Chromene-5-one derivatives for use as fragrances

Abstract

Substituted tetrahydro-(5H)-chromene-5-one and hexahydro-(5H)-chromene-5-one derivatives of formula (I) are disclosed, which have a costus root, pepper flavor, which is associated with a nutgrass flatsedge azulene ketone by a person. Methods of their production and consumer products comprising them are also disclosed.

Description

Technical Field

[0001] The present invention relates to perfume ingredients and compositions containing the same which can be used in perfume applications. It also relates to methods for preparing the same. In particular, the present invention relates to substituted tetrahydro-(5H)-chromene-5-one and hexahydro-(5H)-chromene-5-one derivatives of formula (I) having woody, peppery notes reminiscent of cyperus azulene, an oxygenated sesquiterpene also known as (3S,5R,8S)-3,8-dimethyl-5-(prop-1-en-2-yl)-3,4,5,6,7,8-hexahydroazulene-1(2H)-one. The present invention also relates to methods for preparing the same and perfume compositions containing the same.

[0002] background

[0003] In the flavor and fragrance industry, perfumers and perfumers are constantly looking for new compounds with unique olfactory properties. Cyperus ketone can be found in trace amounts in pepper, marjoram, oregano, rosemary and patchouli oils, for example, but is also found in the aromatic substances of grapefruit, orange, apple and mango. Sensory analysis shows that when cyperus ketone is added at a uniform subthreshold level, it has a significant impact on the overall odor impression.

[0004] Therefore, there is a need for ingredients suitable for use in the flavor and fragrance industry which have woody, peppery notes reminiscent of cyperusazone.

[0005] Surprisingly, the inventors have discovered a new class of ingredients of formula (I) as defined herein below, having a popular woody, peppery fragrance note, reminiscent of cyperusazulene.

[0006] Overview

[0007] According to a first aspect of the present invention, there is provided a compound of formula (I)

[0008]

[0009] in

[0010] R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 alkyl),

[0011] R 2 Selected from hydrogen, C 1 -C 3 Alkyl (eg H or methyl),

[0012] R 3 is selected from hydrogen, methyl and ethyl,

[0013] R 4 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 3 -C 6 Cycloalkyl (e.g. cyclopropyl) and C 5 -C 6 Cycloalkenyl (e.g. cyclopent-2-en-1-yl),

[0014] R 5 is selected from hydrogen and methyl,

[0015] n is 0 or 1, and

[0016] The dashed line together with the CC bond represents a single bond and m is 1, or

[0017] The dashed line together with the CC bond represents a double bond and m is 0.

[0018] According to a second aspect of the present invention, there is provided a perfumed article comprising a compound of formula (I) according to the first aspect as an odorant.

[0019] According to a third 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 adding thereto an olfactorily acceptable amount of a compound of formula (I) of the first aspect or a mixture thereof.

[0020] According to a fourth aspect of the present invention, there is provided a flavor or fragrance composition comprising the compound of formula (I) of the first aspect or a mixture thereof.

[0021] Certain embodiments of any aspect of the invention may provide one or more of the following advantages:

[0022] To provide novel fragrance compounds with woody, peppery notes reminiscent of cyperus azulene,

[0023] Provide high performance compounds with a certain degree of transparency.

[0024] The details, embodiments and preferences provided about any specific one or more described aspects of the present invention will be further described herein and are equally applicable to all aspects of the present invention. Unless otherwise specified in this article, or clearly contradictory with context, any combination of the embodiments, embodiments and preferences described in all possible variations thereof is included in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention is based on the surprising discovery that substituted tetrahydro-(5H)-chromen-5-one and hexahydro-(5H)-chromen-5-one derivatives as defined herein have woody, peppery notes reminiscent of cyperus azulene.

[0027] According to a first aspect of the present invention, there is provided a compound of formula (I)

[0028]

[0029] in

[0030] R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 alkyl),

[0031] R 2 Selected from hydrogen, C 1 -C 3 Alkyl (eg H or methyl),

[0032] R 3 is selected from hydrogen, methyl and ethyl,

[0033] R 4 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 3 -C 6 Cycloalkyl (e.g. cyclopropyl) and C 5 -C 6 Cycloalkenyl (e.g. cyclopent-2-en-1-yl),

[0034] R 5 is selected from hydrogen and methyl,

[0035] n is 0 or 1, and

[0036] The dashed line together with the CC bond represents a single bond and m is 1, or

[0037] The dashed line together with the CC bond represents a double bond and m is 0.

[0038] In a specific embodiment, a compound of formula (I) is provided, wherein R 1 Selected from C 1 To C 5 Alkyl (e.g., C 1 , C 2 , C 3 Alkyl), R 2 , R 3 and R5 is hydrogen, R 4 Selected from C 1 To C 6 Alkyl, C 2 To C 6 Alkenyl and C 3 To C 6 Cycloalkyl, n is 0 or 1 and the dashed line together with the CC bond represents a single bond and m is 1, or the dashed line together with the CC bond represents a double bond and m is 0.

[0039] In another embodiment, a compound of formula (I) is provided, wherein R 1 Selected from C 1 To C 5 Alkyl (e.g., C 1 , C 2 , C 3 Alkyl), R 2 , R 3 and R 5 is hydrogen, R 4 Selected from C 1 To C 6 Alkyl, C 2 To C 6 For alkenyl and cyclopropyl, n is 0 or 1 and the dashed line together with the CC bond represents a single bond and m is 1, or the dashed line together with the CC bond represents a double bond and m is 0.

[0040] In another embodiment, a compound of formula (I) is provided, wherein R 1 Selected from C 1 To C 5 Alkyl (e.g. C 1 , C 2 , C 3 Alkyl), R 2 , R 3 and R 5 is hydrogen, R 4 Selected from C 1 To C 6 Alkyl, C 2 To C 6 For alkenyl and cyclopropyl, n is 1, the dashed line together with the CC bond represents a single bond and m is 1, or the dashed line together with the CC bond represents a double bond and m is 0.

[0041] In another embodiment, a compound of formula (I) is provided, wherein R 1 Selected from C 1 To C 5 Alkyl (e.g. C 1 , C 2 , C 3 Alkyl), R 2 , R 3and R 5 is hydrogen, R 4 Selected from C 1 To C 6 Alkyl, C 2 To C 6 For alkenyl and cyclopropyl, n is 1 and the dashed line together with the CC bond represents a single bond and m is 1.

[0042] In another embodiment, a compound of formula (I) is provided, wherein R 1 Selected from C 1 To C 5 Alkyl (e.g. C 1 , C 2 , C 3 Alkyl), R 2 , R 3 and R 5 is hydrogen, R 4 Selected from C 1 To C 6 Alkyl, C 2 To C 6 Alkenyl, n is 1 and the dashed line together with the CC bond represents a single bond and m is 1.

[0043] In another embodiment, there is provided a compound of formula (II)

[0044]

[0045] in

[0046] R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 alkyl),

[0047] R 2 Selected from hydrogen, C 1 -C 3 Alkyl (eg H or methyl),

[0048] R 3 is selected from hydrogen, methyl and ethyl,

[0049] R 4 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 3 -C 6 Cycloalkyl (e.g. cyclopropyl) and C 5 -C 6 Cycloalkenyl (e.g. cyclopent-2-en-1-yl),

[0050] R 5 is selected from hydrogen and methyl,

[0051] n is 0 or 1, and

[0052] The dashed line together with the CC bond represents a single bond and m is 1, or

[0053] The dashed line together with the CC bond represents a double bond and m is 0.

[0054] In another embodiment, there is provided a compound of formula (III)

[0055]

[0056] in

[0057] R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 alkyl),

[0058] R 2 Selected from hydrogen, C 1 -C 3 Alkyl (eg H or methyl),

[0059] R 4 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 3 -C 6 Cycloalkyl (e.g. cyclopropyl) and C 5 -C 6 Cycloalkenyl (e.g. cyclopent-2-en-1-yl),

[0060] n is 0 or 1 (preferably n is 1), and

[0061] The dashed line together with the CC bond represents a single bond or a double bond, preferably a single bond.

[0062] In another embodiment, a compound of formula (III) is provided, wherein R 1 Selected from C 1 To C 5 Alkyl (e.g. C 1 , C 2 , C 3 Alkyl), R 2 It is hydrogen, C 1 -C 3 Alkyl (eg H or methyl), R 4 Selected from C1 -C 6 Alkyl, C 2 -C 6 Alkenyl and C 3 -C 6 Cycloalkyl (eg cyclopropyl), n is 0 or 1 (preferably n is 1), and

[0063] The dashed line together with the CC bond represents a single bond or a double bond, preferably a single bond.

[0064] As a specific example of a compound of formula (I), one may cite, as a non-limiting example, 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, which has a peppery, woody, green odor characteristic.

[0065] As a further specific example of a compound of formula (I), one may cite, as a non-limiting example, 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, which has woody, peppery, fiber wood, cedarwood odor characteristics.

[0066] As a further specific example of a compound of formula (I), one may cite, as a non-limiting example, 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, which has a woody, cedar, green, bell pepper, vetiver odor character, reminiscent of cyperus azulene.

[0067] In addition to these woody, cedar, green, peppery, vetiver odor characteristics, the compound is also quite attractive because it has excellent trail properties.

[0068] By "trail" it is meant that a fragrance ingredient, when in a directional airflow, can be received at a distance from its source with a reliable and recognizable odor. These properties are attractive, especially in the field of personal fragrance and fine fragrance. The ability of a fragrance ingredient or essence to be perceived in space at a distance from its source is an important characteristic of a fragrance.

[0069] In another specific embodiment, the compound of formula (I) is selected from the group consisting of: 2-(but-2-en-2-yl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-(but-2-en-2-yl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-(but-3-en-2-yl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-(but-3-en-2-yl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-(sec-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; sec-butyl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-(tert-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,2,4-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,3,4-trimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one; 2,4-diethyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one; 2,4-diethyl-3-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,4-diethyl-4,6,7,8-tetrahydro-5H-chromen-5-one; 2,4-diethyl methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,4-dimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one; 2-allyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-allyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-butyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-butyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-cyclopropyl-4-ethyl-2,3, 4,6,7,8-hexahydro-5H-chromen-5-one; 2-cyclopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-ethyl-3,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-ethyl-4-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-ethyl-4,7-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-ethyl-4-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-isobutyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one;2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-(2-methylallyl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-(2-methylprop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 4-Ethyl-2-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-Ethyl-2-(prop-1-en-2-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-Ethyl-2,3-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-Ethyl-2-isobutyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 5-one; 4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-propyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one; 4-ethyl-2-vinyl- 2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-isopropyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-methyl-2-(2-methylprop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; and 4-methyl-2-(prop-1-en-2-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, and isomers thereof. ;

[0070] Compounds as defined by formula (I) (compounds of formula (II) and compounds of formula (III)) contain several chiral centers (two of which are indicated by * in the respective formulas) and can thus exist as mixtures of stereoisomers, or they can be split into isomer-pure forms. Splitting stereoisomers increases the complexity of the manufacture and purification of these compounds, and therefore, only for economic reasons, it is preferred to use these compounds as mixtures of their stereoisomers. However, if it is desired to prepare a single stereoisomer, this can be achieved according to methods known in the art, such as preparative HPLC and GC, crystallization or stereoselective synthesis (including catalytic reactions).

[0071] It was observed that some of these individual isomers have different odor properties both in performance and in olfactory properties. Odor detection threshold measurements revealed that the substituents R 1 and R4 The compound of formula (I) in the trans position has a 1 and R 4 The same compounds in the cis position had up to 30-fold lower odor detection thresholds.

[0072] Therefore, in a further embodiment of the present invention there is provided a compound of formula (I')

[0073]

[0074] in

[0075] R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 alkyl),

[0076] R 2 Selected from hydrogen, C 1 -C 3 Alkyl (eg H or methyl),

[0077] R 3 is selected from hydrogen, methyl and ethyl,

[0078] R 4 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 3 -C 6 Cycloalkyl (e.g. cyclopropyl) and C 5 -C 6 Cycloalkenyl (e.g. cyclopent-3-en-1-yl),

[0079] R 5 is selected from hydrogen and methyl,

[0080] n is 0 or 1, and

[0081] R 1 and R 4 are in trans position to each other.

[0082] In a specific embodiment, a compound of formula (I') is provided, wherein R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 Alkyl), R 2 Selected from hydrogen and C 1 -C 3Alkyl (eg H or methyl), R 3 is hydrogen, R 4 Selected from C 1 -C 6 Alkyl (e.g. C 1 , C 2 , C 3 , or C 4 Alkyl), C 2 -C 6 Alkenyl (e.g. C 2 , C 3 , or C 4 alkenyl) and cyclopropyl, R 5 is selected from hydrogen and methyl, n is 0 or 1, and R 1 and R 4 are in trans position to each other.

[0083] The compounds of formula (I) (which encompasses compounds of formula (II) and (III)) can be used alone, as a mixture of isomers thereof, or in combination with known odorant molecules (such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles) selected from a variety of natural products and currently available synthetic molecules, and / or blended with one or more ingredients or excipients commonly used in conjunction with odorants in perfume compositions (e.g., carrier materials and other adjuvants commonly used in the art).

[0084] As used herein, "carrier material" means a material that is virtually neutral from the perspective of the odorant, ie, a material that does not significantly alter the sensory properties of the odorant.

[0085] The term "adjuvant" refers to an ingredient that may be used in a perfume composition for reasons that are not particularly related to the olfactory properties of the composition. For example, an adjuvant may be an ingredient that is used as an aid in processing one or more perfume ingredients, or a composition containing the one or more ingredients, or it may improve the handling or storage of a perfume ingredient or a composition containing it. It may also be an ingredient that provides additional benefits such as imparting color or texture. It may also be an ingredient that imparts lightfastness or chemical stability to one or more ingredients contained in the perfume composition. A detailed description of the properties and types of adjuvants commonly used in perfume compositions containing them may not be exhaustive, but it must be mentioned that the ingredients are well known to those skilled in the art.

[0086] As used herein, "fragrance composition" means any composition comprising a compound of formula (I) (which encompasses compounds of formula (II) and (III)) or a mixture thereof and a base material (e.g. a diluent commonly used in conjunction with an odorant 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 contain an antioxidant adjuvant. The antioxidant may be selected from TT(BASF), Q (BASF), tocopherol (including its isomers, CAS59-02-9; 364-49-8; 18920-62-2; 121854-78-2), 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT, CAS128-37-0) and related phenols, hydroquinone (CAS121-31-9).

[0087] The following list contains examples of known odorant molecules that can be combined with the compounds of formula (I) or mixtures thereof:

[0088] - essential oils and extracts, for example castoreum, costus vulgaris root oil, oakmoss absolute, geranium oil, tree moss absolute, basil oil, fruit oils such as bergamot and orange oils, myrtle oil, palmarosa oil, patchouli oil, orange leaf oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, guyun balsam oil, lavender oil and / or ylang-ylang oil;

[0089] -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); EbanolTM ((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-ol); 4-allyl)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 MuguetTM ((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-phenylethanol); RhodinolTM (3,7-dimethyloct-6-en-1-ol); SandaloreT M (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 TimberolTM (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;

[0090] - aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde); α-amylcinnamaldehyde (2-benzylideneheptanal); GeorgywoodTM (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); HedioneTM (methyl 3-oxo-2-pentylcyclopentaneacetate); 3-(4-isobutyl-2-methylphenyl)propanal; maltol; methyl cedryl ketone; methyl ionone; verbenone; and / or vanillin;

[0091] -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]);

[0092] - esters and lactones, for example benzyl acetate; cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methyleneazulen-6-yl acetate); δ-decalactone (6-pentyltetrahydro-2H-pyran-2-one); (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl propionate); δ-undecalactone (5-heptyloxacyclopentane-2-one); and / or vetiver acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulene-6-yl) acetate);

[0093] - macrocycles, such as cypermethrin ((Z)-oxahedetadecan-10-en-2-one); brassic acid ethylene glycol ester (1,4-dioxahedetadecan-5,17-dione); and / or (16-oxacyclohexadecane-1-one); and

[0094] - a heterocycle, for example isobutylquinoline (2-isobutylquinoline).

[0095] Thus, in a further aspect of the invention there is provided a fragrance composition comprising a compound of formula (I) (which encompasses compounds of formula (II) and (III)).

[0096] The compound of formula (I) (which encompasses the compound of formula (II) and (III)) can be used in a wide range of perfumed products, such as any advanced and functional perfume (such as perfume, air care products, household products, laundry products, body care products and cosmetics) fields. Depending on the properties and amounts of the specific products and other odorant ingredients, the compound can be used in a very different amount. The ratio is typically 0.00001% to 30% by weight of the product. In one embodiment, the compound can be used in a fabric softener in an amount of 0.0001 to 1% by weight (e.g., 0.001% to 0.1% by weight, including 0.05% and 0.03% by weight). In another embodiment, the compound can be used in a hair care product ((dry cleaning) shampoo, conditioner) in an amount of about 0.1% by weight to about 5% by weight. In another embodiment, the compound can be used in fine perfumery in an amount of 0.00001 to 30 weight percent (e.g. up to about 10 or up to 20 weight percent), more preferably 0.3 to 5 weight percent (e.g. 0.5 to 3 weight percent). However, these values ​​are given by way of example only, as an experienced perfumer can also achieve the effect or can create novel accords with lower or higher concentrations.

