Organic compounds

Abstract

Disclosed are cyclopentyl-2-enone derivatives of formula (I) having a costus root odor profile with some pepper note and their use as perfumes or flavors. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to flavor and fragrance ingredients and compositions containing them for flavor and fragrance applications. The present invention also relates to methods for preparing them. In particular, the present invention relates to certain cyclopent-2-enone derivatives of formula (I) having a strong woody odor characteristic with some peppery notes.

[0002] background

[0003] In the flavor and fragrance industry, perfumers and flavorists are constantly searching for new compounds with unique olfactory properties. For example, there is a need for ingredients suitable for the flavor and fragrance industry that have a woody odor profile. In particular, there is a need for ingredients that have a woody odor profile that is characteristic of pepper, particularly freshly ground black pepper.

[0004] Shoji Watanabe et al. (Aust. J. Chem., 1982, 35, 1739-41) described a new and convenient method for preparing jasmone and related compounds. It is said that cyclopentenones with linear side chains of five or six carbons or with (Z)-substituted double bonds exhibit a sweet taste similar to jasmone. Only two cyclopentanone compounds with branched side chains are disclosed, namely 2-(4,4-dimethylpent-2-yl)-3-methylcyclopent-2-ene-1-one and 2-isopropyl-3-methylcyclopent-2-ene-one, the latter of which is mentioned to have a minty aroma.

[0005] GB2100728A relates to the preparation of 3-substituted-2-cyclopentenone derivatives, such as 3-(2,6-dimethylheptyl)-2-cyclopentenone, which is suitable as an intermediate for producing compounds with insect control properties. As a by-product, a small amount of 3-methyl-2-(6-methylhept-2-yl)cyclopent-2-ene-1-one. However, the patent does not mention any characteristics of the compound. US2017 / 0327449 is directed to the Stetter reaction based on the use of biogenic reagents and catalysts. Although 3-methyl-2-(6-methylhept-2,5-diene-2-yl)cyclopent-2-ene-1-one is mentioned, no further characteristics are provided.

[0006] Surprisingly, the inventors have found a new class of cyclopent-2-enone derivatives of formula (I) as defined below, which have a very popular strong woody odor characteristic with some peppery notes. When used to create perfumes, it was surprisingly observed that these compounds have a certain transparency, although the compounds of formula (I) are very potent.

[0007] Overview

[0008] According to the first aspect of the present invention, there is provided a use of a compound of formula (I) as a fragrance or flavor.

[0009]

[0010] in

[0011] represents a carbon-carbon single or double bond,

[0012] R is hydrogen and R 1 is hydrogen or methyl, or

[0013] R and R 1 Together with the C-atom to which they are attached they form a vinyl group,

[0014] R 2 is selected from methyl and ethyl,

[0015] R 3 and R 4 is hydrogen, or

[0016] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0017] R 2 and R 3 Together they form a methylene group,

[0018] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0019] R 6 is selected from hydrogen and methyl.

[0020] According to a second aspect of the present invention, there is provided a method of improving, enhancing and / or altering a consumer product base or consumable product base by adding thereto an olfactorily acceptable amount of a compound of formula (I) or a mixture thereof.

[0021] According to a third aspect of the present invention, there is provided a composition comprising a compound of formula (I) or a mixture thereof.

[0022] According to a fourth aspect of the present invention, there is provided a fragrance composition comprising a compound of formula (I) or a mixture thereof.

[0023] According to a fifth aspect of the present invention, there is provided a perfumed article comprising a compound of formula (I) or a mixture thereof as an odorant.

[0024] According to a sixth aspect of the present invention there is provided a perfumed product comprising a compound of formula (I) or a mixture thereof.

[0025] According to a seventh aspect of the present invention, there is provided a use of a mixture comprising a compound of formula (I) and a compound of formula (II) as a fragrance.

[0026]

[0027] in

[0028] represents a carbon-carbon single or double bond,

[0029] R is hydrogen,

[0030] R 1 is hydrogen or methyl,

[0031] R 2 is selected from methyl and ethyl,

[0032] R 3 and R 4 is hydrogen, or

[0033] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0034] R 2 and R 3 Together they form a methylene group,

[0035] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0036] R 6 is selected from hydrogen and methyl.

[0037] Certain embodiments of any aspect of the present invention may provide one or more of the following advantages:

[0038] ● Provide new flavors and fragrance compounds with woody odor characteristics and some peppery notes,

[0039] ●Provide high performance compounds with low odor threshold.

[0040] The details, embodiments and preferences related to any specific one or more aspects of the aspects described in the present invention will be further described in this article, and are equally applicable to all aspects of the present invention. Unless otherwise specified herein or context is clearly contradictory, the present invention covers any combination of the embodiments, embodiments and preferences described herein and all possible variations thereof.

[0041] Detailed Description

[0042] The present invention is based on the surprising finding that cyclopent-2-enone derivatives of formula (I) have a strong woody odor characteristic with some peppery notes.

[0043] In a first aspect of the present invention, there is provided a use of a compound of formula (I) as a flavor or fragrance, wherein the compound of formula (I) is in the form of any stereoisomer thereof or a mixture thereof,

[0044]

[0045] in

[0046] represents a carbon-carbon single or double bond,

[0047] R is hydrogen and R 1 is hydrogen or methyl, or

[0048] R and R 1 Together with the C-atom to which they are attached they form a vinyl group,

[0049] R 2 is selected from methyl and ethyl,

[0050] R 3 and R 4 is hydrogen, or

[0051] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0052] R 2 and R 3 Together they form a methylene group,

[0053] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0054] R 6 is selected from hydrogen and methyl.

[0055] In a particular embodiment, the compound is of formula (I), wherein R 2 is methyl and R 3 and R 4 For hydrogen.

[0056] In another specific embodiment, the compound is of formula (I), wherein R 2 is methyl and R3 and R 4 Together with the CC bond it represents a double bond.

[0057] In another specific embodiment, the compound is of formula (I), wherein R 2 and R 3 Together they form a methylene group and R 4 For hydrogen.

[0058] In another specific embodiment, the compound is of formula (I), wherein Represents a carbon-carbon double bond.

[0059] In another specific embodiment, the compound is of formula (I), wherein R 5 Select C containing a double bond 5 To C 7 Straight chain or branched alkenyl (including C 6 For example, R 5 Selected from pent-2-enyl, 3-methyl(but-2-enyl), 3-methyl(pent-2-enyl), hex-2-enyl, 2-methyl(but-1-enyl) and 2-methyl(but-2-enyl).

[0060] In another specific embodiment, the compound is of formula (I), wherein R 5 Selected from C 5 To C 7 Straight or branched chain alkyl (including C 6 alkyl), such as 2-methylbutyl, 3-methylbutyl, pentyl and hexyl.

[0061] In another specific embodiment, the compound is of formula (I), wherein R 2 is methyl, R 3 and R 4 is hydrogen, and R 5 Select C containing a double bond 5 To C 7 Straight chain or branched alkenyl (including C 6 alkenyl) (e.g., R 5 selected from the group consisting of pent-2-enyl, 3-methyl(but-2-enyl), 3-methyl(pent-2-enyl), hex-2-enyl, 2-methyl(but-1-enyl) and 2-methyl(but-2-enyl)).

[0062] In another specific embodiment, there is provided a compound of formula (I) wherein R 2 is methyl, R 3 and R 4 is hydrogen, and R 5 Selected from C containing at most one double bond5 To C 6 Hydrocarbon residues.

[0063] One may cite 3-methyl-2-(non-2-yl)cyclopent-2-en-1-one, which has a peppery, woody odor characteristic with some floral, green, metallic, rooty, fenugreek odor characteristics.

[0064] Another specific example that can be cited is 3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one, which has a peppery, woody odor characteristic with some green, floral qualities. It has been observed that the odor of (R)-3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one is about 15 times stronger than the odor of ((S)-3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one)-3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one. From an olfactory point of view, the (R) enantiomer is slightly superior to the (S) enantiomer because they have a warm black pepper note and a patchouli leaf secondary note.

[0065] In another specific embodiment, a mixture is provided, comprising wherein R 2 and R 3 The compound of formula (I) together forming a methylene group and wherein R 3 and R 4 The compounds of formula (I) together with the CC bond represent a double bond.

