FR2909378A1 - New (pseudo)ceramide compounds useful in the field of hair care, like shampoos, after-shampoos, lotions or hair balms - Google Patents

Abstract

(Pseudo)ceramide compounds (I), are new. (Pseudo)ceramide compounds of formula R1-C(=O)-N(X)-(CH(R2)) m-CH(R3)-(CH 2) n-O-C(=O)-(CH 2) p-N +>R4R5R6 (I), are new. X : H or 1-4C carbon chain, preferably H; R1, R : 4-25C carbon chain (optionally containing 1-2 OH groups); R2 : H, 1-4C alkyl or OH, preferably H; R3 : -R, -O-C(=O)-R or -CH 2-O-C(=O)-R; R4-R6 : optionally unsaturated 1-12C alkyl or aromatic, preferably methyl, ethyl, propyl, butyl or lauryl; Z : halo, preferably Br or Cl; m, n : 0-3, preferably 0-1; and p : 1-3. Independent claims are included for: (1) the preparation of (I); and (2) cosmetic composition comprising (I) in combination/mixture with inert excipients or vehicle.

Description

1 Quaternized ceramides or pseudo-ceramides and compositions

  The present invention relates to the field of chemistry and more particularly to the synthesis of quaternary ammonium salts.

  The present invention relates to compounds corresponding to formula (I): ## STR2 ## wherein: m and n are, independently, one of the compounds of formula (I); other, integers selected from the values 0, 1,2 and 3; p is an integer selected from values 1, 2 and 3; X is selected from hydrogen and a carbon chain having 1 to 4 atoms; carbon - RI is a carbon chain, saturated or unsaturated, containing from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups; R2 is chosen from hydrogen and an alkyl chain containing from 1 to 4 carbon atoms; carbon, linear or branched, which may comprise a hydroxyl group; R 3 is chosen from the following groups: ## STR3 ## where R is a carbon chain, saturated or unsaturated, containing from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups; - R4, R5 and R6 are, independently of each other, an alkyl group having 1 to 12 carbon atoms, which may comprise unsaturations or an aromatic group; Z is a halogen.

  The present invention also relates to the synthesis of the compounds of formula (I) by coupling between a trisubstituted amine and a ceramide or pseudo-ceramide derivative. The present invention also relates to the production of cosmetic compositions containing compounds of formula (I).

The present invention finally relates to the cosmetic use of the compounds of formula (I) or compositions containing them, more particularly in the field of hair care and shampoos.

Due to their washing properties, shampoos are generally formulated with anionic surfactants. However, the latter not only remove the dirt from the hair, but also the natural lipids present on the surface of the hair fibers. They therefore leave the hair in unsatisfactory conditions from a cosmetic point of view, with in particular an undesirable hardness and a dry touch.

The use of conditioners tends to fill these negative effects and nourish the hair. These conditioners are used after application of the shampoo and contain cationic compounds to compensate for the effects of anionic surfactants. In addition, the ability of cationic compounds to interact with hair keratin molecules facilitates disentangling of wet hair and provides great flexibility to dry hair. The cationic compounds are therefore necessary for thorough washing and treatment of the hair (WO9924014, US 2002/0106343, WO 0234219). The present invention relates to quaternary ammonium salts of formula (I), derived from natural ceramides or ceramide analogues, for application in the field of hair care.

Ceramides are among the most important lipid constituents of the stratum corneum. They are in particular constituents of the natural lipids of the hair, produced at the level of the hair bulb. Ceramides or their functional analogues are used in the field of hair care to repair and strengthen damaged hair (EP1504747, FR2788689, US 2005/0160537, US1998 / 0153471).

The quaternary ammonium salts of formula (I) are therefore capable of associating the properties of ceramides and cationic compounds for the care and treatment of the hair. The compounds of formula (I) are synthesized according to the invention from ceramides or pseudo-ceramides of formula (II): ## STR2 ## wherein: ## STR2 ## wherein: other, integers selected from values 0, 1, 2 and 3; X is chosen from hydrogen and a carbon chain containing from 1 to 4 carbon atoms; R1 is a saturated or unsaturated carbon chain containing from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups; - R2 is chosen from hydrogen and an alkyl chain comprising 1 to 4 carbon atoms, linear or branched, may include a hydroxyl group; R 3 is chosen from the following groups: ## STR1 ## where R is a saturated or unsaturated carbon chain containing from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups. Compounds of formula (II) may be natural ceramides, such as those represented below: Ceramide II Ceramide III 14H29 Ceramide VI 14H29 They may also be synthetic compounds, ceramide analogues, as for example Examples of those described in patent EP 1644318. According to a preferred form of the invention, ni is equal to 0. According to another preferred form of the invention, m is equal to 1. According to a preferred form of the invention, n is equal to 0 According to another preferred form of the invention, n is equal to 1.

