Powdery macrocyclic compounds of musk-like odor substances

Abstract

The present invention relates to a composition comprising: a) 0.5 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 30% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one, the percentages being based on the total weight of the composition; and the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of 40:60 to 15:85.

Description

Technical Field

[0001] The present invention relates to the field of fragrances. More specifically, the present invention relates to a) 0.5 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 30% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one comprising a composition, wherein the percentages are based on the total weight of the composition; and the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of 40:60 to 15:85, a composition.

[0002] The above composition is a useful fragrance ingredient, and thus the present invention includes the composition of the present invention as part of a flavoring composition or a flavored consumer product. A method for obtaining the composition of the present invention is also part of the present invention.

[0003] Background of the Invention The components imparting a musk note are highly regarded and widely used in fragrances. This is because they are considered as one of the major fragrance base notes, especially a macrocyclic musk compound. Some of the above-mentioned macrocyclic musk compounds have double bonds that generally result in 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, and the E:Z ratio is between 70:30 and 80:20. The isomer distribution affects the functional properties of the components. Therefore, in order to enrich the palette of fragrance manufacturers, it is necessary to develop means to approach new qualities. In particular, it is necessary to enhance the nitro-musk aspect of Habanolide® while maintaining the ambrette aspect. However, the exact functional properties of each individual isomer are unknown, and in actual synthesis, whether pure isomers can be obtained or a mixture mainly composed of E isomers can be obtained.

[0004] For example, International Publication No. 2018104856 reports a method for obtaining (E)-oxacyclohexadec-12-en-2-one or (E)-oxacyclohexadec-13-en-2-one in high purity. Also, U.S. Patent Application Publication No. 2017211014 discloses the isomerization of Globalide® that provides a mixture of oxacyclohexadec-12-en-2-one and oxacyclohexadec-13-en-2-one with an E:Z ratio of 65:31.

[0005] The present invention provides a novel composition containing a large amount of Z isomers that gives a strong powdery / musk note highly regarded in fragrances. The prior art has not predicted that such a composition would bring about such performance improvement and has not provided a method for enriching Z isomers.

[0006] Description of the Invention A surprising synergistic effect has been discovered among the various isomers of oxacyclohexadec-(12 or 13)-en-2-one, which has led to the compositions of the present invention having a powerful musk / powdery note combined with an ambra aspect.

[0007] Accordingly, a first object of the present invention is a) 0.5 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 30% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one A composition comprising, The percentages are relative to the total weight of the composition; and The weight ratio of the E-diastereoisomers to the Z-diastereoisomers is included in the range of 40:60 to 15:85, a composition.

[0008] The above composition can be used as a flavoring component, for example, to impart a powdery musk-like odor note and further have an ambra aspect.

[0009] The terms "E-diastereoisomers" and "Z-diastereoisomers" mean the usual meanings understood by those skilled in the art, that is, the E-diastereoisomers correspond to (E)-oxacyclohexadec-12-en-2-one and (E)-oxacyclohexadec-13-en-2-one, and the Z-diastereoisomers correspond 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 present composition, the various components described above are in the following amounts: a) 7 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 25% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one are present, the percentages being relative to the total weight of the composition; and the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range from 40:60 to 15:85.

[0011] According to one embodiment of the invention, in the present composition, the various components described above are in the following amounts: a) 0.5 to 5% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 1% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 26% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 65 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one are present.

[0012] According to one embodiment of the invention, in the present composition, the various components described above are in the following amounts: a) 7 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 25% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 60% by weight of (Z)-oxacyclohexadec-13-en-2-one are present.

[0013] According to one embodiment of the invention, in the present composition, the various components described above are in the following amounts: a) 40 - 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 2 - 25% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 - 20% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 - 35% by weight of (Z)-oxacyclohexadec-13-en-2-one are present.

[0014] According to one embodiment of the present invention, in this composition, the various components described above are in the following amounts: a) 40 - 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 2 - 25% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 - 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 - 25% by weight of (Z)-oxacyclohexadec-13-en-2-one are present.

[0015] According to one embodiment of the present invention, in this composition, the various components described above are in the following amounts: a) 50 - 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 5 - 20% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 - 20% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 - 25% by weight of (Z)-oxacyclohexadec-13-en-2-one are present.

[0016] According to one embodiment of the present invention, in this composition, the various components described above are in the following amounts: a) 55 - 80% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 5 - 20% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0.5 to 15% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 25% by weight of (Z)-oxacyclohexadec-13-en-2-one are present.

[0017] According to any one of the above embodiments of the present invention, the composition may comprise about 57 to 78% by weight of (Z)-oxacyclohexadec-12-en-2-one, more specifically 60 to 74% by weight of (Z)-oxacyclohexadec-12-en-2-one.

[0018] According to a particular embodiment of the present invention, the composition may comprise about 0.5 to 15% by weight of (Z)-oxacyclohexadec-12-en-2-one.

[0019] According to any one of the above embodiments of the present invention, the composition may comprise about 10 to 20% by weight of (E)-oxacyclohexadec-12-en-2-one, more specifically about 15 to 20% by weight of (E)-oxacyclohexadec-12-en-2-one.

[0020] According to any one of the above embodiments of the present invention, the composition may comprise about 1 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one, more specifically about 70 to 85% or about 1 to 15% by weight of (Z)-oxacyclohexadec-13-en-2-one.

[0021] According to any one of the above embodiments of the present invention, the composition may comprise about 0.5 to 10% by weight of (E)-oxacyclohexadec-13-en-2-one, more specifically about 0.5 to 8% by weight of (E)-oxacyclohexadec-13-en-2-one.

[0022] According to any one of the above embodiments of the present invention, the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of 35:65 to 15:85, more specifically in the range of 30:70 to 17:83, and more specifically in the range of 25:75 to 18:82.

[0023] According to any one of the above embodiments of the present invention, the weight ratio of the 12-position isomer to the 13-position isomer is in the range of 55:45 to 99:1 or 20:80 to 1:99; more specifically in the range of 70:30 to 99:1; or in the range of 20:80 to 30:70; more specifically in the range of 75:25 to 97:3; more specifically in the range of 80:20 to 90:10.

[0024] The terms "12-position isomer" and "13-position isomer" mean the ordinary meanings understood by those skilled in the art, that is, the 12-position isomer corresponds to (E)-oxacyclohexadec-12-en-2-one, and (Z)-oxacyclohexadec-12-en-2-one and the 13-position isomer correspond to (E)-oxacyclohexadec-13-en-2-one and (Z)-oxacyclohexadec-13-en-2-one.

[0025] As described above, the composition of the present invention has a very strong musk and a persistent odor with a powdery note stronger than expected in the direction of nitromusks. The overall odor profile is highly evaluated by fragrance manufacturers. This is because it creates a new direction in the creativity of fragrance manufacturers when compared with Habanolide (registered trademark), which is a component of the prior art.

[0026] In fact, when comparing the odor of the composition of the present invention with the odor of prior art Habanolide®, the composition of the present invention is distinguished by a clearly different odor profile characterized by a stronger powdery, creamy and ambery note and a much weaker metallic note (characteristic of the prior art compound). Furthermore, the composition of the present invention imparts a clearly stronger and more persistent note while providing more volume to the fragrance composition. The composition of the present invention is also distinguished by exhibiting a better olfactory profile. Overall, Habanolide® is higher in the direction of macrocyclic musks with a slightly metallic aspect, while the present composition is higher in the direction of nitromusks, which are particularly sought after due to the highly restricted use of nitromusks.

[0027] Due to the above differences, the composition of the present invention and the prior art compound are each suitable for different uses, i.e., they give different sensory impressions.

