Odorous compounds and method of preparation thereof

Abstract

The present invention relates to novel odorous compounds denoted by formula (I) and / or formula (II), which are useful as fragrance or flavor materials in particular in providing musky, woody, animalic and / or powdery type notes to perfume, aroma or deodorizing / masking compositions. The present invention also relates to fragrance, flavor and / or deodorizing / masking compositions comprising odorous compounds denoted by formula (I) and / or formula (II). The present invention furthermore refers to the use of said odorants in fragrance, flavor and / or deodorizing / masking compositions of the present invention. The present invention also refers to a process for the production of the said odorants / compounds.

Description

[0001] ODOROUS COMPOUNDS AND METHOD OF PREPARATION THEREOF

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to novel odorous compounds denoted by formula (I) and / or (II), which are useful as fragrance or flavor materials in particular in providing musky, woody, animalic and / or powdery type notes to perfume, aroma or deodorizing / masking compositions. The present invention also relates to fragrance, flavor and / or deodorizing / masking compositions comprising odorous compounds denoted by formula (I) and / or formula (II). The present invention furthermore refers to the use of said odorants in fragrance, flavor and / or deodorizing / masking compositions of the present invention. The present invention also refers to a process for the production of the said odorants / compounds and of the corresponding fragrance, flavor and / or deodorizing / masking compositions containing said odorants / compounds .

[0004] BACKGROUND OF THE INVENTION

[0005] There is huge demand for musk odorants, which typically constitute base note of a fragrance. Musk odorants are indispensable in perfumery for imparting sensuality and erogenous effect. After nitro musks were discontinued due to safety concerns, macrocyclic and polycyclic musks dominated the musk ingredients that were used by perfumers. Amongst these two classes, polycyclic musks (PCMs) had a disproportionately higher share due to their low cost and ease of synthesis. However, the inherent hydrophobicity in the PCMs translates to poor biodegradability, which in turn is suspect in increasing bioaccumulation.

[0006] A new class of musk odorants called alicyclic musks emerged after discovery of Cyclomusk in 1975 by researchers in BASF. Cyclomusk, which possesses a fruity, strawberry-type musk odor, does not belong structurally to any of the three known classes of musk odorants listed above. Two more musk odorants were discovered, namely Helvetolide, which displays musky, fruity, pear notes; and Romandolide that has musky, ambrette and fruity profile.

[0007] 3,7-dimethyloct-6-en-l-yl ethyl oxalate, also known as ethyl citronellyl oxalate (racemic), with its primary profile of floral, powdery and rosy also displays a musky facet. However, it was reported (Kraft, Philip et.al. European Journal of Organic Chemistry 2004, 354-365) that ethyl citronellyl oxalate is not used in perfumery as a musk odorant, its main character is floral, powdery, and rosy, with a relatively high odor threshold. In 2004, T. Yamamoto et al. (Flavour Fragr. J. 2004; 19: 121-133) reported olfactory study on optically active citronellyl derivatives. They reported that only the R isomer of ethyl citronellyl oxalate presents floral musky odor whereas the S isomer displays rose-like floral notes.

[0008] In Struct.-Act. Relat. Chemoreception, Proc. Symp. (“Boelens”) (1976), 197-209, on page 204, where table B mentions musk compounds, citronellyl ethyl oxalate (also known as 3,7- dimethyloct-6-en-l-yl ethyl oxalate) occupies the last place with lowest observed odor quality of 4.00 and lowest estimated odor quality of 4.5.

[0009] 3,7-dimethyloctyl ethyl oxalate is reported to have musk odor in Struct.-Act. Relat. Chemoreception, Proc. Symp. (“Boelens”) (1976), 197-209. However, on page 204, where table B mentions musk compounds, this compound is listed at second last place with lowest observed odor quality of 4.00. This almost matches its estimated odor quality of 4.6.

[0010] 3,7-dimethyloctyl ethyl oxalate is also known as dihydrocitronellol. It has been reported in Maslozhirovaya Promyshlennost (“Kron et al.”) (1985), (10), 28-30 that oxalates of dihydrocitronellol are devoid of musk odor. Thus, there are conflicting reports about musk character of 3,7-dimethyloctyl ethyl oxalate, also known as dihydrocitronellol ethyl oxalate floral, powdery, rosy and musky. musk like odor in one reference Not used anymore as No musk odor in other reference "musk odorant" in perfumery 3,7-dimethyloctyl ethyl oxalate

[0011] Citronellyl ethyl oxalate (ethyl dihydrocitronellyl oxalate )

[0012] Synthesis of 3,7-dimethyloctyl 3-oxobutanoate is reported by Kishimoto et al, Journal of the Chemical Society of Japan, 1975, pages 701-704. by reaction of 3, 7- dimethyloctanol / dihydrocitronellol with ethyl acetoacetate in 44% yield.

[0013] 3,7-dimethyloctyl 3-oxobutanoate

[0014] Increasing limitations on the supply of natural fragrance ingredients have revolutionized the field of synthetic fragrance ingredients. Nowadays, there is an increasing demand for novel odorants / compounds and / or novel fragrance, flavor and / or deodorizing / masking compositions comprising said odorants / compounds. Therefore, novel compounds that possess musky and related odor profile and that are readily biodegradable, are highly desired. Major advantage of alicyclic musks is that they are more price-efficient and predominantly biodegradable.

[0015] It is an advantage of the present invention that novel odorous compounds denoted by formula (I) and / or formula (II) are useful as fragrance or flavor materials in particular in providing musky, woody, animalic and / or powdery type notes to perfume, aroma or deodorizing / masking compositions. The applicants have also surprisingly discovered that introduction of a di substitution at carbon C-5 in the alkyl chain increases the strength and improves the performance of the invention compounds. The present invention also relates to a process for preparation of odorous compounds of formula (I) and / or formula (II).

[0016] INVENTION:

[0017] 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) can be any one of its stereoisomers or a mixture of one or more of these stereoisomers. Further, compounds of formula (I) and / or formula (II) can be one of its regioisomers or a mixture of one or more of its regioisomers.

[0018] The invention further discloses odorous compounds of formula (I) and / or formula (II) per se, as well as its stereoisomers or a mixture thereof and / or regioisomers or a mixture thereof.

[0019] Particularly, the invention discloses fragrance, flavor and / or deodorizing / masking compounds of formula (I) and / or formula (II)

[0020] (I) (II) wherein

[0021] Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0022] R2 = an alkyl or alkylidene group up to 7-carbon atoms

[0023] M = Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl the dotted line represents alternate positions of double bond, and n= 0, 1 or 2, with the proviso that compounds of formula (I) and formula (II) cannot be 3,7-dimethyloctyl ethyl oxalate and 3,7-dimethyloctyl 3-oxobutanoate.

[0024] According to the present invention, radicals Ri and R2 are separated radicals, i.e., they do not form together a ring. It will also be clear to a person skilled in the art that all three dotted lines in formula (I) cannot be double bonds at the same time. Thus, if Ri is bonded with a double bond then R2 will be bonded with a single bond; and if R2 is bonded with a double bond then Ri will be bonded with a single bond.

[0025] In an embodiment, Ri and / or R2 are selected from alkyl or alkylidene groups having up to 7 carbon atoms. Ri and R2 can independently be selected from a group consisting of methyl, ethyl, / / -propyl, isopropyl, / / -butyl, isobutyl, tertiary-butyl, / / -pentyl, / / -hexyl, / / -heptyl, methylidene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, hexylidene, heptylidene.

[0026] In an embodiment, M is a methyl group or an alkoxy group like methoxy, ethoxy, isopropoxy, / / -propoxy, -O-allyl, -O-isobutyl, -O- / / Butyl.

[0027] In an embodiment, compounds of formula (I) and (II) of this invention can be chiral, e.g., they can be used as pure enantiomers or diastereomers or as stereoisomeric (enantiomeric or diastereomeric) mixtures, more specifically as mixture of enantiomers or diastereoisomers; For example, as R isomer, S isomer, a racemic mixture and / or a nonracemic mixture. Further, compounds of formula (I) and (II) can also be advantageously used either as RR isomer, SS isomer, RS isomer, SR isomer, a racemic mixture and / or a non-racemic mixture. Further, compounds of formula (I) & (II) of this invention can be used as any one of its regioisomers or a mixture of its regioisomers.

[0028] By the expression “any one of its regioisomers or a mixture of its regioisomers”, it should be understood by a person skilled in the art that the presence of regioisomers results due to different position of the double bond in the structure of formula (I).

[0029] Further, the compounds of formula (I) and (II) of this invention can be used as pure compounds or as mixtures of geometric isomers (diastereomers); e.g., they can be a mixture of cis and trans isomers or as E and Z isomers. Literature procedure for preparation of oxalate ester involves treatment of readily available alcohol with symmetrical dioxalate in presence of Lewis acid (Kron, A. A. et. al USSR, SU1150247 Al 1985-04-15 and Kron, A. A et al. Maslozhirovaya Promyshlennost (1985), (10), 28-30).

[0030] Herein, we report the reaction of tetrahydropyran derivatives (V) with an oxalate ester / malonate ester / succinate ester / pyruvate ester in presence of catalytic amount of protic acid like TS A, methanesulfonic acid or sulfuric acid directly afforded unsymmetrical oxalates of formula (I) in good yields.

[0031] Our current process gives access to desired alicyclic musk compounds of formula (I) and / or formula (II) in four steps.

[0032] DETAILED DESCRIPTION

[0033] The term "odorant" characterizing the compounds according to the present invention means that in humans it triggers an odor sensation that is preferably pleasant; it is therefore conventionally used for perfuming industrial and sanitary articles, washing agents, cleaning agents, personal hygiene products, cosmetics and the like. For the purposes of the present invention and appended claims, the term “odorant” includes "aroma substances". Aroma substances is the term usually used to designate substances that provide odor and / or flavor to foodstuffs.

[0034] The compounds of formula (I) and (II) may be used alone, as mixtures thereof, or in combination with a base material.

[0035] As used herein, the "base material" includes all known fragrance / flavor materials selected from the extensive range of natural products like: essential oils, extracts, resinoids or isolates and synthetic materials currently available, such as: hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and / or in admixture with one or more ingredients or excipients / adjuvants conventionally used in conjunction with odorants in fragrance and / or flavor compositions, for example: solvents / diluents, stabilizers, carrier materials, and other auxiliary agents commonly used in the art. The compounds of formula (I) and (II) may be used in a broad range of fragrance applications, e.g., in any field of fine and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. The compounds can be employed in widely varying amounts, depending upon the specific application and on the nature and quantity of other odorant ingredients.

[0036] According to a preferred embodiment of the invention, the fragrance, flavor and / or deodorizing / masking composition contains at least one compound according to formula (I) or (II) as previously described, in quantities 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. %, in particular between 1 and 5 wt. %, in each case relative to the entire composition.

[0037] According to a particularly preferred embodiment of the invention, in addition to a compound of formula (I) and / or formula (II) according to the present invention, the fragrance, flavor and / or deodorizing / masking composition according to the present invention contains additional odorants, for example in a quantity of 0.1 to 99.9 wt. %, preferably 5-90 wt. %, in particular 15-70 wt. %, relative to the entire fragrance and / or flavor composition.

[0038] The compounds of formula (I) and (II) as described herein above may be employed in a consumer product base simply by directly mixing at least one compound of formula (I) and / or formula (II), or a fragrance composition comprising said compound or compounds of formula (I) and / or formula (II) with the consumer product base; or they may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and / or nanocapsules, liposomes, film formers, absorbents such as active carbon or zeolites, cyclic oligosaccharides, cyclic glycolurils, and mixtures of two or more thereof, or they may be chemically bonded to substrates, which are adapted to release the fragrance molecule upon application of an external stimulus such as light, enzyme, air, water or the like, and then mixed with the consumer product base.

