DE102007041854A1 - Bifunctional DHA derivatives - Google Patents

Abstract

The invention relates to bifunctional derivatives of dihydroxyacetone and its dimeric compounds, a process for their preparation, preparations containing these derivatives, and their use u. a. for browning of the skin.

Description

The The present invention relates to bifunctional dihydroxyacetone derivatives and their dimers, a process for their preparation, preparations containing these derivatives as well as their use for browning of the skin.

Of the Trend away from the noble paleness towards the "healthy, sporty brown skin "has been unbroken for years people are exposing their skin to sunlight, as this causes pigmentation through melanin formation. However, the UV radiation of sunlight also has a harmful Effect on the skin. In addition to the acute injury (sunburn) Long-term damage occurs when excessive Irradiation with light from the UVB range (wavelength 280-320 nm), such as an elevated one Risk of developing skin cancer. The excessive Influence of UVB and UVA radiation (wavelength: 320-400 nm) leads to a weakening the elastic and collagen fibers of the connective tissue. this leads to to numerous phototoxic and photoallergic reactions and causes premature aging of the skin.

The natural protection against the negative effects of solar radiation provides the tanning (pigmentation) of the skin. The epidermis contains in its lowest layer, the basal layer, beside the basal cells individual pigment-forming cells, the melanocytes. UV light causes the production of melanin in these cells stimulated, which transports into the kerantinocytes (horny cells) and there is visible as a brown skin color. This from the amino acid Tyrosine emanating pigmentation is predominantly through UVB radiation initiated and called "indirect pigmentation" designated. Their development runs over several days; the suntan so obtained is over some weeks. In the "direct pigmentation" with the the sun's rays are predominantly colorless melanin precursors oxidized by UVA radiation to dark colored melanin. Since this oxidation is reversible, it leads to a only short-lasting tanning of the skin.

A Artificial tanning of the skin can be externally with the help of make-up and orally by taking carotenoids produce.

much more popular, however, is the artificial tanning of Skin, which is characterized by applying so-called self-tanner achieve. These compounds indicate as chemical Structural feature keto or aldehyde groups in the vicinity of alcohol functions on. These ketols or aldols belong predominantly to the substance class of sugar.

The Compounds can interact with the proteins and amino acids the horny layer of the skin reacted in the sense of a Maillard reaction Beyond one is not complete enlightened pathway polymers are formed, the Give the skin a brownish hue. This reaction is completed in about 4 to 6 hours. The tan thus achieved is not washable and is only with the normal Hautabschuppung away.

Of the Of course, the prior art knows a variety various self-tanning substances. A particularly common used self-tanning substance is 1,3-dihydroxyacetone (DHA). This is a water-soluble crystalline solid which is under neutral to basic conditions is not stable. This instability also goes with the Development of cosmetically undesirable off-odors associated.

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

It there is still a need for skin-friendly self-tanning substances, which are also used in cosmetic and dermatological preparations suitable.

task The present invention is therefore, alternative substances to provide a tanning effect exhibit. In particular, self-tanning substances should be prepared under neutral to basic conditions are stable. In addition, by the use of more stable derivatives the development of cosmetically undesirable off-odors be avoided.

oder dessen dimeren Derivat der allgemeinen Formel (II)

This object is achieved by providing a bifunctional derivative of the dihydroxyacetone according to the general formula (I)

or its dimeric derivative of the general formula (II)

Where:
XO, S or NR,
wherein R is selected from H, alkyl and aryl of 1 to 20 carbon atoms
R ¹ , R ² , R ³ H,
straight-chain or branched alkyl having 1-20 carbon atoms which may contain one or more double bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 carbon atoms
wherein R ¹ , R ² and R ³ are the same or different,
where these groups may be substituted with further saturated and / or unsaturated alkyl, saturated, partially or completely unsaturated cycloalyl and / or heteroatom substituents in different positions,
wherein one or two carbon atoms in these groups may be replaced by the heteroatoms and / or atomic moieties -O-, -N =, -C (O) -, -C (O) O- and / or -C (O) NH- .
where R ^{2 is} not methyl
and wherein the two R ³ in the dimer derivative of the general formula (II) are substituted on two of the four ring methylene groups.

Under fully unsaturated compounds or substituents and groups also become aromatic for the purposes of the present invention Compounds or aromatic substituents understood.

The compounds according to the invention are formally condensation products of dihydroxyacetone or of a dihydroxyacetone substituted by R ³ with a carboxylic acid and an alcohol.

For the purposes of the present invention, the dimeric derivatives of the general formula (II) are those compounds in which the two substituents R ^{3 are distributed} as follows over the four methylene ring groups, or a mixture thereof:

The Compounds of the invention are characterized from being stable with increasing ambient pH win while other self-tanner such. B. DHA or erythrulose lose stability with increasing pH. Therefore, compounds of the invention provide the Advantage to be used in pH ranges where other self-tanner already subject to decomposition. Especially in the pH range 5 to 8 particularly preferred in the range of 6.0 and 7.5 are inventive Compounds more stable than other self-tanner. Especially There is the advantage that by avoiding the decomposition negative properties be avoided, such. B. the development of malodor DHA decomposition, which also leads to loss of active substance and skin irritation can lead. Your coloring or tanning Effect occurs only by molecular cleavage under physiological acidic conditions (eg after skin application, pH of the skin approx. 5), by enzymes or by amino groups in the sense of the Maillard reaction catalyzes. The fact that it is in the inventive Compounds of oil-soluble self-tanning substances acting brings advantages over other water-soluble ones Self-tanning substances such. Eg DHA. The in the oil phase and not the water phase dissolved inventive Self-tanning substances are thus more stable oxidative or hydrolytic degradation. It also comes by a combination of the inventive oil-soluble Self tanning substances with other water soluble Self-tanning substances such. B. DHA too synergistic Effects on the tanning result of the skin.

in the Compared to known self-tanning substances possess the derivatives of the invention in addition to a self-tanning component at least one second active ingredient in the case of molecular cleavage is freestezt and to a significant benefit of the invention Substance leads.

Further the derivatives of the invention are relatively easy produced.

The derivatives of the formula (I) and (II) according to the invention are capable of causing a skin coloration or a tanning of the skin on or in the skin. Through the acidic skin pH (about 4.5 to 5.5) and / or Enzmye (eg, lipases or the like) and / or amino groups (eg, contained in peptides or amino acids such as lysine) the compound of the invention cleaved and it will be released in addition to the self-tanning substance other active ingredients. As a self-tanner acts dihydroxyacetone or its at the methylene bridge with R ³ substituted derivative. By forming a covalent bond to proteins of the horny layer of the skin (Maillard reaction) it comes to skin tanning.

Of the Term self-tanner is synonymous in the context of this invention also as a self-tanning substance or self-tanning substance used.

The nature of the other released active ingredients is "controllable" via the radicals R ¹ and R ² : From R ¹ , the cleavage of the compounds (I) and / or (II) according to the invention generally results in the carboxylic acid R ¹ -COOH, from R ² , the compound R ² -XH is formed Alternatively, in the case of acid hydrolysis or enzymatically or amino-catalyzed cleavage of the compounds (I) and / or (II) according to the invention, the carboxylic acid derivatives R ¹ -C (O) -XR ² arise.

These further released active ingredients may, for example, have the following effects: preserving action (for example acetic acid, para-hydroxybenzoic acid esters, benzoic acid, salicylic acid, Sor bainic acid), preservative or cooling action (eg ethanol), regulation of skin hydration / moisturizers (eg lactic acid, pyrrolidonecarboxylic acid, amino acids), "immediate lifting effect" (eg dimethylethanolamine), "natural cell protection effect "(eg Ectoin). In addition, as other releasable active ingredients all known substances in question, which are also used as moisturizers, moisturizers, UV filters (eg Ethylhexyl Methoxycinnamate, Octrocrylene, diethylamino hydroxybenzoyl hexyl benzoates, ethylhexyl salicylates), preservatives, dyes, self-tanner, Tanning agents, skin whitening agents, peptides, anti-aging agents (eg 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, inter alia, 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 (cf. Fey, Otte, Dictionary of Cosmetics, 3rd edition, 1991 ).

Without limiting the generality, examples of bifunctional derivatives of dihydroxyacetone according to the invention are:

Preferably has the radical X in the bifunctional derivatives of dihydroxyacetone the meaning O.

The substituent R ³ is in preferred bifunctional derivatives of dihydroxyacetone according to the invention H or - (CHOH) _n -CH ₂ OH, where n is an integer and 0 ≤ n ≤ 5.

Most preferably, the substituent R ^{3 is} H or -CH ₂ OH, ie in the hydrolytic or enzymatic cleavage of the compound according to the invention very particularly preferably arise dihydroxyactone (DHA) or erythrulose.

In inventively preferred compounds (I) and / or (II), the substituents R ¹ and / or R ^{2 are} independently selected from the group
-H, - (CH ₂ ) _o CH ₃ , - (CH ₂ ) _n NH ₂ , - (CH ₂ ) _n N ((CH ₂ ) _o CH ₃ ) ((CH ₂ ) _p CH ₃ ), - (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) -O-R ', -C ₆ H ₆ -CH ₂ CHNR'COOR', -CH ₂ CHNR'COOR ',
where n is an integer and selected from the range 1 to 20,
where o and p are independently an integer and selected from the range 0 to 20,
wherein Ar is an aryl group and may be substituted with further aryl, alkyl and / or heteroatom substituents in different positions,
wherein the radicals R 'are independently selected from H, amino acid residue and peptide residue
and wherein R ^{2 is} not -CH ₃ .

Particularly preferably, the substituent R ^{1 of} the bifunctional derivative of the DHA is selected from the group aminocarboxylic acid radical, carboxylic acid radical, branched or straight-chain, saturated or unsaturated alkyl having 2 to 20 carbon atoms and saturated, partially or completely unsaturated cycloheteroalkyl having 5 to 7 ring atoms,
where the alkyl and the cycloheteroalkyl may be substituted with further aryl, alkyl and / or heteroatom substituents, in particular hydroxyl and / or amino groups, in different positions.

The substituent R ^{1 of} the bifunctional derivative of the DHA is very particularly preferably selected from the group -CH ₃ , -CHOH-CH ₃ , pyrrolidonecarboxylic acid radical, ecto-carboxylic acid radical and aminocarboxylic acid radical.

The substituent R ^{2 of} the bifunctional derivative of the DHA is particularly preferably selected from the group of a physiologically and / or dermatologically tolerated alcohol R ² -OH or a physiologically and / or dermatologically acceptable aminoalcohol R ² -OH,
wherein the radical R ^{2 is} a branched or straight-chain, saturated or unsaturated alkyl or aminoalkyl having 2 to 20 carbon atoms, which may be substituted with further aryl, alkyl and / or heteroatom substituents in different positions.

Most preferably, the substituent R ^{2 of} the bifunctional derivative of the DHA is selected from the group -C ₂ H ₅ or -C ₂ H ₄ N (CH ₃ ) ₂ .

Preferably is the bifunctional derivative of the invention of the dihydroxyactone selected from the group dihydroxyacetone-ortho-ethyl acetate, Dihydroxyacetone-ortho- (2-dimethylamino) -ethylacetate, dihydroxyacetone-ortho-ethyl-lactate, Dihydroxyacetone-ortho-ethyl-ectoine and dihydroxyacetone-ortho-ethyl-pyrrolidone carbonate or its dimers.