[0028] As described above, the present invention relates to the use of the composition of the present invention as a fragrance component. In other words, the present invention relates to a method or process for imparting, enhancing, improving or modifying the odor characteristics of a fragrance composition or a scented article or surface, the method comprising adding an effective amount of the composition of the present invention to the composition or article, for example, including imparting its typical note. It is understood that the final pleasant effect may depend on the exact amount used and the sensory stimulating properties of the composition of the present invention, but in any case, adding the composition of the present invention will impart its typical touch to the final product in the form of a note, touch or aspect depending on the amount used. In addition, the composition of the present invention may be used to enhance the sensory stimulating properties of fragrance components or to reduce unpleasant olfactory impressions such as the metallic, dusty or chemical aspects of some fragrance components.

[0029] It should also be understood that "use of the composition of the present invention" herein refers to the use of any composition containing the composition of the present invention that can be advantageously used in the fragrance industry.

[0030] The above compositions that can be advantageously used as perfume components are also an object of the present invention.

[0031] Therefore, another object of the present invention is i) at least one composition of the present invention as defined above as a perfume component; 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 perfume composition comprising

[0032] As used herein, the "perfume carrier" means a material that is substantially neutral from the perspective of perfume, i.e., does not significantly change the sensory stimulating properties of the perfume component. The carrier can be liquid or solid.

[0033] As liquid carriers, non-limiting examples include emulsion systems, i.e., solvent and surfactant systems, or solvents commonly used in fragrances. A detailed description of the nature and types of solvents commonly used in fragrances cannot be exhaustive. However, non-limiting examples include 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-diacetyloxypropane-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate or mixtures thereof. In the case of compositions containing both a fragrance carrier and a fragrance base, suitable fragrance carriers other than those specified above may be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those known under the trademark Isopar® (manufacturer: Exxon Chemical), or glycol ethers and glycol ether esters, such as those known under the trademark Dowanol® (manufacturer: Dow Chemical Company), or hydrogenated castor oil, such as that known under the trademark Cremophor® RH 40 (manufacturer: BASF).

[0034] A solid carrier means a material to which a fragrance composition or some elements of a fragrance composition can be chemically or physically bonded. Generally, such solid carriers are used to stabilize the composition or to control the evaporation rate of the composition or some of its components. Solid carriers are currently used in the art and those skilled in the art know how to achieve the desired effects. However, non-limiting examples of solid carriers include absorbent gums or polymers or inorganic materials such as porous polymers, cyclodextrins, wood materials, organic or inorganic gels, clays, gypsum talc or zeolites.

[0035] Other non-limiting examples of solid carriers can include encapsulating materials. Examples of such materials include wall-forming and plasticizing materials such as monosaccharides, disaccharides or trisaccharides, natural starch or modified starch, hydrophilic colloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectin, or further materials cited in references such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr’s Verlag GmbH & Co., Hamburg, 1996. Encapsulation is a method well-known to those skilled in the art and can be carried out using techniques such as spray drying, agglomeration or extrusion; or it can consist of coating encapsulation including coacervation and complex coacervation techniques.

[0036] Non-limiting examples of solid carriers include core-shell type capsules containing aminoplast, polyamide, polyester, polyurea or polyurethane type resins or mixtures thereof (all of the aforementioned resins are well-known to those skilled in the art), in particular using techniques such as phase separation processes induced by polymerization, interfacial polymerization, coacervation or all together, optionally in the presence of a polymer stabilizer or a cationic copolymer.

[0037] The resin can be produced by polycondensation of an aldehyde (e.g., formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with an amine such as urea, benzoguanamine, glycoluril, melamine, methylol melamine, methylated methylol melamine, guanazole, and mixtures thereof. Alternatively, preformed resin alkylolated polyamines, e.g., those commercially available under the trade names Urac® (manufacturer: Cytec Technology Corp.), Cymel® (manufacturer: Cytec Technology Corp.), Urecoll® or Luracoll® (manufacturer: BASF) can be used.

[0038] Other resins are produced by polycondensation of a polyol, such as glycerol, with a polyisocyanate, 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 (manufacturer: Mitsui Chemicals, known under the trade name Takenate®), among which those produced by polycondensation of the trimer of xylylene diisocyanate and trimethylolpropane and the biuret of hexamethylene diisocyanate are preferred.

[0039] As some influential literature regarding the encapsulation of flavors by polycondensation of amino resins, i.e., melamine-based resins, and aldehydes, there are papers published by K. Dietrich et al., Acta Polymerica, in 1989, Vol. 40, pages 243, 325 and 683, and in 1990, Vol. 41, page 91, etc. Such papers already describe various parameters that affect the production of such core-shell microcapsules according to prior art methods, and these are also further detailed and exemplified in patent literature. The specification of U.S. Patent No. 4,396,670 by Wiggins Teape Group Limited is an appropriate initial example of the latter. Since then, many other authors have enriched the literature in this field, and it would be impossible to cover all the developments published here, but the general knowledge of encapsulation technology is very important. More recent relevant publications that disclose the appropriate use of such microcapsules are represented, for example, by the paper of K. Bruyninckx and M. Dusselier, ACS Sustainable Chemistry & Engineering, in 2019, Vol. 7, pages 8041 - 8054.

[0040] As used herein, "flavor base" is a composition containing at least one flavor adjunct component.

[0041] As used herein, "flavor adjunct component" means a compound used in a flavor preparation or composition to impart a hedonic effect. In other words, such adjunct components that should be considered flavor components must be recognized by those skilled in the art not merely as having an odor, but as being able to impart or modify the odor of the composition positively or pleasantly.

[0042] The nature and types of the fragrance auxiliary components present in the base are not guaranteed to be described in more detail herein, and these are not exhaustive in any case. Those skilled in the art can select them based on their general knowledge and in accordance with the intended use or application and the desired sensory stimulation effect. Generally speaking, these fragrance auxiliary components 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 the above-mentioned fragrance auxiliary components can be of natural or synthetic origin.

[0043] In particular, fragrance auxiliary components commonly used in fragrance formulations, such as: - Aldehyde components: decanal, dodecanal, 2-methyl-undecanal, 10-undecenal, octanal, nonanal and / or nonenal; - Aromatic-herbal components: eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0~2,7~]undecan-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or alpha-pinene; - Balsamic components: coumarin, ethyl vanillin and / or vanillin; - Citrus components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpene, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-menthadiene; - Floral components: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-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-indanmethanol, 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, berzyl 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 methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, berzyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, propyl (S)-2-(1,1-dimethylpropoxy)propanoate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamic aldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,A mixture of 1-(1,1-dimethylethyl)-1-cyclohexyl acetate, benzyl isobutyrate and / or methyl ionone isomers; - Fruit components: γ-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, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, 3-(3,3-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 components: 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 components: 1,4-dioxaspiro[5.17]heptadecane-5,17-dione, (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-oxoethyl propionate, 3-methyl-5-cyclopentadecen-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-methylpropyl propanoate, oxacyclohexadecan-2-one and / or (1S,1’R)-[1-(3’,3’-dimethyl-1’-cyclohexyl)ethoxycarbonyl]methyl propanoate; - Woody components: 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 undeca[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 (registered trademark), (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 components (e.g., amber, powdery spicy or watery): either dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal may be mentioned.

[0044] According to certain embodiments, the flavoring composition of the present invention contains at least one woody component as a flavoring auxiliary component.

[0045] The perfume base according to the present invention is not limited to the above-mentioned flavoring auxiliary components, and many of these auxiliary components are in any case listed in references such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest edition, or other papers of similar nature, as well as numerous patent documents in the field of perfumery. It is also understood that the above auxiliary components may be compounds known to release various types of flavoring compounds also known as properfumes or profragrances in a controlled manner. Non-limiting examples of suitable properfumes 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, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate or mixtures thereof.

