A macrocyclic molecule with a powdery, musky smell

Abstract

The present invention relates to a composition comprising: a) 0.5-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-10% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-10% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5-98.8% w / w of (Z)-oxacyclohexadec-13-en-2-one, the percentages being based on the total weight of the composition; and the weight ratio of E-diastereoisomer to Z-diastereoisomer being in the range of 14:86 to 0.5:99.5.

Description

[Technical field]

[0001] The present invention relates to the field of perfumery. More particularly, the present invention relates to a composition comprising: a) 0.5 to 98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-10% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-10% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 98.8% w / w of (Z)-oxacyclohexadec-13-en-2-one Including, the percentages being based on the total weight of the composition; the weight ratio of E-diastereoisomer to Z-diastereoisomer is in the range of 14:86 to 0.5:99.5; Concerning the composition.

[0002] The compositions are useful perfume ingredients and, as such, the present invention includes the compositions of the present invention as part of a perfume composition or perfumed consumer product.

[0003] 2. Background of the Invention Ingredients that impart musk notes, especially macrocyclic musk compounds, are highly valued and widely used in perfumery, since they are considered one of the important perfume base notes. Some of said macrocyclic musk compounds usually have double bonds that give rise to a mixture of diastereoisomers and / or positional isomers. An example is Habanolide® (Firmenich SA, Geneva, Switzerland), which mainly contains (Z)-oxacyclohexadec-12-en-2-one, (E)-oxacyclohexadec-12-en-2-one, (E)-oxacyclohexadec-13-en-2-one, and (Z)-oxacyclohexadec-13-en-2-one, with an E:Z ratio comprised between 70:30 and 80:20. The distribution of isomers affects the sensory properties of the ingredient. It is therefore necessary to develop new quality paths to enrich the perfumer's palette. In particular, there is a need to enhance the nitro musk aspect of Habanolides® while maintaining the ambrette facet. However, the exact organoleptic properties of each individual isomer are unknown, and actual syntheses resulting in pure isomers or mixtures are composed primarily of the E isomer.

[0004] For example, WO 2018 / 104856 reports a method for obtaining (E)-oxacyclohexadec-12-en-2-one or (E)-oxacyclohexadec-13-en-2-one in high purity. Furthermore, US 2017 / 211014 discloses the isomerization of Globalide® to give a mixture of oxacyclohexadec-12-en-2-one and oxacyclohexadec-13-en-2-one in an E:Z ratio of 65:31.

[0005] The present invention provides novel compositions containing a high ratio of Z to E isomers that provide the intense powdery / musky notes that are so highly valued in perfumery. The prior art did not anticipate that the compositions of the present invention would provide such a structure in performance and odor profile, nor did it provide a method to significantly enrich the Z isomer.

[0006] Description of the invention A surprising synergy has been discovered between the various isomers of oxacyclohexadec-(12 or 13)-en-2-one resulting in the inventive composition having a strong musky / powdery note combined with an ambrette aspect.

[0007] Therefore, a first object of the present invention is a composition comprising: a) 0.5 to 98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-10% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-10% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 98.8% w / w of (Z)-oxacyclohexadec-13-en-2-one Including, The percentages are based on the total weight of the composition; the weight ratio of E-diastereoisomer to Z-diastereoisomer is in the range of 14:86 to 0.5:99.5; It is a composition.

[0008] Said composition can be used as a perfuming ingredient, for example to impart an odour note of the powdery musk type, also having an amber aspect.

[0009] The terms "E-diastereoisomer" and "Z-diastereoisomer" have their ordinary meaning as understood by those skilled in the art, i.e., the E-diastereoisomer corresponds to (E)-oxacyclohexadec-12-en-2-one and (E)-oxacyclohexadec-13-en-2-one, and the Z-diastereoisomer corresponds to (Z)-oxacyclohexadec-12-en-2-one and (Z)-oxacyclohexadec-13-en-2-one.

[0010] According to one embodiment of the present invention, in the composition, the various components mentioned above are present in the following amounts: a) 55-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-7% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-6% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5-31% w / w of (Z)-oxacyclohexadec-13-en-2-one.

[0011] According to one embodiment of the present invention, in the composition, the various components mentioned above are present in the following amounts: a) 90-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-2.5% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-1% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5-2.5% w / w of (Z)-oxacyclohexadec-13-en-2-one.

[0012] According to one embodiment of the present invention, in the composition, the various components mentioned above are present in the following amounts: a) 0.5-10% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-2.5% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-3% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 55-98.8% w / w of (Z)-oxacyclohexadec-13-en-2-one.

[0013] According to any one of the above embodiments of the invention, the composition may comprise about 58-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one, in particular about 58-70% w / w or about 92-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one, more particularly about 58-65% w / w or about 95-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one.

[0014] According to a particular embodiment of the invention, the composition may comprise about 0.5-15% w / w of (Z)-oxacyclohexadec-12-en-2-one, in particular 1-10% w / w of (Z)-oxacyclohexadec-12-en-2-one, in particular 1.5-8% w / w of (Z)-oxacyclohexadec-12-en-2-one, and even more particularly 3-7% w / w of (Z)-oxacyclohexadec-12-en-2-one.

[0015] According to any one of the above embodiments of the invention, the composition may comprise about 0.1 to 10% w / w of (E)-oxacyclohexadec-12-en-2-one, in particular about 0.1 to 8% w / w of (E)-oxacyclohexadec-12-en-2-one, in particular about 0.1 to 7% w / w of (E)-oxacyclohexadec-12-en-2-one, in particular about 0.1 to 6% w / w of (E)-oxacyclohexadec-12-en-2-one, in particular about 0.1 to 5% w / w of (E)-oxacyclohexadec-12-en-2-one, in particular about 0.1 to 2% w / w of (E)-oxacyclohexadec-12-en-2-one, more particularly about 0.1 to 1.5% w / w of (E)-oxacyclohexadec-12-en-2-one.

[0016] According to any one of the above embodiments of the invention, the composition comprises about 1-97% w / w of (Z)-oxacyclohexadec-13-en-2-one, in particular about 1.5-96% w / w of (Z)-oxacyclohexadec-13-en-2-one, in particular about 2-96% w / w of (Z)-oxacyclohexadec-13-en-2-one, in particular about 2.5-95% w / w of (Z)-oxacyclohexadec-13-en-2-one, in particular about 10- It may comprise 95% w / w of (Z)-oxacyclohexadec-13-en-2-one, in particular about 20-95% w / w of (Z)-oxacyclohexadec-13-en-2-one, in particular about 90-95% w / w or about 1.5-31% w / w of (Z)-oxacyclohexadec-13-en-2-one, even more particularly about 90-95% w / w or about 5-31% w / w of (Z)-oxacyclohexadec-13-en-2-one.

