EP2049075A2

EP2049075A2 - Use of ascorbic acid derivatives for the functionalization of matrices

Info

Publication number: EP2049075A2
Application number: EP07785853A
Authority: EP
Inventors: Thomas Rudolph; Philipp Buehle; Herwig Buchholz
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2006-08-11
Filing date: 2007-06-27
Publication date: 2009-04-22
Also published as: JP5470037B2; DE102006037724A1; CN101686925B; WO2008017346A3; US20100167936A1; WO2008017346A2; US9023889B2; CN101686925A; JP2010505749A

Abstract

The invention relates to the use of at least one ascorbic acid derivative for the functionalization of matrices, and to specific ascorbic acid derivatives and processes for their preparation.

Description

Use of ascorbic acid derivatives for the functionalization of

matrices

The invention relates to the use of at least one ascorbic acid derivative for the functionalization of matrices, and more particularly

Ascorbic acid derivatives and process for their preparation.

The functionalization according to the invention of proteinaceous matrices, in particular the skin, the hair and / or the nails, is effected by covalent anchoring or strong electrostatic interaction. This leads to an immobilization of the desired active ingredients, for example UV filters, dyes, or allows controlled release of active ingredient, for example for pharmacological, antimicrobial, fungicidal, herbicidal, insecticidal or cosmetic active ingredients or for X-ray contrast agents.

A preferred field of application of the use according to the invention is the UV protection. Human skin is subject to certain aging processes that are partly due to intrinsic processes (chronoaging) and partly due to exogenous factors (environmental, e.g., photoaging).

The exogenous factors include, in particular, sunlight or artificial radiation sources with a comparable spectrum and compounds which can be formed by the radiation, such as undefined reactive photoproducts, which can also be free-radical or ionic.

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. Due to lack of skin adhesion but the protection period is limited, especially because conventional UV filters can be washed off very easily, for example, sweat or water. It is a strategy known, for example, from WO 2006/018104 to derivatize UV filters or self-tanning substances in such a way that they can bind covalently to the stratum corneum of the epidermis via a reactive molecular part and thus functionalize the skin with the UV filter or self-tanner. For the effective attachment to proteins and amino acids of the outer skin layers, it is necessary that the corresponding UV filter derivatives or derivatives of other active substances, such as pharmacological, antimicrobial, fungicidal, herbicidal, insecticidal or cosmetic active ingredients, X-ray contrast agents or dyes, as high as possible Reactivity of their bondable moieties have.

There is therefore an increasing need for skin-friendly compounds which are able to functionalize protein-containing matrices and can be incorporated in a suitable manner into cosmetic or pharmacological preparations.

It has now surprisingly been found that ascorbic acid derivatives, in particular of ascorbic acid derivatives substituted in the 6- and / or 5-position by active substance radicals, are outstandingly suitable for the functionalization of matrices. Preferred matrices here are skin, hair and / or nails, whereby the general principle can also be applied to the functionalization of synthetic polymer matrices containing amino groups or thiol groups, isolated proteins or gelatin. The products formed by binding to such matrices may also themselves be used as cosmetic agents for the preparation of cosmetic products. It can be derivatized according to the invention both D- and L-ascorbic acid or mixtures thereof. A first subject of the invention is therefore the use of at least one ascorbic acid derivative, in particular of ascorbic acid derivatives substituted in the 6- and / or 5-position by active substance radicals, for the functionalization of matrices.

Of ascorbic acid (vitamin C), often used as a natural antioxidant in cosmetics or food indus- try, it is known that depending on various parameters such as oxygen, pH, metal ion concentration (eg of iron or copper) or temperature significant losses due to vitamin C Degradation occur. [H.-D. Belitz, W. Grosch, Textbook of Food Chemistry, Springer-Verlag, 1987, 3rd edition, p. 337.]

In EP 0664290 derivatives of ascorbic acid are described, wherein the 2-position or also the 2- and 6-position is esterified by cinnamic acid. These ascorbic acid derivatives are used as antioxidants or according to EP 104631 as NO donors.

EP 0917871 discloses ascorbic acid derivatives whose hydroxy group in the 4-position is substituted by C ₁ -C ₆ -alkoxycarbonyl and their hydroxy groups in the 5- and / or 6-position by C ₁ -C 20 -acyl or C ₁ -C ₆ -alkoxycarbonyl, the acyl chains branching , unbranched, saturated or (multiply) unsaturated, ie based on fatty acids.

Aromatic systems are excluded. These compounds are also used as antioxidants.

EP 1527777 describes ascorbic acid derivatives in which at least one hydroxy group of ascorbic acid is esterified with a benzoic acid, preferably a gallic acid. The compounds are described inter alia as inhibitors of a tyrosinase activity or as an inhibitor for melanin synthesis. The inventive Use for the functionalization of matrices is not mentioned or even suggested.

In G. Tschank et al, Biochem. J., 1994, 300, 75-79 the compounds O ⁶ - (2-acetoxybenzoyl) -L-ascorbate and O ⁵ O ⁶ -bis (2-acetoxybenzoyl) -L-ascorbate are described. These compounds are in the

Able to support the activity of the enzyme prolyl-4-hydroxylase, but the bis-substituted compound has a lower affinity for the enzyme.

For the use according to the invention, in particular at least one ascorbic acid derivative of the formula I is suitable,

in which

R ¹ or R ^{2 are} each independently of one another hydroxy, -O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl,

Alkyl C ₁ -C ₆ -alkyl,

M alkali or alkaline earth metal cation or H,

R ³ or R ^{4 are} each independently hydroxy or a radical B and

B is the radical of a pharmacological, antimicrobial, fungicidal, herbicidal, insecticidal or cosmetic active ingredient, a UV filter, an X-ray contrast agent or a dye, with the proviso that at least one of R ³ or R ^{4 represents} a

Rest B stands.

dC _ß alkyl means an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms, for example methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl or n hexyl. Suitable alkoxy radicals for R ¹ or R ² are those whose alkyl group contains 1 to 6 C atoms, preferably 1 to 4 C atoms. Examples of alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

The group -OPO ₃ M is preferably the -OPO ₃ H group, but it is also possible to use salts of the formula I where M in formula I is an alkali metal cation, for example Na or K, or an alkaline earth metal cation, for example of Mg or Ca, dense.

The attachment of a carbohydrate in position 2 or 3 of ascorbic acid, referred to as O-glycosyl in formula I, can be used, for example, for monosaccharides such as ribose, arabinose xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribulose , Xylulose, psicose, fructose, sorbose or tagatose. In this list both isomers, i. each contain the D or L forms. Preferably, glucose, galactose or fructose, most preferably glucose, are used.

In principle, however, disaccharides are also suitable, such as sucrose (or else called sucrose), lactose, trehalose, maltose, cellobiose, gentiobiose or melibiose. This list includes both the α and β forms. From the group of disaccharides are preferably sucrose or lactose, particularly preferably sucrose used.

Preferably, the radical R ¹ in formula I is hydroxy and R ² is

-O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl, as previously described. Preferably, the radical R ² in formula I is hydroxy and R ¹ is -O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl, as described above.

Particularly preferably, both radicals R ² and R ^{1 are} hydroxy.

R ³ or R ⁴ are each independently hydroxy or a radical B and

B is the residue of a pharmacological, antimicrobial, fungicidal, herbicidal, insecticidal or cosmetic active ingredient, a UV filter, an X-ray contrast agent or a dye.

In a preferred embodiment, the radical R ^{3 is} hydroxy and R ⁴ corresponds to a radical B, as described above and preferred below. However, according to the invention it is also possible to use mixtures of ascorbic acid derivatives of the formula I in which the radical B is both R ³ and R ⁴ , and also R ³ or R ⁴ .

Preferably, the radical B _{1 is} as described above and described in more detail below, linked via an ester function to the 5 and / or 6 of the formula I. Particularly preferably, the radical B is bonded via a carbonyloxy function. In a further embodiment, the radical B is bonded via an ether function.

The radicals R ¹ and R ^{2 of} the ascorbic acid derivatives of the formula I are chosen so that when applied to the matrix, in particular the skin, the hair and / or the nails, or even when applied to isolated proteins or gelatin, bonds to reactive groups of Matrix, such as amino and / or thiol groups. The binding reaction is facilitated if, by oxidation of the hydroxyl groups R ¹ and / or R ^2, activation of the ascorbic acid derivative of the formula I occurs by degradation. The hydroxy groups R ¹ and / or R ² can also when applied to the Matrix by hydrolysis of an ascorbic acid derivative of the formula I with R ¹ and / or R ² ≠ H arise.

The theory of the further functionalization of the matrix is described below via a binding activation by an ascorbic acid degradation, but the functionalization of the matrices should not be bound to this theory.

In Scheme 1, the ascorbic acid derivative decomposes into xylosone and / or A-deoxypentosone, where in the formulas of Scheme 1, R ^{3 is} OH or a radical B and R ^{4 is} a radical B, as described above:

Scheme 1:

The reactive dicarbonyl compounds xylosone and 4-deoxypentosone are able to react with proteins and amino acids in the manner of a Maillard reaction. This step corresponds to an integration of active ingredient-carrying radicals R ³ and / or R ⁴ in the matrix. The matrix is therefore functionalized according to the active ingredient residue.

Compared to, for example, non-binding UV filters, this mechanism has two additional benefits, namely the antioxidant (degradation)

Reaction of the ascorbic acid base body and, if appropriate, a tanning reaction analogous to the Maillard reaction (self-tanning component).

In a variant of the invention it is preferred if the radical B is a residue of a pharmacologically active substance.

Preferably, the substances having a pharmacological action are aromatic and have a carbonyl function.

Examples of substances with pharmacological action are:

1) Anti-inflammatory anti-rheumatics: e.g. those of the acetic acid derivatives, e.g. Indomethacin (CAS: 53-86-1), acemetacin (CAS: 53164-05-9), tolmetin (CAS: 26171-23-3), diclofenac (CAS: 15307-86-5), lonozolac (CAS: 53808- 88-1) and / or those of the propionic acid derivatives, such as Ibuprofen (CAS: 15687-27-1), fenoprofen (CAS: 31879-05-7),

Sodium naproxen (CAS: 26159-34-2), ketoprofen (CAS: 22071-15-4);

2) anti-arteriosclerotic B vitamins: e.g. Aluminum nicotinic acid (CAS: 1976-28-9), aminobenzoic acid (CAS: 150-13-0);

3) anti-arrhythmic, anti-convulsant non-steroids such as e.g. Voltaren / diclofenac (CAS: 15307-86-5);

4) class I, II, II and IV anti-arrythmic beta-sympatholytic substances such as e.g. BW-A-575-C (CAS: 103221-88-1);

5) β-lactam antibiotics: eg those of the penam, crabapenem, oxapenam, cephem, oxacephem and monocyclic β-lactams, such as eg amoxillin (CAS: 26787-78-0), cefoxitin (CAS: 35607- 66-0) and ampicillin (CAS: 69-53-4); 6) antibiotics from the family of penicillins, aminopenicillins, acylaminopenicillins, carboxypenillins or cephalosporins such as tazobactam (CAS: 89786-04-9), cloxacillin-sulfone (CAS: 76788-83-5), sulbactam (CAS: 68373-14- 8th); 7) Antibiotics from the family of tetracyclines such as

Glycine methyltetracycline (CAS: 751-98-4), lymecycline (CAS: 992-21-2), calcium chlortetracycline (CAS: 57122-99-3), apicyclin (CAS: 15599-51-6).

8) Anti-inflammatory prostaglandin antagonists, e.g. Sodium Lobenzarit (CAS: 64808-48-6), Flutiazin (CAS: 7220-56-6), Araprofen (CAS: 15250-13-2);

9) Anti-septic and anti-diabetic drugs from the family of phenyl-sulfonamides, e.g. Carboxytolbutamide (CAS: 2224-10-4);

10) anti-inflammatory agents, analgesics, collagenase inhibitors, and keratolytic agents, e.g. Salicylic acid (CAS: 69-72-7); 11) anti-astmatics e.g. those of the xanthine derivatives, e.g. Acefylline (CAS:

652-37-9);

12) anti-astmatics and anti-anaphylactics such as e.g. Sodium-Ablukast (CAS:

96565-55-8), Amlexanox (CAS: 68302-57-8), AH-7725 (CAS: 68302-57-8),

Calcium nedocromil (CAS: 101626-68-0); 13) Thyroid Hormones and Anti-Arteriosclerotics, e.g. Detrothyronin

(CAS: 5714-08-9), sodium levothyroxine (CAS: 55-03-8), sodium

Dextrothyroxine (CAS: 137-53-1);

14) analgesics, anti-inflammatories, anti-pyretics, e.g. those of

Pyrazolidine derivatives, e.g. Anthradione (CAS: 19854-90-1). 15) chelators, e.g. HBED (CAS: 35998-29-9), calteridol (CAS:

132722-73-7)

16) prostaglandins for ulcer therapy, e.g. Sodium beraprost (CAS: 88475-69-8) or

17) cis- or trans-urocanic acid.