[0046] As used herein, the "perfume adjuvant" means a component that can impart additional advantages such as color, specific light resistance, chemical stability, etc. Although a detailed description of the nature and types of adjuvants commonly used in perfume compositions cannot be exhaustive, it should be mentioned that the above components are well known to those skilled in the art. Specific non-limiting examples include the following: adhesives (e.g., surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light and / or buffer or chelating agents, e.g., BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antibacterial or antibacterial or antifungal or anti-irritant agents), abrasives, skin coolants, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0047] It is understood that those skilled in the art can completely design the formulation optimal for the desired effect by mixing the above components of the perfume composition not only by simply applying the standard knowledge in the technical field but also by the trial-and-error method.

[0048] The composition of the present invention comprising at least one composition as defined above and at least one perfume carrier consists of a specific embodiment of the present invention, and a perfume composition comprising at least one composition as defined above, at least one perfume carrier, at least one perfume base, and optionally at least one perfume adjuvant.

[0049] For clarity, it is also understood that any mixture directly obtained from chemical synthesis, e.g., a reaction medium that has not been appropriately purified and in which the composition of the present invention may be included as a starting, intermediate or final product, cannot be regarded as a perfume composition according to the present invention unless the mixture provides the composition of the present invention in a form suitable for perfume. Thus, unless otherwise specified, unpurified reaction mixtures are generally excluded from the present invention.

[0050] The composition of the present invention can also be advantageously used in all fields of modern perfumery, i.e., perfumes or functional fragrances, to positively impart or modify the odor of the consumer product to which the composition is added. Accordingly, another object of the present invention consists of a perfumed consumer product comprising at least one composition as defined above as a fragrance component.

[0051] The composition of the present invention can be used as such or added as part of the perfuming composition of the present invention.

[0052] For the sake of clarity, "perfumed consumer product" means a consumer product that provides at least a pleasant perfuming effect on the surface or space to which it is applied (e.g., skin, hair, textile, or household surface). In other words, the perfumed consumer product according to the present invention is a perfumed consumer product comprising a functional formulation, as well as any additional beneficial agents corresponding to the desired consumer product, and an olfactorily effective amount of at least one composition of the present invention. For the sake of clarity, the above perfumed consumer product is a non-edible product.

[0053] The nature and type of the components of the perfumed consumer product are not guaranteed to be described in more detail herein (nor will they be exhaustive in any case), and those skilled in the art can select them based on general knowledge and in accordance with the nature and desired effects of the above products.

[0054] Non-limiting examples of suitable perfumed consumer products include fragrances such as perfumes, splash or eau de parfum, cologne or shave or aftershave lotion; fabric care products such as liquid or solid detergents, fabric softeners, liquid or solid aroma boosters, fabric fresheners, ironing water, paper, bleaches, carpet cleaners, curtain care products; body care products such as hair care products (e.g., shampoos, coloring preparations or hair sprays, color care products, hair styling products, dental care products), disinfectants, intimate care products; cosmetics (e.g., skin cream or lotion, vanishing cream or deodorant or antiperspirant (e.g., spray or roll-on), depilatory, tanning products or sunburn products or after-sun products, nail products, skin cleansing, makeup); or skin care products (e.g., soap, shower or bath mousse, oil or gel, or hygiene products or foot / hand care products); air care products such as air fresheners or "ready-to-use" powdered air fresheners that can be used in home spaces (rooms, refrigerators, cupboards, shoes or cars) and / or public spaces (halls, hotels, malls, etc.); or home care products such as mold removers, furniture care products, wipes, dishwashing detergents or hard surface (e.g., floor, bathtub, sanitary or window cleaning) detergents; leather care products; car care products such as polish, wax or plastic cleaner.

[0055] Some of the above perfumed consumer products can be aggressive media towards the compositions of the present invention, so it may be necessary to protect the compositions of the present invention from premature degradation, for example, by encapsulation or by chemically bonding it to another chemical suitable for releasing the components of the present invention in response to appropriate external stimuli such as enzyme, light, heat or pH changes.

[0056] The proportion at which the composition according to the present invention can be incorporated into various of the aforementioned products or compositions varies within a wide range of values. These values depend on the nature of the article to be perfumed, the desired sensory stimulating effect, and the nature of the auxiliary components in a given base when the composition according to the present invention is mixed with perfume auxiliary components, solvents or additives commonly used in the art.

[0057] For example, in the case of perfume compositions, typical concentrations are on the order of 0.001% to 30% by weight, or more, of the composition of the present invention, based on the weight of the composition in which they are incorporated. In the case of perfumed consumer products, typical concentrations are on the order of 0.0001% to 10% by weight, or more, of the composition of the present invention, based on the weight of the consumer product in which they are incorporated.

[0058] Another object of the present invention is a method for producing the composition defined above. The method for producing the above composition is i) 0.5 to 85% by weight of a compound of the formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0059] According to a specific embodiment, the method for producing the composition of the present invention is i) 40 to 85% by weight of the formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0060] For the sake of clarity, the phrase "any one of its stereoisomers or a mixture thereof" or a similar expression has the ordinary meaning understood by those skilled in the art, that is, the compounds of the present invention may be pure or in the form of a mixture of enantiomers or diastereoisomers (for example, carbon 17 may be R, S or a mixture thereof, and compounds 12 and 13 or 13 and 14 have the relative or absolute configuration shown in the figure). According to any one of the above embodiments of the present invention, the stereocenter of carbon 17 can be R or S or a mixture thereof. The other stereocenters have fixed stereochemistry; that is, carbons 12 and 13 or 13 and 14 of the compounds of formulas (I) to (IV) have the absolute (R or S) or relative configuration defined in the drawings.

[0061] According to any one of the above embodiments, R 1 may represent an OR 2 group, where R 2 may represent a C 1~3 alkyl group, and in particular R 2 may represent a methyl group or an ethyl group.

[0062] According to any one of the above embodiments, the thermal desorption is carried out at a temperature of 120 °C to 220 °C, preferably 140 °C to 160 °C.

[0063] According to any one of the above embodiments, the thermal desorption can be carried out in the presence of a carboxylic acid or anhydride, typically at a temperature of 120 to 180 °C.

[0064] According to any one of the above embodiments, the thermal desorption is thermal decomposition at a higher temperature in the absence of a catalyst.

[0065] The reaction can be carried out in the presence or absence of a solvent. If a solvent is required or used for practical reasons, any solvent stream in such reaction types can be used for the purposes of the present invention. Solvents with high boiling points are preferred. Non-limiting examples of solvents include DMSO, DMPU, DMF, DMA, NMP, high-boiling aromatic solvents such as mesitylene, xylene, diisopropylbenzene or carboxylic acid anhydrides or mixtures thereof. The choice of solvent depends on the nature of the substrate and / or catalyst, and those skilled in the art can suitably select the most suitable solvent for each case to optimize the reaction.

[0066] According to any one of the above embodiments, a method for producing a mixture comprising 0.5 to 85% of the compound of formula (I), 0.5 to 85% of the compound of formula (II), 0.5 to 30% of the compound of formula (III), and 0 to 30% of the compound of formula (IV) comprises the following steps: a) Epoxidizing a composition comprising at least 70% of oxacyclohexadec-12-en-2-one and oxacyclohexadec-13-en-2-one having a double bond in the E configuration and at most 30% of oxacyclohexadec-12-en-2-one and oxacyclohexadec-13-en-2-one having a double bond in the Z configuration; b) Hydrolyzing the mixture obtained in step a) to form i) 0.5 to 85% by weight of the diol (12RS,13SR)-12,13-dihydroxyoxacyclohexadecan-2-one; ii) 0.5 to 85% by weight of the diol (13RS,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one; iii) 0.5 to 30% by weight of the diol (12RS,13RS)-12,13-dihydroxyoxacyclohexadecan-2-one; and iv) 0 to 30% by weight of the diol (13SR,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one to form a mixture of diols; c) The diol obtained in step b) is treated with triC1~3 The step of treating with an alkyl orthoformate or a DMF acetal may be included.