[0097] The compound of formula (I) (which encompasses compounds of formula (II) and (III)) can be used in a consumer product base simply by directly mixing the compound or a flavor composition comprising the compound of formula (I) (which encompasses compounds of formula (II) and (III)) or a mixture thereof with the consumer product base, or in an early step it can be encapsulated by an encapsulating material (e.g., 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.

[0098] Thus, the present invention also provides a method for making a perfumed article comprising incorporating a compound of formula (I) (which encompasses compounds of formula (II) and (III)) or a mixture thereof as a perfume ingredient by direct incorporation into a consumer product base or by incorporation into a perfume composition comprising a compound of formula (I) (which encompasses compounds of formula (II) and (III)) or a mixture thereof, which perfume composition can then be mixed with the consumer product base using conventional techniques and methods. By adding an olfactorily acceptable amount of a compound of formula (I) (which encompasses compounds of formula (II) and (III)) or a mixture thereof, the odor notes of the consumer product base will be improved, enhanced, or altered.

[0099] Therefore, the present invention also provides a method for improving, enhancing or modifying a consumer product base by adding thereto an olfactory acceptable amount of a compound of formula (I) (which encompasses compounds of formula (II) and (III)) or a mixture thereof.

[0100] In a further aspect of the invention there is provided a perfumed article comprising

[0101] a) a compound of formula (I), or a mixture thereof

[0102]

[0103] in

[0104] R 1 Selected from C 1 -C 5 Alkyl (e.g. C 1 , C 2 , C 3 alkyl),

[0105] R 2 Selected from hydrogen, C 1 -C 3 Alkyl (eg H or methyl),

[0106] R 3 is selected from hydrogen, methyl and ethyl,

[0107] R 4 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 3 -C 6 Cycloalkyl (e.g. cyclopropyl) and C 5 -C 6 Cycloalkenyl (e.g. cyclopent-2-en-1-yl),

[0108] R 5 is selected from hydrogen and methyl,

[0109] n is 0 or 1, and

[0110] The dashed line together with the CC bond represents a single bond and m is 1, or

[0111] The dashed line together with the CC bond represents a double bond and m is 0;

[0112] and

[0113] b) Consumer product base.

[0114] As used herein, 'consumer product base' means 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 detoilettes; fabric care, household products and personal care products, such as cosmetics, laundry care detergents, rinse conditioners, personal cleaning compositions, detergents for dishwashers, surface cleaners; laundry products, such as softeners, bleaches, detergents; body care products, such as shampoos, shower gels; air care products (including products preferably containing volatile and generally pleasant smelling compounds, which advantageously can even mask unpleasant odors in very small amounts). Air fresheners for living areas contain in particular natural and synthetic essential oils, such as pine needle oil, citrus oil, eucalyptus oil, lavender oil, etc., in amounts of, for example, up to 50% by weight. As aerosols, they tend to contain smaller amounts of such essential oils, as examples, less than 5 wt % or less than 2 wt %, but also include compounds such as acetaldehyde (particularly, <0.5 wt %), isopropyl alcohol (particularly, <5 wt %), mineral oil (particularly, <5 wt %) and propellants.

[0115] Cosmetic products include:

[0116] (a) cosmetic 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;

[0117] (b) cosmetic products with specific effects, in particular sunscreens, tanning products, depigmenting products, deodorants, antiperspirants, depilatories and shaving products;

[0118] (c) cosmetic dental care products, in particular dental and oral care products, tooth care products, cleaning agents for dental restorations, adhesives for dental restorations; and

[0119] (d) Cosmetic hair care products, in particular shampoos, hair care products, hair styling products, hair styling products and hair dyeing products.

[0120] This product list is given as an illustration and should not be considered limiting in any way.

[0121] In one embodiment, the consumer product base is selected from the group consisting of fine fragrances and personal care products, including deodorants, hair care products, soaps, and the like.

[0122] In other embodiments, the consumer product base is selected from fabric care products, including fabric softeners, and household care products, including air fresheners, dishwashing detergents, and the like.

[0123] In another embodiment, the perfume composition comprises a mixture of compounds of formula (I) as defined herein above. For example, the perfume composition may include a mixture comprising 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one and at least a second compound of formula (I) (e.g., 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one, 2-isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one, and / or 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one).

[0124] Compounds of formula (I) (which encompass compounds of formula (II) and (III)), wherein the dashed line together with the CC bond represents a single bond, can be synthesized, for example, by Grignard reaction of 2-hydroxyhexahydro-5H-chromen-5-one or 2-hydroxytetrahydrocyclopenta[b]pyran-5(2H)-one, followed by acid treatment to form hexahydro-(5H)-chromen-5-one or tetrahydrocyclopenta[b]pyran-5(4H)-one derivatives. Hemiacetal (2-hydroxyhexahydro-5H-chromen-5-one or 2-hydroxytetrahydrocyclopenta[b]pyran-5(2H)-one) can be synthesized, for example, by the reaction of 1,3-cyclic dione with α,β-unsaturated aldehyde catalyzed by amino acids and their derivatives (e.g., 2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine), or can be synthesized by domino reaction of 1,3-cyclic dione, aldehyde and enol ether with or without a catalyst (e.g., proline).

[0125] Alternatively, compounds of formula (I) (which encompasses compounds of formula (II) and (III)), in which the dashed line together with the CC bond represents a double bond, may be reacted, for example, by reaction with a Lewis acid such as ZnCl 2 )-catalyzed reaction of 1,3-cyclic diones with α,β-unsaturated ketones to form substituted tetrahydro-(5H)-chromen-5-ones or substituted dihydrocyclopenta[b]pyran-5(4H)-ones.

[0126] Pure cis isomers of formula (I') can be synthesized, for example, by hydrogenating the corresponding tetrahydro-(5H)-chromen-5-one or dihydrocyclopenta[b]pyran-5(4H)-one in the presence of a catalyst (eg 10% Pd / C).

[0127] Additional details regarding reaction conditions are provided in the Examples.

[0128] The present invention will now be further described with reference to the following non-limiting examples. These examples are for illustrative purposes only, and it is to be understood that variations and modifications may be made by those skilled in the art.

[0129] General Method A:

[0130] All reactions were carried out under argon using solvents and reagents from commercial suppliers without further purification. The solvents used for extraction and chromatography were technical grade and used without further purification. Flash chromatography was carried out using TsingdaoHaiyang Chemical silica gel (200-300 mesh) and Santai Technologies silica gel rapid columns. Unless otherwise noted, a mixture of heptane: MTBE was used as eluent. NMR spectrograms were recorded using AW 400MHz Bruker spectrometer. 1 Chemical shifts in H NMR spectra are reported in δ (ppm) referenced to the residual proton signal of the deuterated solvent; coupling constants are expressed in Hertz (Hz). 13 C NMR spectra are referenced to the carbon signal of the deuterated solvent. The following abbreviations are used: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, bs = broad singlet. GC / MS spectral data were obtained from Agilent 6890N and MSD 5975 using a column HP-5MS, 30 m, 0.25 mm, 0.25 μm.

[0131] Example 1-1: 2-Ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0132] 1. To a solution of cyclohexane-1,3-dione (100 g, 0.89 mol, 1.0 eq.) and but-2-enal (69 g, 0.98 mol, 1.1 eq.) in dichloromethane (250 mL) was slowly added 2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine (8.7 g, 27 mmol, 0.03 eq.) in dichloromethane (100 ml) at 0° C. and stirred at room temperature for 16 h under argon. The solvent was removed and the residue was purified by silica gel column chromatography (heptane:MTBE=5:1 to 1:1) to give 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (146 g, 0.80 mol, 90% yield, mixture of diastereomers, dr=4:1) as a white solid.

[0133] 1 H NMR (400 MHz, CDCl 3 , mixture of diastereomers) δ 5.54-5.02 (m, 2H), 2.98-2.64 (m, 1H), 2.60-2.15 (m, 4H), 2.14-1.61 (m, 4H), 1.35-0.99 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl3, Mixture of diastereomers) δ 198.9, 198.7, 170.2, 169.4, 116.5, 115.9, 94.5, 93.2, 37.1, 36.9, 35.7, 35.6, 28.9, 28.7, 23.2, 23.0, 21.0, 20.9, 20.4, 20.3 ppm.

[0134] 2. To a solution of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (120 g, 0.66 mol) in THF (1 L) was added ethylmagnesium chloride (0.88 L, 1.32 mol, 1.5 M) at 0°C and stirred at room temperature for 16 h under argon. Aqueous hydrochloric acid solution was added at 10°C to 15°C to quench the reaction until pH = 3. The mixture was stirred at room temperature for 16 h and then extracted with ethyl acetate (0.5 L*3). The organic layer was washed with saturated NaHCO 3 aqueous solution, brine and MgSO 4 After filtration, the solvent was removed and the crude oil was purified via distillation to give 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (115 g, 0.59 mol, yield: 90%, mixture of diastereomers, trans:cis=1.75:1) as a colorless liquid.

[0135] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.02-3.56 (m, 1H), 2.85-2.57 (m, 1H), 2.44-1.22 (m, 10H), 1.22-0.88 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.0, 171.9, 171.2, 117.3, 116.2, 78.5, 74.3, 37.7, 37.4, 37.2, 33.7, 29.0, 28.9, 28.2, 27.9, 25.8, 22.6, 21.1, 21.0, 20.4, 20.1, 9.5 ppm. GC / MS (EI): m / z (%): 194 (98) [M + ],179(80),165(20),151(90),139(100),125(15),55(26).

[0136] Odor description: Peppery, woody, green.

[0137] The cis / trans isomers in 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (Example 1-1) were further separated by silica gel chromatography (heptane:MTBE=20:1).

[0138] Trans-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: Colorless liquid.

[0139] 1 H NMR (400 MHz, CDCl 3 )δ3.99-3.89(m,1H),2.84-2.73(m,1H),2.43-2.31(m,4H),1.99-1.87(m ,2H),1.79-1.48(m,4H),1.08(d,J=6.9Hz,3H),1.01(t,J=7.4Hz,3H)ppm. 13 CNMR (101MHz, CDCl 3 )δ198.0,171.2,116.2,74.3,37.2,33.6,28.8,28.2,22.6,21.1,21.0,9.4ppm. GC / MS(EI):m / z(%):194(96)[M + ],179(94),165(24),151(100),139(75),55(33).

[0140] Odor description: Woody, green.

[0141] cis-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: Colorless liquid.

[0142] 1 H NMR (400 MHz, CDCl 3 )δ3.70-3.56(m,1H),2.62-2.49(m,1H),2.37-1.17(m,10H),1.10(d,J=6.5Hz,3H),0.92(t,J=7.4Hz,3H)ppm. 13 C NMR (101MHz, CDCl3) δ = 197.9, 171.9, 117.2, 78.4, 37.6, 37.3, 28.9, 27.8, 25.7, 20.3, 20.0, 9.4ppm. GC / MS(EI):m / z(%):194(65)[M + ],179(42),166(12),151(60),139(100),55(23).

[0143] Odor description: green, damp, woody

[0144] Example 1-2: 4-Methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0145] According to the procedure of Example 1-1, the compound (15 mmol, 3.1 g, 77% yield, trans:cis=2.1:1) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 19 mmol) and propylmagnesium bromide (19 mL (2M), 38 mmol).

[0146] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.09-3.71 (m, 1H), 2.85-2.56 (m, 1H), 2.48-1.25 (m, 12H), 1.22-1.06 (m, 3H), 1.05-0.88 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.0, 172.0, 171.2, 117.3, 116.1, 77.1, 72.9, 38.2, 37.3, 37.2, 37.1, 34.1, 29.0, 28.8, 25.8, 22.6, 21.1, 21.0, 20.3, 20.1, 18.4, 18.3, 14.0, 14.0 ppm. GC / MS (EI): m / z (%): 208 (82) [M + ],193(56),179(27),165(17),151(86),139(100),55(30).

[0147] Odor description: Woody, peppery, fibrous, cedar

[0148] trans- and cis-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one were separated from 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0149] Trans-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: Colorless liquid.

[0150] 1 H NMR (400 MHz, CDCl 3 )δ4.18-3.76(m,1H),2.97-2.60(m,1H),2.49-2.19(m,4H),2.10-1.85(m,2H),1.77-1.26(m,6H),1.19-1.04(m,3H),1.02-0.82(m,3H)ppm.13 C NMR (101 MHz, CDCl 3 )δ198.0,171.2,116.2,72.9,37.4,37.2,34.2,28.9,22.6,21.1,21.0,18.4,14.0ppm. GC / MS(EI):m / z(%):208(94)[M + ],193(68),179(34),165(22),151(99),139(100),125(31),55(35).

[0151] Odor description: Woody (cedarwood), peppery

[0152] cis-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: Colorless liquid.

[0153] 1 H NMR (400 MHz, CDCl 3 )δ3.76-3.63(m,1H),2.63-2.50(m,1H),2.41-2.08(m,4H),2.02-1.69( m,3H),1.67-1.16(m,5H),1.10(d,J=6.5Hz,3H),0.89-0.86(m,3H),ppm. 13 CNMR (101MHz, CDCl 3 )δ=197.9,171.9,117.3,77.1,38.2,37.4,37.1,29.0,25.8,20.4,20.1,18.3,14.0ppm. GC / MS(EI):m / z(%):208(55)[M + ],193(32),179(13),165(12),139(100),55(25).

[0154] Odor description: green, woody, cedarene, vetiver, grapefruit

[0155] Example 1-3: 2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0156] According to the procedure of Example 1-1, the compound (75 mmol, 16 g, 65% yield) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (21 g, 115 mmol) and isopropylmagnesium bromide (77 mL, 230 mmol, 3.0 M).

[0157] 1 H NMR (400 MHz, CDCl 3,Mixture of diastereomers) δ 3.76-3.38 (m, 1H), 2.79-2.46 (m, 1H), 2.39-2.08 (m, 4H), 1.99-1.16 (m, 5H), 1.15-0.97 (m, 3H), 0.95-0.77 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, Mixture of diastereomers) δ 197.7, 172.1, 171.2, 117.2, 116.0, 81.8, 77.5, 37.3, 37.1, 34.8, 31.9, 31.8, 30.5, 28.8, 28.6, 26.0, 22.4, 21.0, 20.9, 20.3, 20.0, 18.0, 17.9, 17.7, 17.7 ppm. GC / MS (EI): m / z (%): 208 (63) [M+], 193 (27), 165 (21), 152 (29), 139 (100), 55 (20).

[0158] Odor description: peppery, woody, violet, vetiver, fruity

[0159] The colorless liquid was separated from 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one by silica gel chromatography (heptane:MTBE=20:1). trans-2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one .

[0160] 1 H NMR (400 MHz, CDCl 3 )δ3.93-3.46(m,1H),2.80-2.63(m,1H),2.34-2.18(m,4H),1.94-1.70(m,3H),1.57-1.40(m,2H),1.00(d,J=6.9Hz,3H),0.95-0.82(m,6H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,171.3,116.1,77.6,37.1,32.0,30.6,28.7,22.4,21.0,20.9,18.1,17.8ppm. GC / MS (EI): m / z (%): 208 (71) [M+], 193 (37), 179 (2), 165 (27), 152 (36), 139 (100), 55 (23).

[0161] Odor description: fruity, woody, ambery, peppery

[0162] Example 1-4: 2-(sec-butyl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0163] According to the procedure of Example 1-1, the compound (15 mmol, 3.4 g, 80% yield, trans:cis=3:1) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 19 mmol) and sec-butylmagnesium bromide (38 mL, 38 mmol, 1.0 M).

[0164] 1 H NMR (400 MHz, CDCl 3, Mixture of isomers) δ 3.88-3.50 (m, 1H), 2.79-2.48 (m, 1H), 2.38-1.13 (m, 11H), 1.12-0.98 (m, 3H), 0.92-0.79 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of isomers)δ198.1,172.5,172.3,171.6,171.5,117.4,116.2,116.1,80.8,80.6,76.5,76.3,38.5,38.4,38.4,38.3,37.3,37.2,35.2,34.2,30.7,29 .8,28.9,28.8,28.7,26.2,26.1,25.2,25.1,25.0,22.6,22.4,21.1,21.0, 20.9,20.4,20.4,20.1,14.3,14.2,14.1,14.0,11.7,11.6,11.5,11.4ppm. GC / MS(EI):m / z(%):222(37)[M + ],207(11),193(11),179(2),165(15),151(23),139(100),55(22).

