Fragrance substances

Abstract

The present invention relates to the field of perfumery. More particularly, the present invention relates to a composition of matter comprising a compound of formula (I) as defined below, the weight ratio of the cis-diastereoisomer to the trans-diastereoisomer being in the range of 90:10 to 99.5:0.5, and at least 10% w / w of the cis-(1S,2R) diastereoisomer. Said composition of matter is a useful perfume ingredient, and therefore the present invention comprises the composition of matter of the present invention as part of a perfumed composition or perfumed consumer product.

Description

[Technical Field]

[0001] The present invention relates to the field of perfumery. More particularly, the present invention relates to a composition of matter comprising a compound of formula (I) as defined below, wherein the weight ratio of the cis-diastereoisomer to the trans-diastereoisomer is in the range of 90:10 to 99.5:0.5, and at least 10% w / w of the cis-(1S,2R) diastereoisomer. The composition of matter is a useful perfume ingredient, and therefore the present invention includes the composition of matter of the present invention as part of a perfume composition or perfumed consumer product.

[0002] Background of the Invention The perfume industry is constantly searching for new ingredients to support the creativity of perfumers by diversifying the notes present in the palette. Furthermore, perfumers are looking for strong and robust perfume ingredients that allow them to give any composition a typical character that can be perceived over several hours. However, only a few ingredients that impart fragrance notes are available. Therefore, there is a need to develop alternatives.

[0003] WO 2016079431 and Angew. Chem. Int. Ed., 2016, 55, 13719-13723 report compounds of formula (I) where n is 1 as compounds that impart the aforementioned olfactory properties. Most specifically, this second prior art mentions that the aroma notes are due to two diastereoisomers: cis-(1S,2R)-2-octylcyclopropanecarboxylic acid and trans-(1S,2S)-2-octylcyclopropanecarboxylic acid. However, surprisingly, it has now been found that the trans-diastereoisomer negatively impacts the organoleptic properties of compounds of formula (I), with cis-(1R,2S)-2-octylcyclopropanecarboxylic acid being the key diastereoisomer.

[0004] Thus, the present invention provides a novel composition of matter as defined above having predominantly cis-diastereoisomers that provides a highly potent and substantial odor note combined with a citrus aspect never before reported in the prior art. The prior art did not anticipate that the composition of matter of the present invention would provide an improvement in performance while providing a citrus note.

[0005] Summary of the Invention The present invention relates to a never-disclosed composition of matter as defined above and the use of said composition of matter as a perfuming ingredient, which imparts a citrus odor note in addition to an aromatic odor note.

[0006] A first subject of the present invention is therefore a composition of matter comprising: Formula (I) [ka] [wherein n is 1 or 2] wherein the weight ratio of cis-diastereoisomer to trans-diastereoisomer is in the range of 90:10 to 99.5:0.5; at least 10% w / w of the cis-(1S,2R) diastereoisomer, the percentages being based on the total weight of the composition of matter; It is a composition of matter having the following structure:

[0007] A second subject of the present invention is a method for imparting, enhancing, improving or modifying the odor characteristics of a perfuming composition or a perfumed article or surface, comprising adding to said composition or perfumed article an effective amount of a composition of matter as defined above.

[0008] Another subject of the present invention is the use of the composition of substances defined above as a perfuming ingredient.

[0009] Another subject of the present invention is a perfuming composition comprising: i) a composition of matter 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 flavoring adjuvant The fragrance composition has the following structure:

[0010] A further subject of the present invention is a scented consumer product comprising a composition of matter as defined above or a perfuming composition as defined above.

[0011] Description of the Invention An unexpected synergistic effect has been found between the four diastereoisomers of the compound of formula (I) which leads to compositions of matter of the present invention which impart a strong and substantial odor note and, unexpectedly, a citrus aspect.

[0012] A first subject of the present invention is therefore a composition of matter comprising: Formula (I) [ka] [wherein n is 1 or 2] wherein the weight ratio of cis-diastereoisomer to trans-diastereoisomer is in the range of 90:10 to 99.5:0.5; at least 10% w / w of the cis-(1S,2R) diastereoisomer, the percentages being based on the total weight of the composition of matter; It is a composition of matter having the following structure:

[0013] Said compositions of matter can be used as perfuming ingredients, for example to impart strong substantive odour notes of the perfume type with a citrus phase.

[0014] With regard to the terms "cis-diastereoisomer" and "trans-diastereoisomer," the terms have the ordinary meaning understood by a person skilled in the art, i.e., the cis-diastereoisomer corresponds to cis-(1S,2R)-2-nonylcyclopropanecarboxylic acid and cis-(1R,2S)-2-nonylcyclopropanecarboxylic acid when n is 2, or to cis-(1S,2R)-2-octylcyclopropanecarboxylic acid and cis-(1R,2S)-2-octylcyclopropanecarboxylic acid when n is 1, and the trans-diastereoisomer corresponds to trans-(1S,2S)-2-nonylcyclopropanecarboxylic acid and trans-(1R,2R)-2-nonylcyclopropanecarboxylic acid when n is 2, or to trans-(1S,2S)-2-octylcyclopropanecarboxylic acid and trans-(1R,2R)-2-octylcyclopropanecarboxylic acid when n is 1.

[0015] With respect to the term "cis-(1S,2R) diastereoisomer," this term has the ordinary meaning as understood by those skilled in the art, i.e., when n is 2, it is cis-(1S,2R)-2-nonylcyclopropanecarboxylic acid, and when n is 1, it is cis-(1S,2R)-2-octylcyclopropanecarboxylic acid.

[0016] According to any embodiment of the present invention, the composition of matter of the present invention has at least 15%, 20%, 25%, 30%, 35%, or 40% w / w of the cis-(1S,2R) diastereoisomer, percentages based on the total weight of the composition of matter. In particular, the composition of matter of the present invention has at least 15%, 20%, 25%, 30%, 35%, or 40% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, percentages based on the total weight of the composition of matter.

[0017] According to any embodiment of the present invention, n is 1. In other words, the composition of matter of the present invention comprises: a) 90-99.5% w / w cis-2-octylcyclopropanecarboxylic acid; b) 0.5% to 10% w / w of trans-2-octylcyclopropanecarboxylic acid; and Percentages are based on the total weight of the composition of matter.

[0018] According to any embodiment of the present invention, trans-2-octylcyclopropanecarboxylic acid may be in the form of a pure enantiomer or a mixture of two enantiomers. Trans-2-octylcyclopropanecarboxylic acid may be in racemic or scalemic form. Thus, trans-2-octylcyclopropanecarboxylic acid may be trans-(1S,2S)-2-octylcyclopropanecarboxylic acid, trans-(1R,2R)-2-octylcyclopropanecarboxylic acid, or a mixture thereof. In particular, trans-2-octylcyclopropanecarboxylic acid may be in racemic form, i.e., a 50:50 weight ratio mixture of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid and trans-(1R,2R)-2-octylcyclopropanecarboxylic acid.