One second subject of the present invention is a method for the preparation of the compounds according to the invention.

It it was found that the compounds of the invention can be easily synthesized under mild conditions. The derivatives of the invention are with good Isolated yields.

mit katalytischen Mengen (+/–)-Campher-10-sulfonsäure (oder anderen sauren Katalysatoren wie z. B. para-Toluolsulfonsäure oder polymeren, sauren Katalysatoren) monomerisiert. Anschließend wird mit einem Ortho-Ester der allgemeinen Formel (IV)

umgesetzt.For the preparation of the monomeric bifunctional derivatives of general formula (I) according to the invention, dihydroxyacetone or a dihydroxyacetone of general formula (III) substituted with R ^{3 is} firstly used for this purpose.

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

implemented.

mit katalytischen Mengen (+/–)-Campher-10-sulfonsäure (oder anderen sauren Katalysatoren wie z. B. para-Toluolsulfonsäure oder polymeren, sauren Katalysatoren) und mit einem Ortho-Ester der allgemeinen Formel (IV)

hergestellt.The dimeric bifunctional derivatives of the general formula (II) according to the invention are obtained by reacting dimeric dihydroxyacetone or a dimeric dihydroxyacetone substituted by R ³ of general formula (V)

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

produced.

The heteroatoms X and the substituents R ¹ , R ² and R ^{3 of} the general formula (IV) or (V) are defined in both methods as those in the general formulas (I) and (II).

Prefers Monomerization of the dimeric starting material takes place in the preparation the monomeric derivatives according to the invention at 50 to 100 ° C within about 2 hours. The subsequent Reaction with the compound of general formula (IV) finds preferably within 6 to 48 hours at 50 to 100 ° C instead.

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

purification The compound of the invention takes place in each case by distillation and / or crystallization.

One Another object of the present invention is the use the compound of the formula (I) and / or the Formula (II), as indicated above, for the preparation of a cosmetic Preparation or dermatological preparation intended for artificial Browning and / or browning of the skin are determined.

About that addition, the use of the compound of formula (I) and / or of the formula (II) as a browning agent, as a UV filter, as Preservative, for lifting the skin and for the production a cosmetic and / or dermatological preparation with light protection properties Subject of the present invention.

The Use of the compound of the formula (I) and / or the formula (II) in pharmaceutical and / or cosmetic Preparations or in household products is also an object of the present invention.

Another object of the present invention are preparations containing at least one bifunctional derivative of the dihydroxyacetone of the general formula (I) and / or at least one dimeric bifunktio nelles derivative of dihydroxyacetone of the general formula (II).

at The preparations are usually around topically applicable preparations, for example cosmetic or dermatological formulations. The preparations included in this case a cosmetically or dermatologically suitable carrier and depending on the desired property profile optionally further suitable ingredients. Is it pharmaceutical preparations, so the preparations in this case contain a pharmaceutical compatible carrier and optionally further pharmaceutical Agents. Is it a dietary supplement, so choose a suitable carrier.

These it is in the preparations to perfumes, so it is in a variant of the invention preferred when in addition to the perfumes or perfume oils and the flavonoids and typical carriers, such as water, Solvents, such as alcohols, oils and possibly emulsifiers no further aids are included.

in the The meaning of the present invention is in addition to the term preparation synonymous, the term mean or formulation used.

All Compounds or components used in the preparations can be either known or for sale Acquired or can be synthesized by known methods become.

Further preferred combinations of embodiments are in disclosed in the claims.

In preferred embodiments, the at least one bifunctional derivative of dihydroxyacetone of the general formula (I) and / or the at least one dimeric bifunctional derivative of Dihydroxyacetones of the general formula (II) in the inventive Preparations typically in amounts of 0.01 to 10 wt .-%, preferably in amounts of 0.1 wt .-% to 5 wt .-% and particularly preferably in Amounts of 0.5 to 2 wt .-%, used. It prepares the expert no difficulty the quantities depending on the intended Select the effect of the preparation accordingly.

In the described preparations, according to the invention at least a bifunctional derivative of the dihydroxyacetone of the general Formula (I) and / or at least one dimeric bifunctional derivative of the dihydroxyacetone of the general formula (II) Furthermore, pigments may be included, the layer structure the pigments is not limited.

Preferably should the color pigment at a rate of 0.5 to 5 wt .-% skin colors or brownish. The selection of a corresponding pigment is familiar to the skilled person.

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 the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971 taken. Chemical or other name CIN colour Pigment Green 10006 green Acid Green 1 10020 green 2,4-Dinitrohydroxynaphthalin-7-sulfonic acid 10316 yellow Pigment Yellow 1 11680 yellow Pigment Yellow 3 11710 yellow Pigment Orange 1 11725 orange 2,4-dihydroxyazobenzene 11920 orange Solvent Red 3 12010 red 1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene 12085 red Pigment Red 3 12120 red Ceresrot; Sudan Red; Fat Red G 12150 red Pigment Red 112 12370 red Pigment Red 7 12420 red Pigment Brown 1 12480 brown 4- (2'-methoxy-1'-phenylazo-5'sulfonsäurediethylamid) -3-hydroxy-5 '' - chloro-2 '', 4 '' - dimethoxy-2-naphthoic acid anilide 12490 red Disperse Yellow 16 12700 yellow 1- (4-Sulfo-1-phenylazo) -4-aminobenzene-5-sulfonic acid 13015 yellow 2,4-dihydroxy-azobenzene-4'-sulfonic acid 14270 orange 2- (2,4-Dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene-4-sulfonic acid 14700 red 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid 14720 red 2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid 14815 red 1- (4'-sulfophenylazo) -2-hydroxynaphthalene 15510 orange 1- (2-sulfonic acid 4-chloro-5-carboxylic acid-1-phenylazo) -2-hydroxynaphthalene 15525 red 1- (3-methyl-phenylazo-4-sulfonic acid) -2-hydroxynaphthalene 15580 red 1- (4 ', (8') - Sulfosäurenaphthylazo) -2-hydroxynaphthalene 15620 red 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid 15630 red 3-hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid 15850 red 1- (2-sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxynaphthalene-3-carboxylic acid 15865 red 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid 15880 red 1- (3-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15980 orange 1- (4-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15985 yellow Allura Red 16035 red 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid 16185 red Acid Orange 10 16230 orange 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid 16255 red 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6,8-trisulfonic acid 16290 red 8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red Acid Red 1 18050 red Acid Red 155 18130 red Acid Yellow 121 18690 yellow Acid Red 180 18736 red Acid Yellow 11 18820 yellow Acid Yellow 17 18965 yellow 4- (4-Sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxy-pyrazolone-3-carboxylic acid 19140 yellow Pigment Yellow 16 20040 yellow 2,6- (4'-sulfo-2 '', 4 '' - dimethyl) bis-phenylazo) 1,3-dihydroxybenzene 20170 orange Acid Black 1 20470 black Pigment Yellow 13 21100 yellow Pigment Yellow 83 21108 yellow Solvent Yellow 21230 yellow Acid Red 163 24790 red Acid Red 73 27290 red 2- [4 '- (4''-sulfo-1''- phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-7-aminonaphthalene-3,6-disulfonic acid 27755 black 4- [4 '' - sulfo-1 '' - phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-8-acetyl-aminonaphthalene-3,5-disulfonic acid 28440 black Direct Orange 34, 39, 44, 46, 60 40215 orange Food Yellow 40800 orange trans-β-apo-8'-carotenaldehyde (C ₃₀ ) 40820 orange trans-apo-8'-carotenoic acid (C ₃₀ ) ethyl ester 40850 orange canthaxanthin 40850 orange Acid Blue 1 42045 blue 2,4-disulfo-5-hydroxy-4'-4 '' - bis (diethylamino) triphenyl-carbinol 42051 blue 4 - [(- 4-N-ethyl-p-sulfobenzylamino) -phenyl- (4-hydroxy-2-sulfophenyl) - (methylene) -1- (N-ethylN-p-sulfobenzyl) -2,5-cyclohexadienimine] 42053 green Acid blue 7 42080 blue (N-ethyl-p-sulfobenzyl-amino) -phenyl- (2-sulfophenyl) -methylene- (N-ethyl-N, p-sulfo-benzyl) Δ ^2,5- cyclohexadiene imine 42090 blue Acid Green 9 42100 green Diethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methyl-fuchsonimmonium 42170 green Basic Violet 14 42510 Violet Basic Violet 2 42520 Violet 2'-methyl-4 '- (N-ethyl-Nm-sulfobenzyl) amino-4''- (N-diethyl) amino-2-methyl-N-ethyllN-m-sulfobenzyl-fuchsonimmonium 42735 blue 4 '- (N-Dimethyl) amino-4''- (N-phenyl) -aminonaphtho-N-dimethylfuchsonimmonium 44045 blue 2-hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmonium 44090 green Acid Red 52 45100 red 3- (2'-methylphenylamino) -6- (2'-methyl-4'-sulfophenylamino) -9- (2 '' - carboxyphenyl) -xantheniumsalz 45190 Violet Acid Red 50 45220 red Phenyl-2-oxyfluoron-2-carboxylic acid 45350 yellow 4.5-Dibromofluorescein 45370 orange 2,4,5,7-Tetrabromfluorescein 45380 red Solvent dye 45396 orange Acid Red 98 45405 red 3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromfluorescein 45410 red 4.5-Diiodfluorescein 45425 red 2,4,5,7-tetraiodofluorescein 45430 red quinophthalone 47000 yellow Quinophthalone disulphonic 47005 yellow Acid Violet 50 50325 violet Acid Black 2 50420 black Pigment Violet 23 51319 violet 1,2-dioxyanthraquinone, calcium-aluminum complex 58000 red 3-Oxypyren-5,8,10-sulfonic acid 59040 green 1-hydroxy-4-N-phenyl-aminoanthraquinone 60724 violet 1-hydroxy-4- (4'-methylphenylamino) anthraquinone 60725 violet Acid Violet 23 60730 violet 1,4-di (4'-methylphenylamino) anthraquinone 61565 green 1,4-bis (o-sulfo-p-toluidino) anthraquinone 61570 green Acid Blue 80 61585 blue Acid Blue 62 62045 blue N, N'-dihydro-1,2,1 ', 2'-anthrachinonazin 69800 blue Vat Blue 6; Pigment Blue 64 69825 blue Vat Orange 7 71105 orange indigo 73000 blue Indigo-disulfonic 73015 blue 4,4'-dimethyl-6,6'-dichlorothioindigo 73360 red 5,5'Dichlor-7,7'-dimethylthioindigo 73385 violet Quinacridone Violet 19 73900 violet Pigment Red 122 73915 red Pigment Blue 16 74100 blue phthalocyanines 74160 blue Direct Blue 86 74180 blue Chlorinated phthalocyanines 74260 green Natural Yellow 6, 19; Natural Red 1 75100 yellow Bixin, nor-bixin 75120 orange lycopene 75125 yellow trans-alpha, bet or gamma-carotene 75130 orange Keto and / or hydroxyl derivatives of carotene 75135 yellow Guanine or pearlescing agent 75170 White 1,7-bis (4-hydroxy-3-methoxyphenyl) 1,6-heptadiene-3,5-dione 75300 yellow Complex salt (Na, Al, Ca) of karmic acid 75470 red Chlorophyll a and b; Copper compounds of chlorophylls and chlorophyllins 75810 green aluminum 77000 White alumina hydrate 77002 White Water-containing aluminum silicates 77004 White ultramarine 77007 blue Pigment Red 101 and 102 77015 red barium sulfate 77120 White Bismuth oxychloride and its mixtures with mica 77163 White calcium carbonate 77220 White calcium sulphate 77231 White carbon 77266 black Pigment Black 9 77267 black Carbo medicinalis vegetabilis 77268 black :1 chromium 77288 green Chromium oxide, hydrous 77278 green Pigment Blue 28, Pigment Green 14 77346 green Pigment Metal 2 77400 brown gold 77480 brown Iron oxides and hydroxides 77489 orange iron oxide 77491 red iron oxide 77492 yellow iron oxide 77499 black Mixtures of iron (II) and iron (III) hexacyahoferrate 77510 blue Pigment White 18 77713 White Mangananimoniumdiphosphat 77742 violet Manganese phosphate; Mn ₃ (PO ₄ ) ₂ .7H ₂ O 77745 red silver 77820 White Titanium dioxide and its mixtures with mica 77891 White zinc oxide 77947 White 6,7-dimethyl-9- (1'-D-ribityl) -isoalloxazine, lactoflavin yellow caramel brown Capsanthin, Capsorubin orange betanin red Benzopyrylium salts, anthocyanins red Aluminum, zinc, magnesium and calcium stearate White Bromthymolblau blue

