WO2015091860A1

WO2015091860A1 - Use of at least one hydroxypropyltrialkylammonium derivative as deodorant agent

Info

Publication number: WO2015091860A1
Application number: PCT/EP2014/078565
Authority: WO
Inventors: Maria Dalko; Julien Hitce
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2013-12-20
Filing date: 2014-12-18
Publication date: 2015-06-25
Anticipated expiration: 2016-06-20
Also published as: FR3015239B1; FR3015239A1

Abstract

Use of at least one hydroxypropyltrialkylammonium derivative as deodorant agent The present invention relates to the use of one or more hydroxypropyltrialkylammonium derivatives of formula (I) as defined below for treating body odour, in particular underarm odour. The invention also relates to a process for treating body odour using a composition comprising such compounds. The invention similarly relates to a composition comprising, in a physiologically acceptable medium, one or more hydroxypropyltrialkylammonium derivatives of formula (I) and one or more antiperspirant active agents and/or one or more additional deodorant active agents. The present invention also relates to one or more particular hydroxypropyltrialkylammonium-based compounds.

Description

Use of at least one hydroxypropyltrialkylammonium derivative as deodorant agent

The present invention relates to the use o f one or more hydroxypropyltrialkylammonium derivatives o f formula (I) as defined below for treating body odour, in particular underarm odour. The invention also relates to a process for treating body odour using a composition comprising such compounds .

The invention similarly relates to a composition comprising, in a physio lo gically acceptable medium, one or more hydroxypropyltrialkylammonium derivatives o f formula (I) and one or more antiperspirant active agents and/or one or more additional deodorant active agents .

The present invention also relates to one or more particular hydroxypropyltrialkylammonium-based compounds and also to compositions containing them, especially compositions in a physio logically acceptable medium.

In the cosmetics field, it is well known to use, in topical application, deodorant products containing active substances o f antiperspirant type or of deodorant type for reducing or even preventing body odour, especially underarm odour, which is generally unp leasant.

Eccrine or apocrine sweat generally has little odour when it is secreted. It is its degradation by bacteria via enzymatic reactions that produces malodorous compounds . Deodorant active agents thus have the function o f reducing or preventing the formation o f unpleasant odours.

Deodorant substances generally destroy the resident bacterial flora. Among these substances, the ones mo st commonly used are triclo san (2,4,4'-trichloro-2'-hydroxydiphenyl ether) and farneso l, which generally have the drawback o f substantially modifying the eco logy o f the cutaneous flora. Furthermore, triclosan has the disadvantage of being inhibited by the presence of certain compounds, for instance nonionic surfactants, commonly used in the formulation of cosmetic compositions. Finally, the inso luble nature of triclosan in water does not allow its incorporation into essentially aqueous formulations either.

Deodorant substances may also reduce bacterial growth. Among these substances, mention may be made o f transition-metal chelating agents such as EDTA or DPTA. These materials have the drawback o f depriving the medium o f metals necessary for bacterial growth.

There is thus still a real need to develop active compounds that have satisfactory deodorant activity and that are easy to formulate in compositions for reducing perspiration and/or odours, in particular in humans, and more particularly for combating body odour and more specifically underarm odour.

Certain quaternary hydroxypropylammonium derivatives are known in the cosmetics field from patent application EP 847 986, but their use as deodorant agents is not suggested, and nor are compositions combining these compounds with antiperspirant agents and/or additional deodorant agents .

The Applicant has discovered, surprisingly, that the use o f one or more compounds of formula (I), as defined below, makes it possible effectively to treat body odour, especially underarm odour, and that these compounds can be readily formulated in compositions for reducing perspiration and/or body odour, alone or optionally in combination with conventional antiperspirant active agents and/or deodorant active agents, without encountering the drawbacks mentioned previously.

In particular, the compound(s) of formula (I) according to the invention have effective deodorant activity towards body odour, especially as early as two hours after their application to the surface of the skin.

Furthermore, the compound(s) o f formula (I) according to the invention still have satisfactory deodorant activity after 24 hours . One subj ect of the present invention is thus especially the use for treating body odour, especially underarm odour, of one or more compounds o f formula (I) below, optical isomers thereof and/or geometrical isomers thereof:

(I)

in which formula (I) :

• R represents :

- a linear or branched, saturated or unsaturated C 1 - C29 alkyl radical, optionally substituted with one to six hydroxyl radicals, one to six radicals -NR ' R" in which R' and R " denote, independently o f each other, a hydrogen atom, a C i - C₆ alkyl radical or a C i -C₆ acyl radical,

- a linear or branched, saturated or unsaturated C 1 - C29 aralkyl radical, the aryl part being optionally substituted with one or more hydroxyl radicals,

- an aryl radical optionally substituted with one or more hydroxyl radicals;

• Ri , R₂ and R3 represent, independently o f each other, a linear C i -C₆ alkyl radical;

the electrical neutrality o f the compounds of formula (I) is ensured by an external anion X^"; X^" denoting an organic or mineral anion or mixture of anions.

Advantageously, the anion X^" is chosen such that the compound of formula (I) is physio logically acceptable.

For the purposes o f the present invention, the term "physio logically acceptable compound of formula (I)" means any compound o f formula (I) that is suitable for the topical administration of a composition containing the same.

A physio logically acceptable compound of formula (I) is preferentially a cosmetically or dermatologically acceptable compound of formula (I), that is to say one that has no unpleasant odour or appearance and that is entirely compatible with the topical administration route. In the present case, where the composition is intended to be administered topically, that is to say by application at the surface o f the keratin material under consideration, such a compound is in particular considered as physio logically acceptable when it does not cause stinging, tautness or redness unacceptable to the user.

The compound(s) of formula (I) thus defined may be used, alone or mixed, as deodorant agents, in a composition comprising a physio logically acceptable medium.

