Enolethers and related acetals odorants

Abstract

The present invention relates to specific enolethers of the formula (I) and related acetals of the formula (III) which show an interesting almond note. It has been found that these enolethers and / or acetals can be combined with aldehydes of the formula (II) to obtain a particular pleasant olfactory impression.

Description

[0001] ENOLETHERS AND RELATED ACETALS ODORANTS

[0002] Technical Field

[0003] The present invention relates to the field of specific enolethers as well as the intermediates in their synthesis, and particularly to the field of perfumery ingredients and odorants.

[0004] Background of the invention

[0005] WO 2010 / 052635 A1 discloses different aldehydes, esters and nitriles having a floral and / or anisic type of odor. It discloses also (4E)-2,4-dimethyl-5-(4-methylphenyl)-4-pentenal, the odor characteristics of which is very appealing to perfumers.

[0006] Although, this combination of different notes is very appealing, it is desired to get a further improvement of this odor characteristic.

[0007] Summary of the invention

[0008] Therefore, the problem to be solved by the present invention is to offer some components to improve the overall olfactory sensation.

[0009] Surprisingly, it has been found that the enolether of claim 1 , offers a solution to this problem.

[0010] It has been found that the enolether of formula (I) has a very typical almond odor, which blends particularly well in the olfactory sensation of the aldehyde of formula (II) (2,4-dimethyl-5-(4-methylphenyl)-4-pentenal). The overall olfactory sensation of a combination of formula (I) and aldehyde of formula (II) increases the almond character even further and a very harmonic odor composition is achieved which is very pleasant and, therefore, is very attractive for perfumers.

[0011] Furthermore, it has been found that said enolether of formula (I) can be synthesized from said aldehyde of formula (II) by an intermediate of an acetal of the formula (III). Surprisingly, it has been found that this intermediate acetal of the formula (III) exhibits also a similar almond odor. Therefore, also a combination of this acetal of formula (III) with the aldehyde of the formula (II) leads to a veryharmonic odor composition as similar to the combination of the enolether of formula (I) and the aldehyde of formula (II).

[0012] Further aspects of the invention are subject of further independent claims. Particularly preferred embodiments are subject of dependent claims.

[0013] Detailed description of the invention

[0014] In a first aspect, the present invention relates to a compound of formula (I)

[0015]

[0016] wherein

[0017] R represents either H or a Ci-w-alkyl group; preferably a methyl group;

[0018] R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

[0019] For sake of clarity, some terms used in the present document are defined as follows:

[0020] In the present document, a “Cx-y-alkyl” group is an alkyl group comprising x to y carbon atoms, i.e. , for example, a Ci-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example, -CH(CH3)-CH2-CH3 is considered as a C4-alkyl group.

[0021] In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.The compound of the formula (I) is an enolether.

[0022]

[0023] The substituent R represents either H or a Ci- -alkyl group; preferably a methyl group.

[0024] The substituent R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group.

[0025] In a very preferred embodiment, the compound of the formula (I) is an enolether of the formula (l-A) which is the enolether of the formula (I) R representing a methyl group and R1representing an ethyl group.

[0026]

[0027] The two double bonds may independently from each may be in the Z or the E-configuration.

[0028] In one embodiment the compound of the formula (I), is a mixture of the four isomers having the E / E, E / Z, Z / E or Z / Z configuration at the double bonds, i.e.

[0029] 1 E / 4E, 1 E / 4Z, 1Z / 4E or 1Z / 4Z. It is preferred that the double bond near to the aromatic ring is in the E-configuration (i.e.1 E), or that the isomers having the E-configuration at the double bond near the aromatic ring (i.e. 1 E) is in molar excess to the isomers having the Z-configuration at said double bond (i.e. 1Z).

[0030] The enolether of the formula (I) possesses a typical almond note which makes it very appreciated by perfumers.

[0031] The compound of the formula (I) can be prepared by a process comprising the steps

[0032] a) acetalization of the aldehyde of the formula (II) by an alcohol of formula R1OH to yield a compound of the formula (III)

[0033]

[0034] b) transforming the acetal of the formula (III) to the compound of the formula (I);

[0035] wherein

[0036] R represents either H or a Ci- -alkyl group; preferably a methyl group;

[0037] R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

[0038] The compound of the formula (II), particularly the compound of the formula (l-A), can be prepared as disclosed in WO 2010 / 052635 A1 , particularly as disclosed on page 10, lines 13- page 11 , line 5, in WO 2010 / 052635 A1 , particularly for example from 1-[1-(allyloxy)-2-methyl-2-propenyl]-4-methylbenzene and [RuCl2(PPh3)3], particularly as described in detail on page 16, lines 12- 24 in WO 2010 / 052635 A1.It is preferred to use a mixture of E / Z isomers of formula (II) as starting material for step a) leading accordingly also to a mixture of E / Z isomers of the formula (III).

[0039] The alcohol of the formula R1OH, preferably methanol or ethanol, most preferably ethanol, is reacted with the aldehyde of the formula (II) to yield in step a) the acetal of the formula (III) by a method known by the person skilled in the art, typically in the presence of a Bronsted acid at elevated temperature.

[0040] In a case a mixture of the E / Z isomers of the aldehyde is used in a specific E / Z ratio, the resulting acetal of the formula (III) is also a mixture of the E / Z isomers in the same E / Z ratio.

[0041] In step b), said acetal of the formula (III) is transformed to the enolether of the formula (I). Said transformation is typically performed by heating the acetal of the formula (I) with using sodium p-toluene-sulfonate and removing the alcohol which is formed by distillation from the reaction mixture. By this transformation the acetal of the formula (III) is quantitatively converted to the enolether of the formula (I). In a case a mixture of the E / Z isomers of the acetal is used ratio, the resulting enolether of the formula (I) is also a mixture of the E / Z isomers.

[0042] In step b) a double bond at the 1 position of the enolether of the formula (I) is formed. Said double bond shows an E / Z mixture.

[0043] Both the acetal of the formula (III) and the enolether of the formula (I) are new and inventive.Hence, in a further aspect, the present invention relates to an acetal of the formula (III)

[0044]

[0045] wherein

[0046] R represents either H or a Ci-w-alkyl group; preferably a methyl group;

[0047] R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

[0048] A particularly preferred acetal of the formula (III) is the acetal of the formula (lll-A).

[0049]

[0050] The acetal of the formula (III) possesses a typical almond note which makes it very appreciated by perfumers.

[0051] As pointed out the aldehyde of the formula (II) is a starting material in the synthesis of the enolether of the formula (I). The aldehyde of the formula (II) is known to be used as perfumery ingredient and has an interesting mixture of floral, green and aldehydic notes.

[0052] It has been surprisingly found, that when combining the enolether of formula (I) and the aldehyde of the formula (II), a very harmonic olfactory overallimpression is obtained by adding a significant almond compound to the odor of the aldehyde of formula (II) leading to an overall olfactory profile which is very attractive to perfumers.

