonide +345 mg (= 1eq) creatine

- 500 mg glucuronolactone acetonide + 262 mg (= 1 eq) creatinine

- 500 mg glucuronolactone acetonide

- 345 mg of creatine

- 262mg of creatinine in a 100 ml Erlenmeyer submitted and dissolved with 50 ml of deionized water on the magnetic stirrer. The pH was measured directly from these solutions using the device Portamess Type 911 XpH from Knick. The error of the measurement is between 0.2 and 0.3.

The results are shown in Table 2.

Table 2:

1 2 3 4 5

1%

1% acetonide /

Acetonide / 1 1eq 1% 1eq 1eq eq creatine creatinine acetonide creatine creatinine

Start pH 5.1 6.6 4 6.6 7.6

1h 5.0 6.3 3.9 0 0

24h 4.0 5.8 3.3 6.2 7.1

7d 4.0 5.2 2.9 6.1 7.1

14d 3.9 4.9 2.7 7.9 7.2

4W 4.1 4.6 2.8 8.6 8.2 8W 4.1 4.3 2.7 8.7 8.4

Example 2:

There will be each

0.1 g glucuronolactone acetonide dissolved in 10 ml deionized water (= 1%) in a 25 ml Erlenmeyer on the magnetic stirrer and each

- 0.014 g creatine = 0.2 eq

- 0.028 g creatine = 0.4 eq

, 0.042 g creatine = 0.6 eq

- 0.056 g creatine = 0.8 eq or

0.070 g of creatine = 1.0 eq was added to the glucuronolactone acetonide solutions. From these

Solutions, the pH is measured directly with the device Portamess Type 911 XpH from Knick. The error of the measurement is measured at values of 0.2 to 0.3.

The results are given in Table 3.

Table 3:

1 2 3 4 5

1% 1% 1% 1% 1%

Acetonide / 1 acetonide / acetonide / acetonide acetonide

0.2eq 0.4eq 0.6eq / 0.8eq / 1eq

Creatine Creatine Creatine Creatine Creatine

Start pH

1h 4,6 4,4 4,8 4,8 4,9

24h 3.8 4.0 4.1 4.2 4.3

48h 3.8 3.9 4.0 4.2 4.2

6d 3.5 3.6 3.6 3.9 4.0 8W 3.3 3.6 3.6 4.8 4.1

Formulation example 1: O / W tanning cream

Components / source of supply INCI [weight%] Trade name

A

Tego Care 150 (1) GLYCERYL STEARATE,

STEAR ETH-25-C ETETH - 20, STEAR YL ALCOHOL

Miglyol 812 N (2) CAPRYLIC / CAPRIC

TRIGLYCERIDES

Isopropyl myristate (3) ISOPROPYL MYRISTATE 2 paraffin liquid (4) PARAFFINUM LIQUIDUM 12

(MINERAL OIL)

Paraffin (4) PARAFFIN 2

Propylhydroxybenzoate (4) PROPYLPARABLES 0.15 Compound (1) (6) GLUCURONOLACTONE 4

B

1, 2-Propanediol (4) PROPYLENE GLYCOL 4 Sorbitol F liquid (4) SORBITOL 2 Methyl 4-hydroxybenzoate (4) METHYLPARABEN 0.05 Creatine monohydrate (5) KREATIN 3 Water, demineralized AQUA (WATER) ad 100

Water, demineralized 11.8 D

Perfume (q.s.) PERFUME 0.50 Total 100.00

Production method:

First, phases A and B are heated separately to 75 ° C. Thereafter, phase A is slowly added to phase B with gentle stirring. It is homogenized at 65 ° C for one minute. The mixture is then cooled with stirring to 40 ° C and the phase C was added with stirring, cooled to 35 ° C and the phase D was added, and further cooled.