[0019] According to any embodiment of the present invention, cis-2-octylcyclopropanecarboxylic acid may be in the form of a pure enantiomer or a mixture of two enantiomers. Cis-2-octylcyclopropanecarboxylic acid may be in racemic or scalemic form. Thus, cis-2-octylcyclopropanecarboxylic acid may be cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, cis-(1R,2S)-2-octylcyclopropanecarboxylic acid, or a mixture thereof. In particular, cis-2-octylcyclopropanecarboxylic acid may be in racemic form, i.e., a 50:50 weight ratio mixture of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid and cis-(1R,2S)-2-octylcyclopropanecarboxylic acid.

[0020] According to any embodiment of the present invention, the composition of matter of the present invention may have at least 45% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, the percentage being based on the total weight of the composition of matter.

[0021] According to any embodiment of the present invention, in the composition of matter of the present invention, the various components mentioned above are present in the following amounts: a) 45-99.5% w / w cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) cis-(1R,2S)-2-octylcyclopropanecarboxylic acid up to 49.75% w / w; c) up to 10% w / w of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid; d) trans-(1R,2R)-2-octylcyclopropanecarboxylic acid up to 10% w / w exists in Percentages are based on the total weight of the composition of matter; The weight ratio of cis-diastereoisomer to trans-diastereoisomer is in the range of 90:10 to 99.5:0.5.

[0022] According to one embodiment of the present invention, in the composition of matter of the present invention, the various components mentioned above are present in the following amounts: a) 47.5-99% w / w cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) up to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid; c) trans-(1S,2S)-2-octylcyclopropanecarboxylic acid at a maximum of 5% w / w; d) trans-(1R,2R)-2-octylcyclopropanecarboxylic acid at a maximum of 5% w / w It exists in.

[0023] According to any one of the above embodiments of the invention, the composition of matter of the invention may have about 45 to 95% w / w (cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, particularly about 47.5 to 90% w / w (cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, in particular about 47.5 to 80% w / w (cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, in particular about 47.5 to 70% w / w (cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, in particular about 47.5 to 60% w / w (cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, more in particular about 47.5 to 50% w / w (cis-(1S,2R)-2-octylcyclopropanecarboxylic acid).

[0024] According to a particular embodiment of the present invention, the composition of matter of the present invention comprises about 1 to 49.75% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid, in particular about 5 to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid, in particular about 10 to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid, in particular about 20 to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid. The cis-(1R,2S)-2-octylcyclopropanecarboxylic acid may have about 30 to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid, in particular about 40 to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid, and even more particularly about 45 to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid.

[0025] According to any one of the above embodiments of the invention, the composition of matter of the invention may have about 0.25 to 5% w / w trans-(1S,2S)-2-octylcyclopropanecarboxylic acid, more particularly about 0.5 to 3% w / w trans-(1S,2S)-2-octylcyclopropanecarboxylic acid.

[0026] According to any one of the above embodiments of the invention, the composition of matter of the invention may have about 0.25-5% w / w trans-(1R,2R)-2-octylcyclopropanecarboxylic acid, more particularly about 0.5-3% w / w trans-(1S,2S)-2-octylcyclopropanecarboxylic acid.

[0027] According to one embodiment of the present invention, in the composition of matter of the present invention, the various components mentioned above are present in the following amounts: a) 47.5-49.75% w / w cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) 47.5-49.75% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid; c) 0.5% to 2.5% w / w of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid; d) 0.5% to 2.5% w / w of trans-(1R,2R)-2-octylcyclopropanecarboxylic acid It exists in.

[0028] According to another particular embodiment of the invention, in the composition of matter of the invention, the various components mentioned above are present in the following amounts: a) 10-49.75% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) 45-99.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid; c) up to 10% w / w of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid; d) trans-(1R,2R)-2-octylcyclopropanecarboxylic acid up to 10% w / w It exists in.

[0029] According to any one of the above embodiments of the present invention, the weight ratio of cis-diastereoisomer to trans-diastereoisomer is in the range of 92:8 to 99.5:0.5, more particularly in the range of 95:5 to 99:1, more particularly in the range of 97:3 to 99:1.

[0030] As mentioned above, the compositions of matter of the present invention have a very strong natural aromatic organoleptic profile with citrus notes, while being long-lasting, and are highly valued by perfumers because the overall scent profile opens new directions in their creativity when compared to prior art ingredients.

[0031] Indeed, when comparing the odor of the composition of matter of the present invention with that of a prior art composition of matter having more than 10% w / w of trans isomer, the composition of matter according to the present invention is itself characterized by a distinctly different odor profile with a never-before-reported citrus phase, maintaining an intense and natural fragrance and lacking the fatty and dusty character of the prior art compounds. Moreover, the composition of matter of the present invention imparts distinctly stronger and more substantial notes, while providing more brightness to the perfume composition. The composition of matter of the present invention is itself characterized by exhibiting a more pleasant olfactory stimulation profile.

[0032] Said differences serve the compositions of matter of the present invention and the prior art compounds for different uses, i.e., to provide different organoleptic impressions.

[0033] As mentioned above, the present invention relates to the use of the composition of matter 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 altering the odor characteristics of a perfuming composition or a perfumed article or surface, comprising adding an effective amount of the composition of matter of the present invention to said composition or article, for example, to impart its typical notes. The final hedonic effect may depend on the exact dosage and organoleptic properties of the composition of matter of the present invention, but it is understood that in any case, the addition of the composition of matter of the present invention will impart its typical touch in the form of a note, touch, or aspect to the final product, depending on the dosage. Furthermore, the composition of matter of the present invention may be used to improve the organoleptic properties of perfuming ingredients or to reduce unpleasant olfactory impressions, such as the metallic, dusty, or chemical aspects of some perfuming ingredients.

[0034] By "use of the composition of matter of the invention", this is also understood herein to be the use of any composition comprising the composition of matter of the invention and which can be advantageously used in the perfumery industry.

[0035] Indeed, said compositions which can be advantageously used as perfuming ingredients are also the subject of the present invention.

[0036] Another subject of the present invention is therefore a perfuming composition comprising: i) a composition of the substances of the invention as defined above as perfuming ingredients; ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and iii) optionally at least one flavoring adjuvant The fragrance composition has the following structure:

[0037] By "perfume carrier" is meant herein a material that is substantially neutral from a perfume point of view, i.e., that does not significantly modify the organoleptic properties of the perfuming ingredients. The carrier may be liquid or solid.

[0038] Liquid carriers may include, but are not limited to, emulsifying systems, i.e., solvents or 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.However, but not limited to, 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, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanoate, tri-ethyl citrate or their mixtures, which are most commonly used. For compositions having both a fragrance carrier and a fragrance base, suitable fragrance carriers in addition to those previously specified 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 that known under the trademark Cremophor® RH 40 (supplied by BASF).

