EP1263404A1

EP1263404A1 - Method for obtaining perfuming compositions and perfumed products and resulting products

Info

Publication number: EP1263404A1
Application number: EP01915463A
Authority: EP
Inventors: Isabelle Storet
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2000-03-13
Filing date: 2001-03-13
Publication date: 2002-12-11
Also published as: AU2001242555A1; FR2805991B1; US20030153486A1; WO2001068049A1; JP2003526651A; FR2805991A1

Abstract

The invention concerns a method for obtaining perfuming compositions, perfumed substances and perfumed products for perfumery, characterised in that they contain, as active principle imparting smell, an efficient amount of a 2-hydroxy-3-butenoic acid ester.

Description

PROCESS FOR OBTAINING PERFUMING COMPOSITIONS AND PERFUMED PRODUCTS AND PRODUCTS THUS OBTAINED.

The present invention relates to a process for obtaining perfume compositions and perfumed products and products thus obtained.

The present invention relates in particular to their use in the field of perfumery. Said compounds have interesting olfactory properties and can be used, inter alia, for the preparation of perfume compositions and perfumed products.

The perfume industry is constantly looking for products which, by the originality, the volume and the power of their fragrance, can give the compositions in which they are involved, a very special character.

It has now been found that the esters of 2-hydroxy-3-butenoic acid defined below have original olfactory properties.

It should be noted that it is impossible for a person skilled in the art to predict whether or not a given chemical compound will have an interesting odor from the olfactory point of view capable of being retained in the field of perfumery.

More specifically, the subject of the present invention is a process for obtaining perfume compositions, substances and perfumed products intended for perfumery, characterized in that one adds to the usual constituents of these compositions, substances and finished products, a effective amount of an ester of 2-hydroxy-3-butenoic acid.

The present invention also relates to perfume compositions, substances and perfumed products characterized in that they comprise, as active principle having an influence on the odor, an effective amount of an ester of acid 2- hydroxy-3-butenoic.

The invention therefore resides in a new use of esters of 2-hydroxy-3-butenoic acid, as a perfuming ingredient.

The perfuming ingredient which is the subject of the invention is an ester of 2-hydroxy-3-butenoic acid. It preferably corresponds one to the following general formula (I): R.

H ₂ C = C -CH-COOR ₁

OH _(|) in said formula (I):

- R- | represents a substituted or unsubstituted radical having from 1 to 40 carbon atoms and preferably an aliphatic, acyclic, saturated or unsaturated, linear or branched radical; a carbocyclic or heterocyclic radical, saturated or unsaturated, monocyclic or polycyclic.

- R2 represents an aliphatic radical, saturated with low carbon condensation preferably, less than 4.

In the following description of the present invention, the expression "hydroxybutenoic ester" is used generically to denote all the compounds corresponding to formula (I).

The hydroxybutenoic esters correspond to formula (I) in which the different radicals R-j and R2 have more particularly the following meaning.

The number of carbon atoms in R- | generally varies between 1 and 40 carbon atoms, and preferably between 1 and 12 carbon atoms.

The radical R- | may be a monovalent radical, substituted or unsubstituted, which may be an aliphatic, acyclic, saturated or unsaturated, linear or branched radical; a carbocyclic or heterocyclic radical, saturated or unsaturated, monocyclic or polycyclic. The radical Ri represents an acyclic aliphatic radical, saturated or unsaturated, linear or branched.

More specifically, R-j represents an alkyl, alkenyl, alkadienyl, linear or branched radical preferably having from 1 to 40 carbon atoms.

The hydrocarbon chain can be optionally interrupted by a heteroatom (for example, oxygen or sulfur) or by one of the groups such as in particular: -CO-, -COO-, -and / or carrying one of the following substituents: -OH, -COORβ,: in this formula Rg preferably represents hydrogen or a linear or branched alkyl radical having from 1 to 4 carbon atoms, and more particularly, a methyl or ethyl radical. R | may represent a carbocyclic, monocyclic radical. The number of carbon atoms in the ring can vary widely from 3 to 8 carbon atoms but it is preferably equal to 5 or 6 carbon atoms.

The carbocycle can be saturated or comprising 1 or 2 unsaturations in the cycle, preferably from 1 to 2 double bonds. As examples of carbocycles, mention may, for example, be made of a cycloalkyl or cycloalkenyl radical having 3 to 8 carbon atoms, preferably a cyclohexyl, cyclohexene-yl, cycloheptene-yl radical.

