Organic compounds

Abstract

Disclosed are compounds of formula (I) wherein R1 is selected from H, Me, Et, OMe; R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CH2OMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond possessing powerful spicy woody notes.

Description

[0001] ORGANIC COMPOUNDS

[0002] TECHNICAL FIELD

[0003] The present invention is concerned with flavor and fragrance ingredients, and to compositions containing them that are useful in flavor and fragrance applications. It furthermore relates to a method of making them. In particular, the present invention is concerned with 3-alkylcyclopent- 2-en-1-one derivatives of formula (I) possessing powerful spicy woody notes.

[0004] BACKGROUND

[0005] In the flavor and fragrance industry, perfumers and flavorists are continually looking for new compounds possessing unique olfactory properties. For example, there is a need for ingredients that are suitable for the flavor and fragrance industry possessing spicy, woody notes. Woody and spicy notes are fundamental olfactive families as for instance jasmine and floral. They can not only be a key character of a perfume, but also support and complement perfume accords in general.

[0006] Surprisingly inventors found a new class of ingredients of formula (I) as defined herein below possessing the highly sought-after spicy woody notes. This new class of ingredients supports and nurtures, in particular spicy woody fragrance accords.

[0007] SUMMARY

[0008] In accordance with a first aspect of the present invention there is provided a compound of formula (I) in the form of any one of its stereoisomers or mixture thereof wherein

[0009] Ri is selected from H, Me, Et, OMe;

[0010] R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CH2OMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond.

[0011] In accordance with a second aspect of the present invention there is provided a fragrance or flavor composition comprising a compound of formula (I) as described above.

[0012] In accordance with a third aspect of the present invention there is provided a fragranced article comprising as odorant a compound of formula (I) as described above. In accordance with a fourth aspect of the present invention there is provided a method of improving, enhancing and / or modifying a consumer product base or consumable product base by means of adding thereto an olfactory acceptable amount of a compound of formula (I) as described above.

[0013] In accordance with a fifth aspect of the present invention there is provided a flavored product comprising a compound of formula (I) as described above.

[0014] In accordance with a sixth aspect of the present invention there is provided the use of a compound of formula (I) as described above as flavor or fragrance.

[0015] Certain embodiments of any aspect of the present invention may provide one or more of the following advantages:

[0016] • provision of novel flavor and fragrance compounds with spicy, woody notes,

[0017] • provision of a highly performing compound with low odor threshold.

[0018] The details, examples and preferences provided in relation to any particular one or more of the stated aspects of the present invention will be further described herein and apply equally to all aspects of the present invention. Any combination of the embodiments, examples and preferences described herein in all possible variations thereof is encompassed by the present invention unless otherwise indicated herein, or otherwise clearly contradicted by context.

[0019] DETAILED DESCRIPTION

[0020] The present invention is based on the surprising finding that 3-alkylcyclopent-2-en-1-one derivatives as defined herein possess powerful spicy woody notes.

[0021] In a first aspect of the invention, there is provided a compound of formula (I) in the form of any one of its stereoisomers or mixture thereof wherein

[0022] Ri is selected from H, Me, Et, OMe;

[0023] R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CH2OMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond.

[0024] In one particular embodiment the compound of formula (I) is a compound wherein R1 is H. In one particular embodiment the compound of formula (I) is a compound wherein R1 is H and R2 is methyl.

[0025] In one particular embodiment the compound of formula (I) is a compound wherein Ri is OMe and R2 is methyl.

[0026] In one particular embodiment the compound of formula (I) is a compound wherein the dotted line together with the carbon-carbon bond forms a double bond.

[0027] In another particular embodiment the compounds of formula (I) is selected from the group consisting of 2-(3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2-ethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- (allyloxy)ethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- methoxypropyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- hydroxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one and 2-(3-(2,2- dimethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one.

[0028] The compounds according to the present invention comprise one or more chiral centres and as such may exist as a mixture of stereoisomers, or they may be resolved as isomerically pure forms. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective synthesis.

[0029] As one specific example one may cite 2-(3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3- methylcyclopent-2-en-1-one (compound of formula (V) which is an example of the compound of formula (I)) comprising two stereogenic centers, and thus, the compound may exist as a mixture of up to four stereoisomers ((Va) to (Vd) as shown below), in its diastereomerically pure or even enantiomerically pure forms. Some of the individual isomers have different odor qualities, both in terms of performance as well as olfactory properties.

