Oxamacrocyclic musks as fragrance compounds.

Abstract

The present invention is in the field of perfumery and relates to novel oxamacrocyclic perfume compounds according to general formula (I) with musk-like odor notes, improved biodegradability and improved chemical stability. The present invention also relates to a method for preparing these compounds. Furthermore, the present invention also relates to perfume compositions comprising one or more of the compounds of the present invention. Furthermore, the present invention relates to the use of these compounds or perfume compositions as odorants or for improving the fixation of perfume compounds or perfume compositions, as well as for preparing perfumed products. In addition, the present invention also refers to the use of said compounds or compositions for the preparation of perfumed products, as well as to the perfumed products themselves.

Description

[Technical field]

[0001] The present invention is in the field of perfumery and relates to novel oxamacrocyclic perfume compounds according to general formula (I) with musky odor notes, improved biodegradability and improved stability. The present invention also relates to a method for preparing these compounds. Furthermore, the present invention relates to perfume compounds comprising one or more of the compounds of the present invention. Moreover, the present invention relates to the use of these compounds or perfume compositions as an odorant or for improving the fixation of perfume compounds or perfume compositions, as well as for the preparation of a perfumed product. In addition, the present invention refers to the use of said compounds or compositions for the preparation of a perfumed product, as well as to the perfumed product itself. [ka] [Background technology]

[0002] Musk is a class of aromatic substances that has been established as a basic note in the perfume industry. They include glandular secretions from animals such as the musk deer, numerous plants with similar fragrances, and manmade substances with similar odors. Musk was originally the name given to a strong-smelling substance obtained from the glands of the musk deer. The substance has been used since ancient times as a well-known fragrance fixative and is one of the most expensive animal products in the world. It has been applied to a variety of similar-smelling plants and animals (e.g., musk ox) and has come to encompass a wide variety of perfumery substances with similar odors, despite often differing chemical structures and molecular shapes.

[0003] The only known organic compound with the characteristic musk odor is muscone, a 15-membered ketone with one methyl substituent at the 3-position. It is an oily liquid found in nature as the (-) enantiomer, (R)-3-methyl-cyclopentadecanone. On the downside, muscone is very poorly soluble in water and hardly biodegradable.

[0004] However, there is a great demand for synthetic materials that have strong musk odor characteristics and are also chemically stable and biodegradable.

[0005] In particular, sufficient chemical stability (i.e., high odor stability) is required to ensure the stability of the perfume material within the product formulation, and thus the perfumed product itself, which in turn ensures high product quality with a consistent odor. Decomposition of perfume materials can cause undesirable off-odor notes, color changes, etc.

[0006] Furthermore, in terms of sustainability, there is a high demand for compounds, especially fragrances, with significantly improved biodegradability, therefore enhanced water solubility of the compounds is an immense advantage.

[0007] It is therefore a primary object of the present invention to provide new musk fragrance compounds which exhibit superior odor characteristics while at the same time being chemically stable and biodegradable.

[0008] It has now surprisingly been found that the novel oxamacrocyclic compounds according to general formula (I) provide excellent perfume materials suitable for a wide range of applications, since they not only have a pronounced natural, balanced and powerful musk odor, but also have high stability and enhanced tenacity. Moreover, the novel compounds according to general formula (I) have improved water solubility and are therefore better biodegradable. Summary of the Invention

[0009] In a first aspect, the present invention provides a compound of general formula (I): [ka] or a stereoisomer, particularly an enantiomer, of During the ceremony, X represents methylene or ethylene optionally substituted by a methyl group; Y represents methylene or O; R1 represents H, a methyl group, or an ethyl group; R2 represents H, a methyl group, or an ethyl group; Z represents an optionally substituted C2, C3, C4, C5, C6, or C7 alkyl group; Optionally, there is a C=C double bond at at least one of the dotted lines.

[0010] In a second aspect, the present invention relates to a fragrance composition comprising at least one compound according to the invention and at least one further fragrance substance.

[0011] In a third aspect, the present invention relates to a method for preparing a compound of general formula (I) according to the invention, (1) General formula (II): [ka] preparing an olefin according to the formula: (2) performing olefin metathesis on the olefin prepared in step (1) to obtain a compound of general formula (I).

[0012] In a fourth aspect, the present invention relates to the use of a compound according to the invention or a perfume composition comprising a compound according to the invention as an odorant or perfume compound or for improving the fixing property of a perfume compound or a composition comprising a perfume compound or for preparing a perfumed product.

[0013] In a further aspect, the present invention relates to a perfumed product comprising a compound according to the invention or a perfume composition comprising a compound according to the invention.

[0014] In yet another aspect, the present invention relates to a perfumed product comprising an effective amount of a compound according to the present invention, or a perfume composition comprising a compound according to the present invention, and a carrier or substrate.

[0015] Finally, the present invention relates to a perfumed product defined as comprising a compound according to the invention or a perfume composition comprising a compound according to the invention, where the perfumed product is a perfume oil, a perfume base, a personal hygiene preparation, a cleaning agent or an air freshener.

[0016] The inventors have now established that the novel compounds according to general formula (I) have a pronounced musky odor with a partly creamy, animalic and powdery odor note, together with high adhesion. Furthermore, the compounds according to the present invention show improved chemical stability and improved water solubility, and therefore are improved in terms of their biodegradability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] According to the present invention, the above object is achieved by the preparation of compounds of general formula (I): [ka] or a stereoisomer, particularly an enantiomer, of During the ceremony, X represents methylene or ethylene optionally substituted by a methyl group; Y represents methylene or O; R1 represents H, a methyl group (CH3) or an ethyl group; R2 represents H, a methyl group, or an ethyl group; Z represents an optionally substituted C2, C3, C4, C5, C6, or C7 alkyl group; Optionally, there is a C=C double bond at at least one of the dotted lines.

[0018] The compounds of general formula (I) have a distinctive, balanced and characteristic musky odor profile, with animalic, creamy, chalky and ergonic notes, and outstanding fixativeness.Based on the additional creamy and chalky notes, the compounds currently developed are suitable for use as alternative perfume materials with enhanced secondary properties and thus more natural odor profiles that provide creamy and chalky accords that can be advantageously incorporated into a wide range of formulations to create more vivid scents.Thus, the present invention provides creamy and chalky notes together with animalic and musky notes.

