Seco-Ambroxan Acetal

Abstract

The present invention generally relates to compounds of formula (I) and compositions comprising one, two, three or more compounds of formula (I) or compositions consisting of two, three or more compounds of formula (I). The present invention further relates to methods for preparing compounds of formula (I) or compositions as defined herein, uses of compounds of formula (I) as defined herein as aromatic substances, uses of compositions as defined herein as aromatic mixtures, and uses of compounds of formula (I) or compositions as defined herein for imparting, modifying and / or enhancing one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic odors. In addition, the present invention relates to aromatic compositions and fragrance products as defined herein, methods for producing fragrance products, methods for scenting products, and methods for scenting hair, skin, textile fibers, surfaces and / or ambient air.

Description

Technical Field

[0001] The present invention generally relates to compounds of formula (I) and compositions comprising one, two, three or more compounds of formula (I) or compositions consisting of two, three or more compounds of formula (I). The present invention further relates to methods for preparing compounds of formula (I) or compositions as defined herein, uses of compounds of formula (I) as defined herein as aromatic substances, uses of compositions as defined herein as aromatic mixtures, and uses of compounds of formula (I) or compositions as defined herein for imparting, modifying and / or enhancing one or more olfactory characteristics selected from the group consisting of ambergris, woody fragrance and animalic odor. In addition, the present invention relates to aromatic compositions and fragrance products as defined herein, methods for preparing fragrance products, methods for scenting products, and methods for scenting hair, skin, textile fibers, surfaces and / or ambient air.

[0002] Further aspects and preferred embodiments of the present invention are described with reference to the following explanation, the accompanying examples and in particular the accompanying patent claims. Background Art

[0003] In the perfumery industry, a large number of different compounds are known for imparting pleasant odors. However, there is still a need for new advantageous compounds which, in addition to their primary positive olfactory properties, also possess other positive secondary properties.

[0004] When searching for suitable compounds, technicians face the daunting task of identifying the right aroma from a large pool of known compounds or producing new compounds with desired properties. It is impossible to predict whether a new compound will have an odor, and whether that odor will have desirable or undesirable olfactory properties. Even when a compound with a positive odor is discovered, it remains to be determined what specific type of odor it is and to what extent the compound may also possess positive secondary properties.

[0005] Many currently known fragrances have some significant disadvantages. For example, they often have very limited stability and yield, low adhesion, low emission, low solubility, and usually have to be used in high doses.

[0006] The requirements for new fragrances are also very high. For example, they should be very biodegradable and safe from the perspectives of skin and toxicology.

[0007] The "ambergris" character is a highly sought-after olfactory characteristic in perfume. It imparts a unique and luxurious quality to a fragrance. Originally extracted from the digestive tract of sperm whales, ambergris aromatic substances are now more commonly sourced from other sources. A drawback of many ambergris aromatic substances is that their olfactory impression develops gradually, making it particularly challenging to create an ambergris character in the top notes of a perfume.

[0008] The well-known ambergris fragrance substance ambroxide has the following structure

[0009]

[0010] Described as having a warm, slightly earthy, camphor-like, exotic, woody, and animalic character, it is often used as a fixative due to its high tenacity. Commonly known by the brand name Ambroxan, it is an auto-oxidation product of ambrein, a triterpene alcohol that is the main component of ambergris and is found in the digestive tract of sperm whales.

[0011] WO 2015 / 036402 A1 discloses a compound of the formula

[0012]

[0013] Wherein R is H, methyl, ethyl, O-methyl or O-ethyl, R1 is H, methyl, ethyl, O-methyl or O-ethyl, and n is 1 or 2. Such compounds have ambergris and / or woody olfactory characteristics.

[0014] WO 2016 / 083372 A1 relates to compounds of the formula

[0015]

[0016] Wherein R is methyl or ethyl, R1 is H, methyl, ethyl, O-methyl or O-ethyl, and X represents -CH2- or -CH2-CH2-, such compounds also have ambergris and / or woody olfactory characteristics.

[0017] WO 2018 / 233804 A1 mainly relates to the use of one or more compounds of the following formula as perfumes

[0018]

[0019] wherein R represents a methyl group or an ethyl group, and R1 represents H, a methyl group or an ethyl group, and is particularly used for imparting, modifying and / or enhancing one or more olfactory characteristics selected from the group consisting of ambergris, indole and woody notes. Summary of the Invention

[0020] The object of the present invention is to provide compounds which do not have or which alleviate the above-mentioned disadvantages of the prior art. In particular, the object of the present invention is to make available aromatic substances which are able to impart, modify and / or enhance the olfactory characteristics of ambergris and which also possess positive secondary properties, such as good biodegradability and / or high skin compatibility.

[0021] According to the present invention, the main specified objects are solved by compounds of formula (I)

[0022]

[0023] wherein X and Y are selected from the group consisting of -O- and -CH2-, respectively, and

[0024] The following applies: when X is -O-, then Y is -CH2-, and when X is -CH2-, then Y is -O-.

[0025] Therefore, the compound of formula (I) is a compound of formula (Ia) or formula (Ib), as shown below:

[0026]

[0027] The compounds of formula (I), formula (Ia) or formula (Ib) according to the present invention can be used in any stereoisomeric form. Within the scope of the present invention, any mixture of stereoisomers of the compounds of formula (I) or formula (Ia) or (Ib) can be used, for example a mixture of diastereomers, a mixture of enantiomers or a mixture of racemates. Therefore, for the purposes of this text, the term "compound of formula (I)" also includes the mixture of different stereoisomers of one or more compounds of formula (I). For the purposes of this text, the term "compound of formula (Ia)" includes the mixture of different stereoisomers of the compounds of formula (Ia), and for the purposes of this text, the term "compound of formula (Ib)" includes the mixture of different stereoisomers of the compounds of formula (Ib).

[0028] What is stated herein for compounds of formula (I) or formula (la) or formula (lb) applies correspondingly to mixtures of stereoisomers of one or more compounds of formula (I) or formula (la) or formula (lb), as well as to individual stereoisomers of one or more compounds of formula (I) or formula (la) or formula (lb).

[0029] Furthermore, what is stated herein for the compounds of formula (I) applies correspondingly to the compounds of formula (Ia) and (Ib) within the compounds of formula (I).

[0030] Surprisingly, the compounds according to the invention have an ambergris, woody and / or animalic odor.

[0031] Furthermore, they exhibit high stability and broad distribution, very good adhesion, very high emission, a low odor threshold, very good solubility and miscibility, a low tendency to react with other fragrances, very good skin and toxicological compatibility, and very good biodegradability.

[0032] Another advantage of the compounds of the present invention is their high odor intensity at relatively low doses. This is particularly important for environmental reasons, as the amount of substances released into the environment can be kept to a minimum. Furthermore, the amber or ambergris notes are quickly perceived, making these compounds suitable as top notes in, for example, fragrance oils.

[0033] The compounds of formula (I) are very stable and exhibit high stability also under adverse conditions such as high oxygen content, high oxidizing or reducing agent content, high temperature and extreme pH conditions.

[0034] Particularly preferred compounds of formula (I) and their odor descriptions are shown in Table 1 below:

[0035]

[0036]

[0037] Table 1

[0038] The compounds of formula (I) are characterized by having a particularly complex, diffuse and highly intensive amber or ambergris note at low doses. In addition, they also have a woody odor, thus creating a particularly desirable combination of amber or ambergris and woody notes.

[0039] The present invention also relates to compositions comprising or consisting of one, two, three or more compounds of formula (I).

[0040] Preferably, the present invention relates to compositions comprising one, two, three or more compounds of formula (Ia) and / or one, two, three or more compounds of formula (Ib).

[0041] More preferably, the present invention relates to a composition consisting of two, three or more compounds of formula (Ia) or two, three or more compounds of formula (Ib) or one, two, three or more compounds of formula (Ia) and one, two, three or more compounds of formula (Ib).

[0042] There are several possible routes to the synthesis of compounds of formula (I).

[0043] According to another aspect, the present invention therefore relates to a process for preparing a compound of formula (I) as defined herein or a composition as defined herein, comprising at least one, two, three or more of reaction steps (i) to (v) as shown below.

[0044] The starting materials of step (i) of the process according to the invention, tert-butylcyclohexanone and tert-butyl acrylate, can be synthesized or obtained commercially. They can be reacted with, for example, pyrrolidine, acetic acid and 4-methoxyphenol to obtain the product of step (i) of the process according to the invention.

[0045]

[0046] In step (ii), the ketone obtained in step (i) of the process according to the invention is reacted to give an olefin, for example by Wittig reaction with methyltriphenylphosphonium bromide (MePPh3Br) in diethyl ether.

[0047]

[0048] In step (iii) of the process according to the invention, the ester of the product of step (ii) is cleaved using, for example, alkaline potassium hydroxide in methanol.

[0049]

[0050] In step (iv) of the process according to the invention, the carboxylic acid of the product of step (iii) is reduced to the ketone with the aid of methyllithium in, for example, tetrahydrofuran.

[0051]

[0052] Finally, in step (v) of the process according to the invention, the compound of formula (I) (or formula (Ia)) is obtained by intramolecular cyclization. This can be achieved, for example, by dihydroxylation of the double bond of the ketone obtained in step (iv) followed by in situ cyclization to the compound of formula (I) (or formula (Ia)), or by epoxidation of the double bond of the ketone obtained in step (iv) followed by in situ cyclization to the compound of formula (I) (or formula (Ia)).

[0053]

[0054] Another aspect of the present invention relates to a process for preparing a compound of formula (I) as defined herein or a composition as defined herein, comprising at least one, two, three or more of reaction steps (i) to (vii) as shown below.

[0055] The starting materials of step (i) of the process according to the invention, tert-butylcyclohexanone and tert-butyl acrylate, can be synthesized or obtained commercially. They can be reacted with, for example, pyrrolidine, acetic acid and 4-methoxyphenol to obtain the product of step (i) of the process according to the invention.