[0030] For example, one may cite 2-((1 S,3F?)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3- methylcyclopent-2-en-1-one (Va), 2-((1 F?,3S)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3- methylcyclopent-2-en-1-one (Vb), 2-((1 S,3S)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3- methylcyclopent-2-en-1-one (vc), and 2-((1 fl,3 / ^-3-(2-methoxyethyl)-2,2- dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one (Vd).

[0031] Thus there is provided in another embodiment a compound of formula (la) with a relative configuration at the cyclopropyl of (1 S,3R) as shown by formula (la) wherein

[0032] Ri is selected from H, Me, Et, OMe;

[0033] R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CH2OMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond.

[0034] For example, the compound of formula (la) can be obtained from (+)-A3-carene ((+)-3,7,7- trimethylbicyclo[4.1.0]hept-3-ene) as starting material, which is also available from renewable resources.

[0035] For example, there is provided a compound of formula (la) selected from the group consisting of 2-((1 S,3F?)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2- ((1 S,3F?)-3-(2-ethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2- ((1 S,3F?)-3-(2-(allyloxy)ethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2- ((1 S,3 ?)-3-(2-methoxypropyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2- ((1 S,3 ?)-3-(2-hydroxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one and 2- ((1 S,3 ?)-3-(2,2-dimethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one.

[0036] As used herein Ci - C4 alkyl means methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, and C2 - C4 alkenyl means a residue comprising at least one double bond such as 2-methylprop-1-en-1-yl, prop-1-en-1-yl, vinyl, but-1-en-1-yl, but-2-en-1-yl, but-3-en-1- yl, and buta-1 ,3-dien-1-yl.

[0037] The compounds of formula (I) (which encompasses compounds of formula (la)) may be used alone, as isomeric mixture thereof, or in combination with known odorant molecules selected from the extensive range of natural products, and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and / or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, for example, carrier materials, and other auxiliary agents commonly used in the art.

[0038] As used herein, "carrier material" means a material which is practically neutral from a odorant point of view, i.e. a material that does not significantly alter the organoleptic properties of odorants.

[0039] The term “auxiliary agent" refers to ingredients that might be employed in a fragrance composition for reasons not specifically related to the olfactive performance of said composition. For example, an auxiliary agent may be an ingredient that acts as an aid to processing a fragrance ingredient or ingredients, or a composition containing said ingredient(s), or it may improve handling or storage of a fragrance ingredient or composition containing same. It might also be an ingredient that provides additional benefits such as imparting color or texture. It might also be an ingredient that imparts light resistance or chemical stability to one or more ingredients contained in a fragrance composition. A detailed description of the nature and type of adjuvants commonly used in fragrance compositions containing same cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.

[0040] As used herein, ‘fragrance composition’ means any composition comprising a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof and a base material, e.g. a diluent conventionally used in conjunction with odorants, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (I PM), pentane-1 ,2-diol, triethyl citrate (TEC) and alcohol (e.g. ethanol). Optionally, the composition may comprise an antioxidant adjuvant. Said anti-oxidant may be selected from Tinogard® TT (BASF), Tinogard® Q (BASF), Tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78- 2), 2,6-bis(1 ,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) and related phenols, hydroquinones (CAS 121-31-9).

[0041] The following list comprises examples of known odorant molecules, which may be combined with a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof:

[0042] - essential oils and extracts, e.g. castoreum, costus root oil, oak moss absolute, geranium oil, tree moss absolute, basil oil, fruit oils, such as bergamot oil and mandarine oil, myrtle oil, palmarose oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, gurjun balsam oil, lavender oil and / or ylang-ylang oil;

[0043] - alcohols, e.g. cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol); cis-3-hexenol ((Z)-hex-3- en-1-ol); citronellol (3,7-dimethyloct-6-en-1-ol); dihydro myrcenol (2,6-dimethyloct-7-en-2-ol); Ebanol™ ((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); eugenol (4-allyl- 2-methoxyphenol); ethyl linalool ((E)-3,7-dimethylnona-1,6-dien-3-ol); farnesol ((2E,6Z)- 3,7,11-trimethyldodeca-2,6,10-trien-1-ol); geraniol ((E)-3,7-dimethylocta-2,6-dien-1-ol); Super Muguet™ ((E)-6-ethyl-3-methyloct-6-en-1-ol); linalool (3,7-dimethylocta-1,6-dien-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2,6-octadien-1-ol); phenyl ethyl alcohol (2-phenylethanol); Rhodinol™ (3,7-dimethyloct-6-en-1-ol); Sandalore™ (3- methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3- en-1-yl)propan-2-ol); or Timberol™ (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7- trimethylocta-2,6-dien-1-ol, and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]-methanol;

