5-methylcyclohexanols and derivatives as fragrances

Abstract

The present invention relates to fragrances, primarily to a compound according to formula (I) as defined herein and a method for producing the compound according to formula (I) as defined herein. Furthermore, the present invention relates to a fragrance composition comprising or consisting of one or more compound(s) of formula (I) as defined herein. The present invention also relates to a perfumed product comprising or consisting of a fragrance composition or one or more compound(s) as defined herein and furthermore to a use of a compound or of a fragrance composition as defined herein as fragrance.

Description

[0001] 5-Methylcyclohexanols and derivatives as fragrances

[0002] The present invention primarily relates to a compound according to formula (I) as defined herein and a method for producing the compound according to formula (I) as defined herein. Furthermore, the present invention relates to a fragrance composition comprising or consisting of one or more compound(s) of formula (I) as defined herein and, preferably, further components. The present invention also relates to a perfumed product comprising or consisting of a fragrance composition according to the invention or one or more compound(s) as defined herein as well as further components, and furthermore to a use of a compound or of a fragrance composition as defined herein as fragrance.

[0003] Further aspects of the present invention will arise from the description below, in particular from the examples, as well as from the attached patent claims.

[0004] Although a plurality of fragrances is already available, a general need of novel fragrances still exists in the perfume industry as the consumers frequently request novel and modern fragrances.

[0005] For the creation of novel compositions, there is a constant need of fragrances with special sensory characteristics, which are suitable to serve as a basis for the composition of novel perfumes with complex sensory character.

[0006] The search for suitable substances which led to the present invention was further impeded by the following circumstances:

[0007] The mechanisms of the olfactory perception are not sufficiently known; the relationship between the special olfactory perception on the one side and the chemical structure of the corresponding fragrance on the other side are not sufficiently investigated; often, minor changes in the structural composition of a known fragrance cause substantial changes in the sensory characteristics and impair the tolerance of the human organism.

[0008] Such fragrances should advantageously be suitable to perfume certain products and should further advantageously be easily produced. Furthermore, such fragrances should preferably also fulfil one, more or advantageously all of the following aspects: being easily produced, having a strong effect in low concentration, having no toxic and / or allergic effect on humans, and preferably also one or both of the following aspects, where appropriate: largely or completely colorless, high stability in diverse mixtures or, respectively, preparations, wherein particularly no discoloration and / or separation and / or clouding shall occur.

[0009] Thus, the primary object of the present invention was to provide a compound which can be used as a fragrance e.g. for the use in the perfumery or other areas, particularly as fragrances with a floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, and / or fuzzy characteristic. Furthermore, the object of the present invention was to provide a compound which can be used as a fragrance for enhancing the volume of a floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0010] Another object of the present invention was to provide a method for the manufacturing of compounds with the previously mentioned properties.

[0011] Further objects underlying the present invention follow from the description below and the present patent claims.

[0012] According to a first aspect of the present invention, the stated objects are achieved by a compound according to formula (I) wherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-Ce alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2is selected from the group consisting of methyl group, allyl group and the following groups: wherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-Ce alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2and R3are H, or wherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-Ce alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2is H, and wherein R3is selected from the group consisting of methyl, isopentyl, butyl, C(=O)CH3, C(=O)CH=C(CH3)2and C(=O)OCH2CH3group, and wherein if Ri is isopropyl and R2 is 2-ethyl-1-3-dioxolane R3 is not H, and wherein if R1 is 1 ,4,5,5,-tetramethylcyclopent-1-en and R2 is H R3 is not H.

[0013] It was surprisingly found that fragrances comprising 5-substituted methylcyclohexanols and their derivatives exhibit scents with a floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, and / or fuzzy characteristic. Furthermore, the compounds according to the invention can be used as fragrances for enhancing the volume of a floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0014] In the state of the art, compounds with similar as well as with different chemical structure may be known for being used as a fragrance with a similar odor. However, even though there may be similar compounds, a prediction of the odor of a compound based on the chemical structure is impossible (e.g. Cell, C.S. (2006), Zur Unmbglichkeit der Geruchsvorhersage, Angewandte Chemie, 118:6402-6410). Thus it is not possible to predict the odor of a compound based on the odor of a structurally highly similar compound. Likewise, it is also not possible to "design" a chemical structure based on a desired odor, which is simply synthesized and automatically exhibits the desired odor.

[0015] Certain methods for producing similar structures, e.g. 2-ethyl-5,5-dimethyl-cyclohexanol are known in the state of the art (EP 3681463 B1).

[0016] In EP 0026344 A1 2,2,3-trimethylcycloent-3-en-ylmethyl-substituted acyclic ketones and alcohols, as well as their manufacturing process and their uses as fragrances is disclosed.

[0017] The use of cis-3-cyclopentylcyclohexanol as fragrance ingredient is disclosed in WO 201 1 / 020909 A2, which possesses a strong leathery, suede, animalic type odor.

[0018] WO 2018 / 171871 A1 discloses the use of 2,3,6-trimethylcyclohexanol as a scenting and / or flavoring agent and further relates to new scenting and / or flavoring agent compositions comprising 2,3,6-trimethylcyclohexanol, the use thereof, scented and / or flavored articles comprising 2,3,6-trimethylcyclohexanol, and various processes for imparting, modifying and / or enhancing certain fragrances and / or flavors.

[0019] Muguet type fragrance compounds are disclosed in WO 2022 / 058019 A1 as well as in Helv. Chimic. Acta 2023, 106, e202300040. A preferred embodiment according to the invention is a compound as defined above, wherein Ri is isobutyl, R2 is methyl and / or R3 is H, or R1 is ethyl, R2 is the following group: , and / or R3 is H, or R1 is ethyl, R2 is allyl and / or R3 is H, or R1 is ethyl, R2 is H and / or R3 is H, or R1 is butyl, R2 is H and / or R3 is H, or R1 is hexyl, R2 is H and / or R3 is H, or R1 is phenylethyl, R2 is H and / or R3 is H, or R1 is isobutyl, R2 is H and / or R3 is H, or R1 is isopropyl, R2 is H and / or R3 is C(=O)CH3, or R1 is isobutyl, R2 is H and / or R3 is C(=O)CH3, or R1 is hexyl, R2 is H and / or R3 is C(=O)CH3, or R1 is phenyl, R2 is methyl and / or R3 is H, or R1 is isobutyl, R2 is methyl and / or R3 is H, or R1 is isobutyl, R2 is H and / or R3 is C(=O)CH=C(CH3)2.

[0020] Compounds according to formula (I) with groups as defined above are particularly advantageous, as they preferably can be used as potent fragrances. Another aspect of the present invention is a method for producing a compound of formula (I) as defined above, comprising or consisting of the following steps:

[0021] (a) reacting a compound according to formula (II) , wherein Ri is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, with ethyl acetoacetate to obtain a compound according to formula (III)

[0022] (HI), with R1 as defined above,

[0023] (b) performing a saponification and subsequent decarboxylation reaction with the compound of formula (III) obtained in step (a) to obtain a compound according to formula (IV) with R1 as defined above, and

[0024] (c) performing a reduction reaction with the compound of formula (IV) obtained in step

[0025] (b) to obtain a compound according to formula (VIII) (VIII), with Ri as defined above, or

[0026] (d) performing a hydrogenation reaction with the compound of formula (IV) obtained in step (b) to obtain a compound according to formula (V)

[0027] AR1

[0028] (V), with Ri as defined above, and

[0029] (e) reacting the compound according to formula (V) obtained in step (d) with a compound according to formula (VI)

[0030] R2MgX

[0031] (VI), wherein X is bromine or chlorine and R2is selected from the group consisting of methyl group, allyl group and the following groups: to obtain a compound according to formula (VII) with Ri and R2 as defined above, or f) performing a reduction reaction with the compound of formula (V) obtained in step (d) to obtain a compound according to formula (VIII)

[0032] (VIII), with Ri as defined above, and optionally, subsequent to step (c) or (f), if present,

[0033] (g) performing an ether- / esterification reaction with the compound of formula (VIII) obtained in step (c) or (f) to obtain a compound according to formula (IX)

[0034] (IX), with Ri as defined above, and wherein R3is selected from the group consisting of methyl, isopentyl, butyl, C(=O)CH3, C(=O)CH=C(CH3)2and C(=O)OCH2CH3group.

[0035] A method as defined above is particularly advantageous as it overcomes some or all of the general drawbacks in the manufacture of fragrances reported herein, in particular when performed in a preferred mode as described herein. By incorporating the well-known Hagemannester synthesis as reaction step, a cost-effective and technically easy applicable method is implemented. Furthermore, its implementation provides a method which foregoes without the use of protecting groups.

[0036] A preferred embodiment according to the invention is a method as defined above for producing a compound of formula (III) wherein R1 is cyclohexyl or te / Y-butyl.

[0037] A preferred embodiment according to the invention is a method as defined above for producing a compound of formula (V) wherein R1 is cyclohexyl.

[0038] The disclaimer of compounds according to formula (I) wherein if R1 is isopropyl and R2is 2-ethyl-1-3-dioxolane R3is not H, and wherein if R1 is 1 , 4,5,5, -tetramethylcyclopent-1-en and R2is H R3is not H, preferably applies to the method as well as the other aspects of the present invention as defined herein accordingly.

[0039] Preferably, by applying the method according to the invention as defined above up to and including step e), compounds according to formula (I), - l O -

[0040] (I), wherein Ri is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2 is selected from the group consisting of methyl group, allyl group and the following groups: and wherein R3 is H, are obtained.

[0041] Preferably, by applying the method according to the invention as defined above up to and including step f), compounds according to formula (I),

[0042] (I), wherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2 and Rs are H, preferably are obtained. wherein R3 is H, are obtained.

[0043] Preferably, by applying the method according to the invention as defined above up to and including step g), compounds according to formula (I),

[0044] (I), wherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2 is H, and wherein R3 is selected from the group consisting of methyl, isopentyl, butyl, C(=O)CH3, C(=O)CH=C(CH3)2 and C(=O)OCH2CH3group, are obtained.

[0045] A preferred embodiment according to the invention is a method as defined above, wherein step a) and step b) are performed in a one-pot synthesis.

