DE102009038206A1 - Glyceraldehyde derivatives and their acetals - Google Patents

Abstract

The invention relates to the use of glyceraldehyde derivatives and their acetals for releasing active molecules, new glyceraldehyde derivatives and their acetals, and preparations containing the latter.

Description

The invention relates to the use of Glycerinaldehydderivaten and their acetals for the release of active molecules, new Glycerinaldehydderivate and their acetals and preparations containing the latter.

The trend away from the noble paleness towards the "healthy, sporty brown skin" has been unbroken for years. To achieve this, people expose their skin to solar radiation, as it causes pigmentation through melanin formation.

However, the UV radiation of sunlight also has a damaging effect on the skin. In addition to acute injury (sunburn), long-term damage from excessive exposure to UVB light (wavelength 280-320 nm), such as an increased risk of developing skin cancer. The excessive action of the UVB and UVA radiation (wavelength: 320-400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue. This leads to numerous phototoxic and photoallergic reactions and leads to premature skin aging.

There are a variety of organic and inorganic UV filters and antioxidants known that can absorb UV radiation and trap free radicals. They are thus able to protect human skin. These compounds catalyze the transformation from UV light to heat.

Natural protection against the negative effects of solar radiation is provided by the tanning (pigmentation) of the skin. The epidermis contains in its lowest layer, the basal layer, in addition to the basal cells, individual pigment-forming cells, the melanocytes. UV light in these cells stimulates the production of melanin, which is transported to the keratinocytes (horny cells) where it becomes visible as a brown skin color. This pigment formation originating from the amino acid tyrosine is predominantly initiated by UVB radiation and referred to as "indirect pigmentation". Their development runs over several days; the sun tan will last for several weeks. In the case of "direct pigmentation", which starts with sunlight, predominantly colorless melanin precursors are oxidized by UVA radiation to dark-colored melanin. Since this oxidation is reversible, it leads to a short-lasting tanning of the skin.

An artificial tanning of the skin can be produced externally with the help of make-up and orally by taking carotenoids.

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

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

Of course, the prior art knows a variety of different self-tanning substances, such as α-hydroxycarbonyl compounds (eg dihydroxyacetone or glycolaldehyde). An especially commonly used self-tanning substance is 1,3-dihydroxyacetone (DHA). This is a water-soluble crystalline solid which is not stable under neutral to basic conditions. This instability is also associated with the development of cosmetically undesirable off-odors.

Benzaldehyde derivatives such. As anisaldehyde (4-methoxybenzaldehyde) or vanillin (4-hydroxy-3-methoxy-benzaldehyde) are included as odor or flavoring ingredients in flavors and perfume oils. Anisaldehyde is part of many essential oils, he is z. As in the essences of aniseed, bitter fennel, star anise and Buchu included. Vanillin is known as a valuable ingredient in vanilla and vanilla extracts.

Benzaldehyde derivatives and α-hydroxycarbonyl compounds perform their functions directly, be it because of their volatility (benzaldehydes) or because of their reactivity (α-hydroxycarbonyl compounds). In many applications, this immediate effect is undesirable. Disadvantages are here z. B. to rapid volatilization of aromas and fragrances or the undesired browning and discoloration in the run-up to the application. An example of this is the undesirable discoloration of self-tanning creams.

The object of the present invention was therefore to provide substances which contain active molecules such as self-tanning substances, flavorings or UV filters in stable form and can deliver them in a controlled manner.

It has now been found that certain Glycerinaldehydderivate and their acetals are able to disintegrate under hydrolysis conditions in the described individual components.

worin

• – R1, R2, R4, R5, R14, R15, R17 und R18 unabhängig voneinander für H, OH, C₁- bis C₂₀-Alkyl, C₁- bis C₂₀-Alkoxy, O-(CO)-C₁- bis C₂₀-Alkyl oder O-(CH₂)₂-OH stehen,
• – R3 und R16 unabhängig voneinander für H, OH, C₁- bis C₂₀-Alkyl, C₁- bis C₂₀-Alkoxy, O-(CO)-C₁- bis C₂₀-Alkyl, O-(CH₂)₂-OH oder NR11R12 stehen,
• – R6 für H, C₁- bis C₂₀-Alkyl, C₁- bis C₂₀-Alkoxy, CH₂OH, CHOH-CH₂OH oder (CO)-O-C₁- bis C₂₀-Alkyl steht,
• – R7 und R8 unabhängig voneinander für C₁- bis C₂₀-Alkyl stehen,
• – R9 und R10 unabhängig voneinander für H, C₁- bis C₂₀-Alkyl, CH₂OH, CHOH-CH₂OH oder CHOH-CHOH-CH₂OH stehen, wobei in R9 und R10 die Summe der Kohlenstoffatome der Hydroxyalkylreste 0, 1, 2, 3, 4, 5 oder 6 ist,
• – R11 und R12 unabhängig voneinander für C₁- bis C₂₀-Alkyl stehen,
• – R13 für H oder
  
  steht wobei enthaltene Alkylreste geradkettig, verzweigt oder zyklisch sein können,

zur Freisetzung von Verbindungen, wobei
eine Verbindung der Formel (1) Verbindungen der Formel (4) und/oder (5) freisetzt

eine Verbindung der Formel (2) Verbindungen der Formel (1), (4), (5), (6a) und/oder (6b) freisetzt, wobei Formel (1), (4) und (5) wie zuvor definiert sind

und eine Verbindung der Formel (3) Verbindungen der Formel (1), (4), (5) und/oder (7) freisetzt, wobei Formel (1), (4) und (5) wie zuvor definiert sind

The present invention therefore provides the use of at least one compound of the formula (1), (2) or (3)

wherein

• R ₁ , R 2, R 4, R 5, R 14, R 15, R 17 and R 18 independently of one another are H, OH, C ₁ - to C ₂₀ -alkyl, C ₁ - to C ₂₀ -alkoxy, O- (CO) - C ₁ - to C ₂₀ -alkyl or O- (CH ₂ ) ₂ -OH,
• R 3 and R 16 independently of one another are H, OH, C ₁ - to C ₂₀ -alkyl, C ₁ - to C ₂₀ -alkoxy, O- (CO) -Cl ₁ - to C ₂₀ -alkyl, O- (CH ₂ ) ₂ -OH or NR11R12,
• R 6 is H, C ₁ - to C ₂₀ -alkyl, C ₁ - to C ₂₀ -alkoxy, CH ₂ OH, CHOH-CH ₂ OH or (CO) -OC ₁ - to C ₂₀ -alkyl,
• R7 and R8 independently of one another are C ₁ -C ₂₀ -alkyl,
• R9 and R10 independently of one another are H, C ₁ - to C ₂₀ -alkyl, CH ₂ OH, CHOH-CH ₂ OH or CHOH-CHOH-CH ₂ OH, where in R9 and R 10 the sum of the carbon atoms of the hydroxyalkyl radicals 0, 1, 2, 3, 4, 5 or 6,
• R 11 and R 12 independently of one another represent C ₁ - to C ₂₀ -alkyl,
• - R13 for H or
  
  where included alkyl radicals can be straight-chain, branched or cyclic,

for the release of compounds, wherein
a compound of the formula (1) liberates compounds of the formula (4) and / or (5)

a compound of formula (2) releases compounds of formula (1), (4), (5), (6a) and / or (6b), wherein formula (1), (4) and (5) are as previously defined

and a compound of the formula (3) releases compounds of the formula (1), (4), (5) and / or (7), wherein formula (1), (4) and (5) are as defined above

The compounds may optionally be in the form of dimers or isomers / tautomers (analogous enol or dihydroxyacetone derivatives).

Preference is given to using compounds of the formulas (1) to (3) where R ₁ , R 2, R 4 and R 5 independently of one another are H, OH, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy or O- ( CO) -C ₁ - to C ₈ -alkyl.

Preferably, the radicals R3 and R16 independently of one another are H, OH, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxyl, O- (CO) -C ₁ - to C ₈ -alkyl or NR 11 R 12.

The radical R 6 is preferably H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ -alkyl.

Preferably, the radicals R7 and R8 independently of one another are C ₁ - to C ₈ -alkyl.

Preferably, the radicals R9 and R10 independently of one another are H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH or CHOH-CHOH-CH ₂ OH, where in R9 and R10 the sum of the carbon atoms of the hydroxyalkyl radicals 0, 1, 2, 3, 4, 5 or 6.

The radicals R11 and R12 independently of one another are preferably C ₁ - to C ₈ -alkyl.

The radical R 13 is preferably H or

Preferably, the radicals R14, R15, R17 and R18 independently of one another are H, OH, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy or O- (CO) C ₁ - to C ₈ -alkyl ,

In this case, alkyl radicals contained in the radicals R 1 to R 18 may be straight-chain, branched or cyclic.

The radicals R1, R2, R4 and R5 are particularly preferably selected independently of one another from H, OH, methoxy and tert-butyl.

The radicals R3 and R16 are more preferably independently selected from H, OH, methoxy, tert-butyl and NR11R12.

Most preferably, R11 and R12 are the same and selected from ethyl and hexyl.

The radicals R 14, R 15, R 17 and R 18 are more preferably independently of one another H, OH, methoxy or tert-butyl.

Most preferably, the radicals R1, R2, R4 and R5 are selected from H and methoxy.

R3 and R16 are most preferably independently selected from H, methoxy, tert-butyl and NR11R12.

The radical R ₆ is very particularly preferably selected from H, CH ₂ OH and (CO) -OC ₈ -alkyl.

The radicals R 7 and R 8 are very particularly preferably CH ₂ CH ₃ .