In other words, the invention relates to the use o f one or more compounds o f formula (I), as defined previously, as deodorant agents, alone or as a mixture especially in a composition comprising a physio logically acceptable medium.

The invention also relates to a composition comprising, in a physio logically acceptable medium, one or more compounds o f formula (I) as defined previously and one or more antiperspirant active agents and/or one or more additional deodorant active agents other than the compounds of formula (I) .

Similarly, the invention relates to the use o f the said composition for treating body odour and/or human perspiration.

Another subj ect of the present invention relates to a cosmetic process for treating body odour, in particular underarm odour, which consists in applying to the surface o f a human keratin material, preferably human skin and preferably the armpits, a composition comprising one or more compounds of formula (I) as defined previously.

Moreover, the invention also relates to particular compounds of formula (IA), (IB), (IC), (ID), (IE), (IF), ( 10) or ( 1 1 ) as defined below.

Moreover, a subj ect of the invention is also a composition, especially in a physio logically acceptable medium, comprising one or more compounds o f formula (IA), (IB), (IC), (ID), (IE), (IF), ( 10) or ( 1 1 ) as defined below. Other characteristics and advantages o f the invention will emerge more clearly on reading the description and the examples that fo llow.

In the text hereinbelow, and unless otherwise indicated, the limits of a range of values are included within that range.

The expression "at least one" is equivalent to the expression "one or more" .

For the purposes o f the present invention, the term "physio logically acceptable medium" means a medium that is suitable for the topical administration o f a composition. A physio logically acceptable medium is preferentially a cosmetically or dermatologically acceptable medium, i.e . a medium that has no unpleasant odour or appearance, and that is entirely compatible with the topical administration route. In the present case, where the composition is intended for topical administration, i.e . by app lication at the surface of the keratin material under consideration, such a medium is considered in particular to be physio logically acceptable when it does not cause stinging, tautness or redness that is unacceptable to the user.

In the context of the present invention, the term "deodorant active agent" means any active agent which, by itself, has the effect of masking, absorbing, improving and/or reducing the unpleasant odour resulting from the decomposition o f human sweat. The terms " deodorant active agent" and " deodorant agent" are equivalent in meaning according to the present invention.

The term "antiperspirant active agent" means any substance which, by itself, has the effect of reducing the flow o f sweat, of reducing the sensation on the skin o f moisture associated with human sweat and of masking human sweat. The terms "antiperspirant active agent" and "antiperspirant agent" are equivalent in meaning according to the present invention.

In the present invention, the term "human keratin material" means the skin (body, face, contour of the eyes), human keratin fibres such as the hair, body hairs, the eyelashes and the eyebrows, and the nails. /. Compounds of formula (I)

The compounds according to the present invention are salified hydroxypropyltrialkylammonium derivatives of formula (I) since they comprise in their structure a hydroxypropyltrialkylammonium part. In particular, these compounds are salts of hydroxypropyltrialkylammonium esters.

X^" denotes an organic or mineral anion or mixture of anions. Preferably, X^" is an anion chosen from halides, in particular chloride, bromide and iodide, sulfates, phosphates; carbonate; hydrogen carbonate; methanesulfonate; para-toluenesulfonate; camphorsulfonate; tartrate; citrate; lactate; acetate.

The compounds of formula (I) are preferentially those for which X^" denotes a mineral anion.

More preferentially, the compounds of formula (I) are such that

X^" denotes a halide anion, especially chloride.

According to one embodiment, Ri, R₂ and R₃ represent a methyl radical.

Preferably, in formula (I), compounds according to the present invention are such that, taken together or separately:

• R represents:

- a linear or branched, saturated or unsaturated C₃-C₂₅ alkyl radical,

- an aralkyl radical Ph-L-, in which L represents a linear or branched, saturated or unsaturated Ci-Cio divalent hydrocarbon-based radical,

- a phenyl radical optionally substituted with a hydroxyl radical,

• Ri, R₂ and R₃ represent a methyl radical, X^" denoting a cosmetically acceptable organic or mineral anion or mixture of anions.

Preferably, in formula (I) of the compounds according to the present invention, R, Ri, R₂, R₃ and X^", taken together, correspond to the meaning given previously. More preferably, in formula (I) of the compounds according to the present invention:

• R represents:

- a linear or branched, saturated or unsaturated C3-C25 alkyl radical,

- an aralkyl radical Ph-L- in which L represents a saturated Ci-C₆ divalent radical,

- a phenyl radical optionally substituted with a hydroxyl radical,

· Ri, R₂ and R3 represent a methyl radical, X^" denoting an organic or mineral anion or mixture of anions as defined previously.

According to a preferred embodiment, R represents a linear or branched, saturated or unsaturated C5-C17 alkyl radical; Ri, R₂ and R3 represent a methyl radical and X^" denotes a halide anion, especially chloride.

Preferably, the compounds of formula (I) according to the invention are chosen from the following compounds, and also the geometrical and/or optical isomer forms thereof, especially stereoisomers and diastereoisomers, X^" having the same meaning as previously:

Preferably, the compounds of formula (I) according to the present invention are chosen from compounds (1) to (18) for which X^" corresponds to a halide anion, and more particularly a chloride anion

CI^".

More preferably, the compounds of formula (I) according to the present invention are chosen from compounds 2, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 and 18, and even more preferentially from compounds 2, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 and 18 for which X^" corresponds to a halide anion and more particularly a chloride anion CI^".

The compounds of formula (I) according to the present invention may be obtained in two steps according to the procedure below:

X

Step 1 : The intermediate of 2,3-epoxypropyltrialkylammonium type is obtained by substitution of the epihalohydrin with the corresponding tertiary amine R1R2R3N.

A mixture of the epihalohydrin (1 equivalent) and of the tertiary amine R1R2R3N (1 equivalent) in a polar solvent, such as water or methanol, is stirred at 20-100°C for 12 to 72 hours. The solvent is then evaporated off and the residue is used directly in step 2.