[0046] Another preferred embodiment according to the invention is a method as defined above, wherein performing an ether- / esterification reaction in step (g) is performed by reacting the compound of formula (VIII) obtained in step (f) with a compound selected from the group consisting of alkyl halide, acid anhydride, unsaturated acid and dialkylcarbonate, preferably with a compound selected from the group consisting of methyl iodide, butyl bromide, 3- methylbut-2-enoic acid, diethylcarbonate.

[0047] Advantageously, a method as defined above provides preferably the compounds according to formula (I) with high yields and purity.

[0048] The present invention also relates to a fragrance composition comprising or consisting of one or more compound(s) of formula (I) as defined above, and, optionally, one, two three, four, five, six, seven, eight, nine, ten or more further fragrance(s), preferably selected from the group consisting of i) essential oils and extracts, preferably bergamot oil, coriander oil, galbanum oil, jasmine absolute, lemon oil, limette oil, neroli oil, oak moss absolute, patchouli oil, petitgrain oil, rose oil, woody oil or ylang-ylang oil, ii) alcohols, preferably citronellol, linalool, tetrahydrolinalool, dihydromyrcenol, tetrahydromyrcenol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pent-4- en-2-ol] (Ebanol®), eugenol, geraniol, {[(1 R,2S)-1-methyl-2-{[(1 R,3S,5S)- 1 ,2,2-trimethyl-3-bicyclo[3.1 .0]hexanyl]methyl}-cyclopropyl]-methanol} (Javanol®), phenethyl alcohol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3- enyl)pentan-2-ol] (Sandalore®), terpineol, nopol, benzyl alcohol, 9-decen-1- ol, 3-isocamphylcyclohexanol, cis-3-hexenol, or [1 -(2,2,6- trimethylcyclohexyl)hexan-3-ol] (Timberol®), iii) aldehydes and ketones, preferably a-amylcinnamaldehyde, a-hexylcinnamaldehyde, decanal, (methyl 3-oxo-2- pentylcyclopentaneacetate) (Hedione®), {3-[(4R)-4-(propan-2-yl)cyclohex-1 - en-1-yl]propanal} (Lilybelle®), product mixture resulting from the cyclization of myrcene with (3E)-3-methylpent-3-en-2-one giving [1-(1 ,2,3,4,5,6,7,8- octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1- (1 ,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1-(1 ,2,3,5,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one] (Iso E Super®), [E-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2- one] (Isoraldeine®), 2-methyl-3-(p-isopropylphenyl)propanal (Cyclamen aldehyde), ionones, methylionone, irones, hydroxy citronellal, muscenone, heliotropin, or vanillin, iv) ether and acetals, preferably {(1 R,3S,7R,8 / ?,10 / ?,13 / ?)-5,5,7,9,9,13- Hexamethyl-4,6-dioxatetrayclo[6.5.1 .0(1 ,10).0(3,7)]-tetradecane} (Ambrocenide®), {[3aR-(3aa,5ap,9aa,9bp)]-dodecahydro-3a,6,6,9a- tetramethylnaphtho[2,1-b]furan} (Ambrox®), geranyl methyl ether, (2,4- dimethyl-4,4a,5,9b-tetrahydroindeno[1 ,2-d]-1 ,3-dioxin) (Magnolan®), rose oxide, diphenyl oxide, or {spiro[1 ,3-dioxolane-2,5’-(4’,4’,8’,8’-tetramethyl- hexahydro-3’,9’-methanonaphthalene)]} (Ysamber K®), v) esters and lactones, preferably Ambrettolide, benzyl acetate, benzyl salicylate, coumarin, y-decalactone, ethylene brassylate, {2-[(1 R)-1-[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-[(1 S)-1 -[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-oxo-2-{[(1 S,2S)-2,6,6- trimethylcycloheptyl]oxy}ethyl propanoate} (Ecomusk® R), Macrolide, an isomeric mixture of diethyl 2-methylfumarate and diethyl 2-methylmaleate and diethyl 2-methylenesuccinate, ethyl tetrahydrofuran-2-carboxylate, geranyl acetate, linalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, y- undecalactone, terpinyl acetate, nopyl acetate, p-tertbutylcyclohexyl acetate, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, isononyl acetate, tricyclodecenyl acetate, 4-acetoxy-3-pentyl- tetrahydropyran, or vetiveryl acetate, vi) heterocycles, preferably galbazine, indol, or isobutylquinoline.

[0049] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of one or more compound(s) of formula (III) as defined above, wherein Ri is cyclohexyl or te / Y-butyl , and one, two three, four, five, six, seven, eight, nine, ten or more further frag rance(s), preferably selected from the group consisting of i) essential oils and extracts, preferably bergamot oil, coriander oil, galbanum oil, jasmine absolute, lemon oil, limette oil, neroli oil, oak moss absolute, patchouli oil, petitgrain oil, rose oil, woody oil or ylang-ylang oil, ii) alcohols, preferably citronellol, linalool, tetrahydrolinalool, dihydromyrcenol, tetrahydromyrcenol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pent-4- en-2-ol] (Ebanol®), eugenol, geraniol, {[(1 R,2S)-1-methyl-2-{[(1 R,3S,5S)- 1 ,2,2-trimethyl-3-bicyclo[3.1 .0]hexanyl]methyl}-cyclopropyl]-methanol} (Javanol®), phenethyl alcohol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3- enyl)pentan-2-ol] (Sandalore®), terpineol, nopol, benzyl alcohol, 9-decen-1- ol, 3-isocamphylcyclohexanol, cis-3-hexenol, or [1 -(2,2,6- trimethylcyclohexyl)hexan-3-ol] (Timberol®), iii) aldehydes and ketones, preferably a-amylcinnamaldehyde, a-hexylcinnamaldehyde, decanal, (methyl 3-oxo-2- pentylcyclopentaneacetate) (Hedione®), {3-[(4R)-4-(propan-2-yl)cyclohex-1- en-1-yl]propanal} (Lilybelle®), product mixture resulting from the cyclization of myrcene with (3E)-3-methylpent-3-en-2-one giving [1-(1 ,2,3,4,5,6,7,8- octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1- (1 ,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1-(1 ,2,3,5,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one] (Iso E Super®), [E-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2- one] (Isoraldeine®), 2-methyl-3-(p-isopropylphenyl)propanal (Cyclamen aldehyde), ionones, methylionone, irones, hydroxy citronellal, muscenone, heliotropin, or vanillin, iv) ether and acetals, preferably {(1 R,3S,7R,8 / ?,10 / ?,13 / ?)-5,5,7,9,9,13- Hexamethyl-4,6-dioxatetrayclo[6.5.1 .0(1 ,10).0(3,7)]-tetradecane} (Ambrocenide®), {[3aR-(3aa,5ap,9aa,9bp)]-dodecahydro-3a,6,6,9a- tetramethylnaphtho[2,1-b]furan} (Ambrox®), geranyl methyl ether, (2,4- dimethyl-4,4a,5,9b-tetrahydroindeno[1 ,2-d]-1 ,3-dioxin) (Magnolan®), rose oxide, diphenyl oxide, or {spiro[1 ,3-dioxolane-2,5’-(4’,4’,8’,8’-tetramethyl- hexahydro-3’,9’-methanonaphthalene)]} (Ysamber K®), v) esters and lactones, preferably Ambrettolide, benzyl acetate, benzyl salicylate, coumarin, y-decalactone, ethylene brassylate, {2-[(1 R)-1-[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-[(1 S)-1 -[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-oxo-2-{[(1 S,2S)-2,6,6- trimethylcycloheptyl]oxy}ethyl propanoate} (Ecomusk® R), Macrolide, an isomeric mixture of diethyl 2-methylfumarate and diethyl 2-methylmaleate and diethyl 2-methylenesuccinate, ethyl tetrahydrofuran-2-carboxylate, geranyl acetate, linalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, y- undecalactone, terpinyl acetate, nopyl acetate, p-tertbutylcyclohexyl acetate, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, isononyl acetate, tricyclodecenyl acetate, 4-acetoxy-3-pentyl- tetrahydropyran, or vetiveryl acetate, vi) heterocycles, preferably galbazine, indol, or isobutylquinoline.

[0050] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of compound(s) of formula (V) as defined above, wherein Ri is cyclohexyl, n- hexyl or phenyl, and one, two three, four, five, six, seven, eight, nine, ten or more further fragrance(s), preferably selected from the group consisting of i) essential oils and extracts, preferably bergamot oil, coriander oil, galbanum oil, jasmine absolute, lemon oil, limette oil, neroli oil, oak moss absolute, patchouli oil, petitgrain oil, rose oil, woody oil or ylang-ylang oil, ii) alcohols, preferably citronellol, linalool, tetrahydrolinalool, dihydromyrcenol, tetrahydromyrcenol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pent-4- en-2-ol] (Ebanol®), eugenol, geraniol, {[(1 R,2S)-1-methyl-2-{[(1 R,3S,5S)- 1 ,2,2-trimethyl-3-bicyclo[3.1 .0]hexanyl]methyl}-cyclopropyl]-methanol} (Javanol®), phenethyl alcohol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3- enyl)pentan-2-ol] (Sandalore®), terpineol, nopol, benzyl alcohol, 9-decen-1- ol, 3-isocamphylcyclohexanol, cis-3-hexenol, or [1 -(2,2,6- trimethylcyclohexyl)hexan-3-ol] (Timberol®), iii) aldehydes and ketones, preferably a-amylcinnamaldehyde, a-hexylcinnamaldehyde, decanal, (methyl 3-oxo-2- pentylcyclopentaneacetate) (Hedione®), {3-[(4R)-4-(propan-2-yl)cyclohex-1- en-1-yl]propanal} (Lilybelle®), product mixture resulting from the cyclization of myrcene with (3E)-3-methylpent-3-en-2-one giving [1-(1 ,2,3,4,5,6,7,8- octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1- (1 ,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1-(1 ,2,3,5,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one] (Iso E Super®), [E-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2- one] (Isoraldeine®), 2-methyl-3-(p-isopropylphenyl)propanal (Cyclamen aldehyde), ionones, methylionone, irones, hydroxy citronellal, muscenone, heliotropin, or vanillin, iv) ether and acetals, preferably {(1 R,3S,7R,8 / ?,10 / ?,13 / ?)-5,5,7,9,9,13- Hexamethyl-4,6-dioxatetrayclo[6.5.1 .0(1 ,10).0(3,7)]-tetradecane} (Ambrocenide®), {[3aR-(3aa,5ap,9aa,9bp)]-dodecahydro-3a,6,6,9a- tetramethylnaphtho[2,1-b]furan} (Ambrox®), geranyl methyl ether, (2,4- dimethyl-4,4a,5,9b-tetrahydroindeno[1 ,2-d]-1 ,3-dioxin) (Magnolan®), rose oxide, diphenyl oxide, or {spiro[1 ,3-dioxolane-2,5’-(4’,4’,8’,8’-tetramethyl- hexahydro-3’,9’-methanonaphthalene)]} (Ysamber K®), v) esters and lactones, preferably Ambrettolide, benzyl acetate, benzyl salicylate, coumarin, y-decalactone, ethylene brassylate, {2-[(1 R)-1-[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-[(1 S)-1 -[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-oxo-2-{[(1 S,2S)-2,6,6- trimethylcycloheptyl]oxy}ethyl propanoate} (Ecomusk® R), Macrolide, an isomeric mixture of diethyl 2-methylfumarate and diethyl 2-methylmaleate and diethyl 2-methylenesuccinate, ethyl tetrahydrofuran-2-carboxylate, geranyl acetate, linalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, y- undecalactone, terpinyl acetate, nopyl acetate, p-tertbutylcyclohexyl acetate, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, isononyl acetate, tricyclodecenyl acetate, 4-acetoxy-3-pentyl- tetrahydropyran, or vetiveryl acetate, vi) heterocycles, preferably galbazine, indol, or isobutylquinoline.

