Odorous compounds and methods for their preparation

Abstract

The present invention relates to novel odoriferous compounds represented by formula (I) and / or formula (II) which are useful as fragrance or flavor materials, in particular in providing musk, woody, animalic and / or powdery hedonic fragrance notes to fragrance, aroma or deodorizing / masking compositions. The present invention also relates to fragrance, flavor and / or deodorizing / masking compositions comprising the odoriferous compounds represented by formula (I) and / or formula (II). The present invention also relates to the use of said odorants in the fragrance, flavor and / or deodorizing / masking compositions of the present invention. The present invention also relates to processes for producing said odorants / compounds.

Description

Technical Field

[0001] This invention relates to novel odorous compounds represented by formula (I) and / or (II) that can be used as fragrance or flavoring materials, particularly in providing musky, woody, animalic, and / or powdery fragrance notes to fragrance, aroma, or deodorizing / masking compositions. The invention also relates to fragrance, flavor, and / or deodorizing / masking compositions comprising odorous compounds represented by formula (I) and / or (II). The invention further relates to the use of said odorant in the fragrance, flavor, and / or deodorizing / masking compositions of the invention. The invention also relates to methods for generating said odorant / compound and corresponding fragrance, flavor, and / or deodorizing / masking compositions containing said odorant / compound. Background Technology

[0002] There is a significant demand for musk scent agents, which often form the base notes of fragrance products. Musk scent agents are indispensable in the fragrance category, used to impart sensory and sensual effects. After nitro musk was discontinued due to safety concerns, macrocyclic and polycyclic musks dominated the musk ingredients used by perfumers. Of these two classes, polycyclic musk (PCM) holds a disproportionately larger share due to its lower cost and ease of synthesis. However, the inherent hydrophobicity of PCM translates into poorer biodegradability, which is subsequently believed to increase bioaccumulation.

[0003] Following the discovery of cyclic musk by researchers at BASF in 1975, a new type of musk scent agent known as alicyclic musk emerged. Cyclic musk has a fruity, strawberry-like musky aroma and structurally does not belong to any of the three known types of musk scent agents listed above. Two other musk scent agents were also discovered: helvetolide, which exhibits musky, fruity, and pear-like notes; and Romandolide, which possesses musky, ambrette, and fruity characteristics.

[0004] Its main characteristics are floral, powdery, and rose-scented 3,7-dimethyloctyl-6-en-1-ylethyl oxalate, also known as ethyl citronellol oxalate. racemic It also exhibits musky characteristics. However, it has been reported (Kraft, Philip et al., European Journal of Organic Chemistry 2004, 354-365) that ethyl citronellol oxalate is not used as a musky scenting agent in fragrances; its main characteristics are floral, powdery, and rose-like, with a relatively high odor threshold. In 2004, T. Yamamoto et al. ( Flavour Fragr. J. (2004; 19: 121–133) reported an olfactory study of optically active citronellol derivatives. They reported the olfactory activity of ethyl citronellol oxalate alone.R The isomer exhibits a floral and musky scent, while S The isomer exhibits a rose-like floral fragrance.

[0005] In Struct.-Act. Relat. Chemoreception, Proc. Symp. (“Boelens”) (1976), 197-209, on page 204, where Table B mentions musk compounds, citronellol ethyl oxalate (also known as 3,7-dimethyloct-6-en-1-yl ethyl oxalate) occupies the last position, with the lowest observed odor quality of 4.00 and the lowest expected odor quality of 4.5.

[0006] 3,7-Dimethyloctylethyl oxalate has been reported to have a musky odor in Struct.-Act. Relat. Chemoreception, Proc. Symp. (“Boelens”) (1976), 197-209. However, on page 204, where Table B mentions musky compounds, this compound is listed second to last with the lowest observed odor quality of 4.00. This almost matches its expected odor quality of 4.6.

[0007] 3,7-Dimethyloctylethyl oxalate is also known as dihydrocitronellol. According to Maslozhirovaya Promyshlennost (“Kron et al.”) (1985), (10), 28-30, the oxalate of dihydrocitronellol does not have a musky odor. Therefore, there are conflicting reports regarding the musky characteristics of 3,7-dimethyloctylethyl oxalate (also known as dihydrocitronellol ethyl oxalate).

[0008] By Kishimoto et al. Journal of the Chemistry Society The synthesis of 3,7-dimethyloctyl 3-oxobutyrate was reported in Japan, 1975, pp. 701-704, via the reaction of 3,7-dimethyloctanol / dihydrocitronellol with ethyl acetoacetate, with a yield of 44%.

[0009] 3,7-Dimethyloctyl 3-oxobutyrate The increasing scarcity of natural fragrance ingredients has transformed the field of synthetic fragrance ingredients. There is now a growing demand for novel odorants / compounds and / or novel fragrance, flavor, and / or deodorizing / masking compositions containing said odorants / compounds.

[0010] Therefore, there is a high demand for novel compounds that possess musky and related odor properties and are readily biodegradable. The main advantages of alicyclic musk are their greater economic viability and, in most cases, biodegradability.

[0011] The advantages of this invention are that the novel odorous compounds represented by formula (I) and / or formula (II) can be used as fragrance or flavoring materials, particularly in providing musky, woody, animalic, and / or powdery fragrance notes to fragrance, aromatic, or deodorizing / masking compositions. The applicant has also surprisingly discovered that introducing disubstitution at carbon C-5 in the alkyl chain increases the strength and improves the properties of the compounds of this invention. This invention also relates to methods for preparing odorous compounds of formula (I) and / or formula (II). Summary of the Invention

[0012] This invention discloses fragrance, flavor, and / or deodorizing / masking compositions comprising compounds of formula (I) and / or formula (II). Here, the compounds of formula (I) and / or formula (II) may be any one of its stereoisomers or a mixture of one or more of these stereoisomers. Further, the compounds of formula (I) and / or formula (II) may be one of its regioisomers or a mixture of one or more of its regioisomers.

[0013] The present invention further discloses the odorous compounds of formula (I) and / or formula (II) themselves, as well as their stereoisomers or mixtures thereof and / or regioisomers or mixtures thereof.

[0014] In particular, the present invention discloses fragrance, flavor and / or deodorizing / masking compounds of formula (I) and / or formula (II). in R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl or -O-n-butyl The dashed lines represent alternative locations for the double bond, and n = 0, 1, or 2 The condition is that the compounds of formula (I) and formula (II) cannot be 3,7-Dimethyloctylethyl oxalate and 3,7-Dimethyloctyl 3-oxobutyrate.

[0015] According to the present invention, groups R1 and R2 are separate groups, i.e., they do not form a ring together. It will also be clear to those skilled in the art that all three dashed segments in formula (I) cannot simultaneously be double bonds. Therefore, if R1 is bonded to a double bond, then R2 will be bonded to a single bond; and if R2 is bonded to a double bond, then R1 will be bonded to a single bond.

[0016] In one embodiment, R1 and / or R2 are selected from alkyl or alkylene groups having up to 7 carbon atoms. R1 and R2 may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, and heptylene.

[0017] In one embodiment, M is a methyl or alkoxy group such as methoxy, ethoxy, isopropoxy, n-propoxy, -O-allyl, -O-isobutyl, -O-n-butyl.

[0018] In one embodiment, the compounds of formulas (I) and (II) of the present invention may be chiral, for example, they may be used as pure enantiomers or diastereomers or as mixtures of stereoisomers (enantiomers or diastereomers), more specifically as mixtures of enantiomers or diastereomers; for example, as R isomers S Isomers, racemic mixtures, and / or non-racemic mixtures. Furthermore, compounds of formulas (I) and (II) can be advantageously used as... RR isomers SS isomers RS isomers SR Isomers, racemic mixtures, and / or non-racemic mixtures. Further, the compounds of formulas (I) and (II) of the present invention can be used as any one of their regioisomers or mixtures of their regioisomers.

[0019] By using the phrase “any one of its regioisomers or a mixture of its regioisomers”, those skilled in the art should understand that the existence of regioisomers is due to the different positions of the double bonds in the structure of formula (I).

[0020] Furthermore, the compounds of formulas (I) and (II) of the present invention can be used as pure compounds or as mixtures of geometric isomers (diastereomers); for example, they can be mixtures of cis and trans isomers or as... E and Z Isomers.

[0021] The literature procedures for preparing oxalates involve treating readily available alcohols with symmetrical dioxalates in the presence of Lewis acids (Kron, AA et al., USSR, SU1150247 A1 1985-04-15 and Kron, A. A et al., Maslozhirovaya Promyshlennost (1985), (10), 28-30).

[0022] In this paper, we report the reaction of tetrahydropyran derivatives (V) with oxalate / malonate / succinate / pyruvate proton acids at catalytic amounts. p The reaction in the presence of TSA, methanesulfonic acid or sulfuric acid directly yields the asymmetric oxalate of formula (I) in good yield.

[0023] Our current method yields the desired alicyclic musk compounds of formula (I) and / or formula (II) in four steps. Detailed Implementation

[0024] The term "odorant" used to characterize compounds according to the invention means that it triggers a preferred pleasant odor sensation in humans; therefore, it is conventionally used for flavoring industrial and hygiene products, detergents, cleaning agents, personal hygiene products, cosmetics, etc. For the purposes of this invention and the appended claims, the term "odorant" includes "aromatic substance." Aromatic substance is a term commonly used to refer to substances that provide odor and / or flavor to food.

[0025] The compounds of formulas (I) and (II) can be used alone, as mixtures thereof, or in combination with base materials.

[0026] As used herein, “base materials” include all known aroma / flavor materials selected from a wide range of natural products such as essential oils, extracts, resinoids or isolates, as well as currently available synthetic materials such as hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and / or mixed with one or more ingredients or excipients / adjuvants (e.g., solvents / diluents, stabilizers, carrier materials and other auxiliaries commonly used in the art) that are conventionally used in combination with odorants in aroma and / or flavor compositions.

[0027] Compounds of formulas (I) and (II) can be used in a wide range of fragrance applications, such as in any area of ​​fine and functional fragrances, including perfumes, air care products, household products, laundry products, body care products, and cosmetics. The compounds can be used in a wide variety of amounts, depending on the specific application and the nature and amount of other odorant components.

[0028] According to a preferred embodiment of the invention, the fragrance, flavor, and / or deodorizing / masking composition contains at least one compound as previously described according to formula (I) or (II) in an amount between 0.00001 and 99.9 wt.%, for example between 0.0001 and 95 wt.%, for example between 0.001 and 25 wt.%, preferably between 0.01 and 15 wt.%, more advantageously between 0.1 and 10 wt.%, particularly between 1 and 5 wt.%, in each case relative to the entire composition.

[0029] According to a particularly preferred embodiment of the invention, in addition to the compounds of formula (I) and / or formula (II) according to the invention, the fragrance, flavor and / or deodorizing / masking compositions according to the invention contain additional odorants, for example, in an amount of 0.1-99.9 wt.%, preferably 5-90 wt.%, particularly 15-70 wt.%, relative to the whole fragrance and / or flavor composition.

[0030] Compounds of formulas (I) and (II) as described above may be used in consumer product bases by simply mixing at least one compound of formula (I) and / or formula (II) or a fragrance composition comprising one or more compounds of formula (I) and / or formula (II) directly with the consumer product base; or they may be captured in an earlier step with a capturing material, such as polymers, capsules, microcapsules and / or nanocapsules, liposomes, film-forming agents, absorbents such as activated carbon or zeolite, cyclic oligosaccharides, cycloglycolureas and mixtures of two or more thereof, or they may be chemically bonded to a matrix suitable for releasing fragrance molecules upon application of external stimuli (such as light, enzymes, air, water, etc.) and then mixed with the consumer product base.

[0031] Therefore, the present invention can be used in existing methods for manufacturing fragrance, flavor, and / or deodorizing / masking compositions, methods comprising incorporating one or more compounds of formula (I) and / or formula (II) as fragrance, flavor, and / or deodorizing / masking ingredients by directly mixing compounds with a consumer product base or by mixing a fragrance, flavor, and / or deodorizing / masking composition comprising one or more compounds of formula (I) and / or formula (II) (which may then be mixed with the consumer product base) using conventional techniques and methods. By adding at least one compound of formula (I) and / or formula (II) of the present invention as described above in an olfactory acceptable amount, the odor profile of the consumer product base can be improved, enhanced, and / or altered.

[0032] This invention discloses fragrance, flavor and / or deodorizing / masking compositions comprising compounds of formula (I) and / or formula (II).

