# US 2010/0167936 A1 · Use of ascorbic acid derivatives for the functionalization of matrices

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- Number: US 2010/0167936 A1
- Document ID: US20100167936A1
- Status: Published application
- Kind: A1
- Application number: 12/377,008
- Filed: 2007-06-27
- Published: 2010-07-01
- Earliest claimed: 2006-08-11
- Assignees: Merck Patent GmbH
- Inventors: Thomas Rudolph; Philipp Buehle; Herwig Buchholz
- Web page: https://patentgrep.com/patent/US20100167936A1

## CPC

- A61K 8/676: {Ascorbic acid, i.e. vitamin C}
- A61P 31/04: Antibacterial agents
- A61P 31/10: Antimycotics
- A61Q 17/04: Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
- A61Q 19/00: Preparations for care of the skin
- C07D 307/62: Three oxygen atoms, e.g. ascorbic acid
- C07D 405/12: linked by a chain containing hetero atoms as chain links
- C07D 407/12: linked by a chain containing hetero atoms as chain links
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

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

## Claims

### Claim 1

A process for functionalizing a matrix comprising applying to the matrix at least one ascorbic acid derivative.

### Claim 2 (depends on 1)

A process according to claim 1, characterised in that the matrix is skin, hair or nails.

### Claim 3 (depends on 1)

A process according to claim 1, characterised in that the at least one ascorbic acid derivative conforms to the formula I
where
R1 or R2 each, independently of one another, denote hydroxyl, —O-alkyl, —OC(O)-alkyl, —OPO3M or O-glycosyl,
alkyl denotes C1-C6-alkyl,
M denotes an alkali or alkaline-earth metal cation or H,
R3 or R4 each, independently of one another, denote hydroxyl or a radical B, and
B denotes the radical of a pharmacological, antimicrobial, fungicidal, herbicidal, insecticidal or cosmetic active compound, of a UV filter, of an X-ray contrast agent or of a dye,
with the proviso that at least one of the radicals R3 or R4 stands for a radical B.

### Claim 4 (depends on 3)

A process according to claim 3, characterised in that R2 in formula I denotes hydroxyl.

### Claim 5 (depends on 3)

A process according to claim 3, characterised in that R1 in formula I denotes hydroxyl.

### Claim 6 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of a pharmacological active compound.

### Claim 7 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of an antimicrobial active compound.

### Claim 8 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of a fungicidal, herbicidal or insecticidal active compound.

### Claim 9 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of a cosmetic active compound.

### Claim 10 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of an X-ray contrast agent.

### Claim 11 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of a dye.

### Claim 12 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I denotes the radical of a UV filter.

### Claim 13 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I is bonded via an ester function.

### Claim 14 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I is bonded via an ether function.

### Claim 15 (depends on 3)

A process according to claim 3, characterised 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 4π electrons.

### Claim 16 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I is a substituent which absorbs UV-A and/or UV-B radiation and has a conjugated π electron system of at least 4π electrons.

### Claim 17 (depends on 3)

A process according to claim 3, characterised in that the radical B in formula I is a substituent of the formula II, III, IV, V, VI, VII, VIII, IX, X, XI and/or XII
where
R5 to R16 each, independently of one another, denote H, —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl 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 [NHA2]+ and [NA3]+ or to the anion [SO3]− and
Y and Z are each, independently of one another, -ascorbyl, hydroxyl, —O-2-ethylhexyl, —O-hexyl, —OA or —NH—C(CH3)3.

### Claim 18

A compound of the formula I
where
R1 or R2 is each, independently of one another, hydroxyl, —O-alkyl, —OC(O)-alkyl, —OPO3M or O-glycosyl,
alkyl is C1-C6-alkyl,
M is an alkali or alkaline-earth metal cation or H,
R3 or R4 are each, independently of one another, hydroxyl 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
where
R5 to R16 each, independently of one another, denote H, —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl 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 [NHA2]+ and [NA3]+ or to the anion [SO3]− and
Y and Z are each, independently of one another, -ascorbyl, hydroxyl, —O-2-ethylhexyl, —O-hexyl, —OA or —NH—C(CH3)3,
where for R5 to R9 in formula IV, the radicals H, OH and OA are excluded, apart from the case where at least one substituent from R5 to R9 denotes A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl, and
with the proviso that at least one of the radicals R3 or R4 stands for a radical B.