[0051] A preferred embodiment according to the invention is a fragrance composition as defined above, wherein the weight ratio of the total amount of compound(s) of formula (I) to the total weight of further fragrance(s) is in a range of from 0.01 % to 20%, preferably of from 0.1 % to 10%.

[0052] Advantageously, a fragrance composition as defined above with such a particular weight ratio of the total amount of compound(s) of formula (I) to the total weight of further fragrance(s) provides particularly valuable odor compositions.

[0053] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of one or more compound(s) of formula (III) as defined above, wherein Ri is cyclohexyl or te / Y-butyl, wherein the weight ratio of the total amount of compound(s) of formula (I) to the total weight of further fragrance(s) is in a range of from 0.01 % to 20%, preferably of from 0.1 % to 10%.

[0054] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of compound(s) of formula (V) as defined above, wherein Ri is cyclohexyl, n- hexyl or phenyl, wherein the weight ratio of the total amount of compound(s) of formula (I) to the total weight of further fragrance(s) is in a range of from 0.01 % to 20%, preferably of from 0.1 % to 10%.

[0055] Another preferred embodiment according to the invention is a fragrance composition as defined above, comprising 3-isobutyl-1 ,5-dimethylcyclohexan-1-ol and / or 3-ethyl-5- methylcyclohexan-1-ol. A fragrance composition comprising 3-isobutyl-1 ,5-dimethylcyclohexan-1-ol and / or 3-ethyl- 5-methylcyclohexan-1-ol showed a particularly advantageous odor profile.

[0056] A further preferred embodiment according to the invention is a fragrance composition as defined above, wherein the total amount of compound(s) of formula (I) in the fragrance composition is present in a sensorically effective amount, preferably in an amount sufficient for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0057] Surprisingly, it was found that fragrance compositions as defined above are preferably capable of imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0058] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of one or more compound(s) of formula (III) as defined above, wherein Ri is cyclohexyl or te / Y-butyl, wherein the total amount of compound(s) of formula (III) in the fragrance composition is present in a sensorically effective amount, preferably in an amount sufficient for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0059] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of compound(s) of formula (V) as defined above, wherein Ri is cyclohexyl, n- hexyl or phenyl, wherein the total amount of compound(s) of formula (V) in the fragrance composition is present in a sensorically effective amount, preferably in an amount sufficient for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes. A preferred embodiment according to the invention is a fragrance composition as defined above, wherein the or, respectively, one, several or all of the further fragrances (also) impart, modify and / or enhance one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0060] Furthermore, it was surprisingly found that in a fragrance composition as defined above, one, several or all of the further fragrances (also) impart, modify and / or enhance one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0061] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of one or more compound(s) of formula (III) as defined above, wherein Ri is cyclohexyl or te / Y-butyl, wherein the or, respectively, one, several or all of the further fragrances (also) impart, modify and / or enhance one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0062] A preferred embodiment according to the invention is a fragrance composition comprising or consisting of compound(s) of formula (V) as defined above, wherein Ri is cyclohexyl, n- hexyl or phenyl, wherein the or, respectively, one, several or all of the further fragrances (also) impart, modify and / or enhance one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0063] The present invention also relates to a perfumed product, comprising or consisting of

[0064] (i) a fragrance composition as defined above, or one or more compounds of formula (I) as defined above, and

[0065] (ii) one or more further component(s), preferably at least one or more, preferably one, two, three, four, five, or more additives, excipients and / or active substance(s).

[0066] A perfumed product as defined herein is particularly advantageous as it preferably covers the customers’ needs of a rich and long-lasting odorant.

[0067] A preferred embodiment according to the invention is a perfumed product, comprising or consisting of

[0068] (i) a fragrance composition as defined above, or one or more compounds of formula (III) as defined above, wherein Ri is cyclohexyl or te / Y-butyl , and

[0069] (ii) one or more further component(s), preferably at least one or more, preferably one, two, three, four, five, or more additives, excipients and / or active substance(s).

[0070] A preferred embodiment according to the invention is a perfumed product, comprising or consisting of

[0071] (i) a fragrance composition as defined above, or one or more compound(s) of formula (V) as defined above, wherein Ri is cyclohexyl, n-hexyl or phenyl, and (ii) one or more further component(s), preferably at least one or more, preferably one, two, three, four, five, or more additives, excipients and / or active substance(s).

[0072] A preferred embodiment according to the invention is a perfumed product as defined above, wherein the product is selected from the group consisting of washing and cleaning agents, hygiene or care products, preferably in the field of body and hair care, cosmetics and home care, preferably selected from the group consisting of perfume extraits, eau de parfums, eau de toilettes, aftershaves, eau de colognes, pre-shave-products, splash-colognes, perfumed refreshing tissues, acid, alkaline or neutral cleaning agents, textile refreshing agents, ironing aids, liquid washing agents, washing agents in powder form, laundry pretreatment agents, fabric softeners, laundry soap, laundry tablets, disinfectants, sur-face disinfectants, air refreshers, aerosols, waxes and polishes, body care agents, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair-care products deodorants, anti-perspirants, products of decorative cosmetics, candles, lamp oils, joss sticks, insecticides, repellents and propellants.

[0073] Advantageously a perfumed product as defined herein preferably offers a wide variety of fields, e.g., area of daily life, wherein it can be used.

[0074] Another preferred embodiment according to the invention is a perfumed product as defined above, wherein component (i) is present in a sensorically effective amount, preferably in an amount sufficient for that a consumer perceives one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0075] Another preferred embodiment according to the invention is a perfumed product as defined above, wherein the total amount of compound(s) of formula (I), related to the total amount of the perfumed product, is in a range of from 0.0006 to 1.3 wt.-%, preferably 0.001 to 7 wt.-%.

[0076] A preferred embodiment according to the invention is a perfumed product as defined above, wherein the total amount of compound(s) of formula (III), related to the total amount of the perfumed product, is in a range of from 0.0006 to 1 .3 wt.-%, preferably 0.001 to 7 wt.-%. A preferred embodiment according to the invention is a perfumed product as defined above, wherein the total amount of a compound of formula (V), related to the total amount of the perfumed product, is in a range of from 0.0006 to 1 .3 wt.-%, preferably 0.001 to 7 wt.-%.

[0077] Furthermore, an aspect of the present invention is a method for producing the perfumed product as defined above, comprising or consisting of the following steps:

[0078] (i) Providing a compound or a fragrance composition as defined above,

[0079] (ii) mixing the compound or fragrance composition provided in step i) with one or more further component(s), preferably at least one or more, preferably one, two, three, four, five, or more additives, excipients and / or active substance(s).

[0080] Another aspect of the present invention is a method for perfuming a product, comprising or consisting of the following steps:

[0081] (a) Providing

[0082] (a.1) a fragrance composition as defined above or

[0083] (a.2) one or more compound(s) as defined above, and

[0084] (b) adding the fragrance composition (a.1) or, respectively, compound(s) (a.2) to the product to be perfumed in a sensorically effective amount, preferably in an amount sufficient for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0085] A further aspect of the present invention is a method for perfuming hair, skin, textile fibers, surfaces and / or room air comprising or consisting of the following steps:

[0086] (a) Providing (a.1) a fragrance composition as defined above, or

[0087] (a.2) one or more compound(s) as defined above, or

[0088] (a.3) a perfumed product as defined above, and

[0089] (b) adding the fragrance composition (a.1) or, respectively, the compound(s) (a.2) or, respectively, the perfumed product (a.3) to the hair or, respectively, skin or, respectively, fibers or, respectively, surface or, respectively, in the room air to be perfumed in a sensorically effective amount, preferably in an amount sufficient for that a consumer perceives one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0090] Another aspect of the present invention is a use of a compound as defined above, or of a fragrance composition as defined above as fragrance.

[0091] Advantageously, a compound or fragrance composition as defined above preferably provides the possibility to be used as fragrance in plenty of fields of, e.g., everyday life.

[0092] A preferred embodiment according to the invention is a use as defined above, for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes, preferably use of 3-isobutyl-1 ,5-dimethylcyclohexanol and / or 3-ethyl-5- methylcyclohexan-1-ol, or of a fragrance composition as defined above comprising 3- isobutyl-1 ,5-dimethylcyclohexanol and / or 3-ethyl-5-methylcyclohexan-1-ol for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, freesia, citrus, rossitol, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note, and / or for enhancing leathery impressions and / or for pushing ambery notes.

[0093] The invention will now be described in more detail hereinafter with references to selected examples. Preferred aspects of the present invention are disclosed in the accompanying claims.