[0066] Further non-limiting examples are compounds of formula (I) selected from the group consisting of: 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; -2,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-5-en-2-yl)cyclopent-2-en-1-one; 3,4-dimethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-4-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept- 2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 2-(4,7-dimethyloct-6-en-2-yl)-3-methylcyclopent-2-en-1-one; 2-(6-methylhept-5-en-2-yl)-3-vinylcyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one -2-en-1-one; 3-methyl-2-(oct-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one (including (E)-3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one); and 2-(oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one (including (E)-2-(oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one).

[0067] The compounds of the present invention contain one or more chiral centers and therefore can exist as mixtures of stereoisomers, or can be split into isomeric pure forms. Splitting stereoisomers increases the complexity of the preparation and purification of these compounds, so for economic reasons, it is preferred to use these compounds as mixtures of stereoisomers. However, if it is necessary to prepare a single stereoisomer, it can be achieved according to methods known in the art (e.g., preparative HPLC and GC) or by stereoselective synthesis.

[0068] The compounds of formula (I) can be used alone, as a mixture of their isomers, or in combination with known flavoring agent molecules selected from a wide range of currently available natural products and synthetic molecules, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and / or mixed with one or more ingredients or excipients commonly used with flavoring agents in perfume compositions, such as carrier materials and other adjuvants commonly used in the art.

[0069] As used herein, "carrier material" refers to a material that is substantially neutral from the perspective of the flavorant, ie, a material that does not significantly alter the sensory properties of the flavorant.

[0070] The term "adjuvant" refers to an ingredient that may be used in a perfume composition for reasons not particularly related to the olfactory properties of the composition. For example, an adjuvant may be an ingredient that is an aid in the processing of one or more perfume ingredients or compositions containing said ingredients, or it may improve the handling or storage of perfume ingredients or compositions containing said ingredients. It may also be an ingredient that provides an additional benefit such as imparting color or texture. It may also be an ingredient that imparts lightfastness or chemical stability to one or more ingredients included in the perfume composition. A detailed description of the nature and types of adjuvants commonly used in perfume compositions comprising adjuvants cannot be exhaustive, but it must be mentioned that said ingredients are well known to those skilled in the art.

[0071] As used herein, "flavor composition" refers to any composition comprising a compound of formula (I) (including a compound of formula (Ia)) or a mixture thereof and a matrix material, such as a diluent commonly used with a flavoring agent, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1,2-diol, triethyl citrate (TEC) and an alcohol (e.g., ethanol). Optionally, the composition may include an antioxidant adjuvant. The antioxidant may be selected from TT(BASF), 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, hydroquinone (CAS 121-31-9).

[0072] The following list includes examples of known flavorant molecules which can be combined with the compounds of formula (I) or mixtures thereof:

[0073] - essential oils and extracts, such as castoreum, costus vulgaris root oil, oakmoss absolute, geranium oil, tree moss absolute, basil oil, fruit oils such as bergamot and tangerine oils, myrtle oil, palmarosa oil, patchouli oil, orange leaf oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil;

[0074] - Alcohols, such as cinnamyl 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); dihydromyrcenol (2,6-dimethyloct-7-en-2-ol); Ebanol TM ((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-dimethyloctan-2,6-dien-1-ol); Super Muguet TM ((E)-6-ethyl-3-methyloct-6-en-1-ol); linalool (3,7-dimethyloct-1,6-dien-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); nerol (3,7-dimethyl-2,6-octadien-1-ol); phenylethyl alcohol (2-phenylethyl alcohol); Rhodinol TM (3,7-dimethyloct-6-en-1-ol); Sandalore TM (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 TM (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;

[0075] - aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde); α-amylcinnamaldehyde (2-benzylideneheptanal); Georgywood TM (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 (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); Hedione TM (3-oxo-2-pentylcyclopentaneacetic acid methyl ester); 3-(4-isobutyl-2-methylphenyl) propanal; maltol; methyl cedryl ketone; methyl ionone; verbenone and / or vanillin;

[0076] - ethers and acetals, e.g. (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 (2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[1,3]dioxane]);

[0077] - Esters and lactones, for example benzyl acetate; cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methyleneazulene-6-yl acetate); delta-decalactone (6-pentyltetrahydro-2H-pyran-2-one); (2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methylpropyl propionate); delta-undecanolactone (5-heptyloxolan-2-one) and / or eugenyl acetate (acetic acid (4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulene-6-yl) ester);

[0078] - macrocyclics, such as cypermethrin ((Z)-oxacycloheptadecan-10-en-2-one); brassic acid ethylene ester (1,4-dioxacycloheptadecan-5,17-dione) and / or (16-oxacyclohexadecane-1-one);

[0079] - Heterocyclics, for example isobutylquinoline (2-isobutylquinoline).

[0080] Therefore, in another aspect of the present invention, there is provided a fragrance composition comprising a compound of formula (I).

[0081] Formula (I) compound can be used for wide range of perfumed products, such as any field of fine and functional spices, such as perfume, air care products, household products, laundry products, body care products and cosmetics. The compound can be used in a widely varying amount, depending on the properties and dosage of specific products and other flavoring agent components. The ratio is generally 0.00001 to 3 weight % of the product. In one embodiment, the compound can be used for fabric softener in an amount of 0.0001 to 3 weight % (e.g., 0.001 to 1, including 0.5, 0.3 and 0.05 weight %). In another embodiment, the compound can be used for fine spices in an amount of 0.01 to 30 weight % (e.g., up to about 10 or up to 20 weight %), more preferably 0.01 to 5 weight % (e.g., 0.01 to 0.1 weight %). However, these values ​​are only given as examples, because experienced perfumers can also achieve effects or create new accords by lower or higher concentrations.

[0082] The compound of formula (I) can be used in the consumer product base simply by directly mixing the compound or the fragrance composition comprising the compound of formula (I) or their mixture with the consumer product base, or it can be encapsulated in an earlier step with an encapsulating material, such as 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.

[0083] Therefore, the present invention also provides a method for preparing a perfumed article, the method comprising adding a compound of formula (I) or a mixture thereof as a perfume ingredient, either by mixing directly with a consumer product base, or by mixing a perfume composition comprising a compound of formula (I) or a mixture thereof, and then mixing it with the consumer product base using conventional techniques and methods. By adding an olfactory acceptable amount of a compound of formula (I) or a mixture thereof, the odor profile of the consumer product base will be improved, enhanced or changed.

[0084] Therefore, the present invention also provides a method of improving, enhancing or modifying a consumer product base by adding an olfactory acceptable amount of a compound of formula (I) or a mixture thereof to the consumer product base.

[0085] In another aspect of the present invention, there is provided a perfumed article comprising:

[0086] a) Compounds of formula (I)

[0087]

[0088] in

[0089] represents a carbon-carbon single or double bond,

[0090] R is hydrogen and R 1 is hydrogen or methyl, or

[0091] R and R 1 Together with the C-atom to which they are attached they form a vinyl group,

[0092] R 2 is selected from methyl and ethyl,

[0093] R 3 and R 4 is hydrogen, or

[0094] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0095] R 2 and R 3 Together they form a methylene group,

[0096] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0097] R 6 is selected from hydrogen and methyl;

[0098] and

[0099] b) Consumer product matrix.

[0100] As used herein, "consumer product base" refers to a composition used as a consumer product to achieve a specific effect such as cleaning, softening and care, etc. Examples of such products include fine fragrances, such as perfumes and eau de toilette; fabric care, household products and personal care products, such as cosmetics, laundry care detergents, rinse conditioners, personal cleaning compositions, dishwasher detergents, surface cleaners; laundry products, such as softeners, bleaches, detergents; body care products, such as shampoos, shower gels; air care products (including products containing preferably volatile and generally pleasant smelling compounds, which can advantageously mask unpleasant odors even in very small amounts). Living area air fresheners contain in particular natural and synthetic essential oils, such as pine needle oil, citrus oil, eucalyptus oil, lavender oil, etc., in an amount of, for example, up to 50% by weight. As aerosols, they often contain relatively small amounts of such essential oils, e.g. less than 5 wt % or less than 2 wt %, but also include compounds such as acetaldehyde (especially <0.5 wt %), isopropanol (especially <5 wt %), mineral oil (especially <5 wt %) and propellants.