[0019] Moreover, the ketone-containing oxamacrocyclic compounds described herein unexpectedly have both a strong musky odor and significantly improved water solubility while being chemically stable. These compounds are therefore highly suitable for use as perfumes, in perfume mixtures, and in preparations containing these perfumes or perfume mixtures, which are also better biodegradable, meaning they are more sustainable.

[0020] Such compounds according to the present invention (having general formula (I) X represents methylene; Y represents methylene or O; R1 represents H or a methyl group; R2 represents H or a methyl group; It has been found that compounds having at least one C=C double bond at any of the dotted line positions are highly soluble in water and chemically stable while unexpectedly exhibiting a very strong musk odor.

[0021] It will be apparent to those skilled in the art that, in general, when Y represents O, R1 is empty.

[0022] The present inventors have found that the adhesion to laundry depends on the ring size of the oxamacrocyclic compounds according to the present invention.

[0023] Thus, it has surprisingly been found that compounds according to formula (I) which are 15 or 16 membered rings have significantly improved water solubility combined with improved deposition properties on laundry whilst containing a strong musk odour.

[0024] Therefore, the compound according to the general formula (I) is preferably a 13- to 18-membered ring, more preferably a 14- to 17-membered ring, and particularly preferably a 15- or 16-membered ring.

[0025] The ring size of the oxamacrocycle according to general formula (I) is related to the optionally substituted C2, C3, C4, C5, C6 or C7 alkyl group represented by Z, such that the compound according to general formula (I) is a 14-membered ring and Z represents an optionally substituted C3 alkyl group; or the compound according to general formula (I) is a 15-membered ring and Z represents an optionally substituted C4 alkyl group; or the compound according to general formula (I) is a 16-membered ring and Z represents an optionally substituted C5 alkyl group; or the compound according to general formula (I) is a 17-membered ring and Z represents an optionally substituted C6 alkyl group; or the compound according to general formula (I) is an 18-membered ring and Z represents an optionally substituted C7 alkyl group.

[0026] In a preferred variation, the compounds of general formula (I) according to the invention contain a C=C double bond at the other dotted position shown in the molecule.

[0027] The dotted lines are the simplest way to represent these options in a structural formula, and their meanings will be clear to those skilled in the art, and embodiments thereof can be identified from the Examples.

[0028] However, the best combination of water solubility properties, chemical stability and odor profile was achieved for the embodiment of formula (I) in which R represents H.

[0029] Surprisingly, improved water solubility and odor profile have been found for embodiments of formula (I) in which R2 represents H and X represents methylene.

[0030] However, the best combination of water solubility properties, chemical stability and odor profile was achieved for the embodiment of formula (I) in which X represents methylene, Y represents methylene, R2 represents H, Z represents a C4 alkyl group and the C=C double bond is in the 6- and 7-positions.

[0031] In particular, a preferred embodiment according to the present invention is 1-oxacyclopentadec-6-en-3-one (A).

[0032] In an alternative variation, excellent water solubility properties, chemical stability and odor profile were achieved for an embodiment of formula (I) in which X represents methylene, Y represents methylene, R2 represents H, Z represents a C5 alkyl group and the C=C double bond is in the 6- and 7-positions.

[0033] In particular, another preferred embodiment according to the present invention is 1-oxacyclohexadec-6-en-3-one (B).

[0034] Both compounds A and B have an optimized and well-balanced ratio of hydrophilic and hydrophobic properties, respectively, and thus have improved biodegradability in addition to a strong musk odor.

[0035] The embodiments of general formula (I) in which R2 represents an alkyl group, preferably a methyl or ethyl group, have both good water solubility and chemical stability. Moreover, these embodiments exhibit a strong musk odor.

[0036] Thus, in an alternative variation, the embodiment of formula (I) in which R2 represents a methyl group exhibits good water solubility and chemical stability, whilst exhibiting a distinctly different odour profile.

[0037] In a preferred embodiment, excellent water solubility properties, chemical stability and a strong odor profile are achieved from compounds according to general formula (I) in which X represents methylene, Y represents methylene, R2 represents a methyl group, Z represents a C5 alkyl group and the C=C double bond is in the 6- and 7-positions.

[0038] Therefore, a further preferred embodiment according to the invention is 6-methyl-1-oxa-cyclohexadec-6-en-3-one (C).

[0039] Furthermore, the inventors have discovered that embodiments of formula (I) in which Y represents O have a strong odor profile and further improved water solubility.

[0040] Thus, an alternative variant according to the invention having improved water solubility properties is obtained by a compound of general formula (I) in which X represents methylene and Y represents O, and the compound contains a C=C double bond at the other dotted position shown in the molecule.

[0041] Preferably, the compound of general formula (I) in which X represents ethylene, Y represents O, the compound contains a C=C double bond in the other dotted position shown in the molecule, and in which Z represents a C5 alkyl group.

[0042] Such 16-membered ring compounds have improved solubility behavior in water and high chemical resistance.

[0043] In particular, a further preferred embodiment according to the present invention is 1,5-dioxacyclohexadec-14-en-3-one (D).

[0044] In order to obtain compounds according to general formula (I) with improved water solubility behaviour and chemical resistance in the compounds and further improved adhesion to laundry, Z represents a C6 alkyl group.

[0045] Preferably, the compound of general formula (I) wherein X represents ethylene, Y represents O, the compound contains a C=C double bond at the other dotted position shown in the molecule, and Z represents a C6 alkyl group in the compound.

[0046] In particular, a further preferred embodiment according to the present invention is 1,5-dioxacyclo-heptadec-15-en-3-one (E).

[0047] In a third aspect, the present invention relates to a method for preparing a compound of general formula (I) according to the invention, (1) General formula (II): [ka] preparing an olefin according to the formula: (2) performing olefin metathesis on the olefin prepared in step (1) to obtain a compound of general formula (I).