Most preferably, the radicals R9 and R10 are H.

R11 and R12 are most preferably C ₂ H ₅ .

Most preferably, the radicals R14, R15, R17 and R18 are independently selected from H and OH.

Particularly preferred is the use of compounds selected from the group comprising

The release of the active molecules of formula (1), (2) or (3) can be spontaneous or catalyzed for example by amines such as lysine. Likewise, by varying the pH, a decay can be initiated, such. B. by the acidic conditions as they are present on the skin surface. Disintegration is also favored by the mesomeric stabilization of the product (eg, p-methoxybenzaldehyde).

The acetals according to formulas (2) and (3) are also to be regarded as precursors of the aldehyde according to formula (1) and can be catalytically, for. B. be converted by acid hydrolysis in these. The hydrolysis can be carried out, for example, in contact with the skin. It is also conceivable to effect this hydrolysis biotechnologically or enzymatically. This step is particularly important preparatively (aldehyde synthesis).

Mechanistically z. B. for Methoxyphenylglycerinaldehyddiethylacetal found that after hydrolysis of the acetal to Glycerinaldehyd, this splits off p-methoxybenzaldehyde. In addition, the self-tanning substance glycolaldehyde is formed. As a result, this compound decomposes into the three components p-methoxybenzaldehyde (anisaldehyde), glycolaldehyde and ethanol. Instead of ethanol, dihydroxyacetone is split off in the case of a dihydroxyacetone acetal.

For example, compounds released from selected compounds of formula (1) may be selected from

For example, compounds released from selected compounds of formula (2) may be selected from compounds of formula (1-1) to (1-27), (4-1) to (4-8), (5-1) to ( 5-3) as previously defined, as well

For example, compounds released from selected compounds of formula (3) may be selected from compounds of formula (1-1) to (1-27), (4-1) to (4-8), (5-1) to ( 5-3) as previously defined, as well

Likewise, a Maillardprodukt can be released, which is formed in the course of a Maillardreaktion of an aldehyde of formula (1-1) to (1-27).

The released molecules can perform various functions: p-methoxybenzaldehyde is a flavoring agent, glycolaldehyde and dihydroxyacetone are self-tanning substances, with glycolaldehyde having even better self-tanning properties than dihydroxyacetone. Ethanol can be used as a preservative or coolant. Furthermore, the release of active molecules according to the invention gives rise to the capability of UV absorption, which is due to the intrinsic absorption of the resulting benzaldehyde derivative.

Thus, by means of the present invention, the effects based on the released components can be specifically achieved.

worin

• – R1, R2, R4 und R5 unabhängig voneinander für H, OH, Methoxy, oder tert-Butyl stehen,
• – R3 und R16 unabhängig voneinander für H, OH, Methoxy, tert-Butyl oder NR11R12 stehen,
• – R6 für H, C₁- bis C₈-Alkyl, CH₂OH, CHOH-CH₂OH, CH₂OCH₃ oder (CO)-O-C₁- bis C₈-Alkyl steht,
• – R11 und R12 unabhängig voneinander für C₁- bis C₈-Alkyl stehen,
• – R13 für H oder
  
  steht
• – R14, R15, R17 und R18 unabhängig voneinander für H, OH, Methoxy, oder tert-Butyl stehen,

wobei enthaltene Alkylreste geradkettig, verzweigt oder zyklisch sein können,
und wobei die Verbindungen

ausgeschlossen sind.Another object of the present invention are compounds of formula (1)

wherein

• R1, R2, R4 and R5, independently of one another, are H, OH, methoxy or tert-butyl,
• R3 and R16 independently of one another are H, OH, methoxy, tert-butyl or NR11R12,
• R 6 is H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ -alkyl,
• R 11 and R 12 independently of one another represent C ₁ - to C ₈ -alkyl,
• - R13 for H or
  
  stands
• R14, R15, R17 and R18 independently of one another are H, OH, methoxy or tert-butyl,

where included alkyl radicals may be straight-chain, branched or cyclic,
and wherein the compounds

excluded are.

Preference is given to compounds of the formula (1) in which the radicals R1, R2, R4 and R5 are H.

R3 and R16 are preferably independently selected from H, methoxy, tert-butyl and NR11R12.

The radical R ₆ is preferably selected from H, CH ₂ OH and (CO) -OC ₈ -alkyl. The radicals R11 and R12 are preferably identical and selected from ethyl and hexyl.

Preferably, the radicals R14, R15, R17 and R18 are independently selected from H and OH.

The radicals R11 and R12 are particularly preferably identical and are C ₂ H ₅ .

Very particular preference is given to compounds selected from the group comprising

worin

• – R1, R2, R4 und R5 unabhängig voneinander für H, OH, Methoxy oder tert-Butyl stehen,
• – R3 und R16 unabhängig voneinander für H, OH, Methoxy, tert-Butyl oder NR11R12 stehen,
• – R6 für H, C₁- bis C₈-Alkyl, CH₂OH, CHOH-CH₂OH, CH₂OCH₃ oder (CO)-O-C₁- bis C₈-Alkyl steht,
• – R7 und R8 unabhängig voneinander für C₁- bis C₈-Alkyl stehen,
• – R11 und R12 unabhängig voneinander für C₁- bis C₈-Alkyl stehen,
• – R13 für H oder
  
  steht,
• – R14, R15, R17 und R18 unabhängig voneinander für H, OH, Methoxy oder tert-Butyl stehen,

wobei enthaltene Alkylreste geradkettig, verzweigt oder zyklisch sein können,
und wobei die Verbindungen

ausgeschlossen sind. Compounds of formula (2) are also the subject of the present invention:

wherein

• R1, R2, R4 and R5, independently of one another, are H, OH, methoxy or tert-butyl,
• R3 and R16 independently of one another are H, OH, methoxy, tert-butyl or NR11R12,
• R 6 is H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ -alkyl,
• R7 and R8 independently of one another are C ₁ - to C ₈ -alkyl,
• R 11 and R 12 independently of one another represent C ₁ - to C ₈ -alkyl,
• - R13 for H or
  
  stands,
• R14, R15, R17 and R18 independently of one another are H, OH, methoxy or tert-butyl,

where included alkyl radicals may be straight-chain, branched or cyclic,
and wherein the compounds

excluded are.

Preference is given to compounds of the formula (2) where the radicals R1, R2, R4 and R5 are H or methoxy.

R3 and R16 are preferably independently selected from H, methoxy, tert-butyl and NR11R12.

The radical R6 is preferably selected from H, -CH ₂ OH and (CO) -OC ₈ -alkyl.

The radicals R 7 and R 8 are preferably CH ₂ CH ₃ .

The radicals R11 and R12 are preferably identical and selected from ethyl and hexyl.

Preferably, the radicals R14, R15, R17 and R18 are independently selected from H and OH.

The radicals R11 and R12 are particularly preferably identical and are C ₂ H ₅ .

Very particular preference is given to compounds selected from the group comprising

worin

• – R1, R2, R4 und R5 unabhängig voneinander für H, OH, Methoxy oder tert-Butyl stehen,
• – R3 und R16 unabhängig voneinander für H, OH, Methoxy, tert-Butyl oder NR11R12 stehen,
• – R6 für H, C₁- bis C₈-Alkyl, CH₂OH, CHOH-CH₂OH, CH₂OCH₃ oder (CO)-O-C₁- bis C₈-Alkyl steht,
• – R9 und R10 unabhängig voneinander für H, C₁- bis C₈-Alkyl, CH₂OH, CHOH-CH₂OH oder CHOH-CHOH-CH₂OH stehen, wobei in R9 und R10 die Summe der Kohlenstoffatome der Hydroxyalkylreste 0, 1, 2, 3, 4, 5 oder 6 ist,
• – R11 und R12 unabhängig voneinander für C₁- bis C₈-Alkyl stehen,
• – R13 für H oder
  
  steht,
• – R14, R15, R17 und R18 unabhängig voneinander für H, OH, Methoxy oder tert-Butyl stehen,

wobei enthaltene Alkylreste geradkettig, verzweigt oder zyklisch sein können.Furthermore, compounds of the formula (3) are claimed:

wherein

• R1, R2, R4 and R5, independently of one another, are H, OH, methoxy or tert-butyl,
• R3 and R16 independently of one another are H, OH, methoxy, tert-butyl or NR11R12,
• R 6 is H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ -alkyl,
• R9 and R10 independently of one another are H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH or CHOH-CHOH-CH ₂ OH, where in R9 and R 10 the sum of the carbon atoms of the hydroxyalkyl radicals 0, 1, 2, 3, 4, 5 or 6,
• R 11 and R 12 independently of one another represent C ₁ - to C ₈ -alkyl,
• - R13 for H or
  
  stands,
• R14, R15, R17 and R18 independently of one another are H, OH, methoxy or tert-butyl,

wherein included alkyl radicals may be straight-chain, branched or cyclic.

Preference is given to compounds of the formula (3) where the radicals R1, R2, R4 and R5 are H or methoxy.

R3 and R16 are preferably independently selected from H, methoxy, tert-butyl and NR11R12.

The radical R ₆ is preferably selected from H, CH ₂ OH and (CO) -OC ₈ -alkyl.

The radicals R 7 and R 8 are preferably CH ₂ CH ₃ .

Preferably, the radicals R9 and R10 are H.

The radicals R11 and R12 are preferably identical and selected from ethyl and hexyl.

Preferably, the radicals R14, R15, R17 and R18 are independently selected from H and OH.

The radicals R11 and R12 are particularly preferably identical and are C ₂ H ₅ .