[0067] According to a specific embodiment, a method for producing a mixture containing 40 - 85% of the compound of formula (I), 10 - 80% of the compound of formula (II), 2 - 25% of the compound of formula (III), and 1 - 30% of the compound of formula (IV) comprises the following steps: a) Epoxidizing a composition containing at least 70% of oxacyclohexadec - 12 - en - 2 - one and oxacyclohexadec - 13 - en - 2 - one having a double bond in the E configuration and at most 30% of oxacyclohexadec - 12 - en - 2 - one and oxacyclohexadec - 13 - en - 2 - one having a double bond in the Z configuration; b) Hydrolyzing the mixture obtained in step a) to form a mixture of diols containing: i) 40 - 85% by weight of the diol (12RS,13SR) - 12,13 - dihydroxyoxacyclohexadecane - 2 - one; ii) 10 - 80% by weight of the diol (13RS,14SR) - 13,14 - dihydroxyoxacyclohexadecane - 2 - one; iii) 2 - 25% by weight of the diol (12RS,13RS) - 12,13 - dihydroxyoxacyclohexadecane - 2 - one; and iv) 1 - 30% by weight of the diol (13SR,14SR) - 13,14 - dihydroxyoxacyclohexadecane - 2 - one ; c) The step of treating the diol obtained in step b) with a triC 1~3 The step of treating with an alkyl orthoformate or a DMF acetal may be included.

[0068] The order of epoxidation, hydrolysis, and formation of dioxolane is a well-known order reported in Chem. Lett. 1986, 879. Those skilled in the art are familiar with the conditions for performing such conversions. Epoxidation can be carried out using a peroxide-containing reagent, such as hydrogen peroxide, in the presence of a carboxylic acid or a suitable metal catalyst or metal complex, such as [Fe(BPMEN)(OTf) 2 , TPA(Fe(OTf) 2 (J. Am. Chem. Soc., 2007, 129, 15954), Mn, Fe(ACS Catalysis, 2018, 8, 4528), Mn(II) picolinate (Org. Lett., 2016, 18, 2528), a peracid, such as peracetic acid, m-chloroperbenzoic acid, or enzymatically. A non-exhaustive list of examples of suitable epoxidation conditions is disclosed in Chem Rev., 2003, 103, 2457, Chem Rev. 2006, 106, 2943, or Chem Rev., 1989, 89, 431. Those skilled in the art can successfully select the most convenient conditions. Hydrolysis can be carried out using a suitable organic or mineral acid, preferably in the presence of water, or enzymatically. The kinetic rate of hydrolysis can be different for all the epoxides present in the mixture obtained in step a). Those skilled in the art can successfully select the most appropriate conditions to preferentially effect partial or complete hydrolysis of all the epoxides. Epoxidation and hydrolysis can also be carried out in the same vessel under suitable conditions known to those skilled in the art.

[0069] The formation of dioxolane can be carried out using a DMF acetal, such as 1,1-dimethoxy-N,N-dimethylmethanamine or 1,1-ethoxy-N,N-dimethylmethanamine. Alternatively, the formation of dioxolane can be carried out using triC orthoformate 1~3It can be carried out in the presence of an acid catalyst, such as Amberlyst® A-15 or a similar sulfonic acid, or alternatively in the presence of a suitable carboxylic acid, with or without removal of the alcohol by-product by heating, using an alkyl, such as trimethyl orthoformate or triethyl orthoformate. The formation of the orthoester and its subsequent elimination may be carried out in the same vessel if desired.

[0070] The selective hydrolysis of the 13 cis-epoxides and 13 trans-epoxides present in the mixture of 12- and 13-isomer epoxides could be achieved using a solvent, such as ethyl formate, in the presence of an acid catalyst without adding water. The above conditions unexpectedly resulted in the formation of (RS)-13-((SR)-1,3-dihydroxypropyl)oxacyclotridecan-2-one and (RS)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one, which were further converted to ((13RS,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one and (13RS,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one. The above conversion is carried out in the presence of a suitable acid, such as camphorsulfonic acid, in dichloromethane at ambient temperature.

[0071] In other words, depending on the conditions used for the hydrolysis of the 13-isomer epoxides ((1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-5-one (trans) and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (cis)), (13RS,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one and (13SR,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one and / or (RS)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one and (RS)-13-((SR)-1,3-dihydroxypropyl)oxacyclotridecan-2-one are obtained in pure form or as part of a mixture.

[0072] The compounds of formulas (I), (II), (III) and (IV), 13,14-dihydroxyoxacyclohexadecan-2-one, 12,13-dihydroxyoxacyclohexadecan-2-one and 13-(1,3-dihydroxypropyl)oxacyclotridecan-2-one are novel. Accordingly, a further subject of the present invention is a compound of formula (V) [Chemical formula] [wherein when m is 1, n is 1, or when m is 0, n is 2; the R groups represent hydrogen, or both R groups together represent a C 1~6 alkyl group, CHOR 2 or CHNR 2 2 group, where R 2 represents a C 1~3 alkyl group], which is a compound in the form of any one of its stereoisomers or a mixture of them.

[0073] For the sake of clarity, the expression "any one of its stereoisomers or a mixture of them", or a similar expression, has the ordinary meaning understood by those skilled in the art, i.e., the compound of formula (V) can be a pure enantiomer or a diastereoisomer, or a mixture of enantiomers and / or diastereoisomers. In other words, the compound of formula (V) may have several stereocenters, and each of the above stereocenters can have two different stereochemistries (e.g., R or S). The compound of formula (V) may be in the form of a pure enantiomer, or in the form of a mixture of enantiomers or diastereoisomers. The compound of formula (V) can be in the form of a racemate or a scalemic. Accordingly, the compound of formula (V) can be one stereoisomer, or in the form of a composition containing or consisting of various stereoisomers.

[0074] Examples The present invention will now be described in more detail by the following examples. Abbreviations have their usual meanings in the art, and temperatures are given in degrees Celsius (°C). NMR spectra were obtained using a Bruker Avance II Ultrashield 400 plus operating at 400 MHz ( 1 H) and 100 MHz ( 13 C), or a Bruker Avance III 500 operating at 500 MHz ( 1 H) and 125 MHz ( 13 C), or a Bruker Avance III 600 cryoprobe operating at 600 MHz ( 1 H) and 150 MHz ( 13 C). Spectra were internally referenced to 0.0 ppm of tetramethylsilane. 1 1H NMR signal shifts are expressed in δ ppm, and coupling constants (J) are expressed in Hz using the following multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; b, broad (indicating unresolved coupling), and were interpreted using Bruker Topspin software. 13 13C NMR data are chemical shifts δ ppm and hybridization from DEPT90 and DEPT135 experiments, C, quaternary (s); CH, methine (d); CH 2 , methylene (t); CH 3 , methyl (q). GC method GC-23 (20M, 0.18 mm, 0.2 μm, H 2 , 3 °C / min at 110 °C).