[0165] Odor description: Vetiver, woody, fruity, isomethyl ionone Powdery, orris, peppery, green

[0166] Example 1-5: 2-Isobutyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0167] According to the procedure of Example 1-1, the compound (17 mmol, 3.8 g, 89% yield, trans:cis=2.5:1) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 19 mmol) and isobutylmagnesium bromide (48 ml, 38 mmol, 0.8 M).

[0168] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.12-3.67 (m, 1H), 2.79-2.45 (m, 1H), 2.38-2.14 (m, 4H), 2.01-1.40 (m, 6H), 1.33-1.17 (m, 1H), 1.13-0.98 (m, 3H), 0.92-0.82 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.1, 172.0, 171.2, 117.3, 116.1, 75.6, 71.5, 44.3, 44.1, 38.7, 37.3, 37.2, 34.6, 29.0, 28.9, 25.7, 24.3, 24.3, 23.0, 23.0, 22.6, 22.4, 22.3, 21.1, 21.0, 20.4, 20.1 ppm. GC / MS (EI): m / z (%): 222 (64) [M + ],207(22),179(48),166(46),151(73),139(100),109(20),55(23).

[0169] Odor description: green, woody, amber, peppery

[0170] Example 1-6: 4-methyl-2-(prop-1-en-2-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0171] According to the procedure of Example 1-1, the compound (22 mmol, 4.5 g, 57% yield, trans:cis=2:1) ​​was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (10 g, 38 mmol) and prop-1-en-2-ylmagnesium bromide (154 ml, 77 mmol, 0.5 M).

[0172] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.03-4.84 (m, 2H), 4.39-4.09 (m, 1H), 2.81-2.55 (m, 1H), 2.38-1.38 (m, 11H), 1.14-1.01 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 197.8, 171.5, 170.8, 143.5, 143.2, 117.2, 116.1, 112.7, 112.5, 79.9, 76.0, 37.2, 37.1, 36.8, 33.0, 28.9, 28.7, 25.82, 22.6, 20.9, 20.8, 20.1, 18.2, 18.0 ppm. GC / MS (EI): m / z (%): 206 (65) [M + ],178(8),163(38),151(100),135(20),79(14),68(76).

[0173] Odor description: green, metallic, rooty, woody, iris, isomethyl ionone, peppery

[0174] Example 1-7: 2,4-Dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0175] According to the procedure of Example 1-1, the compound (16 mmol, 2.8 g, 28% yield, trans:cis=1:2.7) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (10.0 g, 54.9 mmol) and methylmagnesium bromide (37 mL, 110 mmol, 3.0 M).

[0176] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.16-3.75 (m, 1H), 2.74-2.50 (m, 1H), 2.37-1.22 (m, 11H), 1.12-0.98 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.9, 171.8, 171.0, 117.1, 115.9, 73.5, 69.4, 40.0, 37.3, 37.1, 35.9, 28.9, 28.8, 25.7, 22.7, 21.1, 21.0, 20.8, 20.3, 20.0 ppm. GC / MS (EI): m / z (%): 180 (38) [M + ],165(62),151(100),137(42),124(35),109(46),79(63),67(81).

[0177] Odor description: woody, cedar, green

[0178] Example 1-8: 2-Cyclopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0179] According to the procedure of Example 1-1, the compound (14 mmol, 2.9 g, 51% yield, trans:cis=3:2) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27.4 mmol) and cyclopropylmagnesium bromide (110 mL, 55 mmol, 0.5 M).

[0180] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.32-3.02 (m, 1H), 2.79-2.48 (m, 1H), 2.42-1.34 (m, 8H), 1.17-0.90 (m, 4H), 0.64-0.16 (m, 4H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.8, 171.6, 170.9, 117.1, 116.0, 81.6, 77.7, 37.9, 37.2, 37.0, 34.0, 28.9, 28.7, 25.7, 22.5, 20.9, 20.8, 20.2, 20.0, 15.0, 14.8, 3.2, 3.2, 1.7, 1.6 ppm. GC / MS (EI): m / z (%): 206 (20) [M + ],191(16),163(17),151(14),139(59),121(18),107(9),91(17),79(28),67(100),53(53).

[0181] Odor description: peppery, woody, green

[0182] Example 1-9: 2-Allyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0183] According to the procedure of Example 1-1, the compound (7.7 mmol, 1.6 g, 28% yield, trans:cis=1.5:1) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) and allylmagnesium bromide (55 mL, 55 mmol, 1.0 M).

[0184] 1 H NMR (400 MHz, CDCl 3,Mixture of diastereomers) δ 5.96-5.69 (m, 1H), 5.27-5.04 (m, 2H), 4.15-3.79 (m, 1H), 2.84-2.56 (m, 1H), 2.51-1.26 (m, 10H), 1.21-1.05 (m, 3H) ppm. 13 CNMR (101MHz, CDCl 3, diastereoisomer mixture) δ = 196.9, 170.7, 169.9, 132.4, 132.2, 116.9, 116.3, 115.2, 75.5, 71.5, 38.5, 38.3, 36.5, 36.3, 36.1, 32.5, 27.9, 27.7, 24.6, 21.5, 20.1, 20.0, 19.3, 19.0 ppm. GC / MS (EI): m / z (%): 206 (38) [M + ],191(12),163(100),149(17),139(66),125(23),109(24),91(18),79(33),67(27),55(26).

[0185] Odor description: Green, vetiver, cedar

[0186] Example 1-10: 2-Butyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0187] According to the procedure of Example 1-1, the compound (16 mmol, 3.7 g, 60% yield, trans:cis=2.4:1) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) and butylmagnesium bromide (69 mL, 55 mmol, 0.8 M).

[0188] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.99-3.63 (m, 1H), 2.78-2.49 (m, 1H), 2.36-1.22 (m, 14H), 1.13-0.98 (m, 3H), 0.90-0.81 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 198.0, 172.0, 171.2, 117.3, 116.1, 77.3, 73.2, 38.2, 37.3, 37.2, 34.9, 34.7, 34.1, 29.0, 28.8, 27.3, 27.2, 25.8, 22.6, 22.5, 21.1, 21.0, 20.3, 20.1, 14.0, 13.9 ppm. GC / MS (EI): m / z (%): 222 (73) [M + ],207(45),193(7),179(23),165(14),151(68),139(100),109(28),55(20).

[0189] Odor description: green, cork, myrrh, woody, peppery

[0190] Example 1-11: 2-(But-2-en-2-yl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0191] According to the procedure of Example 1-1, the compound (14 mmol, 3.0 g, 55% yield) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 25 mmol) and but-2-en-2-ylmagnesium bromide (99 mL, 50 mmol, 0.5 M).

[0192] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ 5.75-5.17 (m, 1H), 4.96-4.15 (m, 1H), 2.84-2.57 (m, 1H), 2.43-2.17 (m, 4H), 1.95-1.74 (m, 3H), 1.69-1.31 (m, 7H), 1.18-0.97 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of isomers) δ 197.8, 172.2, 171.2, 134.0, 133.8, 123.5, 123.1, 123.0, 117.3, 116.0, 78.3, 75.2, 71.0, 37.3, 37.1, 36.4, 32.8, 32.0, 29.0, 28.8, 26.1, 22.6, 21.0, 20.9, 20.2, 20.0, 18.1, 18.0, 13.2, 12.9, 12.8, 11.5 ppm. GC / MS (EI): m / z (%): 220 (41) [M +],205(10),191(4),177(6),165(14),151(100),82(76),67(86).

[0193] Odor description: woody, peppery, green, violet

[0194] Example 1-12: 4-methyl-2-(2-methylprop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromene-5- ketone

[0195] According to the procedure of Example 1-1, the compound (10 mmol, 2.3 g, 54% yield, trans:cis=3.5:1) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 19 mmol) and (2-methylprop-1-en-1-yl)magnesium bromide (77 mL, 38 mmol, 0.5 M).

[0196] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.31-4.96 (m, 1H), 4.76-4.26 (m, 1H), 2.78-2.56 (m, 1H), 2.40-1.36 (m, 14H), 1.15-0.96 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.7, 171.7, 171.0, 137.7, 123.6, 123.4, 117.1, 115.9, 74.3, 70.2, 38.6, 37.2, 37.1, 34.6, 29.0, 28.8, 25.7, 25.5, 22.6, 21.0, 20.9, 20.2, 20.1, 18.2, 18.1 ppm. GC / MS (EI): m / z (%): 220 (43) [M + ],205(4),177(7),151(95),82(100),67(61).

[0197] Odor description: Green, vetiver, grapefruit, woody, peppery

[0198] Example 1-14: 2-(But-3-en-2-yl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0199] According to the procedure of Example 1-1, the compound (19 mmol, 4.1 g, 68% yield) was obtained as a colorless liquid from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) and but-3-en-2-ylmagnesium bromide (61 mL, 55 mmol, 0.9 M).

[0200] 1 H NMR (400 MHz, CDCl 3, Mixture of isomers) δ 6.03-5.49 (m, 1H), 5.19-4.86 (m, 2H), 4.07-3.32 (m, 1H), 2.84-2.45 (m, 1H), 2.43-1.16 (m, 9H), 1.15-0.87 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, ppm (mixture of isomers) δ = 197.9, 172.0, 171.9, 171.2, 171.1, 139.4, 139.3, 139.0, 117.4, 117.3, 116.2, 116.1, 115.6, 115.6, 115.5, 115.4, 80.3, 76.1, 42.0, 41.9, 41.6, 41.4, 37.3, 37.1, 35.3, 35.0, 31.2, 30.7, 28.8, 28.7, 28.6, 25.9, 22.4, 22.4, 21.0, 20.9, 20.2, 20.0, 15.5, 15.4, 15.3 ppm. GC / MS(EI):m / z(%):220(40)[M + ],205(11),191(7),163(100),139(84),109(28),93(27),79(28),67(36),55(43).

[0201] Odor description: violet, woody, cedar, peppery, green

[0202] Example 1-15: 4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0203] 1. According to the synthetic procedure of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one in Example 1-1, 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (0.67 mol, 132 g, 75% yield) was obtained as a white solid by reaction of cyclohexane-1,3-dione (100 g, 0.89 mol, 1.0 eq.) and pent-2-enal (83 g, 0.98 mol, 1.1 eq.).

[0204] 4-Ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400 MHz, CDCl 3, mixture of diastereomers) δ 5.55-5.26 (m, 1H), 4.78 (brs, 1H), 2.74-2.54 (m, 1H), 2.50-1.06 (m, 10H), 1.02-0.65 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of diastereomers) δ 198.8, 198.6, 170.3, 170.1, 115.9, 115.3, 94.9, 93.3, 37.1, 37.0, 31.7, 31.3, 29.7, 29.3, 28.9, 28.8, 27.0, 25.7, 20.9, 20.3, 11.6, 11.1 ppm. GC / MS (EI): m / z (%): 196 (44) [M + ],178(8),167(92),153(68),139(100),125(33),79(30),55(51).

[0205] 2. According to the procedure of Example 1-1, the compound (98 mmol, 19 g, 64% yield, trans:cis=1.8:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (30 g, 153 mmol) and methylmagnesium bromide (306 mL, 306 mmol, 1.0 M).

[0206] 1 H NMR (400 MHz, CDCl 3 , mixture of diastereomers) δ 4.30-3.69 (m, 1H), 2.68-2.41 (m, 1H), 2.40-2.08 (m, 4H), 2.06-1.53 ​​(m, 4H), 1.45-0.98 (m, 5H), 0.94-0.54 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of diastereomers) δ = 198.0, 197.9, 172.5, 170.9, 116.0, 115.4, 73.5, 69.6, 37.3, 37.2, 36.3, 31.5, 31.4, 29.4, 29.1, 28.9, 27.0, 26.0, 21.2, 21.0, 20.9, 20.0, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 194 (32) [M + ],179(9),165(100),153(6),137(25),123(7),109(11),91(10),79(9),67(7),55(12).

[0207] Odor description: Peppery, woody, cedar

[0208] trans- and cis-4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one were separated from 4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0209] Trans-4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400 MHz, CDCl 3 )δ4.26-3.97(m,1H),2.59-2.44(m,1H),2.42-2.23(m,4H),2.03-1.80(m,3H),1. 75-1.57(m,1H),1.50-1.23(m,4H),1.21-1.01(m,1H),0.92(t,J=7.4Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.8,170.9,115.5,69.6,37.3,31.5,29.5,28.9,27.1,21.2,21.1,11.7ppm. GC / MS(EI):m / z(%):194(33)[M + ],179(9),165(100),139(18),109(10),55(10).

[0210] Odor description: peppery, woody, cedar, earthy

[0211] cis-4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400 MHz, CDCl 3 )δ3.95-3.74(m,1H),2.60-2.41(m,1H),2.36-2.12(m,4H),2.06-1.61(m,4H),1.38-1.12(m,5H),0.85-0.67(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,172.5,115.9,73.5,37.3,36.3,31.3,29.0,26.0,20.8,20.0,10.3ppm. GC / MS(EI):m / z(%):194(34)[M +],179(9),165(100),153(8),137(26),109(11),55(13).

[0212] Odor description: woody, cedar, dusty, green

[0213] Example 1-16: 2,4-Diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0214] According to the procedure of Example 1-1, the compound (102 mmol, 21 g, 80% yield, trans:cis=2:1) ​​was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (25 g, 127 mmol) and ethylmagnesium chloride (127 mL, 255 mmol).

[0215] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.98-3.56 (m, 1H), 2.61-2.47 (m, 1H), 2.45-2.17 (m, 4H), 2.11-1.06 (m, 8H), 1.04-0.95 (m, 3H), 0.93-0.77 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.7, 197.7, 172.6, 171.0, 115.9, 115.5, 78.4, 74.3, 37.3, 37.1, 33.9, 31.3, 29.2, 28.9, 28.8, 28.1, 27.9, 26.9, 25.9, 20.9, 19.9, 11.6, 10.3, 9.4, 9.4 ppm. GC / MS (EI): m / z (%): 208 (40) [M + ],193(11),179(100),165(7),153(17),137(21),125(22),55(14).

[0216] Odor description: woody, cedar, green, sweet pepper, vetiver

[0217] trans- and cis-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one were separated from 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0218] Trans-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400 MHz, CDCl 3)δ4.03-3.70(m,1H),2.62-2.47(m,1H),2.46-2.21(m,4H),2.02-1.58(m,6H),1.4 7-1.31(m,1H),1.17-1.05(m,1H),1.01(t,J=7.4Hz,3H),0.91(t,J=7.3Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.8,171.1,115.7,74.5,37.3,29.3,29.1,28.9,28.3,27.1,21.1,11.7,9.5ppm. GC / MS(EI):m / z(%):208(34)[M + ],193(10),179(100),165(6),151(11),137(20),125(23),55(15).

[0219] Odor description: woody, tobacco, straw, kephalis

[0220] cis-2,4-Diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one : 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.72-3.63 (m, 1H), 2.62-2.48 (m, 1H), 2.44-2.21 (m, 4H), 2.09-1.53 ​​(m, 6H), 1.41-1.24 (m, 2H), 1.00 (t, J = 7.5 Hz, 3H), 0.82 (t, J = 7.4 Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.8, 172.6, 116.0, 78.4, 37.3, 33.9, 31.4, 29.0, 28.0, 26.0, 20.0, 10.3, 9.4. GC / MS (EI): m / z (%): 208 (43) [M + ],193(8),179(100),165(9),153(49),137(28),125(29),55(21).

[0221] Odor description: fruity, berry, isomethyl ionone, woody, cedar

[0222] Example 1-17: 4-ethyl-2-vinyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0223] According to the procedure of Example 1-1, the compound (18 mmol, 3.6 g, 86% yield, trans:cis=1.4:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and vinylmagnesium bromide (41 mL, 41 mmol, 1.0 M).

[0224] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.94-5.75 (m, 1H), 5.37-5.08 (m, 2H), 4.44-4.16 (m, 1H), 2.61-1.01 (m, 11H), 0.89-0.73 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.9, 197.8, 171.9, 170.5, 136.9, 136.7, 116.8, 116.6, 116.2, 115.6, 77.4, 73.7, 63.6, 37.3, 37.2, 34.2, 31.0, 29.9, 29.1, 29.0, 28.8, 27.0, 25.9, 21.0, 20.9, 20.1, 11.7, 11.6, 10.4 ppm. GC / MS (EI): m / z (%): 206 (58) [M + ],191(3),177(100),165(27),149(11),137(43),121(11),107(11),91(20),77(22),67(9),55(22).

[0225] Odor description: woody, iris, isomethyl ionone, green, cedar, pepper

[0226] Example 1-18: 4-Ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0227] According to the procedure of Example 1-1, the compound (36 mmol, 7.9 g, 70% yield, trans:cis=2:1) ​​was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (10 g, 51 mmol) and propylmagnesium bromide (51 mL, 102 mmol, 2.0 M).

