Odor compounds

Abstract

The present invention relates to the field of perfume precursors. More specifically, the present invention relates to a compound of formula (I) as defined herein and its use as a perfuming ingredient. Thus, according to the present disclosure, the present invention comprises the compound of the present invention as part of a perfume composition or a perfumed consumer product. Furthermore, the present invention relates to a perfume precursor compound suitable for releasing the compound of formula (I).

Description

[Technical Field]

[0001] Technical Field The present invention relates to the field of perfumery. More specifically, the present invention relates to a compound of formula (I) as defined herein below, and its use as a perfuming ingredient. Thus, according to the content described herein, the present invention comprises the compound of the present invention as part of a perfuming composition or a perfumed consumer product. Furthermore, the present invention relates to a perfume precursor compound suitable for releasing the compound of formula (I).

[0002] Background of the Invention In the perfume industry there is a constant need to provide compounds that impart new organoleptic notes.

[0003] The present invention provides novel perfume ingredients of formula (I) that impart a lactone note and a green note, which have not been reported before.

[0004] To the best of our knowledge, the prior art reports several structural analogues as perfuming ingredients.

[0005] German Patent Application No. 2721002 reports 2,2,5-trimethyl-5-pentylcyclopentan-1-one, also known as Veloutone® (trademark of Firmenich SA, Switzerland), which is described as having a fruity odor. The compound reported in this document not only differs from the compounds of the present invention in terms of their chemical structure, but also in the organoleptic properties they impart.

[0006] Thus, none of these prior art documents reports or suggests the organoleptic properties of compounds of formula (I) or the use of said compounds in the perfumery field.

[0007] Description of the Invention Surprisingly, it has now been found that compounds of formula (I) have lactone and green notes which are particularly valued in perfumery.

[0008] A first subject of the present invention is a compound of formula [ka] [Wherein R is C 2~8 Alkenyl group or C 4~8 represents an alkadienyl group] in the form of any one of its stereoisomers or as a mixture thereof.

[0009] The above compounds can be used as perfuming ingredients to impart lactone-type odor notes with, for example, green nuances.

[0010] According to any one of the above embodiments of the present invention, the compound (I) is 10 ~C 16 Compounds, especially C 11 ~C 14 Compounds, and more specifically C 12 ~C 13 It is a compound.

[0011] For clarity, the expression "any one of its stereoisomers or a mixture thereof" or similar expressions has the usual meaning understood by those skilled in the art, i.e., that the compound of formula (I) may be a pure enantiomer (when optically active) or a diastereomer (e.g., a double bond in the E or Z configuration). In other words, the compound of formula (I) may have one or more stereocenters, and each of said stereocenters may have two different stereochemistries (e.g., R or S). The compound of formula (I) may be in the form of a pure enantiomer or in the form of a mixture of enantiomers or diastereomers. The compound of formula (I) may be in the form of a racemate or a scalemic mixture. Thus, the compound of formula (I) may be a single stereoisomer or in the form of a composition comprising or consisting of various stereoisomers.

[0012] According to any one of the above embodiments of the present invention, the compound may be in the form of its E or Z isomer, or a mixture thereof; for example, the present invention includes a composition consisting of one or more compounds of formula (I) having the same chemical structure but differing in the configuration of the double bond. In certain embodiments, compound (I) may be in the form of a mixture consisting of E and Z isomers, wherein the isomer E is at least 50%, or even at least 75%, of the total mixture (i.e., the mixture E / Z is composed of 75 / 25 to 100 / 0). In another specific embodiment, compound (I) may be in the form of a mixture consisting of E and Z isomers, wherein the isomer Z is at least 50%, or even at least 75%, of the total mixture (i.e., the mixture E / Z is composed of 25 / 75 to 0 / 100).

[0013] The term "alkenyl" or "alkadienyl" is understood to include branched and straight-chain alkenyl and alkadienyl groups, which are understood to contain one or two olefinic double bonds, respectively.

[0014] According to any one of the above embodiments of the present invention, R is C 2~8 In particular, R may be an alkenyl group. 2~6 Even more specifically, R can be a linear C 2~6 It may be an alkenyl group.

[0015] According to any embodiment of the present invention, the compound has the formula [ka] [wherein one dotted line represents a carbon-carbon double bond and the other dotted line represents a carbon-carbon single bond; R 1 is a hydrogen atom or C 1~2 represents an alkyl group] in the form of any one of its stereoisomers or as a mixture thereof.

[0016] For clarity, the phrase "one of the dotted lines represents a carbon-carbon single bond and the other dotted line represents a carbon-carbon single bond" or similar phrases means the ordinary meaning understood by a person skilled in the art, i.e., that all bonds (solid and dotted) between the carbon atoms connected by said dotted lines are carbon-carbon single or double bonds.

[0017] According to any embodiment of the present invention, R 1 represents a hydrogen atom or a methyl group.

[0018] Specific examples of compounds of the present invention include, but are not limited to, 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one, which imparts lactone, sage, and lavender notes.

[0019] Another example is 2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone, which has a similar odor to that mentioned above.

[0020] Other specific, non-limiting examples of compounds of the present invention include the following: [Table 1-1] [Table 1-2]

[0021] According to a particular embodiment of the present invention, the compound of formula (I) is 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one, 2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone, 2-[(1-buten-1-yl]-2,5,5-trimethylcyclopentanone, 2-[1-hexen-1-yl]-2,5,5-trimethylcyclopentanone, 2-allyl-2,5,5-trimethylcyclopentanone, 2-(5-hexen-1-yl)-2,5,5-trimethylcyclopentanone, 2-[3-hexen-1-yl]-2,5,5-trimethylcyclopentanone, 2-[4-hexen-1-yl]-2,5,5-trimethylcyclopentanone,

[0023] The compounds of formula (I) are 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentanone, 2-(hex-2-enyl)-2,5,5-trimethylcyclopentanone, and 2,2,5-trimethyl-5-(pent-2-enyl)cyclopentanone. In particular, the compound of formula (I) is 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one, 2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone, and 2,2,5-trimethyl-5-(pent-2-enyl)cyclopentanone. Even more specifically, the compound of formula (I) is 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one.

[0022] When the odor of the compounds of the present invention is compared with that of the prior art compound Veloutone®, the compounds of the present invention are distinguished by their distinctly strong aromatic sage and lavender notes and the lack of the fruity notes characteristic of the prior art compounds. The odor of the compounds of the present invention is also cleaner and more refreshing than that of the prior art compounds. These differences make the compounds of the present invention and the prior art compounds suitable for different applications, i.e., they provide different sensory impressions.