• 1. natürliche Perlglanzpigmente, wie z. B. • "Fischsilber" (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und • "Perlmutt" (vermahlene Muschelschalen)
• 2. monokristalline Perlglanzpigmente wie z. B. Bismuthoxychlorid (BiOCl)
• 3. Schicht-Substrat Pigmente: z. B. Glimmer/Metalloxid

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

Base for pearlescent pigments are, for example, powdery 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. B. that under the CIN 77163 listed luster pigment.

Also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide: group Coating / colour Silver-white pearlescent pigments TiO ₂ : 40-60 nm silver interference pigments TiO ₂ : 60-80 nm yellow TiO ₂ : 80-100 nm red TiO ₂ : 100-140 nm blue TiO ₂ : 120-160 nm green Color Luster Pigments Fe ₂ O ₃ bronze Fe ₂ O ₃ copper Fe ₂ O ₃ red Fe ₂ O ₃ rotviolett Fe ₂ O ₃ Red Green Fe ₂ O ₃ black combination pigments TiO ₂ / Fe ₂ O ₃ gold tones TiO ₂ / Cr ₂ O ₃ green TiO ₂ / Berlin Blue deep blue

Particular preference is z. For example, the pearlescent pigments available from Merck under the trade names Timiron® ^®, Colorona® ^®, Dichrona® ^{®, ®} or Xirona 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 TiO ₂ and Fe ₂ O 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 are prepared using SiO ₂ . 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 effect pigments which are obtainable under the trade name Metasomes ^® Standard / glitter in different 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 (CI) numbers 19140, 77007, 77289, 77491).

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

preparations with self-tanning properties, especially those that Dihydroxyacetone contain or - as in the present Invention - release tend in the application to the human skin to malodors, presumably through Degradation products of dihydroxyacetone itself or by products of side reactions caused and users sometimes uncomfortable be felt. It has been shown that these malodors when using formaldehyde scavengers and / or flavonoids be avoided. Therefore, the inventive Preparation also formaldehyde scavengers and optionally Flavonoids to improve the odor on the skin.

Preferably the formaldehyde scavenger is selected from Group of alkali metal, alkaline earth metal or ammonium bisulfite. Especially preference is given to a preparation which, as an odor improver, is 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.

The optionally in the preparation according to the invention existing flavonoid acts additionally as a stabilizer for the self-tanner or self-tanning substances and / or reduces or avoids stock-dependent off-odors.

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-sulfate or flavonoid-phosphate, such as preferably rutinsulfates, as a particularly suitable flavonoids proved. Particularly preferred in the sense of the invention Uses are rutin sulfate and troxerutin. Very particularly preferred is the use of troxerutin.

The inventively preferred flavonoids have a non-positively charged Flavangrundkörper. It is believed that by these flavonoids metal ions such. B. Fe ^{2 +} / Cu ^{2+ be} complexed and so auto-oxidation processes in perfumes or compounds whose degradation leads to malodors, prevented or reduced.

Especially preferred is a preparation in addition to the inventive Compounds of the formulas (I) and / or (II) DHA Rapid and sodium bisulfite contain.

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 whose content in this regard expressly also belongs to the disclosure content of the present application.

The inventive preparation can about In addition, preferably also contain further active ingredients, such as Example of repellents, in particular insect repellents, UV filters, Flavone derivatives, chromone derivatives, aryloximes and parabens.

The Most repellent agents belong to the substance classes of Amides, alcohols, esters and ethers. Repellents should usually meet the following conditions: you are allowed do not evaporate too quickly and do not penetrate the skin. she should not be primarily irritating to the skin either They also have a sensitizing effect and should not be toxic be. Their effectiveness must also be 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, dimethyl carbate, di-n-propyl isocine chomeronate, (R) -p-mentha-1,8-diol, 2-ethylhexane-1,3-diol, N-octyl-bi-cyclohepetene-di-carboximide, piperonyl-butoxide, 1- (2 -Methylpropyloxycarbonyl) -2- (hydroxyethyl) -piperidine (Bayrepel ^®; Bayer) or mixtures thereof, and it is particularly preferably selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butylamino) -propionic acid. ethyl ester, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures thereof.

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

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, for example wise from the German publication DE 41 16 123 known. 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 z. B. for the treatment of psoriasis, different types of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages can be used. 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. According to the invention, flavonoids are the glycosides of flavanones, flavones, 3-hydroxyflavones (= flavonols), aurones, isoflavones and rotenoids [ 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, 4,6,3 ', 4'-tetrahydroxybenzylcoumaranone-3 is preferred.

wobei
R¹ und R² gleich oder verschieden sein können und ausgewählt sind aus

• – H, -C(=O)-R⁷, -C(=O)-OR⁷,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen, geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,

R³ steht für H oder geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen,
R⁴ steht für H oder OR⁸,
R⁵ und R⁶ gleich oder verschieden sein können und ausgewählt sind aus

• – -H, -OH,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann und

R⁷ steht für H, geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen, eine Polyhydroxy-Verbindung, wie vorzugsweise einen Ascorbinsäurerest oder glycosidische Reste und
R⁸ steht für H oder geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen,
wobei mindestens 2 der Substituenten R¹, R², R⁴-R⁶ verschieden von H sind oder mindestens ein Substituent aus R¹ und R² für -C(=O)-R⁷ oder -C(=O)-OR⁷ steht.Chromone derivatives are preferably understood as meaning certain chromene-2-one derivatives which are useful as active ingredients for the preventive treatment of human skin and hair against aging processes and harmful environmental influences. At the same time they show a low irritation potential for the skin, positively influence the water binding in the skin, 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 ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ - to C ₂₀ -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 furthermore the alkyl chain may also be interrupted by oxygen, and or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3,

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

• - -H, -OH,
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkyl groups, it being possible for the hydroxy group to be bonded to a primary or secondary carbon atom of the chain, and furthermore for the alkyl chain also to be interrupted by oxygen, and

R ⁷ is H, straight or branched C ₁ to C ₂₀ 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 of R ¹ and R ^{2 is} -C (= O) -R ⁷ or -C (= O) -OR ⁷ stands.

Of the Proportion of one or more compounds selected from Chromone derivatives and Coumaranonen in a preparation preferably from 0.001 to 5% by weight, more 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, being of no difficulty to the skilled person to select fast or delayed acting antioxidants.

In a preferred embodiment is therefore in the preparation of a preparation for the protection of body cells against oxidative stress, in particular to reduce skin aging, characterized in that they in addition to the flavonoids and the Self-tanning substances and possibly other ingredients contains one or more antioxidants.

There are many known and proven substances in the literature that can be used as antioxidants, e.g. For example, amino acids (eg, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their Derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), aurothioglucose, Propylthiouracil and other thiols (e.g., thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinsulfoximine, buthionine sulfones , Penta-, hexa-, heptathionine sulfoximine) in very poor compatibility doses (eg. Pmol to μmol / kg), further (metal) chelators (eg, α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g., citric acid, lactic acid, malic acid), humic acid, bile acids , Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E). acetate), vitamin A and derivatives (eg, vitamin A palmitate), benzoic acid coniferyl benzoate, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and their derivatives, mannose and their 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) ,

worin
R¹ aus der Gruppe -C(O)CH₃, -CO₂R³, -C(O)NH₂ und -C(O)N(R⁴)₂ ausgewählt werden kann,
X O oder NH,
R² lineares oder verzweigtes Alkyl mit 1 bis 30 C-Atomen,
R³ lineares oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
R⁴ jeweils ungabhängig voneinander H oder lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen,
R⁵ lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen oder lineares oder verzweigtes Alkoxy mit 1 bis 8 C-Atomen und
R⁶ lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen bedeutet, vorzugsweise Derivate der 2-(4-Hydroxy-3,5-dimethoxybenzyliden)-malonsäure und/oder 2-(4-Hydroxy-3,5-dimethoxybenzyl)-malonsäure, besonders bevorzugt 2-(4-Hydroxy-3,5-dimethoxybenzyliden)-malonsäure-bis-(2-ethylhexyl)ester (z. B. Oxynex^® ST Liquid) und/oder 2-(4-Hydroxy-3,5-dimethoxybenzy)-malonsäure-bis-(2-ethylhexyl)ester (z. B. RonaCare^® AP).Suitable antioxidants are also compounds of the general formulas A or B.

wherein
R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,
X is O or NH,
R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,
R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,
R ^{4 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, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethylhexyl) ester (z. B. Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3, 5-dimethoxybenzy) malonic acid-bis (2-ethylhexyl) ester (z. B. RonaCare ^® AP).

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercially available mixtures are, for example, mixtures tend, 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 (. eg Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) -. ascorbyl palmitate and citric acid (. eg Oxynex ^® 2004) antioxidants are the Compounds of the invention in such compositions usually in weight percent ratios ranging from 1000: 1 to 1: 1000, preferably used 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 mainly known as plant dyes, frequently have an antioxidant potential. To deal with effects of the substitution pattern of mono- and dihydoxy flavones 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 dihydroxyflavones have in part no antioxidant properties exhibit.

Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) is frequently 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, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 investigate the pH dependence of the antioxidant activity of hydroxyflavones. Quercetin shows the highest activity of the investigated structures over the entire pH range.

wobei
R¹ bis R¹⁰ gleich oder verschieden sein können und ausgewählt sind aus

• – H
• – OR¹¹
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
• – wobei alle OR¹¹ unabhängig voneinander stehen für
• – OH
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkyloxygruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenyloxygruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkoxygruppen, wobei die Hydroxygruppe(n) an ein primäre oder sekundäre Kohlenstoffatome der Kette gebunden sein können und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkyloxygruppen und/oder C₃- bis C₁₂-Cycloalkenyloxygruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können und/oder,
• – Mono- und/oder Oligoglycosylreste,

mit der Maßgabe, dass mindestens 4 Reste aus R¹ bis R⁷ stehen für OH und dass im Molekül mindestens 2 Paare benachbarter Gruppen -OH vorliegen,

• – oder R², R⁵ und R⁶ für OH und die Reste R¹, R³, R⁴ und R^7-10 für H stehen, wie sie in der Deutschen Patentanmeldung DE-A-102 44 282 beschrieben sind.