[0039] Solid carrier means a material that can be chemically or physically bound to the perfume composition or some components of the perfume composition. Generally, such solid carriers are used to stabilize the composition or control the evaporation rate of the composition or some components. Solid carriers are currently used in this field, and those skilled in the art know how to achieve the desired effect. However, non-limiting examples of solid carriers may include absorbent gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, wood-based materials, organic or inorganic gels, clays, gypsum talc, or zeolites.

[0040] Non-limiting examples of solid carriers may include encapsulating materials. Examples of such materials may include wall-forming materials and plasticizing materials, such as monosaccharides, disaccharides, or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins, or pectins, or 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 process well known to those skilled in the art, and may be carried out by using techniques such as spray drying, coagulation, or extrusion, or by coating encapsulation, including coacervation and complex coacervation techniques.

[0041] Non-limiting examples of solid carriers may include core-shell capsules with aminoplast, polyamide, polyester, polyurea or polyurethane type resins or mixtures thereof (all of which are well known to those skilled in the art) using techniques such as polymerization-induced phase separation processes, interfacial polymerization, coacervation or all of which are described in the prior art, optionally in the presence of polymeric stabilizers or cationic copolymers.

[0042] The resins may 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 resin alkylolated polyamines commercially available under the trademarks Urac® (supplied by Cytec Technology Corp.), Cymel® (supplied by Cytec Technology Corp.), Urecoll®, or Luracoll® (supplied by BASF) may be used.

[0043] Other resins are those prepared by polycondensation of polyols, such as glycerol, 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 trademark Takenate®, supplier: Mitsui Chemicals), among which those prepared by polycondensation of the trimer of xylylene diisocyanate with trimethylolpropane and the biuret of hexamethylene diisocyanate are preferred.

[0044] Some of the seminal literature related to the encapsulation of perfumes by polycondensation of amino resins, i.e., melamine-based resins, with aldehydes, includes articles such as those published by K. Dietrich et al. in Acta Polymerica, vol. 40, pp. 243, 325, and 683, 1989, and vol. 41, pp. 91, 1990. These articles already describe the various parameters that influence the preparation of such core-cell microcapsules according to prior art methods, which are further detailed and exemplified in the patent literature. U.S. Pat. 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 advances published here, a general knowledge of encapsulation technology is extremely important. Relevant more recent publications disclosing suitable uses of such microcapsules are e.g. illustrated by the article by K. Bruyninckx and M. Dusselier, ACS Sustainable Chemistry & Engineering, 2019, vol. 7, pages 8041-8054.

[0045] As used herein, a "perfume base" is a composition having at least one perfuming co-ingredient.

[0046] By "perfuming co-ingredient," we mean herein a compound used in a perfuming preparation or composition to impart a hedonic effect. In other words, to be considered a perfuming ingredient, such a co-ingredient must be recognized by those skilled in the art as not merely having a scent, but also being able to impart or modify the scent of the composition in a positive or pleasant way. Perfuming co-ingredients may also impart additional benefits beyond modifying or imparting a scent, such as long-lasting properties, blooming, counteracting malodors, antibacterial effects, antiviral effects, microbial stability, or pest control.

[0047] The nature and type of perfuming co-ingredients present in the base do not warrant a more detailed description herein, and in any case are not exhaustive, and can be selected by a person skilled in the art, based on their general knowledge, according to the intended use or application and the desired organoleptic effect. Generally, these perfuming co-ingredients belong to various chemical classes such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds and essential oils, and said perfuming co-ingredients may be of natural or synthetic origin.

[0048] especially, - 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; - Balsam 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- (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-methyldihydrochloride Rojasmonate, 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 cinnamaldehyde, 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, allylheptanoate, 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, styryl 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-cyclopentane 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 of its stereoisomers, 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 Mention may be made of perfuming co-ingredients commonly used in perfume formulations such as:

[0049] According to a particular embodiment, the perfuming composition of the invention comprises, as perfuming co-ingredient, at least one woody component.

[0050] The perfume base according to the invention may not be limited to the above-mentioned perfuming co-ingredients, many others of which are in any case listed in reference texts, such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest editions, or other works of a similar type, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may be compounds known to release in a controlled manner various types of perfuming compounds, also known as pro-perfumes or pro-fragrances. Non-limiting examples of suitable pro-fragrances 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 copolymer of (3-mercaptopropyl)(methyl)dimethoxysilane, 2-(dodecylthio)octane-4- one, 2-(dodecylsulfonyl)octan-4-one, 4-oxooctan-2-yl dodecanoate, 2-phenylethyloxo(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, (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 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-pentylcyclopentyl) cyclopentylidene)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.

[0051] By "perfuming adjuvants", we mean here ingredients that can impart additional benefits such as color, in particular lightfastness, chemical stability, etc. A detailed description of the nature and type of adjuvants typically 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 modifiers (e.g., surfactants, thickeners, gelling agents 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 anti-irritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0052] It will be understood that a person skilled in the art can perfectly design the optimum formulation for the desired effect by mixing the above-mentioned components of the perfume composition simply by applying standard knowledge in this field as well as by trial and error methodology.

[0053] The composition of the present invention, consisting of at least one composition of matter as defined above and at least one perfume carrier, is a particular embodiment of the present invention, as well as a perfume composition having at least one composition of matter as defined above, at least one perfume carrier, at least one perfume base, and optionally at least one perfume adjuvant.

[0054] For the sake of clarity, it is also understood that any mixture obtained directly from a chemical synthesis, such as a reaction medium containing the composition of matter 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 composition of matter of the invention in a form suitable for perfumery. Unpurified reaction mixtures are therefore generally excluded from the present invention, unless expressly stated otherwise.

[0055] The compositions of matter of the invention can also be used advantageously in any field of modern perfumery, i.e. in fine perfumery or functional perfumery, to positively impart or modify the odor of consumer products to which said compositions of matter are added. Another subject of the present invention therefore consists in perfumed consumer products which, as perfuming ingredient, have at least one composition of matter as defined above.

[0056] The compositions of matter of the present invention may be added as or as part of the perfuming compositions of the present invention.

[0057] 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, fabric, or household surface). In other words, a perfumed consumer product according to the present invention is a perfumed consumer product having a functional formulation, and optionally an additional benefit agent corresponding to the desired consumer product, and an olfactory-effective amount of at least one composition of matter of the present invention. For clarity, said perfumed consumer product is a non-edible product.

[0058] The nature and type of ingredients of perfumed consumer products do not warrant a more detailed description herein, which is in any case not exhaustive and can be selected by a person skilled in the art, based on his general knowledge, according to the nature and desired effect of said product.