[0048] The method according to the invention provides a simple and inexpensive access to oxamacrocyclic perfume compounds according to general formula (I) with musk-based odor notes and improved biodegradability, as well as improved chemical stability.

[0049] The preparation of olefins according to general formula (II) can be carried out by the reaction of a compound according to general formula (III): [ka] can be obtained starting from an allyl alcohol of the formula:

[0050] In the first step, an allylic alcohol according to general formula (III) is reacted with a halogenated acetate to give an ether.

[0051] In the second step, the ether obtained from the first step is reacted with a substituted or unsubstituted allyl halide to give an allylated ether compound.

[0052] In the third step, the allylated ether compound obtained in the second step is decarboxylated.

[0053] Thus, olefins of general formula (II) are readily available from commercially available, inexpensive allylic alcohols of general formula (III).

[0054] Alternatively, depending on the desired compound of general formula (I), the olefin according to general formula (II) may be a compound of general formula (III): [ka] It can be obtained starting from an allyl alcohol of the formula:

[0055] In the first step, allyl alcohol is reacted with an oxirane.

[0056] In the second step, a ring opening reaction of the oxirane obtained from the first step is conducted with an allylalcohol to give a tertiary alcohol.

[0057] In the third step, the tertiary alcohol obtained in the second step is oxidized.

[0058] Thus, olefins of general formula (II) are readily available from commercially available, inexpensive allylic alcohols of general formula (III).

[0059] Olefin metathesis of olefins according to general formula (II) may be achieved by the use of commercially available catalysts, such as Grubbs' catalyst.

[0060] When referring to compounds of general formula (I) in this specification, this is intended to refer to all stereoisomers, in particular all enantiomers, without regard to the isomerically pure stereoisomers or any mixtures of these stereoisomers. For economic reasons, it is preferred to use the compounds as mixtures of their stereoisomers, in particular mixtures of their enantiomers.

[0061] Thus, the compound of formula (I) (a) Optically active pure enantiomers; (b) a racemic mixture of enantiomers; or (c) Optically active mixtures of different enantiomers It exists in the form:

[0062] Thus, the present invention also discloses mixtures of any of the above compounds and / or mixtures of any of the above stereoisomers, as well as the use of such compounds and / or mixtures within the contemplation of the present application.

[0063] In general, in the context of the present invention, the term "compounds of formula (I)" refers both to the individual compounds of formula (I) (as well as their isomeric forms) and to all mixtures of compounds of formula (I) (as well as their isomeric forms) in any mixing ratio. In other words, reference in the following description to "compounds of formula (I)" applies both to single compounds of formula (I), to single isomeric forms and to mixtures consisting of or containing compounds of formula (I) and their isomeric forms in any mixing ratio. The present invention therefore relates to the compounds according to the invention individually per se and to mixtures of compounds according to the invention.

[0064] Furthermore, with reference to general formula (I) and any C=C double bonds contained therein, the compounds exist in the form of geometric isomers, ie, Z and E configurations.

[0065] The compounds of general formula (I) according to the invention can be used as individual substances or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in perfume compositions, e.g. at least one other known perfume substance selected from a wide range of natural and synthetic substances available in numerous perfume mixtures and / or admixtures with carrier substances and other adjuvants commonly used in the art.

[0066] Thus, in a second aspect, the present invention refers to a perfume composition comprising at least one compound according to the invention and at least one further perfume substance.

[0067] The following named flavoring materials may be used as individual materials or in mixtures with at least one, two, three or more flavoring materials in a number of flavor mixtures selected from a wide range of natural and synthetic materials.