[0053] Hence, in a further aspect, the present invention relates to a composition comprising at least one aldehyde of the compound of the formula (II) and at least one compound of the formula (I)

[0054]

[0055] wherein

[0056] R represents either H or a Ci- -alkyl group; preferably a methyl group;

[0057] R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

[0058] It is preferred that the molar ratio of the compound of the formula (II) to the compound of the formula (I) or is in the range of 99:1 to 50:50, preferably of 99:1 to 80: 20, more preferably of 99.1 to 90:10.n a preferred embodiment, said composition comprises a mixture of the compound of formula (ll-E) and (ll-Z).It is particularly preferred that said composition comprises a mixture of the compound of formula (ll-E) and (ll-Z)

[0059]

[0060] It is preferred that in said mixture the compound of the formula (ll-E) is in molar excess over the compound of the formula (ll-Z), particularly that the molar ratio of the compound of the formula (ll-E) to the compound of the formula (ll-Z) is in the range of 99:1 to 50:50, preferably of 95:5 to 60:40, more preferably of 95:5 to 70:30.

[0061] As pointed out the aldehyde of the formula (II) is a starting material in the synthesis of the enolether of the formula (I). The acetal of the formula (III) is an intermediate in the synthesis of the enolether of the formula (I) from aldehyde of the formula (II).

[0062] As mentioned as well, the aldehyde of the formula (II) is known to be used as perfumery ingredient and has an interesting mixture of floral, green and aldehydic notes.

[0063] It has now been surprisingly found, that when combining the acetal of formula (III) and the aldehyde of the formula (II), a very harmonic olfactory overall impression is obtained by adding a significant almond compound to the odor of the aldehyde of formula (II) leading to an overall olfactory profile which is very attractive to perfumers.Hence, in a further aspect, the present invention relates to a composition comprising at least one aldehyde of the compound of the formula (II) and at least one compound of the formula (III)

[0064]

[0065] wherein

[0066] R represents either H or a Ci- -alkyl group; preferably a methyl group;

[0067] R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

[0068] It is preferred that, in this composition, the molar ratio of the compound of the formula (II) to the compound of the formula (III) is in the range of 99:1 to 50:50, preferably of 99:1 to 80: 20, more preferably of 99.1 to 90:10.

[0069] It is particularly preferred that said composition comprises a mixture of the compound of formula (lll-E) and (lll-Z)

[0070]

[0071]

[0072] It is preferred that in said mixture the compound of the formula ( I l-E) is in molar excess over the compound of the formula (ll-Z), particularly that the molar ratio of the compound of the formula ( I l-E) to the compound of the formula (ll-Z) is in the range of 99:1 to 50:50, preferably of 95:5 to 60:40, more preferably of 95:5 to 70:30.

[0073] As pointed above, the compounds of the formula (I) and of the formula (III) have distinct and natural olfactory notes of almonds.

[0074] Consequently, these compounds are very attractive to be used in the field of fragrance and perfumes.

[0075] Therefore, in a further aspect, the present invention relates to a perfuming composition comprising

[0076] i) at least the compound of formula (I) or the compound of the formula (III) as discussed above in great details or a composition as discussed above in great details;

[0077] ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and

[0078] iii) optionally at least one perfumery adjuvant.

[0079] By “perfumery carrier” it is meant here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients. Said carrier may be a liquid or a solid.

[0080] As liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, one can cite as non-limitingexamples, solvents such as butylene or propylene glycol, glycerol, dipropyleneglycol and its monoethers, 1 ,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate 1 ,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, available from DRT), benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1 -ethanol, tri-ethyl citrate or mixtures thereof, which are the most commonly used or also naturally derived solvents like glycerol or various vegetable oils such as palm oil, sunflower oil or linseed oil. For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carriers than those previously specified, can be also ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (origin: Dow Chemical Company), or hydrogenated castors oils such as those known under the trademark Cremophor® RH 40 (origin: BASF).

[0081] As solid carrier is meant to designate a material to which the perfuming composition or some element of the perfuming composition can be chemically or physically bound. In general, such solid carriers are employed either to stabilize the composition, or to control the rate of evaporation of the compositions or of some ingredients. Solid carriers are of current use in the art and a person skilled in the art knows how to reach the desired effect. However, by way of non-limiting examples of solid carriers, one may cite absorbing gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, dextrins, maltodextrins wood based materials, organic or inorganic gels, clays, gypsum, calcium carbonate, silicon dioxide, talc or zeolites.

[0082] As other non-limiting examples of solid carriers, one may cite encapsulating materials. Examples of such materials may comprise wall-forming and plasticizing materials, such as glucose syrups, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinyl alcohols, proteins or pectins, plant gums such as acacia gum (Gum Arabic), urea, sodium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium sulfate, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, carbohydrates, saccharides such as sucrose, mono-, di-, tri- and polysaccharidesand derivatives such as chitosan, starch, cellulose, carboxymethyl methylcellulose, methylcellulose, hydroxyethyl cellulose, ethyl cellulose, propyl cellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol, and isomalt, polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), polyvinyl alcohol, acrylamides, acrylates, polyacrylic acid and related structures, maleic anhydride copolymers, amine-functional polymers, vinyl ethers, styrenes, polystyrenesulfonates, vinyl acids, ethylene glycol-propylene glycol block copolymers, pectins, xanthanes, alginates, carragenans, citric acid or any water soluble solid acid, fatty alcohols or fatty acids and mixtures thereof.

[0083] The encapsulation is a well-known process to a person skilled in the art, and may be performed, for instance, by using techniques such as spray-drying, agglomeration or yet extrusion; or consists of a coating encapsulation, including coacervation and complex coacervation techniques.

[0084] As non-limiting examples of solid carriers, one may cite in particular the core-shell capsules with resins of aminoplast, polyamide, polyester, polyurea or polyurethane type or a mixture thereof (all of said resins are well known to a person skilled in the art) using techniques like phase separation process induced by polymerization, interfacial polymerization, coacervation or altogether (all of said techniques have been described in the prior art), optionally in the presence of a polymeric stabilizer or of a cationic copolymer.

[0085] Resins may be produced by the polycondensation of an aldehyde (e.g. formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with an amine such as urea, benzoguanamine, glycoluril, melamine, methylol melamine, methylated methylol melamine, guanazole and the like, as well as mixtures thereof. Alternatively, one may use preformed resins alkylolated polyamines such as those commercially available under the trademark Urac® (origin: Cytec Technology Corp.), Cymel® (origin: Cytec Technology Corp.), Urecoll® or Luracoll® (origin: BASF).

[0086] Examples of other resins are the ones produced by the polycondensation of a polyol, like glycerol, and a polyisocyanate, like a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or xylylene diisocyanate or a biuret of hexamethylene diisocyanate or a trimer of xylylene diisocyanate with trimethylolpropane (known with the tradename of Takenate®, origin: MitsuiChemicals), among which a trimer of xylylene diisocyanate with trimethylolpropane and a biuret of hexamethylene diisocyanate are preferred.

[0087] Some of the seminal literature related to the encapsulation of perfumes by polycondensation of amino resins, namely melamine based resins with aldehydes includes articles such as those published by K. Dietrich et al. Acta Polymerica, 1989, Vol. 40, pages 243, 325 and 683, as well as 1990, Vol. 41 , page 91. Such articles already describe the various parameters affecting the preparation of such core-shell microcapsules following prior art methods that are also further detailed and exemplified in the patent literature. US 4’396'670, to the Wiggins Teape Group Limited is a pertinent early example of the latter. Since then, many other authors have enriched the literature in this field and it would be impossible to cover all published developments here, but the general knowledge in encapsulation technology is very significant. More recent publications of pertinence, which disclose suitable uses of such microcapsules, are represented for example by the article of K. Bruyninckx and M. Dusselier, ACS Sustainable Chemistry & Engineering, 2019, vol. 7, pages 8041-8054.