In the case where Ri represents a carbocyclic, monocyclic, saturated or unsaturated radical, it is possible that one or more of the carbon atoms of the ring are replaced by a heteroatom, preferably oxygen, nitrogen or sulfur or by a functional group , preferably carbonyl or ester, thus leading to a heterocyclic, monocyclic compound. The number of atoms in the ring can vary widely from 3 to 8 atoms but it is preferably equal to 5 or 6 atoms.

The radical Ri can also be carbocyclic, polycyclic, preferably bicyclic, which means that at least two rings have two carbon atoms in common. In the case of polycyclic radicals, the number of carbon atoms in each cycle varies between 3 and 6: the total number of carbon atoms being preferably equal to 7.

Examples of the commonly encountered bicyclic structure are given below:

[4.1, 0] [2.2.1] [3.1, 1] [3.2.0]

The radical R- | can also be heterocyclic, polycyclic, preferably bicyclic, which means that at least two rings have two atoms in common. In this case, the number of atoms in each cycle varies between 3 and 6 and is more preferably equal to 5 or 6.

The radical R- | may represent a saturated or unsaturated, linear or branched aliphatic radical, carrying a cyclic substituent. As examples of cyclic substituents, it is possible to envisage cycloaliphatic, aromatic or heterocyclic, in particular cycloaliphatic substituents comprising 6 carbon atoms in the ring or benzenic. Mention may more particularly be made of arylalkyl radicals preferably having 6 to 12 carbon atoms, the benzyl or β-phenylethyl radical. It should be noted that if the radical R 1 comprises a ring, it is possible that this ring carries a substituent of any kind. The substituents most often carried by the ring are one or more alkyl or alkoxy radicals preferably having from 1 to 4 carbon atoms, preferably three methyl radicals, a methylene radical (corresponding to an exocyclic bond), a radical alkenyl, preferably an isopropene-yl radical, a halogen atom, preferably chlorine or bromine.

More preferably, the esters of 2-hydroxy-3-butenoic acid correspond to the general formula (la):

H ₂ C = C -CH-COOR ₁

° ^H (la)

in said formula (la):

- Ri represents an alkyl radical, linear or branched, having from 1 to 12 carbon atoms, preferably from 1 to 6; a cydoalkyl radical preferably having 6 carbon atoms, an aralkyl radical having from 6 to 12 carbon atoms, preferably 7 or 8 carbon atoms,

- R2 represents an alkyl radical, linear or branched, having from 1 to 4 carbon atoms, preferably from 1 or 2. The compounds preferably used are those which correspond to formula (la) in which R- | represents an alkyl radical such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl, an allyl radical, a 2-hexenyl radical; a cyclohexyl radical; a benzyl or β-phenylethyl radical and R2 represents a methyl or ethyl radical.

As specific examples of hydroxybutenoic acid esters of formula (I), there may be mentioned, inter alia, the methyl ester of 2-hydroxy-3-methyl-3-butenoic acid or the ethyl ester of l 2-hydroxy-3-methyl-3-butenoic acid. The compounds of formula (I), in particular, the ethyl ester of 2-hydroxy-3-methyl-3-butenoic acid have an autumnal atmosphere by recalling the humid smells of the undergrowth enriched with fruity notes of nuts and of applesauce.

These are products which can be used, as perfume ingredients, in perfume compositions, substances and perfume products.

By "fragrance compositions" is meant mixtures of various ingredients such as solvents, solid or liquid carriers, fixatives, various odorous compounds, etc., in which the esters of 2- acid are incorporated. hydroxy-3-buteneoic formula (I), which are used to provide various types of finished products, the desired fragrance.

Perfume bases constitute preferred examples of perfume compositions in which the esters of 2-hydroxy-3-butenoic acid of formula (I) can be advantageously used.

Toilet waters, aftershave lotions, perfumes, soaps, bath or shower gels or deodorant or antiperspirant products, whether in the form of sticks or lotions, are examples of substances or finished products. in which the esters of 2-hydroxy-3-butenoic acid of formula (I) provide their original note.

They can also be used in shampoos and in hair products of all types.

They can also perfume talcs or powders of any kind.