[0039] Thus, the invention can be useful for existing methods of manufacturing a fragrance, flavor and / or deodorizing / masking composition, comprising the incorporation of one or more compounds of formula (I) and / or formula (II) as a fragrance, flavor and / or deodorizing / masking ingredient, either by directly admixing the compound to the consumer product base or by admixing a fragrance, flavor and / or deodorizing / masking composition comprising said one or more compounds of formula (I) and / or formula (II), which may then be mixed with a consumer product base, using conventional techniques and methods. Through the addition of an olfactory-acceptable amount of at least one compound of formula (I) and / or formula (II) of the present invention as hereinabove described, the odor notes of a consumer product base can be improved, enhanced, and / or modified.

[0040] This invention discloses fragrance, flavour and / or deodorizing / masking compositions comprising compounds of formula (I) and / or formula (II).

[0041] The invention discloses odorous compounds of formula (I) and / or formula (II). Particularly, the invention discloses fragrance, flavour and / or deodorizing / masking compounds of formula (I) and / or formula (II) and their method of synthesis.

[0042] Formula (I) and formula (II) are denoted as

[0043] (I) (II) wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0044] R2 = an alkyl or alkylidene group up to 7-carbon atoms

[0045] M = Me, -OMe, -OEt, -Oz-Pr, -OzzPr, -O-allyl, -O-isobutyl, -O-zzButyl the dotted line represents alternate positions of double bond, and n= 0, 1 or 2, with the proviso that compounds of formula (I) and formula (II) cannot be 3,7-dimethyloctyl ethyl oxalate and 3,7-dimethyloctyl 3-oxobutanoate.

[0046] According to the present invention, radicals Ri and R2 are separated radicals, i.e., they do not form together a ring.

[0047] In an embodiment, Ri and / or R2 is selected from alkyl or alkylidene having up to 6 carbon atoms. Ri and R2 can independently be selected from a group consisting of methyl, ethyl, n- propyl, isopropyl, / / -butyl, isobutyl, tertiary-butyl, w-pentyl, w-hexyl, methylidene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, hexylidene, heptylidene. In an embodiment, M is a methyl group or an alkoxy group like methoxy, ethoxy, isopropoxy, w-propoxy, -O-allyl, -O-isobutyl, -O-wButyl.

[0048] In an embodiment, compounds of formula (I) and / or formula (II) of this invention can be chiral, e.g., they can be used as pure enantiomers or diastereomers or as stereoisomeric (enantiomeric or diastereomeric) mixtures, more specifically as mixture of enantiomers or diastereoisomers; For example, as R isomer, S isomer, a racemic mixture and / or a nonracemic mixture. Further, compounds of formula (I) and / or formula (II) can also be advantageously used either as RR isomer, SS isomer, RS isomer, SR isomer, a racemic mixture and / or a non-racemic mixture. Further, compounds of formula (I) and / or formula (II) of this invention can be used as any one of its regioisomers or a mixture of its regioisomers. Further, the compounds of formula (I) and / or formula (II) of this invention can be used as pure compounds or as mixtures of geometric isomers (diastereomers); e.g., they can be a mixture of cis and trans isomers or as E and Z isomers.

[0049] In an embodiment, compounds of formula (I) are mixtures of regioisomers as well as stereoisomers, as illustrated below.

[0050] It is an advantage of the invention that the disclosed compounds exhibit musky, woody, animalic and / or powdery type odor profiles. In addition, perfumery compositions comprising these novel compounds described herein also exhibit musky, woody, animalic and / or powdery type odor profiles. An embodiment of the present invention relates to an odorous composition comprising compounds of formula (I) and / or formula (II). Particularly, the invention discloses fragrance, flavor and / or deodorizing / masking composition comprising one or more compounds of formula (I) and / or formula (II) and one or more adjuvants.

[0051] In general, 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, for example, solvents, carriers, stabilizers, emulsifiers, moisturizers, dispersants, diluents, thickeners, thinners, other odorants, and / or other adjuvants, and the like.

[0052] In an advantageous embodiment of the present invention, the odorous compounds of formula (I) and / or formula (II) are selected from the following compounds: Compound Number) Name

[0053] 1) 3,7-dimethyl-5-methyleneoctyl ethyl oxalate

[0054] 2) ethyl (3,5,7-trimethyloct-4-en-l-yl) oxalate

[0055] 3) ethyl (3,5,7-trimethyloct-5-en-l-yl) oxalate

[0056] 4) 3,7-dimethyl-5-methyleneoctyl ethyl malonate

[0057] 5) ethyl (3,5,7-trimethyloct-4-en-l-yl) malonate

[0058] 6) ethyl (3,5,7-trimethyloct-5-en-l-yl) malonate

[0059] 7) 3,7-dimethyl-5-methyleneoctyl ethyl succinate

[0060] 8) ethyl (3,5,7-trimethyloct-4-en-l-yl) succinate

[0061] 9) ethyl (3,5,7-trimethyloct-5-en-l-yl) succinate

[0062] 10) 3,7-dimethyl-5-methyleneoctyl 2-oxopropanoate

[0063] 11) 3,5,7-trimethyloct-4-en-l-yl 2-oxopropanoate

[0064] 12) 3,5,7-trimethyloct-5-en-l-yl 2-oxopropanoate

[0065] 13) ethyl (3,5,7-trimethyloctyl) oxalate

[0066] 14) ethyl (3,5,7-trimethyloctyl) malonate

[0067] 15) ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate

[0068] 16) ethyl (3,5,6,6-tetramethylhept-4-en-l-yl) oxalate

[0069] 17) ethyl (3, 5, 6, 6-tetram ethylheptyl) oxalate

[0070] 18) 3,7-dimethyl-5-methyleneoctyl isopropyl oxalate

[0071] 19) isopropyl (3,5,7-trimethyloct-4-en-l-yl) oxalate

[0072] 20) isopropyl (3,5,7-trimethyloct-5-en-l-yl) oxalate 21) isopropyl (3,5,7-trimethyloctyl) oxalate

[0073] 22) 3,7-dimethyl-5-methyleneoctyl propyl oxalate

[0074] 23) propyl (3,5,7-trimethyloct-4-en-l-yl) oxalate

[0075] 24) propyl (3,5,7-trimethyloct-5-en-l-yl) oxalate

[0076] 25) 3,7-dimethyl-5-methyleneoctyl isobutyl oxalate

[0077] 26) isobutyl (3,5,7-trimethyloct-4-en-l-yl) oxalate

[0078] 27) isobutyl (3,5,7-trimethyloct-5-en-l-yl) oxalate

[0079] 28) isobutyl (3,5,7-trimethyloctyl) oxalate

[0080] 29) 3,7-dimethyl-5-methyleneoctyl methyl oxalate

[0081] 30) methyl (3,5,7-trimethyloct-4-en-l-yl) oxalate

[0082] 31) methyl (3,5,7-trimethyloct-5-en-l-yl) oxalate

[0083] 32) methyl (3,5,7-trimethyloctyl) oxalate

[0084] 33) ethyl (3-methyl-5-methyleneoctyl) oxalate

[0085] 34) 3,5-dimethyloct-4-en-l-yl ethyl oxalate

[0086] 35) 3,5-dimethyloct-5-en-l-yl ethyl oxalate

[0087] 36) ethyl (3-methyl-5-methylenedecyl) oxalate

[0088] 37) 3,5-dimethyldec-4-en-l-yl ethyl oxalate

[0089] 38) 3,5-dimethyldec-5-en-l-yl ethyl oxalate

[0090] 39) 3,5-dimethyloctyl ethyl oxalate

[0091] 40) 3,5-dimethyldecyl ethyl oxalate

[0092] 41) 3,7-dimethyloct-4-en-l-yl ethyl oxalate

[0093] 42) 3,7-dimethyloct-5-en-l-yl ethyl oxalate.

[0094] In another embodiment of the present invention, the odorous compounds of formula (I) and / or formula (II) are selected from the following compounds:

[0095] 43) ethyl (5-ethyl-3-methylhept-4-en-l-yl) oxalate

[0096] 44) ethyl (5-ethyl-3-methylhept-5-en-l-yl) oxalate

[0097] 45) ethyl (5-ethyl-3-methylheptyl) oxalate

[0098] 46) ethyl (3,5,6-trimethylhept-4-en-l-yl) oxalate

[0099] 47) ethyl (3,5,6-trimethylhept-5-en-l-yl) oxalate

[0100] 48) 3,6-dimethyl-5-methyleneheptyl ethyl oxalate

[0101] 49) 3,5-dimethylhept-4-en-l-yl ethyl oxalate

[0102] 50) 3,5-dimethylhept-5-en-l-yl ethyl oxalate

[0103] 51) ethyl (3-methyl-5-methyleneheptyl) oxalate ) ethyl (3-methyl-5-methylenenonyl) oxalate ) 3,5-dimethylnon-4-en-l-yl ethyl oxalate ) 3,5-dimethylnon-5-en-l-yl ethyl oxalate ) ethyl (3-methyl-5-propyloct-4-en-l-yl) oxalate ) ethyl (3-methyl-5-propyloct-5-en-l-yl) oxalate ) ethyl (3-methyl-5-propyloctyl) oxalate ) ethyl (3,5,9-trimethyldec-4-en-l-yl) oxalate ) 3,9-dimethyl-5-methylenedecyl ethyl oxalate ) ethyl (3,5,9-trimethyldec-5-en-l-yl) oxalate ) ethyl (5-isobutyl-3,7-dimethyloct-4-en-l-yl) oxalate) ethyl (5-isobutyl-3,7-dimethyloct-5-en-l-yl) oxalate) ethyl (5-isobutyl-3,7-dimethyloctyl) oxalate ) ethyl (5-ethyl-3-methylhept-4-en-l-yl) malonate ) ethyl (5-ethyl-3-methylhept-5-en-l-yl) malonate ) 5-ethyl-3-methylhept-4-en-l-yl 2-oxopropanoate ) 5-ethyl-3-methylhept-5-en-l-yl 2-oxopropanoate ) ethyl (3,5,6-trimethylhept-4-en-l-yl) malonate ) ethyl (3,5,6-trimethylhept-5-en-l-yl) malonate ) 3,6-dimethyl-5-methyleneheptyl ethyl malonate ) ethyl (5-isopropyl-3,6-dimethylhept-4-en-l-yl) oxalate) ethyl (5-isopropyl-3,6-dimethylhept-5-en-l-yl) oxalate) ethyl (5-isopropyl-3,6-dimethylhept-5-en-l-yl) oxalate) ethyl (5-isopropyl-3,6-dimethylheptyl) oxalate ) ethyl (3-methyloct-4-en-l-yl) oxalate ) ethyl (3-methyloct-5-en-l-yl) oxalate ) ethyl (3-methylnon-4-en-l-yl) oxalate ) ethyl (3-methylnon-5-en-l-yl) oxalate ) ethyl (3-methyldec-4-en-l-yl) oxalate ) ethyl (3-methyldec-5-en-l-yl) oxalate ) ethyl (3-methylundec-4-en-l-yl) oxalate ) ethyl (3-methylundec-5-en-l-yl) oxalate ) ethyl (3-methyldodec-4-en-l-yl) oxalate ) ethyl (3-methyldodec-5-en-l-yl) oxalate ) 3,6-dimethylhept-4-en-l-yl ethyl oxalate 86) 3,6-dimethylhept-5-en-l-yl ethyl oxalate

[0104] 87) ethyl (3,6,7-trimethyloct-5-en-l-yl) oxalate

[0105] 88) ethyl (3,6,7-trimethyloct-4-en-l-yl) oxalate

[0106] 89) 3,6-dimethyloct-5-en-l-yl ethyl oxalate

[0107] 90) 3,6-dimethyloct-4-en-l-yl ethyl oxalate

[0108] 91) 3,6-dimethylnon-5-en-l-yl ethyl oxalate

[0109] 92) 3,6-dimethylnon-4-en-l-yl ethyl oxalate

[0110] 93) 3,6-dimethyldec-5-en-l-yl ethyl oxalate

[0111] 94) 3,6-dimethyldec-4-en-l-yl ethyl oxalate

[0112] 95) 3,6-dimethylundec-5-en-l-yl ethyl oxalate

[0113] 96) 3,6-dimethylundec-4-en-l-yl ethyl oxalate.