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 ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -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 furthermore the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3,
• Where all OR ^{11 are} independent of each other
• - OH
• Straight-chain or branched C ₁ -C ₂₀ -alkyloxy groups,
• Straight-chain or branched C ₃ - to C ₂₀ -alkenyloxy groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkoxy groups, where the hydroxy group (s) 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 ₁₀ -cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where 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 at least 2 pairs of adjacent groups -OH are present in the molecule,

• 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 the German patent application DE-A-102 44 282 are described.

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 B ₁ ), riboflavin (vitamin B ₂ ), nicotinamide , Vitamin C (ascorbic acid), Vitamin D, Ergocalciferol (Vitamin D ₂ ), Vitamin E, DL-α-Tocopherol, Tocopherol E-acetate, Tocopherol hydrogen succinate, Vitamin K ₁ , 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 may also serve and contain the sunscreen then next to the bifunctional DHA derivatives and / or their dimers as well as the optional other ingredients also UV filters.

• – 2-Cyano-3,3-diphenylacrylsäure-2-ethylhexylester (z. B. Eusolex^® OCR),
• – 3,3'-(1,4-Phenylendimethylen)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-ylmethansulfonsäure sowie ihre Salze (z. B. Mexoryl^® SX) und
• – 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxi)-1,3,5-triazin (z. B. Uvinul^® T 150)
• – 2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoesäure hexylester (z. B. Uvinul^®UVA Plus, Fa. BASF).

In principle, all UV filters are suitable for combination with the DHA derivatives to be used according to the invention. Particularly preferred are those UV filters whose physiological harmlessness has already been demonstrated. For both UVA and UVB filters, there are many well-known and proven substances from the literature, for. B.
Benzylidenecamphor derivatives, such as 3- (4'-methylbenzylidene) -dl-camphor (. For example Eusolex ^® 6300), 3-benzylidenecamphor (. For example Mexoryl ^® SD), polymers of N - {(2 and 4) - [( 2-oxoborn-3-ylidene) methyl] benzyl} acrylamide (z. B. ^® Mexoryl SW), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (z. B. Mexoryl SK ^®) or (2-oxoborn-3-ylidene) toluene-4-sulfonic acid (z. B. Mexoryl SL ^®),
Benzoyl or dibenzoylmethanes, such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (z. B. Eusolex ^® 9020) or 4-isopropyldibenzoylmethane (z. B. Eusolex ^® 8020),
Benzophenones such as 2-hydroxy-4-methoxybenzophenone (z. B. Eusolex ^® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (eg. As Uvinul ^® MS-40),
Methoxycinnamate such as octyl methoxycinnamate (for. Example Eusolex ^® 2292), isopentyl 4-methoxycinnamate, z. B. as a mixture of isomers (eg., Neo Heliopan ^® E 1000),
Salicylate derivatives such as 2-ethylhexyl salicylate (for. Example Eusolex ^® OS), 4-isopropylbenzyl (z. B. ^® Megasol) or 3,3,5-trimethylcyclohexyl (z. B. Eusolex ^® HMS),
4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester (z. B. Eusolex ^® 6007), ethoxylated ethyl 4-aminobenzoate (z. B. Uvinul ^® P25),
Phenylbenzimidazolesulfonic acids, such as 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine (z. B. Eusolex ^® 232), 2,2- (1,4-phenylene) -bisbenzimidazol-4,6-disulfonic acid or their salts (. for example Neoheliopan ^® AP) or 2,2- (1,4-phenylene) -bisbenzimidazol-6-sulfonic acid;
and other substances like

• - 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl (. For example Eusolex ^® OCR),
• - 3,3 '- (1,4-phenylenedimethylene) bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-ylmethanesulfonic acid and 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)
• - benzoic acid 2- (4-diethylamino-2-hydroxy-benzoyl) benzoate (. For example Uvinul ^® UVA Plus, BASF.).

The Listed compounds are only examples specific. Of course, others can UV filters are used.

• – 2-(2H-Benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol (z. B. Silatrizole^®, Drometrizole, Trisiloxane, Mexoryl^® XL),
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z. B. Uvasorb^® HEB),
• – α-(Trimethylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy(dimethyl [und ca. 6% methyl[2-[p[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] und ca. 1,5% methyl[3-[p-[2,2-bis(ethoxycarbonyl)vinyl)phenoxy)-propenyl) und 0,1 bis 0,4% (methylhydrogen]silylen]] (n ≈ 60) (CAS-Nr. 207 574-74-1)
• – 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (CAS-Nr. 103 597-45-1)
• – 2,2'-(1,4-Phenylen)bis-(1H-benzimidazol-4,6-disulfonsäure, Mononatriumsalz) (CAS-Nr. 180 898-37-7) und
• – 2,4-bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxyl]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (CAS-Nr. 103 597-45-, 187 393-00-6).
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z. B. Uvasorb^® HEB),

Other suitable organic UV filters are z. B.

• 2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol (e.g. B. 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) (z. B. 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'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) (CAS No. 103 597-45-1)
• 2,2'- (1,4-phenylene) bis (1H-benzimidazole-4,6-disulfonic acid, monosodium salt) (CAS No. 180 898-37-7) and
• 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).
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (z. B. Uvasorb HEB ^®),

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

organic UV filters are typically used in an amount of 0.5 to 20% by weight, preferably 1-15 wt .-%, incorporated in formulations.

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

preferred Compounds with UV-filtering properties are 3- (4'-methylbenzylidene) dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) -propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 2-Cyano-3,3-di-phenyl-2-ethylhexyl acrylate, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanol amine salts.

By Combination of one or more of said compounds with UV filtering effect can be protective against harmful Effects of UV radiation can be optimized.

• – Die Hydrophilie der Kapselwand kann unabhängig von der Löslichkeit des UV-Filters eingestellt werden. So können beispielsweise auch hydrophobe UV-Filter in rein wässrige Zubereitungen eingearbeitet werden. Zudem wird der häufig als unangenehm empfundene ölige Eindruck beim Auftragen der hydrophobe UV-Filter enthaltenden Zubereitung unterbunden.
• – Bestimmte UV-Filter, insbesondere Dibenzoylmethanderivate, zeigen in kosmetischen Zubereitungen nur eine verminderte Photostabilität. Durch Verkapselung dieser Filter oder von Verbindungen, die die Photostabilität dieser Filter beeinträchtigen, wie beispielsweise Zimtsäurederivate, kann die Photostabilität der gesamten Zubereitung erhöht werden.
• – In der Literatur wird immer wieder die Hautpenetration durch organische UV-Filter und das damit verbundene Reizpotential beim direkten Auftragen auf die menschliche Haut diskutiert. Durch die hier vorgeschlagene Verkapselung der entsprechenden Substanzen wird dieser Effekt unterbunden.
• – Allgemein können durch Verkapselung einzelner UV-Filter oder anderer Inhaltstoffe Zubereitungsprobleme, die durch Wechselwirkung einzelner Zubereitungsbestandteile untereinander entstehen, wie Kristallisationsvorgänge, Ausfällungen und Agglomeratbildung vermieden werden, da die Wechselwirkung unterbunden wird.

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.
• - Generally, by encapsulation of individual UV filters or other ingredients preparation problems caused by interaction of individual preparation components with each other, such as crystallization processes, precipitation and agglomeration can be avoided because the interaction is prevented.

Therefore It is preferable if one or more of the above UV filters present in encapsulated form. It is advantageous if the Capsules are so small that they are not visible to the naked eye can be observed. To achieve the o. G. effects It is also necessary that the capsules are sufficiently stable and the encapsulated drug (UV filter) not or only slightly Giving circumference to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 B1 describe the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use have walls which are produced by a SolGel process, as described in applications WO 00/09652 . WO 00/72806 and WO 00/71084 described can be obtained. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of appropriate Capsules are known to those skilled in the art, for example, from the cited patent applications, the content of which is expressly also part of the present application.

there the capsules are to be used in accordance with the invention Preparations are preferably contained in such quantities, which ensure that the encapsulated UV filters in the above weight percent ratios present in the preparation.

The can be used according to the invention preparations In addition, other usual skin-friendly or contain skin-care agents. This can be done in principle all agents known to those 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 are also in the German patent application DE-A-10133202 described osmolytes. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids, and in each case their precursors. As osmolytes in the sense of the German patent application DE-A-10133202 especially substances from the group of polyols, such as myo-inositol, mannitol or sorbitol and / or one or more of the following osmolytically active substances understood: 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 are used according to the invention as compatible solute substances selected from the group consisting of pyrimidinecarboxylic acids (like ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic Diphosphoglycerate, N. acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-Mannosylglycerate (Firoin), β-Mannosylglyceramide (Firoin-A) and / or dimannosyl-di-inositol phosphate (DMIP) or an optical Isomer, derivative, e.g. As an acid, a salt or ester used of these compounds or combinations thereof.

there Among the pyrimidinecarboxylic acids are especially ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives. These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents. They stabilize further especially enzymes against denaturing conditions, such as salts, extreme pH levels, surfactants, urea, guanidinium chloride and others Links.

Ectoin and ectoine derivatives such as hydroxyectoine may be advantageous be used in medicines. In particular, hydroxyectoine used for the manufacture of a medicament for the treatment of skin diseases become. Other uses of hydroxyectoine and other ectoin derivatives are typically in areas where z. B. trehalose as an additive is used. Thus, ectoin derivatives, such as hydroxyectoine, as a protective substance in dried yeast and bacterial cells use Find. Also pharmaceutical products such as non-glycosylated, pharmaceutical effective peptides and proteins e.g. B. t-PA can be used 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. Thus, in the European patent application EP-A-0 671 161 specifically described that ectoine and hydroxyectoine are used in cosmetic preparations such as powders, soaps, surfactant-containing cleaning products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.

worin R¹ ein Rest H oder C1-8-Alkyl, R² ein Rest H oder C1-4-Alkyl und R³, R⁴, R⁵ sowie R⁶ jeweils unabhängig voneinander ein Rest aus der Gruppe H, OH, NH₂ und C1-4-Alkyl sind. Bevorzugt werden Pyrimidincarbonsäuren eingesetzt, bei denen R² eine Methyl- oder eine Ethylgruppe ist und R¹ bzw. R⁵ und R⁶ H sind. Insbesondere bevorzugt werden die Pyrimidincarbonsäuren Ectoin ((S)-1,4,5,6-Tetrahydro-2-methyl-4-pyrimidin-carbonsäure) und Hydroxyectoin ((S,S)-1,4,5,6-Tetrahydro-5-hydroxy-2-methyl-4-pyrimidin-carbonsäure) eingesetzt. Dabei enthalten die erfindungsgemäß einzusetzenden Zubereitungen derartige Pyrimidincarbonsäuren vorzugsweise in Mengen bis zu 15 Gew.-%.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. Particular preference is given to the pyrimidinecarboxylic acids ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydrocarboxylic acid). 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.

Especially it is preferred if the compatible solutes selected are di-myo-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), 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, for example, from the German patent application DE-A-41 16 123 known. 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 z. B. for the treatment of psoriasis, different types of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages can be used. 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.

Further can the preparations of the invention at least one self-tanner as another ingredient contain.