[0033] This invention discloses odorous compounds of formula (I) and / or formula (II). In particular, this invention discloses fragrance, flavor, and / or deodorizing / masking compounds of formula (I) and / or formula (II) and methods for synthesizing them.

[0034] Equations (I) and (II) are expressed as Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = Me, -OMe, -OEt, -O i -Pr、-O n Pr, -O-allyl, -O-isobutyl, -O-n-butyl The dashed lines represent alternative locations for the double bond, and n = 0, 1, or 2 The condition is that the compounds of formula (I) and formula (II) cannot be 3,7-Dimethyloctylethyl oxalate and 3,7-Dimethyloctyl 3-oxobutyrate.

[0035] According to the present invention, groups R1 and R2 are separate groups, that is, they do not form a ring together.

[0036] In one embodiment, R1 and / or R2 are selected from alkyl or alkylene groups having up to 6 carbon atoms. R1 and R2 may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, and heptylene.

[0037] In one embodiment, M is a methyl or alkoxy group such as methoxy, ethoxy, isopropoxy, n-propoxy, -O-allyl, -O-isobutyl, -O-n-butyl.

[0038] In one embodiment, the compounds of formula (I) and / or formula (II) of the present invention may be chiral, for example, they may be used as pure enantiomers or diastereomers or as a mixture of stereoisomers (enantiomers or diastereomers), more specifically as a mixture of enantiomers or diastereomers; for example as R isomers S Isomers, racemic mixtures, and / or non-racemic mixtures. Furthermore, compounds of formula (I) and / or formula (II) can also be advantageously used as... RR isomers SS isomers RS isomers SRIsomers, racemic mixtures, and / or non-racemic mixtures. Further, the compounds of formula (I) and / or formula (II) of the present invention can be used as any one of their regioisomers or mixtures of their regioisomers. Further, the compounds of formula (I) and / or formula (II) of the present invention can be used as pure compounds or as mixtures of geometric isomers (diastereomers); for example, they can be mixtures of cis and trans isomers or as... E and Z Isomers.

[0039] In one embodiment, the compound of formula (I) is a mixture of regio isomers and stereoisomers, as shown below.

[0040] The advantage of this invention is that the disclosed compounds exhibit musky, woody, animalic, and / or powdery odor characteristics. Furthermore, fragrance compositions comprising these novel compounds also exhibit musky, woody, animalic, and / or powdery odor characteristics.

[0041] Embodiments of the present invention relate to odorous compositions comprising compounds of formula (I) and / or formula (II). In particular, the present invention discloses fragrance, flavor, and / or deodorizing / masking compositions comprising one or more compounds of formula (I) and / or formula (II) and one or more adjuvants.

[0042] Generally, in addition to the novel odorant and / or fragrance, flavor and / or deodorizing / masking compositions described herein, suitable fragrance, flavor or deodorizing compositions may advantageously include conventional adjuvants such as solvents, carriers, stabilizers, emulsifiers, humectants, dispersants, diluents, thickeners, thinners, other odorants and / or other adjuvants.

[0043] In an advantageous embodiment of the invention, the odorous compounds of formula (I) and / or formula (II) are selected from the following compounds: Compound number) Name 1) 3,7-Dimethyl-5-methylene octylethyl oxalate 2) Ethyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 3) Ethyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 4) 3,7-Dimethyl-5-methylene octyl ethyl malonate 5) Ethyl (3,5,7-trimethyloct-4-en-1-yl)malonate 6) Ethyl (3,5,7-trimethyloct-5-en-1-yl)malonate 7) 3,7-Dimethyl-5-methylene octylethyl succinate 8) Ethyl (3,5,7-trimethyloct-4-en-1-yl)succinate 9) Ethyl (3,5,7-trimethyloct-5-en-1-yl)succinate 10) 3,7-Dimethyl-5-methyleneoctyl-2-oxopropionate 11) 3,5,7-Trimethyloct-4-en-1-yl 2-oxopropionate 12) 3,5,7-Trimethyloct-5-en-1-yl 2-oxopropionate 13) Ethyl (3,5,7-trimethyloctyl)oxalate 14) Ethyl (3,5,7-trimethyloctyl)malonate 15) Ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate 16) Ethyl(3,5,6,6-tetramethylhept-4-en-1-yl)oxalate 17) Ethyl (3,5,6,6-tetramethylheptyl)oxalate 18) 3,7-Dimethyl-5-methylene octyl isopropyl oxalate 19) Isopropyl (3,5,7-trimethyloct-4-en-1-yl)oxalate 20) Isopropyl (3,5,7-trimethyloct-5-en-1-yl)oxalate 21) Isopropyl (3,5,7-trimethyloctyl)oxalate 22) 3,7-Dimethyl-5-methylene octylpropyl oxalate 23) Propyl (3,5,7-trimethyloct-4-en-1-yl) oxalate 24) Propyl (3,5,7-trimethyloct-5-en-1-yl) oxalate 25) 3,7-Dimethyl-5-methylene octyl isobutyl oxalate 26) Isobutyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 27) Isobutyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 28) Isobutyl(3,5,7-trimethyloctyl)oxalate 29) 3,7-Dimethyl-5-methylene octylmethyl oxalate 30) Methyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 31) Methyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 32) Methyl (3,5,7-trimethyloctyl)oxalate 33) Ethyl (3-methyl-5-methylene octyl) oxalate 34) 3,5-Dimethyloct-4-en-1-ylethyl oxalate 35) 3,5-Dimethyloct-5-en-1-ylethyl oxalate 36) Ethyl (3-methyl-5-methylenedecyl) oxalate 37) 3,5-Dimethyldec-4-en-1-ylethyl oxalate 38) 3,5-Dimethyldec-5-en-1-ylethyl oxalate 39) 3,5-Dimethyloctylethyl oxalate 40) 3,5-Dimethyldecylethyl oxalate 41) 3,7-Dimethyloct-4-en-1-ylethyl oxalate 42) 3,7-Dimethyloct-5-en-1-ylethyl oxalate.

[0044] In another embodiment of the invention, the odorous compounds of formula (I) and / or formula (II) are selected from the following compounds: 43) Ethyl (5-ethyl-3-methylhept-4-en-1-yl)oxalate 44) Ethyl (5-ethyl-3-methylhept-5-en-1-yl)oxalate 45) Ethyl (5-ethyl-3-methylheptyl) oxalate 46) Ethyl(3,5,6-trimethylhept-4-en-1-yl)oxalate 47) Ethyl(3,5,6-trimethylhept-5-en-1-yl)oxalate 48) 3,6-Dimethyl-5-methyleneheptylethyl oxalate 49) 3,5-Dimethylhept-4-en-1-ylethyl oxalate 50) 3,5-Dimethylhept-5-en-1-ylethyl oxalate 51) Ethyl (3-methyl-5-methyleneheptyl) oxalate 52) Ethyl (3-methyl-5-methylene nonyl) oxalate 53) 3,5-Dimethylnon-4-en-1-ylethyl oxalate 54) 3,5-Dimethylnon-5-en-1-ylethyl oxalate 55) Ethyl(3-methyl-5-propyloct-4-en-1-yl)oxalate 56) Ethyl(3-methyl-5-propyloct-5-en-1-yl)oxalate 57) Ethyl (3-methyl-5-propyloctyl)oxalate 58) Ethyl(3,5,9-trimethyldec-4-en-1-yl)oxalate 59) 3,9-Dimethyl-5-methylenedecylethyl oxalate 60) Ethyl(3,5,9-trimethyldec-5-en-1-yl)oxalate 61) Ethyl(5-isobutyl-3,7-dimethyloct-4-en-1-yl)oxalate 62) Ethyl(5-isobutyl-3,7-dimethyloct-5-en-1-yl)oxalate 63) Ethyl (5-isobutyl-3,7-dimethyloctyl) oxalate 64) Ethyl (5-ethyl-3-methylhept-4-en-1-yl)malonate 65) Ethyl (5-ethyl-3-methylhept-5-en-1-yl)malonate 66) 5-Ethyl-3-methylhept-4-en-1-yl 2-oxopropionate 67) 5-Ethyl-3-methylhept-5-en-1-yl 2-oxopropionate 68) Ethyl(3,5,6-trimethylhept-4-en-1-yl)malonate 69) Ethyl (3,5,6-trimethylhept-5-en-1-yl)malonate 70) 3,6-Dimethyl-5-methyleneheptylethylmalonate 71) Ethyl(5-isopropyl-3,6-dimethylhept-4-en-1-yl)oxalate 72) Ethyl(5-isopropyl-3,6-dimethylhept-5-en-1-yl)oxalate 73) Ethyl(5-isopropyl-3,6-dimethylhept-5-en-1-yl)oxalate 74) Ethyl (5-isopropyl-3,6-dimethylheptyl) oxalate 75) Ethyl(3-methyloct-4-en-1-yl)oxalate 76) Ethyl(3-methyloct-5-en-1-yl)oxalate 77) Ethyl(3-methylnon-4-en-1-yl)oxalate 78) Ethyl(3-methylnon-5-en-1-yl)oxalate 79) Ethyl(3-methyldec-4-en-1-yl)oxalate 80) Ethyl(3-methyldec-5-en-1-yl)oxalate 81) Ethyl(3-methylundec-4-en-1-yl)oxalate 82) Ethyl(3-methylundec-5-en-1-yl)oxalate 83) Ethyl(3-methyldodec-4-en-1-yl)oxalate 84) Ethyl(3-methyldodec-5-en-1-yl)oxalate 85) 3,6-Dimethylhept-4-en-1-ylethyl oxalate 86) 3,6-Dimethylhept-5-en-1-ylethyl oxalate 87) Ethyl(3,6,7-trimethyloct-5-en-1-yl)oxalate 88) Ethyl(3,6,7-trimethyloct-4-en-1-yl)oxalate 89) 3,6-Dimethyloct-5-en-1-ylethyl oxalate 90) 3,6-Dimethyloct-4-en-1-ylethyl oxalate 91) 3,6-Dimethylnon-5-en-1-ylethyl oxalate 92) 3,6-Dimethylnon-4-en-1-ylethyl oxalate 93) 3,6-Dimethyldec-5-en-1-ylethyl oxalate 94) 3,6-Dimethyldec-4-en-1-ylethyl oxalate 95) 3,6-Dimethylundec-5-en-1-ylethyl oxalate 96) 3,6-Dimethylundec-4-en-1-ylethyl oxalate.

[0045] In embodiments of the invention, the fragrance, flavor, and / or deodorizing / masking composition comprises compounds of formula (I) and / or formula (II), selected from any one of the compounds and / or a mixture of two or more of the 96 compounds given above (e.g., the 42 first group compounds listed above), particularly selected from any one or a mixture of two or more of the 96 compounds given above (e.g., the 42 first group compounds listed above).

[0046] In one embodiment, the applicant has also surprisingly discovered that by introducing a disubstitution at carbon C-5 of the compound of formula II, there is an increase in the intensity of the musky odor.

[0047] In embodiments of the invention, the claimed fragrance, flavor, and / or deodorizing / masking compositions are advantageously used as fragrance compositions. Fragrance compositions according to the invention generally include perfumes, colognes, eau de toilette, and / or eau de parfums. In embodiments of the invention, the claimed fragrance, flavor, and / or deodorizing / masking compositions are advantageously used in cosmetic formulations, personal care products, cleaning products, fabric softeners, and / or air fresheners, etc. Furthermore, within the scope of embodiments of the invention, the novel fragrance, flavor, and / or deodorizing / masking compositions and / or novel compounds of formula (I) and / or formula (II) described herein can be integrated into building materials, wall and floor coverings, vehicle components, etc.