[0059] Non-limiting examples of suitable perfumed consumer products include perfumes, such as fine perfumes, splash or eau de parfum, colognes or shave or aftershave lotions; fabric care products, such as liquid detergents, pod or solid detergents or tablets, fabric softeners, liquid or solid scent boosters, dryer sheets, fabric refreshers, ironing water, paper, bleach, carpet cleaners, curtain care products; body care products, such as hair care products (e.g., shampoos, leave-on or rinse-off hair conditioners, 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, vanishing creams or deodorants or beauty products), body care products, ... antiperspirants (e.g. spray or roll-on), hair remover, tanning or sun or after-sun products, nail products, skin cleansing, make-up); or skin care products (e.g. soap, shower or bath mousse, oil or gel, or hygiene or foot / hand care products); air care products, such as air fresheners or "ready-to-use" powder air fresheners that can be used in home 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 detergents for hard surfaces (e.g. floor, bath, hygiene or window cleaning); leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0060] Some of the previously mentioned perfumed consumer products may represent an aggressive medium for the compositions of matter of the present invention, which may therefore need to be protected from premature degradation, for example by encapsulation or by chemical bonding to other chemicals suitable for releasing the ingredients of the present invention upon a suitable external stimulus, such as enzymes, light, heat or a change in pH.

[0061] The proportions of the composition of matter according to the invention that can be incorporated into the various products or compositions mentioned above vary within wide ranges 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 co-ingredients in a given base, when the composition of matter according to the invention is mixed with perfuming co-ingredients, solvents or additives commonly used in this field.

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

[0063] Example 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 ( 1 H) and 125MHz ( 13 Bruker Avance III 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 given in Hz with the following multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; and b, broad (indicating unresolved couplings) and were interpreted using Bruker Topspin software. 13C NMR data are expressed as chemical shifts δ ppm and hybridization from DEPT 90 and DEWP 135 experiments: C, quaternary (s); CH, methine (d); CH, methylene (t); CH, methyl (q). GC method: GC-23 (20 M, 0.18 mm, 0.2 um, H, 110 °C at 3 °C / min).

[0064] Example 1 Synthesis of Compositions of Matter of the Invention a) Step 1: Preparation of ethyl 2-octylcycloprop-2-ene-1-carboxylate A solution of ethyl diazoacetate (85% w / w in CHCl, 3.24 g, 24.11 mmol) in CHCl (35 mL) was added via syringe pump over 12 h to a mixture of 1-decyne (10.0 g, 72.3 mmol) and Rh(OAc) (107 mg, 0.241 mmol). The solvent was removed in vacuo, and the residue was purified by CC / SiO (cyclohexane / AcOEt 99:1 to 90:10) to give ethyl 2-octylcycloprop-2-ene-1-carboxylate in 76% yield (67% based on ethyl diazoacetate and used / recovered 1-decyne). [ka]

[0065] b) Step 2: Preparation of 2-octylcycloprop-2-ene-1-carboxylic acid LiOH (133 mg, 5.57 mmol) was added to a solution of ethyl 2-octylcycloprop-2-ene-1-carboxylate (1000 mg, 4.46 mmol) in 4:1 THF / HO (15 mL), and the reaction mixture was then heated to reflux for 56 h. The cooled reaction mixture was concentrated in vacuo, diluted with HO (10 mL), and extracted with EtO (3 × 10 mL). The aqueous phase was acidified to pH 1 with 35% aqueous HCl and then re-extracted with EtO (3 × 15 mL). The organic phase was dried (NaSO) and concentrated to give quantitatively pure acid, 2-octylcycloprop-2-ene-1-carboxylic acid. The latter was used crude without distillation for the subsequent hydrogenation step. [ka]

[0066] c) Step 3: Preparation of the Composition of Matter of the Invention A solution of 2-octylcycloprop-2-ene-1-carboxylic acid (210 mg, 1.07 mmol) in AcOEt (10 ml) was hydrogenated over Lindlar's catalyst (2.2 mg, 5% Pd / CaCO) for 3 h (theoretical H224 ml). After complete conversion, the reaction mixture was filtered through a short path of Celite®, then concentrated in vacuo and subjected to bulb-to-bulb distillation to quantitatively obtain a mixture containing 98% cis-(1SR,2RS)-2-octylcyclopropanecarboxylic acid and 2% trans-(1SR,2SR)-2-octylcyclopropanecarboxylic acid.

[0067] Boiling point 150℃ / 0.40mbar.

[0068] The analysis is consistent with that obtained for the optically active version described in Example 3.

[0069] Example 2 Synthesis of Compositions of Matter of the Invention a) Step 1: Preparation of ethyl 2-octylcyclopropane-1-carboxylate A solution of ethyl 2-octylcycloprop-2-ene-1-carboxylate ester (1.8 g, 8.02 mmol) in AcOEt (32 ml) was hydrogenated over Lindlar's catalyst (85 mg, 5% Pd / CaCO) for 3 h (theoretical H2176 ml). After complete conversion, the reaction mixture was filtered through a short path of Celite®, then concentrated in vacuo and bulb-to-bulb distilled to quantitatively obtain ethyl 2-octylcyclopropane-1-carboxylate with a cis:trans ratio of 98:2.

[0070] Boiling point: 150℃ / 0.35mbar. [ka]

[0071] b) Step 2: Preparation of the Composition of Matter of the Invention 10% aqueous LiOH (5 ml) was added to a solution of ethyl cis-2-octylcyclopropane-1-carboxylate (600 mg, 2.86 mmol) in MeOH (5 ml) at 20 °C. The reaction mixture was stirred at this temperature for 12 h, then acidified with 2 N aqueous HCl and extracted with EtO. The organic phase was dried (NaSO) and concentrated to give a mixture containing 98% cis-(1SR,2RS)-2-octylcyclopropanecarboxylic acid and 2% trans-(1SR,2SR)-2-octylcyclopropanecarboxylic acid in 87% yield. Analysis is consistent with that obtained for the optically active version described in Example 3.

[0072] Example 3 Synthesis of Compositions of Matter of the Invention It was obtained from known undec-2-yn-1-ol [Synthesis 1999, 107] according to the procedure published in Angew. Chem. Int. Ed. 2016, 55, 13719. It was then purified by CC / SiO (cyclohexane / AcOEt 99 / 1 to 9 / 1) to achieve a stereochemical purity of 92% (+)-cis-(1S,2R)-2-octylcyclopropanecarboxylic acid and 8% (-)-trans-(1R,2R)-2-octylcyclopropanecarboxylic acid. [ka]

[0073] Example 4 Synthesis of Compositions of Matter of the Invention a) Step 1: Preparation of (+-)-ethyl 2-nonyl-2-cyclopropene-1-carboxylate A solution of ethyl diazoacetate (85% w / w in CHCl, 2.97 g, 21.9 mmol) in CHCl (27 mL) was added via syringe pump over 12 h to a mixture of 1-undecine (10.0 g, 65.67 mmol) and Rh(OAc) (96 mg, 0.44 mmol). After 3 h at 20 °C, the solvent was removed in vacuo, and the residue was purified by CO / SiO (cyclohexane / AcOEt 99:1 to 90:10) to give the desired (+-)-ethyl 2-nonyl-2-cyclopropene-1-carboxylate in 83% yield (87% based on ethyl diazoacetate and used / recovered 1-undecine). [ka]

