Dimethylbicycloheptenyl and dimethylbicycloheptanyl derivatives and their use as odorants

Abstract

Dimethylbicycloheptenyl and dimethylbicycloheptanyl derivatives are disclosed that have odor notes of green galbanum and fruity pineapple.

Description

[Technical Field]

[0001] Technical Field The present invention relates to flavor and fragrance ingredients and compositions containing them useful for flavor and fragrance applications. The present invention also relates to methods for their preparation. In particular, the present invention relates to dimethylbicycloheptenyl and dimethylbicycloheptanyl derivatives of formula (I) having odor notes of green galbanum and fruity pineapple. [Background technology]

[0002] background In the flavor and fragrance industry, perfumers and flavorists are constantly searching for new compounds with unique olfactory properties, for example, ingredients with green fruity pineapple odor notes reminiscent of galbanum are sought after for the flavor and fragrance industry.

[0003] Galbanum oil is a natural fragrance ingredient highly valued by perfumers for its green characteristics. However, its high cost limits its use. Synthetic substitutes with an odor reminiscent of galbanum oil are described, for example, in U.S. Pat. No. 4,147,672, which discloses 3,3-dimethylcyclohexyl and 3,3-dimethylcyclohexenyl derivatives. Fragrance ingredients reminiscent of galbanum oil are also described in EP 913383, which discloses spirocyclic compounds, or in WO 2012110281, which discloses 1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one, which imparts a galbanum-type odor note.

[0004] Galbanum is valued for its ability to impart a rich, spicy, green scent. The green galbanum odor family is very important in creating fragrance accords. Several famous fragrances derive their characteristics from this odor family.

[0005] There is a continuing need for new fragrance ingredients reminiscent of galbanum. In addition to the primary objective of providing new fragrance ingredients of the galbanum odor family, it is desirable that the ingredients be derived from renewable resources. As market demand for new fragrances based on renewable raw materials increases, the use of renewable starting materials is becoming increasingly important as a replacement for at least a portion of ingredients derived from petrochemical feedstocks.

[0006] Surprisingly, the inventors have discovered that a new class of ingredients of formula (I), as defined below, possess the highly sought-after green galbanum and fruity pineapple odor notes, all obtained from renewable starting materials. Summary of the Invention

[0007] overview According to a first aspect of the present invention, compounds of formula (I) are provided in the form of any one of their stereoisomers or mixtures thereof. [ka] During the ceremony, The dotted lines, together with the carbon-carbon bond, form single or double bonds; n is 1 or 0; X is selected from —O— and —CH—, and R 1 is hydrogen or methyl.

[0008] According to a second aspect of the present invention, there is provided an article that is fragranced and comprises as an odorant a compound of formula (I) according to the first aspect.

[0009] 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 consumer product by adding an olfactory acceptable amount of a compound of formula (I) of the first aspect.

[0010] According to a fourth aspect of the present invention there is provided a flavoured product comprising a compound of formula (I) according to the first aspect.

[0011] According to a fifth aspect of the present invention there is provided a fragrance or flavour composition comprising a compound of formula (I) according to the first aspect.

[0012] According to a sixth aspect of the present invention there is provided the use of a compound of formula (I) of the first aspect as a flavour or fragrance.

[0013] Particular embodiments of any aspect of the invention may provide one or more of the following advantages. Green galbanum and fruity pineapple odor profile, Powerful compounds, · Made from natural and / or renewable resources; · It is biodegradable.

[0014] The details, examples, and preferences provided with respect to any particular one or more aspects of the invention are further described herein and apply equally to all aspects of the invention. Unless otherwise specified herein or clearly contradicted by context, any combination of all possible variations of the embodiments, examples, and preferences described herein is encompassed by the invention.

[0015] Detailed Description The present invention is based on the surprising discovery that dimethylbicycloheptenyl derivatives have odour notes of green galbanum and fruity pineapple.

[0016] In a first aspect of the present invention, there is provided a compound of formula (I) [ka] During the ceremony, The dotted lines, together with the carbon-carbon bond, form single or double bonds; n is 1 or 0; X is selected from —O— and —CH—; and R 1 is hydrogen or methyl.

[0017] In one particular embodiment, there is provided a compound of formula (I) wherein n is 1, ie a compound of formula (Ia). [ka] During the ceremony, The dotted lines, together with the carbon-carbon bond, form single or double bonds; X is selected from —O— and —CH—; and R 1 is hydrogen or methyl.

[0018] In another particular embodiment, R 1 Compounds of formula (Ia) are provided wherein is hydrogen.

[0019] In another particular embodiment, there are provided compounds of formula (I) wherein n is 0, ie, compounds of formula (Ib). [ka] The dotted lines, together with the carbon-carbon bond, form single or double bonds; X is selected from —O— and —CH—; and R 1 is hydrogen or methyl.

[0020] In another particular embodiment, compounds of formula (Ib) are provided wherein X is -CH2-.

[0021] In another particular embodiment, the compound of formula (I) is 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one, 1-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)pent-4-en-1-one, Allyl 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate, 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one, 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one, and Allyl 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylate is selected from the group consisting of:

[0022] The compounds of formula (I) contain two or more chiral centers and therefore may exist as mixtures of stereoisomers or may be resolved as isomerically pure forms. Where it is desired to prepare individual stereoisomers, this may be achieved by methods known in the art, such as preparative HPLC and GC, or stereoselective synthesis, or simply by using as starting materials the desired isomerically pure forms available from natural sources.

[0023] In one particular embodiment, the compound of formula (Ia) in which the dotted line forms a single bond together with the carbon-carbon bond is a compound in which the relative configuration of the ring system is (1S,5R), for example, 1-((1S,5R)-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one.

[0024] In another particular embodiment, the compound of formula (Ia) in which the dotted line forms a single bond together with the carbon-carbon bond is a compound in which the relative configuration of the ring system is (1R,5S), for example, allyl(1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate.

[0025] In another particular embodiment, the compound of formula (Ia) in which the dotted line forms a double bond together with the carbon-carbon bond is a compound in which the relative configuration of the ring system is (1S,5S), for example, 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)pent-4-en-1-one.

[0026] The compounds of formula (I) may be used alone, as isomeric mixtures thereof, or in combination with known odor molecules selected from the wide range of currently available natural and synthetic molecules such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and / or in admixture with one or more ingredients or excipients conventionally used in combination with odorants in fragrance compositions, such as carrier materials, and other adjuvants commonly used in the art.

[0027] As used herein, "carrier material" means a material that is substantially neutral from an odor point of view, i.e., a material that does not significantly alter the sensory properties of the odorant.

[0028] The term "adjuvant" refers to an ingredient that may be used in a fragrance composition for reasons not specifically related to the olfactory performance of the composition. For example, an adjuvant may be an ingredient that aids in the processing of the fragrance ingredient(s) or the composition containing said ingredient(s), or may improve the handling or storage of the fragrance ingredient(s) or the composition containing them. 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 fragrance composition. A detailed description of the nature and types of adjuvants commonly used in fragrance compositions containing adjuvants is not exhaustive, but it should be stated that said ingredients are well known to those skilled in the art.