These examples are intended to exemplify the possibilities without the

Restrict selection. In a further variant of the invention it is preferred if the radical B is a residue of an antimicrobial active ingredient.

Particularly suitable are preservatives that

Carboxylic acid derivatives are and also contain a conjugated π-electron system, such as benzoic acid, p-hydroxybenzoic acid or sorbic acid.

These examples are intended to exemplify the possibilities without limiting the selection.

In a further variant of the invention it is preferred if the radical B is a radical of a fungicidal, herbicidal or insecticidal active ingredient. In summary, these substances may also be referred to as pesticides.

By way of example, the following suitable pesticides may be mentioned:

Parathion (-ethyl) parathion-methyl

Bromophos 2,4-D

Benomyl, benlate or trichloroacetic acid (TCA).

In a further variant of the invention, it is preferred if the radical B is a radical of a cosmetic active substance.

Particularly suitable are the substances nicotinic acid, nicotinamide,

retinoic acid,

Biotin, ie with the remainder B = and the aromatic amino acids phenylalanine, tyrosine, tryptophan,

Histidine and tyrosine.

In a further variant of the invention it is preferred if the radical B is a

Remainder of an X-ray contrast agent.

Preferably, the X-ray contrast agents are aromatic and have a carbonyl function.

Examples of X-ray contrast agents are locetamic acid (CAS: 16034-77-8), iodocetylic acid (CAS: 54510-20-2), meglumine acid trizoate (CAS: 22154-43-4), iodohippuric acid (CAS: 147-58-0), Sodium bunamiodate (CAS: 1923-76-8), acetic acid (CAS: 85-36-9), but also diagnostics for other applications such as locanlidine acid (CAS: 74855-17-7), silver fluorescein (CAS : 25931-86-6), Pankensan (CAS: 38219-60-2). These examples are intended to exemplify the possibilities for bound diagnostic substances without restricting the selection.

In a further variant of the invention it is preferred if the radical B is a

Remainder of a dye.

Preferably, organic dyes are used which are carboxylic acid derivatives. By way of example, substances are mentioned which serve the coloring of foods, medicaments and cosmetics, such as

Bixin (contained in Annatto, E160b, Cl. 75120); norbixin; Apocarotic acid ethyl ester, E160f, Cl. 40825; Chlorophyll, E140, Cl. 75810; Erythrosin, E127, Cl. 45430; Carmine, Cochineal, E120, Cl. 75470; Litholubin BK, Cl.5 15850: 1; Phloxine B, Cl. 45410; Rhodamine B, Cl. 45170; Beetroot dye Betanin, E162; Tartrazine, E102, Cl. 19140; Uranin, Cl. 45350 or fluorescein, Cl. 45350: 1st

Further organic dyes, which are carboxylic acid derivatives, can be found in Q "Gisbert Otterstätter: The coloring of food, medicines,

Cosmetics; 2nd revised edition, Behr ^' s Verlag Hamburg, 1995 ", or

FD & C Yellow 5 (Tartrazine), FD & C Yellow 6 (Sunset Yellow FCF), FD & C

Yellow 10, FD & C Red 3 (erythrosine), FD & C Red 6 (litholubin B), FD & C

Red 7 (Lithol Rubin BN), FD & C Red 21, FD & C Red 27, FD & C Red 28 ₅ (Floxine B), FD & C Red 33, Cl. Natural Red 33, FD & C Red 36, FD & C Red

40, Carmine, FD & C Blue 1 (Brilliant Blue FCF), Cl. Natural Green 3

(E141), FD & C Blue, FD & C Black 1 (Brilliant Black).

In general, the pharmacological, antimicrobial, fungicidal, Q herbicides, insecticides or cosmetic active ingredients, dyes or

X-ray contrast agents are also understood as substances that are due to

Their structure is able to absorb UV radiation, provided they have a conjugated π-electron system of at least 4 π-electrons.

In a further variant of the invention it is therefore also preferred if the radical B in formula I is a substituent which absorbs UV radiation and has a conjugated π-electron system of at least 4 π-electrons.

In a further variant of the invention it is particularly preferred if the radical B in formula I is a substituent which absorbs UV-A and / or UV-B radiation. These compounds also usually have a conjugated π-electron system of at least 4 π-electrons. The radical B here is a UV filter, preferably a substituent of the formula II, III, IV, V, VI, VII, VIII, IX, X, XI and / or XI I,

in which

R ⁵ to R ^{16 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -

NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂₎ - [NHA ₂ ] X, - [NA ₃ ] X , -SO ₃ H,

- [SO ₃ ] X or 2H-benzotriazol-2-yl mean and

A is alkyl having 1 to 4 C atoms, n is an integer from 1 to 25,

X is the counterion to the cations [NHA ₂ J ⁺ and [NA ₃ ] ⁺ or the anion [SO ₃ ] ^" and

Y and Z are each independently -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ . In the formulas described above, A is alkyl having 1, 2, 3 or 4 C atoms, for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tert-butyl. Preferably, A is methyl or ethyl, most preferably ethyl.

n is an integer from 1 to 25, preferably an integer from 1, 2, 3, 4 or 5.

X describes the counterion for the cations [NHAa] ⁺ and [NA ₃ ] ⁺ , where A has one of the meanings indicated above, preferably Cl ^" , Br ^" , I ^" or [SO ₄ ] ^2" or the counterion of the anion [SO ₃ ] ^" , preferably one

Ammonium ion or an alkali metal or alkaline earth metal cation such as Na ⁺ , K ⁺ ,

Mg ²⁺ or Ca ²⁺ .

However, it is also possible for partial charges to be balanced in the molecule itself, i. that compounds of the formula I as zwitterionic

Structure may be present.

Compounds of formula I can also be used as salts according to the invention, i. at least one hydroxy group of the

Ascorbinsäuregrundgerüsts is deprotonated and the charge is by a counter cation, such as an alkali or

Alkaline earth metal cation, balanced.

For the substituents of the formula II, the radicals R ⁵ to R ⁹ , R ¹¹ and R ^{12 are} preferably H and R ^{10 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [ SO ₃ ] X or 2H-benzotriazol-2-yl.

R ¹⁰ in formula II is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ , wherein A has one of the meanings given above. For the substituents of the formula III, the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} preferably H and

R ^{7 is} -OH ₁ -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁷ in formula III is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ , wherein A has one of the meanings given above.

For the substituents of the formula IV, the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} preferably H and

R ^{7 is} -OH, -OA, -A ₁ -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁷ in formula IV is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ , wherein A has one of the meanings given above.

Alternatively, for the substituents of formula IV, the radicals R ⁵ , R ⁸ and R ^{9 are} preferably H, R ⁶ is 2H-benzotriazol-2-yl and R ⁷ is -OH, -OA, -A, -NH ₂ , -NHA , -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H or - [SO ₃ ] X. In this substituent arrangement, R ^{7 is more} preferably OH.

For the substituents of the formula V, the radicals R ⁶ , R ⁸ , R ¹¹ and R ^{13 are} preferably H and the substituents R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ^{14 are} each independently H, -OH, -OA ₁ -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ - CH ₂ -O) _n -H ₁ -N [(CH ₂ -CH ₂ -O) _n -H] _2l - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl. R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁴ in formula V are each independently preferably H, -OA, -NH ₂ , -NHA or -NA ₂ , most preferably H, wherein A is one of has previously given meanings.

For the substituents of the formula VI, the radicals R ⁶ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ^{16 are} preferably H and the substituents R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} each independently each other is H, -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NL (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in formula VI are each, independently of one another, preferably H, -OA, -NH ₂ , -NHA or -NA ₂ , very particularly preferably H, where A is one of has previously given meanings.

For the substituents of the formula VII, the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 are} preferably H and Z is -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ .

Z in formula VII is particularly preferably OH.

For the substituents of the formula VIII, the radicals R ⁵ , R ⁶ , R ⁷ and R ^{8 are} preferably H and the substituent R ⁹ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H , - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁹ in formula VIII particularly preferably means -OA.

For the substituents of the formula IX, the radicals R ⁵ , R ⁶ , R ⁷ and R ^{8 are} preferably H and the substituent R ⁹ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl. R ⁹ in formula IX particularly preferably means -OA.

For the substituents of the formula X, the radicals R ⁵ , R ⁷ and R ^{8 are} preferably H and the substituent R ⁶ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , -NH- ( CH ₂ -CH ₂ -O) _n -H, -Nt (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, -

[NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁶ in formula X is particularly preferably -OH.

For the substituents of the formula XI, the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ and R ^{12 are} preferably H and the substituent R ¹⁰ is preferably H, -OH, -OA, -A, - NH _2, -NHA, -NA _2, -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n - H] _2, - [NHA _2] X ₁ - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ¹⁰ in formula XI particularly preferably denotes H.

For the substituents of the formula XII, the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} preferably H and the substituent R ⁷ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H , - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁷ in formula XII particularly preferably denotes A. In a particular variant, compounds of the formula XII which are suitable as substituent R ^{7 are also} the partial structure

Further preferred combinations are disclosed in the claims.

Particularly preferred embodiments of the radical B can be seen in the following substructures:

30

25

30

VIIIb

The invention also relates to the compounds of the formula

in which

R ¹ or R ^{2 are} each independently hydroxy, -O-alkyl, -OC (O) -

Alkyl, -OPO ₃ M or O-glycosyl,

Alkyl C 1 -C 6 -alkyl,

M alkali or alkaline earth metal cation or H ₁

R ³ or R ^{4 are} each independently hydroxy or a radical B and

B is a substituent of the formula II, III, IV, V, VI, VII ₁ VIII, IX, X, Xl and / or XII,

20

30

25

30

30 in which

R ⁵ to R ^{16 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -

NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X , -SO ₃ H,

- [SO ₃ ] X or 2H-benzotriazol-2-yl mean and

A is alkyl having 1 to 4 C atoms, n is an integer from 1 to 25,

X is the counterion to the cations [NHA ₂ J ⁺ and [NA ₃ J ⁺ or the anion [SO ₃ ] ^" and

Y and Z are each independently -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ , wherein for R ⁵ to R ⁹ in formula IV the radicals H , OH and OA except in the case where at least one substituent of R ⁵ to R ^{9 is} A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H , -N [(CH ₂ -CH ₂ -O) _n -

H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl and with the proviso that at least one of the radicals R ³ or R ⁴ for one

Rest B stands.

A, n and X have meaning as described above.

In a variant of the invention, compounds of the formula I are preferred when R ² in formula I denotes hydroxyl. In a variant of the invention, compounds of the formula I are preferred when R ¹ in formula I denotes hydroxyl.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ to R ⁹ , R ¹¹ and R ¹² in formula II are preferably H and

R ^{10 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ¹⁰ in formula II is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ , wherein A has one of the meanings given above.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁸ and R ⁹ in formula III are preferably H and R ^{7 is} -OH, -OA, -A, -NH ₂ , -NHA, - NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X , -SO _{3 is} H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

In a variant of the invention, compounds of formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁸ and R ⁹ of formula IV are preferably H and

R ⁷ -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X ₁ -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁷ in formula IV is preferably -NH ₂ , -NHA, -NA ₂ , - [NHA ₂ ] X or - [NA ₃ ] X, most preferably -NA ₂ , wherein A has one of the meanings given above. In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁸ and R ^{9 of} the formula IV are preferably H, R ^{6 is} 2H-benzotriazol-2-yl and R ^{7 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H,

- [SO ₃ ] X or 2H-benzotriazol-2-yl. Most preferably, R ⁷ in this variant of the invention is -OH.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁶ , R ⁸ , R ¹¹ and R ^{13 of} the formula V are preferably H and the substituents R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁴ each independently of one another are H, -OH, -OA, -A ₁ -NH ₂ , -NHA ₁ -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NI (CH ₂ - CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H ₁ - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁴ in formula V are each independently preferably H, -OA, -NH ₂ , -NHA or -NA ₂ , most preferably H, wherein A is one of has previously given meanings.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁶ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ^{16 of} the formula VI preferably H _{1 are} the substituents R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA ₁ -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H ₁ -NL (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X ₁ -SO ₃ H ₁ - [SO ₃ ] X or 2H-benzotriazol-2-yl and Z hydroxy, Are -O-2-ethylhexyl, OA or -NH-C (CH ₃ ) ₃ .