[0094] Examples

[0095] 1) General Synthesis of compounds according to formula (I)

[0096] General procedure: Haqemannester synthesis

[0097] To a solution of acetoacetic acid (2.5 equiv.) and an aldehyde (1.0 equiv.) according to formula (II) a solution of piperidine (104 mol-%) in ethanol was added over 40 min, keeping the temperature between 23-43 °C. The resulting reaction mixture was heated to 70°C over 2 h. After cooling to ambient temperature, the mixture was treated with water and the aqueous and organic layers were separated. The aqueous layer was extracted with methyl te / Y-butylether and the combined organic layers were concentrated under reduced pressure. The crude product was fractionally distilled and the Hagemannester according to formula (III) was obtained.

[0098] General procedure: Saponification

[0099] A solution of the Hagemannester (1.0 equiv.) according to formula (III) in ethanol was treated with aqueous NaOH solution such that the temperature did not exceed 20°C. Then, the reaction mixture was heated to 82 °C for 5.5 h. After cooling to ambient temperature, the solvent was evaporated under reduced pressure. The residue was taken into methyl te / Y-butylether and water, the layers were separated, and the organic layer was washed with aqueous saturated NH4CI solution, aqueous NaHCOs solution and NaCI solution until neutral. The organic layer was concentrated under reduced pressure to give the crude enone according to formula (IV) which was purified by fractioned distillation.

[0100] General procedure: Hydrogenation

[0101] The enone (1 .0 equiv.) according to formula (IV) was dissolved in isopropanol and Pd / C (5 weight-%) was added. The reaction mixture was treated with H2 at 2-5 bar within a temperature range of 23-30°C. After completion of the reaction, the catalyst was filtered off, the organic layer was concentrated under reduced pressure and the crude product was purified by distillation, yielding in a ketone according to formula (V).

[0102] General procedure: Grignard reaction

[0103] To a solution of Grignard reagent (1.2 equiv.) according to formula (VI) in THF a solution of ketone (1.0 equiv.) according to formula (V) in THF was added over 3 h keeping the temperature at 0 °C. After stirring for another hour at 0 °C, the reaction mixture was warmed to ambient temperature over 2 h. Then, it was poured on 10 °C cooled aqueous saturated NH4CI solution and the layers were separated. The aqueous layer was extracted with methyl te / Y-butylether (MtBE) and the combined organic layers were washed with aqueous saturated NaHCOs solution and water to neutrality. The organic layer was concentrated under reduced pressure and the crude product according to formula (VII) was purified by fractioned distillation.

[0104] General procedure: Reduction

[0105] The ketone (1.0 equiv.) according to formula (V) was dissolved in isopropanol and Ru / C (1-5 weight-%) was added. The reaction mixture was treated with H2 at 5-7 bar within a temperature range of 70-75°C. After completion of the reaction, the catalyst was filtered off and the crude product was distilled to give the corresponding cyclohexanol according to formula (VIII).

[0106] General procedure: Esterification

[0107] To a solution of cyclohexanol (1.0 equiv.) according to formula (VIII) in anhydride (1.4 equiv.), NEts (1.4 equiv.) and DMAP (7 mol-%) were added at ambient temperature with optional cooling upon exothermic reaction. The reaction mixture was stirred at ambient temperature for 30 min. After completion of the reaction, it was diluted with MtBE and washed with aqueous HCI solution. Then, the organic layer was washed with aqueous saturated NaHCOs solution and water to neutrality. The organic layer was concentrated under reduced pressure and the crude product was purified by flash chromatography and distillation to give the acetylated cyclohexanol according to formula (IX).

[0108] 2) Total synthesis of selected compounds according to formula (I)

[0109] Example 1 : 3-lsobutyl-1 ,5-dimethyl-cyclohexanol fcompound according to formula (VI 111 Hagemannester synthesis: Ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate [compound according to formula (lll)1

[0110] To a solution of ethyl acetoacetate (438 g, 3.33 mmol, 2.5 equiv.) and isovaleraldehyde (117 g, 1.33 mmol, 1.0 equiv.) according to formula (II) a solution of piperidine (11.5 g, 0.133 mmol, 104 Mol-%) in ethanol was added dropwise at 24-43°C over 40 min. Afterwards, the reaction mixture was heated under reflux at 70 °C for 255 min. After cooling to ambient temperature water (350 mL) was added to the reaction mixture and the layers were separated. The aqueous layer was extracted with MtBE (2 x 250 mL) and the combined organic layers were concentrated under reduced pressure. After fractioned distillation, Ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate according to formula

[0111] (III) was obtained as liquid (236 g, 97.7%; eff. 231 g = 1 .02 mol). MS: m / z (%) = 238, 223, 207, 195, 181 , 165, 154, 137, 126, 121 , 109, 98, 95, 79, 67, 57, 41.

[0112] Saponification: 5-lsobutyl-3-methyl-cyclohex-2-en-1-one [compound according to formula

[0113] (IV)1

[0114] To a solution of ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate (390 g, 1.59 mmol, 1.0 equiv.) in ethanol (821 g) an aqueous NaOH-solution (2.7 M) was added under slight cooling, keeping the temperature beneath 20°C. Subsequently, the reaction mixture was stirred for 345 min at 82 °C. After the reaction mixture had cooled down, the solvent was evaporated under reduced pressure. The residue was dissolved in MtBE and water and the layers were separated. The organic layer was washed with saturated aqueous NH4CI-solution, aqueous NaHCOs-solution and aqueous saturated NaCI-solution until neutral. The organic layer was concentrated under reduced pressure and after distillation, the enone according to formula (IV) was obtained as liquid (254 g, 96.9% yield; eff. 246 g = 1.48 mol). MS: m / z (%) = 166, 151 , 133, 124, 109, 95, 82, 67, 54, 41.

[0115] Hydrogenation: 3-lsobutyl-5-methyl-cyclohexanone [compound according to formula (V)1

[0116] The 5-isobutyl-3-methyl-cyclohex-2-en-1-one (254 g, 1 ,47mol; 1 .0 equiv.) was dissolved in / so-propanol (393 g) and hydrogenated at 2-5 bar and 23 to 30 °C with a palladium / carbon catalyst (12.5 g, 5 wt.-%) for 115 min. The catalyst was filtered off and the organic layer was concentrated under reduced pressure. After distillation (57.4 - 63.7 °C, 0.72 - 0.68 bar) the ketone according to formula (V) was obtained as liquid (235 g, 97.8%; eff. 230 g = 1 .37 mol). MS: m / z (%) = 168, 153, 135, 125, 1 11 , 97, 83, 69, 55, 41 , 39, 29.

[0117] Grignard reaction: 3-lsobutyl-1 ,5-dimethyl-cyclohexanol [compound according to formula

[0118] I 1D1 To a solution of methylmagnesiumchloride (273 ml, 0.82 mol, 1.2 equiv.) according to formula (VI) in tetra h yd rofurane (THF; 140 ml) a solution of 3-isobutyl-5-methyl- cyclohexanone (118 g, 0.68mol, I .O equiv.) in THF (377 ml) was added dropwise within 189 min while keeping the temperature between 2-8 °C. After the reaction mixture was stirred for 57 min at 0 °C, it was allowed to warm to ambient temperature within 110 min. The reaction mixture was poured into an aqueous saturated solution of ammoniumchloride at 10 °C and the layers were separated. The aqueous layer was extracted with MtBE (2x) and the combined organic layers were washed with an aqueous saturated sodium bicarbonate solution and with water until neutral. The solvents were removed under reduced pressure and after fractioned distillation the cyclohexanol according to formula (VII) was obtained as liquid (242 g, 96.7%; eff. 234 g = 1.27 mol).1H-NMR (400 MHz, CDCh): 6 = 0.36-0.47 (m, 1 H), 0.85-0.87 (m, 6H), 0.87-0.95 (m, 5H), 0.99-1.10 (m, 2H), 1.21 (s, 3H), 1.56-1.80 (m, 6H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.4, 22.8, 23.0, 24.7, 27.9, 30.4, 31.7, 41.5, 45.7, 46.7, 47.6, 70.5 ppm. MS: m / z (%) = 184, 169, 151 , 140, 127, 109, 95, 85, 71 , 55, 43, 29. Odor description: rossitol, floral, citrus, clean, freesia.

[0119] Effective total yield over 4 reaction steps a) - d): 60.2%.

[0120] Example 2: 1,3-Dimethyl-5-phenylcyclohexan-1-ol fcompound according to formula (VI 111

[0121] Haqemannester synthesis: Ethyl-3-methyl-5-oxo-1 ,2,5,6-tetrahydro-[1 ,1 '-biphenyl1-2- carboxylate [compound according to formula (111)1

[0122] The Hagemannester synthesis was performed onto benzaldehyde according to formula (II) in accordance with the general procedure above to give the title compound as liquid. MS: m / z (%) = 258, 230, 212, 185, 154, 126, 98, 77, 65, 53, 29.

[0123] Saponification: 5-methyl-1 ,6-dihydro-[1 ,1 '-biphenyl1-3(2H)-one [compound according to formula (IV)1

[0124] The saponification was performed onto ethyl 3-methyl-5-oxo-1 ,2,5,6-tetrahydro-[1 ,1 '- biphenyl]-2-carboxylate according to formula (III) in accordance with the general procedure above to give the title compound as liquid.1H-NMR (400 MHz, CDCh): 5 = 2.01 (q, J = 0.9 Hz, 3H), 2.50-2.71 (m, 4H), 3.27-3.38 (m, 1 H), 5.98 (s, 1 H), 7.23-7.27 (m, 3H), 7.32-7.38 (m, 2H) ppm.13C-NMR (101 MHz, CDCh): 6 = 24.3, 39.0, 40.7, 43.8, 126.5, 126.7, 128.8, 143.3, 161 .6, 199.13 ppm. MS: m / z (%) = 207, 186, 171 , 158, 142, 129, 104, 91 , 82, 77, 65, 54, 39, 27. Hydrogenation: 3-methyl-5-phenylcyclohexanone [compound according to formula (V)1

[0125] The hydrogenation was performed onto 5-methyl-1 ,6-dihydro-[1 ,1 '-biphenyl]-3(2H)-one according to formula (IV) in accordance with the general procedure above to give the title compound as liguid.1H-NMR (400 MHz, CDCh): 6 = 1 .09 (d, J = 6.2 Hz, 3H), 1 .49-1 .65 (m, 1 H), 1.91-2.13 (m, 3H), 2.38-2.51 (m, 2H), 2.52-2.65 (m, 1 H), 2.97 (tt, J = 12.8, 3.8 Hz, 1 H), 7.18-7.27 (m, 2H), 7.29-7.36 (m, 2H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.4, 33.4, 41 .7, 43.8, 48.4, 49.5, 126.5, 126.7, 128.7, 144.3, 210.7 ppm. MS: m / z (%) = 207, 188, 173, 131 , 1 18, 104, 91 , 78, 56, 41 , 27.