Advantageous self-tanner may be used, inter alia:

sowie das in den Henna-Blättern vorkommende 2-Hydroxy-1,4-naphtochinon (Lawson).Further, 5-hydroxy-1,4-naphthoquinone (juglone), which is extracted from the shells of fresh walnuts

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

Very particular preference is given to 1,3-dihydroxyacetone (DHA), a trivalent sugar occurring in the human body and its derivatives

The bifunctional dihydroxyacetone derivatives and their dimers as well the optionally further active ingredients can in the usual Way, for example by mixing, in cosmetic or dermatological preparations be incorporated.

Suitable are preparations for an external Application, for example as a cream, lotion, gel, or as a solution, which can be sprayed on the skin. For an internal application are dosage forms such as capsules, Dragees, powders, tablet solutions or solutions suitable.

As an application form of the preparations to be used z. As: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing Rei cleansing 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.

Anoint, Pastes, creams and gels can be the usual carriers included, for. B. 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.

powder and sprays can be the usual carriers included, for. Lactose, talc, silicic acid, aluminum hydroxide, Calcium silicate and polyamide powder or mixtures of these substances. Sprays can also use the usual volatile, liquefied propellant, z. As chlorofluorocarbons, propane / butane or dimethyl ether, contain. Also, compressed air is advantageous to use.

solutions and emulsions may be the usual carriers such as solvents, solubilizers and emulsifiers, z. As water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, Benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, especially cottonseed oil, peanut oil, corn oil, olive oil, Castor oil and sesame oil, glycerol fatty acid esters, Polyethylene glycols and fatty acid esters of sorbitan or Mixtures of these substances included.

suspensions can the usual carriers like liquid diluents, e.g. As water, ethanol or Propylene glycol, suspending agent, e.g. B. ethoxylated isostearyl alcohols, Polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline Cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soap can the usual carriers like Alkali salts of fatty acids, salts of fatty acid monoesters, Fatty acid protein hydrolysates, isothionates, lanolin, Fatty alcohol, vegetable oils, plant extracts, glycerin, sugar or mixtures of these substances.

surfactant Cleaning products can be the usual carriers 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 Glycerin fatty acid esters or mixtures of these substances.

facial and body oils can be the usual Carriers such as synthetic oils such as fatty acid esters, fatty alcohols, Silicone oils, natural oils such as vegetable oils and oily extracts, paraffin oils, Lanolin oils or mixtures of these substances.

Further typical cosmetic applications are also lipsticks, lip balms, Powder, emulsion and wax make-up as well as sunscreen, pre-sun and after-sun preparations.

To the preferred preparation forms belong in particular also emulsions.

emulsions are advantageous and contain z. As mentioned fats, oils, Waxes and other fatty substances, as well as water and an emulsifier, as he usually does for such a type of Preparation is used.

• – Mineralöle, Mineralwachse
• – Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z. B. Rizinusöl;
• – Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z. B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;
• – Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.

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 the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group 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.

Further the oil phase can be chosen advantageously from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group the saturated or unsaturated, branched or unbranched alcohols, and the fatty acid triglycerides, namely 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 may be, for example be chosen advantageously from the group of synthetic, semisynthetic and natural oils, e.g. Olive oil, sunflower oil, Soybean oil, peanut oil, rapeseed oil, almond oil, Palm oil, coconut oil, palm kernel oil and the like more.

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

The aqueous phase of the preparations to be used optionally advantageous alcohols, diols or polyols lower C number, and 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 alcohols C number, z. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group Silica, aluminum silicates, polysaccharides or their derivatives, z. Hyaluronic acid, xanthan gum, hydroxypropyl methylcellulose, particularly advantageous from 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.

Especially Mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another Be part of it.

emulsions are advantageous and contain z. As mentioned fats, oils, Waxes and other fatty substances, as well as water and an emulsifier, as he usually does for such a type of Formulation is used.

In a preferred embodiment contain the used Preparations hydrophilic surfactants. The hydrophilic surfactants become preferably selected from the group of alkylglucosides, the Acyllactylate, the betaines and the cocoamphoacetate.

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 represent. 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 like those in the DE-A-43 08 282 have been described, have turned out to be favorable. Preference is given to emulsions. O / W 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 the. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.

Advantageous For example, O / W emulsifiers are chosen as coemulsifiers. primarily from the group of substances with HLB values of 11-16, especially advantageous with HLB values of 14.5-15.5, if the O / W emulsifiers have saturated radicals R and R '. Do the O / W emulsifiers unsaturated radicals R and / or R 'on, or are Isoalkylderivate, the preferred HLB value of such emulsifiers also lower or above lie.

It is advantageous, the fatty alcohol ethoxylates from the group of ethoxylated Stearyl alcohol, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols) to choose. 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 ether (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) isolauryl ether (Isolaureth-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 also advantageous, the fatty acid ethoxylates following Group to choose from: 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.

When ethoxylated alkyl ether carboxylic acid or its salt can Advantageously, the sodium laureth-11-carboxylate can be used. When Alkyl ether sulfate can be advantageously used sodium laureth 1-4 sulfate become. As the ethoxylated cholesterol derivative, polyethylene glycol (30) may advantageously be cholesteryl ether be used. Also, polyethylene glycol (25) sojasterol has become proven. As ethoxylated triglycerides can Advantageously, the polyethylene glycol (60) Evening Primrose Glycerides be used (Evening Primrose = evening primrose).

Farther is advantageous, the Polyethylenglycolglycerinfettsäureester from the group 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 / cprinate, polyethylene glycol (20) glyceryl oleate, Polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate) to choose.

It is also cheap, the sorbitan esters from the group Polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, Polyethylene glycol (20) to choose sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be set:
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-atoms, 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 of saturated and / or unsaturated, branched and or unbranched alcohols of 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 of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a K ettenlänge of 8 to 24, in particular 12-18 C-atoms.

Especially 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.

According to the invention preferred Preparations are also suitable for protecting human skin against aging processes and oxidative stress, d. H. against damage by Radicals, such as B. by sunlight, heat or other influences are generated. She lies in different, for this application usually used dosage forms. So she can especially as 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 pins or be assembled as an aerosol.

The Preparation may contain cosmetic adjuvants present in this Type of preparations commonly used, such as z. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, Foaming agents, perfumes, waxes, lanolin, propellants, Dyes and / or pigments containing the agent itself or the Dye skin, and others in cosmetics usually used ingredients.

you may be an oil as a dispersing or solubilizing agent, Wax or other fat, a low mono alcohol or a lower polyol or mixtures thereof. To the particularly preferred monoalcohols or polyols Ethanol, i-propanol, propylene glycol, glycerol and sorbitol.

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

Further preferred embodiments provide oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, especially 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, represents.

The Preparation may also be present as an alcoholic gel containing a or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickening agent such as silica. The oily-alcoholic gels also contain natural or synthetic oil or wax.

The Solid pens are made of natural or synthetic Waxing and oiling, fatty alcohols, fatty acids, fatty acid esters, Lanolin and other fatty substances.

is a preparation prepared as an aerosol, is used in the Usually the usual propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, preferably alkanes.

The Preparations to be used can with the help of Techniques well known to those skilled in the art.

The Preparations as described above, may be mentioned contain necessary or optional ingredients or comprise, consist essentially of, or consist of.

Also without further explanation 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 only as descriptive, in no way as limiting in any way To understand the revelation. The complete revelation of all above and below listed applications and publications are incorporated by reference into this application. The Weight percentages of the individual ingredients in the preparations of the examples are expressly included for the disclosure of the description and therefore as features be used.

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

Examples

General procedure for the synthesis of DHA ortho esters

dihydroxyacetone is using catalytic amounts (+/-) - camphor-10-sulfonic acid in dioxane at 50-100 ° C for monomerization for stirred for about 2 hours. Subsequently, the to be coupled Ortho-ester fragment added as Trialkyloxy-ortho-ester and for Stirred at 50-100 ° C for 6-48 hrs. 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 in the ortho-ester fragment to be coupled and stirred at 50-100 ° C for 6-48 hrs. Subsequently, the purification is carried out by distillation and / or crystallization. Synthesis of 2-ethoxy-2-methyl- [1,3] dioxan-5-one (dihydroxyacetone-ortho-ethyl-acetate, DHA-OEA)

13 g Dihydroxyacetone (144 mmol) and 335 mg (+/-) - camphor-10-sulfonic acid (CSA, 1.4 mmol, catalyst) are dissolved in 650 ml of dioxane and stirred for 120 min at 60 ° C for DHA monomerization. Then 131 ml of triethyl orthoacetate (721 mmol) are added dropwise and the reaction solution for 16 hrs. At 60 ° C. touched. After purification by vacuum distillation 9.4 g of 2-ethoxy-2-methyl- [1,3] dioxan-5-one (DHA-OEA; 40.7%) as colorless odorless oil.

NMR data of 2-ethoxy-2-methyl- [1,3] dioxan-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, 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 Synthesis of 2,10-diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxa-dispiro [4.2.4.2] tetradecane (dimerene-dihydroxyacetone-bis-ortho-ethyl-acetate, dDHA- OEA)

4 g dimeric dihydroxyacetone (44.4 mmol) and 103 mg (+/-) - camphor-10-sulfonic acid (CSA, 0.4 mmol, catalyst) are dissolved in 40 ml of triethyl orthoacetate (222 mmol) for 16 hrs. At 60 ° C stirred. After purification by crystallization, 2.75 is obtained g 2,10-Diethoxy-2,10-dimethyl-1,3,6,9,11,13-hexaoxa-dispiro [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-dispiro [4.2.4.2] tetradecane (DDHA-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 = 4:08 to 4:16 (3H, 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

In vitro tanning test of 2-ethoxy-2-methyl- [1,3] dioxan-5-one (DHA-OEA)

• (je kleiner L* desto dunkler; a* > 0 rot; a* < 0 grün; b* > 0 gelb; b* < 0 blau)

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 ° C (= Liquidskin model). Subsequently, the Lab values of the solution are measured by UV-VIS spectrometer (Varian Cary-100) and compared with DHA / lysine in the Liquidskin model. a * b * L * DHA / lysine 0.9 0.9 0.5 DHA-OEA / lysine -0.7 4.6 8.1 Blank value (EC / water 94/6) 0 0 100

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

Result:

• • DHA shows a color change, especially by a strong darkening (L * = 0.5).
• • DHA-OEA shows a color change all by a yellow shift (b * = 4,6) and by a darkening (L * = 8,1).