[0048] Compounds of formula (I) and / or formula (II) can be combined with a number of known natural or synthetic fragrance, flavor, and / or deodorizing / masking materials, thus the range of natural ingredients may include not only volatile components but also semi-volatile and microvolatile 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, Volumes 1 and 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 will be apparent from the following non-limiting compilation: Natural products, such as: 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, Celeryseed oil, Chamomile oil, Cinnamon bark oil, Bay leaf oil, Cistus absolute, Cistus oil, Citronella oil Citronella terpenes, citronella sage oil, rectified clove oil, cognac oil (white), coriander seed oil, cumin seed oil, cypress oil, davana oil, dill seed oil, elemi oil, elemi resinoid, eucalyptus oil, fir needle oil, gallanum oil, geranium oil, Indian ginger oil, grapefruit oil, guaiacwood oil, guarjun balsam, jasmin absolute, jatamansi oil, juniper berry oil oil), juniper leaf oil, kachur oil, pure labdanum, labdanum resin form.Resinoids, lavender oil, lemon oil, limonene, lemongrass oil, lime oil, litsea cubeba oil Litsea cubeba oil ), Litsea cubeba terpenes ( Litsea cubeba terpenes), Lobhan choya resin, mandarin oil, peppermint oil Mentha arvensis oil Lemon peppermint oil Mentha citrata oil Pure Mimosa Absolute Oil, Myrrh Resinoid, Nagarmotha Oil, Nutmeg Oil, Pure Oakmoss Absolute Oil, Oakmoss Resinoid, Olibanum Oil, Olibanum Resinoid, Orange Oil, Origanum Oil, Palma Rosa Oil, Patchouli Oil, Peppermint Oil, Peru Balsam Resinoid, Petitgrain Oil, Pineneedle Oil, Pink Pepper Oil, Pure Rose Absolute Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Pure Seaweed Oil absolute), Spearmintoil, Sugandh kokila oil, Sugandhmantri oil, Tageteoil, Tolu Balsam resinoid, Tuberose absolute, Turmeric oil, Turpentine oil, Valerian oil, Vetiver oil, Vetiver terpenes.

[0049] Synthetic raw materials, for example: Esters, such as: C16 aldehyde, gluconate, allyl hexanoate, allyl cyclohexylpropionate, allyl heptaate, allyl phenoxyacetate, isoamyl acetate, amyl benzoate, amyl butyrate, amyl hexanoate, amyl cinnamate, amyl isovalerate, amyl phenylacetate, amyl propionate, isoamyl salicylate, acetylated amyris acetate, anisyl acetate, benzyl acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzyl isoeugenol, benzyl propionate, benzyl salicylate, benzyl benzoate, butyl acetate, butyl butyrate, butyl butyryl lactate, caryophyllene acetate, cedryl acetate Acetate), cinnamon acetate, cinnamon butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl hexanoate, cis-3-hexenyl carboxylate, cis-3-hexenyl isobutyrate, cis-3-hexenyl-2-methylbutyrate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, cis-3-hexenyl citronellyl acetate, citronellyl butyrate, citronellyl formate, citronellyl isobutyrate, citronellyl propionate, citronellyl citronellyl citronellyl acetate, tricyclodecenyl isobutyrate, cyclogalbanate, ethyl cyclohexyl acetate, decyl acetate, dibutyl phthalate, diethyl malonate, diethyl phthalate, dihydromyrcenyl acetate Acetate), dimethyl octyl acetate, dimethyl phenyl ethyl carbinyl acetate, dioctyl adipate, dioctyl phthalate, dimethyl benzyl acetate, dimethyl benzyl 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 heptamate, ethyl hexyl acetate, ethyl isobutyrate, ethyl laurate, ethyl nonanoate, ethyl phenoxyacetate, ethyl phenyl acetate, ethyl phenyl glycidate, ethyl propionate, ethyl safranate, ethyl salicylate, ethyl valerate, eugenol acetate acetate), Evernyl, Fenchyl acetate, Floramat, Frescolat ML, Fructone,Ethyl methyl decanoate, fruitate, geranyl acetate, geranyl butyrate, geranyl formate, geranyl propionate, geranyl terbinate, givescone (2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylate), guaiacol acetate, hedionate, methyl hedione, helvetolide, herbanate, hexyl acetate, hexyl benzoate, n-hexyl butyrate, hexyl hexanoate, hexyl isobutyrate, hexyl propionate, hexyl salicylate, isoborneol acetate, isobutyl acetate, isobutyl phenyl acetate, isobutyl salicylate, isoeugenyl acetate Acetate), isononyl acetate, isopentyrate, isopropyl 2-methylbutyrate, isopropyl myristate, jasmonyl, liffaromecis-3-hexenol methyl carbonate), linalyl acetate, mahagonate, manzanate, menthanyl acetate, menthyl acetate, methyl benzoate, 2-methyl butyl acetate, 2-methyl camomille, methyl cinnamate, methyl cyclogeranate, methyl hepeptine carbonate, methyl laurate, methyl octine carbonate, methyl phenylacetate, methyl salicylate, methyl-2-methylbutyrate, neofolione, nopylacetate, octenyl acetate, octyl acetate, octyl isobutyrate, paracresyl acetate Acetate), p-cresol isobutyrate, p-cresol phenylacetate, pear ester, 2-methylpentanoic acid 2-methylpentanoic acid (Peranat), phenoxyethyl isobutyrate, phenylethyl acetate, phenylethyl butyrate, phenylethyl formate, phenylethyl isobutyrate, phenylethyl phenylacetate, phenylethyl propionate, phenylethyl salicylate, phenylethyl tetroxide, phenylpropyl isobutyrate, prenyl acetate, Romandolide, Sagecete, styrallylacetate, styrallyl propionate, Tangerinol, terpinyl acetate, Thesaron, trans-2-hexenyl acetate, Tropicate, verdox, tricyclodecenyl acetate Acetate), tricyclodecenyl propionate, p-tert-butylcyclohexyl acetate (Vertenex), vetikol acetate, vetiverylacetate, Yasmolys.

[0050] Lactones, such as: Ambrettolide, Arova N, 3-propylidene-1-isobenzofuranone (Celeriax), δ-decanolide, γ-decanolide, δ-dodecanolide, γ-dodecanolide, ethylene lenebrassylate, exaltolide, γ-heptanolide, δ-caprolactone, γ-caprolactone, methyl laitone, methyl octanolide, δ-nonanolide, γ-nonanolide, octahydrocoumarin, δ-octanolide, γ-octanolide, Rootylone, Silvanone supra, δ-undecanolactone, γ-undecanolactone, γ-pentanolide, 10-oxahexadecanolactone (OHD musk), coumarin, cyclopentadecanolactone (Habanolide), and jasmolactone.

[0051] Aldehydes, such as: acetaldehyde, adoxal, C10 aldehyde, iso-C11 aldehyde, C11moa aldehyde, undecylenic aldehyde, undecylic aldehyde, lauraldehyde, aldehyde MNA, anisaldehyde, pentylcinnamaldehyde, benzaldehyde, bourgeonal, campholenaldehyde, cantonal, cetonal, cinnamaldehyde, cis-4-decenal, cis-6-nonenal, citral, citronellal, citronellyloxyacetaldehyde, cocal, cuminaldehyde, curgix, cyclal C, and cyclamen. aldehyde), lily of the valley formaldehyde (Cyclomyral), privet aldehyde (Cyclovertal), decenal 9, Dupical, empetal, ethyl vanillin, floralozone, floral aldehyde, geraldehyde, Helional® (new jasmine aldehyde), heliotropin, hexanal, hexyl cinnamaldehyde, Hivernal® neo (new winter aldehyde), hydrotropaldehyde, hydroxycitronellol, intreleven aldehyde), isobutavanyl, isocyclocitral, isopentanal, lilial, limonenal, macaronal, mefranal, melonal, methyl cinnamaldehyde, trans-2-cis-6-nonadienal, nonanal, octanal, oncidal, paratolyl aldehyde, phenylacetaldehyde, phenylpropional, precyclemone B, safranal, salicylaldehyde, scentenal, syringa aldehyde, trans-4-decenal, trans-2-dodecenal, trans-2-hexenal, trans-2-nonanal, trifernal, vanillin, veratraldehyde, vernaldehyde.

[0052] Ketones, such as: Acetanisol, Acetoin, Acetophenone, Aldron, Allyl ionone, Benzophenone, Benzylacetone, Calone, Camphor, d-Carvone, l-Carvone, Cashmeran, Cedryl methyl ketone, Cepionate, Claritone, Cosmone, Crysolide, Cyclotene, Damascenone, Damascenone α, Damascenone β, Damascenone δ, Damascenone γ, Diacetyl, Dihydro-β-ionone, Dihydro-isojasmone ester. isojasmonate, dimethyloctenone, Dynascone, ethylpentyl ketone, ethyl maltol, fenchone, filbertone, geranylacetone, globanone, heptacyclopentanone, α-ionone, β-ionone, ionone pure, Iriswood, α-iridonone, Iso E Super, isofenchone, isojasmone T, isolone K, isomenthone, isophorone, cis-jasmone cis-), Kambernoir, Kephalis, Koavone (high aromatics), Lavendinal, Maltol, Menthone, Methyl acetophenone, Methyl pentyl ketone, Methyl heptenone, Methyl hexyl ketone, γ-methyl ionone, Methyl naphthyl ketone β, Methyl nonyl ketone, Muscenone, Muscone, Nectaryl, Orinox, OTBC ketone, p-tert-butylcyclohexanone, Patchwood, Phantolid, Pharaone, Piperitone, Plicatone, Raspberryketone, Raspberryketone methyl ether, Safraleine, Spirogalbanone pure, Tonalid, Trimofix O,(Shumufu), Veloutone, Vetikon.

[0053] Alcohols, such as: Alcohol oxo C13, Amber core, Ambermax, Ambrinol, Amyl vinyl carbinol, Anisic alcohol, Bacdanol, Benzyl alcohol, Butanol, Cedrol crystals, Cinnamyl alcohol, Citronellol, Coranol, Decanol, Dimethylbenzyl alcohol, Dimethyloctyl alcohol, Dimethylphenylethyl alcohol, Dimethylheptanol, Fenchol, Hexanol, Isoborneol, Isoborneol, Javanol, Keflorol, Kohinool, Lauryl alcohol, Lilyflore, Linalool. Oxide), Mayol, Menthol, Norlimbanol, Octyl alcohol, Osyrol, p-tert-butylcyclohexanol, Phenoxanol, Phenoxyethanol, Phenylethanol, Phenylpropanol, Propylene glycol, Rosaphen, Rose glycol, Styrallyl alcohol), tricyclodecanediethanol, tetrahydrolinalool, tetrahydromyrcenol, Timberol, Undecavertol, cis-3-hexenol, Citronellollaevo, 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.

[0054] Phenolic compounds, such as: butylated hydroxyanisole, dihydroeugenol, dimethylhydroquinone, dimethylresorcinol, eugenol pure, guaiacol, isoeugenol, m-cresol, methyldiantilis, p-cresol, propenyl guaethol, thymol, and ultravanil.

[0055] Ethers, such as: Ambroxan, Anethole, Anther, Benzyl isopentyl ether, Benzyl isopropyl ether, Benzyl isovalerate, Boisiris, Cedramber, Cetalox, Decyl methyl ether, Dibenzyl ether, Dihydrorose oxide, Diphenyl oxide, Doremox, Estragole, Ethyl linalool, Eucalyptol, Galaxolide, Gyrane, Herbavert, Lime oxide, Madrox, Methyl isoeugenol, Naphthyl isobutyl ether β, Nerol oxide, 2-Naphthylethyl ether bromelia), p-tolyl butyl ether, p-tolyl methyl ether, Petiole, phenyl ethyl methyl ether, 2,4-dimethyl-4-phenyltetrahydrofuran (Rhubafuran), rose oxide, Rosyrane, Trisamber, Vetylbois K, and Yarayara.

[0056] Acetals, such as: acetal CD, acetal R, amberketal, boisambrene forte, citral diacetal, 1,1-diethoxyethane, emeraldine, freshopal, herboxane, indoflor, jacinthaflor, magnolol, spirambrene, viridine, elintaal, gycolierral, karanal, and methylpamplemousse.

[0057] Hydrocarbons, such as: bisabolene, camphene, carene delta 3, caryophyllene, cedrene, cymene para, dipentene, diphenylmethane, isolongifolene, d-limonene, longifolene, myrcene, naphthalene, ocimene, pinene α, pinene β, styrene, terpinolene γ, terpinolene, 1,3,5-undecanetriene, and isopropyl galbanum.

[0058] Sulfur compounds, such as: Corps cassis, dibutyl sulfide, dimethyl sulfide, methyl 2-hexyl-3-oxocyclopentacarboxylate (Exovert), grapefruit thiol, oxane, ribesmercaptan, thiothiazole, and thioocineol.

[0059] Nitriles, such as: Cinnamyl nitrile, Citronellyl nitrile, 3,7-dimethyl-6-octene nitrile, Clonal, Cumin nitrile, Hexylcyclopentanone, Irisnitrile, 3,7-dimethyl-2,6-octadienyl nitrile, Peonile, tridecyl nitrile, Agrumen nitrile, and n-decanoic acid nitrile.

[0060] Oximes, such as: Buccoxime, Labienoxime, Stemone.