The document Journal of Dispersion Science and Technology 2010, 31, pp. 1362-1369 gives an example of this methodology (X =

Step 2: The compounds forming the subject of the present invention may be obtained by reaction between the 2,3- epoxypropyltrialkylammonium derivative and the corresponding carboxylic acid, in basic medium.

The carboxylic acid RCOOH (1 equivalent) is dissolved in a polar solvent such as an isopropanol/acetone mixture. A catalytic amount of base such as NaHC0₃ (0.05 equivalent) and the 2,3 - epoxypropyltrialkylammonium ( 1 equivalent) are then added at room temperature and the reaction mixture is maintained at a temperature which may range from 0 to 100°C for 1 to 48 hours, until the reaction is complete. The expected ester is then isolated according to methods that are well known to those skilled in the art.

As mentioned previously, the invention also relates to the use of one or more compounds o f formula (I), as defined previously, as deodorant agents, alone or as a mixture especially in a composition comprising a physiologically acceptable medium.

The compounds o f the invention may also be obtained according to the process described in EP 847 985. II. Compositions

As indicated previously, the invention also relates to a composition comprising, in a physio lo gically acceptable medium, one or more compounds o f formula (I) as defined previously and one or more antiperspirant active agents and/or one or more additional deodorant active agents other than the compounds of formula (I) .

The invention also relates to a composition, especially in a physio logically acceptable medium, characterized in that it comprises one or more compounds o f formula (IA), (IB), (IC), (ID), (IE), (IF), ( 10) or ( 1 1 ) as defined below.

Preferably, the compounds o f formula (I) used in the said compositions are mineral salts o f the said compounds, especially those for which X^" corresponds to a halide anion, and preferably a chloride anion CI^".

The compound(s) of formula (I) are preferably present in amounts ranging from 0.01 % to 10% by weight, more preferentially from 0.02% to 5 % and even more preferentially from 0. 1 % to 5 % by weight relative to the total weight of the composition. When they are present, the antiperspirant active agents are preferably chosen from aluminium and/or zirconium salts ; complexes of zirconium hydroxychloride and o f aluminium hydroxychloride with an amino acid, such as those described in patent US-3 792 068. Such complexes are generally known under the name ZAG (when the amino acid is glycine) . ZAG complexes ordinarily have an Al/Zr quotient ranging from about 1 .67 to 12.5 and a metal/Cl quotient ranging from about 0.73 to 1 .93. Among these products, mention may be made o f aluminium zirconium octachlorohydrex GLY, aluminium zirconium pentachlorohydrex GLY, aluminium zirconium tetrachlorohydrate GLY and aluminium zirconium trichlorohydrate GLY.

Among the aluminium salts that may be mentioned are aluminium chlorohydrate, aluminium chlorohydrex, aluminium chlorohydrex PEG, aluminium chlorohydrex PG, aluminium dichlorohydrate, aluminium dichlorohydrex PEG, aluminium dichlorohydrex PG, aluminium sesquichlorohydrate, aluminium sesquichlorohydrex PEG, aluminium sesquichlorohydrex PG, alum salts, aluminium sulfate, aluminium zirconium octachlorohydrate, aluminium zirconium pentachlorohydrate, aluminium zirconium tetrachlorohydrate, aluminium zirconium trichlorohydrate and more particularly the aluminium hydroxychloride so ld by the company Reheis under the name Reach 30 1 ® or by the company Guilini Chemie under the name Aloxico ll PF 40® . Aluminium zirconium salts are, for example, the salt so ld by the company Reheis under the name Reach AZP-908-SUF®.

Aluminium chlorohydrate in activated or inactivated form will be used more particularly.

The antiperspirant active agents may be present in the composition according to the invention in a proportion of from 0.00 1 % to 30% by weight and preferably in a proportion o f from 0.5 % to 25 % by weight relative to the total weight of the composition.

The composition according to the invention may contain one or more additional deodorant active agents other than the compounds o f the invention, for instance : - bacteriostatic agents or other bactericidal agents such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 2,4-dichloro-2'- hydroxydiphenyl ether, 3',4',5'-trichlorosalicylanilide, l-(-3',4'- dichlorophenyl)-3-(4'-chlorophenyl)urea (triclocarban) or 3,7,11- trimethyldodeca-2,5,10-trienol (Farnesol); quaternary ammonium salts, for instance cetyltrimethylammonium salts, cetylpyridinium salts; chlorhexidine and salts; diglyceryl monocaprate, diglyceryl monolaurate or glyceryl monolaurate; polyhexamethylene biguanide salts;

- zinc salts, such as zinc salicylate, zinc phenolsulfonate, zinc pyrrolidonecarboxylate (more commonly known as zinc pidolate), zinc sulfate, zinc chloride, zinc lactate, zinc gluconate, zinc ricinoleate, zinc glycinate, zinc carbonate, zinc citrate, zinc chloride, zinc laurate, zinc oleate, zinc orthophosphate, zinc stearate, zinc tartrate, zinc acetate or mixtures thereof;

- odour absorbers such as zeolites, cyclodextrins, metal oxide silicates such as those described in patent application US 2005/063928; metal oxide particles modified with a transition metal, as described in patent applications US 2005/084464 and US 2005/084474, aluminosilicates such as those described in patent application EP 1 658 863, chitosan-based particles such as those described in patent US 6916465;

- substances that block the enzymatic reactions responsible for the formation of odorous compounds, such as arylsulfatase inhibitors; and mixtures thereof.

The additional deodorant active agents may be present in the composition according to the invention in a proportion of from 0.01% to 20% by weight and preferably in a proportion of from 0.1% to 15% by weight relative to the total weight of the composition.