[0126] Grignard reaction: 1 ,3-Dimethyl-5-phenylcyclohexan-1-ol [compound according to formula (Y1D1

[0127] The Grignard reaction was performed onto 3-methyl-5-phenylcyclohexanone according to formula (V) in accordance with the general procedure above to give the title compound as colorless liguid (1.28 g, 6.26 mmol).1H-NMR (400 MHz, CDCh): 6 = 0.94 (d, J = 6.6 Hz, 3H), 1.01-1.11 (m, 2H), 1.26 (s, 3H), 1.44 (d, J = 13.1 Hz, 1 H), 1.66-1.73 (m, 1 H), 1.77- 1.84 (m, 1 H), 1.84-1.90 (m, 1 H), 1.90-2.00 (m, 1 H), 2.98 (tt, J = 12.5, 3.5 Hz, 1 H), 7.14- 7.23 (m, 3H), 7.24-7.31 (m, 2H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.3, 28.3, 31.8, 39.4, 42.2, 46.2, 47.2, 70.7, 126.0, 127.0, 128.4, 146.9 ppm. MS: m / z (%) = 186, 171 , 157, 144, 129, 1 15, 105, 95, 91 , 85, 77, 69, 55, 43, 29. Odor description: floral, fruity, apple.

[0128] Example 3: 1-Allyl-3-ethyl-5-methylcyclohexan-1-ol [compound according to formula (VI 111

[0129] Hagemannester synthesis and saponification as one-pot synthesis: 5-ethyl-3- methylcyclohex-2-en-1-one [compound according to formula (IV)1

[0130] To a solution of ethyl acetoacetate (450 g, 3.46 mmol, 2.5 eguiv.) and propanal (103 mL, 82.9 g, 1 .38 mol) according to formula (II) was added a mixture of piperidine (13.8 mL, 11 .9 g, 138 mmol, 0.1 eguiv.) in EtOH (86 mL) at a temperature below 44°C. After completion of the addition, the mixture was heated to reflux for 4h to perform the synthesis of ethyl 6- ethyl-2-methyl-4-oxocyclohex-2-ene-1 -carboxylate. The intermediate product was not isolated, but directly submitted to saponification. After cooling to ambient temperature, a solution of NaOH (138 g, 3.46 mol) in H2O (751 mL) was added and the reaction mixture was heated to reflux for another 3h. Then, it was cooled to ambient temperature, MtBE and H2O were added, and the layers were separated. The organic layer was washed with agueous saturated NH4CI solution, NaHCOs solution and NaCI solution to neutrality. The crude product of 5-ethyl-3-methylcyclohex-2-en-1-one was concentrated under reduced pressure and used without further purification. MS: m / z (%) = 138, 123, 110, 82, 67, 54, 39, 27.

[0131] Hydrogenation: 3-ethyl-5-methylcyclohexan-1-one [compound according to formula (V)1

[0132] The hydrogenation was performed onto 5-ethyl-3-methylcyclohex-2-en-1-one according to formula (IV) in accordance with the general procedure above to give the title compound as colorless liquid .1H-NMR (400 MHz, CDCh): 6 = 0.91 (t, J = 7.4 Hz, 3H), 0.95-1 .02 (m, 1 H), 1 .03 (d, J = 6.3 Hz, 1 H), 1 .29-1 .46 (m, 2H), 1 .57-1 .71 (m, 1 H), 1 .74-1 .85 (m, 1 H), 1 .86-2.00 (m, 3H), 2.30-2.43 (m, 2H) ppm.13C-NMR (101 MHz, CDCh): 6 = 11.2, 22.5, 29.8, 33.2, 39.8, 40.2, 47.2, 49.8, 211.9 ppm. MS: m / z (%) = 140, 125, 111 , 107, 96, 93, 83, 69, 55, 41 , 29.

[0133] Grignard reaction: 1-Allyl-3-ethyl-5-methylcyclohexan-1-ol [compound according to formula (YlDl

[0134] The Grignard reaction onto 3-ethyl-5-methylcyclohexanone was performed in accordance with the general procedure above to give the title compound as colorless liguid (4.24 g, 23.2 mmol, mixture of isomers is a ratio of ~2:1). 1 H-NMR (400 MHz, CDCI3): 6 = 0.39- 0.56 (m, 2H), 0.83-1.02 (m, 18H), 1 .16-1 .27 (m, 4H), 1.27-1.35 (m, 1 H), 1 .47-1.68 (m, 4H), 1.68-1.80 (m, 3H), 2.17-2.21 (m, 2H), 2.27-2.31 (m, 2H), 5.08-5.18 (m, 4H), 5.84-5.95 (m, 2H) ppm. 13C-NMR (101 MHz, CDCI3): 6 = 1 1.4, 11 .4, 22.5, 22.5, 27.6, 29.5, 29.7, 29.8, 34.4, 36.3, 41.1 , 41.1 , 42.4, 43.3, 44.3, 45.8, 47.1 , 48.8, 71.9, 72.4, 118.7, 18.7, 133.8 ppm. MS: m / z (%) = 181 , 163, 153, 141 , 123, 111 , 97, 81 , 69, 55, 41 , 29. Odor description : fruity, damascene, rose, plum, metallic, minty, facets of tea.

[0135] Example 4: 3-Ethyl-5-methylcyclohexanol [compound according to formula (Vlll)l

[0136] Hagemannester synthesis and saponification as one-pot synthesis: 5-ethyl-3- methylcyclohex-2-en-1-one [compound according to formula (IV)1

[0137] To a solution of ethyl acetoacetate (450 g, 3.46 mmol, 2.5 eguiv.) and propanal (103 mL, 82.9 g, 1 .38 mol) according to formula (II) was added a mixture of piperidine (13.8 mL, 11 .9 g, 138 mmol, 0.1 eguiv.) in EtOH (86 mL) at a temperature below 44°C. After completion of the addition, the mixture was heated to reflux for 4h to perform the synthesis of ethyl 6- ethyl-2-methyl-4-oxocyclohex-2-ene-1 -carboxylate. The intermediate product was not isolated, but directly submitted to saponification. After cooling to ambient temperature, a solution of NaOH (138 g, 3.46 mol) in H2O (751 mL) was added and the reaction mixture was heated to reflux for another 3h. Then, it was cooled to ambient temperature, MtBE and H2O were added, and the layers were separated. The organic layer was washed with aqueous saturated NH4CI solution, NaHCOs solution and NaCI solution to neutrality. The crude product of 5-ethyl-3-methylcyclohex-2-en-1-one was concentrated under reduced pressure and used without further purification. MS: m / z (%) = 138, 123, 110, 82, 67, 54, 39, 27.

[0138] Reduction: 3-Ethyl-5-methylcyclohexanol [compound according to formula (Vlll)l

[0139] A solution of 5-ethyl-3-methylcyclohex-2-en-1-one (60.0 g, 434 mmol) in iPrOH (76 mL) was treated with Ru / C (1 wt-%, 0.63 g) under H2 pressure (20 bar) at 100°C for 5 h. The crude product was purified by simple distillation to give the desired product according to formula (VIII) as a colorless to yellowish liquid (33.6 g, 234 mmol, 54%).1H-NMR (400 MHz, CDCh): 6 = 0.42-0.58 (m, 2H), 0.72-1.52 (m, 25H), 1.15-1.52 (m, 14H), 1.53-1.70 (m, 4H), 1.71-1.82 (m, 5H), 1.83-2.2 (4H), 3.60 (tt, J = 1 1.0, 4.3 Hz, 1 H), 3.70-3.88 (m, 1 H), 4.13- 4.30 (m, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 11 .3, 11.5, 11.5, 12.6, 19.3, 22.3, 22.5, 22.6, 25.5, 26.1 , 26.2, 28.0, 29.5, 29.6, 29.8, 30.7, 32.6, 32.8, 35.6, 37.5, 37.6, 37.7, 38.9, 39.0, 40.7, 41 .4, 41 .4, 41 .6, 41 .7, 42.4, 44.5, 44.8, 66.8, 66.9, 67.4, 70.7 ppm. MS: m / z (%) = 140, 124, 109, 95, 83, 71 , 55, 41 , 29. Odor description: leather, phenol, guajac, smoky, birch tar.

[0140] Example 5: 3-lsobutyl-5-methylcvclohexyl acetate fcompound according to formula (IX)1

[0141] Haqemannester synthesis: Ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate [compound according to formula (lll)1

[0142] To a solution of ethyl acetoacetate (438 g, 3.33 mmol, 2.5 equiv.) and isovaleraldehyde (117 g, 1.33 mmol, 1.0 equiv.) according to formula (II) a solution of piperidine (11.5 g, 0.133 mmol, 104 Mol-%) in ethanol was added dropwise at 24-43°C over 40 minutes (min). Afterwards, the reaction mixture was heated under reflux at 70°C for 255min. After cooling to ambient temperature water (350 mL) was added to the reaction mixture and the layers were separated. The aqueous layer was extracted with MtBE (2 x 250 mL) and the combined organic layers were concentrated under reduced pressure. After fractioned distillation, ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate according to formula (III) was obtained as liquid (236 g, 97.7%; eff. 231 g = 1 .02 mol). MS: m / z (%) = 238, 223, 207, 195, 181 , 165, 154, 137, 126, 121 , 109, 98, 95, 79, 67, 57, 41.