Sources:

(1) Degussa-Goldschmidt AG (2) Sasol Germany GmbH (3) Cognis GmbH (4) Merck KGaA / Rona® (5) Alfa CaesaR (6) ABCR Formulation Example 2: O / W Tanning Cream

Components / source of supply INCI [weight%] Trade name

A

Tego Care 150 (1) GLYCERYL STEARATE,

STEARETH-25, CETETH-20, STEARYL ALCOHOL

Lanette O (2) CETEARYL ALCOHOL 1.5 Luvitol EHO (3) CETEARYL OCTANOATE 5 Miglyol 812 N (4) CAPRYLIC / CAPRIC 5

TRIGLYCERIDES

Paraffin liquid (5) PARAFFINUM LIQUIDUM 3

(MINERAL OIL)

AbilWax 2434 (1) STEAROXY 1.6

DIMETHICONE

Dow Corning 200 Fluid (6) DIMETHICONE 0.5 (350 es)

Propyl 4-hydroxybenzoates (5) PROPYLLPARABINES 0.05 B

1, 2-Propanediol (5) PROPYLENE GLYCOL 3 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 0.15 Creatine monohydrate (9) KREATIN 2 Water, demineralized AQUA (WATER) ad 100 C

Dihydroxyacetones (8) DIHYDROXYACETONE 5 Probiol L 05018 (Empty (7) AQUA, ALCOHOL 5 liposomes) DENAT, LECITHIN,

GLYCERINE, DISODIUM

PHOSPHATE

Water, demineralized AQUA (WATER) 10.00 compound (2) (9) GLUCURONOLACTONE 2

ACETON IDE

Total 100.00

Production method:

First, phases A and B are heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 ° C was added.

Sources: (1) Degussa-Goldschmidt AG, (2) Cognis GmbH, (3) BASF AG, (4) Sasol Germany GmbH, (5) Merck KGaA / Rona®, (6) Dow Corning (7) Kuhs GmbH & Co. KG , (8) Merck KGaA / Rona®, (9) Alfa Aesar

Formulation Example 3: O / W Tanning Lotion

Components / Trade name Source of supply INCI [weight%] A

Montanov 68 (1) CETEARYL ALCOHOL,

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.5 Lanette O (3) CETEARYL ALCOHOL 1 Cosmacol ELI (4) C12-13 ALIKYL 2

LACTATE

Arimol HD (2) ISOHEXADECANE 1 Paraffin highly liquid (5) PARAFFINUM 3

LIQUIDUM (MINERAL

OIL)

Dow Corning 9050 Silicone (6) CYCLOMETHICONE,

Elastomer blend DIMETHICONE

CROSSPOLYMER

RonaCare ^® tocopherol (5) TOCOPHERYL ACETATE 0.5 Acetate

Propyl 1,4-hydroxybenzoate (5) PROPYLPARABENE 0.05

B

RonaCare ^® Ectoine (5) ECTOIN 0.5 Glycerol, anhydrous (5) GLYCERINE 2 Water, demineralized AQUA (WATER) ad 100 Methyl 4-hydroxy benzoate (5) METHYL PARCHES 0.15 Creatinine (5) CREATININE 4

Rhodicare S (7) XANTHAN GUM 0.2 D

Probiol L 05018 (Empty (8) AQUA, ALCOHOL

liposomes) DENAT, LECITHIN,

GLYCERINE,

DISODIUM PHOSPHATES

Compound (2) (10) GLUCURONOLACTONE 3

ACETON ID

Water, demineralized AQUA (WATER) 10 E

Fragrance Cucumber (9) PERFUME 0.2 Total 100.00 Production method:

First, phases A and B are mixed separately and heated to 75 ° C. Thereafter, phase C is added to phase B and added to phase A with stirring. It is homogenized. It is then cooled with stirring and the phases D and E at 40 ° C was added.

Sources:

(1) Seppic (2) Uniqema (3) Cognis GmbH

(4) Condea Chinica D.A.C.S.p.A. (5) Merck KGaA / Rona® (6) Dow

Corning (7) Rhodia GmbH (8) Kuhs GmbH & Co. KG (9) Drom (10) Alfa

Caesar

Formulation example 4: O / W tanning cream with UV A B protection

Components / source of supply INCI [weight%] Trade name

A

Eusolex ' ⁹ 2292 (1) ETHYLHEXYL

METHOXYCINNAMATE,

BHT

Eusolex ^ 4360 (1) BENZOPHENONE-3 0.5 Tego Care 150 (2) GLYCERYL STEARATE, 8

STEARETH-25, CETETH-20, STEARYL ALCOHOL

Lanette O (3) CETEARYL ALCOHOL 1.5 Luvitol EHO (4) CETEARYL OCTANOATE 5 Miglyoll 812 N (5) CAPRYLIC / CAPRIC 5