[0017] According to any one of the above embodiments of the invention, the composition may comprise about 0-10% w / w of (E)-oxacyclohexadec-13-en-2-one, in particular about 0-7% w / w of (E)-oxacyclohexadec-13-en-2-one, more particularly about 0-5% w / w of (E)-oxacyclohexadec-13-en-2-one.

[0018] According to any one of the above embodiments of the invention, the weight ratio of E-diastereoisomer to Z-diastereoisomer is comprised in the range of 12:88 to 1:99, in particular in the range of 10:90 to 1:99, in particular in the range of 9.5:90.5 to 1:99, in particular in the range of 7.5:92.5 to 1:99, in particular in the range of 5:95 to 2:98; more particularly in the range of 3:97 to 2:98.

[0019] According to any one of the above embodiments of the present invention, the weight ratio of the 12-positional isomer to the 13-positional isomer is in the range of 55:45 to 99:1, or in the range of 20:80 to 1:99; more particularly in the range of 65:35 to 99:1, or in the range of 10:90 to 5:95.

[0020] The terms "12-positional isomer" and "13-positional isomer" have their ordinary meaning as understood by one of ordinary skill in the art, i.e., the 12-positional isomer corresponds to (E)-oxacyclohexadec-12-en-2-one and (Z)-oxacyclohexadec-12-en-2-one, and the 13-positional isomer corresponds to (E)-oxacyclohexadec-13-en-2-one and (Z)-oxacyclohexadec-13-en-2-one.

[0021] As previously mentioned, the compositions of the present invention have a very strong musky, long-lasting odor with a stronger than expected powdery note in the direction of nitromusk. The overall odor profile is highly valued by perfumers, as it opens new directions for their creativity when compared to the prior art ingredient Habanolides®.

[0022] In fact, when comparing the odor of the composition of the present invention with that of the prior art Habanolides®, the composition of the present invention is distinguished by a clearly different odor profile, characterized by stronger powdery and ambrette notes and much weaker metallic notes, characteristic of the prior art compounds. Moreover, the composition of the present invention imparts clearly stronger and more present notes while providing more volume to the perfume composition. The composition of the present invention is also distinguished by exhibiting a more appreciated olfactory profile. Overall, while Habanolides® is closer to the direction of macrocyclic musks with a slight metallic aspect, the present composition is closer to the direction of nitro musks, which is particularly sought after, due to the very restrained use of nitro musks.

[0023] Said differences make the compositions of the present invention and the prior art compounds suitable for different applications, i.e. for imparting different organoleptic impressions.

[0024] As mentioned above, the present invention relates to the use of the composition of the present invention as a perfuming ingredient. In other words, the present invention relates to a method or process for imparting, enhancing, improving or modifying the odor characteristics of a perfuming composition or a perfumed article or surface, comprising adding an effective amount of the composition of the present invention to said composition or article, for example to impart its typical note. It is understood that the final hedonic effect may depend on the exact dosage and organoleptic properties of the composition of the present invention, but in any case, the addition of the composition of the present invention imparts its typical touch to the final product in the form of a note, touch or aspect, depending on the dosage. Furthermore, the composition of the present invention can also be used to enhance the organoleptic properties of perfuming ingredients or to reduce the unpleasant olfactory impression of some perfuming ingredients, for example metallic, dusty or chemical facets.

[0025] With regard to "use of the composition of the invention" it is to be understood herein the use of any composition which contains the composition of the invention and which can be advantageously used in the perfumery industry.

[0026] Said compositions, which in fact can be advantageously used as perfuming ingredients, are also an object of the present invention.

[0027] Another object of the present invention is therefore a perfuming composition comprising: i) at least one composition according to the invention as defined above as perfuming ingredient; ii) at least one component selected from the group consisting of a fragrance carrier and a fragrance base; and iii) optionally, at least one flavoring adjuvant; The fragrance composition comprises:

[0028] By "perfume carrier" is meant herein a substance which is practically neutral from the perfume point of view, i.e. which does not significantly alter the organoleptic properties of the perfuming ingredients. Said carrier may be liquid or solid.

[0029] The liquid carrier can be, as a non-limiting example, an emulsifying system, i.e. a solvent and surfactant system, or a solvent commonly used in perfumery.A detailed description of the nature and type of the solvent commonly used in perfumery cannot be exhaustive.However, as a non-limiting example, it can be the most commonly used solvents such as butylene or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate, or mixtures thereof, or it can be naturally derived solvents such as glycerol or various vegetable oils, such as palm oil, sunflower oil, or linseed oil. For compositions containing both a perfume carrier and a perfume base, suitable perfume carriers other than those identified above may be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (supplied by Exxon Chemical), or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (supplied by Dow Chemical Company), or hydrogenated castor oil such as those known under the trademark Cremophor® RH40 (supplied by BASF).

[0030] Solid carrier is intended to represent the substance that perfume composition or some components of perfume composition can be chemically or physically bound.Generally, such solid carrier is used to stabilize composition or control the evaporation rate of composition or some components.Solid carrier is currently used in the art, and the skilled person knows how to achieve the desired effect.However, non-limiting examples of solid carrier can include absorbent gum or polymer or inorganic material, such as porous polymer, cyclodextrin, dextrin, maltodextrin, wood-based material, organic or inorganic gel, clay, gypsum, talc, or zeolite.

[0031] Other non-limiting examples of solid carriers can include encapsulating materials. Examples of such materials include glucose syrup, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectins, vegetable gums such as gum acacia (gum arabic), urea, sodium chloride, sodium sulfate, zeolites, sodium carbonate, sodium bicarbonate, clays, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, carbohydrates, sugars such as sucrose, monosaccharides, disaccharides, trisaccharides, and polysaccharides, and derivatives such as chitosan, starch, cellulose, carboxymethyl methylcellulose, methylcellulose, hydroxyethyl cellulose, ... Examples of suitable polyols / sugar alcohols include sorbitol, maltitol, xylitol, erythritol, and isomalt, polyethylene glycol (PEG), polyvinylpyrrolidine (PVP), polyvinyl alcohol, acrylamide, acrylates, polyacrylic acid and related substances, maleic anhydride copolymers, amine functional polymers, vinyl ethers, styrene, polystyrene sulfonates, vinyl acids, ethylene glycol-propylene glycol block copolymers, vegetable gums, acacia gum, pectin, xanthan, alginates, carrageenan, citric acid or any water soluble solid acid, fatty alcohols or fatty acids, and mixtures thereof, as well as H. Wall forming and plasticizing materials may be included such as those listed in reference texts such as Scherz, Hydrokolloides: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr's Verlag GmbH & Co., Hamburg, 1996.Encapsulation is a process well known to those skilled in the art and can be carried out by using techniques such as spray drying, coagulation, and even extrusion; or it can consist of coating encapsulation, including coacervation and complex coacervation techniques.