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 of ectoine triethoxy ortho ester (173.19 mmol, 1.2 eq.) Are added and the reaction solution is stirred for 16 hrs. At 60 ° C. 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. 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 (+/-) 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 40.06 g of 5-triethoxymethylpyrrolidin-2-one (173.19 mmol, 1.2 eq.) Are added and the reaction solution is stirred at 60 ° C. for 16 hours. After purification by crystallization, 19.5 g of 2-ethoxy-2- (2-methyl-1,4,5,6-tetrahydropyrimidin-4-yl) -1,3-dioxinan-5-one (DHA) are obtained. Ectoine-ethyl-ortho-acetate, 59%) as colorless crystals. Formulation Example 1a: O / W Tanning Cream Ingredients / Trade Name source INCI [% Weight] A Marlipal 1618/11 (1) CETEARETH-11 3:00 Lanette O (2) CETEARYLALCOHOL 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-hydroxybenzoate (5) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (5) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B 1,2-Propanediol (5) PROPYLENE GLYCOL 4:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 70.80 total 100.00

Production method:

First, phase A is heated to 75 ° C and phase B to 80 ° 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 Ingredients / Trade Name source INCI [% Weight] A Marlipal 1618/11 (1) CETEARETH-11 3:00 Lanette O (2) CETEARYLALCOHOL 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-hydroxybenzoate (5) PROPYLPARABEN 12:05 B 1,2-Propanediol (5) PROPYLENE GLYCOL 4:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 60.80 C 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, phase A is heated to 75 ° C and phase B to 80 ° 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 2a: O / W Tanning Cream Ingredients / Trade Name source INCI [% Weight] A Tego Care 150 (1) GLYCERYL STEHRATE, 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-hydroxybenzoate (4) PROPYLPARABEN 12:15 Dihydroxyacetone-ortho (4) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B 1,2-Propanediol (4) PROPYLENE GLYCOL 4:00 Sorbitol F liquid (4) SORBITOL 2:00 Methyl 4-hydroxybenzoate (4) METHYLPARABEN 12:05 Water, demineralized AQUA (WATER) 61.30 C Fragrance (qs) PERFUME 12:50 total 100.00

Production method:

First, phases A and B are heated separately to 75 ° C. Thereafter, phase A is slowly added to phase B with gentle stirring. It is homogenized at 65 ° C for one minute. The mixture is then cooled with stirring to 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 GmbH (2) Sasol Germany (3) Cognis GmbH (4) Merck KGaA / ^Rona® Formulation Example 2b: O / W Tanning Cream Ingredients / Trade Name source INCI [% Weight] A Tego Care 150 (1) GLYCERYL STEHRATE, 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-hydroxybenzoate (4) PROPYLPARABEN 12:15 B 1,2-Propanediol (4) PROPYLENE GLYCOL 4:00 Sorbitol F liquid (4) SORBITOL 2:00 Methyl 4-hydroxybenzoate (4) METHYLPARABEN 12:05 Water, demineralized AQUA (WATER) 49.50 Dihydroxyacetone-ortho-ethyl (4) dihydroxyacetone 5:00 lactate ORTHOETHYLLACTATE C Water, demineralized AQUA (WATER) 11.80 D Fragrance (qs) PERFUME 12:50 total 100.00

Production method:

First, phases A and B are heated separately to 75 ° C. Thereafter, phase A is slowly added to phase B with gentle stirring. It is homogenized at 65 ° C for one minute. The mixture is then cooled with stirring to 40 ° C and the phase C is added. It is then cooled to 35 ° 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 GmbH (2) Sasol Germany (3) Cognis GmbH (4) Merck KGaA / ^Rona® Formulation Example 3a: O / W Tanning Cream Ingredients / Trade Name source 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 TRIGLYCERIDES Paraffin liquid (5) PARAFFINUM LIQUIDUM 3:00 (MINERAL OIL) AbilWax 2434 (1) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLLPARABEN 12:05 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 52.20 C Dihydroxyacetone-ortho (5) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE Probiol L 05018 (Empty (7) AQUA, ALCOHOL DENAT, 5:00 liposomes) LELCITHIN, GLYCERINE, DISODIUM PHOSPHATES Water, demineralized AQUA (WATER) 10:00 total 100.00

Production method:

First, phases A and B are heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 ° C was added. Sources: (1) Degussa Goldschmidt AG (2) Cognis GmbH (3) BASF AG (4) Sasol Germany GmbH (5) Merck KGaA / ^Rona® (6) Dow Corning (7) Kuhs GmbH & Co. KG Formulation Example 3b: O / W Tanning Cream Ingredients / Trade Name source 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 TRIGLYCERIDES Paraffin liquid (5) PARAFFINUM LIQUIDUM 3:00 (MINERAL OIL) AbilWax 2434 (1) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLLPARABEN 12:05 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 52.20 C Dihydroxyacetone-ortho-ethyl (5) dihydroxyacetone 5:00 ectoins ORTHOETHYLECTOINE Probiol L 05018 (Empty (7) AQUA, ALCOHOL DENAT, 5:00 liposomes) LELCITHIN, GLYCERINE, DISODIUM PHOSPHATES Water, demineralized AQUA (WATER) 10:00 total 100.00

Production method:

First, phases A and B are heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 ° C was added. Sources: (1) Degussa Goldschmidt AG (2) Cognis GmbH (3) BASF AG (4) Sasol Germany GmbH (5) Merck KGaA / ^Rona® (6) Dow Corning (7) Kuhs GmbH & Co. KG Formulation Example 4a: O / W Tanning Lotion Ingredients / Trade Name source 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 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (5) dihydroxyacetone 2:50 Ethylacetate ORTHOETHYLACETATE B RonaCare ^® Ectoin (5) ECTOIN 12:50 Glycerol, anhydrous (5) glycerol 2:00 Water, demineralized AQUA (WATER) 60.90 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 C Rhodicare S (7) XANTHAN GUM 12:20 D Probiol L 05018 (Empty (8th) AQUA, ALCOHOL DENAT, 5:00 liposomes) LECITHIN, GLYCERINE, DISODIUM PHOSPHATES Water, demineralized AQUA (WATER) 10:00 e Fragrance Cucumber (9) PERFUME 12:20 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. Sources: (1) Seppic (2) Uniqema (3) Cognis GmbH (4) Condea Chinica DACSpA (5) Merck KGaA / ^Rona® (6) Dow Corning (7) Rhodia GmbH (8) Kuhs GmbH & Co. KG (9) drom Formulation Example 4b: O / W Tanning Lotion Ingredients / Trade Name source 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 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (2- (5) dihydroxyacetone 5:00 dimethyl-amino) ethyl-acetate ORTHO (2-dimethyl- AMINO) ETHYL ACETATE B RonaCare ^® Ectoin (5) ECTOIN 12:50 Glycerol, anhydrous (5) glycerol 2:00 Water, demineralized AQUA (WATER) 60.90 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 C Rhodicare S (7) XANTHAN GUM 12:20 D Probiol L 05018 (Empty (8th) AQUA, ALCOHOL DENAT, 5:00 liposomes) LECITHIN, GLYCERINE, DISODIUM PHOSPHATES Water, demineralized AQUA (WATER) 10:00 e Fragrance Cucumber (9) PERFUME 12:20 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. The pH is adjusted to pH = 6.5 with sodium hydroxide solution or citric acid. Sources: (1) Seppic (2) Uniqema (3) Cognis GmbH (4) Condea Chinica DACSpA (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 source INCI [% Weight] A Dow Corning 3225 C (1) CYCLOMETHICONE, 23.60 DIMETHICONE COPOLYOL Propyl-4-hydroxybenzoate (2) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (2) dihydroxyacetone 2:00 Ethylacetate ORTHOETHYLACETATE B Dihydroxyacetone (2) dihydroxyacetone 3:00 Methyl 4-hydroxybenzoate (2) METHYLPARABEN 12:15 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 adjusted to pH = 6.0 with sodium hydroxide solution or citric acid. Sources: (1) Dow Corning (2) Merck KGaA / ^Rona® Formulation Example 5b: Mild transparent W / O tanning lotion Ingredients / Trade Name source INCI [% Weight] A Dow Corning 3225 C (1) CYCLOMETHICONE, 23.60 DIMETHICONE COPOLYOL Propyl-4-hydroxybenzoate (2) PROPYLPARABEN 12:05 B Dihydroxyacetone-ortho-ethyl (2) dihydroxyacetone 5:00 lactate ORTHOETHYLLACTATE Methyl 4-hydroxybenzoate (2) METHYLPARABEN 12:15 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. Sources: (1) Dow Corning (2) Merck KGaA / ^Rona® Formulation Example 6a: W / O Tanning Lotion Ingredients / Trade Name source INCI [% Weight] A 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 (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 12:30 Dihydroxyacetone-ortho (5) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm Glycerol, anhydrous (5) glycerol 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 source INCI [% Weight] A 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 (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 12:30 Dihydroxyacetone-ortho-ethyl (5) dihydroxyacetone 5:00 pyrrolidoncarbonate ORTHOETHYL PYRROLIDONCARBONATE B 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm Glycerol, anhydrous (5) glycerol 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 Corning (4) drom (5) Merck KGaA / ^Rona® (6) Nipa Laboratories GmbH Formulation Example 7a: Aqueous tanning gel Ingredients / Trade Name source INCI [% 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 12:20 Water, demineralized AQUA (WATER) 28.30 B Natrosol 250 HHR (2) HYDROXYETHYLCELLULOSE 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 Ingredients / Trade Name source INCI [% 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 (1) METHYLPARABEN 12:20 Water, demineralized AQUA (WATER) 28.30 B Natrosol 250 HHR (2) HYDROXYETHYLCELLULOSE 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- (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 Ingredients / Trade Name source INCI [% Weight] Dihydroxyacetone-ortho (5) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE Ethanol 96% (1) ALCOHOL 40.00 Day 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 Ingredients / Trade Name source INCI [% Weight] Dihydroxyacetone-ortho-ethyl (5) dihydroxyacetone 5:00 lactate ORTHOETHYLLACTATE Ethanol 96% (1) ALCOHOL 40.00 Day 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 lactate is dissolved in the water and the remaining ingredients are added with stirring. Sources: (1) Merck KGaA / ^Rona® (2) Degussa Goldschmidt AG Formulation Example 9a: W / Si Tanning Gel Ingredients / Trade Name source INCI [% Weight] A Dow Corning 5225 C (1) CYCLOPEN TASILOXANE, 8:00 pm PEG / PG-18/18 DIMETHICONE DM-fluid-A-6cs (2) DIMETHICONE 4:00 Soybean oil (3) GLYCINE SOY (SOYBEAN OIL) 2:00 RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 12:50 Dihydroxyacetone-ortho (4) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B RonaCare ^® Ectoin (4) ECTOIN 12:30 1,2-Propanediol (4) PROPYLENE GLYCOL 30.00 dipropylene (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), CI 15985 12:25 (FD & C YELLOW NO 6) Water, demineralized AQUA (WATER) 19:25 C Fragrance Melopeach (7) PERFUME 12:20 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. Sources: (1) Dow Corning (2) S. Black GmbH (3) Gustav Heess GmbH (4) Merck KGaA / ^Rona® (5) BASF AG (6) DD Williamson (7) drom Formulation Example 9b: W / Si Tanning Gel Ingredients / Trade Name source INCI [% Weight] A Dow Corning 5225 C (1) CYCLOPEN TASILOXANE, 8:00 pm PEG / PG-18/18 DIMETHICONE DM-fluid-A-6cs (2) DIMETHICONE 4:00 Soybean oil (3) GLYCINE SOY (SOYBEAN OIL) 2:00 RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 12:50 Dihydroxyacetone-ortho-ethyl (4) dihydroxyacetone 5:00 ectoins ORTHOETHYLECTOINE B RonaCare ^® Ectoin (4) ECTOIN 12:30 1,2-Propanediol (4) PROPYLENE GLYCOL 30.00 dipropylene (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), CI 15985 12:25 (FD & C YELLOW NO 6) Water, demineralized AQUA (WATER) 19:25 C Fragrance Melopeach (7) PERFUME 12:20 total 100.00

Production method:

