WO2009030372A1

WO2009030372A1 - Bi-functional dha derivatives

Info

Publication number: WO2009030372A1
Application number: PCT/EP2008/006853
Authority: WO
Inventors: Philipp Buehle; Thomas Rudolph; Herwig Buchholz
Original assignee: Merck Patent Gmbh
Priority date: 2007-09-03
Filing date: 2008-08-20
Publication date: 2009-03-12
Also published as: DE102007041854A1

Abstract

The invention relates to selected bi-functional dihydroxyacetone derivatives, to preparations containing bi-functional dihydroxyacetone derivatives of formula (I) or to dimeric compounds of formula (II) and to their use as self-tanning substances or hair colorants.

Description

Bifunctional DHA derivatives

The present invention relates to selected bifunctional dihydroxyacetone derivatives, preparations containing bifunctional dihydroxyacetone derivatives of the formula (I) or dimeric compounds of the formula (II) and their use as self-tanning substance or hair dye.

The trend away from sophisticated paleness to "healthy, sporty brown skin" has been unbroken for years, and people are exposing their skin to solar radiation, as it causes pigmentation through melanin formation - the UV rays of sunlight However, it also has a damaging effect on the skin: In addition to acute injury (sunburn), long-term damage from excessive exposure to UVB light (wavelength 280-320 nm), such as an increased risk of developing skin cancer Exposure to UVB and UVA radiation (wavelength: 320-400 nm) also weakens the elastic and collagen fibers of the connective tissue, leading to numerous phototoxic and photoallergic reactions and premature skin aging.

Natural protection against the negative effects of solar radiation is provided by the tanning (pigmentation) of the skin. The epidermis contains in its lowest layer, the basal layer, in addition to the basal cells, individual pigment-forming cells, the melanocytes. UV light in these cells stimulates the production of melanin, which is transported to the keratinocytes (horny cells) where it becomes visible as a brown skin color. This pigmentation, which is caused by the amino acid tyrosine, is primarily initiated by UVB radiation and is termed "indirect pigmentation." Its development takes place over several days, and the sun tan thus obtained persists for several weeks.

Pigmentation ", which starts with sun exposure, predominantly colorless melanin precursors are oxidized by UVA radiation to dark colored melanin, and as this oxidation is reversible, it results in only a brief skin tanning.

An artificial tanning of the skin can be produced externally with the help of make-up and orally by taking carotenoids. Far more popular, however, is the artificial tanning of the skin, which can be achieved by applying so-called self-tanner. These compounds have as a chemical structural feature keto or aldehyde groups in the vicinity of alcohol functions. These ketols or aldols belong predominantly to the substance class of sugars.

The compounds can be reacted with the proteins and amino acids of the horny layer of the skin in the manner of a Maillard reaction, whereby polymers which give the skin a brownish hue are formed via a reaction pathway that has not yet been fully elucidated. This reaction is completed in about 4 to 6 hours. The tan thus obtained is not washable and is removed only with the normal Hautabschuppung.

Of course, the state of the art knows a large number of different self-tanning substances. A particularly frequently used

Self-tanning substance is 1, 3-dihydroxyacetone (DHA). This is a water-soluble crystalline solid which is not stable under neutral to basic conditions. This instability is also associated with the development of cosmetically undesirable off-odors.

EP 0 796 838 B1 describes cosmetic or dermatological compositions containing an open-chain precursor of the dihydroxyacetone. WO 99/43667 discloses cyclic 1,3-dioxanes which liberate alcohols and function as "pro-perfumes".

WO 2007/039110 describes a reaction shown in the scheme

R1, R2 = identical or different, consisting for example of H, methyl, ethyl, alkyl, phenyl, aryl wherein the [1, 3] -dioxan-5-one compounds (on the left side of the reaction equation), the starting materials for the Synthesis of Dihydroxyacetonderivaten with UV filter properties represent. In addition to the Suitability of the [1, 3] -dioxan-5-one compounds of WO 2007/039110, in particular the compounds listed 2-methyl-2-methoxy-1, 3-dioxan-5-one or 2-ethoxy-2-methyl -1, 3-dioxan-5-one, as starting materials for the synthesis of the UV filter according to the invention of WO 2007/039110, no further properties or possible uses of these compounds are described.

There is still a need for skin-friendly self-tanning substances, in particular oil-soluble self-tanning substances, which are also suitable for use in cosmetic and dermatological preparations.

The object of the present invention is therefore to provide alternative substances which have a tanning action on the skin and on hair. In particular, self-tanning substances should be provided which are stable under neutral to basic conditions. In addition, the development of cosmetically undesirable off-odors should be avoided by the use of more stable derivatives.

This object is achieved by the use of a compound of the formula (I)

or a d

as a self-tanning substance, wherein the radicals are defined as follows: - A -

X O, S or NR,

R ¹ , R ² H, where R ^{2 may} not be H, straight-chain or branched, unsaturated or saturated alkyl having 1-20 carbon atoms, saturated, partially or completely unsaturated cycloalkyl having 3-7 carbon atoms,

wherein R ¹ and R ² are the same or different,

wherein these groups with saturated and / or unsaturated alkyl groups having 1 to 8 carbon atoms, OR, NR ₂ , saturated, partially or completely unsaturated by OH or OAlkyl 1-8 carbon atoms substituted cycloalkyl with 3-7

Carbon atoms can be substituted,

wherein in these groups one or two carbon atoms are replaced by the heteroatoms and / or atomic moieties -O-, -N =, NR, -C (O) -, -C (O) O- and / or -C (O) NH- could be,

where R is selected from H, straight-chain or branched alkyl having 1 to 20 carbon atoms,

wherein R ^{3 'is} H or -CH ₂ OH and wherein R ^{3 is} H.

In the context of the present invention, completely unsaturated compounds or substituents and groups are also understood to mean aromatic compounds or aromatic substituents.

The compounds of the formula (I) or (II), as described above, are formally condensation products of dihydroxyacetone or of a -CH ₂ OH-substituted dihydroxyacetone (ie the erythrulose) with a carboxylic acid and an alcohol. The compounds of formula (I) or (II) are characterized by the fact that they gain stability with increasing ambient pH while other self-tanning agents such as DHA or erythrulose lose stability with increasing pH. The compounds of the formula (I) or (II) therefore offer the advantage of being usable in pH ranges in which other self-tanning agents are already subject to decomposition. Particularly in the pH range from 5 to 8, particularly preferably in the range of 6.0 and 7.5, the compounds of the formula (I) or (II), in particular of the formula (I) where R ³ = H, are more stable than other self-tanning agents. In particular, there is the advantage that by avoiding the decomposition negative properties are avoided, such as the development of malodour by DHA

Decomposition, which can also lead to loss of active substance and skin irritation. Their coloring or tanning effect can only in selected compounds, in particular in compounds of formula (II), by molecular cleavage under physiological acid conditions (eg after skin application, pH of the skin about 5), by enzymes or by amino groups in the sense of Maillard Reaction catalyzed to occur.

The compounds of the formula (I), preferably compounds of the formula (I) where R ³ = H, are able to directly enter into a tanning reaction with the skin, without the need for molecular cleavage prior to attachment to the stratum corneum. Most preferably, dihydroxyacetone ortho-ethyl acetate is capable of this. Without being bound by theory, the tanning mechanism can be explained by first forming an imine with free amino groups of the stratum corneum and the free keto group of the compounds of formula (I), which then forms an alpha-amino aldehyde under proton transfer and water addition (Amadori rearrangement). This then enters the further reaction steps for Bräungungsreaktion (Maillard reaction) with the stratum corneum.

The following scheme describes this proposed mechanism for the compound dihydroxyacetone-ortho-ethyl acetate or synonymous with 2-ethyloxy-2-methyl- [1,3] dioxan-5-one:

Maillard reaction

The fact that the compounds of the formula (I) or (II) are substituents as defined above or with preferred substituents as described above or below are oil-soluble self-tanning substances brings advantages over other water-soluble self-tanning substances such as DHA. The inventive self-tanning substances dissolved in the oil phase and not the water phase are thus more stable to oxidative or hydrolytic degradation. In addition, a combination of the oil-soluble self-tanning substances of the invention with other water-soluble self-tanning substances such as DHA results in synergistic effects on the tanning result on the skin.

Compounds of the formula (I) or (II), preferably compounds of the formula (I) where R ³ = H, also have an influence on the coloration of hair and are therefore, in particular, also suitable hair colorants.

Another object of the invention is therefore also the use of a compound of formula (I)

or a d

as hair dye, wherein the radicals are defined as follows: XO, S or NR,

wherein R ¹ and R ² are the same or different, ^•

Carbon atoms can be substituted,

wherein R ^{3 'is} H or -CH ₂ OH and wherein R ^{3 is} H.

In comparison to known self-tanning substances, the compounds of the formula (I) or (II) have, in addition to a self-tanning component, at least one second active ingredient which is released in the tanning reaction and which leads to a significant added benefit of the substance used. Therefore, the compounds of formula (I) in the present specification are also referred to as bifunctional derivatives of dihydroxyacetone. Compounds of the formula (II) are also referred to as the dimer derivative of the bifunctional derivatives of the dihydroxyacetone of the formula (I). Furthermore, the compounds of the formula (I) or (II), in particular of the formula (I), are relatively easy to prepare. Very particular preference is given to using the compounds of the formula (I) and their compounds described as being preferred as self-tanning substances for skin and hair or skin or hair.

The term self-tanner is used synonymously in the context of this invention as a self-tanning substance or self-tanning substance.

The nature of the other released active ingredients is via the radicals R ¹ and R ²

"Controllable": From R ¹ (II) is produced in the cleavage of the compounds (I) and / or usually a carboxylic acid R ¹ -COOH, from R ^2, a compound R formed ² -XH Alternatively, in the postulated tanning mechanism. also the carboxylic acid derivatives R ¹ -C (O) -XR ² arise.

These further released active ingredients may have, for example, the following effects: preserving action (eg acetic acid, para-hydroxybenzoic acid ester, benzoic acid, salicylic acid, sorbic acid), preserving or cooling action (eg ethanol), regulation of the water content of the skin / moisturizers (eg lactic acid, pyrrolidonecarboxylic acid, Amino acids), "immediate lifting effect" (eg dimethylethanolamine), "natural cell protection effect" (eg ectoine). In addition, other known releasable active substances are all known substances which are also used as moisturizers, moisturizers, UV filters (for example ethylhexyl methoxycinnamate, octrocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl

Salicylates), preservatives, dyes, self-tanning agents, tanning agents, skin whiteners, peptides, anti-aging agents (e.g., creatine, creatinine), drugs, fragrances, etc.

In particular, substances which are of interest to the person skilled in the art under the term "Natural Moisturizing Factor" (NMF, natural moisturizing substances) are of interest as further releasable active ingredients NMF is a mixture of hygroscopic substances in the horny layer of the skin (stratum corneum) It contains about 40% free amino acids, 12% pyrrolidonecarboxylic acid, 12%

Lactic acid / sodium lactate, 7% urea and also a neutral Carbohydrate mixture, glucosamine and uric acid (see Fey, Otte, Dictionary of Cosmetics, 3rd edition, 1991).

The radical X in the bifunctional derivatives of the dihydroxyacetone of the formula (I) preferably has the meaning O. The radical X in the compounds of the formula (II) preferably has the meaning O.

In the case of compounds of the formula (I), the radical R ³ is preferably H.

Straight-chain or branched, unsaturated or saturated alkyl having 1-20

Carbon atoms in this case comprises alkyl and alkenyl groups having 1-20 C atoms, it being understood that an alkenyl group can be present only from 2 carbon atoms.

The straight-chain or branched alkyl group having 1-20 carbon atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, isobutyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1-, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, 1-ethyl-pentyl, octyl, 1-ethyl-hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl , Octadecyl, nonadecyl or eicosyl.

A straight-chain or branched alkenyl having 2 to 20 C atoms, wherein several double bonds may also be present, is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, iso-butenyl, furthermore 4-pentenyl, iso-pentenyl, hexenyl , Heptenyl, octenyl, -C ₉ Hi ₇ , -Ci ₀ Hig to -C20H39; preferably vinyl. The described alkyl or alkenyl groups may be substituted with further saturated and / or unsaturated alkyl groups of 1-8 carbon atoms, OR, NR ₂ , saturated, partially or fully unsaturated cycloalkyl of 3-7 carbon atoms substituted by OH or Oalkyl of 1-8 carbon atoms , Preferably, the substituted alkyl or alkenyl group is dimethylaminoethyl, 2- (4-methoxyphenyl) vinyl or 1-hydroxyethyl.

Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl,

Cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, phenyl, cycloheptenyl, cyclohepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl, preferably phenyl. These cycloalkyl groups may be substituted with further saturated and / or unsaturated alkyl groups of 1-8 carbon atoms, OR, NR ₂ , saturated, partially or fully unsaturated cycloalkyl of 3-7 carbon atoms substituted by OH or Oalkyl of 1-8 carbon atoms. Preferably, the substituted cycloalkyl of 3-7 carbon atoms is 2-hydroxyphenyl.

Preferably, the substituents R ¹ and / or R ^{2 are} independently selected from the group -H, where R ^{2 may} not be H, - (CH ₂ ) oCH ₃ , - (CH ₂ ) _n NH ₂ , -

CCH ₂₎ _n N ((CH ₂₎ ₀ _CH3) ((CH2) PCH3) - (CHOH) n (CH ₂₎ _o CH _3, - (CHOH) _n (CH ₂₎ _o CH ₂ OH, -

(CHOH) _n (CH ₂ ) _O -Ar, -Ph, -CH ₂ -Ar, -CH = CH-Ar, -OC ₆ H ₆ -C (= O) -OR-C ₆ H ₆ -

CH ₂ CHNR ¹ COOR ', -CH ₂ CHNR ¹ COOR', where n is an integer and selected from the range 1 to 20, preferably 1, 2 or 3 wherein 0 and p are independently an integer and selected from the range 0 to 20, preferably 0, 1 or 2, wherein Ph is phenyl, Ar is an unsubstituted or substituted

Phenyl group, wherein the substituted phenyl group may be substituted by OR or NR ₂ , wherein R is selected from H, straight-chain or branched alkyl having 1 to 20

Carbon atoms and wherein the radicals R 'are independently selected from H,

Amino acid residue and peptide residue.

Preferably, the substituent R ^{1 of} the compounds of formula (I) or (II) is selected from the group of branched or straight-chain, saturated or unsaturated alkyl having 1 to 20 carbon atoms, wherein the saturated

Preferably, the alkyl group may be substituted by OH, and the unsaturated alkyl group may be preferably substituted with phenyl substituted by Oalkyl, and saturated, partially or fully unsaturated cycloalkyl having 3-7

Carbon atoms, which with saturated alkyl groups having 1 to 8

Carbon atoms or OR may be substituted and wherein one or two carbon atoms may be replaced by the heteroatoms and / or atomic groups -N =, NR or -C (O). In this selected group of compounds of the formula (I) or (II), the substituent R ^{1 is} very particularly preferably selected from the group straight-chain or branched alkyl group having 1-20 carbon atoms, -CHOH-CH ₃ , pyrrolidonecarboxylic acid radical, ecto-carboxylic acid radical, 2 -hydroxy-phenyl or (4-methoxyphenyl) -vinyl.

The substituent R ^{2 of} the compounds of the formula (I) or (II) is particularly preferably selected from the group of a physiologically and / or dermatologically tolerated alcohol R ² -OH or a physiologically and / or dermatologically tolerated aminoalcohol R ² -OH, where the R ^{2 is} a branched or straight-chain alkyl having 1-20 carbon atoms, which may be substituted by NR ₂ , wherein R has one of the meanings given above. In this selected group of compounds, it is very particularly preferred if the substituent R ^{2 of} the bifunctional derivative of the DHA of the formula (I) is selected from the group consisting of branched or straight-chain alkyl having 1-20 C atoms and dimethylaminoethyl, preferably R ² but an unsubstituted branched or straight chain alkyl group of 1-20 carbon atoms.