[0143] Saponification: 5-lsobutyl-3-methyl-cyclohex-2-en-1-one [compound according to formula

[0144] (IV)1 To a solution of ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate (390 g, 1.59 mmol, 1.0 equiv.) in ethanol (821 g) an aqueous NaOH-solution (2.7 M) was added under slight cooling, keeping the temperature beneath 20°C. Subsequently, the reaction mixture was stirred for 345min at 82°C. After the reaction mixture had cooled down, the solvent was evaporated under reduced pressure. The residue was dissolved in MtBE and water and the layers were separated. The organic layer was washed with saturated aqueous NH4CI-solution, aqueous NaHCOs-solution and aqueous saturated NaCI-solution until neutral. The organic layer was concentrated under reduced pressure and after distillation, the enone according to formula (IV) was obtained as liquid (254 g, 96.9% yield; eff. 246 g = 1 .48 mol). MS: m / z (%) = 166, 151 , 133, 124, 109, 95, 82, 67, 54, 41.

[0145] Reduction: 3-lsobutyl-5-methylcyclohexanol [compound according to formula (Vlll)l

[0146] A solution of 3-isobutyl-5-methylcyclohexanone (30.0 g, 175 mmol) in / PrOH (254 mL) was treated with Ru / C (3 wt-%, 0.90 g) and H2 (5-7 bar) at 75 °C for 3 h. The crude product was purified by simple distillation to give the desired product 3-isobutyl-5-methylcyclohexanol according to formula (VIII) as a colorless liquid (28.5 g, 168 mmol, 96%, mixture of isomers in a ration ~3:2).1H-NMR (400 MHz, CDCh): 6 = 0.43-0.53 (m, 1 ,8H), 0.74-0.94 (m, 19.8H), 0.97-1.13 (m, 6.4H), 1.37-1.51 (m, 3.5H), 1.57-1.85 (m, 8.6H), 1.91-1.97 (m, 1.7H), 3.60 (app. tt, J = 10.9, 4.2 Hz, 0.7H), 4.13 (br. s, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.3,

[0147] 22.6, 22.8, 22.8, 22.8, 23.0, 24.6, 24.8, 26.1 , 28.6, 30.7, 33.3, 39.7, 41.3, 41.6, 42.0, 42.4,

[0148] 44.6, 46.4, 46.8, 67.4, 70.6 ppm. MS: m / z (%) = 152, 137, 123, 111 , 95, 81 , 69, 57, 41 , 29. Odor description: floral, rosy, jasmine, watery.

[0149] Esterification: 3-lsobutyl-5-methylcyclohexyl acetate [compound according to formula (IX) 1

[0150] A mixture of 3-isobutyl-5-methylcyclohexanol (2.45 g, 14.4 mmol), AC2O (2.08 g, 20.1 mmol, 1.4 equiv.), NEts (2.84 mL, 2.06 g, 20.1 mmol, 1.4 equiv.) and / V, / V-dimethyl aminopyridine (0.12 g, 1 .01 mmol, 0.07 equiv.) was stirred for 1 .5 h at ambient temperature. Then, the mixture was treated with MtBE and washed with aqueous HCI solution (2M). The organic layer was washed with aqueous saturated NaHCCh solution und H2O. The solvent was evaporated under reduced pressure and the residue was distilled to give the target compound according to formula (IX) as colorless liquid (2.44 g, 11 .5 mmol, 80%, mixture of isomers in a ratio of about 5:4).1H-NMR (400 MHz, CDCh): 6 = 0.42-0.58 (m, 2H), 0.80- 0.89 (m, 10H), 0.87 (d, J = 6.0 Hz, 5H), 0.92 (d, J = 6.6 Hz, 3H), 0.88-1 .07 (m, 4H), 1 .05- 1.13 (m, 2H), 1 .39-1.60 (m, 1 H), 1.61-1.79 (m, 4H), 1.81-1.89 (m, 2H), 1 .91-1.99 (m, 2H), 2.02 (s, 2H), 2.04 (s, 3H), 4.72 (dddd, J = 1 1 .4 Hz, 4.4 Hz, 1 H), 5.10 (app. p, J = 3.0 Hz, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 21.4, 21.5, 22.2, 22.5, 22.8, 22.8, 22.9, 22.9,

[0151] 24.6, 24.8, 26.8, 29.3, 30.5, 33.1 , 36.5, 38.3, 38.5, 40.4, 41.2, 41 .6, 46.4, 46.6, 70.7, 73.1 , 170.6, 170.7 ppm. MS: m / z (%) = 213, 169, 152, 137, 109, 95, 81 , 67, 55, 43, 29. Odor description: floral, jasminic, tea.

[0152] Example 6: 3-Hexyl-5-methylcvclohexyl acetate fcompound according to formula (IX)1

[0153] Haqemannester synthesis: Ethyl-3-methyl-5-oxo-1 ,2,5,6-tetrahydro-[1 ,1 '-biphenyl1-2- carboxylate [compound according to formula (111)1

[0154] The Hagemannester synthesis was performed onto benzaldehyde according to formula (II) in accordance with the general procedure above to give the title compound as liquid. MS: m / z (%) = 258, 230, 212, 185, 154, 126, 98, 77, 65, 53, 29.

[0155] Saponification: 5-methyl-1 ,6-dihydro-[1 ,1 '-biphenyl1-3(2H)-one [compound according to formula (IV)1

[0156] The saponification was performed onto Ethyl-3-methyl-5-oxo-1 ,2,5,6-tetrahydro-[1 ,T- biphenyl]-2-carboxylate according to formula (III) in accordance with the general procedure above to give the title compound as liquid.1H-NMR (400 MHz, CDCh): 6 = 1 .09 (d, J = 6.2 Hz, 3H), 1 .49-1.65 (m, 1 H), 1.91-2.13 (m, 3H), 2.38-2.51 (m, 2H), 2.52-2.65 (m, 1 H), 2.97 (tt, J = 12.8, 3.8 Hz, 1 H), 7.18-7.27 (m, 2H), 7.29-7.36 (m, 2H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.4, 33.4, 41.7, 43.8, 48.4, 49.5, 126.5, 126.7, 128.7, 144.3, 210.7 ppm. MS: m / z (%) = 207, 188, 173, 131 , 118, 104, 91 , 78, 56, 41 , 27.

[0157] Reduction: 3-Hexyl-5-methylcyclohexanol [compound according to formula (Vlll)l

[0158] The reduction was performed according with the general procedure above to give the title compound as colourless liquid (8.98 g, 45.3 mmol).1H-NMR (400 MHz, CDCh): 5 = 0.49 (dd, J = 12.1 Hz, 1 H), 0.70-0.85 (m, 2H), 0.85-0.90 (m, 3H), 0.93 (d, J = 6.6 Hz, 3H), 1.12- 1.34 (m, 1 H), 1.34-1.53 (m, 1 H), 1.54-1.69 (m, 1 H), 1.90-2.04 (m, 2H), 3.60 (app. tt, J =

[0159] 10.9, 4.3 Hz, 1 H), 4.21 (br. s, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 14.1 , 22.3, 22.7,

[0160] 26.9, 29.6, 30.7, 31 .9, 35.7, 36.9, 41.1 , 42.2, 44.6, 70.7 ppm. MS: m / z (%) = 197, 180, 165, 152, 139, 123, 110, 95, 82, 69, 57, 41 , 29. Odor description: floral, creamy, rosy.

[0161] Esterification: 3-Hexyl-5-methylcyclohexyl acetate [compound according to formula (IX)1

[0162] The esterification of 3-hexyl-5-methylcyclohexanol (1.51 g, 7.56 mmol) according to formula (VIII) was performed in accordance with the general procedure above to give 3- hexyl-5-methylcyclohexyl acetate according to formula (IX) as colourless liquid (1.52 g, 6.32 mmol, 84%, mixture of isomers).1H-NMR (400 MHz, CDCh): 6 = 0.48-0.56 (m, 1.2H), 0.85-0.94 (m, 9.5H), 1.19-1.31 (m, 13H), 1.35-1.42 (m, 1.2H), 1.45-1.55 (m, 1.2H), 1.60- 1 .69 (m, 1 H), 1 .70-1 .73 (m, 0.4H), 1 .81-1 .89 (m, 0.4H), 1 .90-2.00 (m, 2H), 4.71 (tt, J = 11 .4, 4.4 Hz, 1 H), 5.08-5.11 (m, 0.2H) ppm.13C-NMR (101 MHz, CDCh): 6 = 14.1 , 21.5, 22.2, 22.7, 26.8, 29.6, 30.6, 31.9, 35.6, 36.9, 38.1 , 40.4, 41.0, 73.2, 170.7 ppm. MS: m / z (%) = 207, 180, 165, 152, 137, 124, 110, 95, 82, 68, 55, 43, 29. Odor description: floral, green, fatty, slightly aldehydic, ozonic.

[0163] Example 7: 3-lsobutyl-5-methylcvclohexyl-3-methylbut-2-enoate fcompound according to formula (IX)1

[0164] Haqemannester synthesis: Ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate [compound according to formula (lll)1

[0165] To a solution of ethyl acetoacetate (438 g, 3.33 mmol, 2.5 equiv.) and isovaleraldehyde (117 g, 1.33 mmol, 1.0 equiv.) according to formula (II) a solution of piperidine (11.5 g, 0.133 mmol, 104 Mol-%) in ethanol was added dropwise at 24-43°C over 40 min. Afterwards, the reaction mixture was heated under reflux at 70°C for 255min. After cooling to ambient temperature water (350 mL) was added to the reaction mixture and the layers were separated. The aqueous layer was extracted with MtBE (2 x 250 mL) and the combined organic layers were concentrated under reduced pressure. After fractioned distillation, Ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate according to formula

[0166] (III) was obtained as liquid (236 g, 97.7%; eff. 231 g = 1 .02 mol). MS: m / z (%) = 238, 223, 207, 195, 181 , 165, 154, 137, 126, 121 , 109, 98, 95, 79, 67, 57, 41.