[0074] b) Step 2: Preparation of ethyl 2-nonylcyclopropanecarboxylate A solution of (+-)-ethyl 2-nonyl-2-cyclopropene-1-carboxylate (4.0 g, 16.78 mmol) in AcOEt (65 ml) was hydrogenated over Lindlar's catalyst (170 mg, 5% Pd / CaCO) for 3 h (theoretical H2368 ml). After complete conversion, the reaction mixture was filtered through a short path of Celite®, then concentrated in vacuo and bulb-to-bulb distilled to quantitatively obtain saturated ethyl 2-nonylcyclopropanecarboxylate with a cis:trans ratio of 98:2. Boiling point: 150 °C / 0.25 mbar. [ka]

[0075] c) Step 3: Preparation of (+-)-2-nonyl-2-cyclopropene-1-carboxylic acid LiOH (78 mg, 3.25 mmol) was added to a solution of (+-)-ethyl 2-nonyl-2-cyclopropene-1-carboxylate (310 mg, 1.3 mmol) in 4:1 THF / HO (5 mL), and the reaction mixture was then heated to reflux for 56 h. The cooled reaction mixture was concentrated in vacuo, diluted with HO (5 mL), and extracted with EtO (3 × 10 mL). The aqueous phase was acidified to pH 1 with 35% aqueous HCl and then re-extracted with EtO (3 × 15 mL). The organic phase was dried (NaSO) and concentrated to give quantitatively pure (+-)-2-nonyl-2-cyclopropene-1-carboxylic acid. The latter was used crude for the subsequent hydrogenation step without distillation. [ka]

[0076] d) Step 4: Preparation of (1RS,2SR)-2-nonylcyclopropane-1-carboxylic acid 10% aqueous LiOH (5 mL) was added to a solution of (1RS,2SR)-2-nonylcyclopropanecarboxylate (684 mg, 2.85 mmol) in MeOH (5 mL) at 20° C. The reaction mixture was stirred at this temperature for 18 h, then acidified with 2 N aqueous HCl and extracted with EtO. The organic phase was dried (NaSO) and concentrated to give a mixture containing 98% cis-(1RS,2SR)-2-nonylcyclopropane-1-carboxylic acid and 2% trans-(1RS,2RS)-2-nonylcyclopropanecarboxylic acid in 88% yield.

[0077] It can also be obtained quantitatively by Lindlar hydrogenation of (+-)-2-nonyl-2-cyclopropene-1-carboxylic acid according to the conditions described above. Boiling point: 165° C. / 0.05 mbar. [ka]

[0078] Example 5 Synthesis of Comparative Compositions of Matter a) Step 1: Preparation of undeca-1,3-dien-1-yl acetate An E / Z mixture of commercially available 1-undec-2-enal (10.0 g, 59.4 mmol), AcOK (4.96 g, 50.5 mmol), and AcO (15.14 mL, 16.38 g, 160 mmol) was refluxed for 4 h. The cooled reaction mixture was poured onto ice / HO (100 mL). EtO (150 mL) was added, and the partitioned organic phase was washed with saturated aqueous NaHCO (solid NaHCO) until neutral, then with brine. The organic phase was dried (NaSO) and concentrated, and the resulting oil was purified by bulb-to-bulb distillation to give undeca-1,3-dien-1-yl acetate in 78% yield as a ca. 15:35:20:30 mixture of stereoisomers.

[0079] Boiling point: 130℃ / 1.3mbar. [ka]

[0080] b) Step 2: Preparation of (Z)-undec-2-en-1-yl acetate Undeca-1,3-dien-1-yl acetate (1.0 g, 4.75 mmol), maleic acid (34 mg, 0.295 mmol), [(Cp * )Ru(1,3-COD)][BF] (72 mg, 0.166 mmol) and acetone (6 ml) were charged into an autoclave under N. The autoclave was purged and then pressurized with H. After 18 h at 60 °C / 5 bar, the autoclave was cooled, depressurized, and the reaction mixture was diluted with AcOEt (15 ml). Filtration through SiO (10 g) and concentration gave an oil that was purified by CC / SiO (25 g, cyclohexane / AcOEt 99:1) to give (Z)-undec-2-en-1-yl acetate as an 87:13 mixture of Z / E stereoisomers in 46% yield.

[0081] Rf = 0.22 (99:1). [ka]

[0082] c) Step 3: Preparation of (Z)-undec-2-en-1-ol (Z)-Undec-2-en-1-yl acetate (30 mg, 0.141 mmol) in MeOH (15 mL) was saponified with KOH (9.51 mg, 0.17 mmol) at 70 °C for 3 h. The cooled reaction mixture was concentrated in vacuo, and the residue was partitioned between EtO (10 mL) and H2O (10 mL). The organic phase was washed with brine, dried (Na2SO4), and concentrated. Purification by CC / SiO2 (cyclohexane / AcOEt 99:1 to 9:1) afforded (Z)-undec-2-en-1-ol quantitatively as an 87:13 mixture of Z / E stereoisomers. [ka]

[0083] d) Step 4: Preparation of cis-2-octylcyclopropyl-1-methanol EtZn (1M / hexane, 10 mL, 10 mmol) was added to a solution of 87:13 (Z / E)-undec-2-en-1-ol (332 mg, 1.95 mmol) in hexane (10 mL) at −50° C., followed by CHCl (5.28 g, 19.7 mmol). The reaction mixture was slowly equilibrated at 20° C. and cooled again to −40° C. after 18 h. Saturated aqueous NHCl (20 mL) was added dropwise, and the reaction mixture was equilibrated to 20° C. After partitioning, the aqueous phase was washed with EtO (2 × 25 mL). The combined organic phases were washed with brine, dried (Na2SO4), and concentrated to give an orange oil that was purified by CC / SiO2 (cyclohexane / Et2O 98:2 to 8:2) to give cis-2-octylcyclopropyl-1-methanol (83% yield) as a colorless 84:16 cis / trans mixture.

[0084] Finally, further purification by CC / SiO2 (cyclohexane / AcOEt 99 / 1 to 9 / 1) followed by bulb-to-bulb distillation gave pure 2-octylcyclopropyl-1-methanol in 64% yield with a cis:trans ratio of 98:2.

[0085] Rf=0.18(9:1). Boiling point: 125℃ / 0.66mbar. [ka]

[0086] e) Step 5: Preparation of comparative compositions of matter Jones reagent (CrO, 2.7 M in 36% HSO, 43.3 mL, 117 mmol) was added dropwise to a solution of 2-octylcyclopropyl-1-methanol alcohol (8.7 g, 46.7 mmol, 84:16 cis / trans) in acetone (100 mL) at 0 °C. After 18 h at 20 °C, cold H2O (100 mL) was added and the mixture was extracted with pentane (3 × 50 mL). The organic phase was extracted with 15% NaOH (100 mL). The basic aqueous phase was acidified with 10% aqueous HCl and partitioned with pentane (3 × 100 mL). The organic phase was washed with brine (2 × 50 ml), dried (NaSO), filtered, and concentrated to give the acidic mixture in 70% yield (84:16 cis-(1SR,2RS)-2-octylcyclopropanecarboxylic acid / trans-(1RS,2RS)-2-octylcyclopropanecarboxylic acid). Analysis is consistent with that obtained for the optically active version described in Example 3.