[0029] As used herein, "fragrance composition" refers to a composition comprising a compound of formula (I), or a mixture thereof, and a base material, e.g., diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1,2-diol, triethyl citrate (TEC), alcohol (e.g., ethanol), or other diluents typically used in combination with odorants. Optionally, the composition may also contain an antioxidant adjuvant. The antioxidant may be Tinogard. (R) TT (BASF), Tinogard (R) Q (BASF), tocopherol (including its isomers, CAS 59-02-9, 364-49-8, 18920-62-2, 121854-78-2), 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) and related phenols, hydroquinone (CAS 121-31-9).

[0030] The following list is an example of known odorants that can be combined with the compounds of formula (I), or mixtures thereof: - essential oils and extracts, for example castoreum, costus root oil, oakmoss absolute, geranium oil, tree moss absolute, fruit oils such as basil oil, bergamot oil and mandarin oil, myrtle oil, palmarose oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil.

[0031] alcohols, such as cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol), cis-3-hexenol ((Z)-hex-3-en-1-ol), citronellol (3,7-dimethyloct-6-en-1-ol), dihydromyrcenol (2,6-dimethyloct-7-en-2-ol), Ebanol TM((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol), eugenol (4-allyl-2-methoxyphenol), ethyl linalool ((E)-3,7-dimethylnona-1,6-dien-3-ol), farnesol ((2E,6Z)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol), geraniol ((E)-3,7-dimethylocta-2,6-dien-1-ol); Super Muguet TM ((E)-6-Ethyl-3-methyloct-6-en-1-ol); Linalool (3,7-dimethylocta-1,6-dien-3-ol); Menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2,6-octadien-1-ol); Phenylethyl alcohol (2-phenylethanol); Rhodinol TM (3,7-dimethyloct-6-en-1-ol); Sandalore TM (3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-1-yl)propan-2-ol); or Timberol TM (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7-trimethylocta-2,6-dien-1-ol, and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]-methanol;

[0032] Aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde), alpha-amyl cinnamic aldehyde (2-benzylideneheptanal), Georgywood TM (1-(1,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone), hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal), Iso E Super (R)(1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone), Isoraldeine (R) ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one), Hedione TM (methyl 3-oxo-2-pentylcyclopentaneacetate), 3-(4-isobutyl-2-methylphenyl)propanal, maltol, methyl cedryl ketone, methyl ionone, verbenone, and / or vanillin.

[0033] ethers and acetals, e.g., Ambrox (R) (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta-2,6-diene); and / or Spirambrene (R) (2′,2′,3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5′-[1,3]dioxane]);

[0034] Esters and lactones, such as benzyl acetate, cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methanoazulen-6-yl acetate), delta-decalactone (6-pentyltetrahydro-2H-pyran-2-one), Helvetolide (R) (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropylpropionate), delta-undecalactone (5-heptyloxolan-2-one), and / or vetiveryl acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulen-6-yl)acetate);

[0035] macrocyclic compounds, such as ambrettolide ((Z)-oxacycloheptadec-10-en-2-one), ethylene brassylate (1,4-dioxacycloheptadecane-5,17-dione), and / or exaltolide; (R) (16-oxacyclohexadecan-1-one), and heterocyclic compounds, such as isobutylquinoline (2-isobutylquinoline).

[0036] Thus, in a further aspect of the present invention there is provided a fragrance composition comprising a compound of formula (I).

[0037] The compounds of formula (I) can be used in a wide range of fragranced articles, including perfumes, air care products, household products, laundry products, body care products, cosmetics, and all areas of luxury and functional fragrances. The compounds can be used in a wide range of amounts, depending on the particular article and the nature and amount of other odorants. The amount is typically 0.00001 to 3 weight percent of the article. In one embodiment, the compounds can be used in fabric softeners in an amount of 0.0001 to 3 weight percent (e.g., 0.001 to 1 weight percent, including 0.5, 0.3, and 0.05 weight percent). In another embodiment, the compounds can be used in luxury perfumes in an amount of 0.01 to 30 weight percent (e.g., up to about 10 weight percent, or up to 20 weight percent), more preferably 0.01 to 5 weight percent (e.g., 0.01 to 0.1 weight percent). However, these values ​​are provided by way of example only; experienced perfumers may achieve effects or create new harmonies at lower or higher concentrations.

[0038] The compounds of formula (I) may be applied to a consumer product base by simply mixing the compound, or a fragrance composition comprising a compound of formula (I) or a combination thereof, directly with the consumer product base, or may be entrapped at an earlier stage in an entrapment material such as, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides, and mixtures thereof, and then mixed with the consumer product base.

[0039] Thus, the present invention further provides a method for producing a fragranced article, which comprises either directly mixing a compound of formula (I) or a mixture thereof as a fragrance ingredient into a consumer product base using conventional techniques and methods, or mixing a fragrance composition comprising a compound of formula (I) or a mixture thereof, and then mixing it with a consumer product base. The addition of an olfactory-acceptable amount of a compound of formula (I) or a mixture thereof improves, enhances, or modifies the odor notes of the consumer product base.

[0040] Thus, the present invention further provides a method for improving, enhancing or modifying a consumer product base by adding to the consumer product base an olfactory acceptable amount of a compound of formula (I) or a mixture thereof.

[0041] In a further aspect of the present invention, a) a compound of formula (I) [ka] During the ceremony, The dotted lines, together with the carbon-carbon bond, form single or double bonds; n is 1 or 0; X is selected from —O— and —CH—, and R 1 is hydrogen or methyl; and b) Consumer product base A fragranced article comprising:

[0042] As used herein, "consumer product base" refers to a composition for use as a consumer product that performs specific functions, such as cleaning, softening, and care. Examples of such products include luxury perfumes, such as perfumes and eau de toilette; fabric care products, household products, personal care products, such as cosmetics, laundry detergents, rinse conditioners, personal cleaning agents, dishwasher detergents, and surface cleaners; laundry products, such as fabric softeners, bleaches, and detergents; body care products, such as shampoos and shower gels; and air care products (preferably containing volatile, usually pleasant-smelling compounds, including products that can mask unpleasant odors even in very small amounts). Air fresheners for residential spaces contain, in particular, natural and synthetic essential oils, such as pine needle oil, citrus oil, eucalyptus oil, and lavender oil, in amounts of, for example, up to 50% by weight. As aerosols, they tend to contain lower amounts of such essential oils, for example less than 5% or less than 2% by weight, and also contain additional compounds such as acetaldehyde (especially less than 0.5% by weight), isopropyl alcohol (especially less than 5% by weight), mineral oil (especially less than 5% by weight), propellants, etc.

[0043] Cosmetics include: (a) Skin care cosmetics, in particular bath products, skin cleansing and cleansing products, skin care products, eye make-up, lip care products, nail care products, intimate care products and foot care products; (b) Cosmetics with specific effects, in particular sunscreens, tanning products, bleaching products, deodorants, antiperspirants, depilatories, and shaving products; (c) Dental care cosmetics, in particular dental and oral care products, tooth care products, cleaning agents for dental prostheses, adhesives for dental prostheses; and (d) Hair care cosmetics, in particular hair shampoos, hair care products, hair setting products, hair shaping products and hair coloring products.