[0032] Non-limiting examples of solid supports include core-shell capsules comprising aminoplast, polyamide, polyester, polyurea or polyurethane type resins, or mixtures thereof, using techniques such as phase separation processes induced by polymerization, interfacial polymerization, coacervation, or all of these, optionally in the presence of polymeric stabilizers or cationic copolymers (all of the aforementioned techniques are described in the prior art), optionally in the presence of polymeric stabilizers or cationic copolymers (all of the aforementioned resins are well known to those skilled in the art).

[0033] The resins can be prepared by polycondensation of aldehydes (such as formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid, or glycolaldehyde, and mixtures thereof) with amines, such as urea, benzoguanamine, glycouril, melamine, methylolmelamine, methylated methylolmelamine, guanazole, and mixtures thereof. Alternatively, alkylolated polyamines can be used, which are preformed resins, such as those commercially available under the trademarks Urac® (supplied by Cytec Technology Corp.), Cymel® (supplied by Cytec Technology Corp.), Urecoll®, or Luracoll® (supplied by BASF).

[0034] 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 and trimethylolpropane (known under the trademark Takenate®, supplied by Mitsui Chemicals, Inc.), of which the trimer of xylylene diisocyanate and trimethylolpropane and the biuret of hexamethylene diisocyanate are preferred.

[0035] Some of the seminal publications on the encapsulation of perfumes by polycondensation of amino resins, i.e. melamine-based resins with aldehydes, include articles such as Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683, and 1990, vol. 41, page 91, published by K. Dietrich et al., which already described the various parameters influencing the production of such core-shell microcapsules according to prior art methods, which are further detailed and illustrated 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 while it is impossible to cover all the published developments here, a general knowledge in encapsulation technology is very important. A more recent relevant publication disclosing suitable uses of such microcapsules is, for example, the article by K. Bruyninckx and M. Dusselier in ACS Sustainable Chemistry & Engineering, 2019, vol. 7, pages 8041-8054.

[0036] By "perfume base" herein is meant a composition that includes at least one perfuming co-ingredient.

[0037] By "perfuming co-ingredient" is meant herein a compound used in a perfume formulation or composition that is used for the primary purpose of imparting a hedonic effect, i.e., imparting or modifying odor. In other words, such a co-ingredient must not only have an odor, but must also be recognized by those skilled in the art as being capable of imparting or modifying the odor of the composition in a positive or pleasant way, in order to be considered a perfuming ingredient.

[0038] The nature and type of perfuming co-ingredients present in the base do not warrant a more detailed description here, and in any case are not exhaustive, and can be selected by the skilled person on the basis of their general knowledge and according to the intended use or application and the desired sensory effect.In general terms, these perfuming co-ingredients belong to various chemical classes such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen or sulfur heterocyclic compounds, and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin.

[0039] Mention may in particular be made of co-perfuming 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~]undec-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 α-pinene; - Balsam components: 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, Hexylcinnamaldehyde, 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-cyclohexene -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-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, vergyl acetate, geraniol, p-menth-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 methyl dihydrojasmonate, 3-methyl ethyl-5-phenyl-1-pentanol, vergyl proprionate, 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, amylcinnamaldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-Dimethylethyl)-1-cyclohexyl, vergyl isobutyrate, and / or methyl ionone isomeric mixture;, - 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, 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-cyclopentene tadecen-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® (supplied by 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; - Other ingredients (e.g. amber, powdery, spicy, or watery): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any stereoisomers thereof, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, 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] According to a particular embodiment, the perfuming composition of the invention comprises at least one woody component as a perfuming co-ingredient.

[0041] The perfume base according to the present invention may not be limited to the above-mentioned perfume combinations, and many others of these combinations are listed in reference texts such as the book Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, by S. Arctander, or other works of a similar nature, as well as in the abundant patent literature in the perfumery field. It is also understood that said combinations may be compounds known to release in a controlled manner various types of perfume compounds, also known as pro-perfumes or pro-fragrances. Non-limiting examples of suitable propurfumes 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, 3-(dodecylsulfonyl)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one, linear polysiloxane copolymers of (3-mercaptopropyl)(methyl)dimethoxysilane, 2-(dodecylthio)octane, and the like. -4-one, 2-(dodecylsulfonyl)octan-4-one, 4-oxooctane-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-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, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene))methoxy)ethyl)benzene, 1-methoxy-4-(1-phenethoxyprop-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-pentylcyclopentylidene)methoxy)-4- Propylbenzene, 2-ethoxy-1-((2-methoxy-2-phenylvinyl)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 mixtures thereof.

[0042] By "perfuming adjuvants" is meant herein an ingredient capable of imparting additional benefits such as color, specific lightfastness, chemical stability, etc. A detailed description of the nature and type of auxiliaries commonly used in perfumery 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 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 antiirritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins, and mixtures thereof. By "fixatives", also called "modifiers", is meant herein an agent capable of influencing the odor of the composition to which it is incorporated, and in particular the evaporation rate and intensity, in a way that can be perceived over time by the observer or user, compared to the same perception in the absence of the modifier. In particular, modifiers can extend the time over which a fragrance is perceived.Non-limiting examples of suitable modifiers 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 mixtures thereof; neopentyl glycol diisononanoate; cetearyl ethylhexanoate; panthenol ethyl ether, DL-panthenol, N-hexadecyl n-nonanoate, n-octadecyl n-nonanoate, profragrance, cyclodextrin, encapsulation, and combinations thereof. Up to 20% by weight of the modifier, based on the total weight of the fragrance composition, may be incorporated into the perfumed consumer product.

[0043] It is understood that a person skilled in the art can fully design the optimal formulation for the desired effect by simply applying standard knowledge in the art and by trial and error methodology by mixing the above-mentioned components of the fragrance composition.

[0044] The composition of the present invention, consisting of at least one composition as defined above and at least one perfume carrier, constitutes a particular embodiment of the present invention, as well as a perfume composition containing at least one composition as defined above, at least one perfume carrier, at least one perfume base, and optionally at least one perfume adjuvant.