[0167] Saponification: 5-lsobutyl-3-methyl-cyclohex-2-en-1-one [compound according to formula

[0168] (IV)1

[0169] To a solution of ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate (390 g, 1.59 mmol, 1.0 equiv.) in ethanol (821 g) an aqueous NaOH-solution (2.7 M) was added under slight cooling, keeping the temperature beneath 20°C. Subsequently, the reaction mixture was stirred for 345min at 82°C. After the reaction mixture had cooled down, the solvent was evaporated under reduced pressure. The residue was dissolved in MtBE and water and the layers were separated. The organic layer was washed with saturated aqueous NH4CI-solution, aqueous NaHCCh-solution and aqueous saturated NaCI-solution until neutral. The organic layer was concentrated under reduced pressure and after distillation, the enone according to formula (IV) was obtained as liquid (254 g, 96.9% yield; eff. 246 g = 1.48 mol). MS: m / z (%) = 166, 151 , 133, 124, 109, 95, 82, 67, 54, 41. Reduction: 3-lsobutyl-5-methylcyclohexanol [compound according to formula (Vlll)l

[0170] A solution of 3-isobutyl-5-methylcyclohexanone (30.0 g, 175 mmol) in / PrOH (254 mL) was treated with Ru / C (3 wt-%, 0.90 g) and H2 (5-7 bar) at 75°C for 3 h. The crude product was purified by simple distillation to give the desired product 3-isobutyl-5-methylcyclohexanol according to formula (VI 11) as a colorless liquid (28.5 g, 168 mmol, 96%, mixture of isomers in a ration ~3:2).1H-NMR (400 MHz, CDCh): 6 = 0.43-0.53 (m, 1 ,8H), 0.74-0.94 (m, 19.8H), 0.97-1.13 (m, 6.4H), 1.37-1.51 (m, 3.5H), 1.57-1.85 (m, 8.6H), 1.91-1.97 (m, 1.7H), 3.60 (app. tt, J = 10.9, 4.2 Hz, 0.7H), 4.13 (br. s, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.3,

[0171] 22.6, 22.8, 22.8, 22.8, 23.0, 24.6, 24.8, 26.1 , 28.6, 30.7, 33.3, 39.7, 41.3, 41.6, 42.0, 42.4,

[0172] 44.6, 46.4, 46.8, 67.4, 70.6 ppm. MS: m / z (%) = 152, 137, 123, 111 , 95, 81 , 69, 57, 41 , 29. Odor description: floral, rosy, jasmine, watery.

[0173] Esterification: 3-lsobutyl-5-methylcyclohexyl-3-methylbut-2-enoate [compound according to formula (IX)1

[0174] The esterification of 3-isobutyl-5-methylcyclohexanol (3.00 g, 17.5 mmol) was performed in accordance with the general procedure above to give 3-isobutyl-5-methylcyclohexyl-3- methylbut-2-enoate according to formula (IX) as a colorless liquid (2.45 g, 9.70 mmol, 55%, mixture of isomers in a ratio of ~1 :0.7).1H-NMR (400 MHz, CDCh): 5 = 0.45-0.58 (m, 1 ,7H), 0.78-0.89 (m, 7H), 0.87 (d, J = 7.2 Hz, 7H), 0.91-0.95 (m, 2H), 0.89-1.19 (m, 7H), 1.41-1.60 (m, 1 H), 1 .60-1.81 (m, 6H), 1.81-1.93 (m, 7H), 1.93-2.02 (m, 2H), 2.10-2.23 (m, 5H), 4.76 (app. tt, J = 11.30, 4.30 Hz, 0.7H), 5.11-5.18 (m, 1 H), 5.64 (br. s, 0.7H), 5.68 (br. s, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 20.2 (3x), 22.5, 22.8, 22.9, 24.6, 24.8, 27.0, 27.4 (2x), 29.5, 30.6, 33.2, 36.7, 38.5, 38.6, 40.6, 41 .3, 41 .7, 46.5, 46.7, 69.7, 72.1 , 116.6, 117.0, 155.5, 156.0, 166.3 (2x) ppm. MS: m / z (%) = 281 , 234, 195, 153, 137, 111 , 97, 83, 69, 55, 41 , 29. Odor description: weakly floral

[0175] Example 8: 1-lsobutyl-3-methoxy-5-methylcyclohexane [compound according to formula (IX)1

[0176] Haqemannester synthesis: Ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate [compound according to formula (lll)1

[0177] To a solution of ethyl acetoacetate (438 g, 3.33 mmol, 2.5 equiv.) and isovaleraldehyde (117 g, 1.33 mmol, 1.0 equiv.) according to formula (II) a solution of piperidine (11.5 g, 0.133 mmol, 104 Mol-%) in ethanol was added dropwise at 24-43°C over 40 min. Afterwards, the reaction mixture was heated under reflux at 70°C for 255min. After cooling to ambient temperature water (350 mL) was added to the reaction mixture and the layers were separated. The aqueous layer was extracted with MtBE (2 x 250 mL) and the combined organic layers were concentrated under reduced pressure. After fractioned distillation, ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate according to formula

[0178] (III) was obtained as liquid (236 g, 97.7%; eff. 231 g = 1 .02 mol). MS: m / z (%) = 238, 223, 207, 195, 181 , 165, 154, 137, 126, 121 , 109, 98, 95, 79, 67, 57, 41.

[0179] Saponification: 5-lsobutyl-3-methyl-cyclohex-2-en-1-one [compound according to formula

[0180] (IV)1

[0181] To a solution of ethyl-2-isobutyl-5-methyl-4-oxo-cyclohexanecarboxylate (390 g, 1.59 mmol, 1.0 equiv.) in ethanol (821 g) an aqueous NaOH-solution (2.7 M) was added under slight cooling, keeping the temperature beneath 20°C. Subsequently, the reaction mixture was stirred for 345min at 82°C. After the reaction mixture had cooled down, the solvent was evaporated under reduced pressure. The residue was dissolved in MtBE and water and the layers were separated. The organic layer was washed with saturated aqueous NH4CI-solution, aqueous NaHCOs-solution and aqueous saturated NaCI-solution until neutral. The organic layer was concentrated under reduced pressure and after distillation, the enone according to formula (IV) was obtained as liquid (254 g, 96.9% yield; eff. 246 g = 1.48 mol). MS: m / z (%) = 166, 151 , 133, 124, 109, 95, 82, 67, 54, 41.

[0182] Reduction: 3-lsobutyl-5-methylcyclohexanol [compound according to formula (Vlll)l

[0183] A solution of 3-isobutyl-5-methylcyclohexanone (30.0 g, 175 mmol) in / PrOH (254 mL) was treated with Ru / C (3 wt-%, 0.90 g) and H2 (5-7 bar) at 75°C for 3 h. The crude product was purified by simple distillation to give the desired product 3-isobutyl-5-methylcyclohexanol according to formula (VI 11) as a colorless liquid (28.5 g, 168 mmol, 96%, mixture of isomers in a ration ~3:2).1H-NMR (400 MHz, CDCh): 6 = 0.43-0.53 (m, 1 ,8H), 0.74-0.94 (m, 19.8H), 0.97-1.13 (m, 6.4H), 1.37-1.51 (m, 3.5H), 1.57-1.85 (m, 8.6H), 1.91-1.97 (m, 1.7H), 3.60 (app. tt, J = 10.9, 4.2 Hz, 0.7H), 4.13 (br. s, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.3,

[0184] 22.6, 22.8, 22.8, 22.8, 23.0, 24.6, 24.8, 26.1 , 28.6, 30.7, 33.3, 39.7, 41.3, 41.6, 42.0, 42.4,

[0185] 44.6, 46.4, 46.8, 67.4, 70.6 ppm. MS: m / z (%) = 152, 137, 123, 111 , 95, 81 , 69, 57, 41 , 29. Odor description: floral, rosy, jasmine, watery.

[0186] Etherification: 1-lsobutyl-3-methoxy-5-methylcyclohexane [compound according to formula (IX)1

[0187] The etherification of 3-isobutyl-5-methylcyclohexanol (2.50 g, 14.6 mmol) was performed upon treatment with NaH (60% in mineral oil, 1.2 equiv.) and methyl iodide (2.0 equiv.) to give the title compound as a colorless liquid (1 .53 g, 8.30 mmol, 57%, mixture of isomers).1H-NMR (400 MHz, CDCh): 6 = 0.42-0.55 (m, 2H), 0.63-0.83 (m, 2H), 0.86 (dt, J = 6.5, 1.1 Hz, 16H), 0.90-0.96 (m, 4H), 1.01 (dd, J = 7.1 Hz, 2H), 1 .09 (td, J = 7.1 , 2.2 Hz, 2H), 1.30- 1 .45 (m, 2H), 1 .55-1 .80 (m, 6H), 1 .85-1 .95 (m, 2H), 1 .98-2.05 (m, 2H), 3.14 (tt, J = 1 1 .1 , 4.1 Hz, 1 H), 3.30 (s, 3H), 3.35 (s, 3H), 3.52 (app. p, J = 2.9 Hz, 1 H) ppm.13C-NMR (101 MHz, CDCh): 6 = 22.4, 22.7, 22.8, 22.9, 23.1 , 24.7, 24.8, 26.4, 28.9, 30.6, 33.2, 36.1 , 38.4, 38.6, 40.7, 41.6, 42.0, 46.6, 47.0, 55.6, 55.8, 76.2, 79.3 ppm. MS: m / z (%) = 183, 169, 152, 137, 127, 109, 95, 85, 81 , 71 , 58, 55, 41 , 29. Odor description: fruity, green, apple, pear.

[0188] 3) Perfume compositions

[0189] Example 9: Perfume compositions 1 to 5 A perfumery base oil was prepared with the following ingredients:

[0190] Then, the effect of newly invented compounds was tested in this formula (in parts):

[0191] 1*: not according to the invention

[0192] The fragrance composition 1 gives a fresh green tea accord. Formula 2 pushes the green elements in the fragrance, makes it more fuzzy and citrus like. The formula 3 develops a softer, muskier note in the fragrance, in comparison to base 1 . Formula 4 is softer, creamier and rounder than formula 1. Formula 5 makes the fragrance also softer, rounder, more floral, and in addition muskier facets appear.

Claims

Claims1 . Compound according to formula (I)(I), wherein Ri is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2 is selected from the group consisting of methyl group, allyl group and the following groups:and wherein R3 is H, or wherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2 and Rs are H, orwherein R1 is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, and wherein R2 is H, and wherein R3 is selected from the group consisting of methyl, isopentyl, butyl, C(=O)CH3, C(=O)CH=C(CH3)2 and C(=O)OCH2CH3group, and wherein if R1 is isopropyl and R2 is 2-ethyl-1-3-dioxolane R3 is not H, and wherein if R1 is 1 , 4,5,5, -tetramethylcyclopent-1-en and R2 is H R3 is not H.