[0056]

[0057] In step (ii), the ketone obtained in step (i) of the process according to the invention is reacted to give an olefin, for example by Wittig reaction with methyltriphenylphosphonium bromide (MePPh3Br) in diethyl ether.

[0058]

[0059] In step (iii) of the process according to the invention, the protected carboxylic acid of the product of step (ii) is reduced to an alcohol using, for example, lithium aluminum hydride in tetrahydrofuran.

[0060]

[0061] In step (iv) of the process according to the invention, the alcohol obtained in step (iii) is converted into an aldehyde using, for example, a Dess-Martin periodinane in dichloromethane.

[0062]

[0063] In step (v) of the process according to the invention, the aldehyde obtained in step (iv) is converted into an alcohol using, for example, methyllithium in tetrahydrofuran.

[0064]

[0065] In step (vi) of the process according to the invention, the alcohol obtained in step (v) is converted into a ketone, for example using a Dess-Martin periodinane in dichloromethane.

[0066]

[0067] Finally, in step (vii) of the process according to the invention, the compound of formula (I) (or formula (Ia)) is obtained by intramolecular cyclization. This can be achieved, for example, by dihydroxylation of the double bond of the ketone obtained in step (vi) followed by in situ cyclization to the compound of formula (I) (or formula (Ia)), or by epoxidation of the double bond of the ketone obtained in step (vi) followed by in situ cyclization to the compound of formula (I) (or formula (Ia)).

[0068]

[0069] Another aspect of the present invention relates to a process for preparing a compound of formula (I) as defined herein or a composition as defined herein, comprising at least one, two, three or more of reaction steps (i) to (iv) as shown below.

[0070] The starting material of step (i) of the process according to the present invention, 3-methyl-3-buten-1-ol, can be synthesized or obtained commercially.

[0071] In step (i) of the process according to the invention, the alcohol group is protected by a tosyl (Ts) protecting group, for example by reaction with p-toluenesulfonyl chloride in pyridine.

[0072]

[0073] In step (ii) of the process according to the invention, the product of step (i) is converted into the iodide, for example by reaction with sodium iodide in acetone.

[0074]

[0075] In step (iii) of the process according to the invention, the product of step (ii) is reacted with tert-butyl hexanone.

[0076]

[0077] Finally, in step (iv) of the process according to the invention, the compound of formula (I) (or formula (Ib)) is obtained by intramolecular cyclization. This can be achieved, for example, by dissolving the product of step (iii) in ethyl acetate and acetonitrile and dihydroxylating it with an aqueous solution of ruthenium(III) chloride hydrate and sodium periodate.

[0078]

[0079] Another aspect of the present invention relates to the use of a compound of formula (I) (or formula (la) or formula (lb)) as defined herein as a fragrance substance.

[0080] A further aspect of the present invention relates to the use of a composition as defined herein as a fragrance mixture.

[0081] Preferably, the use of one or more compounds of formula (I) or compositions as defined herein for imparting, modifying and / or enhancing one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic notes, preferably for imparting, modifying and / or enhancing the olfactory characteristics of ambergris.

[0082] Another aspect of the present invention relates to a fragrance composition comprising or consisting of:

[0083] (i) a compound of formula (I) as defined herein, or

[0084] (ii) a composition as defined herein,

[0085] and one or more additional aromatic substances.

[0086] Within the framework of the present text, additional aroma substances are aroma substances other than the compounds of formula (I).

[0087] Examples of additional aromatic substances that can be advantageously combined with the compounds of formula (I) (or formula (la) or formula (lb)) as defined herein within the scope of the present invention are described, for example, in S. Arctander, Flavor and Fragrance Materials, Volumes I and II, Montclair, NJ 1969, Eigenverlag, or K. Bauer et al., Common Flavor and Fragrance Materials, 4th edition, Wiley-VCH, Weinheim 2001.

[0088] Detailed description: Extracts of natural raw materials such as essential oils, concentrates (concretes), absolutes (absolue), resins, resinoids (resinoids), balsams (balsams), tinctures such as

[0089] Ambergris tincture; tallow sandalwood oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; moss absolute; bay oil; wormwood oil; benzoin resin; bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; buchu oil; Brazilian sandalwood oil; juniper oil; calamus oil; camphor oil; cananga oil; cardamom oil; quinoa oil; cinnamon oil; cinnamon absolute; castoreum absolute; cedar leaf oil; cedarwood oil; labdanum oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill oil; dill seed oil; eau de brouts absolute absolue; oakmoss absolute; elemi resin oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; anise oil; spruce needle oil; gabion oil; gabion resin; geranium oil; grapefruit oil; guaiac wood oil; guar balsam; guar balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; blue chamomile oil; Roman chamomile oil; carrot seed oil; quinoa oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavender absolute; lavender oil; lavender absolute; lavender oil; lemongrass oil; round-leaf angelica oil; distilled lime oil; pressed lime oil; agarwood oil; litsea cubeba oil; bay leaf oil; nutmeg oil oil; oregano oil; mandarin oil; cassia bark oil; mimosa absolute; ambrette oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; frankincense absolute; frankincense oil; myrrh oil; neroli absolute; orange oil; oregano oil; palmarosa essential oil; patchouli oil; perilla seed oil; Peru balsam oil; parsley leaf oil; parsley seed oil; orange leaf oil; peppermint oil; pepper oil; allspice oil; pine oil; peppermint oil oil); rose absolute; rosewood oil; rose oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; anise oil; styrax oil; marigold oil; fir oil; tea tree oil; turpentine; thyme oil; tolu balsam; tonka absolue; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper oil; wine yeast oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; musk absolute; cinnamon leaf oil; cinnamon bark oil, and fractions thereof, or fractions isolated therefrom.

[0090] Furthermore, the additional aroma substances may be aroma substances from the following groups:

[0091] Hydrocarbons, such as 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0092] Aliphatic alcohols, such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexanol; 1-octen-3-ol; a mixture of 3,4,5,6,6-pentamethyl-3 / 4-heptan-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; 4-methyl-3-decen-5-ol;

[0093] Aliphatic aldehydes and their acetals, such as hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecanal; (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; citronellyl acetaldehyde ether; 1-(1-methoxy-propyloxy)-(E / Z)-3-hexene;

[0094] Aliphatic ketones and their oximes, such as 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; 6-methyl-5-hepten-2-one;

[0095] Aliphatic sulfur-containing compounds, such as 3-methylthiohexanol; 3-methylthiohexanol acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;

[0096] Aliphatic nitriles, such as 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0097] Esters of aliphatic carboxylic acids, such as (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl 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-ol acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; isobutyric acid (E)- and (Z)-3-hexenyl esters; hexyl crotonate; ethyl isovalerate; ethyl 2-methylvalerate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynoate; methyl 2-nonynoate; allyl 2-isopentyloxyacetate; ethyl methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl-crotonate;

[0098] Acyclic terpene alcohols, such as geraniol; nerol; 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-octadien-2-ol; 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 formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acids and 3-methyl-2-butenoates;

[0099] Acyclic terpene aldehydes and ketones, such as citronellal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial and neral;

[0100] Cyclic terpene alcohols, such as menthol; isopulegol; α-terpineol; terpineol-4; menth-8-ol; menth-1-ol; menth-7-ol; camphenol; isocamphenol; linalool oxide; nopol; cedrol; ambroxanol; vetivol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoates;

[0101] Cyclic terpene aldehydes and ketones, such as menthone; isomenthone; 8-mercaptomenth-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; β-damascenone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-butene-1- -ketone; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methyl-bridged naphthalen-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; naringenone; dihydronaringenone; 4,6,8-megatrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedar oil (methyl cedar ketone);

[0102] Cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0103] Cycloaliphatic alcohols such as 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; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl) -pentan-2-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;

[0104] Cyclic and cycloaliphatic ethers, such as eucalyptol; methyl cedar ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-epoxycedar; 3a,6,6,9a-tetramethyl-dodecahydronaphthalene[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphthalene[2,1b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]tridec-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0105] Cyclic ketones and macrocyclic ketones, such as 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-cyclopentadecenone; 3-methylcyclopentadecenone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1,1,2,3,3-pentylmethyl-4(5H)-indanone; 8-cyclohexadecen-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0106] Alicyclic aldehydes, such as 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0107] Cycloaliphatic ketones, such as 1-(3,3-dimethylcyclohexyl)-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-naphthylmethyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

[0108] Cyclic alcohol esters, such as 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-2- Naphthyl acetate; 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-methano-octahydro-5- or 6-indenyl acetate;

[0109] Esters of cycloaliphatic alcohols, such as ethyl 1-cyclohexylcrotonate;

[0110] Esters of cycloaliphatic carboxylic acids, such as allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl cis- and trans-dihydrojasmonate; methyl cis- and trans-jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate;

[0111] Aromatic aliphatic alcohols, such as benzyl alcohol; 1-phenylethanol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 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; 1-(4-isopropylphenyl)ethanol;

[0112] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, such as 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-dimethylphenethyl acetate; α,α-dimethylphenethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0113] Aromatic aliphatic ethers, such as 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl-1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated atropine dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

[0114] Aromatic and aromatic aliphatic aldehydes, such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroataldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyde; α-hexylcinnamaldehyde; 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; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0115] Aromatic and araliphatic ketones, such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanmethylketone; 6-tert-butyl-1,1-dimethyl-4-indanmethylketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indanyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthylacetonone;

[0116] Aromatic and araliphatic carboxylic acids and esters thereof, such as benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidyl propionate; ethyl 3-methyl-3-phenylglycidyl propionate;

[0117] 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-pentenenitrile; 3-methyl-5-phenyl-valeronitrile; 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-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; methylindole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0118] Phenol, phenyl ethers and phenyl esters, such as estragole; anethole; eugenol methyl ether; isoeugenol; isoeugenol 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;

[0119] Heterocyclic compounds such as 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;

[0120] Lactones, such as 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecanolactone; 1,4-dodecanolactone; 1,5-decanolactone; 1,5-dodecanolactone; 4-methyl-1,4-decanolactone; 1,15-pentadecanolactone; 1,16-hexadecanolactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecanolactone; 11-oxa-1,16-hexadecanolactone; 12-oxa-1,16-hexadecanolactone; vinyl 1,12-dodecanoate; vinyl 1,13-tridecanoate; 2,3-dihydrocoumarin; octahydrocoumarin.