[0228] 1 H NMR (400 MHz, CDCl 3, mixture of diastereomers) δ 4.08-3.63 (m, 1H), 2.63-2.47 (m, 1H), 2.47-2.15 (m, 4H), 2.10-1.61 (m, 5H), 1.60-1.20 (m, 5H), 1.04-0.78 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.9, 197.8, 172.6, 171.0, 116.1, 115.6, 77.1, 73.1, 37.4, 37.3, 37.2, 34.5, 31.4, 29.6, 29.3, 29.1, 28.9, 27.0, 26.0, 21.0, 20.0, 18.4, 18.3, 14.0, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 222 (34) [M + ],207(8),193(100),179(5),165(13),153(25),137(33),125(54),55(39).

[0229] Odor description: woody, cedar, slightly green, grapefruit, vetiver, pepper

[0230] The trans / cis isomers were separated from 4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0231] trans-4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0232] 1 H NMR (400MHz, CDCl3) δ4.09-3.84(m,1H),2.59-2.47(m,1H),2.44-2.25(m,4H),1.96-1.90(m,2H) ,1.87-1.79(m,1H),1.77-1.60(m,2H),1.59-1.33(m,4H),1.17-1.02(m,1H),0.98-0.89(m,6H). 13 C NMR (101 MHz, CDCl 3 )δ197.8,171.0,115.7,73.1,37.4,37.2,29.6,29.3,28.9,27.0,21.0,18.4,14.0,11.7ppm. GC / MS(EI):m / z(%):222(35)[M +],207(7),193(100),137(15),125(39),55(14).

[0233] cis-4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0234] 1 H NMR (400MHz, CDCl3) δ3.83-3.66(m,1H),2.63-2.49(m,1H),2.46-2.15(m,4H),2.10-1.76( m,4H),1.74-1.61(m,1H),1.59-1.20(m,5H),1.00-0.90(m,3H),0.82(t,J=7.5Hz,3H)ppm. 13 C NMR (101MHz, CDCl3) δ197.8,172.6,116.1,77.0,37.4,37.2,34.5,31.4,29.0,26.0,20.0,18.3,13.9,10.3ppm. GC / MS(EI):m / z(%):222(46)[M + ],207(9),193(100),165(14),153(60),137(29),125(48),55(21).

[0235] Example 1-19: 4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0236] According to the procedure of Example 1-1, the compound (32 mmol, 7.1 g, 63% yield, trans:cis=2.1:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (10 g, 51 mmol) and isopropylmagnesium bromide (102 mL, 102 mmol, 1.0 M).

[0237] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.85-3.38 (m, 1H), 2.63-2.46 (m, 1H), 2.44-2.14 (m, 4H), 2.08-1.65 (m, 6H), 1.45-1.04 (m, 3H), 0.99-0.95 (m, 4H), 0.93-0.74 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 198.0, 197.9, 173.0, 171.3, 116.2, 115.8, 82.0, 77.8, 37.4, 37.3, 32.1, 32.0, 31.7, 31.1, 29.2, 29.1, 28.9, 27.0, 26.1, 26.0, 21.1, 20.1, 18.1, 17.9, 17.8, 11.7, 10.4 ppm. GC / MS (EI): m / z (%): 222 (52) [M + ],207(16),193(100),179(11),153(46),137(75),125(42),91(27),79(37),67(24),55(67).

[0238] Odor description: woody, green, rooty, vetiver, slightly ambery, powdery, iris, isomethyl ionone, peppery

[0239] The trans / cis isomers were separated from 4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0240] trans-4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0241] 1 H NMR (400 MHz, CDCl 3 )δ3.73(dd,J=11.9,5.6Hz,1H),2.61-2.49(m,1H),2.43-2.27(m,4H),2.03-1.64(m, 5H), 1.43-1.35 (m, 1H), 1.18-1.04 (m, 1H), 1.03-0.95 (m, 6H), 0.91 (t, J = 7.4Hz, 3H). 13 C NMR (101 MHz, CDCl 3 )δ197.8,171.2,115.7,77.7,37.2,32.1,29.1,28.8,26.9,25.9,21.0,18.1,17.7,11.6. GC / MS(EI):m / z(%):222(50)[M + ],207(16),193(100),151(25),137(47),125(31),55(25).

[0242] cis-4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0243] 1 H NMR (400 MHz, CDCl3 )δ3.50(dd,J=11.4,5.6Hz,1H),2.61-2.48(m,1H),2.46-2.15(m,4H),2.07- 1.79(m,6H),1.40-1.21(m,2H),1.04-0.93(m,6H),0.82(t,J=7.4Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,172.9,116.1,81.9,37.4,32.0,31.6,31.1,29.0,26.0,20.0,18.1,17.8,10.3ppm. GC / MS(EI):m / z(%):222(53)[M + ],207(6),193(75),153(100),137(52),125(36),55(28).

[0244] Example 1-20: 4-ethyl-2-(prop-1-en-2-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0245] According to the procedure of Example 1-1, the compound (14 mmol, 3.0 g, 67% yield, trans:cis=3.3:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and prop-1-en-2-ylmagnesium bromide (82 mL, 41 mmol, 0.5 M).

[0246] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.19-4.87 (m, 2H), 4.48-4.06 (m, 1H), 2.65-2.51 (m, 1H), 2.48-2.19 (m, 4H), 2.14-1.69 (m, 7H), 1.65-1.05 (m, 2H), 1.00-0.76 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.8, 197.7, 172.3, 170.7, 143.6, 143.4, 116.1, 115.6, 112.7, 112.5, 80.1, 76.2, 37.3, 37.2, 33.3, 31.6, 29.3, 29.0, 28.8, 28.6, 26.9, 25.9, 21.0, 20.0, 18.3, 18.0, 11.7, 10.4 ppm. GC / MS (EI): m / z (%): 220 (86) [M +],205(4),191(100),177(23),164(29),151(45),137(50),55(31).

[0247] Odor description: Green, woody, peppery

[0248] Example 1-21: 2-Cyclopropyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0249] According to the procedure of Example 1-1, the compound (16 mmol, 3.5 g, 62% yield, trans:cis=1:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and cyclopropylmagnesium bromide (102 mL, 51 mmol, 0.5 M).

[0250] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.22-2.80 (m, 1H), 2.47-2.33 (m, 1H), 2.31-1.09 (m, 10H), 0.92-0.82 (m, 1H), 0.81-0.64 (m, 3H), 0.56-0.05 (m, 4H) ppm. 13 CNMR (101MHz, CDCl 3, diastereoisomer mixture) δ = 197.5, 197.4, 172.2, 170.7, 115.8, 115.4, 81.5, 77.7, 37.1, 37.0, 34.1, 31.3, 29.5, 29.1, 28.9, 28.7, 26.8, 25.9, 20.9, 19.9, 15.1, 14.9, 11.5, 10.2, 3.2, 1.7, 1.6 ppm. GC / MS (EI): m / z (%): 220 (13) [M + ],191(52),177(11),153(41),125(57),95(21),77(22),67(100),55(53).

[0251] Odor description: green, fatty, woody, peppery

[0252] Example 1-22: 4-ethyl-2-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0253] According to the procedure of Example 1, the compound (9.9 mmol, 2.2 g, 39% yield, trans:cis=1.3:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and prop-1-en-1-ylmagnesium bromide (51 mL, 51 mmol, 1.0 M).

[0254] 1 H NMR (400 MHz, CDCl 3, Mixture of isomers) δ 5.85-5.56 (m, 1H), 5.55-5.30 (m, 1H), 4.83-4.07 (m, 1H), 2.66-2.40 (m, 1H), 2.40-2.10 (m, 4H), 2.05-1.56 (m, 7H), 1.54-1.34 (m, 1H), 1.33-0.95 (m, 1H), 0.94-0.65 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of isomers)δ197.8,197.7,172.3,172.1,170.8,170.6,130.0,129.7,129.6,129.3,129.2,129.1,128.4,128.3,116.1,115.5,115.4,77.7,74.0,73.1,6 9.2,37.3,37.2,34.7,34.5,31.2,31.1,30.2,30.0,29.3,29.2,29.1,28.9 ,27.1,27.0,26.1,26.0,21.0,20.1,17.8,13.4,13.3,11.8,11.7,10.4ppm. GC / MS(EI):m / z(%):220(61)[M + ],205(7),191(66),177(11),165(100),153(21),137(48),68(78).

[0255] Odor description: woody, fruity, powdery, isomethyl ionone, iris, peppery

[0256] Example 1-23: 2-Allyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0257] According to the procedure of Example 1-1, the compound (7.1 mmol, 1.6 g, 28% yield, trans:cis=1.3:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and allylmagnesium bromide (51 mL, 51 mmol, 1.0 M).

[0258] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.93-5.49 (m, 1H), 5.26-4.88 (m, 2H), 4.18-3.36 (m, 1H), 2.50-2.08 (m, 7H), 2.03-1.55 (m, 4H), 1.40-0.94 (m, 2H), 0.88-0.66 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.8, 197.7, 172.4, 170.8, 133.3, 133.3, 117.9, 117.8, 116.1, 115.6, 72.6, 39.5, 39.4, 37.3, 37.2, 33.8, 31.2, 29.2, 29.0, 28.9, 28.7, 26.9, 25.9, 21.0, 20.0, 11.6, 10.3 ppm. GC / MS (EI): m / z (%): 220 (45) [M + ],205(9),191(59),177(26),153(100),137(31),125(98),55(34).

[0259] Odor description: woody, peppery, green

[0260] Example 1-24: 4-ethyl-2-(2-methylprop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromene-5- ketone

[0261] According to the procedure of Example 1-1, the compound (13 mmol, 3.0 g, 63% yield, trans:cis=3.5:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and (2-methylprop-1-en-1-yl)magnesium bromide (82 mL, 41 mmol, 0.5 M).

[0262] 1 H NMR (400 MHz, CDCl 3,Mixture of diastereomers) δ 5.95-5.73 (m, 1H), 5.19-4.86 (m, 2H), 4.11-3.61 (m, 1H), 2.64-2.47 (m, 1H), 2.43-2.11 (m, 6H), 2.04-1.59 (m, 6H), 1.51-1.00 (m, 2H), 0.96-0.74 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.7, 172.4, 170.9, 137.7, 137.6, 123.8, 123.6, 116.0, 115.4, 74.4, 70.4, 37.3, 37.1, 34.9, 31.2, 30.2, 29.3, 29.1, 28.9, 27.0, 26.0, 25.7, 21.0, 20.0, 18.3, 18.2, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 234 (43) [M + ],205(29),191(7),177(9),165(76),82(100),67(57).

[0263] Odor description: Green, grapefruit, bell pepper, woody.

[0264] Example 1-25: 4-Ethyl-2-isobutyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0265] According to the procedure of Example 1-1, the compound (16 mmol, 3.8 g, 79% yield, trans:cis=2.5:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and isobutylmagnesium bromide (51 mL, 41 mmol, 0.8 M).

[0266] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.17-3.68 (m, 1H), 2.63-2.45 (m, 1H), 2.42-2.17 (m, 4H), 2.07-1.57 (m, 6H), 1.46-1.02 (m, 3H), 0.99-0.75 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 197.9, 197.8, 172.7, 171.0, 116.1, 115.6, 75.6, 71.6, 44.4, 44.2, 37.4, 37.2, 35.0, 31.4, 30.1, 29.3, 29.1, 28.9, 27.1, 26.0, 24.4, 24.3, 23.1, 23.0, 22.4, 22.3, 21.0, 20.0, 11.8, 10.3 ppm. GC / MS (EI): m / z (%): 236 (70) [M + ],221(10),207(100),193(71),165(20),151(96),139(35),125(53),55(23).

[0267] Odor description: green, fruity, woody, cedar, peppery

[0268] Example 1-26: 2-(sec-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0269] According to the procedure of Example 1-1, the compound (15 mmol, 3.6 g, 75% yield, trans:cis=2.8:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and sec-butylmagnesium bromide (41 ml, 41 mmol, 1.0 M).

[0270] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.92-3.54 (m, 1H), 2.61-2.46 (m, 1H), 2.44-2.17 (m, 4H), 2.06-1.88 (m, 2H), 1.87-1.65 (m, 2H), 1.64-1.17 (m, 4H), 1.16-1.02 (m, 1H), 1.00-0.77 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3,mixture of diastereomers) δ 197.8, 197.7, 173.1, 173.0, 171.3, 171.2, 116.1, 115.7, 115.6, 80.8, 80.6, 76.6, 76.4, 38.6, 38.6, 38.4, 38.3, 37.4, 37.2, 31.8, 31.6, 31.4, 30. 5,29.3,29.1,29.0,28.8,28.7,26.9,26.1,26.0,25.2,25.1,25.0,24.9,21.0, 20.0,14.3,14.2,14.1,14.0,11.8,11.7,11.6,11.5,11.4,11.3,10.4,10.3ppm. GC / MS(EI):m / z(%):236(48)[M + ],221(7),207(100),189(5),179(9),165(10),153(41),137(27),125(30),109(7),95(8),79(12),67(7),55(18).

[0271] Odor description: Woody, fruity, powdery, isomethyl ionone, orris, peppery.

[0272] Example 1-27: 2-(But-2-en-2-yl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0273] According to the procedure of Example 1-1, the compound (14 mmol, 3.2 g, 67% yield, trans:cis=2.3:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and but-2-en-2-ylmagnesium bromide (82 mL, 41 mmol, 0.5 M).

[0274] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.60-5.23 (m, 1H), 4.92-4.20 (m, 1H), 2.53 (m, 1H), 2.39-2.10 (m, 4H), 2.00-1.40 (m, 11H), 1.28-1.00 (m, 1H), 0.94-0.68 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 197.8, 197.7, 172.9, 171.1, 171.0, 134.2, 133.9, 123.4, 123.1, 122.9, 116.1, 115.5, 115.4, 78.5, 75.3, 71.1, 37.3, 37.2, 32.8, 31.6, 29.4, 29.1, 28.8, 28.3, 27.5, 27.0, 26.9, 26.1, 21.0, 20.0, 18.1, 17.9, 13.2, 12.9, 12.7, 11.8, 11.7, 11.5, 10.4 ppm. GC / MS (EI): m / z (%): 234 (59) [M + ],205(46),191(29),177(23),165(95),151(26),137(43),82(90),67(100).

[0275] Odor description: green, coniferous, terpenic, woody, tobacco, fiber, gurjum, peppery

[0276] Example 1-28: 2-(But-3-en-2-yl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0277] According to the procedure of Example 1-1, the compound (2.2 mmol, 0.5 g, 15% yield, trans:cis=1.3:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (3.0 g, 15 mmol) and but-3-en-2-ylmagnesium bromide (34 mL, 31 mmol, 0.9 M).

[0278] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.85-5.52 (m, 1H), 5.13-4.85 (m, 2H), 3.90-3.42 (m, 1H), 2.53-2.08 (m, 6H), 2.03-1.55 (m, 4H), 1.43-1.11 (m, 2H), 1.10-0.94 (m, 3H), 0.88-0.68 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,mixture of diastereomers)δ197.9,197.8,172.8,172.7,171.1,171.0,139.5,139.4,139.1,139.1,116.2,116.1,115.8,115.7,115.6,115.6,80.4,80.3,76.3,76.2,42.1,42.0, 41.7,41.6,37.4,37.2,31.7,31.5,31.4,31.3,29.1,29.0,28.8,28.7,26.9,26.8 ,26.6,26.1,26.0,25.9,21.0,20.0,15.5,15.4,15.3,11.7,11.6,10.3,10.2ppm. GC / MS(EI):m / z(%):234(57)[M + ],219(10),205(60),177(68),163(22),153(100),137(40),125(76),81(72),55(64).

[0279] Odor description: woody, tobacco, cedar

[0280] Example 1-29: 2-(tert-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0281] According to the procedure of Example 1-1, the compound (16 mmol, 3.7 g, 61% yield) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 25.5 mmol, 1.0 equiv) and tert-butylmagnesium chloride (51 mL, 51 mmol, 1.0 M).

[0282] 1 H NMR (400MHz, CDCl3 , Mixture of diastereomers) δ 3.66-3.32 (m, 1H), 2.64-2.48 (m, 1H), 2.44-2.15 (m, 4H), 2.10-1.64 (m, 4H), 1.43-1.04 (m, 2H), 0.97 (s, 9H), 0.93-0.77 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 197.6, 197.5, 173.0, 171.2, 115.9, 115.5, 84.6, 80.3, 37.2, 37.1, 33.5, 33.4, 31.9, 29.2, 29.0, 28.8, 28.6, 26.7, 25.9, 25.6, 25.5, 23.5, 20.9, 19.9, 11.5, 10.2 ppm. GC / MS (EI): m / z (%): 236 (21) [M + ],207(43),189(15),151(43),95(21),79(31),57(100).

[0283] Odor description: Green, woody

[0284] Example 1-30: 2-Butyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0285] According to the procedure of Example 1-1, the compound (14 mmol, 3.4 g, 57% yield, trans:cis=2.5:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 25 mmol) and butylmagnesium bromide (64 mL, 51 mmol, 0.8 M).