[0114] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises a compound of formula (I) and / or formula (II) that is selected from any of the compounds and / or from a mixture of two or more of the said 96 compounds given above, for example of the said 42 first compounds cited above, in particular from any one or a mixture of two or more of the said 96 compounds given above, for example of the said 42 first compounds cited above.

[0115] In an embodiment, the applicants have also surprisingly discovered that by introducing a disubstitution on carbon C-5 from the compounds of formula II, there is an increase in the strength of the musk odor.

[0116] In an embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking composition is advantageously used as a perfumery composition. Perfumery compositions according to the present invention generally include a perfume, a cologne, an eau du toilette, and / or an eau de parfum. In an embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking composition is advantageously used in a cosmetic formulation, a personal care product, a cleansing product, a fabric softener, and / or air freshener, and the like. Furthermore, it is within the purview of embodiments of the invention that the novel fragrance, flavor and / or deodorizing / masking composition(s) and / or novel compound(s) of formula (I) and / or formula (II) described herein may be integrated into building materials, wall and floor coverings, vehicle components, and the like. The compounds of formula (I) and / or formula (II) can combine with numerous known natural or synthetic fragrance, flavor and / or deodorizing / masking materials, whereby the range of the natural ingredients can embrace not only readily-volatile but also semi-volatile and slightly- volatile components and the range of the synthetic ingredients can embrace representatives from many classes of substances, such as described in Steffen Arctander, Perfume and Flavor Chemicals, vol.l&2, Montclair, N.J., 1969; Steffen Arctander, Perfume and Flavor Materials of Natural Origin, Elizabeth, N.J., 1960 or Horst Surburg, Johannes Panten, Common Fragrance and Flavor Materials, Wiley-VCH, Weinheim, 2016 and as will be evident from the following nonlimitting compilation:

[0117] Natural products such as:

[0118] 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, Citronella oil, Citronella terpenes, Clary sage oil, Clove oil rectified, 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, Galbanum oil, Geranium oil, Ginger oil Indian, Grapefruit oil, Guaiacwood oil, Gurjun balsam, Jasmin absolute, Jatamansi oil, Juniper berry oil, Juniper leaf oil, 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 resinoid, Mandarin oil, Mentha arvensis oil, Mentha citrata oil, Mimosa absolute, Myrrh resinoid, Nagarmotha oil, Nutmeg oil, Oakmoss absolute, Oakmoss resinoid, Olibanum oil, Olibanum resinoid, Orange oil, Origanum oil, Palma rosa oil, Patchouli oil, Peppermint oil, Peru Balsam resinoid, Petitgrain oil, Pine needle oil, Pink pepper oil, Rose absolute, 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, Vetiver terpenes.

[0119] Synthetic raw materials for instance:

[0120] Esters such as: Aldehyde Cl 6, Allyl amyl glycolate, Allyl caproate, Allyl cyclohexyl propionate, Allyl heptoate, Allyl phenoxy acetate, Amyl acetate iso, Amyl benzoate, Amyl butyrate, Amyl caproate, Amyl cinnamate, Amyl isovalerate, Amyl phenyl acetate, Amyl propionate, Amyl salicylate iso, Amyris acetate, Anisyl acetate, Benzyl acetate, Benzyl benzoate, Benzyl butyrate, Benzyl cinnamate, Benzyl formate, Benzyl isobutyrate, Benzyl isoeugenol, Benzyl propionate, Benzyl salicylate, Benzyl tiglate, Butyl acetate, Butyl butyrate, Butyl butyryl lactate, Caryophyllene acetate, Cedryl acetate, Cinnamyl acetate, Cinnamyl butyrate, Cis-3-hexenyl acetate, Cis-3-hexenyl benzoate, Cis-3-hexenyl caproate, Cis-3- hexenyl formate, Cis-3-hexenyl isobutyrate, Cis-3 -hexenyl -2 -methyl butyrate, Cis-3-hexenyl propionate, Cis-3-hexenyl salicylate, Cis-3-hexenyl tiglate, Citronellyl acetate, Citronellyl butyrate, Citronellyl formate, Citronellyl isobutyrate, Citronellyl propionate, Citronellyl tiglate, Cyclabute, Cyclogalbanate, Cyclohexyl ethyl acetate, Decyl acetate, Dibutyl phthalate, Diethyl malonate, Diethyl phthalate, Dihydromyrcenyl acetate, Dimethyl octanyl acetate, Dimethyl phenyl ethyl carbinyl acetate, Dioctyl adipate, Dioctyl phthalate, Dimethyl benzyl carbinyl acetate, Dimethyl benzyl carbinyl butyrate, Ethyl linalyl acetate, Ethyl 2-methyl butyrate, Ethyl 3 -phenyl propionate, Ethyl acetate, Ethyl acetoacetate, Ethyl benzoate, Ethyl butyrate, Ethyl caprate, Ethyl caproate, Ethyl caprylate, Ethyl cinnamate, Ethyl heptoate, Ethyl hexyl acetate, Ethyl isobutyrate, Ethyl laurate, Ethyl pelargonate, Ethyl phenoxy acetate, Ethyl phenyl acetate, Ethyl phenyl glycidate, Ethyl propionate, Ethyl safranate, Ethyl salicylate, Ethyl valerate, Eugenyl acetate, Evernyl, Fenchyl acetate, Floramat, Frescolat ML, Fructone, Fruitate, Geranyl acetate, Geranyl butyrate, Geranyl formate, Geranyl propionate, Geranyl tiglate, Givescone, Guaiol acetate, Hedionate, Hedione, Helvetolide, Herbanate, Hexyl acetate, Hexyl benzoate, n-Hexyl butyrate, Hexyl caproate, Hexyl isobutyrate, Hexyl propionate, Hexyl salicylate, Isobornyl acetate, Isobutyl acetate, Isobutyl phenyl acetate, Isobutyl salicylate, Isoeugenyl acetate, Isononyl acetate, Isopentyrate, Isopropyl 2-methyl butyrate, Isopropyl myristate, Jasmonyl, Liffarome, Linalyl acetate, Mahagonate, Manzanate, Menthanyl acetate, Menthyl acetate, Methyl benzoate, 2-Methyl butyl acetate, Methyl camomille, Methyl cinnamate, Methyl cyclogeranate, Methyl heptine carbonate, Methyl laurate, Methyl octine carbonate, Methyl phenyl acetate, Methyl salicylate, Methyl-2 -methyl butyrate, Neofolione, Nopyl acetate, Octenyl acetate, Octyl acetate, Octyl isobutyrate, Para cresyl acetate, Para cresyl isobutyrate, Para cresyl phenyl acetate, Pear ester, Peranat, Phenoxy ethyl isobutyrate, Phenyl ethyl acetate, Phenyl ethyl butyrate, Phenyl ethyl formate, Phenyl ethyl isobutyrate, Phenyl ethyl phenyl acetate, Phenyl ethyl propionate, Phenyl ethyl salicylate, Phenyl ethyl tiglate, Phenyl propyl isobutyrate, Prenyl acetate, Romandolide, Sagecete, Styrallyl acetate, Styrallyl propionate, Tangerinol, Terpinyl acetate, Thesaron, Trans-2 -hexenyl acetate, Tropicate, Verdox, Verdyl acetate, Verdyl propionate, Vertenex, Vetikol acetate, Vetiveryl acetate, Yasmolys. Lactones such as: Ambrettolide, Arova N, Celeriax, Decalactone delta, Decalactone gamma, Dodecalactone delta, Dodecalactone gamma, Ethylene brassylate, Exaltolide, Heptalactone gamma, Hexalactone delta, Hexalactone gamma, Methyl laitone, Methyl octalactone, Nonalactone delta, Nonalactone gamma, Octahydrocoumarine, Octalactone delta, Octalactone gamma, Rootylone, Silvanone supra, Undecalactone delta, Undecalactone gamma, Valerolactone gamma, 10-OxaHexaDecanolide (OHD musk), Coumarin, Habanolide, Jasmolactone.

[0121] Aldehydes such as: Acetaldehyde, Adoxal, Aldehyde CIO, Aldehyde Cl l iso, Aldehyde Cl l moa, Aldehyde Cl l undecylenic, Aldehyde Cl l undecylic, Aldehyde C12 lauric, Aldehyde C12 MNA, Anisaldehyde, Amyl cinnamaldehyde, Benzaldehyde, Bourgeonal, Campholenaldehyde, Cantonal, Cetonal, Cinnamic aldehyde, Cis-4-decenal, Cis-6-nonenal, Citral, Citronellal, Citronellyl oxyacetaldehyde, Cocal, Cuminaldehyde, Curgix, Cyclal C, Cyclamen aldehyde, Cyclomyral, Cyclovertal, Decenal 9, Dupical, Empetal, Ethyl vanillin, Floralozone, Florhydral, Geraldehyde, Helional®, Heliotropin, Heptanal, Hexanal, Hexyl cinnamaldehyde, Hivemal® neo, Hydratropaldehyde, Hydroxycitronellal, Intreleven aldehyde, Isobutavan, Isocyclocitral, Isovaleraldehyde, Lilial, Limonenal, Maceal, Mefranal, Melonal, Methyl cinnamaldehyde, Nonadien-al trans-2 cis-6, Nonanal, Octanal, Oncidal, Para tolyl aldehyde, Phenyl acetaldehyde, Phenyl propyl aldehyde, Precyclemone B, Safranal, Salicylaldehyde, Scentenal, Syringa aldehyde, Trans-4-decenal, Trans-2-dodecenal, Trans-2- hexenal, Trans-2 -nonenal, Trifernal, Vanillin, Veratraldehyde, Vernaldehyde

[0122] Ketones such as: Acetanisol, Acetoin, Acetophenone, Aldron, Allyl ionone, Benzophenone, Benzyl acetone, Calone, Camphor, Carvone d-, Carvone 1-, Cashmeran, Cedryl methyl ketone, Cepionate, Claritone, Cosmone, Crysolide, Cyclotene, Damascenone, Damascene alpha, Damascene beta, Damascene delta, Damascene gamma, Diacetyl, Dihydro beta ionone, Dihydro isojasmonate, Dimethyl octenone, Dynascone, Ethyl amyl ketone, Ethyl maltol, Fenchone, Filbertone, Geranyl acetone, Globanone, Heptyl cyclopentanone, Ionone alpha, Ionone beta, Ionone pure, Iriswood, Irone alpha, Iso E Super, Isofenchone, Isojasmone T, Isolene K, Isomenthone, Isophorone, Jasmone cis-, Kambemoir, Kephalis, Koavone, Lavendinal, Maltol, Menthone, Methyl acetophenone, Methyl amyl ketone, Methyl heptenone, Methyl hexyl ketone, Methyl ionone gamma, Methyl naphthyl ketone beta, Methyl nonyl ketone, Muscenone, Muscone, Nectaryl, Orinox, OTBC Ketone, Para tertbutylcyclohexanone, Patchwood, Phantolid, Pharaone, Piperitone, Plicatone, Raspberry ketone, Raspberry ketone methyl ether, Safraleine, Spirogalbanone pure, Tonalid, Trimofix O, Veloutone, Vetikon.