[0088] As “perfumery base” is meant a composition comprising at least one perfuming co-ingredient which is not the compound of formula (I) or (II) or (III). Moreover, by “perfuming co-ingredient” it is meant here a compound, which is used in a perfuming preparation or a composition to impart a hedonic effect, i.e. used for the primary purpose of conferring or modulating an odor. In other words, such a co-ingredient, to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor. The perfuming ingredient may impart an additional benefit beyond that of modifying or imparting an odor, such as long-lasting, blooming, malodour counteraction, antimicrobial effect, antiviral effect, microbial stability, or pest control.

[0089] The nature and type of the perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong tochemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, thiols, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin.

[0090] In particular one may cite perfuming co-ingredients which are commonly used in perfume formulations, such as:

[0091] Aldehydic ingredients: decanal, dodecanal, 2-methyl-undecanal, 10- undecenal, octanal, nonanal and / or nonenal;

[0092] Aromatic-herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5- methyltricyclo[6.2.1 ,02,7]undecan-4-one, 1-methoxy-3-hexanethiol, 2-ethyl- 4,4-dimethyl-1 ,3-oxathiane, 2, 2, 7 / 8, 9 / 10-tetramethylspiro[5.5]undec-8-en-1 - one, menthol and / or alpha-pinene;

[0093] Balsamic ingredients: coumarin, ethylvanillin and / or vanillin;

[0094] Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-p-menthen-8-yl acetate and / or 1 ,4(8)-p-menthadiene;

[0095] Floral ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl- 4(2H)-pyranol, beta ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl- 4-(2,6,6-trimethyl-2-cyclohexen-1 -yl)-3-buten-2-one, (1 E)-1 -(2 ,6, 6-trim ethy I- 2-cyclohexen-1 -yl)-1 -penten-3-one, 1 -(2, 6, 6-trim ethy 1-1 ,3-cyclohexadien-1 - yl)-2-buten-1 -one, (2E)-1 -(2,6,6-trimethyl-2-cyclohexen-1 -yl)-2-buten-1 -one, (2E)-1 -[2,6,6-trimethyl-3-cyclohexen-1 -yl]-2-buten-1 -one, (2E)-1 -(2,6,6- trim ethy 1-1 -cyclohexen-1 -yl)-2-buten-1 -one, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexene-1 -carboxylate, 3-(4,4-dimethyl-1 -cyclohexen-1 - yl)propanal, 3-(3,3 / 1 ,1-dimethyl-5-indanyl)propanal, hexyl salicylate, 3,7- dimethyl-1 ,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate, geraniol, p-menth-1-en-8-ol, 4-(1 ,1-dimethylethyl)-1-cyclohexyle acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate , high cis methyl dihydrojasmonate, 3-methyl-5-phenyl-1- pentanol, verdyl proprionate, geranyl acetate, tetrahydro linalool, cis-7-p- menthanol, propyl (S)-2-(1 ,1-dimethylpropoxy)propanoate, 2-methoxy- naphthalene, 2, 2, 2-trichloro-1 -phenylethyl acetate, 4 / 3-(4-hydroxy-4-methyl-pentyl)-3-cyclohexene-1-carbaldehyde, amylcinnamic aldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyle acetate, 4-(1 , 1 -dimethylethyl)-1 -cyclohexyl acetate, verdyl isobutyrate and / or mixture of methylionones isomers;

[0096] Fruity ingredients: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1 ,3-oxathiane, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gammanonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1 ,3-dioxolane-2-acetate, diethyl 1 ,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl [3-ethyl-2-oxiranyl]-acetate and / or diethyl 1 ,4-cyclohexane dicarboxylate;

[0097] Green ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclo-hexene-1-carbaldehyde, 2-tert-butyl-1 -cyclohexyl acetate, styrallyl acetate, allyl (2-methylbutoxy)acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1 -ol and / or 1 -(5,5-dimethyl-1 -cyclohexen-1 -yl)-4-penten-1 -one;

[0098] Musk ingredients: 1 ,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopenta-decen-1 -one, 3-methylcyclopentadecanone, 1 -oxa-12-cyclohexadecen-2-one, 1 -oxa-13-cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-1-one, 2-{(1 S)-1 -[(1 R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3-methyl-5-cyclopentadecen-1 -one, 4,6,6,7,8,8-hexamethyl-1 , 3, 4, 6,7,8-hexahydrocyclopenta[g]isochromene, (1 S, 1 ' R)-2-[1 -(3' , 3'-d imethy 1-1 '-cyclohexyl)ethoxy]-2-methylpropyl propanoate, oxacyclohexadecan-2-oneand / or (1 S, 1'R)-[1 -(3' , 3'-d im ethy 1-1 '-cyclohexyl)ethoxycarbonyl]methyl propanoate;

[0099] Woody ingredients: 1-[(1 RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1 R)-2,2,3-trimethyl-3-cyclopenten-1 -yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxirane-2,9'-tricyclo[6.2.1 ,02’7]undec[4]ene, (1-ethoxyethoxy)-cyclododecane, 2,2,9, 11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-1 -ethanone, patchouli oil, terpenes fractions of patchouli oil, Clearwood® (Origin: Firmenich SA), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1 ,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1 -one and / or isobornyl acetate;

[0100] Other ingredients (e.g. amber, powdery spicy or watery): dodecahydroSa, 6,6, 9a-tetramethyl-naphtho[2,1-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(1 ,3- benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1 ,5-benzodioxepin-3(4H)- one, 2,5,5-trimethyl-1 ,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl- 1-phenyl)butanal.

[0101] A perfumery base according to the invention may not be limited to the above-mentioned perfuming co-ingredients, and many other of these coingredients are in any case listed in reference texts such as the book by S.

[0102] Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds also known as properfume or profragrance. Non-limiting examples of suitable properfume may include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1 -cyclohexen-1 -yl)-2-butanone, trans-3-(dodecylthio)-1 -(2 , 6, 6-trim ethy I-3-cyclohexen-1 -yl)-1 -butanone, 3-(dodecylsulfonyl)-1 -(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one, a linear polysiloxane co-polymer of (3-mercaptopropyl)-(methyl)dimethoxysilane, 3-(dodecylthio)-1 -(6-ethyl-2,6-dimethylcyclohex-3-en-1 -yl)butan-1-one, 2-(dodecylthio)octan-4-one, 2-(dodecylsulfonyl)octan-4-one, 4-oxooctan-2-yl dodecanoate, 2-phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1 -yl oxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1 -yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1 -yl) succinate, (2E,6Z)-2,6-nonadienyl hexadecanoate, (2E,6Z)-2,6-nonadien-1-yl tetradecanoate, (2E,6Z)-2,6-nonadien-1-yl dodecanoate, (2-((2-methylundec-1-en-1 -yl)oxy)ethyl)benzene, 1 -methoxy-4-(3-methyl-4-phenethoxybut-3-en-1 -yl)-benzene, (3-methyl-4-phenethoxybut-3-en-1 -yl)benzene, 1 -(((Z)-hex-3-en-1 -yl)oxy)-2-methylundec-1 -ene, (2-((2-methylundec-1 -en-1 -yl)oxy)ethoxy)benzene, 2-methyl-1 -(octan-3-yloxy)undec-1 -ene, 1 -methoxy-4-(1 -phenethoxyprop-1 -en-2-yl)benzene, 1 -methyl-4-(1 -phenethoxyprop- 1 -en-2-yl)benzene, 2-(1 -phenethoxy-prop-1 -en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1 -((3,7-dimethyloct-6-en-1 -yl)oxy)prop-1 -en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)-ethyl)benzene, 4-allyl-2-methoxy-1 -((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1 -methoxy-4-(1 -phenethoxy-prop-1 -en-2-yl)benzene, (2-((2-methyl-4-(2,6,6-trimethylcyclohex-1 -en-1 -yl)but-1 -en-1 -yl)oxy)ethyl)benzene, 1 -methoxy-4-(2-methyl-3-phenethoxyallyl)benzene, (2-((2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene, 1 -isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentyl-cyclopentylidene)methoxy)-4-propylbenzene, 2-ethoxy-1-((2-methoxy-2-phenyl-vinyl)oxy)-4-methylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)-benzaldehyde, 1 -isopropyl-2-((2-methoxy-2-phenylvinyl)oxy)-4-methylbenzene, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or a mixture thereof.