Without restricting generality, examples of compounds of the formula I where X = O and R ^{3 '} = H:

DHA-ortho-DHA-ortho- (2-dimethyl-DHA-ortho-ethyl-acetate-amino) ethyl-acetate ethyl-lactate

DHA-ortho-ethyl-ectoine DHA-ortho-ethyl-pyrrolidone carbonate,

DHA-ortho-DHA-ortho- (2-dimethyl-DHA-ortho- (2-dimethyl- (2-dimethylamino-amino-ethyl) -ecto-amino-amino) -pyrrolidone-ethyl) -lactate carbonate

2- (2-ethylhexyloxy) -2-methyl- [1,3] dioxan-5-one,

2-isopropoxy-2-methyl- [1,3] dioxan-5-one,

2-hexyloxy-2-methyl- [1,3] dioxan-5-one,

2-methyl-2-octyloxy [1,3] dioxan-5-one,

2-decyloxy-2-methyl- [1,3] dioxan-5-one,

2-Dodecyloxy-2-methyl- [1,3] dioxan-5-one,

2-methyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2-methyl- [1,3] dioxan-5-one,

2-methyl-2-octadecyloxy [1,3] dioxan-5-one,

2-ethoxy-2- (1-ethylpentyl) - [1,3] dioxan-5-one, 2- (2-Ethyl-hexyloxy) -2- (1-ethylpentyl) - [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2- (1-ethylpentyl) - [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-isopropoxy [1,3] dioxan-5-one,

2- (1-ethyl-pentyl) -2-hexyloxy-2- [1,3-dioxan-5-one, 2- (1-ethyl-pentyl) -2-octyloxy- [1,3-dioxane-5-one] on, 2-decyloxy-2- (1-ethyl-pentyl) - [1,3] dioxan-5-one,

2-Dodecyloxy-2- (1-ethyl-pentyl) - [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-tetradecyloxy [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-hexadecyloxy- [1,3-dioxan-5-one, 2- (1-ethylpentyl) -2-octadecyloxy- [1,3] dioxan-5-one, 2-ethoxy-2-heptyl- [1,3] dioxan-5-one,

2- (2-ethyl-hexyloxy) -2-heptyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-heptyl [1,3] dioxan-5-one,

2-Heptyl-2-isopropoxy - [1,3] dioxan-5-one, 2-heptyl-2-hexyloxy- [1,3] dioxan-5-one, 2-heptyl-2-octyloxy- [1,3,5-] ] dioxane-5-one,

2-decyloxy-2-heptyl- [1,3] dioxan-5-one,

2-dodecyloxy-2-heptyl- [1,3-dioxan-5-one,

2-Heptyl-2-tetradecyloxy- [1,3] dioxan-5-one, 2-hexadecyloxy-2-heptyl- [1,3] dioxan-5-one, 2-heptyl-2-octadecyloxy- [1, 3 ] dioxane-5-one,

2-ethoxy-2-nonyl- [1,3] dioxan-5-one,

2- (2-ethylhexyloxy) -2-nonyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-nonyl- [1,3] dioxan-5-one, 2-isopropoxy-2-nonyl- [1,3] dioxan-5-one,

2-hexyloxy-2-nonyl- [1,3] dioxan-5-one,

2-nonyl-2-octyloxy [1,3] dioxan-5-one,

2-Decyloxy-2-nonyl- [1,3] dioxan-5-one, 2-dodecyloxy-2-nonyl- [1,3] dioxan-5-one, 2-nonyl-2-tetradecyloxy- [1,3 ] dioxane-5-one,

2-hexadecyloxy-2-nonyl- [1,3] dioxan-5-one,

2-nonyl-2-octadecyloxy [1,3] dioxan-5-one,

2-ethoxy-2-undecyl- [1,3] dioxan-5-one, 2- (2-ethyl-hexyloxy) -2-undecyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-undecyl- [1,3] dioxan-5-one,

2-isopropoxy-2-undecyl [1, 3] dioxan-5-one,

2-hexyloxy-2-undecyl [1, 3] dioxan-5-one,

2-Octyloxy-2-undecyl- [1,3] dioxan-5-one, 2-decyloxy-2-undecyl- [1,3] dioxan-5-one, 2-dodecyloxy-2-undecyl- [1,3,5 ] dioxane-5-one,

2-tetradecyloxy-2-undecyl [1, 3] dioxan-5-one,

2-hexadecyloxy-2-undecyl [1, 3] dioxan-5-one,

2-octadecyloxy-2-undecyl- [1,3] dioxan-5-one, 2-ethoxy-2-tridecyl- [1,3] dioxan-5-one,

2- (2-ethyl-hexyloxy) -2-tridecyl [1.3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-tridecyl- [1,3] dioxan-5-one,

2-isopropoxy-2-tridecyl [1,3] dioxan-5-one,

2-hexyloxy-2-tridecyl [1,3] dioxan-5-one, 2-octyloxy-2-tridecyl [1,3] dioxan-5-one,

2-decyloxy-2-tridecyl [1,3] dioxan-5-one,

2-dodecyloxy-2-tridecyl [1,3] dioxan-5-one,

2-tetradecyloxy-2-tridecyl- [1,3] dioxan-5-one, 2-hexadecyloxy-2-tridecyl- [1,3] dioxan-5-one,

2-octadecyloxy-2-tridecyl [1,3] dioxan-5-one,

2-ethoxy-2-pentadecyl [1,3] dioxan-5-one,

2- (2-ethylhexyloxy) -2-pentadecyl [1,3] dioxan-5-one,

2- (2-Dimethylamino-ethoxy) -2-pentadecyl- [1,3] dioxan-5-one, 2-isopropoxy-2-pentadecyl- [1,3] dioxan-5-one, 2-hexyloxy-2- pentadecyl [1,3] dioxan-5-one,

2-octyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-decyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-Dodecyloxy-2-pentadecyl- [1,3] dioxan-5-one, 2-pentadecyl-2-tetradecyloxy- [1,3] dioxane-5-o, 2-hexadecyloxy-2-pentadecyl- [1,3 ] dioxane-5-one,

2-octadecyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-ethoxy-2-heptadecyl [1,3] dioxan-5-one,

2- (2-ethylhexyloxy) -2-heptadecyl- [1,3] dioxan-5-one, 2- (2-dimethylamino-ethoxy) -2-heptadecyl- [1,3] dioxan-5-one, 2-isopropoxy-2-heptadecyl [1,3] dioxan-5-one,

2-hexyloxy-2-heptadecyl [1,3] dioxan-5-one,

2-heptadecyl-2-octyloxy [1,3] dioxan-5-one,

2-decyloxy-2-heptadecyl- [1,3] dioxan-5-one, 2-dodecyloxy-2-heptadecyl [1,3] dioxan-5-one,

2-heptadecyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-heptadecyl-2-hexadecyloxy [1,3] dioxan-5-one,

2-heptadecyl-2-octadecyloxy [1,3] dioxan-5-one, 2-ethoxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxane 5-one,

2- (2-ethyl-hexyloxy) -2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2-isopropoxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2-Hexyloxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one, 2 - [(E) -2- (4-methoxy-phenyl ) vinyl] -2-octyloxy- [1,3] dioxan-5-one, 2-decyloxy-2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxane -5-one,

2-Dodecyloxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2 - [(E) -2- (4-methoxyphenyl) vinyl] -2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one, 2 - [(E) -2- (4-methoxy-phenyl ) vinyl] -2-octadecyloxy [1,3] dioxan-5-one, 2-ethoxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2- (2-ethylhexyloxy) -2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2-isopropoxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2-hexyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2- (2-hydroxy-phenyl) -2-octyloxy- [1,3] dioxan-5-one,

2-decyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2-Dodecyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2- (2-hydroxyphenyl) -2-tetradecyloxy [1,3] dioxan-5-one, 2-hexadecyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2- (2-Hydroxy-phenyl) -2-octadecyloxy [1,3] dioxan-5-one.

The new compounds of this list listed for compounds of formula (I) with X = O and R ³ = H are also the subject of this application.

A particularly particularly preferred self-tanning substance which dyes skin and hair is dihydroxyacetone-ortho-ethyl acetate. The substance has the very positive quality of a cosmetic oil that allows direct application as a pure substance. This is a decisive advantage for use as a hair dye.

Without restricting the generality, an example of compounds of the formula (II) where X = O and R ³ = H is:

Bis-ortho-ethyl-acetate of DHA dimer (dDHA-bOEA) or synonym 2,10-diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxa-dispiro [4.2.4.2] tetradecane.

The new compound of this list listed for compounds of formula (II) with X = O and R ³ = H are also the subject of this application.

Without restricting generality, examples of compounds of the formula I where X = O and R ^{3 '} = CH ₂ OH:

Erythrulose 1, 3-ortho-erythrulose-1,3-ortho-erythrulose 1,3-ortho-ethyl-acetate (2-dimethylaminoethyl-lactate-ethyl) -acetate

The new compounds of this list listed for compounds of formula (I) with X = O and R ³ = CH ₂ OH are also the subject of this application.

Without loss of generality, examples of compounds are the

Formula I with X = S and R ^{3 '} = H:

DHA-ortho-thio-DHA-ortho-thio-DHA-ortho-thio

(2-dimethylamino ethyl acetate ethyl lactate ethyl) lactate.

The new compounds of this list listed for compounds of formula (I) with X = S and R ³ = H are also the subject of this application.

The compound of the formula (I) for the use according to the invention is preferably selected from the group consisting of dihydroxyacetone-ortho-ethyl acetate, dihydroxyacetone-ortho- (2-dimethylamino) -ethyl acetate, dihydroxyacetone-ortho-ethyl-lactate, dihydroxyacetone-ortho-ethyl-ectoine and dihydroxyacetone-ortho-ethyl-pyrrolidone carbonate.

The compounds of the formula (I) or formula (II) can be easily synthesized under mild conditions. The compounds are isolated in good yields.

For the preparation of the monomeric compounds of the formula (I) is first dihydroxyacetone or erythrulose (here R ³ = CH ₂ OH) of the formula (III)

with catalytic amounts (+/-) - camphor-10-sulfonic acid (or other acidic catalysts such as para-toluenesulfonic acid or polymeric, acidic catalysts). Subsequently, with an ortho-ester of the formula (IV)

implemented, wherein the substituents X, R ¹ and R ² correspond to a previously given definition, in particular correspond to a substituent of the described individual compounds of said lists. The person skilled in the art of synthetic chemistry is able to determine the substituents R ¹ , R ² and X from the disclosed individual compounds, so that this reaction equation is a disclosure for the synthesis of all the listed individual compounds.

The dimeric bifunctional derivatives of the formula (II) are prepared by reacting dimeric dihydroxyacetone of the formula (V) with R ³ = H

with catalytic amounts of (+/-) - camphor-10-sulfonic acid (or other acidic catalysts such as para-toluenesulfonic acid or polymeric acidic catalysts) and with an ortho-ester of formula (IV)

prepared, wherein the substituents X, R ¹ and R ² correspond to a previously given definition. Preferably, monomerization of the dimeric starting material takes place in the preparation of the monomeric derivatives at 50 to 100 ^° C. within about 2 hours. The subsequent reaction with the compound of the formula (IV) preferably takes place within 6 to 48 hours at 50 to 100 ^° C.

The preferred conditions for the preparation of the dimeric compounds are 6 to 48 hours and 50 to 100 ^° C.

Purification of the compound is carried out in each case by distillation and / or crystallization.

Another object of the present invention is the use of the compound according to formula (I) and / or formula (II), as indicated above, for the preparation of a preparation, in particular a cosmetic or a dermatological preparation, preferably for artificial tanning and / or or browning of the skin or the coloring of the hair.

Moreover, the use of the compound of the formula (I) and / or the formula (II) as a UV filter, as a preservative, for lifting the skin as well as for the preparation of a cosmetic and / or dermatological preparation with light protection properties is possible. The compounds 2-ethoxy-2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxan-5-one, 2- (2-ethyl-hexyloxy) -2- [ (E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxan-5-one, 2- (2-dimethylamino-ethoxy) -2 - [(E) -2- (4- methoxyphenyl) vinyl] - [1,3] dioxan-5-one, 2-isopropoxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxane 5-one, 2-hexyloxy-2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxan-5-one, 2 - [(E) -2- (4 -Methoxy-phenyl) -vinyl] -2-octyloxy- [1,3-dioxan-5-one, 2-decyloxy-2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1 , 3] dioxan-5-one, 2-dodecyloxy-2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxan-5-one, 2 - [(E) -2- (4-Methoxy-phenyl) -vinyl] -2-tetradecyloxy [1,3] dioxan-5-one, 2-hexadecyloxy-2 - [(E) -2- (4-methoxy-phenyl) - vinyl] - [1,3] dioxane-5-one, 2 - [(E) -2- (4-methoxy-phenyl) -vinyl] -2-octadecyloxy- [1,3] dioxan-5-one, 2 - Ethoxy-2- (2-hydroxy-phenyl) - [1,3-dioxan-5-one, 2- (2-ethyl-hexyloxy) -2- (2-hydroxyphenyl) - [1,3] dioxane 5-one, 2- (2-dimethylaminoethoxy) -2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2-isopropoxy-2- (2-hydroxy-phenyl) - [1, 3 ] dioxan-5-one, 2-hexyloxy 2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2- (2-hydroxy-phenyl) -2-octyloxy- [1,3-dioxan-5-one, 2-decyloxy- 2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2-dodecyloxy-2- (2-hydroxy-phenyl) - [1,3-dioxan-5-one, 2- (2 -Hydroxy-phenyl) -2-tetradecyloxy- [1,3-dioxan-5-one, 2-hexadecyloxy-2- (2-hydroxy-phenyl) - [1,3-dioxane-5-one, 2- (2 -Hydroxy-phenyl) -2-octadecyloxy- [1,3] dioxan-5-one are particularly suitable for this purpose since they carry UV-active substituents on the [1,3] dioxan-5-one ring.

The use of the compound according to formula (I) and / or formula (II) in pharmaceutical and / or cosmetic preparations or in household products is also important.

Another object of the present invention are compositions containing at least one bifunctional derivative of the dihydroxyacetone of the formula (I) or at least one dimeric bifunctional derivative of the dihydroxyacetone of the formula (II) or preferably specified compounds of the formula (I) or (II) or the listed Single compounds included.

The preparations are usually topically applicable preparations, for example cosmetic or dermatological formulations. The preparations in this case contain a cosmetically or dermatologically suitable carrier and, depending on the 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 dietary supplement, then a suitable carrier is to be selected.

If the preparations are perfumes, it is preferred in a variant of the invention if, in addition to the fragrances or perfume oils and the flavonoids and typical carrier substances, such as water, solvents, such as alcohols, oils and, if appropriate, emulsifiers, no further auxiliaries are present.

For the purposes of the present invention, the term agent or formulation is used synonymously in addition to the term preparation. All compounds or components that can be used in the formulations are either known and commercially available or can be synthesized by known methods.

Further preferred combinations of embodiments are disclosed in the claims.

The invention also provides a process for preparing a preparation as described above, wherein at least one compound of the formula (I) or at least one compound of the formula (II) is mixed with a carrier suitable for topical applications. Suitable carriers are described in detail in the following part.

In preferred embodiments, the at least one bifunctional derivative of the dihydroxyacetone of the formula (I) or the at least one dimeric bifunctional derivative of the dihydroxyacetone of the formula (II) having the defined substituents or preferred individual compounds in the preparations according to the invention is typically in amounts of from 0.01 to 10 % By weight, preferably in amounts of from 0.1% by weight to 5% by weight and more preferably in amounts of from 0.5 to 2% by weight. The expert does not have any difficulties in selecting the quantities according to the intended effect of the preparation.

In the described preparations which contain according to the invention at least one bifunctional derivative of the dihydroxyacetone of the formula (I) or at least one dimeric bifunctional derivative of the dihydroxyacetone of the formula (II), pigments may furthermore also be present, the layer structure of the pigments not being limited.

Preferably, the color pigment should be skin colored or brownish at a level of from 0.5 to 5% by weight. The selection of a corresponding pigment is familiar to the person skilled in the art.

Examples of advantageous color pigments are titanium dioxide, mica, iron oxides (eg Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971.

Particularly preferred are the types of pearlescent pigments listed below:

1. natural pearlescent pigments, such as. B. "fish-silver" (guanine / hypoxanthine mixed crystals from fish scales) and

• "mother of pearl" (ground mussel shells)

2. monocrystalline pearlescent pigments such. B. bismuth oxychloride (BiOCl)

3rd layer substrate pigments: z. Mica / metal oxide

The basis for pearlescent pigments are, for example, pulverulent pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide, and Bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is z. For example, listed under the CIN 77163 luster pigment.

Also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide:

Particular preference is z. For example, the pearlescent pigments available from Merck under the trade names Timiron®, Colorona®, Dichrona®, Xirona® or Ronastar®.

Of course, the list of pearlescent pigments mentioned should not be limiting. Pearlescent pigments which are advantageous in the context of the present invention are obtainable in numerous ways known per se. For example, other substrates except mica can be coated with other metal oxides such. As silica and the like. Advantageous z. B. with Tiθ2 and Fβ2θ ₃ coated SiO ₂ particles ("Ronaspheren"), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles.

It may also be advantageous to completely dispense with a substrate such as mica. Particularly preferred are pearlescent pigments, which under the Use of SiO ₂ are produced. Such pigments, which may also have additional gonichromatic effects are, for. B. under the trade name Sicopearl Fantastico available from BASF.

Further advantageous pigments of Engelhard / Mearl based on calcium sodium borosilicate, which are coated with titanium dioxide, can be used. These are available under the name Reflecks®. Due to their particle size of 40-80 μm, they have a glittering effect in addition to the color.

Also particularly advantageous are also effect pigments, which under the

Trade name Metasomes® standard / glitter available in various colors (yellow, red, green, blue) from Flora Tech. The glitter particles are present in mixtures with various auxiliaries and dyes (such as the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).

Particularly suitable pigments in premixes are, for example, Ronastar® Silver or Colorona® Bronze.