[0044] - aldehydes and ketones, e.g. anisaldehyde (4-methoxybenzaldehyde); alpha amyl cinnamic aldehyde (2-benzylideneheptanal); Georgywood™ (1-(1,2,8,8-tetramethyl- 1 ,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); Hydroxycitronellal (7-hydroxy-3,7- dimethyloctanal); Iso E Super® (1-(2,3,8,8-tetramethyl-1 ,2,3,4,5,6,7,8-octahydronaphthalen- 2-yl)ethanone); Isoraldeine® ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2- one); Hedione™ (methyl 3-oxo-2-pentylcyclopentaneacetate); 3-(4-isobutyl-2- methylphenyl)propanal; maltol; methyl cedryl ketone; methylionone; verbenone; and / or vanillin;

[0045] - ether and acetals, e.g. Ambrox® (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro- 1H-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta-2,6- diene); and / or Spirambrene® (2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'- [1 ,3]dioxane]) ;

[0046] - esters and lactones, e.g. benzyl acetate; cedryl acetate ((1 S,6R,8aR)-1 , 4,4,6- tetramethyloctahydro-1H-5,8a-methanoazulen-6-yl acetate); delta-decalactone (6- pentyltetrahydro-2H-pyran-2-one); Helvetolide® (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2- methylpropyl propionate); delta-undecalactone (5-heptyloxolan-2-one); and I or vetiveryl acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1 H-azulen-6-yl) acetate);

[0047] - macrocycles, e.g. Ambrettolide ((Z)-oxacycloheptadec-10-en-2-one); ethylene brassylate (1,4-dioxacycloheptadecane-5, 17-dione); and I or Exaltolide® (16- oxacyclohexadecan-1-one); and

[0048] - heterocycles, e.g. isobutylquinoline (2-isobutylquinoline).

[0049] Thus there is provided in a further aspect of the invention a fragrance composition comprising a compound of formula (I) (which encompasses compounds of formula (la)). The compounds of formula (I) (which encompasses compounds of formula (la)) may be used in a broad range of fragranced articles, e.g. in any field of fine and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. The compound can be employed in widely varying amounts, depending upon the specific article and on the nature and quantity of other odorant ingredients. The proportion is typically from 0.00001 to 3 weight per cent of the article. In one embodiment, the compound may be employed in a fabric softener in an amount from 0.0001 to 1 weight per cent (e.g. 0.001 to 0.1 including 0.05 and 0.03 weight %). In another embodiment, the compound may be used in fine perfumery in amounts from 0.00001 to 30 weight per cent (e.g. up to about 10 or up to 20 weight per cent), more preferably between 0.01 and 5 weight per cent (e.g. 0.01 to 0.1 weight per cent). However, these values are given only by way of example, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations.

[0050] In another embodiment the compounds of formula (I) (which encompasses compounds of formula (la)) may be used in a broad range of flavored products including alcoholic and nonalcoholic beverages, e.g. teas, frozen dairy desserts, confectionary and bakery goods, gelatines, puddings, meat and meat products, and tobacco. The compounds of formula (I) (which encompasses compounds of formula (la)) may also be used as for flavour compositions, for example, in grape flavours, plum flavours, dried fruit flavours, red berry flavours such as raspberry, blackberry or gooseberry flavours. They may also be used as flavour enhancers, for example, in pepper, ginger, basil, rosemary, cardamom, nutmeg, cinnamon, peppermint, grape (such as Shiraz grape), juniper and grapefruit flavours.

[0051] When used in flavoured products, the compounds of the present invention may be present in amounts ranging from 0.01 ppb (10'11) to 10 ppb (10'8) by weight based on the consumable product, more preferably from 0.1 ppb (10'1°) to 1 ppb (10'9) by weight. However, these values should not be limiting on the present invention, since the experienced flavourist may also achieve effects or may create novel accords with lower or higher concentrations.