Very particular preference is given to compounds selected from the group comprising

Compounds according to formula (1) can be prepared by acid hydrolysis (mineral acids, organic acids, acid ion exchangers) of the acetal from the compounds of formula (2) or (3). This is shown here by way of example on the compounds (1-7) and (2-7) or (3-7):

Therefore, a process for producing a compound of the formula (1) as described above is also an object of the present invention, wherein a compound of the formula (2) or (3) is converted to a compound of the formula (1) by acid hydrolysis.

direkt hergestellt werden, wie beispielhaft an Verbindung (1-14) gezeigt:

Furthermore, compounds of the formula (1) can be prepared by dihydroxylation (osmium tetroxide, ruthenium chloride) of the corresponding α, β-unsaturated aromatic aldehydes (formula (8))

can be prepared directly as exemplified by compound (1-14):

Compounds of the formula (2) and (3) can be prepared from the α, β-unsaturated aromatic aldehydes (formula (8)) by acetalization and subsequent dihydroxylation, as described here with reference to the compounds (2-4) or (3-4 ) is shown.

The present invention therefore also provides a process for preparing a compound of the formula (2) or (3) as described above, wherein a compound of the formula (8) as described above by acetalization and subsequent dihydroxylation in a compound of formula (2) or (3) is transferred.

Compounds such as compounds (1-9) can be obtained by reacting aromatic aldehydes with α-hydroxymalonic aldehydes in an aldol-type reaction. Depending on the derivative, the α-hydroxy group for the reaction is provided with a protective group (eg PG = tert-butyl-dimethylsilyl), which can later be split off again (for example with tetra-butylammonium fluoride).

Other compounds such as (1-5), (1-8), (2-11) and (3-12) can also be prepared by this method.

The starting compounds of the described synthetic routes are commercially available or can be prepared by simple syntheses.

According to the present invention, alkyl is an abbreviation for alkyl group. The C ₁ -C ₂₀ -alkyl radical may be straight-chain, branched or cyclic and is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3- Methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, 1-ethyl-pentyl, octyl, 1-ethyl-hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl. The cycloalkyl groups may be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclopentenyl, which may be substituted by further alkyl groups.

Alkoxy stands as an abbreviation for alkoxy group. Examples of C ₁ to C ₂₀ alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

Substances according to the invention can be provided as a particulate dosage form. The average particle sizes may be 0.001-10 μm, preferably 0.1-5 μm. Particularly preferred is a distribution with a d50 value (laser diffraction) of 100 nm-1 micron. The active compounds can be used alone or mixed with carrier materials such. For example, sorbitol or mannitol. In topical application, the substances in this dosage form can have a depot effect and gradually release the active substance to the skin. This is done by means of the follicular, transcellular and intercellular (corneocyte) penetration route. The substances according to the invention can furthermore be provided in the form of oily blends with typical oils / emollients of the pharmaceutical or cosmetics industry. It comes to the use of dispersants.

The present invention also provides a preparation comprising at least one compound of the formula (1), (2) or (3) whose radicals are defined as described above.

Preference is given to a preparation containing at least one compound of the formula (1), (2) or (3), the radicals of which are preferably as defined above.

The preparations are usually topically applicable preparations, for example cosmetic or dermatological formulations or medical products. The preparations in this case contain a cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients. In the case of pharmaceutical preparations, the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients.

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

The preparations may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. All compounds or components in the Preparations can be used, are either known and commercially available or can be synthesized by known methods.

It is preferably a cosmetic or pharmaceutical preparation.

The present invention also provides a process for preparing a preparation as described above, characterized in that at least one compound of the formula (1), (2) or (3) is mixed with a carrier and optionally with further active or auxiliary substances , Suitable carriers and active or auxiliary substances are described in detail in the following part.

In preferred embodiments, the at least one compound of the formula (1), (2) or (3) with the defined or preferred substituents or preferred individual compounds in the preparations according to the invention is typically present in amounts of from 0.05 to 10% by weight, preferably in amounts of 0.1 wt .-% to 5 wt .-% and particularly preferably in amounts of 0.5 to 2 wt .-%, used. The expert does not have any difficulties in selecting the quantities according to the intended effect of the preparation.

In the described preparations which according to the invention comprise at least one compound of the formula (1), (2) or (3), color pigments may furthermore also be present, the layer structure of the pigments not being limited.

Preferably, the color pigment when used from 0.5 to 5 wt .-% should be skin-colored or brownish. The selection of a corresponding pigment is familiar to the person skilled in the art.

In addition to the compounds of the formula (1), (2) or (3) and any other ingredients, preferred preparations contain further self-tanning substances and / or UV filters.

Organic UV filters, so-called hydrophilic or lipophilic sunscreen filters, are effective in the UVA range and / or UVB range and / or IR and / or VIS range (absorbers) .These substances can be particularly useful with cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, triazine derivatives , β, β-Diphenylacrylatderivaten, p-aminobenzoic acid derivatives and polymeric filters and silicone filters, in the application WO-93/04665 be selected. Further examples of organic filters are in the patent application EP-A 0 487 404 specified. In the following, the named UV filters are usually named according to the INCI nomenclature.

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

Salicylates: Homosalates are sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. under the name "Neo Heliopan OS" from the company. Haarmann and Reimer, Dipropylene glycol salicylate, z. B. under the name "Dipsal" from the company. Scher, TEA salicylate, z. B. under the name "Neo Heliopan TS" from the company Haarmann and Reimer.

β, β-diphenylacrylate derivatives: octocrylenes, e.g. B. under the name "Uvinul N539" from BASF, Etocrylene, z. B. under the name "Uvinul N35" from BASF.

Benzophenone Derivatives: Benzophenone-1, e.g. B. operated under the name "Uvinul 400"; Benzophenone-2, e.g. B. operated under the name "Uvinul D50"; Benzophenone-3 or oxybenzone, e.g. B. operated under the name "Uvinul M40"; Benzophenone-4, e.g. B. operated under the name "Uvinul MS40"; Benzophenone-9, e.g. B. under the name "Uvinul DS-49" from the company. BASF, Benzophenone-5, Benzophenone-6, z. B. under the name "Helisorb 11" from the company. Norquay, Benzophenone-8, z. Sold under the name "Spectra-Sorb UV-24" by American Cyanamid, Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, marketed by Fa. Merck, Darmstadt under the name Eusolex ^® 4360th

Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. B. under the name "Mexoryl SD" from the company Chimex, 4-Methylbenzylidenecamphor, z. B. under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. sold under the name "Mexoryl SL" from the Fa. Chimex, Camphor benzalkonium methosulfate, z. B. under the name "Mexoryl SO" from the company. Chimex, Terephthalylidenedicamphorsulfonsäure, z. B. sold under the name "Mexoryl SX" from the Fa Chimex, Polyacrylamidomethylbenzylidenecamphor operated under the name "Mexoryl SW" from the company Chimex.

Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B. under the name "Eusolex 232" from the company Merck, disodium phenyl dibenzimidazole tetrasulfonate, z. B. under the name "Neo Heliopan AP" from the company Haarmann and Reimer.

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

Triazine derivatives: ethylhexyltriazone, e.g. B. under the name "Uvinul T150" from the Fa. BASF, Diethylhexylbutamidotriazone, z. From the company Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines or 2,4,6-tris (biphenyl) -1, 3,5-triazines.

Anthraniline derivatives: menthyl anthranilate, e.g. B. under the name "Neo Heliopan MA" from the company Haarmann and Reimer.

Imidazole derivatives: Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate derivatives: Polyorganosiloxanes containing functional benzalmalonate groups, such as. B. polysilicone-15, z. B. sold under the name "Parsol SLX" by Hoffmann LaRoche.

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

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

Piperazine derivatives such as the compound

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

Suitable organic UV-protective substances are preferably selected from the following list: ethylhexyl salicylate, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4- Methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate, methylenebis (benzotriazolyl) tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxane, polysilicone-15, 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, 2, 4-Bis [5-1 (dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines and mixtures thereof.

These organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.

Preferred preparations contain, in addition to the compounds of the formula (1), (2) or (3) and the optionally organic UV filters, as described above, further inorganic UV filters, so-called particulate UV filters.

These combinations with particulate UV filters are possible both as a powder and as a dispersion or paste of the following types.

In this case, both those from the group of titanium dioxides such. For example, coated titanium dioxide (for. Example Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO, Eusolex ^® T-OLEG), zinc oxides (eg. As Sachtotec® ^®), iron oxides and also cerium and / or zirconium oxides are preferred.

Furthermore, combinations with pigmentary zinc oxide or Titandixoxid are possible, wherein the particle size of these pigments is greater than or equal to 200 nm, for example COS Hombitec ^®.

It may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53 64 described, were treated. Here, one or more of the following aftertreatment components may be selected: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially Collagen or elastin), alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.