Preparations with self-tanning properties, in particular those which

Contain dihydroxyacetone, when applied to the human skin to malodor, which are believed to be caused by degradation products of the dihydroxyacetone itself or by products of side reactions and which are perceived by the users in part as unpleasant. It has been found that these off-odors are avoided when using formaldehyde scavengers and / or flavonoids. Even when using the compounds of the formula (I) or formula (II) or in combined use with known self-tanner such as DHA, the formation of off-odors can not be excluded. Therefore, the preparation according to the invention may preferably also contain formaldehyde scavengers and optionally flavonoids for improving the odor.

Preferably, the formaldehyde scavenger is selected from the group consisting of alkali metal, alkaline earth metal or ammonium bisulfite. Particularly preferred is a preparation containing in combination DHA Plus, a mixture of DHA, sodium bisulfite and magnesium stearate. DHA Plus is a product blend containing sodium bisulfite, equivalent to Na ₂ S ₂ O ₅ or INCI: sodium disulfite, for the masking, elimination or neutralization of formaldehyde. The addition of sodium bisulfite in finished formulations significantly reduces or eliminates the unpleasant odor. DHA Plus is distributed by Merck, Darmstadt.

The flavonoid optionally present in the preparation according to the invention additionally acts as a stabilizer for the self-tanner or self-tanning substances and / or reduces or avoids or improves storage-dependent off-odors, which can also be caused by additives or auxiliaries.

Preferably, it is a flavonoid in which one or more phenolic hydroxy groups are blocked by etherification or esterification. For example, hydroxyethyl-substituted flavonoids, such as preferably troxerutin, troxequercetin, troxeisoquercetin or troxeluteolin, and flavonoid sulfates or flavonoid phosphates, such as preferably rutosulfates, have proven to be particularly suitable flavonoids. Particularly preferred in the context of the use according to the invention are rutin sulfate and troxerutin. Very particularly preferred is the use of troxerutin.

The preferred flavonoids have a non-positively charged Flavangrundkörper. It is believed that these flavonoids complex metal ions such as Fe ² VCu ²⁺ , thus contributing to autooxidation events

Fragrances or compounds whose degradation leads to malodors, prevented or reduced.

Particular preference is given to a preparation which, in addition to the compounds of the formulas (I) or (II), contains DHA Rapid and / or sodium bisulfite. DHA Rapid is a product mixture containing dihydroxyacetone and troxerutin, Merck, Darmstadt.

Corresponding premixes and preparations which contain formaldehyde scavengers and, if appropriate, flavonoids for improving the odor on the skin are described in the German patent application with the registration file DE 10 2007 013 368.7, the contents of which are expressly also part of the disclosure of the present application.

In addition, the preparation according to the invention may preferably also contain other active substances, such as, for example, repellents, in particular insect repellents, UV filters, flavone derivatives, chromone derivatives, aryloximes and parabens.

Most repellent agents belong to the classes of amides, alcohols, esters and ethers. Repellents are usually the following

Meet conditions: They must not evaporate too quickly and should not penetrate the skin. They should not be primarily irritating or sensitizing to the skin, nor should they be toxic. Their effectiveness must also be preserved under the action of skin fluid and / or UV radiation.

Preferred repellents are selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl-amino) -propionic acid ethyl ester, dimethyl phthalate, butopyronoxyl, 2,3 ₎ 4,5-bis (2-butylene) -tetrahydro- 2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, N- (2-ethylhexyl) -8,9,10-trinorborn-5-ene-2,3-dicarboximide, Dimethylcarbate, di-n-propyl isocine chomeronate, (R) -p-mentha-i, 8-diol, 2-ethylhexane-1,3-diol, N-octyl-bi-cyclohepetane-di-carboximide, piperonyl-butoxide, 1- (2 -Methylpropyloxycarbonyl) -2- (hydroxyethyl) - piperidine (Bayrepel ^®; Fa. Bayer) or mixtures thereof, and it is particularly preferably selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl- amino) - propionic acid ethyl ester, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures thereof.

Parabens are 4-hydroxybenzoic acid esters which are used in free form or as sodium salts for the preservation of preparations in the field of food, cosmetics and pharmaceuticals. The effect of the esters is directly proportional to the chain length of the alkyl radical, but conversely the solubility decreases with increasing chain length. As non-dissociating compounds, the esters are largely pH independent and operate in a pH range of 3.0-8.0. The antimicrobial mechanism of action is based on damage. the microbial membranes by the surface activity of the PHB esters as well as on the protein denaturation. In addition, interactions with coenzymes occur. The effect is directed against fungi, yeasts and bacteria. The preservative The most important parabens are methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate and butyl 4-hydroxybenzoate.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products is known for example from German patent application DE 41 16 123. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases associated with inflammation. It is known that such preparations, e.g. can be used for the treatment of psoriasis, various eczema forms, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages. Compositions according to the invention which, in addition to the compound (s) mentioned, additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising anti-inflammatory suitability. The preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.

According to the invention, flavone derivatives are flavonoids and coumaranones. Flavonoids according to the invention are the glycosides of flavanones, flavones, 3-hydroxyflavones (= flavonols), aurones, isoflavones and rotenoids conceived [Römpp Chemie Lexikon, Volume 9, 1993]. In the context of the present invention, however, this also includes the aglycones, ie the sugar-free constituents, and the derivatives of the flavonoids and the aglycones. Furthermore, in the context of the present invention, the term flavonoid is also understood to mean anthocyanidin (cyanidin). In the context of the present invention, coumaranones are also understood as meaning their derivatives. Among the coumaranones is 4,6,3 ^', ^4' tetrahydroxybenzylcoumaranone coumaranone-3 preferred.

Chromone derivatives are preferably understood to mean certain chromene-2-one derivatives which are suitable as active ingredients for the preventive treatment of human skin and hair according to aging processes and damaging environmental influences. At the same time, they show a low irritation potential for the skin, influencing the water binding in the skin positively, maintain or increase the elasticity of the skin and thus promote a smoothing of the skin. These compounds preferably correspond to the following formula

in which

R ¹ and R ^{2 may be the} same or different and are selected from

- H, -C (= O) -R ⁷ , -C (= O) -OR ⁷ , - straight-chain or branched C _r to C ₂ o-alkyl groups,

- linear or branched C ₃ - to C2o-alkenyl, straight-chain or branched Cr to _{C2o-hydroxyalkyl} groups, where the hydroxyl group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or - C ₃ - to C-io-cycloalkyl and / or C ₃ - to C ₂ cycloalkenyl groups, where the rings may each also by - _n groups with n = 1 to 3 can be bridged (CH _2),

R ³ is H or straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,

R ⁴ is H or OR ⁸ ,

R ⁵ and R ^{6 may be the} same or different and are selected from

- ₁ -H -OH ₁ - straight-chain or branched d- to _C2o-alkyl groups,

straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,

straight-chain or branched C _r to C ₂ o-hydroxyalkyl groups, where the hydroxy group can be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain can also be interrupted by oxygen, and R ⁷ is H, straight or branched Cr to C ₂ o-alkyl groups, a polyhydroxy compound, such as preferably an ascorbic acid residue or glycosidic residues and

R ⁸ is H or straight-chain or branched C ₁ - to C 20 -alkyl groups, where at least 2 of the substituents R ¹ , R ² , R ⁴ -R ^{6 are} different from H or at least one substituent from R ¹ and R ² for C (= O) -R ⁷ or -C (= O) -OR ⁷ .

The proportion of one or more compounds selected from chromone derivatives and coumaranones in a preparation is preferably from

0.001 to 5 wt.%, Particularly preferably from 0.01 to 2 wt.% Based on the total preparation.

The protective effect of preparations against oxidative stress or against the action of radicals can be improved if the preparations contain one or more antioxidants, wherein the skilled person has no difficulty in selecting suitable fast or delayed-acting antioxidants.

In a preferred embodiment, therefore, the preparation is a preparation for protecting body cells against oxidative stress, in particular for reducing skin aging, characterized in that it contains, in addition to the self-tanning substances of the formula (I) or (II), the optional flavonoids and optionally containing other ingredients, one or more 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, (e.g., urocanic acid) and derivatives thereof, peptides such as D, L-camosine, D-carnosine, L-carnosine, and the like

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) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their Derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and Sulfoximinverbindungen (eg Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, Heptathioninsulfoximin) in very low tolerated dosages (eg pmol to mol / kg), further ( Metal) chelators, (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, 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) and coniferyl benzoate of benzoin, rutinic acid and derivatives thereof, α-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 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 ₁ ^'

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 are} each independently of one another 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, more preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester (eg

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 cosmetic 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-α-tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (for example Oxynex ^® 2004) , Such antioxidants are used with the compounds of the invention in such compositions usually in weight percent ratios in the range of 1000: 1 to 1: 1000, preferably in weight percent ratios of 100: 1 to 1: 100.

Among the phenols which can be used according to the invention, the polyphenols, which occur in part as natural substances, are of particular interest for applications in the pharmaceutical, cosmetic or nutritional field. For example, the flavonoids or bioflavonoids, which are known mainly as plant dyes, frequently have an antioxidant potential. Effects of the substitution pattern of mono- and dihydoxy flavones are dealt with by K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108. It is observed there that dihydroxyflavones having an OH group adjacent to the keto function or OH groups in the 3'4 'or 6,7 or 7,8 position have antioxidant properties while other mono- and Dihydroxyflavone partially have no antioxidant properties.

Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) is often cited as a particularly effective antioxidant (eg, CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A.E.M.F. Soffers and I.M.C.M. Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH dependence of the antioxidant activity of hydroxyflavones, and quercetin shows the highest activity of the investigated structures over the entire pH range.

Suitable antioxidants are furthermore compounds of the formula (C)

in which

R ¹ to R ^{10 may be the} same or different and are selected from H

OR 11 straight-chain or branched C _r to C ₂ o-alkyl groups, straight-chain or branched C ₃ - to C ₂ o-alkenyl groups, straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkyl groups, where the

Hydroxy group may be bonded to a primary or secondary carbon atom of the chain and further the alkyl chain may also be interrupted by oxygen, and / or

C ₃ - to C-io-cycloalkyl and / or C ₃ - to C ₂ cycloalkenyl groups, where the rings may each also by - (CH ₂₎ _n groups, where n = 1 to 3 can be bridged, where all OR ^{11 are} independently stand each other for

OH straight-chain or branched Cr to _{C2o-alkyloxy,} straight-chain or branched C ₃ - to C ₂ o-alkenyloxy groups, straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkoxy groups, wherein the hydroxy group (s) to a primary or secondary carbon atoms of the chain and the alkyl chain can also be interrupted by oxygen, and / or C ₃ - to Cio-cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, where the rings are each also denoted by - (CH ₂ ) _n - groups may be bridged with n = 1 to 3 and / or, - mono- and / or oligoglycosyl radicals, with the proviso that at least 4 radicals from R ¹ to R ⁷ are OH and that in the molecule at least 2 pairs of adjacent groups -OH , or R ² , R ⁵ and R ^{6 are} OH and the radicals R ¹ , R ³ , R ⁴ and R ^{7 "10 are} H, as described in German Patent Application DE-A-102 44 282.

The preparations to be used may contain vitamins as further ingredients. 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 Ki, esculin (vitamin P active ingredient), thiamine (vitamin B ₁ ), 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 -α-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. Nutritional physiology applications are based on the recommended vitamin requirement.

Preferred preparations can also serve for sunscreen and then contain, in addition to the bifunctional DHA derivatives of the formula (I) or the dimers of the formula (M) and optionally other ingredients, UV filters.

In principle, all UV filters are suitable for combination with the DHA derivatives to be used according to the invention. Particular preference is given to such UV Filters whose physiological safety has already been proven. Both for UVA and UVB filters, there are many well-known and proven substances from the literature, eg

Benzylidenecamphor derivatives, such as 3- ^{(4'-methylbenzylidene)} -dl-camphor (for example Eusolex 6300), 3-benzylidenecamphor (for example Mexoryl® SD) ₁ polymers of N - {(2 and 4) - [(2-3- oxobom yliden) methyl] benzyl} -acrylamide (eg Mexoryl® SW), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (eg Mexoryl® SK) or (2-oxoborn-3-yl) yliden) toluene-4-sulfonic acid (eg Mexoryl® SL),

Benzoyl or dibenzoylmethanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (e.g., Eusolex® 9020) or 4-isopropyldibenzoylmethane (e.g., Eusolex® 8020),

Benzophenones such as 2-hydroxy-4-methoxybenzophenone (e.g., Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (e.g., Uvinul® MS-40),

Methoxycinnamate such as octyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl A-methoxycinnamate, e.g. as a mixture of isomers (e.g., Neo Heliopan® E 1000),

Salicylate derivatives such as 2-ethylhexyl salicylate (eg Eusolex® OS), 4-isopropylbenzyl salicylate (eg Megasol®) or 3,3,5-trimethylcyclohexyl salicylate (eg Eusolex® HMS) ₁

4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 2-ethylhexyl 4- (dimethylamino) benzoate (e.g., Eusolex® 6007), ethoxylated 4-aminobenzoic acid ethyl ester (e.g., Uvinul® P25),

Phenylbenzimidazole sulfonic acids, such as 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (eg Eusolex® 232), 2,2- (1,4-phenylene) bisbenzimidazole-4,6-disulfonic acid or salts thereof ( eg Neoheliopan® AP) or 2,2- (1,4-phenylene) bisbenzimidazole-6-sulfonic acid;

and other substances like 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (eg Eusolex® OCR),

- 3,3 ^ 1 ^ -phenylenedimethylene ^ bis- ^ -dimethyl ^ -oxobicyclo-1-hept-1-ylmethanesulfonic acid and their salts (for example Mexoryl® SX) and

- 2, 4,6-trianilino- (p-carbo-2 ^{^{'-ethylhexyl-1'}} -oxi) -1, 3,5-triazine (for example Uvinul T 150) - 2- (4-diethylamino-2-hydroxy benzoyl) benzoic acid hexyl ester (eg

Uvinul® UVA Plus, BASF).

The compounds listed in the list are examples only. Of course, other UV filters can be used.

Other suitable organic UV filters are e.g.

2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol (eg silatrizole ^® , Drometrizole, Trisiloxane, Mexoryl® XL),. 4,4 ^' - [(6- [4- ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) ( for example Uvasorb HEB ^®),

α- (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl) and about 6% methyl [2- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy] -1-methylenethyl] and about 1.5% methyl [3- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy) propenyl) and 0.1 to 0.4% (methylhydrogen] silylene]] (n "60) (CAS No. 207 574-74-1)

- 2,2 ^{'methylene-bis-} (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol) (CAS No. 103 597-45-1).

- 2,2 ^'- (1, 4-phenylene) bis- (1 H-benzimidazol-4,6-disulfonic acid, monosodium salt) and (CAS No. 180 898-37-7.) - 2,4-bis- { [4- (2-ethyl-hexyloxy) -2-hydroxyl] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (CAS No. 103 597-45, 187 393-00- 6).

Other suitable UV filters are also Methoxyflavone ensprechend the German patent application DE-A-10232595.

Organic UV filters are usually incorporated in formulations in an amount of 0.5 to 20 percent by weight, preferably 1 to 15 percent by weight.

In order to ensure optimized UV protection, it is further preferred if preparations with light protection properties also contain inorganic UV filters. Conceivable inorganic UV filters are those from the group of titanium dioxides, such as coated titanium dioxide (for example Eusolex® T-2000, Eusolex ^® T-AQUA, Eusolex® T-AVO), zinc oxides (eg Sachtotec®), iron oxides or even cerium oxides are conceivable. These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 percent by weight, preferably 2 to 10 wt .-%, in cosmetic preparations.

Preferred compounds having UV-filtering properties are 3- (4 ^'- methylbenzylidene) -dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) -Pro-pan-1, 3-dione , 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxy-benzophenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4- (dimethylamino) -benzoic acid 2-ethyl-hexyl-ester, 2-cyano 3,3-di-phenyl-2-ethylhexyl acrylate, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts.

By combining one or more of said compounds 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 advantageous to use organic UV filters in encapsulated form. In detail, there are the following advantages:

- The hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter. For example, hydrophobic UV filters can also be incorporated into purely aqueous preparations. In addition, the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.

Certain UV filters, in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that affect the photostability of these filters, such as cinnamic acid derivatives, the photostability of the entire formulation can be increased.

In the literature, the skin penetration through organic UV filters and the associated irritation potential during direct application to the human skin is discussed again and again. The encapsulation of the corresponding substances proposed here prevents this effect. In general, the encapsulation of individual UV filters or other ingredients can result in problems with the preparation which result from the interaction of individual constituents of the preparation, such as crystallization operations, precipitation and agglomeration are avoided because the interaction is suppressed.

Therefore, it is preferred if one or more of the above-mentioned UV filters are present in encapsulated form. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the o.g. Effects it is still necessary that the capsules are sufficiently stable and donate the encapsulated active ingredient (UV filter) not or only to a small extent to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, US Pat. No. 6,242,099 B1 describes the preparation of suitable capsules having walls made of chitin, chitin derivatives or polyhydroxylated polyamines. Particularly preferred capsules have walls which can be obtained by a SolGel process as described in applications WO 00/09652, WO 00/72806 and WO 00/71084. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.