2. Compound according to claim 1 , wherein R1 is isobutyl, R2 is methyl and / or R3 is H,or Ri is ethyl, R2 is the following group: , and / or R3 is H, or R1 is ethyl, R2 is allyl and / or Ra is H, or R1 is ethyl, R2 is H and / or R3 is H, or R1 is butyl, R2 is H and / or R3 is H, or R1 is hexyl, R2 is H and / or R3 is H, or R1 is phenylethyl, R2 is H and / or R3 is H, or R1 is isobutyl, R2 is H and / or R3 is H, or R1 is isopropyl, R2 is H and / or R3 is C(=O)CH3,or Ri is isobutyl, R2 is H and / or Ra is C(=O)CH3, or Ri is hexyl, R2 is H and / or Ra is C(=O)CH3, or Ri is phenyl, R2 is methyl and / or R3 is H, or Ri is isobutyl, R2 is methyl and / or R3 is H, or Ri is isobutyl, R2 is H and / or R3 is C(=O)CH=C(CH3)2.

3. Method for producing a compound of formula (I) according to claim 1 or 2, comprising or consisting of the following steps:(a) reacting a compound according to formula (II)(II), wherein Ri is selected from the group consisting of H and linear, branched or cyclic C2-C6 alkyl or aryl groups, preferably from the group consisting of H, ethyl, propyl, isopropyl, butyl, isobutyl, te / Y-butyl, pentyl, 3-pentyl, hexyl, cyclohexyl, phenyl, phenylethyl, furyl and 1 , 4,5,5, -tetramethylcyclopent-1-en group, with ethyl acetoacetate to obtain a compound according to formula (III)(HI), with Ri as defined above,(b) performing a saponification and subsequent decarboxylation reaction with the compound of formula (III) obtained in step (a) to obtain a compound according to formula (IV)O A K1(IV), with Ri as defined above, and(c) performing a reduction reaction with the compound of formula (IV) obtained in step (b) to obtain a compound according to formula (VIII)(VIII), with Ri as defined above, or(d) performing a hydrogenation reaction with the compound of formula (IV) obtained in step (b) to obtain a compound according to formula (V)K1(V),with Ri as defined above, and(e) reacting the compound according to formula (V) obtained in step (d) with a compound according to formula (VI) R2MgX(VI), wherein X is bromine or chlorine and R2 is selected from the group consisting of methyl group, allyl group and the following groups:to obtain a compound according to formula (VII)(VII), with R1 and R2 as defined above, or(f) performing a reduction reaction with the compound of formula (V) obtained in step (d) to obtain a compound according to formula (VIII)with Ri as defined above, and optionally, subsequent to step (c) or (f), if present,(g) performing an ether- / esterification reaction with the compound of formula (VIII) obtained in step (c) or (f) to obtain a compound according to formula (IX)(IX), with Ri as defined above, and wherein R3 is selected from the group consisting of methyl, isopentyl, butyl, C(=O)CH3, C(=O)CH=C(CH3)2and C(=O)OCH2CH3group.

4. Method according to claim 3, wherein performing an ether- / esterification reaction in step (g) is performed by reacting the compound of formula (VIII) obtained in step (f) with a compound selected from the group consisting of alkyl halide, acid anhydride, unsaturated acid and dialkylcarbonate, preferably with a compound selected from the group consisting of methyl iodide, butyl bromide, 3-methylbut-2-enoic acid, and diethylcarbonate.

5. Fragrance composition comprising or consisting of one or more compound(s) of formula (I) as defined in claim 1 or 2, and one, two three, four, five, six, seven, eight, nine, ten or more further frag rance(s), preferably selected from the group consisting ofi) essential oils and extracts, preferably bergamot oil, coriander oil, galbanum oil, jasmine absolute, lemon oil, limette oil, neroli oil, oak moss absolute, patchouli oil, petitgrain oil, rose oil, woody oil or ylang-ylang oil, ii) alcohols, preferably citronellol, linalool, tetrahydrolinalool, dihydromyrcenol, tetrahydromyrcenol, [(E)-3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pent- 4-en-2-ol], eugenol, geraniol, {[(1R,2S)-1-methyl-2-{[(1R,3S,5S)-1 ,2,2- trimethyl-3-bicyclo[3.1 .0]hexanyl]methyl}-cyclopropyl]-methanol}, phenethyl alcohol, [3-methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pentan-2-ol], terpineol, nopol, benzyl alcohol, 9-decen-1-ol, 3-isocamphylcyclohexanol, cis- 3-hexenol, or [1-(2,2,6-trimethylcyclohexyl)hexan-3-ol], iii) aldehydes and ketones, preferably a-amylcinnamaldehyde, a-hexylcinnamaldehyde, decanal, (methyl 3-oxo-2- pentylcyclopentaneacetate), {3-[(4R)-4-(propan-2-yl)cyclohex-1-en-1- yl]propanal}, product mixture resulting from the cyclization of myrcene with (3E)-3-methylpent-3-en-2-one giving [1-(1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8- tetramethyl-2-naphthyl)ethan-1-one and 1-(1 ,2,3,4,6,7,8,8a-octahydro- 2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one and 1-(1 ,2,3,5,6,7,8,8a- octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one], [E-3-methyl-4-(2,6,6- trimethylcyclohex-2-en-1-yl)but-3-en-2-one], 2-methyl-3-(p- isopropylphenyl)propanal (Cyclamen aldehyde), ionones, methylionone, irones, hydroxy citronellal, muscenone, heliotropin, or vanillin, iv) ether and acetals, preferably {(1R,3S,7R,8 / ?,10 / ?,13 / ?)-5,5,7,9,9,13-Hexamethyl-4,6-dioxatetrayclo[6.5.1 .0(1 ,10).0(3,7)]-tetradecane}, {[3aR-(3aa,5ap,9aa,9bp)]-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan}, geranyl methyl ether, (2,4-dimethyl-4,4a,5,9b-tetrahydroindeno[1 ,2-d]-1 ,3- dioxin), rose oxide, diphenyl oxide, or {spiro[1 ,3-dioxolane-2,5’-(4’,4’,8’,8’- tetramethyl-hexahydro-3’,9’-methanonaphthalene)]}, v) esters and lactones, preferably Ambrettolide, benzyl acetate, benzyl salicylate, coumarin, y-decalactone, ethylene brassylate, {2-[(1R)-1-[(1R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-[(1 S)-1 -[(1 R)-3,3- dimethylcyclohexyl]ethoxy]-2-oxoethyl propanoate; 2-oxo-2-{[(1 S,2S)-2,6,6- trimethylcycloheptyl]oxy}ethyl propanoate}, Macrolide, an isomeric mixture of diethyl 2-methylfumarate and diethyl 2-methylmaleate and diethyl 2- methylenesuccinate, ethyl tetrahydrofuran-2-carboxylate, geranyl acetate, linalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, y-undecalactone,terpinyl acetate, nopyl acetate, p-tertbutylcyclohexyl acetate, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, isononyl acetate, tricyclodecenyl acetate, 4-acetoxy-3-pentyl-tetrahydropyran, or vetiveryl acetate, vi) heterocycles, preferably galbazine, indol, or isobutylquinoline.

6. Fragrance composition according to claim 5, wherein the weight ratio of the total amount of compound(s) of formula (I) to the total weight of further fragrance(s) is in a range of from 0.01 % to 20%, preferably of from 0.1 % to 10%.

7. Fragrance composition according to claim 5 or 6, comprising 3-isobutyl-1 ,5- dimethylcyclohexan-1-ol and / or 3-ethyl-5-methylcyclohexan-1-ol.

8. Fragrance composition according to any one of the claims 5 to 7, wherein the total amount of compound(s) of formula (I) in the fragrance composition is present in a sensorically effective amount, preferably in an amount sufficient for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

9. Fragrance composition according to any one of the claims 5 to 8, wherein the or, respectively, one, several or all of the further fragrances (also) impart, modify and / or enhance one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

10. Perfumed product, comprising or consisting of(i) a fragrance composition according to any one of the claims 5 to 9, or one or more compounds of formula (I) according to claim 1 or 2,and(ii) one or more further components), preferably at least one or more, preferably one, two, three, four, five, or more additives, excipients and / or active substance(s).

11. Perfumed product according to claim 10, wherein the product is selected from the group consisting of washing and cleaning agents, hygiene or care products, preferably in the field of body and hair care, cosmetics and home care, preferably selected from the group consisting of perfume extraits, eau de parfums, eau de toilettes, aftershaves, eau de colognes, pre-shave-products, splash-colognes, perfumed refreshing tissues, acid, alkaline or neutral cleaning agents, textile refreshing agents, ironing aids, liquid washing agents, washing agents in powder form, laundry pretreatment agents, fabric softeners, laundry soap, laundry tablets, disinfectants, surface disinfectants, air refreshers, aerosols, waxes and polishes, body care agents, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair-care products deodorants, anti-perspirants, products of decorative cosmetics, candles, lamp oils, joss sticks, insecticides, repellents and propellants.

12. Perfumed product according to claim 10 or 11 , wherein component (i) is present in a sensorically effective amount, preferably in an amount sufficient for that a consumer perceives one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note and / or for enhancing leathery impressions and / or for pushing ambery notes.

13. Perfumed product according to any one of the claims 10 to 12, wherein the total amount of compound(s) of formula (I), related to the total amount of the perfumed product, is in a range of from 0.0006 to 1 .3 wt.-%, preferably 0.001 to 7 wt.-%.

14. Use of a compound according to claim 1 or 2, or of a fragrance composition according to any one of the claims 5 to 9 as fragrance.

15. Use according to claim 14, for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, citrus, woody, fruity, metallic, smoky, leathery, gujac, aromatic, musky, creamy, fuzzy, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesianote and / or for enhancing leathery impressions and / or for pushing ambery notes, preferably use of 3-isobutyl-1 ,5-dimethylcyclohexanol and / or 3-ethyl-5- methylcyclohexan-1-ol, or of a fragrance composition according to any one of the claims 5 to 9 comprising 3-isobutyl-1 ,5-dimethylcyclohexanol and / or 3-ethyl-5- methylcyclohexan-1-ol for imparting, modifying and / or enhancing one or more scents selected from the group consisting of the scents floral, freesia, citrus, rossitol, and / or for enhancing the volume of the floral scent and / or for emphasizing a greener freesia note, and / or for enhancing leathery impressions and / or for pushing ambery notes.

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