[0123] Alcohols such as: Alcohol oxo C13, Amber core, Ambermax, Ambrinol, Amyl vinyl carbinol, Anisic alcohol, Bacdanol, Benzyl alcohol, Butanol, Cedrol crystals, Cinnamic alcohol, Citronellol, Coranol, Decanol, Dimethyl benzyl carbinol, Dimethyl octanol, Dimethyl phenyl ethyl carbinol, Dimetol, Fenchol, Hexanol, Isobomeol, Isobornyl cyclohexanol, Javanol, Keflorol, Kohinool, Lauryl alcohol, Lilyflore, Linalool oxide, Mayol, Menthol, Norlimbanol, Octanol, Osyrol, Para tertbutylcyclohexanol, Phenoxanol, Phenoxyethanol, Phenyl ethyl alcohol, Phenyl propyl alcohol, Propylene glycol, Rosaphen, Rose glycol, Styrallyl alcohol, Tricyclodecane dimethanol, Tetrahydro linalool, Tetrahydro myrcenol, Timberol, Undecavertol, Cis-3-hexenol, Citronellol laevo, Cyclofloranol, Dihydrolinalool, Dihydromyrcenol, Dimyrcetol, Ebanol, Geraniol, Isopulegol, Linalool, Nerol, Nerolidol, Nonadien-ol trans-2 cis-6, Polysantol, Rosalva, Sandalmysore core, Sandalore, Terpinen-4-ol, Terpineol, Trans-2 -hexenol

[0124] Phenols such as: Butylated hydroxyanisole, Dihydroeugenol, Dimethyl hydroquinone, Dimethyl resorcinol, Eugenol pure, Guaiacol, Isoeugenol, Meta cresol, Methyl diantilis, Para cresol, Propenyl guaethol, Thymol, Ultravanil.

[0125] 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, Naphthyl isobutyl ether beta, Nerol oxide, Nerolin bromelia, Para cresyl butyl ether, Para cresyl methyl ether, Petiole, Phenyl ethyl methyl ether, Rhubafuran, Rose oxide, Rosyrane, Trisamber, Vetylbois K, Yara yara

[0126] Acetals such as: Acetal CD, Acetal R, Amberketal, Boisambrene forte, Citrathal, 1,1- Diethoxyethane, Emeraldine, Freshopal, Herboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Elintaal, Glycolierral, Karanal, Methyl pamplemousse,

[0127] Hydrocarbons such as: Bisabolene, Camphene, Carene delta 3, Caryophyllene, Cedrene, Cymene para, Dipentene, Diphenyl methane, Isolongifolene, Limonene d-, Longifolene, Myrcene, Naphthalene, Ocimene, Pinene alpha, Pinene beta, Styrene, Terpinene gamma, Terpinolene, 1,3,5-Undecatriene, Verdoracine.

[0128] Sulphur compounds such as: Corps cassis, Dibutyl sulphide, Dimethyl sulphide, Exovert, Grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

[0129] Nitriles such as: Cinnamyl nitrile, Citronellyl nitrile, Citronitrile, Clonal, Cumin nitrile, Hexyl cyclopentanone, Irisnitrile, Lemonile, Peonile, Tridecyl nitrile, Agrumen nitrile, n-decyl nitrile.

[0130] Oximes such as: Buccoxime, Labienoxime, Stemone.

[0131] Nitrogen heterocycles such as: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, Corps racine, 2-ethyl-3,5(or 6)-dimethylpyrazine, Furfuryl pyrrole, Indole, Isobutyl quinoline, 2- Isobutyl-3(or 6)-m ethoxypyrazine, Isopropyl quinoline, Maritima, p-m ethyl quinoline, Skatol, 2,3,5-trimethylpyrazine.

[0132] Nitro compound such as: Musk Ketone.

[0133] Schiff bases such as: Aurantiol, Helianthral, Ligantraal, Verdantiol.

[0134] Other materials such as: Acetanilide, Gardamide, Paradisamide, Dimethyl anthranilate, Methyl anthranilate, n-Butyric acid, Capric acid, Caproic acid, Caprylic acid, Phenylacetic acid, Caryophyllene oxide, Cedroxyde, Tobacarol.

[0135] The compounds of formula (I) and / or formula (II) can accordingly be used for the production of compositions and as will be evident from the foregoing compilation, a wide range of known odorants / fragrance, flavor and / or deodorizing / masking materials. In the production of such compositions, the known fragrance, flavor and / or deodorizing / masking materials referred to earlier can be used according to methods that are known to the perfumer such as, for example, according to W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th Edition, Chapman and Hall, London 1974.

[0136] In an embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking composition comprises in addition to the compound(s) of formula (I) and / or formula (II), at least one ester and / or one alcohol (other than compound (I) and formula (II) if present), preferably at least a mixture of ester and alcohol; the said ester and / or alcohol are preferably selected from the list defined herein above. In an embodiment of the present invention, the claimed odorant composition is characterised by a total content of the compound(s) of formula (I) and / or formula (II) together with the ester(s) and / or alcohol(s) which is superior to 25 wt.%, preferably superior to 50 wt.%, for example superior to 75 wt.%, or even superior to 90 wt.%.

[0137] PREPARATION / SYNTHESIS

[0138] In an embodiment, the compounds of formula (I) and / or formula (II) refer to both stereoisomeric and / or regioisomeric mixtures or individually isolated isomers. In an embodiment of the present invention, as depicted in the following chemical scheme, aldehydes or ketones (III) are subjected to Prins reaction with isoprenol using para-toluene sulfonic acid ( TSA) as catalyst and toluene as solvent; to afford products of general formula (IV). Alternatively, the reaction proceeds in presence of methanesulfonic acid (MSA) as catalyst, without any solvent to afford compounds of formula (IV). Catalytic hydrogenation of compounds (IV) yields compound of formula (V). Surprisingly, we found that treatment of compound (V) with dialkyl oxalates (VI) in presence of catalytic amount of TSA at higher temperature 160-180 °C directly afforded compounds of formula (I). Instead of TSA, one can use methanesulfonic acid or sulfuric acid for above process. Interestingly, we also found that apart from oxalates; even pyruvates, malonates and succinates reacted with compounds of formula (V) under the conditions described above to afford compounds of general formula (I).

[0139] Further hydrogenation of these compounds using Pd / C yielded compounds of formula (II).

[0140] Thus, we have developed a novel three step process to get unsaturated oxalate / pyruvate / malonate / succinate derivatives of formula (I), which on hydrogenation, afforded the corresponding saturated oxalate / pyruvate / malonate / succinate derivatives of general formula (II).

[0141] The literature procedure for preparation of oxalate ester involves treatment of alcohol with symmetrical dioxalate in presence of Lewis acid (Kron, A. A. et. al USSR, SU1150247 Al 1985-04-15 and Kron, A. A et al. Maslozhirovaya Promyshlennost (1985), (10), 28-30).

[0142] Herein, we report that reaction of tetrahydropyran derivatives (V) with an oxalate ester in presence of catalytic amount of protic acid like TSA, methanesulfonic acid or sulfuric acid directly afforded unsymmetrical oxalates of formula (I) in good yields. Our current process gives access to desired alicyclic musk compounds of formula (I) in three steps and / or formula (II) in four steps.

[0143] Further, compounds (I) were hydrolyzed with aqueous sodium hydroxide to afford alcohols (VII). Alcohols (VII) were treated with diethyl malonate, diethyl succinate or ethyl pyruvate to afford compounds from examples 2, 3 and 4 respectively. Product from example 2 was hydrogenated to give compound from example 6.

[0144] The process that we have optimized may also involve 7 steps as follows:

[0145] Step 1 : Reaction of compound of formula (III) with isoprenol to get a compound of formula

[0146] (IV).

[0147] Step 2: The resulting regioisomeric mixture of pyrans (IV) was hydrogenated using Raney nickel and hydrogen under pressure at elevated temperature to afford a tetrahydropyran derivative (V).

[0148] Step 3: Reaction of compound of formula (V) with a dialkyl oxalate / malonate / succinate / ethyl pyruvate in presence of catalytic amount of TSA or methanesulfonic acid or sulfuric acid led to opening of tetrahydropyran ring to obtain a compound of formula (I) where n = 0,1,2.

[0149] Step 4: The resulting regioisomeric mixture of oxalates / pyruvates / malonates / succinates (I) was hydrogenated using Raney nickel or Palladium on carbon and hydrogen under pressure at elevated temperature to afford saturated oxalate derivatives of formula (II).

[0150] Step 5: Compounds of formula (I) are hydrolyzed with aqueous NaOH to give alcohols of formula (VII).

[0151] VII

[0152] Step 6: Alcohols of formula (VII) are reacted with dialkyl mal onates (n = 1) or dialkyl succinates (n = 2) or ethyl pyruvate (n = 0 and M = Me) to afford novel compounds of formula (I). n = 1 ,2; M = -Oalkyl n = 0; M = Me

[0153] Step 7: Mai onates or succinates or pyruvates of formula (I) are hydrogenated using Raney nickel and hydrogen under pressure at elevated temperature to afford compounds of formula (II): malonates (n = 1) or succinates (n = 2) or pyruvate (n = 0 and M = Me). n = 1 ,2; M = -Oalkyl n = 0; M = Me

[0154] In an embodiment, a process for preparation of the compounds of formula (I) and / or formula wherein

[0155] Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0156] R2 = an alkyl or alkylidene group up to 7-carbon atoms

[0157] M = Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl the dotted line represents alternate positions of double bond, and n= 0, 1 or 2 comprises the following steps:

[0158] Step 1 : Reaction of compound of formula (III) with isoprenol to get a regioisomeric mixture of pyrans of formula (IV). wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0159] R2 = an alkyl or alkylidene group up to 7-carbon atoms

[0160] In the above scheme, the reaction advantageously proceeds with methanesulfonic acid (MSA) as a catalyst; this step can be done in the absence of solvent. Alternatively, another acid can be used, e.g. CF3SO3H or para-toluene sulfonic acid ( / ?TSA); in this instance, a solvent can also be used, e.g. toluene or methyl cyclohexane.

[0161] Step 2: The regioisomeric mixture of pyrans (IV) of step 1 is hydrogenated in the presence of Raney nickel or Palladium on carbon and hydrogen to afford a tetrahydropyran derivative (V). wherein Ri = H or an alkyl group up to 7-carbon atoms

[0162] R2 = an alkyl group up to 7-carbon atoms

[0163] This step can advantageously be performed under pressure (under 200 psi pressure) and at elevated temperature (e.g. between 100 and 130°C, for example around 120°C).

[0164] Step 3 : The tetrahydropyran derivative of formula (V) of step 2 is reacted with a dialkyl oxalate / malonate / succinate / ethyl pyruvate to obtain a regioisomeric mixture of compounds of formula (I) where n = 0,1,2. wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0165] R2 = an alkyl or alkylidene group up to 7-carbon atoms

[0166] M = -Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl. Said dialkyl oxalate is advantageously selected from dimethyl, Diethyl, di-i-propyl, diallyl, di-n-butyl or di-iso-butyl oxalate. R = -OMe, -OEt, -Oi-Pr, -O-nPr, -O-allyl, -O-isobutyl, or - O-nButyl.

[0167] Said dialkyl malonate / succinate is also advantageously selected from dimethyl, Diethyl, di-i- propyl, diallyl, di-n-butyl or di-iso-butyl oxalate. R = -OMe, -OEt, -Oi-Pr, -O-nPr, -O-allyl, - O-isobutyl, or -O-nButyl.

[0168] This step can advantageously be performed in the presence of a catalytic amount of TSA or methanesulfonic acid or sulfuric acid, leading to the opening of the tetrahydropyran ring.

[0169] Optional and additional Step 4: The regioisomeric mixture of oxalates / pyruvate / malonate / succinate (I) of step 3 is hydrogenated in the presence of Raney nickel or Palladium on carbon and hydrogen to afford saturated oxalate derivatives of formula (II) where n = 0, 1, 2 wherein Ri = H or an alkyl group up to 7-carbon atoms

[0170] R2 = an alkyl group up to 7-carbon atoms

[0171] M = -Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl.

[0172] This step can advantageously be performed under pressure (under 200 psi pressure) and at elevated temperature (e.g. between 100 and 130°C, for example around 120°C).