[0101] Cosmetics include:

[0102] (a) cosmetic and skin care products, in particular bath products, skin washing and cleansing products, skin care products, eye make-up, lip care products, nail care products, intimate care products and foot care products;

[0103] (b) cosmetics with special effects, in particular sunscreens, tanning products, depigmenting products, deodorants, antiperspirants, depilatories and shaving products;

[0104] (c) cosmetic dental care products, in particular dental and oral care products, tooth care products, denture cleansers, denture adhesives; and

[0105] (d) Cosmetic hair care products, in particular shampoos, hair care products, hair setting products, hair styling products and hair dyeing products.

[0106] This product list is for illustrative purposes only and should not be considered limiting in any way.

[0107] In a particular embodiment, the consumer product base is selected from fine fragrances and personal care products, including deodorants, hair care products, soaps, etc. In a particular embodiment, the consumer product base is a hair care product.

[0108] In further specific embodiments, the consumer product substrate is selected from fabric care products (including fabric softeners) and household care products (including air fresheners, dishwashers, etc.).

[0109] Although some studies have been described in the literature, 5 Compounds of formula (I) selected from 3-methyl(butyl) and 3-methyl(but-2-enyl) are useful as intermediates for the preparation of insect growth regulators (Liebigs Ann. Chem. 1986, 509-524), but most of the compounds themselves are novel.

[0110] Therefore, in another aspect of the present invention, there is provided a compound of formula (I)

[0111]

[0112] in

[0113] represents a carbon-carbon single or double bond,

[0114] R is hydrogen and R 1 is hydrogen or methyl, or

[0115] R and R 1 Together with the C-atom to which they are attached they form a vinyl group,

[0116] R 2 is selected from methyl and ethyl,

[0117] R 3 and R 4 is hydrogen, or

[0118] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0119] R 2 and R 3 Together they form a methylene group,

[0120] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0121] R 6 is selected from hydrogen and methyl;

[0122] Provided that the compound is not one in which R 2 is methyl, R, R 1 , R 3 , R 4 and R 6 is hydrogen and R 5 A compound of formula (I) selected from 3-methyl(but-2-enyl) and 3-methyl(butyl) and other than 3-methyl-2-(6-methylhepta-2,5-dien-2-yl)cyclopent-2-en-1-one.

[0123] Where R is hydrogen and R 1 Compounds of formula (I) wherein is hydrogen or methyl can be synthesized, for example, by intramolecular aldol condensation of the corresponding diketone (III) under basic conditions (eg NaOH) to give A compound of formula (I) having a carbon-carbon double bond, optionally subsequently hydrogenated to give The compounds of formula (I) representing a carbon-carbon single bond are described below.

[0124]

[0125] The preparation of the diketone (III) is well known in the art. It can be prepared, for example, by reacting the diketone (III) under alkaline conditions (e.g. Cs 2 CO 3 , TEA, sodium L-ascorbate) is completed by a 1,4 addition reaction (such as the Stettel reaction) of the corresponding aldehyde with the corresponding α,β-unsaturated ketone catalyzed by a thiazolium salt (such as thiamine hydrochloride, 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide).

[0126] When operating according to the above method, a mixture containing a compound of formula (I) and a compound of formula (II) can be obtained.

[0127]

[0128] in

[0129] R 1 is hydrogen or methyl,

[0130] R 2 is selected from methyl and ethyl,

[0131] R 3 and R 4 is hydrogen, or

[0132] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0133] R 2 and R 3 Together they form a methylene group,

[0134] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0135] R 6 is selected from hydrogen and methyl.

[0136] Therefore, in another aspect of the present invention, there is provided a use of a mixture comprising a compound of formula (I) and a compound of formula (II) as a flavor or fragrance.

[0137]

[0138] in

[0139] R is hydrogen,

[0140] R 1 is hydrogen or methyl,

[0141] R 2 is selected from methyl and ethyl,

[0142] R 3 and R 4 is hydrogen, or

[0143] R 3 and R 4 Together with the CC bond it represents a double bond, or

[0144] R 2 and R 3 Together they form a methylene group,

[0145] R 5 Selected from C 5 -C 7 Alkyl and C 5 -C 7 alkenyl, and

[0146] R 6 is selected from hydrogen and methyl.

[0147] In another aspect of the invention, there is provided a perfume composition or perfumed article comprising a mixture comprising a compound of formula (I) and a compound of formula (II), for example in a ratio of 99:1 to about 1:99, for example from about 90:10 to about 10:90, including ratios of 80:20 to 20:80, 70:30 to 30:70, 95:5 to 85:15.

[0148] Alternatively, the compound of formula (I) can be synthesized, for example, by in situ addition of 1,3-cyclopentanone to the corresponding ketone, followed by reduction of diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate catalyzed by proline. Methanol is added to the diketone thus formed under acidic conditions to form the corresponding 3-methoxycyclopentenone derivative, followed by a Grignard reaction under acidic conditions.

[0149] The present invention will now be further described with reference to the following non-limiting examples. These examples are for illustrative purposes only and variations and modifications may be made by those skilled in the art.

[0150] Example 1-1: 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one

[0151] a) A suspension of 3-methylnona-2,6-dienal (11.0 g, 72 mmol), Lindela Pd (palladium, 5%, on calcium carbonate, lead poisoned, 0.5 g) and potassium carbonate (10.0 g, 72 mmol) in ethyl acetate was stirred at 4 °C for 2 h. 2 The mixture was stirred for 28 h. The mixture was filtered through a short silica gel pad, the solvent was removed, and the residual oil was purified by silica gel column chromatography to give 3-methylnon-6-enal (9.0 g, 58 mmol, yield: 81%, E / Z=9:1) as a light yellow oil.

[0152] b) A suspension of triethylamine (2.9 g, 29 mmol) and 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide (2.9 g, 12 mmol) in ethanol (80 mL) was stirred at room temperature for 10 min, and then but-3-ene-2-one (8.2 g, 117 mmol) and 3-methylnon-6-enal (9.0 g, 58 mmol) were added. The mixture was refluxed overnight under argon. Water (80 mL) was added and extracted with MTBE (80 mL*2). The solvent was removed and the residual oil was purified by silica gel column chromatography to give 7-methyltridec-10-ene-2,5-dione (9.2 g, 41 mmol, yield: 71%, E:Z=9:1) as a light yellow oil.

[0153] c) To a solution of 7-methyltridec-10-ene-2,5-dione (8.7 g, 38.8 mmol) in ethanol (80 mL) was added aqueous NaOH (0.5 M, 80 mL), and the resulting solution was heated under reflux overnight. The solution was extracted with MTBE (50 mL*2), the solvent was removed, and the residual oil was purified by silica gel column chromatography to obtain 3-methyl-2-(oct-5-ene-2-yl)cyclopent-2-ene-1-one (5.2 g, 25 mmol, yield: 64%, E / Z isomer, E / Z=9:1) as a colorless oil, and 3-(2-methyloct-5-ene-1-yl)cyclopent-2-ene-1-one (170 mg, 0.8 mmol, yield: 2%, E:Z=6:1) as a colorless oil.

[0154] 3-Methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one:

[0155] 1 H NMR (400 MHz, CDCl 3 )δ=5.48-5.20(m, 2H), 2.74-2.53(m, 1H), 2.48-2.44(m, 2H), 2.38-2.25(m, 2H), 2.04(s, 3H), 2.01-1.91 (m, 2H), 1.90-1.45 (m, 4H), 1.18-1.09 (m, 3H), 0.94 (t, J=7.5Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , E isomer) δ = 209.5, 169.8, 143.4, 132.1, 129.0, 34.6, 34.0, 31.8, 31.1, 29.8, 25.6, 18.5, 17.5, 13.9 ppm. GC / MS (EI): m / z (%): 206 (11) [M +],191(5),177(3),150(18),124(100),109(22),67(21),55(19).

[0156] Odor description: peppery, woody, floral, fruity, green

[0157] 3-(2-Methyloct-5-en-1-yl)cyclopent-2-en-1-one:

[0158] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ = 5.94 (s, 1H), 5.54-5.29 (m, 2H), 2.66-1.15 (m, 13H), 1.05-0.86 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=210.1, 210.1, 182.1, 182.0, 132.4, 132.0, 130.6, 128.6, 128.5, 41.1, 41.0, 36.9, 36.7, 35.3, 31.7, 31.0, 30.9, 29.9, 25.5, 24.5, 20.5, 19.6, 14.3, 13.9ppm. GC / MS(EI): m / z(%): 206(3)[M + ],191(5),177(3),163(4),149(14),123(100),110(61),96(35).

[0159] Odor description: Green, metallic, marine, oyster, oily.