[0023] As mentioned above, the present invention relates to the use of compounds of formula (I) as perfuming ingredients. In other words, the present invention relates to a method or process for imparting, enhancing, improving or modifying the olfactory properties of a perfuming composition or a perfumed article or surface, which method comprises adding an effective amount of at least one compound of formula (I) to the composition or article, for example, to impart its typical note. The final hedonic effect may depend on the exact amount and organoleptic properties of the compounds of the present invention used, but it is understood that in any case, the addition of the compounds of the present invention will impart its typical feel to the final product in the form of a note, feel or aspect depending on the amount used.

[0024] "Use of a compound of formula (I)" in this specification must also be understood as the use of any composition containing compound (I) that can be advantageously used in the perfumery industry.

[0025] Such compositions, which may in fact be advantageously used as perfuming ingredients, are also an object of the present invention.

[0026] Therefore, another subject of the present invention is i) as perfuming ingredient, at least one compound of the invention as defined above; ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and iii) optionally at least one perfume adjuvant A perfume composition comprising:

[0027] By "perfume carrier" is meant herein a material that is substantially neutral from a perfumery point of view, i.e., that does not significantly alter the organoleptic properties of the perfuming ingredients. The carrier may be liquid or solid.

[0028] Liquid carriers can include, but are not limited to, emulsifying systems, i.e., solvents and surfactant systems, or solvents commonly used in perfumery.The detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive.But, but not limited to, solvents such as butylene glycol or propylene glycol, glycerol, dipropylene glycol and its monoether, 1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate or their mixtures are the most commonly used. In the case of compositions comprising both a perfume carrier and a perfume base, other suitable perfume carriers than those specified above may be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (manufactured by Exxon Chemical), or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (manufactured by Dow Chemical Company), or hydrogenated castor oil such as those known under the trademark Cremophor® RH 40 (manufactured by BASF).

[0029] Solid carrier refers to a material to which the perfume composition or some components of the perfume composition can be chemically or physically bound. Generally, such solid carriers are used to stabilize the composition or to control the evaporation rate of the composition or some components. Solid carriers are currently used in the art, and those skilled in the art know how to achieve the desired effect. However, non-limiting examples of solid carriers include absorbent gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, wood materials, organic or inorganic gels, clays, gypsum talc, or zeolites.

[0030] Other non-limiting examples of solid carriers can include encapsulating materials.Examples of such materials can include wall-forming and plasticizing materials, such as monosaccharides, disaccharides or trisaccharides, natural starch or modified starch, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, protein or pectin, or the materials cited in references such as H. Scherz, Hydrokolloides: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr's Verlag GmbH & Co., Hamburg, 1996.Encapsulation is a method well known to those skilled in the art, and can be carried out using techniques such as spray drying, coagulation or even extrusion; or consist of coating encapsulation, including coacervation and complex coacervation techniques.

[0031] Non-limiting examples of solid carriers include core-shell capsules comprising resins of the aminoplast, polyamide, polyester, polyurea or polyurethane type or mixtures thereof (all of the above resins are well known to those skilled in the art) using techniques such as polymerization, interfacial polymerization, coacervation or all of these induced phase separation processes, optionally in the presence of polymeric stabilizers or cationic copolymers.

[0032] The resins can be prepared by polycondensation of aldehydes (e.g., formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid, or glycolaldehyde, and mixtures thereof) with amines, such as urea, benzoguanamine, glycoluril, melamine, methylolmelamine, methylated methylolmelamine, guanazole, and mixtures thereof. Alternatively, preformed resinous alkylolated polyamines, such as those commercially available under the Urac® (manufactured by Cytec Technology Corp.), Cymel® (manufactured by Cytec Technology Corp.), Urecoll®, or Luracoll® (manufactured by BASF) trademarks, can be used.

[0033] Other resins are produced by polycondensation of polyols, such as glycerol, with polyisocyanates, such as the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate or xylylene diisocyanate, or the biuret of hexamethylene diisocyanate, or the trimer of xylylene diisocyanate with trimethylolpropane (known under the trade name Takenate®, manufactured by Mitsui Chemicals), with the trimer of xylylene diisocyanate with trimethylolpropane and the biuret of hexamethylene diisocyanate being preferred.

[0034] Some influential publications on the encapsulation of perfumes by polycondensation of amino resins, i.e., melamine-based resins, with aldehydes, include articles such as those published by K. Dietrich et al. in Acta Polymerica, Vol. 40, pp. 243, 325, and 683 (1989) and Vol. 41, p. 91 (1990). These articles already describe the various parameters affecting the production of such core-shell microcapsules according to prior art methods, which are further detailed and exemplified in the patent literature. U.S. Patent No. 4,396,670 to Wiggins Teape Group Limited is a good 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 the developments published here, but a general knowledge of encapsulation technology is very important. More recent relevant publications disclosing the suitable use of such microcapsules are represented, for example, by the article by K. Bruyninckx and M. Dusselier in ACS Sustainable Chemistry & Engineering, 2019, Vol. 7, pp. 8041-8054.

[0035] As meant herein, a "perfume base" is a composition that includes at least one perfuming co-ingredient.

[0036] The perfuming co-ingredient is not of formula (I). Furthermore, the term "perfuming co-ingredient" as used herein means a compound used in a perfuming preparation or composition to impart a hedonic effect. In other words, such a co-ingredient to be considered a perfuming ingredient must be recognized by those skilled in the art not simply as having an odor, but as being able to impart or modify the odor of the composition in a beneficial or pleasant way.

[0037] The nature and type of perfuming co-ingredients present in the base do not warrant a more detailed description herein, which is in any case not exhaustive and which the skilled person can select based on his general knowledge and according to the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming co-ingredients belong to various chemical classes such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocycles and essential oils, and said perfuming co-ingredients may be of natural or synthetic origin.