[0103] By “perfumery adjuvant”, it is meant here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfuming composition cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art. One may cite as specific non-limiting examples the following: viscosity agents (e.g. surfactants, thickeners, gelling and / or rheology modifiers), stabilizing agents (e.g. preservatives, antioxidant, heat / light and or buffers or chelating agents, such as BHT (=3,5-Di-tert-butyl-4-hydroxytoluene)), coloring agents (e.g. dyes and / or pigments), preservatives (e.g. antibacterial or antimicrobial or antifungal or anti irritant agents), abrasives, skin cooling agents, fixatives, insect repellants, ointments, vitamins and mixtures thereof.

[0104] By “fixative” also called “modulator”, it is understood here an agent having the capacity to affect the manner in which the odor, and in particular the evaporation rate and intensity, of the compositions incorporating said modulator can be perceived by an observer or user thereof, over time, as compared to the same perception in the absence of the modulator. In particular, the modulator allows prolonging the time during which their fragrance is perceived. Non-limiting examples of suitable modulators may include methyl glucoside polyol; ethyl glucoside polyol; propyl glucoside polyol; isocetyl alcohol; PPG-3 myristyl ether;neopentyl glycol diethylhexanoate; sucrose laurate; sucrose dilaurate, sucrose myristate, sucrose palmitate, sucrose stearate, sucrose distearate, sucrose tristearate, hyaluronic acid disaccharide sodium salt, sodium hyaluronate, propylene glycol propyl ether; dicetyl ether; polyglycerin-4 ethers; isoceteth-5; isoceteth-7, isoceteth-10; isoceteth-12; isoceteth-15; isoceteth-20; isoceteth-25; isoceteth-30; disodium lauroamphodipropionate; hexaethylene glycol monododecyl ether; and their mixtures; neopentyl glycol diisononanoate; cetearyl ethylhexanoate; panthenol ethyl ether, DL-panthenol, n-hexadecyl n-nonanoate, n-octadecyl n-nonanoate, a profragrance, cyclodextrin, an encapsulation, and a combination thereof. Typically, at most 20% by weight, based on the total weight of the perfuming composition, of the modulator may be incorporated into the perfumed consumer product.

[0105] It is understood that a person skilled in the art is perfectly able to design optimal formulations for the desired effect by admixing the above mentioned components of a perfuming composition, simply by applying the standard knowledge of the art as well as by trial and error methodologies.

[0106] According to a particular embodiment, the perfuming composition is in the form of a microcapsule, preferably a microcapsule slurry, comprising at least one compound of formula (I) and / or (II) and / or (II). In one embodiment, the at least one compound of formula (I) and / or (II) and / or (III) is encapsulated in a core-shell microcapsule wherein the at least one compound of formula (I) and / or (II) and / or (III) is contained in the core surrounded by the shell. In one embodiment, the shell of the microcapsule protects the compound of formula (I) and / or (II) and / or (III) from the environment. The shell is made of material which is able to release the at least one compound of formula (I) and / or (II) and / or (III). In one embodiment, the shell is made of material which is able to release the compound of formula (I) and / or (II) and / or (III) upon breakage of the shell and / or by diffusion through the shell. A person skilled in the art is well aware of processes to prepare said microcapsules. The core of the core-shell microcapsule, in addition to compound of formula (I) and / or (II) and / or (III), may further comprise at least one liquid carrier as defined above and / or at least one perfuming co-ingredient as defined above. The core-shell microcapsules or the core-shell microcapsule slurry comprising at least one compound of formula (I) and / or (II) and / or (III) may be dispersed into atleast one liquid carrier as defined above. Said liquid carrier may further comprise at least one compound of formula (I) and / or (II) and / or (III) and / or at least one perfuming co-ingredient as defined above.

[0107] According to a particular embodiment, the shell of the microcapsule comprises a material selected from the group consisting of polyurea, polyurethane, polyamide, polyester, poly(meth)acrylate (i.e. polyacrylate and / or polymethacrylate), polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal and mixtures thereof. The shell can also be hybrid, namely organic-inorganic such as a hybrid shell composed of at least two types of inorganic particles that are cross-linked, or yet a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macro-monomeric composition.

[0108] According to a particular embodiment, the core-shell microcapsule(s) can be also derived by using different or more than one encapsulation method.

[0109] In a preferred embodiment, the shell of the microcapsules may be, each independently, selected from the group of am inoplast, polyamide, polyester, polyurea and polyurethane shells and mixtures thereof.

[0110] In a particular embodiment, the shell of the microcapsules comprise an am inoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine formaldehyde or melamine glyoxal.

[0111] In a particular embodiment, the shell of the microcapsules is polyurea-based made from, for example but not limited to, isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules comprise a polyurea wall which is the reaction product of the polymerization between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (for example a water-soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated perfume.

[0112] However, the use of an amine can be omitted.

[0113] In a particular embodiment, the colloidal stabilizer includes an aqueous solution of between 0.1% and 0.4% of polyvinyl alcohol, between 0.6% and 1% of a cationic copolymer of vinylpyrrolidone and of a quaternized vinylimidazole (all percentages being defined by weight relative to the total weight of the colloidal stabilizer). In a particular embodiment, the emulsifier is an anionic or amphiphilicbiopolymer, which may be for example chosen from the group consisting of Gum Arabic, soy protein, gelatin, sodium caseinate and mixtures thereof.

[0114] In a particular embodiment, the shell of the microcapsules is polyurethane-based made from, for example but not limited to, polyisocyanate and polyols, polyamide, polyester, etc.

[0115] In a particular embodiment, the microcapsules have a polymeric shell resulting from complex coacervation wherein the shell is possibly cross-linked.

[0116] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsules comprise an oil-based core comprising a hydrophobic active, preferably at least one compound of formula (I) and / or (II) and / or (III), and a composite shell comprising a first material and a second material, wherein the first material and the second material are different, the first material is a coacervate, the second material is a polymeric material.

[0117] In a particular embodiment, the weight ratio between the first material and the second material is comprised between 50:50 and 99.9:0.1.