[0121] According to a preferred embodiment of the fragrance composition according to the present invention, one or more compounds of formula (I) (or formula (Ia) and / or (Ib)) according to the present invention are combined with one or more, particularly preferably with two, three, four, five or more additional fragrance substances.

[0122] The fragrance composition according to the invention containing one or more compounds of formula (I) (or formula (Ia) or formula (Ib)) may be in liquid form, undiluted or diluted with a solvent. Preferred solvents are ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, triacetic acid and diacetic acid.

[0123] Furthermore, the aromatic composition according to the invention can be adsorbed onto a carrier, thereby ensuring a fine distribution of the aromatic substance in the product and a controlled release upon application. Such carriers can be porous inorganic materials such as hydroxysulfates, silica gels, zeolites, gypsum, clays, clay particles, aerated concrete, etc., or organic materials such as wood, cellulose-based materials, sugars, dextrins (e.g., maltodextrin), or plastics such as PVC, polyvinyl acetate, or polyurethane. The combination of an aromatic composition according to the invention and a carrier can also be understood as an aromatic substance according to the invention or can be present as a product according to the invention (as described below).

[0124] The fragrance substance compositions or products according to the invention (as described below) can also be present in microencapsulated form, spray-dried form, as inclusion complexes or as extruded products and, in the case of fragrance substance compositions, can be added in this form to the product to be perfumed (as described below).

[0125] With a view to further optimizing the more targeted fragrance release, such modified compositions or products can, if applicable, be so-called "coated" with a suitable material, preferably a waxy plastic such as polyvinyl alcohol. The resulting product is in turn a product according to the invention.

[0126] Microencapsulation can be achieved, for example, by a so-called coacervation process using capsule materials such as polyurethanes or soft gelatin.

[0127] The spray-dried product is preferably prepared by spray drying an emulsion or dispersion containing the aroma composition, wherein modified starches, proteins, dextrins and vegetable-based gums may be used as carriers.

[0128] Inclusion complexes can be prepared, for example, by incorporating a dispersion of the fragrance composition and the cyclodextrin or urea derivative into a suitable solvent, such as water.

[0129] Extruded products can be obtained by melting and extruding the fragrance composition with a suitable waxy substance and subsequently solidifying, if applicable, in a suitable solvent such as isopropanol.

[0130] Another aspect of the present invention relates to a fragrance product comprising a compound of formula (I) as defined herein or a composition as defined herein or a fragrance substance composition as defined herein.

[0131] Preferably, the fragrance product according to the invention is selected from the group consisting of detergents and cleaning agents, hygiene or care products, preferably for the body and hair care, cosmetics and household sectors, preferably from the group consisting of perfume extracts, eau de parfums, eau de toilette, aftershave, cologne, pre-shave products, splash cologne, fragrant refreshing wipes, acidic, alkaline or neutral detergents, textile refreshers, ironing aids, liquid detergents, powder detergents, laundry pretreatments, fabric softeners, washing soaps, washing bars, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, body care products, hand creams and hand lotions, foot creams and foot lotions, depilatory creams and depilatory lotions, aftershave creams and aftershave lotions, tanning creams and tanning lotions, hair care products, deodorants, antiperspirants, decorative cosmetic products, candles, lamp oil, incense sticks, insecticides, insect repellents and fuel.

[0132] Preferably, in the fragrance product according to the present invention, one or more compounds of formula (I) are contained in a sensory effective amount, preferably an amount sufficient for the consumer to detect one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animal notes, preferably an amount for the consumer to detect the olfactory characteristics of ambergris.

[0133] More preferably, in the fragrance product according to the invention as defined herein, the total amount of one or more compounds of formula (I) is in the range of 0.00001 wt.-% to 10 wt.-%, preferably 0.0001 wt.-% to 5 wt.-%, more preferably 0.001 wt.-% to 2 wt.-%, more preferably 0.005 wt.-% to 1 wt.-%, based on the total weight of the product.

[0134] Another aspect of the present invention relates to a process for preparing a fragrance product, preferably a fragrance product as defined herein, comprising or consisting of the following steps:

[0135] (i) providing a compound of formula (I) as defined herein or a composition as defined herein or a fragrance composition as defined herein,

[0136] (ii) providing one or more other components of the fragrance product to be produced, and

[0137] (iii) contacting or mixing the other components provided in step (ii) with the organoleptically effective amount of the components provided in step (i).

[0138] Another aspect of the present invention relates to a method for flavoring a product, the method comprising or consisting of the following steps:

[0139] (a) Provide

[0140] (i) a compound of formula (I) as defined herein, or

[0141] (ii) a composition as defined herein, or

[0142] (iii) a fragrance composition as defined herein, and

[0143] (b) adding (i) a compound of formula (I) as defined herein, or (ii) a composition as defined herein, or (iii) a fragrance substance composition as defined herein to the product to be perfumed in a sensory effective amount, preferably an amount sufficient to impart, modify and / or enhance one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic notes, preferably the olfactory characteristics of ambergris.

[0144] Thus, in step (b) of said process for perfumery of a product, (i) a compound of formula (I) as defined herein, or (ii) a composition as defined herein, or (iii) a composition of aromatic substances as defined herein is added in an amount sufficient for the consumer of the product to detect one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic notes, preferably an amount for the consumer to detect the olfactory characteristics of ambergris.

[0145] Another aspect of the present invention relates to a method for scenting hair, skin, textile fibers, surfaces and / or ambient air, said method comprising or consisting of the following steps:

[0146] (a) Provide

[0147] (i) a compound of formula (I) as defined herein, preferably also a surfactant or a mixture of surfactants, or

[0148] (ii) a composition as defined herein, preferably comprising a surfactant or a mixture of surfactants, or

[0149] (iii) a fragrance composition as defined herein, preferably comprising a surfactant or a mixture of surfactants, or

[0150] (iv) a fragrance product as defined herein, preferably comprising a surfactant or a mixture of surfactants, and

[0151] (b) applying or introducing the (i) compound, preferably also a surfactant or a mixture of surfactants, or (ii) the composition, or (iii) the fragrance composition, or (iv) the perfume product of step (a) to the hair or skin or fibers or surfaces to be perfumed, or to the ambient air to be perfumed, in an organoleptically effective amount, preferably an amount sufficient for the consumer to detect one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic notes, preferably an amount for the consumer to detect the olfactory characteristics of ambergris.

[0152] For the preferred embodiments of the compounds of formula (I) (or compounds of formula (Ia) or (Ib)) described herein, what has been said in connection with the (fragrance) compositions, fragrance products, methods and uses according to the invention applies correspondingly, and vice versa.

[0153] Hereinafter, the present invention will be explained in more detail with reference to examples. DETAILED DESCRIPTION

[0154] Example:

[0155] 1. Synthesis route 1 of compound of formula (Ia)

[0156] 1.1 Synthesis of tert-butyl 3-((1'R,5'R)-5'-(tert-butyl)-2'-oxocyclohexyl) propionate

[0157]

[0158] Tert-butyl cyclohexanone (3.13 g, 20.07 mmol, 1.33 equivalents) was heated to 50° C. Pyrrolidine (0.25 mL, 3.01 mmol, 0.2 equivalents), CH COOH (17 μL, 0.30 mmol, 0.03 equivalents) and 4-methoxyphenol (20 mg, 0.20 mmol, 0.02 equivalents) were added. The solution was heated to 70° C. and tert-butyl acrylate (1.5 mL, 10.04 mmol, 0.67 equivalents) was added dropwise. The mixture was stirred at 125° C. for 24 hours. Since tert-butyl acrylate had already reacted (GC control), additional tert-butyl acrylate (0.75 mL, 5.02 mmol, 0.33 equivalents) was added dropwise. The reaction mixture was stirred for another 16 hours and then cooled to room temperature. 10% NH Cl solution (20 mL) was added and phase separated. The aqueous phase was extracted with methyl-tert-butyl ether (MTBE, 2 x 30 mL) and the combined organic phases were washed with water (50 mL). The extract was dried over Na SO , filtered, and volatile components were removed under reduced pressure. The crude product was purified by Kugelrohr distillation (T = 110° C., p = 0.64 mbar to T = 170° C., p = 0.59 mbar). The product obtained was a colorless liquid (2.67 g, 9.44 mmol, 63% as a 4:1 isomer mixture (cis / trans)).