[0044] This list of products is provided by way of example and is not intended to be limiting in any way.

[0045] In one particular embodiment, the consumer product base is selected from luxury perfumes and personal care products, including deodorants, hair care products, soaps, etc. In one particular embodiment, the consumer product base is a hair care product.

[0046] In more particular embodiments, the consumer product base is selected from fabric care products, including fabric softeners, and home care products, including air fresheners, dishwashers, and the like.

[0047] The compound of formula (I) where n is 1 and X is -CH2- may be synthesized, for example, by oxidation of α-pinene to the corresponding aldehyde myrtenal, followed by a Grignard reaction, and then oxidation to give the corresponding ketone. Alternatively, the compound may be synthesized, for example, by oxidation of α-pinene to the corresponding aldehyde myrtenal, followed by hydrogenation, a Grignard reaction, and then oxidation to give the corresponding ketone.

[0048] Compounds of formula (I) where n is 1 and X is oxygen may be further elaborated, for example, by stepwise oxidation of α-pinene to the corresponding acids, followed by esterification to the corresponding esters.

[0049] For example, α-pinene is found in the oils of many species of conifers, particularly pine. Pinene exists in two enantiomers, (1S,5S)- or (-)-α-pinene and (1R,5R)- or (+)-α-pinene, both of which occur naturally. (-)-α-pinene is found predominantly in European pine trees, while (+)-α-pinene is found predominantly in North America. Racemic mixtures are also found in some oils, such as eucalyptus oil and orange peel oil.

[0050] Compounds of formula (I) where n is 0 may be synthesized, for example, by isomerization of 3-carene epoxide to 3(10)-caren-4-ol, followed by oxidation, Grignard reaction, and then oxidation to give the corresponding ketone. Alternatively, compounds of formula (I) where n is 0 may be synthesized, for example, by isomerization of acetylcarene followed by α-allylation to form the corresponding ketone.

[0051] Compounds of formula (I) where n is 0 and X is oxygen may be synthesized, for example, by isomerization of 3-carene epoxide to 3(10)-caren-4-ol, followed by oxidation to the corresponding acid, followed by Grignard reaction and oxidation to form the corresponding ester.

[0052] 3-Carene epoxide is obtained by epoxidation of 3-carene (3,7,7-trimethylbicyclo[4.1.0]hept-3-ene) and is commonly found in essential oils such as turpentine, juniper, and pine needle oil. Two enantiomers exist: (+)-3-carene or (1S,6R)-3-carene and (-)-3-carene or (1R,6S)-3-carene, both of which occur naturally.

[0053] The present invention is further described with reference to the following non-limiting examples, which are for illustrative purposes only and it will be understood that variations and modifications may occur to those skilled in the art.

[0054] example All reactions were carried out under argon using commercially available solvents and reagents without further purification. Solvents for extraction and chromatography were of industrial grade and used without further purification. Flash chromatography was performed using Tsingdao Haiyang Chemical silica gel (200-300 mesh) and Santai Technologies silica flash columns. Unless otherwise noted, a mixture of heptane:MTBE was used as the eluent. NMR spectra were recorded on an AW 400 MHz Bruker spectrometer. 1Chemical shifts for 1 H NMR spectra are reported in δ (ppm) referenced to the residual proton signal of the deuterated solvent, and coupling constants are expressed in Hertz (Hz). 13 C NMR spectra were 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 = double doublet, and bs = broad singlet. GC / MS spectral data were acquired on an Agilent 6890 N and MSD 5975 using an HP-5 MS, 30 m, 0.25 mm, 0.25 μm column.

[0055] Example 1: 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one a. To a solution of α-pinene (20.0 g, 147 mmol) and selenium dioxide (16.3 g, 147 mmol) in 1,4-dioxane (100 mL) was added acetic acid (13.2 g, 220 mmol) slowly at 0 °C and stirred at 80 °C for 16 h. The reaction was quenched by adding saturated NH4Cl solution, and the mixture was diluted with ethyl acetate (150 mL). * The mixture was extracted with 3). The organic layer was washed with saturated NaHCO3 solution, brine, and dried over MgSO4. The solvent was removed, and the residue was distilled to give myrtenal (6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde) (14.6 g, 97 mmol, 66% yield) as a colorless liquid.

[0056] 1 H NMR (400 MHz, CDCl3) δ 9.44 (s, 1H), 6.75 - 6.69 (m, 1H), 2.87 (t, J = 5.5 Hz, 1H), 2.64 - 2.45 (m, 3H), 2.22 - 2.16 (m, 1H), 1.34 (s, 3H), 1.06 (d, J = 9.2 Hz, 1H), 0.75 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 191.2, 151.5, 147.8, 40.7, 38.1, 37.6, 33.0, 31.1, 25.7, 20.9 ppm. GC / MS (EI): m / z (%): 150 (1) [M + ], 135 (14), 107 (74), 91 (40), 79 (100).

[0057] b. To a solution of but-3-en-1-yl magnesium chloride (121 mL, 61 mmol, 0.5 M) in tetrahydrofuran (100 mL), myrtenal (6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde, 7.0 g, 47 mmol) in tetrahydrofuran (50 mL) was added at 10 °C and stirred at room temperature for 3 h. The reaction was quenched with saturated NH4Cl solution and ethyl acetate (150 mL) was added. * The mixture was extracted with 3). The combined organic layers were washed with saturated NaHCO3 solution and brine, and dried over MgSO4. The solvent was removed, and the residue was purified by silica gel chromatography (PE:MTBE=4:1) to give 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol (5.9 g, 29 mmol, yield: 61%) as a pale yellow liquid.

[0058] 1 H NMR (400 MHz, CDCl3,mixture of isomers) δ 5.96 - 5.67 (m, 1H), 5.48 - 5.39 (m, 1H), 5.10 - 4.89 (m, 2H), 4.07 - 3.97 (m, 1H), 2.48 - 2.00 (m, 7H), 1.61 - 1.30 (m, 6H), 1.17 - 1.12 (m, 1H), 0.90 - 0.77 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3,mixture of isomers) δ 150.5, 150.0, 138.6, 138.5, 118.1, 117.6, 114.7, 114.7, 74.4, 74.3, 42.1, 41.8, 41.0, 41.0, 37.8, 37.8, 33.9, 33.6, 31.8, 31.8, 31.2, 31.1, 30.2, 30.0, 26.2, 26.1, 21.4, 21.4 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 188 (2), 173 (4), 163 (24), 145 (55), 107 (99), 91 (100), 79 (77), 67 (88).

[0059] c. A mixture of 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol (4.0 g, 19.4 mmol), aluminum tri-sec-butoxide (1.4 g, 5.8 mmol), and acetic acid (0.1 g, 1.9 mmol) in MTBE (100 mL) was stirred at rt for 20 min, then benzaldehyde (8.2 g, 78 mmol) was added at rt and stirred for an additional 3 h. The reaction was quenched with water and MTBE (100 mL) was added. * The mixture was extracted with 3). The organic layer was dried over MgSO. The solvent was removed, and the residue was purified by silica gel chromatography (PE:MTBE=4:1) to give 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one (3.6 g, 18 mmol, yield: 91%) as a colorless liquid.