[0052] The compounds of formula (I) (which encompasses compounds of formula (la)) may be employed in a consumer product base simply by directly mixing the compound, or a fragrance composition comprising a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof, with the consumer product base, or it may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base. Thus, the invention additionally provides a method of manufacturing a fragranced article or flavored product, comprising the incorporation a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof as a flavor and / or fragrance ingredient, either by directly admixing to the consumer product base or by admixing a fragrance I flavor composition comprising a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof, which may then be mixed with a consumer product base, using conventional techniques and methods. Through the addition of an olfactory acceptable amount of a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof the odor notes of a consumer product base will be improved, enhanced, or modified.

[0053] Thus, the invention furthermore provides a method for improving, enhancing or modifying a consumer product base by means of the addition thereto of an olfactorily acceptable amount of a compound of formula (I) (which encompasses compounds of formula (la)), or a mixture thereof.

[0054] There is provided in a further aspect of the present invention a fragranced article comprising: a) a compound of formula wherein

[0055] Ri is selected from H, Me, Et, OMe;

[0056] R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CFWMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond, and b) a consumer product base.

[0057] As used herein, ‘consumer product base’ means a composition for use as a consumer product to fulfill specific actions, such as cleaning, softening, and caring or the like. Examples of such products include fine perfumery, e.g. perfume and eau de toilette; fabric care, household products and personal care products such as cosmetics, laundry care detergents, rinse conditioner, personal cleansing composition, detergent for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body-care products, e.g. shampoo, shower gel; air care products (includes products that contain preferably volatile and usually pleasantsmelling compounds which advantageously can even in very small amounts mask unpleasant odors). Air fresheners for living areas contain, in particular, natural and synthetic essential oils such as pine needle oils, citrus oil, eucalyptus oil, lavender oil, and the like, in amounts for example of up to 50% by weight. As aerosols they tend to contain smaller amounts of such essential oils, by way of example less than 5% or less than 2% by weight, but additionally include compounds such as acetaldehyde (in particular, <0.5% by weight), isopropyl alcohol (in particular, <5% by weight), mineral oil (in particular, <5% by weight), and propellants.

[0058] Cosmetic products include:

[0059] (a) cosmetic skincare products, especially bath products, skin washing and cleansing products, skincare products, eye makeup, lip care products, nail care products, intimate care products, foot care products;

[0060] (b) cosmetic products with specific effects, especially sunscreens, tanning products, depigmenting products, deodorants, antiperspirants, hair removers, and shaving products;

[0061] (c) cosmetic dental-care products, especially dental and oral care products, tooth care products, cleaners for dental prostheses, adhesives for dental prostheses; and

[0062] (d) cosmetic hair care products, especially hair shampoos, hair care products, hair setting products, hair-shaping products, and hair coloring products.

[0063] This list of products is given by way of illustration, and is not to be regarded as being in any way limiting.

[0064] In one particular embodiment the consumer product base is selected form fine perfumery, and personal care products, including deodorants, hair care products, soaps, and the like.

[0065] In a further particular embodiment the consumer product base is selected from fabric care products, including fabric softener, and home care products, including air fresheners, dish washers and the like.

[0066] There is provided in a further aspect a flavored product comprising: a) a compound of formula (I) wherein

[0067] Ri is selected from H, Me, Et, OMe;

[0068] R2is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CH2OMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond, and b) a consumable product base.

[0069] As used herein, ‘consumable product base’ means a composition for use as consumable product, such as foodstuff and beverages, or personal care products that are intended to be introduced into the oral cavity of a human or animal and remain there for a certain period of time before being ingested or removed from the mouth. Such products include composition in there processed, partially processed or unprocessed state.

[0070] The compounds of formula (I) (which encompasses compounds of formula (la)) may be synthesized by common steps known to a person skilled in the art.

[0071] The invention is now further described with reference to the following non-limiting examples. These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art.