[0286] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.98-3.52 (m, 1H), 2.54-2.39 (m, 1H), 2.35-2.10 (m, 4H), 2.03-0.94 (m, 12H), 0.90-0.63 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.8, 197.7, 172.6, 171.0, 116.1, 115.6, 77.3, 73.3, 37.3, 37.2, 35.0, 34.8, 34.5, 31.4, 29.5, 29.3, 29.0, 28.9, 27.3, 27.2, 27.0, 26.0, 22.6, 22.5, 21.0, 20.0, 14.0, 13.9, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 236 (41) [M + ],221(8),207(100),193(13),165(13),153(22),125(40),55(14).

[0287] Odor description: Green fragrance, cedar fragrance

[0288] Example 1-31: 4-ethyl-2-(2-methylallyl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0289] According to the procedure of Example 1-1, the compound (6.8 mmol, 1.6 g, 27% yield, trans:cis=1.1:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 25 mmol) and (2-methylallyl)magnesium bromide (64 mL, 51 mmol, 0.8 M).

[0290] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.08-4.66 (m, 2H), 4.25-3.70 (m, 1H), 2.70-2.14 (m, 7H), 2.13-1.64 (m, 7H), 1.47-1.02 (m, 2H), 0.98-0.70 (m, 3H). 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.8, 197.7, 172.5, 170.8, 141.3, 141.2, 116.2, 115.7, 113.2, 75.6, 71.8, 43.5, 43.4, 37.3, 37.2, 34.2, 31.3, 29.3, 29.2, 29.0, 28.8, 27.0, 26.0, 22.9, 22.8, 21.0, 20.0, 11.7, 10.3. GC / MS (EI): m / z (%): 234 (45) [M + ],219(6),205(44),191(12),177(100),153(42),81(57),67(20),55(38).

[0291] Odor description: Green, woody

[0292] Example 1-32: 2-Ethyl-4-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0293] According to the procedure of Example 1-1, the compound (40 mmol, 8.8 g, 83% yield) was obtained as a colorless liquid from 2-hydroxy-4-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (10 g, 48 mmol) and ethylmagnesium bromide (48 mL, 95 mmol, 2.0 M).

[0294] 1 H NMR (400 MHz, CDCl 3,Mixture of diastereomers) δ 4.07-3.58 (m, 1H), 2.76-2.54 (m, 1H), 2.50-2.17 (m, 4H), 2.01-1.78 (m, 3H), 1.75-1.52 (m, 3H), 1.46-1.18 (m, 4H), 1.04-0.83 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.9, 197.8, 172.4, 171.0, 116.5, 115.7, 98.7, 78.5, 74.4, 37.4, 37.2, 36.7, 36.0, 34.6, 30.2, 29.7, 29.0, 28.9, 28.2, 28.0, 27.4, 21.0, 20.3, 20.0, 19.5, 14.3, 14.1, 9.5, 9.4. GC / MS (EI): m / z (%): 222 (14) [M + ],193(1),179(100),151(10),137(7),125(15).

[0295] Odor description: green, woody, peppery, fruity

[0296] Example 1-33: 4-Isopropyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0297] 1. According to the synthetic procedure of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one in Example 1-1, 2-hydroxy-4-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (166 mmol, 35 g, 75% yield) was obtained as a white solid by reaction of cyclohexane-1,3-dione (25 g, 223 mmol) and 4-methylpent-2-enal (22 g, 223 mmol).

[0298] GC / MS(EI):m / z(%):210(11)[M + ],192(4),167(100),151(35),139(75),55(25).

[0299] 2. According to the procedure of Example 1-1, 4-isopropyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (14 mmol, 3.0 g, 71% yield, trans:cis=1:1) was obtained as a colorless liquid from 2-hydroxy-4-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 20 mmol) and methylmagnesium bromide (14 mL, 40 mmol, 3.0 M).

[0300] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.23-3.74 (m, 1H), 2.72-2.52 (m, 1H), 2.50-2.08 (m, 5H), 1.97-1.04 (m, 7H), 0.96-0.36 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, ppm (mixture of diastereomers) δ = 198.0, 197.9, 173.3, 171.1, 115.7, 113.9, 73.5, 70.6, 64.8, 37.4, 37.2, 35.5, 32.8, 32.2, 31.6, 31.0, 30.3, 29.9, 29.3, 29.2, 29.1, 26.4, 23.2, 21.4, 21.0, 20.9, 20.8, 20.7, 20.6, 20.5, 20.3, 20.0, 19.3, 15.0 ppm.

[0301] Odor description: Green, woody, amber, peppery.

[0302] Example 1-34: 2-Ethyl-3,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0303] 1. According to the synthetic procedure of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one in Example 1-1, 2-hydroxy-3,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (23 mmol, 4.5 g, 13% yield) was obtained as a light yellow solid by reaction of cyclohexane-1,3-dione (20 g, 178 mmol) and 2-methylbut-2-enal (18 g, 214 mmol).

[0304] GC / MS(EI):m / z(%):196(32)[M + ],177(5),167(21),153(12),139(100),55(16).

[0305] 2. According to the procedure of Example 1-1, 2-ethyl-3,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (9.4 mmol, 2.0 g, 37% yield) was obtained as a colorless liquid from 2-hydroxy-3,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and ethylmagnesium bromide (51 mL, 51 mmol, 1.0 M).

[0306] 13 C NMR (101 MHz, CDCl3, mixture of isomers) 198.6, 198.3, 198.0, 197.7, 171.6, 171.2, 170.7, 170.6, 117.4, 117.2, 115.4, 114.7, 83.1, 82.5, 78.0, 77.0, 39.7, 37.6, 37.3, 37.0, 34.9, 34.9, 33.4, 32 .5,31.0,30.5,28.8,28.7,28.6,28.6,27.8,25.1,25.0,24.9,24.5,21.5,21.1,2 1.1,20.3,20.1,19.0,15.8,15.7,14.7,13.8,12.4,10.5,10.1,8.8,8.6,7.5ppm. GC / MS(EI):m / z(%):208(85)[M + ],193(91),179(65),165(94),151(45),139(73),123(20),108(24),90(39),82(67),55(100).

[0307] Odor description: Fruity, peppery, woody

[0308] Example 1-35: 4-ethyl-2,3-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0309] 1. According to the synthetic procedure of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one in Example 1-1, 4-ethyl-2-hydroxy-3-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (285 mmol, 60 g, 53% yield) was obtained as a white solid by reaction of cyclohexane-1,3-dione (60 g, 535 mmol) and 2-methylpent-2-enal (63 g, 642 mmol).

[0310] 13 C NMR (101 MHz, CDCl 3 , mixture of isomers) δ = 198.9,198.8,198.1,169.7,169.2,168.3,128.9,115.8,114.6,113.9,98.5,97.9,97.5,94.6,77.3,49.4,38.0,37.2,37.2,37.0,36.9,36.0,34.4,33.3,33.2,32.4,28.8,28.5,27.0,26.9,26.9,23.7,22.9,21.0,20.8,20.6,20.4,17.0,13.6,12.7,11.5,11.3,10.6,8.4 ppm.

[0311] 2. According to the procedure of Example 1-1, 4-ethyl-2,3-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (14 mmol, 2.9 g, 59% yield) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-3-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 24 mmol) and methylmagnesium chloride (48 mL, 48 mmol, 1.0 M).

[0312] 13 C NMR (101 MHz, CDCl 3 , mixture of isomers)δ198.7,198.5,198.1,197.7,173.0,171.8,170.5,170.4,116.1,115.2,114.8,113.9,78.3,77.5,75.1,71.5,38.2,37.9,37.7,37.4,37.3,37.2,37.1,37 .0,36.9,33.2,33.0,31.7,29.0,28.9,28.7,27.6,23.7,21.6,21.1,20.9,20.8,2 0.2,20.0,19.6,18.9,18.0,17.9,16.3,14.6,13.1,12.4,11.8,11.7,8.5,5.9ppm. GC / MS(EI):m / z(%):208(26)[M + ],193(14),179(100),151(30),137(69),79(40),55(61).

[0313] Odor description: woody, tobacco, fiber, pepper, green, myrrh, mushroom

[0314] Example 1-36: 2,4-Diethyl-3-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0315] According to the procedure of Example 1-1, the compound (19 mmol, 4.2 g, 79% yield) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-3-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 24 mmol) and ethylmagnesium chloride (24 mL, 48 mmol, 2.0 M).

[0316] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ 3.92-3.33 (m, 1H), 2.66-1.04 (m, 12H), 1.03-0.59 (m, 9H) ppm.13 C NMR (101 MHz, CDCl 3 , mixture of isomers)δ=198.6,198.4,198.0,197.6,172.9,171.9,170.6,170.5,116.0,114.8,114.1,83.2,82.8,79.3,38.0,37.9,37.7,37.4,37.3,37.2,36.9,34.1,33.8,33.2,3 1.1,29.8,28.9,28.8,28.6,27.6,25.5,25.2,25.1,24.9,23.7,21.9,21.1,20.9,20 .8,20.2,19.9,16.4,14.4,13.0,12.5,11.7,11.6,10.2,10.1,9.1,8.7,8.5,5.9ppm. GC / MS(EI):m / z(%):222(56)[M + ],207(11),193(100),153(76),137(57),55(28).

[0317] Odor description: sweet, caramel, woody, guaiac Tobacco, cedar, pepper, green

[0318] Example 1-37: 2-Ethyl-4,7-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0319] 1. According to the synthetic procedure of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one in Example 1-1, 2-hydroxy-4,7-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one (285 mmol, 60.g, 53% yield) was obtained as a white solid by reaction of 5-methylcyclohexane-1,3-dione (50 g, 396 mmol) and but-2-enal (31 g, 436 mmol).

[0320] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ 5.76-5.15 (m, 2H), 3.02-2.69 (m, 1H), 2.63-1.63 (m, 7H), 1.47-0.92 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of isomers) δ 198.8, 198.5, 169.7, 169.6, 116.2, 115.5, 115.3, 94.9, 93.9, 93.3, 93.2, 45.5, 45.4, 45.3, 45.0, 37.0, 36.8, 36.8, 36.4, 35.6, 34.2, 28.8, 28.6, 28.1, 27.6, 23.5, 22.8, 21.8, 21.1, 21.1, 21.0, 20.9, 20.8, 20.4, 20.0 ppm. GC / MS(EI): m / z(%): 196(65)[M + ],181(6),167(100),153(88),69(30).

[0321] 2. According to the procedure of Example 1-1, 2-ethyl-4,7-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (16 mmol, 3.4 g, 64% yield) was obtained as a colorless liquid from 2-hydroxy-4,7-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and ethylmagnesium chloride (51 mL, 51 mmol, 1.0 M).

[0322] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ 4.16-3.57 (m, 1H), 2.87-2.55 (m, 1H), 2.51-1.24 (m, 9), 1.21-0.84 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of isomers, main peak) δ = 198.1, 197.7, 170.7, 170.6, 170.1, 116.0, 115.7, 115.6, 78.3, 74.4, 74.3, 45.7, 45.2, 37.7, 37.3, 37.2, 37.0, 36.9, 36.7, 33.6, 33.5, 28.8, 28.2, 28.1, 27.9, 27.8, 27.4, 25.8, 25.4, 22.7, 22.3, 21.3, 21.2, 20.9, 20.8, 20.5, 20.3, 20.1, 9.6, 9.5, 9.4 ppm. GC / MS(EI):m / z(%):208(95)[M + ],193(99),179(24),165(100),153(83),138(28),55(25).

[0323] Odor description: woody, fruity, allyl ionone, green

[0324] Example 1-38: 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethyl-4-methyl 2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0325] According to the procedure of Example 1-1, a compound as a colorless liquid (692 mmol, 144 g, 87% yield, containing 90% of 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, wherein trans / cis=2.3:1) was obtained from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (145 g, 796 mmol, 1.0 eq.) and ethylmagnesium chloride (80 mL, 159 mmol, 2.0 M, 0.2 eq.) and propylmagnesium chloride (716 mL, 1432 mmol, 2.0 M, 1.8 eq.)

[0326] 13 C NMR (101 MHz, CDCl 3 , mixture of isomers, main peak) δ = 198.1, 172.0, 171.3, 117.3, 116.1, 74.3, 72.9, 63.4, 38.2, 37.4, 37.2, 37.1, 37.1, 34.1, 33.6, 29.0, 28.8, 28.7, 28.6, 28.2, 25.8, 22.6, 21.7, 21.1, 21.0, 20.9, 20.4, 20.4, 20.1, 18.4, 18.3, 14.0, 9.4 ppm.

[0327] Odor description: spicy, peppery, woody, acet guayil, fruity, berry

[0328] Example 1-39: 2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethyl-4-methyl 2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0329] According to the method of Example 1-1, a colorless liquid compound (31 mmol, 6.5 g, 81% yield, containing 90% of 2-isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, wherein trans / cis=2.2:1) was obtained from 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (7.0 g, 38 mmol, 1.0 equiv.) and ethylmagnesium chloride (3.9 mL, 7.7 mmol, 2.0 M, 0.2 equiv.) and isopropylmagnesium chloride (35 mL, 69 mmol, 2.0 M, 1.8 equiv.).

[0330] 13 C NMR (101 MHz, CDCl3, Mixture of isomers, main peak) δ = 197.7, 172.0, 171.2, 117.2, 116.0, 81.8, 78.3, 77.5, 74.2, 37.6, 37.2, 37.1, 34.8, 33.5, 31.9, 31.8, 30.5, 28.9, 28.8, 28.7, 28.6, 28.1, 27.8, 25.9, 25.7, 22.5, 22.4, 21.0, 20.9, 20.3, 20.0, 18.0, 17.9, 17.7, 17.7, 9.3, 9.3 ppm.

[0331] Odor description: violet, fruity, woody, peppery

[0332] Example 1-40: 2-Ethyl-4-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0333] 1. According to the synthetic procedure of 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one in Example 1-1, 2-hydroxy-4-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (45 mmol, 5.1 g, 55% yield) was obtained as a thick oil by reaction of cyclohexane-1,3-dione (5.0 g, 45 mmol, 1.0 eq.) and E,E-2,4-hexadienal (4.7 g, 49 mol, 1.1 eq.).

[0334] 2-Hydroxy-4-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: GC / MS (EI): m / z (%): 208 (23) [M + ],190(5),180(31),163(61),149(100),139(83),111(55),55(60).

[0335] 2. According to the procedure of Example 1-1, the compound (98.0 mmol, 0.41 g, 11% yield, trans:cis=1:1) was obtained as a colorless liquid from 2-hydroxy-4-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (3.5 g, 17 mmol, 1.0 eq.) and ethylmagnesium bromide (34 mL, 34 mmol, 1.0 M, 2.0 eq.).

[0336] 1 H NMR (400 MHz, CDCl 3)Trans isomer: δ5.53-5.38 (m, 1H), 5.34-5.19 (m, 1H), 3.96-3.84 (m, 1H), 3.36-3.33 (m, 1H), 2.51-2.26 (m, 4H), 2.04-1.91 (m, 2H), 1.80-1.46 (m, 7H), 0.99 (t, J = 7.4 Hz, 3H), cis isomer δ5.53-5.36 (m, 2H), 3.80-3.73 (m, 1H), 3.24-3.14 (m, 1H), 2.44-2.20 (m, 4H), 2.03-1.46 (m, 9H), 0.98 (t, J = 7.5 Hz, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 ) trans isomer δ = 197.4, 171.9, 133.5, 125.8, 112.9, 74.7, 37.2, 31.9, 30.1, 29.0, 28.0, 21.1, 17.9, 9.4, cis isomer δ = 197.4, 172.1, 133.9, 124.1, 115.0, 78.3, 37.3, 35.3, 33.1, 29.1, 27.9, 20.1, 18.0, 9.5 ppm. GC / MS (EI): m / z (%): trans isomer: 220 (42) [M + ],205(15),191(100),179(41),163(35),149(54),91(30),55(35); cis isomer: 220(50)[M + ],205(14),191(100),179(25),163(36),149(61),91(28),55(32).

[0337] Odor description: Woody, peppery, green, fruity.

[0338] Example 2-1: 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethyl-4-methyl-2, 3,4,6,7,8-Hexahydro-5H-chromen-5-one

[0339] 1. Under argon, a mixture of cyclohexane-1,3-dione (240 g, 2.1 mol, 1.0 eq), propionaldehyde (175 g, 3.0 mol, 1.41 eq), ethoxyethylene (222 g, 3.1 mol, 1.44 eq) and L-proline (2.5 g, 21 mmol, 0.01 eq) was stirred in an autoclave bottle at 135° C. (oil temperature) for 16 hours. The solvent was removed to give 503 g of a yellow liquid. The residue was distilled via kugelrohr distillation to give a mixture of 2-ethoxy-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethoxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one as a light yellow oil (459 g, containing 95% of 2-ethoxy-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, yield: 95%).