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

[0046] The compositions of the invention can also be advantageously used in all areas of modern perfumery, i.e. fine perfumery or functional perfumery, to positively impart or modify the odor of consumer products to which said compositions are added. Another object of the invention therefore consists of perfumed consumer products comprising, as perfuming ingredient, at least one composition as defined above.

[0047] The compositions of the present invention can be added as is or as part of the perfume composition of the present invention.

[0048] For clarity, "perfumed consumer product" is intended 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, fabric, or household surface).In other words, the perfumed consumer product according to the present invention is a perfumed consumer product that contains a functional formulation corresponding to a desired consumer product and an optional additional beneficial agent, and an olfactory effective amount of at least one composition 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 does not warrant a more detailed description here and is in any case not exhaustive: a person skilled in the art can select them on the basis of his general knowledge and depending on the nature of said product and the desired effect.

[0050] Non-limiting examples of suitable perfumed consumer products include fragrances such as fine fragrances, splashes or eau de parfums, colognes, or shave or aftershave lotions; liquid or solid detergents, optionally in the form of pods or tablets, fabric softeners, liquid or solid scent enhancers, dryer sheets, fabric deodorants, ironing water, paper, bleach, carpet cleaners, curtain care products, and other fabric care products; hair care products (e.g., shampoos, leave-on or rinse-off hair conditioners, color formulations or hairsprays, color care products, hair shaping products, dental care products), disinfectants, body care products, such as intimate care products; cosmetics (e.g., skin creams or lotions, vanishing creams or deodorants). or antiperspirants (e.g. sprays or roll-ons), depilatories, tanning products, tanning products, after-sun products, nail products, skin cleansers, makeup); or skin care products (e.g. soaps, shower or bath mousses, oils or gels, or hygiene products, or foot / hand care products); air care products such as air fresheners and "ready to use" powder air fresheners that can be used in domestic spaces (rooms, refrigerators, cupboards, shoes, or cars) and / or public spaces (hall, hotel, mall, etc.); or home care products such as mould removers, furniture care products, wipes, dishwashing detergents, or hard surface (e.g. floor, bath, sanitary, or window cleaners) cleaners; leather care products; car care products such as polishes, waxes, or plastic cleaners.

[0051] According to any embodiment of the present invention, the perfumed consumer product of the present invention is characterized by a pH greater than or equal to 1. In particular, the perfumed consumer product of the present invention has a pH comprised between 1 and 12, or between 1 and 8. Even more particularly, the perfumed consumer product of the present invention has a pH comprised between 1 and 6.

[0052] According to a particular embodiment, the perfumed consumer product of the present invention is in the form of a personal care, home care or fabric care consumer product, in particular a shower gel, shampoo, soap, fabric detergent or softener and general-purpose cleaner, which contains ingredients that are common in such consumer products. The main functional ingredients of the perfumed consumer product are surfactants and / or softener ingredients that can clean and / or soften fabrics and / or textiles of various natures, such as clothing, curtain fabrics, carpet and furniture fabrics, or other household surfaces, skin or hair, and are typically used in a large amount of water or water-based solvent. Thus, these are formulations in which the amount of water is typically 50-99% by weight of the perfumed consumer product, except for soaps or solid detergents, where the amount of water is at most 20%.

[0053] A more detailed description of such fabric cleaner and / or softener formulations is not warranted here, and descriptions of many of the current liquid formulations can be found in the cleaner / fabric softener patents and other relevant literature, such as the text by Louis Ho Tan Tai, "Detergents et Produits de Soins Corporels, Chapters 1 to 7 in particular, Dunod, Paris, 1999, or other similar and / or more recent texts on the art of liquid fabric softener and general-purpose cleaner formulations. Patent publication WO 2010 / 105873 also lists by way of example, particularly on pages 9 to 21, to the extent that it describes typical current ingredients other than perfume of such liquid products. Of course, many other examples of liquid cleaner and / or fabric softener formulations can be found in the literature. Any such liquid formulation, i.e., liquid fabric cleaner or conditioner and / or general-purpose cleaner, can be used in the compositions described herein.

[0054] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a liquid fabric softener comprising a fabric softener active base in an amount comprised between 85 and 100% by weight based on the total weight of the perfumed consumer product. The main component of the fabric softener active base is water or a water-based solvent. The fabric softener active base may comprise dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts, Hamburg ester quats, triethanolamine quats, silicones, and mixtures thereof. Optionally, the fabric softener active base of the composition may further comprise a viscosity modifier, preferably selected from the group consisting of calcium chloride, in an amount comprised between 0.05 and 1% by weight based on the total weight of the liquid base.

[0055] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a general purpose cleaner comprising a general purpose cleaner active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The main component of the general purpose cleaner active base is water or a water-based solvent. The general purpose active base may comprise a linear alkyl benzene sulfonate (LAS) in an amount of 1-2%, a non-ionic surfactant in an amount of 2%-4%, and an acid such as citric acid in an amount of 0.1-0.5%.

[0056] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a liquid detergent comprising a liquid detergent active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The main component of the active base of the liquid detergent is water or a water-based solvent. The liquid detergent active base may comprise anionic surfactants such as alkyl benzene sulfonate (ABS), linear alkyl benzene sulfonate (LAS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), sodium lauryl ether sulfate (SLES), methyl ester sulfonate (MES); nonionic surfactants such as alkyl amines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides; or mixtures thereof.

[0057] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a solid detergent comprising a solid detergent active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The solid detergent active base may comprise at least one surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic surfactants and mixtures thereof. The surfactant in the solid detergent active base is preferably selected from the group consisting of linear alkene benzene sulfonates (LABS), sodium laureth sulfate, sodium lauryl ether sulfate (SLES), sodium lauryl sulfate (SLS), alpha-olefin sulfonates (AOS), methyl ester sulfonates (MES), alkyl polyglycosides (APG), primary alcohol ethoxylates, in particular lauryl alcohol ethoxylates (LAE), primary alcohol sulfonates (PAS), soaps, and mixtures thereof. The solid detergent active base may contain additional ingredients commonly used in powder detergent consumer products selected from the group consisting of bleaching agents such as TAED (tetraacetylethylenediamine); buffering agents; builders such as zeolites, sodium carbonate, or mixtures thereof; soil releasing or suspending polymers; granulated enzyme particles such as cellulase, lipase, protease, mannanase, pectinase, or mixtures thereof; corrosion inhibitors; antifoam agents; suds suppressors; dyes; fillers such as sodium silicate, sodium sulfate, or mixtures thereof; hydrogen peroxide sources such as sodium percarbonate or sodium perborate; and mixtures thereof.