[0118] In a particular embodiment, the coacervate comprises a first polyelectrolyte, preferably selected among proteins (such as gelatin), polypeptides or polysaccharides (such as chitosan), most preferably gelatin, and a second polyelectrolyte, preferably alginate salts, cellulose derivatives, guar gum, pectinate salts, carrageenan, polyacrylic and methacrylic acid or xanthan gum, or yet plant gums such as acacia gum (Gum Arabic), most preferably Gum Arabic.

[0119] The first coacervate material can be hardened chemically using a suitable cross-linker such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin or can be hardened enzymatically using an enzyme such as transglutaminase.

[0120] The second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount less than 3 wt.%, preferably less than 1 wt.% based on the total weight of the microcapsule slurry.

[0121] The preparation of an aqueous dispersion / slurry of core-shell microcapsules is well known by a skilled person in the art. In a particular embodiment, the microcapsule wall material may comprise any suitable resin and especiallyincluding melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include the reaction product of an aldehyde and an amine, suitable aldehydes include, formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include, methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof. Suitable urea include, dimethylol urea, methylated dimethylol urea, urea-resorcinol, and mixtures thereof. Suitable materials for making may be obtained from one or more of the following companies Solutia Inc. (St Louis, Missouri U.S.A.), Cytec Industries (West Paterson, New Jersey U.S.A.), Sigma-Aldrich (St. Louis, Missouri U.S.A.).

[0122] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsules comprise

[0123] an oil-based core comprising a hydrophobic active, preferably comprising at least one compound of formula (I) and / or (II) and / or (III),

[0124] optionally an inner shell made of a polymerized polyfunctional monomer; a biopolymer shell comprising a protein, wherein at least one protein is cross-linked.

[0125] According to a particular embodiment, the protein is chosen from the group consisting of milk proteins, caseinate salts such as sodium caseinate or calcium caseinate, casein, whey protein, hydrolyzed proteins, gelatins, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate.

[0126] According to a particular embodiment, the protein comprises sodium caseinate and a globular protein, preferably chosen from the group consisting of whey protein, beta-lactoglobulin, ovalbumine, bovine serum albumin, vegetable proteins, and mixtures thereof.

[0127] The protein is preferably a mixture of sodium caseinate and whey protein. According to a particular embodiment, the biopolymer shell comprises a crosslinked protein chosen from the group consisting of sodium caseinate and / or whey protein.

[0128] According to a particular embodiment, the microcapsule slurry comprises at least one microcapsule made of:

[0129] an oil-based core comprising the hydrophobic active, preferably comprising at least one compound of formula (I) and / or (II) and / or (III);an inner shell made of a polymerized polyfunctional monomer; preferably a polyisocyanate having at least two isocyanate functional groups;

[0130] a biopolymer shell comprising a protein, wherein at least one protein is cross-linked; wherein the protein contains preferably a mixture comprising sodium caseinate and a globular protein, preferably whey protein; optionally at least an outer mineral layer.

[0131] According to an embodiment, sodium caseinate and / or whey protein is (are) cross-linked protein(s).

[0132] The weight ratio between sodium caseinate and whey protein is preferably comprised between 0.01 and 100, preferably between 0.1 and 10, more preferably between 0.2 and 5.

[0133] In a particular embodiment, the microcapsule is a one-shell aminoplast core-shell microcapsule obtainable by a process comprising the steps of:

[0134] 1 ) admixing a perfume oil with at least a polyisocyanate having at least two isocyanate functional groups to form an oil phase;

[0135] 2) dispersing or dissolving into water an aminoplast resin and optionally a stabilizer to form a water phase;

[0136] 3) preparing an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 100 microns, by admixing the oil phase and the water phase;

[0137] 4) performing a curing step to form the wall of said microcapsule; and

[0138] 5) optionally drying the final dispersion to obtain the dried core-shell microcapsule.

[0139] In a particular embodiment, the core-shell microcapsule is a formaldehyde-free capsule. A typical process for the preparation of an aminoplast formaldehyde-free microcapsule slurry comprises the steps of

[0140] T) preparing an oligomeric composition comprising the reaction product of, or obtainable by reacting together:

[0141] a’, a polyamine component in the form of melamine or of a mixture of melamine and at least one C1-C4 compound comprising two NH2 functional groups;b’. an aldehyde component in the form of a mixture of glyoxal, a C4-62,2- dialkoxy-ethanal and optionally a glyoxalate, said mixture having a molar ratio glyoxal / C4-62,2-dialkoxy-ethanal comprised between 1 / 1 and10 / 1; and

[0142] c’. a protic acid catalyst;

[0143] 2’) preparing an oil-in-water dispersion, wherein the droplet size is comprised between 1 and 600 microns, and comprising:

[0144] a”, an oil;

[0145] b”. a water medium;

[0146] c”. at least an oligomeric composition as obtained in step T;

[0147] d”. at least a cross-linker selected amongst:

[0148] i”. C4-C12 aromatic or aliphatic di- or tri-isocyanates and their biurets, triurets, trimmers, trimethylol propane-adduct and mixtures thereof; and / or

[0149] ii”. a di- or tri-oxiran compound of formula:

[0150] Q-(oxiran-2-ylrnethyl)m

[0151] wherein m is 2 or 3 and Q represents a C2-C6 group optionally comprising from 2 to 6 nitrogen and / or oxygen atoms;

[0152] e”. optionally a C1-C4 compounds comprising two NH2 functional groups; 3’) heating the dispersion; and

[0153] 4’) cooling the dispersion.

[0154] The above process is described in more detail in WO 2013 / 068255.

[0155] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsule is a polyamide core-shell microcapsule comprising:

[0156] an oil-based core comprising an hydrophobic active, preferably comprising at least one compound of formula (I) and / or (II) and / or (III), and

[0157] a polyamide shell comprising or being obtainable from:

[0158] • an acyl chloride,

[0159] • a first amino compound, and

[0160] • a second amino compound.

[0161] According to a particular embodiment, the polyamide core-shell microcapsule comprises:- an oil-based core comprising an hydrophobic active, preferably comprising at least one compound of formula (I) and / or (II) and / or (III), and

[0162] - a polyamide shell comprising or being obtainable from:

[0163] • an acyl chloride, preferably in an amount comprised between 5 and 98%, preferably between 20 and 98%, more preferably between 30 and 85% w / w;

[0164] • a first amino compound, preferably in an amount comprised between 1 % and 50% w / w, preferably between 7 and 40% w / w;

[0165] • a second amino compound, preferably in an amount comprised between 1 % and 50% w / w, preferably between 2 and 25% w / w;

[0166] • a stabilizer, preferably a biopolymer, preferably in an amount comprised between 0 and 90%, preferably between 0.1 and 75%, more preferably between 1 and 70%.

[0167] According to a particular embodiment, the polyamide core-shell microcapsule comprises:

[0168] an oil-based core comprising a hydrophobic active, preferably comprising at least one compound of formula (I) and / or (II) and / or (III), and

[0169] a polyamide shell comprising or being obtainable from:

[0170] • an acyl chloride,

[0171] • a first amino-compound being an amino-acid, preferably chosen from the group consisting of L-Lysine, L-Arginine, L-Histidine, L-Tryptophane and / or a mixture thereof.

[0172] • a second amino. compound chosen from the group consisting of ethylene diamine, diethylene triamine, cystamine and / or a mixture thereof, and

[0173] • a biopolymer chosen from the group consisting of casein, sodium caseinate, bovin serum albumin, whey protein, and / or a mixture thereof.

