WO2022248263A1 - Oxidation products of methionylmethionine - Google Patents
Oxidation products of methionylmethionine Download PDFInfo
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- WO2022248263A1 WO2022248263A1 PCT/EP2022/063139 EP2022063139W WO2022248263A1 WO 2022248263 A1 WO2022248263 A1 WO 2022248263A1 EP 2022063139 W EP2022063139 W EP 2022063139W WO 2022248263 A1 WO2022248263 A1 WO 2022248263A1
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- Prior art keywords
- hair
- methionylmethionine
- weight
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- compound
- Prior art date
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- ZYTPOUNUXRBYGW-UHFFFAOYSA-N methionyl-methionine Chemical compound CSCCC(N)C(=O)NC(C(O)=O)CCSC ZYTPOUNUXRBYGW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 108010085203 methionylmethionine Proteins 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims description 32
- 238000007254 oxidation reaction Methods 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 238000009472 formulation Methods 0.000 claims abstract description 54
- 239000002537 cosmetic Substances 0.000 claims abstract description 22
- 210000004209 hair Anatomy 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 230000006378 damage Effects 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 230000004792 oxidative damage Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- -1 permanganate Chemical compound 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000003664 tensile strength of the hair Effects 0.000 claims description 2
- 230000003685 thermal hair damage Effects 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 abstract description 6
- 150000003462 sulfoxides Chemical class 0.000 abstract description 6
- ZYTPOUNUXRBYGW-HTQZYQBOSA-N (2r)-2-[[(2r)-2-azaniumyl-4-methylsulfanylbutanoyl]amino]-4-methylsulfanylbutanoate Chemical compound CSCC[C@@H]([NH3+])C(=O)N[C@@H](C([O-])=O)CCSC ZYTPOUNUXRBYGW-HTQZYQBOSA-N 0.000 abstract description 3
- ZYTPOUNUXRBYGW-JGVFFNPUSA-N (2r)-2-[[(2s)-2-azaniumyl-4-methylsulfanylbutanoyl]amino]-4-methylsulfanylbutanoate Chemical compound CSCC[C@H]([NH3+])C(=O)N[C@@H](C([O-])=O)CCSC ZYTPOUNUXRBYGW-JGVFFNPUSA-N 0.000 abstract description 3
- ZYTPOUNUXRBYGW-SFYZADRCSA-N (2s)-2-[[(2r)-2-azaniumyl-4-methylsulfanylbutanoyl]amino]-4-methylsulfanylbutanoate Chemical compound CSCC[C@@H]([NH3+])C(=O)N[C@H](C([O-])=O)CCSC ZYTPOUNUXRBYGW-SFYZADRCSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000006399 aminohydroxylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FCFWEOGTZZPCTO-QMMMGPOBSA-N (2s)-3,6-dimethoxy-2-propan-2-yl-2,5-dihydropyrazine Chemical compound COC1=N[C@@H](C(C)C)C(OC)=NC1 FCFWEOGTZZPCTO-QMMMGPOBSA-N 0.000 description 1
- ZYTPOUNUXRBYGW-YUMQZZPRSA-N Met-Met Chemical compound CSCC[C@H]([NH3+])C(=O)N[C@H](C([O-])=O)CCSC ZYTPOUNUXRBYGW-YUMQZZPRSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- AFJYYKSVHJGXSN-KAJWKRCWSA-N selamectin Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1C(/C)=C/C[C@@H](O[C@]2(O[C@@H]([C@@H](C)CC2)C2CCCCC2)C2)C[C@@H]2OC(=O)[C@@H]([C@]23O)C=C(C)C(=N\O)/[C@H]3OC\C2=C/C=C/[C@@H]1C AFJYYKSVHJGXSN-KAJWKRCWSA-N 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/447—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof containing sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/007—Preparations for dry skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/002—Preparations for repairing the hair, e.g. hair cure
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
Definitions
- the invention relates to oxidation products of methionylmethionine, to their preparation and use.
- EP 2 835 151 discloses cosmetic formulations containing at least one methionylmethionine stereoisomer chosen from the group D-methionyl-L-methionine, L-methionyl-D-methionine and D- methionyl-D-methionine and also the use of methionylmethionine for nail and/or hair treatment. Supplemental of J. Am. Chem. Soc., 1998, 120(14), 3345-3356, discloses the di- and monosulfoxides of the methionylmethionine stereoisomer L-methionyl-L-methionine.