[0060] 1H NMR (400 MHz, CDCl3) δ 6.81 - 6.69 (m, 1H), 5.94 - 5.70 (m, 1H), 5.10 - 4.92 (m, 2H), 3.00 - 2.91 (m, 1H), 2.85 - 2.64 (m, 2H), 2.56 - 2.28 (m, 5H), 2.17 - 2.07 (m, 1H), 1.33 (s, 3H), 1.02 (d, J = 9.1 Hz, 1H), 0.74 (s, 3H) ppm. 13 GC / MS (EI): m / z (%): 204 (1) [M + ], 189 (3), 161 (27), 105 (100), 91 (25), 77 (22), 55 (48). Odor description: Green galbanum, fruity pineapple, metallic, fatty.

[0061] Example 2: 1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one a. (1R)-(-)-Myrtenal (50.0 g, 333 mmol) was reacted with but-3-en-1-yl magnesium chloride (433 mL, 433 mmol) according to the procedure in Example 1 (step b) to give 1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol as a colorless liquid (248 mmol, 51.1 g, 74% yield).

[0062] GC / MS (EI): m / z (%): 206 (1) [M + ], 188 (1), 173 (4), 163 (23), 145 (54), 107 (94), 91 (100), 79 (85), 67 (73), 55 (65).

[0063] b. 1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol (40.0 g, 194 mmol) and benzaldehyde (82.0 g, 775 mmol) were reacted according to the procedure in Example 1 (step c) to give 1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one as a colorless liquid (142 mmol, 29.1 g, 74% yield).

[0064] 1 H NMR (400 MHz, CDCl3) δ 6.71 - 6.63 (m, 1H), 5.88 - 5.64 (m, 1H), 5.03 - 4.83 (m, 2H), 2.94 - 2.81 (m, 1H), 2.77 - 2.54 (m, 2H), 2.52 - 2.22 (m, 5H), 2.09 - 2.01 (m, 1H), 1.25 (s, 3H), 0.95 (d, J = 9.0 Hz, 1H), 0.67 (s, 3H) ppm. 13 GC / MS (EI): m / z (%): 204 (1) [M + ], 189 (3), 161 (26), 105 (100), 55 (55). Odor description: Green, galbanum, fruity, fatty, metallic, pineapple.

[0065] Example 3: 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one a. (1S)-(+)-Myrtenal ((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde, 8.1 g, 54 mmol) was reacted with but-3-en-1-yl magnesium chloride (140 mL, 70 mmol) according to the procedure in Example 1 (step b) to give 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol as a colorless liquid (28 mmol, 5.7 g, 51% yield).

[0066] 1 H NMR (400 MHz, CDCl 3, mixture of isomers) δ 5.93 - 5.72 (m, 1H), 5.52 - 5.33 (m, 1H), 5.09 - 4.87 (m, 2H), 4.03 - 3.97 (m, 1H), 2.48 - 2.01 (m, 7H), 1.62 - 1.41 (m, 3H), 1.32 - 1.28 (m, 3H), 1.18 - 1.12 (m, 1H), 0.87 - 0.80 (m, 3H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of isomers) δ 150.5, 150.0, 138.6, 138.5, 118.0, 117.6, 114.7, 114.6, 74.4, 74.3, 42.1, 41.9, 41.0, 40.9, 37.8, 37.7, 33.9, 33.6, 31.9, 31.8, 31.2, 31.1, 30.2, 30.0, 26.2, 26.1, 21.5, 21.4 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 188 (3), 173 (3), 145 (44), 107 (68), 91 (100), 79 (68), 67 (83), 55 (59).

[0067] b. 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol (4.1 g, 20 mmol) and benzaldehyde (8.4 g, 82 mmol) were reacted according to the procedure in Example 1 (step c) to give 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one as a colorless liquid (16 mmol, 3.3 g, 81% yield).

[0068] 1 H NMR (400 MHz, CDCl3) δ 6.75 - 6.61 (m, 1H), 5.80 - 5.71 (m, 1H), 5.03 - 4.84 (m, 2H), 2.88 (dt, J = 1.0, 5.6 Hz, 1H), 2.77 - 2.59 (m, 2H), 2.50 - 2.21 (m, 5H), 2.12 - 1.99 (m, 1H), 1.25 (s, 3H), 0.95 (d, J = 9.0 Hz, 1H), 0.66 (s, 3H) ppm. 13 C NMR (101 MHz, CDCl3) 198.5, 149.1, 137.5, 136.5, 115.0, 40.2, 39.5, 37.3, 36.1, 32.5, 31.1, 28.9, 25.8, 20.8 ppm. GC / MS (EI): m / z (%): 204 (1) [M + ], 189 (2), 161 (18), 105 (100), 91 (24), 55 (59). Odor description: Green galbanum, fruity pineapple, metallic.

[0069] Example 4: 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)pent-4-en-1-one a. To a solution of (1R)-(-)-myrtenal (20.0 g, 133 mmol) in EA (150 mL) was added 10% Pd / C (1.4 g) at room temperature, and the resulting suspension was hydrogenated at 1 atm and room temperature (rt) for 16 h. The product was purified by Kugelrohr distillation to give (1S,5S)-6,6-dimethylbicyclo[3.1.1]heptane-2-carbaldehyde (20.1 g, 132 mmol, yield: 99%) as a colorless liquid.

[0070] b. (1S,5S)-6,6-Dimethylbicyclo[3.1.1]heptane-2-carbaldehyde (15.0 g, 99 mmol) was reacted with but-3-en-1-yl magnesium chloride (128 mL, 128 mmol, 1.0 M) according to the procedure in Example 1 (step b) to give 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]heptane-2-yl)pent-4-en-1-ol as a pale yellow liquid (13.6 g, 65 mmol, yield: 66%). GC / MS (EI): m / z (%): 208 (1) [M + ], 193(6), 179 (2), 139 (14), 105 (15), 82 (81), 67 (100), 55 (86).

[0071] c. To a solution of 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)pent-4-en-1-ol (10.0 g, 48 mmol) in DCM (200 mL) was added pyridinium chlorochromate (11.4 g, 53 mmol) in portions at 10 °C and stirred at rt for 3 h. The reaction was quenched by adding hexane (300 mL), and the suspension was filtered through a short silica gel pad. The solvent in the filtrate was removed to give a crude oil. This was purified by silica gel chromatography (PE:MTBE=96:4) to give 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)pent-4-en-1-one (1.9 g, 9.2 mmol, yield: 19%) as a colorless liquid.