[0160] Example 1-2: 3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one

[0161] According to the general method of Example 1-1, a mixture of 3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one and 3-(2,6-dimethylhept-5-en-1-yl)cyclopent-2-en-1-one was obtained from 7,11-dimethyldodec-10-ene-2,5-dione (5.0 g, 22.3 mmol) and sodium hydroxide (0.9 g, 22.3 mmol). 3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one was a colorless liquid (17.4 mmol, 3.6 g, 78% yield), and 3-(2,6-dimethylhept-5-en-1-yl)cyclopent-2-en-1-one was a colorless liquid (1.9 mmol, 0.4 g, 9% yield).

[0162] 3-Methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one:

[0163] 1 H NMR (400 MHz, CDCl 3 )δ=5.15-4.96(t, J=5.6Hz, 1H), 2.71-2.52(m, 1H), 2.50-2.41(m, 2H), 2.34-2.30(m, 2H), 2.04 (s, 3H), 1.94-1.69 (m, 3H), 1.66 (s, 3H), 1.58-1.43 (m, 4H), 1.14 (d, J = 7.1Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.5, 169.8, 143.4, 131.3, 124.6, 34.6, 34.2, 31.7, 29.9, 26.6, 25.7, 18.6, 17.6, 17.4ppm. GC / MS(EI): m / z(%): 206(22)[M + ],191(3),150(15),137(21),124(100),109(23),67(22).

[0164] Odor description: woody, peppery, green, floral

[0165] 3-(2,6-Dimethylhept-5-en-1-yl)cyclopent-2-en-1-one:

[0166] 1 H NMR (400 MHz, CDCl 3 ) δ = 5.94 (s, 1H), 5.10-5.06 (t, J = 5.1Hz, 1H), 2.66-1.74 (m, 9H), 1.69 (s, 3H), 1.61 (s, 3H), 1.39-1.20 (m, 2H), 0.92 (d, J = 6.6Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=210.1, 182.1, 131.7, 130.7, 124.2, 41.1, 36.9, 35.4, 31.7, 31.1, 25.7, 25.4, 19.7, 17.7ppm. GC / MS(EI): m / z(%): 206(4)[M + ],191(3),149(7),123(100),96(36).

[0167] Odor description: Green, lemongrass, waxy

[0168] Example 1-3: 3-methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one and 3-methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one

[0169] According to the general method described in Example 1-1, 7,11-dimethyltrideca-6,10-diene-2,5-dione was obtained from 3,7-dimethylnona-2,6-dienal (10.0 g, 60.2 mmol) and but-3-en-2-one (4.2 g, 60.2 mmol) as a light yellow liquid (13.1 mmol, 3.1 g, 22% yield).

[0170] A mixture of 3-methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one and 3-methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one was obtained from 7,11-dimethyltrideca-6,10-diene-2,5-dione (3.0 g, 12.7 mmol) and sodium hydroxide (0.5 g, 12.7 mmol). 3-Methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one is a colorless liquid (2.4 mmol, 0.5 g, 19% yield, two isomers: 5:7), while 3-methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one is a colorless liquid (0.7 g, 3.3 mmol, 26% yield, 4 isomers).

[0171] 3-Methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one:

[0172] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ = 5.20 (s, 1H), 5.11-4.98 (m, 1H), 4.79 (s, 1H), 2.60-2.29 (m, 6H), 2.08 (s, 3H), 2.05-1.89 (m, 4H), 1.65, 1.55 (s, 3H), 1.00-0.89 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of isomers) δ = 207.9, 207.9, 171.5, 142.2, 142.2, 141.8, 141.7, 137.2, 137.0, 123.5, 122.3, 115.6, 35.5, 35.3, 34.6, 32.2, 31.7, 26.3, 26.0, 24.7, 22.8, 18.0, 18.0, 15.9, 12.7 ppm. GC / MS (EI): m / z (%): 218 (3) [M + ],189(8),161(96),121(29),91(51),55(100).

[0173] Odor description: Woody, peppery, fruity

[0174] 3-Methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one:

[0175] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ = 5.47-4.81 (m, 2H), 2.83-2.24 (m, 6H), 2.05-1.41 (m, 11H), 0.96-0.73 (m, 3H) ppm. GC / MS (EI): m / z (%): 218 (16) [M + ],203(11),189(15),161(34),121(29),148(58),123(52),91(100).

[0176] Odor description: woody, oily, green, floral, woody.

[0177] Example 1-4: 3-methyl-2-(6-methyloct-5-en-2-yl)cyclopent-2-en-1-one

[0178] According to the general method described in Example 1-1,

[0179] a) 7,11-dimethyltrideca-10-ene-2,5-dione (E / Z=4:3) was obtained from 3,7-dimethylnon-6-enal (14.5 g, 86.2 mmol) and but-3-en-2-one (30.2 g, 430.8 mmol) as a pale yellow liquid (8.1 mmol, 1.9 g, 9% yield, E / Z=4:3).

[0180] b) 3-Methyl-2-(6-methyloct-5-en-2-yl)cyclopent-2-en-1-one was obtained from 7,11-dimethyltrideca-10-ene-2,5-dione (1.8 g, 7.4 mmol) and sodium hydroxide (0.3 g, 7.4 mmol) as a colorless liquid (3.1 mmol, 0.7 g, 42% yield, E / Z=4:3).

[0181] 1 H NMR (400 MHz, CDCl 3 , mixture of E / Z isomers) δ = 5.08-5.01 (m, 1H), 2.65-2.59 (m, 1H), 2.47-2.45 (m, 2H), 2.33-2.31 (m, 2H), 2.04 (s, 3H), 1.98-1.69 (m, 5H), 1.65, 1.54 (s, 3H), 1.58-1.44 (m, 1H), 1.15-1.13 (m, 3H), 0.98-0.91 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of E / Z isomers) δ = 209.5, 209.5, 169.7, 143.5, 137.1, 137.1, 136.8, 136.8, 124.2, 124.2, 123.0, 123.0, 34.6, 34.6, 34.3, 32.3, 31.7, 29.9, 29.9, 26.4, 26.1, 24.7, 22.9, 18.6, 17.5, 17.4, 15.9, 12.8 ppm. GC / MS (EI): m / z (%): E isomer: 220 (11) [M + ], 205(2), 191(1), 150(10), 137(21), 124(100), 109(21), 55(44); Z isomer: 220(9)[M + ],205(1),191(1),150(11),137(22),124(100),109(21),55(43).

[0182] Odor description: woody, peppery, waxy, green

[0183] Example 1-5: 3-methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one and 3-methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one

[0184] According to the general method described in Example 1-1,

[0185] a) 7-Methyltrideca-6,10-diene-2,5-dione was obtained from 3-methylnona-2,6-dienal (15.5 g, 101.8 mmol) and but-3-en-2-one (14.3 g, 203.6 mmol) as a light yellow liquid (2.9 g, 13.0 mmol, 13% yield).

[0186] b) A mixture of 3-methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one and 3-methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one was obtained from 7-methyltrideca-6,10-diene-2,5-dione (400 mg, 1.8 mmol) and sodium hydroxide (72 mg, 1.8 mmol). 3-Methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one was a colorless liquid (71 mg, 19% yield, mixture of isomers), and 3-methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one was a colorless liquid (68 mg, 18% yield, mixture of isomers, E / Z=8:1).

[0187] 3-Methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one (mixture of isomers):

[0188] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ 5.64-5.11 (m, 3H), 2.91-2.35 (m, 6H), 2.11-1.92 (m, 5H), 1.85-1.76 (m, 3H), 1.02-0.89 (m, 3H). GC / MS (EI): m / z (%): 204 (31) [M + ],189(20),175(35),161(35),147(55),135(55),119(55),105(70),91(100),77(70).

[0189] Odor description: woody, oily, green, floral, fruity (peach)

[0190] 3-Methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one (mixture of isomers, E / Z=8:1):

[0191] 1 H NMR (400 MHz, CDCl 3, E / Z mixture) δ 5.44-5.23 (m, 2H), 5.17-5.08 (m, 1H), 4.81-4.65 (m, 1H), 2.48 (br d, J = 4.1 Hz, 2H), 2.42-2.24 (m, 4H), 2.12-1.84 (m, 7H), 0.87 (t, J = 7.4 Hz, 3H) ppm. 13 C NMR (400 MHz, CDCl 3 , E isomer) δ 208.0, 171.5, 142.3, 141.5, 132.3, 128.3, 115.7, 35.2, 34.6, 31.7, 30.9, 25.5, 18.0, 13.8 ppm. GC / MS (EI): m / z (%): 204 (20) [M + ],189(18),175(45),161(100),147(45),135(50),121(45),91(95),77(80).