[0174] The first amino-compound can be different from the second aminocompound.

[0175] Typically, a process for preparing a polyamide-based microcapsule includes the following steps:a) dissolving at least one acyl chloride in a hydrophobic material, preferably a perfume to form an oil phase;

[0176] b) dispersing the oil phase obtained in step a) into a water phase comprising a first amino compound to form an oil-in water emulsion;

[0177] c) performing a curing step to form polyamide microcapsules in the form of a slurry;

[0178] wherein a stabilizer is added in the oil phase and / or in the water phase, and wherein at least a second amino-compound is added in the water phase before the formation of the oil-in-water emulsion and / or in the oil-in water emulsion obtained after step b).

[0179] In a particular embodiment, the shell of the microcapsule is polyurea-or polyurethane-based. Examples of processes for the preparation of polyurea and polyureathane-based microcapsule slurries are for instance described in WO 2007 / 004166, EP 2300146, and EP 2579976. Typically, a process for the preparation of polyurea or polyurethane-based microcapsule slurries include the following steps:

[0180] a) dissolving at least one polyisocyanate having at least two isocyanate groups in an oil to form an oil phase;

[0181] b) preparing an aqueous solution of an emulsifier or colloidal stabilizer to form a water phase;

[0182] c) adding the oil phase to the water phase to form an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 500 pm, preferably between 5 and 50 pm; and

[0183] d) applying conditions sufficient to induce interfacial polymerization and form microcapsules in form of a slurry.

[0184] In a particular embodiment, the microcapsule can be in form of a powder, which in particular may be obtained by submitting the microcapsule slurry to a drying step, like spray-drying, to provide the microcapsules as such, i.e. in a powdery form. It is understood that any standard method known by a person skilled in the art to perform such drying is also applicable. In particular the slurry may be spray-dried, preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, gum Arabic, vegetable gums, pectins, xanthans, alginates, carrageenans or cellulose derivatives to provide microcapsules in a powder form.However, one may also cite other drying methods such as extrusion, plating, spray granulation or fluidized bed processes, or even drying at room temperature using materials (carrier, desiccant) that meet specific criteria as disclosed in WO 2017 / 134179.

[0185] According to a particular embodiment, the compositions mentioned above, comprise more than one compound of formula (I) and / or (II) and / or (III) and enable the perfumer to prepare accords or perfumes possessing the odor tonality of various compounds of the invention, creating thus new building block for creation purposes.

[0186] For the sake of clarity, it is also understood that any mixture resulting directly from a chemical synthesis, e.g. a reaction medium without an adequate purification, in which the compound of the invention would be involved as a starting, intermediate or end-product could not be considered as a perfuming composition according to the invention as far as said mixture does not provide the inventive compound in a suitable form for perfumery. Thus, unpurified reaction mixtures are generally excluded from the present invention unless otherwise specified.

[0187] The invention’s compound can also be advantageously used in all the fields of modem perfumery, i.e. fine or functional perfumery, to positively impart or modify the odor of a consumer product into which said compound (I) and / or (II) and / or (III) is added.

[0188] Consequently, another object of the present invention consists of a perfumed consumer product comprising,

[0189] at least one compound of formula (I) as described above in great details; or at least one compound of formula (III) as described above in great details; or a composition comprising at least one aldehyde of the compound of the formula (II) and at least one compound of the formula (I) as described above in great details; or

[0190] a composition comprising at least one aldehyde of the compound of the formula (II) and at least one compound of the formula (III) as described above in great details; or

[0191] a perfuming composition as described above in great details.

[0192] The invention’s compound can be added as such or as part of an invention’s perfuming composition.In a preferred embodiment, said composition is a perfume or fragrance composition.

[0193] In another preferred embodiment, said perfuming composition is a composition of daily use, particularly a cosmetic product or a grooming, fabric or home care product.

[0194] For the sake of clarity, “perfumed consumer product” is meant to designate a consumer product which delivers at least a pleasant perfuming effect to the surface or space to which it is applied (e.g. skin, hair, textile, or home surface). In other words, a perfumed consumer product according to the invention is a perfumed consumer product which comprises a functional formulation, as well as optionally additional benefit agents, corresponding to the desired consumer product, and an olfactive effective amount of at least one invention’s compound. For the sake of clarity, said perfumed consumer product is a non-edible product.

[0195] The nature and type of the constituents of the perfumed consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of said product.

[0196] Non-limiting examples of suitable perfumed consumer products include a perfume, such as a fine perfume, a splash or eau de parfum, a cologne or a shave or after-shave lotion; a fabric care product, such as a liquid or solid detergent optionally in the form of a pod or tablet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product; a body-care product, such as a hair care product (e.g. a shampoo, a leave-on or rinse-off hair conditioner, a coloring preparation or a hair spray, a color-care product, a hair shaping product, a dental care product), a disinfectant, an intimate care product; a cosmetic preparation (e.g. a skin cream or lotion, a vanishing cream or a deodorant or antiperspirant (e.g. a spray or roll on), a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup); or a skin-care product (e.g. a soap, a shower or bath mousse, oil or gel, or a hygiene product or a foot / hand care products); an air care product, such as an air freshener or a “ready to use” powdered air freshener which can be used in the home space (rooms,refrigerators, cupboards, shoes or car) and / or in a public space (halls, hotels, malls, etc..); or a grooming, fabric or home care product, such as a mold remover, a furnisher care product, a wipe, a dish detergent or a hard-surface (e.g. a floor, bath, sanitary or a window-cleaning) detergent, a laundry product, a fabric washing powder, a fabric washing gel, a soluble laundry sheet; a leather care product; a car care product, such as a polish, a wax or a plastic cleaner.

[0197] According to any embodiments of the invention, the perfumed consumer product of the invention is characterized by a pH of 1 or more. Particularly, the perfumed consumer product of the invention has a pH comprised between 1 and 12, or between 1 and 8. Even more particularly, the perfumed consumer product of the invention has a pH comprised between 1 and 6.

[0198] According to a particular embodiment, the invention’s perfumed consumer product is in the form of a personal care, a home care or fabric care consumer product comprising ingredients that are common in personal, home or fabric care consumer products, in particular shower gels, shampoos, soaps, fabric detergents or softeners and all-purpose cleaners. The main functional constituents of perfumed consumer products are surfactants and / or softener components capable of cleaning and / or softening fabrics and / or textiles of varied nature, such as clothes, curtain fabrics, carpets and furniture fabrics, etc. or other home surfaces, skin or hair, and typically used in a large amount of water or water-based solvents. These are therefore formulations wherein the amount of water is typically comprised between 50 and 99% by weight of the perfumed consumer product with the exception of soaps or solid detergents wherein the amount of water is at most 20%.

[0199] A more detailed description of such fabric cleaning and / or softening formulations is not warranted here, many descriptions of current liquid formulations can be found in the cleaner / fabric softener’s patent and other pertinent literature, such as for example the textbook of Louis Ho Tan Tai, “Detergents et Produits de Soins Corporals, Chapters 1 to 7 in particular, Dunod, Paris, 1999, or any other similar and / or more recent textbooks pertaining to the art of liquid softener and all-purpose cleaners formulations. A patent publication, WO 2010 / 105873, is also cited byway of example, in as much as it describes typical currant ingredients, other than perfumes, of such liquid products, particularly in pages 9 to 21. Of course, many other examples of liquid cleaner and / or fabricsoftener formulations can be found in the literature. Any such liquid formulations, namely liquid fabric cleaners or conditioners and / or all-purpose cleaners, can be used in the here-described compositions.

