Dimethyldicycloheptenyl and dimethyldicycloheptyl derivatives and their use as flavor enhancers

Abstract

Disclosed are dimethyl dicycloheptenyl and dimethyl dicycloheptyl derivatives having a green-agrimonia pilosa and fruity-pineapple scent scent.

Description

Technical Field

[0001] The present invention relates to flavor and fragrance ingredients and compositions containing them that can be used in flavor and fragrance applications. The present invention also relates to methods for preparing them. In particular, the present invention relates to dimethylbicycloheptenyl and dimethylbicycloheptyl derivatives of formula (I) having green-galbanum and fruity-pineapple odor aromas.

[0002] background

[0003] In the flavor and fragrance industry, perfumers and flavorists are constantly looking for new compounds with unique olfactory properties. For example, there is a need for ingredients suitable for the flavor and fragrance industry that have a green fruity-pineapple odor note reminiscent of galbanum.

[0004] Glechoma oil is a natural aromatic ingredient highly appreciated by perfumers for its green aroma. However, its use is limited by high costs. Synthetic alternatives with odors reminiscent of glechoma oil are described, for example, 3,3-dimethylcyclohexyl and 3,3-dimethylcyclohexenyl derivatives are disclosed in US4147672. Fragrance ingredients reminiscent of glechoma oil are also described in EP913383, in which spirocyclic compounds are disclosed, or 1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one is disclosed in WO2012110281, which imparts a glechoma type odor aroma.

[0005] Gepong is valued for its ability to emit a rich, spicy, green aroma. The Green Gepong odor family is very important in the creation of spice accords. Several well-known spices derive their characteristics from this odor family.

[0006] There is still a need for new fragrance ingredients reminiscent of galbanum. Besides the main purpose of providing new fragrance ingredients of the galbanum odor family, said ingredients should preferably be derivable from renewable resources. The use of renewable raw materials is becoming more and more important, because the market demand for new fragrances based on renewable raw materials and thus at least partially constituting alternatives to ingredients obtained from petrochemical raw materials is constantly increasing.

[0007] Surprisingly, the inventors have discovered a new class of ingredients of formula (I) as defined below, having very popular green-garbage and fruity-pineapple odor notes, all of which can be derived from renewable raw materials.

[0008] Overview

[0009] According to a first aspect of the present invention, there is provided a compound of formula (I) in the form of any stereoisomer thereof or a mixture thereof

[0010]

[0011] in

[0012] The dashed line forms a single or double bond together with the carbon-carbon bond.

[0013] n is 1 or 0;

[0014] X is selected from -O- and -CH2-, and

[0015] R 1 is hydrogen or methyl.

[0016] 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.

[0017] According to a third aspect of the present invention, there is provided a method of improving, enhancing and / or altering a consumer product base or consumable product base by adding thereto an olfactory acceptable amount of a compound of formula (I) according to the first aspect.

[0018] According to a fourth aspect of the present invention, there is provided a perfumed product comprising a compound of formula (I) according to the first aspect.

[0019] According to a fifth aspect of the present invention, there is provided a flavor or fragrance composition comprising the compound of formula (I) according to the first aspect.

[0020] According to a sixth aspect of the present invention, there is provided use of the compound of formula (I) according to the first aspect as a flavor or fragrance.

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

[0022] ●Green-Gabon and fruity-pineapple aroma characteristics,

[0023] ●Potent compounds,

[0024] ● Made from natural and / or renewable resources, and

[0025] ●Biodegradable.

[0026] Details, embodiments and preferences related to any specific one or more aspects of the aspects described in the present invention will be further described herein, and are equally applicable to all aspects of the present invention. Unless otherwise specified herein or context clearly contradicts, the present invention covers any combination of the embodiments, embodiments and preferences described herein and all possible variations thereof.

[0027] Detailed Description

[0028] The present invention is based on the surprising discovery that dimethylbicycloheptenyl derivatives have green-galbanum and fruity-pineapple odor aromas.

[0029] In a first aspect of the present invention, there is provided a compound of formula (I),

[0030]

[0031] in

[0032] The dashed lines form single or double bonds together with the carbon-carbon bonds;

[0033] n is 1 or 0;

[0034] X is selected from -O- and -CH2-; and

[0035] R 1 is hydrogen or methyl.

[0036] In one embodiment, there is provided a compound of formula (I) wherein n is 1, ie, a compound of formula (Ia)

[0037]

[0038] in

[0039] The dashed lines form single or double bonds together with the carbon-carbon bonds;

[0040] X is selected from -O- and -CH2-; and

[0041] R 1 is hydrogen or methyl.

[0042] In another specific embodiment, there is provided wherein R 1 The compound of formula (Ia) is hydrogen.

[0043] In another specific embodiment, there is provided a compound of formula (I) wherein n is 0, i.e., a compound of formula (Ib)

[0044]

[0045] The dashed lines form single or double bonds together with the carbon-carbon bonds;

[0046] X is selected from -O- and -CH2-; and

[0047] R 1 is hydrogen or methyl.

[0048] In another specific embodiment, a compound of formula (Ib) is provided, wherein X is -CH2-.