R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in formula VI are each, independently of one another, preferably H, -OA, -NH ₂ , -NHA or -NA ₂ , very particularly preferably H ₁ where A is one of has previously given meanings. Z in formula VI is more preferably hydroxy, -O-2-ethylhexyl or -NH-C (CH ₃ ) ₃ . In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 of} the formula VII are H and Z is ascorbyl, hydroxy, -O-2-ethylhexyl, O-hexyl, -OA or -NH-C (CH ₃ ) 3 means. Most preferably Z is -OH.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula VIII are H and R ^{9 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, - SO _{3 is} H, - [SO ₃ ] X or 2H-benzotriazol-2-yl. Particularly preferred R ⁹ in formula VIII is A or 2-ethylhexyl.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula IX are H and R ^{9 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl. R ⁹ in formula IX is particularly preferably A or 2-ethylhexyl.

In a variant of the invention, compounds of formula I are preferred when the radicals R ⁵ , R ⁷ and R ⁸ in formula X are H and R ^{6 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH - (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H , - [SO ₃ ] X or 2H-benzotriazol-2-yl. Particularly preferred R ⁶ in formula X is -OH.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ and R ¹² in formula XI are H and R ^{10 is} H, -OH, -OA ₁ - A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA _3] X, -SO ₃ H ₁ - [SO _3] X or 2H-benzotriazol-2-yl. R ¹⁰ in formula XI H. is particularly preferred.

In a variant of the invention, compounds of the formula I are preferred when the radicals R ⁵ , R ⁶ , R ⁸ and R ⁹ in formula XII are H and R ^{7 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [ NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl. R ⁷ is particularly preferably in formula XII A.

Further preferred combinations are disclosed in the claims.

Particularly preferred embodiments of compounds of the formula I are in the partial structures Ila-Ilf, HIa, IVa-IVo, Va VIa-VIc, VIIa-VIIb, VIIIa VIIIb, IXa-IXb, Xa, XIa and / or XIIa-XIIb for the To see rest B, as previously described.

The preparation in general of the compounds of the formula I ₁ as described above can be carried out by methods known to the person skilled in the art from methods known per se. The reaction conditions for esterifications or etherifications are well known in the art and selecting the appropriate reaction conditions is one of the standard knowledge of the artisan.

The invention likewise provides a process for the preparation of compounds of the formula I as described above, where the meaning of the subformulae XI and XII is excluded for the radical B, characterized in that a) a compound of the formula XIII

wherein R ¹ or R ^{2 have} one of the meanings previously given for the formula I or for preferred meanings, directly with a compound of formula XIV BM XIV

wherein B may have one of the meanings described above, wherein the subformulae Xl and XII are excluded, and M is alkali metal or alkaline earth metal cation or H is reacted or

b) the hydroxy groups of the compound of the formula XIII ₁ as described above are protected to give a compound of the formula XV,

wherein

R ¹ or R ^{2 have} one of the meanings described above for the formula I and SG is a protective group, in a subsequent step, the radicals R ¹ and / or R ² , if these

Hydroxy groups are protected by a second protective group, which are cleavable again under other reaction conditions such as the protective group SG, the protecting groups SG of the compounds of formula XV again cleaved and the resulting compound with a compound of formula XIV

B-M XIV, wherein B has one of the meaning previously described for the formula I, wherein the subformulae Xl and XII are excluded, and

M alkali metal or alkaline earth metal cation or H, and then deprotected the radicals R ¹ and / or R ² to the hydroxy group and optionally these hydroxy groups in another radical R ¹ or

R ² ≠ OH, as previously described, converts. The direct esterification of the compounds of the formula XIII with compounds of the formula XIV, if they are bonded via a carbonyloxy function, takes place in the presence of concentrated sulfuric acid and preferably under inert gas conditions. Advantageously, the

Mixture of the components manufactured at temperatures <5 ° C. The actual reaction temperature is between 10 and 60 ^° C., preferably between 15 and 30 ^° C. Particularly preferably, the reaction takes place at room temperature.

Some of the starting materials of formulas XIII and XIV are commercially available, for example ascorbic acid, ascorbic acid phosphate, sodium and magnesium ascorbyl phosphate, ascorbic acid glucoside, salicylic acid, p-methoxycinnamic acid, p-hydroxycinnamic acid, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid or 2 - (4-methoxy-2-hydroxybenzoyl) benzoic acid, or can be synthesized by methods such as in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart are described, under reaction conditions, which are known and suitable for the reactions mentioned. One can also make use of known per se, not mentioned here variants.

In the case of direct esterification, a mixture of ascorbic acid C-6 esters and ascorbic acid C-5 esters is produced by synthesis, as a rule the ascorbic acid C-6 ester predominates. Ascorbic acid C-6 esters are compounds of formula I wherein R ^{4 is} B. Ascorbic acid C-5 esters are compounds of formula I ₁ wherein R ^{3 is} B. Of course, these mixtures are separable by methods known to those skilled in the art.

Ether formation by reaction of compounds of the formula XIV in which B corresponds to the partial formulas VIII, IX or X, and in which M = H means with compounds of formula XIII, preferably in the presence of triphenylphosphine and diisopropyl azodicarboxylate, in an inert solvent, for example a halogenated hydrocarbon such as dichloromethane, an ether such as tetrahydrofuran or dioxane, an amide such as DMF or dimethylacetamide, a nitrile such as acetonitrile, in dimethylsulfoxide or in the presence of these solvents, at temperatures between about -10 and 40, preferably between 0 and 30 °. The reaction time is between a few minutes and several days, depending on the conditions used.

Are for the synthesis of the compounds of formula I in which B corresponds to one of the substructures VIII, IX or X, starting compounds of the formula XVIII

B'-Hal XVIII, wherein Hal is Cl, Br or I and

B ^{1 of} the partial formula VIIT, IX ¹ or X ', where all substituents have the meaning given above, are used,

thus a classical nucleophilic substitution takes place. The appropriate protecting group chemistry, as described below, should be used. The reaction conditions of a nucleophilic substitution are well known to the synthetic artisan.

The alternative preparation of the compounds according to the invention is essentially based on a protective group chemistry of the hydroxyl groups of the compounds of the formula XIII ₁ as defined above, so that the esterification in position 5 and / or 6 of the ascorbic acid main body can take place in a targeted manner. However, the esterification with compounds of the formula XIV can also be carried out without prior protection group chemistry, the reaction conditions being well known to the person skilled in the art.

As a rule, the protective groups are chosen differently from each other so that they can be selectively split (see: TW Greene, PGM Wuts, Protective Groups in Organic Chemistry, 2nd Ed., Wiley, New York 1991 or PJ. Kocienski, Protecting Groups, 1st ed., Georg Thieme Verlag, Stuttgart - New York, 1994, H. Kunz, H. Waldmann in Comprehensive Organic Synthesis, Vol. 6 (eds. BM Trost, I. Fleming, E. Winterfeldt ), Pergamon, Oxford, 1991, pp. 631-701).

The term "hydroxy protecting group" is also well known and refers to groups which are suitable for protecting a hydroxy group from chemical reactions. Typical of such groups are unsubstituted or substituted aryl, aralkyl, aroyl or acyl groups, and also alkyl groups, alkyl, aryl or aralkyl silyl groups or O ₁ O or O, S-acetals. The nature and size of the hydroxy protecting groups is not critical because they are removed after the desired chemical reaction or reaction sequence; preferred are groups having 1-20, in particular 1-10 C-atoms. Examples of hydroxy-protecting groups include aralkyl groups such as benzyl, 4-methoxybenzyl or 2,4-dimethoxybenzyl, aroyl groups such as benzoyl or p-nitrobenzoyl, acyl groups such as acetyl or pivaloyl, p-toluenesulfonyl, alkyl groups such as methyl or tert-butyl, but also allyl, Alkylsilyl groups such as trimethylsilyl (TMS), triisopropylsilyl (TIPS), tert-butyldimethylsilyl (TBS) or triethylsilyl, trimethylsilylethyl, aralkylsilyl groups such as tert-butyldiphenylsilyl (TBDPS), cyclic acetals such as isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene, p- Methoxybenzylidene or o, p-dimethoxybenzylidene acetal, acyclic acetals such as tetrahydropyranyl (Thp), methoxymethyl (MOM), methoxyethoxymethyl (MEM), benzyloxymethyl (BOM) or methylthiomethyl (MTM). Particularly preferred hydroxy protecting groups are benzyl, acetyl, tert-butyl or TBS.

As starting material of the synthesis, preference is given to using ascorbic acid, the hydroxyl groups of which are in the 5- and 6-position by protective groups SG, as described above, according to known methods Compounds of formula XV are protected. Advantageously, a cyclic protecting group is selected which effectively simultaneously protects both positions 5 and 6. Examples of compounds of formula XV are accordingly 5,6-isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene, p-methoxybenzylidene or o, p-dimethoxybenzylidene ascorbate.

Preference is given to using 5,6-isopropylidene ascorbate.

Subsequently, the hydroxy groups in position 2 and 3 are protected by means of protective groups as described above, advantageously an aralkyl group or an alkylsilyl group is selected, particularly preferably an aralkyl group, for example the benzyl group.

After releasing the protected in the first step hydroxy groups is reacted with a compound of formula XIV, wherein B and M have a meaning previously described or with compounds of formula XVIII.

When reacted with a compound of formula XIV wherein M is H and B is preferably a partial formula II, III, IV, V, VI or VII, the coupling reaction preferably takes place in the presence of a dehydrating agent, e.g. a carbodiimide like

Dicyclohexylcarbodiimide (DCC), N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide hydrochloride (EDC) or diisopropylcarbodiimide (DIC), furthermore propanephosphonic anhydride (see Angew Chem. 1980, 92, 129), diphenylphosphorylazide or 2 -Thethoxy-N-ethoxycarbonyl-1, 2-dinydroquinoline, in an inert solvent, for example a halogenated hydrocarbon such as dichloromethane, an ether such as tetrahydrofuran or dioxane, an amide such as DMF or dimethylacetamide, a nitrile such as acetonitrile, in dimethyl sulfoxide or in the presence of these Solvent, at temperatures between about -10 and 40, preferably between 0 and 30 ° instead. The reaction time is between a few minutes and several days, depending on the conditions used. Instead of compounds of the formula XIV, as defined above, it is also possible to use derivatives of the formula XIV, preferably a preactivated carboxylic acid, or a carboxylic acid halide, a symmetrical or mixed anhydride or an active ester. Such residues for activation of the carboxy group in typical

Acylation reactions are described in the literature (e.g., in the standard works such as Houben-Weyl, Methoden der organischen Chemie, Georg-Thieme-Verlag, Stuttgart). Activated esters are conveniently formed in situ, e.g. by addition of HOBt (1-hydroxybenzotriazole) or N-hydroxysuccinimide.

The reaction is generally carried out in an inert solvent, using a halide of the formula XIV in the presence of an acid-binding agent, preferably an organic base such as triethylamine, dimethylaniline, pyridine, dimethylaminopyridine or quinoline.

Also, the addition of an alkali or alkaline earth metal hydroxide, carbonate or bicarbonate or other salt of a weak acid of the alkali or alkaline earth metals, preferably of potassium, sodium, calcium or cesium may be beneficial.

After the coupling, and thus introduction of the active substance-forming radical, in the base body of the ascorbic acid, the hydroxy groups are deprotected in position 2 and 3 and are obtained compounds of formula I, wherein R ¹ and R ² is hydroxy. The conversion of these hydroxy groups into other radicals R ¹ and R ² , as defined above, succeeds according to standard methods, for example an etherification, an esterification or a glycosylation.

By changing the reaction conditions or, in general, the esterification method, it is also possible to carry out the synthesis of the current secondary component, the ascorbic acid C-5-ester (specifically for example 1). (4-Diethylamino-2-hydroxy-benzoyl) benzoic acid (R) -1 - ((R) -3,4-dihydroxy-5-OX-O-2, 5-dihydro-furan-2-yl) -2- hydroxy ethyl ester) such that this product forms the major component and the ascorbic acid C-6 ester (specifically, for example 1 2- (4-diethylamino-2-hydroxy-benzoyl) benzoic acid- (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxy-ethyl ester) with 0 to 25%. Suitable esterification methods are, for example, enzymatic esterifications.