[0200] According to a particular embodiment of the invention, the invention’s perfumed consumer product is a liquid fabric softener comprising a fabric softener active base in amount comprised between 85 and 100% by weight, based on the total weight of the perfumed consumer product. The main constituent of the fabric softener active base is water or water-based solvents. The fabric softener active base may comprise dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts, Hamburg esterquat, triethanolamine quat, silicones and mixtures thereof. Optionally, the fabric softener active base of the composition may further comprise a viscosity modifier in an amount comprised between 0.05 and 1% by weight, based on the total weight of the liquid base; preferably chosen in the group consisting of calcium chloride.

[0201] According to a particular embodiment of the invention, the invention’s perfumed consumer product is an all-purpose cleaner comprising an all-purpose cleaner active base in amount comprised between 85 and 100% by weight, based on the total weight of the perfumed consumer product. The main constituent of the all-purpose cleaner active base is water or water-based solvents The all-purpose active base may comprise linear alkylbenzene sulfonates (LAS) in an amount comprised between 1 and 2%, nonionic surfactant in an amount comprised between 2 and 4% and acid such as citric acid in an amount comprised between 0.1 and 0.5%.

[0202] According to a particular embodiment of the invention, the invention’s perfumed consumer product is a liquid detergent comprising a liquid detergent active base in amount comprised between 85 and 100% by weight, based on the total weight of the perfumed consumer product. The main constituent of the liquid detergent active base is water or water-based solvents. The liquid detergent active base may comprise anionic surfactant such as alkylbenzenesulfonate (ABS), linear alkylbenzene sulfonates (LAS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), sodium lauryl ether sulfate (SLES), methyl ester sulfonate (MES); nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol poly(ethylene glycol) ether, fatty alcohol ethoxylate(FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides; ormixtures thereof.

[0203] According to a particular embodiment of the invention, the invention’s perfumed consumer product is a solid detergent comprising a solid detergent active base in amount comprised between 85 and 100% by weight, based on the total weight of the perfumed consumer product. The solid detergent active base may comprise at least one surfactant chosen in the group consisting of anionic, nonionic, cationic, zwitterionic surfactant and mixtures thereof. The surfactant in the solid detergent active base is preferably chosen in the group consisting of linear alkene benzene sulfonate (LABS), sodium laureth sulphate, sodium lauryl ether sulfate (SLES), sodium lauryl sulfate (SLS), alpha olefin sulfonate (AOS), methyl ester sulfonates (MES), alkyl polyglyucosides (APG), primary alcohol ethoxylates and in particular lauryl alcohol ethoxylates (LAE), primary alcohol sulphonates (PAS), soap and mixtures thereof. The soild detergent active base may comprise a further component, commonly used in powder detergent consumer product, selected from the group consisting of bleaching agents such as TAED (tetraacetylethylenediamine); buffering agent; builders such as zeolites, sodium carbonate or mixture thereof; soil release or soil suspension polymers; granulated enzyme particles such as cellulase, lipase, protease, mannanase, pectinase or mixtures thereof; corrosion inhibitor; antifoaming; sud suppressing agents; dyes; fillers such as sodium silicate, sodium sulfate or mixture thereof; source of hydrogen peroxide such as sodium percarbonate or sodium perborate; and mixtures thereof.

[0204] According to a particular embodiment of the invention, the invention’s perfumed consumer product is shampoo or a shower gel comprising a shampoo or shower gel active base in amount comprised between 85 and 100% by weight, based on the total weight of the perfumed consumer product. The main constituent of the shampoo or a shower gel active base is water or water-based solvents The shampoo shower gel active base may comprise sodium alkylether sulfate, ammonium alkylether sulfates, alkylamphoacetate, cocam idopropyl betaine, cocamide MEA, alkylglucosides and aminoacid based surfactants.

[0205] According to a particular embodiment of the invention, the invention’s perfumed consumer product is a soap bar comprising a soap active base in amount comprised between 85 and 100% by weight, based on the total weight ofthe perfumed consumer product. The soap bar active base may comprise salt of a weak acid, typically, a salt of weak acid, which may be a fatty acid and strong base like sodium hydroxide.

[0206] Some of the above-mentioned perfumed consumer products may represent an aggressive medium for the invention’s compounds, so that it may be necessary to protect the latter from premature decomposition, for example by encapsulation or by chemically binding it to another chemical which is suitable to release the invention’s ingredient upon a suitable external stimulus, such as an enzyme, light, heat or a change of pH.

[0207] The proportions in which the compounds according to the invention can be incorporated into the various aforementioned products or compositions vary within a wide range of values. These values are dependent on the nature of the article to be perfumed and on the desired organoleptic effect as well as on the nature of the co-ingredients in a given base when the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.

[0208] For example, in the case of perfuming compositions, typical concentrations are in the order of 0.001 % to 10 % by weight, or even more, of the compounds of the invention based on the weight of the composition into which they are incorporated. In the case of perfumed consumer product, typical concentrations are in the order of 0.01 % to 1 % by weight, or even more, of the compounds of the invention based on the weight of the consumer product into which they are incorporated.

[0209] Therefore, the perfumed consumer product is preferably a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

[0210] More preferably, the perfumed consumer product is a fine perfume, a splash or eau de parfum, a cologne, a shave or after-shave lotion, a liquid or solid detergent optionally in the form of a pod or tablet, a laundry sheet, a soluble laundry sheet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtaincare product, a shampoo, a leave-on or rinse-off hair conditioner, a coloring preparation, a color-care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, skin cream or lotion, avanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, oil or gel, a foot / hand care product, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard-surface detergent, a leather care product, a car care product

[0211] As pointed out above, the compound of the formula (I) and of formula (III) has a typical and natural odor of almonds.

[0212] Therefore, in a further aspect, the present invention relates also to the use of the formula (I) or compound of the formula (III) to impart an almond odor to a composition.

[0213] As pointed out, above the composition comprising at least one aldehyde of the formula (II) and at least one compound of the formula (I) and / or at least one compound of the formula (III) provides a very unique and harmonic impression completing the olfactory characteristic of aldehyde of formula (II) with the almond component of compound of the formula (I) and / or (III).

[0214] Therefore, in a further aspect, the present invention relates also to the use of said composition to impart a balanced mixture of floral, green, aldehydic and strong almond notes to a composition

[0215] Furthermore, in a further aspect, the present invention relates to a method to confer or enhance or improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I), as described above in great details, and / or at least a compound of the formula (III), as described above in great details, or a composition comprising at least one aldehyde of the compound of the formula (II) and at least one a compound of formula (I) and / or (III), as described above in great details.