[0068] Fragrance materials which are advantageously suitable for combination are described in S. Arctander, Perfume and Flavor Materials, volumes I and II, Montclair, NJ 1969, private publication, and / or in H. Surburg, J. Panten, Common Fragrance and Flavor Materials, vol. 6. th edition, Wiley-VCH, Weinheim, 2016. The following list contains examples of known odorants which are advantageously suitable for combination with the compounds of the invention and their mixtures: For example, ambergris tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; cocoa absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; bucco leaf oil; cabreuva oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute; cedar leaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaiba balsa mugwort;copaiba balsam oil;coriander oil;costus root oil;cumin oil;cypress oil;davana oil;dill weed oil;dill seed oil;eau de brows absolute;oak moss absolute;elemi oil;tragon oil;eucalyptus citriodora oil;eucalyptus oil;fennel oil;pine needle oil;galbanum oil;galbanum resin;geranium oil;grapefruit oil;guaiac wood oil;gruyun balsam;gruyun balsam oil;helichrysum absolute;helichrysum oil;ginger oil;iris root absolute;iris root oil;jasmine absolute;calamus oil;Camellia oil blue;Camellia oil roman;Carrot seed oil;Cascarilla oil;Pine needle oil;Spearmint oil;Caraway oil;Labdanum oil;Labdanum absolute;Labdanum resin;Lavandin absolute;Lavandin oil;Lavender absolute;Lavender oil;Lemongrass oil;Lovage oil;Distilled lime oil;Pressed lime oil;Linalool oil;Limonaria oil;Bay leaf oil;Mashi oil;Marjoram oil;Mandarin oil;Massoiabark oil;Mimosa absolute;Ambrette oil;Must tincture;Muscat sage oil;Nutmeg oil;Myrrh absolute t;myrrh oil;myrtle oil;clove leaf oil;clove flower oil;neroli oil;olibanum absolute;olibanum oil;oponax oil;orange blossom absolute;orange oil;oregano oil;palmarosa oil;patchouli oil;shiso oil;peru balsam oil;parsley leaf oil;parsley seed oil;petitgrain oil;peppermint oil;pepper oil;pimento oil;pine oil;pennyroyal oil;rose absolute;rosewood oil;rose oil;rosemary oil;sage oil dalmatian;sage oil spanish;sandalwood oil;celery seed oil;spike lavender oil;Star anise oil;Styrax oil;Tagetes oil;Fir needle oil;Tea tree oil;Turpentine oil;Thyme oil;Tolu balsam;Tonka absolute;Tuberose absolute;Vanilla extract;Violet leaf absolute;Verbena oil;Vetiver oil;Juniper berry oil;Cognac oil;Mugwort oil;Oil of wintergreen;Ylang-ylang oil;Aesop's oil;Civet absolute;Cinnamon leaf oil;Extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams and tinctures, such as cinnamon bulk oil, and fractions thereof or components isolated therefrom; For example, 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; famecene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; and hydrocarbons such as diphenylmethane; Aliphatic alcohols such as, for example, hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3,4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol, and 4-methyl-3-decen-5-ol. Aliphatic aldehydes and their acetals, such as, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-9-undecenal, 2,6,10-trimethyl-5,9-undecadienal, heptanal diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde, and 1-(1-methoxypropoxy)-(E / Z)-3-hexene; Aliphatic ketones and their oximes, such as, for example, 2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime, 2,4,4,7-tetramethyl-6-octen-3-one, and 6-methyl-5-hepten-2-one; Aliphatic sulfur-containing compounds such as, for example, 3-methylthio-hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol; Aliphatic nitriles such as, for example, 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; and 3,7-dimethyl-6-octenoic acid nitrile; For example, (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl-isobutyric acid; hexyl crotonic acid. Esters of aliphatic carboxylic acids such as xyl;ethyl isovalerate;ethyl 2-methyl pentanoate;ethyl hexanoate;allyl hexanoate;ethyl heptanoate;allyl heptanoate;ethyl octanoate;ethyl (E,Z)-2,4-decadienoate;methyl 2-octynate;methyl 2-nonynate;allyl 2-isoamyloxyacetate;methyl 3,7-dimethyl-2,6-octadienoate;4-methyl-2-pentyl-crotonate; For example, citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-oct acyclic terpene alcohols such as 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their esters with formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, pentanoic acid, hexanoic acid, crotonic acid, tiglic acid and 3-methyl-2-butenoic acid; For example, aldehydes and ketones of acyclic terpenes such as geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranylacetone, and the dimethyl acetals and diethyl acetals of geranial, neral, and 7-hydroxy-3,7-dimethyloctanal; Cyclic terpene alcohols such as, for example, menthol, isopulegol, α-terpineol, terpinenol-4, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambulinol, vetiverol, guaiol, and their esters with formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, pentanoic acid, hexanoic acid, crotonic acid, tiglic acid, and 3-methyl-2-butenoic acid; For example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascone; β-damascone; β-damascenone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3, 4,6,7,8a-Hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one;2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal;Nootkatone;Dihydronootkatone;4,6,8-Megastigmatrien-3-one;α-Sinensal;β-Sinensal;Aldehydes and ketones of cyclic terpenes such as acetylated cedarwood oil (methyl cedryl ketone); Cyclic alcohols such as, for example, 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; For example, α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl alicyclic alcohols such as 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; Cyclic and alicyclic ethers such as, for example, cineole; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodeca-hydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane; For example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentenone 3-Methylcyclopentadecanone;4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;4-tert-pentylcyclohexanone;5-Cyclohexadecen-1-one;6,7-Dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;8-Cyclohexadecen-1-one;9-Cycloheptadecen-1-one;Cyclopentadecanone;Cyclohexadecanone and macrocyclic ketones; For example, alicyclic aldehydes such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; Alicyclic ketones such as, for example, 1-(3,3-dimethyl-cyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone; For example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl acetate Esters of cyclic alcohols such as 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl acetate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl propionate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate;4,7-methanooctahydro-5- or 6-indenyl acetate; For example, esters of alicyclic alcohols such as 1-cyclohexylethyl crotonate; Esters of alicyclic carboxylic acids such as, for example, allyl-3-cyclohexyl propionate; allylcyclohexyl oxyacetate; cis- and trans-methyl dihydrojasmate; cis- and trans-methyl jasmate; methyl-2-hexyl-3-oxocyclopentane carboxylate; ethyl-2-ethyl-6,6-dimethyl-2-cyclohexene carboxylate; ethyl-2,3,6,6-tetramethyl-2-cyclohexene carboxylate; 2-ethyl-2-methyl-1,3-dioxolane ethyl acetate; Aromatic aliphatic alcohols such as, for example, benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; and 1-(4-isopropylphenyl)ethanol. Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids such as, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenylethyl acetate, α,α-dimethylphenyl-ethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, and 4-methoxybenzyl acetate; Aromatic aliphatic ethers such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxine; and 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine. For example, benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropic aldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; α-bu Aromatic and araliphatic aldehydes such as 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methyl-3-(4-methoxyphenyl)propanal; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; For example, acetophenone; 4-methyl-acetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; Benzophenone; 1,1,2,3,3,6-hexafluorophenyl Aromatic and araliphatic ketones such as 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; Aromatic and araliphatic carboxylic acids and their esters, such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenylethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl-2,4-dihydroxy-3,6-dimethylbenzoate; ethyl-3-phenyl glycidate; ethyl-3-methyl-3-phenyl glycidate; For example, nitrogen-containing aromatic compounds such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenoic acid nitrile; 3-methyl-5-phenylpentanoic acid nitrile; methyl anthranilate; methyl-N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; Phenols, phenyl ethers and phenyl esters such as, for example, estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate; Heterocyclic compounds such as, for example, 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; For example, 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis- and trans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen-1,15-olide. The individual fragrance substances from the groups including: 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; lactones such as octahydrocoumarin; as well as mixtures of the above substances.

[0069] In such perfume compositions, the compounds according to the invention show a positive impact on the overall fragrance code by clearly enhancing the musk of the final composition, which is accompanied by an animal-based odor note, while at the same time providing good fixation, retention and substantivity.Thus, the presently described compounds according to the invention can be used as efficient and stable perfume compounds.

[0070] In the fragrance composition, the amount of the compound according to the present invention used is preferably in the range of 0.0001 to 90% by weight, more preferably 0.01 to 70% by weight, particularly preferably 0.1 to 50% by weight, based on the total amount of the fragrance composition.

[0071] The perfume compounds according to the invention and the perfume compositions comprising or containing at least one compound according to the invention may be used for perfumery applications in liquid form, undiluted or diluted with a solvent.Suitable solvents for this purpose are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, triacetin, vegetable oils, etc.

