Odorants and compositions containing odorants

Abstract

The present invention relates to a new class of odorous tetrahydropyran-4-ol derivatives of formula X and / or olefin derivatives thereof of formula Y1 and Y2, which can be used as fragrance or flavor materials, especially in providing camphor, wood, earthy and / or patchouli-like notes to perfumes, aromas or deodorizing / masking compositions. The present invention also relates to fragrance, flavor and / or deodorizing / masking compositions comprising the new class of odorous tetrahydropyran-4-ol derivatives and / or olefin derivatives thereof.

Description

Technical Field

[0001] The present invention relates to a new class of odorous tetrahydropyran-4-ol derivatives and / or olefin derivatives thereof, which can be used as fragrance or flavor materials, in particular in providing camphor, wood, earthy and / or patchouli-like notes to perfumes, aromas or deodorizing / masking compositions. The present invention also relates to fragrance, flavor and / or deodorizing / masking compositions comprising said new class of odorous tetrahydropyran-4-ol derivatives and / or olefin derivatives thereof. The present invention further relates to said odorants which can be used in the novel fragrance, flavor and / or deodorizing / masking compositions of the present invention. The present invention also relates to methods for producing said odorants / compounds and corresponding fragrance, flavor and / or deodorizing / masking compositions containing said odorants / compounds.

[0002] More particularly, the present invention relates to 2,6-disubstituted-3,3,4-trimethyltetrahydro-2 H -pyran-4-ol derivatives (X) and / or 2,6-disubstituted-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran derivatives (Y 1 ) and / or 2,6-disubstituted-3,3,4-trimethyl-3,6-dihydro-2 H -pyran derivatives (Y 2 ) (odorants) which are useful as fragrance or flavor materials, particularly in providing camphor, woody, earthy and / or patchouli-like notes to perfume, fragrance or deodorizing / masking compositions. Background Art

[0003] The increasing limitations on the supply of natural fragrance ingredients have revolutionized the field of synthetic fragrance ingredients.Today, there is an increasing demand for new odorants / compounds and / or new fragrance, flavor and / or deodorizing / masking compositions comprising the same.

[0004] Patchouli oil is a very important natural oil that is widely used in fragrance creation. Patchouli oil is produced by steam distillation of dried and fermented leaves of the patchouli shrub. Patchouli oil exhibits a woody balsamic aroma, and this odor profile perfectly blends camphor, wood and earthy notes. Although (-)-patchouli alcohol, which is present in patchouli oil at about 35-40%, has been described as its main odor component, its synthesis is extremely challenging. There is an increasing demand for new compounds that can be easily synthesized, blending wood, camphor and earthy notes, and giving the composition a patchouli-like odor profile.

[0005] US2009263336 (A1) claims a method for preparing a compound of formula (A),

[0006] #timg# wherein R represents a linear or branched C5 alkyl group,

[0007] The method comprises reacting a compound of formula (B) with prenol,

[0008] #timg# wherein R is as defined for formula (A),

[0009]

[0010] In the presence of an acid, the reaction is refluxed in an organic solvent selected from toluene, xylene, trimethylbenzene, cyclohexane and methylcyclohexane at a temperature of about 70° C., preferably at 80° C.-90° C., and even more preferably at about 80° C. The acid is preferably selected from p-toluenesulfonic acid (PTSA), sulfuric acid and other supported acids.

[0011] M.Markert, I.Buchem, H.Krüger and R.Mahrwald published a paper on LiClO in Tetrahedron [Volume 60, Issue 4, 19 January 2004, Pages 993-999]. 4 -Article on stereo- and regioselective alkylation of activated aldehydes.

[0012]

[0013] For example, they disclose a scheme in which in the presence of LiClO 4 In the case of ethyl p-toluenesulfonate, an aldehyde (benzaldehyde or an aliphatic aldehyde) is reacted with an alcohol or the corresponding titanium (IV)-alkoxide to give a tertiary pyranol. By this method, one can only synthesize those pyranols with identical substitutions at positions 2 and 6. Further, as mentioned in the article, the yields using benzaldehyde (yields 46-77%) are generally higher than those where an aliphatic aldehyde is used (yields 26-36%).

[0014] It is known that 2-alkyl-4-methyltetrahydro-2 H -pyran-4-ol derivatives have a floral, lily-of-the-valley aroma. Lily-of-the-valley pyran or 2-isobutyl-4-methyltetrahydro-2 H -pyran-4-ol has a rose and lily of the valley smell. Rossiter, K. reported in Chimia, Vol. 55 (2001), pp. 388-396 that the introduction of two methyl groups (or dimethylation) at the 5-position of the lily of the valley pyran structure destroys the lily of the valley characteristics. In fact, the cis-isomer of the resulting compound 4,5,5-trimethyl-2-(2-methylpropyl)tetrahydropyran-4-ol has a sulfur, rubber and oily smell, while its trans-isomer is odorless.

[0015] Surprisingly, we have found that, along with the introduction of two methyl groups at the 5-position of the tetrahydropyran-4-ol moiety (or dimethylation), if an alkyl group is introduced in the immediate vicinity of the oxygen atom but at a different position from the initial alkyl group, the resulting 2,6-dialkyl-3,3,4-trimethyltetrahydro-2 H -Pyran-4-ol derivatives have camphorous, woody, earthy, patchouli-like characteristics.

[0016] Only one such 2,6-disubstituted-3,3,4-trimethyl-substituted tetrahydropyranol has been reported. For example, Markert, M. et al., Tetrahedron, Vol. 60, 2004, pp. 993-999, reported 3,3,4-trimethyl-2,6-diphenyltetrahydro-2 H -pyran-4-ol, wherein the compound is prepared as a mixture of diastereomers (83:17) by reaction between benzaldehyde and tetrakis(2,3-dimethylbutan-2-yl)oxy)titanium in the presence of lithium perchlorate. However, no fragrance, flavor and / or deodorizing / masking compositions are disclosed in the article, and there is absolutely no evidence or any indication of the presence of 3,3,4-trimethyl-2,6-diphenyltetrahydro-2 H - Any olfactory properties associated with 4-pyranol.

[0017] There are no reports of 2,6-disubstituted-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran derivatives (Y 1 There is no report providing any evidence or any indication of the existence of 2,6-disubstituted-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran derivatives (Y 1 ) any olfactory properties associated with

[0018] Similarly, there are no reports of 2,6-disubstituted-3,3,4-trimethyl-3,6-dihydro-2 H -pyran derivatives (Y 2 There is no report providing any evidence or any indication of the existence of 2,6-disubstituted-3,3,4-trimethyl-3,6-dihydro-2 H -pyran derivatives (Y 2 ) any olfactory properties associated with Summary of the invention

[0019] The present invention discloses a novel fragrance, flavor and / or deodorizing / masking composition, the composition comprises a 2,6-disubstituted-3,3,4-trimethyltetrahydro-2- H -pyran-4-ol derivatives and / or selected from the group consisting of formula (Y 1) compounds and / or 2,6-disubstituted-3,3-dimethyl-4-methylenetetrahydro-2H-pyran derivatives selected from the formula (Y 2 2,6-disubstituted-3,3,4-trimethyl-3,6-dihydro-2 H -pyran derivatives, wherein the formula (X), (Y 1 ) and (Y 2 )for

[0020]

[0021] Where R 1 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group or a substituted phenyl group; R 2 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms; R 3 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group or a substituted phenyl group and R 4 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms, provided that (X) cannot be 3,3,4-trimethyl-2,6-diphenyltetrahydro-2H-pyran-4-ol.

[0022] Therefore, according to the present invention, (X) cannot be 3,3,4-trimethyl-2,6-diphenyltetrahydro-2 H -pyran-4-ol.

[0023] In one embodiment of the present invention, R 1 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms; R 2 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms; R 3 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms and R 4 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms.

[0024] According to the invention, the group R 1 and R 2 are separate groups, ie they do not form a ring together. According to the invention, the group R 3 and R 4 are separate groups, ie they do not form a ring together.

[0025] In one embodiment of the present invention, R 1is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl, 2-hexyl, 3-hexyl, vinyl, 1-propenyl, prop-1-en-2-yl, allyl, 1-butenyl, 2-butenyl, but-3-en-2-yl, 1-pentenyl, pent-2-en-1-yl, pent-3-en-1-yl, pent-4-en-1-yl, pent-1-en-2-yl, 2-pentenyl, pent-3-en-2-yl, pent-4-en-2-yl, pent-2-en-3-yl, pent-1-en-3-yl, 1-hexenyl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, hex-1-en-2-yl, 2-hexenyl, hex-3-en-2-yl, hex-4-en-2-yl, hex-5-en-2-yl, 3-hexenyl, hex-1-en-3-yl, hex-2-en-3-yl, hex-3-en-3-yl, hex-4-en-3-yl or hex-5-en-3-yl, phenyl or substituted phenyl.