### Claim 19 (depends on 18)

A compound according to claim 18, characterised in that R2 in formula I denotes hydroxyl.

### Claim 20 (depends on 18)

A compound according to claim 18, characterised in that R1 in formula I denotes hydroxyl.

### Claim 21 (depends on 18)

A compound according to claim 18, characterised in that R5 to R9, R11 and R12 in formula II denote H and R10 is —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 22 (depends on 18)

A compound according to claim 18, characterised in that R5, R6, R8 and R9 in formula III are H and R7 denotes —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 23 (depends on 18)

A compound according to claim 18, characterised in that R5, R6, R8 and R9 in formula IV are H and R7 denotes -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 24 (depends on 18)

A compound according to claim 18, characterised in that R6 in formula IV denotes 2H-benzotriazol-2-yl, R5, R8 and R9 are H and R7 is —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H or —[SO3]X.

### Claim 25 (depends on 18)

A compound according to claim 18, characterised in that the substituents R6, R8, R11 and R13 in formula V are H and the substituents R5, R7, R9, R10, R12 and R14 are each, independently of one another, H, —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 26 (depends on 18)

A compound according to claim 18, characterised in that the substituents R6, R8, R9, R12, R13 and R16 of the formula VI are preferably H, the substituents R5, R7, R10, R11, R14 and R15 are each, independently of one another, H, —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl and Z is hydroxyl, —O-2-ethylhexyl, OA or —NH—C(CH3)3.

### Claim 27 (depends on 18)

A compound according to claim 18, characterised in that the substituents R5, R6, R7, R8, R9 and R10 in formula VII are H and Z denotes -ascorbyl, hydroxyl, —O-2-ethylhexyl, —O-hexyl, —OA or —NH—C(CH3)3.

### Claim 28 (depends on 18)

A compound according to claim 18, characterised in that the substituents R5, R6, R7 and R8 in formula VIII are H and R9 denotes —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 29 (depends on 18)

A compound according to claim 18, characterised in that the substituents R5, R6, R7 and R8 in formula IX are H and R9 denotes —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 30 (depends on 18)

A compound according to claim 18, characterised in that the substituents R5, R7 and R8 in formula X are H and R6 denotes —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 31 (depends on 18)

A compound according to claim 18, characterised in that the substituents R5, R6, R7, R8, R9, R11 and R12 in formula XI are H and R10 denotes H, —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 32 (depends on 18)

A compound according to claim 18, characterised in that the substituents R5, R6, R8 and R9 in formula XII are H and R7 denotes —OH, —OA, -A, —NH2, —NHA, —NA2, —NH—(CH2—CH2—O)n—H, —N[(CH2—CH2—O)n—H]2, —[NHA2]X, —[NA3]X, —SO3H, —[SO3]X or 2H-benzotriazol-2-yl.

### Claim 33 (depends on 18)

A process for the preparation of a compound according to claim 18, characterised in that
a) a compound of the formula XIII
in which
R1 or R2 has a meaning described in claim 18,
is reacted directly with a compound of the formula XIV
B-M XIV
in which B has a meaning described in claim 18, where the sub-formulae XI and XII are excluded, and
M denotes an alkali metal or alkaline-earth metal cation or H, or
b) the hydroxyl groups of the compound of the formula XIII, as described above, are protected to give a compound of the formula XV
in which
R1 or R2 has a meaning described in claim 18,
the radicals R1 and/or R2, if these are hydroxyl groups, are subsequently protected by a second protecting group which can be cleaved off again under different reaction conditions to the protecting group SG,
the protecting groups SG of the compounds of the formula XV are cleaved off again, and the resultant compound is reacted with a compound of the formula XIV
B-M XIV,
where B has a meaning described in claim 18, where the sub-formulae XI and XII are excluded, and
M denotes an alkali metal or alkaline-earth metal cation or H, and the radicals R1 and/or R2 for the hydroxyl group are subsequently deprotected as hydroxyl group and these hydroxyl groups are, if desired, converted into another radical R1 or R2≠OH.