[0159] TLC:R f =0.24 (ethyl acetate / cyclohexane, 5:95)

[0160] Boiling point (bp): T b =120℃-122℃(p=98mbar)

[0161] 1 H-NMR (400MHz, CDCl3)δ=2.43–2.20(m,5H,C(=O)CH2,(CH3)3COC(=O)CH2,C(=O)CH),2.16–2.06(m,2H,2x C q CHC(H)H'),2.06–1.98(m,1H,CHC(H)H'CH2),1.62–1.54(m,1H,C q CH),1.46–1.42(m,2H,C q CHC(H)H',CHC(H)H'CH2),1.44(s,9H,C(=O)OC(CH3)3),1.16(q,J=12.7Hz,1H,C q CHC(H)H'),0.91(s,9H,C(CH3)3)

[0162] 13C-NMR(101MHz, CDCl3)δ=212.94(C=O),173.07(C(=O)OR),80.08(C q (CH3)3O),48.86(C(=O)CH),47.15(C q CH), 41.71(C(=O)CH2), 35.22(C q CHCH2),33.12(ROC(=O)CH2),32.46(C(CH3)3),28.79(C q CHCH2),28.14(OC(CH3)3),27.66(C(CH3)3),24.89(CHCH2CH2)

[0163] IR (GC / FT-IR): 2878(w),1732(s),1372(m),1250(w),1158(s)cm -1

[0164] HRMS (ESI-TOF): calculated for C17H30O3 [M+Na] + 305.2093; true value 305.2087

[0165] 1.2 Synthesis of tert-butyl 3-((1'R,5'R)-5'-(tert-butyl)-2'-methylenecyclohexyl) propionate

[0166]

[0167] When carrying out the Wittig reaction, MePPh Br (39.4 g, 110 mmol, 1.3 equivalents) was dissolved in 200 mL of Et O. KOtBu (14.3 g, 127 mmol, 1.5 equivalents) was added and the suspension was stirred at 38° C. under reflux for 1 hour. The mixture was then cooled and added dropwise to the reaction product (25.0 g, 84.9 mmol) described in item 1.1 above in 250 mL of Et O. After stopping the addition, the mixture was heated to 38° C. again and stirred at this temperature for 6 hours. The reaction was cooled to room temperature and H O (150 mL) and pentane (150 mL) were added. After filtering and phase separation, the aqueous phase was extracted with Et O (3 x 100 mL). The combined organic phases were washed with H O (300 mL) and dried with Na SO. After filtering, the volatile components were removed under reduced pressure. The accumulated solid was filtered off and washed with pentane (300 mL). The volatile components of the filtrate were removed under reduced pressure. The crude product was purified by Kugelrohr distillation (T = 90 ° C, p = 0.69 mbar to T = 137 ° C, p = 0.67 mbar) to obtain a colorless liquid (20.2 g, 71.5 mmol, 81%, 96:4 isomer mixture (cis / trans)).

[0168] TLC:R f =0.27 (ethyl acetate / cyclohexane, 2.5:97.5)

[0169] 1 H-NMR (400MHz, CDCl3) δ = 4.69 (d, J = 1.1Hz, 1H, C = C(H)H'), 4.57 (d, J = 1.1Hz, 1H, C = C(H)H'), 2.36 (dt, J = 12.8,3.7Hz,1H,C(=CH2)C(H)H'),2.33–2.27(m,2H,ROC(=O)CH2),2.02–1.82(m,5H,C(=CH2)C(H)H',2x C q CHC(H)H',C(=CH2)CH,CHC(H)H'CH2),1.64–1.54(m,1H,CHC(H)H'CH2),1.45(s,9H,C(=O)OC(CH3)3),1.23(tt,J=12.2,3.1Hz,1H,C q CH),1.12–0.98(m,1H,C q CHC(H)H'),0.85(s,9H,C(CH3)3),0.73(q,J=11.6Hz,1H,C q CHC(H)H')

[0170] 13C-NMR (101MHz, CDCl3)δ=173.44(C(=O)OR),152.60(C=CH2),103.97(C=CH2),79.98(C q (CH3)3O),48.13(C q CH),42.01(C(=O)CH),37.03(C(=O)CH2),35.33(C q CHCH2),33.51(ROC(=O)CH2),32.45(C(CH3)3),29.62(C q CHCH2),28.15(OC(CH3)3),27.77(CHCH2CH2),27.65(C(CH3)3

[0171] IR (GC / FT-IR): 2950(s),2875(m),1744(s),1371(m),1250(m),1153(s)cm -1

[0172] HRMS (ESI-TOF): calculated value C 18 H 32 O2[M+H] + 281.2481; true value 281.2473

[0173] 1.3 Synthesis of 3-((1'R,5'R)-5'-(tert-butyl)-2'-methylenecyclohexyl)-propionic acid

[0174]

[0175] The reaction product described in item 1.2 above (4.02g, 14.2mmol) was dissolved in KOH (5% in MeOH, 20mL) and stirred at room temperature for 2 days. 10% NH4Cl solution (60mL) was added and the product was extracted with Et2O (3x 40mL). The combined organic phase was washed with water (100mL), dried with Na2SO4, filtered, and volatile components were removed under reduced pressure. The product obtained was a colorless liquid (3.15g, 14.0mmol, 99% as a 96:4 isomer mixture (cis / trans)) and could be proceeded to the next step without further purification.

[0176] TLC:R f =0.36 (ethyl acetate / cyclohexane, 10:90)

[0177] 11H-NMR (600 MHz, CDCl3) δ = 4.71 (d, J = 1.5 Hz, 1H, C=C(H)H'), 4.56 (d, J = 1.4 Hz, 1H, C=C(H)H'), 2.47–2.44 (m, 1H, C(H)H'COOH), 2.36 (ddd, J = 13.0, 4.0, 2.8 Hz, 1H, CH2=CCH(H)H'), 2.05–1.94 (m, 2H, CH2=CCH(H)H', CHC(H)H’CH2), 1.92–1.85 (m, 3H, 2x C q CHC(H)H', CH2=CCH), 1.67–1.59 (m, 1H, CHC(H)H’CH2), 1.25 (tt, J = 12.1, 3.2 Hz, 1H, C q CH), 1.06 (qd, J = 12.5, 4.1 Hz, 1H, C q CHC(H)H'), 0.85 (s, 9H, C q (CH3)3), 0.76 (q, J = 12.7 Hz, 1H, C q CHC(H)H')

[0178] 13 13C-NMR (151 MHz, CDCl3) δ = 179.77 (COOH), 152.33 (C=CH2), 104.07 (C=CH2), 48.05 (C q CH), 41.94 (CH2=CCH), 37.00 (CH2=CCH2), 35.48 (C q CHCH2), 32.46 (C(CH3)3), 31.96 (CH2COOH), 29.63 (C q CHCH2), 27.64 (C(CH3)3), 27.48 (CHCH2CH2)

[0179] IR (GC / FT-IR): 3089 (w), 2953 (s), 2874 (m), 1777 (s), 1371 (m), 1123 (s), 894 (w) cm -1

[0180] MS (EI): m / z = 224 [M] + , 167 [M-(CH3)3C] + , 57 [(CH3)3C] +

[0181] HRMS (ESI-TOF): Calculated for C 14 H 24O2[M+H] + 225.1855; true value 225.1849

[0182] 1.4 Synthesis of 4-((1'S,5'S)-5'-(tert-butyl)-2'-methylenecyclohexyl)butan-2-one

[0183]

[0184] The reaction product (7.00g, 28.5mmol) described in item 1.3 above was dissolved in 60mL THF and cooled to -78°C. MeLi (to a 1.6M solution of 39.1mL in Et2O, 62.6mmol, 2.2 equivalents) was added dropwise and the solution was stirred at -78°C for 5 hours. The solution was then heated to room temperature and water (40mL) was added. Phase separation was carried out and the aqueous phase was extracted with Et2O (3x 50mL). The organic phases were combined and washed with 5% NaCl solution (100mL). The extract was dried, filtered, and volatile components were removed under reduced pressure. The crude product was purified by column chromatography (250mL SiO2, 4% to 5% EtOAc, in cyclohexane). The product obtained was a colorless liquid (4.53g, 20.4mmol, 72%, 96:4 isomer mixture (cis / trans)).

[0185] TLC:R f =0.40 (ethyl acetate / cyclohexane, 5:95)

[0186] 1 H-NMR (400MHz, CDCl3) δ = 4.69 (q, J = 1.5Hz, 1H, C(H)H'), 4.54 (q, J = 1.4Hz, 1H, C(H)H'), 2.52 (t, J = 7.6Hz, 2H, O = C CH2),2.36(ddd,J=12.8,3.9,2.6Hz,1H,CH2=CC(H)H'),2.15(s,3H,O=CCH3),2.02–1.78(m,5H,CH2=CC(H)H',2x C q CHC(H)H',CH2=CCH,CHC(H)H'),1.64–1.50(m,1H,CHC(H)H'),1.24(tt,J=12.1,3.1Hz,1H,C q CH),1.05(qd,J=12.6,4.0Hz,1H,C q CHC(H)H'),0.85(s,9H,3x CH3),0.75(q,J=11.7Hz,1H,C q CHC(H)H')

[0187] 13 C-NMR (101MHz, CDCl3) δ = 209.27 (C = O), 152.63 (C = CH2), 103.98 (C = CH2), 48.11 (C q CH),42.09(CH2=CCH),41.75(O=CCH2),37.03(CH2=CCH2),35.73(C q CHCH2),32.45(C q ),29.98(O=CCH3),29.66(C q CHCH2),27.64(C q (CH3)3), 26.41(CH2=CCHCH2)

[0188] IR (GC / FT-IR): 2952(s),2874(w),1732(m),1368(m),893(w)cm -1

[0189] MS (EI): m / z = 222 [M] + ,165[M-(CH3)3C] + ,57[(CH3)3C] +

[0190] HRMS (ESI-TOF): calculated value C 15 H 26 O[M+H] + 223.2062; true value 223.2058

[0191] 1.5 Synthesis of 4-((3'R,4'R,6'R)-6'-(tert-butyl)-1-oxaspiro[2.5]octan-4'-yl)butan-2-one (epoxide (a)) and 4-((3'S,4'R,6'R)-6'-(tert-butyl)-1-oxaspiro[2.5]octan-4'-yl)butan-2-one (epoxide (b))

[0192]

[0193] The reaction product described in item 1.4 above (1.90 g, 8.46 mmol) was dissolved in 20 mL of CH2Cl2 and cooled to 0°C. At this temperature, mCPBA (meta-chloroperbenzoic acid, 2.63 g, 15.2 mmol, 1.8 equivalents) was added and the reaction mixture was stirred at room temperature for 4 hours. Water (10 mL) was added and the phases were separated. Subsequently, the mixture was extracted with EtOAc (2 x 10 mL), and the combined organic phases were washed with 5% Na2CO3 solution (10 mL) and saturated NaCl solution (2 x 10 mL). The extract was dried over Na2SO4, filtered, and volatile components were removed under reduced pressure. The crude product was purified by column chromatography (300 mL of SiO2, 10% EtOAc in cyclohexane). In this method, epoxides (a) (559 mg, 2.34 mmol, 26%) and (b) (1.19 g, 5.01 mmol, 59%) were each separated as a colorless liquid. The ratio of the two isomers is 3:7.