They can also be suitable for room air fresheners or any cleaning product.

The content of the compositions according to the invention in ester of 2-hydroxy-3-butenoic acid of formula (I) expressed as a percentage by weight in the composition considered depends on the nature of said composition (base for perfume or eau de toilette for example) and the power and nature of the desired effect at the final product level. It goes without saying that in a perfume base the ester content of 2-hydroxy-3-butenoic acid of formula (I) can be very high, for example greater than 50% by weight and can reach 90% by weight while in a perfume, an eau de toilette or an after shave lotion, this content may be much less than 50% by weight. Thus the lower limit of the ester content of 2-hydroxy-3-butenoic acid of formula (I) may be that which causes a perceptible change in the smell of the fragrance or of the note of the finished product. In certain cases, this minimum content can be of the order of 0.01% by weight. It is obviously possible to use contents which are not within the limits of the contents indicated above without thereby departing from the scope of the present invention.

It can also be used in scented shampoos at a rate of 0.5 to 2% or to scent any hair product.

A particular application of esters of 2-hydroxy-3-butenoic acid as a perfume is in the field of soap making.

Soap is essentially a mixture of alkali metal salts, preferably sodium or potassium, of saturated or unsaturated fatty acids, with long chain, generally having from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms.

Examples of fatty acids that may be mentioned are saturated fatty acids such as caprylic acid Ce, capric acid CJ O, lauric acid C- | 2 _> myristic acid C14, palmitic acid C- | 6, Ci8 stearic acid _> 'unsaturated fatty acids having a single double bond such as linderic acid C-12. myristoleic acid C14, palmitoleic acid C-is, oleic acid C- | 8 ',' unsaturated fatty acids having two double bonds such as linoleic acid

C- | 8; ^'Are unsaturated fatty acids containing 3 double bonds such as linolenic acid C18; unsaturated fatty acids carrying a hydroxyl group such as ricinoleic acid C <| 8 as well as their mixtures.

The soap is prepared by saponification of triglycerides from various fatty substances: for example, tallow, peanut oil, palm oil, coconut oil, olive oil, etc. The choice of fatty mixture is linked to economic considerations as well as the desired characteristics.

A conventional soap-making process called the "Marseilles" process comprises the following steps: saponification carried out with soda, cooking, washing, liquidation which puts the soap in a physical form such that it can be used easily thereafter.

After the previous steps, the liquid soap is transformed into pieces used by the consumer. This last phase, called finishing, includes the operations of drying, kneading, roving, cutting, stamping and packaging. During mixing, a number of ingredients are added which give the characteristics to talc products, fillers, dyes, sequestrants, deodorants, perfumes. Thus, the esters of 2-hydroxy-3-butenoic acid can be added at this stage of manufacture.

The ester content of 2-hydroxy-3-butenoic acid can be in the soaps, of the order of 1 to 2%.

Another example of compositions in which said compounds can be advantageously introduced, is represented by the usual detergent compositions for washing clothes (industrial or household washing). These compositions generally comprise one or more of the following ingredients: anionic, cationic or amphoteric surfactants, bleaching agents, optical brighteners, various fillers, anti-redeposition agents. They generally comprise at least one surfactant, in an amount generally of the order of 5 to 60% by weight, preferably of 8 to

50% by weight. Among these, there may preferably be mentioned the anionic or nonionic surfactants usually used in the field of detergents for washing clothes.

They can also comprise usual additives, such as mineral or organic detergency builders, in an amount such that the total amount of detergency builders is of the order of 5 to 80% of the weight of said composition. , preferably 8 to 40% by weight, anti-fouling agents, anti-redeposition agents, bleaching agents, fluorescent agents, foam suppressants, softening agents, enzymes and other additives.

The perfuming ingredient, object of the present invention, namely the ester of 2-hydroxy-3-butenoic acid can be used in an amount of approximately 0.5 to 2.5%, preferably from 1 to 2%. by weight relative to the detergent composition.

The nature of the various components of the detergent composition is not critical and the esters of 2-hydroxy-3-butenoic acid of formula (I) can be added to any type of detergent composition. They can be introduced into fabric softeners, in liquid form or in compositions deposited on a support, most often a nonwoven, intended for use in tumble dryers.