### Claim 34 (depends on 18)

A process for the preparation of a compound according to claim 18, characterised in that
a) a compound of the formula XIII
in which
R1 or R2 have a meaning described in claim 18,
is reacted with a compound of the formula XVI or XVII
in which R5 to R12 have a meaning described in claim 18, and
Hal denotes Cl, Br, I or active ester, or
b) the hydroxyl groups of the compound of the formula XIII, as described above, are protected to give a compound of the formula XV
in which
R1 or R2 have a meaning described in claim 18,
the radicals R1 and/or R2, if these are hydroxyl groups, are subsequently protected by a second protecting group which can be cleaved off again under different reaction conditions to the protecting group SG,
the protecting groups SG of the compounds of the formula XV are cleaved off again, and the resultant compound
is reacted with a compound of the formula XVI or XVII
in which R5 to R12 have a meaning described in claim 18, and
Hal denotes Cl, Br, I or active ester, and the radicals R1 and/or R2 are subsequently deprotected as hydroxyl group, and these hydroxyl groups are, if desired, converted into another radical R1 or R2≠OH.

### Claim 35 (depends on 18)

An agent comprising at least one compound according to claim 18.

### Claim 36

An agent comprising at least one compound of the formula I
where
R1 or R2 each, independently of one another, denote hydroxyl, —O-alkyl, —OC(O)-alkyl, —OPO3M or O-glycosyl,
alkyl denotes C1-C6-alkyl,
M denotes an alkali or alkaline-earth metal cation or H,
R3 or R4 each, independently of one another, denote hydroxyl or a radical B, and
B denotes the radical of a pharmacological, fungicidal, herbicidal, insecticidal or cosmetic active compound, of an X-ray contrast agent or of a dye,
with the proviso that at least one of the radicals R3 or R4 stands for a radical B.

### Claim 37 (depends on 35)

An agent according to claim 35, characterised in that said agent further comprises a cosmetically or pharmacologically compatible vehicle.

### Claim 38 (depends on 35)

An agent according to claim 35, characterised in that the at least one compound of the formula I is present in an amount of 0.05 to 10% by weight.

### Claim 39 (depends on 35)

An agent according to claim 35, characterised in that at least one further organic UV filter which is able to absorb UV-A and/or UV-B rays is present.

### Claim 40 (depends on 35)

An agent according to claim 35, characterised in that at least one inorganic UV filter is present.

### Claim 41 (depends on 35)

An agent according to claim 35, characterised in that at least one further ascorbic acid derivative, preferably from the group ascorbic acid, magnesium ascorbyl phosphate or ascorbyl palmitate, is present.

### Claim 42 (depends on 35)

An agent according to claim 35, characterised in that at least one antioxidant is present.

### Claim 43 (depends on 35)

An agent according to claim 35, characterised in that at least one antiageing active compound and/or at least one anti-cellulite active compound is present.

### Claim 44 (depends on 35)

An agent according to claim 35, characterised in that at least one vitamin derivative is present.

### Claim 45 (depends on 35)

An agent according to claim 35, characterised in that at least one further auxiliary, selected from the group thickeners, softeners, moisturisers, surface-active agents, emulsifiers, preservatives, antifoams, perfumes, waxes, lanolin, propellants, dyes and/or pigments which colour the agent itself or the skin, is present.

### Claim 46 (depends on 35)

A process for the preparation of an agent according to claim 35, characterised in that said at least one compound is mixed with a vehicle and optionally with further active compounds or auxiliaries.