In this case, the capsules in preparations to be used according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the above-indicated weight percentages.

The preparations to be used according to the invention may additionally contain further customary skin-friendly or skin-care active substances. In principle, these can be all active ingredients known to the person skilled in the art.

Particularly preferred active ingredients, in particular for skin-care preparations, are, for example, also so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. suitable Osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors. Within the meaning of the German patent application DE-A-10133202, osmolytes are understood as meaning, in particular, substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below: taurine, choline, betaine, Phosphorylcholine, glycerophosphorylcholine, glutamine, glycine, α-alanine, glutamate, aspartate, proline, and taurine. Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z. B. Compounds that are converted to osmolytes by metabolic steps.

Preferably, according to the invention, as compatible solute substances are selected from the group consisting of pyrimidinecarboxylic acids (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic diphosphoglycerate, N.-

Acetylomithine, trimethylamine N-oxide di-myo ¹ inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), β-mannosylglycerate (firoin), β-mannosylglyceramide ( Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, for example an acid, a salt or ester of these compounds or combinations thereof.

In particular, ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S ₁ S) -1, 4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives. These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents. In particular, they stabilize enzymes against denaturing conditions such as salts, extreme pH, surfactants, urea, guanidinium chloride and other compounds.

Ectoine and ectoine derivatives such as hydroxyectoine can be used to advantage in medicines. In particular, hydroxyectoine can be used for the manufacture of a medicament for the treatment of skin diseases. Other fields of use of hydroxyectoine and other ectoin derivatives are typically in areas in which, for example, trehalose is used as an additive. Thus, ectoine derivatives, such as hydroxyectoine, can be used as a protective substance in dried yeast and bacterial cells. Also Pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins such as t-PA can be protected with ectoine or its derivatives.

Among the cosmetic applications, the use of ectoine and ectoine derivatives for the care of aged, dry or irritated skin should be mentioned in particular. For example, European Patent Application EP-A-0 671 161 describes in particular that ectoine and hydroxyectoine are used in cosmetic preparations such as powders, soaps, surfactant-containing cleansing products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.

In this case, a pyrimidinecarboxylic acid according to the following formula is preferably used,

wherein R ^{1 is} a radical H or C 1-8 -alkyl, R ^{2 is} a radical H or C 1-4 -alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and C1-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particularly preferred are the pyrimidinecarboxylic acids ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidine-carboxylic acid) and hydroxyectoine ((S, S) -1, 4,5,6-tetrahydro-) 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). In this case, the preparations to be used according to the invention preferably contain such pyrimidinecarboxylic acids in amounts of up to 15% by weight.

It is particularly preferred if the compatible solutes are selected from di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), ß-mannosylglycerate (Firoin ),

Mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP), ectoine, hydroxyectoine or mixtures thereof. Among the aryl oximes also preferably used is preferably 2-hydroxy-5-methyllaurophenonoxim, which is also referred to as HMLO, LPO or F5 used. Its suitability for use in cosmetic products is known for example from the German patent application DE-A-41 16 123. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are associated with inflammation. It is known that such preparations can be used, for example, for the therapy of psoriasis, different forms of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages. Compositions according to the invention which additionally contain an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show anti-inflammatory suitability. The preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.

Furthermore, the preparations according to the invention may contain at least one self-tanner as further ingredient.

Advantageous self-tanner may be used, inter alia:

HC = OH ₂ (> OH

HC = O HC = O CH ₂ H (> 0

HC-O C = OCH ₂ C

I ²

I

H ₂ CO ₂ H ₂ C-OH HC = OH ₂ C-OH

Glycerol aldehyde hydroxymethylglyoxal γ-dialdehyde erythrulose

H ₂ C-OH

HC = O 6-aldo-D-fructose ninhydrin

Furthermore, the 5-hydroxy-1, 4-naphthoquinone (juglone) may be mentioned, which consists of the

Peels of fresh walnuts is extracted

5-hydroxy-1,4-naphthoquinone (juglone)

and 2-hydroxy-1,4-naphthoquinone (Lawson) found in henna leaves.

2-hydroxy-1,4-naphthoquinone (Lawson)

Very particular preference is the 1, 3-dihydroxyacetone (DHA), occurring in the human body trivalent sugars and its derivatives H ₂ C-OH

C = O

HX-OH 2

1, 3-dihydroxyacetone (DHA)

The bifunctional dihydroxyacetone derivatives of the formula (I) and the dimeric compounds of the formula (II) and optionally further active compounds can be incorporated in the customary manner, for example by mixing, into cosmetic or dermatological preparations.

Suitable preparations for external use, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin. For internal use, administration formulas such as capsules, dragees, powders, tablet solutions or solutions are suitable. AIs application of the preparations to be used are, for example: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays. Preferred forms of application are also shampoos, sun baths and shower baths, which are also known as so-called "spray tanning, airbrush tanning or sun showers" from commercial self-tanning studios.

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, 1, 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 of these substances contain.

Suspensions may contain 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 contain the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.

Facial and body oils may contain the usual excipients 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.

Further typical cosmetic application forms are also lipsticks, lip balm sticks, powder, emulsion and wax make-up as well as 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 sense of the present invention is advantageously selected from

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 unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from Group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms. The fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

If appropriate, the aqueous phase of the preparations to be used advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C-number alcohols, eg. For example, ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous aüs the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another ingredient.

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 formulation.

In a preferred embodiment, the preparations to be used contain hydrophilic surfactants. The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and coco amphoacetates.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic).

The cosmetic and dermatological preparations can be in various forms. So they can z. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. Oil-in-water (W / O / W), a gel, a solid stick, an ointment or even an aerosol. It is also advantageous to present Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g. As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-A-43 08 282, have been found to be favorable. Preference is given to emulsions. ONSI emulsins are especially preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.

For example, O / W emulsifiers are selected as co-emulsifiers, principally from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W Emulsifiers have saturated radicals R and R ¹ . If the O / W emulsifiers have unsaturated radicals R and / or R ¹ , or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers may also be lower or higher.

It is advantageous to choose the fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols). Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), polyethylene. glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) - isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16) , Polyethylene glycol (17) - isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) - isostearyl ether (isosteareth-20), polyethylene glycol (13 ) cetyl ether (ceteth-13), polyethylene glycol (14) cetyl ethers (ceteth-14), polyethylene glycol (15) cetyl ether (ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether (ceteth-17), polyethylene glycol (18) cetyl ether (ceteth-18 Polyethylene glycol (19) Cetyl ether (Ceteth-19), Polyethylene glycol (20) Cetyl ether (Ceteth-20), Polyethylene glycol (13) Isocetyl ether (Isoceteth-13), Polyethylene glycol (14) - Isocetyl ether (Isoceteth-14). , Polyethylene glycol (15) isocetyl ether (isoceteth-15), polyethylene glycol (16) isocetyl ether (isoceteth-16), polyethylene glycol (17) - isocetyl ether (Isoceteth-17), polyethylene glycol (18) isocetyl ether (Isoceteth-18), polyethylene glycol (19) isocetyl ether (Isoceteth-19), polyethylene glycol (20) - isocetyl ether (Isoceteth-20), polyethylene glycol (12) oleyl ether (Oleth-12 ), Polyethylene glycol (13) oleyl ether (oleth-13), polyethylene glycol (14) oleyl ether (oleth-14), polyethylene glycol (15) oleyl ether (oleth-15), polyethylene glycol (12) lauryl ether (laureth-12), polyethylene glycol (12) isolethyl ether (isoleaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth- 16), polyethylene glycol (17) cetyl stearyl ether (ceteareth-17), polyethylene glycol (18) cetyl stearyl ether (ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (ceteareth-19), polyethylene glycol (20) cetyl stearyl ether (ceteareth-20).

It is further advantageous to choose the fatty acid ethoxylates of the following group: polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20 ) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate , Polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate.

As the ethoxylated alkyl ether carboxylic acid or its salt, the sodium laureth-11-carboxylate can be advantageously used. As the alkyl ether sulfate, sodium laureth-4 sulfate can be advantageously used. As the ethoxylated cholesterol derivative, polyethylene glycol (30) cholesteryl ether can be advantageously used. Also polyethylene glycol (25) soybean oil has been proven. As ethoxylated triglycerides, the polyethylene glycol (O) Evening Primrose Glycerides can advantageously be used (Evening Primrose = evening primrose). It is furthermore advantageous to use the polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20) glyceryl oleate,

Polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoat).

It is also favorable to use the sorbitan esters from the group consisting of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate,

Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:

Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C-, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ether saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms and sorbitan esters more saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a Chain length of 8 to 24, in particular 12-18 C atoms.

Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate,

Sorbitan monocaprylate, sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, isobehenyl alcohol, Selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate.

Compositions which are preferred according to the invention are also suitable for protecting human skin against aging processes as well as against oxidative stress, i. against damage by radicals, as e.g. be generated by sunlight, heat or other influences. It is present in various dosage forms commonly used for this application. Thus, it can be used in particular as a lotion or emulsion, such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, as solid pens or be formulated as an aerosol.

The preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, e.g. Thickeners, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent or the skin, and others commonly used in cosmetics ingredients.

It is possible to use as dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof. Particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerine and sorbitol.

A preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

Further preferred embodiments are oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily-alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as Propylene glycol, and / or a polyol such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.

The preparation may also be in the form of an alcoholic gel comprising one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickener, such as silica. The oily-alcoholic gels also contain natural or synthetic oil or wax.

The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.

If a preparation is formulated as an aerosol, the usual blowing agents are generally used, such as alkanes, fluoroalkanes and chlorofluoroalkanes, preferably alkanes.

The preparations to be used can be prepared using techniques that are well known to the person skilled in the art.

The compositions as described above may contain or comprise, consist essentially of or consist of the necessary or optional ingredients.

Even without further statements, it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments and examples are therefore to be considered as merely illustrative, in no way limiting, disclosure. 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.

The following examples of the subject matter of the invention are merely illustrative and by no means limit the present invention in any way. Moreover, the described invention is executable throughout the claimed range. All compounds or components that can be used in the preparations are either known and are commercially available or can be synthesized by known methods. The INCI names of the raw materials used are specified (the INCI names are given by definition in English).

Examples

General Procedure for the Synthesis of DHA Ortho-Esters

Dihydroxyacetone is reacted with catalytic amounts of (+/-) - camphor-10-sulfonic acid was stirred in dioxane at 50-100 ⁰ C for monomerization for about 2 hours.

Subsequently, the ortho-ester fragment to be coupled is added as trialkyloxy ortho-ester and stirred for 6-48 hrs. At 50-100 ⁰ C Subsequently, the purification is carried out by distillation and / or crystallization.

General procedure for the synthesis of dimeric DHA-ortho-esters

Dihydroxyacetone is added to a solution of catalytic amounts of (+/-) - camphor 10-sulfonic acid and stirred at 50-100 ⁰ C for 6-48 hours in the to be coupled ortho ester fragment.. Subsequently, the purification is carried out by distillation and / or crystallization.

Example 1:

Synthesis of 2-ethoxy-2-methyl- [1,3] dioxan-5-one (dihydroxyacetone-ortho-ethyl-acetate, DHA-OEA)

triethyl

Dioxane, CSA

13 g of dihydroxyacetone (144 mmol) and 335 mg (+/-) of camphor-10-sulfonic acid

(CSA, 1, 4 mmol, catalyst) are dissolved in 650 ml of dioxane and stirred for 120 min at 60 ⁰ C for DHA monomerization. Then 131 ml of triethyl orthoacetate (721 mmol) are added dropwise and the reaction solution for 16 hrs. At 60 ⁰ C stirred. After purification by vacuum distillation, 9.4 g of 2-ethoxy-2-methyl- [1,3-dioxan-5-one (DHA-OEA, 40.7%) are obtained as a colorless, odorless oil.

NMR data of 2-ethoxy-2-methyl-π.33dioxan-5-one (DHA-OEA) The NMR spectra were measured on a Bruker DPX spectrometer ( ¹ H: 250 MHz, ¹³ C: 62.9 MHz ).

¹ H-NMR (CDCl ₃ ): δ = 4.31 (2H, d, J = 18.3 Hz), 4.13 (2H, d, J = 18.5 Hz), 3.36 (2H ₁ q, J = 7.1 14.1 Hz), 1.59 ( 3H, s), 1.24 (3H, t, J = 7.0 Hz) ppm ¹³ C-NMR (CDCl ₃ ): δ = 205.0, 112.2, 67.6, 51.5, 21.3, 15.2 ppm

Example 2:

Synthesis of 2,10-diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxadispiro [4.2.4.2] tetradecane (dimeric dihydroxyacetone-bis-ortho-ethyl-acetate, dDHA- OEA)

4 g of dimeric dihydroxyacetone (44.4 mmol) and 103 mg (+/-) - camphor-10-sulfonic acid (CSA, 0.4 mmol; catalyst) in 40 ml of triethylorthoacetate (222 mmol) for 16 h at 60 ^{the 0th} C stirred. After purification by crystallization, 2.75 g of 2, 10-diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxadispiro [4.2.4.2] tetradecane (dDHA-bOEA; 19, 3%) as colorless crystals.

NMR data 2,10-Diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxa-dispiroF4.2.4.2l-tetradecane (dDHA-bOEA):

The NMR spectra were measured on a Bruker DPX spectrometer ( ¹ H:

250 MHz, ¹³ C: 62.9 MHz).

¹ H-NMR (CDCl ₃ ): δ = 4.08-4.16 (3H ₁ m), 3.99 (1H, d, J = 9.0 Hz), 3.54-3.80 (8H, m), 1.65 (3H, s), 1.57 ( 3H, s), 1.20 (6H, dt, J = 2.1, 7.0 Hz) ppm

¹³ C-NMR (CDCl ₃ ): δ = 123.9, 123.7, 99.3, 98.9, 71.6, 71.3, 65.5, 65.1, 64.2, 57.6,

56.9, 24.2, 23.2, 14.9, 14.7 ppm

Example 3: In vitro browning test of 2-ethoxy-2-methyl-π, 31-dioxan-5-one (DHA-OEA)

160 mg of 2-ethoxy-2-methyl- [1,3] dioxan-5-one (DHA-OEA; 1 mmol) is mixed with 146 mg of DL-lysine (1 mmol) in 94 ml of ethylene glycol and 6 ml of water (potassium hydrogen phthalate). buffered to pH 4) and stirred for 24 hours at 37 ⁰ C (= Liquids / f / π model). Subsequently, the Lab values of the solution are measured by UV-Vis spectrometer (Varian Cary-100) and with DHA / lysine (90 mg / 146 mg) and erythrulose / lysine (120 mg / 146 mg) in the liquid / c / n model compared. After 24 h, a 1/10 mixture of the DHA / lysine solution with ethylene glycol is prepared and also compared with Erythrulose by Lab.

(the smaller L ^* the darker, a *> 0 red, a ^* <0 green, b ^* > 0 yellow, b * <0 blue)

As a second reading is using the GC headspace method (device: Perkin bucket Clarus 600 + Turbo matrix head-space autosampler; separation column: DB624 / 30 m / 0.32 mm ID / 1, 8μm film thickness; temperature program: 60-220 ° C / 20 ° C * min ^{~ 1;} HS parameters: tempering time: 60 min; tempering temperature: 80 ⁰ C; needle temperature: 9O ⁰ C, transfer temperature: 100 ° C; injection time: 0.08 min), the content of formed ethanol during the browning reaction. For this purpose, samples of the in vitro browning test are diluted with DMSO, heated to 80 ° C and analyzed from the gas space samples by GC. An increasing ethanol content was observed in parallel to the increasing browning:

*: For the values 0-168 hours, the blank value has already been subtracted

Result:

• DHA shows a color change, mainly due to a strong darkening (L * = 0.5).

• DHA-OEA shows a color change, mainly due to a yellow shift (b ^* = 4,6) and a darkening (L * = 8,1).

• DHA-OEA releases ethanol during the tanning reaction. Example 4:

Synthesis of 2-ethoxy-2- (2-methyl-1, 4,5,6-tetrahydropyrimidin-4-yl) -

[1,3] dioxan-5-one (dihydroxyacetone-ortho-ethyl-ectoine, DHA-EEOE)

13 g of dihydroxyacetone (144 mmol) and 335 mg (+/-) of camphor-10-sulfonic acid (1.4 mmol, catalyst) are dissolved in 130 ml of dioxane and stirred for 120 min at 60 ^° C. for DHA monomerization. Then, 42.31 g Ectoin triethoxy ortho ester (173.19 mmol, 1.2 eq.) Was added and the reaction solution for 16 hrs. At 60 ⁰ C stirred. After purification by crystallization, 22.7 g of 2-ethoxy-2- (2-methyl-1, 4,5,6-tetrahydropyrimidin-4-yl) -1,3-dioxinan-5-one (DHA-) are obtained. EEOE; 65%) as colorless crystals.