The esters of 2-hydroxy-3-butenoic acid which are used, according to the invention, as perfuming ingredients, are known products and described in the literature.

For their synthesis, reference may be made in particular to the articles by Burr C. Hartman et al [J. Org. Chem. 57, n ° 7, p. 943-946 (1972)] and E. Voget el al [Helvetica Chimica Acta 33, 1, n ° 19, p. 119 (1950)].

A preferred preparation method, which is illustrated in the example, consists in reacting

- a ketone corresponding to formula (II):

O

I ¹ i,

^R 2 ^CH 3 (||) in which R ₂ has the meaning given above,

- With an ester of a haloacetic acid of formula (III): XCH _S -COOR _T (III) in which X represents a bromine or chlorine atom and Ri has the meaning given above. The reaction takes place in the presence of a strong base, in particular the sodium or potassium methylate or ethylate.

It is carried out at a temperature ranging from 0 ° C to room temperature (most often between 15 ° C and 25 ° C). The reaction is advantageously carried out in the presence of an organic solvent which dissolves the product obtained and thus makes it possible to separate it from the reaction medium.

As preferred solvents, aliphatic or aromatic hydrocarbons are used, and more particularly benzene, toluene, xylenes or petroleum fractions of the alkybenzene type. Toluene is advantageously chosen.

The product recovered in the organic phase corresponds to formula (IV):

in which Ri and R ₂ have the meaning given above.

The ester of 2-hydroxy-3-butenoic acid is obtained by carrying out the isomerization of the compound of formula (IV). This operation takes place by heating the organic phase comprising the compound of formula (IV).

The reaction temperature takes place between 100 and 150 ° C.

The reaction is preferably carried out under atmospheric pressure.

The compound of formula (I) is obtained which is separated from the organic phase. in a conventional manner, in particular by distillation.

The ester of 2-hydroxybutenoic acid thus obtained can be advantageously used in the perfume compositions of the invention.

An exemplary embodiment of the invention is given below, given by way of illustration and without limitation.

In Example 1, the abbreviation EHMB means "ethyl ester of 2-hydroxy-3-methylbutenoic acid".

Example 1

1 - In this example, the ethyl ester of 2-hydroxy-3-methylbutenoic acid (EHMB) is prepared, according to a process which consists in isomerizing ethyl dimethyl glycidate.

a - preparation of ethyl dimethyl glycidate 756 g (10 mol) of sodium ethylate, 5 l of toluene are loaded into a flask.

Cooled to 5 ° C and poured dropwise over a period of 4 h, a mixture consisting of 639 g (11 mol) of acetone and 1226 g (10 mol) of ethyl chloroacetate.

The reaction medium is brought to room temperature and left to act for 12 h.

5 I of water are added.

We decant. The aqueous phase is washed with 2 times 1 l of toluene.

The organic phases are combined and the resulting phase is washed with 3 l of water.

The organic phase is dried over magnesium sulfate.

b - preparation of the EHMB

The toluene solution prepared above is heated at 110 ° C. for 3 h, in the presence of 1.5 g of p-toluenesulfonic acid.

It is cooled and then neutralized with sodium bicarbonate. The toluene is removed at 130 mbar. Ethyl 2-hydroxy-3-methyl-3-buteneate is rectified under 10 mbar (boiling point 68 ° C).

A colorless liquid is thus recovered with a yield of 55% over the 2 stages.

2 - The EHMB is a powerful top note. It recreates an autumnal atmosphere by recalling the humid smell of oak moss or the barrel that has aged a good wine.

All the woody richness is enriched by the nutty notes that emanate from it. A fruity side of applesauce comes to end up brightening up the olfactory bouquet of this molecule.

Example 2

98.5 g of a shampoo base are incorporated into 1.5 g of a 33% by weight solution of ethyl 2-hydroxy-3-methyl-3-buteneate in polysorbate 20 (sorbitol ester and fatty acids (lauric, stearic, oleic) ethoxylated by 20 EO

The shampoo has the following weight composition: . sodium lauryl sulfate + ethoxylated sodium lauryl sulfate. 30% + disodium cocoamphodiacetate + hexylene glycol (MIRACARE 2MCA S / E) cocamidopropylamine oxide and lichen extract 1% (USNATE AO DRAIN)

. indian cress extract (CAPUCINE HS) 1%

. preservative (GERMABEN II) 0.2%

. citric acid qs pH 6.0 to 6.2

. demineralized water 67.3%

. fragrance 0.5%

The scented shampoo is stable in color and odor over a period of 3 months when it is stored at 50 ° C away from light and when it is stored at 20 ° C in daylight.