[0192] Odor description: woody, peppery, green floral, fruity

[0193] Example 1-6: 3-methyl-2-(non-2-yl)cyclopent-2-en-1-one

[0194] a) According to the method reported in the literature (Helv.Chim.Acta 2017, 100, e1700200), 3-methyldec-2,6-dienal was prepared from 1,1-diethoxy-3-methylbut-2-ene (70.0 g, 389 mmol) and hex-2-en-1-ol (50.7 g, 506 mmol) as a colorless liquid (33.3 g, 200 mmol, 51% yield).

[0195] b) According to the general method described in Example 1-1 (step b), 7-methyltetradec-6,10-diene-2,5-dione was obtained from 3-methyldec-2,6-dienal (30.0 g, 180 mmol) and but-3-en-2-one (25.3 g, 361 mmol) as a light yellow liquid (6.8 g, 29.0 mmol, 16% yield).

[0196] c) 7-Methyltetradec-6,10-diene-2,5-dione (4.4 g, 18.6 mmol, 1.0 equiv) and Pd / C (10%, 200 mg) were hydrogenated in methanol (50 mL) for 16 h to give 7-methyltetradecane-2,5-dione as a light yellow liquid (3.5 g, 14.6 mmol, 78% yield).

[0197] d) According to the general method described in Example 1-1 (step c), 3-methyl-2-(non-2-yl)cyclopent-2-en-1-one was obtained as a colorless liquid (7.3 mmol, 1.6 g, 51% yield) from 7-methyltetradecane-2,5-dione (3.4 g, 14.1 mmol) and sodium hydroxide (0.6 g, 14.1 mmol).

[0198] 1 H NMR (400 MHz, CDCl 3 )δ=2.67-2.52(m, 1H), 2.50-2.40(m, 2H), 2.36-2.25(m, 2H), 2.05(s, 3H), 1.69 -1.65 (m, 1H), 1.54-1.40 (m, 1H), 1.32-1.10 (m, 14H), 0.87 (t, J=6.9Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.4, 169.4, 143.7, 34.5, 34.3, 31.9, 31.7, 30.3, 29.6, 29.3, 28.2, 22.6, 18.6, 17.5, 14.1ppm. GC / MS(EI): m / z(%): 222(17)[M + ],207(100),193(6),151(23),137(46),124(97).

[0199] Odor description: peppery, woody, green, metallic, rooty, jasmone, fenugreek.

[0200] Example 1-7: 3-methyl-2-(non-5-en-2-yl)cyclopent-2-en-1-one

[0201] According to the general method described in Example 1-1,

[0202] a) 3-Methyldec-6-enal (30.0 mmol, 5.0 g, 80% yield, E / Z isomers, E / Z=6:1) was obtained from 3-methyldec-2,6-dienal (5.6 g, 33.7 mmol) as a colorless liquid.

[0203] b) 7-Methyltetradec-10-ene-2,5-dione was obtained from 3-methyldec-6-enal (4.9 g, 29.1 mmol) and but-3-en-2-one (4.1 g, 58.2 mmol) as a light yellow liquid (17.0 mmol, 4.1 g, 59% yield, E / Z isomers, E / Z=3:1).

[0204] c) The title compound was obtained from 7-methyltetradec-10-ene-2,5-dione (4.0 g, 16.8 mmol) and sodium hydroxide (0.7 g, 16.8 mmol) as a colorless liquid (1.3 g, 6.0 mmol, 36% yield, mixture of E / Z isomers: E / Z=10:1).

[0205] 1 H NMR (400 MHz, CDCl 3 , mixture of E / Z isomers) δ = 5.47-5.26 (m, 2H), 2.68-2.54 (m, 1H), 2.51-2.43 (m, 2H), 2.35-2.28 (m, 2H), 2.05, 2.04 (s, 3H), 1.98-1.72 (m, 5H), 1.62-1.48 (m, 1H), 1.41-1.27 (m, 2H), 1.17-1.10 (m, 3H), 0.92-0.84 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , major Z isomer) δ = 209.4, 169.7, 143.4, 130.3, 130.2, 129.8 (Z), 129.7 (Z), 34.7, 34.6, 34.0, 31.7, 31.1, 29.8, 22.7, 18.5, 17.5, 13.6 ppm. GC / MS (EI): m / z (%): 220 (8) [M + ],205(3),177(2),150(16),124(100),55(27).

[0206] Odor description: woody, green, metallic, rooty, jasmone, fenugreek, peppery, pepperwood

[0207] Example 1-8: 3,4-dimethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one

[0208] According to the general method described in Example 1-1,

[0209] a) 3,7-dimethyloct-6-enal (10.0 g, 64.8 mmol) and 3-methylbut-3-en-2-one (8.2 g, 97.2 mmol) were used to obtain 3,7,11-trimethyldodec-10-ene-2,5-dione as a pale yellow liquid (17.0 mmol, 4.1 g, 27% yield, mixture of isomers: 1:1).

[0210] b) 3,4-dimethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one was obtained from 3,7,11-trimethyldodec-10-ene-2,5-dione (4.0 g, 16.8 mmol) and sodium hydroxide (0.7 g, 16.8 mmol) as a colorless liquid (10.0 mmol, 2.3 g, 62% yield, mixture of isomers: 1:1).

[0211] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ = 5.07 (t, J = 9.8 Hz, 1H), 2.74-2.45 (m, 3H), 2.02-1.96 (m, 3H), 1.96-1.69 (m, 4H), 1.68-1.63 (m, 3H), 1.57-1.46 (m, 4H), 1.19-1.10 (m, 6H) ppm . 13 C NMR (101 MHz, CDCl 3 , mixture of isomers) δ = 208.5, 208.5, 173.8, 173.7, 142.9, 142.8, 131.3, 131.3, 124.6, 124.6, 43.5, 43.4, 37.2, 34.2, 34.2, 30.1, 29.9, 26.6, 26.5, 25.7, 19.0, 17.7, 17.6, 15.0, 14.9 ppm. GC / MS (EI): m / z (%): 220 (46) [M + ],205(2),177(5),164(8),151(20),138(82),123(100).

[0212] Odor description: Green, mushroom, milk, woody, cedar.

[0213] Example 2-1: 3-methyl-2-(5-methylhept-4-en-2-yl)cyclopent-2-en-1-one

[0214] a) To a solution of 2-methylfuran (7.4 g, 90.0 mmol) in THF (100 mL) was added butyl lithium (75 mmol, 1.6 M hexane solution, 50 mL) at -78 °C and stirred for another hour, then the reaction solution was warmed and stirred at room temperature for 4 h. Cooled to -78 °C, 2,5-dimethylhept-4-enal (9.5 g, 67.5 mmol) was added dropwise. After the addition was complete, the mixture was warmed to room temperature within 1 hour and stirred at room temperature overnight. The reaction was heated with dilute NH 4The mixture was quenched with Cl solution (150 mL) and extracted with MTBE (100 mL*2). The combined organic phases were washed with MgSO 4 After drying, the solvent was removed by rotary evaporation and the residual oil was purified by silica gel column chromatography to give 2,5-dimethyl-1-(5-methylfuran-2-yl)hept-4-en-1-ol (10.7 g, 48 mmol, yield: 71%).

[0215] b) To a solution of 2,5-dimethyl-1-(5-methylfuran-2-yl)hept-4-en-1-ol (10.5 g, 47.2 mmol) in DCE (200 mL) was added zinc (II) iodide (22.6 g, 70.8 mmol) and sodium cyanoborohydride (22.3 g, 354.2 mmol) at 10°C. The resulting mixture was stirred at room temperature for 1 h. The reaction mixture was diluted with MTBE (200 mL), the entire mixture was filtered, the solvent was removed by rotary evaporation, and the residual oil was purified by silica gel column chromatography to give 2-(2,5-dimethylhept-4-en-1-yl)-5-methylfuran (5.6 g, 27 mmol, yield: 58%, mixture of E / Z isomers, E / Z=7:5) as a colorless liquid.