- the present invention accordingly relates to sulfoxides and sulfones of the methionylmethionine stereoisomers D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D- methionine.
- An additional object is cosmetic formulations comprising sulfoxides and sulfones of methionylmethionine and also the use of the sulfoxides and sulfones of methionylmethionine contained.
- the oxidation products are thermally stable. It is a further advantage of the present invention that the oxidation products are non-toxic.
- the oxidation products are biodegradable.
- the oxidation products are hygroscopic and moisturizing.
- the present invention accordingly relates to a cosmetic formulation comprising at least one oxidation product of methionylmethionine chosen from the group of the general formulae
- DD and LL behave towards each other as image and mirror image, i.e. they are enantiomers and therefore also have the same physical properties.
- the same is true for the pair DL and LD.
- the two pairs DD/LL and DL/LD are in comparison diastereomeric relative to one another, i.e. they have different physical data.
- Preferred cosmetic formulations according to the invention are characterized in that at least one X is equal to SO or SO2, particularly preferably SO; very particularly preferably, X is equal to SO.
- Cosmetic formulations according to the invention are preferably characterized in that the total amount of the oxidation products of methionylmethionine present is from 0.01 % by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight, particularly preferably from 0.1% by weight to 10% by weight, the percentages by weight being with reference to the total formulation.
- the total amount of LL is less than or equal to 50% by weight, preferably less than 35% by weight, particularly preferably less than 18% by weight.
- the ratio by weight of DL and LD to DD and LL in the cosmetic formulation according to the invention is preferred according to the invention for the ratio by weight of DL and LD to DD and LL in the cosmetic formulation according to the invention to be from 9:1 to 2:3, preferably 8:2 to 1 :1, in particular 6:3 to 4:2, where per enantiomer pair in each case the sum of the individual enantiomers is taken into consideration.
- the abovementioned formulation does not exclude the possibility of only one of the enantiomers of an enantiomer pair being present in the formulation.
- the ratio by weight of DL and LD to DD and LL in the formulation according to the invention is from 10:80 to 0.01 :110.
- Preferred cosmetic formulations according to the invention are characterized in that they represent an aqueous solution, an emulsion or suspension.
- the formulations according to the invention can comprise e.g. at least one additional component chosen from the group of emollients, surfactants, emulsifiers, thickeners/viscosity regulators/stabilizers,
- UV light protection filters antioxidants, hydrotropes (or polyols), solids and fillers, film formers, pearlescence additives, deodorant and antiperspirant active substances, insect repellents, self-tanning agents, preservatives, conditioning agents, perfumes, colourants, odour absorbers, cosmetic active substances, care additives, superfatting agents, solvents.
- An additional object of the present invention is a compound chosen from the general formulae (DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S.
- Preferred compounds according to the invention are characterized in that X is equal to SO or SO2, particularly preferably SO.
- An additional object of the present invention is a process for the preparation of at least one compound chosen from the general formulae (DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S, comprising the stages of:
- the oxidizing agent is chosen from hydrogen peroxide, ozone, peracetic acid, sodium hypochlorite, potassium hypochlorite, perborates, percarbonates, iodine, bromine, chlorine, permanganate, dichromate and bromate, preferably hydrogen peroxide, peracetic acid and sodium hypochlorite, particularly preferably hydrogen peroxide.
- Another object of the present invention is a process for the preparation of the cosmetic formulations according to the invention comprising the stages: A2) making available at least one compound chosen from the group of the general formulae
- An additional object of the present invention is the use of at least one oxidation product of methionylmethionine as present in the formulations according to the invention for the treatment of nails and hair, for the conditioning of hair, for increasing the gloss of the hair, for increasing the tensile strength of the hair and/or for increasing the volume of hair.
- An additional object of the present invention is the use of at least one oxidation product of methionylmethionine as present in the formulations according to the invention for increasing the colour intensity of the hair, for increasing the load-bearing capacity of the hair, for protecting the hair from UV damage, for protecting the hair from oxidative damage, for protecting the hair from thermal damage and/or for protecting the hair from chemical damage.