The invention also provides a process for the preparation of compounds of the formula I, in which the radical B corresponds to the partial structures of the formula XI and / or XII, characterized in that a) a compound of the formula XIII

wherein

R ¹ or R ^{2 have} one of the meanings previously described for the formula I, with a compound of formula XVI or XVII

wherein R ⁵ to R ^{12 have} one of the meaning previously described for the formula I, and

Hal Cl ₁ Br, I or Aktivester means, is reacted b), the hydroxy groups of the compound of formula XIII, as described previously protected, to a compound of formula XV,

wherein

R ¹ or R ^{2 have} one of the meanings previously described for the formula I, hereinafter the radicals R ¹ and / or R ² , if these are hydroxy, are protected by a second protective group, among others

Reaction conditions such as the protecting group SG are again cleavable, the protecting groups SG of the compounds of formula XV again cleaved and the resulting compound with a compound of formula XVI or XVII

implements, wherein R ⁵ to R ^{12 have} one of the meaning previously described for the formula I, and

Hal is Cl, Br, I or active ester and then deprotected the radicals R ¹ and / or R ² as hydroxy and optionally converts these hydroxy groups into another radical R ¹ or R ² ≠ OH as described above.

In formulas XVI or XVII, Hal is preferably Cl, Br or I, more preferably Cl or Br, most preferably Cl.

The reaction of the compounds of the formula XIII with compounds of the formula XVI or XVII is generally carried out in an inert solvent, in the presence of an acid-binding agent, preferably an organic base such as triethylamine, dimethylaniline, pyridine, dimethylaminopyridine or quinoline.

Of course, the reaction can also be carried out here via the classical protective group strategy or chemistry, as described above. The remarks and steps also apply to this reaction according to the invention, as described above.

The ascorbic acid derivatives described are capable of binding to textiles or textile fibers and thus unfolding their respective effect on the remainder B, for example UV protection, protection against oxidation or they also serve for impregnation. Unwanted material damage will be reduced. The ascorbic acid derivatives according to the invention, wherein the radical B is a substituent which absorbs UV radiation and has a conjugated π-electron system of at least 4 π-electrons, preferably the UVA _r UV-B or UV (A + B) -absorbing UV For example, filters or the substructures of formulas II, III, IV, V, VI, VII, VIII, IX, X, XI and / or XII also have anti-aging effects and have the skin-derived benefits of ascorbic acid For example, they serve for skin regeneration and cause wrinkle reduction of (light) aged skin, they further increase, for example, the skin relief density or enhance, for example, the dermis-epidermis compound (papilla index). They protect the skin from UV-induced damage or, for example, have a skin-bleaching effect. They have, for example, an antibacterial effect, ie they can reduce sweat odor or improve the appearance of skin blemishes and / or acne.

The ascorbic acid derivatives according to the invention, wherein the radical B is a substituent which absorbs UV radiation and has a conjugated π-electron system of at least 4 π-electrons, preferably the UVA, UV-B or UV (A + B) -absorbing UV -Filter or the substructures of the formulas II, III, IV, V, VI, VII, VIII, IX, X, XI and / or XII, are able to bind to hair and can thus by UV light or Prevent the damage caused by oxidation hair damage, especially with regard to color and morphology.

For example, you can protect it from fading hair.

The ascorbic acid derivatives according to the invention, where the radical B is a substituent which absorbs UV radiation and has a conjugated π-

Has electron system of at least 4 π-electrons, preferably the

UVA, UV-B or UV (A + B) absorbing UV filters or the

Partial structures of the formulas II, III, IV, V, VI, VII, VI, IX, X, XI and / or XII means are able to bind not only to nitrogen-containing, but also to sulfur-containing hair functionalities, such as to thiol groups. Due to the good reduction properties of the compounds, the ascorbic acid derivatives according to the invention can be used, for example, by controlled reduction of disulfide bridges, in hair treatment products for de-crimping or in the formation of perms.

EP 1728501 describes the use of U VA photoprotective filters bound to a polypeptide. Analogously to the teaching of EP 1728501, the ascorbic acid derivatives according to the invention, wherein the radical B is a substituent which absorbs UV radiation and has a conjugated π-electron system of at least 4 π-electrons, preferably the UVA, UV-B or UV (A + B) -absorbing UV filter or the partial structures of the formulas II, III, IV, V, VI, VII, VIII ₁ IX, X, XI and / or XII, before application with an amino acid, a peptide or be combined with a protein or bound to an amino acid, to a peptide or to a protein.

Another object of the present invention is according to the preferred use of the compounds according to the invention for the functionalization of matrices, an agent, for example a cosmetic, dermatological or pharmaceutical preparation or

Composition containing at least one compound of the formula I,

in which R ¹ or R ^{2 are} each independently hydroxy, -O-alkyl, -OC (O) -

Alkyl, -OPO ₃ M or O-glycosyl,

Alkyl d-Ce-alkyl,

M alkali or alkaline earth metal cation or H,

R ³ or R ^{4 are} each independently hydroxy or a radical B and

B is the remainder of a pharmacological, fungicidal, herbicidal, insecticidal or cosmetic active ingredient, an X-ray contrast agent or a

Dye or a substituent of the formula II, III, IV is ₁ V, VI, VII, VIII, IX, X, XI and / or XII,

in which

R ⁵ to R ^{16 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -

NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H,

- [SO ₃ ] X or 2H-benzotriazol-2-yl mean and

A is alkyl having 1 to 4 C atoms, n is an integer from 1 to 25,

X is the counterion to the cations [NHA ₂ J ⁺ and [NA ₃ J ⁺ or the anion [SO ₃ J ^" and

Rest B stands.

Advantages of the compounds or preparations according to the invention are, in particular, in addition to the absorbing action as a UV filter, as exemplified in FIG. 1 for DHAB (2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid benzoate) synthesized according to Example 1, the antioxidant effect, which unfolds in the functionalization of the matrix by disintegration of the Ascorbinsäuregrundkörpers, optionally the Selbstbräunerwirkung resulting from the Maillardreaktion and in particular the functionalization of the matrix, depending on the active ingredient residue B in the compounds of formula I immobilization of the active ingredient and thus, for example, corresponds to an immobilized UV protective effect or corresponds to a controlled release of active ingredient, for example a pharmacologically active substance. However, the compounds according to the invention also have a structurally related antioxidant effect.

For the purposes of the present invention, the term preparation or formulation is used synonymously.

The compositions are usually either topically applicable preparations, for example cosmetic, pharmaceutical or dermatological formulations. The preparations in this case contain a cosmetically, pharmaceutically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients. The topical preparations are preferably used as a cosmetic or dermatological preparation, particularly preferably as a cosmetic preparation.

The compounds of formula I according to the invention typically in amounts of 0.01 to 20 wt .-%, preferably in amounts of 0.05 wt.

% to 10 wt .-% used. It prepares the expert no

Difficulty the quantities depending on the intended effect of

Preparation to select accordingly.

The functionalization of the matrix or the binding detection can be checked by means of some binding tests. These binding tests are in the

Example part described. The agents according to the invention preferably contain as little oxygen as possible, ie the agents should be prepared under inert gas conditions. Furthermore, it is advantageous to keep the water content low. It is also advantageous to limit the presence of (heavy) metal ions, as they are known to destabilize antioxidants. Thus, the agents according to the invention may contain, for example, complexing agents. During production and also during storage, the substances according to the invention and the agents containing the substances according to the invention should be protected from UV radiation, light and heat. When the agents contain water, the pH should preferably be made acidic. All measures in this regard are known in the art.

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

There are many known and proven substances known from the literature which can be used as antioxidants, eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), Aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , γ-linoleyl, cholesteryl and glyceryl esters) and their salts, Dilaurylthiodipropionat, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin , EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (eg vitamin A) palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine,

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

Suitable antioxidants are also compounds of the general formulas A or B.

wherein

R ^{1 can be selected} from the group consisting of -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 are} each independently of one another H or linear or branched alkyl having 1 to 8 C atoms,

R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and

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

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

In the compositions or preparations according to the invention may as further

Ingredients contain vitamins. Preference is given to vitamins and vitamin

Derivatives selected from vitamin A, vitamin A propionate, vitamin A

Palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (Vitamin Bi), riboflavin (vitamin B2), nicotinic acid amide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D ₂ ), vitamin E, DL-α-tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin KL esculin ( Vitamin P active ingredient), thiamine (vitamin BO, nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), pantothenic acid,

Contain biotin, folic acid and cobalamin (vitamin B ₁₂ ) in the cosmetic preparations of the invention, particularly preferably retinol, nicotinamide, vitamin A palmitate, vitamin C and its derivatives, DL-α-tocopherol, tocopherol E acetate, nicotinic acid, pantothenic acid and biotin, most preferably retinol or nicotinic acid amide. Vitamins are used with compounds of the formula I usually in ratios in the range of 1000: 1 to 1: 1000, preferably used in amounts of 100: 1 to 1: 100.

Particularly preferred agents or preparations according to the invention contain, in addition to the compounds of the formula I, also pure UV filters.

In principle, all UV filters are suitable for combination with the compounds of the formula I according to the invention. Particularly preferred are those UV filters whose physiological harmlessness has already been demonstrated. For both UVA and UVB filters, there are many known and proven substances in the literature, e.g.

Benzylidenecamphor derivatives, such as 3- ^{(4'-methylbenzylidene)} -dl-camphor (for example Eusolex 6300), 3-benzylidenecamphor (for example Mexoryl® SD), polymers of N - {(2 and 4) - [(2-oxoborn-3- ylidene) methyl] benzyl} -acrylamide (eg Mexoryl® SW), N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (eg Mexoryl® SK) or (2-oxoborn-3-yl) yliden) toluene-4-sulfonic acid (eg Mexoryl® SL), Benzoyl or dibenzoylmethanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (eg Eusolex® 9020) or A-isopropyldibenzoylmethane (eg Eusolex® 8020),

Benzophenones such as 2-hydroxy-4-methoxybenzophenone (e.g., Eusolex®

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

Methoxycinnamic acid esters such as octyl methoxycinnamate (e.g., Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of isomers (e.g., Neo Heliopan® E 1000),

Salicylate derivatives such as 2-ethylhexyl salicylate (e.g., Eusolex® OS), A-isopropylbenzyl salicylate (e.g., Megasol®), or 3,3,5-trimethylcyclohexyl salicylate (e.g., Eusolex® HMS),

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

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

and other substances like

2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester (e.g., Eusolex® OCR),

- 3,3 ^'- (1, 4-phenylenedimethylene) bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-ylmethanesulfonic acid and salts thereof (for example Mexoryl SX ^®) and

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

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

These organic UV filters are incorporated usually in an amount of 0.5 to 10 weight percent, preferably 1 to 8 wt .-%, in cosmetic Formu-lations.

Other suitable organic UV filters are e.g.

2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-i -)

(trimethylsiiyloxy) disiloxanyl) propyl) phenol (INCI: Drometrizole Trisiloxane, for example Mexoryl XL ^®),

α- (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl) and about 6% methyl [2- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy] -1-methylenethyl] and about 1.5% methyl [3- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy) propenyl) and 0.1-0.4% (methylhydrogensilylene]] (n "60) (CAS -No 207 574- 74-1) (INCI:. Polysilicone-15, for example, Parsol ^® SLX),

- 2,2 ^{'methylene-bis-} (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethyl- butyl) phenol) (CAS No. 103 597-45-. 1) (INCI: Methylene bis- benzotriazolyl Tetramethylbutylphenol, including Tinosorb ^® M),

- 2,2 ^'- (1, 4-phenylene) bis- (1 H-benzimidazol-4,6-disulfonic acid, monosodium salt) (CAS No. 180 898-37-7).

2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxyl] -phenyl} -6- (4-methoxyphenyl) -

(. INCI: Bis- Ethylhexyloxyphenol Methoxyphenyl Triazine, e.g., Tinosorb S ^®) 1, 3,5-triazine (CAS No. 103 597-45-, 187 393-00-6.) Or

4 ₎ 4 ^' - [(6- [4 - ((1, 1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (2-ethylhexyl benzoate) (INCI: Diethylhexyl

Butamido Triazone such Uvasorb® ^® HEB). Organic UV filters are usually incorporated in an amount of 0.5 to 20 percent by weight, preferably 1 to 15 wt .-%, in cosmetic formulations.