Example 3

98.5 g of a shower gel base are incorporated with 1.5 g of a 33% by weight solution of ethyl 2-hydroxy-3-methyl-3-buteneate in polysorbate 20.

The shower gel has the following weight composition:. sodium ethoxylated lauryl sulfate + 37.30% sodium cocoamphoacetate + MIPA cocamide (MIRACARE CS)

. HS chamomile 2.00%

. hydroxypropylated guar (JAGUAR C162) 0.30%

. preservative (GERMABEN II E) 0.20%

. demineralized water 59.7%

. citric acid qs pH 5.9

. perfume 0.50% The perfumed shower gel is stable in color and odor over a period of 3 months, when it is stored at 50 ° C protected from light and when it is stored at 20 ° C daylight.

Example 4 0.3 g of ethyl 2-hydroxy-3-methyl-3-butene is incorporated into 99.7 g of a hydrating cream base.

The moisturizing cream base is prepared by mixing the following two phases with the following weight composition: Phase A. capryl / capric triglyceride (DERMOL M5) 4% . mineral oil (MARCOL 82) 2%

. stearyl alcohol 3%

. isopropyl myristate (WICKENOL 111) 2%

. glyceryl stearate + polyethylene glycol 100 (ARLACEL 6% 165)

. dimethicone (MIRASIL DM 300) 4% Phase B

. deionized water 70.7%

. glycerol 8%

. preservative (GERMABEN II) 0.3% The scented moisturizer is stable in color and odor over a period of 3 months when it is stored at 50 ° C protected from light and when it is stored at 20 ° C in daylight.

Example 5

0.2 g of ethyl 2-hydroxy-3-methyl-3-butene is incorporated into 99.8 g of detergent powder.

The detergent powder has the following weight composition:

. linear sodium alkylbenzenesulfonate (LABS NANSA) 10%

. SOAP 5%

. ethoxylated alcohol C12, 7OE (SINPERONIC A7) 2%

. sodium tripolyphosphate (RHODIAPHOS HPA 3,5) 25%

. sodium carbonate 10%

. sodium silicate R2 5%

. sodium sulfate qs%

. sodium carboxymethyl cellulose 1%

. sodium perborate 15%

. TAED 5%

. diethylenetriaminepenta (methylenephosphonic acid) 1%

(DEQUEST 2066)

. anti-foam (RHODORSIL 20448) 1%

. optical brightener (TINOPAL DMS) 0.2%

The scented detergent powder has a satisfactory stability in coloring and odor over a period of 3 months when it is stored at 50 ° C away from light and when it is stored at 20 ° C under light of the day. Example 6

Perfumed soap is prepared by incorporating 10 g of ethyl 2-hydroxy-3-methyl-3-buteneate into 1000 g of soap strips which are shaped by successive passages in a extruder.

The scented soap is stable in color and odor over a period of 3 months when it is stored at 50 ° C away from light and when it is stored at 20 ° C in daylight.

Claims

1 - Process for obtaining perfuming compositions, substances and perfumed products intended for perfumery characterized in that one adds to the usual constituents of these compositions, substances and finished products, an effective amount of an ester of l 2-hydroxy-3-butenoic acid.

2 - Process according to claim 1 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (I):

R

in said formula (I):

- R- | represents a substituted or unsubstituted hydrocarbon radical having from 1 to 40 carbon atoms and preferably an aliphatic, acyclic, saturated or unsaturated, linear or branched radical; a carbocyclic or heterocyclic, saturated or unsaturated, monocyclic or polycyclic radical.

3 - Method according to one of claims 1 and 2 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (la):

in said formula (la):

- R- | represents an alkyl radical, linear or branched, having from 1 to 12 carbon atoms, preferably from 1 to 6; a cydoalkyl radical preferably having 6 carbon atoms, an aralkyl radical having from 6 to 12 carbon atoms, preferably 7 or 8 carbon atoms,

- R2 represents an alkyl radical, linear or branched, having from 1 to 4 carbon atoms, preferably from 1 or 2.