[0216] c) To a mixture of 2-(2,5-dimethylhept-4-en-1-yl)-5-methylfuran (5.5 g, 26.7 mmol) and acetic acid (24.0 g, 399.8 mmol) was added 0.2 g of concentrated H 2 SO 4 The resulting solution was heated to reflux for 3 h. Cooled to room temperature and water (50 mL) was added. The resulting solution was extracted with MTBE (50 mL*2) and the combined organic solution was washed with saturated NaHCO 3 solution (30 mL) and brine (20 mL), and MgSO 4 The solvent was removed by rotary evaporation and the residual oil was purified by silica gel column chromatography to give 7,10-dimethyldodec-9-ene-2,5-dione and 7,10-dimethyldodec-10-ene-2,5-dione (3.3 g, 14 mmol, 54%) as brown liquids.

[0217] d) A solution of 7,10-dimethyldodec-9-ene-2,5-dione and 7,10-dimethyldodec-10-ene-2,5-dione (2.0 g, 8.9 mmol) and sodium hydroxide (0.4 g, 8.9 mmol) in ethanol (60 mL) was heated to reflux overnight. The mixture was cooled to room temperature, and water (30 mL) was added, extracted with MTBE (60 mL*2), the solvent was removed by rotary evaporation, and the residual oil was purified by silica gel column chromatography to obtain 3-methyl-2-(5-methylhept-4-en-2-yl)cyclopent-2-en-1-one and 3-methyl-2-(5-methylhept-5-en-2-yl)cyclopent-2-en-1-one (1.3 g, 6.1 mmol, yield: 69%) as colorless oils.

[0218] GC / MS(EI): m / z(%): 206(19)[M + ], 178(2), 164(8), 136(8), 124(100), 109(10), 95(9), 83(19), 67(18), 55(48)ppm.

[0219] Odor description: woody, green, rooty, jasmone, aromatic, coniferous, pine forest.

[0220] Example 2-2: 3-methyl-2-(5-methylhept-2-yl)cyclopent-2-en-1-one

[0221] a) 7,10-dimethyldodec-9-ene-2,5-dione and 7,10-dimethyldodec-10-ene-2,5-dione (1.0 g, 4.4 mmol) were obtained by hydrogenation of 7,10-dimethyldodec-9-ene-2,5-dione (1.0 g, 4.4 mmol) catalyzed by Pd / C (10%, 100 mg) in EA (50 mL) as a light yellow liquid (0.9 g, 3.9 mmol, 88% yield, mixture of isomers, 1:1).

[0222] b) According to the general method described in Example 2-1 (step d), 3-methyl-2-(5-methylhept-2-yl)cyclopent-2-en-1-one was obtained from 7,10-dimethyldodecane-2,5-dione (0.9 g, 4.0 mmol) and sodium hydroxide (0.2 g, 4.0 mmol) as a colorless liquid (1.5 mmol, 0.3 g, 39% yield, mixture of isomers: 1:1).

[0223] 1 H NMR (400 MHz, CDCl 3, mixture of two isomers) δ = 2.58-2.52 (m, 1H), 2.49-2.45 (m, 2H), 2.36-2.27 (m, 2H), 2.05 (s, 3H), 1.77-1.37 (m, 2H), 1.37-0.80 (m, 14H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of two isomers) δ = 209.5, 169.5, 169.5, 143.8, 143.7, 35.1, 35.0, 34.5, 34.4, 34.4, 31.8, 31.7, 31.7, 30.6, 30.5, 29.5, 29.3, 19.3, 19.2, 18.7, 18.6, 17.5, 11.4, 11.3 ppm. GC / MS (EI): m / z (%): 208 (5) [M + ],193(19),179(5),151(42),125(100),109(31),79(29).

[0224] Odor description: woody, green, rooty, jasmine, waxy.

[0225] Example 3: 2-(4,7-dimethyloct-6-en-2-yl)-3-methylcyclopent-2-en-1-one

[0226] a) To a solution of 2-methylfuran (5.0 g, 60.9 mmol) in THF (100 mL) was added butyl lithium (60.9 mmol, 38 mL, 1.6 M hexane solution) dropwise at -78 °C over 30 min. After 1 h, the solution was warmed to room temperature and stirred overnight. 8-Bromo-2,5,7-trimethyloct-2-ene (12.9 g, 55.4 mmol) was then added dropwise at 0 °C, and the mixture was stirred at room temperature overnight. Water (60 mL) was added to quench the reaction, the mixture was extracted with MTBE (50 mL*2), and the combined organic phases were washed with MgSO 4 The solvent was removed and the residue was purified by silica gel column chromatography to give 2-methyl-5-(2,4,7-trimethyloct-6-en-1-yl)furan (6.7 g, 29.0 mmol, yield: 52%) as a pale yellow liquid.

[0227] b) 2-Methyl-5-(2,4,7-trimethyloct-6-en-1-yl)furan (6.0 g, 25.6 mmol) in 36 mL 75% acetic acid solution (75 g acetic acid and 25 g water and 0.6 g concentrated H 2 SO 4) was added, and the mixture was heated to reflux for 3 h. After cooling to room temperature, water (50 mL) was added, the solution was extracted with MTBE (50 mL*3), and the organic layer was washed with saturated NaHCO 3 The solution was washed with 20 mL of 4-nitropropene-2-ylpyridin-1-ylpyridin ...

[0228] c) A solution of 7,9,12-trimethyltridec-11-ene-2,5-dione (3.5 g, 14.0 mmol) and aqueous sodium hydroxide solution (0.6 g, 14.0 mmol) in ethanol (28 mL) was heated to reflux overnight. Water (70 mL) was added to the cooled reaction mixture, the solution was extracted with MTBE (50 mL*2), the solvent was removed by rotary evaporation, and the residual oil was purified by silica gel column chromatography to give 2-(4,7-dimethyloct-6-en-2-yl)-3-methylcyclopent-2-en-1-one (1.9 g, 8.1 mmol, 58%) as a colorless oil.

[0229] 1 H NMR (400 MHz, CDCl 3 , mixture of two isomers) δ = 5.19-4.97 (m, 1H), 2.87-2.64 (m, 1H), 2.54-2.38 (m, 2H), 2.36-2.26 (m, 2H), 2.05 (s, 3H), 2.01-1.04 (m, 14H), 0.85-0.80 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of two isomers) δ = 209.5, 209.5, 169.5, 169.2, 144.1, 143.5, 132.0, 132.0, 123.3, 123.1, 41.3, 41.3, 35.8, 35.0, 34.6, 34.5, 32.0, 31.7, 31.7, 31.7, 27.7, 27.7, 25.8, 25.8, 19.7, 19.4, 19.3, 18.5, 17.8, 17.8, 17.5 ppm. GC / MS (EI): m / z (%): 234 (10) [M + ],219(4),165(22),123(100),110(59),67(28),55(30).

[0230] Odor description: woody, green, metallic, oily, rooty, jasmone, peach, floral, β-ionone.

[0231] Example 4-1: 2-(6-methylhept-5-en-2-yl)-3-vinylcyclopent-2-en-1-one

[0232] a) A mixture of cyclopentane-1,3-dione (20.0 g, 204 mmol), L-proline (1.76 g, 15 mmol), diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (56.8 g, 224 mmol) and 6-methylhept-5-en-2-one (38.6 g, 306 mmol) in 1,2-dichloroethane (200 mL) was heated to reflux for 48 h. The solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography to give 3-hydroxy-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one (21.0 g, 101 mmol, yield: 49%) as a pale yellow solid.

[0233] b) A mixture of 2-(6-methylhept-5-en-2-yl)cyclopent-1,3-dione (8.60 g, 41 mmol), methanol (39.7 g) and 4-methylbenzenesulfonic acid hydrate (0.78 g, 4 mmol) in toluene (150 mL) was refluxed overnight in a Dean-Stark reactor to remove water. The mixture was concentrated by rotary evaporation and the residue was purified by silica gel column chromatography to give 3-methoxy-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one (7.2 g, 32 mmol, yield: 78%) as a colorless liquid.

[0234] c) A solution of 3-methoxy-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one (3.0 g, 13 mmol) in THF (80 mL) was added dropwise to a solution of vinylmagnesium bromide (1 M THF solution, 40 mL) at 0°C. The resulting mixture was stirred at room temperature for 3 h. A 1.6 M HCl solution (100 mL) was added at 0°C to quench the reaction. The mixture was stirred at room temperature for 2 h and extracted with MTBE (50 mL*2). The organic layer was washed with MgSO 4 After drying, the solvent was removed and the residual oil was purified by silica gel column chromatography to give 2-(6-methylhept-5-en-2-yl)-3-vinylcyclopent-2-en-1-one (1.5 g, 6.9 mmol, 53%) as a colorless liquid.