As inorganic UV filters are those from the group of titanium dioxides such as coated titanium dioxide (eg Eusolex®T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO), zinc oxides (eg Sachtotec®), iron oxides or cerium oxides conceivable. These inorganic UV filters are usually incorporated in an amount of 0.5 to 20 weight percent, preferably 2-10%, in cosmetic preparations.

By combining one or more compounds of the formula I with further UV filters, the protective effect against harmful effects of the UV radiation can be optimized. This results in broadband protection systems that can be supplemented by the addition of inorganic UV filters.

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 have photostability such filters, such as cinnamic acid derivatives, can increase the photostability of the entire formulation.

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. By the here proposed

Encapsulation of the corresponding substances, this effect is prevented.

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

Therefore, it is preferred according to the invention if one or more of the abovementioned 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 the encapsulated

Active ingredient (UV filter) not or only to a small extent to the environment.

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

The capsules in compositions or preparations according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the amounts indicated above.

The compositions or preparations according to the invention may additionally contain further anti-aging active ingredients, anti-cellulite active ingredients or customary skin-friendly or skin-care active ingredients. Skin-sparing or skin-care active ingredients can, in principle, be all active ingredients known to the person skilled in the art.

Particularly preferred anti-aging agents are pyrimidinecarboxylic acids, aryloximes, bioflavonoids, bioflavonoid-containing extracts, chromones or retinoids.

Pyrimidinecarboxylic acids occur in halophilic microorganisms and play a role in the osmoregulation of these organisms

(E.A. Galinski et al., Eur. J. Biochem., 149 (1985) p. 135-139). Among the pyrimidinecarboxylic acids, in particular ectoine ((S) -1, 4,5,6-

Tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S ₁ S) -

To call 1, 4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylic acid and derivatives thereof. These compounds stabilize enzymes and others

Biomolecules in aqueous solutions and organic solvents.

Furthermore, they stabilize especially enzymes against denaturing

Conditions such as salts, extreme pH, surfactants, urea,

Guanidinium chloride and other compounds.

Ectoine and ectoine derivatives such as hydroxyectoine can be used to advantage in medicines. In particular, hydroxyectoine may be used for Production of a drug used to treat skin diseases. Other fields of use of hydroxyectoine and other ectoin derivatives are typically in areas in which, for example, trehalose is used as an additive. For example, ectoine derivatives, such as hydroxyectoine, can be used as a protective agent in dried yeast and bacterial cells

Find use. Also pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins e.g. t-PA can be protected with Ectoin or its derivatives.

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

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

wherein R ^{1 is} a radical H or Ci _-8 alkyl, R ^{2 is} a radical H or Ci _-4 alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and _d-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particular preference is given to the pyrimidinecarboxylic acids ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1, 4,5, 6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). The inventive Preparations such Pyrimidincarbonsäuren preferably in amounts up to 15 wt .-%. The pyrimidinecarboxylic acids are preferably used in ratios of 100: 1 to 1: 100 to give the compounds of the formula I, with ratios in the range from 1:10 to 10: 1 being particularly preferred.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products is known for example from the German patent application DE-A-41 16 123. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are associated with inflammation. The preparations preferably contain from 0.01 to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05 to 5% by weight of aryloxime.

Known bioflavonoids are, for example, troxerutin, tiliroside, α-glucosylrutin, rutin or isoquercetin, the said selection not being intended to be restrictive.

Bioflavonoidhaltige extracts are for example Gingko Biloba or Emblica.

Known anti-aging substances are also chromones, as described, for example, in EP 1508327 or retinoids, for example retinol (vitamin A), retinoic acid, retinaldehyde or else synthetically modified compounds of vitamin A.

The described chromones and retinoids are also effective anti-cellulite agents. Another well known anti-cellulite drug is caffeine. The agents may include or include, but are not limited to, the essential or optional ingredients or restrictions mentioned. Any compounds or components that can be used in the compositions or preparations are either known and commercially available or can be synthesized by known methods.

The one or more compounds of the formula I can be incorporated in the usual way into cosmetic or dermatological preparations. Suitable preparations for external use, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin.

As an application form of the preparations according to the invention, e.g. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays. Other applications are e.g. Sticks, shampoos and shower baths. Any customary carrier substances, adjuvants and optionally further active ingredients can be added to the preparation.

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

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

Powders and sprays may contain the usual excipients, for example lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can additionally the usual propellants, eg chlorofluorohydrocarbons, propane / butane or dimethyl ether.

Solutions and emulsions may contain the customary carriers such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate,

Propylene glycol, 1, 3-butylglycol, dimethyl capramide, dimethyl isosorbide,

Oils, in particular 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.

In a preferred application, the ascorbic acid derivatives according to the invention, as described, are converted into an application-appropriate formulation shortly before application. For example, the substance is dissolved in a carrier as described above and applied directly to skin or preferably to hair. Particularly suitable carriers in this sense are Arlasolve DMI (dimethylisosorbide), butylene glycol, Finsolv® PG-22 (dipropylene glycol dibenzoate) or Pelemol® BIP (butylphthalimide isopropylphthalimide).

Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

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

Surfactant-containing cleaning products may contain the usual carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfo acid monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.

Facial and body oils may contain the usual excipients such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.

Other typical cosmetic application forms are also lipsticks, lip balm, mascara, eyeliner, eye shadow, rouge, powder, emulsion and wax make-up and sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms according to the invention include in particular emulsions.

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

The lipid phase can advantageously be selected from the following substance group:

- mineral oils, mineral waxes

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

- Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, eg with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with low C-alkanoic acids or with fatty acids; - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of from 3 to 30 carbon atoms, from the group consisting of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of from 3 to 30 carbon atoms. atoms. Such ester oils can then be advantageously selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate,

2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and also synthetic, semisynthetic 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. 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.

The oil phase is advantageously selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _{_2-15} -alkyl, caprylic capric triglyceride, dicapryl ether.

Particularly advantageous are mixtures of C _{_2-15} alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _{_2-15} alkyl benzoate and isotridecyl isononanoate and mixtures of C ₂ --i ₅ alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene are to be used advantageously in the context of the present invention.

Advantageously, the oil phase can also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils.

Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the silicone oil to be used according to the invention. However, other silicone oils are also advantageous for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane). Also particularly advantageous are mixtures of cyclomethicone and Iso tridecylisononanoat, from cyclomethicone and 2-Ethylhexylisostearat.

If appropriate, the aqueous phase of the preparations according to the invention advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol,

Glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether,

Propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g. As ethanol, isopropanol, 1, 2-propanediol,

Glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group

Silica, aluminum silicates, polysaccharides or their derivatives, e.g.

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 of

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 of the invention are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is usually used for such a type of Formu- tion.

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

The alkylglucosides in turn are advantageously selected from the group of alkylglucosides, which are represented by the structural formula

in which R is a branched or unbranched alkyl radical

Represents 4 to 24 carbon atoms and wherein DP means a mean Glucosylierungsgrad of up to 2.

The value DP represents the degree of glucosidation of the alkylglucosides used in the invention and is defined as

Pi P2 P3 Pi

DP = 1 + 2 + 3 + ... = Σ /

100 100 100 100

In this case, pi, P2, P ₃ ... Or p 1 represent the proportion of products which are mono-, di-trisubstituted ... times glucosylated in weight percentages. According to the invention, products having degrees of glucosylation of 1-2, in particular advantageously of 1 , 1 to 1, 5, very particularly advantageously selected from 1, 2-1, 4, in particular from 1, 3.

The value DP takes into account the fact that alkylglucosides are usually mixtures of mono- and oligoglucosides represent. Advantageously in accordance with the invention is a relatively high content of monoglucosides, typically of the order of 40-70% by weight.

Alkylglylcosides used particularly advantageously according to the invention are selected from the group octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecylglucopyranoside.

It is also advantageous, natural or synthetic raw materials and auxiliary 0 employ substances or mixtures which are distinguished by an effective content of the inventively used active compounds, for example Plantaren ^® 1200 (Henkel KGaA), Oramix ^® NS 10 (Seppic) ,

In turn, the acyl lactylates are advantageously selected from the group of substances which are represented by the structural formula

in which R ¹ denotes a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of the alkali ions and the group of the ammonium ions substituted by one or more alkyl and / or by ₍ - one or more hydroxyalkyl radicals; corresponds to half the equivalent of an alkaline earth metal ion.

For example, sodium is advantageous, for example the product Pathionic ^® ISL from the American Ingredients Company _Q. The betaines are advantageously selected from the group of substances which are defined by the structural formula

characterized in that R ^{2 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms.

Particularly advantageously, R ^{2 is} a branched or unbranched alkyl radical having 6 to 12 carbon atoms.

It is advantageous for example capramidopropylbetaine, for example the product Tego ^® betaine 810 from Th. Goldschmidt AG.

, Sodium, for example, selected as inventively advantageous cocoamphoacetate as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The preparations according to the invention are advantageously characterized in that the hydrophilic surfactant or surfactants in concentrations of 0.01-20 wt .-%, preferably 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, respectively based on the total weight of the composition, is present or present.

For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a quantity sufficient in the manner customary for cosmetics. Cosmetic and dermatological preparations according to the invention can be present in various forms. So they can z. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. oil-in-water

(W / O / W), a gel, a solid stick, an ointment or even an aerosol. It is also advantageous to present Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g. As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-OS 43 08 282, have been found 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 OΛ / V emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsions according to the invention.

According to the invention, suitable co-emulsifiers are, for example, O / W emulsifiers, primarily 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 W emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ¹ , or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers may also be lower or higher.

It is advantageous to choose the fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols). Particularly preferred are: polyethylene glycol (13) stearyl ether

(Steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), polyethylene glycol (17) stearyl ether (steareth-

17), polyethylene glycol (18) stearyl ether (steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene. glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) - isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16), polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) - isostearyl ether (isosteareth-20), polyethylene glycol (13) cetyl ether (cetyl ether). 13), polyethylene glycol (14) cetyl ether (ceteth-14), polyethylene glycol (15) cetyl ether (ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether (ceteth-17), polyethylene glycol ( 18) - cetyl ether (ceteth-18), polyethylene glycol (19) cetyl ether (ceteth-19), polyethylene glycol (20) ce tyl ether (ceteth-20), polyethylene glycol (13) isocetyl ether (isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14), polyethylene glycol (15) isocetyl ether (isoceteth-15), polyethylene glycol (16) isocetyl ether (isocetethoxy) 16), polyethylene glycol (17) - isocetyl ether (isoceteth-17), polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (isoceteth-19), polyethylene glycol (20) isocetyl ether (isoceteth-20), Polyethylene glycol (12) oleyl ether (Oleth-12), polyethylene glycol (13) oleyl ether (Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15), polyethylene glycol (12) lauryl ether (laureth-12), polyethylene glycol (12) - isolauryl ether (isolaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (ceteareth-15 ), Polyethylene glycol (16) cetyl stearyl ether (ceteareth-16), polyethylene glycol (17) cetyl stearyl ether (ceteareth-17), poly ethylene glycol (18) cetylstearyl ether (Ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (Ceteareth-19), polyethylene glycol (20) cetyl stearyl ether (Ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates of the following group:

Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol ( 14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate,

As the ethoxylated alkyl ether carboxylic acid or its salt, the sodium laureth-11-carboxylate can be advantageously used. As the alkyl ether sulfate, sodium laureth-4 sulfate can be advantageously used. As the ethoxylated cholesterol derivative, polyethylene glycol (30) cholesteryl ether can be advantageously used. Also polyethylene glycol (25) soybean oil has been proven. As ethoxylated triglycerides, the polyethylene glycol (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 favorable to choose 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 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 saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids 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 Chain length of 8 to 24, in particular 12-18 C atoms. Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate,

Sorbitan monocaprylate, sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl mono- caprylate or PEG-30 dipolyhydroxystearate.

The compositions or preparations described are particularly useful for protecting human skin against UV radiation, aging processes and oxidative stress, i. against damage by radicals. They are present in various dosage forms commonly used for this application. Thus, the preparation in particular as a lotion or emulsion, such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic Gels or solutions, be present as solid pens or formulated as an aerosol.