• – unbehandelte Titandioxide wie z. B. die Produkte Microtitanium Dioxide MT 500 B der Fa. Tayca; Titandioxd P25 der Fa. Degussa,
• – Nachbehandelte mikronisierte Titandioxide mit Aluminiumoxid und Siliciumdioxid Nachbahandlung wie z. B. das Produkt „Microtitanium Dioxide MT 100 SA der Tayca; oder das Produkt „Tioveil Fin” der Fa. Uniqema,
• – Nachbehandelte mikronisierte Titandioxide mit Aluminiumoxid und/oder Aluminiumstearate/laurate Nachbehandlung wie z. B. Microtitanium Dioxide MT 100 T der Fa. Tayca, Eusolex T-2000 der Firma Merck,
• – Nachbehandelte mikronisierte Titandioxide mit Eisenoxid und/oder Eisenstearate Nachbehandlung wie z. B. das Produkt „Microtitanium Dioxide MT 100 F” der Fa. Tayca,
• – Nachbehandelte mikronisierte Titandioxide mit Siliciumdioxide, Aluminiumoxid und Silicon Nachbehandlung wie z. B. das Produkt ”Microtitanium Dioxide MT 100 SAS”, der Fa. Tayca,
• – Nachbehandelte mikronisierte Titandioxide mit Natrumhexameta-phosphate, wie z. B. das Produkt ”Microtitanium Dioxide MT 150 W” der Fa. Tayca.

Preferably used particulate UV filters are:

• - untreated titanium dioxides such. The products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,
• - Aftertreated micronized titanium dioxides with alumina and silica Nachbahandlung such. For example, the product "Microtitanium Dioxide MT 100 SA from Tayca; or the product "Tioveil Fin" from Uniqema,
• - Aftertreated micronized titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment such. B. Microtitanium Dioxide MT 100 T from. Tayca, Eusolex T-2000 from Merck,
• - Aftertreated micronized titanium dioxides with iron oxide and / or iron stearates aftertreatment such. B. the product "Microtitanium Dioxide MT 100 F" Fa. Tayca,
• - Aftertreated micronized titanium dioxides with silicas, alumina and silicon aftertreatment such. B. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,
• - Aftertreated micronized titanium dioxides with Natrumhexameta-phosphate, such as. As the product "Microtitanium Dioxide MT 150 W" Fa. Tayca.

• – Octyltrimethoxysilane; wie z. B. das Produkt Tego Sun T 805 der Fa. Degussa,
• – Siliciumdioxid; wie z. B. das Produkt Parsol T-X der Fa. DSM,
• – Aluminiumoxid und Stearinsäure; wie z. B. das Produkt UV-Titan M160 der Fa. Kemira,
• – Aluminium und Glycerin; wie z. B. das Produkt UV-Titan der Fa. Kemira,
• – Aluminium und Silikonölen, wie z. B. das Produkt UV-Titan M262 der Fa. Kemira,
• – Natriumhexamethaphosphat und Polyvinylpyrrolidon,
• – Polydimethylsiloxane, wie z. B. das Produkt 70250 Cardre UF TiO2SI3” der Fa. Cardre,
• – Polydimethylhydrogensiloxane, wie z. B. das Produkt Microtitanium Dioxide USP Grade Hydrophobic” der Fa. Color Techniques.

The treated micronized titanium dioxides used for combination may also be post-treated with:

• - octyltrimethoxysilanes; such as B. the product Tego Sun T 805 from Degussa,
• - silica; such as B. the product Parsol TX from DSM,
• Alumina and stearic acid; such as B. the product UV titanium M160 Fa. Kemira,
• - aluminum and glycerin; such as B. the product UV titanium from. Kemira,
• - Aluminum and silicone oils, such as. B. the product UV titanium M262 Fa. Kemira,
• Sodium hexamethaphosphate and polyvinylpyrrolidone,
• - Polydimethylsiloxane, such as. Example, the product 70250 Cardre UF TiO2SI3 "the Fa. Cardre,
• - Polydimethylhydrogensiloxane, such as. Example, the product Microtitanium Dioxide USP Grade Hydrophobic "from the company Color Techniques.

• – Unbehandelte Zinkoxide wie z. B. das Produkt Z-Cote der Fa. BASF (Sunsmart), Nanox der Fa. Elementis
• – Nachbehandelte Zinkoxide wie z. B die folgenden Produkte:
• • ”Zinc Oxide CS-5” der Fa. Toshibi (ZnO nachbehandelt mit polymethylhydrogenosiloxane)
• • Nanogard Zinc Oxide FN der Fa. Nanophase Technologies
• • ”SPD-Z1” der Fa Shin-Etsu (ZnO nachbehandelt mit einem Silikongepfropften Acrylpolymer, dispergiert in Cyclodimethylsiloxane
• • ”Escalol Z100” der Fa ISP (Aluminiumoxid nachbehandeltes ZnO dispergiert in einer ethylhexyl methoxycinnamate/PVP-hexadecene/methicone copolymer Mischung)
• • ”Fuji ZNO-SMS-10” der Fa. Fuji Pigment (ZnO nachbehandelt mit Siliciumdioxid und Polymethylsilesquioxan);
• • Unbehandeltes Ceroxide Mikropigment z. B. mit der Bezeichnung ”Colloidal Cerium Oxide” der Fa Rhone Poulenc
• • Unbehandelte und/oder nachbehandelte Eisenoxide mit der Bezeichnung Nanogar der Fa. Arnaud.

Furthermore, the combination with the following products may also be advantageous:

• - Untreated zinc oxides such. For example, the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis
• - After-treated zinc oxides such. B the following products:
• "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with polymethylhydrogenosiloxane)
• • Nanogard Zinc Oxide FN from Nanophase Technologies
• "SPD-Z1" from Shin-Etsu (ZnO post-treated with a silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxanes
• "Escalol Z100" from ISP (alumina aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer blend)
• Fuji ZNO-SMS-10 from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane);
• • untreated ceroxide micropigment z. B. with the name "Colloidal Cerium Oxide" Fa Rhone Poulenc
• • Untreated and / or post-treated iron oxides called Nanogar from Arnaud.

By way of example, mixtures of various metal oxides, such as. As titanium dioxide and cerium oxide are used with and without Nachbenhandlung, such. As the product Sunveil A Fa. Ikeda. In addition, mixtures of alumina, silica and silicon post-treated titanium dioxide, zinc oxide mixtures such. B. the product UV titanium M261 Fa. Kemira be used in combination with the UV protection agent according to the invention.

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

By combining one or more of said compounds with UV filter action, the protective effect 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, 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.
• - In general, by encapsulation of individual UV filters or other ingredients preparation problems that are avoided by interaction of individual preparation components with each other, such as crystallization processes, precipitation and agglomeration, since the interaction is prevented.

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

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 B1 the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxy-polyamines described. Capsule walls can also consist of PMMA. 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 such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.

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

Furthermore, the preparations according to the invention may contain at least one further self-tanner as further ingredient. Advantageous self-tanning agents which can be used include: 1,3-dihydroxyacetone, glycerolaldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, Ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2-hydroxy-1,4-naphthoquinone (Lawson). Very particular preference is given to 1,3-dihydroxyacetone, erythrulose or their combination.

Preferred formulations may also contain at least one other cosmetic active ingredient, for example selected from antioxidants, anti-aging agents, anti-cellulite agents, skin lightening agents or vitamins.

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

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), furthermore (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid , Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E). acetate), vitamin A and derivatives (eg, vitamin A palmitate), 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 unabhängig 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-dimethoxybenzyl)-malonsäure-bis-(2-ethylhexyl)ester (z. B. RonaCare^® AP).Suitable antioxidants are also compounds of the formulas A or B.

wherein
R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,
XO or NH,
R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,
R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,
R ⁴ each independently of one another are H or linear or branched alkyl having 1 to 8 C atoms,
R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
R ⁶ denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethylhexyl) ester (z. B. Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3, 5-dimethoxybenzyl) -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 commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (. 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).. Such antioxidants are used with the compounds of the invention in such compositions usually in weight percent ratios in the range of 1000: 1 to 1: 1000, preferably in weight percent ratios of 100: 1 to 1: 100.

Among the phenols which can be used according to the invention, the polyphenols, which occur in part as natural substances, are of particular interest for applications in the pharmaceutical, cosmetic or nutritional field. For example, the flavonoids or bioflavonoids, which are mainly known as plant dyes, frequently have an antioxidant potential. With effects of the substitution pattern of mono- and dihydroxyflavones deal 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 sometimes have no antioxidant properties ,

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.

Suitable anti-aging active substances, in particular for skin-care preparations, are preferably 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 according to the invention as compatible solute substances selected from the group consisting of Pyrimidincarbonsäuren (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic diphosphoglycerate, N. acetylornithine, trimethylamine N-oxide di-myo-inositol-phosphate (DIP) , cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (firoin), β-mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, e.g. As an acid, a salt or ester of these compounds or combinations thereof.

In particular, ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((8,8) -1,4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives.

The preparations may also contain one or more further skin-lightening active ingredients or synonymously depigmentation active ingredients. In principle, skin-lightening active ingredients can be all active ingredients known to the person skilled in the art. Examples of compounds with skin-lightening activity are hydroquinone, kojic acid, arbutin, aloesin or rucinol.

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.

The described retinoids are also effective anti-cellulite agents. Another well-known anti-cellulite drug is caffeine.

The said constituents of the preparation can be incorporated in the usual way, by means of techniques which are well known to the person skilled in the art.

Suitable preparations for external use, for example as a cream or milk (O / W, W / O, O / W / O, W / O / W), as a lotion or emulsion, in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions can be sprayed onto the skin. They can be present as solid pens or be packaged as aerosol. For internal use, administration formulas such as capsules, dragees, powders, tablet solutions or solutions are 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 cleaning preparations, oils, aerosols and sprays.

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

Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. As animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or mixtures of these substances.

Powders and sprays may contain the usual excipients, for. As lactose, talc, silica, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can additionally the usual volatile, liquefied propellant, z. For example, chlorofluorocarbons, propane / butane or dimethyl ether. Also, compressed air is advantageous to use.