[0194] Epoxide (a):

[0195] TLC:R f =0.19 (ethyl acetate / cyclohexane, 10:90)

[0196] 1 H-NMR (400MHz, CDCl3) δ = 2.76 (dd, J = 4.5, 1.9Hz, 1H, CC (H) H'O), 2.54–2.36 (m, 2 H,CC(H)H'O,CH2C=O),2.13(s,3H,(C=O)CH3),1.98–1.81(m,3H,C(O)C(H)H',2x C q CHC(H)H'),1.67(ddt,J=12.1,8.3,4.2Hz,1H,C(O)CH),1.59–1.51(m,1H,CHC(H)H'CH2),1.37–1.29(m,1H,C(O)C(H)H'),1.23–1.06(m,3H,C q CH,C q CHC(H)H',CHC(H)H'CH2),0.88(s,9H,C(CH3)3),0.91–0.82(m,1H,C q CHC(H)H')

[0197] 13 C-NMR (101MHz, CDCl3) δ = 209.06 (C = O), 62.07 (C (O) CH2), 49.59 (CCH2O), 47.52 (C qCH),42.16(CH2C=O),39.95(C(O)CH),35.50(C(O)CH2),33.35(C q CHCH2),32.42(C(CH3)3),29.90((C=O)CH3),27.66(C(CH3)3),26.67(C q CHCH2),23.50(CHCH2CH2)

[0198] MS (EI): m / z = 238 [M] + ,181[M-(CH3)3C] + ,57[(CH3)3C] + ,43[CH3C(=O)] +

[0199] HRMS (ESI-TOF): calculated value C 15 H 26 O2[M+H] + 239.2011; true value 239.2000

[0200] Epoxide (b):

[0201] TLC:R f =0.16 (ethyl acetate / cyclohexane, 10:90)

[0202] 1 H-NMR (400MHz, CDCl3)δ=2.94(d,J=4.2Hz,1H,CC(H)H'O),2.54–2.43(m,1H,C(H)H'C=O),2.49(d,J=4.2Hz,1H,CC(H)H'O),2.36 (ddd,J=17.0,9.0,6.4Hz,1H,C(H)H'C=O),2.13(s,3H,(C=O)CH3),1.89–1.82(m,1H,C(O)C(H)H'),1.81–1.69(m,3H,C(O)CH,2xC q CHC(H)H'),1.52(dddd,J=13.8,9.0,6.4,4.5Hz,1H,CHC(H)H'CH2),1.40–1.22(m,3H,C(O)C(H)H',C q CHC(H)H',CHC(H)H'CH2),1.15(tt,J=11.7,2.9Hz,1H,C q CH),1.04(ddd,J=13.1,10.6Hz,1H,C qCHC(H)H'),0.88(s,9H,C(CH3)3)

[0203] 13 C-NMR (101MHz, CDCl3) δ = 208.91 (C = O), 60.29 (C (O) CH2), 51.08 (CCH2O), 47.79 (C q CH),41.20(CH2C=O),38.12(C(O)CH),35.17(C(O)CH2),32.59(C(CH3)3),30.72(C q CHCH2),29.97((C=O)CH3),27.60(C(CH3)3),24.75(C q CHCH2),22.72(CHCH2CH2)

[0204] IR (GC / FT-IR): 2957(s),2878(w),1732(m),1368(w)cm -1

[0205] MS (EI): m / z = 238 [M] + ,181[M-(CH3)3C] + ,57[(CH3)3C] + ,43[CH3C(=O)] +

[0206] HRMS (ESI-TOF): calculated value C 15 H 26 O2[M+H] + 239.2011; true value 239.2002

[0207] 1.6 Synthesis of Compounds 1 and 2

[0208]

[0209] The epoxide (b) (152mg, 608μmol) obtained in the above-mentioned 1.5 item is dissolved in 8mL CH2Cl2 and BF3 (8mg, 61mmol, 0.1 equivalent) is added dropwise at -78 ℃. Stir at this temperature for 5 hours, then make the reaction warm up to room temperature and stop. Add water (10mL) and carry out phase separation. The aqueous phase is extracted with MTBE (2x 10mL), and the organic phase merged is washed with 5%NaHCO3 solution (20mL), saturated NaCl solution (20mL) and water (20mL) successively. The extract is dried, filtered, and volatile components are removed under reduced pressure. The mixture of compound 1 and 2 obtained (134mg, 562μmol, 92%, GC isomer ratio 13:76%) is a colorless solid. Compound 1 and 2 are separated by column chromatography.

[0210] Compound 1:

[0211] Melting point (mp): T m =51℃ to 52℃

[0212] TLC:R f =0.37 (ethyl acetate / cyclohexane, 5:95)

[0213] [α] 25 D =-31.7° (c=0.24M, EtOH, enantiomer 1a), [α] 25 D = +33.0° (c = 0.49 M, EtOH, enantiomer 1b)

[0214] 1 H-NMR (600MHz, C6D6) δ = 3.98 (d, J = 7.0Hz, 1H, C q (O)C(H)H'O),3.36(dd,J=6.9,1.1Hz,1H,C q (O)C(H)H'O),1.79(dt,J=12.6,3.5Hz,1H,C q (O)C(H)H'),1.71(ddd,J=13.9,12.5,3.9Hz,1H,C q (O)C(H)H'),1.66–1.62(m,2H,CH3C q CH2),1.55(s,3H,C q CH3),1.53–1.48(m,1H,C q (O)CH), 1.48–1.42 (m, 3H, 2x C q CHC(H)H',CHC(H)H'CH2Cq ),1.37(dtd,J=12.9,4.8,2.5Hz,1H,CHC(H)H'CH2C q ),0.92(tt,J=12.2,3.3Hz,1H,C q CH),0.74(s,9H,C(CH3)3),0.61(dt,J=13.2,11.8Hz,1H,C q CHC(H)H'),0.51–0.44(m,1H,C q CHC(H)H')

[0215] 13 C-NMR (151MHz, C6D6) δ = 107.05 (CH3C q (O)O),82.84(C q (O)),70.78(C q CH2O),47.68(C q CH),40.65(C q (O)CH),36.34(CH3C q CH2),35.07(C(O)C q CH2),32.15(C q (CH3)3),32.03(C q CHCH2),27.64(C(CH3)3),25.84(CHCH2CH2C q ),25.41(C q CHCH2),24.88(C q CH3)

[0216] IR (GC / FT-IR): 2881(m),1389(w)1259(w),1201(w),1150(w),1038(m),859(w)cm -1

[0217] MS (EI): m / z = 238 [M] + ,57[(CH3)3C] +

[0218] HRMS (ESI-TOF): calculated value C 15 H 26 O2[M+H] + 239.2011; true value 239.2010

[0219] Odor description: Amber, ambergris, woody

[0220] Compound 2:

[0221] TLC:R f =0.37 (ethyl acetate / cyclohexane, 5:95)

[0222] 1 H-NMR (600MHz, C6D6) δ = 3.69 (d, J = 6.6Hz, 1H, C q (O)C(H)H'O),3.42(d,J=6.6Hz,1H,C q (O)C(H)H'O),2.08(ddt,J=13.8,12.8,6.4Hz,1H,CHC(H)H'CH2C q ),1.70(dt,J=13.5,3.3Hz,1H,C q (O)C(H)H'),1.66–1.60(m,1H,CH3C q C(H)H'),1.59–1.56(m,1H,C q CHC(H)H'),1.56–1.51(m,2H,C q CHCH2),1.50(s,3H,C q CH3),1.47(ddd,J=13.3,6.4,1.4Hz,1H,CH3C q C(H)H'),1.30(dtd,J=12.4,3.5,1.4Hz,1H,C q CHC(H)H'),1.16–1.09(m,2H,C q (O)C(H)H',CHC(H)H'CH2C q ),1.05(dddd,J=12.9,6.6,3.9,1.1Hz,1H,C q (O)CH), 0.94–0.88 (m, 1H, C q CH), 0.87(s,9H,C(CH3)3)

[0223] 13 C-NMR (151MHz, C6D6) δ = 108.16 (CH3C q (O)O),80.60(C q (O)),74.74(C q CH2O),47.74(C q CH),38.24(C q (O)CH),33.12(C(O)C q CH2),32.12(C q(CH3)3),31.85(CH3C q CH2),28.87(C q CHCH2),27.45(C(CH3)3),24.88(C q CH3),24.48(CHCH2CH2C q ),23.35(C q CHCH2)

[0224] IR (GC / FT-IR): 2881(m),1389(w)1201(w),1150(w),1038(m),859(w)cm -1

[0225] MS (EI): m / z = 238 [M] + ,57[(CH3)3C] +

[0226] Odor description: Woody, cedar, slightly animalic

[0227] 2. Synthetic Route II of Compound of Formula (Ia)

[0228] The synthetic steps described in Items 1.1 and 1.2 above were performed to obtain tert-butyl 3-((1'R,5'R)-5'-(tert-butyl)-2'-methylenecyclohexyl)propanoate (the reaction product described in Item 1.2 above). The product was used in the alternative synthetic route described below to obtain the compound of formula (Ia).