[0038] Mention may in particular be made of perfuming co-ingredients known to have similar olfactory notes, such as:

[0039] Mention may in particular be made of perfuming co-ingredients commonly used in perfume formulations, such as: - aldehyde components: decanal, dodecanal, 2-methyl-undecanal, 10-undecenal, octanal, nonanal and / or nonenal; - Aromatic-Herbal Ingredients: Eucalyptus Oil, Camphor, Eucalyptol, 5-Methyltricyclo[6.2.1.0 2,7 ]undecane-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; - Balsamic ingredients: coumarin, ethyl vanillin and / or vanillin; - 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; - Floral Ingredients: Methyl Dihydrojasmonate, Linalool, Citronellol, Phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, Hexyl Cinnamaldehyde, 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, (1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-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-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one, 2,5-dimethyl-2-indanethanol, 2,6,6-trimethyl-3-cyclohexen Cyclohexene-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, vermicelli acetate, geraniol, p-mentha-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis-methyldihydrodiphenyl ether Jasmonate, 3-methyl-5-phenyl-1-pentanol, vergyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, propyl (S)-2-(1,1-dimethylpropoxy)propanoate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamic aldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, vermicelli isobutyrate and / or a mixture of methyl ionone isomers; - Fruity ingredients: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanolide, ethyl 2-methylpentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, 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-cyclohexanedicarboxylate; - Green ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-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; - Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3-methyl-5-cyclopentadecanone entadecen-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-g-2-benzopyran, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, oxacyclohexadecan-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate; - Woody ingredients: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxirane-2,9'-tricyclo[6.2.1.0 2,7 ]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-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, Clearwood®, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopentene-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; Other ingredients (e.g., amber, powdery spicy, or watery): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of its stereoisomers, heliotropin, anisaldehyde, 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.

[0040] The perfume base according to the present invention is not limited to the above-mentioned perfuming co-ingredients, many others of which are listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest edition, or other treatises of a similar nature, as well as the extensive patent literature in the field of perfumery. It is also understood that the above-mentioned co-ingredients may be compounds known to release, in a controlled manner, various types of perfuming compounds, also known as perfume precursors or profragrances.Non-limiting examples of suitable perfume precursors 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-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyloxalate ... oxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hex-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (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-

[0033] The methyl 4-(1-phenethoxyprop-1-en-2-yl)benzene may include 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-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 or mixtures thereof.

[0041] By "perfuming adjuvant" herein is meant an ingredient that can impart additional benefits such as color, specific light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfumed compositions cannot be exhaustive, but it must be mentioned that said ingredients are well known to those skilled in the art. Specific, non-limiting examples include: viscosity agents (e.g., surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light stabilizers and / or buffers or chelating agents, e.g., BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antibacterial or antimicrobial or antifungal or anti-irritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0042] It will be understood that a person skilled in the art is perfectly capable of designing the optimum formulation for the desired effect by mixing the ingredients of the perfuming compositions described above, not only by applying standard knowledge in the art, but also by trial and error.

[0043] The compositions of the present invention comprising at least one compound of formula (I) and at least one perfume carrier comprise specific embodiments of the present invention, as well as perfume compositions comprising at least one compound of formula (I), at least one perfume carrier, at least one perfume base, and optionally at least one perfume adjuvant.

[0044] According to a particular embodiment, the above-mentioned compositions comprise two or more compounds of formula (I), allowing the perfumer to prepare accords or perfumes with the odour notes of the various compounds of the invention, thus creating new building blocks for creative purposes.

[0045] For the sake of clarity, it is also understood that any mixture obtained directly from a chemical synthesis, for example a reaction medium that may contain a compound of the invention as a starting material, intermediate or final product, without appropriate purification, cannot be considered a perfuming composition according to the invention, unless said mixture provides the compound of the invention in a form suitable for perfumery.Unless otherwise stated, unpurified reaction mixtures are therefore generally excluded from the present invention.

[0046] The compounds of the invention can also be used advantageously in all fields of modern perfumery, i.e. perfumes or functional perfumery, to actively impart or modify the odor of consumer products to which said compounds (I) are added. Consequently, another subject of the invention consists of perfumed consumer products comprising at least one compound of formula (I), as defined above, as a perfuming ingredient.

[0047] The compounds of the present invention can be added as such or as part of the perfuming composition of the present invention.

[0048] For clarity, "perfumed consumer product" is meant to refer to a consumer product that provides at least a pleasant fragrance effect to the surface or space to which it is applied (e.g., skin, hair, textile, or household surface). In other words, the perfumed consumer product according to the present invention is a perfumed consumer product that includes a functional formulation, and optionally an additional benefit agent corresponding to the desired consumer product, and an olfactory-effective amount of at least one compound of the present invention. For clarity, the perfumed consumer product is a non-edible product.

[0049] The nature and type of ingredients of perfumed consumer products do not warrant a more detailed description herein (which would in any case not be exhaustive), and those skilled in the art can select them on the basis of general knowledge and according to the nature and desired effect of said product.

[0050] Non-limiting examples of suitable perfumed consumer products include fragrances, such as perfumes, splashes or eau de parfum, colognes or shave or aftershave lotions; fabric care products, such as liquid or solid detergents, fabric softeners, liquid or solid fragrance enhancers, fabric refreshers, ironing water, paper, bleach, carpet cleaners, curtain care products; body care products, such as hair care products (e.g., shampoos, color preparations or hair sprays, color care products, hair styling products, dental care products), disinfectants, intimate care products; cosmetics (e.g., skin creams or lotions); or skin care products (e.g. soaps, shower or bath mousses, oils or gels, or hygiene or foot / hand care products); air care products, such as air fresheners or "ready to use" powdered air fresheners that may be used in domestic spaces (rooms, refrigerators, cupboards, shoes or cars) and / or in public spaces (hall, hotel, mall, etc.); or home care products, such as mould removers, furniture care products, wipes, dishwashing detergents or detergents for hard surfaces (e.g. floor, bath, sanitary or window washing); leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0051] The proportions in which the compounds according to the invention can be incorporated into the various products or compositions mentioned above vary within a wide range of values, which depend on the nature of the article to be perfumed and the desired organoleptic effect, as well as the nature of the auxiliary ingredients in a given base, when the compounds according to the invention are mixed with perfuming auxiliary ingredients, solvents or additives commonly used in the art.

[0052] For example, in perfumed compositions, typical concentrations of the compounds of the invention are on the order of 0.001% to 10% by weight, or more, based on the weight of the composition in which they are incorporated. In perfumed consumer products, typical concentrations of the compounds of the invention are on the order of 0.0001% to 5% by weight, or more, based on the weight of the consumer product in which they are incorporated.

[0053] Some of the above-mentioned perfumed consumer products may be aggressive media for the compounds of the present invention and may therefore need to be protected from premature degradation, for example by encapsulating them or chemically binding them to another chemical suitable for releasing the component of the present invention upon a suitable external stimulus such as an enzyme, light, heat or a change in pH.