[0075] Example 1 Synthesis of the composition of the present invention a) Epoxidation of commercially available Habanolide® i. Buffered with sodium acetate Under a nitrogen atmosphere, a solution of peracetic acid (39% aqueous solution, 108 mL, approximately 1.3 equivalents) was slowly added dropwise to a suspension of Habanolide® (100.0 g, 420 mmol, 92% purity) and sodium acetate (6.9 g, 0.2 equivalents) in DCM (400 mL), cooled to 0 °C in an ice bath. The emulsion was slowly warmed to ambient temperature. After 21 hours at room temperature, the mixture was diluted with ether. The organic phase was washed with water, carefully with saturated sodium bicarbonate solution, and then with 5% sodium sulfite solution until the Merck peroxide test strip was negative, then dried over anhydrous sodium sulfate, filtered, and the solvent removed under vacuum to give 105 g of a crude epoxide mixture. Light impurities were removed by distillation at 0.1 mbar, 180 - 190 °C using a 30 cm Fisher column to give 9.0 g of a head fraction containing exaltolide and co-eluting impurities. The residue (93 g) was redistilled by Kugelrohr bulb-to-bulb distillation at 0.1 mbar, 155 - 160 °C to give 85.6 g (81%) of an epoxide mixture (13E (25.4%), 12E (45.2%), 13Z (7.6%), 12Z, (19.8%)) in addition to 2.7 g of residue.

Table 1

[0076] ii. Non-buffered Under a nitrogen atmosphere, a solution of peracetic acid (39% aqueous solution, 12.5 mL, approximately 1.3 equivalents) was slowly added dropwise to a solution of Habanolide® (11.0 g, 46.1 mmol) in DCM (50 mL), cooled to 0 °C in an ice bath. The emulsion was slowly warmed to room temperature over 2 hours and stirred at room temperature for a further 15 hours, then diluted with ether. The organic phase was washed with water, carefully with saturated sodium bicarbonate solution, and then with 5% sodium sulfite solution until the Merck peroxide test strip was negative, then dried over anhydrous sodium sulfate, filtered, and the solvent removed under vacuum to give 12.1 g of a crude epoxide mixture. Further purification was carried out by chromatography (Purifrash 330 g cartridge 30 μM) using heptane:MTBE (gradient 95:5 - 60:40) as the eluent, Pure (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, 1.0 g Pure (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one, 0.9 g were obtained. Next, further elution was carried out to obtain 3.2 g of the diol as a mixture of isomers.

[0077] b) Hydrolysis of the epoxide obtained in step a)i. to the diol A solution of the epoxy mixture (30.0 g, 118 mmol) prepared in step a)i. in THF (250 mL) and 5% H 2 SO 4 (50 mL) was heated under reflux (65 °C) for 10 hours, then cooled and diluted with ether. The organic phase was washed with water, saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under vacuum to obtain a mixture of diols (27.2 g, 84%), which was used directly without further purification in the next step.

[0078] c) Conversion of the mixture of diols obtained in step b) to orthoester Amberlyst® A-15 (5.5 g) was added to a stirred solution of the diol mixture (27.0 g, 99 mmol) prepared in step b) and trimethyl orthoformate (40.0 g, 377 mmol), and the suspension was stirred at ambient temperature for 6 hours. Solid sodium carbonate (500 mg) and ether (50 mL) were added, and the suspension was stirred for a further 30 minutes, then filtered and the solvent was removed under vacuum to obtain the crude orthoester as a mixture of isomers, 29.0 g, 93%.

[0079] d) Removal of the orthoester obtained in step c) i. Removal with acetic anhydride A solution of the orthoester obtained in step c) (29.0 g, 92 mmol) and acetic anhydride (50 mL) was heated at reflux (140 °C) for 7 hours, then cooled and diluted with ether and water. Stirred at room temperature for 30 minutes, the organic phase was washed several times with saturated sodium bicarbonate solution and brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under vacuum to obtain 24.4 g of crude Habanolide. Further purified by Kugelrohr bulb-to-bulb distillation at 140 - 145 °C at 0.5 mbar to obtain 12.65 g (Z:E, 75:25) of the composition of the present invention containing about 63 wt% of (Z)-oxacyclohexadec-12-en-2-one, about 16 wt% of (E)-oxacyclohexadec-12-en-2-one, about 7.4 wt% of (E)-oxacyclohexadec-13-en-2-one and about 13 wt% of (Z)-oxacyclohexadec-13-en-2-one.

Table 2

[0080] ii. Removal without using an acid The mixture of orthoesters prepared in step c) was heated at 200 °C at 20 mbar, then at 15 mbar, and the distillate was analyzed by GC. About 65% of Habanolide (63 wt% of (Z)-oxacyclohexadec-12-en-2-one, about 16 wt% of (E)-oxacyclohexadec-12-en-2-one, about 7.4 wt% of (E)-oxacyclohexadec-13-en-2-one and about 13 wt% of (Z)-oxacyclohexadec-13-en-2-one) and about 20 - 25% of orthoester.

[0081] iii. Thermal decomposition with non-volatile acid The mixture of the orthoester prepared in step c) and 1 wt% of tetracosanedioic acid was heated at 200 °C under 20 mbar and then under 15 mbar or heated at 150 °C under 5 mbar, and the distillate was analyzed by GC. Approximately 85% of the composition of the present invention (63 wt% (Z)-oxacyclohexadec-12-en-2-one, approximately 16 wt% (E)-oxacyclohexadec-12-en-2-one, approximately 7.4 wt% (E)-oxacyclohexadec-13-en-2-one and approximately 13 wt% (Z)-oxacyclohexadec-13-en-2-one) and approximately 7% of the orthoester.

[0082] Example 2 Synthesis of the composition of the present invention a) Selective hydrolysis of (1SR,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one The epoxy mixture obtained in Example 1 a) i. (15.0 g, 59 mmol) was dissolved in ethyl formate (30 mL), Amberlyst® A-15 (750 mg, 5 wt%) was added, and the suspension was stirred at ambient temperature for 22 h and then poured into saturated NaHCO 3 and the aqueous phase was re-extracted with EtOAc, the organic phase was washed with brine, and MgSO 4It was dried, filtered, and the solvent was removed in vacuo to obtain a mixture of the diol and the epoxide as a colorless liquid. Filtration through a silica plug (100 mL) with 1:9 EtOAc:heptane (2×250 mL) fr1 and fr2 gave 7.0 g of 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 (trans:cis, 80:20). Elution was further carried out with 1:6 EtOAc:heptane (2×100 mL). Next, 6.5 g of a mixture of (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one and (SR)-13-((SR)-1,3-dihydroxypropyl)oxacyclotridecan-2-one was obtained as an oil with 70:30 EtOAc:heptane (500 mL) as the eluent and finally EtOAc (500 mL).

Table 3

[0083] b) Isomerization of (SR)-13-((RS)-1,3-dihydroxypropyl)oxacyclotridecan-2-one and (SR)-13-((SR)-1,3-dihydroxypropyl)oxacyclotridecan-2-one to (13SR,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one and (13SR,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one The diol mixture (6.5 g) prepared above was dissolved in DCM (50 mL), racemic camphorsulfonic acid (100 mg) was added, and the mixture was stirred at ambient temperature overnight. Saturated NaHCO 3 was diluted, re-extracted with DCM, the organic phase was washed with brine, dried over MgSO 4 and filtered, and the solvent was removed under vacuum to obtain 6.0 g of a crude mixture containing (13SR,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one and (13SR,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one.

Table 4

[0084] c) Formation of orthoester A suspension of the mixture (3.0 g) of (13SR,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one and (13SR,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one prepared above in trimethyl orthoformate (10 mL) and Amberlyst® A-15 (250 mg) was stirred at ambient temperature for 4 h. The suspension was then poured into saturated NaHCO 3 and the aqueous phase was re-extracted with EtOAc, the organic phase was washed with brine, dried over MgSO 4 and filtered, and the solvent was removed under vacuum to give a mixture of orthoesters (3.5 g) as a colorless liquid, which was used without further purification in the next step.