According to a preferred form of the invention, X is a hydrogen atom. According to a preferred form of the invention, R2 is a hydrogen atom.

According to a preferred form of the invention, R 3 is chosen from the following groups: ## STR2 ## where R is a carbon chain, saturated or unsaturated, comprising from 4 to 25 carbon atoms and optionally from 1 to 2 groups hydroxyl, derived from a fatty acid or a fatty acid derivative. According to one preferred form of the invention, R4, R5 and R6 are chosen, independently of one another, from methyl, ethyl, propyl and butyl groups.

According to another preferred form of the invention, at least one of the groups R4, R5 and R6 is a lauryl group. According to a preferred form of the invention, Z is chosen from bromine and chlorine.

The compounds of formula (I) are synthesized according to the invention by a two-step process, starting from a natural ceramide or a ceramide analog, to obtain a ceramide, or a ceramide analog, quaternized. Several methods for quaternizing molecules are known. Lindstedt and. al. refer to the synthesis of quaternized products of the primary alcohol type (American Society for Microbiology, Antimicrobial agents and chemotherapy, Oct. 1990, 1949-1954). Ansgar and. al. (US2005054551) disclose the formation of betaine esters from alkyl- or alkylene-oligoglycosides. Several documents, such as US2005020474, describe the quaternization of tertiary amines using an alkyl halide.

The synthesis method according to the invention corresponds to the following scheme: ## STR2 ## Step 1 p = 1.2 or 3 (IV) Y = Br or Cl Z = Br 2 Cl 2 O O Step 2 N R 4 R5R6 Y p (III) R1 ~ \ N 'nO ~ YZ p X R3 R2 O R4 \, R5 R1 ~ \ NOX R3 Z- (I) Scheme 1 The haloester of formula (IV) is obtained as an intermediate product. This is a classic quaternization scheme, in particular similar to that of Lindstedt et. al. (op cit). However, the operating conditions developed by the Applicant are new and provide an improvement to the process, especially in terms of exploitation on an industrial scale.

Indeed, step I of chloroacetylation usually requires a halogenated solvent, such as chloroform or dichloromethane. These solvents pose toxicity problems for industrial application. Surprisingly, the Applicant has developed a procedure employing a non-halogenated inert solvent, especially ethyl acetate. The second coupling step can also be carried out in this solvent. Non-toxic and easily accessible, ethyl acetate allows easy adaptation of the process on a large scale. According to a preferred form of the invention, step I is carried out between 10 and 70 ° C., more preferably at room temperature. According to a preferred form of the invention, step II is carried out between 25 and 75 ° C., more preferably around 50 ° C.

Alternatively, acetone can be used as a solvent in step II. However, ethyl acetate will be used preferentially. The present invention also relates to the production of cosmetic compositions containing compounds of formula (I).

According to a preferred form of the invention, the content of the compositions of compounds of formula (I) is from 0.001 to 20% relative to the total weight of the composition.

The compositions according to the invention comprise an inert, non-toxic, cosmetically acceptable carrier, in combination or in admixture with the active ingredient. They may contain adjuvants commonly used in the cosmetics field, such as, for example, softening agents, gelling agents, antioxidants, solvents, filters, preservatives, pigments or perfumes.

The compositions according to the invention are in a form compatible with topical application, such as an aqueous, hydroalcoholic, hydroglycolic or oily solution, a dispersion, a suspension, an oil-in-water or water-in-oil emulsion, an aqueous gel or oily, cream, milk, ointment, lotion, paste, mousse or aerosol. The compositions according to the invention may especially be in the form of a shampoo, a conditioner, a lotion or a hair balm, or any other composition that can be applied to the hair or leather scalp. The compounds of formula (I) or compositions containing them may be used cosmetically, in particular in the field of hair care, in order to combine the beneficial effects of cationic agents and ceramides on the hair and scalp.

EXAMPLES Example 1 Synthesis of the ctuaternized pseudo-ceramide of formula (Ia) ## STR16 ## The starting pseudo-ceramide of formula (IIa): ## STR2 ## ) Can be prepared according to the method described in patent EP 1644318. Step I: 1 g of the compound (IIa) is dissolved in 4 ml of ethyl acetate. 1.2 equivalents of chloroacetyl chloride (CAS [79-04-9]) is added dropwise at room temperature.