[0054] Therefore, another subject of the present invention is a compound of the formula [ka] [Wherein R is C 2~8 Alkenyl group or C 4~8 represents an alkadienyl group] in the form of any one of its stereoisomers or as a mixture thereof.

[0055] The compounds of the present invention may be prepared according to standard methods known in the art, as described herein below. [Example]

[0056] The invention will now be described in further detail by the following examples, in which abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (°C). NMR spectra were obtained at 400 MHz, 1 H) and 100MHz ( 13 Bruker Avance II Ultrashield 400 plus or 500MHz (operating at 1 H) and 125MHz ( 13Bruker Avance III operating at 500 or 600MHz ( 1 H) and 150MHz ( 13 The spectra were acquired using a Bruker Avance III 600 cryoprobe operating at 1000 Hz (C). The spectra were internally referenced to tetramethylsilane at 0.0 ppm. 1 H NMR signal shifts are expressed in δ ppm and coupling constants (J) are expressed in Hz with the following multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; and b, broad (indicating unresolved coupling) and were interpreted using Bruker Topspin software. 13 C NMR data are expressed as chemical shifts δ ppm and hybridization from DEPT90 and DEPT135 experiments: C, quaternary; CH, methine; CH, methylene; CH, methyl.

[0057] Example 1: Synthesis of Compound of Formula (I) 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl 1-(but-3-en-1-yl)-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-cyclopentanecarboxylate (20 g, 128 mmol, 1 equiv.), potassium carbonate (39.8 g, 288 mmol, 2.25 equiv.), and potassium iodide (6.38 g, 38.4 mmol, 0.3 equiv.) in acetone (256 mL) was added 4-bromobut-1-ene (13.3 mL, 131 mol, 1.02 equiv.) dropwise at room temperature. The reaction was refluxed for 2 days. It was allowed to cool, and the acetone was evaporated under reduced pressure. A saturated solution of ammonium chloride was added, and the residue was extracted three times with ether. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was used directly in the next step.

[0058] Step 2: 2-(but-3-en-1-yl)cyclopentan-1-one: To a solution of ethyl 1-(but-3-en-1-yl)-2-oxocyclopentane-1-carboxylate (26.9 g, 128 mmol, 1 equiv.) in methanol (300 mL), 6 M aqueous HCl (150 mL, 900 mmol, 7 equiv.) was added, and the mixture was refluxed for 3 days. It was allowed to cool, and the methanol was evaporated under reduced pressure. The residue was extracted three times with ether. The combined organic extracts were washed with a saturated solution of sodium bicarbonate, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by bulb-to-bulb distillation (105–110 °C, 2–4 mbar) to give 2-(but-3-en-1-yl)cyclopentan-1-one as an oil (6.41 g, 36% yield over two steps). [ka]

[0059] Step 3: 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one: A suspension of KH (30% in oil, 3.87 g, 28.9 mmol, 4 equiv.) was introduced into a three-necked flask equipped with a thermometer and an addition funnel. This was washed three times with pentane to remove most of the oil. 10 mL of THF was added dropwise, followed by the dropwise addition of a solution of 2-(but-3-en-1-yl)cyclopentan-1-one (1 g, 7.24 mmol, 1 equiv.) in 5 mL of THF. After stirring at room temperature for 3 hours, iodomethane (1.81 mL, 28.9 mmol, 4 equiv.) was added dropwise. After stirring at room temperature for 1 hour, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by bulb-to-bulb distillation (10 mbar, 120 °C) to give 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one as an oil (850 mg, 65% yield). [ka]

[0060] 2-Allyl-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl 1-allyl-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-cyclopentanecarboxylate (25 g, 160 mmol, 1 equiv.), potassium carbonate (48.7 g, 352 mmol, 2.2 equiv.), and potassium iodide (7.97 g, 48.0 mmol, 0.3 equiv.) in acetone (457 mL) was added allyl bromide (13.9 mL, 160 mmol, 1 equiv.) dropwise at room temperature. The reaction was refluxed for 17 hours. It was allowed to cool, and the acetone was evaporated under reduced pressure. A saturated solution of ammonium chloride was added, and the residue was extracted three times with ether. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was used directly in the next step.

[0061] Step 2: 2-Allylcyclopentan-1-one: To a solution of ethyl 1-allyl-2-oxocyclopentane-1-carboxylate (31.4 g, 160 mmol, 1 equiv.) in methanol (400 mL) was added 6 M aqueous HCl (192 mL, 1.15 mol, 7.2 equiv.), and the mixture was refluxed for 38 h. It was allowed to cool, and the methanol was evaporated under reduced pressure. The residue was extracted three times with ether. The combined organic extracts were washed with a saturated solution of sodium bicarbonate, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by bulb-to-bulb distillation (100–105 °C, 50 mbar) to give 2-allylcyclopentan-1-one as an oil (14.5 g, 73% yield over two steps). [ka]

[0062] Step 3: 2-Allyl-2,5,5-trimethylcyclopentan-1-one: A suspension of KH (30% in oil, 43.1 g, 322 mmol, 4 equiv.) was introduced into a three-neck flask equipped with a thermometer and an addition funnel. This was washed three times with pentane to remove most of the oil. 100 mL of THF was added dropwise, followed by the dropwise addition of a solution of 2-allylcyclopentan-1-one (10 g, 80.5 mmol, 1 equiv.) in 60 mL of THF. After stirring at room temperature for 10 minutes, iodomethane (30.2 mL, 483 mmol, 6 equiv.) was added dropwise. After stirring at room temperature for 1 hour, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by bulb-to-bulb distillation (25 mbar, 105 °C) to give 2-allyl-2,5,5-trimethylcyclopentan-1-one as an oil (10.4 g, 78% yield). [ka]

[0063] 2-(hex-5-en-1-yl)-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl 1-(hex-5-en-1-yl)-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-oxocyclopentane-1-carboxylate (56 mL, 375 mmol, 1 equiv.) in acetone (871 mL) at room temperature was rapidly added potassium carbonate (118 g, 845 mmol, 2.25 equiv.) and potassium iodide (20 g, 120 mmol, 0.32 equiv.). After stirring for 10 minutes, a solution of 6-bromohex-1-ene (51 mL, 381 mmol, 1.01 equiv.) in acetone (232 mL) was added, and the reaction was refluxed for 19 hours. Diethyl ether (900 mL) was added, the mixture was filtered through a pad of Celite, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give ethyl 1-(hex-5-en-1-yl)-2-oxocyclopentane-1-carboxylate as an oil (93.3 g, 91% purity, 95% yield). [ka]