[0058] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a shampoo or shower gel comprising a shampoo or shower gel active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The main component of the shampoo or shower gel active base is water or a water-based solvent. The shampoo shower gel active base may comprise sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside, and amino acid based surfactant.

[0059] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a bar soap comprising a soap active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The bar soap active base may comprise a salt of a weak acid, typically a salt of a weak acid, which may be a fatty acid, and a strong base, such as sodium hydroxide.

[0060] Some of the perfumed consumer products mentioned above may represent aggressive media for the compositions of the invention and may therefore require the latter to be protected against premature degradation, for example by encapsulation or by chemically binding the ingredients of the invention with other chemicals suitable for releasing them upon an appropriate external stimulus, such as enzymes, light, heat or a pH change.

[0061] The proportions in which the compositions according to the invention can be incorporated into the various products or compositions mentioned above vary within wide ranges of values, depending on the nature of the article to be perfumed and the desired sensory effect, as well as on the nature of the perfuming co-ingredients in a given base, when the compositions according to the invention are mixed with them, solvents or additives commonly used in the art.

[0062] For example, in the case of fragrance compositions, typical concentrations are on the order of 0.001% to 30% or even more by weight of the compositions of the present invention based on the weight of the composition in which they are incorporated, and in the case of perfumed consumer products, typical concentrations are on the order of 0.0001% to 10% or even more by weight of the compositions of the present invention based on the weight of the consumer product in which they are incorporated.

[0063] The compositions of the present invention can be prepared according to the methods described hereinafter. EXAMPLES

[0064] Hereinafter, the present invention will be described in more detail by the following examples. The abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (°C). NMR spectra were obtained using a 400 MHz (1 H) and 100MHz ( 13 C) operated Bruker Avance II Ultrashield 400 plus, or 500MHz ( 1 H) and 125MHz ( 13 C) operated Bruker Avance III 500 or 600MHz ( 1 H) and 150MHz ( 13 The spectra were acquired using a Bruker Avance III 600 cryoprobe operated at 40°C. Spectra were internally referenced to tetramethylsilane at 0.0 ppm. 1 H NMR signal shifts are expressed in δ ppm, coupling constants (J) are expressed in Hz and the following multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; and b, broad (indicating unresolved couplings) and were analyzed using Bruker Topspin software. 13 C NMR data are expressed as chemical shifts δ ppm and hybridization from DEPT90 and DEPT135 experiments: C, quaternary (s); CH, methine (d); CH2, methylene (t); CH3, methyl (q). Gas chromatography was performed using an Agilent 6850 instrument equipped with a DB-23 column (20M, 0.18 mm, 0.2 μm, H2, 110 °C, 3 °C / min) at 2.0 mL / min, injection volume of 1.0 μL, split of 100:1, using hydrogen as carrier gas. Relative compositions were given in % using FID detection.

[0065] Example 1 Synthesis of the Compositions of the Invention a) Epoxidation of Commercially Available Habanolides® mCPBA (<75% tech. 40.5 g, 1.2 equiv., 176 mmol) was added portionwise to a stirred solution of commercial Habanolide® (35.0 g, 147 mmol) in toluene (150 mL) cooled to 5° C. in an ice bath. The suspension was stirred at ambient temperature for 4 h, then diluted with water, the aqueous phase re-extracted with diethyl ether, the organic phase washed with saturated sodium bicarbonate solution, 10% sodium sulfite solution, dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 40.1 g of crude epoxide mixture. Further purification by Kugelrohr distillation at 135-140° C. and 0.8 mbar gave 36.7 g of epoxide mixture. (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one [ka] (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one [ka] (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one [ka] (1SR,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one [ka]

[0066] b) Selective hydrolysis of (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one To a stirred solution of the epoxide mixture prepared in step a) (20.0 g, 78.7 mmol) in ethyl formate (100 mL) was added Amberlyst® A-15 (2.0 g, 10 wt %) and the suspension was stirred at ambient temperature for 18 h. The suspension was diluted with diethyl ether, washed with saturated sodium bicarbonate solution, brine, the organic phase dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 21.2 g of a mixture of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one, and (SR)-13-((SR)-1,3-dihydroxypropyl)oxacyclotridecan-2-one. Further purification by filtration through a short plug of silica (18 cm, 400 mL) with a gradient of ethyl acetate:heptane 5:95 to 15:85 gave a mixture of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (10.2 g) and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, mixed fractions (5.2 g) which on further elution gave a mixture of (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one and (SR)-13-((SR)-1,3-dihydroxypropyl)oxacyclotridecan-2-one (6.25 g).Further purification of the mixture of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (10.2 g) was carried out by flash chromatography (column 330 g Puriflash® 40 μM using a gradient of ethyl acetate:heptane 1:99 to 5:95 as eluent) to give (1SR,16SR)-5,17-dioxabicyclo[1 4.1.0]heptadecan-6-one (5.1 g, as the major isomer) was obtained, which on further elution gave a mixture of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (58 / 39, E / Z, 1.95 g) and pure (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (1.6 g).

[0067] c) Hydrolysis of a mixture containing (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one as the major isomer (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (major isomer) (5.1 g, 20 mmol) obtained in step b) in THF (70 mL) containing 10% H2SO4 (10 mL) was heated at 65° C. for 12 h. The cooled mixture was diluted with saturated sodium bicarbonate solution, extracted with diethyl ether, the organic phase was washed with brine, dried over anhydrous sodium sulfate, filtered and the solvent was removed in vacuo to give 4.7 g of crude diol, which was used directly in the next step without further purification. (12RS,13SR)-12,13-dihydroxyoxacyclohexadecan-2-one [ka]

[0068] d) Conversion of the diol mixture obtained in step c) into orthoesters and elimination. A suspension of citric acid (170 mg, 0.9 mmol), a mixture of the diol prepared in step c) (4.8 g, 17.6 mmol), and trimethyl orthoformate (9.5 g, 89 mmol) was heated at 70° C. for 45 minutes using a rotary evaporator to form the intermediate orthoester. The solvent was removed in vacuum, the residue was dissolved in acetic anhydride (14.0 g, 140 mmol), and the mixture was heated at 150° C. for 60 minutes using an Anton Parr Monowave50 in 3×1.5 g batches, then cooled. The batches were combined, diluted with diethyl ether (50 mL), washed with sodium carbonate solution, then saturated sodium bicarbonate solution, brine, dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuum to give 3.7 g of crude composition of the invention. Further purification by flash chromatography (220 g, Puriflash® column, 40 μM silica) eluting with heptane:ethyl acetate (99:1 to 97:3) gave 2.4 g of pure inventive composition, which was Kugelrohr distilled (130° C., 0.8 mbar). 2.2 g of pure inventive composition was obtained, containing 97% w / w (Z)-oxacyclohexadec-12-en-2-one, about 1.1% w / w (E)-oxacyclohexadec-12-en-2-one, and about 1.6% w / w (Z)-oxacyclohexadec-13-en-2-one. (Z)-Oxacyclohexadec-12-en-2-one [ka]