[0061] Nitrogen heterocyclic compounds, such as: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, 2-(3-phenylpropyl)pyridine (Corps racine), 2-ethyl-3,5 (or 6)-dimethylpyrazine, furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3 (or 6)-methoxypyrazine, isopropylquinoline, Maritima, p-methylquinoline, 3-methylindole (Skatol), 2,3,5-trimethylpyrazine.

[0062] Nitro compounds, such as Musk Ketone.

[0063] Schiff bases, such as: nerol, helianthral, ​​ligantraal, and verdantiol.

[0064] Other materials include: acetanilide, cyclic amine (Gardamide), fruit amide (Paradisamide), dimethyl anthranilate, methyl anthranilate, butyric acid, capric acid, hexanoic acid, octanoic acid, phenylacetic acid, caryophyllene oxide, cedroxyde, and Tobacarol.

[0065] Therefore, compounds of formula (I) and / or formula (II) can be used to produce compositions and a wide range of known odorants / fragrances, flavors, and / or deodorants / masking materials as will be apparent from the foregoing compilation. In the production of such compositions, previously referred to known fragrances, flavors, and / or deodorants / masking materials may be used according to methods known to perfumers, such as those described in WA Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London 1974.

[0066] In embodiments of the invention, the claimed fragrance, flavor, and / or deodorizing / masking compositions, in addition to compounds of formula (I) and / or formula (II), contain at least one ester and / or one alcohol (if present, different from compounds (I) and (II)), preferably a mixture of at least esters and alcohols; said esters and / or alcohols are preferably selected from the list defined above herein. In embodiments of the invention, the claimed odorant compositions are characterized in that the total content of compounds of formula (I) and / or formula (II) together with esters and / or alcohols exceeds 25 wt.%, preferably exceeds 50 wt.%, for example exceeds 75 wt.% or even exceeds 90 wt.%.

[0067] Preparation / Synthesis In one embodiment, the compounds of formula (I) and / or formula (II) refer to both stereoisomers and / or regioisomers, or individually separated isomers. In embodiments of the invention, p-toluenesulfonic acid is used as described in the following chemical scheme. p Using TSA as a catalyst and toluene as a solvent, the aldehyde or ketone (III) undergoes a Prince reaction with isopentenol to obtain the product of general formula (IV). Alternatively, the reaction is carried out in the presence of methanesulfonic acid (MSA) as a catalyst without the use of any solvent to obtain a compound of formula (IV). Catalytic hydrogenation of compound (IV) yields a compound of formula (V). Surprisingly, we found that using dialkyl oxalate (VI) at a catalytic amount... pCompound (V) is directly obtained by treating it at a higher temperature of 160-180°C in the presence of TSA. Methanesulfonic acid or sulfuric acid can be used instead. p TSA was used in the above methods. Interestingly, we also found that, in addition to oxalate esters, even pyruvate esters, malonate esters, and succinate esters react with compounds of formula (V) under the above conditions to yield compounds of general formula (I).

[0068] Further hydrogenation of these compounds using Pd / C produces compounds of formula (II).

[0069] Therefore, we have developed a novel three-step method to obtain unsaturated oxalate / pyruvate / malonate / succinate derivatives of formula (I), which, upon hydrogenation, yield the corresponding saturated oxalate / pyruvate / malonate / succinate derivatives of general formula (II).

[0070] The literature procedures for preparing oxalates involve treating alcohols with symmetrical dioxalates in the presence of Lewis acids (Kron, AA et al. USSR, SU1150247 A1 1985-04-15 and Kron, A. A et al. Maslozhirovaya Promyshlennost (1985), (10), 28-30).

[0071] In this paper, we report the reaction of tetrahydropyran derivatives (V) with oxalate esters at catalytic levels of protic acids such as... p The reaction in the presence of TSA, methanesulfonic acid or sulfuric acid directly yields the asymmetric oxalate of formula (I) in good yield.

[0072] Our current method yields the desired alicyclic musk compound of formula (I) in three steps and / or the desired compound of formula (II) in four steps.

[0073] Further, compound (I) was hydrolyzed with an aqueous sodium hydroxide solution to obtain alcohol (VII). Alcohol (VII) was treated with diethyl malonate, diethyl succinate, or ethyl pyruvate to obtain the compounds in Examples 2, 3, and 4, respectively. The product in Example 2 was hydrogenated to obtain the compound in Example 6.

[0074] Our optimized method can also involve the following 7 steps: Step 1: The compound of formula (III) is reacted with isopentenol to give the compound of formula (IV).

[0075] Step 2: Hydrogenate the resulting regioisomeric mixture of pyran(IV) under pressure and elevated temperature using Raney nickel and hydrogen to obtain tetrahydropyran derivative(V).

[0076] Step 3: The compound of formula (V) reacts with dialkyl oxalate / malonate / succinate / ethyl pyruvate in a catalytic amount p The reaction occurs in the presence of TSA, methanesulfonic acid, or sulfuric acid, resulting in the opening of the tetrahydropyran ring to obtain a compound of formula (I), where n = 0, 1, 2.

[0077] Step 4: Hydrogenate the resulting regioisomeric mixture of oxalate / pyruvate / malonate / succinate (I) over carbon and hydrogen using Raney nickel or palladium under pressure and elevated temperature to obtain a saturated oxalate derivative of formula (II).

[0078] Step 5: Hydrolyze the compound of formula (I) with NaOH aqueous solution to obtain the alcohol of formula (VII).

[0079] Step 6: The alcohol of formula (VII) is reacted with dialkyl malonate (n = 1) or dialkyl succinate (n = 2) or ethyl pyruvate (n = 0 and M = Me) to obtain the novel compound of formula (I).

[0080] Step 7: Hydrogenate the malonate, succinate or pyruvate of formula (I) under pressure and elevated temperature using Raney nickel and hydrogen to obtain the compound of formula (II): malonate (n = 1) or succinate (n = 2) or pyruvate (n = 0 and M = Me).

[0081] In one embodiment, a method for preparing compounds of formula (I) and / or formula (II) comprises the following steps: in R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = Me, -OMe, -OEt, -O i -Pr、-O- nPr, -O-allyl, -O-isobutyl or -O-n-butyl The dashed lines represent alternative locations for the double bond, and n = 0, 1, or 2; Step 1: The compound of formula (III) is reacted with isopentenol to give a regioisomeric mixture of pyrans of formula (IV).

[0082] Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms In the above scheme, the reaction is advantageously carried out using methanesulfonic acid (MSA) as a catalyst; this step can be completed in the absence of a solvent. Alternatively, other acids, such as CF3SO3H or p-toluenesulfonic acid, can be used. p TSA); in this case, solvents such as toluene or methylcyclohexane may also be used.

[0083] Step 2: Hydrogenate the regioisomeric mixture of pyran (IV) from Step 1 on carbon and hydrogen in the presence of Raney nickel or palladium to obtain a tetrahydropyran derivative (V).

[0084] Where R1 = H or an alkyl group with up to 7 carbon atoms. R2 = Alkyl group with up to 7 carbon atoms This step can be advantageously performed under pressure (at 200 psi) and at elevated temperatures (e.g., between 100 and 130°C, such as about 120°C).

[0085] Step 3: The tetrahydropyran derivative of formula (V) from step 2 is reacted with dialkyl oxalate / malonate / succinate / ethyl pyruvate to obtain a regioisomeric mixture of compounds of formula (I), where n = 0, 1, 2.

[0086] Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = -Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl or -O-n-butyl.

[0087] The dialkyl oxalate is advantageously selected from dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, diallyl oxalate, di-n-butyl oxalate, or diisobutyl oxalate. R = -OMe, -OEt, -Oi-Pr, -O-nPr, -O-allyl, -O-isobutyl, or -O-n-butyl.

[0088] The dialkyl malonic acid ester / succinate is also advantageously selected from dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, diallyl oxalate, di-n-butyl oxalate, or diisobutyl oxalate. R = -OMe, -OEt, -Oi-Pr, -O-nPr, -O-allyl, -O-isobutyl, or -O-n-butyl.

[0089] This step can advantageously reduce the catalytic amount p The process takes place in the presence of TSA, methanesulfonic acid, or sulfuric acid, resulting in the opening of the tetrahydropyran ring.

[0090] Optional and additional step 4: Hydrogenation of the regioisomeric mixture of oxalate / pyruvate / malonate / succinate (I) from step 3 over carbon and hydrogen in the presence of Raney nickel or palladium to obtain a saturated oxalate derivative of formula (II), where n = 0, 1, 2 Where R1 = H or an alkyl group with up to 7 carbon atoms. R2 = Alkyl group with up to 7 carbon atoms M = -Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl or -O-n-butyl.

[0091] This step can be advantageously performed under pressure (at 200 psi) and at elevated temperatures (e.g., between 100 and 130°C, such as about 120°C).

[0092] Optional and additional step 5 (after step 3): hydrolyze the regioisomeric mixture of oxalate / pyruvate / malonate / succinate (I) from step 3 to obtain a regioisomeric mixture of alcohols of formula (VII).

[0093] Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms This step can be advantageously carried out in the presence of an aqueous NaOH solution.

[0094] Optional and additional step 6: The regioisomeric mixture of alcohols of formula (VII) is reacted with dialkyl malonate (n = 1, M = -O-alkyl) or dialkyl succinate (n = 2, M = -O-alkyl) or ethyl pyruvate (n = 0 and M = Me) to obtain a regioisomeric mixture of compounds of formula (I).

[0095] Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene groups with up to 7 carbon atoms.

[0096] Higher dialkyl groups can be used in step 6 for malonate / succinate / pyruvate (e.g., diisopropyl, diallyl, di-n-butyl or diisobutyl), with dimethyl or diethyl being preferred.

[0097] Optional and additional step 7: Hydrogenate the regioisomeric mixture of formula (I) of step 6 to obtain the compound of formula (II): malonate (n = 1, M = -O-alkyl) or succinate (n = 2, M = -O-alkyl) or pyruvate (n = 0 and M = Me).

[0098] Where R1 = H or an alkyl group with up to 7 carbon atoms. R2 = Alkyl group with up to 7 carbon atoms This step can advantageously be carried out on carbon and hydrogen in the presence of Raney nickel or palladium. This step can advantageously be carried out under pressure (at 200 psi) and at elevated temperatures (e.g., between 100 and 130 °C, such as about 120 °C).

[0099] The following are the synthetic procedures and characterization data for some of the selected compounds. Example

[0100] Example 1: A mixture of 3,7-dimethyl-5-methylene octyl ethyl oxalate (compound 1), ethyl (3,5,7-trimethyloct-4-en-1-yl) oxalate (compound 2), and ethyl (3,5,7-trimethyloct-5-en-1-yl) oxalate (compound 3) was synthesized using 4-methylpentan-2-one and isopentenol. Step 1: Synthesis of 2-isobutyl-2-methyl-4-methylenetetrahydro-2 H -Pyran, 2-Isobutyl-2,4-dimethyl-3,6-dihydro-2 H -Pyran and 6-isobutyl-4,6-dimethyl-3,6-dihydro-2H -A mixture of pyrans: Methanesulfonic acid (57.3 g, 0.59 mol) was added to 4-methylpentan-2-one (200.0 g, 1.99 mol) at 25 °C for 15 min. The reaction mixture was stirred for 15 min and 3-methylbut-3-en-1-ol (206.5 g, 2.39 mol) was added at 25 °C for 30 min. An exothermic reaction was generated during the addition, which was controlled by external cooling with water. After the addition was complete, the reaction mixture was heated at 60 °C for 24 h. The reaction mixture was cooled to 25 °C and the acid layer was removed. The organic layer was washed with 60 mL of 5% sodium bicarbonate aqueous solution, followed by washing with water (100 mL) and saturated brine (2 x 100 mL). The crude residue (345.0 g) containing 57% product was distilled by GC analysis to obtain 137.5 g (41% yield) of the desired product.

[0101] IR (pure): 2953.5, 1719.0, 1609.4, 1447.6 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.30-5.16 (m, 1 H), 4.01- 3.97 (m, 1 H), 3.73 -3.63 (m, 2 H), 1.98 – 1.68 (m, 3 H). 1.65 (s, 2 H), 1.43 – 1.20 (m, 2H), 1.10-1.08 (m,3 H), 0.91- 0.82 (m, 6 H). GC-MS (m / z): 168.2 (M+), 153.1, 140.1, 111.1.