[0064] Step 2: 2-(hex-5-en-1-yl)cyclopentan-1-one: To a solution of ethyl 1-(hex-5-en-1-yl)-2-oxocyclopentane-1-carboxylate (93.3 g, 91% purity, 356 mmol, 1 equiv.) in methanol (860 mL) was added dropwise 6 M aqueous HCl (428 mL, 2.57 mol, 7.2 equiv.) at room temperature. The reaction was refluxed for 6 days. Diethyl ether was added, and the aqueous layer was extracted twice with ether. The combined organic extracts were washed successively with water, a saturated solution of sodium bicarbonate, water, and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by distillation on a Vigreux column (92–93 °C, 1.5 mbar) to give 2-(hex-5-en-1-yl)cyclopentan-1-one as an oil (42.0 g, 71% yield). [ka]

[0065] Step 3: 2-(hex-5-en-1-yl)-2,5,5-trimethylcyclopentan-1-one: A suspension of KH (30% in oil, 3.54 g, 26.5 mmol, 4 equiv.) was introduced into a three-neck flask equipped with a thermometer and an addition funnel. This was washed three times with pentane to remove most of the oil. 8 mL of THF was added dropwise, followed by the dropwise addition of a solution of 2-(hex-5-en-1-yl)cyclopentan-1-one (1.1 g, 6.62 mmol, 1 equiv.) in 5 mL of THF. After stirring at room temperature for 10 minutes, iodomethane (2.48 mL, 39.7 mmol, 6 equiv.) was added dropwise. After stirring at room temperature for 1 hour, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by bulb-to-bulb distillation (2–4 mbar, 120 °C) to give 2-(hex-5-en-1-yl)-2,5,5-trimethylcyclopentan-1-one as an oil (1.30 g, 94% yield). [ka]

[0066] (Z)-2-(hex-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl (Z)-1-(hex-3-en-1-yl)-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-oxocyclopentane-1-carboxylate (4.63 mL, 31.1 mmol, 1 equiv.) in acetone (73 mL) at room temperature was rapidly added potassium carbonate (9.8 g, 70.2 mmol, 2.26 equiv.) and potassium iodide (1.65 g, 9.94 mmol, 0.32 equiv.). After stirring for 10 minutes, a solution of (Z)-1-chlorohex-3-ene (3.71 g, 31.3 mmol, 1.01 equiv.) in acetone (19 mL) was added, and the reaction was refluxed for 6 days. Diethyl ether was added, the mixture was filtered through a pad of Celite, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was used directly in the next step.

[0067] Step 2: (Z)-2-(hex-3-en-1-yl)cyclopentan-1-one: To a solution of ethyl (Z)-1-(hex-3-en-1-yl)-2-oxocyclopentane-1-carboxylate (5.56 g, 18.2 mmol, 1 equiv.) in methanol (47 mL) was added 6 M aqueous HCl (24 mL, 144 mmol, 7.9 equiv.) dropwise at room temperature. The reaction was refluxed for 4 days. Diethyl ether was added, and the aqueous layer was extracted twice with ether. The combined organic extracts were washed successively with water, saturated sodium bicarbonate solution, water, and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 95:5) and bulb-to-bulb distillation (0.9–1.0 mbar, 105–125 °C) to give (Z)-2-(hex-3-en-1-yl)cyclopentan-1-one as an oil (1.46 g, 48% yield). [ka]

[0068] Step 3: (Z)-2-(hex-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one: A suspension of KH (30% in oil, 2.99 g, 22.4 mmol, 4.6 equiv.) was added to a three-neck flask equipped with a thermometer and an addition funnel. This was washed three times with pentane to remove most of the oil. 7 mL of THF was added dropwise, followed by (Z)-2-(hex-3-en-1-yl)cyclopentan-1-one (806 mg, 4.85 mmol, 1 equiv.) in 4 mL of THF. After stirring at room temperature for 10 minutes, iodomethane (1.90 mL, 30.2 mmol, 6.2 equiv.) was added dropwise. After stirring at room temperature for 20 minutes, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 98:2) and bulb-to-bulb distillation (1.5 mbar, 115 °C) to give (Z)-2-(hex-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one as an oil (608 mg, 60% yield). [ka]

[0069] (E)-2-(hex-4-en-1-yl)-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl (E)-1-(hex-4-en-1-yl)-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-oxocyclopentane-1-carboxylate (7.41 mL, 49.7 mmol, 1 equiv.) in acetone (117 mL) at room temperature was rapidly added potassium carbonate (15.7 g, 112 mmol, 2.26 equiv.) and potassium iodide (2.64 g, 15.9 mmol, 0.32 equiv.). After stirring for 10 minutes, a solution of (E)-hex-4-en-1-yl methanesulfonate (8.93 g, 50.1 mmol, 1.01 equiv.) in acetone (30 mL) was added, and the reaction was refluxed for 17 hours. Diethyl ether was added, the mixture was filtered through a pad of Celite, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was used directly in the next step.

[0070] Step 2: (E)-2-(hex-4-en-1-yl)cyclopentan-1-one: To a solution of ethyl (E)-1-(hex-4-en-1-yl)-2-oxocyclopentane-1-carboxylate (12.6 g, 44.4 mmol, 1 equiv.) in methanol (115 mL) was added dropwise 6 M aqueous HCl (57 mL, 342 mmol, 7.7 equiv.) at room temperature. The reaction was refluxed for 3 days. Diethyl ether was added, and the aqueous layer was extracted twice with ether. The combined organic extracts were washed successively with water, a saturated solution of sodium bicarbonate, water, and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 95:5) and bulb-to-bulb distillation (4:9 to 6:6:10). -3 mbar, 60-65° C.) to give (E)-2-(hex-4-en-1-yl)cyclopentan-1-one as an oil (4.74 g, 64% yield). [ka]