[0229] 2.1 Synthesis of 3-((1'R,5'R)-5'-(tert-butyl)-2'-methylenecyclohexyl)propan-1-ol

[0230]

[0231] LiAlH 4 (164 mg, 4.23 mmol, 1.2 equivalents) is placed in 5 mL THF and cooled to 0° C. The reaction product described in item 1.2 above (1.00 g, 3.52 mmol) is dissolved in 5 mL THF and slowly added dropwise while stirring. It is stirred at 0° C. for 1 hour, heated to room temperature and added ice water (20 mL). Phase separation is carried out, and the aqueous phase is extracted with MTBE (3x20 mL). The combined organic extracts are washed with 5% NaHCO 3 solution (30 mL), saturated NaCl solution (30 mL) and water (30 mL) in sequence. The extract is then dried, filtered and volatile components are removed under reduced pressure. The product obtained is a colorless liquid (717 mg, 3.41 mmol, 97%, 96:4 isomer mixture (cis / trans)) and can be used for the next step without further purification.

[0232] TLC:R f =0.46 (ethyl acetate / cyclohexane, 20:80)

[0233] 1 H-NMR (400MHz, CDCl3) δ = 4.68 (d, J = 1.7Hz, 1H, C = C(H)H'), 4.55 (d, J = 1.5Hz, 1H, C = C(H)H'), 3.67 (t, J = 6. 2Hz,2H,CH2OH),2.36(dt,J=12.9,3.6Hz,1H,CH2=CC(H)H'),2.00–1.83(m,4H,CH2=CC(H)H',CH2=CCH,2x C q CHC(H)H'),1.78–1.62(m,3H,CHC(H)H'CH2),1.35–1.20(m,2H,CHC(H)H'CH2,C q CH),1.05(qd,J=12.4,3.8Hz,1H,C q CHC(H)H'),0.85(s,9H,C(CH3)3),0.73(q,J=12.0Hz,1H,C q CHC(H)H')

[0234] 13 C-NMR (101MHz, CDCl3) δ = 153.33 (C = CH2), 103.76 (C = CH2), 63.44 (CH2OH), 48.16 (C q CH),42.35(CH2=CCH),37.11(CH2=CCH2),35.65(C qCHCH2),32.47(C(CH3)3),30.64(CH2CH2OH),29.70(C q CHCH2),28.65(CHCH2CH2),27.66(C(CH3)3)

[0235] IR (GC / FT-IR): 3089(w),2949(s),2875(w),1371(w),1054(w)892(w)cm -1

[0236] MS (EI): m / z = 210 [M] + ,57[(CH3)3C] +

[0237] HRMS (ESI-TOF): calculated value C 14 H 26 O[M+H] + 211.2062; true value 211.2053

[0238] 2.2 Synthesis of 3-((1'R,5'R)-5'-(tert-butyl)-2'-methylenecyclohexyl)propanal

[0239]

[0240] The reaction product described in above-mentioned 2.1 (2.10g, 9.73mmol) is dissolved in 25mL CH Cl In. Add Dess-Martin periodinane (4.95g, 11.68mmol, 1.2 equivalents), and at room temperature stir reaction mixture 4 hours. Use Et O (50mL) dilution and add 5% NaOH solution (10mL). Carry out phase separation, aqueous phase Et O (10mL) extraction. The organic extract merged is washed with saturated NaCl solution (50mL) and water (50mL). It is used Na SO Dry, filter and remove volatile components under reduced pressure. The crude product is purified by column chromatography (100mL SiO , 3% to 5% EtOAc, in cyclohexane). The product obtained is a colorless liquid (1.84g, 8.86mmol, 91%, 97:3 isomer mixture (cis / trans)).

[0241] TLC:R f =0.49 (ethyl acetate / cyclohexane, 5:95)

[0242] 1H-NMR (400MHz, CDCl3) δ = 9.80 (dd, J = 1.7Hz, 1H, CHO), 4.71 (d, J = 1.6Hz, 1H, C = C(H)H'), 4.54 (d, J = 1.5Hz, 1H, C = C(H)H'), 2.57–2.50 (m, 2H ,CH2CHO),2.37(ddd,J=12.8,4.0,2.8Hz,1H,CH2=CC(H)H'),2.02–1.92(m,2H,CH2=CC(H)H',CHC(H)H'CH2),1.91–1.84(m,3H,CH2=CCH,2x C q CHC(H)H'),1.67–1.56(m,1H,CHC(H)H'CH2),1.24(tt,J=12.1,3.1Hz,1H,C q CH),1.06(qd,J=12.6,4.0Hz,1H,C q CHC(H)H'),0.85(s,9H,C(CH3)3),0.76(q,J=12.9Hz,1H,C q CHC(H)H')

[0243] 13 C-NMR (101MHz, CDCl3) δ = 202.74 (CHO), 152.40 (C = CH2), 104.08 (C = CH2), 48.07 (C q CH),42.01(CH2=CCH,CH2CHO),36.98(CH2=CCH2),35.61(C q CHCH2),32.45(C(CH3)3),29.62(C q CHCH2),27.63(C(CH3)3),24.63(CHCH2CH2)

[0244] IR (GC / FT-IR): 2952(s),2873(w),2711(w)1742(m)1370(w),893(w)cm -1

[0245] MS (EI): m / z = 208 [M] + ,57[(CH3)3C] + ,[CH2CH2COH] +

[0246] Odor description: Pojhónal, floral, lily of the valley, cucumber, very strong, slightly fruity melon

[0247] 2.3 Synthesis of 4-((1'R,5'R,2R / S)-5'-(tert-butyl)-2'-methylenecyclohexyl)butan-2-ol

[0248]

[0249] The reaction product described in above-mentioned 2.2 (315mg, 1.29mmol) is dissolved among the 5mL THF and is cooled to-78 ℃.At this temperature, slowly drip MeLi (1.61mL, be placed in Et 1.6M solution among the O, 2.57mmol, 2 equivalents) and stir 4 hours.It is heated to room temperature, and adds water (5mL).Carry out phase separation, aqueous phase Et O (3x 5mL) extraction.The organic extract Na merging SO Dry and filter.Under decompression, remove volatile component, crude product is by column chromatography (100mLSiO , 10%EtOAc in cyclohexane) purifying.The product obtained is colorless liquid (259mg, 1.15mmol, 90%, 96:4 isomer mixture (cis / trans)). Both isomers also consist of a 1:1 isomeric mixture through stereogenic carbon atoms and secondary hydroxyl groups, which cannot be identified by gas chromatography but can be identified by nuclear magnetic resonance (NMR).

[0250] TLC:R f =0.21 (ethyl acetate / cyclohexane, 10:90)

[0251] 1 H-NMR (400MHz, CDCl3) δ = 4.68 (d, J = 1.7Hz, 1H, C = C(H)H'), 4.56 (d, J = 1.4Hz, 1H, C = C(H)H'), 3.88–3. 76(m,1H,CH(OH)CH3),2.36(dt,J=12.8,3.1Hz,1H,CH2=CC(H)H'),2.02–1.90(m,2H,CH2=CC(H)H',C q CHC(H)H'),1.89–1.80(m,1H,CH2=CCH,C q CHC(H)H'),1.78–1.66(m,1H,CHC(H)H'CH2),1.59–1.45(m,1H,CH2C(H)OH),1.43–1.36(m,1H,C q CH), 1.23 (d, J = 2.2 Hz, 3H / 2, CH(OH)CH3 (first isomer)), 1.21 (d, J = 2.3 Hz, 3H / 2CH(OH)CH3 (second isomer)), 1.05 (qd, J = 12.5, 4.0 Hz, 1H, C qCHC(H)H'),0.85(s,9H,C(CH3)3),0.73(qd,J=12.0,1.8Hz,1H,C q CHC(H)H')

[0252] 13 C-NMR (101MHz, CDCl3) δ = 153.39 (aC = CH2), 153.29 (bC = CH2), 103.79 (aC = CH2), 103.75 (bC = CH2), 68.64 (a-CH (OH) CH3), 68.62 (b-CH (OH) CH3), 48.18 (C q CH),42.61(a-CH2=CCH),42.59(b-CH2=CCH),37.14(a-CH2=CCH2,a-CH2C(H)OH),37.12(b-CH2=CCH2,b-CH2C(H)OH),35.76(aC q CHCH2),35.68(bC q CHCH2),32.46(C(CH3)3),29.72(C q CHCH2),28.72(a-CHCH2CH2),28.64(b-CHCH2CH2),27.66(C(CH3)3),23.61(a-CH(OH)CH3),23.50(b-CH(OH)CH3)

[0253] IR (GC / FT-IR): 3089(w),2950(s),2878(w),1371(w),892(w)cm -1

[0254] MS (EI): m / z = 224 [M] + ,167[M-(CH3)3C] + ,57[(CH3)3C] +

[0255] HRMS (ESI-TOF): calculated value C 15 H 28 O[M+H] + 225.2218; true value 225.2210

[0256] 2.4 Synthesis of 4-((1'R,5'R)-5'-(tert-butyl)-2'-methylenecyclohexyl)butan-2-one

[0257]

[0258] The reaction product described in above-mentioned item 2.3 (145mg, 630μmol) is dissolved in 4mL CH Cl In. Dess-Martin periodinane (321mg, 756μmol, 1.2 equivalents) is added to the solution and stirred at room temperature for 3 hours. The reaction mixture is diluted with Et O (10mL) and 5% NaOH solution (4mL) is added. Phase separation is carried out, and the aqueous phase is extracted with Et O (5mL). The organic phase merged is washed with saturated NaCl solution (10mL) and water (10mL) successively. The extract is dried, filtered, and volatile components are removed under reduced pressure. The crude product is purified by column chromatography (50mL SiO , 4% to 5% EtOAc in cyclohexane), and the product obtained is a colorless liquid (116mg, 553μmol, 83%, 95:5 isomer mixture (cis / trans)). The analytical data of products therefrom are consistent with the data in above-mentioned item 1.4.