Solutions and emulsions may contain the usual carriers such as solvents, solubilizers and emulsifiers, eg. 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 ,

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

Suspensions may be the usual carriers such as liquid diluents, for. For example, water, ethanol or propylene glycol, suspending, z. For example, ethoxylated isostearyl, Polyoxyethylensorbitester and Polyoxyethylensorbitanester, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar and tragacanth or mixtures of these substances.

Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.

Surfactant-containing cleaning products may contain the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyltaurates, 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 may contain the usual excipients such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.

Further typical cosmetic application forms are also lipsticks, lip balm sticks, powder, emulsion and wax-make-up as well as sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms include, in particular, emulsions.

Emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of preparation.

• – 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 acid, also natural oils such. Castor oil;
• - Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with alcohols of low C number, z. With isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 C atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 C 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 C 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-octyldodecyl palmitate, oleyl oleate, oleyl erucate, Erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, eg. B. jojoba oil.

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

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

If appropriate, the aqueous phase of the preparations to be used advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g. For example, ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides and their derivatives, for. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, 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.

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

Emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of formulation.

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

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. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.

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

It is advantageous to choose the fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).

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

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

It is furthermore advantageous to use the polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol ( 20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate).

It is also convenient to select the sorbitan esters from the group of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:
Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 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 ethers of saturated and / or unsaturated, branched and / or or unbranched alcohols having a chain length of 8 to 24, in particular 12-18 C atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms and sorbitan esters saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a K ettenlänge of 8 to 24, in particular 12-18 C-atoms.

Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl, glyceryl monomyristate, glyceryl, diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol, sorbitan, sorbitan, sorbitan, Sorbitanmonoisooleat, sucrose, cetyl alcohol, stearyl, arachidyl, behenyl, Isobehenylalkohol, selachyl, Chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate or PEG-30 dipolyhydroxystearate.

The preparation may contain cosmetic adjuvants, which are commonly used in this type of preparations, such as. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.

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

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

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

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

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

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

Even without further statements, it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments and examples are therefore to be considered as merely illustrative, in no way limiting, disclosure. The complete disclosure of all applications and publications cited above and below are incorporated by reference into this application. The weight percentages of the individual ingredients in the formulations of the examples are expressly intended to disclose the description and may therefore be used as features.

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

Examples:

Example 1: Synthesis of 1 - ((E) -3,3-Diethoxy-propenyl) -4-methoxy-benzene

20 g of para-methoxy-cinnamaldehyde (123.3 mmol) are dissolved in 21.6 ml of ethanol and 22.3 ml of triethyl orthoformate (135.6 mmol, 1.1 eq.) And 308 mg of ammonium chloride (catalyst, 0.05 eq .) was added. It is refluxed for 75 min. It is then cooled and the reaction mixture to 50 ml of cold sat. NaHCO ₃ solution poured. The aqueous phase is extracted 3 times with MTBE. The combined organic phases are dried over sodium sulfate. After fractional vacuum distillation, 22.61 g of 1- ((E) -3,3-diethoxy-propenyl) -4-methoxybenzene (74.4%) are obtained as an oil.

Example 2: Synthesis of 3,3-Diethoxy-1- (4-methoxyphenyl) -propane-1,2-diol

10.35 g of 1 - ((E) -3,3-diethoxy-propenyl) -4-methoxy-benzene (42.6 mmol) are added to a cooled to 0 ° C mixture of 5.49 g of N-methyl-morpholine N-oxide (46.9 mmol, 1.1 eq.) And 2.6 ml of aqueous osmium tetroxide solution (4%, 1 mol%) in 20 ml of water and 60 ml of acetone. After 16 hours reaction time at 0 ° C to room temperature, the solvent is removed in vacuo. The residue is between ethyl acetate and sat. NaCl solution is distributed and extracted. The organic phase is dried over sodium sulfate and the solvent removed in vacuo. Obtained after purification by crystallization from MTBE / n-heptane 8.98 g (78%) of 3,3-diethoxy-1- (4-methoxyphenyl) propane-1,2-diol as a crystalline solid.

Example 3: Synthesis of 2,3-Dihydroxy-3- (4-methoxyphenyl) propionaldehyde

4.88 g of 3,3-diethoxy-1- (4-methoxyphenyl) -propane-1,2-diol (18.05 mmol) is suspended in 49 ml of 0.5% sulfuric acid and for 110 hours at Room temperature stirred. There are added 1.59 g of barium carbonate and stirred for 60 min. After filtration, white solid precipitates several times, which is filtered off. A total of 421 mg of 2,3-dihydroxy-3- (4-methoxyphenyl) propionaldehyde is obtained as a white solid (11.9%). Structure determination: The HPLC-APCI-MS shows the product as dimer-NH ₄ ⁺ complex with M = 410.

Example 4:

2,3-Dihydroxy-3- (4-methoxyphenyl) propionaldehyde: Formation of UV Absorption on Skin Contact (Liquidskin Model):

2,3-Dihydroxy-3- (4-methoxy-phenyl) -propionaldehyde (0.01 M) (MP-GLD) is incorporated into the Lyskinskin model consisting of 94% ethylene glycol, 6% water and optionally lysine (0 , 01 M) and stirred at 37 ° C for 12 h with exclusion of oxygen. The reaction of MP-GLD in the presence of lysine (a) is compared with the reaction in the absence of lysine (b). In addition, glyceraldehyde (GLD) is reacted with lysine (c).

The result is in In the cases a and c, the reaction solutions have turned dark brown, ie in the course of the reaction a Maillardbräunung has taken place. In contrast to c, in addition a UV absorption with an absorption maximum at 277 nm has arisen in a, which is due to the formation of anisaldehyde. The starting component MP-GLD can not structurally absorb in this area. Solution b can not undergo a tanning reaction because lysine was missing. Nevertheless, hydrolysis has produced the qualitatively identical UV absorption as in a but to a lesser extent. It can be concluded that in a the degradation of MP-GLD by lysine is additionally catalyzed.

Formulation Examples 5 to 22:

Sources:

• (1) Sasol Germany GmbH
• (2) Cognis GmbH
• (3) BASF AG
• (4) Degussa Goldschmidt AG
• (5) Merck KGaA / ^Rona®
• (6) Dow Corning
• (7) Kuhs GmbH & Co. KG
• (8) Seppic
• (9) Uniqema
• (10) Condea Chinica D.A.C.S. p. A.
• (11) Rhodia GmbH
• (12) drom
• (13) ISP Global Technologies
• (14) Nipa Laboratories GmbH
• (15) Aqualon GmbH
• (16) S. Black GmbH
• (17) Gustav Heess GmbH
• (18) D.D. Williamson
• (19) Les Colorants Wackherr SA
• (20) Bell Flavors & Fragrances