[0340] 2-Ethoxy-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (containing 5% 2-ethoxy-4-methyl 2,3,4,6,7,8-hexahydro-5H-chromen-5-one): 13 C NMR (101 MHz, CDCl 3 , mixture, main peak) 197.9, 197.7, 169.0, 168.4, 116.1, 115.5, 99.8, 99.3, 98.7, 65.1, 64.8, 64.7, 37.3, 37.2, 34.1, 30.1, 30.0, 29.4, 28.9, 28.7, 28.7, 26.9, 25.6, 20.9, 20.6, 20.5, 20.3, 15.2, 15.2, 11.6, 11.2 ppm.

[0341] 2. A solution of 2-ethoxy-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethoxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (400 g, 1.8 mol, 1.0 eq.) and acetic acid (268 g, 4.5 mol, 2.5 eq.) in THF (140 mL) and water (420 mL) was stirred at 120° C. for 48 h under argon, and then cooled and poured into NaHCO 3 (438 g, 5.2 mol, 2.9 eq.) in 2 L of water, and then extracted with EA (500 mL*4), the organic layer was purified by MgSO 4Dry and remove the solvent by rotary evaporation to give a solid, which is recrystallized to give 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one as white solids (317 g, containing 95% of 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, yield: 90%).

[0342] 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 8-Hexahydro-5H-chromen-5-one: 13 C NMR (101 MHz, CDCl 3 , mixture of isomers, main peak) δ 198.7, 198.5, 170.1, 169.7, 115.9, 115.3, 94.8, 93.3, 37.1, 37.0, 31.6, 31.3, 29.7, 29.3, 28.9, 28.8, 27.0, 25.7, 20.9, 20.3, 11.6, 11.1 ppm.

[0343] 3. To a solution of 4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (310 g, 1.6 mol, 1.0 equiv) in THF (1.5 L) was added ethylmagnesium bromide (1.58 L, 2.0 M, 3.2 mol, 2.0 equiv) at 10° C. to 15° C., and the mixture was stirred at room temperature under an argon atmosphere for 16 hours. The mixture was cooled with an ice bath, and hydrogen chloride (1.16 L, 3.0 M, 3.5 mol, 2.2 equiv) was slowly added, the temperature was controlled below 20° C., and the mixture was stirred at room temperature for 16 h. The organic layer was collected, and the aqueous phase was extracted with EA (500 mL*4), and then the organic layers were combined and washed with NaHCO 3 The organic phase was washed with MgSO 4 The mixture was dried and filtered, and the solvent was removed by rotary evaporation to give a crude oil. The oil was purified by distillation via kugelrohr distillation to give the products 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one and 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one (301 g, trans / cis=1.75:1, containing 95% of 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one, yield: 92%).

[0344] 1 H NMR (400 MHz, CDCl 3, mixture of isomers) δ 3.98-3.58 (m, 1H), 2.61-2.48 (m, 1H), 2.44-2.16 (m, 4H), 2.11-1.78 (m, 4H), 1.75-1.23 (m, 4H), 1.21-1.06 (m, 1H), 1.04-0.96 (m, 3H), 0.95-0.79 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of isomers, main peak) δ 198.0, 197.9, 172.7, 171.1, 116.1, 115.7, 78.5, 74.5, 37.4, 37.3, 34.0, 31.4, 29.3, 29.1, 29.0, 28.9, 28.8, 28.2, 28.0, 27.0, 26.1, 21.1, 20.0, 11.7, 10.4, 9.5, 9.5 ppm.

[0345] Odor description: fruity, woody, violet, cedar

[0346] Example 2-2: 2,4-Diethyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one

[0347] 1. According to the procedure of Example 2-1, 2-ethoxy-4-ethyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one was obtained as a colorless liquid from cyclopentane-1,3-dione (20 g, 204 mmol, 1.0 eq.) and propionaldehyde (36 g, 612 mmol, 3.0 eq.) and ethoxyethylene (16 g, 224 mmol, 1.2 eq.), which was further purified via silica gel chromatography to give a pure product (88 mmol, 19 g, 43% yield, trans: cis = 1:1).

[0348] 2-Ethoxy-4-ethyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one: 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.41-5.05 (m, 1H), 4.10-3.84 (m, 1H), 3.77-3.48 (m, 1H), 2.70-2.30 (m, 5H), 2.19-1.85 (m, 2H), 1.83-1.62 (m, 1H), 1.57-0.77 (m, 7H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ = 203.8, 203.7, 181.8, 181.7, 118.2, 118.1, 102.6, 100.7, 65.2, 65.1, 33.5, 33.4, 31.1, 30.8, 29.4, 27.7, 26.0, 25.9, 25.0, 24.5, 15.1, 15.0, 11.1, 11.0 ppm. GC / MS (EI): m / z (%): 210 (27) [M + ],195(1),181(100),153(19),138(30),125(48),55(14).

[0349] 2. According to the procedure of Example 2-1, 4-ethyl-2-hydroxy-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one (13 g, 69 mmol, yield: 81%) was obtained as a white solid by hydrolysis of 2-ethoxy-4-ethyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one (18 g, 86 mmol). 1 H NMR (400 MHz, CDCl 3 )δ5.71-5.49(m,2H),2.83-1.17(m,12H),0.97-0.79(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 , main peak)δ204.8,183.2,118.1,95.7,33.5,31.8,27.9,26.2,25.6,11.2ppm.

[0350] 3. According to the method of Example 2-1, according to the method of Example 2-1, the title compound (13 mmol, 2.5 g, 59% yield, trans: cis = 1: 1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one (4.0 g, 22 mmol) and ethylmagnesium bromide (22 mL, 44 mmol, 2.0 M).

[0351] 13 C NMR (101 MHz, CDCl 3, Mixture of diastereomers) δ 203.9, 203.8, 184.8, 184.1, 118.7, 117.6, 81.4, 77.6, 32.8, 31.6, 29.7, 29.0, 28.1, 27.8, 26.3, 23.8, 11.6, 10.5, 9.6, 9.5 ppm.

[0352] Odor description: Woody, peppery.

[0353] Example 2-3: 4-ethyl-2-propyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one

[0354] According to the procedure of Example 2-1, the title compound (7.7 mmol, 1.6 g, 35% yield, trans:cis=1:1) was obtained as a colorless liquid from 4-ethyl-2-hydroxy-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one (4.0 g, 22 mmol) and propylmagnesium bromide (22 mL, 44 mmol, 2.0 M).

[0355] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.30-3.92 (m, 1H), 2.62-1.92 (m, 6H), 1.87-1.69 (m, 2H), 1.67-1.13 (m, 5H), 1.08-0.73 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 203.8, 203.8, 184.8, 184.0, 118.6, 117.5, 79.9, 76.2, 37.2, 36.9, 33.5, 33.4, 33.3, 31.6, 30.2, 29.0, 26.9, 26.2, 25.9, 23.8, 18.4, 18.3, 13.9, 11.6, 10.4 ppm. GC / MS (EI): m / z (%): 208 (64) [M + ],193(2),179(45),139(100),125(28),111(46),55(26).

[0356] Odor description: Fruity, woody

[0357] Example 2-4: 2,2,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0358] 1. A mixture of cyclohexane-1,3-dione (10 g, 89 mmol, 1.0 eq.), acetaldehyde (5.9 g, 13 mmol, 1.5 eq.) and 2-methoxyprop-1-ene (9.7 g, 13 mmol, 1.5 eq.) was stirred in an autoclave bottle at 135° C. (oil temperature) for 16 h. The solvent was removed to give 19.2 g of a yellow liquid. The residue was purified by column chromatography on silica gel (hexane: MTBE = 3: 1) to give 2-methoxy-2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (14.5 g, 69 mmol, yield: 77%, trans: cis = 1.2: 1) as a light yellow oil.

[0359] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.37-3.19 (m, 3H), 2.75-1.39 (m, 12H), 1.23-1.14 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, Mixture of diastereomers) δ 198.0, 197.9, 167.9, 167.8, 117.8, 116.2, 101.2, 99.9, 49.3, 49.2, 42.1, 38.5, 37.4, 37.3, 28.6, 22.9, 22.7, 22.5, 22.2, 20.7, 20.1, 19.8, 19.4 ppm.

[0360] 2. A solution of 2-methoxy-2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (11 g, 49 mmol, 1.0 eq.) and acetic acid (30 g, 490 mmol, 10 eq.) in THF (20 mL) and water (60 mL) was stirred at 120° C. under an argon atmosphere for 24 h. The mixture was cooled and added to NaHCO 3 of the mixture, and then extracted with EA (150 mL*4), the organic layer was dried over MgSO4 and filtered, and the solvent was removed by rotary evaporation to give a solid, the solid was washed with solvent (PE:MTBE=20:1) 50 mL*3 to give the product 2-hydroxy-2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (9.2 g, 47 mmol, yield: 96%) as a white solid.

[0361] 1 H NMR (400 MHz, CDCl 3 , mixture of diastereomers) δ 3.84 (d, J = 3.2 Hz, 1H), 3.31-2.64 (m, 1H), 2.51-2.02 (m, 5H), 1.98-1.74 (m, 3H), 1.64-1.44 (m, 3H), 1.23 (m, 3H) ppm. 13 CNMR (101MHz, CDCl 3,diastereoisomer mixture) δ 198.4, 198.3, 169.0, 168.8, 116.5, 115.6, 99.3, 97.9, 49.2, 41.6, 39.5, 37.3, 37.2, 29.8, 29.2, 29.1, 28.1, 27.7, 24.5, 23.3, 22.2, 20.6, 20.2, 19.8, 19.6, 18.8 ppm. GC / MS (EI): m / z (%): 196 (18) [M + ],181(1),153(100),139(56),55(21).

[0362] 3. According to the procedure of Example 2-1, the title compound (10 mmol, 2.0 g, 81% yield) was obtained as a colorless liquid from 2-hydroxy-2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (2.5 g, 13 mmol) and methylmagnesium bromide (26 ml, 26 mmol, 1.0 M).

[0363] 1 H NMR (400 MHz, CDCl 3 )δ2.65-2.52(m,1H),2.46-2.16(m,4H),1.97-1.76(m,3H),1.51-1.39(m,1H),1.36(s,3H),1.19(s,6H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,170.2,115.6,77.0,43.0,37.4,29.5,29.0,24.2,23.0,20.2,19.9ppm. GC / MS(EI):m / z(%):194(42)[M + ],179(14),161(8),151(100),139(54),55(13).

[0364] Odor description: weak, woody, fruity, allyl ionone, green, cork.

[0365] Example 3-1: 2,4-Dimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one

[0366] To a suspension of a solution of cyclohexane-1,3-dione (10.0 g, 89.0 mmol, 1.0 eq.) and pent-3-en-2-one (7.5 g, 89 mmol, 1.0 eq.) in toluene (250 mL) was added zinc (II) chloride (9.7 g, 71 mmol, 0.8 eq.) dropwise at room temperature and stirred for 36 h at 120° C. The solvent was removed and the residue was purified by column chromatography on silica gel (PE: MTBE = 2: 1) to give 2,4-dimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one (20 mmol, 3.6 g, 22% yield) as a light yellow liquid.

[0367] 1 H NMR (400 MHz, CDCl 3 )δ4.78(d,J=4.1Hz,1H),3.26-3.02(m,1H),2.50-2.25(m,4H),2.05-1.92(m,2H),1.81(s,3H),1.08(d,J=6.6Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ198.3,166.8,145.5,115.0,105.9,37.2,27.7,23.8,23.6,20.6,18.5ppm. GC / MS(EI):m / z(%):178(54)[M + ],163(90),135(30),121(100),107(34),91(43),77(67),65(23),55(53).

[0368] Odor description: woody, tobacco, cedar, peppery, green, honey, aromatic

[0369] Example 3-2: 2,4-Dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0370] To a solution of 2,4-dimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one (1 g, 5.6 mmol) in methanol (50 mL) was added 10% Pd / C (0.1 g) and stirred under hydrogen atmosphere for 1 h, the Pd / C was filtered off, and the product was purified by chromatography to give 2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (3.5 mmol, 0.63 g, 62% yield) as a colorless liquid.

[0371] 1 H NMR (400 MHz, CDCl 3)δ3.99-3.85(m,1H),2.71-2.61(m,1H),2.45-1.77(m,8H),1.40-1.24(m,3H),1.17(d,J=6.5Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ198.0,171.8,117.2,73.5,40.1,37.4,29.0,25.8,20.9,20.3,20.1ppm.

[0372] Odor description: Woody, peppery, green, fruity.

[0373] Example 3-3: cis-2,4-diethyl-4,6,7,8-tetrahydro-5H-chromen-5-one

[0374] According to the procedure of Example 3-1, the compound (9.4 mmol, 1.9 g, 10% yield) was obtained as a colorless liquid from cyclohexane-1,3-dione (10 g, 89 mmol) and (E)-hept-4-en-3-one (10 g, 89 mmol).

[0375] 1 H NMR (400 MHz, CDCl 3 )δ4.76(d,J=4.8Hz,1H),3.18(dd,J=9.9,4.4Hz,1H),2.56-2.25(m,4H),2.21-2.09(m,2H ), 2.06-1.88(m,2H),1.55-1.37(m,2H),1.08(t,J=7.5Hz,3H),0.78(t,J=7.5Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ198.3,167.9,151.9,113.1,101.8,37.3,29.3,28.3,27.7,25.7,20.6,11.2,9.2ppm. GC / MS(EI):m / z(%):206(1)[M + ],177(100),149(6),135(19),(16).

[0376] Odor description: woody, peppery, warm, animalic, honey Example 3-4: 2, 3, 4- Trimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one

[0377] According to the procedure of Example 3-1, the title compound (9.9 mmol, 1.9 g, 11% yield) was obtained as a colorless liquid from cyclohexane-1,3-dione (10.0 g, 89 mmol) and 3-methylpent-3-en-2-one (9.6 g, 98 mmol).

[0378] 1 H NMR (400 MHz, CDCl 3 )δ3.13-2.86(m,1H),2.58-2.22(m,4H),2.06-1.91(m,2H),1.83(s,3H),1.66(s,3H),1.06(d,J=5.6Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ=198.2,166.7,140.3,114.9,111.3,37.1,28.5,27.5,20.7,20.6,15.5,15.3ppm. GC / MS(EI):m / z(%):192(4)[M + ],177(100),163(1),149(3),135(4),121(5),105(2),91(9),77(9),65(3),55(6).

[0379] Odor description: fruity, berry, sweet, maltol, woody.

[0380] Example 4-1: (4R)-2-Ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0381] 1. To a solution of cyclohexane-1,3-dione (50.0 g, 446 mmol, 1.0 eq.) and but-2-enal (34 g, 491 mmol, 1.1 eq.) in dichloromethane (250 mL) was added (S)-2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine (15 g, 45 mmol, 0.1 eq.) in dichloromethane (100 mL) at 0°C and stirred under argon for 6 h. The solvent was removed and a crude oil was obtained. The residue was purified by column chromatography on silica gel (hexane:MTBE=5:1 to 1:1) to give (4R)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (66 g, 362 mmol, 81% yield) as a white solid.

[0382] 1 H NMR (400 MHz, CDCl 3, mixture of diastereomers) δ 5.80-5.03 (m, 2H), 3.07-2.67 (m, 1H), 2.51-2.25 (m, 4H), 2.13-1.67 (m, 4H), 1.32-1.06 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 198.8, 198.6, 170.0, 169.2, 116.5, 115.9, 94.4, 93.1, 37.1, 36.9, 35.7, 35.6, 28.8, 28.7, 23.1, 22.9, 21.0, 20.9, 20.4, 20.3 ppm. GC / MS (EI): m / z (%): 182 (72) [M + ],167(6),153(99),139(100),126(24),111(25),97(16),83(29),69(25),55(40).

[0383] 2. To a solution of (4R)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) in tetrahydrofuran (100 mL) was added ethylmagnesium bromide (55 ml, 55 mmol, 1.0 M) in tetrahydrofuran (50 mL) at -10°C and stirred at room temperature under argon for 6 h. NH 4 Cl aqueous solution, and the organic layer is concentrated and the residue is dissolved in toluene (100mL), and 4-methylbenzenesulfonic acid (0.5g, 2.7mmol, 0.1 equivalent) is added, and the mixture is stirred at 100°C for 16h. The solvent is removed to give 4.2g of yellow liquid. The residue is purified by column chromatography on silica gel (hexane: MTBE = 9: 1) to give (4R)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one (3.3g, 17mmol, yield: 62%) as a colorless liquid.

[0384] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.11-3.57 (m, 1H), 2.84-2.55 (m, 1H), 2.47-2.16 (m, 4H), 2.11-1.24 (m, 6H), 1.20-1.05 (m, 3H), 1.04-0.94 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 197.9, 171.9, 171.1, 117.3, 116.1, 78.4, 74.3, 37.6, 37.3, 37.2, 33.6, 28.9, 28.8, 28.1, 27.9, 25.7, 22.5, 21.1, 21.0, 20.3, 20.1, 9.4 ppm. GC / MS (EI): m / z (%): 194 (100) [M + ],179(98),165(25),151(99),139(74),125(18),55(30).