TRIGLYCERIDES

Paraffin liquid (1) PARAFFINUM LIQUIDUM 3

(MINERAL OIL)

Abil-Wax 2434 (2) STEAROXY 1.6

dimeticones

Dow Corning 200 Fluid (6) DIMETICONE 0.5 (350 es)

Propyl 4-hydroxybenzoates (1) PROPYLPARABENES 0.05 Compound (3) CINEMA ACID 2

glucuronolactone acetonide

B

1, 2-Propanediol (1) PROPYLENE GLYCOL 3 Methyl 4-hydroxybenzoates (1) SODIUM 0.17 sodium salt METHYLPARABEN

Water, demineralized AQUA (WATER) ad 100 Creatine Monohydrate (8) CREATINE 2 C

Dihydroxyacetone (7) D I H YD ROXYAC ETO N E 5

Water, demineralized 10

Total 100.00

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized and cooled to 40 ° C and added phase C, then cooled to room temperature.

Sources:

(1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH (4) BASF AG (5) Sasol Germany GmbH (6) Dow Corning

(7) Merck KGaA / Rona® (8) Alfa Caesar

Formulation Example 5: O / W Shimmering Tanning Lotion

Components / source of supply INCI [weight%] Trade name

A

Montanov 68 (1) CETEARYL ALCOHOL,

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.5 Lanette O (3) CETEARYL ALCOHOL 1 Cosmacol ELI (4) C12-13 ALKYL 3

LACTATE

Cosmacol EMI (4) DI-C12-13 ALKYL 1

MALATE

Dow Corning 9040 Silicone (5) CYCLOMETHICONE, 1 Elastomer Blend DIMETICONE

CROSSPOLYMER

Arlamol HD (2) ISOHEXADECANE 3

RonaCare ^® tocopherol (6) TOCOPHERYL ACETATE 0.5 Acetate

Propyl-4-hydroxybenzoate (6) PROPYLPARABEN 0.05 · Compound (9) BENZYL 1

GLUCURONOLACTONE ACETONE ID

B

RonaCare ^® ectoine (6) ECTOIN 0.5 Colorona Red Gold ^® (6) MICA, Cl 77891 2

(TITANIUM DIOXIDE), Cl

77491 (ION OXIDES)

Glycerol, anhydrous (6) GLYCERIN 2

Caramel 250 (7) CARAMEL 1

FD & C Yellow No6 W082 (8) Cl 15985 0.01

Water, demineralized AQUA (WATER) ad 100

Methyl 4-hydroxybenzoates (6) METHYLPARABES 0.15

Creatine Monohydrate (11) CREATINE 0.5

C

Sepigel 305 (1) LAURETH-7, 0.5

polyacrylamides,

C13-14 ISOPARAFFIN

Dihydroxyacetone (10) DIHYDROXY ACETONE 5 Water demineralized 10 E

Fragrance Babylon (9) PERFUME 0.2

Total 100.00 Production method:

First, phases A and B are heated separately to 75 ° C. Thereafter, Phase A is slowly added to Phase B with stirring. At 60 ° C, Phase C is added to A / B and it is homogenized. It is then cooled to 40 ° C and the phases D and E are added successively.

Sources:

(1) Seppic (2) Uniqema (3) Cognis GmbH

(4) Condea Chimica D.A.C.S.p.A. (5) Dow Corning (6) Merck

KGaA / Rona®

(7) D.D. Williamson (8) Les Colorants Wackherr SA (9) Drom

(10) Merck KGaA / Rona® (11) Alfa Aesar

Claims

claims

1. mixture of creatine and / or creatinine with a compound of formula I.