Example 5:

Synthesis of 5- (2-ethoxy-5-oxo [1,3] dioxan-2-yl) -pyrrolidin-2-one

(Dihydroxyacetone-ortho-ethyl-pyrrolidone carbonate, DHA-PEOE)

13 g of dihydroxyacetone (144 mmol) and 335 mg (+/-) - camphor-10-sulfonic acid (1.4 mmol, catalyst) are dissolved in 130 ml of dioxane and stirred for 120 min at 6O ⁰ C for DHA monomerization. Then, 40.06 g of 5-Triethoxymethyi- are pyrrolidin-2-one (173.19 mmol; 1, 2 eq.) Was added and the reaction stirred for 16 h at 60 ⁰ C.. After purification by crystallization to obtain 19.5 g 2-ethoxy-2- (2-methyl-1, 4,5,6-tetrahydro-pyrimidin-4-yl) -1,3-dioxinan-5-one (DHA-ectoine-ethyl-ortho-acetate; 59 %) as colorless crystals. Example 6: Hair dyeing experiments

Experiment 1: Hair dyeing with DHA-OEA in the sealed sample glass:

70 mg blonde bleached hair, 1-2 cm long cut, are weighed. 4 ml NaOH (c = 0.1 N) are added and after 5 min the supernatant solution is taken off with a pipette.

4 ml of ethylene glycol / phosphate buffer (94/6 solvent ratio) pH = 7 (Liquids / c / n model) are added and after a short time the supernatant solution is removed with the pipette.

4 ml ethylene glycol / phosphate buffer (in solvent ratio 94/6) pH = 7 and

10 drops of DHA-OEA are added to the mixture.

The mixture is closed for four days and allowed to stand at room temperature and in daylight.

After four days, the hair is filtered through a pleated filter, washed with water and then dried in air.

Experiment 2: Hair dyeing with DHA-OEA in a sealed test tube: 70 mg of blonde bleached hair, cut 1-2 cm long, are weighed. 4 ml of ethylene glycol / phosphate buffer (in solvent ratio 94/6) pH = 7

(Liquids / c / n model) are added. Subsequently, 10 drops of DHA-OEA are added to the mixture.

Experiment 3: Hair dyeing with DHA-OEA in the closed test tube: 70 mg of blonde bleached hair, cut 1-2 cm long, are weighed. 40

42 drops of DHA-OEA are added to the mixture.

The mixture is sealed for four days and at room temperature

Daylight left.

Experiment 4: Hair dyeing with DHA-OEA in the closed sample glass: 70 mg blonde bleached hair, 1-2 cm long cut, are weighed. 40-42 drops of DHA-OEA are added to the mixture. The mixture is sealed for three days and allowed to stand at room temperature and in daylight. Then a little water (about 1 ml) is added and allowed to stand for a further day.

Experiment 1 shows that after pretreatment of the hair with NaOH and hair coloring in the experiment shown a barely perceptible color change of the hair is observed.

In experiments 2 and 3, after visual assessment of several subjects, a

Color change observed.

In experiment 4, i. without pretreatment of the hair and with addition of water in pure DHA-OEA, in the visual assessment of several test persons, a clearly visible color change of the hair is observed.

Experiment 5: Hair Dyeing DHA-OEA on Slides:

Strands of blonde bleached hair are prepared by soaking a portion of the strands for about 15 minutes in 10% ammonia solution, another portion of the strands are soaked in 0.1 N NaOH for about 15 minutes and another portion of the strands becomes soaked in pure water. Of the soaked strands of hair, each half over the Heißluftfön (about 120 ⁰ C) dried. Subsequently, the individual differently pretreated hair strands, each wet or dry placed on slides.

The respective strands of hair on the slides are wetted with pure DHA-OEA. Another slide is placed with the rough side over the tress, pressed firmly and left for two days at room temperature and daylight.

Experiment 5 shows that DHA-OEA shows strong staining after pretreatment of hair with wet ammonia on wet hair after visual assessment of several subjects. After pretreatment of the hair with NaOH on damp hair and on hair hair which has not been pretreated, a color change is also observed after visual assessment of several test persons. Formulation Example 1a: O / W Tanning Cream

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

Marlipal 1618/11 (D CETEARETH-11 3.00 Lanette O (2) CETEARYL ALCOHOL 7.00 Luvitol EHO (3) CETEARYLOCTANOATE 5.00 Tegosoft TN (4) C12-15 ALKYL BENZOATE 2.50 Miglyol 812 N (1) CAPRYLIC / CAPRIC 2.50

TRIGLYCERIDES

Propyl 4-hydroxybenzoates (5) PROPYLPARABLES 0.05

Dihydroxyacetone-ortho- (5) DIHYDROXYACETONE 5.00 ethylacetate ORTHOETHYL ACETATE

B

1, 2-Propanediol (5) PROPYLENE GLYCOL 4.00 Methyl 4-hydroxybenzoates (5) METHYLPARABENES 0.15 Water, demineralized AQUA (WATER) 70.80

Total 100.00

Production method:

First, the phase A to 75 ° C and the phase B is heated to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A and stirred until a homogeneous mixture is formed. After homogenization, the formulation is stirred until it cools to room temperature. The pH is adjusted to pH = 6.5 with sodium hydroxide solution or citric acid.

Sources:

(1) Sasol Germany GmbH (2) Cognis GmbH (3) BASF AG

(4) Degussa-Goldschmidt AG (5) Merck KGaA / Rona®

Formulation Example 1b: O / W Tanning Cream

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

A

M

Marlipal 1618/11 (1) CETEARETH-11 3.00

Lanette O (2) CETEARYLALCOHOL 7.00

Luvitol EHO (3) CETEARY LOCTANOATE 5.00

Tegosoft TN (4) C12-15 ALKYL BENZOATE 2.50

Miglyol 812 N (D CAPRYLIC / CAPRIC 2.50

TRIGLYCERIDES

Propyl 4-hydroxybenzoates (5) PROPYLPARABLES 0.05

B

1,2-Propanediol (5) PROPYLENE GLYCOL 4.00

Methyl 4-hydroxybenzoates (5) METHYLPARABES 0.15

Water, demineralized AQUA (WATER) 60.80

Dihydroxyacetone-ortho- (2- (5) -DIHYDROXYACETONE 5.00 dimethyl-amino) ethyl-acetate ORTHO (2-DIMETHYL-AMINO) ETHYL ACETATE

Water, demineralized AQUA (WATER) 10.00 Total 100.00

Production method:

First, the phase A to 75 ° C and the phase B is heated to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A and stirred until a homogeneous mixture is formed. After homogenization and cooling of the emulsion, the phase C is added at 40 ° C. Subsequently, the formulation is stirred until it cools to room temperature. The pH is adjusted to pH = 7.0 with sodium hydroxide solution or citric acid.

Sources:

(1) Sasol Germany GmbH (2) Cognis GmbH (3) BASF AG

(4) Degussa-Goldschmidt AG (5) Merck KGaA / Rona® Formulation Example 1c: Alcohol-free O / W tanning cream

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

Λ n

Marlipal 1618/11 (1) CETEARETH-11 3.00

Isopropyl myristate (2) ISOPROPYL MYRISTATE 7.00

Luvitol EHO (3) CETEARY LOCTANOATE 5.00

Tegosoft TN (4) C12-15 ALKYL BENZOATE 2.50

Miglyol 812 N (1) CAPRYLIC / CAPRIC 2.50

TRIGLYCERIDES

Propyl 4-hydroxybenzoates (5) PROPYLPARABLES 0.05

B

Methyl 4-hydroxybenzoates (5) METHYLPARABES 0.15

Water, demineralized AQUA (WATER) 74.80

Total 100.00

Production method:

Sources:

(1) Sasol Germany GmbH (2) Cognis GmbH (3) BASF AG

(4) Degussa-Goldschmidt AG (5) Merck KGaA / Rona®

Formulation Example 2a: O / W Tanning Cream

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

M A

Tego Care 150 (1) GLYCERYL STEARATE, 8.00

STEARETH-25 CETETH-20,

STEARYL ALCOHOL

Miglyol 812 N (2) CAPRYLIC / CAPRIC 3.00

TRIGLYCERIDES

Isopropyl myristate (3) ISOPROPYL MYRISTATE 2.00

Paraffin liquid (4) PARAFFINUM LIQUIDUM 12.00

(MINERAL OIL)

Paraffin (4) PARAFFIN 2.00

Propyl 4-hydroxybenzoates (4) PROPYL PARABETES 0.15

Dihydroxyacetone-ortho- (4) DIHYDROXYACETONE 5.00 ethylacetate ORTHOETHYL ACETATE

B

1,2-Propanediol (4) PROPYLENE GLYCOL 4.00

Sorbitol F liquid (4) SORBITOL 2.00

Methyl 4-hydroxybenzoates (4) METHYLPARABES 0.05

Water, demineralized AQUA (WATER) 61.30

C

Fraαrance (α.s.) PERFUME 0.50

Total 100.00

Production method:

First, the phases A and B are heated separately to 75 ⁰ C. Thereafter, phase A is slowly added to phase B with gentle stirring. It is homogenized at 65 ⁰ C for one minute. The mixture is then cooled with stirring to 35 ° C and the phase C added with stirring, and further cooled. The pH is adjusted to pH = 7.5 with sodium hydroxide solution or citric acid.

Sources:

(1) Degussa-Goldschmidt AG (2) Sasol Germany GmbH (3) Cognis GmbH

(4) Merck KGaA / Rona® Formulation Example 2b: O / W Tanning Cream

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

A

M

Tego Care 150 (1) GLYCERYL STEARATE, 8.00

STEARETH-25 CETETH-20,

STEARYL ALCOHOL

Miglyol 812 N (2) CAPRYLIC / CAPRIC 3.00

TRIGLYCERIDES

Isopropyl myristate (3) ISOPROPYL MYRISTATE 2.00

Paraffin liquid (4) PARAFFINUM LIQUIDUM 12.00

(MINERAL OIL)

Paraffin (4) PARAFFIN 2.00

Propyl 4-hydroxybenzoates (4) PROPYL PARABETES 0.15

B

1, 2-propanediol (4) PROPYLENE GLYCOL 4.00

Sorbitol F liquid (4) SORBITOL 2.00

Methyl 4-hydroxybenzoates (4) METHYLPARABES 0.05

Water, demineralized AQUA (WATER) 49.50

Dihydroxyacetone-ortho-ethyl- (4) DIHYDROXYACETONE 5.00 lactate ORTHOETHYL LACTATE

Water, demineralized AQUA (WATER) 11.80

Fragrance (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 ⁰ C for one minute. The mixture is then cooled with stirring to 40 ° C and the phase C is added. It is then cooled to 35 ⁰ C and the phase D added with stirring, and further cooled. The pH is adjusted to pH = 6.5 with sodium hydroxide solution or citric acid.

Sources:

(1) Degussa-Goldschmidt AG (2) Sasol Germany GmbH (3) Cognis GmbH

(4) Merck KGaA / Rona® Formulation Example 3a: O / W Tanning Cream

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

Tego Care 150 (1) GLYCERYL STEARATE, 8.00 STEARETH-25, CETETH-20,

STEARYL ALCOHOL

Lanette O (2) CETEARYL ALCOHOL 1.50 Luvitol EHO (3) CETEARYL OCTANOATE 5.00 Miglyol 812 N (4) CAPRYLIC / CAPRIC 5.00 TRIGLYCERIDE

Paraffin liquid (5) PARAFFINUM LIQUIDUM 3.00 (MINERAL OIL)

AbilWax 2434 (1) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (5) PROPYLL PARKS 0.05

B

1,2-Propanediol (5) PROPYLENE GLYCOL 3.00

Methyl 4-hydroxybenzoates (5) METHYLPARABES 0.15

Water, demineralized AQUA (WATER) 52.20

C

Probiol L 05018 (Empty (7) AQUA, ALCOHOL DENATE, 5.00 liposomes) LELCITHIN, GLYCERINE,

DISODIUM PHOSPHATES

Water, demineralized AQUA (WATER) 10.00

Total 100.00

Production method:

First, the phases A and B are heated to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 ⁰ C 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 Formulation Example 3b: O / W Tanning Cream

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

Tego Care 150 (1) GLYCERYL STEARATE, 8.00 STEARETH-25, CETETH-20,

STEARYL ALCOHOL

La nice O (2) CETEARYL ALCOHOL 1.50 Luvitol EHO (3) CETEARYL OCTANOATE 5.00 Miglyol 812 N (4) CAPRYLIC / CAPRIC 5.00 TRIGLYCERIDE

Paraffin liquid (5) PARAFFINUM LIQUIDUM 3.00 (MINERAL OIL)

AbilWax 2434 (1) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (5) PROPYLL PARKS 0.05

B

1, 2-Propanediol (5) PROPYLENE GLYCOL 3.00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 0.15 Water, demineralized AQUA (WATER) 52.20

Dihydroxyacetone-ortho-ethyl- (5) DIHYDROXYACETONE 5.00 ectoine ORTHOETHYLECTOINE

Probiol L 05018 (Empty (7) AQUA, ALCOHOL DENATE, 5.00 tiposomes) LELCITHIN, GLYCERINE,

DISODIUM PHOSPHATES

Water, demineralized AQUA (WATER) 10.00

Total 100.00

Production method:

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 Formulation Example 4a: O / W Tanning Lotion

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

/ Λλ

Montanov 68 (1) CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.50

Lanette O (3) CETEARYL ALCOHOL 1.00

Cosmacol ELI (4) C12-13 ALIKYL LACTATE 2.00

Arimol HD (2) ISOHEXADECANE 1.50

Paraffin highly liquid (5) PARAFFINUM LIQUIDUM 3.50

(MINERAL OIL)

Dow Corning 9050 Silicone (6) CYCLOMETHICONE, 2.00

Elastomer blend DIMETHICONE

CROSSPOLYMER

RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 0.50

Propyl 4-hydroxybenzoates (5) PROPYLPARABLES 0.05

Dihydroxyacetone-ortho- (5) DIHYDROXYACETONE 2.50 ethyl acetate ORTHOETHYL ACETATE

B

RonaCare ^® Ectoin (5) ECTOIN 0.50

Glycerol, anhydrous (5) GLYCERINE 2.00

Water, demineralized AQUA (WATER) 60.90

Methyl 4-hydroxybenzoates (5) METHYLPARABES 0.15

C

Rhodicare S (7) XANTHAN GUM 0.20

D

Probiol L 05018 (Empty (8) AQUA, ALCOHOL DENATE, 5.00 liposomes) LECITHIN, GLYCERINE,

DISODIUM PHOSPHATES

Water, demineralized AQUA (WATER) 10.00

Fragrance Cucumber (9) PERFUME 0.20

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. Bezuqsquellen:

(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

Formulation Example 4b: O / W Tanning Lotion

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

Montanov 68 (1) CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.50 Lanette O (3) CETEARYL ALCOHOL 1.00 Cosmacol ELI (4) C12-13 ALIKYL LACTATE 2.00 Arimol HD (2) ISOHEXADECANE 1.50 Paraffin highly liquid (5) PARAFFINUM LIQUIDUM 3.50

(MINERAL OIL)

Dow Corning 9050 Silicone (6) CYCLOMETHICONE, 2.00 Elastomer Blend DIMETHICONE

CROSSPOLYMER

RonaCare ^® Tocopherol Acetate (5) Tocopheryl Acetate 00:50 propyl 4-hydroxybenzoate (5) PROPYLPARABEN 00:05 Dihydroxyacetone-ortho- (2- (5) Dihydroxyacetone 5:00 dimethyl-amino) ethyl-acetate 0RTH0 (2-dimethyl-

AMINO) ETHYL ACETATE

B

RonaCare ^® ectoine (5) ECTOIN 00:50 glycerol, anhydrous (5) GLYCERINE 2:00 Water, demineralized Aqua (Water) 60.90 methyl 4-hydroxybenzoate (5) 12:15 METHYLPARABEN

C

Rhodicare S (7) XANTHAN GUM 0.20

Probiol L 05018 (Empty (8) AQUA, ALCOHOL DENATE 5.00 liposomes) LECITHIN, GLYCERINE, DISODIUM PHOSPHATE

Water, demineralized AQUA (WATER) 10.00

Fragrance Cucumber O) PERFUME 0.20

Total 100.00 Method of Preparation:

First, the phases A and B are mixed separately and heated to 75 ⁰ C. Thereafter, phase C is added to phase B and added to phase A with stirring. It is homogenized. Then it is cooled with stirring and the phases D and E at 40 ⁰ C added. The pH is adjusted to pH = 6.5 with sodium hydroxide solution or citric acid.

Where to buy: (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

Formulation Example 5a: mild transparent W / O tanning lotion

Ingredients / Trade name gsquell Ie INCI [% by weight] A

Dow Corning 3225 C (1) CYCLOMETHICONE, 23.60

DIMETHICONE COPOLYOL

Propyl 4-hydroxybenzoates (2) PROPYLPARABES 0.05

Dihydroxyacetone-ortho- (2) DIHYDROXYACETONE 2.00 ethylacetate ORTHOETHYL ACETATE

B

Dihydroxyacetones (2) DIHYDROXYACETONE 3.00 Methyl 4-hydroxybenzoates (2) METHYLPARABENES 0.15 1, 2-propanediol (2) PROPYLENE GLYCOL 35.90 Water, demineralized AQUA (WATER) 35.30

Total 100.00

Production method:

First, phase B is dissolved and then it is given to phase A. The pH is with

Sodium hydroxide solution or citric acid adjusted to the value pH = 6.0.