[0102] Step 2: Synthesis of 2-isobutyl-2,4-dimethyltetrahydro-2 H -Pyran(V) In an autoclave, Raney nickel (10.6 g, 0.12 mol) was added to a solution of the mixture from step 1 (218.0 g, 1.29 mol) in 2-propanol (110 mL). The reaction mixture was heated at 120 °C under 200 psi hydrogen pressure and maintained for 18 h. The reaction mixture was cooled to 30 °C and filtered through a hyflow bed. The hyflow bed was washed with 2-propanol (2 x 50 mL). The organic layer was concentrated to obtain 217.0 g (96% yield) of the desired product.

[0103] IR (pure): 2951.2, 1457.2, 1373.2 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 3.66 – 3.58 (m, 2 H), 1.80 – 1.73 (m, 3 H), 1.52 – 1.34 (m, 4 H), 1.21 – 1.14 (m, 4 H), 0.99 – 0.84 (m, 9 H). GC-MS (m / z): 171.1 (M+), 155.2, 113.1.

[0104] Step 3: Synthesize a mixture of 3,7-dimethyl-5-methylene octyl ethyl oxalate (compound 1), ethyl (3,5,7-trimethyloct-4-en-1-yl) oxalate (compound 2) and ethyl (3,5,7-trimethyloct-5-en-1-yl) oxalate (compound 3): 2-Isobutyl-2,4-dimethyltetrahydro- 2H A solution of pyran (100.0 g, 0.58 mol), 4-methylbenzenesulfonic acid hydrate (11.7 g, 0.058 mol), and diethyl oxalate (171.6 g, 1.17 mol) was heated at 160–165 °C for 4 h. The ethanol formed was removed by downward distillation. The reaction mixture was cooled to room temperature and washed with water (3 x 100 ml), followed by washing with brine. Excess diethyl oxalate was removed by vacuum distillation at a pressure of 5 mbar and a top temperature of 48–52 °C. The desired product, in the form of a regioisomeric mixture, was obtained using a vacuum of 1.0 mbar and a top temperature of 80–85 °C to give the desired compound (98.0 g, 60%) as a colorless liquid.

[0105] Scent characteristics: musky, woody, powdery, dry.

[0106] IR (pure): 2957.7, 1769.1, 1743.2 cm⁻¹ -1 1H NMR (400 MHz, CDCl3): δ 5.02 – 4.73 (m, 1H), 4.38 – 4.28 (m, 3H), 4.26 – 4.16 (m, 1 H), 2.60 – 2. 43 (m, 1 H), 1.92 -1.73 (m, 4 H), 1.63 – 1.54 (m, 4 H), 1.38 – 1.35 (m, 3 H), 0.97 – 0.81 (m, 9 H). GC-MS (m / z): 270.1 (M+), 252.2, 197.2, 152.2.

[0107] Example 2: Synthesize a mixture of 3,7-dimethyl-5-methylene octyl ethyl malonate (compound-4), ethyl (3,5,7-trimethyloct-4-en-1-yl) malonate (compound-5), ethyl (3,5,7-trimethyloct-5-en-1-yl) malonate (compound-6): 2-Isobutyl-2,4-dimethyltetrahydro- 2H A solution of pyran (100.0 g, 0.58 mol), 4-methylbenzenesulfonic acid hydrate (11.7 g, 0.058 mol), and diethyl malonate (187.4 g, 1.17 mol) was heated at 160–165 °C for 4 h. The ethanol formed was removed by downward distillation. The reaction mixture was cooled to room temperature and washed with water (3 x 100 ml), followed by washing with brine. Excess diethyl malonate was removed by vacuum distillation at a pressure of 5 mbar and a top temperature of 52–55 °C. The desired product, in the form of a regioisomeric mixture, was obtained using a vacuum of 1.0 mbar and a top temperature of 85–90 °C to give the desired compound (66.8 g, 40%) as a colorless liquid.

[0108] Example 2: Alternative Synthesis A mixture of 3,7-dimethyl-5-methylene octyl ethyl malonate (compound-4), ethyl (3,5,7-trimethyloct-4-en-1-yl) malonate (compound-5), and ethyl (3,5,7-trimethyloct-5-en-1-yl) malonate (compound-6) was synthesized. Step 1: The general procedure for preparing the compound of formula VII is as follows: At 0 °C, a solution of sodium hydroxide dissolved in water (2.2 eq) was slowly added to a solution of Example-1 (compound of formula I) (1.0 eq) in MeOH and water (1:4). The reaction mixture was stirred at room temperature for 3 h. After the reaction, methanol was evaporated using a rotary evaporator, and the aqueous fraction was neutralized with dilute hydrochloric acid and extracted with ethyl acetate (3 x 200 mL). The combined organic layers were washed with water, followed by washing with brine. The solvent was evaporated on a rotary evaporator to give the alcohol of formula VII. The crude product was used in the next step without further purification.

[0109] Step 2: The product is synthesized from the alcohol of formula VII as follows.

[0110] A solution of alcohol VII (100 g, 0.58 mol) and diethyl malonate (232.2 g, 1.45 mol) was heated at 160–165 °C for 4 h. The ethanol formed was removed by downward distillation. The reaction mixture was cooled to room temperature and washed with water (3 x 100 mL), followed by washing with brine. Excess diethyl malonate was removed by vacuum distillation at a pressure of 5 mbar and a top temperature of 52–55 °C. The desired product, in the form of a regioisomeric mixture, was obtained using a vacuum of 1.0 mbar and a top temperature of 85–90 °C to give the desired compound (49.3 g, 29%) as a colorless liquid.

[0111] Scent characteristics: powdery, mild fruity, musky IR (pure): 2957.2, 2931.3, 1751.6, 1770.1, 1734.6 cm⁻¹ -1 1H NMR (400 MHz, CDCl3): δ 5.00-4.80 (m, 1 H), 4.21-4.15 (m, 3 H), 4.14 - 4.00 (m, 1 H), 3.36-3.32 (m, 2 H), 2.54-2.41 (m, 1H), 1.96-1.86 (m, 1H), 1.85-1.77 (m, 1 H), 1.76-1.64 (m, 2 H), 1.61 (dd, J = 9.6 Hz and 1.2 Hz, 1 H), 1.54 (dd, J = 4.8 Hz and 1.2 Hz, 2 H), 1.51-1.32 (m, 1 H), 1.26 (t, J= 6.8 Hz, 3H), 0.96-0.78 (m, 9 H). GC-MS (m / z): 284.1(M+), 239.2, 197.2, 152.2, 123.1.

[0112] Example 3: A mixture of 3,7-dimethyl-5-methylene octyl ethyl succinate (compound 7), ethyl (3,5,7-trimethyloct-4-en-1-yl) succinate (compound 8), and ethyl (3,5,7-trimethyloct-5-en-1-yl) succinate (compound 9) was synthesized. The product, which is a mixture of regioisomeric compounds, is obtained by the reaction described in step 3 of Example-1, where diethyl succinate is used instead of diethyl oxalate.

[0113] Alternatively, the product can also be synthesized from an alcohol of formula VII in the form of a regioisomeric mixture using the method described in step 2 of Example-2, wherein diethyl succinate is used instead of diethyl oxalate: Odor characteristics: spicy, musky IR (pure): 2957.0, 2870.7, 1734.6, 1156.0 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 5.02-4.70 (m, 1 H), 4.13 (q, J = 14 Hz, 2 H),4.09-3.95 (m, 2 H), 2.60 (d, J = 2 Hz, 4 H), 2.53-2.42 (m, 1 H), 1.97-1.87 (m,1 H), 1.85-1.1.63 (m, 3 H), 1.61 (dd, J = 6.8 Hz, 1.2 Hz. 1 H), 1.54 (dd, J = 5.6Hz, 1.2 Hz, 2 H), 1.50-1.323 (m, 1 H), 1.24 (t, J = 7.2 Hz, 3 H), 0.96-0.78 (m,9 H). GC-MS (m / z): 298.1 (M+), 253.2, 152.2.

[0114] Example 4: A mixture of 3,7-dimethyl-5-methylene octyl 2-oxopropionate (compound 10), 3,5,7-trimethyloct-4-en-1-yl 2-oxopropionate (compound 11), and 3,5,7-trimethyloct-5-en-1-yl 2-oxopropionate (compound 12) was synthesized. The product, which is a mixture of regioisomeric compounds, is obtained by the reaction described in step 3 of Example-1, where ethyl pyruvate is used instead of diethyl oxalate.

[0115] Alternatively, the product, which is in the form of a regioisomeric mixture, can also be synthesized from an alcohol of formula VII using the method described in step 2 of Example-2, here with ethyl pyruvate instead of diethyl oxalate: Scent characteristics: strong musk, leather, and woody.

[0116] IR (pure): 2956.8, 2929.6, 1730.4, 1136.6 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 5.04-4.70 (m, 1 H), 436-4.12 (m, 2 H), 2.57-2.42 (m, 3 H), 2.02-1.67 (m, 4 H), 1.62 (dd, J = 9.6 and 1.2 Hz, 2 H), 1.60-1.50(m, 2 H), 1.49-1.23 (m, 1 H), 1.00-0.76 (m, 9 H). GC-MS (m / z): 240.2, 197.1, 169.1, 151.1, 123.1, 95.1.

[0117] Example 5: Synthesis of ethyl (3,5,7-trimethyloctyl)oxalate (compound 13): In an autoclave, 5% Pd / C (2.4 g) was added to a solution of Example-1 (48.0 g, 0.18 mol) in ethanol (150 mL), and a slight exothermic reaction was observed under a hydrogen pressure of 15 kg. The reaction mixture was heated at 70 °C under a hydrogen pressure of 15 kg and maintained for 7 h. The reaction mixture was cooled to room temperature and filtered through a diatomaceous earth bed. The diatomaceous earth bed was washed with ethanol (2 x 50 mL). The organic layer was concentrated to obtain 48.0 g of crude product. The crude product was purified by vacuum distillation. A pure product was obtained using a 1.0 mbar vacuum and a top temperature of 82–86 °C to obtain the desired compound (40.0 g, 82%) as a colorless liquid.

[0118] Scent characteristics: musky, sweet, powdery.

[0119] IR (pure): 2958.4, 2911.4, 1770.1, 1743.1, 1156.6 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 4.36 -4.28 (m, 4 H), 1.68-1.54 (m, 5 H), 1.36 (t, J = 7.2 Hz, 3 H), 1.23 – 0.95 (m, 4 H), 0.89 -0.79 (m, 12 H).

[0120] Example 6: Synthesis of ethyl (3,5,7-trimethyloctyl)malonate (compound 14): This product was synthesized from the product of Example 2 using the method described in Example-5.

[0121] Scent characteristics: woody, musky, and fruity.

[0122] IR (pure): 2957.3, 2910.3, 1751.7, 1735.0 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 4.22-4.10 (m, 4 H), 3.36-3.33 (m, 2 H), 1.75-1.30 (m, 5 H), 1.26 (t, J = 7.2 Hz, 3 H), 1.21-0.89 (m, 4 H), 0.88-0.75 (m, 12 H). GC-MS (m / z): 287.3 (M+H), 241.2, 223.2, 205.1, 187.1, 133.1.

[0123] Example 7: A mixture of ethyl (3,6,6-trimethyl-5-methyleneheptyl)oxalate (compound 15) and ethyl (3,5,6,6-tetramethylhept-4-en-1-yl)oxalate (compound 16) was synthesized. Step 1: Synthesize a mixture of 2-(tert-butyl)-2-methyl-4-methylenetetrahydro-2H-pyran, 2-(tert-butyl)-2,4-dimethyl-3,6-dihydro-2H-pyran and 6-(tert-butyl)-4,6-dimethyl-3,6-dihydro-2H-pyran: Methanesulfonic acid (57.31 g, 0.59 mol) was added to 3,3-dimethylbut-2-one (200.0 g, 1.99 mol) at 25 °C for 15 min. The reaction mixture was stirred for 15 min, and 3-methylbut-3-en-1-ol (206.5 g, 2.39 mol) was added to it at 25 °C for 30 min. An exothermic reaction was generated during the addition, which was controlled by external cooling with water. After the addition was complete, the reaction mixture was heated at 60 °C for 24 h. The reaction mixture was cooled to 25 °C and the acid layer was removed. The organic layer was washed with 60 mL of 5% sodium bicarbonate aqueous solution, followed by washing with water (100 mL) and saturated brine (2 x 100 mL). The crude residue (345.0 g) containing 57% product was distilled by GC analysis to obtain 124.3 g (37% yield) of the desired product as a mixture of regioisomers.