[0069] Example 2 Synthesis of the Compositions of the Invention Peracetic acid (39% in acetic acid, 120 mmol, 23.4 g) was slowly added dropwise over 2 h to a stirred amount of commercial Habanolide® (25.0 g, 97%, 105 mmol) heated to 50° C. Then 10% H2SO4 (5 g) was added dropwise slowly and heating was continued at 50° C. for an additional 2 h. The mixture was cooled, diluted with ethyl acetate and 10% sodium sulfite solution, the aqueous phase was re-extracted with ethyl acetate, then the organic phase was washed with saturated sodium bicarbonate solution, brine, dried over anhydrous MgSO4, filtered and the solvent removed in vacuo to give 29.2 g of a crude mixture of diols. The diol mixture was purified by filtration through a short plug of silica (200 mL) with heptane:ethyl acetate (1:9) (2×250 mL), then heptane:ethyl acetate (1:6) (2×250 mL), then heptane:ethyl acetate (3:7) (500 mL), and finally heptane:ethyl acetate (1:1), followed by pure ethyl acetate (500 mL) to give the diol mixture as an oil, which slowly crystallized. 11 g. A portion of the diol mixture (5.0 g, 18.4 mmol) was dissolved in dichloromethane (20 mL), rac-camphorsulfonic acid (250 mg, 1.07 mmol, catalytic amount) was added, and the mixture was stirred at ambient temperature for 15 h. The mixture was diluted with diethyl ether, washed with saturated sodium bicarbonate solution, brine, dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 5.3 g of the desired diol mixture.

[0070] A solution of C-24 dicarboxylic acid (455 mg, 1.14 mmol), the diol mixture prepared above (5.3 g, 19.5 mmol), and trimethyl orthoformate (2.5 g, 23.5 mmol) was heated in a Kugelrohr flask at 70° C. for 45 minutes to form the intermediate orthoester. The solvent was removed in vacuo and the residue was placed under vacuum (0.8 mbar) and slowly heated to 155° C.-165° C. to give 4.2 g of crude inventive composition. Further purification by flash chromatography (220 g, Puriflash® column, 40 mM silica) using heptane:ethyl acetate (99:1-97:3) as eluent gave 2.1 g of pure inventive composition. This was subjected to Kugelrohr distillation (130° C., 0.8 mbar) to give 2.0 g of a pure composition of the invention containing 61.5% w / w (Z)-oxacyclohexadec-12-en-2-one, about 6.1% w / w (E)-oxacyclohexadec-12-en-2-one, about 3.4% w / w (E)-oxacyclohexadec-13-en-2-one, and about 28.7% w / w (Z)-oxacyclohexadec-13-en-2-one.

[0071] Example 3 Synthesis of the Compositions of the Invention a) Selective hydrolysis of (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one To a stirred solution of the epoxide mixture prepared in Example 1a) (28.0 g, 110 mmol) in THF (100 mL) was added dilute sulfuric acid (10 mL, 5%, 0.05 equiv.) and stirred at ambient temperature for 48 h. The reaction mixture was diluted with MTBE, then washed with saturated sodium bicarbonate solution, brine, dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 20.9 g of a mixture of (12SR,13SR)-12,13-dihydroxyoxacyclohexadecan-2-one, (13RS,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one, (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, and (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one. Further purification by filtration through a small silica plug (15 cm, 200 mL) and heptane:ethyl acetate (99:1 to 95:5) as eluent (100 mL fractions) afforded 7.3 g of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one. (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one [ka] (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one [ka]

[0072] b) Selective hydrolysis of a mixture containing (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one To a stirred solution of the mixture containing (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one (12:13 isomers, 65:35, 7.3 g, 28.7 mmol) prepared in the previous step in ethyl formate (20 mL) was added Amberlyst® A-15 (0.7 g, 10 wt %) and the suspension was stirred at ambient temperature for 15 h. The reaction mixture was diluted with diethyl ether, washed with saturated sodium bicarbonate solution, brine, the organic phase dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 8.1 g of a mixture of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one. Further purification by filtration through a short plug of silica (10 cm, 200 mL) with a gradient of ethyl acetate:heptane 5:95 to 50:50 gave 4.7 g of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, which on further elution gave 2.35 g of (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one. (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one [ka]

[0073] c) Isomerization of (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one To a solution of (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one (2.35 g, 8.6 mmol) prepared in the previous step in dichloromethane (20 mL) was added rac-camphorsulfonic acid (200 mg, 0.8 mmol) and the mixture was stirred at ambient temperature for 15 h. The mixture was diluted with diethyl ether, washed with saturated sodium bicarbonate solution, brine, dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 2.0 g of the desired (13RS,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one and (13RS,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one. (13RS,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one [ka]

[0074] d) Formation and elimination of orthoesters i) One-pot process using citric acid The diol prepared in step c) (1.0 g, 3.67 mmol) was dissolved in trimethyl orthoformate (2.0 g, 18.9 mmol), citric acid (35 mg, 0.18 mmol) was added and the mixture was heated in an Anton Parr Monowave 50 at 175° C. for 2 hours and then cooled. The reaction mixture was diluted with diethyl ether and saturated sodium bicarbonate solution. The aqueous phase was re-extracted with diethyl ether, then the combined organic phase was washed with saturated sodium bicarbonate solution, then with brine, dried over anhydrous sodium sulfate, filtered and the solvent removed in vacuo to give 0.9 g of crude composition of the invention still containing about 20% of orthoester. Further purification by chromatography using Puriflash® (40 g cartridge, 30 mM) with 99:1 to 97:3 heptane:ethyl acetate as eluent gave 0.6 g of composition of the invention. This was further purified by Kugelrohr distillation (145° C. at 0.5 mbar) to give 0.45 g of a pure composition of the invention containing about 5.4% w / w (Z)-oxacyclohexadec-12-en-2-one, about 0.3% w / w (E)-oxacyclohexadec-12-en-2-one, about 0.6% w / w (E)-oxacyclohexadec-13-en-2-one, and about 93.7% w / w (Z)-oxacyclohexadec-13-en-2-one. (Z)-Oxacyclohexadec-13-en-2-one [ka]