[0385] Odor description: green, fruity, peppery, woody, guaiac, myraldyl.

[0386] (2R,4R)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and (2S,4R)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one were separated as colorless liquids from (4R)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0387] (2R,4R)-2-Ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400 MHz, CDCl 3 )δ4.06-3.81(m,1H),2.90-2.70(m,1H),2.47-2.24(m,4H),2.06-1.86(m,2H),1.80-1.46(m,4H),1.21-0.84(m,6H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ=197.9,171.1,116.1,74.2,37.2,33.6,28.8,28.1,22.5,21.1,21.0,9.4ppm. GC / MS(EI):m / z(%):194(100)[M + ],179(97),165(24),151(99),139(74),125(18),111(18),55(31).

[0388] Odor description: animalic, smokey, burnt, leathery, suede, styrax, pyrogenee, cade

[0389] (2S,4R)-2-Ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400 MHz, CDCl 3 )δ3.81-3.58(m,1H),2.73-2.55(m,1H),2.51-2.17(m,4H),2.11-1.79(m,3H), 1.76-1.53(m,2H),1.39-1.26(m,1H),1.24-1.12(m,3H),1.06-0.88(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ=197.9,171.9,117.3,78.4,37.6,37.3,28.9,27.9,25.7,20.3,20.1,9.4ppm. GC / MS(EI):m / z(%):194(67)[M + ],179(42),166(12),151(60),139(100),55(22).

[0390] Odor description: violet, woody, fatty, fruity, green

[0391] Example 4-2: (4S)-2-Ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0392] 1. According to the procedure of Example 4-1, a mixture of cyclohexane-1,3-dione (20 g, 178 mmol, 1.0 eq.) and but-2-enal (14 g, 196 mmol, 1.1 eq.) was catalyzed by (R)-2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine (5.8 g, 18 mmol, 0.1 eq.) to give (4S)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (84 mmol, 15 g, 47% yield) as a white solid.

[0393] 1 H NMR (400 MHz, CDCl 3 , mixture of diastereomers) δ 5.55-5.30 (m, 1H), 4.88-4.31 (m, 1H), 2.95-2.65 (m, 1H), 2.49-2.26 (m, 4H), 2.10-1.86 (m, 3H), 1.82-1.67 (m, 1H), 1.31-1.04 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of diastereomers) δ 198.6, 198.4, 169.7, 168.8, 116.5, 115.9, 94.4, 93.1, 37.1, 37.0, 35.7, 35.6, 28.8, 28.6, 23.1, 22.8, 21.0, 20.9, 20.4, 20.3 ppm. GC / MS (EI): m / z (%): 182 (56) [M + ],167(5),153(89),139(100),126(26),111(33),55(67).

[0394] 2. According to the procedure of Example 4-1, the compound (6.2 mmol, 1.2 g, 11% yield, trans:cis=1.8:1) was obtained as a colorless liquid from (4S)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (10.0 g, 55 mmol) and ethylmagnesium bromide (110 ml, 110 mmol, 1.0 M).

[0395] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.06-3.50 (m, 1H), 2.91-2.48 (m, 1H), 2.45-2.15 (m, 4H), 2.04-1.26 (m, 6H), 1.21-1.05 (m, 3H), 1.05-0.93 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.8, 171.8, 171.1, 117.2, 116.1, 78.4, 74.2, 37.6, 37.3, 37.2, 33.6, 28.9, 28.8, 28.1, 27.9, 25.7, 22.5, 21.1, 21.0, 20.3, 20.1, 9.5, 9.4 ppm. GC / MS (EI): m / z (%): 194 (86) [M + ],179(86),165(23),151(100),139(85),123(20),55(49).

[0396] Odor description: fruity, peppery, woody, myraldyl, isomethyl ionone, guaiac

[0397] The colorless liquid was separated from (4S)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one by silica gel chromatography (heptane:MTBE=20:1). (2S,4S)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5- ketone .

[0398] 1 H NMR (400 MHz, CDCl 3 )δ3.95-3.77(m,1H),2.71(dd,J=9.3,3.9Hz,1H),2.41-2.19(m,4H),1.86(m,2H),1.70-1.41(m,4H),1.07-0.87(m,6H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ198.0,171.2,116.2,74.3,37.2,33.6,28.8,28.2,22.6,21.1,21.0,9.5ppm. GC / MS(EI):m / z(%):194(100)[M + ],179(95),165(25),151(99),139(73),55(30).

[0399] Odor description: warm, fruity, woody, acet guayil, cedar, myraldyl, isomethyl ionone

[0400] The colorless liquid was separated from (4S)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one by silica gel chromatography (heptane:MTBE=20:1). (2R,4S)-2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5- ketone .

[0401] 1 H NMR (400 MHz, CDCl 3 )δ4.03-3.59(m,1H),2.89-2.54(m,1H),2.48-2.18(m,4H),2.08-1.99(m,1H),1.97-1.7 9(m,2H),1.77-1.51(m,2H),1.38-1.24(m,1H),1.21-1.06(m,3H),1.04-0.94(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,171.9,171.1,117.3,116.1,78.4,74.3,37.6,37.3,37.2,33.6,28.9,28.8,28.1,27.9,25.7,22.5,21.1,21.0,20.3,20.1,9.4ppm. GC / MS(EI):m / z(%):194(64)[M +],179(41),166(12),151(64),139(100),55(32).

[0402] Odor description: Fruity, woody, peppery.

[0403] Example 4-3: (4R)-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0404] According to the procedure of Example 4-1, the compound (15 mmol, 3.1 g, 54% yield) was obtained as a colorless liquid from (4R)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) and propylmagnesium bromide (27 ml, 55 mmol, 2.0 M).

[0405] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.08-3.50 (m, 1H), 2.80-2.45 (m, 1H), 2.42-2.09 (m, 4H), 2.04-1.17 (m, 8H), 1.17-0.96 (m, 3H), 0.95-0.79 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.0, 171.9, 171.1, 117.3, 116.2, 77.1, 72.9, 38.2, 37.4, 37.2, 37.1, 34.2, 29.0, 28.9, 25.8, 22.6, 21.1, 21.0, 20.4, 20.1, 18.4, 18.3, 14.0 ppm. GC / MS (EI): m / z (%): 208 (80) [M + ],193(53),179(26),151(83),139(100),125(26),109(24),55(29).

[0406] Odor description: pepper, green, woody, cedarene, vetiver, grapefruit

[0407] The product was purified by silica gel chromatography (heptane: MTBE = 20:1). (4R)-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro- 5H-chromen-5-one Isolation of (2R,4R)-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0408] (2R,4R)-isomer: 1 H NMR (400 MHz, CDCl 3)δ4.12-3.71(m,1H),2.88-2.59(m,1H),2.48-2.25(m,4H),2.05-1.80(m,2H),1.74-1.37(m,6H),1.08(d,J=6.9Hz,3H),1.01-0.88(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,171.1,116.1,72.9,37.3,37.2,34.1,28.8,22.6,21.1,21.0,18.3,14.0ppm. GC / MS(EI):m / z(%):208(91)[M + ],193(68),179(36),151(99),139(100),125(33),55(36).

[0409] Odor description: peppery, green, woody

[0410] Example 4-4: (4S)-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0411] According to the procedure of Example 4-1, the compound (14 mmol, 2.9 g, 51% yield, trans:cis=2.1:1) was obtained as a colorless liquid from (4S)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) and propylmagnesium bromide (27 ml, 55 mmol, 2.0 M).

[0412] (2S,4S)-4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one: 1 H NMR (400MHz, CDCl3) δ4.11-3.91(m,1H),2.88-2.69(m,1H),2.46-2.27(m,4H), 2.04-1.84(m,2H),1.74-1.38(m,6H),1.15-1.03(m,3H),1.02-0.90(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.9,171.1,116.1,72.9,37.3,37.2,34.1,28.8,22.6,21.1,21.0,18.3,14.0ppm. GC / MS(EI):m / z(%):208(99)[M + ],193(73),179(37),151(100),139(98),125(33),55(33).

[0413] (2R,4S)-4-Methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one :1 H NMR (400 MHz, CDCl 3 )δ3.99-3.58(m,1H),2.82-2.48(m,1H),2.39-2.10(m,4H),2.02-1.70(m,3H),1.66-1.19(m,5H),1.13-0.99(m,3H),0.93-0.82(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ198.0,171.9,171.1,117.3,116.1,72.9,38.2,37.4,37.2,37.1,34. 1,29.0,28.8,25.8,22.6,21.1,21.0,20.3,20.1,18.4,18.3,14.0ppm. GC / MS(EI):m / z(%):208(55)[M + ],193(32),179(12),165(12),151(63),139(100),(33).

[0414] Odor description: fruity, green, acet vetikol, woody, cedar

[0415] Example 4-5: (4R)-2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0416] According to the procedure of Example 4-1, the compound (14 mmol, 2.9 g, 84% yield, trans:cis=3:1) was obtained as a colorless liquid from (4R)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (3.0 g, 16 mmol) and isopropylmagnesium chloride (16 ml, 33 mmol, 2.0 M).

[0417] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.83-3.43 (m, 1H), 2.87-2.51 (m, 1H), 2.45-2.17 (m, 4H), 2.07-1.24 (m, 5H), 1.21-1.04 (m, 3H), 1.02-0.92 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3,diastereoisomer mixture) δ 197.9, 172.2, 171.3, 117.2, 116.1, 81.9, 77.6, 37.3, 37.1, 34.8, 32.0, 31.8, 30.6, 28.9, 28.7, 26.0, 22.4, 21.0, 21.0, 20.3, 20.0, 18.1, 18.0, 17.8, 17.7 ppm. GC / MS (EI): m / z (%): 208 (59) [M + ],193(29),152(30),139(100),55(22).

[0418] Odor description: peppery, creamy, woody, cedar, berry, orris, fruity

[0419] Example 4-6: (4S)-2-Isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0420] According to the procedure of Example 4-1, the compound (8.3 mmol, 1.9 g, 27% yield, trans:cis=1:1) was obtained as a colorless liquid from (4S)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (6.0 g, 33 mmol, 1.0 equiv) and isopropylmagnesium bromide (66 ml, 66 mmol, 1.0 M).

[0421] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.85-3.46 (m, 1H), 2.88-2.54 (m, 1H), 2.46-2.16 (m, 4H), 2.00 (m, 1H), 1.96-1.80 (m, 3H), 1.62-1.53 ​​(m, 1H), 1.30 (m, 1H), 1.13 (dd, J = 41.4, 6.7 Hz, 3H), 1.03-0.94 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.0, 172.2, 171.4, 117.3, 116.2, 82.0, 77.7, 37.4, 37.2, 34.9, 32.1, 31.9, 30.6, 28.9, 28.8, 26.1, 22.5, 21.1, 21.0, 20.4, 20.1, 18.1, 18.0, 17.9, 17.8 ppm. GC / MS (EI): m / z (%): 208 (51) [M + ],193(21),165(19),152(26),139(100),55(20).

[0422] Odor description: woody, isomethyl ionone, fruity, raspberry, sweet, peppery

[0423] Example 4-7: (4R)-2-(sec-butyl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0424] According to the procedure of Example 4-1, the compound (5.4 mmol, 1.2 g, 20% yield) was obtained as a colorless liquid from (4R)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 27 mmol) and sec-butylmagnesium bromide (41 ml, 41 mmol, 1.0 M).

[0425] 1 H NMR (400 MHz, CDCl 3, Mixture of isomers) δ 3.93-3.53 (m, 1H), 2.91-2.00 (m, 6H), 1.97-0.99 (m, 11H), 0.92-0.74 (m, 4H) ppm. 13 C NMR (101 MHz, CDCl 3, Mixture of isomers) δ = 198.0, 197.7, 171.5, 171.4, 169.0, 117.3, 116.3, 116.2, 116.1, 99.2, 98.4, 96.6, 96.2, 80.8, 80.6, 78.1, 76.5, 76.3, 75.8, 75.0, 38.5, 38.4, 38.3, 38.2, 37.3, 37.2, 37.1, 35.2, 35.1, 34. 8,34.2,30.7,29.9,29.8,29.3,28.9,28.7,26.2,26.0,25.2,25.1,24.9,22.9,22.7,22.6,22.4,21 .1,21.0,20.9,20.8,20.7,20.6,20.3,20.0,19.2,19.1,14.2,14.0,11.6,11.5,11.4,9.8,9.7ppm. GC / MS(EI):m / z(%):222(36)[M + ],207(11),193(11),179(2),165(15),151(23),139(100),55(23).

[0426] Odor description: fruity, creamy, woody, cedar, peppery

[0427] Example 4-8: (4S)-2-(sec-butyl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0428] According to the procedure of Example 4-1, the compound (16 mmol, 3.5 g, 47% yield, trans:cis=2:1) ​​was obtained as a colorless liquid from (4S)-2-hydroxy-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (6.0 g, 33 mmol) and sec-butylmagnesium bromide (66 ml, 66 mmol, 1.0 M).

[0429] 1H NMR (400MHz, CDCl 3, Mixture of isomers) δ 3.96-3.56 (m, 1H), 2.72 (m, 1H), 2.44-2.16 (m, 4H), 2.02-1.83 (m, 2H), 1.76-1.20 (m, 5H), 1.18 (d, J = 6.5 Hz, 1H), 1.08 (m, 2H), 1.00-0.85 (m, 6H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of diastereomers) δ 197.9, 172.3, 172.2, 171.5, 171.4, 117.4, 116.2, 116.1, 80.8, 80.6, 76.5, 76.3, 38.6, 38.5, 38.4, 38.3, 37.4, 37.2, 35.2, 34.3, 30.8, 2 9.8,28.9,28.8,28.7,26.2,26.1,25.2,25.1,25.0,24.9,22.6,22.5,21.1 ,21.0,20.4,20.3,20.1,14.3,14.2,14.1,14.0,11.6,11.5,11.5,11.5ppm. GC / MS(EI):m / z(%):222(45)[M + ],207(13),193(12),139(100),55(21).

[0430] Odor description: woody, acet Cyperus ketone, peppery, fatty, fruity, isomethyl ionone

[0431] Example 4-9: (4R)-4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0432] 1. According to the procedure of Example 4-1, (4R)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (294 mmol, 59 g, 66% yield) was obtained as a white solid from cyclohexane-1,3-dione (50 g, 446 mmol, 1.0 equiv) and pent-2-enal (41 g, 491 mmol, 1.1 equiv) catalyzed by (S)-2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine (14.5 g, 44.6 mmol, 0.1 equiv).

[0433] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.67-5.01 (m, 2H), 2.75-2.54 (m, 1H), 2.49-2.23 (m, 4H), 2.15-1.41 (m, 5H), 1.30-1.05 (m, 1H), 1.01-0.73 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of diastereomers) δ 198.6, 170.3, 169.9, 115.8, 115.2, 94.8, 93.3, 37.1, 36.9, 31.7, 31.3, 29.7, 29.3, 28.9, 28.7, 26.9, 25.6, 20.9, 20.3, 11.6, 11.0 ppm. GC / MS (EI): m / z (%): 196 (38) [M + ],178(8),167(86),153(59),139(100),125(33),79(30),55(47).

[0434] 2. According to the procedure of Example 4-1, the compound (5.2 mmol, 1.0 g, 20% yield) was obtained as a colorless liquid from (4R)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and methylmagnesium bromide (13 ml, 38 mmol, 3.0 M).

[0435] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.23-3.77 (m, 1H), 2.65-2.47 (m, 1H), 2.46-2.14 (m, 4H), 2.09-1.60 (m, 4H), 1.47-1.02 (m, 5H), 0.98-0.73 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl3, diastereoisomer mixture) δ 197.9, 197.8, 172.5, 170.9, 116.0, 115.4, 73.5, 69.5, 37.3, 37.2, 36.3, 31.5, 31.4, 29.4, 29.0, 28.9, 27.0, 26.0, 21.1, 21.0, 20.9, 20.0, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 194 (35) [M + ],179(9),165(100),151(6),137(23),55(13).

[0436] Odor description: woody, cedar, powdery, green

[0437] Example 4-10: (4S)-4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0438] 1. According to the procedure of Example 4-1, (4S)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (68 mmol, 13.3 g, 76% yield) was obtained as a white solid from cyclohexane-1,3-dione (10.0 g, 89 mmol, 1.0 equiv) and pent-2-enal (8.3 g, 98 mmol, 1.1 equiv) catalyzed by (R)-2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine (3.2 g, 45 mmol, 0.1 equiv).

[0439] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 5.45-5.32 (m, 1H), 4.97-4.30 (m, 1H), 2.70-2.54 (m, 1H), 2.49-2.25 (m, 4H), 2.16-1.41 (m, 5H), 1.33-1.06 (m, 1H), 1.00-0.83 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.3, 169.8, 169.8, 169.4, 115.9, 115.3, 94.7, 93.2, 37.1, 37.0, 31.5, 31.3, 29.7, 29.2, 28.9, 28.7, 26.9, 25.7, 20.9, 20.3, 11.6, 11.1 ppm. GC / MS (EI): m / z (%): 196 (53) [M +],178(10),167(99),153(66),139(100),125(31),107(24),97(20),79(26),69(16),55(45).