[0124] IR (pure): 2960.8, 2912.5, 1686.3, 1365.1 cm⁻¹ -1 1H NMR (400 MHz, CDCl3): δ 5.39 – 5.37 (m, 1 H), 4.05 – 4.03 (m, 1 H), 3.80 – 3.61 (m, 1 H), 2.26 – 2.15 (m, 2 H), 1.67 (s, 3 H), 1.05 (m, 3 H), 0.91(s, 9 H).

[0125] Step 2: Synthesis of 2-(tert-butyl)-2,4-dimethyltetrahydro-2H-pyran In an autoclave, Raney nickel (10.6 g, 0.12 mol) was added to a solution of the mixture from step-1 (218.0 g, 1.29 mol) in 2-propanol (110 mL). The reaction mixture was heated at 120 °C under 200 psi of hydrogen and maintained for 18 h. The reaction mixture was cooled to 30 °C and filtered through a hyflow bed. The hyflow bed was washed with 2-propanol (2 x 50 mL). The organic layer was concentrated to obtain 209.5 g (95% yield) of the desired product.

[0126] IR (pure): 2954.0, 2923.1, 1456.2, 1365.1 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 3.78 – 3.56 (m, 2 H), 1.97 – 1.76 (m, 1 H), 1.75 – 1.69 (m, 2 H), 1.48 –1.44 (m, 2 H), 1.14 (s, 3 H), 0.98 (d, J = 6.8 Hz, 3 H), 0.91 (s, 9 H). GC-MS (m / z): 171.1 (M+), 155.1, 113.1.

[0127] Step 3: Synthesis of a mixture of ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate (compound 15) and ethyl (3,5,6,6-tetramethylhept-4-en-1-yl) oxalate (compound 16): The product was synthesized from 2-(tert-butyl)-2,4-dimethyltetrahydro-2H-pyran using the method described in step 3 of Example-1 as a mixture of regioisomers: Scent characteristics: mild musky and powdery, fatty, floral.

[0128] IR (pure): 2960.7, 2871.5, 1768.2, 1742.8, 1177.0 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 4.93-4.88 (m, 1 H), 4.33 (q, J = 7.2 Hz, 2 H), 4.25-4.15 (m, 2 H), 2.56-2.44 (m, 1 H), 1.85-1.72 (m, 1 H), 1.58 (d,J = 1.2Hz, 3 H), 1.56-1.50 (m, 1 H), 1.36 (t, J = 7.2 Hz, 3 H), 1.03-0.98 (m, 9 H), 0.95 (d, J = 6.8 Hz, 3 H). GC-MS (m / z): 270.1 (M+), 214.1, 137.1, 95.1.

[0129] Example 8: Synthesis of ethyl (3,5,6,6-tetramethylheptyl) oxalate (compound 17): This product was synthesized from the product of Example 7 using the method described in Example-5.

[0130] Scent characteristics: mild musk, powdery.

[0131] IR (pure): 2961.3, 2873.2, 1769.1, 1743.4, 1177.3 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 4.42-4.22 (m, 4 H), 1.95-1.52 (m, 3 H), 1.40-1.30 (m, 4 H), 1.23-1.14 (m, 1 H), 1.04- 0.85 (m, 5 H), 0.85-0.72 (m, 11H). GC-MS (m / z): 273.1 (M+H), 239.2, 217.2, 143.1, 120.1.

[0132] Example 9: A mixture of 3,7-dimethyl-5-methylene octyl isopropyl oxalate (compound 18), isopropyl (3,5,7-trimethyloct-4-en-1-yl) oxalate (compound 19), and isopropyl (3,5,7-trimethyloct-5-en-1-yl) oxalate (compound 20) was synthesized. This product was synthesized from the product of step 2 of Example 1 using the method described in step 3 of Example 1 as a mixture of regioisomers, with diisopropyl oxalate used instead of diethyl oxalate: Scent characteristics: Musk, woody, cedar-like IR (pure): 2957.3, 2871.0, 1766.4, 1740.4, 1173.1 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.16- 5.10 (m, 1 H), 4.90 – 4.80 (m, 1 H), 4.30 – 4.19 (m, 2 H), 2.51 – 2.45 (m, 1 H), 1.94 – 1.86 (m, 1 H), 1.80 – 1.72(m, 4 H),1.61 – 1.52 (m, 3 H), 1.32 (d, J = 6.4 Hz, 6 H), 0.95 - 0. 80 (m, 9H). GC-MS (m / z): 284.1 (M+), 241.2, 197.1, 152.2, 123.1, 95.1.

[0133] Example 10: Synthesis of isopropyl (3,5,7-trimethyloctyl) oxalate (compound 21): The product was synthesized from the product of Example 9 using the method described in Example-5.

[0134] Scent characteristics: Musk, woody IR (pure): 2957.3, 2911.2, 1766.9, 1740.8, 1174.5 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.23 - 5.10 (m, 1 H), 4.33 - 4.27 (m, 2 H), 1.79 - 1.46 (m, 5 H), 1.35 (d, J = 6.4 Hz, 6 H), 1.05 – 0.91 (m, 4 H), 0.89 –0.78 (m, 12 H).

[0135] Example 11: A mixture of 3,7-dimethyl-5-methylene octylpropyl oxalate (compound 22), propyl (3,5,7-trimethyloct-4-en-1-yl) oxalate (compound 23), and propyl (3,5,7-trimethyloct-5-en-1-yl) oxalate (compound 24) was synthesized. This product was synthesized from the product of step 2 of Example 1 using the method described in step 3 of Example 1 as a mixture of regioisomers, with dipropyl oxalate used instead of diethyl oxalate: Scent characteristics: Musk, woody IR (pure): 2958.7, 2871.7, 1769.5, 1743.1, 1169.8 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.05- 4.80 (m, 1 H), 4.34 - 4.16 (m, 4 H), 2.60- 2.42 (m, 1 H), 2.00 - 1.43 (m, 10 H), 1.02 - 0.80 (m, 12 H). GC-MS (m / z): 284.1 (M+), 266.1, 197.1, 152.2.

[0136] Example 12: A mixture of 3,7-dimethyl-5-methylene octyl isobutyl oxalate (compound 25), isobutyl(3,5,7-trimethyloct-4-en-1-yl) oxalate (compound 26), and isobutyl(3,5,7-trimethyloct-5-en-1-yl) oxalate (compound 27) was synthesized. This product was synthesized from the product of step 2 of Example 1 using the method described in step 3 of Example 1 as a mixture of regioisomers, with diisobutyl oxalate used instead of diethyl oxalate: Scent characteristics: woody, smoky, musky, animalic IR (pure): 2958.4, 2872.6, 1769.8, 1742.7, 1157.2 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.01 -4.82 (m, 1 H), 4.34 – 4.18 (m, 2 H), 4.02 (d, J = 6.8 Hz, 2 H), 2.55 – 2.46 (m, 1 H), 2.07 – 1.53 (m, 10 H), 0.99 –0.80 (m, 14 H). GC-MS (m / z): 299.2 (M+H), 280.1, 197.2, 137.1.

[0137] Example 13: Synthesis of isobutyl(3,5,7-trimethyloctyl) oxalate (compound 28): The product was synthesized from the product of Example 12 using the method described in Example-5.

[0138] Scent characteristics: Musk, mild woody IR (pure): 2958.4, 2911.4, 1770.1, 1743.1, 1156.6 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 4.36 – 4.28 (m, 2 H), 4.07 – 4.00 (m, 2 H), 2.08 – 1.96 (m, 2 H), 1.80 – 1.42 (m, 6 H), 1.22 – 0.76 (m, 18 H).

[0139] Example 14: A mixture of 3,7-dimethyl-5-methylene octyl methyl oxalate (compound 29), methyl (3,5,7-trimethyloct-4-en-1-yl) oxalate (compound 30), and methyl (3,5,7-trimethyloct-5-en-1-yl) oxalate (compound 31) was synthesized. This product was synthesized from the product of step 2 of Example 1 using the method described in step 3 of Example 1 as a mixture of regioisomers, with dimethyl oxalate used instead of diethyl oxalate: Scent characteristics: woody, musky, oily 1 H NMR (400 MHz, CDCl3): δ 4.98 - 4.79 (m, 1 H), 4.39-4.14 (m, 2 H), 3.97-3.85 (m, 3 H), 2.60-2.39 (m, 1 H), 1.99-1.43 (m, 8 H), 1.06-0.72 (m, 9H). GC-MS (m / z): 256.1 (M+), 238.2, 197.2, 152.2, 123.1, 95.1.

[0140] Example 15: Synthesis of methyl (3,5,7-trimethyloctyl)oxalate (compound 32): The product was synthesized from the product of Example 14 using the method described in Example-5.

[0141] Scent characteristics: strong musk, woody IR (pure): 2957.2, 2911.0, 1772.9, 1744.7, 1155.6 cm⁻¹ -1 1H NMR (400 MHz, CDCl3): δ 4.40-4.24 (m, 2 H), 3.90 (s, 3 H), 1.81-1.60 (m, 6 H), 1.27-1.16 (m, 1 H), 1.11- 0.78 (m, 14 H). GC-MS (m / z): 259.1 (M+H), 199.2, 125.1, 97.1.

[0142] Example 16: A mixture of ethyl (3-methyl-5-methylene octyl) oxalate (compound 33), 3,5-dimethyl oct-4-en-1-yl ethyl oxalate (compound 34) and 3,5-dimethyl oct-5-en-1-yl ethyl oxalate (compound 35) was synthesized. Step 1: Synthesis of 2-methyl-4-methylene-2-propyltetrahydro-2-methyl H -Pyran, 4,6-dimethyl-6-propyl-3,6-dihydro-2 H -Pyran, 2,4-Dimethyl-2-propyl-3,6-dihydro-2 H A mixture of pyrans: Trifluoromethanesulfonic acid (10.44 g, 0.070 mol) was slowly added to a solution of penta-2-one (200.0 g, 2.32 mol) at 25 °C for 20 min, and the reaction mixture was stirred for 15 min. Then, 3-methylbut-3-en-1-ol (205.0 g, 2.32 mol) was added at room temperature for 30 min. An exothermic reaction was generated during the addition, which was controlled by external cooling with water. After the addition, the reaction mixture was heated to 75–80 °C for 15 h. The reaction mixture was cooled to room temperature, and then methyl tert-butyl ether (500 mL) was added to it. The organic layer was washed with a 5% sodium bicarbonate aqueous solution (100 mL), followed by washing with water (4 x 200 mL) to neutral pH. The organic solvent was evaporated under reduced pressure to obtain 260 g of crude product. The crude product was distilled (70-71 °C at 17-13 mbar) to obtain a regioisomeric mixture of the desired product (98.0 g, 31%).

[0143] 1 H NMR (400 MHz, CDCl3): δ 5.29 – 5.16 (m, 2 H), 4.04 – 3.97 (m, 2 H), 3.72 – 3.60 (m, 2 H), 1.51 -1.14 (m, 4 H), 1.08-1.03 (m, 4 H), 0.87 – 0.77(m, 4H). GC-MS (m / z): 154.2 (M + ).

[0144] Step 2: Synthesis of 2,4-dimethyl-2-propyltetrahydro-2 H -Pyran: In an autoclave, Raney Ni (6.77 g, 0.079 mol) was added to a solution of the mixture of products obtained in step 1 (122.0 g, 0.79 mol) in isopropanol (244 mL). The reaction mixture was heated at 80 °C for 5 h under 200 psi hydrogen pressure. The reaction mixture was then heated at 120 °C for 16 h under 300 psi hydrogen pressure. After the reaction was complete, the reaction mixture was cooled to room temperature. The reaction mixture was filtered and then concentrated under reduced pressure. The crude residue was distilled (56–58 °C, at 10⁻⁸ mbar) to obtain the desired product (84.5 g, 68%).

[0145] 1 H NMR (400 MHz, CDCl3): δ 3.63 – 3.31 (m, 2 H), 1.70 – 1.58 (m, 2 H), 1.45 – 1.15 (m, 10 H), 1.08 -0.78 (m, 6 H). GC-MS (m / z): 155.2 (M + ), 113.1.

[0146] Step 3: Synthesize a mixture of ethyl (3-methyl-5-methylene octyl) oxalate (compound 33), 3,5-dimethyloct-4-en-1-yl ethyl oxalate (compound 34), and 3,5-dimethyloct-5-en-1-yl ethyl oxalate (compound 35): The product was synthesized from 2,4-dimethyl-2-propyltetrahydro-2H-pyran using the method described in step 3 of Example-1 as a mixture of regioisomers: Scent characteristics: musk, woody.