Example 5a: O / W Tanning Cream Ingredients / Trade Name source INCI [Wt .-%] 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 TRIGLYCERIDE 2:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 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. Example 5b: O / W Tanning Cream Ingredients / Trade Name source INCI [Wt .-%] 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 TRIGLYCERIDE 2:50 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 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 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. Example 5c: Non-alcoholic O / W tanning cream Ingredients / Trade Name source INCI [Wt .-%] A Marlipal 1618/11 (1) CETEARETH-11 3:00 Isopropyl myristate (2) ISOPROPYL MYRISTATE 7:00 Luvitol EHO (3) CETEARYLOCTANOATE 5:00 Tegosoft TN (4) C12-15 ALKYL BENZOATE 2:50 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 2:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 5:00 B Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 74.80 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. Example 6a: O / W tanning cream Ingredients / Trade Name source INCI [Wt .-%] A Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25-CETETH-20, STEARYL ALCOHOL 8:00 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 3:00 Isopropyl myristate (2) ISOPROPYL MYRISTATE 2:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 12:00 paraffin (5) PARAFFIN 2:00 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:15 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 4:00 Sorbitol F liquid (5) SORBITOL 2:00 Methyl 4-hydroxybenzoate (5) 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. Example 6b: O / W tanning cream Ingredients / Trade Name source INCI [Wt .-%] A Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25-CETETH-20, STEARYL ALCOHOL 8:00 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 3:00 Isopropyl myristate (2) ISOPROPYL MYRISTATE 2:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 12:00 paraffin (5) PARAFFIN 2:00 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:15 B 1,2-Propanediol (5) PROPYLENE GLYCOL 4:00 Sorbitol F liquid (5) SORBITOL 2:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:05 Water, demineralized AQUA (WATER) 49.50 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 5:00 C Water, demineralized AQUA (WATER) 9.80 Dihydroxyacetone dihydroxyacetone 2:00 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. Example 7a: O / W Tanning Cream Ingredients / Trade Name source INCI [Wt .-%] A Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 AbilWax 2434 (4) 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 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 2:50 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 2:50 Probiol L 05018 (Empty liposomes) (7) AQUA, ALCOHOL DENATE, LELCITHIN, GLYCERINE, DISODIUM PHOSPHATE 5:00 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. Example 7b: O / W Tanning Cream Ingredients / Trade Name source INCI [Wt .-%] A Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 AbilWax 2434 (4) 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 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 Probiol L 05018 (Empty liposomes) (7) AQUA, ALCOHOL DENATE, LELCITHIN, GLYCERINE, DISODIUM PHOSPHATE 5:00 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. Example 8a: O / W tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Span 60 (9) SORBITAN STEARATE 1:50 Lanette O (2) CETEARYL ALCOHOL 1:00 Cosmacol ELI (10) C12-13 ALIKYL LACTATE 2:00 Arimol HD (9) Isohexadecane 1:50 Paraffin highly liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:50 Dow Corning 9050 Silicone Elastomer Blend (6) CYCLOMETHICONE, DIMETHICONE CROSSPOLYMER 2:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 2:50 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Glycerol, anhydrous (5) GLYCERINE 2:00 Water, demineralized AQUA (WATER) 60.90 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 C Rhodicare S (11) XANTHAN GUM 12:20 D Probiol L 05018 (Empty liposomes) (7) AQUA, ALCOHOL DENATE, LECITHIN, GLYCERINE, DISODIUM PHOSPHATE 5:00 Water, demineralized AQUA (WATER) 10:00 e Fragrance Cucumber (12) 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. Example 8b: O / W tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Span 60 (9) SORBITAN STEARATE 1:50 Lanette O (2) CETEARYL ALCOHOL 1:00 Cosmacol ELI (10) C12-13 ALIKYL LACTATE 2:00 Arimol HD (9) Isohexadecane 1:50 Paraffin highly liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:50 Dow Corning 9050 Silicone Elastomer Blend (6) CYCLOMETHICONE, DIMETHICONE CROSSPOLYMER 2:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Glycerol, anhydrous (5) GLYCERINE 2:00 Water, demineralized AQUA (WATER) 60.90 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 C Rhodicare S (11) XANTHAN GUM 12:20 D Probiol L 05018 (Empty liposomes) (7) AQUA, ALCOHOL DENATE, LECITHIN, GLYCERINE, DISODIUM PHOSPHATE 5:00 Water, demineralized AQUA (WATER) 10:00 e Fragrance Cucumber (12) 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. Example 9a: mild transparent W / O tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Dow Corning 3225 C (6) CYCLOMETHICONE, DIMETHICONE COPOLYOL 23.60 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 2:00 B Dihydroxyacetone (5) dihydroxyacetone 3:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 1,2-Propanediol (5) 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. Example 9b: Mild transparent W / O tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Dow Corning 3225 C (6) CYCLOMETHICONE, DIMETHICONE COPOLYOL 23.60 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 B 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 1,2-Propanediol (5) 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. Example 10a: W / O tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Abil EM 97 (4) BIS-PEG / PPG-14/14 DIMETHICONE, CYCLOPENTASILOXANE 1:50 Abil EM 90 (4) CETYL PEG / PPG-10/1 DIMETHICONE 1.30 Ceraphyl 368 (12) ETHYLHEXYL PALMITATE 2:00 Tegosoft DEC (4) DIETHYLHEXYL CARBONATE 5:00 Dow Corning 345 (6) CYCLOMETHICONE 13:00 Dow Corning 9041 Silicone Elastomer Blend (6) DIMETHICONE CROSSPOLYMER, DIMETHICONE 3:00 Fragrance Babylon (12) PERFUME 12:30 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm Glycerol, anhydrous (5) GLYCERINE 3:00 Magnesium sulphate heptahydrate (5) MAGNESIUM SULPHATE 2:00 Phenonip (14) PHENOXYETHANOL, BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN 1:00 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. Example 10b: W / O tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Abil EM 97 (4) BIS-PEG / PPG-14/14 DIMETHICONE, CYCLOPENTASILOXANE E 1:50 Abil EM 90 (4) CETYL PEG / PPG-10/1 DIMETHICONE 1.30 Ceraphyl 368 (13) ETHYLHEXYL PALMITATE 2:00 Tegosoft DEC (4) DIETHYLHEXYL CARBONATE 5:00 Dow Corning 345 (6) CYCLOMETHICONE 13:00 Dow Corning 9041 Silicone Elastomer Blend (6) DIMETHICONE CROSSPOLYMER, DIMETHICONE 3:00 Fragrance Babylon (12) PERFUME 12:30 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm Glycerol, anhydrous (5) GLYCERINE 3:00 Magnesium sulphate heptahydrate (5) MAGNESIUM SULPHATE 2:00 Phenonip (14) PHENOXYETHANOL, BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN 1:00 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. Example 11a: Aqueous tanning gel Ingredients / Trade Name source INCI [Wt .-%] A 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 1,2-Propanediol (5) PROPYLENE GLYCOL 2:50 Sorbitol F liquid (5) SORBITOL 2:50 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:20 Water, demineralized AQUA (WATER) 28.30 B Natrosol 250 HHR (15) 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. Example 11b: Aqueous tanning gel Ingredients / Trade Name source INCI [Wt .-%] A 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 5:00 1,2-Propanediol (5) PROPYLENE GLYCOL 2:50 Sorbitol F liquid (5) SORBITOL 2:50 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:20 Water, demineralized AQUA (WATER) 28.30 B Natrosol 250 HHR (15) 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. Example 12a: aqueous-alcoholic tanning lotion for pump sprays Ingredients / Trade Name source INCI [Wt .-%] 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 Ethanol 96% (5) ALCOHOL 40.00 Day L 2 (15) PEG-20 GLYCERYL LAU RATE 7:00 1,2-Propanediol (5) 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. Example 12b: aqueous-alcoholic tanning lotion for pump sprays Ingredients / Trade Name source INCI [Wt .-%] 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 Ethanol 96% (4) ALCOHOL 40.00 Day L 2 (4) PEG-20 GLYCERYL LAU RATE 7:00 1,2-Propanediol (5) 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. Example 13a: W / Si Tanning Gel Ingredients / Trade Name source INCI [Wt .-%] A Dow Corning 5225 C (6) CYCLOPEN TASILOXANE, PEG / PG-18/18 DIMETHICONE 8:00 pm DM-fluid-A-6cs (16) DIMETHICONE 4:00 Soybean oil (17) GLYCINE SOY (SOYBEAN OIL) 2:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B RonaCare ^® Ectoin (5) ECTOIN 12:30 1,2-Propanediol (5) PROPYLENE GLYCOL 30.00 dipropylene (3) DIPROPYLENE GLYCOL 10:00 Sodium chloride (5) SODIUM CHLORIDE 1:00 Etanol 96% (5) ALCOHOL 5:00 1% caramel in water (18) CARAMEL 2:50 1% FD & C Yellow No. 6 in water (3) AQUA (WATER), Cl 15985 (FD & C YELLOW NO. 6) 12:25 Water, demineralized AQUA (WATER) 19:25 C Fragrance Melopeach (12) 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. Example 13b: W / Si Tanning Gel Ingredients / Trade Name source INCI [Wt .-%] A Dow Corning 5225 C (6) CYCLOPEN TASILOXANE, PEG / PG-18/18 DIMETHICONE 8:00 pm DM-fluid-A-6cs (16) DIMETHICONE 4:00 Soybean oil (17) GLYCINE SOY (SOYBEAN OIL) 2:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B RonaCare ^® Ectoin (5) ECTOIN 12:30 1,2-Propanediol (5) PROPYLENE GLYCOL 30.00 dipropylene (3) DIPROPYLENE GLYCOL 10:00 Sodium chloride (5) SODIUM CHLORIDE 1:00 Etanol 96% (5) ALCOHOL 5:00 1% caramel in water (18) CARAMEL 2:50 1% FD & C Yellow No. 6 in water (3) AQUA (WATER), CI 15985 (FD & C YELLOW NO. 6) 12:25 Water, demineralized AQUA (WATER) 19:25 C Fragrance Melopeach (12) 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. Example 14a: O / W tanning cream with UV A / B protection Ingredients / Trade name source INCI [Wt .-%] A Eusolex ^® 2292 (5) ETHYLHEXYL METHOXYCINNAMATE, BHT 3:00 Eusolex ^® 4360 (5) BENZOPHENONE-3 12:50 Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyoll 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate sodium salt (5) SODIUM METHYLPARABEN 12:17 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. Example 14b: O / W tanning cream with UV A / B protection Ingredients / Trade Name source INCI [weight A Eusolex ^® 2292 (5) ETHYLHEXYL METHOXYCINNAMATE, BHT 3:00 Eusolex ^® 4360 (5) BENZOPHENONE-3 12:50 Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyoll 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 1:00 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 2:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate sodium salt (5) SODIUM METHYLPARABEN 12:17 Water, demineralized AQUA (WATER) 53.18 C Dihydroxyacetone (5) 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. Example 14c: O / W tanning cream with UV A / B protection Ingredients / Trade Name source INCI [Wt .-%] A Eusolex ^® 2292 (5) ETHYLHEXYL METHOXYCINNAMATE, BHT 3:00 Eusolex ^® 4360 (5) BENZOPHENONE-3 12:50 Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyoll 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate sodium salt (5) SODIUM METHYLPARABEN 12:17 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. Example 14d: O / W tanning cream with UV A / B protection Ingredients / Trade Name source INCI [Wt .