[0259] In order to obtain the compound of formula (Ia), the reaction steps described in the above items 1.5 and 1.6 are carried out.

[0260] 3. Synthetic route of compound of formula (Ib)

[0261] 3.1 Synthesis of methyl 3-methylbut-3-en-1-yl-4-benzenesulfonate

[0262]

[0263] Alcohol (10mL, 98.7mmol) is dissolved in 50mL pyridine and is cooled to 0 ℃.At this temperature, p-methylbenzenesulfonyl chloride (TsCl, 21.8g, 113.5mmol, 1.15 equivalents) is added in small portions and stirred 2.5 hours at this temperature.It is warming up to room temperature, reaction stops with 2M HCl solution (100mL).Phase separation, aqueous phase is extracted with MTBE (2x 100mL).The organic phase merged is washed with 10%NH4Cl solution (100mL), 5%NaHCO3 solution (100mL) and saturated NaCl solution (100mL) successively.Organic phase Na2SO4 drying, filtration, and remove volatile components under reduced pressure.The product obtained is a colorless liquid (21.2g, 88.2mmol, 89%), and can be used for next step without any purification.

[0264] TLC:R f =0.49 (ethyl acetate / cyclohexane, 20:80)

[0265] GC: DB-1 column: t R =13.4 minutes

[0266] 1 H-NMR (400MHz, CDCl3) δ = 7.79 (d, J = 8.3Hz, 2H, 2x ArH), 7.35 (d, J = 8.1Hz, 1H, 2x ArH),4.79(s,1H,C=C(H)H'),4.68(s,1H,C=C(H)H'),4.13(t,J=6.9Hz,2H,CH2OTs ),2.45(s,3H,ArCH3),2.35(t,J=6.8Hz,2H,C(=CH2)CH2),1.66(s,3H,C(=CH2)CH3)

[0267] 13 C-NMR (101MHz, CDCl3) δ = 144.73 (CH3C (Ar)), 140.13 (C = CH2), 133.16 (SO2C (Ar)), 129.81 (2x Ar), 127.91 (2x Ar),113.10(C=CH2),68.54(CH2OTs),36.76(C(=CH2)CH2),22.34C(=CH2)CH3),21.65(ArCH3)

[0268] IR (GC / FT-IR): 2968(m),2937(w),1392(m)1188(s),1088(m),1025(s),973(m)cm -1

[0269] MS (EI): m / z = 155 [Ts] + ,91[(C6H4)CH3] + ,55[(CH3)C(=CH2)CH2] +

[0270] 3.2 Synthesis of 4-iodo-2-methylbut-1-ene

[0271]

[0272] NaI (53.2 g, 351 mmol, 4 equivalents) was dissolved in 300 mL of acetone. The reaction product (21.2 g, 87.8 mmol) described in item 3.1 above was added dropwise at room temperature and stirred at this temperature for 24 hours. Water (125 mL) was added and the product was extracted with hexane (3 × 100 mL). The combined organic phases were washed with water (100 mL) and saturated NaCl solution (100 mL) in turn. The organic phase was dried, filtered, and volatile components were removed under reduced pressure. The product obtained was a light yellow liquid (10.9 g, 55.3 mmol, 63%) and was used in the next step without any further purification.

[0273] 1 H-NMR (400MHz, CDCl3) δ = 4.86 (d, J = 0.8Hz, 1H, C = C(H)H'), 4.76 (d, J = 1.0Hz, 1H, C = C(H)H'), 3.2 6(t,J=7.6Hz,2H,CH2I),2.59(t,J=7.5Hz,2H,C(=CH2)CH2),1.74(t,J=1.1Hz,3H,C(=CH2)CH3)

[0274] 13 C-NMR (101MHz, CDCl3) δ = 143.90 (C = CH2), 112.29 (C = CH2), 41.88 (C ( = CH2) CH2), 21.68C ( = CH2) CH3), 3.52 (CH2I)

[0275] IR (GC / FT-IR): 2983(s),2943(m),1851(m),1447(m),1239(s),1171(s),899(s)cm -1

[0276] MS (EI): m / z = 196 [M] + ,127[I] + ,69[(CH3)C(=CH2)CH2CH2] + ,41[CH3C=CH2] +

[0277] 3.3 Synthesis of (2R,4R)-4-(tert-butyl)-2-(3'-methylbut-3'-en-1'-yl)cyclohexane-1-one

[0278]

[0279] Tert-butylcyclohexanone (4.92 g, 31.6 mmol, 1.25 equivalents) was dissolved in 50 mL of toluene, KOtBu (3.40 g, 30.3 mmol, 1.2 equivalents) was added, and the mixture was stirred at room temperature for 1 hour. The reaction product described in Item 3.2 above (5.00 g, 25.3 mmol) was added dropwise to the solution and stirred at room temperature for 4 days. 10% NH4Cl solution (50 mL) was added and the phases were separated. The aqueous phase was extracted with MTBE (3 x 50 mL), and the combined organic phases were washed with saturated NaCl solution (100 mL). After drying over Na2SO4, the mixture was filtered, and the volatile components were removed under reduced pressure. The crude product was purified by Kugelrohr distillation (1.0 mbar, 120°C to 1.2 mbar, 178°C) and then by column chromatography (100 mL SiO2, 5% EtOAc in cyclohexane). The product was obtained as a colorless liquid (557 mg, 2.51 mmol, 10%, 8:1 isomer mixture (cis / trans)).

[0280] TLC:R f =0.49 (ethyl acetate / cyclohexane, 5:95)

[0281] 1 H-NMR (600MHz, CDCl3) δ = 4.69 (ddt, J = 20.8, 2.4, 1.4Hz, 2H, C = CH2), 2.41–2.36 (m, 1H, C ( = O) C ( H) H'), 2.33 ( ddd,J=13.5,5.9,1.3Hz,1H,C(=O)C(H)H'),2.31–2.24(m,1H,C(=O)CH),2.15(ddt,J=12.9,5.2,3.3Hz,1H,C q CHC(H)H'CH),2.09(ddt,J=12.8,5.9,3.0Hz,1H,C q CHC(H)H'CH2),2.07–1.95(m,3H,C(=O)CHC(H)H'CH2C q ),1.72(t,J=1.2Hz,3H,C(=CH2)CH3),1.58(tt,J=12.2,3.2Hz,1H,C q CH),1.44(qdd,J=12.1,4.6,1.2Hz,1H,C q CHC(H)H'CH2),1.30–1.22(m,1H,C q CHC(H)H'),1.17–1.10(m,1H,C qCHC(H)H'CH),0.92(d,J=1.2Hz,9H,C(CH3)3)

[0282] 13 C-NMR (151MHz, CDCl3) δ = 213.47 (C = O), 145.78 (C = CH2), 110.02 (C = CH2), 49.02 (C ( = O) CH), 47.19 (C q CH),41.76(C(=O)CH2),35.21(CH2C=CH2),35.12(C q CHCH2CH),32.48(C(CH3)3),28.80(C q CHCH2CH2),27.67(C(CH3)3),27.09(C(=O)CHCH2),22.35(C(=CH2)CH3)

[0283] IR (GC / FT-IR): 2967(s),2877(w),1728(s),1453(w),1223(w),891(w)cm -1

[0284] MS (EI): m / z = 222 [M] + ,[(CH3)3C] +

[0285] HRMS (ESI-TOF): calculated value C 15 H 26 O[M+H] + 223.2062; true value 223.2055

[0286] 3.4 Synthesis of compounds 3 and 4

[0287]

[0288] The reaction product described in above-mentioned 3.3 (52mg, 213μmol) is dissolved in 1.5mL EtOAc and MeCN respectively.Stir the solution at room temperature, and slowly drip and be placed in 0.7mL H o among the RuCl 3H o (4mg, 21μmol, 0.1 equivalent) and NaIO solution (70mg, 320μmol, 1.5 equivalent).Stir at room temperature 10 minutes, then add 10% Na s o solution (5mL).Phase separation, aqueous phase is extracted with EtOAc (3x 5mL).The organic extract water (20mL) that merges is washed, uses Na s o dry and filter.Under decompression, remove volatile component, crude product is purified by preparative gas chromatography to obtain compound 3 (30%) and compound 4 (32%).