- An additional object of the present invention is the use of at least one oxidation product of methionylmethionine as present in the formulations according to the invention known for improving the mechanical properties of nails.
- Figure 1 mechanical properties of hair after oxidative damage.
- Figure 2 skin moisture measurements Examples:
- the mixture of the stereoisomers of methionylmethionine was used.
- the pure stereoisomers of methionylmethionine can be prepared by selective synthesis according to
- Sharpless asymmetric aminohydroxylation (AA) according to Sharpless a) G. Li, H.-T. Chang and K. B. Sharpless, Angew. Chem. Int. Ed., 1996, 35, 451-454; b) G. Li and K. B. Sharpless, Acta Chem. Scand., 1996, 50, 649-651) or according to Schollkopf (the Schollkopf bis-lactim ether method for the synthesis of enantiomerically pure a-amino acids a) U. Schollkopf, T. Tiller and J. Bardenhagen, Tetrahedron, 1988, 44, 5293-5305; b) U. Schollkopf, Tetrahedron, 1983, 39, 2085- 2091). Accordingly, even the pure stereoisomers of the oxidation products are consequently available.
- AA asymmetric aminohydroxylation
- Example 3 Improvement in the mechanical properties of oxidatively damaged hair
- the hair thus bleached was immersed for 30 min in aqueous solutions of different concentrations of the substance obtained in Example 1.
- the hair was subsequently rinsed with tap water at a temperature of 35°C for a time of 1 min.
- the hair was finally dried.
- each time 50 hairs were tested in a Diastron Cyc 801 for fatigue (constant stress at 0.0145 g/pm 2 , max 100 000 cycles, trigger load 10 gmf, frequency 50 mm/s).
- Figure 1 shows the results and that the use of Example 1 restores the mechanical properties of hair after oxidative damage.
- FIG. 2 shows the results and that the use of Example 1 improves the skin moisture.
- Example 5 Improved smell
- Formulation X had the basic recipe 5 % TEGO® Alkanol 1618 0.5 % TEGINACID C 1 % Varisoft BT85 qs preservative ad 100% water were prepared additionally containing X:
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to sulfoxides and sulfones of the methionylmethionine stereoisomers D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D-methionine. An additional object is cosmetic formulations comprising sulfoxides and sulfones of methionylmethionine and also the use of the sulfoxides and sulfones of methionylmethionine contained.
Description
Oxidation products of methionylmethionine
Field of the invention
The invention relates to oxidation products of methionylmethionine, to their preparation and use. Prior art
EP 2 835 151 discloses cosmetic formulations containing at least one methionylmethionine stereoisomer chosen from the group D-methionyl-L-methionine, L-methionyl-D-methionine and D- methionyl-D-methionine and also the use of methionylmethionine for nail and/or hair treatment. Supplemental of J. Am. Chem. Soc., 1998, 120(14), 3345-3356, discloses the di- and monosulfoxides of the methionylmethionine stereoisomer L-methionyl-L-methionine.
It is an object of the invention to make available compositions which exhibit, compared with methionylmethionine, a reduced odour.
Description of the invention
It has been found that, surprisingly, the oxidation products of methionylmethionine described below are able to solve the problem addressed by the invention.
The present invention accordingly relates to sulfoxides and sulfones of the methionylmethionine stereoisomers D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D- methionine. An additional object is cosmetic formulations comprising sulfoxides and sulfones of methionylmethionine and also the use of the sulfoxides and sulfones of methionylmethionine contained.
It is an advantage of the oxidation products of methionylmethionine that these exhibit, compared with methionylmethionine itself, an increased solubility in water.
It is an advantage of the oxidation products of methionylmethionine that the solubility in water can be controlled via the oxidation stages.
It is a further advantage of the present invention that the oxidation products of methionylmethionine can be incorporated very well in cosmetic formulations
It is an additional advantage of the present invention that the oxidation products are odourless.
It is a further advantage of the present invention that the oxidation products are colourless.
It is an additional advantage of the present invention that the oxidation products are thermally stable. It is a further advantage of the present invention that the oxidation products are non-toxic.
It is an additional advantage of the present invention that the oxidation products can be easily prepared and isolated.