wherein R ¹ and R ^{2 are} each independently

H

aryl,

where the alkyl group having 1 to 30 carbon atoms and / or the

Alkenyl group having 1 to 30 carbon atoms can be substituted with aryl and / or the aryl group having 6 to 12 carbon atoms by alkyl, OH, OAlkyl, NH ₂ , NH-alkyl, N (alkyl) ₂ , C (O) alkyl , OC (O) alkyl and / or C (O) -OAlkyl may be substituted, R ³ hl, a straight-chain or branched alkyl group having 1 to 30 C atoms or -C (O) R ⁵ ,

R ^{4 is} H or OR ⁶ ,

an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms by alkyl, vinyl, OH, OAlkyl, NH ₂ , NH alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O ) Alkyl and / or C (O) Oalkyl may be substituted, or

a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms by alkyl, OH, OAlkyl, NH ₂ , NHAlkyl , N (alkyl) ₂ , C (O) alkyl, O-C (O) alkyl and / or C (O) Oalkyl may be substituted and

in which

Aryl is an aryl group having 6 to 12 carbon atoms, the

optionally substituted by alkyl, OH, Oalkyl, NH ₂ , NH-alkyl, N (alkyl) ₂ , C (O) alkyl, OC (O) alkyl or C (O) -Oalkyl, and alkyl may be a straight-chain or branched alkyl group with 1 to 30 carbon atoms,

2. Mixture according to claim 1, characterized in that

R ¹ and R ^{2 are} H or

R ¹ and R ² together form a five-membered ring, which may be substituted by at least one straight-chain or branched alkyl group having 1 to 10 C atoms;

and / or by at least one straight-chain or branched one

Alkenyl group having 1 to 10 carbon atoms containing one or more double bonds may be substituted, which may be substituted by at least one phenyl group, wherein the phenyl group by alkyl, OH, OAlkyl, C (O) alkyl, OC (O) alkyl and / or C (O) -Oalkyl may be substituted;

and / or may be substituted by a phenyl group, where the phenyl group may be substituted by alkyl, OH, OAlkyl, C (O) alkyl, O-C (O) alkyl and / or C (O) -OAlkyl,

R ^{3 is} H or -C (O) R ⁵ ,

R ^{4 is} H and

an aryl group having 6 to 12 C atoms, where the aryl group having 6 to 12 C atoms is alkyl, vinyl, OH, O-alkyl, NH ₂ , NH, alkyl, N (alkyl) ₂ , C (O) alkyl, OC ( O) alkyl and / or C (O) OAlkyl may be substituted or

a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, which may be substituted by an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms by alkyl, OH, OAlkyl, NH ₂ , NHAlkyl , N (alkyl) ₂ , C (O) alkyl, O-C (O) alkyl and / or C (O) Oalkyl may be substituted

and

Alkyl represents a straight-chain or branched alkyl group having 1 to 12 C atoms.

3. Mixture according to claim 1, characterized in that the

Compound of the formula (I) is selected from the compounds (1) to (29)

Preparation comprising creatine and / or creatinine and at least one compound of the formula I according to one or more of claims 1 to 3 and / or their salts, tautomers, stereoisomers and / or solvates, including mixtures thereof in all ratios, or containing a mixture according to one or more of claims 1 to 3.

A preparation according to claim 4, characterized in that creatine and / or creatinine and the compound (s) of the formula I are present in a molar ratio of 3: 1 to 0.4: 1 in the preparation.

Preparation according to claim 4 or 5, characterized in that one for cosmetic, pharmaceutical or dermatological

Preparations of suitable carriers is included.

Preparation according to one or more of claims 4 to 6, characterized in that at least one further

Self-tanning substance is included.

A preparation according to claim 7, characterized in that the self-tanning substance is dihydroxyacetone. Process for the preparation of a preparation according to claim 6, 7 or 8, characterized in that the at least one compound according to formula I together with at least one for cosmetic,

Pharmaceutical, dermatological preparations suitable carrier and optionally adjuvants and / or fillers and / or

Active ingredients is mixed.

10. Use of a mixture according to one or more of claims 1 to 3 in cosmetic, pharmaceutical or dermatological preparations.

11. Use of creatine and / or creatinine for the stabilization of

at least one compound of the formula I according to one or more of claims 1 to 3 in a preparation.

12. Use of creatine and / or creatinine for improving the skin feel of a preparation comprising at least one compound of the formula I according to one or more of claims 1 to 3.