[0071] Step 3: (E)-2-(hex-4-en-1-yl)-2,5,5-trimethylcyclopentan-1-one: A suspension of KH (30% in oil, 4.61 g, 34.5 mmol, 5.7 equiv.) was introduced into a three-neck flask equipped with a thermometer and an addition funnel. This was washed three times with pentane to remove most of the oil. 8 mL of THF was added dropwise, followed by the dropwise addition of a solution of (E)-2-(hex-4-en-1-yl)cyclopentan-1-one (1 g, 6.01 mmol, 1 equiv.) in 5 mL of THF. After stirring for 10 minutes at room temperature, iodomethane (2.30 mL, 36.6 mmol, 6.1 equiv.) was added dropwise. After stirring for 1 hour and 40 minutes at room temperature, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 95:5) and bulb-to-bulb distillation (0.5 mbar, 125 °C) to give (£)-2-(hex-4-en-1-yl)-2,5,5-trimethylcyclopentan-1-one as an oil (983 mg, 78% yield). [ka]

[0072] (Z)-2-(hex-4-en-1-yl)-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl (Z)-1-(hex-4-en-1-yl)-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-oxocyclopentane-1-carboxylate (4.80 mL, 32.2 mmol, 1 equiv.) in acetone (73 mL) at room temperature was rapidly added potassium carbonate (9.80 g, 70.2 mmol, 2.18 equiv.) and potassium iodide (1.65 g, 9.94 mmol, 0.31 equiv.). After stirring for 10 minutes, a solution of (Z)-6-chlorohex-2-ene (4.60 mL, 32.1 mmol, 1 equiv.) in acetone (19 mL) was added, and the reaction was refluxed for 5 days. Diethyl ether was added, the mixture was filtered through a Celite pad, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was used directly in the next step.

[0073] Step 2: (Z)-2-(hex-4-en-1-yl)cyclopentan-1-one: To a solution of ethyl (Z)-1-(hex-4-en-1-yl)-2-oxocyclopentane-1-carboxylate (7.65 g, 29.2 mmol, 1 equiv.) in methanol (76 mL) was added 6 M aqueous HCl (38 mL, 228 mmol, 7.8 equiv.) dropwise at room temperature. The reaction was refluxed for 4 days. Diethyl ether was added, and the aqueous layer was extracted twice with ether. The combined organic extracts were washed successively with water, saturated sodium bicarbonate solution, water, and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 95:5) and bulb-to-bulb distillation (0.2–0.3 mbar, 100–120 °C) to give (Z)-2-(hex-4-en-1-yl)cyclopentan-1-one as an oil (1.97 g, 64% yield). [ka]

[0074] Step 3: (Z)-2-(hex-4-en-1-yl)-2,5,5-trimethylcyclopentan-1-one: A suspension of KH (30% in oil, 3.19 g, 19.9 mmol, 4.34 equiv.) was introduced into a three-neck flask equipped with a thermometer and an addition funnel. This was washed three times with pentane to remove most of the oil. 7 mL of THF was added dropwise, followed by the dropwise addition of a solution of (Z)-2-(hex-4-en-1-yl)cyclopentan-1-one (778 mg, 4.59 mmol, 1 equiv.) in 4 mL of THF. After stirring at room temperature for 10 minutes, iodomethane (1.80 mL, 28.6 mmol, 6.24 equiv.) was added dropwise. After stirring at room temperature for 40 minutes, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 98:2) and bulb-to-bulb distillation (1.6 mbar, 115-120 °C) to give (Z)-2-(hex-4-en-1-yl)-2,5,5-trimethylcyclopentan-1-one as an oil (567 mg, 58% yield). [ka]

[0075] (E)-2-(hex-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one Step 1: Ethyl (E)-1-(hex-3-en-1-yl)-2-oxocyclopentane-1-carboxylate: To a solution of ethyl 2-oxocyclopentane-1-carboxylate (7.41 mL, 49.7 mmol, 1 equiv.) in acetone (117 mL) at room temperature was rapidly added potassium carbonate (15.7 g, 112 mmol, 2.26 equiv.) and potassium iodide (2.64 g, 15.9 mmol, 0.32 equiv.). After stirring for 10 minutes, a solution of (E)-hex-3-en-1-yl methanesulfonate (8.98 g, 50.4 mmol, 1.01 equiv.) in acetone (30 mL) was added, and the reaction was refluxed for 4 days. Diethyl ether was added, the mixture was filtered through a pad of Celite, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was used directly in the next step.

[0076] Step 2: (E)-2-(hex-3-en-1-yl)cyclopentan-1-one: To a solution of ethyl (E)-1-(hex-3-en-1-yl)-2-oxocyclopentane-1-carboxylate (10.8 g, 41.4 mmol, 1 equiv.) in methanol (107 mL) was added 6 M aqueous HCl (53 mL, 318 mmol, 7.7 equiv.) dropwise at room temperature. The reaction was refluxed for 4 days. Diethyl ether was added, and the aqueous layer was extracted twice with ether. The combined organic extracts were washed successively with water, saturated sodium bicarbonate solution, water, and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 95:5) and bulb-to-bulb distillation (0.1–0.2 mbar, 95–105 °C) to give (£)-2-(hex-3-en-1-yl)cyclopentan-1-one as an oil (4.27 g, 62% yield). [ka]

[0077] Step 3: (E)-2-(hex-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one: A three-necked flask equipped with a thermometer and a dropping funnel was charged with a suspension of KH (30% in oil, 8.30 g, 51.7 mmol, 8.6 equiv.). This was washed three times with pentane to remove most of the oil. 10 mL of THF was added dropwise, followed by the dropwise addition of a solution of (E)-2-(hex-3-en-1-yl)cyclopentan-1-one (1 g, 6.01 mmol, 1 equiv.) in 6 mL of THF. After stirring at room temperature for 10 minutes, iodomethane (2.40 mL, 38.2 mmol, 6.3 equiv.) was added dropwise. After stirring at room temperature for 15 minutes, the reaction was quenched with a saturated solution of ammonium chloride and extracted twice with ether. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane / AcOEt 98:2) and bulb-to-bulb distillation (1.3–1.4 mbar, 115–120 °C) to give (E)-2-(hex-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one as an oil (1.07 g, 84% yield). [ka]