It is a further advantage of the present invention that the oxidation products are biodegradable.
It is a further advantage of the present invention that the oxidation products are hygroscopic and moisturizing.
The present invention accordingly relates to a cosmetic formulation comprising at least one oxidation product of methionylmethionine chosen from the group of the general formulae
(DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S.
As can be seen above, four different stereoisomers of the oxidation product of methionylmethionine exist. The letters D and L held in brackets describe the stereochemistry of the oxidation products of methionylmethionine.
Here, DD and LL behave towards each other as image and mirror image, i.e. they are enantiomers and therefore also have the same physical properties. The same is true for the pair DL and LD. The two pairs DD/LL and DL/LD are in comparison diastereomeric relative to one another, i.e. they have different physical data.
The use according to the invention, where it is the case of a use on a living species, is exclusively a cosmetic and a non-therapeutic use.
Unless otherwise indicated, all stated percentages (%) are percentages by weight.
Preferred cosmetic formulations according to the invention are characterized in that at least one X is equal to SO or SO2, particularly preferably SO; very particularly preferably, X is equal to SO.
Cosmetic formulations according to the invention are preferably characterized in that the total amount of the oxidation products of methionylmethionine present is from 0.01 % by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight, particularly preferably from 0.1% by weight to 10% by weight, the percentages by weight being with reference to the total formulation.
Preferably, the total amount of LL, with reference to the total weight of all oxidation products of methionylmethionine present in the formulation according to the invention, is less than or equal to 50% by weight, preferably less than 35% by weight, particularly preferably less than 18% by weight.
It is preferred according to the invention for the ratio by weight of DL and LD to DD and LL in the cosmetic formulation according to the invention to be from 9:1 to 2:3, preferably 8:2 to 1 :1, in particular 6:3 to 4:2, where per enantiomer pair in each case the sum of the individual enantiomers is taken into consideration. The abovementioned formulation does not exclude the possibility of only one of the enantiomers of an enantiomer pair being present in the formulation.
In an alternatively preferred embodiment, the ratio by weight of DL and LD to DD and LL in the formulation according to the invention is from 10:80 to 0.01 :110. Preferred cosmetic formulations according to the invention are characterized in that they represent an aqueous solution, an emulsion or suspension.
The formulations according to the invention can comprise e.g. at least one additional component chosen from the group of emollients, surfactants, emulsifiers, thickeners/viscosity regulators/stabilizers,
UV light protection filters, antioxidants, hydrotropes (or polyols), solids and fillers, film formers, pearlescence additives,
deodorant and antiperspirant active substances, insect repellents, self-tanning agents, preservatives, conditioning agents, perfumes, colourants, odour absorbers, cosmetic active substances, care additives, superfatting agents, solvents.
Substances which can be used as exemplary representatives of the individual groups are known to a person skilled in the art and can be taken, for example, from German Patent Application DE
102008001788.4. This patent application is hereby incorporated as reference and thus forms part of the disclosure.
As regards further optional components and also the amounts employed of these components, reference is expressly made to the relevant handbooks known to a person skilled in the art, for example K. Schrader, “Grundlagen und Rezepturen der Kosmetika” [Fundamentals and Formulations of Cosmetics], 2nd edition, pages 329 to 341, HOthig Buch Verlag, Heidelberg.
The amounts of the respective additives depend on the intended use. Typical starting formulations for the relevant applications are known prior art and are contained for example in the brochures of the manufacturers of the relevant base materials and active substances. These existing formulations can generally be adopted unchanged. However, if necessary, for adjustment and optimization, the desired modifications can be executed in a straightforward manner through simple tests.
An additional object of the present invention is a compound chosen from the general formulae
(DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S. Preferred compounds according to the invention are characterized in that X is equal to SO or SO2, particularly preferably SO.
An additional object of the present invention is a process for the preparation of at least one compound chosen from the general formulae
(DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S, comprising the stages of:
A) making available at least one compound chosen from DD, DL and LD, where all X = S, B) bringing the at least one compound chosen in process stage A) into contact with an oxidizing agent and oxidizing at least one X = S to give SO and/or SO2, and C) optionally isolating the oxidized at least one compound.