[0072] Furthermore, the perfume compounds according to the invention or perfume compositions which contain or comprise the compounds according to the invention may be adsorbed on carriers which ensure both a fine distribution of the perfume substances in the final product and a controlled release during use. Such carriers may be porous inorganic materials such as, for example, sodium sulfate, silica gel, zeolites, gypsum, clay, clay granules, aerated concrete, etc., or organic materials such as, for example, wood, cellulosic substances, sugars, dextrins (for example maltodextrin) or plastics such as PVC, polyvinyl acetate or polyurethane.

[0073] The perfume compounds according to the invention as represented by formula (I) and perfume compositions comprising or containing the compound(s) according to the invention may also be microencapsulated, spray dried, provided as an inclusion complex or as an extruded product (i.e. a product according to the invention).

[0074] Optionally, the properties of the perfume compound or perfume composition so modified may be further optimized with regard to targeted perfume release by "coating" with a suitable material, for this purpose waxy plastics such as polyvinyl alcohol are preferably used, the resulting product being now the product according to the invention.

[0075] The perfume compounds according to the invention or the perfume compositions according to the invention may be encapsulated, for example by the coacervation method, with the aid of an encapsulant made of polyurethane type substances or soft gelatine.

[0076] Spray-dried perfume formulations based on the perfume compounds according to the invention and on perfume compositions comprising or containing the perfume compound(s) according to the invention may for example be produced by spray-drying emulsions or dispersions comprising or containing the perfume compounds or perfume compositions, whereby modified starches, proteins, dextrins and vegetable gums may be used as carriers. Inclusion complexes may for example be produced by introducing the perfume compound or perfume composition and cyclodextrin or urea derivatives into a suitable solvent, for example water.

[0077] The extruded product may be prepared by melting the perfume compound or perfume composition together with a suitable waxy material, optionally extruding in a suitable solvent, for example isopropanol, and then solidifying.

[0078] In another aspect, the present invention therefore relates to the use of the compounds according to general formula (I) or of perfume compositions comprising or containing the compounds according to the invention as efficient odorants or perfume compounds. The comments made above apply accordingly to the preferred compounds and mixtures.

[0079] The present invention relates to the use of the compounds according to the invention or compositions comprising or containing the compounds according to the invention as perfume substances while at the same time improving the fixation of perfume compounds, and to the use of perfume compositions comprising or containing the compounds according to the general formula (I) or at least one compound according to the invention for preparing perfumed products. With regard to the preferred selection of the compounds and mixtures according to the invention, the comments given above naturally apply accordingly.

[0080] The present invention therefore relates to the use of said compounds and compositions for improving the deposition of perfume compounds or for preparing perfumed products.

[0081] The compounds according to the invention or compositions comprising or containing the compounds according to the invention may be incorporated into products which are perfumed or are intended to be perfumed, in particular preparations useful for personal hygiene, such as perfume oils, perfume bases, preparations for personal hygiene, cleaning agents or fragrances.

[0082] Therefore, in another aspect, the present invention also refers to a perfumed product comprising or containing a compound according to formula (I) or a perfume composition comprising or containing at least one compound according to the present invention.

[0083] According to a preferred variant, the perfumed product according to the invention comprising or containing the compound according to the invention or a perfume composition comprising or containing the compound according to the invention is produced by incorporating the compound according to the invention or a composition comprising or containing the compound according to the invention in pure form without solvent, as a solution with a solid or liquid carrier and optionally other auxiliary agents and / or stabilizers, or in the form of a mixture, in order to form a basic preparation useful for personal hygiene, such as, for example, a cleaning agent.

[0084] The present invention therefore also provides a perfumed product comprising or containing an effective amount of a compound of general formula (I), or a perfume composition comprising or containing at least one compound according to the present invention, in combination with a carrier or substrate.

[0085] By sensory effective amount is meant that the proportion of the substance according to general formula (I) is already sufficient to give off a pleasant perceptible perfume impression, in particular a musky odor impression, which is generally achieved when at least 0.001% by weight of the compound according to general formula (I) is present in the final preparation / formulation.

[0086] In addition to their intense sensory properties, the compounds of formula (I) described herein have additional beneficial secondary properties, such as high stability under certain application conditions, particularly in acidic media, which makes the compounds of the invention suitable for a wide range of uses and processing.

[0087] Perfumed products according to the invention are, for example, perfumed acidic, alkaline and neutral cleaning agents, such as floor cleaners, window cleaners, dishwashing detergents, bath and toilet cleaners, stain remover creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, textile deodorizers, ironing aids, liquid detergents, washing powders, laundry pretreatment agents, such as bleaches, soaking agents and stain removers, laundry softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, and air fresheners in liquid or gel form. or solid carriers, aerosol sprays, waxes and polishes, such as furniture polishes, floor waxes and shoe polishes, as well as body care products, such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, such as skin creams and lotions, facial creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products, such as hair sprays, hair gels, strengthening hair lotions, hair rinses, permanent and semi-permanent hair dyes, hair shaping agents, such as cold perm agents and hair straighteners, hair tonics, hair creams and lotions, deodorants and antiperspirants, e.g. underarm sprays, roll-ons, deodorant sticks, deodorant creams or decorative cosmetic products, e.g. eye shadows, nail polishes, make-up, lipsticks, mascaras, as well as candles, lamp oil, incense, insecticides, insect repellents and fuels, or oral and / or dental care products, e.g. toothpastes, dental gels, dental powders, mouthwashes, chewing gums and other oral care products.

[0088] The product according to the invention may also be a semi-finished product comprising an effective amount of a compound of general formula (I) or a perfume composition which contains or comprises at least one compound according to the invention.

[0089] The proportion of the compound of general formula (I) or the perfume composition containing or comprising at least one compound according to the invention used may vary within wide limits, ranging for example from a few parts per thousand in mass market products such as detergents to a maximum of a few percent in alcoholic extracts for fine perfumery. However, even small amounts of the novel compound according to the invention or the perfume composition containing or comprising at least one compound according to the invention efficiently provide a rich sandalwood or woody note to the perfumed preparation / product. Preferably, the compound of general formula (I) or the perfume composition containing or comprising at least one compound according to the invention is used in an amount of 0.0001 to 90% by weight, preferably 0.01 to 70% by weight, particularly preferably 0.1 to 50% by weight, based on the total weight of the final (product) formulation.