[0087] Example 6 Synthesis of Comparative Compositions of Matter a) Step 1: Preparation of ethyl undeca-2,3-dienoate EtN (4.4 ml, 31.6 mmol) was added to a solution of ethyl 2-(triphenylphosphoranylidene)acetate (10 g, 28.7 mmol) in CHCl (80 ml) at 0 °C. After 5 min at 0 °C, a solution of nonanoyl chloride (6.59 g, 37.3 mmol) in CHCl (20 ml) was added dropwise at 0 °C. After 18 h at 20 °C, the solvent was concentrated under vacuum. The residue was diluted with EtO (80 ml) and then filtered. This process was repeated four times to precipitate PhPO. Further purification with SiO (80 g, cyclohexane / AcOEt 99:1 to 8:2) afforded pure ethyl undeca-2,3-dienoate in 72% yield. [ka]

[0088] b) Step 2: Preparation of undeca-2,3-dien-1-ol A solution of ethyl undeca-2,3-dienoate ester (1.3 g, 5.19 mmol) in CHCl (10 mL) was added dropwise to a solution of DIBAH (1.2 M in toluene, 9.09 mL, 10.9 mmol) in CHCl (15 mL) at 0 °C over 30 min. After 2 h, MeOH (10 mL) was carefully added, followed by 3 N HCl. The aqueous phase was extracted with EtO. The organic phase was washed with 10% NaOH, dried (NaSO), filtered, and concentrated in vacuo to give pure undeca-2,3-dien-1-ol in 45% yield (72% yield if used in the next step without further purification). [ka]

[0089] c) Step 3: Preparation of (2-octylidenecyclopropyl)methanol EtZn (1 M in hexane, 1.41 mL, 1.41 mmol) was added to ClCHCHCl (5 mL) and the solution was cooled to −15°C. CHCl (473 mg, 1.76 mmol) in ClCHCHCl (5 mL) was added dropwise over 1 h via syringe pump, resulting in the formation of a white precipitate. After an additional 30 min at −15°C, a solution of undeca-2,3-dien-1-ol (250 mg, 1.41 mmol) in ClCHCHCl (4 mL) was added dropwise over 30 min. After a further period of 3 h at −15°C, the temperature was allowed to equilibrate to −10°C and then slowly warmed to 20°C. The white solution was carefully poured into saturated aqueous NHCl and then partitioned with EtO. The organic phase was washed with 5% HCl, then saturated aqueous NaHCO, then HO, and dried (NaSO). Concentration gave a 66:33 mixture of stereoisomers. Further purification using cyclohexane / AcOEt (99:1 to 9:1) on SiO2 / AgNO3 afforded each of the diastereoisomers in 26% yield. [ka]

[0090] d) Step 4: Preparation of 2-octylcyclopropyl-1-methanol The crude (2-octylidenecyclopropyl)methanol (as a 66:33 (Z) / (E) mixture) was hydrogenated over Lindlar's catalyst in the usual manner to give a quantitative 60:40 cis / trans mixture of 2-octylcyclopropyl-1-methanol.

[0091] The analysis corresponds to that reported in Example 5, Step 4 for 2-octylcyclopropyl-1-methanol.

[0092] e) Step 5: Preparation of comparative compositions of matter Conventional Jones oxidation of the 60:40 cis / trans mixture of 2-octylcyclopropyl-1-methanol described above, followed by purification on CC / SiO (cyclohexane / AcOEt 8:2) and bulb-to-bulb distillation, gave a 52:48 mixture of cis-(1SR,2RS)-2-octylcyclopropanecarboxylic acid / trans-(1RS,2RS)-2-octylcyclopropanecarboxylic acid.

[0093] The analysis is consistent with that obtained for the optically active stereoisomers described in Examples 3 and 8.

[0094] Example 7 Synthesis of Comparative Compositions of Matter a) Step 1: Preparation of ethyl 2-octylcyclopropane-1-carboxylate A solution of ethyl diazoacetate (85% / CHCl, 7.5 g, 55.9 mmol) in 1-decene (10.0 g, 71.4 mmol) was added dropwise to a suspension of anhydrous CuSO (2.0 g, 12.5 mmol) in 1-decene (9.0 g, 64.3 mmol) at 100°C over 6 hours. The addition was accompanied by N evolution. Upon completion, the temperature was maintained until evolution ceased. The CuSO was filtered, and the reaction mixture was purified by CHCl / SiO (cyclohexane / AcOEt 99:1 to 9:1). Unreacted 1-decene was recovered, as well as the ester, ethyl cis-2-octylcyclopropane-1-carboxylate, in 42% yield (80% yield based on used / recovered) as a 40:60 cis / trans mixture of stereoisomers.

[0095] The analysis of the cis-diastereoisomer is reported in Example 2. 13 C-NMR: Trans isomer tentatively estimated from the mixture: 174.7(s); 60.3(t); 33.1(t) 29.6(t); 29.4(t); 29.3(t); 29.1(t); 23.0(d); 22.7(t); 20.3(d); 15.6(t); 14.3(q); 14.1(q); 13.2(t).

[0096] b) Step 2: Preparation of comparative compositions of matter

[0097] A 40:60 cis / trans mixture of ethyl cis-2-octylcyclopropane-1-carboxylate (3130 mg, 13.83 mmol) and LiOH (828 mg, 34.6 mmol) in THF (10 mL) and HO (2.5 mL) was heated to reflux for 56 h. The cooled reaction mixture was partitioned between EtO (4 × 25 mL) and HO (4 × 25 mL). The aqueous phase was acidified to pH 1 with 37% HCl, then re-extracted with EtO (4 × 25 mL), washed with HO (2 × 25 mL), dried (NaSO), and concentrated to give a 96% pure 40:60 mixture of cis-(1SR,2RS)-2-octylcyclopropanecarboxylic acid / trans-(1SR,2SR)-2-octylcyclopropanecarboxylic acid in 90% yield. The analysis is consistent with that obtained for the optically active stereoisomers described in Examples 3 and 8.

[0098] Example 8 Synthesis of the comparative compound (+)-trans-(1S,2S)-2-octylcyclopropanecarboxylic acid It was obtained from known undec-2-yn-1-ol [Synthesis 1999, 107] according to the procedure published in Angew. Chem. Int. Ed. 2016, 55, 13719. Subsequent purification by CC / SiO2 (cyclohexane / AcOEt 99 / 1 to 9 / 1) achieved a chemical purity of 98.9%. f =0.42 (c-hexane / AcOEt 7:3). [α] D 20 = +63.1 (c = 0.045, CHCl3). [ka]

[0099] Example 9 Synthesis of Comparative Compositions of Matter It was obtained from the known undec-2-yn-1-ol [Synthesis 1999, 107] according to the procedure published in Angew. Chem. Int. Ed. 2016, 55, 13719. It was then purified by CC / SiO2 (cyclohexane / AcOEt 99 / 1 to 9 / 1) to achieve a stereochemical purity of 94% (-)-cis-(1R,2S)-2-octylcyclopropanecarboxylic acid and 6% (+)-trans-(1S,2S)-2-octylcyclopropanecarboxylic acid. Boiling point: 175 °C / 3 mbar. [α] D 20 =-29.0 (c=0.039, CHCl3). For analysis, see Example 3.