The compositions according to the invention may be in any galenical form conventionally used for topical application and especially in the form of aqueous gels, or aqueous or aqueous- alcoholic solutions. By adding a fatty or oily phase, they may also be provided in the form of dispersions of lotion type, of emulsions of liquid or semi-liquid consistency o f milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or conversely (W/O), or of suspensions or emulsions o f so ft, semi-solid or so lid consistency o f the cream or gel type, or alternatively o f multiple emulsions (W/O/W or 0/W/O), of microemulsions, of vesicular dispersions of ionic and/or nonionic type, or o f wax/aqueous phase dispersions . These compositions are prepared according to the usual methods.

The compositions may especially be packaged in pressurized form in an aerosol device or in a pump-action bottle; packaged in a device equipped with a perforated wall, especially a grille; packaged in a device equipped with a ball applicator ("roll-on"); packaged in the form o f wands (sticks) or in the form o f loose or compacted powder. In this regard, they contain the ingredients generally used in products of this type, which are well known to those skilled in the art.

According to another particular form o f the invention, the compositions according to the invention can be anhydrous .

The term "anhydrous composition" is intended to mean a composition containing less than 2% by weight of water, indeed less than 0.5 % o f water, and especially free of water, the water not being added during the preparation o f the composition but corresponding to the residual water contributed by the mixed ingredients .

According to another particular form o f the invention, the compositions according to the invention may be so lid, in particular in wand or stick form.

The term " so lid composition" means that the measurement o f the maximum force measured by texturometry during the penetration of a probe into the sample o f formulation must be at least equal to 0.25 newtons, in particular at least equal to 0.30 newtons and especially at least equal to 0.35 newtons, assessed under precise measurement conditions as fo llows.

The formulations are poured hot into jars 4 cm in diameter and 3 cm deep . Cooling is performed at room temperature. The hardness of the formulations produced is measured after an interval o f 24 hours. The j ars containing the samp les are characterized by texturometry using a texture analyser such as the machine so ld by the company Rheo TA-XT2, according to the fo llowing protocol: a stainless-steel ball probe 5 mm in diameter is brought into contact with the sample at a speed of 1 mm/s . The measurement system detects the interface with the sample, with a detection threshold equal to 0.005 newtons. The probe penetrates 0.3 mm into the sample, at a speed of 0. 1 mm/s . The measuring machine records the change in force measured in compression over time, during the penetration phase . The hardness of the samp le corresponds to the average of the maximum force values detected during penetration, over at least three measurements .

Aqueous phase

The compositions according to the invention intended for cosmetic use may comprise at least one aqueous phase. They are in particular formulated as aqueous lotions or as water-in-oil or oil-in- water emulsions or as multiple emulsions (oil-in-water-in-oil or water- in-oil-in-water triple emulsions (such emulsions are known and described, for example, by C . Fox in "Cosmetics and Toiletries" - November 1986 - Vol. 1 01 - pages 101 - 1 12)) .

The aqueous phase of the said compositions contains water and generally other water-so luble or water-miscible so lvents . The water- so luble or water-miscible so lvents comprise short-chain monoalcoho ls, for examp le o f C 1 - C 4 , for instance ethano l or isopropanol; diols or polyo ls.

The compositions according to the invention preferably have a pH ranging from 3 to 9, depending on the chosen support.

When the composition(s) are in emulsion form, they generally contain, depending on the nature o f the emulsion, one or more emulsifying surfactants .

The total amount of emulsifiers will preferably be, in the composition(s) according to the invention, in active material contents ranging from 1 % to 8% by weight and more particularly from 2% to 6% by weight relative to the total weight of the composition. Fatty phase

The compositions according to the invention may contain at least one water-immiscible organic liquid phase, known as a fatty phase. This phase generally comprises one or more hydrophobic compounds which render the said phase water-immiscible . The said phase is liquid (in the absence o f structuring agent) at room temperature (20-25 °C). Preferentially, the water-immiscible organic liquid phase in accordance with the invention generally comprises at least one volatile oil and/or one non-vo latile oil and optionally at least one structuring agent.

The term "oil" means a fatty substance that is liquid at room temperature (25 °C) and atmospheric pressure (760 mmHg, i. e . 1 .05x l 0⁵ Pa) . The oil may be volatile or non-vo latile.

For the purposes of the invention, the term "vo latile oil" means an oil that is capable o f evaporating on contact with the skin or the keratin fibre in less than one hour, at room temperature and atmospheric pressure. The vo latile oils of the invention are vo latile cosmetic oils which are liquid at room temperature and which have a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging in particular from 0. 13 Pa to 40 000 Pa ( 10^~3 to 300 mmHg), in particular ranging from 1 .3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1 .3 Pa to 1300 Pa (0.0 1 to 10 mmHg) .

The term "non- vo latile oil" means an oil that remains on the skin or the keratin fibre at room temperature and atmospheric pressure for at least several hours, and that especially has a vapour pressure o f less than 10^"3 mmHg (0. 13 Pa) .

The oil may be chosen from any physio lo gically acceptable oil and in particular cosmetically acceptable oil, especially mineral, animal, plant or synthetic oils; in particular vo latile or non-vo latile hydrocarbon-based oils and/or silicone oils and/or fluoro oils, and mixtures thereof. More precisely, the term "hydrocarbon-based oil" means an oil mainly comprising carbon and hydrogen atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. Generally, the oil has a viscosity o f from 0.5 to 100 000 mPa. s, preferably from 50 to 50 000 mPa. s and more preferably from 100 to 300 000 mPa.s .

As examples o f vo latile oils that may be used in the invention, mention may be made of:

- vo latile hydrocarbon-based oils chosen from hydrocarbon- based oils containing from 8 to 1 6 carbon atoms, and especially Cs- C i 6 isoalkanes of petroleum origin (also known as isoparaffins) .