[0026] In one embodiment of the present invention, R 2 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl, 2-hexyl, 3-hexyl, vinyl, 1-propenyl, prop-1-en-2-yl, allyl, 1-butenyl, 2-butenyl, but-3-en-2-yl, 1-pentenyl, pent-2-en-1-yl, pent-3-en-1-yl, pent-4-en-1-yl, pent-1-en-2-yl, 2-pentenyl, pent-3-en-2-yl, pent-4-en-1-yl, pent-1-en-2-yl, pent-2-en-3-en-2-yl, pent-4-en-1-yl, pent-3-en-2-yl, pent-4-en-1-yl, pent-3-en-2-yl, pent-4-en-2-yl, pent-3-en-2-yl, pent-4-en-2-yl, pent-4-en-1-yl, pent-1-en-2-yl, pent-2-en-3-en-2-yl, pent-4-en-4-yl, pent-3-en-2-yl, pent-4-en-4-yl, pent-4-en-2-yl, pent-3-en-2-yl, pent-4 ...4-en- In some embodiments, the present invention comprises the following: 1-enyl, pent-2-en-3-yl, pent-2-en-3-yl, pent-1-en-3-yl, 1-hexenyl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, hex-1-en-2-yl, 2-hexenyl, hex-3-en-2-yl, hex-4-en-2-yl, hex-5-en-2-yl, 3-hexenyl, hex-1-en-3-yl, hex-2-en-3-yl, hex-3-en-3-yl, hex-4-en-3-yl or hex-5-en-3-yl.

[0027] In one embodiment of the present invention, R 3is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl, 2-hexyl, 3-hexyl, vinyl, 1-propenyl, prop-1-en-2-yl, allyl, 1-butenyl, 2-butenyl, but-3-en-2-yl, 1-pentenyl, pent-2-en-1-yl, pent-3-en-1-yl, pent-4-en-1-yl, pent-1-en-2-yl, 2-pentenyl, pent-3-en-2-yl, pent-4-en-2-yl, pent-2-en-3-yl, pent-1-en-3-yl, 1-hexenyl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, hex-1-en-2-yl, 2-hexenyl, hex-3-en-2-yl, hex-4-en-2-yl, hex-5-en-2-yl, 3-hexenyl, hex-1-en-3-yl, hex-2-en-3-yl, hex-3-en-3-yl, hex-4-en-3-yl or hex-5-en-3-yl, phenyl or substituted phenyl.

[0028] In one embodiment of the present invention, R 4 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl, 2-hexyl, 3-hexyl, vinyl, 1-propenyl, prop-1-en-2-yl, allyl, 1-butenyl, 2-butenyl, but-3-en-2-yl, 1-pentenyl, pent-2-en-1-yl, pent-3-en-1-yl, pent-4-en-1-yl, pent-1-en-2-yl, 2-pentenyl, pent-3-en-2-yl, pent-4-en-1-yl, pent-1-en-2-yl, pent-2-en-3-en-2-yl, pent-4-en-1-yl, pent-3-en-2-yl, pent-4-en-1-yl, pent-3-en-2-yl, pent-4-en-2-yl, pent-3-en-2-yl, pent-4-en-2-yl, pent-4-en-1-yl, pent-1-en-2-yl, pent-2-en-3-en-2-yl, pent-4-en-4-yl, pent-3-en-2-yl, pent-4-en-4-yl, pent-4-en-2-yl, pent-3-en-2-yl, pent-4 ...4-en- In some embodiments, the present invention comprises the following: 1-enyl, pent-2-en-3-yl, pent-2-en-3-yl, pent-1-en-3-yl, 1-hexenyl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, hex-1-en-2-yl, 2-hexenyl, hex-3-en-2-yl, hex-4-en-2-yl, hex-5-en-2-yl, 3-hexenyl, hex-1-en-3-yl, hex-2-en-3-yl, hex-3-en-3-yl, hex-4-en-3-yl or hex-5-en-3-yl.

[0029] In another embodiment, the compounds of formula (X) according to the invention may be chiral, for example they may be used as mixtures of stereoisomers (enantiomers or diastereomers), more particularly as mixtures of enantiomers; RRR Isomers, SSS Isomers, RSR Isomers, SRS Isomers, SSR Isomers, RRS Isomers, SRR Isomers, RSS Isomers, RRR , SSS , RSR , SRS , SSR , RRS , RSS , SRR In another embodiment, the formula (Y 1 ) or (Y 2 ) The compound may be chiral, for example it may be used as a mixture of stereoisomers (enantiomers or diastereomers), more particularly as a mixture of enantiomers; it may also be advantageous to use RR Isomers, SS Isomers, RS Isomers, SR Isomers, RR , SS , RS , SR In another embodiment, the alcohol compound of formula (X) and / or the alcohol compound of formula (Y) 1 ) and / or (Y 2 ) can also advantageously be used in pure form.

[0030] The simplified structure (Y) can be advantageously used to depict 2,6-disubstituted-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran derivatives (Y 1 ) and 2,6-disubstituted-3,3,4-trimethyl-3,6-dihydro-2 H -pyran derivatives (Y 2 ) Two types of compounds; group R 1 , R 2 , R 3 and R 4 As defined above.

[0031] DETAILED DESCRIPTION

[0032] The term "odorant" characterizing the compounds of the invention means that they induce a preferably pleasant odor sensation in humans; therefore, they are conventionally used to perfume industrial and sanitary products, detergents, cleaning agents, personal hygiene products, cosmetics, etc. For the purposes of the present invention and the appended claims, the term "odorant" includes "aroma substances". Aroma substances are terms generally used to designate substances that provide an odor and / or flavor to food.

[0033] The alcohol compound of formula (X) and / or the alcohol compound of formula (Y 1 ) and / or (Y 2) may be used alone, as a mixture thereof or in combination with the base material.

[0034] "Base material" as used herein includes all known aroma / flavor materials selected from a wide range of natural products, such as essential oils, extracts, resins or isolates and currently available synthetic materials, such as hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and / or mixtures with one or more ingredients or excipients / adjuvants conventionally used in combination with odorants in aroma and / or flavor compositions (e.g. solvents / diluents, stabilizers, carrier materials and other auxiliary agents commonly used in the art).

[0035] The alcohol compound of formula (X) and / or the alcohol compound of formula (Y 1 ) and / or (Y 2 ) can be used for a wide range of fragrance applications, for example in any fine and functional fragrance industry, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. Depending on the specific application and the nature and amount of other odorant ingredients, the compound can be used in a widely varying amount.

[0036] According to a preferred embodiment of the present invention, the fragrance, flavor and / or deodorizing / masking composition of the present invention contains at least one alcohol compound of formula (X) as previously described and / or formula (Y) in an amount of between 0.00001-99.9 wt.%, for example between 0.0001-95 wt.%, for example between 0.001-25 wt.%, preferably between 0.01-15 wt.%, more advantageously between 0.1-10 wt.%, in particular between 1-5 wt.%, relative to the entire composition in each case. 1 ) and / or (Y 2 ) of olefins.

[0037] According to a particularly preferred embodiment of the present invention, in addition to the alcohol compound of formula (X) and / or formula (Y 1 ) and / or (Y 2 ) in addition to the olefins, the fragrance, flavor and / or deodorizing / masking composition of the present invention contains additional odorants, for example in an amount of 0.1-99.9 wt.%, preferably 5-90 wt.%, in particular 15-70 wt.%, relative to the entire fragrance and / or flavor composition.

[0038] As described above, the alcohols of formula (X) and / or formula (Y 1 ) and / or (Y 2 ) can be prepared simply by directly mixing at least one compound of formula (X) and / or at least one compound of formula (Y 1 ) compounds and / or at least one compound of formula (Y2 ) or a compound comprising the formula (X) and / or (Y 1 ) and / or (Y 2 ) compounds and a consumer product base for use in a consumer product base; or it can be captured at an earlier step using a capturing material such as a polymer, capsule, microcapsule and / or nanocapsule, liposome, film former, absorbent (such as activated carbon or zeolite), cyclic oligosaccharide, cyclic glycoluril and a mixture of two or more thereof, or it can be chemically bonded to a matrix suitable for releasing the fragrance molecules upon application of an external stimulus (such as light, enzyme, air, water, etc.) and then mixed with the consumer product base.

[0039] Thus, the present invention can be used in existing processes for making fragrance, flavor and / or deodorizing / masking compositions by mixing the compounds directly into a consumer product base, or by mixing a product containing one or more of the formula (X) and / or (Y) 1 ) and / or (Y 2 ) compounds, which can then be mixed with a consumer product base using conventional techniques and methods to introduce one or more compounds of formula (X) and / or (Y) as fragrance, flavor and / or deodorizing / masking ingredients. 1 ) and / or (Y 2 ) compounds. By adding an olfactory acceptable amount of at least one of the above-described formula (X) and / or (Y) of the present invention. 1 ) and / or (Y 2 ) compounds that can improve, enhance and / or modify the odor notes of consumer product bases.