[0072] EXAMPLES i-3- methylcyclopent-2-en-1-one a) 1-((1S,3R)-3-(2-hydroxyethyl)-2,2-dimethylcyclopropyl)propan-2-ol

[0073] To a stirred solution of 2-((1 R,3S)-2,2-dimethyl-3-(2-oxopropyl)cyclopropyl)acetaldehyde (20 g, 119 mmol, I .O equiv, prepared according to Shi, L. et al., Chem. Commun. 2020, 56, 531) in MeOH (200 mL) was added sodium borohydride (6.75 g, 178 mmol, 1.5 equiv) at -10 °C. The reaction was stirred at room temperature for 6 hours. Upon completion of the reaction as confirmed by TLC, the reaction mixture was quenched with water (50 mL), and methanol was concentrated under reduced pressure. The obtained residue was diluted with ethyl acetate (300 mL), washed with water (75 mL), brine (50 mL). The organic layer was dried over sodium sulfate, filtered and concentrated to afford crude 1-((1S,3R)-3-(2-hydroxyethyl)-2,2- dimethylcyclopropyl)propan-2-ol (15.2 g, 74% yield), which was used for the next step without further purification. b) 1-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)propan-2-ol

[0074] To a 1 L autoclave reactor containing a stirred solution of 1-((1S,3R)-3-(2-hydroxyethyl)-2,2- dimethylcyclopropyl)propan-2-ol (15.0 g, 87 mmol, I .O equiv) in THF (150 mL) was added silver(l) oxide (60.5 g, 261 mmol, 3.0 equiv) and stirred for 15 min at room temperature, lodomethane (150 mL, 2.41 mol, 28 equiv) was added to the reaction mixture. After stirring for 40 hours at room temperature, the reaction mixture was filtered over celite, washed with ethyl acetate (200 mL) and concentrated under reduced pressure. The crude was purified by column chromatography (silica gel, eluting with 0-15% ethyl acetate in petroleum ether) to afford 1- ((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)propan-2-ol (9.6 g, 59% yield).

[0075] 1H-NMR (400 MHz, DMSO-d6, 5 / ppm): 4.35 (d, J = 4.4 Hz, 1 H), 3.63-3.56 (m, 1 H), 3.40 - 3.34 (m, 2H), 3.23 (s, 3H), 1.44 - 1.39 (m, 2H), 1.35 - 1.12 (m, 2H), 1.05 (dd, J = 7.2, 1.2 Hz, 3H), 1.00 (d, J = 2 Hz, 3H), 0.88 (d, J = 2 Hz, 3H), 0.55 - 0.39 (m, 2H). c) 1-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)propan-2-one

[0076] To a stirred solution of 1-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)propan-2-ol (5.00 g, 26.8 mmol, 1.3 equiv) in CH2CI2 (75 mL) was added Dess-Martin-Periodinane (14.8 g, 34.9 mmol, 1.3 equiv) at 0 °C. The reaction was stirred at room temperature for 4 hours. After full consumption of the starting material, the reaction mixture was quenched with aq. 10% NaHCOs solution (50 mL), filtered through celite and washed with CH2CI2 (100 mL). The filtrate was washed with aq. 10% NaHCOs solution (25 mL), water (50 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was triturated with n-hexane (100 mL), filtered and concentrated under reduced pressure to give 1- ((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)propan-2-one (4.5 g, 81% yield).

[0077] 1H-NMR (300 MHz, DMSO-d6, 5 / ppm): 3.29 (t, J = 6.9 Hz, 2H), 3.22 (s, 3H), 2.47 - 2.30 (m, 2H), 2.10 (s, 3H), 1.48 - 1.34 (m, 2H), 1.03 (s, 3H), 0.86 (s, 3H), 0.77-0.69 (m, 1 H), 0.55 - 0.48 (m, 1 H). d) 1-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)hexane-2, 5-dione

[0078] To a stirred solution of diisopropylamine (6.92 g, 68.4 mmol, 1.5 equiv) in THF (85 mL) was added n-butyllithium (29.2 mL, 72.9 mmol, 1.6 equiv, 2.5 M in hexane) at -78 °C, and stirred for 30 min. Then, a solution of 1-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)propan- 2-one (8.40 g, 45.6 mmol, 1.0 equiv) in THF (85 mL) was added to the reaction mixture. After stirring for 30 min at -78 °C, 1-chloropropan-2-one (6.33 g, 68.4 mmol, 1.5 equiv) was added to the reaction mixture at the same temperature. After stirring at -70 °C for 30 min, 0 °C for 30 min and at room temperature for 4 hours, the reaction mixture was quenched with brine (60 mL) and extracted with ethyl acetate (3x 100 m). The combined organic extracts were washed with water (100 mL), brine and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. The crude was purified by column chromatography (silica gel, eluting with 14% ethyl acetate in petroleum ether) to afford pure 1-((1S,3R)-3-(2-methoxyethyl)-2,2- dimethylcyclopropyl)hexane-2, 5-dione (3.7 g, 33% yield).