As examples o f non-vo latile oils that may be used in the invention, mention may be made of:

- hydrocarbon-based plant oils such as liquid triglycerides o f fatty acids o f 4 to 24 carbon atoms, for instance caprylic/capric acid triglycerides such as those sold by the company Stearineries Dubois or those so ld under the names Miglyo l 8 10, 8 12 and 8 1 8 by the company Dynamit Nobel, and jojoba oil,

- linear or branched hydrocarbons o f mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum j elly, polydecenes, polybutenes, hydrogenated polyisobutene, such as Parleam, or squalane;

- synthetic ethers containing from 10 to 40 carbon atoms;

- synthetic esters such as isononyl isononanoate, isopropyl myristate, isopropyl palmitate or C _{1 2} to C _{1 5} alkyl benzoates;

silicone oils such as linear (dimethicone) or cyclic (cyclomethicone) non-vo latile po lydimethylsiloxanes (PDMSs) .

The compositions according to the invention may also comprise one or more cosmetic adjuvants chosen from emollients, antioxidants, opacifiers, stabilizers, moisturizers, vitamins, bactericides, preserving agents, polymers, fragrances, a structuring agent for a fatty phase, in particular chosen from waxes, pasty compounds, gelling agents; organic or mineral fillers; thickeners or suspending agents, propellants or any other ingredient normally used in cosmetics for this type of application.

Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s) .

Aerosols

The compositions according to the invention may be pressurized and may be packaged in an aerosol device formed by:

(A) at least one container comprising a composition according to the invention,

(B) at least one propellant and at least one means for dispensing the said composition in aerosol form.

The propellants generally used in products of this type and that are well known to those skilled in the art are, for instance, dimethyl ether (DME); vo latile hydrocarbons such as n-butane, propane, isobutane and mixtures thereof, optionally with at least one chlorohydrocarbon and/or fluorohydrocarbon; among these propellants, mention may be made o f the compounds so ld by the company DuPont de Nemours under the names Freon® and Dymel® , and in particular mono fluorotrichloromethane, difluorodichloromethane, tetrafluorodichloroethane and 1 , 1 - difluoroethane so ld especially under the trade name Dymel 152 A® by the company DuPont. Use may also be made, as propellant, of carbon dioxide gas, nitrous oxide, nitrogen or compressed air.

The compositions containing one or more compounds o f formula (I) as defined previously and one or more antiperspirant active agents and/or one or more additional deodorant active agents other than the compounds o f formula (I) and/or the compositions especially in a physio logically acceptable medium, characterized in that they comprise one or more compounds of formula (IA), (IB), (IC), (ID), (IE), (IF), ( 10) or ( 1 1 ) as defined previously and the propellant(s) may be in the same compartment or in different compartments in the aerosol container. According to the invention, the concentration o f propellant generally ranges from 5 % to 95 % by pressurized weight and more preferentially from 50% to 85 % by weight relative to the total weight of the pressurized composition.

The dispensing means, which forms a part of the aerosol device, generally consists o f a dispensing valve controlled by a dispensing head, which itself comprises a nozzle via which the aerosol composition is vaporized. The container containing the pressurized composition may be opaque or transparent. It may be made o f glass, a polymer or a metal, optionally coated with a protective varnish coat.

III. Treatment process

The invention also relates to a cosmetic process for treating body odour, in particular underarm odour, which consists in applying to the surface o f a human keratin material, in particular the skin and more particularly the armpits, a composition comprising one or more compounds o f formula (I) as defined previously.

The cosmetic treatment process according to the present invention may be used on the surface o f the skin, preferably on the armpits.

The composition is applied to the surface of the keratin material, especially the skin and in particular the armpits, at room temperature.

Preferably, the composition is not rinsed off after it has been applied to the surface of the keratin material. IV. Hydroxypropyltrialkylammonium compounds

As indicated previously, the invention also relates to compounds o f formula (IA), (IB), (IC), (ID), (IE) or (IF) as defined below, and also compound ( 1 0) or ( 1 1 ) as defined previously. In particular, the compounds according to the invention correspond to formula (IA) below, and the optical isomers and/or geometrical isomers thereof:

(IA)

in which formula (IA) R₄ denotes a saturated or unsaturated branched C 3 - C 6 alkyl radical and X^" has the same meaning as in formula (I) .

Preferably, the compound o f formula (IA) denotes the compound o f formula (8) :

(8)

in particular that for which X^" represents a halide anion and in particular a chloride anion.

Similarly, the compounds according to the invention may correspond to formula (IB) below, and the optical isomers and/or geometrical isomers thereof:

(IB)

in which formula (IB) R5 represents an aryl radical optionally substituted with a hydroxyl radical (OH) and X^" has the same meaning as in formula (I) . Preferably, R₅ denotes a phenyl radical optionally substituted with a hydroxyl radical.

Preferably, the compounds of formula (IB) are chosen from the compounds ( 16) and ( 17) below:

)

in particular those for which X^" represents a halide anion and in particular a chloride anion.

The compounds according to the invention may also correspond to formula (IC) below, and the optical isomers and/or geometrical isomers thereof:

(IC)

in which formula (IC) R₆ represents a linear or branched, saturated or unsaturated C 1 - C29 aralkyl radical, the aryl part being optionally substituted with a hydroxyl radical and X^" having the same meaning as in formula (I) .

Preferably, R₆ denotes an aralkyl radical Ph-L-, in which L represents a linear or branched, saturated or unsaturated, preferably saturated, divalent C 1 -C 10 hydrocarbon-based radical, and X^" has the same meaning as in formula (I) .

Preferably, the compound o f formula (IC) is compound ( 1 8) below :

( 1 8)

in particular compound ( 1 8) for which X^" represents a halide anion and in particular a chloride anion.

The compounds according to the invention may also correspond to formula (ID) below, and the optical isomers and/or geometrical isomers thereof:

(ID)

in which formula (ID) R₇ represents a saturated linear C 1 - C29 alkyl radical and Z^" represents an anion or a mixture o f anions chosen from iodide, sulfate, phosphate, carbonate, hydrogen carbonate, para- toluenesulfonate, camphorsulfonate, tartrate, citrate and lactate.