[0078] (+-)-2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone (E)-2-Pentylidene-1-cyclopentanone (3.4 g, 22.3 mmol, prepared according to R. Mahrwald, H. Schick, Synthesis, 1990, 592; T. Nakano et al., J. Org. Chem. 1987, 52, 2239) was added dropwise over 10 min to a solution of tBuOK (9.76 g, 67 mmol) in THF (80 ml) at 20–25°C. After 2 h at 50°C, the red solution was cooled to 20°C, and MeI (9.5 g, 67 mmol) was added dropwise, ensuring the temperature did not exceed 27°C. The reaction was stirred at 20°C for 1 h and then refluxed (75°C) for 2 h. The reaction was poured into ice / water and then extracted with ether. The organic phase was washed twice with HO and brine, dried over NaSO, filtered, and concentrated to give 4 g of an orange oil. Purification on a 50 g SiO cartridge with cyclohexane / AcOEt 99 / 1 gave 1.68 g with 77% purity. A second chromatography on 40 g AlO with the same solvent mixture gave 1.23 g as a 92:8 E / Z mixture after bulb-to-bulb distillation at Bp 60 °C / 0.07 mbar (28% yield). [ka]

[0079] (+-)-2-[(1E)-1-buten-1-yl]-2,5,5-trimethylcyclopentanone (E)-2-Butylidene-1-cyclopentanone (5.5 g, 37.8 mmol, prepared according to E. Delort et al. J. Agric. Food. Chem. 2011, 59, 11752; R. Arnacke et al. Lieb. Ann. Chem. 1994, 891) was added dropwise over 10 min to a solution of tBuOK (14.85 g, 132.3 mmol) in THF (120 ml) at 20–25°C. After 2 h at 50°C, the red solution was cooled to 20°C and MeI (17.17 g, 121.0 mmol) was added dropwise, ensuring the temperature did not exceed 35°C. The reaction was stirred at room temperature for 1 h, then heated to 50°C for 2 h, and then refluxed (75°C) for 2 h. The reaction was poured into ice / water and then extracted with EtO. The organic phase was washed twice with H2O and brine, dried over Na2SO4, filtered and evaporated to give 6.2 g of an orange oil. Purification on a 120 g SiO2 cartridge with cyclohexane / AcOEt 99 / 1 gave: Fr7-15 1.0g 77%(E)+9%(Z);Fr16-27 1.5g 89%(E)+5%(Z);Fr28-36 308mg 90%(E)+4%(Z).

[0080] All fractions were combined and bulb-to-bulb distilled at 100 °C / 0.36 mbar to give 1276 mg in 94% (E) + 6% (Z) (19% yield). [ka]

[0081] (+-)-2-[(1E)-1-Hexen-1-yl]-2,5,5-trimethylcyclopentanone (2E)-2-Hexylidenecyclopentanone (2.15 g, 12 mmol, prepared according to W. Wang et al. Org. Lett. 2005, 7, 601; Science & Technology Corp. WO 2006 / 7586) was added dropwise over 10 minutes to a solution of tBuOK (4.04 g, 36 mmol) in THF (35 ml) at 20-25°C. After 3 hours, MeI (5.11 g, 36 mmol) was added dropwise below 35°C. The reaction was stirred at 20°C for 1 hour, then heated to 50°C for 2 hours and refluxed (75°C) for 2 days. The reaction mixture was poured into ice / water and extracted with EtO. The organic phase was washed twice with H2O and brine, dried over Na2SO4, filtered, and concentrated to give an orange oil. Purification on an 80 g SiO2 cartridge with cyclohexane / ethyl acetate 99 / 1 gave: Fr 18-24 890 mg 93:7 (E / Z) mixture; Fr 25-31 460 mg 85:15 (E / Z) mixture (54% yield). [ka]

[0082] (+-)-2,2,5-trimethyl-5-[(2Z)-2-penten-1-yl]cyclopentanone Step 1: (+-)-2,2,5-trimethyl-5-(2-pentyn-1-yl)cyclopentanone 2-(Pent-2-yn-1-yl)cyclopentan-1-one (3.0 g, 19.97 mmol, [4]) was added dropwise over 10 min to a suspension of 30% KH (8.0 g, 59.91 mmol) in mineral oil in THF (10 ml) at 20–25 °C. After 1 h, MeI (8.5 g, 59.91 mmol) was added dropwise below 30 °C. The reaction was stirred at 20 °C for 1 h, then the reaction mixture was poured onto ice / water and extracted with EtO. The organic phase was washed twice with H2O and brine, dried over Na2SO4, filtered, and concentrated to give an orange oil. Purification on an 80 g SiO2 cartridge using cyclohexane / ethyl acetate 99 / 1 afforded the pure title compound in 85% yield after bulb-to-bulb distillation. Bp 100 °C / 0.29 mbar. [ka]

[0083] Step 2: (+-)-2,2,5-trimethyl-5-[(2Z)-2-penten-1-yl]cyclopentanone A solution of (+-)-2,2,5-trimethyl-5-(2-pentyn-1-yl)cyclopentanone (1.0 g, 5.2 mmol) in cyclohexane (10 mL) was hydrogenated over Lindlar's catalyst (55.3 mg). After absorbing 1.0 molar equivalent of H, the reaction mixture was concentrated in vacuo and purified on CC / SiO with cyclohexane / AcOEt 99:1 to give the pure material in 35% yield. [ka]

[0084] (E)-2,2,5-trimethyl-5-(pent-2-en-1-yl)cyclopentan-1-one First Step: (E)-2-(pent-2-en-1-yl)cyclopentan-1-one An autoclave was charged with citric acid (15.6 g, 81 mmol), triethylamine (8.2 g, 81 mmol), pent-1-en-3-ol (126.8 g, 1473 mmol), and 1,1-diethoxycyclopentane (233 g, 1473 mmol). The mixture was heated to 160 °C for 15 h. It was cooled to room temperature, quenched with HCl (5%), extracted with AcOEt, washed with HO and brine, dried over MgSO, filtered, and concentrated to give 234.4 g of crude product. The crude product was purified by fractional distillation at 100 °C / 6.4 mbar to give 179 g (80% yield). [ka]

[0085] Second step: (E)-2,2,5-trimethyl-5-(pent-2-en-1-yl)cyclopentan-1-one To a suspension of KH (2.6 g, 19.7 mmol) in THF (20 mL) at room temperature, (E)-2-(pent-2-en-1-yl)cyclopentan-1-one (1 g, 6.6 mmol) was added while maintaining the reaction temperature below 30 °C. After 30 min at room temperature, MeI (2.8 g, 19.7 mmol) was added dropwise over 20 min to control the strongly exothermic reaction (maximum temperature: 43 °C). The slurry was stirred at room temperature for 40 min and then heated at 40 °C for 2 h. Partial conversion was observed. The reaction mixture was cooled to room temperature, quenched with NH Cl, and then extracted with Et O. The organic phase was washed twice with HO and brine, dried over Na SO , filtered, and concentrated to give 3.1 g of crude product. After purification by bulb-to-bulb distillation, 1.2 g of partially permethylated product was obtained. The previous material was reacted again under the aforementioned reaction conditions to give 0.9 g of the desired product (75% yield) after purification. [ka]