[0072] 1H NMR (400 MHz, CDCl3) δ 5.91 - 5.64 (m, 1H), 5.05 - 4.95 (m, 2H), 2.81 - 2.79 (m, 1H), 2.57 - 2.25 (m, 7H), 2.00 - 1.70 (m, 4H), 1.25 - 1.15 (m, 4H), 0.72 (s, 3H) ppm. 13 C NMR (101 MHz, CDCl3) δ 212.0, 137.5, 115.0, 53.1, 43.0, 40.7, 39.2, 38.9, 30.1, 28.1, 27.3, 24.9, 22.0, 13.8 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 191 (5), 163 (7), 151 (11), 123 (46), 95 (30), 67 (43), 55 (100). Odor description: Fruity pineapple, fatty, green galbanum.

[0073] Example 5: Allyl 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate a. To a solution of myrtenal (6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde, 3.0 g, 20 mmol), 2-methylbut-2-ene (7.0 g, 100 mmol), and 2-methylpropan-2-ol (7.4 g, 100 mmol) in water (100 mL) was slowly added sodium chlorite (5.4 g, 60 mmol) and potassium phosphate (13.6 g, 100 mmol) in water (200 mL) at 10 °C, and the mixture was stirred at rt for 16 h. The reaction mixture was cooled to 100 °C with MTBE (100 mL). * The crude oil was extracted with 3), washed with NaHCO3 solution and brine, and dried over MgSO4. The solvent was removed, and the resulting crude oil was purified by distillation to give 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid (3.0 g, 18 mmol, yield: 90%) as a colorless liquid.

[0074] b. To a solution of 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid (1.5 g, 9.0 mmol) and potassium carbonate (1.6 g, 11.7 mmol) in DMF (25 mL) was added 3-bromoprop-1-ene (1.2 g, 9.9 mmol) and stirred at rt for an additional 16 h. The reaction was diluted with MTBE (50 mL). * The crude oil was extracted with 2) and dried over MgSO. The concentrated crude oil was purified by silica gel chromatography (PE:MTBE=97:3) to give allyl 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate (1.9 g, 8.2 mmol, 91% yield) as a colorless liquid.

[0075] 1 H NMR (400 MHz, CDCl3) δ 6.97 - 6.78 (m, 1H), 6.01 - 5.92 (m, 1H), 5.41 - 5.12 (m, 2H), 4.63 (d, J = 5.6 Hz, 2H), 2.88 - 2.78 (m, 1H), 2.55 - 2.33 (m, 3H), 2.14 - 2.11 (m, 1H), 1.33 (s, 3H), 1.12 (d, J = 9.1 Hz, 1H), 0.80 (s, 3H) ppm. 13 C NMR (101 MHz, CDCl3) δ 165.8, 140.1, 136.7, 132.6, 117.7, 64.9, 41.2, 40.3, 37.7, 32.2, 31.3, 25.9, 20.9 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 191 (1), 165 (10), 149 (9), 105 (100), 91 (46), 79 (38). Odor description: Aromatic, resinous, coniferous, metallic, fatty, fruity pineapple, green galbanum.

[0076] Example 6: Allyl (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate a. (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid was obtained as a colorless liquid (16 mmol, 2.6 g, 94% yield) from the reaction of (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde (2.5 g, 17 mmol), 2-methylbut-2-ene (5.8 g, 83 mmol), 2-methylpropan-2-ol (6.2 g, 83 mmol) and sodium chlorite (4.6 g, 51 mmol) according to the procedure of Example 5 (step a).

[0077] b. Following the procedure of Example 5 (step b), (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid (1.5 g, 9.0 mmol) was reacted with 3-bromoprop-1-ene (1.2 g, 9.9 mmol) to give allyl (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate as a colorless liquid (7.8 mmol, 1.6 g, 86% yield).

[0078] 1 H NMR (400 MHz, CDCl3) δ 6.91 - 6.80 (m, 1H), 6.01 - 5.91 (m, 1H), 5.37 - 5.14 (m, 2H), 4.63 (d, J = 5.6 Hz, 2H), 2.82 - 2.80 (m, 1H), 2.51 - 2.32 (m, 3H), 2.17 - 2.07 (m, 1H), 1.33 (s, 3H), 1.12 (d, J = 9.1 Hz, 1H), 0.80 (s, 3H) ppm. 13 C NMR (101 MHz, CDCl3) δ 165.8, 140.1, 136.7, 132.6, 117.7, 64.9, 41.2, 40.3, 37.7, 32.2, 31.3, 25.9, 20.9 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 191 (1), 165 (7), 105 (100), 91 (51), 79 (45). Odor description: Green galbanum, metallic, carrot, garlic, fatty, fruity pineapple.

[0079] Example 7: Allyl (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate a. (1R,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid was obtained as a colorless liquid (130 mmol, 21.6 g, 97% yield) from the reaction of (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde (20.0 g, 133 mmol), 2-methylbut-2-ene (46.7 g, 666 mmol), 2-methylpropan-2-ol (49.3 g, 666 mmol) and sodium chlorite (36.0 g, 399 mmol) according to the procedure of Example 5 (Step 1).

[0080] b. (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid (5.0 g, 30 mmol) was reacted with 3-bromoprop-1-ene (4.0 g, 33 mmol) according to the procedure in Example 5 (step b) to give allyl (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate as a colorless liquid (27 mmol, 5.6 g, 90% yield).

[0081] 1 H NMR (400 MHz, CDCl3) δ 6.88 - 6.84 (m, 1H), 6.01 - 5.91 (m, 1H), 5.35 - 5.21 (m, 2H), 4.63 (d, J = 5.5 Hz, 2H), 2.83 - 2.80 (m, 1H), 2.52 - 2.33 (m, 3H), 2.17 - 2.03 (m, 1H), 1.33 (s, 3H), 1.12 (d, J = 9.1 Hz, 1H), 0.80 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 165.8, 140.0, 136.8, 132.6, 117.7, 64.9, 41.2, 40.3, 37.7, 32.2, 31.3, 25.9, 20.9 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 191 (1), 165 (7), 105 (100), 91 (53), 79 (46). Odor description: Green, metallic, galbanum, aromatic.

[0082] Example 8: 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one a. To a solution of diisopropylamine (47.9 g, 473 mmol) in THF (200 mL) was added n-butyllithium (296 mL, 473 mmol) slowly at -78 °C and stirred at rt for 30 min under an argon atmosphere. Next, 3-carene epoxide (3,8,8-trimethyl-4-oxatricyclo[5.1.0.0]) in THF (200 mL) was added. 3,5 ]octane (60.0 g, 394 mmol) was added slowly at -78 °C and stirred at rt for 5 h. Saturated NH4Cl (100 mL) was added and MTBE (200 mL) was added. * The organic layer was washed with NaHCO3 solution and brine, and dried over MgSO4. The solvent was removed, and the crude oil was distilled to give 3(10)-caren-4-ol (7,7-dimethyl-4-methylenebicyclo[4.1.0]heptan-3-ol, 56.6 g, 372 mmol, 94% yield) as a colorless liquid.