[0075] ii) Alternative method: formation of orthoester followed by pyrolysis with acetic anhydride The diol prepared in step c) (1.0 g, 3.67 mmol) was dissolved in trimethyl orthoformate (2.0 g, 18.9 mmol) and citric acid (35 mg, 0.18 mmol) was heated at 75° C. for 45 min, then cooled and the excess orthoformic acid was evaporated in vacuo to give the crude orthoester. (3aSR,17aRS)-2-Methoxytetradecahydro-7H-[1,3]dioxolo[4,5-d][1]oxacyclohexadecin-7-one [ka]

[0076] The crude orthoester was used without further purification and was dissolved in acetic anhydride (2.0 g, 19.6 mmol) and heated at 150° C. for 1 h, then cooled. The mixture was diluted with diethyl ether and water and stirred at ambient temperature for 1 h. The aqueous phase was re-extracted with diethyl ether, then the combined organic phase was washed with saturated sodium bicarbonate solution, then with brine, dried over anhydrous sodium sulfate, filtered, and the solvent removed in vacuo to give 0.8 g of crude inventive composition. Further purification by chromatography using a Puriflash® (40 g cartridge, 30 mM) with 99:1 to 97:3 heptane:ethyl acetate as eluent gave 0.5 g of inventive composition. This was further purified by Kugelrohr distillation (145° C. at 0.5 mbar) to give 0.4 g of pure ca. 5.5% w / w (Z)-oxacyclohexadec-12-en-2-one, ca. 0.2% w / w (E)-oxacyclohexadec-12-en-2-one, ca. 0.6% w / w (E)-oxacyclohexadec-13-en-2-one, and ca. 93.7% w / w (Z)-oxacyclohexadec-13-en-2-one.

[0077] Example 4 Preparation of the Perfume Composition A fine fragrance composition was prepared by mixing the following ingredients: [Table 1-1] [Table 1-2]

[0078] The addition of 2000 parts by weight of the composition described in Example 1 to the above fine fragrance composition imparts to the latter a musky character in the direction of nitro musk with a strong powdery character. The blends of the compositions of the invention blend particularly well with powdery elements such as coumarin and oriental notes such as vanillin.

[0079] The addition of 2000 parts by weight of the composition according to Example 2 to the above fine fragrance composition imparted to the latter a musky character in the direction of nitromusks with a strong powdery character, as well as creamy oriental notes. The blend of the composition of the invention is particularly well matched with powdery elements such as coumarin, oriental notes such as vanillin, and woody-sandalwood elements such as (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol and 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol.

[0080] The addition of the same amount of Habanolide® also imparted a musky character in the direction of macrocyclic musks but with a woody aspect. The resulting composition lacks powdery, creamy and oriental characteristics. The Habanolide® blend is particularly well matched with woody-cedar elements such as cedarwood oil and 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone.

[0081] The addition of the composition of the present invention to the above fine fragrance compositions gives the composition more volume, an effect that can also be achieved with Habanolide®, but to a lesser extent.

[0082] Example 5 Preparation of Eau de Toilettes Containing the Compositions of the Invention An eau de toilette was prepared by adding 12% by weight of the inventive composition of Example 4 to ethanol, relative to the total weight of the eau de toilette.

[0083] Example 6 Preparation of liquid detergents containing the compositions of the present invention [Table 2]

[0084] A liquid detergent is prepared by adding 0.5-1.5% by weight of the inventive composition of Example 4, based on the total weight of the liquid detergent, to the unscented liquid detergent formulation of Table 1 with gentle shaking.

[0085] Example 7 Preparation of Fabric Softeners Comprising the Compositions of the Present Invention [Table 3]

[0086] The softener is prepared by weighing methyl bis[ethyl(tallow fatty acid)]-2-hydroxyethyl ammonium methyl sulfate, which is heated to 65°C. Then, water and 1,2-benzisothiazolin-3-one are placed in a reactor and heated to 65°C with stirring. To the above mixture, methyl bis[ethyl(tallow fatty acid)]-2-hydroxyethyl ammonium methyl sulfate is added. The mixture is stirred for 15 minutes and CaCl2 is added. Then, 0.5-2% by weight of the composition of the present invention from Example 4, based on the total weight of the softener, is added. The mixture is stirred for 15 minutes and cooled to room temperature with stirring (viscosity measurement: result 35 + / - 5 mPas. (shear rate 106 sec -1 )).

[0087] Example 8 Preparation of a clear isotropic shampoo containing the composition of the present invention [Table 4]

[0088] The shampoo is prepared by dispersing Polyquaternium-10 in water. The remaining ingredients of Phase A are mixed separately by adding them one after the other with thorough mixing after each addition. This premix is ​​added to the Polyquaternium-10 dispersion and mixed for an additional 5 minutes. Then premixed Phase B and premixed Phase C are added with stirring (Monomuls 90L-12 is heated in Texapon NSO IS to melt). Phase D and Phase E are added with stirring. The fragrance-free shampoo formulation is obtained by adjusting the PH with citric acid solution until the pH is 5.5-6.0.

[0089] The fragranced shampoo is prepared by adding 0.4-0.8% by weight of the inventive composition of Example 4, based on the total weight of the shampoo, to the unscented shampoo formulation of Table 3 with gentle shaking.

[0090] Example 9 Preparation of structured shower gels containing the compositions of the present invention [Table 5]

[0091] The shower gel is prepared by adding 0.5-1.5% by weight of the inventive composition of Example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 4 with gentle shaking.

[0092] Example 10 Preparation of a clear shower gel containing the composition of the present invention [Table 6]

[0093] A clear shower gel is prepared by adding 0.5-1.5% by weight of the inventive composition of Example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 5 with gentle shaking.

[0094] Example 11 Preparation of a milky white shower gel containing the composition of the present invention [Table 7]

[0095] A clear shower gel is prepared by adding 0.5-1.5% by weight of the inventive composition of Example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 6 with gentle shaking.

[0096] Example 12 Preparation of pearlescent shampoo containing the composition of the present invention [Table 8-1] [Table 8-2]

[0097] The shampoo is prepared by dispersing guar hydroxypropyltrimonium chloride and polyquaternium-10 in water and tetrasodium EDTA. After Phase A is uniform, add 10% NaOH solution (Phase B). Then premixed Phase C is added and the mixture is heated to 75°C. Phase D ingredients are added and mixed until uniform. The mixture is cooled. At 45°C, add Phase E ingredients with mixing. Final viscosity is adjusted with 25% NaCl solution and pH of 5.5-6 is adjusted with 10% NaOH solution.

[0098] A fragranced pearlescent shampoo is prepared by adding 0.4-0.8% by weight of the inventive composition of Example 4, based on the total weight of the shampoo, to the unscented shampoo formulation of Table 7 with gentle shaking.