[0147] 1 H NMR (400 MHz, CDCl3): δ 4.98 - 4.79 (m, 1 H), 4.39-4.14 (m, 2 H), 3.97-3.85 (m, 3 H), 2.60-2.39 (m, 1 H), 1.99-1.43 (m, 8 H), 1.06-0.72 (m, 9H). GC-MS (m / z): 256.1 (M+), 238.2, 183.2, 138.1, 111.1, 95.1.

[0148] Example 17: A mixture of ethyl (3-methyl-5-methylenedecyl) oxalate (compound 36), 3,5-dimethyldec-4-en-1-ylethyl oxalate (compound 37), and 3,5-dimethyldec-5-en-1-ylethyl oxalate (compound 38) was synthesized. Step 1: Synthesize a mixture of 2-methyl-4-methylene-2-pentyltetrahydro-2H-pyran, 2,4-dimethyl-2-pentyl-3,6-dihydro-2H-pyran and 4,6-dimethyl-6-pentyl-3,6-dihydro-2H-pyran: Methanesulfonic acid (50.4 g, 0.52 mol) was added to heptan-2-one (200.0 g, 1.75 mol) for 15 min at 25 °C. The reaction mixture was stirred for 15 min, and 3-methylbut-3-en-1-ol (180.9 g, 2.1 mol) was added to it for 30 min at 25 °C. An exothermic reaction was generated during the addition, which was controlled by external cooling with water. After the addition was complete, the reaction mixture was heated at 60 °C for 24 h. The reaction mixture was cooled to 25 °C and the acid layer was removed. The organic layer was washed with 60 mL of 5% sodium bicarbonate aqueous solution, followed by washing with water (100 mL) and saturated brine (2 x 100 mL). The crude residue (370.0 g) containing 65% of the product was distilled by GC analysis to obtain 200.9 g (63% yield) of the desired product.

[0149] IR (pure): 2932.5, 2862.6, 1680.8, 1456.2, 1378.0 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.38 – 5.25 (m, 1 H), 3.78 – 3.73 (m, 2 H), 2.04 – 1.96 (m, 1 H), 1.84 – 1.79 (m, 1 H), 1.60 (s, 3 H), 1.36 – 1.23 (m, 8H), 1.15 (s,3 H), 0.90 – 0. 85 (m, 3 H). GC-MS (m / z): 182.2 (M + ), 167.2, 139.1, 111.1.

[0150] Step 2: Synthesis of 2,4-dimethyl-2-pentyltetrahydro-2H-pyran In an autoclave, Raney nickel (4.69 g, 0.054 mol) was added to a solution of the mixture from step-1 (100.0 g, 0.55 mol) in 2-propanol (50 mL). The reaction mixture was heated at 120 °C under 200 psi of hydrogen and maintained for 18 h. The reaction mixture was cooled to 30 °C and filtered through a hyflow bed. The hyflow bed was washed with 2-propanol (2 x 50 mL). The organic layer was concentrated to obtain 88.8 g (88% yield) of the desired product.

[0151] IR (pure): 2928.4, 2860.9, 1457.4, 1375.1 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 3.81 – 3.55 (m, 2 H), 1.85 – 1.73 (m, 1 H), 1.52 – 1.25 (m, 12 H), 1.15 – 1.12 (m, 3 H), 0.91 – 0.85 (m, 6 H). GC-MS (m / z): 183.2 (M - ), 169.2, 113.1.

[0152] Step 3: Synthesize a mixture of ethyl (3-methyl-5-methylenedecyl) oxalate (compound 36), 3,5-dimethyldec-4-en-1-ylethyl oxalate (compound 37), and 3,5-dimethyldec-5-en-1-ylethyl oxalate (compound 38): The product was synthesized from 2,4-dimethyl-2-pentyltetrahydro-2H-pyran using the method described in step 3 of Example-1 as a mixture of regioisomers: Scent characteristics: musk, woody.

[0153] IR (pure): 2959.0, 2928.4, 1769.0, 1743.2, 1157.6 cm⁻¹ -1 1H NMR (400 MHz, CDCl3): δ 4.98 - 4.79 (m, 1 H), 4.39-4.14 (m, 2 H), 3.97-3.85 (m, 3 H), 2.60-2.39 (m, 1 H), 1.99-1.43 (m, 8 H), 1.06-0.72 (m, 9H). GC-MS (m / z): 284.1 (M+), 266.1, 211.2, 166.2, 123.1, 95.1.

[0154] Example 18: Synthesis of 3,5-dimethyloctylethyl oxalate (compound 39): This product was synthesized from the product of Example 16 and using the reaction conditions of Example 5: Scent characteristics: Musk, smoky, woody, amber, sweet.

[0155] IR (pure): 2959.1, 2928.5, 1768.1, 1742.6 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 4.39-4.25 (m, 4 H), 2.01-1.40 (m, 6 H), 1.36 (t, J = 6.8 Hz, 3 H), 1.32-0.93 (m, 4 H), 0.92-0.78 (m, 9 H). GC-MS (m / z): 256.1(M+), 238.1, 183.1, 138.1, 109.1.

[0156] Example 19: Synthesis of 3,5-dimethyldecylethyl oxalate (compound 40): This product was synthesized from the product of Example 17 and using the reaction conditions of Example 5: Scent characteristics: sweet, musky, woody.

[0157] IR (pure): 2958.8, 2926.3, 1769.5, 1743.8 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 4.39-4.25 (m, 4 H), 1.83-1.42 (m, 5 H), 1.37(t, J= 6.8 Hz, 3 H), 1.33-1.16 (m, 6 H), 1.15-0.94 (m, 3 H), 0.93-0.77 (m, 9H). GC-MS (m / z): 286.1 (M+), 268.2, 213.2, 139.2, 115.1, 97.1.

[0158] Example 20: A mixture of 3,7-dimethyloct-4-en-1-ylethyl oxalate (compound 41) and 3,7-dimethyloct-5-en-1-ylethyl oxalate (compound 42) was synthesized: The product was synthesized from 2-isobutyl-4-methyltetrahydro-2H-pyran using the method described in step 3 of Example-1 as a mixture of regioisomers.

[0159] Scent characteristics: Musk, fruity, powdery IR (pure): 2958.7, 2931.5, 1768.6, 1742.7 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 5.42 – 5.09 (m, 2 H), 4.36 – 4.17 (m, 4 H), 2.22 – 2.17 (m, 1 H), 2.01 – 1.36 (m, 5 H), 1.35 (t, J = 8.0 Hz, 3 H), 1.00 –0.83 (m, 9 H). GC-MS (m / z): 254.1 (MH), 183.1, 139.2, 123.1, 95.1.

[0160] Therefore, only a few compounds that fall within the scope of this invention are disclosed. It should be noted that the disclosed compounds do not limit the scope of this invention.

[0161] The above description of the present invention is for illustrative purposes only and is not intended to be restrictive. Since modifications to the disclosed embodiments may occur to those skilled in the art incorporating the spirit and substance of the invention, the invention should be construed as including everything within the scope of this disclosure.

[0162] Composition Evaluation Examples: In the following invention, as shown in Table 1, a composition (C) containing compounds from Example-1 (a mixture of 3,7-dimethyl-5-methylene octyl ethyl oxalate, ethyl (3,5,7-trimethyl oct-4-en-1-yl) oxalate and ethyl (3,5,7-trimethyl oct-5-en-1-yl) oxalate) was compared with compositions containing commercially available materials such as 3,7-dimethyl oct-6-en-1-yl ethyl oxalate (citronellol ethoxylate, composition G), ethylene glycol brassinate (composition B), and muskrat (composition I). (Composition A = blank), DPG = dipropylene glycol.

[0163] Table 1: Examples 1 (Compounds 1 / 2 / 3) in Shampoo: When the compound from Example-1 was applied to the shampoo at 10% w / w, composition C imparted an impactful musky character. Compared to other compositions B, G, and I, which respectively contain the commercially available compounds ethylene glycol brassinate, 3,7-dimethyloctyl-6-en-1-ylethyl oxalate (citronellol ethoxylate), and romaine musk, composition C exhibited a more intense, very rounded, and fuller character. On odor test strips, the compound from Example-1 was found to be significantly stronger than ethylene glycol brassinate, citronellol ethoxylate, and romaine musk.

[0164] In the following invention, as shown in Table 2: a composition (A) containing the compound from Example-1 (a mixture of 3,7-dimethyl-5-methylene octyl ethyl oxalate, ethyl (3,5,7-trimethyl oct-4-en-1-yl) oxalate and ethyl (3,5,7-trimethyl oct-5-en-1-yl) oxalate) was compared with a composition of commercially available cyclopentadecanolactone ((12E)-oxetane-12-en-2-one, composition B), with composition C serving as a blank (isopropyl myristate IPM).

[0165] Table 2: Examples 1 (Compounds 1 / 2 / 3) in Shampoo: In the above floral, fruity, and musky accompaniments, when comparing composition A containing Example-1 with composition B containing the commercially available compound cyclopentadecanolactone, it was observed that adding Example-1 imparted a more natural volume and a greater fullness and creaminess to the accompaniment compared to cyclopentadecanolactone. Indeed, it has been found that using Example-1 in many accompaniments resulted in enhanced fullness and creaminess. Therefore, Example-1 is suitable for a wide range of applications due to its high performance.

[0166] In the following inventions, as shown in Table 3, compositions (D) containing the compound (ethyl 3,5,7-trimethyloctyl oxalate) from Example-5 are compared with compositions of the following materials: Composition H (3,7-dimethyloctyl ethyl oxalate (dihydrocitronellol ethoxylate)), Composition B (ethylene glycol brassinate), and Example I (rohmann musk). (Composition A = blank), DPG = dipropylene glycol.

[0167] When the compound from Example-5 (compound 13: ethyl 3,5,7-trimethyloctyl oxalate) was added to the shampoo at 10% w / w, it imparted a powerful musky character to the composition. Composition D exhibited a strong, very rounded character compared to other compositions B, H, and I, which respectively contained the commercially available compounds ethylene glycol brassinate, 3,7-dimethyloctyl ethyl oxalate (dihydrocitronellol ethoxylate), and romaine musk. On odor test strips, the compound from Example-5 was found to be more potent than ethylene glycol brassinate, 3,7-dimethyloctyl ethyl oxalate, and romaine musk.

[0168] Table 3: Example 5 (Compound 13) in shampoo: .

Claims

1. Compounds of general formula (I) and / or formula (II) in R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl, -O-n-butyl The dashed lines represent alternative locations for the double bond, and n = 0, 1, or 2 The condition is that compounds of general formula (I) and / or formula (II) cannot be 3,7-Dimethyloctylethyl oxalate and 3,7-Dimethyloctyl 3-oxobutyrate.

2. The compound according to claim 1, wherein R1 and R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, and heptylene.