[0040] The present invention discloses novel fragrance, flavor and / or deodorizing / masking compositions comprising 2,6-disubstituted-3,3,4-trimethyltetrahydro-2- H -pyran-4-ol derivatives and / or 2,6-disubstituted-3,3-dimethyl-4-methylenetetrahydro-2- H -pyran derivatives and / or 2,6-disubstituted-3,3,4-trimethyl-3,6-dihydro-2- H -Pyran derivatives.

[0041] In a particular embodiment of the present invention, protection is claimed for compounds of formula (X) and / or (Y) as defined above. 1 ) and / or (Y 2 ) compounds; said compounds can be used in the perfume, fragrance and / or deodorizing / masking compositions of the present invention.

[0042] In one embodiment, the compound of formula (X) used in the fragrance, flavor and / or deodorizing / masking composition is selected from the following compounds:

[0043] 1) 2,6-Diethyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol

[0044] 2) 2,3,3,4,6-pentamethyltetrahydro-2H-pyran-4-ol

[0045] 3) 2-Isopropyl-3,3,4,6-tetramethyltetrahydro-2H-pyran-4-ol

[0046] 4) 6-ethyl-2-isopropyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol

[0047] 5) 6-ethyl-2,3,3,4-tetramethyltetrahydro-2H-pyran-4-ol

[0048] 6) 2,3,3,4-Tetramethyl-6-propyltetrahydro-2H-pyran-4-ol

[0049] 7) 6-isopropyl-2,3,3,4-tetramethyltetrahydro-2H-pyran-4-ol

[0050] 8) 2-Ethyl-2,4,5,5,6-pentamethyltetrahydro-2H-pyran-4-ol

[0051] 9) 2-Ethyl-3,3,4,6-tetramethyltetrahydro-2H-pyran-4-ol

[0052] 10) 2-Ethyl-3,3,4-trimethyl-6-propyltetrahydro-2H-pyran-4-ol

[0053] 11) 2-Ethyl-6-isopropyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol

[0054] 12) 2-Ethyl-6-isobutyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol

[0055] 13) 6-ethyl-2,2,4,5,5-pentamethyltetrahydro-2H-pyran-4-ol

[0056] 14) 2,6-Diethyl-2,4,5,5-tetramethyltetrahydro-2H-pyran-4-ol

[0057] 15) 6-ethyl-3,3,4-trimethyl-2-propyltetrahydro-2H-pyran-4-ol

[0058] 16) 6-isopropyl-3,3,4-trimethyl-2-propyltetrahydro-2H-pyran-4-ol

[0059] 17) 6-ethyl-2-isobutyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol

[0060] 18) 2-(2,3-dimethylbut-3-en-2-yl)-2,4,5,5,6-pentamethyltetrahydro-2H-pyran-4-ol

[0061] 19) 2-(2,3-dimethylbut-3-en-2-yl)-2-ethyl-4,5,5,6-tetramethyltetrahydro-2H-pyran-4-ol

[0062] In one embodiment, the compound of formula (Y) used in the fragrance, flavor and / or deodorizing / masking composition is selected from the following compounds:

[0063] 20) 2,3,3-trimethyl-4-methylene-6-propyltetrahydro-2H-pyran or 2,3,3,4-tetramethyl-6-propyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0064] 21) 6-ethyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran and 6-ethyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or preferably mixtures thereof,

[0065] 22) 2,3,3,6-tetramethyl-4-methylenetetrahydro-2H-pyran and 2,3,3,4,6-pentamethyl-3,6-dihydro-2H-pyran, or preferably mixtures thereof,

[0066] 23) 6-isopropyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran or 6-isopropyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0067] 24) 6-isobutyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran or 6-isobutyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0068] 25) 6-butyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran or 6-butyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0069] 26) 2-ethyl-3,3,6-trimethyl-4-methylenetetrahydro-2H-pyran or 2-ethyl-3,3,4,6-tetramethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0070] 27) 2,6-diethyl-3,3-dimethyl-4-methylenetetrahydro-2H-pyran or 2,6-diethyl-3,3,4-trimethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0071] 28) 2-ethyl-3,3-dimethyl-4-methylene-6-propyltetrahydro-2H-pyran or 2-ethyl-3,3,4-trimethyl-6-propyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0072] 29) 6-butyl-2-ethyl-3,3-dimethyl-4-methylenetetrahydro-2H-pyran or 6-butyl-2-ethyl-3,3,4-trimethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0073] 30) 6-ethyl-3,3-dimethyl-4-methylene-2-propyltetrahydro-2H-pyran or 6-ethyl-3,3,4-trimethyl-2-propyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0074] 31) 2-ethyl-6-(4-methoxyphenyl)-3,3-dimethyl-4-methylenetetrahydro-2H-pyran or 2-ethyl-6-(4-methoxyphenyl)-3,3,4-trimethyl-3,6-dihydro-2H-pyran, or preferably a mixture thereof,

[0075] In one embodiment of the invention, the fragrance, flavour and / or deodorising / masking composition comprises a compound of formula (X) or formula (Y) selected from any of the compounds mentioned above and / or from a mixture of two or more of said compounds.

[0076] The applicant surprisingly found that, from an olfactory point of view, the compounds of formula (X) and (Y) have a patchouli-like odor. In fact, compounds (X) and (Y) present a balanced blend of fresh camphor and earthy and woody notes. Compounds (X) and (Y) are very retentive and highly diffusible on blotting paper. In fact, compounds (X) and (Y) perform extremely well in woody, fougere and floral notes. These compounds blend very well with other woody and musky notes.

[0077] In one embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking compositions are advantageously used as perfumery compositions. The perfumery compositions of the present invention typically include perfumes, colognes, eau de toilettes and / or perfumes. In one embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking compositions are advantageously used in cosmetic preparations, personal care products, cleaning products, fabric softeners and / or air fresheners, etc. Furthermore, it is within the scope of embodiments of the present invention that the novel fragrance, flavor and / or deodorizing / masking compositions and / or the novel compounds of formula (X) or formula (Y) described herein may be integrated into building materials, wall and floor coverings, automotive parts, etc.

[0078] Typically, in addition to the novel odorants and / or fragrance, flavor and / or deodorizing / masking compositions described herein, suitable fragrance, flavor or deodorizing compositions may advantageously include conventional ingredients such as solvents, carriers, stabilizers, emulsifiers, humectants, dispersants, diluents, thickeners, diluents, other odorants and / or adjuvants, etc.

[0079] The compounds of formula (X) or (Y) are combined with a number of known natural or synthetic fragrance, flavor and / or deodorizing / masking materials, wherein the range of natural ingredients may include not only readily volatile but also semi-volatile and slightly volatile components, and the range of synthetic ingredients may include representatives from many classes of substances, such as those described in Steffen Arctander, Perfume and Flavor Chemicals, vol. 1 & 2, Montclair, NJ, 1969; Steffen Arctander, Perfume and Flavor Materials of Natural Origin, Elizabeth, NJ, 1960 or Horst Surburg, Johannes Panten, Common Fragrance and Flavor Materials, Wiley-VCH, Weinheim, 2016, and as is apparent from the following non-limiting compilation:

[0080] Natural products such as:

[0081] Ajowan oil, Amyris oil, Armoise oil, Artemisia oil, Basil oil, Bees wax absolute, Bergamot oil, Birch tar oil, Black pepper oil, Black pepper oleoresin, Camphor oil, Cananga oil, Caraway oil, Cardamom oil, Carrot seed oil, Castoreum absolute, Cedar leaf oil, Cedarwood oil, Celery seed oil, Chamomile oil, Cinnamon bark oil, Cinnamon leaf oil, Cistus absolute, Cistus oil oil, Citronella oil, Citronella terpenes, Clary sage oil, Clove oil rectified, Cognac oil white, Corianderseed oil, Cumin seed oil, Cypress oil, Davana oil, Dill seed oil, Elemi oil, Elemi resinoid, Eucalyptus oil, Fir needle oil, Galbanum oil, Geranium oil, Ginger oil Indian, Grapefruit oil, Guaiacwood oil, Gurjun balsam, Jasmin absolute, Jatamansi oil, Juniper oil berry oil), Juniper leaf oiloil), Kachur oil, Labdanum absolute, Labdanum resinoid, Lavender oil, Lemon oil, Lemon oil terpenes, Lemongrass oil, Lime oil, Litsea cubeba oil, Litsea cubeba terpenes, Lobhan choya resin, Mandarin oil, Mentha arvenisoil, Mentha citrata oil, Mimosa absolute, Myrrh resinoid, Nagarmotha oil, Nutmeg oil, Oakmoss absolute, Oakmoss resinoid, Olibanum oil, Olibanum resinoid, Orange oil oil, Origanum oil, Palma rosa oil, Patchouli oil, Peppermint oil, Peru Balsam resinoid, Petitgrain oil, Pine needle oil, Pink pepper oil, Rose absolut, Rose oil, Rosemary oil, Sandalwood oil, Seaweed absolute, Spearmint oil, Sugandh kokila oil, Sugandh mantri oil, Tagete oil, Tolu Balsam resinoid, Tuberose absolute, Turmeric oil, Turpentine oil, Valerian oil, Vetiver oil oil), Vetiver terpenes.