[0289] The first stereoisomer (compound 3):

[0290] TLC:R f =0.41 (ethyl acetate / cyclohexane, 5:95)

[0291] 1 H-NMR (600MHz, C6D6) δ = 3.68 (d, J = 6.7Hz, 1H, C q C(H)H'O),3.39(dd,J=6.7,1.9Hz,1H,C q C(H)H'O),2.10–2.02(m,2H,OC q (O)C(H)H',C q CHC(H)H'),1.73(ddd,J=13.7,13.0,4.5Hz,1H,OC q (O)C(H)H'),1.65–1.59(m,2H,C q CHC(H)H'CH2,CH3C q C(H)H'),1.56–1.49(m,3H,C q CHC(H)H'CH,OC q (O)CH,C q CHC(H)H'CH2),1.43–1.38(m,1H,C q CHC(H)H'CH),1.15(ddd,J=13.7,5.8,1.4Hz,1H,C q CHC(H)H'),1.10(s,3H,CH3C q ),1.04(ddd,J=13.4,6.3,1.5Hz,1H,CH3C q C(H)H'),1.01–0.96(m,1H,Cq CH),0.84(s,9H,C(CH3)3)

[0292] 13 C-NMR (151MHz, C6D6) δ = 109.21 (C q (O)O),79.87(CH3C q O),73.31(C q CH2O),47.85(C q CH),40.48(OC q (O)CH),35.94(OC q (O)CH2),32.36(C(CH3)3),31.46(CH3C q CH2),31.14(C q CHCH2CH),27.90(C(CH3)3),25.19(C q CHCH2CH2), 24.55C q CHCH2CH2C q CH3),23.39(C q CH3)

[0293] IR (GC / FT-IR): 2885(m),1370(w),1325(w),1114(w),1062(m)cm -1

[0294] MS (EI): m / z = 238 [M] + ,210[M-CH2CH2] + ,208[M-CH2O] + ,181[M-[(CH3)3C] + ,57[(CH3)3C] +

[0295] Odor description: Amber, woody

[0296] The second stereoisomer (Compound 4):

[0297] TLC:R f =0.39 (ethyl acetate / cyclohexane, 5:95)

[0298] 1 H-NMR (600MHz, C6D6) δ = 3.62 (d, J = 6.7Hz, 1H,, C q C(H)H'O),3.36(dd,J=6.7,2.0Hz,1H,C qC(H)H‘O),2.07(dt,J=12.9,3.4Hz,1H,OC q (O)C(H)H‘),1.75(td,J=13.4,4.4Hz,1H,OC q (O)C(H)H‘),1.66–1.61(m,1H,C q CHC(H)H’CH2),1.60–1.53(m,1H,CH3C q C(H)H‘),1.53–1.47(m,3H,C q CHC(H)H’CH,C q CHC(H)H’CH2,OC q (O)CH),1.44–1.31(m,2H,OC q (O)CHCH2),1.24–1.19(m,1H,C q CHC(H)H’CH),1.13(s,1H,CH3C q ),0.99(tt,J=12.2,2.9Hz,1H,C q CH),0.84(s,9H,C(CH3)3)

[0299] 13 C-NMR(151MHz,C6D6)δ=108.61(C q (O)O),79.02(CH3C q O),73.95(C q CH2O),47.54(C q CH),41.84(OC q (O)CH),35.44(OC q (O)CH2),35.24(CH3C q CH2),32.35(C(CH3)3),32.16(C q CHCH2CH),27.79(C(CH3)3),25.97(C q CHCH2CH2C q CH3),24.85(C q CHCH2CH2),22.93(C q CH3)

[0300] IR(GC / FT-IR): 2885(m),1374(w),1233(w),1138(w),1031(w)cm -1

[0301] MS (EI): m / z = 238 [M] + ,210[M-CH2CH2] + ,208[M-CH2O] + ,181[M-[(CH3)3C] + ,57[(CH3)3C] +

[0302] Odor description: Woody, ambergris-like

[0303] 4. Aromatherapy oils

[0304] The values ​​shown in Tables 2 and 3 below are by weight.

[0305] Fragrance Oil 1

[0306]

[0307]

[0308] Table 2: (middle column) Component contents of aromatic oil 1; (right column) Component contents of aromatic oil 1 according to the invention with compound 1 or with compound 2 or with a mixture of compounds 3+4 (the weight ratio of compound 3 to compound 4 is 1:1).

[0309] After adding Compound 1 or Compound 2 or the mixture of Compounds 3+4 to the fragrance oil 1 listed above (see Table 2, middle column), the obtained fragrance oil (see Table 2, right column) smells more harmonious, more floral and more natural.

[0310] Fragrance Oil 2

[0311]

[0312]

[0313] Table 3: (middle column) Component contents of aromatic oil 2; (right column) Component contents of aromatic oil 2 according to the present invention with compound 1 or with compound 2 or with a mixture of compounds 3+4 (the weight ratio of compound 3 to compound 4 is 1:1).

[0314] After adding Compound 1 or Compound 2 or the mixture of Compounds 3+4 to the fragrance oil 2 listed above (see Table 3, middle column), the obtained fragrance oil (see Table 3, right column) has more diffusivity and is mellower and more harmonious.

Claims

1. A compound of formula (I) wherein X and Y are selected from the group consisting of -O- and -CH2-, respectively, and When X is -O-, then Y is -CH2-; when X is -CH2-, then Y is -O-, Wherein the compound of formula (I) is selected from the group consisting of the following compounds:

2. A composition comprising one, two, three or more compounds of formula (I).

3. A method for preparing the compound according to claim 1 or the composition according to claim 2, comprising the following reaction steps:

4. A method for preparing the compound according to claim 1 or the composition according to claim 2, comprising the following reaction steps:

5. A method for preparing the compound according to claim 1 or the composition according to claim 2, comprising the following reaction steps:

6. Use of the compound according to claim 1 as an aromatic substance.

7. Use of the composition according to claim 2 as a fragrance mixture.

8. Use according to claim 6 or 7, for imparting, modifying and / or enhancing one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic notes.

9. The use according to claim 8, for imparting, modifying and / or enhancing the olfactory characteristics of ambergris.

10. A fragrance composition comprising the following substances: (i) a compound according to claim 1, or (ii) a composition according to claim 2, and one or more additional aromatic substances.

11. A fragrance product comprising the compound according to claim 1, the composition according to claim 2, or the aromatic substance composition according to claim 10.

12. Fragrance product according to claim 11, wherein the product is selected from the group consisting of detergents and cleaning agents, hygiene or care products.

13. The fragrance product according to claim 12, wherein the product is used in the cosmetic and household fields.

14. The fragrance product according to claim 12, wherein the product is used in the field of body and hair care.

15. The fragrance product of claim 12, wherein the product is selected from the group consisting of perfume extracts, eau de parfum, eau de toilette, cologne, pre-shave products, scented refreshing wipes, acidic, alkaline or neutral detergents, textile refreshers, ironing aids, laundry pretreatments, fabric softeners, disinfectants, air fresheners, aerosol sprays, waxes and polishes, body care products, depilatory creams and lotions, aftershave creams and lotions, self-tanning creams and lotions, hair care products, deodorants, antiperspirants, decorative cosmetic products, candles, lamp oil, incense sticks, insecticides, insect repellents and fuel.

16. The fragrance product of claim 12, wherein the product is selected from the group consisting of: splash cologne, liquid detergent, powder detergent, detergent soap, and detergent bars.

17. The fragrance product of claim 12, wherein the product is selected from the group consisting of: surface disinfectants, hand creams and lotions, and foot creams and lotions.

18. A fragrance product according to any one of claims 11 to 17, wherein the one or more compounds of formula (I) are contained in an organoleptically effective amount.

19. The fragrance product of claim 18, wherein the one or more compounds of formula (I) are contained in an amount sufficient for a consumer to detect one or more olfactory characteristics selected from the group consisting of ambergris, woody notes, and animalic notes.

20. The fragrance product of claim 18, wherein the one or more compounds of formula (I) are contained in an amount sufficient for a consumer to detect the olfactory characteristics of ambergris.

21. A method for preparing a fragrance product, the method comprising the steps of: (i) Provide A compound according to claim 1 or a composition according to claim 2 or a fragrance substance composition according to claim 10, (ii) providing one or more other components of the fragrance product to be produced, and (iii) contacting or mixing the other components provided in step (ii) with the organoleptically effective amount of the components provided in step (i).

22. A method for flavoring a product, the method comprising the steps of: (a) Provide (i) a compound according to claim 1, or (ii) a composition according to claim 2, or (iii) the aromatic substance composition according to claim 10, and (b) the above (i) The compound according to claim 1 or said (ii) The composition according to claim 2 or (iii) the fragrance composition according to claim 10 is added to the product to be scented in an organoleptically effective amount.

23. The method according to claim 22, wherein in step (b), the (i) compound according to claim 1 or the (ii) The composition according to claim 2 or (iii) the fragrance composition according to claim 10 is added to the product to be perfumed in an amount sufficient to impart, enhance and / or modify one or more olfactory characteristics selected from the group consisting of ambergris, woody notes and animalic notes.

24. The method according to claim 22, wherein in step (b), the (i) compound according to claim 1 or the (ii) The composition according to claim 2 or (iii) the fragrance substance composition according to claim 10 is added to the product to be perfumed in an amount sufficient to impart, enhance and / or modify the olfactory characteristics of ambergris.

25. A method for scenting hair, skin, textile fibers, surfaces and / or ambient air, said method comprising the steps of: (a) Provide (i) a compound according to claim 1, or (ii) a composition according to claim 2, or (iii) the aromatic substance composition according to claim 10, or (iv) a fragrance product according to any one of claims 11 to 20, as well as (b) applying or introducing the (i) compound, or the (ii) composition, or the (iii) fragrance composition, or the (iv) perfume product of step (a) in an organoleptically effective amount to the hair or skin or textile fibers or surfaces to be scented, or applying or introducing into the ambient air to be scented.

26. The process according to claim 25, wherein in step (a), (i) a compound according to claim 1 and a surfactant or a mixture of surfactants are provided.

27. The method of claim 25, wherein in step (a) there is provided (ii) a composition according to claim 2 comprising a surfactant or a mixture of surfactants.

28. The method according to claim 25, wherein in step (a), (iii) a fragrance substance composition according to claim 10 is provided, which comprises a surfactant or a surfactant mixture.

29. A method according to claim 25, wherein in step (a) there is provided (iv) a fragrance product according to any one of claims 11 to 20 comprising a surfactant or a mixture of surfactants.

30. The method of claim 25, wherein the (i) compound, or the (ii) composition, or the (iii) fragrance composition, or the (iv) perfume product of step (a) is applied to the hair or skin or textile fibers or surfaces to be perfumed, or introduced into the ambient air to be perfumed, in an amount sufficient for a consumer to detect one or more olfactory characteristics selected from the group consisting of ambergris, woody notes, and animalic notes.

31. The method of claim 25, wherein the (i) compound, or the (ii) composition, or the (iii) fragrance composition, or the (iv) perfume product of step (a) is applied to the hair or skin or textile fibers or surfaces to be perfumed, or introduced into the ambient air to be perfumed, in an amount sufficient for a consumer to detect the olfactory characteristics of ambergris.

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