[0090] Finally, the present invention relates to a perfumed product, wherein the perfumed product is preferably a perfume oil, a perfume base, a preparation for personal hygiene, a cleaning agent or an air freshener. EXAMPLES

[0091] The following compounds were prepared according to the methods indicated below. Spectroscopic structure determinations were carried out by known techniques.

[0092] As indicated above, all compounds disclosed herein, as well as all chemical formulae, should generally encompass both pure stereoisomers, particularly enantiomers, and mixtures of stereoisomers, particularly mixtures of enantiomers, and all intermediates obtained from the process can occur in various isomeric forms, and should therefore encompass both pure stereoisomers and mixtures of stereoisomers.

[0093] Example 1: Preparation of 1-oxacyclopentadec-6-en-3-one (A)

[0094] Step 1: Preparation of diethyl 4-dec-9-enoxy-3-oxobutanoate

[0095] To a mixture of 9-decen-1-ol (0.64 mol) in anhydrous THF and DMF under N2 at 20°C, NaH (1.28 mol) was added in portions. The mixture was stirred at 20°C for 1 h, then ethyl 4-chloroacetoacetoate (0.77 mol) was added dropwise at 20°C, and the mixture was stirred at 25°C overnight. The reaction mixture was quenched with H2O and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo at 45°C to give the crude product, which was purified by column chromatography to give 2-ethyl 4-dec-9-enoxy-3-oxo-butanoate. 1 H-NMR:(400MHz,CDCl3)δ1.19-1.23(m,11H),1.47-1.56(m,4H),1.94-1.99(m,2H),3. 40-3.45(m,4H),4.01(s,2H),4.09-4.15(m,2H),4.84-4.94(m,2H),5.70-5.77(m,1H).

[0096] Step 2: Preparation of ethyl 2-(2-dec-9-enoxyacetyl)pent-4-enoate

[0097] To 2-ethyl 4-dec-9-enoxy-3-oxo-butanoate (0.56 mol) in anhydrous EtOH was added EtONa (2.25 mol) in portions under N2 at 20°C. The mixture was stirred at 20°C for 1 h, then 3-bromoprop-1-ene (1.12 mol) was added dropwise and the mixture was stirred at 80°C overnight. The reaction mixture was quenched with H2O, concentrated to remove EtOH, and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo at 45°C to give the crude product, which was purified by column chromatography to give ethyl 2-(2-dec-9-enoxyacetyl)pent-4-enoate. 1H-NMR:(400MHz,CDCl3)δ1.23-1.36(m,13H),1.56-1.60(m,2H),2.02-2.05(m,2H),2.57-2.63(m,2H), 3.45(t,J=6.8Hz,2H),3.71(t,J=7.2Hz,1H),4.09-4.19(m,4H),4.90-5.11(m,4H),5.74-5.83(m,2H).

[0098] Step 3: Preparation of 1-dec-9-enoxyhex-5-en-2-one

[0099] To a mixture of ethyl 2-(2-dec-9-enoxyacetyl)pent-4-enoate (0.092 mol) in DMSO and H2O under N2 at 20°C, LiCl (0.18 mol) was added in one portion, then the mixture was stirred at 200°C overnight. The reaction mixture was quenched with H2O and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo at 45°C to give the crude product, which was purified by column chromatography to give 1-dec-9-enoxyhex-5-en-2-one. 1 H-NMR:(400MHz,CDCl3)δ1.24-1.36(m,10H),1.57-1.62(m,2H),2.00-2.03(m,2H),2.32-2.34( m,2H),2.54-2.58(m,2H),3.44-3.47(m,2H),4.00(s,2H),4.90-5.05(m,4H),5.76-5.83(m,2H).

[0100] Preparation of 1-oxacyclopentadec-6-en-3-one (A)

[0101] 1-Dece-9-enoxyhex-5-en-2-one (0.039 mol) and Hoveyda-Grubbs 2 in anhydrous DCM ndThe mixture was stirred under Ar at 45° C. overnight. The reaction mixture was concentrated in vacuo at 40° C. to give the crude product, which was purified by column chromatography followed by recrystallization and preparative HPLC to give 1-oxacyclopentadec-6-en-3-one (A). 1 H-NMR:(400MHz,CDCl3)δ1.25-1.34(m,8H),1.43-1.45(m,2H),1.53-1.57(m,2H),2.01-2.04(m,2H) ,2.34-2.36(m,2H),2.53-2.56(m,2H),3.55-3.58(t,J=5.6Hz,2H),4.02(s,2H),5.37-5.46(m,2H). Scent: Creamy, animalic and musky

[0102] Example 2: Preparation of 1-oxacyclohexadec-6-en-3-one (B)

[0103] Step 1: Preparation of ethyl 3-oxo-4-undec-10-enoxy-butanoate

[0104] To a mixture of compound 10-undecen-1-ol (0.58 mol) in anhydrous THF and DMF under N2 at 20°C, NaH (1.17 mol) was added in portions. The mixture was stirred at 20°C for 1 h, then ethyl 4-chloroacetoacetoate (0.70 mol) was added at 20°C, and the mixture was stirred at 25°C overnight. The reaction mixture was quenched with H2O and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuum at 45°C to give the crude product, which was purified by column chromatography to give ethyl 3-oxo-4-undec-10-enoxy-butanoate. 1 H-NMR:(400MHz,CDCl3)δ1.25-1.36(m,15H),1.56-1.60(m,2H),2.01-2.03(m,2H),3.45-3.4 8(m,2H),3.51(s,2H),4.07(s,2H),4.15-4.21(m,2H),4.90-4.99(m,2H),5.76-5.83(m,1H).