[0099] Example 13 Preparation of structured shower gels containing the compositions of the present invention [Table 9]

[0100] A clear shower gel is prepared by adding 0.5-1.5% by weight of the inventive composition of Example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 8 with gentle shaking.

[0101] Example 14 Preparation of anhydrous antiperspirant spray formulations containing the compositions of the present invention [Table 10]

[0102] The anhydrous antiperspirant spray formulation is prepared using a high speed mixer. Silica and Quaternium-18-Hectorite are added to the mixture of isopropyl myristate and cyclomethicone. After complete swelling, aluminum chlorohydrate is added in small portions with stirring until the mixture is homogenous and free of lumps. The perfume oil, which is the composition of the present invention from Example 4, is then added.

[0103] Example 15 Preparation of Deodorant Spray Emulsion Formulations Comprising the Compositions of the Invention [Table 11]

[0104] The deodorant spray emulsion formulation is prepared by mixing and dissolving all ingredients according to the order in Table 10. Fill into aerosol cans, crimp and add propellant. Aerosol Fill: 40% active solution 60% propane / butane (2.5 bar).

[0105] Example 16 Preparation of Deodorant Stick Formulations Comprising the Compositions of the Invention [Table 12]

[0106] The deodorant stick formulation is obtained by weighing all the ingredients of Part A and heating to 70-75°C. Ceteareth-25 is added after mixing and heating the other Part A ingredients. After Ceteareth-25 is dissolved, stearic acid is added. Part B is prepared by dissolving Triclosan in 1,2-propylene glycol. The evaporated water is replaced. Part B is then poured into Part A while mixing slowly. The perfume oil (phase C), which is the composition of the invention of Example 4, is added while shaking gently. For storage, the plastic bag is placed in a bucket and sealed after cooling. The mould is filled at about 70°C.

[0107] Example 17 Preparation of Deodorant Roll-On Formulations Comprising the Compositions of the Present Invention [Table 13]

[0108] Part A is prepared by sprinkling hydroxyethyl cellulose into water in small portions while stirring rapidly with a turbine until the hydroxyethyl cellulose is completely swollen and forms a clear gel. Slowly pour Part B into Part A while continuing to stir until the entire mixture is homogenous. Then add Parts C and D while shaking gently.

[0109] Example 18 Preparation of a day cream-based O / W emulsion containing the composition of the present invention [Table 14]

[0110] The day cream base O / W emulsion is prepared by heating phase A and phase B separately to 70-75°C. Phase A is added to phase B, followed by vacuuming. The mixture is stirred and cooled to 55°C for 15 minutes. After cooling to room temperature, when the temperature reaches 45°C, phenoxyethanol (and) piroctone olamine (part C) are added. The mixture is stirred for 5 minutes, after which sodium carbomer (part D) and the perfume oil (part E), the composition of the invention of Example 4, are added. The mixture is stirred for 3 minutes, after which stirring is stopped for 15 minutes. When the temperature of the mixture reaches 30°C, stirring is resumed for another 15 minutes, until the cream is homogenous, glossy and free of lumps. If necessary, adjust the pH to 6.70-7.20 with Glydant, Phenonip, or Nipaguard PO5, or to 6.30-7.00 with Nikkoguard.

Claims

1. 1. A composition comprising: a) 0.5 to 98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-10% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-10% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 98.8% w / w of (Z)-oxacyclohexadec-13-en-2-one (The percentages are based on the total weight of the composition.) Including, A composition, wherein the weight ratio of E-diastereoisomer to Z-diastereoisomer is in the range of from 14:86 to 0.5:99.

5.

2. The composition, a) 55-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-7% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-6% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 31% w / w of (Z)-oxacyclohexadec-13-en-2-one The composition of claim 1 , comprising:

3. The composition, a) 90-98.8% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-2.5% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-1% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 2.5% w / w of (Z)-oxacyclohexadec-13-en-2-one The composition of claim 1 , comprising:

4. The composition, a) 0.5-10% w / w of (Z)-oxacyclohexadec-12-en-2-one; b) 0.1-2.5% w / w of (E)-oxacyclohexadec-12-en-2-one; c) 0-3% w / w of (E)-oxacyclohexadec-13-en-2-one; and d) 55-98.8% w / w of (Z)-oxacyclohexadec-13-en-2-one The composition of claim 1 , comprising:

5. The composition of any one of claims 1 to 4, wherein the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of from 10:90 to 1:

99.

6. The composition of any one of claims 1 to 4, wherein the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of 9.5:90.5 to 1:

99.

7. The composition of any one of claims 1 to 4, wherein the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of from 7.5:92.5 to 1:

99.

8. The composition of any one of claims 1 to 4, wherein the weight ratio of the 12-positional isomer to the 13-positional isomer is in the range of from 55:45 to 99:1, or in the range of from 20:80 to 1:

99.

9. A method for imparting, enhancing, improving or modifying the odor characteristics of a perfume composition or a perfumed article, comprising adding to said composition or perfumed article an effective amount of a composition according to any one of claims 1 to 4.

10. 5. Use of a composition according to any one of claims 1 to 4 as a perfuming ingredient.

11. A fragrance composition comprising: i) at least the composition according to claim 1; ii) at least one component selected from the group consisting of a perfume carrier and a perfume base; and iii) optionally at least one perfume adjuvant; A fragrance composition comprising:

12. A perfumed consumer product comprising at least a composition according to any one of claims 1 to 4 or a perfume composition according to claim 11.

13. 13. The perfumed consumer product of claim 12, wherein the perfumed consumer 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.

14. The perfume consumer product may be a fine fragrance, a splash or eau de parfum, a cologne, a shave or aftershave lotion, a liquid or solid detergent, optionally in the form of a pod or tablet, a fabric softener, a liquid or solid scent enhancer, a dryer sheet, a fabric freshener, an ironing water, paper, a bleach, a carpet cleaner, a curtain care product, a shampoo, a leave-on or rinse-off hair conditioner, a color formulation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair conditioner ...

14. The perfumed consumer product of claim 13 which is an aspirin, a skin cream or lotion, a vanishing cream, a deodorant or antiperspirant, a depilatory, a tanning product, a tanning product, an after-sun product, a nail product, a skin cleanser, a makeup, a perfumed soap, a shower or bath mousse, an oil or gel, a foot care / hand care product, a hygiene product, an air freshener, a "ready-to-use" powder air freshener, a mold remover, an furniture care product, a wipe, a dishwashing detergent or a hard surface cleaner, a leather care product, a car care product.