Where to buy: (1) Dow Corning (2) Merck KGaA / Rona® Formulation Example 5b: Mild transparent W / O tanning lotion

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

Dow Corning 3225 C (1) CYCLOMETHICONE, 23.60 DIMETHICONE COPOLYOL

Propyl 4-hydroxybenzoates (2) PROPYLPARABES 0.05

B

Dihydroxyacetone-ortho-ethyl- (2) DIHYDROXYACETONE 5.00 lactate ORTHOETHYL LACTATE

Methyl 4-hydroxybenzoates (2) METHYLPARABES 0.15

1,2-propanediol (2) PROPYLENE GLYCOL 35.90

Water, demineralized AQUA (WATER) 35.30

Total 100.00

Production method:

First, phase B is dissolved and then it is given to phase A.

Where to buy: (1) Dow Corning (2) Merck KGaA / Rona®

Formulation Example 6a: W / O Tanning Lotion

Components / Trade name Source of supply INCI [Gew-%] r Λ \

Abil EM 97 (1) BIS-PEG / PPG-14/14 1.50

DIMETHICONE,

Cyclopentasiloxane

Abil EM 90 (1) CETYL PEG / PPG-10/1 1.30

DIMETHICONE

Ceraphyl 368 (2) ETHYLHEXYL PALMITATE 2.00

Tegosoft DEC (D DIETHYLHEXYL CARBONATE 5.00

Dow Corning 345 (3) CYCLOMETHICONE 13.00

Dow Corning 9041 Silicone (3) DIMETHICONE 3.00

Elastomer Blend CROSSPOLYMER,

DIMETHICONE

Fragrance Babylon (4) PERFUME 0.30

B

1, 2-propanediol (5) PROPYLENE GLYCOL 20.00

Glycerol, anhydrous (5) GLYCERINE 3.00

Magnesium sulphate (5) MAGNESIUM SULPHATE 2.00 heptahydrate

Phenonip (6) PHENOXYETHANOL, 1.00

butyl paraben,

ethyl paraben,

pROPYLPARABEN,

METHYLPARABEN

Ethanol 96% (5) ALCOHOL 8.00

Water, demineralized AQUA (WATER) 34.90

Total 100.00

Production method:

First, the magnesium sulfate heptahydrate is dissolved in the water of phase B. Then the remaining components of phase B are added. Phase B is slowly added to Phase A with stirring. It is quickly stirred for a further 2 minutes and homogenized. The pH is adjusted to pH = 7.5 with sodium hydroxide solution or citric acid.

Sources:

(1) Degussa-Goldschmidt AG (2) ISP Global Technologies (3) Dow Corning

(4) Drom (5) Merck KGaA / Rona® (6) Nipa Laboratories GmbH Formulation Example 6b: W / O Tanning Lotion

Ingredients / Trade name gsquel Ie INCI [% by weight] A

Abil EM 97 (D BIS-PEG / PPG-14/14 1.50

DIMETHICONE,

Cyclopentasiloxane

Abil EM 90 (1) CETYL PEG / PPG-10/1 1.30

DIMETHICONE

Ceraphyl 368 (2) ETHYLHEXYL PALMITATE 2.00

Tegosoft DEC (1) DIETHYLHEXYL CARBONATE 5.00

Dow Corning 345 (3) CYCLOMETHICONE 13.00

Dow Corning 9041 Silicone (3) DIMETHICONE 3.00

Elastomer Blend CROSSPOLYMER,

DIMETHICONE

Fragrance Babylon (4) PERFUME 0.30

Dihydroxyacetone-ortho-ethyl- (5) DIHYDROXYACETONE 5.00 pyrrolidone carbonate ORTHOETHYL

PYRROLIDONCARBONATE

B

1,2-Propanediol (5) PROPYLENE GLYCOL 20.00 Glycerol, anhydrous (5) GLYCERINE 3.00 Magnesium sulphate (5) MAGNESIUM SULPHATE 2.00 heptahydrate Phenonip (6) PHENOXYETHANOL, 1.00

butyl paraben,

ethyl paraben,

pROPYLPARABEN,

METHYLPARABEN

Ethanol 96% (5) ALCOHOL 8.00 Water, demineralized AQUA (WATER) 34.90

Total 100.00

Production method:

First, the magnesium sulfate heptahydrate is dissolved in the water of phase B. Then the remaining components of phase B are added. Phase B is slowly added to Phase A with stirring. It is quickly stirred for a further 2 minutes and homogenized.

Sources:

(1) Degussa-Goldschmidt AG (2) ISP Global Technologies (3) Dow Coming (4) Drom (5) Merck KGaA / Rona® (6) Nipa Laboratories GmbH Formulation Example 7a: Aqueous tanning gel

Components / Trade name Source of supply I INNCCII [% by weight] A

Dihydroxyacetone-ortho- (1) DIHYDROXYACETONE 5.00 ethylacetate ORTHOETHYLACETATE 1, 2-propanediol (1) PROPYLENE GLYCOL 2.50 sorbitol F liquid (1) SORBITOL 2.50 methyl 4-hydroxybenzoate (1) METHYLPARABEN 0.20 Water, demineralized AQUA (WATER) 28.30

B

Natrosol 250 HHR (2) HYDROXYETHYL CELLULOSE 1.50 Water, demineralized AQUA (WATER) 60.00

Total 100.00

Production method:

The Natrosol is added to the vortex of vigorously stirred Phase B water. The rate of addition must be slow enough to allow the particles to separate and to have their surface moistened individually, but should be fast enough to minimize the viscosity of the aqueous phase during polymer addition. The dihydroxyacetone ortho-ethyl acetate is dissolved in the water of phase A and the remaining ingredients are added with stirring. Phases A and B are added together and homogenized.

Sources:

(1) Merck KGaA / Rona® (2) Aqualon GmbH

Formulation Example 7b: Aqueous tanning gel

Components / Trade name Source of supply I INNCCII [% by weight] A

Dihydroxyacetone-ortho- (2- (1) -DIHYDROXYACETONE 5.00 dimethyl-amino) ethyl-acetate ORTHO (2-DIMETHYL)

AMINO) ETHYL ACETATE

1, 2-Propanediol (1) PROPYLENE GLYCOL 2.50 Sorbitol F liquid (1) SORBITOL 2.50 Methyl 4-hydroxybenzoate (D METHYLPARABEN 0.20 Water, demineralized AQUA (WATER) 28.30

B

Total 100.00

Production method:

The Natrosol is added to the vortex of vigorously stirred Phase B water. The rate of addition must be slow enough to allow the particles to separate and to have their surface moistened individually, but should be fast enough to minimize the viscosity of the aqueous phase during polymer addition. The dihydroxyacetone-ortho- (2-dimethylamino) ethyl-acetate is dissolved in the water of phase A and the remaining ingredients are added with stirring. Phases A and B are added together and homogenized.

Sources:

(1) Merck KGaA / Rona® (2) Aqualon GmbH

Formulation example 8a: aqueous-alcoholic tanning lotion for pump sprays

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

Ethanol 96% (D ALCOHOL 40.00

Tagat L 2 (2) PEG-20 GLYCERYL LAURATE 7.00

1, 2-Propanediol (1) PROPYLENE GLYCOL 5.00

Water, demineralized AQUA (WATER) 43.00

Total 100.00

Production method:

The dihydroxyacetone ortho-ethyl acetate is dissolved in the water and the remaining ingredients are added with stirring.

Formulation example 8b: aqueous-alcoholic tanning lotion for pump sprays

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

Dihydroxyacetone-ortho-ethyl- (5) DIHYDROXYACETONE 5.00 lactate ORTHOETHYL LACTATE

Ethanol 96% (D ALCOHOL 40.00

Tagat L 2 (2) PEG-20 GLYCERYL LAURATE 7.00

1, 2-Propanediol (1) PROPYLENE GLYCOL 5.00

Water, demineralized AQUA (WATER) 43.00

Total 100.00

Method of preparation: The dihydroxyacetone ortho-ethyl lactate is dissolved in the water and the remaining ingredients are added with stirring.

References: (1) Merck KGaA / Rona® (2) Degussa Goldschmidt AG Formulation Example 9a: W / Si Tanning Gel

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

M A

Dow Corning 5225 C (1) CYCLOPEN TASILOXANE, 20.00

PEG / PG-18/18 DIMETHICONE

DM-Fluid-A-6cs (2) DIMETHICONE 4.00

Soybean OiI (3) GLYCINE SOY (SOYBEAN OIL) 2.00

RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 0.50

B

RonaCare ^® Ectoin (4) ECTOIN 0.30

1, 2-propanediol (4) PROPYLENE GLYCOL 30.00

Dipropylene glycol (5) DIPROPYLENE, GLYCOL 10.00

Sodium Chloride (4) SODIUM CHLORIDE 1.00

Etanol 96% (4) ALCOHOL 5.00

1% caramel in water (6) CARAMEL 2.50

1% FD & C Yellow No. 6 in water (5) AQUA (WATER), Cl 15985 0.25

(FD & C YELLOW NO 6)

Water, demineralized AQUA (WATER) 19:25

C

Fragrance Melopeach (7) PERFUME 0.20

Total 100.00

Production method:

Phase B is released and added to Phase A. Phases C and D are added successively with stirring. It is homogenized. The pH is adjusted to pH = 6.5 with sodium hydroxide solution or citric acid.

Where to buy: (1) Dow Corning (2) S. Black GmbH (3) Gustav Heess GmbG (4) Merck KGaA / Rona® (5) BASF AG (6) DD Williamson (7) Drom Formulation Example 9b: W / Si Tanning Gel

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

Dow Corning 5225 C (1) CYCLOPEN TASILOXANE, 20.00

PEG / PG-18/18 DIMETHICONE

DM-Fluid-A-6cs (2) DIMETHICONE 4.00

Soybean OiI (3) GLYCINE SOY (SOYBEAN OIL) 2.00

RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 0.50

Dihydroxyacetone-ortho-ethyl- (4) DIHYDROXYACETONE 5.00 ectoine ORTHOETHYLECTOINE

B

RonaCare ^® Ectoin (4) ECTOIN 0.30

1, 2-propanediol (4) PROPYLENE GLYCOL 30.00

Dipropylene glycol (5) DIPROPYLENE GLYCOL 10.00

Sodium Chloride (4) SODIUM CHLORIDE 1.00

Etanol 96% (4) ALCOHOL 5.00

1% caramel in water (6) CARAMEL 2.50

1% FD & C Yellow No. 6 in water (5) AQUA (WATER), Cl 15985 0.25

(FD & C YELLOW NO 6)

Water, demineralized AQUA (WATER) 19:25

C

Fragrance Melopeach (7) PERFUME 0.20

Total 100.00

Production method:

Phase B is released and added to Phase A. Phase C is gradually submerged

Stirring added. It is homogenized.

Where to buy: (1) Dow Coming (2) S. Black GmbH (3) Gustav Heess GmbG

(4) Merck KGaA / Rona® (5) BASF AG (6) DD Williamson (7) Drom Formulation Example 10a: O / W tanning cream with UV A / B protection

Ingredients / Trade name gsquel! Ie INCI [% by weight] A

Eusolex ^® 2292 (1) ETHYLHEXYL 3:00

METHOXYCINNAMATE, BHT

Eusolex ^® 4360 (1) BENZOPHENONE-3 0.50 Tego Care 150 (2) GLYCERYL STEARATE, 8.00

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

Lanette O (3) CETEARYL ALCOHOL 1.50 Luvitol EHO (4) CETEARYL OCTANOATE 5.00 Miglyoll 812 N (5) CAPRYLIC / CAPRIC 5.00

TRIGLYCERIDES

Paraffin liquid (1) PARAFFINUM LIQUIDUM 3.00

(MINERAL OIL)

Abil-Wax 2434 (2) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (1) PROPYLPARABENES 0.05

Dihydroxyacetone-ortho- (1) DIHYDROXYACETONE 5.00 ethylacetate ORTHOETHYL ACETATE

B

1, 2-Propanediol (1) PROPYLENE GLYCOL 3.00

Methyl 4-hydroxybenzoates (1) SODIUM METHYLPARABLES 0.17 sodium salt

Water, demineralized AQUA (WATER) 63.18

Total 100.00

Production method:

First, the phases A and B are mixed separately and heated to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized and cooled to room temperature. The pH is adjusted to pH = 7.0 with sodium hydroxide solution or citric acid.

Sources:

(1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH (4) BASF AG (5) Sasoi Germany GmbH (6) Dow Corning Formulation Example 10b: O / W tanning cream with UV A / B protection

Ingredients / Trade name is INCI [% by weight] A

Eusolex ^® 2292 (1) ETHYLHEXYL 3:00

METHOXYCINNAMATE, BHT

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

TRIGLYCERIDES

Paraffin liquid (1) PARAFFINUM LIQUIDUM 3.00

(MINERAL OIL)

Abil-Wax 2434 (2) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (1) PROPYLPARABENES 0.05

Dihydroxyacetone-ortho- (2- (1) -DIHYDROXYACETONE 3.00 d imethyl-ino) ethyl-acetate 0RTHO (2-DIMETHYL-

AMINO) ETHYL ACETATE

B

1, 2-Propanediol (1) PROPYLENE GLYCOL 3.00

Methyl 4-hydroxybenzoates (1) SODIUM METHYLPARABLES 0.17 sodium salt

Water, demineralized AQUA (WATER) 53.18

Dihydroxyacetones (1) DIHYDROXYACETONE 2.00 water, demineralized AQUA (WATER) 10.00

Total 100.00

Production method:

First, the phases A and B are mixed separately and heated to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 ⁰ C added.

Sources of supply: (1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH (4) BASF AG (5) Sasol Germany GmbH (6) Dow Corning Formulation Example 10c: O / W tanning cream with UV A / B protection

Ingredients / Trade name gsquel Ie INCI [% by weight] A

Eusolex ^® 2292 (1) ETHYLHEXYL 3:00

METHOXYCINNAMATE, BHT

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

La nice O (3) CETEARYL ALCOHOL 1.50 Luvitol EHO (4) CETEARYL OCTANOATE 5.00 Miglyoll 812 N (5) CAPRYLIC / CAPRIC 5.00

TRIGLYCERIDES

Paraffin liquid (1) PARAFFINUM LIQUIDUM 3.00

(MINERAL OIL)

Abil-Wax 2434 (2) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (1) PROPYLPARABENES 0.05

Dihydroxyacetone-ortho-ethyl- (1) DIHYDROXYACETONE 5.00 lactate ORTHOETHYL LACTATE

B

1,2-propanediol (D PROPYLENE GLYCOL 3.00

Methyl 4-hydroxybenzoates (1) SODIUM METHYLPARABLES 0.17 sodium salt

Water, demineralized AQUA (WATER) 53.18

Water, demineralized AQUA (WATER) 10.00

Total 100.00

Production method:

Sources of supply: (1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH (4) BASF AG (5) Sasol Germany GmbH (6) Dow Corning Formulation Example 10d: O / W tanning cream with UV A / B protection

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

Eusolex ^® 2292 (1) ETHYLHEXYL 3:00

METHOXYCINNAMATE, BHT

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

Lanette O (3) CETEARYL ALCOHOL 1.50 Luvitol EHO (4) CETEARYL OCTANOATE 5.00 Miglyolt 812 N (5) CAPRYLIC / CAPRIC 5.00

TRIGLYCERIDES

Paraffin liquid (1) PARAFFINUM LIQUIDUM 3.00

(MINERAL OIL)

Abil-Wax 2434 (2) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (1) PROPYLPARABENES 0.05

B

1, 2-Propanediol (1) PROPYLENE GLYCOL 3.00

Methyl 4-hydroxybenzoates (1) SODIUM METHYLPARABLES 0.17 sodium salt

Water, demineralized AQUA (WATER) 53.18

Dihydroxyacetone-ortho-ethyl- (1) DIHYDROXYACETONE 5.00 ectoine ORTHOETHYLECTOINE

Water, demineralized AQUA (WATER) 10.00

Total 100.00

Production method:

First, the phases A and B are mixed separately and heated to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 ° C was added. The pH is adjusted to pH = 7.0 with sodium hydroxide solution or citric acid.