[0440] 2. According to the procedure of Example 4-1, (4S)-4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (13 mmol, 2.5 g, 43% yield) was obtained as a colorless liquid from (4S)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (6.0 g, 31 mmol) and methylmagnesium bromide (20 ml, 61 mmol, 3.0 M).

[0441] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.22-3.78 (m, 1H), 2.65-2.46 (m, 1H), 2.45-2.17 (m, 4H), 2.13-1.59 (m, 4H), 1.49-1.03 (m, 5H), 0.99-0.71 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.9, 197.8, 172.6, 171.0, 116.1, 115.7, 77.1, 73.1, 37.5, 37.4, 37.3, 37.2, 34.5, 31.4, 29.6, 29.3, 29.1, 28.9, 27.0, 26.1, 21.1, 20.1, 18.4, 18.3, 14.0, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 194 (35) [M + ],179(9),165(100),151(6),137(21),55(10).

[0442] Odor description: woody, green, peppery

[0443] Example 4-11: (4R)-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0444] According to the procedure of Example 4-1, the title compound (9.1 mmol, 1.9 g, 36% yield, trans:cis=1.8:1) was obtained as a colorless liquid from (4R)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and ethylmagnesium bromide (51 ml, 51 mmol, 1.0 M).

[0445] 1H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.00-3.54 (m, 1H), 2.63-2.47 (m, 1H), 2.45-2.16 (m, 4H), 2.10-1.19 (m, 8H), 1.13-0.96 (m, 3H), 0.95-0.77 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 198.0, 197.9, 172.6, 171.0, 116.1, 115.7, 78.5, 74.4, 37.4, 37.2, 33.9, 31.4, 29.3, 29.1, 29.0, 28.9, 28.2, 28.0, 27.0, 26.0, 21.0, 20.0, 11.7, 10.3, 9.5, 9.4 ppm. GC / MS (EI): m / z (%): 208 (31) [M + ],193(10),179(100),165(8),153(18),137(27),55(27).

[0446] Odor description: woody, cedar, green, peppery

[0447] The product was purified by silica gel chromatography (heptane: MTBE = 20:1). (4R)-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H- Chromene-5-one Separation of colorless liquid (2R,4R)-2,4-Diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one .

[0448] 1 H NMR (400 MHz, CDCl 3 )δ3.98-3.82(m,1H),2.59-2.48(m,1H),2.44-2.25(m,4H),1.99-1.89(m,2H),1.87-1.79(m,1H),1. 77-1.55(m,3H),1.45-1.33(m,1H),1.16-1.05(m,1H),1.04-0.97(m,3H),0.92(t,J=7.4Hz,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.8,171.0,115.6,74.4,37.2,29.2,29.0,28.8,28.2,27.0,21.0,11.7,9.4ppm. GC / MS(EI):m / z(%):208(38)[M + ],193(10),179(100),137(18),125(21),55(12).

[0449] Odor description: Woody, cedar, peppery

[0450] Example 4-12: (4S)-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0451] According to the procedure of Example 4-1, the title compound (16 mmol, 3.4 g, 64% yield, trans:cis=1.7:1) was obtained as a colorless liquid from (4S)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and ethylmagnesium bromide (51 ml, 51 mmol, 1.0 M).

[0452] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.99-3.57 (m, 1H), 2.64-2.45 (m, 1H), 2.45-2.18 (m, 4H), 2.15-1.55 (m, 6H), 1.50-0.96 (m, 5H), 0.95-0.74 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.9, 197.8, 172.6, 171.0, 116.0, 115.6, 78.4, 74.4, 37.3, 37.1, 33.9, 31.3, 29.2, 29.1, 29.0, 28.8, 28.2, 27.9, 26.9, 26.0, 21.1, 20.0, 11.6, 10.3, 9.5, 9.4 ppm. GC / MS (EI): m / z (%): 208 (42) [M + ],193(10),179(100),153(20),137(21),125(23),55(13).

[0453] Odor description: woody, peppery, green, fruity

[0454] (2S,4S)-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one was separated as a colorless liquid from (4S)-2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one via silica gel chromatography (heptane:MTBE=20:1).

[0455] 1 H NMR (400 MHz, CDCl 3)δ3.99-3.82(m,1H),2.62-2.47(m,1H),2.45-2.26(m,4H),2.01-1.80(m,3H),1.78-1.5 5(m,3H),1.48-1.32(m,1H),1.17-1.05(m,1H),1.04-0.96(m,3H),0.95-0.86(m,3H)ppm. 13 C NMR (101 MHz, CDCl 3 )δ197.8,171.0,115.6,74.4,37.2,29.2,29.0,28.8,28.2,26.9,21.0,11.6,9.4ppm. GC / MS(EI):m / z(%):208(35)[M + ],193(10),179(100),151(11),137(18),55(13).

[0456] Odor description: Woody, peppery, green.

[0457] Example 4-13: (4R)-4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0458] According to the procedure of Example 4-1, the compound (17 mmol, 3.7 g, 65% yield, trans:cis=2.5:1) was obtained as a colorless liquid from (4R)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 26 mmol) and propylmagnesium bromide (26 ml, 51 mmol, 2.0 M).

[0459] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.08-3.58 (m, 1H), 2.65-2.48 (m, 1H), 2.46-2.16 (m, 4H), 2.10-1.81 (m, 3H), 1.76-1.28 (m, 6H), 1.22-0.55 (m, 7H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 197.9, 197.8, 172.6, 171.0, 116.1, 115.7, 77.1, 73.1, 37.5, 37.4, 37.3, 37.2, 34.5, 31.4, 29.6, 29.3, 29.1, 28.9, 27.0, 26.1, 21.1, 20.1, 18.4, 18.3, 14.0, 11.7, 10.3 ppm. GC / MS (EI): m / z (%): 222 (37) [M +],207(7),193(100),179(3),165(10),153(15),137(15),125(40),55(15).

[0460] Odor description: woody, peppery, guayil, green

[0461] Example 4-14: (4S)-4-Ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0462] According to the procedure of Example 4-1, the compound (13 mmol, 2.9 g, 73% yield, trans:cis=2.1:1) was obtained as a colorless liquid from (4S)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (3.5 g, 18 mmol) and propylmagnesium bromide (18 ml, 36 mmol, 2.0 M).

[0463] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 4.09-3.58 (m, 1H), 2.64-2.47 (m, 1H), 2.46-2.16 (m, 4H), 2.05-1.24 (m, 9H), 1.19-0.70 (m, 7H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ 198.0, 197.9, 172.7, 171.1, 116.1, 115.7, 77.1, 73.1, 37.5, 37.4, 37.3, 34.5, 31.4, 29.6, 29.3, 29.1, 28.9, 27.0, 26.1, 21.1, 20.0, 18.4, 18.3, 14.0, 11.7, 10.4 ppm. GC / MS (EI): m / z (%): 222 (38) [M + ],207(7),193(100),165(11),153(18),125(40),55(14).

[0464] Odor description: green, woody, vetiver, root, cedarene, pepper

[0465] Example 4-15: (4R)-4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0466] According to the procedure of Example 4-1, the compound (13 mmol, 2.8 g, 62% yield, trans:cis=3.2:1) was obtained as a colorless liquid from (4R)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (4.0 g, 20.4 mmol, 1.0 equiv) and isopropylmagnesium bromide (20 ml, 41 mmol, 2.0 M).

[0467] 1 H NMR (400 MHz, CDCl 3, Mixture of diastereomers) δ 3.94-3.31 (m, 1H), 2.63-2.48 (m, 1H), 2.45-2.17 (m, 4H), 2.10-1.61 (m, 5H), 1.51-1.05 (m, 2H), 1.02-0.76 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3, diastereoisomer mixture) δ = 197.9, 197.8, 172.9, 171.2, 116.1, 115.7, 81.9, 77.7, 37.4, 37.2, 32.1, 32.0, 31.6, 31.1, 29.1, 29.0, 28.8, 26.9, 26.0, 25.9, 21.1, 20.0, 18.1, 17.9, 17.8, 11.6, 10.3. GC / MS (EI): m / z (%): 222 (57) [M + ],207(14),193(100),153(40),137(47),125(30),55(20).

[0468] Odor description: woody, green, rooty, vetiver, slightly ambery, powdery, iris, isomethyl ionone, peppery

[0469] Example 4-16: (4S)-4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0470] According to the procedure of Example 4-1, the compound (6.8 mmol, 1.5 g, 44% yield, trans:cis=6:1) was obtained as a colorless liquid from (4S)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (3.0 g, 15 mmol) and isopropylmagnesium bromide (16 ml, 31 mmol, 2.0 M).

[0471] 1 H NMR (400 MHz, CDCl 3, mixture of diastereomers) δ 4.00-3.43 (m, 1H), 2.67-2.16 (m, 5H), 2.11-1.47 (m, 5H), 1.46-1.05 (m, 2H), 1.03-0.77 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3 , mixture of diastereomers) δ 197.9, 197.8, 172.9, 171.2, 116.0, 115.7, 115.5, 81.9, 77.7, 37.3, 37.2, 32.0, 31.9, 31.6, 29.1, 29.0, 28.8, 26.9, 26.0, 25.9, 21.0, 20.0, 18.1, 17.8, 17.7, 11.6, 11.5, 10.3 ppm. GC / MS (EI): m / z (%): 222 (54) [M + ],207(15),193(100),153(32),137(47),125(31),55(23).

[0472] Odor description: violet, woody, peppery, fruity

[0473] Example 4-17: (4R)-2-(sec-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0474] According to the procedure of Example 4-1, the compound (18 mmol, 4.2 g, 70% yield, trans:cis=2.1:1) was obtained as a colorless liquid from (4R)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 25 mmol) and sec-butylmagnesium bromide (51 ml, 51 mmol, 1.0 M).

[0475] 1 H NMR (400 MHz, CDCl 3, Mixture of isomers) δ 3.94-3.48 (m, 1H), 2.62-2.47 (m, 1H), 2.45-2.14 (m, 4H), 2.06-1.52 (m, 6H), 1.49-1.04 (m, 3H), 1.01-0.77 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3,mixture of isomers) δ = 197.8, 197.7, 173.0, 172.9, 171.3, 171.2, 116.1, 115.8, 115.7, 80.8, 80.5, 38.6, 38.5, 38.4, 38.3, 37.3, 37.2, 31.8, 31.6, 31.4, 30.4, 29.3 ,29.1,29.0,28.9,28.8,26.9,26.1,26.0,25.2,25.1,25.0,24.9,21.1,20. 0,14.3,14.2,14.1,14.0,11.9,11.8,11.7,11.6,11.5,11.4,10.4,10.3ppm. GC / MS(EI):m / z(%):236(48)[M + ],221(7),207(100),153(45),137(27),125(31),55(19).

[0476] Odor description: green, citrus, grapefruit, green, woody, peppery

[0477] Example 4-18: (4S)-2-(sec-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0478] According to the procedure of Example 4-1, the compound (18 mmol, 4.3 g, 71% yield, trans:cis=2:1) ​​was obtained as a colorless liquid from (4S)-4-ethyl-2-hydroxy-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (5.0 g, 2 mmol) and sec-butylmagnesium bromide (51 ml, 51 mmol, 1.0 M).

[0479] 1 H NMR (400 MHz, CDCl 3 , mixture of isomers) δ 3.96-3.53 (m, 1H), 2.60-2.49 (m, 1H), 2.45-2.17 (m, 4H), 2.05-1.88 (m, 2H), 1.82-1.65 (m, 2H), 1.64-1.03 (m, 5H), 0.99-0.78 (m, 9H) ppm. 13 C NMR (101 MHz, CDCl 3,mixture of isomers)δ197.9,197.8,173.1,173.0,171.4,171.3,116.2,115.8,115.8,80.9,80.6,76.6,76.5,38.7,38.6,38.5,38.4,37.4,37.3,31.9,31.7,31.5,30 .5,29.4,29.2,29.1,28.9,28.8,26.9,26.1,26.0,25.2,25.1,25.0,24.9,21 .1,20.1,14.4,14.3,14.2,14.1,11.7,11.7,11.6,11.6,11.5,11.5,10.4ppm. GC / MS(EI):m / z(%):236(48)[M + ],221(6),207(100),189(4),153(51),137(29),125(32),55(21).

[0480] Odor description: fruity, woody, peppery, green, grapefruit

[0481] Example 5: High-grade spices and aromatic fragrances

[0482]

[0483]

[0484] The above perfume accord is a powdery floral oriental accord, for example, suitable for application at 10 wt % to ethanol (85 vol %).

[0485] By replacing 10 parts of DPG with 10 parts of a mixture comprising 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (Example 2-1), a accord with a powdery amber fragrance note is obtained, with a very natural soft peppery and powdery cedar impression. This addition leads to a significant increase in persistence, which obviously benefits the overall performance of the accord.

[0486] By replacing 10 parts of DPG with 10 parts of a mixture comprising 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (Example 1-38), a accord with full, creamy incense notes is obtained, with very natural peppery and sandalwood impressions. This addition results in a significant increase in persistence, which clearly benefits the overall performance of the accord.

[0487] By replacing 10 parts of DPG with 10 parts of 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (Example 1-1), a accord with a fruity musky blackberry note is obtained, with a very natural peppery and creamy sandalwood impression. Again, this addition leads to a significant increase in persistence, which is clearly beneficial to the overall performance of the accord. In addition, the addition of 2-ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one enhances the peppery, woody and cyperus azulene notes.

Claims

1. A compound of formula (I) in R 1 Selected from C1-C5 alkyl, R 2 is selected from hydrogen, C1-C3 alkyl, R 3 is selected from hydrogen, methyl and ethyl, R 4 is selected from C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl and C5-C6 cycloalkenyl, R 5 is selected from hydrogen and methyl, n is 0 or 1, and The dashed line together with the CC bond represents a single bond and m is 1, or The dashed line together with the CC bond represents a double bond and m is 0.

2. The compound according to claim 1, wherein the compound of formula (I) is a compound of formula (II) in R 1 Selected from C1-C5 alkyl, R 2 is selected from hydrogen, C1-C3 alkyl, R 3 is selected from hydrogen, methyl and ethyl, R 4 is selected from C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl and C5-C6 cycloalkenyl, n is 0 or 1, and The dashed line together with the CC bond represents a single bond and m is 1, or The dashed line together with the CC bond represents a double bond and m is 0.

3. The compound according to claim 1, wherein the compound of formula (I) is a compound of formula (III) in R 1 Selected from C1-C5 alkyl, R 2 is selected from hydrogen, C1-C3 alkyl, R 4 is selected from C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl and C5-C6 cycloalkenyl, n is 0 or 1, and The dashed line together with the CC bond represents a single bond or a double bond.

4. A compound according to claim 1, selected from the group consisting of: 2-(but-2-ene-2-yl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one; 2-(but-2-ene-2-yl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one; 2-(but-3-ene-2-yl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one; 2-(but-3-ene-2-yl)-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one; 2-(sec-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromene-5-one; 2-(tert-butyl)-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,2,4-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,3,4-trimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one; 2,4-diethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,4-diethyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one; 2,4-diethyl-3-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2 ,4-diethyl-4,6,7,8-tetrahydro-5H-chromen-5-one; 2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2,4-dimethyl-4,6,7,8-tetrahydro-5H-chromen-5-one; 2-allyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-allyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-butyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-butyl-4-methyl-2,3,4, 6,7,8-Hexahydro-5H-chromen-5-one; 2-Cyclopropyl-4-ethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-Cyclopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-Ethyl-3,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-Ethyl-4-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-Ethyl-4,7-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-Ethyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one;2-Ethyl-4-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-isobutyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 2-isopropyl-4-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-(2-methylallyl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4 -ethyl-2-(2-methylprop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-(prop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-(prop-1-en-2-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2,3-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-isobutyl-2,3 ,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-isopropyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-ethyl-2-propyl-3,4,6,7-tetrahydrocyclopenta[b]pyran-5(2H)-one; 4-ethyl-2-vinyl-2,3,4,6, 7,8-Hexahydro-5H-chromen-5-one; 4-isopropyl-2-methyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-methyl-2-(2-methylprop-1-en-1-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; 4-methyl-2-(prop-1-en-2-yl)-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; and 4-methyl-2-propyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one; and mixtures thereof. ; 5. A fragrance composition comprising a compound of formula (I) as defined in any one of claims 1 to 4 or a mixture thereof.

6. A perfumed article comprising a compound of formula (I) as defined in any one of claims 1 to 4 or a mixture thereof and a consumer product base.

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

8. Use of a compound of formula (I) as defined in any one of claims 1 to 4 or a mixture thereof as a fragrance.

9. A method of improving, enhancing and / or modifying a consumer product base by adding thereto an olfactorily acceptable amount of a compound of formula (I) as defined in any one of claims 1 to 4 or a mixture thereof.

Images