-%] A Eusolex ^® 2292 (5) ETHYLHEXYL METHOXYCINNAMATE, BHT 3:00 Eusolex ^® 4360 (5) BENZOPHENONE-3 12:50 Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyoll 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 hydroxybenzoate sodium salt (5) SODIUM METHYLPARABEN 12:17 Water, demineralized AQUA (WATER) 53.18 C 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 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. The pH is adjusted to pH = 7.0 using sodium hydroxide solution or citric acid. Example 14d: O / W tanning cream with UV A / B protection Ingredients / Trade Name source INCI [Wt .-%] A Eusolex ^® 2292 (5) ETHYLHEXYL METHOXYCINNAMATE, BHT 3:00 Eusolex ^® 4360 (5) BENZOPHENONE-3 12:50 Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Luvitol EHO (3) CETEARYL OCTANOATE 5:00 Miglyoll 812 N (1) CAPRYLIC / CAPRIC 5:00 TRIGLYCERIDES Paraffin liquid (5) PARAFFINUM LIQUIDUM (MINERAL OIL) 3:00 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.60 Dow Corning 200 Fluid (350 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 Methyl 4-hydroxybenzoate sodium salt (5) SODIUM METHYLPARABEN 12:17 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. Example 15a: O / W shimmering tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Span 60 (9) SORBITAN STEARATE 1:50 Lanette O (2) CETEARYL ALCOHOL 1:00 Cosmacol ELI (10) C12-13 ALKYL LACTATE 3:00 Cosmacol EMI (10) DI-C12-13 ALKYL MALATE 1:50 Dow Corning 9040 Silicone Elastomer Blend (6) CYCLOMETHICONE, DIMETHICONE CROSSPOLYMER 1:00 Arlamol HD (9) Isohexadecane 3:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 12:50 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Colorona® ^® Red Gold (5) MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (ION OXIDES) 2:00 Glycerol, anhydrous (5) GLYCERIN 2:00 Caramel 250 (18) CARAMEL 1:00 FD & C Yellow No 6 W082 (19) CI 15985 12:01 Water, demineralized AQUA (WATER) 73.09 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 C Sepigel 305 (18) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 12:50 D Fragrance Babylon (12) 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. Example 15b: O / W shimmering tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Span 60 (9) SORBITAN STEARATE 1:50 Lanette O (2) CETEARYL ALCOHOL 1:00 Cosmacol ELI (10) C12-13 ALKYL LACTATE 3:00 Cosmacol EMI (10) DI-C12-13 ALKYL MALATE 1:50 Dow Corning 9040 Silicone Elastomer Blend (6) CYCLOMETHICONE, DIMETHICONE CROSSPOLYMER 1:00 Arlamol HD (9) Isohexadecane 3:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 5:00 12:50 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Colorona® ^® Red Gold (5) MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (ION OXIDES) 2:00 Glycerol, anhydrous (5) GLYCERIN 2:00 Caramel 250 (18) CARAMEL 1:00 FD & C Yellow No 6 W082 (19) CI 15985 12:01 Water, demineralized AQUA (WATER) 73.09 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 C Sepigel 305 (8th) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 12:50 D Fragrance Babylon (12) 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 NB and it is homogenized. It is then cooled to 40 ° C and the phase D is added successively. Example 16a: O / W shimmering tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Span 60 (9) SORBITAN STEARATE 1:50 Lanette O (2) CETEARYL ALCOHOL 1:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Cosmacol ELI (10) C12-13 ALKYL LACTATE 3:00 Cosmacol EMI (10) DI-C12-13 ALKYL MALATE 1:50 Arlamol HD (9) Isohexadecane 3:00 Dow Corning 9040 Silicone Elastomer Blend (6) CYCLOMETHICONE, DIMETHICONE CROSSPOLYMER 1:00 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Timiron ^® Starluster MP-115 (5) MICA, CI 77891 (TITANIUM DIOXIDE) 1:00 Glycerol, anhydrous (5) GLYCERIN 2:00 Caramel 250 (18) CARAMEL 0.60 FD & C Yellow No 6 W082 (19) CI 15985 12:01 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 59.49 C Sepigel 305 (8th) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 12:50 D Probiol L 05018 (Empty liposomes) (7) AQUA, ALCOHOLDENATE, LECITHIN, GLYCERINE, DISODIUM PHOSPHATE 5:00 Water, demineralized AQUA (WATER) 10:00 e Fragrance Babylon (12) 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 NB 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. Example 16b: O / W shimmering tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Span 60 (9) SORBITAN STEARATE 1:50 Lanette O (2) CETEARYL ALCOHOL 1:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 Cosmacol ELI (10) C12-13 ALKYL LACTATE 3:00 Cosmacol EMI (10) DI-C12-13 ALKYL MALATE 1:50 Arlamol HD (9) Isohexadecane 3:00 Dow Corning 9040 Silicone Elastomer Blend (6) CYCLOMETHICONE, DIMETHICONE CROSSPOLYMER 1:00 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Timiron ^® Starluster MP-115 (5) ME, CI 77891 (TITANIUM DIOXIDE) 1:00 Glycerol, anhydrous (5) GLYCERIN 2:00 Caramel 250 (18) CARAMEL 0.60 FD & C Yellow No 6 W082 (19) CI 15985 12:01 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 59.49 C Sepigel 305 (8th) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 12:50 D 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 Probiol L 05018 (Empty liposomes) (7) AQUA, ALCOHOLDENATE, LECITHIN, GLYCERINE, DISODIUM PHOSPHATE 5:00 Water, demineralized AQUA (WATER) 10:00 e Fragrance Babylon (12) 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 using sodium hydroxide solution or citric acid. Example 17a: clear W / O shimmering tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Abil EM 97 (4) BIS-PEG / PPG-14/14 DIMETHICONE, CYCLOPENTASILOXANE 1.20 Abil EM 90 (4) CETYL PEG / PPG-10/1 DIMETHICONE 1:00 Mirasil CM 5 (11) CYCLOMETHICONE 12:00 Ceraphyl 368 (13) ETHYLHEXYL PALMITATE 2:00 Dow Corning 9041 Silicone Elastomer Misery (6) DIMETHICONE CROSSPOLYMER, DIMETHICONE 1.60 Tegosoft DEC (4) DIETHYLHEXYL CARBONATE 5:00 Fragrance Babylon (12) PERFUME 12:30 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Caramel 250 (18) CARAMEL 0.60 Timiron ^® Starluster MP-115 (5) ME, CI 77891 (TITANIUM DIOXIDE) 1:00 FD & C Yellow No 6 W082 (19) CI 15985 12:01 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm Glycerol, anhydrous (5) GLYCERIN 3:00 Magnesium sulfate heptahydrate (5) MAGNESIUM SULFATE 2:00 Ethanol 96% (5) ALCOHOL 8:00 Phenonip (5) PHENOXYETHANOL, BUTAYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN 1:00 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. Example 17b: clear W / O shimmering tanning lotion Ingredients / Trade Name source INCI [Wt .-%] A Abil EM 97 (4) BIS-PEG / PPG-14/14 DIMETHICONE, CYCLOPENTASILOXANE 1.20 Abil EM 90 (4) CETYL PEG / PPG-10/1 DIMETHICONE 1:00 Mirasil CM 5 (11) CYCLOMETHICONE 12:00 Ceraphyl 368 (13) ETHYLHEXYL PALMITATE 2:00 Dow Corning 9041 Silicone Elastomer Misery (6) DIMETHICONE CROSSPOLYMER, DIMETHICONE 1.60 Tegosoft DEC (4) DIETHYLHEXYL CARBONATE 5:00 Fragrance Babylon (12) PERFUME 12:30 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 5:00 B RonaCare ^® Ectoin (5) ECTOIN 12:50 Caramel 250 (18) CARAMEL 0.60 Timiron ^® Starluster MP-115 (5) ME, CI 77891 (TITANIUM DIOXIDE) 1:00 FD & C Yellow No 6 W082 (19) CI 15985 12:01 1,2-Propanediol (5) PROPYLENE GLYCOL 8:00 pm Glycerol, anhydrous (5) GLYCERIN 3:00 Magnesium sulfate heptahydrate (5) MAGNESIUM SULFATE 2:00 Ethanol 96% (5) ALCOHOL 8:00 Phenonip (14) PHENOXYETHANOL, BUTAYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN 1:00 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. Example 18: Skin protection cream giving a summer-like complexion Ingredients / Trade Name source INCI [Wt .-%] A Eusolex ^® OCR (5) OCTOCRYLENE 5:00 Eusole ^® 9020 (5) BUTYL METHOXY-DIBENZOYLMETHANE 1:00 Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Tegosoft liquid (4) CETEARYL ETHYLHEXANOATE 3:50 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 3:50 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.20 Dow Corning 200 (100 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 3,3-diethoxy-1- (4-methoxy-phenyl) propanes-1,2-diol (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE diethyl 2:00 B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 RonaCare ^® Ectoin (5) ECTOIN 12:30 Methyl 4-hydroxybenzoate (5) METHYLPARABEN 12:15 Water, demineralized AQUA (WATER) 70.20 C Fragrance (20) PERFUME 12:10 "Sunshine for cream D" 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. Example 19: Skin protection cream giving a light summer tan Ingredients / Trade Name source INCI [Wt .-%] A Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Tegosoft liquid (4) CETEARYL ETHYLHEXANOATE 6:50 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 6:50 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.20 Dow Corning 200 (100 cs) (6) DIMETHICONE 12:50 Propyl-4-hydroxybenzoate (5) PROPYLPARABEN 12:05 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 0.75 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" (20) 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. Example 20: velvety body lotion for a natural color Ingredients / Trade Name source INCI [Wt .-%] A Abil EM 07 (4) BIS-PEG / PPG-14/14 DIMETHICONE, CYCLOPENTASILOXANE 1:50 Abil EM 90 (4) CETYL PEG / PPG-10/1 DIMETHICONE 1.30 Ceraphyl 368 (13) ETHYLHEXYLPALMITATE 2:00 Tegosoft DEC (4) DIETHYLHEXYL CARBONATE 5:00 Dow Corning 345 (6) CYCLOMETHICONE 13:00 Dow Corning 9041 Silicone Elastomer Blend (6) DIMETHICONE CROSSPOLYMER, DIMETHICONE 3:00 Fragrance Babylon (12) PERFUME 12:30 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 1:00 B Dihydroxyacetone (5) dihydroxyacetone 1:00 erythrulose ERYTHRULOSE 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 heptahydrate (5) MAGNESIUM SULFATE 2:00 Ethanol 96% (5) ALCOHOL 8:00 Phenonip (14) PHENOXYETHANOL, BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN 1:00 Water, demineralized AQUA (WATER) 36.40 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. Example 21: gentle tanning cream with silver glitter Ingredients / Trade Name source INCI [Wt .-%] A Montanov 68 (8th) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Cosmacol ELI (10) C12-13 ALKYL LACTATE 4:00 Arlamol HD (9) Isohexadecane 3:00 Span 60 (9) SORBITAN STEARATE 1:50 Cosmacol EMI (10) DI-C12-13 ALKYL MALATE 2:50 Lanette O (2) CETEARYL ALCOHOL 1:00 Phenonip (14) PHENOXYETHANOL, BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN 0.80 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 1:00 B RonaCare ^® Tocopherol Acetate (5) TOXOPHERYLACETATE 12:50 C Ronastar ^® Silver (5) CALCIUM ALUMINUM BOROSILICATE, SILICA, CI 77891 (TITANIUM DIOXIDE), TIN OXIDE 1:00 Glycerol, anhydrous (5) GLYCERIN 3:00 RonaCare ^® Ectoin (5) ECTOIN 12:50 Water, demineralized AQUA (WATER) 69.50 D Sepigel 305 (8th) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 0.60 e Dihydroxyacetone (5) dihydroxyacetone 1:00 Water, demineralized AQUA (WATER) 4:00 F Germall 115 (13) IMIDAZOLIDINYL UREA 12:30 Water, demineralized AQUA (WATER) 1:50 G Fragrance Melopeach (12) 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. Example 22: Day Care Cream Ingredients / Trade Name source INCI [Wt .-%] A Tego Care 150 (4) GLYCERYL STEARATE, STEARETH-25, CETETH-20, STEARYL ALCOHOL 8:00 Lanette O (2) CETEARYL ALCOHOL 1:50 Tegosoft liquid (4) CETEARYL ETHYLHEXANOATE 6:50 Miglyol 812 N (1) CAPRYLIC / CAPRIC TRIGLYCERIDE 6:50 Abil wax 2434 (4) STEAROXY DIMETHICONE 1.20 Dow Corning 200 (100 cs) (6) 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 2,3-dihydroxy-3- (4-methoxy-phenyl) propionaldehyde (5) DIHYDROXY-METHOXY-PHENYL PROPIONALDEHYDE 3:00 Dihydroxyacetone dihydroxyacetone 1:00 Water, demineralized AQUA (WATER) 09:00 D Fragrance "sunshine for cream D" (20) 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.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 93/04665 [0094]
• EP 0 487 404 A [0094]
• US 6242099 B1 [0123]
• WO 00/09652 [0123]
• WO 00/72806 [0123]
• WO 00/71084 [0123]
• DE 10133202 A [0133, 0133]
• DE 4308282 A [0163]