Sources:

(1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH

(4) BASF AG (5) Sasol Germany GmbH (6) Dow Corning Formulation Example 10e: O / W tanning cream with UV A / B protection

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

At

Eusolex ^® 2292 (1) ETHYLHEXYL 3:00

METHOXYCINNAMATE, BHT

Eusolex ^® 4360 (1) Benzophenone-3 00:50

Tego Care 150 (2) GLYCERYL STEARATE, 8.00

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

Lanette O (3) CETEARYL ALCOHOL 1.50

Luvitol EHO (4) CETEARYL OCTANOATE 5.00

Miglyoll 812 N (5) CAPRYLIC / CAPRIC 5.00

TRIGLYCERIDES

Paraffin liquid (1) PARAFFINUM LIQUIDUM 3.00

(MINERAL OIL)

Abil-Wax 2434 (2) STEAROXY DIMETHICONE 1.60

Dow Corning 200 Fluid (350 es) (6) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (D PROPYLPARABEN 0.05

Dihydroxyacetone-ortho-ethyl- (D DIHYDROXYACETONE 5.00 pyrrolidone carbonate ORTHOETHYL

PYRROLIDONCARBONATE

B

1, 2-Propanediol (1) PROPYLENE GLYCOL 3.00

Methyl 4-hydroxybenzoates (D SODIUM METHYLPARABENES 0.17 sodium salt

Water, demineralized AQUA (WATER) 63.18

Total 100.00

Production method:

First, the phases A and B are mixed separately and heated to 80 ⁰ C. After that will

Add Phase B slowly to Phase A with stirring. It is homogenized.

Sources:

(1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH

(4) BASF AG (5) Sasol Germany GmbH (6) Dow Corning Formulation Example 11a: O / W shimmering tanning lotion

Ingredients / Trade name gsquel Ie INCI [% by weight] A

Montanov 68 (1) CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.50

Lanette O (3) CETEARYL ALCOHOL 1.00

Cosmacol ELI (4) C12-13 ALKYL LACTATE 3.00

Cosmacol EMI (4) DI-C12-13 ALKYL MALATE 1.50

Dow Corning 9040 Silicone (5) CYCLOMETHICONE, 1.00

Elastomer blend DIMETHICONE

CROSSPOLYMER

Arlamol HD (2) ISOHEXADECANE 3.00

RonaCare ^® Tocopherol Acetate (6) Tocopheryl Acetate 00:50

Propyl 4-hydroxybenzoates (6) PROPYLPARABES 0.05

Dihydroxyacetone-ortho- (6) DIHYDROXYACETONE 5.00 ethyl acetate ORTHOETHYL ACETATE

12:50

B

RonaCare ^® ectoine (6) ECTOIN 00:50 Colorona Red Gold ^® (6) MICA, Cl 77891 (TITANIUM 2:00

DIOXIDES), Cl 77491 (1ON

OXIDES)

Glycerol, anhydrous (6) GLYCERIN 2.00

Caramel 250 (7) CARAMEL 1.00

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

Water, demineralized AQUA (WATER) 73.09

Methyl 4-hydroxybenzoates (6) METHYLPARABES 0.15

C

Sepigel 305 (1) LAURETH-7, POLYACRYL-0.50

AMIDE, C13-14 ISOPARAFFIN

D

Fragrance Babylon (9) PERFUME 0.20

Total 100.00 Herstellunαsverfahren:

First, the phases A and B are heated separately to 75 ⁰ 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 ⁰ C and the phase D is 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

Formulation Example 11b: O / W shimmering tanning lotion

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

M A

Montanov 68 (1) CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.50

Lanette O (3) CETEARYL ALCOHOL 1.00

Cosmacol ELI (4) C12-13 ALKYL LACTATE 3.00

Cosmacol EMI (4) DI-C12-13 ALKYL MALATE 1.50

Dow Corning 9040 Silicone (5) CYCLOMETHICONE, 1.00

Elastomer blend DIMETHICONE

CROSSPOLYMER

Arlamol HD (2) ISOHEXADECANE 3.00

RonaCare ^® Tocopherol Acetate (6) Tocopheryl Acetate 00:50

Propyl 4-hydroxybenzoates (6) PROPYLPARABES 0.05

Dihydroxyacetone-ortho- (2- (6) -DIHYDROXYACETONE 5.00 dimethyl-amino) ethyl-acetate 0RTHO (2-DIMETHYL-

AMINO) ETHYL ACETATE

12:50

B

RonaCare ^® Ectoin (6) ECTOIN 0.50

Colorona Red Gold ^® (6) MICA, Cl 77891 (TITANIUM 2:00

DIOXIDES), Cl 77491 (1ON

OXIDES)

Glycerol, anhydrous (6) GLYCERIN 2.00

Caramel 250 (7) CARAMEL 1.00

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

Water, demineralized AQUA (WATER) 73.09

Methyl 4-hydroxybenzoates (6) METHYLPARABES 0.15 Sepigel 305 (1) LAURETH-7, POLYACRYL0.50

AMIDE, C13-14 ISOPARAFFIN

Fragrance Babylon O) PERFUME 0.20

Total 100.00

Production method:

First, the phases A and B are heated separately to 75 ⁰ 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 ⁰ C and the phase D is added successively.

Where to buy: (1) Seppic (2) Uniqema (3) Cognis GmbH

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

(7) DD Williamson (8) Les Colorants Wackherr SA (9) Drom

Formulation Example 12a: O / W shimmering tanning lotion

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

Montanov 68 (1) CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.50

Lanette O (3) CETEARYL ALCOHOL 1.00

RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 0.50

Cosmacol ELI (5) C12-13 ALKYL LACTATE 3.00

Cosmacol EMI (5) DI-C12-13 ALKYL MALATE 1.50

Arlamol HD (2) ISOHEXADECANE 3.00

Dow Corning 9040 Silicone (6) CYCLOMETHICONE, 1.00

Elastomer blend DIMETHICONE

CROSSPOLYMER

Propyl 4-hydroxybenzoates (4) PROPYLPARABLES 0.05

B

RonaCare ^® ectoine (4) ECTOIN 12:50 Timiron ^® Star Luster MP-115 (4) MICA, Cl 77891 (TITANIUM 1:00

DIOXIDE)

Glycerol, anhydrous (4) GLYCERIN 2.00

Caramel 250 (7) CARAMEL 0.60

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

Methyl 4-hydroxybenzoates (4) METHYLPARABLES 0.15

Water, demineralized AQUA (WATER) 59.49

C

Sepigel 305 (1) LAURETH-7, POLYACRYL0.50

AMIDE, C13-14 ISOPARAFFIN

Probiol L 05018 (Empty (9) AQUA, ALCOHOLDENATE, 5.00 liposomes) LECITHIN, GLYCERIN, DISODIUM PHOSPHATE

Water, demineralized AQUA (WATER) 10.00

Fragrance Babylon (10) PERFUME 0.20

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 becomes homogenized. It is then cooled to 40 ° C and the phase D and E are added successively. The pH is adjusted to pH = 7.0 with sodium hydroxide solution or citric acid.

Sources:

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

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

(7) D.D. Williamson (8) Les Colorants Wackherr SA (9) Kuhs GmbH & Co. KG

(10) drom

Formulation Example 12b: O / W shimmering tanning lotion

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

M

Montanov 68 (1) CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Span 60 (2) SORBITAN STEARATE 1.50

La Nice O (3) CETEARYL ALCOHOL 1.00

RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 0.50

Cosmacol ELI (5) C12-13 ALKYL LACTATE 3.00

Cosmacol EMI (5) DI-C12-13 ALKYL MALATE 1.50

Arlamol HD (2) ISOHEXADECANE 3.00

Dow Corning 9040 Silicone (6) CYCLOMETHICONE, 1.00

Elastomer blend DIMETHICONE

CROSSPOLYMER

Propyl 4-hydroxybenzoates (4) PROPYLPARABLES 0.05

B

RonaCare ^® Ectoin (4) ECTOIN 0.50

Timiron ^® Starluster MP-115 (4) MICA ₁ Cl 77891 (TITANIUM 1.00

DIOXIDE)

Glycerol, anhydrous (4) GLYCERIN 2.00

Caramel 250 (7) CARAMEL 0.60

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

Methyl 4-hydroxybenzoates (4) METHYLPARABES 0.15

Water, demineralized AQUA (WATER) 59.49

C

Sepigel 305 (D LAURETH-7, POLYACRYL-0.50

AMIDE, C13-14 ISOPARAFFIN

Dihydroxyacetone-ortho-ethyl- (4) DIHYDROXYACETONE 5.00 pyrrole idoncarbonate ORTHOEΠΉYL PYRROLIDONE CARBONATE

Water, demineralized AQUA (WATER) 10.00

Fragrance Babylon (10) PERFUME 0.20

Total 100.00

Production method:

First, the phases A and B are heated separately to 75 ⁰ C. Thereafter, Phase A is slowly added to Phase B with stirring. At 60 ^° C., phase C is added to A / B and homogenized. It is then cooled to 40 ⁰ C and the phase D and E are added successively. The pH is adjusted to pH = 7.5 with sodium hydroxide solution or citric acid.

Sources:

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

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

(7) D.D. Williamson (8) Les Colorants Wackherr SA (9) Kuhs GmbH & Co. KG

(10) drom

Formulation Example 13a: clear W / O shimmering tanning lotion

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

M Λ

Abil EM 97 (1) BIS-PEG / PPG-14/14 1.20

DIMETHICONE,

Cyclopentasiloxane

Abil EM 90 (1) CETYL PEG / PPG-10/1 1.00

DIMETHICONE

Mirasil CM 5 (2) CYCLOMETHICONE 12.00

Ceraphyl 368 (3) ETHYLHEXYL PALMITATE 2.00

Dow Corning 9041 Silicone (4) DIMETHICONE 1.60

Elastomer Blend CROSSPOLYMER,

DIMETHICONE

Tegosoft DEC (D DIETHYLHEXYL CARBONATE 5.00

Fragrance Babylon (5) PERFUME 0.30

B

RonaCare ^® Ectoin (6) ECTOIN 0.50

Caramel 250 (7) CARAMEL 0.60

Timiron ^® Star Luster MP-115 (6) MICA, Cl 77891 (TITANIUM 1:00

DIOXIDE)

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

1, 2-propanediol (6) PROPYLENE GLYCOL 20.00

Glycerol, anhydrous (6) GLYCERIN 3.00

Magnesium sulphates heptahydrate. (6) MAGNESIUM SULFATE 2.00

Ethanol 96% (6) ALCOHOL 8.00

Phenonip (9) PHENOXYETHANOL, 1.00

BUTAYLPARABEN,

ethyl paraben,

pROPYLPARABEN,

METHYLPARABEN

Water, demineralized AQUA (WATER) 35.79

Total 100.00

Production method:

First, the magnesium sulfate heptahydrate is dissolved in the water of phase B. Then the remaining components of phase B are added. Phase B is slowly added to Phase A with stirring. It is quickly stirred for a further 2 minutes and homogenized. The pH is adjusted to pH = 6.5 with sodium hydroxide solution or citric acid. Sources:

(1) Degussa Goldschmidt AG (2) Rhodia GmbH (3) Global Technologies

(4) Dow Coming (5) Drom (6) Merck KGaA / Rona®

(7) D.D. Williamson (8) Les Colorants Wackherr SA (9) Nipa Laboratories GmbH

Formulation Example 13b: Clear W / O shimmering tanning lotion

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

M A

Abil EM 97 (1) BIS-PEG / PPG-14/14 1.20

DIMETHICONE,

Cyclopentasiloxane

Abil EM 90 (1) CETYL PEG / PPG-10/1 1.00

DIMETHICONE

Mirasil CM 5 (2) CYCLOMETHICONE 12.00

Ceraphyl 368 (3) ETHYLHEXYL PALMITATE 2.00

Dow Corning 9041 Silicone (4) DIMETHICONE 1.60

Elastomer Blend CROSSPOLYMER,

DIMETHICONE

Tegosoft DEC (1) DIETHYLHEXYL CARBONATE 5.00

Fragrance Babylon (5) PERFUME 0.30

Dihydroxyacetone-ortho-ethyl- (6) DIHYDROXYACETONE 5.00 ectoine ORTHOETHYLECTOINE

B

RonaCare ^® Ectoin (6) ECTOIN 0.50

Caramel 250 (7) CARAMEL 0.60

Timiron ^® Star Luster MP-115 (6) MICA, Cl 77891 (TITANIUM 1:00

DIOXIDE)

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

1, 2-propanediol (6) PROPYLENE GLYCOL 20.00

Glycerol, anhydrous (6) GLYCERIN 3.00

Magnesium sulfate heptahydrate (6) MAGNESIUM SULFATE 2.00

Ethanol 96% (6) ALCOHOL 8.00

Phenonip (9) PHENOXYETHANOL, 1.00

BUTAYLPARABEN,

ethyl paraben,

pROPYLPARABEN,

METHYLPARABEN

Water, demineralized AQUA (WATER) 35.79

Total 100.00 Method of Preparation:

Sources:

(1) Degussa Goldschmidt AG (2) Rhodia GmbH (3) Global Technologies

(4) Dow Corning (5) Drom (6) Merck KGaA / Rona® (7) DD Williamson (8) Les Colorants Wackherr SA (9) Nipa Laboratories GmbH

Formulation Example 14:

Skin protection cream that gives a summer-like complexion

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

M A

Eusolex OCR ^® (1) 5:00 OCTOCRYLENE

Eusole ^® 9020 (1) BUTYL METHOXYDIBENZ- 1:00

OYLMETHANE

Tego Care 150 (2) GLYCERYL STEARATE, 8.00

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

Lanette O (3) CETEARYL ALCOHOL 1.50

Tegosoft liquid (2) CETEARYL ETHYLHEXANOATE 3.50

Miglyol 812 N (4) CAPRYLIC / CAPRIC 3.50

TRIGLYCERIDES

Abil-Wax 2434 (2) STEAROXY DIMETHICONE 1.20

Dow Corning 200 (100cs) (5) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (1) PROPYLPARABENES 0.05

Dihydroxyacetone-ortho- (1) DIHYDROXYACETONE 2.00 ethylacetate ORTHOETHYL ACETATE

B

1, 2-Propanediol (1) PROPYLENE GLYCOL 3.00

RonaCare ^® Ectoin (1) ECTOIN 0.30

Methyl 4-hydroxybenzoates (D METHYLPARABES 0.15

Water, demineralized AQUA (WATER) 70.20

C

Fragrance "sunshine for cream D" (6) PERFUME 0.10

Total 100.00

Production method:

First, the phases A and B are heated separately to 80 ⁰ C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 ⁰ C added.

Sources:

(1) Merck KGaA / Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH

(4) Dow Corning (6) Bell Flavors & Fragrances Formulation Example 15:

Skin protection cream that gives a light summer tan

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

Tego Care 150 (1) GLYCERYL STEARATE, 8.00

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

Lanette O (2) CETEARYL ALCOHOL 1.50

Tegosoft liquid (1) CETEARYL ETHYLHEXANOATE 6.50

Miglyol 812 N (3) CAPRYLIC / CAPRIC 6.50

TRIGLYCERIDES

Abil-Wax 2434 (D STEAROXY DIMETHICONE 1.20

Dow Corning 200 (100cs) (4) DIMETHICONE 0.50

Propyl 4-hydroxybenzoates (5) PROPYLPARABLES 0.05

Dihydroxyacetone-ortho- (5) DIHYDROXYACETONE 0.75 ethyl acetate ORTHOETHYL ACETATE

B

1, 2-Propanediol (5) PROPYLENE GLYCOL 3.00

Ectoin (5) ECTOIN 0.30

Methyl 4-hydroxybenzoates (5) METHYLPARABES 0.15

Water, demineralized AQUA (WATER) 71.45

Fragrance "sunshine for cream D" (6) PERFUME 0.10

Total 100.00

Production method:

Sources:

(1) Degussa-Goldschmidt AG (2) Cognis GmbH (3) Sasol Germany GmbH

(4) Dow Coming (5) Merck KGaA / Rona® (6) Bell Flavors & Fragrances Formulation example 16: velvety body lotion for a natural color

Ingredients / Trade name is INCI [% by weight] A

Abil EM 07 (1) BIS-PEG / PPG-14/14 1.50

DIMETHICONE,

C YCLOPENTAS ILOXAN E

Abil EM 90 (1) CETYL PEG / PPG-10/1 1.30

DIMETHICONE

Ceraphyl 368 (2) ETHYLHEXYLPALMITATE 2.00

Tegosoft DEC (1) DIETHYLHEXYL CARBONATE 5.00

Dow Corning 345 (3) CYCLOMETHICONE 13.00

Dow Corning 9041 Silicone (3) DIMETHICONE 3.00

Elastomer Blend CROSSPOLYMER,

DIMETHICONE

Fragrance Babylon (4) PERFUME 0.30

Dihydroxyacetone-ortho- (5) DIHYDROXYACETONE 1.00 ethylacetate ORTHOETHYL ACETATE

B

Dihydroxyacetones (5) DIHYDROXYACETONE 1.00

RonaCare ^® Ectoin (5) ECTOIN 0.50

1, 2-propanediol (5) PROPYLENE GLYCOL 20.00

Glycerol, anhydrous (5) GLYCERIN 3.00

Magnesium sulphate (5) MAGNESIUM SULFATE 2.00 heptahydrate

Ethanol 96% (5) ALCOHOL 8.00

Phenonip (6) PHENOXYETHANOL, 1.00

butyl paraben,

ethyl paraben,

pROPYLPARABEN,

METHYLPARABEN

Water, demineralized AQUA (WATER) 37.40

Total 100.00

Production method:

First, the magnesium sulfate heptahydrate is dissolved in the water of phase B. Then the remaining components of phase B are added. Phase B is slowly added with stirring to phase A and it is homogenized.