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

Dyes used are preferably approved dyes listed in the Cosmetics Regulation, Appendix 3 as a positive list. As preservatives preferably approved preservatives are used, which are listed in the Cosmetics Regulation, Appendix 6 as a positive list or antimicrobial pigments, as described for example in WO 2004/0092283 or WO 2004/091567.

Suitable preservatives are therefore also alkyl esters of p-hydroxybenzoic acid, hydantoin derivatives, propionate salts or a variety of ammonium compounds.

Very particularly preferred preservatives are methylparaben, propylparaben, imidazolidinyl urea, sodium dehydroxyacetate or benzyl alcohol. Preservatives are used in amounts between 0.5 to 2% by weight.

Emollients or plasticizers are often incorporated into cosmetic preparations. They are preferably used in 0.5 to 50% by weight, preferably between 5 and 30% by weight, based on the total composition. In general, plasticizers can be classified into classes, such as the category of esters, fatty acids or fatty alcohols, polyols, hydrocarbons and oils containing at least one amide structure unit.

Representative oils containing at least one amide structure unit together with their synthesis are described in particular in EP 1044676 and EP 0928608. A particularly preferred compound is isopropyl N-lauroyl sarcosinate, which is commercially available under the product name Eldew SL-205 from Ajinomoto.

Among the esters, mono or diesters may be selected. Examples in this regard are dibutyl adipate, diethyl sebacate, diisopropyl dimerate or dioctyl succinate. Branched fatty acid esters are, for example, 2-ethylhexyl myristate, isopropyl stearate or isostearyl palmitate. Tribasic esters For example, trisopropyl trilinoleate or trilauryl citrate. Straight-chain fatty acid esters are, for example, lauryl palmitate, myristyl lactate, oleyl eurcat or stearyl oleate. Preferred esters are coco-caprylates / caprate (= INCI name, esters of coconut oil fatty alcohols with saturated medium-chain fatty acids), propylene glycol myristyl ether acetate, diisopropyl adipate or cetyl octanoate.

Suitable fatty alcohols and acids are compounds having 10 to 20 carbon atoms. Particularly preferred compounds are cetyl, myristyl, palmitic or stearic alcohol or acid.

Suitable polyols are linear or branched-chain alkyl polyhydroxy compounds, for example propylene glycol, sorbitol or glycerol. However, it is also possible to use polymeric polyols, for example polypropylene glycol or polyethylene glycol. Butylene and propylene glycol are also particularly suitable compounds for enhancing the penetration.

Exemplary hydrocarbons as plasticizers are compounds that generally have 12 to 30 carbon atoms. Specific examples are arylalkyl benzoates, alkyl benzoates, mineral oils, petrolatum, squalene or isoparaffins.

Further emollients or water repellents are preferably C 12 to C 15 alkyl benzoates, dioctyl adipate, octyl stearate, octyl dodecanol, hexyl laurate, octyl dodecyl neopentanoate, cyclomethicones, dicapryl ethers, dimethicones, phenyltrimethicones, isopropyl myristate, capriylic / capric glycerides, propylene glycol dicaprylate / dicaprate or decyl oleate.

Another category of functional ingredients of cosmetic preparations in the context of the invention are thickeners. Thickeners are usually in quantities between 0.1 to 20 Wt .-%, preferably between 0.5 to 10 wt .-% based on the total amount used. Exemplary of these compounds are crosslinked polyacrylate materials, available commercially under the Carbopol brand from BF Goodrich Company. It is also possible to use thickeners, such as xanthan gum, carrageenan gum, gelatine gum,

Karaya gum, pectin gum or locust bean gum.

In some circumstances, it is possible that a compound may be both a thickener and a plasticizer. Examples of these are silicone gums (kinematic viscosity> 10 centistokes), esters such as glycerol stearate or cellulose derivatives, for example hydroxypropyl cellulose.

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 in addition to the compound or compounds of formula I, for example fatty alcohols, fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of Contains 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 like glycerine, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.

The preparation or agent of the invention 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 are made 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 customary propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.

The cosmetic preparation may also be used to protect the hair against photochemical damage to prevent changes in hues, discoloration or damage of a mechanical nature. In this case, it is suitably carried out as a shampoo, lotion, gel or emulsion for rinsing, wherein the respective preparation is applied before or after shampooing, before or after dyeing or decolouring or before or after perming. It is also possible to choose a preparation as a lotion or gel for hairdressing and treatment, as a lotion or gel for brushing or laying a wave of water, as hair lacquer, perming agent, dyeing or decolorizing the hair. The formulation with photoprotective properties may contain, in addition to the compound (s) of the formula I, various adjuvants used in this type of mediator, such as surfactants, thickeners, polymers, emollients, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, Anti-grease, dyes and / or pigments which dye the agent itself or the hair or other ingredients commonly used for hair care.

Further objects of the present invention are a process for preparing an agent as described above, characterized in that at least one compound of the formula I is mixed with a carrier and optionally with further active or auxiliary substances.

The present invention also provides a process for

Preparation of a preparation, which is characterized in that at least one compound of the formula I is mixed with radicals as described above, with a cosmetically, pharmaceutically or dermatologically suitable carrier.

The preparations or compositions according to the invention can be prepared using techniques which are well known to the person skilled in the art.

The mixing may result in dissolution, emulsification or dispersion of the compound according to formula I in the carrier.

In the following the invention is explained in more detail by means of examples, the invention is executable throughout the claimed range and not limited to the examples mentioned here.

Examples:

List of abbreviations used:

Eq. equivalent

DCC dicyclohexylcarbodiimide

DMAP dimethylaminopyridine

DMSO dimethyl sulfoxide EDC N- (3-dimethylaminopropyl) -N-ethyl-carbodiimide hydrochloride

EE vinegar

EG ethylene glycol sat. saturated conc. concentrated

1N HCl 1N hydrochloric acid i-PrOH isopropanol

Solution. Solution

MeCN acetonitrile

MTBE methyl t-butyl ether org. organic

RT room temperature

Hour

T temperature

THF tetrahydrofuran

Example 1 :

Synthesis of 2- (4-diethylamino-2-hydroxy-benzoyl) -benzoic acid- (R) -2- ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl 2-hydroxyethyl ester (or synonymously 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid azo-chloro ester)

conc. H ₂ SO ₄ , RT Vitamin C (14.1 g, 79.78 mmol, 5 eq.) Is concentrated in an argon-purged apparatus in 70 ml conc. Sulfuric acid added in portions. The internal temperature is kept below 5 ^° C. by ice-cooling. Subsequently, 5 g of 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid (16 mmol, 1 eq.) Also at T <5 ° C added in portions. After 96 hours reaction time (thawing to room temperature), the reaction solution is poured onto 350 ml of ice water. Under cooling, 140 ml of 32% NaOH solution. dropwise. This forms a violet oil that separates from the aqueous solution (Lsg.). The aqueous solution is poured off and extracted 3 times with ethyl acetate. After drying over sodium sulfate, the solvent is removed in vacuo. The product is obtained as a yellow foam (5.5 g, 73.8%). Melting interval: 90-120 ° C.

Due to the nature of this reaction, the compound 2- (4-diethylamino-2-hydroxy-benzoyl) -benzoic acid (R) -1 - ((R) -3,4-dihydroxy-5-O-O-O-5-dihydro) also falls due to the nature of the synthesis -furan-2-yl) -2-hydroxyethyl ester. The proportion of this compound in the mixture is between 0 and 25%.

A UV spectrum of the product of Example 1 is shown in FIG.

Depending on the pH, these compounds may carry partial charges, as follows for the compound 2- (4-diethylamino-2-hydroxy-benzoyl) - benzoic acid (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxy-ethyl ester is shown:

as ammonium compound,

as a zwitterionic compound or

as ascorbate.

NMR data of 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid (R) -2- ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2 yl) -2-hydroxy-ethyl ester

1 H-NMR (D ₆ -DMSO): 1.10 (t, 6H), 3.39 (q, 4H), 3.98 (m, 1H), 4.13 (dd, 1H), 4.20 (dd, 1H) 4.57 (d, 1H), 5.35 (d, 1H) ₁ 6.07 (d, 1H), 6.18 (dd, 1H), 6.81 (d, 1H) ₁ 7.43 (dd, 1H), 7.65 ( dt, 1H), 7.74 (dt, 1H), 8.08, (dd, 1H), 8.33 (br, 1H), 11.03 (br, 1H), 12.47 (s, 1H) ppm. ¹³ C NMR (D ₆ -DMSO): 12.4, 20.7, 44.1, 65.3, 74.9, 96.4, 104.1, 109.0, 118.1, 127.9, 128.1, 129.5, 130.2, 132.6, 134.2, 140.2, 152.1, 153.7, 164.8, 165.0 , 169.9, 197.5 ppm.

Example 2:

Alternative synthesis of 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid 2- (3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxyethyl ester

A)

10 g of 5,6-isopropylidene-ascorbate (46.3 mmol, 1 eq., Available from Merck-Schuchardt: 8.18234) are dissolved in 30 ml of THF and 35 ml of DMSO, 19.2 g of potassium carbonate are added and 13 ml of benzyl bromide (110 mmol, 2.4 eq.). After 3 hrs. At 50 ° C, the gas evolution is complete. The solid is filtered off and extracted 3 times with 100 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate and the solvent removed in vacuo. The product is obtained almost quantitatively without further purification.

B)

The doubly benzyl-protected 5,6-isopropylidene-ascorbate is dissolved in 65 ml of THF and 30 ml of 2N HCl added slowly at room temperature. After 48 hours, 150 ml of MTBE and solid sodium chloride are added to saturation and extracted. The organic phase is dried over sodium sulfate and the solvent removed in vacuo. The product is obtained almost quantitatively without further purification.

C)

The doubly benzyl-protected ascorbate (2.14 g, 6 mmol, 1 eq.) From step B) is treated with DMAP (73 mg, 0.6 mmol, 0.1 eq.) And 1.88 g of 2- (4- Diethylamino-2-hydroxybenzoyl) benzoic acid (6 mmol, 1 eq.) Dissolved in 11 ml acetonitrile in an argon-purged flask. Then, at ⁰ ° C., the EDC (1.7 g, 9 mmol, 1.5 eq.) Is added in portions. It is warmed to RT and after 22 hours, the solvent removed in vacuo. The residue is washed with 50 ml of ethyl acetate and 50 ml of 1 N NaOH solution. recorded and extracted. The org. Phase is then with 2 x 50 ml of 1 N HCl and 1 x 50 ml sat. NaCl solution. extracted The organic phase is dried over sodium sulfate and the solvent removed in vacuo. The product is obtained after filtration through silica gel.

D)

The educt from stage C) is dissolved in ethyl acetate and reduced under 1-5 bar hydrogen pressure with Pd-C catalyst. After filtration of the catalyst, the product is purified by filtration through silica gel.

Example 3:

Synthesis of fluorescein 6-O-ascorbate (2- (6-hydroxy-3-oxo-3H-xanthene)

9-yl) -benzoic acid 2- (3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxyethyl ester)

In an argon-flushed 3-necked flask, 50 ml of conc. Submitted sulfuric acid and cooled to 0 ⁰ C. There are added portionwise 14.05 g (79.8 mmol, 5 eq.) Of ascorbic acid and then 6.05 g of fluorescein sodium (15.96 mmol, 1 eq.). After 16 hours reaction time at room temperature, the reaction solution is poured onto 250 g of ice, saturated with 80 g of sodium chloride and extracted 3 times with 150 ml of ethyl methyl ketone. The united org. Phases are saturated with 100 ml. NaCl solution, dried over sodium sulfate and the solvent removed in vacuo. After crystallization from ethyl acetate, the product is obtained as a red solid. Example 4:

Synthesis of sorbic acid 6-O-ascorbate [(2E, 4E) -hexa-2,4-dienoic acid-2

(3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxy-ethyl]

N-OH succinimide

DCC, dioxane, water

In a 3-necked flask 5 g of sorbic acid are dissolved in 50 ml of dioxane and successively 5.6 g of N-hydroxy-succinimide (49 mmol, 1, 1 eq.) And 10.1 g of DCC (49 mmol, 1, 1 Äq.) Was added. After a reaction time of 16 hours at room temperature, 39.3 g (223 mmol, 5 eq.) Of ascorbic acid dissolved in 50 ml of water are added and the mixture is stirred at room temperature for 16 h. The solvent is removed in vacuo, the residue is partitioned between 100 ml of dichloromethane and 100 ml of water and extracted. After drying over sodium sulfate, the solvent is removed in vacuo. After crystallization from ethyl acetate, the product is obtained as a white solid.