[0082] Synthetic raw materials such as:

[0083] Esters such as: C16 aldehyde, galbanum ester, allyl hexanoate, allyl cyclohexyl propionate, allyl heptanoate, allyl phenoxyacetate, isopentyl acetate, amyl benzoate, amyl butyrate, amyl hexanoate, amyl cinnamate, amyl isovalerate, amyl phenylacetate, amyl propionate, isopentyl salicylate, acetylated agarwood oil (Amyris acetate), anisyl acetate, benzyl acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzylisoeugenol, benzyl propionate, benzyl salicylate, benzyl tiglate, butyl acetate, butyl butyrate, butyl butyrolactate, caryophyllene acetate, cedryl acetate, cinnamyl acetate, cinnamyl butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl hexanoate, cis-3-hexenyl formate, cis-3-hexenyl isobutyrate, cis- 3-Hexenyl-2-methylbutyrate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, cis-3-hexenyl tiglate, citronellyl acetate, citronellyl butyrate, citronellyl formate, citronellyl isobutyrate, citronellyl propionate, citronellyl tiglate, cycloclabute, cyclogalbanate, cyclohexyl ethyl acetate, decyl acetate, dibutyl phthalate, diethyl malonate, diethyl phthalate, dihydromyrcenyl acetate, dimethyl octyl acetate, dimethyl phenethyl acetate phenyl ethyl carbinyl acetate), dioctyl adipate, dioctyl phthalate, dimethyl benzyl carbinyl acetate, dimethyl benzyl carbinyl butyrate, ethyl linalyl acetate, ethyl 2-methylbutyrate, ethyl 3-phenylpropionate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl decanoate, ethyl hexanoate, ethyl octanoate, ethyl cinnamate, ethyl heptanoate, ethyl hexyl acetate, ethyl isobutyrate, ethyl laurate, ethyl pelargonate, ethyl phenoxyacetate, ethyl phenyl acetate, ethyl phenyl glycidate, ethyl propionate, ethyl crocetin, ethyl salicylate, ethyl valerate, eugenyl acetate, evernyl, fenchyl acetate acetate), Floramat, FrescolatML, ethyl methyl dicyclopentane acetate (Fructone), ethyl tricyclodecane carboxylate (Fruitate), geranyl acetate (Geranyl acetateacetate), Geranyl butyrate, Geranyl formate, Geranyl propionate, Geranyl tiglate, Givescone, Guaiol acetate, Hedione, Helvetolide, Herbanate, Hexyl acetate, Hexyl benzoate, Hexyl butyrate, Hexyl caproate, Hexyl isobutyrate, Hexyl propionate, Hexyl salicylate, Isoborneol acetate, Isobutyl acetate, Isobutylphenyl acetate, Isobutyl salicylate, Isoeugenol acetate, Isononyl acetate, Isopentyrate, Isopropyl 2-methylbutyrate, Isopropyl myristate myristate), Jasmonyl, Liffarome, Linalyl acetate, Mahagonate, Manzanate, Menthanylacetate, Menthyl acetate, Methyl benzoate, 2-methylbutyl acetate, Methyl camomille, Methyl cinnamate, Methyl cyclogeranate, Methyl heptinecarbonate, Methyl laurate, Methyl octine carbonate, Methyl phenyl acetate, Methyl salicylate, Methyl-2-methylbutyrate, Neofolione, Nopyl acetate, Octenyl acetate, Octyl acetate, Octyl isobutyrate, Para cresyl acetate, Para cresyl isobutyrate, Para cresyl phenyl acetate, phenyl acetate), pear ester, peranat, phenoxyethyl isobutyrate, phenethyl acetate, phenethyl butyrate, phenethyl formate, phenethyl isobutyrate, phenethyl phenylacetate, phenethyl propionate, phenethyl salicylate, phenethyl tiglate, phenylpropyl isobutyrate, prenyl acetate, romandolide, sagecete, styrallyl acetate, styrallyl propionatepropionate), Tangerinol, Terpinyl acetate, Thesaron, trans-2-hexenyl acetate, Tropicate, Verdox, Verdyl acetate, Verdyl propionate, Vertenex, Vetikolacetate, Vetiveryl acetate, Yasmolys.

[0084] Lactones such as: Ambrettolide, Arova N, Celeriax, Decanolide δ, Decanolide γ, Dodecanolactone δ, Dodecanolactone γ, Brassic acid glycol ester, Exaltolide, Heptanolide γ, Caprolactone δ, Caprolactone γ, Methyl laitone, Methyl octanolactone, Nonanolide δ, Nonanolide γ, Octahydrocoumarin, Octanolide δ, Octanolide γ, Rootylone, Silvanonesupra, Undecanolide δ, Undecanolide γ, Valerolactone γ, 10-OxaHexaDecanolide (OHD Musk), Coumarin, Habanolide, Jasmolactone.

[0085] Aldehydes such as: acetaldehyde, adoxal, C10 aldehyde, iso-C11 aldehyde, C11 moa aldehyde (Aldehyde C11moa), C11 undecenal, C11 undecyl aldehyde, C12 lauric aldehyde, C12 MNA aldehyde, anisaldehyde, amyl cinnamaldehyde, benzaldehyde, bourgeonal, campholenaldehyde, cantonal, cetonal, cinnamaldehyde, cis-4-decenal, cis-6-nonenal, citral, citronellal, citronellal, cocal, cuminaldehyde, curgix, cyclal c, cyclamen aldehyde), cyclomyral, cyclovertal, decanal 9, dupical, empetal, ethyl vanillin, floralozone, florhydral, geranaldehyde, neoheterol, heptaldehyde, hexanal, hexylcinnamaldehyde, hivernal neo, hydratropaldehyde, hydroxycitronellal, intreleven aldehyde), Isobutavan, Isocyclocitral, Isovaleraldehyde, Lilial, Limonenal, Maceal, Mefranal, Melonal, Methylcinnamaldehyde, Trans-2-cis-6-nonadienal, Nonanal, Octanal, Oncidal, p-Tolualdehyde, Phenylacetaldehyde, Phenylpropionaldehyde, Methyl Precyclemone B, Safranal, Salicylaldehyde, Scentenal, Syringaaldehyde, Trans-4-Decenal, Trans-2-Dodecenal, Trans-2-Hexenal, Trans-2-Nonenal, Trifernal, Vanillin, Veratraldehyde, Vernaldehyde.

[0086] Ketones such as: Acetanisol, Acetoin, Acetophenone, Aldron, Allyl ionone, Benzophenone, Benzyl acetone, Calone, Camphor, Carvone d-, l-Carvone, Cashmeran, Cedryl methylketone, Cepionate, Claritone, Cosmone, Crysolide, Cyclotene, Damascenone, Damascone alpha, Damascone beta, Damascone delta, Damascone gamma, Diacetyl, Dihydro beta ionone, Dihydroisojasmonate isojasmonate), Dimethyl octenone, Dynascone, Ethyl amyl ketone, Ethyl maltol, Fenchone, Filbertone, Geranyl acetone, Globanone, Heptyl cyclopentanone, Ionone α, Ionone β, Pure Ionone, Iriswood, Irone α, Ambergrisone, Isofenchone, Isolone K, Isomenthone, Isophorone, Jasmone cis-, Kambernoir, Kephalis, Koavone, Lavendinal, Maltol, Menthone, Methylacetophenone, Methylamyl ketone, Methylhexyl ketone, Methylionone gamma, Methyl naphthyl ketone beta, Methylnonyl ketonenonylketone), Muscenone, Muscone, Nectaryl, Orinox, OTBC ketone, tert-butylcyclohexanone, Patchwood, Phantolid, Pharaone, Piperitone, Plicatone, Raspberry ketone, Raspberryketone methyl ether, Safraleine, Spirogalbanone pure, Tonalid, Trimofix O, Veloutone, Vetikon.

[0087] Alcohols such as: Alcohol oxo C13, Amber core, Ambermax, Ambrinol, Amyl vinyl carbinol, Anisic alcohol, Bacdanol, Benzyl alcohol, Butyl alcohol, Cedrol crystals, Cinnamyl alcohol, Citronellol, Coranol, Decyl alcohol, Dimethyl benzyl carbinol, Dimethyl octanol, Dimethyl phenethyl carbinol, Dimetol, Fenchol, Hexanol, Isoborneol, Isobornyl cyclohexanol, Javanol, Keflorol, Kohinool, Lauryl alcohol, Lilyflore, Linalool oxide oxide), Mayol, Menthol, Norlimbanol, Octanol, Osyrol, tert-butyl cyclohexanol, Phenoxanol, Phenoxyethanol, Phenylethanol, Phenylpropanol, Propylene glycol, Rosaphen, Rose glycol, Styrallyl alcohol, Tricyclodecanedimethanol, Tetrahydrolinalool, Tetrahydro myrcenol, Timberol, Undecavertol, Citronellol laevo), Cyclofloranol, Dihydrolinalool, Dihydromyrcenol, Dimyrcetol, Ebanol, Geraniol, Isopulegol, Linalool, Nerol, Nerolidol, Trans-2-cis-6-nonadienol, Polysantol, Rosalva, Sandalmysore core, Sandalore, Terpinen-4-ol, Terpineol, Trans-2-hexenol.