4 - Method according to one of claims 1 to 3 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (I) in which R- | represents an alkyl radical such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl; an allyl radical; a 2-hexenyl radical; a cyclohexyl radical; a benzyl or β-phenylethyl radical and R2 represents a methyl or ethyl radical.

5 - Method according to one of claims 1 to 4 characterized in that the ester of 2-hydroxy-3-butenoic acid is the methyl or ethyl ester of 2-hydroxy-3-methyl- 3-butenoic.

6 - Fragrance compositions, perfumed substances and products characterized in that they comprise, as active principle having an influence on the odor, an effective amount of an ester of 2-hydroxy-3-butenoic acid.

7 - Compositions according to Claim 6, characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (I):

in said formula (I):

8 - Compositions according to one of claims 6 and 7 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (la):

H-Cs C -CH-COOR,

° ^H (la) in said formula (la):

- Ri represents an alkyl radical, linear or branched, having from 1 to 12 carbon atoms, preferably from 1 to 6; a cydoalkyl radical preferably having 6 carbon atoms, an aralkyl radical having from 6 to 12 carbon atoms, preferably 7 or 8 carbon atoms, - R2 represents an alkyl radical, linear or branched, having from 1 to 4 carbon atoms, preferably from 1 or 2.

9 - Compositions according to one of claims 6 to 8 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (I) in which R- | represents an alkyl radical such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl, an allyl radical; a 2-hexenyl radical; a cyclohexyl radical; a benzyl or β-phenylethyl radical and R2 represents a methyl or ethyl radical.

10 - Compositions according to one of claims 6 to 9 characterized in that the ester of 2-hydroxy-3-butenoic acid is the methyl or ethyl ester of 2-hydroxy-3-methyl- 3-butenoic.

11 - Scented article in the form of perfume, eau de toilette, after shave lotions, perfumes, soaps, bath or shower gels, deodorant or antiperspirant products, shampoos or any hair product, talcs or powders of any kind, air fresheners, any cleaning product or detergent compositions, fabric softeners characterized in that it comprises at least one ester of 2-hydroxy-3- acid butene described in one of claims 6 to 10.

12 - Scented article in the form of perfume, eau de toilette, after shave lotions, perfumes, soaps, bath or shower gels, deodorant or antiperspirant products, shampoos or any hair product, talcs or powders of all kinds, air fresheners, any cleaning product or detergent compositions, fabric softeners characterized in that it comprises at least one methyl or ethyl ester of 2-hydroxy acid -3-methyl-3-butenoic.

13 - Use as a perfuming ingredient, esters of 2-hydroxy-3-butenoic acid. 14 - Use according to claim 13 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (I):

R.

H ₂ C = C -CH ~ COOR ₁

OH _(|) in said formula (I): - R- _| represents a substituted or unsubstituted hydrocarbon radical having from 1 to 40 carbon atoms and preferably an aliphatic, acyclic, saturated or unsaturated, linear or branched radical; a carbocyclic or heterocyclic radical, saturated or unsaturated, monocyclic or polycyclic.

15 - Use according to one of claims 13 and 14 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (la):

R

H ₂ C = C -CH— COOR ₁ ^H (la) in said formula (la):

- R- | represents an alkyl radical, linear or branched, having from 1 to 12 carbon atoms, preferably from 1 to 6; a cydoalkyl radical preferably having 6 carbon atoms, an aralkyl radical having from 6 to 12 carbon atoms, preferably 7 or 8 carbon atoms, - R2 represents an alkyl radical, linear or branched, having from 1 to 4 atoms carbon, preferably 1 or 2.

16 - Use according to one of claims 13 to 15 characterized in that the ester of 2-hydroxy-3-butenoic acid corresponds to the general formula (I) in which R- | represents an alkyl radical such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl; an allyl radical, a 2-hexenyl radical; a cyclohexyl radical; a benzyl or β-phenylethyl radical and R2 represents a methyl or ethyl radical.

17 - Use according to one of claims 13 to 16 characterized in that the ester of 2-hydroxy-3-butenoic acid is the methyl or ethyl ester of 2-hydroxy-3-methyl- 3-butenoic. 18 - Use of the methyl or ethyl ester of 2-hydroxy-3-methyl-3-butenoic acid as an autumnal note of the wet smell type of oak moss associated with a nut smell.