Table 5

[0085] d) Removal of orthoester A solution of the crude orthoester (5.2 g, 16.5 mmol) prepared above was heated at 150 °C for 60 min using acetic anhydride (10 mL, 98 mmol) (in 4 × 1.7 g, 5.4 mmol lots using an Anton Parr Monowave 50 apparatus), and then cooled. The lots were combined and diluted with ether and water. The organic phase was washed with water and then stirred with saturated NaHCO 3 for 30 min. The organic phase was again stirred with saturated NaHCO 3The solution was washed with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under vacuum to obtain 4.2 g of a crude Habanolide mixture. By Kugelrohr bulb-to-bulb distillation (130 - 135 °C at 0.8 mbar), a mixture was obtained containing 1.7 wt% of (Z)-oxacyclohexadec-12-en-2-one, about 1.1 wt% of (E)-oxacyclohexadec-12-en-2-one, about 15.9 wt% of (E)-oxacyclohexadec-13-en-2-one, and about 81.3 wt% of (Z)-oxacyclohexadec-13-en-2-one (2.1 g).

[0086] Example 3 Synthesis of the composition of the present invention a) Hydrolysis of a mixture containing (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one A solution of (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one (5.5 g, trans:cis, 80:20) obtained from fractions 1 and 2 of Example 2a) in THF (20 mL) and 10% H 2 SO 4 (5 mL) was heated at 65 °C for 2 hours and then cooled. Diluted with saturated NaHCO 3 and re-extracted with EtOAc. The organic phase was washed with brine, dried over MgSO 4 and filtered, and the solvent was removed under vacuum to obtain 5.8 g of a crude diol mixture. [Table 6]

[0087] b) Formation of orthoester A suspension of a mixture containing (12RS,13SR)-12,13-dihydroxyoxacyclohexadecan-2-one and (12SR,13SR)-12,13-dihydroxyoxacyclohexadecan-2-one (5.0 g) in trimethyl orthoformate (10 mL) and Amberlyst® A-15 (250 mg) was stirred at ambient temperature for 4 hours. The suspension was then poured into saturated NaHCO 3 and the aqueous phase was re-extracted with EtOAc. The organic phase was washed with brine, dried over MgSO 4 , filtered, and the solvent removed in vacuo to give 6.0 g of a mixture of orthoesters as a colorless liquid, which was used without further purification in the next step.

Table 7

[0088] c) Removal of orthoesters i. Removal with acetic anhydride Starting with the mixture of orthoesters prepared above, removal was carried out as in Example 1d)i. to give 76 wt% of (Z)-oxacyclohexadec-12-en-2-one, about 18 wt% of (E)-oxacyclohexadec-12-en-2-one, about 1 wt% of (E)-oxacyclohexadec-13-en-2-one and about 2 wt% of (Z)-oxacyclohexadec-13-en-2-one.

[0089] ii. Removal with acetic anhydride under pressure A solution of the crude orthoester (6.1 g, 19.4 mmol) prepared from Example 3b) was heated at 150 °C for 60 minutes using acetic anhydride (10 mL, 98 mmol) (in 4 × 4 g lots using an Anton Parr Monowave apparatus), then cooled. The lots were combined and diluted with ether and water. The organic phase was washed with water and then stirred with saturated NaHCO 3 for 30 minutes. The organic phase was again stirred with saturated NaHCO 3The solution was washed with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under vacuum to obtain 4.3 g of a crude Habanolide mixture. Further purification was carried out by flash chromatography (200 g cartridge, 40 micron) using gradient elution of 1:99 to 1:9 EtOAc:heptane, followed by Kugelrohr bulb-to-bulb distillation (130 - 135 °C at 0.8 mbar), to give 70 wt% of (Z)-oxacyclohexadec-12-en-2-one, 23.4 wt% of (E)-oxacyclohexadec-12-en-2-one, about 0.6 wt% of (E)-oxacyclohexadec-13-en-2-one, and 4 wt% of (Z)-oxacyclohexadec-13-en-2-one (1.95 g).

[0090] Example 4 Synthesis of the composition of the present invention - One-pot formation and removal of orthoester A suspension of a mixture containing (13SR,14RS)-13,14-dihydroxyoxacyclohexadecan-2-one and (13SR,14SR)-13,14-dihydroxyoxacyclohexadecan-2-one (each in a ratio of 75:25, obtained in Example 2b) (1.5 g, 5.5 mmol) in citric acid (about 48 mg, cat.) and trimethyl orthoformate (3.5 g, xs) was heated in an Anton Paar Monowave 450 at 75 °C for 30 minutes and then at 175 °C for an additional 4 hours. The reaction was cooled, diluted with saturated NaHCO 3 and re-extracted with EtOAc. The organic phase was washed with brine, dried over MgSO 4 and filtered, and the solvent was removed under vacuum to obtain 1.5 g of (E)-oxacyclohexadec-13-en-2-one and (Z)-oxacyclohexadec-13-en-2-one. Further purification was carried out by Kugelrohr bulb-to-bulb distillation at 5.0×10-1 mbar at 135 - 145 °C to give 0.73 g of (Z)-oxacyclohexadec-13-en-2-one:(E)-oxacyclohexadec-13-en-2-one (75:24). DB-23 analysis 12E (1.2%), 13E (21.7%), 13Z (76%), 12Z (1.2%)

[0091] Example 5 Synthesis of the composition of the present invention a) Hydrolysis of (1RS,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one, (1SR,16RS)-4,17-dioxabicyclo[14.1.0]heptadecan-6-one, (1SR,16SR)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one and (1SR,16RS)-5,17-dioxabicyclo[14.1.0]heptadecan-6-one The mixture of epoxides prepared in Example 1 a) i. (9.0 g, 35.4 mmol above) was dissolved in THF (27 g) containing 10% H 2 SO 4 (4.0 g), heated at 70 °C for 3 hours, then cooled. Saturated NaHCO 3 was added, the aqueous phase was extracted with EtOAc, the combined organic phases were washed with brine, dried over MgSO 4 , filtered, and the solvent was removed under vacuum to give 6.8 g of a crude diol mixture. This diol mixture (6.8 g, 25 mmol) was dissolved in DCM (50 ml), CSA (100 mg) was added, and the solution was stirred at ambient temperature overnight. Saturated NaHCO 3 was added, the aqueous phase was extracted with DCM, the combined organic phases were washed with brine, dried over MgSO 4 , filtered, and the solvent was removed under vacuum to give 6.3 g, 23.2 mmol, 65% of a crude diol mixture.

[0092] b) Formation of orthoester Amberlyst A-15 (0.95 g) was added to the diol mixture prepared above (6.3 g, 23.2 mmol) in trimethyl orthoformate (12.0 g, 11.3 mmol), stirred at ambient temperature for 90 minutes, then filtered. The filtrate was diluted with ether, washed with saturated NaHCO 3 solution, and anhydrous Na 2 SO 4It was dried, filtered, and the solvent was removed under vacuum to obtain 7.1 g of crude orthoester (a complex mixture of isomers), which was used without purification in the next step.