The compounds according to the invention may also correspond to formula (IE) below, and the optical isomers and/or geometrical isomers thereof:

(IE)

in which formula (IE) Rs represents an alkyl radical - (CH₂)xCH₃ with x = 1 , 3 , 4, 5 , 12, 15 , 17 to 19 and 21 to 28 and W represents an anion chosen from chloride, methane sulfate and acetate, preferably chloride . Preferably, x denotes 1 , 3 , 4, 5 , 12 and W^" represents an anion chosen from chloride, methane sulfate and acetate, preferably chloride.

Preferably, the compounds (IE) are chosen from compounds (2) and (6) below for which X^" represents an anion chosen from chloride, methane sulfate and acetate :

and in particular compounds (2) and (6) for which X^" represents a halide anion and preferably chloride .

The compounds according to the invention may also correspond to formula (IF) below, and the optical isomers and/or geometrical isomers thereof:

(IF)

in which formula (IF) R9 represents a linear unsaturated (ethylenic double bond) C2 - C24 alkyl radical and X^" has the same definition as previously, X^" preferably denoting a halide anion and more particularly a chloride anion, with the exception o f the compounds (9) of structure :

for which X^" denotes a chloride or bromide anion and the compound for which R9 denotes a radical -(CH₂)5-CH=CH-CH2- CH=CH-(CH₂)4-Me and X^" denotes a chloride anion.

The compounds according to the invention may also denote compound (10) or (11) of structures:

for which X^" has the same meaning as for the compounds of structure (I) and in particular compound (10) or (11) for which X^" denotes a halide anion and in particular a chloride anion.

Thus, the compounds of formula (IA), (IB), (IC), (ID), (IE),

(IF), (10) or (11) as defined above make it possible to treat body odour, especially underarm odour.

The invention also relates to a composition, especially in a physiologically acceptable medium, characterized in that it comprises one or more compounds of formula (IA), (IB), (IC), (ID), (IE), (IF),

(10) or (11) as defined above. The following examples serve to illustrate the invention without, however, exhibiting a limiting nature.

EXAMPLES

A) Synthesis examples

Synthesis of compound (2) for which X^" denotes a chloride anion:

Hexanoic acid (2.32 g, 20 mmol, 1 eq.) is dissolved in an isopropanol (10 mL)/acetone (80 mL) mixture. A catalytic amount of NaHCOs (87 mg, 0.5 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (3.0 g, 20 mmol, 1 eq.) are then added at room temperature, and the reaction mixture is heated at 60°C for 16 hours. The reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (CEhCh/MeOH: 10/1) to isolate the expected ester in the form of a white solid (1.15 g, 25% yield).

The NMR spectrum (DMSO-d6) and the mass spectrum confirm the structure of the expected product (2) for which X^" denotes a chloride anion.

Synthesis of compound (8) for which X^" denotes a chloride anion:

Isovaleric acid (1 g, 10 mmol, 1 eq.) is dissolved in an isopropanol (22 mL)/acetone (33 mL) mixture. A catalytic amount of NaHCOs (42 mg, 0.5 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (1.51 g, 10 mmol, 1 eq.) are then added at room temperature, and the reaction mixture is heated at 80°C for 16 hours. The reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (CIHhCh/MeOH: 10/1) to isolate the expected ester in the form of a white solid (1.7 g, 70% yield). The ¹H NMR spectrum (DMSO-d6) and the mass spectrum confirm the structure of the expected product (8) for which X^" denotes a chloride anion. Synthesis of compound (9) for which X^" denotes a chloride anion:

Oleic acid (2.8 g, 10 mmol, 1 eq.) is dissolved in an isopropanol (22 mL)/acetone (33 mL) mixture. A catalytic amount of NaHCOs (42 mg, 0.5 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (1.51 g, 10 mmol, 1 eq.) are then added at room temperature, and the reaction mixture is heated at 80°C for 16 hours. The reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (CIHhCh/MeOH: 10/1) to isolate the expected ester in the form of a pale yellow oil (3.0 g, 79% yield).

The NMR spectrum (CD3OD) and the mass spectrum confirm the structure of the expected product (9) for which X^" denotes a chloride anion.

Synthesis of compound (10) for which X^" denotes a chloride anion:

Geranic acid (3.2 g, 20 mmol, 1 eq.) is dissolved in an isopropanol (22 mL)/acetone (33 mL) mixture. A catalytic amount of NaHCOs (84 mg, 1 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (3.0 g, 20 mmol, 1 eq.) are then added at room temperature, and the reaction mixture is heated at 80°C for 16 hours. The reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (CIHhCh/MeOH: 10/1) to isolate the expected ester in the form of a pale yellow oil (5 g, 79% yield). The ¹ H NMR spectrum (CD3OD) and the mass spectrum confirm the structure of the expected product ( 10) for which X^" denotes a chloride anion. Synthesis of compound ( 1 1 ) for which X^" denotes a chloride anion:

The product is obtained by catalytic hydrogenation o f compound 10 described above.

The catalyst 10% Pd/C ( 1 .5 g) is suspended in a so lution o f compound 10 (3 g, 9.4 mmo l) in a methano l (50 mL)/acetic acid (5 mL) mixture. The reaction mixture is heated at 60°C for 16 h under an atmosphere o f dihydrogen. After filtering off the catalyst, the filtrate is concentrated under reduced pressure to give the expected product in the form of a white solid (3 g, 1 00% yield) .