A preferred process according to the invention is characterized in that the oxidizing agent is chosen from hydrogen peroxide, ozone, peracetic acid, sodium hypochlorite, potassium hypochlorite, perborates, percarbonates, iodine, bromine, chlorine, permanganate, dichromate and bromate, preferably hydrogen peroxide, peracetic acid and sodium hypochlorite, particularly preferably hydrogen peroxide.
Another object of the present invention is a process for the preparation of the cosmetic formulations according to the invention comprising the stages: A2) making available at least one compound chosen from the group of the general formulae
(DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S,
B2) bringing the at least one compound chosen in process stage A2) into contact with an oxidizing agent and oxidizing at least one X = S to give SO and/or SO2, and
02) incorporating the at least one oxidized compound, optionally isolated beforehand, in a cosmetic formulation, in particular in the form of an emulsion.
An additional object of the present invention is the use of at least one oxidation product of methionylmethionine as present in the formulations according to the invention for the treatment of nails and hair, for the conditioning of hair, for increasing the gloss of the hair, for increasing the tensile strength of the hair and/or for increasing the volume of hair.
An additional object of the present invention is the use of at least one oxidation product of methionylmethionine as present in the formulations according to the invention for increasing the colour intensity of the hair, for increasing the load-bearing capacity of the hair, for protecting the hair from UV damage, for protecting the hair from oxidative damage, for protecting the hair from thermal damage and/or for protecting the hair from chemical damage.
An additional object of the present invention is the use of at least one oxidation product of methionylmethionine as present in the formulations according to the invention known for improving the mechanical properties of nails.
According to the invention, the abovementioned formulations according to the invention can in particular be used, preferred formulations according to the invention preferably being used according to the invention. The present invention is described by way of example in the examples cited below, without the invention, the scope of application of which results from the entirety of the description and from the claims, being restricted to the embodiments mentioned in the examples. The following figures are an integral part of the examples:
Figure 1 : mechanical properties of hair after oxidative damage. Figure 2: skin moisture measurements Examples:
For the present examples, the mixture of the stereoisomers of methionylmethionine was used. The possibility exists of separating the individual stereoisomers by crystallization to start with and thus of attaining the oxidation products enriched in a stereoisomer. Apart from this, the pure stereoisomers of methionylmethionine can be prepared by selective synthesis according to
Sharpless (asymmetric aminohydroxylation (AA) according to Sharpless a) G. Li, H.-T. Chang and K. B. Sharpless, Angew. Chem. Int. Ed., 1996, 35, 451-454; b) G. Li and K. B. Sharpless, Acta Chem. Scand., 1996, 50, 649-651) or according to Schollkopf (the Schollkopf bis-lactim ether method for the synthesis of enantiomerically pure a-amino acids a) U. Schollkopf, T. Tiller and J. Bardenhagen, Tetrahedron, 1988, 44, 5293-5305; b) U. Schollkopf, Tetrahedron, 1983, 39, 2085- 2091). Accordingly, even the pure stereoisomers of the oxidation products are consequently available.
Example 1: Oxidation of methionylmethionine to give the disulfoxide
5.6 g (0.02 mol) of methionylmethionine were suspended in 20 ml of demineralized water. 4.2 ml (0.04 mol) of 30% hydrogen peroxide were slowly added thereto dropwise at 20°C, so that the reaction temperature 35°C was not exceeded. After the total amount of hydrogen peroxide had been added, the mixture was heated at 50°C for one hour. The complete conversion of the starting
compounds was verified by HPLC. The water was subsequently distilled off and the white residue was dried a 50°C and 30 mbar. The complete conversion to the disulfoxide was analytically confirmed by 1H NMR and 13C NMR. The substance was odourless.
Example 2: Oxidation of methionylmethionine to give the disulfone
5.6 g (0.02 mol) of methionylmethionine were suspended in 20 ml of demineralized water. 8.4 ml (0.08 mol) of 30% hydrogen peroxide were slowly added thereto dropwise at 20°C, so that the reaction temperature 35°C was not exceeded. After the total amount of hydrogen peroxide had been added, the mixture was heated at 90°C for three hours. The complete conversion of the starting compounds was verified by HPLC. The water was subsequently distilled off and the white residue was dried a 50°C and 30 mbar. The complete conversion to the disulfone was analytically confirmed by 1H NMR and 13C NMR. The substance was odourless.
Example 3: Improvement in the mechanical properties of oxidatively damaged hair
Caucasian hair (21 cm long, colour 6/0, blend 852) from Kerling was chemically bleached. A mixture of 9% aqueous hydrogen peroxide and Basle bleach paste in the ratio 2:1 was prepared for this and was applied to the hair in the ratio 4 g/1 g of hair. After an action time of 50 min at AT, the hair was rinsed with warm water at 35°C for 2 min. The hair was subsequently dried.
The hair thus bleached was immersed for 30 min in aqueous solutions of different concentrations of the substance obtained in Example 1. The hair was subsequently rinsed with tap water at a temperature of 35°C for a time of 1 min. The hair was finally dried. For the measurements, each time 50 hairs were tested in a Diastron Cyc 801 for fatigue (constant stress at 0.0145 g/pm2, max 100 000 cycles, trigger load 10 gmf, frequency 50 mm/s).
Figure 1 shows the results and that the use of Example 1 restores the mechanical properties of hair after oxidative damage.
Example 4: Improvement in the moisture content of the skin
A moisture study was carried out. In this connection, two formulations were compared with each other (Vehicle and Formulation 1) 20 micrograms of the formulation were each time applied to the forearm. The skin moisture was measured after 2 hours and compared with the skin moisture before application.
Figure 2 shows the results and that the use of Example 1 improves the skin moisture. Example 5: Improved smell
The following compositions were assessed by a trained panel of 10 persons regarding their smell from 0 to 5, with 0 = no detectable smell and 5 = very strong smell
Formulation X had the basic recipe 5 % TEGO® Alkanol 1618 0.5 % TEGINACID C
1 % Varisoft BT85 qs preservative ad 100% water were prepared additionally containing X:
Example 6: Effect on nails
The Formulation Example 8) Body Care Composition below was applied (2ml) onto one side’s hand’s nail only on a trained panel of 10 persons for 3 weeks daily until total absorption was achieved. The other side’s hand was treated with the same Formulation without the active.
All persons considered the nails of the side treated with example 1 containing composition to be stronger, less bridle and having a more even and glossy surface than the side treated with just the vehicle.
Formulation examples:
Formulation Example 1) Pearlized Shampoo
Formulation Example 2) Rinse-Off Conditioner
Formulation Example 3) Rinse-Off Conditioner
Formulation Example 4) Rinse-Off Conditioner
Formulation Example 5) Leave-In Conditioner Spray
Formulation Example 6) Leave-in Conditioner Foam
Formulation Example 7) Strong Hold Styling Gel
Formulation Example 8) Body Care Composition
Formulation Example 9) Mild Foam Bath
Formulation Example 10: Hot Oil Treatment
Formulation Example 11 : Moisturizing Cream
Formulation Example 12: Moisturizing Cream
Claims
1. Cosmetic formulation comprising at least one oxidation product of methionylmethionine chosen from the group of the general formulae
(DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S.
2. Cosmetic formulation according to Claim 1 , characterized in that at least one X is equal to SO or SO2, particularly preferably SO; very particularly preferably, X is equal to SO.
3. Cosmetic formulation according to Claim 1 or 2, characterized in that the total amount of the oxidation products of methionylmethionine present is from 0.01% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight, particularly preferably from 0.1% by weight to 10% by weight, the percentages by weight being with reference to the total formulation.
4. Cosmetic formulation according to at least one of the preceding claims, characterized in that the ratio by weight of DL and LD to DD and LL is from 9:1 to 2:3, preferably 8:2 to 1 :1 , in particular 6:3 to 4:2.
5. Cosmetic formulation according to at least one of Claims 1 to 3, characterized in that the ratio by weight of DL and LD to DD and LL is from 10:80 to 0.01 :110.
6. Cosmetic formulation according to at least one of the preceding claims, characterized in that it represents an aqueous solution, an emulsion or suspension.
7. Compound chosen from the general formulae
(DL) (LD) with X, independently of one another, identically or differently chosen from S, SO and SO2, with the proviso that at least one X in each general formula is not equal to S.