[0093] c) Removal of orthoester Using an Anton Parr Monowave 50 apparatus, a mixture of the crude orthoester prepared in step b) above (1.5 - 1.7 g, 4.8 - 5.4 mmol) in acetic anhydride (2.0 g, 19.6 mmol) was heated at 150 °C for 60 minutes and then cooled. This was repeated 5 times and all the lots were combined. The excess acetic anhydride was rendered ineffective by diluting with ether and water. The organic phase was washed again with water and then stirred with saturated NaHCO 3 for 30 minutes. The organic phase was washed again with saturated NaHCO 3 solution, brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under vacuum to obtain a crude mixture. By Kugelrohr bulb - to - bulb distillation (130 - 135 °C at 0.8 mbar), 40.1 wt% of (Z) - oxacyclohexadec - 12 - en - 2 - one, about 16.7 wt% of (E) - oxacyclohexadec - 12 - en - 2 - one, about 7.5 wt% of (E) - oxacyclohexadec - 13 - en - 2 - one and 33.5 wt% of (Z) - oxacyclohexadec - 13 - en - 2 - one (3.0 g, 12.6 mmol) were obtained.

[0094] Example 6 Synthesis of the composition of the present invention - Formation of N,N-dimethylorthoamide General procedure 0.5 - 1.0 mmol of diol was dissolved in DMF dimethoxyacetal (1.0 g), the solution was heated at 100 °C for 60 minutes, then cooled, diluted with MTBE, washed with water, NaHCO 3 , brine, dried over MgSO 4 and filtered, and the solvent was removed under vacuum to obtain the desired orthoamide as a 1:1 mixture of diastereoisomers.

Table 8

[0095] Formation and removal of N,N-dimethylorthoamide A solution of the diol (1.0 g, 3.68 mmol) prepared in Example 2b) in DMF dimethoxyacetal (2.0 g) was heated at 100 °C for 60 minutes and then cooled. The solution was concentrated until dry and then Ac 2 O (2.0 g) was added and the solution was heated at 150 °C for 1 hour in an Anton Parr Monowave 50 apparatus.

[0096] The reaction product was diluted with MTBE, transferred to a round-bottom flask, and the solvent was removed under vacuum to obtain 1.2 g of crude orthoamide, which was used as such in the removal step. The crude orthoamide was dissolved in Ac 2 O (3.0 g) and the mixture was heated at 150 °C for 60 minutes. The mixture was diluted with MTBE and water and then re-extracted with MTBE. The combined organic phases were washed with saturated NaHCO 3 , brine, dried over anhydrous MgSO 4 4, filtered, and the solvent was removed in vacuo to obtain 0.93 g of crude Habanolide. Further purification by Kugelrohr distillation at 150 °C under 1 mbar gave 0.45 g of (Z)-oxacyclohexadec-12-en-2-one (1.9 wt%), about 5.6 wt% of (E)-oxacyclohexadec-12-en-2-one, about 20 wt% of (E)-oxacyclohexadec-13-en-2-one, and about 72 wt% of (Z)-oxacyclohexadec-13-en-2-one (3.0 g, 12.6 mmol). GC analysis with DB-23 showed 12E (5.6%), 13E (20%), 13Z (72%), 12Z (1.9%).

[0097] Example 7 Preparation of a fragrance composition An aroma composition for fine fragrances was prepared by mixing the following ingredients:

Table 9-1

Table 9-2

[0098] When 2000 parts by weight of the composition described in Example 1 was added to the above fine fragrance composition, it was imparted with a musky property in the direction of nitromusk having a strong powdery property, as well as creamy and oriental notes. The composition of the present invention blends particularly well with powdery elements such as coumarin and oriental notes such as vanillin and woody-sandalwood.

[0099] By adding the same amount of Habanolide (registered trademark), a musky property in the direction of macrocyclic musk but having a woody aspect was also imparted. The composition obtained by the above addition does not have powdery, creamy and oriental characteristics. Habanolide (registered trademark) blends particularly well with woody-cedar elements such as cedarwood oil and 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone.

[0100] By adding the composition of the present invention to the above fine fragrance composition, more volume is given to the composition by the composition. The above effect can also be obtained with Habanolide (registered trademark), but the degree is low.

[0101] Example 8 Preparation of an eau de toilette containing the composition of the present invention An eau de toilette was prepared by adding 12% by weight of the composition of Example 6 of the present invention to ethanol with respect to the total weight of the eau de toilette.

[0102] Example 9 Preparation of a liquid detergent containing the compound of the present invention

Table 10

[0103] To the fragrance-free liquid detergent composition in Table 1, 0.5 to 1.5% by weight of the composition of Example 7 of the present invention, based on the total weight of the liquid detergent, is added while gently shaking to prepare the liquid detergent.

[0104] Example 10 Preparation of a fabric softener containing the compound of the present invention

Table 11

[0105] The softener is prepared by weighing methylbis[ethyl(tallowate)]-2-hydroxyethylammonium methyl sulfate heated to 65°C. Then, water and 1,2-benzisothiazolin-3-one are placed in a reactor and heated to 65°C with stirring. Methylbis[ethyl(tallowate)]-2-hydroxyethylammonium methyl sulfate is added to the above mixture. The mixture is stirred for 15 minutes, and CaCl 2 is added. Next, 0.5 to 2% by weight of the composition of Example 7 of the present invention, 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 ))).

[0106] Example 11 Preparation of a transparent isotropic shampoo containing the composition of the present invention

Table 12

[0107] The shampoo is prepared by dispersing polyquaternium-10 in water. The remaining components of Phase A are mixed separately by adding them sequentially while mixing well after each addition. This premix is added to the polyquaternium-10 dispersion and mixed for an additional 5 minutes. Then, the premixed Phase B and premixed Phase C are added with stirring (Monomuls 90L-12 is heated and dissolved in Texapon NSO IS). Phases D and E are added with stirring. The pH is adjusted to 5.5 - 6.0 with a citric acid solution to obtain a fragrance-free shampoo formulation. A fragrant shampoo is prepared by adding 0.4 - 0.8 wt% of the composition of Example 7 of the present invention to the fragrance-free shampoo formulation in Table 3 while gently shaking.

[0108] Example 12 Preparation of a structured shower gel containing the composition of the present invention

Table 13

[0109] A shower gel is prepared by adding 0.5 - 1.5 wt% of the composition of Example 7 of the present invention to the fragrance-free shower gel formulation in Table 4 while gently shaking.

[0110] Example 13 Preparation of a transparent shower gel containing the composition of the present invention

Table 14

[0111] A transparent shower gel is prepared by adding 0.5 - 1.5 wt% of the composition of Example 7 of the present invention to the fragrance-free shower gel formulation in Table 5 while gently shaking.

[0112] Example 14 Preparation of a milky white shower gel containing the composition of the present invention

Table 15

[0113] A transparent shower gel is prepared by adding 0.5 to 1.5% by weight of the composition of Example 7 of the present invention to the fragrance-free shower gel formulation in Table 6 while gently shaking.

[0114] Example 15 Preparation of a shiny shampoo containing the composition of the present invention

Table 16-1

Table 16-2

[0115] The shampoo is prepared by dispersing guar hydroxypropyltrimonium chloride and polyquaternium-10 in water and sodium EDTA tetra. After phase A becomes homogeneous, a 10% NaOH solution (phase B) is added. Then, the premixed phase C is added. And the mixture is heated to 75 °C. The phase D components are added and mixed until homogeneous. The mixture is cooled. At 45 °C, the phase E components are added while mixing. The final viscosity is adjusted with a 25% NaCl solution, and the pH is adjusted to 5.5 - 6 with a 10% NaOH solution.

[0116] A scented and glossy shampoo is prepared by adding 0.4 to 0.8% by weight of the composition of Example 7 of the present invention to the fragrance-free shampoo formulation in Table 7 while gently shaking.

[0117] Example 16 Preparation of a structured shower gel containing the composition of the present invention

Table 17

[0118] A transparent shower gel is prepared by adding 0.5 to 1.5% by weight of the composition of Example 7 of the present invention to the total weight of the shower gel while gently shaking it into the fragrance-free shower gel formulation in Table 8.