[0173] Optional and additional Step 5 (following step 3): The regioisomeric mixture of oxalates / pyruvate / malonate / succinate (I) of step 3 are hydrolyzed to give a regioisomeric mixture of alcohols of formula (VII).

[0174] VII wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0175] R2 = an alkyl or alkylidene group up to 7-carbon atoms

[0176] This step can advantageously be performed in the presence of aqueous NaOH. Optional and additional Step 6: The regioisomeric mixture of alcohols of formula (VII) are reacted with dialkyl mal onates (n = 1, M = -O-alkyl) or dialkyl succinates (n = 2, M = -O-alkyl) or ethyl pyruvate (n = 0 and M = Me) to afford a regioisomeric mixture of compounds of formula (I)

[0177] When n = 0, M = Me

[0178] When n = 1 or 2; M = -Oalkyl

[0179] Here, M = -OMe, -OEt, -O / -Pr, -On-Pr,

[0180] -OAllyl, -On-Bu, -O / -Bu wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms

[0181] R2 = an alkyl or alkylidene group up to 7-carbon atoms.

[0182] Higher di-alkyl groups can be used for the malonates / succinates / pyruvates in step 6 (for example di-z-propyl, diallyl, di - / / -butyl or di-i.w-butyl), dimethyl or diethyl are advantageously selected.

[0183] Optional and additional Step 7: The regioisomeric mixture of mal onates or succinates or pyruvates of formula (I) of step 6 are hydrogenated to afford compounds of formula (II): mal onates (n = 1, M = -O-alkyl) or succinates (n = 2, M = -O-alkyl) or pyruvate (n = 0 and M = Me).

[0184] When n = 0, M = Me

[0185] When n = 1 or 2; M = -Oalkyl

[0186] Here, M = -OMe, -OEt, -O / -Pr, -On-Pr,

[0187] -OAllyl, -On-Bu, -O / -Bu wherein Ri = H or an alkyl group up to 7-carbon atoms

[0188] R2 = an alkyl group up to 7-carbon atoms

[0189] This step can advantageously be performed in the presence of Raney nickel or Palladium on carbon and hydrogen. This step can advantageously be performed under pressure (under 200 psi pressure) and at elevated temperature (e.g. between 100 and 130°C, for example around 120°C).

[0190] Synthetic procedures and characterization data of some selected compounds are given below.

[0191] Examples:

[0192] Example 1:

[0193] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl oxalate (compound 1), ethyl (3,5,7-trimethyloct-4-en-l-yl) oxalate (compound 2) and ethyl (3,5,7-trimethyloct-5-en-l- yl) oxalate (compound 3) using 4-methylpentan-2-one and isoprenol

[0194] Step-1: Synthesis of a mixture of 2-isobutyl-2-methyl-4-methylenetetrahydro-2Z7-pyran, 2-isobutyl-2,4-dimethyl-3,6-dihydro-2Z7-pyran and 6-isobutyl-4,6-dimethyl-3,6-dihydro- 2H- pyran:

[0195] To 4-methylpentan-2-one (200.0 g, 1.99 mol) was added methanesulfonic acid (57.3 g, 0.59 mol) over 15 min at 25 °C. The reaction mixture was stirred 15 min and to it was added 3- methylbut-3-en-l-ol (206.5 g, 2.39 mol) over 30 min at 25 °C. An exotherm was generated during the addition, which was controlled by external cooling with water. After completion of addition, 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% aqueous sodium bicarbonate solution followed by washing with water (100 mL) and saturated brine (2 x 100 mL). The crude residue (345.0 g) containing 57% product by GC analysis, was distilled to afford 137.5 g (41% yield) of desired product.

[0196] IR (Neat): 2953.5, 1719.0, 1609.4, 1447.6 cm’1

[0197] ’H NMR (400 MHz, CDCh): 8 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, 2 H), 1.10-1.08 (m, 3 H), 0.91- 0.82 (m, 6 H).

[0198] GC-MS (m / z): 168.2 (M+), 153.1, 140.1, 111.1

[0199] Step-2: Synthesis of 2-isobutyl-2.4-dimethyltetr:ihydro-2 / / -pyr:in (V)

[0200] To a solution of a mixture from step-1 (218.0 g, 1.29 mol) in 2-propanol (110 mL) in an autoclave was added Raney nickel (10.6 g, 0.12 mol). The reaction mixture heated at 120 °C under 200 psi pressure of hydrogen and maintained for 18 h. The reaction mixture was cooled to 30 °C and filtered through a bed of hyflow. The hyflow bed was washed with 2-propanol (2 x 50 mL). The organic layer was concentrated to afford 217.0 g (96% yield) of desired product. IR (Neat): 2951.2, 1457.2, 1373.2 cm’1

[0201] ’H NMR (400 MHz, CDCh): 8 3.66 - 3.58 (m, 2 H), 1.80 - 1.73 (m, 3 H), 1.52 - 1.34 (m, 4

[0202] H), 1.21 - 1.14 (m, 4 H), 0.99 - 0.84 (m, 9 H).

[0203] GC-MS (m / z): 171.1 (M+), 155.2, 113.1.

[0204] Step-3: Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl oxalate (compound

[0205] I), ethyl (3,5,7-trimethyloct-4-en-l-yl) oxalate (compound 2) and ethyl (3,5,7- trimethyloct-5-en-l-yl) oxalate (compound 3):

[0206] A solution of 2-isobutyl-2,4-dimethyltetrahydro-2J / -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. Ethanol formed was removed using downward distillation. The reaction mixture was cooled to room temperature, washed with water (3 x 100 ml) followed by washing with brine. Excess diethyl oxalate was removed by vacuum distillation at 5 mbar pressure and top temperature 48-52 °C. Desired product in the form of regioisomeric mixture was obtained using 1.0 mbar vacuum and top temperature 80-85 °C to afford (98.0 g, 60%) of desired compound as colourless liquid.

[0207] Odor profile: Musky, woody, powdery, dry.

[0208] IR (Neat): 2957.7, 1769.1, 1743.2 cm’1

[0209] ‘HNMR (400 MHz, CDCh): 6 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).

[0210] GC-MS (m / z): 270.1 (M+), 252.2, 197.2, 152.2

[0211] Example 2:

[0212] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl malonate (compound-4), ethyl (3,5,7-trimethyloct-4-en-l-yl) malonate (compound 5), ethyl (3,5,7-trimethyloct-5- en-l-yl) malonate (compound-6):

[0213] A solution of 2-isobutyl-2,4-dimethyltetrahydro-2J / -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. Ethanol formed was removed using downward distillation. The reaction mixture was cooled to room temperature, washed with water (3 x 100 ml) followed by washing with brine. Excess diethyl malonate was removed by vacuum distillation at 5 mbar pressure and top temperature 52-55 °C. Desired product in the form of regioisomeric mixture was obtained using 1.0 mbar vacuum and top temperature 85-90 °C to afford (66.8 g, 40%) of desired compound as colourless liquid.

[0214] Example-2: Alternate Synthesis

[0215] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl malonate(compound-4), ethyl (3,5,7-trimethyloct-4-en-l-yl) malonate (compound 5), ethyl (3,5,7-trimethyloct-5- en-l-yl) malonate (compound-6):

[0216] Step 1:

[0217] General procedure for preparation of compounds of formula VII: To the solution of Example-1 (a compound of formula I) (1.0 eq) in MeOH and water (1 : 4) at 0 °C was slowly added solution of sodium hydroxide (2.2 eq) dissolved in water. The reaction mixture was stirred at room temperature for 3 h. After the reaction, methanol was evaporated using rota- evaporator and aqueous part was neutralized with dilute hydrochloric acid and extracted with ethyl acetate (3 x 200 mL). Combined organic layer was washed with water followed by brine. Solvent was evaporated on rota-evaporator to give alcohol of formula VII. Crude was used for next step without further purification.

[0218] Step 2:

[0219] This product was synthesized from alcohol of formula VII as follows.

[0220] 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. Ethanol formed was removed using downward distillation. The reaction mixture was cooled to room temperature, washed with water (3 x 100 ml) followed by washing with brine. Excess diethyl malonate was removed by vacuum distillation at 5 mbar pressure and top temperature 52-55 °C. Desired product in the form of regioisomeric mixture was obtained using 1.0 mbar vacuum and top temperature 85-90 °C to afford (49.3 g, 29%) of desired compound as colourless liquid.

[0221] Odor profile: Powdery, mild fruity, musky

[0222] IR (Neat): 2957.2, 2931.3, 1751.6, 1770.1, 1734.6 cm’1

[0223] 1H NMR (400 MHz, CDCh): 8 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, 1 H), 1.96-1.86 (m, 1 H), 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, 3 H), 0.96-0.78 (m, 9 H).

[0224] GC-MS (m / z): 284.1(M+), 239.2, 197.2, 152.2, 123.1.

[0225] Example-3:

[0226] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl succinate (compound 7), ethyl (3,5,7-trimethyloct-4-en-l-yl) succinate (compound 8), ethyl (3,5,7-trimethyloct-5- en-l-yl) succinate (compound 9):

[0227] This product in the form of regioisomeric mixture was obtained from a reaction described in step-3 in Example- 1, here diethyl succinate was used instead of diethyl oxalate.

[0228] Alternatively, this product was also synthesized in the form of regioisomeric mixture from alcohol of formula VII, using the method described in step-2 in example-2, here diethyl succinate was used instead of diethyl oxalate:

[0229] Odor profile: Spicy, musky

[0230] IR (Neat): 2957.0, 2870.7, 1734.6, 1156.0 cm’1

[0231] 'H-NMR (400 MHz, CDCh): 8 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= 5.6 Hz, 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).

[0232] GC-MS (m / z):298.1 (M+), 253.2, 152.2.

[0233] Example-4:

[0234] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl 2-oxopropanoate (compound 10), 3,5,7-trimethyloct-4-en-l-yl 2-oxopropanoate (compound 11), 3,5,7-trimethyloct-5- en-l-yl 2-oxopropanoate (compound 12):

[0235] This product in the form of regioisomeric mixture was obtained from a reaction described in step-3 in Example- 1, here ethyl pyruvate was used instead of diethyl oxalate.

[0236] Alternatively, this product in the form of regioisomeric mixture was also synthesized from alcohol of formula VII, using the method described in step-2 in example-2, here ethyl pyruvate was used instead of diethyl oxalate:

[0237] Odor profile: Strong musky, leathery, woody.

[0238] IR (Neat): 2956.8, 2929.6, 1730.4, 1136.6 cm’1 ’H-NMR (400 MHz, CDCh): 6 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).

[0239] GC-MS (m / z): 240.2, 197.1, 169.1, 151.1, 123.1, 95.1.

[0240] Example-5:

[0241] Synthesis of ethyl (3,5,7-trimethyloctyl) oxalate (compound 13):

[0242] To a solution of Example-1 (48.0 g, 0.18 mol) in ethanol (150 mL) in an autoclave was added 5% Pd / C (2.4 g) then hydrogen pressure 15 kg was applied, slight exotherm was observed. The reaction mixture was heated at 70 °C under 15 kg pressure of hydrogen and maintained for 7 h. The reaction mixture was cooled to room temperature and filtered through a bed of celite. The celite bed was washed with ethanol (2 x 50 mL). The organic layer was concentrated to afford 48.0 g of crude product. Crude product purified by vacuum distillation. Pure product was obtained using 1.0 mbar vacuum and top temperature 82-86 °C to afford the desired compound (40.0 g, 82%) as colourless liquid.

[0243] Odor profile: Musky, sweet, powdery.

[0244] IR (Neat): 2958.4, 2911.4, 1770.1, 1743.1, 1156.6 cm-1

[0245] 'H-NMR (400 MHz, CDCh): 8 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).

[0246] Example-6:

[0247] Synthesis of ethyl (3,5,7-trimethyloctyl) malonate (compound 14):

[0248] This product was synthesized from the products of example 2 using the method described in example-5.