Example 5:

Synthesis of indomethacin 6-O-ascorbate {[1- (4-chloro-benzoyl) -5-methoxy]

2-methyl-1H-indol-3-yl] -acetic acid 2- (3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxyethyl ester}

In an argon-flushed 3-necked flask, 50 ml of conc. Submitted sulfuric acid and cooled to 0 ^c C. There are portionwise 14.05 g (79.8 mmol, 5 eq.) Ascorbic acid and then 5.71 g lndomethacin (15.96 mmol, 1 eq.) was added. After 16 hours reaction time at room temperature, the reaction solution is poured onto 250 g of ice, saturated with 80 g of sodium chloride and extracted 3 times with 150 ml of ethyl methyl ketone. The united org. Phases are saturated with 100 ml. NaCl solution, dried over sodium sulfate and the solvent removed in vacuo. After crystallization from ethyl acetate, the product is obtained as a white solid.

Example 6:

Synthesis of 2,4,6-triiodo-3-aminoacetylbenzoic acid O-ascorbate [3

Acetylamino-2,4,6-triiodo-benzoic acid 2- (3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxyethyl ester]

In an argon-flushed 3-necked flask, 50 ml of conc. Submitted sulfuric acid and cooled to ^{0 0} C. There are added portionwise 14.05 g (79.8 mmol, 5 eq.) Of ascorbic acid and then 8.89 g of 2,4,6-triiodo-3-aminoacetyl-benzoic acid (15.96 mmol, 1 eq.). After 16 hours reaction time at room temperature, the reaction solution is poured onto 250 g of ice, saturated with 80 g of sodium chloride and extracted 3 times with 150 ml of ethyl methyl ketone. The united org. Phases are saturated with 100 ml. NaCl solution, dried over sodium sulfate and the solvent removed in vacuo. After crystallization from ethyl acetate, the product is obtained as a white solid.

Example 7:

Synthesis of para-diethylaminobenzoic acid 6-O-ascorbate

In an argon-flushed 3-necked flask, 40 ml of conc. Submitted sulfuric acid and cooled to 0 ° C. 11.39 g (64.69 mmol, 5 eq.) Of ascorbic acid and then 2.5 g of para-diethylaminobenzoic acid (12.94 mmol, 1 eq.) Are added in portions. Then 8 ml of oleum (sulfuric acid with 65% SO ₃ ) are added dropwise. After 16 hrs reaction time at 60 ⁰ C, the reaction solution is poured onto 120 g of ice, saturated with 60 g of sodium chloride and extracted 3 times with 100 ml of ethyl methyl ketone. The united org. Phases are saturated with 80 ml. NaCl solution, dried over sodium sulfate and the solvent removed in vacuo. After crystallization from ethyl acetate, the product is obtained as a solid.

Due to the nature of this reaction, the compound para-diethylaminobenzoic acid 5O-ascorbate also accumulates. The proportion of this compound in the mixture is between 0 and 25%.

para-diethylaminobenzoic-5-ascorbate

Example 8:

Synthesis of 3-benzotriazol-2-yl-4-hydroxy-benzoic acid (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2 hydroxy-ethyl ester

In an argon-flushed 3-necked flask, 265 ml conc. Submitted sulfuric acid and cooled to 0 ⁰ C. 124.2 g (0.705 mol, 3 eq.) Of ascorbic acid and then 60 g of 3-benzotriazol-2-yl-4-hydroxybenzoic acid (0.235 mol, 1 eq.) Are added in portions. Then 73.7 ml of oleum (sulfuric acid with 65% SO ₃ ) are added dropwise. After 5 hrs reaction time at 45 ° C, the reaction solution is poured onto 1000 g of ice, saturated with 200 g of sodium chloride and extracted 3 times with 1000 ml of ethyl methyl ketone. The united org. Phases are saturated with 500 ml. NaCl solution, dried over sodium sulfate and the solvent removed in vacuo. After crystallization from ethyl acetate, the product is obtained as a white solid.

Example 9:

Synthesis of (E) -3- {4 - [(R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxy] ethoxy] -phenyl} -acrylic acid 2-ethylhexyl ester

In an argon-purged 3-necked flask, 20 g of ascorbic acid (113.5 mmol; 1 Eq.) Was dissolved in 100 ml of dimethylformamide, 32.76 g of triphenylphosphine was added at 0 ⁰ C 25.3 g of diisopropyl azodicarboxylate (124.9 mmol, 1.1 eq) is added dropwise slowly. To The (E) -3- (4-hydroxyphenyl) -acrylic acid 2-ethylhexyl ester (32.95 g, 1.05 eq, 119.2 mmol), dissolved in 45 ml of dimethylformamide, is added dropwise for 30 minutes. After 30 minutes at ⁰ ° C. stirring is continued for 6 hours at room temperature. The reaction solution is evaporated to dryness, suspended in 100 ml of ethyl acetate / hexane 1: 2, filtered and the product precipitated as a white solid by addition of 100 ml of hexane.

Example 10:

Synthesis of 2-phenyl-3H-benzimidazole-5-sulfonic acid (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxy ethyl

There are 45.1 g of ascorbic acid (255.2 mmol;. 3 eq) was dissolved in in 100 ml of DMF, 521 mg of 4-dimethylamino-pyridine (4.27 mmol; 0.05 eq.) Was added and at 0 C ⁰ 25 g of 2-phenyl-3H-benzimidazole-5-sulfonyl chloride (85.4 mmol, 1 eq.) dissolved in 66 ml of DMF was added dropwise. The mixture is then warmed to room temperature and, after 6 hours, 100 ml of water and 100 ml of chloroform are added, extracted, dried and the solvent is removed in vacuo. The residue is recrystallized in toluene. The product is obtained as a pale beige solid.

Example 11:

Synthesis of (R) -5 - [(R) -2- (3-Benzotriazol-2-yl-4-hydroxy-benzyloxy) -1-hydroxy-ethyl] -3,4-dihydroxy-5H-furan-2-ol on

There are 35 g of (R) -3,4-bis-benzyloxy-5 - ((R) -1,2-dihydroxy-ethyl) -5H-furan-2-one (98.2 mmol, 1 eq.) In Dissolved 250 ml of THF under inert gas atmosphere and at 0 ⁰ C 3.93 g of sodium hydroxide (98.2 mmol, 1 eq.) Was added. After 30 min the dissolved in 100 ml of THF 2-benzotriazole-2-yl-4-bromomethyl-phenol (35.8 g; 117.9 mmol; 1, 2 eq.) Is added dropwise for 60 min at 0 ⁰ C, and Stirred for 7 hours at 70 ^c C. The reaction solution is added after cooling to room temperature with 2 g of Pd-C and hydrogenated at 3 bar and 5O ⁰ C for 5 hours under hydrogen atmosphere. After filtration through a Celite pad, the solution is neutralized with 2N HCl solution. The extraction is done twice with 250 ml sat. NaHCO ₃ solution and 100 ml sat. NaCl solution. From the org. Phase is precipitated with 370 ml of heptane the product.

Example 12:

Synthesis of 5 - ((3aR, 6S, 6aS) -2-oxo-hexahydro-thieno [3,4-d] imidazol-6-yl) -pentanoic acid (R) -2 - ((R) -3,4- dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxyethyl ester

Under inert gas 54.1 g of ascorbic acid (306.9 mmol, 5 eq.) And 15 g of biotin (61, 4 mmol, 1 eq.) Dissolved in 180 ml of anhydrous acetone, treated with 1 g of lipase (Candida antarctica) and shaken at 40 ⁰ C for 32 h. The enzyme is filtered off, the solution is mixed with 50 ml of water and the product is precipitated by pouring onto toluene.

Binding demonstration:

Example I:

Binding evidence (skin model):

A mixture of two isomers of 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid 2- (3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2- hydroxyethyl ester, prepared according to Example 1 or 2, abbreviated to DHAB below, 4% solutions are prepared in various solvent systems. Of these, 40 .mu.l are applied to 2.5 x 7.5 cm gelatin plates and stored at 87% humidity for 24 hours. Thereafter, the plates are eluted with 50 ml of iPrOH in an ultrasonic bath for 5 min. The binding to the gelatin is carried out by comparison with a corresponding standard solution:

Table 1 :

DHAB also means diethylamino hydroxybenzoyl ascorbyl benzoate. DHHB means below diethylamino hydroxybenzoyl hexyl benzoate, a non-binding UV filters, known as Uvinul ^® A Plus.

Example II:

Proof of binding to chicken skin:

A) DHAB is 2% dissolved in dimethyl isosorbide. The solution is applied to chicken skin at an application rate of 2.66 μL / cm ² . After 16 hours of exposure, the samples are extracted in an ultrasonic bath with isopropanol. The extracts are measured photometrically at 354 nm and compared with a 100% value (= application solution without application). The Difference in recovery compared to the 100% value corresponds to the amount of active ingredient bound to the skin. For DHAB, a binding fraction of 76% results, while the non-binding comparative substance DHHB is expected to have a low value of only 3%.

B) Proof of binding to pigskin: The following materials are prepared:

2% solution of DHAB in Arlasolve DMI sample (A) and pelemol BIP sample (B)

Formulation with 1% DHAB sample (C) [= 54-07-5-A, from Example V]

2% solution of DHHB in Arlasolve DMI sample (D) and isopropyl myristate sample (E)

Formulations with 0.84% DHHB Sample Sample (F) [= 54-07-5-B from Example V] and 0.84% DHHB + 0.37% Vitamin C Sample (G) [= 54-07-5- C from Example V].

• Pig skin is cut to 2.5x7.5 cm and placed on Plexiglas slides.

Execution:

From the samples (A) to (G) are each 50 .mu.l dripped onto the slides with pig skin, spread with a plastic spatula and the slides in a desiccator [87% humidity by sat. KCl solution] for 24 h at room temperature. The slides are then rinsed with 50 ml of isopropanol in a volumetric flask, treated in an ultrasound bath for 5 min, filtered cleanly via a syringe filter (turbidity due to detached skin constituents) and measured by UV spectrometer (400-250 nm, UV _max ~ 355 nm) (residue 1 to 7). To serve as a 100% comparison value

50 ml of isopropanol solutions of 50 μl each of samples (A) to (G) which are also measured by UV spectrometer. The results are summarized in Table 2:

100% comparison values (= direct measurement without order on pig skin)

sample

DHAB 2% in Arlasolve DMI 1, 501

B DHAB 2% in pelemol GDP 1, 375

DHAB 1% in W / O 54-07-5-A 0.459

DHHB 2% in Arlasolve DMI 2.023

DHHB 2% in isopropyl myristate 1, 504

DHHB 0.84% in W / O 54-07-5-B 0.730

DHHB + 0.84% in W / O 54-07-5-C .781 Vitamin C

^* : The term "bond" is to be equated with the term "non-extractable residue". The extraction was carried out with isopropanol. The samples were additionally treated with ultrasound for 5 min.

Example III:

Binding evidence of hair:

Human hair samples are stirred with a 0.2% ethanolic solution of DHAB or DHHB (ethanol / water = 80/20) for 8 h, then rinsed with ethanol / water = 80/20 and added to the SEM measurement (SEM = scanning Electron Microscope). The comparison between DHAB and DHHB shows that in the DHAB-SEM picture areas are more clearly recognizable, which are interpreted as active ingredient attachment to the haircuticle.

Example IV: Antioxidant activity:

Basis for the determination of the antioxidant efficacy is the so-called DPPH test as in Bünger et. al. [Buenger, J., Ackermann, H., Jentzsch, A., Mehling, A., Pfizner, I., Ripening, K.-A., Schroeder, K.-R., and Wollenweber U., An interlaboratory comparison of methods used to assess antioxidant potentials, Int. J. Cosm. Sci., 28 (2006) 1-12]. The antioxidant activity of DHAB is determined in the DPPH test. The EC50 value for DHAB is 0.32 μmol / L, reflecting the excellent radical scavenging properties of DHAB. This is comparable to ascorbic acid itself, the value of which is determined to be 0.29 μmol / L. DHHB is only 36 μmol / L and can be described as DPPH-inactive.

The following example describes formulations for cosmetic preparations:

Example V: W / O emulsion

Preservative 1, 00 1, 00 1, 00 1, 00 1, 00

Water Ad 100 Ad 100 Ad 100 Ad 100 Ad 100

NaCl 0, 50 0, 50 0, 50 0, 50 0, 50

EDTA 0, 10 0, 10 0, 10 0, 10 0, 10

Citric acid q.S.