[0079] 1H-NMR (300 MHz, DMSO-d6, 5 / ppm): 3.28 (t, J = 6.9 Hz, 2H), 3.22 (s, 3H), 2.63 (s, 4H), 2.48 - 2.31 (m, 2H), 2.10 (s, 3H), 1.48 - 1.35 (m, 2H), 1.02 (s, 3H), 0.86 (s, 3H), 0.77 - 0.69 (m, 1 H), 0.55 - 0.47 (m, 1 H). e) 2-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one

[0080] To a stirred solution of 1-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)hexane-2,5- dione (3.70 g, 15.4 mmol, 1.0 equiv) in EtOH (74 mL) was added sodium hydroxide in water (55.4 mL, 27.7 mmol, 1.8 equiv, 0.5 M aq. solution) at room temperature. After stirring for 40 hours at room temperature, the reaction mixture was concentrated under reduced pressure to remove ethanol. The obtained residue was dissolved in ethyl acetate (100 mL), washed with water (50 mL) and brine (30 mL), dried over sodium sulfate, filtered and concentrated. The crude product was purified by column chromatography (silica gel, eluting with 20% ethyl acetate in petroleum ether) to afford 2-((1S,3R)-3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)- 3-methylcyclopent-2-en-1-one (2.3 g, 67% yield).

[0081] 1H NMR (400 MHz, CDCI3, b / ppm): 3.41 - 3.31 (m, 2H), 3.27 (s, 3H), 2.46 - 2.40 (m, 2H), 2.32 - 2.26 (m, 2H), 2.03 (s, 3H), 1.75 - 1.67 (m, 1 H), 1.13 (s, 3H), 1.12 - 1.03 (m, 1 H), 1.03 - 0.97 (m, 1 H), 0.83 (s, 3H), 0.82 - 0.77 (m, 1 H).13C NMR (101 MHz, CDCI3, b / ppm): 209.3, 174.9, 137.5, 72.9, 58.4, 34.6, 31.4, 28.8, 26.7, 23.2, 21.5, 18.9, 17.7, 16.6. GC / MS (El): m / z (%): 222 (0.1 , [M]+*), 148 (100), 147 (83), 134 (34), 133 (91), 119 (44), 105 (49), 91 (57), 79 (35), 45 (79), 41 (46).

[0082] [a]D24= +75.5° [c = 0.95, EtOH],

[0083] IR (neat, v / crm1): 2920, 2863, 1698s, 1634, 1440, 1382, 1288, 1185, 1114, 1058.

[0084] GC-HRMS (El): m / z calcd for CI3HI8O [M+>- CH3OH]: 190.1352, found: 190.1353.

[0085] Odor description: woody, guaiac wood, guayil acetate, spicy, peppery, rotundone, musky, warm, round, cashmeran.

[0086] 2: Preparation of 2-((1S,3R)-3-(2,2-dimethoxyethyl)-2,2-dimethylcyclopropyl)-3- methylcyclopent-2-en-1-one a) Methyl 2-(2-((1S,3R)-3-(2,2-dimethoxyethyl)-2,2-dimethylcyclopropyl)acetyl)-4- oxopentanoate

[0087] A suspension of methyl 4-((1S,3R)-3-(2,2-dimethoxyethyl)-2,2-dimethylcyclopropyl)-3- oxobutanoate (35.5 g, 130 mmol, 1.0 equiv, prepared according to Shi, L. et al. Chem. Commun. 2020, 56, 531), K2CO3 (72.1 g, 521 mmol, 4.0 equiv), 1-chloropropan-2-one (12.7 g, 137 mmol, 1.05 equiv) in acetone (220 mL) was refluxed for 5 hours in a 500 mL sulfonation flask equipped with a reflux condenser. The reaction mixture was filtered, poured on water (250 mL) and extracted with MTBE (250 mL). The layers were separated and the organic layer was washed with water (2x 200 mL), brine (150 mL) and dried over MgSO4. The solvent was reduced under reduced pressure to afford crude methyl 2-(2-((1S,3R)-3-(2,2-dimethoxyethyl)- 2,2-dimethylcyclopropyl)acetyl)-4-oxopentanoate (25 g, 58% yield) as a clear, brown liquid. b) 1-((1S,3R)-3-(2,2-Dimethoxyethyl)-2,2-dimethylcyclopropyl)hexane-2, 5-dione