[0083] b. To a solution of 3(10)-caren-4-ol (7,7-dimethyl-4-methylenebicyclo[4.1.0]heptan-3-ol, 15.0 g, 99 mmol) in toluene (50 mL) was added (((oxovanadio)oxy)triphenyl-15-syl)((triphenyl(((triphenyl(11-phosphanyl)-15-syl)oxy)-12-phosphanyl)-15-syl)oxy)-12-phosphane (5.8 g, 5.9 mmol) at 10° C. and stirred at 100° C. for 6 h. After cooling to rt, water (50 mL) was added and MTBE (100 mL) was added. * The organic layer was extracted with 3) and dried over MgSO. The organic layer was concentrated and the resulting crude oil was purified by silica gel chromatography (PE:MTBE=9:1) to give 3-carene-10-ol ((7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)methanol, 6.8 g, 45 mmol, yield: 45%) as a pale yellow liquid.

[0084] c. To a solution of 3-caren-10-ol ((7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)methanol, 5.0 g, 33 mmol) in DCM (100 mL) was added pyridinium chlorochromate (9.2 g, 43 mmol) and stirred at rt for 5 h. Hexane (200 mL) was added, and the resulting suspension was filtered. The filtrate was concentrated, and the resulting crude oil was purified by silica gel chromatography (PE:MTBE=97:3) to give 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carbaldehyde (1.3 g, 8.7 mmol, yield: 26%) as a colorless liquid.

[0085] d. Following the procedure of Example 1 (step b), but-3-en-1-yl magnesium chloride (17.5 mL, 8.7 mmol, 0.5 M) was reacted with 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carbaldehyde (1.0 g, 6.7 mmol) to give 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-ol (1.0 g, 4.8 mmol, 73% yield) as a pale yellow liquid.

[0086] 1 H NMR (400 MHz, CDCl3) δ 5.88 - 5.71 (m, 1H), 5.59 - 5.53 (m, 1H), 5.10 - 4.88 (m, 2H), 4.03 - 3.95(m, 1H), 2.47 - 1.78 (m, 5H), 1.68 - 1.59 (m, 2H), 1.43 - 1.25 (m, 2H), 1.04, 1.04 (s, 3H), 0.93 - 0.62 (m, 5H) ppm. 13 C NMR (101 MHz, CDCl3) δ 138.5, 138.4, 137.6, 137.5, 122.4, 121.6, 114.7, 114.6, 76.5, 76.0, 34.2, 33.9, 30.2, 30.1, 28.4, 28.3, 20.6, 20.5, 18.6, 17.8, 17.7, 17.6, 17.4, 17.2, 17.0, 13.4, 13.4 ppm.

[0087] e. Following the procedure of Example 1 (step b), 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-ol (0.9 g, 4.4 mmol) was reacted with aluminum tri-sec-butoxide (0.3 g, 1.3 mmol) and benzaldehyde (1.9 g, 17.0 mmol) to give 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one (0.50 g, 2.5 mmol, 57% yield) as a colorless liquid.

[0088] 1H NMR (400 MHz, CDCl3) δ 6.88 - 6.72 (m, 1H), 5.86 - 5.77 (m, 1H), 5.04 - 4.94 (m, 2H), 2.74 - 2.57 (m, 3H), 2.57 - 2.46 (m, 1H), 2.40 - 2.28 (m, 2H), 2.27 - 2.14 (m, 2H), 1.05 (s, 3H), 0.88 - 0.78 (m, 1H), 0.74 - 0.66 (m, 4H) ppm. 13 GC / MS (EI): m / z (%): 204 (6) [M + ], 189 (5), 175 (2), 161 (28), 105 (100), 55 (56). Odor description: Green, fatty, metallic, galbanum, aromatic, coniferous, fir needle.

[0089] Example 8.1: 1-((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one a. To a solution of (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carbaldehyde (7.0 g, 47 mmol) in THF (25 mL) was added a solution of but-3-en-1-ylmagnesium chloride (121 mL, 61 mmol, 0.5 M) in THF (50 mL) at 10 °C and stirred at rt for 5 h. Saturated aqueous NH4Cl (100 mL) was added. The mixture was diluted with EA (200 mL). *The resulting mixture was extracted with 3). The combined organic layers were washed with saturated NaHCO3 solution (100 mL) and brine (100 mL), then dried over MgSO4 and filtered. The solvent was removed by rotary evaporation, and the resulting crude oil was purified by silica gel chromatography (heptane:MTBE = 4:1) to give 1-((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-ol (7.1 g, 34 mmol, yield: 74%) as a colorless liquid.

[0090] 1 H NMR (400 MHz, CDCl3, mixture of isomers) δ 5.87 - 5.77 (m, 1H), 5.58 - 5.51 (m, 1H), 5.08 - 4.90 (m, 2H), 4.01 - 3.95 (m, 1H), 2.42 - 1.26 (m, 9H), 1.04 - 0.64 (m, 8H) ppm. 13 C NMR (101 MHz, CDCl 3, mixture of isomers) δ 138.5, 138.4, 137.6, 137.5, 122.3, 121.5, 114.7, 114.6, 76.4, 75.9, 34.2, 33.9, 30.2, 30.1, 28.4, 28.3, 20.5, 20.4, 18.6, 17.8, 17.7, 17.4, 17.2, 17.0, 13.4, 13.3 ppm. GC / MS (EI): m / z (%): 206 (12) [M + ], 191 (10), 173 (9), 163 (29), 145 (40), 119 (21), 105 (77), 91 (99), 79 (100), 67 (70), 55 (74).

[0091] b. A mixture of 1-((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-ol (7.0 g, 34 mmol), aluminum tri-sec-butoxide (2.5 g, 10 mmol), and acetic acid (204 mg, 3.4 mmol) in MTBE (100 mL) was stirred at rt for 10 min. 4-Nitrobenzaldehyde (11.5 g, 76 mmol) was added and stirred at rt for 6 h. Water (50 mL) was added, and the resulting mixture was diluted with MTBE (200 mL). * The resulting mixture was extracted with 3). The combined organic layers were dried over MgSO and filtered. The solvent was removed using a rotary evaporator, and the resulting crude oil was purified by silica gel chromatography (heptane:MTBE = 96:4) to give 1-((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one (6.6 g, 32 mmol, yield: 95%) as a colorless liquid.

[0092] 1 H NMR (400 MHz, CDCl3) δ 6.83 -6.81 (m, 1H), 5.86 -5.77 (m, 1H), 5.07 - 4.95 (m, 2H), 2.75 - 2.46 (m, 4H), 2.37 - 3.31 (m, 2H), 2.27 - 2.12 (m, 2H), 1.05 (s, 3H), 0.85 - 0.69 (m, 2H), 0.69 (s, 3H) ppm. 13 C NMR (101 MHz, CDCl3) δ 200.2, 138.5, 137.6, 137.2, 114.9, 36.4, 28.7, 28.1, 22.1, 18.1, 17.8, 17.5, 16.6, 13.5 ppm. GC / MS (EI): m / z (%): 204 (6) [M + ], 189 (4), 161 (27), 149 (17), 121 (31), 105 (100), 77 (35), 55 (59). Odor description: Green, galbanum, fatty, fruity

[0093] Example 9: Allyl 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylate a. 7,7-Dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid was obtained as a white solid (2.1 g, 11.0 mmol, purity: 90%, yield: 66%) from the reaction of 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carbaldehyde (4.0 g, 17.3 mmol), 2-methylbut-2-ene (6.1 g, 86.5 mmol), 2-methylpropan-2-ol (6.4 g, 86.5 mmol) and sodium chlorite (4.7 g, 51.9 mmol) according to the procedure of Example 5 (Step 1).

[0094] 13 C NMR (101 MHz, CDCl3) δ 171.7, 139.9, 126.8, 27.1, 21.0, 17.7, 16.7, 16.6, 15.5, 12.4 ppm.

[0095] b. 7,7-Dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid (2.1 g, 11.0 mmol, purity: 90%) was reacted with 3-bromoprop-1-ene (2.1 g, 17.1 mmol) according to the procedure in Example 5 (step b) to give allyl 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylate (1.6 g, 7.8 mmol, yield: 68%) as a colorless liquid.

[0096] 1 H NMR (400 MHz, CDCl3) δ 7.04 - 6.77 (m, 1H), 5.98 - 5.90 (m, 1H), 5.39 - 5.17 (m, 2H), 4.64 - 4.62 (m, 2H), 2.69 - 2.53 (m, 2H), 2.28 - 2.09 (m, 2H), 1.06 (s, 3H), 0.87 - 0.64 (m, 5H) ppm. 13C NMR (101 MHz, CDCl3) δ 167.0, 138.5, 132.5, 128.2, 117.7, 64.9, 28.2, 21.8, 19.0, 17.8, 17.5, 16.6, 13.4 ppm. Odor description: Green, fruity pineapple, galbanum.

[0097] Example 9.1: Allyl (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylate a. To a solution of (1S,6R)-3,7,7-trimethylbicyclo[4.1.0]hept-3-ene (50.0 g, 367 mmol) in CHCl3 (400 mL), m-CPBA (80.5 g, 85% Wt, 396 mmol) was slowly added at 23-27 °C and stirred at rt overnight. Heptane (200 mL) was added and the solid was filtered. EA (500 mL) was added and the resulting mixture was diluted with NaHSO3 (200 mL). * 3), saturated NaHCO3 aqueous solution (200mL * The resulting organic layer was dried over MgSO4 and then filtered. The solvent was removed by rotary evaporation. The crude product was purified by silica gel chromatography (heptane:MTBE = 94:6) to give (1S,7R)-3,8,8-trimethyl-4-oxatricyclo[5.1.0.0]. 3,5 ]octane (51.6 g, 339 mmol, yield: 92%) was obtained as a colorless liquid.

[0098] 1 H NMR (400 MHz, CDCl3) δ 2.84 - 2.79 (m, 1H), 2.33 - 2.11 (m, 2H), 1.66 - 1.47 (m, 2H), 1.26 (s, 3H), 1.01 (s, 3H), 0.73 (s, 3H), 0.57 - 0.41 (m, 2H) ppm. 13 C NMR (101 MHz, CDCl3) δ 58.1, 55.8, 27.7, 23.3, 23.1, 19.2, 16.0, 15.9, 14.6, 13.8 ppm.

[0099] b. To a solution of 2,2,6,6-tetramethylpiperidine (50.1 g, 355 mmol) in THF (500 mL), n-butyllithium (222 mL, 1.6 M, 355 mmol) was added slowly at 0 °C and stirred at rt for 30 min under argon. Diethylaluminum chloride (359 mL, 1.0 M, 358 mmol) was added slowly at 0 °C and stirred at rt for 30 min. Next, (1S,7R)-3,8,8-trimethyl-4-oxatricyclo[5.1.0.0] in THF (50 mL) was added. 3,5 ]octane (30.0 g, 177 mmol) was slowly added at 0° C. and stirred at rt for 16 h. The mixture was quenched by adding 500 mL of 10% aqueous HCl, and the resulting mixture was diluted with MTBE (300 mL * The oil was extracted with 3). The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried over MgSO4, and filtered. The solvent was removed, and the crude oil was distilled by Kugelrohr distillation (0.11 mbar, 120 °C) to give 85% pure (1R,6S)-7,7-dimethyl-4-methylenebicyclo[4.1.0]heptan-3-ol as a colorless liquid (29.2 g, 160 mmol, 92% yield).

[0100] c. To a solution of (1R,6S)-7,7-dimethyl-4-methylenebicyclo[4.1.0]heptan-3-ol (16.0 g, 85% wt, 89 mmol) in toluene (300 mL), tris(triphenylsiloxy)vanadium oxide (5.3 g, 5.4 mmol) was added at 10 °C and stirred at 110 °C for 6 h. Water (50 mL) and MTBE (200 mL) were added, and the mixture was diluted with MTBE (200 mL). * The resulting mixture was extracted with 3). The combined organic layers were washed with saturated aqueous NaHCO3 (200 mL) and brine (200 mL), dried over MgSO4, and filtered. The solvent was removed, and the resulting crude oil was purified by silica gel chromatography (heptane:MTBE = 9:1) to give ((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)methanol (12.1 g, 80 mmol, yield: 89%) as a colorless liquid.

[0101] 1H NMR (400 MHz, CDCl3) δ 5.60 - 5.50 (m, 1H), 3.95 (s, 2H), 2.46 - 2.25 (m, 2H), 2.01 - 1.88 (m, 2H), 1.65 (s, 1H), 1.04 (s, 3H), 0.80 - 0.70 (m, 4H), 0.70 - 0.59 (m, 1H) ppm. 13 C NMR (101 MHz, CDCl3) δ 135.3, 121.7, 67.7, 28.3, 20.5, 20.4, 17.8, 17.1, 16.9, 13.3 ppm.

[0102] d. A mixture of ((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)methanol (12.0 g, 79 mmol), sodium ethanolate (8.4 g, 102 mmol), and MgSO (10 g) in DCM (200 mL) was stirred at 10 °C for 10 min. Then, a mixture of pyridinium chlorochromate (22.1 g, 102 mmol) and silica gel (30 g) was slowly added and stirred at rt for 6 h. MTBE (200 mL) was added, and the mixture was filtered through a short silica gel column. The solvent was removed, and the resulting crude oil was purified by silica gel chromatography (heptane:MTBE=97:3) to give (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carbaldehyde (8.6 g, 57 mmol, yield: 83%) as a colorless liquid.

[0103] 1 H NMR (400 MHz, CDCl3) δ 9.40 (s, 1H), 6.72 - 6.71 (m, 1H), 2.77 - 2.18 (m, 4H), 1.07 (s, 3H), 0.83 - 0.70 (m, 5H) ppm. 13 C NMR (101 MHz, CDCl3) δ 194.1, 150.6, 139.9, 28.2, 22.5, 17.7, 17.6, 17.1, 16.6, 13.5 ppm. GC / MS (EI): m / z (%): 150 (4) [M+ ], 135 (11), 121 (19), 107 (100), 91 (33), 79 (79).