[0100] Example 10 Preparation of fragrance composition A fine fragrance composition was prepared by mixing the following ingredients: [Table 1-1] [Table 1-2]

[0101] The addition of 200 parts by weight of the composition of the substances of the invention described in Example 1 diluted at 10% in dipropylene glycol to the fine fragrance composition described above gave the latter composition an intense and natural fragrance effect that provided a great deal of strength and diffusion to the fragrance. The compositions of matter of the present invention blend particularly well with citrus components such as 6,6-dimethoxy-2,5,5-trimethyl-2-hexene, (E)-2-dodecenal, (Z)-3-dodecenal and dodecanal, woody-powdery components such as 4-(2,2,C-3,T-6-tetramethyl-R-1-cyclohexyl)-3-buten-2-one and 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and isomer mixtures, and amber components, especially (-)-(3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0102] The addition of 200 parts by weight of the comparative composition described in Example 5 diluted to 10% in dipropylene glycol in the same amount imparts a fragrant and citrus character, but with a fatty and dusty note, and the resulting fine fragrance composition lacks a cleansing effect.

[0103] Addition of 200 parts by weight of the comparative composition of matter described in Example 6 diluted 10% in dipropylene glycol in the same amount imparted a similar effect to the addition of the comparative composition of matter described in Example 5, with a stronger, undesirable fatty and dusty note, and was also less potent than the composition of the present invention.

[0104] Addition of 200 parts by weight of the comparative composition of matter described in Example 7 diluted 10% in dipropylene glycol in the same amount imparted a predominantly unpleasant fatty and dusty character, and was also less potent than the composition of the present invention.

[0105] Addition of 200 parts by weight of the comparative composition of matter described in Example 8 diluted 10% in dipropylene glycol in the same amount imparted a predominantly unpleasant fatty character, and was also less potent than the composition of the present invention.

[0106] Example 11 Preparation of an Eau de Toilette with a Composition of Matter of the Invention An eau de toilette was prepared by adding 15% by weight, based on the total weight of the eau de toilette, of the composition of the present invention of Example 10 to ethanol.

[0107] Example 12 Preparation of Liquid Detergents with Compounds of the Invention [Table 2]

[0108] A liquid detergent is prepared by adding, with gentle shaking, 0.5 to 1.5% by weight of the inventive composition of Example 10, based on the total weight of the liquid detergent, to an unperfumed liquid detergent formulation of Table 1, having 200 parts by weight of the inventive composition of matter described in Example 1 diluted at 10% in dipropylene glycol.

[0109] Example 13 Preparation of Fabric Softeners with Compounds of the Invention [Table 3]

[0110] The softener is prepared by weighing out bis[ethyl(tallowate)]-2-hydroxyethylammonium methyl methyl sulfate, which has been heated to 65°C. Water and 1,2-benzisothiazolin-3-one are then placed in a reactor and heated to 65°C with stirring. To the mixture is added bis[ethyl(tallowate)]-2-hydroxyethylammonium methyl methyl sulfate. The mixture is stirred for 15 minutes, and CaCl2 is added. Next, 0.5-2% of the composition of the present invention from Example 10, based on the total weight of the softener, is added, which contains 200 parts by weight of the composition of the present invention described in Example 1 diluted 10% in dipropylene glycol. The mixture is stirred for 15 minutes and allowed to cool to room temperature with stirring (viscosity measurement: 35 + / - 5 mPas (shear rate 106 sec-1)).

[0111] Example 14 Preparation of a clear isotropic shampoo with the composition of the present invention [Table 4]

[0112] 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. Premixed Phase B and premixed Phase C are then added with stirring (Monomuls 90L-12 is dissolved in Texapon NSO IS with heat). Phases D and E are added with stirring. The pH is adjusted to pH 5.5-6.0 with citric acid solution to form an unscented shampoo formulation.

[0113] A perfumed shampoo is prepared by adding, with gentle shaking, 0.4 to 0.8% by weight, based on the total weight of the shampoo, of the composition of the present invention of Example 10, having 200 parts by weight of the composition of matter of the present invention described in Example 1 diluted at 10% in dipropylene glycol, to the unflavored shampoo formulation of Table 3.

[0114] Example 15 Preparation of structured shower gels with compositions of the present invention [Table 5]

[0115] A shower gel is prepared by adding, with gentle shaking, 0.5 to 1.5% by weight, based on the total weight of the shower gel, of the inventive composition of Example 10 to the unperfumed shower gel formulation of Table 4, having 200 parts by weight of the inventive composition of matter described in Example 1 diluted at 10% in dipropylene glycol.

[0116] Example 16 Preparation of a clear shower gel with the composition of the present invention [Table 6]

[0117] A clear shower gel is prepared by adding, with gentle shaking, 0.5 to 1.5% by weight, based on the total weight of the shower gel, of the inventive composition of Example 10 to the unperfumed shower gel formulation of Table 5, having 200 parts by weight of the inventive composition of matter described in Example 1 diluted at 10% in dipropylene glycol.

[0118] Example 17 Preparation of a milky white shower gel with the composition of the present invention [Table 7]

[0119] A milky white shower gel is prepared by adding, with gentle shaking, 0.5 to 1.5% by weight, based on the total weight of the shower gel, of the inventive composition of Example 10 to the unperfumed shower gel formulation of Table 6, having 200 parts by weight of the inventive composition of matter described in Example 1 diluted at 10% in dipropylene glycol.

[0120] Example 18 Preparation of pearly shampoo with the composition of the present invention [Table 8-1] [Table 8-2]

[0121] The shampoo is prepared by dispersing in water and tetrasodium EDTA, guar hydroxypropyltrimonium chloride, and polyquaternium-10. A 10% solution of NaOH (Phase B) is added once Phase A is uniform. The premixed Phase C is then 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, Phase E ingredients are added with mixing. The final viscosity is adjusted with 25% NaCl solution, and the pH is adjusted to 5.5-6 with 10% NaOH solution.

[0122] A perfumed pearlescent shampoo is prepared by adding, with gentle shaking, 0.4 to 0.8% by weight, based on the total weight of the shampoo, of the composition of the present invention of Example 10, having 200 parts by weight of the composition of matter of the present invention described in Example 1 diluted at 10% in dipropylene glycol, to the unflavored shampoo formulation of Table 7.

[0123] Example 19 Preparation of structured shower gels with compositions of the present invention [Table 9]

[0124] A clear shower gel is prepared by adding, with gentle shaking, 0.5 to 1.5% by weight, based on the total weight of the shower gel, of the inventive composition of Example 10 to the unperfumed shower gel formulation of Table 8, having 200 parts by weight of the inventive composition of matter described in Example 1 diluted at 10% in dipropylene glycol.