[0088] Phenols such as: Butylated hydroxyanisole, dihydroeugenol, dimethylhydroquinone, dimethyl resorcinol, Eugenol pure, guaiacol, isoeugenol, meta cresol, methyl diantilis, paracresol, propenyl guaethol, thymol, ultravanil.

[0089] Ethers such as: Ambroxan, Anethole, Anther, Benzyl Isoamyl Ether, Benzyl Isopropyl Ether, Benzyl Isovalerate, Boisiris, Cedramber, Cetalox, Decyl Methyl Ether, Dibenzyl Ether, Dihydro Rose Oxide, Diphenyl Oxide, Doremox, Estragole, Ethyl Linalool, Eucalyptol, Galaxolide, Gyrane, Herbavert, Lime Oxide, Madrox, Methyl Isoeugenol, β-Naphthyl Isobutyl Ether, Nerol Oxide, Nerolinbromelia, Para cresyl butyl ether, Para cresyl methylether), Petiole, phenethyl methyl ether, 2,4-dimethyl-4-phenyltetrahydrofuran (Rhubafuran), rose oxide (Rose oxide), aromatic rose ether (Rosyrane), Trisamber, Vetylbois K, β-naphthyl methyl ether (Yarayara).

[0090] Acetals such as: Acetal CD, Acetal R, Amberketal, Boisambrene forte, Citrathal, 1,1-diethoxyethane, Emeraldine, Freshopal, Herboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Elintaal, Glycolierral, Caraflor, Methyl pamplemousse.

[0091] Hydrocarbons such as: Bisabolene, Camphene, Carene delta 3, Caryophyllene, Cedrene, Cymene para, Dipentene, Diphenylmethane, Isolongifolene, Limonene d-, Longifolene, Myrcene, Naphthalene, Ocimene, Pinene alpha, Pinene beta, Styrene, Terpinene gamma, Terpinolene, Undecatriene, Verdoracine.

[0092] Sulfur-containing compounds such as Corps cassis, dibutyl sulfide, dimethyl sulfide, Exovert, Grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

[0093] Nitriles such as: cinnamon nitrile, citronellyl nitrile, citronitrile, clonal, cumin nitrile, hexylcyclopentanone, iris nitrile, lemon nitrile, peony nitrile, tridecyl nitrile, agrumen nitrile, and n-dodecyl nitrile.

[0094] Oximes such as Buccoxime, Labienoxime, and Stemone.

[0095] Nitrogen-containing heterocyclic rings such as: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, 2-(3-phenylpropyl)pyridine (Corps racine), 2-ethyl-3,5 (or 6)-dimethylpyrazine, 1-furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3 (or 6)-methoxypyrazine, isopropylquinoline, Maritima, p-methylquinoline, skatol, 2,3,5-trimethylpyrazine.

[0096] Nitro compounds such as Musk Ketone.

[0097] Schiff bases such as: Aurantiol, helianthral, ​​ligantraal, and lingorhizine.

[0098] Other materials include: acetanilide, cyclic amine (Gardamide), fruit amide (Paradisamide), dimethyl anthranilate (Dimethyl anthranilate), methyl anthranilate (Methyl anthranilate), butyric acid, capric acid, caproic acid, caprylic acid, phenylacetic acid, caryophyllene oxide, cedroxyde, and Tobacarol.

[0099] Thus, compounds of formula (X) or (Y) and a wide range of known odorants / fragrances, flavors and / or deodorizing / masking materials (as will be apparent from the foregoing compilation) may be used to produce compositions. In the production of such compositions, the previously mentioned known fragrances, flavors and / or deodorizing / masking materials may be used according to methods known to perfumers, such as according to WA Pocket, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London 1974.

[0100] In one embodiment of the invention, the claimed fragrance, flavor and / or deodorizing / masking composition comprises, in addition to the compound of formula (X) or (Y), at least one ester and / or one alcohol (in addition to compound (X), if present), preferably at least one mixture of esters and alcohols; the esters and / or alcohols are preferably selected from the list defined above. In one embodiment of the invention, the claimed odorant composition is characterized by a total content of the compound of formula (X) or (Y) and the esters and / or alcohols together, higher than 25 wt%, preferably higher than 50 wt%, for example higher than 75 wt%, or even higher than 90 wt%.

[0101] preparation

[0102] Various acids were screened for the selective formation of 2,6-diethyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol (X) by reacting 4,4,5-trimethylhex-5-en-3-ol and propionaldehyde. All reactions were carried out at room temperature (25° C.) in toluene containing 0.5 equivalents of the corresponding acid.

[0103]

[0104]

[0105] Obviously, phosphoric acid, trifluoroacetic acid and ferric chloride are much better in selectively forming the desired tertiary alcohol (X), while the isomeric olefins (Y 1 +Y 2 ) are formed to a much lesser extent. All other acids, on the other hand, give the desired alcohol (X) in poor yields and / or in most cases predominantly form isomeric olefins.

[0106] Trifluoroacetic acid is an expensive and corrosive acid, while ferric chloride is harmful, corrosive, and can be very dangerous. 3 PO 4 ) is a relatively weaker acid than trifluoroacetic acid and ferric chloride. Moreover, phosphoric acid is much less corrosive than trifluoroacetic acid and ferric chloride.

[0107] To avoid the use of toluene, various concentrations of phosphoric acid in water were used for the reaction between 4,4,5-trimethylhex-5-en-3-ol and propionaldehyde. Surprisingly, the reaction was found to work very well and to form the desired product, 2,6-diethyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol, in good yield. Aqueous phosphoric acid was found to work well and to form the compound represented by formula (X) in good yield.

[0108] In a preferred embodiment of the present invention, the compound represented by the general formula (X) can be advantageously synthesized in one step from the corresponding alcohol of formula (I) and the carbonyl compound (aldehyde or ketone) of formula (II) in the presence of phosphoric acid, preferably aqueous (preferably 10% to 85% by weight) phosphoric acid, more particularly between 30% and 60% aqueous phosphoric acid, more particularly between 55% and 60% aqueous phosphoric acid (0.1-1.0 equivalents), at a temperature between 0°C and 45°C. In this case, a small amount of the corresponding compound (Y) can also be advantageously formed. In this context, each compound Y is preferably an exo-isomer Y 1 and endo isomer Y 2 mixture.

[0109]

[0110] Where R 1 , R 2 , R 3 and R 4 As defined above.

[0111] For example, R 1 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group or a substituted phenyl group; R 2 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms; R 3 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms and R 4 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms.

[0112]

[0113] In the literature, Prince cyclization of homoallylic alcohols (such as isoprenol) with carbonyl compounds (such as aldehydes or ketones) to give 2,4-disubstituted tetrahydropyran-4-ols is known. However, there are no examples of Prince reactions of homoallylic alcohols represented by formula (I) with carbonyl compounds. In fact, it can be expected that under acidic conditions, the corresponding secondary or tertiary alcohols represented by formula (I) may undergo dehydration or rearrangement followed by dehydration.

[0114] In one embodiment of the present invention, it was surprisingly found that in the presence of an appropriate concentration (e.g., 55-60%) of aqueous phosphoric acid (0.1-1.0 equivalents), an alcohol of formula (I) undergoes Prince cyclization with a carbonyl compound at 0°C-45°C to give a 2,6-disubstituted-3,3,4-trimethyltetrahydro-2 H -pyran-4-ol derivatives (X);

[0115]

[0116] Where R 1 , R 2 , R 3 and R 4 As defined above.

[0117] For example, R 1 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group or a substituted phenyl group; R 2 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms; R 3 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms and R 4 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms.

[0118] The group R of the compound of formula (I) and the compound of formula (II) 1 , R 2 , R 3 and R 4 and formula (X) and / or formula (Y 1 ) and / or formula (Y 2 ) and / or the radical R of the corresponding synthetic compound and / or its mixture 1 , R 2 , R 3 and R 4 same.

[0119] According to the invention, the group R 1 and R 2 are separate groups, ie they do not form a ring together. According to the invention, the group R 3 and R 4 are separate groups, ie they do not form a ring together.