The ¹ H NMR spectrum (CD3OD) and the mass spectrum confirm the structure of the expected product ( 1 1 ) for which X^" denotes a chloride anion. Synthesis of compound ( 12) for which X^" denotes a chloride anion:

The preparation o f this compound and its characterization are described in document EP 847 985 (Example 2) Synthesis of compound ( 13) for which X^" denotes a chloride anion:

The preparation o f this compound and its characterization are described in document EP 847 985 (Example 4) Synthesis of compound ( 14) for which X^" denotes a chloride anion:

The preparation o f this compound and its characterization are described in document EP 847 985 (Example 3) Synthesis of compound (15) for which X^" denotes a chloride anion:

The preparation of this compound and its characterization are described in document EP 847985 (Example 1)

Synthesis of compound (16) for which X^" denotes a chloride anion:

Benzoic acid (3.66 g, 30 mmol, 1 eq.) is dissolved in an isopropanol (15 mL)/acetone (100 mL) mixture. A catalytic amount of NaHCOs (0.13 g, 1.5 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (6.8 g, 45 mmol, 1.5 eq.) are then added at room temperature, and the reaction mixture is heated at 60°C for 16 hours. The reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (CEhCh/MeOH: 10/1) to isolate the expected ester in the form of a white solid (2.1 g, 26% yield).

The NMR spectrum (CD3OD) and the mass spectrum confirm the structure of the expected product (16) for which X^" denotes a chloride anion.

Synthesis of compound (17) for which X^" denotes a chloride anion: Compound 17 for which X^" denotes a chloride anion is synthesized in two steps according to the scheme below.

Step 1

O-Benzylsalicylic acid (2.2 g, 10 mmol, 1 eq.) is dissolved in an isopropanol (22 mL)/acetone (33 mL) mixture. A catalytic amount of NaHCOs (42 mg, 0.5 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (1.51 g, 10 mmol, 1 eq.) are then added at room temperature, and the reaction mixture is heated at 80°C for 16 hours. The reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (ClHhCh/MeOH: 10/1) to isolate the benzyl intermediate A in the form of a white solid (2.5 g, 73% yield).

Step 2

The catalyst 10%> Pd/C (0.46 g) is suspended in a solution of compound A obtained previously (2.3 g, 6 mmol) in a methanol (50 mL)/acetic acid (5 mL) mixture. The reaction mixture is heated at 60°C for 16 h under an atmosphere of dihydrogen. After filtering off the catalyst, the filtrate is concentrated under reduced pressure to give the expected product 17 in the form of a pale pink solid (1.8 g, 100%) yield).

The ¹H NMR spectrum (CD3OD) and the mass spectrum confirm the structure of the expected product (17) for which X^" denotes a chloride anion.

Synthesis of compound (18) for which X^" denotes a chloride anion:

3-Phenylpropanoic acid (1.5 g, 10 mmol, 1 eq.) is dissolved in an isopropanol (22 mL)/acetone (33 mL) mixture. A catalytic amount of NaHCOs (42 mg, 0.5 mmol, 0.05 eq.) and 2,3- epoxypropyltrimethylammonium chloride (1.51 g, 10 mmol, 1.5 eq.) are then added at room temperature, and the reaction mixture is heated at 80°C for 16 hours. The reaction medium is concentrated under reduced pressure and the residue is purified by chromatography on silica gel (ClHhCh/MeOH: 10/1) to isolate the expected ester in the form of a white solid (2 g, 76%> yield).

The ¹H NMR spectrum (DMSO-d6) and the mass spectrum confirm the structure of the expected product (18) for which X^" denotes a chloride anion. B) Examples - deodorant activity

Compound ( 14) for which X^"=C1^" represented below is formulated in a gel, the composition of which is given below.

Compound ( 14) (X^" = CI )

Preparation o f the gel

The water of phase (A) is introduced cold into a beaker. The acrylate polymer is added to the surface of the water and left to hydrate, and the mixture is then homogenized by mechanical stirring. Phase (B) is added, the mixture is homogenized and then phase (C) is added containing compound ( 14) for which X^"=C1^".

The antimicrobial activity o f this compound formulated in gel form was tested on Cory 'neb acterium xerosis, this microorganism being placed under optimum growth conditions .

Protocol:

The mo del strain used is : Cory neb acterium xerosis CIP 52 1 6 This strain is placed in contact with the test formulation in a suitab le liquid culture medium in the following ratios :

- 1 0% of the microbial inoculum at 1 0⁸ microorganisms/ml

- 1 0% of the test formulation,

- 80%) of liquid culture medium (tryptocasein soya broth)

In parallel, a growth control, in which the test formulation is replaced with diluent, is prepared for the microorganism under the same conditions .

The samples are placed in a water bath at 35 ° C and stirred throughout the duration o f the test. After 2, 6 and 24 hours of contact, the number o f revivable microorganisms remaining in the mixture is evaluated. The results are expressed as a logarithm o f the number of microorganisms per millilitre o f mixture. The results obtained on the sample containing the test formulation are compared with those for the growth control and the difference is expressed as a Log number of difference at T 24 hours.

Results : Change in the number o f revivable microorganisms pe millilitre of sample (in Log) on the test formulation

Relative to the control, after 2 hours, the abatement is greater than 5 Log. The compound studied thus has activity classed as excellent within 2 hours on C. xerosis.

After 24 hours o f contact, the reduction relative to the control exceeds -6 Log.

The antibacterial activity may also be evaluated on the microorganism C. xerosis by measuring the smallest concentration o f test compound that significantly limits growth relative to a control (inhibitory concentration, MIC) . Thus, the bacteriostatic activity o f compounds (9), ( 10), ( 1 1 ), ( 16) and ( 1 8) for which X =C1 was evaluated according to the protocol described below. Principle:

The model strain used is: Cory 'neb acterium xerosis CIP 5216

1) The product is placed in contact on a microplate, at a concentration that is double the test concentration, with a double- concentrated nutrient broth containing a titre of approximately between 2 and 6xl0⁵ CFU/ml.

2) After incubating the microplate at 36°C for a given time, optical reading at 620 nm of the cloudiness produced by the microorganism growth is performed, and the results are expressed as a growth percentage calculated relative to a growth control.