[0249] Odor profile: woody, musky, fruity.

[0250] IR (Neat): 2957.3, 2910.3, 1751.7, 1735.0 cm’1

[0251] ’H NMR (400 MHz, CDCh): 6 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).

[0252] GC-MS (m / z): 287.3 (M+H), 241.2, 223.2, 205.1, 187.1, 133.1

[0253] Example 7:

[0254] Synthesis of a mixture of ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate (compound 15) and ethyl (3,5,6,6-tetramethylhept-4-en-l-yl) oxalate (compound 16) Step-1: Synthesis of 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:

[0255] To 3,3-dimethylbutan-2-one (200.0 g, 1.99 mol) was added methanesulfonic acid (57.31 g, 0.59 mol) over 15 min at 25 °C. The reaction mixture was stirred 15 min and to it was added 3-methylbut-3-en-l-ol (206.5 g, 2.39 mol) over 30 min at 25 °C. An exotherm was generated during the addition, which was controlled by external cooling with water. After completion of addition, 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% aqueous sodium bicarbonate solution followed by washing with water (100 mL) and saturated brine (2 x 100 mL). The crude residue (345.0 g) containing 57% product by GC analysis, was distilled to afford 124.3 g (37% yield) of desired product as a mixture of regioisomers.

[0256] IR (Neat): 2960.8, 2912.5, 1686.3, 1365.1 cm’1

[0257] 1H NMR (400 MHz, CDC13): 5 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).

[0258] Step-2: Synthesis of 2-(tert-butyl)-2,4-dimethyltetrahydro-2H-pyran

[0259] To a solution of a mixture from step-1 (218.0 g, 1.29 mol) in 2-propanol (110 mL) in an autoclave was added Raney nickel (10.6 g, 0.12 mol). The reaction mixture heated at 120 °C under 200 psi pressure of hydrogen and maintained for 18 h. The reaction mixture was cooled to 30 °C and filtered through a bed of hyflow. The hyflow bed was washed with 2-propanol (2 x 50 mL). The organic layer was concentrated to afford 209.5 g (95% yield) of desired product. IR (Neat): 2954.0, 2923.1, 1456.2, 1365.1 cm’1‘HNMR (400 MHz, CDC13): 5 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).

[0260] GC-MS (m / z): 171.1 (M+), 155.1, 113.1.

[0261] Step-3: Synthesis of a mixture of ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate (compound 15), ethyl (3,5,6,6-tetramethylhept-4-en-l-yl) oxalate (compound 16):

[0262] This product was synthesized as a mixture of regioisomers from 2-(tert-butyl)-2,4- dimethyltetrahydro-2H-pyran using the method described in step-3 in example-1 :

[0263] Odor profile: mild musky and powdery, fatty, floral.

[0264] IR (Neat): 2960.7, 2871.5, 1768.2, 1742.8, 1177.0 cm-1XH NMR (400 MHz, CDCh): 5 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= 1.2 Hz, 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).

[0265] GC-MS (m / z): 270.1 (M+), 214.1, 137.1, 95.1.

[0266] Example 8:

[0267] Synthesis of ethyl (3,5,6,6-tetramethylheptyl) oxalate (compound 17):

[0268] This product was synthesized from the product in example 7, using the method described in in example-5.

[0269] Odor profile: Mild musk, powdery.

[0270] IR (Neat): 2961.3, 2873.2, 1769.1, 1743.4, 1177.3 cm’1

[0271] ’H NMR (400 MHz, CDCh): 5 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, 11 H).

[0272] GC-MS (m / z): 273.1 (M+H), 239.2, 217.2, 143.1, 120.1.

[0273] Example 9:

[0274] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl isopropyl oxalate (Compound 18), isopropyl (3,5,7-trimethyloct-4-en-l-yl) oxalate (compound 19), isopropyl (3,5,7- trimethyloct-5-en-l-yl) oxalate (compound 20):

[0275] This product was synthesized as a mixture of regioisomers from the product in step-2 example 1 using the method described in step-3 in example- 1, here diisopropyl oxalate was used instead of diethyl oxalate:

[0276] Odor profile: Musky, woody, Cedar like

[0277] IR (Neat): 2957.3, 2871.0, 1766.4, 1740.4, 1173.1 cm’1

[0278] XH NMR (400 MHz, CDCh): 5 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, 9 H).

[0279] GC-MS (m / z): 284.1 (M+), 241.2, 197.1, 152.2, 123.1, 95.1.

[0280] Example 10:

[0281] Synthesis of isopropyl (3,5,7-trimethyloctyl) oxalate (compound 21):

[0282] This product was synthesized from the product from example 9 using the method described in example-5. Odor profile: Musky, woody

[0283] IR (Neat): 2957.3, 2911.2, 1766.9, 1740.8, 1174.5 cm’1

[0284] ‘H NMR (400 MHz, CDCh): 6 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).

[0285] Example 11:

[0286] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl propyl oxalate (compound 22), propyl (3,5,7-trimethyloct-4-en-l-yl) oxalate (compound 23), propyl (3,5,7-trimethyloct- 5-en-l-yl) oxalate (compound 24):

[0287] This product was synthesized as a mixture of regioisomers from the product in step-2 example 1 using the method described in step-3 in example-1, here dipropyl oxalate was used instead of diethyl oxalate:

[0288] Odor profile: Musky, woody

[0289] IR (Neat): 2958.7, 2871.7, 1769.5, 1743.1, 1169.8 cm-1

[0290] ‘HNMR (400 MHz, CDCh): 8 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).

[0291] GC-MS (m / z): 284.1 (M+), 266.1, 197.1, 152.2.

[0292] Example 12:

[0293] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl isobutyl oxalate (compound 25), isobutyl (3,5,7-trimethyloct-4-en-l-yl) oxalate (compound 26), isobutyl (3,5,7- trimethyloct-5-en-l-yl) oxalate (compound 27):

[0294] This product was synthesized as a mixture of regioisomers from the product in step-2 example

[0295] 1 using the method described in step-3 in example-1, here diisobutyl oxalate was used instead of diethyl oxalate:

[0296] Odor profile: Woody, smoky, Musky, animalic like

[0297] IR (Neat): 2958.4, 2872.6, 1769.8, 1742.7, 1157.2 cm’1

[0298] ‘HNMR (400 MHz, CDCh): 6 5.01 -4.82 (m, 1 H), 4.34 - 4.18 (m, 2 H), 4.02 (d, J= 6.8 Hz,

[0299] 2 H), 2.55 - 2.46 (m, 1 H), 2.07 - 1.53 (m, 10 H), 0.99 - 0.80 (m, 14 H).

[0300] GC-MS (m / z): 299.2 (M+H), 280.1, 197.2, 137.1.

[0301] Example 13:

[0302] Synthesis of isobutyl (3,5,7-trimethyloctyl) oxalate (compound 28): This product was synthesized from the product from example 12 using the method described in example-5.

[0303] Odor profile: Musky, mild woody

[0304] IR (Neat): 2958.4, 2911.4, 1770.1, 1743.1, 1156.6 cm-1

[0305] ’H NMR (400 MHz, CDCh): 8 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).

[0306] Example 14:

[0307] Synthesis of a mixture of 3,7-dimethyl-5-methyleneoctyl methyl oxalate (compound 29), methyl (3,5,7-trimethyloct-4-en-l-yl) oxalate (compound 30), methyl (3,5,7-trimethyloct- 5-en-l-yl) oxalate (compound 31):

[0308] This product was synthesized as a mixture of regioisomers from the product in step-2 example 1 using the method described in step-3 in example-1, here dimethyl oxalate was used instead of diethyl oxalate:

[0309] Odor profile: Woody, musky, oily

[0310] ’H NMR (400 MHz, CDCh): 6 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, 9 H).

[0311] GC-MS (m / z): 256.1 (M+), 238.2, 197.2, 152.2, 123.1, 95.1

[0312] Example 15:

[0313] Synthesis of methyl (3,5,7-trimethyloctyl) oxalate (compound 32):

[0314] This product was synthesized from the product from example 14 using the method described in example-5.

[0315] Odor profile: Strong musky, woody

[0316] IR (Neat): 2957.2, 2911.0, 1772.9, 1744.7, 1155.6 cm-1

[0317] ‘H NMR (400 MHz, CDCh): 6 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).

[0318] GC-MS (m / z): 259.1 (M+H), 199.2, 125.1, 97.1

[0319] Example 16:

[0320] Synthesis of a mixture of ethyl (3-methyl-5-methyleneoctyl) oxalate (compound 33), 3,5- dimethyloct-4-en-l-yl ethyl oxalate (compound 34) and 3,5-dimethyloct-5-en-l-yl ethyl oxalate (compound 35)

[0321] Step-1: Synthesis of a mixture of 2-methyl-4-methylene-2-propyltetrahydro-2 / / -pyr:in. 4,6-dimethyl-6-propyl-3,6-dihydro-2EZ-pyran, 2,4-dimethyl-2-propyl-3,6-dihydro-2EZ- pyran: To a solution of pentan-2-one (200.0 g, 2.32 mol) was slowly added triflic acid (10.44 g, 0.070 mol) over 20 min at 25 °C and the reaction mixture was stirred for 15 min. Then 3- methylbut-3-en-l-ol (205.0 g, 2.32 mol) was added over 30 min at room temperature. An exotherm was generated during addition, which was controlled by external cooling with water. After addition, the reaction mixture was heated to 75-80 °C for 15 h. The reaction mixture was cooled to room temperature and then to it was added (500 mL) methyl tert-butyl ether. The organic layer was washed with 5% aqueosus sodium bicarbonate solution (100 mL) followed by water (4 x 200 mL) to neutral pH. The organic solvent was evaporated under reduced pressure to afford 260 g of crude product. The crude product was distilled (70-71°C at 17-13 mbar) to afford a regioisomeric mixture of desired products (98.0 g, 31 %).

[0322] ’H NMR (400 MHz, CDCh): 8 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, 4 H).

[0323] GC-MS (m / z): 154.2 (M+).

[0324] Step-2: Synthesis of 2.4-diniethyl-2-propyltetrahydro-2 / / -pyr:in:

[0325] To a solution of a mixture of products obtained in step-1 (122.0 g, 0.79 mol) in isopropanol (244 mL) was added Raney Ni (6.77 g, 0.079 mol) in an autoclave. The reaction mixture was heated at 80 °C, under 200 psi pressure of hydrogen gas for 5 h. Then the reaction mixture was heated at 120°C using 300 psi hydrogen pressure for 16 h. After completion of the reaction, 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 afford the desired product (84.5 g, 68%).

[0326] ‘HNMR (400 MHz, CDCh): 6 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).

[0327] GC-MS (m / z): 155.2 (M+), 113.1.

[0328] Step 3: Synthesis of a mixture of ethyl (3-methyl-5-methyleneoctyl) oxalate (compound 33), 3,5-dimethyloct-4-en-l-yl ethyl oxalate (compound 34) and 3,5-dimethyloct-5-en-l-yl ethyl oxalate (compound 35):

[0329] This product was synthesized as a mixture of regioisomers from 2,4-dimethyl-2- propyltetrahydro-2H-pyran using the method described in step-3 in example-1 :

[0330] Odor profile: Musky, woody.

[0331] ’H NMR (400 MHz, CDCh): 6 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, 9 H). GC-MS (m / z): 256.1 (M+), 238.2, 183.2, 138.1, 111.1, 95.1.