[0088] A mixture of methyl 2-(2-((1S,3R)-3-(2,2-dimethoxyethyl)-2,2-dimethylcyclopropyl)acetyl)-4- oxopentanoate (25.0 g, 76.1 mmol, I .O equiv) and KOH (4.27 g, 76.1 mmol, I .O equiv) in ethanol (150 mL) and water (50 mL) was refluxed for 1 hour. The reaction mixture was diluted with water (150 mL) and extracted with pentane (150 mL). The layers were separated and the organic layer was washed with water (2x 150 mL), brine (100 mL) and dried over MgSO4 to afford recovered starting material (8.15 g, 33%).

[0089] The combined aqueous layers were extracted with MTBE (150 mL) and the organic layer was washed with water (2x 150 mL), brine (100 mL) and dried over MgSO4. The crude was purified by column chromatography (heptane / MTBE 1 :1) to afford 1-((1S,3R)-3-(2,2-dimethoxyethyl)- 2, 2-dimethylcyclopropyl)hexane-2, 5-dione (3.2 g, 16% yield) as a yellow liquid. c) 2-((1S,3R)-3-(2,2-Dimethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one To a solution of 1-((1S,3R)-3-(2,2-dimethoxyethyl)-2,2-dimethylcyclopropyl)hexane-2, 5-dione (3.20 g, 11.8 mmol, I .O equiv) in ethanol (50 mL) was added at room temperature NaOH (0.38 g, 9.50 mmol, 0.8 equiv). After refluxing for 1 hour, the reaction mixture was diluted with water (100 mL) and extracted with MTBE (100 mL). The organic layer was washed with water (2x 100 mL), brine (100 mL) and dried over MgSCL. The crude was purified by column chromatography (heptane / MTBE 1 :1) to give 2-((1S,3R)-3-(2,2-dimethoxyethyl)-2,2- dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one (1.60 g, 53% yield) as a yellow oil.

[0090] 1H NMR (500 MHz, CDCI3, b / ppm): 4.46 (dd, J = 5.2, 6.7 Hz, 1 H), 3.33 (s, 3H), 3.32 (s, 3H), 2.53 - 2.45 (m, 2H), 2.35 - 2.31 (m, 2H), 2.06 (s, 3H), 1.76 (ddd, J = 5.3, 6.5, 14.4 Hz, 1 H), 1.19 (s, 3H), 1.18 - 1.10 (m, 1 H), 1.09 - 1.00 (m, 1 H), 0.97 - 0.88 (m, 1 H), 0.87 (s, 3H).13C NMR (126 MHz, CDCI3, b / ppm): 209.4, 175.3, 137.5, 105.0, 53.5, 52.9, 34.7, 31.5, 29.9, 28.8, 21.9, 21.5, 19.0, 17.8, 17.1. GC / MS (El): mlz (%): 237 (0, [M+' - CH3]), 147 (18), 120 (30), 119 (23), 111 (24), 105 (20), 91 (25), 75 (100), 71 (19), 47 (19), 41 (24). [a]D24= +70.0° [c = 1.42, EtOH], IR (neat, v / crm1): 2935, 2829, 1698s, 1634, 1440, 1380, 1290, 1186, 1121 , 1058, 967, 882, 746, 707, 664, 616, 586, 533. GC-HRMS (El): m / z calcd for C14H21O3 [M+>- CH3J: 237.1491 , found: 237.1487.

[0091] Odor description: spicy, peppery, black pepper, woody, vetiver, slightly green, terpenic, rooty.

[0092] Example 3: Fragrance composition

[0093] Ingredient parts by weight

[0094] 2-NONENAL @1 % TEC 10

[0095] AMBERMAX1@ 50% in DOWANOL™ TPM 4

[0096] AMYL SALICYLATE 80

[0097] BERGAMOT OIL 50 BOISIRIS (2-ethoxy-9-methylen-2,6,6-trimethylbicyclo[3.3.1]-nonane) 20