Phase B is released and added to Phase A. Phase C is added successively with stirring. It is homogenized. Sources: (1) Dow Corning (2) S. Black GmbH (3) Gustav Heess GmbH (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 source INCI [% Weight] A Eusolex ^® 2292 (1) ETHYLHEXYL 3:00 METHOXYCINNAMATE, BHT Eusolex ^® 4360 (1) BENZOPHENONE-3 12:50 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 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (1) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (1) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B 1,2-Propanediol (1) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (1) SODIUM METHYLPARABEN 12:17 sodium salt Water, demineralized AQUA (WATER) 63.18 total 100.00

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized and cooled to 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) Sasol Germany GmbH (6) Dow Corning Formulation Example 10b: O / W tanning cream with UV A / B protection Ingredients / Trade Name source INCI [% Weight] A Eusolex ^® 2292 (1) ETHYLHEXYL 3:00 METHOXYCINNAMATE, BHT Eusolex ^® 4360 (1) BENZOPHENONE-3 12:50 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 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (1) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (2- (1) dihydroxyacetone 3:00 dimethyl-amino) ethyl-acetate ORTHO (2-DIMETHYL AMINO) ETHYL ACETATE B 1,2-Propanediol (1) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (1) SODIUM METHYLPARABEN 12:17 sodium salt Water, demineralized AQUA (WATER) 53.18 C Dihydroxyacetone (1) dihydroxyacetone 2:00 Water, demineralized AQUA (WATER) 10:00 total 100.00

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 ° C was added. Sources: (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 source INCI [% Weight] A Eusolex ^® 2292 (1) ETHYLHEXYL 3:00 METHOXYCINNAMATE, BHT Eusolex ^® 4360 (1) BENZOPHENONE-3 12:50 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 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (1) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho-ethyl (1) dihydroxyacetone 5:00 lactate ORTHOETHYLLACTATE B 1,2-Propanediol (1) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (1) SODIUM METHYLPARABEN 12:17 sodium salt Water, demineralized AQUA (WATER) 53.18 C Water, demineralized AQUA (WATER) 10:00 total 100.00

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. The mixture is then cooled with stirring and the phase C at 40 ° C was added. Sources: (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 Ingredients / Trade Name source INCI [% Weight] A Eusolex ^® 2292 (1) ETHYLHEXYL 3:00 METHOXYCINNAMATE, BHT Eusolex ^® 4360 (1) BENZOPHENONE-3 12:50 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 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (1) PROPYLPARABEN 12:05 B 1,2-Propanediol (1) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (1) SODIUM METHYLPARABEN 12:17 sodium salt Water, demineralized AQUA (WATER) 53.18 C Dihydroxyacetone-ortho-ethyl (1) dihydroxyacetone 5:00 ectoins ORTHOETHYLECTOINE Water, demineralized AQUA (WATER) 10:00 total 100.00

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. 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 Ingredients / Trade Name source INCI [% Weight] A Eusolex ^® 2292 (1) ETHYLHEXYL 3:00 METHOXYCINNAMATE, BHT Eusolex ^® 4360 (1) BENZOPHENONE-3 12:50 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 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (1) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho-ethyl (1) dihydroxyacetone 5:00 pyrrolidoncarbonate ORTHOETHYL PYRROLIDONCARBONATE B 1,2-Propanediol (1) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate (1) SODIUM METHYLPARABEN 12:17 sodium salt Water, demineralized AQUA (WATER) 63.18 total 100.00

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized. 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 source INCI [% Weight] A Montanov 68 (1) CETEARYL ALCOHOL, 4:00 CETEARYL GLUCOSIDE Span 60 (2) SORBITAN STEHRATE 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 12:50 Propyl-4-hydroxybenzoate (6) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (6) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE 12:50 B RonaCare ^® Ectoin (6) ECTOIN 12:50 Colorona® ^® Red Gold (6) ME, CI 77891 (TITANIUM 2:00 DIOXIDES), CI 77491 (ION OXIDES) Glycerol, anhydrous (6) GLYCERIN 2:00 Caramel 250 (7) CARAMEL 1:00 FD & C Yellow No6 W082 (8th) CI 15985 12:01 Water, demineralized AQUA (WATER) 73.09 Methyl 4-hydroxybenzoate (6) METHYLPARABEN 12:15 C Sea urchin 305 (1) LAURETH-7, POLYACRYL 12:50 AMIDE, C13-14 ISOPARAFFIN D Fragrance Babylon (9) PERFUME 12:20 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 is homogenized. It is then cooled to 40 ° C and the phase D is added successively. Sources: (1) Seppic (2) Uniqema (3) Cognis GmbH (4) Condea Chimica DACSpA (5) Dow Corning (6) Merck KGaA / ^Rona® (7) DD Williamson (8) Les Colorants Wackherr SA (9) drom Formulation Example 11b: O / W shimmering tanning lotion Ingredients / Trade Name source INCI [% Weight] A Montanov 68 (1) CETEARYL ALCOHOL, 4:00 CETEARYL GLUCOSIDE Span 60 (2) SORBITAN STEHRATE 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 12:50 Propyl-4-hydroxybenzoate (6) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (2- (6) dihydroxyacetone 5:00 dimethyl-amino) ethyl-acetate ORTHO (2-dimethyl- AMINO) ETHYL ACETATE 12:50 B RonaCare ^® Ectoin (6) ECTOIN 12:50 Colorona® ^® Red Gold (6) ME, CI 77891 (TITANIUM 2:00 DIOXIDES), CI 77491 (ION OXIDES) Glycerol, anhydrous (6) GLYCERIN 2:00 Caramel 250 (7) CARAMEL 1:00 FD & C Yellow No6 W082 (8th) CI 15985 12:01 Water, demineralized AQUA (WATER) 73.09 Methyl 4-hydroxybenzoate (6) METHYLPARABEN 12:15 C Sepigel 305 (1) LAURETH-7, POLYACRYL 12:50 AMIDE, C13-14 ISOPARAFFIN D Fragrance Babylon (9) PERFUME 12:20 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 is homogenized. It is then cooled to 40 ° C and the phase D is added successively. Sources: (1) Seppic (2) Uniqema (3) Cognis GmbH (4) Condea Chimica DACSpA (5) Dow Corning (6) Merck KGaA / ^Rona® (7) DD Williamson (8) Les Colorants Wackherr SA (9) drom Formulation Example 12a: O / W shimmering tanning lotion Ingredients / Trade Name source INCI [% Weight] A Montanov 68 (1) CETEARYL ALCOHOL, 4:00 CETEARYL GLUCOSIDE Span 60 (2) SORBITAN STEHRATE 1:50 Lanette O (3) CETEARYL ALCOHOL 1:00 RonaCare ^® Tocopherol Acetate (4) TOCOPHERYL ACETATE 12:50 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-hydroxybenzoate (4) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (4) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B RonaCare ^® Ectoin (4) ECTOIN 12:50 Timiron ^® Starluster MP-115 (4) ME, CI 77891 (TITANIUM 1:00 DIOXIDE) Glycerol, anhydrous (4) GLYCERIN 2:00 Caramel 250 (7) CARAMEL 0.60 FD & C Yellow No6 W082 (8th) CI 15985 12:01 Methyl 4-hydroxybenzoate (4) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 59.49 C Sea urchin 305 (1) LAURETH-7, POLYACRYL 12:50 AMIDE, C13-14 ISOPARAFFIN D Probiol L 05018 (Empty (9) AQUA, ALCOHOLDENATE, 5:00 liposomes) LECITHIN, GLYCERINE, DISODIUM PHOSPHATES Water, demineralized AQUA (WATER) 10:00 e Fragrance Babylon (10) PERFUME 12:20 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 is 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 DACSpA (6) Dow Corning (7) DD Williamson (8) Les Colorants Wackherr SA (9) Kuhs GmbH & Co. KG (10) drom Formulation Example 12b: O / W shimmering tanning lotion Ingredients / Trade Name source 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 12:50 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-hydroxybenzoate (4) PROPYLPARABEN 12:05 B RonaCare ^® Ectoin (4) ECTOIN 12:50 Timiron ^® Starluster MP-115 (4) MICA, CI 77891 (TITANIUM 1:00 DIOXIDE) Glycerol, anhydrous (4) GLYCERIN 2:00 Caramel 250 (7) CARAMEL 0.60 FD & C Yellow No6 W082 (8th) CI 15985 12:01 Methyl 4-hydroxybenzoate (4) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 59.49 C Sepigel 305 (1) LAURETH-7, POLYACRYL 12:50 AMIDE, C13-14 ISOPARAFFIN D Dihydroxyacetone-ortho-ethyl (4) dihydroxyacetone 5:00 pyrrolidoncarbonate ORTHOETHYL PYRROLIDONCARBONATE Probiol L 05018 (Empty (9) AQUA, ALCOHOLDENATE, 5:00 liposomes) LECITHIN, GLYCERINE, DISODIUM PHOSPHATES Water, demineralized AQUA (WATER) 10:00 e Fragrance Babylon (10) PERFUME 12:20 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 is homogenized. It is then cooled to 40 ° 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 DACSpA (6) Dow Corning (7) DD Williamson (8) Les Colorants Wackherr SA (9) Kuhs GmbH & Co. KG (10) drom Formulation Example 13a: clear W / O shimmering tanning lotion Ingredients / Trade Name source INCI [% Weight] 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 12:30 Dihydroxyacetone-ortho (6) dihydroxyacetone 5:00 Ethylacetate ORTHOETHYLACETATE B RonaCare ^® Ectoin (6) ECTOIN 12:50 Caramel 250 (7) CARAMEL 0.60 Timiron ^® Starluster MP-115 (6) ME, CI 77891 (TITANIUM 1:00 DIOXIDE) FD & C Yellow No6 W082 (8th) CI 15985 12:01 1,2-Propanediol (6) PROPYLENE GLYCOL 8:00 pm 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

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 Corning (5) drom (6) Merck KGaA / ^Rona® (7) DD Williamson (8) Les Colorants Wackherr SA (9) Nipa Laboratories GmbH Formulation Example 13b: Clear W / O shimmering tanning lotion Ingredients / Trade Name source INCI [% Weight] 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 12:30 Dihydroxyacetone-ortho-ethyl (6) dihydroxyacetone 5:00 ectoins ORTHOETHYLECTOINE B RonaCare ^® Ectoin (6) ECTOIN 12:50 Caramel 250 (7) CARAMEL 0.60 Timiron ^® Starluster MP-115 (6) ME, CI 77891 (TITANIUM 1:00 DIOXIDE) FD & C Yellow No6 W082 (8th) CI 15985 12:01 1,2-Propanediol (6) PROPYLENE GLYCOL 8:00 pm 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