[0049] In another specific embodiment, the compound of formula (I) is selected from 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one, 1-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)pent-4-en-1-one, 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester, 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 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid allyl ester.

[0050] The compounds of formula (I) contain two or more chiral centers and may therefore exist as mixtures of stereoisomers, or they may be separated into isomerically pure forms. If it is desired to prepare individual stereoisomers, this may be accomplished by methods known in the art, such as preparative HPLC and GC or by stereoselective synthesis, or simply by using the desired isomerically pure form available from natural resources as starting materials.

[0051] In one embodiment, the compound of formula (Ia) in which the dotted line together with the carbon-carbon bond forms a single 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.

[0052] In another specific embodiment, the compound of formula (Ia) in which the dashed line together with the carbon-carbon bond forms a single bond is a compound in which the relative configuration of the ring system is (1R,5S), for example (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester.

[0053] In another specific embodiment, the compound of formula (Ia) in which the dotted line together with the carbon-carbon bond forms a double 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]hept-2-yl)pent-4-en-1-one.

[0054] The compounds of formula (I) can be used alone, as a mixture of their isomers, or in combination with known flavoring agent molecules selected from a wide range of currently available natural products and synthetic molecules, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and / or mixed with one or more ingredients or excipients commonly used with flavoring agents in perfume compositions, such as carrier materials and other adjuvants commonly used in the art.

[0055] As used herein, "carrier material" refers to a material that is substantially neutral from the perspective of the flavorant, ie, a material that does not significantly alter the sensory properties of the flavorant.

[0056] The term "adjuvant" refers to an ingredient that may be used in a perfume composition for reasons not particularly related to the olfactory properties of the composition. For example, an adjuvant may be an ingredient that is an aid in the processing of one or more perfume ingredients or compositions containing said ingredients, or it may improve the handling or storage of perfume ingredients or compositions containing said ingredients. It may also be an ingredient that provides an additional benefit such as imparting color or texture. It may also be an ingredient that imparts lightfastness or chemical stability to one or more ingredients included in the perfume composition. A detailed description of the nature and types of adjuvants commonly used in perfume compositions comprising adjuvants cannot be exhaustive, but it must be mentioned that said ingredients are well known to those skilled in the art.

[0057] As used herein, "flavor composition" refers to any composition comprising a compound of formula (I) or a mixture thereof and a matrix material, such as a diluent commonly used with a flavoring agent, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1,2-diol, triethyl citrate (TEC) and an alcohol (e.g., ethanol). Optionally, the composition may contain an antioxidant adjuvant. The antioxidant may be selected from TT(BASF), Q (BASF), tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2), 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) and related phenols, hydroquinone (CAS 121-31-9).

[0058] The following list includes examples of known flavorant molecules which can be combined with the compounds of formula (I) or mixtures thereof:

[0059] - essential oils and extracts, such as castoreum, costus vulgaris root oil, oakmoss absolute, geranium oil, tree moss absolute, basil oil, fruit oils such as bergamot and tangerine oils, myrtle oil, palmarosa oil, patchouli oil, orange leaf oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil;

[0060] - 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-yl)pent-4-en-2-ol); Eugenol (4-allyl-2-methoxyphenol); Ethyl linalool ((E)-3,7-dimethylnona-1,6-dien-3-ol); Farnesol ((2E,6Z)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol); Geraniol ((E)-3,7-dimethyloctan-2,6-dien-1-ol); Super Muguet TM ((E)-6-ethyl-3-methyloct-6-en-1-ol); linalool (3,7-dimethyloct-1,6-dien-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); nerol (3,7-dimethyl-2,6-octadien-1-ol); phenylethyl alcohol (2-phenylethyl alcohol); Rhodinol TM (3,7-dimethyloct-6-en-1-ol); Sandalore TM (3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-1-yl)propan-2-ol); or Timberol TM (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7-trimethylocta-2,6-dien-1-ol and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]-methanol;

[0061] - aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde); α-amylcinnamaldehyde (2-benzylideneheptanal); Georgywood TM (1-(1,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); Hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal); Iso E (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); Hedione TM (3-oxo-2-pentylcyclopentaneacetic acid methyl ester); 3-(4-isobutyl-2-methylphenyl) propanal; maltol; methyl cedryl ketone; methyl ionone; verbenone and / or vanillin;

[0062] - 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]);

[0063] - Esters and lactones, for example benzyl acetate; cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methyleneazulene-6-yl acetate); delta-decalactone (6-pentyltetrahydro-2H-pyran-2-one); (2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methylpropyl propionate); delta-undecanolactone (5-heptyloxolan-2-one) and / or eugenyl acetate (acetic acid (4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulene-6-yl) ester);

[0064] - macrocyclics, such as cypermethrin ((Z)-oxacycloheptadecan-10-en-2-one); brassic acid ethylene ester (1,4-dioxacycloheptadecan-5,17-dione) and / or (16-oxacyclohexadecane-1-one);

[0065] - Heterocyclics, for example isobutylquinoline (2-isobutylquinoline).

[0066] Therefore, in another aspect of the present invention, there is provided a fragrance composition comprising a compound of formula (I).