[0098] CASHMERAN (6,7-dihydro-1 ,1 ,2,3,3-pentamethyl-4(5h)-indanone) 5

[0099] CEDARWOOD OIL 15

[0100] DAMASCONE DELTA 3

[0101] DIPROPYLENE GLYCOL 8.1

[0102] ETHYL MALTOL (3-hydroxy-2-ethyl-4h-pyran-4-one) 2

[0103] ETHYL VANILLIN (3-ethoxy-4-hydroxybenzaldehyde) 20

[0104] GALAXOLIDE S (1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylindeno[5,6-c]pyran) 40 HELIOTROPINE CRYSTALS (1 ,3-benzodioxole-5-carboxaldehyde) 15

[0105] ISO E SUPER (2-acetyl-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetra-methylnaphtalene) 250 ISORALDEINE 95 ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one ) 60 JAVANOL22

[0106] METHYL LAITONE3@ 10% in TEC 20

[0107] MYSTIKAL(methylundecanoic acid) @ 10% in TEC 3

[0108] OLIBANUM OIL 50

[0109] PATCHOULI OIL 15

[0110] 2-cyclohexylethyl acetate 4

[0111] NONALACTONE GAMMA (4-nonanolide ) 10

[0112] RADJANOL SUPER (2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol) 15

[0113] RHUBAFURAN (2,4-dimethyl-4-phenyltetrahydrofuran) 0.5

[0114] SAFRALEINE (2,3,3-trimethylindan-1-one) 3

[0115] VANILLIN 40

[0116] VETHYMINE (2,4-diethoxy-5-methylpyrimidine) @ 1% in TEC 5

[0117] VIOLET NITRILE (nona-2-6-dienenitrile) @ 10% in TEC 0.1

[0118] ZINARINE (2(2,4-dimethylcyclohex-1-yl)pyridine) 0.3

[0119] ISOPAR™ M 250

[0120] 1000

[0121] 1> mixture of 2-(2,2,7,7-tetramethyltricyclo[6.2.1.0((1 ,6)]undec-5(4)-en-5-yl)propan-1-ol

[0122] 2> 1-methyl-2-(1 ,2,2-trimethylbicyclo(3.1.0)-hex-3-ylmethyl)cyclopropyl)methanol

[0123] 3> 8-methyl-1-oxaspiro[4.5]decan-2-one

[0124] The fragrance composition is suitable to be admixed to candles @, e.g., 4 wt%, or, for example, for room freshener with rattan sticks.

[0125] The fragrance accord represents a woody floral accord with iris and vetiver as main characters. By replacing 5 parts ISOPAR™ M with 5 parts 2-((1S,3R)-3-(2-methoxyethyl)-2,2- dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one @ 10% in TEC, the diffusion is clearly enhanced, and the character improves in depth and naturality, with richer orris and sandalwood facets.

Claims

Claims1. A compound of formula (I) in the form of any one of its stereoisomers or mixture thereofwhereinR1 is selected from H, Me, Et, OMe;R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CFWMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond.

2. A compound according to claim 1 , wherein the relative configuration is in I S.Sfl as shown by formula (la)whereinR1 is selected from H, Me, Et, OMe;R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CFWMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond.

3. A compound according to claim 1 selected from the group consisting of 2-(3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3- (2-ethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- (allyloxy)ethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- methoxypropyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- hydroxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one and 2-(3-(2,2- dimethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one.

4. A flavour or fragrance composition comprising a compound of formula (I) in the form of any one of its stereoisomers or mixture thereofwhereinRi is selected from H, Me, Et, OMe;R2 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, CFWMe, COCH3, COC2H5; and the dotted line together with the carbon-carbon bond forms a single bond or a double bond.

5. A flavour or fragrance composition according to claim 4 wherein the compound of formula (I) is selected from the group consisting of 2-(3-(2-methoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3- (2-ethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- (allyloxy)ethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- methoxypropyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one, 2-(3-(2- hydroxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one and 2-(3-(2,2- dimethoxyethyl)-2,2-dimethylcyclopropyl)-3-methylcyclopent-2-en-1-one.

6. A fragranced article comprising a compound of formula (I) according to claim 1 in the form of any one of its stereoisomers or mixture thereof.

7. A flavored product comprising a compound of formula (I) according to claim 1 in the form of any one of its stereoisomers or mixture thereof.

8. The use as flavor or fragrance of a compound of formula (I) according to claim 1 in the form of any one of its stereoisomers or mixture thereof.

9. A method of improving, enhancing and / or modifying a consumer product base or consumable product base by means of adding thereto an olfactory acceptable amount of a compound of formula (I) according to claim 1 in the form of any one of its stereoisomers or mixture thereof.

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