The reaction is stirred for 24 hours at room temperature. The reaction mixture is then washed with 2 × 5 mL of 5% aqueous NaHCO 3 solution / m 2 and then with 2 × 5 mL of water. The organic phase is then used directly in the next step. Step II: At room temperature, 4 equivalents of triethylamine (CAS [121-44-8D] are added dropwise to the reaction mixture over a total of 20 minutes, and the reaction is stirred at 50 ° C. for 48 hours. cooling, the mixture is concentrated, the compound (Ia) is crystallized from acetone and then recrystallized from ethyl acetate Yield: 60% 1H NMR (ppm) 0.81 (t, 6H, CH 3) 1.11-1.28 (m, 38H, CH 2); 1.30 (t, 9H, NCH 2 CH 3); 1.36-1.51 (m, 4H, CH 2); 1.85-1.93; (m, 4H, CH 2); 2.09-2.23 (m, 4H, CH 2); 2.58-2.69 (m, 2H, CH 2); 3.00-3.12 (m, 1H, CH), 3.67 (q, 6H, NCH2CH3), 4.07-4.29 (m, 4H, CH2), 5.02-5.42 (m, 6H, 4 CH = and CH2N +); 45 (t, 1H, NH) 13 C NMR (ppm) 8174.6 (NHC = O), 173.2 (C (= O) O), 164.6 (C (= O) O); EXAMPLE II Synthesis of Quaternized Pseudo-Ceramide of Formula (Ia ') The compound (Ia ') is prepared by the following formula: ## STR2 ## n a process similar to that of Example I from the compound (IIa). In step II, the triethylamine is replaced by dimethylethylamine. The reaction is complete after stirring for 6 hours at 50 ° C. EXAMPLE III: S thesis of the uterineized para-ceramide of formula (Ib): O + and O / O and 30 -131C1 -O Cl (Ib) starting pseudo-ceramide, of formula (IIb): ## STR1 ## may be prepared according to the method described in patent EP 1644318. Compound (Ib) is prepared according to a process similar to that of Example I at from the compound (I1h). EXAMPLE IV Synthesis of the Quaternized Ceramide of Formula (Ic): ## STR2 ## The compound (Ic) is prepared according to a process similar to that of Example I, starting with the natural ceramide II. EXAMPLE V Synthesis of the Quaternized Ceramide of Formula (Id): ## STR3 ## The compound (Id) is prepared according to a process similar to that of Example I starting from the ceramide Natural III. EXAMPLE VI Synthesis of the Quaternized Ceramide of Formula (Ie): The compound (Ie) is prepared according to a process similar to that of Example (I) from natural ceramide VI.

EXAMPLE VII Compositions Containing a Quaternary Ammonium Salt of Formula (I) Example VII-1: Hair Mask INGREDIENTS NOMENCLATURE INCI 0o PHASE A - Nikkomulese 61H Polyglyceryl-10 pentastearate / behenyl 2.00 alcohol / stearamidopropyl dimethylamine lactate - Behenyl alcohol Behenyl alcohol 3.00 Phenyltrimethicone Phenyl trimethicone 3.00 Crodamol CAP Cetearyl ethylhexanoate / isopropyl myristate 2.00 Miglyol 812 Caprylic / capric triglyceride 2.00 Quaternized ceramide (Ia) _ 0.20 PHASE B _ Aqua water ù qs Butylene glycol Butylene glycol _ 1.50 Cosmedia Guar Guar H ux ro l trimonium chloride 0.30 PHASE C Date Glycolysate Propylene glycol / Aqua / Phoenix dactylifera 3.00 Cyclomethicone Cyclomethicone 1.00 __-_ PHASE D .. Perfume _ 0.30 DC Yellow 6 CI 15985 qs Preservative _ qs Rheocare CTH (E) Polyquaternium-37 / propylene glycol 0.75 dicaprylate / Example VIII-2: Hair Care INGREDIENTS NOMENCLATUR E INCI% PHASE A Miglyol 812 Caprylic / Capric Triglyceride 2.00 Propylene Glycol Dipelargonate Propylene Glycol Dipelargonate 3.00 Grape Seed Oil _ 1.00 Vitis vinifera (grape) seed oil Quaternized Ceramide (the _ _ 0.50 PHASE B Aqua Water ù qs Milk of Tears of bamboo Aqua / Propylene glycol dicaprylate / dicaprate 0.50 / Bambusa vulgaris extract sap / Xanthan gum Rheocare CTH (E) Polyquaternium-37 / propylene glycol 1.50 dicaprylate / dicaprate / PPG-1 trideceth-6 PHASE C _ 0.20 Fragrance FDC Red 40 _ qs CI 16035 Preservative Example VII-3: Shampoo INGREDIENTS NOMENCLATURE INCI% PHASE A Water _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Polyquaternium-10 0.30 Xanthan gum _ 0.20 Xanthan gum Glycerin Glycerin 1.30 _Benzophenone -4 Benzophenone-4 0.40 Tiare Monoi Milk, Aqua / Cocos nucifera / Gardenia tahitensis / 2.00 xanthan gum Lauryl sodium sulfosuccinate Disodium laureth sulfosuccinate 10.00 Decyl glucoside _ 12.00 Decyl glucoside Cocoamph sodium oacetate Sodium cocoamphoacetate ù 8.00 PHASE B Water _ Aqua 30.00 Arlatone Duo '_ 10.00 Disodium lauryl sulphosuccinate / Sodium cocoyl isethionate / Zea mays / Cetearyl alcohol / Aqua / Hydrogenated castor oil / Glycerin / Titanium dioxide Quaternized ceramide (lb) 0.10 PHASE C Promidium 2 _ _ 2.25 PPG-2 Hydroxyethyl coco / isostearamide Fragrance 0.30 Preservative ___ _.__. . FDC Red 40 ___-qs CI 16035 10