Production: PELEMOL ^® GDP Arlasolv DMI and emulsifiers are presented. DHAB and Uvinul ^® A Plus are dissolved in it. The remaining components of the oil phase are added and mixed homogeneously. With stirring, the adjusted to pH = 4-5 water phase is emulsified. Subsequently, it is homogenized. The emulsions can be prepared under mild conditions at room temperature. By increasing the content of ascorbic acid DHAB can be stabilized. Ideally, the production is carried out under inertization (exclusion of oxygen).

Example VI: Waterproof sunscreen spray

Preparation: The components of phase A are combined at room temperature and stirred until a clear solution is obtained. Subsequently, phase B is mixed and added with stirring to phase B. Continue stirring until finally the clear product is present. To the addition of antioxidants such as Oxynex ^® ST Liquid, RonaCare ^® AP or ascorbyl the stability of the substances of the invention can be increased.

Example VII: Pump Hairspray

Preparation: Pre-dissolve phase A until a clear solution is obtained. Add phase B to phase A with stirring. Premix phase C and add to the rest, stirring until a homogeneous mixture has formed.

Example VIII: W / O Emulsions

Example IX: Hair Care Formulation

Example X: Hair Care Formulation

Example XI: O / W emulsions

Example XII: O / W Emulsions

Example XIII: OΛ / V Emulsions

Example XIV: Hydrodisperions (lotions and sprays)

Example XV: aqueous and aqueous / alcoholic formulations

Example XVI: cosmetic foams

Example XVII: Cosmetic foams

Claims

claims

I. Use of at least one ascorbic acid derivative for the functionalization of matrices.

2. Use according to claim 1, characterized in that the matrix is skin, hair or nails.

3. Use according to claim 1 or 2, characterized in that the at least one ascorbic acid derivative of the formula I.

corresponds, where

R ¹ or R ^{2 are} each independently hydroxy, -O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl, alkyl-C 1 -C 6 -alkyl, M alkali or alkaline earth metal cation or H,

R ³ or R ^{4 are} each independently hydroxy or a radical B and B is the radical of a pharmacological, antimicrobial, fungicidal, herbicidal, insecticidal or cosmetic active ingredient, a UV filter, an X-ray contrast agent or a dye, with the proviso that at least one the radicals R ³ or R ^{4 is} a radical B.

4. Use according to claim 3, characterized in that R ² in formula I is hydroxy.

5. Use according to claim 3 or 4, characterized in that R ¹ in formula I is hydroxy.

6. Use according to one or more of claims 3 to 5, characterized in that the radical B in formula I is the radical of a pharmacologically active ingredient.

7. Use according to one or more of claims 3 to 6, characterized in that the radical B in formula I is the radical of an antimicrobial active ingredient.

8. Use according to one or more of claims 3 to 7, characterized in that the radical B in formula I is the radical of a fungicidal, herbicidal or insecticidal active ingredient.

9. Use according to one or more of claims 3 to 8, characterized in that the radical B in formula I is the radical of a cosmetic

Active ingredient means.

10. Use according to one or more of claims 3 to 9, characterized in that the radical B in formula I means the rest of an X-ray contrast agent.

11. Use according to one or more of claims 3 to 10, characterized in that the radical B in formula I is the radical of a dye.

12. Use according to one or more of claims 3 to 11, characterized in that the radical B in formula I is the radical of a UV filter.

13. Use according to one or more of claims 3 to 12, characterized in that the radical B in formula I is bonded via an ester function.

14. Use according to one or more of claims 3 to 12, characterized in that the radical B in formula I is bonded via an ether function.

15. Use according to one or more of claims 3 to 14, characterized in that the radical B in formula I is a substituent which absorbs UV radiation and has a conjugated π-electron system of at least 4 π-electrons.

16. Use according to one or more of claims 3 to 15, characterized in that the radical B in formula I is a substituent which absorbs UV-A and / or UV-B radiation and a conjugated π-electron system of at least 4 has π-electrons.

17. Use according to one or more of claims 3 to 16, characterized in that the radical B in formula I is a substituent of formula II, IM, IV, V, VI, VII, VIII, IX, X, XI and / or XII is

in which

R ⁵ to R ^{16 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -

- [SO ₃ ] X or 2H-benzotriazol-2-yl mean and

A is alkyl having 1 to 4 C atoms, n is an integer from 1 to 25,

Y and Z are each independently -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ .

18. Compounds of the formula in which

R ¹ or R ^{2 are} each independently hydroxy, -O-alkyl, -OC (O) -

Alkyl, -OPO ₃ M or O-glycosyl,

Alkyl d-Ce-alkyl,

M alkali or alkaline earth metal cation or H,

R ³ or R ^{4 are} each independently hydroxy or a radical B and

B is a substituent of the formula II, III, IV, V, VI, VII, VIII, IX, X, XI and / or XII,

in which

R ⁵ to R ^{16 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -

NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] _{2 l} - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H,

- [SO ₃ ] X or 2H-benzotriazol-2-yl mean and

A is alkyl having 1 to 4 C atoms, n is an integer from 1 to 25,

Y and Z are each independently -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ , wherein for R ⁵ to R ⁹ in formula IV the radicals H , OH and OA except in the case where at least one substituent of R ⁵ to R ^{9 is} A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H , -N [(CH ₂ -CH ₂ -O) _n - H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl and with the proviso that at least one of the radicals R ³ or R ^{4 is} a radical B is.

19. Compounds according to claim 18, characterized in that R ² in formula I is hydroxy.

20. Compounds according to claim 18 or 19, characterized in that R ¹ in formula I is hydroxy.

21. Compounds according to one or more of claims 18 to 20, characterized in that R ⁵ to R ⁹ , R ¹¹ and R ¹² in formula II are H and R ^{10 is} -OH, -OA, -A, -NH ₂ , - NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

22. Compounds according to one or more of claims 18 to 20, characterized in that R ⁵ , R ⁶ , R ⁸ and R ⁹ in formula III are H and R ^{7 is} -OH, -OA, -A, -NH ₂ , - NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X ₁ -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

23. Compounds according to one or more of claims 18 to 20, characterized in that R ⁵ , R ⁶ , R ⁸ and R ⁹ in formula IV are H and

R ⁷ -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H ₁ -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X ₁ -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

24. Compounds according to one or more of claims 18 to 20, characterized in that R ⁶ in formula IV is 2H-benzotriazol-2-yl, R ⁵ , R ⁸ and R ^{9 are} H and R ^{7 is} -OH ₁ -OA, -A ₁ -NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -Nt (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H or - [SO ₃ ] X is.

25. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁶ , R ⁸ , R ¹¹ and R ¹³ in

Formula VH and the substituents R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ^{14 are} each independently H ₁ -OH, -OA ₁ -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ - CH ₂ -O) _n -H ₁ -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

26. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁶ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ^{16 of} the formula VI are preferably H, the substituents R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, - NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n - H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazole 2-yl and Z are hydroxy, -O-2-ethylhexyl, OA or -NH-C (CH ₃ ) ₃ .

27. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in formula VII are H and Z is ascorbyl, hydroxy, -O 2-ethylhexyl, -O-hexyl, - OA or -NH-C (CH ₃ ) ₃ .

28. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ in

Formula VIII is H and R ^{9 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NKCH ₂ -CH ₂ - O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H ₁ - [SO ₃ ] X or 2H-benzotriazol-2-yl.

29. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula IX are H and R ^{9 is} -OH ₁ -OA, -A ₁ -NH ₂ , -NHA ₁ -NA ₂ , -NH- (CH ₂ -CH ₂ - O) _n -H, -Nt (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H - Benzotriazol-2-yl means.

30. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁵ , R ⁷ and R ⁸ in formula X.

H and R ^{6 are} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NKCH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

31. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ and R ¹² in formula XI are H and R ^{10 is} H, - OH, -OA, -A ₁ -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NI (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

32. Compounds according to one or more of claims 18 to 20, characterized in that the substituents R ⁵ , R ⁶ , R ⁸ and R ⁹ in formula XII are H and R ^{7 is} -OH ₁ -OA ₁ -A, -NH ₂ , -NHA ₁ -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X ₁ -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

33. A process for the preparation of compounds according to one or more of claims 18 to 30, characterized in that a) a compound of formula XIII

wherein

R ¹ or R ² have the meaning described in claims 18 to 30, directly with a compound of formula XIV

B-M XIV

wherein B has a meaning described in claims 18 to 30, wherein the partial formulas are excluded Xl and XII, and

M is alkali metal or alkaline earth metal cation or H is reacted or b) the hydroxy groups of the compound of formula XIII ₁ as described above, are protected to a compound of formula XV,

wherein

R ¹ or R ^{2 have} a meaning described in claims 18 to 30, hereinafter the radicals R ¹ and / or R ² , if these are hydroxy groups, are protected by a second protecting group, which are cleavable again under other reaction conditions such as the protective group SG , the protecting groups SG of the compounds of formula XV again cleaved and the resulting compound with a compound of formula XIV

BM XIV, wherein B has a meaning described in claims 18 to 30, wherein the subformulae Xl and XII are excluded, and M is alkali metal or alkaline earth metal cation or H, and then the radicals R ¹ and / or R ² as Deprotected hydroxy group and optionally converts these hydroxy groups into another radical R ¹ or R ² ≠ OH.

34. A process for the preparation of compounds according to one or more of claims 18 to 20 and 31 to 32, characterized in that a) a compound of formula XIII

wherein

R ¹ or R ^{2 is} one described in claims 18 to 20 and 31 to 32

Meaning, with a compound of formula XVI or XVII

wherein R ⁵ to R ^{12 have} a meaning described in claims 18 to 20 and 31 to 32, and

Hal is Cl, Br, I or active ester, or b) the hydroxy groups of the compound of the formula XIII, as described above, are protected to give a compound of the formula XV, wherein

R ¹ or R ² have a meaning described in claims 18 to 20 and 31 to 32, hereinafter the radicals R ¹ and / or R ² , if these are hydroxy groups, are protected by a second protective group, among others

wherein R ⁵ to R ¹² have a meaning as described in claims 18 to 20 and 31 to 32, and

HaI Cl, Br ₁ I or active ester and then deprotected the radicals R ¹ and / or R ² as the hydroxy group and optionally this

Hydroxy groups in another radical R ¹ or R ² ≠ OH converts.

35. Composition containing at least one compound according to one or more of claims 18 to 32.

36. Composition containing at least one compound of the formula I ₁

in which

R ¹ or R ^{2 are} each independently hydroxy, -O-alkyl, -OC (O) -

Alkyl, -OPO ₃ M or O-glycosyl,

Alkyl d-Ce-alkyl,

M alkali or alkaline earth metal cation or H, R ³ or R ^{4 are} each independently hydroxy or a radical B and

Dye means, with the proviso that at least one of R ³ or R ^{4 is} a radical B.

37. Composition according to claim 35 or 36, characterized in that it contains a cosmetically or pharmacologically acceptable carrier.

38. Composition according to one or more of claims 35 to 37, characterized in that the at least one compound of formula I is contained in amounts of 0.05 to 10% by weight.

39. Composition according to one or more of claims 35 to 38, characterized in that at least one further organic UV filter is included, which can absorb UV-A and / or UV-B rays.

40. Composition according to one or more of claims 35 to 39, characterized in that at least one inorganic UV filter is included.

41. Composition according to one or more of claims 35 to 40, characterized in that at least one further ascorbic acid derivative, preferably from the group of ascorbic acid, magnesium ascorbyl phosphate or ascorbyl palmitate, is included.

42. Composition according to one or more of claims 35 to 41, characterized in that at least one antioxidant is contained.

43. Composition according to one or more of claims 35 to 42, characterized in that at least one anti-aging active ingredient and / or at least one anti-cellulite active ingredient is included.

44. Composition according to one or more of claims 35 to 43, characterized in that at least one vitamin derivative is contained.

45. Composition according to one or more of claims 35 to 44, characterized in that at least one further adjuvant selected from the group consisting of thickeners, emollients, humectants, surface-active agents, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, Propellants, dyes and / or pigments which dye the agent itself or the skin is included.

46. A process for preparing a composition according to one or more of claims 35 to 45, characterized in that at least one compound according to one or more of claims 18 to 32 is mixed with a carrier and optionally with further active or auxiliary substances.