[0119] Example 17 Preparation of an anhydrous antiperspirant spray formulation containing the composition of the present invention

Table 18

[0120] An anhydrous antiperspirant spray formulation is prepared using a high-speed stirrer. Silica and quaternium-18-hectonite are added to a mixture of isopropyl myristate and cyclomethicone. Once fully swollen, chlorhydroxyaluminum is added portion-wise with stirring until the mixture is homogeneous and free of lumps. Next, the perfume oil, which is the composition of Example 7 of the present invention, is added.

[0121] Example 18 Preparation of a deodorant spray emulsion formulation containing the composition of the present invention

Table 19

[0122] A deodorant spray emulsion formulation is prepared by mixing and dissolving all the components in the order in Table 10. The aerosol can is filled, and the propellant is compressed and added. Aerosol filling: 40% active solution, 60% propane / butane (2.5 bar).

[0123] Example 19 Preparation of a deodorant stick formulation containing the composition of the present invention

Table 20

[0124] The deodorant stick formulation is obtained by weighing all the components of Part A and heating them to 70 - 75°C. Mix the other components of Part A, and after heating, add Cetearyl-25. When dissolving Cetearyl-25, add stearic acid. Prepare Part B by dissolving triclosan in 1,2-propylene glycol. Make up for the evaporated water. Then, pour Part B into Part A while mixing slowly. Add the perfume oil (Phase C), which is the composition of Example 7 of the present invention, while gently shaking. For storage, put the plastic bag into the bucket and seal it after cooling. The mold was filled at about 70°C.

[0125] Example 20 Preparation of a deodorant roll-on formulation containing the composition of the present invention

Table 21

[0126] Prepare Part A by gradually adding hydroxyethyl cellulose to water while stirring at high speed with a turbine until the hydroxyethyl cellulose is completely swollen and a transparent gel is obtained. Pour Part B slowly into Part A while continuing to stir until the whole mixture becomes homogeneous. Then, add Part C and D while gently shaking.

[0127] Example 21 Preparation of a day cream-based O / W emulsion containing the composition of the present invention

Table 22

[0128] An O / W emulsion based on a day cream 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 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 before adding sodium carbomer (part D) and essential oil (part E), which is the composition of Example 7 of the present invention. After stirring the mixture for 3 minutes, stirring is stopped for 15 minutes. When the temperature of the mixture reaches 30 °C, stirring is restarted for an additional 15 minutes until the cream is homogeneous, shiny, and free of lumps. If necessary, the pH is adjusted to 6.70 - 7.20 with Glydant, Phenonip or Nipaguard PO5, or to 6.30 - 7.00 with Nikkoguard.

Claims

1. a) 0.5 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 30% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one A composition comprising, The percentages are based on the total weight of the composition; and A composition in which the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of 40:60 to 15:

85.

2. The composition is a) 7 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 0.5 to 25% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 30% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 85% by weight of (Z)-oxacyclohexadec-13-en-2-one The composition according to claim 1, comprising.

3. The composition is a) 40 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 2 to 25% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 20% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 35% by weight of (Z)-oxacyclohexadec-13-en-2-one The composition according to claim 1 or 2, comprising.

4. The composition is a) 50 to 85% by weight of (Z)-oxacyclohexadec-12-en-2-one; b) 5 to 20% by weight of (E)-oxacyclohexadec-12-en-2-one; c) 0 to 20% by weight of (E)-oxacyclohexadec-13-en-2-one; and d) 0.5 to 25% by weight of (Z)-oxacyclohexadec-13-en-2-one The composition according to any one of claims 1 to 3, comprising.

5. The composition according to any one of claims 1 to 4, wherein the weight ratio of the E-diastereoisomer to the Z-diastereoisomer is in the range of 30:70 to 17:

83.

6. A method for imparting, enhancing, improving or modifying the odor characteristics of a fragrance composition or a perfumed article, comprising adding an effective amount of the composition defined in any one of claims 1 to 5 to the composition or consumer product.

7. Use as a fragrance component of the composition defined in any one of claims 1 to 5.

8. A fragrance composition comprising: i) at least one composition defined in any one of claims 1 to 5; 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 containing the same.

9. A perfumed consumer product comprising at least one compound of formula (I) defined in any one of claims 1 to 5 or the fragrance composition defined in claim 8.

10. The perfumed consumer product according to claim 9, 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.

11. The perfumed consumer product according to claim 10, wherein the perfumed consumer product is a perfume, a splash or eau de parfum, a cologne, a shaving or aftershave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, paper, a bleaching agent, a carpet cleaner, a curtain care product, a shampoo, a coloring preparation, a color care product, a hair styling product, a dental care product, a disinfectant, an intimate care product, a hair spray, a vanishing cream or a deodorant or antiperspirant, a depilatory, a tanning product or a sunburn product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, an oil or gel, or a foot / hand care product, a sanitary product, an air freshener, an "instant use" powdered air freshener, a mold remover, a furniture care product, a wipe, a dishwashing or hard surface detergent, a leather care product, a car care product.

12. A method for producing the composition defined in any one of claims 1 to 5, comprising: i) 0.5 to 85% by weight of the formula 【Chemical 1】 [Wherein, R １ represents an OR ２ or NR ２ ２ group, where R ２ represents a C １～３ alkyl group], a compound in the form of any one of its stereoisomers or a mixture thereof ii) 0.5 to 85% by weight of the formula 【Chemical 2】 [wherein, R １ has the same meaning as defined above], which is a compound in the form of any one of its stereoisomers or a mixture thereof, iii) 0.5 to 30% by weight of the formula [Chemical Formula 3] [wherein, R １ has the same meaning as defined above], a compound in the form of any one of its stereoisomers or a mixture thereof, and iv) 0 to 30% by weight of the formula [Chemical Formula 4] [wherein, R １ has the same meaning as defined above], which is a compound in the form of any one of its stereoisomers or a mixture thereof A method comprising thermal desorption of a mixture containing the same.

13. The production of a mixture containing 0.5 to 85% of a compound of formula (I), 0.5 to 85% of a compound of formula (II), 0.5 to 30% of a compound of formula (III), and 0 to 30% of a compound of formula (IV) comprises the following steps: a) Epoxidizing a composition comprising at least 70% of oxacyclohexadec-12-en-2-one and oxacyclohexadec-13-en-2-one having a double bond in the E configuration, and at most 30% of oxacyclohexadec-12-en-2-one and oxacyclohexadec-13-en-2-one having a double bond in the Z configuration; b) Hydrolyzing the mixture obtained in step a) to i) 0.5 to 85% by weight of the diol (12RS,13SR)-12,13-dihydroxyoxacyclohexadecane-2-one; ii) 0.5 to 85% by weight of the diol (13RS,14SR)-13,14-dihydroxyoxacyclohexadecane-2-one; iii) 0.5 to 30% by weight of the diol (12RS,13RS)-12,13-dihydroxyoxacyclohexadecane-2-one; and iv) 0 to 30% by weight of the diol (13SR,14SR)-13,14-dihydroxyoxacyclohexadecane-2-one to form a mixture of diols; and c) treating the diol obtained in step b) with tri C １～３ alkyl orthoformate or DMF acetal A method according to claim 12, comprising **Claim 14** Formula 【Chemical Formula 5】 [In the formula, when m is 1, n is 1, or when m is 0, n is 2; the R group represents hydrogen, or both R groups together form a C １～６ alkyl group, CHO ２ R or CHNR ２ ２ group, where R ２ represents a C １～３ alkyl group], a compound in the form of any one of their stereoisomers or a mixture thereof. **Claim 15** 13-(1,3-dihydroxypropyl)oxacyclotridecan-2-one, in the form of any one of its stereoisomers or a mixture thereof.

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