Cited non-patent literature

• Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53 64 [0114]
• K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108 [0131]
• CA Rice-Evans, NJ Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159 [0132]
• K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, AEMF Soffers and IMCM Rietjens (Free Radical Biology & Medicine 2001, 31 (7), 869-881 [0132]

Claims (15)

Use of at least one compound of the formula (1), (2), or (3)

wherein - R1, R2, R4, R5, R14, R15, R17 and R18 independently represent H, OH, C ₁ - to C ₂₀ -alkyl, C ₁ - to C ₂₀ -alkoxy, -O- (CO) -C ₁ - to C ₂₀ -alkyl or O- (CH ₂ ) ₂ -OH, - R 3 and R 16 independently of one another are H, OH, C ₁ - to C ₂₀ -alkyl, C ₁ - to C ₂₀ -alkoxy, O- ( CO) -C ₁ - to C ₂₀ -alkyl, O- (CH ₂ ) ₂ -OH or NR 11 R 12, - R 6 is H, C ₁ - to C ₂₀ -alkyl, C ₁ - to C ₂₀ -alkoxy, CH ₂ OH, CHOH-CH ₂ OH or (CO) -OC ₁ - to C ₂₀ -alkyl, - R 7 and R 8 independently of one another are C ₁ - to C ₂₀ -alkyl, - R 9 and R 10 are each independently H, C ₁ to C ₂₀ -alkyl, CH ₂ OH, CHOH-CH ₂ OH or CHOH-CHOH-CH ₂ OH, where in R9 and R10 the sum of the carbon atoms of the hydroxyalkyl radicals 0, 1, 2, 3, 4, 5 or 6 R 11 and R 12 independently of one another are C ₁ - to C ₂₀ -alkyl, - R 13 is H or

wherein alkyl radicals may be straight-chain, branched or cyclic, to release compounds, wherein a compound of the formula (1) liberates compounds of the formula (4) and / or (5)

a compound of formula (2) releases compounds of formula (1), (4), (5), (6a) and / or (6b), wherein formula (1), (4) and (5) are as previously defined

and a compound of the formula (3) releases compounds of the formula (1), (4), (5) and / or (7), wherein formula (1), (4) and (5) are as defined above

Use according to claim 1, characterized in that - R1, R2, R4, R5, R14, R15, R17 and R18 independently of one another are H, OH, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxy or O- (CO) -C ₁ - to C ₈ -alkyl, - R 3 and R 16 independently of one another are H, OH, C ₁ - to C ₈ -alkyl, C ₁ - to C ₈ -alkoxyl, O- (CO) -C ₁ - to C ₈ -alkyl or NR 11 R 12 - R 6 is H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C _8- alkyl, - R7 and R8 independently of one another are C ₁ - to C ₈ -alkyl, - R 9 and R 10 are each independently H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH or CHOH-CHOH-CH ₂ OH, where in R9 and R10 the sum of the carbon atoms of the hydroxyalkyl radicals is 0, 1, 2, 3, 4, 5 or 6, - R11 and R12 independently of one another are C ₁ - to C ₈ -alkyl stand, - R13 for H or

wherein alkyl radicals may be straight-chain, branched or cyclic. Use according to claim 1 or 2, characterized in that it is a compound selected from the group comprising

is. Use according to one or more of claims 1 to 3, characterized in that the released compound is a UV filter, a skin tanning substance, a preservative or a coolant. Compound of the formula (1)

in which - R1, R2, R4 and R5 independently of one another are H, OH, methoxy or tert-butyl, - R3 and R16 independently of one another are H, OH, methoxy, tert-butyl or NR11R12, - R6 is H, C C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ -alkyl, - R 11 and R 12 independently of one another represent C ₁ - to C ₈ -Alkyl, - R13 is H or

R14, R15, R17 and R18 independently of one another are H, OH, methoxy or tert-butyl, it being possible for the alkyl radicals contained to be straight-chain, branched or cyclic, and the compounds

excluded are. Compound of the formula (2)

in which - R1, R2, R4 and R5, independently of one another, are H, OH, methoxy or tert-butyl, - R3 and R16 independently of one another are H, OH, methoxy, tert-butyl or NR11R12, - R6 is H, C ₁ - to C ₈ -alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ -alkyl, - R 7 and R ₈ independently of one another represent C ₁ - to C ₈ - Alkyl, - R11 and R12 independently of one another are C ₁ - to C ₈ -alkyl, - R 13 is H or

R14, R15, R17 and R18 independently of one another are H, OH, methoxy or tert-butyl, it being possible for the alkyl radicals contained to be straight-chain, branched or cyclic, and the compounds

excluded are. Compounds of the formula (3)

in which - R1, R2, R4 and R5, independently of one another, are H, OH, methoxy or tert-butyl, - R3 and R16 independently of one another are H, OH, methoxy, tert-butyl or NR11R12, - R6 is H, C ₁ - to C ₈ alkyl, CH ₂ OH, CHOH-CH ₂ OH, CH ₂ OCH ₃ or (CO) -OC ₁ - to C ₈ alkyl, - R9 and R10 independently of one another for H, C ₁ - to C _8- alkyl, CH ₂ OH, CHOH-CH ₂ OH or CHOH-CHOH-CH ₂ OH, where in R9 and R10 the sum of the carbon atoms of the hydroxyalkyl radicals is 0, 1, 2, 3, 4, 5 or 6, R11 and R12 independently of one another are C ₁ - to C ₈ -alkyl, - R 13 is H or

R14, R15, R17 and R18 independently of one another are H, OH, methoxy or tert-butyl, it being possible for the alkyl radicals contained to be straight-chain, branched or cyclic. A process for producing a compound of the formula (1) according to claim 1, wherein a compound of the formula (2) or (3) according to claim 1 is converted to a compound of the formula (1) by acid hydrolysis. Process for the preparation of a compound of formula (2) or (3) according to claim 1, wherein a compound of formula (8)

is converted by acetalization and subsequent dihydroxylation into a compound of formula (2) or (3). A preparation comprising at least one compound of the formula (1), (2) or (3) according to one or more of claims 1 to 3. Preparation according to claim 10, characterized in that it is a cosmetic or pharmaceutical preparation. A preparation according to claim 10 or 11, characterized in that the at least one compound of the formula (1), (2) or (3) is contained in amounts of 0.05 to 10 wt .-%. Preparation according to one or more of claims 10 to 12, characterized in that it contains further self-tanning substances and / or UV filters. Preparation according to one or more of claims 10 to 13, characterized in that it contains one or more antioxidants and / or one or more vitamins. Process for the preparation of a preparation according to one or more of Claims 10 to 14, characterized in that at least one compound of the formula (1), (2) or (3) is mixed with a carrier and optionally with further active or auxiliary substances