3. The compound according to claim 1, wherein the compound is selected from the following compounds: 1) 3,7-Dimethyl-5-methylene octylethyl oxalate 2) Ethyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 3) Ethyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 4) 3,7-Dimethyl-5-methylene octyl ethyl malonate 5) Ethyl (3,5,7-trimethyloct-4-en-1-yl)malonate 6) Ethyl (3,5,7-trimethyloct-5-en-1-yl)malonate 7) 3,7-Dimethyl-5-methylene octylethyl succinate 8) Ethyl (3,5,7-trimethyloct-4-en-1-yl)succinate 9) Ethyl (3,5,7-trimethyloct-5-en-1-yl)succinate 10) 3,7-Dimethyl-5-methyleneoctyl-2-oxopropionate 11) 3,5,7-Trimethyloct-4-en-1-yl 2-oxopropionate 12) 3,5,7-Trimethyloct-5-en-1-yl 2-oxopropionate 13) Ethyl (3,5,7-trimethyloctyl)oxalate 14) Ethyl (3,5,7-trimethyloctyl)malonate 15) Ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate 16) Ethyl(3,5,6,6-tetramethylhept-4-en-1-yl)oxalate 17) Ethyl (3,5,6,6-tetramethylheptyl)oxalate 18) 3,7-Dimethyl-5-methylene octyl isopropyl oxalate 19) Isopropyl (3,5,7-trimethyloct-4-en-1-yl)oxalate 20) Isopropyl (3,5,7-trimethyloct-5-en-1-yl)oxalate 21) Isopropyl (3,5,7-trimethyloctyl)oxalate 22) 3,7-Dimethyl-5-methylene octylpropyl oxalate 23) Propyl (3,5,7-trimethyloct-4-en-1-yl) oxalate 24) Propyl (3,5,7-trimethyloct-5-en-1-yl) oxalate 25) 3,7-Dimethyl-5-methylene octyl isobutyl oxalate 26) Isobutyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 27) Isobutyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 28) Isobutyl(3,5,7-trimethyloctyl)oxalate 29) 3,7-Dimethyl-5-methylene octylmethyl oxalate 30) Methyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 31) Methyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 32) Methyl (3,5,7-trimethyloctyl)oxalate 33) Ethyl (3-methyl-5-methylene octyl) oxalate 34) 3,5-Dimethyloct-4-en-1-ylethyl oxalate 35) 3,5-Dimethyloct-5-en-1-ylethyl oxalate 36) Ethyl (3-methyl-5-methylenedecyl) oxalate 37) 3,5-Dimethyldec-4-en-1-ylethyl oxalate 38) 3,5-Dimethyldec-5-en-1-ylethyl oxalate 39) 3,5-Dimethyloctylethyl oxalate 40) 3,5-Dimethyldecylethyl oxalate 41) 3,7-Dimethyloct-4-en-1-ylethyl oxalate 42) 3,7-Dimethyloct-5-en-1-ylethyl oxalate 43) Ethyl (5-ethyl-3-methylhept-4-en-1-yl)oxalate 44) Ethyl (5-ethyl-3-methylhept-5-en-1-yl)oxalate 45) Ethyl (5-ethyl-3-methylheptyl) oxalate 46) Ethyl(3,5,6-trimethylhept-4-en-1-yl)oxalate 47) Ethyl(3,5,6-trimethylhept-5-en-1-yl)oxalate 48) 3,6-Dimethyl-5-methyleneheptylethyl oxalate 49) 3,5-Dimethylhept-4-en-1-ylethyl oxalate 50) 3,5-Dimethylhept-5-en-1-ylethyl oxalate 51) Ethyl (3-methyl-5-methyleneheptyl) oxalate 52) Ethyl (3-methyl-5-methylene nonyl) oxalate 53) 3,5-Dimethylnon-4-en-1-ylethyl oxalate 54) 3,5-Dimethylnon-5-en-1-ylethyl oxalate 55) Ethyl(3-methyl-5-propyloct-4-en-1-yl)oxalate 56) Ethyl(3-methyl-5-propyloct-5-en-1-yl)oxalate 57) Ethyl (3-methyl-5-propyloctyl)oxalate 58) Ethyl(3,5,9-trimethyldec-4-en-1-yl)oxalate 59) 3,9-Dimethyl-5-methylenedecylethyl oxalate 60) Ethyl(3,5,9-trimethyldec-5-en-1-yl)oxalate 61) Ethyl(5-isobutyl-3,7-dimethyloct-4-en-1-yl)oxalate 62) Ethyl(5-isobutyl-3,7-dimethyloct-5-en-1-yl)oxalate 63) Ethyl (5-isobutyl-3,7-dimethyloctyl) oxalate 64) Ethyl (5-ethyl-3-methylhept-4-en-1-yl)malonate 65) Ethyl (5-ethyl-3-methylhept-5-en-1-yl)malonate 66) 5-Ethyl-3-methylhept-4-en-1-yl 2-oxopropionate 67) 5-Ethyl-3-methylhept-5-en-1-yl 2-oxopropionate 68) Ethyl(3,5,6-trimethylhept-4-en-1-yl)malonate 69) Ethyl (3,5,6-trimethylhept-5-en-1-yl)malonate 70) 3,6-Dimethyl-5-methyleneheptylethylmalonate 71) Ethyl(5-isopropyl-3,6-dimethylhept-4-en-1-yl)oxalate 72) Ethyl(5-isopropyl-3,6-dimethylhept-5-en-1-yl)oxalate 73) Ethyl(5-isopropyl-3,6-dimethylhept-5-en-1-yl)oxalate 74) Ethyl (5-isopropyl-3,6-dimethylheptyl) oxalate 75) Ethyl(3-methyloct-4-en-1-yl)oxalate 76) Ethyl(3-methyloct-5-en-1-yl)oxalate 77) Ethyl(3-methylnon-4-en-1-yl)oxalate 78) Ethyl(3-methylnon-5-en-1-yl)oxalate 79) Ethyl(3-methyldec-4-en-1-yl)oxalate 80) Ethyl(3-methyldec-5-en-1-yl)oxalate 81) Ethyl(3-methylundec-4-en-1-yl)oxalate 82) Ethyl(3-methylundec-5-en-1-yl)oxalate 83) Ethyl(3-methyldodec-4-en-1-yl)oxalate 84) Ethyl(3-methyldodec-5-en-1-yl)oxalate 85) 3,6-Dimethylhept-4-en-1-ylethyl oxalate 86) 3,6-Dimethylhept-5-en-1-ylethyl oxalate 87) Ethyl(3,6,7-trimethyloct-5-en-1-yl)oxalate 88) Ethyl(3,6,7-trimethyloct-4-en-1-yl)oxalate 89) 3,6-Dimethyloct-5-en-1-ylethyl oxalate 90) 3,6-Dimethyloct-4-en-1-ylethyl oxalate 91) 3,6-Dimethylnon-5-en-1-ylethyl oxalate 92) 3,6-Dimethylnon-4-en-1-ylethyl oxalate 93) 3,6-Dimethyldec-5-en-1-ylethyl oxalate 94) 3,6-Dimethyldec-4-en-1-ylethyl oxalate 95) 3,6-Dimethylundec-5-en-1-ylethyl oxalate 96) 3,6-Dimethylundec-4-en-1-ylethyl oxalate.

4. The compound according to claim 1, wherein the compound is selected from the following compounds: 1) 3,7-Dimethyl-5-methylene octylethyl oxalate 2) Ethyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 3) Ethyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 4) 3,7-Dimethyl-5-methylene octyl ethyl malonate 5) Ethyl (3,5,7-trimethyloct-4-en-1-yl)malonate 6) Ethyl (3,5,7-trimethyloct-5-en-1-yl)malonate 7) 3,7-Dimethyl-5-methylene octylethyl succinate 8) Ethyl (3,5,7-trimethyloct-4-en-1-yl)succinate 9) Ethyl (3,5,7-trimethyloct-5-en-1-yl)succinate 10) 3,7-Dimethyl-5-methyleneoctyl-2-oxopropionate 11) 3,5,7-Trimethyloct-4-en-1-yl 2-oxopropionate 12) 3,5,7-Trimethyloct-5-en-1-yl 2-oxopropionate 13) Ethyl (3,5,7-trimethyloctyl)oxalate 14) Ethyl (3,5,7-trimethyloctyl)malonate 15) Ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate 16) Ethyl(3,5,6,6-tetramethylhept-4-en-1-yl)oxalate 17) Ethyl (3,5,6,6-tetramethylheptyl)oxalate 18) 3,7-Dimethyl-5-methylene octyl isopropyl oxalate 19) Isopropyl (3,5,7-trimethyloct-4-en-1-yl)oxalate 20) Isopropyl (3,5,7-trimethyloct-5-en-1-yl)oxalate 21) Isopropyl (3,5,7-trimethyloctyl)oxalate 22) 3,7-Dimethyl-5-methylene octylpropyl oxalate 23) Propyl (3,5,7-trimethyloct-4-en-1-yl) oxalate 24) Propyl (3,5,7-trimethyloct-5-en-1-yl) oxalate 25) 3,7-Dimethyl-5-methylene octyl isobutyl oxalate 26) Isobutyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 27) Isobutyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 28) Isobutyl(3,5,7-trimethyloctyl)oxalate 29) 3,7-Dimethyl-5-methylene octylmethyl oxalate 30) Methyl(3,5,7-trimethyloct-4-en-1-yl)oxalate 31) Methyl(3,5,7-trimethyloct-5-en-1-yl)oxalate 32) Methyl (3,5,7-trimethyloctyl)oxalate 33) Ethyl (3-methyl-5-methylene octyl) oxalate 34) ,5-Dimethyloct-4-en-1-ylethyl oxalate 35) 3,5-Dimethyloct-5-en-1-ylethyl oxalate 36) Ethyl (3-methyl-5-methylenedecyl) oxalate 37) 3,5-Dimethyldec-4-en-1-ylethyl oxalate 38) 3,5-Dimethyldec-5-en-1-ylethyl oxalate 39) 3,5-Dimethyloctylethyl oxalate 40) 3,5-Dimethyldecylethyl oxalate 41) 3,7-Dimethyloct-4-en-1-ylethyl oxalate 42) 3,7-Dimethyloct-5-en-1-ylethyl oxalate.

5. A regioisomeric mixture of the compound of formula (I) according to any one of claims 1-4.

6. A mixture of compounds of formula (I) and formula (II) according to any one of claims 1-5.

7. A fragrance, flavor, and / or deodorizing / masking composition comprising a compound according to any one of claims 1-4 or a mixture according to claim 5 or claim 6.

8. A fragrance, flavor, and / or deodorizing / masking composition comprising the regional isomeric mixture according to claim 5.

9. The fragrance, flavor and / or deodorizing / masking composition according to any one of claims 7 to 8, comprising, in addition to the compound of formula (I) or formula (II), at least one ester and / or one alcohol, wherein the total content of the compound of formula (I) and formula (II) together with the ester and alcohol exceeds 25 wt%.

10. The fragrance, flavor and / or deodorizing / masking composition according to claim 9, wherein the total content of the compounds of formula (I) and formula (II) together with the esters and alcohols exceeds 50 wt%.

11. Use of the fragrance, flavor, and / or deodorizing / masking composition according to any one of claims 7 to 10 in a perfumery or flavoring product exhibiting a musky, woody, animalic, and / or powdery fragrance note.

12. Use of the compound according to any one of claims 1-4 or the mixture according to any one of claims 5 or 6 in a fragrance or flavoring product exhibiting a musky, woody, animalic, and / or powdery aroma.

13. Methods for preparing compounds of formula (I) and / or (II) in R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl or -O-n-butyl The dashed lines represent alternative locations for the double bond, and n = 0, 1 or 2 It includes the following steps: Step 1: The compound of formula (III) is reacted with isopentenol to obtain a regioisomer mixture of pyrans of formula (IV). Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene groups with up to 7 carbon atoms. Step 2: Hydrogenate the regioisomeric mixture of pyran (IV) from Step 1 over carbon and hydrogen in the presence of Raney nickel or palladium to obtain a tetrahydropyran derivative (V). Where R1 = H or an alkyl group with up to 7 carbon atoms. R2 = alkyl group with up to 7 carbon atoms. Step 3: The tetrahydropyran derivative of formula (V) from step 2 is reacted with dialkyl oxalate / malonate / succinate / ethyl pyruvate to obtain a regioisomeric mixture of compounds of formula (I), where n = 0, 1, 2 Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene group with up to 7 carbon atoms M = -Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl or -O-n-butyl.

14. The method of claim 13 for preparing compounds of formula (I) and / or (II), wherein the regioisomeric mixture of oxalate / pyruvate / malonate / succinate (I) in step 3 - Hydrogenation over carbon and hydrogen in the presence of Raney nickel or palladium (step 4) to obtain saturated oxalate / pyruvate / malonate / succinate derivatives of formula (II), where n = 0, 1, 2 Where R1 = H or an alkyl group with up to 7 carbon atoms. R2 = alkyl group with up to 7 carbon atoms M = -Me, -OMe, -OEt, -O i -Pr、-O- n Pr, -O-allyl, -O-isobutyl or -O-n-butyl, or - Hydrolyzed (step 5) to obtain a regioisomeric mixture of alcohols of formula (VII). Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene groups with up to 7 carbon atoms.

15. The method of claim 14 for preparing compounds of formula (I) and / or (II), wherein the regioisomeric mixture of alcohols of formula (VII) from step 5 is reacted with dialkyl malonate (n = 1, M = -O-alkyl) or dialkyl succinate (n = 2, M = -O-alkyl) or ethyl pyruvate (n = 0 and M = Me) (step 6) to obtain a regioisomeric mixture of compounds of formula (I). Where R1 = H or an alkyl or alkylene group with up to 7 carbon atoms. R2 = alkyl or alkylene groups with up to 7 carbon atoms.

16. The method of claim 15 for preparing compounds of formula (I) and / or (II), wherein the regioisomeric mixture of malonate, succinate, or pyruvate of formula (I) in step 6 is hydrogenated (step 7) to obtain compounds of formula (II): malonate (n = 1, M = -O-alkyl) or succinate (n = 2, M = -O-alkyl) or pyruvate (n = 0 and M = Me). Where R1 = H or an alkyl group with up to 7 carbon atoms. R2 = Alkyl group with up to 7 carbon atoms.

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