[0120] The compound represented by the general formula (Y) can be advantageously synthesized in one step from the corresponding alcohol (I) and the carbonyl compound (II, aldehyde or ketone) in the presence of a protic acid such as p-toluenesulfonic acid (0.1-1.0 equivalent) at 2°C-45°C in an organic solvent such as ethylene dichloride (EDC). In fact, a typical compound Y is preferably an exo-isomer Y 1 and endo isomer Y 2 In this case, a small amount of the corresponding compound (X) may also be formed, wherein R 1 , R 2 , R 3 and R 4 As defined above.

[0121]

[0122] Compounds of general formula (I) can be synthesized as in WO2019228903.

[0123] or

[0124] The compounds of general formula (I) can be prepared by sodium borohydride-mediated reduction of the corresponding carbonyl compounds of formula (III) or by addition of an appropriate Grignard reagent R to (III). 2 MgX is used to prepare;

[0125]

[0126] Where R 1 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group or a substituted phenyl group; R 2 is an alkyl or alkenyl group having up to 6 carbon atoms.

[0127] The compound of general formula (III) can be prepared from 2,3-dimethylbut-1-ene or 2,3-dimethylbut-2-ene and the corresponding anhydride or carboxylic acid R 1 The acyl chloride of COOH is reacted with any Lewis acid (such as AlCl 3 or ZnCl 2 ) or a protic acid (such as methanesulfonic acid).

[0128] Example 1

[0129] 2,6-Diethyl-3,3,4-trimethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0130]

[0131] Method A: To a solution of 4,4,5-trimethylhex-5-en-3-ol (250 g, 1.75 mmol) and phosphoric acid (84.1 g of 85% solution, 71.5 g, 0.73 mmol) in water (50 g) was slowly added propionaldehyde (125 g, 2.15 mmol) over 4 hours at 25°C. After stirring the reaction mixture at 25°C for 2 h, it was diluted with water (500 mL) and the aqueous layer was separated. The organic layer was washed with 10% sodium bicarbonate solution (300 mL) and then water (500 mL). The organic layer was concentrated in vacuo and the resulting crude product was fractionated (66°C, 3 mbar) to give 2,6-diethyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol (220.0 g, 62%) as a mixture of two diastereomers (92:8, colorless liquid).

[0132] 1 H NMR (400 MHz, CDCl 3), major diastereomer: δ 3.22-3.28 (m, 1H), 3.01 (dd, J = 2.4 Hz, 10.0 Hz, 1H), 1.52-1.61 (m, 1H), 1.41-1.61 (m, 2H), 1.30-1.39 (m,2H), 1.26 (s, 3H), 0.92-1.01 (m, 10 H), 0.81 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ 83.6, 73.3, 43.8, 41.2, 29.2, 23.2, 22.7, 19.2, 15.9, 11.8, 10.2.

[0133] Odor Profile: Patchouli-like, fresh, camphorous, earthy, woody.

[0134] Example 2

[0135] 2,3,3,4,6-pentamethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0136]

[0137] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and acetaldehyde.

[0138] 1 H NMR (400 MHz, CDCl 3 ), a mixture of two diastereomers in a ratio of 77:23; the major diastereomer δ 3.57-3.49 (m, 1H), 3.37 (q, J = 6.4 Hz, 1H), 1.61-1.55 (m, 1H), 1.37 (dd, J =12.8, 2.4 Hz, 1H), 1.21 (s, 3H), 1.13 (d, J = 4.4 Hz, 3H), 1.03 (d, J = 6.4Hz, 3H), 0.90 (s, 3H), 0.75 (s, 3H).

[0139] Odor Profile: Dry woody, aromatic.

[0140] Example 3

[0141] Synthesis of 2-Isopropyl-3,3,4,6-tetramethyltetrahydro-2H-pyran-4-ol

[0142]

[0143] Obtained using Method A from 2,4,4,5-tetramethylhex-5-en-3-ol and acetaldehyde.

[0144] Odor profile: Camphor, patchouli-like.

[0145] Example 4

[0146] Synthesis of 6-ethyl-2-isopropyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol

[0147]

[0148] Obtained using Method A from 2,4,4,5-tetramethylhex-5-en-3-ol and propionaldehyde.

[0149] Odor profile: Camphor, patchouli-like.

[0150] Example 5

[0151] 6-ethyl-2,3,3,4-tetramethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0152]

[0153] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and propionaldehyde.

[0154] Odor Profile: Intense woody.

[0155] Example 6

[0156] 2,3,3,4-Tetramethyl-6-propyltetrahydro-2 H Synthesis of -pyran-4-ol

[0157]

[0158] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and butyraldehyde.

[0159] 1 H NMR (400 MHz, CDCl 3), a mixture of two diastereomers in a ratio of 55:45; δ 3.50-3.43 (m, 1H), 3.38-3.31 (m, 2H), 3.09-3.06 (m, 1H), 1.59-1.52 (m, 5H), 1.39-1.33 (m, 3H), 1.32-1.26 (m, 4H), 1.21 (s, 3H), 1.20 (s, 3H), 1.12 (d, J = 6.4 Hz,3H), 1.02 (d, J = 6.4 Hz, 3H), 0.89 (s, 3H), 0.88 (s, 3H), 0.84 (t, J = 7.2Hz, 3H), 0.83 (t, J = 7.2 Hz, 3H), 0.75 (s, 3H), 0.74 (s, 3H).

[0160] Odor Profile: Woody.

[0161] Example 7

[0162] 6-isopropyl-2,3,3,4-tetramethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0163]

[0164] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and isobutyraldehyde.

[0165] 1 H NMR (400 MHz, CDCl 3 ), a mixture of two diastereomers in a ratio of 60:40; major diastereomer δ 3.48-3.38 (m, 1H), 2.89-2.88 (m, 1H), 1.2 (s, 3H), 1.82-1.74 (m, 1H), 1.62-1.52 (m, 2H), 1.09 (d, J = 6.4 Hz, 3H), 0.88-0.86 (overlapping peaks, 6H), 0.8 (s, 6H).

[0166] Odor Profile: Woody.

[0167] Example 8

[0168] 2-Ethyl-2,4,5,5,6-pentamethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0169]

[0170] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and 2-butanone.

[0171] Odor Profile: Woody camphor, aromatic pine.

[0172] Example 9

[0173] 2-Ethyl-3,3,4,6-tetramethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0174]

[0175] Obtained using Method A from 4,4,5-trimethylhex-5-en-3-ol and acetaldehyde.

[0176] 1 H NMR (400 MHz, CDCl 3 ) δ 3.52-3.40 (m, 1H), 3.0-2.91 (dd, 1H), 1.62-1.54 (m, 1H), 1.40-1.35 (m, 2H), 1.32-1.25 (m, 1H), 1.21 (s, 3H), 1.13 (d, J = 6.0 Hz, 3H), 0.91 (t, J = 7.2 Hz, 3H), 0.88 (s, 3H), 0.75 (s, 3H).

[0177] Odor Profile: Woody.

[0178] Example 10

[0179] 2-Ethyl-3,3,4-trimethyl-6-propyltetrahydro-2 H Synthesis of -pyran-4-ol

[0180]

[0181] Obtained using Method A from 4,4,5-trimethylhex-5-en-3-ol and butyraldehyde.

[0182] Odor profile: Cedar woody notes, fruity.

[0183] Embodiment 11

[0184] 2-Ethyl-6-isopropyl-3,3,4-trimethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0185]

[0186] Obtained using Method A from 4,4,5-trimethylhex-5-en-3-ol and isobutyraldehyde.

[0187] Odor profile: Woody, camphorous.

[0188] Example 12

[0189] 2-Ethyl-6-isobutyl-3,3,4-trimethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0190]

[0191] Obtained using Method A from 4,4,5-trimethylhex-5-en-3-ol and isovaleraldehyde.

[0192] Sensory profile: Grassy (green), woody, hay, eucalyptus-like.

[0193] Embodiment 13

[0194] 6-Ethyl-2,2,4,5,5-pentamethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0195]

[0196] Obtained using Method A from 4,4,5-trimethylhex-5-en-3-ol and acetone.

[0197] Odor profile: woody, slightly cresol.

[0198] Embodiment 14

[0199] 2,6-Diethyl-2,4,5,5-tetramethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0200]

[0201] Obtained using Method A from 4,4,5-trimethylhex-5-en-3-ol and 2-butanone.

[0202] 1 H NMR (400 MHz, CDCl 3) δ 3.21-3.18 (m, 1H), 3.04-2.95 (m, 1H), 1.59-1.46 (m, 3H), 1.42-1.30 (m, 3H), 1.21 (s, 3H), 0.94-0.87 (overlapping 4 Me signals, 12H), 0.75 (s, 3H).

[0203] Odor Profile: Dry woody.

[0204] Embodiment 15

[0205] 6-ethyl-3,3,4-trimethyl-2-propyltetrahydro-2 H Synthesis of -pyran-4-ol

[0206]

[0207] Obtained by method A from 2,3,3-trimethylhept-1-en-4-ol and propionaldehyde as a mixture of stereoisomers.

[0208] Odor Profile: Woody.

[0209] Example 16

[0210] 6-isopropyl-3,3,4-trimethyl-2-propyltetrahydro-2 H Synthesis of -pyran-4-ol

[0211]

[0212] Obtained by Method A from 2,3,3-trimethylhept-1-en-4-ol and isobutyraldehyde as a mixture of stereoisomers.

[0213] Odor Profile: Woody.

[0214] Embodiment 17

[0215] 6-ethyl-2-isobutyl-3,3,4-tributyltetrahydro-2 H Synthesis of -pyran-4-ol

[0216]

[0217] Obtained from Method A using 2,3,3,6-tetramethylhept-1-en-4-ol and propionaldehyde.

[0218] 1 H NMR (400 MHz, CDCl 3 ), a mixture of two diastereomers in a 90:10 ratio; major diastereomer δ 3.23-3.16 (m, 1H), 3.13 (dd, J= 10.4, 1.6 Hz, 1H), 2.95 (dd, J = 10.4, 2.4 Hz, 1H).

[0219] Odor Profile: Woody.

[0220] Embodiment 18

[0221] 2-(2,3-dimethylbut-3-en-2-yl)-2,4,5,5,6-pentamethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0222]

[0223] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and 3,3,4-trimethylpent-4-en-2-one.

[0224] Sensory profile: Camphoraceous, aromatic.

[0225] Embodiment 19

[0226] 2-(2,3-dimethylbut-3-en-2-yl)-2-ethyl-4,5,5,6-tetramethyltetrahydro-2 H Synthesis of -pyran-4-ol

[0227]

[0228] Obtained using Method A from 3,3,4-trimethylpent-4-en-2-ol and 4,4,5-trimethylhex-5-en-3-one.

[0229] Sensory profile: Woody, aromatic.

[0230] Embodiment 20

[0231] 2,3,3-Trimethyl-4-methylene-6-propyltetrahydro-2 H -pyran or 2,3,3,4-tetramethyl-6-propyl-3,6-dihydro-2 H -Synthesis of pyran

[0232]

[0233] Method B: To a solution of 3,3,4-trimethylpent-4-en-2-ol (10 g, 38 mmol) and p-toluenesulfonic acid monohydrate (2.97 g, 15.60 mmol) in 1,2-dichloroethane (100 mL) was added butyraldehyde (6.75 g, 94 mmol) dropwise over 1 h. The resulting reaction mixture was stirred at room temperature for 2 h and then diluted with water and quenched by the addition of saturated NaHCO3 The mixture was neutralized and extracted with dichloromethane (3 x 50 mL). The organic layer was washed with water, brine, and then purified by anhydrous Na 2 SO 4 The mixture was dried and filtered. The organic solvent was removed under reduced pressure to give a crude compound which was purified by column chromatography (230-400 mesh silica gel) using 0-20% ethyl acetate / hexane to give 4.2 g of olefin (Example 29) and 4.8 g of alcohol (Example 4). Both products were distilled using a Kugelrohr apparatus to give the corresponding samples for olfactory evaluation (combined yield of 63%).

[0234] Odor Profile: Woody.

[0235] Embodiment 21

[0236] 6-ethyl-2,3,3-trimethyl-4-methylenetetrahydro-2 H -pyran and 6-ethyl-2,3,3,4-tetramethyl-3,6-dihydro-2 H -Synthesis of pyran

[0237] Obtained using Method B from 3,3,4-trimethylpent-4-en-2-ol and propionaldehyde as a mixture of diastereomers and exo / endo isomers.

[0238]

[0239] Odor profile: Woody, camphorous.

[0240] Embodiment 22

[0241] 2,3,3,6-Tetramethyl-4-methylenetetrahydro-2 H -pyran and 2,3,3,4,6-pentamethyl-3,6-dihydro-2 H -Synthesis of pyran

[0242]

[0243] Obtained using Method B from 3,3,4-trimethylpent-4-en-2-ol and acetaldehyde as a mixture of diastereomers and exo / endo isomers.

[0244] 1 H NMR (400 MHz, CDCl 3 )

[0245] Odor Profile: Mossy, woody, sweet pea notes.

[0246] Embodiment 23

[0247] 6-isopropyl-2,3,3-trimethyl-4-methylenetetrahydro-2 H-pyran and 6-isopropyl-2,3,3,4-tetramethyl-3,6-dihydro-2 H -Synthesis of pyran

[0248] Obtained using Method B from 3,3,4-trimethylpent-4-en-2-ol and isobutyraldehyde as a mixture of diastereomers and exo / endo isomers.

[0249]

[0250] Odor Profile: Woody camphor.

[0251] Embodiment 24

[0252] 6-isobutyl-2,3,3-trimethyl-4-methylenetetrahydro-2 H -pyran and 6-isobutyl-2,3,3,4-tetramethyl-3,6-dihydro-2 H -Synthesis of pyran

[0253] Obtained using Method B from 3,3,4-trimethylpent-4-en-2-ol and isovaleraldehyde as a mixture of diastereomers and exo / endo isomers.

[0254]

[0255] Odor Profile: Woody.

[0256] Embodiment 25

[0257] 6-Butyl-2,3,3-trimethyl-4-methylenetetrahydro-2 H -pyran and 6-butyl-2,3,3,4-tetramethyl-3,6-dihydro-2 H -Synthesis of pyran

[0258] Obtained using Method B from 3,3,4-trimethylpent-4-en-2-ol and butyraldehyde as a mixture of diastereomers and exo / endo isomers.

[0259]

[0260] Odor Profile: Woody.

[0261] Embodiment 26

[0262] 2-Ethyl-3,3,6-trimethyl-4-methylenetetrahydro-2 H -pyran and 2-ethyl-3,3,4,6-tetramethyl-3,6-dihydro-2 H -Synthesis of pyran

[0263]

[0264] Obtained using method B from 4,4,5-trimethylhex-5-en-3-ol and acetaldehyde as a mixture of diastereomers and exo / endo isomers.

[0265] Odor profile: Camphor, woody.

[0266] Embodiment 27

[0267] 2,6-Diethyl-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran and 2,6-diethyl-3,3,4-trimethyl-3,6-dihydro-2 H -Synthesis of pyran

[0268]

[0269] Obtained using method B from 4,4,5-trimethylhex-5-en-3-ol and propionaldehyde as a mixture of diastereomers and exo / endo isomers.

[0270] Odor profile: Woody, camphorous.

[0271] Embodiment 28

[0272] 2-Ethyl-3,3-dimethyl-4-methylene-6-propyltetrahydro-2 H -pyran and 2-ethyl-3,3,4-trimethyl-6-propyl-3,6-dihydro-2 H -Synthesis of pyran

[0273]

[0274] Obtained using method B from 4,4,5-trimethylhex-5-en-3-ol and butyraldehyde as a mixture of diastereomers and exo / endo isomers.

[0275] Odor Profile: Woody powdery, gourmand, caramel, liquorice, tarragon, jasmine,

[0276] Embodiment 29

[0277] 6-Butyl-2-ethyl-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran and 6-butyl-2-ethyl-3,3,4-trimethyl-3,6-dihydro-2 H -Synthesis of pyran

[0278] Obtained using method B from 4,4,5-trimethylhex-5-en-3-ol and valeraldehyde as a mixture of diastereomers and exo / endo isomers.

[0279]

[0280] Odor profile: Woody, aldehyde, grassy, ​​raw sugar cane-like, floral, tea, tobacco, fenugreek.

[0281] Embodiment 30

[0282] 6-ethyl-3,3-dimethyl-4-methylene-2-propyltetrahydro-2 H -pyran and 6-ethyl-3,3,4-trimethyl-2-propyl-3,6-dihydro-2 H -Synthesis of pyran

[0283]

[0284] Obtained using Method B from 2,3,3-trimethylhept-1-en-4-ol and propionaldehyde as a mixture of diastereomers and exo / endo isomers.

[0285] Odor Profile: Woody.

[0286] Embodiment 31

[0287] 2-ethyl-6-(4-methoxyphenyl)-3,3-dimethyl-4-methylenetetrahydro-2 H -pyran and 2-ethyl-6-(4-methoxyphenyl)-3,3,4-trimethyl-3,6-dihydro-2 H -Synthesis of pyran

[0288]

[0289] Obtained using method B from 4,4,5-trimethylhex-5-en-3-ol and 4-methoxybenzaldehyde as a mixture of diastereomers and exo / endo isomers.

[0290] Odor Profile: Woody, powdery, floral, aniseed.

[0291] Composition Evaluation Example

[0292] In the following invention, various wood composition accords containing different benchmark compounds were evaluated and compared to composition accords containing the compound from Example 1. Composition A contained the compound from Example 1, 2,6-diethyl-3,3,4-trimethyltetrahydro-2 H -pyran-4-ol as a 10% w / w solution in IPM (isopropyl myristate). Composition B contained the commercial compound Clearwood, composition C contained the commercial compound PTBC ketone, composition D contained the commercial compound OTBC ketone; and finally, composition E contained only IPM and was used as a blank.

[0293] All of the above compositions are used in shampoos as well as fabric softeners.

[0294] Example A B C D E Raw materials (parts by weight) Kambernoir SHK 10 10 10 10 10 Tanalol 8 8 8 8 8 Cedryl Methyl Ketone 8 8 8 8 8 Eugenyl acetate 0.5 0.5 0.5 0.5 0.5 Ambergris 40 40 40 40 40 Isoborneol acetate 10 10 10 10 10 Isoborneol cyclohexylate (IBCH) 8 8 8 8 8 4-tert-Butylcyclohexyl acetate (PTBCA) 10 10 10 10 10 2,6-Diethyl-3,3,4-trimethyltetrahydro-2-pyran-4-ol as a 10% w / w solution in IPM 5.5 0 0 0 0 1% in IPM Clearwood 0 5.5 0 0 0 PTBC Ketone 0 0 5.5 0 0 OTBC Ketone 0 0 0 5.5 0 IPM 0 0 0 0 5.5 total 100 100 100 100 100

[0295] Apparently, 5.5% by weight of 2,6-diethyl-3,3,4-trimethyltetrahydro-2 H -4-pyranol gives a strong woody patchouli-like effect. When used in shampoo, it gives a fuller feel and gives heaviness to the blend. On the other hand, when 1% by weight of Clearwood in IPM is used in the above blend, only a soft woody effect is observed. The use of PTBC ketone presents a camphorous and woody effect, while the OTBC ketone composition gives a minty and woody character to the blend.

Claims

1. Compounds of formula (X) and / or formula (Y1) and / or formula (Y2) providing camphor, woody, earthy and / or patchouli-like notes to perfume, fragrance or deodorant / masking compositions It is selected from: 2,6-Diethyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol 2,3,3,4,6-Pentamethyltetrahydro-2H-pyran-4-ol 2-Isopropyl-3,3,4,6-tetramethyltetrahydro-2H-pyran-4-ol 6-Ethyl-2-isopropyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol 6-Ethyl-2,3,3,4-tetramethyltetrahydro-2H-pyran-4-ol 2,3,3,4-Tetramethyl-6-propyltetrahydro-2H-pyran-4-ol 6-Isopropyl-2,3,3,4-tetramethyltetrahydro-2H-pyran-4-ol 2-Ethyl-2,4,5,5,6-pentamethyltetrahydro-2H-pyran-4-ol 2-Ethyl-3,3,4,6-tetramethyltetrahydro-2H-pyran-4-ol 2-Ethyl-3,3,4-trimethyl-6-propyltetrahydro-2H-pyran-4-ol 2-Ethyl-6-isopropyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol 2-Ethyl-6-isobutyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol 6-Ethyl-2,2,4,5,5-pentamethyltetrahydro-2H-pyran-4-ol 2,6-Diethyl-2,4,5,5-tetramethyltetrahydro-2H-pyran-4-ol 6-Ethyl-3,3,4-trimethyl-2-propyltetrahydro-2H-pyran-4-ol 6-Isopropyl-3,3,4-trimethyl-2-propyltetrahydro-2H-pyran-4-ol 6-Ethyl-2-isobutyl-3,3,4-trimethyltetrahydro-2H-pyran-4-ol 2-(2,3-Dimethylbut-3-en-2-yl)-2,4,5,5,6-pentamethyltetrahydro-2H-pyran-4-ol 2-(2,3-Dimethylbut-3-en-2-yl)-2-ethyl-4,5,5,6-tetramethyltetrahydro-2H-pyran-4-ol Or selected from: 2,3,3-Trimethyl-4-methylene-6-propyltetrahydro-2H-pyran or 2,3,3,4-tetramethyl-6-propyl-3,6-dihydro-2H-pyran, or a mixture thereof, 6-ethyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran and 6-ethyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 2,3,3,6-Tetramethyl-4-methylenetetrahydro-2H-pyran and 2,3,3,4,6-pentamethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 6-isopropyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran or 6-isopropyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 6-isobutyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran or 6-isobutyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 6-butyl-2,3,3-trimethyl-4-methylenetetrahydro-2H-pyran or 6-butyl-2,3,3,4-tetramethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 2-ethyl-3,3,6-trimethyl-4-methylenetetrahydro-2H-pyran or 2-ethyl-3,3,4,6-tetramethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 2,6-diethyl-3,3-dimethyl-4-methylenetetrahydro-2H-pyran and 2,6-diethyl-3,3,4-trimethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 2-ethyl-3,3-dimethyl-4-methylene-6-propyltetrahydro-2H-pyran and 2-ethyl-3,3,4-trimethyl-6-propyl-3,6-dihydro-2H-pyran, or a mixture thereof, 6-butyl-2-ethyl-3,3-dimethyl-4-methylenetetrahydro-2H-pyran or 6-butyl-2-ethyl-3,3,4-trimethyl-3,6-dihydro-2H-pyran, or a mixture thereof, 6-ethyl-3,3-dimethyl-4-methylene-2-propyltetrahydro-2H-pyran or 6-ethyl-3,3,4-trimethyl-2-propyl-3,6-dihydro-2H-pyran, or a mixture thereof, 2-ethyl-6-(4-methoxyphenyl)-3,3-dimethyl-4-methylenetetrahydro-2H-pyran or 2-ethyl-6-(4-methoxyphenyl)-3,3,4-trimethyl-3,6-dihydro-2H-pyran, or a mixture thereof.

2. A mixture of compounds of formula (X) and formula (Y1) according to claim 1.

3. A mixture of compounds of formula (X) and formula (Y2) according to claim 1.

4. A mixture of compounds of formula (Y1) and formula (Y2) according to claim 1.

5. A mixture of compounds of formula (X), (Y1) and (Y2) according to claim 1.

6. A fragrance, flavour and / or deodorising / masking composition comprising a compound or mixture as claimed in any one of the preceding claims.

7. The fragrance, flavor and / or deodorizing / masking composition of claim 6, wherein the content of the compound of formula (X) and / or formula (Y1) and / or formula (Y2) is comprised between 0.00001-99.9 wt.%.

8. The fragrance, flavor and / or deodorizing / masking composition according to claim 7, wherein the content of the compound of formula (X) and / or formula (Y1) and / or formula (Y2) is comprised between 0.0001 and 95 wt%.

9. A fragrance, flavour and / or deodorising / masking composition according to any of claims 6 to 8, additionally comprising at least one ester and / or one further alcohol in addition to compound (X), if compound (X) is present.

10. A fragrance, flavour and / or deodorising / masking composition according to any of claims 6 to 8, further comprising at least one mixture of an ester and a further alcohol in addition to compound (X), if compound (X) is present.

11. A fragrance, flavour and / or deodorising / masking composition according to claim 9, wherein the content of the compound of formula (X) and / or formula (Y1) and / or formula (Y2) together with the ester and / or alcohol is greater than 25 wt%.

12. A fragrance, flavour and / or deodorising / masking composition according to claim 9, wherein the content of the compound of formula (X) and / or (Y1) and / or (Y2) together with the ester and / or alcohol is greater than 75 wt%.

13. A process for preparing compounds of formula (X) and / or formula (Y1) and / or formula (Y2) and / or mixtures thereof, wherein R1 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group; R2 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms; R3 is an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms or a phenyl group and R4 is H or an alkyl group having up to 6 carbon atoms or an alkenyl group having up to 6 carbon atoms, in In the event of any of the following: - Phosphoric acid, or - another protonic acid, The compound of formula (I) reacts with the compound of formula (II), To form the compounds of formula (X) and / or formula (Y1) and / or formula (Y2) and / or mixtures thereof, wherein the groups R1, R2, R3 and R4 of the compounds of formula (I) and (II) are the same as the groups R1, R2, R3 and R4 of the compounds of formula (X) and / or formula (Y1) and / or formula (Y2) and / or mixtures thereof.

14. A process for preparing a compound of formula (X) according to claim 13, wherein the phosphoric acid is aqueous phosphoric acid.

15. A process for preparing a compound of formula (X) according to claim 13, wherein the reaction is carried out in the presence of aqueous phosphoric acid having a phosphoric acid content of 10% to 85% by weight.

16. A process for preparing a compound of formula (X) according to claim 13, wherein the reaction is carried out in the presence of aqueous phosphoric acid having a phosphoric acid content of 30% to 60% by weight.

17. A process for preparing compounds of the formula (Y1) and / or formula (Y2) according to claim 13, wherein the reaction is carried out in the presence of p-toluenesulfonic acid as another protic acid and in an organic solvent.

18. A process for preparing compounds of the formula (Y1) and / or formula (Y2) according to claim 13, wherein the reaction is carried out in the presence of p-toluenesulfonic acid as another protic acid and in ethylene dichloride.

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