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) 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 giving a summer-like complexion Ingredients / Trade Name source INCI [% Weight] A Eusolex ^® OCR (1) OCTOCRYLENE 5:00 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 (100 cs) (5) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (1) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (1) dihydroxyacetone 2:00 Ethylacetate ORTHOETHYLACETATE B 1,2-Propanediol (1) PROPYLENE GLYCOL 3:00 RonaCare ^® Ectoin (1) ECTOIN 12:30 Methyl 4-hydroxybenzoate (1) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 70.20 C Fragrance "sunshine for cream D" (6) PERFUME 12:10 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 phase C at 40 ° C was added. Sources: (1) Merck KGaA / ^Rona® (2) Degussa-Goldschmidt AG (3) Cognis GmbH (4) Sasol Germany GmbH (5) Dow Corning (6) Bell Flavors & Fragrances Formulation Example 15: Skin protection cream giving a light summer tan Ingredients / Trade Name source INCI [% Weight] A Tego Care 150 (1) GLYCERYL STEARATE, 8:00 STEARETH-25, CETETH-20, STEARYL ALCOHOL Lanette (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 (100 cs) (4) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 Dihydroxyacetone-ortho (5) dihydroxyacetone 0.75 Ethylacetate ORTHOETHYLACETATE B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Ectoin (5) ECTOIN 12:30 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 71.45 C Fragrance "sunshine for cream D" (6) PERFUME 12:10 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 phase C at 40 ° C was added. Sources: (1) Degussa Goldschmidt AG (2) Cognis GmbH (3) Sasol Germany GmbH (4) Dow Corning (5) Merck KGaA / ^Rona® (6) Bell Flavors & Fragrances Formulation example 16: velvety body lotion for a natural color Ingredients / Trade Name source INCI [% Weight] A Abil EM 07 (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) 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 12:30 Dihydroxyacetone-ortho (5) dihydroxyacetone 1:00 Ethylacetate ORTHOETHYLACETATE B Dihydroxyacetone (5) dihydroxyacetone 1:00 RonaCare ^® Ectoin (5) ECTOIN 12:50 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm 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. Sources: (1) Degussa Goldschmidt AG (2) ISP Global Technologies (3) Dow Corning (4) drom (5) Merck KGaA / ^Rona® (6) Nipa Laboratories GmbH Formulation Example 17: Gentle Tanning Cream with Silver Glitter Ingredients / Trade Name source INCI [% Weight] A Montanov 68 (1) CETEARYL ALCOHOL, 4:00 CETEARYL GLUCOSIDE Cosmacol ELI (2) C12-13 ALKYL 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 ORTHOETHYLACETATE B RonaCare ^® Tocopherol Acetate (6) TOXOPHERYLACETATE 12:50 C Ronastar ^® Silver (6) CALCIUM ALUMINUM 1:00 BOROSILICATE, SILICA, CI77891 (TITANIUM DIOXIDE), TIN OXIDE Glycerol, anhydrous (6) GLYCERIN 3:00 RonaCare ^® Ectoin (6) ECTOIN 12:50 Water, demineralized AQUA (WATER) 69.50 D Sepigel 305 (1) LAURETH-7, POLYACRYL 0.60 AMIDE, C13-14 ISOPARAFFIN e Dihydroxyacetone (6) dihydroxyacetone 1:00 Water, demineralized AQUA (WATER) 4:00 F Germall 115 (7) IMIDAZOLIDINYL UREA 12:30 Water, demineralized AQUA (WATER) 1:50 G Fragrance Melopeach (8th) PERFUME 12:30 total 100.00

Production method:

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. Sources: (1) Seppic (2) Condea Chimica DACSpA (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 Ingredients / Trade Name source 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 (1) STEAROXY DIMETHICONE 1.20 Dow Corning 200 (100 cs) (4) DIMETHICONE 12:50 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 B 1,2-Propanediol (5) 3:00 Methyl 4-hydroxybenzoate (5) PROPYLENE GLYCOL 12:15 Water, demineralized METHYLPARABEN 59.00 AQUA (WATER) C DHA-OEA-Rapid (5) dihydroxyacetone 3:00 ORTHOETHYLACETATE, TROXERUTINE Water, demineralized AQUA (WATER) 10:00 D Fragrance "sunshine for cream D" (6) PERFUME 12:10 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 ° C was added. Phase D is added. Sources: (1) Degussa Goldschmidt AG (2) Cognis GmbH (3) Sasol Germany GmbH (4) Dow Corning (5) Merck KGaA / ^Rona® (6) Bell Flavors & Fragrances

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• EP 0796838 B1 [0008]
• WO 99/43667 [0008]
• - DE 102007013368 [0072]
• - DE 4116123 A [0077, 0111]
• - DE 10244282 A [0088]
• - DE 10232595 A [0094]
• US 6242099 B1 [0101]
• WO 00/09652 [0101]
• WO 00/72806 [0101]
• WO 00/71084 [0101]
• - DE 10133202 A [0104, 0104]
• EP 0671161 A [0108]
• DE 4308282 A [0139]

Cited non-patent literature

• - Fey, Otte, Dictionary of Cosmetics, 3rd edition, 1991 [0023]
• Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971. [0055]
• - Römpp Chemie Lexikon, Vol. 9, 1993 [0078]
• K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108 [0086]
• CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159 [0087]
• - K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 [0087]

Claims (27)

Bifunctional derivative of the dihydroxyacetone of the general formula (I)

or its dimeric derivative of the general formula (II)

in which the radicals are defined as follows: X = O, S or NR, where R is selected from H, alkyl and aryl having 1 to 20 carbon atoms R ¹ , R ² , R ³ = H, straight-chain or branched alkyl with 1 20 carbon atoms, which may contain one or more double bonds, saturated, partially or completely unsaturated cycloalkyl having 3-7 carbon atoms wherein R ¹ , R ² and R ^{3 are} each the same or different, these groups with further saturated and / or unsaturated alkyl, saturated, partially or fully unsaturated cycloalyl and / or heteroatom substituents may be substituted in various positions, wherein these groups one or two carbon atoms by the heteroatoms and / or atomic groups -O-, -N =, -C (O) -, -C (O) O- and / or -C (O) NH- can be replaced, wherein R ^{2 is} not methyl and wherein the two R ³ in the dimeric derivative of the general formula (II) at two of the four ring methylene Groups are substituted. Derivative according to Claim 1, characterized that the radical X is O. A derivative according to claim 1 or 2, characterized in that the radical R ^{3 is} H or - (CHOH) _n -CH ₂ OH where n = 0 to 5. A derivative according to claim 3, characterized in that the radical R ^{3 is} H or -CH ₂ OH. Derivative according to one or more of claims 1 to 4, characterized in that the radicals R ¹ and / or R ^{2 are} independently selected from the group -H, - (CH ₂ ) _o CH ₃ , - (CH ₂ ) _n NH ₂ , - (CH ₂ ) _n N ((CH ₂ ) _o CH ₃ ) ((CH ₂ ) _p CH ₃ ), - (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) -O-R ' , -C ₆ H ₆ -CH ₂ CHNR'COOR ', -CH ₂ CHNR'COOR', wherein n is an integer and selected from the range 1 to 20, wherein o and p are independently an integer selected from the Range 0 to 20, wherein Ar is an aryl group and may be substituted with other aryl, alkyl and / or heteroatom substituents in different positions, wherein the radicals R 'are independently selected from H, amino acid residue and peptide residue and R ² does not mean -CH ₃ . Derivative according to one or more of claims 1 to 5, characterized in that the radical R ^{1 is} selected from the group aminocarboxylic acid radical, carboxylic acid radical, branched or straight-chain, saturated or unsaturated alkyl having 2 to 20 carbon atoms and saturated, partially or completely unsaturated cycloheteroalkyl with 5 to 7 ring atoms, wherein the alkyl and the cycloheteroalkyl may be substituted with further aryl, alkyl and / or heteroatom substituents, in particular hydroxy and / or amino groups, in different positions. A derivative according to claim 6, characterized in that the radical R ^{1 is} selected from the group -CH ₃ , -CHOH-CH ₃ , Pyrrolidoncarbonsäurerest, EctoincarbonsÄureeste and AminocarbonsÄureeste. Derivative according to one or more of claims 1 to 7, characterized in that the radical R ^{2 is} selected from the group of a physiologically and / or dermatologically tolerated alcohol R ² -OH or a physiologically and / or dermatologically acceptable aminoalcohol R ² -OH, wherein R ² is a branched or linear chain, a saturated or unsaturated alkyl or aminoalkyl group having 2 to 20 carbon atoms which may be substituted with other aryl, alkyl, and / or heteroatom substituents in different positions, means. A derivative according to claim 8, characterized in that the radical R ^{2 is} selected from the group -C ₂ H ₅ or -C ₂ H ₄ N (CH ₃ ) ₂ . Derivative according to one or more of the claims 1 to 9, characterized in that the derivative is selected is from dihydroxyacetone-ortho-ethyl acetate, dihydroxyacetone-ortho- (2-dimethylamino) -ethyl acetate, dihydroxyacetone ortho-ethyl-lactate and dihydroxyacetone ortho ethyl ectoine or its dimers. Process for the preparation of a bifunctional derivative of the general formula (I) according to one or more of Claims 1 to 10, characterized in that first dihydroxyacetone or a dihydroxyacetone substituted by R ^{3 of} the general formula (III)

with catalytic amounts (+/-) - camphor-10-sulfonic acid and then reacted with an ortho-ester of the general formula (IV)

where the radicals X, R ^1, R ² and R ³ are as defined in claim. 1 Process for the preparation of a bifunctional dimer derivative of the general formula (II) according to one or more of Claims 1 to 10, characterized in that dimeric dihydroxyacetone or a dimeric dihydroxyacetone substituted by R ^{3 of} the general formula (V)

reacted with catalytic amounts (+/-) - camphor-10-sulfonic acid and with an ortho-ester of the general formula (IV)

where the radicals X, R ^1, R ² and R ³ are as defined in claim. 1 Use of a compound of the general formula (I) and / or the general formula (II) for the preparation of a cosmetic Preparation for artificial tanning and / or Browning of the skin is determined. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 for the preparation of a dermatological Preparation for artificial tanning and / or Browning of the skin is determined. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 as a browning agent. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 for the preparation of a cosmetic and / or dermatological preparation with photoprotective properties. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 as a UV filter. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 as a preservative. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 for lifting the skin. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 in pharmaceutical and / or cosmetic Preparations. Use of a compound of the general formula (I) and / or the general formula (II) after one or more of claims 1 to 10 in household products. Preparation containing at least one bifunctional Derivative of dihydroxyacetone of the general formula (I) and / or at least one dimeric bifunctional derivative of the dihydroxyacetone of the general formula (II) in which the radicals are as in one or are defined in any one of claims 1 to 10. Preparation according to Claim 22, characterized that the preparation is the at least one derivative of the general Formula (I) and / or the at least one dimeric derivative of the general Formula (II) in a total amount of 0.01 to 10 wt .-%, preferably from 0.1 to 2% by weight. Composition according to Claim 22 or 23, characterized that they contain at least one formaldehyde scavenger and / or at least contains a flavonoid. Preparation according to one or more of the claims 22 to 24, characterized in that they contain further active substances selected from repellents, UV filters, flavone derivatives, Chromone derivatives, aryloximes and parabens contains. Preparation according to one or more of the claims 22 to 25 to protect body cells against oxidative Stress, in particular to reduce skin aging, thereby in that, in addition to the at least one derivative of the general formula (I) and / or the at least one dimeric derivative of general formula (II) one or more further antioxidants and / or contains vitamins, preferably selected are vitamin A palmitate, vitamin C and its derivatives, DL-α-tocopherol, Tocopherol E acetate, nicotinic acid, pantothenic acid and biotin. Preparation according to one or more of the claims 22 to 26, characterized in that they in addition to the at least a derivative of the general formula (I) and / or the at least a dimeric derivative of the general formula (II) one or more Contains UV filter, which is preferably selected are from 3- (4'-methylbenzylidene) dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-isopropyl-dibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethylcyclohexylsalicylate, 4- (dimethylamino) benzoic acid 2-ethylhexylester, 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts.