FR2732965A1 - NEW SERINE DERIVATIVES AND THEIR USE IN COSMETICS - Google Patents
NEW SERINE DERIVATIVES AND THEIR USE IN COSMETICS Download PDFInfo
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- FR2732965A1 FR2732965A1 FR9504411A FR9504411A FR2732965A1 FR 2732965 A1 FR2732965 A1 FR 2732965A1 FR 9504411 A FR9504411 A FR 9504411A FR 9504411 A FR9504411 A FR 9504411A FR 2732965 A1 FR2732965 A1 FR 2732965A1
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- Prior art keywords
- serine
- lactyl
- glycolyl
- acetyl
- methyl ester
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- 239000002537 cosmetic Substances 0.000 title claims abstract description 4
- 150000003354 serine derivatives Chemical class 0.000 title description 2
- 150000001408 amides Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 16
- RCZXERBGUFBLEP-BKLSDQPFSA-N (2S)-3-hydroxy-2-(2-hydroxypropanoylamino)propanoic acid Chemical compound C(C(O)C)(=O)N[C@@H](CO)C(=O)O RCZXERBGUFBLEP-BKLSDQPFSA-N 0.000 claims description 15
- 150000004702 methyl esters Chemical class 0.000 claims description 15
- RMHVXEWQMAUERF-VKHMYHEASA-N (2s)-3-hydroxy-2-[(2-hydroxyacetyl)amino]propanoic acid Chemical compound OC[C@@H](C(O)=O)NC(=O)CO RMHVXEWQMAUERF-VKHMYHEASA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 7
- WTLNOANVTIKPEE-UHFFFAOYSA-N 2-acetyloxypropanoic acid Chemical compound OC(=O)C(C)OC(C)=O WTLNOANVTIKPEE-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000006071 cream Substances 0.000 claims description 3
- -1 unsaturated alkyl radical Chemical group 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000010511 deprotection reaction Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 229940061720 alpha hydroxy acid Drugs 0.000 claims 1
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims 1
- 238000007127 saponification reaction Methods 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract 2
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract 1
- 150000001413 amino acids Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 19
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QMDTZORUMHSABR-YFKPBYRVSA-N (2s)-3-acetyloxy-2-[(2-hydroxyacetyl)amino]propanoic acid Chemical compound CC(=O)OC[C@@H](C(O)=O)NC(=O)CO QMDTZORUMHSABR-YFKPBYRVSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960001153 serine Drugs 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- YVAZYIKZQGUQGG-AKGZTFGVSA-N COC([C@@H](NC(C(O)C)=O)CO)=O Chemical compound COC([C@@H](NC(C(O)C)=O)CO)=O YVAZYIKZQGUQGG-AKGZTFGVSA-N 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- ANSUDRATXSJBLY-VKHMYHEASA-N methyl (2s)-2-amino-3-hydroxypropanoate Chemical compound COC(=O)[C@@H](N)CO ANSUDRATXSJBLY-VKHMYHEASA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PLSFURRHKBPYOY-RZKHNPSRSA-N (2S)-3-acetyloxy-2-(2-hydroxypropanoylamino)propanoic acid Chemical compound C(C)(=O)OC[C@H](NC(C(O)C)=O)C(=O)O PLSFURRHKBPYOY-RZKHNPSRSA-N 0.000 description 1
- MLXDUYUQINCFFV-UHFFFAOYSA-N 2-acetyloxyacetic acid Chemical compound CC(=O)OCC(O)=O MLXDUYUQINCFFV-UHFFFAOYSA-N 0.000 description 1
- KWFCSMSCNOVLBA-UHFFFAOYSA-N 2-hydroxy-3-oxobutanoic acid Chemical compound CC(=O)C(O)C(O)=O KWFCSMSCNOVLBA-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UWTATZPHSA-N D-Serine Chemical compound OC[C@@H](N)C(O)=O MTCFGRXMJLQNBG-UWTATZPHSA-N 0.000 description 1
- 229930195711 D-Serine Natural products 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- ZLUOHLNAAZHALG-GSVOUGTGSA-N acetyl (2R)-2-hydroxypropanoate Chemical compound C[C@@H](O)C(=O)OC(C)=O ZLUOHLNAAZHALG-GSVOUGTGSA-N 0.000 description 1
- ZLUOHLNAAZHALG-VKHMYHEASA-N acetyl (2S)-2-hydroxypropanoate Chemical compound C(C)(=O)OC([C@@H](O)C)=O ZLUOHLNAAZHALG-VKHMYHEASA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NDNDYXWSKRSTBR-BYPYZUCNSA-N methyl (2S)-3-hydroxy-2-[(2-hydroxyacetyl)amino]propanoate Chemical compound COC([C@@H](NC(CO)=O)CO)=O NDNDYXWSKRSTBR-BYPYZUCNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/12—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
NOUVEAUX DERIVES DE LA SERINE
ET LEUR EMPLOI EN COSMETIQUE
La présente invention se rapporte au domaine de la chimie organique et plus particulièrement à celui des amides d'acides a-hydroxylés. NEW SERINE DERIVATIVES
AND THEIR EMPLOYMENT IN COSMETICS
The present invention relates to the field of organic chemistry and more particularly to that of amides of α-hydroxylated acids.
Elle a plus précisément pour objet un amide choisi dans le groupe constitué par la N-glycolyl-sérine, la N-lactylsérine, et les ester de ces produits répondant à la formule générale I
dans laquelle R1 représente de l'hydrogène ou un radical méthyle
R2 représente de l'hydrogène ou le reste acyle d'un acide organique carboxylique ayant de 1 à 10 atomes de carbone et R représente de l'hydrogène ou un radical alcoyle saturé ou non saturé ayant de 1 à 10 atomes de carbone en chaîne droite ou ramifiée notamment l'ester méthylique de N-(O-acétyl-glycolyl)sérine, l'ester méthylique de N-(O-acétyl-lactyl)-sérine, l'ester méthylique de N-glycolyl-sérine et l'ester méthylique de N-lactyl-sérine.More specifically, it relates to an amide chosen from the group consisting of N-glycolyl-serine, N-lactylserine, and the esters of these products corresponding to the general formula I
in which R1 represents hydrogen or a methyl radical
R2 represents hydrogen or the acyl residue of an organic carboxylic acid having from 1 to 10 carbon atoms and R represents hydrogen or a saturated or unsaturated alkyl radical having from 1 to 10 carbon atoms in a straight chain or branched in particular the methyl ester of N- (O-acetyl-glycolyl) serine, the methyl ester of N- (O-acetyl-lactyl) -serine, the methyl ester of N-glycolyl-serine and the ester N-lactyl-serine methyl.
L'invention a également pour objet un procédé de préparation, dans lequel dans un premier temps, on estérifie la fonction alcool de l'acide lactique ou de l'acide glycolique, ensuite on condense cet ester avec un ester d'alcoyle de sérine. L'ester amide ainsi réalisé est saponifié, le cas échéant, en amide libre.The invention also relates to a preparation process, in which firstly, the alcohol function of the lactic acid or of the glycolic acid is esterified, then this ester is condensed with a serine alkyl ester. The amide ester thus produced is saponified, where appropriate, into a free amide.
La synthèse de la N-glycolyl-sérine [I] et de la N-lactylsérine [II] est effectuée plus précisément en deux étapes à partir de l'ester méthylique de la sérine et de l'a-acétoxy acide correspondant, dont les formules sont reportées dans les schémas de synthèse ci-joints.The synthesis of N-glycolyl-serine [I] and of N-lactylserine [II] is carried out more precisely in two stages starting from the methyl ester of serine and the corresponding α-acetoxy acid, the formulas are shown in the attached summary diagrams.
La sérine existe sous forme racémique ou sous forme dédoublée. Il existe de ce fait, deux formes optiquementactives, la D-sérine et la L-sérine. Il en est de même pour l'acide O-acétyllactique qui existe sous forme racémique ou sous forme optiquement active (acide O-acétyl-D-lactique et acide O-acétyl-L-lactique).Serine exists in racemic form or in split form. There are therefore two optically active forms, D-serine and L-serine. It is the same for O-acetyllactic acid which exists in racemic form or in optically active form (O-acetyl-D-lactic acid and O-acetyl-L-lactic acid).
La présente demande englobe les dérivés issus de la forme D, de la forme L et de tout mélange de la forme D et de la forme L, des deux produits de départ, mentionnés ci-dessus.The present application includes derivatives derived from form D, from form L and from any mixture of form D and from form L, of the two starting products mentioned above.
La présente demande décrit, à titre de composés nouveaux, les esters O-acylé de lactyl- et de glycolyl-sérine, les esters d'alcoyle de O-acétyl lactyl- et de O-acétylglycolyl sérine ainsi que les esters d'alcoyle de lactyl- et de glycolyl sérine.The present application describes, as new compounds, the O-acylated esters of lactyl- and glycolyl-serine, the alkyl esters of O-acetyl lactyl- and of O-acetylglycolyl serine as well as the alkyl esters of lactyl- and glycolyl serine.
La première étape du procédé selon l'invention consiste à acyler la fonction amine de la sérine. Cette acylation peut être effectuée notamment de la manière suivante : on part d'un ester d'alcoyle de sérine ou de son chlorhydrate et d'une base organique comme la N-méthylmorpholine dans l'acétate d'éthyle. Les réactifs sont introduits lentement dans un mélange dla-acétoxy acide (par exemple, l'acide Oacétyl lactique ou l'acide O-acétyl glycolique), en présence de chloroformiate d'éthyle et de N-méthylmorpholine refroidi à -100 à OOC. Après agitation à température ambiante pendant 16 à 20 heures, le mélange est hydrolysé avec de l'eau et extrait à l'acétate d'éthyle. Le résidu de l'évaporation de la phase organique est purifié.Les produits de formules III et IV sont recristallisés dans l'acétate d'éthyle ou l'éther éthylique ou un mélange des deux solvants.The first step of the process according to the invention consists in acylating the amine function of the serine. This acylation can be carried out in particular in the following manner: one starts from an ester of alkyl of serine or of its hydrochloride and from an organic base such as N-methylmorpholine in ethyl acetate. The reagents are introduced slowly into a mixture of the acetoxyacid (for example, acetyl lactic acid or acetyl glycolic acid), in the presence of ethyl chloroformate and of N-methylmorpholine cooled to -100 to OOC. After stirring at room temperature for 16 to 20 hours, the mixture is hydrolyzed with water and extracted with ethyl acetate. The residue from the evaporation of the organic phase is purified. The products of formulas III and IV are recrystallized from ethyl acetate or ethyl ether or a mixture of the two solvents.
Les structures des produits isolés, ester alcoylique de N (O-acétyl-glycolyl)-sérine [III] et ester méthylique de N (O-acétyl-lactyl)-sérine [IV], sont confirmées par leurs propriétés physico-chimiques.The structures of the isolated products, alkyl ester of N (O-acetyl-glycolyl) -serine [III] and methyl ester of N (O-acetyl-lactyl) -serine [IV], are confirmed by their physicochemical properties.
L'examen des spectres IR (CH2Cl2) des composés III et IV
-1 montre deux bandes intenses à 1690 et 1740 cm caractéristiques des carbonyles de l'amide et respectivement des esters.Examination of the IR (CH2Cl2) spectra of compounds III and IV
-1 shows two intense bands at 1690 and 1740 cm characteristic of the carbonyls of the amide and of the esters respectively.
Les masses moléculaires des deux produits ci-dessus, sont en parfait accord avec les structures proposées.The molecular weights of the two products above are in perfect agreement with the structures proposed.
Au deuxième stade du procédé, on hydrolyse en milieu fortement basique les composés de formule III et IV, obtenus ci-dessus, par exemple, comme suit
les esters de formule III et IV purifiés, sont hydrolysés
en a-hydroxy amide de formule I et II, par saponification
avec une solution aqueuse basique comme la soude ou la
potasse, puis acidification et élimination des sels.In the second stage of the process, the compounds of formulas III and IV, obtained above, for example, are hydrolyzed in a highly basic medium, as follows
the purified esters of formulas III and IV are hydrolyzed
to a-hydroxy amide of formula I and II, by saponification
with a basic aqueous solution like soda or
potash, then acidification and elimination of salts.
les produits de formule I et II sont isolés. Ces produits
se distinguent en IR (film) par 3 bandes à 3380-3400, 1730
-1
et 1660 cm , correspondant à la vibration des liaisons N -1 -1
H, O-H (3380-3400 cm ); carbonyle de l'ester (1730 cm
-1
et carbonyle de l'amide (1660 cm ). the products of formula I and II are isolated. These products
stand out in IR (film) by 3 bands at 3380-3400, 1730
-1
and 1660 cm, corresponding to the vibration of the N -1 -1 bonds
H, OH (3380-3400 cm); ester carbonyl (1730 cm
-1
and carbonyl of the amide (1660 cm).
Les spectres [1H]RMN des produits I et II se différencient de ceux des produits III et IV par l'absence de proton des groupes méthyles de l'acétyle et de l'ester. The [1 H] NMR spectra of products I and II differ from those of products III and IV by the absence of protons from the acetyl and ester methyl groups.
Les produits I et II peuvent également être obtenus à partir des esters correspondants V et VI par hydrolyse basique.Products I and II can also be obtained from the corresponding esters V and VI by basic hydrolysis.
L'ester méthylique de N-glycolyl-sérine [V] et l'ester méthylique de N-lactyl-sérine [VI] sont obtenus par déprotection sélective du groupe hydroxy en position a d'amides correspondants III et IV, dans un solvant approprié, par exemple dans le méthanol en présence d'une quantité catalytique d'acide minéral.The methyl ester of N-glycolyl-serine [V] and the methyl ester of N-lactyl-serine [VI] are obtained by selective deprotection of the hydroxy group in position a of corresponding amides III and IV, in an appropriate solvent , for example in methanol in the presence of a catalytic amount of mineral acid.
A notre connaissance, les produits I, II, III, IV, V et VI ne sont pas décrits dans la littérature.To our knowledge, products I, II, III, IV, V and VI are not described in the literature.
Les exemples non limitatitfs suivants illustrent les composés nouveaux et la mise en oeuvre des procédés selon l'invention
Exemple 1
Ester méthylique de N- (L-O-acetyl-lactyl) -L-sérine [IV]
Dans une solution refroidie au bain de glace contenant 50 g d'acide O-acétyl lactique, 42 ml de N-méthylmorpholine dans 250 ml d'acétate d'éthyle, ajouter une solution de 36 ml de chloroformiate d'éthyle dans 50 ml d'acétate d'éthyle et laisser sous agitation pendant 30 minutes. Ensuite, additionner un mélange de 56 g de chlorhydrate de l'ester méthylique de la sérine, 42 ml de N-méthylmorpholine et 500 ml d'acétate d'éthyle. Après 16-20 heures d'agitation à température ambiante, hydrolyser avec 500 ml d'eau, extraire à l'acétate d'éthyle, évaporer le solvant sous vide.The following nonlimiting examples illustrate the new compounds and the implementation of the methods according to the invention
Example 1
N- (LO-acetyl-lactyl) -L-serine methyl ester [IV]
In a solution cooled in an ice bath containing 50 g of O-acetyl lactic acid, 42 ml of N-methylmorpholine in 250 ml of ethyl acetate, add a solution of 36 ml of ethyl chloroformate in 50 ml of ethyl acetate and leave to stir for 30 minutes. Then add a mixture of 56 g of hydrochloride of the serine methyl ester, 42 ml of N-methylmorpholine and 500 ml of ethyl acetate. After 16-20 hours of stirring at room temperature, hydrolyze with 500 ml of water, extract with ethyl acetate, evaporate the solvent in vacuo.
Reprendre le résidu dans l'acétate d'éthyle, laisser cristalliser.Take up the residue in ethyl acetate, allow to crystallize.
Poids 38 g - P.F : 146-1510C
Exemple 2
Ester méthylique de N- (O-acétyl-glycolyl) -sérine [III]
Le procédé est identique à celui décrit ci-dessus, excepté le remplacement de l'acide O-acétyl lactique par l'acide Oacétyl glycolique. Acide O-acétyl glycolique 20 g; chlorhydrate de l'ester méthylique de sérine 25 g.Weight 38 g - PF: 146-1510C
Example 2
N- (O-acetyl-glycolyl) -serine methyl ester [III]
The process is identical to that described above, except for the replacement of O-acetyl lactic acid by Oacetyl glycolic acid. O-acetyl glycolic acid 20 g; hydrochloride of serine methyl ester 25 g.
Le produit isolé est cristallisé dans l'acétate d'éthyle.The isolated product is crystallized from ethyl acetate.
Poids 18 g - P.F : 62-640C
Exemple 3
N-glycolyl-sérine à partir du produit III
A 15 g d'ester méthylique de N-(O-acétyl-glycolyl)-sérine dans 150 ml d'eau, ajouter une solution de 50,6 ml de soude dans 112 ml d'eau. Après 1 h 30, ajuster le pH de la solution à 2. Concentrer sous vide et additionner 150 ml d'isopropanol. Filtrer les sels, et concentrer le filtrat sous vide.Weight 18 g - PF: 62-640C
Example 3
N-glycolyl-serine from product III
To 15 g of N- (O-acetyl-glycolyl) -serine methyl ester in 150 ml of water, add a solution of 50.6 ml of sodium hydroxide in 112 ml of water. After 1 h 30, adjust the pH of the solution to 2. Concentrate under vacuum and add 150 ml of isopropanol. Filter the salts, and concentrate the filtrate under vacuum.
Poids 6,3 g de produit I
Exemple 4
N-lactyl-sérine à partir du produit IV
A une solution d'ester méthylique de N-(O-acétyl-lactyl)- sérine (5g) dans l'eau (50 ml), ajouter une solution de soude (16 ml) dans l'eau (35 ml). Après 1 h d'agitation à température ambiante, acidifier la solution à pH 2.Weight 6.3 g of product I
Example 4
N-lactyl-serine from product IV
To a solution of methyl ester of N- (O-acetyl-lactyl) - serine (5g) in water (50 ml), add a solution of sodium hydroxide (16 ml) in water (35 ml). After 1 h of stirring at room temperature, acidify the solution to pH 2.
Concentrer sous vide et additionner de 50 ml d'isopropanol.Concentrate under vacuum and add 50 ml of isopropanol.
Filtrer les sels, et concentrer le filtrat sous vide.Filter the salts, and concentrate the filtrate under vacuum.
Poids 3 g de produit II (huile). Weight 3 g of product II (oil).
Exemple 5
Ester méthylique de N-glycolyl-sérine [V]
A une solution de 9 g d'ester méthylique de N-(O-acétylglycolyl)-sérine dans 180 ml de méthanol, ajouter 0,4 ml d'acide chlorhydrique. Chauffer à 600C et y maintenir sous vive agitation pendant 9 h. Concentrer sous vide et purifier le produit obtenu sur colonne de gel de silice.Example 5
N-glycolyl-serine methyl ester [V]
To a solution of 9 g of N- (O-acetylglycolyl) -serine methyl ester in 180 ml of methanol, add 0.4 ml of hydrochloric acid. Heat to 600C and keep there with vigorous stirring for 9 h. Concentrate under vacuum and purify the product obtained on a silica gel column.
Poids 7 g de V
Exemple 6
Ester méthylique de N-lactyl-sérine [VI]
Procédé identique à l'exemple 5, à l'exception de la matière première il s'agit de l'ester méthylique de N-(O-acétyllactyl)-sérine (10 g) dans 200 ml de méthanol et 0,8 ml d'acide chlorhydrique.Weight 7 g of V
Example 6
N-lactyl-serine methyl ester [VI]
Process identical to Example 5, with the exception of the raw material it is the methyl ester of N- (O-acetylactyl) -serine (10 g) in 200 ml of methanol and 0.8 ml of 'hydrochloric acid.
Produit obtenu : 6,4 g de VI.Product obtained: 6.4 g of VI.
Exemple 7
N-glycolyl-sérine à partir de V
Le procédé est identique à celui de l'exemple 3, excepté que le produit III est remplacé par l'ester méthylique de Nglycolyl-sérine (5,4 g) . L'hydrolyse est effectuée avec 8,5 ml de soude dans 80 ml d'eau.Example 7
N-glycolyl-serine from V
The process is identical to that of Example 3, except that product III is replaced by the methyl ester of Nglycolyl-serine (5.4 g). The hydrolysis is carried out with 8.5 ml of sodium hydroxide in 80 ml of water.
Poids obtenu : 4,5 g de I.Weight obtained: 4.5 g of I.
Exemple 8
N-lactyl-sérine à partir de VI
A partir d'ester méthylique de N-lactyl-sérine (5 g) et de soude (7 ml) dans l'eau (50 ml), selon le procédé décrit dans l'exemple 4.Example 8
N-lactyl-serine from VI
From methyl ester of N-lactyl-serine (5 g) and sodium hydroxide (7 ml) in water (50 ml), according to the process described in Example 4.
Poids obtenu : 4,3 g de II. Weight obtained: 4.3 g of II.
Les composés décrit dans la présente demande de brevet, trouvent un emploi en cosmétologie, notamment comme principe actif dans la réalisation de crèmes, de pommades, de formulations externes antirides ou assouplissantes ou comme principe actif de crèmes hydratantes.The compounds described in the present patent application find use in cosmetology, in particular as an active ingredient in the production of creams, ointments, external anti-wrinkle or softening formulations or as an active ingredient in moisturizing creams.
Ces composés jouent un rôle dans les préparations dermiques à action exfoliante, et/ou hydratante et/ou keratorégulatrice. These compounds play a role in dermal preparations with exfoliating, and / or hydrating and / or keratorregulating action.
Claims (11)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9504411A FR2732965B1 (en) | 1995-04-12 | 1995-04-12 | NEW SERINE DERIVATIVES AND THEIR USE IN COSMETICS |
| PCT/FR1996/000558 WO1996032372A1 (en) | 1995-04-12 | 1996-04-12 | Serine derivatives and use thereof in cosmetics |
| AU56521/96A AU5652196A (en) | 1995-04-12 | 1996-04-12 | Serine derivatives and use thereof in cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9504411A FR2732965B1 (en) | 1995-04-12 | 1995-04-12 | NEW SERINE DERIVATIVES AND THEIR USE IN COSMETICS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2732965A1 true FR2732965A1 (en) | 1996-10-18 |
| FR2732965B1 FR2732965B1 (en) | 1997-07-11 |
Family
ID=9478051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR9504411A Expired - Fee Related FR2732965B1 (en) | 1995-04-12 | 1995-04-12 | NEW SERINE DERIVATIVES AND THEIR USE IN COSMETICS |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU5652196A (en) |
| FR (1) | FR2732965B1 (en) |
| WO (1) | WO1996032372A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2763842B1 (en) * | 1997-05-27 | 2000-09-15 | Sederma Sa | COSMETIC OR DERMOPHARMACEUTICAL COMPOSITIONS CONTAINING THREONINE OR SERINE DERIVATIVES |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021572A (en) * | 1975-07-23 | 1977-05-03 | Scott Eugene J Van | Prophylactic and therapeutic treatment of acne vulgaris utilizing lactamides and quaternary ammonium lactates |
| EP0413528A1 (en) * | 1989-08-15 | 1991-02-20 | Ruey J. Dr. Yu | Amphoteric compositions and polymeric forms of alpha hydroxyacids, and their therapeutic use |
| EP0498728A1 (en) * | 1991-02-06 | 1992-08-12 | L'oreal | Glycyl-serine amides and cosmetic, pharmaceutical or alimentary compositions containting them |
| FR2707647A1 (en) * | 1993-07-16 | 1995-01-20 | Rocher Yves Biolog Vegetale | Derivatives of alpha -hydroxy acids and cosmetic or pharmaceutical composition containing them |
| WO1995003811A1 (en) * | 1993-07-30 | 1995-02-09 | Beauticontrol Cosmetics, Inc. | Therapeutic skin composition |
-
1995
- 1995-04-12 FR FR9504411A patent/FR2732965B1/en not_active Expired - Fee Related
-
1996
- 1996-04-12 WO PCT/FR1996/000558 patent/WO1996032372A1/en not_active Ceased
- 1996-04-12 AU AU56521/96A patent/AU5652196A/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021572A (en) * | 1975-07-23 | 1977-05-03 | Scott Eugene J Van | Prophylactic and therapeutic treatment of acne vulgaris utilizing lactamides and quaternary ammonium lactates |
| EP0413528A1 (en) * | 1989-08-15 | 1991-02-20 | Ruey J. Dr. Yu | Amphoteric compositions and polymeric forms of alpha hydroxyacids, and their therapeutic use |
| EP0498728A1 (en) * | 1991-02-06 | 1992-08-12 | L'oreal | Glycyl-serine amides and cosmetic, pharmaceutical or alimentary compositions containting them |
| FR2707647A1 (en) * | 1993-07-16 | 1995-01-20 | Rocher Yves Biolog Vegetale | Derivatives of alpha -hydroxy acids and cosmetic or pharmaceutical composition containing them |
| WO1995003811A1 (en) * | 1993-07-30 | 1995-02-09 | Beauticontrol Cosmetics, Inc. | Therapeutic skin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AU5652196A (en) | 1996-10-30 |
| FR2732965B1 (en) | 1997-07-11 |
| WO1996032372A1 (en) | 1996-10-17 |
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