[0235] 1 H NMR (400 MHz, CDCl 3)δ=6.97 (dd, J=10.8, 17.4Hz, 1H), 5.72 (dd, J=1.1, 17.3Hz, 1H), 5.47 (dd, J=1.0, 10.8Hz, 1H), 5.06-5.02 (m, 1H), 2.80-2.71 (m , 1H), 2.65-2.61(m, 2H), 2.47-2.31(m, 2H), 1.90-1.72(m, 3H), 1.69-1.60(m, 3H), 1.60-1.45(m, 4H), 1.18(d, J=7.0Hz, 3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.5, 163.3, 144.5, 131.4, 131.3, 124.4, 120.6, 34.3, 34.1, 29.9, 26.5, 25.7, 24.8, 18.9, 17.6ppm.

[0236] Odor description: peppery, woody, green, metallic, fresh citrus, linalool, bergamot.

[0237] Example 4-2: 3-ethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one

[0238] According to the general method described in Example 4-1, the title compound was obtained from 3-methoxy-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one (3.0 g, 13.5 mmol) and ethylmagnesium bromide (20 mL, 1.0 M) as a colorless liquid (0.5 g, 2.0 mmol, 20% yield).

[0239] 1 H NMR (400 MHz, CDCl 3 )δ=5.04-4.89(m, 1H), 2.62-2.47(m, 1H), 2.46-2.29(m, 4H), 2.29-2.19(m, 2H), 1.84-1.39(m, 10H), 1.08-1.04(m, 6H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.9, 175.0, 142.7, 131.3, 124.6, 34.6, 34.2, 30.0, 28.5, 26.7, 25.7, 24.3, 18.8, 17.6, 12.2ppm. GC / MS(EI): m / z(%): 220(25)[M +],205(2),191(12),163(4),138(100),123(22),109(29).

[0240] Odor description: woody, peppery, green, rooty, aged water, iris.

[0241] Example 4-3: 3-methyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one

[0242] According to the general method described in Example 4-1,

[0243] a) 2-(6-Methylhept-2-yl)cyclopentan-1,3-dione (10.0 g, 48.0 mmol) was used to obtain 2-(6-methylhept-5-en-2-yl)cyclopentan-1,3-dione as a light yellow solid (47.5 mmol, 10.0 g, 99% yield).

[0244] b) 3-Methoxy-2-(6-methylhept-2-yl)cyclopent-2-en-1-one was obtained from 2-(6-methylhept-2-yl)cyclopent-1,3-dione (10.0 g, 47.6 mmol) as a light yellow liquid (38.4 mmol, 8.6 g, 81% yield).

[0245] c) 3-Methyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one (1.50 g, 6.7 mmol) and methylmagnesium bromide (4.5 mL, 3.0 M) was used to obtain 3-methyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one as a colorless liquid (2.0 mmol, 0.42 g, 30% yield).

[0246] 1 H NMR (400 MHz, CDCl 3 )δ=2.68-2.52(m, 1H), 2.50-2.42(m, 2H), 2.38-2.27(m, 2H), 2.05(s, 3H), 1.68 -1.63 (m, 1H), 1.52-1.43 (m, 2H), 1.25-1.04 (m, 7H), 0.83 (q, J=6.6Hz, 6H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.5, 169.5, 143.7, 38.9, 34.5, 34.5, 31.7, 30.2, 27.8, 25.9, 22.7, 22.5, 18.6, 17.5ppm. GC / MS(EI): m / z(%): 208(25)[M +],193(41),165(25),151(18),137(52),124(100),109(30).

[0247] Odor description: woody, green, jasmone, straw, anise, metallic, rooty.

[0248] Example 4-4: 3-ethyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one

[0249] According to the general method described in Example 4-1, 3-ethyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one was obtained from 3-methoxy-2-(6-methylhept-2-yl)cyclopent-2-en-1-one (3.0 g, 13.4 mmol) and ethylmagnesium bromide (20 mL, 20.1 mmol, 1.0 M) as a colorless liquid (2.5 mmol, 0.56 g, 19% yield).

[0250] 1 H NMR (400 MHz, CDCl 3 )δ=2.59-2.55(m, 1H), 2.49-2.43(m, 4H), 2.36-2.27(m, 2H), 1.72-1.59(m, 1H), 1.49-1.46 (m, 2H), 1.22-1.04 (m, 10H), 0.83 (dd, J=6.6, 3.0Hz, 6H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.9, 174.7, 143.0, 38.9, 34.6, 34.5, 30.4, 28.5, 27.9, 26.0, 24.3, 22.7, 22.6, 18.8, 12.2ppm. GC / MS(EI): m / z(%): 222(33)[M + ],207(3),193(100),179(6),151(28),138(57),123(19),109(18).

[0251] Odor description: woody, green, oily, and stale water.

[0252] Example 4-5: 3-methyl-2-(oct-2-yl)cyclopent-2-en-1-one

[0253] According to the general method described in Example 4-1,

[0254] a) 3-Hydroxy-2-(oct-2-yl)cyclopent-2-en-1-one was obtained from cyclopentane-1,3-dione (10.0 g, 101.9 mmol) and octan-2-one (39.2 g, 305.8 mmol) as a white solid (63.7 mmol, 13.4 g, 63% yield).

[0255] b) 3-Methoxy-2-(oct-2-yl)cyclopent-2-en-1-one was obtained from 2-(oct-2-yl)cyclopent-1,3-dione (10.0 g, 47.6 mmol) as a light yellow liquid (38.0 mmol, 8.6 g, 81% yield).

[0256] c) 3-Methyl-2-(oct-2-yl)cyclopent-2-en-1-one (3.0 g, 13.4 mmol) and methylmagnesium bromide (6.7 mL, 3.0 M) was obtained as a colorless liquid (2.7 mmol, 0.56 g, 20% yield).

[0257] 1 H NMR (400 MHz, CDCl 3 )δ=2.67-2.51(m, 1H), 2.51-2.41(m, 2H), 2.36-2.27(m, 2H), 2.05(s, 3H), 1.75-1.58(m, 1H), 1.56-1.39(m, 1H), 1.36 -1.02 (m, 11H), 0.86 (t, J = 6.9Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.6, 169.6, 143.7, 34.6, 34.3, 31.8, 31.7, 30.3, 29.3, 28.2, 22.7, 18.6, 17.5, 14.1ppm. GC / MS(EI): m / z(%): 208(11)[M + ],193(88),179(7),165(8),151(22),137(45),124(100),109(26).

[0258] Odor description: green, rooty, fibrous, balsamic, woody, spicy, peppery, guayil.

[0259] Example 4-6: (E)-3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one

[0260] According to the general method described in Example 4-1,

[0261] a) (E)-3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one was obtained from cyclopentane-1,3-dione (27.3 g, 278.1 mmol) and (E)-oct-5-en-2-one (27.0 g, 213.9 mmol) as a light yellow solid (10.7 g, 46% yield, purity: 90%).

[0262] b) (E)-3-Methoxy-2-(oct-5-en-2-yl)cyclopent-2-en-1-one was obtained from (E)-2-(oct-5-en-2-yl)cyclopent-1,3-dione (10.0 g, 48.0 mmol) as a pale yellow liquid (29.0 mmol, 6.8 g, 61% yield).

[0263] c) (E)-3-Ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one was obtained from (E)-3-methoxy-2-(oct-5-en-2-yl)cyclopent-2-en-1-one (6.0 g, 27.0 mmol) and ethylmagnesium bromide (54.0 mL, 1.0 M) as a colorless liquid (4.8 mmol, 1.1 g, 18% yield).

[0264] 1 H NMR (400 MHz, CDCl 3 )δ=5.48-5.22(m, 2H), 2.72-2.54(m, 1H), 2.46-2.42(m, 4H), 2.36-2.24(m, 2H), 2.09-1.91 (m, 2H), 1.91-1.71 (m, 3H), 1.63-1.46 (m, 1H), 1.20-1.07 (m, 6H), 0.94 (t, J = 7.5Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.8, 174.8, 142.7, 132.0, 129.0, 34.6, 34.0, 31.1, 29.9, 28.5, 25.6, 24.6, 18.8, 13.9, 12.2ppm. GC / MS(EI): m / z(%): 220(11)[M + ], 205(1), 191(29), 150(33), 138(100), 123(23), 109(31)ppm.