8. Compound according to Claim 7, characterized in that X is equal to SO or SO2, particularly preferably is SO.
9. Process for the preparation of at least one compound according to Claim 7, comprising the stages:
A) making available at least one compound chosen from DD, DL and LD, where all X =
S,
B) bringing the at least one compound chosen in process stage A) into contact with an oxidizing agent and oxidizing at least one X = S to give SO and/or SO2, and
C) optionally isolating the oxidized at least one compound.
10. Process according to Claim 9, characterized in that the oxidizing agent is chosen from hydrogen peroxide, ozone, peracetic acid, sodium hypochlorite, potassium hypochlorite, perborates, percarbonates, iodine, bromine, chlorine, permanganate, dichromate and bromate, preferably hydrogen peroxide, peracetic acid and sodium hypochlorite, particularly preferably hydrogen peroxide.
11. Process for the preparation of a cosmetic formulation according to at least one of Claims 1 to 6, comprising the stages
A2) making available at least one compound chosen from DD, LL, DL and LD, where all X = S,
B2) bringing the at least one compound chosen in process stage A2) into contact with an oxidizing agent and oxidizing at least one X = S to give SO and/or SO2, and
C2) incorporating the at least one oxidized compound, optionally isolated beforehand, in a cosmetic formulation, in particular in the form of an emulsion.
12. Use of at least one oxidation product of methionylmethionine as mentioned in at least one of Claims 1 to 6 for the treatment of nails and hair, for the conditioning of hair, for increasing the gloss of the hair, for increasing the tensile strength of the hair and/or for increasing the volume of hair.
13. Use of at least one oxidation product of methionylmethionine as mentioned in at least one of Claims 1 to 6 for increasing the colour intensity of the hair, for increasing the load-bearing capacity of the hair, for protecting the hair from UV damage, for protecting the hair from oxidative damage, for protecting the hair from thermal damage and/or for protecting the hair from chemical damage.
14. Use of at least one oxidation product of methionylmethionine as mentioned in at least one of Claims 1 to 6 for improving the mechanical properties of nails.
15. Use according to at least one of Claims 12 to 14, characterized in that a formulation according to one of Claims 1 to 6 is used.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2835151A1 (en) | 2013-08-06 | 2015-02-11 | Evonik Industries AG | Methionyl-methionine stereoisomers and use thereof in cosmetics |
| DE102014225221A1 (en) * | 2014-12-09 | 2016-01-21 | Henkel Ag & Co. Kgaa | Oxidation stain with a dipeptide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2835151A1 (en) | 2013-08-06 | 2015-02-11 | Evonik Industries AG | Methionyl-methionine stereoisomers and use thereof in cosmetics |
| DE102014225221A1 (en) * | 2014-12-09 | 2016-01-21 | Henkel Ag & Co. Kgaa | Oxidation stain with a dipeptide |
Non-Patent Citations (7)
| Title |
|---|
| G. LIK. B. SHARPLESS, ACTA CHEM. SCAND., vol. 50, 1996, pages 649 - 651 |
| J. AM. CHEM. SOC., vol. 120, no. 14, 1998, pages 3345 - 3356 |
| K. B. SHARPLESS, ANGEW. CHEM. INT. ED., vol. 35, 1996, pages 451 - 454 |
| K. SCHRADER: "Fundamentals and Formulations of Cosmetics", vol. 2nd, HUTHIG BUCH VERLAG, article "Grundlagen und Rezepturen der Kosmetika", pages: 329 - 341 |
| MILLER BRIAN L. ET AL: "One-Electron Photooxidation of N -Methionyl Peptides. Mechanism of Sulfoxide and Azasulfonium Diastereomer Formation through Reaction of Sulfide Radical Cation Complexes with Oxygen or Superoxide", vol. 120, no. 14, 1 April 1998 (1998-04-01), pages 3345 - 3356, XP055859666, ISSN: 0002-7863, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/ja973084t> [retrieved on 20211110], DOI: 10.1021/ja973084t * |
| U. SCHOLLKOPF, T. TILLER; J.BARDENHAGEN, TETRAHEDRON, vol. 44, 1988, pages 5293 - 5305 |
| U. SCHOLLKOPF, TETRAHEDRON, vol. 39, 1983, pages 2085 - 2091 |
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