[0105] Step 2: Preparation of ethyl 2-(2-undec-10-enoxyacetyl)pent-4-enoate

[0106] To a mixture of ethyl 2-(2-undec-10-enoxyacetyl)pent-4-enoate (0.33 mol) in anhydrous EtOH under N2 at 20°C, EtONa (1.34 mol) was added in portions. The mixture was stirred at 20°C for 1 h, then 3-bromoprop-1-ene (0.67 mol) was added dropwise, and the mixture was stirred at 80°C overnight. The reaction mixture was quenched with H2O, concentrated to remove EtOH, and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo at 45°C to give the crude product, which was purified by column chromatography to give ethyl 2-(2-undec-10-enoxyacetyl)pent-4-enoate. 1 H-NMR:(400MHz,CDCl3)δ1.24-1.36(m,15H),1.57-1.60(m,2H),2.00-2.03(m,2H),2.57-2.63(m,2H ),3.43-3.46(m,2H),3.70(t,J=7.2Hz,1H),4.09-4.17(m,4H),4.90-5.10(m,4H),5.74-5.83(m,2H).

[0107] Step 3: Preparation of 1-undec-10-enoxyhex-5-en-2-one

[0108] To a mixture of ethyl 2-(2-undec-10-enoxyacetyl)pent-4-enoate (0.088 mol) in DMSO and H2O under N2 at 20°C, LiCl (0.18 mol) was added in one portion and the mixture was stirred at 200°C overnight. The reaction mixture was quenched with H2O and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo at 45°C to give the crude product, which was purified by column chromatography to give 1-undec-10-enoxyhex-5-en-2-one. 1 H-NMR:(400MHz,CDCl3)δ1.27-1.36(m,12H),1.56-1.62(m,2H),2.00-2.03(m,2H),2.33-2.36( m,2H),2.54-2.58(m,2H),3.44-3.47(m,2H),4.02(s,2H),4.90-5.05(m,4H),5.76-5.85(m,2H)

[0109] Preparation of (6)-1-oxacyclohexadec-6-en-3-one (B)

[0110] 1-Undec-10-enoxyhex-5-en-2-one (0.037 mol) and Hoveyda-Grubbs 2 in anhydrous DCM nd The mixture was stirred overnight under Ar at 45° C. The reaction mixture was concentrated in vacuo at 40° C. to give the crude product, which was purified by column chromatography followed by recrystallization, distillation and preparative HPLC to give (6)-1-oxacyclohexadec-6-en-3-one (B). 1 H-NMR:(400MHz,CDCl3)δ1.26-1.45(m,12H),1.64(m,2H),2.03(m,2H),2. 32(m,2H),2.62-2.64(m,2H),3.53(m,2H),3.98(s,2H),5.31-5.41(m,2H) Scent: Musk, animal scent

[0111] Example 3: Preparation of 6-methyl-1-oxacyclohexadec-6-en-3-one (C)

[0112] 6-Methyl 1-oxacyclohexadec-6-en-3-one (C) was prepared analogously to 1-oxacyclopentadec-6-en-3-one (B) using 3-bromo-2-methylpropene. 1H-NMR(400MHz,CDCl3)δ1.17-1.41(m,10H),1.41-1.52(m,2H),1.62(s,3H),1.64(t,J=6.4Hz,2H),2.03(q,J=6.8Hz ,2H),2.27(t,J=7.4Hz,2H),2.69(t,J=7.4Hz,2H),3.52(t,J=5.5Hz,2H),3.97(s,2H),5.15(tt,J=5.9,1.4Hz,1H). 13 C-NMR(101MHz,CDCl3)δ16.4,25.5,26.8,27.0,27.4,27.7,28.0,28.5,29.2,32.9,38.1,71.2,76.4,125.8,133.8,210.6. Smell: Strong musk, ergonic, powdery. Creamy.

[0113] Example 4: Preparation of 1,5-dioxacyclohexadec-14-en-3-one (D)

[0114] Preparation of 2-(dec-9-enoxymethyl)oxirane

[0115] A mixture of NaOH (0.96 mol) and 9-decen-1-ol (0.32 mol) was stirred for 4 h at 20° C. Then 2-(chloromethyl)oxirane (0.64 mol) was added and the mixture was stirred for 18 h at 40° C. The mixture was then evaporated to give the crude product, which was purified by chromatography to give 2-(dec-9-enoxy-methyl)oxirane. 1 H-NMR:(400MHz,CDCl3)δ1.22-1.30(m,11H),1.49-1.53(m,2H),1.96-1.98(m,2H),2.53-2.55(m,1H),2.72(t ,J=4.4Hz,1H),3.05-3.11(m,1H),3.32-3.43(m,3H),3.61-3.64(m,1H),4.85-4.94(m,2H),5.71-5.77(m,1H).

[0116] Step 2: Preparation of 1-allyloxy-3-dec-9-enoxy-propan-2-ol

[0117] To 2-propen-1-ol (350 mL) was added Na (0.85 mol) portionwise under N2. After the solution was stirred for 2 h, 2-(dec-9-enoxymethyl)oxirane (0.28 mol) was added to the mixture and the mixture was stirred at 20° C. for 2 h. The mixture was evaporated to give the crude product, which was purified by column chromatography to give 1-allyloxy-3-dec-9-enoxy-propan-2-ol. 1 H-NMR:(400MHz,CDCl3)δ1.18-1.32(m,12H),1.45-1.48(m,2H),1.94-1.99(m,2H),3.37- 3.44(m,6H),3.88-3.96(m,3H),4.84-4.94(m,2H),5.11-5.23(m,2H),5.73-5.87(m,2H).

[0118] Step 3: Preparation of 1-allyloxy-3-dec-9-enoxy-propan-2-one

[0119] To a solution of 1-allyloxy-3-dec-9-enoxy-propan-2-ol (0.26 mol) in DCM at 0° C. was added DMP (0.4 mol), and the mixture was stirred overnight at 20° C. The mixture was then washed with brine and 5% NaHCO3, dried over Na2SO4, and evaporated to give the crude product, which was purified by column chromatography to give 1-allyloxy-3-dec-9-enoxy-propan-2-one as a colorless oil. 1 H-NMR:(400MHz,CDCl3)δ1.18-1.30(m,12H),1.53-1.55(m,2H),1.94-1.99(m,2H),3.41(t,J=6.8Hz,2H), 3.99(d,J=5.6Hz,2H),4.13(s,2H),4.17(s,2H),4.84-4.94(m,2H),5.16-5.25(m,2H),5.70-5.84(m,2H).