[0086] (E)-2-(hex-2-en-1-yl)-2,5,5-trimethylcyclopentan-1-one First Step: (E)-2-(hex-2-en-1-yl)cyclopentan-1-one To a solution of Cu(OAc) (1.8 g, 0.009 mol, 0.15 equiv.) in AcOH (30 mL) was added cyclopentanone (25 g, 0.3 mol, 5 equiv.), 1-hexene (5 g, 0.06 mol), and Mn(OAc) (16 g, 0.06 mol, 1 equiv.). The mixture was heated at 60 °C for 1 h 30 min. The mixture was cooled to room temperature. The suspension was filtered through Celite / filter Cel, and the pad was washed with EtO (50 mL), water (3 × 20 mL), saturated NaHCO (1 × 20 mL), brine (1 × 20 mL), and dried over NaSO. The suspension was filtered and concentrated in vacuo. The crude product was purified by flash distillation to remove excess cyclopentanone. Subsequent purification by silica gel chromatography (CyH / Et2O) gave (E)-2-(hex-2-en-1-yl)cyclopentan-1-one (27%) with a purity of 98%. [ka]

[0087] Second step: (E)-2-(hex-2-en-1-yl)-2,2,5-trimethylcyclopentan-1-one To KH (30% in oil, 2.4 g, 0.018 mol, 3 eq.) in THF (20 mL) was added (E)-2-(hex-2-en-1-yl)cyclopentan-1-one dropwise while controlling the internal temperature. The suspension was stirred at room temperature for 30 min. CHI (2.6 g, 0.018 mol, 3 eq.) was then added dropwise over 25 min (a strong exotherm was observed). The white suspension was stirred at room temperature for 40 min and then heated at 40 °C for 2 h (80% conversion). The mixture was cooled to room temperature. The reaction was quenched with saturated NH Cl (50 mL), extracted with Et O (2 × 25 mL), washed with water (1 × 25 mL) and brine (1 × 25 mL), and dried over MgSO . The suspension was filtered and concentrated in vacuo. The crude product was purified by flash distillation to give 1 g (80%) of (E)-2-(hex-2-en-1-yl)-2,5,5-trimethylcyclopentan-1-one with a purity of 98%. [ka]

[0088] Example 2: Preparation of Perfumed Composition A perfume composition for shampoo was prepared by mixing the following ingredients: [Table 2-1] [Table 2-2]

[0089] To the above-mentioned perfume composition, 400 parts by weight of a compound of the present invention described in Example 1, for example, 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one or 2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone, was added.

Claims

1. A method for imparting, enhancing, improving or modifying the odor characteristics of a perfumed composition or perfumed article, comprising adding to said composition or said article an effective amount of at least one compound of formula 【Chemistry 1】 wherein R is C ２～８ Alkenyl group or C ４～８ represents an alkadienyl group] in the form of any one of its stereoisomers or as a mixture thereof.

2. R is C ２～６ The method of claim 1 , wherein the alkyl group represents an alkenyl group.

3. R is linear C ２～６ 3. The method of claim 1 or 2, wherein the alkyl group represents an alkenyl group.

4. The compound has the formula 【Chemistry 2】 wherein one dotted line represents a carbon-carbon double bond and the other dotted line represents a carbon-carbon single bond; R １ is a hydrogen atom or C １～２ 4. The method according to claim 1, wherein the compound is a compound of the formula: wherein R represents an alkyl group; in the form of any one of its stereoisomers or as a mixture thereof.

5. R １ The method of claim 4, wherein represents a hydrogen atom or a methyl group.

6. The compound of formula (I) is 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one, 2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone, 2-[(1-buten-1-yl)-2,2,5-trimethylcyclopentanone, 2-[1-hexen-1-yl]-2,5,5-trimethylcyclopentanone, 2-allyl-2,5,5-trimethylcyclopentanone, 2-(5-hexen- 6. The method of any one of claims 1 to 5, wherein the methylcyclopentanone is selected from the group consisting of 2-[3-hexen-1-yl]-2,5,5-trimethylcyclopentanone, 2-[4-hexen-1-yl]-2,5,5-trimethylcyclopentanone, 2-(hex-2-enyl)-2,5,5-trimethylcyclopentanone, and 2,2,5-trimethyl-5-(pent-2-enyl)cyclopentanone.

7. 7. The process of any one of claims 1 to 6, wherein the compound of formula (I) is selected from the group consisting of 2-(but-3-en-1-yl)-2,5,5-trimethylcyclopentan-1-one, 2,2,5-trimethyl-5-[(1E)-1-penten-1-yl]cyclopentanone, and 2,2,5-trimethyl-5-(pent-2-enyl)cyclopentanone.

8. Use of a compound of formula (I) as defined in claims 1 to 7 as a perfuming ingredient.

9. A compound of formula (I) as defined in claims 1 to 7.

10. A perfuming composition comprising: i) at least one compound of formula (I) as defined in claim 9; ii) at least one ingredient selected from the group consisting of a perfume carrier and a perfume base; and iii) optionally at least one perfume adjuvant A perfume composition comprising:

11. A scented consumer product comprising at least one compound of formula (I) as defined in claim 9 or a scenting composition as defined in claim 10.

12. 12. The scented consumer product of claim 11, wherein the product is a fragrance, a fabric care product, a body care product, a cosmetic, a skin care product, an air care product, or a home care product.

13. 13. The perfumed consumer product of claim 12, characterized in that it is a perfume, splash or eau de parfum, cologne, shave or aftershave lotion, liquid or solid detergent, fabric softener, fabric refresher, ironing water, paper, bleach, carpet cleaner, curtain care product, shampoo, color preparation, color care product, hair styling product, dental care product, disinfectant, intimate care product, hairspray, vanishing cream, deodorant or antiperspirant, depilatory, tanning product or suntanning product, nail product, skin cleansing, make-up, scented soap, shower or bath mousse, oil or gel, foot / hand care product, hygiene product, air freshener, "ready to use" powdered air freshener, mould remover, furniture care product, wipe, dish detergent or hard surface cleaner, leather care product, car care product.

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