3) The first concentration (MIC) of test product that makes it possible to obtain a growth percentage of less than or equal to 20% is considered as inhibitory, given that the chosen concentration range was: 0.01%-0.05%-0.1%-0.25%-0.5%-l%.

Results:

Test compound MIC (w/w%)

Compound (9), X^" = CI^" <0.01

Compound (16), X^" = CI^" 1

Compound (18), X^" = CI^" > 1

Compound (10), X^" = CI^" ≤ 0.01

Compound (11), X^" = CI^" <0.01

Claims

CLAIMS l. Use for treating body odour, especially underarm odour, of one or more compounds of formula (I) below, and the optical isomers and/or geometrical isomers thereof:

in which formula (I):

• R represents:

- a linear or branched, saturated or unsaturated C1-C29 alkyl radical, optionally substituted with one to six hydroxyl radicals, one to six radicals -NR'R" in which R' and R" denote, independently of each other, a hydrogen atom, a Ci-C₆ alkyl radical or a Ci-C₆ acyl radical,

- a linear or branched, saturated or unsaturated C1-C29 aralkyl radical, the aryl part being optionally substituted with one or more hydroxyl radicals,

- an aryl radical optionally substituted with a hydroxyl radical,

• Ri, R₂ and R3 represent, independently of each other, a linear Ci-C₆ alkyl radical;

the electrical neutrality of the compounds of formula (I) is ensured by an external anion X^"; X^" denoting an organic or mineral anion or mixture of anions.

2. Use according to Claim 1, characterized in that Ri, R₂ and R3 represent a methyl radical.

3. Use according to either of Claims 1 and 2, characterized in that, in formula (I), are such that, taken together or separately:

• R represents:

- a linear or branched, saturated or unsaturated C3-C25 alkyl radical, - an aralkyl radical Ph-L-, in which L represents a linear or branched, saturated or unsaturated Ci-Cio divalent hydrocarbon-based radical,

- a phenyl radical optionally substituted with a hydroxyl radical,

• Ri, R₂ and R3 represent a methyl radical, X^" denoting an organic or mineral anion or mixture of anions.

4. Use according to any one of Claims 1 to 3, characterized in that R represents a linear or branched, saturated or unsaturated C5-C17 alkyl radical; Ri, R₂ and R3 represent a methyl radical and X^" denotes a halide anion, especially chloride.

5. Use according to any one of the preceding claims, characterized in that the compounds of formula (I) are chosen from the following compounds, and also the geometrical and/or optical isomer forms thereof, especially stereoisomers and diastereoisomers:

X^" denoting an organic or mineral anion.

6. Use according to Claim 5, characterized in that the compound(s) of formula (I) are chosen from compound(s) (1) to (18) for which X^" corresponds to a halide anion, and more particularly a chloride anion CI^".

7. Use according to Claim 6, characterized in that the compound(s) of formula (I) are chosen from compounds 2, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 and 18, and even more preferentially from compounds 2, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 and 18 for which X corresponds to a halide anion and more particularly a chloride anion CI^".

8. Compounds corresponding to formula (IA) below, and the optical isomers and/or geometrical isomers thereof:

(IA)

in which formula (IA) R₄ denotes a saturated or unsaturated branched C3-C6 alkyl radical and X^" has the same meaning as in formula (I) as defined in the preceding claims.

9. Compounds corresponding to formula (IB) below, and the optical isomers and/or geometrical isomers thereof:

(IB)

in which formula (IB) R₅ represents an aryl radical optionally substituted with a hydroxyl radical (OH) and X^" has the same meaning as in formula (I) as defined in the preceding claims .

10. Compounds corresponding to formula (IC) below, and the optical isomers and/or geometrical isomers thereof:

(IC)

1 1 . Compounds corresponding to formula (ID) below, and the optical isomers and/or geometrical isomers thereof:

(ID)

in which formula (ID) R7 represents a saturated linear C 1 - C29 alkyl radical and Z^" represents an anion or a mixture o f anions chosen from io dide, sulfate, pho sphate, carbonate, hydrogen carbonate, p to luenesulfonate, camphorsulfonate, tartrate, citrate and lactate .

12. Compounds corresponding to formula (IE) below, and th optical isomers and/or geometrical isomers thereof:

(IE)

in which formula (IE) Rs represents an alkyl radical - (CH₂)xCH₃ with x = 1 , 3 , 4, 5 , 12, 15 , 17 to 19 and 21 to 28 and W represents an anion chosen from chloride , methane sulfate and acetate, preferably chloride .

13. Compounds corresponding to formula (IF) below, and the optical isomers and/or geometrical isomers thereof:

(IF)

in which formula (IF) R9 represents a linear unsaturated (ethylenic doub le bond) C₂-C₂₄ alkyl radical and X^" has the same definition as previously, X^" preferably denoting a halide anion and more particularly a chloride anion, with the exception o f the compounds (9) of structure :

for which X^" denotes a chloride or bromide anion and the compound for which R₉ denotes a radical -(CH₂)₅-CH=CH-CH₂-CH=CH-(CH₂)₄- Me and X^" denotes a chloride anion.

14. Compound ( 10) or ( 1 1 ) having the following structure :

for which X^" has the same meaning as in formula (I) as defined in the preceding claims, in particular represents a halide anion and in particular a chloride anion.

15. Composition characterized in that it comprises, in a physio logically acceptable medium, one or more compounds o f formula (I) as defined according to any one o f Claims 1 to 7, one or more antiperspirant active agents and/or one or more additional deodorant active agents other than the compounds of formula (I) .

16. Composition characterized in that it comprises, in a physio logically acceptable medium, one or more compounds chosen from those o f formula (IA), (IB), (IC), (ID), (IE), (IF), ( 10) or ( 1 1 ) as defined according to any one of Claims 8 to 14.