[0120] Preparation of 1,5-dioxacyclohexadec-14-en-3-one (D)

[0121] 1-Allyloxy-3-dec-9-enoxy-propan-2-one (0.029 mol) in anhydrous DCM, Hoveyda-Grubbs 2 nd The mixture was stirred overnight under Ar at 45° C. The reaction mixture was concentrated in vacuo at 40° C. to give the crude product, which was purified by column chromatography followed by recrystallization and preparative HPLC to give 1,5-dioxacyclohexadec-14-en-3-one (D). 1 H-NMR:(400MHz,CDCl3)δ1.25-1.47(m,12H),2.04-2.07(m,2H),3.39-3.43(m,2H) ,3.94(s,2H),4.02-4.03(m,2H),4.35(s,2H),5.36-5.43(m,1H),5.54-5.60(m,1H)

[0122] Example 5: Preparation of 1,5-dioxacycloheptadec-15-en-3-one (E)

[0123] 1,5-Dioxacycloheptadec-15-en-3-one (E) was prepared analogously to 1,5-dioxacyclohexadec-14-en-3-one (D) by starting from 10-undecen-1-ol. 1 H-NMR:(400MHz,CDCl3)δ1.26-1.40(m,H),1.40-1.49(m,4H),1.55-1.64(m,2H),2.09-2.16(m,2H),3.49(dd,J=5.8,4.9Hz,2H) ,4.02(s,2H),4.10(dd,J=6.5,1.1Hz,2H),4.40(s,2H),5.48(dtt,J=15.6,6.5,1.4Hz,1H),5.65(dtt,J=15.1,6.9,1.3Hz,1H). 13C-NMR(101MHz,CDCl3)δ26.6,27.1,27.8,28.2,28.5,28.6,29.0,31.6,71.4,71.7,72.1,75.8,126.5,136.8,206.6. Smell: Powdery, musky

Claims

1. General formula (I): 【Chemistry 1】 or a stereoisomer, particularly an enantiomer, of During the ceremony, X represents methylene or ethylene optionally substituted by a methyl group; Y represents methylene or O; R1 represents H, a methyl group or an ethyl group; R2 represents H, a methyl group or an ethyl group; Z represents an optionally substituted C2, C3, C4, C5, C6, or C7 alkyl group; Optionally, there is a C═C double bond at at least one position of the dotted line.

2. the compound is a 14-membered ring and Z represents an optionally substituted C3 alkyl group; or the compound is a 15-membered ring and Z represents an optionally substituted C4 alkyl group; or the compound is a 16-membered ring and Z represents an optionally substituted C5 alkyl group; or the compound is a 17-membered ring and Z represents an optionally substituted C6 alkyl group; or The compound of claim 1, wherein the compound is an 18-membered ring and Z represents an optionally substituted C7 alkyl group.

3. In the above general formula (I), X represents methylene; Y represents methylene or O; R1 represents H or a methyl group; R2 represents H or a methyl group; 2. The compound of claim 1, wherein the compound has at least one C=C double bond at any of the positions of the dotted lines.

4. The compound of claim 3 , wherein the compound is a 15- or 16-membered ring.

5. The compound (a) pure optically active enantiomers; (b) a racemic mixture of said enantiomers; or (c) Optically active mixtures of the various enantiomers The compound according to any one of claims 1 to 4, which is present in the form

6. The compound of general formula (I) is the compound: 【Chemistry 2】 The compound according to any one of claims 1 to 5, selected from the group consisting of:

7. A fragrance composition comprising: (a) at least one compound according to any one of claims 1 to 6, and optionally (b) at least one additional fragrance material.

8. A process for preparing a compound of general formula (I) according to any one of claims 1 to 6, comprising the steps of: (1) General formula (II): 【Chemistry 3】 The olefin according to the formula n is 7 or 8; R represents H, methyl or ethyl; Y represents methylene or O; (2) performing olefin metathesis on the olefin prepared in step (1) to obtain a compound of general formula (I).

9. The olefin according to general formula (II) has general formula (III): 【Chemistry 4】 wherein n is 7 or 8, In a first step, the allyl alcohol is reacted with a halogenated acetate to give an ether; In a second step, the ether obtained in the first step is reacted with a substituted or unsubstituted allylic halide to produce an allylic ether compound; 9. The method according to claim 8, wherein in the third step, the allylated ether compound obtained from the second step is decarboxylated.

10. The olefin according to general formula (II) has general formula (III): 【Chemistry 5】 wherein n is 7 or 8, In a first step, the allyl alcohol is reacted with an oxirane; In a second step, a ring-opening reaction of the oxirane obtained in the first step is carried out with allyl alcohol to give a tertiary alcohol; 9. The method according to claim 8, wherein in a third step, the tertiary alcohol obtained from the second step is oxidized.

11. 1. A method for creating, enhancing or modifying a musk odor in a formulation, comprising: The following steps: Providing a compound according to any one of claims 1 to 6 or a fragrance composition according to claim 7; Providing a composition with other components; (a) to produce a musky odor in the resulting intimate mixture; or (b) to enhance the musk odor of the other components present in the composition; or (c) To modify the musk odor present in the composition of the other components. and mixing said composition of other components with a compound according to any one of claims 1 to 6 or a fragrance composition according to claim 7 in an amount sufficient to obtain said composition of other components.

12. Use of a compound according to any one of claims 1 to 6 or a fragrance composition according to claim 7 as an odorant.

13. Use of a compound according to any one of claims 1 to 6 or a perfume composition according to claim 7 for improving the fixation of perfume compounds or for preparing a perfumed product.

14. A perfumed product comprising an effective amount of a compound according to any one of claims 1 to 6, or a perfume composition according to claim 7, optionally together with a carrier or substrate.

15. 15. The perfumed product of claim 14, wherein the perfumed product is a perfume oil, a perfume base, a personal hygiene preparation, a cleaning product or a laundry product.

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