[0125] Example 20 Preparation of anhydrous antiperspirant spray formulations with compositions of the present invention [Table 10]

[0126] An anhydrous antiperspirant spray formulation is prepared using a high-speed mixer. Silica and quaternium-18-hectorite are added to a mixture of isopropyl myristate and cyclomethicone. Once fully swollen, aluminum chlorohydrate is added in small increments with stirring until the mixture is uniform and free of lumps. Then, perfume oil, which is the composition of the present invention from Example 10, is added, containing 200 parts by weight of the composition of the present invention described in Example 1, diluted 10% in dipropylene glycol.

[0127] Example 21 Preparation of Deodorant Spray Emulsion Formulations with the Compositions of the Present Invention [Table 11]

[0128] The deodorant spray emulsion formulation is prepared by mixing and dissolving all ingredients according to the order in Table 10. Fill into an aerosol can and add the propellant by crimping. Aerosol Fill: 40% active solution 60% propane / butane (2.5 bar).

[0129] Example 22 Preparation of Deodorant Stick Formulations with the Compositions of the Invention [Table 12]

[0130] The deodorant stick formulation is obtained by weighing all the ingredients of Part A and heating to 70-75°C. Once the other Part A ingredients are mixed and heated, add Ceteareth-25. Once Ceteareth-25 is dissolved, add stearic acid. Part B is prepared by dissolving triclosan in 1,2-propylene glycol. Distilled water is supplemented. Part B is then slowly poured into Part A while mixing. A perfume oil (Phase C), which is the composition of the present invention of Example 10, having 200 parts by weight of the composition of the present invention described in Example 1 diluted 10% in dipropylene glycol, is added with gentle shaking. For storage, the plastic bag is placed in a bucket and sealed after cooling. The mold is filled at approximately 70°C.

[0131] Example 23 Preparation of deodorant roll-on formulations with the compositions of the present invention [Table 13]

[0132] Part A is prepared by sprinkling hydroxyethyl cellulose in water in small portions with rapid turbine stirring until the hydroxyethyl cellulose is completely swollen and a clear gel is obtained. Part B is slowly poured into Part A while continuing to stir until the entire mixture is uniform. Parts C and D are then added with gentle shaking.

[0133] Example 24 Preparation of a day cream based O / W emulsion with the composition of the present invention [Table 14]

[0134] The day cream base O / W emulsion is prepared by heating phases A and B separately to 70-75°C. Phase A is added to phase B, and then a vacuum is applied. The mixture is stirred and cooled to 55°C in 15 minutes. After cooling to room temperature, when a temperature of 45°C is reached, phenoxyethanol and piroctone olamine (Part C) are added. The mixture is stirred for 5 minutes, followed by sodium carbomer (Part D) and perfume oil (Part E), the composition of the invention of Example 10, containing 200 parts by weight of the composition of the invention described in Example 1 diluted at 10% in dipropylene glycol. The mixture is stirred for 3 minutes, and then 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 homogeneous, 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. A composition of substances as perfuming ingredients, comprising: Formula (I) 【Chemistry 1】 wherein n is 1 or 2. wherein the weight ratio of cis-diastereoisomer to trans-diastereoisomer is in the range of from 90:10 to 99.5:0.5; at least 10% w / w of the cis-(1S,2R) diastereoisomer, the percentages being based on the total weight of the composition of matter; 1. A composition of matter as a perfuming ingredient, comprising:

2. The composition of matter comprises: a) 90-99.5% w / w of cis-2-octylcyclopropanecarboxylic acid; b) 0.5% to 10% w / w of trans-2-octylcyclopropanecarboxylic acid and The percentages are based on the total weight of the composition of matter.

10. The composition of matter of claim 1.

3. 3. The composition of matter of claim 1 or 2, wherein the composition of matter has at least 45% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid, said percentage being based on the total weight of the composition of matter.

4. The composition of matter comprises: a) 45-99.5% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) up to 49.75% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid; c) up to 10% w / w of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid; d) up to 10% w / w of trans-(1R,2R)-2-octylcyclopropanecarboxylic acid; and the percentages are based on the total weight of the composition of matter; the weight ratio of the cis-diastereoisomer to the trans-diastereoisomer is in the range of 90:10 to 99.5:0.5; A composition of matter according to any one of claims 1 to 3.

5. The composition of matter comprises: a) 47.5 to 99% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) up to 49.5% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid; c) up to 5% w / w of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid; d) maximum 5% w / w of trans-(1R,2R)-2-octylcyclopropanecarboxylic acid 5. The composition of matter of any one of claims 1 to 4, having:

6. 6. The composition of matter of any one of claims 1 to 5, wherein the weight ratio of said cis-diastereoisomer to said trans-diastereoisomer is in the range of 95:5 to 99:

1.

7. 7. The composition of matter of any one of claims 1 to 6, wherein the cis-2-octylcyclopropanecarboxylic acid and the trans-2-octylcyclopropanecarboxylic acid are racemic.

8. The composition of matter comprises: a) 47.5-49.75% w / w of cis-(1S,2R)-2-octylcyclopropanecarboxylic acid; b) 47.5-49.75% w / w of cis-(1R,2S)-2-octylcyclopropanecarboxylic acid; c) 0.5% to 2.5% w / w of trans-(1S,2S)-2-octylcyclopropanecarboxylic acid; d) 0.5% to 2.5% w / w of trans-(1R,2R)-2-octylcyclopropanecarboxylic acid 8. The composition of matter of any one of claims 1 to 7, having:

9. A method for imparting, enhancing, improving or modifying the scent characteristics of a perfumed composition or a perfumed article or surface, comprising adding to said composition or perfumed article an effective amount of a composition of matter as defined in any one of claims 1 to 8.

10. 10. Use of a composition of matter according to any one of claims 1 to 8 as a perfuming ingredient.

11. A fragrance composition comprising: i) a composition of matter according to any one of claims 1 to 8; 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 fragrance composition comprising:

12. A scented consumer product comprising a composition of matter according to any one of claims 1 to 8 or a scenting composition according to claim 11.

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

14. The scented consumer product may be a luxury perfume, a splash or eau de parfum, a cologne, a shave or aftershave lotion, a liquid detergent, a detergent pod or solid detergent or tablet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, paper, bleach, a carpet cleaner, a curtain care product, a shampoo, a leave-on or rinse-off hair conditioner, a color preparation, a color care product, a hair styling product, a dental care product, a disinfectant, an intimate 14. The perfumed consumer product of claim 13, which is a care product, hair spray, skin cream or lotion, vanishing cream, deodorant or antiperspirant, hair remover, tanning or sun or after-sun product, nail product, skin cleanser, make-up, perfumed soap, shower or bath mousse, oil or gel, foot care or hand care product, hygiene product, air refresher, "ready-to-use" powder air refresher, mold remover, furniture care, wipe, dish detergent or hard surface cleaner, leather care product, or car care product.

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