[0067] Formula (I) compound can be used for wide range of perfumed products, such as any field of fine and functional spices, such as perfume, air care products, household products, laundry products, body care products and cosmetics. The compound can be used in a widely varying amount, depending on the properties and dosage of specific products and other flavoring agent components. The ratio is generally 0.00001 to 3 weight % of the product. In one embodiment, the compound can be used for fabric softener in an amount of 0.0001 to 3 weight % (e.g., 0.001 to 1, including 0.5, 0.3 and 0.05 weight %). In another embodiment, the compound can be used for fine spices in an amount of 0.01 to 30 weight % (e.g., up to about 10 or up to 20 weight %), more preferably 0.01 to 5 weight % (e.g., 0.01 to 0.1 weight %). However, these values ​​are only given as examples, because experienced perfumers can also achieve effects or create new accords by lower or higher concentrations.

[0068] The compound of formula (I) can be used in the consumer product base simply by directly mixing the compound or the fragrance composition comprising the compound of formula (I) or their mixture with the consumer product base, or it can be encapsulated in an earlier step with an encapsulating material, such as polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base.

[0069] Therefore, the present invention also provides a method for preparing a perfumed article, the method comprising adding a compound of formula (I) or a mixture thereof as a perfume ingredient, either by mixing directly with a consumer product base, or by mixing a perfume composition comprising a compound of formula (I) or a mixture thereof, and then mixing it with the consumer product base using conventional techniques and methods. By adding an olfactory acceptable amount of a compound of formula (I) or a mixture thereof, the odor profile of the consumer product base will be improved, enhanced or changed.

[0070] Therefore, the present invention also provides a method of improving, enhancing or modifying a consumer product base by adding an olfactory acceptable amount of a compound of formula (I) or a mixture thereof to the consumer product base.

[0071] In another aspect of the present invention, there is provided a perfumed article comprising:

[0072] a) Compounds of formula (I)

[0073]

[0074] in

[0075] The dashed line forms a single or double bond together with the carbon-carbon bond.

[0076] n is 1 or 0;

[0077] X is selected from -O- and -CH2-, and

[0078] R 1 is hydrogen or methyl;

[0079] and

[0080] b) Consumer product matrix.

[0081] As used herein, "consumer product base" refers to a composition used as a consumer product to achieve a specific effect such as cleaning, softening and care, etc. Examples of such products include fine fragrances, such as perfumes and eau de toilette; fabric care, household products and personal care products, such as cosmetics, laundry care detergents, rinse conditioners, personal cleaning compositions, dishwasher detergents, surface cleaners; laundry products, such as softeners, bleaches, detergents; body care products, such as shampoos, shower gels; air care products (including products containing preferably volatile and generally pleasant smelling compounds, which can advantageously mask unpleasant odors even in very small amounts). Living area air fresheners contain in particular natural and synthetic essential oils, such as pine needle oil, citrus oil, eucalyptus oil, lavender oil, etc., in an amount of, for example, up to 50% by weight. As aerosols, they often contain relatively small amounts of such essential oils, e.g. less than 5 wt % or less than 2 wt %, but also include compounds such as acetaldehyde (especially <0.5 wt %), isopropanol (especially <5 wt %), mineral oil (especially <5 wt %) and propellants.

[0082] Cosmetics include:

[0083] (a) cosmetic and skin care products, in particular bath products, skin washing and cleansing products, skin care products, eye make-up, lip care products, nail care products, intimate care products and foot care products;

[0084] (b) cosmetics with special effects, in particular sunscreens, tanning products, depigmenting products, deodorants, antiperspirants, depilatories and shaving products;

[0085] (c) cosmetic dental care products, in particular dental and oral care products, tooth care products, denture cleansers, denture adhesives; and

[0086] (d) Cosmetic hair care products, in particular shampoos, hair care products, hair setting products, hair styling products and hair dyeing products.

[0087] This product list is for illustrative purposes only and should not be considered limiting in any way.

[0088] In a particular embodiment, the consumer product base is selected from fine fragrances and personal care products, including deodorants, hair care products, soaps, etc. In a particular embodiment, the consumer product base is a hair care product.

[0089] In further specific embodiments, the consumer product substrate is selected from fabric care products (including fabric softeners) and household care products (including air fresheners, dishwashers, etc.).

[0090] For example, compounds of formula (I) wherein n is 1 and X is -CH2- can be synthesized by oxidizing α-pinene to its corresponding aldehyde myrtenal, followed by a Grignard reaction, and then oxidation to obtain the corresponding ketone. Alternatively, the compound can also be synthesized, for example, by oxidizing α-pinene to its corresponding aldehyde myrtenal, followed by hydrogenation, a Grignard reaction, and then oxidation to obtain the corresponding ketone.

[0091] For example, compounds of formula (I) wherein n is 1 and X is oxygen can be further synthesized by stepwise oxidation of α-pinene to its corresponding acid followed by esterification to the corresponding ester.

[0092] For example, α-pinene is found in the oils of many coniferous trees, especially pine. It has two enantiomers, (1S,5S)- or (-)-α-pinene and (1R,5R)- or (+)-α-pinene, both of which occur in nature. (-)-α-pinene is more common in European pine, while (+)-α-pinene is more common in North America. Racemic mixtures are also found in some oils, such as eucalyptus oil and orange peel oil.

[0093] Compounds of formula (I) wherein n is 0 can be synthesized, for example, by isomerization of 3-carene epoxide to 3(10)-carene-4-ol, followed by oxidation, Grignard reaction, and then oxidation to give the corresponding ketone. Alternatively, compounds of formula (I) wherein n is 0 can be synthesized, for example, by isomerization of acetylcarene, followed by α-allylation to form the corresponding ketone.

[0094] For example, compounds of formula (I) wherein n is 0 and X is oxygen can be synthesized by isomerization of 3-carene epoxide to 3(10)-carene-4-ol, followed by oxidation to the corresponding acid, followed by Grignard reaction and oxidation to form the corresponding ester.

[0095] 3-Carene epoxide is obtained by epoxidation of 3-carene (3,7,7-trimethylbicyclo[4.1.0]hept-3-ene), which is commonly found in, for example, essential oils such as turpentine, juniper oil, and pine needle oil. It has two enantiomers, (+)-3-carene or (1S,6R)-3-carene and (-)-3-carene or (1R,6S)-3-carene, both of which exist in nature.

[0096] The present invention will now be further described with reference to the following non-limiting examples. These examples are for illustrative purposes only and variations and modifications may be made by those skilled in the art. Example

[0097] All reactions were carried out under argon, and the solvents and reagents used were from commercial suppliers without further purification. The solvents used for extraction and chromatography were all technical grade and used without further purification. Flash chromatography adopted TsingdaoHaiyang Chemical silica gel (200-300 mesh) and Santai Technologies silica gel rapid column. Unless otherwise stated, heptane: MTBE mixture was used as eluent. NMR spectrum adopted AW 400MHz Bruker spectrometer to record. 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 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 = doublet of doublets, bs = broad singlet. GC / MS spectral data were obtained by Agilent 6890N and MSD 5975 using a chromatographic column HP-5MS, 30 m, 0.25 mm, 0.25 μm.

[0098] Example 1: 1-(6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one

[0099] a. Slowly add acetic acid (13.2 g, 220 mmol) 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) at 0°C, and then stir at 80°C for 16 h. The reaction was quenched by adding saturated NH4Cl solution, and the mixture was extracted with ethyl acetate (150 mL*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 obtain myrtle aldehyde (6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxaldehyde) (14.6 g, 97 mmol, 66% yield) as a colorless liquid.

[0100] 1 H NMR (400MHz, CDCl3) δ9.44 (s, 1H), 6.75-6.69 (m, 1H), 2.87 (t, J = 5.5Hz, 1H), 2.64-2 .45(m,3H),2.22-2.16(m,1H),1.34(s,3H),1.06(d,J=9.2Hz,1H),0.75(s,3H)ppm. 13C NMR (101MHz, CDCl3) δ 191.2, 151.5, 147.8, 40.7, 38.1, 37.6, 33.0, 31.1, 25.7, 20.9ppm. GC / MS (EI): m / z (%): 150 (1) [M + ],135(14),107(74),91(40),79(100).

[0101] b. To a solution of but-3-en-1-ylmagnesium chloride (121 mL, 61 mmol, 0.5 M) in tetrahydrofuran (100 mL) was added a solution of myrtenal (6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde, 7.0 g, 47 mmol) in tetrahydrofuran (50 mL) at 10°C and stirred at room temperature for 3 h. The reaction was quenched with saturated NH4Cl solution and extracted with ethyl acetate (150 mL*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-ene-2-yl)pent-4-ene-1-ol (5.9 g, 29 mmol, yield: 61%) as a light yellow liquid.

[0102] 1 H NMR (400 MHz, CDCl3, isomer mixture) 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, Isomer mixture) 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).

[0103] 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 room temperature for 20 min, then benzaldehyde (8.2 g, 78 mmol) was added at room temperature and stirred for another 3 h. The reaction was quenched with water and then extracted with MTBE (100 mL*3). The organic layer was 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-one (3.6 g, 18 mmol, yield: 91%) as a colorless liquid.

[0104] 1 H NMR (400MHz, CDCl3) δ6.81-6.69(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=9.1Hz,1H),0.74(s,3H)ppm. 13 C NMR (101MHz, CDCl3) δ 198.4, 149.1, 137.6, 136.5, 115.0, 40.3, 39.6, 37.3, 36.1, 32.5, 31.1, 28.9, 25.9, 20.9ppm. GC / MS (EI): m / z (%): 204 (1) [M + ],189(3),161(27),105(100),91(25),77(22),55(48).

[0105] Odor description: Green-German, Fruity-Pineapple, Metallic, Oily.

[0106] Example 2: 1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one

[0107] a. According to the method in Example 1 (step b), (1R)-(-)-myrtle aldehyde (50.0 g, 333 mmol) was reacted with but-3-en-1-ylmagnesium chloride (433 mL, 433 mmol) to obtain 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).

[0108] 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).

[0109] b. According to the method in Example 1 (step c), 1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-ol (40.0 g, 194 mmol) was reacted with benzaldehyde (82.0 g, 775 mmol) to obtain 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).

[0110] 1 H NMR (400MHz, CDCl3) δ6.71-6.63(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=9.0Hz,1H),0.67(s,3H)ppm. 13 C NMR (101MHz, CDCl3) δ 198.5, 149.1, 137.6, 136.5, 115.0, 40.3, 39.6, 37.3, 36.1, 32.5, 31.1, 28.9, 25.9, 20.9ppm. GC / MS (EI): m / z (%): 204 (1) [M + ],189(3),161(26),105(100),55(55).

[0111] Odor description: green, sorbet, fruity, oily, metallic, pineapple.

[0112] Example 3: 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)pent-4-en-1-one

[0113] a. According to the method in Example 1 (step b), (1S)-(+)-myrtlene ((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-ylmagnesium chloride (140 mL, 70 mmol) to obtain 1-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-yl)pent-4-ene-1-ol as a colorless liquid (28 mmol, 5.7 g, 51% yield).

[0114] 1 H NMR (400 MHz, CDCl3, isomer mixture) 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, Isomer mixture) 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).

[0115] b. According to the method in Example 1 (step c), 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 to obtain 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).

[0116] 1 H NMR (400MHz, CDCl3) δ6.75-6.61(m,1H),5.80-5.71(m,1H),5.03-4.84(m,2H),2.88(dt,J=1.0,5.6Hz,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=9.0Hz,1H),0.66(s,3H)ppm. 13 C NMR (101MHz, 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, 20.8ppm. GC / MS (EI): m / z (%): 204 (1) [M + ],189(2),161(18),105(100),91(24),55(59).

[0117] Odor description: Green-German, Fruity-Pineapple, Metallic.

[0118] Example 4: 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-yl)pent-4-en-1-one

[0119] 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 for 16 h at room temperature (rt). 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.

[0120] b. According to the method in Example 1 (step b), (1S,5S)-6,6-dimethylbicyclo[3.1.1]heptane-2-carbaldehyde (15.0 g, 99 mmol) was reacted with but-3-en-1-ylmagnesium chloride (128 mL, 128 mmol, 1.0 M) to obtain 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-yl)pent-4-en-1-ol as a light yellow liquid (13.6 g, 65 mmol, yield: 66%).

[0121] GC / MS(EI): m / z(%): 208(1)[M +],193(6),179(2),139(14),105(15),82(81),67(100),55(86).

[0122] c. Pyridinium chlorochromate (11.4 g, 53 mmol) was added in portions to a solution of 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-yl)pent-4-en-1-ol (10.0 g, 48 mmol) in DCM (200 mL) at 10°C and stirred at room temperature for 3 h. The reaction was quenched by adding hexane (300 mL), and the suspension was filtered through a short pad of silica gel, and the solvent of the filtrate was removed to give a crude oil. Purification by silica gel chromatography (PE:MTBE=96:4) gave 1-((1S,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-yl)pent-4-en-1-one (1.9 g, 9.2 mmol, yield 19%) as a colorless liquid.

[0123] 1 H NMR (400MHz, CDCl3) δ5.91-5.64(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 (101MHz, CDCl3) δ212.0,137.5,115.0,53.1,43.0,40.7,39.2,38.9,30.1,28.1,27.3,24.9,22.0,13.8ppm.GC / MS(EI): m / z(%): 206(1)[M + ],191(5),163(7),151(11),123(46),95(30),67(43),55(100).

[0124] Odor description: Fruity-pineapple, oily, green-grape.

[0125] Example 5: Allyl 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylate

[0126] a. To a solution of myrtle aldehyde (6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxaldehyde, 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 a solution of 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 room temperature for 16 h. The reaction mixture was extracted with MTBE (100 mL*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.

[0127] b. Add 3-bromoprop-1-ene (1.2 g, 9.9 mmol) 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) and stir at room temperature for another 16 h. The reaction was extracted with MTBE (50 mL*2) and dried over MgSO4. The concentrated crude oil was purified by silica gel chromatography (PE:MTBE=97:3) to give 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester (1.9 g, 8.2 mmol, yield 91%) as a colorless liquid.

[0128] 1 H NMR (400MHz, CDCl3) δ6.97-6.78(m,1H),6.01-5.92(m,1H),5.41-5.12(m,2H),4.63(d,J=5.6Hz,2H),2.8 8-2.78(m,1H),2.55-2.33(m,3H),2.14-2.11(m,1H),1.33(s,3H),1.12(d,J=9.1Hz,1H),0.80(s,3H)ppm. 13 C NMR (101MHz, 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, 20.9ppm. GC / MS (EI): m / z (%): 206 (1) [M + ],191(1),165(10),149(9),105(100),91(46),79(38).

[0129] Odor description: aromatic, resinous, coniferous, metallic, oily, fruity-pineapple, green-gabon.

[0130] Example 6: (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester

[0131] a. According to the method in Example 5 (step a), (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxaldehyde (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) were reacted to obtain (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid as a colorless liquid (16 mmol, 2.6 g, 94% yield).

[0132] b. According to the method in 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 obtain (1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester as a colorless liquid (7.8 mmol, 1.6 g, 86% yield).

[0133] 1 H NMR (400MHz, CDCl3) δ6.91-6.80(m,1H),6.01-5.91(m,1H),5.37-5.14(m,2H),4.63(d,J=5.6Hz,2H),2.8 2-2.80(m,1H),2.51-2.32(m,3H),2.17-2.07(m,1H),1.33(s,3H),1.12(d,J=9.1Hz,1H),0.80(s,3H)ppm. 13 C NMR (101MHz, 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, 20.9ppm. GC / MS (EI): m / z (%): 206 (1) [M + ],191(1),165(7),105(100),91(51),79(45).

[0134] Odor description: Green aroma - galbanum, metallic aroma, carrot, garlic, oily aroma, fruity aroma - pineapple.

[0135] Example 7: (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester

[0136] a. According to the method in Example 5 (step 1), (1R, 5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxaldehyde (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) were reacted to obtain (1R, 5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid as a colorless liquid (130 mmol, 21.6 g, 97% yield).

[0137] b. According to the method in Example 5 (step 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) to obtain (1R, 5S)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-carboxylic acid allyl ester as a colorless liquid (27 mmol, 5.6 g, 90% yield).

[0138] 1 H NMR (400MHz, CDCl3) δ6.88-6.84(m,1H),6.01-5.91(m,1H),5.35-5.21(m,2H),4.63(d,J=5.5Hz,2H),2.8 3-2.80(m,1H),2.52-2.33(m,3H),2.17-2.03(m,1H),1.33(s,3H),1.12(d,J=9.1Hz,1H),0.80(s,3H)ppm. 13 C NMR (101MHz, 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, 20.9ppm. GC / MS (EI): m / z (%): 206 (1) [M + ],191(1),165(7),105(100),91(53),79(46).

[0139] Odor description: Green, metallic, fuzzy, aromatic.

[0140] Example 8: 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one

[0141] a. Slowly add n-butyl lithium (296 mL, 473 mmol) to a solution of diisopropylamine (47.9 g, 473 mmol) in THF (200 ml) at -78°C, and stir at room temperature under argon for 30 min. Then slowly add 3-carene epoxide (3,8,8-trimethyl-4-oxatricyclo[5.1.0.0 3,5 ] octane, 60.0 g, 394 mmol) in THF (200 mL) and stirred at room temperature for 5 h. Saturated NH4Cl (100 mL) was added, and the mixture was extracted with MTBE (200 mL*3), and the organic layer was washed with NaHCO3 solution and brine, and then dried over MgSO4. The solvent was removed and the crude oil was distilled to obtain 3(10)-carene-4-ol (7,7-dimethyl-4-methylenebicyclo[4.1.0]heptan-3-ol, 56.6 g, 372 mmol, 94% yield) as a colorless liquid.

[0142] 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 (((vanadyl)oxy)triphenyl-15-silyl)((triphenyl(((triphenyl(11-phosphinyl)-15-silyl)oxy)-12-phosphinyl)-15-silyl)oxy)-12-phosphane (5.8 g, 5.9 mmol) at 10° C. and stirred at 100° C. for 6 h. The mixture was cooled to room temperature and water (50 mL) was added, followed by extraction with MTBE (100 mL*3), and the organic layer was dried over MgSO4. The organic layer was concentrated and the resulting crude oil was purified by silica gel chromatography (PE:MTBE=9:1) to give 3-caren-10-ol ((7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)methanol, 6.8 g, 45 mmol, yield: 45%) as a light yellow liquid.

[0143] 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 room temperature 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.

[0144] d. According to the method in Example 1 (step b), but-3-en-1-ylmagnesium 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 obtain 1-(7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-yl)pent-4-ene-1-ol (1.0 g, 4.8 mmol, yield: 73%) as a light yellow liquid.

[0145] 1 H NMR (400MHz, CDCl3) δ5.88-5.71(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 (101MHz, CDCl3) δ138.5,138.4,137.6,137.5,122.4,121.6,114.7,114.6,76.5,76.0,34.2,3 3.9,30.2,30.1,28.4,28.3,20.6,20.5,18.6,17.8,17.7,17.6,17.4,17.2,17.0,13.4,13.4ppm.

[0146] e. According to the method in 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 obtain 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.

[0147] 1 H NMR (400MHz, CDCl3) δ6.88-6.72(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. 13C NMR (101MHz, CDCl3) δ200.2,138.5,137.7,137.2,114.9,36.5,28.7,28.1,22.1,18.1,17.8,17.5,16.6,13.5ppm.GC / MS(EI): m / z(%): 204(6)[M + ],189(5),175(2),161(28),105(100),55(56).

[0148] Odor description: green, oily, metallic, gabby, aromatic, coniferous, fir needles.

[0149] Example 8.1: 1-((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one

[0150] 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 room temperature for 5 h. A saturated aqueous solution of NH4Cl (100 mL) was added. The mixture was extracted with EA (200 mL*3). The combined organic layers were washed with a 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.

[0151] 1 H NMR (400 MHz, CDCl3, isomer mixture) 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. 13C NMR (101 MHz, CDCl3, isomer mixture) 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.

[0152] 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).

[0153] 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 room temperature for 10 min. 4-nitrobenzaldehyde (11.5 g, 76 mmol) was added and stirred at room temperature for 6 h. Water (50 mL) was added and the resulting mixture was extracted with MTBE (200 mL*3). The combined organic layers were 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=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.

[0154] 1 H NMR(400MHz, CDCl3)δ6.83 -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 CNMR(101MHz, CDCl3)δ200.2,138.5,137.6,137.2,114.9,36.4,28.7,28.1,22.1,18.1,17.8,17.5,16.6,13.5ppm.

[0155] GC / MS(EI): m / z(%): 204(6)[M + ],189(4),161(27),149(17),121(31),105(100),77(35),55(59).

[0156] Odor description: Green, frankincense, oily, fruity

[0157] Example 9: 7,7-Dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid allyl ester

[0158] a. According to the method in Example 5 (step 1), 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxaldehyde (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) were reacted to obtain 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid as a white solid (2.1 g, 11.0 mmol, purity: 90%, yield: 66%).

[0159] 13 C NMR (101MHz, CDCl3) δ171.7,139.9,126.8,27.1,21.0,17.7,16.7,16.6,15.5,12.4ppm.

[0160] b. According to the method in Example 5 (step 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) to obtain 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid allyl ester (1.6 g, 7.8 mmol, yield: 68%) as a colorless liquid.

[0161] 1 H NMR (400MHz, CDCl3) δ7.04-6.77(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 (101MHz, CDCl3) δ167.0,138.5,132.5,128.2,117.7,64.9,28.2,21.8,19.0,17.8,17.5,16.6,13.4ppm.

[0162] Odor description: Green, fruity-pineapple, bergamot.

[0163] Example 9.1: (1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid allyl ester

[0164] a. Slowly add m-CPBA (80.5 g, 85% Wt, 396 mmol) 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) at 23-27°C and stir overnight at room temperature. Add heptane (200 mL) and filter out the solid. Add 500 mL of EA and wash the resulting mixture with NaHSO3 (200 mL*3), saturated NaHCO3 aqueous solution (200 mL*3) and brine (200 mL). The resulting organic layer is dried over MgSO4 and then filtered. The solvent is removed by rotary evaporation and the crude product is purified by silica gel column 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%), a colorless liquid.

[0165] 1 H NMR (400MHz, CDCl3) δ2.84-2.79(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 (101MHz, CDCl3) δ58.1,55.8,27.7,23.3,23.1,19.2,16.0,15.9,14.6,13.8ppm.

[0166] b. To a solution of 2,2,6,6-tetramethylpiperidine (50.1 g, 355 mmol) in THF (500 mL) was slowly added n-butyllithium (222 mL, 1.6 M, 355 mmol) at 0°C and stirred at room temperature for 30 min under argon. Diethylaluminum chloride (359 mL, 1.0 M, 358 mmol) was slowly added at 0°C and stirred at room temperature for 30 min. Then (1S,7R)-3,8,8-trimethyl-4-oxatricyclo[5.1.0.0 3,5 ] octane (30.0 g, 177 mmol) in THF (50 mL) and stirred at room temperature for 16 h. The mixture was quenched by adding 500 mL of 10% HCl aqueous solution and the resulting mixture was extracted with MTBE (300 mL*3). The combined organic layers were washed with saturated NaHCO3 aqueous solution and brine, then dried over MgSO4 and filtered. The solvent was removed and the crude oil was distilled by Kugelroh distillation (0.11 mbar, 120°C) to give (1R,6S)-7,7-dimethyl-4-methylenebicyclo[4.1.0]heptan-3-ol with a purity of 85% as a colorless liquid (29.2 g, 160 mmol, 92% yield).

[0167] 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) was added tris(triphenylsilyloxy)vanadium oxide (5.3 g, 5.4 mmol) at 10°C and stirred at 110°C for 6 h. Water (50 mL) and MTBE (200 mL) were added, and the mixture was extracted with MTBE (200 mL*3). The combined organic layers were washed with saturated aqueous NaHCO3 solution (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.

[0168] 1 H NMR (400MHz, CDCl3) δ5.60-5.50(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. 13C NMR (101MHz, CDCl3) δ135.3,121.7,67.7,28.3,20.5,20.4,17.8,17.1,16.9,13.3ppm.

[0169] d. A mixture of ((1S,6R)-7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)methanol (12.0 g, 79 mmol), sodium ethoxide (8.4 g, 102 mmol) and MgSO4 (10 g) in DCM (200 mL) was stirred at 10 °C for 10 min. A mixture of pyridinium chlorochromate (22.1 g, 102 mmol) and silica gel (30 g) was then slowly added and stirred at room temperature 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.

[0170] 1 H NMR (400MHz, CDCl3) δ9.40(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 (101MHz, CDCl3) δ194.1,150.6,139.9,28.2,22.5,17.7,17.6,17.1,16.6,13.5ppm.

[0171] GC / MS(EI): m / z(%): 150(4)[M + ],135(11),121(19),107(100),91(33),79(79).

[0172] 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 room temperature for 16 h. Saturated NH4Cl (300 mL) solution was added. The mixture was extracted with EA (100 mL*3). The combined organic layers were washed with saturated aqueous NaHCO3 and brine, then 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.

[0173] 1 H NMR (400MHz, CDCl3) δ7.13-6.96(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 (101MHz, CDCl3) δ172.6,140.9,127.7,28.2,22.1,18.7,17.7,17.6,16.5,13.4ppm.

[0174] GC / MS(EI): m / z(%): 166(16)[M + ],123(87),105(52),91(32),79(100).

[0175] 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 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 (1S, 6R)-7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid allyl ester (26.6 g, 129 mmol, yield: 86%) as a colorless liquid.

[0176] 1 H NMR (400MHz, CDCl3) δ6.99-6.87(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 (101MHz, CDCl3) δ167.0,138.5,132.5,128.2,117.7,64.9,28.2,21.8,19.0,17.7,17.5,16.5,13.4ppm.

[0177] GC / MS(EI): m / z(%): 206(1)[M + ],191(1),165(22),123(100),105(57),91(36),79(48).

[0178] Odor description: Green, gabby, metallic, greasy.

[0179] Example 10: 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one

[0180] 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 room temperature and stirred at room temperature for 12 h. NH4Cl solution (100 mL) was added, and the mixture was extracted with MTBE (150 mL*3), and the combined organic layers were dried over MgSO4. 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, yield 16%) was obtained as a colorless liquid.

[0181] 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 slowly added bis(trimethylsilyl)amide lithium solution (4.0 mL, 20 mmol) at -20°C over 30 min, and stirred for another 30 min at -20°C under argon. 3-Bromoprop-1-ene (2.1 g, 17 mmol) was added at 0°C, and stirred at room temperature for 12 h. Saturated NH4Cl solution (100 mL) was added, and the mixture was extracted with MTBE (100 mL*3), and the combined organic layers were dried over MgSO4. 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.

[0182] 1 H NMR (400MHz, CDCl3) δ5.88-5.78(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. 13 C NMR (101MHz, CDCl3) δ207.2,137.5,136.1,131.7,115.1,40.8,28.0,27.9,27.9,21.9,21.1,17.9,17.2,17.0,13.5ppm.GC / MS(EI): m / z(%): 218(64)[M + ],203(42),175(32),163(67),147(74),119(100),91(87),55(96).

[0183] Odor description: green, rubbery, metallic, gummy, aromatic.

[0184] Example 11: Fragrance Accords

[0185]

[0186] 1)(1-methyl-2-(1,2,2-trimethylbicyclo(3.1.0)-hex-3-ylmethyl)cyclopropyl)methanol

[0187] The above fragrance accord is a classic fresh, clean accord, for example, suitable for mixing with a heavy-duty fabric liquid detergent (HDLD). The fragrance accord can be mixed with a HDLD base, for example, at about 0.6 wt % or about 0.8 wt %.

[0188] By replacing 15 parts of DPG with 15 parts of 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), the fragrance performance is significantly improved in use, especially in the wet stage evaluation, while also benefiting dry fabrics after 24 hours. The addition of the compound of formula (I) brings a classic fresh and clean green, pineapple accord that combines well with the accords and is very much in line with the consumer's expectations for freshness and cleanliness.

Claims

1. Compound of formula (I) in The dashed lines form single or double bonds together with the carbon-carbon bonds; n is 1 or 0; X is selected from -O- and -CH2-; and R 1 is hydrogen or methyl.

2. The compound according to claim 1, wherein the compound of formula (I) is a compound of formula (Ia) in The dashed lines form single or double bonds together with the carbon-carbon bonds; X is selected from -O- and -CH2-; and R 1 is hydrogen or methyl.

3. A compound according to claim 1 or claim 2, wherein the dashed line together with the carbon-carbon bond forms a double bond.

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

5. The compound according to claim 1, wherein the compound is selected from 1-(6,6-dimethylbicyclo[ 3.1.1]hept-2-en-2-yl)pent-4-en-1-one, 1-(6,6-dimethylbicyclo[ 3.1.1]hept-2-yl)pent-4-en-1-one, 6,6-dimethylbicyclo[ 3.1.1]hept-2-ene-2-carboxylic acid allyl ester, 1-(7,7-dimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one, 7,7-dimethylbicyclo[4.1.0]hept-3-ene-3-carboxylic acid allyl ester and 1-(4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-yl)pent-4-en-1-one.

6. Perfumed article comprising as flavoring agent a compound of formula (I) as defined in claims 1 to 5 or a mixture thereof and a consumer product base.

7. The perfumed article according to claim 6, wherein the consumer product substrate is selected from the group consisting of fine perfumes, household products, laundry products, body care products, cosmetics and air care products.

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

9. A method of improving, enhancing or modifying a consumer product base by adding to said consumer product base an olfactory acceptable amount of a compound of formula (I) as defined in claim 1.

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