Where to buy: (1) Degussa-Goldschmidt AG (2) ISP Global Technologies (3) Dow Coming (4) Drom (5) Merck KGaA / Rona® (6) Nipa Laboratories GmbH Formulation Example 17: Gentle Tanning Cream with Silver Glitter

Ingredients / Trade name gsquell Ie INCI [% by weight] A

Montanov 68 (D CETEARYL ALCOHOL, 4.00

CETEARYL GLUCOSIDE

Cosmacol ELI (2) C12-13ALKYL LACTATE 4.00 Arlamol HD (3) ISOHEXADECANE 3.00 Span 60 (3) SORBITAN STEARATE 1.50 Cosmacol EMI (2) DI-C12-13 ALKYL MALATE 2.50 Lanette O (4) CETEARYL ALCOHOL 1.00 Phenonip (5) PHENOXYETHANOL, 0.80

butyl paraben,

ethyl paraben,

pROPYLPARABEN,

METHYLPARABEN

Dihydroxyacetone-ortho- (6) DIHYDROXYACETONE 1.00 ethylacetate ORTHOETHYL ACETATE

B

RonaCare ^® Tocopherol Acetate (6) TOXOPHERYL ACETATE 0.50

Ronastar Silver (6) CALCIUMALUMINUM 1.00

BOROSILICATE, SILICA, CI77891

(TITANIUM DIOXIDE), TIN OXIDE

Glycerol, anhydrous (6) Glycerin 3:00 RonaCare ^® ectoine (6) ECTOIN 00:50 Water, demineralized Aqua (Water) 69.50

D

Sepigel 305 (1) LAURETH-7, POLYACRYL0.60

AMIDE, C13-14 ISOPARAFFIN

Dihydroxyacetones (6) DIHYDROXYACETONE 1.00 water, demineralized AQUA (WATER) 4.00

Germall 115 (7) IMIDAZOLIDINYL UREA 0.30 Water, demineralized AQUA (WATER) 1.50

Fragrance Melopeach (8) PERFUME 0.30

Total 100.00 Method of Preparation:

First, the phases A and C are heated separately to 75 ° C. Thereafter, Phase A is slowly added to Phase C with stirring. At 50 ^° C., phases B and D are added to A / C and homogenized (with a hand mixer). It is then cooled to 40 ° C and the phases E, F and G are added.

Where to buy: (1) Seppic (2) Condea Chimica DAC.S.p.A. (3) Uniqema

(4) Cognis GmbH (5) Nipa Laboratories GmbH (6) Merck KGaA / Rona®

(7) ISP Global Technologies (8) Drom

Formulation Example 18: Day Care Cream

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

Tego Care 150 (1) GLYCERYL STEARATE, 8.00

STEARETH-25, CETETH-20,

STEARYL ALCOHOL

La nice O (2) CETEARYL ALCOHOL 1.50 Tegosoft liquid (1) CETEARYL ETHYLHEXANOATE 6.50 Miglyol 812 N (3) CAPRYLIC / CAPRIC 6.50

TRIGLYCERIDES

Abil-Wax 2434 (1) STEAROXY DIMETHICONE 1.20

Dow Corning 200 (100cs) (4) DIMETHICONE 0.50

RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 0.50

Propyl 4-hydroxybenzoates (5) PROPYLPARABLES 0.05

B

1, 2-Propanediol (5) 3.00 Methyl 4-hydroxybenzoate (5) PROPYLENE GLYCOL 0.15 Water, demineralized METHYL PARADE 59.00

AQUA (WATER)

DHA-OEA-Rapid (5) DIHYDROXYACETONE 3.00

ORTHOETHYL ACETATE, TROXERUTIN

Water, demineralized AQUA (WATER) 10.00

Fragrance "sunshine for cream D" (6) PERFUME 0.10

Total 100.00

Production method:

First, the phases A and B are heated separately to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phases C at 40 ⁰ C added. Phase D is added.

Sources:

(1) Degussa-Goldschmidt AG (2) Cognis GmbH (3) Sasol Germany GmbH (4) Dow Coming (5) Merck KGaA / Rona® (6) Bell Flavors & Fragrances

Claims

claims

1. Use of a

or e

as a self-tanning substance, wherein the radicals are defined as follows:

X O, S or NR,

wherein R ¹ and R ² are the same or different,

these groups may be substituted by saturated and / or unsaturated alkyl groups of 1 to 8 carbon atoms, OR, NR ₂ , saturated, partially or completely unsaturated cycloalkyl of 3-7 carbon atoms substituted by OH or Oalkyl of 1-8 carbon atoms, wherein in these groups one or two carbon atoms are replaced by the heteroatoms and / or atomic moieties -O-, -N =, NR, -C (O) -, -C (O) O- and / or -C (O) NH- could be,

wherein R ^{3 'is} H or -CH ₂ OH and wherein R ^{3 is} H.

2. Use of a compound of the formula (I)

or a dimer derivative of the formula (II)

as hair dye, wherein the radicals are defined as follows:

X is O, S or NR ₁

R ¹ , R ² H, where R ^{2 may} not be H, straight-chain or branched, unsaturated or saturated alkyl having 1-20 carbon atoms, saturated, partially or completely unsaturated cycloalkyl having 3-7 carbon atoms, wherein R ¹ and R ² are the same or different,

these groups may be substituted by saturated and / or unsaturated alkyl groups of 1 to 8 carbon atoms, OR, NR ₂ , saturated, partially or completely unsaturated cycloalkyl of 3-7 carbon atoms substituted by OH or Oalkyl of 1-8 carbon atoms,

wherein in these groups one or two carbon atoms through the

Heteroatoms and / or atomic groups -O-, -N =, Nr ₁ -C (O) -, -C (O) O- and / or -C (O) NH- can be replaced,

wherein R is selected from H, straight-chain or branched alkyl having 1 to 20 carbon atoms,

wherein R ^{3 'is} H or -CH ₂ OH and wherein R ^{3 is} H.

3. Use according to claim 1 or 2, characterized in that in the compounds of formula (I) or (II) the radical X is O.

4. Use according to claim 1 or 2, characterized in that compounds of the formula I are used.

5. Use according to one or more of claims 1 to 4, characterized in that in the compounds of formula (I) or (II) the radical R ^{1 is} selected from the group of branched or straight-chain, saturated or unsaturated alkyl having 1 to 20 Carbon atoms, wherein the saturated alkyl group may be preferably substituted with OH, and the unsaturated alkyl group may be preferably substituted with phenyl substituted by Oalkyl, and saturated, partially or fully unsaturated cycloalkyl having 3-7

Carbon atoms which may be substituted with saturated alkyl groups having 1 to 8 carbon atoms or OR and wherein one or two carbon atoms may be replaced by the heteroatoms and / or atomic groups -N =, NR or -C (O).

6. Use according to one or more of claims 1 to 5, characterized in that in the compounds of formula (I) or (II) the radical R ^{2 is} selected from the group of branched or straight-chain alkyl having 1-20 carbon atoms, which by NR ₂ may be substituted, wherein R is selected from H, straight-chain or branched alkyl having 1 to 20

Carbon atoms.

7. compounds selected from the group consisting of dihydroxyacetone-ortho- (2-dimethylamino-ethyl) -acetate, dihydroxyacetone-ortho-ethyl-lactate, dihydroxyacetone-ortho-ethyl-ectoine,

Dihydroxyacetone ortho-ethyl-pyrrolidone carbonate,

Dihydroxyacetone ortho- (2-dimethylamino-ethyl) lactate,

Dihydroxyacetone ortho- (2-dimethylamino-ethyl) -ectoin,

Dihydroxyacetone-ortho- (2-dimethylamino-ethyl) -pyrrolidone carbonate, 2- (2-ethylhexyloxy) -2-methyl- [1,3] dioxan-5-one,

2-isopropoxy-2-methyl- [1,3] dioxan-5-one,

2-hexyloxy-2-methyl- [1,3] dioxan-5-one,

2-methyl-2-octyloxy [1,3] dioxan-5-one,

2-decyloxy-2-methyl- [1,3] dioxan-5-one, 2-dodecyloxy-2-methyl- [1,3] dioxan-5-one,

2-methyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2-methyl- [1,3] dioxan-5-one,

2-methyl-2-octadecyloxy [1,3] dioxan-5-one,

2-Ethoxy-2- (1-ethyl-pentyl) - [1,3] dioxan-5-one, 2- (2-ethyl-hexyloxy) -2- (1-ethyl-pentyl) - [1, 3] dioxane-5-one,

2- (2-dimethylamino-ethoxy) -2- (1-ethylpentyl) - [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-isopropoxy [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-hexyloxy-2- [1,3] dioxan-5-one, 2- (1-ethylpentyl) -2-octyloxy- [1,3] dioxan-5-one,

2-decyloxy-2- (1-ethylpentyl) - [1,3] dioxan-5-one,

2-Dodecyloxy-2- (1-ethyl-pentyl) - [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-tetradecyloxy [1,3] dioxan-5-one, 2- (1-ethylpentyl) -2-hexadecyloxy- [1,3] dioxan-5-one,

2- (1-ethylpentyl) -2-octadecyloxy [1,3] dioxan-5-one,

2-ethoxy-2-heptyl- [1,3] dioxan-5-one,

2- (2-ethyl-hexyloxy) -2-heptyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-heptyl- [1,3] dioxan-5-one, 2-heptyl-2-isopropoxy - [1,3] dioxan-5-one,

2-heptyl-2-hexyloxy [1,3] dioxan-5-one,

2-heptyl-2-octyloxy [1,3] dioxan-5-one,

2-decyloxy-2-heptyl [1,3] dioxan-5-one,

2-dodecyloxy-2-heptyl- [1,3] dioxan-5-one, 2-heptyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2-heptyl [1,3] dioxan-5-one,

2-heptyl-2-octadecyloxy [1,3] dioxan-5-one,

2-ethoxy-2-nonyl- [1,3] dioxan-5-one,

2- (2-ethylhexyloxy) -2-nonyl- [1,3] dioxan-5-one, 2- (2-dimethylamino-ethoxy) -2-nonyl- [1,3] dioxan-5-one,

2-isopropoxy-2-nonyl- [1,3] dioxan-5-one,

2-hexyloxy-2-nonyl- [1,3] dioxan-5-one,

2-nonyl-2-octyloxy [1,3] dioxan-5-one,

2-decyloxy-2-nonyl- [1,3] dioxan-5-one, 2-dodecyloxy-2-nonyl- [1,3] dioxan-5-one,

2-nonyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2-nonyl- [1,3] dioxan-5-one,

2-nonyl-2-octadecyloxy [1,3] dioxan-5-one, 2-ethoxy-2-undecyl- [1,3] dioxan-5-one,

2- (2-ethyl-hexyloxy) -2-undecyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-undecyl- [1,3] dioxan-5-one,

2-isopropoxy-2-undecyl [1, 3] dioxan-5-one,

2-hexyloxy-2-undecyl- [1,3] dioxan-5-one, 2-octyloxy-2-undecyl- [1,3] dioxan-5-one,

2-decyloxy-2-undecyl [1, 3] dioxan-5-one,

2-dodecyloxy-2-undecyl- [1,3] dioxan-5-one,

2-tetradecyloxy-2-undecyl [1, 3] dioxan-5-one,

2-hexadecyloxy-2-undecyl- [1,3] dioxan-5-one, 2-octadecyloxy-2-undecyl- [1,3] dioxan-5-one,

2-ethoxy-2-tridecyl [1,3] dioxan-5-one,

2- (2-ethylhexyloxy) -2-tridecyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-tridecyl- [1 ₎ 3] dioxan-5-one,

2-isopropoxy-2-tridecyl- [1,3] dioxan-5-one, 2-hexyloxy-2-tridecyl- [1,3] dioxan-5-one,

2-octyloxy-2-tridecyl [1,3] dioxan-5-one,

2-decyloxy-2-tridecyl [1,3] dioxan-5-one,

2-dodecyloxy-2-tridecyl [1,3] dioxan-5-one,

2-tetradecyloxy-2-tridecyl [1,3] dioxan-5-one, 2-hexadecyloxy-2-tridecyl [1,3] dioxan-5-one,

2-octadecyloxy-2-tridecyl [1,3] dioxan-5-one,

2-ethoxy-2-pentadecyl [1,3] dioxan-5-one,

2- (2-ethyl-hexyloxy) -2-pentadecyl- [1,3] dioxan-5-one, 2- (2-dimethylamino-ethoxy) -2-pentadecyl- [1,3] dioxan-5-one,

2-isopropoxy-2-pentadecyl [1,3] dioxan-5-one,

2-hexyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-octyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-decyloxy-2-pentadecyl- [1,3] dioxan-5-one, 2-dodecyloxy-2-pentadecyl- [1,3] dioxan-5-one,

2-pentadecyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-octadecyloxy-2-pentadecyl [1,3] dioxan-5-one,

2-ethoxy-2-heptadecyl- [1,3] dioxan-5-one, 2- (2-ethylhexyloxy) -2-heptadecyl- [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2-heptadecyl [1,3] dioxan-5-one,

2-isopropoxy-2-heptadecyl [1,3] dioxan-5-one,

2-hexyloxy-2-heptadecyl [1,3] dioxan-5-one,

2-heptadecyl-2-octyloxy [1,3] dioxan-5-one, 2-decyloxy-2-heptadecyl [1,3] dioxan-5-one,

2-dodecyloxy-2-heptadecyl [1,3] dioxan-5-one,

2-heptadecyl-2-tetradecyloxy [1,3] dioxan-5-one,

2-heptadecyl-2-hexadecyloxy [1,3] dioxan-5-one,

2-heptadecyl-2-octadecyloxy [1,3] dioxan-5-one, 2-ethoxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2- (2-Dimethylamino-ethoxy) -2 - [(E) -2- (4-methoxyphenyl) -vinyl] - [1,3] dioxan-5-one,

2-isopropoxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2-hexyloxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2 - [(E) -2- (4-Methoxy-phenyl) -vinyl] -2-octyloxy- [1,3-dioxan-5-one, 2-decyloxy-2 - [(E) -2- (4 -methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2-Dodecyloxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2 - [(E) -2- (4-methoxyphenyl) vinyl] -2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2 - [(E) -2- (4-methoxy-phenyl) -vinyl] - [1,3] dioxan-5-one,

2 - [(E) -2- (4-Methoxy-phenyl) -vinyl] -2-octadecyloxy- [1,3-dioxan-5-one, 2-ethoxy-2- (2-hydroxy-phenyl) - [ 1, 3] dioxan-5-one,

2- (2-ethylhexyloxy) -2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2- (2-dimethylamino-ethoxy) -2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2-isopropoxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2-hexyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2- (2-hydroxy-phenyl) -2-octyloxy- [1,3-dioxan-5-one]

2-decyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2-Dodecyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one,

2- (2-Hydroxy-phenyl) -2-tetradecyloxy [1,3] dioxan-5-one,

2-hexadecyloxy-2- (2-hydroxy-phenyl) - [1,3] dioxan-5-one, 2- (2-hydroxy-phenyl) -2-octadecyloxy- [1,3] dioxan-5-one.

8. Compound 2,10-Diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxadispiro [4.2.4.2] tetradecane.

9. compounds selected from erythrulose 1, 3-ortho-ethyl-acetate,

Erythrulose 1, 3-ortho- (2-dimethylamino-ethyl) -acetate, erythrulose-1,3-ortho-ethyl-lactate.

10. compounds selected from dihydroxyacetone-ortho-thio (2-dimethylamino-ethyl) -lactate, dihydroxyacetone-ortho-thio-ethyl-acetate,

Dihydroxyacetone ortho-thio-ethyl lactate.

11. A preparation containing at least one compound of the formula (I)

or

where the radicals are defined as follows:

X O, S or NR,

wherein R ¹ and R ² are the same or different,

these groups having saturated and / or unsaturated alkyl groups having 1 to 8 carbon atoms, OR, NR ₂ , saturated, partially or completely unsaturated by OH or OAlkyl 1-8

Carbonyl-substituted cycloalkyl of 3-7 carbon atoms may be substituted,

where one or two carbon atoms in these groups are represented by the heteroatoms and / or atomic groups -O-, -N =, Nr, -C (O) -,

-C (O) O- and / or -C (O) NH- can be replaced,

wherein R ^{3 is} H or -CH ₂ OH and wherein R ^{3 is} H.

12. A preparation according to claim 11, characterized in that the preparation contains the at least one derivative of the formula (I) or the at least one dimer derivative of the formula (II) in a total amount of 0.01 to 10 wt .-%.

13. A preparation according to claim 11 or 12, characterized in that it contains at least one flavonoid and / or a formaldehyde scavenger.

14. Preparation according to one or more of claims 11 to 13, characterized in that it contains further self-tanning substances.

15. Preparation according to one or more of claims 11 to 14, characterized in that it contains one or more antioxidants, one or more vitamins and / or one or more UV filters.

16. A process for the preparation of a preparation as claimed in one or more of claims 11 to 15, wherein at least one compound of the formula (I) or at least one compound of the formula (II) is mixed with a carrier suitable for topical applications.