[0216] Examples

[0217] The following examples are provided to further illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.Synthesis of 1-[(1E, Z,4E, Z)-5-ethoxy-2,4-dimethyl-penta-1 ,4-dienyl]-4- of the formula

[0218] step a) synthesis of 1-[(E, Z)-5,5-diethoxy-2,4-dimethyl-pent-1-enyl]-4-methyl- benzene (compound of formula (lll-A))

[0219] In a 500 ml round bottomed flask, equipped with a distillation device, were charged p-toluene-sulfonic acid (0.47 g, 2.5 mmol), (E,Z)-2,4-dimethyl-5-(p- tolyl)pent-4-enal (50 g, 245 mmol) (ratio E / Z = 80 / 20) and ethanol (175 g). This solution was stirred and heated at 100°C until wet ethanol distilled slowly.

[0220] Distillation of ethanol was realized for a period of 12h; during this period some more ethanol (125 g) was added and distilled. Reaction mixture was cooled down to 25°C and was quenched with sodium ethylate (21% solution in ethanol) until pH reached 12. Toluene (65 g) was added followed by water (60 g). After decantation, phases were separated. Organic phase was washed twice with water and evaporated down to yield crude 1-[(E,Z)-5,5-diethoxy-2,4-dimethyl-pent-1-enyl]-4- methylbenzene (72 g) which was purified by distillation under reduced pressure (56.7 g, 83% yield, ratio E / Z = 80 / 20).

[0221] step b) synthesis of 1-[(1E, Z,4E, Z)-5-ethoxy-2,4-dimethyl-penta-1,4-dienyl]-4- methylbenzene (compound of formula (I- A))

[0222] In a 50 ml round bottomed flask, equipped with a distillation device, were charged sodium p-toluene-sulfonate (0.76 g, 3.9 mmol) and 1-[(E, Z)-5,5-diethoxy- 2,4-dimethyl-pent-1-enyl]-4-methylbenzene (25.1 g, 95.3%, 86.5 mmol) (ratio E / Z = 80 / 20) (produced by above step a). This suspension was stirred and heated up to 100-120°C until ethanol distilled slowly. When distillation of ethanol ceased, pressure was lowered regularly down to 25 mbar to continue the distillation. Crude 1-[(1 E,Z,4E,Z)-5-ethoxy-2,4-dimethyl-penta-1 ,4-dienyl]-4-methylbenzene) was purified by distillation under reduced pressure (18.2 g, 91% yield, ratio E / Z = 80 / 20).

[0223]

[0224] >

[0225] The compounds or compositions according to table 1 have been prepared and applied on a paper smelling strip and characterized by a professional and experienced perfumer. This characterization has been compiled in table 1.

[0226]

[0227] Example 7: Preparation of a perfuming composition

[0228] AA cologne, of the floral-watery type, was prepared by admixing the following ingredients:

[0229] Ingredient Parts by weight 10%* Phenylacetic aldehyde 20

[0230] 16-Hexadecanolide 40

[0231] Dihydro Beta Ionone 350

[0232] 7-Methyl-2H,4H-1 ,5-benzodioxepin-3-one 80 Citronellol 300

[0233] Allyl (cyclohexyloxy)-acetate 20

[0234] Decal 20

[0235] 2,6-dimethyl-2-heptanol 2010%* Ethy I van i 11 ine 100 Eugenol 80 pentadecanolide 360 70%** 1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl- cyclopenta-g-2-benzopyrane 2200 methyl dihydrojasmonate 1000 10%* lndol 150 Beta Ionone 20 1 -(octahydro-2, 3, 8, 8-tetramethyl-2-naphtalenyl)

[0236] -1 -ethanone 1300 3-(4-tert-butylphenyl)-2-methylpropanal 1150 Linalool 270 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene- 1-carbaldehyde 250 10%* 2,6-Dimethyl-5-heptanal 50 (+)-methyl (1 R)-cis-3-oxo-2-pentyl-1 - cyclopentaneacetate 100 Phenethylol 70 10%* 2,4-Dimethyl-3-cyclohexene-1 -carbaldehyde 50 Composition of Example 4 300

[0237] 8300 * in dipropyleneglycol

[0238] ** in isopropyle myristate

Claims

ClaimswhereinR represents either H or a Ci-w-alkyl group; preferably a methyl group; R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

2. The compound of the formula (I) according to claim 1 , characterized in that R represents a methyl group and R1represents an ethyl group.

3. A composition comprising at least one aldehyde of the compound of the formula (II) and at least one compound of the formula (I)R represents either H or a Ci-w-alkyl group; preferably a methyl group; R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

4. A composition comprising at least one aldehyde of the compound of the formula (II) and at least one compound of the formula (III)whereinR represents either H or a Ci- -alkyl group; preferably a methyl group;R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the Econfiguration.

5. The composition according to claim 3 or 4, characterized in that the molar ratio of the compound of the formula (II) to the compound of the formula (I) or (III) is in the range of 99:1 to 50:50, preferably of 99:1 to 80: 20, more preferably of 99.1 to 90: 10.6 The composition according to any of the preceding claims 3 or 4 or 5, characterized in that the composition comprises a mixture of the compound of formula (ll-E) and (ll-Z)7. The composition according to any of the preceding claims 3 to 6, characterized in that the molar ratio of the compound of the formula ( I l-E) to the compound of the formula (I l-Z) is in the range of 99:1 to 50:50, preferably of 95:5 to 60:40, more preferably of 95:5 to 70:30.

8. A process of preparing the compound of the formula (I) comprising the steps a) acetalization of the aldehyde of the formula (II) by an alcohol of formula R1OH to yield a compound of the formula (III)b) transforming the acetal of the formula (III) to the compound of the formula (I);whereinR represents either H or a Ci-w-alkyl group; preferably a methyl group;R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

9. A compound of the formula (III)whereinR represents either H or a Ci- -alkyl group; preferably a methyl group;R1represents a Ci-w-alkyl group; preferably a methyl or ethyl group; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

10. A perfuming composition comprisingi) at least the compound of formula (I) according to any of the preceding claims 1 to 2; or a compound of the formula (III) according to claim 9 or a composition according to any of the preceding claims 3 to 7; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; andiii) optionally at least one perfumery adjuvant.

11. The perfuming composition according to claim 10, characterized in that the composition is a composition of daily use, particularly a cosmetic product or a grooming, fabric or home care product.

12. A perfumed consumer product comprisingat least one compound of formula (I) according to any of the preceding claims 1 to 2, oror a compound of the formula (III) according of claim 9a composition according to any of the preceding claims 3 to 7; ora perfuming composition according to claim 10 or 11.

13. The perfumed consumer product according to claim 12, characterized in that the perfumed consumer product is a perfume, a fabric care product, a bodycare product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

14. The perfumed consumer product according to claim 12 or 13, characterized in that the perfumed consumer product is a fine perfume, a splash or eau de parfum, a cologne, a shave or after-shave lotion, a liquid or solid detergent optionally in the form of a pod or tablet, a laundry sheet, a soluble laundry sheet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtaincare product, a shampoo, a leave-on or rinse-off hair conditioner, a coloring preparation, a color-care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, skin cream or lotion, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, oil or gel, a foot / hand care product, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard-surface detergent, a leather care product, a car care product.

15. The use of the compound of the formula (I) according to claim 1 or 2 or compound of formula (III) according to claim 9 to impart an almond odor to a composition.

16. The use of the composition according to any of the preceding claims 3 to 7 to impart a balanced mixture of floral, green, aldehydic and strong almond notes to a composition.

17. A method to confer or enhance or improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I) according to claim 1 or 2 or of formula (III) according to claim 9 or a composition according to any of the claims 3 to 7.

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