[0265] Odor description: woody, green, violet leaves, undecavertol, soft, transparent, iso e super, sylvamber, suede pepper.

[0266] Example 4-7: (E)-2-(Oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one

[0267] According to the general method described in Example 4-1, (E)-2-(oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one was obtained from (E)-3-methoxy-2-(oct-5-en-2-yl)cyclopent-2-en-1-one (2.5 g, 11.2 mmol) and vinylmagnesium bromide (45.0 mL, 1.0 M) as a colorless liquid (6.1 mmol, 1.4 g, 54% yield).

[0268] 1 H NMR (400 MHz, CDCl 3 )δ=6.96 (dd, J=10.8, 17.4Hz, 1H), 5.80-5.22 (m, 4H), 2.83-2.61 (m, 3H), 2.42-2 .36 (m, 2H), 2.03-1.52 (m, 6H), 1.18 (d, J = 7.1Hz, 3H), 0.94 (t, J = 7.4Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 )δ=209.5, 163.3, 144.4, 132.3, 131.3, 128.7, 120.6, 34.2, 31.0, 29.8, 25.6, 24.8, 18.8, 13.9ppm. GC / MS(EI): m / z(%): 218(13)[M + ],203(20),189(26),149(82),136(91),121(75),91(100),77(71).

[0269] Odor description: peppery, woody, green, metallic, rooty, tagetone, jasmine.

[0270] Example 5: 3-methyl-2-(6-methylhept-2-yl)cyclopentan-1-one

[0271] According to the method of Example 2-2 (step a), 3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one (1.5 g, 7.3 mmol) was fully hydrogenated to obtain 3-methyl-2-(6-methylhept-2-yl)cyclopent-1-one (1.2 g, 78% yield) as a colorless liquid.

[0272] 13 C NMR (101 MHz, CDCl 3, mixture of isomers) δ = 221.7, 220.9, 219.9, 219.5, 61.2, 60.8, 59.0, 58.9, 39.3, 39.2, 39.2, 39.0, 35.7, 35.4, 35.4, 35.0, 34.7, 34.4, 33.3, 33.2, 33.0, 32.6, 32.2, 30.2, 30.1, 29.9, 29.8, 28.0, 27.9, 27.9, 25.6, 25.6, 24.7, 24.3, 22.7, 22.7, 22.6, 21.2, 20.5, 17.9, 17.5, 17.0, 16.8, 15.1, 14.9 ppm. GC / MS(EI): m / z(%): 210(3)[M + ],195(1),181(1),125(12),98(50),83(100).

[0273] Odor description: Peppery, woody, green, fruity.

[0274] Example 6: Spices Harmony

[0275]

[0276]

[0277] 1) Cyclopropanecarboxylic acid (E)-2-(3,5-dimethylhex-3-en-2-yloxy)-2-methylpropyl ester

[0278] The fragrance accord is a fresh citrus cologne accord, for example, suitable for use in alcohol, at a dosage of 10 wt% (85% vol) in ethanol, it is considered a fresh citrus cologne.

[0279] Replacing 30 parts of DPG with 30 parts of 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one results in a richer and longer lasting accord. The addition of 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one softens the citrusy lemon top note and brings in a woody amber cypress quality with a peppery edge.

Claims

1. Use of the compound of formula (I) or its mixture as a fragrance or flavor, in represents a carbon-carbon single or double bond, R is hydrogen and R 1 is hydrogen or methyl, or R and R 1 Together with the C-atom to which they are attached they form a vinyl group, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl.

2. The use according to claim 1, wherein the compound of formula (I) is selected from 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-Methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-Methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-Methyl-2-(octa-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-5-en-2-yl)cyclopent-2-en-1-one; 3,4-dimethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-4-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-2-yl)cyclopent-2-en-1-one; 2-(4,7-dimethyloct-6-en-2-yl)-3-methylcyclopent-2-en-1-one; 2-(6-methylhept-5-en-2-yl)-3-vinylcyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one; 3-Methyl-2-(oct-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; and 2-(Oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one.

3. Contains the definition of claim 1 and wherein Use of a mixture of a compound of formula (I) and a compound of formula (II) representing a carbon-carbon double bond as a fragrance or flavor, in R 1 is hydrogen or methyl, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl.

4. A fragrance composition comprising a compound of formula (I) or a mixture thereof, in represents a carbon-carbon single or double bond, R is hydrogen and R 1 is hydrogen or methyl, or R and R 1 Together with the C-atom to which they are attached they form a vinyl group, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl; and At least one other flavoring agent.

5. A fragrance composition comprising a compound according to claim 1, wherein the compound is selected from 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-Methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-5-en-2-yl)cyclopent-2-en-1-one; 3,4-dimethyl-2-(6-methyl-2-cyclopent-2-en-1-one 2-(6-Methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-4-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-2-yl)cyclopent-2-en-1-one; 2-(4,7-dimethyloct-6-en-2-yl)-3-methylcyclopent-2-en-1-one; 2-(6-methylhept-5-en-2-yl)-3-vinylcyclopent-2-en-1 -one; 3-ethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; and 2-(oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one.

6. A scented product comprising a) Compounds of formula (I) as flavoring agents in represents a carbon-carbon single or double bond, R is hydrogen and R 1 is hydrogen or methyl, or R and R 1 Together with the C-atom to which they are attached they form a vinyl group, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl; and b) Consumer product matrix.

7. The perfumed article according to claim 6, wherein the flavorant compound is represents a compound of formula (I) having a carbon-carbon double bond.

8. The perfumed article according to claim 7, further comprising a compound of formula (II) as a perfume enhancer in R 1 is hydrogen or methyl, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl.

9. A perfumed article according to claim 6 or claim 8, wherein the consumer product base is selected from the group consisting of fine perfumes, personal care products and fabric care products.

10. A method for improving, enhancing or modifying a consumer product matrix by adding an olfactory acceptable amount of a compound of formula (I) or a mixture thereof to the consumer product matrix in represents a carbon-carbon single or double bond, R is hydrogen and R 1 is hydrogen or methyl, or R and R 1 Together with the C-atom to which they are attached they form a vinyl group, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl.

11. The method according to claim 10, comprising a mixture comprising a compound of formula (I) and a compound of formula (II) in R is hydrogen, R 1 is hydrogen or methyl, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl.

12. Compounds of formula (I) in represents a carbon-carbon single or double bond, R is hydrogen and R 1 is hydrogen or methyl, or R and R 1 Together with the C-atom to which they are attached they form a vinyl group, R 2 is selected from methyl and ethyl, R 3 and R 4 is hydrogen, or R 3 and R 4 Together with the CC bond it represents a double bond, or R 2 and R 3 Together they form a methylene group, R 5 is selected from C5-C7 alkyl and C5-C7 alkenyl, and R 6 is selected from hydrogen and methyl; Provided that the compound is not one in which R 2 is methyl, R, R 1 , R 3 , R 4 and R 6 is hydrogen and R 5 A compound of formula (I) selected from 3-methyl(but-2-enyl) and 3-methyl(butyl) and other than 3-methyl-2-(6-methylhepta-2,5-dien-2-yl)cyclopent-2-en-1-one.

13. The compound according to claim 7, wherein the compound is selected from 3-methyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(6-methyloct-5-en-2-yl)cyclopent-2-en-1-one; )cyclopent-2-en-1-one; 3-methyl-2-(oct-2,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-1,5-dien-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(non-5-en-2-yl)cyclopent-2-en-1-one; 3,4-dimethyl-2-(6-methylhept-5 -en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-4-en-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(5-methylhept-2-yl)cyclopent-2-en-1-one; 2-(4,7-dimethyloct-6-en-2-yl)-3-methylcyclopent-2-en-1-one; 2-(6-methylhept-5-en-2-yl)-3-vinylcyclopent-2-en-1-one cyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-5-en-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(6-methylhept-2-yl)cyclopent-2-en-1-one; 3-methyl-2-(oct-2-yl)cyclopent-2-en-1-one; 3-ethyl-2-(oct-5-en-2-yl)cyclopent-2-en-1-one; and 2-(oct-5-en-2-yl)-3-vinylcyclopent-2-en-1-one.

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