Claims (14)

  1. Ceramide or pseudo-ceramide-type compounds corresponding to formula (I): ## STR3 ## in which: m and n are, independently of one another; other, integers selected from the values 0, 1, 2 and 3; p is an integer selected from values 1, 2 and 3; X is chosen from hydrogen and a carbon chain containing from 1 to 4 carbon atoms; - R1 is a carbon chain, saturated or unsaturated, having from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups; - R2 is chosen from hydrogen and an alkyl chain comprising 1 to 4 carbon atoms, linear or branched, may include a hydroxyl group; - R3 is chosen from the following groups: where R is a carbon chain, saturated or unsaturated, having from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups; - R4, R5 and R6 are, independently of each other, an alkyl group having 1 to 12 carbon atoms, which may comprise unsaturations or an aromatic group; Z is a halogen.   2. Compounds according to claim 1, characterized in that R3 is chosen from the following groups: ## STR2 ## where R is a carbon chain, saturated or unsaturated, containing from 4 to 25 carbon atoms and optionally from 1 to: 2 hydroxyl groups; 2909378 12   3. Compounds according to claim 1 or claim 2, characterized in that m and n are, independently of one another, selected from the values 0 and 1.   4. Compounds according to one of the preceding claims, characterized in that X and R2 are 5 hydrogen atoms.   5. Compounds according to one of the preceding claims, characterized in that R4, R5 and R6 are chosen, independently of each other, from methyl, ethyl, propyl and butyl groups.   6. Compounds according to one of claims 1 to 4, characterized in that at least one of the groups R4, R5 and R6 is a lauryl group.   7. Compounds according to one of the preceding claims, characterized in that Z is selected from bromine and chlorine.   8. Process for the synthesis of the compounds according to one of the preceding claims, characterized in that a compound of formula (II): ## STR1 ## in which: and n are, independently of each other, integers selected from values 0, 1, 2 and 3; X is selected from hydrogen and a carbon chain having from 1 to 4 carbon atoms; - R1 is a carbon chain, saturated or unsaturated, having from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups; - R2 is chosen from hydrogen and an alkyl chain comprising 1 to 4 carbon atoms, linear or branched, may include a hydroxyl group; R3 is chosen from the following groups: ## STR3 ## where R is a saturated or unsaturated carbon chain containing from 4 to 25 carbon atoms and optionally from 1 to 2 hydroxyl groups, is coupled to a compound of formula (III): in which - p = 1.2 or 3 - Y = Cl or Br Z = Cl or Br in a non-halogenated inert solvent, to obtain a haloester, which is reacted with a tertiary amine NR4R5R6, to give a quaternary ammonium salt of formula (I).   9. Process according to claim 8, characterized in that the non-halogenated inert solvent is ethyl acetate.   10. Process according to claim 8 or claim 9, characterized in that the coupling between the compounds (II) and (III) is carried out at room temperature.   11. Method according to one of claims 8 to 10, characterized in that the coupling of the haloester with the tertiary amine NR4R5R6 is carried out in a solvent selected from ethyl acetate and acetone.   12. Cosmetic compositions characterized in that they comprise, as active ingredient, at least one compound of formula (I), in combination or in admixture with one or more inert, non-toxic, cosmetically acceptable excipients or carriers.   13. Cosmetic compositions according to claim 12, characterized in that the content of compound of formula (I) is from 0.001 to 20% relative to the total weight of the composition.   14. Use of the compositions according to one of claims 12 to 13 in the field of hair care, in particular as shampoos, hair conditioners, lotions or hair balms. Ger-o, J (r V7 5 10 20