[0332] Example 17:

[0333] Synthesis of a mixture of ethyl (3-methyl-5-methylenedecyl) oxalate (compound 36), 3,5- dimethyldec-4-en-l-yl ethyl oxalate (compound 37), 3,5-dimethyldec-5-en-l-yl ethyl oxalate (compound-38):

[0334] Step-1: Synthesis of 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:

[0335] To heptan-2-one (200.0 g, 1.75 mol) was added methanesulfonic acid (50.4 g, 0.52 mol) over 15 min at 25 °C. The reaction mixture was stirred 15 min and to it was added 3-methylbut-3- en-l-ol (180.9 g, 2.1 mol) over 30 min at 25 °C. An exotherm was generated during the addition, which was controlled by external cooling with water. After completion of addition, 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% aqueous sodium bicarbonate solution followed by washing with water (100 mL) and saturated brine (2 x 100 mL). The crude residue (370.0 g) containing 65% product by GC analysis, was distilled to afford 200.9 g (63% yield) of desired product.

[0336] IR (Neat): 2932.5, 2862.6, 1680.8, 1456.2, 1378.0 cm’1

[0337] ’H NMR (400 MHz, CDCh): 8 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, 8 H), 1.15 (s, 3 H), 0.90 - 0. 85 (m, 3 H).

[0338] GC-MS (m / z): 182.2 (M+), 167.2, 139.1, 111.1.

[0339] Step-2: Synthesis of 2,4-dimethyl-2-pentyltetrahydro-2H-pyran

[0340] To a solution of a mixture from step-1 (100.0 g, 0.55 mol) in 2-propanol (50 mL) in an autoclave was added Raney nickel (4.69 g, 0.054mol). The reaction mixture was heated at 120 °C under 200 psi pressure of hydrogen and maintained for 18 h. The reaction mixture was cooled to 30 °C and filtered through a bed of hyflow. The hyflow bed was washed with 2- propanol (2 x 50 mL). The organic layer was concentrated to afford 88.8 g (88% yield) of desired product.

[0341] IR (Neat): 2928.4, 2860.9, 1457.4, 1375.1 cm’1

[0342] 1H NMR (400 MHz, CDCh): 6 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).

[0343] GC-MS (m / z): 183.2 (M ), 169.2, 113.1. Step-3: Synthesis of a mixture of ethyl (3-methyl-5-methylenedecyl) oxalate (compound 36), 3,5-dimethyldec-4-en-l-yl ethyl oxalate (compound 37), 3,5-dimethyldec-5-en-l-yl ethyl oxalate (compound-38):

[0344] This product was synthesized as a mixture of regioisomers from 2,4-dimethyl-2- pentyltetrahydro-2H-pyran using the method described in step-3 in example-1 :

[0345] Odor profile: Musky, woody.

[0346] IR (Neat): 2959.0, 2928.4, 1769.0, 1743.2, 1157.6 cm’1

[0347] ’H NMR (400 MHz, CDCh): 8 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, 9 H).

[0348] GC-MS (m / z): 284.1 (M+), 266.1, 211.2, 166.2, 123.1, 95.1.

[0349] Example 18:

[0350] Synthesis of 3,5-dimethyloctyl ethyl oxalate (compound 39):

[0351] This product was synthesized from product of example 16 and using reaction conditions of example 5:

[0352] Odor profile: Musky, smoky, woody, ambery, sweet.

[0353] IR (Neat): 2959.1, 2928.5, 1768.1, 1742.6 cm’1

[0354] ’H NMR (400 MHz, CDCh): 6 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).

[0355] GC-MS (m / z): 256.1(M+), 238.1, 183.1, 138.1, 109.1.

[0356] Example 19:

[0357] Synthesis of 3,5-dimethyldecyl ethyl oxalate (compound 40):

[0358] This product was synthesized from product of example 17 and using reaction conditions of example 5:

[0359] Odor profile: Sweet, musky, woody.

[0360] IR (Neat): 2958.8, 2926.3, 1769.5, 1743.8 cm’1

[0361] ’H NMR (400 MHz, CDCh): 6 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, 9 H).

[0362] GC-MS (m / z): 286.1 (M+), 268.2, 213.2, 139.2, 115.1, 97.1.

[0363] Example 20: Synthesis of a mixture of 3,7-dimethyloct-4-en-l-yl ethyl oxalate (compound 41) and 3,7- dimethyloct-5-en-l-yl ethyl oxalate (compound 42):

[0364] This product was synthesized as a mixture of regioisomers from 2-isobutyl-4- methyltetrahydro-2H-pyran using the method described in step-3 in example-1.

[0365] Odor profile: musky, fruity, powdery

[0366] IR (Neat): 2958.7, 2931.5, 1768.6, 1742.7 cm’1

[0367] ’H NMR (400 MHz, CDCh): 8 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).

[0368] GC-MS (m / z): 254.1 (M-H), 183.1, 139.2, 123.1, 95.1

[0369] Few compounds encompassed by the scope of the present invention are disclosed herewith. It must be noted that the disclosed compounds do not limit the scope of the present invention.

[0370] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to person skilled in the art, the invention should be construed to include everything within the scope of the disclosure.

[0371] COMPOSITION EVALUATION EXAMPLES:

[0372] In the following invention, as shown in Table-1 : Composition (C) containing the compound from Example-1 (a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl oxalate, ethyl (3,5,7- trimethyloct-4-en-l-yl) oxalate and ethyl (3,5,7-trimethyloct-5-en-l-yl) oxalate), was compared with compositions of commercially available materials like 3,7-dimethyloct-6-en-l- yl ethyl oxalate (citronellyl ethoxylate, composition G), Ethylene brassylate (composition B) and Romandolide (Composition I) respectively. (Composition A = blank), DPG = Dipropylene glycol.

[0373] Table -1 : Example-1 (Comp-1 / 2 / 3) in Shampoo:

[0374]

[0375] When compound from Example- 1 was dosed at 10% w / w in shampoo, an impactful musky character was imparted to the composition C. Compared to other compositions B, G and I which contained commercial compounds ethylene brassylate, 3,7-dimethyloct-6-en-l-yl ethyl oxalate (citronellyl ethoxylate) and Romandolide respectively, composition C had stronger, very rounded and fuller character. On an odor strip, compound from Example- 1 was found to be much stronger than ethylene brassylate, citronellyl ethoxylate and Romandolide.

[0376] In the following invention, as shown in Table-2: Composition (A) containing the compound from Example-1 (a mixture of 3,7-dimethyl-5-methyleneoctyl ethyl oxalate, ethyl (3,5,7- trimethyloct-4-en-l-yl) oxalate and ethyl (3,5,7-trimethyloct-5-en-l-yl) oxalate), was compared with composition of commercially available Habanolide ((12E)-Oxacyclohexadec- 12-en-2-one, composition B) with Composition C serving as Blank (Isopropyl myristate IPM). Table -2-: Example-1 (Comp- 1 / 2 / 3) in Shampoo: In the above floral fruity musky accord, when composition A containing Example-1 is compared against composition B containing commercial compound Habanolide, it was observed that compared to Habanolide, the addition of Example-1 imparted more natural volume and brought more richness and creaminess to this accord. In fact, it was found that use of Example-1 in many accords resulted in enhanced richness and creaminess to those accords. Thus, Example- 1 can be used across various applications due to its high performance.

[0377] In the following invention, as shown in Table 3, composition (D) containing the compound from Example-5 (ethyl 3,5,7-trimethyloctyl oxalate), was compared with compositions of materials like composition H (3,7-dimethyloctyl ethyl oxalate (Dihydrocitronellyl ethoxylate)), composition B (Ethylene brassylate) and Example I (Romandolide) respectively. (Composition A = blank), DPG = Dipropylene glycol.

[0378] When compound from Example-5 (compound 13: ethyl 3,5,7-trimethyloctyl oxalate) was dosed at 10% w / w in shampoo, an impactful musky character was imparted to the composition. Compared to other compositions B, H and I which contained commercial compounds ethylene brassylate, 3,7-dimethyloctyl ethyl oxalate (Dihydrocitronellyl ethoxylate) and Romandolide respectively, composition D had strong, well-rounded character. On an odor strip, compound from Example-5 was found to be stronger than ethylene brassylate, 3,7-dimethyloctyl ethyl oxalate and Romandolide.

[0379] Table -3: Example-5 (Compound-13) in Shampoo:

Claims

CLAIMS:

1. Compounds of general formula (I) and / or formula (II)whereinRi = H or an alkyl or alkylidene group up to 7-carbon atomsR2 = an alkyl or alkylidene group up to 7-carbon atomsM = Me, -OMe, -OEt, -Oz-Pr, -O-z / Pr, -O-allyl, -O-isobutyl, -O-z / Butyl the dotted line represents alternate positions of double bond, and n= 0, 1 or 2, with the proviso that compounds of general formula (I) and / or formula (II) cannot be 3,7-dimethyloctyl ethyl oxalate and 3,7-dimethyloctyl 3-oxobutanoate.

2. Compounds according to claim 1 wherein Ri and R2 are independently selected from a group consisting of methyl, ethyl, / / -propyl, isopropyl, / / -butyl, isobutyl, tertiary-butyl, / / -pentyl, n- hexyl, methylidene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, hexylidene, heptylidine.