[0104] e. To a mixture of (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carbaldehyde (25.0 g, 166 mmol), KH2PO4 (113 g, 832 mmol), 2-methylbut-2-ene (58.4 g, 832 mmol), and 2-methylpropan-2-ol (61.7 g, 832 mmol) in water (200 mL) was added a solution of sodium chlorite (45.2 g, 499 mmol) in water (100 mL) at 10 °C and stirred at rt for 16 h. Saturated NH4Cl (300 mL) solution was added. The mixture was diluted with EA (100 mL). * The oil was extracted with 3). The combined organic layers were washed with saturated aqueous NaHCO3 and brine, dried over MgSO4, and filtered. The solvent was removed, and the crude oil was purified by silica gel chromatography (heptane:MTBE = 9:1) to give (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid (25.2 g, 152 mmol, yield: 91%) as a colorless liquid.

[0105] 1 H NMR (400 MHz, CDCl3) δ 7.13 - 6.96 (m, 1H), 2.65 - 2.47 (m, 2H), 2.28 - 2.10 (m, 2H), 1.06 (s, 3H), 0.87 - 0.78 (m, 1H), 0.76 - 0.65 (m, 4H) ppm. 13 C NMR (101 MHz, CDCl3) δ 172.6, 140.9, 127.7, 28.2, 22.1, 18.7, 17.7, 17.6, 16.5, 13.4 ppm. GC / MS (EI): m / z (%): 166 (16) [M + ], 123 (87), 105 (52), 91 (32), 79 (100).

[0106] f. A suspension of (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid (25.0 g, 150 mmol), 3-bromoprop-1-ene (27.3 g, 226 mmol), and potassium carbonate (41.6 g, 301 mmol) in DMF (200 mL) was stirred at 80 °C for 6 h. EA (100 mL) was added and the mixture was filtered. The solvent was removed by rotary evaporation, and the resulting crude oil was purified by silica gel chromatography (heptane:MTBE = 98:2) to give allyl (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylate (26.6 g, 129 mmol, 86% yield) as a colorless liquid.

[0107] 1 H NMR (400 MHz, CDCl3) δ 6.99 - 6.87 (m, 1H), 6.00 - 5.86 (m, 1H), 5.35 - 5.21 (m, 2H), 4.64 - 4.62 (m, 2H), 2.65 - 2.48 (m, 2H), 2.28 - 2.09 (m, 2H), 1.06 (s, 3H), 0.88 - 0.65 (m, 5H) ppm. 13 C NMR (101 MHz, CDCl3) δ 167.0, 138.5, 132.5, 128.2, 117.7, 64.9, 28.2, 21.8, 19.0, 17.7, 17.5, 16.5, 13.4 ppm. GC / MS (EI): m / z (%): 206 (1) [M + ], 191 (1), 165 (22), 123 (100), 105 (57), 91 (36), 79 (48). Odor description: Green, galbanum, metallic, fatty.

[0108] Example 10: 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one a. To a solution of acetylcarene (1-(4,7,7-trimethylbicyclo[4.1.0]hept-4-en-3-yl)ethan-1-one, 10.0 g, 56 mmol) in tetrahydrofuran (200 mL) was added DBU (25.6 g, 168 mmol) at rt and stirred at rt for 12 h. NH4Cl solution (100 mL) was added and MTBE (150 mL) was added. * The crude oil was purified by distillation after extraction with 3) and the combined organic layers were dried over MgSO. The solvent was removed and the crude oil was purified by distillation. 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)ethan-1-one (1.7 g, 9.0 mmol, 16% yield) was obtained as a colorless liquid.

[0109] b. To a solution of 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)ethan-1-one (3.2 g, 18 mmol) in tetrahydrofuran (100 mL) was added lithium bis(trimethylsilyl)amide solution (4.0 mL, 20 mmol) slowly over 30 min at -20 °C and stirred at -20 °C for an additional 30 min under argon. 3-Bromoprop-1-ene (2.1 g, 17 mmol) was added at 0 °C and stirred at rt for 12 h. Saturated NH4Cl solution (100 mL) was added and MTBE (100 mL) was added. * The combined organic layer was dried over MgSO. The solvent was removed, and the residue was purified by silica gel chromatography (PE:MTBE=96:4) to give 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one (0.31 g, 1.4 mmol, yield: 8%) as a colorless liquid.

[0110] 1 H NMR (400 MHz, CDCl3) δ 5.88 - 5.78 (m, 1H), 5.10 - 4.89 (m, 2H), 2.66 - 2.30 (m, 6H), 2.20 - 1.94 (m, 2H), 1.73 (s, 3H), 1.04 (s, 3H), 0.82 - 0.66 (m, 5H) ppm. 13GC / MS (EI): m / z (%): 218 (64) [M + ], 203 (42), 175 (32), 163 (67), 147 (74), 119 (100), 91 (87), 55 (96). Odor description: green, rubbery, metallic, galbanum, aromatic

[0111] Example 11: Fragrance Accord [Table 1]

[0112] The fragrance accord described above is a classically fresh, clean accord suitable for blending into, for example, heavy duty liquid fabric detergents (HDLDs). The fragrance accord may be blended at, for example, about 0.6 wt % or about 0.8 wt % of the HDLD base.

[0113] Replacing 15 parts DPG with 15 parts 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one (e.g., 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one) significantly improves fragrance performance during application, particularly in the wet phase and on dry fabrics after 24 hours. The addition of the compound of formula (I) imparts a classically fresh and clean green, galbanum-pineapple character that blends very well with the accord and meets consumer expectations of freshness and cleanliness.

Claims

1. Equation (I) 【Chemistry 1】 During the ceremony, The dotted lines form single or double bonds along with carbon-carbon bonds. n is either 1 or 0; X is -O- and -CH ２ - Selected from, and R １ is hydrogen or methyl, A compound of [unclear].

2. The compound of formula (I) is, 【Chemistry 2】 During the ceremony, The dotted lines, along with carbon-carbon bonds, form single or double bonds; X is -O- and -CH ２ - Selected from; and R １ is hydrogen or methyl The compound according to claim 1, which is a compound of the above.

3. The compound according to claim 1, wherein the dotted line forms a double bond together with the carbon-carbon bond.

4. The compound according to claim 2, wherein the dotted line forms a double bond together with a carbon-carbon bond, and the relative configuration of the ring system is (1S, 5R).

5. The compound according to claim 1, wherein the compound is selected from the group consisting of 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pento-4-en-1-one, 1-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)pento-4-en-1-one, allyl 6,6-dimethylbicyclo[3.1.1]hept-2-en-2-carboxylate, 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pento-4-en-1-one, allyl 7,7-dimethylbicyclo[4.1.0]hept-3-en-3-carboxylate, and 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)pento-4-en-1-one.

6. A fragranced article comprising a compound of formula (I) as defined in any one of claims 1 to 5, or a mixture thereof, as an odorant, and a consumer product base.

7. The fragrance-infused article according to claim 6, wherein the consumer product base is selected from luxury fragrances, household goods, laundry products, body care products, cosmetics, and air care products.

8. Use of a compound of formula (I) as defined in any one of claims 1 to 5 as a fragrance.

9. A method for improving, enhancing, or modifying a consumer product base by adding an olfactory-acceptable amount of a compound of formula (I) as defined in any one of claims 1 to 5.

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