3. Compounds according to claim 1 selected from the following compounds:1) 3,7-dimethyl-5-methyleneoctyl ethyl oxalate2) ethyl (3,5,7-trimethyloct-4-en-l-yl) oxalate3) ethyl (3,5,7-trimethyloct-5-en-l-yl) oxalate4) 3,7-dimethyl-5-methyleneoctyl ethyl malonate5) ethyl (3,5,7-trimethyloct-4-en-l-yl) malonate6) ethyl (3,5,7-trimethyloct-5-en-l-yl) malonate7) 3,7-dimethyl-5-methyleneoctyl ethyl succinate8) ethyl (3,5,7-trimethyloct-4-en-l-yl) succinate9) ethyl (3,5,7-trimethyloct-5-en-l-yl) succinate10) 3,7-dimethyl-5-methyleneoctyl 2-oxopropanoate11) 3,5,7-trimethyloct-4-en-l-yl 2-oxopropanoate12) 3,5,7-trimethyloct-5-en-l-yl 2-oxopropanoate13) ethyl (3,5,7-trimethyloctyl) oxalate14) ethyl (3,5,7-trimethyloctyl) malonate15) ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate16) ethyl (3,5,6,6-tetramethylhept-4-en-l-yl) oxalate17) ethyl (3, 5, 6, 6-tetram ethylheptyl) oxalate18) 3,7-dimethyl-5-methyleneoctyl isopropyl oxalate19) isopropyl (3,5,7-trimethyloct-4-en-l-yl) oxalate20) isopropyl (3,5,7-trimethyloct-5-en-l-yl) oxalate21) isopropyl (3,5,7-trimethyloctyl) oxalate22) 3,7-dimethyl-5-methyleneoctyl propyl oxalate23) propyl (3,5,7-trimethyloct-4-en-l-yl) oxalate24) propyl (3,5,7-trimethyloct-5-en-l-yl) oxalate25) 3,7-dimethyl-5-methyleneoctyl isobutyl oxalate26) isobutyl (3,5,7-trimethyloct-4-en-l-yl) oxalate27) isobutyl (3,5,7-trimethyloct-5-en-l-yl) oxalate28) isobutyl (3,5,7-trimethyloctyl) oxalate29) 3,7-dimethyl-5-methyleneoctyl methyl oxalate30) methyl (3,5,7-trimethyloct-4-en-l-yl) oxalate31) methyl (3,5,7-trimethyloct-5-en-l-yl) oxalate32) methyl (3,5,7-trimethyloctyl) oxalate33) ethyl (3-methyl-5-methyleneoctyl) oxalate34) 3,5-dimethyloct-4-en-l-yl ethyl oxalate35) 3,5-dimethyloct-5-en-l-yl ethyl oxalate36) ethyl (3-methyl-5-methylenedecyl) oxalate37) 3,5-dimethyldec-4-en-l-yl ethyl oxalate38) 3,5-dimethyldec-5-en-l-yl ethyl oxalate39) 3,5-dimethyloctyl ethyl oxalate40) 3,5-dimethyldecyl ethyl oxalate41) 3,7-dimethyloct-4-en-l-yl ethyl oxalate42) 3,7-dimethyloct-5-en-l-yl ethyl oxalate43) ethyl (5-ethyl-3-methylhept-4-en-l-yl) oxalate44) ethyl (5-ethyl-3-methylhept-5-en-l-yl) oxalate45) ethyl (5-ethyl-3-methylheptyl) oxalate46) ethyl (3,5,6-trimethylhept-4-en-l-yl) oxalate47) ethyl (3,5,6-trimethylhept-5-en-l-yl) oxalate48) 3,6-dimethyl-5-methyleneheptyl ethyl oxalate49) 3,5-dimethylhept-4-en-l-yl ethyl oxalate50) 3,5-dimethylhept-5-en-l-yl ethyl oxalate51) ethyl (3-methyl-5-methyleneheptyl) oxalate52) ethyl (3-methyl-5-methylenenonyl) oxalate53) 3,5-dimethylnon-4-en-l-yl ethyl oxalate54) 3,5-dimethylnon-5-en-l-yl ethyl oxalate55) ethyl (3-methyl-5-propyloct-4-en-l-yl) oxalate56) ethyl (3-methyl-5-propyloct-5-en-l-yl) oxalate57) ethyl (3-methyl-5-propyloctyl) oxalate58) ethyl (3,5,9-trimethyldec-4-en-l-yl) oxalate59) 3,9-dimethyl-5-methylenedecyl ethyl oxalate60) ethyl (3,5,9-trimethyldec-5-en-l-yl) oxalate61) ethyl (5-isobutyl-3,7-dimethyloct-4-en-l-yl) oxalate62) ethyl (5-isobutyl-3,7-dimethyloct-5-en-l-yl) oxalate63) ethyl (5-isobutyl-3,7-dimethyloctyl) oxalate64) ethyl (5-ethyl-3-methylhept-4-en-l-yl) malonate65) ethyl (5-ethyl-3-methylhept-5-en-l-yl) malonate66) 5-ethyl-3-methylhept-4-en-l-yl 2-oxopropanoate67) 5-ethyl-3-methylhept-5-en-l-yl 2-oxopropanoate68) ethyl (3,5,6-trimethylhept-4-en-l-yl) malonate69) ethyl (3,5,6-trimethylhept-5-en-l-yl) malonate70) 3,6-dimethyl-5-methyleneheptyl ethyl malonate71) ethyl (5-isopropyl-3,6-dimethylhept-4-en-l-yl) oxalate72) ethyl (5-isopropyl-3,6-dimethylhept-5-en-l-yl) oxalate73) ethyl (5-isopropyl-3,6-dimethylhept-5-en-l-yl) oxalate74) ethyl (5-isopropyl-3,6-dimethylheptyl) oxalate75) ethyl (3-methyloct-4-en-l-yl) oxalate76) ethyl (3-methyloct-5-en-l-yl) oxalate77) ethyl (3-methylnon-4-en-l-yl) oxalate78) ethyl (3-methylnon-5-en-l-yl) oxalate79) ethyl (3-methyldec-4-en-l-yl) oxalate80) ethyl (3-methyldec-5-en-l-yl) oxalate81) ethyl (3-methylundec-4-en-l-yl) oxalate82) ethyl (3-methylundec-5-en-l-yl) oxalate83) ethyl (3-methyldodec-4-en-l-yl) oxalate84) ethyl (3-methyldodec-5-en-l-yl) oxalate85) 3,6-dimethylhept-4-en-l-yl ethyl oxalate86) 3,6-dimethylhept-5-en-l-yl ethyl oxalate87) ethyl (3,6,7-trimethyloct-5-en-l-yl) oxalate88) ethyl (3,6,7-trimethyloct-4-en-l-yl) oxalate89) 3,6-dimethyloct-5-en-l-yl ethyl oxalate90) 3,6-dimethyloct-4-en-l-yl ethyl oxalate91) 3,6-dimethylnon-5-en-l-yl ethyl oxalate92) 3,6-dimethylnon-4-en-l-yl ethyl oxalate93) 3,6-dimethyldec-5-en-l-yl ethyl oxalate94) 3,6-dimethyldec-4-en-l-yl ethyl oxalate95) 3,6-dimethylundec-5-en-l-yl ethyl oxalate96) 3,6-dimethylundec-4-en-l-yl ethyl oxalate.

4. Compounds according to claim 1 selected from the following compounds:1) 3,7-dimethyl-5-methyleneoctyl ethyl oxalate2) ethyl (3,5,7-trimethyloct-4-en-l-yl) oxalate3) ethyl (3,5,7-trimethyloct-5-en-l-yl) oxalate4) 3,7-dimethyl-5-methyleneoctyl ethyl malonate5) ethyl (3,5,7-trimethyloct-4-en-l-yl) malonate6) ethyl (3,5,7-trimethyloct-5-en-l-yl) malonate7) 3,7-dimethyl-5-methyleneoctyl ethyl succinate8) ethyl (3,5,7-trimethyloct-4-en-l-yl) succinate9) ethyl (3,5,7-trimethyloct-5-en-l-yl) succinate10) 3,7-dimethyl-5-methyleneoctyl 2-oxopropanoate11) 3,5,7-trimethyloct-4-en-l-yl 2-oxopropanoate12) 3,5,7-trimethyloct-5-en-l-yl 2-oxopropanoate13) ethyl (3,5,7-trimethyloctyl) oxalate14) ethyl (3,5,7-trimethyloctyl) malonate15) ethyl (3,6,6-trimethyl-5-methyleneheptyl) oxalate16) ethyl (3,5,6,6-tetramethylhept-4-en-l-yl) oxalate17) ethyl (3, 5, 6, 6-tetram ethylheptyl) oxalate18) 3,7-dimethyl-5-methyleneoctyl isopropyl oxalate19) isopropyl (3,5,7-trimethyloct-4-en-l-yl) oxalate20) isopropyl (3,5,7-trimethyloct-5-en-l-yl) oxalate21) isopropyl (3,5,7-trimethyloctyl) oxalate22) 3,7-dimethyl-5-methyleneoctyl propyl oxalate23) propyl (3,5,7-trimethyloct-4-en-l-yl) oxalate24) propyl (3,5,7-trimethyloct-5-en-l-yl) oxalate25) 3,7-dimethyl-5-methyleneoctyl isobutyl oxalate26) isobutyl (3,5,7-trimethyloct-4-en-l-yl) oxalate27) isobutyl (3,5,7-trimethyloct-5-en-l-yl) oxalate28) isobutyl (3,5,7-trimethyloctyl) oxalate29) 3,7-dimethyl-5-methyleneoctyl methyl oxalate30) methyl (3,5,7-trimethyloct-4-en-l-yl) oxalate31) methyl (3,5,7-trimethyloct-5-en-l-yl) oxalate32) methyl (3,5,7-trimethyloctyl) oxalate33) ethyl (3-methyl-5-methyleneoctyl) oxalate34) 3,5-dimethyloct-4-en-l-yl ethyl oxalate35) 3,5-dimethyloct-5-en-l-yl ethyl oxalate36) ethyl (3-methyl-5-methylenedecyl) oxalate37) 3,5-dimethyldec-4-en-l-yl ethyl oxalate38) 3,5-dimethyldec-5-en-l-yl ethyl oxalate39) 3,5-dimethyloctyl ethyl oxalate40) 3,5-dimethyldecyl ethyl oxalate41) 3,7-dimethyloct-4-en-l-yl ethyl oxalate42) 3,7-dimethyloct-5-en-l-yl ethyl oxalate5. Regioisomeric mixture of compounds of formula (I) according to any of claims 1 to 4.

6. Mixture of compounds of formula (I) and formula (II) according to any of claims 1 to 5.

7. Fragrance, flavor and / or deodorizing / masking compositions comprising a compound according to any of claims 1 to 4 or a mixture according to claim 5 or to claim 6.

8. Fragrance, flavor and / or deodorizing / masking compositions comprising a regioisomeric mixture according to claim 5.

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

10. Fragrance, flavor and / or deodorizing / masking composition according to claim 9 wherein the total content of the compound(s) of formula (I) and formula (II) together with the ester(s) and alcohol(s) is superior to 50 wt%.

11. Use of a fragrance, flavour and / or deodorizing / masking composition according to any of claims 7 to 10 in a perfumed or flavoured product exhibiting musky, woody, animalic and / or powdery type notes.

12. Use of a compound according to any of claims 1 to 4 or a mixture according to any of claims 5 or 6 in a perfumed or flavoured product exhibiting musky, woody, animalic and / or powdery type notes.

13. Process for preparation of the compounds of formula (I) and / or (II)(I) (II) whereinRi = H or an alkyl or alkylidene group up to 7-carbon atomsR-2 = an alkyl or alkylidene group up to 7-carbon atomsM = Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl the dotted line represents alternate positions of double bond, and n= 0, 1 or 2 comprising the following steps:• Step 1 : Reaction of compound of formula (III) with isoprenol to get a regioisomeric mixture of pyrans of formula (IV).wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms R2 = an alkyl or alkylidene group up to 7-carbon atoms,• Step 2: The regioisomeric mixture of pyrans (IV) of step 1 is hydrogenated in the presence of Raney nickel or Palladium on carbon and hydrogen to afford a tetrahydropyran derivative (V)wherein Ri = H or an alkyl group up to 7-carbon atoms R2 = an alkyl group up to 7-carbon atoms,• Step 3: The tetrahydropyran derivative of formula (V) of step 2 is reacted with a dialkyl oxalate / malonate / succinate / ethyl pyruvate to obtain a regioisomeric mixture of compounds of formula (I) where n = 0, 1, 2wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atomsR2 = an alkyl or alkylidene group up to 7-carbon atomsM = -Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl.

14. Process for preparation of the compounds of formula (I) and / or (II) according to claim 13 wherein the regioisomeric mixture of oxalates / pyruvate / malonate / succinate (I) of step 3 are- either hydrogenated (Step 4) in the presence of Raney nickel or Palladium on carbon and hydrogen to afford saturated oxalate / pyruvate / malonate / succinate derivatives of formula (II) where n = 0, 1, 2wherein Ri = H or an alkyl group up to 7-carbon atomsR2 = an alkyl group up to 7-carbon atomsM = -Me, -OMe, -OEt, -Oz-Pr, -O-zzPr, -O-allyl, -O-isobutyl, or -O-zzButyl, or hydrolyzed (Step 5) to give a regioisomeric mixture of alcohols of formula (VII)VII wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms R2 = an alkyl or alkylidene group up to 7-carbon atoms.

15. Process for preparation of the compounds of formula (I) and / or (II) according to claim 14 wherein the regioisomeric mixture of alcohols of formula (VII) from Step 5 are reacted (Step 6) with dialkyl mal onates (n = 1, M = -O-alkyl) or dialkyl succinates (n = 2, M = -O-alkyl) or ethyl pyruvate (n = 0 and M = Me) to afford a regioisomeric mixture of compounds of formula (I)When n = 0, M = MeWhen n = 1 or 2; M = -OalkylHere, M = -OMe, -OEt, -O / -Pr, -On-Pr,-OAllyl, -On-Bu, -O / -Bu wherein Ri = H or an alkyl or alkylidene group up to 7-carbon atoms R2 = an alkyl or alkylidene group up to 7-carbon atoms.

16. Process for preparation of the compounds of formula (I) and / or (II) according to claim 15 wherein the regioisomeric mixture of malonates or succinates or pyruvates of formula (I) ofstep 6 are hydrogenated (Step 7) to afford compounds of formula (II): mal onates (n = 1, M = - O-alkyl) or succinates (n = 2, M = -O-alkyl) or pyruvate (n = 0 and M = Me)When n = 0, M = MeWhen n = 1 or 2; M = -OalkylHere, M = -OMe, -OEt, -O / -Pr, -On-Pr,-OAllyl, -On-Bu, -O / -Bu wherein Ri = H or an alkyl group up to 7-carbon atoms R-2 = an alkyl group up to 7-carbon atoms.

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